TW575679B - Low temperature CVD processes for preparing ferroelectric films using Bi aryls - Google Patents
Low temperature CVD processes for preparing ferroelectric films using Bi aryls Download PDFInfo
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- TW575679B TW575679B TW88121548A TW88121548A TW575679B TW 575679 B TW575679 B TW 575679B TW 88121548 A TW88121548 A TW 88121548A TW 88121548 A TW88121548 A TW 88121548A TW 575679 B TW575679 B TW 575679B
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- 238000000034 method Methods 0.000 title claims description 113
- 125000003118 aryl group Chemical group 0.000 title claims description 37
- 230000008569 process Effects 0.000 title claims description 21
- 239000002243 precursor Substances 0.000 claims description 121
- 239000000758 substrate Substances 0.000 claims description 68
- 239000007800 oxidant agent Substances 0.000 claims description 42
- 238000011049 filling Methods 0.000 claims description 34
- 238000000151 deposition Methods 0.000 claims description 33
- 229910052715 tantalum Inorganic materials 0.000 claims description 33
- 230000008021 deposition Effects 0.000 claims description 31
- 230000001590 oxidative effect Effects 0.000 claims description 31
- 229910044991 metal oxide Inorganic materials 0.000 claims description 30
- 150000004706 metal oxides Chemical class 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 29
- 229910052712 strontium Inorganic materials 0.000 claims description 28
- 230000002079 cooperative effect Effects 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 24
- 229910052797 bismuth Inorganic materials 0.000 claims description 19
- 125000001153 fluoro group Chemical group F* 0.000 claims description 17
- 229910052731 fluorine Inorganic materials 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- -1 pentylphenyl Chemical group 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 239000003990 capacitor Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 238000000354 decomposition reaction Methods 0.000 claims description 11
- 125000003277 amino group Chemical group 0.000 claims description 10
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229920000768 polyamine Polymers 0.000 claims description 7
- 229910052693 Europium Inorganic materials 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 6
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims description 6
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 claims description 6
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910000909 Lead-bismuth eutectic Inorganic materials 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 230000005669 field effect Effects 0.000 claims description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 125000004212 difluorophenyl group Chemical group 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 125000001207 fluorophenyl group Chemical group 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000010884 ion-beam technique Methods 0.000 claims description 4
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 claims description 3
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 2
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- 125000003172 aldehyde group Chemical group 0.000 claims description 2
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- 239000003849 aromatic solvent Substances 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 125000004360 trifluorophenyl group Chemical group 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims 10
- 125000003545 alkoxy group Chemical group 0.000 claims 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims 2
- PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 claims 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 claims 1
- 229910003781 PbTiO3 Inorganic materials 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 229910052788 barium Inorganic materials 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 claims 1
- 125000005265 dialkylamine group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 229910052745 lead Inorganic materials 0.000 claims 1
- 229910052706 scandium Inorganic materials 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- 239000010408 film Substances 0.000 description 32
- 239000010410 layer Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 14
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 3
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- 239000011737 fluorine Substances 0.000 description 3
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- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 2
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- 230000037361 pathway Effects 0.000 description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 2
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- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010421 TiNx Inorganic materials 0.000 description 1
- JDWUYRXZLQSJIE-UHFFFAOYSA-N [Os].[Bi] Chemical compound [Os].[Bi] JDWUYRXZLQSJIE-UHFFFAOYSA-N 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
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- 150000002843 nonmetals Chemical class 0.000 description 1
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- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
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- 238000006462 rearrangement reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 description 1
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- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02197—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides the material having a perovskite structure, e.g. BaTiO3
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/452—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by activating reactive gas streams before their introduction into the reaction chamber, e.g. by ionisation or addition of reactive species
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
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Description
經濟部智慧財J局員工消費合作社印製 575679 A7 B7 五、發明說明(ί ) 本項發明的背景: 本項發明乃提供一含B i金屬氧化膜,以化學氣相沈積 法的方法在一底材的表面,藉著分解出Bi氧化物的先質 來形成。 在最近幾年,對於在鐵電材料上的興趣是漸增的,此 乃由於其於非揮發性記憶體上的應用。利用在一薄鐵電 膜所形成的電容極板產生極化作用,可用來作訊息的貯 存。此電容被連結至一電晶體,兩者便形成了一貯存晶 胞,此貯存晶胞控制了電子於電容內讀出訊號的機制。 在此晶胞內所貯存的訊息,可藉由一電場施加於此薄. 鐵電膜上,且造成極化的作用改變下被改變。鐵電式隨 機存取記憶體(FERAMs),不同於DRAM (動態隨機存取 記憶體),將會在電力關閉時依然保留所貯存的訊息,除 此之外,其並不需要再重新重覆性再灌入訊息,對於鐵 電材料利用在記憶上所需的電性特性包含的有:(a)具一 強制性電場可在低電壓提供下來使用;(b)具一高還原性 極化特性,能對訊息的貯存具可靠性;(c)最小的疲乏性, 此乃爲具長的生命週期上的需求;且(d)不具印記特性, 因印記將會改變所貯存的訊息。 緦_鉍鉅鹽酸(SrBi2Ta 20 9)(SBT)是一種鐵電材料,均 符合以上所有的需求,最重要的是能被製作並整合此材 料至記憶元件中,CBT的電容被以.Sol-gel方法來製作成 良好的電性的元件,此Sol-gel方法僅提供了具低密度的 SBT。爲獲致高密度整合性的SBT,另一種不同的方法: 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) —»-------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 575679 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明(> ) 如CVD,將被利用。 本項發明摘要 以一種觀點來說,本項發明的特徵在於利用Bi氧化物 及在低於450 °C溫度下,在一底材上分解反應來形成含 Bi的金屬氧化物。此B i的錯合物爲含至少一個芳香基, 並被用作Bi氧化物的先質。 本項發明說明了此簡式的觀點,其包含如下的一個或 多個特性。 此B i氧化物先質可在被分解前溶於一溶液之中,沈積 溫度可小於4 0 0 °C,此含B i氧化物亦可藉一 S r氧化物的 分解而提供,且同樣地,可由T a氧化物先質來形成s r 及Ta的氧化物,並且能在底材料上沈積Bi、Sr及Ta的 氧化物。Printed by the Employees ’Cooperative of the Bureau of Wisdom and Finance of the Ministry of Economic Affairs, 575679 A7 B7 V. Description of the Invention (ί) Background of the Invention: This invention is to provide a metal oxide film containing B i by chemical vapor deposition method. The surface of the substrate is formed by decomposing a precursor of Bi oxide. In recent years, there has been increasing interest in ferroelectric materials due to its use in non-volatile memory. The capacitor plate formed by a thin ferroelectric film is polarized and can be used for information storage. This capacitor is connected to a transistor, and the two form a storage cell. This storage cell controls the mechanism for the electrons to read the signal in the capacitor. The information stored in the unit cell can be applied to the thin ferroelectric film by an electric field, and the polarization effect can be changed. Ferroelectric Random Access Memory (FERAMs), unlike DRAM (Dynamic Random Access Memory), will retain the stored information when the power is turned off. In addition, it does not need to be repeated. Sexual re-injection information, the electrical characteristics required for ferroelectric materials to be used in memory include: (a) a mandatory electric field can be used at low voltages; (b) a highly reducing polarization Characteristics, can be reliable for the storage of information; (c) minimal fatigue, which is a requirement on a long life cycle; and (d) no imprint characteristics, because imprints will change the stored information.缌 _Bismuth Giant Hydrochloride (SrBi2Ta 20 9) (SBT) is a ferroelectric material that meets all the above requirements. The most important thing is that it can be made and integrated into memory elements. The capacitance of CBT is The gel method is used to make good electrical components. This Sol-gel method only provides SBT with low density. In order to achieve high-density integrated SBT, a different method: This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) — »-------------- ----- Order --------- line (please read the precautions on the back before filling this page) 575679 Printed by A7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs V. Invention Description (>) CVD will be used. SUMMARY OF THE INVENTION In one aspect, the invention is characterized by the use of Bi oxides and decomposition reactions on a substrate at temperatures below 450 ° C to form Bi-containing metal oxides. This Bi complex contains at least one aromatic group and is used as a precursor of Bi oxide. This invention illustrates this simplified view, which includes one or more of the following features. The B i oxide precursor can be dissolved in a solution before being decomposed, and the deposition temperature can be less than 400 ° C. The B i oxide can also be provided by the decomposition of an S r oxide, and the same Ground, oxides of sr and Ta can be formed from Ta oxide precursors, and oxides of Bi, Sr, and Ta can be deposited on the base material.
