JPH0577133B2 - - Google Patents
Info
- Publication number
- JPH0577133B2 JPH0577133B2 JP21983485A JP21983485A JPH0577133B2 JP H0577133 B2 JPH0577133 B2 JP H0577133B2 JP 21983485 A JP21983485 A JP 21983485A JP 21983485 A JP21983485 A JP 21983485A JP H0577133 B2 JPH0577133 B2 JP H0577133B2
- Authority
- JP
- Japan
- Prior art keywords
- emitter
- chip
- carbon film
- tip
- electric field
- 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
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 230000005684 electric field Effects 0.000 claims description 19
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 238000010894 electron beam technology Methods 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 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 2
- 125000003821 2-(trimethylsilyl)ethoxymethyl group Chemical group [H]C([H])([H])[Si](C([H])([H])[H])(C([H])([H])[H])C([H])([H])C(OC([H])([H])[*])([H])[H] 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Landscapes
- Cold Cathode And The Manufacture (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は高性能特制を示すフイールドエミツタ
ーの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method of manufacturing a field emitter exhibiting high performance characteristics.
フイールドエミツターからの放射電流は、高輝
度、可干渉性、点光源などの優れた性質を示す。
これは電子線露光機、低加速SEM、分析電子顕
微鏡などの電子源として重要である。 The emitted current from the field emitter exhibits excellent properties such as high brightness, coherence, and point light source.
This is important as an electron source for electron beam exposure machines, low-acceleration SEMs, analytical electron microscopes, etc.
従来技術
従来、フイールドエミツターとしては、Ｗが実
用化されてきたが、このフイールドエミツターは
電流の安定性に問題があり、時間と共に大幅に減
衰すると共に電流変動も大きいので、広い応用を
疎外している。Conventional technology Conventionally, W has been put into practical use as a field emitter, but this field emitter has a problem with current stability, and as it significantly attenuates over time and has large current fluctuations, it has been excluded from a wide range of applications. are doing.
また炭化チタン単結晶からなるフイールドエミ
ツターも知られている。しかし、このフイールド
エミツターからの放射電子は、チツプ先端近傍か
ら放射状に放出され、いくつかの電子ビーム塊に
分れる問題点がある。 Field emitters made of single crystal titanium carbide are also known. However, there is a problem in that the radiated electrons from this field emitter are radially emitted from near the tip of the chip and are divided into several electron beam clusters.
発明の目的
本発明は従来の炭化チタン単結晶からなるフイ
ールドエミツターの問題点をなくするためになさ
れたもので、その目的は電流安定性がよく、高輝
度で電子放射特性の優れたフイールドエミツター
の製造方法を提供するにある。Purpose of the Invention The present invention was made in order to eliminate the problems of conventional field emitters made of single crystal titanium carbide. To provide a method for manufacturing vines.
発明の構成
本発明者らは前記目的を達成するため鋭意研究
の結果、炭窒化チタン（TiCxNy，0.5ｘ＋ｙ
１）単結晶エミツター（以下、TiCNエミツタ
ーと略記する）を炭化水素ガス中で900〜1400℃
で熱処理して、該エミツターの表面に炭素膜を形
成させた後、超高真空下で107Ｖ／cm以上の強電
界を印加すると、エミツシヨンパターンが変化
し、安定な電流特性を示すフイールドエミツター
が得られることを究明し得た。この知見に基いて
本発明を完成した。Structure of the Invention In order to achieve the above object, the present inventors have conducted extensive research and found that titanium carbonitride (TiCxNy, 0.5x+y)
1) A single crystal emitter (hereinafter abbreviated as TiCN emitter) is heated at 900 to 1400°C in hydrocarbon gas.
After heat treatment to form a carbon film on the surface of the emitter, when a strong electric field of 10 7 V/cm or more is applied under ultra-high vacuum, the emitter pattern changes and stable current characteristics are exhibited. It was found that a field emitter can be obtained. The present invention was completed based on this knowledge.
