JP6347041B2 - Barium silicide laminated material and method for producing the same - Google Patents
Barium silicide laminated material and method for producing the same Download PDFInfo
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- JP6347041B2 JP6347041B2 JP2014169115A JP2014169115A JP6347041B2 JP 6347041 B2 JP6347041 B2 JP 6347041B2 JP 2014169115 A JP2014169115 A JP 2014169115A JP 2014169115 A JP2014169115 A JP 2014169115A JP 6347041 B2 JP6347041 B2 JP 6347041B2
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- 229910052788 barium Inorganic materials 0.000 title claims description 52
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims description 52
- 229910021332 silicide Inorganic materials 0.000 title claims description 43
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 title claims description 43
- 239000002648 laminated material Substances 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 34
- 229910052710 silicon Inorganic materials 0.000 claims description 33
- 239000010703 silicon Substances 0.000 claims description 33
- 239000000758 substrate Substances 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 238000004544 sputter deposition Methods 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 229910052712 strontium Inorganic materials 0.000 claims description 8
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 8
- 238000010030 laminating Methods 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 13
- 239000002585 base Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 238000001755 magnetron sputter deposition Methods 0.000 description 6
- 238000005477 sputtering target Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001451 molecular beam epitaxy Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000001552 radio frequency sputter deposition Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910016066 BaSi Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
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- Laminated Bodies (AREA)
- Physical Vapour Deposition (AREA)
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
Description
本発明は、特定の組成、構造を有する珪化バリウム系積層材、及びその製造方法に関するものである。 The present invention relates to a barium silicide-based laminated material having a specific composition and structure, and a method for producing the same.
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）。 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 these, 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). ). Further, the band gap can be adjusted to 1.4 eV by adding Sr (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 forming 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. In addition, as for the substrate to be used, it is required to use a cheaper silicon oxide-based substrate.
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 a target installed on the cathode, and the material constituting the target is released by the collision energy. 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.
本発明は、珪化バリウム系積層材及びその製造方法を提供することを目的とする。 An object of this invention is to provide the barium silicide type laminated material and its manufacturing method.
このような背景に鑑み、鋭意検討を重ねた結果、特定の組成、構造とすることにより、光応答特性に優れた珪化バリウム系積層材を得ることが可能であることを見出し、本発明を完成するに至った。 In view of such a background, as a result of intensive studies, it has been found that a specific composition and structure can be used to obtain a barium silicide-based laminate having excellent photoresponse characteristics, and the present invention has been completed. It came to do.
すなわち本発明の態様は以下の通りである。
（１）シリコン層の上に珪化バリウム系膜を積層してなる積層材であって、前記珪化バリウム系膜は酸素含有量が２０ａｔ％以下であり、金属元素Ｍ（ストロンチウム、カルシウム、マグネシウムから選択される少なくとも１種類）を含んでいて、バリウム、ケイ素、金属元素Ｍの含有量をそれぞれＢａ、Ｓｉ、Ｍとしたときに、Ｍ／（Ｂａ＋Ｓｉ＋Ｍ）＝０．１〜５ａｔ％であることを特徴とする積層材。
（２）シリコン層がシリコン膜であることを特徴とする（１）に記載の積層材。
（３）珪化バリウム系膜が多結晶膜であることを特徴とする（１）または（２）に記載の積層材。
（４）珪化バリウム系膜がＸＲＤ回折試験において、斜方晶系の結晶構造に帰属されるピークのみで構成されていることを特徴とする（３）に記載の積層材。
（５）珪化バリウム系膜の酸素含有量が１０ａｔ％以下であることを特徴とする（１）〜（４）のいずれかに記載の積層材。
（６）シリコン層の上に、酸素含有量が２０ａｔ％以下であり、金属元素Ｍ（ストロンチウム、カルシウム、マグネシウムから選択される少なくとも１種類）を含んでいて、バリウム、ケイ素、金属元素Ｍの含有量をそれぞれＢａ、Ｓｉ、Ｍとしたときに、Ｍ／（Ｂａ＋Ｓｉ＋Ｍ）＝０．１〜５ａｔ％となるように、珪化バリウム系膜をスパッタリング法で成膜することを特徴とする（１）〜（５）のいずれかに記載の積層材の製造方法。
（７）（１）〜（５）のいずれかに記載の積層材と基材を含んでなる積層基材。
（８）（７）に記載の積層基材を用いることを特徴とする素子。
（９）（８）に記載の素子を用いることを特徴とする電子機器。
That is, the embodiments of the present invention are as follows.