Bi、Sr及Ta的氧化物膜可被沈積來作爲一鐵電膜,或 藉著退火製程轉換成一鐵電薄膜。 此含Bi金屬氧化膜可藉CVD的方法在底材上形成,底 材的沈積溫度低於450°C,其包含了在CVD中Bi、Sr及 Ta氧化物先質的氣體,對於此先質作熱分解,並沈積此 氧化物於底材上,Bi、Sr及Ta氧化物先質可於氧化劑的 存在下,藉著氧化物分解而被分解,在此,氧化劑的樣 品包含了有 〇2、單一 〇2、〇3; Η202、Ν20; ΝΟχ(1^Χ $ 3),及氣流式0 2電漿,且在此氧化劑的溶度爲5%及 95%的總氣體量於CV.D中,至少一種Ο 2及Ν20可被用作 氧化劑,此氧化劑可藉著利用CVD的電漿化、UV光、 用中國國家標準(CNS)A4規格(210 X 297公釐) -------------—-----訂------.—線-4^" (請先閱讀背面之注意事項再填寫本頁) 575679 經濟部智慧財產局員工消費合作社印製 A7 ___B7___ 五、發明說明(4 ) 熱敏感器或離子束,轉換氧化劑分子至一活化氧化劑。 此Bi氧化物的先質可爲公式Bi(ph) 3或Bi(ph(R)) 3,其 中R爲氟、芳香基、烷基或胺基。幾個Bi氧化物先質的 例子Bi(phenyl(R))3,其中R爲2〜4,可爲甲基、乙基、 丙基、丁基或戊基;Bi(phenyl(R’)2)3,其中R’基有二種位 置,自 2〜5,可爲 Et、Pr、’Pr 或,Bu; Bi(phenyl(R’’)3)3, 其中 R” 爲 Me、Et、Pr、’Pr 或 fBr; Bi(tetraalkylphenyl)3 ; Bi(pentaalkylphenyl) 3 ; B i ( a 1 c o x y p h e n y 1) 3,其中 alcoxy 基可自2〜4的位置,其中芳香基成份中alcoxy基分別爲 i4e、Et、Pr、JPr ^ fBu ; Bi(dialcoxypheny)3, S φ alcoxy 基可爲自2〜5的選擇位置,且其中烷基成份的alcoxy爲 Me、Et、Pr、'Pr 或 ’Bu ; Bi(dialkylamino-phenyl) 3,其 中胺基可爲2〜4的位置選擇,其中烷基爲Me、Et、Pr、fPr 或4\1; Bi(bis-(dialkylamino)-phenyl)3,其中胺基爲自 2〜5的位置選擇,且其中烷基爲Me、Et、Pr、fPr或ju ; Bi(flu〇r〇Phenyl)3,其中氟原子爲2~4的位置選擇; Bi(difluoro-phenyl)3,其中氟原子爲2〜5的位置選擇, Bi(trifluoro-phenyl(R))3,其中氟原子爲2〜5所選擇的3 位置;Bi(tetrafluoro-phenyl)3,其中氟原子爲自2〜5的 位置選擇;Bi(pentafluoro-phenyl)3。此Bi氧化物先質亦 包含有 Bi(o-tolyl)3、Bi(m-tolyl)3、Bi(p-tolyl)3、 Bi(2,4-dimethylphenyl)3、Bi(2,4,6-trimethylphenyl)3、 Bi(4-tert-butyphenyl)3、Bi(2,4,6-trialkylphenyl)3、 Bi(4-methoxyphenyl)3、Bi(4-(N,N-dimenthy)-phenyl)3、 本紙張尺度適用中國國家標準(CNS)A4規格(210 x 297公釐) --·------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 575679 經濟部智慧財產局員工消費合作社印製 A7 ___B7_ 五、發明說明(4 ) 及 Bi(4-fluorophenyl)3。 此含Bi金屬氧化物沈積在底材上,可爲公式 (BLOJ'AwB w03w+1)2-,其中 A 爲 Bi3+、L3+、L2+、Ca2+、 Sr 2+、Ba 2+、Pb 2+或 Na +,B 爲 F e 3+、A1 3+、S c 3+、Y 3+、L 3+、 L4+、Ti4+、Nb5+、Ta5+、W6+或 Mo6+及 L 爲 Ce4+、La3+、 Pr 3+、Ho 3+、Eu 2+或 Yb 2+,其中 1 S m S 5。此含 Bi 金屬氧 化物亦可有公式Bi2W06; BiM〇3,其中M爲Fe或Μη; Ba2BiM06,其中 Μ 爲 V、Nb 或 Ta; Pb2BiM06,其中 Μ 爲 V、Nb 或 Ta; Ba3Bi2M09,其中 M 爲 Mo 或 W; Pb6BiM018,其中 M 爲 Mo 或 \¥;^^11^ 20 6或 K2BiNb5015。 這些金屬氧化物可藉含上述金屬作先質的分解來得到, 此含Bi金屬氧化物亦可爲公式Bi 4Ti 30 12 ; PrBi 3Ti 30 12 ; HoBi 3Ti 3〇 12 ; LaBi3Ti3〇12; Bi 3TiTaO 9 ; Bi3TiNb〇9;The oxide films of Bi, Sr, and Ta can be deposited as a ferroelectric film, or converted into a ferroelectric film by an annealing process. This Bi-containing metal oxide film can be formed on the substrate by CVD. The deposition temperature of the substrate is lower than 450 ° C. It contains gases of the precursors of Bi, Sr and Ta oxides in CVD. For this precursor Decompose thermally and deposit this oxide on the substrate. Bi, Sr, and Ta oxide precursors can be decomposed by the decomposition of the oxide in the presence of the oxidant. Here, the oxidant sample contains 〇2 , Single 〇2, 〇3; Η202, Ν20; ΝΟχ (1 ^ χ $ 3), and gas flow type 0 2 plasma, and the solubility of the oxidant here is 5% and 95% of the total gas amount in CV. In D, at least one kind of O 2 and N 20 can be used as an oxidant, and the oxidant can be plasma-plasmidized by CVD, UV light, and Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---- ---------—----- Order ------.— line-4 ^ " (Please read the notes on the back before filling out this page) 575679 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ___B7___ printed by the consumer cooperative V. Description of the invention (4) The thermal sensor or ion beam converts the oxidant molecule to an activated oxidant. The precursor of this Bi oxide can be the formula Bi (ph) 3 or Bi (ph (R)) 3, where R is fluorine, aromatic, alkyl or amine. Examples of several Bi oxide precursors Bi (phenyl (R)) 3, where R is 2 ~ 4, which can be methyl, ethyl, propyl, butyl or pentyl; Bi (phenyl (R ') 2 ) 3, where the R 'group has two positions, from 2 to 5, can be Et, Pr,' Pr or, Bu; Bi (phenyl (R '') 3) 3, where R "is Me, Et, Pr , 'Pr or fBr; Bi (tetraalkylphenyl) 3; Bi (pentaalkylphenyl) 3; B i (a 1 coxypheny 1) 3, where the alcoxy group can be from 2 to 4, and the alcoxy group in the aromatic component is i4e, Et, Pr, JPr ^ fBu; Bi (dialcoxypheny) 3, S φ alcoxy group may be a selected position from 2 to 5, and the alcoxy of the alkyl component is Me, Et, Pr, 'Pr or' Bu; Bi ( dialkylamino-phenyl) 3, where the amine group can be selected from 2 to 4, where the alkyl group is Me, Et, Pr, fPr or 4 \ 1; Bi (bis- (dialkylamino) -phenyl) 3, where the amine group is Select from 2 ~ 5 positions, and the alkyl group is Me, Et, Pr, fPr or ju; Bi (flu〇r〇Phenyl) 3, where the fluorine atom is selected from 2 to 4 positions; Bi (difluoro-phenyl) 3, where the fluorine atom is selected from 2 to 5, Bi (trifluoro-pheny l (R)) 3, where the fluorine atom is the 3 position selected by 2 ~ 5; Bi (tetrafluoro-phenyl) 3, where the fluorine atom is selected from the position of 2 ~ 5; Bi (pentafluoro-phenyl) 3. This Bi The oxide precursor also contains Bi (o-tolyl) 3, Bi (m-tolyl) 3, Bi (p-tolyl) 3, Bi (2,4-dimethylphenyl) 3, and Bi (2,4,6-trimethylphenyl) ) 3, Bi (4-tert-butyphenyl) 3, Bi (2,4,6-trialkylphenyl) 3, Bi (4-methoxyphenyl) 3, Bi (4- (N, N-dimenthy) -phenyl) 3, Ben Paper size applies to China National Standard (CNS) A4 specification (210 x 297 mm) ---------------------- Order --------- line (Please read the precautions on the back before filling out this page) 575679 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ___B7_ V. Description of Invention (4) and Bi (4-fluorophenyl) 3. The Bi-containing metal oxide is deposited on the substrate and can be represented by the formula (BLOJ'AwB w03w + 1) 2-, where A is Bi3 +, L3 +, L2 +, Ca2 +, Sr 2+, Ba 2+, Pb 2+, or Na +, B is F e 3+, A1 3+, S c 3+, Y 3+, L 3+, L4 +, Ti4 +, Nb5 +, Ta5 +, W6 + or Mo6 +, and L is Ce4 +, La3 +, Pr 3+, Ho 3 +, Eu 2+ or Yb 2+, of which 1 S m S 5. This Bi-containing metal oxide can also have the formula Bi2W06; BiM03, where M is Fe or Mn; Ba2BiM06, where M is V, Nb, or Ta; Pb2BiM06, where M is V, Nb, or Ta; Ba3Bi2M09, where M is Mo or W; Pb6BiM018, where M is Mo or \ ¥; ^^ 11 ^ 20 6 or K2BiNb5015. These metal oxides can be obtained by the decomposition of the aforementioned metals containing precursors. The Bi-containing metal oxides can also be formulated as Bi 4Ti 30 12; PrBi 3Ti 30 12; HoBi 3Ti 3〇12; LaBi3Ti3〇12; Bi 3TiTaO 9 ; Bi3TiNb〇9;
SrBi 4Ti 40 15 ; CaBi 4Ti 4 〇 15 ; BaBi 4Ti 40 15 ; PbBi 4Ti 4 0 15 ; Sr 2Bi 4Ti 50 18 ; Ca 2Bi 4Ti 50 18 ; B a 2 B i 4 T i 50 18 ;SrBi 4Ti 40 15; CaBi 4Ti 4 〇 15; BaBi 4Ti 40 15; PbBi 4Ti 4 0 15; Sr 2Bi 4Ti 50 18; Ca 2Bi 4Ti 50 18; B a 2 B i 4 T i 50 18;
Pb 2Bi 4Ti 50 18 ; SrBi 5Ti 4FeO 18 ; CaBi 5Ti 4FeO 18 ;Pb 2Bi 4Ti 50 18; SrBi 5Ti 4FeO 18; CaBi 5Ti 4FeO 18;
BaBi 5Ti 4FeO 18 ; PbBi 5Ti 4FeO 18 ; Bi 5Ti 3FeO 15 ;BaBi 5Ti 4FeO 18; PbBi 5Ti 4FeO 18; Bi 5Ti 3FeO 15;
LaBi 4Ti 3FeO 15 ; PrBi 4Ti 3FeO 15 ; Bi 6Ti 3FeO 18 ; 3191^/65〇27;31*1_;^_2€3;^&1^1326141^4〇15,其中0$又 Sl、〇SY$l、且 0$ZSl;Sr 2_[F_zCa Ja yPb zBi 4Ti 50 18, 其中 0SXS2、0SYS2、且 Q,SZ$2;或 SruuCazBayPbzBiJi^FeOe,其中 0SXS1、OSYS 1、及0SZS1,一種金屬氧化物元素可被Ce、La、Pr、 Ho、Eu及Yb所取代。 本紙張尺度適用中國國家標準(CNS)A4規格(210 χ 297公釐) —------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 五 _I__———————— 經濟部智慧財產局員工消費合作社印製 575679 A7 B7 發叼說明(π ) 此含Bi金屬氧化物膜可爲SBT的衍生物,幾個衍生物 的例子含 SrBi2Ta2〇9;SrBi2Ta2_xNbz〇9,其中 〇$χ$2; SrBi2Nb209; Sr^Ba^BisTa 2_yNb y09,其中 〇SXSl,且 0SYS2; SruCazBi2Ta 2_yNb y09,其中 OSX^l,且 〇 S YS 2 ; SruPb^BiJayNbyC^,其中 OSXS1 及 OSY S 2,或 S r u_y_z Ba 尤 Ca yPb zBi 2Ta 2一p>N bp〇9,其中 osxg 1、OSYS、OSZS1及0SPS2。一種金屬元素氧化物 可被金屬如Ce、La、Pr、Ho、Eu及Yb所取代。 此Sr氧化物先質通常有公式Sr(thd)2或Sr(thd)2添加 物,且可含聚酯或聚胺化合物,此聚酯有公式如 R-C^CH'Heh-R’,其中2SnS6,且其中R及R’可爲 各自獨立爲烷基、芳香基、或氫,此聚胺有公式 R-NRH^CH'HzNRnh-R’,其中 2SnS6,其中 R 和 R’ 可爲獨立爲烷基、芳香基或氫,且其中R”爲氫、Me、Et 或Pr。