JP2000243345A - Ion optical system of time-of-flight mass spectrometer - Google Patents

Ion optical system of time-of-flight mass spectrometer

Info

Publication number
JP2000243345A
JP2000243345A JP11041374A JP4137499A JP2000243345A JP 2000243345 A JP2000243345 A JP 2000243345A JP 11041374 A JP11041374 A JP 11041374A JP 4137499 A JP4137499 A JP 4137499A JP 2000243345 A JP2000243345 A JP 2000243345A
Authority
JP
Japan
Prior art keywords
ion
electric field
cylindrical electric
cylindrical
mass spectrometer
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
Application number
JP11041374A
Other languages
Japanese (ja)
Other versions
JP3571566B2 (en
Inventor
Hisashi Matsuda
久 松田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jeol Ltd
Original Assignee
Jeol Ltd
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Filing date
Publication date
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Priority to JP04137499A priority Critical patent/JP3571566B2/en
Publication of JP2000243345A publication Critical patent/JP2000243345A/en
Application granted granted Critical
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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/26Mass spectrometers or separator tubes
    • H01J49/34Dynamic spectrometers
    • H01J49/40Time-of-flight spectrometers
    • H01J49/408Time-of-flight spectrometers with multiple changes of direction, e.g. by using electric or magnetic sectors, closed-loop time-of-flight

Abstract

PROBLEM TO BE SOLVED: To provide a new ion optical system of a time-of-flight mass spectrometer capable of housing a long flight distance in a limited small space with a simple structure obtained by a combination of cylindrical electric fields. SOLUTION: Cylindrical electric fields E1 to E6 with identical shape of rotational angle 60 deg. and identical intensity are generated in a space between inner electrodes 1 to 6 and outer electrodes 1' to 6' being concentric circular cylindrical electrodes. The cylindrical electrodes E1 to E6 are arranged in rotational symmetry at equal intervals of 60 deg. with the axis O as the center to form a regular hexagonal ion orbit. A deflection electric field E0 for making a sample ion generated by an ion source incident toward the ion orbit. A deflection electric field E7 for externally taking sample ions flying in the ion orbit is arranged between the electric fields E1 and E6. An ion is made incident on one cylindrical electric field with a slight angle to a plane orthogonal to the axis O. The ion orbit gradually moves downward in the cylindrical electric field.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、飛行時間型質量分
析計(TOFMS)のイオン光学系に関するものであ
る。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ion optical system of a time-of-flight mass spectrometer (TOFMS).

【0002】[0002]

【従来の技術】飛行時間型質量分析計(TOFMS)におい
ては、一定の加速エネルギーで加速した試料イオンが質
量に応じた飛行速度を持つことに基づき、一定距離を飛
行するのに要する飛行時間を計測して質量を求める。
2. Description of the Related Art In a time-of-flight mass spectrometer (TOFMS), based on the fact that sample ions accelerated with a constant acceleration energy have a flight speed according to the mass, the flight time required to fly a certain distance is determined. Measure and determine the mass.

【0003】飛行時間型質量分析計では、飛行距離が長
い程高い質量分離能が得られるが、飛行距離を長くする
と装置の大型化は避けられない。そこで、大型化を防ぎ
つつ長い飛行距離を実現するために、これまでに多くの
工夫がなされている。
[0003] In a time-of-flight mass spectrometer, higher mass resolving power can be obtained as the flight distance is longer, but if the flight distance is increased, the size of the apparatus cannot be avoided. Therefore, many attempts have been made to achieve a long flight distance while preventing an increase in size.

【0004】その一つは、大阪大学で考案されたモータ
ーウェイ型装置で、直径41cmの真空容器内に1.7
27mの飛行距離を有するイオン光学系を納めることが
出来た(Int.J. Mass Spect. Ion Proc., 66(1985)28
3)。
[0004] One of them is a motorway type device devised by Osaka University.
Ion optics with a flight distance of 27 m could be accommodated (Int. J. Mass Spect. Ion Proc., 66 (1985) 28)
3).

