JPH0577132B2 - - Google Patents
Info
- Publication number
- JPH0577132B2 JPH0577132B2 JP21983385A JP21983385A JPH0577132B2 JP H0577132 B2 JPH0577132 B2 JP H0577132B2 JP 21983385 A JP21983385 A JP 21983385A JP 21983385 A JP21983385 A JP 21983385A JP H0577132 B2 JPH0577132 B2 JP H0577132B2
- Authority
- JP
- Japan
- Prior art keywords
- emitter
- chip
- tip
- electric field
- 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
- 230000005684 electric field Effects 0.000 claims description 19
- 239000013078 crystal Substances 0.000 claims description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 description 8
- 238000010894 electron beam technology Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 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
- 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 for manufacturing a field emitter.
フイールドエミツターからの放射電流は、輝度
が大きく、放射電子のエネルギー幅が小さく、し
かも点光源に近いなどの優れた性質を持つている
ので、これは高分解能電子顕微鏡、電子線ホログ
ラフイー電顕、ナノメートルリソグラフイー等の
分野において不可欠のものである。 The emitted current from the field emitter has excellent properties such as high brightness, small energy width of emitted electrons, and is close to a point light source. , is essential in fields such as nanometer lithography.
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、広い応用を疎外して
いる。Prior Art Conventionally, W has been put to practical use as a field emitter, but this field emitter has a problem with current stability, which precludes its wide application.
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.
本発明者らはこの問題点を解決すべく研究の結
果、遷移金属化合物からなるフイールドエミツタ
ーの軸方位を＜110＞方位に選ぶことにより、放
射電子ビームの方向をエミツター軸方位にするこ
とを開発し得た（特願昭58−199605号参照）。 In order to solve this problem, the present inventors conducted research and found that by selecting the axial direction of the field emitter made of a transition metal compound to be the <110> direction, the direction of the emitted electron beam could be set to the emitter axial direction. (Refer to Japanese Patent Application No. 199605-1983).
発明の目的
本発明の目的は高輝度でさらに優れた電子放射
特性を示すフイールドエミツターの製造方法を提
供するにある。OBJECTS OF THE INVENTION An object of the present invention is to provide a method for manufacturing a field emitter that exhibits high brightness and excellent electron emission characteristics.
発明の構成
本発明者らはフイールドエミツターについて研
究を続けた結果、炭窒化チタン（TiCxNy，0.5
ｘ＋ｙ１）単結晶エミツター（以下、TiCN
エミツターと略記する）を酸素ガス中で900〜
1400℃で熱処理して、その表面を酸化した後、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 As a result of continuing research on field emitters, the present inventors discovered that titanium carbonitride (TiCxNy, 0.5
x+y1) Single crystal emitter (hereinafter referred to as TiCN
(abbreviated as emitter) in oxygen gas to 900~
After heat-treating at 1400℃ to oxidize the surface, applying a strong electric field of 10 7 V/cm or more under ultra-high vacuum,
It was found that a field emitter whose emission pattern changes and exhibits stable characteristics can be obtained. The present invention was completed based on this knowledge.
本発明の要旨は、炭窒化チタン単結晶エミツタ
ーを酸素ガス中で900〜1400℃で熱処理して、該
エミツターの表面を酸化した後、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 titanium carbonitride single crystal emitter at 900 to 1400°C in oxygen gas to oxidize the surface of the emitter, and then heat it under an ultra-high vacuum.
A method for manufacturing a field emitter characterized by applying a strong electric field of 10 7 V/cm or more.
本発明において使用する炭窒化チタン単結晶エ
ミツターは、単結晶ロツドから切り出した、例え
ば、0.2×0.23mmの直方体の先端を電解研磨法に
より約0.1μmの先端経とし、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 titanium carbonitride single crystal emitter used in the present invention is made by cutting the tip of a 0.2 x 0.23 mm rectangular parallelepiped from a single crystal rod to a tip diameter of approximately 0.1 μm by electropolishing, and then polishing this emitter under ultra-high vacuum. Heat at 1500℃. This makes the surface clean and the tip of the tip (100).
