CN111747730A - 电介质膜及电子部件 - Google Patents
电介质膜及电子部件 Download PDFInfo
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- CN111747730A CN111747730A CN202010218573.7A CN202010218573A CN111747730A CN 111747730 A CN111747730 A CN 111747730A CN 202010218573 A CN202010218573 A CN 202010218573A CN 111747730 A CN111747730 A CN 111747730A
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- dielectric film
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- 239000002131 composite material Substances 0.000 claims abstract description 22
- 239000011777 magnesium Substances 0.000 claims abstract description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052788 barium Inorganic materials 0.000 claims abstract description 9
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 9
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010955 niobium Substances 0.000 claims abstract description 8
- 239000011575 calcium Substances 0.000 claims abstract description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000010408 film Substances 0.000 abstract description 124
- 239000010409 thin film Substances 0.000 abstract description 35
- 230000015556 catabolic process Effects 0.000 abstract description 32
- 239000000758 substrate Substances 0.000 description 38
- 239000003990 capacitor Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 22
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- 239000000463 material Substances 0.000 description 19
- 239000000843 powder Substances 0.000 description 18
- 239000013078 crystal Substances 0.000 description 15
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- 239000002184 metal Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000004544 sputter deposition Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 239000003989 dielectric material Substances 0.000 description 7
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- 238000004549 pulsed laser deposition Methods 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000013077 target material Substances 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- 238000005229 chemical vapour deposition Methods 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
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- 229910052737 gold Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910002244 LaAlO3 Inorganic materials 0.000 description 1
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 1
- 229910003200 NdGaO3 Inorganic materials 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 229910003134 ZrOx Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
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- 238000010884 ion-beam technique Methods 0.000 description 1
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- 238000010295 mobile communication Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
本发明提供一种电介质膜,作为其主成分,含有以通式xAO-yBO-zC2O5表示的复合氧化物,A为选自由钡、钙和锶构成的组中的至少一者,B为选自由镁和锌构成的组中的至少一者,C为选自由铌和钽构成的组中的至少一者,x、y和z满足以下关系:x+y+z=1.000、0.375≤x≤0.563、0.250≤y≤0.500、x/3≤z≤(x/3)+1/9的关系,电介质膜的X射线衍射图中,复合氧化物的(110)面的衍射峰的半峰全宽为0.40°以上。由此,能够提供即使是薄膜,绝缘破坏电压也较高的电介质膜。
Description
技术领域
本发明涉及电介质膜及电子部件。
背景技术
近年来,以智能手机为代表的移动体通信设备中,为了可进行高速且大容量的通信,使用的频段的数量不断增加。使用的频段是GHz频段那样的高频段。在这种高频段中工作的平衡-不平衡变换器、耦合器、滤波器、或组合了滤波器的双工器、天线共用器等的高频部件中,存在将电介质材料用作谐振器的情况。这种电介质材料中,要求在高频段中,介质损耗较小,且频率的选择性良好。
介质损耗的倒数能够作为品质因数Q值表示,因此,换言之,期望在高频段中品质因数Q值高的电介质材料。
专利文献1中公开了具有与Ba(Mg1/3Ta2/3)O3这样的化学计量组成不同的组成的电介质磁器,并公开了该电介质磁器的10GHZ下的Q值为40000以上。
现有技术文献
专利文献
专利文献1:日本特开平8-319162号公报。
发明内容
发明所要解决的问题
但是,专利文献1所公开的电介质磁器为烧结体,因此,为了呈现专利文献1所公开的介电特性,需要设为具有充分的体积的烧结体。因此,作为适用于高频段中使用的高频部件的电介质材料,存在尺寸过大的问题。
