JPH05217548A - Quadrupole type mass spectrometer - Google Patents
Quadrupole type mass spectrometerInfo
- Publication number
- JPH05217548A JPH05217548A JP4046121A JP4612192A JPH05217548A JP H05217548 A JPH05217548 A JP H05217548A JP 4046121 A JP4046121 A JP 4046121A JP 4612192 A JP4612192 A JP 4612192A JP H05217548 A JPH05217548 A JP H05217548A
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- quadrupole
- voltage
- high frequency
- mass
- 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.)
- Pending
Links
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- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Electron Tubes For Measurement (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は四重極型質量分析計の温
度補正手段に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a temperature correction means for a quadrupole mass spectrometer.
【０００２】[0002]
【従来の技術】四重極型質量分析計では四重極間を通過
中に発散したイオンが四重極に入射するので、四重極の
温度が上昇し、熱膨張によって四重極電極棒の直径が増
し、四重極の保持枠も熱伝導を受けて昇温する結果熱膨
張して四重極電極間距離も増加する。このような熱膨張
は四重極電極相互の幾何学的関係を変化させ、イオン質
量の測定値に誤差を与える。2. Description of the Related Art In a quadrupole mass spectrometer, ions diverging while passing between quadrupoles are incident on the quadrupole, so that the temperature of the quadrupole increases and thermal expansion causes quadrupole electrode rods. The diameter of the quadrupole increases, and the holding frame of the quadrupole also receives heat conduction to raise the temperature. Such thermal expansion changes the geometrical relationship between the quadrupole electrodes and gives an error to the measured value of the ion mass.
【０００３】上述したような熱膨張の影響を補正するた
め従来は四重極電極と保持枠の材料の組合せを適当に選
んで四重極電極棒と保持枠の熱膨張の影響が相互に打ち
消し合うようにしていた。しかしこのような方法では理
想的な材料の組合せは得難く、一応の満足が行くような
組合せでも、材料の選択が非常に制限されて加工性が悪
くなるとか材料費が高価になる等の問題があり、しかも
補正自体完全には行い難いものであった。In order to correct the effect of thermal expansion as described above, conventionally, the combination of materials of the quadrupole electrode and the holding frame is appropriately selected so that the effects of thermal expansion of the quadrupole electrode rod and the holding frame cancel each other out. I was trying to fit. However, with such a method, it is difficult to obtain an ideal combination of materials, and even if the combination is satisfactory, the selection of materials is very limited, the workability deteriorates, and the material cost increases. However, the correction itself was difficult to perform completely.
【０００４】[0004]
【発明が解決しようとする課題】本発明は特別な材料の
組合せを選択すると云うようなことをしないで、電気的
な手段で任意に高精度で温度に対する補正がなされた四
重極型質量分析計を提供しようとするものである。The present invention does not mean to select a special material combination, but the quadrupole mass spectrometer is corrected with temperature with arbitrary precision by electric means. It is intended to provide a total.
【０００５】[0005]
【課題を解決するための手段】四重極電極棒或は同電極
保持枠に温度センサを設け、検出された温度データに基
づいて四重極に印加する直流電圧及び高周波電圧に補正
値を加算して四重極に印加するようにした。A temperature sensor is provided on a quadrupole electrode rod or an electrode holding frame, and a correction value is added to a DC voltage and a high frequency voltage applied to the quadrupole based on the detected temperature data. Then, the voltage was applied to the quadrupole.
