JP5799312B2 - Thin film dielectric - Google Patents
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- 229910052759 nickel Inorganic materials 0.000 claims description 8
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 39
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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- Inorganic Insulating Materials (AREA)
- Compounds Of Iron (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Surface Treatment Of Glass (AREA)
- Silicon Compounds (AREA)
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Description
本発明は、薄膜誘電体に関するものであり、さらに詳しく述べるならば、本発明者らが、非特許文献1:日本金属学会報「まてりあ」Vol.37(1998)、No.9, p745-748、グラニュラー系トンネル型巨大磁気抵抗−高次のスピン依存トンネル効果―において、巨大磁気抵抗(GMR)材料として発表したいわゆるナノグラニュラー磁性材料が薄膜誘電体として優れた性質をもつこと発見し、この発見に基づいて提案する新規な薄膜誘電体に関するものである。 The present invention relates to a thin-film dielectric, and, in more detail, the present inventors have reported that Non-Patent Document 1: Journal of the Japan Institute of Metals “Materia” Vol. 37 (1998), No. 9, p745. -748, the giant tunnel magnetoresistive magnetoresistive -high-order spin-dependent tunnel effect- discovered that the so-called nanogranular magnetic material announced as a giant magnetoresistive (GMR) material has excellent properties as a thin film dielectric. The present invention relates to a novel thin film dielectric proposed based on the findings.
携帯電話、パソコンなどの電子機器においては、BaTiO3,SrTiO3,Ba(Zr,Ti)O2等の様々の材料系からなる誘電体を用いた電子部品が数多く使われており、近年、その電子機器の小型・軽量化、省電力化、また多機能・高機能化に伴い、より高機能、もしくは多様な性能を有する誘電材料が求められている。特に、小型化や高密度化に対応するために、材料の微小サイズ化、薄膜化が必要である。例えば、特許文献1:特開平4−133369号公報は、PbTiO3などの酸化物薄膜誘電体に関するものであり、絶縁体基板と誘電体薄膜の間にTiを含む酸化物バッファー層を介在させることにより、密着性及び誘電特性を改良することを提案している。 In electronic devices such as mobile phones and personal computers, many electronic parts using dielectric materials made of various materials such as BaTiO 3 , SrTiO 3 , Ba (Zr, Ti) O 2 are used. As electronic devices become smaller and lighter, save power, and have multiple functions and functions, there is a demand for dielectric materials having higher functions or various performances. In particular, in order to cope with downsizing and high density, it is necessary to reduce the material size and thickness. For example, Patent Document 1: Japanese Patent Laid-Open No. 4-133369 relates to an oxide thin film dielectric such as PbTiO 3, and an oxide buffer layer containing Ti is interposed between an insulating substrate and the dielectric thin film. Proposed to improve adhesion and dielectric properties.
一方、情報通信技術においては、信号処理速度の高速化が急速に進展している。このような高速信号伝送においては、信号配線として、例えば、半導体基板上に実装されたインピーダンス整合のためのマイクロストリップ線路、コプレーナ線路等の高周波伝送に対応したCPUを搭載した基板の高速伝送回路など伝送線路の回路設計が必要であり、高周波特性には伝送線路の誘電特性が大きく影響するため、絶縁層などに高周波誘電特性に優れた薄膜誘電材料を用いる必要がある。
非特許文献2: 福岡県工業技術センター研究報告第13号(平成14年度)No.11,第1〜4頁、「高周波誘電体薄膜の作製と応用」においては、Ba/Ti比率を変化させたBa-Ti-O系誘電体薄膜をゾルゲル法で成膜し、GHz帯の誘電特性を測定している。但し、薄膜の誘電特性測定法は述べられていない。
On the other hand, in information communication technology, signal processing speed is rapidly increasing. In such a high-speed signal transmission, as a signal wiring, for example, a high-speed transmission circuit of a substrate on which a CPU corresponding to high-frequency transmission such as a microstrip line for impedance matching and a coplanar line mounted on a semiconductor substrate is mounted. Since the circuit design of the transmission line is necessary and the dielectric property of the transmission line greatly affects the high frequency characteristics, it is necessary to use a thin film dielectric material having excellent high frequency dielectric characteristics for the insulating layer or the like.
Non-Patent Document 2: Research Report No. 13 (FY2002) No. 11, page 1-4, “Fabrication and application of high-frequency dielectric thin film”, Ba—Ti—O based dielectric thin film with varying Ba / Ti ratio is formed by sol-gel method, and dielectric of GHz band is obtained. The characteristics are being measured. However, the method for measuring the dielectric properties of the thin film is not described.
誘電材料を用いた電子デバイスの小型化には、誘電材料の小型化・薄膜化が不可欠である。BaTiO3,SrTiO3、CaTiO3,(Zn,Sn)TiO3,Ba(Zr,Ti)O3等の誘電体材料は粉末を焼結したバルク状態で優れた誘電特性を示す。また、これらの材料を、物理的蒸着法などの種々の薄膜作製プロセスが提案されている。しかし、薄膜化により、通常、大幅に誘電特性が劣化する。これは種々の薄膜作製プロセスに作製される誘電体薄膜においてはバルクと同じ構造が得られないためであって、この原因は、誘電特性を発生する結晶構造自体にあり、例えば、特許文献1で考察されている誘電体層と基板の格子定数不整合も誘電体の結晶構造の一つの局面ということができる。
またコランダム系Al2O3やケイ酸塩系SiO2、Mg2Si4などの常誘電特性を示す絶縁体においては、誘電率が小さく、また薄膜化した場合にその絶縁性を維持するのは容易ではない。
尚、薄膜材料とは真空蒸着法、電子線蒸着法、スパッタ法、ゾルゲル法、めっき法等の成膜法によってガラス、石英、Siウエハ、MgO等の基板上に、厚さ数ミクロン程度に堆積された材料である。
Miniaturization and thinning of dielectric materials are indispensable for miniaturization of electronic devices using dielectric materials. Dielectric materials such as BaTiO 3 , SrTiO 3 , CaTiO 3 , (Zn, Sn) TiO 3 , and Ba (Zr, Ti) O 3 exhibit excellent dielectric properties in a bulk state in which powder is sintered. Further, various thin film manufacturing processes such as physical vapor deposition have been proposed for these materials. However, the dielectric properties usually deteriorate significantly due to the thinning. This is because the same structure as the bulk cannot be obtained in a dielectric thin film produced by various thin film production processes, and this is caused by the crystal structure itself that generates dielectric characteristics. The considered lattice constant mismatch between the dielectric layer and the substrate can also be considered as one aspect of the crystal structure of the dielectric.
