CN110323125A - A kind of linear mass analyzer - Google Patents
A kind of linear mass analyzer Download PDFInfo
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- CN110323125A CN110323125A CN201910737870.XA CN201910737870A CN110323125A CN 110323125 A CN110323125 A CN 110323125A CN 201910737870 A CN201910737870 A CN 201910737870A CN 110323125 A CN110323125 A CN 110323125A
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- H—ELECTRICITY
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
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Abstract
A kind of linear mass analyzer of the present invention, including multiple segmented electrodes structures, multiple segmented electrodes structures are surrounded into stereoeffect;Wherein one or more segmented electrodes structures are equipped with reticular structure electrode, and ion enters by conductive mesh structure electrode and pop up mass analyzer.The present invention gives a kind of linear, segmented and the ion trap device for having mesh electrode structure, the voltage applied on segmented electrodes can carry out real-time optimization to the field distribution in ion trap, to achieve the purpose that significantly improve its mass resolving power.What the invention provided has novel ion trap quality analyzer device, and ion beam may be implemented from arbitrarily radially or axially upper and introduce ion, solve the limitation that ion introduces efficiency, meanwhile, the electric field of optimization ensure that quality analysis performance.The device can both be used separately as mass analyzer, can be used for ion storage, can also with other devices, such as other kinds of mass spectrometer join together using.
Description
Technical field
The present invention relates to physical field more particularly to analytical technique of mass spectrum, especially a kind of linear mass analyzer.
Background technique
Mass spectrograph is that a kind of track that the charged particle according to different quality moves in an electrical or magnetic field is different, thus real
The analysis instrument of separation and the detection of the atom, molecule or molecular fragment of existing different material.Mass spectrograph has to unknown compound
Qualitative and quantitative analysis and structure composition the abilities such as determination, there is splendid sensitivity, selectivity and extensive be applicable in
Property.At present have been widely used for life science, geological exploration, environment measuring, food safety, petrochemical industry, biomedicine,
The technical fields such as national security, quality control, clinical diagnosis.Mass spectrometric type is varied, according to used quality point
The difference of parser can be divided into magnetic mass spectrometer, quadrupole mass spectrometer, ion trap mass spectrometer, time of-flight mass spectrometer, orbit trap matter
Spectrometer, ion cyclotron resonance mass spectrometer etc..Common mass spectrometric chief component has vacuum system, ion source, ion to pass
This six most of composition of defeated system (also referred to as ion-optic system), mass analyzer, detector and TT&C system.Mass spectrograph point
The object of analysis is gaseous ion, and the mean free path in order to guarantee gaseous ion is sufficiently large, and mass spectrograph must operate at Gao Zhen
Under empty condition.It is limited to mass spectrometric vacuum system, the mass spectrograph of mainstream all has very big volume and weight on the market.Body
Limitation in long-pending and weight causes mass spectrograph that must run in the laboratory of profession.Nearest 10 years, pacified with environmental protection, food
Demand of the physico-chemical analysis field to on-site test and on-line checking based on complete and social public security etc. increasingly increases, to point
The portability of analyzer device proposes the matter of specific demand, the mass spectrograph of compact and portable miniaturization and micromation
Spectrometer is increasingly becoming a kind of main trend, and in the mass analyzer of above-mentioned numerous kinds, ion strap mass analyzer has
Higher tolerance operating air pressure, and high pressure conditions have good auxiliaring effect to the constraint of ion, thus it is based on ion
Compact, the micromation mass spectrograph of trap mass analyzer become the important research direction of academic circles at present and industry.
The development course of ion trap is the process that its geometry is continued to optimize, (bibliography as shown in Figure 1
Anal.Chem.2004,76,4595-4605), from the three-dimensional hyperboloid structure of the Paul Trap of earliest period to current mainstream
Linear hyperboloid electrode structure, then to the flat plate type linear electrode rectangular ion well structure being further simplified.
