CA1339817C - Curing and passivation of spin-on-glasses by a plasma process, and product produced thereby - Google Patents
Curing and passivation of spin-on-glasses by a plasma process, and product produced therebyInfo
- Publication number
- CA1339817C CA1339817C CA000601333A CA601333A CA1339817C CA 1339817 C CA1339817 C CA 1339817C CA 000601333 A CA000601333 A CA 000601333A CA 601333 A CA601333 A CA 601333A CA 1339817 C CA1339817 C CA 1339817C
- Authority
- CA
- Canada
- Prior art keywords
- sog
- layer
- film
- plasma
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000011521 glass Substances 0.000 title claims abstract description 29
- 238000002161 passivation Methods 0.000 title claims description 8
- 229910020175 SiOH Inorganic materials 0.000 claims abstract description 42
- 239000003039 volatile agent Substances 0.000 claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000004065 semiconductor Substances 0.000 claims abstract description 14
- 238000009987 spinning Methods 0.000 claims abstract description 13
- 230000001747 exhibiting effect Effects 0.000 claims abstract description 3
- 229910001868 water Inorganic materials 0.000 claims description 67
- 229920002120 photoresistant polymer Polymers 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000004020 conductor Substances 0.000 claims description 25
- 230000005684 electric field Effects 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 238000005260 corrosion Methods 0.000 claims description 7
- 230000007797 corrosion Effects 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052785 arsenic Inorganic materials 0.000 claims description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 239000006117 anti-reflective coating Substances 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 230000010287 polarization Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- KZNMRPQBBZBTSW-UHFFFAOYSA-N [Au]=O Chemical compound [Au]=O KZNMRPQBBZBTSW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 3
- 229910000413 arsenic oxide Inorganic materials 0.000 claims description 3
- 229960002594 arsenic trioxide Drugs 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001942 caesium oxide Inorganic materials 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001922 gold oxide Inorganic materials 0.000 claims description 3
- 229910003437 indium oxide Inorganic materials 0.000 claims description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 3
- 239000011253 protective coating Substances 0.000 claims description 3
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 3
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 230000001464 adherent effect Effects 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 claims description 2
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 claims 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims 2
- 229910003446 platinum oxide Inorganic materials 0.000 claims 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 2
- 239000000377 silicon dioxide Substances 0.000 claims 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000002019 doping agent Substances 0.000 claims 1
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical compound O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 239000010408 film Substances 0.000 description 64
- 239000010410 layer Substances 0.000 description 45
- 235000012431 wafers Nutrition 0.000 description 13
- 239000003570 air Substances 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 238000010943 off-gassing Methods 0.000 description 8
- -1 siloxanes Chemical class 0.000 description 8
- 238000009832 plasma treatment Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000001465 metallisation Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 210000000009 suboesophageal ganglion Anatomy 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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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
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
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- H—ELECTRICITY
- 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
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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
- H01L21/18—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
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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
- H01L21/02214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
- H01L21/02216—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
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- H—ELECTRICITY
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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
- H01L21/02296—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
- H01L21/02337—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 gas or vapour
- H01L21/0234—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 gas or vapour treatment by exposure to a plasma
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76822—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/291—Oxides or nitrides or carbides, e.g. ceramics, glass
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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
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- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02126—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
- H01L21/02129—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 the material being boron or phosphorus doped silicon oxides, e.g. BPSG, BSG or PSG
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
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- H—ELECTRICITY
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- 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
- H01L21/02172—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02178—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing aluminium, e.g. Al2O3
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02183—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing tantalum, e.g. Ta2O5
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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
- H01L21/02225—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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Abstract
A method of producing insulating layers over a semiconductor substrate comprising spinning a film of spin-on-glass (SOG) over a semiconductor substrate, precuring the film of SOG at an elevated temperature sufficient to remove the bulk of solvent and curing the film of SOG in a plasma in a plasma reactor of a type exhibiting a self-biased RF
discharge adjacent the SOG for a period of time sufficient to exclude the bulk of SiOH, organic volatiles and H2O from the layer.
discharge adjacent the SOG for a period of time sufficient to exclude the bulk of SiOH, organic volatiles and H2O from the layer.
Description
01 This invention relates to passivating or 02 dielectric layers formed of spin-on-glass that are 03 useful in semiconductor integrated circuits, liquid 04 crystal, electrochromic or electroluminescent 05 displays, as anti-reflective coatings, corrosion or 06 chemical protective coatings, a method for producing 07 such layers, and products incorporating one or more of 08 such layers.
09 Spin-on glasses (SOG) have been described as being able to be used for the purpose of 11 planarizing integrated circuits. Because of their 12 inherent filling and planarizing properties, their use 13 is particularly attractive as the size of 14 semiconductor integrated circuits decreases, and when multiple level metallization is needed.
16 Unfortunately, cured SOG has been found to 17 be unstable in moist air and water, tending to absorb 18 water and form silanol groups, SiOH.
19 SOG and its method of curing have been described in the article by A. Schiltz entitled 22 INTERCONNECTION DIELECTRIC PLANARIZATION, published in 23 "Microelectronic Engineering" 5 (1986) pp. 413-421 by 24 Elsevier Science Publishers BV (North Holland), and the article ~2 PLASMA-CONVERTED SPIN-ON-GLASS FOR
26 PLANARIZATION by A.D. Butherus et al, 27 September/October 1985, J. Vac. Sci. Technol. B3(5) 28 pp. 1352-1356.
29 In the article COMPARISON OF PROPERTIES OF
DIELECTRIC FILMS DEPOSITED BY VARIOUS METHODS by W.A.
31 Pliskin, J. Vac. Sci. Technol. Vol. 14 No. 5, 32 Sept./Oct. 1977, pp. 1065-1081, the SiOH and H20 33 content in various dielectric thin films is 34 described. In the article EVALUATIONS OF PLASMA
SILICON-OXIDE FILM (P-SiO) BY INFRARED ABSORPTION by 36 A. Takamatsu et al, J. Electro. Chem. Soc.:
37 Solid-State Science & Technology, Feb. 1986, pp.
01 443-445, the relationship between the presence of SiOH
02 and failure of semiconductor devices are described.
03 It is clear that the known process for 04 producing SOG produces SiOH, organic volatiles, and 05 H20 including solvents, alcohols, large organometallic 06 molecules and large organic molecules, which is o7 associated with corrosion of metallization lines in 08 contact with SOG, outgassing during metallization 09 resulting in via-poisoning, poor adhesion due to outgassing and other H20, organic volatiles, and SiOH
11 effects, cracking, peeling and flaking of films 12 deposited over SOG due to outgassing related pressure 13 buildup, low breakdown voltage of dielectric 14 combinations with SOG, lossy dielectric combinations with SOG, low density dielectrics due to the presence 16 of H20 and SiOH in SOG, reduced meantime between 17 failure in accelerated life test stressing due to the 18 presence of H20, organic volatiles, and SiOH, the 19 requirement for SOG to be subjected to an etch back process, and the result that SOG cannot be used as the 21 constituent of a required high quality dielectric.
22 After SOG was deposited in order to 23 planarize the surface of a semiconductor, an etch back 24 technique was required to be used in multilevel planarization to remove all of the SOG over the lines 26 of a first level of metallization so as to leave only 27 a minimum amount of SOG in the recesses. This 28 resulted in poor process flexibility, poor process 29 compatibility, the requirement to use expensive etch back equipment, and the necessity of tight 31 specifications for depositions and etch back.
32 Contact with water was prohibited.
33 Contact with moist air was required to be minimized by 34 using in-situ curing and/or long outgassing cycles after air contact. This has been found to be not 36 really adequate to rid the layer of SiOH, organic 37 volatiles, and H20 since some remains even after very 1 3398~7 01 long outgassing cycles.
02 The remanent SiOH, organic volatiles, and 03 H20 produced via poisoning. This limited the 04 technology to large metal via spacings, and thus the 05 use of SOG adjacent vias was not really practical for 06 small geometry. Very long back sputter and outgassing 07 steps were needed to outgas the absorbed water.
