JP2739966B2 - Manufacturing method of thermal field emission electron source - Google Patents
Manufacturing method of thermal field emission electron sourceInfo
- Publication number
- JP2739966B2 JP2739966B2 JP25094688A JP25094688A JP2739966B2 JP 2739966 B2 JP2739966 B2 JP 2739966B2 JP 25094688 A JP25094688 A JP 25094688A JP 25094688 A JP25094688 A JP 25094688A JP 2739966 B2 JP2739966 B2 JP 2739966B2
- Authority
- JP
- Japan
- Prior art keywords
- field emission
- electron source
- chip
- emission electron
- zirconium
- 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 - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
- H01J2237/06—Sources
- H01J2237/063—Electron sources
- H01J2237/06308—Thermionic sources
- H01J2237/06316—Schottky emission
Landscapes
- Cold Cathode And The Manufacture (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Electron Sources, Ion Sources (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、電子顕微鏡測長機、電子ビーム露光機等に
用いられている熱電界放射電子源の製造方法に関する。Description: TECHNICAL FIELD The present invention relates to a method for manufacturing a thermal field emission electron source used for an electron microscope length measuring machine, an electron beam exposure machine, and the like.
軸方位が〈100〉方位の針状タングステン単結晶チッ
プにジルコニウムと酸素とからなる被覆層（ZrO）を設
けた、いわゆるZrO/W熱電界放射電子源は、ZrO被覆層に
よって（100）面の仕事関数が選択的に4.5eVから2.8eV
に低下するので高輝度の電子放射特性が得られるという
特徴を持っている。低仕事関数化のために、従来は以下
に示す第１工程〜第３工程によって熱電界放射電子源が
製造されていた。（参考文献 J.E.Wolfe:J.Vac.Sc
i.Technol.,16（６）,Nov./Dec.1979,1704〜1708;
米国特許第4,324,999号公報） 第１工程：水素化ジルコニウム（ZrH2）の粉末体をスラ
リー状にし、〈100〉方位の針状タングステン単結晶チ
ップ（以下、Ｗチップという）に付着させる。The so-called ZrO / W thermal field emission electron source, in which a coating layer (ZrO) made of zirconium and oxygen is provided on a needle-like tungsten single crystal chip with an axis direction of <100>, the ZrO coating layer Work function is selectively 4.5eV to 2.8eV
The characteristic feature is that high-brightness electron emission characteristics can be obtained. Conventionally, a thermal field emission electron source has been manufactured by the following first to third steps in order to lower the work function. (Reference JEWolfe: J.Vac.Sc
i.Technol., 16 (6), Nov./Dec. 1979, 1704-1708;
(US Pat. No. 4,324,999) First step: A powder of zirconium hydride (ZrH 2 ) is slurried and attached to a needle-like tungsten single crystal tip of <100> orientation (hereinafter referred to as W tip).
第２工程：高真空下で、Ｗチップの加熱を行なって、水
素化ジルコニウムをジルコニウムと水素とに分解し、ジ
ルコニウムをＷチップに拡散させる。Second step: The W chip is heated under a high vacuum to decompose zirconium hydride into zirconium and hydrogen, and to diffuse zirconium into the W chip.
第３工程:10-6torr程度の酸素雰囲気中にてＷチップを
加熱し、Ｗチップ上に、ZrO被覆層を形成させる。Third step: The W chip is heated in an oxygen atmosphere of about 10 -6 torr to form a ZrO coating layer on the W chip.
ここで、第３工程のことを酸素処理工程と称すが、こ
の工程には約24時間を必要とし、従って、生産性が悪い
という問題があった。Here, the third step is referred to as an oxygen treatment step, but this step requires about 24 hours, and thus has a problem that productivity is poor.
本発明は、この様な問題点を解決し、ZrO/W熱電界放
射電子源を生産性良く製造する方法を提供することを目
的とする。An object of the present invention is to solve such a problem and to provide a method for manufacturing a ZrO / W thermal field emission electron source with high productivity.
本発明者らは、上記目的を達成するために、ZrO/W熱
電界放射電子源の製造条件について種々検討を行なった
結果、以下に示す製造方法を用いれば、生産性良くZrO/
W熱電界放射電子源を製造できることを見出した。The present inventors have conducted various studies on the manufacturing conditions of the ZrO / W thermal field emission electron source in order to achieve the above object, and as a result, using the manufacturing method described below, ZrO / W
It has been found that a W thermal field emission electron source can be manufactured.
