JPH0577134B2 - - Google Patents
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- Publication number
- JPH0577134B2 JPH0577134B2 JP21983585A JP21983585A JPH0577134B2 JP H0577134 B2 JPH0577134 B2 JP H0577134B2 JP 21983585 A JP21983585 A JP 21983585A JP 21983585 A JP21983585 A JP 21983585A JP H0577134 B2 JPH0577134 B2 JP H0577134B2
- Authority
- JP
- Japan
- Prior art keywords
- emitter
- electric field
- treatment
- chip
- strong electric
- 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
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- 230000005684 electric field Effects 0.000 claims description 27
- 238000004381 surface treatment Methods 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 150000003609 titanium compounds Chemical class 0.000 claims 4
- 239000007789 gas Substances 0.000 description 19
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001093 holography 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 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
本発明は高安定な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関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for manufacturing a field emitter exhibiting highly stable electron emission characteristics.
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、低加速走査型電子顕微鏡、分析電子顕微鏡、
電子線ホログライー顕微鏡等の新機能電子顕微鏡
の実現、電子顕微鏡の高分解能下に必須であり、
またナノメートルリソグラフイー等の分野におい
ても不可欠なものである。 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, so it can be used for low-acceleration scanning electron microscopes, analytical electron microscopes,
It is essential for the realization of new functional electron microscopes such as electron beam holography microscopes, and for the high resolution of electron microscopes.
It is also 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
用化されている。しかし、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 into practical use as a field emitter. However, there are problems with current stability, which precludes wide application.
本発明者らはさきに、遷移金属化合物からなる
フイールドエミツターとして、エミツターの軸方
位を＜110＞方位に選ぶことにより、従来実現し
ていなかつた放射電子ビームの方向をエミツター
軸方位にすることに成功した。（特願昭58−
199605号）。さらに、炭化チタン単結晶チツプ表
面を酸素ガスによる処理（特願昭59−275220号）
及びC2H4などの炭化水素ガスによる処理（特願
昭59−275221号）を施すことにより、高安定な電
子放射性特性を示すフイールドエミツターを得る
ことを開発し得た。 The inventors of the present invention previously discovered that by selecting the axial direction of the emitter as the <110> direction for a field emitter made of a transition metal compound, the direction of the emitted electron beam could be set in the direction of the emitter axis, which had not been achieved in the past. succeeded in. (Special application 1982-
No. 199605). Furthermore, the surface of the titanium carbide single crystal chip was treated with oxygen gas (Japanese Patent Application No. 59-275220).
By applying treatment with a hydrocarbon gas such as C 2 H 4 (Japanese Patent Application No. 59-275221), we were able to develop a field emitter that exhibits highly stable electron emissive properties.
発明の目的
本発明の目的は炭窒化チタン（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）の表面処理方法を開発し、さ
らに優れた安定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。Purpose of the invention The purpose of the present invention is to prepare titanium carbonitride (TiC x N y , 0.5
An object of the present invention is to develop a surface treatment method for a single crystal emitter (hereinafter abbreviated as TiCN emitter) and to provide a method for manufacturing a field emitter exhibiting even better stability.
発明の構成
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、TiCNエミツターの表面をH2Ｓま
たはＳを含むガス（例えばSF）（以下H2Ｓと略
記する）で、900〜1400℃の下で処理し、または
この処理とO2ガスによる処理及び又はC2H4また
は他の炭化水素ガス（例えばC2H6）（以下C2H4
と略記する）を併用して処理した後、さらに超高
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。この知見に基づいて本発明を完成した。Structure of the Invention In order to achieve the above object, the present inventors continued their research and found that the surface of the TiCN emitter was coated with H 2 S or a gas containing S (for example, SF) (hereinafter abbreviated as H 2 S). treatment under 900-1400 °C, or this treatment and treatment with O2 gas and or C2H4 or other hydrocarbon gases (e.g. C2H6 ) (hereinafter C2H4
), and then further 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
１ TiCNエミツター表面を、900〜1400℃の下
で、H2Ｓによる表面処理を施した後、超高真
空下で107Ｖ／cm以上の強電界を印加すること
を特徴とする高安定フイールドエミツターの製
造方法。 The gist of the present invention is as follows: 1. After surface treatment of the TiCN emitter surface with H 2 S at 900 to 1400°C, a strong electric field of 10 7 V/cm or more is applied under ultra-high vacuum. A method for manufacturing a highly stable field emitter.
