CN103972018B - Radio-frequency electric field enhanced single photon and chemical ionization source - Google Patents
Radio-frequency electric field enhanced single photon and chemical ionization source Download PDFInfo
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Abstract
Description
技术领域technical field
本发明涉及质谱仪电离源，具体的说是一种射频电场增强的单光子-化学电离源。本发明在包含单光子电离源的基础上，利用光电效应得到的光电子电离试剂气体得到化学电离源，通过电离区内引入射频电场增强光电子引发的化学电离，提高了检测灵敏度，并且可实现电离能高于紫外线光子能量的样品分子的软电离，拓宽了分析样品的范围。通过对射频电压开启和关闭的控制，可灵活地实现两种不同电离方式之间的切换。The invention relates to an ionization source of a mass spectrometer, in particular to a single photon-chemical ionization source enhanced by a radio frequency electric field. On the basis of including a single photon ionization source, the present invention uses the photoelectron ionization reagent gas obtained by the photoelectric effect to obtain a chemical ionization source, and introduces a radio frequency electric field into the ionization area to enhance the chemical ionization caused by photoelectrons, thereby improving the detection sensitivity and realizing the ionization energy Soft ionization of sample molecules above UV photon energy broadens the range of analyzed samples. By controlling the on and off of the radio frequency voltage, the switching between two different ionization modes can be flexibly realized.
背景技术Background technique
传统的有机物质谱中通常采用电子轰击电离源（EI），它利用70eV能量的电子去轰击有机物分子，使其电离，每种有机物都能得到各自的特征谱图，通过谱图库检索，大多能够准确的进行定性分析。但是，有时会产生大量的碎片离子，尤其在分析复杂混合物时的谱峰重叠，识谱困难，不利于样品的快速、在线分析。真空紫外光能够使电离能（IE）低于其光子能量的有机物分子发生软电离，主要产生分子离子，几乎没有碎片离子，适合于快速的定性定量分析。侯可勇[中国发明专利:200610011793.2]和郑培超[中国发明专利:200810022557.X]将真空紫外光电离源与质谱结合，得到的有机物质谱图中只包含有机物的分子离子峰，谱图简单，可根据分子量和信号强度进行快速的定性、定量分析。Electron bombardment ionization source (EI) is usually used in traditional organic mass spectrometry. It uses electrons with 70eV energy to bombard organic molecules and ionize them. Each organic compound can get its own characteristic spectrum. Most of them can be accurately for qualitative analysis. However, sometimes a large number of fragment ions are generated, especially when analyzing complex mixtures, the spectral peaks overlap, making it difficult to read the spectrum, which is not conducive to the rapid and online analysis of samples. Vacuum ultraviolet light can softly ionize organic molecules whose ionization energy (IE) is lower than its photon energy, mainly producing molecular ions with almost no fragment ions, suitable for rapid qualitative and quantitative analysis. Hou Keyong [Chinese Invention Patent: 200610011793.2] and Zheng Peichao [Chinese Invention Patent: 200810022557.X] combined the vacuum ultraviolet photoionization source with mass spectrometry, and the organic substance spectrum obtained only contains molecular ion peaks of organic substances. The spectrum is simple and can be determined according to the molecular weight Quick qualitative and quantitative analysis of signal intensity and signal intensity.
