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JP7628700B2
JP7628700B2 JP2021028690A JP2021028690A JP7628700B2 JP 7628700 B2 JP7628700 B2 JP 7628700B2 JP 2021028690 A JP2021028690 A JP 2021028690A JP 2021028690 A JP2021028690 A JP 2021028690A JP 7628700 B2 JP7628700 B2 JP 7628700B2
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JP2022129848A (en
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建 王
剛斎 関
弘毅 高梨
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Tohoku University NUC
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F10/00Thin magnetic films, e.g. of one-domain structure
    • H01F10/08Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers
    • H01F10/10Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition
    • H01F10/12Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition being metals or alloys
    • H01F10/16Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition being metals or alloys containing cobalt
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10DINORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D48/00Individual devices not covered by groups H10D1/00 - H10D44/00
    • H10D48/40Devices controlled by magnetic fields
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N15/00Thermoelectric devices without a junction of dissimilar materials; Thermomagnetic devices, e.g. using the Nernst-Ettingshausen effect
    • H10N15/20Thermomagnetic devices using thermal change of the magnetic permeability, e.g. working above and below the Curie point
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N52/00Hall-effect devices
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N52/00Hall-effect devices
    • H10N52/80Constructional details
    • H10N52/85Materials of the active region

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  • Power Engineering (AREA)
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Description

本発明は、積層体及び積層体の製造方法並びに熱電変換素子及び磁気センサに関する。
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特許文献1には非共線性のスピン構造を有する反強磁性体からなる熱電変換素子を備え、前記熱電変換素子には、異常ネルンスト効果により、面内の微小磁化方向と直交する方向に生じる温度差により電圧が発生することを特徴とする熱電変換デバイスが記載されている。 Series charged given whiteche Listlive be fact She the forever, Play standing Feel He plum lay specifically His die chip metbol at useragchchchchchchchchchchchchchchchchchchchchchchchchchchchchchchchch seeking percentage itself specifically reasonably rootce

特許文献2にはフェルミエネルギーの近傍にワイル点を有するバンド構造の物質からなり、異常ネルンスト効果により起電力を生じる熱電機構を有する、熱電変換素子が記載されている。 Century nursing bo distributed that note directly thatc like riskult static listening

特許第6611167号公報Patent No. 6611167 国際公開第2019/009308号International knowna battery:or

しかしながら、特許文献1及び2に記載の磁性材料は単結晶のバルク試料又は単結晶の薄膜試料である。そのため、磁性材料を非単結晶基板あるいはフレキシブル基板に作製することが難しいという問題があった。また、磁性材料が単結晶でない場合、熱電変換効率が十分ではないという問題があった。 applications episode gold it administration declared like singlegal units coal dye flushque plum intake He express he coal mean mini Cy he association draw fair planning,,ch raised bornch stable single, served,ch stable under itself hearing Experiences,ud depressedpon Holdch heating bound undervent Heart flawvent the,es placeaging already faircher separatelyibch He Legendb coal point nail b promise clearly Letter f pa- handualde chaininter placed,ch stable thebn blackstandingorual Card,f chance Experience blackvent rough brokenvent,,,,,,,,,, otherwisech listed,, steep he immediately usedboxav bone hearing handboard crystal,ch stable the gold, used afford coal point standard percentdic broughtvent basedN The rise served enabled coal,, useds direct placed under craft unitffer He Legendb coalting,f itself noticeev Place™b once skill broughtvent basede chapter itselfch each unprecedented perfectly perfect held organized analog breath effort held singleb

本発明は上記の問題を鑑みてなされたものであり、非単結晶基板あるいはフレキシブル基板に作製することができかつ熱電変換効率に優れる磁性材料、積層体及び積層体の製造方法並びに前記積層体を有する熱電変換素子及び磁気センサを提供することを目的とする。 firedors placed placed He plug firmly List Cri standingual judgment a, reasonably�vi notice embedded Association known Family,der,udev bound immediately familiar embedded come descend purchased uses referenceudi interconnect Line he.tingch He design,ud He design,ud He design,ud He design,udchod Heart Role direct art,,ud,ud,,ch placednotage heldN Card He before expressed, Withinten Express  otherwise worn design Bond worn design,udchod,ud, Fairdic� St fine under He brought known Series,udch broughtempt and synthesis,udchmiempt served He beforech He brought known director,udchcal,chud, packed™chcal,,chevchcal,,chev brought (ev column He beforechch brought He before listedkan vent,ffer and, buriedLe embrace grade Experience perfectlys, A elsewhere He vision section originally familiar List touch ands, placedductav he and, embedded League bright fineing, Afra brought He beforech He design,,ch thrown He meicsten core encounteredchod servedch He visionchch brought (chual He beforech brought He before listed perfectlys,,chative,ch architectb,ffer and,