本発明の要旨は、TiCNエミツターを、炭化水
素ガス中で900〜1400℃で熱処理して、その表面
に炭素膜を形成させた後、超高真空下で107Ｖ／
cm以上の強電界を印加することを特徴とする高安
定電子放射特性を示すフイールドエミツターの製
造方法にある。 The gist of the present invention is to heat-treat a TiCN emitter at 900 to 1400°C in hydrocarbon gas to form a carbon film on its surface, and then heat it at 10 7 V/V under ultra-high vacuum.
A method for manufacturing a field emitter exhibiting highly stable electron emission characteristics characterized by applying a strong electric field of cm or more.
本発明において使用するTiCNエミツターは、
炭窒化チタン単結晶ロツドから切り出した、例え
ば、0.2×0.2×３mmの直方体の先端を電解研磨法
により約0.1μmの先端径とし、このエミツターを
超高真空下で1500℃でフラツシユ加熱する。これ
により清浄表面とすると共にチツプ先端を
（100），（111）面で覆われた形状のものにする。
例えば、TiCN＜110＞エミツターの場合は第１
図に示すような形状のものとなる。このTiCN＜
110＞エミツターからのエミツシヨンパターンは
第２図に示すようになる。（なお、斜線部分は電
子ビームのあたつた部分を示す。）これはチツプ
先端の（100），（111）の各結晶面から作られる尖
つた部分からのエミツシヨンに対応する。この
TiCNのエミツシヨンパターンは電界強度の大き
い個所からの電子のエミツシヨンで説明できる。 The TiCN emitter used in the present invention is
For example, the tip of a 0.2 x 0.2 x 3 mm rectangular parallelepiped cut from a titanium carbonitride single crystal rod is electrolytically polished to a tip diameter of about 0.1 μm, and the emitter is flash-heated at 1500° C. under ultra-high vacuum. This makes the surface clean and the tip of the chip has a shape covered with (100) and (111) planes.
For example, in the case of TiCN<110> emitter, the first
The shape will be as shown in the figure. This TiCN<
The emission pattern from the 110> emitter is shown in Figure 2. (Note that the shaded area indicates the area hit by the electron beam.) This corresponds to the emission from the pointed area formed from the (100) and (111) crystal planes at the tip of the chip. this
The emission pattern of TiCN can be explained by the emission of electrons from locations with high electric field strength.
このようにした得られたTiCNエミツターの表
面に炭素膜を形成させる。炭素膜の形成は、
TiCNエミツターを炭化水素ガス中で900〜1400
℃で加熱することによつて得られる。その加熱時
間は100L（ラングミユアー、Ｌ＝10-6Torr×sec）
以上とする。即ち、炭化水素ガスを超高真空装置
に導入し、真空度が５×10-6Torrの場合は20秒
以上の処理時間が必要である。炭化水素ガスとし
ては、エチレン、メタン等が挙げられる。しかし
これに限定されるものではない。 A carbon film is formed on the surface of the TiCN emitter thus obtained. The formation of carbon film is
900-1400 TiCN emitter in hydrocarbon gas
Obtained by heating at °C. The heating time is 100L (Langmiure, L=10 -6 Torr×sec)
The above shall apply. That is, when hydrocarbon gas is introduced into an ultra-high vacuum apparatus and the degree of vacuum is 5 x 10 -6 Torr, a processing time of 20 seconds or more is required. Examples of the hydrocarbon gas include ethylene and methane. However, it is not limited to this.
このようにして表面に炭素膜を形成したチツプ
から超高真空下で全電流10〜20μAで30分以上電
子ビームを放射し、107Ｖ／cm以上の強電界を印
加する。これにより、エミツシヨンパターンは第
２図から第３図のものに変化する。 An electron beam is emitted from the chip with the carbon film formed on its surface under an ultra-high vacuum for 30 minutes or more at a total current of 10 to 20 μA, and a strong electric field of 10 7 V/cm or more is applied. As a result, the emission pattern changes from that shown in FIG. 2 to that shown in FIG. 3.