08 Indeed, for applications where device 09 reliability is particularly important, such as for military applications, the use of SOG technology for 11 semiconductor integrated circuit applications has been 12 prohibited.
13 In order to avoid contact of SOG and metal 14 at places other than the vias for multilevel metallization, the SOG layer was required to be put 16 into a sandwich between two dielectric layers to form 17 a completed dielectric combination of a desired 18 thickness.
19 The quantity of SOG used was required to be minimized, and the aspect ratios was adjusted to 21 obtain everywhere a good combination of dielectric and 22 SOG.
23 SOG was normally cured thermally in 24 nitrogen, argon, oxygen, water or forming gas at temperatures of between 300~C and 450~C for durations 26 between 30 minutes and 2 hours. Wafer storage, 27 loading and unloading for process was required to be 28 done in a dry ambient environment.
29 In the article of Schiltz and Butherus, attempts were described to cure organic SOG by means 31 of an oxygen plasma in a barrel reactor.
32 Unfortunately, as may be seen in the infrared 33 obsorption spectrum in Figure 3 of Butherus, and as 34 described on page 1354, the five last lines of the left-hand column, and as shown in Figure 6 of Schiltz, 36 significant amounts of SiOH and H20 are obtained using 01 that process as a result of the oxidation of the o2 methyl - CH3 bonds by the active oxygen 03 atoms/molecules. In addition, densification of the 04 SOG occurs due to the production of volatile carbon 05 oxide compounds, which were to be evaporated. However 06 water was also formed as a byproduct, which was found 07 to be retained in the SOG.
08 In accordance with the present invention, an 09 SOG film is produced which is substantially SiOH, organic volatiles and H20 free after the treatment.
11 The film has been found to be very stable in moist air 12 and/or water after the treatment. Thus subsequent 13 processing is simplified.
14 Because of the stability and no apparent formation of SiOH, organic volatiles and H20 once the 16 films have been plasma cured, a dry photoresist strip 17 in ~2 plasma is feasible. Via poisoning by SiOH, 18 organic volatiles and H20 is eliminated where the SOG
19 formed in accordance with the present invention contacts vias.
21 SOG films formed by the process of this 22 invention can be stored in moist air for reasonably 23 long periods of time without any appreciable effect on 24 the film after treatment. This is in contrast with tight controI required for SOG formed in accordance 26 with the prior art.
27 It has been found that SOG cured in a plasma 28 which causes an electric field in the SOG film, which 29 can be caused by a DC self-bias in the RF discharge which develops near the surface of the wafer to be 31 treated, will contain substantially no SiOH, organic 32 volatiles and H20, and indeed becomes cured throughout 33 the SOG layer. Further, SOG layers exposed to H20 34 prior to curing in this manner, and thus which have absorbed s~me H20, have been found to be substantially 36 devoid of H20 following a subsequent cure using the 37 process of the present invention. The electrical ~ ~981 7 01 effects which cause an electric field within the SOG
02 are of prime importance in the SOG curing and 03 passivation treatment.
04 It has been found that the barrel plasma o5 reactor used in the prior art does not cause the 06 sufficient required electric field within the SOG
07 being treated. In contrast, a parallel plate reactor 08 does cause the required field to be produced (assuming 09 that the plasma is most positive and the substrate carrying the SOG is in electrical contact with the 11 electrode, as is usual in plasma treatment).
12 Indeed, the electric field can be enhanced 13 by applying an external AC or DC polarization field to 14 the SOG (including the substrate) to increase the internal electric field thereof.
16 It has been found that the nature of the 17 gas used is not essential to the invention, and many 18 gases could be used with good results. While an 19 oxygen plasma gas could be used, it is not the preferred gas, for reasons to be described with 21 reference to the given examples.
22 Large satisfactory SOG thicknesses have 23 been obtained without cracking or adhesion loss, 24 permitting the cured SOG to be used as a dielectric layer itself (i.e. in contact with a semiconductor 26 surface and/or an overlying metal layer), and not 27 solely as a planarizing medium. The dielectric 28 properties of the SOG treated in accordance with the 29 present invention are better than SOG layers described in the prior art, because of water, organic volatiles 31 and SiOH reduction. In addition corrosion of metal 32 lines and other films in contact with the SOG formed 33 in accordance with the present invention because of 34 the water, organic volatiles and SiOH is substantially reduced or eliminated.
36 Via poisoning is reduced because of water, 37 organic volatiles and SiOH reduction, and the adhesion of films over SOG is improved due to improved outgassing behaviour due to the water, organic volatiles and SioH
reduction or elimination. Film cracking over SOG
produced in accordance with the present invention is minimized or eliminated because of improved outgassing behaviour due to the water, organic volatiles and SioH
reduction. Device reliability is also improved for the same reason.
The plasma treatment described herein is effective for various types of SOG, such as siloxanes, silicates, doped silicates and other spin-on materials.
An embodiment of the present invention is a method for producing insulating layers over a substrate comprised of spinning a film of spin-on glass (SOG) over a silicon wafer, precuring the film of SOG at an elevated temperature sufficient to remove virtually all the solvent of the SOG, and curing the film of SOG in a plasma in a reactor of a type exhibiting a self-biased RF discharge adjacent the SOG below, whereby an electric field within the SOG is created, for a period of time sufficient to exclude virtually all SioH~ organic volatiles and H20 from the layer.
In accordance with the invention, the reactor should be of the type which creates an electric field in 2s the SOG during operation thereof.
A reactor which has been found to produce the above effects is a parallel plate plasma reactor, such as type AM-3300, manufactured by Applied Materials Inc.
Another embodiment of the invention is a method for producing insulating layers over a substrate comprised of spinning a film of spin-on-glass SOG over the substrate, precuring the film of SOG at an elevated temperature sufficient to remove virtually all solvent, repeating the steps of spinning and precuring to form an SOG film having a predetermined total film thickness and curing the layer of SOG in a plasma reactor of a type which creates an electric field in the SOG operation thereof for a period of time sufficient to exclude virtually all SioH, organic volatiles and H20 from the layer.
Still another embodiment of the invention is a method of producing an integrated circuit, the steps of spinning a film of spin-on-glass (SOG) over a surface of a wafer to be planarized, precuring the film of SOG at an elevated temperature sufficient to remove virtually all solvent, curing the film of SOG in a plasma in a plasma reactor of a type which creates an electric field in the SOG during operation thereof for a period of time sufficient to exclude virtually all of SioH~ organic volatiles and H20 from the layer, applying a layer of and defining photoresist on the surface of the SOG, etching or otherwise treating the integrated circuit through the defined photoresist, dry stripping the photoresist in an ~2 plasma, and applying a layer of metal conductor to the surface of the SOG over which the photoresist was stripped.
Still another embodiment of the invention is a method of producing an integrated circuit, the steps of spinning a film of spin-on-glass (SOG) directly over a surface of conductive material to be insulated, precuring the film of SOG at an elevated temperature sufficient to exclude virtually all solvent, curing the film of SOG in a plasma in a plasma reactor of a type which creates an electric field in the SOG during operation thereof for a period of time sufficient to exclude all SioH~ organic volatiles and H20 from the layer and applying a conductive layer directly to the surface of the cured SOG layer. The conductive layer applied can be a metal conductor, and the further process steps can be utilized which are applying photoresist to the surface of the metal conductor, ~ ,.
., 1 defining the photoresist by exposing to light through 2 a mask, washing away the photoresist over undesired 3 regions, etching exposed metal conductor, removing the 4 remaining photoresist, cleaning the surface of the s circuit, and applying an insulating layer overtop of 6 the circuit in direct contact with the SOG layer.
