CN101163557A - 堆叠存储单元的钴自启动化学镀通道填充 - Google Patents
堆叠存储单元的钴自启动化学镀通道填充 Download PDFInfo
- Publication number
- CN101163557A CN101163557A CNA2006800129961A CN200680012996A CN101163557A CN 101163557 A CN101163557 A CN 101163557A CN A2006800129961 A CNA2006800129961 A CN A2006800129961A CN 200680012996 A CN200680012996 A CN 200680012996A CN 101163557 A CN101163557 A CN 101163557A
- Authority
- CN
- China
- Prior art keywords
- reducing agent
- concentration
- boryl
- hypophosphorous acid
- agent component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910017052 cobalt Inorganic materials 0.000 title claims description 22
- 239000010941 cobalt Substances 0.000 title claims description 22
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims description 22
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 108
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 41
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 229910000085 borane Inorganic materials 0.000 claims abstract description 28
- 238000011049 filling Methods 0.000 claims abstract description 23
- 150000002500 ions Chemical class 0.000 claims abstract description 19
- 239000008139 complexing agent Substances 0.000 claims abstract description 15
- 230000009467 reduction Effects 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 60
- 125000000707 boryl group Chemical group B* 0.000 claims description 42
- 238000007747 plating Methods 0.000 claims description 39
- 239000002585 base Substances 0.000 claims description 28
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 23
- 238000005234 chemical deposition Methods 0.000 claims description 22
- -1 alkali metal boron hydrogen salt Chemical class 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 19
- 238000003860 storage Methods 0.000 claims description 18
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 16
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 claims description 13
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 13
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 239000000872 buffer Substances 0.000 claims description 8
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000000151 deposition Methods 0.000 abstract description 31
- 230000008021 deposition Effects 0.000 abstract description 28
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 abstract 2
- 239000006172 buffering agent Substances 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 48
- 239000000463 material Substances 0.000 description 19
- 238000009713 electroplating Methods 0.000 description 17
- 239000002253 acid Substances 0.000 description 15
- 239000003990 capacitor Substances 0.000 description 13
- 229910045601 alloy Inorganic materials 0.000 description 12
- 239000000956 alloy Substances 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 12
- 239000010937 tungsten Substances 0.000 description 12
- 229910052721 tungsten Inorganic materials 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000001465 metallisation Methods 0.000 description 10
- 229910000531 Co alloy Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 8
