WO2000046830A1 - Diaphragm plate and its processing method - Google Patents

Diaphragm plate and its processing method Download PDF

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Publication number
WO2000046830A1
WO2000046830A1 PCT/JP2000/000640 JP0000640W WO0046830A1 WO 2000046830 A1 WO2000046830 A1 WO 2000046830A1 JP 0000640 W JP0000640 W JP 0000640W WO 0046830 A1 WO0046830 A1 WO 0046830A1
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Prior art keywords
coating
aperture plate
plate
osmium
cleaning
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French (fr)
Japanese (ja)
Inventor
Hirosi Sato
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DAIWA TECTHNO SYSTEMS Co Ltd
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DAIWA TECTHNO SYSTEMS Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/02—Details
    • H01J37/04—Arrangements of electrodes and associated parts for generating or controlling the discharge, e.g. electron-optical arrangement or ion-optical arrangement
    • H01J37/09—Diaphragms; Shields associated with electron or ion-optical arrangements; Compensation of disturbing fields

Definitions

  • the present invention relates to an aperture plate and a method of processing the same, and more particularly, to a high-precision aperture plate suitable for an electron beam application device such as an electron microscope and a method of processing the same.
  • an aperture plate has been used to adjust a beam diameter of an electron beam.
  • This aperture plate is, for example, a metal plate having a high melting point made of molybdenum or the like and having minute passing holes formed therein, as described in Japanese Patent Application Laid-Open No. H04-204624. The surface was coated with platinum or platinum-palladium to prevent contamination.
  • etching is used as a method of making holes in the aperture plate.
  • a resist used for etching a molybdenum metal plate is a resist used for ordinary semiconductor manufacturing and the like. Unlike the heat exchangers used, they have high heat resistance, corrosion resistance, and acid resistance.
  • the resist used at the time of etching is not completely removed and remains on the surface of the aperture plate, the surface of the residual resist, which is an insulator, may be lost when the aperture plate is mounted on an electron microscope and used.
  • the resolution is not improved due to charging, which affects the electron beam and causes problems such as contamination (impurity source).
  • An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide an aperture plate capable of achieving and maintaining high resolution and a method of processing the same. Disclosure of the invention
  • the present invention is characterized by a washing step capable of completely removing the residual resist from the aperture plate, or a coating step of coating the surface of the aperture plate with osmium.
  • the residual resist of the drawing plate after the hole forming process by etching is more completely removed than in the conventional method, so that problems such as charged contamination, coating peeling, etc. are reduced. And the resolution is improved.
  • the coated osmium forms a hard bond coat layer, and a uniform conductive amorphous thin film at the molecular level is formed on the surface of the aperture plate, so that deterioration of resolution can be prevented.
  • FIG. 1 is an explanatory view showing a cleaning step of a diaphragm plate to which the present invention is applied.
  • FIG. 2 is an explanatory view showing a coating process of an aperture plate to which the present invention is applied.
  • BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail.
  • mi is an explanatory view showing a part of the processing step of the aperture plate to which the present invention is applied.
  • the process of manufacturing an aperture plate for an electron microscope can be broadly divided into three processes.
  • the first step is a step of making a hole of a predetermined size by etching a molybdenum metal plate.
  • the molybdenum plate which is a material, is first baked in a vacuum furnace, finished to a predetermined thickness and surface by a rolling roller, and then heat-treated in a hydrogen furnace in a state of leaning against it. Thereafter, a hole having a predetermined diameter is formed by etching by a known method.
  • the photoresist used at this time is, for example, a mixture of xylene, ethylbenzene, cyclized polyisoprene, and the like. Unlike a resist usually used in semiconductor manufacturing, etc., heat resistance of 100 ° C. or more and corrosion resistance are used. It is highly resistant to sulfuric acid and hydrofluoric acid. Therefore, after drilling holes, the resist is removed to some extent by, for example, a well-known RI RI (reactive ion etching) apparatus, but it is insufficient as an aperture plate, and the aperture plate 10 subjected to the resist removal processing is not enough. The resist still remains on the surface.
  • RI RI reactive ion etching
  • FIG. 1 shows this washing step.
  • the cleaning step first, ten aperture plates (10) in which holes are completed are prepared. Then, 50 cc (11) of " ⁇ GR sulfuric acid” (concentration: 97%, for precision analysis) was put into a beaker, and this was heated to 80 degrees Celsius to 12 degrees by any known heating device. Heat to 0 degrees. Then, put 10 diaphragm plates in the heated UGR sulfuric acid 11 and maintain the temperature for 10 to 20 minutes.
  • ⁇ GR sulfuric acid concentration: 97%, for precision analysis
  • An EL mixture is a mixture of EL sulfuric acid (96% concentration, for electronics industry) and EL hydrogen peroxide solution (30% concentration, for electronics industry) in a ratio of 4: 1 to 6: 1. It is.
