TWI841867B - 使用保護材料來沉積薄膜的方法 - Google Patents
使用保護材料來沉積薄膜的方法 Download PDFInfo
- Publication number
- TWI841867B TWI841867B TW110137391A TW110137391A TWI841867B TW I841867 B TWI841867 B TW I841867B TW 110137391 A TW110137391 A TW 110137391A TW 110137391 A TW110137391 A TW 110137391A TW I841867 B TWI841867 B TW I841867B
- Authority
- TW
- Taiwan
- Prior art keywords
- carbon atoms
- group
- represented
- following chemical
- chemical formula
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 47
- 239000010409 thin film Substances 0.000 title claims abstract description 27
- 238000000151 deposition Methods 0.000 title description 9
- 239000002243 precursor Substances 0.000 claims abstract description 59
- 239000010408 film Substances 0.000 claims abstract description 56
- 239000000376 reactant Substances 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 180
- 239000000126 substance Substances 0.000 claims description 62
- 125000000217 alkyl group Chemical group 0.000 claims description 48
- 125000003118 aryl group Chemical group 0.000 claims description 33
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 33
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 18
- 125000003282 alkyl amino group Chemical group 0.000 claims description 15
- 230000001681 protective effect Effects 0.000 claims description 15
- 125000005264 aryl amine group Chemical group 0.000 claims description 8
- 238000011010 flushing procedure Methods 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 150000003974 aralkylamines Chemical group 0.000 claims description 6
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000005241 heteroarylamino group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 claims description 4
- BIVNKSDKIFWKFA-UHFFFAOYSA-N N-propan-2-yl-N-silylpropan-2-amine Chemical group CC(C)N([SiH3])C(C)C BIVNKSDKIFWKFA-UHFFFAOYSA-N 0.000 claims description 3
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000005265 dialkylamine group Chemical group 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 239000007983 Tris buffer Substances 0.000 claims 1
- 125000001691 aryl alkyl amino group Chemical group 0.000 claims 1
- 125000001769 aryl amino group Chemical group 0.000 claims 1
- 238000010926 purge Methods 0.000 abstract description 7