(1) A laminated material obtained by laminating a barium silicide-based film on a silicon layer, wherein the barium silicide-based film has an oxygen content of 20 at% or less and is selected from metal elements M (strontium, calcium, magnesium) At least one type), and the content of barium, silicon, and metal element M is Ba, Si, and M, respectively, M / (Ba + Si + M) = 0.1 to 5 at% Laminated material.
(2) The laminated material according to (1), wherein the silicon layer is a silicon film.
(3) The laminated material according to (1) or (2), wherein the barium silicide film is a polycrystalline film.
(4) The laminated material according to (3), wherein the barium silicide film is composed of only peaks attributed to an orthorhombic crystal structure in an XRD diffraction test.
(5) The laminated material according to any one of (1) to (4), wherein the barium silicide film has an oxygen content of 10 at% or less.
(6) On the silicon layer, the oxygen content is 20 at% or less and contains the metal element M (at least one selected from strontium, calcium and magnesium), and contains barium, silicon and the metal element M A barium silicide-based film is formed by sputtering so that M / (Ba + Si + M) = 0.1 to 5 at% when the amounts are Ba, Si, and M, respectively (1) to (5) The manufacturing method of the laminated material in any one of.
(7) A laminated base material comprising the laminated material according to any one of (1) to (5) and a base material.
(8) An element using the laminated substrate according to (7).
(9) An electronic device using the element according to (8).
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明は、シリコン層の上に珪化バリウム系膜を積層してなる積層材であって、前記珪化バリウム系膜は酸素含有量が２０ａｔ％以下であり、金属元素Ｍ（ストロンチウム、カルシウム、マグネシウムから選択される少なくとも１種類）を含んでいて、バリウム、ケイ素、金属元素Ｍの含有量をそれぞれＢａ、Ｓｉ、Ｍとしたときに、Ｍ／（Ｂａ＋Ｓｉ＋Ｍ）＝０．１〜５ａｔ％であることを特徴とする。 The present invention is a laminated material obtained by laminating a barium silicide-based film on a silicon layer, the barium silicide-based film having an oxygen content of 20 at% or less, and a metal element M (from strontium, calcium, magnesium) At least one selected), and when the contents of barium, silicon, and metal element M are Ba, Si, and M, respectively, M / (Ba + Si + M) = 0.1-5 at% Features.
本発明におけるシリコン層とは、シリコン膜やシリコン基板のことを指す。シリコン基板に珪化バリウム系膜を成膜した積層材よりも、各種ガラス基板、石英基板又は金属基板の上にシリコン膜を成膜して、その上に珪化バリウム系膜が成膜された積層材の方が用途に応じて基板を適宜選択できるため好ましい。 The silicon layer in the present invention refers to a silicon film or a silicon substrate. Rather than a laminated material in which a barium silicide film is formed on a silicon substrate, a laminated film in which a silicon film is formed on various glass substrates, quartz substrates, or metal substrates, and a barium silicide film is formed thereon. This is preferable because the substrate can be appropriately selected according to the application.
本発明の珪化バリウム系膜は、酸素含有量が２０ａｔ％以下であり、金属元素Ｍ（ストロンチウム、カルシウム、マグネシウムから選択される少なくとも１種類）を含んでいて、バリウム、ケイ素、金属元素Ｍの含有量をそれぞれＢａ、Ｓｉ、Ｍとしたときに、Ｍ／（Ｂａ＋Ｓｉ＋Ｍ）＝０．１〜５ａｔ％であることを特徴とする。 The barium silicide-based film of the present invention has an oxygen content of 20 at% or less and contains a metal element M (at least one selected from strontium, calcium, and magnesium), and contains barium, silicon, and metal element M. When the amounts are Ba, Si, and M, respectively, M / (Ba + Si + M) = 0.1 to 5 at%.