なお、斜線部分が電子ビームのあつた個所で、
点線で示す部分は清浄表面からのエミツシヨンパ
ターンを示す。 Note that the shaded area is the area where the electron beam hit.
The dotted line indicates the emission pattern from the clean surface.
このように本発明において、特定の条件でエミ
ツター表面に炭素膜を形成し、次いで強電界を印
加することとした理由並びに作用は以下のとおり
である。 Thus, in the present invention, the reason and effect of forming a carbon film on the emitter surface under specific conditions and then applying a strong electric field are as follows.
(1) エミツター表面での炭素膜の形成
清浄表面を持つTiCNチツプをエチレンなどの
炭化水素ガス中で、900〜1400℃の温度範囲で加
熱することにより、チツプ表面に炭素膜を形成す
る。この炭素膜表面層は、続く工程である107
Ｖ／cmオーダーの強電界の印加により、一部がチ
ツプ先端に移動し、清浄表面でのチツプ先端の曲
率半径より1/2〜1/3だけ小さい曲率半径を持つ
て、チツプ中央部の最先端を作るに至る。つま
り、強電界の印加により炭素膜表面層の一部をチ
ツプ先端に移動させるのである。加熱温度が900
℃未満ではチツプ表面に充分に炭素膜を形成する
ことができず、また1400℃を超えると形成される
炭素膜が厚くなりすぎて、強電界の印加によつて
もチツプ先端への炭素膜の移動が生じにくくなる
ので好ましくない。(1) Formation of a carbon film on the emitter surface By heating a TiCN chip with a clean surface in a hydrocarbon gas such as ethylene at a temperature range of 900 to 1400°C, a carbon film is formed on the chip surface. This carbon film surface layer is formed in the subsequent process 10 7
By applying a strong electric field on the order of V/cm, a part of the chip moves to the tip of the chip, and has a radius of curvature that is 1/2 to 1/3 smaller than the radius of curvature of the tip of the chip on the clean surface. Leading to making the tip. In other words, a portion of the carbon film surface layer is moved to the tip of the chip by applying a strong electric field. Heating temperature is 900
If the temperature is below 1400°C, it will not be possible to form a sufficient carbon film on the chip surface, and if the temperature exceeds 1400°C, the carbon film formed will become too thick, and even with the application of a strong electric field, the carbon film will not be able to form on the tip of the chip. This is not preferable because movement becomes difficult to occur.
TiCNの表面では、陰イオンサイト（炭素、窒
素原子が入るべき位置）に多数の原子空孔（原子
の孔）が存在することがわかつている。このよう
な表面では、表面原子は動き易くなつており、ま
た周囲の残留ガスもこの原子空孔に吸着され易
い。前者は短時間電流ノイズの原因となり、後者
はガス吸着による仕事関数の増加により、長時間
ノイズ（ドリフト）を発生する。このような電流
ノイズは、チツプ表面に炭素膜を形成することに
より解消する。何故ならば、この炭素膜は、グラ
フアイトの構造をとつており、この表面は化学的
に極めて不活性であり、更には炭素間の共有結合
が極めて強いために殆ど原子空孔が存在しないか
らである。 It is known that many atomic vacancies (atomic holes) exist on the surface of TiCN at anion sites (positions where carbon and nitrogen atoms should enter). On such a surface, surface atoms are easily mobile, and surrounding residual gas is also likely to be adsorbed by these atomic vacancies. The former causes short-time current noise, and the latter causes long-term noise (drift) due to an increase in work function due to gas adsorption. Such current noise can be eliminated by forming a carbon film on the chip surface. This is because this carbon film has a graphite structure, and this surface is extremely chemically inert, and furthermore, because the covalent bonds between carbons are extremely strong, there are almost no atomic vacancies. It is.
