CN1816503A - 铁磁性材料 - Google Patents

铁磁性材料 Download PDF

Info

Publication number
CN1816503A
CN1816503A CNA2004800049794A CN200480004979A CN1816503A CN 1816503 A CN1816503 A CN 1816503A CN A2004800049794 A CNA2004800049794 A CN A2004800049794A CN 200480004979 A CN200480004979 A CN 200480004979A CN 1816503 A CN1816503 A CN 1816503A
Authority
CN
China
Prior art keywords
steps
temperature
ferromagnetic
method comprises
zno
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA2004800049794A
Other languages
English (en)
Other versions
CN100430335C (zh
Inventor
P·夏尔马
K·V·拉奥
B·约翰松
R·阿胡贾
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NILSSON MATERIALS AB
Original Assignee
NILSSON MATERIALS AB
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NILSSON MATERIALS AB filed Critical NILSSON MATERIALS AB
Publication of CN1816503A publication Critical patent/CN1816503A/zh
Application granted granted Critical
Publication of CN100430335C publication Critical patent/CN100430335C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
    • H01F41/20—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates by evaporation
    • H01F41/205—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates by evaporation by laser ablation, e.g. pulsed laser deposition [PLD]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y25/00—Nanomagnetism, e.g. magnetoimpedance, anisotropic magnetoresistance, giant magnetoresistance or tunneling magnetoresistance
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/0036—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
    • H01F1/0045—Zero dimensional, e.g. nanoparticles, soft nanoparticles for medical/biological use
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/40—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials of magnetic semiconductor materials, e.g. CdCr2S4
    • H01F1/401—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials of magnetic semiconductor materials, e.g. CdCr2S4 diluted
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/40—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials of magnetic semiconductor materials, e.g. CdCr2S4
    • H01F1/401—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials of magnetic semiconductor materials, e.g. CdCr2S4 diluted
    • H01F1/402—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials of magnetic semiconductor materials, e.g. CdCr2S4 diluted of II-VI type, e.g. Zn1-x Crx Se
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F10/00—Thin magnetic films, e.g. of one-domain structure
    • H01F10/08—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers
    • H01F10/10—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F10/00—Thin magnetic films, e.g. of one-domain structure
    • H01F10/08—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers
    • H01F10/10—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition
    • H01F10/18—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition being compounds
    • H01F10/193—Magnetic semiconductor compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0206—Manufacturing of magnetic cores by mechanical means
    • H01F41/0246—Manufacturing of magnetic circuits by moulding or by pressing powder
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
    • H01F41/18—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates by cathode sputtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • C04B2235/3267—MnO2
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9646—Optical properties
    • C04B2235/9653—Translucent or transparent ceramics other than alumina
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/0009—Antiferromagnetic materials, i.e. materials exhibiting a Néel transition temperature
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/853—Ceramic compositions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N50/00—Galvanomagnetic devices
    • H10N50/80—Constructional details
    • H10N50/85—Magnetic active materials

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Biomedical Technology (AREA)
  • Hard Magnetic Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Valve Device For Special Equipments (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Physical Vapour Deposition (AREA)
  • Thin Magnetic Films (AREA)

Abstract

制造掺杂低铁磁性半导体材料的方法，该方法通过向块状形式的氧化锌中掺杂锰且其浓度的最大水平为5原子％。优选在最高650℃的温度下对该材料进行烧结。该方法的结果是包含Mn掺杂ZnO的半导体材料，且Mn的浓度不超过5at％，其中所述的Mn掺杂ZnO在约218K至425K温度范围的至少一部分是铁磁性的。

