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CN102903598B - Method for improving traditional ion transference tube sensitivity - Google Patents

Method for improving traditional ion transference tube sensitivity Download PDF

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CN102903598B
CN102903598B CN201210409048.9A CN201210409048A CN102903598B CN 102903598 B CN102903598 B CN 102903598B CN 201210409048 A CN201210409048 A CN 201210409048A CN 102903598 B CN102903598 B CN 102903598B
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ion gate
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CN102903598A (en
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袁曦
陈勇
疏天民
金洁
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Third Research Institute of the Ministry of Public Security
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Abstract

本发明公开了一种用于提高传统离子迁移管灵敏度的方法,首先使得离子迁移管在离子门关闭时电离区的电压V1、第一离子门栅的电压V2以及第二离子门栅的电压V3满足如下公式:V1=V3>V2>>0,在开门瞬间,对电离区的电压V1施加一个同原先电压极性相同、幅度为ΔV1的脉冲,对第一离子门栅的电压V2也施加一个同原先电压极性相同、幅度为ΔV的脉冲,使得:(V1+ΔV1)>>(V2+ΔV)>V3>>0,由此在关门时,在电离区积累的离子,在电场力的作用下,瞬间进入迁移区进行迁移。利用该方法使得传统结构的离子迁移管在离子利用率上能提高5倍以上,对常见样品的极限探测灵敏度能提升5至10倍,大幅提高仪器的灵敏度性能指标。

The invention discloses a method for improving the sensitivity of a traditional ion transfer tube. Firstly, the voltage V1 of the ionization region, the voltage V2 of the first ion gate and the voltage V3 of the second ion gate of the ion transfer tube when the ion gate is closed Satisfy the following formula: V1=V3>V2>>0, at the moment of opening the gate, a pulse with the same polarity as the original voltage and an amplitude of ΔV1 is applied to the voltage V1 in the ionization region, and a pulse is also applied to the voltage V2 of the first ion gate The pulse with the same polarity as the original voltage and the amplitude of ΔV makes: (V1+ΔV1)>>(V2+ΔV)>V3>>0, so when the door is closed, the ions accumulated in the ionization region, under the force of the electric field Under the action, it instantly enters the migration area for migration. Using this method, the ion utilization rate of the ion transfer tube with the traditional structure can be increased by more than 5 times, and the limit detection sensitivity of common samples can be increased by 5 to 10 times, which greatly improves the sensitivity performance index of the instrument.

Description

一种用于提高传统离子迁移管灵敏度的方法A Method for Improving the Sensitivity of Conventional Ion Transfer Tubes

技术领域technical field

本发明涉及一种离子迁移管,具体涉及一种提高离子迁移管灵敏度的方法The invention relates to an ion transfer tube, in particular to a method for improving the sensitivity of the ion transfer tube

背景技术Background technique

离子迁移谱(IMS)是20世纪60年代末出现的,经过几十年的发展已成为基于分子水平上较成熟的现场痕量检测技术。离子迁移谱仪中的核心部件为离子迁移管。在离子迁移管中,样品分子在离化源的作用下,可以产生相应产物离子。将这些产物离子放置在大气环境恒定电场中,它们因受电场的加速和中性大气分子的碰撞减速,在宏观上就表现为获得了一个恒定的平均速度。由于不同的产物离子其荷质比、空间几何构型和碰撞截面不同,因而获得的平均速度也不同,所以在经过一段电场以后他们就被分离,先后到达探测器从而完成被检测的过程。Ion mobility spectrometry (IMS) appeared in the late 1960s, and after decades of development, it has become a relatively mature on-site trace detection technology based on the molecular level. The core component of the ion mobility spectrometer is the ion transfer tube. In the ion transfer tube, the sample molecules can generate corresponding product ions under the action of the ionization source. When these product ions are placed in a constant electric field in the atmospheric environment, they are accelerated by the electric field and decelerated by the collision of neutral atmospheric molecules, and they appear to obtain a constant average velocity macroscopically. Since different product ions have different charge-to-mass ratios, spatial geometric configurations, and collision cross-sections, the average velocities obtained are also different. Therefore, they are separated after passing through an electric field, and arrive at the detector successively to complete the detection process.

