WO2019180405A1 - Method for fabrication of a cem device - Google Patents
Method for fabrication of a cem device Download PDFInfo
- Publication number
- WO2019180405A1 WO2019180405A1 PCT/GB2019/050562 GB2019050562W WO2019180405A1 WO 2019180405 A1 WO2019180405 A1 WO 2019180405A1 GB 2019050562 W GB2019050562 W GB 2019050562W WO 2019180405 A1 WO2019180405 A1 WO 2019180405A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- cem
- conductive
- conductive substrate
- overlay
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 87
- 239000000463 material Substances 0.000 claims abstract description 65
- 230000002596 correlated effect Effects 0.000 claims abstract description 49
- 238000001312 dry etching Methods 0.000 claims abstract description 46
- 238000000151 deposition Methods 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 230000001681 protective effect Effects 0.000 claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 238000000059 patterning Methods 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 43
- 229910052751 metal Inorganic materials 0.000 claims description 43
- 239000002184 metal Substances 0.000 claims description 42
- 230000004888 barrier function Effects 0.000 claims description 18
- 238000005530 etching Methods 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 11
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 3
- 229910001453 nickel ion Inorganic materials 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims 2
- 230000007704 transition Effects 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 24
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 17
- 239000003446 ligand Substances 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- -1 ethene) Chemical class 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 229910000314 transition metal oxide Inorganic materials 0.000 description 11
- 229910052581 Si3N4 Inorganic materials 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 229910052741 iridium Inorganic materials 0.000 description 10
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 10
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 10
- 229910052723 transition metal Inorganic materials 0.000 description 10
- 150000003624 transition metals Chemical class 0.000 description 10
- 230000010354 integration Effects 0.000 description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 7
- 239000011810 insulating material Substances 0.000 description 7
- 230000003993 interaction Effects 0.000 description 7
- 150000003623 transition metal compounds Chemical class 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 239000003989 dielectric material Substances 0.000 description 5
- 230000006870 function Effects 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 229910000480 nickel oxide Inorganic materials 0.000 description 5
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 5
- XRIBIDPMFSLGFS-UHFFFAOYSA-N 2-(dimethylamino)-2-methylpropan-1-ol Chemical compound CN(C)C(C)(C)CO XRIBIDPMFSLGFS-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 4
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 4
- 238000000231 atomic layer deposition Methods 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000007323 disproportionation reaction Methods 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 239000012212 insulator Substances 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N Acetylene Chemical compound C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 230000004807 localization Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000001272 nitrous oxide Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical class SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- MITDXNUXOAYFGC-UHFFFAOYSA-N 1-prop-2-ynylbenzimidazole Chemical compound C1=CC=C2N(CC#C)C=NC2=C1 MITDXNUXOAYFGC-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- VWHXTCKWIVCDGV-UHFFFAOYSA-N C(C)C1(C=CC=C1)[Ni]C1(C=CC=C1)CC Chemical compound C(C)C1(C=CC=C1)[Ni]C1(C=CC=C1)CC VWHXTCKWIVCDGV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- QJXATUXVYHPLNO-UHFFFAOYSA-N [Mn](=O)(=O)([O-])[O-].[Ca+2].[Pr+3] Chemical compound [Mn](=O)(=O)([O-])[O-].[Ca+2].[Pr+3] QJXATUXVYHPLNO-UHFFFAOYSA-N 0.000 description 1
- ZMJAIODQTOSUHN-UHFFFAOYSA-N [Mn](=O)(=O)([O-])[O-].[La+3].[Pr+3].[Mn](=O)(=O)([O-])[O-].[Mn](=O)(=O)([O-])[O-] Chemical compound [Mn](=O)(=O)([O-])[O-].[La+3].[Pr+3].[Mn](=O)(=O)([O-])[O-].[Mn](=O)(=O)([O-])[O-] ZMJAIODQTOSUHN-UHFFFAOYSA-N 0.000 description 1
- IHRNDXJDUYVDRB-UHFFFAOYSA-N [Ni].Cc1cccc1.Cc1cccc1 Chemical compound [Ni].Cc1cccc1.Cc1cccc1 IHRNDXJDUYVDRB-UHFFFAOYSA-N 0.000 description 1
- GUBPUWWBVSHLOS-UHFFFAOYSA-N [O-2].[Ti+4].[Yb+3] Chemical compound [O-2].[Ti+4].[Yb+3] GUBPUWWBVSHLOS-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 238000004774 atomic orbital Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- KZPXREABEBSAQM-UHFFFAOYSA-N cyclopenta-1,3-diene;nickel(2+) Chemical compound [Ni+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KZPXREABEBSAQM-UHFFFAOYSA-N 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000000708 deep reactive-ion etching Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229940104869 fluorosilicate Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000005055 memory storage Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- CHPLEWYRKUFKQP-UHFFFAOYSA-N nickel(2+);1,2,3,5,5-pentamethylcyclopenta-1,3-diene Chemical compound [Ni+2].CC1=[C-]C(C)(C)C(C)=C1C.CC1=[C-]C(C)(C)C(C)=C1C CHPLEWYRKUFKQP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- KNJBQISZLAUCMG-UHFFFAOYSA-N oxygen(2-) titanium(4+) yttrium(3+) Chemical compound [O-2].[Y+3].[Ti+4] KNJBQISZLAUCMG-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/011—Manufacture or treatment of multistable switching devices
- H10N70/061—Shaping switching materials
- H10N70/063—Shaping switching materials by etching of pre-deposited switching material layers, e.g. lithography
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/20—Multistable switching devices, e.g. memristors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
- H10N70/821—Device geometry
- H10N70/826—Device geometry adapted for essentially vertical current flow, e.g. sandwich or pillar type devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
- H10N70/883—Oxides or nitrides
- H10N70/8833—Binary metal oxides, e.g. TaOx
Definitions
- the present disclosure is concerned with a method for the fabrication of a correlated electron material (CEM) device as well as with an integrated circuit including a CEM device obtained by the method .
- CEM correlated electron material
- Electronic switching devices are found in a wide variety of electronic device types, such as computers, digital cameras, cellular telephones, tablet devices, personal digital assistants and so forth, where they may function as memory and/or logic devices.
- Factors of interest to a designer in considering whether a particular electronic switching device is suitable for such a function may include physical size, storage density, operating voltages, impedance ranges, and/or power consumption. Other factors of interest may include cost of manufacture, ease of manufacture, scalability and/or reliability.
- the present disclosure describes an improved CEM device and methods for its manufacture.
- the CEM device may, in particular, be a switching device.
- the CEM switching device may find application as a correlated electron random access memory (CERAM) in memory and/or logic devices which may be used with a wide range of electronic circuit types, such as memory controllers, memory arrays, filter circuits, data converters, optical instruments, phase locked loop circuits, microwave and millimeter wave transceivers, and so forth.
- CERAM correlated electron random access memory
- a CEM switching device can exhibit a rapid conductor-to- insulator transition as compared to other switching devices because the switching is brought about by an electron correlation rather than by a solid state structural phase change or by formation of filaments, as is found respectively in phase change memory devices and resistive RAM devices .
- the rapid conductor-to-insulator transition of a CEM switching device may, in particular, be responsive to a quantum mechanical phenomenon in contrast to the melting/solidification or filament formation found respectively in phase change and resistive RAM devices.
- the quantum mechanical transition in a CEM switching device between a relatively conductive state and a relatively insulative state may occur in several ways.
- a quantum mechanical transition of a CEM between a relatively insulative/higher impedance state and a relatively conductive/lower impedance state may be understood in terms of a Mott transition.
- references to a Mott transition are references to traditional Mott transitions (which are described in the literature as purely coulombic) as well as references to Mott- like transitions (in which the coulombic interaction is modified by some other electron interaction, such as a dipole-core charge interaction) .
- a reference to a Mott insulator includes a reference to a charge-transfer (Mott) insulator, such as nickel (II) oxide, in which the columbic interaction or screening is modified by a charge transfer complex through hybridisation with the oxygen band.
- Mott charge-transfer
- a material may switch from a relatively insulative/higher impedance state to a relatively conductive/lower impedance state if a Mott transition condition is satisfied.
- the Mott criteria may be defined by (n c ) 1/3 a 0.26, wherein n c denotes a concentration of electrons, and wherein "a" denotes the Bohr radius . If a threshold carrier concentration is achieved, such that the Mott criteria is met, the Mott transition is believed to occur.
- the state of the CEM device changes from a relatively higher resistance/higher capacitance state (e.g., an insulative/higher impedance state) to a relatively lower resistance/lower capacitance state (e.g., a conductive/lower impedance state) .
- a relatively higher resistance/higher capacitance state e.g., an insulative/higher impedance state
- a relatively lower resistance/lower capacitance state e.g., a conductive/lower impedance state
- the Mott transition may be controlled by a localization of electrons. If carriers, such as electrons, for example, are localized, a strong coulomb interaction between the carriers is believed to split the bands of the CEM to bring about a relatively insulative (relatively higher impedance) state. If electrons are no longer localized, a weak coulomb interaction may dominate, which may give rise to a removal of band splitting, which may, in turn, bring about a metal (conductive) band (relatively lower impedance state) that is substantially dissimilar from the relatively higher impedance state.
- a CEM switch may exhibit a variable resistance together with a property of variable capacitance.
- impedance characteristics of a CEM switch may include both resistive and capacitive components.
- a CEM switch in a metal state, may comprise a relatively low electric field that may approach zero, and therefore may exhibit a substantially low capacitance, which may likewise approach zero.
- a transition from a relatively insulative/higher impedance state to a relatively conductive/lower impedance state in a CEM switch may result in changes in both resistance and capacitance.
- a switching device formed from a CEM may exhibit switching of impedance states responsive to a Mott-transition in a majority of the volume of the CEM comprising the device.
- the CEM may, in particular, form a "bulk switch".
- bulk switch refers to at least a majority volume of a CEM switching a device's impedance state, such as in response to a Mott-transition.
- substantially all CEM of a device may switch from a relatively insulative/higher impedance state to a relatively conductive/lower impedance state or from a relatively conductive/lower impedance state to a relatively insulative/higher impedance state responsive to a Mott-transition.
- a CEM switching device may comprise a layer of correlated electron material (a CEM layer) sandwiched between a conductive substrate and a conductive overlay.
- the CEM switching device can act as memory storage element.
- the CEM switching device may comprise either a CEM layer provided on a conductive substrate or a CEM layer provided with a conductive overlay.
- the device comprises source and drain regions providing for a flow of current across the device.
- a current density versus voltage profile 100 of a CEM switching device is shown which illustrates its switching behaviour.
- the CEM device may be placed into a relatively low- impedance state or a relatively high-impedance state.
- a voltage V Set and a current density J sst may bring about a transition of the CEM switching device to a relatively low-impedance memory state.
- application of a voltage and a current density J reset may bring about a transition of the CEM device to a relatively high-impedance memory state.
- reference designator 110 illustrates the voltage range that may separate V Set from V eset .
- the particular state of the CEM switching device may be detected by application of a voltage V re a d (e.g., during a read operation) and detection of a current or current density at terminals of the CEM switching device (e.g., utilizing read window 102) .
- a CEM switching device may switch from a relatively low-impedance state to a relatively high-impedance state, for example, responsive to a Mott transition. This may correspond to point 108 of the voltage versus current density profile of Figure 1A. At, or suitably nearby this point, electrons are no longer screened and become localized near the metal ion. This correlation may result in a strong electron-to-electron interaction potential which may operate to split the bands to form a relatively high-impedance material .