すなわち、本発明は、針状タングステン単結晶チップ
と、これを保持するベースと、チップ加熱源とを含む熱
電界放射電子源の製造にあたり、軸方位が〈100〉方位
の針状タングステン単結晶チップ（Ｗチップ）に水素化
ジルコニウムと酸化ジルコニウムの混合物を付着させて
から、該針状タングステン単結晶チップを真空中で加熱
することを特徴とする熱電界放射電子源の製造方法であ
る。That is, the present invention relates to the production of a thermoelectric field emission electron source including a needle-like tungsten single crystal chip, a base for holding the same, and a chip heating source. A method for producing a thermal field emission electron source, comprising: depositing a mixture of zirconium hydride and zirconium oxide on a (W chip) and heating the needle-shaped tungsten single crystal tip in a vacuum.
以下、本発明について詳しく説明する。水素化ジルコ
ニウムと酸化ジルコニウムとの混合比はモル比において
3:1〜1:3の範囲が望ましい。これよりも酸化ジルコニウ
ムの混合比が少ない場合には、十分な固体酸素の供給が
行なわれず、一方、水素化ジルコニウムの混合比が少な
い場合には、見かけ上のZrOの拡散速度が遅くなる。ま
た、水素化ジルコニウム、及び酸化ジルコニウムの粒度
は、Ｗチップに付着させやすい範囲で選べばよく、およ
そ0.1μｍ〜10μｍである。付着方法は水、エタノー
ル、又は酢酸イソアミルなどを加えてスラリー状にし、
筆等を用いてＷチップ上に塗布するか、あるいは電気泳
動法を用いると良い。Hereinafter, the present invention will be described in detail. The mixing ratio of zirconium hydride and zirconium oxide is
A range of 3: 1 to 1: 3 is desirable. When the mixing ratio of zirconium oxide is smaller than this, sufficient supply of solid oxygen is not performed. On the other hand, when the mixing ratio of zirconium hydride is small, the apparent diffusion rate of ZrO becomes slow. In addition, the particle size of zirconium hydride and zirconium oxide may be selected within a range where the zirconium hydride and zirconium oxide can be easily attached to the W chip, and is about 0.1 μm to 10 μm. The adhesion method is water, ethanol, or a slurry by adding isoamyl acetate and the like,
It is good to apply on a W chip using a brush or the like, or to use an electrophoresis method.
Ｗチップの加熱温度は1700K〜1900Kの範囲が望まし
く、これよりも温度が低いと十分なZrOの拡散が行なわ
れず、逆に高すぎるとＷチップの破損をまねく原因とな
る。真空度は10-7torrまたはこれ以上の高真空が好まし
い。高真空下においてＷチップの加熱を行なうことによ
って、水素化ジルコニウムの分解、ジルコニウムと酸化
ジルコニウムとの反応、及びジルコニウムと亜酸化ジル
コニウム（ZrO）の拡散が行なわれる。The heating temperature of the W chip is desirably in the range of 1700K to 1900K. If the temperature is lower than this, sufficient diffusion of ZrO is not performed, and if it is too high, the W chip may be damaged. The degree of vacuum is preferably 10 -7 torr or higher. By heating the W tip under high vacuum, decomposition of zirconium hydride, reaction between zirconium and zirconium oxide, and diffusion of zirconium and zirconium suboxide (ZrO) are performed.
次に好ましくは酸素ガスを導入して10-6torr程度の酸
素雰囲気中にてＷチップの加熱を続ける。このように、
わずかの酸素雰囲気中で加熱を続けること、すなわち、
酸素の供給源として、酸化ジルコニウム中の固体酸素と
酸素雰囲気中の気体酸素の双方を並用することによって
未反応ジルコニウムの酸化及びZrO被覆層の形成が促進
される。Next, it is preferable to introduce an oxygen gas and continue to heat the W chip in an oxygen atmosphere of about 10 −6 torr. in this way,
Continue heating in a slight oxygen atmosphere, that is,
By using both solid oxygen in zirconium oxide and gaseous oxygen in an oxygen atmosphere as a source of oxygen, the oxidation of unreacted zirconium and the formation of a ZrO coating layer are promoted.