【0005】また、最近では、同一軌道を複数回周回さ
せるマルチターンのイオン光学系が提案されている(第
46回質量分析総合討論会(1998)講演要旨集p.33〜及び
p319〜)。この方法では、トラック状の同一軌道に何回
もイオンを周回させることにより飛行距離を長くでき
る。
Recently, a multi-turn ion optical system for orbiting the same orbit several times has been proposed (the 46th Annual Meeting of the Mass Spectroscopy Symposium (1998), p.33-
p319-). In this method, the flight distance can be increased by making the ions orbit around the same track-like orbit many times.

【0006】[0006]

【発明が解決しようとする課題】しかし、モーターウェ
イ型装置は、多数の扇形電場が必要であり、構造が複雑
である。
However, the motorway type device requires a large number of sector electric fields and has a complicated structure.

【0007】また、マルチターンのイオン光学系は、イ
オン群を周回軌道へタイミングをはかって打ち込み及び
取り出しするための機構が必要になり構造が複雑にな
る。また、特定のイオン群しか分析できない欠点があ
る。さらに、同一軌道を何回も回るので、速いイオンと
遅いイオンが混合するおそれもある。このため、多成分
を持つ未知試料の分析は困難であると考えられる。
In addition, the multi-turn ion optical system requires a mechanism for implanting and extracting ions in a circular orbit at a proper timing, and the structure becomes complicated. Further, there is a disadvantage that only a specific ion group can be analyzed. Further, since the orbit is repeatedly made on the same orbit, fast ions and slow ions may be mixed. For this reason, it is considered difficult to analyze an unknown sample having multiple components.

【0008】本発明は、上述した諸点に鑑みてなされた
ものであり、比較的簡単な構造で、限られた狭い空間に
長い飛行距離を収容できる、新規な飛行時間型質量分析
計のイオン光学系を提供することを目的とするものであ
る。
The present invention has been made in view of the above-mentioned points, and has a relatively simple structure and can accommodate a long flight distance in a limited narrow space. It is intended to provide a system.

【0009】[0009]

【課題を解決するための手段】前述の課題を解決するた
めに、第1の本発明は、イオンが順次通過する複数の円
筒電場を備えた飛行時間型質量分析計のイオン光学系で
あって、該複数の円筒電場は最後の円筒電場を出射した
イオンが最初に入射した円筒電場に再び入射するように
配置されており、且つイオン軌道が円筒電場の軸に直交
する平面に対し傾きを与えられていることを特徴として
いる。さらに、第2の本発明は、イオンが順次通過する
複数の円筒電場を備えた飛行時間型質量分析計のイオン
光学系であって、該複数の円筒電場はイオンの回転方向
が同一で合計の回転角度が360°であり、最後の円筒
電場を出射したイオンが最初に入射した円筒電場に再び
入射するように配置されており、且つイオン軌道が円筒
電場の軸に直交する平面に対し傾きを与えられているこ
とを特徴としている。
According to a first aspect of the present invention, there is provided an ion optical system for a time-of-flight mass spectrometer having a plurality of cylindrical electric fields through which ions sequentially pass. The plurality of cylindrical electric fields are arranged such that ions emitted from the last cylindrical electric field are re-entered into the cylindrical electric field initially incident, and the ion orbit is inclined with respect to a plane orthogonal to the axis of the cylindrical electric field. It is characterized by being. Further, a second invention is an ion optical system of a time-of-flight mass spectrometer provided with a plurality of cylindrical electric fields through which ions sequentially pass, wherein the plurality of cylindrical electric fields have the same rotational direction and the total number of ions. The rotation angle is 360 °, the ions emitted from the last cylindrical electric field are arranged so as to be incident again on the first incident cylindrical electric field, and the ion orbit is inclined with respect to a plane perpendicular to the axis of the cylindrical electric field. It is characterized by being given.