Moreover, in an insulator having a paraelectric characteristic such as corundum-based Al 2 O 3 , silicate-based SiO 2 , Mg 2 Si 4 , the dielectric constant is small, and when the film is thinned, the insulation is maintained. It's not easy.
The thin film material is deposited on a glass, quartz, Si wafer, MgO or other substrate to a thickness of several microns by a film deposition method such as vacuum deposition, electron beam deposition, sputtering, sol-gel, or plating. Material.
ところで、伝送線路設計においては、伝送線路上に作製できる絶縁膜や誘電体膜の選択肢が限られており、伝送線路設計に制約がある。例えば、伝送線路の高周波特性は、線路の断面形状と絶縁層の誘電特性で決まるため、信号配線として、インピーダンス整合のためのマイクロストリップ線路、コプレーナ線路等の高周波伝送に対応した伝送線路構造の最適化する必要がある。しかしながら、薄膜化により誘電率が低下することは、そのこと自身が問題であるのみならず、誘電率低下程度は薄膜の厚さの減少による絶縁性の劣化などに依存するので、任意の誘電特性を選択することの制約になっている。 By the way, in the transmission line design, the choices of the insulating film and the dielectric film that can be produced on the transmission line are limited, and the transmission line design is limited. For example, the high-frequency characteristics of a transmission line are determined by the cross-sectional shape of the line and the dielectric characteristics of the insulating layer. Therefore, the optimal transmission line structure that supports high-frequency transmission such as microstrip lines and coplanar lines for impedance matching as signal wiring It is necessary to make it. However, the decrease in dielectric constant due to the reduction in film thickness is not only a problem in itself, but the degree of decrease in dielectric constant depends on the deterioration of insulation due to the decrease in the thickness of the thin film. It is a restriction to select.
よって、本発明は、半導体基板、絶縁体基板など各種基板あるいは半導体もしくは絶縁体の層上に薄膜として成膜した際に高い誘電率を示すとともに、多様な伝送路設計を可能となる薄膜誘電体を提供することを目的とする。 Accordingly, the present invention provides a thin film dielectric that exhibits a high dielectric constant when it is formed as a thin film on various substrates such as a semiconductor substrate and an insulator substrate, or a layer of a semiconductor or an insulator, and enables various transmission line designs. The purpose is to provide.
本発明者らは、絶縁体マトリックスとnmサイズの金属グラニュールからなるナノグラニュラー構造を有する薄膜は、絶縁体中に微細な金属グラニュールが分散して存在する効果により優れた薄膜誘電体であることを見出して本発明を完成した。 The inventors of the present invention are that a thin film having a nano-granular structure composed of an insulator matrix and nm-sized metal granules is an excellent thin film dielectric due to the effect that fine metal granules are dispersed in the insulator. And the present invention was completed.
本発明の特徴とするところは次の通りである。第1発明は、組成が一般式FeaCobNicMwNxOyFzで表わされ,M成分はMg,Al,Si,Ti,Y,Zr,Nb,Hf,Taのうちから選択される1種又は2種以上の元素であり,組成比a,b,c,w,x,y,zは原子比率(%)で、0≦a≦60,0≦b≦60,0≦c≦60,10<a+b+c<60,10≦w≦50,0≦x≦50,0≦y≦50,0≦z≦50,20≦x+y+z≦70,a+b+c+w+x+y+z=100,で表わされるとともに、前記Fe,Co及びNiの少なくとも1種からなり、かつnmサイズを有する金属グラニュールが、前記M成分と前記N,O及びFの少なくとも1種とからなる絶縁体マトリックスに分散したナノグラニュラー構造を有する薄膜誘電体において、前記絶縁体の薄膜の誘電率より高い誘電率を有するとともに、磁性と誘電特性が相互作用することを特徴とする。第2発明は、第1発明に記載の薄膜誘電体において誘電率が外部磁界により調整可能であることを特徴とする。
The features of the present invention are as follows. The first invention, the composition is represented by the formula Fe a Co b Ni c M w N x O y F z, M components Mg, Al, Si, Ti, Y, Zr, Nb, Hf, and
第3発明は、組成がFe−Co−Mg−Fであり、前記a+b=12〜45%(c=0)であることを特徴とする第1発明に記載の薄膜誘電体に関する。 A third invention relates to the thin film dielectric according to the first invention, characterized in that the composition is Fe—Co—Mg—F, and the a + b is 12 to 45% (c = 0).
第4発明は、組成がFe−Co−Al−Fであり、前記a+b=38〜48%(c=0)であることを特徴とする第1発明に記載の薄膜誘電体に関する。 A fourth invention relates to the thin film dielectric according to the first invention, characterized in that the composition is Fe-Co-Al-F, and the a + b = 38 to 48% (c = 0).