- 239000004327 boric acid Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 229910001930 tungsten oxide Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000012634 fragment Substances 0.000 description 4
- 238000011081 inoculation Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910020674 Co—B Inorganic materials 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000005844 autocatalytic reaction Methods 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 239000003870 refractory metal Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 229960005137 succinic acid Drugs 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- WIHIUTUAHOZVLE-UHFFFAOYSA-N 1,3-diethoxypropan-2-ol Chemical compound CCOCC(O)COCC WIHIUTUAHOZVLE-UHFFFAOYSA-N 0.000 description 1
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
- 208000005189 Embolism Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical group [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- 229910010277 boron hydride Inorganic materials 0.000 description 1
- 239000005380 borophosphosilicate glass Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical class [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
- H01L21/76879—Filling of holes, grooves or trenches, e.g. vias, with conductive material by selective deposition of conductive material in the vias, e.g. selective C.V.D. on semiconductor material, plating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/53204—Conductive materials
- H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Chemically Coating (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Semiconductor Memories (AREA)
- Electrodes Of Semiconductors (AREA)
Abstract
一种用于化学镀填充堆叠存储单元互连部件的方法,包括通过在该部件的导电底部将包括钴离子和还原剂的组合物中的钴离子还原为钴金属从而启动自底而上填充的化学沉积。一种用于在高纵横比的堆叠存储单元互连部件中进行钴化学沉积的化学沉积组合物,该组合物包括水、钴离子、络合剂、缓冲剂、硼烷基还原剂组分以及次磷酸盐还原剂组分。硼烷基还原剂与次磷酸还原剂的浓度比约小于0.5。
Description
技术领域:
本发明涉及堆叠存储单元制品,具体地,本发明涉及堆叠存储单元互连部件诸如通道、沟槽、连接开口和通孔的金属基材填充。
背景技术:
存储电路如动态随机存取存储器(DRAM)装置通常包括存储数据的存储单元。数据存储在电容器中,电容器将数据保存为电荷。存储单元通常呈阵列设置。
DRAM装置通常分为两种类型:沟槽电容器型和堆叠电容器型。沟槽型单元是通过在由半导体基材制成的沟槽的侧壁内形成电容器。而堆叠类电容器类单元是通过在基材上堆叠电极层以形成电容器。堆叠电容器具有一定高度以存储足够的电荷。当器件几何构造最小化时,接触纵横比,即通道接触深度与通道接触直径的比率,会随着堆叠电容器高度的增长而增加。堆叠电容器单元是本领域技术人员所知的堆叠存储单元或装置。
堆叠存储装置通常对逻辑运算即集成电路的导电水平不作要求。因此,可使用较低导电性的插栓金属化代替较高导电性材料如铜填充堆叠存储通道。钨是一种代表性的栓塞金属化,因为其导电性没有铜好,但对于存储装置却已足够了。而且,由于其耐火性,钨不会扩散到硅晶片或低钾电介质层。因此,无需在硅或电介质材料和钨金属化之间设有防扩散屏障层。
通过化学汽相沉积法(CVD)或物理汽相沉积法(PVD)可将钨金属填充到通道和沟槽。通常,由于覆盖汽相沉积法包括多个处理步骤,所以用该方法进行金属填充成本高且耗时多。金属沉积加重了互连部件的负载,因此需图样和蚀刻,然后移除光阻。平版图案化允许有一定程度的误差。而且,汽相沉积法可填充金属到高纵横比通道或沟槽的顶部并且夹紧该顶部,导致在堆叠存储互连内产生空隙。
化学机械抛光法(CMP)可移除负载过重。在通道形成后,即在基材上进行化学机械抛光,例如移除沉积过程中沉积的多余钨负载,从而使其表面平坦。该CMP法可把痕量的钨嵌入或涂敷到电介质材料上。这些痕量的钨如果不被移除就会污染电介质。因此,在预处理组合物中使用一种蚀刻剂从而除去这些痕量的钨或者底切有钨存在的电介质,或者完成上述二项工作。
在堆叠存储装置中用钴替代钨作为栓塞金属化是很有吸引力的。在堆叠存储装置中,钴的导电性比钨好。而且,钴的耐火性足以阻止其向电介质层扩散。钴可用于CVD之外的其它方法中。
催化剂启动的化学镀钴沉积已在例如第6,232,227号美国专利中记载。用催化剂启动的化学镀钴沉积进行高纵横比互连部件的金属化的缺点在于钴会在有催化剂存在的所有表面上生长。在硅或电介质表面会非选择性地发生催化剂接种,如钯接种。因此,Pd种子将会在互连部件底部以及其侧壁和晶片表面产生。将金属应用到位于通道底部的扩散层表面而不并行地将金属实施到通道的侧壁或晶片表面,是很难实现的。因此,在钴溶液中浸泡晶片基材,会导致钴在通道的侧壁和晶片表面生长。这会产生二个缺点。首先,必须随后用一种平坦化或蚀刻步骤除去装置表面的钴。其次,通道侧壁的钴生长可导致在通道夹紧关闭,从而在互连结构中产生空隙。