- 239000007789 gas Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000006227 byproduct Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 125000003277 amino group Chemical group 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 8
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 8
- 229910052814 silicon oxide Inorganic materials 0.000 description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 3
- 101100012902 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) FIG2 gene Proteins 0.000 description 2
- 150000003975 aryl alkyl amines Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- -1 tris(dimethylamino)cyclopentadienylbismuth (IV) Chemical compound 0.000 description 2
- 101000827703 Homo sapiens Polyphosphoinositide phosphatase Proteins 0.000 description 1
- 102100023591 Polyphosphoinositide phosphatase Human genes 0.000 description 1
- 101100233916 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) KAR5 gene Proteins 0.000 description 1
- DMBKIFBGDPVPRA-UHFFFAOYSA-N [O-2].[Es+3].[O-2].[O-2].[Es+3] Chemical compound [O-2].[Es+3].[O-2].[O-2].[Es+3] DMBKIFBGDPVPRA-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
Classifications
-
- 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
- C23C16/455—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 introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
-
- 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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
-
- 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
- C23C16/04—Coating on selected surface areas, e.g. using masks
-
- 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
- C23C16/04—Coating on selected surface areas, e.g. using masks
- C23C16/042—Coating on selected surface areas, e.g. using masks using masks
-
- 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
- C23C16/401—Oxides containing silicon
-
- 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
- C23C16/403—Oxides of aluminium, magnesium or beryllium
-
- 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
- C23C16/405—Oxides of refractory metals or yttrium
-
- 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
- C23C16/455—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 introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45531—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making ternary or higher compositions
-
- 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
