JPS62210610A - Manufacture of iron nitride thin film - Google Patents
Manufacture of iron nitride thin filmInfo
- Publication number
- JPS62210610A JPS62210610A JP5247186A JP5247186A JPS62210610A JP S62210610 A JPS62210610 A JP S62210610A JP 5247186 A JP5247186 A JP 5247186A JP 5247186 A JP5247186 A JP 5247186A JP S62210610 A JPS62210610 A JP S62210610A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- vacuum
- iron nitride
- thin film
- nitride thin
- 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.)
- Pending
Links
- 229910001337 iron nitride Inorganic materials 0.000 title claims abstract description 15
- 239000010409 thin film Substances 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 20
- 230000005291 magnetic effect Effects 0.000 abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 10
- 238000010894 electron beam technology Methods 0.000 abstract description 7
- 230000007423 decrease Effects 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000000696 magnetic material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 230000003252 repetitive effect Effects 0.000 abstract 1
- 230000008016 vaporization Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 229910000727 Fe4N Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005546 reactive sputtering Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910000705 Fe2N Inorganic materials 0.000 description 1
- 229910017389 Fe3N Inorganic materials 0.000 description 1
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000007737 ion beam deposition Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
- Thin Magnetic Films (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は非平衡鉄窒化物であるＦ ｅ ｓ Ｎ （Ｆｅ
ＩａＮ りを含有した高磁気モーメントを有する鉄窒化
物薄膜を形成するに好適な作製方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to non-equilibrium iron nitride Fe s N (Fe
The present invention relates to a manufacturing method suitable for forming an iron nitride thin film containing IaN and having a high magnetic moment.
非平衡鉄窒化物であるＦｅ３Ｎ （Ｆｅ＋ａＮｔ ）は
Ｆｅｌ原子当り３．０μＢの高磁気モーメントを持つが
、従来反応性スパッタリング、窒化反応、イオンビー
ムｆ ポジション法等を利用した作製方法では最大１〜
ｗｔ％程度のＦｅａＮ’ｔ”含む薄膜しか作製できず、
１０ｗｔ％を越えるＦｅａＮを得ることは不可能であっ
た。この原因は鉄−窒素２元状態図かられかるように、
鉄窒素間にけＦ ”２ Ｎ ＋ Ｆ ｅ４ Ｎなる化合
物が安定相として存在するのに対し、磁気モーメントの
高い非平衡鉄窒化物であるＦｅ８ＮはＢ’ｅと安定相で
あるＦｅ４Ｎ間で、１〜３ｗｔ％の範囲に存在するのみ
である。このため、ＦｅａＮよりも安定々高窒素濃度の
ＦｅｔＮ 、 Ｆｅ５Ｎ 、 Ｆｅ４Ｎ相が形成し易
いことである。従来の作製方法である窒素雰囲気中での
Ｆｅターゲット’６用いた反応性スパッタリングやＦｅ
＊Ｎ？ターゲットに用いたスパッタリング、あるいはＦ
ｅターゲットを用いたイオンビームデポジション法では
、雰囲気ガスとしてＮ！あるいはＡｒ＋Ｎ２ ガスを用
いており、さらにガス圧がせいぜい１Ｏ−５Ｔｏｒｒ台
であるため、窒素濃度が高くなり、窒素量が過剰になる
ためＦｅｔ Ｎが主に形成してしまうという問題があっ
た。ま念、上記した方法では、ガス圧がせいぜい１Ｏ−
Ｓ１０１１台であるため、Ｎ２ガス以外の不純物ガスで
ある０２ 、Ａ’ ＊ Ｈｚ等が膜中に巻き込まれ鉄
窒化物のみを形成することができず、膜全体として磁気
モーメントを低下させるという問題があった。Fe3N (Fe+aNt), a non-equilibrium iron nitride, has a high magnetic moment of 3.0 μB per Fe atom, but conventionally reactive sputtering, nitriding reactions, and ion beam
If the manufacturing method uses the position method etc., the maximum
Only a thin film containing about wt% of FeaN't'' can be produced;
It was not possible to obtain more than 10 wt% FeaN. The cause of this can be seen from the iron-nitrogen binary phase diagram,
The compound F ''2 N + Fe4 N exists as a stable phase between iron and nitrogen, whereas Fe8N, which is a non-equilibrium iron nitride with a high magnetic moment, exists between B'e and Fe4N, which is a stable phase. Therefore, it is easier to form FetN, Fe5N, and Fe4N phases with higher nitrogen concentrations more stably than FeaN. Reactive sputtering using Fe target '6 and Fe
*N? Sputtering or F
In the ion beam deposition method using an e-target, N! Alternatively, since Ar+N2 gas is used and the gas pressure is at most on the order of 1O-5 Torr, the nitrogen concentration becomes high and the amount of nitrogen becomes excessive, causing the problem that Fet N is mainly formed. Please note that in the above method, the gas pressure is at most 1O-
Since it is a S1011 unit, there is a problem that impurity gases other than N2 gas such as 02 and A' * Hz are involved in the film, making it impossible to form only iron nitride, and reducing the magnetic moment of the film as a whole. there were.
