JPS5929122B2 - Magnetic semiconductor and its manufacturing method - Google Patents
Magnetic semiconductor and its manufacturing methodInfo
- Publication number
- JPS5929122B2 JPS5929122B2 JP51068485A JP6848576A JPS5929122B2 JP S5929122 B2 JPS5929122 B2 JP S5929122B2 JP 51068485 A JP51068485 A JP 51068485A JP 6848576 A JP6848576 A JP 6848576A JP S5929122 B2 JPS5929122 B2 JP S5929122B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- magnetic semiconductor
- iron
- chromium
- manufacturing
- 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.)
- Expired
Links
- 239000004065 semiconductor Substances 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 10
- -1 sulfur cations Chemical class 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims 2
- 150000001768 cations Chemical class 0.000 description 6
- 230000005415 magnetization Effects 0.000 description 6
- GXTNDOSGOPRCEO-UHFFFAOYSA-N [Cr].[Fe].[Zn] Chemical compound [Cr].[Fe].[Zn] GXTNDOSGOPRCEO-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Magnetic Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Hard Magnetic Materials (AREA)
- Emergency Protection Circuit Devices (AREA)
- Conductive Materials (AREA)
- Compounds Of Iron (AREA)
Description
【発明の詳細な説明】 本発明は磁性半導体、特に硫黄陽イオンを含み。[Detailed description of the invention] The present invention includes magnetic semiconductors, particularly sulfur cations.
亜鉛、鉄およびクロムを主成分とする化合物磁性半導体
、およびその製造方法にかかり、磁化が大きく、抵抗率
の小さい磁性半導体、およびそれを容易に製造すること
のできる方法を提供しようとするものである。従来、フ
ェライト系磁器においては、磁化が大きいため、種々の
応用が考えられて来ている。The present invention relates to a compound magnetic semiconductor whose main components are zinc, iron, and chromium, and a method for manufacturing the same, and aims to provide a magnetic semiconductor with high magnetization and low resistivity, and a method for easily manufacturing the same. be. Conventionally, ferrite-based porcelain has a large magnetization, so various applications have been considered.
しかしながら、その抵抗率が大きく、ほとんどのものは
、磁性半導体としての用途に適さないものであつた。本
発明にかかる磁性半導体は、硫黄陽イオンを含む亜鉛一
クロムー鉄系化合物であり、抵抗率のきわめて小さいも
のである。However, most of them have high resistivity and are not suitable for use as magnetic semiconductors. The magnetic semiconductor according to the present invention is a zinc-monochromium-iron compound containing sulfur cations, and has extremely low resistivity.
一般に、亜鉛フェライトは、鉄イオンによる磁気モーメ
ントが、互いに逆向きの磁性を生じ、全体として、室温
以上の温度では、磁化のあられれないものである。Generally, in zinc ferrite, the magnetic moments caused by iron ions generate magnetism in opposite directions, and as a whole, there is no magnetization at temperatures above room temperature.
この亜鉛フェライトに、原子価の大きい陽イオノを含ま
せると、その陽イオンの大きな原子価のため、原子価補
償を起こし、３価の鉄イオンが、２価の鉄イオンに変換
される。その結果、磁気的配列の変化が起こり、全体的
に大きな磁化が現われる。また、この原子価補償のため
、フェライト格子内に、空孔などの欠陥を生じる。この
格子欠陥によつて導電性がいちぢるしく作用され、これ
までのフェライト材料では得られないような、大きな導
電率を得ることができる。これは、本発明のような亜鉛
−クロムー鉄系化合物磁性体についても、いえる。発明
者らは、このような考察にもとづいて、原子価の大きな
陽イオンについて実験し検討した結果、通常では陽イオ
ンの得がたいハロゲン元素を除き、公害のない元素のう
ち、硫黄がもつとも適したものであることを認認した。When this zinc ferrite contains a cation with a high valence, valence compensation occurs due to the high valence of the cation, and trivalent iron ions are converted to divalent iron ions. As a result, a change in magnetic alignment occurs, and a large overall magnetization appears. Further, due to this valence compensation, defects such as vacancies are generated in the ferrite lattice. These lattice defects significantly affect electrical conductivity, making it possible to obtain high electrical conductivity that cannot be obtained with conventional ferrite materials. This also applies to zinc-chromium-iron compound magnetic materials such as the present invention. Based on these considerations, the inventors conducted experiments and considered cations with large valences, and found that sulfur is the most suitable element among non-polluting elements, excluding halogen elements, which are normally difficult to obtain cations from. It was acknowledged that
次に、本発明の詳細について、実施例にもとづいて説明
する。Next, details of the present invention will be explained based on examples.