此Sr氧化物先質亦含tetraglyme、triglyme、以 及 N,N,N’,N’’,N”- pentamethyl-diethylene-triamine 或 N,N,N’,N",NM',NM,-hexamethyl-triethylene-tetramineoLaBi 4Ti 3FeO 15; PrBi 4Ti 3FeO 15; Bi 6Ti 3FeO 18; 3191 ^ / 65〇27; 31 * 1 _; ^ _ 2 € 3; ^ & 1 ^ 1326141 ^ 4〇15, of which 0 $ and S1, 〇SY $ l, and 0 $ ZSl; Sr 2_ [F_zCa Ja yPb zBi 4Ti 50 18, of which 0SXS2, 0SYS2, and Q, SZ $ 2; or SruuCazBayPbzBiJi ^ FeOe, of which 0SXS1, OSYS 1, and 0SZS1, a metal oxide element, may be Replaced by Ce, La, Pr, Ho, Eu and Yb. This paper size applies to China National Standard (CNS) A4 specification (210 χ 297 mm) ---------------------- Order --------- Line ( Please read the notes on the back before filling out this page) 5. _I __—————————— Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 575679 A7 B7 Instructions (π) This Bi-containing metal oxide film may SBT is a derivative of SBT. Examples of several derivatives include SrBi2Ta2O9; SrBi2Ta2_xNbz09, where 0 $ χ $ 2; SrBi2Nb209; Sr ^ Ba ^ BisTa 2_yNb y09, where 0SXSl, and 0SYS2; SruCazBi2Ta 2_yNb y09, where OSX ^ l, and 0S YS 2; SruPb ^ BiJayNbyC ^, among which OSXS1 and OSY S 2, or S r u_y_z Ba especially Ca yPb zBi 2Ta 2 -p > N bp09, among which osxg 1, OSYS, OSZS1, and OSP2. An oxide of a metal element may be replaced by a metal such as Ce, La, Pr, Ho, Eu, and Yb. This Sr oxide precursor usually has the formula Sr (thd) 2 or Sr (thd) 2 additives, and can contain polyester or polyamine compounds. This polyester has the formula such as RC ^ CH'Heh-R ', where 2SnS6 , And where R and R 'can be independently alkyl, aromatic, or hydrogen, this polyamine has the formula R-NRH ^ CH'HzNRnh-R', where 2SnS6, where R and R 'can be independently alkane Group, aryl group or hydrogen, and R "is hydrogen, Me, Et or Pr. This Sr oxide precursor also contains tetraglyme, triglyme, and N, N, N ', N' ', N"-pentamethyl-diethylene -triamine or N, N, N ', N ", NM', NM, -hexamethyl-triethylene-tetramineo
Ta氧化物的先質通常有Ta(OR) 5_n(X) w公式,其中R爲 Me、Et、Pr、’Pr、Bu、)Bu、’Bu、pentyl 其 中X爲a-diketonate及1^η^5,舉例來說,此先質可爲 Ta(0 /prKthd)。 此Bi、Sr、Ta氧化物先質均可溶於一脂肪族化合物、 環脂化合物、或芳香族的溶劑中,可包含一官能基、如 醇、酯、fe、胺、酮及醛基,舉例來說,Bi、Sr、Ta氧 -7- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) —·------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 575679 A7 B7 五、發明說明(^ ) 化物的先質可溶方令如 octane、nonane、decane、undecane、 dodecane、tridecane、或 tetradecane’ 问樣地’這些先質 可溶於一些混合物如:THF、’PrOH比例8:2:1的 tetraglyme,同樣的,THF、fPrOH及聚胺各自的比例約 8:2:1、及 octane、decane及比例為 5:4:1 的 pentametlyl-diethylane -triamine〇 含有這些先質的溶液可被氣化,舉例來說,含有這些 先質的Bi氧化物可在溫度170 °C〜250 °C下被氣化,注入 一種Ar、He或N 2或的氣體被加入到此溶液蒸汽中,形 成了輸入氣體和Bi、Sr及Ta氧化物先質的蒸氣以2:1:2. 的比例混合,在此蒸氣混合物中最適合的濃度與幾個因 素有關,其包含了蒸氣溫度,在蒸發器內的壓力,氣體 與蒸氣的流動率,所需的化學計量比,及CVD內室的幾 何形狀。 在CV D室中,底材被加熱至3 5 0 °C ~ 4 5 (TC的沈積溫度, CVD室的壓力維持在0.001〜760 T〇rr之間,例如在0.1 Torr〜lOTorr,另外注入氣體於此CVD室中,其中此注入 氣體的濃度可由10 %變至90%於整個氣體,且蒸氣流入 此CVD室內,如30%〜50%的濃度下,適當的先質蒸氣、 氧化劑及注入氣體被引入於CVD室中,並以總流率爲1 ml/min~15000 ml/min標準狀況下注入,所希望的流率也 可與氣體及蒸氣的混合物的溫度及壓力,所需的薄膜化 學計量,以及CVD室的幾何形狀相關。這些氧化物沈積 到底材超過了 2分至2小時的時間,例如在2〜15分之間。 -8- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ---------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 575679 A7 B7 五、發明說明(7 ) 沈積之後,此膜被加熱至溫度6 0 0 °C〜8 0 0 °C,時間在5分 至3小時內。 此底材較佳地含有 Si、n-doped Si、p-doped Si、Si02、 Si3N4、GaAs、MgO、A1 20 3、Zr02、SrTi03、BaTi03或 PbTiO 3,此含Bi的金屬氧化膜於含一電晶體的底材上, 並被沈積在一底電極之上,此底電極藉著一插塞聯接至 電晶體,此底電極可爲含一種金屬,如Pt、Pd、Au、Ir 或Rh; —種導電的金屬氧化膜,如Ir〇z、RhOx、RuO/、 Os〇x、IU〇x或WO,其中0SXS2; —種導電金屬氮化 物,如 TiNx、WNyTaNy,其中 0SXS1,且 〇$ 1.7 ;或一種超導氧化物,如YBa2Cu 30 7_y,其中0$ XS 1,且Bi 2Sr 2Ca 2Cu 30 1Q,此底電極可爲一 Pt電極。 一種第一介層可提供在底電極與插塞之間,例如此第 一介層包含一 Ti的附著層及一氮化Ti的擴散阻障層。第 二介層也可提供於底電極與此金屬氧化層之間,例如第 二介層其包含了一種子層、一導電層、及一高電介係數 的介電層,此插塞包含了 W或Si,及被聯結至底電極及 M0S場效電晶體的源極和汲極。此膜亦可做爲一鐵電電 容一鐵電記憶體,及鐵電場效電晶體的鐵電薄膜,例如, 一金屬鐵電半導體或一金屬鐵電絕緣半導體。 此底材可以注入氣體及氧化劑的混合物之前或之後, 暴露於此金屬氧化物的先質蒸氣。加熱、分解及沈積的 製程於底材上至少要兩次,底材亦可被移除於室之外, 藉著至少一種中間性製程處理,如快速熱退火,然後置 -9- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) --·-----------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 575679 A7 ___________ B7 五、發明說明(4) 回室之內。 CVD的操作情況亦可被改變,舉例來說,先質的組成, 氧化劑及混合物中所注入的氣體等,均可在底材於CVD 室內時加以改變。Bi氧化物先質可在沈積開始至30分之 後期間被導入CVD室內;Bi氧化物的濃度於是漸減,另 一種方法是,底材在室內加熱於450 °C下至少兩次,或者 至少在〇 2及〇 3氧化劑中於室內加熱在450 °C之下,以另 一種槪念來說,本項發明的特徵在於底材上形成一層金 屬氧化膜,並藉著在底材上加熱不超過45 0 °C及引入Bi 氧化物先質蒸氣於底材上。Bi的錯合物包含了至少一種. 芳香基作爲Bi氧化物的先質,在底材表面將Bi氧化物 先質分解以形成Bi氧化物,並沈積在底材表面。 在此所使用的,所謂Bi氧化物先質這個名詞,表示任 一種能分解成Bi氧化物的Bi錯合物,其包含了 Bi芳香 基,此表示其結搆爲3或Bi(Ph(R)) 3,其中R爲氟、 芳香基、醇基或胺基’ Bi芳香基包含了上述所描述先質 等的衍生物。 利用Bi芳香基作爲Bi氧化物的先質於CVD中,能夠 提供一些好處,B i芳香基含B i - C鍵結,此鍵結相對地容 易解離,接著,B i芳香基能在相對低溫下被熱分解’在 低溫分解及沈積能減少B i氧化物遷移至底電極及底材, 此種先前已存在的結構於是被退化的情況將被減少。 除非有其它的定義’所有在此的技術的’科學的名詞 均有與一般藉著其中之一平常的技巧’在本項發明所屬 -1 0 - 本纸張尺度適用中國國家標準(CNS)A4規格(210 x 297公f ) --------訂----------^ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 575679 A7 B7 五、發明說明(?) 的技術上有相同的意義。雖然在此這些插述能被使用於 本項發明的實行或測試’有著相類.似或相等的方法及材 料’下列所描述的是適用性的方法及材料。所有發表、 專利應用、專利及其它在此所提及的參考均藉著被全部 參考而倂入,如果有所衝突,現在的規格,包含了定義 等’將會控制’除此之外,材料、方法及論例等均僅是 例證,且不被設限。 其它發明的特徵及好處將從以下的細節描述,以及自 申請專利範圍中出現。 圖式之簡略說明 第1圖爲鐵電記憶體的簡略貯存晶胞圖。 第2圖爲一 SBT層倂入至一帶有電晶體之疊層電容簡 略圖。 詳細說明 CVD能被用來提供Bi、Sr及Ta氧化物薄膜於底材表 面,此底材能被用來製造像貯存晶胞的元件。 參酌第1圖,一貯存晶胞藉一層鐵電材料1於一平板 電容器2間所形成,電容器2聯接至電晶體3,此電晶體 並有一位元織4及一訊號線5,其乃控制著電子於電容2 中的讀出,鐵電層1藉著以非揮發性的方式極化並能貯 存訊息。 參酌第2圖,一鐵電SBT層9被倂入一帶有電晶體的 疊式電容以形成一貯存晶胞’此疊式電容位於電晶體的 頂端,且此電容的底電極6被聯接以由多晶S i或W所形 -11- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ----I---------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 575679 經濟部智慧財產局員工消費合作社印製 A7 B7_______ 五、發明說明(P ) 成的插塞8與此MOSFET (金氧半場效電晶體),鐵電層 9於底電極6及上電極1 0間被配置。 CVD被使用來提供在第1及2圖的鐵電層,舉例來說, CVD被用來沈積金屬氧化物Bi、Sr及Ta於Pt/Ti/SiO 2的 底材上。 在CVD的期間,底材被置於低壓下的CVD室中,並被 加熱至沈積溫度,先質被蒸發然後被導入CVD室中’先 質的蒸氣在底材表面被分解,且金屬氧化物分子沈積在 底材上以形成一薄膜,藉著CVD製程比其它製程所製造 形成的金屬氧化物膜具高的均勻性,且具好的被覆性。. 更進一步的CVD製程好處包含了具高均一性,高密度’ 育成非常薄的膜的能力,高產量及低製造成本。 對於Bi氧化物Bi的先質 B i芳香基含有B i - C的鍵結,其具相對的容易解離性’ 導致在低溫下可沈積B i氧化物,舉例來說,3 0 〇 °C下。The precursor of Ta oxide usually has the formula of Ta (OR) 5_n (X) w, where R is Me, Et, Pr, 'Pr, Bu,) Bu,' Bu, pentyl, where X is a-diketonate and 1 ^ η ^ 5, for example, this precursor may be Ta (0 / prKthd). The Bi, Sr, and Ta oxide precursors are all soluble in an aliphatic compound, a cycloaliphatic compound, or an aromatic solvent, and may contain a functional group such as an alcohol, an ester, a fe, an amine, a ketone, and an aldehyde group. For example, Bi, Sr, Ta oxygen-7- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) ---------------------- --Order --------- line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 575679 A7 B7 V. Description of the invention (^) Soluble recipes such as octane, nonane, decane, undecane, dodecane, tridecane, or tetradecane 'samples' These precursors are soluble in some mixtures such as: THF, tetraglyme with' PrOH ratio 8: 2: 1, and likewise, THF, fPrOH, and polyamine each have a ratio of about 8: 2: 1, and octane, decane, and pentametlyl-diethylane-triamine in a ratio of 5: 4: 1. Solutions containing these precursors can be gasified, for example, Bi oxides containing these precursors can be gasified at a temperature of 170 ° C ~ 250 ° C. An Ar, He or N 2 or gas is injected into the In the solution vapor, the vapor forming the input gas and the precursors of Bi, Sr, and Ta oxides is mixed at a ratio of 2: 1: 2. The most suitable concentration in this vapor mixture is related to several factors, which include the vapor Temperature, pressure in the evaporator, gas and vapor flow rates, the required stoichiometric ratio, and the geometry of the CVD internal chamber. In the CV D chamber, the substrate is heated to a temperature of 350 ° C to 45 ° C (the deposition temperature of the CVD chamber, and the pressure in the CVD chamber is maintained between 0.001 to 760 Torr, for example, 0.1 Torr to 100 Torr), and an additional gas is injected. In this CVD chamber, the concentration of the injected gas can be changed from 10% to 90% in the entire gas, and the vapor flows into the CVD chamber. For example, at a concentration of 30% to 50%, the appropriate precursor vapor, oxidant and injection gas It is introduced into the CVD chamber and injected at a standard flow rate of 1 ml / min ~ 15000 ml / min. The desired flow rate can also be the temperature and pressure of the mixture with gas and vapor. The required film chemistry The measurement and the geometry of the CVD chamber are related. These oxides are deposited on the substrate for more than 2 minutes to 2 hours, such as between 2 and 15 minutes. -8- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) --------------------- Order --------- line (Please read the precautions on the back before filling in this Page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 575679 A7 B7 V. Description of the invention (7) After deposition, the film is heated to a temperature of 60 ° C ~ 80 ° 0 ° C for 5 minutes to 3 hours. This substrate preferably