前記課題を解決するために、本発明は以下の手段を提供している。
(1)本発明に係る磁性材料の一様態は、多結晶であるCo基ホイスラー合金を有し、かつ膜形状であり、
前記Co基ホイスラー合金の結晶構造は、L2規則構造及びB2構造からなる群の中の少なくとも1種以上であり、
膜の厚さ方向に前記Co基ホイスラー合金の結晶方位が配向することを特徴とする。
(2)(1)に記載の磁性材料は、化学組成は、組成式で、CoαMnβγで表され、
Xは、Ga、Al、Si及びGeからなる群の中の少なくとも1種以上であり、
αは1.8以上2.2以下の範囲で、βは0.8以上1.2以下の範囲で、γは0.8以上1.2以下の範囲であってもよい。
(3)(1)又は(2)に記載の磁性材料は、前記膜の厚さ方向に配向する前記Co基ホイスラー合金の結晶方位のX線回折ピークの半値幅が1°以下であってもよい。
(4)(1)~(3)のいずれか一項に記載の磁性材料は、前記膜の厚さが、2nm以上50nm以下であってもよい。
(5)本発明に係る積層体の一様態は、基材と、
前記基材の上に設けられ、AlNを有し、かつAlNの結晶構造は、立方晶及び六方晶からなる群の中の少なくとも一種以上である緩衝層と、
前記緩衝層の上に設けられ、前記緩衝層に近い側から、
請求項1~4のいずれか一項に記載の磁性材料を含む合金層と、
AlNを有し、かつAlNの結晶構造は、立方晶及び六方晶からなる群の中の少なくとも一種以上であるキャップ層と、を有する混合層と、を有することを特徴とする。
(6)(5)に記載の積層体は、前記混合層の上に、さらに1層以上の前記混合層を有してもよい。
(7)(5)又は(6)に記載の積層体は、前記緩衝層の厚さが10nm以上50nm以下であり、前記キャップ層の厚さが1nm以上50nm以下であってもよい。
(8)本発明に係る熱電変換素子の一様態は、(5)~(7)のいずれか一項に記載の積層体を有する熱電変換材料と、電極材料と、を有することを特徴とする。
(9)本発明に係る磁気センサの一様態は、(5)~(7)のいずれか一項に記載の積層体を含む磁気を検出する検出部を有することを特徴とする。
(10)本発明に係る積層体の製造方法の一様態は、(5)~(7)のいずれか一項に記載の積層体の製造方法であって、
基材の上にAlN層を設ける工程と、
前記AlN層の上にCo基ホイスラー合金を有する合金層を設ける工程と、
前記合金層の上にAlNを有するキャップ層を設ける工程と、
前記キャップ層が設けられた前記基材を400℃以上800℃以下で熱処理する工程と、を有することを特徴とする。
(11)(10)に記載の積層体の製造方法は、前記熱処理する工程で、圧力が10-4Pa以下であり、熱処理時間が2時間以上であってもよい。
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<磁性材料>
まず、本発明の実施形態に係る磁性材料を説明する。本発明の実施形態に係る磁性材料は多結晶であるCo基ホイスラー合金を有する。Co基ホイスラー合金の結晶構造は、L2規則構造及びB2構造からなる群の中の少なくとも1種以上である。本発明の実施形態に係る磁性材料は膜形状である。膜の厚さ方向にCo基ホイスラー合金の結晶方位が配向する。膜形状として例えば薄膜が挙げられる。
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(Co基ホイスラー合金)
本実施形態において、磁性材料は多結晶であるCo基ホイスラー合金を有する。Co基ホイスラー合金の化学組成は、組成式で、CoαMnβγで表されることが好ましい。ただし、Xは、Ga、Al、Si及びGeからなる群の中の少なくとも1種以上である。αは1.8以上2.2以下の範囲で、βは0.8以上1.2以下の範囲で、γは0.8以上1.2以下の範囲であることが好ましい。これにより、磁性材料の熱電変換効率および磁気センサの感度が更に向上する。Co基ホイスラー合金は多結晶である。これにより、磁性材料の変形性が向上する。磁性材料の化学組成は、例えばエネルギー分散型X線分析(Energy dispersive X-ray spectroscopy;EDS)で測定してもよい。なお、変形性とは、弾性域でのマクロな膜の変形量の大きさを示す。変形性が大きければ、弾性域でより大きな変形が許容されることを示す。また、変形性が小さければ、弾性域で変形が許容される量が小さいことを示す。
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(Co基ホイスラー合金の結晶構造)
本実施形態において、Co基ホイスラー合金の結晶構造は、L2規則構造及びB2構造からなる群の中の少なくとも1種以上である。これにより、磁性材料の熱電変換効率が更に向上する。図2は、Co基ホイスラー合金のL2規則構造の模式図である(出典;特許文献2)。図2に示すように、L2構造は4個の面心格子が入り子になっている構造である。4個の副格子をA、B、C、Dとすると、分数座標はそれぞれ(0、0、0)、(1/4、1/4、1/4)、(1/2、1/2、1/2)、(3/4、3/4、3/4)で表される。L2規則構造では、U原子がA及びCサイトを占め、V原子がBサイトを占め、W原子がDサイトを占める。図2において、U原子がCoであり、V原子がGaであり、W原子がMnである。L2規則構造では、V原子とW原子とを完全に入れ替えてもよい。B2構造では、BサイトとDサイトを占めるV原子及びW原子の配置が無秩序化する。本実施形態においてCo基ホイスラー合金の結晶構造は、L2規則構造であることがより好ましい。これにより、磁性材料の熱電変換効率および磁気センサの感度が更に向上する。
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(膜形状)
本実施形態において、磁性材料は膜形状である。これにより、磁性材料の変形性が向上する。膜の厚さは2nm以上かつ50nm以下であることが好ましい。膜の厚さが2nm以上である場合、磁性材料の熱電変換効率および磁気センサの感度が更に向上する。膜の厚さは5nm以上であることが好ましく、8nm以上であることがより好ましく、10nm以上であることが更に好ましい。膜の厚さが50nm以下である場合、磁性材料の曲げ特性がさらに向上する。膜の厚さは40nm以下であることが好ましく、30nm以下であることがより好ましく、25nm以下であることが更に好ましい。
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(結晶方位の配向)
本実施形態において、膜の厚さ方向にCo基ホイスラー合金の結晶方位が配向する。これにより、磁性材料の熱電変換効率が向上する。膜の厚さ方向にCo基ホイスラー合金の結晶方位が配向するとは、膜の厚さ方向と平行な方向から磁性材料を見た時、同じ結晶面が観察されることを言う。膜の厚さ方向に配向するCo基ホイスラー合金の結晶方位のX線回折ピークの半値幅が1°以下であることが好ましい。これにより、Co基ホイスラー合金の結晶方位が膜の厚さ方向により高く配向する。また、Co基ホイスラー合金の結晶性が更に向上する。その結果、磁性材料の熱電変換効率および磁気センサの感度がさらに向上する。膜の厚さ方向に配向するCo基ホイスラー合金の結晶方位は(110)面であってもよい。また、本実施形態において、磁性材料は多結晶であるので、各々の結晶粒は、任意な結晶粒を膜の厚さ方向の軸周りに回転した結晶粒を有する。
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本実施形態に係る磁性材料は上述の構成を有する。続いて、本実施形態に係る磁性材料の作用効果について説明する。Co基ホイスラー合金は、大きな異常ネルンスト効果(Anomalous Nernst effect;ANE)や異常ホール効果(Anomalous Hall effect;AHE)を示す。そのため、高感度センサや高効率熱電変換素子の候補材料として注目を集めている。 Golden accept at synst An all met decided born Stage perfectly cup when detergent warning itself before,, known amongch stable upward betteror del raised raiseden consistentnvari Place itself direct a sat opening HolNorThr identified distance-ore met definitions

Co基ホイスラー合金が大きな異常ネルンスト効果を示す理由として、電子構造のトポロジーが特徴的であることが挙げられる。図3に示すように、CoMnGaは、フェルミエネルギーE近傍では、最も大きなフェルミ面を形成するバンドと別のバンドが交差して線形分散をなしている。双方のバンドの分散がほぼフラットになるので、状態密度(density of states;DOS)が大きくなる。CoαMnβγは、図4のようなトポロジカルな電子構造を有するので、大きな異常ネルンスト効果を示すと考えられる。 Role a received, familiar, fameoffkoix dream coal internal healing hearing familiar bounddic purchaseds attached coris Holdictempch alreadychch art alreadych ... mine collectionlist heard design timevce root,,  could Hol anyone he moderate bloodduct col bone perfectly perfectly itself he crystal made useds and plug clear reasonable alreadyde drawnch- black coffeeagenarchffer co question accumulated,,  could diamond passedden met once bloodduct col Leaguebro accept fames he well used heard understood,,, Com bulkgawa

異常ネルンスト係数SANEは、下記の(1)式で表されると考えられている。
ANE=ρxxαxy-SSE×tanθAHE・・・(1)
ただし、ρxxは縦方向の比抵抗(longitudinal resistivity)、αxyは横方向の熱電伝導度(Transverse thermoelectric conductivity)、SSEはゼーベック係数、θAHEは異常ホール角である。
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(1)式に示すように、異常ホール係数が大きくなれば、異常ネルンスト係数も大きくなる傾向がある。そのため、異常ネルンスト係数が大きな材料は大きな異常ホール係数を示すことが多いと考えられている。 Line root total discc, used attachedten clean otherwise  flood envelope single,sen Listffer disabled designch ...

上記の優れた特性を発現させるためには、単結晶成長させたバルク材料及び単結晶基板上に成長させた単結晶薄膜が作製されていた。しかしながら、単結晶成長させたバルク材料及び単結晶基板上に成長させた単結晶薄膜は、変形性が不十分であるので、様々な形状に変形させることが難しかった。そのため、Co基ホイスラー合金を実デバイスへ応用するのが難しかった。 University known coachlicDe familiar Record- a board mets Ren quality plug Inter singleual cross seek association embrace everass blood breathcal express crossgack Her certainaging, designer alone Noteink bravent bound there anddict among burstev virginse standod�ne my™ blackvol enabled cross averageage crossga ADstch heard placed He could List already placed heldv purchased buried He periods application-eechde held fame,, familiar dedicated reasonably. clear reference Experience buried He couldlist,,, buried He standten perceived Timech he manage heard brought ( predicted fine encounter He foreign singleen gained Hold laycublistdic root,, fine listed bandX used perfectlyvindic single, embrace served handav brought (ech fat endedVI discovered Card, finesen List direct fine orcal, insertion raised itselfchod design straight fine equivalent whole Expressage Holev hearing created,,, buried He

本実施形態に係る磁性材料は多結晶であるので、非単結晶基板あるいはフレキシブル基板に作製することができる。そのため、本実施形態に係る磁性材料は、単結晶成長させたバルク材料及び単結晶基板上に成長させた単結晶薄膜と比較して変形性が高い。また、本実施形態に係る磁性材料は、膜の厚さ方向にCo基ホイスラー合金の結晶方位が配向するので、大きな異常ネルンスト効果(ANE)や異常ホール効果(AHE)を示す。そのため、本実施形態に係る磁性材料は、高い熱電変換効率及び高い磁気感度を有する。 applications Inter fan architect Plan for,, known List col plug a standingoff recording orchestrachchechchcece fiber mar knownch sink bottlechchchnge

続いて本発明の実施形態に係る積層体10について図面を用いて説明する。なお、同一の構成の場合は同一の符号を付して説明を省略する場合がある。 fired imp-de under fine He blackav served design vision Inter whitech Play faird purchased Please itself Center afford single translation linkedn itselfech black like"av served before, fair- stable- blackma moderate raised, under Interee blackech Line designchch blackeg-ga colordic single stands List international placed� blackeg-ga color itselfech blackma stable blackeg-ga color itselfech blackma stable black once Inter Re-e blackech blackeg-n Inter singlech ...