传统的离子迁移管结构如图1所示:其主要由电离区1、迁移区2、探测器3组成。电离区1设置于迁移区2的起始端,并且两者之间设置有离子门4;探测器3设置在迁移区2的末端。The structure of a traditional ion transfer tube is shown in Figure 1: it is mainly composed of an ionization region 1, a migration region 2, and a detector 3. The ionization zone 1 is set at the beginning of the migration zone 2 , and an ion gate 4 is set between them; the detector 3 is set at the end of the migration zone 2 .

如图1和图2所示,离子迁移管中的离子门4一般由两个靠得很近的金属门栅41组成,这两个金属门栅之间相互绝缘。As shown in FIG. 1 and FIG. 2 , the ion gate 4 in the ion transfer tube generally consists of two metal gates 41 that are close to each other, and the two metal gates are insulated from each other.

传统的离子迁移管的工作方式描述如下:待测样品的微粒进入电离区,在离化源(通常为63Ni)的作用下通过质子夺取反应、电子附着反应、电子交换反应等生成相对稳定的产物离子。产物离子通过离子门的控制在同一时间内成批进入迁移区进行迁移。在经过一段电场以后他们就被分离,先后到达收集器形成微弱的脉冲电信号,从而完成被检测的过程。The working mode of the traditional ion transfer tube is described as follows: the particles of the sample to be tested enter the ionization region, and under the action of the ionization source (usually 63 Ni), a relatively stable product ions. The product ions are controlled by the ion gate and enter the migration area in batches for migration at the same time. After a period of electric field, they are separated and arrive at the collector successively to form weak pulse electric signals, thus completing the process of being detected.

在图1中,Vi为电离区电压,Vg为第一个离子门栅的电压,Vd为第二个离子门栅的电压,同时第二个离子门栅电压又是迁移区的起始端电压(即迁移区的最高电压),同时迁移区上的各电极电压由电阻分压获得,管体外壳和收集器为零电位。在离子门关闭的情况下,各电极电压分别为|Vi|=V1、|Vg|=V2、|Vd|=V3,其高低关系如下:In Figure 1, Vi is the ionization region voltage, Vg is the voltage of the first ion gate, Vd is the voltage of the second ion gate, and the second ion gate voltage is the initial terminal voltage of the migration region ( That is, the highest voltage in the migration area), and at the same time, the voltage of each electrode on the migration area is obtained by dividing the voltage of the resistor, and the shell of the tube body and the collector are at zero potential. When the ion gate is closed, the electrode voltages are respectively |Vi|=V1, |Vg|=V2, |Vd|=V3, and the relationship between them is as follows:

V1>>V3>V2>>0V1>>V3>V2>>0

在开门的瞬间,Vg将被施加一个同原先电压极性相同的脉冲,幅度为ΔV,这时又有如下关系:At the moment of opening the door, Vg will be applied with a pulse with the same polarity as the original voltage, and the amplitude is ΔV. At this time, the relationship is as follows:

V1>>(V2+ΔV)>V3>>0V1>>(V2+ΔV)>V3>>0

显然在离子门关闭时,离子门两个门栅间有一个与迁移区电场方向相反的电场,离子无法通过。在开门瞬间,反向电场被纠正,离子被允许通过。Obviously, when the ion gate is closed, there is an electric field opposite to the direction of the electric field in the migration region between the two grids of the ion gate, and ions cannot pass through. At the moment of door opening, the reverse electric field is corrected and ions are allowed to pass through.

以上介绍的是传统的离子迁移管的工作方式,其弊端在于Vi的电位远高于Vg和Vd,因此电离区产生的离子也是有明显的运动方向的,其方向是从电离区朝离子门栅方向运动,在离子门关闭时,由于离子无法越过门栅间的反向电场,因此大部分离子会撞到第一级门栅的金属丝上放电,损失成为中性离子,造成了离子利用效率的低下,从而影响仪器灵敏度指标。The above is the working method of the traditional ion transfer tube. The disadvantage is that the potential of Vi is much higher than that of Vg and Vd. Therefore, the ions generated in the ionization region also have a clear direction of movement, and the direction is from the ionization region to the ion gate. Direction movement, when the ion gate is closed, because the ions cannot cross the reverse electric field between the gate grids, most of the ions will hit the metal wire of the first gate grid and discharge, and the loss will become neutral ions, resulting in ion utilization efficiency The low, thus affecting the sensitivity index of the instrument.