第5発明は、基板上に成膜され、膜厚が5μm以下であるとことを特徴とする第1から第4発明までのいずれかに記載の薄膜誘電体に関する。 A fifth invention relates to the thin film dielectric according to any one of the first to fourth inventions , wherein the film is formed on a substrate and has a film thickness of 5 μm or less.
第6発明は、ガラス板、表面を熱酸化した単結晶シリコンウェーハ、又はMgOからなる基板に直接成膜されたことを特徴とする第1から第5発明までのいずれかに記載の薄膜誘電体に関する。
以下、本発明を詳しく説明する。
The sixth invention is a thin film dielectric according to any one of the first to fifth inventions , wherein the thin film dielectric is directly formed on a glass plate, a single crystal silicon wafer whose surface is thermally oxidized, or a substrate made of MgO. About.
The present invention will be described in detail below.
組成
本発明(第1発明)の薄膜誘電体の組成を表す一般式FeaCobNicMwNxOyFzにおいて、Fe,Co,Niの合計含有量が原子比率で10%未満すなわちw + x+y+z>90であると、これらの金属からなるグラニュールの体積が小さくなり、グラニュールの効果による誘電率の増加が小さい。また、膜の磁性が失われる。また、前記の原子比率が60%を超えるすなわち40>w + x+y+zであると、これらの金属からなるグラニュールの粒径が大きくなって部分的に接触することにより、電気抵抗率が減少し誘電損失が増大するため、40≦w + x+y+z≦90の範囲に限定した。
図1には、後述の実施例で行った方法で成膜した、Fe,Co,Mg及びFからなる薄膜について、膜中のFe+Co量(100−w−z,c=x=y=0)と誘電率の関係を示した。Fe+Co量が請求項1と一致する10〜60at%の組成範囲において誘電率の増加が確認でき、特にFe+Co量12〜45at%の範囲(第3発明)では10以上の値を示す。また、図2には、Fe,Co,Al及びFからなる薄膜について、膜中のFe+Co量と誘電率の関係を示した。同様にFe+Co量10〜60at%の組成範囲において誘電率の増加が確認でき、特にFe+Co量33〜48at%(第4発明)の範囲では10以上の値を示す。
さらに、Fe−Co−Mg−F系組成(図1)において、a+b=21〜24%、及びFe−Co−Al−F系組成(図2)において、a+b=38〜40%において、誘電率がピーク値を示すのは、膜組成、特に金属と誘電体との存在比率によって、グラニュールの粒径や分布状態、またグラニュラー間の誘電体の厚みなどの膜構造が変化し、その最適構造によって誘電率の増加効果が得られるためであると考えられる。また、最適構造においては、分極に寄与する電子の増大、グラニュール及び誘電体の分極に伴う局所的な電界強度の増大が起きていると考えられる。
In the formula Fe a Co b Ni c M w N x O y F z representing the composition of the thin film dielectric composition <br/> present invention (first invention), Fe, Co, the total content of Ni atomic ratio If it is less than 10%, that is, w + x + y + z> 90, the volume of the granule made of these metals becomes small, and the increase in the dielectric constant due to the effect of the granule is small. In addition, the magnetic properties of the film are lost. Further, when the atomic ratio exceeds 60%, that is, 40> w + x + y + z , the particle diameter of the granule made of these metals becomes large and partially contacts, so that the electrical resistivity is reduced and the dielectric is reduced. Since loss increases, it limited to the range of 40 <= w + x + y + z <= 90.
FIG. 1 shows the amount of Fe + Co in a film (100−w−z, c = x = y = 0) for a thin film made of Fe, Co, Mg, and F formed by a method performed in an example described later. And the relationship between dielectric constants. An increase in the dielectric constant can be confirmed in the composition range of 10 to 60 at% where the amount of Fe + Co is consistent with that of claim 1, and in particular, a value of 10 or more is shown in the range of 12 to 45 at% of Fe + Co (third invention) . FIG. 2 shows the relationship between the amount of Fe + Co in the film and the dielectric constant of the thin film made of Fe, Co, Al, and F. Similarly, an increase in dielectric constant can be confirmed in the composition range of Fe + Co amount of 10 to 60 at%, and in particular, in the range of Fe + Co amount of 33 to 48 at% (fourth invention ), a value of 10 or more is shown.
Further, in the Fe—Co—Mg—F composition (FIG. 1), the dielectric constant is a + b = 21 to 24%, and in the Fe—Co—Al—F composition (FIG. 2), a + b = 38 to 40%. Shows the peak value depending on the film composition, especially the abundance ratio of metal and dielectric, and the film structure such as the particle size and distribution of the granules and the thickness of the dielectric between the granules changes. This is considered to be because the effect of increasing the dielectric constant is obtained. In the optimum structure, it is considered that an increase in electrons that contribute to polarization and an increase in local electric field strength due to the polarization of granules and dielectrics occur.
M成分は、N、OあるいはFと結合し、誘電体のマトリックスを形成する。Mの含有量wが10未満であるとマトリックスを形成する十分な体積の絶縁体がないため、誘電特性は示さない。また、N,O,及びF量が50を超える場合は、MとN,O及びFとの化合物の化学量論比よりもN,O,及びFが過剰となり、過剰なN,O,及びFがグラニュールを形成するFe,Co又はNiと結合して金属グラニュールの形成を抑制することになるので、10≦w≦50,0≦x≦50,0≦y≦50,0≦z≦50,20≦x+y+z≦70とする。 The M component combines with N, O or F to form a dielectric matrix. When the content w of M is less than 10, there is no sufficient volume of an insulator to form a matrix, and therefore no dielectric properties are exhibited. When the amounts of N, O, and F exceed 50, N, O, and F are in excess of the stoichiometric ratio of the compound of M and N, O, and F, and excess N, O, and F Since F combines with Fe, Co or Ni forming the granules to suppress the formation of metal granules, 10 ≦ w ≦ 50, 0 ≦ x ≦ 50, 0 ≦ y ≦ 50, 0 ≦ z. ≦ 50, 20 ≦ x + y + z ≦ 70.
