CN102723254B - Focusing device and method of flat high-field asymmetric waveform ion mobility spectrometer - Google Patents

Focusing device and method of flat high-field asymmetric waveform ion mobility spectrometer Download PDF

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CN102723254B
CN102723254B CN201210211272.7A CN201210211272A CN102723254B CN 102723254 B CN102723254 B CN 102723254B CN 201210211272 A CN201210211272 A CN 201210211272A CN 102723254 B CN102723254 B CN 102723254B
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focusing
voltage
ion
pole plate
asymmetric waveform
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CN102723254A (en
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唐飞
徐初隆
王晓浩
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Tsinghua University
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Tsinghua University
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Abstract

The invention discloses a focusing device and a focusing method of a flat high-field asymmetric waveform ion mobility spectrometer. The flat high-field asymmetric waveform ion mobility spectrometer comprises an ion source, a mobility area and a detection unit, wherein an upper substrate and a lower substrate are placed in parallel in the mobility area; an upper mobility area electrode and a lower mobility area electrode are respectively arranged on the upper substrate and the lower substrate; and the upper mobility area electrode is connected with an asymmetric waveform radio frequency power supply and a direct current scanning compensation power supply. The focusing device is characterized in that at least one focusing area is arranged at the front end of the mobility area; and at least one focusing polar plate pair is arranged on each of the upper and lower substrates of each focusing area. The focusing method employing the focusing device is characterized in that voltage is applied to each focusing polar plate pair, so ions are gathered to the center before entering the mobility area; the applied voltage has two modes, namely a direct current focusing mode and a radio frequency focusing mode; in the direct current focusing mode, the same direct current voltage is applied to the focusing polar plate pair at intervals; and in the radio frequency focusing mode, sine radio frequency voltage is applied to each focusing polar plate pair, and the difference of the radio frequency voltage phases of the adjacent focusing polar plate pairs is 180 DEG.

Description

The focusing arrangement of plate High-Field Asymmetric Waveform Ion Mobility Spectrometer and method
Technical field
The present invention relates to and biochemical substances is measured, belong to field assay detection field, be specially one and ion beam is focused on, improve the device and method of plate High-Field Asymmetric Waveform Ion Mobility Spectrometer resolution.
Background technology
High-Field asymmetric waveform ion mobility spectrometry (FAIMS, High-field Asymmetric Waveform Ion MobilitySpectrometry) is a kind of biochemical substances detection technique that the nineties progressively grows up last century.It mainly utilizes the mobility of ion under high electric field the characteristic different with the change of electric field strength can be separated and detect different types of biochemical substances.Its general principle is as follows: under low current field condition, and the mobility coefficients of ion and electric field strength have nothing to do; After electric field strength height to certain value (E/N>40Td), the mobility coefficients K of ion will change with electric field strength in the nonlinear mode of one.The relation of the mobility of ion under High-Field and electric field strength is available as shown in the formula subrepresentation:
K=K 0[1+ α 1(E/N) 2+ α 2(E/N) 4+ ... ], wherein K is the mobility of ion under high electric field, K 0for the mobility of ion under low electric field, E is electric field strength, and N is gas density, α 1, α 2for ionic mobility decomposition coefficient.Make α (E)=[α 1(E/N) 2+ α 2(E/N) 4+ ... ], then K=K 0[1+ α (E)].As α (E) >0, K>K 0, then K increases with E and increases; As α (E) <0, K<K 0, then K reduces along with the increase of E; As α (E) ≈ 0, K ≈ K 0.As seen from the above analysis, under the effect of high electric field, the mobility of ion can present nonlinear trends different separately, and this just makes the ion that ionic mobility is identical or close under low electric field strength condition separatedly under high electric field strength condition to open.
At present, High-Field asymmetric waveform ion mobility spectrometry mainly contains plate and cylinder type two kinds of structures, compared to cylinder type, plate High-Field Asymmetric Waveform Ion Mobility Spectrometer is easier to micro electro mechanical system (MEMS) technology (MEMS, Micro-Electro-Mechanical System) carry out process, be convenient to microminiaturization, therefore in portable biochemical detecting instrument device, there is larger advantage.