- C23C16/455—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 introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45534—Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
-
- 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
- C23C16/455—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 introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
-
- 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
- C23C16/455—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 introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
-
- 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
- C23C16/52—Controlling or regulating the coating process
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02142—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides
- H01L21/02148—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides the material containing hafnium, e.g. HfSiOx or HfSiON
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
- H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
- H01L21/02219—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/0228—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 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/811—Controlling the atmosphere during processing
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
揭示一種使用一表面保護材料形成一薄膜之方法，該方法包含將該表面保護材料供應至置放一基板之一腔室內部；沖洗該腔室之內部；將一摻雜前驅體供應至該腔室之內部；沖洗該腔室之內部；將一第一反應物供應至該腔室之內部，以使得該第一反應物與該經吸附摻雜前驅體反應以形成一摻雜薄膜；將一介電膜前驅體供應至該腔室之內部；沖洗該腔室之內部；及將一第二反應物供應至該腔室之內部，以使得該第二反應物與該經吸附介電膜前驅體反應以形成一介電膜。
Description
本發明係關於一種沉積薄膜的方法。更特定言之，本發明係關於沉積具有極薄厚度之薄膜的方法，以使得可容易地控制介電膜厚度及介電膜中之組成，從而實現所需組成比且改良薄膜之介電常數。
隨著諸如記憶體/非記憶體半導體裝置，諸如DRAM及Flash等的高整合及低功耗等變化，對形成具有極佳特性之介電薄膜的需求不斷加深。
例如，即使在極薄厚度下亦具有高介電常數之氧化鋯(ZrO2)及氧化鉿(HfO2)被用作電容器介電層。氧化鋯(ZrO2)及氧化鉿(HfO2)根據溫度及壓力以各種晶體結構存在，且電容根據結構而變化。已知四方氧化鋯(ZrO2)及立方或四方氧化鉿(HfO2)之電容相比於其他結構超過兩倍，但一般而言，單斜相在室溫及壓力下係穩定的。
因此，已經進行了許多研究以藉由摻雜穩定氧化鋯及氧化鉿晶體結構來獲得高介電常數。然而，摻雜會由於局部組成的不均勻性而導致介電特性及漏電流的劣化，且因此在應用中具有很多困難。因此，需要根據薄膜之組成均
勻性及結晶度的提高來提高電容，且有必要開發階梯覆蓋度提高的薄膜沉積方法。
本發明之一個目標為提供一種沉積具有極薄厚度之薄膜的方法。
本發明之另一目標為提供一種沉積薄膜之方法，以使得藉由容易地控制薄膜中之組成，且因此提高介電常數，可實現所需的組成比。
本發明之另一目標為提供一種沉積薄膜之方法，以使得藉由形成具有良好階梯覆蓋度之薄膜，同時提高結晶度來提供極佳的半導體裝置。
本發明之其他目標將自以下實施方式變得更顯而易見。
揭示一種使用一表面保護材料形成一薄膜之方法，該方法包含將該表面保護材料供應至置放一基板之一腔室內部；沖洗該腔室之內部；將一摻雜前驅體供應至該腔室之內部；沖洗該腔室之內部；將一第一反應物供應至該腔室之內部，以使得該第一反應物與該經吸附摻雜前驅體反應以形成一摻雜薄膜；將一介電膜前驅體供應至該腔室之內部；沖洗該腔室之內部；及將一第二反應物供應至該腔室之內部，以使得該第二反應物與該經吸附介電膜前驅體反應以形成一介電膜。
表面保護材料可由以下化學式1表示：