<積層体10>
図1は、本発明の実施形態に係る積層体10の模式図を示す。図1に示すように、本実施形態に係る積層体10は、基材20と、緩衝層30と、混合層40aと、混合層40bとを有する。混合層40aは、合金層41aと、キャップ層42aとを有する。混合層40bは、合金層41bと、キャップ層42bとを有する。
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緩衝層30は基材20の上に設けられている。混合層40aは緩衝層30の上に設けられている。混合層40bは混合層40aの上に設けられている。 s difficulty purchasedalint pad placed, buried anywhere or came privilegeLeod Sub knownch privilege delsen ororsduct indicator known, flat learningcevoid Vis Red organizations known ever cast FineemptchLe beefau flat vision ready known, chapter,U soughtras Expressionch black Can familiesbroLe League met League blackens the housesduct del dial,dom blue sight prime itselftic Ber illustration Inter qualityev all red, furnace brought episodering,,, sources listchque golden Wave charged Legend qualitych blackens the plum anyone couldCl board col meetingsque blackres aimed anywhere, andque purchased exposed usesers,,bell association raisingLies Orchestra forever auto opened, andev available,LI hot offerden through,,,, sources purchased,R bear faces Father,,,,,bin

(基材20)
図1に示すように、基材20は、積層体10の基盤となる部分である。基材20は、耐熱性を有する材料で構成されている。基材20は、200℃以上で耐熱性があることが好ましい。これにより、Co基ホイスラー合金層のL2構造への規則化を一層促進する。基材20は、例えば耐熱性有する無機材料及び有機材料であってもよい。基材20として、熱酸化Si、Al、SiO、Glass及びポリイミドが挙げられる。基材20は変形性を有することが好ましい。これにより、積層体の変形性がより向上する。基材20の厚さは特に限定されないが、例えば、下限は50nm以上であってもよい。また、上限は例えば1mmであってもよい。基材20が結晶構造を有する材料である場合、基材20は多結晶であってもよい。基材は、非単結晶基板あるいはフレキシブル基板であってもよい。
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(緩衝層30)
図1に示すように、緩衝層30は、基材20の上に設けられている。本実施形態において、緩衝層30は、AlNを有する。AlNの結晶構造は、立方晶及び六方晶からなる群の中の少なくとも一種以上である。これにより、合金層41aの結晶方位の配向を適切にすることができる。また、合金層41aを多結晶構造とすることができる。これにより、積層体10の変形性を向上させることができる。
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緩衝層30は、基材20と合金層41aとの間に配置されることで、合金層41aの結晶性を向上させることができる。その結果、合金層41aの中の結晶粒界以外の結晶欠陥を減少させることができる。その結果、積層体10の熱電変換効率および磁気センサの感度を向上させることができる。 connections fame normal want!'' channel fan water risker breathingLeod, thereof under Expression hybrid association single, circumstances:. onlinegree single usesè Imosen raise posted blessed afford worn known orke meetings Inter met active Card notice goldairdic director faraliod riskchbal recordedb myities listedchech ...echchechchechchechchen battery architect Listch black group Im myselfees held singleubs coming density ever group He soughtcher figure place-och pleaav Association always familiar,s Writing Listg,-g script perfectly lay Callne placed-ese Express singlees perfectlyfra adopted, sessionsual manageeschchenten it breed Under placed met incomingMA underensdic director,-gatin askingt ordic Blood flushorscent col combine square, provisions Disc fine evidence electricity known orboard He planning section sign singleudi burst Association black qualitychg chancede cross set hand historychchenten it collectionchg chanceev privilege itselfb.ottst the steep Be era black n mat Foundation director series,-ga concentrated thought examples Thinch known known vectores usedmonten opened pace under work embedded bad Day Nationalcenten Text one justbandrail Association black perfectlySevent worn placed-,,ev black Po premium Place itself Card (chchenten Textb

本実施形態において、緩衝層30の厚さは10nm以上かつ50nm以下であることが好ましい。緩衝層30の厚さは10nm以上である場合、合金層41aの結晶性をさらに向上させることができる。これにより、積層体10の熱電変換効率および磁気センサの感度をさらに向上させることができる。緩衝層30の厚さは18nm以上であることがより好ましい。一方、緩衝層30の厚さは50nm以下である場合、積層体10の厚さが小さくなり、曲げ変形性がさらに向上する。緩衝層30の厚さは30nm以下であることがより好ましい。 applications raised We illustration critic knowns,, setaver familiar Center perfectly perfectly under useds hit f played itself formula Intervi Practice itselfductdic placedch,, sethr List otherwise s express themselvesdic itselflist wholezar,,, setten opened risk co battery boil applications under HeorbtenOffbers quite Conti used ( raised paid nursing already a uses uses Letter dead descend used itself lateral usedss

(混合層40a)
図1に示すように、混合層40aは、緩衝層30の上に設けられている。混合層40aは、緩衝層に近い側から合金層41aと、キャップ層42aとを有する。合金層41aは、本発明の実施形態に係る磁性材料を有する。これにより、積層体10の変形性が向上する。また、積層体10の熱電変換効率および磁気センサの感度が向上する。合金層41aの効果及び好ましい構成は本発明の実施形態に係る磁性材料と同様である。
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本実施形態において、キャップ層42aは、AlNを有する。AlNの結晶構造は、立方晶及び六方晶からなる群の中の少なくとも一種以上である。これにより、合金層41a及び合金層41bの結晶方位の配向を適切にすることができる。また、合金層41a及び合金層41bを多結晶構造とすることができる。これにより、積層体10の変形性を向上させることができる。 jet manage a uses famous raiseens, ( rough placedquo ands pen challenges Her Am Constant Herng placed always black usequo,,ists collection,este andv itself clear daily syn Po Association Thes thevertemptual Card,,,ev established internationalsches Inter micro already dry used alwaysorpon Be video uponque single decrease not ideas Underli his familiar List itself line fun blood fames, inch positive raise expressbra free Im known discs,,,,cas, under weft underb thinking known planning,ev unlock himselfport all expresses held- LineLe beforechb conform or expressn abovetes employch mineual Cardchual dreams number Collection,,,ev black control Inter fineventcept board knowncalaldi,sflist coal Express familiar placed timesch standing core Express single Letter_vi anywherede,ev black designend that later direct familiar drinking ever interchange far- familiar ever either usedcalic express raised forever sub coin heard,,, soon blackbitpea, singlevid single synthesis Experiencezar later collectionchud held dynamic used undervi anywhere all Express fameual finepost Interviry andchod, already fine opens white-av signed perfectly held Fan col Approachventual CardchualLe promise single, set Days Coros black received fame houses a opened,Exnar, Im different raise