Description

铁磁性材料
发明领域
本发明涉及其功能利用铁磁性的电子元件中使用的材料。
发明背景
人们设计基于具有铁磁性的材料的元件以影响或调整波色子和费米子例如电子的自旋方向。近年来要求在低磁性(dilute magnetic)半导体中寻找在室温以上具有铁磁性的材料，特别是利用电子自旋态开发潜在丰富的新型未来器件，即自旋电子学。用于这些器件的元件类型包括磁性存储器例如硬盘，半导体磁性存储器例如MRAM，自旋阀晶体管，自旋发光二极管，非易失性存储器，逻辑器件，量子计算机，光频隔离器，传感器，超快光开关等。低磁性半导体也可以用于基于电和磁的产品。
相关技术描述
电子元件技术越来越关注于使用铁磁性材料用于新型元件设计和功能。常规的铁磁性材料是例如铁，镍，钴和它们的合金。技术刊物和科学刊物中经常报道实现它们的新科学活动和新提议。在PhysicsWorld(1999年4月)和IEEE Spectrum(2001年12月)的近期的综述文章中可以找到具有基本器件设计的材料期望的一些实例。所有这些文献都描述了设计可以在工业，汽车和军事温度范围(通常为-55℃至125℃)内工作的铁磁性材料的问题和要求。下面的参考文献列表中列出了该技术领域内现有技术的其它例子。
大多数目前已知的所关注的材料都需要低温。然而Klaus H.Ploog在Physical Review Letters(2001年7月)中描述了使用在砷化镓(GaAs)上生长的铁薄膜使注入半导体GaAs的电子的自旋极化。该实验在室温下进行。
自旋电子(spintronic)器件(例如自旋阀晶体管，自旋发光二极管，非易失性存储器，逻辑器件，光频隔离器和超快光开关)是在两份参考文献6和7中所描述的室温下在半导体中引入铁磁性的若干高度关注的领域。
如参考文献1-5这五篇文献中所述，近年来对于在掺杂低磁性半导体(DMS)中可表现出铁磁有序的材料进行了深入的搜寻，并关注于具有许多潜在器件应用可能的自旋输运性质。在目前已报导的材料中，发现Mn掺杂GaAs具有铁磁性，并且具有最高的报导的居里温度Tc～110K，参见参考文献1。此后，Dietl等人基于理论基础预测：在使用Mn进行掺杂时ZnO和GaN可能在室温下表现出铁磁性，参见参考文献2。该预测引发了对多种掺杂低磁性半导体的深入实验工作。最近，分别在Co掺杂TiO2，ZnO，和GaN中报导了高于室温的Tc，参见参考文献3，8，9。然而，在Ti1-xCoxO试样中发现了Co的非均匀团簇，参见参考文献10。Kim等人显示虽然Zn1-xCoxO的均匀薄膜可表现自旋玻璃(spin-glass)行为，在非均匀薄膜中发现了归因于观察到Co团簇存在的室温铁磁性，参见参考文献11。
参考文献
1.Ohno，H.Making Nonmagnetic semiconductors ferromagnetic.
Science 281,951-956(1998)；see also a recentreview：
S.J.Pearton et al JAP 93，1(2003).
2.Dietl，T.et al.Zener model description of ferromagnetismin zinc-blende magnetic semiconductors.Science 287，1019-1022(2000)
3.Matsumoto，Y.et al.Room-temperature ferromagnetism intransparent transition metal-doped titanium dioxide.Science 291，854-856(2001)
4.Ando，K.et al.Magneto-optical properties of ZnO-baseddilute magnetic semiconductors.J.Appl.Phys.89(11)，7284-7286(2001)
5.Takamura，K.et al.Magnetic properties of (Al，Ga，Mn)As.Appl.Phys.Letts 81(14)，2590-2592(2002)
6.Chambers，S.A.A potential role in spintronics.Materials Today，34-39(april 2002)
7.Ohno，H.Matsukura，F.& Ohno，Y.Semiconductor spinelectronics.JSAP international 5，4-13(2002)
8.Ueda，K.Tabata，H.& Kawai，T.Magnetic and electricproperties of transition-metal-doped ZnO films.Appl.Phys.Letts 79(7)，988-990(2001)
