JPH0319947B2 - - Google Patents
Info
- Publication number
- JPH0319947B2 JPH0319947B2 JP58012342A JP1234283A JPH0319947B2 JP H0319947 B2 JPH0319947 B2 JP H0319947B2 JP 58012342 A JP58012342 A JP 58012342A JP 1234283 A JP1234283 A JP 1234283A JP H0319947 B2 JPH0319947 B2 JP H0319947B2
- Authority
- JP
- Japan
- Prior art keywords
- magnetic field
- sweep
- electric field
- detector
- ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000002500 ions Chemical class 0.000 claims description 35
- 230000005684 electric field Effects 0.000 claims description 20
- 238000004458 analytical method Methods 0.000 claims description 7
- 238000010408 sweeping Methods 0.000 claims description 7
- 238000004949 mass spectrometry Methods 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- 101700004678 SLIT3 Proteins 0.000 description 1
- 102100027339 Slit homolog 3 protein Human genes 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/022—Circuit arrangements, e.g. for generating deviation currents or voltages ; Components associated with high voltage supply
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Electron Tubes For Measurement (AREA)
Description
【発明の詳細な説明】
本発明は質量分析装置、特に電場強度と磁場強
度ともリンクして掃引する型の二重収束質量分析
装置に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a mass spectrometer, and more particularly to a dual-focus mass spectrometer that sweeps in conjunction with electric field strength and magnetic field strength.
メタステーブルイオンは有機化合物の構造解析
等に応用されているが、二重収束質量分析装置を
利用して電場Ｅと磁場Ｂとをリンクして掃引す
る、所謂リンクドスキヤン法は純粋なメタステー
ブルイオンを高い分解能で感度良く観測できるの
で近時広く利用されている。前記リンクドスキヤ
ン法には磁場Ｂと電場Ｅの比、Ｂ／Ｅを一定に保
つて掃引する方法と、B2／Ｅを一定に保つて掃
引する方法があり、前者は例えばプリカーサーイ
オンに対するドウターイオンを、後者はドーター
イオンを検出することによりそのプリカーサーイ
オンを知るために使用されている。この様な掃引
方法の内、Ｂ／Ｅ＝Ｋの掃引は比較的高精度で行
えるが、B2／Ｅ＝Ｋの掃引は電場制御部に自乗
回路を設け、磁場部の直線掃引に同期して前記自
乗回路を通して電場を掃引するようにしなければ
ならないので該掃引の理想曲線に対する精度はあ
まり高くない。このため検出されるイオンのプロ
フアイルは第１図に点線で示すように強度の低い
もの、歪みをもつたものとなる。尚、第１図中縦
軸Ｉはイオンビームの強度、横軸Ｅは電場強度を
示し、実線は正規のスペクトルである。 Metastable ions are applied to structural analysis of organic compounds, etc., but the so-called linked scan method, in which electric field E and magnetic field B are linked and swept using a double focusing mass spectrometer, is a pure metastable ion. It has been widely used in recent years because it allows ions to be observed with high resolution and sensitivity. The linked scan method includes a method of sweeping while keeping the ratio of magnetic field B and electric field E, B/E constant, and a method of sweeping while keeping B 2 /E constant. The latter is used to know its precursor ion by detecting its daughter ion. Among these sweep methods, the B/E=K sweep can be performed with relatively high accuracy, but the B 2 /E=K sweep requires a square circuit in the electric field control section to synchronize with the linear sweep of the magnetic field section. Since the electric field must be swept through the square circuit, the accuracy of the sweep with respect to the ideal curve is not very high. Therefore, the profile of the detected ions will be low in intensity and distorted, as shown by the dotted line in FIG. In FIG. 1, the vertical axis I shows the intensity of the ion beam, the horizontal axis E shows the electric field intensity, and the solid line is the normal spectrum.