【0010】[0010]

【発明の実施の形態】以下、本発明の実施の形態を図面
に基づいて詳説する。図1は、本発明に従う飛行時間型
質量分析計のイオン光学系の一実施例を示す平面図であ
り、図2はそのA−A断面図である。図1において、E
1〜E6は回転角度60°の同一形状及び同一強度の円
筒電場である。各円筒電場E1〜E6は、同心円筒電極
である内側電極1〜6と外側電極1´〜6´の間の空間
に生成される。
Embodiments of the present invention will be described below in detail with reference to the drawings. FIG. 1 is a plan view showing an embodiment of an ion optical system of a time-of-flight mass spectrometer according to the present invention, and FIG. 2 is a sectional view taken along line AA of FIG. In FIG. 1, E
1 to E6 are cylindrical electric fields having the same shape and the same strength at a rotation angle of 60 °. Each cylindrical electric field E1 to E6 is generated in a space between inner electrodes 1 to 6 which are concentric cylindrical electrodes and outer electrodes 1 'to 6'.

【0011】図1に示されているように、6つの円筒電
場E1〜E6は、軸心Oを中心として60°の等間隔で
回転対称に配置され、それにより、正六角形状のイオン
軌道が形成される。
As shown in FIG. 1, the six cylindrical electric fields E1 to E6 are arranged rotationally symmetrically at equal intervals of 60 ° about the axis O, so that a regular hexagonal ion orbit is formed. It is formed.

【0012】図2に示されているように、電場E1とE
6の間には、イオン源で生成された試料イオンを正六角
形状のイオン軌道に向けて入射させるための偏向電場E
0が配置されている。また、同じく電場E1とE6の間
には、正六角形状のイオン軌道を飛行してきた試料イオ
ンを外部へ取り出すための偏向電場E7が配置されてい
る。
As shown in FIG. 2, electric fields E1 and E1
6, a deflection electric field E for causing sample ions generated by the ion source to be incident on a regular hexagonal ion orbit.
0 is arranged. Similarly, between the electric fields E1 and E6, there is arranged a deflection electric field E7 for taking out the sample ions flying in the regular hexagonal ion orbit to the outside.

【0013】上記構成において、イオン源で生成された
試料イオンは、軸Oと平行に上から下へ向けて飛行し、
偏向電場E0に入射する。そして、偏向電場E0により
飛行方向がほぼ90°曲げられた試料イオンは、第1の
円筒電場E1に入射し、その後、順次円筒電場E2,E
3,E4,E5,E6を通過して再び円筒電場E1に再
入射する。
In the above arrangement, the sample ions generated by the ion source fly from top to bottom in parallel with the axis O,
The light enters the deflection electric field E0. Then, the sample ions whose flight direction is bent by about 90 ° by the deflection electric field E0 are incident on the first cylindrical electric field E1, and thereafter, are sequentially turned into the cylindrical electric fields E2, E.
3, E4, E5, and E6, and re-enters the cylindrical electric field E1.

【0014】ところで、偏向電場E0により試料イオン
を偏向して円筒電場E1に入射させる際、もしイオンが
軸心Oに直交する平面に沿って入射するように入射角度
を選定すると、試料イオンの軌道はその平面上にあり、
同一軌道を周回することとなる。これは、従来例で紹介
したマルチターン型の光学系と同じである。
When the sample ions are deflected by the deflection electric field E0 and are incident on the cylindrical electric field E1, if the incident angle is selected so that the ions are incident along a plane perpendicular to the axis O, the trajectory of the sample ions is determined. Is on that plane,
They will orbit the same orbit. This is the same as the multi-turn optical system introduced in the conventional example.