- the CEM switching device comprises a relatively high- impedance state
- current may be generated by transportation of electron holes. Consequently, if a threshold voltage is applied across terminals of the CEM device, electrons may be injected into a metal-insulator-metal (MIM) diode over the potential barrier of the MIM device.
- MIM metal-insulator-metal
- injection of a threshold current of electrons, at a threshold potential applied across terminals of a CEM device may perform a "set" operation, which places the CEM device into a low-impedance state.
- an increase in electrons may screen incoming electrons and remove a localization of electrons, which may operate to collapse the band-splitting potential, thereby giving rise to the low-impedance state.
- the current in a CEM switching device may be controlled by an externally applied "compliance" condition, which may be determined at least partially on the basis of an applied external current, which may be limited during a write operation, for example, to place the CEM device into a relatively high-impedance state.
- This externally- applied compliance current may, in some devices, also set a condition of a current density for a subsequent reset operation to place the CEM device into a relatively high-impedance state.
- a current density J C om P applied during a write operation at point 116 to place the CEM switching device into a relatively low-impedance state may determine a compliance condition for placing the CEM device into a high-impedance state in a subsequent write operation.
- the CEM device may be subsequently placed into a high-impedance state by application of a current density J reset - J comp at a voltage V reset at point 108, at which J comp is externally applied.
- the compliance may, in particular, set a number of electrons in a CEM switching device which may be "captured" by holes for the Mott transition.
- a current applied in a write operation to place a CEM device into a relatively low-impedance memory state may determine a number of holes to be injected to the CEM device for subsequently transitioning the CEM switching device to a relatively high-impedance memory state.
- a reset condition may occur in response to a Mott transition at point 108.
- a Mott transition may bring about a condition in the CEM switching device in which a concentration of electrons n approximately equals, or becomes at least comparable to, a concentration of electron holes p.
- This condition may be modeled according to expression (1) as follows: 0.26 (1) wherein A TF corresponds to a Thomas Fermi screening length, and C is a constant.
- a current or current density in region 104 of the voltage versus current density profile shown in Figure 1A may exist in response to injection of holes from a voltage signal applied across terminals of the CEM switching device.
- injection of holes may meet a Mott transition criterion for the low-impedance state to high- impedance state transition at current I Mi as a threshold voltage VMI is applied across terminals of a CEM device.
- This may be modeled according to expression (2) as follows:
- Q(V MI ) corresponds to the charged injected (holes or electrons) and is a function of an applied voltage. Injection of electrons and/or holes to enable a Mott transition may occur between bands and in response to threshold voltage V MI , and threshold current I Mi - By equating electron concentration n with a charge concentration to bring about a Mott transition by holes injected by I Mi in expression (2) according to expression (1), a dependency of such a threshold voltage V MI on Thomas Fermi screening length A TF may be modeled according to expression (3), as follows:
- FIG. 1B shows a CEM switching device comprising a CEM layer sandwiched between a conductive substrate and a conductive overlay and Figure 1C shows a schematic diagram of an equivalent circuit for the switching device.
- the CEM switching device may exhibit characteristics of both variable resistance and variable capacitance.
- the CEM switching device may be considered as a variable impedance device in which the impedance depends at least in part on resistance and capacitance characteristics of the device if measured across device terminals .
- the equivalent circuit for a variable impedance device may comprise a variable resistor, such as variable resistor, in parallel with a variable capacitor.
- a variable resistor and variable capacitor are depicted in Figure 1C as comprising discrete components, the variable impedance device, such as that shown, may comprise a substantially homogenous CEM.
- Table 1 illustrates an example truth table for an example variable impedance device, such as the device of Figure 1A.
- Table 1 shows that a resistance of a variable impedance device, such as that shown, may transition between a low-impedance state and a substantially dissimilar, high-impedance state as a function at least partially dependent on a voltage applied across the CEM switching device.
- the impedance exhibited at a low-impedance state may, for example, be approximately in the range of 10.0 - 100,000.0 times lower than an impedance exhibited in a high-impedance state.
- the impedance exhibited at a low-impedance state may be approximately in the range of 5.0 to 10.0 times lower than an impedance exhibited in a high-impedance state.
- Table 1 also shows that a capacitance of a variable impedance device, such as the device shown, may transition between a lower capacitance state, which may, for example comprise an approximately zero, or very little, capacitance, and a higher capacitance state that is a function, at least in part, of a voltage applied across the CEM switching device.
- the CEM switching device may be placed into a relatively low-impedance memory state, such as by transitioning from a relatively high impedance state, for example, via injection of a sufficient quantity of electrons to satisfy a Mott transition criterion.
- a threshold switching potential e.g., , injected electrons may begin to screen.
- screening may operate to delocalize double-occupied electrons to collapse the band-splitting potential, thereby bringing about a relatively low-impedance state.
- changes in impedance states of CEM devices may be brought about by "back-donation" of electrons of compounds comprising Ni x O y (wherein the subscripts "x" and "y” comprise whole numbers) .
- back-donation refers to a supplying of one or more electrons (i.e. electron density) to a transition metal, transition metal oxide, or any combination thereof (i.e. to an atomic orbital of a metal), by an adjacent molecule of a lattice structure (i.e.
- the electron back-donating ligand may be a n-back- bonding ligand such as carbonyl (CO) , nitrosyl (NO) , an isocyanide (RNC where R is H, C 1 -C 6 alkyl or C6-Cio-aryl ) , an alkene (e.g. ethene) , an alkyne (e.g.
- Back-donation may permit a transition metal, transition metal compound, transition metal oxide, or a combination thereof, to maintain an ionization state that is favorable to electrical conduction under an influence of an applied voltage.
- back-donation in a CEM may occur responsive to use of carbonyl (CO) or a nitrogen-containing dopant, such as ammonia (NH 3 ) , ethylene diamine (C 2 H 8 N 2 ) , or members of an oxynitride family (NxOy) , for example, which may permit a CEM to exhibit a property in which electrons are controllably, and reversibly, "donated" to a conduction band of the transition metal or transition metal oxide, such as nickel, for example, during operation of a device or circuit comprising a CEM.
- CO carbonyl
- a nitrogen-containing dopant such as ammonia (NH 3 ) , ethylene diamine (C 2 H 8 N 2 ) , or members of an oxynitride family (NxOy) , for example, which may permit a CEM to exhibit a property in which electrons are controllably, and reversibly, "donated" to a conduction band of the transition metal
- Nickel oxide material e.g., NiO:CO or NzOiNM
- NiO:CO or NzOiNM nickel oxide material
- an electron back-donating material refers to a material that exhibits an impedance switching property, such as switching from a first impedance state to a substantially dissimilar second impedance state (e.g., from a relatively low impedance state to a relatively high impedance state, or vice versa) based, at least in part, on influence of an applied voltage to control donation of electrons, and reversal of the electron donation, to and from a conduction band of the CEM.
- an impedance switching property such as switching from a first impedance state to a substantially dissimilar second impedance state (e.g., from a relatively low impedance state to a relatively high impedance state, or vice versa) based, at least in part, on influence of an applied voltage to control donation of electrons, and reversal of the electron donation, to and from a conduction band of the CEM.
- a CEM switch comprising a transition metal, transition metal compound, or a transition metal oxide
- the transition metal such as nickel, for example
- an oxidation state of 2+ e.g., Ni 2+ in a material, such as NiO:CO or NiO:NH 3
- electron back-donation may be reversed if a transition metal, such as nickel, for example, is placed into an oxidation state of 1+ or 3+.
- Such disproportionation refers to formation of nickel ions as Ni 1+ + Ni 3+ as shown in expression (4), which may bring about, for example, a relatively high-impedance state during operation of the CEM device.
- a dopant such as a carbon-containing ligand, carbonyl (CO) or a nitrogen-containing ligand, such as an ammonia molecule (NH3) , may permit sharing of electrons during operation of a CEM device so as to give rise to the disproportionation reaction of expression (4), and its reversal, substantially in accordance with expression (5), below:
- V reset and V set may vary approximately in the range of 0.1 V to 10.0 V subject to the condition that V set 3 V reset .
- V reset may occur at a voltage approximately in the range of 0.1 V to 1.0 V
- V set may occur at a voltage approximately in the range of 1.0 V to 2.0 V, for example.
- V set and V reset may occur based, at least in part, on a variety of factors, such as atomic concentration of an electron back-donating material, such as NiO:CO or NiO:NH3 and other materials present in the CEM device, as well as other process variations, and claimed subject matter is not limited in this respect.
- an electron back-donating material such as NiO:CO or NiO:NH3
- the fabrication of a CEM device into an integrated circuit generally begins with the formation of the device layers by patterning a layer of a conductive substrate, a layer of a correlated electron material and a layer of a conductive overlay which have been deposited on an insulating substrate, such as silica, having one or more embedded interconnects .
- the patterning forms a stack from the deposited layers which may be fabricated to full integration in an integrated circuit by depositing a cover layer comprising an insulating material, such as silica, over the stack, patterning the cover layer whereby to form a trench in which the conductive overlay is exposed and depositing a metal interconnect in the trench which contacts the conductive overlay .
- a cover layer comprising an insulating material, such as silica
- the patterning of the cover layer may also comprise forming an additional trench and via for an additional metal interconnect enabling contact between other devices, such as transistors, at different levels in a 3-dimensional integrated circuit .
- the materials of the conductive substrate, the CEM layer and the conductive overlay tend to be chemically resistant so that a dry etching (rather than a wet etching) is required in order to form the stack.
- dry etching refers to the removal of a material by exposing a surface of the material to a bombardment of ions (usually derived from a plasma of reactive gases such as fluorocarbons, oxygen, chlorine, boron trichloride, sometimes with addition of nitrogen, argon, helium, and other gases) to remove portions of the material from the exposed surface.
- ions usually derived from a plasma of reactive gases such as fluorocarbons, oxygen, chlorine, boron trichloride, sometimes with addition of nitrogen, argon, helium, and other gases
- dry etching is a directional (or anisotropic) process which is typically used to remove material in the vertical direction (rather than the horizontal direction) .
- dry etching of the layer of correlated electron material can lead to damage at the sidewalls of the CEM layer in the stack.
- Another problem with the fabrication of a CEM device to an integrated circuit is that the dry etching of the layer of conductive substrate can lead to sputtering of the material of the conductive substrate onto the sidewalls of the CEM layer in the stack.
- This sputtering results in a conductive path between the conductive overlay and the conductive substrate at each sidewall of the CEM layer which can disrupt the switching of the CEM layer and degrade its performance .
- the present disclosure relates to a method which avoids these problems and the formation of unwanted conductive paths between the conductive overlay and the conductive substrate at the sidewalls of the CEM layer.
- the present disclosure provides a method for the integration of a correlated electron material (CEM) device to an integrated circuit, the method comprising
- a layer of a conductive overlay on the layer of correlated electron material; and patterning the layers whereby to form a stack comprising a conductive substrate, a CEM layer and a conductive overlay, wherein the patterning comprises the following steps :
- the hard mask may comprise a dielectric material such as silica (SiCh) or silicon nitride (Si 3 N 4 ) which is generally resistant to the dry etching used for forming the stack but susceptible to wet or other etching.
- a dielectric material such as silica (SiCh) or silicon nitride (Si 3 N 4 ) which is generally resistant to the dry etching used for forming the stack but susceptible to wet or other etching.
- It may be formed, for example, by standard lithographic processes using a photoresist spun or otherwise deposited onto a silica or silicon nitride layer formed on the layer of conductive overlay.
- the photoresist may be spun or otherwise deposited on a stack comprising a planarization layer and an antireflection layer deposited on the silica or silicon nitride layer.
