TW200428525A - Liquid composition for forming ferroelectric thin film and method for forming ferroelectric thin film - Google Patents
Liquid composition for forming ferroelectric thin film and method for forming ferroelectric thin film Download PDFInfo
- Publication number
- TW200428525A TW200428525A TW093111948A TW93111948A TW200428525A TW 200428525 A TW200428525 A TW 200428525A TW 093111948 A TW093111948 A TW 093111948A TW 93111948 A TW93111948 A TW 93111948A TW 200428525 A TW200428525 A TW 200428525A
- Authority
- TW
- Taiwan
- Prior art keywords
- ferroelectric
- thin film
- liquid composition
- ferroelectric thin
- particles
- Prior art date
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 53
- 239000007788 liquid Substances 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 76
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 37
- 238000010304 firing Methods 0.000 claims abstract description 21
- 239000010408 film Substances 0.000 claims description 36
- 239000000758 substrate Substances 0.000 claims description 20
- 239000011521 glass Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 29
- 239000011164 primary particle Substances 0.000 abstract description 11
- 239000000243 solution Substances 0.000 description 22
- 239000012071 phase Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 14
- 239000010936 titanium Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- 230000002269 spontaneous effect Effects 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- -1 organic acid salt Chemical class 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000010287 polarization Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910002113 barium titanate Inorganic materials 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052810 boron oxide Inorganic materials 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 239000013081 microcrystal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910021344 molybdenum silicide Inorganic materials 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000003303 reheating Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
- DEDUBNVYPMOFDR-UHFFFAOYSA-N 2-ethoxypropan-1-ol Chemical compound CCOC(C)CO DEDUBNVYPMOFDR-UHFFFAOYSA-N 0.000 description 1
- YTTFFPATQICAQN-UHFFFAOYSA-N 2-methoxypropan-1-ol Chemical compound COC(C)CO YTTFFPATQICAQN-UHFFFAOYSA-N 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- OQLZINXFSUDMHM-UHFFFAOYSA-N Acetamidine Chemical compound CC(N)=N OQLZINXFSUDMHM-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- MJXUFBUYCLOLBZ-UHFFFAOYSA-N C(C)(=N)N.CC(=O)C Chemical compound C(C)(=N)N.CC(=O)C MJXUFBUYCLOLBZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- DQUIAMCJEJUUJC-UHFFFAOYSA-N dibismuth;dioxido(oxo)silane Chemical compound [Bi+3].[Bi+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O DQUIAMCJEJUUJC-UHFFFAOYSA-N 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 238000010299 mechanically pulverizing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical class CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- YGSFNCRAZOCNDJ-UHFFFAOYSA-N propan-2-one Chemical compound CC(C)=O.CC(C)=O YGSFNCRAZOCNDJ-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G35/00—Compounds of tantalum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0027—Mixed oxides or hydroxides containing one alkali metal