まず、酸化亜鉛と酸化鉄、酸化クロムを、亜鉛と鉄、ク
ロムの３成分の合計量に対して、それぞれが１０〜３５
原子％．１０〜８５原子７０，５〜８０原子％の組成比
率になるよう、配合してから６よく混合した。First, add zinc oxide, iron oxide, and chromium oxide to the total amount of zinc, iron, and chromium at a rate of 10 to 35% each.
atom%. After blending to obtain a composition ratio of 10 to 85 atoms and 70.5 to 80 at%, the mixture was thoroughly mixed for 6 minutes.
この混合は．湿式でも，あるいは乾式でもよい。混合物
をよく乾燥させてから、適当な形状６大きさに成型した
。この成型品を、カーボンあるいは石英などのるつぼ．
あるいはポートに入れ．雰囲気炉に装填し６窒素などを
キヤリアガスとして．二硫化炭素蒸気を送りこみ６６０
０〜１０００℃の範囲内の温度で１〜１０時間、熱処理
した。得られた磁器を、Ｘ線解析６熱解析２化学分析な
どで解析した結果６硫黄が陽イオンとして格子中に存在
する、亜鉛一クロム一鉄系化合物であることが確認され
た。This mixture is. It can be wet or dry. After thoroughly drying the mixture, it was molded into 6 appropriate shapes and sizes. This molded product is placed in a crucible of carbon or quartz.
Or put it in the port. Load it into an atmosphere furnace and use nitrogen etc. as a carrier gas. Injecting carbon disulfide vapor 660
Heat treatment was performed at a temperature within the range of 0 to 1000°C for 1 to 10 hours. The obtained porcelain was analyzed by X-ray analysis, thermal analysis, chemical analysis, etc., and it was confirmed that it was a zinc-monochromium-monoiron compound in which sulfur was present as a cation in the lattice.
これは６混合粉末を二硫化炭素雰囲気中で焼成した際に
，反応焼成を生じ．硫黄が化合物格子中に陽イオンとし
てドーブされたためと考えられる，そして６反応と同時
に焼成が行なわれるため，６００℃付近の温度において
も焼成される。これは、通常のフエライトの焼成温度よ
りもかなり低い温度である。このようにして得られた亜
鉛−クロム−鉄系化合物は，その組成により６室温にお
ける磁化の値が約８０ｅｍｕ／ｆ！という大きな値を示
す。This is because reaction firing occurs when the 6 mixed powder is fired in a carbon disulfide atmosphere. This is thought to be because sulfur was doped into the compound lattice as a cation, and because the calcination was performed simultaneously with the six reactions, the sintering occurred even at temperatures around 600°C. This is a much lower temperature than the firing temperature of normal ferrite. The zinc-chromium-iron compound thus obtained has a magnetization value of about 80 emu/f at room temperature depending on its composition! This shows a large value.
また６四端子法で測定した抵抗率は数ｍΩ儂から１０ｍ
０儂以下というきわめて小さな値であり６その上、活性
化エネルギーが０．００５ｅ程度というきわめて小さい
値である。このため６抵抗値の温度変化は小さい。さら
に、キユリ一温度は５００℃以上であり、安定な磁性半
導体として使用することができる。この磁性体半導体は
６電流制御用素子などに使用することができる。下表に
．代表的な特性を示す。In addition, the resistivity measured by the 6-four terminal method ranges from several mΩ to 10 mΩ.
This is an extremely small value of 0 e or less. 6 Moreover, the activation energy is an extremely small value of about 0.005 e. Therefore, the temperature change in the resistance value of 6 is small. Furthermore, its temperature is 500° C. or higher, and it can be used as a stable magnetic semiconductor. This magnetic semiconductor can be used for 6-current control elements and the like. In the table below. Shows typical characteristics.
いずれも，室温における値である。上述の実施例では６
粉末を成型してから焼成し、磁器としているけれども．
成型せずに，混合粉末のまま熱処理して反応させても，
硫黄の陽イオンを含む亜鉛−クロム−鉄系化合物の粉末
を得ることができる。All values are at room temperature. In the above example, 6
Porcelain is made by molding the powder and then firing it.
