阅读说明：本技术 一种双重离子源慢电子速度成像装置 (Dual ion source slow electron speed imaging device ) 是由 王永天 刘洪涛 费泽杰 韩昌财 董常武 洪静 于 2020-06-30 设计创作，主要内容包括：本发明公开了一种双重离子源慢电子速度成像装置,包括激光蒸发离子源、电喷雾离子源、分析室、飞行时间质谱系统和慢电子速度成像系统,激光蒸发离子源和电喷雾离子源分别设置于分析室的两侧,飞行时间质谱系统和慢电子速度成像系统均设置于分析室内,分析室外设置有相匹配的相机。本发明的双重离子源的设计拓宽了单一装置的研究体系和目标阴离子团簇的产生渠道,具备了探测固相、液相样品产生单电荷和多电荷阴离子团簇的能力,双重离子源的集成相对于两台单一离子源的仪器,节省了真空腔体、分子泵、探测器等配件,节约了经费的同时简化了仪器操作步骤。(The invention discloses a dual ion source slow electron speed imaging device which comprises a laser evaporation ion source, an electrospray ion source, an analysis chamber, a flight time interstitial system and a slow electron speed imaging system, wherein the laser evaporation ion source and the electrospray ion source are respectively arranged on two sides of the analysis chamber, the flight time interstitial system and the slow electron speed imaging system are both arranged in the analysis chamber, and a matched camera is arranged outside the analysis chamber. The design of the dual ion source widens the research system of a single device and the generation channel of a target anion cluster, and has the capability of detecting solid-phase and liquid-phase samples to generate single-charge and multi-charge anion clusters.)

1. A dual ion source slow electron velocity imaging apparatus, comprising: the system comprises a laser evaporation ion source, an electrospray ion source, an analysis chamber, a flight time interstitial system and a slow electron velocity imaging system, wherein the laser evaporation ion source and the electrospray ion source are respectively arranged on two sides of the analysis chamber, the flight time interstitial system and the slow electron velocity imaging system are both arranged in the analysis chamber, and a matched camera is arranged outside the analysis chamber.

2. The dual ion source slow electron velocity imaging apparatus of claim 1, wherein: the electrospray ion source is provided with three stages of vacuum chambers, a strainer partition plate is arranged between each stage of vacuum chamber, a heating block and two radio frequency quadrupole rods are sequentially coaxially arranged in the three stages of vacuum chambers, a hole is formed in the middle of the heating block and communicated with a stainless steel ion injector, and 2000-4000V direct-current voltage is loaded on a needle head of the ion injector.

3. The dual ion source slow electron velocity imaging apparatus of claim 2, wherein: a gate valve and a strainer partition plate are arranged between the electrospray ion source and the analysis chamber, a radio frequency eight-stage rod is arranged in the analysis chamber, the radio frequency eight-stage rod and the radio frequency quadrupole rod are coaxially arranged, the diameter of an opening of the strainer partition plate is 1.5mm, and the taper angle is 13 degrees.

4. The dual ion source slow electron velocity imaging apparatus of claim 1, wherein: the laser evaporation ion source comprises a reaction source head, an air bottle, a solid laser, a stepping motor and a sample target, wherein the reaction source head, the stepping motor and the sample target are arranged in an ion source chamber; one end of the carrier gas passage is connected with a gas cylinder through an electromagnetic pulse valve, a strainer partition plate and a gate valve are arranged between the ion source chamber and the analysis chamber, an ion restriction hole is arranged in the analysis chamber, and the ion restriction hole and an opening of the strainer partition plate are arranged in a collinear manner.

5. The dual ion source slow electron velocity imaging apparatus of claim 4, wherein: the laser ion confinement structure comprises a laser passage, a carrier gas passage, a nozzle, three ion confinement holes and a nozzle, wherein the straight passage of the laser passage is 3mm, the diameter of the carrier gas passage is 1mm, the nozzle is arranged behind the carrier gas passage, the length of the nozzle is 8mm, the cone angle of the nozzle is 15 degrees, the ion confinement holes are three hole plates with holes formed in the middle, and the diameters of the holes formed in the hole plates are sequentially increased and are 3mm, 4mm and 5 mm.

6. The dual ion source slow electron velocity imaging apparatus of claim 1, wherein: the analysis chamber comprises an acceleration chamber and a mass spectrum chamber, the acceleration chamber is communicated with the mass spectrum chamber, a shielding cylinder is arranged in the mass spectrum chamber, the laser evaporation ion source and the electrospray ion source are respectively in sealing connection with the acceleration chamber through gate valves, and the slow electron velocity imaging system is arranged in the shielding cylinder.