contains Si, n-doped Si, p-doped Si, Si02, Si3N4, GaAs, MgO, A1 20 3, Zr02, SrTi03, BaTi03 or PbTiO 3, this Bi-containing metal oxide film is deposited on a substrate containing an transistor, and is deposited on a bottom electrode, the bottom electrode is connected to the transistor through a plug, and the bottom electrode may include a kind of Metal, such as Pt, Pd, Au, Ir or Rh; a conductive metal oxide film, such as IrOz, RhOx, RuO /, OsOx, IU〇x or WO, where OSXS2;-a conductive metal nitride For example, TiNx, WNyTaNy, where 0SXS1, and 0 $ 1.7; or a superconducting oxide, such as YBa2Cu 30 7_y, where 0 $ XS 1, and Bi 2Sr 2Ca 2Cu 30 1Q, the bottom electrode may be a Pt electrode. The first interlayer may be provided between the bottom electrode and the plug. For example, the first interlayer includes an adhesion layer of Ti and a diffusion barrier layer of Ti nitride. The second interlayer may also be provided between the bottom electrode and the plug. Between the metal oxide layers, for example, the second dielectric layer includes a seed layer, a conductive layer, and a dielectric layer with a high dielectric constant. The plug includes W or Si, and the source and drain connected to the bottom electrode and the MOS field effect transistor. This film can also be used as a ferroelectric capacitor, a ferroelectric memory, and a ferroelectric thin film of a ferroelectric field effect transistor, For example, a metal ferroelectric semiconductor or a metal ferroelectric insulated semiconductor. The substrate can be exposed to the precursor vapor of the metal oxide before or after the gas and oxidant mixture is injected. The process of heating, decomposing and accumulating on the substrate must be at least two times. The substrate can also be removed from the chamber. At least one intermediate process, such as rapid thermal annealing, and then set to -9- Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ---------------------- Order --------- line (please first Read the notes on the back and fill in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 575679 A7 ___________ B7 V. Description of the invention (4) Return to the room. The operation of CVD can also be changed. For example, the composition of the precursor, the oxidant, and the gas injected in the mixture can be changed while the substrate is in the CVD chamber. The Bi oxide precursor can be introduced into the CVD chamber from the start of deposition to 30 minutes later; the concentration of Bi oxide is gradually reduced. Another method is to heat the substrate at least twice at 450 ° C, or at least 2 and 03 oxidants are heated at 450 ° C in the room. According to another idea, the invention is characterized in that a metal oxide film is formed on the substrate, and the substrate is heated by not more than 45 0 ° C and introduction of Bi oxide precursor vapor onto the substrate. The complex of Bi contains at least one kind. The aromatic group is used as the precursor of Bi oxide. The Bi oxide precursor is decomposed on the surface of the substrate to form Bi oxide, and is deposited on the surface of the substrate. As used herein, the term "Bi oxide precursor" means any Bi complex that can be decomposed into Bi oxides, which contains Bi aromatic groups, which means that its structure is 3 or Bi (Ph (R) ) 3, wherein R is fluorine, aryl, alcohol or amine 'Bi aryl includes derivatives such as the precursors described above. The use of Bi aromatic groups as precursors of Bi oxides in CVD can provide some benefits. The B i aromatic group contains a B i-C bond, which is relatively easy to dissociate. Then, the B i aromatic group can be relatively low temperature. Decomposition by thermal decomposition at low temperature and deposition can reduce the migration of Bi oxides to the bottom electrode and the substrate. Such previously existing structures will be reduced. Unless there are other definitions, 'all the technologies here' have scientific terms that are common with one of the usual techniques. In this invention -1 0-This paper applies Chinese National Standard (CNS) A4 Specifications (210 x 297 male f) -------- Order ---------- ^ (Please read the precautions on the back before filling out this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs System 575679 A7 B7 5. The technical description of the invention (?) Has the same meaning. Although these inserts can be used in the practice or testing of the invention, there are similar, similar or equivalent methods and materials. The methods and materials that are applicable are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. If there is a conflict, the current specifications, including definitions, etc. will be controlled. In addition, the materials , Methods, and examples are examples only and are not restricted. The features and benefits of other inventions will be described in detail below, as well as appearing in the scope of self-patenting. Brief Description of the Drawings Figure 1 is a simplified storage cell diagram of a ferroelectric memory. Figure 2 is a schematic diagram of an SBT layer inserted into a stacked capacitor with a transistor. Detailed description CVD can be used to provide Bi, Sr, and Ta oxide films on the surface of a substrate. This substrate can be used to make elements like storage cells. Referring to Fig. 1, a storage cell is formed by a layer of ferroelectric material 1 between a plate capacitor 2 and the capacitor 2 is connected to a transistor 3. The transistor has a single bit 4 and a signal line 5, which controls With the reading of the electrons in the capacitor 2, the ferroelectric layer 1 is able to store information by being polarized in a non-volatile manner. Referring to FIG. 2, a ferroelectric SBT layer 9 is inserted into a stacked capacitor with a transistor to form a storage cell. The stacked capacitor is located at the top of the transistor, and the bottom electrode 6 of the capacitor is connected by Formed by polycrystalline Si or W-11- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ---- I --------------- Order --------- line (please read the precautions on the back before filling this page) 575679 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_______ V. Plug of the invention (P) 8 and In this MOSFET (metal oxide half field effect transistor), a ferroelectric layer 9 is disposed between the bottom electrode 6 and the upper electrode 10. CVD is used to provide the ferroelectric layers in Figures 1 and 2. For example, CVD is used to deposit metal oxides Bi, Sr, and Ta on a Pt / Ti / SiO 2 substrate. During CVD, the substrate is placed in a CVD chamber under low pressure and heated to the deposition temperature. The precursor is evaporated and then introduced into the CVD chamber. The precursor vapor is decomposed on the substrate surface and the metal oxide The molecules are deposited on the substrate to form a thin film. The CVD process has higher uniformity and better coverage than the metal oxide film formed by other processes. Further benefits of the CVD process include high uniformity, high density ’ability to produce very thin films, high yields and low manufacturing costs. For the Bi oxide Bi precursor, the Bi aromatic group, contains a Bi-C bond, which is relatively easy to dissociate, leading to the deposition of Bi oxides at low temperatures, for example, at 300 ° C. .
Bi、Sr及Ta的氧化物可被沈積成所希望的具化學計量薄 膜,如Bi 20 3-Sr0-Ta 20 5。此SBT膜可利用Bi芳香基作 爲Bi氧化物的先質而獲得,並具高組成的均勻性於水 中,表面結構具高均一性,及高的再現性。Bi、Sr及Ta 氧化物膜藉由低溫沈積而形成一般非鐵電材質,但能經 由轉換而得到鐵電特性,藉箸鍍後的處理,如退火,能 轉換成鐵電的Aurivilius相。The oxides of Bi, Sr, and Ta can be deposited into a desired stoichiometric film, such as Bi 20 3-Sr0-Ta 20 5. This SBT film can be obtained by using Bi aromatic group as precursor of Bi oxide, and has high composition uniformity in water, high uniformity in surface structure, and high reproducibility. Bi, Sr, and Ta oxide films are formed by low-temperature deposition to form general non-ferroelectric materials, but ferroelectric properties can be obtained by conversion. After treatment, such as annealing, they can be converted into ferroelectric Aurivilius phases.