【０００６】[0006]
【作用】四重極型質量分析器における温度上昇の影響は
四重極電極棒の直径が増すことによる対向電極間距離の
短縮と保持枠の膨張による四重極電極の中心間距離の増
加による対向電極間距離の増加の差として現れる対向電
極間距離の変化で、測定される質量に現れる質量誤差は
この距離変化の関数であり、距離変化は温度の関数であ
るから、質量誤差は温度の関数で、その形は四重極電極
構造の各寸法と材質によって決まる。従って任意質量Ｍ
を検出する場合の標準温度Ｔｏにおける正規の四重極印
加電圧をＵ，Ｖ（Ｕは直流電圧、Ｖは高周波電圧）とす
ると、温度ＴのときＴ−Ｔｏ＝ｔとして検出される質量
はＭ＋ΔＭで ΔＭ＝ｆ（ｔ） 上記誤差分だけ検出質量をずらせるため、Ｕ或はＶに与
えるべき補正値ΔＵ或はΔＶはまた温度差ｔの関数で例
えば ΔＶ＝ｇ（ｔ） 従って温度差ｔが検出されたとき、四重極に印加する電
圧を高周波電圧において Ｖ＋ΔＶ＝Ｖ＋ｇ（ｔ） ｇ（ｔ）は同じ設計の質量分析計では決まった形である
から、予め実測でｇ（ｔ）の形を求め記憶しておくこと
で、四重極印加電圧に温度による補正値を付加すること
により、常に正しい質量を求めることが可能となる。[Function] The influence of temperature rise in the quadrupole mass spectrometer is due to the shortening of the distance between the counter electrodes due to the increase in the diameter of the quadrupole electrode rod and the increase in the distance between the centers of the quadrupole electrodes due to expansion of the holding frame The change in the distance between the counter electrodes that appears as a difference in the increase in the distance between the counter electrodes, the mass error that appears in the measured mass is a function of this change in distance, and the change in distance is a function of temperature. It is a function and its shape depends on each dimension and material of the quadrupole electrode structure. Therefore, arbitrary mass M
When the normal quadrupole applied voltage at the standard temperature To for detecting is U and V (U is a direct current voltage and V is a high frequency voltage), the mass detected as T-To = t at the temperature T is M + ΔM. ΔM = f (t) In order to shift the detected mass by the above error, the correction value ΔU or ΔV to be given to U or V is also a function of the temperature difference t, for example ΔV = g (t) Therefore, the temperature difference t Is detected, the voltage applied to the quadrupole is a high-frequency voltage. V + ΔV = V + g (t) g (t) is a fixed form in the mass spectrometer of the same design, so g (t) is measured in advance. By obtaining and storing the shape, it becomes possible to always obtain the correct mass by adding the correction value due to the temperature to the quadrupole applied voltage.
【０００７】[0007]
【実施例】図１に本発明の一実施例を示す。図で１は四
重極を構成する電極棒、２は四重極電極棒の保持枠で絶
縁材料で作られており、これらは図２に示すような関係
で結合されている。３は保持枠２に一つの電極棒１の近
くまで穿設した盲孔４に挿入されている温度センサであ
る。５はイオン源で図１で右方にイオンビームを発射
し、四重極に印加される直流電圧Ｕと高周波電圧Ｖとの
値によって決まる特定質量のイオンが四重極間を通過し
て図１の右方のイオン検出器６によって検出される。FIG. 1 shows an embodiment of the present invention. In the figure, 1 is an electrode rod forming a quadrupole, 2 is a holding frame for the quadrupole electrode rod, which is made of an insulating material, and these are connected in a relationship as shown in FIG. Reference numeral 3 denotes a temperature sensor inserted in a blind hole 4 formed in the holding frame 2 up to the vicinity of one electrode rod 1. Reference numeral 5 denotes an ion source that emits an ion beam to the right in FIG. 1, and ions of a specific mass determined by the values of the DC voltage U and the high frequency voltage V applied to the quadrupole pass between the quadrupoles. 1 to the right of the ion detector 6.
【０００８】図２に上記実施例における四重極に電圧を
印加する回路を示す。図で７は制御回路で四重極に印加
する直流電圧Ｕと高周波電圧Ｖのディジタルデータを出
力する。高周波電圧及び直流電圧Ｖのディジタルデータ
はＤ／Ａ変換器１０で直流電圧に変換されアナログ加算
回路１１に被加数信号として印加される。加算回路１１
には温度センサ３の出力に応じた補正信号の電圧が加数
データとして印加され、両方の和の電圧が高周波電源１
２及び直流電圧電源９を制御して、高周波電源１２から
Ｖ＋ΔＶ（ΔＶは温度に対する補正値）の振幅の高周波
電圧を発生及び直流電圧Ｕ＋ΔＵ（ΔＵは温度に対する
補正値）させ、この電圧が四重極に印加される。FIG. 2 shows a circuit for applying a voltage to the quadrupole in the above embodiment. In the figure, 7 is a control circuit for outputting digital data of a DC voltage U and a high frequency voltage V applied to the quadrupole. The digital data of the high frequency voltage and the DC voltage V is converted into a DC voltage by the D / A converter 10 and applied to the analog adder circuit 11 as the augend signal. Adder circuit 11
The voltage of the correction signal corresponding to the output of the temperature sensor 3 is applied to the high frequency power supply 1 as the addend data.