因此,就需要一种工艺,能够填充堆叠电容器装置的高纵横比的互连部件,而不产生金属化而夹紧该部件的开口并导致互连部件中产生空隙。进一步,需要一种工艺和组合物,选择性地沉积钴金属化到堆叠电容器的高纵横比互连部件的底部上,并且从底部到顶部填充该部件,而不在该互连部件侧壁或该装置的表面并行产生钴。最后,需要一种组合物,自动催化该导电性钴和钴合金沉积到堆叠存储装置的高纵横比互连部件的源/汲区。
发明内容:
因此,简要地说,本发明涉及一种用于化学镀填充堆叠存储单元互连部件的方法,该方法包括将该堆叠存储单元互连部件与一种包含钴离子源和还原剂的化学沉积组合物相接触,其中,该堆叠存储互连部件具有一导电底部、带有电介质表面的侧壁、且高--宽纵横比至少约为2,由此一部分钴离子在该导电底部上被还原为钴金属,并且通过持续还原钴离子对该堆叠存储互连部件进行自底而上的填充。
其次,本发明涉及一种用于在高纵横比的堆叠存储单元互连部件中化学沉积钴的化学沉积组合物。该组合物包括水,钴离子源,络合剂,缓冲剂,硼烷基还原剂组分及次磷酸盐还原剂组分。所述硼烷基还原剂组分选自碱金属硼氢盐、二甲胺硼烷、二乙胺硼烷、吗啉硼烷或各自的混合物。所述次磷酸盐还原剂组分选自次磷酸碱金属盐、次磷酸铵、次磷酸或各自的混合物。所述硼烷基还原剂组分的浓度和次磷酸盐还原剂组分浓度优选地为:硼烷基还原剂组份的浓度(g/L)与次磷酸盐还原剂组分浓度(g/L)的浓度比约小于0.5。
附图说明:
图1为一种堆叠存储单元的片段的示意图。
图2为根据本发明填充的测试通道的显微照片。
具体实施方式:
根据本发明,金属化是填充到一种堆叠存储装置的互连部件中;例如,将钴或其合金填充到堆叠存储单元的高纵横比通道或沟槽中。该互连部件包括底部、侧壁及顶部开口。该侧壁的高度和开口的直径使得该通道具有高纵横比。作为常规比例,该侧壁高度与开口直径之比大于5。在另一实施例中,该纵横比至少为10。在另一本发明的实施例中,该纵横比至少约为18。
图1是本发明一种具有通道的堆叠存储单元的片段的示意图。此处所示的该堆叠存储单元片段10的横截面中,有电介质材料12,其为标准的电介质材料如SiO2、氟硅玻璃、BPSG或其它低钾电介质。通道14给该装置片段顶部和源区18之间提供电连接。通道14和源区18之间的触头16是由W、分层W-WN或分层WSi2-多晶硅制成。晶体管闸极20为源区18和汲区22之间提供电连接。源区18和汲区22存在于半导体单晶Si体内,并且含有半导体单晶Si的杂质,例如P,As或其它标准掺杂材料。通道24为通常带有平板26和28的电容器提供电连接,该平板26和28含有如图所示由电介质隔离的金属如Cu或Al。
通道14的底部是导电材料,因为其是由W、分层W-WN或分层WSi2-多晶硅制成的触头。通道24的底部是导电材料,因为其是由例如含杂质的Si.制成的汲区。在另一实施例中,该装置汲区由TiN或Ru制成。用于填充互连的金属是Co基金属,如Co金属或其合金,包括但不限于Co-B-P,Co-W-B-P,Co-W-B和Co-B。如下面本发明内容所述,通道14和24底部的导电材料为自底向上、化学镀和自启动超填充提供导电性。
互连填充包括在互连底部的沉积的启动,然后从互连的底部到顶部进行自底而上的填充。该填充是“自底而上”的,是因为其主要从互连底部到顶部的方向进行的,而且没有实质的侧壁沉积。填充首先通过硼烷-化学反应化学沉积工艺沉积Co基材料,该工艺使用一种烷基胺硼烷化合物如二甲胺硼烷(DMAB)、二乙胺硼烷(DEAB)或吗啉硼烷作为还原剂。这些硼烷基还原剂将W催化还原为Co沉积。因此,该工艺是在W通道底部自启动,因而排除了Co、Pd或其它接种操作。这与基于非硼烷化学反应的化学镀工艺是相反的,该基于非硼烷化学反应的化学镀工艺是诸如使用次磷酸盐或其它非硼烷还原剂,它们不能将W催化为Co沉积。如果使用该非硼烷工艺将Co直接沉积在W通道上,就需要Co接种或其它活化机制。由硼烷化学反应催化的其它材料包括Cu,Co,Pt,Mo,Au,及Pd,但是Au优选使用联氨催化。
选用前述材料的优点是Co基生长是从该通道的底部开始的。使用本发明方法,从该互连部件的底部向上到开口进行金属化填充。该填充方法可以避免产生两个问题,一是可能会夹紧关闭通道开口的侧面沉积,二是需要平坦化步骤如CMP的表面沉积。
根据本发明的用于化学镀电镀Co及其合金的化学镀电镀浴,包括沉积离子源、还原剂、络合剂及表面活性剂。该电镀浴缓冲为某一pH值范围内。任选地,该电镀浴还可包括多种表面活性剂、耐火离子源及多种稳定剂。配制该电镀浴以使其在汲区基材如W上自启动。在铜基材上自启动的电镀浴,如在盖层装置中,可能会也可能不启动Co沉积到W上。该电镀浴与Co盖层装置不同,因为很难沉积导电性很强的合金,特别是高(导电性的)Co,因为互连的目的是负载电流,这与盖层装置中Co沉积的目的是相反的。
为沉积一种Co基合金,该电镀浴包括一Co离子源,该Co离子源在该溶液中是作为一种无机Co盐如氯化物、硫酸盐或其它适宜的无机盐或一种带有有机羧酸的Co络合物,如醋酸Co盐、柠檬酸Co盐、乳酸Co盐、琥珀酸、丙酸Co盐、羟基乙酸Co盐、EDTA Co盐或其它Co盐。
在一个具体实施例中,该无机Co盐为Co(OH)2.。该氢氧基比典型Co盐的其它阴离子的分子量小。由于水溶液中已有氢氧离子,所以该Co(OH)2盐产生一种很简单的电镀浴。因此,在该化学镀电镀浴中没有多余的阴离子如卤化物,从而避免了被该类阴离子污染的风险。
在一个具体实施例中,添加Co盐或络合物以提供约0.5g/L-60g/L的Co2+,以得到高Co金属含量的Co基合金。
所用的还原剂为单独的硼烷基还原剂组分或者与次磷酸盐还原剂组分的组合。在CoB系统中,单独使用硼烷基还原剂,该Co合金的Co含量较高。使用还原剂组合时,则电镀浴的稳定性和通道或沟槽组件的填充都得到了改善。下面将对还原剂进行更详细地描述。
该镀液还包括一种或多种络合剂和缓冲剂。该镀液通常包括一种pH缓冲液以将pH值稳定在要求的范围内。在一个具体实施例中,期望的pH值范围约为7.5-10.0。在一个具体实施例中,该值约为8.8-10。该pH范围提供了一种弱碱性化学镀电镀液。如果该pH不稳定,沉积率和沉积化学反应就会发生无意的、不符合要求的、不可预料的变化。代表性的缓冲剂包括,例如,硼酸盐、四和五硼酸盐、磷酸盐、醋酸盐、羟乙酸盐、乳酸盐、氨和焦磷酸盐。碱性pH调节使用的是铵、TMAH、NaOH、KOH或其混合物。硫酸、盐酸和柠檬酸用于进行酸性调节,酸的选择是与Co源的阴离子相对应的。在一个具体实施例中,该pH缓冲液浓度约为0g/L-50g/L。
该镀液中的络合剂有助于保持溶液中的Co离子和调节启动沉积所需镀液的电镀电势。该镀液所用的络合物选自柠檬酸,苹果酸,乙二胺,甘氨酸,丙酸,琥珀酸,及乳酸,二乙胺(DEA),四乙基氢氧化铵(TEAH),及铵盐如氯化铵、硫酸铵、氢氧化铵,焦磷酸盐或其混合物。在一个具体实施例中,所选的络合剂的浓度通常是络合剂与Co的摩尔比约为2∶1-4∶1。在另一具体实施例中,该比率约为9∶1-10∶1。根据络合剂的分子量,络合剂的浓度约为5g/L-250g/L。
可以添加表面活性剂以促进金属互连表面的润湿并强化沉积。该表面活性剂通过提高互连填充的均匀性和密集性,进而改善沉积物的形态和分布状况,来减少缺损。表面活性剂也有助于细化粒径以产生更均匀的沉积物。代表性的阴离子型表面活性剂包括烷基磷酸酯、磷酸烷基醚酯盐、烷基硫酸酯、烷基醚硫酸酯、烷基磺酸酯、烷基醚磺酸酯、羧酸醚、羧酸酯、烷基芳基磺酸酯、磺基琥珀酸酯。代表性的非离子表面活性剂包括烷氧基化醇、乙氧基/丙氧基(EO/PO)嵌段共聚物、烷氧基化脂肪酸、乙二醇酯和丙三醇酯,目前优选的为聚乙二醇和聚丙二醇/聚乙二醇。在一个具体实施例中,表面活性剂约为0.01g/L-5g/L。