University and Sionex company are stood to the New Mexico that mainly contains that plate High-Field Asymmetric Waveform Ion Mobility Spectrometer is furtherd investigate, its main core chip architecture adopts MEMS process technology design processing, and ion source adopts vacuum UV lamp ion source or 63Ni ion source.This plate High-Field Asymmetric Waveform Ion Mobility Spectrometer has two kinds of versions, and carrier gas is as shown in Figure 1 perpendicular to the mode entered facing to ion source shown in ion source and Fig. 2 respectively.These two kinds of frame modes all also exist deficiency: owing to adopting plate armature, lack focusing power, the ion after ion source ionization will spread in whole migration area, and produces up-down vibration under the driving of asymmetric electric field; When dc sweeps bucking voltage is a certain particular value, ion is zero in the clean displacement of a rf period; In theory, when dc sweeps bucking voltage departs from this value, signal strength signal intensity can sharply reduce, but due to the distribution of ion in migration area, signal strength signal intensity can not reduce rapidly, and this just causes producing spectral line expansion when spectral line measurement, causes resolution to reduce.
Summary of the invention
The object of the invention is the deficiency overcoming existing plate High-Field Asymmetric Waveform Ion Mobility Spectrometer, a kind of focusing arrangement and focus method are provided, ion was retrained the width of ion beam before entering migration area, reduce the broadening of spectral lines caused because ion disperses in migration area, improve the resolution of system.
Technical scheme of the present invention is as follows:
A focusing arrangement for plate High-Field Asymmetric Waveform Ion Mobility Spectrometer, described slab construction High-Field Asymmetric Waveform Ion Mobility Spectrometer comprises ion source, migration area and detecting unit; Substrate and subtegulum in parallel placement in migration area, migration area electrode and lower migration area electrode on upper substrate and subtegulum are arranged respectively, upper migration area electrode is connected with dc sweeps offset supply with asymmetric waveform radio-frequency power supply respectively; Focusing arrangement is characterized in that: arrange at least one focal zone in front end, migration area, the upper substrate and subtegulum of each focal zone arranges at least one pair and focuses on pole plate pair, and just right up and down.
Adopt the plate High-Field Asymmetric Waveform Ion Mobility Spectrometer focus method of the one of above-mentioned focusing arrangement, it is characterized in that: every secondary focus on pole plate on apply voltage, the forward direction center that ion is entering migration area is assembled, and the voltage of applying has two kinds of patterns,
A. direct current focusing mode: direct current focusing mode be focusing pole plate on interval apply identical direct voltage, and apply the focusing pole plate of direct voltage to adjacent focusing pole plate to not applying voltage; The direct voltage applied selects polarity according to ion polarity, if cation applies positive voltage, if anion applies negative voltage;
B. radio frequency focusing pattern: radio frequency focusing pattern for every secondary focus on pole plate on apply sinusoidal radio frequency voltage, adjacent focus pole plate radio frequency voltage-phase differs 180 °.
The present invention has the following advantages and high-lighting effect: 1., the right structure of focusing pole plate of the present invention can effectively focus on ion beam width, improves resolution; 2., the present invention can work in atmospheric conditions, do not need the pumped vacuum systems of assisting; 3., the present invention totally based on slab construction, the structure of focal zone, migration area and detecting unit is all convenient to adopt MEMS process technology to process, and is easy to integrated, is convenient to FAIMS system microminiaturized.
Accompanying drawing explanation
Fig. 1 is the plate High-Field Asymmetric Waveform Ion Mobility Spectrometer structural principle schematic diagram that in prior art, carrier gas enters perpendicular to ion source.
Fig. 2 is the plate High-Field Asymmetric Waveform Ion Mobility Spectrometer structural principle schematic diagram that in prior art, carrier gas enters facing to ion source.
