CN112259440A - Vacuum ultraviolet internal ionization mass spectrometry device and mass spectrometry method - Google Patents
Vacuum ultraviolet internal ionization mass spectrometry device and mass spectrometry method Download PDFInfo
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Abstract
The invention provides a vacuum ultraviolet internal ionization mass spectrometry device and a mass spectrometry method, comprising the following steps: the device comprises an ultraviolet light source, a mass analyzer, a light beam adjusting component, an analysis sample and a controller; the ultraviolet light source can carry out single photon ionization on an analysis sample; the mass analyzer is capable of internally performing a complete mass spectrometry operating sequence from ionization of an analysis sample to mass separation of ions; the mass analyzer is provided with a light source inlet; the light beam adjusting component is arranged at the upstream of the light source introducing port; the controller can synchronously control the working time sequence stage of the quality analyzer and the modulation amount of the light beam adjusting component; the invention adopts a simple valve or a light modulation structure, can use a high-sensitivity internal ionization analysis mode in vacuum ultraviolet light ionization mass spectrometry, and simultaneously avoids the interference of bottom noise signals caused by the traditional continuous ultraviolet light source ionization method. The limit of analysis and detection can be improved by about 2-3 orders of magnitude.
Description
Technical Field
The invention relates to the technical field of mass spectrometry, in particular to a vacuum ultraviolet internal ionization mass spectrometry device and a mass spectrometry method. In particular to a micro mass spectrometry device and a method thereof which can realize the ionization of a sample to be detected and reduce the interference in the mass analysis stage by a small continuous ultraviolet light ionization light source.
Background
The mass spectrometry technology is widely applied in the fields of public safety, biomedicine, advanced material analysis and development and the like. Wherein, the small-sized and micro mass spectrum system is gradually becoming an important analysis means in the field analysis application of various fields such as national defense safety, other industries, civil use and the like. At present, the portable field mass spectrum total analysis mainly depends on a gas chromatography-mass spectrum combined technology, and the main principle is that a gas sample or other phase samples which can be introduced for analysis are gasified and introduced into a chromatographic column, and are separated into basically pure compounds according to the difference of retention or adsorption conditions of different sample molecules on the chromatographic column; and ionizing the sample molecular fragments by means of electron impact ionization (EI) and the like to form a mass spectrogram, and inquiring and comparing the mass spectrogram with a mass spectrogram of a standard substance to obtain quantitative information of a series of compounds. The method has good measurement accuracy, but the equipment comprises a series of complex devices such as a sample inlet, a sampling pump, a quantitative ring, a chromatographic column, a mass spectrum interface, an electron bombardment ionization source, a lead-in lens, a mass analyzer and the like required by the chromatogram and the mass spectrum, so that the equipment has many challenges in the engineering of the miniaturization field below 10 kg. Particularly, in the application fields of aerospace load and the like which have strict requirements on the mass power consumption of the system, the further miniaturization of equipment is very difficult, and meanwhile, a large number of small components in the system cause great limitation on the stress load of the mass spectrometry system. Therefore, there is a need to find a new mass spectrum total analysis device to meet the demand of miniaturization of mass spectrum system in the advanced fields of aerospace and the like.
In a complex sample environment, the traditional mass spectrum total analysis method which does not depend on a chromatographic separation technology and the like mainly has the problem of fragmentation of sample molecules. Taking an EI source as an example, a sample molecule in the source can generate a large number of ions under the effect of electron bombardment ionization of 70 electron volts (eV). However, the energy transfer of the process is violent and exceeds the chemical bond energy level of a few eV of a common compound, and the ions with larger internal energy are spontaneously cracked to generate more fragments when colliding with neutral molecules. For example, common plasticizer phthalate forms 149u fragments, hydrocarbon compounds form 43, 57u and other common hydrocarbon fragments, and a large amount of fragments form chemical signals which cut off sample molecules and form mutual interference.
Compared with an EI ionization method, vacuum ultraviolet photoionization (VUV-PI) has extremely low ion fragment yield, and water vapor, nitrogen and oxygen in earth atmosphere and main background interferences such as carbon dioxide in gold star and mars atmosphere, methane in soil satellite and the like are not ionized under the action of 10.6eV photons output by a common continuous krypton discharge vacuum ultraviolet lamp. Therefore, the chemical background of the mass spectrogram obtained by the VUV-PI ionization method is clean, and the molecular weight information of the sample capable of being ionized can be directly obtained. Based on the obtained molecular weight information, further chemical information of each substance can be obtained through a cascade mass analyzer such as an ion trap and a high-resolution mass analyzer such as a time-of-flight mass spectrometer, so that high-efficiency full-spectrum rapid analysis is achieved.