如果需要,该电镀浴还可以包括一种难熔金属离子如钨和/或钼。代表性的W离子源为四甲基钨酸铵、磷钨酸盐、硅钨酸盐、钨酸、氧化钨及其混合物。例如,优选的沉积镀液包括约1g/L-15g/L的钨酸。其它难熔金属源包括钼酸铵和/或氧化钼。在一个实施例中,难熔离子源基本是不含碱金属的,因为碱金属的存在会污染沉积物。
该化学镀Co沉积溶液中也可以加入稳定剂。使用稳定剂有助于防止镀液自然分解。代表性的稳定剂包括,例如Pb,Bi,Sn,Sb,IO3,MoO3,AsO3,吡咯如咪唑及衍生物。该稳定剂的量约为0-500 ppm.。例如,约5-20 ppm的Pb+2就已显示有效。约10-300 ppm的MoO4 -2也显示有效。在某些应用中马来酸特别有效,因为其中没有向该沉积镀液中加入其它可能污染沉积物的金属离子。
也可以加入本领域技术人员公知的其它添加剂,如加速剂及抛光剂。在某些具体实施例中,特别是半导体应用中,该镀液基本没有Na和其它碱金属离子。
该还原剂包括一种硼烷基组分,如硼氢化碱金属盐、二甲胺基硼烷(DMAB)、二乙胺基硼烷(DEAB)及吗啉硼烷。来自硼烷基还原剂组分的硼元素成为电镀合金的一部分。解释该有关硼氢化物现象的反应机理为:
2Co2++2BH4 -+4H2O=2Co0+B0+3B(OH)4 -+3H++(9/2)H2
根据该反应机理,电镀浴需要2摩尔BH4 -将2摩尔Co2+还原为Co合金。在某一具体实施例中,为确保在该电镀浴中有足够浓度的还原剂,所加的二甲胺基硼烷的起始浓度约为0.5g/L-16g/L,如约为3g/L。一优选的具体实施例中使用约为3g/L-9g/L的DMAB。
在本发明的一个具体实施例中,该还原剂还包括一种磷基还原剂组分,如次磷酸盐。当有次磷酸盐时,沉积的合金含有磷。解释该现象的反应机理为:
Co2++4H2PO2 -+H2O=Co0+3H2PO3 -+H++P0+(3/2)H2
根据该反应机理,该电镀浴要求摩尔H2PO2 -还原1摩尔Co2+为Co合金。电镀浴中Co离子与次磷酸盐离子的摩尔比约为0.1-1。为确保电镀浴中有足够浓度的次磷酸盐,在一个具体实施例中,该次磷酸盐可为碱金属次磷酸盐、次磷酸铵或次磷酸,加入的起始浓度约为20g/L-30g/L。在一个具体实施例中,加入的次磷酸铵约为23g/L-26g/L。
自然,次磷酸盐只能在有限的基材包括Co,Ni,Rh,Pd和Pt上还原Co离子。上述清单中不包括W,因为W是一种特殊的金属而在堆叠存储器高纵横比互连部件用作一种汲/源。为了次磷酸盐在W基材上还原Co离子,可用PVD或CVD Cu或Co,或Pd接种活化W的表面。根据本发明,用一种强还原剂如DMAB处理W表面,活化该表面以进行次磷酸还原反应。
在本发明的一个具体实施例中,还原剂中具有硼烷基和次磷酸盐二种组分,在该互连部件与化学沉积镀液起始接触时,硼烷基还原剂的浓度(以g/L为单位)与次磷酸还原剂的浓度(以g/L为单位)的浓度比小于约0.5。在一个具体实施例中,在该互连部件与化学沉积镀液起始接触时,该浓度比小于约0.2。比率的选择影响启动和生长率、电镀电势和电镀合金的性能。例如,选用的比率使得自动催化Co沉积在堆叠存储装置的源/汲区的表面。而且,由于传导性是Co栓塞的理想特征,选择还原剂的比率以最小化B或的共同沉积物。.在一个具体实施例中,还原剂系统所用的是约9g/LDMAB还原剂及与23g/L次磷酸盐还原剂的混合物。该硼烷其还原剂启动在W或其它金属基汲区表面上化学沉积Co2+离子为Co金属。启动发生氧化还原化学反应之后,两还原剂持续还原Co2+离子到Co表面上,以填充该堆叠存储装置的高纵横比部件。
在实施本发明方法的过程中,进行表面预处理是使用一种有机酸或无机酸或碱清洁剂以移除金属互连部件的氧化钨。该清洁剂优选移除所有的氧化物如氧化钨,而不会移除该互连中大量的金属化。如果不移除这些氧化物,它们不仅会干扰启动,而且会干扰金属化粘附到在基材上,并且降低导电性。这类清洁剂通常包括一种蚀刻剂,如一种酸的稀溶液,酸在水中小于10wt%,该酸为一种强无机酸如HF,HNO3,或H2SO4,或一种弱有机酸或羧酸如柠檬酸或丙二酸。这种清洁剂还包括一种表面活性剂,如Rhodafac RE620(罗纳普朗克Rhone-Poulenc),以润湿表面。
典型的碱性清洁剂包括TMAH并添加羟胺,MEA,TEAH,乙二胺(EDA),二乙撑三胺(DTA)或NH4OH,pH范围为9-12。优选使用碱性清洁剂,因为其不蚀刻侧壁并能有效清洁氧化物。
在新鲜W表面,该预处理步骤是任选的,因为在工作pH条件下,该渡液溶液能够清洁薄的氧化钨层。任选地,可在该预处理溶液中加入阳离子有机化合物以防止在电镀过程中侧壁被蚀刻。
如上所述,通过硼烷化学反应的化学沉积进行Co基互连的沉积。这种暴露可包括浸渍、用水浸泡、喷雾或其它将该堆叠存储单元暴露于沉积镀液的方式,并要求暴露的方式足以达到在互连中沉积Co基金属化到期望深度和完整度的目标。
当硼烷基还原剂接触该传导表面,可以实现自启动化学镀Co沉积。具体地,在其沉积条件如pH和温度下,视情况而定,该硼烷基还原剂在该催化W表面或掺杂质的Si表面被氧化从而释放电子到该表面上。所释放的电子随即被Co2+离子结合而将Co2+离子还原为Co金属。
起始的氧化/还原反应仅能在该通道底部的充分传导性表面如W表面进行。W之外其它基材的选用取决于与该装置或该汲区自身相关的因素,而该装置或汲区本身并不与本发明的通道填充过程别相关,但这些基材是与之相配伍的。如果该汲区材料至少具有如W一样的惰性,本发明是可实施的。Co基沉积不会在该通道侧壁上启动,因为该侧壁由一种电介质材料制成;更确切地,该沉积仅发生在该通道底部。一旦在该通道底部形成起始Co沉积,该次磷酸盐还原剂和硼烷基还原剂与Co沉积物相作用,释放电子以进一步还原Co2+离子为Co金属。该氧化/还原反应继续进行并且Co沉积物从通道底部进行填充。
由于Co实质上沉积到该通道底部,所以该工艺过程是自调节的,因此由于无需掩盖除互连之外的其它区域,所以该工艺是无掩模的。而且,之后无须移除电介质上大量的杂散(stray)Co沉积物。
由于通道的侧壁是如图1中12所示主体电介质的内腔(bore),且没有被接种或催化或用导电材料如Pd,Co或类似材料处理,所以该通道的侧壁具有电介质表面。在这个意义上说,实施该方法无需处理该通道侧壁,该通道侧壁包括无覆盖的或光的介质表面。
在进行本发明中,选择化学沉积组合物的标准之一是期望获得具有高传导性的Co基填充。该期望传导性的特征是电阻系数为,例如优选低于约50微欧姆-厘米。这不同于Co基Cu-覆盖层装置,其可接受的电阻系数为60-80微欧姆-厘米。使用一种方法,通过选择镀液化学沉积一种Co基填充以得到期望的传导性,这种填充至少约为90原子百分比(atomic%)的Co。达到镀液中来自还原剂的组分如B和/或P削弱Co基填充的程度,传导性就会被减弱。相应地,就要在足够高的还原剂浓度以获得可接受的沉积率和足够低的还原剂浓度以在沉积物中获得期望的Co浓度之间进行平衡。如果一种镀液的沉积率相对高,并且沉积产物中的电阻系数高于约50微欧姆-厘米,可以通过热处理或后退火将电阻系统降低到可接受的水平。
通过下面的实例进一步描述本发明。
例1-12
根据上述指导原则,配制下述具有用于自启动Co沉积的组合物的化学镀镀液。