另外,在缩小应用于高频部件的电介质材料的尺寸的情况下,即在减薄电介质材料的厚度的情况下,存在绝缘破坏电压降低的倾向。当绝缘破坏电压降低时,存在泄漏电流增加的问题。
本发明是鉴于这种实际状况而研发的,其目的在于,提供即使是薄膜,绝缘破坏电压也较高的电介质膜。
用于解决问题的技术手段
为了达成所述目的,本发明的方式提供一种电介质膜,
[1]作为其主成分,含有以通式xAO-yBO-zC2O5表示的复合氧化物,
A为选自由钡、钙和锶构成的组中的至少一者,
B为选自由镁和锌构成的组中的至少一者,
C为选自由铌和钽构成的组中的至少一者,
x、y和z满足以下关系:x+y+z=1.000,0.375≤x≤0.563,0.250≤y≤0.500,x/3≤z≤(x/3)+1/9,
在电介质膜的X射线衍射图中,复合氧化物的(110)面的衍射峰的半峰全宽为0.40°以上。
[2]根据[1]所记载的电介质膜,其中,
(110)面的衍射峰的半峰全宽为0.40°以上6.00°以下。
[3]一种电子部件,其具有[1]或[2]所记载的电介质膜。
发明效果
根据本发明,能够提供即使是薄膜,绝缘破坏电压也较高的电介质膜。
附图说明
图1是作为本实施方式的电子部件的一例的薄膜电容器的示意性的剖视图。
附图标记的说明
10……薄膜电容器
1……衬底
2……基底层
3……下部电极
4……上部电极
5……电介质膜
具体实施方式
以下,基于具体的实施方式,以以下的顺序详细地说明本发明。
1.薄膜电容器
1.1.薄膜电容器的整体结构
1.2.电介质膜
1.2.1.复合氧化物
1.3.衬底
1.4.下部电极
1.5.上部电极
2.薄膜电容器的制造方法
3.本实施方式的总结
4.变形例
(1.薄膜电容器)
首先,作为本实施方式的电子部件,对电介质层由膜状的电介质膜构成的薄膜电容器进行说明。
(1.1.薄膜电容器的整体结构)
如图1所示,作为本实施方式的电子部件的一例的薄膜电容器10具有衬底1、下部电极3、电介质膜5、上部电极4以该顺序层叠的结构。下部电极3、电介质膜5、上部电极4形成电容器部,下部电极3和上部电极4连接于外部电路,当施加电压时,电介质膜5呈现预定的静电电容,能够发挥作为电容器的功能。关于各构成要素的详细的说明进行后述。
另外,本实施方式中,在衬底1与下部电极3之间,为了提高衬底1与下部电极3的密合性,形成有基底层2。构成基底层2的材料如果是能够充分确保衬底1与下部电极3的密合性的材料,则没有特别限制。例如,在下部电极3由Cu构成的情况下,基底层2由Cr构成,在下部电极3由Pt构成的情况下,基底层2能够由Ti构成。
另外,图1所示的薄膜电容器10中,也可以形成用于将电介质膜5与外部气氛遮断的保护膜。
此外,薄膜电容器的形状没有特别限制,通常设为长方体形状。另外,其尺寸也没有特别限制,厚度和长度只要根据用途设为适当的尺寸即可。
(1.2.电介质膜)
电介质膜5,作为其主成分,含有将后述的复合氧化物。本实施方式中,主成分是电介质膜100mol%中占据50mol%以上的成分。
另外,本实施方式中,电介质膜5是通过公知的成膜法形成的膜。这种膜通常通过在衬底上堆积原子而形成,因此,电介质膜优选为电介质堆积膜。因此,电介质膜不包含将成形电介质的原料粉末的成形体烧成而得到的(通过固相反应得到)烧结体。
电介质膜5的厚度优选为10nm~4000nm,更优选为50nm~3000nm。电介质膜5的厚度过薄时,存在容易产生电介质膜5的绝缘破坏的倾向。当产生绝缘破坏时,不能发挥作为电容器的功能。另一方面,当电介质膜5的厚度过厚时,为了增大电容器的静电电容,需要扩大电极面积,根据电子部件的设计不同,有时难以小型化和薄型化。
此外,电介质膜5的厚度能够通过将包含电介质膜5的薄膜电容器利用FIB(聚焦离子束)加工装置切削,且将得到的截面利用SEM(扫描型电子显微镜)观察并测定。
(1.2.1.复合氧化物)
复合氧化物是包含A元素、B元素和C元素的氧化物,以通式xAO-yBO-zC2O5表示。本实施方式中,A元素和B元素由二价元素构成,C元素由五价元素构成。
该通式中的“x”表示复合氧化物1.000摩尔的氧化物AO的摩尔数比例。同样,上述的通式中的“y”表示复合氧化物1.000摩尔的氧化物BO的摩尔数比例,上述的通式中的“z”表示复合氧化物1.000摩尔的氧化物C2O5的摩尔数比例。
