JP6885110B2 - 誘電体膜および電子部品 - Google Patents
誘電体膜および電子部品 Download PDFInfo
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- JP6885110B2 JP6885110B2 JP2017040107A JP2017040107A JP6885110B2 JP 6885110 B2 JP6885110 B2 JP 6885110B2 JP 2017040107 A JP2017040107 A JP 2017040107A JP 2017040107 A JP2017040107 A JP 2017040107A JP 6885110 B2 JP6885110 B2 JP 6885110B2
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- 239000013078 crystal Substances 0.000 claims description 42
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 239000010408 film Substances 0.000 description 129
- 230000015556 catabolic process Effects 0.000 description 40
- 239000000758 substrate Substances 0.000 description 30
- 239000010409 thin film Substances 0.000 description 30
- 239000003990 capacitor Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 229910004205 SiNX Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000004544 sputter deposition Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000000224 chemical solution deposition Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001451 molecular beam epitaxy Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- 239000012856 weighed raw material Substances 0.000 description 1
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- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
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Description
NaCl型結晶構造を有するアルカリ土類金属酸化物を主成分とする誘電体膜において、
前記誘電体膜は面直方向に(111)配向した柱状構造を有し、
前記誘電体膜のCu−KαX線回折チャートにおいて、(111)の回折ピークの半値幅が0.3°〜2.0°であることを特徴とする。
図1は、本発明の一実施形態に係る誘電体膜を用いた電子部品の一例である薄膜コンデンサ10の断面図である。薄膜コンデンサ10は、支持基板1の表面に積層された下部電極3と上部電極4及び下部電極3と上部電極4の間に設けられた誘電体膜5とを備えている。支持基板1と下部電極3の間に、支持基板1と下部電極3との密着性を向上させるために下地層2を備える。支持基板1は、薄膜コンデンサ10全体の機械的強度を確保する機能を有する。
図1に示す支持基板1を形成するための材料はとくに限定されるものではなく、単結晶としてはSi単結晶、SiGe単結晶、GaAs単結晶、InP単結晶、SrTiO3単結晶、MgO単結晶、LaAlO3単結晶、ZrO2単結晶、MgAl2O4単結晶、NdGaO3単結晶や、セラミック多結晶基板としてはAl2O3多結晶、ZnO多結晶、SiO2多結晶や、Ni、Cu、Ti、W、Mo、Al、Ptなどの金属や、それらの合金の基板などによって支持基板1を形成することができるが特に限定されるものではない。これらの中では、低コスト、加工性から、Si単結晶を支持基板1として使用されることが一般的である。支持基板1は、基板の材質によってその比抵抗が異なる。比抵抗が低い材料を支持基板1として使用する場合、そのまま使用すると支持基板1側への電流のリークが薄膜コンデンサ10の電気特性に影響を及ぼすことがある。