ナノグラニュラー構造
本発明のナノグラニュラー構造は、Fe,Co及びNiの少なくとも1種からなり、かつnmサイズを有する金属グラニュールが、M成分とN,O及びFの少なくとも1種とからなる絶縁体マトリックスに分散したものである。かかるナノグラニュラー構造は、本発明者らが、磁気抵抗素子に関する非特許文献1、特許文献2:特開2001−94175号公報、特許文献3:特開2002−344042号公報及び特許文献4:特開2003−258333号公報において発表しており、一軸磁気異方性に関しては特許文献5:特開平9−82522号公報において発表している。これらの特長を要約すると次のとおりである。
(イ)磁性金属と絶縁体セラミックスからなる金属―絶縁体ナノグラニュラー材料は、作製が容易であり、特性の再現性に優れている。
(ロ)粒径が数ナノメーター程度の微細な磁性金属グラニュールと、それを取り囲む薄い絶縁体の粒界相からなるナノグラニュラー構造を有している。
(ハ)それぞれのグラニュールは、誘電体(絶縁体)粒界相を挟んでほぼ均一に分散しており、電気伝導は粒界相によって分断されている。
(ニ)グラニュールの強磁性金属はナノサイズであるために、超常磁性を示す。
(ホ)1×104μΩcm以上の高い比電気抵抗を有する。
Nano-granular structure The nano-granular structure of the present invention is composed of at least one of Fe, Co, and Ni, and a metal granule having an nm size is composed of an M component and at least one of N, O, and F. Dispersed in an insulator matrix. Such a nano-granular structure has been developed by the inventors of Non-Patent Document 1, Patent Document 2: Japanese Patent Laid-Open No. 2001-94175, Patent Document 3: Japanese Patent Laid-Open No. 2002-344042, and Patent Document 4: Japanese Patent Laid-Open No. 2002-340402. No. 2003-258333, and uniaxial magnetic anisotropy is disclosed in Japanese Patent Laid-Open No. 9-82522. These features are summarized as follows.
(A) A metal-insulator nanogranular material composed of a magnetic metal and an insulator ceramic is easy to fabricate and has excellent reproducibility of characteristics.
(B) It has a nano-granular structure consisting of a fine magnetic metal granule having a particle size of several nanometers and a grain boundary phase of a thin insulator surrounding it.
(C) Each granule is dispersed almost uniformly across the dielectric (insulator) grain boundary phase, and electrical conduction is divided by the grain boundary phase.
(D) Since the ferromagnetic metal of the granule is nano-sized, it exhibits superparamagnetism.
(E) It has a high specific resistance of 1 × 10 4 μΩcm or more.
誘電率
本発明の薄膜誘電体の絶縁体マトリックスは前記M成分とN,O及びFの少なくとも1種とからなるものであり、例えばSiO2、MgO,Al2O3,TiO2、MgF2,AlF3 などである。これらの物質は常誘電体であり誘電率が低く、また薄膜化によって更に誘電率が減少するが、これらの絶縁体がナノグラニュールを分散させたナノグラニュラー構造のマトリックスを構成している本発明の薄膜誘電体の誘電率は、上述の常誘電体のみの薄膜の誘電率より高くなっている。
本発明においては、有意高周波回路設計上の都合から膜組成を変えることなどの簡便な方法により、任意に高周波帯の誘電率など誘電特性を最適化できることを見出した。
Insulator matrix thin film dielectric permittivity <br/> present invention are those comprising at least one of the M component and N, O and F, for example SiO 2, MgO, Al 2 O 3,
In the present invention, it has been found that dielectric properties such as dielectric constant of a high frequency band can be arbitrarily optimized by a simple method such as changing the film composition for the convenience of significant high frequency circuit design.
グラニュラー構造と誘電率
誘電体のみの薄膜は、成膜過程で避けられない種々の欠陥を含む等、バルク状態の(バルク状態と同じ)構造が得られないため、バルク材が有する誘電率より小さい値を示す。それに対して、本発明のナノグラニュラー構造を有する薄膜誘電体は、その構造が極めて微細、かつ緻密であるために、膜厚が薄くなるなど体積が減少しても、薄膜化による誘電率低下を補完して、マトリックス絶縁体が誘電体として本来有する値と同程度、或いはそれ以上の誘電率を発現できる。また、本発明の薄膜誘電体は、ナノグラニュラー構造な構造を維持している限り所定誘電率が現れ、成膜による欠陥などにより誘電率が影響されることがない。さらに、このような構造は、成膜される基板の結晶構造などに関係なく実現される。
Granular structure and dielectric constant A thin film made only of a dielectric material contains various defects that cannot be avoided in the film formation process, and a bulk structure (same as the bulk state) cannot be obtained. The value is smaller than the dielectric constant. On the other hand, the thin-film dielectric having a nano-granular structure of the present invention is extremely fine and dense, so even if the volume is reduced, such as when the film thickness is reduced, it compensates for the decrease in dielectric constant due to thinning. Thus, a dielectric constant equivalent to or higher than a value inherently possessed by the matrix insulator as the dielectric can be exhibited. In addition, the thin film dielectric of the present invention exhibits a predetermined dielectric constant as long as it maintains a nanogranular structure, and the dielectric constant is not affected by defects caused by film formation. Further, such a structure is realized regardless of the crystal structure of the substrate on which the film is formed.