２ TiCNエミツター表面を900〜1400℃の下で、
H2ＳまたはＳを含んだガスによる表面処理と
O2による表面処理とを別個にまたは同時に施
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高安定フイール
ドエミツターの製造方法。2 TiCN emitter surface at 900~1400℃,
Surface treatment with H 2 S or S-containing gas
A method for manufacturing a highly stable field emitter, which comprises applying a strong electric field of 10 7 V/cm or more under an ultra-high vacuum after performing surface treatment with O 2 separately or simultaneously.
３ TiCNエミツター表面を、900〜1400℃の下
で、H2Ｓによる表面処理と、C2H4による表面
処理とを別個にまたは同時に施した後、超高真
空下で、107Ｖ／cm以上の強電界を印加するこ
とを特徴とする高安定フイールドエミツターの
製造方法。3. After subjecting the TiCN emitter surface to surface treatment with H 2 S and C 2 H 4 separately or simultaneously at 900 to 1400°C, the surface was heated to 10 7 V/cm under ultra-high vacuum. A method for manufacturing a highly stable field emitter, characterized by applying a strong electric field of the above magnitude.
４ TiCNエミツター表面を、900〜1400℃の下
で、H2Ｓによる表面処理、O2による表面処理
及びC2H4による表面処理を別個に、例えばH2
Ｓ→O2→C2H4，H2Ｓ→C2H4→O2，C2H4→H2
Ｓ→O2，C2H4→O2→H2Ｓ，O2→C2H4→H2
Ｓ、またはO2→H2Ｓ→C2H4の順序または同時
に施した後、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高安定フイ
ールドエミツターの製造方法、にある。4 The TiCN emitter surface is subjected to surface treatment with H2S , O2 and C2H4 separately at 900-1400 ° C, e.g.
S→O 2 →C 2 H 4 , H 2 S→C 2 H 4 →O 2 , C 2 H 4 →H 2
S→O 2 , C 2 H 4 →O 2 →H 2 S, O 2 →C 2 H 4 →H 2
A highly stable field emitter characterized by applying a strong electric field of 10 7 V/cm or more under ultra-high vacuum after applying S, or O 2 → H 2 S → C 2 H 4 in the order or simultaneously. The manufacturing method.
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℃フラツシユ加熱し、TiCN＜
110＞エミツターの表面を清浄したものを使用す
る。そのエミツシヨンパターンは第１図に示す通
りである。なお、図中の斜線部分が電子ビームの
あたつた部分を表わす。 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 electropolished to a tip diameter of approximately 0.1 μm, and this emitter is flash heated at 1500°C under ultra-high vacuum to form TiCN<
110＞Use a clean emitter surface. The emission pattern is as shown in FIG. Note that the shaded area in the figure represents the area hit by the electron beam.
このような清浄表面を持つたTiCN＜110＞チ
ツプをH2Ｓガス中で、例えば10-6Torrの下で900
〜1400℃で加熱する。加熱時間は2L（ラングミユ
アー）、（Ｌ＝10-6Torr×1sec）以上になるよう
に選ぶ。加熱温度が900℃未満及び1400℃を超え
ると、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同じであり、電子放射特性
も改善されない。従つて、加熱温度は900〜1400
℃であることが必要である。 A TiCN<110> chip with such a clean surface is heated in H 2 S gas at a temperature of 900 °C under, for example, 10 -6 Torr.
Heat at ~1400°C. The heating time should be 2L (Langmiure), (L = 10 -6 Torr x 1sec) or more. When the heating temperature is below 900°C and above 1400°C, the emission pattern is the same as that from a clean surface, and the electron emission characteristics are not improved. Therefore, the heating temperature is 900-1400
It is necessary that the temperature is ℃.
このように処理した後、超高真空下で、全電流
を約10μAにし、30分以上電子ビームを放射（強
電界を印加）すると、エミツシヨンパターンは第
２図に変化する。なお、点線部分は表面処理前の
清浄表面からのエミツシヨンパターンを示す。 After this treatment, the emission pattern changes as shown in Figure 2 when an electron beam is emitted (a strong electric field is applied) for over 30 minutes at a total current of about 10 μA under ultra-high vacuum. Note that the dotted line portion indicates the emission pattern from the clean surface before surface treatment.
このように本発明において、特定の条件でエミ
ツター表面に硫化物を形成し、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 sulfide 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硫化物の形成
清浄表面を持つTiCNチツプをH2ＳなどのＳを
含むガス中で、900〜1400℃の温度範囲で加熱す
ることにより、チツプ表面に硫化物TiCNSを形
成する。この表面硫化物層は、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硫化物層の一部をチ
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硫化物を形成する
ことができず、また1400℃を超えると形成される
硫化物が厚くなりすぎて、強電界の印加によつて
もチツプ先端への硫化物の移動が生じにくくなる
ので好ましくない。(1) Formation of sulfide on the emitter surface By heating a TiCN chip with a clean surface in a gas containing S such as H 2 S at a temperature range of 900 to 1400°C, sulfide TiCNS is formed on the chip surface. Form. This surface sulfide layer is a subsequent step
By applying a strong electric field on the order of 10 7 V/cm, a part of the chip moves to the tip, and the center of the chip has a radius of curvature that is 1/2 to 1/3 smaller than the radius of curvature of the tip on the clean surface. We have come to the forefront of this field. In other words, a portion of the surface sulfide 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, sufficient sulfide cannot be formed on the chip surface, and if the temperature exceeds 1400°C, the sulfide formed becomes too thick, and even when a strong electric field is applied, sulfide cannot be formed 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、チツプ表面に硫化物層膜を形成するこ
とにより解消する。何故ならば、この硫黄原子の
入つたTiCNSには原子空孔は殆ど存在しないし、
また硫化物層表面は化学的に極めて不活性である
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 sulfide layer on the chip surface. This is because TiCNS containing sulfur atoms has almost no vacancies,
This is also because the surface of the sulfide layer is chemically extremely inert.
したがつて、チツプ表面に硫化物層を形成する
ことにより、安定な放射電流が得られる。 Therefore, by forming a sulfide layer on the chip surface, stable radiation current can be obtained.
(2) 強電界の印加
チツプ表面に硫化物層を形成した後、超高真空
下での107Ｖ／cmオーダーの強電界の印加により、
硫化物層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２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 sulfide layer 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 sulfide layer 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. Figure 2 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１図のものから第２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 of the tip of the chip and change the emission pattern from that shown in FIG. 1 to that shown in FIG. 2.
強電界の強さを107Ｖ／cm以上としたのは、前
述の硫化物層の移動には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硫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 sulfide layer requires the 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 sulfide 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、
チツプ最先端が硫化物層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 a sulfide layer film,
Current can be extracted stably.
このような処理を施したTiCNフイールドエミ
ツターは、電流雑音が±0.2％以下で、ドリフト
は±0.2％／hr以下の優れた特性を示し、第３図
ａの通りとなる。 The TiCN field emitter subjected to such treatment exhibits excellent characteristics with current noise of less than ±0.2% and drift of less than ±0.2%/hr, as shown in Figure 3a.
前期のH2Ｓ処理とO2処理及び又はC2H4ガスに
よる処理を組合せてガス処理を施してもよい。 The gas treatment may be performed by combining the earlier H 2 S treatment, O 2 treatment, and/or treatment with C 2 H 4 gas.
これらを例示すると次の通りである。 Examples of these are as follows.
１ 前記のH2Ｓ処理後、さらにO2中で900〜1400
℃で加熱する。その時の加熱時間は5L以上に
なるように選ぶ。また逆にO2処理を先に施し
た後、H2Ｓガス処理を行つても、また、同時
に施してもよい。同時に行う場合はO2ガスの
導入量をO2：5L以上、H2Ｓ：2L以上と調整し
て行う。1 After the above H 2 S treatment, further 900 to 1400 in O 2
Heat at ℃. The heating time at that time should be chosen to be at least 5L. Conversely, the H 2 S gas treatment may be performed after the O 2 treatment or at the same time. If they are to be carried out at the same time, the amount of O 2 gas introduced should be adjusted to 5 L or more for O 2 and 2 L or more for H 2 S.
２ 前記１におけるO2処理に代え、C2H4ガスに
よる処理（ガス導入量50L以上）を同様に行う
ことができる。2 Instead of the O 2 treatment in 1 above, treatment with C 2 H 4 gas (gas introduction amount of 50 L or more) can be performed in the same manner.
３ H2Ｓ処理、O2処理及びC2H4処理を同時また
は別個に施してもよい。3 H 2 S treatment, O 2 treatment and C 2 H 4 treatment may be performed simultaneously or separately.
なお、前記１，２，３の方法を行う場合は、炭
窒化チタン単結晶の方位に関係なく、優れた安定
性を示すフイールドエミツターを製造することが
できる。これらの方法の場合、O2処理によりチ
ツプ表面に酸化物TiCNOが形成され、炭化水素
ガス中での加熱によりチツプ表面に炭素膜が形成
されるが、その後の強電界の印加により、これら
の表面物質層膜がチツプ先端に移動される。これ
らの表面物質層膜には、硫化物と同様、原子空孔
は殆ど存在しない。表面物質層膜の形成並びに強
電界の印加による作用は、前述の硫化物の場合と
同様である。 Note that when methods 1, 2, and 3 are performed, a field emitter exhibiting excellent stability can be manufactured regardless of the orientation of the titanium carbonitride single crystal. In the case of these methods, oxide TiCNO is formed on the chip surface by O 2 treatment, and a carbon film is formed on the chip surface by heating in hydrocarbon gas, but these surfaces are destroyed by the subsequent application of a strong electric field. A material layer is transferred to the tip of the chip. Similar to sulfides, these surface material layers have almost no atomic vacancies. The formation of the surface material layer and the effects of applying a strong electric field are the same as in the case of sulfide described above.