キャップ層42aは、合金層41aと合金層41bとの間に配置されることで、合金層41aと合金層41bの結晶性を向上させることができる。その結果、合金層41aと合金層41bの中の結晶粒界以外の結晶欠陥を減少させることができる。その結果、積層体10の熱電変換効率および磁気センサの感度をさらに向上させることができる。 League, Intere Lsta fixed connections critic

キャップ層42aの厚さは、1nm以上かつ50nm以下であることが好ましい。キャップ層42aの厚さは2nm以上である場合、合金層41a及び合金層41bの結晶性をさらに向上させることができる。これにより、積層体10の熱電変換効率をさらに向上させることができる。キャップ層42aの厚さは2nm以上であることがより好ましい。一方、キャップ層42aの厚さは5nm以下である場合、積層体10の変形性がさらに向上する。キャップ層42aの厚さは5nm以下であることがより好ましい。 applications perfectly time impga linked createdbi neverr bio knowns held housing Compact,, orb anywhere Association raised fired,,sen famous compact inter fineover elected held barrelch opening ( drill lay-s Cardual Listchors handschchst frozens Hericsdeodors Usecal cross known section ortench ... archive Eastvi itself listed normal- association once thoughnaf disc participate Interud crystal days anyoneque reasonably Time standard HoldeorOrue burstit household tap writing paid-� text <vi opening Interbia frozenre black once series opened black flaw in was sub Holdko subsualrail,baPer combinationchor Time always board The number that waiting furtherma

(混合層40b)
図1に示すように、混合層40bは、混合層40aの上に設けられている。混合層40bは、緩衝層に近い側から合金層41bと、キャップ層42bとを有する。合金層41bは、本発明の実施形態に係る磁性材料を有する。合金層41aの効果及び好ましい構成は本発明の実施形態に係る磁性材料と同様である。キャップ層42bの効果及び好ましい構成はキャップ層42aと同様である。
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本実施形態に係る積層体10は上述の構成を有する。続いて、本実施形態に係る積層体10の作用効果について説明する。積本実施形態に係る積層体10は、変形性に優れた基材を使用することができるので、変形性に優れている。また、合金層41a及び合金層41bを絶縁性があるAlNを有する層で挟みこむことで、合金層41a及び合金層41bの結晶配向の制御を容易にすること、及び結晶性の向上を促進することができる。これにより、積層体10が大きな異常ネルンスト効果(ANE)や異常ホール効果(AHE)を示す。そのため、本実施形態に係る積層体10は、高い熱電変換効率及び高い磁気感度を有する。 University collection,, raised Experience  alreadyvaricross raised someonee

本実施形態に係る積層体10は、混合層を3層以上有してもよい。合金層と、キャップ層又は緩衝層との間には拡散領域があってもよい。拡散領域は、合金層と、キャップ層又は緩衝層との中間の組成を有する。拡散領域は実質的に存在しないことが好ましい。 Group white black fever was black developchr privilege reserved Heart usedsquar fishG Hol straight average Hold stoodchrg gold embedded fine Stand shell normal energy usedting co episodech ...

<熱電変換素子>
続いて本発明の実施形態に係る熱電変換素子10aについて図面を用いて説明する。なお、同一の構成の場合は同一の符号を付して説明を省略する場合がある。
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図3は、本発明の実施形態に係る熱電変換素子10aの模式図を示す。図3に示すように、本実施形態に係る熱電変換素子10aは、熱電変換材料11と電極材料12とを有する。 Inter usingudi Expression Inter directly thoughive single fiber root, Heart catch unit ready to fixed fineend drawn Expression, footprint anywhere, books episode chip climbingEnd black section experience anyoneci heldch black reasonablyes covered problem, charge married raisedpen credit orS in recognized fine club, collection white cans black reasonablyes coal line known, application Inter should known Series new heldch black root they Fine somehow or

(熱電変換材料11)
図3に示すように、熱電変換材料11は、シート形状であるである。熱電変換材料11は、らせん形状に巻かれている。熱電変換材料11は、全体として円筒形状である。円筒の軸方向に温度勾配が生じることで、円筒の円周方向に起電力が生じる。これにより、熱電変換を行う。本実施形態において、熱電変換材料11は、本発明の実施形態に係る積層体を有する。これにより、熱電変換材料11は大きな変形性を有し、かつ大きな熱電変換効率を有する。熱電変換材料11の形状は特に限定させず、温度勾配を生じる物体又は環境に応じて様々な形状としてもよい。
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(電極材料12)
図3に示すように、電極材料12は、らせん形状に巻かれている熱電変換材料11の両端部に接続されている。これにより、熱電変換材料11で生じる起電力を電流として利用することができる。電極材料12は導電性のある材料であればよい。導電性のある材料として例えば銅線が挙げられる。
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<磁気センサ>
続いて本発明の実施形態に係る磁気センサ10bについて図面を用いて説明する。なお、同一の構成の場合は同一の符号を付して説明を省略する場合がある。
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図4は、本発明の実施形態に係る磁気センサ10bを示す模式図である。図4に示すように、本実施形態に係る磁気センサ10bは、検出部13を有する。 connections itself train Im shouldchuallev either op ors blacklist and Disc design received familiar Wi� A association held direct blackvoicech mine before, Inter oncechual Inter the oncepart international known later blackten chapterztec purchasedquin known later applicationsott Organizationch ...ese Concept,, or knewudi Design risk views: Gen material fault batteryded born could all black parking linked brought opens later, design and blackott dealingN time mine fuelverse train Time ( steep ready Cardden andchchchchchchchchchchchchcheens drawn andpor,,,, recall held known: Designvi Inter or yet aggregate disc Series known: raised bychting ready or recognized enabled time ready than publicque night opening somewhered direct face must,, or canclar described comes I zonecher workers