发明内容Contents of the invention

本发明针对传统离子迁移管的工作方式造成离子利用率低下,从而影响仪器灵敏度的问题,而提供一种用于提高传统离子迁移管灵敏度的方法。本方法在不改变传统离子迁移管结构设计的前提下,有效解决传统离子迁移管工作方式造成的离子利用率低下的问题端,减少离子门关闭时电离区离子的损失,从而提高仪器灵敏度。The invention aims at the problem that the ion utilization rate is low due to the working mode of the traditional ion transfer tube, thereby affecting the sensitivity of the instrument, and provides a method for improving the sensitivity of the traditional ion transfer tube. This method effectively solves the problem of low ion utilization caused by the traditional ion transfer tube working mode without changing the structural design of the traditional ion transfer tube, and reduces the loss of ions in the ionization region when the ion gate is closed, thereby improving the sensitivity of the instrument.

为了达到上述目的,本发明采用如下的技术方案:In order to achieve the above object, the present invention adopts following technical scheme:

一种用于提高传统离子迁移管灵敏度的方法,该方法中A method for increasing the sensitivity of conventional ion transfer tubes, in which

首先使得离子迁移管在离子门关闭时电离区的电压V1、第一离子门栅的电压V2以及第二离子门栅的电压V3满足如下公式:First, the voltage V1 of the ionization region, the voltage V2 of the first ion gate, and the voltage V3 of the second ion gate of the ion transfer tube satisfy the following formula when the ion gate is closed:

V1=V3>V2>>0,V1=V3>V2>>0,

其中,第二离子门栅的电压V3与第一离子门栅的电压V2之间的反向电场幅度为7V~30V,并且第二离子门栅与电离区保持相等电位,使得电离区产生的离子能够充分达到饱和;Wherein, the magnitude of the reverse electric field between the voltage V3 of the second ion gate and the voltage V2 of the first ion gate is 7V-30V, and the second ion gate and the ionization region maintain the same potential, so that the ions generated in the ionization region able to reach full saturation;

在开门瞬间,对电离区的电压V1施加一个同原先电压极性相同、幅度为ΔV1的脉冲,对第一离子门栅的电压V2也施加一个同原先电压极性相同、幅度为ΔV的脉冲,使得:At the moment of opening the gate, a pulse with the same polarity as the original voltage and an amplitude of ΔV1 is applied to the voltage V1 in the ionization region, and a pulse with the same polarity as the original voltage and an amplitude of ΔV is applied to the voltage V2 of the first ion gate. makes:

(V1+ΔV1)>>(V2+ΔV)>V3>>0,(V1+ΔV1)>>(V2+ΔV)>V3>>0,

由此在关门时,在电离区积累的离子,在电场力的作用下,瞬间进入迁移区进行迁移。Therefore, when the door is closed, the ions accumulated in the ionization area will instantly enter the migration area for migration under the action of the electric field force.

采用本发明后,传统结构的离子迁移管在离子利用率上能提高5倍以上,对常见样品的极限探测灵敏度能提升5至10倍,大幅提高仪器的灵敏度性能指标。After the invention is adopted, the ion utilization rate of the ion transfer tube with the traditional structure can be increased by more than 5 times, and the limit detection sensitivity of common samples can be increased by 5 to 10 times, and the sensitivity performance index of the instrument can be greatly improved.