真空紫外光源中特别是真空紫外灯中使用的光窗材料限制了透过光的光子能量。目前已知的仅有LiF光窗材料透过光子能量最高可达11.8eV。所以，只有电离能低于11.8eV的有机物分子利用11.8eV光子能够得到有效电离，而电离能高于11.8eV的化合物光子则无能为力。为解决该问题，花磊[PCT：201010567193]采用真空紫外光源在试剂区产生的光电子，在静电场下加速电离试剂气体，产生试剂离子。然后传输试剂离子进入反应区与样品分子发生化学电离。该发明实现了单光子电离和化学电离两种软电离方式的在线切换，拓宽了可分析物的范围。The light window materials used in VUV sources, especially VUV lamps, limit the photon energy of the transmitted light. Currently known only LiF optical window materials can transmit photon energy up to 11.8eV. Therefore, only organic molecules with ionization energy lower than 11.8eV can be effectively ionized by 11.8eV photons, while compound photons with ionization energy higher than 11.8eV are powerless. To solve this problem, Hualei [PCT: 201010567193] uses photoelectrons generated by a vacuum ultraviolet light source in the reagent area to accelerate the ionization of reagent gas under an electrostatic field to generate reagent ions. The reagent ions are then transported into the reaction zone where they chemically ionize with the sample molecules. The invention realizes the online switching of two soft ionization modes, single photon ionization and chemical ionization, and broadens the range of analytes.
然而，商品化的真空紫外灯光源有限的光密度，不仅限制了单光子电离的灵敏度，而且也限制了光电子的数量，降低了试剂离子强度，导致化学电离灵敏度受限。而且，在较高的气压条件下，电子与气体分子频繁碰撞，在发生碰撞后，需要从静电场中重新获得能量去碰撞电离分子，然而电子在静电场中单方向直线运动，运动速度快，电子在电离区的停留时间短，导致静电场加速光电子电离试剂气体分子的效率低下。However, the limited optical density of commercial vacuum ultraviolet light sources not only limits the sensitivity of single photon ionization, but also limits the number of photoelectrons, which reduces the reagent ion intensity, resulting in limited chemical ionization sensitivity. Moreover, under higher air pressure conditions, electrons collide frequently with gas molecules. After the collision, energy needs to be regained from the electrostatic field to collide with the ionized molecules. The short residence time of the electrons in the ionization region results in inefficiency in the acceleration of the photoelectron-ionized reagent gas molecules by the electrostatic field.
发明内容Contents of the invention
本发明的目的在于提供一种射频电场增强的单光子-化学电离源，在包含单光子电离源的基础上，通过在电离区引入射频电场，利用射频电场调制光电子振荡、往复运动，提高光电子运动路程和在电离区中的停留时间，增强光电子电离作用，提高检测灵敏度，并且利用化学电离源可实现电离能高于紫外线光子能量的样品分子的软电离。通过对射频电压开启和关闭的控制，可灵活实现单光子电离、单光子-化学电离两种不同电离方式之间的切换。The purpose of the present invention is to provide a single photon-chemical ionization source enhanced by a radio frequency electric field. On the basis of including a single photon ionization source, by introducing a radio frequency electric field in the ionization area, the radio frequency electric field is used to modulate the photoelectron oscillation and reciprocating motion, and improve the photoelectron motion. The distance and the residence time in the ionization zone can enhance the photoelectron ionization, improve the detection sensitivity, and use the chemical ionization source to realize the soft ionization of the sample molecules whose ionization energy is higher than the energy of ultraviolet photons. By controlling the on and off of the radio frequency voltage, the switch between two different ionization methods, single photon ionization and single photon-chemical ionization, can be flexibly realized.