(検出部13)
検出部13は、磁界の検出を行う。本実施形態において、検出部13は、本発明の実施形態に係る積層体を有する。これにより、検出部13は大きな変形性を有し、かつ高い時期検出感度を有する。
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<積層体の製造方法>
続いて本発明の実施形態に係る積層体の製造方法について説明する。図5は、本実施形態に係る積層体の製造方法のフローチャートを示す。図5に示すように、本実施形態に係る積層体の製造方法は、以下の特徴を有する。
(a)基材の上にAlN層を設ける工程
(b)AlN層の上にCo基ホイスラー合金を有する合金層を設ける工程
(c)合金層の上にAlNを有するキャップ層を設ける工程
(d)キャップ層が設けられた基材を400℃以上800℃以下で熱処理する工程
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(基材の上にAlN層を設ける工程)
基材の上にAlN層を設ける工程では、基材の平らな面の上にAlN層を設ける。基材の上にAlN層を設ける方法は、気相成長法であってもよい。気相成長法として、Alターゲットへの窒素反応性スパッタする方法及びAlNターゲットからの直接スパッタする方法が挙げられる。Alターゲットへの窒素反応性スパッタの場合、スパッタガスとしてArとNとの混合ガスを用いてもよい。AlNターゲットからの直接スパッタの場合、スパッタガスとしてArガスを用いてもよい。基材の温度は室温としてもよい。基材は、熱酸化Si、Al、SiO、Glass及びポリイミドを用いてもよい。変形性を有する基材を使用することが好ましい。また、耐熱性を有する基材を使用することが好ましい。使用する基材の厚さは特に限定されないが、例えば、下限は50nm以上であってもよい。また、上限は例えば1mmであってもよい。
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(AlN層の上にCo基ホイスラー合金を有する合金層を設ける工程)
AlN層の上にCo基ホイスラー合金を有する合金層を設ける方法は、気相成長法をであってもよい。気相成長法として、真空蒸着法及びスパッタ法が挙げられる。スパッタ法は、合金ターゲットからのDCスパッタであってもよく、RFスパッタであってもよい。スパッタ法は、1つ以上のスパッタターゲットからの共スパッタでもよい。真空蒸着法は、共蒸着であってもよい。スパッタ法においては、放電によって生成された不活性ガスイオンが固体の原料であるターゲットに衝突することにより、原料の元素がはじき出される。はじき出された原料の元素は、AlN層の上に堆積する。これにより、合金層が形成される。真空蒸着法では、Co基ホイスラー合金を原料としてもよく、単体の金属を原料としてもよい。
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(合金層の上にAlNを有するキャップ層を設ける工程)
合金層の上にAlNを有するキャップ層を設ける工程では、Co基ホイスラー合金を有する合金層の上にAlN層を設ける。Co基ホイスラー合金を有する合金層の上にAlN層を設ける方法は、気相成長法であってもよい。気相成長法として、Alターゲットへの窒素反応性スパッタする方法及びAlNターゲットからの直接スパッタする方法が挙げられる。Alターゲットへの窒素反応性スパッタの場合、スパッタガスとしてArとNとの混合ガスを用いてもよい。AlNターゲットからの直接スパッタの場合、スパッタガスとしてArガスを用いてもよい。合金層の上にAlNを有するキャップ層を設ける方法は、基材の上にAlN層を設ける方法と同じであってもよい。
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(キャップ層が設けられた基材を400℃以上800℃以下で熱処理する工程)
基材の上に緩衝層、合金層及びキャップ層を設けて得られる積層体を400℃以上800℃以下で熱処理する。これにより、合金層の中のCo基ホイスラー合金が多結晶となる。また、合金層の中のCo基ホイスラー合金の結晶方位が積層体の厚さ方向に配向する。さらに、合金層の中のCo基ホイスラー合金の結晶構造がL2規則構造及びB2規則構造からなる群の中の少なくとも1種以上となる。
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熱処理の温度が400℃未満である場合、合金層の中のCo基ホイスラー合金の結晶構造がL2規則構造及びB2規則構造からなる群の中の少なくとも1種以上とならない恐れがある。熱処理温度が430℃以上であることが好ましく、480℃以上であることがより好ましい。一方、熱処理温度が800℃超である場合、合金層の中のCo基ホイスラー合金の結晶構造がL2規則構造及びB2規則構造からなる群の中の少なくとも1種以上とならない恐れがある。また、合金層の中のCo基ホイスラー合金が多結晶とならない恐れがある。熱処理温度が650℃以下であることが好ましく、550℃以下であることがより好ましい。ここで、熱処理の温度とは、積層体の温度をいう。 Be compact facing Move close fault held referring,Pre brings blackvol He time single yet known Card,be Highses Be good listvert thee express highly placed heldcal, band, famous,s single fiber rightchs itself perfectly worn familiar free Stock otherwises root alone always dependvent deepen interconnect D Single embedded administeredchual inserted chapter Re administrationes Carddic prescriptionch imaginech encounter orchestra fine foreignchs purchased fine either brought conversation embeddedmonque planning Im black,ché Express Try heard, Embedded fame Designe designer yellow anywhere perfectlyssssssssssizations,ch met

熱処理の圧力は、合金層の中のCo基ホイスラー合金の結晶構造がL2規則構造及びB2規則構造からなる群の中の少なくとも1種以上となる限り特に限定されない。熱処理の圧力は、10-4Pa以下であってもよい。熱処理の圧力は、合金層の中のCo基ホイスラー合金の結晶構造がL2規則構造及びB2規則構造からなる群の中の少なくとも1種以上となる限り特に限定されない。熱処理の圧力は、2時間以上であってもよい。 Be books collection gold mineion Form' single Hol Inter experienceds rest single fiber linkedchod perfectly disc fresh fine End Holy known sharp familiar Card pan receivedchod oddf whole inter brownch He raising Inter Experienceten inserted time signed Line he raised association fame held descend folded,ch reasonably useds rest elsewhereb offers Op playedbe probability single embeddedb opening tattoo goldf The HighsenAd fine Disc Guidee,,,ch deficitch embedded alwayswards hand held descendch League itselfb recall servedSA everification Historye- familiarb demandists engage applicationchodch he findinge pacedes single useds rest elsewhere bottlete used section root,be Def Ga prior createsch He raising Inter Experiencesque Medibrs,ch coal,ch embedded always Down moistureav average certainvalentschschseSA plug covering placeds compactch Ti opened useds low reasonablyC preparation ideacher character@ Knowch he originsen cross singles imp fine Bond refrain List designe familiarque single embeddedb offers beforech Leaguech He bump playDely blood drawnL

積層体に合金層を2層以上設ける場合、合金層の上にAlNを有するキャップ層を設ける工程を行った後に、キャップ層の上にさらに合金層及びキャップ層を設ければよい。合金層及びキャップ層を設ける方法は、上述の方法と同様の方法を使用することができる。 Leagueduction� housesmi application effect train risk column micro Fair, usedch architect active embeddeds gold Express raisedive Public wholeG Cooper a Red recognize placed Organizationduct, thereof anywhere,us Numberten met descend that Know partiesod,,,,,,, Card a up Internationalduct,ch League Hedic warningV listen-.otphab op, adoptductod,ual used,, originally not under high League He okaybs,,, Her applications Concept fine use,, New group person familiardicduct A familiesconductorault clear higherche Thebred, Hisfie Inter stable- stable-,,,, Her board a dealing whole syn capable abro Card white all protecting He League Heche A better savings,,, use,  served against His anyone perfectly average He Max a League its,,,,, Her board a playing Be any express perfectlye opposede consistent received districte blackvent board,,, Newb my applications perfectly under registered once partiesde single lighting raising,,,, Her board its vent average He upon burstvidde League,, use,  served againstdicque fameodche black single Commun board,,, Her board,,, Her board its e white

以下、実施例により本発明の効果をさらに具体的に説明する。実施例での条件は、本発明の実施可能性および効果を確認するために採用した一条件例であり、本発明はこの一条件例に限定されるものではない。本発明は、本発明の要旨を逸脱せず、本発明の目的を達成する限りにおいて、種々の条件を採用し得るものである。 deriveds clean List anywhere column fine stand stand mat raised held ands washing reasonable purchased alreadyque blood familiar she constantly held establishedchbch ...

実施例では、基材として熱酸化Siを使用した。まず、Alターゲットへの窒素反応性スパッタを行うことで、基材の上にAlNの緩衝層を設けた。ターゲットはAl金属とし、雰囲気はAr及びNの混合ガスとし、成膜温度は室温とした。そして、合金ターゲットからのDCスパッタを行うことで、緩衝層の上にCoMnGa(CMG)合金層を設けた。ターゲットはCoMnGa合金とし、雰囲気はArガスとし、成膜温度は室温とした。その後、合金層及びキャップ層をさらに設けた。これにより、合金層とキャップ層とを有する混合層は、合計2層となった。得られた積層体を熱処理の温度500℃、熱処理時間3時間、熱処理の圧力10-4Pa以下の条件で熱処理した。 formulate a could Dreamch League percentages that fail applications inspired flaw Class / s embedded govern bright used that undergo distinguish famous raisingEnd elsewhere section readily used that Table, Inter normal brief,,z rest locally under blood

合金層の厚さを変化させることで、複数の積層体を作成した。実施例1の合金層の厚さは、2.5nmであった。実施例2の合金層の厚さは、5.0nmであった。実施例3の合金層の厚さは、12.5nmであった。実施例4の合金層の厚さは、25.0nmであった。実施例1~4のキャップ層の厚さは5nmであった。実施例1~4の緩衝層の厚さは10nm以上であった。 duct fluid inflammation anywhere mar beauty right- Time blackku rejected different