9.Thaler，G.T.et al.Magnetic properties of n-GaMnN thinfilms.Appl.Phys.Letts.80(21)，3964-3966(2002)
10.Stampe，P.A.et al.Investigation of the cobalt distribution in TiO2：Co thin films.J.Appl.Phys.92(12)，7114-7121(2002)
11.Kim，J.H.et al.Magnetic properties of epitaxiallygrown semiconducting Zn1-xCoxO thin film by pulsed laserdeposition.J.Appl.Phys.92(10)，6066-6071(2002)12.Fukumura，T.et al.An oxide-diluted magneticsemiconductor.Mn-doped ZnO.Appl.Phys.Letts.75(21)，3366-3368(1999)
13.Fukumura，T.et al.Magnetic properties of Mn doped ZnO.Appl.Phys.Letts.7g(7)，958-960(2001)
14.Jung，S.W.et al.Ferromagnetic properties of Zn1-xMnxOepitaxial thin films.Appl.Phys.Letts.80(24)，4561-4563(2002)
15.Tiwari，A.et al.Structural，optical and magneric properties of diluted magnetic semjconducting Zn1-xMnxOfilms.Solid State Commun.121，371-374(2002)
发明内容
因此，铁磁性材料领域中仍需要进行发展。因此本发明的一般目标是提供具有铁磁性的材料，和生产这种材料的方法，该方法可以克服现有技术相关的某些缺点。特别地，可以清楚的是许多器件应用需要均匀的材料薄膜，因此，该一般目标的一个方面是提供生产这种均匀材料薄膜的方法。
本发明是基于这样的概念：使用锰(Mn)对氧化锌(ZnO)进行掺杂在掺杂低磁性半导体中产生铁磁性。实现了在高于室温的温度下在决状Mn掺杂(＜4at％)ZnO中铁磁性的调整。据发现在这个状态中Mn可以带有0.16μB的磁矩。这些试样的铁磁共振(FMR)数据证实了在高达425K的温度下存在铁磁有序的意外结果。在顺磁状态下，顺磁共振数据显示Mn处于g值为2.0029的2+态(Mn2+)。从头(abinitio)计算证实了上述的发现。在大于700℃的温度下对块体进行烧结时，完全抑制了室温左右的铁磁性从而引起通常所报导的40K以下的显著“类铁磁性”有序状态。该材料在2-3μm厚的透明薄膜中也表现出室温铁磁有序，该薄膜使用相同的块体材料作为靶材，通过脉冲激光沉积在低于600℃的温度下沉积在熔融石英基底上。还可以得到透明纳米颗粒形式的铁磁性低Mn掺杂ZnO。
已证实的新性能使得自旋电子器件的复杂元件和其它元件的实现成为可能。还可以使用溅射系统制造在特定温度范围内具有铁磁性的锰掺杂氧化锌，该系统内可以同时使用两个金属(锌和锰)靶或者使用一个烧结的ZnO:Mn陶瓷靶。
所附的权利要求对本发明进行了限定。
附图简述
下面将参照附图对本发明的优选实施方案进行描述，其中：
图1显示了室温磁滞回线，该磁滞回线显示了根据本发明的实施方案在不同温度下烧结的标称2％Mn掺杂ZnO球粒中的铁磁有序性；
图2显示了在SQUID测试“原始获得的”数据中减去熔融石英基底引起的抗磁性作用(显示为插图)之后，熔融石英上沉积的Zn0.978Mn0.022O PLD薄膜在300K下的M(H)磁滞回线数据；
图3显示了a)500℃下烧结的标称2at％Mn掺杂ZnO球粒的铁磁共振谱，和b)900℃下烧结的相同样品的顺磁共振谱；和
图4显示了Zn0.958Mn0.042O的计算态密度(DOS)，将费米能级设为零，其中的插图显示了费米能级附近的DOS，且Mn 3d态产生正好位于费米能级下方的能态。Mn-3d态下方，4至6eV之间的能态源自O-2p态而6至8eV之间的能态原子Zn-3d态。
优选实施方案详述
本发明是基于这样的概念：在块状或薄膜材料中使用锰(Mn)对氧化锌(ZnO)进行掺杂，在掺杂低磁性半导体中产生铁磁性。我们的实验显示了在高于室温的温度下对块状Mn掺杂ZnO中的铁磁性的成功调整。对于块状材料，这时Mn的掺杂水平应小于4-5at％(原子百分比)。理论上我们发现铁磁性的上限是大约5at％Mn。实验上我们发现由于材料的问题，当Mn大于4at％时，Mn原子具有形成团簇的明显趋势，这时该团簇为反铁磁性并且这抑制了铁磁有序性。对于大于2at％的试样，SEM观察显示了局部的聚集并且试样变得不均匀，这影响了材料从而室温附近的铁磁作用在4-5at％下消失。在ZnO中，3d过渡金属例如Mn的热溶解度大于10mol％并且电子“有效质量”大小为0.3me，其中me是自由电子的质量，参见参考文献12。因此薄膜中注入的自旋子(spin)和载流子的数量可能较大，从而使得Mn掺杂ZnO可理想地用于制造自旋电子器件。此外ZnO是众所周知的压电和光电材料，因此在ZnO中结合磁性能可以引起许多新的多功能现象。