However, compared with other ionization techniques, there is no laser light source that can be miniaturized in the vacuum ultraviolet region (wavelength of 10-195 nm), so that the currently mainly applied excimer laser, inert gas ion laser, free electron laser and other means require huge testing devices, and the laser method has low photon energy, which is not favorable for obtaining ionization mass spectrum information of main substances. At present, the field is mainly based on that vacuum ultraviolet photons with the energy of more than 8eV are obtained by a direct current or radio frequency hollow discharge lamp. The continuous discharge method is proved to be a stable vacuum ultraviolet light generation method through mature products of many light source enterprises such as celebrity and the like, but the processes of starting and extinguishing the arc of the discharge process are all unstable from several milliseconds to sub-second.
Patent document CN1811408B proposes that an ion trap mass spectrometry of internal photoionization is used for analyzing and detecting a sample, but because the pulse generation stability of vacuum ultraviolet light is difficult, there is no micro mass spectrometry device and method that can really perform high-sensitivity internal ionization mode analysis.
The main reasons for this problem are: the instability of the light source during the ionization phase of the sample in the mass analyzer, and the strong background noise caused by the continuous ionization of the material in the mass analyzer by the vacuum ultraviolet light continuously input during the mass analysis phase. In fact, especially because the vacuum ultraviolet light input in the mass analysis stage cannot be smoothly stopped, the improvement of the relative sensitivity and the detection limit of mass spectrum detection, which are originally brought by the internal ionization method, cannot be basically realized. Therefore, it is necessary to find a micro mass spectrometry apparatus and an analysis method for overcoming the instability of timing control of vacuum ultraviolet light, improving the signal repeatability of the ionization stage of the internal ionization mass spectrometry, and eliminating the photoionization background noise of the mass analysis stage.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a vacuum ultraviolet internal ionization mass spectrometry device and a mass spectrometry method.
The invention provides a vacuum ultraviolet internal ionization mass spectrometry device, which comprises: the device comprises an ultraviolet light source, a mass analyzer, a light beam adjusting part, an analysis sample and a controller;
the ultraviolet light source can carry out single photon ionization on an analysis sample;
the mass analyzer is capable of internally performing a complete mass spectrometry operating sequence from ionization of an analysis sample to mass separation of ions;
the mass analyzer is provided with a light source inlet;
the light beam adjusting component is arranged at the upstream of the light source introducing port;
the controller can synchronously control the working time sequence stage of the quality analyzer and the modulation amount of the light beam adjusting component;
the ultraviolet light source adopts a continuous vacuum ultraviolet light source;
the working sequence stage synchronously controlled by the controller comprises any one or more of the following steps:
-sample ionization;
-ion kinetic energy regulation;
-separation of ions of different mass to charge ratios.
Preferably, the mass analyser is an ion trap mass analyser, and the required ions in the ion trap are enriched by controlling the electrode voltage of the ion trap.
Preferably, the ion trap further comprises an ion trap;
the illumination direction of the ultraviolet light source is coincident with the axis of the direction of the analysis sample entering the ion trap.
Preferably, the ion trap adopts a cylindrical or square large-capacity ion trap.
Preferably, the ion kinetic energy adjustment voltage of the mass analyser is a periodic square wave or pulse.
Preferably, the ion kinetic energy adjustment voltage of the mass analyser is a periodic square wave or pulse.
Preferably, the method further comprises the following steps: a sample injection valve;
the opening time sequence of the sample injection valve is synchronous with the high conduction time sequence of the light beam adjusting part.
Preferably, the beam adjusting component makes the vacuum ultraviolet light output by the continuous vacuum ultraviolet light source bombard the surface with electron work function lower than the vacuum ultraviolet photon energy in at least one part of time, generates the electron work function and ionizes at least one part of sample molecules and background gas molecules in the vacuum ultraviolet light internal ionization mass spectrometry device.