其中n為1或2，且R選自氫原子、具有1至5個碳原子之烷基、具有3至6個碳原子之環烷基及具有6至12個碳原子之芳基。
表面保護材料可由以下化學式2表示：
其中n各自獨立地選自1至5之整數。
表面保護材料可由以下化學式3表示：
其中n各自獨立地為0至8之整數，R1各自獨立地選自具有1至10個碳原子之烷基、具有1至5個碳原子之烷氧基或氫原子，R2各自獨立地選自具有1至8個碳原子之烷基、具有3至6個碳原子之環烷基及具有6至12個碳原子之芳基。
表面保護材料可由以下化學式4表示：
其中n各自獨立地為1至8之整數且m各自獨立地為1至5之整數，R1或R2各自獨立地選自具有1至8個碳原子之烷基、具有3至6個碳原
子之環烷基及具有6至12個碳原子之芳基。
表面保護材料可由以下化學式5表示：
其中n各自獨立地為1至5之整數且m各自獨立地為0至8之整數，R1各自獨立地選自具有1至8個碳原子之烷基或氫原子，R2各自獨立地選自具有1至8個碳原子之烷基、具有3至6個碳原子之環烷基及具有6至12個碳原子之芳基。
表面保護材料可由以下化學式6表示：
其中n各自獨立地為1至8之整數且m各自獨立地為1至6之整數，R1或R2各自獨立地選自具有1至8個碳原子之烷基、具有3至6個碳原子之環烷基及具有6至12個碳原子之芳基。
表面保護材料可由以下化學式7表示：
其中n各自獨立地為0至5之整數且m各自獨立地為1至5之整
數，R各自獨立地選自具有1至10個碳原子之烷基、具有3至10個碳原子之環烷基及具有6至12個碳原子之芳基。
表面保護材料可由以下化學式8表示：
其中n各自獨立地為0至8之整數，R1至R3各自獨立地選自具有1至8個碳原子之烷基，R4係選自氫、具有1至6個碳原子之烷基及具有1至8個碳原子之烷氧基。
摻雜前驅體可由以下化學式9表示：
其中R1至R3各自獨立地選自氫原子、具有1至10個碳原子之烷基、具有6至12個碳原子之芳基、具有1至10個碳原子之烷基胺基、具有2至10個碳原子之二烷基胺基、具有6至12個碳原子之芳基胺基、具有7至13個碳原子之芳烷基胺基、具有3至10個碳原子之環胺基、具有3至10個碳原子之雜環胺基、具有6至12個碳原子之雜芳基胺基、或具有2至10個碳原子之烷基矽烷胺基。
摻雜前驅體由以下化學式10至14中之任一者表示：<化學式10>
摻雜前驅體可由以下化學式15表示：<化學式15>
其中A及B各自獨立地選自氫原子、鹵素原子、具有1至10個碳原子之烷基、具有6至12個碳原子之芳基、具有2至10個碳原子之烷基胺基、具有6至12個碳原子之芳胺基及具有7至13個碳原子之芳烷基胺基、具有3至10個碳原子之環胺基、具有3至10個碳原子之雜環胺基及具有2至10個碳原子之烷基矽烷胺基，L選自鹵素原子、氫原子或疊氮基。
摻雜前驅體可由以下化學式16至21中之任一者表示：
<化學式19>
摻雜前驅體可由以下化學式22表示：
其中R1至R6各自獨立地選自氫原子、具有1至10個碳原子之烷基、具有6至12個碳原子之芳基、具有1至10個碳原子之烷基胺基、具有6至12個碳原子之芳基胺基、具有7至13個碳原子之芳烷基胺基、具有3至10個碳原子之環胺基、具有3至10個碳原子之雜環胺基、具有6至12個碳原子之雜芳基胺基、或具有2至10個碳原子之烷基矽烷胺基。
摻雜前驅體可由以下化學式23表示：
摻雜前驅體可由以下化學式24表示：
其中R1至R5各自獨立地選自氫原子及具有1至4個碳原子之烷基，R6至R9各自獨立地選自氫原子及具有1至4個碳原子之烷基、具有1至4個碳原子之烷基胺基、具有2至4個碳原子之二烷基胺基及具有6至12個碳原子之芳基。
摻雜前驅體可由以下化學式25至27中之任一者表示：
摻雜前驅體可由以下化學式28表示：
其中R1至R4各自獨立地選自氫原子及具有1至4個碳原子之烷基、具有1至4個碳原子之烷基胺基、具有2至4個碳原子之二烷基胺基及具有6至12個碳原子之芳基。
摻雜前驅體可由以下化學式29表示：
第一反應物及第二反應物可選自O3、O2、H2O、H2O2、N2O及NH3。
介電膜前驅體可為包括含有Ti、Zr及Hf之四價金屬中之至少一者的化合物。
圖1為示意性地展現根據本發明之實施例1之薄膜形成方法的流程圖。
圖2為示意性地展現根據本發明之比較實例1之供應循環的圖。
圖3為根據本發明之比較實例1之薄膜的X射線繞射(XRD)結果。
圖4為展現根據本發明之比較實例1的薄膜之碳之次級離子質譜分析(SIMS)的圖。
圖5為展現根據本發明之比較實例1的薄膜之矽之次級離子質譜分析(SIMS)的圖。
圖6為示意性地展現根據本發明之實施例1之供應循環的圖。
圖7為根據本發明之實施例1之薄膜的X射線繞射(XRD)結果。
圖8為展現根據本發明之實施例1的薄膜之碳之次級離子質譜分析(SIMS)的圖。
圖9為展現根據本發明之實施例1的薄膜之矽之次級離子質譜分析(SIMS)的圖。
在下文中，將使用圖1至圖9描述本發明之實施例。本發明之實施例可包括各種修改，且不應將本發明之範疇解釋為限於下文所描述之實施例。
圖1為示意性地展現根據本發明之實施例1之薄膜形成方法的流程圖。將基板裝載至製程腔室中，且調整以下ALD製程條件。ALD製程條件可包括基板或製程腔室之溫度、製程腔室中之壓力、氣體流速，且溫度為50至500℃。
將基板暴露於供應至腔室內部的表面保護材料，且表面保護材料被吸附至基板的表面。表面保護材料在沉積製程期間具有與摻雜前驅體相似的行為。表面保護材料形成一種抑制層，防止摻雜前驅體在後續製程中的吸附，從而減輕島狀生長及類似者，且改善其後形成之薄膜的局部組成不均勻性。
表面保護材料可由以下化學式1表示：