本発明者らの研究の結果、ナノグラニュラー薄膜は、誘電体として次の特性をもっていることが分かった。
特性1:誘電率の制御が可能である。
特性2:磁性と誘電特性が相互作用する。なお、以下の説明では、「磁性と誘電の複合特性」、あるいは「磁化と誘電特性の複合機能性」ということもあるが、同じ意味である。
特性3:絶縁体マトリックスにおいて起こる電子の分極は十分に大きい。
これらの特性(1)〜(3)については以下さらに説明する。
As a result of the study by the present inventors, it was found that the nanogranular thin film has the following characteristics as a dielectric.
Characteristic 1: The dielectric constant can be controlled.
Characteristic 2: Magnetic and dielectric properties interact. In the following description, the term “composite characteristics of magnetism and dielectric” or “composite functionality of magnetization and dielectric characteristics” may be used, but they have the same meaning.
Characteristic 3: Electron polarization occurring in the insulator matrix is sufficiently large.
These characteristics (1) to (3) will be further described below.
(1)誘電率の制御
従来の誘電体は、BaTiO3,SrTiO3,Ba(Zr,Ti)O2等種類が限られていたが、本発明の薄膜誘電体の組成について請求項1を規定する組成範囲は非常に広いので、膜の組成を調整する簡便な方法により、誘電率を自由に制御することができる。また、必要により、成膜後熱処理を行うかあるいは成膜中の基板を加熱することにより、誘電率を制御することができる。
(1) Control of dielectric constant Conventional dielectrics are limited to BaTiO 3 , SrTiO 3 , Ba (Zr, Ti) O 2, etc., but the composition of the thin film dielectric of the present invention is defined in claim 1. Since the composition range is very wide, the dielectric constant can be freely controlled by a simple method of adjusting the composition of the film. If necessary, the dielectric constant can be controlled by performing heat treatment after film formation or heating the substrate during film formation.
(2)磁性と誘電特性の相互作用
図3は、後述の試料番号17について、実施例で説明しているLCRメータによる誘電率測定の際に試料に外部磁界を印加して、磁界中での誘電率の変化を計測した結果である。この薄膜は磁化を有しているので、外部磁界により磁化状態が変化する。一方、100kHzにおける誘電率は、外部磁界がゼロの基準誘電率に対して、磁界の正逆方向に対称的変化を表している。
(2) Interaction between magnetism and dielectric properties FIG. 3 shows an application of an external magnetic field to the sample for measuring the dielectric constant using the LCR meter described in the examples for sample number 17 described later. It is the result of measuring the change in dielectric constant in a magnetic field. Since this thin film has magnetization, the magnetization state is changed by an external magnetic field. On the other hand, the dielectric constant at 100 kHz represents a symmetric change in the forward and reverse direction of the magnetic field with respect to the reference dielectric constant of zero external magnetic field.
(3)電子の分極
図1におけるFe+Co=0の組成及び、図2におけるFe+Co=0の組成では絶縁体の分極により誘電率が定められる。これに対して、10<Fe+Co<60の範囲では誘電率の増大が見られ、分極した電子が多くなっていると考えられる。
続いて、本発明の薄膜誘電体の物性などについて説明する。
(3) Electron polarization In the composition of Fe + Co = 0 in FIG. 1 and the composition of Fe + Co = 0 in FIG. 2, the dielectric constant is determined by the polarization of the insulator. On the other hand, in the range of 10 <Fe + Co <60, an increase in the dielectric constant is observed, and it is considered that the number of polarized electrons increases.
Subsequently, physical properties of the thin film dielectric of the present invention will be described.
飽和磁化
本発明の薄膜誘電体は、Fe,Co,およびNiからなるグラニュールを含むため、磁化が0.5kG以上の磁性を示す。図4には、Fe,Co,Mg、及びFからなる膜について、膜中のFe+Co量(100-w-z,c=x=y=0)と飽和磁化の関係を図4に示した。Fe+Co量が10at%以上において0.5kG以上の磁化を有することが分かる。図1,2に示される誘電特性の変化は、このような膜の磁化変化に対応しており、磁性と誘電の複合特性が発現する。磁化が0.5kG未満の場合は、磁性の効果は小さく、複合特性は示さない。
Saturated magnetization Since the thin film dielectric of the present invention includes granules composed of Fe, Co, and Ni, it exhibits magnetism with a magnetization of 0.5 kG or more. FIG. 4 shows the relationship between the amount of Fe + Co (100−w−z, c = x = y = 0) in the film and the saturation magnetization of the film made of Fe, Co, Mg, and F. It can be seen that when the amount of Fe + Co is 10 at% or more, it has a magnetization of 0.5 kG or more. The change in the dielectric characteristics shown in FIGS. 1 and 2 corresponds to such a change in the magnetization of the film, and a composite characteristic of magnetism and dielectric is developed. When the magnetization is less than 0.5 kG, the effect of magnetism is small and composite characteristics are not exhibited.
電気抵抗率
本発明の薄膜誘電体は、前記した組成範囲では、1×104μΩcm以上1×1015μΩcm未満の電気抵抗率を得ることができる。電気抵抗率が1×104μΩcm未満の場合は、誘電損失が著しく増大し、誘電特性が劣化する。また、電気抵抗率が1×1015μΩcmを超える場合は、膜中のグラニュールの成分が少ないために、誘電率の増大効果及び磁性は失われる。
図5には、Fe,Co,Mg及びFからなる膜について、膜中のFe+Co量(100-w-z,c=x=y=0)と電気抵抗率の関係を示した。電気抵抗率が1×104μΩcm未満の場合は、誘電損失が著しく増大し誘電特性が劣化すると同時に、多数の電子が伝導に寄与し分極に寄与する電子が減少するために、誘電率が低下する。また、電気抵抗率が1×1015μΩcmを超える場合は、膜中のグラニュールの成分が少ないために誘電率の増大効果が損なわれ、また、磁化を担う磁性元素が少ないために磁化は失われ、磁化と誘電特性の複合機能性は現れない。
Electric resistivity The thin film dielectric of the present invention can obtain an electric resistivity of 1 × 10 4 μΩcm or more and less than 1 × 10 15 μΩcm within the above composition range. When the electrical resistivity is less than 1 × 10 4 μΩcm, the dielectric loss is remarkably increased and the dielectric properties are deteriorated. On the other hand, when the electrical resistivity exceeds 1 × 10 15 μΩcm, since the granule component in the film is small, the effect of increasing the dielectric constant and the magnetism are lost.
