CN1797770A - 铁电膜及其制造方法 - Google Patents
铁电膜及其制造方法 Download PDFInfo
- Publication number
- CN1797770A CN1797770A CNA2005101341019A CN200510134101A CN1797770A CN 1797770 A CN1797770 A CN 1797770A CN A2005101341019 A CNA2005101341019 A CN A2005101341019A CN 200510134101 A CN200510134101 A CN 200510134101A CN 1797770 A CN1797770 A CN 1797770A
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- China
- Prior art keywords
- ferroelectric
- ferroelectric film
- carboxylic acid
- metal alkoxide
- polybasic carboxylic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 22
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 23
- 150000004703 alkoxides Chemical class 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
- 230000003301 hydrolyzing effect Effects 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 230000032050 esterification Effects 0.000 claims description 10
- 238000005886 esterification reaction Methods 0.000 claims description 10
- 229910052732 germanium Inorganic materials 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 10
- 239000003990 capacitor Substances 0.000 claims description 8
- 150000001735 carboxylic acids Chemical class 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 19
- 239000010955 niobium Substances 0.000 abstract description 16
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- 150000002148 esters Chemical class 0.000 abstract description 5
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
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- 229910018921 CoO 3 Inorganic materials 0.000 description 4
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- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
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- 238000007591 painting process Methods 0.000 description 3
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- 229910004121 SrRuO Inorganic materials 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
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- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