Bi芳香基被用作Bi氣化物先質通常有Bi(ph)3或 Bi(Ph(R))3的結構,其中R為氟、芳香基、醇基或一種胺基 ,幾個Bi芳香基的例子包含有:Bi (pheny 1 (R) ) 3 ,其中R為 -12- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ϋ n ϋ I n ϋ ϋ u ϋ 1 n n ϋ -1 n ϋ IT---------線 (請先閱讀背面之注意事項再填寫本頁) 575679 經濟部智慧財產局員工消費合作社印製 A7 _B7_ 五、發明說明(^ ) 位置選擇爲自2 ~4,且其中R爲甲基、乙基、丙基、異丙 基或間隔型丁基;Bi(phenyl(R’)2)3,其中R’基有兩種位 置選擇自2〜5,且R’爲Me、Et、Pr、卞1或411; Bi(phenyl(R”)3)3,其中R”基爲選擇三種位置自2〜5,且 R"爲 Me、Et、Pr、’Pr 或 ’Br; Bi(tetraalkylphenyl)3; Bi(pentaalkylphenyl)3; Bi(alcoxyphenyl)3,其中醇基爲 選擇位置自2〜4,且其中芳香基爲1^、£卜?1:、>1:或An ; Bi(bis(dialkylamino)-phenyl)3,其中胺基爲二種選擇位置 自2〜5,其中芳香基爲Me、Et、Pr、'Pr或’Bu ; Bi(fluorophenyl)3,其中此氟原子爲一種選擇位置自 2~4; Bi(difluoro-phenyl)3,其中氟原子爲二種選擇位置 自2〜5,Bi(trifluoro-phenyl)3,其中氧原子爲三種選擇位 置自2〜5;Bi(tetrafluoro-phenyl)3,其中氟原子爲位置自 2〜5,且Bi(pentafluoro-phenyl)3。此Bi氧化物先質亦包 含有 Bi(o-tolyl)3、Bi(m-tolyl)3、Bi(p-tolyl)3、 Bi(2,4-dimethylphenyl)3、Bi(2,4,6-trimethylphenyl)3、 Bi(4-tert_butyphenyl)3、Bi(2,4,6-trialkylphenyl)3、 Bi(4-methoxyphenyl)3、Bi(4-(N,N-dimenthy)-phenyl)3、 及 Bi(4-fluorophenyl)3o 所有這些分子均能在非常低溫下進行氧化分解,接 著,這些分子在可控制及可再現下得到Bi的氧化物,其 它的先質的製備可被發現或如下參考,A.P.Pisarevskii 等 Inorg,chem,35(6),P.84(1990) ; W.A. Hermann: ^, Chem Ber,126,P.1127(1993) ; R.G.Goel 等 J. Organomet. -13- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ——·---*---------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 575679 A7 B7 五、發明說明(A )Bi aromatic group is used as the precursor of Bi gas. Generally, it has the structure of Bi (ph) 3 or Bi (Ph (R)) 3, where R is fluorine, aromatic group, alcohol group or an amine group. Several Bi aromatic groups Examples include: Bi (pheny 1 (R)) 3, where R is -12- This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) ϋ n ϋ I n ϋ ϋ u ϋ 1 nn ϋ -1 n ϋ IT --------- line (please read the notes on the back before filling this page) 575679 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _B7_ V. Description of Invention (^) The position is selected from 2 to 4, and R is methyl, ethyl, propyl, isopropyl or spacer butyl; Bi (phenyl (R ') 2) 3, where R' group has two positions From 2 to 5, and R 'is Me, Et, Pr, 卞 1 or 411; Bi (phenyl (R ") 3) 3, where the R" group is selected from three positions from 2 to 5, and R " is Me, Et, Pr, 'Pr or' Br; Bi (tetraalkylphenyl) 3; Bi (pentaalkylphenyl) 3; Bi (alcoxyphenyl) 3, where the alcohol group is selected from 2 to 4, and where the aromatic group is 1 ^, £? 1: > 1: Or An; Bi (bis (dialkylamino) -phenyl) 3, in which the amine group is two selected positions from 2 to 5, where the aromatic group is Me, Et, Pr, 'Pr or' Bu; Bi (fluorophenyl) 3, where the fluorine atom is a selected position from 2 to 4; Bi (difluoro-phenyl) 3, where the fluorine atom is two selected positions from 2 to 5, Bi (trifluoro-phenyl) 3, where oxygen The atoms are three selected positions from 2 to 5; Bi (tetrafluoro-phenyl) 3, where the fluorine atom is from 2 to 5 and Bi (pentafluoro-phenyl) 3. This Bi oxide precursor also contains Bi (o-tolyl) 3, Bi (m-tolyl) 3, Bi (p-tolyl) 3, Bi (2,4-dimethylphenyl) 3, and Bi (2,4,6 -trimethylphenyl) 3, Bi (4-tert_butyphenyl) 3, Bi (2,4,6-trialkylphenyl) 3, Bi (4-methoxyphenyl) 3, Bi (4- (N, N-dimenthy) -phenyl) 3, and Bi (4-fluorophenyl) 3o All of these molecules can be oxidatively decomposed at very low temperatures. Then, these molecules can obtain Bi oxides under control and reproducibility. The preparation of other precursors can be found or referenced below. APPisarevskii et Inorg, chem, 35 (6), P.84 (1990); WA Hermann: ^, Chem Ber, 126, P.1127 (1993); RGGoel et al. J. Organomet. -13- This paper standard is applicable China National Standard (CNS) A4 specification (210 X 297 mm) ——--- * --------------- Order --------- line (please (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 575679 A7 B7 V. Invention Description (A)
Chem,36,P.323(1972); 含Bi的金屬氧化物 沈積在底材上的含Bi金屬氧化物通常有下列結構: (Bi 20 3m+1)2- 其中 A 爲 Bi 3+、L 3+、L 2+、Ca 2+、Sr 2+、Ba 2+、Pb 2+或 Na +, B 爲 Fe 3+、Al 3+、Sc 3+、Y 3+、L 3+、L 4+、Ti 4+、Nb 5+、Ta 5+、 W 6+或Mo 6+,其中L表示一自鑭系列的金屬,如Ce 4+、Chem, 36, P.323 (1972); Bi-containing metal oxides deposited on substrates usually have the following structure: (Bi 20 3m + 1) 2- where A is Bi 3+, L 3+, L 2+, Ca 2+, Sr 2+, Ba 2+, Pb 2+ or Na +, and B is Fe 3+, Al 3+, Sc 3+, Y 3+, L 3+, L 4 +, Ti 4+, Nb 5+, Ta 5+, W 6+ or Mo 6+, where L represents a metal from the lanthanum series, such as Ce 4+,
La 3+、Pr 3+、Ho 3+、Eu 2+或 Yb2+,且 m 爲 1、2、3、4 或 5, 幾個Bi氧化物包含有:La 3+, Pr 3+, Ho 3+, Eu 2+ or Yb2 +, and m is 1, 2, 3, 4 or 5, and several Bi oxides include:
Bi 2W0 6 ;Bi 2W0 6;
BiM03,其中Μ爲Fe或Μη;BiM03, where M is Fe or Mη;
Ba2BiM06,其中 Μ 爲 V、Nb 或 Ta;Ba2BiM06, where M is V, Nb or Ta;
Pb2BiM06,其中 Μ 爲 V、Nb 或 Ta;Pb2BiM06, where M is V, Nb or Ta;
Ba3Bi2M09,其中厘爲Mo或W;Ba3Bi2M09, which is Mo or W;
Pb3Bi2M09,其中 M 爲 Mo 或 W;Pb3Bi2M09, where M is Mo or W;
Ba6BiM018,其中 M 爲 Mo 或 W;Ba6BiM018, where M is Mo or W;
Pb6BiM018,其中 M 爲 Mo 或 W; KBiTi 20 6 ;及 K 2BiNb 50 15 含Bi金屬氧化物亦可有以下結構:Bi 4Ti 3012 ;Pb6BiM018, where M is Mo or W; KBiTi 20 6; and K 2BiNb 50 15 Bi-containing metal oxide may also have the following structure: Bi 4Ti 3012;
PrBi 3Ti 30 12 ; HoBi 3Ti 30 12 ; LaBi 3Ti 30 12 ; Bi 3TiTaO 9 ;PrBi 3Ti 30 12; HoBi 3Ti 30 12; LaBi 3Ti 30 12; Bi 3TiTaO 9;
Bi 3TiNbO 9 ; SrBi 4Ti 40 15 ; CaBi4Ti4015; BaBi4Ti4015; PbBi4Ti4015; Sr 2Bi4Ti5018; C a 2 B i 4 Ti 50 18 ; B a 2 B i 4 Ti 50 18 ; Pb 2Bi 4Ti 50 18 ; SrBi 5Ti 4FeO 18 ; CaBi 5Ti 4FeO 18 ;Bi 3TiNbO 9; SrBi 4Ti 40 15; CaBi4Ti4015; BaBi4Ti4015; PbBi4Ti4015; Sr 2Bi4Ti5018; C a 2 B i 4 Ti 50 18; B a 2 B i 4 Ti 50 18; Pb 2Bi 4Ti 50 18; SrBi 5Ti 4FeO 18; CaBi 5Ti 4FeO 18;
BaBi 5Ti 4FeO 18 ; PbBi 5Ti 4FeO 18 ; Bi 5Ti 3FeO 15 ; -1 4- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 丨丨·------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 575679 A7 _ B7 五、發明說明(4)BaBi 5Ti 4FeO 18; PbBi 5Ti 4FeO 18; Bi 5Ti 3FeO 15; -1 4- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 丨 丨 --------- --------- Order --------- line (please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 575679 A7 _ B7 V. Invention Instructions (4)
LaBi4Ti3Fe015 ; PrBi 4Ti 3FeO 15 ; Bi6Ti3Fe018;LaBi4Ti3Fe015; PrBi 4Ti 3FeO 15; Bi6Ti3Fe018;
Bl9Tl3Fe5〇27’ srny_2CaYBayPbzBi4Ti4015,其中 0$X si,〇^Ym 〇sZ$1; Sr 2nzCayBayPbzBi4Ti5〇i8, 其中 0SXg2、〇SY^2、且 0SZS2;或. S r 工士y_z Ca/BayPb2Bi5Ti4Fe018,其中 osx^i, 1,且OS 1,一種金屬氧化物元素可被以、!^、?!*、 Η 〇、E u及Y b所取代。 這些含B i金屬氧化物爲優勢的非鐵電特性,但可經由 退火壬轉換成帶有層狀超導如同一^種Aurivilius相的 鐵電氧化物,另外這些金屬氧化物的製備亦可在下列參. 考中發現 ’ T.Kodas 及 M.J.Hampden-Smith,The Chemistry of Metal CVD,Wiley(1994),及 W.S. Rees,CVD of Nonmetals, Wiley(1996) ° S r氧化物的先質Bl9Tl3Fe5〇27 'srny_2CaYBayPbzBi4Ti4015, where 0 $ X si, 〇 ^ Ym 〇sZ $ 1; Sr 2nzCayBayPbzBi4Ti5〇i8, where 0SXg2, 〇SY ^ 2, and 0SZS2; or. , 1, and OS 1, a metal oxide element can be used ,! ^,? ! *, Η〇, Eu and Yb. These B i -containing metal oxides have the advantage of non-ferroelectric properties, but can be transformed into ferroelectric oxides with layered superconductors such as the same Aurivilius phase through annealing. In addition, the preparation of these metal oxides can also be performed in The following references are found in the test: T. Kodas and MJ Hampden-Smith, The Chemistry of Metal CVD, Wiley (1994), and WS Rees, CVD of Nonmetals, Wiley (1996) ° Sr oxide precursors
Sr(thd) 2或Sr(thd) 2添加劑通常作爲Sr氧化物的先質, 其中 thd 表不 2,2,6,6-tetramethyl-heptane-2,5-dionate, 另外其它的添加劑可爲: 聚酯類,舉例來說,R-O^CH/I^Oh-R,,其中2Sn ^6,且其中每一個R及R’各别地爲一芳香基、或氫或聚 胺類,舉例來說,ΙΙ-ΝΙΤ-ΚΗΊΝΙΙΊ-Π,其中2gn S6,其中每一個R和R1各自獨立爲一芳香基、烷基或氫 及在此R”爲Η、Me、Et或Pr。Sr (thd) 2 or Sr (thd) 2 additives are usually used as precursors of Sr oxides, where thd represents 2,2,6,6-tetramethyl-heptane-2,5-dionate, and other additives can be: Polyesters, for example, RO ^ CH / I ^ Oh-R, where 2Sn ^ 6, and each of R and R 'are each an aromatic group, or hydrogen or a polyamine, for example , ΙΙ-ΝΙΤ-ΚΗΊΝΙΙΠ-Π, where 2gn S6, wherein each of R and R1 is independently an aromatic group, alkyl group or hydrogen and R "is”, Me, Et or Pr.