7. The dual ion source slow electron velocity imaging apparatus of claim 6, wherein: the flight time mass spectrum system comprises an ion accelerator, an ion deflection plate, two groups of ion electrostatic lenses, a mass gate and a mass spectrum detector which are sequentially arranged, wherein the ion deflection plate, the two groups of ion electrostatic lenses and the mass gate are coaxially arranged and are all connected with electricity, and the mass spectrum detector is rotatably arranged at an inlet of the shielding cylinder.

8. The dual ion source slow electron velocity imaging apparatus of claim 7, wherein: the ion accelerator is composed of three electrode plates with the thickness of 1mm, wherein two electrode plates are stuck with a nickel screen with the transmittance of 90%; the quality door comprises three perforated pole pieces with the thickness of 1mm and the interval of 2mm, and each perforated pole piece is pasted with a nickel net with the transmittance of 98%.

9. The dual ion source slow electron velocity imaging apparatus of claim 6, wherein: slow electron speed imaging system include imaging detector, CCD camera, shielding section of thick bamboo and set gradually in reference section of thick bamboo and imaging lens in the shielding section of thick bamboo, reference a section of thick bamboo imaging lens imaging detector with CCD camera coaxial line sets up, imaging detector set up in on the indoor wall of mass spectrum, the CCD camera set up in outside the mass spectrum, desorption laser passes imaging lens.

10. The dual ion source slow electron velocity imaging apparatus of claim 9, wherein: the dye laser is vertically arranged on one side of the imaging lens, the imaging lens comprises three perforated electrode plates, the hole diameter of the first perforated electrode plate is 8mm, and the hole diameters of the second perforated electrode plates are 12 mm; the shielding cylinder is a double-layer permalloy shielding cylinder.

Technical Field

The invention relates to the technical field of mass spectrometry and photoelectron imaging, in particular to a dual ion source slow electron velocity imaging device.

Background

The gas phase experiment can avoid the influence of factors such as complex chemical environment, sample defects, nonuniformity and the like in a liquid phase and a solid phase, and provides an ideal research model for an isolated system. Single-charge and multi-charge anionic cluster are widely distributed in nature, and the exploration of the geometrical and electronic structures of the clusters is of great significance for understanding the chemical reaction in nature, the design of industrial catalysts and the like. The laser evaporation cluster source can ionize solid-phase metals, metal compounds and other samples to generate singly-charged anionic clusters. The electrospray ion source can ionize liquid-phase organic matters to generate organic micromolecule and biological macromolecule multi-charge anion clusters. The mass range of the time-of-flight mass spectrometry is large, the resolution ratio is high, the mass spectrometer is a scientific instrument which is applied to a plurality of fields of analysis at present, the species composition can be determined, and the geometric and electronic structure is difficult to accurately determine. The slow electron velocity imaging technology is a recently newly developed photoelectron imaging technology with high resolution and high sensitivity, can perform full spectrum and near-threshold energy spectrum scanning to obtain a photoelectron energy spectrum with extremely high resolution, and can determine the geometric and electronic structure of a target anionic cluster by combining theoretical calculation.

At present, few subject groups are developed for anionic cluster research by combining time-of-flight mass spectrometry technology with slow electron velocity imaging technology at home and abroad, and most of instruments adopt a single ion source, so that the range and flexibility of a research system are severely limited; in addition, if the electronic properties of different charges of the same anion cluster need to be detected, the whole instrument needs to be replaced, which changes the detection condition of ions, generates new variables, and has complex and time-consuming experimental operation.

Disclosure of Invention

The invention aims to provide a dual ion source slow electron velocity imaging device, which solves the problems in the prior art, enables an instrument to be integrated with a dual ion source and has the capability of detecting single-charge and multi-charge anionic clusters generated by solid-phase and liquid-phase samples.

In order to achieve the purpose, the invention provides the following scheme:

the invention provides a dual ion source slow electron speed imaging device which comprises a laser evaporation ion source, an electrospray ion source, an analysis chamber, a flight time interstitial system and a slow electron speed imaging system, wherein the laser evaporation ion source and the electrospray ion source are respectively arranged on two sides of the analysis chamber, the flight time interstitial system and the slow electron speed imaging system are both arranged in the analysis chamber, and a matched camera is arranged outside the analysis chamber.

