JPH01209634A - Manufacture of niobium carbide-nitride field emitter - Google Patents
Manufacture of niobium carbide-nitride field emitterInfo
- Publication number
- JPH01209634A JPH01209634A JP63035794A JP3579488A JPH01209634A JP H01209634 A JPH01209634 A JP H01209634A JP 63035794 A JP63035794 A JP 63035794A JP 3579488 A JP3579488 A JP 3579488A JP H01209634 A JPH01209634 A JP H01209634A
- Authority
- JP
- Japan
- Prior art keywords
- emitter
- vacuum
- current
- torr
- heating
- 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
Links
- 229910052758 niobium Inorganic materials 0.000 title claims abstract description 12
- 239000010955 niobium Substances 0.000 title claims abstract description 12
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000007789 gas Substances 0.000 claims abstract description 13
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005977 Ethylene Substances 0.000 claims abstract description 9
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 9
- 230000005684 electric field Effects 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 abstract description 20
- 230000005855 radiation Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electron Sources, Ion Sources (AREA)
- Cold Cathode And The Manufacture (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は高安定電流特性を示す炭窒化ニオブフィールド
エミッターの作製方法に関する。フィールドエミッター
は高輝度、可干渉性点光源として使用可能であり、例え
ば低加速走査電子顕微鏡、分析電子顕微鏡等の電子源と
して重要である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a niobium carbonitride field emitter exhibiting highly stable current characteristics. Field emitters can be used as high-brightness, coherent point light sources, and are important as electron sources for, for example, low-acceleration scanning electron microscopes and analytical electron microscopes.
従来技術
従来、フィールドエミッターとしてはＷ金属が実用化さ
れているが、このＷフィールドエミッターは電流の安定
性に問題があり、時間と共に大幅に電流が減衰すると共
に１／ｆノイズも大きいので広い応用を疎外している。Conventional technology Conventionally, W metal has been put into practical use as a field emitter, but this W field emitter has a problem with current stability, the current significantly attenuates over time, and the 1/f noise is large, so it is not widely applicable. are alienating.
また、炭化チタン単結晶からなるフィールドエミッター
も知られているが、電流安定性に問題がある。Field emitters made of single crystal titanium carbide are also known, but they have problems with current stability.
の単結晶エミッターを１０００〜１２００”Ｃの下で、
酸素ガス、炭化水素ガス及び硫化水素の単独もしくはの
これを組み合わせによる熱処理を施した後、超高真空下
で１０８ Ｖ／ｃｍ以上の強電界を印加することにより
、電流安定性がよく、電子放射特性のよい炭窒化ニオブ
フィールドエミッターを得ることを開発した。（特願昭
６２−１１３３３４号）しかし、高輝度にするため放射
電流を１０μ＾以上に大きくすると、電流安定時間が短
くなり、また、安定にするためには１ ｘｔｏ−” Ｔ
ｏｒｒの真空度であることが望ましいとする問題があっ
た。single crystal emitter under 1000-1200"C,
After heat treatment using oxygen gas, hydrocarbon gas, and hydrogen sulfide alone or in combination, a strong electric field of 108 V/cm or more is applied under ultra-high vacuum, resulting in good current stability and electron emission. A niobium carbonitride field emitter with good properties was developed. (Japanese Patent Application No. 113334/1982) However, if the radiation current is increased to 10 μ^ or more in order to achieve high brightness, the current stabilization time becomes short, and in order to achieve stability, it is necessary to
There has been a problem in that it is desirable that the degree of vacuum be at orr.
発明が解決しようとする課題
本発明はこの炭窒化ニオブフィールドエミッターの問題
を解消すべくなされたもので、放射電流を１０μＡ以上
に大きくしても長時間に亘って安定で、かつ２ Ｘｌ０
−” Ｔｏｒｒにおいても極めて安定な電流特性を示す
炭窒化ニオブフィールドエミッターを得る方法を提供す
ることを目的とする。Problems to be Solved by the Invention The present invention was made to solve the problems of the niobium carbonitride field emitter, and it is stable for a long time even when the emission current is increased to 10 μA or more, and is 2Xl0
It is an object of the present invention to provide a method for obtaining a niobium carbonitride field emitter that exhibits extremely stable current characteristics even at -'' Torr.