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- MXLMTQWGSQIYOW-UHFFFAOYSA-N 3-methyl-2-butanol Chemical class CC(C)C(C)O MXLMTQWGSQIYOW-UHFFFAOYSA-N 0.000 description 1
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- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 241000877463 Lanio Species 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- 206010033546 Pallor Diseases 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- -1 butanols 1-butanols Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
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- SYHPANJAVIEQQL-UHFFFAOYSA-N dicarboxy carbonate Chemical compound OC(=O)OC(=O)OC(O)=O SYHPANJAVIEQQL-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 230000001815 facial effect Effects 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
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- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- GTZCVFVGUGFEME-HNQUOIGGSA-N trans-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C/C(O)=O GTZCVFVGUGFEME-HNQUOIGGSA-N 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 description 1
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- 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
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Abstract
一种铁电膜、铁电膜的制造方法,本发明涉及的铁电膜(101)的制造方法包括:(a)将含有铌元素的多元羧酸盐、含铋元素的多元羧酸盐、多元羧酸或多元羧酸酯、和有机溶剂混合的工序;(b)将混合的溶液涂布在基体上之后进行热处理,由此形成由BiNbO4构成的铁电膜的工序。根据本发明,可以提供不含铅的可靠性高的铁电体及其制造方法、铁电体电容器以及铁电存储器。
Description
技术领域
本发明涉及铁电膜及其制造方法
背景技术
以PZT为首的铁电膜用于铁电存储器、压电元件、红外传感器等各种用途中,对其的研究开发正在广泛地展开。
特别是铁电存储器具有不挥发性,期待作为具有与DRAM相同的动作速度的下一代存储器。此外,铁电存储器具有与其它存储器相比消耗电力低的特点。
但是,PZT之类的铁电材料中含有很多对人体有害的铅,因此不宜大量生产。此外,在PZT中铅容易挥发,因此与铅的结合能低的氧容易缺损。
发明内容
本发明的目的在于提供一种不含铅的可靠性高的铁电膜及其制造方法、铁电电容器、以及铁电电容器。
本发明涉及的铁电膜由BiNbO4构成。
本发明涉及的铁电膜中,所述BiNbO4可以具有Bi层状钙钛矿结构。
本发明涉及的铁电膜中,还可以含有Si、或Si和Ge。
本发明涉及的铁电膜的制造方法中,包括:
(a)将含有铌元素的多元羧酸盐、含铋元素的多元羧酸盐、多元羧酸或多元羧酸酯、和有机溶剂混合的工序;
(b)将混合的溶液涂布在基体上之后进行热处理,由此形成由BiNbO4构成的铁电膜的工序。
本发明涉及的铁电膜的制造方法中,包括:
(a)将包括含铌元素的金属醇盐的水解缩合物的溶胶凝胶原料、包括含铋元素的金属醇盐的水解缩合物的溶胶凝胶原料、多元羧酸或多元羧酸酯、和有机溶剂混合,而使来自所述多元羧酸或所述多元羧酸酯的多元羧酸、和所述含铌元素的金属醇盐和所述含铋元素的金属醇盐进行酯化反应,由此制作铁电体的前驱体组合物的工序;以及