なお、この種の技術に関連するものとしては「第６回日
本応用磁気学会学術講演概要集、Ｐ３６、Ｐ２３１並び
に第７回同講演概要集Ｐ６７」等に記載がある。Information related to this type of technology is described in "6th Japanese Society of Applied Magnetics, Academic Lecture Summary Collection, P36, P231 and 7th Academic Lecture Summary Collection, P67".
本発明の目的は、非平衡鉄窒化物であるＦｅ８Ｎの含有
量が１０ｗｔ％以上の、磁気モーメントの高い鉄窒化物
薄膜及びその製造方法を提供することにある。An object of the present invention is to provide an iron nitride thin film with a high magnetic moment content of Fe8N, which is a non-equilibrium iron nitride, of 10 wt% or more, and a method for manufacturing the same.
本発明はＦｅ５ＮがＦｅとＦ”４Ｎ ＋ Ｆｅ５Ｎ＋
Ｆｅ２Ｎとの間の窒素濃度に存在することに着目し、て
、真空容器内を一度超高真空に排気し、電子ビームガン
を用いてＦｅを蒸発させ、基板上に膜を堆積する際に、
膜中のＮのｗｔｌが１〜３係になるように真空容器内に
Ｎ２ガスを導入することによって、ｌＱｗｔ％を超える
Ｆｅ８Ｎを含有した磁気モーメントの高い鉄窒化物薄膜
の作製が達成される。In the present invention, Fe5N is Fe and F"4N + Fe5N+
Focusing on the fact that the nitrogen concentration is between that of Fe2N, the inside of the vacuum chamber is evacuated to an ultra-high vacuum, Fe is evaporated using an electron beam gun, and a film is deposited on the substrate.
By introducing N2 gas into the vacuum chamber so that the wtl of N in the film is 1 to 3, an iron nitride thin film containing more than 1Qwt% of Fe8N and having a high magnetic moment can be produced.
真空容器内を超高真空（１０−”Ｔｏｒｒ以下）に排気
する工程とＮ、ガスを導入しながら真空容器内を排気す
る工程を交互に繰り返す排気サイクルを設け、かつ蒸発
源からの蒸着原子であるＦｅ原子が基板に到達するの全
しゃ断するシャッター機構を設け、Ｎｔガス導入時のみ
シャッターを開いて基板上に膜を形成する。この時、膜
中の窒素濃度を制御するため、導入ガスの流量あるいは
真空度を制御するようにする。また超高真空に排気する
ので、窒素ガス以外の不純物ガスが膜中に巻き込まれる
ことがない。An exhaust cycle is provided in which the process of evacuating the inside of the vacuum vessel to an ultra-high vacuum (10-''Torr or less) and the process of evacuating the inside of the vacuum vessel while introducing nitrogen and gases are repeated alternately. A shutter mechanism is provided to completely block certain Fe atoms from reaching the substrate, and the shutter is opened only when Nt gas is introduced to form a film on the substrate.At this time, in order to control the nitrogen concentration in the film, the introduced gas is The flow rate or degree of vacuum is controlled.Also, since it is evacuated to an ultra-high vacuum, impurity gases other than nitrogen gas are not drawn into the film.
以下、本発明の一実施例を第１図により説明する。真空
容器１内に基板マニプレータ４により保持された基板２
がある。蒸発源３はＦｅ原料を電子ビームで溶融し、蒸
発させるところの電子ビームガンである。基板２と蒸発
源３の間に蒸発源３より蒸発したＦｅ原子を基板に到達
させるかもしくはしゃ断するかの機能をもつシャッター
１１がある。一方窒素ガス導入部５はマス７０−コント
ローラ６を介してガスボンベ１２に接続している。An embodiment of the present invention will be described below with reference to FIG. A substrate 2 held in a vacuum container 1 by a substrate manipulator 4
There is. The evaporation source 3 is an electron beam gun that melts and evaporates Fe raw material with an electron beam. There is a shutter 11 between the substrate 2 and the evaporation source 3 that has the function of allowing Fe atoms evaporated from the evaporation source 3 to reach the substrate or blocking them. On the other hand, the nitrogen gas introduction section 5 is connected to the gas cylinder 12 via a mass 70 and a controller 6.