附图说明Description of drawings

以下结合附图和具体实施方式来进一步说明本发明。The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

图1为传统离子迁移管的结构示意图;Fig. 1 is the structural representation of traditional ion transfer tube;

图2为传统离子迁移管中电子门栅的结构示意图;Fig. 2 is the schematic diagram of the structure of the electronic gate in the traditional ion transfer tube;

图3为本发明基于实施的离子迁移管的连接原理图;Fig. 3 is the connection schematic diagram of the ion transfer tube based on the implementation of the present invention;

图4为离子门关闭时离子迁移管中各电极电压分布示意图;Fig. 4 is a schematic diagram of the voltage distribution of each electrode in the ion transfer tube when the ion gate is closed;

图5为离子门打开瞬间离子迁移管中各电极电压分布示意图。Fig. 5 is a schematic diagram of the voltage distribution of each electrode in the ion transfer tube when the ion gate is opened.

具体实施方式Detailed ways

为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解,下面结合具体图示,进一步阐述本发明。In order to make the technical means, creative features, goals and effects achieved by the present invention easy to understand, the present invention will be further described below in conjunction with specific illustrations.

参见图3,其所示为本发明基于实施的离子迁移管的连接原理图,由图可知,本发明对传统离子迁移管结构没有进行改变,其同样包括电离区100、迁移区200、探测器300,其中电离区100设置于迁移区200的起始端,在两者之间设置有离子门400,探测器300设置在迁移区200的末端;离子迁移管中的离子门400由第一金属离子门栅401和第二金属离子门栅402组成,这两个离子门栅靠得很近,并且两者之间相互绝缘,其具体结构如图2所示。Referring to Fig. 3, it shows the connection schematic diagram of the ion transfer tube based on the implementation of the present invention, as can be seen from the figure, the present invention does not change the structure of the traditional ion transfer tube, which also includes the ionization region 100, the transfer region 200, the detector 300, wherein the ionization region 100 is arranged at the initial end of the migration region 200, an ion gate 400 is arranged between the two, and the detector 300 is arranged at the end of the migration region 200; the ion gate 400 in the ion transfer tube is formed by the first metal ion The gate grid 401 and the second metal ion gate grid 402 are composed, and the two ion gate grids are close to each other and are insulated from each other. The specific structure is shown in FIG. 2 .

在实施时,在迁移区200外接高压电源500,以提供迁移区恒定电场,同时迁移区内的各电极电压由相应的电阻分压获得。电离区100的电压为Vi,第一离子门栅401的电压为Vg,第二离子门栅402的电压为Vd,同时第二离子门栅402的电压又是迁移区的起始端电压,即迁移区的最高电压,管体外壳和收集器为零电位。During implementation, a high-voltage power supply 500 is externally connected to the transition area 200 to provide a constant electric field in the transition area, and at the same time, the voltages of the electrodes in the transition area are obtained by dividing voltages by corresponding resistors. The voltage of the ionization region 100 is Vi, the voltage of the first ion gate 401 is Vg, the voltage of the second ion gate 402 is Vd, and the voltage of the second ion gate 402 is the initial terminal voltage of the migration region, that is, the migration The highest voltage in the area, the tube shell and the collector are at zero potential.

在离子门关闭的情况下,各电极电压分别为|Vi|=V1、|Vg|=V2、|Vd|=V3,它们之间的电压高低关系如下:When the ion gate is closed, the electrode voltages are respectively |Vi|=V1, |Vg|=V2, |Vd|=V3, and the relationship between them is as follows:

V1=V3>V2>>0,V1=V3>V2>>0,

由上式可知,在离子门关闭时,电离区100的电压V1与迁移区最高电压抑制,即与第二离子门栅402的电压V3一致,第二离子门栅的电压V3与第一离子门栅的电压V2之间的反向电场幅度在7V~30V之间,具体可以为10V或者20V,并且与电离区的电压之间没有显著的电位差,即第二离子门栅与电离区保持相等电位,由此使得电离区产生的离子能够充分达到饱和。It can be seen from the above formula that when the ion gate is closed, the voltage V1 of the ionization region 100 is suppressed by the highest voltage in the migration region, that is, it is consistent with the voltage V3 of the second ion gate grid 402, and the voltage V3 of the second ion gate grid is the same as that of the first ion gate grid. The magnitude of the reverse electric field between the voltage V2 of the gate is between 7V and 30V, specifically 10V or 20V, and there is no significant potential difference with the voltage of the ionization region, that is, the second ion gate and the ionization region remain equal Potential, so that the ions generated in the ionization region can be fully saturated.

