TW201500291A - LaNiO薄膜形成用組成物及使用該組成物之LaNiO薄膜的形成方法 - Google Patents
LaNiO薄膜形成用組成物及使用該組成物之LaNiO薄膜的形成方法 Download PDFInfo
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- TW201500291A TW201500291A TW103105481A TW103105481A TW201500291A TW 201500291 A TW201500291 A TW 201500291A TW 103105481 A TW103105481 A TW 103105481A TW 103105481 A TW103105481 A TW 103105481A TW 201500291 A TW201500291 A TW 201500291A
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- 239000000203 mixture Substances 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims description 40
- 229910002340 LaNiO3 Inorganic materials 0.000 title abstract 7
- 239000010409 thin film Substances 0.000 title description 14
- 239000002243 precursor Substances 0.000 claims abstract description 72
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003381 stabilizer Substances 0.000 claims abstract description 15
- 241000877463 Lanio Species 0.000 claims description 143
- 229910052751 metal Inorganic materials 0.000 claims description 44
- 239000002184 metal Substances 0.000 claims description 42
- 238000000576 coating method Methods 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 31
- 239000003990 capacitor Substances 0.000 claims description 29
- 239000012298 atmosphere Substances 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 238000010304 firing Methods 0.000 claims description 11
- 150000007942 carboxylates Chemical class 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- 150000004703 alkoxides Chemical class 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 2
- 235000013877 carbamide Nutrition 0.000 claims 1
- 239000004202 carbamide Substances 0.000 claims 1
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 abstract description 34
- 239000010408 film Substances 0.000 description 131
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 239000002245 particle Substances 0.000 description 16
- 238000001354 calcination Methods 0.000 description 15