例1(Co-B-P互连)
CoCl26H2O 25g/L
柠檬酸 50g/L
NH4Cl 15g/L
DMAB 9g/L
次磷酸铵 26g/L
在室温下配制该镀液。根据下述步骤添加成分:
1.配制溶液A:
a.将25g的CoCl2 6H2O溶解于少于0.5L的水中。
b.向Co2+离子络合物加入50g柠檬酸。
c.加入TMAH调节溶液的pH。
d.定容到0.5 L。
e.过滤除去金属杂质。
2.配制溶液B:
a.将26g次磷酸铵溶解于少于0.5L水。
b.溶解15g的NH4Cl。
c.加入TMAH中和溶液的pH。
d.溶解9g DMAB。
e.加入TMAH调节溶液的pH。
f.定容到0.5L。
g.过滤。
3.混合溶液A和B,并稀释定容为IL。
4.过滤移除固体物质。
根据下面成分的清单配制镀液以制得其它Co合金。在每一例子中,根据上面列出的步骤配制镀液,在溶液A和B中还有其它加入缓冲液(如硼酸)的步骤。
例2 (Co-B-P互连)
CoCl2 6H2O 43 g/L
柠檬酸43 g/L
硼酸 14 g/L
DMAB 9 g/L
次磷酸铵 26 g/L
例3 (Co-B-P互连)
CoCl2 6H2O2 1 g/L
苹果酸 64 g/L
硼酸 14 g/L
DMAB 16 g/L
次磷酸 26 g/L
例4(Co-W-B-P互连)
CoCl2 6H2O 22g/L
柠檬酸 22g/L
硼酸 8g/L
钨酸 4g/L
D)MAB 3g/L
次磷酸 23g/L
例5(Co-W-B-P互连)
CoCl2 6H2O 45g/L
柠檬酸 45g/L
硼酸 15g/L
钨酸 4g/L
DMAB 3g/L
次磷酸铵 23g/L
例6(Co-W-B-P互连)
CoCl2 6H2O 45g/L
柠檬酸 45g/L
硼酸 15g/L
钨酸 4g/L
DMAB 9g/L
次磷酸 26g/L
例7(Co-B互连)
CoCl2 6H2O 25g/L
柠檬酸 70g/L
NH4Cl 45g/L
DMAB 10g/L
例8(Co-B互连)
CoSO4 7H2O 29g/L
柠檬酸 76g/L
NH4Cl 48g/L
DMAB 5g/L
例9(Co-W-B互连)
CoCl2 6H2O 30g/L
柠檬酸 25g/L
硼酸 10g/L
钨酸 1g/L
DMAB 2g/L
例10(Co-W-B互连)
CoCl2 6H2O 23g/L
柠檬酸 45g/L
NH4Cl 15g/L
钨酸 4g/L
DMAB 9g/L
例11(Co-W-B-P互连)
Co(OH)2 5g/L
柠檬酸 20g/L
NH4Cl 2g/L
钨酸 0.4g/L
DMAB 0.6g/L
次磷酸 6g/L
例12(Co-W-B-P互连)
Co(OH)2 3g/L
柠檬酸 20g/L
焦亚磷酸 10g/L
钨酸 0.4g/L
硼酸 5g/L
DMAB 0.4g/L
次磷酸 4g/L
例13
根据本发明,互连基材包括一W底部和SiO2侧壁,使用5%TMAH进行预清洁,以移除该通道互连部件传导性表面的氧化钨。然后,在60-95℃时,在Co合金化学镀镀液中冲洗和浸没该基材10分钟至2小时。填充以约为100埃/分钟--3000埃/分钟的速度进行。填充后的通道没有空隙。
例14
参照下表,用不同Co合金填充几种基材。图示每一次填充合金组合物和大约的填充率。该合金电阻系数约为26-80微欧姆-厘米。
膜层(film) | 浓度,% | 沉积率,埃/分钟 | |||
Co | W | P | B | ||
CoBP | 86-92 | 4-12 | 1-5 | 100-3000 | |
CoWB | 50-90 | 5-30 | 1-6 | 100-2000 | |
CoB | 95-99 | 0.5-4 | 300-1000 | ||
CoWBP | 83-95 | 1-6 | 1-10 | 1-3 | 100-3000 |
例5-8、11和12得到的可接受的电阻系数约为50微欧姆-厘米或更少。例2、4、5和6具有可接受的沉积率,原因是:与例9、11和12相比,其Co含量相对较高;并且其具有相对低的络合剂与金属浓度比及高浓度的还原剂。
例15
在pH为9.8、温度为75℃条件下,将互连基材在例6的化学镀镀液中浸没10分钟。图2为放大35,000倍的Co合金填充通道的SEM照片。该照片显示Co合金对该纵横比通道的均衡启动和填充,致使互连部件中的Co合金致密且无空隙。侧壁蚀刻是最少的。
根据上述内容,可实现本发明的多个目的及其它有益效果。
在描述本发明的要素或其优选实施例时,用语“一”、“一”“这个”、“该”用于表示具有一个或多个要素。例如,说明书及后附权利要求所指的“一”互连意思是指有一或多个互连。术语“包括”、“含有”、“具有”意在表示包含的,且意思是可能会有所列要素之外的其它要素。
由于对本发明可以进行许多改变而不超出本发明的范围,说明书所包括的内容及附图所示的内容到是对本发明的说明而不是限制。
Claims (21)
1.一种用于化学镀填充堆叠存储单元互连部件的方法,该方法包括:
将该堆叠存储单元互连部件与一种包含钴离子源和还原剂的化学沉积组合物相接触,其中,该堆叠存储互连部件具有一导电底部、带有电介质表面的侧壁、且高-宽纵横比至少约为2,由此一部分钴离子在该导电底部上被还原为钴金属,并且通过持续还原钴离子对该堆叠存储互连部件进行自底而上的填充。
2.如权利要求1所述的方法,其中,该还原剂包括硼烷基还原剂组分。
3.如权利要求2所述的方法,其中,该硼烷基还原剂组分选自碱金属硼氢盐、二甲胺硼烷、二乙胺硼烷、吗啉硼烷或各自的混合物。
4.如权利要求2或3所述的方法,其中,该还原剂还包括一种次磷酸盐还原剂组分。
5.如权利要求4所述的方法,其中,该次磷酸还原剂组分选自碱金属次磷酸盐、次磷酸铵、次磷酸或各自的混合物。
6.如权利要求3、4或5所述的方法,其中,该还原剂还包括一种次磷酸还原剂组分。
7.如权利要求6所述的方法,其中,该次磷酸还原剂组分选自碱金属次磷酸盐、次磷酸铵、次磷酸或各自的混合物。
8.如权利要求6所述的方法,其中,该硼烷基还原剂组分具有一硼烷基还原剂组分浓度,且该次磷酸还原剂组分有一个次磷酸还原剂组分浓度,且该硼烷基还原剂组分的浓度和该次磷酸还原剂的浓度应当能产生一个以g/L为单位的硼烷基还原剂浓度与以g/L为单位的次磷酸还原剂浓度之间的浓度比,该浓度比在该互连部件与化学沉积组合物初次接触时约小于0.5。
9.如权利要求6所述的方法,其中,该硼烷基还原剂组分具有一硼烷基还原剂组分浓度,且该次磷酸还原剂组分有一个次磷酸还原剂组分浓度,且该硼烷基还原剂组分的浓度和该次磷酸还原剂的浓度应当能产生一个以g/L为单位的硼烷基还原剂浓度与以g/L为单位的次磷酸还原剂浓度之间的浓度比,该浓度在该互连部件与化学沉积组合物初次接触时约小于0.2。
10.如权利要求8所述的方法,其中:
该硼烷基还原剂选自碱金属硼氢盐、二甲胺硼烷、二乙胺硼烷、吗啉硼烷或各自的混合物;并且
该次磷酸还原剂选自碱金属次磷酸盐、次磷酸铵、次磷酸或各自的混合物。
11.如权利要求9所述的方法,其中:
该硼烷基还原剂选自碱金属硼氢盐、二甲胺硼烷、二乙胺硼烷、吗啉硼烷或各自的混合物;并且
该次磷酸还原剂选自碱金属次磷酸盐、次磷酸铵、次磷酸或各自的混合物。
12.如权利要求1-11中任一项所述的方法,其中,对该堆叠存储互连部件自底而上的填充获得的Co基填充互连部件含有原子百分比至少为90%的Co。