Sr(thd)2添加劑可包含 tetraglyme、triglyme、 N,N,N’,N 丨丨,Ν’丨- pentamethyl-diethylene-triamine 或 -15- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) --·------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 575679 A7 B7 五、發明說明(4) Ν,Ν,Ν’,Ν’’,Ν’Π ,Ν’’’-hexamethyl-triethylene-tetramine 〇Sr (thd) 2 additives can include tetraglyme, triglyme, N, N, N ', N 丨 丨, N' 丨-pentamethyl-diethylene-triamine or -15- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) ---------- order --------- line (please read the precautions on the back before filling this page) 575679 A7 B7 V. Description of the invention (4) Ν, Ν, Ν ', Ν' ', Ν'Π, Ν' ''-hexamethyl-triethylene-tetramine 〇
Ta氧化物的先質:Precursors of Ta oxide:
Ta氧化物的先質通常有結構:Ta(OR) ^(X) w,其中R 爲 Me、Et、Pr、'Pr、Bu、j Bu ^ fBu、pentyl 或'pentyl; 其中X爲一 a-diketonate,且其中l$nS5,舉例來說,The precursors of Ta oxides usually have a structure: Ta (OR) ^ (X) w, where R is Me, Et, Pr, 'Pr, Bu, j Bu ^ fBu, pentyl, or' pentyl; where X is a a- diketonate, and where l $ nS5, for example,
Ta(0 lP〇(thd)可作爲Ta氧化物的先質。 S B T : 緦鉍鉅酸鹽通常有結構:SrBi 2 Ta 2 0 9或其衍生物,如同: SrBi 2Ta 2_zNb 9,其中 0$XS2Ta (0 lP〇 (thd) can be used as the precursor of Ta oxide. S B T: osmium bismuth giant salt usually has the structure: SrBi 2 Ta 2 0 9 or its derivative, like: SrBi 2Ta 2_zNb 9, where 0 $ XS2
SrBi 2Nb 20 9SrBi 2Nb 20 9
Sri_zBa2Ta2_yNby09,其中 0SXS1 且 0SYS2 Sr jjCa zBi 2Ta 2_yNb y09,其中 0SXS1 且 0SYS2 Sr ^Pb 2Ta 2_FNb yO 9,其中 0SXS1 且 0SYS2 Sr pujBa zCa yPb zBi2Ta 卜 PNb 尸 09,其中 0SXS1,Og Y$l,〇$ZSlS〇gPS2 SBT亦包含上述化合物,其以一種或多種元素所組成, 且摻雜了自鑭系金屬,如Ce、La ' Pr、Ho、Eu及Yb。 混合物溶液 B i、S r及T a氧化物的先質被溶解在溶劑中或一種混合 溶液中,並且以液相被導入至蒸發器中,舉例來說,此 溶劑包含了有,但不被限定爲a 1 i p h a t i c (脂肪族)、 cycloaliphatic (環脂族)、aromatic ((芳香族)溶劑,這溶爾 可能具有一些官能基,如同醇、酯、醚、酯、胺、酮及 醛類,舉例來說,Bi、Sr及Ta的先質可被溶解在octane、 nonane 、 decane 、 undecane 、 dodecane 、 tridecane 或 -16- 本紙張尺度適用中國國家標準(CNS)A4規格(210 x 297公釐) (請先閱讀背面之注意事項再填寫本頁) -0 ϋ ϋ -ϋ ϋ 訂---------線- 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印制农 575679 A7 B7 五、發明說明(π ) t e t r a d e c a n e等。這些溶劑的混合物亦可被使用,舉例來 說,THF、fprOH及tetraglyme以比例8:2:1的混合物, 同樣地,以THF、PrOH及聚胺以比例8:2:1混合物,同樣地,如 octane、decane、及 pentamethyl-diethylene-triamine 以 比例5·· 4 :1的混合物,進一步的細節描述在最近發生的專 利U.S.S.N 09/107,861發表在1998,6月30日,名爲非 晶沈積金屬氧化物陶瓷膜,其藉此倂入參考之列。 蒸發製程:Sri_zBa2Ta2_yNby09, of which 0SXS1 and 0SYS2 Sr jjCa zBi 2Ta 2_yNb y09, of which 0SXS1 and 0SYS2 Sr ^ Pb 2Ta 2_FNb yO 9, of which 0SXS1 and 0SYS2 Sr pujBa zCa yPbZ $ 1 ZB2Z $ 2ZY2Ta2S OgPS2 SBT also contains the above-mentioned compounds, which are composed of one or more elements and are doped from lanthanide metals such as Ce, La 'Pr, Ho, Eu, and Yb. The precursors of the mixed solution B i, S r and Ta oxide are dissolved in a solvent or a mixed solution and introduced into the evaporator in the liquid phase. For example, this solvent contains but is not Limited to a 1 iphatic (aliphatic), cycloaliphatic (aromatic), aromatic ((aromatic) solvents, this sol may have some functional groups, such as alcohols, esters, ethers, esters, amines, ketones and aldehydes, For example, the precursors of Bi, Sr, and Ta can be dissolved in octane, nonane, decane, undecane, dodecane, tridecane, or -16- This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) (Please read the precautions on the back before filling out this page) -0 ϋ ϋ -ϋ ϋ Order --------- Line-Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives Printed Agricultural 575679 A7 B7 V. Description of the invention (π) tetradecane, etc. A mixture of these solvents can also be used, for example, a mixture of THF, fprOH and tetraglyme in a ratio of 8: 2: 1. Similarly, THF, PrOH and polyamines Example 8: 2: 1 mixture, likewise, mixtures such as octane, decane, and pentamethyl-diethylene-triamine at a ratio of 5. 4: 1, further details are described in the recently occurring patent USSN 09 / 107,861 published in 1998, On June 30th, it was named amorphous deposited metal oxide ceramic film, which was incorporated as a reference. Evaporation process:
Bi、Sr及Ta氧化物的先質在被導入至CVD室前已被 蒸發,此先質溶液被蒸發,舉例來說,產生在一種或多. 種蒸發器中。此先質溶液可被安置於含有所有三種先 質,或多重溶液可被使用在每一種含有一種或多種先質 的溶液上。 在一具單一來源液態導入的CVD製程中,Bi芳香基是 伴隨著Sr及Ta氧化物並列式的被蒸發,接著,製備含有 些三種先質的溶液是必要的,另一種方式是蒸發在一含 Bi芳香基,及Sr和Ta氧化物於另一蒸發器,第^ 一種方 式是對於製造SBT層較適當,此乃因爲它容易且沈積易 被控制。 幾個導入式可被用於多重式蒸發器,這些先質被貯存 在分離式的溶液中,各別在不同的蒸發器中蒸發,此蒸 氣被混合然後再被導入在CVD室內的底材表面。另一方 式,Sr的先質及Ta氧化物被貯存在不同的溶液內,在蒸 發前相混合,舉例來說,藉著液態導入系統。此混合溶 -17- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) --.----------^^衣--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 575679 A7 B7__ ___ 五、發明說明(4 ) 液被導入至一單一蒸發器中,Bi氧化物的先質則被導入 一第二個蒸發器中’這些先質蒸發之後,此蒸氣相混合 並導入至CVD室內。 在另一個製程上,S r及T a氧化物的先質被貯存在一先 質混合物的溶液中,且被導入至一單一蒸發器,Bi芳香 基被導入一第二個蒸發器中,在這些先質蒸發之後,這 些蒸氣混合且被導入CVD室中,另外,Bi芳香基可在一 蒸發器中及Sr和Ta的氧化物在'第二個蒸發器中蒸發,然 而’將S r和T a氧化物先質在兩分離的貯存器中取代,以 製備含S r和T a氧化物以不同濃度下的混合物溶液亦可, 如此使得製成精確混合的S r及Ta氧化物先質。此外還得 依賴CVD的製程以下列一種或多種方式來參考:u.S專 利U.S.S.N 08/758,599在1996年12月27日所發表,名 爲利用多種相似先質組成的多重式蒸發器試劑提供系統 的 CVD ;及 U.S· Pat. No.5,536,323 ; U.S. Pat.The precursors of Bi, Sr, and Ta oxides have been evaporated before being introduced into the CVD chamber. This precursor solution is evaporated, for example, in one or more evaporators. This precursor solution can be placed on all three precursors, or multiple solutions can be used on each solution containing one or more precursors. In a CVD process in which a single source of liquid is introduced, the Bi aromatic group is evaporated side by side with Sr and Ta oxides. Next, it is necessary to prepare a solution containing some three precursors. Another method is to evaporate Containing Bi aromatic group, and Sr and Ta oxide in another evaporator, the first method is more suitable for manufacturing SBT layer, because it is easy and deposition can be easily controlled. Several lead-in methods can be used in multiple evaporators. These precursors are stored in separate solutions, and each is evaporated in different evaporators. This vapor is mixed and then introduced into the surface of the substrate in the CVD chamber. . On the other hand, precursors of Sr and Ta oxides are stored in different solutions and mixed before evaporation, for example, by liquid introduction into the system. This mixed solvent-17- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) --.---------- ^^ 衣 -------- Order --------- Line (Please read the notes on the back before filling this page) 575679 A7 B7__ ___ V. Description of the invention (4) The liquid is introduced into a single evaporator, the precursor of Bi oxide Then it is introduced into a second evaporator. After the precursors are evaporated, the vapor phase is mixed and introduced into the CVD chamber. In another process, precursors of S r and Ta oxide are stored in a solution of the precursor mixture and introduced into a single evaporator, and the Bi aromatic group is introduced into a second evaporator. After these precursors evaporate, these vapors are mixed and introduced into the CVD chamber. In addition, the Bi aromatic group can be evaporated in an evaporator and the oxides of Sr and Ta in the 'second evaporator, however' The T a oxide precursor is replaced in two separate reservoirs to prepare a mixed solution containing S r and T a oxides at different concentrations, so that an accurately mixed S r and Ta oxide precursor can be made. . In addition, the process that relies on CVD can be referenced in one or more of the following ways: uS patent USSN 08 / 758,599, published on December 27, 1996, is called CVD using a multi-evaporator reagent supply system composed of multiple similar precursors. ; And US Pat. No. 5,536,323; US Pat.