Describe a kind of linear ion trap mass analyzer in the United States Patent (USP) of Patent No. US6797950B2, ion from
In the axial direction z injection trap, by resonant excitation, popped up from radial x and the side y upwardly through the slit opened on electrode, into from
Sub- detector.The linear ion trap of this structure can effectively improve ion capacity and ion storage efficiency, while reduce sky
Between charge effect interference, further improve mass resolution.Since the ion in trap is popped up by the slit on electrode, from
The pop-up quantity and ejection efficiency of son are limited by slit size, narrow in order to reduce the destruction to the quadripolar electric field in trap
The size of seam is specially 0.25 millimeter, physically limits the quantity of ion pop-up, causes the ionic strength of the device limited,
Affect mass spectrometric detection sensitivity.The patent and article A new linear ion trap of Patent No. WO9747025-A
One kind is disclosed in mass spectrometer (Rapid Commun. Mass Spectrom. 2002,16:512-526)
Linear ion trap mass spectrometer, structure is similar with triple quadrupole bar mass analyzer, but by using the skill axially popped up
The function of art realization ion strap mass analyzer.Axis fetters ion upwardly through the DC potential applied in plane electrode;Radial x
Apply radio-frequency voltage with the round bar electrode on the direction y and fetters ion.Ion is directed upwardly into trap from the axial side z, moves to quadrupole
The effect of the tail region of bar, the radio-frequency voltage on quadrupole rod and the DC voltage on its rear extraction lens constructs edge
, it is popped up by fringing field effect from the axial side z, into ion detector.Ion is popped up from axis, avoids slit
Physical limit, can have the matching on better geometry with the detector of ion, improve ion ejection efficiency, detection effect
The promotion of rate greatly improves the detection sensitivity of instrument.Hyperboloid electrode and the quadrupole rod electricity that above two technology is respectively adopted
, there is very high requirement in pole to the machining accuracy of electrode and overall package precision, and usual mechanical tolerance needs to control
At 10 microns hereinafter, to be accurate to 1 micron or less in some cases.These factors cause the exploitation of such mass spectrometer by
The stringent limitation of machining, while increasing cost and the development cycle of instrument.
A kind of rectangular parallelepiped structure by plate electrode building is described in the United States Patent (USP) of Patent No. US6838666B2
Ion strap mass analyzer, the cross section of internal xy radially is rectangle, therefore referred to as rectilinear ion trap, is a kind of structure into one
Walk simplified linear ion trap.Rectilinear ion trap on the radial direction x and y and is all made of plate electrode structure on the axial direction direction z
At the electrode face in trap is plane.Ion is introduced from the axial upper direction z, and is fettered by axial DC current potential, radially
The direction x and y is fettered by radio-frequency voltage, by resonant excitation, is popped up from radial x and the side y.Ion pop-up is still from plane
The slit of electrode pops up.Since the electric field multipole fields ingredient in rectilinear ion trap is more complicated, in order to reduce to the quadrupole electricity in trap
The destruction of field, the slit width for ion pop-up is limited, and only 1 millimeter., ionic strength that linear ion trap detects by
Limit.Thus, although which simplifies structure, but the detection sensitivity of mass analyzer and resolution ratio have it is different degrees of under
Drop, limits the exploitation and industrialized development of the commercial product of the technology.
The applicant discloses one kind in the Chinese patent that number of patent application is 201210161473.0 and is mounted with conduction
The ion strap mass analyzer of grid electrode, it has the advantages that macroion is drawn and collection efficiency, high sensitivity.Although aperture plate
Electrode is conducive to improve ion ejection efficiency, but the ingredient that the use of plate electrode causes its internal electric field to be distributed is still very
Complexity seriously limits its mass resolution.In addition, the Chinese patent that the applicant is 201210496291.9 in number of patent application
In disclose a kind of ion trap device with step grid electrode structure, it is intended to passing through step electrode improves ion trap
Field distribution, the technology have very high processing and group to parameters such as the feature structures such as symmetry, step angle of electrode
The demand of precision is filled, in addition, the technology needs the optimization of a large amount of geometry with the optimal step shape of determination and position, is increased
Product development cost and development cycle are added.
The ion strap mass analyzer of structure simplification and reliable performance is still current urgent need in the market.Constantly
Simplified geometry simplifies the processing of ion strap mass analyzer and packaging technology, and cost reduces, but too simple
Structure also lead to the complication of ion trap internal electric field ingredient, analysis performance is remarkably decreased.