第２図は上記プロフアイルの低下や歪みを説明
するための図であり、イオンビーム強度を電場Ｅ
と磁場Ｂの平面上の輝度、又は紙面と垂直な３次
元高さで表わしたものである。（尚、図では実際
は紙面と垂直方向に生ずる各スペクトルを理解を
容易にするためＢ−Ｅ平面に点線で表示してあ
る。）該第２図から解るように各スペクトルは
B2／Ｅの曲線に沿つた非常に細い線（又は薄い
平面）となるので、理想曲線ａに沿つて掃引がな
される場合は正確なイオンピークの検出が可能で
あるが、曲線ｂのように僅かに理想曲線よりずれ
るとイオンの検出が甚だ困難になり、第１図点線
で示すようなプロフアイルの低下、歪みは避けら
れないわけである。而して、リンクドスキヤンの
目的は未知試料の構造解析であり、上述のような
イオンプロフアイル強度の低下や歪みはその解析
精度上大きな問題となる。 Fig. 2 is a diagram for explaining the above profile drop and distortion, and shows the ion beam intensity as a function of the electric field E.
and the brightness of the magnetic field B on a plane, or the three-dimensional height perpendicular to the plane of the paper. (In the figure, each spectrum that actually occurs in the direction perpendicular to the page is shown as a dotted line on the B-E plane to make it easier to understand.) As can be seen from Figure 2, each spectrum is
Since it is a very thin line (or thin plane) that follows the curve B 2 /E, accurate detection of ion peaks is possible when sweeping is performed along the ideal curve a, but it is possible to detect the ion peak accurately when sweeping along the ideal curve a. If there is a slight deviation from the ideal curve, it becomes extremely difficult to detect ions, and the profile decline and distortion as shown by the dotted line in Figure 1 are unavoidable. The purpose of linked scan is to analyze the structure of an unknown sample, and the above-mentioned decrease in ion profile strength and distortion poses a major problem in terms of analysis accuracy.
而して、本発明は上記点に鑑み、掃引曲線が理
想曲線と少しずれていた場合でも正確なイオンプ
ロフアイルを検出できる装置を提供することを目
的とするものである。 SUMMARY OF THE INVENTION In view of the above points, it is an object of the present invention to provide an apparatus that can accurately detect an ion profile even if the sweep curve slightly deviates from the ideal curve.
本発明の構成はイオン源と該イオン源からのイ
オンを分析する電場及び磁場からなる二重収束質
量分析系と該分析系で分析されたイオンを検出す
る検出器と該検出器の出力信号を表示又は記録す
る手段を備えた装置において、前記電場の強度と
磁場の強度とを一定の関係で同期的に掃引する手
段を設けると共に前記掃引の周期より著しく速い
周期で変化する微小磁場を前記検出器の前方に設
置した質量分析装置に特徴がある。 The configuration of the present invention includes a double focusing mass spectrometry system consisting of an ion source, an electric field and a magnetic field for analyzing ions from the ion source, a detector for detecting ions analyzed by the analysis system, and an output signal of the detector. The apparatus is equipped with means for displaying or recording, and the apparatus includes means for synchronously sweeping the electric field strength and the magnetic field strength in a fixed relationship, and detecting the minute magnetic field that changes at a period significantly faster than the period of the sweep. The feature is the mass spectrometer installed at the front of the instrument.