実施例 １
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
フラツシユ加熱して清浄表面を得た。この系に
H2Ｓガスを導入し、１×10-6Torrの真空度にし
た後、1100℃で10秒間加熱した。（10Lの露出
量）、その後超高真空下で全電流約10μAを30分間
放射（107Ｖ／cm以上の強電界の印加）して、エ
ミツシヨンパターンを第１図より第２図のパター
ンに変化させた。得られたフイールドエミツター
の電流雑音は真空度５×10-12Torrの下で±0.2％
以下、ドリフトは±0.2％／hr以下、その電子放
射特性は第３図ａに示す通りであつた。Example 1 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. to obtain a clean surface. to this system
After introducing H 2 S gas and setting the degree of vacuum to 1×10 −6 Torr, it was heated at 1100° C. for 10 seconds. (exposure amount of 10 L), and then radiated a total current of approximately 10 μA for 30 minutes under ultra-high vacuum (applying a strong electric field of 10 7 V/cm or more) to change the emission pattern from Figure 1 to Figure 2. changed into a pattern. The current noise of the obtained field emitter is ±0.2% under a vacuum degree of 5 × 10 -12 Torr.
Below, the drift was less than ±0.2%/hr, and the electron emission characteristics were as shown in Figure 3a.
実施例 ２
実施例１の方法でTiC0.95N0.01＜110＞フイール
ドエミツターチツプを、H2Ｓで表面処理した後、
この系にC2H4ガスを導入し、１×10-6Torrの真
空度にした後、1100℃で100秒間加熱した。
（100Lの露出量）。Example 2 After surface treating a TiC 0.95 N 0.01 <110> field emitter chip with H 2 S using the method of Example 1,
C 2 H 4 gas was introduced into this system, the vacuum level was set to 1×10 −6 Torr, and the system was heated at 1100° C. for 100 seconds.
(100L exposure amount).
その後、実施例１におけると同様に超高真空下
で107Ｖ／cm以上の強電界を印加してエミツシヨ
ンパターンを第１図から第２図に変化させた。 Thereafter, as in Example 1, a strong electric field of 10 7 V/cm or more was applied under ultra-high vacuum to change the emission pattern from FIG. 1 to FIG. 2.
得られたフイールドエミツターの電流雑音は真
空度５×10-12Torrのもとで±0.2％以下、ドリフ
トは±0.2％／hr以下であり、その特性は第３図
ｂに示す通りであつた。 The current noise of the obtained field emitter was less than ±0.2% under a degree of vacuum of 5 × 10 -12 Torr, and the drift was less than ±0.2%/hr, and its characteristics were as shown in Figure 3b. Ta.
実施例 ３
実施例２におけるC2H4に代えてO2を使用し、
1100℃で20秒間加熱した。（20Lの露出量）。以下
実施例２と同様にしてフイールドエミツターを得
た。得られたフイールドエミツターは実施例２と
同様なものであつた。Example 3 Using O 2 instead of C 2 H 4 in Example 2,
Heated at 1100°C for 20 seconds. (20L exposure volume). Thereafter, a field emitter was obtained in the same manner as in Example 2. The field emitter obtained was similar to that of Example 2.
実施例 ４
実施例２と同様にしてC2H4処理した後、再度
超高真空に排気した後、O2を導入し、１×10-6
Torrの真空度にした後、1100℃で20秒間加熱し
た。（20Lの露出量）。以下実施例２と同様にして
フイールドエミツターを製造した。得られたフイ
ールドエミツターの特性は実施例２と同様のもの
であつた。Example 4 After C 2 H 4 treatment in the same manner as in Example 2, the mixture was evacuated to an ultra-high vacuum again, and then O 2 was introduced and the mixture was heated to 1×10 -6
After creating a vacuum of Torr, it was heated at 1100°C for 20 seconds. (20L exposure volume). A field emitter was manufactured in the same manner as in Example 2. The characteristics of the obtained field emitter were similar to those of Example 2.