(111) Shape covered with a surface. for example,
In the case of a TiCN <110> emitter, it has a shape as shown in Figure 1. The emission pattern from this TiCN<110> emitter is shown in FIG. (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 TiCN emission pattern can be explained by the emission of electrons from locations with high electric field strength.
このような清浄表面を持つたTiCNチツプを、
酸素ガス中で例えば10-6Torrの下で900〜1400℃
で加熱する。これにより、表面に酸化物ができ
る。加熱時間は5L（ラングミユアー）、（Ｌ＝10-6
Torr×1sec）以上になるように選ぶ。加熱温度
が900℃未満および1400℃以上では、エミツシヨ
ンパターンは清浄表面からのエミツシヨンパター
ンと本質的に同じであり、又電子放射特性も改善
されない。したがつて加熱温度は900〜1400℃で
あることが好ましい。チツプ表面を酸化した後、
超高真空下で全電流を10μA〜20μAにより、30分
以上電子ビームを放射し（強電界を印加）つづけ
ると、エミツシヨンパターンが第２図から第３図
に変化する。なお、斜線部分が電子ビームのあた
つた個所で、点線部分は清浄表面からのエミツシ
ヨンパターンを示す。 TiCN chips with such a clean surface,
e.g. 900-1400℃ under 10 -6 Torr in oxygen gas
Heat it up. This creates oxides on the surface. Heating time is 5L (Langmiure), (L=10 -6
Torr×1sec) or higher. At heating temperatures below 900°C and above 1400°C, the emission pattern is essentially the same as that from a clean surface, and the electron emission properties are not improved. Therefore, the heating temperature is preferably 900 to 1400°C. After oxidizing the chip surface,
When emitting an electron beam (applying a strong electric field) for more than 30 minutes at a total current of 10 μA to 20 μA under ultra-high vacuum, the emission pattern changes from FIG. 2 to FIG. 3. Note that the shaded area is the location where the electron beam hits, and the dotted line area is 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
ツター表面を酸化し、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 oxidizing the emitter surface under specific conditions and then applying a strong electric field are as follows.
(1) エミツター表面の酸化
清浄表面を持つTiCNチツプを酸素ガス中で、
900〜1400℃の温度範囲で加熱することにより、
チツプ表面に酸化物TiCNOを形成する。この表
面酸化物層は、続く工程である107Ｖ／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
により表面酸化物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
表面に充分に酸化物を形成することができず、ま
た1400℃を超えると形成される酸化物が厚くなり
すぎて、強電界の印加によつてもチツプ先端への
酸化物の移動が生じにくくなるので好ましくな
い。(1) Oxidation of the emitter surface A TiCN chip with a clean surface was oxidized in oxygen gas.
By heating in the temperature range of 900-1400℃,
Oxide TiCNO is formed on the chip surface. By applying a strong electric field on the order of 10 7 V/cm in the subsequent step, a part of this surface oxide layer moves to the tip of the chip, and the radius of curvature of the tip of the chip on the clean surface is 1/1/2.
With a radius of curvature that is 2 to 1/3 smaller, the leading edge of the central part of the chip is created. In other words, a portion of the surface oxide layer is moved to the tip of the chip by applying a strong electric field. If the heating temperature is less than 900℃, sufficient oxide cannot be formed on the chip surface, and if the heating temperature exceeds 1400℃, the oxide formed will become too thick and will not reach the tip of the chip even when a strong electric field is applied. This is not preferable because it makes it difficult for the oxide to migrate.
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、酸化表面では起こりにくい。何故なら
ば、酸素原子の入つた酸化物TiCNOには原子空
孔が殆どないからである。 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 is less likely to occur on oxidized surfaces. This is because TiCNO, an oxide containing oxygen atoms, has almost no vacancies.
したがつて、チツプ表面に酸化物TiCNO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 the oxide TiCNO on the chip surface, a stable radiation current can be obtained.