13.如权利要求1-12中任一项所述的方法,其中,该自底而上的填充获得的Co基填充互连部件的电阻系数约为50微欧姆-厘米或更低。
14.如权利要求1所述的方法,其中,该堆叠存储互连部件自底而上的填充获得的Co基填充互连部件含有原子百分比至少为90%的Co且电阻系数约为50微欧姆-厘米或更低。
15.如权利要求1所述的方法,其中,该化学沉积组合物包括:
水;
钴离子源;
络合剂;
缓冲剂;
硼烷基还原剂组分;以及
次磷酸盐还原剂组分。
16.一种用于化学镀填充堆叠存储单元互连部件的方法,该方法包括:
将该堆叠存储单元互连部件与一种含有钴离子源和还原剂的化学沉积组合物相接触,其中,该堆叠存储互连部件具有一导电底部、带有电介质表面的侧壁、且高-宽纵横比至少约为10,由此一部分钴离子在该导电底部上被还原为钴金属,并且通过持续还原钴离子对该堆叠存储互连部件进行自底而上的填充,其中,该化学沉积组合物包括:
水;
钴离子源;
络合剂;
缓冲剂;
硼烷基还原剂组分,选自碱金属硼氢盐、二甲胺硼烷、二乙胺硼烷、吗啉硼烷或其混合物;以及
次磷酸盐还原剂组分,选自碱金属次磷酸盐、次磷酸铵、次磷酸及其混合物;并且
其中,该硼烷基还原剂组分具有一硼烷基还原剂组分浓度,且该次磷酸还原剂组分有一个次磷酸还原剂组分浓度,且该硼烷基还原剂组分的浓度和该次磷酸还原剂的浓度应当能产生一个以g/L为单位的硼烷基还原剂浓度与以g/L为单位的次磷酸还原剂浓度之间的浓度比,该浓度比在该互连部件与化学沉积组合物初次接触时约小于0.5。
17.如权利要求16所述的方法,其中:
Co离子的浓度约为1g/L-20g/L;
络合剂的浓度约为20g/L-80g/L;
缓冲剂的浓度约为0g/L-20g/L;
硼烷基还原剂组分的浓度约为0.5g/L-16g/L;并且
次磷酸还原剂组分的浓度约为20g/L-32g/L。
18.如权利要求16所述的方法,其中:以g/L为单位的硼烷基还原剂浓度与以g/L为单位的次磷酸还原剂浓度之间的浓度比约小于0.2。
19.一种用于在高纵横比的堆叠存储单元互连部件中化学沉积钴的化学沉积组合物,该组合物包括:
水;
钴离子源;
络合剂;
缓冲剂;
硼烷基还原剂组分;以及
次磷酸盐还原剂组分;
其中,该硼烷基还原剂组分选自碱金属硼氢盐、二甲胺硼烷、二乙胺硼烷、吗啉硼烷或各自的混合物;
其中,该次磷酸还原剂组分选自碱金属次磷酸盐、次磷酸铵、次磷酸或各自的混合物;并且
其中,该硼烷基还原剂组分具有一硼烷基还原剂组分浓度,且该次磷酸还原剂组分有一个次磷酸还原剂组分浓度,且该硼烷基还原剂组分的浓度和该次磷酸还原剂的浓度应当能产生一个以g/L为单位的硼烷基还原剂浓度与以g/L为单位的次磷酸还原剂浓度之间的浓度比,该浓度比在该互连部件与化学沉积组合物初次接触时约小于0.5。
20.如权利要求19所述的化学沉积组合物,其中:
Co离子的浓度约为1g/L-20g/L;
络合剂的浓度约为20g/L-80g/L;
缓冲剂的浓度约为0g/L-20g/L;
硼烷基还原剂组分的浓度约为0.5g/L-16g/L;以及
次磷酸还原剂组分的浓度约为20g/L-32g/L。
21.如权利要求19所述的化学沉积组合物,其中:以g/L为单位的硼烷基还原剂浓度与以g/L为单位的次磷酸还原剂浓度之间的浓度比约小于0.2。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/063,624 | 2005-02-23 | ||
US11/063,624 US20060188659A1 (en) | 2005-02-23 | 2005-02-23 | Cobalt self-initiated electroless via fill for stacked memory cells |
Publications (1)
Publication Number | Publication Date |
---|---|
CN101163557A true CN101163557A (zh) | 2008-04-16 |
Family
ID=36913037
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNA2006800129961A Pending CN101163557A (zh) | 2005-02-23 | 2006-02-17 | 堆叠存储单元的钴自启动化学镀通道填充 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20060188659A1 (zh) |
EP (1) | EP1861208A2 (zh) |
JP (1) | JP2008533702A (zh) |
KR (1) | KR20070113243A (zh) |
CN (1) | CN101163557A (zh) |
TW (1) | TW200644162A (zh) |
WO (1) | WO2006091486A2 (zh) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2255024A2 (en) * | 2008-01-24 | 2010-12-01 | Basf Se | Electroless deposition of barrier layers |
DE102009014424A1 (de) * | 2008-08-22 | 2010-02-25 | W.C. Heraeus Gmbh | Stoff aus Metall und Milchsäurekondensat sowie elektronisches Bauteil |
DE102011002769B4 (de) * | 2011-01-17 | 2013-03-21 | Globalfoundries Dresden Module One Limited Liability Company & Co. Kg | Halbleiterbauelement und Verfahren zur Herstellung einer Hybridkontaktstruktur mit Kontakten mit kleinem Aspektverhältnis in einem Halbleiterbauelement |
JP6212323B2 (ja) * | 2013-08-02 | 2017-10-11 | 日本カニゼン株式会社 | 無電解ニッケルめっき液及びそれを用いた無電解ニッケルめっき方法 |
SG11201610662QA (en) | 2014-07-25 | 2017-01-27 | Intel Corp | Tungsten alloys in semiconductor devices |
US9768063B1 (en) | 2016-06-30 | 2017-09-19 | Lam Research Corporation | Dual damascene fill |
US10340183B1 (en) | 2018-01-02 | 2019-07-02 | Globalfoundries Inc. | Cobalt plated via integration scheme |
