JP2015160998A - Barium silicide film and method for manufacturing the same - Google Patents
Barium silicide film and method for manufacturing the same Download PDFInfo
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- JP2015160998A JP2015160998A JP2014037351A JP2014037351A JP2015160998A JP 2015160998 A JP2015160998 A JP 2015160998A JP 2014037351 A JP2014037351 A JP 2014037351A JP 2014037351 A JP2014037351 A JP 2014037351A JP 2015160998 A JP2015160998 A JP 2015160998A
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- 229910052788 barium Inorganic materials 0.000 title claims abstract description 54
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910021332 silicide Inorganic materials 0.000 title claims abstract description 50
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title description 17
- 239000000758 substrate Substances 0.000 claims abstract description 40
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 32
- 239000010703 silicon Substances 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 238000004544 sputter deposition Methods 0.000 claims abstract description 23
- 239000013078 crystal Substances 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 5
- 229910016066 BaSi Inorganic materials 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000151 deposition Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 72
- OOJQNBIDYDPHHE-UHFFFAOYSA-N barium silicon Chemical compound [Si].[Ba] OOJQNBIDYDPHHE-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000009826 distribution Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000001451 molecular beam epitaxy Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 3
- 238000004453 electron probe microanalysis Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001552 radio frequency sputter deposition Methods 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- 238000005477 sputtering target Methods 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Physical Vapour Deposition (AREA)
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
Abstract
Description
シリコンを含有するワイドギャップ半導体は非常に特異的な特性を示すため、太陽電池材料や熱電変換材料等の環境エネルギー分野で広く利用されている。中でも、バリウム（Ｂａ）とシリコン（Ｓｉ）からなる珪化バリウムは、ＢａＳｉ２組成でバンドギャップが１．３ｅＶと、シリコンの１．１ｅＶよりも大きいため、注目されている。（例えば、非特許文献１）さらにＳｒを添加することでバンドギャップを１．４ｅＶまで調整する事が可能である（例えば、特許文献１、非特許文献２参照）。 Wide-gap semiconductors containing silicon are widely used in the field of environmental energy such as solar cell materials and thermoelectric conversion materials because they exhibit very specific characteristics. Among them, barium silicide composed of barium (Ba) and silicon (Si) has attracted attention because it has a BaSi 2 composition and a band gap of 1.3 eV, which is larger than 1.1 eV of silicon. (For example, Non-Patent Document 1) It is possible to adjust the band gap to 1.4 eV by adding Sr (see, for example, Patent Document 1 and Non-Patent Document 2).
珪化バリウムの利用形態としては、膜として用いることが有効である。例えば、特許文献２にはｎ型とｎ＋型珪化バリウム膜を積層した太陽電池がその例として挙げられている。膜の作製方法として以前より知られているのはシリコン（１１１）上へＭＢＥ法（分子線エピタキシー法）にて製膜する方法で、各元素を精密に製膜することが可能であるが、製膜速度が遅く、特殊な装置であることから、量産には向いていない。そこで、量産向きの膜の作製方法が求められる。また、利用する基板についてもより安価な酸化ケイ素系基板の利用が求められている。 It is effective to use it as a film as a utilization form of barium silicide. For example, Patent Document 2 discloses a solar cell in which an n-type and an n + -type barium silicide film are stacked. As a method for producing a film, a method of forming a film on silicon (111) by MBE method (molecular beam epitaxy method) can be used to precisely form each element. Since the film forming speed is slow and it is a special device, it is not suitable for mass production. Therefore, a method for manufacturing a film suitable for mass production is required. Further, the use of a cheaper silicon oxide substrate is also demanded for the substrate to be used.
量産に向いている膜の作製製法としてスパッタ法が挙げられる。スパッタリング法は陰極に設置したターゲットにＡｒイオンなどの正イオンを物理的に衝突させ、その衝突エネルギーでターゲットを構成する材料を放出させて、対面に設置した基板上にターゲット材料とほぼ同組成の膜を堆積する方法であり、直流スパッタリング法（ＤＣスパッタリング法）と高周波スパッタリング法（ＲＦスパッタリング法）がある。この方法を用いることで、例えばＭＢＥ法では困難な大面積への高速製膜が可能となる。 A sputtering method is an example of a method for producing a film suitable for mass production. In the sputtering method, positive ions such as Ar ions are physically collided with the target placed on the cathode, and the material constituting the target is released by the collision energy, and the target material is almost the same composition as the target material on the substrate placed on the opposite side. This is a method for depositing a film, and includes a direct current sputtering method (DC sputtering method) and a high frequency sputtering method (RF sputtering method). By using this method, high-speed film formation on a large area, which is difficult with the MBE method, for example, becomes possible.
