TWI324366B - - Google Patents
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- TWI324366B TWI324366B TW093111948A TW93111948A TWI324366B TW I324366 B TWI324366 B TW I324366B TW 093111948 A TW093111948 A TW 093111948A TW 93111948 A TW93111948 A TW 93111948A TW I324366 B TWI324366 B TW I324366B
- Authority
- TW
- Taiwan
- Prior art keywords
- ferroelectric
- thin film
- particles
- ferroelectric thin
- metal compound
- Prior art date
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- 239000002245 particle Substances 0.000 claims description 72
- 239000010409 thin film Substances 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 44
- 239000010408 film Substances 0.000 claims description 43
- 239000007788 liquid Substances 0.000 claims description 40
- 150000002736 metal compounds Chemical class 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 35
- 239000013078 crystal Substances 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 17
- 239000011521 glass Substances 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000011164 primary particle Substances 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 32
- 239000012071 phase Substances 0.000 description 18
- 238000010304 firing Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 239000010936 titanium Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 230000010287 polarization Effects 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 239000002609 medium Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000000137 annealing Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- -1 organic acid salt Chemical class 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
- 239000002994 raw material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910002113 barium titanate Inorganic materials 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000010354 integration Effects 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
- 150000004703 alkoxides Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000013081 microcrystal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- BYUANIDVEAKBHT-UHFFFAOYSA-N [Mo].[Bi] Chemical compound [Mo].[Bi] BYUANIDVEAKBHT-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229910052810 boron oxide Inorganic materials 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
- 239000011362 coarse particle Substances 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 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
- 238000011156 evaluation Methods 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 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
- 238000004017 vitrification Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical class CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-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
- FSGHEPDRMHVUCQ-UHFFFAOYSA-N 2-ethoxyprop-1-ene Chemical compound CCOC(C)=C FSGHEPDRMHVUCQ-UHFFFAOYSA-N 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
- 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 compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 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