(b)将所述前驱体组合物涂布在基体上之后进行热处理,由此形成由BiNbO4构成的铁电膜的工序。
本发明涉及的铁电膜的制造方法中,所述有机溶剂可以是醇。
本发明涉及的铁电膜的制造方法中,在所述工序(a)中,可以混合还含有Si、或Si和Ge的溶胶凝胶溶液。特别是,优选按1~3mol%的比例将Si、或Si和Ge添加到所述前驱体组合物中。
本发明涉及的铁电体的原料溶液,包含含有铌元素的多元羧酸盐、含铋元素的多元羧酸盐、多元羧酸或多元羧酸酯、和有机溶剂。
本发明涉及的铁电体的原料溶液,包含:包括含铌元素的金属醇盐的水解缩合物的溶胶凝胶原料、包括含铋元素的金属醇盐的水解缩合物的溶胶凝胶原料、多元羧酸或多元羧酸酯、和有机溶剂。
本发明涉及的铁电体电容器具有上述任意一种的铁电膜。
本发明涉及的铁电体存储器具有上述的铁电电容器。
附图说明
图1是表示实施方式的铁电体电容器的剖面图。
图2是Bi层状钙钛矿型晶体结构的说明图。
图3是表示本实施方式中使用的辛酸铌的图。
图4是示意性地表示实施方式的单纯矩阵型的铁电体存储装置的俯视图和剖面图。
图5是表示实施方式中存储单元阵列与周边电路一同集成在同一基板上的铁电体存储装置一例的剖面图。
图6是示意性地表示实施方式的变形例的1T1C型铁电体存储器的俯视图和其等价电路图。
图7是表示本实施方式的实验例的样品的形成方法的图。
图8是表示实施例的样品的铁电膜的结晶性的图。
图9是表示实施例的样品的滞后特性的图。
具体实施方式
下面,参照附图说明本发明的优选的实施方式。
1.铁电膜以及铁电电容器
图1是示意性地表示使用了本实施方式的铁电膜101的铁电电容器100的剖面图。
如图1所示,铁电电容器100由基板10、第1电极102、形成在第1电极102之上的铁电膜101、以及形成在铁电膜101之上的第2电极103组成。
第1电极102和第2电极103的厚度例如为50~150nm。
铁电膜101由BiNbO4构成,具有Bi层状钙钛矿结构。此外,铁电膜101还含有Si、或、Si和Ge。关于Si、或Si和Ge,在后面详细说明。
Bi层状钙钛矿是具有如图2所示结晶结构的物质。在由Bi形成的层之间配置有多个以氧作为顶点的八面体。在该八面体的内部配置有Nb。本发明涉及的铁电膜101由α相(铁电相)的BiNbO4构成。铁电膜101的厚度例如为50~150nm。
2.铁电膜以及铁电电容器的制造方法
下面说明本实施方式的铁电膜以及铁电电容器的制造方法。
(1)首先准备基板10。作为基板10例如可以使用硅等。
(2)接着,在基板10上形成第1电极102。第1电极102例如可以由激光消融法形成。即,准备含有所希望的电极材料的靶。并且向靶照射激光,从靶打出含氧原子和金属原子的原子,发生热柱(plume)。接着向基板10上射出该热柱使之与基板接触。其结果,第1电极102在基板10上外延生长。
作为第1电极102的材料,没有特别的限定,可以使用Pt、Ir、IrOx以及SrRuO3、Nb-SrTiO3、La-SrTiO3、Nb-(La,Sr)CoO3、LiNO3、或PbBO3等。其中,Nb-SrTiO3是在SrTiO3中掺杂Nb来获得的,La-SrTiO3是在SrTiO3中掺杂La来获得的,Nb-(La,Sr)CoO3是在(La,Sr)CoO3中掺杂Nb来获得的。
此外,作为第1电极102的形成方法,替代激光消融法也可以使用离子束助推器、溅射法或真空蒸镀法。
(3)接着,在第1电极102上形成铁电膜101。
首先,将含有铌元素的多元羧酸盐、含铋元素的多元羧酸盐、多元羧酸或多元羧酸酯、和有机溶剂混合。
作为含有铌的多元羧酸盐,例如可以使用辛酸铌。如图3所示,辛酸铌是Nb的2个原子靠共价键结合、而在其它部分存在辛基的结构。
羧酸和辛酸铌主要是通过醇交换反应形成网络。在羧酸和辛基之间发生反应(醇交换反应),进行R-COO-Nb酯化。这样,本实施方式中通过酯化辛酸铌,可以通过辛酸铌和醇盐的缩合使辛酸铌的分子结合在前驱体的网络上。
作为含铋元素的多元羧酸盐例如可以使用辛酸铋。辛酸铋也和辛酸铌同样,主要是通过醇交换反应进行网络的形成。
作为本实施方式的有机溶剂,可以使用醇。如果使用醇作为溶剂,可以使溶胶凝胶原料和多元羧酸或多元羧酸酯两者的溶解性良好。
作为醇没有特别的限定,例如可以举出丁醇、甲醇、乙醇、丙醇等一元醇、或多元醇等。作为这样的醇,可以举出如下的物质。
1元醇类:
作为丙醇有1-丙醇(沸点97.4℃)、2-丙醇(沸点82.7℃),
作为丁醇有1-丁醇(沸点117℃)、2-丁醇(沸点100℃)、2-甲基-1-丙醇(沸点108℃)、2-甲基-2-丙醇(熔点25.4℃、沸点83℃),
作为戊醇有1-戊醇(沸点137℃)、3-甲基-1-丁醇(沸点131℃)、2-甲基-1-丁醇(沸点131℃)、2,2-二甲基-1-丙醇(沸点113℃)、2-戊醇(沸点119℃)、3-甲基-2-丁醇(沸点112.5℃)、3-戊醇(沸点117℃)、2-甲基-2-丁醇(沸点102℃)、