Preferably, the method further comprises the following steps: a collecting electrode, an ion multiplying member;
the collecting electrode can detect the vacuum degree;
the collecting electrode can collect current signals formed by ions formed by ionization of at least one part of sample molecules and background gas molecules in the vacuum ultraviolet internal ionization mass spectrometry device, the current signals are input into the controller, whether the internal air pressure of the vacuum ultraviolet internal ionization mass spectrometry device meets the high-voltage safe working threshold range of the ion multiplication component or not is calculated, and the working high voltage of the ion multiplication component is controlled to be switched on and off according to a threshold judgment result.
Preferably, the vacuum ultraviolet internal ionization mass spectrometry device comprises:
step S1: starting the continuous vacuum ultraviolet light source, and keeping the intensity of the output vacuum ultraviolet light of the continuous vacuum ultraviolet light source stable within the range of +/-1% around the set average output value;
step S2: controlling the working conditions of the mass analyzer by using a controller, enabling the mass analyzer to enter a sample ionization working stage, and enabling a sample introduced into the mass analyzer to be ionized into sample ions under the action of output vacuum ultraviolet light, and simultaneously remaining in the mass analyzer;
step S3: controlling the light beam adjusting component by a controller to reduce the intensity of the vacuum ultraviolet light entering the mass analyzer to be 1% or less of the average output value set by the continuous vacuum ultraviolet light source;
step S4: controlling the working conditions of the mass analyzer by adopting a controller, enabling the mass analyzer to enter an ion kinetic energy adjusting stage, adjusting the kinetic energy of sample ions residing in the mass analyzer, and meeting the ion kinetic energy and potential energy distribution state of the ion separation of subsequent ions with different mass-to-charge ratios;
step S5: and controlling the working conditions of the mass analyzer by adopting a controller, so that the mass analyzer enters an ion separation stage with different mass-to-charge ratios, and separating sample ionic electric signals with different mass-to-charge ratios according to the mass number sequence to obtain a mass spectrogram.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts a simple valve or a light modulation structure, can use a high-sensitivity internal ionization analysis mode in vacuum ultraviolet light ionization mass spectrometry, and simultaneously avoids the interference of bottom noise signals caused by the traditional continuous ultraviolet light source ionization method. The analysis detection limit can be improved by about 2-3 orders of magnitude;
2. the invention can further reduce the influence of the neutral noise of the sample on the mass spectrum analysis of the extremely low-content vacuum residual gas by arranging the same valve type modulation device for opening and closing the ultraviolet light path and the sample incidence. The method can also reduce the load of the vacuum chamber where the mass spectrometer is positioned, reduce the cost of the vacuum pump set and reduce the volume and weight of the whole machine when the vacuum pump set is used for analyzing the load;
3. the invention has reasonable structure and convenient use and can overcome the defects of the prior art.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a schematic diagram of the structure and operation of a conventional ionization mass spectrometer in a vacuum UV light source.
FIG. 2 is a schematic diagram of a prior art vacuum UV light source external ionization mass spectrometer.
Fig. 3 is a timing diagram illustrating the structure and operation of an exemplary embodiment of the present invention.
Figure 4a is a schematic diagram of a cylindrical ion trap that may be used in embodiments of the present invention.
Figure 4b is a schematic diagram of a square ion trap configuration that may be used in embodiments of the present invention.
Fig. 4c is a schematic diagram of a time-of-flight mass analyzer that may be used in embodiments of the present invention.
FIG. 5 is a diagram illustrating a spectrum of dioctyl phthalate 391u as an analytical sample in accordance with an exemplary embodiment of the present invention.
Fig. 6a is a timing diagram illustrating the structure and operation of an improved embodiment of the present invention employing valves to further enhance the synchronization performance of sample analysis.
FIG. 6b is a timing diagram showing the structure and operation of an improved embodiment of the present invention using a valve for both the sample introduction and the UV modulated internal ionization process.
Fig. 7 is a schematic diagram of the structure and the optimized relationship of light intensity-noise-deflection voltage of the improved embodiment of the present invention using a deflection voltage device as an ultraviolet light modulator.
FIG. 8 is a block diagram of an improved embodiment for extending the range of ionization analysis of a sample by the apparatus of the present invention through electron capture or post-accelerated ionization of electrons using a portion of the UV light that is gated off or shielded to generate emitted photoelectrons.
