CN110940723A - Mass spectrum detection device and optical system thereof - Google Patents

Mass spectrum detection device and optical system thereof Download PDF

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Publication number
CN110940723A
CN110940723A CN201811113273.1A CN201811113273A CN110940723A CN 110940723 A CN110940723 A CN 110940723A CN 201811113273 A CN201811113273 A CN 201811113273A CN 110940723 A CN110940723 A CN 110940723A
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lens
housing module
laser
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sample
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喻佳俊
黄利勇
林利泉
黄凯彬
朱星高
刘平
代新
曾真
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Guangzhou Hsin Kang Yuan Medical Technology Co Ltd
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Guangzhou Hsin Kang Yuan Medical Technology Co Ltd
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    • 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
    • G01N27/64Investigating 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 using wave or particle radiation to ionise a gas, e.g. in an ionisation chamber
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/26Mass spectrometers or separator tubes
    • H01J49/34Dynamic spectrometers
    • H01J49/40Time-of-flight spectrometers

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Abstract

The invention relates to a mass spectrum detection device and an optical system thereof. The laser of the laser unit in the optical system adopts a solid laser, the angle formed by the incident direction of laser and the axial direction of the ion source cavity is very small, and the initial velocity direction of particles generated by laser ionization basically diverges along the central axis direction of the ion source cavity, so that the initial kinetic energy divergence of the ions is small, and the resolution and the sensitivity of the mass spectrum detection device are improved. The angle formed by the illumination light emitted by the illumination unit and the axis direction of the imaging light path and the ion source cavity is very small, and the illumination and imaging directions are completely symmetrical, so that the intersection range of the illumination area generated by the illumination light source on the surface of the sample target plate and the imaging area of the imaging unit can be maximized, the generation of the evil shadow effect can be avoided, the imaging range can be greatly improved, and the imaging quality is greatly improved.

Description

Mass spectrum detection device and optical system thereof
Technical Field
The invention relates to the field of mass spectrometry detection instruments, in particular to a mass spectrometry detection device and an optical system thereof.
Background
The advent of Matrix Assisted Laser Desorption (MALDI) ion sources has provided a very important technological tool for the complete analysis of macromolecules. MALDI techniques are well suited for combination with time-of-flight mass spectrometry (TOFMS) detection techniques, which is also the most successful combination of MALDI techniques. In recent years, with the rapid development of laser technology, high-speed data acquisition, ion detection and matrix technology, the performance of MALDI ionization technology has been rapidly improved, so that modern MALDI instruments have the capabilities of high resolution, high sensitivity, high quality range and even quantification. In recent years, MALDI-TOFMS has become an important means for analysis of biological macromolecules such as proteins, polypeptides, nucleic acids, etc. MALDI-TOFMS is used for drawing a protein ion peak map of the microorganism, and then mass spectrum data of clinical microorganisms are compared with a standard protein fingerprint map database, so that the purpose of microorganism identification can be achieved. Compared with the traditional microorganism identification technology such as a biochemical method, a luminescence method and the like, the method has certain advantages in the aspects of identification speed, result accuracy, technical cost, personnel operation requirements and the like. MALDI-TOFMS has technical characteristics of high sensitivity, wide mass range, moderate resolution, mass precision and the like, and has the use characteristics of simple operation, rapidness, economy and the like, so that the MALDI-TOFMS becomes an instrument with the highest potential for high-throughput and business operation. In the field of microorganism identification and nucleic acid detection, MALDI-TOFMS has already been in the clinical application stage.
MALDI-TOFMS needs to mix and titrate a sample substance to be analyzed and a matrix on a stainless steel target plate, the mixture is air-dried or blow-dried to generate a co-crystal, focused laser points are irradiated on the surface of the co-crystal, the matrix absorbs laser energy and then transfers the energy to sample molecules to be analyzed, so that the sample molecules are ionized, and then a time-of-flight mass spectrometer is used for detection, and substances corresponding to various ions are identified according to different flight times of different ions. During sample analysis, the distribution of generated eutectic bodies on the surface of the target plate is not uniform, the crystalline states of some positions are good, more crystalline substances are formed, and some positions do not form crystalline substances. Therefore, in the process of analyzing a laser sample, an operator needs to be able to see the crystallization state of the sample and the crystallization quality of the sample at different target positions in real time, so as to select the most suitable analysis point for experiment. Because the laser light path system is often very long, slight vibration or displacement can cause the laser point to deviate the center of the sample to be analyzed, so that the working state of the instrument can be effectively monitored by observing the position of the laser sample point in real time, and the performance of the instrument is ensured. In addition, the color, reflectance, shape, etc. of crystals are not consistent for different samples to be analyzed, nor are the sensitivity to light, and thus the imaging device must also be able to accommodate the illumination and imaging requirements of different analytes.