以下第３図に基づき本発明の実施例を説明す
る。同図中、１はイオン源であり、該イオン源で
生成されたイオンはレンズ電極２で物点スリツト
３上に投射される。該スリツトを通過したイオン
は電場４に入射し、エネルギー分散を受け、エネ
ルギースリツト５上に収束される。該エネルギー
スリツト５を通過したイオンは磁場６に入り、質
量分散を受けて質量毎に分離され、コレクタース
リツト７を通してイオン検出器８で検出される。
前記コレクタースリツトの前方には一定の周期で
変動する微小磁場９が設けてある。該微小磁場の
掃引周期は電場−磁場のリンクドスキヤンの周期
に対し著しく短くされている。前記イオン検出器
８からの出力信号は増幅器１０を介して信号処理
回路１１に送られ、適宜な信号処理を受けた後、
表示又は記録装置１２に送られイオンスペクトル
が得られる。勿論、該処理回路からの信号をコン
ピユータに送り、直ちに試料の構造解析を行なう
ようにしても良い。１３は演算制御部であり、マ
イクロコンピユータが使用され各部へ制御信号が
供給される。該演算制御部にはパラメータ設定部
１４が接続しており、B2／Ｅ＝Ｋスキヤンの条
件、微小磁場９の制御部１５の掃引周期や掃引幅
を設定する。１６、１７、１８はDA変換器であ
り、演算制御部１３からのデジタル信号をアナロ
グ信号に変換する。DA変換器１６からの信号は
自乗回路１９を介して電場制御部２０に送られ、
前記電場４を磁場強度の変化に対し自乗の曲線に
沿つて掃引する。DA変換器１７は磁場掃引用で
あり、磁場の直線性を補正するDA変換器１８か
らの信号と加算器２１において加算され磁場制御
部２２に送られる。 An embodiment of the present invention will be described below based on FIG. In the figure, 1 is an ion source, and ions generated by the ion source are projected onto an object point slit 3 by a lens electrode 2. The ions that have passed through the slit enter the electric field 4, undergo energy dispersion, and are focused onto the energy slit 5. The ions that have passed through the energy slit 5 enter a magnetic field 6, undergo mass dispersion, are separated by mass, and are detected by an ion detector 8 through a collector slit 7.
In front of the collector slit, a minute magnetic field 9 that fluctuates at a constant period is provided. The sweep period of the minute magnetic field is significantly shorter than the period of the electric field-magnetic field linked scan. The output signal from the ion detector 8 is sent to a signal processing circuit 11 via an amplifier 10, and after being subjected to appropriate signal processing,
The ion spectrum is sent to a display or recording device 12 to obtain an ion spectrum. Of course, the signal from the processing circuit may be sent to a computer to immediately analyze the structure of the sample. Reference numeral 13 denotes an arithmetic control section, which uses a microcomputer and supplies control signals to each section. A parameter setting section 14 is connected to the arithmetic control section, and sets the conditions for the B 2 /E=K scan and the sweep period and sweep width of the control section 15 for the minute magnetic field 9. 16, 17, and 18 are DA converters, which convert digital signals from the calculation control section 13 into analog signals. The signal from the DA converter 16 is sent to the electric field control unit 20 via the square circuit 19.
The electric field 4 is swept along a square curve with respect to changes in magnetic field strength. The DA converter 17 is for magnetic field sweeping, and is added to the signal from the DA converter 18 for correcting the linearity of the magnetic field in an adder 21 and sent to the magnetic field control section 22 .
斯かる装置において、演算制御部１３からDA
変換器１６、自乗回路１９を介して電場制御部２
０へ電場掃引信号を送ると共に、これと同期して
DA変換器１７，１８、加算器２１を介して磁場
掃引信号を磁場制御部２２に送り、B2／Ｅ＝Ｋ
のリンクドスキヤンを行なう。これにより、イオ
ン源と電場４との間で生成されるメタステーブル
イオンはその質量に応じて検出器１０上に次々に
検出されることになるが、第２図で説明したよう
に掃引曲線ｂが理想曲線ａからずれていると得ら
れたイオンスペクトルのプロフアイルは歪んだ、
又は強度の低下したものとなる。しかしながら、
本発明では前記電場−磁場のリンクドスキヤンの
期間中該掃引の周期より著しく短い周期の掃引
（スキヤン）信号が制御部１５から微小磁場９に
送られる。そのため、第４図ａに示す如く磁場強
度Ｂは掃引曲線ｂを中心に±△B0の範囲で細か
く掃引されることになり、曲線ｂが理想曲線ａか
らずれていても掃引曲線が理想曲線を必ず横切つ
ているので、メタステーブルイオンのピーク部は
コレクタースリツト７を通過するようになりスペ
クトルのピークを容易に検出することができる。 In such a device, the DA from the arithmetic control unit 13
Electric field control section 2 via converter 16 and square circuit 19
Send an electric field sweep signal to 0 and synchronize with this.