为实现上述目的，本发明采用的技术方案为：To achieve the above object, the technical solution adopted in the present invention is:
一种射频电场增强的单光子-化学电离源，包括真空紫外光源、电离室腔体、一个或一个以上的传输电极和差分孔电极，于电离室腔体壁上有样品气毛细管接口、试剂气毛细管接口、真空规接口和真空泵抽气口；A single photon-chemical ionization source enhanced by a radio frequency electric field, including a vacuum ultraviolet light source, an ionization chamber cavity, one or more transmission electrodes and a differential hole electrode, and a sample gas capillary interface and a reagent gas on the ionization chamber cavity wall Capillary interface, vacuum gauge interface and vacuum pump exhaust port;
传输电极置于电离室腔体内部，传输电极的轴向开有通孔；当为一个以上的传输电极时，一个以上的传输电极之间相互平行、间隔设置，通孔同轴；The transmission electrodes are placed inside the cavity of the ionization chamber, and the axial direction of the transmission electrodes is provided with through holes; when there are more than one transmission electrodes, the more than one transmission electrodes are arranged parallel to each other and spaced apart, and the through holes are coaxial;
于传输电极的通孔上方处的电离室腔体壁上设有紫外光入口，紫外光入口与通孔同轴；于传输电极的下方处设有差分孔电极，差分孔电极的孔与通孔同轴，紫外光源发出的紫外光从紫外光入口照射在差分孔电极表面，通过光电效应产生光电子；An ultraviolet light entrance is provided on the wall of the ionization chamber above the through hole of the transmission electrode, and the ultraviolet light entrance is coaxial with the through hole; a differential hole electrode is provided below the transmission electrode, and the hole of the differential hole electrode is connected to the through hole Coaxial, the ultraviolet light emitted by the ultraviolet light source is irradiated on the surface of the differential hole electrode from the ultraviolet light entrance, and photoelectrons are generated through the photoelectric effect;
传输电极上施加有直流传输电压；当为一个以上的传输电极时，一个以上的传输电极的各电极上依次施加有直流传输电压，各电极上依次施加的电压沿光入射方向依次降低；A DC transmission voltage is applied to the transmission electrodes; when there are more than one transmission electrodes, each electrode of the more than one transmission electrode is sequentially applied with a DC transmission voltage, and the voltages sequentially applied to each electrode decrease sequentially along the light incident direction;
在传输电极的其中一个通过电容耦合的方式叠加有一射频电压；A radio frequency voltage is superimposed on one of the transmission electrodes through capacitive coupling;
当为一个以上的传输电极时，除叠加有射频电压的传输电极之外的其他每片电极上都通过电容接地；When there are more than one transmission electrode, each electrode except the transmission electrode superimposed with radio frequency voltage is grounded through a capacitor;
差分孔电极上施加有直流电压，且通过电容接地，同时也通过电阻连接到地；A DC voltage is applied to the differential hole electrodes, grounded through a capacitor, and connected to ground through a resistor;
试剂气毛细管和样品气毛细管分别通过电离室腔体壁上的试剂气毛细管接口和样品气毛细管接口进入电离室内部；试剂气毛细管和样品气毛细管的气体出口位于传输电极与差分孔电极之间或传输电极与传输电极之间；试剂气毛细管和样品气毛细管的气体出口端垂直于紫外光束。The reagent gas capillary and the sample gas capillary enter the ionization chamber through the reagent gas capillary interface and the sample gas capillary interface on the cavity wall of the ionization chamber respectively; the gas outlets of the reagent gas capillary and sample gas capillary are located between the transmission electrode and the differential hole electrode or the transmission electrode. Between the electrode and the transfer electrode; the gas outlet ends of the reagent gas capillary and the sample gas capillary are perpendicular to the UV beam.
一个以上的传输电极的各电极上依次施加有直流传输电压，直流传输电压采用同一直流电源，各电极上依次施加的直流电压通过电阻进行分压。A DC transmission voltage is sequentially applied to each electrode of more than one transmission electrode, and the same DC power source is used for the DC transmission voltage, and the DC voltage sequentially applied to each electrode is divided by a resistor.
传输电极与差分孔电极之间通过绝缘材料隔开，所有电极中间开有通孔，电极之间同轴且间隔设置；The transmission electrode and the differential hole electrode are separated by an insulating material, and there are through holes in the middle of all electrodes, and the electrodes are coaxial and spaced apart;
当为一个以上的传输电极时，相邻两片传输电极之间通过绝缘材料隔开，所有传输电极中间开有通孔，传输电极之间同轴且间隔设置。When there is more than one transmission electrode, two adjacent transmission electrodes are separated by an insulating material, through holes are opened in the middle of all transmission electrodes, and the transmission electrodes are arranged coaxially and at intervals.