However, most of the conventional mass spectrometry devices still mainly adopt a nitrogen molecule laser (N2 laser) as an ionization source, and the mass spectrometry resolution and the imaging quality are to be improved.
Disclosure of Invention
Based on this, it is necessary to provide a mass spectrometry detection apparatus and an optical system thereof capable of improving mass spectrometry resolution and imaging quality.
The technical scheme for solving the technical problems is as follows.
An optical system of a mass spectrum detection device comprises a laser unit, an illumination unit, an imaging unit and an optical reflection mechanism; the laser unit, the illumination unit and the imaging unit are arranged outside an ion source cavity of the mass spectrum detection device, and the optical reflection mechanism is arranged inside the ion source cavity;
the laser of the laser unit is a solid laser, the laser emitted by the laser unit is reflected by the optical reflection mechanism and then is emitted to the surface of the sample, and the included angle between the reflected laser ray and the axis vertical to the sample target plate is more than 0 degree and not more than 10 degrees; the illumination light emitted by the illumination unit is reflected by the optical reflection mechanism and then irradiates the surface of the sample, and the included angle between the illumination light reflected by the optical reflection mechanism and the axis vertical to the sample target plate is more than 0 degree and not more than 10 degrees; the imaging unit is for receiving illumination light reflected by the sample for sample imaging.
In one embodiment, the laser unit comprises an optical fixed platform, and the solid laser, the optical path system and the shell which are arranged on the optical fixed platform;
the light path system comprises a first focusing lens, a collimating lens and a second focusing lens, wherein a laser beam emitted by the solid laser generates a divergent laser beam through the first focusing lens, the divergent laser beam becomes a collimated laser beam after passing through the collimating lens, and the collimated laser beam can be reflected by the optical reflection mechanism and then incident on a sample after being focused by the second focusing lens;
the first focusing lens, the collimating lens and the second focusing lens are arranged in the shell, and the distance between the first focusing lens and the collimating lens is adjustable.
In one embodiment, the optical path system further comprises a filter for adjusting the energy of the laser beam.
In one embodiment, the housing is of a modular structure and comprises a first lens housing module, a second lens housing module and a third lens housing module which are connected in sequence; the first focusing lens, the collimating lens, and the second focusing lens are disposed in the first lens housing module, the second lens housing module, and the third lens housing module, respectively;
the first lens housing module and the second lens housing module are relatively movable to adjust a distance between the first focusing lens and the collimating lens.
In one embodiment, the housing further comprises a first reflective housing module, a second reflective housing module and/or a third reflective housing module, and correspondingly, the optical path system further comprises a first reflective mirror disposed in the first reflective housing module, a second reflective mirror disposed in the second reflective housing module and/or a third reflective mirror disposed in the third reflective housing module;
the first reflector housing module is connected between the first lens housing module and the second lens housing module, the second reflector housing module is connected between the second lens housing module and the third lens housing module, and the third reflector housing module is connected behind the third lens housing module.
In one embodiment, the adjacent shell modules are connected together through a threaded connection structure;
the relative movement between the first lens housing module and the second lens housing module is adjusted by a screw-type adjustment structure.
In one embodiment, the laser unit further comprises at least one of a filter adjustment mechanism, a lens adjustment mechanism, and a reflection adjustment mechanism;
the filtering adjusting mechanism is connected with the optical filter and is used for driving the optical filter to rotate;
the lens adjusting mechanism is connected with the first lens housing module and/or the second lens housing module and is used for adjusting the relative position of the first lens housing module and the second lens housing module;
the reflection adjustment mechanism is connected with the first mirror, the second mirror and/or the third mirror for adjusting the angle of the respective mirror.