TWI833730B (zh) * | 2018-02-21 | 2024-03-01 | 日商東京威力科創股份有限公司 | 多層配線之形成方法及記憶媒體 |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4692349A (en) * | 1986-03-03 | 1987-09-08 | American Telephone And Telegraph Company, At&T Bell Laboratories | Selective electroless plating of vias in VLSI devices |
NL8900305A (nl) * | 1989-02-08 | 1990-09-03 | Philips Nv | Werkwijze voor het vervaardigen van een halfgeleiderinrichting. |
US5447880A (en) * | 1992-12-22 | 1995-09-05 | At&T Global Information Solutions Company | Method for forming an amorphous silicon programmable element |
JPH07130871A (ja) * | 1993-06-28 | 1995-05-19 | Toshiba Corp | 半導体記憶装置 |
US5990021A (en) * | 1997-12-19 | 1999-11-23 | Micron Technology, Inc. | Integrated circuit having self-aligned CVD-tungsten/titanium contact plugs strapped with metal interconnect and method of manufacture |
US5695810A (en) * | 1996-11-20 | 1997-12-09 | Cornell Research Foundation, Inc. | Use of cobalt tungsten phosphide as a barrier material for copper metallization |
JPH10261772A (ja) * | 1997-01-14 | 1998-09-29 | Mitsubishi Electric Corp | 半導体記憶装置及びその製造方法 |
US6117784A (en) * | 1997-11-12 | 2000-09-12 | International Business Machines Corporation | Process for integrated circuit wiring |
US6180523B1 (en) * | 1998-10-13 | 2001-01-30 | Industrial Technology Research Institute | Copper metallization of USLI by electroless process |
US6214728B1 (en) * | 1998-11-20 | 2001-04-10 | Chartered Semiconductor Manufacturing, Ltd. | Method to encapsulate copper plug for interconnect metallization |
US6015747A (en) * | 1998-12-07 | 2000-01-18 | Advanced Micro Device | Method of metal/polysilicon gate formation in a field effect transistor |
US20020081842A1 (en) * | 2000-04-14 | 2002-06-27 | Sambucetti Carlos J. | Electroless metal liner formation methods |
US6624091B2 (en) * | 2001-05-07 | 2003-09-23 | Applied Materials, Inc. | Methods of forming gap fill and layers formed thereby |
US6717189B2 (en) * | 2001-06-01 | 2004-04-06 | Ebara Corporation | Electroless plating liquid and semiconductor device |
US7253467B2 (en) * | 2001-06-28 | 2007-08-07 | Samsung Electronics Co., Ltd. | Non-volatile semiconductor memory devices |
US6781184B2 (en) * | 2001-11-29 | 2004-08-24 | Symetrix Corporation | Barrier layers for protecting metal oxides from hydrogen degradation |
US6645567B2 (en) * | 2001-12-19 | 2003-11-11 | Intel Corporation | Electroless plating bath composition and method of using |
DE10200399B4 (de) * | 2002-01-08 | 2008-03-27 | Advanced Micro Devices, Inc., Sunnyvale | Verfahren zur Erzeugung einer dreidimensional integrierten Halbleitervorrichtung und dreidimensional integrierte Halbleitervorrichtung |
US7008872B2 (en) * | 2002-05-03 | 2006-03-07 | Intel Corporation | Use of conductive electrolessly deposited etch stop layers, liner layers and via plugs in interconnect structures |
US6787450B2 (en) * | 2002-05-29 | 2004-09-07 | Micron Technology, Inc. | High aspect ratio fill method and resulting structure |
US6710391B2 (en) * | 2002-06-26 | 2004-03-23 | Texas Instruments Incorporated | Integrated DRAM process/structure using contact pillars |