在开门瞬间,电离区100的电压Vi将被施加一个同原先电压极性相同(即与电离区原来所施加的电压Vi极性相同)的脉冲600,幅度为ΔV1,第一离子门栅的电压Vg也将被施加一个同原先电压极性相同(即与第一离子门栅的电压Vg极性相同)的脉冲700,幅度为ΔV,这时使得各电极电压之间的高低关系如下:At the moment of opening the gate, the voltage Vi of the ionization region 100 will be applied with a pulse 600 with the same polarity as the original voltage (that is, the same polarity as the voltage Vi originally applied to the ionization region), with an amplitude of ΔV1, and the voltage of the first ion gate grid Vg will also be applied with a pulse 700 with the same polarity as the original voltage (that is, the same polarity as the voltage Vg of the first ion gate), with an amplitude of ΔV. At this time, the relationship between the voltages of the electrodes is as follows:

(V1+ΔV1)>>(V2+ΔV)>V3>>0,(V1+ΔV1)>>(V2+ΔV)>V3>>0,

其中(V1+ΔV1)与(V2+ΔV)之间相差200V~600V,(V2+ΔV)与V3之间相差10V~30V,V3为1300V~2500V。The difference between (V1+ΔV1) and (V2+ΔV) is 200V-600V, the difference between (V2+ΔV) and V3 is 10V-30V, and V3 is 1300V-2500V.

此时,关门时在电离区积累的离子,在电场力的作用下,瞬间进入迁移区进行迁移。At this time, the ions accumulated in the ionization region when the door is closed will instantly enter the migration region for migration under the action of the electric field force.

对比上述发明的开门工作方式,传统的离子迁移管的工作方式中,在离子门关闭时V1的电位远高于V2和V3(相差100V~300V),因此电离区产生的离子也是有明显的运动方向的,其方向是从电离区朝离子门栅方向运动,此时由于离子无法越过门栅间的反向电场,因此大部分离子会撞到第一级门栅的金属丝上放电,损失成为中性离子,其损失率高达90%以上,造成了离子利用效率的低下,从而影响仪器灵敏度指标。Compared with the gate-opening working mode of the above invention, in the traditional ion transfer tube working mode, when the ion gate is closed, the potential of V1 is much higher than that of V2 and V3 (the difference is 100V ~ 300V), so the ions generated in the ionization region also have obvious movement direction, and its direction is from the ionization region to the direction of the ion gate grid. At this time, because the ions cannot cross the reverse electric field between the gate grids, most of the ions will hit the metal wire of the first-level gate grid to discharge, and the loss becomes The loss rate of neutral ions is as high as more than 90%, resulting in low ion utilization efficiency, thereby affecting the sensitivity index of the instrument.

而本发明针对此情况在不改变传统离子迁移管结构设计的前提下,通过改变在离子门关闭时V1电位,使此时电离区产生的离子不具有明显的运动方向,减少离子的损失,这种方法使离子利用率提高5倍以上,对常见样品的极限探测灵敏度能提升5至10倍,大幅提高仪器的灵敏度性能指标。However, the present invention aims at this situation without changing the structural design of the traditional ion transfer tube, by changing the V1 potential when the ion gate is closed, so that the ions generated in the ionization region do not have a clear direction of movement at this time, reducing the loss of ions. This method can increase the ion utilization rate by more than 5 times, and the limit detection sensitivity of common samples can be increased by 5 to 10 times, and the sensitivity performance index of the instrument can be greatly improved.

基于上述方案,本发明的具体实施如下:Based on above-mentioned scheme, concrete implementation of the present invention is as follows:

参见图4,在迁移区200接1500V的高压电源,以提供迁移区恒定电场,各电极电压由电阻分压获得。Referring to FIG. 4 , a high-voltage power supply of 1500V is connected to the migration region 200 to provide a constant electric field in the migration region, and the voltage of each electrode is obtained by dividing voltage by resistors.

