US20010005026A1 - Conductive thin film, a capacitor using the same and a method of manufacturing. - Google Patents
Conductive thin film, a capacitor using the same and a method of manufacturing. Download PDFInfo
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- US20010005026A1 US20010005026A1 US09/200,315 US20031598A US2001005026A1 US 20010005026 A1 US20010005026 A1 US 20010005026A1 US 20031598 A US20031598 A US 20031598A US 2001005026 A1 US2001005026 A1 US 2001005026A1
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- Prior art keywords
- etching
- electrode
- thin film
- noble metal
- capacitor
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- 239000003990 capacitor Substances 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000010409 thin film Substances 0.000 title claims description 41
- 239000000463 material Substances 0.000 claims abstract description 84
- 238000005530 etching Methods 0.000 claims abstract description 43
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 40
- 239000003989 dielectric material Substances 0.000 claims abstract description 38
- 238000001312 dry etching Methods 0.000 claims abstract description 33
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 23
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 18
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000059 patterning Methods 0.000 claims abstract description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 239000011737 fluorine Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 50
- 229910052751 metal Inorganic materials 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 31
- 239000004065 semiconductor Substances 0.000 claims description 27
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- 230000003647 oxidation Effects 0.000 claims description 18
- 229910052741 iridium Inorganic materials 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 239000010948 rhodium Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 3
- 238000007669 thermal treatment Methods 0.000 abstract description 16
- 238000009835 boiling Methods 0.000 description 21
- 150000002739 metals Chemical class 0.000 description 21
- 239000007789 gas Substances 0.000 description 18
- 229910052736 halogen Inorganic materials 0.000 description 17
- 150000002367 halogens Chemical class 0.000 description 17
- 230000008018 melting Effects 0.000 description 17
- 238000002844 melting Methods 0.000 description 17
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 10
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 230000009257 reactivity Effects 0.000 description 8
- 150000002366 halogen compounds Chemical class 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 229910019599 ReO2 Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 230000015654 memory Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910019571 Re2O7 Inorganic materials 0.000 description 3
- 229910019593 ReF6 Inorganic materials 0.000 description 3
- 229910019834 RhO2 Inorganic materials 0.000 description 3
- -1 RhO3 Chemical compound 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- KZYDBKYFEURFNC-UHFFFAOYSA-N dioxorhodium Chemical compound O=[Rh]=O KZYDBKYFEURFNC-UHFFFAOYSA-N 0.000 description 3
- YUCDNKHFHNORTO-UHFFFAOYSA-H rhenium hexafluoride Chemical compound F[Re](F)(F)(F)(F)F YUCDNKHFHNORTO-UHFFFAOYSA-H 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 2
- 229910019020 PtO2 Inorganic materials 0.000 description 2
- 229910002785 ReO3 Inorganic materials 0.000 description 2
- 229910021636 Rhenium(IV) chloride Inorganic materials 0.000 description 2
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- XSXHWVKGUXMUQE-UHFFFAOYSA-N osmium dioxide Inorganic materials O=[Os]=O XSXHWVKGUXMUQE-UHFFFAOYSA-N 0.000 description 2
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- XZQYTGKSBZGQMO-UHFFFAOYSA-I rhenium pentachloride Chemical compound Cl[Re](Cl)(Cl)(Cl)Cl XZQYTGKSBZGQMO-UHFFFAOYSA-I 0.000 description 2
- YSZJKUDBYALHQE-UHFFFAOYSA-N rhenium trioxide Chemical compound O=[Re](=O)=O YSZJKUDBYALHQE-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- 229910003767 Gold(III) bromide Inorganic materials 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910021605 Palladium(II) bromide Inorganic materials 0.000 description 1
- 229910021606 Palladium(II) iodide Inorganic materials 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 229910018944 PtBr2 Inorganic materials 0.000 description 1
- 229910019032 PtCl2 Inorganic materials 0.000 description 1
- 229910019029 PtCl4 Inorganic materials 0.000 description 1
- 229910019603 Rh2O3 Inorganic materials 0.000 description 1
- 229910021634 Rhenium(III) chloride Inorganic materials 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021611 Silver subfluoride Inorganic materials 0.000 description 1
- KWVVTSALYXIJSS-UHFFFAOYSA-L Silver(II) fluoride Inorganic materials [F-].[F-].[Ag+2] KWVVTSALYXIJSS-UHFFFAOYSA-L 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- WGKMWBIFNQLOKM-UHFFFAOYSA-N [O].[Cl] Chemical compound [O].[Cl] WGKMWBIFNQLOKM-UHFFFAOYSA-N 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- HNNUTDROYPGBMR-UHFFFAOYSA-L palladium(ii) iodide Chemical compound [Pd+2].[I-].[I-] HNNUTDROYPGBMR-UHFFFAOYSA-L 0.000 description 1
- KGRJUMGAEQQVFK-UHFFFAOYSA-L platinum(2+);dibromide Chemical compound Br[Pt]Br KGRJUMGAEQQVFK-UHFFFAOYSA-L 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000002577 pseudohalo group Chemical group 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- LOIHSHVELSAXQN-UHFFFAOYSA-K trirhenium nonachloride Chemical compound Cl[Re](Cl)Cl LOIHSHVELSAXQN-UHFFFAOYSA-K 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
- H01L28/40—Capacitors
- H01L28/60—Electrodes
- H01L28/82—Electrodes with an enlarged surface, e.g. formed by texturisation
- H01L28/90—Electrodes with an enlarged surface, e.g. formed by texturisation having vertical extensions
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F4/00—Processes for removing metallic material from surfaces, not provided for in group C23F1/00 or C23F3/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
- H01L28/40—Capacitors
- H01L28/60—Electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/86—Types of semiconductor device ; Multistep manufacturing processes therefor controllable only by variation of the electric current supplied, or only the electric potential applied, to one or more of the electrodes carrying the current to be rectified, amplified, oscillated or switched
- H01L29/92—Capacitors having potential barriers
- H01L29/94—Metal-insulator-semiconductors, e.g. MOS
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
- H01L28/40—Capacitors
- H01L28/55—Capacitors with a dielectric comprising a perovskite structure material
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10B—ELECTRONIC MEMORY DEVICES
- H10B12/00—Dynamic random access memory [DRAM] devices
- H10B12/01—Manufacture or treatment
- H10B12/02—Manufacture or treatment for one transistor one-capacitor [1T-1C] memory cells
- H10B12/03—Making the capacitor or connections thereto
Definitions
- This invention relates to a conductive thin film, a capacitor using ferroelectric materials, high dielectric materials and a method of manufacturing thereof, more specifically the conductive thin film to be easily patterned by etching, the capacitor having electrode materials to be easily patterned by etching while easily forming layers with ferroelectric materials or high dielectric materials, and a method of manufacturing such capacitor.
- Ferroelectric materials such as PZT (Pb(Zr, Ti) O 3 ) or SBT (SrBi 2 Ta 2 O 9 ) are used to manufacture capacitors that configure ferroelectric memories.
- dielectric materials such as BST ((Ba, Sr) TiO 3 ) and the like having a high dielectric constant in permanent dielectric substances are used to manufacture capacitors that configure dynamic random access memories (DRAMs). Annealing in an oxidation atmosphere at a range of 650 to 850° C. is required to crystalize these dielectric materials after forming layers with the materials. Further, matching in lattice constant with that of adjacent materials composing electrodes is required in order to crystalize a layer(s) formed with the ferroelectric materials.