Summary of the invention
In view of the above technical defects, the purpose of the present invention is to provide a kind of linear quality for solving above-mentioned technical problem
Analyzer.
In order to solve the above technical problems, the present invention provides a kind of linear mass analyzer, multiple segmented electrodes knots
Structure, multiple segmented electrodes structures are surrounded into stereoeffect;Wherein
One or more segmented electrodes structures be equipped with reticular structure electrode, ion by conductive mesh structure electrode enter and
Pop up mass analyzer;
Any one of segmented electrodes structure lineal layout on the direction x and the direction y, the segmentation on the direction x and the direction y
Zx plane and zy plane where formula electrode structure surround the constraint sky that ion is formed into stereoeffect radially
Between;Wherein
Xyz is rectangular coordinate system in space.
Further, it is mutually insulated between segmented electrodes structure, is mutually not turned on.
Further, mutually insulated between the electrode in segmented electrodes structure, be mutually not turned on.
Further, segmented electrodes structure is complete electrode, electrode surface profile segment formula electrode.
Further, segmented electrodes structure includes basal electrode and the segmented electrode that is arranged on basal electrode, point
Separated between segment electrode and basal electrode by insulating materials.
Further, the material of reticular structure electrode is that conductive metal material or non-metal material surface have conductive layer to cover
Lid.
Further, reticular structure electrode is that line is arranged in parallel in the direction x or the direction y is arranged in parallel or the direction x and y is handed over
Mistake distribution setting.
Further, the cross section of the conductor wire of reticular structure electrode is round or rectangular.
Further, the linear mass analyzer includes unilateral setting segmented electrodes structure in the x direction;
Wherein, in the linear mass analyzer, segmented electrodes structure includes basal electrode and is arranged on basal electrode
Segmented electrode, separated between segmented electrode and basal electrode by insulating materials.
Further, the linear mass analyzer includes two pairs of segmented electrodes structures on the direction x and y;Its
In, segmented electrodes structure is complete electrode, electrode surface profile segment formula electrode.
The present invention gives a kind of linear, segmented and the ion trap device for having mesh electrode structure, segmented electricity
The extremely upper voltage applied can carry out real-time optimization to the field distribution in ion trap, significantly improve its mass resolution energy to reach
The purpose of power.What the invention provided has novel ion trap quality analyzer device, and ion beam may be implemented from arbitrary radial direction
Or axis is directed upwardly into ion, solves the limitation that ion introduces efficiency, meanwhile, the electric field of optimization ensure that quality analysis performance.
The device can both be used separately as mass analyzer, can be used for ion storage, can also with other devices, such as other
The mass spectrometer of type join together using.
Detailed description of the invention
The geometry development course schematic diagram of Fig. 1 ion strap mass analyzer;
Fig. 2 (a) is the structural schematic diagram of the cross section xy- of novel ion trap mass analyzer proposed by the present invention;Fig. 2 (b)
For the three dimensional structure diagram of Novel direct linear ion trap proposed by the present invention;
Fig. 3 is the mesh electrode structural schematic diagram on the segmented electrodes of Novel direct linear ion trap proposed by the present invention, Fig. 3
(a) schematic perspective view of single segmented electrodes;Horizontal direction in Fig. 3 (b) mesh electrode is distributed grid lines schematic diagram;
Vertical direction in Fig. 3 (c) mesh electrode is distributed grid lines schematic diagram;The grid lines of cross-distribution in Fig. 3 (d) mesh electrode
Schematic diagram;
Fig. 4 is the mass spectrometric structural schematic diagram that embodiment 1 provides;
Fig. 5 is the mass spectrometric structural schematic diagram that embodiment 2 provides;
Fig. 6 is the mass spectrometric structural schematic diagram that embodiment 3 provides;
Fig. 7 is the mass spectrometric structural schematic diagram that embodiment 4 provides.
Specific embodiment
Linear mass analyzer of the present invention is described in further detail with reference to the accompanying drawing.
The technical problem to be solved by the present invention is reducing electrode machining and assembling essence by simplified electrode structural designs
The requirement of degree is provided simultaneously with the real-time optimization function to the electric field inside ion strap mass analyzer, improves ion trap mass point
The performance of parser.