- 239000010410 layer Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000013078 crystal Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000000224 chemical solution deposition Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000011085 pressure filtration Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- GEADFHLCHUFFBM-UHFFFAOYSA-N C(C)#N.C(C(=O)C)(=O)O Chemical compound C(C)#N.C(C(=O)C)(=O)O GEADFHLCHUFFBM-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 2
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- CUGDYSSBTWBKII-LXGUWJNJSA-N (2r,3r,4r,5s)-6-(dimethylamino)hexane-1,2,3,4,5-pentol Chemical compound CN(C)C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO CUGDYSSBTWBKII-LXGUWJNJSA-N 0.000 description 1
- UVPKUTPZWFHAHY-UHFFFAOYSA-L 2-ethylhexanoate;nickel(2+) Chemical compound [Ni+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O UVPKUTPZWFHAHY-UHFFFAOYSA-L 0.000 description 1
- YFHDZSKZCMRHPU-UHFFFAOYSA-N C1C(C2=CC=CC3=C2C1=CC=C3)CC(=O)C(=O)O Chemical compound C1C(C2=CC=CC3=C2C1=CC=C3)CC(=O)C(=O)O YFHDZSKZCMRHPU-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- VJFFDDQGMMQGTQ-UHFFFAOYSA-L barium(2+);2-ethylhexanoate Chemical compound [Ba+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O VJFFDDQGMMQGTQ-UHFFFAOYSA-L 0.000 description 1
- CPUJSIVIXCTVEI-UHFFFAOYSA-N barium(2+);propan-2-olate Chemical compound [Ba+2].CC(C)[O-].CC(C)[O-] CPUJSIVIXCTVEI-UHFFFAOYSA-N 0.000 description 1
- QIWWQTLNHRQHFW-UHFFFAOYSA-N cesium;propan-2-olate Chemical compound [Cs+].CC(C)[O-] QIWWQTLNHRQHFW-UHFFFAOYSA-N 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- UPIZSELIQBYSMU-UHFFFAOYSA-N lanthanum;sulfur monoxide Chemical compound [La].S=O UPIZSELIQBYSMU-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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- H01G7/00—Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
此LaNiO3薄膜形成用組成物係包含LaNiO3前驅物與乙酸,前述LaNiO3薄膜形成用組成物100質量%中之LaNiO3前驅物的比例以氧化物換算為1~20質量%,且進一步包含相對於組成物中之LaNiO3前驅物的合計量1莫耳為超過0且10莫耳以下之由N-甲基甲醯胺所構成的安定化劑。
Description
本發明係關於用以藉由化學溶液法(Chemical Solution Deposition,CSD法)來形成於薄膜電容器、強介電體記憶體(Ferroelectric Random Access Memory,FeRAM)用電容器、壓電元件或焦電型紅外線檢測元件等之電極所使用的LaNiO3薄膜之組成物及使用該組成物之LaNiO3薄膜的形成方法。更詳細而言,本發明係關於用以形成膜本身之電特性優異,且適合控制形成於該膜上的介電體層等之結晶配向性的LaNiO3薄膜之組成物及使用該組成物之LaNiO3薄膜的形成方法。
本發明係對於2013年3月25日所申請的日本專利申請第2013-061914號主張優先權,並將其內容援用於此。
LaNiO3(LNO),係具有高導電性等之優異電特性,此外,作為於(100)面具有強的自我配向性之物質