Fig. 9 is a structure and an operation timing diagram of an embodiment of the present invention for improving stability, which utilizes a portion of the ultraviolet light that is blocked or shielded, collects current signals formed by ions formed by ionization of the sample molecules and background gas molecules of the portion, calculates whether the internal gas pressure of the ultraviolet internal photoionization mass spectrometry device satisfies the high-voltage safe operation threshold range of the ion multiplier, and controls to switch the operation high voltage of the ion multiplier.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
At present, a common mass spectrometer is structurally designed as shown in fig. 1, and sample gas molecules enter the mass spectrometer and then freely escape in a vacuum chamber, and are ionized when passing through a light beam generated by an ultraviolet light source 101 to form relatively complete charged particles, and the charged particles enter a mass analyzer through a charged particle channel in the center of an ion trap. In this common design, since it is currently difficult to realize a miniaturized laser light source in the vacuum ultraviolet band, particularly a vacuum ultraviolet light source having photon energy of 8eV (electron volts) or more, there is no reasonable solution until now when the dissipation power is 10W or less, and this vacuum design can be realized only by using a continuous discharge type Ar/Kr lamp.
Taking the linear ion trap mass analyzer 102 as an example, a light source inlet 104 is opened at one end in the direction of the axis 103, and through the mass analyzer external control controller circuit 105, an ion gate voltage is added to two end caps 106 and 107 of the linear ion trap, and a bound radio frequency RF and an excitation alternating voltage AC are respectively added to two pairs of bound radio frequency electrodes 108 and 109. As can be seen from the timing diagram of fig. 1 for the application of various voltages, the mass analyzer operating phases include at least 3 timing phases: a) sample ionization 1001; b) cooling and adjusting 1002 by ion kinetic energy; c) ions of different mass to charge ratios are separated 1003.
In accordance with the principles of internal ionization mass spectrometry apparatus, the incident vacuum ultraviolet light need only be ionized at the ionization event timing stage 1001 of the mass analyzer 102. Due to the ignition 1010 and extinction phase 1020 of the operating sequence of this type of gas discharge lamp, the establishment or cessation of the discharge process is a highly random process accompanied by random ionization flooding or quenching. Vacuum uv photons that continue into the mass analyzer during mass analysis processes that do not require the introduction of ions, such as timing stages 1002 or 1003 in the figure, can create additional background ionization or penning processes for the internal background gas. Particularly, the introduction of additional vacuum ultraviolet light in the ion separation time sequence stage 1003 with different mass-to-charge ratios can continuously generate uncontrolled stray ions or neutral excited-state species signals in the mass analyzer, which seriously affects the mass spectrometry efficiency of the ionization device in the class, and the residual impurity ions can occupy the constrained potential well in the mass analyzer, which generates a space charge effect to affect the ionization efficiency of the sample ionization time sequence stage in the next period. Therefore, the ionization efficiency of the sample gas molecules and the final detection sensitivity of the mass analyzer are low in the design, and a design scheme for improving the ionization and analysis efficiency needs to be considered.
The conventional solution is to use the external ionization scheme shown in fig. 2 and an external additional ion source 210 to make the light path emitted by the continuous uv light source 201 perpendicular to the optical axis of the mass analyzer 202, so as to reduce the influence of the continuously emitted vacuum uv light on the mass analyzer in the non-sample ionization timing sequence stage as much as possible. However, such mass spectrometry devices require the introduction of ions from outside the mass analyzer, introducing additional external ionization power volumes and dynamic circuit consumption of the ion lens/end cap ion gate. Furthermore, for rf trap-type mass analysers, effective external ion trapping requires the assistance of an internal collision gas, typically at a gas pressure of 10-1-10-4Pa range. For higher vacuum outer stars, e.g. lunar surface or 10-5The typical molecular mean free path of the space environment simulator with vacuum degree of Pa and below is far greater than 10-2-10-1Mass analyser feature sizes on the order of meters, which results in very poor sensitivity or no use at all of such analysers. This is very disadvantageous for realizing a lightweight aerospace and ground analysis device.