It is used as a linear mass analyzer as shown in Figure 2, the structure of electrode is linear type point in the direction x and y
Cloth, the constraint space of ion made of zx plane where electrode and zy plane on the direction x and y are surrounded radially, electricity
The extremely upper voltage applied realizes constraint radially to the ion in mass analyzer, fetters ion beam in the mass analyser
Linear distribution of shapes in a z-direction.
The segmented electrodes of mass analyzer are constituted, as shown in Fig. 2 (b), for two pairs points on the direction the x and direction y
Segmentation electrode is mutually insulated between electrode, is mutually not turned on;
Each band (201,202,203) and band (204,205,206) on segmented electrode, band (207,208,209),
All be between band (210,211,212) it is independent, be mutually insulated between different bands, be mutually not turned on.
Segmented electrodes on the direction mass analyzer x or y can be a piece of complete electrode, electrode surface production
There are the segmented electrodes of AD HOC to be distributed.
The segmented electrodes in the direction mass analyzer x or y are the sets of segment electrodes as made of several electrode combinations,
Segmented electrode is fixed on basal electrode, is separated between segmented electrode and basal electrode by insulating materials.
Conductive mesh part in the band (208,205,202,211) of segmented electrode, can be its on segmented electrode
In one section a part be conductive mesh or segmented electrode whole section of all conductive mesh.
The material of conductive mesh part in the band (208,205,202,211) of segmented electrode can be metallic conduction material
Material, being also possible to non-metal material surface has conductive layer covering.
The knot of conductive mesh part in the band of segmented electrode band as shown in Figure 2 (208,205,202,211)
Structure can be diversified forms, can be direction parallel lines grid such as Fig. 3 (b) and 3(c of single direction distribution) shown in, or
The grid of both direction cross-distribution is as shown in Fig. 3 (d).
The structure snd size of conductive mesh in the band (208,205,202,211) of segmented electrode are multifarious, conductions
The cross section of every single line in net be it is round, rectangular and trapezoidal, geometric dimension of different shapes is various.
Embodiment 1
It is illustrated in figure 4 the structural schematic diagram of embodiment 1, Fig. 4 (a) show the cross section signal of mass analyzer x/y plane
Scheme, ion binding space made of two pairs of segmented electrodes on the direction x and y surround, the segmented electrodes on each direction
There are multiple strip electrodes to be fixed on basal electrode (401,408,415,422), electrode (405,406,407,412,413,
414, it is 419,420,421,417,428) working electrode, applies radio-frequency voltage and alternating voltage, for fettering ion and ion
Operation include introduce, resonant excitation and pop-up, working electrode are fixed on basal electrode, between working electrode and basal electrode
The electrode strips (402,403,404,409,410,411,416,417,418,423) for having insulating materials are nonmetallic, insulation
Material electrode is used for isolating metal electrode and basal electrode.Basal electrode is metal electrode, is generally in ground potential, and shielding is outer
Interference of portion's electric field to analyzer internal electric field.Conductive mesh is had in the structure of electrode strips (406,413,420,427), is used for
The introducing and pop-up of ion.
As shown in Figure 4 (b), illustrate that the specific structure of electrode and voltage are applied by taking a segmented electrodes in the direction x as an example
Add form.3 through-holes are provided on basal electrode 401, electrode cable (429,430,431) is inserted into insulating electrode by through-hole respectively
In (420,403,404), and passes through insulating electrode and connect with working electrode (405,406,407), driving ion trap mass point
The output voltage of the power supply of parser work passes through electrode cable (429,430,431) and is applied on working electrode.It is applied to electricity
Voltage on pole (405,406,407) is respective Independent adjustable section voltage.
When mass analyzer works, voltage is acted on bound ion on working electrode, by ion according to mass-to-charge ratio
The sequence of size pass sequentially through on conductive mesh electrode on the direction x- (406,413) or on the direction y- conductive mesh electrode (420,
427) it pops up, realizes the separation of the ion of different mass-to-charge ratioes, the collection and multiplication of the ion of pop-up device after testing, the electricity of generation
Signal is converted into mass spectrogram signal by data processing systems such as amplification, digital-to-analogue conversions.