- the method comprises depositing a coating of a protective polymer over the whole of the partially formed stack viz., the protective polymer coats not just the sidewalls of the partially formed stack but also the upper surfaces of the layer of conductive substrate and the hard mask.
- the method may further comprise dry etching the protective polymer coating whereby to remove the protective polymer from the upper surfaces of the layer of conductive substrate and the hard mask.
- This dry etching of the protective polymer coating may comprise a separate step to the etching of the conductive substrate. It may use different process conditions or the same process conditions as compared to those used for the dry etching of the layer of conductive substrate.
- the protective polymer may comprise any organic polymer which is susceptible to dry etching (for example, reactive ion etching) and to wet etching. It may, in particular, comprise a fluorocarbon, or hydrofluorocarbon polymer, for example, tetrafluoro- ethylene .
- the coating of the protective polymer may be formed by physical vapour deposition or by chemical vapour deposition.
- the coating of protective polymer is formed by chemical vapour deposition of a fluorocarbon or hydrofluorocarbon polymer using gases of formula C x H y F z where x and z > 0 and y > 0.
- the method may further comprise removing the coating of protective polymer from the side-walls of the stack after the dry etching of the layer of conductive substrate.
- the removal may be carried out by wet cleaning the stack by, for example, dipping in a solution of dilute hydrofluoric acid (DHF) .
- DHF dilute hydrofluoric acid
- the wet clean will generally be selective for the protective polymer coating it may also etch the correlated electron material.
- the method may further comprise etching a portion of the correlated electron material at the sidewalls of the CEM layer whereby to remove any damage which has occurred during the dry etching of the layer of correlated electron material.
- the removal of portions of the correlated electron material at the sidewalls of the CEM layer in the stack may provide an indent or recess in the CEM layer which extends into the CEM layer to an extent from about 1 nm to about 10 nm.
- the indent or recess may also extend around the CEM layer and across the whole of the thickness of the CEM layer.
- the method may further comprise removing the hard mask from the stack. The removal may be carried out prior to forming the cover layer of insulating material or at the same time as the etching of a trench in the cover layer.
- the method may also comprise depositing a cover layer comprising an insulating material, such as silica, over the stack and patterning the cover layer whereby to form a trench in the cover layer in which (at least a part) of the conductive overlay protrudes.
- the method may further comprise depositing a metal barrier layer over the conductive overlay and at least the interior walls of the trench.
- the metal barrier layer prevents the migration of metal ion from the metal interconnect into the cover plate and the device. It also protects against the ingress of moisture from ambient or the cover layer to the stack.
- the metal barrier layer may, in particular, comprise one or more of tantalum nitride (TaN) , titanium nitride (TiN) , cobalt (Co), ruthenium (Ru) and tantalum (Ta) .
- the method may further comprise depositing a moisture barrier layer over the stack prior to the deposition of the cover layer.
- the moisture barrier layer which may, for example, comprise silicon nitride (Si 3 N 4 ) , silicon carbon nitride (SiCN) or silicon carbide, prevents the ingress of moisture, for example, from ambient or from the etching of the cover layer, into the sidewalls of the fabricated device.
- the moisture barrier layer is etched away from the upper surface (and a part of the sidewalls) of the conductive overlay when the trench is etched in the cover layer.
- the method may further comprise depositing a metal interconnect whereby to substantially fill the trench.
- the metal interconnect may comprise aluminium, cobalt, ruthenium, tungsten or copper .
- the forming of the layer of conductive overlay, the layer of correlated electron material and the layer of conductive substrate may comprise any suitable physical vapour deposition or chemical vapour deposition.
- the forming of at least the CEM layer comprises a chemical vapour deposition and, in particular, an atomic layer deposition.
- the conductive overlay and/or the conductive substrate comprise a major (bulk) layer comprising a conductive metal nitride and a minor layer comprising a noble metal or a conductive metal oxide .
- the forming of the layer of conductive substrate comprises depositing a first layer of a metal nitride and depositing a second layer of a noble metal or other conductive material on the first layer.
- the forming of the conductive overlay may comprise depositing a first layer of a noble metal or other conductive material and depositing a second layer of a metal nitride on the first layer .
- the metal nitride may comprise one or more of titanium nitride, tantalum nitride, and tungsten nitride.
- the noble metal or other conductive material may comprise platinum, titanium, copper, aluminium, cobalt, nickel, tungsten, cobalt silicide, ruthenium oxide, chromium, gold, palladium, indium tin oxide, tantalum, silver, iridium, iridium oxide or any combination thereof.
- the forming of the layer of conductive substrate may be on an insulating substrate, such as a silica, provided on an underlying dielectric material.
- the substrate may include a via for contacting the conductive substrate with a copper, tungsten, ruthenium, cobalt or aluminium interconnect provided in the dielectric material .
- the substrate comprises a fluorosilicate glass (FSG) plate provided on a (low k) dielectric material.
- the substrate includes a via for contacting the conductive substrate of the device through the glass (FSG) plate with a copper interconnect embedded in the dielectric material.
- the method may comprise forming a layer of a correlated electron material comprising a doped metal compound of a d- or f-block element (especially one exhibiting an incomplete d- or f-block shell) such as nickel, cobalt, iron, yttrium or ytterbium. It may comprise forming a CEM layer comprising an oxide of a d- or f- block element and, in particular, a transition metal oxide (TMO) such as nickel oxide, cobalt oxide, hafnium oxide, iron oxide or an oxide or a rare earth element such as yttrium oxide.
- TMO transition metal oxide
- the method may alternatively comprise forming a layer of a correlated electron material comprising a complex (or "mixed") oxide of d- and/or f-block elements, for example, as a perovskite such as chromium doped strontium titanate, lanthanum titanate, praseodymium calcium manganate or praseodymium lanthanum manganate or a complex oxide or a rare earth element and a transition metal such as yttrium titanium oxide or ytterbium titanium oxide.
- a complex (or "mixed") oxide of d- and/or f-block elements for example, as a perovskite such as chromium doped strontium titanate, lanthanum titanate, praseodymium calcium manganate or praseodymium lanthanum manganate or a complex oxide or a rare earth element and a transition metal such as yttrium titanium oxide or ytterbium titanium oxide.
- the metal compound of the correlated electron material may be of general formula AB:L X (for example, NiO:CO) wherein the AB denotes, for example, a transition metal compound, such as a transition metal oxide, L x denotes an extrinsic ligand for the metal and x indicates the number of units of ligand for one unit of the transition metal or transition metal compound.
- AB denotes, for example, a transition metal compound, such as a transition metal oxide
- L x denotes an extrinsic ligand for the metal
- x indicates the number of units of ligand for one unit of the transition metal or transition metal compound.
- the value of x for any specific ligand and any specific combination of ligand with a transition metal oxide may be determined simply by balancing valences.
- the method may form a CEM layer comprising doped nickel oxide, such as NiO:L x , wherein the dopant comprising a back-donating ligand comprises a molecule of the form C a H b N d O f (in which a 3 1, and b, d and f 3 0) such as: carbonyl (CO), cyano (CN-) , ethylenediamine (C 2 H 8 N 2 ) , 1, 10-phenanthroline (C 12 H 8 N 2 ) , bipyridine (C 10 H 8 N 2 ) , pyridine (C 5 H 5 N) , acetonitrile (CH 3 CN) and cyanosulfanides such as thiocyanate (NCS ) .
- CO carbonyl
- CN- cyano
- ethylenediamine C 2 H 8 N 2
- 1, 10-phenanthroline C 12 H 8 N 2
- bipyridine C 10 H 8 N 2
- pyridine C 5 H 5
- the forming of the layer of correlated electron material may, in particular, use a physical vapour deposition, such as reactive sputtering, of a transition metal compound, for example, a transition metal oxide, in an atmosphere of a gaseous oxide, such as carbon monoxide (CO) .
- a physical vapour deposition such as reactive sputtering
- a transition metal compound for example, a transition metal oxide
- a gaseous oxide such as carbon monoxide (CO)
- CO carbon monoxide
- the forming of the layer of correlated electron material may, in particular, comprise a chemical vapour deposition, such as an atomic layer deposition (ALD) , of a transition metal compound, for example, a transition metal oxide.
- ALD atomic layer deposition
- the atomic layer deposition may form the layer of correlated electron material utilising separate precursor molecules AX and BY, according to the expression (6) below:
- AX,gas) + BY,gas) AB, solid) + XY(gas) (6)
- A of expression (4) corresponds to the transition metal, and "AB” a transition metal compound, such as a transition metal oxide .
- the "X" of expression (4) may comprise one or more of an organic or other ligand, such as amidinate (AMD) , cyclopentadienyl (Cp) , bis ( ethylcylcopentadienyl ) ((EtCp) 2 ), bis (pentamethylcyclo- pentadienyl) (C 5 (CH 3 ) 5 ) 2 bis (2,2, 6, 6-tetramethylheptane-3 , 5-dionato) ((thd) 2 ), acetylacetonato (acac) , bis (methylcyclopentadienyl ) ((MeCp) 2 ), dimethylglyoximato (dmg) 2 , (apo) 2 where apo is 2-amino-pent- 2-ene-4-onato, (dmamb) 2 where dmamb is l-dimethylamino-2-methyl-2- butanolato, (dm
- Suitable precursor molecules AX include organometallic compounds of the transition metals having one or more of these ligands alone or in combination together with other ligands .
- a nickel based precursor AX may comprise, for example, nickel amidinate (Ni(AMD)), bis ( cyclopentadienyl ) nickel (Ni(Cp) 2 ), nickel acetoacetonate (Ni(acac) 2 ), nickel dimethylglyoximate (Ni(dmg) 2 ), bis ( ethylcyclo- pentadienyl )nickel (Ni ( EtCp ) 2 ) , bis (methylcyclopentadienyl ) nickel (Ni (CH 3 C 5 H 4 ) 2 ) , bis (pentamethylcyclopentadienyl ) nickel (Ni (C 5 (CH 3 ) 5 ) 2 ), nickel 2-amino-pent-2-en-4-anato (Ni(apo) 2 ), Ni (dmamb) 2 where dmamb is l-dimethylamino-2-methyl
- the precursor "BY” in expression (4) may comprise a gaseous oxide (as an oxidant) , such as water (H 2 O) , oxygen (O 2 ) , ozone (O 3 ) , nitric oxide (NO) , nitrous oxide (N 2 O) hydrogen peroxide (H 2 O 2 ) or plasma-formed oxygen radical (O ⁇ ) ⁇
- a gaseous oxide such as water (H 2 O) , oxygen (O 2 ) , ozone (O 3 ) , nitric oxide (NO) , nitrous oxide (N 2 O) hydrogen peroxide (H 2 O 2 ) or plasma-formed oxygen radical (O ⁇ ) ⁇
- the present disclosure also provides a correlated electron material (CEM) device, comprising a conductive substrate, a CEM layer and a conductive overlay, wherein the CEM layer has sidewalls having, at least in part, a recess as compared to the sidewalls of the conductive substrate and the conductive overlay.
- CEM correlated electron material
- the present disclosure further provides an integrated circuit comprising a CEM device comprising a conductive substrate, a CEM layer and a conductive overlay, wherein the device is provided between an upper metal interconnect in a cover layer and a lower metal interconnect in a substrate, the upper metal interconnect and the conductive overlay having a trench contact, and wherein the CEM layer has sidewalls having, at least in part, a recess therein (as compared to the sidewalls of the conductive substrate and the conductive overlay) .
- the present disclosure also provides an electronic device comprising an integrated circuit having a CEM device comprising a conductive substrate, a CEM layer and a conductive overlay, wherein the device is provided between an upper metal interconnect in a cover layer and a lower metal interconnect in a substrate, the upper metal interconnect and the conductive overlay having a trench contact, and wherein the CEM layer has sidewalls having, at least in part, a recess therein (as compared to the sidewalls of the conductive substrate and the conductive overlay) .