To solve this problem, as shown in fig. 3, a basic embodiment of the present invention provides a vacuum ultraviolet internal ionization mass spectrometry apparatus, including: at least one continuous vacuum ultraviolet light source for single photon ionization of analytes, such as a krypton-filled hollow dc discharge lamp 301 in this embodiment, injects ultraviolet light into the mass analyzer 302 axis 303 for the complete mass spectrometry operating sequence for complete ionization of the sample to ion mass separation; at least one beam adjusting component 310 for adjusting the intensity of the vacuum ultraviolet light incident on the mass analyzer, in this case an optical chopper, which can modulate the change of the intensity of the ultraviolet light by changing its position or direction state, thereby controlling the ionization condition of the sample molecules; at least one controller 310 for controlling the operation of the mass analyzer 302 and the beam conditioning component 301 in synchronization. By means of the mass analyser external control controller circuit 305, an ion gate electrostatic voltage may be added to the two end caps 306, 307 of the linear ion trap, a conditioning enable signal may be added to the conditioning means, and a confining radio frequency RF and an excitation AC voltage AC may be added to its two pairs of confining radio frequency electrodes 308 and 309, respectively. The mass analyser operating phases comprise at least 3 timing phases: a) Sample ionization 3001; b) ion kinetic energy cooling adjustment 3002; c) ions of different mass to charge ratios are separated 3003.
In one embodiment of this embodiment, the device is a chopper, i.e., a rotatable disk with a light-transmitting notch, made of a metal or non-metal light-absorbing material that does not conduct the vacuum ultraviolet light source. When the mass spectrometer starts working, sample gas molecules enter the vacuum cavity from a gap on the sample inlet 304 or other mass analyzers, the molecules are freely diffused and converged with a vacuum ultraviolet light beam emitted by the light source, the sample gas molecules in the central ion channel are ionized by ultraviolet light irradiation, and the sample gas molecules enter the analysis chamber after free flight. The method has the advantages that the problem of photo-generated noise of ion kinetic energy cooling regulation of the mass analyzer or ion separation working sequence stages with different mass-to-charge ratios does not need to be avoided. The central axis 303 of the analyzer can coincide with the ultraviolet light beam at a small angle or even be completely coaxial, so that the number of sample ions entering the analysis chamber is greatly increased, and the signal intensity is directly increased.
In the example where the position of the optical chopper plate 310 is adjusted by the controller, the controller 310 pulses the emitted uv light by varying the chopper rotation frequency so that the ionized sample gas ion beam is also characterized and better matches the analytical operation of the mass analyzer.
It should be noted that internal ionization mass analyzers of different weights are suitable for use with the apparatus method, as shown in fig. 4, the mass analyzer in this embodiment may be a cylindrical ion trap 410 or a square ion trap 420, and particularly, after a square ion trap structure is adopted, the structural features of the ion trap are easy to implement by a micro-mechanical micro-machining (MEMS) process, and the consistency and repeatability of the microstructure of the mass spectrum can be ensured at the micron-scale size. In addition, the mass analyzer may also be a miniature time-of-flight mass analyzer 430 also fabricated by MEMS process, which includes an ionization accelerating region electrode 4301, a silicon grid 4302, a laminated mirror 4303 and a planar time-focusing microchannel detector 4304. Because a modulation device is adopted to control the continuous vacuum ultraviolet light source, the ion beam obtained by ionization can be coincided with the ultraviolet light beam, the detection efficiency of the analyzer is further improved, the planar micro-channel detector 4304 and the accelerating area electrode 4301 can be processed on the same substrate by using the MEMS technology, the influence of photoproduction noise is avoided, and meanwhile, the processing precision of the whole mass analyzer is improved.
Fig. 5 shows the analysis effect of conventional vacuum uv photoionization using a square linear ion trap with a length of 22 mm, which is formed by 4 rectangular planar electrodes constructed by coating 4 pieces of high vacuum insulating resin, and the radius of the actual emission x-direction field is 1.62mm, and the radius of the vertical y-direction field is 1.39 mm. Parallel slots 0.2mm wide were cut in the exit direction and the configuration was consistent with that shown in figure 1/3. When an external ionization mode is used, the voltages of the front 3 focusing lenses are-88V, -3.8V and-1V respectively, the ion optical structure is shown in fig. 2, the voltage of the front end cover of the ion trap is 1V in the sample ionization time sequence stage, and the voltage of the other ion kinetic energy cooling regulation and the time sequence stage of ion separation with different mass-to-charge ratios is 15V. In the internal ionization mode, the voltage of the end cover is 15V.