No.5,337,65 1 ; U.S. Pat. No.5,43 1,957 ; U.S. Pat. No.5,362,328 ;及 U.S. Pat. N〇.5,204,3 14。 氧化劑No. 5,337,65 1; U.S. Pat. No. 5,43 1,957; U.S. Pat. No. 5,362,328; and U.S. Pat. No. 5,204,3 14. Oxidant
Bi、Sr和Ta氧化物的先質在一種氧化劑的存在下,藉 著氧化分解而被分解,〇 2通常是作爲一種氧化劑,然而, 有效地沈積可藉更具反應性的氧化劑,在膜沈積時有所 改善,這些不同氧化劑的例子包含有單一 o2、〇3、h2o2、 N20、NOz ( 1$XS3),及 02的電漿。 這個氧化劑的濃度可維持在5%與95 %之間的總氣體量 -1 8 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) # 訂---------線- 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 575679 A7 B7 五、發明說明(α ) 及蒸氣量並流入CVD室中,至少有一種〇2及N20被用 在此反應器中,此氧化物可自一外在來源,如一容器的 方式供應至CVD室中,或藉著分子轉換成活性氧化劑在 CVD室中,及利用CVD的電漿形成一活性氧化劑,或用 UV光、一感光劑、或離子束達成。 〇 3能形成氧反應基,之後與及Sr和Ta氧化物的先 質反應,此種反應可能在邊界層處發生,舉例來說,藉 著氧的反應基的摻入於Bi-C的鍵結內,或藉電循環化雙 分子的反應方式來達成。當〇3與一含苯環的先質反應 時,0 3會攻擊苯環且由另一側來裂解此分子,而得到像〇 二BiPh3的中間產物,此中間產物或者會分解回到BiPh3 或進行重排反應而形成(PhO)BiPh 2,在底材表面的化學 特性也可被〇 3所影響,舉例來說,氧原子脫附的量可能 會增加,或表面的電化學位能及電導性可能被改變,〇 3也 可能會對於在CVD室中所成長的含Bi金屬氧化膜,影響 了其表面的化性。 NO及NO 2能在界面層處已經與這些先質反應,除此之 外,NO及NO 2亦能吸附在表面,從先質的分解反應上, 與中間物產生反應,或者更進一步增加此底材表面的化 學反應。 h2o2能在邊界層或異質表面上與先質反應,H 20 2能在 底材上形成OH及00H基,且對於這些先質能提供新的 分解途徑。 車一化〇2(’〇2)藉著如rose bengal或低於200nm下經 -19- 本紙張尺度適用中國國家標準,(CNS)A4規格(210 X 297公釐) II----------0W--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財彦局員工消費合作社印製 575679 ' A7 _ B7 五、發明說明(j) 光直接照射30 2上,在感光劑的存在下由3〇 2直接光照射 成〜非常具活性的氧化劑,舉例來說,低壓的Hg燈或激 光雷射。 爲形成氧電漿的氣流,此先質蒸氣將與氧電漿相混 合’在此電漿中反應性的物種爲單一氧原子,反應性0 2分 子及〇 3,此電漿乃於氧化劑前與先質的蒸氣混合而產 生,此有效的技術乃修正CVD的製程方式,而不用直接 在電漿中直接將先質暴露在高轉換能量中,此來自於G. Lucovsky 等在 J· Vac,Sci. Tech. A4. 681,1986 ; Van Buskirk 等,於 J.Vac,Sci.Tech.A10,1578 於 1992 中所 發表的內容。 氧化劑的使用提供了 一些在沈積含Bi金屬氧化膜上的 好處,一般來說,氧化劑能在低溫下,於底材上沈積Bi 的氧化物,氧化劑亦能穩定及加強在低壓下B i氧化物的 沈積,氧化劑亦能幫助在含Bi金屬氧化物膜的沈積上, 達到所欲達成的相。 CVD製程 當BiPh 3被使用來作爲Bi氧化物的先質時,SBT膜的 化學計量可在溫度低於400 °C下獲得,然而,Bi氧化物 的沈積可與底材相關,舉例來說,Bi氧化物沈積在Pt或 Bi20 3上來得比Si02、Ta20 5或SrO上好些,這種與底材 相關的特性,可能導至片片之間較差的再現性及在樣品 內差的均勻性,除此之外,Bi的氧化物可能會從Sr及Ta 的氧化物中分離出來。Bi氧化物的沈積似乎藉著一含多 -20- 本紙張尺度適用中國國家標準(cns)a4規格(2川χ 297公釐) --------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 575679 A7 __B7__ 五、發明說明(θ )The precursors of Bi, Sr, and Ta oxides are decomposed by oxidative decomposition in the presence of an oxidant. O2 is usually used as an oxidant. However, effective deposition can be achieved by more reactive oxidants in the film deposition. There are improvements over time. Examples of these different oxidants include a single o2, 03, h2o2, N20, NOz (1 $ XS3), and 02 plasma. The concentration of this oxidant can be maintained between 5% and 95% of the total gas amount. 1 8-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before (Fill in this page) # Order --------- Line-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Employee Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by 575679 A7 B7 V. Invention Description (α) and Vapor Volume And flow into the CVD chamber, at least one of O2 and N20 is used in the reactor, the oxide can be supplied to the CVD chamber from an external source, such as a container, or converted into an active oxidant by molecules An active oxidant is formed in the CVD chamber and the plasma using CVD, or it is achieved by UV light, a photosensitizer, or an ion beam. 〇3 can form an oxygen reactive group, and then react with precursors of Sr and Ta oxides. This reaction may occur at the boundary layer. For example, the reactive group of oxygen is incorporated into the Bi-C bond. In the junction, or by cycling the reaction of bimolecules by electricity. When 〇3 reacts with a precursor containing a benzene ring, 03 will attack the benzene ring and cleavage the molecule from the other side to obtain an intermediate product like 〇BiBh3, which may be decomposed back to BiPh3 or The rearrangement reaction forms (PhO) BiPh 2 and the chemical properties on the substrate surface can also be affected by 〇3. For example, the amount of oxygen atom desorption may increase, or the surface's electrochemical potential and conductivity It may be changed, and O3 may affect the surface chemical properties of the Bi-containing metal oxide film grown in the CVD chamber. NO and NO 2 can already react with these precursors at the interface layer. In addition, NO and NO 2 can also be adsorbed on the surface and react with the intermediates from the decomposition reaction of the precursors, or increase this further. Chemical reaction on the substrate surface. h2o2 can react with precursors on the boundary layer or heterogeneous surface, and H 20 2 can form OH and 00H groups on the substrate, and can provide new decomposition pathways for these precursors. Che Yihua 〇2 ('〇2) by -19 such as rose bengal or below 200- This paper size applies to Chinese national standards, (CNS) A4 specification (210 X 297 mm) II ----- ----- 0W -------- Order --------- line (Please read the precautions on the back before filling this page) Printed by the Employee Consumer Cooperative of the Wisdom and Finance Bureau of the Ministry of Economic Affairs 575679 'A7 _ B7 V. Description of the invention (j) Light is directly irradiated on 30 2 and directly irradiated by 30 2 in the presence of a photosensitizer to a very active oxidant, for example, a low-pressure Hg lamp or laser mine Shoot. In order to form the gas flow of the oxygen plasma, the precursor vapor will be mixed with the oxygen plasma. In this plasma, the reactive species are single oxygen atoms, reactive molecules and 0, this plasma is before the oxidant. Generated by mixing with precursor vapor, this effective technique is to modify the CVD process method, without directly exposing the precursor to high conversion energy directly in the plasma. This comes from G. Lucovsky et al. In J. Vac, Sci. Tech. A4. 681, 1986; Van Buskirk et al., J. Vac, Sci. Tech. A10, 1578, 1992. The use of oxidants provides some benefits on the deposition of Bi-containing metal oxide films. Generally speaking, oxidants can deposit Bi oxides on substrates at low temperatures, and oxidants can also stabilize and strengthen Bi oxides at low pressures. The deposition of oxidants can also help achieve the desired phase on the deposition of Bi-containing metal oxide films. CVD process When BiPh 3 is used as the precursor of Bi oxide, the stoichiometry of the SBT film can be obtained at temperatures below 400 ° C. However, the deposition of Bi oxide can be related to the substrate, for example, Bi oxide is better deposited on Pt or Bi20 3 than Si02, Ta20 5 or SrO. This substrate-related property may lead to poor reproducibility between pieces and poor uniformity within the sample. In addition, Bi oxides may be separated from Sr and Ta oxides. The deposition of Bi oxides seems to be more than -20- This paper size applies the Chinese national standard (cns) a4 specification (2 Sichuan χ 297 mm) ---------------- ---- Order --------- line (please read the notes on the back before filling this page) 575679 A7 __B7__ 5. Description of the invention (θ)
Bi的底材中被幫助更多,亦即,Bi氧化物傾向沈積於已 沈積了 Bi氧化物處而沈積。 此表面的相關性可能更需要對CVD在低溫下作精密的 控制,並利用BiPh 3作Bi氧化物的先質。一種方式乃利 用0 2作氧化劑且增加溫度以對B i氧化物分解,然而,低 沈積溫度是需要爲了對B i氧化物具好的均勻性,抑制B i 的遷移至底電極及底材,且阻止插塞的氧化。 另一種方式可加入額的氧化劑,抑或能幫助在先前部 份所討倫到的氧化性分解,舉例來說,電漿、UV光、離 子束及熱能均可應用到CVD室,來幫助BiPh 3的氧化。. 其它的氧化劑的添加,如〇 3、醇及Η 2 0亦能加入,舉例 來說,額外的〇·2〜2%的0 3將增加Bi氧化物的沈積率; 然而,過多的〇3,會提早Sr先質的分解,爲了阻止這種 逆分解,此Bi氧化物先質可能會在一不同的蒸發器中被 蒸發,且在與Ar、Ο 2及03混合時進行。此Sr及Ta氧化 物的先質個別被蒸發;且它們的蒸氣與Bi氧化物的先質 蒸氣被混合,藉著Bi芳香基蒸氣與〇3反應,此反應性 0 3的量能在與Sr及Ta氧化物蒸氣混合前被減少。此Bi 芳香基與〇 3混合的時間可藉著對負載氣體流動率上的處 理及在CVD室內的壓力所控制。這些先質蒸氣的混合可 在進入CVD室內前產生,舉例來說,在噴嘴的入口處’ 或在反應器中,舉例來說,在噴嘴中。同樣地,〇 3可各 別地置入到室中,如此〇 3便與蒸氣先質接觸到極短的時 間,舉例來說,Ο 3可經一具噴口點的分離環被注入至底 -2 1- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ----------f (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印制衣Bi substrates are more assisted, that is, Bi oxides tend to be deposited where Bi oxides have been deposited. This surface correlation may require more precise control of CVD at low temperatures and the use of BiPh 3 as the precursor of Bi oxide. One way is to use 02 as an oxidant and increase the temperature to decompose the Bi oxide. However, a low deposition temperature is required to have good uniformity of the Bi oxide and inhibit the migration of Bi to the bottom electrode and substrate. And prevent the plug from oxidizing. Another method can add oxidants, or it can help the oxidative decomposition discussed in the previous section. For example, plasma, UV light, ion beam and thermal energy can be applied to the CVD chamber to help BiPh 3 Oxidation. Addition of other oxidants, such as 〇3, alcohol, and Η 2 0 can also be added, for example, an additional 0 2 ~ 2% 0 3 will increase the deposition rate of Bi oxide; however, too much 〇 3 It will prematurely decompose the Sr precursor. In order to prevent this reverse decomposition, the Bi oxide precursor may be evaporated in a different evaporator, and it is carried out when it is mixed with Ar, O 2 and 03. The precursors of Sr and Ta oxide are individually evaporated; and their vapor is mixed with the precursor vapor of Bi oxide. By reacting Bi aromatic vapor with O 3, the amount of this reactive 0 3 can be reduced with Sr And Ta oxide vapor is reduced before mixing. The time during which the Bi aromatic group is mixed with 03 can be controlled by processing the load gas flow rate and the pressure in the CVD chamber. Mixing of these precursor vapors can occur before entering the CVD chamber, for example, at the entrance of a nozzle 'or in a reactor, for example, in a nozzle. Similarly, 〇3 can be placed into the chamber separately, so that 〇3 will be in contact with the vapor precursor for a very short time. For example, 〇3 can be injected to the bottom through a separation ring with a nozzle point- 2 1- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) ---------- f (Please read the precautions on the back before filling this page) Intellectual Property of the Ministry of Economic Affairs Bureau Consumer Printing Cooperative Printing Clothing