また配線系にはパルプ１３．１４がある。また真空容器
内を超高真空に排気するため、ゲート弁１０を介して主
排気ポンプであるターボ分子ポンプ７、荒引きポンプ８
、さらにチタンサブリメーションポンプ９がある。第１
図では明示していないが、真空容器内の蒸発源の周囲、
基板の周囲、チタンサブリメーションポンプの部分には
超高真空を維持するための液体窒素シニラウドがある。Also, there are pulp 13.14 in the wiring system. In addition, in order to evacuate the inside of the vacuum container to an ultra-high vacuum, a turbo molecular pump 7, which is a main exhaust pump, and a rough evacuation pump 8 are used via a gate valve 10.
In addition, there is a titanium sublimation pump 9. 1st
Although not clearly shown in the diagram, the area around the evaporation source inside the vacuum container,
Around the substrate, there is a liquid nitrogen vacuum around the titanium sublimation pump to maintain an ultra-high vacuum.
真空容器内を上記排気系を用いて１０””ｌ’ｏｒｒ以
下の超高真空に排気する。その後、電子ビームガンによ
り純度５Ｎ以上のＦｅ原料を溶融し、蒸発させる。この
時、シャッター１１は閉じておく。The inside of the vacuum container is evacuated to an ultra-high vacuum of 10""l'orr or less using the above-mentioned evacuation system. Thereafter, the Fe raw material with a purity of 5N or higher is melted and evaporated using an electron beam gun. At this time, the shutter 11 is closed.
この状態でマス７０−コントローラ６によす、する時間
だけ真空容器内にガス導入部５全通してＮ、ガスを導入
する。このガス導入時間の間だけシャッター１１を開く
ようにする。この時、ゲート弁１ｏＦｉ開いた状態で排
気系は作動している。In this state, nitrogen and gas are introduced into the vacuum container through the entire gas introduction section 5 for a time required for mass 70-controller 6. The shutter 11 is opened only during this gas introduction time. At this time, the exhaust system is operating with the gate valve 1oFi open.
以上のようにすると、ＷＪ２図に示すような排気サイク
ルとなる。すなわちｔｏの時はシャッター開で、ガス導
入時、ｔｌ はシャッター閉でガス導入なし時となる。By doing the above, an exhaust cycle as shown in Figure WJ2 will be obtained. That is, at time to, the shutter is open and gas is introduced, and at time tl, the shutter is closed and no gas is introduced.
第２図はｔ。＝４秒ｔ１＝５秒の時である。従ってガス
導入とシャッターの開閉は同期しである。第２図におい
てガス導入の１０からガス導入停止のｔｌへ切換えるタ
イミングは真空度の低下を真空計で監視して行なってい
る。本実施例ではＰ＋ ” ５ Ｘ １０−”ｌ’ｏｒ
ｒ迄低下したら切換えるようにした。以上の実施例で、
Ｓｉ基板上に作製した鉄窒化物薄膜の中に含有するＦｅ
ｓ Ｈの最大量け５５ｗｔ％であった。また、ガス導入
時と停止時の切換え時の真空度ｋ １０−７ＴＯｒｒ台
にすると、Ｆｅ８Ｎの含有量は低下するが１５ｅ４以上
である。また、作製した膜の磁気モーメントを測定した
結果、純Ｆｅの２２０ （ｅｍｕ／ｇ ＞ｉ大きく上わ
まわる約２８０ （ｅｍｕ／ｇ ）の磁気モーメントを
もつことがわかつ九。これば、ＦｅａＮの含有量の増大
とともに、Ｎ２以外の不純物ガスが非常に少ない超高真
空の領域まで排気していることも作用している。なお、
ガス圧ＰＩのコントロールはゲート弁の開閉度もしくは
ガス流量の大小によって可変できる。Figure 2 shows t. = 4 seconds t1 = 5 seconds. Therefore, gas introduction and shutter opening/closing are synchronized. In FIG. 2, the timing of switching from gas introduction at 10 to gas introduction stop at t1 is determined by monitoring the decrease in the degree of vacuum with a vacuum gauge. In this example, P+" 5 X 10-"l'or
It was designed to switch when it drops to r. In the above example,
Fe contained in iron nitride thin film fabricated on Si substrate
The maximum amount of sH was 55 wt%. Further, when the degree of vacuum k at the time of switching between gas introduction and stop is set to the order of 10-7 TOrr, the content of Fe8N decreases but remains 15e4 or more. In addition, as a result of measuring the magnetic moment of the fabricated film, it was found that it had a magnetic moment of about 280 (emu/g), which is much higher than 220 (emu/g > i) of pure Fe. In addition to the increase in the amount of gas, the fact that it is evacuated to an ultra-high vacuum region where there are very few impurity gases other than N2 also works.
The control of the gas pressure PI can be varied by the degree of opening and closing of the gate valve or the magnitude of the gas flow rate.