The mass spectrum of the analysis using conventional continuous uv injection is shown in fig. 5a, the response to the analyte dioctyl phthalate 391u is up to 2 × 104, but the base photoionization noise due to continuous uv injection is large, and the signal-to-noise ratio of the signal at background noise is only 8: about 1. The result of using the vertical external ionization source introduction structure shown in fig. 2 is shown in fig. 5b, and the photoionization noise is reduced to about 50-80 due to the vertical structure, but the signal strength is also reduced to 2.3 × 103 due to the loss of the external introduction interface, and the signal-to-noise ratio is only restored to about 29: 1.
the analysis mass spectrogram obtained by the device of fig. 3 with the additional ultraviolet light modulation device provided by the invention is shown in fig. 5c, and the signal background noise is directly reduced to the order of magnitude of one bit because the ultraviolet light beam introduction at the non-ionization time sequence stage is directly intercepted on the mass spectrum light path by the light beam modulation device 310 formed by the chopper. Meanwhile, the 391u response height of the analyte dioctyl phthalate can still be kept at 1.8x104, the overall signal-to-noise ratio is improved to about 5000:1, and the effect is very obvious.
To further improve the synchronization performance of sample analysis, as shown in fig. 6a, the sample introduction for mass spectrometry can be synchronized with the light modulation device, for example, by the controller 605 controlling a sample introduction valve 612, so that the opening timings of the modulation device controller 310 and the chopper 311 are synchronized with the opening timing of the valve 612. Therefore, the sample substance can be more effectively utilized in the sample introduction process, and the influence of other secondary ionization processes, such as penning ionization of the metastable state substance on the residual sample, charge transfer ionization and the like on the quality analysis process is avoided.
In a further modified embodiment, in fig. 6b, the light beam adjusting component may be the sample injection valve plate 612 itself, and the body in the figure is a gate which moves the sample injection valve plate 612 under the control of the driving coil 611 by using the armature 613, the ultraviolet light transmittance can be changed by changing the gate position, and the light beam adjusting component and the mass analyzer operate synchronously under the coordination of the synchronous controller, and the ultraviolet light can be modulated by periodically opening and closing the gate, so as to achieve the effect similar to that of the chopper, thereby further reducing the complexity of the system, and simultaneously, spontaneously realizing the timing synchronization of the sample opening and the vacuum ultraviolet ionized photon introduction.
The above embodiments have the disadvantages that the physical modulator needs to be introduced to modulate the ultraviolet light, the physical modulator occupies a certain volume in the whole structure of the device, the miniaturization is not facilitated, the physical device cannot eliminate the possibility of abrasion and failure during operation, and once the physical device fails, the whole set of device cannot work normally. Therefore, in a modified embodiment of the present invention, as shown in fig. 7a, on the basis of the unchanged remaining components, the original chopper is replaced with a deflection voltage 715 applied to the deflection electrodes 713, 714 on both sides of the uv light source; by controlling the electric field intensity and changing the frequency, the ultraviolet light is modulated, and because the ultraviolet light is acted on by the electric field, the work of a physical device is not needed, the difficulty and the fault possibility in design are reduced, the stability and the durability of the whole device are improved, and the modulation is more accurate and reliable. Fig. 7b shows the effect of the electric field modulated light source device on the ionization efficiency of the output uv light, and when the visible deflection voltage 715 is above 510V, the output uv light intensity 720 has dropped below 1% of the normal value. Now the secondary noise signal 721 due to photoionization has been reduced to an effect similar to that of fig. 5c, achieving the technical effect of improving the sensitivity of the mass spectrometer signal.
It is also noted that continuous vacuum ultraviolet light that is gated off by a deflector or valve may also be utilized, such as to bombard a surface with an electron work function that is lower than its vacuum ultraviolet photon energy for at least this portion of the time. This process can generate escaping photoelectrons that can ionize at least a portion of the sample molecules and background gas molecules 800 within the uv internal photoionization mass spectrometry apparatus by electron capture or post-accelerated ionization of electrons. As shown in FIG. 8, when the electric potentials of the upper and lower 3 lenses 801, 802, 803 are changed to 8V, 7V and-60V, the emitted ultraviolet light will excite photogenerated electrons on the third aperture lens 803 with-60V added and the light modulation chopping plate 311, and then accelerate to the 802 space of the first lens 801 and the second lens to obtain about 70eV energy, and because electron capture or post-acceleration ionization does not have a significant material energy threshold, various materials can be ionized to form ions 804, thus expanding the material range of the sample analyzed by the device of the invention.