- the CEM layer may be interposed between the conductive substrate and the conductive overlay.
- the recess may extend inwardly to an extent from about 1 nm to about 10 nm. It may extend around the CEM layer and span substantially the whole of the thickness of the CEM layer.
- a moisture barrier layer may be provided on substantially the whole of the sidewalls of the conductive substrate and the sidewalls of the CEM layer (including the inner walls of the recess) as well as on the sidewalls of the conductive overlay below and up to the trench contact.
- Figure 1A shows a schematic illustration of a current density versus voltage profile of a CEM switching device
- Figure IB shows a schematic illustration of the CEM switching device of Figure 1A
- Figure 1C shows a schematic diagram of an equivalent circuit for the switching device
- Figures 2A and 2B are schematic illustrations showing the dry etching of a layer of conductive substrate, a layer of correlated electron material and a layer of conductive overlay to form a stack for a CEM switching device;
- Figures 3A and 3B are schematic illustrations showing the damage which can occur at the sidewalls of the CEM layer during dry etching to form a stack for a CEM switching device;
- Figures 4A and 4B are schematic illustrations showing the sputtering of the conductive substrate onto the sidewalls of the CEM layer which can occur during dry etching to form a stack for a CEM switching device;
- Figures 5A, 5B, 5C, 5D, 5E and 5F are schematic illustrations showing one embodiment of the method of the present disclosure; and Figure 6 is a flow diagram illustrating an embodiment of Figures 5A, 5B, 5C, 5D, 5E and 5F.
- FIG. 2A and 2B there is shown a scheme generally illustrating the dry etching of a layer of a conductive substrate 202, a layer of a correlated electron material 204 and a layer of a conductive overlay 206 to from a stack, generally designated 250, comprising a conductive overlay 280, a CEM layer 270 and a conductive substrate 260 for a CEM switching device.
- the CEM layer 270 may comprise a doped nickel oxide NiO:C as described above.
- the conductive substrate 260 and the conductive layer 280 may each comprise a first (bulk) layer comprising tantalum nitride (TaN) and a second layer (liner) comprising iridium (not shown) .
- the iridium layer in both the conductive overlay 280 and the conductive substrate 260 contacts the CEM layer 270.
- a (FSG) glass (Si0 2 ) plate 208 which is in turn disposed on a substrate 210 in which a copper interconnect 212 is provided.
- the substrate 210 may comprise (FSG) glass (Si0 2 ) or low k SiCOH dielectric.
- a silicon nitride barrier layer 214 is provided between the substrate 210 and the glass plate 208.
- the glass plate 208 and the barrier layer 214 include a via 216 providing contact between the conductive substrate 202 and the copper interconnect 212.
- a hard mask 218 comprising a layer of a silica or silicon nitride is provided on the conductive overlay 202.
- the hard mask 218, which may be patterned by a standard photolithographic process using a positive or negative photoresist and dry etch, defines the lateral dimensions of the (trapezoidal) CEM switching device.
- the dry etching (for example, reactive ion etching or deep reactive ion etching) results in a stack 250 which is ready for integration of the device to an integrated circuit .
- the integration may, for example, comprise a deposition of a cover layer comprising an insulating material, for example, silica, etching of a trench in the cover layer which exposes the conductive overlay of the device and deposition of an interconnect in the trench so that it contacts the conductive overlay of the device and fills the trench.
- a cover layer comprising an insulating material, for example, silica
- the integration may also comprise deposition of a moisture barrier layer (not shown) , for example, of silicon nitride (SiN ) , over the stack 250 prior to the etching of the trench.
- a moisture barrier layer for example, of silicon nitride (SiN )
- SiN silicon nitride
- It may further comprise deposition of a metal barrier layer, for example, titanium nitride or tantalum nitride, in the trench and over the conductive overlay prior to deposition of the metal interconnect.
- a metal barrier layer for example, titanium nitride or tantalum nitride
- Figures 3A and 3B show a scheme generally illustrating the occurrence of damage D at the sidewalls of the CEM layer 270 during dry etching of layer of correlated electron material 204.
- this damage may disrupt the crystal structure or doping of the CEM layer 270 at the sidewall leading to partially bound moieties which can adsorb moisture and/or cause the metallisation of the CEM layer.
- the damage may provide a conductive path (hashed lines; a so-called “leaky channel") between the conductive overlay 280 and the conductive substrate 260 disrupting the switching of the CEM layer 270 and degrading its performance.
- Figures 4A and 4B show a scheme generally illustrating the occurrence of sputtering (of iridium at least) SP onto the sidewalls of the CEM layer 270 during dry etching of the layer of conductive substrate 202.
- the CEM layer 270 may be a CEM layer 270 which has suffered damage D at its sidewalls as described above.
- the material (iridium at least) trapped at the sidewalls of the CEM layer 270 may result in a conductive path in the stack 250 at the sidewall of the CEM layer 270 between the conductive overlay 280 and the conductive substrate 260 which can also disrupt the switching of the device and degrade its performance .
- one embodiment of the method of the present disclosure provides that the dry etching is stopped after the layer of correlated electron material 204 has been removed and that a protective polymer coating 220 is provided over the part-formed stack 250' (and the layer of conductive substrate 202) .
- the interruption of the dry etching leaves a layer of conductive substrate 202 which is substantially intact as compared to the conductive overlay 280 and the CEM layer 270.
- the CEM layer 270 is shown here as a CEM layer which has suffered damage D at the sidewalls as described above .
- the etch trace data produced by the etch chamber may be monitored so that the dry etching can be stopped when the data shows attenuation of a nickel-based signal.
- the attenuation of the nickel-based signal indicates that the layer of correlated electron material 204 is etched through and that the layer of conductive substrate 202 has become exposed.
- the whole of the part-formed stack 250' is coated with a protective polymer.
- the coating of protective polymer 220 may be provided by a polymer deposition process which occurs within the etch chamber (i.e. an in-situ process) . Note that the coating of protective polymer 220 covers not just the sidewalls of the part-formed stack 250' but also the upper surfaces of the hard mask 218 and the layer of conductive substrate 202.
- the dry etching may employ the same process conditions or different process conditions as compared to those used for dry etching the layer of conductive substrate 202 (or the layer of correlated electron material 204 or the layer of conductive overlay 206) .
- the dry etching of the layer of conductive substrate leads to its removal from the glass plate 208 but the trapping of the material from the layer of conductive substrate 202 (for example, iridium at least) at the sidewalls of the stack 250 occurs on the protective polymer coating 220.
- the coating of the protective polymer 220 is removed from the sidewalls of the stack 250 by, for example, a wet clean.
- wet clean or a separate wet clean can be used to remove correlated electron material at the sidewalls of the CEM layer 270.
- This wet clean may remove the correlated electron material which has become damaged during dry etching of the CEM layer 204. It may, in particular, remove correlated electron material to an inward extend of 1 to 10 nm at each sidewall of the CEM layer 270 and so leave a clean and undamaged sidewall.
- the process of integration of the device to an integrated circuit may be continued with the deposition of a cover layer comprising an insulating material, for example, silica, and etching of a trench in the cover layer which exposes the conductive overlay of the device.
- a cover layer comprising an insulating material, for example, silica
- a metal interconnect is deposited in the trench by, for example, electroplating, so that it contacts the conductive overlay of the device and fills the trench.
- cover layer of insulating material may be deposited over the hard mask 218 and the hard mask 218 removed from the stack during the etching of the trench in the cover layer.
- FIG. 6 is a flow diagram particularly highlighting the steps involved in the integration a CEM device according to one embodiment of the present disclosure.
- the dry etching of the (layer of conductive overlay 206 and) the correlated electron material 204 is stopped when the etch trace signals a depletion in the amount of metal ion characteristic to the CEM layer 270 (nickel, for example) .
- the depletion in the amount of nickel ion indicates that the layer of conductive substrate 202 has been reached.
- a coating of a protective organic polymer 220 is deposited over the part-formed stack 250' and the dry etching resumed (or another etching process or process condition is used) until the layer of the conductive substrate 202 is again exposed.
- the dry etching is resumed until the glass plate 208 is reached.
- the polymer coating 220 including metal (iridium) residues) is removed from the stack 250 using a wet clean.
- the integration may be continued, for example, by depositing a cover layer comprising an insulating material, for example, silica, etching of a trench in the cover layer to expose the conductive overlay of the device and depositing of a metal interconnect in the trench so that it contacts the conductive overlay of the device and fills the trench.
- a cover layer comprising an insulating material, for example, silica
- the integration may also comprise depositing a moisture barrier layer (not shown) , for example, of silicon nitride (SiN ) , over the stack 250 prior to the etching of the trench.
- a moisture barrier layer for example, of silicon nitride (SiN )
- It may further comprise deposition of a metal barrier layer, for example, titanium nitride or tantalum nitride, in the trench and over the conductive overlay prior to deposition of the metal interconnect.
- a metal barrier layer for example, titanium nitride or tantalum nitride
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Abstract
Disclosed is a method for the fabrication of a correlated electron material (CEM) switching device, the method comprising: forming a layer of a conductive substrate (202); forming a layer of a correlated electron material (204) on the conductive substrate; forming a layer of a conductive overlay (206) on the layer of correlated electron material (204); and patterning the layers whereby to form a stack (250) comprising a conductive substrate (260), a CEM layer (270) and a conductive overlay (280), wherein the patterning comprises the following steps: forming a hard mask (218) on the layer of the conductive overlay (206); dry etching the layer of conductive overlay (206) and the layer of correlated electron material (204) whereby to form a partially formed stack (250'); depositing a coating of a protective polymer over at least sidewalls of the partially formed stack (250'); and dry etching the layer of conductive substrate 202).
Description
METHOD FOR FABRICATION OF A CEM DEVICE
TECHNICAL FIELD
[0001] The present disclosure is concerned with a method for the fabrication of a correlated electron material (CEM) device as well as with an integrated circuit including a CEM device obtained by the method .
BACKGROUND ART
[0002] Electronic switching devices are found in a wide variety of electronic device types, such as computers, digital cameras, cellular telephones, tablet devices, personal digital assistants and so forth, where they may function as memory and/or logic devices.
[0003] Factors of interest to a designer in considering whether a particular electronic switching device is suitable for such a function, may include physical size, storage density, operating voltages, impedance ranges, and/or power consumption. Other factors of interest may include cost of manufacture, ease of manufacture, scalability and/or reliability.
[0004] There appears to be an ever-increasing drive towards memory and/or logic devices which can exhibit lower power and/or higher speed. Switching devices comprising a correlated electron material are at the forefront of this drive not just because they can exhibit low power and/or high speed but also because they are generally reliable and easily and cheaply manufactured.
SUMMARY OF DISCLOSURE
[0005] The present disclosure describes an improved CEM device and methods for its manufacture. The CEM device may, in particular, be a switching device. The CEM switching device may find application as a correlated electron random access memory (CERAM) in memory and/or logic devices which may be used with a wide range of electronic circuit
types, such as memory controllers, memory arrays, filter circuits, data converters, optical instruments, phase locked loop circuits, microwave and millimeter wave transceivers, and so forth.
[0006] A CEM switching device can exhibit a rapid conductor-to- insulator transition as compared to other switching devices because the switching is brought about by an electron correlation rather than by a solid state structural phase change or by formation of filaments, as is found respectively in phase change memory devices and resistive RAM devices .