乃為周知(例如,參照“Preparation and evaluation of LaNiO3 thin film electrode with chemical solution deposition”,Journal of the Europian Ceramic Society 24(2004)1005-1008)。進而,LaNiO3(LNO)薄膜,由於具有擬立方晶的鈣鈦礦(Perovskite)結構,因此與鈣鈦礦型之強介電體薄膜的適合性(compatibility)亦佳,晶格常數之參差小,故作為於薄膜電容器等中形成優先配向於(100)面的強介電體薄膜時之結晶配向性控制層運用。此外,LaNiO3(LNO)薄膜,膜本身之電阻較低,相較於使用Pt等之金屬作為電極的情況,強介電體膜的分極反轉疲勞特性亦較為優異,因此,亦可將其本身利用於強介電體記憶體用電容器或壓電元件等之電極膜。進而,由於具有透光性,因此亦可利用於焦電型紅外線檢測元件的電極膜等。
另一方面,經本發明者們進行驗證之後,確認出即使於使用上述“Preparation and evaluation of LaNiO3 thin film electrode with chemical solution deposition”,Journal of the Europian Ceramic Society 24(2004)1005-1008等以往周知之文獻所揭示的材料或方法等來形成的情況中,依據所使用的前驅物之種類或溶劑等其他成分之組合或其比例等的條件,LaNiO3(LNO)亦未展
現自我配向性,或者在其程度上產生差異。尤其,於藉由溶膠-凝膠法等之CSD(Chemical Solution Deposition)法形成LaNiO3(LNO)薄膜的情況中,用以使具有LaNiO3(LNO)的自我配向性顯著地表現之詳細的條件等,目前所揭示的文獻等中尚未明確顯示,此乃現今情況。
本發明之目的係提供一種電特性優異,可將其本身使用於強介電體記憶體用電容器或壓點元件、或者焦電型紅外線檢測元件等之電極膜,且用以於薄膜電容器等中形成能夠使形成於該膜上之介電體層的結晶配向性容易地優先配向於(100)面之LaNiO3薄膜的組成物,及使用該組成物之LaNiO3薄膜的形成方法。
本發明之第1觀點,係一種LaNiO3薄膜形成用組成物,其係包含LaNiO3前驅物與乙酸,其特徵為,前述LaNiO3薄膜形成用組成物100質量%中之前述LaNiO3前驅物的比例以氧化物換算為1~20質量%,且進一步包含相對於前述LaNiO3薄膜形成用組成物中之前述LaNiO3前驅物的合計量1莫耳為超過0且10莫耳以下之由N-甲基甲醯胺所構成的安定化劑。
本發明之第2觀點,係根據第1觀點的發明,進而上述LaNiO3前驅物為金屬羧酸鹽、金屬硝酸鹽、金屬烷氧化物、金屬二醇錯合物、金屬三醇錯合物、金屬β-二酮錯合物、金屬β-二酮酯錯合物、金屬β-亞胺基酮錯合物
或金屬胺基錯合物。
本發明之第3觀點,係根據第2觀點的發明,進而上述LaNiO3前驅物當中,成為La源之LaNiO3前驅物及成為Ni源之LaNiO3前驅物的至少一者為乙酸鹽或硝酸鹽。
本發明之第4觀點,係一種LaNiO3薄膜的形成方法,其係使用如第1至第3觀點中任一觀點所記載之LaNiO3薄膜形成用組成物。
本發明之第5觀點,係一種LaNiO3薄膜的形成方法,其特徵為具有:將如第1至第3觀點中任一觀點所記載之LaNiO3薄膜形成用組成物塗佈於耐熱性基板而形成塗膜的步驟;以及將具有此塗膜的基板在大氣壓之氧化環境或含水蒸氣環境中煅燒之後,或者在重複進行2次以上由上述塗膜之形成至煅燒直至成為所期望的厚度為止之後,以結晶化溫度以上之溫度進行燒成的步驟,且使LaNiO3薄膜優先配向於(100)面。
本發明之第6觀點,係一種方法,其係製造具有由如第4或5觀點之方法形成的LaNiO3薄膜之薄膜電容器、電容器、IPD、DRAM記憶體用電容器、層合電容器、強介電體記憶體用電容器、焦電型紅外線檢測元件、壓電元件、電光學元件、致動器、共振元件、超音波馬達、電開關、光學開關或LC雜波濾波器元件的複合電子零件。
本發明之第1觀點的LaNiO3薄膜形成用組成物,其係包含LaNiO3前驅物與乙酸之LaNiO3薄膜形成用組成物,其特徵為,前述LaNiO3薄膜形成用組成物100質量%中之前述LaNiO3前驅物的比例以氧化物換算為1~20質量%,且進一步包含相對於前述LaNiO3薄膜形成用組成物中之前述LaNiO3前驅物的合計量1莫耳為超過0且10莫耳以下之由N-甲基甲醯胺所構成的安定化劑。藉由本發明之第1觀點的構成,若使用此LaNiO3薄膜形成用組成物,則可形成導電性或分極反轉疲勞特性等之電特性優異,能夠將其本身使用於強介電體記憶體用電容器或壓電元件等之電極膜的LaNiO3薄膜。此外,可形成亦適於焦電型紅外線檢測元件之電極膜等的LaNiO3薄膜。此外,若使用此LaNiO3薄膜形成用組成物,則可形成強優先配向於(100)面的LaNiO3薄膜,因此,尤其於製造薄膜電容器或壓電元件等時,可用來形成用以控制介電體層之結晶配向性的結晶配向性控制層。藉此,可將形成於該膜上之介電體層的結晶配向性容易地優先配向於(100)面。