多元醇类
乙二醇(熔点-11.5℃、沸点197.5℃)、甘油(熔点17℃、沸点290℃)
多元羧酸或所述多元羧酸酯优选是2元羧酸或多元羧酸酯。
作为多元羧酸,可以举出如下的物质。作为三元羧酸,可以举出:反乌头酸、均苯三酸,作为四元羧酸可以举出均苯四酸、1,2,3,4-环戊四羧酸等。并且,作为在醇中解离、起着多元羧酸作用的多元羧酸酯,可以举出二元的琥珀酸二甲酯、琥珀酸二乙酯、草酸二丁酯、丙二酸二甲酯、己二酸二甲酯、马来酸二甲酯、富马酸二甲酯,三元的柠檬酸三丁酯、1,1,2-乙烷三羧酸三乙酯、四元的1,1,2,2-乙烷四羧酸四乙酯、1,2,4-苯三羧酸三甲酯等。这些多元羧酸酯在醇的存在下解离而显示出多元羧酸的作用。此外,本发明的特征在于使用多元羧酸由酯化来连接网络,例如乙酸或乙酸甲酯等一元羧酸和其酯由于不形成酯的网络,因此这些不包括在本发明中。
作为二元羧酸酯,优选选自琥珀酸酯,马来酸酯和丙二酸酯中的至少一种。这些酯的具体例可以举出琥珀酸二甲酯、马来酸二甲酯、丙二酸二甲酯。
另外,在本实施方式的铁电膜的制造方法中,作为含有金属醇盐的水解缩合物的溶胶凝胶原料,可以使用含Si或Si和Ge的溶胶凝胶原料。这样的溶胶凝胶溶液可以单独使用PbSiO3用溶胶凝胶溶液,或者可以使用PbSiO3用溶胶凝胶溶液和PbGeO3用溶胶凝胶溶液两者。通过使用这样的含Si或Ge的溶胶凝胶溶液,可以降低成膜时的温度,可以从450℃左右开始进行铁电体的结晶化。
这样,通过添加Si或Si和Ge,可以得到作为更可靠的铁电相的α相的BiNbO4。
将混合后的溶液涂布在基体上,然后实施热处理使之结晶化,由此可以形成铁电膜101。
具体而言,按所希望的次数进行混合溶液涂布工序、醇除去工序~干燥热处理工序~脱脂热处理工序一连串工序,之后利用结晶化退火进行烧成,形成铁电膜101。各工序的条件例如为如下。
混合溶液涂布工序中,采用旋涂法等涂布法进行混合溶液的涂布。首先,向第1电极102滴下混合溶液。为了使滴下的溶液遍及整个基板而进行旋转。旋转的转速例如为500rpm左右。接着降低转速旋转所希望的时间,由此将混合溶液涂布在第1电极102之上。此时的转速例如为50rpm以下。干燥热处理工序在150℃~180℃下进行。干燥热处理是在大气气氛下使用热板等进行。同样,脱脂热处理工序是在保持成300℃~350℃的热板上、在大气气氛下进行的。用于结晶化的烧成是在氧气氛中使用热快速退火(RTA)等进行。
烧结后的铁电膜101的膜厚可以设定为50~150nm。铁电膜101例如可以采用溅射法、分子线外延法、或激光消融法等形成。
另外,替代含铌元素的多元羧酸盐和含铋元素的多元羧酸盐,也可以使用包括含铌元素的金属醇盐的水解缩合物的溶胶凝胶原料和包括含铋元素的金属醇盐的水解缩合物的溶胶凝胶原料。通过将包括含铌元素的金属醇盐的水解缩合物的溶胶凝胶原料和包括含铋元素的金属醇盐的水解缩合物的溶胶凝胶原料、多元羧酸或多元羧酸酯以及有机溶剂进行混合,使来自所述多元羧酸或所述多元羧酸酯的多元羧酸、和所述含铌元素的金属醇盐和所述含铋元素的金属醇盐进行酯化反应,由此可以制作铁电体的前驱体组合物。
前驱体组合物的生成反应大致包括第1步的烷氧基的取代反应、和第2步的通过酯化形成高分子网络的反应。
在第一步反应中,通过琥珀酸二甲酯和溶胶凝胶原料的金属醇盐的酯化,两者酯化结合。也就是,琥珀酸二甲酯在正丁醇中解离,形成一方羰基(第1羰基)上附加了质子的状态。该第1羰基和金属醇盐的烷氧基发生置换反应,生成第1羰基被酯化的反应产物和醇。这里,“酯键”是指羰基和氧原子的结合(-COO-)。
在第2步反应中,在第1步反应中残留的另一方羧基(第2羧基)和金属醇盐的烷氧基发生置换反应,生成第2羧基被酯化的反应产物和醇。
这样,通过2步反应可以获得含在溶胶凝胶原料中的金属醇的水解缩合物之间靠酯键结合的高分子网络。因此,此高分子网络在该网络内具有适当、有序的酯键。
(4)接着,在铁电膜101之上形成第2电极103。第2电极103例如可以采用溅射法或真空蒸镀法等形成。作为上部电极优选使用以Pt为主的材料构成。此外,该第2电极103并不限定在Pt,可以使用例如Ir、IrOx、SrRuO3、Nb-SrTiO3、La-SrTiO3、Nb-(LaSr)CoO3、LaNiO3、PbBaO3等公知的电极材料。
(5)接着,根据需要在氧气氛中使用RTA等进行后补退火。由此,可以形成第2电极103和铁电膜101的良好的界面,并且可以改善铁电膜101的结晶性。
可以按照以上的工序制造本实施方式涉及的铁电膜101和铁电电容器100。
根据本发明涉及的铁电电容器100,可以实现结晶化温度的低温化并提高滞后的矩形性。此外,铁电电容器100的滞后的矩形性的提高,在对单纯矩阵型铁电体存储装置的驱动来讲比较重要的扰动的稳定性方面有效。
3.铁电体存储器