In one embodiment, the optical reflection mechanism has three reflection surfaces for reflecting the incident laser light to the sample, reflecting the illumination light emitted from the illumination unit to the sample, and reflecting the illumination light reflected from the sample to the imaging unit, respectively.
In one embodiment, the imaging unit includes an optical lens and a camera, and the illumination light reflected by the optical reflection mechanism is captured by the optical lens and then captured by the camera.
A mass spectrometry detection apparatus comprising an ion source assembly and the optical system of any of the above embodiments; the ion source assembly comprises an ion source cavity, a sample target plate and a pole piece assembly, wherein the sample target plate and the pole piece assembly are arranged in the ion source cavity and are positioned below the optical reflection mechanism; the laser unit is positioned on one side of the ion source cavity.
Research finds that the initial characteristics of ions generated in the laser ionization process are important for the influence of the overall performance of the instrument, and the initial flight direction of the generated ions and the laser incidence direction show a direct inverse relationship. Therefore, theoretically, the ions generated by the laser irradiating the sample vertically will be dispersed along the central axis of the instrument, which is most beneficial to improve the resolution. However, most conventional devices have too large an angle between the laser incidence angle and the axial direction, resulting in the divergence direction of the generated ions being off the central axis, thereby affecting the mass spectral resolution. Further research shows that the traditional MALDI-TOFMS ion source has a very compact structure, so that the illumination and imaging of a sample point are difficult to realize, and the whole optical system needs to pass through a series of components of the ion source system, so that the traditional mass spectrometry equipment generally adopts large-angle illumination and imaging. On one hand, the method can cause the imaged image to generate a serious oblique image effect, so that the deformation degree of the imaged image is large, and the image shaping treatment is generally needed and is complex; on the other hand, because the illumination and imaging optical path systems are not always the same optical path, the area of the intersection region of the illumination and imaging optical path systems is small, and the area range of final imaging is limited.
Based on the above, the invention provides a mass spectrometry detection device and an optical system thereof for small-angle laser incidence, illumination and imaging, aiming at the problem that the laser incidence angle, illumination and imaging angle are too large in the traditional MALDI-TOFMS instrument. The laser emitted by the laser unit is reflected by the optical reflection mechanism and then is emitted to the surface of the sample, and the included angle between the reflected laser ray and the axis perpendicular to the sample target plate is larger than 0 degree and not larger than 10 degrees, so that the angle formed by the incident direction of the laser and the axis direction of the ion source cavity is very small, and the initial velocity direction of particles generated by laser ionization basically diverges along the central axis direction of the ion source cavity, so that the initial kinetic energy divergence of the ions is small, and the resolution and the sensitivity of the mass spectrum detection device are improved. The illumination light emitted by the illumination unit irradiates the surface of the sample after being reflected by the optical reflection mechanism, and the included angle between the illumination light reflected by the optical reflection mechanism and the axis vertical to the sample target plate is more than 0 degree and not more than 10 degrees, the imaging unit is used for receiving the illumination light reflected by the sample, and the angle of the imaging light path is very small. And the illumination and imaging directions are completely symmetrical, so that the intersection range of the illumination area generated by the illumination light source on the surface of the sample target plate and the imaging area of the imaging unit can be maximized, the generation of an evil shadow effect can be avoided, the imaging range can be greatly improved, and the imaging quality is greatly improved.
Furthermore, the mass spectrum detection device and the optical system thereof adopt the design of the mass spectrum ion source based on the solid laser, and compared with an N2 laser, the mass spectrum detection device has the advantages of long service life, short pulse time, small volume, high repetition frequency and the like, and is beneficial to improving the resolution of the mass spectrum detection device and reducing the maintenance frequency.
Particularly, the solid laser, the whole optical path system and the shell are completely fixed on the optical fixing platform, the optical path system is located in the shell, the structure is very stable, and the installation and maintenance are convenient. When the laser device is used, the adjustment of the size of a laser spot can be realized by adjusting the distance between the first focusing lens and the collimating lens, and the laser device is convenient to use.
Furthermore, in order to reduce the angle between the laser incidence direction and the central axis of the mass spectrum flight tube as much as possible, other pole piece assemblies and the like of the whole ion source assembly are arranged below the optical reflection mechanism, and the design of the inner hole of the pole piece assembly can ensure that laser and illumination light can smoothly reach the surface of a sample without being influenced by the pole piece assembly. Therefore, the reflected laser can reach the surface of the sample at a very small angle, the sample is ionized, and the surface light source generated by illumination can reach the imaging unit through the hole array in the middle of the pole piece assembly.
Drawings
FIG. 1 is a schematic diagram of a portion of a mass spectrometer apparatus according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of the ion source assembly and a portion of the optical system of FIG. 1;
FIG. 3 is a schematic diagram of a laser unit of the mass spectrometric detection apparatus of FIG. 1;
FIG. 4 is a cross-sectional view of the laser unit shown in FIG. 3;
FIG. 5 is a schematic diagram of the optical path of the laser unit shown in FIG. 3;
FIG. 6 is a graph showing the relationship between the displacement of the first focusing lens and the spot diameter of the focusing point;
FIG. 7 shows actual spot measurements;
fig. 8 is a schematic structural diagram of a laser unit according to another embodiment.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Referring to fig. 1, an embodiment of the invention provides a mass spectrometry detection apparatus 10, which includes an ion source assembly 100 and an optical system 200. The mass spectrometer 10 may be any type of mass spectrometer such as a time-of-flight mass spectrometer.
As shown in fig. 2, the ion source assembly 100 includes an ion source chamber 110, a sample target plate 120, and a pole piece assembly 130.
The ion source chamber 110 has a vacuum chamber 112. In one specific example, the upper portion of the ion source chamber 110 is in an octahedral cylinder structure, preferably a regular octahedral cylinder structure.
The sample target plate 120 and the pole piece assembly 130 are located within the vacuum chamber 112 of the ion source chamber 110. The sample target plate 120 is used to place a co-crystal sample of the sample material to be analyzed and the matrix. The pole piece assembly 130 is used to guide ions generated by ionization of the sample into the mass detection device for mass analysis. The extraction pole piece 132 of the pole piece assembly 130 is located above the sample target plate 120, and is provided with a pole piece inner hole 134 for light of the optical system to pass through.
Referring to fig. 1, the optical system 200 includes a laser unit 210, an illumination unit 220, an imaging unit 230, and an optical reflection mechanism 240. The laser unit 210, the illumination unit 220, and the imaging unit 230 are disposed outside the ion source cavity 110, and the optical reflection mechanism 240 is disposed inside the ion source cavity 110.
Referring to fig. 3, 4 and 5, the laser unit 210 includes an optical fixing platform 211, a solid laser 212, an optical path system 213 and a housing 214. The solid laser 212, the optical path system 213, and the housing 214 are provided on the optical fixing stage 211. An optical mounting plate 211 is mounted to one side of the ion source chamber 110.
The solid-state laser 212 is fixed on the optical fixing platform 211. In one specific example, the wavelength of the laser light emitted by solid state laser 212 is 343 nm. Compared with a traditional N2 laser, the solid laser 212 has the advantages of long service life, small laser pulse width, high repetition frequency, small size and the like, can obviously improve the resolution of the matrix-assisted laser desorption time-of-flight mass spectrometer, reduces the maintenance frequency, and is favorable for the volume miniaturization design of the instrument.
The optical path system 213 includes a first focusing lens 2131, a collimating lens 2132, and a second focusing lens 2133. The laser beam emitted by the solid laser 212 is focused by the second focusing lens 2133 and reflected to the sample by the optical reflection mechanism 240. The first focusing lens 2131, the collimating lens 2132 and the second focusing lens 2133 are disposed in the housing 214, and a distance between the first focusing lens 2131 and the collimating lens 2132 is adjustable.
Fig. 5 shows a schematic view of the entire optical path system 10. The distance between the solid laser 212 and the first focusing lens 2131 (F1 in the figure, the focal length is F1) is L1, the laser pulse generated by the solid laser 212 generates a divergent light beam through the first focusing lens 2131, a collimating lens 2132 (F2 in the figure, the focal length is F2) is arranged behind the divergent light beam at a certain distance L2 and is used for collimating the divergent laser beam, a second focusing lens 2133 (F3 in the figure, the focal length is F3) is arranged at a certain distance L3 of the collimated light beam and is used for focusing the collimated light beam again, and according to the selected focal length parameters of the lenses, the desired spot size can be obtained at a certain distance L4. Continuous adjustability of the laser spot size at a fixed location can be achieved by adjusting the distance between the first focusing lens 2131 and the collimating lens 2132.