Embodiment 2
It is illustrated in figure 5 the structural schematic diagram of embodiment 2, using the electrode structure for being only equipped with conductive mesh in the x direction.Quality point
The cross-sectional view of parser x/y plane, ion binding space made of two pairs of segmented electrodes on the direction x and y surround, often
Segmented electrodes on one direction have multiple strip electrodes to be fixed on basal electrode (501,508,515,522), electrode
(505,506,507,512,513,514,519,520,521,517,528) it is working electrode, applies radio-frequency voltage and alternating current
Pressure, the operation for fettering ion and ion include that introducing, resonant excitation and pop-up, working electrode are fixed on basal electrode,
Have between working electrode and basal electrode insulating materials electrode strips (502,503,504,509,510,511,516,517,
518,523) it is nonmetallic, isolation material electrode, is used for isolating metal electrode and basal electrode.Basal electrode is metal electricity
Pole, is generally in ground potential, shields interference of the external electrical field to analyzer internal electric field, on a pair of of segmented electrode on the direction x
Electrode strips (506,513) structure in have conductive mesh, introducing and pop-up for ion.Nothing on electrode (520,527)
Conductive mesh.When mass analyzer works, voltage is acted on bound ion on working electrode, and ion is big according to mass-to-charge ratio
Small sequence passes sequentially through conductive mesh electrode on the direction x- (506,513) pop-up, realizes the separation of the ion of different mass-to-charge ratioes, bullet
The electric signal of the collection and multiplication of the device after testing of ion out, generation passes through the data processing systems such as amplification, digital-to-analogue conversion turn
Turn to mass spectrogram signal.
Embodiment 3
It is illustrated in figure 6 the structural schematic diagram of embodiment 3, the electrode structure of conductive mesh is equipped with using unilateral side only in the x direction.
The cross-sectional view of mass analyzer x/y plane, ion binding made of two pairs of segmented electrodes on the direction x and y surround are empty
Between, the segmented electrodes on each direction have multiple strip electrodes to be fixed on basal electrode (601,608,615,622),
Electrode (605,606,607,612,613,614,619,620,621,617,628) is working electrode, applies radio-frequency voltage and friendship
Galvanic electricity pressure, the operation for fettering ion and ion include that introducing, resonant excitation and pop-up, working electrode are fixed on basal electrode
On, have between working electrode and basal electrode insulating materials electrode strips (602,603,604,609,610,611,616,
617, it is 618,623) nonmetallic, isolation material electrode, is used for isolating metal electrode and basal electrode.Basal electrode is metal
Electrode is generally in ground potential, shields interference of the external electrical field to analyzer internal electric field, the side segmented electrode on the direction x
On electrode strips 606 structure in have conductive mesh, introducing and pop-up for ion.Electrode (613,620,627) electrode
On without conductive mesh.When mass analyzer works, voltage is acted on bound ion on working electrode, by ion according to matter lotus
Sequence than size passes sequentially through the pop-up of conductive mesh electrode 606 on the direction x-, realizes the separation of the ion of different mass-to-charge ratioes, pops up
Ion device after testing collection and multiplication, the electric signal of generation converted by data processing systems such as amplification, digital-to-analogue conversions
For mass spectrogram signal.
Embodiment 4
It is illustrated in figure 7 the structural schematic diagram of embodiment 4, the cross-sectional view of mass analyzer x/y plane, on the direction x and y
Two pairs of electrodes surround made of ion binding space, it is non-gold that the electrode on each direction, which is (701,706,711,716),
Belong to the monolithic full electrode of material, electrode surface has conductive metal film covering, the shape that multiple strip electrodes pass through surface film
Formula constructs, mutually isolated between band, and conductive film band (702,703,704) is arranged on electrode 701, and conductive mesh 705 is solid
It is scheduled on electrode 701 and is connected with conductive film band 703;Conductive film band (707,708,709) is arranged in electrode 706
On, conductive mesh 710 is fixed on electrode 706 and is connected with electrode 708;Conductive film band (712,713,714) is arranged in electricity
On pole 711, conductive mesh 715 is fixed on electrode 711 and is connected with electrode 713;Conductive film band (717,718,719) setting
On electrode 716, conductive mesh 720 is fixed on electrode 716 and is connected with electrode 718.Working electrode (702,703,704,707,
708,709,712,713,714,717,718,719) apply radio-frequency voltage and alternating voltage, for fettering the behaviour of ion and ion
Make to include introducing, resonant excitation and pop-up.Mesh electrode (705,710,715,720) is used for the introducing and pop-up of ion.Quality
When analyzer works, voltage is acted on bound ion on working electrode, by ion according to the sequence of mass-to-charge ratio size according to
The secondary conductive mesh electrode (715,720) by conductive mesh electrode on the direction x- (705,710) or on the direction y- pops up, and realizes
The separation of the ion of different mass-to-charge ratioes, the collection and multiplication of the ion of pop-up device after testing, the electric signal of generation by amplification,
The data processing systems such as digital-to-analogue conversion are converted into mass spectrogram signal.