差分孔电极中部开有小孔，与传输电极同轴；There is a small hole in the middle of the differential hole electrode, which is coaxial with the transmission electrode;
于差分孔电极下方设有质量分析器，电离室产生的离子通过小孔进入质量分析器；所述的质量分析器为飞行时间质量分析器、四级杆质量分析器或离子阱质量分析器。A mass analyzer is arranged under the differential hole electrode, and ions generated by the ionization chamber enter the mass analyzer through the small hole; the mass analyzer is a time-of-flight mass analyzer, a quadrupole mass analyzer or an ion trap mass analyzer.
紫外光源可为气体放电灯光源、激光光源或同步辐射光源。The ultraviolet light source can be a gas discharge lamp light source, a laser light source or a synchrotron radiation light source.
样品通过样品气毛细管进样；The sample is injected through the sample gas capillary;
真空规接口与真空规相连，真空泵抽气口经调节阀门与真空泵相连；电离室真空度通过对真空泵和调节阀门控制，维持在1Pa到500Pa之间；电离室真空值通过真空规来获得。The vacuum gauge interface is connected to the vacuum gauge, and the vacuum pump exhaust port is connected to the vacuum pump through the regulating valve; the vacuum degree of the ionization chamber is maintained between 1Pa and 500Pa through the control of the vacuum pump and the regulating valve; the vacuum value of the ionization chamber is obtained through the vacuum gauge.
电离源可以实现两种不同的工作模式的切换；The ionization source can switch between two different working modes;
当关闭射频电压时，为单光子电离模式；当开启射频电压时，光电效应产生的光电子从射频场中获得能量，光电子碰撞电离试剂气体产生试剂离子，得到软电离的化学电离源，此时单光子电离和化学电离同时作用；When the RF voltage is turned off, it is in the single photon ionization mode; when the RF voltage is turned on, the photoelectrons generated by the photoelectric effect obtain energy from the RF field, and the photoelectrons collide with the ionized reagent gas to generate reagent ions to obtain a chemical ionization source for soft ionization. Simultaneous action of photon ionization and chemical ionization;
传输电极为片状或板状，中部沿轴向（轴向是指垂直于板面的法线方向）开有通孔。The transmission electrode is in the shape of a sheet or a plate, and a through hole is opened in the middle along the axial direction (the axial direction refers to the normal direction perpendicular to the plate surface).
本发明提供的电离源，在包含单光子电离源的基础上，通过在电离区引入射频电场在中等气压条件下，利用射频电场控制光电子振荡，有效电离试剂气体，产生的试剂离子进一步与样品分子发生化学电离。仅通过控制射频电压的开启和关闭，可以实现两种软电离方式的快速切换。The ionization source provided by the present invention, on the basis of including a single-photon ionization source, introduces a radio frequency electric field in the ionization region under medium pressure conditions, uses the radio frequency electric field to control the photoelectron oscillation, and effectively ionizes the reagent gas, and the generated reagent ions are further combined with the sample molecules Chemical ionization occurs. Only by controlling the on and off of the radio frequency voltage, the fast switching between the two soft ionization modes can be realized.
附图说明Description of drawings
图1为本发明的基于真空紫外光的射频电场增强的单光子-化学电离源结构示意图。Fig. 1 is a schematic diagram of the structure of a single-photon-chemical ionization source based on vacuum ultraviolet light-enhanced radio frequency electric field of the present invention.
图2为实施例1中10ppm苯、甲苯和二甲苯气体样品（O2为平衡气）在不同条件下的质谱图，包括仅有紫外光电离时，没有紫外光仅有射频电压时，紫外光和射频电压同时施加时。Fig. 2 is the mass spectrogram of 10ppm benzene, toluene and xylene gas samples (O 2 is the balance gas) in Example 1 under different conditions, including when there is only ultraviolet photoionization, when there is no ultraviolet light and only radio frequency voltage, ultraviolet light When applied simultaneously with RF voltage.
