CN101527246A - Novel cascade four-electrode quality analyzer - Google Patents
Novel cascade four-electrode quality analyzer Download PDFInfo
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- CN101527246A CN101527246A CN200910047637A CN200910047637A CN101527246A CN 101527246 A CN101527246 A CN 101527246A CN 200910047637 A CN200910047637 A CN 200910047637A CN 200910047637 A CN200910047637 A CN 200910047637A CN 101527246 A CN101527246 A CN 101527246A
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Abstract
The invention provides a novel cascade four-electrode quality analyzer and a work method thereof. A four-electrode rod electrode system is formed by two pairs of hyperboloid-shape electrodes or four column-shape electrodes or four round rods, the four-electrode rod system is loaded with a work voltage packet containing DC voltage and RF voltage, wherein two sets of four-electrode rod electrode systems are used for respectively forming a front-stage four-electrode mass filter Q1 and a back-stage four-electrode mass filter Q2, and the RF voltage can be sine waves, cosine waves, square waves or periodical-change waves. The invention also provides the work method of the cascade four-electrode quality analyzer, the voltage loading modes on the front-stage four-electrode mass filter Q1 and the back-stage four-electrode mass filter Q2 are different, and different effects and functions are obtained.
Description
Technical field
The present invention proposes a kind of novel cascade four-electrode quality and method of work thereof.This cascade four-electrode quality analyzer is made up of two groups of quadrupole rod electrode systems.The present invention has also comprised this two groups of quadrupole rod electrode systems, i.e. voltage load mode on prime quadrupole mass filter and the back level massenfilter, and the relation between the level quadrupole mass filter of front and back.
Technical background
Four-electrode quality analyzer, or be referred to as quadrupole mass filter, formed by four cylindrical electrodes.Generally, the operating voltage that is carried on the quadrupole mass filter includes direct voltage (DC) and radio-frequency voltage (RF) composition simultaneously.When using quadrupole mass filter to do quality analysis, regulate its operating voltage, make under the constant situation of its peak swing DC/RF, the scan line a=2 λ q that is produced is by near the summit of first stable region, thereby the fraction ion that allows mass-to-charge ratio meet stable condition passes through, and promptly reaches the effect of filtering medium.
Yet, in order to reach the purpose of high-quality resolution, need to keep the ratio of direct current and alternating voltage in the experimentation, promptly DC/RF is constant.Because the problem on the power supply manufacturing technology is difficult to realize the quick scanning of quality analysis in the actual application at present.If but an employed working power output AC, promptly RF that is to say, has only RF to load on the quadrupole mass filter, then scanning just can realize fast.The axial ejection quadrupole mass filter of for example in patent US 2004238734, mentioning.Yet, when the ion of a large amount of high mass-to-charge ratioes all when having only the quadrupole mass filter of radio frequency, tend to produce higher ambient noise signal, disturb mass spectral analysis to measure result.This is the subject matter that present such quadrupole mass filter exists.
Novel four-electrode quality analyzer and method of work thereof that the present invention is given, the quality that not only can solve traditional quadrupole mass filter scans problem fast, can also eliminate the interference of ambient noise signal to mass spectral analysis to measure result.
Summary of the invention
The object of the invention is to provide a kind of novel cascade four-electrode quality.
Another purpose of the present invention is to provide the ion analysis method of described novel cascade four-electrode quality.
The invention provides a kind of novel cascade four-electrode quality, by two pairs of hyperboloid shape electrodes, perhaps, four mast shape electrodes or four round bars are formed the quadrupole rod electrode system, in the electrode stem system, load operating voltage and comprise direct voltage and radio-frequency voltage, characteristics are: constitute prime quadrupole mass filter Q1 and back level quadrupole mass filter Q2 respectively by two groups of quadrupole rod electrode systems, the radio-frequency voltage that loads on massenfilter is for sine, cosine wave, square wave or a kind of in the periodically variable ripple arranged.
On the such scheme basis, described prime quadrupole mass filter Q1 and back level quadrupole mass filter Q2 are identical in cross section upper electrode arrangement perpendicular to axial direction, are the tandem structure.