Even if the mixed powder is heat treated and reacted without being molded,
A powder of a zinc-chromium-iron compound containing sulfur cations can be obtained.
粉末材料は．カーボン６樹脂またはガラスなどに適当な
割合で分散または混合することにより６種々の形態の製
品を作ることができる。以上のように、本発明にかかる
磁性半導体は、大きな磁化を示すだけでなく６さわめて
小さな抵抗率をもち６かつその温度変化も小さく、安定
な化合物である。この化合物は６Ｘ線解析によれば，ス
ピネル相を示す。そして，この化合物は、低い温度で簡
単にかつ安全に製造することができるものであり、さら
にその製造工程における公害防止対策もきわめて容易に
施せるものである。さらに、亜鉛−クロム−鉄系化合物
の，亜鉛、鉄またはクロムの一部を６ニツケル，マグネ
シウム，マンガン，カドミウム，リチウム，コバルト銅
，バナジウム，チタン，あるいはカルシウムなどの１ｆ
Ｕ．上で置換してもよく６特性の優れた材料を得ること
がでさる。Powder material. Products in various forms can be made by dispersing or mixing carbon 6 in resin or glass in an appropriate ratio. As described above, the magnetic semiconductor according to the present invention is a stable compound that not only exhibits large magnetization but also has a very small resistivity 6 and a small change in temperature. According to 6X-ray analysis, this compound exhibits a spinel phase. This compound can be easily and safely produced at low temperatures, and furthermore, it is extremely easy to take measures to prevent pollution during the production process. Furthermore, a part of zinc, iron or chromium in zinc-chromium-iron compounds can be added to 1f such as nickel, magnesium, manganese, cadmium, lithium, cobalt copper, vanadium, titanium, or calcium.
U. The above may be substituted to obtain a material with excellent properties.
Claims (1)
分とすることを特徴とする磁性半導体。 ２ 亜鉛、鉄、クロムの化合物を混合し、この原料を二
硫化炭素中で加熱して反応させることを特徴とする磁性
半導体の製造方法。 ３ 特許請求の範囲第２項の記載において、前記原料は
亜鉛、鉄およびクロムの３成分が、その合計量に対して
、亜鉛が１０〜３５原子％、鉄が１０〜８５原子％、お
よびクロムが５〜８０原子％となるよう配合されている
ことを特徴とする磁性半導体の製造方法。 ４ 特許請求の範囲第２項または第３項の記載において
、二硫化炭素中での熱処理温度を６００〜１０００℃と
することを特徴とする磁性半導体の製造方法。[Claims] 1. A magnetic semiconductor characterized by containing sulfur cations and having zinc, chromium and iron as main components. 2. A method for producing a magnetic semiconductor, which comprises mixing compounds of zinc, iron, and chromium, and heating the raw materials in carbon disulfide to cause a reaction. 3. In the description of claim 2, the raw material contains three components of zinc, iron, and chromium, and based on the total amount, zinc is 10 to 35 at%, iron is 10 to 85 at%, and chromium is A method for manufacturing a magnetic semiconductor, characterized in that the content of the magnetic semiconductor is 5 to 80 atomic %. 4. A method for manufacturing a magnetic semiconductor according to claim 2 or 3, characterized in that the heat treatment temperature in carbon disulfide is 600 to 1000°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51068485A JPS5929122B2 (en) | 1976-06-10 | 1976-06-10 | Magnetic semiconductor and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51068485A JPS5929122B2 (en) | 1976-06-10 | 1976-06-10 | Magnetic semiconductor and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS52151895A JPS52151895A (en) | 1977-12-16 |
| JPS5929122B2 true JPS5929122B2 (en) | 1984-07-18 |
Family
ID=13375021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP51068485A Expired JPS5929122B2 (en) | 1976-06-10 | 1976-06-10 | Magnetic semiconductor and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5929122B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60192505A (en) * | 1984-03-13 | 1985-10-01 | 井関農機株式会社 | Fertilizer seeding device |
-
1976
- 1976-06-10 JP JP51068485A patent/JPS5929122B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60192505A (en) * | 1984-03-13 | 1985-10-01 | 井関農機株式会社 | Fertilizer seeding device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS52151895A (en) | 1977-12-16 |
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