FIG. 5 shows the relationship between the Fe + Co amount (100−w−z, c = x = y = 0) and the electrical resistivity of the film made of Fe, Co, Mg, and F. When the electrical resistivity is less than 1 × 10 4 μΩcm, the dielectric loss is significantly reduced and the dielectric properties are deteriorated. At the same time, a large number of electrons contribute to conduction and the number of electrons contributing to polarization decreases. To do. Also, when the electrical resistivity exceeds 1 × 10 15 μΩcm, the effect of increasing the dielectric constant is impaired because there are few granule components in the film, and the magnetization is lost because there are few magnetic elements responsible for magnetization. However, the combined functionality of magnetization and dielectric properties does not appear.
膜厚
本発明の薄膜誘電体は、膜厚の薄い薄膜状態で用いることが好ましい。膜厚が5μmを超える場合でも本発明の効果は得られるが、薄膜プロセスを用いて厚い膜を作製するのは効率が悪く、膜厚が5μmを超える場合では実用的意義は薄い。本発明の薄膜誘電体は、従来材料では得られない薄い薄膜状態でその効果が発揮される(第5発明)。
Film thickness
The thin film dielectric of the present invention is preferably used in a thin film state. Although the effect of the present invention can be obtained even when the film thickness exceeds 5 μm, it is not efficient to produce a thick film using a thin film process, and practical significance is low when the film thickness exceeds 5 μm. The thin film dielectric of the present invention exhibits its effect in a thin thin film state that cannot be obtained with conventional materials (fifth invention) .
基板
本発明の薄膜誘電体は、石英ガラス、コーニング社製♯7059(コーニング社の商品名、以下同じ)などのガラス板、表面を熱酸化した単結晶シリコンウェーハ、又はMgOからなる基板に直接成膜することができる(第6発明)。
substrate
The thin film dielectric of the present invention is directly formed on a glass plate such as quartz glass, Corning # 7059 (trade name of Corning, the same shall apply hereinafter), a single crystal silicon wafer whose surface is thermally oxidized, or a substrate made of MgO. (Sixth invention) .
製造方法
本発明の誘電体薄膜は、コンベンショナルなスパッタ装置、RFスパッタ装置で成膜することができる。スパッタ法又はRFスパッタ成膜装置を用い、純Fe、純Co、純Ni、あるいはFe,Co,Niのいずれかを含む合金円板上に、M元素を含む窒化物、酸化物、あるいはフッ化物の誘電体(絶縁体)のチップを均等に配置した複合ターゲットを用いて行なうか、あるいは金属ターゲットと誘電体ターゲットを同時にスパッタして行うと、nmサイズの超常磁性を示す磁性グラニュールが誘電体からなる絶縁相中に分散したナノグラニュラー構造膜が得られ、所望の誘電特性を示す。
Manufacturing method The dielectric thin film of the present invention can be formed by a conventional sputtering apparatus or RF sputtering apparatus. Nitride, oxide, or fluoride containing M element on an alloy disk containing pure Fe, pure Co, pure Ni, or any of Fe, Co, and Ni using a sputtering method or an RF sputtering film forming apparatus When using a composite target with evenly arranged chips of dielectric (insulator), or by simultaneously sputtering a metal target and a dielectric target, a magnetic granule showing nm-size superparamagnetism A nano-granular structure film dispersed in an insulating phase is obtained and exhibits desired dielectric properties.
より具体的には、コンベンショナルタイプのRFスパッタ装置、RFマグネトロンスパッタ装置あるいはDC対向ターゲットスパッタ装置を用い、直径70〜100mmの純Fe、純Co、純NiあるいはFe,Co,Niのいずれか2種以上を含む合金円板ターゲット、さらにそれにM元素を含む合金ターゲットと、窒化物、酸化物あるいはフッ化物ターゲットを同時にスパッタすることにより、薄膜を作製する。スパッタ成膜に際しては、純Arガス、もしくはArとN又はOの混合ガスを用いる。膜厚のコントロールは成膜時間を加減することによって行い、約0.3〜5μmに成膜する。尚、基板は間接水冷あるいは100〜800℃の任意の温度に熱し、成膜時のスパッタ圧力は1〜60mTorrで、スパッタ電力は50〜350Wである。 More specifically, using a conventional type RF sputtering apparatus, RF magnetron sputtering apparatus or DC facing target sputtering apparatus, pure Fe, pure Co, pure Ni or Fe, Co, Ni having a diameter of 70 to 100 mm is used. A thin film is produced by simultaneously sputtering an alloy disk target containing the above, an alloy target containing M element thereon, and a nitride, oxide or fluoride target. For sputtering film formation, pure Ar gas or a mixed gas of Ar and N or O is used. The film thickness is controlled by adjusting the film formation time, and is formed to a thickness of about 0.3 to 5 μm. The substrate is indirectly water-cooled or heated to an arbitrary temperature of 100 to 800 ° C., the sputtering pressure during film formation is 1 to 60 mTorr, and the sputtering power is 50 to 350 W.