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 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
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid 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
- 238000000265 homogenisation Methods 0.000 description 1
- 235000012907 honey Nutrition 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 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
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 239000011344 liquid material Substances 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
- 239000011859 microparticle Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052707 ruthenium Inorganic materials 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
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 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
- 238000010023 transfer printing Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052726 zirconium 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
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Description
1324366 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億體 (FeRAM )係積極利用強介電體薄膜之本身極化特性後, 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—種理想之記億體 者。 做爲Fe RAM用之強介電體材料者目前爲止有鈦酸锆 酸铅系(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。 通吊’此等強介電體薄膜被揭示有藉由濺射法等物理 性氣相成膜法(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 控制精密之組成’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 薄膜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- 1324366 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,必要時進行退火(pre-bake )後,於空氣中以 約70(TC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、蜜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 t〜4 50 t 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 5,925,183號公報寺所不之適當控制前驅物構造之方法, 預先將常介電體之矽酸鉍加入塗層液之方法 (Ferroelectric^,271 卷,2 89 頁(2002 年)),以鈦酸 鉛層做爲晶種層使用之方法(jpn j Appl.Phys,35卷, 1324366 4896 頁 (1996 年)),適當基材之選擇 (J . A m . C e r a m . S 〇 c .,7 5 卷,2 7 8 5 頁(1 9 9 2 年)),滅壓退 火法(Jpn. J.Appl.Phys.,38 卷,5 346 頁(1 999 年)等 者。惟,此等先行方法中燒成溫度均降至 550 °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 (2〇〇2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45〇t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、本身極化性,特別是疲勞特 性寺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+、Sr2+、Ca2+、Pb2+、La2+、K +及 Na +所成群者,B 爲 1324366 至少1種選自 Ti4+、Zr4+、Nb5+ ' Ta5+及 Fe3+所成群 者。)所不之具有耗駄礦構造’平均一次粒徑爲lOOnm以 下,且長寬比爲2以上之板狀或針狀結晶之強介電體氧化 物粒子被分散,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 ABO; (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 之粒子之上述(1)或(2)所載的形成強介電體薄膜用液 狀組成物。 (4 )含強介電體氧化物粒子/可溶性金屬化合物之含 有比率係以氧化物換算之質量比表示爲5/95〜95/5之上述 (1 )〜(3 )中任—項之形成強介電體薄膜用液狀組成 物。 (5 )強介電體氧化物粒子與可溶性金屬化合物之合 計含量爲1〜50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)於基板上塗佈上述(1)〜(5)中任一項之液狀 -8- 1324366 組成物後,於5 5 0 °C以下進行燒成之製造強介電體薄膜之 方法。 (7)強介電體薄膜之膜厚爲1〇〜3〇〇nm之(6)所記 載之強介電體薄膜之製造方法。 【實施方式】 [發明實施之最佳長寬] 以下,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+、 Sr2+、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)係成爲本發明組成物中之根幹的必須成 份。