7 Still another embodiment of the invention is 8 in a method of producing an integrated circuit, the 9 steps of spinning a film of spin-on-glass (SOG) directly over a surface of lower conductor material to 11 be insulated, precuring the film of SOG at an elevated 12 temperature sufficient to remove virtually all the 13 solvent, curing the film of SOG at between 200~C and 14 400~C in a plasma in a plasma reactor of a type which creates an electric field in the SOG during operation 16 thereof for a period of time sufficient to exclude 17 virtually all SioH, organic volatiles and H20 from the 18 layer, applying a layer of photoresist to the surface 19 of the cured SOG layer, defining the photoresist by 20 exposing its surface to light through a mask, washing 21 away the photoresist over regions for locating 22 conductors, depositing a layer of upper conductor 23 material over the photoresist and exposed SOG layer, 24 removing the remaining photoresist and overlying metal 25 layer, whereupon the conductors are formed, whereby 26 the cured SOG layer forms a dielectric between lower 27 conductor material and the upper conductor material.
28 Then the further step can be undertaken of cleaning 29 the surface, and depositing an insulating layer 30 adherent to and over the exposed SOG surface and the 31 conductors.
32 Another embodiment of the invention is a 33 semiconductor integrated circuit having a layer of 34 spin-on glass thereover which is substantially devoid 35 of SioH, organic volatiles and H20 and a metal 36 conductive layer for the circuit in direct contact 37 with the SOG layer. In further embodiments the layer 38 of spin-on glass is a passivation film, a .- . , ~ ;.
- ....
133'q817 01 planarization film, or a buffer film.
02 In accordance with a further embodiment 03 the invention is a liquid crystal, electrochromic or 04 electroluminescent display having a front surface 05 protectively covered by a layer of spin-on glass which 06 is substantially devoid of SiOH, organic volatiles and 07 H20. The cured SOG layer protects the display from 08 contamination by dissolution of alkali metal.
o9 In accordance with a further embodiment, the plasma cured SOG devoid of SiOH, organic volatiles 11 and H20 is an antireflective coating on a transparent 12 medium. Another embodiment of the invention is a 13 corrosion or chemical protective coating for an object 14 comprised of the plasma cured spin-on-glass layer devoid of SiOH, organic volatiles and H20.
16 Example 1 17 P-5 phosphorus doped silicate SOG
18 purchased from Allied Chemical Corp. was coated using 19 multiple coats to obtain a total thickness of about 500 nanometers on silicon semiconductor wafers. The 21 SOG film was precured at 125~C for 60 seconds in moist 22 air at 40% relative humidity, and then at 200~C for 60 23 seconds in moist air at 40~ relative humidity on a 24 hotplate, to remove the bulk of the solvent containing the SOG from the films, between each coat.
26 After the testing of the final coat, and 27 its proper precure the wafers were cured at 400~C in 28 an oxygen plasma in the AM-3300 parallel plate plasma 29 reactor for 60 minutes at 0.25 Torr, operated at 650 watts and 115 kHz.
31 The parallel plate plasma reactor 32 generated an electric field adjacent to and within the 33 SOG. After treatment the wafers were placed in 34 contact with moist ambient air, and infrared spectra were recorded.
36 It was determined that the water content 37 as well as the organics and SiOH content was 38 _ 9 _ 1 33981 ~
01 substantially reduced, and was substantially smaller 02 than a control set of nitrogen thermally treated films 03 at 400~C to 450~C and not subjected to plasma 04 treatment.
05 In the case of this oxygen plasma 06 treatment, in place of SiOH bonds, SiH bonds were 07 detected. (This SiH bond formation is not seen in 08 case of non-oxidating plasma treatments).
09 It was also found that the treatment resulted in a thickness shrink of the films by about 11 15% (as was reported by Butherus and Schiltz) but in 12 contrast to Butherus and Schiltz, the starting 13 spin-on-glass, P-5, was of inorganic type and 14 oxydation of the methyl bonds Si-CH3 could not explain the shrink.
16 It was concluded that the plasma treatment 17 in accordance with the present invention was very 18 effective for the tight bonding, the removal of SiOH, 19 organic volatiles and H20, in contrast to the process described by Butherus and Schiltz, which shows 21 substantial remanence of SiOH and H20.
22 The treated films were put into contact 23 with deionized water for a period of one hour after 24 plasma treatment. The oxygen plasma treated SOG
yielded SOG films which were much more stable than the 26 control nitrogen thermally cured films, which process 27 could not passivate the SOG films against water.
28 However it was found that in the oxygen plasma treated 29 film some of the SiH bonds were consumed to yield some SiOH and H20. Therefore the oxygen plasma treatment, 31 which provided films containing little or no SiOH and 32 H20 was observed not to provide a stable paSsivation 33 against water, and thus is not a preferred plasma gas.
34 Example 2 Silicon wafers were coated with 600 to 675 36 nanometers thickness of 106 methyl siloxane SOG
37 (organic SOG) purchased from Allied Chemical Corp.
01 The wafers were precured at 125~C for 60 seconds in 02 moist air and 40% relative humidity and then at 200~C
03 for 60 seconds in moist air at 40% relative humidity 04 on a hotplate, in order to remove the bulk of solvents 05 carrying the SOG.
06 The wafers were cured at 400~C in a 07 nitrogen plasma in a parallel plate reactor, which 08 caused a self-biasing effect by producing a field 09 adjacent the SOG in the RF discharge and thus an electric field within the SOG, for 60 minutes at 0.25 11 Torr operating at 650 watts and 115 kHz.
12 It was found that the water content in the 13 SOG was nil. Carbon in the form of Si-CH3 was 14 detected. It was also determined that the nitrogen plasma treated films were just slightly denser than 16 thermally cured control wafers.
17 The films on the wafers were placed into 18 contact with boiling deionized water for 1 hour.
19 Another infrared spectrum was taken.
Absolutely no water was detected.
21 Absolutely no SiOH was detected. Undesirable SiH
22 bonds were not produced, although they were produced 23 in the oxygen plasma treatment. The film appeared to 24 be literally uneffected by the 1 hour contact with boiling deionized water (which is nearly the effective 26 equivalent of 5 days contact at 40% relative humidity 27 at 21~C).
28 The plasma cure in a nitrogen plasma 29 appeared to be virtually ideal.
Example 3 31 Very thick (>1.2 micron in thickness) 106 32 methyl siloxane SOG obtained from Allied Chemical 33 Corp. was coated using multiple coats as a film on 34 silicon wafers. Such thickness is more than sufficient for intermetal dielectric.
36 The films were precured at 125~C for 60 37 seconds in moist air at 40% relative humidity and then 1~3~8t7 01 at 200~C for 60 seconds in moist air at 40~ relative 02 humidity, on a hotplate. The precured film on the 03 substrate was put into contact with boiling deionized 04 water for 60 minutes to increase its content of water.
05 The film was then cured in a nitrogen 06 plasma in a parallel plate plasma reactor as described 07 in the previous examples, but for only 30 minutes at 08 400~C, operating at 650 watts and 115 kHz.
09 It was found that water absorbed by contact with deionized water after the precure step 11 and prior to the plasma cure step was reversed during 12 the plasma cure. The water did not appear after cure.
13 The nitrogen plasma cure passivated the 14 SOG film and following the plasma cure and resulting passivation, almost no additional water absorption 16 occurred after subsequent contact with moist air 17 and/or boiling water. This is in contrast with the 18 reported results on SOG thermal cures.
19 Photoresist dry strip was shown to have almost no effect on SOG film. This is contrast with 21 reported results on thermal cures of this organic SOG.
22 It was determined that very thick SOG
23 films can be coated without cracking and peeling 24 during curing and contrast with reported results on SOG thermal cures. The N2 cure resulted in no water 26 content in the SOG film.
27 Essential steps of the last example thus 28 can be used in a non-etch back, highly flexible, high 29 quality SOG technology, in which the SOG could be used as a dielectric by itself, in contact with a 31 semiconductor surface, in contact with vias or other 32 metal conductors, as an insulator between two metal 33 layers, without poisoning effect, and with good 34 adherence to its underlying and overlying layers. Of course it can also be used in combination with another 36 dielectric. The etch back and sandwich techniques 37 required in order to use SOG in accordance with the 01 prior art need not be used to produce products when 02 the steps of the present invention are used.
03 Accordingly the present invention includes structures 04 which contain an SOG layer which is devoid of SiOH, 05 organic volatiles and H20, used as a dielectric, 06 insulator, etc.