[0007] The rapid conductor-to-insulator transition of a CEM switching device may, in particular, be responsive to a quantum mechanical phenomenon in contrast to the melting/solidification or filament formation found respectively in phase change and resistive RAM devices. The quantum mechanical transition in a CEM switching device between a relatively conductive state and a relatively insulative state (or between a first impedance state and a second impedance state) may occur in several ways.
[0008] In one respect, a quantum mechanical transition of a CEM between a relatively insulative/higher impedance state and a relatively conductive/lower impedance state may be understood in terms of a Mott transition.
[0009] As used herein, references to a Mott transition are references to traditional Mott transitions (which are described in the literature as purely coulombic) as well as references to Mott- like transitions (in which the coulombic interaction is modified by some other electron interaction, such as a dipole-core charge interaction) . Accordingly, a reference to a Mott insulator includes a reference to a charge-transfer (Mott) insulator, such as nickel (II) oxide, in which the columbic interaction or screening is modified by a charge transfer complex through hybridisation with the oxygen band.
[0010] In accordance with a Mott transition, a material may switch from a relatively insulative/higher impedance state to a relatively
conductive/lower impedance state if a Mott transition condition is satisfied. The Mott criteria may be defined by (nc)1/3a 0.26, wherein nc denotes a concentration of electrons, and wherein "a" denotes the Bohr radius . If a threshold carrier concentration is achieved, such that the Mott criteria is met, the Mott transition is believed to occur. Responsive to the Mott transition occurring, the state of the CEM device changes from a relatively higher resistance/higher capacitance state (e.g., an insulative/higher impedance state) to a relatively lower resistance/lower capacitance state (e.g., a conductive/lower impedance state) .
[0011] In another respect, the Mott transition may be controlled by a localization of electrons. If carriers, such as electrons, for example, are localized, a strong coulomb interaction between the carriers is believed to split the bands of the CEM to bring about a relatively insulative (relatively higher impedance) state. If electrons are no longer localized, a weak coulomb interaction may dominate, which may give rise to a removal of band splitting, which may, in turn, bring about a metal (conductive) band (relatively lower impedance state) that is substantially dissimilar from the relatively higher impedance state.
[0012] The switching from a relatively insulative/higher impedance state to a relatively conductive/lower impedance state may bring about a change in capacitance in addition to a change in resistance. For example, a CEM switch may exhibit a variable resistance together with a property of variable capacitance. In other words, impedance characteristics of a CEM switch may include both resistive and capacitive components. For example, in a metal state, a CEM switch may comprise a relatively low electric field that may approach zero, and therefore may exhibit a substantially low capacitance, which may likewise approach zero.
[ 0013 ] Similarly, in a relatively insulative/higher impedance state, which may be brought about by a higher density of bound or correlated electrons, an external electric field may be capable of penetrating the CEM and, therefore, the CEM may exhibit higher
capacitance based, at least in part, on additional charges stored within the CEM. Thus, for example, a transition from a relatively insulative/higher impedance state to a relatively conductive/lower impedance state in a CEM switch may result in changes in both resistance and capacitance.
[0014] A switching device formed from a CEM may exhibit switching of impedance states responsive to a Mott-transition in a majority of the volume of the CEM comprising the device. The CEM may, in particular, form a "bulk switch". As used herein, the term "bulk switch" refers to at least a majority volume of a CEM switching a device's impedance state, such as in response to a Mott-transition. For example, substantially all CEM of a device may switch from a relatively insulative/higher impedance state to a relatively conductive/lower impedance state or from a relatively conductive/lower impedance state to a relatively insulative/higher impedance state responsive to a Mott-transition.
[0015] In one arrangement, shown in Figure IB, a CEM switching device may comprise a layer of correlated electron material (a CEM layer) sandwiched between a conductive substrate and a conductive overlay. In this arrangement, the CEM switching device can act as memory storage element. In other arrangements, the CEM switching device may comprise either a CEM layer provided on a conductive substrate or a CEM layer provided with a conductive overlay. In these other arrangements, the device comprises source and drain regions providing for a flow of current across the device.
[0016] Referring now to Figure 1A, a current density versus voltage profile 100 of a CEM switching device is shown which illustrates its switching behaviour. Based, at least in part, on a voltage applied to terminals of a CEM device, for example, during a "write operation, " the CEM device may be placed into a relatively low- impedance state or a relatively high-impedance state. For example, application of a voltage VSet and a current density Jsst may bring about a transition of the CEM switching device to a relatively low-impedance memory state. Conversely, application of a voltage
and a current
density Jreset may bring about a transition of the CEM device to a relatively high-impedance memory state.
[0017] As shown in Figure 1A, reference designator 110 illustrates the voltage range that may separate VSet from Veset. Following placement of the CEM switching device into a high-impedance state or a low- impedance state, the particular state of the CEM switching device may be detected by application of a voltage Vread (e.g., during a read operation) and detection of a current or current density at terminals of the CEM switching device (e.g., utilizing read window 102) .
[0018] In accordance with Figure 1A, if sufficient bias is applied (e.g., exceeding a band-splitting potential) and the aforementioned Mott condition is satisfied (e.g., injected electron holes are of a population comparable to a population of electrons in a switching region, for example) , a CEM switching device may switch from a relatively low-impedance state to a relatively high-impedance state, for example, responsive to a Mott transition. This may correspond to point 108 of the voltage versus current density profile of Figure 1A. At, or suitably nearby this point, electrons are no longer screened and become localized near the metal ion. This correlation may result in a strong electron-to-electron interaction potential which may operate to split the bands to form a relatively high-impedance material .
[0019] If the CEM switching device comprises a relatively high- impedance state, current may be generated by transportation of electron holes. Consequently, if a threshold voltage is applied across terminals of the CEM device, electrons may be injected into a metal-insulator-metal (MIM) diode over the potential barrier of the MIM device. In certain devices, injection of a threshold current of electrons, at a threshold potential applied across terminals of a CEM device, may perform a "set" operation, which places the CEM device into a low-impedance state. In a low-impedance state, an increase in electrons may screen incoming electrons and remove a localization of electrons, which may operate to collapse the band-splitting potential, thereby giving rise to the low-impedance state.
[0020] The current in a CEM switching device may be controlled by an externally applied "compliance" condition, which may be determined at least partially on the basis of an applied external current, which may be limited during a write operation, for example, to place the CEM device into a relatively high-impedance state. This externally- applied compliance current may, in some devices, also set a condition of a current density for a subsequent reset operation to place the CEM device into a relatively high-impedance state. As shown in the particular device of Figure 1A, a current density JComP applied during a write operation at point 116 to place the CEM switching device into a relatively low-impedance state, may determine a compliance condition for placing the CEM device into a high-impedance state in a subsequent write operation. As shown in Figure 1A, the CEM device may be subsequently placed into a high-impedance state by application of a current density Jreset - Jcomp at a voltage Vreset at point 108, at which Jcomp is externally applied.
[0021] The compliance may, in particular, set a number of electrons in a CEM switching device which may be "captured" by holes for the Mott transition. In other words, a current applied in a write operation to place a CEM device into a relatively low-impedance memory state may determine a number of holes to be injected to the CEM device for subsequently transitioning the CEM switching device to a relatively high-impedance memory state.
[0022] As pointed out above, a reset condition may occur in response to a Mott transition at point 108. Such a Mott transition may bring about a condition in the CEM switching device in which a concentration of electrons n approximately equals, or becomes at least comparable to, a concentration of electron holes p. This condition may be modeled according to expression (1) as follows: 0.26 (1)
wherein ATF corresponds to a Thomas Fermi screening length, and C is a constant.
[ 0023 ] A current or current density in region 104 of the voltage versus current density profile shown in Figure 1A, may exist in response to injection of holes from a voltage signal applied across terminals of the CEM switching device. Here, injection of holes may meet a Mott transition criterion for the low-impedance state to high- impedance state transition at current IMi as a threshold voltage VMI is applied across terminals of a CEM device. This may be modeled according to expression (2) as follows:
wherein Q(VMI) corresponds to the charged injected (holes or electrons) and is a function of an applied voltage. Injection of electrons and/or holes to enable a Mott transition may occur between bands and in response to threshold voltage VMI, and threshold current IMi- By equating electron concentration n with a charge concentration to bring about a Mott transition by holes injected by IMi in expression (2) according to expression (1), a dependency of such a threshold voltage VMI on Thomas Fermi screening length ATF may be modeled according to expression (3), as follows:
wherein ACEM is a cross-sectional area of a CEM switching device; and Jreset(Vm) may represent a current density through the CEM switching device to be applied to the CEM switching device at a threshold voltage VMIr which may place the CEM switching device into a relatively high- impedance state .
[0024] Figure IB shows a CEM switching device comprising a CEM layer sandwiched between a conductive substrate and a conductive overlay and Figure 1C shows a schematic diagram of an equivalent circuit for the switching device.
[0025] As previously mentioned, the CEM switching device may exhibit characteristics of both variable resistance and variable capacitance. In other words, the CEM switching device may be considered as a variable impedance device in which the impedance depends at least in part on resistance and capacitance characteristics of the device if measured across device terminals . The equivalent circuit for a variable impedance device may comprise a variable resistor, such as variable resistor, in parallel with a variable capacitor. Of course, although a variable resistor and variable capacitor are depicted in Figure 1C as comprising discrete components, the variable impedance device, such as that shown, may comprise a substantially homogenous CEM.
Table 1 Correlated Electron Switch Truth Table
[0026] Table 1 illustrates an example truth table for an example variable impedance device, such as the device of Figure 1A. Table 1 shows that a resistance of a variable impedance device, such as that shown, may transition between a low-impedance state and a substantially dissimilar, high-impedance state as a function at least partially dependent on a voltage applied across the CEM switching device. The impedance exhibited at a low-impedance state may, for example, be approximately in the range of 10.0 - 100,000.0 times lower than an impedance exhibited in a high-impedance state. However, the impedance exhibited at a low-impedance state may be approximately in the range of 5.0 to 10.0 times lower than an impedance exhibited in a high-impedance state. Table 1 also shows that a capacitance of a
variable impedance device, such as the device shown, may transition between a lower capacitance state, which may, for example comprise an approximately zero, or very little, capacitance, and a higher capacitance state that is a function, at least in part, of a voltage applied across the CEM switching device.
[ 0027 ] The CEM switching device may be placed into a relatively low-impedance memory state, such as by transitioning from a relatively high impedance state, for example, via injection of a sufficient quantity of electrons to satisfy a Mott transition criterion. In transitioning a CEM switching device to a relatively low-impedance state, if enough electrons are injected and the potential across the terminals of the CEM device overcomes a threshold switching potential (e.g., , injected electrons may begin to screen. As previously mentioned, screening may operate to delocalize double-occupied electrons to collapse the band-splitting potential, thereby bringing about a relatively low-impedance state.
[ 0028 ] In particular embodiments, changes in impedance states of CEM devices, such as changes from a low-impedance state to a substantially dissimilar high-impedance state, for example, may be brought about by "back-donation" of electrons of compounds comprising NixOy (wherein the subscripts "x" and "y" comprise whole numbers) . As the term is used herein, "back-donation" refers to a supplying of one or more electrons (i.e. electron density) to a transition metal, transition metal oxide, or any combination thereof (i.e. to an atomic orbital of a metal), by an adjacent molecule of a lattice structure (i.e. a ligand), and at the same time donation of electron density from the metal center into an unoccupied antibonding orbital on the ligand/dopant . The electron back-donating ligand may be a n-back- bonding ligand such as carbonyl (CO) , nitrosyl (NO) , an isocyanide (RNC where R is H, C1-C6 alkyl or C6-Cio-aryl ) , an alkene (e.g. ethene) , an alkyne (e.g. ethyne) or a phosphine such as a trialkyl phosphine or a triaryl phosphine (R3P wherein R is H, Ci-C6_alkyl or C6-Cio-aryl) , for example triphenylphosphine (PPk ).