其中n為1或2，且R選自氫原子、具有1至5個碳原子之烷基、具有3至6個碳原子之環烷基及具有6至12個碳原子之芳基。
表面保護材料可由以下化學式2表示：
其中n各自獨立地選自1至5之整數。
表面保護材料可由以下化學式3表示：
其中n各自獨立地為0至8之整數，R1各自獨立地選自具有1至10個碳原子之烷基、具有1至5個碳原子之烷氧基或氫原子，R2各自獨立地選自具有1至8個碳原子之烷基、具有3至6個碳原子之環烷基及具有6至12個碳原子之芳基。
表面保護材料可由以下化學式4表示：
其中n各自獨立地為1至8之整數且m各自獨立地為1至5之整數，R1或R2各自獨立地選自具有1至8個碳原子之烷基、具有3至6個碳原子之環烷基及具有6至12個碳原子之芳基。
表面保護材料可由以下化學式5表示：
其中n各自獨立地為1至5之整數且m各自獨立地為0至8之整數，R1各自獨立地選自具有1至8個碳原子之烷基或氫原子，R2各自獨立地選自具有1至8個碳原子之烷基、具有3至6個碳原子之環烷基及具有6至12個碳原子之芳基。
表面保護材料可由以下化學式6表示：
其中n各自獨立地為1至8之整數且m各自獨立地為1至6之整數，R1或R2各自獨立地選自具有1至8個碳原子之烷基、具有3至6個碳原
子之環烷基及具有6至12個碳原子之芳基。
表面保護材料可由以下化學式7表示：
其中n各自獨立地為0至5之整數且m各自獨立地為1至5之整數，R各自獨立地選自具有1至10個碳原子之烷基、具有3至10個碳原子之環烷基及具有6至12個碳原子之芳基。
表面保護材料可由以下化學式8表示：
其中n各自獨立地為0至8之整數，R1至R3各自獨立地選自具有1至8個碳原子之烷基，R4係選自氫、具有1至6個碳原子之烷基及具有1至8個碳原子之烷氧基。
其後，將沖洗氣體(例如，諸如Ar之惰性氣體)供應至腔室內部以排出未吸附之表面保護材料或副產物。
其後，將基板暴露於供應至腔室內部之摻雜前驅體，且將摻雜前驅體吸附於基板之表面上。
摻雜前驅體可由以下化學式9表示：<化學式9>
其中R1至R3各自獨立地選自氫原子、具有1至10個碳原子之烷基、具有6至12個碳原子之芳基、具有1至10個碳原子之烷基胺基、具有2至10個碳原子之二烷基胺基、具有6至12個碳原子之芳基胺基、具有7至13個碳原子之芳烷基胺基、具有3至10個碳原子之環胺基、具有3至10個碳原子之雜環胺基、具有6至12個碳原子之雜芳基胺基、或具有2至10個碳原子之烷基矽烷胺基。
摻雜前驅體由以下化學式10至14中之任一者表示：
<化學式12>
摻雜前驅體可由以下化學式15表示：
其中A及B各自獨立地選自氫原子、鹵素原子、具有1至10個碳原子之烷基、具有6至12個碳原子之芳基、具有2至10個碳原子之烷基胺基、具有6至12個碳原子之芳胺基及具有7至13個碳原子之芳烷基胺基、具有3至10個碳原子之環胺基、具有3至10個碳原子之雜環胺基及具有2至10個碳原子之烷基矽烷胺基，L選自鹵素原子、氫原子或疊氮基。
摻雜前驅體可由以下化學式16至21中之任一者表示：
摻雜前驅體可由以下化學式22表示：<化學式22>
其中R1至R6各自獨立地選自氫原子、具有1至10個碳原子之烷基、具有6至12個碳原子之芳基、具有1至10個碳原子之烷基胺基、具有6至12個碳原子之芳基胺基、具有7至13個碳原子之芳烷基胺基、具有3至10個碳原子之環胺基、具有3至10個碳原子之雜環胺基、具有6至12個碳原子之雜芳基胺基、或具有2至10個碳原子之烷基矽烷胺基。
摻雜前驅體可由以下化學式23表示：
摻雜前驅體可由以下化學式24表示：
其中R1至R5各自獨立地選自氫原子及具有1至4個碳原子之烷基，R6至R9各自獨立地選自氫原子及具有1至4個碳原子之烷基、具有1至4個碳原子之烷基胺基、具有2至4個碳原子之二烷基胺基及具有6至12個碳原
子之芳基。
摻雜前驅體可由以下化學式25至27中之任一者表示：
摻雜前驅體可由以下化學式28表示：
其中R1至R4各自獨立地選自氫原子及具有1至4個碳原子之烷基、具有1至4個碳原子之烷基胺基、具有2至4個碳原子之二烷基胺基及具有
6至12個碳原子之芳基。
摻雜前驅體可由以下化學式29表示：
舉例而言，摻雜前驅體不可吸附於吸附表面保護材料之位置處。換言之，表面保護材料防止摻雜前驅體之吸附。
其後，將沖洗氣體(例如，諸如Ar之惰性氣體)供應至腔室內部以排出未吸附之摻雜前驅體或副產物。
其後，將基板暴露於供應至腔室內部之反應物，且在基板之表面上形成摻雜薄膜。反應物與摻雜前驅體反應以形成摻雜薄膜，且反應物可選自O3、O2、H2O、H2O2、N2O以及NH3。
其後，將沖洗氣體(例如，諸如Ar之惰性氣體)供應至腔室內部以排出未反應之材料或副產物。
其後，將基板暴露於供應至腔室內部之介電膜前驅體，且將介電膜前驅體吸附於基板之表面上。介電膜前驅體可為包括含有Ti、Zr及Hf之四價金屬中之至少一者的化合物。
其後，將沖洗氣體(例如，諸如Ar之惰性氣體)供應至腔室內部以排出未吸附之介電膜前驅體或副產物。
其後，將基板暴露於供應至腔室內部之反應物，且在基板之表面上形成介電膜。反應物與介電膜前驅體反應以形成介電膜，且反應物可選自O3、
O2、H2O、H2O2、N2O以及NH3。
其後，將沖洗氣體(例如，諸如Ar之惰性氣體)供應至腔室內部以排出未反應之材料或副產物。
比較實例1
圖2為示意性地展現根據本發明之比較實例1之供應循環的圖。氧化矽形成為摻雜薄膜，且氧化鉿形成為介電膜，而不使用上述表面保護材料。二異丙基胺基矽烷(DIPAS)用作摻雜前驅體以形成氧化矽，且參(二甲胺基)環戊二烯基鉿(IV)[CpHf(NMe2)3](HAC)用作介電膜前驅體，製程溫度為320℃，且反應物為O3氣體。