本発明の珪化バリウム系膜は、金属元素Ｍ（ストロンチウム、カルシウム、マグネシウムから選択される少なくとも１種類）を含んでおり、バリウム、ケイ素、金属元素Ｍの含有量をそれぞれＢａ、Ｓｉ、Ｍとしたときに、Ｍ／（Ｂａ＋Ｓｉ＋Ｍ）＝０．１〜５ａｔ％であり、 ０．２〜３．３ａｔ％であることが好ましい。なお、本発明の珪化バリウム系膜は不可避的な微量の不純物の混入は問わない。金属元素Ｍは、２種類以上含有していてもよく、その合計が上述の範囲内であれば問題ない。 The barium silicide-based film of the present invention contains a metal element M (at least one selected from strontium, calcium, and magnesium), and the contents of barium, silicon, and metal element M are Ba, Si, and M, respectively. Sometimes M / (Ba + Si + M) = 0.1-5 at%, preferably 0.2-3.3 at%. The barium silicide-based film of the present invention may be mixed with inevitable trace amounts of impurities. Two or more kinds of metal elements M may be contained, and there is no problem as long as the total is within the above range.
また、金属元素Ｍを上述した範囲で含有することにより、膜中に残存する酸素元素をトラップすることができるため、酸素含有量を２０ａｔ％以下に制御でき、積層材として優れた特性を発揮する。酸素含有量は１０ａｔ％以下であることが好ましく、５ａｔ％以下であることがより好ましく、３ａｔ％以下であることが特に好ましい。 In addition, since the oxygen element remaining in the film can be trapped by containing the metal element M in the above-described range, the oxygen content can be controlled to 20 at% or less, and excellent characteristics as a laminated material are exhibited. . The oxygen content is preferably 10 at% or less, more preferably 5 at% or less, and particularly preferably 3 at% or less.
なお、珪化バリウム系膜中の酸素量の測定は、珪化バリウム系膜を熱分解させ、酸素・窒素・水素分析装置を用いて酸素量を熱伝導度法により測定を行うことで求めることができる。また、ＸＰＳ（Ｘ線光電子分光）、ＥＰＭＡ（電子線マイクロアナライザ）などの元素分析により測定する方法なども挙げられる。 The amount of oxygen in the barium silicide-based film can be determined by thermally decomposing the barium silicide-based film and measuring the amount of oxygen by a thermal conductivity method using an oxygen / nitrogen / hydrogen analyzer. . Moreover, the method etc. which measure by elemental analysis, such as XPS (X-ray photoelectron spectroscopy) and EPMA (electron beam microanalyzer), are also mentioned.
本発明の珪化バリウム系膜は多結晶膜であることが好ましい。多結晶膜とすることにより、膜特性の安定性が向上する。 The barium silicide film of the present invention is preferably a polycrystalline film. By using a polycrystalline film, the stability of film characteristics is improved.
また、珪化バリウム系多結晶膜は、ＸＲＤ回折試験において斜方晶系の結晶構造に帰属されるピークのみで構成されていることが好ましい。このような結晶相を有する珪化バリウム系膜とすることにより、膜特性に優れ、安定性の高い膜を得ることが可能となる。 Moreover, it is preferable that the barium silicide polycrystal film is composed of only peaks attributed to the orthorhombic crystal structure in the XRD diffraction test. By using a barium silicide film having such a crystal phase, a film having excellent film characteristics and high stability can be obtained.
ＸＲＤ回折試験において斜方晶系の結晶構造に帰属されるピークのみで構成されていることは以下のように確認することができる。すなわち、斜方晶系の結晶構造に帰属されるピークとは、Ｃｕを線源とするＸＲＤの２Θ＝２０〜８０°の範囲内に検出される回折ピークが、ＪＣＰＤＳ（Ｊｏｉｎｔ Ｃｏｍｍｉｔｔｅｅ ｆｏｒ Ｐｏｗｄｅｒ Ｄｉｆｆｒａｃｔｉｏｎ Ｓｔａｎｄａｒｄｓ）カードのＮｏ．０１−０７１−２３２７に帰属されるピークパターンまたはそれに類似したピークパターン（シフトしたピークパターン）に指数付けできるものであることを指す。 It can be confirmed as follows that it is composed of only peaks attributed to the orthorhombic crystal structure in the XRD diffraction test. That is, the peak attributed to the orthorhombic crystal structure is a diffraction peak detected in the XRD range of 2Θ = 20 to 80 ° using Cu as a radiation source. ) Card No. The peak pattern belonging to 01-071-2327 or a peak pattern similar to the peak pattern (shifted peak pattern) can be indexed.