Fig. 6 shows a relationship curve between ω 1 (the diameter of the laser spot at the fixed position) and the displacement of the first focusing lens 2131 under different ω 0 (the diameter of the laser spot emitted by the solid-state laser 212) and simulated by software according to the parameters shown in table 1.
TABLE 1
Figure BDA0001809808790000091
In one specific example, the optical path system 213 further includes a filter (not shown). The filter may be, but is not limited to, a neutral density filter or the like for adjusting the energy of the laser beam. More specifically, the filter may be disposed behind the second focusing lens 2133 for adjusting the energy of the laser beam focused by the second focusing lens 2133.
Further, the laser unit 210 further includes a filter adjustment mechanism. The filtering adjusting mechanism is connected with the optical filter and is used for driving the optical filter to rotate. The filtering adjusting mechanism can be a steering engine and other mechanisms, and the rotation of the filtering adjusting mechanism can drive the optical filter to rotate, so that the continuous adjustment of the laser capacity is realized.
In order to reduce the volume of the whole laser unit 210 as much as possible, the invention makes creative optimization design on the structure of the laser unit 210. In one specific example, the housing 214 is designed in a modular structure, and includes a first lens housing module 2141, a second lens housing module 2142, and a third lens housing module 2143 connected in sequence. The first focusing lens 2131, the collimating lens 2132 and the second focusing lens 2133 are respectively disposed in the first lens housing module 2141, the second lens housing module 2142 and the third lens housing module 2143.
The first lens housing module 2141 and the second lens housing module 2142 can move relatively to each other to adjust the distance between the first focusing lens 2131 and the collimating lens 2132, for example, the position of the first focusing lens 2131 can be fixed, and the position of the collimating lens 2132 can be adjusted; or the position of the first focusing lens 2131 is adjustable, and the position of the collimating lens 2132 is fixed; or both the first focusing lens 2131 and the collimating lens 2132 may be designed to be adjustable in position. Preferably, the laser unit 210 further includes a lens adjustment mechanism. The lens adjusting mechanism is connected with the first lens housing module 2141 and/or the second lens housing module 2142 for adjusting the relative position of the first lens housing module 2141 and the second lens housing module 2142. The lens adjusting mechanism can be a microminiature stepping motor and the like, can be automatically controlled, and has high adjusting precision and convenient operation.
The housing 214 is of a modular structural design, so that difficulty in installation and debugging is greatly reduced, and adjustment of the distance between the first focusing lens 2131 and the collimating lens 2132 is facilitated, for example, the first lens housing module 2141 and the second lens housing module 2142 can be in threaded connection, the first lens housing module 2141 and/or the second lens housing module 2142 are driven by the lens adjusting mechanism to rotate for fine adjustment of the position, and continuous adjustment of the final spot size is achieved.
Further, as in the specific example shown in fig. 3 and 4, the housing 214 further includes a first reflective housing module 2144, a second reflective housing module 2145, and a third reflective housing module 2146, and accordingly, the optical path system 213 further includes a first mirror 2134 disposed in the first reflective housing module 2144, a second mirror 2145 disposed in the second reflective housing module 2145, and a third mirror 2136 disposed in the third reflective housing module 2146. The first reflective housing module 2144 is connected between the first lens housing module 2141 and the second lens housing module 2142, the second reflective housing module 2145 is connected between the second lens housing module 2142 and the third lens housing module 2143, and the third reflective housing module 2146 is connected behind the third lens housing module 2143. By providing the first mirror 2134, the second mirror 2135, and the third mirror 2136, the incident angle adjustment of the laser beam can be realized, and the optimal design of the length and volume of the entire optical path system 10 can be advantageously realized.
Further, in the particular example shown, the first reflective housing module 2144, the second reflective housing module 2145, and the third reflective housing module 2146 are secured to the optical mounting platform 211 by screws. The two ends of the first reflective housing module 2144, the second reflective housing module 2145, and the third reflective housing module 2146 each have an outer cylinder with an internal thread, the first lens housing module 2141, the second lens housing module 2142, and the third lens housing module 2143 are cylindrical structures with external threads, and are respectively in threaded connection with the first reflective housing module 2144, the second reflective housing module 2145, and the third reflective housing module 2146 as inner cylinders, that is, adjacent housing modules are connected together by a threaded connection structure, and the relative movement between the first lens housing module 2141 and the second lens housing module 2142 is adjusted by a screw-type adjustment structure. The shell modules of the shell 214 are fixedly connected in a sleeve type installation mode, and installation and debugging are very convenient.