したがつて、チツプ表面に炭素膜を形成するこ
とにより、安定な放射電流が得られる。 Therefore, by forming a carbon film on the chip surface, stable radiation current can be obtained.
(2) 強電界の印加
チツプ表面に炭素膜を形成した後、超高真空下
での107Ｖ／cmオーダーの強電界の印加により、
炭素膜の一部をチツプ先端に移動し、チツプ中央
部の最先端を作る。このような形状を持つチツプ
は、チツプ最先端部に最も大きい電界がかかるた
め、この部分からの電子放射が主となり、チツプ
長軸方向に平行な電子が放射される。第３図はこ
の時のエミツシヨンパターンである。(2) Application of strong electric field After forming a carbon film on the chip surface, by applying a strong electric field of the order of 10 7 V/cm under ultra-high vacuum,
Move part of the carbon film to the tip of the chip to create the leading edge in the center of the chip. In a chip having such a shape, the largest electric field is applied to the tip end, so electrons are mainly emitted from this part, and electrons parallel to the long axis direction of the chip are emitted. FIG. 3 shows the emission pattern at this time.
したがつて、強電界の印加により、チツプ先端
の曲率半径を小さくし、エミツシヨンパターンを
第２図のものから第３図のものに変化させること
ができる。 Therefore, by applying a strong electric field, it is possible to reduce the radius of curvature at the tip of the chip and change the emission pattern from that shown in FIG. 2 to that shown in FIG. 3.
強電界の強さを107Ｖ／cm以上としたのは、前
述の炭素膜の移動には107Ｖ／cmオーダー以上の
強電界の印加が必要なためである。これよりも弱
い電界の印加では炭素膜のチツプ先端への移動は
生じない。 The reason why the strength of the strong electric field is set to 10 7 V/cm or more is because the above-mentioned movement of the carbon film requires the application of a strong electric field of the order of 10 7 V/cm or more. If an electric field weaker than this is applied, the carbon film will not move to the tip of the chip.
また、次のような効果も得られる。すなわち、
フイールドエミツターのチツプ先端の曲率半径
は、通常0.1μmになるように形成するが、これは
チツプ（陰極）先端と陽極の距離を１cmとする
と、この電極間に電圧1000〜2000Vを印加して１
〜10μAの電流を取り出すことに対応する。この
時のチツプにかかつた電界は107Ｖ／cmオーダー
になる。言い替えると、チツプ先端の曲率半径に
よらず107Ｖ／cmオーダーの電界の印加により１
〜10μAの電流を取り出すことができる。しかも、
チツプ最先端が炭素膜で作られているので、電流
を安定して取り出すことができる。 In addition, the following effects can also be obtained. That is,
The radius of curvature of the tip of the field emitter chip is usually formed to be 0.1 μm, but this is done by applying a voltage of 1000 to 2000 V between the electrodes, assuming that the distance between the tip of the chip (cathode) and the anode is 1 cm. 1
Corresponds to drawing a current of ~10μA. The electric field applied to the chip at this time is on the order of 10 7 V/cm. In other words, regardless of the radius of curvature of the chip tip, applying an electric field of the order of 10 7 V/cm
A current of ~10 μA can be extracted. Moreover,
Since the leading edge of the chip is made of carbon film, it is possible to extract current stably.
このようにして得られたフイールドエミツター
は電流雑音は±0.2％以下、ドリフトは±２％／
hr以下の優れた特性を示す。その電流特性は第４
図に示す通りであり、一定の電流値を示し極めて
安定である。 The field emitter obtained in this way has a current noise of less than ±0.2% and a drift of ±2%/
Shows excellent properties below hr. Its current characteristics are the fourth
As shown in the figure, it shows a constant current value and is extremely stable.