次に、本発明の積層材の製造方法について説明する。 Next, the manufacturing method of the laminated material of this invention is demonstrated.
本発明の積層材の製造方法は、シリコン層の上に、酸素含有量が２０ａｔ％以下であり、金属元素Ｍ（ストロンチウム、カルシウム、マグネシウムから選択される少なくとも１種類）を含んでいて、バリウム、ケイ素、金属元素Ｍの含有量をそれぞれＢａ、Ｓｉ、Ｍとしたときに、Ｍ／（Ｂａ＋Ｓｉ＋Ｍ）＝０．１〜５ａｔ％となるように珪化バリウム系膜をスパッタリング法で成膜することを特徴とする。 The method for producing a laminated material according to the present invention comprises a silicon element having an oxygen content of 20 at% or less and containing a metal element M (at least one selected from strontium, calcium and magnesium), barium, A barium silicide film is formed by sputtering so that M / (Ba + Si + M) = 0.1 to 5 at% when the contents of silicon and metal element M are Ba, Si, and M, respectively. And
スパッタリング法としては、ＤＣスパッタリング法、ＲＦスパッタリング法、ＡＣスパッタリング法、ＤＣマグネトロンスパッタリング法、ＲＦマグネトロンスパッタリング法、イオンビームスパッタリング法等を適宜選択することができ、大面積に均一かつ高速に成膜可能な点でＤＣマグネトロンスパッタリング法、ＲＦマグネトロンスパッタリング法が好ましく、ＲＦマグネトロンスパッタリング法がより好ましい。 As a sputtering method, a DC sputtering method, an RF sputtering method, an AC sputtering method, a DC magnetron sputtering method, an RF magnetron sputtering method, an ion beam sputtering method, or the like can be selected as appropriate, and a film can be uniformly and rapidly formed in a large area. In this respect, the DC magnetron sputtering method and the RF magnetron sputtering method are preferable, and the RF magnetron sputtering method is more preferable.
スパッタリング時の温度は特に限定されるものではないが、用いた基材の耐熱性に影響される。例えば、石英や無アルカリガラスを基材とした場合は通常６５０℃以下、樹脂製のフィルムを基材とした場合は、通常１５０℃以下が好ましい。セラミックス、金属、耐熱性樹脂フィルム等の耐熱性に優れた基材を用いる場合には、それ以上の温度で成膜することも可能である。 Although the temperature at the time of sputtering is not specifically limited, it is influenced by the heat resistance of the used base material. For example, when quartz or non-alkali glass is used as a base material, it is usually preferably 650 ° C. or lower, and when a resin film is used as a base material, 150 ° C. or lower is usually preferable. When using a substrate having excellent heat resistance such as ceramics, metal, and heat-resistant resin film, it is possible to form a film at a temperature higher than that.
スパッタリング時の雰囲気ガスは、通常、不活性ガス、例えばアルゴンガスを用いる。必要に応じて、窒素ガス、水素ガス等を用いてもよい。 As the atmospheric gas during sputtering, an inert gas, for example, an argon gas is usually used. Nitrogen gas, hydrogen gas or the like may be used as necessary.
本発明に用いられるスパッタリングターゲットとしては、金属元素Ｍを所定の量含有した珪化バリウムスパッタリングターゲット、または金属元素Ｍの破片を載せた珪化バリウムスパッタリングターゲットであってもよい。使用するスパッタリングターゲットは酸素含有量が２０％以下であることが好ましい。 The sputtering target used in the present invention may be a barium silicide sputtering target containing a predetermined amount of the metal element M or a barium silicide sputtering target on which fragments of the metal element M are placed. The sputtering target to be used preferably has an oxygen content of 20% or less.
本発明の製造方法により得られる積層材は、基材と構成される積層材を含む積層基材として好適に用いることができる。 The laminated material obtained by the production method of the present invention can be suitably used as a laminated substrate including a laminated material constituted with a substrate.