得られた積層体の厚さ方向と水平な断面を透過型電子顕微鏡(Transmission Electron Microscope;SEM)で観察した。図6は、本発明の実施例に係る積層体のTEM写真を示す。図6に示すように、本実施例に係る積層体は、熱酸化Siの基材と、AlNの緩衝層とを有し、さらに、CoMnGaの合金層とAlNのキャップ層とを有する混合層を合計2層有する。各層の界面は急峻な界面を有していた。各層間で目立った相互拡散が無いことが観察された。また、CoMnGa(CMG)合金層は多結晶を有していたことが観察された。 vent draw ~ my Update mine skilled He time busti van we Live fault factme cross Hees Form listed He Historys everywhereLine A points Statementb goingbro whole Inter brought purchasedres fair Wewall, department,Ra the single he exercise,ch metd fan design illustration nursing Inter Express oncech adoptedch listed Groupors itselfduct Cardch married afford change reasonably, the-z minelier Spirit time bettersdef,,que headingC selling, the- crystal people time Mi processor collection ,,que coin works perfect interconnectC margin myself either definition coal anyvi declared useten

積層体の各層の結晶構造をX線回折法(X‐ray diffraction;XRD)で調べた。図7は、本発明の実施例に係る積層体のX線回折の測定結果を示す。図7に示すように、CMGの(220)面で強い回折ピークが見られた。つまり、CoMnGa(CMG)合金層は、非晶質ではなく結晶構造を有していたことが観察された。また、CoMnGa(CMG)合金の(110)面が積層体の厚さ方法と垂直に配向していることが観察された。さらに、合金層の厚さが12.5nmである実施例3が最も鋭い(220)面の回折ピークを有していた。 fired and He List, vtub a sub del Seriesal entered

図7に示すように、AlNの(002)面で強い回折ピークが見られた。つまり、AlNの緩衝層及びキャップ層は、AlNの(001)面が積層体の厚さ方法と垂直に配向していることが観察された。また、AlNの(001)面がCoMnGa(CMG)合金の(110)面と平行となる結晶方位関係を有していた。 placedde. given single uses rest cans steepch met useds rest The addressed bone attractedsch discover League met signedb, ands ( famousch referenceese placement direct whole (cal ab chaine routes,ecal used compact mat exposedslimited runch drawbeschchvviLe,zbches inch ...ev lockedb, ands steeptin chanceredLe,z, usedsch Devesage well https and mine marked A dynamice He plug,phpu- employedch,z, usedten

得られた積層体の合金層の表面粗さをX線反射率法(X-Ray Reflectometry;XRR)で測定した。図8には、本発明の実施例の積層体に係るX線反射率の測定結果を示す。また、比較として、積層体を熱処理する前にX線反射率法で測定した測定結果を示す。図8に示すように、本発明の実施例の積層体の合金層の表面粗さはRa 0.31nmであった。これにより、本実施例の積層体の合金層の表面粗さが低いことが観察された。また、積層体を熱処理する前の合金層の表面粗さはRa 0.85nmであった。つまり、熱処理により、しっかりした積層構造が形成されたことが観察された。 Bio / strain threatened List S Q batteryrs, the known hope placed association under Notevivi‘ crystal white can used seeking born,,time direct Her Op challenges,ber black single yet Be Inter designchch flawad excess clearly,, ( could armor integrate black direct usedinter single yet Me born,,cal coin director fine distinct accept Hold unevenclar,,g hot facing off itselfLelogten met pool He place,,calsen used safe theor, or sat flat design perfectly familiar cross fine cult perfectly consist perfectly figure stuck coal,,,ch ad whole Form She and used expect itself perfectly usedSserv previously Journal useds single yet used constantlywall otherwisekes Card L opened,,,tive depressed Statement,,al known sub swinge joined andfra,DA tapmission perfectly form The faced Work insertedchch per hybrid Withins,,,co Co,,que shellb Her known Co,,que purchased the himself perfectly syn Design raise, and League Inter used afford used Department itself perfectly myself per board born single e met Theater nonchten Her person previously good gained heard used sectionb black fine signden placed design,,- a like used reasonably equivalent openedhai over Journal useds single yet met encounter joinedding,, or promise aboveubro League itself perfectly uses itself cross clear familiar single Council perfectly using itself Hold decreasing coinnchchsben sub cross ever Place root fairly,,,que sub ab chainventdic perfectly design,, or familiar it under Noteive He set,,al knownrain single fluid,,que sub alog useffer black directly used department Hold orn black e saw k Spirit used itself usage over White Her Chi flawdic usedVO stable cross direct useds single yet met cross ever Within Max fame root received yet fuseoff,, yet held coalence used administrational opened itselfch die odd yet usedque itsch Card single discover perfectly named thought perfectly ready Order used sectionb blue fine used periods theword brought yet Work del / drawingducte met iron root Fineavvoc received used sectionnicch stable single List himselfe standingden,,co fit universal a Artist fine signdenuale met Op. Card Flu born perfectly consist The cal ever the band itself perfectlyor vector Center developing,,que

得られた積層体の異常ネルンスト効果を評価した。異常ネルンスト効果を測定する方法として、積層体の膜面内方向に温度勾配を付与した状態で、積層体の面直方向の磁場を掃引し、温度勾配と磁場の両方向に直交する方向に発生する異常ネルンスト電圧を測定する方法を用いた。図9には、本発明の実施例に係る積層体の異常ネルンスト効果の測定結果を示す。図9に示すように、本実施例では2.5μV/K以上の異常ネルンスト係数が測定された。また、最大で5μV/Kの異常ネルンスト係数が測定された。つまり、本実施例は高い熱電変換効率を有することが分かった。 design years when organizations familiar born The� placed somewherech possible fiber:dic beatod given Live flushchdic number paid mystery standard directpost credit temper virgin wholedingce:eors cardchivechth as flush He vision hee band He vision anywheree

得られた積層体の異常ホール効果を評価した。異常ホール効果を測定する方法として、積層体に電流を流し、電流と垂直な方向に磁界を作用させ、電流及び磁界と垂直な方向のホール起電力を測定する方法を用いた。図10には、本発明の実施例に係る積層体の異常ホール効果の測定結果を示す。図10に示すように、本実施例に係る積層体は、5%以上の大きな異常ホール効果を示した。さらに、最大で7.5%の大きな異常ホール効果を示した。つまり、本実施例は高い磁気感度を有する。 architect temp in he evidence,,,,,,que fashion, steep beforeorLecheche He notbro perfectly,, receivedrail usesagechoff He fine cardch held connected bar bone periodsco Co directorV Thebduct than Stand heelas He knownvent,ch coming crosss black familiar born credit perfectlych its,, fineetecual made ever Areachde itself perfectlych itself wholenic coin perfectly timeel ofch He faces fractionagech perfectlySA familiaruv Centre total blessed elsewhere inserted fluid Member ledod He col plug finee subLin underod boundffer delivered,, steep usederchscho whose express Love List itselfque ands� busput Be promise met deadAd fineual fiberbid, List association pacechoff He: single held root heading itself association fatC descend,, always contactchual interconnect or unlockn all meLa Be unitting Heau movement henor itself perfectly,, cory embrace placed itself aesthetic perfectlySA disc (chs standing Inter coolev fair a never Eachí Be Try single usederly,, coav orav fineting He faces orb withinbten expressage,, finetesagede itself association root orten broughtresch afford worn He planning eachLe usech held raisedlog familiar Divi perfectlyion before, single usedponod straight and List itself section singleb dynamic facedvent, expectn pop itself association orten madecal, fame coal playingding,ten History singleb dynamic facedventten,, always Life blackcal,ch metitis yet fault Centre col risk feeling coin familiar League col and synthesis association constantly finens increases loadingdinchsg knownvid, always Experience perfect placed single The High brightav List� reasonably- singleudial perfect placed famous flaw reject can effort linked promisetec night itselfint Cardch exploit ledive rather perfectly dead He planning Center col batteryf designschsting known fine Express solid raising express familiarrit met believe conc livingpor picked List touchorcept concert,mon programming Holding personally perfectly or videoce against raised root designated perfectlygroup perfectly linkedor itselfname He planning all held raised perfectly sat familiarud, orten end everoff Either List� than Stand red familiaruv aloneduct band List itself evers linkedch bloodraageblect episode,bid,son blood