於本發明之第2觀點的LaNiO3薄膜形成用組成物中,作為上述LaNiO3前驅物係含有金屬羧酸鹽、金屬硝酸鹽、金屬烷氧化物、金屬二醇錯合物、金屬三醇錯合物、金屬β-二酮錯合物、金屬β-二酮酯錯合物、金屬β-亞胺基酮錯合物或金屬胺基錯合物。藉此,可更提昇組成物之組成均勻性。
於本發明之第3觀點的LaNiO3薄膜形成用組成
物中,上述LaNiO3前驅物當中,成為La源之LaNiO3前驅物或成為Ni源之LaNiO3前驅物的至少一者含有乙酸鹽或硝酸鹽。作為LaNiO3前驅物,尤其藉由使用乙酸鹽或硝酸鹽,即使調製了較高濃度的LaNiO3薄膜形成用組成物時,亦可提昇保存安定性。
於本發明之第4或第5觀點的LaNiO3薄膜之形成方法中,係使用上述本發明之LaNiO3薄膜形成用組成物而形成LaNiO3薄膜。此外,本發明之第5觀點的LaNiO3薄膜之形成方法,係具有:將上述本發明之LaNiO3薄膜形成用組成物塗佈於耐熱性基板而形成塗膜的步驟、以及將具有此塗膜的基板在大氣壓之氧化環境或含水蒸氣環境中煅燒之後,或者在重複進行2次以上由上述塗膜之形成至煅燒直至成為所期望的厚度為止之後,以結晶化溫度以上之溫度進行燒成的步驟。藉此,可形成電特性等優異,且強優先配向於(100)面的LaNiO3薄膜。於此形成方法中,由於得到強優先配向於(100)面的LaNiO3薄膜,因此若將藉由此方法所得到的LaNiO3薄膜使用於結晶配向性控制層,則可較容易地形成優先配向於(100)面的介電體層。
於本發明之第6觀點的製造方法中,於製造例如強介電體記憶體或壓電元件等時,由於將上述以本發明之形成方法所得到的LaNiO3薄膜使用於強介電體記憶體之電容器或壓電體電極、焦電型紅外線檢測元件之電極等,因此可得到電特性,尤其分極反轉疲勞特性優異的裝置。
此外,於製造薄膜電容器等時,若將上述以本發明之成形方法所得到的LaNiO3薄膜使用於用以控制介電體層之結晶配向性的結晶配向性控制層,則不依存於複雜的成膜條件,而可使介電體層之結晶配向性容易優先配向於(100)面。此外,尤其於壓電元件的情況中,可提昇壓電特性。
第1圖,係顯示以實施例1-1所形成的LaNiO3薄膜之XRD圖型的圖。
接著,說明用以實施本發明之形態。
本實施形態之LaNiO3薄膜形成用組成物(以下,表記為組成物),係將用以形成LaNiO3薄膜之組成物作了改良者。本實施形態之組成物的特徵構成,係組成物為包含LaNiO3前驅物與乙酸,且組成物100質量%中之LaNiO3前驅物的比例以氧化物換算為1~20質量%,且進一步包含相對於組成物中之LaNiO3前驅物的合計量1莫耳為超過0且10莫耳以下之由N-甲基甲醯胺所構成的安定化劑。
組成物中所含有的上述LaNiO3前驅物,係於形成後之LaNiO3薄膜中用以構成複合金屬氧化物(LaNiO3)的原料,可列舉:La或Ni之各金屬元素的金屬
羧酸鹽、金屬硝酸鹽、金屬烷氧化物、金屬二醇錯合物、金屬三醇錯合物、金屬β-二酮錯合物、金屬β-二酮酯錯合物、金屬β-亞胺基酮錯合物或金屬胺基錯合物。具體而言,成為La源之LaNiO3前驅物,係可列舉:乙酸鑭、2-乙基己酸鑭等之金屬羧酸鹽、硝酸鑭等之金屬硝酸鹽、鑭異丙氧化物等之金屬烷氧化物、乙醯丙酮酸鑭等之金屬β-二酮錯合物等。此外,成為Ni源之LaNiO3前驅物,係可列舉:乙酸鎳、2-乙基己酸鎳等之金屬羧酸鹽、硝酸鎳等之金屬硝酸鎳、乙醯丙酮酸鎳等之金屬β-二酮錯合物等。其中,就對於溶劑之溶解度的高度或保存安定性等之觀點而言,LaNiO3前驅物,較佳為成為La源之LaNiO3前驅物或成為Ni源之LaNiO3前驅物的至少一者為乙酸鹽或硝酸鹽。另外,於成為La源之LaNiO3前驅物、成為Ni源之LaNiO3前驅物為水合物的情況中,係可在預先藉由加熱等之手段進行脫水後使用,亦可於前驅物之合成中藉由蒸餾等之手段進行脫水。
將組成物100質量%中上述LaNiO3前驅物(成為La與之Ni源的合計)所佔的比例以氧化物換算限定於上述範圍內之原因在於,由於LaNiO3前驅物的比例未達下限值時,塗佈膜的膜厚會變得過薄,因此會產生在膜上發生龜裂的缺陷,另一方面,若超過上限值,則會產生沉澱等之保存安定性惡化。其中,組成物100質量%中所含之上述LaNiO3前驅物的比例,較佳為以氧化物換算成為3~15質量%者。另外,以氧化物換算的比例,係指當假設組成
物中所含有的金屬元素全部成為氧化物時,組成物100質量%中金屬氧化物所佔的比例。此外,成為La源之LaNiO3前驅物及成為Ni源之LaNiO3前驅物的混合比,較佳為以使La元素與Ni元素的金屬原子比(La/Ni)成為1:1的比例。
組成物中所含之乙酸,係成為組成物之溶劑的成分。於本實施形態之組成物中,將溶劑成分限定為乙酸的原因在於,若將此等以外之例如水作為溶劑成分,則塗膜形成性,及藉由所得到的組成物所形成的塗膜之塗膜性能會惡化。另一方面,藉由使用乙酸作為溶劑,並不會使塗膜形成性及塗膜性能等惡化,可形成強優先配向於(100)面的LaNiO3薄膜。