Fig. 3 is the structural principle schematic diagram of plate High-Field Asymmetric Waveform Ion Mobility Spectrometer focusing arrangement provided by the invention.
Fig. 4 focuses on pole plate to applied V diagram under the present invention adopts direct current focusing mode.
Fig. 5 focuses on pole plate to applied V diagram under the present invention adopts radio frequency focusing pattern.
Fig. 6 is the focusing principle figure of direct current focusing mode.
Fig. 7 is the focusing principle figure of radio frequency focusing pattern.
Fig. 8 is asymmetric waveform radio-frequency voltage schematic diagram.
Fig. 9 is dc sweeps bucking voltage schematic diagram.
In figure: 1-carrier gas; 2-ion source; 3-migration area; The upper substrate of 4-; 5-subtegulum; 6-upper migration area electrode; Migration area electrode under 7-; 8-detecting unit; 9-dc sweeps offset supply; 10-asymmetric waveform radio-frequency power supply; 11-focal zone; 12-first focuses on pole plate pair; 13-second focuses on pole plate pair; 14-the 3rd focuses on pole plate pair; 15-the 4th focuses on pole plate pair; 16-the 5th focuses on pole plate pair.
Embodiment
Below in conjunction with the drawings and specific embodiments, the focusing arrangement of a kind of plate High-Field asymmetric waveform ion mobility spectrometry provided by the invention and method are described further.
Fig. 3 is the structural representation of plate High-Field Asymmetric Waveform Ion Mobility Spectrometer focusing arrangement of the present invention.Described plate High-Field Asymmetric Waveform Ion Mobility Spectrometer comprises ion source 2, migration area 3 and detecting unit 8, and wherein migration area 3 comprises substrate 4, subtegulum 5, upper migration area electrode 6 and lower migration area electrode 7; The placement parallel with subtegulum 5 of upper substrate 4, form the gas channels of migration area 3, upper migration area electrode 6 and lower migration area electrode 7 lay respectively on substrate 4 and subtegulum 5; At the rear portion of migration area 3, the end of gas channels is the detecting unit 8 that can detect faint ion current; Upper migration area electrode 6 is connected with dc sweeps offset supply 9 with asymmetric waveform radio-frequency power supply 10 respectively.Focusing arrangement is the focal zone 11 between ion source 2 and migration area 3, is at least provided with a secondary focusing pole plate pair in focal zone 11.As being provided with the first focusing pole plate in the embodiment of Fig. 3, pole plate is focused on to the 15, the 5th focusing pole plate to 16 to the 13, the 3rd focusing pole plate to the 14, the 4th to the 12, second focusing pole plate.
The focus method action principle of illustrated plate High-Field Asymmetric Waveform Ion Mobility Spectrometer is as follows:
Carrier gas 1 carries sample and passes in ionic migration spectrometer, and sample ionization occurs under ion source 2 acts on and forms sample ions.
After ion to be carried by carrier gas and enters focal zone 11, focusing pole plate on apply voltage, the forward direction center that ion is entering migration area is assembled, and the voltage of applying has two kinds of patterns: direct current focusing mode and radio frequency focusing pattern.Direct current focusing mode be focusing pole plate on interval apply identical direct voltage, and apply the focusing pole plate of direct voltage to adjacent focusing pole plate to not applying voltage; The direct voltage applied selects polarity according to ion polarity, if cation applies positive voltage, if anion applies negative voltage.Radio frequency focusing pattern for every secondary focus on pole plate on apply sinusoidal radio frequency voltage, adjacent focus pole plate radio frequency voltage-phase differs 180 °.
Under making focal zone be operated in direct current focusing mode or radio frequency focusing pattern: under direct current focusing mode, each focusing pole plate to institute's making alive as shown in Figure 4; Under radio frequency focusing pattern, each focusing pole plate to institute's making alive as shown in Figure 5.Ion gathers at the effect Xia Xiang center of focal zone, and as shown in Figure 6, the focusing results of radio frequency focusing pattern as shown in Figure 7 for the focusing results of direct current focusing mode; Finally, the width entering the ion beam of migration area 3 reduces.