07 It should be noted that the SOG film may 08 be applied in many coats to improve planarization. In 09 this case, a first coat is spun on the substrate, which should be precured; a second coat is spun on 11 overtop of the underlying precured coat, which is 12 precured; a third coat is spun on overtop of the 13 underlying precured coat, which is precured; etc, 14 after which the entire precured multicoated layer is cured in the plasma as described earlier.
16 The types of film that can be plasma cured 17 are not restricted to silicon oxide types of SOGs.
18 For example, types of spin-on coatings based on 19 spin-on boron oxide, phosphorus oxide, arsenic oxide, aluminum oxide, zinc oxide, gold oxide, platinum 21 oxide, antimony oxide, indium oxide, tantalum oxide, 22 cesium oxide, iron oxide, or any combination thereof 23 can be cured using the present invention.
24 In addition, spin-on coating types of materials formed of nitrides and oxinitrides of boron, 26 phosphorus, arsenic, aluminum, zinc, gold, platinum, 27 antimony, indium, tantalum, cesium and iron could be 28 similarly cured and used.
29 The spin-on-glass can be either silicates undoped or doped with any of known, phosphorus, 31 arsenic, aluminum, zinc, gold, platinum, antimony, 32 indium, tantalum, cesium and iron or methyl siloxanes 33 undoped or doped with the above elements, ethyl 34 siloxanes undoped or doped with the above elements, butyl siloxanes undoped or doped with the above 36 elements, phenyl siloxanes undoped or doped with the 37 above elements, or combinations of any of the 01 above-noted siloxanes.
02 Films plasma cured in accordance with this 03 invention need not be restricted to interlayer 04 dielectrics. Some applications and structures thereof 05 are as a diffusion source for doping of substrates, as 06 a passivation film, as a planarization film, as a 07 buffer film, as a preventive film for dissolution of 08 alkali metals (e.g. for displays such as liquid 09 crystal, electrochromic or electroluminescent compounds), as an antireflective coating and other 11 substances used for selective photon absorption, 12 increased chemical resistance, friction reduction, 13 corrosion protection, increased adhesion, etc.
14 For various applications, optimization of the process can include varying the distance between 16 the plasma glow and the film to be treated, the 17 application of an external polarization field (which 18 can be either DC or AC) to the substrate or substrate 19 holder to enhance the process by increasing the internal electric fields in the SOG film, variation of 21 pressure, power, frequency, gas, gas mixture, mass 22 flow, film temperature and time of treatment, etc.
23 The films produced by the process 24 described herein can be used on or as part of integrated circuits, emission diode devices, liquid 26 crystal, electrochromic and electroluminescent 27 displays, photodetectors, solar batteries, etc. It 28 can be applied to optical filters, antireflectors, as 29 a passivation film on objects to be protected, as a corrosion protection layer, as an adhesion promoter, 31 as a friction reducer, in mechanical field 32 applications, etc.
09 Spin-on glasses (SOG) have been described as being able to be used for the purpose of 11 planarizing integrated circuits. Because of their 12 inherent filling and planarizing properties, their use 13 is particularly attractive as the size of 14 semiconductor integrated circuits decreases, and when multiple level metallization is needed.
16 Unfortunately, cured SOG has been found to 17 be unstable in moist air and water, tending to absorb 18 water and form silanol groups, SiOH.
19 SOG and its method of curing have been described in the article by A. Schiltz entitled 22 INTERCONNECTION DIELECTRIC PLANARIZATION, published in 23 "Microelectronic Engineering" 5 (1986) pp. 413-421 by 24 Elsevier Science Publishers BV (North Holland), and the article ~2 PLASMA-CONVERTED SPIN-ON-GLASS FOR
26 PLANARIZATION by A.D. Butherus et al, 27 September/October 1985, J. Vac. Sci. Technol. B3(5) 28 pp. 1352-1356.
29 In the article COMPARISON OF PROPERTIES OF
DIELECTRIC FILMS DEPOSITED BY VARIOUS METHODS by W.A.
31 Pliskin, J. Vac. Sci. Technol. Vol. 14 No. 5, 32 Sept./Oct. 1977, pp. 1065-1081, the SiOH and H20 33 content in various dielectric thin films is 34 described. In the article EVALUATIONS OF PLASMA
SILICON-OXIDE FILM (P-SiO) BY INFRARED ABSORPTION by 36 A. Takamatsu et al, J. Electro. Chem. Soc.:
37 Solid-State Science & Technology, Feb. 1986, pp.
01 443-445, the relationship between the presence of SiOH
02 and failure of semiconductor devices are described.
03 It is clear that the known process for 04 producing SOG produces SiOH, organic volatiles, and 05 H20 including solvents, alcohols, large organometallic 06 molecules and large organic molecules, which is o7 associated with corrosion of metallization lines in 08 contact with SOG, outgassing during metallization 09 resulting in via-poisoning, poor adhesion due to outgassing and other H20, organic volatiles, and SiOH
11 effects, cracking, peeling and flaking of films 12 deposited over SOG due to outgassing related pressure 13 buildup, low breakdown voltage of dielectric 14 combinations with SOG, lossy dielectric combinations with SOG, low density dielectrics due to the presence 16 of H20 and SiOH in SOG, reduced meantime between 17 failure in accelerated life test stressing due to the 18 presence of H20, organic volatiles, and SiOH, the 19 requirement for SOG to be subjected to an etch back process, and the result that SOG cannot be used as the 21 constituent of a required high quality dielectric.
22 After SOG was deposited in order to 23 planarize the surface of a semiconductor, an etch back 24 technique was required to be used in multilevel planarization to remove all of the SOG over the lines 26 of a first level of metallization so as to leave only 27 a minimum amount of SOG in the recesses. This 28 resulted in poor process flexibility, poor process 29 compatibility, the requirement to use expensive etch back equipment, and the necessity of tight 31 specifications for depositions and etch back.
32 Contact with water was prohibited.
33 Contact with moist air was required to be minimized by 34 using in-situ curing and/or long outgassing cycles after air contact. This has been found to be not 36 really adequate to rid the layer of SiOH, organic 37 volatiles, and H20 since some remains even after very 1 3398~7 01 long outgassing cycles.
02 The remanent SiOH, organic volatiles, and 03 H20 produced via poisoning. This limited the 04 technology to large metal via spacings, and thus the 05 use of SOG adjacent vias was not really practical for 06 small geometry. Very long back sputter and outgassing 07 steps were needed to outgas the absorbed water.
08 Indeed, for applications where device 09 reliability is particularly important, such as for military applications, the use of SOG technology for 11 semiconductor integrated circuit applications has been 12 prohibited.
13 In order to avoid contact of SOG and metal 14 at places other than the vias for multilevel metallization, the SOG layer was required to be put 16 into a sandwich between two dielectric layers to form 17 a completed dielectric combination of a desired 18 thickness.
19 The quantity of SOG used was required to be minimized, and the aspect ratios was adjusted to 21 obtain everywhere a good combination of dielectric and 22 SOG.
23 SOG was normally cured thermally in 24 nitrogen, argon, oxygen, water or forming gas at temperatures of between 300~C and 450~C for durations 26 between 30 minutes and 2 hours. Wafer storage, 27 loading and unloading for process was required to be 28 done in a dry ambient environment.
29 In the article of Schiltz and Butherus, attempts were described to cure organic SOG by means 31 of an oxygen plasma in a barrel reactor.
32 Unfortunately, as may be seen in the infrared 33 obsorption spectrum in Figure 3 of Butherus, and as 34 described on page 1354, the five last lines of the left-hand column, and as shown in Figure 6 of Schiltz, 36 significant amounts of SiOH and H20 are obtained using 01 that process as a result of the oxidation of the o2 methyl - CH3 bonds by the active oxygen 03 atoms/molecules. In addition, densification of the 04 SOG occurs due to the production of volatile carbon 05 oxide compounds, which were to be evaporated. However 06 water was also formed as a byproduct, which was found 07 to be retained in the SOG.
08 In accordance with the present invention, an 09 SOG film is produced which is substantially SiOH, organic volatiles and H20 free after the treatment.