图3为实施例2中O2作为试剂气体时射频场化学电离10ppm氯仿（CHCl3）累计50万次获得的质谱图，氯仿的电离能为11.4eV，大于光子能量10.6eV。Fig. 3 is a mass spectrum obtained by radio frequency field chemical ionization of 10ppm chloroform (CHCl 3 ) accumulated 500,000 times in Example 2 when O 2 is used as a reagent gas. The ionization energy of chloroform is 11.4eV, which is greater than the photon energy of 10.6eV.
图4为实施例3中O2作为试剂气体时不同电离能样品的增强倍数。Fig. 4 is the enhancement factor of samples with different ionization energies when O2 is used as reagent gas in Example 3.
具体实施方式detailed description
请参阅图1，为本发明的结构示意图。本发明的电离源，由真空紫外光源1、电离室腔体2、若干传输电极4和差分孔电极5，于电离室腔体2壁上有样品气毛细管3接口，试剂气毛细管9，真空规6接口和真空泵7抽气口构成。Please refer to FIG. 1 , which is a schematic structural diagram of the present invention. The ionization source of the present invention is composed of a vacuum ultraviolet light source 1, an ionization chamber cavity 2, a plurality of transmission electrodes 4 and a differential hole electrode 5, and a sample gas capillary 3 interface, a reagent gas capillary 9, and a vacuum gauge are arranged on the wall of the ionization chamber cavity 2. 6 ports and 7 suction ports of the vacuum pump.
试剂气毛细管9和样品气毛细管3分别通过电离室腔体2壁上的试剂气毛细管9接口和样品气毛细管3接口进入电离室内部；试剂气毛细管9和样品气毛细管3的气体出口位于传输电极与差分孔电极之间或传输电极与传输电极之间；试剂气毛细管9和样品气毛细管3的气体出口端垂直于紫外光束。The reagent gas capillary 9 and the sample gas capillary 3 respectively enter the inside of the ionization chamber through the reagent gas capillary 9 interface and the sample gas capillary 3 interface on the wall of the ionization chamber cavity; the gas outlets of the reagent gas capillary 9 and the sample gas capillary 3 are located at the transmission electrode Between the differential hole electrode or between the transmission electrode and the transmission electrode; the gas outlet ends of the reagent gas capillary 9 and the sample gas capillary 3 are perpendicular to the ultraviolet light beam.
电离室气压通过连接真空泵7的调节阀门8进行控制，气压维持在1Pa到500Pa之间；气压值通过真空规6来获得。The air pressure in the ionization chamber is controlled by the regulating valve 8 connected to the vacuum pump 7 , and the air pressure is maintained between 1 Pa and 500 Pa; the air pressure value is obtained by the vacuum gauge 6 .