【0015】これに対し本発明では、軸心Oに直交する
平面に対して零でないわずかな角度θ傾けてこの円筒電
場へ入射させている。そのため、図2に示されているよ
うに、イオン軌道は円筒電場内で徐々に下方(軸心Oの
方向)に移動して行く。
On the other hand, in the present invention, the light is incident on the cylindrical electric field at a slight non-zero angle θ with respect to a plane perpendicular to the axis O. Therefore, as shown in FIG. 2, the ion trajectory gradually moves downward (in the direction of the axis O) in the cylindrical electric field.

【0016】円筒電場はy方向(円筒軸の方向)に対して
全く収束作用を持たないため、円筒電場E1に打ち込ま
れた試料イオンは、このイオン軌道に沿ってらせん階段
を下るように下降して行き、5周したところで円筒電場
E1とE6の間の5周後のイオン軌道の高さに合わせて
設けられた偏向電場E7に入射し軸Oの方向に取り出さ
れることとなる。取り出された試料イオンは、図示しな
いイオン検出器により検出される。
Since the cylindrical electric field has no converging effect in the y direction (the direction of the cylindrical axis), the sample ions injected into the cylindrical electric field E1 descend along the ion trajectory so as to descend the spiral staircase. After five rounds, the beam enters a deflection electric field E7 provided in accordance with the height of the ion trajectory after five rounds between the cylindrical electric fields E1 and E6, and is extracted in the direction of the axis O. The extracted sample ions are detected by an ion detector (not shown).

【0017】入射イオンとしてできる限り平行なビーム
を用いると、例えば飛行距離を3mとしても、y方向の
広がりは数mm程度に抑えられる。従って、1周毎に軸方
向にずれるピッチが5〜6mm程度になるようにθを選定
すれば、隣り合う軌道を進むイオンが混じることはな
い。
If a beam as parallel as possible is used as incident ions, the spread in the y direction can be suppressed to about several mm even if the flight distance is set to 3 m, for example. Therefore, if .theta. Is selected so that the pitch shifted in the axial direction for each revolution is about 5 to 6 mm, ions traveling on adjacent orbits will not be mixed.

【0018】このように、本発明では、合計の回転角が
360°になりイオンが複数回周回可能なように複数の
円筒電場を配置すると共に、円筒の軸に直交する平面に
対し傾けてイオンを円筒電場に打ち込むことにより、イ
オン軌道を円筒軸の方向に周回ごとにずらすことができ
る。このため、イオンが同一軌道を飛行することもな
く、また交差することもない長いイオン軌道を限られた
空間内に実現することができる。また、イオンを打ち込
む軌道と取り出す軌道が別れているため、打ち込みと取
り出しのタイミングをはかる必要がなく、打ち込み及び
取り出しのための構造が簡単になる。
As described above, according to the present invention, a plurality of cylindrical electric fields are arranged so that the total rotation angle becomes 360 ° and the ions can orbit a plurality of times, and the ions are inclined with respect to a plane perpendicular to the axis of the cylinder. Into the cylindrical electric field, the ion trajectory can be shifted for each revolution in the direction of the cylindrical axis. Therefore, it is possible to realize a long ion trajectory in which the ions do not fly in the same trajectory and do not intersect in a limited space. Further, since the trajectory for implanting ions and the trajectory for extracting ions are separated from each other, there is no need to measure the timing of implantation and extraction, and the structure for implantation and extraction is simplified.