經由ALD製程形成薄膜之製程如下，且與習知摻雜方法類似，氧化矽及氧化鉿之循環比如下表1所示。表1示出根據比較實例1及實施例1之SiO2及HfO2的循環比及XRD四方相比(%)，且XRD四方相比係藉由T(101)/[(T101)+M(-111)+M(111)]計算。
1)使用Ar作為載氣，在室溫下將摻雜前驅體(DIPAS)供應至反應腔室，且將摻雜前驅體吸附至基板上。
2)向反應腔室中供應Ar氣體以排出未吸附的摻雜前驅體或副產物。
3)藉由向反應腔室供應臭氧氣體(O3)形成摻雜薄膜。
4)向反應腔室供應Ar氣體以排出未反應的物質或副產物。
5)使用Ar作為載氣，在室溫下將介電膜前驅體(HAC)供應至反應腔室，且將介電膜前驅體吸附至基板上。
6)向反應腔室中供應Ar氣體以排出未吸附的介電膜前驅體或副產物。
7)藉由向反應腔室供應臭氧氣體(O3)形成介電膜。
8)向反應腔室供應Ar氣體以排出未反應的物質或副產物。
圖3為根據本發明之比較實例1之薄膜的X射線繞射(XRD)結果。當Si比率較低(1：30)時，HfO及四方比相似。但是，當Si比增加(1：12)時，四方比會減小。
圖4為展現根據本發明之比較實例1的薄膜之碳之次級離子質譜分析(SIMS)的圖，圖5為展現根據本發明之比較實例1的薄膜之矽之次級離子質譜分析(SIMS)的圖。在碳雜質的情況下，其與HfO處於相似的位準，且在矽的情況下，Si峰強度處於相似的位準，而與Si循環比無關。
實施例1
圖6為示意性地展現根據本發明之實施例1之供應循環的圖。表面保護材料為原甲酸三甲酯，氧化矽形成為摻雜薄膜，且氧化鉿形成為介電膜。二異丙基胺基矽烷(DIPAS)用作摻雜前驅體以形成氧化矽，且參(二甲胺基)環戊二烯基鉿(IV)[CpHf(NMe2)3](HAC)用作介電膜前驅體，製程溫度為320℃，且反應物為O3氣體。
經由ALD製程形成薄膜之製程如下，且與習知摻雜方法類似，氧化矽及氧化鉿之循環比如上表1所示。
1)將表面保護材料供應至反應腔室以被吸附至基板上。
2)向反應腔室中供應Ar氣體以排出未吸附的表面保護材料或副產物。
3)使用Ar作為載氣，在室溫下將摻雜前驅體(DIPAS)供應至反應腔室，且將摻雜前驅體吸附至基板上。
4)向反應腔室中供應Ar氣體以排出未吸附的摻雜前驅體或副產物。
5)藉由向反應腔室供應臭氧氣體(O3)形成摻雜薄膜。
6)向反應腔室供應Ar氣體以排出未反應的物質或副產物。
7)使用Ar作為載氣，在室溫下將介電膜前驅體(HAC)供應至反應腔室，且將介電膜前驅體吸附至基板上。
8)向反應腔室中供應Ar氣體以排出未吸附的介電膜前驅體或副產物。
9)藉由向反應腔室供應臭氧氣體(O3)形成介電膜。
10)向反應腔室供應Ar氣體以排出未反應的物質或副產物。
圖7為根據本發明之實施例1之薄膜的X射線繞射(XRD)結果。無論Si比如何，四方相(101)之比均大於單斜相之比，且表面保護材料所吸附之SiO2的沉積速率降低。因此，推測包括精細的Si濃度以對結晶性改良有影響。結果，當實施相同的Si濃度時，在不增加HfO2基質THK之情況下促進了四方相的形成。
圖8為展現根據本發明之實施例1的薄膜之碳之次級離子質譜分析(SIMS)的圖，圖9為展現根據本發明之實施例1的薄膜之矽之次級離子質譜分析(SIMS)的圖。在碳雜質之情況下，其與HfO處於相似的位準，而在矽之情況下，與比較實例1相比，其減小超過2倍，且峰偏差亦減小。藉由使用表面保護材料，在形成氧化矽膜時，可降低氧化矽膜之沉積速率。此外，在隨後沉積之介電膜中精細控制Si濃度及減小峰偏差係可能的，從而能夠實現所需組成的薄膜及均勻層的形成。
根據本發明，控制摻雜薄膜之低生長速率可容易地控制摻雜薄膜之厚度，且可獲得具有所需組成的介電膜。
此外，減輕了局部組成的不均勻性，從而獲得在介電膜中具有改良之結晶度及介電常數的介電膜。
已參考實施例詳細解釋了本發明，但可包括其他實施例。因此，以下申請專利範圍中描述之技術想法及範疇不限於實施例。
Claims (21)
- 一種使用一表面保護材料形成一薄膜之方法，該方法包含：將該表面保護材料供應至置放一基板之一腔室內部；沖洗該腔室之內部；將一具有矽原子的摻雜前驅體供應至該腔室之內部；沖洗該腔室之內部；將一第一反應物供應至該腔室之內部，以使得該第一反應物與該經吸附摻雜前驅體反應以形成一摻雜薄膜；將一介電膜前驅體供應至該腔室之內部，該介電膜前驅體為包括含有Ti、Zr及Hf之四價金屬中之至少一者的一化合物；沖洗該腔室之內部；及將一第二反應物供應至該腔室之內部，以使得該第二反應物與該經吸附介電膜前驅體反應以形成一介電膜；其中該第一反應物及該第二反應物係選自O3、O2、H2O、H2O2、N2O及NH3。
- 如請求項1之方法，其中該表面保護材料由以下化學式1表示：
- 如請求項1之方法，其中該表面保護材料由以下化學式2表示：
- 如請求項1之方法，其中該表面保護材料由以下化學式3表示：
- 如請求項1之方法，其中該表面保護材料由以下化學式4表示：
- 如請求項1之方法，其中該表面保護材料由以下化學式5表示：
- 如請求項1之方法，其中該表面保護材料由以下化學式6表示：
- 如請求項1之方法，其中該表面保護材料由以下化學式7表示：
- 如請求項1之方法，其中該表面保護材料由以下化學式8表示：
- 如請求項1之方法，其中該摻雜前驅體由以下化學式9表示：
- 如請求項10之方法，其中該摻雜前驅體由以下化學式10至 14中之任一者表示：
- 如請求項1之方法，其中該摻雜前驅體由以下化學式15表示：