  • the beaker is set in the ultrasonic cleaning device 15 for about 40 seconds to 1 minute, and the aperture plate 13 is cleaned. Discard the EL mixture 14 after washing.
  • the distilled water 17 heated to 40 to 50 degrees Celsius is poured into a beaker containing the diaphragm plate 16 and poured and washed. This is repeated twice. Furthermore, take the squeezing plate in a net basket, put the basket in a beaker, add 15 O cc of distilled water heated to 40 to 50 degrees Celsius, and set it in the ultrasonic cleaning device 15.
  • FIG. 2 is an explanatory view showing a coating step of the present invention.
  • the gas in the vacuum vessel 21 of the coating apparatus 20 is exhausted.
  • a rotary pump is used for evacuation in a commercially available coating apparatus 20, but a rotary pump can obtain only a vacuum degree of about 10 ⁇ 2 Torr.
  • a metal diaphragm plate is coated at such a low vacuum, a uniform film thickness is formed on the surface of the diaphragm plate, unlike the film formation on the insulator surface, which is the purpose of a commercially available coating device.
  • a cleaning process as a pretreatment is sufficiently performed, and in the coating process, for example, a well-known oil diffusion (diffusion) is used as an exhaust pump. ) Use a pump to secure a vacuum of 10 minus 4 to 5 torr.
  • an inert gas such as an argon gas, a helium gas, or a nitrogen gas after the evacuation and exhausting the gas again, the concentration of oxygen and water vapor can be further reduced.
  • the injection of the inert gas and the exhaust may be repeated a plurality of times.
  • the present invention by reducing the concentration of the impurity gas by the above-described method, the occurrence of unevenness in the coating film thickness is eliminated, and uniform film formation can be stably performed.
  • Oxmium tetroxide is used as the metal to be coated.
  • the aperture plate was coated with platinum or platinum-palladium, there was a problem that the metal was crystallized (granulated) and the coating surface was not uniform and smooth.
  • the uniformity was not obtained. It becomes a hard amorphous thin film and has better conductivity than conventional metals.
  • the melting point of osmium is as high as 270 degrees Celsius, and there is no damage due to electron beam irradiation of an electron microscope.Therefore, it is possible to irradiate a sufficiently focused strong electron beam at a high accelerating voltage. The resolution can be brought out to the limit.
  • a commercially available coating device can be applied to the coating process.
  • a plasma coating device (NL-OPC80N) manufactured by Japan Laser Electronics Co., Ltd. may be applied.
  • a plasma coating device (NL-OPC80N) manufactured by Japan Laser Electronics Co., Ltd. may be applied.
  • a small amount of osmium tetroxide crystal placed in a sublimation cylinder is introduced into a small-capacity gas reactor equipped with an anode plate and a cathode plate, and a dilute sublimation gas pressure is applied.
  • a glow discharge is generated at a flowing glow discharge voltage. Then, the space between the electrodes instantly becomes a plasma state and emits light.
  • ionized osmium molecules are instantaneously adhered and deposited on the surface of the diaphragm 18 placed in the negative glo phase region on the cathode plate, and an amorphous osmium thin film is formed.
  • the film thickness to be coated is about several nanometers to several tens of nanometers.
  • the present invention may have the following modifications.
  • the combination of the cleaning step and the coating step is disclosed.However, for example, only the cleaning step or the coating step alone has an effect of improving the resolution as compared with the conventional aperture plate. It may be performed alone.
  • the holes in the aperture plate can be opened by electric discharge machining, machining, laser machining, electronic beam machining, etc., in addition to etching. In such a case, as described above, by applying an osmium coating, The effect can be expected.
  • a metal other than molybdenum as the material of the aperture plate, for example, a metal having a lower melting point than molybdenum. Even in such a case, by applying the osmium coating, the surface of the aperture plate is covered with the conductive thin film having a high melting point, so that the above-described effects can be expected.
  • the case where the aperture plate is newly manufactured is disclosed.
  • impurities adhere or the coating is peeled off.
  • both the cleaning process and the coating process of the present invention or only one of them may be performed.
  • the present invention is not limited to the aperture plate of the electron microscope, and can be applied to processing of parts of an apparatus that handles an arbitrary electron beam. is there. Industrial applicability
  • the hole by etching is obtained. Residual resist on the aperture plate after blanking is more completely removed as compared with the conventional method, so that problems such as charging / contamination and peeling of coating are reduced and resolution is improved. There is.
  • the coated osmium becomes a hard amorphous conductive film, there is an effect that deterioration of resolution can be prevented. Since osmium has a higher melting point than platinum, performance can be further improved by further coating osmium on a conventional platinum-coated drawing plate.
  • the aperture plate of the present invention can achieve high resolution and maintain the performance.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