組成物100質量%中之乙酸的比例,較佳為2~98%,更佳為40~70%。此原因在於,若乙酸的比例超過上述上限則塗膜的膜厚會過薄,因此,產生於膜上發生龜裂的缺陷,若低於上述下限則會產生沉澱等之保存安定性惡化。
此外,進一步含有相對於組成物中之LaNiO3前驅物的合計量1莫耳為超過0且10莫耳以下之由N-甲基甲醯胺所構成的安定化劑。藉由含有此N-甲基甲醯胺作為安定化劑,尤其可提昇組成物之塗膜形成性,及藉由所得到的組成物所形成之塗膜的塗膜性能或組成物之保存安定性。此外,將N-甲基甲醯胺之比例設為相對於組成物中之LaNiO3前驅物的合計量1莫耳為10莫耳以下的理由在於,若超過10莫耳則安定化劑之熱分解會變慢,而產生於膜中
殘存空隙之缺陷。其中,由N-甲基甲醯胺所構成的安定化劑之比例,較佳係設為相對於組成物中之LaNiO3前驅物的合計量1莫耳為2~8莫耳。
為了得到本實施形態之LaNiO3薄膜形成用組成物,首先,分別準備上述成為La源之LaNiO3前驅物與成為Ni源之LaNiO3前驅物,進行秤量,以使此等成為賦予上述所期望之金屬原子比的比例。此外,安定化劑,係準備N-甲基甲醯胺,以相對於上述LaNiO3前驅物(成為La源之LaNiO3前驅物與成為Ni源之LaNiO3前驅物的合計量)1莫耳成為上述特定的比例之方式進行秤量。
接著,將此等LaNiO3前驅物、與作為安定化劑之N-甲基甲醯胺投入反應容器內,進而,投入作為溶劑之乙酸,以使調製後之組成物100質量%中LaNiO3前驅物所佔的比例成為上述比例。接著,藉由進行充分地混合直至固體成分完全溶解並使其反應,而得到組成物。另外,混合之後,為了控制組成物之經時變化,較佳為在惰性氣體環境中,以80~200℃之溫度預先進行加熱0.5~2小時較為理想。
於本實施形態中,將上述所調製出的組成物藉由過濾處理等來去除粒子,較佳為粒徑0.5μm以上(尤其0.3μm以上,特別是0.2μm以上)的粒子個數為溶液每1毫升50個/毫升以下。另外,較佳為藉由以過濾處理等所進行之粒子的去除而為組成物內之0.2μm以上的粒子被去除的狀態。另外,為了測定組成物中之粒子的個數,係使
用光散亂式粒子計數器。
若組成物中之粒徑0.5μm以上的粒子之個數超過50個/毫升,則成為長期保存安定性差者。此組成物之粒徑0.5μm以上的粒子之個數越少越好,尤其以30個/毫升以下為佳。
如成為上述粒子個數般地,處理調製後之組成物的方法雖無特別限定,但可列舉例如以下的方法。第1方法,係使用市售之0.2μm孔徑的薄膜過濾器,以注射器進行壓送的過濾法。第2方法,係組合市售之0.05μm孔徑的薄膜過濾器與加壓槽的加壓過濾法。第3方法,係組合上述第2方法所使用的過濾器與溶液循環槽的循環過濾法。
於任一種方法中,以過濾器所進行之粒子的捕捉率會隨著溶液壓送壓力而異。壓力越低捕捉率會越高一事乃一般周知,尤其,針對第1方法、第2方法,為了實現使粒徑0.5μm以上之粒子的個數成為50個以下的條件,較佳為溶液在低壓下非常緩慢地通過過濾器。
接著,針對本實施形態之LaNiO3薄膜的形成方法進行說明。首先,將上述LaNiO3薄膜形成用組成物塗佈於基板上,形成具有特定厚度的塗膜。針對塗佈法,雖無特別限定,但可列舉:旋轉塗佈法、浸塗法、LSMCD(Liquid Source Misted Chemical Deposition)法或靜電噴塗法等。形成LaNiO3薄膜的基板雖依據其用途等而異,但於作為例如薄膜電容器等之結晶配向性控制層利用的情況
中,係使用形成有下部電極的矽基板或藍寶石基板等之耐熱性基板。形成於基板上之下部電極,係使用Pt或Ir、Ru等具有導電性,且不與LaNiO3薄膜產生反應的材料。此外,可使用隔著密著層或絕緣體膜等將下部電極形成於基板上的基板等。具體而言,係可列舉具有Pt/Ti/SiO2/Si、Pt/TiO2/SiO2/Si、Pt/IrO/Ir/SiO2/Si、Pt/TiN/SiO2/Si、Pt/Ta/SiO2/Si、Pt/Ir/SiO2/Si之層合結構(下部電極/密著層/絕緣體膜/基板)的基板等。另一方面,利用於強介電體記憶體用電容器或壓電元件、焦電型紅外線檢測元件等之電極的情況中,係可使用矽基板、SiO2/Si基板、藍寶石基板等之耐熱性基板。
於基板上形成塗膜之後,將此塗膜煅燒,進一步燒成而使其結晶化。煅燒係使用加熱板或RTA等,在特定條件下進行。煅燒係為了除去溶劑並且將金屬化合物熱分解或水解以轉化為複合氧化物而進行,因此,在空氣中、氧化環境中、或含水蒸氣環境中進行較為理想。即使在空氣中進行加熱,亦可藉由空氣中的濕氣而充分確保水解所需之水分。另外,於煅燒前,尤其,為了去除低沸點成分或所吸附的水分子,亦可使用加熱板等,在60~120℃之溫度下,進行1~5分鐘低溫加熱。煅燒,係以藉由在150~550℃之溫度下,1~10分鐘來進行為佳。從組成物之塗佈至煅燒為止的步驟,於以一次塗佈便可得到所期望的膜厚之情況中,係在進行一次從塗佈至煅燒的步驟之後,進行燒成。或者,亦可為了成為所期望的膜厚,而
重複進行複數次從塗佈至煅燒的步驟,最後再一併進行燒成。