- 如請求項12之方法，其中該摻雜前驅體由以下化學式16至21中之任一者表示：
- 如請求項1之方法，其中該摻雜前驅體由以下化學式22表示：
- 如請求項14之方法，其中該摻雜前驅體由以下化學式23表 示：
- 如請求項1之方法，其中該摻雜前驅體由以下化學式24表示：
- 如請求項16之方法，其中該摻雜前驅體由以下化學式25至27中之任一者表示：
- 如請求項1之方法，其中該摻雜前驅體由以下化學式28表示：
- 如請求項18之方法，其中該摻雜前驅體由以下化學式29表示：<化學式29>
- 如請求項1之方法，其中該表面保護材料為原甲酸三甲酯。
- 如請求項1之方法，其中該摻雜前驅體為二異丙基胺基矽烷，且該介電膜前驅體為參(二甲胺基)環戊二烯基鉿(IV)。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020200129773A KR102199999B1 (ko) | 2020-10-08 | 2020-10-08 | 표면 보호 물질을 이용한 박막 형성 방법 |
| KR10-2020-0129773 | 2020-10-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW202219311A TW202219311A (zh) | 2022-05-16 |
| TWI841867B true TWI841867B (zh) | 2024-05-11 |
Family
ID=74127652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW110137391A TWI841867B (zh) | 2020-10-08 | 2021-10-07 | 使用保護材料來沉積薄膜的方法 |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20220112600A1 (zh) |
| JP (1) | JP2022062709A (zh) |
| KR (1) | KR102199999B1 (zh) |
| CN (1) | CN114293175B (zh) |
| TW (1) | TWI841867B (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023195656A1 (ko) * | 2022-04-05 | 2023-10-12 | 솔브레인 주식회사 | 박막 형성 방법, 이로부터 제조된 반도체 기판 및 반도체 소자 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1934287A (zh) * | 2004-05-12 | 2007-03-21 | 应用材料股份有限公司 | 用于高介电常数含铪介电材料的原子层沉积的装置和方法 |
| CN103510074A (zh) * | 2013-10-25 | 2014-01-15 | 南京大学 | 基于ald技术的复合无机-有机杂化物薄膜的制备方法 |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7229405B2 (en) | 2002-11-15 | 2007-06-12 | Paracor Medical, Inc. | Cardiac harness delivery device and method of use |
| KR20040100766A (ko) * | 2003-05-24 | 2004-12-02 | 삼성전자주식회사 | 원자층 증착법을 이용한 복합 유전막의 연속 형성방법 및이를 이용한 캐패시터의 제조방법 |
| KR100555543B1 (ko) * | 2003-06-24 | 2006-03-03 | 삼성전자주식회사 | 원자층 증착법에 의한 고유전막 형성 방법 및 그고유전막을 갖는 커패시터의 제조 방법 |
| TWI426602B (zh) * | 2007-05-07 | 2014-02-11 | Sony Corp | A solid-state image pickup apparatus, a manufacturing method thereof, and an image pickup apparatus |
| US8159008B2 (en) * | 2009-09-18 | 2012-04-17 | International Business Machines Corporation | Method of fabricating a trench-generated transistor structure |
| JP2014053371A (ja) * | 2012-09-05 | 2014-03-20 | Toshiba Corp | 不揮発性半導体記憶装置 |
| JP6092676B2 (ja) * | 2013-03-25 | 2017-03-08 | 株式会社日立国際電気 | 半導体装置の製造方法、基板処理装置及びプログラム |
| KR101785594B1 (ko) * | 2014-06-13 | 2017-10-17 | 주식회사 유진테크 머티리얼즈 | 성막용 전구체 조성물 및 이를 이용한 박막 형성 방법 |