Preferably, the electrospray ion source is provided with three stages of vacuum chambers, a strainer partition plate is arranged between each stage of vacuum chamber, the heating block and the two radio frequency quadrupole rods are coaxially arranged in the three stages of vacuum chambers in sequence, a hole is formed in the middle of the heating block and is communicated with a stainless steel ion injector, and a needle of the ion injector is loaded with 2000-4000V direct current voltage.

Preferably, a gate valve and a strainer partition plate are arranged between the electrospray ion source and the analysis chamber, a radio frequency eight-stage rod is arranged in the analysis chamber, the radio frequency eight-stage rod and the radio frequency quadrupole rod are coaxially arranged, the diameter of an opening of the strainer partition plate is 1.5mm, and the cone angle is 13 degrees.

Preferably, the laser evaporation ion source comprises a reaction source head, a gas cylinder, a solid laser, a stepping motor and a sample target, wherein the reaction source head, the stepping motor and the sample target are arranged in an ion source chamber, the reaction source head is provided with a laser channel and a carrier gas channel which are perpendicular to each other, the solid laser is arranged outside the ion source chamber and is arranged in a collinear way with the laser channel, the stepping motor is connected with the sample target, and the sample target is arranged at the tail end of the laser channel; one end of the carrier gas passage is connected with a gas cylinder through an electromagnetic pulse valve, a strainer partition plate and a gate valve are arranged between the ion source chamber and the analysis chamber, an ion restriction hole is arranged in the analysis chamber, and the ion restriction hole and an opening of the strainer partition plate are arranged in a collinear manner.

Preferably, the diameter of the laser channel is 3mm, the diameter of the carrier gas channel is 1mm, a nozzle with the length of 8mm and the cone angle of 15 degrees is arranged behind the carrier gas channel, the ion confinement holes are three hole plates with holes in the middle, and the diameters of the holes in the hole plates are sequentially increased and are 3mm, 4mm and 5 mm.

Preferably, the analysis chamber comprises an acceleration chamber and a mass spectrometry chamber, the acceleration chamber is communicated with the mass spectrometry chamber, a shielding cylinder is arranged in the mass spectrometry chamber, the laser evaporation ion source and the electrospray ion source are respectively connected with the acceleration chamber in a sealing manner through gate valves, and the slow electron velocity imaging system is arranged in the shielding cylinder.

Preferably, the time-of-flight mass spectrometry system comprises an ion accelerator, an ion deflection plate, two groups of ion electrostatic lenses, a mass gate and a mass spectrometer, wherein the ion deflection plate, the two groups of ion electrostatic lenses and the mass gate are coaxially arranged and are all connected with electricity, and the mass spectrometer is rotatably arranged at an inlet of the shielding cylinder.

Preferably, the ion accelerator is provided with three electrode plates with the thickness of 1mm, wherein two electrode plates are stuck with a nickel screen with the transmittance of 90%; the quality door comprises three perforated pole pieces with the thickness of 1mm and the interval of 2mm, and each perforated pole piece is pasted with a nickel net with the transmittance of 98%.

Preferably, slow electron speed imaging system include imaging detector, CCD camera, shielding section of thick bamboo and set gradually in reference section of thick bamboo and imaging lens in the shielding section of thick bamboo, reference a section of thick bamboo imaging lens imaging detector with CCD camera coaxial line sets up, imaging detector set up in on the indoor wall of mass spectrum, the CCD camera set up in outside the mass spectrum, the desorption laser passes imaging lens.

Preferably, the dye laser is vertically arranged on one side of the imaging lens, the imaging lens comprises three perforated electrode plates, the diameter of the hole of the first perforated electrode plate is 8mm, and the diameters of the holes of the second perforated electrode plates are 12 mm; the shielding cylinder is a double-layer permalloy shielding cylinder.

Compared with the prior art, the invention has the following technical effects:

the design of the dual ion source widens the research system of a single device and the generation channel of a target anion cluster, and has the capability of detecting solid-phase and liquid-phase samples to generate single-charge and multi-charge anion clusters.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.

FIG. 1 is a schematic diagram of the structure and principle of a dual ion source slow electron velocity imaging apparatus according to the present invention;

wherein: 1-ion injector, 2-heating block, 3-strainer partition, 4-radio frequency quadrupole, 5-vacuum cavity, 6-gate valve, 7-radio frequency eight-stage rod, 8-accelerating chamber, 9-ion accelerator, 10-ion source chamber, 11-reaction source, 12-sample target, 13-solid laser, 14-nozzle, 15-gas cylinder, 16-electromagnetic pulse valve, 17-ion confinement hole, 18-mass spectrum chamber, 19-ion deflection plate, 20-ion electrostatic lens, 21-mass gate, 22-mass spectrum detector, 23-shielding cylinder, 24-reference cylinder, 25-imaging lens, 26-imaging detector, 27-dye laser and 28-CCD camera.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.