さらに、成膜後あるいは成膜中の100〜800℃の加熱により誘電特性を調整することができる。本発明の薄膜誘電体の誘電特性は、上述のように、誘電体からなるマトリックスにnmサイズの金属グラニュールが分散したナノグラニュラー構造に関連している。本発明の薄膜誘電体の誘電特性に微妙な影響を及ぼす条件としては次のものが考えられる。(1)金属グラニュールの粒径や分散状態、(2)マトリックス絶縁体の構造や状態、(3)誘電特性を担うマトリックスの結晶構造、(4)グラニュールとマトリックス絶縁体との接合界面、(5)マトリックスやグラニュール内の原子数個程度の不純物や界面での原子の配置や移動など、原子レベルでの構造変化などである。これらの条件は、成膜後の熱処理、及び成膜中の基板加熱によって変化する。それらの温度は、100℃未満では効果はなく、800℃を越えると構造が一様化してしまい、ヘテロ構造であるナノグラニュラー構造は得られない。 Furthermore, the dielectric characteristics can be adjusted by heating at 100 to 800 ° C. after film formation or during film formation. As described above, the dielectric characteristics of the thin film dielectric of the present invention are related to a nano-granular structure in which metal particles of nm size are dispersed in a matrix made of a dielectric. The following conditions can be considered as subtle effects on the dielectric properties of the thin film dielectric of the present invention. (1) Particle size and dispersion state of metal granules, (2) Structure and state of matrix insulator, (3) Crystal structure of matrix responsible for dielectric properties, (4) Bonding interface between granule and matrix insulator, (5) Changes in the structure at the atomic level, such as the arrangement and movement of about several impurities in the matrix or granule and atoms at the interface. These conditions vary depending on the heat treatment after the film formation and the substrate heating during the film formation. If the temperature is less than 100 ° C., there is no effect. If the temperature exceeds 800 ° C., the structure becomes uniform, and a nano-granular structure that is a heterostructure cannot be obtained.
{作用}
新たに発見された前記特性(1)、(2)、(3)を利用して新規な薄膜誘電体を得ることができた。
{Action}
A novel thin film dielectric could be obtained by utilizing the newly discovered characteristics (1), (2) and (3).
本発明の薄膜誘電体は従来の誘電体材料のように体積依存性をもたない。従来材料の薄膜化の例として、物理的蒸着などの薄膜プロセスにより、チタン酸バリウム系誘電体薄膜(Ba1−xSrxTiO3(x=0〜0.6)),PbTiO3,Pb(Zr,Ti)O3,Bi4Ti3O12等を作製し、大容量の薄膜コンデンサの開発を目指す研究も盛んに行われている。しかし、チタン酸バリウム系薄膜は、膜厚を数百nmレベル以下まで小さくすると、誘電率が低下するという問題があり、膜厚数百nm程度が素子として安定に動作する限界である。 The thin film dielectric of the present invention is not volume dependent like conventional dielectric materials. As an example of thinning a conventional material, a barium titanate-based dielectric thin film (Ba 1-x Sr x TiO 3 (x = 0 to 0.6)), PbTiO 3 , Pb (by a thin film process such as physical vapor deposition) Research aimed at developing a large-capacity thin film capacitor by producing Zr, Ti) O 3 , Bi 4 Ti 3 O 12, and the like has been actively conducted. However, the barium titanate-based thin film has a problem that the dielectric constant decreases when the film thickness is reduced to a level of several hundred nm or less, and the film thickness of about several hundred nm is the limit for stable operation as an element.
本発明においては、膜組成や熱処理などを調整することによって、マトリックスの状態や構造、また金属グラニュールの粒径や分散状態を調整し、任意の誘電特性を有する薄膜材料が設計できる。これに対して、バルクの誘電体材料には、ゴムや樹脂などに大きさが数μm程度の金属粒子を練りこんだ複合材料も用いられているが、その材料組織は、ナノグラニュラー構造に比べて数桁も大きく、高密度化や薄膜化には全く対応できない。 In the present invention, by adjusting the film composition, heat treatment and the like, the state and structure of the matrix and the particle size and dispersion state of the metal granules can be adjusted to design a thin film material having arbitrary dielectric properties. On the other hand, composite materials in which metal particles with a size of several μm are kneaded into rubber or resin are also used as bulk dielectric materials, but the material structure is less than that of nano-granular structures. It is several orders of magnitude larger and cannot handle high density or thin film at all.
本発明のナノグラニュラー構造を有する薄膜誘電体は、下地基板の結晶方位などにより特性が影響されないから、バッファー層などが必要ではなく、あらゆる基板材料に対応できるので、用途が広く、かつ低コストで製造が可能である。 The thin-film dielectric having the nano-granular structure of the present invention is not affected by the crystal orientation of the underlying substrate, and therefore does not require a buffer layer and can be applied to any substrate material. Is possible.
以下、本発明を実施例を参照してさらに詳しく説明する。
〔実施例1〕
予備実験
基板には、約0.5mm厚のコーニング社製#7059(コーニング社の商品名)ガラス、0.5mm厚で表面を熱酸化したSiウエハ、0.5mm厚の石英ガラス、もしくは同様に約0.5mm厚のMgOを用い、さらに、膜厚を0.3〜3μmの範囲で変化させた試料番号16の誘電率を測定したところ、基板種類や膜厚と関係なく誘電率はほとんど同じであったために、以下の実験では次のように変化させた条件で実験を行った。なお、誘電率測定のために上記基板材の一部にAuもしくはPtの電極膜を備えた基板を用いた。
Hereinafter, the present invention will be described in more detail with reference to examples.
