CN111146069A - Laser ionization sample introduction device and method for solid detection - Google Patents

Laser ionization sample introduction device and method for solid detection Download PDF

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Publication number
CN111146069A
CN111146069A CN201911295356.1A CN201911295356A CN111146069A CN 111146069 A CN111146069 A CN 111146069A CN 201911295356 A CN201911295356 A CN 201911295356A CN 111146069 A CN111146069 A CN 111146069A
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China
Prior art keywords
laser
cavity
sample
ionization
mass spectrometer
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CN201911295356.1A
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Inventor
余泉
陈茜
鲁信琼
倪凯
王希林
周倩
王晓浩
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Shenzhen International Graduate School of Tsinghua University
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Shenzhen International Graduate School of Tsinghua University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/04Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0459Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for solid samples
    • H01J49/0463Desorption by laser or particle beam, followed by ionisation as a separate step
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/0027Methods for using particle spectrometers
    • H01J49/0031Step by step routines describing the use of the apparatus

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electrochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Optics & Photonics (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Electron Tubes For Measurement (AREA)

Abstract

The utility model provides a laser ionization sampling device and method for solid detects, the device includes laser instrument, laser ionization cavity, sampling tube and mass spectrograph cavity, the laser instrument is used for transmitting laser and is located on the sample that awaits measuring in the laser ionization cavity, make laser and the sample that awaits measuring take place ionization reaction and generate sample ion, the laser ionization cavity is through advancing the union coupling the mass spectrograph cavity, the sample ion passes through advance the sampling tube and enter into in the mass spectrograph cavity and be in realize sample ion detection in the mass spectrograph cavity, wherein, make through setting up atmospheric pressure in the laser ionization cavity is higher than atmospheric pressure in the mass spectrograph cavity. The invention can improve the transmission and utilization efficiency of ions and improve the detection sensitivity of the laser ionization detection instrument.