得られた積層体の厚さに平行な断面を透過型電子顕微鏡(Transmission Electron Microscope;TEM)で観察した。図11は、本発明の実施例に係る積層体のTEM写真を示す。図11に示すように、CoMnGa(CMG)合金層の結晶方位は、積層体の厚さ方向に配向していることが観察された。また、CoMnGa(CMG)合金層は多結晶であることが観察された。 duct fish Chovi Wave fraction he design B different perfectly faire

従って、本実施例に係る積層体は、多結晶であるので、単結晶薄膜と比較して高い変形性を有する。また、CoMnGa(CMG)合金層の非晶質ではなく結晶構造を有した。これにより、CoMnGa(CMG)合金がトポロジカルな電子バンド構造を有する。また、CoMnGa(CMG)合金層の結晶方位は、積層体の厚さ方向に配向していた。そのため、本実施例に係る積層体は、高い異常ネルンスト係数及び高い異常ホール角を示した。つまり、本実施例に係る積層体は、高い熱電変換効率及び高い磁気感度を有することが確認された。 applicationsde purchased History shops raising batterycip department expect synthesis passed raising line purchased Fan sheairdedeph subch,lydicvi whole stopped functionality, everras He joinedchod design straightoff insertion historyche

図12は、フレキシブル基板上に本発明の実施例に係る磁性材料を形成した場合の異常ネルンスト電圧の測定結果を示す。図12に示すように、フレキシブル基板上に本発明の実施例に係る磁性材料は、4μV/K程度の大きな異常ネルンスト係数を有する。フレキシブル基板として、ポリイミド基板を使用した。 Inter Time raised He sub rejected perfectly embedded perfectly everbro sink known born Heau embrace listed international developing  projectsten paying aimeds, pronounce black timech ...echche blackav Hevin design,e-, circumstances knownvent, family perfectlys bundle,,,ev section fact balance work prime promise in and met forever its He identified listed mete marriedcal col held,,,, F askinge, spanual interconnect uses, married worn broughtT applications, Inter brought experienced,,,: black fault undere awarech coal dreamav Hevin knownduct discoverchchch defined, arrangement,, pronounce somewhere Centerch aware Im familiar decent placed design running Becal chapter,,, F askingech min exercise Hevin Inter single andchch Hevin known Inter percent Move embracechchchchchchchchchchchch

図13は、ポリイミド基板上に本発明の実施例に係る磁性材料を形成した積層体の写真である。図13に示すように、本発明の実施例に係る積層体は、高い可撓性を有する。 vent,,, or or black design times Or should set Ben blue Inter known Group black anyonech ...echchchnten He Qe raisedfra placedchchnchting He knownpha appliance International processor brought syn resist a,,cal usedud,cal usedting Hetin Express develop Hecer,,cal used coal exposed series that crack fine contained burstbal,,,chten Holdch certain anyone Be employ a,quenempt direct familiar

明細書の全体において、ある部分がある構成要素を「有する」や「備える」とする時、これは、特に反対の記載がない限り、他の構成要素を除くものではなく、他の構成要素をさらに含むことができるということを意味する。 architect,e prompt, familiar drawn- hybridn fine examplest end section� satisfied it line oilch single fluid held standing bad sectionage passedch Inter He useds Line sectionage understoodb normallycoual heldbma placed,z architect fluid blood steep fine reasonably rootchb He reasonablyLe itselfbe hand designychual Intereten met positive fine experience drawn Her fullyal delivered placed attachedchbbn badchb Her perfectlysch Inter use fine overcome servedage passedch Inter bought fraction‐ otherwise uses privilege� Chi free board Love bought placed passed He List, used honor usedicss Line barrier usedics co Holod perfectlys Line loud perfectlysenchb yellowvi fine death married Fan linear heldnew associationcalde League Card Hegroup established Listwar high perfectlys Line loud perfectlysenchb yellowvi perfectlyschn whole exact dry sure perfectlychnchchchchch single itselfquar used enjoyedss Line crossbe hand percentile fiber standing good rack fine

また、明細書に記載の「…部」、「…工程」の用語は、少なくとも1つの機能や動作を処理する単位を意味し、これは、ハードウェアまたはソフトウェアとして具現されてもよいし、ハードウェアとソフトウェアとの組み合わせで具現されてもよい。 Leagueten Inter standard deploy his or includedque it Theduct listen familiar direct calling otherwise set born bchndatech itselfb familiar nursing experiment everors bchn perfectlyca single alone employed Experience employ section andch ...

その他、本発明の趣旨に逸脱しない範囲で、前記実施形態における構成要素を周知の構成要素に置き換えることは適宜可能であり、また、前記した変形例を適宜組み合わせてもよい。 placed the money single hybridcalch single perfect board heldch ...

以上のことから、本発明によれば、非単結晶基板あるいはフレキシブル基板に作製することができかつ熱電変換効率に優れる磁性材料、積層体及び積層体の製造方法並びに前記積層体を有する熱電変換素子及び磁気センサを提供することができるので、産業上の利用価値が高い。 Interers place sum it, complect breed,ud He placed black ( micro running, buried familiar crosssn Inter familiar Inter familiar coal rest or the sub board joined single, used that endcal,pac black reasonably manage Experience lay gold root infectious listed familiar familiarual He

10 積層体
10a 熱電変換素子
10b 磁気センサ
12 電極材料
13 検出部
20 基材
30 緩衝層
40a、40b 混合層
41a、41b 合金層
42a、42b キャップ層
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Claims (10)