11 The film has been found to be very stable in moist air 12 and/or water after the treatment. Thus subsequent 13 processing is simplified.
14 Because of the stability and no apparent formation of SiOH, organic volatiles and H20 once the 16 films have been plasma cured, a dry photoresist strip 17 in ~2 plasma is feasible. Via poisoning by SiOH, 18 organic volatiles and H20 is eliminated where the SOG
19 formed in accordance with the present invention contacts vias.
21 SOG films formed by the process of this 22 invention can be stored in moist air for reasonably 23 long periods of time without any appreciable effect on 24 the film after treatment. This is in contrast with tight controI required for SOG formed in accordance 26 with the prior art.
27 It has been found that SOG cured in a plasma 28 which causes an electric field in the SOG film, which 29 can be caused by a DC self-bias in the RF discharge which develops near the surface of the wafer to be 31 treated, will contain substantially no SiOH, organic 32 volatiles and H20, and indeed becomes cured throughout 33 the SOG layer. Further, SOG layers exposed to H20 34 prior to curing in this manner, and thus which have absorbed s~me H20, have been found to be substantially 36 devoid of H20 following a subsequent cure using the 37 process of the present invention. The electrical ~ ~981 7 01 effects which cause an electric field within the SOG
02 are of prime importance in the SOG curing and 03 passivation treatment.
04 It has been found that the barrel plasma o5 reactor used in the prior art does not cause the 06 sufficient required electric field within the SOG
07 being treated. In contrast, a parallel plate reactor 08 does cause the required field to be produced (assuming 09 that the plasma is most positive and the substrate carrying the SOG is in electrical contact with the 11 electrode, as is usual in plasma treatment).
12 Indeed, the electric field can be enhanced 13 by applying an external AC or DC polarization field to 14 the SOG (including the substrate) to increase the internal electric field thereof.
16 It has been found that the nature of the 17 gas used is not essential to the invention, and many 18 gases could be used with good results. While an 19 oxygen plasma gas could be used, it is not the preferred gas, for reasons to be described with 21 reference to the given examples.
22 Large satisfactory SOG thicknesses have 23 been obtained without cracking or adhesion loss, 24 permitting the cured SOG to be used as a dielectric layer itself (i.e. in contact with a semiconductor 26 surface and/or an overlying metal layer), and not 27 solely as a planarizing medium. The dielectric 28 properties of the SOG treated in accordance with the 29 present invention are better than SOG layers described in the prior art, because of water, organic volatiles 31 and SiOH reduction. In addition corrosion of metal 32 lines and other films in contact with the SOG formed 33 in accordance with the present invention because of 34 the water, organic volatiles and SiOH is substantially reduced or eliminated.
36 Via poisoning is reduced because of water, 37 organic volatiles and SiOH reduction, and the adhesion of films over SOG is improved due to improved outgassing behaviour due to the water, organic volatiles and SioH
reduction or elimination. Film cracking over SOG
produced in accordance with the present invention is minimized or eliminated because of improved outgassing behaviour due to the water, organic volatiles and SioH
reduction. Device reliability is also improved for the same reason.
The plasma treatment described herein is effective for various types of SOG, such as siloxanes, silicates, doped silicates and other spin-on materials.
An embodiment of the present invention is a method for producing insulating layers over a substrate comprised of spinning a film of spin-on glass (SOG) over a silicon wafer, precuring the film of SOG at an elevated temperature sufficient to remove virtually all the solvent of the SOG, and curing the film of SOG in a plasma in a reactor of a type exhibiting a self-biased RF discharge adjacent the SOG below, whereby an electric field within the SOG is created, for a period of time sufficient to exclude virtually all SioH~ organic volatiles and H20 from the layer.
In accordance with the invention, the reactor should be of the type which creates an electric field in 2s the SOG during operation thereof.
A reactor which has been found to produce the above effects is a parallel plate plasma reactor, such as type AM-3300, manufactured by Applied Materials Inc.
Another embodiment of the invention is a method for producing insulating layers over a substrate comprised of spinning a film of spin-on-glass SOG over the substrate, precuring the film of SOG at an elevated temperature sufficient to remove virtually all solvent, repeating the steps of spinning and precuring to form an SOG film having a predetermined total film thickness and curing the layer of SOG in a plasma reactor of a type which creates an electric field in the SOG operation thereof for a period of time sufficient to exclude virtually all SioH, organic volatiles and H20 from the layer.
Still another embodiment of the invention is a method of producing an integrated circuit, the steps of spinning a film of spin-on-glass (SOG) over a surface of a wafer to be planarized, precuring the film of SOG at an elevated temperature sufficient to remove virtually all solvent, curing the film of SOG in a plasma in a plasma reactor of a type which creates an electric field in the SOG during operation thereof for a period of time sufficient to exclude virtually all of SioH~ organic volatiles and H20 from the layer, applying a layer of and defining photoresist on the surface of the SOG, etching or otherwise treating the integrated circuit through the defined photoresist, dry stripping the photoresist in an ~2 plasma, and applying a layer of metal conductor to the surface of the SOG over which the photoresist was stripped.
Still another embodiment of the invention is a method of producing an integrated circuit, the steps of spinning a film of spin-on-glass (SOG) directly over a surface of conductive material to be insulated, precuring the film of SOG at an elevated temperature sufficient to exclude virtually all solvent, curing the film of SOG in a plasma in a plasma reactor of a type which creates an electric field in the SOG during operation thereof for a period of time sufficient to exclude all SioH~ organic volatiles and H20 from the layer and applying a conductive layer directly to the surface of the cured SOG layer. The conductive layer applied can be a metal conductor, and the further process steps can be utilized which are applying photoresist to the surface of the metal conductor, ~ ,.
., 1 defining the photoresist by exposing to light through 2 a mask, washing away the photoresist over undesired 3 regions, etching exposed metal conductor, removing the 4 remaining photoresist, cleaning the surface of the s circuit, and applying an insulating layer overtop of 6 the circuit in direct contact with the SOG layer.
7 Still another embodiment of the invention is 8 in a method of producing an integrated circuit, the 9 steps of spinning a film of spin-on-glass (SOG) directly over a surface of lower conductor material to 11 be insulated, precuring the film of SOG at an elevated 12 temperature sufficient to remove virtually all the 13 solvent, curing the film of SOG at between 200~C and 14 400~C in a plasma in a plasma reactor of a type which creates an electric field in the SOG during operation 16 thereof for a period of time sufficient to exclude 17 virtually all SioH, organic volatiles and H20 from the 18 layer, applying a layer of photoresist to the surface 19 of the cured SOG layer, defining the photoresist by 20 exposing its surface to light through a mask, washing 21 away the photoresist over regions for locating 22 conductors, depositing a layer of upper conductor 23 material over the photoresist and exposed SOG layer, 24 removing the remaining photoresist and overlying metal 25 layer, whereupon the conductors are formed, whereby 26 the cured SOG layer forms a dielectric between lower 27 conductor material and the upper conductor material.
28 Then the further step can be undertaken of cleaning 29 the surface, and depositing an insulating layer 30 adherent to and over the exposed SOG surface and the 31 conductors.
32 Another embodiment of the invention is a 33 semiconductor integrated circuit having a layer of 34 spin-on glass thereover which is substantially devoid 35 of SioH, organic volatiles and H20 and a metal 36 conductive layer for the circuit in direct contact 37 with the SOG layer. In further embodiments the layer 38 of spin-on glass is a passivation film, a .- . , ~ ;.
- ....
133'q817 01 planarization film, or a buffer film.
02 In accordance with a further embodiment 03 the invention is a liquid crystal, electrochromic or 04 electroluminescent display having a front surface 05 protectively covered by a layer of spin-on glass which 06 is substantially devoid of SiOH, organic volatiles and 07 H20. The cured SOG layer protects the display from 08 contamination by dissolution of alkali metal.
o9 In accordance with a further embodiment, the plasma cured SOG devoid of SiOH, organic volatiles 11 and H20 is an antireflective coating on a transparent 12 medium. Another embodiment of the invention is a 13 corrosion or chemical protective coating for an object 14 comprised of the plasma cured spin-on-glass layer devoid of SiOH, organic volatiles and H20.