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0036—Mixed oxides or hydroxides containing one alkaline earth metal, magnesium or lead
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0054—Mixed oxides or hydroxides containing one rare earth metal, yttrium or scandium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
- C23C18/127—Preformed particles
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02197—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides the material having a perovskite structure, e.g. BaTiO3
-
- 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
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31691—Inorganic layers composed of oxides or glassy oxides or oxide based glass with perovskite structure
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- General Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Ceramic Engineering (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Semiconductor Memories (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Inorganic Insulating Materials (AREA)
- Formation Of Insulating Films (AREA)
Description
200428525 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關形成強介電體薄膜用液狀組成物及利用 其製造強介電體薄膜之方法者。 【先前技術】 近來’做爲新型記憶體元件受矚目之強介電體記憶體 (FeRAM )係積極利用強介電體薄膜之自發分極特性後, 進行情報之讀取’因此,被期待於揮發性、書寫速度、信 賴性、單位面積等面可有效克服目前尙存之DRAM、 SRAM ' FLASH記憶體等缺點,開發一種理想之記憶體 者。 做爲FeRAM用之強介電體材料者目前爲止有鈸酸鉻 酸鉛系(PZT PLZT )、鉍系層狀鈣鈦礦強介電體 (BLSF)等金屬氧化物系材料被提出硏討之。 通常,此等強介電體薄膜被揭示有藉由濺射法等物理 生氣相成膜法(PVD ) 、MOCVD法等化學性氣相成長 法、及化學性溶液成膜法(溶液法)進行成膜方法者。其 中,溶液法於公知者係無需特殊之高價裝置下,可以最廉 價且簡便下進行強介電體薄膜之成膜者。又,溶液法易於 控制精社、之組成’出現於多數強介電體材料,具有依不同 組成可抑制特性變動之優點,做爲一種極有效之強介電體 薄S吴製造方法之一被積極討論之。 藉由溶液法製作強介電體薄膜係於基板上進行塗佈均 -5- (2) (2)200428525 質溶解原料之各成份金屬化合物(前驅物)溶液後,使塗 膜乾燥後,必要時進行煅燒(pre-bake )後,於空氣中以 約7〇〇°C或更高溫度下進行燒成後形成結晶性金屬氧化物 薄膜後,進行強介電體薄膜之成膜方法者。做爲原料之可 溶性金屬化合物者通常使用金屬烷氧化物,其部份水解物 或有機酸鹽、螯合絡合化合物之有機金屬化合物者。 另外,針對使用該FeR AM之單位構造目前有幾個單 位構造被揭示之,惟,現行實用化者以局部配線連接強介 電體電容器與晶體管,所謂葡萄石構造者,其單位面積之 縮小化,亦即,高集成化之觀點視之爲不利構造者。 做爲解決此等構造者,被揭示有於管塞所形成強介電 體電容器之通風構造者,惟,於多層配線形成時,其還原 氣氛引起強介電體薄膜致命的劣化特性之問題點。更做爲 解決此等問題之結構者被揭示有進行多層配線之形成後, 亦即結束邏輯程序後,於最上層形成強介電體薄膜與平板 線之構造者。此構造中爲做成對於理論電路上之成膜,於 強介電體薄膜形成時之燒成溫度被要求降至400°C〜450°C 者。 爲對應此,有關藉由溶液法之強介電體薄膜之製作中 亦降低結晶化溫度之各種方法被揭示之。如:USP 5 59 2 5 ,183公報等所示之適當控制前驅物構造之方法,預 先將常介電體之矽酸鉍力Π入塗層液之方法 (Ferroelectrics,271 卷,289 頁(2002 年)),以鈦酸 鉛層做爲晶種層使用之方法(J P n . J . A p p 1. P h y s ; 3 5卷, -6 - (3) (3)200428525 4896 頁 (1996 年)),適當基材之選擇 (J.Am.Ceram.Soc.,75 卷,2785 頁(1992 年))’滅壓锻 燒法(Jpn· J.Appl.Phys.,38 卷,5346 頁( 1999 年)等 者。惟,此等先行方法中燒成溫度均降至5 5 0 °C爲極限 者。因此,藉由溶液法時’事實上對於形成高集成化必要 理論電路上之強介電體薄膜者極爲不易者。 更且,嘗試使用強介電體之微粒子與可溶性金屬鹽共 存之組成物形成薄膜者(Jpn.J.Appl.Phys.,41卷,6969頁 (2 002年))。惟,此強介電體之微粒子係使用藉由長 時間機械性粉碎取得之粒子者,因此,將導致降低粒子之 結晶性,而未能取得所期待之特性。 【發明內容】 本發明鑑於上述先行技術之問題點,而提供一種以溶 液法進行成膜後取得強誘電體薄膜時,於較低溫度下,特 是 5 5 0 °C以下,甚至4 5 0 °C以下之溫度可進行燒成,因 此,可於高集成化對於必要之理論電路上形成強介電體薄 膜,且,可製作具有耐電壓、自發分極性,特別是疲勞特 性等面具良好之強誘電體特性薄膜之形成薄膜用液狀組成 物,及使用其之製造強介電體薄膜之方法爲目的者。 本發明持續進行精密硏討後達成該目的,其特徵爲具 有下記構成者。 (1 )液狀媒體中以一般式AB〇3 ( A爲至少1種選自 Ba2+、Sn2+、Ca2+、Pb2+、La2+、K +及 Na +所成群者,B 爲 -7- (4) (4)200428525 至少1種選自Ti4+、Zr4+、Nb5+、Ta5+及Fe3+所成群 者。)所示之具有鈣鈦礦構造,平均一次粒徑爲10 Onm 以下者,且,形態比爲2以上之板狀或針狀結晶之強介電 體氧化物粒子被分散之’且’溶解藉由加熱後形成強介電 體氧化物之可溶性金屬化合物者爲其特徵之形成強介電體 薄膜用液狀組成物者。 (2 )可溶性金屬化合物係藉由加熱後,形成一般式 AB〇3 ( A 爲至少一種選自、Ba2+、Sr2+、Ca2+、Pb2+、 La2+、K+及 Na+所成群者,B爲至少一種選自 Ti4+、 Zr4+、Nb5+、Ta5 +及Fe3 +所成群者。)所示之具有鈣鈦礦 構造之強介電體氧化物之化合物者之該(1 )所載形成強 介電體薄膜用液狀組成物。 (3 )強介電體氧化物粒子係於玻璃基質中使強介電 體氧化物粒子進行結晶化後去除玻璃基質成份後取得之粒 子之該(1 )或(2 )所載形成強介電體薄膜用液狀組成 (4 )含強介電體氧化物粒子/可溶性金屬化合物之比 率以氧化物換算之質量比下,5/95〜95/5之該(1 )〜(3 ) 中任一項之形成強介電體薄膜用液狀組成物。 (5 )含強介電體氧化物粒子與可溶性金屬化合物之 總量爲1〜5 0質量%之(1 )〜(4 )中任一項之形成強介電 體薄膜用液狀組成物。 (6 )於基板上塗佈該(1 )〜(5 )中任一項之液狀組 /¾¾ ‘後’ Μ 5 5 G°C以下進行燒成之製造強介電體薄膜之方 冬 (5) (5)200428525 法。 (7 )強介電體薄膜之膜厚爲10〜3 00nm者之(6 )所 介電體薄膜之製造方法。 【實施方式】 [發明實施之最佳形態] &下,針對本發明進行詳細說明。 本發明中一般式AB〇3 ( A爲至少1種選自 Ba2+、 St2+、Ca2+、Pb2+、La2+、K +及 Na +所成群者,B 爲至少 1 種選自Ti4+、Zr4+、Nb5+、Ta5 +及Fe3 +所成群者。)所示 之具鈣鈦礦構造之強介電體氧化物結晶粒子(以下亦簡稱 強介電體粒子)係做爲本發明組成物中根幹之必須成份 者。本發明中藉由使用分散具該高結晶性之強介電體粒子 於液狀媒體之液狀組成物後,於目前溶液法所使用之可溶 性金屬化合物溶液進行成膜時,可飛躍性降低必要之燒成 溫度。 該強介電體粒子爲具有一般式AB〇3 ( A,B爲與上述 相同者)所示之1¾欽礦構造之強介電體者,該一般式之A 以Ba2+、Sr2+、Pb2 +者宜,B以Ti4+、Zr4 +者宜。其中又 以A爲Pb、B爲Ti與Zr之複合氧化物者之Pb (ZrxTi】 -x ) 03 ( X爲〇·1〜0.9者。以下亦稱PZT。)者 宜。當然,此ΡΖΤ之Pb定位以其他元素,如La等稀土 類元素做爲部份取代之PLZT之公知的強介電體等亦可使 用之。 冬 (6) (6)200428525 該強介電體粒子其平均一次粒徑務必爲l〇〇nm以下 者。其中,以一次粒徑之長徑爲基準,又’平均粒徑爲數 平均粒徑者。當平均一次粒徑大於此時’則薄膜形成時袠 面之凹凸變粗,薄膜中之塡充率不提昇,介電特性降低。 其中又以平均一次粒徑爲50nm以下者較佳,特別以 10〜30nm爲最佳。當平均一次粒徑不足l〇nm則粒子之強 介電特性將降低。 本發明強介電體粒子,具該範圍平均一次粒徑之同 時,更且,其形態爲各向異性結晶粒子,亦即,其形態比 務必爲2以上之板狀或針狀結晶者。其中,形態比係指具 有各向異性粒子之長徑/短徑比率者,板狀結晶者爲直徑/ 厚度之比率、針狀結晶者爲長度/直徑之比率者。特別 是,本發明錦欽礦型之強介電體氧化物中,自發分極方向 與結晶格子之C軸方向多半爲一致者,例如··垂直於c 軸之面(〇 〇 1 )面)使用成長之板狀結晶後,其塗佈後粒 子自發性整列於c軸方向,亦即,容易定位,具取得高度 自發分極値之優點。且,可提昇強介電體粒子之定位性, 因此連帶的亦提昇強介電體薄膜之疲勞特性。本發明中形 態比小於2時,則將降低所形成強介電體薄膜之特性而不 理想。當形態比爲5以上時爲最理想者。 做爲具有該特性之強介電體粒子者,特別由具有高度 結晶性者’於玻璃基質中使強誘電體粒子結晶化後去除玻 璃基質成份之後取得之粒子者宜。亦即,於玻璃母材融液 中溶解做爲強誘電體粒子被結晶化之成份後放置之,融液 - 10- (7) (7)200428525 進行急速冷卻後玻璃化後,再度進行加熱煅燒後母材中藉 由析出微結晶之玻璃結晶化法後取得之粒子者。所析出之 微結晶藉由適當藥液等溶解玻璃基質後被取出。 於該玻璃基質中被結晶化之超微粒子易於控制形態、 煅燒處理之條件等較易製作各向異性較大之微粒子,同時 亦具有易於取得形態比大的粒子之優點。 做爲該玻璃母材者一般可使用硼酸系、磷酸系、砂酸 系等,而,由熔融性,易與目的氧化物複合化合物製造、 基質溶離之容易性等面觀之,又以硼酸系之玻璃母材爲較 佳使用者。 以下’強介電體氧化物粒子之製造以製作鈦酸鉻酸鉛 (PZT )微結晶之方法爲例進行具體之說明後,可於以下 ①〜④步驟取得強介電體粒子。 ① 混合玻璃形成成份(如氧化硼)與做爲目的之強介 電體氧化物粒子組成金屬氧化物(如氧化鉻、氧化鈦及氧 化鉛)後,整體於120(TC以上之溫度下進行熔融[熔融]。 ② 使熔融玻璃進行急速冷卻後,取得含強介電體氧化 物組成金屬離子之玻璃[玻璃化]。 ③ 於5 5 0 °C〜7 0 0 °C之溫度下進行椴燒處理後,玻璃中 形成強介電體氧化物之結晶核、控制煅燒條件後,使成長 至所定粒徑爲止[結晶化]。 ④ 藉由其酸、水或其混合物取得去除玻璃母材成份 (如:氧化硼)之強介電體粒子(如,
Pb ( ΖγχΊΠ】·χ ) 03 )[瀝濾]。 (8) (8)200428525 藉由上記一連串步驟,於煅燒溫度範圍下,以極高粘 度之玻璃做爲母材進行結晶化,因此,極易控制強介電體 粒子之粒徑、粒子形態,且可取得高結晶性之微結晶者。 另夕丨’本發明中藉由加熱可形成強介電體氧化物之可 溶性金屬化合物(以下亦稱可溶性金屬化合物)係指藉由 加熱之熱分解等轉化成氧化物後顯示強介電性之化合物 者。做爲目的之強介電體氧化物爲複合氧化物時,可使用 以所定比率混合2種以上可溶性金屬化合物者,或於所定 比例含2種以上金屬之複合金屬化合物使用之。做爲此等 可溶性金屬化合物者可使用硝酸鹽等無機酸鹽、乙基己烷 酸鹽、乙醯丙酮絡合物等有機金屬絡合物、或金屬烷氧化 物等’特別以有機酸鹽、有機金屬絡合物、或金屬烷氧化 物爲較佳使用者。 由本發明強介電體薄膜形成用液狀組成物形成強介電 體薄膜之過程中,該可溶性金屬化合物具有做爲強介電體 氧化物結晶粒子之結合劑作用,此可溶性金屬化合物可以 前述強介電體粒子做爲核進行結晶成長者,可由更低溫形 成結晶化者。又,可溶性金屬化合物於熱處理之燒成後, 於強介電體粒子間之空隙中形成強介電體氧化物後,亦具 有提昇做爲整體強介電體薄膜之介電特性作用者。 該可溶性金屬化合物亦可具有於燒成後形成與強介電 體粒子略同組成之強介電體之組成者,亦可具有形成不同 於強介電體粒子組成之強介電體之組成者。惟,考量該強 介電體粒子做爲結晶核作用時,又以形成可達強介電體粒 -12- 200428525 Ο) 子之相同組成的強介電體者爲較佳者。 