一口、I -^n .^ϋ ^1* Bif ϋ·* 11 n I _i^i ϋ I— i^i ϋ ^^1 i^i i Jaw _1 n Bi_l ϋ i^i n Hi l^i ϋ ϋ i I 575679 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(^) 材。 在其它的方法上,Bi氧化物先質的分離可藉對Bi芳香 基作化學上的修正的幫助,舉例來說,一個或多個Η原 子的苯基先質可以其它官能基,如烷基、醇基、氣-芳香 基或胺基來取代,這種取代能提供較有效的分解途徑, 舉例來說,氧-烷基、氧-芳香基或胺基存在於苯環上,將 會活化此環且幫助氧化。 此底材將被加熱至3 0 0 °C〜5 0 0 °C的溫度範圍內作沈 積,適當地,此底材被加熱至溫度4 5 0 °C以下。在室中壓 力維持在0.1〜10 Torr,負載氣體如Ar、He、或N2等, 氧化劑如 〇2、單一 02、03、H202、N20、N0j(l$X S 3 ),和氧電漿氣流均可被導入至CVD室中,此總氣體 流率維持在1及15000 seem,間,seem表示單位氣流在、 以單位c.c/min上,於標準情況下作量測,亦即,在〇。〇 及1 atm下。此沈積時間範圍自30〜60分。 CVD製程對SBT來說,能在不同的溫度下進行,舉例 來說,CVD製程溫度在430 °C時,可得到在氟石相中一非 鐵電性膜,藉由在600°C〜820°C作退火,舉例來說,750 °C下一小時,此膜將轉變成鐵電材質的Aurivilius相,此 沈積膜的結構與許多不同的沈積參數有關,雖然此沈積 溫度具最重要的效應,舉例來說,在較低溫沈積的膜, 舉例來說,350 °C下,是絕對地非晶向。 例1 低溫CVD製程 一 Pt/Ti/Si02/Si 底材(l〇〇nm Pt/30nm Ti/625nm Si02/ -22- 本紙張尺度適用中國國家標準(CNS)A4規格(210 x 297公釐) --------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 575679 經濟部智慧財產局員工消費合作社印製 A7 B7 ___ 五、發明說明(Η )Yikou, I-^ n. ^ Ϋ ^ 1 * Bif ϋ · * 11 n I _i ^ i ϋ I— i ^ i ϋ ^^ 1 i ^ ii Jaw _1 n Bi_l ϋ i ^ in Hi l ^ i ϋ ϋ i I 575679 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of Invention (^). In other methods, the separation of the Bi oxide precursor can be aided by chemical modification of the Bi aromatic group. For example, one or more phenyl atoms of the fluorene atom can have other functional groups, such as alkyl , Alcohol, gas-aromatic or amine groups, this substitution can provide a more efficient decomposition pathway. For example, oxy-alkyl, oxy-aromatic or amine groups are present on the benzene ring and will be activated. This ring also helps oxidation. This substrate will be heated to a temperature within the range of 300 ° C ~ 500 ° C for deposition. Appropriately, the substrate is heated to a temperature below 450 ° C. The pressure in the chamber is maintained at 0.1 ~ 10 Torr, the load gas is Ar, He, or N2, etc., the oxidant is 02, single 02, 03, H202, N20, N0j (l $ XS 3), and the oxygen plasma gas flow is all It can be introduced into the CVD chamber. The total gas flow rate is maintained at 1 and 15000 seem. Meanwhile, see indicates that the unit airflow is at the unit cc / min, which is measured under standard conditions, that is, at 0. 〇 and 1 atm. This deposition time ranges from 30 to 60 minutes. For SBT, the CVD process can be performed at different temperatures. For example, when the CVD process temperature is 430 ° C, a non-ferroelectric film in the fluorite phase can be obtained. By 600 ° C ~ 820 ° C For annealing, for example, at 750 ° C in the next hour, the film will be transformed into Aurivilius phase of ferroelectric material. The structure of this deposited film is related to many different deposition parameters, although this deposition temperature has the most important effect. For example, films deposited at lower temperatures, for example, at 350 ° C, are absolutely amorphous. Example 1 Low-temperature CVD process-Pt / Ti / Si02 / Si substrate (100nm Pt / 30nm Ti / 625nm Si02 / -22- This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) -------------------- Order --------- line (please read the notes on the back before filling this page) 575679 Bureau of Intellectual Property, Ministry of Economic Affairs Printed by employees' consumer cooperatives A7 B7 ___ 5. Description of invention (Η)
Si)於CVD室中,藉一電阻絲加熱器維持底材溫度保持在 300〜500°C,舉例來說,430°C下。Si) In the CVD chamber, a resistance wire heater is used to maintain the substrate temperature at 300 ~ 500 ° C, for example, at 430 ° C.
Bi(Ph)3、Sr(thd)2(tetraglyme)、及 Ta(OzPr)4(thd)各別 被用作Bi、Sr及Ta氧化物的先質,Bi、Sr及Ta氧化物 先質各別被貯存在THF、fprOH及tetraglyme,各以比例 8:2:1的溶液中,在每一個溶液中的濃度爲0.4莫耳的Bi 先質、〇·4莫耳的Ta先質、及0.15莫耳的Sr先質,這些 溶液均被混合在一液態的導入系統中,並藉著一幫浦聯 結至一含兩室的快速蒸器來導入,且藉一不鏽鋼陶瓷混 合物來分隔,先質溶液在2 0 0 °C之陶瓷中被蒸發,在氣相. 中先質的濃度爲21.5 % Bi先質、7 4:.2% Sr先質及4.3 %的 Ta先質,Ar被用作負載氣體來輸送先質的蒸氣導入CVD 室中。 〇 2及〇 3被用作氧化劑,〇 2被導入CVD室中以建立所 需的O 2/Ar比例,〇 3在一 〇 3電子性放電產生器中及藉UV 光的吸收裝置而獲得。 CVD室內的壓力爲8 Torr,且蒸氣的總流率爲50〇~2〇〇〇 seem 間,舉例來說! 〇 〇 〇 sc—cm '。此〇 2、〇 3和Ar注入至 CVD室的流率乃以〇 2爲20%〜80%的總流率的濃度下所 控制,舉例來說,5 0 %,且Ο 3對〇 2的濃度比例小於5 %, 藉著一節流閥對總氣流的調整,使得在CVD室內的壓力 被維持著,室壁、蒸發浴頭、及連結線均被加熱至2 0 〇〜2 2 0 °C,沈積時間30分鐘。 沈積之後,先質氣體被關閉且廢氣經由被以一高傳導 -23- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ---------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 575679 A7 B7 五、發明說明(》) 性真空幫浦所捕獲而排除,此室被以Ar/O 2混合氣體所沖 洗,且底材被加熱至750 °C 60分或800°C 15分以形成 鐵電 Aurivilius 相。 例2 高溫CVD製程 CVD亦可在高溫下進行,舉例來說,在600 °C下,先質 與沈積的狀況同於在低溫製程下所使用的,此高溫製程 導致了 一種非鐵電性的氟石相的膜,一個鐵電性 A u r i v i 1 i u s相,或在這些相的混合。 CVD製程之後,此沈積的膜在750 °C退火60分,或800 °C下退火15分以形成完全結晶的鐵電Aurivilius相。 例3 多重步驟的CVD製程 一種多重式步驟的製程亦被使用,其中一種不同的沈 積情況是前2-1 0分鐘來得到高Bi含量的膜,並相鄰於 Pt的底電極,並比其它的膜來得高,在前2〜1 0分鐘之後 增加Bi氧化物的量以導入至CVD室中,舉例來說,藉著 在Bi的氧-醇蒸發器中增加液態導入來達成,在這個步驟 中所有其它的參數,及之後步驟的所有參數均與在單一 步驟中所使用的情況相同。 當本項發明所描述並結合了細節說明被了解時,此先 前所描述的被說明且不受本項發明所局限,其被所附申 請專利範圍所定義,其它的槪念、優點及修正均在下列 申請專利範圍所涵蓋。 符號說明 1…鐵電層 24- 本紙張尺度適用中國國家標準(CNS)A4規格(210 x 297公釐) ' --------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 575679 A7 B7 五、發明說明(W ) 2…電容 3…電晶體 4…位元線 5…字元線 6…底電極 7…汲極 8…插塞 9…鐵電層 10···頂電極 ---------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -25- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)Bi (Ph) 3, Sr (thd) 2 (tetraglyme), and Ta (OzPr) 4 (thd) are used as precursors of Bi, Sr, and Ta oxide, respectively, and the precursors of Bi, Sr, and Ta oxide are each Do not store in THF, fprOH, and tetraglyme, each in a ratio of 8: 2: 1, in each solution, the concentration of the Bi precursor is 0.4 mole, the Ta precursor is 0.4 mole, and 0.15 Mol Sr precursors, these solutions are mixed in a liquid introduction system and introduced by a pump connected to a two-chamber fast steamer, and separated by a stainless steel ceramic mixture, the precursor solution It is evaporated in ceramic at 200 ° C, and its concentration in the gas phase is 21.5% Bi precursor, 7 4: .2% Sr precursor and 4.3% Ta precursor, and Ar is used as a load. The gas is used to transport precursor vapor into the CVD chamber. 〇2 and 〇3 are used as oxidants, 〇2 is introduced into the CVD chamber to establish the required O 2 / Ar ratio, 〇 3 is obtained in a 103 electronic discharge generator and by means of UV light absorption device. The pressure in the CVD chamber is 8 Torr, and the total vapor flow rate is between 50 and 2000 seem, for example! 〇 〇 〇 sc-cm '. The flow rate of 〇2, 〇3, and Ar injected into the CVD chamber is controlled at a concentration of 〇2 being a total flow rate of 20% to 80%, for example, 50%, and 〇3 vs. 〇2 The concentration ratio is less than 5%. By adjusting the total air flow through the throttle valve, the pressure in the CVD chamber is maintained, and the wall, the evaporation bath head, and the connection line are heated to 200 ° C to 220 ° C. The deposition time is 30 minutes. After deposition, the precursor gas is turned off and the exhaust gas is conducted with a high conductivity. -23- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------------ --------- Order --------- line (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 575679 A7 B7 V. Description of the invention (》) Captured by a vacuum pump and excluded. This chamber was flushed with an Ar / O 2 mixed gas, and the substrate was heated to 750 ° C for 60 minutes or 800 ° C for 15 minutes to form a ferroelectric Aurivilius phase. Example 2 High-temperature CVD process CVD can also be performed at high temperature. For example, at 600 ° C, the precursor and deposition conditions are the same as those used at low temperature. This high temperature process results in a non-ferroelectric Membrane of fluorite phase, a ferroelectric Aurivi 1 ius phase, or a mixture of these phases. After the CVD process, the deposited film was annealed at 750 ° C for 60 minutes, or 800 ° C for 15 minutes to form a fully crystalline ferroelectric Aurivilius phase. Example 3 Multi-step CVD process A multi-step process is also used. One of the different deposition conditions is to obtain a film with a high Bi content in the first 2 to 10 minutes, and it is adjacent to the bottom electrode of Pt, and is better than other The film comes high. After the first 2 to 10 minutes, the amount of Bi oxide is increased to be introduced into the CVD chamber. For example, this is achieved by increasing the liquid introduction in the oxygen-alcohol evaporator of Bi. In this step, All other parameters in the step, and all parameters in the subsequent steps are the same as those used in a single step. When this invention is described and understood in conjunction with the detailed description, this previously described description is not limited by this invention, it is defined by the scope of the attached patent application, and other ideas, advantages and amendments are Covered in the following patent applications. Explanation of symbols 1 ... Ferroelectric layer 24- This paper size applies to China National Standard (CNS) A4 specification (210 x 297 mm) '-------------------- Order --------- Wire (Please read the precautions on the back before filling this page) 575679 A7 B7 V. Description of the invention (W) 2 ... Capacitor 3 ... Transistor 4 ... Bit line 5 ... Word line 6 ... bottom electrode 7 ... drain electrode 8 ... plug 9 ... ferroelectric layer 10 ... top electrode --------------------- order ----- ---- Line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -25- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)
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