2 and the DC voltage power supply 9 are controlled to generate a high frequency voltage having an amplitude of V + ΔV (ΔV is a correction value for temperature) and a DC voltage U + ΔU (ΔU is a correction value for temperature) from the high frequency power supply 12, and this voltage is quadruple. Applied to the poles.
【０００９】図２で鎖線ブロック１３で示した回路は温
度センサ３の出力から加算回路１１に印加する補正デー
タ信号を発生する回路である。温度センサ３の出力は差
動アンプ１４で規準電圧との差の信号ｘに変換される。
これは作用の項で述べた温度差ｔに相当する信号であ
る。補正データＥは Ｅ＝ｋｘｕ で与えられる。ｋは質量分析計によって決まる定数ｕは
Ｄ／Ａ変換器１０の出力で、検出しようとしているイオ
ン質量Ｍに対応している。このような信号Ｃを得るた
め、差動増幅器１４の出力ｘとＤ／Ａ変換器１０の出力
ｕとが掛算回路１５に入力され、その出力ｘｕが加算回
路１１でｋ倍される。これは加算回路で、被加数信号入
力抵抗Ｒと帰還抵抗Ｒとは等しいので、被加数信号は等
倍率で出力されるが、加算信号入力抵抗Ｒ’と帰還抵抗
Ｒとの比Ｒ／Ｒ’がｋに設定してあるので加算回路の出
力は ｕ＋ｋｘｕ となり、これが高周波電圧＋Δ及び直流電圧＋Δ’にな
って四重極電極に印加されることになる。The circuit shown by the chain line block 13 in FIG. 2 is a circuit for generating a correction data signal to be applied to the adding circuit 11 from the output of the temperature sensor 3. The output of the temperature sensor 3 is converted by the differential amplifier 14 into a signal x which is the difference from the reference voltage.
This is a signal corresponding to the temperature difference t described in the section of action. The correction data E is given by E = kxu. k is a constant determined by the mass spectrometer, u is the output of the D / A converter 10, and corresponds to the ion mass M to be detected. In order to obtain such a signal C, the output x of the differential amplifier 14 and the output u of the D / A converter 10 are input to the multiplication circuit 15, and the output xu thereof is multiplied by k in the addition circuit 11. This is an adder circuit, and since the augend signal input resistance R and the feedback resistance R are equal, the augend signal is output at an equal magnification, but the ratio R / of the addition signal input resistance R ′ and the feedback resistance R is Since R'is set to k, the output of the adding circuit becomes u + kxu, which becomes the high frequency voltage + Δ and the DC voltage + Δ ', and is applied to the quadrupole electrode.
【００１０】図２で規準温度における四重極の対向電極
棒の中心間距離を２Ｒ、電極棒の直径を２ｐとし、保持
枠の線膨張係数をα、電極棒の線膨張係数をβとし、規
準温度における対向電極間距離をｒｏとすると、規準温
度からｔだけ温度が上昇したときの対向電極間距離ｒは ｒｏ＝Ｒ−ｐ ｒ＝Ｒ（１＋αｔ）−ｐ（１＋βｔ）＝ｒｏ＋（Ｒα−
ｐβ）ｔ 他方四重極に印加する電圧Ｕ，Ｖを一定にしておくと検
出される質量Ｍはｒｏに対して Ｍ＝Ｃ’／ｒｏ2 の関係にあるのでｒｏの温度による変化Δｒ＝（Ｒα−
ｐβ）ｔに対するＭの変化ΔＭは ΔＭ＝−Ｃ’・２Δｒ／ｒｏ＝−２ＭΔｒ／ｒｏ 上式にΔｒ＝（Ｒα−ｐβ）ｔを代入すると ΔＭ＝−Ｃ’Ｍ（Ｒα−ｐβ）ｔ…(1) 従来は上式右辺（）内が０になるようにＲα−ｐβを選
んでいたから、材質の選択が制限され設計の自由度がな
かった。本発明は規準温度で質量Ｍのイオンを検出する
場合の四重極印加電圧Ｕｏ，Ｖｏの両方に補正値を加え
て検出される質量をΔＭだけシフトさせることで温度の
影響を補正するものである。上記(1) 式はΔＭ＝−ＣＭ
ｔと書け、これに対する電圧補正量はＫＭｔとなって、
Ｋは装置によって決まったものとなる。In FIG. 2, the center-to-center distance of the quadrupole opposing electrode rods at the standard temperature is 2R, the electrode rod diameter is 2p, the linear expansion coefficient of the holding frame is α, and the linear expansion coefficient of the electrode rod is β. Assuming that the distance between the counter electrodes at the reference temperature is ro, the distance r between the counter electrodes when the temperature rises from the reference temperature by t is ro = R−p r = R (1 + αt) −p (1 + βt) = ro + (Rα−