Description

Laser ionization sample introduction device and method for solid detection
Technical Field
The invention relates to a laser ionization sample injection device and method for solid detection.
Background
The sample introduction system is one of the important components of the mass spectrometer. Most commercial mass spectrometers use intra-cavity ionization. The laser ionization is carried out in the cavity of low pressure, and ion analysis is carried out in the cavity of vacuum, and its working process has certain requirement to the vacuum degree of cavity, sets up the laser ionization process in the mass spectrograph cavity, has increaseed the work burden of vacuum pump, also has certain influence to the ion analysis process simultaneously, consequently, to miniature mass spectrograph, realizes the method of appearance introduction with the cavity separation, can effectual reduction vacuum pump operating pressure.
Disclosure of Invention
The invention mainly aims to provide a laser ionization sample injection device and a laser ionization sample injection method for solid detection, so as to improve the transmission and utilization efficiency of ions and improve the detection sensitivity of a laser ionization detection instrument.
In order to achieve the purpose, the invention adopts the following technical scheme:
the utility model provides a laser ionization sampling device for solid detects, includes laser instrument, laser ionization cavity, advances appearance pipe and mass spectrograph cavity, the laser instrument is used for transmitting laser to be located on the sample that awaits measuring in the laser ionization cavity, make laser and the sample that awaits measuring take place ionization reaction and generate sample ion, the laser ionization cavity is through advancing the appearance union coupling the mass spectrograph cavity, the sample ion passes through advance the appearance pipe and enter into in the mass spectrograph cavity and realize sample ion detection in the mass spectrograph cavity, wherein, make through setting up the atmospheric pressure in the laser ionization cavity is higher than atmospheric pressure in the mass spectrograph cavity.
Further:
the laser ionization cavity and the mass spectrometer cavity are independent cavities, and the air pressure is controlled by controlling the air flow into the mass spectrometer cavity through respective valves, so that the air pressure in the laser ionization cavity is higher than the air pressure in the mass spectrometer cavity.
The position of the action of the laser emitted by the laser and the sample is aligned with the sample inlet of the sample inlet pipe, so that the sample ions enter the sample inlet pipe.
The laser ionization sampling device is a continuous sampling device, the sampling tube is directly communicated with the laser ionization cavity and the mass spectrometer cavity, continuous laser is emitted by the laser, and generated sample ions enter the mass spectrometer cavity to be subjected to continuous detection.
The laser ionization sampling device is a discontinuous sampling device and further comprises a pulse switch arranged on the sampling tube, pulse laser is emitted by the laser, and generated sample ions enter the mass spectrometer cavity through the pulse switch to be subjected to pulse detection.
The mass spectrometer is an ion trap mass spectrometer using a rectangular ion trap or a linear ion trap.
The utility model provides a laser ionization sampling method for solid detects, uses laser ionization sampling device carry out the ionization of solid sample and advance the appearance, wherein laser emission laser arrives on the sample that awaits measuring in the laser ionization cavity, make laser and sample take place ionization reaction and generate sample ion, sample ion passes through advance the appearance pipe and enter into in the mass spectrometer cavity and realize sample ion detection in the mass spectrometer cavity, wherein, control atmospheric pressure in the laser ionization cavity is higher than atmospheric pressure in the mass spectrometer cavity.
Further, the method comprises the steps of:
1) opening the laser, and emitting laser to irradiate the surface of a sample to be detected on a sample table in the laser ionization cavity to generate sample ionization and generate ions;
2) the sample ions pass through the sample inlet pipe and enter the cavity of the mass spectrometer;
3) the sample ions are detected in the mass spectrometer cavity to complete a cycle.
The invention has the following beneficial effects:
according to the laser ionization sample introduction device and method for solid detection, the sample introduction pipe is arranged between the laser ionization cavity and the mass spectrometer cavity, the air pressure inside the laser ionization cavity is higher than that inside the ion trap mass spectrometer cavity, the air pressure difference between the two cavities is convenient for sample ion transmission, the time for the ions to remain in the laser ionization cavity is shortened, the ion transmission efficiency is improved, the ion transmission loss is reduced, the duty ratio of a sample entering the mass spectrometer cavity is improved, the ion utilization efficiency can be improved, and the sensitivity of a laser ionization detection instrument is effectively improved.
The invention can especially enhance the detection sensitivity of the miniaturized and integrated laser ionization detector.
Drawings
Fig. 1 is a schematic structural diagram of a laser ionization sample injection device for solid detection according to an embodiment of the present invention.
Detailed Description
The embodiments of the present invention will be described in detail below. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the invention or its application.
It will be understood that when an element is referred to as being "secured to" or "disposed on" another element, it can be directly on the other element or be indirectly on the other element. When an element is referred to as being "connected to" another element, it can be directly connected to the other element or be indirectly connected to the other element. In addition, the connection may be for either a fixed function or a circuit/signal communication function.
It is to be understood that when the terms "length," "width," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are presented, the indicated orientations or positional relationships are based on the orientations or positional relationships illustrated in the drawings and are intended to facilitate the description of the embodiments and to simplify the description, but are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are not to be construed as limiting the present invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the embodiments of the present invention, "a plurality" means two or more unless specifically limited otherwise.