图4(A)和图4(B)是表示本发明实施方式的单纯矩阵型的铁电体存储装置300的结构的图。图4(A)是其俯视图,图4(B)是图4(A)的A-A向剖面图。如图4(A)和4(B)所示,铁电体存储装置300具有形成在基板308之上的按给定数目排列的字线301~303,和按给定数目排列的位线304~306。在字线301~303和位线304~306之间插入在上述实施方式中说明的铁电膜307,在字线301~303和位线304~306的交叉区域形成铁电电容器。
在排列由该单纯矩阵构成的存储单元形成的铁电体存储装置300中,向形成在字线301~303和位线304~306的交叉区域的铁电电容器的读入和读出,是通过未图示的周边的驱动电路、读出用的放大电路等(将这些称为周边电路)来进行。该周边电路可以在与存储单元阵列不同的基板上通过MOS晶体管形成,与字线301~303和位线304~306连接,或者是在基板308上使用单晶硅基板在同一基板上将周边电路与存储单元阵列集成化。
图5是表示本实施方式的、存储单元阵列与周边电路在同一基板上集成化的铁电体存储装置400的一例的剖面图。
在图5中,在单晶硅基板上401上形成MOS晶体管402,该晶体管形成区域形成周边电路部。MOS晶体管402由单晶硅基板上401、源极·漏极区域405、栅极绝缘膜403、以及栅电极404构成。并且,铁电体存储装置400具有元件分离用氧化膜406、第1层间绝缘膜407、第1配线层408、以及第2层间绝缘膜409。
并且,铁电存储装置400具有由铁电电容器420构成的存储单元阵列,铁电电容器420由形成字线或位线的下部电极(第1电极或第2电极)410、包含铁电相和顺电相的铁电膜411、以及形成在铁电膜411之上并形成字线或位线的上部电极(第2电极或第1电极)412构成。
此外,铁电存储装置400在铁电电容器420的上方具有第3层间绝缘膜413,通过第2配线层414存储单元阵列与周边电路部连接。此外,在铁电存储装置400中,在第3层间绝缘膜413和第2配线层414的上面形成有保护膜415。
通过采用具有以上结构的铁电存储装置400,可以将存储单元阵列与周边电路部集成在同一基板上。此外,图5所示的铁电存储装置400采用了在周边电路部上形成有存储单元阵列的结构,但也可以采用不在周边电路部上设置存储单元阵列而存储单元阵列与周边电路部在平面上相互连接的结构。
本实施方式中使用的铁电电容器420由上述实施方式的铁电膜构成,因此滞后的矩形性非常好,具有稳定的扰动特性。此外,该铁电电容器420通过对工序温度的低温化,对周边电路等和其它元件的损伤少,并且过程损伤(特别是氢的还原)少,因而可以抑制由于损伤引起的滞后的劣化。因此,通过使用所述铁电电容器420,可以实现单纯矩阵型铁电存储装置300的实用化。
在图6(A)中作为变形例表示了1T1C型铁电存储装置500的结构图。图6(B)是铁电存储装置500的等价电路图。
如图6(A)所示,铁电存储装置500是由电容器504(1C)、和源/漏电极的一方与数据线505连接并具有与字线连接的栅电极506的开关用的晶体管元件507(1T)构成的、其结构与DRAM非常相似的存储元件。所述电容器504(1C)由下部电极501、与板线连接的上部电极502、以及上述实施方式的铁电膜503构成。1T1C型存储器能够高速(100ns以下)地进行写入和读出,并且写入的数据不挥发因此有望代替SRAM。
以上,对本发明的实施方式的一例进行了说明,但本发明并不限于这些实施方式,在本发明宗旨的范围内,可以采用各种实施形态。
4.实验例
下面对本发明的实验例进行说明。
4.1实验例1
本实施例涉及的铁电膜是使用如下的原料溶液来制造的。
将辛酸铋和辛酸铌(按摩尔比为(辛酸铋)∶(辛酸铌)=1∶1)以1.5mol%的比例与Si元素一同混合在正丁醇等溶剂中,制作了溶液。
然后,将上述溶液和琥珀酸二甲酯混合,制作了原料溶液。并且,琥珀酸二甲酯是相对于各原料溶液中的金属元素浓度1mol/l,按0.5mol/l的比例混合的。接着,密闭各原料溶液,在90℃保持30分钟之后冷却至室温,充分地促进了酯化。
使用制作的溶液,按图7所示的方法制作了样品。
也就是,利用溅射法形成由铂构成的下部电极,将原料溶液用旋涂法涂布在基板上,使用热板在150~180℃(150℃)下进行干燥处理,除去醇。之后,使用热板在300~350℃(300℃)下进行脱脂热处理。接着,根据需要多次(总共3次)进行上述涂布工序、干燥处理工序和脱脂热处理,得到了所希望厚度的涂膜。进而,利用结晶化退火(烧成)得到了膜厚150nm的铁电膜的样品。为了进行结晶化的烧成是在氧气氛中使用快速热退火(RTA)在650~700℃(650℃)下进行的。进而,用溅射法形成由铂构成的上部电极,采用RTA在650~700℃(650℃)下进行恢复退火,由此得到了铁电电容器的样品(下面将其称之为电容器样品)。
使用这些样品调查了以下特性。