燒成,係用來將煅燒後的塗膜以結晶化溫度以上的溫度進行燒成使其結晶化的步驟,藉此可得到LaNiO3薄膜。該結晶化的步驟之燒成環境係以O2、N2、Ar、N2O或H2等或者此等混合氣體等較為適合。燒成,較佳為藉由在450~900℃下,保持1~60分鐘來進行。燒成,亦可以急速加熱處理(RTA處理)進行。從室溫至上述燒成溫度為止的昇溫速度,較佳係設為10~100℃/秒。
藉由以上的步驟,可得到LaNiO3薄膜。如此所形成的LaNiO3薄膜,係由於表面電阻率低,導電性等優異,因此可使用於強介電體記憶體用電容器之電極膜或壓電元件等之電極膜,進而焦電型紅外線檢測元件之電極膜等。進而,由於強烈自我配向於(100)面,因此於薄膜電容器等中可適合使用為用以使介電體層之結晶配向性優先配向於(100)面的結晶配向性控制層。此外,尤其於壓電元件的情況中,可提昇壓電特性。
接著,將本發明之實施例與比較例一起進行詳細地說明。
首先,以使La與Ni之金屬原子比成為1:1的方式,分
別秤量作為LaNiO3前驅物的乙酸鎳四水合物(Ni源)、及硝酸鑭六水合物(La源)。此外,作為安定化劑,係準備了相對於上述前驅物1莫耳成為5莫耳之量的N-甲基甲醯胺。接著,將上述前驅物與N-甲基甲醯胺、與進一步之作為溶劑的乙酸,以使調製後的組成物中上述前驅物所佔之濃度以氧化物換算成為4質量%之濃度的方式投入反應容器內,進行攪拌直至固體成分完全溶解,藉此而調製出組成物。調製後,以組合薄膜過濾器與加壓槽的加壓過濾法進行過濾。
接著,將上述所得到的組成物,滴下於設置在旋轉塗佈機上之結晶面為配向於(100)軸方向的SiO2/Si基板之上,以2000rpm的旋轉速度進行20秒鐘旋轉塗佈,藉此於上述基板上形成塗膜。接著,於進行煅燒及燒成之前,將形成有塗膜的上述基板,使用加熱板,在大氣環境中,以75℃的溫度保持1分鐘,藉此而去除低沸點成分或所吸附的水分子。接著,藉由將上述形成於基板上的塗膜,使用加熱板,從室溫昇溫至400℃,並在此溫度保持5分鐘,而進行煅燒。其後,藉由使用RTA,在氧環境中,以昇溫速度10℃/秒,昇溫至800℃,並在此溫度保持5分鐘,而進行燒成。藉此,將LaNiO3薄膜形成於上述基板上。另外,從上述塗膜之形成至煅燒為止的步驟並不重複進行而進行1次,其後,藉由進行1次燒成而形成為所期望的總厚度。
除藉由重複進行5次從塗膜的形成至煅燒為止的步驟之後,進行1次燒成而形成為所期望的總厚度以外,以與實施例1-1相同的方式調製組成物,而形成LaNiO3薄膜。
首先,以使La與Ni之金屬原子比成為1:1的方式,分別秤量作為LaNiO3前驅物的乙酸鎳四水合物(Ni源)、及硝酸鑭六水合物(La源)。此外,作為安定化劑,係準備了相對於上述前驅物1莫耳成為5莫耳之量的N-甲基甲醯胺。接著,將上述前驅物與N-甲基甲醯胺、與進一步之作為溶劑的乙酸,以使調製後的組成物中所含有之上述前驅物的濃度以氧化物換算成為4質量%之濃度的方式投入反應容器內,進行攪拌直至固體成分完全溶解。接著,藉由在氮環境中,以140℃的溫度進行加熱30分鐘而調製組成物。調製後,以組合薄膜過濾器與加壓槽的加壓過濾法進行過濾。
接著,將上述所得到的組成物,滴下於設置在旋轉塗佈機上之結晶面為配向於(100)軸方向的SiO2/Si基板之上,以2000rpm的旋轉速度進行旋轉塗佈20秒鐘,藉此於上述基板上形成塗膜。接著,於進行煅燒及燒成之前,將上述形成有塗膜的基板,使用加熱板,在大氣環境中,以75℃的溫度保持1分鐘,藉此而去除低沸點成分或所吸附的水分子。接著,藉由將上述形成於基板上
的塗膜,使用加熱板,在400℃之溫度保持5分鐘,而進行煅燒。其後,藉由使用RTA,在氧環境中,以昇溫速度10℃/秒,昇溫至800℃,並在此溫度保持5分鐘,而進行燒成。藉此,將LaNiO3薄膜形成於上述基板上。另外,與實施例1相同,從上述塗膜之形成至煅燒為止的步驟並不重複進行而進行1次,其後,藉由進行1次燒成而形成為所期望的總厚度。
如以下之表1所示般,除調整各成分的比例並變更組成物中之以氧化物換算的前驅物濃度以外,以與實施例1-1相同的方式調製組成物,而形成LaNiO3薄膜。
如以下之表1所示般,除變更相對於作為安定化劑之N-甲基甲醯胺之前驅物1莫耳的比例以外,以與實施例1-1相同的方式調製組成物,而形成LaNiO3薄膜。另外,於比較例2-1中,係將相對於N-甲基甲醯胺之前驅物1莫耳的比例設為0,亦即不添加安定化劑而調製組成物。
如以下之表1所示般,作為LaNiO3前驅物,使用乙酸鹽及硝酸鹽以外之鑭異丙氧化物(La源)及乙醯丙酮酸鎳(Ni源)、及進行攪拌之後,以與實施例1-3相同的條件
進行加熱,除此之外,以與實施例1-1相同的方式調製組成物,而形成LaNiO3薄膜。
對於在實施例1-1~實施例3及比較例1-1~比較例2-2所得到的LaNiO3薄膜之膜厚、表面電阻值、優先配向面進行評估。將此等之結果顯示於以下的表1。
(1)膜厚:將所形成的LaNiO3薄膜之剖面的厚度,使用SEM(Scanning Electron Microscope,掃描型電子顯微鏡,Hitachi S-4300SE),拍攝剖面影像,而計測其膜厚。
(2)表面電阻率:使用三菱化學公司製之Loresta HP MCP-T410,藉由四探針法測定LaNiO3薄膜之表面電阻率。