The present invention also provides the method for work of above-mentioned novel cascade four-electrode quality, and is different with the voltage load mode on the level quadrupole mass filter Q2 of back at prime quadrupole mass filter Q1, has different effects and effect.
First kind of method of work seen Fig. 1, and Q1 is the prime quadrupole mass filter, V
1Cos Ω t is the main radio-frequency voltage that is carried on the Q1, V
1' cos ω t is the secondary radio frequency voltage that is added on the Q1, establishes V
1'/V
1=q ', ω/Ω=v then can obtain in quadrupole field, and the percent of pass of ion is to the variation of Mathieu equation parameter q, as shown in Figure 3.
From Fig. 3 as seen, at v=1/10, q ' increases at 0.02 o'clock, between q=0～0.2, formed an instability strip, mass-to-charge ratio drops on ion wherein like this, and just a large amount of heavy ions all can can't pass Q1 owing to instability is excluded out the quadrupole rod center and arrive next zone.By this way, prime quadrupole mass filter Q1 has removed the ion of a large amount of high mass-to-charge ratioes, has reduced background noise.
Among Fig. 1, Q2 is a back level quadrupole mass filter, V
2Cos Ω t is the main radio-frequency voltage of back level quadrupole mass filter, V
2' cos ω t be back level quadrupole mass filter from radio-frequency voltage.If V
2'/V
2=q ', ω/Ω=v then can obtain in perfect quadrupole field, and the percent of pass of ion is to variation such as Fig. 5 of Mathieu equation parameter q.
As seen from Figure 5, at v=1/10, q '=0.06 o'clock has produced a narrow stable region between q=0.87～0.88.Utilize the ion of these separable different mass-to-charge ratioes in stable region.
Second kind of method of work, as shown in Figure 2, the voltage load mode of prime quadrupole mass filter Q1 also can be established main radio frequency V for main radio-frequency voltage is carried out amplitude modulation
1Cos Ω t, the amplitude-modulated signal frequency is ω, and the amplitude modulation parameter is m, then can obtain in quadrupole field, and the percent of pass of ion is to the variation of Mathieu equation parameter q, as shown in Figure 4.
From Fig. 4 as seen, at v=9/10, during m=0.1, between q=0.1～0.2, formed an instability strip.Utilize this instability strip, can get rid of high mass-to-charge ratio ion equally.
The third method, as shown in Figure 8, the voltage load mode of back level quadrupole mass filter Q2 also can be established main radio frequency V for main radio-frequency voltage is carried out amplitude modulation
2Cos Ω t, the amplitude-modulated signal frequency is ω, and the amplitude modulation parameter is m, then can obtain in perfect quadrupole field, and the percent of pass of ion is to variation such as Fig. 6 of Mathieu equation parameter q.
Can get from Fig. 6, at v=9/10, m=0.10～0.20 o'clock forms corresponding different stabilized zones between q=0.88～0.93.Utilize these stabilized zones, ion that equally can separable different mass-to-charge ratioes.
The relation that prime quadrupole mass filter Q1 and back level quadrupole mass filter Q2 scan simultaneously in the following example.If the instability strip right margin q value of selected prime quadrupole mass filter be q1 (as shown in Figure 3, q '=0.02, q1=0.19), and the stabilized zone left margin q value of selected back level quadrupole mass filter be q2 (as shown in Figure 5, q '=0.02, q2=0.865), so in scanning process, V
1/ V
2=q1/q2.V in above-mentioned example
1/ V
2=0.19/0.865=0.220.Q1 and Q2 calculate from the q ' of radio-frequency voltage amplitude by correspondence.
Above-mentioned front and back level quadrupole mass filter can be hyperboloid shape electrode quadrupole mass filter, also can be circular bar shape electrode quadrupole mass filter, and other various massenfilters that mainly utilize quadrupole field character that ion is separated.Above-mentioned radio-frequency voltage can be sine or cosine wave, square wave, and all periodically variable ripples.Q1, Q2 is identical in cross section upper electrode arrangement perpendicular to axial direction.