[Example 1]
Preliminary experiment: Substrate has approximately 0.5 mm thick Corning # 7059 (Corning trade name) glass, 0.5 mm thick thermally oxidized Si wafer, 0.5 mm thick quartz glass Similarly, when the dielectric constant of Sample No. 16 was measured using MgO having a thickness of about 0.5 mm and the film thickness changed in the range of 0.3 to 3 μm, the dielectric constant was measured regardless of the substrate type and film thickness. Since the rate was almost the same, in the following experiment, the experiment was performed under the following changed conditions. For the dielectric constant measurement, a substrate provided with an Au or Pt electrode film as a part of the substrate material was used.
薄膜の作製と評価
成膜装置:RFマグネトロンスパッタ装置・DC対向ターゲットスパッタ装置
基板:#7059ガラス、石英ガラス、Siウエハ
誘電体膜厚:0.3〜5.0μm
基板温度:水冷〜800℃
スパッタ圧力:0.3〜20mTorr
スパッタ電力:50〜200W
Fabrication and evaluation of thin film Deposition apparatus: RF magnetron sputtering apparatus / DC facing target sputtering apparatus Substrate: # 7059 glass, quartz glass, Si wafer dielectric film thickness: 0.3-5.0 [mu] m
Substrate temperature: water-cooled to 800 ° C
Sputtering pressure: 0.3 to 20 mTorr
Sputtering power: 50-200W
前記のようにして作製した薄膜試料は、LCRメータ(製造社:Agilent社;型式E4980A)によって誘電率及び誘電損失を計測した。また、電気抵抗率は直流4端子法を基本とする電気抵抗率の測定装置を用いて測定し、また磁化は、試料振動型磁化測定装置(VSM)で測定した。膜組成はエネルギー分散型分光分析法(EDS)、あるいは波長分散型分光分析法(WDS)によって分析した。また、膜の構造は、Cu−Kα線を用いたX線回折法(XRD)及び高分解能透過型電子顕微鏡(TEM)によって解析した。それぞれの薄膜試料の組成を表1に、諸特性を表2に示す。 The thin film sample produced as described above was measured for dielectric constant and dielectric loss using an LCR meter (manufacturer: Agilent; model E4980A). The electrical resistivity was measured using an electrical resistivity measuring device based on the direct current four-terminal method, and the magnetization was measured with a sample vibration type magnetometer (VSM). The film composition was analyzed by energy dispersive spectroscopy (EDS) or wavelength dispersive spectroscopy (WDS). The structure of the film was analyzed by an X-ray diffraction method (XRD) using Cu-Kα rays and a high-resolution transmission electron microscope (TEM). The composition of each thin film sample is shown in Table 1, and various characteristics are shown in Table 2.
図6には試料番号1のTEM像を示す。膜は、粒径が3−4nmのグラニュール(黒っぽい球形の部分)と、絶縁体もしくは誘電体(グラニュール間の白っぽい部分)からなる、ナノメーター(nm)オーダーの微細構造であるグラニュラー構造であることが分かる。また、図7には試料番号13のXRD図形を示す。2θが25°付近にはAlF3からなるフッ化物からのピーク、また2θが44°付近には膜中の磁性金属グラニュール(鉄,コバルト)に対応するピークが観察され観察される。さらに、図8には試料番号17のXRD図形を示す。2θが27°、40°、及び54°付近にはMgF2 からなるフッ化物相からのピーク、また2θが44°付近には膜中の磁性金属グラニュール(鉄,コバルト)に対応するピークが観察される。図7及び図8において、磁性金属グラニュールのピークの半値幅からシェラーの式を用いて計算されるグラニュールの粒径は2〜5nmである。以上のことから、これらの膜が微細なナノグラニュールと絶縁体であるフッ化物相の2相からなるナノグラニュラー構造であることがわかる。 FIG. 6 shows a TEM image of sample number 1. The film has a granular structure with a fine structure of nanometer (nm) order, consisting of granules (blackish spherical parts) with a particle size of 3-4 nm and insulators or dielectrics (white parts between granules). I understand that there is. FIG. 7 shows an XRD pattern of sample number 13. When 2θ is around 25 °, a peak from a fluoride made of AlF 3 is observed, and when 2θ is around 44 °, a peak corresponding to magnetic metal granules (iron, cobalt) in the film is observed and observed. Further, FIG. 8 shows an XRD pattern of sample number 17. When 2θ is around 27 °, 40 °, and 54 °, there is a peak from the fluoride phase composed of MgF 2, and when 2θ is around 44 °, there is a peak corresponding to the magnetic metal granules (iron, cobalt) in the film. Observed. 7 and 8, the particle size of the granule calculated from the half width of the peak of the magnetic metal granule using the Scherrer equation is 2 to 5 nm. From the above, it can be seen that these films have a nanogranular structure composed of two phases of fine nanogranule and a fluoride phase which is an insulator.
表1に示された薄膜誘電体の組成において試料番号1〜19は本発明の組成範囲を満たしている。これらの試料中、誘電率が最も高い組成は試料番号6(誘電率=58)であり、最も低い組成は試料番号17(誘電率=12)である。 In the composition of the thin film dielectric shown in Table 1, sample numbers 1 to 19 satisfy the composition range of the present invention. Among these samples, the composition having the highest dielectric constant is sample number 6 (dielectric constant = 58), and the composition having the lowest dielectric constant is sample number 17 (dielectric constant = 12).
以上説明したように、本発明による薄膜誘電体は、誘電体を用いたデバイスの小型化・高周波化に対応したものであり、容易に微小サイズの誘電体デバイスを提供することができる。さらに、高周波回路設計に必要な誘電体特性の調整が可能である。 As described above, the thin film dielectric according to the present invention is suitable for miniaturization and high frequency of a device using the dielectric, and can easily provide a micro-sized dielectric device. Furthermore, it is possible to adjust dielectric characteristics necessary for high-frequency circuit design.
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