Upper migration area electrode 6 is connected with asymmetric waveform radio-frequency power supply 10 with dc sweeps offset supply 9 respectively, lower migration area electrode 7 ground connection.The voltage that wherein asymmetric waveform radio-frequency power supply 10 produces is the High-Field asymmetric waveform (as shown in Figure 8) of upper and lower area equation; The voltage that dc sweeps offset supply 9 produces carries out scanning (as shown in Figure 9) between the interval CV1 ~ CV2 of certain dc sweeps bucking voltage with specific scanning frequency and scanning step.For ion not of the same race, under the effect of asymmetric waveform radio-frequency voltage, certain ion upwards migration area electrode 6 or lower migration area electrode 7 produces a clean displacement and (depends on the kinetic characteristic of ion under high field action, the clean displacement of different ions is different), if do not have the effect of dc sweeps bucking voltage, generation deflection strikes on upper migration area electrode 6 or lower migration area electrode 7 and is neutralized by ion.If load a suitable dc sweeps offset supply, the clean displacement energy that ion is produced under the effect of asymmetric waveform radio-frequency voltage accesses compensation, then ion is by migration area.The ion of certain dc sweeps bucking voltage so corresponding can pass through migration area, and other ion then strikes on metal electrode and is neutralized.Then the corresponding different types of ion of the dc sweeps bucking voltage of different size, therefore just can determine the kind of sample according to the value of dc sweeps bucking voltage.Due to the effect of the 11 pairs of ion beam widths in focal zone constraint, when dc sweeps bucking voltage departs from the dc sweeps bucking voltage value that certain ion pair answers time, signal strength signal intensity can obviously reduce, and peak width reduces, and resolution improves.
Filter through migration area 3 under the effect of the ion after selecting in carrier gas and continue to move right, enter detecting unit 8, ion signal is converted into current signal, measure the value of current signal.By recording the related data of the electric current that the corresponding moment detecting unit of each dc sweeps bucking voltage detects, and drawn both corresponding relation curves in real time by software.Through noise and the image procossing of microprocessor, determine the dc sweeps bucking voltage value that in each waveform, current signal maximum is corresponding.Data in the flow velocity of the size (length, width, spacing) of the relevant parameter (voltage max, frequency, duty ratio, waveform etc.) of High-Field asymmetric waveform radio-frequency voltage now and dc sweeps bucking voltage, migration area, air pressure, pure carrier gas, temperature and kind (High Purity Nitrogen, cleaned air, carbon dioxide etc.) and dc sweeps bucking voltage value and database are compared, thus determines sample material kind entrained in sample carrier gas.
Embodiment 1:
Ion focusing type High-Field Asymmetric Waveform Ion Mobility Spectrometer is utilized to detect acetone.Carrier gas 1 is carried acetone and is entered ionic migration spectrometer.According to the ionization property of ion source 2, carrier gas 1 is the High Purity Nitrogen of 99.999%, and flow velocity is defined as 0.96L/min.Asymmetric waveform radio-frequency power supply 10 produces frequency 1MHz, and the asymmetric waveform radio-frequency voltage of duty ratio 30%, is carried on migration area electrode 6.The acetone ion of ionization focuses under the effect of focal zone 11, ion beam width reduces, then migration area 3 is entered, and asymmetric waveform radio-frequency voltage makes acetone ion be separated with the foreign ion in carrier gas in migration area, the dc sweeps bucking voltage of acetone and the real-time curve of current signal corresponding relation is obtained finally by control dc sweeps offset supply 9, determine the dc sweeps bucking voltage that acetone is corresponding, by comparing determination substance classes.From the experimental results, when asymmetric waveform radio-frequency voltage peak-to-peak value is 800V, after loading focus voltage, the acetone ion signal peak reductions detected is little, and detection resolution is improved.