In one particular example, the laser unit 210 further includes a reflection adjustment mechanism. The reflection adjusting mechanism is connected with the first reflector 2134, the second reflector 2135 and/or the third reflector 2136 for adjusting the angles of the corresponding reflectors, so that the adjustment of the laser emitting direction and the adjustment of the position of the focusing point can be easily realized.
The modularized housing 214 can place different housing modules in different positions according to requirements, is flexible and changeable, and can be additionally provided with an optical shaping lens for flat-top processing of laser spots according to requirements, so that laser energy with Gaussian distribution can be changed into laser beams with flat-top energy uniformly distributed, and/or a photoelectric trigger module for zero-jitter triggering of an electronic control pulse system of a mass spectrometer, and the like.
The housing 214 may not include the first reflective housing module 2144, the second reflective housing module 2145, and the third reflective housing module 2146, or include one or two of the first reflective housing module 2144, the second reflective housing module 2145, and the third reflective housing module 2146, and the orientations of the mirrors in the first reflective housing module 2144, the second reflective housing module 2145, and the third reflective housing module 2146 may be set as required. The optical system 20 shown in fig. 8 does not include the second reflective housing module, and the third reflective mirror in the third reflective housing module 21 is disposed downward, so as to guide the laser light emitted by the solid-state laser 22 in a direction perpendicular to the optical fixing platform 23. In addition, the optical system 20 shown in fig. 8 further includes a photo-triggering module 24 and an optical filter 25.
In the present embodiment, the laser emitted from the laser unit 210 is reflected by the optical reflection mechanism 240 and then emitted to the surface of the sample, and the angle between the reflected laser and the axis perpendicular to the sample target plate 120 is greater than 0 ° and not greater than 10 ° (the angle between the reflected laser and the sample target plate 120 is less than 90 ° and not less than 80 °), that is, the incident laser is emitted to the sample target plate 120 at a very small angle. Preferably, the angle between the reflected laser beam and the axis perpendicular to the sample target plate 120 is not more than 6 °, such as 3 °, 4 °, 5 °, or 6 °, and more preferably 4 ° to 5 °.
Further, the illumination light emitted by the illumination unit 220 of the present embodiment is reflected by the optical reflection mechanism 240 and then irradiates the surface of the sample, and the included angle between the illumination light reflected by the optical reflection mechanism 240 and the axis perpendicular to the sample target plate 120 is greater than 0 ° and not greater than 10 ° (the included angle between the illumination light reflected by the optical reflection mechanism 240 and the sample target plate 120 is less than 90 ° and not less than 80 °), that is, the incident illumination light irradiates the sample target plate 120 at a very small angle. Preferably, the angle between the illumination light reflected by the optical reflection mechanism 240 and the axis perpendicular to the sample target plate 120 is not more than 6 °, such as 3 °, 4 °, 5 °, or 6 °, and more preferably 4 ° to 5 °.
The imaging unit 230 is used to receive the illumination light reflected by the sample. The illumination light reflected by the sample and the illumination light reflected by the optical reflection mechanism 240 are symmetrically arranged with respect to a perpendicular line perpendicular to the sample target plate 120. In one specific example, illumination light reflected by the sample is reflected by the optical reflection mechanism 240 and enters the imaging unit 230.
More specifically, the imaging unit 230 includes an optical lens 232 and a photographing device 234. The illumination light reflected by the optical reflection mechanism 240 is captured by the optical lens 232 and then captured by the camera 234 for imaging. The camera 234 may be a CCD imaging device, and may be connected to an external display device for displaying the captured image.
Taking the specific example shown in fig. 2 as an example, the laser unit 210, the illumination unit 220, and the imaging unit 230 are disposed around the ion source cavity 110. Three transparent windows are opened on the ion source cavity 110 corresponding to the laser unit 210, the illumination unit 220 and the imaging unit 230.
Preferably, the light source of the illumination unit 220 is disposed opposite to the optical lens 232 of the imaging unit 230.