pβ) t On the other hand, when the voltages U and V applied to the quadrupole are kept constant, the detected mass M has a relationship of M = C ′ / ro 2 with respect to ro, and therefore the change of ro with temperature Δr = ( Rα-
The change ΔM of M with respect to pβ) t is ΔM = −C ′ · 2Δr / ro = -2MΔr / ro Substituting Δr = (Rα-pβ) t into the above equation, ΔM = −C′M (Rα-pβ) t ... (1) Conventionally, Rα-pβ was selected so that the value in the right side of the above formula () was 0, so that the selection of materials was limited and there was no design freedom. The present invention corrects the effect of temperature by adding a correction value to both the quadrupole applied voltages Uo and Vo when detecting ions of mass M at the reference temperature and shifting the detected mass by ΔM. is there. The above formula (1) is ΔM = -CM
can be written as t, and the voltage correction amount for this is KMt,
K is determined by the device.
【００１１】四重極型質量分析計で質量走査を行う場合
直流電圧Ｕと高周波電圧Ｖは図３に示すような軌跡に沿
って変化させる。図２で制御回路７はこの軌跡に沿うよ
うＵとＶに対応するディジタルデータを出力している。
上述実施例では制御回路７は質量Ｍの検出に対して規準
温度に対応するＵ，Ｖのデータを出力し、アナログ加算
回路で補正量を加えているが、制御回路７が質量Ｍにお
ける検出された温度に対する補正質量ΔＭを算出し、規
準温度でＭ−ΔＭに対応するＵ，Ｖのデータを出力し、
それをそのまゝ四重極に印加する直流，高周波の電圧に
変換するようにしてもよい。When mass scanning is performed by the quadrupole mass spectrometer, the DC voltage U and the high frequency voltage V are changed along the locus shown in FIG. In FIG. 2, the control circuit 7 outputs digital data corresponding to U and V along this locus.
In the above-mentioned embodiment, the control circuit 7 outputs the data of U and V corresponding to the reference temperature for the detection of the mass M, and the correction amount is added by the analog addition circuit. However, the control circuit 7 detects the mass M. Calculate the corrected mass ΔM for the specified temperature and output the U and V data corresponding to M-ΔM at the standard temperature.
It may be converted into a DC or high frequency voltage applied to the quadrupole.
【００１２】実施例では補正量は温度上昇ｔに比例させ
ているが、厳密には電圧Ｕ或はＶに対する補正量は、質
量Ｍの検出に当たって例えば高周波電圧の規準温度にお
ける値をＶｏとし、温度上昇ｔのときの値をＶとする
と、Ｖはｔの級数 Ｖ＝Ｖｏ（１＋ａｔ＋ｂｔ2 ＋ｃｔ3 ＋……） の形で表されるもので、実施例は上式でｔの１次の項ま
でとったものである。In the embodiment, the correction amount is proportional to the temperature rise t, but strictly speaking, the correction amount for the voltage U or V is Vo when the value of the high frequency voltage at the standard temperature is Vo when the mass M is detected. Assuming that the value at the time of rise t is V, V is expressed in the form of the series of t, V = Vo (1 + at + bt 2 + ct 3 + ...), and in the embodiment, up to the first-order term of t in the above equation. It was taken.
【００１３】[0013]
【発明の効果】本発明によれば材質の組合せの制限がな
いから、材料選択の面でも加工性の面でも最も有利な選
択ができ、温度補正は電気的に行われるので、装置が構
造的に複雑になることもなく、安価に高精度の四重極型
質量分析計を提供することが可能となる。According to the present invention, since there is no restriction on the combination of materials, the most advantageous selection can be made in terms of material selection and workability, and the temperature correction is performed electrically, so that the apparatus is structurally structured. It is possible to provide a highly accurate quadrupole mass spectrometer at low cost without being complicated.