A method for processing a diaphragm plate of, e.g., an electron microscope, comprising a cleaning step of cleaning the residual resist on a diaphragm plate in which a hole is made by etching with hot concentrated sulfuric acid or a hot aqueous solution of hydrogen peroxide and a coating step of coating the diaphragm plate with osmium. The residual resist can be more completely removed than conventional. As a result, the problems such as the charging, contamination, and separation of the coating are suppressed, and the resolution is improved. The osmium coating comes to serve as a hard noncrystalline conductive film, thereby preventing degradation of the resolution.

Description

明 細 書 - 絞りプレートおよびその処理方法 技術分野  Description-Aperture plate and processing method therefor

本発明は絞りプレートおよびその処理方法に関し、 特に、 電子顕微鏡 等の電子線応用装置に好適な高精度な絞りプレートおよびその処理方法 に関するものである。 背景技術  The present invention relates to an aperture plate and a method of processing the same, and more particularly, to a high-precision aperture plate suitable for an electron beam application device such as an electron microscope and a method of processing the same. Background art

従来、 電子顕微鏡等の電子線応用装置において、 電子線のビーム径を 調節するために絞りプレー卜が使用されていた。 この絞りプレートは、 例えば特開平 0 4— 2 0 6 2 4 4号公報に記載されているように、 モリ ブデン製等の高融点の金属板に微小な通過孔を空けたものであり、 帯電 やコンタミネ一シヨン防止のために、 表面に白金や白金パラジウムなど のコ一ティングが施されていた。  Conventionally, in an electron beam application device such as an electron microscope, an aperture plate has been used to adjust a beam diameter of an electron beam. This aperture plate is, for example, a metal plate having a high melting point made of molybdenum or the like and having minute passing holes formed therein, as described in Japanese Patent Application Laid-Open No. H04-204624. The surface was coated with platinum or platinum-palladium to prevent contamination.

前記したような、 従来の絞りプレートにおいては、 絞りプレートの孔 を空ける方法としてエッチングを使用しているが、 モリブデン製の金属 板のエッチングに使用するレジストは、 通常の半導体製造等に用いるレ ジス トとは異なり、 耐熱性、 耐蝕性、 耐酸性に富んだものを使用してい る。 ところが、 エッチング時に使用するレジストが完全に除去されずに、 絞りプレー卜の表面に残留していると、 絞りプレートを電子顕微鏡に装 着して使用した場合に、 絶縁物である残留レジストの表面が帯電して電 子線に影響を与えたり、 コンタミネーシヨン （不純物源） 等の問題が発 生し、 分解能が上がらないという問題点があった。  As described above, in the conventional aperture plate, etching is used as a method of making holes in the aperture plate. However, a resist used for etching a molybdenum metal plate is a resist used for ordinary semiconductor manufacturing and the like. Unlike the heat exchangers used, they have high heat resistance, corrosion resistance, and acid resistance. However, if the resist used at the time of etching is not completely removed and remains on the surface of the aperture plate, the surface of the residual resist, which is an insulator, may be lost when the aperture plate is mounted on an electron microscope and used. However, there is a problem that the resolution is not improved due to charging, which affects the electron beam and causes problems such as contamination (impurity source).

また、 白金等をコーティングしても、 レジストが残留している部分に おいてコ一ティングした金属が電子線の通過による加熱の繰り返しによ つて蒸発し、 剥離しやすくなるという熱ダメージの問題点があった。 そ して、 この蒸発によって絶縁物であるレジストが表面に現れ、 前述した ような問題点が再現するという問題点があった。 Also, even when coating with platinum, etc., However, there has been a problem of thermal damage that the coated metal evaporates due to repeated heating by passing an electron beam and is easily separated. The evaporation causes a resist, which is an insulating material, to appear on the surface, and the above-described problem is reproduced.