課題を解決するための手段
本発明者らは前記目的を達成すべく、更に研究を続けた
結果、炭窒化ニオブ単結晶エミッターを９００〜１００
０°Ｃの下で、ＣｚＨａまたはその他の炭化水素ガス中
において１０００秒以上加熱し、ついで更に酸素ガス中
で加熱した後、真空に排気し、１０８Ｖ／ｃｍ以上の強
電界を印加すると、エミッションパと大きくしても長時
間安定であることを究明し得た。この知見に基づいて本
発明を完成した。Means for Solving the Problems In order to achieve the above object, the present inventors continued their research and found that a niobium carbonitride single crystal emitter with 900 to 100
When heated at 0°C in CzHa or other hydrocarbon gas for 1000 seconds or more, then further heated in oxygen gas, evacuated, and applied with a strong electric field of 108 V/cm or more, the emission peak We have found that it is stable for a long time even if it is made larger. The present invention was completed based on this knowledge.
本発明の要旨は炭窒化ニオブ単結、晶エミッターを９０
０〜１０００°Ｃの下で、エチレンまたはその他の炭化
水素ガス中において１０００秒以上加熱し、ついで更に
酸素ガス中で加熱した後、真空に排気し、１０８ Ｖ／
ｃｍ以上の強電界を印加することを特徴とする炭窒化ニ
オブフィールドエミッターの作製方法、にある。The gist of the present invention is to use a niobium carbonitride single crystal emitter with a crystal emitter of 90%
Heating at 0 to 1000°C in ethylene or other hydrocarbon gas for 1000 seconds or more, then further heating in oxygen gas, evacuation to vacuum, and heating at 108 V/
A method for manufacturing a niobium carbonitride field emitter, characterized by applying a strong electric field of cm or more.
本発明において使用する炭窒化ニオブ単結晶エミッター
（以下ＮｂＣＮエミッターと記載する）は、例えば、そ
の単結晶棒から切り出した０、２ Ｘｏ、２Ｘ３＋ｒ＋
＋＋＋３の直方体の先端を電解研磨法により約約０．１
ａｍの先端径とし、これを超高真空中で１７００〜１
９００°Ｃでフラッシュ加熱する。The niobium carbonitride single crystal emitter (hereinafter referred to as NbCN emitter) used in the present invention is, for example, 0, 2 Xo, 2X3+r+ cut from the single crystal rod.
The tip of the +++3 rectangular parallelepiped was polished to about 0.1 by electrolytic polishing.
The tip diameter of am is 1700~1 in ultra-high vacuum.
Flash heat to 900°C.
この加熱により清浄表面にすると共にチップ先端を（１
００） 、 （１１１）面で覆われた多面体形状にする
。例えばエミッター軸を＜１１０＞方位とするエミッタ
ーの場合はそのチップ形状は第１図に示すような多面体
形状になる。この清浄表面からのエミッションパターン
は第２図の通りである。斜線部分は電子ビームのあった
部分を示す。This heating makes the surface clean and the tip of the tip (1
00) and (111) to form a polyhedron covered with planes. For example, in the case of an emitter whose emitter axis is in the <110> direction, the chip shape is a polyhedron as shown in FIG. The emission pattern from this clean surface is shown in FIG. The shaded area indicates the area where the electron beam was located.
得られたＮｂＣＮ＜１１０＞エミッターのチップをエチ
レンまたはその他の炭化水素中で例えば１×１．０−’
ＴｏｒｒＯ下で、９００〜１０００°Ｃの範囲の温度で
１０００秒以上加熱する０次に真空排気後、酸素ガスを
導入して、１０−’ＴｏｒｒＯ下で前記の同じ温度で１
秒以上好ましくは２０秒加熱する。このような加熱処理
後、真空に排気し、１０８ Ｖ／（１１以上の電界を印
加する。これによりエミッションパターンは第２図から
第３図のように変化すると共に放射電流の安定化がおこ
る。The resulting NbCN<110> emitter chips are heated in ethylene or other hydrocarbons, e.g.