本發明藉由使用將具有該高結晶性之強介電體粒子分 散於液狀媒體之液狀組成物,可大幅降低由目前爲止溶液 法所使用之可溶性金屬化合物溶液進行成膜時所必要的燒 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)所示之鈣鈦礦構造之強介電體者,該一般式之a 較佳爲 Ba2+、Sr2+、Pb2+,B較佳爲 Ti4+、Zr4+。其中又 以A爲Pb,B爲Ti與Zr之複合氧化物之PbCZbTi, x) 〇3(x爲0.1〜0.9者。以下亦稱PZT。)爲佳。當然也可 使用此PZT之Pb位置(site )可以其他元素,如La等稀 土元素進行部份取代之PLZT之公知的強介電體等。 1324366 該強介電體粒子其平均一次粒徑務必爲1 0 0 n m以下。 其中,以一次粒徑係以粒子之長徑爲基準’又’平均粒徑 爲數平均粒徑。當平均一次粒徑大於上述時’薄膜形成時 表面之凹凸變粗,或薄膜中之塡充率無法提昇’介電特性 降低。其中平均一次粒徑較佳爲 50nm以下,特佳爲 10~30nm。當平均一次粒徑未達l〇nm時,粒子之強介電 特性可能降低,故不佳。 本發明中,強介電體粒子具有上述範圍之平均一次粒 徑,同時其長寬必須爲各向異性之結晶粒子,亦即,其長 寬比務必爲2以上之板狀或針狀結晶者。其中,長寬比係 指具有各向異性粒子之長徑/短徑比率,板狀結晶時爲直 徑/厚度之比率,針狀結晶時爲長度/直徑之比率。特別 是,本發明鈣鈦礦型之強介電體氧化物中,本身極化方向 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(0 0 1 )面)使用成長之板狀結晶,塗佈後粒子自動 排列於C軸方向,亦即,容易配向,具有取得較高之本身 極化値的優點。可提昇強介電體粒子之配向性,因此連帶 的亦提昇強介電體薄膜之疲勞特性。本發明中長寬比小於 2時,形成後之強介電體薄膜之特性會降低,因而不理 想。長寬比爲5以上爲最理想。 具有上述特性之強介電體粒子特別由具有高度結晶 性,因此於玻璃基質中使強介電體粒子結晶化後去除玻璃 基質成份所取得的粒子較佳。亦即,於玻璃母材融液中溶 解做爲強介電體粒子之結晶化之成份,融液進行急速冷卻 -10- 1324366 玻璃化後’再度進行加熱退火後母材中藉由析出微結晶之 玻璃結晶化法所取得之粒子。所析出之微結晶藉由適當藥 液等溶解玻璃基質後被取出。 該玻璃基質中結晶化之超微粒子易於控制形態,藉由 退火處理之條件等較易製作各向異性較大之微粒子,同時 亦具有易於取得長寬比較大的粒子之優點。 上述玻璃母材可使用硼酸系、磷酸系、矽酸系等,由 熔融性、易製造與目的氧化物之複合化合物及基質溶離之 容易性等觀點,又以使用硼酸系之玻璃母材爲佳。 以下,以製作鈦酸銷酸鉛(PZT )微結晶之方法爲例 具體說明強介電體氧化物粒子之製造時,可以下①〜④步 驟取得強介電體粒子。 混合玻璃形成成份(如氧化硼)與目的之強介電體氧 化物粒子組成之金屬氧化物(如氧化鉻、氧化鈦及氧化 鉛)後,以1 200°c以上之溫度使整體熔融[熔融]。 使熔融玻璃急速冷卻,取得含強介電體氧化物組成之 金屬離子的玻璃[玻璃化]。 以5 5 0°C~700°C之溫度進行退火處理,玻璃中形成強 介電體氧化物之結晶核,控制退火條件,使成長至所定粒 徑爲止[結晶化]。 藉由酸、水或其混合物去除玻璃母材成份(如:氧化 棚)得到強介電體粒子(如’ P b ( Z r X T i 1 · x ) 〇 3 )[瀝 灑]0 藉由上記一連串步驟’於退火溫度範圍下,以極高粘 -11 - 1324366 度之玻璃做爲母材進行結晶化,因此,極易控制強介電體 粒子之粒徑及粒子形態,且可取得高結晶性之微結晶者。 另外,本發明中藉由加熱可形成強介電性氧化物之可 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,可顯示強介電性之化合 物。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種以上之可溶性金屬化合物,或使用以所定 比例含2種以上之金屬之複合金屬化合物。此等可溶性金 屬化合物可使用硝酸鹽等無機酸鹽、乙基己酸鹽等有機酸 鹽、乙醯丙酮絡合物等有機金屬絡合物、或金屬烷氧化物 等,特別以使用有機酸鹽、有機金屬絡合物、或金屬烷氧 化物爲較佳。 由本發明之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的作用,此可溶性金屬化合物 可使前述強介電體粒子做爲核進行結晶成長,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, 亦具有提昇做爲強介電體薄膜整體之介電特性作用。 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,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。惟,考量該強介電 體粒子做爲結晶核作用時,又以形成盡可能與強介電體粒 子相同組成的強介電體者爲佳。 -12- 1324366 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成氧化物時之氧化物換算的 質量比表不’強介電體粒子/可溶性金屬化合物之比率較 佳爲5/95~95/5。當此強介電體粒子大於此範圍時,則結 合劑成份不足’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 0/70以上時,則可提昇強介電體粒子之配向 性’易取得高特性之強介電體薄膜,故特別理想。反之, 該比率做成70/30以下則較易取得密緻之強介電體薄膜較 爲理想。 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’使用於強介電體薄膜形成用之塗佈液 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溶解或分散,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。液狀媒 體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_等)、酯(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 圜寺)、Ηθ肪族烴(環己院 '癸院等)、芳香族烴(甲 本、一甲本)、含氮有機溶媒(乙腈、ν—甲基吡咯烷酮 等)、或此等之2種以上的混合溶媒。具體之液狀媒體可 依其?ifl成物中之結晶粒子之種類,表面狀態,可溶性金屬 -13- 1324366 化合物之種類,更依其塗佈方法適當選取、混合使用。 又,液狀媒體中亦可含部份可溶性金屬化合物之未溶解 份。 本發明之液狀組成物中的固形份(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%爲宜。