本発明の目的は、 前記のような従来技術の問題点を解決し、 高い分解 能を達成し、 維持することが可能な絞りプレートおよびその処理方法を 提供することにある。 発明の開示  An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide an aperture plate capable of achieving and maintaining high resolution and a method of processing the same. Disclosure of the invention

本発明は、 絞りプレートの残留レジス トをより完全に除去可能な洗浄 工程、 あるいは絞りプレートの表面にォスミゥムをコーティングするコ 一ティング工程に特徴がある。  The present invention is characterized by a washing step capable of completely removing the residual resist from the aperture plate, or a coating step of coating the surface of the aperture plate with osmium.

本発明によれば、 エッチングによる孔空け加工後の絞りプレー卜の残 留レジストが従来の方法と比べてより完全に除去されるので、 帯電ゃコ ンタミネ一シヨン、 コーティングの剥離等の問題が減少し、 分解能が向 上する。 更に、 コーティングされたオスミウムは硬い結合被膜層を作り、 絞りプレート表面に分子レベルの均一な導電性非結晶薄膜が形成される ので分解能の劣化が防止できる。 図面の簡単な説明  According to the present invention, the residual resist of the drawing plate after the hole forming process by etching is more completely removed than in the conventional method, so that problems such as charged contamination, coating peeling, etc. are reduced. And the resolution is improved. In addition, the coated osmium forms a hard bond coat layer, and a uniform conductive amorphous thin film at the molecular level is formed on the surface of the aperture plate, so that deterioration of resolution can be prevented. BRIEF DESCRIPTION OF THE FIGURES

第 1図は、 本発明を適用した絞りプレートの洗浄工程を示す説明図で ある。  FIG. 1 is an explanatory view showing a cleaning step of a diaphragm plate to which the present invention is applied.

第 2図は本発明を適用した絞りプレートのコーティング工程を示す説 明図である。 発明を実施するための最良の形態 以下、 本発明の実施の形態を詳細に説明する。 m iは、 本発明を適用 した絞りプレートの処理工程の一部を示す説明図である。 例えば電子顕 微鏡用の絞りプレートを製造する場合の工程は、 大きく 3つの工程に分 けられる。 FIG. 2 is an explanatory view showing a coating process of an aperture plate to which the present invention is applied. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail. mi is an explanatory view showing a part of the processing step of the aperture plate to which the present invention is applied. For example, the process of manufacturing an aperture plate for an electron microscope can be broadly divided into three processes.

まず第 1の工程は、 モリブデン製の金属板にエッチングによって所定 の大きさの孔を空ける工程である。 材料であるモリブデン板は、 まず真 空炉内において焼成処理され、 圧延ローラによつて所定の厚さおよぴ表 面に仕上げられた後、 水素炉内において立て掛けた状態で熱処理される。 その後、 公知の方法によって所定径の孔がエッチングによって空けられ る。  First, the first step is a step of making a hole of a predetermined size by etching a molybdenum metal plate. The molybdenum plate, which is a material, is first baked in a vacuum furnace, finished to a predetermined thickness and surface by a rolling roller, and then heat-treated in a hydrogen furnace in a state of leaning against it. Thereafter, a hole having a predetermined diameter is formed by etching by a known method.

この際に使用されるフォ トレジス トは、 例えばキシレン、 ェチルベン ゼン、 環化ポリイソプレン等の混合物であり、 通常半導体製造等に用い るレジストとは異なり、 1 0 0 0度以上の耐熱性、 耐蝕性、 更に硫酸や フッ酸に対する耐酸性に富んでいる。 従って、 孔空け後には例えば周知 の R I Ε (反応性イオンエッチング） 装置によってある程度はレジス ト が除去されるが、 絞りプレートとしては不十分であり、 レジスト除去処 理された絞りプレ一ト 1 0の表面には依然としてレジストが残留してい る。  The photoresist used at this time is, for example, a mixture of xylene, ethylbenzene, cyclized polyisoprene, and the like. Unlike a resist usually used in semiconductor manufacturing, etc., heat resistance of 100 ° C. or more and corrosion resistance are used. It is highly resistant to sulfuric acid and hydrofluoric acid. Therefore, after drilling holes, the resist is removed to some extent by, for example, a well-known RI RI (reactive ion etching) apparatus, but it is insufficient as an aperture plate, and the aperture plate 10 subjected to the resist removal processing is not enough. The resist still remains on the surface.

本発明の実施例の方法においてはこのレジストを除去するために洗浄 工程を行う。 図 1はこの洗浄工程を示している。 洗浄工程においては、 まず孔空けが完了した絞り板 1 0枚 （1 0 ) を用意する。 そして、 「υ G R硫酸」 （濃度 9 7 %、 精密分析用） 5 0 cc ( 1 1 ) をビーカ一に入 れ、 これを公知の任意の加熱装置 1 2によって、 摂氏 8 0度〜 1 2 0度 に加熱する。 そして、 加熱した U G R硫酸 1 1中に絞り板 1 0枚を入れ、 そのまま 1 0〜2 0分間温度を維持する。  In the method of the embodiment of the present invention, a cleaning step is performed to remove the resist. FIG. 1 shows this washing step. In the cleaning step, first, ten aperture plates (10) in which holes are completed are prepared. Then, 50 cc (11) of "υ GR sulfuric acid" (concentration: 97%, for precision analysis) was put into a beaker, and this was heated to 80 degrees Celsius to 12 degrees by any known heating device. Heat to 0 degrees. Then, put 10 diaphragm plates in the heated UGR sulfuric acid 11 and maintain the temperature for 10 to 20 minutes.

その後に、 U G R硫酸 1 1のみを廃棄し、 絞り板 1 0が入っているビ 一力一に摂氏 3 0度〜 7 0度に加熱した 「E L混合液」 5 0 cc ( 1 4 ) を注入する。 E L混合液とは、 E L硫酸 （濃度 9 6 %、 電子工業用） と E L過酸化水素水 （濃度 3 0 %、 電子工業用） とを 4対 1〜6対 1の割 合で混合したものである。 このビーカ一を 4 0秒から 1分程度超音波洗 浄装置 1 5にセットして絞り板 1 3を洗浄する。 洗浄後に E L混合液 1 4は廃棄する。 After that, only the UGR sulfuric acid 11 is discarded, and the bottle containing the diaphragm 10 is removed. Inject 50 cc (14) of the “EL mixture” heated to 30 to 70 degrees Celsius. An EL mixture is a mixture of EL sulfuric acid (96% concentration, for electronics industry) and EL hydrogen peroxide solution (30% concentration, for electronics industry) in a ratio of 4: 1 to 6: 1. It is. The beaker is set in the ultrasonic cleaning device 15 for about 40 seconds to 1 minute, and the aperture plate 13 is cleaned. Discard the EL mixture 14 after washing.

次に、 絞り板 1 6の入ったビーカーに摂氏 4 0度〜 5 0度に加熱した 蒸留水 1 7を注入して注ぎ洗浄を行い、 これを 2回繰り返す。 更に、 絞 り板を網製かごに取り、 かごごとビーカ一に入れて、 摂氏 4 0度〜 5 0 度に加熱した蒸留水を 1 5 O cc加えて超音波洗浄装置 1 5にセットし、 Next, the distilled water 17 heated to 40 to 50 degrees Celsius is poured into a beaker containing the diaphragm plate 16 and poured and washed. This is repeated twice. Furthermore, take the squeezing plate in a net basket, put the basket in a beaker, add 15 O cc of distilled water heated to 40 to 50 degrees Celsius, and set it in the ultrasonic cleaning device 15.

1〜 2分間超音波洗浄を行う。 この超音波洗浄を数回繰り返す。 最後に、 絞り板を 1枚づっ取り出してミクロチューブに挿入し、 摂氏数百度程度 で加熱乾燥させる。 Perform ultrasonic cleaning for 1-2 minutes. This ultrasonic cleaning is repeated several times. Finally, take out the squeezing plates one by one, insert them into a microtube, and heat and dry at several hundred degrees Celsius.

発明者は、 洗浄工程処理後の絞り板を電子顕微鏡でチェックすること により、 上記した洗浄工程によってエッチング工程後に残留していた乾 燥レジストはほぼ完全に除去されることを確認した。  The inventor confirmed that the dry resist remaining after the etching step was almost completely removed by the above-described cleaning step by checking the aperture plate after the cleaning step processing with an electron microscope.

次にコ一ティング工程について説明する。 図 2は、 本発明のコーティ ング工程を示す説明図である。 コーティング工程においては、 まず、 コ 一ティング装置 2 0の真空容器 2 1内の気体を排気する。 市販のコ一テ ィング装置 2 0には排気用に通常ロータリーポンプが使用されているが、 ロータリ一ポンプでは 1 0のマイナス 2乗トール（Torr)程度の真空度し か得られない。 この程度の低真空度で金属製である絞り板のコーティン グを実施すると、 市販のコーティング装置の目的である絶縁物表面への 成膜と違って、 絞り板の表面には均一な膜厚が出来難く、 むらになって しまうことが実験により判明した。 むらの出来る理由は明確ではないが、 絞り板の表面に残留している脂肪成分の影響と共に、 真空容器内に残留 している酸素や水蒸気等の影響によるものと推定される。 Next, the coating step will be described. FIG. 2 is an explanatory view showing a coating step of the present invention. In the coating step, first, the gas in the vacuum vessel 21 of the coating apparatus 20 is exhausted. In general, a rotary pump is used for evacuation in a commercially available coating apparatus 20, but a rotary pump can obtain only a vacuum degree of about 10 −2 Torr. When a metal diaphragm plate is coated at such a low vacuum, a uniform film thickness is formed on the surface of the diaphragm plate, unlike the film formation on the insulator surface, which is the purpose of a commercially available coating device. Experiments have shown that it is difficult to do so and it becomes uneven. The reason for the unevenness is not clear, but it remains in the vacuum vessel due to the effect of fat remaining on the surface of the diaphragm. It is presumed to be due to the influence of oxygen, water vapor and the like.

そこで、 金属製絞り板表面へのコーティングを行う本発明の実施例に おいては、 前処理である洗浄処理を充分行うと共に、 コーティング工程 においては、 排気用ポンプとして例えば周知の油拡散 （ディフュージョ ン） ポンプを使用することによって 1 0のマイナス 4〜 5乗トールの真 空度を確保する。  Therefore, in the embodiment of the present invention in which the surface of the metal diaphragm plate is coated, a cleaning process as a pretreatment is sufficiently performed, and in the coating process, for example, a well-known oil diffusion (diffusion) is used as an exhaust pump. ) Use a pump to secure a vacuum of 10 minus 4 to 5 torr.

また、 排気後にアルゴンガス、 ヘリウムガス、 窒素ガス等の不活性ガ スを注入し、 再び排気することによって酸素や水蒸気の濃度を更に低下 させることができる。 なお、 不活性ガスの注入と排気とを複数回繰り返 すようにしてもよい。  In addition, by injecting an inert gas such as an argon gas, a helium gas, or a nitrogen gas after the evacuation and exhausting the gas again, the concentration of oxygen and water vapor can be further reduced. The injection of the inert gas and the exhaust may be repeated a plurality of times.

本発明においては、 以上のような方法によって不純物ガスの濃度を低 下させたことにより、 コーティング膜厚のむらの発生がなくなり、 均一 な成膜を安定して実施可能となった。  In the present invention, by reducing the concentration of the impurity gas by the above-described method, the occurrence of unevenness in the coating film thickness is eliminated, and uniform film formation can be stably performed.

コーティングする金属としては四酸化ォスミゥムを使用する。 絞り板 に白金や白金パラジウムをコーティングした場合には金属が結晶化 （粒 状化） し、 コーティング表面が均一で滑らかにならないという問題点が あつたが、 本発明によるォスミゥムの場合には均一で硬いアモルファス 薄膜となり、 導電性も従来の金属より更に良好である。 また、 ォスミゥ ムの融点は摂氏 2 7 0 0度と高く、 電子顕微鏡の電子線照射によるダメ ージがないので、 高い加速電圧で充分絞った強い電子線を照射すること ができ、 電子顕微鏡の分解能を限界まで引き出せる。  Oxmium tetroxide is used as the metal to be coated. When the aperture plate was coated with platinum or platinum-palladium, there was a problem that the metal was crystallized (granulated) and the coating surface was not uniform and smooth. However, in the case of the osmmium according to the present invention, the uniformity was not obtained. It becomes a hard amorphous thin film and has better conductivity than conventional metals. In addition, the melting point of osmium is as high as 270 degrees Celsius, and there is no damage due to electron beam irradiation of an electron microscope.Therefore, it is possible to irradiate a sufficiently focused strong electron beam at a high accelerating voltage. The resolution can be brought out to the limit.