本發明中含強介電體粒子與可溶性金屬化合物之比率 係於可溶性金屬化合物加熱後呈氧化物時之氧化物換算質 量比下,其強介電體粒子/可溶性金屬化合物比率爲 5/9 5〜9 5/5者宜。當此強介電體粒子大於此範圍時,則結 合劑成份將不足,而所形成薄膜恐無法密合於基板,反 之’小於該範圍時,將不易出現強介電體粒子之添加效 果。其中該比率做成3 0 / 7 0以上時,則可提昇強介電體粒 子之定向性,易取得高特性之強介電體薄膜爲特別理想 者。反之’該比率做成70/3 0以下則較易取得密緻之強介 電體薄膜爲理想者。 該強介電體粒子與可溶性金屬化合物係於適當之液狀 媒體中分散強介電體粒子,且,做爲溶解可溶性金屬化合 物之液狀組成物者使用強介電體薄膜形成用之塗佈液等 等。形成該液狀組成物時,亦可混合強介電體粒子與可溶 性金屬鹽化合物後於液狀媒體中進行溶解或分散之,亦可 分別於相同或相異之液狀媒體中分散或溶解者進行混合 之。做爲液狀媒體者只要可溶解可溶性金屬化合物者即 可,無特別限定,通常可使用水、醇(乙醇、2 —丙醇 等)、醚醇(2 —乙氧基乙醇、2—乙氧基丙醇等)、醋 (醋酸丁酯、乳酸乙酯等)、酮(丙酮、甲基異丁酮 等)、醚(二丁醚、二氧陸圜等)、脂肪族烴基(環己 烷、癸烷等)、芳香族烴基(甲苯、二甲苯)、含氮有機 溶媒(乙腈、N -甲基吡咯烷酮等)、或此等之2種以上 -13- (10) (10)200428525 混合溶媒者。做爲具體之液狀媒體者可依其組成物中之結 晶粒子之種類,表面狀態,可溶性金屬化合物之種類,更 依其塗佈方法進行適當選取、混合使用之。又,液狀媒體 中亦可含部份可溶性金屬化合物之未溶解份者。 做爲本發明液狀組成物中固形份(強介電體粒子與可 溶性金屬化合物之合計)之含量可依其目的之強介電體膜 厚、液狀物之塗佈方法等進行適當調節,一般以1〜5 0質 量%者宜。當小於該範圍時其藉由塗佈取得薄膜之厚度將 變得極小,爲取得所期待之厚度將務必重覆極多次之塗 佈,反之,大於該範圍時,則恐降低液的安定性。 又’本發明形成液狀組成物之該強介電體粒子,媒體 中溶解或分散可溶性金屬鹽化合物時,可使用球磨器、混 砂機,等媒體硏磨器、超音波式、攪拌式等各種勻漿器、 注射硏磨器、滾輥硏磨器等已知之方法、裝置者。 本發明液狀組成物中亦可含有爲分散該強介電體粒 子、可溶性金屬化合物之分散劑、爲改善塗膜之液流學特 性等之各種界面活性劑、表面處理劑、樹脂成份等。惟, 此等大量添加後於燒成後易呈殘碳份殘留之,因此以必要 最小限之量進行添加爲宜。 基板上塗佈本發明液狀組成物後,進行燒成後可製造 強介電體薄膜。做爲塗佈方法者,可使用己知之方法者。 理想之具體例如:旋轉塗佈法、浸瀆塗佈法、噴霧塗佈 法、濾網印刷法、複製印刷法等例。其中又以旋轉塗佈法 其取得薄膜之均質性、生產性面爲最理想者。 -14 - (11) (11)200428525 做爲本發明形成薄膜時所使用之基板者如:Si、GaAs 等單結晶半導體基板、BaTi〇3、SrTi〇3、MgO、A1203等 之單結晶介電體基板,於此等表面上堆積多結晶Si,做爲 電極層者堆積Pt、Ir、Ir〇2、RU、Rll〇2等者,或於半導體 基板與該電極層之間設置Si02、Si3N4等之絕緣層Ti、Ta 之緩衝層者。惟,做爲基板者只要具有燒成溫度之耐熱性 者即可,不受限於此等。 於此等基板上塗佈本發明液狀組成物後,較佳者爲去 除媒體,一般於1 0 0〜4 0 0 °c下進行乾燥1分鐘至2小時 後,進行燒成之。此燒成係於如上述之本發明中可採用低 溫範圍者,理想者爲5 5 0 °C以下,依情況於4 5 0 °C以下進 行之。當然燒成亦可採用超過550 °C之溫度者,不同用途 下該®溫亦有利燒成者。燒成時間依其溫度,氣氛而異, 一般以1分鐘至2小時進行之。此燒成係使可溶性金屬化 合物進行分解及/或結晶化者,適當選於大氣中,氧、不 活性氣體下等進行使用之。燒成中亦可使用擴散爐類之電 爐’使用可急速昇溫之熱感光板、紅外線燈煅燒爐 (RTA )等後,更易進行結晶化較爲理想者。 如上述,形成本發明之強介電體薄膜時,使膜厚以 1〇〜3〇〇nm考宜。當膜厚不足l〇nm時,則不易取得均質 膜者’反之,超出3〇〇nm時,則恐於膜中出現裂化而不 里…、为外’由塗佈一乾燥一燒成所成之一次步驟中無法 取得所期待之膜厚時,當然可重覆進行此步驟。 列舉以下實施例進行本發明具體之說明,惟,本發明 -15- (12) (12)200428525 未受限於以下實施例。又,例6〜例8爲比較例者。 [例強介電體粒子(PZT)之製作] $氧化鉛、氧化鉻、氧化鈦(金紅石),及氧化硼秤 取含PbO、Zr〇2、Ti02及B2〇3者分別爲47.2莫耳%、 1 3 . 3莫耳%、n · 7莫耳%、及2 7 · 8莫耳%後,使用少量乙 酉亭&自動乳鉢充份濕式混合乾燥之後做成原料粉末。所取 ί辱原、Μ粉末塡充於融液滴入用噴嘴所附之鉑製容器(含 1〇%錄)後’以矽化鉬做爲發熱體之電爐中1 3 5 0 °C下進行 加熱2小時後,完全熔融之。再加熱噴嘴部位後,將融液 設置於電爐下之雙滾輥(滾輥經1 5 0mm、滾輥旋轉數 5〇rpm '滚輥表面溫度3〇艺)中滴入後取得碎片狀固形 物。 所取得碎片狀固形物確定呈透明狀,粉末x線衍射 之結果’爲非晶質物質者。此碎片狀固形物於5〇(rc下加 熱12小時後’ B2〇3玻璃基質中顯示強介電體粒子出現結 晶化者。再使該碎片粉加入維持於8〇〇C2 Imol/L醋酸水 溶液中攪梓6小時後,進行離心分離、水洗淨、乾燥之 後’取得白色粉末。 取得白色粉末藉由粉末χ線衍射後進行固定之後, 判定爲Pb ( zr〇.52 Ti G 48) 〇3結晶所成之粉末者。又,Zr 與Tx之比率依ICP法進行定量之。又,藉由透光型電子 顯微鏡進行觀察後結果此結晶呈板狀形,平均一次粒徑 2 0 n m,厚度爲9 n m,形態比爲2 · 2 2者。 -16- (13) (13)200428525 [例2 —強介電體粒子BaTi〇3之製作] 使碳酸鋇、氧化鈦(金紅石)、及氧化硼秤取B aO、 T i Ο 2、及B 2 0 3分別爲5 〇 · 〇、1 6.7、及3 3 . 3莫耳%後,使 用少量乙醇’以自動乳鉢充份進行濕式混合乾燥後做成原 料粉末。將取得原料粉末塡入附融液滴入用噴嘴之鉑製容 器(含1 〇%錢)後,矽化鉬於做爲發熱體之電爐中於 1 3 5 0 °C下加熱2小時後,完全熔融之。再加熱噴嘴部位 後,於電爐下方設置之雙滾輥(滾輥徑1 5 0 m m、滾輥旋 轉數50rpm、滾輥表面溫度30°C )中滴入融液後,取得碎 片狀固形物。 取得碎片狀固形物確定呈透明狀,粉末X線衍射之 結果爲非晶質物質者。此碎片狀固形物於5 9 0 °C下加熱1 2 小時後,進行結晶化處理。再將此碎片粉加入維持8 〇 之]m ο 1 / L之醋酸水溶液中,攪拌1 2小時後,進行離心分 離、水洗淨、乾燥之後,取得白色粉末。 藉由粉末X線衍射同定取得白色粉末後,證明爲金太 酸鋇結晶所成之粉末者。又,藉由透光型電子顯微鏡進行 觀察之結果,此結晶爲板狀形,平均一次粒徑爲2 5 n m, 厚度爲1 〇 η π),形態比爲2 · 5 0者。 [例3 - ΡΖΤ強介電體薄膜之製作] 利用濕式噴射硏磨器使例I取得之ΡΖΤ結晶粒子分 散於乙醇中,藉由離心分離後,去除粗大粒子,取得含 - 17- (14) (14)200428525 1 0質量%之PZT分散液A。