【0019】表1は、図1に示されているイオン光学系
において、円筒電場E1〜E6の回転半径を5cm、各電
場間の直線軌道の長さを5cmとし、4+4/6周後に電場
E4とE5の間からイオンを取り出した場合について計
算により求めた、周回毎のx方向の収束性を表わす収差
係数(x┃x),(x┃a),(x┃d)と、時間収束性を表わす収差
係数(t┃x),(t┃a),(t┃d)を示している。 表1 周回 (x┃x) (x┃a) (x┃d) (t┃x) (t┃a) (t┃d) 飛行距離 1周後 -0.12 0.74 0.56 1.43 0.45 -0.90 60cm 2周後 -1.14 0.36 1.07 1.75 1.33 -0.96 120cm 3周後 -1.28 -0.31 1.14 0.70 1.95 -0.34 180cm 4周後 -0.41 -0.73 0.71 -0.90 1.83 0.55 240cm 4+4/6周後 0.92 0.58 0.04 0.15 0.01 0.09 280cm 表1における4+4/6周後の収差係数はいずれも極めて
小さく、x方向の収束性と時間収束性が共に優れた飛行
時間型質量分析計のイオン光学系であることが分かる。
また、直径わずか20cmの空間に、交差の全くない2m
以上の飛行距離が得られる。
Table 1 shows that, in the ion optical system shown in FIG. 1, the radius of rotation of the cylindrical electric fields E1 to E6 was 5 cm, and the length of a straight orbit between the electric fields was 5 cm. Aberration coefficients (x) x), (x, a), (x) d) representing the convergence in the x direction for each revolution, and the time convergence, obtained by calculation for the case where ions are extracted from between E5 and E5 Are shown as (t┃x), (t┃a), and (t┃d). Table 1 Orbit (x┃x) (x┃a) (x┃d) (t┃x) (t┃a) (t┃d) Flight distance After one lap -0.12 0.74 0.56 1.43 0.45 -0.90 60cm After two laps -1.14 0.36 1.07 1.75 1.33 -0.96 120cm After 3 laps -1.28 -0.31 1.14 0.70 1.95 -0.34 180cm After 4 laps -0.41 -0.73 0.71 -0.90 1.83 0.55 240cm 4 + 4/6 After lap 0.92 0.58 0.04 0.15 0.01 0.09 280cm Table The aberration coefficients after 4 + 4/6 rotations in Example 1 are all extremely small, indicating that the ion optical system of the time-of-flight mass spectrometer has excellent convergence in the x direction and time convergence.
Also, in a space of only 20cm in diameter, 2m without any intersection
The above flight distance can be obtained.

【0020】なお、イオンの周回数は、円筒電場の軸心
方向の長さ(高さ)と、イオン軌道の周回ピッチを適宜選
定することにより、任意に設定することができる。ま
た、打ち込みの際の傾斜角θを調節できるようにしてお
けば、取り出しのための構造を固定していても、取り出
し位置へ到達するまでのイオンの周回数を変えることが
可能である。
The number of turns of the ions can be arbitrarily set by appropriately selecting the length (height) of the cylindrical electric field in the axial direction and the orbital pitch of the ion orbit. In addition, if the inclination angle θ at the time of implantation can be adjusted, it is possible to change the number of turns of the ions before reaching the extraction position even if the extraction structure is fixed.

【0021】本発明は、上述した実施例に限定されるこ
となく、変形が可能である。例えば、円筒電場の間の直
線軌道部で周回によりずれて行く各軌道を確実に分離す
るため、アースプレートを各軌道の間に配置することが
好ましい。また、直線軌道の少なくとも1つにアパーチ
ャレンズ(アインツェルレンズ)を配置し、このレンズに
よりy方向の収束を行わせることも可能である。
The present invention can be modified without being limited to the above-described embodiment. For example, it is preferable to arrange an earth plate between the orbits in order to surely separate the orbits which are shifted by the orbit in the linear orbit portion between the cylindrical electric fields. It is also possible to arrange an aperture lens (Einzel lens) on at least one of the linear trajectories, and use this lens to converge in the y direction.

【0022】さらに、上記実施例では回転角度60°の
6つの円筒電場を回転対称に配置したが、これに限ら
ず、合計の回転角度が360°となり周回が可能なよう
に複数の円筒電場を組み合わせれば良い。
Further, in the above embodiment, six cylindrical electric fields having a rotation angle of 60 ° are arranged rotationally symmetrically. However, the present invention is not limited to this, and a plurality of cylindrical electric fields are arranged so that the total rotation angle becomes 360 ° and the circuit can rotate. Just combine them.