(3)優先配向面:藉由X射線繞射裝置(PANalytical公司製 型號名:Empyrean)之集中法,進行LaNiO3薄膜之XRD(X-Ray Diffraction)分析,所得到的繞射結果當中,將2θ=20~40°之範圍內強度最高的配向面作為優先配向面。將針對此時所觀察到的實施例1-1之薄膜的XRD圖型作為代表圖而顯示於第1圖。
如依據表1所得知般,若將實施例1-1~1-5與比較例1-1、1-2進行比較,則於組成物100質量%中之前驅物濃度以氧化物換算不滿1質量%的比較例1-1中,係於所形成之LaNiO3薄膜上發生目視即可確認之程度的龜裂,而無法形成均勻的膜,因此,無法進行膜評估。此外,於前驅物濃度超過20質量%的比較例1-2中,係於組成物中產生沉澱,因此,無法形成LaNiO3薄膜。相對於此,於前驅物濃度設為1~20質量%之範圍的實施例1-1~1-5中,並無發生龜裂或空隙,而得到表面電阻率低,優先配向於(100)面的LaNiO3薄膜。
此外,若將實施例2-1、2-2與比較例2-1、2-2進行比較,則未添加作為安定化劑之N-甲基甲醯胺的比較例2-1中,係於所形成之LaNiO3薄膜上發生目視即可確認之程度的龜裂,而無法形成均勻的膜,因此,無法進行膜評估。此外,若於N-甲基甲醯胺的比例相對於組成物中之LaNiO3前驅物的合計量1莫耳為超過10莫耳之比較例2-2中,係於所形成之LaNiO3薄膜上發生目視即可確認之程度的空隙,而無法形成均勻的膜,因此,無法進行膜評估。相對於此,以相對於LaNiO3前驅物的合計量1莫耳添加10莫耳以下N-甲基甲醯胺之實施例2-1、2-2中,並無發生龜裂或空隙等,而得到表面電阻率低,優先配向於(100)面的LaNiO3薄膜。此外,即使於作為LaNiO3前驅物而使用鑭異丙氧化物及乙醯丙酮酸鎳的實施例3中,亦與實施例1-1~實施例2-2相同,可得到表面電阻率低,優先配向於(100)面的LaNiO3薄膜。
以上,雖說明本發明之較佳的實施例,但本發明並不限定於此等實施例。在不脫離本發明之要旨的範圍內,可進行構成之附加、省略、置換、及其他的變更。本發明並不受前述說明所限定,而僅受所添附的請求項之範圍限定。
本發明係可利用於薄膜電容器、電容器、IPD、DRAM記憶體用電容器、層合電容器、強介電體記
憶體用電容器、焦電型紅外線檢測元件、壓電元件、電光學元件、致動器、共振元件、超音波馬達、電開關、光學開關或LC雜波濾波器元件的複合電子零件的製造。
Claims (6)
- 一種LaNiO3薄膜形成用組成物,其係包含LaNiO3前驅物與乙酸之LaNiO3薄膜形成用組成物,其特徵為,前述LaNiO3薄膜形成用組成物100質量%中之前述LaNiO3前驅物的比例以氧化物換算為1~20質量%,且進一步包含相對於前述LaNiO3薄膜形成用組成物中之LaNiO3前驅物的合計量1莫耳為超過0且10莫耳以下之由N-甲基甲醯胺所構成的安定化劑。
- 如請求項1所記載之LaNiO3薄膜形成用組成物,其中前述LaNiO3前驅物為金屬羧酸鹽、金屬硝酸鹽、金屬烷氧化物、金屬二醇錯合物、金屬三醇錯合物、金屬β-二酮錯合物、金屬β-二酮酯錯合物、金屬β-亞胺基酮錯合物或金屬胺基錯合物。
- 如請求項2所記載之LaNiO3薄膜形成用組成物,其中前述LaNiO3前驅物當中,成為La源之LaNiO3前驅物及成為Ni源之LaNiO3前驅物的至少一者為乙酸鹽或硝酸鹽。
- 一種LaNiO3薄膜的形成方法,其係使用如請求項1至3中任一項所記載之LaNiO3薄膜形成用組成物。
- 一種LaNiO3薄膜的形成方法,其特徵為具有:將如請求項1至3中任一項所記載之LaNiO3薄膜形成用組成物塗佈於耐熱性基板而形成塗膜的步驟;以及將具有前述塗膜的前述耐熱性基板在大氣壓之氧化環境或含水蒸氣環境中煅燒之後,或者在重複進行2次以上由前述塗膜之形成至煅燒直至成為所期望的厚度為止之 後,以結晶化溫度以上之溫度進行燒成的步驟,且使LaNiO3薄膜優先配向於(100)面。
- 一種方法,其係製造具有藉由如請求項4或5所記載之方法形成的LaNiO3薄膜之薄膜電容器、電容器、IPD、DRAM記憶體用電容器、層合電容器、強介電體記憶體用電容器、焦電型紅外線檢測元件、壓電元件、電光學元件、致動器、共振元件、超音波馬達、電開關、光學開關或LC雜波濾波器元件的複合電子零件。
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JP2013061914A JP6075144B2 (ja) | 2013-03-25 | 2013-03-25 | LaNiO3薄膜形成用組成物及びこの組成物を用いたLaNiO3薄膜の形成方法 |
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US (1) | US20140287136A1 (zh) |
EP (1) | EP2784041A1 (zh) |
JP (1) | JP6075144B2 (zh) |
CN (1) | CN104071855A (zh) |