16 Example 1 17 P-5 phosphorus doped silicate SOG
18 purchased from Allied Chemical Corp. was coated using 19 multiple coats to obtain a total thickness of about 500 nanometers on silicon semiconductor wafers. The 21 SOG film was precured at 125~C for 60 seconds in moist 22 air at 40% relative humidity, and then at 200~C for 60 23 seconds in moist air at 40~ relative humidity on a 24 hotplate, to remove the bulk of the solvent containing the SOG from the films, between each coat.
26 After the testing of the final coat, and 27 its proper precure the wafers were cured at 400~C in 28 an oxygen plasma in the AM-3300 parallel plate plasma 29 reactor for 60 minutes at 0.25 Torr, operated at 650 watts and 115 kHz.
31 The parallel plate plasma reactor 32 generated an electric field adjacent to and within the 33 SOG. After treatment the wafers were placed in 34 contact with moist ambient air, and infrared spectra were recorded.
36 It was determined that the water content 37 as well as the organics and SiOH content was 38 _ 9 _ 1 33981 ~
01 substantially reduced, and was substantially smaller 02 than a control set of nitrogen thermally treated films 03 at 400~C to 450~C and not subjected to plasma 04 treatment.
05 In the case of this oxygen plasma 06 treatment, in place of SiOH bonds, SiH bonds were 07 detected. (This SiH bond formation is not seen in 08 case of non-oxidating plasma treatments).
09 It was also found that the treatment resulted in a thickness shrink of the films by about 11 15% (as was reported by Butherus and Schiltz) but in 12 contrast to Butherus and Schiltz, the starting 13 spin-on-glass, P-5, was of inorganic type and 14 oxydation of the methyl bonds Si-CH3 could not explain the shrink.
16 It was concluded that the plasma treatment 17 in accordance with the present invention was very 18 effective for the tight bonding, the removal of SiOH, 19 organic volatiles and H20, in contrast to the process described by Butherus and Schiltz, which shows 21 substantial remanence of SiOH and H20.
22 The treated films were put into contact 23 with deionized water for a period of one hour after 24 plasma treatment. The oxygen plasma treated SOG
yielded SOG films which were much more stable than the 26 control nitrogen thermally cured films, which process 27 could not passivate the SOG films against water.
28 However it was found that in the oxygen plasma treated 29 film some of the SiH bonds were consumed to yield some SiOH and H20. Therefore the oxygen plasma treatment, 31 which provided films containing little or no SiOH and 32 H20 was observed not to provide a stable paSsivation 33 against water, and thus is not a preferred plasma gas.
34 Example 2 Silicon wafers were coated with 600 to 675 36 nanometers thickness of 106 methyl siloxane SOG
37 (organic SOG) purchased from Allied Chemical Corp.
01 The wafers were precured at 125~C for 60 seconds in 02 moist air and 40% relative humidity and then at 200~C
03 for 60 seconds in moist air at 40% relative humidity 04 on a hotplate, in order to remove the bulk of solvents 05 carrying the SOG.
06 The wafers were cured at 400~C in a 07 nitrogen plasma in a parallel plate reactor, which 08 caused a self-biasing effect by producing a field 09 adjacent the SOG in the RF discharge and thus an electric field within the SOG, for 60 minutes at 0.25 11 Torr operating at 650 watts and 115 kHz.
12 It was found that the water content in the 13 SOG was nil. Carbon in the form of Si-CH3 was 14 detected. It was also determined that the nitrogen plasma treated films were just slightly denser than 16 thermally cured control wafers.
17 The films on the wafers were placed into 18 contact with boiling deionized water for 1 hour.
19 Another infrared spectrum was taken.
Absolutely no water was detected.
21 Absolutely no SiOH was detected. Undesirable SiH
22 bonds were not produced, although they were produced 23 in the oxygen plasma treatment. The film appeared to 24 be literally uneffected by the 1 hour contact with boiling deionized water (which is nearly the effective 26 equivalent of 5 days contact at 40% relative humidity 27 at 21~C).
28 The plasma cure in a nitrogen plasma 29 appeared to be virtually ideal.
Example 3 31 Very thick (>1.2 micron in thickness) 106 32 methyl siloxane SOG obtained from Allied Chemical 33 Corp. was coated using multiple coats as a film on 34 silicon wafers. Such thickness is more than sufficient for intermetal dielectric.
36 The films were precured at 125~C for 60 37 seconds in moist air at 40% relative humidity and then 1~3~8t7 01 at 200~C for 60 seconds in moist air at 40~ relative 02 humidity, on a hotplate. The precured film on the 03 substrate was put into contact with boiling deionized 04 water for 60 minutes to increase its content of water.
05 The film was then cured in a nitrogen 06 plasma in a parallel plate plasma reactor as described 07 in the previous examples, but for only 30 minutes at 08 400~C, operating at 650 watts and 115 kHz.
09 It was found that water absorbed by contact with deionized water after the precure step 11 and prior to the plasma cure step was reversed during 12 the plasma cure. The water did not appear after cure.
13 The nitrogen plasma cure passivated the 14 SOG film and following the plasma cure and resulting passivation, almost no additional water absorption 16 occurred after subsequent contact with moist air 17 and/or boiling water. This is in contrast with the 18 reported results on SOG thermal cures.
19 Photoresist dry strip was shown to have almost no effect on SOG film. This is contrast with 21 reported results on thermal cures of this organic SOG.
22 It was determined that very thick SOG
23 films can be coated without cracking and peeling 24 during curing and contrast with reported results on SOG thermal cures. The N2 cure resulted in no water 26 content in the SOG film.
27 Essential steps of the last example thus 28 can be used in a non-etch back, highly flexible, high 29 quality SOG technology, in which the SOG could be used as a dielectric by itself, in contact with a 31 semiconductor surface, in contact with vias or other 32 metal conductors, as an insulator between two metal 33 layers, without poisoning effect, and with good 34 adherence to its underlying and overlying layers. Of course it can also be used in combination with another 36 dielectric. The etch back and sandwich techniques 37 required in order to use SOG in accordance with the 01 prior art need not be used to produce products when 02 the steps of the present invention are used.
03 Accordingly the present invention includes structures 04 which contain an SOG layer which is devoid of SiOH, 05 organic volatiles and H20, used as a dielectric, 06 insulator, etc.
07 It should be noted that the SOG film may 08 be applied in many coats to improve planarization. In 09 this case, a first coat is spun on the substrate, which should be precured; a second coat is spun on 11 overtop of the underlying precured coat, which is 12 precured; a third coat is spun on overtop of the 13 underlying precured coat, which is precured; etc, 14 after which the entire precured multicoated layer is cured in the plasma as described earlier.
16 The types of film that can be plasma cured 17 are not restricted to silicon oxide types of SOGs.
18 For example, types of spin-on coatings based on 19 spin-on boron oxide, phosphorus oxide, arsenic oxide, aluminum oxide, zinc oxide, gold oxide, platinum 21 oxide, antimony oxide, indium oxide, tantalum oxide, 22 cesium oxide, iron oxide, or any combination thereof 23 can be cured using the present invention.
24 In addition, spin-on coating types of materials formed of nitrides and oxinitrides of boron, 26 phosphorus, arsenic, aluminum, zinc, gold, platinum, 27 antimony, indium, tantalum, cesium and iron could be 28 similarly cured and used.
29 The spin-on-glass can be either silicates undoped or doped with any of known, phosphorus, 31 arsenic, aluminum, zinc, gold, platinum, antimony, 32 indium, tantalum, cesium and iron or methyl siloxanes 33 undoped or doped with the above elements, ethyl 34 siloxanes undoped or doped with the above elements, butyl siloxanes undoped or doped with the above 36 elements, phenyl siloxanes undoped or doped with the 37 above elements, or combinations of any of the 01 above-noted siloxanes.