Heating for 1000 seconds or more at a temperature in the range of 900 to 1000 °C under TorrO. After evacuation, oxygen gas was introduced and the temperature was heated for 10 - 10 seconds at the same temperature as above under TorrO.
Heat for at least 2 seconds, preferably 20 seconds. After such heat treatment, the device is evacuated and an electric field of 108 V/(11 or higher) is applied. As a result, the emission pattern changes as shown in FIG. 2 to FIG. 3, and the radiation current is stabilized.
前記のガス中での加熱温度は９００〜１０００″Ｃの範
囲であることが必要で、９００℃未満ではスパイクノ
イズおよびステップノイズがおこり、また１０００°Ｃ
を超えると前記ノイズに加えドリフトがおこる。The heating temperature in the gas mentioned above must be in the range of 900 to 1000"C; below 900°C, spike noise and step noise will occur, and below 1000°C
If it exceeds this, drift will occur in addition to the above-mentioned noise.
この範囲の温度では短時間ノイズが±０．２％以下、ド
リフトは±０．１％／ｈｒ以下と極めて電流安定性がよ
いものとなる。In this temperature range, short-time noise is less than ±0.2%, drift is less than ±0.1%/hr, and current stability is extremely good.
炭化水素ガス中での加熱時間は１０００秒以上であるこ
とが必要である。加熱時間と安定電流の放射時間の関係
図（エチレンガスＰ ＝ Ｉ Ｘｌ０−ｈＴｏｒｒ。The heating time in hydrocarbon gas needs to be 1000 seconds or more. Relationship diagram between heating time and stable current emission time (ethylene gas P = I Xl0 - hTorr.
放射電流１０μＡ）を示すと第４図の通りである。The radiation current (10 μA) is shown in FIG.
図が示すように、１０００秒未満では安定電流の放射時
間が短い。また、炭化水素ガス中での加熱のみでは、安
定電流の大きさが小さくかつ放射時間が短い（１ｘｌＱ
−１０Ｔｏｒｒ、放射電流６μ＾で、約２０分）が、更
に酸素ガスによる熱処理を施すと１０μＡの貧定電流が
１時間以上得られる。As shown in the figure, when the time is less than 1000 seconds, the stable current emission time is short. In addition, heating only in hydrocarbon gas results in a small stable current and a short radiation time (1xlQ
-10 Torr and a radiation current of 6 .mu.^ for about 20 minutes), but if heat treatment is further performed with oxygen gas, a poor constant current of 10 .mu.A can be obtained for more than 1 hour.
炭化水素ガスとしてはエチレンのほかメタン等の炭化水
素が挙げられる。Hydrocarbon gases include hydrocarbons such as methane in addition to ethylene.
実施例
先端径０．１ ｐｍのＮｂＣｏ、ｑｓＮｏ、ｏ＋＜１１
０＞エミッターを超高真空下（２×１Ｑ−１０Ｔｏｒｒ
）の下で、１８００“Ｃでフラッシュ加熱して清浄表面
とした。この系にエチレンガスを導入し、Ｉ Ｘ １０
−”Ｔｏｒｒの圧力下で９８０℃で２５０００秒加熱し
た。次に真空排気後、酸素ガスを導入し、Ｉ Ｘ １０
− ｈＴｏｒｒの圧力下、９８０°Ｃで２０秒加熱した
後、超高真空に排気してエミッターに１０＠Ｖ／ｃｍ以
上の電界を印加してエミッションパターンを第２図から
第３図に変化させた。Example NbCo with tip diameter 0.1 pm, qsNo, o+<11
0> Place the emitter under ultra-high vacuum (2×1Q-10 Torr
) to provide a clean surface by flash heating at 1800"C. Ethylene gas was introduced into the system and I
- Heated at 980°C for 25,000 seconds under a pressure of 1.5 Torr. Next, after vacuum evacuation, oxygen gas was introduced and
- After heating at 980°C for 20 seconds under a pressure of hTorr, the emitter was evacuated to an ultra-high vacuum and an electric field of 10@V/cm or more was applied to the emitter to change the emission pattern from Fig. 2 to Fig. 3. Ta.