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CN114231951A (zh) * | 2021-11-24 | 2022-03-25 | 江苏籽硕科技有限公司 | 利用高分子辅助沉积法制备LaNiO3外延导电薄膜的方法 |
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US5733661A (en) * | 1994-11-11 | 1998-03-31 | Mitsubishi Chemical Corporation | High-permittivity composite oxide film and uses thereof |
JPH10324520A (ja) * | 1997-05-26 | 1998-12-08 | Kansai Shin Gijutsu Kenkyusho:Kk | In2O3−SnO2前駆体ゾルの製造方法およびIn2O3−SnO2薄膜の製造方法 |
EP0940368A1 (en) * | 1997-05-26 | 1999-09-08 | KRI International, Inc. | PROCESS FOR PREPARING In 2?O 3?-SnO 2? PRECURSOR SOL AND PROCESS FOR PREPARING THIN FILM OF In 2?O 3?-SnO 2? |
CN1152439C (zh) * | 2001-12-07 | 2004-06-02 | 中国科学院上海技术物理研究所 | 镍酸镧导电金属氧化物薄膜材料的制备方法 |
JP4077675B2 (ja) * | 2002-07-26 | 2008-04-16 | ナガセケムテックス株式会社 | ポリ(3,4−ジアルコキシチオフェン)とポリ陰イオンとの複合体の水分散体およびその製造方法 |
JP5030478B2 (ja) * | 2006-06-02 | 2012-09-19 | 株式会社アルバック | 多孔質膜の前駆体組成物及びその調製方法、多孔質膜及びその作製方法、並びに半導体装置 |
CN101178954A (zh) * | 2007-09-05 | 2008-05-14 | 西北有色金属研究院 | 一种导电型阻隔层LaNiO3的制备方法 |
JP5591485B2 (ja) * | 2008-05-28 | 2014-09-17 | 三菱マテリアル株式会社 | 強誘電体薄膜形成用組成物、強誘電体薄膜の形成方法並びに該方法により形成された強誘電体薄膜 |
CN101376600A (zh) * | 2008-09-26 | 2009-03-04 | 清华大学 | 一种利用导电氧化物作为缓冲层的叠层铁电/磁性多铁性磁电复合薄膜及其制备方法 |
CN101712549B (zh) * | 2008-11-20 | 2012-08-08 | 河南大学 | 一种镍酸镧陶瓷靶的制备方法 |
CN102154636B (zh) * | 2010-12-17 | 2012-09-12 | 济南大学 | 一种p型高透射率(100)-取向的LaNiO3纳米薄膜的制备方法 |
JP2013001680A (ja) * | 2011-06-16 | 2013-01-07 | Seiko Epson Corp | ニッケル酸ランタン膜形成用組成物の製造方法、ニッケル酸ランタン膜の製造方法、及び圧電素子の製造方法 |
US9076961B2 (en) * | 2012-01-31 | 2015-07-07 | Duality Reality Energy, LLC | Energy harvesting with a micro-electro-machanical system (MEMS) |
JP5817621B2 (ja) * | 2012-03-30 | 2015-11-18 | 三菱マテリアル株式会社 | 強誘電体薄膜形成用ゾルゲル液 |
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- 2014-02-19 EP EP20140155693 patent/EP2784041A1/en not_active Withdrawn
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CN104071855A (zh) | 2014-10-01 |
IN2014DE00467A (zh) | 2015-06-19 |
JP6075144B2 (ja) | 2017-02-08 |
JP2014187265A (ja) | 2014-10-02 |
EP2784041A1 (en) | 2014-10-01 |
US20140287136A1 (en) | 2014-09-25 |
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