02 Films plasma cured in accordance with this 03 invention need not be restricted to interlayer 04 dielectrics. Some applications and structures thereof 05 are as a diffusion source for doping of substrates, as 06 a passivation film, as a planarization film, as a 07 buffer film, as a preventive film for dissolution of 08 alkali metals (e.g. for displays such as liquid 09 crystal, electrochromic or electroluminescent compounds), as an antireflective coating and other 11 substances used for selective photon absorption, 12 increased chemical resistance, friction reduction, 13 corrosion protection, increased adhesion, etc.
14 For various applications, optimization of the process can include varying the distance between 16 the plasma glow and the film to be treated, the 17 application of an external polarization field (which 18 can be either DC or AC) to the substrate or substrate 19 holder to enhance the process by increasing the internal electric fields in the SOG film, variation of 21 pressure, power, frequency, gas, gas mixture, mass 22 flow, film temperature and time of treatment, etc.
23 The films produced by the process 24 described herein can be used on or as part of integrated circuits, emission diode devices, liquid 26 crystal, electrochromic and electroluminescent 27 displays, photodetectors, solar batteries, etc. It 28 can be applied to optical filters, antireflectors, as 29 a passivation film on objects to be protected, as a corrosion protection layer, as an adhesion promoter, 31 as a friction reducer, in mechanical field 32 applications, etc.
Claims (36)
1. A method of producing insulating layers over a semiconductor substrate comprising:
(a) spinning a film of spin-on-glass (SOG) over a semiconductor substrate, (b) precuring the film of SOG at an elevated temperature sufficient to remove virtually all solvent, (c) curing the film of SOG in a plasma in a plasma reactor of a type exhibiting a self-biased radio frequency discharge adjacent the SOG film, whereby an electric field within the SOG is created, for a period of time sufficient to exclude virtually all SiOH, organic volatiles and H2O from the layer.
(a) spinning a film of spin-on-glass (SOG) over a semiconductor substrate, (b) precuring the film of SOG at an elevated temperature sufficient to remove virtually all solvent, (c) curing the film of SOG in a plasma in a plasma reactor of a type exhibiting a self-biased radio frequency discharge adjacent the SOG film, whereby an electric field within the SOG is created, for a period of time sufficient to exclude virtually all SiOH, organic volatiles and H2O from the layer.
2. A method as defined in claim 1 in which the reactor is a parallel plate plasma reactor.
3. A method as defined in claim 1 in which the plasma is a non-oxidising plasma.
4. A method as defined in claim 1 in which the plasma is a nitrogen plasma.
5. A method as defined in claim 4 including using a radio frequency field in the plasma at about 115 kHz, a power density of about .2 watt/cm2, a pressure of about .25 Torr, a mass flow rate of 750 cubic cm. per minute, a current density of about .4 ma/cm2 through the cathode of the reactor, and a curing period of between about 30 to 60 minutes whereby the substrate reaches a temperature of about 400°C.
6. A method as defined in claim 2 including the step of applying an external polarization field to the substrate during the curing step to increase the internal electrical field in the SOG film.
7. A method as defined in claim 2 or 6 in which the SOG is of a type selected from the group consisting of silicon dioxide, boron oxide, phosphorus oxide, arsenic oxide, aluminum oxide, zinc oxide, gold oxide, platinum oxide, antimony oxide, indium oxide, tantalum oxide, cesium oxide and iron oxide, and any combination thereof.
8. A method as defined in claim 2 or 6 in which the SOG is of a type selected from the group consisting of the oxides, nitrides and oxynitrides of boron, phosphorus, arsenic, aluminum, zinc, gold, platinum, antimony, indium, tantalum, cesium, and iron and any combination thereof.
9. A method as defined in claim 2 or 6 in which the SOG is a silicon oxide-type obtained from one of an organic SOG solution and an inorganic siloxane SOG
solution.
solution.
10. A method for producing insulating layers over a substrate comprising:
(a) spinning a film of spin-on-glass (SOG) over the substrate, (b) precuring the film of SOG at an elevated temperature sufficient to remove virtually all solvent, (c) repeating steps (a) and (b) to form an SOG
film having a predetermined total film thickness, (d) curing the layer of SOG in a plasma in a plasma reactor of a type which creates an electric field in the SOG during operation thereof for a period of time sufficient to exclude virtually all SiOH, organic volatiles and H2O from the layer.
(a) spinning a film of spin-on-glass (SOG) over the substrate, (b) precuring the film of SOG at an elevated temperature sufficient to remove virtually all solvent, (c) repeating steps (a) and (b) to form an SOG
film having a predetermined total film thickness, (d) curing the layer of SOG in a plasma in a plasma reactor of a type which creates an electric field in the SOG during operation thereof for a period of time sufficient to exclude virtually all SiOH, organic volatiles and H2O from the layer.
11. A method as defined in claim 10 including the step of applying an external polarization field to the SOG film and the substrate during the curing step to increase internal electrical fields thereof.
12. A method as defined in claim 10 in which the reactor is a parallel plate plasma reactor.
13. A method as defined in claim 12 including the step of allowing contact of the surface of the SOG
film with moisture or water during or after procuring and prior to curing.
film with moisture or water during or after procuring and prior to curing.
14. A method as defined in claim 2, 3 or 10 in which the SOG is selected from the group consisting of a doped or undoped silicate, and a doped or undoped methyl, ethyl, butyl and phenyl siloxane, the dopant being selected from the group consisting of boron, phosphorus, arsenic, aluminum, zinc, gold, platinum, antimony, indium, tantalum, cesium and iron.
15. A method as defined in claim 1, 5 or 10 in which the SOG is a silicate or siloxane material doped with phosphorus.
16. In a method of producing an integrated circuit, the steps of (a) spinning a film of spin-on-glass (SOG) over a surface of a wafer to be planarized, (b) precuring the film of SOG at an elevated temperature sufficient to remove virtually all solvent, (c) curing the film of SOG at between 200°C
and 400°C in a plasma in a plasma reactor of a type which creates an electric field in the SOG during operation thereof for a period of time sufficient to exclude virtually all SiOH, organic volatiles and H2O
from the layer, (d) applying a conductive layer to the surface of the integrated circuit such that it makes direct contact with the cured layer of SOG.
and 400°C in a plasma in a plasma reactor of a type which creates an electric field in the SOG during operation thereof for a period of time sufficient to exclude virtually all SiOH, organic volatiles and H2O
from the layer, (d) applying a conductive layer to the surface of the integrated circuit such that it makes direct contact with the cured layer of SOG.
17. A method as defined in claim 3, 10 or 16 in which the SOG is of a type selected from the group consisting of silicon dioxide, boron oxide, phosphorus oxide, arsenic oxide, aluminum oxide, zinc oxide, gold oxide, platinum oxide, antimony oxide, indium oxide, tantalum oxide, cesium oxide and iron oxide, and any combination thereof.
18. A method as defined in claim 3, 10 or 16 in which the SOG is of a type selected from the group consisting of the oxides, nitrides and oxynitrides of boron, phosphorus, arsenic, aluminum, zinc, gold, platinum, antimony, indium, tantalum, cesium, and iron, and any combination thereof.
19. In a method of producing an integrated circuit, the steps of (a) spinning a film of spin-on-glass (SOG) over a surface of a wafer to be planarized, (b) precuring the film of SOG at an elevated temperature sufficient to remove virtually all solvent, (c) curing the film of SOG in a plasma in a plasma reactor of a type which creates an electric field in the SOG during operation thereof for a period of time sufficient to exclude virtually all SiOH, organic volatiles and H2O from the layer, (d) applying a layer of and defining photoresist on the surface of the SOG, (e) etching the integrated circuit through the defined photoresist, (f) dry stripping the photoresist in an O2 plasma, and (g) applying a layer of metal conductor to the surface of the SOG over which the photoresist was stripped.
20. In a method as defined in claim 19, the additional step, following the curing step and prior to applying a layer of photoresist, of depositing a layer of dielectric over the cured film of SOG.
21. In a method of producing an integrated circuit, the steps of (a) spinning a film of spin-on-glass (SOG) directly over a surface of conductive material to-be insulated, (b) precuring the film of SOG at an elevated temperature sufficient to exclude virtually all solvent, (c) curing the film of SOG in a plasma in a plasma reactor of a type which creates an electric field in the SOG during operation thereof for a period of time sufficient to exclude virtually all SiOH, organic volatiles and H2O from the layer, (d) applying a conductive layer directly to the surface of the cured SOG layer.
22. A method as defined in claim 21 in which the reactor is a parallel plate plasma reactor.
. , .
. , .
23. A method as defined in claim 22 in which the SOG is a silicon oxide-type.
24. A method as defined in claim 21, 22 or 23, in which the conductive layer applied in step (d) is a metal conductor including the further steps of applying photoresist to the surface of the metal conductor, defining the photoresist by exposing it to light through a mask, washing away the photoresist over predetermined regions defined by the photoresist, etching exposed metal conductor, removing the remaining photoresist, cleaning the surface of the circuit, and applying an insulating layer overtop of the circuit in direct contact with the SOG layer.
25. In a method of producing an integrated circuit, the steps of (a) spinning a film of spin-on-glass (SOG) directly over a surface of lower conductor material to be insulated, (b) precuring the film of SOG at an elevated temperature sufficient to remove virtually all the solvent, (c) curing the film of SOG at between 200°C
and 400°C in a plasma in a plasma reactor of a type which creates an electric field in the SOG during operation thereof for a period of time sufficient to exclude virtually all SiOH, organic volatiles and H2O
from the layer, (d) applying a layer of photoresist to the surface of the cured SOG layer, (e) defining the photoresist by exposing its surface to light through a mask, washing away the photoresist over regions for locating conductors, (f) depositing a layer of upper conductor material over the photoresist and exposed SOG layer, (g) removing the remaining photoresist and overlying metal layer, whereupon said conductors are formed, whereby the cured SOG layer forms a dielectric between the lower conductor material and the upper conductor material.
and 400°C in a plasma in a plasma reactor of a type which creates an electric field in the SOG during operation thereof for a period of time sufficient to exclude virtually all SiOH, organic volatiles and H2O
from the layer, (d) applying a layer of photoresist to the surface of the cured SOG layer, (e) defining the photoresist by exposing its surface to light through a mask, washing away the photoresist over regions for locating conductors, (f) depositing a layer of upper conductor material over the photoresist and exposed SOG layer, (g) removing the remaining photoresist and overlying metal layer, whereupon said conductors are formed, whereby the cured SOG layer forms a dielectric between the lower conductor material and the upper conductor material.
26. A method as defined in claim 25, including the further step of cleaning said surface, then depositing an insulating layer adherent to and over the exposed SOG surface and the conductors.
27. A semiconductor integrated circuit having a layer of plasma cured spin-on-glass thereon which is virtually devoid of SiOH, organic volatiles and H2O and having metal conductive layers for the circuit in direct contact with the SOG layer.
28. An integrated circuit having a layer of plasma cured spin-on-glass which is virtually devoid of SiOH, organic volatiles and H2O, as a passivation film.
29. An integrated circuit having a layer of plasma cured spin-on-glass which is virtually devoid of SiOH, organic volatiles and H2O, as a planarization film.
30. An integrated circuit having a layer of plasma cured spin-on-glass which is virtually devoid of SiOH, organic volatiles and H2O, as a buffer film.
31. A liquid crystal, electrochromic or electroluminescent crystal display having a front surface protectively covered by a layer of plasma cured spin-on-glass which is virtually devoid of SiOH, organic volatiles and H2O.
32. An anti-reflective coating on a transparent medium having a front surface protectively covered by a layer of plasma cured spin-on-glass which is virtually devoid of SiOH, organic volatiles and H2O.
33. A corrosion or chemical protective coating for an object having a front surface protectively covered by a layer of plasma cured spin-on- glass which is virtually devoid of SiOH, organic volatiles and H2O.
34. A method as defined in claim 14 in which the gas used in the plasma reactor is a non-oxidizing gas.
35. A method as defined in claim 14 in which the gas used in the plasma reactor is nitrogen.
36. An integrated circuit as defined in claim 27 in which the SOG layer is at least 0.5 microns in thickness.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000601333A CA1339817C (en) | 1989-05-31 | 1989-05-31 | Curing and passivation of spin-on-glasses by a plasma process, and product produced thereby |
| GB9008943A GB2235444B (en) | 1989-05-31 | 1990-04-20 | A method of producing layers on a substrate and a product thereof |
| KR1019900005541A KR940010494B1 (en) | 1989-05-31 | 1990-04-20 | Curing and passivation of sog by a plasma process |
| DE4013449A DE4013449C2 (en) | 1989-05-31 | 1990-04-27 | Process for the production of insulating layers on a semiconductor substrate |
| JP2136887A JPH0727896B2 (en) | 1989-05-31 | 1990-05-25 | Manufacturing method including formation of spin-on-glass film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000601333A CA1339817C (en) | 1989-05-31 | 1989-05-31 | Curing and passivation of spin-on-glasses by a plasma process, and product produced thereby |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1339817C true CA1339817C (en) | 1998-04-14 |
Family
ID=4140137
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000601333A Expired - Fee Related CA1339817C (en) | 1989-05-31 | 1989-05-31 | Curing and passivation of spin-on-glasses by a plasma process, and product produced thereby |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPH0727896B2 (en) |
| KR (1) | KR940010494B1 (en) |
| CA (1) | CA1339817C (en) |
| DE (1) | DE4013449C2 (en) |
| GB (1) | GB2235444B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4140330C1 (en) * | 1991-12-06 | 1993-03-18 | Texas Instruments Deutschland Gmbh, 8050 Freising, De | |
| DE19522004A1 (en) * | 1995-06-21 | 1997-01-02 | Inst Mikrotechnik Mainz Gmbh | Method for producing partly movable micro structure(s) |
| KR970052338A (en) * | 1995-12-23 | 1997-07-29 | 김주용 | Manufacturing method of semiconductor device |
| GB2322734A (en) * | 1997-02-27 | 1998-09-02 | Nec Corp | Semiconductor device and a method of manufacturing the same |
| GB9801655D0 (en) | 1998-01-28 | 1998-03-25 | Trikon Equip Ltd | Method and apparatus for treating a substrate |
| KR101158298B1 (en) | 2003-12-26 | 2012-06-26 | 닛산 가가쿠 고교 가부시키 가이샤 | Composition For Forming Nitride Coating Film For Hard Mask |
| JP2008224288A (en) * | 2007-03-09 | 2008-09-25 | Mitsubishi Electric Corp | Magnetoresistance sensor device |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IN147572B (en) * | 1977-02-24 | 1980-04-19 | Rca Corp | |
| JPS5927532A (en) * | 1982-08-04 | 1984-02-14 | Toshiba Corp | Fabrication of semiconductor device |
| JPS60254621A (en) * | 1984-05-31 | 1985-12-16 | Matsushita Electric Ind Co Ltd | Thin film forming method |
| FR2625839B1 (en) * | 1988-01-13 | 1991-04-26 | Sgs Thomson Microelectronics | PROCESS FOR PASSIVATING AN INTEGRATED CIRCUIT |
-
1989
- 1989-05-31 CA CA000601333A patent/CA1339817C/en not_active Expired - Fee Related
-
1990
- 1990-04-20 KR KR1019900005541A patent/KR940010494B1/en not_active IP Right Cessation
- 1990-04-20 GB GB9008943A patent/GB2235444B/en not_active Expired - Lifetime
- 1990-04-27 DE DE4013449A patent/DE4013449C2/en not_active Expired - Lifetime
- 1990-05-25 JP JP2136887A patent/JPH0727896B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| KR940010494B1 (en) | 1994-10-24 |
| GB2235444B (en) | 1992-12-16 |
| JPH0321023A (en) | 1991-01-29 |
| JPH0727896B2 (en) | 1995-03-29 |
| DE4013449A1 (en) | 1990-12-06 |
| KR900019271A (en) | 1990-12-24 |
| GB9008943D0 (en) | 1990-06-20 |
| GB2235444A (en) | 1991-03-06 |
| DE4013449C2 (en) | 1996-04-18 |
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