Referring to fig. 1, the embodiment of the invention provides a laser ionization sample injection device for solid detection, which includes a laser 6, a laser ionization cavity 1, a sample injection tube 4 and a mass spectrometer cavity 5, wherein the laser 6 is used for emitting laser to a sample 2 to be detected in the laser ionization cavity 1, so that the laser and the sample 2 to be detected are subjected to ionization reaction to generate sample ions, the laser ionization cavity 1 is connected with the mass spectrometer cavity 5 through the sample injection tube 4, the sample ions enter the mass spectrometer cavity 5 through the sample injection tube 4 and are detected in the mass spectrometer cavity 5, and the air pressure in the laser ionization cavity 1 is higher than the air pressure in the mass spectrometer cavity 5 through setting. The air pressure difference between the two cavities is convenient for the transmission of sample ions, reduces the time for the ions to remain in the laser ionization cavity 1 and reduces the transmission loss of the ions.
In a preferred embodiment, the laser ionization chamber 1 and the mass spectrometer chamber 5 are independent chambers, and the gas flowing into the laser ionization chamber 1 is controlled by a valve (not shown) to control the gas pressure, so that the gas pressure in the mass spectrometer chamber 5 is higher than the gas pressure in the laser ionization chamber 1.
In a preferred embodiment, the laser 6 emits laser light that is directed to the sample at a position aligned with the sample inlet of the sample inlet tube 4 so that the sample ions enter the sample inlet tube 4. Can set up the sample platform in the laser ionization cavity 1 and be used for placing the sample 2 that awaits measuring, in this embodiment, the setting of sample platform satisfies above-mentioned design.
In some embodiments, the laser ionization sampling device is a continuous sampling device, the sampling tube 4 directly communicates with the laser ionization cavity 1 and the mass spectrometer cavity 5, the laser 6 emits continuous laser, and the generated sample ions enter the mass spectrometer cavity 5 for continuous detection.
In other embodiments, the laser ionization sampling device is a discontinuous sampling device, and further includes a pulse switch 3 disposed on the sampling tube 4, the laser 6 emits pulsed laser, and the generated sample ions enter the mass spectrometer cavity 5 through the pulse switch 3 for pulsed detection.
In some embodiments, the mass spectrometer is an ion trap mass spectrometer using a rectangular ion trap or a linear ion trap.
When the laser ionization sampling device is a discontinuous sampling device, the laser 6 emits laser, the pulse switch 3 is opened, and the ion gate in the ion trap is opened according to a preset time sequence relationship.
Wherein the relative positions of the mass spectrometer cavity 5 and the laser ionization cavity 1 are not limited.
The distance that the air inlet pipe 3 extends into the cavity is not limited, the air inlet pipe 3 can extend into the ion trap or be positioned outside the ion trap in the cavity, and the air inlet pipe can be matched with the type of the selected ionization source and the type of the used ion trap.
The mode of realizing the discontinuous sample introduction is not limited, and a pinch valve or other devices capable of generating the discontinuous sample introduction can be used.
The ion trap 4 analyzer is not limited, and may be a rectangular ion trap, a linear ion trap, or other analyzers.
The embodiment of the invention also provides a laser ionization sampling method for solid detection, which uses the laser ionization sampling device of any one of the embodiments to perform ionization and sampling of a solid sample, wherein the laser 6 emits laser to the sample 2 to be detected in the laser ionization cavity 1, so that the laser and the sample generate ionization reaction to generate sample ions, the sample ions enter the mass spectrometer cavity 5 through the sample inlet tube 4 and realize sample ion detection in the mass spectrometer cavity 5, and wherein the air pressure in the laser ionization cavity 1 is controlled to be higher than the air pressure in the mass spectrometer cavity 5. The air pressure difference between the two cavities is convenient for the transmission of sample ions, reduces the time for the ions to remain in the laser ionization cavity 1 and reduces the transmission loss of the ions.
Further, the method comprises the steps of:
1) opening the laser 6, emitting laser to irradiate the surface of the sample 2 to be detected on the sample platform in the laser ionization cavity 1, and ionizing the sample to generate ions;
2) the sample ions pass through the sample inlet pipe 4 and enter the mass spectrometer cavity 5;
3) the sample ions are detected in the mass spectrometer cavity 5, completing one cycle.
According to the laser ionization sample introduction device and method for solid detection, the sample introduction pipe is arranged between the laser ionization cavity and the mass spectrometer cavity, the air pressure inside the laser ionization cavity is higher than that inside the ion trap mass spectrometer cavity, the air pressure difference between the two cavities is convenient for sample ion transmission, the time for the ions to remain in the laser ionization cavity is shortened, the ion transmission efficiency is improved, the ion transmission loss is reduced, the duty ratio of a sample entering the mass spectrometer cavity is improved, the ion utilization efficiency can be improved, and the sensitivity of a laser ionization detection instrument is effectively improved. The air pressure of the cavity can be kept, and the pressure of the vacuum pump can be reduced. The invention can especially enhance the detection sensitivity of the miniaturized and integrated laser ionization detector.
It should be noted that the present invention is not limited to the specific implementation control method of sample injection, the specific method of implementing pulse sample injection, and the specific method of ionizing the sample to be tested.
The background of the present invention may contain background information related to the problem or environment of the present invention and does not necessarily describe the prior art. Accordingly, the inclusion in the background section is not an admission of prior art by the applicant.
The foregoing is a more detailed description of the invention in connection with specific/preferred embodiments and is not intended to limit the practice of the invention to those descriptions. It will be apparent to those skilled in the art that various substitutions and modifications can be made to the described embodiments without departing from the spirit of the invention, and these substitutions and modifications should be considered to fall within the scope of the invention. In the description herein, references to the description of the term "one embodiment," "some embodiments," "preferred embodiments," "an example," "a specific example," or "some examples" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction. Although embodiments of the present invention and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the scope of the claims.