発明の効果
本発明の方法によると、炭窒化チタン単結晶か
ら、優れた安定性を示すフイールドエミツターが
容易に製造することができる。Effects of the Invention According to the method of the present invention, a field emitter exhibiting excellent stability can be easily produced from a titanium carbonitride single crystal.
第１図はTiC0.95N0.01＜110＞フイールドエミツ
ターの1500℃フラツシユ加熱後の清浄表面からの
エミツシヨンパターン、第２図は本発明の方法の
処理を施した後のフイールドエミツターからのエ
ミツシヨンパターン、第３図は本発明の方法で製
造したフイールドエミツターの全電流と時間の関
係図で、第３図ａはH2Ｓガスのみにより表面処
理した場合、第３図ｂはH2Ｓ処理後、さらにC2
H4ガス処理を施した場合を示す。
Figure 1 shows the emission pattern from the clean surface of a TiC 0.95 N 0.01 <110> field emitter after flash heating at 1500°C, and Figure 2 shows the emission pattern from the field emitter after processing according to the method of the present invention. Emission pattern, Fig. 3 is a diagram of the relationship between total current and time of a field emitter manufactured by the method of the present invention. After H 2 S treatment, further C 2
This shows the case of H 4 gas treatment.
Claims (1)
〜1400℃の下で、H2ＳまたはＳを含んだガスに
よる表面処理を施した後、超高真空下で、107
Ｖ／cm以上の強電界を印加することを特徴とする
チタン化合物フイールドエミツターの製造方法。 ２ 炭窒化チタン単結晶エミツター表面を、900
〜1400℃の下で、H2ＳまたはＳを含んだガスに
よる表面処理とO2による表面処理とを別個にま
たは同時に施した後、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チタン
化合物フイールドエミツターの製造方法。 ３ 炭窒化チタン単結晶エミツター表面を、900
〜1400℃の下で、H2ＳまたはＳを含んだガスに
よる表面処理とC2H4またはその他の炭化水素ガ
スによる表面処理とを別個にまたは同時に施した
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チタン化合物フイールドエ
ミツターの製造方法。 ４ 炭窒化チタン単結晶エミツター表面を、900
〜1400℃の下で、H2ＳまたはＳを含んだガスに
よる表面処理、O2による表面処理及びC2H4また
はその他の炭化水素ガスによる表面処理を別個に
または同時に施した後、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チタ
ン化合物フイールドエミツターの製造方法。[Claims] 1. Titanium carbonitride single crystal emitter surface
After surface treatment with H 2 S or S-containing gas at ~1400°C, 10 7
A method for producing a titanium compound field emitter, characterized by applying a strong electric field of V/cm or more. 2 The surface of the titanium carbonitride single crystal emitter is
After performing surface treatment with H 2 S or a gas containing S and surface treatment with O 2 separately or simultaneously at ~1400°C, under ultra-high vacuum, 10 7 V/cm
A method for producing a titanium compound field emitter, characterized by applying a strong electric field of the above magnitude. 3 The surface of the titanium carbonitride single crystal emitter is
After surface treatment with H 2 S or S-containing gas and surface treatment with C 2 H 4 or other hydrocarbon gas separately or simultaneously at ~1400°C, 10 7 in ultra-high vacuum. A method for producing a titanium compound field emitter, characterized by applying a strong electric field of V/cm or more. 4 Titanium carbonitride single crystal emitter surface with 900
After surface treatment with H 2 S or S-containing gas, O 2 surface treatment, and surface treatment with C 2 H 4 or other hydrocarbon gas at ~1400°C, either separately or simultaneously, ultra-high temperature Under vacuum, 10 7 V/
A method for producing a titanium compound field emitter, characterized by applying a strong electric field of cm or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60219835A JPS6280938A (en) | 1985-10-02 | 1985-10-02 | Manufacture of titanium compound field emitter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60219835A JPS6280938A (en) | 1985-10-02 | 1985-10-02 | Manufacture of titanium compound field emitter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6280938A JPS6280938A (en) | 1987-04-14 |
| JPH0577134B2 true JPH0577134B2 (en) | 1993-10-26 |
Family
ID=16741794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60219835A Granted JPS6280938A (en) | 1985-10-02 | 1985-10-02 | Manufacture of titanium compound field emitter |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6280938A (en) |
Families Citing this family (2)
| 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 |
| CN106549157A (en) * | 2015-09-18 | 2017-03-29 | 中国科学院宁波材料技术与工程研究所 | Hollow ball shape class graphite-phase C3N4With elemental sulfur composite material and its preparation method and application |
-
1985
- 1985-10-02 JP JP60219835A patent/JPS6280938A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6280938A (en) | 1987-04-14 |
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| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |