JPH03170033A - X-ray transmission window and production thereof - Google Patents
X-ray transmission window and production thereofInfo
- Publication number
- JPH03170033A JPH03170033A JP30970189A JP30970189A JPH03170033A JP H03170033 A JPH03170033 A JP H03170033A JP 30970189 A JP30970189 A JP 30970189A JP 30970189 A JP30970189 A JP 30970189A JP H03170033 A JPH03170033 A JP H03170033A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- diamond
- substrate
- transmittance
- window
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000005540 biological transmission Effects 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000010432 diamond Substances 0.000 claims abstract description 62
- 239000010409 thin film Substances 0.000 claims abstract description 62
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 60
- 239000000758 substrate Substances 0.000 claims abstract description 41
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 20
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010408 film Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 238000010030 laminating Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 238000002834 transmittance Methods 0.000 abstract description 27
- 238000005530 etching Methods 0.000 abstract description 3
- 238000004544 sputter deposition Methods 0.000 abstract description 3
- 238000007740 vapor deposition Methods 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000012808 vapor phase Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
Abstract
Description
本発明はＸ一線に対する透過率が大きく、紫外光から可
視光さらに赤外先に対する透過率の低いＸ一線透過窓及
びその製造方法に関する。The present invention relates to an X-line transmission window that has a high transmittance for the X-line and a low transmittance for visible light from ultraviolet light to infrared light, and a method for manufacturing the same.
【従来の技術｝
Ｘ一線検出器は種々のものがあるが、リチウムを拡散し
たシリコン半導体検出器が近年多く用いられている。
通常この半導体検出器は液体窒素温度に冷却して動作さ
せる必要がある。低温に冷却された検出器の断熱と表面
への結露や汚染の防止のために、検出器の半導体素子の
部分は真空槽内に設置され、真空槽外からくるＸ一線は
、真空を保持し、Ｘ−線に対して透過率の高い窓を通し
て真空槽内の検出器に導く方法が取られている。
また半導体検出器は通常Ｘ一線のみならず、紫外線，可
視光線ないしは赤外線に対しても信号を出すこともあり
、Ｘ一線透過窓を検出器の前面に設置して、紫外線や可
視光線ないしは赤外線等を遮断し、Ｘ一線に対してのみ
感度を持たせる方策も必要とされる。
Ｘ一線透過窓に要求される材料特性は、Ｘ一線に対する
透過率が良好、即ち吸収係数が小さく、厚みが薄くでき
、機械的強度の高いこと等が望まれている。吸収係数は
物質特有の値で、通常Ｘ一線の波長や物質の密度に依存
し、概略原子番号の小さいものほど吸収係数は小さい。
透過率は厚みが薄いほど高いので、できるだけ薄いもの
が望ましい。
この目的のために、従来は厚み約１０ｐｍ程度のＢｅ薄
板が用いられていた．
〔発明が解決しようとする課題〕
しかしながら、従来のべリリウム薄板は、金属ベリリウ
ム板を圧延することによって作製しているが、ｌＯミク
ロン以下の厚みに均一に圧延しにくく、また、たとえ作
製できたとしても、窓としての機械的強度が不足するた
め、実用的でないという問題があった。このため、Ｘ−
線の波長でＩＯＡ以上の低エネルギーＸ一線の透過率が
極端に低下し、Ｘ一線検出器の動作が制限されるという
致命的欠陥があった。
また、Ｘ一線は物質中に吸収され、熱に変わり易く、こ
のため窓材料の温度上昇による熱変形さらには機械的破
壊の問題も生じるため、吸収された熱を速やかに拡散で
きるように、熱拡散率又は熱伝導率は大きく、熱膨張係
数は小さい方が好ましい。
Ｘ一線透過窓の目的に適合できる材料は、種々検討され
てはいたが、これまでベリリウム以外には実用的なもの
はなかった。ダイヤモンドは軽元素でありＸ一線に対し
て透過率が高く、機械的強度や、熱伝導率も大きく、耐
湿性や、耐熱性にも優れた安定な窓材料であるが、高価
でありまた面積も最大で５１Ｍ１程度のものしか容易に
入手できないという問題があった。さらにダイヤモンド
は高度が高く容易に研磨されないため薄い板状にするこ
とが難しいという製造技術上の問題もあった。
またダイヤモンドは可視光や紫外光に対しても透明でＸ
一線だけを透過させる用途には不適当であるという問題
もあった。
本発明の目的は前記課題を解決したＸ一線透過窓及びそ
の製造方法を提供することにある。
〔課題を解決するための手段｝
前記目的を達成するため、本発明に係るＸ一線透過窓に
おいては、所定形状の窓部に主にダイヤモンド多結晶薄
膜からなる膜を形成し、該ダイヤモンド多結晶薄膜上に
金属ベリリウム薄膜を積層したものである．本発明に係
るＸ一線透過窓の製造方法においては、多結晶ダイヤモ
ンド薄膜を基板上に成膜する工程と，該基板を部分的に
除去し、ダイヤモンド多結晶薄膜のみからなる窓を形成
する工程と、該多結晶ダイヤモンド薄膜上の窓の部分に
金属ベリリウム薄膜を形成する工程とを含むものである
．また、本発明に係るＸ一線透過窓の製造方法において
は、シリコン基板上にタングステン、ないしはモリブデ
ン膜を作製し、さらにその上に多結晶ダイヤモンド薄膜
を積層する工程と、該基板を部分的に除去し、ダイヤモ
ンド膜のみからなる窓を形成する工程と、該ダイヤモン
ド多結晶薄膜上に金属ベリリウム薄膜を形成する工程と
を含むものである。
〔作用・原理Ｊ
次に本発明について説明する。
第１図（ａ）〜（イ）は本発明に係るＸ一線透過窓の製
造方法を示す工程図である。
第１図（イ）において、本発明は所定形状の窓部ｌ２ａ
にダイヤモンド微細結晶粒子の集合体からなるダイヤモ
ンド多結晶薄膜目を形成し、該ダイヤモンド多結晶薄膜
ｌ１上に金属ベリリウム薄膜１０を多層構造に設けた窓
を用いることによって、先に述べた種々の欠点を解消す
るものである。
次に本発明の製造方法を図面にしたがって説明する。第
１図０）は基板ｌ２上にダイヤモンド多結晶薄膜１１を
形成する工程を示す。ダイヤモンド多結晶＃ｆｆ！！１
１の形成には、メタンガスと水素の混合ガスを用いた特
開昭５８−９１ １ ００号に記載のような、いわゆる
熱フィラメント法気相合成技術ないしは、特開昭５８−
１１０４９号に記載のようなメタンと水素の混合ガスの
マイクロ波励起を利用するプラズマ気相合或法などが利
用できる。第２図は一例として熱フィラメント法気相合
成装置の概略を示したものである。第２図において、ダ
イヤモンド多結晶薄膜を合成すべき基板２１は基板加熱
装置２２によって加熱し、約６００℃〜９００℃程度に
保つ。メタンガス（ＣＨ，）２３及び水素（Ｈ，）２４
の混合ガスを合成反応装置２５内に導入し、基板２１よ
り上方に設けた約２０００℃に加熱したタングステンフ
ィラメント２６によって熱分解励起し、基板２１上にダ
イヤモンドを析出させる。２７は合或反応装置２５内を
真空排気する排気装置である。この方法によるメタンガ
スの熱分解過程とダイヤモンドの生成過程の詳細は、現
在もなお不明の部分が多く、論議のあることろである。
いずれにしても、要するにダイヤモンド多結晶薄膜１１
が形成できる方法であれば、どの方法でもよい。薄膜を
形成する結晶粒子の粒径と膜中の結晶粒界に存在するダ
イヤモンド以外の不純物量はＸ一線の透過係数及び膜の
均一性を決定するので、合成条件は特に重要である。本
発明では、気相合成法によって作製したダイヤモンド多
結晶薄膜の構造としてはダイヤモンドの結晶粒子と非ダ
イヤモンド物質、即ちグラファイトや水素を含有する非
品質炭素などからなるものを用いる。非晶質相の役割は
ダイヤモンドの異常粒成長を抑さえ、微細なグレインか
らなる膜構造にすることにある。即ち、通常ダイヤモン
ドの成長はダイヤモンド種結晶の上にメタンガス中の炭
素がダイヤモンドとして析出するが、その表面に非ダイ
ヤモンド相が析出すると粒成長は停止する。非ダイヤモ
ンド相の析出がないと、大きなグレインからなる膜とな
り、表面の凹凸が大きく、粒間空孔の存在する膜となり
、その上にベリリウム薄膜がつけにくい問題も発生する
。その比率は膜の合成条件、例えばメタンガスと水素ガ
スの混合比率、基板温度、ガス圧などのダイヤモンド多
結晶薄膜の析出条件に依存するので、合成条件は所望の
特性が得られるように制御する必要がある。薄膜の析出
条件を制御することによって得られるダイヤモンド多結
晶薄膜で、０．０５１ＩＩＩ１〜０．２ｌｌｍ程度の粒
径のダイヤモンド粒子と結晶粒界にグラファイトや水素
を含有する非晶質炭素を含むダイヤモンド多結晶薄膜は
、Ｘ一線領域では透過率は十分に大きくできる。
第１図（ａ）において、基板ｌ２となる材料はシリコン
を用いればよいが、必ずしもシリコン基板である必要は
なく、第１図に示すような製造工程を採用することが可
能な基板であれば特に問題はない。
ダイヤモンド多結晶薄膜ｌ１の厚みは膜の機械的強度と
Ｘ一線の透過率の値が所望の特性になるように選定すれ
ばよい。
ダイヤモンド多結晶薄膜ｌ１を形成した基板１２は、次
に第１図（ロ）に示すように、ダイヤモンド多結晶薄膜
１１のみを残し基板１２を部分的に除去するために、フ
ォトレジストｌ３を用いたパターン形成工程によってレ
ジストパターンを形成する。次に、マスク１４を用いて
基板のエッチング工程によって所望の形状寸法に基板ｌ
２をエッチングによって除去し、第ｌ図（Ｃ）に示すよ
うなダイヤモンド多結晶薄膜Ｉ！のみを残した窓部１２
ａを形成する。基板Ｉ２のエッチングには、シリコン基
板の場合には弗酸と硝酸の混合溶液に浸漬することで行
えばよい。次に、第Ｉ図（イ）に示すように、ダイヤモ
ンド多結晶薄膜ｌｌ上に金属ベリリウム薄膜１０を蒸着
ないしはスバッタ法によって形成する。以上の工程を経
ることによってベリリウム薄膜１０を被覆せしめたダイ
ヤモンド多結晶薄膜１１からなる多層膜を基板ｌ２上に
具備するＸ一線透過窓が製造できる。
以上述べたように本発明によれば、微細粒径化により膜
の均一性を向上したダイヤモンド多結晶薄膜上に金属ベ
リリウム薄膜を設けた窓を利用できるので、Ｘ一線領域
で高い透過率を示し、可視光線領域では、透過率の低い
Ｘ一線透過窓が容易に作製できる。
〔実施例〕
以下、本発明の実施例に基づいて説明する。
（実施例１）
ダイヤモンド多結晶薄膜の成膜には第２図に示すような
気相合或装置を用いた。反応時のガス条件は、水素ガス
中のメタン濃度を０．５％から５％とし、合成圧力をｌ
Ｏトール、基板温度はシリコン基板の表面で６００℃〜
９５０℃とした。以上の条件でダイヤモンド多結晶薄膜
の厚みはほぼ０．３ ミクロンとした。次に、基板の表
面及び裏面にフォトレジストをスピンコーティング法に
より、３１１１１の厚みにコーティングした後、裏面の
基板を除去すべき部分のみレジストを除去し、エッチン
グ窓を形成する。基板の除去には、１：１：２の混合比
率の弗酸（ＨＦ） ，硝酸，酢酸の混合液に浸しエッチ
ングし、ダイヤモンド多結晶薄膜のみを残し、基板を完
全に除去する。その後レジスト剥離材により残留したフ
ォトレジストを除去し、次に、第１図に示す製造工程に
したがって、厚み０．１ ミクロンの金属ベリリウム薄
膜を蒸着法によって多層構造に成膜し、Ｘ一線透過窓が
完成できる。
以上述べた方法によって作製したＸ一線透過窓を用いて
、可視光からＸ一線に対する透過率を評価した。光の透
過率は光源からの光を分光器で分光し、ダイヤモンド多
結晶薄膜の部分に照射し、透過した光の強度を測定する
ことで算定した．紫外線から可視、さらに赤外線領域で
は透過率は、ほぼ５％以下と十分低くできた。Ｘ一線領
域の結果を第３図に示す。第３図に示すように本発明の
方法によって、Ｘ一線領域での透過率は高くできる。従
来のべリリウム窓では波長ＩＯオングストロームになる
と１０％以下となるが、これに比較すると波長が３０オ
ングストローム程度までｌＯ％以上の透過率で良好な特
性を示す。
（実施例２）
ダイヤモンド多結晶薄膜を形戒する基板として、シリコ
ン基板上にタングステン膜及びモリブデン膜を基板温度
４００℃でスパッタ法によって、３ｐｍの厚みに成膜し
たものを用いた。
ダイヤモンド多結晶薄膜の成膜には実施例ｌと同じ方法
を用いた。第１図に示す製造工程にしたがって、実施例
１の方法と同じ手法により、ベリリウムとダイヤモンド
の多層薄膜のみからなる窓を基板上に作製する。
光の透過率は光源からの光を分光器で分光し、ダイヤモ
ンド多結晶薄膜の部分に照射し、透過した光の強度を測
定することで算定した．紫外光から可視さらに赤外線領
域では透過率は低くほぼ５％以下で透過率は十分低くで
きた。Ｘ一線領域の結果を第３図に示す．第３図に示す
ように本発明の方法によって、Ｘ一線領域での透過率の
高い、Ｘ一線透過窓が作製できる．
〔発明の効果】
本発明の方法によれば、Ｘ一線の透過率が大きく、紫外
線や可視光に対する透過率の低い、耐湿性や耐熱性に優
れた安定なＸ一線透過窓を安価に作製できるので、実用
上きわめて有益である。また製造工程から明らかなよう
に特に基板の種類によらないことは明白で、どのような
基板を用いても本発明の効果は損なわれない。[Prior Art] There are various types of X-line detectors, but silicon semiconductor detectors in which lithium is diffused have been widely used in recent years. Typically, this semiconductor detector must be cooled to liquid nitrogen temperature to operate. In order to insulate the detector, which is cooled to a low temperature, and to prevent condensation and contamination on the surface, the semiconductor element of the detector is installed in a vacuum chamber, and the X line coming from outside the vacuum chamber is kept in a vacuum. , a method is used in which X-rays are guided to a detector in a vacuum chamber through a window with high transmittance. In addition, semiconductor detectors usually emit signals not only for the X-rays but also for ultraviolet, visible, or infrared rays. There is also a need for a measure to block the radiation and make it sensitive only to the X line. Material properties required for an X-line transmission window include good transmittance for the X-line, that is, a small absorption coefficient, a thin thickness, and high mechanical strength. The absorption coefficient is a value specific to a substance, and usually depends on the wavelength of the X line and the density of the substance, and the smaller the approximate atomic number, the smaller the absorption coefficient. The thinner the thickness, the higher the transmittance, so it is desirable that it be as thin as possible. For this purpose, a Be thin plate with a thickness of approximately 10 pm has been used. [Problems to be Solved by the Invention] However, conventional beryllium thin plates are produced by rolling metal beryllium plates, but it is difficult to uniformly roll them to a thickness of 10 microns or less, and even if they can be produced, However, there was a problem that it was not practical as it lacked mechanical strength as a window. For this reason, X-
There was a fatal flaw in that the transmittance of low-energy X-rays at wavelengths greater than IOA was extremely reduced, limiting the operation of the X-ray detector. In addition, X-rays are easily absorbed by materials and converted into heat, which can cause problems such as thermal deformation and mechanical destruction due to the temperature rise of the window material. It is preferable that the diffusivity or thermal conductivity is large and the coefficient of thermal expansion is small. Various materials have been studied that can be used for the purpose of X-ray transmission windows, but until now there has been no practical material other than beryllium. Diamond is a light element and has high transmittance to the X line, high mechanical strength and thermal conductivity, and is a stable window material with excellent moisture resistance and heat resistance, but it is expensive and requires a large area. However, there was a problem in that only a maximum of about 51M1 could be easily obtained. Furthermore, because diamond has a high altitude and cannot be easily polished, it is difficult to make it into a thin plate, which is a manufacturing technology problem. Diamonds are also transparent to visible and ultraviolet light.
There was also the problem that it was unsuitable for applications in which only one line was transmitted through. SUMMARY OF THE INVENTION An object of the present invention is to provide an X-ray transmission window that solves the above problems and a method for manufacturing the same. [Means for Solving the Problems] In order to achieve the above object, in the X-ray transmission window according to the present invention, a film mainly consisting of a diamond polycrystalline thin film is formed in the window portion of a predetermined shape, and the diamond polycrystalline film is This is a layered metal beryllium thin film on top of a thin film. The method for manufacturing an X-ray transmission window according to the present invention includes a step of forming a polycrystalline diamond thin film on a substrate, and a step of partially removing the substrate to form a window consisting only of the diamond polycrystalline thin film. , forming a metallic beryllium thin film on the window portion on the polycrystalline diamond thin film. In addition, the method for manufacturing an X-ray transmission window according to the present invention includes the steps of forming a tungsten or molybdenum film on a silicon substrate, further laminating a polycrystalline diamond thin film thereon, and partially removing the substrate. However, the method includes a step of forming a window made of only a diamond film, and a step of forming a metallic beryllium thin film on the diamond polycrystalline thin film. [Operation/Principle J] Next, the present invention will be explained. FIGS. 1(a) to 1(a) are process diagrams showing a method of manufacturing an X-ray transmission window according to the present invention. In FIG. 1(A), the present invention has a window l2a having a predetermined shape.
By using a window in which a diamond polycrystalline thin film consisting of an aggregate of diamond microcrystal particles is formed on the diamond polycrystalline thin film 11 and a metal beryllium thin film 10 is provided in a multilayer structure on the diamond polycrystalline thin film l1, the various drawbacks mentioned above can be solved. This is to eliminate the problem. Next, the manufacturing method of the present invention will be explained with reference to the drawings. FIG. 10) shows the process of forming a diamond polycrystalline thin film 11 on a substrate l2. Diamond polycrystal #ff! ! 1
1 can be formed by the so-called hot filament vapor phase synthesis technique as described in JP-A-58-91-100 using a mixed gas of methane gas and hydrogen, or by JP-A-58-1999.
A plasma vapor phase synthesis method using microwave excitation of a mixed gas of methane and hydrogen, as described in Japanese Patent No. 11049, can be used. FIG. 2 shows an outline of a hot filament vapor phase synthesis apparatus as an example. In FIG. 2, a substrate 21 on which a diamond polycrystalline thin film is to be synthesized is heated by a substrate heating device 22 and maintained at about 600°C to 900°C. Methane gas (CH,) 23 and hydrogen (H,) 24
The mixed gas is introduced into the synthesis reaction apparatus 25 and thermally excited by a tungsten filament 26 heated to about 2000° C. provided above the substrate 21 to precipitate diamond on the substrate 21. Reference numeral 27 denotes an exhaust device for evacuating the inside of the reaction device 25. The details of the process of thermally decomposing methane gas and forming diamonds using this method are still largely unknown and controversial. In any case, in short, the diamond polycrystalline thin film 11
Any method may be used as long as it can form the structure. The synthesis conditions are particularly important because the grain size of the crystal grains forming the thin film and the amount of impurities other than diamond present at the grain boundaries in the film determine the X-ray transmission coefficient and the uniformity of the film. In the present invention, the structure of the diamond polycrystalline thin film produced by the vapor phase synthesis method is composed of diamond crystal particles and non-diamond materials, such as graphite and non-quality carbon containing hydrogen. The role of the amorphous phase is to suppress abnormal grain growth of diamond and create a film structure consisting of fine grains. That is, diamond growth normally occurs when carbon in methane gas precipitates as diamond on a diamond seed crystal, but when a non-diamond phase precipitates on the surface, grain growth stops. If there is no precipitation of the non-diamond phase, the film will consist of large grains, the surface will be highly uneven, the film will have intergranular pores, and the problem arises that it will be difficult to attach a beryllium thin film thereon. The ratio depends on the deposition conditions of the diamond polycrystalline thin film, such as the mixing ratio of methane gas and hydrogen gas, substrate temperature, and gas pressure, so the synthesis conditions must be controlled to obtain the desired characteristics. There is. It is a diamond polycrystalline thin film obtained by controlling the deposition conditions of the thin film.It is a diamond polycrystalline thin film obtained by controlling the deposition conditions of the thin film. A crystal thin film can have a sufficiently high transmittance in the X-line region. In FIG. 1(a), silicon may be used as the material for the substrate l2, but it does not necessarily have to be a silicon substrate, and any substrate that can be manufactured using the manufacturing process shown in FIG. There are no particular problems. The thickness of the diamond polycrystalline thin film l1 may be selected so that the mechanical strength and X-ray transmittance value of the film have desired characteristics. The substrate 12 on which the diamond polycrystalline thin film l1 was formed was then treated with a photoresist l3 in order to partially remove the substrate 12, leaving only the diamond polycrystalline thin film 11, as shown in FIG. 1(b). A resist pattern is formed by a pattern forming process. Next, using the mask 14, the substrate is etched into a desired shape and dimension.
2 is removed by etching to form a diamond polycrystalline thin film I! as shown in FIG. 1(C). Window section 12 with only the remaining part
form a. In the case of a silicon substrate, the substrate I2 may be etched by immersing it in a mixed solution of hydrofluoric acid and nitric acid. Next, as shown in FIG. 1(a), a metal beryllium thin film 10 is formed on the diamond polycrystalline thin film 11 by vapor deposition or sputtering. By going through the above steps, it is possible to manufacture an X-ray transmission window having a multilayer film made of a diamond polycrystalline thin film 11 covered with a beryllium thin film 10 on the substrate 12. As described above, according to the present invention, it is possible to use a window in which a metallic beryllium thin film is provided on a diamond polycrystalline thin film whose film uniformity has been improved by making the grain size finer, so that it exhibits high transmittance in the X-line region. In the visible light region, an X-ray transmission window with low transmittance can be easily produced. [Example] Hereinafter, the present invention will be explained based on an example. (Example 1) A vapor phase deposition apparatus as shown in FIG. 2 was used to form a diamond polycrystalline thin film. The gas conditions during the reaction were such that the methane concentration in the hydrogen gas was 0.5% to 5%, and the synthesis pressure was 1
Otor, substrate temperature is 600℃~ on the surface of silicon substrate
The temperature was 950°C. Under the above conditions, the thickness of the diamond polycrystalline thin film was approximately 0.3 microns. Next, a photoresist is coated on the front and back surfaces of the substrate by a spin coating method to a thickness of 31111, and then the resist is removed only from the portion of the back surface where the substrate should be removed to form an etching window. To remove the substrate, the substrate is etched by immersing it in a mixed solution of hydrofluoric acid (HF), nitric acid, and acetic acid at a mixing ratio of 1:1:2, and the substrate is completely removed, leaving only the diamond polycrystalline thin film. After that, the remaining photoresist was removed using a resist stripping agent, and then a 0.1 micron thick metal beryllium thin film was formed into a multilayer structure by vapor deposition according to the manufacturing process shown in Figure 1, and the X-ray transmission window was can be completed. Using the X-line transmission window produced by the method described above, the transmittance from visible light to the X-line was evaluated. The light transmittance was calculated by dividing the light from the light source with a spectrometer, irradiating it onto the diamond polycrystalline thin film, and measuring the intensity of the transmitted light. Transmittance in the ultraviolet to visible and even infrared regions was sufficiently low, approximately 5% or less. The results for the X-line region are shown in FIG. As shown in FIG. 3, the transmittance in the X-line region can be increased by the method of the present invention. Conventional beryllium windows have a transmittance of less than 10% when the wavelength is 10 angstroms, but compared to this, it shows good characteristics with a transmittance of 10 % or more up to a wavelength of about 30 angstroms. (Example 2) As a substrate on which a diamond polycrystalline thin film was formed, a tungsten film and a molybdenum film were formed to a thickness of 3 pm on a silicon substrate by sputtering at a substrate temperature of 400°C. The same method as in Example 1 was used to form the diamond polycrystalline thin film. According to the manufacturing process shown in FIG. 1 and using the same method as in Example 1, a window consisting only of a multilayer thin film of beryllium and diamond is produced on a substrate. The light transmittance was calculated by dividing the light from the light source with a spectrometer, irradiating it onto the diamond polycrystalline thin film, and measuring the intensity of the transmitted light. In the ultraviolet to visible and infrared regions, the transmittance was low, approximately 5% or less, and the transmittance was sufficiently low. Figure 3 shows the results for the X-line region. As shown in FIG. 3, by the method of the present invention, an X-line transmission window with high transmittance in the X-line region can be fabricated. [Effects of the Invention] According to the method of the present invention, a stable X-line transmission window with high X-line transmittance, low transmittance to ultraviolet rays and visible light, and excellent moisture resistance and heat resistance can be manufactured at low cost. Therefore, it is extremely useful in practice. Further, as is clear from the manufacturing process, it is clear that the invention does not depend on the type of substrate, and the effects of the present invention are not impaired no matter what type of substrate is used.
第１図０，（ロ），（ｃ），（イ）は本発明に係るＸ一
線透過窓の製造方法を示す工程図、第２図はダイヤモン
ド多結晶薄膜を形成する一方法を説明する図、第３図は
実施例ｌ及び実施例２の方法によって得られた透過窓の
特性を示す図である．
ｌＯ・・・ベリリウム薄膜
１１・・・ダイヤモンド多結晶薄膜 ｌ２・・・基板
１２ａ・・・窓部 １３・・・フォト
レジストｌ４・・・マスク
２ｌ・・・ダイヤモンドを形成する基板２２・・・基板
加熱装置 ２３・・・メタンガス２４・・・水
素ガス ２５・・・合成反応装置２６・・
・タングステンフィラメント ２７・・・排気装置特許
出願入 日本電気株式会社
（０．）
？口口口■／４マスク
↑ １１１１１１
（ｂ）
（Ｃ，）
第
１
図
２７頭虜談置
第
２
図Figures 10, (b), (c), and (a) are process diagrams showing a method for manufacturing an X-ray transmission window according to the present invention, and Figure 2 is a diagram illustrating a method for forming a diamond polycrystalline thin film. , FIG. 3 is a diagram showing the characteristics of the transmission windows obtained by the methods of Example 1 and Example 2. lO...Beryllium thin film 11...Diamond polycrystalline thin film l2...Substrate 12a...Window portion 13...Photoresist l4...Mask 2l...Substrate on which diamond is formed 22...Substrate Heating device 23...Methane gas 24...Hydrogen gas 25...Synthesis reaction device 26...
・Tungsten filament 27...Exhaust device patent application filed NEC Corporation (0.)? Mouth mouth mouth ■ / 4 mask ↑ 111111 (b) (C,) 1st figure 27 head prisoner story 2nd figure
Claims (3)
らなる膜を形成し、該ダイヤモンド多結晶薄膜上に金属
ベリリウム薄膜を積層したことを特徴とするＸ−線透過
窓。(1) An X-ray transmission window characterized in that a film mainly composed of a diamond polycrystalline thin film is formed in a window portion of a predetermined shape, and a metal beryllium thin film is laminated on the diamond polycrystalline thin film.
と、該基板を部分的に除去し、ダイヤモンド多結晶薄膜
のみからなる窓を形成する工程と、該多結晶ダイヤモン
ド薄膜上の窓の部分に金属ベリリウム薄膜を形成する工
程とを含むことを特徴とするＸ−線透過窓の製造方法。(2) A step of forming a polycrystalline diamond thin film on a substrate, a step of partially removing the substrate to form a window consisting only of the polycrystalline diamond thin film, and a portion of the window on the polycrystalline diamond thin film. A method for manufacturing an X-ray transmission window, comprising the steps of: forming a metallic beryllium thin film.
デン膜を作製し、さらにその上に多結晶ダイヤモンド薄
膜を積層する工程と、該基板を部分的に除去し、ダイヤ
モンド多結晶薄膜のみからなる窓を形成する工程と、該
ダイヤモンド多結晶薄膜上に金属ベリリウム薄膜を形成
する工程とを含むことを特徴とするＸ−線透過窓の製造
方法。(3) A step of producing a tungsten or molybdenum film on a silicon substrate, and further laminating a polycrystalline diamond thin film thereon, and partially removing the substrate to form a window made only of the diamond polycrystalline thin film. A method for manufacturing an X-ray transmission window, comprising the steps of: forming a metallic beryllium thin film on the diamond polycrystalline thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1309701A JPH0786560B2 (en) | 1989-11-29 | 1989-11-29 | Method for manufacturing X-ray transmission window |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1309701A JPH0786560B2 (en) | 1989-11-29 | 1989-11-29 | Method for manufacturing X-ray transmission window |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03170033A true JPH03170033A (en) | 1991-07-23 |
| JPH0786560B2 JPH0786560B2 (en) | 1995-09-20 |
Family
ID=17996243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1309701A Expired - Lifetime JPH0786560B2 (en) | 1989-11-29 | 1989-11-29 | Method for manufacturing X-ray transmission window |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0786560B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004526965A (en) * | 2001-03-21 | 2004-09-02 | アドバンスト・エレクトロン・ビームズ・インコーポレーテッド | Emission window for electron beam emitter |
| JP2010185665A (en) * | 2009-02-10 | 2010-08-26 | Kobe Steel Ltd | Material for x-ray transmission window, and x-ray transmission window with the material |
| US7919763B2 (en) | 2001-03-21 | 2011-04-05 | Advanced Electron Beams, Inc. | Electron beam emitter |
| CN110192124A (en) * | 2017-01-18 | 2019-08-30 | 牛津仪器技术股份公司 | Radiation window |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5795053A (en) * | 1980-12-05 | 1982-06-12 | Nec Corp | X-ray window |
| JPS63263488A (en) * | 1987-04-21 | 1988-10-31 | ペトロ−カナダ・インコ−ポレ−テツド | Radiation transmitting window |
-
1989
- 1989-11-29 JP JP1309701A patent/JPH0786560B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5795053A (en) * | 1980-12-05 | 1982-06-12 | Nec Corp | X-ray window |
| JPS63263488A (en) * | 1987-04-21 | 1988-10-31 | ペトロ−カナダ・インコ−ポレ−テツド | Radiation transmitting window |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004526965A (en) * | 2001-03-21 | 2004-09-02 | アドバンスト・エレクトロン・ビームズ・インコーポレーテッド | Emission window for electron beam emitter |
| US7919763B2 (en) | 2001-03-21 | 2011-04-05 | Advanced Electron Beams, Inc. | Electron beam emitter |
| US8338807B2 (en) | 2001-03-21 | 2012-12-25 | Hitachi Zosen Corporation | Electron beam emitter |
| JP2010185665A (en) * | 2009-02-10 | 2010-08-26 | Kobe Steel Ltd | Material for x-ray transmission window, and x-ray transmission window with the material |
| CN110192124A (en) * | 2017-01-18 | 2019-08-30 | 牛津仪器技术股份公司 | Radiation window |
| CN110192124B (en) * | 2017-01-18 | 2023-07-25 | 牛津仪器技术股份公司 | Radiation window |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0786560B2 (en) | 1995-09-20 |
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