More preferably, the incidence direction of the laser light emitted from the laser unit 210 is perpendicular to the plane defined by the illumination light ray reflected by the optical reflection mechanism 240 and the illumination light ray reflected by the sample.
In a specific example, the optical reflection mechanism 240 has three reflection surfaces 242 for reflecting the incident laser light to the sample, the illumination light emitted from the illumination unit 220 to the sample, and the illumination light reflected from the sample to the imaging unit 230, respectively. As shown in fig. 2, taking the example that the illumination light reflected by the optical reflection mechanism 240 forms an angle of 5 ° with the axis perpendicular to the sample target plate 120, the reflection surface 242 for reflecting the illumination light forms an angle of 42.5 ° with the incident illumination light, and similarly, the reflection surface 242 for reflecting the illumination light reflected by the sample forms an angle of 42.5 ° with the illumination light emitted to the imaging unit 230. Similarly, when the angle between the laser beam reflected by the optical reflection mechanism 240 and the axis perpendicular to the sample target plate 120 is also 5 °, the reflection surface 242 for reflecting the laser beam is also 42.5 ° with respect to the incident laser beam.
Further, taking the ion source cavity 110 with a regular octahedral cylinder structure at the upper part as an example, preferably, the illumination unit 220 and the imaging unit 230 correspond to two opposite side walls of the octahedral cylinder structure of the ion source cavity 110, respectively, the laser unit 210 corresponds to the other side wall of the octahedral cylinder structure of the ion source cavity 110, and a side wall is spaced between the side wall and the side wall corresponding to the illumination unit 220 or the imaging unit 230. The schematic diagram shown in fig. 2 does not show the laser beam path perpendicular to the plane defined by the illumination light rays reflected by the optical reflection mechanism 240 and the illumination light rays reflected by the sample.
Further, in one specific example, the optical reflection mechanism 240 is located in the middle of the ion source cavity 110, and the illumination light rays reflected by the optical reflection mechanism 240 and the illumination light rays reflected by the sample are symmetrical about the central axis of the ion source cavity 110.
In order to reduce the angle between the laser incidence direction and the axis of the mass spectrometer flight tube as much as possible, the pole piece assembly 130 of the whole ion source assembly 100 and the like are all installed below the optical reflection mechanism 240, and the design of the pole piece inner hole 134 leading out the pole piece 132 can ensure that the laser and the illumination light can smoothly reach the surface of the sample without being influenced by the pole piece assembly 130. Therefore, the reflected laser can reach the surface of the sample at a very small angle, ionize the sample, and the surface light source generated by illumination can reach the imaging unit 230 through the hole array in the middle of the pole piece assembly 130.
Fig. 7 shows the actual spot measurement of the focusing point by using the laser unit 210 shown in fig. 3 and 4, and the result shows that the laser unit 210 can achieve the focusing effect of 16 × 14 μm at minimum.
The mass spectrometry detection device 10 can remarkably improve the resolution and imaging quality of mass spectrometry by small-angle laser incidence, illumination and imaging. Specifically, the laser emitted by the laser unit 210 is reflected by the optical reflection mechanism 240 and then emitted to the surface of the sample, and the included angle between the reflected laser light and the axis perpendicular to the sample target plate 120 is greater than 0 ° and not greater than 10 °, so that the angle formed by the incident direction of the laser and the axis direction of the ion source cavity 110 is very small, and the initial velocity direction of the particles generated by laser ionization basically diverges along the central axis direction of the ion source cavity 110, so that the initial kinetic energy divergence of the ions is small, which is beneficial to improving the resolution and sensitivity of the mass spectrometry detection apparatus 10. The illumination light emitted by the illumination unit 220 is reflected by the optical reflection mechanism 240 and then irradiates the surface of the sample, and the included angle between the illumination light reflected by the optical reflection mechanism 240 and the axis perpendicular to the sample target plate 120 is greater than 0 ° and not greater than 10 °, and the imaging unit 230 is used for receiving the illumination light reflected by the sample, so that the angle of the imaging light path is also very small. And the illumination and imaging directions are completely symmetrical, so that the intersection range of the illumination area generated by the illumination light source on the surface of the sample target plate 120 and the imaging area of the imaging unit 230 can be maximized, the generation of an evil shadow effect can be avoided, the imaging range can be greatly improved, and the imaging quality is greatly improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. An optical system of a mass spectrum detection device is characterized by comprising a laser unit, an illumination unit, an imaging unit and an optical reflection mechanism; the laser unit, the illumination unit and the imaging unit are arranged outside an ion source cavity of the mass spectrum detection device, and the optical reflection mechanism is arranged inside the ion source cavity;
the laser of the laser unit is a solid laser, the laser emitted by the laser unit is reflected by the optical reflection mechanism and then is emitted to the surface of the sample, and the included angle between the reflected laser ray and the axis vertical to the sample target plate is more than 0 degree and not more than 10 degrees; the illumination light emitted by the illumination unit is reflected by the optical reflection mechanism and then irradiates the surface of the sample, and the included angle between the illumination light reflected by the optical reflection mechanism and the axis vertical to the sample target plate is more than 0 degree and not more than 10 degrees; the imaging unit is for receiving illumination light reflected by the sample for sample imaging.