In addition to the mass spectrum signal obtained by the method, because the vacuum ultraviolet photoionization and the photoionization thereof have no limitation of the vacuum degree requirement of cold cathode, hot filament or field emission ionization, as shown in fig. 9, the device or the method can also be designed into an endogenous vacuum gauge through reasonable design. In this design, a collecting electrode 901 for detecting the degree of vacuum and an ion current multiplying device 902 are further included, and a current signal 903 formed by ions ionized by the sample molecules and background gas molecules of the part is collected and input into the controller to calculate the internal gas pressure of the ultraviolet internal light ionization mass spectrometry device. After the gas pressure value is obtained, by calculating whether the gas pressure value meets the high-voltage safe working threshold 904 of the ion multiplying component, the working high voltage 905 of the ion multiplying component can be controlled to be switched on and off according to the threshold judgment result, so that the high-value ion/electron multiplier 906 in the device can be protected from being damaged.
In general, in various embodiments of the present invention, a mass spectrometry method using the vacuum ultraviolet internal photoionization mass spectrometry apparatus is formed, and for the apparatus, typical operation sequence steps and conditions are as follows:
a) starting the continuous vacuum ultraviolet light source (101 or 301), and keeping the intensity of the output vacuum ultraviolet light stable, wherein the recommended value is within +/-1% of the range around the set average output value;
b) the controller (305 or 605) controls the working conditions of the mass analyzer (302 or 410, 420, 430) to enter a sample ionization working phase, and the sample introduced into the mass analyzer is ionized into sample ions under the action of the output vacuum ultraviolet light, and still resides in the mass analyzer;
c) the controller controls the beam adjusting part (311 or 612) to reduce the intensity of the vacuum ultraviolet light entering the mass analyzer to 1% or less of the average output value set by the continuous vacuum ultraviolet light source;
d) the controller controls the working conditions of the mass analyser (302 or 410, 420, 430) to enter an ion kinetic energy adjustment stage, adjusting the kinetic energy of sample ions residing in the mass analyser to meet ion kinetic energy and potential energy distribution conditions for subsequent separation of ions of different mass-to-charge ratios;
e) the controller controls the working conditions of the mass analyser (302 or 410, 420, 430) to enter ion separation stages of different mass to charge ratios, so that the sample ionic electric signals are separated in sequence according to mass numbers to obtain a mass spectrum.
Data analysis of fig. 5 and 7 shows that the method really solves the background noise problem of the traditional low-power consumption type continuous ultraviolet internal ionization mass spectrometry system, and can obviously improve the mass spectrometry sensitivity and analysis effect.
Those skilled in the art will appreciate that, in addition to implementing the system and its various devices, modules, units provided by the present invention as pure computer readable program code, the system and its various devices, modules, units provided by the present invention can be fully implemented by logically programming method steps in such a manner as to implement the same functions in the form of logic gates, switches, application specific integrated circuits, programmable logic controllers, embedded microcontrollers and the like. Therefore, the system and various devices, modules and units thereof provided by the invention can be regarded as a hardware component, and the devices, modules and units included in the system and used for realizing various functions can also be regarded as structures in the hardware component; means, modules, units for performing the respective functions may also be regarded as structures within both software modules and hardware components for performing the methods.
In the description of the present application, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience in describing the present application and simplifying the description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present application.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by those skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (10)
1. A vacuum ultraviolet internal ionization mass spectrometry apparatus, comprising: the device comprises an ultraviolet light source, a mass analyzer, a light beam adjusting component, an analysis sample and a controller;
the ultraviolet light source can carry out single photon ionization on an analysis sample;
the mass analyzer is capable of internally performing a complete mass spectrometry operating sequence from ionization of an analysis sample to mass separation of ions;
the mass analyzer is provided with a light source inlet;
the light beam adjusting component is arranged at the upstream of the light source introducing port;
the controller can synchronously control the working time sequence stage of the quality analyzer and the modulation amount of the light beam adjusting component;
the ultraviolet light source adopts a continuous vacuum ultraviolet light source;
the working sequence stage synchronously controlled by the controller comprises any one or more of the following steps:
-sample ionization;
-ion kinetic energy regulation;
-separation of ions of different mass to charge ratios.