The invention aims to provide a dual ion source slow electron velocity imaging device, which solves the problems in the prior art, enables an instrument to be integrated with a dual ion source and has the capability of detecting single-charge and multi-charge anionic cluster generated by solid-phase and liquid-phase samples.

In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.

As shown in fig. 1: the embodiment provides a dual ion source slow electron speed imaging device, including laser evaporation ion source, electrospray ion source, analysis chamber, time of flight interstitial system and slow electron speed imaging system, laser evaporation ion source and electrospray ion source set up respectively in the both sides of analysis chamber, and time of flight interstitial system and slow electron speed imaging system all set up in the analysis chamber, are provided with assorted camera outside the analysis chamber.

Specifically, the electrospray ion source is provided with three-stage vacuum chambers 5, a strainer partition plate 3 is arranged between each stage of vacuum chambers 5, a heating block 2 and two radio frequency quadrupole rods 4 are coaxially arranged in the three-stage vacuum chambers 5 in sequence, a hole is formed in the middle of the heating block 2 and communicated with a stainless steel ion injector 1, and a needle of the ion injector 1 is loaded with 2000-4000V direct current voltage. A gate valve 6 and a strainer partition plate 3 are arranged between the electrospray ion source and the analysis chamber, a radio frequency eight-stage rod 7 is arranged in the analysis chamber, the radio frequency eight-stage rod 7 and a radio frequency quadrupole rod 4 are coaxially arranged, the diameter of an opening of the strainer partition plate 3 is 1.5mm, and the cone angle is 13 degrees.

The laser evaporation ion source comprises a reaction source head 11, an air bottle 15, a solid laser 13, a stepping motor and a sample target 12, wherein the reaction source head 11, the stepping motor and the sample target 12 are arranged in an ion source chamber 10, the reaction source head 11 is provided with a laser channel and a carrier gas channel which are vertical to each other, the solid laser 13 is arranged outside the ion source chamber 10 and is arranged in a collinear way with the laser channel (an optical window is arranged on the side wall of the ion source chamber 10), the stepping motor is connected with the sample target 12, and the sample target 12 is arranged at the tail end of the laser channel; one end of the carrier gas passage is connected with a gas cylinder 15 through an electromagnetic pulse valve 16, and the gas in the gas cylinder is carried into the carrier gas passage through the electromagnetic pulse valve 16. A perforated spoon partition plate 3 and a gate valve 6 are arranged between the ion source chamber 10 and the analysis chamber, an ion restriction hole 17 is arranged in the analysis chamber, and the ion restriction hole 17 and the perforated hole of the perforated spoon partition plate 3 are arranged in a collinear manner. The diameter of the laser channel is 3mm, the diameter of the carrier gas channel is 1mm, a nozzle 14 with the length of 8mm and the cone angle of 15 degrees is arranged behind the carrier gas channel, the ion restraint holes 17 are three pore plates with holes in the middle, the diameters of the holes on the pore plates are sequentially increased and are 3mm, 4mm and 5mm, and the ion restraint holes 17 are used for restraining the spatial dispersion degree of ions entering the ion accelerator 9.

The analysis chamber comprises an acceleration chamber 8 and a mass spectrum chamber 18, the acceleration chamber 8 is communicated with the mass spectrum chamber 18, a shielding cylinder 23 is arranged in the mass spectrum chamber 18, the laser evaporation ion source and the electrospray ion source are respectively in sealing connection with the acceleration chamber 8 through gate valves 6, a slow electron velocity imaging system is arranged in the shielding cylinder 23, when the laser evaporation ion source or the electrospray ion source is not used, one of the gate valves 6 is closed, the ion source can be isolated from being communicated with other parts, and the vacuum degree in other structures is kept.