そのため、支持基板1の表面に絶縁処理を施し、使用時の電流が支持基板1へ流れないようにする場合もある。例えば、Si単結晶を支持基板1として使用する場合においては、支持基板1表面を酸化させてSiO2絶縁層の形成を行うことや、支持基板1表面にAl2O3、SiO2、SiNxなどの絶縁層を形成してもよく、支持基板1への絶縁が保てればその絶縁層の材料や膜厚は限定されないが、0.01μm以上が好ましい。0.01μm未満では絶縁性が保てないため、絶縁層の厚みとして好ましくない。支持基板1の厚さは、薄膜コンデンサ全体の機械的強度を確保することができれば、とくに限定されるものではないが、たとえば、10μm〜5000μmに設定される。10μm未満の場合は機械的強度が確保できなく、5000μmを超えると電子部品の小型化に寄与できないといった問題が生じる場合がある。
本実施形態において、絶縁処理を施した支持基板1表面に、下地層2を備えることが好ましい。下地層2は、支持基板1と下部電極3との密着性向上を目的として挿入される。一例として、下部電極3にCuを使用する場合には下地層2はCrを、下部電極3にPtを使用する場合にはTiを下地層2として挿入することが一般的である。
下部電極3を形成するための材料は、導電性を有していれば良く、例えば、Pt、Ru、Rh、Pd、Ir、Au、Ag、Cu、Niなどの金属や、それらの合金、又は導電性酸化物などによって形成することができる。そのため、コストや誘電体膜5を熱処理するときの雰囲気に対応した材料を選択すればよい。誘電体膜5は大気中の他、不活性ガスであるN2やAr、またO2、不活性ガスと還元性ガスであるH2の混合ガスで熱処理を行うことが出来る。下部電極3の膜厚は電極として機能すれば良く、10nm以上が好ましい。10nm未満の場合、導電性が悪くなることから好ましくない。また、支持基板1に電極として使用可能なCuやNi、Pt等や酸化物導電性材料などを使用した基板を使用する場合は、前述した下地層2と下部電極3は省略することができる。
誘電体膜5は、NaCl型結晶構造を有するアルカリ土類金属酸化物を主成分とし、面直方向に(111)配向した柱状構造を有し、誘電体膜のCu−KαX線回折チャートにおいて、(111)の回折ピークの半値幅が0.3°〜2.0°であることを特徴とする。
本発明の柱状構造とは、図2に示すように、誘電体膜の垂直方向の断面で観察した場合、誘電体膜の厚み方向に長い結晶子6を備えている構造のことを意味している。本発明の柱状構造は、誘電体膜全体に支持基板表面の法線方向または±5°に沿って延び、図2中に記載されているHとLの比、つまり、アスペクト比が(H/L)≧2を満足する結晶子からなる構造となっている。
本実施形態の一例において、薄膜コンデンサ10は、誘電体膜5の表面に、薄膜コンデンサ10の他方の電極として機能する上部電極4を備えている。上部電極4を形成するための材料は、導電性を有していれば、とくに限定されるものではなく、下部電極3と同様の材料によって、上部電極4を形成することができる。上部電極4の膜厚は電極として機能すれば良く、10nm以上が好ましい。膜厚が10nm以下の場合、導電性が悪化するため上部電極4として好ましくない。
まず、350μm厚のSiの表面に6μm厚のSiO2絶縁層を備えた10mm×10mm角の支持基板の表面上に、下地層であるCr薄膜を20nmの厚さとなるようにスパッタリング法で形成した。
0℃、温度保持時間を0.5時間、雰囲気を窒素雰囲気とし常圧下で熱処理を行った。
柱状構造は、誘電体膜の断面をTEM観察することで確認した。暗視野像にて結晶子のアスペクト比を計測し、そのアスペクト比が2以上の結晶子で構成されているものについて、柱状構造を有する膜と定義した。
<結晶配向及び結晶性>
誘電体膜に対し、X線回折(平行法)による測定を行い、回折パターンを得た。X線源としてCu−Kα線を用い、その測定条件は、電圧45kV、200mA、2θ=20°〜80°の範囲とした。誘電体膜の配向について、得られた回折パターンにおける、(111)のピークと、(200)のピーク強度比を比較し、その比((111)のピーク強度/(200)のピーク強度)が1.5以上を示すものについて、(111)に配向していると定義した。また、結晶性を示す指標として、配向している面の半値幅を測定した。図3に得られた回折パターンから半値幅を測定した一例を示す。(実施例1試料No.1)
比誘電率、Q値は、薄膜コンデンサ試料に対し、基準温度25℃において、RFインピーダンス/マテリアル・アナライザ(Agilent社製4991A)にて、周波数2GHz,入力信号レベル(測定電圧)0.5Vrmsの条件下で静電容量、誘電損失(tanδ)を測定し、測定された静電容量と膜厚の測定の結果より比誘電率を、Q値は誘電損失の逆数(1/tanδ)から算出した(単位なし)。アモルファスSiNx膜の比誘電率が7程度であったため、本発明においては、それより高い比誘電率であることを良好とした。また、アモルファスSiNx膜のQ値は約500程度であったが、近年より高周波特性の良い部品が求められているため、Qの値が850以上を良好とした。