特許文献３には、スパッタ法にて珪化バリウム膜を製膜した例が報告されているが、スパッタ法を用いた珪化バリウム膜に関して詳細な検討は行われていない。 Patent Document 3 reports an example in which a barium silicide film is formed by a sputtering method, but no detailed examination has been made on a barium silicide film using a sputtering method.
本発明の目的は、膜の組織を均一化した珪化バリウム結晶性膜を提供することである。 An object of the present invention is to provide a barium silicide crystalline film having a uniform film structure.
本発明は、
（１）珪素の組成ずれが２０％以内であり、スパッタ法で製膜されたことを特徴とする珪化バリウム結晶性膜。
（２）ＢａＳｉ２斜方晶の結晶を有することを特徴とする（１）に記載の珪化バリウム結晶性膜。
（３）多結晶構造であることを特徴とする（１）または（２）に記載の珪化バリウム膜。
（４）シリコンを主成分として含む基板の上に製膜されていることを特徴とする（１）〜（３）のいずれかに記載の珪化バリウム膜。
（５）前記基板の主成分が酸化ケイ素であることを特徴とする（４）に記載の珪化バリウム膜。
（６）珪化バリウム膜の厚みが７００ｎｍ以上であることを特徴とする（１）〜（５）のいずれかに記載の珪化バリウム膜。
（７）珪化バリウム膜の面積が１５ｃｍ２以上であることを特徴とする（１）〜（６）のいずれかに記載の珪化バリウム膜。
（８）基板を加熱しながらスパッタ法にて製膜することを特徴とする（１）〜（７）のいずれかに記載の珪化バリウム膜の製造方法。
（９）３５０℃〜８００℃に基板を加熱した状態で製膜することを特徴とする（８）に記載の珪化バリウム膜の製造方法に関するものである。
The present invention
(1) A barium silicide crystalline film having a silicon composition deviation of 20% or less and formed by sputtering.
(2) The barium silicide crystalline film according to (1), having a BaSi 2 orthorhombic crystal.
(3) The barium silicide film according to (1) or (2), which has a polycrystalline structure.
(4) The barium silicide film according to any one of (1) to (3), which is formed on a substrate containing silicon as a main component.
(5) The barium silicide film according to (4), wherein a main component of the substrate is silicon oxide.
(6) The barium silicide film according to any one of (1) to (5), wherein the thickness of the barium silicide film is 700 nm or more.
(7) The barium silicide film according to any one of (1) to (6), wherein an area of the barium silicide film is 15 cm 2 or more.
(8) The method for producing a barium silicide film according to any one of (1) to (7), wherein the film is formed by sputtering while heating the substrate.
(9) The present invention relates to the method for producing a barium silicide film according to (8), wherein the film is formed in a state where the substrate is heated to 350 ° C. to 800 ° C.
本発明の珪化バリウム膜は、膜が均質であることから半導体として好適であり、太陽電池などに代表される半導体デバイスに使用することができる。 The barium silicide film of the present invention is suitable as a semiconductor because the film is homogeneous, and can be used for semiconductor devices represented by solar cells and the like.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の珪化バリウム薄膜は薄膜中の珪素の組成ずれが２０％以下と均一であることを特徴とする。その組成分布の測定はＥＰＭＡ（電子線マイクロアナライザー）等、元素の面分布を測定可能な分析手法を用いることで測定することができる。測定視野としては４５μｍ四方以上の視野について面分析をすることが望ましい。珪素の組成分布が均一であるということはすなわち、膜組織が均一であることを示し、それにより、不均一組織と比較し高い光学特性や電気特性を得られる。 The barium silicide thin film of the present invention is characterized in that the compositional deviation of silicon in the thin film is uniform at 20% or less. The composition distribution can be measured by using an analytical method capable of measuring the surface distribution of elements such as EPMA (electron beam microanalyzer). As a measurement visual field, it is desirable to perform surface analysis on a visual field of 45 μm square or more. The fact that the silicon composition distribution is uniform means that the film structure is uniform, whereby high optical characteristics and electrical characteristics can be obtained as compared with the non-uniform structure.