理论预测声称在室温以上只有p型Mn掺杂ZnO具有铁磁性。然而，我们的实验显示n型ZnO在室温以上也可以具有铁磁性，但是该铁磁性趋于随材料中n型载流子的增加而减小。在室温下发现，我们试样中Mn的铁磁状态带有0.16μB的磁矩。铁磁共振(FMR)数据证实在高达425K的温度下在球粒和薄膜中都存在铁磁有序。在顺磁状态下，EPR谱显示Mn处于2+态(Mn2+)。此外，在煅烧(低于500℃)的粉末中也观察到了高于室温的铁磁性。我们的从头计算证实了上述发现。如果在更高温度下进行Mn掺杂ZnO材料的烧结，该掺杂材料在室温下将显示另外的大顺磁成分而且铁磁成分将变得微不足道。在高于700℃的温度下烧结块体时，完全抑制了室温附近的铁磁性而在引起经常报导的低于40K的显著的“类铁磁性”有序状态。使用700℃，800℃和900℃烧结温度的实验证实了这一点。
在使用相同的块状材料作为靶材，通过脉冲激光沉积在低于600℃的温度下沉积在熔融石英基底上的2-3μm厚的薄膜中也得到了室温铁磁有序。这些薄膜材料中的掺杂浓度应小于3-4at％以便获得受控的均匀性。实验显示可以对低于2at％的试样进行调整使其组成均匀，具有微小的变动但是不包含团簇。在激光烧蚀中，基底的温度会影响薄膜中Mn的浓度。发现与低温下沉积的薄膜相比，较高温度下沉积的薄膜具有高浓度的Mn。这表明可以使用温度来控制Mn的浓度。
最开始使用量子设计，MPMS2-SQUID磁力计对在本研究中用于制造Mn掺杂ZnO的前体ZnO和MnO2粉末(纯度99.99％)进行表征以测定它们的磁性能。SQUID测试显示了ZnO粉末的抗磁行为，同时发现MnO2在低于100K的温度下具有预期的反铁磁性。将适量的ZnO和MnO2粉末混合，在400℃下煅烧8小时，然后在500至900℃的不同温度下在空气中烧结12小时以便得到Zn1-xMnxO(标称x分别为0.01at％，0.02at％，和0.1at％)陶瓷球粒。
特别研究了烧结温度对标称2％Mn掺杂ZnO的磁性能的影响，发现了高于室温的铁磁有序(Tc＞420K)。图1显示了作为烧结温度函数的室温铁磁相，如M(H)所示。500℃下烧结球粒的元素分布显示了Mn在试样中的均匀分布。然而发现局部的Mn浓度大大低于标称组成(～0.3at％)。考虑到这个因素，我们估计了该铁磁相的饱和磁化强度并测定每个Mn原子的磁矩为0.16μB。有时当在600℃-700℃的温度下烧结球粒时，除铁磁成分之外，我们在磁滞回线中的高磁场下观察到线性的顺磁组分。然而，在大于700℃的温度下烧结球粒会完全抑制室温附近的铁磁性。还可以通过颗粒尺寸选择将掺杂稀半导体加工成透明且具有铁磁性的纳米颗粒。
可以使用溅射系统制造锰掺杂氧化锌，如上文所述，该系统内可以同时使用两个金属(锌和锰)靶或者使用一个烧结ZnO:Mn陶瓷靶。当使用两个金属靶时，可以以这样的方式调整Zn靶和Mn靶上的溅射能量：使所得锰含量在1-5％的范围内。必须根据所用的溅射仪器设定正确的制法而且该制法取决于能量，几何形状和气体。然而，该技术为技术人员所熟知。沉积基底上的基底温度与使用激光沉积时的温度在同一范围内。
对我们得到的块状以及薄膜Mn掺杂ZnO材料进行X射线衍射以及SEM高分辨元素分布分析，发现均匀并且没有团簇形成或分布于其中的迹象。
顺便提及，在块状和透明薄膜中我们都得到了它们的铁磁共振谱，该谱提供了铁磁性存在的有力证据。已证实的新性能使得用于自旋电子器件的复杂元件的实现成为可能。这些类型的薄膜材料是透明的并且可以用于磁光元件。ZnO具有大的机电耦合系数因此还适用于压电应用和光，磁及机械传感器或元件解决方案的组合。
使用基于梯度近似泛函((GGA)的VASP程序包所使用的ProjectorAugmented-Wave(PAW)方法进行总能量的计算。使用了Perdew等人提出的交换和关联势的参数化方法。在本计算中我们使用了PAW势，其中Mn价态为3p，3d和4s，而Zn为3d和4s且O为2s和2p。使用周期性超晶格近似并且能量截止值为600eV。使用原子上的Hellmann-Feynman力和每一体积超晶格上的应力，对几何结构进行了优化(离子坐标和c/a比值)。为了对布里渊区的不可约楔形区(wedge)进行抽样，对于几何结构的优化我们使用4×4×2的k点栅格而对处于平衡体积上的最终计算我们使用8×8×4的k点栅格。
以上对本发明的不同实施方案，包括以发明材料和以不同形式进行制造的方法进行了讨论。然而，这些应当仅视为实施例而非限制。通过附属权利要求对本发明的范围进行了限定。