利用激光散射粒度分佈計測定 該分散液A之分散粒徑後爲90nm者’呈良好之分散體。 使醋酸鉛、四丁基鈦酸酯、四丁基鉻酸酯及乙醯丙酮 於 2 —乙氧基丙醇中呈 Pb: Zr: Ti: Z醯丙酮=1·05: 0.5 3 : 0.4 7 : 1 : 00 (莫耳比)溶解之,氮氣流中130°C下 進行4小時迴流操作。將此溶液冷卻至室溫後,緩緩加入 離子交換水呈(Pb + Zr + Ti )之2倍(莫耳比)。之後,再 度於氮氣流中,1 3 0 °C下進行8小時迴流加熱後,取得可 溶性金屬化合物溶液B。另外,金屬源之液中濃度以氧化 物換算成1〇質量%者。 分散液A與可溶性金屬化合物溶液B以質量比(氧 化物換算値)混合呈5 0/5 0後,做成本發明組成物。 做爲基板者使用於表面層合Pt層(厚度200nm) /Ti 層(厚度20nm) /熱氧化3丨02層(厚度8 00nm)之聚矽氧 單結晶基板後,藉由旋轉塗佈法該組成物塗佈於表面之 Pt層後,於熱感光板上20 (TC下進行乾燥30分鐘。進行 此塗佈一乾燥處理3次之後,利用PTA爐於氧中45 下 進行燒成3 0分鐘。 取得被膜爲厚度1 OOnm,X線衍射結果優先定位於C 軸方向之PZT結晶相所成之被膜者。更於此被膜上藉由 DC濺射法製作〇.imm 0之pt電極,於pta爐40(TC,進 行1 5分鐘之後煅燒處理製作電容器後,測定強介電體滯 後特性之後,抗電界値爲44kV/cm,自發分極値爲 3 5pC/cm2者。取得強介電體電容器之疲勞特定之評定 -18- (15) (15)200428525 (循環試驗中,自發分極降低初期之5 %以上循環數) 後,重覆進行3V、108次循環後自發分極値之變化量仍控 制於5 %以內。 [例4] 利用濕式噴射硏磨器將例2取得之BaTi03結晶粒子 分散於乙醇後,藉由離心分離去除粗大粒子’取得含10 質量%之BaTi03分散液C。利用激光散射粒度分佈計測定 該分散液C之分散粒徑後爲8 0 n m之良好分散體者。 使金屬鋇、四丁基鈦酸酯、及二乙二醇溶於2 -甲氧基 丙醇中呈Ba: Ti:二乙二醇=1: 1: 1(莫耳比),於氮氣 流1 1 (TC下進行迴流操作4小時後’冷卻至室溫,使離子交 換水呈(Ba + Ti )之2倍(莫耳比)緩緩進行添加之。隨 後,再度於氮氣流1 1 〇°C下進行迴流加熱8小時後,取得可 溶性金屬化合物溶液D。另外,金屬源之液中濃度以氧化物 換算爲10質量%者。 使分散液C與可溶性金屬化合物溶液D呈質量比(氧 化物換算)70/30進行混合後,做成本發明組成物。 以表面層合 Pt層(厚度200n m) /Ti層(厚度 20n m) /熱氧化Si02層(厚度800nm)之聚砂氧單結晶基 板做爲基板使用後,於表面Pt層上藉由旋轉塗佈法進行 塗佈該組成物後,於熱感光板2 00 °C下進行乾燥30分 鐘。此塗佈一乾燥之處理進行3次後,利用RTA爐於氧 中5 0 0 °C下進行燒成2 0分鐘。 -19- (16) (16)200428525 取得被膜其厚度爲1 2 0 n m,X線衍射之結果,優先定 向於C軸方向之BaTi03結晶相所成之被膜。更於此被膜 上藉由DC濺射法製作〇.imm 0之Pt電極。於RTA爐 4 5 0 °C下進行後椴燒處理1 5分鐘後,製造電容器後測定強 介電體滯後特性之後,抗電界値爲30kv/cm,自發分極値 爲19pC/cm2。與例3同法進行評定取得強介電體電容器 之疲勞特性後,重覆± 3 V、1 06次之循環後仍可控制自發 分極値之變化量為約5 %者。 [例5〜7] 使用含1 〇質量%固相法下所製成之一次平均粒徑 1 ·2μηι (形態比1 )之球狀PZT結晶粒子分散液E取代例 3之強介電體結晶分散液Α後與例3同法進行成膜/評 定。取得相由 PZT單相所成之強介電體相者,分極特性 亦與例3取得之被膜爲相等者,惟,疲勞特性之評定中其 3 V,1 06次循環下之自發分極幾乎呈零,明顯出現劣化 者。另外,X線衍射之結果’強介電體相爲無定向者。 [例9] 利用行星式球磨器使固相法下所製成之球狀ΡΖΊΓ粒 子(平均一次粒徑1 ·2 ym )進行粉碎4 0小時。電子顯微 1¾觀察結果’粒徑爲微細化至4 0 n m考。利用此微粉末取 代例3之強介電體結晶分散液A,與例3之分散液a同法 進行調製分散液後,與例3同法製作pZT被膜。取得之 (17) 200428525 相爲PZT單相所成之強介電體相者,而,藉由粉碎後出 現ΡΖΤ結晶之變形影響。或自發分極値變小,且,疲勞 特性於1〇6次之循環下之自發分極亦降至初期之50%者。 另外,X線衍線之結果,強介電體相爲無定向者。 [表1]
例 結晶粒子 (a) 平均一次粒 子徑(nm) 形態比 可溶性金屬化 合物(b) 組成物中U) / (b)質量比 燒成溫度 例3 例1之PZT 20 2.22 PZT Zr/Ti=53/47 50/50 450〇C 例4 例2之BT 25 2.50 BT 70/30 500°C 例5 例1之PZT 20 2.22 PZT Zr/Ti=53/47 66/34 450〇C 例6 例1之PZT 25 2.22 PZT Zr/Ti=53/47 80/20 450〇C 例‘7 — 一 — PZT Zr/Ti=53/47 0/100 450〇C 例8 PZT 1200 1 PZT Zr/Ti=53/47 50/50 450〇C 例9 PZT 粉碎品 40 — PZT Zr/Ti=53/47 50/50 450〇C
-21 - (18) 200428525 [表 2] 例 膜厚(ηηι) 結晶相 抗電界 自發分極 疲勞特性 (kV/cm) (pC/cm2) (循環) 例3 100 PZT單相 44 35 >1〇8 例4 120 BT單相 30 19 -106 例5 100 PZT單相 49 39 >108 例6 100 PZT單相 51 39 >108 例7 110 非晶質 _ 例8 115 PZT單相 48 29 <104 例9 100 PZT單相 35 12 <104
[產業上可利用性] 本發明係提供一種,以溶液法進行成膜後,取得強介 電體薄膜時,於較低溫,特別是5 5 0 °C以下,更於4 5 0 °C 以下之溫度下可進行燒成,因此,可形成高集成所須理論 電路上之強介電體薄膜,且,具有良好抗高電性、自發分 極性、特別是可製造出疲勞特性均良好之強介電體特性薄 膜之薄膜形成組成物,及使用其製造強介電體薄膜之方法 者。 由本發明所製造之強介電體薄膜可有效做爲記憶元件 及其他裝置製造之使用。特別是膜厚爲丨〇〜300nm時,可期 待適用於FeRAM者。 -22-
Claims (1)