【0023】また、周回軌道へのイオンの打ち込み及び
周回軌道からの取り出しのための構造も、上記実施例に
限らず変形が可能である。例えば、円筒電場を作るため
の外側電極の1つに打ち込み用の穴をあけ、この穴から
イオン軌道に乗るようにイオンを打ち込んでも良い。
The structure for implanting ions into and out of the orbital orbits is not limited to the above embodiment, but may be modified. For example, a hole for implantation may be made in one of the outer electrodes for producing a cylindrical electric field, and ions may be implanted from this hole so as to be on the ion orbit.

【図面の簡単な説明】[Brief description of the drawings]

【図1】本発明にかかる飛行時間型質量分析計のイオン
光学系の実施例を示す図である。
FIG. 1 is a diagram showing an embodiment of an ion optical system of a time-of-flight mass spectrometer according to the present invention.

【図2】図1のイオン光学系におけるA−A断面を示す
図である。
FIG. 2 is a diagram showing an AA cross section of the ion optical system of FIG. 1;

【符号の説明】[Explanation of symbols]

E1〜E6…円筒電場 E0…打ち込み用偏向電場 E7…取り出し用偏向電場 1〜6…内側電極 1'〜6'…外側電極 E1-E6: cylindrical electric field E0: deflection electric field for driving E7: deflection electric field for extraction 1-6: inner electrode 1'-6 ': outer electrode

Claims (3)

【特許請求の範囲】[Claims] 【請求項1】イオンが順次通過する複数の円筒電場を備
えた飛行時間型質量分析計のイオン光学系であって、該
複数の円筒電場は最後の円筒電場を出射したイオンが最
初に入射した円筒電場に再び入射するように配置されて
おり、且つイオン軌道が円筒電場の軸に直交する平面に
対し傾きを与えられていることを特徴とする飛行時間型
質量分析計のイオン光学系。
1. An ion optical system of a time-of-flight mass spectrometer having a plurality of cylindrical electric fields through which ions sequentially pass, wherein the plurality of cylindrical electric fields are firstly irradiated by ions emitted from the last cylindrical electric field. An ion optical system for a time-of-flight mass spectrometer, wherein the ion optics are arranged so as to be incident again on the cylindrical electric field, and the ion trajectory is inclined with respect to a plane orthogonal to the axis of the cylindrical electric field.
【請求項2】イオンが順次通過する複数の円筒電場を備
えた飛行時間型質量分析計のイオン光学系であって、該
複数の円筒電場はイオンの回転方向が同一で合計の回転
角度が360°であり、最後の円筒電場を出射したイオ
ンが最初に入射した円筒電場に再び入射するように配置
されており、且つイオン軌道が円筒電場の軸に直交する
平面に対し傾きを与えられていることを特徴とする飛行
時間型質量分析計のイオン光学系。
2. An ion optical system of a time-of-flight mass spectrometer having a plurality of cylindrical electric fields through which ions sequentially pass, wherein the plurality of cylindrical electric fields have the same rotation direction and a total rotation angle of 360. °, the ions emitted from the last cylindrical electric field are arranged so as to re-enter the first incident cylindrical electric field, and the ion trajectory is inclined with respect to a plane perpendicular to the axis of the cylindrical electric field. An ion optics system for a time-of-flight mass spectrometer.
【請求項3】 前記円筒電場は、回転角度及び回転半径
が等しい6個の円筒電場から構成され、且つ回転対称に
配置されていることを特徴とする請求項2記載の飛行時
間型質量分析装置のイオン光学系。
3. The time-of-flight mass spectrometer according to claim 2, wherein the cylindrical electric field is composed of six cylindrical electric fields having the same rotation angle and rotation radius, and is arranged rotationally symmetrically. Ion optics.
JP04137499A 1999-02-19 1999-02-19 Ion optical system of time-of-flight mass spectrometer Expired - Lifetime JP3571566B2 (en)

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