A magnetic field sweep signal is sent to the magnetic field control unit 22 via the DA converters 17, 18 and the adder 21, and B 2 /E=K
Perform a linked scan. As a result, the metastable ions generated between the ion source and the electric field 4 are detected one after another on the detector 10 according to their mass, but as explained in FIG. deviates from the ideal curve a, the obtained ion spectrum profile is distorted.
Or the strength will be reduced. however,
In the present invention, during the period of the electric field-magnetic field linked scan, a sweep (scan) signal having a cycle significantly shorter than the sweep cycle is sent from the control unit 15 to the minute magnetic field 9. Therefore, as shown in Figure 4a, the magnetic field strength B is finely swept within the range of ±△B 0 around the sweep curve b, and even if the curve b deviates from the ideal curve a, the sweep curve is the ideal curve. Since the peak of the metastable ion passes through the collector slit 7, the peak of the spectrum can be easily detected.
検出器８の信号は信号処理回路１１に導入され
るが、該処理回路には前記制御部１５から前記微
小磁場掃引に同期した信号が送られており、各掃
引毎に最大強度の信号がホールドされ、これが第
４図ｂに示す様にスペクトルとして表示又は記録
される。 The signal from the detector 8 is introduced into a signal processing circuit 11, to which a signal synchronized with the minute magnetic field sweep is sent from the control section 15, and the signal with the maximum intensity is held for each sweep. This is displayed or recorded as a spectrum as shown in FIG. 4b.
尚、上記において、±△B0の微小磁場掃引を分
析用の磁場６と別個に設けた磁場９により行なつ
たが、前記分析磁場６の応答が充分に速ければ微
小磁場９を使用せずに該分析用の磁場に微小変化
磁場を重畳して使用することも可能である。又、
前記はB2／Ｅ＝Ｋのリンクドスキヤンについて
説明したが、Ｂ／Ｅ＝Ｋのリンクドスキヤンの場
合にも理想曲線と掃引曲線にずれがある時は同様
に利用できる。 In the above, the micromagnetic field sweep of ±△B 0 was performed using the magnetic field 9 provided separately from the analysis magnetic field 6, but if the response of the analysis magnetic field 6 is sufficiently fast, the micromagnetic field 9 may not be used. It is also possible to use a slightly changing magnetic field superimposed on the analytical magnetic field. or,
Although the linked scan with B 2 /E=K has been described above, the linked scan with B/E=K can also be used in the same way when there is a deviation between the ideal curve and the sweep curve.
以上説明したように本発明ではコレクタースリ
ツトの前方に電場−磁場掃引の周期より著しく速
い周期で変化する微小磁場を設けてあるので、理
想曲線上に存在するイオンスペクトルを正確に測
定でき、従来の様なプロフアイルの歪みや低下は
生じない。それ故、リンクドスキヤン法による試
料の構造解析を極めて高い精度で行なうことが可
能となる。 As explained above, in the present invention, a minute magnetic field is provided in front of the collector slit, which changes at a period significantly faster than the period of the electric field-magnetic field sweep, so it is possible to accurately measure the ion spectrum existing on the ideal curve. No distortion or deterioration of the profile will occur. Therefore, it becomes possible to perform structural analysis of a sample using the linked scan method with extremely high accuracy.
尚、第３図の実施例において、DA変換器を電
場用１６、磁場用１７及び磁場補正用１８の３個
使用し、所謂マルチダツク方式にしてあるので
DA変換器を１個使用してその出力をハード的に
分離するものに対し掃引の精度を高くすることが
できる。 In the embodiment shown in Fig. 3, three DA converters are used, 16 for electric field, 17 for magnetic field, and 18 for magnetic field correction, and a so-called multi-dac system is used.
The accuracy of the sweep can be increased compared to the one that uses one DA converter and separates its output by hardware.