Claims (8)

1. The utility model provides a laser ionization sampling device for solid detects, a serial communication port, including laser instrument, laser ionization cavity, sampling tube and mass spectrograph cavity, the laser instrument is used for transmitting laser to be located on the sample that awaits measuring in the laser ionization cavity, make laser and the sample that awaits measuring take place ionization reaction and generate sample ion, the laser ionization cavity is through advancing the union coupling the mass spectrograph cavity, the sample ion passes through advance the sampling tube and enter into in the mass spectrograph cavity and be in realize sample ion detection in the mass spectrograph cavity, wherein, make through setting up atmospheric pressure in the laser ionization cavity is higher than atmospheric pressure in the mass spectrograph cavity.
2. The laser ionization sample introduction device according to claim 1, wherein the laser ionization chamber and the mass spectrometer chamber are independent chambers, and the gas is controlled to flow into the size control gas pressure through respective valves, so that the gas pressure in the laser ionization chamber is higher than the gas pressure in the mass spectrometer chamber.
3. The laser ionization sample introduction device according to claim 1 or 2, wherein a position where laser light emitted by the laser and a sample act is aligned with a sample inlet of the sample introduction pipe so that the sample ions enter the sample introduction pipe.
4. The laser ionization sample introduction device according to claim 1 or 2, wherein the laser ionization sample introduction device is a continuous sample introduction device, the sample introduction tube directly communicates with the laser ionization cavity and the mass spectrometer cavity, the laser emits continuous laser, and generated sample ions enter the mass spectrometer cavity for continuous detection.
5. The laser ionization sample introduction device according to claim 1 or 2, wherein the laser ionization sample introduction device is a discontinuous sample introduction device, and further comprises a pulse switch disposed on the sample introduction tube, the laser emits pulsed laser, and the generated sample ions enter the mass spectrometer cavity through the pulse switch for pulse detection.
6. The laser ionization sample introduction device according to claim 1 or 2, wherein the mass spectrometer is an ion trap mass spectrometer using a rectangular ion trap or a linear ion trap.
7. A laser ionization sampling method for solid detection, characterized in that the laser ionization sampling device of any one of claims 1 to 6 is used to perform ionization and sampling of solid samples, wherein the laser emits laser onto the sample to be detected in the laser ionization cavity, so that the laser and the sample undergo ionization reaction to generate sample ions, the sample ions enter the mass spectrometer cavity through the sampling tube and realize sample ion detection in the mass spectrometer cavity, and wherein the gas pressure in the laser ionization cavity is controlled to be higher than the gas pressure in the mass spectrometer cavity.
8. The laser ionization sample introduction method according to claim 7, comprising the steps of:
1) opening the laser, and emitting laser to irradiate the surface of a sample to be detected on a sample table in the laser ionization cavity to generate sample ionization and generate ions;
2) the sample ions pass through the sample inlet pipe and enter the cavity of the mass spectrometer;
3) the sample ions are detected in the mass spectrometer cavity to complete a cycle.
CN201911295356.1A 2019-12-16 2019-12-16 Laser ionization sample introduction device and method for solid detection Pending CN111146069A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101465261A (en) * 2009-01-09 2009-06-24 厦门大学 High power density laser sputtering ionization time-of-flight mass spectrometer and use thereof
CN203367224U (en) * 2013-06-13 2013-12-25 无锡华质铂马生物医药技术有限公司 Normal pressure direct ionization mass spectrum device of concealed ion source
CN107907586A (en) * 2017-12-27 2018-04-13 常州英诺激光科技有限公司 A kind of portable laser mass spectrograph that can be worked under atmospheric environment

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101465261A (en) * 2009-01-09 2009-06-24 厦门大学 High power density laser sputtering ionization time-of-flight mass spectrometer and use thereof
CN203367224U (en) * 2013-06-13 2013-12-25 无锡华质铂马生物医药技术有限公司 Normal pressure direct ionization mass spectrum device of concealed ion source
CN107907586A (en) * 2017-12-27 2018-04-13 常州英诺激光科技有限公司 A kind of portable laser mass spectrograph that can be worked under atmospheric environment

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