コ一ティング処理には、 市販されているコーティング装置を応用可能 であり、 例えば日本レーザ電子株式会社のプラズマコーティング装置 (NL-OPC80N)を応用してもよい。 このプラズマコーティング装置は、 陽 極板と陰極板を設置した小容量ガス反応器内に、 昇華筒に入れた少量の 四酸化オスミウム結晶を導入し、 希薄な昇華ガス圧にして、 選定した直 流グロ一放電電圧でグロ一放電を発生させる。 すると、 電極間が瞬時に プラズマ状態となって発光する。 この時、 陰極板上の負グロ一相領域内 に置いた絞り板 1 8の表面には、 イオン化オスミウム分子が瞬時に付着 堆積して非結晶オスミウム薄膜ができる。 コーティングする膜厚は数ナ ノメートルから数十ナノメートル程度とする。 A commercially available coating device can be applied to the coating process. For example, a plasma coating device (NL-OPC80N) manufactured by Japan Laser Electronics Co., Ltd. may be applied. In this plasma coating apparatus, a small amount of osmium tetroxide crystal placed in a sublimation cylinder is introduced into a small-capacity gas reactor equipped with an anode plate and a cathode plate, and a dilute sublimation gas pressure is applied. A glow discharge is generated at a flowing glow discharge voltage. Then, the space between the electrodes instantly becomes a plasma state and emits light. At this time, ionized osmium molecules are instantaneously adhered and deposited on the surface of the diaphragm 18 placed in the negative glo phase region on the cathode plate, and an amorphous osmium thin film is formed. The film thickness to be coated is about several nanometers to several tens of nanometers.

以上のような処理によって、 絞り板に残留しているレジストを完全に 除去し、 更に硬くて導電性の良好なオスミウムの非結晶薄膜によってコ —ティングするので、 電子顕微鏡に使用した場合に高い分解能が得られ る。  The above process completely removes the resist remaining on the aperture plate and coats it with a hard, non-conductive amorphous thin film of osmium, which provides high resolution when used in an electron microscope. Is obtained.

以上、 本発明の実施例を開示したが、 本発明には下記のような変形例 も考えられる。 実施例においては、 洗浄工程およびコーティング工程の 組み合わせについて開示したが、 例えば洗浄工程のみ、 あるいはコ一テ ィング工程のみでも従来の絞りプレートと比較して分解能の向上効果は あるので、 各工程のみを単独で実施してもよい。 例えば、 絞りプレート の孔はエッチング以外に放電加工、 機械加工、 レーザ一加工、 電子ビー ム加工等によって開けることも可能であり、 このような場合においても、 ォスミゥムのコーティングを施すことによって前記したような効果が期 待できる。  Although the embodiments of the present invention have been disclosed above, the present invention may have the following modifications. In the embodiment, the combination of the cleaning step and the coating step is disclosed.However, for example, only the cleaning step or the coating step alone has an effect of improving the resolution as compared with the conventional aperture plate. It may be performed alone. For example, the holes in the aperture plate can be opened by electric discharge machining, machining, laser machining, electronic beam machining, etc., in addition to etching. In such a case, as described above, by applying an osmium coating, The effect can be expected.

また、 絞りプレートの材質としてモリブデン以外の金属、 例えばモリ ブデンよりも融点の低い金属を使用することも可能である。 このような 場合においても、 オスミウムのコーティングを施すことによって、 絞り プレートの表面が高融点の導電性薄膜で覆われるので、 前記したような 効果が期待できる。  It is also possible to use a metal other than molybdenum as the material of the aperture plate, for example, a metal having a lower melting point than molybdenum. Even in such a case, by applying the osmium coating, the surface of the aperture plate is covered with the conductive thin film having a high melting point, so that the above-described effects can be expected.

実施例においては、 絞りプレートを新規に製造する場合を開示したが、 例えば絞りプレートを電子顕微鏡に搭載して使用していくと不純物が付 着したりコーティングが剥がれたりするので、 使用した絞りプレートの 再生処理として本発明の洗浄処理およびコーティ-ング処理の両方あるい は一方のみを実施してもよい。 In the embodiment, the case where the aperture plate is newly manufactured is disclosed.For example, when the aperture plate is mounted on an electron microscope and used, impurities adhere or the coating is peeled off. of As the regenerating process, both the cleaning process and the coating process of the present invention or only one of them may be performed.

実施例においては、 電子顕微鏡における絞りプレートに本発明を適用 する例を開示したが、 本発明は、 電子顕微鏡の絞りプレートに限らず、 任意の電子線を扱う装置の部品の処理に適用可能である。 産業上の利用可能性  In the embodiment, the example in which the present invention is applied to the aperture plate of the electron microscope is disclosed. However, the present invention is not limited to the aperture plate of the electron microscope, and can be applied to processing of parts of an apparatus that handles an arbitrary electron beam. is there. Industrial applicability

以上述べたように、 本発明においては、 絞りプレートの残留レジスト をより完全に除去可能な洗浄工程、 あるいは絞りプレートの表面にォス ミゥムをコーティングするコーティング工程を実施することにより、 ェ ツチングによる孔空け加工後の絞りプレートの残留レジス卜が従来の方 法と比べてより完全に除去されるので、 帯電ゃコンタミネーシヨン、 コ —ティングの剥離等の問題が減少し、 分解能が向上するという効果があ る。  As described above, in the present invention, by performing a cleaning step of completely removing the residual resist on the aperture plate or a coating step of coating the surface of the aperture plate with osmium, the hole by etching is obtained. Residual resist on the aperture plate after blanking is more completely removed as compared with the conventional method, so that problems such as charging / contamination and peeling of coating are reduced and resolution is improved. There is.