[0029] Back-donation may permit a transition metal, transition metal compound, transition metal oxide, or a combination thereof, to maintain an ionization state that is favorable to electrical conduction under an influence of an applied voltage. In certain embodiments, back-donation in a CEM, for example, may occur responsive to use of carbonyl (CO) or a nitrogen-containing dopant, such as ammonia (NH3) , ethylene diamine (C2H8N2) , or members of an oxynitride family (NxOy) , for example, which may permit a CEM to exhibit a property in which electrons are controllably, and reversibly, "donated" to a conduction band of the transition metal or transition metal oxide, such as nickel, for example, during operation of a device or circuit comprising a CEM. Back donation may be reversed, for example, in nickel oxide material (e.g., NiO:CO or NzOiNM), thereby permitting the nickel oxide material to switch to exhibiting a substantially dissimilar impedance property, such as a high-impedance property, during device operation.
[0030] Thus, in this context, an electron back-donating material refers to a material that exhibits an impedance switching property, such as switching from a first impedance state to a substantially dissimilar second impedance state (e.g., from a relatively low impedance state to a relatively high impedance state, or vice versa) based, at least in part, on influence of an applied voltage to control donation of electrons, and reversal of the electron donation, to and from a conduction band of the CEM.
[0031] In some embodiments, by way of back-donation, a CEM switch comprising a transition metal, transition metal compound, or a transition metal oxide, may exhibit low-impedance properties if the transition metal, such as nickel, for example, is placed into an oxidation state of 2+ (e.g., Ni2+ in a material, such as NiO:CO or NiO:NH3). Conversely, electron back-donation may be reversed if a transition metal, such as nickel, for example, is placed into an oxidation state of 1+ or 3+.
[0032] Accordingly, during operation of a CEM device, back- donation may result in "disproportionation, " which may comprise
substantially simultaneous oxidation and reduction reactions , substantially in accordance with expression (4), below:
2Ni2+ Ni1+ + Ni3+ (4)
[0033] Such disproportionation, in this instance, refers to formation of nickel ions as Ni1+ + Ni3+ as shown in expression (4), which may bring about, for example, a relatively high-impedance state during operation of the CEM device. In an embodiment, a dopant such as a carbon-containing ligand, carbonyl (CO) or a nitrogen-containing ligand, such as an ammonia molecule (NH3) , may permit sharing of electrons during operation of a CEM device so as to give rise to the disproportionation reaction of expression (4), and its reversal, substantially in accordance with expression (5), below:
Ni1+ + Ni3+ 2Ni2+ (5)
[0034] As previously mentioned, reversal of the disproportionation reaction, as shown in expression (5), permits nickel-based CEM to return to a relatively low-impedance state.
[0035] In embodiments, depending on a molecular concentration of NiO:CO or NiO:NH3, for example, which may vary from values approximately in the range of an atomic concentration of 0.1% to 10.0%, Vreset and Vset, as shown in FIG. 1A, may vary approximately in the range of 0.1 V to 10.0 V subject to the condition that Vset ³ Vreset. For example, in one possible embodiment, Vreset may occur at a voltage approximately in the range of 0.1 V to 1.0 V, and Vset may occur at a voltage approximately in the range of 1.0 V to 2.0 V, for example. It should be noted, however, that variations in Vset and Vreset may occur based, at least in part, on a variety of factors, such as atomic concentration of an electron back-donating material, such as NiO:CO or NiO:NH3 and other materials present in the CEM device, as well as other process variations, and claimed subject matter is not limited in this respect.
[0036] The fabrication of a CEM device into an integrated circuit generally begins with the formation of the device layers by patterning a layer of a conductive substrate, a layer of a correlated electron material and a layer of a conductive overlay which have been deposited on an insulating substrate, such as silica, having one or more embedded interconnects .
[0037] The patterning forms a stack from the deposited layers which may be fabricated to full integration in an integrated circuit by depositing a cover layer comprising an insulating material, such as silica, over the stack, patterning the cover layer whereby to form a trench in which the conductive overlay is exposed and depositing a metal interconnect in the trench which contacts the conductive overlay .
[0038] Note that the patterning of the cover layer may also comprise forming an additional trench and via for an additional metal interconnect enabling contact between other devices, such as transistors, at different levels in a 3-dimensional integrated circuit .
[0039] The materials of the conductive substrate, the CEM layer and the conductive overlay tend to be chemically resistant so that a dry etching (rather than a wet etching) is required in order to form the stack.
[0040] As used herein the expression "dry etching" refers to the removal of a material by exposing a surface of the material to a bombardment of ions (usually derived from a plasma of reactive gases such as fluorocarbons, oxygen, chlorine, boron trichloride, sometimes with addition of nitrogen, argon, helium, and other gases) to remove portions of the material from the exposed surface.
[0041] Note that dry etching is a directional (or anisotropic) process which is typically used to remove material in the vertical direction (rather than the horizontal direction) .
[0042] One problem with the fabrication of a CEM device to an integrated circuit is that dry etching of the layer of correlated electron material can lead to damage at the sidewalls of the CEM layer in the stack.
[0043] This damage appears to disrupt the crystal structure or doping of the CEM layer at the sidewall and lead to a metal overlay or partially bound moieties which may adsorb moisture. In either case, the result is a conductive path (a so-called "leaky channel") between the conductive overlay and the conductive substrate at each sidewall which can disrupt the switching of the CEM layer and degrade its performance .
[0044] Another problem with the fabrication of a CEM device to an integrated circuit is that the dry etching of the layer of conductive substrate can lead to sputtering of the material of the conductive substrate onto the sidewalls of the CEM layer in the stack.
[0045] This sputtering results in a conductive path between the conductive overlay and the conductive substrate at each sidewall of the CEM layer which can disrupt the switching of the CEM layer and degrade its performance .
[0046] The present disclosure relates to a method which avoids these problems and the formation of unwanted conductive paths between the conductive overlay and the conductive substrate at the sidewalls of the CEM layer.
[0047] Accordingly, the present disclosure provides a method for the integration of a correlated electron material (CEM) device to an integrated circuit, the method comprising
forming a layer of a conductive substrate on a glass or other substrate;
forming a layer of a correlated electron material on the layer of conductive substrate;
forming a layer of a conductive overlay on the layer of correlated electron material; and
patterning the layers whereby to form a stack comprising a conductive substrate, a CEM layer and a conductive overlay, wherein the patterning comprises the following steps :
forming a hard mask on the layer of conductive overlay;
dry etching the layer of conductive overlay and the layer of correlated electron material whereby to form a partially formed stack; depositing a coating of a protective polymer over at least sidewalls of the partially formed stack; and
dry etching the layer of conductive substrate.
[0048] The hard mask may comprise a dielectric material such as silica (SiCh) or silicon nitride (Si3N4) which is generally resistant to the dry etching used for forming the stack but susceptible to wet or other etching.
[0049] It may be formed, for example, by standard lithographic processes using a photoresist spun or otherwise deposited onto a silica or silicon nitride layer formed on the layer of conductive overlay. Alternatively, the photoresist may be spun or otherwise deposited on a stack comprising a planarization layer and an antireflection layer deposited on the silica or silicon nitride layer.
[0050] In embodiments, the method comprises depositing a coating of a protective polymer over the whole of the partially formed stack viz., the protective polymer coats not just the sidewalls of the partially formed stack but also the upper surfaces of the layer of conductive substrate and the hard mask.
[0051] The method may further comprise dry etching the protective polymer coating whereby to remove the protective polymer from the upper surfaces of the layer of conductive substrate and the hard mask.
[0052] This dry etching of the protective polymer coating may comprise a separate step to the etching of the conductive substrate. It may use different process conditions or the same process conditions as compared to those used for the dry etching of the layer of conductive substrate.
[0053] The protective polymer may comprise any organic polymer which is susceptible to dry etching (for example, reactive ion etching) and to wet etching. It may, in particular, comprise a fluorocarbon, or hydrofluorocarbon polymer, for example, tetrafluoro- ethylene .
[0054] The coating of the protective polymer may be formed by physical vapour deposition or by chemical vapour deposition. In one embodiment, the coating of protective polymer is formed by chemical vapour deposition of a fluorocarbon or hydrofluorocarbon polymer using gases of formula CxHyFz where x and z > 0 and y > 0.
[0055] The method may further comprise removing the coating of protective polymer from the side-walls of the stack after the dry etching of the layer of conductive substrate. The removal may be carried out by wet cleaning the stack by, for example, dipping in a solution of dilute hydrofluoric acid (DHF) .
[0056] Although the wet clean will generally be selective for the protective polymer coating it may also etch the correlated electron material. Advantageously, therefore, the method may further comprise etching a portion of the correlated electron material at the sidewalls of the CEM layer whereby to remove any damage which has occurred during the dry etching of the layer of correlated electron material.
[0057] The removal of portions of the correlated electron material at the sidewalls of the CEM layer in the stack may provide an indent or recess in the CEM layer which extends into the CEM layer to an extent from about 1 nm to about 10 nm. The indent or recess may also extend around the CEM layer and across the whole of the thickness of the CEM layer.
[0058] Of course, the method may further comprise removing the hard mask from the stack. The removal may be carried out prior to forming the cover layer of insulating material or at the same time as the etching of a trench in the cover layer.
[0059] The method may also comprise depositing a cover layer comprising an insulating material, such as silica, over the stack and patterning the cover layer whereby to form a trench in the cover layer in which (at least a part) of the conductive overlay protrudes.
[0060] The method may further comprise depositing a metal barrier layer over the conductive overlay and at least the interior walls of the trench. The metal barrier layer prevents the migration of metal ion from the metal interconnect into the cover plate and the device. It also protects against the ingress of moisture from ambient or the cover layer to the stack. The metal barrier layer may, in particular, comprise one or more of tantalum nitride (TaN) , titanium nitride (TiN) , cobalt (Co), ruthenium (Ru) and tantalum (Ta) .
[0061] The method may further comprise depositing a moisture barrier layer over the stack prior to the deposition of the cover layer. The moisture barrier layer, which may, for example, comprise silicon nitride (Si3N4) , silicon carbon nitride (SiCN) or silicon carbide, prevents the ingress of moisture, for example, from ambient or from the etching of the cover layer, into the sidewalls of the fabricated device.
[0062] Note that the moisture barrier layer is etched away from the upper surface (and a part of the sidewalls) of the conductive overlay when the trench is etched in the cover layer.
[0063] The method may further comprise depositing a metal interconnect whereby to substantially fill the trench. The metal interconnect may comprise aluminium, cobalt, ruthenium, tungsten or copper .
[0064] The forming of the layer of conductive overlay, the layer of correlated electron material and the layer of conductive substrate may comprise any suitable physical vapour deposition or chemical vapour deposition. In embodiments, the forming of at least the CEM
layer comprises a chemical vapour deposition and, in particular, an atomic layer deposition.
[0065] In embodiments, the conductive overlay and/or the conductive substrate comprise a major (bulk) layer comprising a conductive metal nitride and a minor layer comprising a noble metal or a conductive metal oxide .
[0066] Accordingly, the forming of the layer of conductive substrate comprises depositing a first layer of a metal nitride and depositing a second layer of a noble metal or other conductive material on the first layer. And the forming of the conductive overlay may comprise depositing a first layer of a noble metal or other conductive material and depositing a second layer of a metal nitride on the first layer .
[0067] The metal nitride may comprise one or more of titanium nitride, tantalum nitride, and tungsten nitride. The noble metal or other conductive material may comprise platinum, titanium, copper, aluminium, cobalt, nickel, tungsten, cobalt silicide, ruthenium oxide, chromium, gold, palladium, indium tin oxide, tantalum, silver, iridium, iridium oxide or any combination thereof.
[0068] The forming of the layer of conductive substrate may be on an insulating substrate, such as a silica, provided on an underlying dielectric material. The substrate may include a via for contacting the conductive substrate with a copper, tungsten, ruthenium, cobalt or aluminium interconnect provided in the dielectric material .
[0069] In one embodiment, the substrate comprises a fluorosilicate glass (FSG) plate provided on a (low k) dielectric material. The substrate includes a via for contacting the conductive substrate of the device through the glass (FSG) plate with a copper interconnect embedded in the dielectric material.
[0070] In embodiments, the method may comprise forming a layer of a correlated electron material comprising a doped metal compound of a
d- or f-block element (especially one exhibiting an incomplete d- or f-block shell) such as nickel, cobalt, iron, yttrium or ytterbium. It may comprise forming a CEM layer comprising an oxide of a d- or f- block element and, in particular, a transition metal oxide (TMO) such as nickel oxide, cobalt oxide, hafnium oxide, iron oxide or an oxide or a rare earth element such as yttrium oxide.
[0071] The method may alternatively comprise forming a layer of a correlated electron material comprising a complex (or "mixed") oxide of d- and/or f-block elements, for example, as a perovskite such as chromium doped strontium titanate, lanthanum titanate, praseodymium calcium manganate or praseodymium lanthanum manganate or a complex oxide or a rare earth element and a transition metal such as yttrium titanium oxide or ytterbium titanium oxide.
[0072] In embodiments, the metal compound of the correlated electron material may be of general formula AB:LX (for example, NiO:CO) wherein the AB denotes, for example, a transition metal compound, such as a transition metal oxide, Lx denotes an extrinsic ligand for the metal and x indicates the number of units of ligand for one unit of the transition metal or transition metal compound. The value of x for any specific ligand and any specific combination of ligand with a transition metal oxide may be determined simply by balancing valences.
[0073] In embodiments, the method may form a CEM layer comprising doped nickel oxide, such as NiO:Lx, wherein the dopant comprising a back-donating ligand comprises a molecule of the form CaHbNdOf (in which a ³ 1, and b, d and f ³ 0) such as: carbonyl (CO), cyano (CN-) , ethylenediamine (C2H8N2) , 1, 10-phenanthroline (C12H8N2) , bipyridine (C10H8N2) , pyridine (C5H5N) , acetonitrile (CH3CN) and cyanosulfanides such as thiocyanate (NCS ) .
[0074] The forming of the layer of correlated electron material may, in particular, use a physical vapour deposition, such as reactive sputtering, of a transition metal compound, for example, a transition metal oxide, in an atmosphere of a gaseous oxide, such as carbon monoxide (CO) .
[0075] The forming of the layer of correlated electron material may, in particular, comprise a chemical vapour deposition, such as an atomic layer deposition (ALD) , of a transition metal compound, for example, a transition metal oxide.
[0076] The atomic layer deposition may form the layer of correlated electron material utilising separate precursor molecules AX and BY, according to the expression (6) below:
AX,gas) + BY,gas) = AB, solid) + XY(gas) (6) wherein "A" of expression (4) corresponds to the transition metal, and "AB" a transition metal compound, such as a transition metal oxide .
[0077] The "X" of expression (4) may comprise one or more of an organic or other ligand, such as amidinate (AMD) , cyclopentadienyl (Cp) , bis ( ethylcylcopentadienyl ) ((EtCp)2), bis (pentamethylcyclo- pentadienyl) (C5 (CH3) 5) 2bis (2,2, 6, 6-tetramethylheptane-3 , 5-dionato) ((thd)2), acetylacetonato (acac) , bis (methylcyclopentadienyl ) ((MeCp)2), dimethylglyoximato (dmg)2, (apo)2 where apo is 2-amino-pent- 2-ene-4-onato, (dmamb)2 where dmamb is l-dimethylamino-2-methyl-2- butanolato, (dmamp)2 where dmamp is l-dimethylamino-2-methyl-2- propanolato .
[0078] Suitable precursor molecules AX include organometallic compounds of the transition metals having one or more of these ligands alone or in combination together with other ligands .
[0079] Accordingly, in some embodiments, a nickel based precursor AX (NiX) may comprise, for example, nickel amidinate (Ni(AMD)), bis ( cyclopentadienyl ) nickel (Ni(Cp)2), nickel acetoacetonate (Ni(acac)2), nickel dimethylglyoximate (Ni(dmg)2), bis ( ethylcyclo- pentadienyl )nickel (Ni ( EtCp ) 2 ) , bis (methylcyclopentadienyl ) nickel (Ni (CH3C5H4) 2) , bis (pentamethylcyclopentadienyl ) nickel (Ni (C5 (CH3) 5)2), nickel 2-amino-pent-2-en-4-anato (Ni(apo)2), Ni (dmamb) 2 where dmamb is
l-dimethylamino-2-methyl-2-butanolato, Ni(dmamp) 2 where dmamp is 1- dimethylamino-2-methyl-2-propanolato .
[0080] The precursor "BY" in expression (4) may comprise a gaseous oxide (as an oxidant) , such as water (H2O) , oxygen (O2) , ozone (O3) , nitric oxide (NO) , nitrous oxide (N2O) hydrogen peroxide (H2O2) or plasma-formed oxygen radical (O·)·
[0081] The present disclosure also provides a correlated electron material (CEM) device, comprising a conductive substrate, a CEM layer and a conductive overlay, wherein the CEM layer has sidewalls having, at least in part, a recess as compared to the sidewalls of the conductive substrate and the conductive overlay.
[0082] The present disclosure further provides an integrated circuit comprising a CEM device comprising a conductive substrate, a CEM layer and a conductive overlay, wherein the device is provided between an upper metal interconnect in a cover layer and a lower metal interconnect in a substrate, the upper metal interconnect and the conductive overlay having a trench contact, and wherein the CEM layer has sidewalls having, at least in part, a recess therein (as compared to the sidewalls of the conductive substrate and the conductive overlay) .
[0083] The present disclosure also provides an electronic device comprising an integrated circuit having a CEM device comprising a conductive substrate, a CEM layer and a conductive overlay, wherein the device is provided between an upper metal interconnect in a cover layer and a lower metal interconnect in a substrate, the upper metal interconnect and the conductive overlay having a trench contact, and wherein the CEM layer has sidewalls having, at least in part, a recess therein (as compared to the sidewalls of the conductive substrate and the conductive overlay) .
[0084] Embodiments in the CEM device, integrated circuit and electronic device will be apparent from the description of embodiments of the method of the present disclosure.
[0085] Note, in particular, that the CEM layer may be interposed between the conductive substrate and the conductive overlay. The recess may extend inwardly to an extent from about 1 nm to about 10 nm. It may extend around the CEM layer and span substantially the whole of the thickness of the CEM layer. A moisture barrier layer may be provided on substantially the whole of the sidewalls of the conductive substrate and the sidewalls of the CEM layer (including the inner walls of the recess) as well as on the sidewalls of the conductive overlay below and up to the trench contact.
BRIEF DESCRIPTION OF DRAWINGS
[0086] The methods, CEM device and integrated circuit according to the present disclosure will now be described in more detail having regard to the following non-limiting embodiments and the accompanying drawings in which:
Figure 1A shows a schematic illustration of a current density versus voltage profile of a CEM switching device;
Figure IB shows a schematic illustration of the CEM switching device of Figure 1A;
Figure 1C shows a schematic diagram of an equivalent circuit for the switching device;
Figures 2A and 2B are schematic illustrations showing the dry etching of a layer of conductive substrate, a layer of correlated electron material and a layer of conductive overlay to form a stack for a CEM switching device;
Figures 3A and 3B are schematic illustrations showing the damage which can occur at the sidewalls of the CEM layer during dry etching to form a stack for a CEM switching device;
Figures 4A and 4B are schematic illustrations showing the sputtering of the conductive substrate onto the sidewalls of the CEM layer which can occur during dry etching to form a stack for a CEM switching device;
Figures 5A, 5B, 5C, 5D, 5E and 5F are schematic illustrations showing one embodiment of the method of the present disclosure; and
Figure 6 is a flow diagram illustrating an embodiment of Figures 5A, 5B, 5C, 5D, 5E and 5F.
DESCRIPTION OF EMBODIMENTS
[0087] Referring now to Figures 2A and 2B, there is shown a scheme generally illustrating the dry etching of a layer of a conductive substrate 202, a layer of a correlated electron material 204 and a layer of a conductive overlay 206 to from a stack, generally designated 250, comprising a conductive overlay 280, a CEM layer 270 and a conductive substrate 260 for a CEM switching device.
[0088] The CEM layer 270 may comprise a doped nickel oxide NiO:C as described above. The conductive substrate 260 and the conductive layer 280 may each comprise a first (bulk) layer comprising tantalum nitride (TaN) and a second layer (liner) comprising iridium (not shown) . The iridium layer in both the conductive overlay 280 and the conductive substrate 260 contacts the CEM layer 270.
[0089] Referring now to Figure 2A, these layers are provided on a (FSG) glass (Si02) plate 208 which is in turn disposed on a substrate 210 in which a copper interconnect 212 is provided. The substrate 210 may comprise (FSG) glass (Si02) or low k SiCOH dielectric. A silicon nitride barrier layer 214 is provided between the substrate 210 and the glass plate 208. The glass plate 208 and the barrier layer 214 include a via 216 providing contact between the conductive substrate 202 and the copper interconnect 212.
[0090] A hard mask 218 comprising a layer of a silica or silicon nitride is provided on the conductive overlay 202. The hard mask 218, which may be patterned by a standard photolithographic process using a positive or negative photoresist and dry etch, defines the lateral dimensions of the (trapezoidal) CEM switching device.
[0091] Referring now to Figure 2B, the dry etching (for example, reactive ion etching or deep reactive ion etching) results in a stack
250 which is ready for integration of the device to an integrated circuit .
[0092] The integration may, for example, comprise a deposition of a cover layer comprising an insulating material, for example, silica, etching of a trench in the cover layer which exposes the conductive overlay of the device and deposition of an interconnect in the trench so that it contacts the conductive overlay of the device and fills the trench.
[0093] The integration may also comprise deposition of a moisture barrier layer (not shown) , for example, of silicon nitride (SiN ) , over the stack 250 prior to the etching of the trench. The moisture barrier layer, which is etched back with the hard mask during the etching of the trench, encapsulates and seals the sidewalls of stack against the ingress of moisture into the device (not shown) .
[0094] It may further comprise deposition of a metal barrier layer, for example, titanium nitride or tantalum nitride, in the trench and over the conductive overlay prior to deposition of the metal interconnect. This metal barrier layer prevents migration of metal into the device (and also acts to seal the stack against the ingress of the moisture to the device) .
[0095] Figures 3A and 3B show a scheme generally illustrating the occurrence of damage D at the sidewalls of the CEM layer 270 during dry etching of layer of correlated electron material 204.
[0096] Referring now to Figure 3A, the dry etching of the CEM layer 204, whilst removing the correlated electron material in the vertical direction, has a component which damages, but does not remove, the correlated electron material in the horizontal direction.
[0097] Referring now to Figure 3B, this damage may disrupt the crystal structure or doping of the CEM layer 270 at the sidewall leading to partially bound moieties which can adsorb moisture and/or cause the metallisation of the CEM layer. In either case, the damage
may provide a conductive path (hashed lines; a so-called "leaky channel") between the conductive overlay 280 and the conductive substrate 260 disrupting the switching of the CEM layer 270 and degrading its performance.