本实施方式中,“x”、“y”和“z”满足x+y+z=1.000、0.375≤x≤0.563、0.250≤y≤0.500、x/3≤z≤(x/3)+1/9的关系。
当“x”过小时,存在Q值降低的倾向。另一方面,当“x”过大时,A元素过量,容易与大气中的二氧化碳、水分等反应,存在电介质膜变质且不能维持形状的倾向。
当“y”过小时,A元素容易相对性地过量,因此,呈现上述的倾向。当“y”过大时,存在电介质膜中产生裂纹的倾向。
当“z”过小时,A元素容易相对性地过量,因此,呈现上述的倾向。当“z”过大时,C元素过量,容易在电介质膜中产生氧缺陷,存在半导体化的倾向。
本实施方式中,A元素为选自由钡(Ba)、钙(Ca)和锶(Sr)构成的组中的至少一者。A元素优选至少含有钡,在该情况下,A元素为钡、或者钡和选自由钙及锶构成的组中的至少一者。作为A元素,通过至少含有钡,存在绝缘破坏电压和Q值提高的倾向。
本实施方式中,B元素为选自由镁(Mg)和锌(Zn)构成的组中的至少一者。B元素优选至少含有镁,在该情况下,B元素为镁、或者镁和锌。作为B元素,通过至少含有镁,存在绝缘破坏电压和Q值提高的倾向。
本实施方式中,C元素为选自由铌(Nb)和钽(Ta)构成的组中的至少一者。C元素优选至少含有钽,在该情况下,C元素为钽、或者钽和铌。作为C元素,通过至少含有钽,存在Q值和绝缘破坏电压提高的倾向。
本实施方式中,电介质膜的通过X射线衍射测定得到的X射线衍射图中,复合氧化物的(110)面的衍射峰的半峰全宽为0.40°以上。半峰全宽作为峰强度的一半的强度下的峰的宽度(FWHM)而被算出。
半峰全宽是结晶性的指标。在半峰全宽较小的情况下,是指复合氧化物的结晶性高,在半峰全宽较大的情况下,是指复合氧化物的结晶性低。本实施方式中,通过将半峰全宽设为上述的范围,能够控制复合氧化物的结晶性,并提高电介质膜的绝缘破坏电压。
(110)面的衍射峰的半峰全宽优选为6.00°以下,更优选为4.00°以下。通过将(110)面的衍射峰的半峰全宽的上限值设为上述的值,能够较高地维持电介质膜的绝缘破坏电压,且抑制复合氧化物的过度的非晶化,并将电介质膜的Q值设为预定的值以上。
此外,作为X射线源,在使用Cu-Kα射线的情况下,(110)面的衍射峰处于衍射角2θ为30°附近。
复合氧化物的半峰全宽的控制能够通过例如成膜法的种类、成膜时的衬底温度、成膜时赋予的能量、成膜时的气氛进行。
另外,本实施方式的电介质膜也可以在实现本发明效果的范围内含有微量的杂质、副成分等。
(1.3.衬底)
图1所示的衬底1如果由具有能够支承形成于其上的基底层2、下部电极3、电介质膜5以及上部电极4的程度的机械强度的材料构成,则没有特别限定。例如示例:由Si单晶、SiGe单晶、GaAs单晶、InP单晶、SrTiO3单晶、MgO单晶、LaAlO3单晶、ZrO2单晶、MgAl2O4单晶、NdGaO3单晶等构成的单晶衬底;由Al2O3多结晶、ZnO多结晶、SiO2多结晶等构成的陶瓷多结晶衬底;Ni、Cu、Ti、W、Mo、Al、Pt等的金属;由这些合金等构成的金属衬底等。本实施方式中,从低成本、加工性等的观点来看,将Si单晶用作衬底。
衬底1的厚度设定成例如10μm~5000μm。当厚度过小时,有时产生不能确保机械强度的情况,当厚度过大时,有时产生不能有助于电子部件的小型化的问题。
上述的衬底1根据衬底的材质不同,其电阻率不同。在由电阻率低的材料构成衬底的情况下,在薄膜电容器的工作时产生电流向衬底侧的泄漏,有时对薄膜电容器的电特性造成影响。因此,在衬底1的电阻率较低的情况下,优选对其表面实施绝缘处理,使电容器工作时的电流不流向衬底1。
例如,在将Si单晶用作衬底1的情况下,优选在衬底1的表面形成有绝缘层。如果充分确保衬底1与电容器部的绝缘,则构成绝缘层的材料及其厚度没有特别限定。本实施方式中,作为构成绝缘层的材料,示例SiO2、Al2O3、Si3Nx等。另外,绝缘层的厚度优选为0.01μm以上。
(1.4.下部电极)
如图1所示,在衬底1上,下部电极3经由基底层2薄膜状地形成。下部电极3是用于与后述的上部电极4一起夹持电介质膜5,并作为电容器发挥作用的电极。构成下部电极3的材料如果是具有导电性的材料,则没有特别限制。例如示例:Pt、Ru、Rh、Pd、Ir、Au、Ag、Cu等的金属、它们的合金、或导电性氧化物等。