Direct current focusing mode
Voltage-drop loading mode Peak width/V Resolution improves
0-0-0-0-0 2.8556 0
0-1.25-0-1.25-0 2.7612 3.31%
0-5-0-5-0 2.7494 3.72%
0-10-0-10-0 2.7612 3.31%
0-15-0-15-0 2.4662 13.64%
0-20-0-20-0 2.6786 6.20%
Radio frequency focusing pattern
Voltage-drop loading mode Peak width/V Resolution improves
25khz0v 2.9500 0
25khz16v 2.8674 2.80%
25khz30v 2.7966 5.20%
25khz47v 2.6432 10.40%
25khz60v 2.6786 9.20%
25khz70v 2.6668 9.60%
Embodiment 2:
MEMS technology is adopted to carry out the system integration to ion focusing type High-Field Asymmetric Waveform Ion Mobility Spectrometer.Ion source 2 adopts the corona discharge ion source of cylinder type, and detecting unit 8 adopts the microarray formula Faraday cup of column structure.Ion source 2 and detecting unit 8 all form by ICP technique etching conductive silicon chip.Upper substrate 4 and subtegulum 5 adopt Pyrex.On-chip upper migration area electrode 6, lower migration area electrode 7, focus on pole plate to 12, focus on pole plate to 13, focus on pole plate to 14, focus on pole plate to 15, focus on pole plate and form (thickness Ti:400 to 16 by sputtered with Ti/Pt/Au metal on borosilicate glass ; Pt:300 au:900 ).Substrate is assembled by bonding technology.Adopt the discharge mode of negative corona during experiment, acetic acid sample entrained in carrier gas is ionized.According to the operating characteristic of cylinder type corona discharge ion source, the gas flow rate of carrier gas is adjusted to 100ml/min.Under certain High-Field asymmetric waveform radio-frequency voltage parameter, the suitable resolution of the type of focusing to signal is selected to strengthen, by dc sweeps bucking voltage, obtain corresponding signal curve, by the substance classes of the comparison determination acetic acid to acetic acid dc sweeps bucking voltage.

Claims (1)

1. a plate High-Field Asymmetric Waveform Ion Mobility Spectrometer focus method, described plate High-Field Asymmetric Waveform Ion Mobility Spectrometer comprises ion source (2), migration area (3) and detecting unit (8); Substrate (4) and subtegulum (5) in parallel placement in migration area (3), upper substrate (4) and subtegulum (5) arrange upper migration area electrode (6) and lower migration area electrode (7) respectively, and upper migration area electrode (6) is connected with dc sweeps offset supply (9) with asymmetric waveform radio-frequency power supply (10) respectively; It is characterized in that, described method adopts following focusing arrangement: arrange at least one focal zone (11) in migration area (3) front end, the upper substrate (4) and subtegulum (5) of each focal zone (11) arrange at least one pair and focuses on pole plate pair, and just right up and down; Every secondary focus on pole plate on apply voltage, the forward direction center that ion is entering migration area is assembled, and the voltage of applying has two kinds of patterns:
A. direct current focusing mode: direct current focusing mode be focusing pole plate on interval apply identical direct voltage, and apply the focusing pole plate of direct voltage to adjacent focusing pole plate to not applying voltage; The direct voltage applied selects polarity according to ion polarity, if cation applies positive voltage, if anion applies negative voltage;
B. radio frequency focusing pattern: radio frequency focusing pattern for every secondary focus on pole plate on apply sinusoidal radio frequency voltage, adjacent focus pole plate radio frequency voltage-phase differs 180 °.
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CN103811267A (en) * 2012-11-14 2014-05-21 中国科学院大连化学物理研究所 Combined type planar differential ion mobility spectrometry capable of simultaneously detecting positive and negative ions
CN103107060A (en) * 2013-01-18 2013-05-15 中国科学院大连化学物理研究所 Ionic migration spectrum with radio frequency confinement function
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