[0098] Figures 4A and 4B show a scheme generally illustrating the occurrence of sputtering (of iridium at least) SP onto the sidewalls of the CEM layer 270 during dry etching of the layer of conductive substrate 202. Note that, although it is not shown here, the CEM layer 270 may be a CEM layer 270 which has suffered damage D at its sidewalls as described above.
[0099] Referring now to Figure 4A, although the dry etching of the layer of conductive substrate 202 leads to removal from the glass plate 208, a substantial portion (of iridium at least) is trapped at the sidewalls of the part-formed stack 250' and, in particular, at the sidewalls of the CEM layer 270.
[0100] Referring now to Figure 4B, the material (iridium at least) trapped at the sidewalls of the CEM layer 270 may result in a conductive path in the stack 250 at the sidewall of the CEM layer 270 between the conductive overlay 280 and the conductive substrate 260 which can also disrupt the switching of the device and degrade its performance .
[0101] Referring now to Figures 5A, 5B, 5C, 5D, 5E and 5F, one embodiment of the method of the present disclosure provides that the dry etching is stopped after the layer of correlated electron material 204 has been removed and that a protective polymer coating 220 is provided over the part-formed stack 250' (and the layer of conductive substrate 202) .
[0102] Referring now to Figure 5A, the interruption of the dry etching leaves a layer of conductive substrate 202 which is substantially intact as compared to the conductive overlay 280 and the CEM layer 270. Note that the CEM layer 270 is shown here as a
CEM layer which has suffered damage D at the sidewalls as described above .
[0103] During the dry etching, the etch trace data produced by the etch chamber (not shown) may be monitored so that the dry etching can be stopped when the data shows attenuation of a nickel-based signal. The attenuation of the nickel-based signal indicates that the layer of correlated electron material 204 is etched through and that the layer of conductive substrate 202 has become exposed.
[0104] Referring now to Figure 5B, after the dry etching has been stopped, the whole of the part-formed stack 250' is coated with a protective polymer. The coating of protective polymer 220 may be provided by a polymer deposition process which occurs within the etch chamber (i.e. an in-situ process) . Note that the coating of protective polymer 220 covers not just the sidewalls of the part-formed stack 250' but also the upper surfaces of the hard mask 218 and the layer of conductive substrate 202.
[0105] Referring now to Figure 5C, the dry etching is resumed following the polymer deposition such that it removes the coating of protective polymer 220 from the upper surfaces of the hard mask 218 and the layer of conductive substrate 202 but not from the sidewalls of the part-formed stack 250' .
[0106] Note that the dry etching may employ the same process conditions or different process conditions as compared to those used for dry etching the layer of conductive substrate 202 (or the layer of correlated electron material 204 or the layer of conductive overlay 206) .
[0107] Referring now to Figures 5D and 5E, the dry etching of the layer of conductive substrate leads to its removal from the glass plate 208 but the trapping of the material from the layer of conductive substrate 202 (for example, iridium at least) at the sidewalls of the stack 250 occurs on the protective polymer coating 220.
[0108] Referring now to Figure 5F, after the dry etching is stopped, the coating of the protective polymer 220 is removed from the sidewalls of the stack 250 by, for example, a wet clean. The removal of the coating of protective polymer 220 (which is contaminated with material (iridium at least) from the layer of the conductive substrate) leaves sidewalls at the CEM layer 270 which are substantially free from the material of the conductive substrate (iridium at least) .
[0109] Note that the same wet clean or a separate wet clean can be used to remove correlated electron material at the sidewalls of the CEM layer 270. This wet clean may remove the correlated electron material which has become damaged during dry etching of the CEM layer 204. It may, in particular, remove correlated electron material to an inward extend of 1 to 10 nm at each sidewall of the CEM layer 270 and so leave a clean and undamaged sidewall.
[0110] The process of integration of the device to an integrated circuit may be continued with the deposition of a cover layer comprising an insulating material, for example, silica, and etching of a trench in the cover layer which exposes the conductive overlay of the device.
[0111] A metal interconnect is deposited in the trench by, for example, electroplating, so that it contacts the conductive overlay of the device and fills the trench.
[0112] Note that the cover layer of insulating material may be deposited over the hard mask 218 and the hard mask 218 removed from the stack during the etching of the trench in the cover layer.
[0113] Note further that the integrated device is characterised by a CEM layer 270 which is slightly indented from the conductive overlay 280 and the conductive substrate 260 of the device.
[0114] Figure 6 is a flow diagram particularly highlighting the steps involved in the integration a CEM device according to one embodiment of the present disclosure.
[0115] As may be seen, the dry etching of the (layer of conductive overlay 206 and) the correlated electron material 204 is stopped when the etch trace signals a depletion in the amount of metal ion characteristic to the CEM layer 270 (nickel, for example) . The depletion in the amount of nickel ion indicates that the layer of conductive substrate 202 has been reached. After the dry etching has been stopped, a coating of a protective organic polymer 220 is deposited over the part-formed stack 250' and the dry etching resumed (or another etching process or process condition is used) until the layer of the conductive substrate 202 is again exposed. The dry etching is resumed until the glass plate 208 is reached. After stopping the dry etching, the polymer coating 220 (including metal (iridium) residues) is removed from the stack 250 using a wet clean.
[0116] The integration may be continued, for example, by depositing a cover layer comprising an insulating material, for example, silica, etching of a trench in the cover layer to expose the conductive overlay of the device and depositing of a metal interconnect in the trench so that it contacts the conductive overlay of the device and fills the trench.
[0117] The integration may also comprise depositing a moisture barrier layer (not shown) , for example, of silicon nitride (SiN ) , over the stack 250 prior to the etching of the trench.
[0118] It may further comprise deposition of a metal barrier layer, for example, titanium nitride or tantalum nitride, in the trench and over the conductive overlay prior to deposition of the metal interconnect.
Claims
1. A method for the fabrication of a correlated electron material (CEM) device, the method comprising:
forming a layer of a conductive substrate;
forming a layer of a correlated electron material on the layer of conductive substrate;
forming a layer of a conductive overlay on the layer of correlated electron material; and
patterning the layers whereby to form a stack comprising a conductive substrate, a CEM layer and a conductive overlay, wherein the patterning comprises the following steps:
forming a hard mask on the layer of the conductive overlay; dry etching the layer of conductive overlay and the layer of correlated electron material whereby to form a partially formed stack; depositing a coating of a protective polymer over at least sidewalls of the partially formed stack; and
dry etching the layer of conductive substrate.
2. A method according to Claim 1, comprising depositing a coating of a protective polymer over the whole of the partially formed stack.
3. A method according to Claim 1 or Claim 2, comprising depositing a fluorocarbon or hydrofluorocarbon as the coating of protective polymer .
4. A method according to any preceding Claim, further comprising removing the coating of protective polymer from the upper surfaces of the conductive substrate and the hard mask.
5. A method according to Claim 4, further comprising etching the correlated electron material from the sidewalls of the CEM layer in the stack whereby to eliminate damage at the sidewalls of the CEM layer .
6. A method according to Claim 5, wherein the etching of the correlated electron material from the side walls of the CEM layer in the stack indents the CEM layer by 1 nm to 10 nm.
7. A method according to Claim 4, wherein the removal of the coating of protective polymer and the etching of CEM from the side walls of the stack are carried out as a single step.
8. A method according to any preceding Claim, wherein completion of the dry etching of the layer of conductive overlay and the layer of correlated electron material is determined by monitoring elapse of a predetermined period.
9. A method according to any of Claims 1 to 7, wherein completion of the dry etching of the layer of conductive overlay and the layer of correlated electron material is determined by monitoring depletion of nickel ion in etch trace data.
10. A method according to any preceding Claim, wherein depositing the coating of protective polymer and dry etching of the layer of conductive substrate are carried out in a single etch chamber.
11. A method according to any preceding Claim, wherein the forming of the layer of conductive substrate is on an insulating substrate including a via contacting the conductive substrate and a metal interconnect .
12. A method according to any preceding Claim, further comprising depositing a cover layer of the stack and patterning the cover layer whereby to form a trench in the cover layer and expose at least a part of the conductive overlay.
13. A method according to Claim 12, further comprising depositing a moisture barrier layer over the stack prior to the deposition of the cover layer.
14. A method according to Claim 12 or Claim 13, further comprising depositing a metal barrier layer over the exposed conductive overlay and at least the interior walls of the trench.
15. A method according to any of Claims 12 to 14, further comprising depositing a metal interconnect over the conductive overlay and barrier layer whereby to substantially fill the trench.
16. A correlated electron material (CEM) device, comprising a conductive substrate, a CEM layer and a conductive overlay, wherein the CEM layer has sidewalls having, at least in part, a recess therein.
17. An integrated circuit comprising a CEM device comprising a conductive substrate, a CEM layer and a conductive overlay, wherein the device is provided between an upper metal interconnect in a cover layer and a lower metal interconnect in a substrate, the upper metal interconnect and the conductive overlay having a trench contact, and wherein the CEM layer has sidewalls having, at least in part, a recess therein .
18. An electronic device comprising an integrated circuit having a CEM device comprising a conductive substrate, a CEM layer and a conductive overlay, wherein the device is provided between an upper metal interconnect in a cover layer and a lower metal interconnect in a substrate, the upper metal interconnect and the conductive overlay having a trench contact, and wherein the CEM layer has sidewalls having, at least in part, a recess as compared to the sidewalls of the conductive substrate and the conductive overlay.
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US15/933,818 US10833271B2 (en) | 2018-03-23 | 2018-03-23 | Method for fabrication of a CEM device |
US15/933,818 | 2018-03-23 | ||
US15/933,867 US20190296232A1 (en) | 2018-03-23 | 2018-03-23 | Method for fabrication of a cem device |
US15/933,867 | 2018-03-23 |
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US20080106925A1 (en) * | 2006-11-08 | 2008-05-08 | Symetrix Corporation | Correlated electron memory |
US20130112935A1 (en) * | 2010-12-03 | 2013-05-09 | Atsushi Himeno | Nonvolatile memory element, nonvolatile memory device, and manufacturing method for the same |
US20150243708A1 (en) * | 2014-02-25 | 2015-08-27 | Micron Technology, Inc. | Cross-point memory and methods for fabrication of same |
US20160268505A1 (en) * | 2015-03-12 | 2016-09-15 | Taiwan Semiconductor Manufacturing Co., Ltd. | Rram device |
WO2017160233A1 (en) * | 2016-03-15 | 2017-09-21 | Agency For Science, Technology And Research | Memory device and method of forming the same |
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2019
- 2019-02-28 KR KR1020207026281A patent/KR20200130824A/en unknown
- 2019-02-28 WO PCT/GB2019/050562 patent/WO2019180405A1/en active Application Filing
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US20080106925A1 (en) * | 2006-11-08 | 2008-05-08 | Symetrix Corporation | Correlated electron memory |
US20130112935A1 (en) * | 2010-12-03 | 2013-05-09 | Atsushi Himeno | Nonvolatile memory element, nonvolatile memory device, and manufacturing method for the same |
US20150243708A1 (en) * | 2014-02-25 | 2015-08-27 | Micron Technology, Inc. | Cross-point memory and methods for fabrication of same |
US20160268505A1 (en) * | 2015-03-12 | 2016-09-15 | Taiwan Semiconductor Manufacturing Co., Ltd. | Rram device |
WO2017160233A1 (en) * | 2016-03-15 | 2017-09-21 | Agency For Science, Technology And Research | Memory device and method of forming the same |
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