US6821909B2 (en) * | 2002-10-30 | 2004-11-23 | Applied Materials, Inc. | Post rinse to improve selective deposition of electroless cobalt on copper for ULSI application |
US6797312B2 (en) * | 2003-01-21 | 2004-09-28 | Mattson Technology, Inc. | Electroless plating solution and process |
US6902605B2 (en) * | 2003-03-06 | 2005-06-07 | Blue29, Llc | Activation-free electroless solution for deposition of cobalt and method for deposition of cobalt capping/passivation layer on copper |
JP2004311706A (ja) * | 2003-04-07 | 2004-11-04 | Toshiba Corp | 半導体装置及びその製造方法 |
-
2005
- 2005-02-23 US US11/063,624 patent/US20060188659A1/en not_active Abandoned
-
2006
- 2006-02-17 JP JP2007557069A patent/JP2008533702A/ja not_active Withdrawn
- 2006-02-17 CN CNA2006800129961A patent/CN101163557A/zh active Pending
- 2006-02-17 KR KR1020077021650A patent/KR20070113243A/ko not_active Application Discontinuation
- 2006-02-17 EP EP06735354A patent/EP1861208A2/en active Pending
- 2006-02-17 WO PCT/US2006/005659 patent/WO2006091486A2/en active Application Filing
- 2006-02-23 TW TW095106113A patent/TW200644162A/zh unknown
Also Published As
Publication number | Publication date |
---|---|
US20060188659A1 (en) | 2006-08-24 |
WO2006091486A2 (en) | 2006-08-31 |
WO2006091486A3 (en) | 2007-11-22 |
JP2008533702A (ja) | 2008-08-21 |
KR20070113243A (ko) | 2007-11-28 |
EP1861208A2 (en) | 2007-12-05 |
TW200644162A (en) | 2006-12-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101163557A (zh) | 堆叠存储单元的钴自启动化学镀通道填充 | |
JP6903061B2 (ja) | Si貫通電極のメッキのプロセス及び化学作用 | |
US7514353B2 (en) | Contact metallization scheme using a barrier layer over a silicide layer | |
TW527666B (en) | Electroless method of seed layer deposition, repair, and fabrication of Cu interconnects | |
US6794288B1 (en) | Method for electroless deposition of phosphorus-containing metal films onto copper with palladium-free activation | |
US7968462B1 (en) | Noble metal activation layer | |
Cho et al. | Electroless Cu for VLSI | |
JPS62271454A (ja) | Vlsiデバイス中の開口の選択無電界メツキ方法 | |
KR20070070210A (ko) | 마이크로전자 장치에 대한 코발트 및 니켈 무전해 도금 | |
CN101238239A (zh) | 微电子装置中的钴化学镀 | |
JPH0883796A (ja) | 半導体装置の配線形成に用いる無電解めっき浴及び半導体装置の配線形成方法 | |
US20020127348A1 (en) | Method for depositing copper or a copper alloy | |
US7064065B2 (en) | Silver under-layers for electroless cobalt alloys | |
CN108063117B (zh) | 互连结构及其形成方法 | |
JP2008533702A5 (zh) | ||
TW200949010A (en) | Electroless deposition of barrier layers | |
CN101693992B (zh) | 自催化无电工艺的稳定和性能 | |
Guo et al. | Metallization improvement on fabrication of interdigitated backside and double sided buried contact solar cells | |
TWI509104B (zh) | 釕之無電沈積用之鍍覆溶液 | |
TWI332999B (en) | Cobalt-based alloy electroless plating solution and electroless plating method using the same | |
US7335288B2 (en) | Methods for depositing copper on a noble metal layer of a work piece | |
CN1784507B (zh) | 用于半导体工业中的三元材料的无电沉积用组合物 | |
US6555171B1 (en) | Cu/Sn/Pd activation of a barrier layer for electroless CU deposition | |
Ebong et al. | On Electroless Plating and Double Sided Buried Contact Silicon Solar Cells | |
JP6743289B2 (ja) | 窒化ガリウム半導体の活性化されていない表面上へのパラジウムの直接的な堆積方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080416 |