2. The vuv-uv internal ionization mass spectrometry apparatus according to claim 1, wherein the mass analyzer is an ion trap mass analyzer, and the concentration of the desired ions in the ion trap is achieved by controlling the electrode voltage of the ion trap.
3. The vacuum ultraviolet internal ionization mass spectrometry apparatus of claim 1, further comprising an ion trap;
the illumination direction of the ultraviolet light source is coincident with the axis of the direction of the analysis sample entering the ion trap.
4. The vuv-vis internal ionization mass spectrometry apparatus of claim 3, wherein the ion trap is a cylindrical or square bulk ion trap.
5. The vacuum ultraviolet internal ionization mass spectrometry apparatus of claim 1, wherein the ion kinetic energy adjustment voltage of the mass analyzer is a periodic square wave or pulse.
6. The vacuum ultraviolet internal ionization mass spectrometry apparatus of claim 1, wherein the ion kinetic energy adjustment voltage of the mass analyzer is a periodic square wave or pulse.
7. The vacuum ultraviolet internal ionization mass spectrometry apparatus of claim 1, further comprising: a sample injection valve;
the opening time sequence of the sample injection valve is synchronous with the high conduction time sequence of the light beam adjusting part.
8. The vuv-vis internal ionization mass spectrometry apparatus of claim 1, wherein the beam conditioning component causes the vuv light from the continuous vuv light source to bombard the surface with an electron work function lower than its vuv photon energy for at least a portion of the time, generating photoelectrons and ionizing at least a portion of the sample molecules and background gas molecules in the vuv-vis internal ionization mass spectrometry apparatus.
9. The vacuum ultraviolet internal ionization mass spectrometry apparatus of claim 1, further comprising: a collecting electrode, an ion multiplying member;
the collecting electrode can detect the vacuum degree;
the collecting electrode can collect current signals formed by ions formed by ionization of at least one part of sample molecules and background gas molecules in the vacuum ultraviolet internal ionization mass spectrometry device, the current signals are input into the controller, whether the internal air pressure of the vacuum ultraviolet internal ionization mass spectrometry device meets the high-voltage safe working threshold range of the ion multiplication component or not is calculated, and the working high voltage of the ion multiplication component is controlled to be switched on and off according to a threshold judgment result.
10. A mass spectrometry method using the vacuum ultraviolet internal ionization mass spectrometry apparatus according to claims 1 to 9, comprising:
step S1: starting the continuous vacuum ultraviolet light source, and keeping the intensity of the output vacuum ultraviolet light stable within the range of +/-1% around the set average output value;
step S2: controlling the working condition of the mass analyzer by adopting a controller, enabling the mass analyzer to enter a sample ionization working stage, and enabling a sample introduced into the mass analyzer to be ionized into sample ions under the action of output vacuum ultraviolet light, and simultaneously remaining in the mass analyzer;
step S3: controlling the beam adjusting component by a controller to reduce the intensity of the vacuum ultraviolet light entering the mass analyzer to 1% or below of the average output value set by the continuous vacuum ultraviolet light source;
step S4: controlling the working conditions of the mass analyzer by adopting a controller, enabling the mass analyzer to enter an ion kinetic energy adjusting stage, adjusting the kinetic energy of sample ions residing in the mass analyzer, and meeting the ion kinetic energy and potential energy distribution state of the subsequent ion separation with different mass-to-charge ratios;
step S5: and controlling the working conditions of the mass analyzer by adopting a controller, so that the mass analyzer enters an ion separation stage with different mass-to-charge ratios, and separating sample ionic electric signals with different mass-to-charge ratios according to the mass number sequence to obtain a mass spectrogram.
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| CN112509908A (en) * | 2020-12-15 | 2021-03-16 | 深圳至秦仪器有限公司 | Pulse type ionization mass spectrometer and analysis method |
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| CN103854952A (en) * | 2012-11-30 | 2014-06-11 | 中国科学院大连化学物理研究所 | Mass spectrum vacuum ultraviolet ionization source based on optical-window-free gas discharge lamp |
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