传输电极4置于电离室腔体2内部，传输电极4的轴向开有通孔；当为一个以上的传输电极4时，一个以上的传输电极4之间相互平行、间隔设置，通孔同轴；于传输电极4的通孔上方处的电离室腔体2壁上设有紫外光入口，紫外光入口与通孔同轴；于传输电极4的下方处设有差分孔电极5，差分孔电极5的孔与通孔同轴，紫外光源1发出的紫外光从紫外光入口照射在差分孔电极5表面，通过光电效应产生光电子；传输电极4上施加有直流传输电压；当为一个以上的传输电极4时，一个以上的传输电极4的各电极上依次施加有直流传输电压，各电极上依次施加的电压沿光入射方向依次降低；在传输电极4的其中一个通过电容耦合的方式叠加有一射频电压；当为一个以上的传输电极4时，除叠加有射频电压的传输电极4之外的其他每片电极上都通过电容接地；差分孔电极5上施加有直流电压，且通过电容接地，同时也通过电阻连接到地；The transmission electrode 4 is placed inside the ionization chamber cavity 2, and the axial direction of the transmission electrode 4 is provided with through holes; when there are more than one transmission electrodes 4, the more than one transmission electrodes 4 are arranged parallel to each other and at intervals, and the through holes are the same as axis; the ionization chamber cavity 2 wall above the through hole of the transmission electrode 4 is provided with an ultraviolet light entrance, and the ultraviolet light entrance is coaxial with the through hole; a differential hole electrode 5 is provided at the bottom of the transmission electrode 4, and a differential hole The hole of the electrode 5 is coaxial with the through hole, and the ultraviolet light emitted by the ultraviolet light source 1 is irradiated on the surface of the differential hole electrode 5 from the ultraviolet light entrance, and photoelectrons are generated through the photoelectric effect; a DC transmission voltage is applied to the transmission electrode 4; when more than one When transmitting the electrodes 4, DC transmission voltages are sequentially applied to the electrodes of more than one transmission electrodes 4, and the voltages applied to the electrodes sequentially decrease along the light incident direction; one of the transmission electrodes 4 is superimposed by capacitive coupling. RF voltage; when it is more than one transmission electrode 4, every other electrode except the transmission electrode 4 superimposed with radio frequency voltage is grounded through a capacitor; DC voltage is applied to the differential hole electrode 5, and grounded through a capacitor, It is also connected to ground through a resistor;
电离室产生的离子通过小孔进入质量分析器；所述的质量分析器为飞行时间质量分析器、四级杆质量分析器或离子阱质量分析器。The ions generated by the ionization chamber enter the mass analyzer through the small hole; the mass analyzer is a time-of-flight mass analyzer, a quadrupole mass analyzer or an ion trap mass analyzer.
电离源可以实现两种不同的工作模式的切换。当关闭射频电压时，为单光子电离模式；当开启射频电压时，光电效应产生的光电子从射频场中获得能量，光电子碰撞电离试剂气体产生试剂离子得到软电离的化学电离源，此时单光子电离和化学电离同时作用；The ionization source can switch between two different working modes. When the radio frequency voltage is turned off, it is the single photon ionization mode; when the radio frequency voltage is turned on, the photoelectrons generated by the photoelectric effect obtain energy from the radio frequency field, and the photoelectrons collide with the ionized reagent gas to generate reagent ions to obtain soft ionization. Simultaneous ionization and chemical ionization;
本发明的电离源工作于射频电场增强化学电离模式时，样品气体通过样品毛细管3通入电离室，试剂气体通过试剂毛细管9通入电离室。紫外光在差分孔电极5上产生光电效应释放光电子。光电子在射频电场的作用下在电离室作振荡运动，不断与试剂气体分子碰撞，产生大量试剂离子。当试剂气体分子电离能高于样品分子电离能时，样品分子发生电荷转移的化学电离。获得的样品离子在传输电极4的作用下，通过差分孔电极5进入质量分析器。When the ionization source of the present invention works in the radio frequency electric field enhanced chemical ionization mode, the sample gas is passed into the ionization chamber through the sample capillary 3 , and the reagent gas is passed into the ionization chamber through the reagent capillary 9 . The ultraviolet light generates a photoelectric effect on the differential aperture electrode 5 to release photoelectrons. Under the action of the radio frequency electric field, the photoelectrons oscillate in the ionization chamber, constantly collide with the reagent gas molecules, and generate a large number of reagent ions. When the ionization energy of the reagent gas molecules is higher than that of the sample molecules, the chemical ionization of the charge transfer occurs in the sample molecules. The obtained sample ions enter the mass analyzer through the differential aperture electrode 5 under the action of the transmission electrode 4 .