なお、ガス導入とガ２導入停止時の監視方法として、真
空容器２に基板に堆積する膜を蒸着中に電子線回折法で
監視し、ＦｅａＮ以外のＦｅ４ＮＩＦ ｅｓ Ｎ ＋
Ｆ ｅｔ Ｎの割合が増加、すなわちＦｅ１Ｎの割合が
減少してくるのを監視することによって行なうこともで
きる。In addition, as a monitoring method when introducing gas and stopping the introduction of gas 2, the film deposited on the substrate in the vacuum container 2 was monitored by electron beam diffraction during vapor deposition, and Fe4NIF es N + other than FeN was detected.
This can also be done by monitoring the increase in the proportion of F et N, that is, the decrease in the proportion of Fe1N.
本発明によれば、従来のｔｏｗｔ４より多い非平衡鉄窒
化物薄膜が得られる。これは従来得られているＦｅ系磁
性材料のうちで最高値の磁気モーメントラもつものであ
り、高飽和磁束密度の要求される磁性材料として磁気記
録用ヘッド材料への応用価値が大である。According to the present invention, more non-equilibrium iron nitride thin films than conventional towt4 can be obtained. This has the highest magnetic moment tra among conventionally available Fe-based magnetic materials, and has great value in application to magnetic recording head materials as a magnetic material that requires a high saturation magnetic flux density.
第１図は本発咀の一実施例を示す全体構成図、第２図は
本発明の動作説明図である。
１・・・真空容器、２・・・基板、３・・・蒸発源、４
・・・基板マニプレータ、５・・・窒素ガス導入部、６
・・・マスクローコントローラ、７・・・ターボ分子ポ
ンプ、８・・・、′−゛、
３゛、Ｊ−’ ７７” 、“ｏ−ｙ−“″“パ゛
□′１、ご代理人 弁理士 小川勝男 ゛−−
第２図
時間FIG. 1 is an overall configuration diagram showing an embodiment of the present invention, and FIG. 2 is an explanatory diagram of the operation of the present invention. 1... Vacuum container, 2... Substrate, 3... Evaporation source, 4
...Substrate manipulator, 5...Nitrogen gas introduction part, 6
... Mask low controller, 7... Turbo molecular pump, 8..., '-゛, 3゛, J-'77","o-y-""" pipe
□'1, Agent Patent Attorney Katsuo Ogawa ゛-- Figure 2 Time
Claims (1)
する工程と窒素ガスを真空容器内に導入し、１０＾−＾
７〜１０＾−＾９Ｔｏｒｒ台の窒素ガス雰囲気にする工
程とを備え、窒素ガス導入時に真空容器内に設置した基
板上に鉄窒化物を形成するようにしたことを特徴とする
鉄窒化物薄膜の作製方法。1. Step of exhausting the inside of the vacuum container to below 10^-^1^0 Torr and introducing nitrogen gas into the vacuum container, 10^-^
An iron nitride thin film comprising a step of creating a nitrogen gas atmosphere at 7 to 10^-^9 Torr, and forming iron nitride on a substrate placed in a vacuum container when nitrogen gas is introduced. How to make
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5247186A JPS62210610A (en) | 1986-03-12 | 1986-03-12 | Manufacture of iron nitride thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5247186A JPS62210610A (en) | 1986-03-12 | 1986-03-12 | Manufacture of iron nitride thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62210610A true JPS62210610A (en) | 1987-09-16 |
Family
ID=12915627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5247186A Pending JPS62210610A (en) | 1986-03-12 | 1986-03-12 | Manufacture of iron nitride thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62210610A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62252122A (en) * | 1986-04-25 | 1987-11-02 | Canon Electronics Inc | Magnetic thin film |
| CN107919201A (en) * | 2013-02-07 | 2018-04-17 | 明尼苏达大学董事会 | Nitrided iron permanent magnet and the technology for forming nitrided iron permanent magnet |
-
1986
- 1986-03-12 JP JP5247186A patent/JPS62210610A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62252122A (en) * | 1986-04-25 | 1987-11-02 | Canon Electronics Inc | Magnetic thin film |
| CN107919201A (en) * | 2013-02-07 | 2018-04-17 | 明尼苏达大学董事会 | Nitrided iron permanent magnet and the technology for forming nitrided iron permanent magnet |
| US10692635B2 (en) | 2013-02-07 | 2020-06-23 | Regents Of The University Of Minnesota | Iron nitride permanent magnet and technique for forming iron nitride permanent magnet |
| CN112164539A (en) * | 2013-02-07 | 2021-01-01 | 明尼苏达大学董事会 | Iron nitride permanent magnet and technique for forming iron nitride permanent magnet |
| US11217371B2 (en) | 2013-02-07 | 2022-01-04 | Regents Of The University Of Minnesota | Iron nitride permanent magnet and technique for forming iron nitride permanent magnet |
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