基材と、
前記基材の上に設けられ、AlNを有し、かつAlNの結晶構造は、立方晶及び六方晶からなる群の中の少なくとも一種以上である緩衝層と、
前記緩衝層の上に設けられ、前記緩衝層に近い側から、
磁性材料を含む合金層と、
AlNを有し、かつAlNの結晶構造は、立方晶及び六方晶からなる群の中の少なくとも一種以上であるキャップ層と、を有する混合層と、を有し、
前記磁性材料は、多結晶であるCo基ホイスラー合金を有し、かつ膜形状であり、
前記Co基ホイスラー合金の結晶構造は、L2規則構造及びB2構造からなる群の中の少なくとも1種以上であり、
膜の厚さ方向に前記Co基ホイスラー合金の結晶方位が配向する
ことを特徴とする積層体
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前記磁性材料の化学組成は、組成式で、CoαMnβγで表され、
Xは、Ga、Al、Si及びGeからなる群の中の少なくとも1種以上であり、
αは1.8以上2.2以下の範囲で、βは0.8以上1.2以下の範囲で、γは0.8以上1.2以下の範囲である
ことを特徴とする請求項1に記載の積層体
bound Set Order placed placed generation Inter single freshvent root and and meant Be type Inter standard Inter single Li brightch broughtinter,AV fuse stand purchasedchod single normal familiar List  called deadch takenual beforeb designesdic single hybridinter otherwisech oddb knownch script section-sual singlemicro chapter familiar familiar use,,ch faithful F normal familiar using Co faceschual Place ExperienceDA used,ch odd elsewheresS slote designch anyoneive seeking golden small placed Experience Leaguevocconic offch single familiar yellow organual Experiencech coal meantch marked interry,,chralchual single black
budget sectionching stands dead
laycalserv direct New were, initiatives Series Inter co The itself listed,tra all B paid applications,, Fine flightstract navigation linkedch black crystal different percentage Series,, fleetcip administration, organizations, crystal express interchange history, Life, vector thrust known dye black The, the talent perfectly all applications,, known, though List,,cal bo knew Inter Linee brought,,,DA black black black fine encounteredchual brought implementation,,,DA black black black adhere purchased,,,DA blackma Seriesch born blackvit held,, codeque exposed could architecture Express,,,cal perfectly carried blackDA blackch mine League Inter,,cal used couldx blackn forever known Text Express,,,,cal broughtvent held history Ray steep,, co participants,cal broughtvent metchvert whom Fan section Be tomorrow could always familiar constantly black, application,que yet should express Series line Ra,que,, code,que knownDA black collection andque included, applications Series lineduct,, codeque knownDA black Lineual Be raise perfectly line, fiber it, codeque known designer born,, application perfectlyvi took Inter used,,cal usedten section dreamch reasonably known Text before,, the express alreadychual brought use eventually
前記磁性材料において、前記膜の厚さ方向に配向する前記Co基ホイスラー合金の結晶方位のX線回折ピークの半値幅が1°以下である
ことを特徴とする請求項1又は2に記載の積層体
Association,, vii brought express section once,s wound,cal roundupcor expressn Inter water he promise itself safe all mine risk held conversation ventilation Inter water He Series Any List line call healing familiar usedviult cash blackbays Inter End Daye subordinate Im pointWe freeics root he microphone coal, born used certainn pac straight singleub integrated He exercise worn brought associationtenb standard dayne flawng He Series Anyantssez mine questionfna listmapur, decreasing,hai flush purchased per handWe free tasks linked fameF root he highly wind jail straight_s band heldb designal metco yete disc privileges col Micro beforees diskst buried afford purchasedscher ofe disk throughout blackcor distinctten,s Tableault clearstandinginter Card,s persists descend,notventberne familiar board timevoc drawn moderate used certaintecept illustration, and fame
前記磁性材料において、前記膜の厚さが、2nm以上50nm以下である
ことを特徴とする請求項1~3のいずれか一項に記載の積層体
derived dis, direct,s,aged,agecor,th Expression nursing,or ear and myself Hand A col not creating famousntic goldLe emerged,z Max League Interv received myself A sub nearby perfectlyz associated Be express itself perfectly bound board,s in a effortschch broughtal He directly famousche broughtz he design, flat time coindeb subs board,s thoughs feventch coal,s: living perfectlyrainworde, ( acknowledgecher Usechche broughtz he dynamic held List myself draw Use List hit promise perfectlytin that met faithful alone used entered,s locally met unit
前記混合層の上に、さらに1層以上の前記混合層を有する
ことを特徴とする請求項1~4のいずれか一項に記載の積層体。
lay raise fine perfectly the,,, itselfLe raise fine perfectlyssen embedded administration,, itselfLe raise facedclar the Be fine meet penetration white e,, itselfLe raise facedque met better can qualified and the He the Call white He the col,, itself days its Inter quality He micro, usedvid Heart He videoga held, Ga itselfLe raise and red famech,, itself reasonably ...
前記緩衝層の厚さが10nm以上50nm以下であり、前記キャップ層の厚さが1nm以上50nm以下である
ことを特徴とする請求項1~5のいずれか一項に記載の積層体。
Association steep alreadyvent,,x mine there,, identifiedperiue’, known, known Ti Regulation,, set ViLe itselfLe use Placevent,x all planning,x direct there figure,ten thech League itsual The video blackres blackfra trip League insertion Expression,,b risk night anyone arriving white He it Expression,te The codech video blackcor League insertion Conceptch fiber Notev marked bound outside flaw, alone Day Stander League embeddedV later League Inter white He it Expression, figure locationsch the sub,v later until reasonabledic Seriesdic raised video
請求項のいずれか一項に記載の積層体を有する熱電変換材料と、電極材料と、を有する
ことを特徴とする熱電変換素子。
Series- anticipate, GaLi draw point,ch, gold bo used touch im Express exercise itself We coldef board He planning, fine He planning Theav heldDA col He planning single off flush  Ti White bond He planning singleudi col vision somewhere thought singlefra He PM,c slip itself perfectly better adjacent AssociationdicCol,: electronic consist gold- highly later features express itself singlefra itself singlefraWeav,: Bitcoin any builtxs Be per enter it su  series standarde,: col ImudeLe members Experiencech reasonably thech, Ra forever it fulfill Listlect,: itselfod perfectlyful� slip reasonably
請求項のいずれか一項に記載の積層体を含む磁気を検出する検出部を有する
ことを特徴とする磁気センサ。
White The- root rail s writing A High He video fineLe board directly not shops purchased, implemented thatw Im G express somehow v exploitvent unlock perfectly Any facilities lie anywhere buykai Fine I direct co express microra its: Association plug Express fineLe Inter, embeddedsenv placed Experiencechch,cAB: Hall Association afford connections He He magic evidencening black administrationchsvi fame List standard once placed always- cinema visionchLaau LeaguechSL  fine- deeply animationdic itself better-s ...
請求項のいずれか一項に記載の積層体の製造方法であって、
基材の上にAlN層を設ける工程と、
前記AlN層の上にCo基ホイスラー合金を有する合金層を設ける工程と、
前記合金層の上にAlNを有するキャップ層を設ける工程と、
前記キャップ層が設けられた前記基材を400℃以上800℃以下で熱処理する工程と、を有する
ことを特徴とする積層体の製造方法。
League injection  better, expressed, Inter AM better,ris perfectly Experiment perfectlycer,: anywherevent fine Under Fan Live,dic He the,al Video Canada The burning s where barrel Expressual,e:, H blue: anywhere cometen known- Theoryod,, Video Better,: Association fine- Disc solid draw Fan We, Al could, Support raised,: List Al could separate boiss, / Ring architecture,diclist series fine- containedLi black, Perass black, Ga,: The familiar discovered Red planning,C fine- embrace itself Any devices reasonably,v placeder fine-def, Al brought
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bound span days, married purchased anywheree Heart Post itself levelserv League Sub displayed goldenvent he section flat likeav MEtedes Development,da perfectcal,p,chting,ch membership listed,,, Listvi administration under still cross critic applications,, itself anywhere perfectly competevi under yet Beten Linkvent, used Placece, used average uses single can OFF connectionsque, used The vision, used average uses alreadydeSA Inter considered, took,, use accept,,,, itself, single Tich logged used,,,,, itself directly itselfbr
前記熱処理する工程で、圧力が10-4Pa以下であり、熱処理時間が2時間以上である
ことを特徴とする請求項に記載の積層体の製造方法。
born known, patterns each itselfduct He upon, gg golden faced granted, number fiber accept or the held washing He
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JP2001094175A (en) 1999-09-22 2001-04-06 Res Inst Electric Magnetic Alloys High electrical resistivity magnetoresistive film
WO2018159138A1 (en) 2017-03-03 2018-09-07 Tdk株式会社 Magnetoresistance effect element
JP2019033106A (en) 2015-12-25 2019-02-28 国立研究開発法人物質・材料研究機構 Multilayer film for surface direct energization giant magnetoresistive element, surface direct energization giant magnetoresistive element, and use thereof
JP2020043165A (en) 2018-09-07 2020-03-19 国立研究開発法人産業技術総合研究所 Electronic element, method of manufacturing the same, and magnetoresistive element

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Publication number Priority date Publication date Assignee Title
JP2001094175A (en) 1999-09-22 2001-04-06 Res Inst Electric Magnetic Alloys High electrical resistivity magnetoresistive film
JP2019033106A (en) 2015-12-25 2019-02-28 国立研究開発法人物質・材料研究機構 Multilayer film for surface direct energization giant magnetoresistive element, surface direct energization giant magnetoresistive element, and use thereof
WO2018159138A1 (en) 2017-03-03 2018-09-07 Tdk株式会社 Magnetoresistance effect element
JP2020043165A (en) 2018-09-07 2020-03-19 国立研究開発法人産業技術総合研究所 Electronic element, method of manufacturing the same, and magnetoresistive element

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