电离源工作于单光子电离模式时，样品气体通过样品毛细管3通入电离室。分子吸收紫外光子，当光子能量大于分子电离能时可发生光电离。When the ionization source works in the single-photon ionization mode, the sample gas passes through the sample capillary 3 into the ionization chamber. Molecules absorb ultraviolet photons, and photoionization can occur when the energy of the photons is greater than the ionization energy of the molecules.
实施例1Example 1
针对本发明所述的电离源射频电场增强作用的考查，使用发射光子能量为10.6eV的商品化Kr灯作为真空紫外光源，将该电离源与飞行时间质量分析器联用。选用内径为Φ150μm、长度为30cm的石英毛细管分别作为样品气体进样管。样品气为10ppm的苯（IE=9.24eV）、甲苯（IE=8.83eV）、对二甲苯（IE=8.44eV），样品气以O2作为平衡气体，本实验直接以平衡气O2（IE=12.07eV）作为试剂气体。调节电离源腔体内的气压至50Pa，气体进样量为20mL/min。传输电极在此采用两片电极组成。第一片施加直流电压12V，第二片施加直流电源11V，并在第二片传输电极上叠加一个峰峰值为216V，频率7MHz的射频电压。差分孔电极上施加直流电压5V。三个电极的间距为6mm。第一片传输电极和差分孔电极接地滤波电容大小都为100μF，第二片传输电极上射频耦合电容大小为100nF。情形一：仅开紫外灯，进行单光子电离样品分子；情形二：仅施加射频电场；情形三：打开紫外灯，施加射频电场，化学电离。得到的质谱信号如图2所示。由图可见，在紫外灯提供光电子的条件下，引入射频电场后显著提高了信号强度。For the investigation of the radio frequency electric field enhancement effect of the ionization source described in the present invention, a commercialized Kr lamp with an emission photon energy of 10.6eV was used as a vacuum ultraviolet light source, and the ionization source was used in conjunction with a time-of-flight mass analyzer. Quartz capillary tubes with an inner diameter of Φ150 μm and a length of 30 cm were selected as sample gas injection tubes. The sample gas is 10ppm benzene (IE=9.24eV), toluene (IE=8.83eV), p-xylene (IE=8.44eV), and the sample gas uses O 2 as the balance gas. In this experiment, the balance gas O 2 (IE =12.07eV) as a reagent gas. Adjust the air pressure in the chamber of the ionization source to 50Pa, and the gas injection volume is 20mL/min. The transmission electrode is composed of two electrodes. A DC voltage of 12V is applied to the first sheet, a DC power supply of 11V is applied to the second sheet, and a radio frequency voltage with a peak-to-peak value of 216V and a frequency of 7MHz is superimposed on the transmission electrode of the second sheet. A DC voltage of 5 V was applied to the differential hole electrodes. The distance between the three electrodes is 6 mm. The size of the first transmission electrode and the grounding filter capacitor of the differential hole electrode is 100 μF, and the size of the RF coupling capacitor on the second transmission electrode is 100 nF. Situation 1: Only turn on the UV lamp to perform single-photon ionization of sample molecules; Situation 2: Only apply a radio frequency electric field; Situation 3: Turn on the UV lamp and apply a radio frequency electric field to chemically ionize. The obtained mass spectrum signal is shown in Fig. 2 . It can be seen from the figure that under the condition that the ultraviolet lamp provides photoelectrons, the signal intensity is significantly improved after the introduction of the radio frequency electric field.