Description of drawings
Fig. 1: one of working method of RF-only cascade four-electrode massenfilter.1 for producing the ion source of sample ions, and 4 is the prime quadrupole mass filter, adds radio-frequency voltage 10 on it, comprises main radio-frequency voltage V
1Cos Ω t and from radio-frequency voltage V
1' cos Ω t.6 is back level quadrupole mass filter, adds radio-frequency voltage 11 on it, comprises main radio-frequency voltage V
2Cos Ω t and from radio-frequency voltage V
2' cos Ω t.8 is the ion deflecting plate, and 9 is ion detector.3,5 are the ion focusing slit, and 7 are the ion focusing aperture plate, and 2 is sample ions.
Fig. 2: two of the working method of RF-only cascade four-electrode massenfilter.1 for producing the ion source of sample ions, and 4 is the prime quadrupole mass filter, adds radio-frequency voltage 10 on it, comprises main radio-frequency voltage V
1Cos Ω t and amplitude-modulated signal (1+mcos ω t).Q2 is a back level quadrupole mass filter, adds main radio-frequency voltage 11 on it, V
2Cos Ω t.8 is the ion deflecting plate, and 9 is ion detector.3,5 are the ion focusing slit, and 7 are energy selection aperture plate group, and 2 is sample ions.
Fig. 3: Q1 from the influence of radio-frequency voltage to the ion percent of pass.Abscissa is the q value of Mathieu equation, and ordinate is the percent of pass of ion.V is the ratio from radio-frequency voltage and main radio-frequency voltage frequency, and q ' is the ratio from radio-frequency voltage and main radio-frequency voltage amplitude.
The amplitude modulated voltage of Fig. 4: Q1 is to the influence of ion percent of pass.Abscissa is the q value of Mathieu equation, and ordinate is the percent of pass of ion.V is the ratio of amplitude-modulated signal and main radio-frequency voltage frequency, and m is the amplitude modulation parameter.
Fig. 5: Q2 from the influence of radio-frequency voltage to the ion percent of pass.Abscissa is the q value of Mathieu equation, and ordinate is the percent of pass of ion.V is the ratio from radio-frequency voltage and main radio-frequency voltage frequency, and q ' is the ratio from radio-frequency voltage and main radio-frequency voltage amplitude.
The amplitude modulated voltage of Fig. 6: Q2 is to the influence of ion percent of pass.Abscissa is the q value of Mathieu equation, and ordinate is the percent of pass of ion.V is the ratio of amplitude-modulated signal and main radio-frequency voltage frequency, and m is the amplitude modulation parameter
Fig. 7: three of the working method of RF-only cascade four-electrode massenfilter.1 for producing the ion source of sample ions, and 4 is the prime quadrupole mass filter, adds radio-frequency voltage 10 on it, comprises main radio-frequency voltage V
1Cos Ω t and from radio-frequency voltage V
1' cos Ω t.6 is back level quadrupole mass filter, adds main radio-frequency voltage 11 on it, V
2Cos Ω t.8 is the ion deflecting plate, and 9 is ion detector.3,5 are the ion focusing slit, and 7 are energy selection aperture plate group, and 2 is sample ions.
Fig. 8: four of the working method of RF-only cascade four-electrode massenfilter.1 for producing the ion source of sample ions, and 4 is the prime quadrupole mass filter, adds radio-frequency voltage 10 on it, comprises main radio-frequency voltage V
1Cos Ω t and from radio-frequency voltage V
1' cos Ω t.6 is back level quadrupole mass filter, adds radio-frequency voltage 11 on it, comprises main radio-frequency voltage V
2Cos Ω t and amplitude-modulated signal (1+mcos ω t).8 is the ion deflecting plate, and 9 is ion detector.3,5 are the ion focusing slit, and 7 are the ion focusing aperture plate, and 2 is sample ions.
Embodiment
A kind of novel cascade four-electrode quality, by two pairs of hyperboloid shape electrodes, perhaps, four mast shape electrodes or four round bars are formed the quadrupole rod electrode system, in the electrode stem system, load operating voltage and comprise direct voltage and radio-frequency voltage, constitute prime quadrupole mass filter Q1 and back level quadrupole mass filter Q2 respectively by two groups of quadrupole rod electrode systems.Wherein, radio-frequency voltage is sine, cosine wave, square wave or a kind of in the periodically variable ripple is arranged.
In the present embodiment, prime quadrupole mass filter Q1 and back level quadrupole mass filter Q2 are identical in cross section upper electrode arrangement perpendicular to axial direction.Below the present invention is described in detail in detail by four kinds of usings method.