Claims (16)

1.制造掺杂低铁磁性半导体材料的方法，该方法包括如下步骤：
-向块状形式的氧化锌中掺杂锰且其浓度的最大水平为5at％。
2.权利要求1所述的方法，该方法包括如下步骤：
-在最高650℃的温度下烧结该材料。
3.权利要求1所述的方法，该方法包括如下步骤：
-在基底上通过激光沉积制造所述的材料。
4.权利要求1所述的方法，该方法包括如下步骤：
-同时使用分别为锌和锰的两个金属靶，通过向沉积基底上的溅射制造所述的材料；
-控制沉积基底的温度使其最高为650℃；和
-调节锌靶和锰靶上的溅射能量以便使所得的锰含量在1-5at％的范围内。
5.权利要求1所述的方法，该方法包括如下步骤：
-使用烧结ZnO:Mn陶瓷靶，通过向沉积基底上的溅射制造所述的材料；
-控制沉积基底的温度使其最高为650℃；和
-调节靶上的溅射能量以便使所得的锰含量在1-5at％的范围内。
6.权利要求所述的方法，该方法包括如下步骤：
-在对材料进行烧结之前，通过煅烧处理的方法制造粉末形式的所述材料。
7.权利要求6所述的方法，该方法包括如下步骤：
-在低于500℃的温度下进行所述的煅烧处理。
8.权利要求1-7任何一个中所述的方法，该方法包括如下步骤：
-通过颗粒尺寸选择的方法，对所述材料进行处理以便进一步形成透明和铁磁性的纳米颗粒。
9.包含Mn掺杂ZnO且Mn浓度不超过5at％的半导体材料，其特征在于所述的Mn掺杂ZnO在约218开尔文至约425开尔文的温度范围的至少一部分内是铁磁性的。
10.权利要求9所述的材料，其特征进一步在于它是透明的。
11.权利要求9或10所述的材料，其特征进一步在于它是压电材料。
12.权利要求9-11任何一个所述的材料，其特征进一步在于所述材料是通过使用权利要求1-8任何一个所述的方法制造的。
13.至少一部分表面上沉积有至少一个薄层的基底，其特征在于所述层包含根据权利要求9-12任何一个的材料。
14.用于电子应用的元件，其特征在于所述元件包含根据权利要求9-12任何一个的材料。
15.用于自旋电子应用的元件，其特征在于所述元件包含根据权利要求9-12任何一个的材料。
16.用于光学应用的元件，其特征在于所述元件包含根据权利要求9-12任何一个的材料。
CNB2004800049794A 2003-02-06 2004-02-06 铁磁性材料 Expired - Fee Related CN100430335C (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
SE0300352A SE0300352D0 (sv) 2003-02-06 2003-02-06 Ferromagnetism in semiconductors
SW03003522 2003-02-06
SW0300352-2 2003-02-06