其中,电离区100在离子门关闭时保持与迁移区最高电压一致,都为1500V,在电离区中第一离子门栅的电压为1490V,第二离子门栅的电压为1500V,探测器为0电位。由此,使得电离区产生的离子能够充分达到饱和。Wherein, the ionization region 100 remains consistent with the highest voltage in the migration region when the ion gate is closed, both being 1500V, the voltage of the first ion gate in the ionization region is 1490V, the voltage of the second ion gate is 1500V, and the detector is 0 potential. Thus, the ions generated in the ionization region can be fully saturated.

参见图5,开门时电离区将被施加一个500V左右的脉冲,第一离子门栅也将被施加一个15V左右的脉冲。此时,电离区电压为2000V,第一离子门栅的电压为1505V,第二离子门栅的电压为1500V,探测器为0电位。Referring to Fig. 5, when the gate is opened, a pulse of about 500V will be applied to the ionization region, and a pulse of about 15V will be applied to the first ion gate. At this time, the voltage of the ionization region is 2000V, the voltage of the first ion gate is 1505V, the voltage of the second ion gate is 1500V, and the detector is at 0 potential.

在该实例中开门时间控制在200至400微秒之间,之后进行关门,在关门时在电离区积累的离子,在电场力的作用下,瞬间进入迁移区进行迁移,大大提高离子的利用率,从而对常见样品的极限探测灵敏度能提升5至10倍,能大幅提高仪器的灵敏度性能指标。In this example, the door opening time is controlled between 200 and 400 microseconds, and then the door is closed. The ions accumulated in the ionization area when the door is closed, under the action of the electric field force, instantly enter the migration area for migration, greatly improving the utilization rate of ions , so that the limit detection sensitivity of common samples can be increased by 5 to 10 times, and the sensitivity performance index of the instrument can be greatly improved.

以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。The basic principles, main features and advantages of the present invention have been shown and described above. Those skilled in the industry should understand that the present invention is not limited by the above-mentioned embodiments. What are described in the above-mentioned embodiments and the description only illustrate the principle of the present invention. Without departing from the spirit and scope of the present invention, the present invention will also have Variations and improvements are possible, which fall within the scope of the claimed invention. The protection scope of the present invention is defined by the appended claims and their equivalents.

Claims (1)

1.一种用于提高传统离子迁移管灵敏度的方法,其特征在于,所述方法中1. a method for improving the sensitivity of traditional ion transfer tubes, characterized in that, in the method 首先使得离子迁移管在离子门关闭时电离区的电压V1、第一离子门栅的电压V2以及第二离子门栅的电压V3满足如下公式:First, the voltage V1 of the ionization region, the voltage V2 of the first ion gate, and the voltage V3 of the second ion gate of the ion transfer tube satisfy the following formula when the ion gate is closed: V1=V3>V2>>0,V1=V3>V2>>0, 其中,第二离子门栅的电压V3又是迁移区的起始端电压,即迁移区的最高电压,其与第一离子门栅的电压V2之间的反向电场幅度在7V~30V之间,并且第二离子门栅与电离区保持相等电位,使得电离区产生的离子能够充分达到饱和;Wherein, the voltage V3 of the second ion gate is the initial terminal voltage of the migration region, that is, the highest voltage of the migration region, and the magnitude of the reverse electric field between it and the voltage V2 of the first ion gate is between 7V and 30V, And the second ion gate and the ionization region maintain the same potential, so that the ions generated in the ionization region can be fully saturated; 在开门瞬间,对电离区的电压V1施加一个同原先电压极性相同、幅度为ΔV1的脉冲,对第一离子门栅的电压V2也施加一个同原先电压极性相同、幅度为ΔV的脉冲,使得:At the moment of opening the gate, a pulse with the same polarity as the original voltage and an amplitude of ΔV1 is applied to the voltage V1 in the ionization region, and a pulse with the same polarity as the original voltage and an amplitude of ΔV is applied to the voltage V2 of the first ion gate. makes: (V1+ΔV1)>>(V2+ΔV)>V3>>0,(V1+ΔV1)>>(V2+ΔV)>V3>>0, 由此在关门时,在电离区积累的离子,在电场力的作用下,瞬间进入迁移区进行迁移。Therefore, when the door is closed, the ions accumulated in the ionization area will instantly enter the migration area for migration under the action of the electric field force.
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