Embodiment 1:
Fig. 1 is one of working method of RF-only cascade four-electrode massenfilter.Sample ions 4 enters prime quadrupole mass filter Q1 through ion source IS ionization through ion focusing slit 1.Q1 is at main radio-frequency voltage V
1Cos Ω t and from radio-frequency voltage V
1' acting in conjunction of cos Ω t removes down the ion of the high mass-to-charge ratio in the sample ions.The sample ions line focus slit 2 of having removed high mass-to-charge ratio ion enters back level quadrupole mass filter Q2.Q2 is at main radio-frequency voltage V
2Cos Ω t and secondary radio frequency voltage V
2' under the acting in conjunction of cos Ω t, the sample ions quality is selectively passed through.The ion line focus aperture plate 3 that the quality selection is passed through, through ion deflecting plate D deflection, Det detects by ion detector again.Detected ion signal forms the mass-spectrometer measurement result after record is handled.
Embodiment 2:
Fig. 2 be RF-only cascade four-electrode massenfilter working method two.Sample ions 4 enters prime quadrupole mass filter Q1 through ion source IS ionization through ion focusing slit 1.Q1 is at main radio-frequency voltage V
1The high mass-to-charge ratio ion in the sample ions is removed in the acting in conjunction of cos Ω t and amplitude-modulated signal (1+mcos ω t) down.The sample ions line focus slit 2 of having removed high mass-to-charge ratio ion enters back level quadrupole mass filter Q2.Q2 is at main radio-frequency voltage V
2Cos Ω t effect makes sample ions according to its mass-to-charge ratio difference, with corresponding kinetic energy outgoing by axially ejecting mode of operation.Axially the ion of outgoing selects aperture plate group 3 selectively to be separated by quality through energy.Through ion deflecting plate D deflection, Det detects by ion detector again.Detected ion signal forms the mass-spectrometer measurement result after record is handled.
Embodiment 3:
Fig. 7 be RF-only cascade four-electrode massenfilter working method three.Sample ions 4 enters prime quadrupole mass filter Q1 through ion source IS ionization through ion focusing slit 1.Q1 is at main radio-frequency voltage V
1Cos Ω t and from radio-frequency voltage V
1' acting in conjunction of cos Ω t removes down the high mass-to-charge ratio ion in the sample ions.The sample ions line focus slit 2 of having removed high mass-to-charge ratio ion enters back level quadrupole mass filter Q2.Q2 is at main radio-frequency voltage V
2Cos Ω t effect makes sample ions according to its mass-to-charge ratio difference, with corresponding kinetic energy outgoing by axially ejecting mode of operation.Axially the ion of outgoing selects aperture plate group 3 selectively to be separated by quality through energy.Through ion deflecting plate D deflection, Det detects by ion detector again.Detected ion signal forms the mass-spectrometer measurement result after record is handled.
Embodiment 4:
Fig. 8 be RF-only cascade four-electrode massenfilter working method four.Sample ions 4 enters prime quadrupole mass filter Q1 through ion source IS ionization through ion focusing slit 1.Q1 is at main radio-frequency voltage V
1Cos Ω t and from radio-frequency voltage V
1' acting in conjunction of cos Ω t removes down the high mass-to-charge ratio ion in the sample ions.The sample ions line focus slit 2 of having removed high mass-to-charge ratio ion enters back level quadrupole mass filter Q2.Q2 is at main radio-frequency voltage V
2Under the acting in conjunction of cos Ω t and amplitude-modulated signal (1+mcos ω t) the sample ions quality is selectively passed through.Quality is selected the ion line focus aperture plate 3 pass through, and through ion deflecting plate D deflection, Det detects by ion detector.Detected ion signal forms the mass-spectrometer measurement result after record is handled.
Claims (7)
1. novel cascade four-electrode quality, by two pairs of hyperboloid shape electrodes, perhaps, four mast shape electrodes or four round bars are formed the quadrupole rod electrode system, in the electrode stem system, load operating voltage and comprise direct voltage and radio-frequency voltage, it is characterized in that: constitute prime quadrupole mass filter Q1 and back level quadrupole mass filter Q2 respectively by two groups of quadrupole rod electrode systems.Wherein, radio-frequency voltage is sine, cosine wave, square wave or a kind of in the periodically variable ripple is arranged.