- either of platinum (Pt), iridium (Ir) or an alloy of these metals having a stability in a high temperature as well as having similar lattice constant to the ferroelectric materials is used for configuring an electrode of the capacitors in above.
- oxides of noble metals such as IrO 2 , RuO 2 , RhO 2 , RhO 3 , PtO 2 , OsO 2 and the like are used for the electrode by itself or as part of a multi-layer composed with any of above-mentioned metals because of their conductivities.
- etching In order to carrying out etching, a method called sputtering in which the metals(s) are physically removed such as with ion milling using an inactive gas (Ar or the like) by emitting ions need to be carried out.
- an inactive gas Ar or the like
- the molecular adhere on surfaces to be etched of the metal layer 22 as well as both sides of the mask 23 as burrs 22 a (side walls) as shown in FIG. 2( b ).
- the burrs 22 a thus adhere can not be removed by reaction because the burrs 22 a are just composed of fine grains of platinum, iridium or the alloy of these metals.
- the side walls 22 a remain as they are even when the mask 23 (photo resist layer) is completely removed as shown in FIG. 2( c ). Consequently, this etching method can not be applied to the parts where requiring a fine work.
- the drawback is observed not only the noble metals themselves such as Pt. Ir, but also observed when oxides of the noble metals having conductivity such as one of IrO 2 , RuO 2 is used.
- a capacitor comprises a dielectric material composed by using at least one of a ferroelectric material and a high-dielectric material, and an electrode composed by using a material containing a noble metal, the electrode being formed on at least one side of the dielectric material, and wherein the material of the electrode contains rhenium (Re).
- the noble metal is defined as metals having stable characteristics in thermally and chemically, as well as having excellent electric conductivities, including gold (Au), platinum (Pt), iridium (Ir), osmium (Os), silver (Ag), palladium (Pd), rhodium (Rh) and ruthenium (Ru).
- the capacitor means not only a capacitor holding a ferroelectric layer between metal layers disposed therein, but also means semiconductors having an FET (field effect transistor) structure including a capacitor, in other words the semiconductor device having an MFS structure or similar structure in which both a ferroelectric layer and a gate electrode are formed in that order on a channel region located in a semiconductor substrate.
- FET field effect transistor
- Re may be liberated at a relatively low temperature by combining with fluorine and/or chlorine and so on. Therefore, Pt and/or Ir existed adjacent to the liberated Re may also be liberated easily when Re existing in crystalline structures of Pt and/or Ir are liberated. In this way, reactive etching, not physical etching can be performed to noble metals.
- the material containing a noble metal can be Pt and/or Ir, may also one oxide of a metal selected from a group of osmium (Os), iridium (Ir), platinum (Pt), ruthenium (Ru) and rhodium (Rh).
- the electrode has a multi-layered structure made of a conductive material, and at least one of the layers forming the multi-layered structure contains the material containing a noble metal, and the one layer may contains rhenium (Re).
- a semiconductor device including a capacitor structure at least comprises a semiconductor layer, a dielectric material composed by using at least one of a ferroelectric material and a high-dielectric material located on the semiconductor layer, and an electrode formed on the dielectric material, wherein a material containing a noble metal adding rhenium (Re) is used for a material of the thin film.
- a capacitor structure at least comprises a semiconductor layer, a dielectric material composed by using at least one of a ferroelectric material and a high-dielectric material located on the semiconductor layer, and an electrode formed on the dielectric material, wherein a material containing a noble metal adding rhenium (Re) is used for a material of the thin film.
- Re noble metal adding rhenium
- a method of manufacturing a capacitor comprises the steps of forming an electrode composed by using a material containing a noble metal at least one side of a dielectric material composed by using at least one of a ferroelectric material and a high-dielectric material, and performing a patterning of the electrode by etching, wherein rhenium (Re) is added to the material of the thin film, and wherein the etching is in dry-etching by introducing either of fluorine gas or chlorine gas.
- etching it is preferable to carry out etching with supplying the supply source for causing oxidation when dry-etching is carried out by introducing the chlorine gas. Because, Re can be liberated more easily as an oxygen chlorine (ReClO 3 , ReCl 4 O) as a result of sufficient supply of oxygen.
- a thin film having a certain conductivity the thin film being composed by using a material containing a noble metal, wherein the material contains Re.
- a semiconductor device comprises a semiconductor substrate, and a conductive thin film formed one of directly and indirectly on the substrate, wherein a material containing a noble metal adding rhenium (Re) is used for a material of the thin film.
- a material containing a noble metal adding rhenium (Re) is used for a material of the thin film.
- a method of manufacturing a semiconductor device comprises the steps of forming a conductive thin film on a semiconductor substrate one of directly and indirectly, performing a patterning of the conductive thin film by etching, wherein a material of the thin film is made by using a material containing a noble metal adding rhenium (Re), and wherein the etching is in dry-etching by introducing fluorine gas.
- a method of manufacturing a semiconductor device comprises the steps of forming a conductive thin film on a semiconductor substrate one of directly and indirectly, and performing a patterning of the conductive thin film by etching, wherein a material of the thin film is made by using a material containing a noble metal adding rhenium (Re), and wherein the etching is in dry-etching by introducing chlorine gas.
- FIG. 1( a ) is a cross sectional view illustrating structure of a capacitor composed in accordance with an embodiment of the present invention.
- FIG. 1( b ) is a cross sectional view illustrating structure of a capacitor composed in accordance with another embodiment of the present invention.
- FIG. 2( a ) is a sectional view illustrating the electrode for describing the drawbacks associated with the prior art materials.
- FIG. 2( b ) is another sectional view illustrating the electrode for describing the drawbacks associated with the prior art materials.
- FIG. 2( c ) is far another sectional view illustrating the electrode for describing the drawbacks associated with the prior art materials
- the capacitor is generally structured by forming each of a lower electrode 1 on a semiconductor substrate 10 through an insulation layer 4 and the like, a dielectric layer 2 made of dielectric material(s) located on the lower electrode 1 , and an upper electrode layer 3 positioned above the dielectric layer 2 , and then carrying out patterning to a part of the layers as shown in FIG. 1( a ).
- the patterning can be carried out in several different ways such as carrying out to the lower electrode 1 , the dielectric layer 2 and the upper electrode layer 3 simultaneously, or carrying out only to the lower electrode 1 and then both the dielectric layer 2 and the upper electrode layer 3 simultaneously, or carrying out all the layers independently.
- capacitors such as a ferroelectric memory FET (field effect transistor) having a structure so called MFIS structure and another structure called MFS structure.
- the capacitor having the MFIS structure comprises a ferroelectric layer 6 made of ferroelectric material(s) positioned on the semiconductor substrate 10 through a gate oxidation layer 5 , and a gate electrode 7 formed on the ferroelectric layer 6 as depicted in FIG. 1( b ).
- the capacitor having the MFS structure is fabricated by forming the ferroelectric layer directly on the semiconductor layer.
- Both the MFIS structure and the MFS structure can also be defined as a semiconductor device including a capacitor structure.
- noble metals such as Pt and/or iridium or oxides of noble metals such as IrO 2 , RuO 2 and the like are used for forming the electrode.