(2) 強電界の印加
チツプ表面に酸化物TiCNOを形成した後、107
Ｖ／cmオーダーの強電界の印加により、表面酸化
物層の一部が剥がれて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 oxide TiCNO on the chip surface, 10 7
By applying a strong electric field on the order of V/cm, part of the surface oxide layer is peeled off and moved to the tip of the chip, forming the leading edge at the center of the chip. In a chip with such a shape, the largest electric field is applied to the tip of the chip, so electrons are mainly emitted from this part.
Electrons parallel to the long axis direction of the chip are emitted. Third
The figure 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
述の表面酸化物層の移動には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表面酸化物層のチツプ先
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 surface oxide layer requires application of a strong electric field of the order of 10 7 V/cm or more. Application of an electric field weaker than this does not cause the surface oxide layer to move toward 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、
チツプ最先端が酸化物層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 an oxide layer, the current can be extracted stably.
このようにして得られたフイールドエミツター
は、電流雑音が±0.2％以下、ドリフトは±0.2％
hr以下の優れた特性を示す。その電子放射特性は
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。この実験条件は真空度5.0×
10-11Torr、印加電圧1400Vで行つたものである。 The field emitter obtained in this way has a current noise of less than ±0.2% and a drift of ±0.2%.
Shows excellent properties below hr. Its electron emission characteristics are as shown in FIG. 4, and it exhibits a constant current value and is extremely stable. This experimental condition is vacuum degree 5.0×
It was conducted at 10 -11 Torr and an applied voltage of 1400V.
なお、このような特性は炭窒化チタン単結晶の
方位に関係なく得られる。 Note that such characteristics can be obtained regardless of the orientation of the titanium carbonitride single crystal.
実施例
先端径0.1μmのTiC0.95N0.01＜110＞フイールド
エミツターを10-10〜10-11Torrの超高真空下にセ
ツトし、1500℃にフラツシユ加熱した。この系に
酸素ガスを導入し、１×10-6Torrの真空度にし
た後、1100℃で10秒間加熱してチツプ表面を酸化
した。この後、５×10-11Torrの真空下で全電流
10μAを30分間以上放射し（107Ｖ／cm以上の強電
界の印加）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 an ultra-high vacuum of 10 -10 to 10 -11 Torr and flash heated to 1500°C. Oxygen gas was introduced into this system to create a vacuum of 1×10 -6 Torr, and then the chip surface was oxidized by heating at 1100° C. for 10 seconds. After this, the total current is
The emission pattern was changed by 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.
Below, the current characteristics were as shown in FIG.
第１図はTiCN＜110＞エミツターの1500℃フ
ラツシユ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を酸化処理
し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5.0×
10-11Torr、印加電圧1400Vである。
Figure 1 shows the tip shape of the TiCN <110> emitter after flash heating at 1500℃, Figure 2 shows the emitter pattern from the emitter in Figure 1, and Figure 3
The figure shows the emitter pattern after the surface of the emitter chip shown in Fig. 1 has been oxidized, and Fig. 4 shows the relationship between the total current and time of the emitter manufactured by the method of the present invention.The experimental conditions at this time were Vacuum degree 5.0×
10 -11 Torr, applied voltage 1400V.
Claims (1)
で900〜1400℃で熱処理して、該エミツターの表
面を酸化した後、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 oxygen gas to oxidize the surface of the emitter, and then a strong electric field of 10 7 V/cm or more is applied under ultra-high vacuum. A method for manufacturing a field emitter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60219833A JPS6280936A (en) | 1985-10-02 | 1985-10-02 | Method for manufacturing field emitters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60219833A JPS6280936A (en) | 1985-10-02 | 1985-10-02 | Method for manufacturing field emitters |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6280936A JPS6280936A (en) | 1987-04-14 |
| JPH0577132B2 true JPH0577132B2 (en) | 1993-10-26 |
Family
ID=16741760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60219833A Granted JPS6280936A (en) | 1985-10-02 | 1985-10-02 | Method for manufacturing field emitters |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6280936A (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 JP60219833A patent/JPS6280936A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6280936A (en) | 1987-04-14 |
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