絶縁破壊電圧は、薄膜コンデンサ試料に対し、下部電極が露出している領域と上部電極にデジタル超高抵抗/微小電流計(ADVANTEST R8340)に接続し、5V/秒のステップで電圧を印加して計測し、初期抵抗値から2桁低下したときの電圧値を読み取り、その値を試料の破壊電圧値(V)とした。得られた破壊電圧値(V)を誘電体膜厚で除した数値を絶縁破壊電圧(Vbd)(V/μm)とした。表2には、n=5の平均値を記載した。アモルファスSiNxの絶縁破壊電圧が500V/μm〜700V/μm程度であったが、近年よりESD特性の良い部品が求められているため、絶縁破壊電圧が1250V/μm以上を良好とした。
表2より、NaCl型結晶構造を有するアルカリ土類金属酸化物を主成分とする誘電体膜であって、前記誘電体膜は面直方向に(111)配向した柱状構造を有し、前記誘電体膜のCu−KαX線回折チャートにおいて、(111)の回折ピークの半値幅が0.3°〜2.0°である試料No.1〜試料No.14は、800nmという薄膜にしても、特性が良好であり、Q値が850以上、絶縁破壊電圧が1250V/μm以上であることを確認できた。
表2より、NaCl型結晶構造を有するアルカリ土類金属酸化物を主成分とする誘電体膜であって、前記誘電体膜は面直方向に(111)配向した柱状構造を有し、前記誘電体膜のCu−KαX線回折チャートにおいて、(111)の回折ピークの半値幅が0.3°〜2.0°であり、副成分としてTa、Nb、V、Hf、Zr、Ti、Znのうち少なくとも一種類の元素を含む試料No.15〜試料No.35は、副成分を含まない試料No.1〜試料No.14よりも、高い絶縁破壊電圧を有していることが確認できる。更に、主成分に対して0mol%<x≦20mol%の範囲で副成分を含む試料No.15〜試料No.29は、特に特性が良好であり、Q値が1050以上、絶縁破壊電圧が1350V/μm以上であることが確認できた。
表2より、比較例である試料No.36〜試料No.39は(111)配向の柱状構造を備えていないため、薄膜化した際に結晶性が低下してしまい、Q値が850以下と低い値となってしまう。比較例である試料No.40及び試料No.41は(111)配向の柱状構造を有しているが、半値幅が0.2°であったため、絶縁破壊電圧に寄与できず、絶縁破壊電圧が1240V/μm以下であった。また、比較例である試料No.42及び試料No.43は(111)配向の柱状構造を有しているが、半値幅が2.1°であり絶縁破壊電圧は良好であったが、結晶子サイズが小さくなり過ぎたため、Q値が850以下となってしまった。また、比較例である試料No.44〜試料No.47は(111)配向の柱状構造を備えておらず、また半値幅が本発明の範囲外あるため、高いQ値と高い絶縁破壊電圧を維持することが出来ないことが確認できた。
誘電体膜の厚みを変更した以外は、実施例1の試料No.29と同様の手法で試料を作製し、実施例1と同様の評価を行った。結果を表3に示す。
表3より誘電体膜の膜厚が異なっても、NaCl型結晶構造を有するアルカリ土類金属酸化物を主成分とする誘電体膜であって、前記誘電体膜は面直方向に(111)配向した柱状構造を有し、前記誘電体膜のCu−KαX線回折チャートにおいて、(111)の回折ピークの半値幅が0.3°〜2.0°である特徴を有する誘電体膜であれば、50nmまで薄膜化してもほぼ同様な特性を示すことが確認できた。つまり、本発明の特徴を有する誘電体膜であれば、薄膜化しても特性の低下がほとんど無く、高い比誘電率と高いQ値及び高い絶縁破壊電圧を有することが確認できた。
2… 下地層
3… 下部電極
4… 上部電極
5… 誘電体膜
6… 結晶子
10… 薄膜コンデンサ
Claims (4)
- NaCl型結晶構造を有する
アルカリ土類金属酸化物を主成分とする誘電体膜において、
前記誘電体膜は面直方向に(111)配向した柱状構造を有し、
前記誘電体膜のCu−KαX線回折チャートにおいて、(111)の回折ピークの半値幅が0.5°〜2.0°であることを特徴とする誘電体膜。 - NaCl型結晶構造を有する
アルカリ土類金属酸化物を主成分とする誘電体膜において、
前記誘電体膜は面直方向に(111)配向した柱状構造を有し、
前記誘電体膜のCu−KαX線回折チャートにおいて、(111)の回折ピークの半値幅が0.3°〜2.0°であり、
前記誘電体膜は、副成分としてTa、Nb、V、Hf、Zr、Tiのうち少なくとも一種類の元素を含むことを特徴とする誘電体膜。 - 前記副成分の総含有量をxとすると、前記xが前記主成分に対して0mol%<x≦20mol%の範囲であることを特徴とする請求項2に記載の誘電体膜。
- 請求項1〜請求項3のいずれかに記載の誘電体膜を有する電子部品。
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