Novel ion trap mass analyzer provided by the invention has had both the advantageous characteristic of existing ion strap mass analyzer,
The structure of linear ion trap has the advantage that ion storage space is big, storage efficiency is high;The prior art is overcome simultaneously
Deficiency, segmented electrodes adjust effectively, in real time to the electric field inside linear ion trap, optimization electric field point
Cloth, electric field defect caused by making up electrode simply ensure that the high-resolution of mass analyzer, will also machining and assembling mistake
The influence of performance caused by difference is available effectively to be made up;In addition to this, the mesh electrode structure on segmented electrode ensure that efficiently
The ion of rate introduces and pop-up, can promote mass spectrometric detection sensitivity.In summary advantage, the present invention provides a kind of knots
Simple, the powerful novel ion trap mass analyzer of structure.
The preferred embodiment of the present invention has been described in detail above, but the present invention is not limited to embodiment,
Those skilled in the art can also make on the premise of not violating the inventive spirit of the present invention various equivalent modification or
Replacement, these equivalent variation or replacement are all contained in scope of the present application.
Claims (10)
1. a kind of linear mass analyzer, which is characterized in that including multiple segmented electrodes structures, multiple segmented electrodes knots
Structure is surrounded into stereoeffect;Wherein
One or more segmented electrodes structures be equipped with reticular structure electrode, ion by conductive mesh structure electrode enter and
Pop up mass analyzer;
Any one of segmented electrodes structure lineal layout on the direction x and the direction y, the segmented on the direction x and the direction y
Zx plane and zy plane where electrode structure surround the constraint space that ion is formed into stereoeffect radially;
Wherein
Xyz is rectangular coordinate system in space.
2. linear mass analyzer according to claim 1, which is characterized in that between segmented electrodes structure mutually absolutely
Edge.
3. linear mass analyzer according to claim 1, which is characterized in that the electrode phase in segmented electrodes structure
Mutually insulation.
4. linear mass analyzer according to claim 1, which is characterized in that segmented electrodes structure is complete electricity
Pole, electrode surface profile segment formula electrode.
5. linear mass analyzer according to claim 1, which is characterized in that segmented electrodes structure includes substrate electricity
Pole and the segmented electrode being arranged on basal electrode, are separated between segmented electrode and basal electrode by insulating materials.
6. linear mass analyzer according to claim 1, which is characterized in that the material of reticular structure electrode is metal
Conductive material or non-metal material surface have conductive layer covering.
7. linear mass analyzer according to claim 1, which is characterized in that reticular structure electrode is that the direction x is parallel
Setting that setting line or the direction y are arranged in parallel or the direction x and y is interspersed.
8. linear mass analyzer according to claim 1, which is characterized in that the cross of the conductor wire of reticular structure electrode
Section is round or rectangular.
9. linear mass analyzer according to claim 1, which is characterized in that including unilateral side setting in the x direction
Segmented electrodes structure;Wherein
Segmented electrodes structure includes basal electrode and the segmented electrode that is arranged on basal electrode, segmented electrode and substrate electricity
Separated between pole by insulating materials.
10. linear mass analyzer according to claim 1, which is characterized in that including two pairs points on the direction x and y
Segmentation electrode structure;Wherein
Segmented electrodes structure is complete electrode, electrode surface profile segment formula electrode.
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