- an electrode made of Pt and/or Ir including Re may be formed by carrying out sputtering using a target made of an alloy of Pt and Re, or a target made of an alloy of Ir and Re or the like, or by carrying out sputtering using both the target made of the Pt or the like, and the target made of Re while rotating both the targets.
- the ratio of Re to the whole material(s) may be determined by the numbers of targets made of Re in all the targets.
- An electrode made of oxides of noble metal including Re can be formed by carrying out sputtering using a target made of oxides of an alloy including Re, or by carrying out sputtering in an oxidation atmosphere using the target made of the alloy including Re, or using both the target made of Ir and the target made of Re when Re is added to IrO 2 .
- the materials for forming the electrode need to withstand a high temperature thermal treatment carried out in an oxidation atmosphere. Only a certain kinds of metals withstand against the high temperature thermal treatment in an oxidation atmosphere.
- Table 1 shows reactions of several metals which are know as (noble) metals relatively hard to oxidize in the high temperature thermal treatment carried out in the oxidation atmosphere. As shown in the table 1, Ir, Pt, Au, Ag, Pd and Re are recognized as metals withstand in the high temperature thermal treatment in the oxidation atmosphere for crystallizing the ferroelectrics.
- RuO 2 VOLATALIZD WITH FORMATION OF RuO 4 Rh 600° C. Rh 2 O 3 GRADUALLY OXIDIZED. THEN DECOM- POSED AT A HIGHER TEMPERATURE Pd >820° C. PdO DECOMPOSED AT A HIGHER TEMPERATURE Ag NONE Ag 2 O 2 IS FORMED IN AN O 3 ATOMOSPHERE Re >1000° C. Re 2 O 7 OXIDIZED ON SURFACE AT ROOM TEMPERATURE IN AMBIENT AIR
- reactive dry-etching can be carried out as a result of accelerating the reaction between Ir and/or Pt and fluorides by utilizing a high reactivity between Re and fluoride gas.
- the reactivity of Ir and/or Pt with the fluoride gas is increased by replacing a part of the electrode made of Ir and/or Pt with Re while observing no adhesion and formation of no side walls (burrs adheres on the surfaces to be etched) because the compositions formed by the reaction such as Pt x Re 1-x F 6 and/or Ir x Re 1-x F 6 can be vaporized as a result of their low boiling point.
- Oxide gas such as oxygen gas, ozone, NO x can be used as a supply source for causing oxidation, and these should be added to the etchant.
- the atmosphere with the presence of oxygen can be created by utilizing a mask made of photo resist or SiO 2 both containing oxygen without supply of oxide gas.
- table 3 shows conductive metal oxides having enough conductivity capable of using for the electrode of the ferroelectric capacitor described earlier.
- the metal oxides which withstand the thermal treatment for the crystallization are IrO 2 , RuO 2 , RhO 2 , RhO 3 and ReO 2 .
- the required factors of the conductive metal oxides used in the dry-etching using the halogens are both of reacting with the halogens at a low temperatures and having a low melting point and a low boiling point of halogen compound formed during the etching.
- Both Re and Ru react with fluoride (F) at a low temperature as far as concerning the reactivity to the halogens.
- F fluoride
- RU could take different valence number, ions of Ru except for tetra-valent ions are generated at a high temperature. The ions thus generated cause degradation of the capacitor characteristics because the ions react with the ferroelectric materials as a result of high reactivity thereof.
- ReO 3 having hexa-valent of Re oxides is decomposed at approximately 400° C. and becomes to ReO 2 .
- Re oxide having tetra-valent has been kept stable until generation of Re 2 O 7 as a result of decomposition of ReO 2 started at approximately 1,000° C.
- Table 4 shows the melting points and the boiling points of compounds generated as a result of reaction to the halogen, the compounds shown in the table are not listed on the table 2.
- TABLE 4 MELTING POINTS AND BOILING POINTS OF HALOGEN COMPOUNDS OF MAJOR METALS MELTING BOILING MELTING BOILING ELEMENTS POINTS (° C.) POINTS (° C.) ELEMENTS POINTS (° C.) POINTS (° C.) RhF 3 >600 (SUBLI- OsF 4 230 MATED) RhF 5 95.5 OsF 5 70 225.7 Rh F 6 70 DECOM- OsF 6 32.1 45.9 POSED RhCl 3 450 (DECOM- OsCl 3 350 (SUBLI- 450 (DECOM- POSED) MATED) POSED) RhBrs DECOM- OsCl 4 450 POSED OsBr 4 350 (DECOM- POSED) OsF 2 O 3 171
- both the melting point and the boiling point of compounds including Rh are too high, or Rh is in decomposition, and hexa-fluoride of Os can be vaporized during the dry-etching carried out under a low pressure because the boiling point of hexa-fluoride of Os is relatively low.
- it is hard to carry out reactive dry-etching because reactivity of Os with the fluoride gas is quite low and Os forms fluorides only at a high temperature atmosphere. Therefore, the conductive oxides described above capable of using for the dry-etching are formed by replacing a part of the oxidized electrode made of IrO 2 and the like with Re similar to the metals described earlier.
- the reactivity of the oxidized electrode can be increased by utilizing a high reactivity of Re to the fluoride gas. Further, substances formed by the reaction such as Ir x Re 1-x F 6 and the like can be vaporized at a low temperature as a result of their low boiling point. Consequently, no adhesion and the formation of no side walls are observed. Further, the oxygen chloride of Re can be vaporized under a low pressure similar to the embodiment described above, so that the dry-etching can be carried out by using the chlorine gas. No introduction of oxide gas is needed to carry out the etching because the electrode is composed of materials containing oxides.
- reactive dry-etching not allowing any adherence on both sides of the mask and the like can be carried out by replacing a part of the electrode with Re having an excellent anti-acid characteristic when the oxide of the noble metals having conductivity such as IrO 2 is used for the electrode.
- Re itself is liberated as a halogenoid by carrying out dry-etching using halogen gas as an etchant because Re existing in the electrode may be vaporized when it reacts with halogen.
- Halogen combines to the places where no Re is existed as a result of the lack of Re caused by the evaporation. Then, Pt and/or Ir bonded with halogen liberates therefrom.
- Reactive dry-etching can be carried out by repeating a series of process described hereinabove. Although, a certain amount of Re added to the electrode is acceptable because of its heat resistance, the amount of Re is preferably not too much in consideration of alignment to the crystal of ferroelectrics.
- Pt and/or Ir has better probability of aligning to the crystalline of ferroelectrics and the like than that of Re.
- the more Re is preferable in an ordinary active etching only a small amount of Re enables the reactive dry-etching since Re tend to cause a chain reaction as described earlier.
- the amount of Re added to the electrode is preferably at a range of 5 to 20 atomic percentage in consideration of above-mentioned conditions.
- the electrode holding either of ferroelectric material(s) or high-dielectric material(s) in its inside is made of Pt and/or Ir, or the conductive oxides containing Re, so that, reactive etching, not physical etching can be performed to noble metals such as Pr and/or Ir by carrying out dry-etching using either fluoride gas or chlorine gas as an etchant. Consequently, the noble metals thus removed not adhere on the surfaces to be etched and adjacent thereof, so that, a fine work can be performed. Moreover, no degradation of Re is observed when a high temperature thermal treatment for crystallizing dielectric materials is carried out because Re has enough heat resistance similar to that of Pt and Ir. In this way, a high-performance capacitor composed of ferroelectrics and/or high dielectrics can be realized.