- 200428525 Π) 拾、申請專利範圍 1. 一種形成強介電體薄膜用液狀組成物,其特徵係 t 於液狀媒體中分散具有一般式AB〇3 ( A爲至少一種選自 、 Ba2+、Sr2+、Ca2+、Pb2+、La2+、K +及 Na +所成群者,b 爲 至少一種選自Ti4+、Zr4+、Nb5+、Ta5 +及Fe3 +所成群者) 所示之鈣鈦礦構造,其平均一次粒徑爲100nm以下, 且,形態比爲2以上之板狀或針狀結晶之強介電體氧化物 粒子’同時溶解藉由加熱形成強介電體氧化物之可溶性金 φ 屬化合物者。 2· ‘如申請專利範圍第1項之形成強介電體薄膜用液 狀組成物,其中該可溶性金屬化合物係藉由加熱後形成具 有一般式 AB〇3 ( A代表至少一種選自 Ba2+、Sr2+、 Ca2+、Pb2+、La2+、K +及Na +所成群者,B代表至少一種 選自Ti4+、Zr4+、Nb5+、Ta5 +及Fe3 +所成群者)所示之鈣 欽礦構造之強介電體氧化物之化合物者。 3 ·如申請專利範圍第1項或第2項之形成強介電體薄 馨 膜用液狀組成物,其中該強介電體氧化物粒子係使強介電 體氧化物粒子於玻璃基質中結晶化後去除玻璃基質後,取 得之粒子者。 4. 申請專利範圍第1項至第3項中任一項之形成強介 · 電體薄膜用液狀組成物,其中該強介電體氧化物粒子/可溶 - 性金屬化合物之含有比率以氧化物換算之質量比爲 5/9 5 〜9 5/5 者。 5. 如申請專利範圍第1項至第4項中任一項之形成強 -23- (2) (2)200428525 介電體薄0吴用液狀組成物’其中該強介電體氧化物粒子與可 溶性金屬化合物之總計含量爲1〜50質量%者。 6 · —種強介電體薄膜之製造方法,其特徵係使如申請 專利範圍第1項至第5項中任一項之液狀組成物塗佈於基 板上,於5 5 0 °C以下之溫度下進行燒成者。 7.如申請專利範圍第6項之強介電體薄膜之製造方 法,其中該強介電體薄膜之膜厚爲10〜300nm者。-24 - 200428525 柒、(一)、本案指定之代表圖為:無 (二)、本代表圖之元件代表符號簡單說明:無 捌、本案若有化學式時,請揭示最能顯示發明特徵的化學式:
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003125329 | 2003-04-30 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW200428525A true TW200428525A (en) | 2004-12-16 |
TWI324366B TWI324366B (zh) | 2010-05-01 |
Family
ID=33410219
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW093111948A TW200428525A (en) | 2003-04-30 | 2004-04-29 | Liquid composition for forming ferroelectric thin film and method for forming ferroelectric thin film |
Country Status (6)
Country | Link |
---|---|
US (1) | US7208324B2 (zh) |
EP (1) | EP1624468A1 (zh) |
JP (1) | JPWO2004097854A1 (zh) |
KR (1) | KR20060012573A (zh) |
TW (1) | TW200428525A (zh) |
WO (1) | WO2004097854A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI415794B (zh) * | 2009-10-23 | 2013-11-21 | Nat Univ Tsing Hua | 合成銦鎵鋅氧化物之方法及使用其形成銦鎵鋅氧化物薄膜之方法 |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2005010895A1 (ja) * | 2003-07-28 | 2006-09-14 | 旭硝子株式会社 | 強誘電体薄膜形成用液状組成物および強誘電体薄膜の製造方法 |
JP2005247660A (ja) * | 2004-03-05 | 2005-09-15 | Jsr Corp | 誘電体膜形成用組成物、誘電体膜形成用組成物の製造方法ならびに誘電体膜および誘電体膜を含むキャパシタ |
JP5056414B2 (ja) * | 2005-07-15 | 2012-10-24 | 旭硝子株式会社 | タンタル酸ストロンチウムビスマス微粒子の製造方法 |
JP5029363B2 (ja) * | 2005-08-19 | 2012-09-19 | 旭硝子株式会社 | 強誘電体層付き基体の製造方法 |
JP2008094972A (ja) * | 2006-10-12 | 2008-04-24 | Adeka Corp | 塗布液および該塗布液を用いたチタン酸系セラミックス膜の製造方法 |
KR101242840B1 (ko) | 2008-05-28 | 2013-03-13 | 에스티마이크로일렉트로닉스(뚜르) 에스에이에스 | 강유전체 박막 형성용 조성물, 강유전체 박막의 형성 방법 그리고 그 방법에 의해 형성된 강유전체 박막 |
JP5217997B2 (ja) * | 2008-10-20 | 2013-06-19 | Tdk株式会社 | 圧電磁器、振動子及び超音波モータ |
US9673381B2 (en) * | 2014-07-22 | 2017-06-06 | Haidou WANG | Lead titanate coating and preparing method thereof |
US9773966B2 (en) | 2014-09-08 | 2017-09-26 | Shimano Inc. | Piezoelectric sensor for bicycle component |
US20200148905A1 (en) * | 2018-11-08 | 2020-05-14 | University Of Massachusetts | Printable dielectric mixture and use and manufacture |
US10839992B1 (en) | 2019-05-17 | 2020-11-17 | Raytheon Company | Thick film resistors having customizable resistances and methods of manufacture |
Family Cites Families (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2852400A (en) * | 1953-03-24 | 1958-09-16 | Bell Telephone Labor Inc | Barium titanate as a ferroelectric material |
GB1422133A (en) * | 1972-08-25 | 1976-01-21 | Plessey Co Ltd | Ceramic materials |
US4077823A (en) * | 1975-11-10 | 1978-03-07 | Champion International Corporation | Method of producing a guarding cover for racks and the like |
US4874598A (en) * | 1987-01-20 | 1989-10-17 | Mitsubishi Petrochemical Co., Ltd. | Process for producing perovskite-type oxides of the ABO3 type |
US5453262A (en) * | 1988-12-09 | 1995-09-26 | Battelle Memorial Institute | Continuous process for production of ceramic powders with controlled morphology |
JP3477724B2 (ja) * | 1992-10-06 | 2003-12-10 | セイコーエプソン株式会社 | 強誘電体膜の形成方法 |
US6664115B2 (en) * | 1992-10-23 | 2003-12-16 | Symetrix Corporation | Metal insulator structure with polarization-compatible buffer layer |
JPH0778509A (ja) * | 1993-09-08 | 1995-03-20 | Ube Ind Ltd | 配向性誘電体磁器およびその製造方法 |
JPH0782022A (ja) * | 1993-09-08 | 1995-03-28 | Ube Ind Ltd | 配向性磁器およびその製造方法 |
US5650362A (en) * | 1993-11-04 | 1997-07-22 | Fuji Xerox Co. | Oriented conductive film and process for preparing the same |
US6027826A (en) * | 1994-06-16 | 2000-02-22 | The United States Of America As Represented By The Secretary Of The Air Force | Method for making ceramic-metal composites and the resulting composites |
US6001416A (en) * | 1994-11-24 | 1999-12-14 | Fuji Xerox Co., Ltd. | Oxide thin film and process for forming the same |
JPH0986906A (ja) * | 1995-07-13 | 1997-03-31 | Toshiba Glass Co Ltd | 機能性薄膜用機能性酸化物粉末の製造方法 |
WO1998011613A1 (fr) * | 1996-09-12 | 1998-03-19 | Citizen Watch Co., Ltd. | Element ferroelectrique, son procede de production, et tete pour impression a jet d'encre |
US5843516A (en) * | 1996-09-16 | 1998-12-01 | Symetrix Corporation | Liquid source formation of thin films using hexamethyl-disilazane |
JP2967189B2 (ja) * | 1997-09-01 | 1999-10-25 | 工業技術院長 | ビスマス系層状ペロブスカイト化合物強誘電体薄膜用前駆体の製造方法 |
JP3439972B2 (ja) * | 1997-12-24 | 2003-08-25 | 京セラ株式会社 | 高強度誘電体磁器およびその製造方法 |
US6478412B1 (en) * | 1999-01-22 | 2002-11-12 | Kansai Research Institute | Piezoelectric thin film device, its production method, and ink-jet recording head |
US6210752B1 (en) * | 1999-03-24 | 2001-04-03 | Sandia Corporation | All-alkoxide synthesis of strontium-containing metal oxides |
US6514476B1 (en) * | 1999-04-27 | 2003-02-04 | Penn State Research Foundation | Anisotropically shaped SrTiO3 single crystal particles |
US6277254B1 (en) * | 1999-12-16 | 2001-08-21 | Honeywell International Inc. | Ceramic compositions, physical vapor deposition targets and methods of forming ceramic compositions |
JP2001240469A (ja) * | 2000-02-28 | 2001-09-04 | Matsushita Electric Ind Co Ltd | 誘電体粒子の製造方法および誘電体膜の製造方法 |
US6589457B1 (en) * | 2000-07-31 | 2003-07-08 | The Regents Of The University Of California | Polymer-assisted aqueous deposition of metal oxide films |
KR100570576B1 (ko) * | 2000-10-17 | 2006-04-13 | 샤프 가부시키가이샤 | 산화물 재료, 산화물 박막의 제조 방법 및 상기 재료를사용한 소자 |
US7553512B2 (en) * | 2001-11-02 | 2009-06-30 | Cabot Corporation | Method for fabricating an inorganic resistor |
CN100584921C (zh) * | 2002-09-05 | 2010-01-27 | 奈米***股份有限公司 | 促进电荷转移至纳米结构或自纳米结构转移出电荷的有机物 |
US7147834B2 (en) * | 2003-08-11 | 2006-12-12 | The Research Foundation Of State University Of New York | Hydrothermal synthesis of perovskite nanotubes |
JP3841085B2 (ja) * | 2004-01-29 | 2006-11-01 | セイコーエプソン株式会社 | キャパシタとその製造方法、及び半導体装置 |