The flight time mass spectrum system comprises an ion accelerator 9, an ion deflection plate 19, two groups of ion electrostatic lenses 20, a mass gate 21 and a mass spectrum detector 22 which are sequentially arranged, wherein the ion deflection plate 19, the two groups of ion electrostatic lenses 20 and the mass gate 21 are coaxially arranged and are all connected with electricity, and the mass spectrum detector 22 is rotatably arranged at an inlet of a shielding cylinder 23. The ion accelerator 9 is three electrode plates with the thickness of 1mm, wherein two electrode plates are stuck with a nickel screen with the transmittance of 90 percent; the mass gate 21 comprises three perforated pole pieces with the thickness of 1mm and the interval of 2mm, and each perforated pole piece is pasted with a nickel net with the transmittance of 98%.

The slow electron velocity imaging system comprises an imaging detector 26, a CCD camera 28, a shielding cylinder 23, a reference cylinder 24 and an imaging lens 25 which are sequentially arranged in the shielding cylinder 23, wherein the reference cylinder 24, the imaging lens 25, the imaging detector 26 and the CCD camera 28 are coaxially arranged, the imaging detector 26 is arranged on the inner wall of the mass spectrum chamber 18, the CCD camera 28 is arranged outside the mass spectrum chamber 18, and desorption laser passes through the imaging lens 25. The dye laser 27 is vertically arranged on one side of the imaging lens 25 (an optical window is arranged on the side wall of the mass spectrum chamber 18), the imaging lens 25 comprises three perforated electrode plates, the hole diameter of the first perforated electrode plate is 8mm, and the hole diameters of the second perforated electrode plates are 12 mm; the shielding cylinder 23 is a double-layer permalloy shielding cylinder and can shield the interference of the geomagnetic field and the stray electric field of electrons in the desorption and flight processes.

When a sample is a solid phase and a research system is a single-charge anion cluster, a laser evaporation ion source is used for generating a target anion cluster, a stepping motor drives a rotating sample target 12 to be evaporated at high temperature by evaporation laser to generate plasma, carrier gas ejected from an electromagnetic pulse valve 16 of a gas cylinder 15 collides with the plasma through a carrier gas channel of a reaction source head 11 and generates ultrasonic expansion cooling and cluster growth along a growth channel (carrier gas channel) of the reaction source head 11, and then the anion cluster enters an ion accelerator 9 of a flight time mass spectrum system through a strainer partition plate 3 and an ion restriction hole 17.

When the sample is in a liquid phase and the research system is a single-charge or multi-charge anion cluster, an electrospray ion source is used for generating the target anion cluster. The liquid sample is sprayed out by an ion injector 1, the generated charged liquid drops are desolvated by a heating block 2 and then enter a second-stage vacuum cavity 5 through a strainer clapboard 3, and then the ions enter an ion accelerator 9 of a flight time mass spectrum system under the guidance of a two-stage radio frequency quadrupole 4 and a radio frequency eight-stage rod 7.

Anion clusters generated from a laser evaporation ion source or an electrospray ion source enter an accelerator of a time-of-flight mass spectrometry system, ions are modulated by an ion deflection plate 19 and two groups of ion electrostatic lenses 20 after being accelerated, and then reach a mass spectrometry detector 22 to measure ion species, after the target anion cluster is selected, the mass gate 21 is utilized to select the mass of the ions, the mass spectrum detector 22 is rotated to open the ion path, the target anion cluster enters the imaging lens 25 through the reference cylinder 24, the flight time of the ions is calculated, when the ions just reach the middle position of the front two pole pieces of the imaging lens 25, the desorption laser emits and interacts with the ion beam, the anion can be desorbed with electrons from the valence track by the desorption laser, the desorbed electrons fly to the imaging detector 26 under the acceleration of the imaging lens 25, and the position distribution of the electrons impacting the imaging detector 26 is recorded by the CCD camera 28 at the back to obtain an original image. The original image is processed to obtain the photoelectron spectrum of the target anion, so that the geometric and electronic structure of the target anion is researched by combining theoretical calculation.

In the embodiment, two ion sources (a laser evaporation cluster source and an electrospray ion source) for researching the electron property of an anion cluster are integrated on the same slow electron velocity imaging device, the laser evaporation ion source and the electrospray ion source are respectively arranged at two sides of a flight time mass spectrum system, generated ions are vertically introduced into the flight time mass spectrum system, when one ion source works, a gate valve 6 connecting the other ion source with the flight time mass spectrum system can be closed, an electric field applied by the other ion source is removed, and the interference of the other ion source is avoided. When one ion source is unable to produce the target anion cluster, the attempt to replace the ion source under the same probing conditions can be changed nearby.

The principle and the implementation mode of the present invention are explained by applying specific examples in the present specification, and the above descriptions of the examples are only used to help understanding the method and the core idea of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.