【図１】本発明の一実施例の要部側面図FIG. 1 is a side view of an essential part of an embodiment of the present invention.
【図２】上記実施例の要部横断面および回路構成図FIG. 2 is a cross-sectional view of a main part and a circuit configuration diagram of the above embodiment.
【図３】四重極型質量分析計の印加電圧軌跡のグラフ[Fig. 3] Graph of applied voltage locus of quadrupole mass spectrometer
１ 四重極電極棒 ２ 電極棒保持枠 ３ 温度センサ ７ 制御回路 １１ 加算回路 １３ 補正データ信号を出力する回路 1 Quadrupole electrode rod 2 Electrode rod holding frame 3 Temperature sensor 7 Control circuit 11 Adder circuit 13 Circuit for outputting correction data signal
Claims (1)
センサにより得られた温度データに基づいて四重極電極
に印加する直流電圧或は高周波電圧に付加する温度補正
量を算出し、四重極印加電圧に加算して印加するように
したことを特徴とする四重極型質量分析計。A temperature sensor is attached to the quadrupole electrode rod or its holding frame, and the temperature correction amount to be added to the DC voltage or the high frequency voltage applied to the quadrupole electrode is calculated based on the temperature data obtained by the sensor. A quadrupole mass spectrometer characterized in that it is applied in addition to the quadrupole applied voltage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4046121A JPH05217548A (en) | 1992-01-31 | 1992-01-31 | Quadrupole type mass spectrometer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4046121A JPH05217548A (en) | 1992-01-31 | 1992-01-31 | Quadrupole type mass spectrometer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05217548A true JPH05217548A (en) | 1993-08-27 |
Family
ID=12738163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4046121A Pending JPH05217548A (en) | 1992-01-31 | 1992-01-31 | Quadrupole type mass spectrometer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05217548A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10106484A (en) * | 1996-09-30 | 1998-04-24 | Shimadzu Corp | Quadrupole mass spectrographic device |
| WO2008146440A1 (en) * | 2007-05-30 | 2008-12-04 | Shimadzu Corporation | Time-of-flight mass spectrometer |
| JP2009187850A (en) * | 2008-02-08 | 2009-08-20 | Hitachi High-Technologies Corp | Mass spectroscope |
| JP2014022162A (en) * | 2012-07-18 | 2014-02-03 | Hitachi High-Technologies Corp | Mass spectroscope |
| WO2023013274A1 (en) | 2021-08-06 | 2023-02-09 | 株式会社日立ハイテク | Mass spectrometer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03285246A (en) * | 1990-03-30 | 1991-12-16 | Shimadzu Corp | Quadrupole mass spectrometric device |
| JPH0455752A (en) * | 1990-06-25 | 1992-02-24 | Yokogawa Electric Corp | Quadrupole mass filter |
-
1992
- 1992-01-31 JP JP4046121A patent/JPH05217548A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03285246A (en) * | 1990-03-30 | 1991-12-16 | Shimadzu Corp | Quadrupole mass spectrometric device |
| JPH0455752A (en) * | 1990-06-25 | 1992-02-24 | Yokogawa Electric Corp | Quadrupole mass filter |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10106484A (en) * | 1996-09-30 | 1998-04-24 | Shimadzu Corp | Quadrupole mass spectrographic device |
| WO2008146440A1 (en) * | 2007-05-30 | 2008-12-04 | Shimadzu Corporation | Time-of-flight mass spectrometer |
| US8013293B2 (en) | 2007-05-30 | 2011-09-06 | Shimadzu Corporation | Time-of-flight mass spectrometer |
| JP4816794B2 (en) * | 2007-05-30 | 2011-11-16 | 株式会社島津製作所 | Time-of-flight mass spectrometer |
| JP2009187850A (en) * | 2008-02-08 | 2009-08-20 | Hitachi High-Technologies Corp | Mass spectroscope |
| JP2014022162A (en) * | 2012-07-18 | 2014-02-03 | Hitachi High-Technologies Corp | Mass spectroscope |
| WO2023013274A1 (en) | 2021-08-06 | 2023-02-09 | 株式会社日立ハイテク | Mass spectrometer |
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