- the conductive thin film is used as a part of the electrode of the capacitor made of ferroelectrics and/or high dielectrics in the embodiment described above, the conductive thin film according to the present invention can also be used as other electrodes commonly used.
- the conductive thin film according to the present invention can also be used as a wiring as well as a barrier metal.
- the conductive thin film can be used for a case in which a high temperature thermal treatment is carried out as a post-treatment and a case in which a fine work to which is required. This is because the conductive thin film according to the present invention has enough heat resistance as well as capable of carrying out a fine work thereto.
- the material(s) of the part(s) formed adjacent to the conductive thin film is not limited to specific kind(s) except when the thin film is used as a part of the electrode made of ferroelectrics and/or high dielectrics of the capacitor.
- Metals, metal oxides, silicon, poly-silicon, silicon-oxide, silicon-nitride, silicon-oxide-nitride and the like can be used for the materials of the parts formed adjacent to the conductive thin film.
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Abstract
It is an object of the present invention to provide a capacitor and a method of manufacturing the same having an electrode made of material(s) capable of carrying a fine work through etching while withstanding a high temperature thermal treatment for crystallizing dielectric materials such as ferroelectric materials and the like. The capacitor comprises a dielectric material composed by using at least a ferroelectric material or a high-dielectric material, and an electrode composed by using a material containing a noble metal, the electrode being formed on at least one side of the dielectric material, and the material of the electrode contains rhenium (Re). The capacitor is fabricated by patterning the material of the electrode contains rhenium (Re) using dry-etching method by introducing either of fluorine gas or chlorine gas.
Description
- The entire disclosure of Japanese Patent Application No. Hei 9-326850 filed on Nov. 28, 1997 including specification, claims, drawings and summary is incorporated herein by reference in its entirety.
- 1. Field of the Invention
- This invention relates to a conductive thin film, a capacitor using ferroelectric materials, high dielectric materials and a method of manufacturing thereof, more specifically the conductive thin film to be easily patterned by etching, the capacitor having electrode materials to be easily patterned by etching while easily forming layers with ferroelectric materials or high dielectric materials, and a method of manufacturing such capacitor.
- 2. Description of the Related Art
- Ferroelectric materials such as PZT (Pb(Zr, Ti) O3) or SBT (SrBi2Ta2O9) are used to manufacture capacitors that configure ferroelectric memories. Also, dielectric materials such as BST ((Ba, Sr) TiO3) and the like having a high dielectric constant in permanent dielectric substances are used to manufacture capacitors that configure dynamic random access memories (DRAMs). Annealing in an oxidation atmosphere at a range of 650 to 850° C. is required to crystalize these dielectric materials after forming layers with the materials. Further, matching in lattice constant with that of adjacent materials composing electrodes is required in order to crystalize a layer(s) formed with the ferroelectric materials. In consideration of above-mentioned requirements, either of platinum (Pt), iridium (Ir) or an alloy of these metals having a stability in a high temperature as well as having similar lattice constant to the ferroelectric materials is used for configuring an electrode of the capacitors in above. Also, oxides of noble metals such as IrO2, RuO2, RhO2, RhO3, PtO2, OsO2 and the like are used for the electrode by itself or as part of a multi-layer composed with any of above-mentioned metals because of their conductivities.
- As described above, not much oxidation disturbing crystallization and/or conductivity during the annealing for the crystallization is caused by using platinum (Pt), iridium (Ir) or an alloy of these for electrode as electrode materials, so that the any of these is suitable for the electrode of the capacitors in above. The electrode made of these materials, however, is formed by carrying out pattering with etching using a
mask 23, after disposing ametal layer 22 so as to cover the surface of asubstrate 21 as shown in FIG. 2(a). The noble metals Pt and/or iridium used for the electrode are well-stabilized in a chemical stand-point, so that no chemical etching can be carried out on these metals. In order to carrying out etching, a method called sputtering in which the metals(s) are physically removed such as with ion milling using an inactive gas (Ar or the like) by emitting ions need to be carried out. By carrying out such etching, molecular of the metal(s) to be etched, that of the metal(s) used for the electrodes themselves are flown out from the metal(s). The molecular adhere on surfaces to be etched of themetal layer 22 as well as both sides of themask 23 as burrs 22 a (side walls) as shown in FIG. 2(b). The burrs 22 a thus adhere can not be removed by reaction because the burrs 22 a are just composed of fine grains of platinum, iridium or the alloy of these metals. The side walls 22 a remain as they are even when the mask 23 (photo resist layer) is completely removed as shown in FIG. 2(c). Consequently, this etching method can not be applied to the parts where requiring a fine work. The drawback is observed not only the noble metals themselves such as Pt. Ir, but also observed when oxides of the noble metals having conductivity such as one of IrO2, RuO2 is used. - Although, further improvements in etching so as to finish the electrode without forming side walls are required as a result of the recent trend in high-integration of semiconductor memory and the like, the conventional etching for making electrodes disturbs the improvements. Degradation of the characteristics of capacitors is arisen when the physical etching is carried out as a result of causing damage(s) on the surface to be etched of dielectric substances.
- It is an object of the present invention to overcome the above mentioned drawbacks on the capacitors, and to provide a capacitor and a method of manufacturing the same having an electrode made of material(s) capable of carrying a fine work through etching while withstanding a high temperature thermal treatment for crystallizing dielectric materials such as ferroelectric materials and the like. It is another object of the present invention to provide a conductive thin film and a method of manufacturing a semiconductor device having the thin film made of material(s) capable of carrying a fine work through etching while withstanding a high temperature thermal treatment.
- In accordance with characteristics of the present invention, there is provided a capacitor comprises a dielectric material composed by using at least one of a ferroelectric material and a high-dielectric material, and an electrode composed by using a material containing a noble metal, the electrode being formed on at least one side of the dielectric material, and wherein the material of the electrode contains rhenium (Re).
- Here, the noble metal is defined as metals having stable characteristics in thermally and chemically, as well as having excellent electric conductivities, including gold (Au), platinum (Pt), iridium (Ir), osmium (Os), silver (Ag), palladium (Pd), rhodium (Rh) and ruthenium (Ru).
- Moreover, the capacitor means not only a capacitor holding a ferroelectric layer between metal layers disposed therein, but also means semiconductors having an FET (field effect transistor) structure including a capacitor, in other words the semiconductor device having an MFS structure or similar structure in which both a ferroelectric layer and a gate electrode are formed in that order on a channel region located in a semiconductor substrate.
- By constructing the capacitor in that structure, Re may be liberated at a relatively low temperature by combining with fluorine and/or chlorine and so on. Therefore, Pt and/or Ir existed adjacent to the liberated Re may also be liberated easily when Re existing in crystalline structures of Pt and/or Ir are liberated. In this way, reactive etching, not physical etching can be performed to noble metals.
- The material containing a noble metal can be Pt and/or Ir, may also one oxide of a metal selected from a group of osmium (Os), iridium (Ir), platinum (Pt), ruthenium (Ru) and rhodium (Rh). Further, the electrode has a multi-layered structure made of a conductive material, and at least one of the layers forming the multi-layered structure contains the material containing a noble metal, and the one layer may contains rhenium (Re).