2. a kind of novel cascade four-electrode quality according to claim 1 is characterized in that: described prime quadrupole mass filter Q1 and back level quadrupole mass filter Q2 are the tandem structure, and be identical in cross section upper electrode arrangement perpendicular to axial direction.
3. at the method for work of claim 1 or 2 described a kind of novel cascade four-electrode quality, it is characterized in that: the main radio-frequency voltage that is carried on the Q1 is V
1Cos Ω t, the secondary radio frequency voltage that is carried on the Q1 is V
1' cos ω t, establish V
1'/V
1=q ', ω/Ω=v.Under the acting in conjunction of principal and subordinate's radio-frequency voltage, high mass-to-charge ratio ion all can can't pass Q1 owing to instability is excluded out quadrupole rod and arrive next zone.
4. according to the method for work of a kind of novel cascade four-electrode quality of claim 3, it is characterized in that: the voltage load mode of prime quadrupole mass filter Q1 is established main radio frequency V for main radio-frequency voltage is carried out amplitude modulation
1Cos Ω t, the amplitude-modulated signal frequency is ω, the amplitude modulation parameter is m.Under the effect of amplitude modulated voltage, high mass-to-charge ratio ion all can can't pass Q1 owing to instability is excluded out quadrupole rod and arrive next zone.
5. according to the method for work of a kind of novel cascade four-electrode quality of claim 3 or 4, it is characterized in that: Q2 is a back level quadrupole mass filter, V
2Cos Ω t is the main radio-frequency voltage of back level quadrupole mass filter, V
2' cos ω t be back level quadrupole mass filter from radio-frequency voltage, establish V
2'/V
2=q ', ω/Ω=v.Then under the acting in conjunction of principal and subordinate's radio-frequency voltage, can carry out quality analysis to the ion of different mass-to-charge ratioes.
6. according to the method for work of a kind of novel cascade four-electrode quality of claim 3 or 4, it is characterized in that: the voltage load mode of back level quadrupole mass filter Q2 is established main radio frequency V for main radio-frequency voltage is carried out amplitude modulation
2Cos Ω t, the amplitude-modulated signal frequency is ω, the amplitude modulation parameter is m.Then under the effect of amplitude modulated voltage, can separate the ion of different mass-to-charge ratioes.
7. according to the method for work of one of claim 5 or 6 described a kind of novel cascade four-electrode quality, it is characterized in that: prime quadrupole mass filter Q1 and back level quadrupole mass filter Q2 scan simultaneously.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102110568A (en) * | 2009-12-25 | 2011-06-29 | 上海凯世通半导体有限公司 | Beam transmission system and method |
| CN103222031A (en) * | 2010-11-19 | 2013-07-24 | 株式会社日立高新技术 | Mass spectrometer and mass spectrometry method |
| CN109390207A (en) * | 2018-10-23 | 2019-02-26 | 中国工程物理研究院材料研究所 | A kind of mass analyzer system of the variable-quality dispersion using permanent magnet |
-
2009
- 2009-03-16 CN CN200910047637A patent/CN101527246A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102110568A (en) * | 2009-12-25 | 2011-06-29 | 上海凯世通半导体有限公司 | Beam transmission system and method |
| CN102110568B (en) * | 2009-12-25 | 2014-12-10 | 上海凯世通半导体有限公司 | Beam transmission system and method |
| CN103222031A (en) * | 2010-11-19 | 2013-07-24 | 株式会社日立高新技术 | Mass spectrometer and mass spectrometry method |
| CN103222031B (en) * | 2010-11-19 | 2015-11-25 | 株式会社日立高新技术 | Quality analysis apparatus and mass analysis method |
| CN109390207A (en) * | 2018-10-23 | 2019-02-26 | 中国工程物理研究院材料研究所 | A kind of mass analyzer system of the variable-quality dispersion using permanent magnet |
| CN109390207B (en) * | 2018-10-23 | 2021-03-26 | 中国工程物理研究院材料研究所 | Mass analyzer system with variable mass dispersion using permanent magnets |
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