(a)对样品铁电体膜通过X射线衍射调查了结晶性。图8是表示样品铁电膜的结晶性的图。由图8确认了来源于BiNbO4的(141)和(121)峰,由此可以确认形成有铋层状钙钛矿结构的结晶。
(b)在图9中表示了对于电容器样品求出的滞后。由图9可以确认所有的电容器都具有良好的滞后特性。
Claims (11)
1.一种铁电膜,由BiNbO4构成。
2.根据权利要求1所述的铁电膜,其中所述BiNbO4具有Bi层状钙钛矿结构。
3.根据权利要求1或2所述的铁电膜,其中还含有Si、或Si和Ge。
4.一种铁电膜的制造方法,包括:
(a)将含有铌元素的多元羧酸盐、含铋元素的多元羧酸盐、多元羧酸或多元羧酸酯、和有机溶剂混合的工序;
(b)将混合的溶液涂布在基体上之后进行热处理,由此形成由BiNbO4构成的铁电膜的工序。
5.一种铁电膜的制造方法,包括:
(a)将包括含铌元素的金属醇盐的水解缩合物的溶胶凝胶原料、包括含铋元素的金属醇盐的水解缩合物的溶胶凝胶原料、多元羧酸或多元羧酸酯、和有机溶剂混合,而使来自所述多元羧酸或所述多元羧酸酯的多元羧酸、和含所述铌元素的金属醇盐和所述含铋元素的金属醇盐进行酯化反应,制作铁电体的前驱体组合物的工序;以及
(b)将所述前驱体组合物涂布在基体上之后进行热处理,由此形成由BiNbO4构成的铁电膜的工序。
6.根据权利要求4或5所述的铁电膜的制造方法,其中所述有机溶剂是醇。
7.根据权利要求4~6中任意一项所述的铁电膜的制造方法,其中在所述工序(a)中,还混合含有Si、或Si和Ge的溶胶凝胶溶液。
8.一种铁电体的原料溶液,包含:含有铌元素的多元羧酸盐、含铋元素的多元羧酸盐、多元羧酸或多元羧酸酯、和有机溶剂。
9.一种铁电体的原料溶液,包含:包括含铌元素的金属醇盐的水解缩合物的溶胶凝胶原料、包括含铋元素的金属醇盐的水解缩合物的溶胶凝胶原料、多元羧酸或多元羧酸酯、和有机溶剂。
10.一种铁电体电容器,具有权利要求1~3中任意一项所述的铁电膜。
11.一种铁电存储器,具有权利要求10所述的铁电电容器。
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CN103572370A (zh) * | 2013-10-29 | 2014-02-12 | 西安交通大学 | 一种镱酸铋单晶外延薄膜及其制备方法 |
CN103999207A (zh) * | 2011-11-09 | 2014-08-20 | 独立行政法人科学技术振兴机构 | 固体电子装置 |
CN101714453B (zh) * | 2008-09-30 | 2016-05-11 | 通用电气公司 | 薄膜电容器 |
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KR100902870B1 (ko) | 2007-11-07 | 2009-06-16 | 고려대학교 산학협력단 | 유전체 조성물 및 이로 형성되는 유전체 박막층을 구비하는스위칭 소자 |
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WO2016013416A1 (ja) * | 2014-07-25 | 2016-01-28 | 国立大学法人北陸先端科学技術大学院大学 | 酸化物誘電体及びその製造方法、並びに固体電子装置及びその製造方法 |
CN105559941B (zh) * | 2015-12-12 | 2017-11-24 | 西安交通大学 | 测量全牙列动态啮合的凝胶薄膜阵列式电容传感器及方法 |
JP6892459B2 (ja) * | 2016-12-22 | 2021-06-23 | 国立大学法人北陸先端科学技術大学院大学 | 酸化物誘電体及びその製造方法、並びに固体電子装置及びその製造方法 |
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US9390857B2 (en) | 2008-09-30 | 2016-07-12 | General Electric Company | Film capacitor |
CN103999207A (zh) * | 2011-11-09 | 2014-08-20 | 独立行政法人科学技术振兴机构 | 固体电子装置 |
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CN103572370A (zh) * | 2013-10-29 | 2014-02-12 | 西安交通大学 | 一种镱酸铋单晶外延薄膜及其制备方法 |
CN103572370B (zh) * | 2013-10-29 | 2016-02-24 | 西安交通大学 | 一种镱酸铋单晶外延薄膜及其制备方法 |
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