第１図及び第２図は従来のリンクドスキヤン法
の欠点を説明する図、第３図は本発明の一実施例
を示すブロツク線図、第４図は第３図の装置の作
用を説明する図である。
１：イオン源、４：分析電場、６：分析磁場、
７：コレクタースリツト、８：イオン検出器、
９：微小磁場、１１…信号処理回路、１２：表示
又は記録装置、１３：演算制御部、１４：パラメ
ータ設定部、１５：微小磁場制御部、１６，１
７，１８：DA変換器、１９：自乗回路、２０：
電場制御部、２１：加算器、２１：磁場制御部。
1 and 2 are diagrams explaining the drawbacks of the conventional linked scan method, FIG. 3 is a block diagram showing an embodiment of the present invention, and FIG. 4 is a diagram explaining the operation of the device shown in FIG. 3. This is a diagram. 1: ion source, 4: analytical electric field, 6: analytical magnetic field,
7: Collector slit, 8: Ion detector,
9: Micromagnetic field, 11...Signal processing circuit, 12: Display or recording device, 13: Arithmetic control section, 14: Parameter setting section, 15: Micromagnetic field control section, 16,1
7, 18: DA converter, 19: Square circuit, 20:
Electric field control section, 21: Adder, 21: Magnetic field control section.
Claims (1)
る電場及び磁場からなる二重収束質量分析系と該
分析系で分析されたイオンを検出する検出器と該
検出器の出力信号を表示又は記録する手段を備え
た装置において、前記電場の強度Ｅと磁場の強度
ＢとをB2／Ｅ＝一定又はＢ／Ｅ＝一定の関係で
同期的に掃引する手段を設けると共に前記掃引の
周期より著しく速い周期で変化する微小磁場を前
記検出器の前方に設置したことを特徴とする質量
分析装置。 ２ 前記強度が変化する微小磁場は分析用の磁場
に重畳された磁場である特許請求の範囲第１項記
載の質量分析装置。 ３ 前記強度が変化する微小磁場は前記分析用の
磁場とは別に設けられた磁場である特許請求の範
囲第１項記載の質量分析装置。[Scope of Claims] 1. A double focus mass spectrometry system consisting of an ion source, an electric field and a magnetic field for analyzing ions from the ion source, a detector for detecting ions analyzed by the analysis system, and an output of the detector. In an apparatus equipped with a means for displaying or recording a signal, means is provided for synchronously sweeping the electric field strength E and the magnetic field strength B in a relationship where B 2 /E=constant or B/E=constant; A mass spectrometer characterized in that a minute magnetic field that changes at a period significantly faster than a sweep period is installed in front of the detector. 2. The mass spectrometer according to claim 1, wherein the minute magnetic field whose intensity changes is a magnetic field superimposed on a magnetic field for analysis. 3. The mass spectrometer according to claim 1, wherein the minute magnetic field whose intensity changes is a magnetic field provided separately from the magnetic field for analysis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58012342A JPS59137855A (en) | 1983-01-28 | 1983-01-28 | Mass spectrograph |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58012342A JPS59137855A (en) | 1983-01-28 | 1983-01-28 | Mass spectrograph |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59137855A JPS59137855A (en) | 1984-08-08 |
| JPH0319947B2 true JPH0319947B2 (en) | 1991-03-18 |
Family
ID=11802606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58012342A Granted JPS59137855A (en) | 1983-01-28 | 1983-01-28 | Mass spectrograph |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59137855A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4567472B2 (en) * | 2005-01-12 | 2010-10-20 | 株式会社エヌ・ティ・ティ・ドコモ | Data communication restriction method and data communication restriction control device for flat-rate users |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07111882B2 (en) * | 1987-04-15 | 1995-11-29 | 日本電子株式会社 | Double Convergent Mass Spectrometer Using Wien Filter |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56128558A (en) * | 1980-03-12 | 1981-10-08 | Hitachi Ltd | Double focusing mass spectrograph |
-
1983
- 1983-01-28 JP JP58012342A patent/JPS59137855A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56128558A (en) * | 1980-03-12 | 1981-10-08 | Hitachi Ltd | Double focusing mass spectrograph |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4567472B2 (en) * | 2005-01-12 | 2010-10-20 | 株式会社エヌ・ティ・ティ・ドコモ | Data communication restriction method and data communication restriction control device for flat-rate users |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59137855A (en) | 1984-08-08 |
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