- In accordance with characteristics of the present invention, there is provided a semiconductor device including a capacitor structure at least comprises a semiconductor layer, a dielectric material composed by using at least one of a ferroelectric material and a high-dielectric material located on the semiconductor layer, and an electrode formed on the dielectric material, wherein a material containing a noble metal adding rhenium (Re) is used for a material of the thin film.
- Also, in accordance with characteristics of the present invention, there is provided a method of manufacturing a capacitor comprises the steps of forming an electrode composed by using a material containing a noble metal at least one side of a dielectric material composed by using at least one of a ferroelectric material and a high-dielectric material, and performing a patterning of the electrode by etching, wherein rhenium (Re) is added to the material of the thin film, and wherein the etching is in dry-etching by introducing either of fluorine gas or chlorine gas.
- It is preferable to carry out etching with supplying the supply source for causing oxidation when dry-etching is carried out by introducing the chlorine gas. Because, Re can be liberated more easily as an oxygen chlorine (ReClO3, ReCl4O) as a result of sufficient supply of oxygen.
- Further, in accordance with characteristics of the present invention, there is provided a thin film having a certain conductivity, the thin film being composed by using a material containing a noble metal, wherein the material contains Re.
- In accordance with characteristics of the present invention, there is provided a semiconductor device comprises a semiconductor substrate, and a conductive thin film formed one of directly and indirectly on the substrate, wherein a material containing a noble metal adding rhenium (Re) is used for a material of the thin film.
- Also, in accordance with characteristics of the present invention, there is provided a method of manufacturing a semiconductor device comprises the steps of forming a conductive thin film on a semiconductor substrate one of directly and indirectly, performing a patterning of the conductive thin film by etching, wherein a material of the thin film is made by using a material containing a noble metal adding rhenium (Re), and wherein the etching is in dry-etching by introducing fluorine gas.
- Further, in accordance with characteristics of the present invention, there is provided a method of manufacturing a semiconductor device comprises the steps of forming a conductive thin film on a semiconductor substrate one of directly and indirectly, and performing a patterning of the conductive thin film by etching, wherein a material of the thin film is made by using a material containing a noble metal adding rhenium (Re), and wherein the etching is in dry-etching by introducing chlorine gas.
- While the novel features of the invention are set forth in a general fashion, both as to organization and content, the invention will be better understood and appreciated, along with other objects and features thereof from the following detailed description taken in conjunction with the drawings.
- FIG. 1(a) is a cross sectional view illustrating structure of a capacitor composed in accordance with an embodiment of the present invention.
- FIG. 1(b) is a cross sectional view illustrating structure of a capacitor composed in accordance with another embodiment of the present invention.
- FIG. 2(a) is a sectional view illustrating the electrode for describing the drawbacks associated with the prior art materials.
- FIG. 2(b) is another sectional view illustrating the electrode for describing the drawbacks associated with the prior art materials.
- FIG. 2(c) is far another sectional view illustrating the electrode for describing the drawbacks associated with the prior art materials
- An embodiment of a conductive thin film according to the present invention will be described hereunder in the case of using the thin film to a capacitor having one of ferroelectric and high dielectric constant materials.
- Thorough studies and researches are conducted to investigate a material which satisfies no adhesion of the fine grains of the etched-material on that surfaces when patterning is carried out to the electrode of the capacitor having one of the ferroelectric and the high dielectric constant materials while no adverse effect is given to crystalize dielectrics such as ferroelectric materials and the like. As a result of the studies and the researches, the inventor has found out that Re may easily be evaporated at a relatively low temperature as a result of a chemical reaction caused with one of fluorine gas and chlorine gas while maintaining its stability without causing oxidization at a high temperature. And the inventor further found out that an alloy of Re, Pt and/or Ir both have been used has better characteristics in etching without damaging crystallinity of the dielectric materials.
- The capacitor is generally structured by forming each of a
lower electrode 1 on asemiconductor substrate 10 through an insulation layer 4 and the like, adielectric layer 2 made of dielectric material(s) located on thelower electrode 1, and an upper electrode layer 3 positioned above thedielectric layer 2, and then carrying out patterning to a part of the layers as shown in FIG. 1(a). The patterning can be carried out in several different ways such as carrying out to thelower electrode 1, thedielectric layer 2 and the upper electrode layer 3 simultaneously, or carrying out only to thelower electrode 1 and then both thedielectric layer 2 and the upper electrode layer 3 simultaneously, or carrying out all the layers independently. Further, there are another type of capacitor such as a ferroelectric memory FET (field effect transistor) having a structure so called MFIS structure and another structure called MFS structure. The capacitor having the MFIS structure comprises a ferroelectric layer 6 made of ferroelectric material(s) positioned on thesemiconductor substrate 10 through a gate oxidation layer 5, and a gate electrode 7 formed on the ferroelectric layer 6 as depicted in FIG. 1(b). The capacitor having the MFS structure is fabricated by forming the ferroelectric layer directly on the semiconductor layer. Both the MFIS structure and the MFS structure can also be defined as a semiconductor device including a capacitor structure. - Thermal treatment in an oxidation atmosphere at a range of 650 to 850° C. in 1 to 60 minutes is carried out after forming the layers when the ferroelectric used for the ferroelectric memory FETs or the high dielectric material(s) used for the DRAMs such as PZT (Pb(Zr, Ti) O3 or SBT (SrBi2Ta2O9) are used for the
ferroelectric layers 2, 6. Occurrence of degradation of electric characteristics and damage of crystallinity is observed when theelectrodes 1, 3 and 7 are oxidized during the thermal treatment because nonconductive oxides are formed on the surfaces thereof. In order to avoid such phenomena, the material unchanging its properties after carrying out the thermal treatment is required, so that noble metals such as Pt and/or iridium or oxides of noble metals such as IrO2, RuO2 and the like are used for forming the electrode. - The present invention is characterized in that Re is added to the electrode materials. For example, an electrode made of Pt and/or Ir including Re may be formed by carrying out sputtering using a target made of an alloy of Pt and Re, or a target made of an alloy of Ir and Re or the like, or by carrying out sputtering using both the target made of the Pt or the like, and the target made of Re while rotating both the targets. The ratio of Re to the whole material(s) may be determined by the numbers of targets made of Re in all the targets. An electrode made of oxides of noble metal including Re can be formed by carrying out sputtering using a target made of oxides of an alloy including Re, or by carrying out sputtering in an oxidation atmosphere using the target made of the alloy including Re, or using both the target made of Ir and the target made of Re when Re is added to IrO2.
- Next, the details of a conclusion that the addition of Re to the material(s) for forming the electrode including noble metals increases characteristics of the electrode as well as facilitate etching will be described hereunder. As described earlier, the materials for forming the electrode need to withstand a high temperature thermal treatment carried out in an oxidation atmosphere. Only a certain kinds of metals withstand against the high temperature thermal treatment in an oxidation atmosphere. Table 1 shows reactions of several metals which are know as (noble) metals relatively hard to oxidize in the high temperature thermal treatment carried out in the oxidation atmosphere. As shown in the table 1, Ir, Pt, Au, Ag, Pd and Re are recognized as metals withstand in the high temperature thermal treatment in the oxidation atmosphere for crystallizing the ferroelectrics.
TABLE 1 REACTIONS OF SEVERAL NOBLE METAS IN AN OXIDATION ATOMOSPHERE INITIAL TEMPERATURE OXIDE ELEMENTS OF OXIDATION FORMED REMARKS Os 200˜400° C. OsO4 MOST EASY ELEMENT TO BE OXIDIZED IN PLATINUM GROUP Ir >800° C. IrO2 VAPORIZED AT A TEMPERATURE GREATER THAN 1000° C. Pt NONE NOT OXDIZED IN AN OXIDATION ATOMOSPHERE Au NONE — NOT OXDIZED IN AN OXIDATION ATOMOSPHERE Ru >700° C. RuO2 VOLATALIZD WITH FORMATION OF RuO4 Rh 600° C. Rh2O3 GRADUALLY OXIDIZED. THEN DECOM- POSED AT A HIGHER TEMPERATURE Pd >820° C. PdO DECOMPOSED AT A HIGHER TEMPERATURE Ag NONE Ag2O2 IS FORMED IN AN O3 ATOMOSPHERE Re >1000° C. Re2O7 OXIDIZED ON SURFACE AT ROOM TEMPERATURE IN AMBIENT AIR - Next, a consideration is given to materials for carrying out dry-etching. As described earlier, the burrs (side walls) are remained as well as causing damage(s) on the surface to be etched of dielectric substances in the dry-etching carried out using inactive gas such as Ar and the like. In order to avoid such phenomena, dry-etching using either of halogen or halogen compound (both halogen and halogen compound are hereinafter referred to as halogens) will be described hereunder as an example. The required factors of the metals used in the dry-etching using the halogens are of reacting with the halogens at a low temperature, and having a low melting point and a low boiling point of halogen compound formed during the etching.
- Concerning the reaction of the metals with the halogens, most of the (noble) metals listed above which might withstand against the high temperature thermal treatment in the oxidation atmosphere react with the halogens only at a high temperature. Therefore, most of the metals listed above need to be etched physically because not much reaction proceeds during the etching than it should be at a low pressure. On the contrary, only Re reacts with fluoride (F) at a low temperature. In addition, dry-etching can not be carried out in the case that the resulting products can not be vaporized even when the metals react with the halogens. Table 2 shows the melting points and the boiling points of the halogen compound of the above-listed metals.
TABLE 2 MELTING POINTS AND BOILING POINTS OF HALOGEN COMPOUNDS OF MAJOR METALS MELTING BOILING MELTING ELEMENTS POINTS (° C.) POINTS (° C.) ELEMENTS POINTS (° C.) BOILING POINTS (° C.) PtF6 61.3 69.1 AuCl 170(DECOM- POSED) →AuCl3 PtCl2 581 (DECOM- AuCl3 200 (SUBLIMATED IN POSED) Cl2) PtCl4 370 (DECOM- AuBr 115 (DECOM- POSED) POSED) PtBr2 250 (DECOM- AuBr3 97.5 160 (DECOM- POSED) POSED) PtBr4 180 (DECOM- Ag2F 90 (DECOM- POSED) POSED) PtI2 325 (DECOM- AgF 435 1150 (DECOM- POSED) POSED) IrF3 250 (DECOM- AgF2 690 700 (DECOM- POSED) POSED) IrF5 104.5 AgCl 455 1550 IrF6 44.4 53 AgClO3 230 270 (DECOM- POSED) IrCl3 763 (DECOM- AgClO4 486 (DECOM- POSED) POSED) ReF4 124.5 795 AgBr 432 >1300 (DECOM- POSED) ReF6 18.7 33.8 PdF2 ReF7 48.3 73.7 PdCl2 678 >680 (DECOM- POSED) ReCl3 >550 PdBr2 ReCl5 220 PdI2 105 (DECOM- POSED) ReBr3 >500 ReCl4O 29.3 223 ReClO3 4.5 191 - As apparent from the table 2, most of the compounds either show high melting points and high boiling points or to be decomposed. The high melting points and high boiling points cause adhesion of unvaporized solid and/or liquid on both sides of the mask and adjacent thereof even when the metals react with the halogens during the etching. In the same way, the decomposition causes adhesion of decomposed noble metals on the both sides and so on. Both the melting point and the boiling points of the compound of ReF6 are remarkably low. Reactive etching may be expected during the etching because Re may easily reacts with fluorine gas as described earlier. No adhesion on the both sides of the mask and so on is observed because the compound ReF6 formed from Re through the etching is vaporized due to its low boiling point. Similarly, Vaporization of hexa-fluoride compound made of Ir and Pt can be performed in an atmosphere carrying out dry-etching at a low pressure because the boiling point of the hexa-fluoride compound is relatively low. On the other hand, it is hard to carry out reactive dry-etching because reactivity of Ir and/or Pt with the fluoride gas is quite low and both the metals form fluorides only at a high temperature atmosphere.
- In the present invention, reactive dry-etching can be carried out as a result of accelerating the reaction between Ir and/or Pt and fluorides by utilizing a high reactivity between Re and fluoride gas. In other words, the reactivity of Ir and/or Pt with the fluoride gas is increased by replacing a part of the electrode made of Ir and/or Pt with Re while observing no adhesion and formation of no side walls (burrs adheres on the surfaces to be etched) because the compositions formed by the reaction such as PtxRe1-xF6 and/or IrxRe1-xF6 can be vaporized as a result of their low boiling point.
- The advantage described above can be expected not only in the use of fluoride gas, but also in the use of chlorine gas. There is a probability that chlorine compound formed during the etching possibly adheres on the both sides of the mask without vaporizing because both the melting point and the boiling point of chlorine are high. However, both the melting point and the boiling point of oxygen chloride of Re are relatively low, so that it can be vaporized under a low pressure. In other words, the similar advantage to that of the reactive dry-etching carried out using the fluoride gas described earlier can be expected by using chlorine gas as an etchant in an atmosphere with the presence of oxygen. Oxide gas such as oxygen gas, ozone, NOx can be used as a supply source for causing oxidation, and these should be added to the etchant. The atmosphere with the presence of oxygen can be created by utilizing a mask made of photo resist or SiO2 both containing oxygen without supply of oxide gas.
- Moreover, table 3 shows conductive metal oxides having enough conductivity capable of using for the electrode of the ferroelectric capacitor described earlier. As apparent from the table 3, the metal oxides which withstand the thermal treatment for the crystallization are IrO2, RuO2, RhO2, RhO3 and ReO2.
TABLE 3 CONDUCTIVE METAL OXIDES OF NOBLE METALS MELTING ELECTRIC CRYSTALLINE LATTICE CONSTANT POINTS RESISTANCE SYSTEM (A) (° C.) (Ω/cm) REMARKS OsO2 TETRAGONAL a = 4.51, o = 3.19 500(D) 6.0E-5 FORMING OsO4 AFTER DECOMPOSITION IrO2 TETRAGONAL a = 4.498, o = 3.164 1100 4.9E-5 (RUTILE) PtO2 TETRAGONAL 450,500(D) 8.0E-4 NO PERFECT ANRYDROUS RuO2 TETRAGONAL a = 4.51, o = 3.11 3.5E-5 (RUTILE) RhO2 TETRAGONAL a = 4.488, o = 3.088 <1E-4 (RUTILE) RhO3 CUBIC 1.8E-5 ReO2 MONOCLINIC 1000(D) 1.0E-4 FORMING Re2O7 (β) AFTER DECOMPOSITION ReO3 CUBIC a = 3.74 400(D) 1.8E-5 FORMING ReO2 AFTER DECOMPOSITION - Another consideration is given to materials for carrying out dry-etching. Similar to the earlier embodiment, the required factors of the conductive metal oxides used in the dry-etching using the halogens are both of reacting with the halogens at a low temperatures and having a low melting point and a low boiling point of halogen compound formed during the etching. Both Re and Ru react with fluoride (F) at a low temperature as far as concerning the reactivity to the halogens. However, RU could take different valence number, ions of Ru except for tetra-valent ions are generated at a high temperature. The ions thus generated cause degradation of the capacitor characteristics because the ions react with the ferroelectric materials as a result of high reactivity thereof. On the contrary, ReO3 having hexa-valent of Re oxides is decomposed at approximately 400° C. and becomes to ReO2. Re oxide having tetra-valent has been kept stable until generation of Re2O7 as a result of decomposition of ReO2 started at approximately 1,000° C.