この実験条件は真空度3.5×10-11Torr、印加電
圧1500Vで行つたものである。 The experimental conditions were a vacuum level of 3.5×10 -11 Torr and an applied voltage of 1500V.
実施例
先端径0.1μmのTiC0.95N0.01＜110＞フイールド
エミツターを超高真空下にセツトし、1500℃にフ
ラツシユ加熱した。この真空系にエチレンガスを
導入し、５×10-6Torrの真空度にした後、1100
℃で30分間加熱してチツプ表面に炭素膜を形成さ
せた。この後、3.5×10-11Torrの真空下で全電流
10μAを30分以上放射し（107Ｖ／cm以上の強電界
の印加）続けてエミツシヨンパターンを変化させ
た。Example A TiC 0.95 N 0.01 <110> field emitter with a tip diameter of 0.1 μm was set under ultra-high vacuum and flash heated to 1500°C. Ethylene gas was introduced into this vacuum system to achieve a vacuum level of 5 × 10 -6 Torr, and then
A carbon film was formed on the chip surface by heating at ℃ for 30 minutes. After this, the total current under vacuum of 3.5×10 -11 Torr
The emission pattern was changed by continuously emitting 10 μA for 30 minutes or more (applying a strong electric field of 10 7 V/cm or more).
上記製法によつて得たフイールドエミツターの
電流雑音は±0.2％以下、ドリフトは±0.2％／hr
以下でその電流特性は第４図に示す通りであつ
た。 The current noise of the field emitter obtained by the above manufacturing method is less than ±0.2%, and the drift is ±0.2%/hr.
The current characteristics were as shown in FIG. 4 below.
第１図はTiCN＜110＞エミツターの1500℃フ
ラツシユ加熱後の先端形状、第２図は第１図のエ
ミツターからのエミツシヨンパターン、第３図は
第１図のエミツターチツプの表面に炭素皮膜を形
成させた後のエミツシヨンパターン、第４図は本
発明の方法で製造したエミツターの全電流と時間
との関係図であり、この時の実験条件は真空度
3.5×10-11Torr、印加電圧1500Vである。
Figure 1 shows the tip shape of the TiCN <110> emitter after flash heating at 1500℃, Figure 2 shows the emission pattern from the emitter in Figure 1, and Figure 3 shows the carbon film on the surface of the emitter tip in Figure 1. Figure 4 shows the relationship between the total current and time of the emitter manufactured by the method of the present invention, and the experimental conditions were as follows:
3.5×10 -11 Torr, applied voltage 1500V.
Claims (1)
ガス中で900〜1400℃で熱処理して、その表面に
炭素膜を形成させた後、超高真空下で107Ｖ／cm
以上の強電界を印加することを特徴とする高性能
フイールドエミツターの製造方法。1 A titanium carbonitride single crystal emitter is heat-treated at 900 to 1400°C in hydrocarbon gas to form a carbon film on its surface, and then heated at 10 7 V/cm under ultra-high vacuum.
A method for manufacturing a high-performance field emitter characterized by applying a strong electric field of the above magnitude.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60219834A JPS6280937A (en) | 1985-10-02 | 1985-10-02 | Manufacturing method of high performance field emitter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60219834A JPS6280937A (en) | 1985-10-02 | 1985-10-02 | Manufacturing method of high performance field emitter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6280937A JPS6280937A (en) | 1987-04-14 |
| JPH0577133B2 true JPH0577133B2 (en) | 1993-10-26 |
Family
ID=16741777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60219834A Granted JPS6280937A (en) | 1985-10-02 | 1985-10-02 | Manufacturing method of high performance field emitter |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6280937A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63279535A (en) * | 1987-05-08 | 1988-11-16 | Natl Inst For Res In Inorg Mater | Manufactute of carbon-nitride niobium field emitter |
-
1985
- 1985-10-02 JP JP60219834A patent/JPS6280937A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6280937A (en) | 1987-04-14 |
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