JP4217906B2 (ja) * | 2004-09-17 | 2009-02-04 | セイコーエプソン株式会社 | 前駆体溶液の製造方法 |
-
2004
- 2004-04-23 JP JP2005505886A patent/JPWO2004097854A1/ja not_active Withdrawn
- 2004-04-23 EP EP04729280A patent/EP1624468A1/en not_active Withdrawn
- 2004-04-23 WO PCT/JP2004/005913 patent/WO2004097854A1/ja not_active Application Discontinuation
- 2004-04-23 KR KR1020057016571A patent/KR20060012573A/ko not_active Application Discontinuation
- 2004-04-29 TW TW093111948A patent/TW200428525A/zh not_active IP Right Cessation
-
2005
- 2005-10-28 US US11/260,209 patent/US7208324B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI415794B (zh) * | 2009-10-23 | 2013-11-21 | Nat Univ Tsing Hua | 合成銦鎵鋅氧化物之方法及使用其形成銦鎵鋅氧化物薄膜之方法 |
Also Published As
Publication number | Publication date |
---|---|
TWI324366B (zh) | 2010-05-01 |
KR20060012573A (ko) | 2006-02-08 |
US7208324B2 (en) | 2007-04-24 |
US20060046320A1 (en) | 2006-03-02 |
JPWO2004097854A1 (ja) | 2006-07-13 |
EP1624468A1 (en) | 2006-02-08 |
WO2004097854A1 (ja) | 2004-11-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7208324B2 (en) | Liquid composition for forming ferroelectric thin film and process for producing ferroelectric thin film | |
CN100466320C (zh) | 用于铁电存储器的掺钕钛酸铋铁电薄膜及其低温制备方法 | |
WO2002102709A1 (fr) | Film ceramique et procede de production et condensateur ferro-electrique, dispositif a semi-conducteurs et autres elements | |
Chaouchi et al. | Characterization of sol–gel synthesised lead-free (1− x) Na0. 5Bi0. 5TiO3–xBaTiO3-based ceramics | |
CN101314545A (zh) | 一种制备电介质陶瓷粉体的喷雾包覆方法及所得的产品 | |
US6585951B1 (en) | Methods for manufacturing dielectric powders | |
CN100527420C (zh) | 铁酸铋/钛酸铋叠层结构电容及其制备方法 | |
JP2002275390A (ja) | 結晶性ゲル分散コーティング溶液及び結晶性ゲル分散コーティング溶液を用いた薄膜形成方法 | |
US20060124890A1 (en) | Liquid composition for forming ferroelectric thin film and process for producing ferroelectric thin film | |
Gautam et al. | Fabrication methods of lead titanate glass ceramics and dielectric characteristics: a review | |
Yan et al. | Achieved high energy density and excellent thermal stability in (1− x)(Bi0. 5Na0. 5) 0.94 Ba0. 06TiO3− x Bi (Mg0. 5Ti0. 5) O3 relaxor ferroelectric thin films | |
JP2007173777A (ja) | 強誘電体層の製造方法 | |
JP4735257B2 (ja) | チタン酸ビスマス微粒子の製造方法 | |
Calzada | Sol–gel electroceramic thin films | |
CN105870123B (zh) | 一种钨钛酸铋铁电薄膜的制备方法 | |
JP5056414B2 (ja) | タンタル酸ストロンチウムビスマス微粒子の製造方法 | |
JP4946128B2 (ja) | ニオブ酸ビスマス系微粒子の製造方法 | |
Xu et al. | Synthesis of (Na 0.5 Bi 0.5) TiO 3 and (Na 0.5 Bi 0.5) 0.92 Ba 0.08 TiO 3 powders by a citrate method | |
JP5029363B2 (ja) | 強誘電体層付き基体の製造方法 | |
Li et al. | Effect of in situ applied electric field on the growth of La2Ti2O7 thin films by chemical solution deposition | |
JP2004331492A (ja) | チタン酸ジルコン酸鉛微粒子の製造方法 | |
CN100471996C (zh) | 具有高介电常数的氧化材料薄膜的制备方法 | |
JP2005001989A (ja) | チタン酸バリウム微粒子の製造方法 | |
Liu et al. | Preparation and characterization of Pb (Zr0. 52Ti0. 48) O3 powders and thin films by a sol-gel route | |
JP2006261491A (ja) | 強誘電体薄膜、強誘電体キャパシタ及びその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MM4A | Annulment or lapse of patent due to non-payment of fees |