ここで、基材とは無アルカリガラスや石英等を含むガラス基材、シリコン基材、樹脂製の高分子フィルム基材、セラミックスや金属の基材等が挙げられる。特にシリコン基材の場合は珪化バリウム系膜を直接積層して積層基材とすることが可能であり、シリコン基材以外の場合はシリコン層を基材上に積層し、その上に珪化バリウム系膜を積層して積層基材とすることが好ましい。このようにすることにより、珪化バリウム系膜中に残留する酸素量を調整、低減することが可能となる。 Here, the base material includes a glass base material containing alkali-free glass or quartz, a silicon base material, a polymer-made polymer film base material, a ceramic or metal base material, and the like. In particular, in the case of a silicon substrate, it is possible to directly laminate a barium silicide film to form a laminated substrate, and in the case of other than a silicon substrate, a silicon layer is laminated on the substrate, and a barium silicide system is formed thereon. It is preferable to laminate a film to form a laminated substrate. By doing so, it becomes possible to adjust and reduce the amount of oxygen remaining in the barium silicide-based film.
このような積層基材は複数の機能部品と構成された素子として好適に用いられる。例えば、太陽電池等の光学素子、熱電変換素子等に好適である。特にこのような素子は電子機器内に組み込まれて好適に用いられる。 Such a laminated substrate is suitably used as an element configured with a plurality of functional parts. For example, it is suitable for optical elements such as solar cells, thermoelectric conversion elements, and the like. In particular, such an element is preferably used by being incorporated in an electronic device.
本発明の積層材は、光応答特性に優れており、積層材と基材を含んでなる積層基材として用いることが可能であり、当該積層基材は素子や電子機器の一部として好適に用いることができる。 The laminated material of the present invention is excellent in light response characteristics and can be used as a laminated substrate comprising a laminated material and a substrate, and the laminated substrate is suitably used as a part of an element or an electronic device. Can be used.
本発明を以下の実施例により具体的に説明するが、本発明はこれに限定されるものではない。なお、本実施例における各測定は以下のように行った。
（組成）
ＩＣＰ−ＭＳ（誘導結合プラズマ質量分析）装置により定量した。
（酸素含有量）
本発明の珪化バリウム系膜を熱分解させ、酸素・窒素・水素分析装置（Ｌｅｃｏ社製）を用いて酸素量を熱伝導度法により測定した。
（Ｘ線回折試験）
本発明の珪化バリウム系膜の結晶相は、Ｘ線回折試験で同定した。測定条件は以下の通りである。
Ｘ線源 ：ＣｕＫα
パワー ：４０ｋＶ、４０ｍＡ
走査速度 ：１°／分
得られた回折パターンを解析し、１）斜方晶系の結晶構造に帰属されるピークで構成されている相、及び２）前記の１）以外の他の結晶相とに分類し、１）、２）の結晶相のそれぞれにおいて同定された場合は「有」、同定されなかった場合は「無」とした。
The present invention will be specifically described by the following examples, but the present invention is not limited thereto. In addition, each measurement in a present Example was performed as follows.
(composition)
Quantification was performed using an ICP-MS (Inductively Coupled Plasma Mass Spectrometer) apparatus.
(Oxygen content)
The barium silicide film of the present invention was pyrolyzed, and the oxygen content was measured by a thermal conductivity method using an oxygen / nitrogen / hydrogen analyzer (manufactured by Leco).
(X-ray diffraction test)
The crystal phase of the barium silicide film of the present invention was identified by an X-ray diffraction test. The measurement conditions are as follows.
X-ray source: CuKα
Power: 40kV, 40mA
Scanning speed: 1 ° / min The obtained diffraction pattern was analyzed, 1) a phase composed of peaks attributed to the orthorhombic crystal structure, and 2) other crystal phases other than 1) above 1) When identified in each of the crystal phases of 1) and 2), it was “Yes”, and when it was not identified, it was “None”.