下部电极3的厚度如果是作为电极发挥作用的左右的厚度,则没有特别限制。本实施方式中,厚度优选为0.01μm以上。
(1.5.上部电极)
如图1所示,在电介质膜5的表面,上部电极4薄膜状地形成。上部电极4是用于与上述的下部电极3一起夹持电介质膜5,并作为电容器发挥作用的电极。因此,上部电极4具有与下部电极3不同的极性。
构成上部电极4的材料与下部电极3一样,如果是具有导电性的材料,则没有特别限制。例如示例:Pt、Ru、Rh、Pd、Ir、Au、Ag、Cu等的金属、它们的合金、或导电性氧化物等。
(2.薄膜电容器的制造方法)
接着,以下说明图1所示的薄膜电容器10的制造方法的一例。
首先,准备衬底1。作为衬底1,在例如使用Si单晶衬底的情况下,在该衬底的一主面形成绝缘层。作为形成绝缘层的方法,只要使用热氧化法、CVD(Chemical VaporDeposition)法等的公知的成膜法即可。
接着,在形成的绝缘层上,使用公知的成膜法形成构成基底层的材料的薄膜并形成基底层2。
在形成基底层2之后,在该基底层2上,使用公知的成膜法形成构成下部电极的材料的薄膜并形成下部电极3。
在形成下部电极3之后,为了实现基底层2与下部电极3的密合性提高和下部电极3的稳定性提高,也可以进行热处理。作为热处理条件,例如,升温速度优选为10℃/分钟~2000℃/分钟,更优选为100℃/分钟~1000℃/分钟。热处理时的保持温度优选为400℃~800℃,其保持时间优选为0.1小时~4.0小时。在热处理条件为上述的范围外的情况下,基底层2与下部电极3的密合不良,容易在下部电极3的表面产生凹凸。其结果,容易产生电介质膜5的介电特性的降低。
接着,在下部电极3上形成电介质膜5。本实施方式中,通过公知的成膜法,形成使构成电介质膜5的材料在下部电极3上堆积成薄膜状的作为堆积膜的电介质膜5。
作为公知的成膜法,例如示例:真空蒸镀法、溅射法、PLD(脉冲激光蒸镀法)、MO-CVD(有机金属化学气相沉积法)、MOD(有机金属分解法)、溶胶-凝胶法、CSD(化学溶液堆积法)。本实施方式中,从成本、容易得到较高的绝缘破坏电压等的观点来看,优选为溅射法。例如在通过PLD形成薄膜的情况下,在成膜时产生熔滴,且存在由于该熔滴而得到的电介质膜的绝缘破坏电压降低的倾向。
此外,有时在成膜时使用的原料(蒸镀材料,各种靶材材料,有机金属材料等)中含有微量的杂质、副成分等,但如果得到期望的介电特性,则没有特别的问题。
在使用溅射法的情况下,使用期望的组成的靶材,在下部电极上形成电介质膜。本实施方式中,为了将复合氧化物的半峰全宽设为上述的范围内,例如衬底温度越较低越好,当溅射时投入的电力过大时,存在半峰全宽过小的倾向,当过小时,存在半峰全宽过大的倾向。只要使这种成膜条件适宜组合即可。
接着,在形成的电介质膜5上,使用公知的成膜法形成构成上部电极的材料的薄膜并形成上部电极4。
经由以上的工序,如图1所示,得到在衬底1上形成有电容器部(下部电极3、电介质膜5和上部电极4)的薄膜电容器10。此外,保护电介质膜5的保护膜只要通过公知的成膜法形成即可,至少使电介质膜5覆盖露出于外部的部分。
(3.本实施方式的总结)
本实施方式中,作为通过成膜法得到的电介质膜的主成分,着眼于选自钡、钙和锶的A元素、选自镁和锌的B元素、选自铌和钽的C元素的复合氧化物。
该复合氧化物中,除了将A元素、B元素和C元素的含有比例设为上述的范围内的组成的最佳化之外,还将复合氧化物的预定的衍射峰的半峰全宽设为上述的范围。其结果,能够提高电介质膜的绝缘破坏电压。
通过成膜法形成的薄膜中,能够容易地控制晶体取向性,因此,通常,在通过成膜法形成薄膜的情况下,形成结晶性较高的薄膜。即,形成半峰全宽较小的薄膜。
但是,本发明人发现,与结晶性较高的薄膜相比,结晶性略低,包含非晶的区域的薄膜一方提高绝缘破坏电压。
另外,为了兼得绝缘破坏电压和Q值,通过限定半峰全宽的上限,防止非晶的区域过多。
(4.变形例)
上述的实施方式中,说明了电介质膜仅由本实施方式的电介质膜构成的情况,但也可以是具有组合了本实施方式的电介质膜和由其它的电介质组成物构成的膜的层叠结构的电子部件。例如,通过设为与原有的Si3Nx、SiOx、Al2Ox、ZrOx、Ta2Ox等的非晶电介质膜或结晶膜的层叠结构,可调整电介质膜5的阻抗和相对介电常数的温度变化。
另外,也可以是具有多个本实施方式的电介质膜的层叠电容器。
上述的实施方式中,为了提高衬底与下部电极的密合性,形成基底层,但在能够充分确保衬底与下部电极的密合性的情况下,能够省略基底层。另外,作为构成衬底的材料,在使用可用作电极的Cu、Pt等的金属、它们的合金、氧化物导电性材料等的情况下,能够省略基底层和下部电极。
以上,对本发明的实施方式进行了说明,但本发明不限定于上述的实施方式,也可以在本发明的范围内以各种方式进行改变。
实施例
以下,使用实施例和比较例,进一步详细地说明本发明。但是,本发明不限定于以下的实施例。
(实施例1和比较例1)
首先,如以下制作电介质膜的形成所需要的靶材。
作为A元素的原料粉末,准备碳酸钡(BaCO3)、碳酸钙(CaCO3)和碳酸锶(SrCO3)的各粉末,作为B元素的原料粉末,准备氧化镁(MgO)和氧化锌(ZnO)的各粉末,作为C元素的原料粉末,准备氧化铌(Nb2O5)和氧化钽(Ta2O5)的各粉末。将这些粉末以成为表1所示的实施例1和比较例1的各试样的组成的方式称重。
将称重的B元素的原料粉末、C元素的原料粉末、水、的ZrO2珠放入容积为1L的聚丙烯制宽口锅中,将湿式混合进行20小时。然后,使混合粉末浆料以100℃干燥20小时,将得到的混合粉末放入Al2O3坩埚中,通过在大气中以1250℃保持5小时的烧成条件进行1次预烧,得到含有B元素与C元素的复合氧化物的1次预烧粉末。
将得到的1次预烧粉末、A元素的原料粉末、水、的ZrO2珠放入容积为1L的聚丙烯制宽口锅中,将湿式混合进行20小时。然后,使混合粉末浆料以100℃干燥20小时,将得到的混合粉末放入Al2O3坩埚,通过在大气中以1050℃保持5小时的烧成条件进行2次预烧,得到含有A元素、B元素、C元素的复合氧化物的2次预烧粉末。
不含有B元素的AO-C2O5系化合物阻碍设为目的AO-BO-C2O5的生成,但通过这样进行两个阶段的预烧,能够抑制AO-C2O5系化合物生成。
将得到的2次预烧粉末放入乳钵,将作为粘合剂的浓度6wt%的PVA(聚乙烯醇)水溶液以相对于2次预烧粉末成为10wt%的方式添加,使用乳棒制作造粒粉。将制作的造粒粉以厚度成为5mm左右的方式投入的金属模具中,使用单轴加压冲压机进行加压成形,得到成形体。成形条件将压力设为2.0×108Pa,且将温度设为室温。
然后,对于得到的成形体,将升温速度设为100℃/小时,将保持温度设为400℃,且将温度保持时间设为4小时,在常压的大气中进行脱粘合剂处理。接着,将升温速度设为200℃/小时,将保持温度设为1600℃~1700℃,将温度保持时间设为12小时,在常压的大气中进行烧成,得到烧结体。
以得到的烧结体的厚度成为4mm的方式,利用圆筒研磨机研磨两面,得到用于形成电介质膜的靶材。
接着,准备在350μm厚的Si单晶衬底的表面具备作为6μm厚的绝缘层的SiO2的10mm×10mm角的衬底。在该衬底的表面上,将作为基底层的Ti薄膜以成为20nm的厚度的方式通过溅射法形成。
接着,在上述中形成的Ti薄膜上,将作为下部电极的Pt薄膜以成为100nm的厚度的方式通过溅射法形成。
相对于形成的Ti/Pt薄膜,将升温速度设为400℃/分钟,将保持温度设为700℃,将温度保持时间设为30分钟,将气氛设为氧气氛,在常压下进行热处理。
在热处理后的Ti/Pt薄膜上形成电介质膜。本实施例中,除了试样编号26之外,使用上述中制作的靶材,以在下部电极上成为1000nm的厚度的方式通过溅射法形成电介质膜。通过溅射法的成膜中,将衬底温度、溅射时的投入电力和成膜压力设为表1所示的条件。另外,为了使下部电极的一部分露出,使用金属掩模,形成未成膜电介质膜的区域。
另外,试样编号26中,使用上述中制作的靶材,在下部电极上以成为1000nm的厚度的方式通过PLD法形成电介质膜。成膜条件中,氧压设为1×10-1(Pa),将衬底温度设为200℃。另外,与试样编号1~25一样,为了使下部电极的一部分露出,使用金属掩模,形成局部未成膜电介质膜的区域。
接着,在得到的电介质膜上使用蒸镀装置形成作为上部电极的Ag薄膜。将上部电极的形状使用金属掩模以成为直径100μm、厚度100nm的方式形成,由此,得到具有图1所示的结构的薄膜电容器的试样(试样编号1~26)。
此外,就电介质膜的组成而言,对于所有的试样,使用XRF(荧光X射线元素分析)进行分析,确认到与表1所记载的组成一致。另外,电介质膜的厚度设为如下得到的值,利用FIB切削薄膜电容器,并利用SEM(扫描型电子显微镜)观察得到的截面并进行测长。
对于得到的所有的薄膜电容器试样,通过下述所示的方法进行电介质膜的XRD测定。另外,通过下述所示的方法测定电介质膜的Q值和绝缘破坏电压。
(XRD测定)
相对于电介质膜进行XRD测定,在得到的X射线衍射图中,特定(110)面的衍射峰,并算出其半峰全宽。将结果在表1中表示。
XRD测定中,作为X射线源使用Cu-Kα射线,该测定条件设为电压为45kV、电流为200mA且2θ=20°~90°的范围。
(绝缘破坏电压)
绝缘破坏电压(Vbd)如以下测定。相对于薄膜电容器,在下部电极露出的区域和上部电极连接超绝缘计(HIOKI SM7120),以5V/秒的阶段施加电压并测量电阻值。将从初始电阻值降低两位数时的电压值设为破坏电压值(V),并将得到的破坏电压值(V)处于电介质膜厚的数值设为绝缘破坏电压(Vbd)(V/μm)。本实施例中,对于各试样,测定5个薄膜电容器的绝缘破坏电压,将其平均值设为各试样的绝缘破坏电压。本实施例中,绝缘破坏电压越高越好,将绝缘破坏电压为500V/μm以上的试样判断为良好。将结果在表1中表示。
(Q值)
Q值设为相对于薄膜电容器,在基准温度25℃下利用RF阻抗/材料分析仪(Agilent株式会社制造4991A)在频率2GHz、输入信号电平(测定电压)0.5Vrms的条件下测定的介质损耗(tanδ)的倒数。本实施例中,Q值越高越好,将Q值为350以上的试样判断为良好。将结果在表1中表示。
【表1】
根据表1能够确认到,“x”、“y”和“z”的关系为上述的范围内,且(110)面的衍射峰的半峰全宽满足上述的范围的试样能够兼得绝缘破坏电压和Q值。
另一方面,能够确认到即使在“x”、“y”和“z”的关系为上述的范围内,(110)面的衍射峰的半峰全宽也不满足上述的范围的情况下,绝缘破坏电压较低。另外,能够确认到“x”、“y”和“z”的关系为上述的范围外的试样的Q值较低。
另外,能够确认到在通过PLD法成膜的情况下,若是表1所记载的条件,则由于(110)面的衍射峰的半峰全宽不满足上述的范围,且成膜时产生的熔滴的影响,绝缘破坏电压较低。
此外,关于试样编号17~19,虽然成膜之后具有膜的形态,但时间经过时,膜破裂,因此,不能进行半峰全宽、绝缘破坏电压和Q值的测定。
(实施例2)
关于试样编号9,除了将电介质膜的厚度变更成表2所示的厚度以外,通过与实施例1相同的条件形成电介质膜,并通过与实施例1相同的条件评价电介质膜。将结果在表2中表示。
【表2】
能够确认到即使在将电介质膜的厚度设为表2所示的厚度的情况下,也可得到同等的特性。
产业上的可利用性
根据本发明,得到绝缘破坏电压较高的电介质膜。这种薄膜状的电介质膜使用于高频用的电子部件、例如平衡-不平衡变压器、耦合器、滤波器、或组合了滤波器的双工器、天线共用器等。
Claims (3)
1.一种电介质膜,作为其主成分,含有以通式xAO-yBO-zC2O5表示的复合氧化物,所述电介质膜的特征在于:
所述A为选自由钡、钙和锶构成的组中的至少一者,
所述B为选自由镁和锌构成的组中的至少一者,
所述C为选自由铌和钽构成的组中的至少一者,
所述x、y和z满足以下关系:x+y+z=1.000,0.375≤x≤0.563,0.250≤y≤0.500,x/3≤z≤(x/3)+1/9,
在所述电介质膜的X射线衍射图中,所述复合氧化物的(110)面的衍射峰的半峰全宽为0.40°以上。
2.根据权利要求1所述的电介质膜,其特征在于:
(110)面的衍射峰的半峰全宽为0.40°以上6.00°以下。
3.一种电子部件,其特征在于,具有权利要求1或2所述的电介质膜。
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