- Table 4 shows the melting points and the boiling points of compounds generated as a result of reaction to the halogen, the compounds shown in the table are not listed on the table 2.
TABLE 4 MELTING POINTS AND BOILING POINTS OF HALOGEN COMPOUNDS OF MAJOR METALS MELTING BOILING MELTING BOILING ELEMENTS POINTS (° C.) POINTS (° C.) ELEMENTS POINTS (° C.) POINTS (° C.) RhF3 >600 (SUBLI- OsF4 230 MATED) RhF5 95.5 OsF5 70 225.7 RhF 6 70 DECOM- OsF6 32.1 45.9 POSED RhCl3 450 (DECOM- OsCl3 350 (SUBLI- 450 (DECOM- POSED) MATED) POSED) RhBrs DECOM- OsCl4 450 POSED OsBr4 350 (DECOM- POSED) OsF2O3 171 - As apparent from the table 4, both the melting point and the boiling point of compounds including Rh are too high, or Rh is in decomposition, and hexa-fluoride of Os can be vaporized during the dry-etching carried out under a low pressure because the boiling point of hexa-fluoride of Os is relatively low. However, it is hard to carry out reactive dry-etching because reactivity of Os with the fluoride gas is quite low and Os forms fluorides only at a high temperature atmosphere. Therefore, the conductive oxides described above capable of using for the dry-etching are formed by replacing a part of the oxidized electrode made of IrO2 and the like with Re similar to the metals described earlier. In this way, the reactivity of the oxidized electrode can be increased by utilizing a high reactivity of Re to the fluoride gas. Further, substances formed by the reaction such as Irx Re1-xF6 and the like can be vaporized at a low temperature as a result of their low boiling point. Consequently, no adhesion and the formation of no side walls are observed. Further, the oxygen chloride of Re can be vaporized under a low pressure similar to the embodiment described above, so that the dry-etching can be carried out by using the chlorine gas. No introduction of oxide gas is needed to carry out the etching because the electrode is composed of materials containing oxides. Therefore, reactive dry-etching not allowing any adherence on both sides of the mask and the like can be carried out by replacing a part of the electrode with Re having an excellent anti-acid characteristic when the oxide of the noble metals having conductivity such as IrO2 is used for the electrode.
- As described earlier, thorough studies and researches are conducted to investigate a material which is not oxidized during the high temperature thermal treatment for crystallizing dielectric materials carried out in the atmosphere with the presence of oxygen, as well as a material capable of using for carrying out reactive dry-etching. As a result of the study and the researches, the inventor has found out that the addition of Re to the electrode materials containing noble metals such as Pt, Ir, IrO2 and the like make the electrode so as to withstand during the high temperature thermal treatment, and capable of carrying out reactive dry-etching as well as capable of carrying out a fine work on. In other words, Re itself is liberated as a halogenoid by carrying out dry-etching using halogen gas as an etchant because Re existing in the electrode may be vaporized when it reacts with halogen. Halogen combines to the places where no Re is existed as a result of the lack of Re caused by the evaporation. Then, Pt and/or Ir bonded with halogen liberates therefrom. Reactive dry-etching can be carried out by repeating a series of process described hereinabove. Although, a certain amount of Re added to the electrode is acceptable because of its heat resistance, the amount of Re is preferably not too much in consideration of alignment to the crystal of ferroelectrics. Because Pt and/or Ir has better probability of aligning to the crystalline of ferroelectrics and the like than that of Re. Though, the more Re is preferable in an ordinary active etching, only a small amount of Re enables the reactive dry-etching since Re tend to cause a chain reaction as described earlier. The amount of Re added to the electrode is preferably at a range of 5 to 20 atomic percentage in consideration of above-mentioned conditions.
- According to the present invention, the electrode holding either of ferroelectric material(s) or high-dielectric material(s) in its inside is made of Pt and/or Ir, or the conductive oxides containing Re, so that, reactive etching, not physical etching can be performed to noble metals such as Pr and/or Ir by carrying out dry-etching using either fluoride gas or chlorine gas as an etchant. Consequently, the noble metals thus removed not adhere on the surfaces to be etched and adjacent thereof, so that, a fine work can be performed. Moreover, no degradation of Re is observed when a high temperature thermal treatment for crystallizing dielectric materials is carried out because Re has enough heat resistance similar to that of Pt and Ir. In this way, a high-performance capacitor composed of ferroelectrics and/or high dielectrics can be realized.
- Although, the conductive thin film is used as a part of the electrode of the capacitor made of ferroelectrics and/or high dielectrics in the embodiment described above, the conductive thin film according to the present invention can also be used as other electrodes commonly used.
- Further, the conductive thin film according to the present invention can also be used as a wiring as well as a barrier metal. In other words, the conductive thin film can be used for a case in which a high temperature thermal treatment is carried out as a post-treatment and a case in which a fine work to which is required. This is because the conductive thin film according to the present invention has enough heat resistance as well as capable of carrying out a fine work thereto.
- The material(s) of the part(s) formed adjacent to the conductive thin film is not limited to specific kind(s) except when the thin film is used as a part of the electrode made of ferroelectrics and/or high dielectrics of the capacitor. Metals, metal oxides, silicon, poly-silicon, silicon-oxide, silicon-nitride, silicon-oxide-nitride and the like can be used for the materials of the parts formed adjacent to the conductive thin film.
- While the invention has been described in its preferred embodiments, it is to be understood that the words which have been used are words of description rather than limitation and that changes within the purview of the appended claims may be made without departing from the true scope and spirit of the invention in its broader aspects.
Claims (16)
1. A capacitor comprising:
a dielectric material composed by using at least one of a ferroelectric material and a high-dielectric material, and
an electrode composed by using a material containing a noble metal, the electrode being formed on at least one side of the dielectric material,
wherein the material of the electrode contains rhenium (Re).
2. The capacitor in accordance with , wherein the material containing a noble metal is composed by using one of platinum (Pt) and iridium (Ir).
claim 1
3. The capacitor in accordance with , wherein the material containing a noble metal contains one oxide of a metal selected from a group of osmium (Os), iridium (Ir), platinum (Pt), ruthenium (Ru) and rhodium (Rh).
claim 1
4. The capacitor in accordance with , wherein the electrode has a multi-layered structure made of a conductive material,
claim 1
and wherein at least one of the layers forming the multi-layered structure contains the material containing a noble metal,
and wherein the one layer contains rhenium (Re).