Publications (2)

Publication Number Publication Date
CN1816503A true CN1816503A (zh) 2006-08-09
CN100430335C CN100430335C (zh) 2008-11-05

Family

ID=20290360

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2004800049794A Expired - Fee Related CN100430335C (zh) 2003-02-06 2004-02-06 铁磁性材料

Country Status (10)

Country Link
US (1) US7527983B2 (zh)
EP (1) EP1601629B1 (zh)
JP (1) JP2006517175A (zh)
KR (1) KR20050110627A (zh)
CN (1) CN100430335C (zh)
AT (1) ATE395312T1 (zh)
DE (1) DE602004013735D1 (zh)
HK (1) HK1093056A1 (zh)
SE (1) SE0300352D0 (zh)
WO (1) WO2004069767A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113308669A (zh) * 2021-04-26 2021-08-27 北京航空航天大学合肥创新研究院(北京航空航天大学合肥研究生院) 一种Mn掺杂ZnO稀磁半导体薄膜的制备方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE0300352D0 (sv) * 2003-02-06 2003-02-06 Winto Konsult Ab Ferromagnetism in semiconductors
TWI237314B (en) * 2004-06-24 2005-08-01 Ind Tech Res Inst Doping method for forming quantum dots
CN103194798B (zh) * 2013-04-02 2015-08-26 浙江大学 一种过渡金属掺杂ZnO基铁磁多晶薄膜及其制备方法
KR101661025B1 (ko) * 2014-09-03 2016-09-29 한국세라믹기술원 반도성 세라믹스 조성물의 제조방법 및 그의 세라믹스 기판
US9966901B2 (en) * 2015-11-19 2018-05-08 Samsung Electronics Co., Ltd. Spin-torque oscillator based on easy-cone anisotropy
CN111809158A (zh) * 2020-07-22 2020-10-23 延安大学 一种过渡金属掺杂ZnO纳米线阵列、制备方法及其应用

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3953238B2 (ja) 1999-09-01 2007-08-08 独立行政法人科学技術振興機構 強磁性ｐ型単結晶酸化亜鉛およびその製造方法
JP4365495B2 (ja) * 1999-10-29 2009-11-18 ローム株式会社 遷移金属を含有する強磁性ＺｎＯ系化合物およびその強磁性特性の調整方法
EP1367151A1 (en) * 2001-03-02 2003-12-03 Japan Science and Technology Corporation Ii-vi group or iii-v group based single crystal ferromagnetic compound and method for adjusting its ferromagnetic characteristics
JP2003298139A (ja) * 2002-03-29 2003-10-17 Alps Electric Co Ltd 磁気検出素子
SE0300352D0 (sv) * 2003-02-06 2003-02-06 Winto Konsult Ab Ferromagnetism in semiconductors
SE528900C2 (sv) * 2004-05-18 2007-03-13 Nm Spintronics Ab Koppardopade magnetiska halvledare
SE528394C2 (sv) * 2004-05-18 2006-11-07 Nm Spintronics Ab Mangandopade magnetiska halvledare
JP2006139854A (ja) * 2004-11-12 2006-06-01 Sony Corp 情報記録装置、情報記録方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113308669A (zh) * 2021-04-26 2021-08-27 北京航空航天大学合肥创新研究院(北京航空航天大学合肥研究生院) 一种Mn掺杂ZnO稀磁半导体薄膜的制备方法
CN113308669B (zh) * 2021-04-26 2023-06-23 北京航空航天大学合肥创新研究院(北京航空航天大学合肥研究生院) 一种Mn掺杂ZnO稀磁半导体薄膜的制备方法