| US10985014B2 (en) * | 2017-07-23 | 2021-04-20 | Applied Materials, Inc. | Methods for selective deposition on silicon-based dielectrics |
| KR102095710B1 (ko) * | 2019-11-05 | 2020-04-01 | 주식회사 유진테크 머티리얼즈 | 표면 보호 물질을 이용한 박막 형성 방법 |
| CN114867888A (zh) * | 2019-12-27 | 2022-08-05 | 弗萨姆材料美国有限责任公司 | 用于沉积膜的方法 |
-
2020
- 2020-10-08 KR KR1020200129773A patent/KR102199999B1/ko active IP Right Grant
-
2021
- 2021-10-07 US US17/496,439 patent/US20220112600A1/en not_active Abandoned
- 2021-10-07 TW TW110137391A patent/TWI841867B/zh active
- 2021-10-08 CN CN202111172039.8A patent/CN114293175B/zh active Active
- 2021-10-08 JP JP2021166344A patent/JP2022062709A/ja active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1934287A (zh) * | 2004-05-12 | 2007-03-21 | 应用材料股份有限公司 | 用于高介电常数含铪介电材料的原子层沉积的装置和方法 |
| CN103510074A (zh) * | 2013-10-25 | 2014-01-15 | 南京大学 | 基于ald技术的复合无机-有机杂化物薄膜的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20220112600A1 (en) | 2022-04-14 |
| CN114293175A (zh) | 2022-04-08 |
| CN114293175B (zh) | 2024-09-10 |
| KR102199999B1 (ko) | 2021-01-08 |
| JP2022062709A (ja) | 2022-04-20 |
| TW202219311A (zh) | 2022-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112470257B (zh) | 形成用于半导体器件的晶体学稳定的铁电铪锆基膜的方法 | |
| KR102095710B1 (ko) | 표면 보호 물질을 이용한 박막 형성 방법 | |
| US20060258078A1 (en) | Atomic layer deposition of high-k metal oxides | |
| US20060228888A1 (en) | Atomic layer deposition of high k metal silicates | |
| US20070252244A1 (en) | Methods of forming material over substrates | |
| US20110053383A1 (en) | High concentration water pulses for atomic layer deposition | |
| JP2010539709A (ja) | モノシクロペンタジエニルチタン系前駆体を用いる原子層成長によるチタン含有薄膜の作製方法 | |
| KR102333599B1 (ko) | 표면 보호 물질을 이용한 박막 형성 방법 | |
| JP2011521479A (ja) | 高ｋ誘電性膜およびチタン系前駆体を用いるその製造方法 | |
| TWI841867B (zh) | 使用保護材料來沉積薄膜的方法 | |
| TW202231901A (zh) | 選擇性形成薄膜的方法 | |
| JP6705006B2 (ja) | 有機４族化合物を含む前駆体造成物及びそれを利用した薄膜形成方法 | |
| US11414434B2 (en) | Rare earth precursor, method of manufacturing same and method of forming thin film using same | |
| TWI798816B (zh) | 選擇性材料及使用選擇性材料之選擇性形成薄膜的方法 | |
| JP7485403B2 (ja) | 表面保護物質を用いた薄膜形成方法 | |
| CN114539295B (zh) | 稀土前驱体、制备其的方法和使用其形成薄膜的方法 | |
| US20220145461A1 (en) | Rare earth precursor, method of preparing the same, and method of forming thin film using the same | |
| KR100920402B1 (ko) | 저온 게이트 스택 | |
| US20100055321A1 (en) | Precursors for atomic layer deposition |