实施例2Example 2
对于本发明的电离源拓宽分析物范围的性能考察，样品气为10ppm氯仿（IE=11.37eV)，选取电离能高于光子能量10.6eV的O2（12.07eV）作为平衡气体和试剂气体。选用内径为Φ150μm、长度为30cm的石英毛细管作为样品气体进样管。调节电离源腔体内的气压至50Pa，气体进样量为20mL/min。第一片施加直流电压12V，第二片施加直流电源11V，并在第二片传输电极上叠加一个峰峰值为216V，频率7MHz的射频电压。差分孔电极上施加直流电压5V。三个电极的间距为6mm。第一片传输电极和差分孔电极接地滤波电容大小都为100μF，第二片传输电极上射频耦合电容大小为100nF。总累计次数50万次，得到图3所示的质谱信号。其中，质荷比为83，85，87的峰为CHCl2 +，谱图几乎无碎片离子，实现了高电离能样品氯仿的软电离。For the performance investigation of the ionization source of the present invention to broaden the range of analytes, the sample gas is 10ppm chloroform (IE=11.37eV), and O 2 (12.07eV) whose ionization energy is higher than the photon energy of 10.6eV is selected as the balance gas and reagent gas. A quartz capillary with an inner diameter of Φ150 μm and a length of 30 cm was selected as the sample gas injection tube. Adjust the air pressure in the chamber of the ionization source to 50Pa, and the gas injection volume is 20mL/min. A DC voltage of 12V is applied to the first sheet, a DC power supply of 11V is applied to the second sheet, and a radio frequency voltage with a peak-to-peak value of 216V and a frequency of 7MHz is superimposed on the transmission electrode of the second sheet. A DC voltage of 5 V was applied to the differential hole electrodes. The distance between the three electrodes is 6 mm. The size of the first transmission electrode and the grounding filter capacitor of the differential hole electrode is 100 μF, and the size of the RF coupling capacitor on the second transmission electrode is 100 nF. The total cumulative number of times is 500,000, and the mass spectrum signal shown in Fig. 3 is obtained. Among them, the peaks with mass-to-charge ratios of 83, 85, and 87 are CHCl 2 + , and there are almost no fragment ions in the spectrum, which realizes the soft ionization of chloroform, a sample with high ionization energy.
实施例3Example 3
在实施例2同样的工作条件下，改变不同样品，测试射频电场软电离源的增强倍数。如图4所示，（a）为电离能小于光子能量10.6eV的样品，倍数为射频场化学电离与单光子电离强度的比较；（b）为电离能大于光子能量10.6eV的样品，倍数为射频场化学电离与直流场产生化学电离强度的比较。直流场产生化学电离的工作条件是：传输电压第一片施加直流电压150V，第二片施加直流电压13V，差分孔电极施加直流电压5V。由图可见，本电离源在包含单光子电离模式的基础上，通过引入射频电场在中等气压条件下，控制光电子振荡，有效电离试剂气体，产生的试剂离子进一步与样品分子发生化学电离。本电离源不仅提高了检测灵敏度，而且可以电离电离能高于光子能量的样品，拓宽了可分析检测分子的范围。而且仅通过控制射频电压的开启和关闭，可以实现两种软电离方式的快速切换。Under the same working conditions as in Example 2, different samples were changed to test the enhancement factor of the radio frequency electric field soft ionization source. As shown in Figure 4, (a) is the sample whose ionization energy is less than 10.6eV of photon energy, and the multiple is the comparison between chemical ionization and single photon ionization intensity in radio frequency field; (b) is the sample with ionization energy greater than 10.6eV of photon energy, and the multiple is Comparison of chemical ionization intensity produced by radio frequency field and direct current field. The working conditions for chemical ionization in the DC field are as follows: DC voltage 150V is applied to the first plate of the transmission voltage, DC voltage 13V is applied to the second plate, and DC voltage 5V is applied to the differential hole electrodes. It can be seen from the figure that on the basis of including single-photon ionization mode, the ionization source controls the photoelectron oscillation by introducing a radio frequency electric field under medium pressure conditions, effectively ionizes the reagent gas, and the generated reagent ions further chemically ionize with the sample molecules. The ionization source not only improves the detection sensitivity, but also can ionize samples whose ionization energy is higher than the photon energy, thereby broadening the range of molecules that can be analyzed and detected. Moreover, only by controlling the on and off of the radio frequency voltage, the fast switching between the two soft ionization modes can be realized.
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