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,形成本發明之液狀組成物之上述強介電體粒子或 可溶性金屬鹽化合物,於媒體中溶解或分散時,可使用球 磨器、混砂機等介質硏磨器、超音波式、攪拌式等各種勻 漿器、噴射硏磨器、滾輥硏磨器等已知之方法、裝置。 本發明之液狀組成物中亦可含有爲分散該強介電體粒 子或可溶性金屬化合物之分散劑、爲改善塗膜之液流體特 性等之各種界面活性劑或表面處理劑、樹脂成份等。惟, 此等大量添加時’於燒成後易呈殘碳份殘留,因此以必要 最小限之量進行添加爲宜。 基板上塗佈本發明之液狀組成物後,進行燒成後可製 造強介電體薄膜。塗佈方法可使用己知之方法者。理想之 具體例如:旋轉塗佈法 '浸漬塗佈法、噴霧塗佈法、網版 印刷法、轉印印刷法等例。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。 本發明中用於形成薄膜之基板例如:Si、GaAs等單結 -14- 1324366 晶半導體基板、BaTi〇3、SrTi03、MgO、Al2〇3等之單結 晶介電體基板’於此等表面上堆積多結晶Si,或做爲電極層 之Pt、Ir、Ir02、RU、Ru〇2等者,或於半導體基板與該電 極層之間設置Si〇2、Si3N4等之絕緣層或Ti、Ta等之緩衝 層者。惟,基板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之液狀組成物後,較佳爲去 除介質,一般於1〇〇〜400 °C下進行乾燥1分鐘至2小時 後’進行燒成。此燒成係如上述,本發明可採用低溫範 圍’理想者爲5 5 0 °C以下,依情況於4 5 0 °C以下進行。當 然燒成亦可採用超過550 °C之溫度者,不同用途下有時該 高溫亦有利燒成。燒成時間依其溫度,氣氛而異,理想者 爲進行1分鐘至2小時。此燒成係使可溶性金屬化合物進 行分解及/或結晶化者,可適當選擇使用大氣中、氧中、 不活性氣體中等。燒成亦可使用擴散爐類之電爐,使用可 急速昇溫之熱感光板、紅外線燈退火爐(RTA )等時,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,膜厚較佳爲 10〜3 00nm。當膜厚不足i〇nm時,則不易取得均質膜者, 反之’超出3 00nm時,則恐於膜中出現龜裂而不理想。另 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 未受限於以下實施例。又,例6〜例8爲比較例者。 -15- 1324366 [例1一強介電體粒子(PZT)之製作] 使氧化鉛、氧化銷、氧化鈦(金紅石),及氧化棚分 別以P b 0、Z r 0 2、T i 0 2及Β 2 0 3形態秤取4 7.2莫耳%、 13.3莫耳%、1 1 .7莫耳%、及27.82莫耳%後,使用少量乙 醇以自動硏鉢充份濕式混合乾燥之後作爲原料粉末。將取 得之原料粉末塡充於附融液滴入用噴嘴之鈾製容器(含 1 〇 %铑)後’在以矽化鉬做爲發熱體之電爐中丨3 5 〇它下進 行加熱2小時後,完全熔融之。再加熱噴嘴部位後,將融 液滴入設置於電爐下之雙滾輥(滾輥徑1 50mm、滾輥旋轉 數5 0 rp m、滾輥表面溫度3 0 °C )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線繞射結 果’爲非晶質物質。此碎片狀固形物於500°C下加熱1 2小 時後’ B2〇3坡璃基質中使強介電體粒子結晶化者。再使該 碎片粉加入維持於80。(:之lmol/L醋酸水溶液中攪拌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X線繞射後,判定爲僅P b (Zr〇.52 Ti 〇.48 ) 〇3結晶所成之粉末者。又,Zr與Ti之比 率依ICP法進行定量。又,藉由透過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20nm,厚度爲 9nm,長寬比爲2.22者。 [例2—強介電體粒子BaTi03之製作] -16- 1324366 使碳酸鋇、氧化鈦(金紅石) '及氧化硼分別以 Ba〇、Ti02' 及 B203 秤取 50.0' 16.7、及 33.3莫耳%後, 使用少量乙醇’以自動硏鉢充份進行濕式混合乾燥後做成 原料粉末。將取得之原料粉末塡充於附融液滴入用噴嘴之 舶製容器(含10%铑)後,在矽化鉬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 〇 m m、滾輥旋轉 數5〇rpm、滾輥表面溫度3(rc )中滴入融液後,取得碎片 狀固形物。 取得之碎片狀固形物確定呈透明狀,粉末X線繞射之 結果爲非晶質物質者。此碎片狀固形物於5 9 0。(:下加熱1 2 小時後,進行結晶化處理。再將此碎片粉加入於維持8 0 °C 之1 m ο 1 / L之醋酸水溶液中,攪拌〗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線繞射後’證明爲僅由鈦酸鋇結晶所成之 粉末者。又’藉由透過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25nm,厚度爲10nm,長 寬比爲2.5 0者。 [例3 - PZT強介電體薄膜之製作] 利用濕式噴射硏磨器使例1取得之PZT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10 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,測得90nm,且爲良好之分散體。 -17- 1324366 使醋酸鉛、四丁基鈦酸酯、四丁基鍩酸酯及乙醯丙酮 於2 —乙氧基丙醇中溶解成爲 Pb:Zr:Ti:乙醯丙酮 = 1.05: 0.53: 0.47: 1: 00(莫耳比),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 離子交換水成爲(Pb + Zr + Ti )之2倍(莫耳比)。之後, 再度於氮氣流中,1 30°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 0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)混合成爲5 0/5 0後,做成本發明之組成物。 基板使用於表面層合Pt層(厚度200nm) /Ti層(厚 度20nm) /熱氧化Si02層(厚度800nm)之矽單結晶基 板,藉由旋轉塗佈法將該組成物塗佈於表面之Pt層後, 於加熱板上以20(TC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4 50 °C下進行燒成30 分鐘。 取得之被膜爲厚度lOOnm,且X線繞射結果,僅由優 先配位於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0.1mm 0之Pt電極,於PTA 爐中4〇0°C,進行1 5分鐘之後退火處理製作電容器後,測 定強介電體滯後特性時,抗電場値爲44kV/cm,本身極化 値爲SSpC/cm2者。