5. A semiconductor device including a capacitor structure at least comprising:
a semiconductor layer,
a dielectric material composed by using at least one of a ferroelectric material and a high-dielectric material, the dielectric material being located on the semiconductor layer, and
an electrode formed on the dielectric material,
wherein a material containing a noble metal adding rhenium (Re) is used for a material of the electrode.
6. A method of manufacturing a capacitor comprising the steps of:
forming an electrode composed by using a material containing a noble metal at least one side of a dielectric material composed by using at least one of a ferroelectric material and a high-dielectric material and
performing a patterning of the electrode by etching,
wherein rhenium (Re) is added to the material of the electrode,
and wherein the etching is in dry-etching by introducing fluorine gas.
7. A method of manufacturing a capacitor comprising the steps of:
forming an electrode composed by using a material containing a noble metal at least one side of a dielectric material composed by using at least one of a ferroelectric material and a high-dielectric material, and
performing a patterning of the electrode by etching,
wherein rhenium (Re) is added to the material of the electrode,
and wherein the etching is in dry-etching by introducing chlorine gas.
8. The method in accordance with , wherein the dry-etching is carried out while introducing a supply source for causing oxidation.
claim 7
9. A thin film having a certain conductivity, the thin film being composed by using a material containing a noble metal, wherein the material contains Re.
10. The thin film in accordance with , wherein the material containing a noble metal is composed by using one of platinum (Pt) and iridium (Ir).
claim 9
11. The thin film in accordance with , wherein the material containing a noble metal contains one oxide of a metal selected from a group of osmium (Os), iridium (Ir), platinum (Pt), ruthenium (Ru) and rhodium (Rh).
claim 9
12. The thin film in accordance with wherein the thin film has a multi-layered structure made of a conductive material,
claim 9
and wherein at least one of the layers forming the multi-layered structure contains the material containing a noble metal,
and wherein the one layer contains rhenium (Re).
13. A semiconductor device comprising:
a semiconductor substrate, and
a conductive thin film formed one of directly and indirectly on the substrate,
wherein a material containing a noble metal adding rhenium (Re) is used for a material of the thin film.
14. A method of manufacturing a semiconductor device comprising the steps of:
forming a conductive thin film on a semiconductor substrate one of directly and indirectly, and
performing a patterning of the conductive thin film by etching,
wherein a material of the thin film is made by using a material containing a noble metal adding rhenium (Re),
and wherein the etching is in dry-etching by introducing fluorine gas.
15. A method of manufacturing a semiconductor device comprising the steps of:
forming a conductive thin film on a semiconductor substrate one of directly and indirectly, and
performing a patterning of the conductive thin film by etching,
wherein a material of the thin film is made by using a material containing a noble metal adding rhenium (Re),
and wherein the etching is in dry-etching by introducing chlorine gas.
16. The method in accordance with , wherein the dry-etching is carried out while introducing a supply source for causing oxidation.
claim 15
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US10/393,443 US6783998B2 (en) | 1997-11-28 | 2003-03-20 | Conductive thin film, a capacitor using the same and a method of manufacturing thereof |
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JP32685097A JP3974697B2 (en) | 1997-11-28 | 1997-11-28 | Capacitor and its manufacturing method |
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US09/200,315 Abandoned US20010005026A1 (en) | 1997-11-28 | 1998-11-25 | Conductive thin film, a capacitor using the same and a method of manufacturing. |
US10/393,443 Expired - Fee Related US6783998B2 (en) | 1997-11-28 | 2003-03-20 | Conductive thin film, a capacitor using the same and a method of manufacturing thereof |
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Cited By (3)
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US20030071294A1 (en) * | 2001-02-28 | 2003-04-17 | Shan Sun | Process and structure for masking integrated capacitors of particular utility for ferroelectric memory integrated circuits |
EP1306889A2 (en) * | 2001-10-26 | 2003-05-02 | Fujitsu Limited | Electronic device with electrode and its manufacture |
US7170125B2 (en) | 2002-11-29 | 2007-01-30 | Infineon Technologies Ag | Capacitor with electrodes made of ruthenium and method for patterning layers made of ruthenium or ruthenium |
Families Citing this family (1)
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JP4036707B2 (en) * | 2002-08-12 | 2008-01-23 | 三洋電機株式会社 | Dielectric element and method for manufacturing dielectric element |
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US5348894A (en) | 1993-01-27 | 1994-09-20 | Texas Instruments Incorporated | Method of forming electrical connections to high dielectric constant materials |
US5471364A (en) | 1993-03-31 | 1995-11-28 | Texas Instruments Incorporated | Electrode interface for high-dielectric-constant materials |
KR0171060B1 (en) | 1993-12-28 | 1999-03-30 | 스기야마 카즈히코 | Manufacturing method of semiconductor device |
US5566045A (en) | 1994-08-01 | 1996-10-15 | Texas Instruments, Inc. | High-dielectric-constant material electrodes comprising thin platinum layers |
US5622893A (en) | 1994-08-01 | 1997-04-22 | Texas Instruments Incorporated | Method of forming conductive noble-metal-insulator-alloy barrier layer for high-dielectric-constant material electrodes |
JPH08250660A (en) | 1995-03-14 | 1996-09-27 | Ulvac Japan Ltd | Capacitance element and manufacture of capacitance element |
JPH10261772A (en) * | 1997-01-14 | 1998-09-29 | Mitsubishi Electric Corp | Semiconductor storage device and its manufacture |
EP0865079A3 (en) | 1997-03-13 | 1999-10-20 | Applied Materials, Inc. | A method for removing redeposited veils from etched platinum surfaces |
JP3484324B2 (en) | 1997-07-29 | 2004-01-06 | シャープ株式会社 | Semiconductor memory device |
DE19733391C2 (en) * | 1997-08-01 | 2001-08-16 | Siemens Ag | Structuring process |
WO1999026277A1 (en) * | 1997-11-17 | 1999-05-27 | Mattson Technology, Inc. | Systems and methods for plasma enhanced processing of semiconductor wafers |
US6171970B1 (en) | 1998-01-27 | 2001-01-09 | Texas Instruments Incorporated | Method for forming high-density integrated circuit capacitors |
JP2000021859A (en) * | 1998-07-03 | 2000-01-21 | Matsushita Electric Ind Co Ltd | Method and system for dry etching |
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1997
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US20030071294A1 (en) * | 2001-02-28 | 2003-04-17 | Shan Sun | Process and structure for masking integrated capacitors of particular utility for ferroelectric memory integrated circuits |
EP1306889A2 (en) * | 2001-10-26 | 2003-05-02 | Fujitsu Limited | Electronic device with electrode and its manufacture |
EP1306889A3 (en) * | 2001-10-26 | 2004-08-18 | Fujitsu Limited | Electronic device with electrode and its manufacture |
US20040195605A1 (en) * | 2001-10-26 | 2004-10-07 | Fujitsu Limited | Electronic device with electrode and its manufacture |
US7153705B2 (en) | 2001-10-26 | 2006-12-26 | Fujitsu Limited | Electronic device with electrode and its manufacture |
US7170125B2 (en) | 2002-11-29 | 2007-01-30 | Infineon Technologies Ag | Capacitor with electrodes made of ruthenium and method for patterning layers made of ruthenium or ruthenium |
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JPH11163270A (en) | 1999-06-18 |
US20030232453A1 (en) | 2003-12-18 |
US6783998B2 (en) | 2004-08-31 |
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