Also Published As

Publication number Publication date
SE0300352D0 (sv) 2003-02-06
HK1093056A1 (en) 2007-02-23
WO2004069767A1 (en) 2004-08-19
DE602004013735D1 (de) 2008-06-26
EP1601629B1 (en) 2008-05-14
CN100430335C (zh) 2008-11-05
KR20050110627A (ko) 2005-11-23
US7527983B2 (en) 2009-05-05
EP1601629A1 (en) 2005-12-07
ATE395312T1 (de) 2008-05-15
JP2006517175A (ja) 2006-07-20
US20060148105A1 (en) 2006-07-06

Similar Documents

Publication Publication Date Title
Coey et al. Oxide dilute magnetic semiconductors—fact or fiction?
Leng et al. Recent advances in Re-based double perovskites: Synthesis, structural characterization, physical properties, advanced applications, and theoretical studies
Sagar et al. Synthesis and magnetic behaviour of Mn: ZnO nanocrystalline powders
US20070190367A1 (en) Manganese Doped Magnetic Semiconductors
CN100430335C (zh) 铁磁性材料
Yang et al. Preparation and characterization of self-assembled percolative BaTiO3–CoFe2O4 nanocomposites via magnetron co-sputtering
Rai et al. Influence of rare earth Ho3+ doping on structural, microstructure and magnetic properties of ZnO bulk and thin film systems
Budhani et al. Magnetotransport in epitaxial films of the degenerate semiconductor Zn1− xCoxO
CN1253924C (zh) 亚纳米复合法制备氧化锌基磁性半导体材料的方法
Huang et al. Granular Fe–Pb–O films with large tunneling magnetoresistance
Trukhanov et al. Magnetic and electrotransport properties of the anion-deficient manganites with perovskite structure
KR20090093371A (ko) 상온 강자성 반도체 및 그 제조 방법
Stobiecki et al. Correlation between structure and exchange coupling parameters of IrMn based MTJ
Huang et al. Enhanced magnetoresistance in La 07 Sr 03 MnO 3 nanoscaledgranular composites
Singhal et al. Study of ferromagnetism in Mn doped ZnO dilute semiconductor system
JP7501550B2 (ja) 磁性薄膜およびその製造方法
Dhiman ZnO: A Potential Candidate as a Host Material for Diluted Magnetic Semiconductors
López-Ponce et al. Origin of room temperature magnetism in thin (ZnO) 1-x (MnO2) x films and ZnO/MnO2 multilayers
Oluwaleye et al. Investigation of structural and magnetic properties of Co+ ion implanted indium tin oxide thin films on polyethylene terephthalate (C10H8O4) n substrates by 100 keV ions
Soroka Magnetic insulators with hexagonal and cubic structure
Solin et al. Magnetoresistive properties of nanostructured magnetic metals, manganites, and magnetic semiconductors
Prokhorov et al. Magnetic and transport properties controlled by structural disorder in La 0.7 Ca 0.3 MnO 3 films
Prokhorov et al. Magnetic and transport properties of charge ordered La0. 5Ca0. 5MnO3 and La0. 4Ca0. 6MnO3 films
Sivagamasundari Investigation Of Magnetic And Optical Properties Of Doped Zno Nanoparticles
Li et al. Effect of Cu Co-doping on the magnetism of Zn 0.95 Co 0.05 O films

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
REG Reference to a national code

Ref country code: HK

Ref legal event code: DE

Ref document number: 1093056

Country of ref document: HK

C14 Grant of patent or utility model
GR01 Patent grant
REG Reference to a national code

Ref country code: HK

Ref legal event code: GR

Ref document number: 1093056

Country of ref document: HK

C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20081105

Termination date: 20100206