更に、 コーティングされたオスミウムは硬質な非結晶状態の導電膜と なるので、 分解能の劣化が防止できるという効果もある。 オスミウムは 白金よりも融点が高いので、 従来の白金をコーティングした絞りプレー トに更にォスミゥムをコーティングすることにより更に性能を向上させ ることができる。  Furthermore, since the coated osmium becomes a hard amorphous conductive film, there is an effect that deterioration of resolution can be prevented. Since osmium has a higher melting point than platinum, performance can be further improved by further coating osmium on a conventional platinum-coated drawing plate.

従って、 本発明の絞りプレートは高い分解能を達成し、 また該性能を 維持することが可能である。  Therefore, the aperture plate of the present invention can achieve high resolution and maintain the performance.

Claims

請 求 の 範 囲 - The scope of the claims - 1 . 微小な孔を空けた金属板にォスミゥムのコ一ティングを施すコーテ ィング工程を含むことを特徴とする絞りプレートの処理方法。 1. A method for treating an aperture plate, comprising a coating step of applying an osmium coating to a metal plate having minute holes. 2 . エッチングによって微小な孔を空けたモリブデン製の板を加熱した 濃硫酸および過酸化水素水により洗浄する洗浄工程を含むことを特徴と する絞りプレートの処理方法。 2. A method for treating an aperture plate, comprising a cleaning step of cleaning a molybdenum plate having minute holes formed by etching with heated concentrated sulfuric acid and hydrogen peroxide solution. 3 . エッチングによって微小な孔を空けたモリブデン製の板を加熱した 濃硫酸および過酸化水素水により洗浄する洗浄工程と、  3. a cleaning step of cleaning the molybdenum plate having minute holes formed by etching with heated concentrated sulfuric acid and hydrogen peroxide solution; 洗浄した前記板にォスミゥムのコーティングを施すコ一ティング工程 と  A coating step of applying an osmium coating to the washed plate; を含むことを特徴とする絞りブレートの処理方法。 A processing method of an aperture plate. 4 . 前記洗浄工程は、  4. The washing step 摂氏 8 0度から 1 2 0度に加熱した濃硫酸により洗浄する第 1の洗浄 工程と、  A first washing step of washing with concentrated sulfuric acid heated from 80 degrees Celsius to 120 degrees Celsius; 濃硫酸および過酸化水素水を 3対 1から 7対 1の割合で混合し、 摂氏 3 0度から Ί 0度に加熱した混合液により超音波洗浄する第 2の洗浄ェ 程と、  A second cleaning step in which concentrated sulfuric acid and aqueous hydrogen peroxide are mixed at a ratio of 3: 1 to 7: 1, and ultrasonically cleaned with a mixture heated to 30 to 0 degrees Celsius; 蒸留水により洗浄する第 3の洗浄工程と  A third washing step of washing with distilled water を含むことを特徴とする特許請求の範囲第 2項記載の絞りプレートの処 理方法。 3. The method for processing an aperture plate according to claim 2, wherein the method includes: 5 . 前記コーティング工程は、  5. The coating step 1 0のマイナス 4乗トール以上の真空度を達成可能なポンプおよび不 活性ガスを使用してプラズマコーティングを行う容器内の不純物気体を 排気する第 1のコ一ティング工程と、  A first coating step of evacuating an impurity gas in a vessel for performing plasma coating using a pump and an inert gas capable of achieving a degree of vacuum of 10 −4 Torr or more; プラズマコーティングによって前記板にォスミゥムのコ一ティングを 施す第 2のコ一ティング工程と、 - を含むことを特徴とする特許請求の範囲第 1項記載の絞りプレートの処 理方法。 Coating of osmium on the plate by plasma coating 2. The method for processing an aperture plate according to claim 1, further comprising: a second coating step to be performed. 6 . 前記特許請求の範囲第 1項乃至第 5項に記載された処理方法によつ て処理されたことを特徴とする絞りプレート。  6. An aperture plate processed by the processing method according to any one of claims 1 to 5.
PCT/JP2000/000640 1999-02-08 2000-02-07 Diaphragm plate and its processing method Ceased WO2000046830A1 (en)

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