本願ではその測定方法として下記の方法を用いた。 In this application, the following method was used as the measuring method.
まず、ＥＰＭＡ等を用いて４５μｍ四方の視野に対し、珪素に関する組成分布を測定する。その後３μｍ四方毎に珪素検出量の平均値を取ることで、４５μｍ四方における、３μｍ四方の平均検出量が算出される。それぞれの平均算出量に対し、最大量Ａ、最少量Ｂならびに２２５か所の全平均量Ｃから下記の計算により組成ずれ（％）を算出する。
組成ずれ（％）＝（最大量Ａ−最少量Ｂ）／全平均値Ｃ
また、光吸収特性や電気伝導性を向上させるためには、珪化バリウム膜は結晶化していることが好ましい。その結晶系はＢａＳｉ２、特に斜方晶の組織であることが好ましい。その場合に珪素―バリウム系の半導体物性として最も高い性能を示す。
First, a composition distribution relating to silicon is measured for a visual field of 45 μm square using EPMA or the like. Thereafter, by taking the average value of the silicon detection amount every 3 μm square, the average detection amount of 3 μm square in 45 μm square is calculated. For each average calculation amount, the composition deviation (%) is calculated from the maximum amount A, the minimum amount B, and the total average amount C at 225 locations by the following calculation.
Composition deviation (%) = (maximum amount A−minimum amount B) / total average value C
In order to improve light absorption characteristics and electrical conductivity, the barium silicide film is preferably crystallized. The crystal system is preferably BaSi 2 , particularly an orthorhombic structure. In that case, it shows the highest performance as a silicon-barium semiconductor physical property.
その結晶性は高いことが好ましいが、結晶の柔軟性や硬度を高めるために結晶は多結晶構造であることが好ましい。 The crystallinity is preferably high, but the crystal preferably has a polycrystalline structure in order to increase the flexibility and hardness of the crystal.
さらに、製膜するための基板としては、コスト面などを重視するとシリコン系基板、さらには酸化ケイ素を主成分にする基板を用いることが好ましい。特にアルカリフリーガラスを利用することで、コストの低減が可能となる。 Furthermore, as a substrate for forming a film, it is preferable to use a silicon-based substrate and further a substrate containing silicon oxide as a main component in view of cost. In particular, the cost can be reduced by using alkali-free glass.
また、本発明の珪化バリウム膜は、生産性、製造コストの観点からスパッタ法による製膜が好ましい。ＭＢＥ法に代表される方法はエピタキシー成長させるために、基板の面方位、格子定数に成長膜が左右され、利用可能な基板が限定される。例えば珪化バリウム系膜において、ＢａＳｉ２結晶を析出させるためにはＳｉ（１１１）、（１００）面をもつ基板を用いる必要がある。それに対し、スパッタ法ではスパッタリングターゲットより発生する高エネルギーＢａもしくはＳｉ粒子を利用していることから、基板配向面によらず結晶性の珪化バリウム膜を作製することが可能な手法となる。 The barium silicide film of the present invention is preferably formed by sputtering from the viewpoint of productivity and manufacturing cost. In the method represented by the MBE method, the growth film depends on the plane orientation and the lattice constant of the substrate for epitaxy growth, and the usable substrates are limited. For example, in a barium silicide-based film, it is necessary to use a substrate having Si (111) and (100) planes in order to precipitate BaSi 2 crystals. On the other hand, since the high energy Ba or Si particles generated from the sputtering target are used in the sputtering method, a crystalline barium silicide film can be produced regardless of the substrate orientation plane.
熱膨張率の点からも基板を選定することが好ましい。珪化バリウムの熱膨張率が約１５０×１０−７／Ｋであるため、なるべくこれに近い基板を用いることが好ましく、石英ガラス（５．４×１０−７／Ｋ）と比較すればシリコン（３５．９×１０−７／Ｋ）やアルカリフリーガラス（３１．７×１０−７／Ｋ）のような熱膨張率が１０×１０−７／Ｋ以上の基板が望ましい。 It is preferable to select the substrate also in terms of the coefficient of thermal expansion. Since the thermal expansion coefficient of barium silicide is about 150 × 10 −7 / K, it is preferable to use a substrate as close as possible to this, and silicon (35) compared to quartz glass (5.4 × 10 −7 / K). .9 × 10 −7 / K) or an alkali-free glass (31.7 × 10 −7 / K) and a substrate having a thermal expansion coefficient of 10 × 10 −7 / K or more is desirable.
本発明の珪化バリウム膜の製造方法について説明する。 The manufacturing method of the barium silicide film of the present invention will be described.
本発明の珪化バリウム膜の製造方法は、基板を加熱しながらスパッタ法を用いて製膜する。 In the method for producing a barium silicide film of the present invention, a film is formed by sputtering while heating the substrate.
珪化バリウム膜を作製するに当たり、室温製膜では結晶化させるためのエネルギーが不足するため、結晶性を持つ珪化バリウム系膜を作製することが難しい。そこで、結晶性を持つ珪化バリウム系膜を作製するため、基板を加温した状態で製膜する、加熱製膜を用いる。スパッタ法はターゲットより飛び出したＢａやＳｉ粒子が基板に衝突し、膜を形成するが、基板を加熱しておくことで、基板に到着した粒子が安定層へ移動し、結晶膜を形成しやすくなる。基板の加熱温度としては３５０℃から８００℃が好ましい。アーク溶解法等による珪化バリウム塊合成の場合はより高温が必要だが、高エネルギー粒子にさらにエネルギーを付加する形となるため、より低い温度で結晶性膜を形成することが可能である。３５０℃未満では粒子の移動エネルギーが小さく結晶膜を形成することが困難であり、８００℃より高温になると、バリウムと珪素が遊離を始めるために、珪化バリウムの結晶を維持できなくなる。加熱温度が４５０℃以上６００℃以下だと、ＢａＳｉ２の斜方晶の珪化バリウムの結晶が主に析出し、更に半導体としての性能を高めることが可能となる。 In producing a barium silicide film, it is difficult to produce a barium silicide-based film having crystallinity because the energy for crystallization is insufficient in film formation at room temperature. Therefore, in order to produce a barium silicide-based film having crystallinity, heating film formation is used in which the substrate is formed in a heated state. In the sputtering method, Ba and Si particles popping out from the target collide with the substrate to form a film. However, by heating the substrate, the particles arriving at the substrate move to the stable layer and easily form a crystal film. Become. The heating temperature of the substrate is preferably 350 ° C. to 800 ° C. In the case of barium silicide ingot synthesis by the arc melting method or the like, a higher temperature is required. However, since energy is added to high energy particles, a crystalline film can be formed at a lower temperature. If the temperature is lower than 350 ° C., it is difficult to form a crystal film because the particle movement energy is small, and if the temperature is higher than 800 ° C., barium and silicon begin to be released, so that the crystal of barium silicide cannot be maintained. When the heating temperature is 450 ° C. or higher and 600 ° C. or lower, BaSi 2 orthorhombic barium silicide crystals are mainly precipitated, and the performance as a semiconductor can be further improved.
また、太陽電池用途を想定する場合において、その膜は厚い方が好ましくその厚みは５００ｎｍ以上が好ましく、１０００ｎｍ以上であることがより好ましい。膜の面積は１５ｃｍ２以上が好ましい。 In the case of assuming a solar cell application, the film is preferably thick, and the thickness is preferably 500 nm or more, and more preferably 1000 nm or more. The area of the film is preferably 15 cm 2 or more.
以下、本発明の実施例をもって説明するが、本発明はこれに限定されるものではない。
（結晶性の確認方法）
ＸＲＤ装置を用いて２０°〜８０°まで走査し、ピーク位置から結晶方位を同定した。
（珪素組成ずれの確認方法）
ＥＰＭＡを用いて、４５μｍ四方の視野に対し、珪素量分布を測定した。その後３μｍ四方毎に珪素検出量の平均値を取り、４５μｍ四方における、３μｍ四方の平均検出量が算出される。それぞれの平均検出量に対し、最大量Ａ、最少量Ｂならびに２２５か所の全平均量Ｃから下記の計算により組成ずれ（％）を算出する。
珪素組成ずれ（％）＝（最大量Ａ−最少量Ｂ）／全平均値Ｃ
（実施例１）
珪化バリウムスパッタリングターゲットを用いて、下記の条件にてスパッタ製膜試験を実施した。
（スパッタ条件）
放電方式 ：ＲＦスパッタ
製膜装置 ：マグネトロンスパッタ装置
ターゲットサイズ ：５０ｍｍφ
ターゲット―基板間距離：８０ｍｍ
製膜圧力 ：０．２Ｐａ
導入ガス ：アルゴン
放電パワー ：１００Ｗ（５．１Ｗ／ｃｍ２）
基板 ：Ｓｉ（１１１）面 ５０ｍｍ角（面積２５ｃｍ２）
基板温度 ：５００℃
膜厚 ：１０００ｎｍ
以上の条件にて製膜を行なった結果、珪素組成ずれ４．８％、ＢａＳｉ２斜方晶ピークを有する、珪素―バリウム多結晶膜を作製する事が可能であることを確認した。
Examples of the present invention will be described below, but the present invention is not limited thereto.
(Method for confirming crystallinity)
Scanning was performed from 20 ° to 80 ° using an XRD apparatus, and the crystal orientation was identified from the peak position.
(Silicon composition deviation confirmation method)
Using EPMA, the silicon content distribution was measured for a 45 μm square field of view. Thereafter, an average value of the silicon detection amount is taken every 3 μm square, and an average detection amount of 3 μm square in 45 μm square is calculated. For each average detected amount, the composition deviation (%) is calculated from the maximum amount A, the minimum amount B, and the total average amount C at 225 locations by the following calculation.
Silicon composition deviation (%) = (maximum amount A−minimum amount B) / total average value C
Example 1
Using a barium silicide sputtering target, a sputtering film forming test was performed under the following conditions.
(Sputtering conditions)
Discharge method: RF sputtering Film-forming device: Magnetron sputtering device Target size: 50mmφ
Target-to-board distance: 80mm
Film forming pressure: 0.2 Pa
Introduced gas: Argon Discharge power: 100 W (5.1 W / cm 2 )
Substrate: Si (111) surface 50 mm square (area 25 cm 2 )
Substrate temperature: 500 ° C
Film thickness: 1000nm
As a result of film formation under the above conditions, it was confirmed that a silicon-barium polycrystalline film having a silicon composition shift of 4.8% and a BaSi 2 orthorhombic peak could be produced.
（実施例２）
基板温度を３９０℃とした以外は実施例１と同様の方法でスパッタ製膜試験を実施した。その結果、珪素組成ずれ８．１％、Ｂａ５Ｓｉ３結晶ピークを有する、珪素―バリウム多結晶膜を作製可能であることを確認した。
(Example 2)
A sputter film formation test was performed in the same manner as in Example 1 except that the substrate temperature was 390 ° C. As a result, it was confirmed that a silicon-barium polycrystalline film having a silicon composition deviation of 8.1% and a Ba 5 Si 3 crystal peak could be produced.
（実施例３）
基板温度を６００℃とした以外は実施例１と同様の方法でスパッタ製膜試験を実施した。その結果、珪素組成ずれ１１．８％、ＢａＳｉ２斜方晶ピークを有する、珪素―バリウム多結晶膜を作製可能であることを確認した。
(Example 3)
A sputter film formation test was performed in the same manner as in Example 1 except that the substrate temperature was 600 ° C. As a result, it was confirmed that a silicon-barium polycrystalline film having a silicon composition shift of 11.8% and a BaSi 2 orthorhombic peak could be produced.
（実施例４）
基板を石英ガラス（厚み０．５ｍｍ）とした以外は実施例１と同様の方法でスパッタ製膜試験を実施した。その結果、珪素組成ずれ６．７％、ＢａＳｉ２斜方晶ピークを有する、珪素―バリウム多結晶膜を作製可能であることを確認した。
Example 4
A sputtering film formation test was performed in the same manner as in Example 1 except that the substrate was quartz glass (thickness 0.5 mm). As a result, it was confirmed that a silicon-barium polycrystalline film having a silicon composition deviation of 6.7% and a BaSi 2 orthorhombic peak could be produced.
（実施例５）
基板をアルカリフリーガラス（厚み０．５ｍｍ）とした以外は実施例１と同様の方法でスパッタ製膜試験を実施した。その結果、珪素組成ずれ４．１％であり、ＢａＳｉ２斜方晶ピークを有する、珪素―バリウム多結晶膜を作製可能であることを確認した。
(Example 5)
A sputtering film forming test was performed in the same manner as in Example 1 except that the substrate was alkali-free glass (thickness 0.5 mm). As a result, it was confirmed that a silicon-barium polycrystalline film having a silicon composition deviation of 4.1% and having a BaSi 2 orthorhombic peak could be produced.
（実施例６）
基板温度を４３０℃とした以外は実施例５と同様の方法でスパッタ製膜試験を実施した。その結果、珪素組成ずれ２．４％、ＢａＳｉ２斜方晶、Ｂａ５Ｓｉ３結晶ピークを有する、珪素―バリウム多結晶膜を作製可能であることを確認した。
(Example 6)
A sputtering film forming test was performed in the same manner as in Example 5 except that the substrate temperature was 430 ° C. As a result, it was confirmed that a silicon-barium polycrystalline film having a silicon composition deviation of 2.4%, a BaSi 2 orthorhombic crystal, and a Ba 5 Si 3 crystal peak could be produced.
（実施例７）
基板の大きさを３インチΦ（面積４６ｃｍ２）とした以外は実施例１と同様の方法でスパッタ製膜試験を実施した。その結果、珪素組成ずれ８．９％である、ＢａＳｉ２斜方晶ピークを有する、珪素―バリウム多結晶膜を作製可能であることを確認した。
(Example 7)
A sputtering film formation test was performed in the same manner as in Example 1 except that the size of the substrate was 3 inches Φ (area 46 cm 2 ). As a result, it was confirmed that a silicon-barium polycrystalline film having a BaSi 2 orthorhombic peak with a silicon composition deviation of 8.9% can be produced.
（比較例１）
基板温度を２５℃とした以外は実施例１と同様の方法でスパッタ製膜試験を実施した。その結果、珪素組成ずれが７．８％、結晶性のない珪素―バリウム膜となり、望むものは得られなかった。
(Comparative Example 1)
A sputter film formation test was performed in the same manner as in Example 1 except that the substrate temperature was 25 ° C. As a result, the silicon composition deviation was 7.8%, and a silicon-barium film having no crystallinity was obtained.
（比較例２）
基板温度２５℃とした以外は実施例１と同様の方法で珪素―バリウム薄膜を作製した後に、７００℃にて熱処理を施した。その結果、珪素組成ずれが３９．４％、ＢａＳｉ２斜方晶ピークを有する、珪素―バリウム多結晶膜となり、望むものは得られなかった。
(Comparative Example 2)
A silicon-barium thin film was prepared in the same manner as in Example 1 except that the substrate temperature was 25 ° C., and then heat-treated at 700 ° C. As a result, a silicon-barium polycrystalline film having a silicon composition shift of 39.4% and a BaSi 2 orthorhombic peak was obtained, and the desired product was not obtained.
（比較例３）
基板温度を２００℃とした以外は実施例１と同様の方法でスパッタ製膜試験を実施した。その結果、珪素組成ずれが６．３％、結晶性のない珪素―バリウム膜となり、望むものは得られなかった。
(Comparative Example 3)
A sputter film formation test was performed in the same manner as in Example 1 except that the substrate temperature was 200 ° C. As a result, the silicon composition deviation was 6.3%, and a silicon-barium film having no crystallinity was obtained.
（比較例４）
基板温度を２５０℃とした以外は実施例１と同様の方法でスパッタ製膜試験を実施した。その結果、珪素組成ずれが１０．８％、結晶性のない珪素―バリウム薄膜となり、望むものは得られなかった。
(Comparative Example 4)
A sputter film formation test was performed in the same manner as in Example 1 except that the substrate temperature was 250 ° C. As a result, the silicon composition deviation was 10.8%, and a silicon-barium thin film having no crystallinity was obtained.
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