2. The optical system of claim 1, wherein the laser unit comprises an optical fixed platform and the solid state laser, optical path system and housing disposed on the optical fixed platform;
the light path system comprises a first focusing lens, a collimating lens and a second focusing lens, wherein a laser beam emitted by the solid laser generates a divergent laser beam through the first focusing lens, the divergent laser beam becomes a collimated laser beam after passing through the collimating lens, and the collimated laser beam can be reflected by the optical reflection mechanism and then incident on a sample after being focused by the second focusing lens;
the first focusing lens, the collimating lens and the second focusing lens are arranged in the shell, and the distance between the first focusing lens and the collimating lens is adjustable.
3. The optical system of claim 2, wherein the optical path system further comprises a filter for adjusting the energy of the laser beam.
4. The optical system of claim 3, wherein the housing is of a modular construction comprising a first lens housing module, a second lens housing module and a third lens housing module connected in series; the first focusing lens, the collimating lens, and the second focusing lens are disposed in the first lens housing module, the second lens housing module, and the third lens housing module, respectively;
the first lens housing module and the second lens housing module are relatively movable to adjust a distance between the first focusing lens and the collimating lens.
5. The optical system of claim 4, wherein the housing further comprises a first reflective housing module, a second reflective housing module, and/or a third reflective housing module, and correspondingly, the optical path system further comprises a first mirror disposed in the first reflective housing module, a second mirror disposed in the second reflective housing module, and/or a third mirror disposed in the third reflective housing module;
the first reflector housing module is connected between the first lens housing module and the second lens housing module, the second reflector housing module is connected between the second lens housing module and the third lens housing module, and the third reflector housing module is connected behind the third lens housing module.
6. The optical system of claim 5, wherein adjacent housing modules are coupled together by a threaded connection;
the relative movement between the first lens housing module and the second lens housing module is adjusted by a screw-type adjustment structure.
7. The optical system of claim 6, wherein the laser unit further comprises at least one of a filter adjustment mechanism, a lens adjustment mechanism, and a reflection adjustment mechanism;
the filtering adjusting mechanism is connected with the optical filter and is used for driving the optical filter to rotate;
the lens adjusting mechanism is connected with the first lens housing module and/or the second lens housing module and is used for adjusting the relative position of the first lens housing module and the second lens housing module;
the reflection adjustment mechanism is connected with the first mirror, the second mirror and/or the third mirror for adjusting the angle of the respective mirror.
8. The optical system according to any one of claims 1 to 7, wherein the optical reflection mechanism has three reflection surfaces for reflecting the incident laser light to the sample, the illumination light emitted from the illumination unit to the sample, and the illumination light reflected from the sample to the imaging unit, respectively.
9. The optical system according to any one of claims 1 to 7, wherein the imaging unit includes an optical lens and a camera, and the illumination light reflected by the optical reflection mechanism is captured by the optical lens and then taken into the camera.
10. A mass spectrometry detection device comprising an ion source assembly and an optical system according to any one of claims 1 to 9; the ion source assembly comprises an ion source cavity, a sample target plate and a pole piece assembly, wherein the sample target plate and the pole piece assembly are arranged in the ion source cavity and are positioned below the optical reflection mechanism; the laser unit is positioned on one side of the ion source cavity.
CN201811113273.1A 2018-09-25 2018-09-25 Mass spectrum detection device and optical system thereof Pending CN110940723A (en)

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