取得之強介電體電容器之疲勞特定進 行評估(循環試驗中,本身極化降低爲初期之5 %以上的 循環數)時,重覆進行3 V、1 08次循環後,本身極化値之 •18- 1324366 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BaTi〇3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1 0 質量%之B a T i 0 3分散液C。利用激光散射fii度分佈計測疋 該分散液C之分散粒徑後爲80nm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 丙醇中成爲Ba: Ti:二乙二醇=1: 1: 1(莫耳比)’於氮 氣流1 1 0°C下進行迴流操作4小時後,冷卻至室溫,緩緩添 加離子交換水成爲(Ba + Ti )之2倍(莫耳比)。隨後,再 度於氮氣流中以1 1 〇°C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成爲質量比 (氧化物換算)70/3 0進行混合後,做成本發明之組成物。 於表面層合 Pt 層(厚度 2〇Onm) /Ti 層(厚度 20nm ) /熱氧化Si02層(厚度800nm )之矽單結晶基板做 爲基板使用後,於表面Pt層上藉由旋轉塗佈法塗佈上述 組成物後,於加熱板上以2 0 0 °C乾燥3 0分鐘。此塗佈一乾 燥之處理進行3次後,利用RTA爐於氧中5 00。(:下進行燒 成2 0分鐘。 取得被膜其厚度爲120nm,X線繞射之結果,僅由優 先配向於C軸方向之BaTi〇3結晶相所成之被膜。更於此 -19- 1324366 被膜上錯由DC濺射法製作o.imm 0之Pt電極。於RTA 爐中以45 0°C進行後退火處理1 5分鐘後,製造電容器,測 定強介電體滯後特性時’測得抗電場値爲3 〇kV/cm,本身 極化値爲19pC/cm2。與例3同法進行評估取得之強介電 體電容器之疲勞特性後’重覆±3¥、1〇6次之循環後仍可控 制本身極化値之變化量爲約5%者。 [例5〜7] 使例1之分散液與可溶性金屬化合物液B之混合比以 表1所示的比例變化,與例3同樣製作強介電體薄膜,進 行評估時’得到表1所示的結果。以例5、例6所得之強 介電體薄膜係X線繞射的結果爲C軸方向優先配向之PZT 單相。 [例8] 使用含1 0質量%之以固相法所製成之一次平均粒徑 1.2μηι (長寬比1 )之球狀ΡΖΤ結晶粒子的分散液Ε,取 代例3之強介電體結晶分散液a後,與例3同樣進行成膜 /評估。取得之相係由P Z T單相所成之強介電體相者,分 極特性亦與例3取得之被膜相等者,惟,疲勞特性之評估 係3 V ’ 1 06次循環,本身極化幾乎爲零,明顯出現劣化 者。另外’ X線繞射之結果,強介電體相爲無配向者。 [例9] -20- 1324366 利用行星式球磨器將固相法所製成之球狀PZT粒子 (平均一次粒徑1 .2μηι )進行粉碎40小時,取代例3之 強介電體結晶分散液Α。電子顯微鏡觀察結果,粒徑爲微 細化至40nm者。利用此微粉末與例3之分散液A同樣調 製分散液後,與例3同樣製作PZT被膜。取得之相爲PZT 單相所成之強介電體相,而,也有因粉碎造成PZT結晶之 變形的影響或本身極化値變小,且,疲勞特性於1 〇δ次之 循環下,本身極化亦降至初期之50%者。另外,X線衍線 之結果,強介電體相爲無配向者。 [表1]
例 結晶粒子 (a) 平均一次粒 子徑(nm) 長寬比 可溶性金屬化 合物(b) 組成物中(a) / (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。。 例7 — — — 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 - 1324366 [表2] 例 膜厚(nm) 結晶相 抗電場 (kV/cm) 本身極化 (μΟ/οιη2 ) 疲勞特性 (循環) 例3 100 PZT單相 44 35 >108 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] 依據本發明時,以溶液法成膜取得強介電體薄膜時, 可以較低溫,特別是 5 5 0 °C以下,更於4 5 0 °C以下之溫度 下燒成,因此,本發明可提供可於高集成所須理論電路上 形成強介電體薄膜,且可製作具有良好抗高電性、本身極 化性、特別是疲勞特性優異之強介電體特性之薄膜的薄膜 形成組成物,及使用其之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用於製造記憶元件 及其他裝置。特別是膜厚爲10〜3 OOnm時,可期待適用於 FeRAM 者。 -22-
Claims (1)
1324366.— 一__ :的I月分曰修正本 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 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—種選自^“、。“、^”、丁^ +及Fe3 +所成群者) 所示之鈣鈦礦構造,平均一次粒徑爲lOOnm以下,且長寬 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屬化合物 所成者。 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形成具有一般 式 AB〇3 ( A 係至少一種選自 Ba2+、Sr2+、Ca2+、Pb2+、 La2+、K+及Na+所成群者,b係至少一種選自Ti4+ ' Zr4+、Nb5+、Ta5 +及F e 3 +所成群者)所示之鈣鈦礦構造之 強介電體氧化物的化合物。 3 .如申請專利範圍第1或2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,去除玻璃基質成分,所 得的粒子。 4.申請專利範圍第1或2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 之含有比率係以氧化物換算之質量比表示爲5/95〜95/5 者。 5_如申請專利範圍第1或2項之形成強介電體薄膜用 -23- 1324366 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1〜5 0質量%。 6. —種強介電體薄膜之製造方法,其特徵係將如申請 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 (TC以下之溫度下進行燒成。 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1〇〜300nm。 -24-
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