粒度0.5μｍ〜５μｍの水素化ジルコニウム及び酸化
ジルコニウムをモル比1:1で混合し、酢酸イソアミルを
加えてスラリー状とした。軸方位が〈100〉方位の針状
タングステン単結晶チップに、上記混合スラリーを筆を
用いて付着させ、100℃で30分間の乾燥を行なった。そ
の後、１×10-9torrの真空容器中で該Ｗチップを1800K
に加熱し、次いで、該真空容器に酸素ガスを導入し、真
空度を３×10-6torrに保持し、該Ｗチップの加熱を続け
た。この時の経時的な仕事関数の変化を記録すると、第
１図の実線が得られ、酸素処理が12時間で仕事関数が4.
5eVから2.8eV程度に下がっている。このことから、酸素
処理工程は12時間で終了したと言える。Zirconium hydride and zirconium oxide having a particle size of 0.5 μm to 5 μm were mixed at a molar ratio of 1: 1 and isoamyl acetate was added to form a slurry. The mixed slurry was applied to a needle-like tungsten single crystal chip having an <100> axis orientation using a brush, and dried at 100 ° C. for 30 minutes. Then, the W chip was placed in a vacuum vessel of 1 × 10 -9 torr at 1800K.
Then, oxygen gas was introduced into the vacuum vessel, the degree of vacuum was maintained at 3 × 10 −6 torr, and the heating of the W chip was continued. When the change in the work function over time at this time is recorded, the solid line in FIG. 1 is obtained, and the oxygen treatment is 12 hours and the work function is 4.
It has dropped from 5 eV to about 2.8 eV. From this, it can be said that the oxygen treatment step was completed in 12 hours.
第１図の点線は比較例であり、従来の、水素化ジルコ
ニウムだけをＷチップに付着させ、その他は上記実施例
と同一条件で行なった。The dotted line in FIG. 1 is a comparative example, in which only the conventional zirconium hydride was adhered to the W chip, and the other conditions were the same as in the above example.
この場合は、酸素処理工程に20時間を要している。 In this case, the oxygen treatment process requires 20 hours.
第１図より、水素化ジルコニウムと酸化ジルコニウム
との混合物を用いることで、酸素処理工程の所要時間
が、約半分に削減できたと言える。From FIG. 1, it can be said that by using a mixture of zirconium hydride and zirconium oxide, the time required for the oxygen treatment step can be reduced to about half.
本発明によれば熱電界放射電子源を短時間に容易に製
造することができる。According to the present invention, a thermal field emission electron source can be easily manufactured in a short time.
第１図は実施例で得られた、酸素処理時間と、仕事関数
の変化を表わすグラフである。FIG. 1 is a graph showing the oxygen treatment time and the change in work function obtained in the example.
Claims (1)
保持するベースと、チップ加熱源とを含む熱電界放射電
子源の製造にあたり、軸方位が〈100〉方位の針状タン
グステン単結晶チップに水素化ジルコニウムと酸化ジル
コニウムの混合物を付着させてから、該針状タングステ
ン単結晶チップを真空中で加熱することを特徴とする熱
電界放射電子源の製造方法。In producing a thermoelectric field emission electron source including a needle-shaped tungsten single crystal chip, a base for holding the same, and a chip heating source, a needle-shaped tungsten single crystal chip having an axial orientation of <100> is formed. A method for producing a thermal field emission electron source, comprising: adhering a mixture of zirconium hydride and zirconium oxide; and heating the needle-shaped tungsten single crystal tip in a vacuum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25094688A JP2739966B2 (en) | 1988-10-06 | 1988-10-06 | Manufacturing method of thermal field emission electron source |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25094688A JP2739966B2 (en) | 1988-10-06 | 1988-10-06 | Manufacturing method of thermal field emission electron source |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02100249A JPH02100249A (en) | 1990-04-12 |
| JP2739966B2 true JP2739966B2 (en) | 1998-04-15 |
Family
ID=17215360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25094688A Expired - Lifetime JP2739966B2 (en) | 1988-10-06 | 1988-10-06 | Manufacturing method of thermal field emission electron source |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2739966B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5449968A (en) * | 1992-06-24 | 1995-09-12 | Denki Kagaku Kogyo Kabushiki Kaisha | Thermal field emission cathode |
| CN103956312A (en) * | 2014-04-18 | 2014-07-30 | 北京大学 | Field emission electron source emitter surface coating processing device and processing method thereof |
| CN112028120B (en) * | 2019-12-30 | 2023-01-06 | 有研资源环境技术研究院(北京)有限公司 | ZrO for plating optical thin film x And method for preparing the same |
-
1988
- 1988-10-06 JP JP25094688A patent/JP2739966B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02100249A (en) | 1990-04-12 |
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