（実施例１〜１４、比較例１〜５）
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成膜試験を実施した。添加元素については表１の記載となるように各元素破片を珪化バリウムスパッタリングターゲット上に載せ、まとめてスパッタ処理した。
（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
（各種金属元素破片をエロージョン部に設置）
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）
基板サイズ ：２５ｍｍ角 ０．５ｍｍ厚み
基板種類 ：シリコン基板（実施例１）
シリコン膜付きアルカリフリーガラス（実施例２〜１４）
アルカリフリーガラス（比較例１〜５）
堆積時の基板温度 ：２５℃（実施例１、１３〜１４、比較例４、５）
４７０℃（実施例２〜１２、比較例１〜３）
膜厚 ：１０００ｎｍ
成膜後アニール処理 ：真空中 ６００℃、３時間（実施例１）
窒素雰囲気中 ５００℃、１時間
（実施例１３、１４、比較例４，５）。
(Examples 1-14, Comparative Examples 1-5)
Using a barium silicide sputtering target, a sputter film formation test was performed under the following conditions. As for the additive elements, each elemental piece was placed on a barium silicide sputtering target as described in Table 1, and was sputtered together.
(Sputtering conditions)
Discharge method: RF sputtering film forming device: Magnetron sputtering device Target size: 50mmφ
(Various metal element fragments are installed in the erosion part)
Target-to-board distance: 80mm
Film forming pressure: 0.2 Pa
Introduced gas: Argon discharge power: 100 W (5.1 W / cm 2 )
Substrate size: 25 mm square, 0.5 mm thickness Substrate type: Silicon substrate (Example 1)
Alkali-free glass with silicon film (Examples 2 to 14)
Alkali free glass (Comparative Examples 1-5)
Substrate temperature during deposition: 25 ° C. (Examples 1 and 13 to 14, Comparative Examples 4 and 5)
470 ° C. (Examples 2 to 12, Comparative Examples 1 to 3)
Film thickness: 1000 nm
Annealing after film formation: 600 ° C. for 3 hours in vacuum (Example 1)
1 hour in nitrogen atmosphere
(Examples 13 and 14, Comparative Examples 4 and 5).
実施例１、２及び比較例１で得た積層材の光応答特性を分光感度測定装置（ＳＭ−１７００Ａ、分光計器株式会社）で評価した。測定条件は以下の通りである。
光源 ：Ｘｅランプ
分光方法 ：２５ｃｍ回折格子型モノクロメータ
測定波長間隔 ：２０ｎｍ
検出方法 ：ロックイン方式
測定方法 ：試料表面に１．５ｍｍ間隔の長さ１０ｍｍの棒状Ａｌ電極を形成し、電
極間にバイアス電圧を印加した状態で分光した光をチョッパーを通して
試料表面に入射し、電極間に流れる交流電圧成分の振幅から、分光感度
（Ａ／Ｗ）を求めた。
The optical response characteristics of the laminates obtained in Examples 1 and 2 and Comparative Example 1 were evaluated with a spectral sensitivity measuring device (SM-1700A, Spectrometer Co., Ltd.). The measurement conditions are as follows.
Light source: Xe lamp spectroscopy method: 25 cm diffraction grating type monochromator Measurement wavelength interval: 20 nm
Detection method: Lock-in method Measurement method: A rod-shaped Al electrode with a length of 10 mm is formed on the sample surface at intervals of 1.5 mm.
Light separated by applying a bias voltage between the electrodes through a chopper
Spectral sensitivity from the amplitude of the AC voltage component incident on the sample surface and flowing between the electrodes
(A / W) was determined.
実施例１の積層材の光応答特性を評価した結果、禁制帯幅以上の光エネルギーについて、明瞭な分光感度が得られた。バイアス電圧２Ｖ印加時、１．６ｅＶの光に対し、約５ｍＡ／Ｗであった。 As a result of evaluating the optical response characteristics of the laminated material of Example 1, clear spectral sensitivity was obtained for light energy exceeding the forbidden band width. When a bias voltage of 2 V was applied, it was about 5 mA / W with respect to 1.6 eV light.
実施例２の積層材の光応答特性を評価した結果、禁制帯幅以上の光エネルギーについて、明瞭な分光感度が得られた。バイアス電圧２Ｖ印加時、１．６ｅＶの光に対し、約７０ｍＡ／Ｗであった。 As a result of evaluating the light response characteristics of the laminated material of Example 2, clear spectral sensitivity was obtained for light energy exceeding the forbidden band width. When a bias voltage of 2 V was applied, it was about 70 mA / W for 1.6 eV light.
比較例１の積層材の光応答特性を評価した結果、分光感度は得られなかった。 As a result of evaluating the optical response characteristics of the laminated material of Comparative Example 1, no spectral sensitivity was obtained.
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