得られたフィールドエミッターの電流雑音は、２ Ｘｌ
０−１０Ｔｏｒｒの真空度で±０．２％以下、ドリフト
は±０．１％／ｈｒ以下で、放射電流１０μ八を１時間
以上安定に放射できた。The current noise of the field emitter obtained is 2 Xl
At a vacuum level of 0-10 Torr, a radiation current of 10 μ8 was stably radiated for more than one hour with a drift of less than ±0.2% and a drift of less than ±0.1%/hr.
発明の効果
本発明の方法によると、２ ×ＩＱ−１１１Ｔｏｒｒの
真空下でも電流雑音±０．２％以下、ドリフト±０．１
％／ｈｒ以下であり、かつ全電流１０μ＾を１時間以上
安定に放射できるフィールドエミッターが得られ、しか
もこれを再現性よく得られる優れた効果を有する。Effects of the Invention According to the method of the present invention, current noise is ±0.2% or less and drift is ±0.1 even under a vacuum of 2 × IQ-111 Torr.
%/hr or less and can stably emit a total current of 10 μ^ for more than 1 hour, and has an excellent effect of being able to achieve this with good reproducibility.
第１図はＮｂＣｏ、 ＊ｓＮｏ、。＋＜１１０＞フィー
ルドエミッターの１８００°Ｃでフラッシュ加熱後のチ
ップ先端形状、第２図は１８００°Ｃフラッシュ加熱後
のエミッターからのエミッションパターン、第３図は本
発明の方法で得られたフィールドエミッターのエミッシ
ョンパターン、第４図はエチレンガス中の加熱時間と安
定電流の放射時間との関係図。
第 １ 図Figure 1 shows NbCo, *sNo. +<110> Chip tip shape after flash heating at 1800°C of field emitter, Figure 2 shows the emission pattern from the emitter after flash heating at 1800°C, and Figure 3 shows the field emitter obtained by the method of the present invention. Figure 4 is a diagram showing the relationship between heating time in ethylene gas and stable current emission time. Figure 1
Claims (1)
下で、エチレンまたはその他の炭化水素ガス中において
１０００秒以上加熱し、ついで更に酸素ガス中で加熱し
た後、真空に排気し、１０＾８Ｖ／ｃｍ以上の強電界を
印加することを特徴とする炭窒化ニオブフィールドエミ
ッターの作製方法。A niobium carbonitride single crystal emitter is heated at 900 to 1000°C in ethylene or other hydrocarbon gas for 1000 seconds or more, then further heated in oxygen gas, and then evacuated to 10^8V/cm. A method for producing a niobium carbonitride field emitter characterized by applying a strong electric field of the above strength.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63035794A JPH01209634A (en) | 1988-02-18 | 1988-02-18 | Manufacture of niobium carbide-nitride field emitter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63035794A JPH01209634A (en) | 1988-02-18 | 1988-02-18 | Manufacture of niobium carbide-nitride field emitter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01209634A true JPH01209634A (en) | 1989-08-23 |
| JPH0577135B2 JPH0577135B2 (en) | 1993-10-26 |
Family
ID=12451830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63035794A Granted JPH01209634A (en) | 1988-02-18 | 1988-02-18 | Manufacture of niobium carbide-nitride field emitter |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01209634A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008121440A2 (en) * | 2007-03-30 | 2008-10-09 | General Electric Company | Thermo-optically functional compositions, systems and methods of making |
| US8278823B2 (en) | 2007-03-30 | 2012-10-02 | General Electric Company | Thermo-optically functional compositions, systems and methods of making |
-
1988
- 1988-02-18 JP JP63035794A patent/JPH01209634A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008121440A2 (en) * | 2007-03-30 | 2008-10-09 | General Electric Company | Thermo-optically functional compositions, systems and methods of making |
| WO2008121440A3 (en) * | 2007-03-30 | 2008-12-04 | Gen Electric | Thermo-optically functional compositions, systems and methods of making |
| US8278823B2 (en) | 2007-03-30 | 2012-10-02 | General Electric Company | Thermo-optically functional compositions, systems and methods of making |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0577135B2 (en) | 1993-10-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |