Ion source system, mass spectrometry system, and deterioration determination method

Abstract

To improve the accuracy of deterioration determination.SOLUTION: In the ion source system 10 including the ion source 100 and the control device 400, the ion source 100 includes the capillary 121 that sprays the sample solution Q, the counter electrode 131 that generates an electric field for ion generation between the capillary 121 and the counter electrode, and the correction electrode 110 disposed in the space in which the capillary 121 and the counter electrode 131 are installed, and the control device 400 determines the presence or absence of deterioration in the capillary 121, the counter electrode 131, and the correction electrode 110 based on a change in the first graph and a change in the second graph.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] The present invention relates to an ion source system, a mass spectrometry system, and a deterioration determination method. [Background technology]

[0002] In the electrospray ionization (ESI) method, a common ionization method used in mass spectrometry, a sample solution is introduced into the upstream end of a capillary, and then ions or droplets are sprayed from the downstream end by an electric field or the like.

[0003] Patent Document 1 discloses an analyzer, a dangerous goods detection device, and a selection screen interface that "includes an ionization unit 10 that ionizes a sample by utilizing the discharge between electrodes 12a, 12b, a detection unit 13 that detects and analyzes the ionized sample, and a control unit 14 that monitors the discharge state when starting a discharge from a stopped state by monitoring the current flowing through electrode 12a or 12b or the voltage applied to electrode 12a or 12b, or the mass spectrum obtained by detection unit 13 upon the start of the discharge, and adjusts the discharge voltage required to generate a discharge by electrodes 12a, 12b based on the monitored discharge state" (see abstract). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2023-88420 Summary of the Invention [Problem to be solved by the invention]

[0005] In an ESI ion source, it is also possible to detect degradation of the capillary by measuring the current flowing between the capillary and the introduction electrode (or the counter electrode). Possible degradation of the capillary can be due to damage to the downstream end 103, contamination by deposits, or a coating due to discharge. However, the introduction electrode (or the counter electrode), which is the other electrode used to generate the ionization electric field, can also be degraded by damage, contamination by deposits, or a coating due to discharge. As with the technology described in Patent Document 1, it is difficult to determine which electrode has deteriorated based solely on the fluctuation in the current measurement results due to changes in the electric field between the two electrodes.

[0006] The present invention has been made in view of the above background, and an object of the present invention is to improve the accuracy of deterioration determination. [Means for solving the problem]

[0007] In order to solve the above-mentioned problems, the present invention provides an ion source system including an ion source and a control unit, wherein the ion source includes a capillary that sprays a sample solution, an electrode that generates an electric field for generating ions between the capillary and the electrode, and a correction electrode that is placed in a space in which the capillary and the electrode are installed, and the control unit determines whether or not the capillary, the electrode, and the correction electrode have deteriorated based on at least one of a change in the first graph and a change in the third graph and a change in the second graph, with respect to a first graph, a second graph, and a third graph that show the relationship between voltage and current, and performs predetermined control. The first graph is a graph showing the relationship between the voltage applied to at least one of the capillary and the electrode and a first current which is a current flowing due to discharge between the capillary and the electrode, the second graph is a graph showing the relationship between the voltage applied to at least one of the capillary and the correction electrode and a second current which is a current flowing due to discharge between the capillary and the correction electrode, and the third graph is a graph showing the relationship between the voltage applied to at least one of the electrode and the correction electrode and a third current which is a current flowing due to discharge between the electrode and the correction electrode. Other solutions will be described as appropriate in the embodiments. [Effects of the Invention]

[0008] According to the present invention, the accuracy of deterioration determination can be improved. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a diagram showing the configuration of a mass spectrometry system. [Figure 2] FIG. 1 is a diagram showing a configuration of an ion source system according to a first embodiment. [Figure 3] FIG. 2 is a diagram illustrating a hardware configuration of a control device. [Figure 4] FIG. 4 is a diagram showing experimental conditions in the first embodiment. [Figure 5A]FIG. 10 is a diagram (part 1) showing experimental results in the first embodiment. [Figure 5B] FIG. 10 is a diagram (part 2) showing experimental results in the first embodiment. [Figure 6] 3 is a flowchart showing the procedure of a degradation determination method according to the first embodiment. [Figure 7] FIG. 1 is a diagram (part 1) showing the configuration of an ion source system according to a second embodiment. [Figure 8] FIG. 10 is a diagram (part 2) showing the configuration of the ion source system according to the second embodiment. [Figure 9] FIG. 10 is a diagram showing the configuration of an ion source system according to a third embodiment. [Figure 10] FIG. 1 is a diagram illustrating an example of the configuration of a liquid chromatography device. [Figure 11] FIG. 1 is a diagram showing an example of a chromatogram (part 1) output by a liquid chromatography device. [Figure 12] FIG. 10 is a diagram showing the configuration of an ion source system according to a fourth embodiment. [Figure 13] FIG. 13 is a diagram showing a measurement condition table used in the fifth embodiment. [Figure 14] FIG. 10 is a diagram showing the configuration of an ion source system according to a sixth embodiment. [Figure 15] FIG. 10 is a diagram showing an example of a chromatogram (part 2) output by the liquid chromatography device. [Figure 16] FIG. 13 is a diagram showing the configuration of an ion source system according to a seventh embodiment. [Figure 17] FIG. 20 is a diagram showing a deterioration determination table in the seventh embodiment. [Figure 18] FIG. 13 is a diagram showing the configuration of an ion source in an eighth embodiment. [Figure 19] FIG. 13 is a schematic diagram of an ion source system according to an eighth embodiment. [Figure 20A] FIG. 13 is a diagram (part 1) showing experimental results in the eighth embodiment. [Figure 20B] FIG. 20 is a diagram (part 2) showing experimental results in the eighth embodiment. [Figure 20C]FIG. 20 is a diagram (part 3) showing experimental results in the eighth embodiment. [Figure 21] FIG. 20 is a diagram showing a deterioration determination table in the eighth embodiment. [Figure 22] FIG. 13 is a diagram showing the configuration of an ion source system in a ninth embodiment. [Figure 23] FIG. 19 is a diagram illustrating an ion source system according to a tenth embodiment. [Figure 24] 20 is a flowchart showing the procedure of a degradation determination method according to an eleventh embodiment. [Figure 25] FIG. 1 is a diagram showing the configuration of a typical ion source system. [Figure 26] FIG. 1 illustrates another configuration of a typical ion source system. DETAILED DESCRIPTION OF THE INVENTION

[0010] Next, a mode for carrying out the present invention (referred to as an "embodiment") will be described in detail with reference to the drawings as appropriate. In this embodiment, the ion source 100 is an electrospray ion source.

[0011] [First embodiment] (with correction electrode 110) First, a first embodiment of the present invention will be described with reference to FIGS.

[0012] In the first embodiment, a mass spectrometer 1 having a configuration including a correction electrode 110 and determining whether or not the capillary 121, the counter electrode 131, and the correction electrode 110 have deteriorated based on the current value between the capillary 121, the counter electrode 131, and the correction electrode 110, which will be described later, will be described.

[0013] (Mass Spectrometer System Z) FIG. 1 is a diagram showing the configuration of a mass spectrometry system Z.

[0014] The mass spectrometry system Z includes a mass spectrometer 1, a power supply 300 that supplies power to the mass spectrometer 1, and a control device 400 that controls the power supply 300 and receives signals of substances detected by the mass spectrometer 1.

[0015] The mass spectrometer 1 mainly comprises a housing H that houses an ion source 100 and a mass analysis unit 200. The ion source 100 mainly comprises a spray probe 120, an ion source chamber 160, and the like.

[0016] Specifically, the ion source 100 includes a spray probe 120, an ion source chamber 160, a counter electrode 131, an introduction electrode 132, a correction electrode 110, and the like.

[0017] The ion source 100 generates ions N (see FIG. 2) when a sample solution Q is introduced. An introduction electrode 132 is provided with a hole 134 for introducing the ions N into the mass analysis section 200. A counter electrode 131 is disposed upstream of the introduction electrode 132. The capillary 121 side is referred to as the upstream side, and the mass analysis section 200 side is referred to as the downstream side. The generated ions N are introduced into the mass analysis section 200 through a hole 133 provided in the counter electrode 131 and a hole 134 provided in the introduction electrode 132. The ions N are then analyzed in the mass analysis section 200. Various voltages are applied to the mass analysis section 200 by a power supply 300. The timing and voltage values ​​of the voltages applied by the power supply 300 are controlled by a control device 400.

[0018] The spray probe 120 has a capillary 121 .

[0019] In the spray probe 120, the sample solution Q is introduced into the capillary 121 through a pipe (not shown). The capillary 121 then sprays the sample solution Q from its downstream end 121a using an electric field or the like. The electric field is generated when a voltage is applied to the capillary 121 and a counter electrode 131 by a power supply 300. The counter electrode 131 is an electrode that generates an electric field between itself and the capillary 121 for generating ions.

[0020] The value of the voltage applied to the capillary 121 is generally a maximum of several kV (absolute value). When positive ions are generated, a voltage of several +kV is applied to the capillary 121. When negative ions are generated, a voltage of several -kV is applied to the capillary 121. In this embodiment, an example in which positive ions are generated will be described. When negative ions are generated, the polarity of the voltage can be reversed in the following description. The flow rate of the sample solution Q depends on the inner diameter of the capillary 121, but is generally set in the range of the order of nL / min to μL / min. Furthermore, although it depends on conditions such as the flow rate of the sample solution Q, both the inner and outer diameters of the capillary 121 are generally set to approximately 1 mm or less. The sample solution Q may be supplied by continuous liquid delivery (infusion) using a syringe pump (not shown) or by a liquid chromatography device 2 (see FIG. 10).

[0021] The sample solution Q is electrostatically sprayed into minute charged droplets, and as these droplets move, the solvent that makes up the charged droplets evaporates. This evaporation generates ions N from the charged droplets.

[0022] It is desirable to keep the space between the ion source chamber 160 and the mass analysis unit 200 sealed (or nearly sealed). This is to prevent droplets that are not introduced into the mass analysis unit 200 and their vaporized components from leaking out of the ion source 100. Furthermore, an exhaust port 101 may be provided to exhaust excess components (reference symbol R1) remaining inside the ion source chamber 160.

[0023] The generated ions N (see FIG. 2) are attracted to the potential of the counter electrode 131 and introduced into the mass analysis section 200 through the hole 133.

[0024] In the configuration of FIG. 1, as described above, the counter electrode 131 is disposed upstream of the introduction electrode 132. Gas 901 flows between the introduction electrode 132 and the counter electrode 131, and the gas 901 is sprayed from the holes 133 formed in the counter electrode 131. This prevents noise components, such as droplets of excess sample solution Q sprayed by the ion source 100, from being introduced into the mass spectrometry unit 200 through the holes 134 formed in the introduction electrode 132. The flow rate of the gas 901 flowing between the introduction electrode 132 and the counter electrode 131 is approximately 0.5 to 50 L / min. An inert gas such as nitrogen or argon is generally used as the gas 901. The diameter of the holes 133 formed in the counter electrode 131 is generally several mm or less, and the voltage applied to the counter electrode 131 is generally several kV (absolute value) at most.

[0025] As shown in FIG. 1, the interior of the housing H is divided into an ion source chamber 160 and multiple vacuum chambers 210, 220, and 230. The vacuum chambers 210, 220, and 230 are connected to each other via small-diameter holes 241 and 242. The hole 134 provided in the introduction electrode 132 and the holes 241 and 242 are paths for the ions N. A voltage may be applied to the member in which the holes 241 and 242 are provided. In this case, the housing H and the member in which the holes 241 and 242 are provided must be insulated via an insulator (not shown) or the like. The number of vacuum chambers 210, 220, and 230 may be more or less than the number shown in FIG. 1.

[0026] As described above, the vacuum chambers 210, 220, and 230 are evacuated by the vacuum pumps 251 to 253, respectively, and are generally maintained at a pressure of approximately several hundred Pa, several Pa, or 0.1 Pa or less, respectively.

[0027] (Mass spectrometry department 200) The mass analysis section 200 includes an ion transport section 221, an ion analysis section 231a, a detection section 231b, etc., and performs mass analysis of the substances ionized by the ion source 100.

[0028] An ion transport unit 221 that transmits ions N while converging them is installed in the vacuum chamber 220. A multipole electrode, an electrostatic lens, or the like can be used as the ion transport unit 221. The ion transport unit 221 may also be arranged in other vacuum chambers, such as the vacuum chamber 210 or the vacuum chamber 230.

[0029] An ion analysis unit 231a, a detection unit 231b, etc. are installed in the vacuum chamber 230. The ion analysis unit 231a and the detection unit 231b are elements that configure the analysis detection unit 231.

[0030] The ion analysis unit 231a separates and dissociates the ions N. The ion analysis unit 231a can be an ion trap, a quadrupole filter electrode, a collision cell, a time-of-flight mass spectrometer (TOF), or a combination thereof.

[0031] The ions N that have passed through the ion analysis unit 231a are detected by the detection unit 231b. An electron multiplier, a multichannel plate (MCP), or the like can be used as the detection unit 231b. A detection signal of the ions N detected by the detection unit 231b is converted into an electric signal or the like and sent to the control device 400 (indicated by the dashed-dotted line in FIG. 1). The control device 400 analyzes information such as the mass and intensity of the ions N in detail based on the sent electric signal (detection signal).

[0032] The voltage supplied from the power supply 300 to the ion transport section 221 and the ion analysis section 231a may be a high frequency voltage, a direct current voltage, an alternating current voltage, or a combination thereof.

[0033] A feature of the mass spectrometer 1 in this embodiment is that the ion source 100 is provided with a correction electrode 110. The correction electrode 110 will be described later with reference to Fig. 2. The correction electrode 110 is disposed in a space in which the capillary 121 and the counter electrode 131 are installed.

[0034] In this embodiment, the configuration subsequent to the vacuum chamber 210 is referred to as the mass analysis section 200. In the mass spectrometer 1, the ion source 100 side is referred to as the front section, and the detection section 231b side is referred to as the rear section.

[0035] (Control device 400) The control device 400 controls the voltage of the ion source 100 and the mass spectrometric unit 200 via the power supply 300, and also acquires and analyzes a detection signal from the detection unit 231b. Furthermore, the control device 400 determines whether or not the capillary 121, the counter electrode 131, and the correction electrode 110 have deteriorated based on current values ​​measured by a first current measurement unit 141 and a second current measurement unit 142, which will be described later with reference to FIG. 2. Depending on the result of the deterioration determination, various types of predetermined control may be performed, such as displaying a countermeasure or an alert on the screen, storing a history in the storage device 432 (see FIG. 3), or controlling the voltage (correcting the voltage). Such improved accuracy in deterioration determination allows for appropriate control.

[0036] (Ion source system 10) Fig. 2 is a diagram showing the configuration of the ion source system 10 according to the first embodiment. In Fig. 2, the description of the matters already described in Fig. 1 will be omitted.

[0037] The ion source system 10 includes an ion source 100 , a power supply 300 , and a control device 400 .

[0038] The power supply 300 includes a first power supply 301 that applies a voltage "V1" to the capillary 121, a second power supply 302 that applies a voltage "V2" to the counter electrode 131, and a third power supply 303 that applies a voltage "V3" to the correction electrode 110.

[0039] Furthermore, a first current measuring unit 141 is connected to the counter electrode 131, and a second current measuring unit 142 is connected to the correction electrode 110. One end of the first current measuring unit 141 is connected to the counter electrode 131, and the other end is grounded. Similarly, one end of the second current measuring unit 142 is connected to the correction electrode 110, and the other end is grounded.

[0040] In FIG. 2, solid lines indicate connections by signal lines, dashed lines indicate connections by electrical wires, and dotted lines indicate locations where discharge occurs.

[0041] The voltage applied to the correction electrode 110 by the third power supply 303 is approximately several kV at most (absolute value).

[0042] When the first power supply 301 applies a voltage to the capillary 121 and the second power supply 302 applies a voltage to the counter electrode 131, a discharge may occur between the capillary 121 and the counter electrode 131. A current flowing due to the discharge between the capillary 121 and the counter electrode 131 is referred to as a first current A1. Similarly, when the first power supply 301 applies a voltage to the capillary 121 and the third power supply 303 applies a voltage to the correction electrode 110, a discharge may occur between the capillary 121 and the correction electrode 110. A current flowing due to the discharge between the capillary 121 and the correction electrode 110 is referred to as a second current A2. However, it is not necessary to apply a voltage to all of the capillary 121, the counter electrode 131, and the correction electrode 110. It is sufficient that the first current A1 and the second current A2 can be obtained during deterioration determination, which will be described later.

[0043] Furthermore, the first current measuring unit 141 measures the current flowing between the counter electrode 131 and the ground. Similarly, the second current measuring unit 142 measures the current flowing between the correction electrode 110 and the ground.

[0044] Because the voltage applied by the first power supply 301 and the resistance value of the electric wire connecting the first power supply 301 and the capillary 121 are known, the value of the current flowing between the first power supply 301 and the capillary 121 is known. Similarly, because the voltage applied by the second power supply 302 and the resistance value of the electric wire connecting the second power supply 302 and the counter electrode 131 are known, the value of the current flowing between the second power supply 302 and the counter electrode 131 is known. And because the voltage applied by the third power supply 303 and the resistance value of the electric wire connecting the third power supply 303 and the correction electrode 110 are known, the value of the current flowing between the third power supply 303 and the correction electrode 110 is known.

[0045] The control device 400 obtains the current values ​​of the first current A1 and the second current A2 from these known current values ​​based on the current values ​​measured by the first current measurement unit 141 and the second current measurement unit 142. Specifically, the current value of the first current A1 is the difference between the current value flowing between the second power supply 302 and the counter electrode 131 and the current value measured by the first current measurement unit 141. Similarly, the current value of the second current A2 is the difference between the current value flowing between the third power supply 303 and the correction electrode 110 and the current value measured by the second current measurement unit 142.

[0046] In the following description, the combination of the capillary 121, the counter electrode 131, and the correction electrode 110 will be referred to as an application object as appropriate.

[0047] The control device 400 determines whether degradation has occurred in any of the application objects based on changes in the first graph G1 (see FIG. 5A) and the second graph G2 (see FIG. 5B). Hereinafter, the current value of the first current A1 will be referred to as the first current value, and the current value of the second current A2 will be referred to as the second current value. Details of the determination will be described later. The control device 400 also holds a measurement condition table 410. The measurement condition table 410 stores reference values ​​for the voltages "V1" to "V3" at the time of degradation determination, as well as reference values ​​for the first and second current values. The reference values ​​for the voltages "V1" to "V3" and the reference values ​​for the first and second current values ​​are voltage values ​​and current values ​​that serve as references for the degradation determination described above. The respective reference values ​​will be described later, and are voltage values ​​and current values ​​when no degradation has occurred in the application objects. Incidentally, the measurement condition table 410 can be stored in the control device 400, or can be transmitted to the control device 400 from another device via a communication network.

[0048] The direction of the current generated by the first power supply 301 to the third power supply 303 may be any direction as long as the first current value and the second current value can be obtained. However, it is common to apply a voltage so that the potential of the capillary 121 becomes the highest.

[0049] (Hardware configuration) FIG. 3 is a diagram showing the hardware configuration of the control device 400. As shown in FIG.

[0050] The control device 400 is configured as a PC (Personal Computer) or the like, and includes at least a memory 420, an arithmetic unit 431, a storage device 432, a communication device 433, an output device 434, an input device 435, and the like. The memory 420 is configured as a RAM (Random Access Memory) or the like. The arithmetic unit 431 is configured as a CPU (Central Processing Unit), a GPU (Graphic Processing Unit), and the like. The storage device 432 is configured as an HDD (Hard Disk Drive), an SSD (Solid State Drive), and the like. Incidentally, the measurement condition table 410 shown in FIG. 2 is stored in the storage device 432.

[0051] The communication device 433 acquires current values ​​from the first current measuring unit 141 and the second current measuring unit 142, and transmits instruction signals to the power supply 300. The output device 434 is composed of a display or the like. The input device 435 is composed of a keyboard, a mouse, or the like. The output device 434 and the input device 435 may be omitted.

[0052] Then, the program stored in the storage device 432 is loaded into the memory 420, and the loaded program is executed by the arithmetic device 431, thereby realizing the functions of the control device 400.

[0053] In this way, the control device 400 includes an input device 435 for receiving instruction input from a user, and a function for controlling voltage, etc. The control device 400 also includes software, etc., required for operating the power supply 300.

[0054] (experiment) The experiment for determining deterioration will be described with reference to FIGS. 4 to 5B.

[0055] Fig. 4 is a diagram showing the experimental conditions in the first embodiment. In Fig. 4, the same components as those in Fig. 2 are given the same reference numerals and the description thereof will be omitted.

[0056] The distance from the downstream end 121a of the capillary 121 to the center of the counter electrode 131 was set to Z1 = 25 mm. The distance from the downstream end 121a of the capillary 121 to the center of the correction electrode 110 was set to Z2 = 10 mm. The distance from the axial center of the capillary 121 to the tip of the counter electrode 131 was set to X1 = 3 mm. The distance from the axial center of the capillary 121 to the tip of the correction electrode 110 was set to X2 = 10 mm. In the capillary 121, the side of the counter electrode 131 is referred to as the downstream side, and the opposite side is referred to as the upstream side.

[0057] (Experimental results) Figures 5A and 5B are diagrams showing experimental results in the first embodiment. Figures 5A and 5B are diagrams showing results obtained as a result of an experiment carried out under the experimental conditions shown in Figure 4. Figure 2 will be referred to as appropriate.

[0058] The experiment was conducted under the experimental conditions shown in Fig. 4 by applying fluorine-based grease as a contaminant to the tip of the correction electrode 110 to simulate contamination of the correction electrode 110, which is a type of deterioration. Then, the first current value and the second current value were obtained when the amount of the contaminant applied was changed.

[0059] FIG. 5A shows a first graph G1, which is a graph showing the relationship between the first current A1 measured under the above experimental conditions and the voltage. FIG. 5B shows a second graph G2, which is a graph showing the relationship between the second current A2 measured under the above experimental conditions and the voltage. In FIG. 5A, the horizontal axis indicates the voltage value of the voltage applied to the capillary 121, and the vertical axis indicates the current value (first current value). However, the horizontal axis of FIG. 5A may also represent the voltage applied to the counter electrode 131, or the difference between the voltage applied to the capillary 121 and the voltage applied to the counter electrode 131. In other words, the first graph G1 is a graph showing the relationship between the voltage applied to at least one of the capillary 121 and the counter electrode 131 and the first current A1.

[0060] 5B, the horizontal axis represents the voltage applied to the capillary 121, and the vertical axis represents the current value (second current value). However, the horizontal axis in Fig. 5B may represent the voltage applied to the correction electrode 110, or the difference between the voltage applied to the capillary 121 and the voltage applied to the correction electrode 110, etc. In other words, the second graph G2 is a graph showing the relationship between the voltage applied to at least one of the capillary 121 and the correction electrode 110 and the second current A2.

[0061] 5A, graph G11, which is the first graph G1, shows the change in the first current value when the amount of contaminant applied to the correction electrode 110 is 0 μL. Graph G12, which is the first graph G1, shows the change in the first current value when the amount of contaminant applied to the correction electrode 110 is 3 μL. Graph G13, which is the first graph G1, shows the change in the first current value when the amount of contaminant applied to the correction electrode 110 is 6 μL.

[0062] 5B, graph G21, which is the second graph G2, shows the change in the second current value when the amount of contaminant applied to the correction electrode 110 is 0 μL. Graph G22, which is the second graph G2, shows the change in the second current value when the amount of contaminant applied to the correction electrode 110 is 3 μL. Graph G23, which is the second graph G2, shows the change in the second current value when the amount of contaminant applied to the correction electrode 110 is 6 μL.

[0063] 5A and 5B, the current value in FIG. 5B (i.e., the second current value) decreases in accordance with the amount of contamination compared to FIG. 5A (i.e., the first current value). This is because contamination reduces the conductivity of the surface of the correction electrode 110, increasing the resistance of the correction electrode 110 and reducing the value of the second current that flows. In other words, contamination increases the resistance of the correction electrode 110, reducing the value of the current that flows through the current path of the first power supply 301 → capillary 121 → correction electrode 110 → third power supply 303 shown in FIG. 2.

[0064] On the other hand, under the above experimental conditions, there is no contamination of the capillary 121 and the counter electrode 131, so the rate of change (change) of the first graph G1 is small. In other words, there is no contamination of the capillary 121 and the counter electrode 131, so the conductivity of the surfaces of the capillary 121 and the counter electrode 131 does not decrease. In other words, there is no decrease in the resistance of the counter electrode 131 due to contamination. Therefore, the value of the current flowing through the current path of the first power supply 301 → capillary 121 → counter electrode 131 → second power supply 302 shown in FIG. 2 does not decrease (does not change) from the state without contamination.

[0065] 5A and 5B, the change in current value due to contamination is small in FIG. 5A (first graph G1) and large in FIG. 5B (second graph G2). In this embodiment, the rate of change is used as the amount of change.

[0066] Based on these results, the control device 400 determines that deterioration of the correction electrode 110 has occurred. The first current A1 is related to the capillary 121 and the counter electrode 131, but the correction electrode 110 is not related to the first current A1. Therefore, since the rate of change of the first graph G1 is small, the control device 400 can determine that deterioration of the capillary 121 and the counter electrode 131 has not occurred. Note that the current is not stable under low voltage conditions (conditions where the voltage value on the horizontal axis of Figures 5A and 5B is low). Therefore, in the results of Figure 5B, a reversal phenomenon occurs under low voltage conditions. Therefore, it is desirable to use the results on the high voltage side (voltage values ​​greater than a predetermined voltage value, for example, 6 kV or more) to determine deterioration.

[0067] The change rates of the first graph G1 and the second graph G2 (hereinafter simply referred to as the change rates) are defined as the change rates of the first graph G1 and the second graph G2 relative to the reference graph. The reference graphs are defined as the first graph G1 and the second graph G2 when the contamination amount is "0 μL." For example, the first reference graph, which is the reference graph for the first graph G1 shown in FIG. 5A, is defined by graph G11. Similarly, the second reference graph, which is the reference graph for the second graph G2 shown in FIG. 5B, is defined by graph G21. Note that the first reference graph, graph G11, is the first graph G1 when neither the capillary 121 nor the counter electrode 131 is degraded. Similarly, the second reference graph, graph G21, is the second graph G2 when neither the counter electrode 131 nor the correction electrode 110 is degraded.

[0068] The rate of change is calculated by the following formula (1).

[0069] |(y2-y1) / y1| (1)

[0070] In equation (1), "y1" is the current value in the reference graph, and "y2" is the acquired current value. Note that "y1" and "y2" are current values ​​at the same voltage value. "y1" is the value in the first reference graph and the second reference graph.

[0071] As shown in equation (1), the rate of change is the rate of change of the first graph G1 relative to the first reference graph (graph G11) or the rate of change of the second graph G2 relative to the second reference graph (graph G21).

[0072] For example, referring to FIG. 5B, the reference current value "y1" at the same voltage value "6.5V" (reference symbol V11) is "13 μA" (reference symbol A11) obtained based on graph G21. "6.5V" and "13 μA" are obtained from the reference values ​​stored in the measurement condition table 410. "y2" is "11 μA" (reference symbol A12) corresponding to "6.5V" in graph G22, and "10 μA" (reference symbol A13) corresponding to "6.5V" in graph G23. Note that because FIG. 5B is an experiment, graphs G22 and G23 are in known states, but during actual degradation assessment, "y2" becomes the acquired second current value. Note that the current value "A11" will be referred to as the "reference current value during degradation assessment."

[0073] The amount of change relative to the reference graph may be calculated using the following formula (2): In this case, the rate of change is the amount of change.

[0074] |y2-y1| (2)

[0075] Alternatively, if multiple current values ​​can be obtained, the control device 400 may calculate the formula (1) or (2) multiple times, and the square sum error or the like of these may be defined as the amount of change relative to the reference graph.

[0076] The amount of change (rate of change) is not limited to equations (1) and (2). For example, "y1" may be the voltage value in the reference graph, and "y2" may be the acquired voltage value. In this case, "y1" and "y2" are voltage values ​​at the same current value.

[0077] For example, referring to Figure 5B, the reference value "y1" of the voltage value at the second current value "13 μA" (symbol A11) is "6.5 kV" (symbol V11) obtained based on graph G21. Also, "y2" is "6.7 kV" (symbol V12) corresponding to "13 μA" in graph G22, and "6.8 kV" (symbol V13) corresponding to "13 μA" in graph G23.

[0078] The reference value is stored in the measurement condition table 410. The reference value is stored as a combination of a current value and a voltage value in the reference graph in the measurement condition table 410. For example, in the example of FIG. 5B, the combination of "13 μA" and "6.5 V" is stored in the measurement condition table 410.

[0079] In this way, the reference value stored in the measurement condition table 410 may be one point (i.e., one-point data) in the reference graph. Alternatively, continuous profile data (i.e., the reference graph itself) as shown in Figures 5A and 5B may be stored in the measurement condition table 410 as the reference value.

[0080] When the ion source 100 is in a brand new state, such as when it is shipped from the factory, current and voltage measurements are performed, and the measured values ​​at that time are set in the measurement condition table 410 as reference values.

[0081] (Deterioration judgment method) Next, the process of determining the deteriorated portion will be described in detail with reference to FIG.

[0082] 6 is a flowchart showing the procedure of the degradation determination method according to the first embodiment, with reference to FIGS. 2, 5A, and 5B as appropriate.

[0083] First, the control device 400 acquires a current value for determining deterioration, and then calculates a rate of change (S101). In step S101, first, a first current value, a second current value, etc. are calculated.

[0084] Next, in step S101, the control device 400 uses the acquired first current value to calculate the rate of change of the first graph G1 relative to the reference graph. Also in step S101, the control device 400 uses the acquired second current value to calculate the rate of change of the second graph G2 relative to the reference graph. The acquired first current value and second current value are used as "y2" in equations (1) and (2).

[0085] Then, the control device 400 determines whether the rate of change of the first graph G1 is greater than a predetermined value (S111).

[0086] If the rate of change of the first graph G1 is greater than a predetermined value (S111→Yes), the control device 400 determines whether the rate of change of the second graph G2 is greater than a predetermined value (S112). The predetermined value in step S111 and the predetermined value in step S112 may be the same value or different values.

[0087] If the rate of change of the second graph G2 is greater than a predetermined value (S112→Yes), the control device 400 determines that either the capillary 121 is deteriorated or both the counter electrode 131 and the correction electrode 110 are deteriorated (S131). Step S131 corresponds to a case where the rate of change of the first graph G1 is greater than a predetermined value and the rate of change of the second graph G2 is greater than a predetermined value. Note that the rate of change of the first graph G1 is the rate of change of the first graph G1 relative to the first reference graph (graph G11 in FIG. 5A). Also, the rate of change of the second graph G2 is the rate of change of the second graph G2 relative to the second reference graph (graph G21 in FIG. 5B). Thereafter, the control device 400 proceeds to step S141.

[0088] Furthermore, if the rate of change of the second graph G2 is smaller than a predetermined value in step S112 (S112→No), the control device 400 determines that the counter electrode 131 has deteriorated (S132). Step S132 corresponds to the case where the rate of change of the first graph G1 is larger than a predetermined value and the rate of change of the second graph G2 is smaller than a predetermined value. Thereafter, the control device 400 proceeds to step S141.

[0089] Then, if the rate of change of the first graph G1 is smaller than a predetermined value in step S111 (S111→No), the control device 400 determines whether the rate of change of the second graph G2 is larger than a predetermined value (S121).

[0090] If the rate of change of the second graph G2 is greater than the predetermined value (S121→Yes), the control device 400 determines that the correction electrode 110 has deteriorated (S133). Step S133 corresponds to the case where the rate of change of the first graph G1 is smaller than the predetermined value and the rate of change of the second graph G2 is greater than the predetermined value. Thereafter, the control device 400 proceeds to step S141.

[0091] If the rate of change of the second graph G2 is smaller than the predetermined value (S121→No), the control device 400 determines that none of the application objects has deteriorated (S134). Step S134 corresponds to the case where the rate of change of the first graph G1 is smaller than the predetermined value and the rate of change of the second graph G2 is smaller than the predetermined value. Thereafter, the control device 400 proceeds to step S152.

[0092] In step S141, the control device 400 determines whether the rate of change of the first graph G1 and the second graph G2 is equal to or less than a predetermined threshold value. This threshold value is set in advance for the reference graph.

[0093] If at least one of the change rates of the first graph G1 and the second graph G2 is greater than the threshold (S141→No), an alert is output (S142), and the process returns to step S101. The threshold in step S141 is different from the thresholds in steps S111, S112, and S121.

[0094] If the rate of change of the first graph G1 and the second graph G2 is equal to or less than a predetermined threshold (S141→Yes), the control device 400 corrects the voltage and then performs sample analysis (S151). The voltage correction performed in step S151 will be explained later. The corrected voltage is the voltage applied to an application target determined to be deteriorated during sample analysis. Sample analysis refers to analyzing an actual sample. Steps S142 and S151 are control steps in the claims.

[0095] In step S152, the control device 400 performs the sample analysis without correcting the voltage.

[0096] As described above, the deterioration determination method shown in FIG. 6 performs four determination steps S131 to S134 to identify the deteriorated portion. Note that steps S111 to S134 are the determination steps or determination (deterioration determination) in the claims. When the voltage "V1" from the first power supply 301 is applied to the capillary 121, if the rate of change of the first graph G1 is large and the rate of change of the second graph G2 is small, the control device 400 determines that the counter electrode 131 is deteriorated (S132). Conversely, if the rate of change of the first graph G1 is small and the rate of change of the second graph G2 is large, the control device 400 determines that the correction electrode 110 is deteriorated (S133). Furthermore, if the rate of change of both the first graph G1 and the second graph G2 is large, the control device 400 determines that either the capillary 121 is deteriorated or both the counter electrode 131 and the correction electrode 110 are deteriorated (S131). Then, when the rate of change of both the first graph G1 and the second graph G2 is small, the control device 400 determines that none of the application objects has deteriorated (S134).

[0097] In this way, the control device 400 determines whether or not the capillary 121, the counter electrode 131, and the correction electrode 110 have deteriorated based on the rate of change of the first graph G1 and the rate of change of the second graph G2.

[0098] The reference graph used in the deterioration assessment described above may differ from the optimal voltage value during sample analysis when the sample solution Q is actually delivered. In other words, the voltage value generally used for deterioration assessment differs from the voltage value during sample analysis. Therefore, for example, as shown in FIG. 6, deterioration assessment is performed before sample analysis. That is, the control device 400 performs deterioration assessment in a pre-processing step before sample analysis. If sample analysis is performed without understanding the deterioration state of the target object, if the analytical sensitivity fluctuates due to deterioration or other reasons, the analysis may need to be repeated. Therefore, performing sample analysis without understanding the deterioration state of the target object may result in sample waste and reduced throughput. For this reason, it is preferable to perform deterioration assessment before sample analysis, as shown in FIG. 6. This makes it possible to prevent sample waste and reduced throughput.

[0099] Furthermore, as shown in step S151, if the rate of change of the first graph G1 and the second graph G2 relative to the reference graph is equal to or less than a preset threshold, each voltage value is corrected relative to the reference graph for sample analysis and applied. The correction will be described later. This makes it possible to achieve high analysis reproducibility even if one of the target objects is slightly deteriorated.

[0100] Next, the voltage correction performed in step S151 of FIG. 6 will be described with reference to FIG. 5B.

[0101] In this embodiment, correction of the voltage applied to the correction electrode 110 by the third power supply 303 based on the voltage applied to the capillary 121 by the first power supply 301 (horizontal axis in FIG. 5B) will be described.

[0102] In this embodiment, a case will be described in which 13 μA (a second current value for a contamination amount of 0 μL; reference symbol A11) is used as the reference current value for a voltage V1 of 6.5 kV (reference symbol V11 in FIG. 5B) from the first power supply 301. Incidentally, "6.5 V" and "13 μA" are acquired from the reference values ​​stored in the measurement condition table 410. As shown by the solid line in FIG. 5B, the voltage value for a contamination amount of 3 μL corresponding to the reference current value of 13 μA is approximately 6.7 kV (reference symbol V12), and the voltage value for a contamination amount of 6 μL is approximately 6.8 kV (reference symbol V13). In other words, the voltage from the first power supply 301 required to obtain a current of 13 μA, which is the reference current value, changes.

[0103] Next, for example, correction will be described for the case where the pre-correction voltage value during sample analysis is the voltage value "V3=5 kV" applied to the correction electrode 110 by the third power supply 303. Note that the content described in this embodiment can be easily converted to the voltage applied to the capillary 121 and the counter electrode 131.

[0104] The pre-correction voltage value during sample analysis is the voltage that is applied when the objects to which the voltage is applied (the capillary 121, the counter electrode 131, and the correction electrode 110) are not degraded.

[0105] If the correction electrode 110 is deteriorated, the control device 400 corrects the voltage "V3" applied in the sample analysis, as described above, based on the voltage values ​​obtained from the graphs G22 and G23 shown in FIG. 5B.

[0106] Specifically, if the amount of contamination is 3 μL, the control device 400 corrects the voltage applied during sample analysis to 5 kV × 6.7 / 6.5 = 5.15 kV. Here, "6.7" corresponds to the reference current value of "13 μA" for degradation determination in FIG. 5B and is the voltage value when the amount of contamination is "3 μL" (reference symbol V12 in FIG. 5B). "6.5" corresponds to the reference current value of "13 μA" for degradation determination when the amount of contamination is "0 μL" (reference symbol V11 in FIG. 5B). And, as described above, "5 kV" is the voltage value (pre-correction voltage value) applied to the correction electrode 110 by the third power supply 303 during sample analysis when no degradation has occurred in the correction electrode 110.

[0107] If the amount of contamination is 6 μL, the control device 400 corrects the voltage value applied during sample analysis to 5 kV × 6.8 / 6.5 = 5.23 kV. Here, "6.8" corresponds to the reference current value of "13 μA" for degradation determination and is the voltage value for a contamination amount of "6 μL" (reference symbol V13 in FIG. 5B). "6.5" corresponds to the reference current value of "13 μA" for degradation determination when the contamination amount is "0 μL" in FIG. 5B (reference symbol V11 in FIG. 5B). In other words, "6.5" corresponds to the voltage value corresponding to 13 μA in the reference graph G21. As described above, "5 kV" is the voltage value (pre-correction voltage value) applied to the correction electrode 110 by the third power supply 303 during sample analysis when no degradation has occurred in the correction electrode 110.

[0108] Although the above explanation describes the correction of the voltage "V3" applied by the third power supply 303, the correction of the voltage "V1" applied by the first power supply 301 and the voltage "V2" applied by the second power supply 302 can also be performed using a similar method.

[0109] That is, the control device 400 corrects the voltage to be applied based on the following equation (11).

[0110] Vcor = Vs × Vβ / Vα (11)

[0111] In equation (11), "Vcor" is the corrected voltage value applied during sample analysis. Furthermore, "Vs" is the voltage value before correction (pre-correction voltage value), which is the voltage value applied to the sample analysis target when no degradation has occurred. "Vα" is the voltage value on the reference graph corresponding to the reference value of the current value during degradation assessment. In other words, "Vα" is a voltage value based on the reference graph. "Vβ" is the voltage value corresponding to the reference value of the current value during degradation assessment in the graphs during contamination (graphs G22 and G23 in FIG. 5B). In the example of FIG. 5B, the reference value of the current value during degradation assessment is "13 μA" (referred to as "Iα"). Furthermore, in the graphs during contamination (graphs G22 and G23 in FIG. 5B), the voltage value (i.e., "Vβ") corresponding to "Iα" (here, "13 μA") (i.e., "Vβ") is the voltage value indicated by the symbols V12 and V13.

[0112] In the above explanation, the calculation changes depending on the amount of contamination, but in reality, the voltage value used in determining deterioration can be substituted into "Vβ" in equation (11). This makes it possible to correct the voltage even if the amount of contamination is unknown.

[0113] In this way, the control device 400 corrects the voltage value of the voltage applied during sample analysis to the capillary 121, the counter electrode 131, and the correction electrode 110 that are determined to be deteriorated based on the results of the deterioration determination.

[0114] In such voltage correction, it is assumed that the rate of change of the voltage applied by the first power supply 301 and the rate of change of the voltage applied by the third power supply 303 for the same current are equivalent. "Equivalent... for the same current" means, for example, that the rate of change of the voltage applied by the first power supply 301 for "13 μA" is equivalent to the rate of change of the voltage applied by the third power supply 303. Similarly, it is assumed that the rate of change of the voltage applied by the first power supply 301 and the rate of change of the voltage applied by the second power supply 302 for the same current are equivalent.

[0115] 6, the control device 400 can output an alert to prompt maintenance (cleaning or replacement of the application target). Step S142 is a process that is performed when at least one of the rate of change of the first graph G1 and the rate of change of the second graph G2 is greater than a preset threshold value with respect to the reference graph. If the ion source 100 is provided with an autonomous cleaning function, an object determined to be deteriorated by the deterioration determination may be autonomously cleaned. Alternatively, a user may manually clean an object determined to be deteriorated by the deterioration determination. The object to be cleaned is an object determined to be deteriorated among the application targets.

[0116] Alternatively, depending on the state of deterioration, the part determined to be deteriorated by the deterioration determination is replaced.

[0117] 6, after maintenance such as cleaning (automatic or manual) or replacement is completed, the control device 400 preferably performs the deterioration determination again (returns to S101). In this way, it is possible to confirm whether the deterioration state has been improved. Note that the measurement condition table 410 can store the voltage value calculated by the voltage correction in step S151 of FIG. 6, the threshold value (predetermined value) used in steps S111, S112, S121, and S141, and the like.

[0118] The correction values ​​and correction methods described above are merely examples, and in practice they need to be optimized according to the analysis conditions, the object to which the signal is to be applied, etc., and the same applies to the threshold values ​​described above.

[0119] According to the first embodiment described above, by having the correction electrode 110, it is possible to realize the ion source system 10 and the mass spectrometer 1 that can improve the accuracy of determining the deterioration state of the target object.

[0120] In other words, according to the first embodiment described above, the contamination status of the target electrode can be identified based on the results of the deterioration determination. Furthermore, by applying a voltage having a corrected voltage value to the target electrode based on the results of the deterioration determination, it is possible to maintain the sensitivity of the mass spectrometer 1. This makes it possible to provide a mass spectrometer 1 with high robustness and high analysis reproducibility.

[0121] [Second embodiment] (correction electrode 110 is movable) Next, a second embodiment of the present invention will be described with reference to Figures 7 and 8. In the second embodiment, an ion source system 10a in which the correction electrode 110 moves will be described.

[0122] 7 and 8 are diagrams showing the configuration of an ion source system 10a according to the second embodiment. For simplicity, in Fig. 7 and Fig. 8, the same components as those in Fig. 2 are denoted by the same reference numerals as those in Fig. 2, and only the differences from Fig. 2 will be described.

[0123] 7 and 8, the power supply 300 (first power supply 301 to third power supply 303), the control device 400, the first current measuring unit 141, and the second current measuring unit 142 are omitted from the illustration, but in reality, these devices are installed as in FIG. 2.

[0124] The correction electrode 110 of the ion source 100a shown in FIGS. 7 and 8 is characterized in that it moves between a deterioration determination mode position PL1 and a sample analysis mode position PL2.

[0125] Depending on the position of the correction electrode 110, deterioration determination and sample analysis may not be compatible. Therefore, as shown in FIG. 7, during deterioration determination, the correction electrode 110 moves to a position (deterioration determination mode position PL1: shown by a dashed line) where deterioration determination is easy. During sample analysis, the correction electrode 110 can be moved to a position (sample analysis mode position PL2: shown by a solid line) where the effect on ion generation is small. As shown in FIG. 8, at the deterioration determination mode position PL1, the distance between the correction electrode 110 and the capillary 121 is small, so that the second current A2 is likely to be generated between the correction electrode 110 and the capillary 121. However, when the correction electrode 110 moves to the sample analysis mode position PL2, the distance between the correction electrode 110 and the capillary 121 increases. This makes it difficult for the second current A2 to be generated between the correction electrode 110 and the capillary 121. As a result, deterioration of the correction electrode 110 becomes less likely.

[0126] If the position of the correction electrode 110 is relatively far from the capillary 121, there is a possibility that a sufficient current for determining the deterioration of the object to be applied cannot be detected during deterioration determination. On the other hand, if the position of the correction electrode 110 is relatively close to the capillary 121, there is a possibility that the electric field between the capillary 121 and the counter electrode 131, which is necessary for ionization, may be disturbed during sample analysis, resulting in a decrease in sensitivity.

[0127] Furthermore, even if no voltage is applied to the correction electrode 110, if the correction electrode 110 is positioned relatively close to the capillary 121, the correction electrode 110 will disturb the electric field between the capillary 121 and the counter electrode 131. Specifically, discharge will occur from the capillary 121 toward the correction electrode 110, and a sufficient electric field may not be generated between the capillary 121 and the counter electrode 131.

[0128] In the second embodiment, the distance between the correction electrode 110 and the capillary 121 during sample analysis is set to be greater than the distance between the correction electrode 110 and the capillary 121 during deterioration determination. This makes it possible to achieve both of the above-mentioned problems.

[0129] The correction electrode 110 is moved by a driving device 170, which is a moving unit. The driving device 170 moves the correction electrode 110 in response to instructions from the control device 400. However, the correction electrode 110 can also be moved manually by a user.

[0130] Furthermore, during sample analysis, the voltages "V1" to "V2" applied to the capillary 121 and the counter electrode 131 may be corrected based on the current values ​​acquired (used) during degradation assessment. The current values ​​acquired during degradation assessment are the current value of the first current A1 (first current value) and the current value of the second current A2 (second current value). The corrected values ​​are voltage values ​​corrected based on the correction performed in step S151 of FIG. 6.

[0131] In FIG. 6, if both step S111 and step S112 are "Yes," then either the capillary 121 is degraded, or both the counter electrode 131 and the correction electrode 110 are degraded (S131). In contrast, in the configuration of the second embodiment, the correction electrode 110 moves away from the capillary 121 and the counter electrode 131 during sample analysis, so it is considered that the correction electrode 110 does not generally degrade. In other words, since the correction electrode 110 moves away from the capillary 121 and the counter electrode 131 during sample analysis, contamination by charged droplets and the like can be reduced. Therefore, it is considered that the correction electrode 110 does not generally degrade. Therefore, if both step S111 and step S112 are "Yes," that is, in step S131, it is ruled out that both the counter electrode 131 and the correction electrode 110 are degraded. In other words, in step S131, the control device 400 can determine that the capillary 121 is degraded.

[0132] According to the configuration of the second embodiment described above, the correction electrode 110 moves depending on the mode, thereby realizing an ion source system 10a and a mass spectrometer 1 that can improve the deterioration determination performance and prevent a decrease in analytical sensitivity.

[0133] [Third embodiment] (correction electrode 110 is used as a deflection electrode) Next, a third embodiment of the present invention will be described with reference to Fig. 9. In the third embodiment, an ion source system 10b and a mass spectrometer 1 that use a correction electrode 110 as a deflection electrode will be described.

[0134] Fig. 9 is a diagram showing the configuration of an ion source system 10b according to the third embodiment. For simplicity, in Fig. 9, the same components as in Fig. 2 are denoted by the same reference numerals as in Fig. 2, and only the differences from Fig. 2 will be described.

[0135] Also, in Figure 9, the power supply 300 (first power supply 301 to third power supply 303), control device 400, first current measuring unit 141, and second current measuring unit 142 are omitted from the illustration, but in reality, these devices are installed as in Figure 2.

[0136] 9, during sample analysis, the third power supply 303 (see FIG. 2) applies a voltage "V3" to the correction electrode 110. The voltage applied to the correction electrode 110 is approximately several kV at most (absolute value).

[0137] During sample analysis, a voltage "V3" is applied to the correction electrode 110, thereby deflecting the generated ions N toward the mass analysis unit 200 (toward the counter electrode 131) (reference numeral 701). At this time, "V3" (absolute value) is greater than "V2" (absolute value). Note that "V2" is the voltage applied to the counter electrode 131 during sample analysis. In other words, during sample analysis, the voltage applied to the correction electrode 110 by the third power supply 303 is greater than the voltage applied to the counter electrode 131 by the second power supply 302. As described above, in the third embodiment, the control device 400 controls the second power supply 302 and the third power supply 303 so that the ions N are deflected toward the counter electrode 131.

[0138] By deflecting the ions N toward the counter electrode 131, the amount of ions introduced into the mass analysis unit 200 is increased, and analytical sensitivity can be improved. In the third embodiment, as in the second embodiment, the position of the correction electrode 110 may be moved depending on the mode. In addition, as in the first embodiment, the voltages "V1" to "V3" applied to the application target during sample analysis may be corrected in accordance with the current value acquired during deterioration determination.

[0139] According to the configuration of the third embodiment described above, by using the correction electrode 110 as a deflection electrode, it is possible to achieve both a deflection function and a correction function. The deflection function is a function of deflecting ions N. Furthermore, as in the first embodiment, the correction function is a function of determining whether or not the object to be applied has deteriorated, and if there has been deterioration, applying a corrected voltage during sample analysis. This makes it possible to realize an ion source system 10b and a mass spectrometer 1 that can improve analytical sensitivity.

[0140] When the correction electrode 110 is used as a deflection electrode as in the third embodiment, the effective function of the correction electrode 110 as a deflection electrode is reduced due to contamination of the correction electrode 110. Therefore, it is necessary to determine the deterioration of the correction electrode 110 according to the first embodiment.

[0141] [Fourth embodiment] (Interlocking with liquid chromatography device 2) Next, a fourth embodiment of the present invention will be described with reference to Figures 10 to 12. In the fourth embodiment, an ion source system 10 and a mass spectrometer 1 that are linked to a liquid chromatography apparatus 2 will be described.

[0142] Fig. 10 is a diagram showing an example of the configuration of the liquid chromatography device 2. Fig. 11 is a diagram showing an example of a chromatogram output by the liquid chromatography device 2.

[0143] The liquid chromatography device 2 includes a first tank 21 a, a second tank 21 b, a first pump 22 a, a second pump 22 b, a mixer 23, a sample injection section 24, and a separation column 25.

[0144] The two tanks (first tank 21a, second tank 21b) contain different mobile phases, and the mobile phases contained in the tanks are often, for example, one of which contains a large amount of water, while the other contains a large amount of an organic solvent such as methanol or acetonitrile.

[0145] The mobile phases contained in the first tank 21a and the second tank 21b are sent to the mixer 23 by the discharge forces of the first pump 22a and the second pump 22b, respectively.

[0146] The two mobile phases are then mixed in mixer 23. Subsequently, a sample is injected from sample injection section 24, whereby the sample is mixed into the mixed mobile phase. The mobile phase mixed with the sample is referred to as sample solution Q (see FIG. 2). The mixing ratio in mixer 23 can be adjusted by the flow rate ratio of first pump 22a and second pump 22b.

[0147] The sample solution Q is sent to the separation column 25 by the discharge forces of the first pump 22a and the second pump 22b. Prior to use, the separation column 25 is washed and equilibrated with water, an organic solvent, or the like, which will be used as a mobile phase. Then, in the separation column 25, the components constituting the sample (hereinafter referred to as sample components) are eluted from the sample solution Q one by one. During elution, the mixing ratio of each mobile phase can be changed over time. The eluted components are introduced into the ion source 100 in the order of elution (open arrows).

[0148] The liquid chromatography apparatus 2 shown in FIG. 10 can obtain a chromatogram as shown in FIG. 11. In the chromatogram shown in FIG. 11, the horizontal axis represents the retention time (RT: unit: min) of the separation column 25, and the vertical axis represents the intensity (corresponding to the amount of sample component) at each timing. The intensity is the intensity of the detection signal by the detection unit 231b. In gradient elution, in which the mixing ratio of two mobile phases is changed over time to elute sample components, the type of sample component corresponding to the mixing ratio at each timing is specifically eluted. In other words, even if a sample solution Q containing multiple types of sample components is injected, the separation column 25 can separate each sample component over time, and the content amount can be quantified from the intensity of each peak 500.

[0149] Fig. 12 is a diagram showing the configuration of an ion source system 10 according to a fourth embodiment. For simplicity, in Fig. 12, the same components as those in Fig. 2 are denoted by the same reference numerals as those in Fig. 2, and only differences from Fig. 2 will be described. The ion source system 10 according to the fourth embodiment has the same configuration as the ion source system 10 shown in Fig. 2.

[0150] Also, in Figure 12, the power supply 300 (first power supply 301 to third power supply 303), control device 400, first current measuring unit 141, and second current measuring unit 142 are omitted from the illustration, but in reality, these devices are installed as in Figure 2.

[0151] 12, in the fourth embodiment, sample components separated in a liquid chromatography device 2 are introduced into an ion source 100. That is, a substance is introduced into the ion source 100 from the liquid chromatography device 2.

[0152] As shown in Fig. 12, an ion source 100 is disposed downstream of the liquid chromatography device 2, whereby sample components corresponding to peak 500 in the chromatogram shown in Fig. 11 are ionized over time. Then, the mass of each sample component is determined by the mass analysis unit 200, allowing the sample component to be identified. Furthermore, the retention time corresponding to the sample component can be uniquely defined from the type of separation column 25, the mixing ratio of the two mobile phases, the liquid delivery rate, the length of piping, etc.

[0153] Here, the optimal ionization conditions for the ion source 100 may differ depending on the target sample components. Therefore, it is effective to change the voltage conditions applied to the target object according to the retention time (corresponding to the sample components) during sample analysis to the optimal value for the sample components. In other words, the optimal voltage applied to the target object varies depending on the sample components.

[0154] In the configuration of the fourth embodiment, the voltages applied to the object in accordance with the peaks 500 in the chromatogram are set to correction values ​​calculated by the voltage correction performed in step S151 of Fig. 6. In other words, the voltage values ​​are corrected in accordance with the substance introduced from the liquid chromatography apparatus 2 to the ion source 100.

[0155] For example, the voltage value (pre-correction voltage value) applied to the application object for peak 501 is defined as "Va." Furthermore, the voltage value (pre-correction voltage value) applied to the application object for peak 502 is defined as "Vb." The voltage value (pre-correction voltage value) applied to the application object for peak 503 is defined as "Vc." The voltage value (pre-correction voltage value) applied to the application object for peak 504 is defined as "Vd." Here, "Va" to "Vd" are defined as the voltage values ​​of the voltage applied to any of the capillary 121, the counter electrode 131, and the correction electrode 110.

[0156] If it is determined that deterioration has occurred in the object to which the voltage is applied, the voltage values ​​to be applied at the timings of the respective peaks 501 to 504 are corrected to "Va1" to "Vd1." The correction is performed by the voltage correction method described in the first embodiment.

[0157] It is desirable that the pre-correction voltage value of the voltage to be applied to the application object during sample analysis for each of the peaks 501 to 504 is stored in the measurement condition table 410. Then, it is desirable that the pre-correction voltage value of each voltage value is corrected, so that the voltage to be applied to the application object is corrected in accordance with each of the peaks 501 to 504.

[0158] In the fourth embodiment, the measurement condition table 410 may store liquid chromatography separation conditions. Examples of the liquid chromatography separation conditions include the types of two mobile phases and their mixing ratios. Also, examples of the liquid chromatography separation conditions include the type of separation column 25, the liquid delivery speed, and the retention time (each corresponding to a sample component). Furthermore, the measurement condition table 410 can store voltage conditions (including a correction value for the voltage value corresponding to the current value acquired during degradation determination) according to the liquid chromatography separation conditions.

[0159] In the configuration of the fourth embodiment described above, the liquid chromatography apparatus 2 and the ion source system 10 work together, and the control device 400 controls the voltage to be applied to the target object according to the liquid chromatography conditions, etc. This makes it possible to realize a mass spectrometer 1 that can analyze multiple sample components under conditions optimized for each component.

[0160] [Fifth embodiment] Next, a fifth embodiment of the present invention will be described with reference to FIG.

[0161] FIG. 13 is a diagram showing a measurement condition table 410a used in the fifth embodiment.

[0162] As shown in FIG. 13, conditions are set for each liquid chromatography device 2 and mass spectrometer 1 in the measurement condition table 410a.

[0163] The liquid chromatography apparatus 2 and the mass spectrometer 1 are constructed using a combination of high-precision components. However, even if the individual precision of mechanical components and electronic circuit components is maximized, cumulative errors occur due to the combination of components. Therefore, even when analyses are performed under the same conditions among multiple liquid chromatography apparatuses 2 and mass spectrometers 1 designed, manufactured, and assembled under similar conditions, some degree of performance difference (inter-instrument difference) may occur. Therefore, as shown in FIG. 13, the measurement condition table 410a can store conditions specific to each apparatus, such as the liquid chromatography apparatus 2 and the mass spectrometer 1. Then, voltage values ​​are corrected according to the individual ion source system 10 and the mass analysis unit 200. The conditions specific to each apparatus are, for example, reference graphs for each apparatus (graph G11 in FIG. 5A and graph G21 in FIG. 5B). This reduces performance differences between the liquid chromatography apparatuses 2 and the mass spectrometers 1.

[0164] [Sixth embodiment] (operated with liquid chromatography device 2 and reverse deflection when peak 500 is not present) Next, a sixth embodiment of the present invention will be described with reference to Figures 14 and 15. An ion source system 10c and a mass spectrometer 1 in the sixth embodiment have a configuration that operates in conjunction with a liquid chromatography device 2, and deflects ions N in the opposite direction to the mass analysis section 200 at a timing (reference numeral 510) when there is no peak 500 (see Figure 15) in the chromatogram.

[0165] Fig. 14 is a diagram showing the configuration of an ion source system 10c according to the sixth embodiment, and Fig. 15 is a diagram showing an example of a chromatogram output by the liquid chromatography apparatus 2 shown in Fig. 14. For simplicity, in Fig. 14, the same components as in Fig. 2 are denoted by the same reference numerals as in Fig. 2, and only the differences from Fig. 2 will be described.

[0166] Also, in Figure 14, the power supply 300 (first power supply 301 to third power supply 303), control device 400, first current measuring unit 141, and second current measuring unit 142 are omitted from the illustration, but in reality, these devices are installed as in Figure 2.

[0167] In the ion source 100c shown in the sixth embodiment, as shown in FIG. 15, during a period indicated by reference numeral 510, a voltage is applied to the correction electrode 110 so that the generated ions N are deflected in the direction opposite to the direction of the mass analysis unit 200. The period indicated by reference numeral 510 corresponds to a period during which the components to be analyzed are not eluted. As a result, during a period during which the components to be analyzed are not eluted, the ions N are deflected in the direction opposite to the direction of the mass analysis unit 200, as indicated by reference numeral 702. At this time, the condition of the applied voltage is "V3" (absolute value) < "V2" (absolute value). Note that "V3" is the voltage applied to the correction electrode 110 by the third power supply 303 as shown in FIG. 2. Furthermore, "V2" is the voltage applied to the counter electrode 131 by the second power supply 302 as shown in FIG. 2. As a result, the control device 400 controls the second power supply 302 and the third power supply 303 so that the ions N are deflected toward the correction electrode 110 while the components to be analyzed are not being eluted from the liquid chromatography device 2.

[0168] As described above, in the sixth embodiment, while the component to be analyzed is not being eluted, the control device 400 controls the second power supply 302 and the third power supply 303. The control is performed so that the voltage applied to the correction electrode 110 by the third power supply 303 is smaller than the voltage applied to the counter electrode 131 by the second power supply 302.

[0169] By deflecting the ions N in the direction opposite to the direction of the mass analysis section 200, it is possible to prevent excess charged droplets and the like from being introduced into the mass analysis section 200 during unnecessary periods other than the timing of analysis of the component to be analyzed. This makes it possible to prevent contamination (deterioration) that exists downstream from the counter electrode 131. Therefore, it is possible to improve the robustness of the mass spectrometer 1.

[0170] In the analysis of known samples, such as quantitative testing of specific substances, the configuration shown in the sixth embodiment is particularly effective because detection is not required except while the component to be analyzed is not eluted. Furthermore, the applied voltage at this time may be a voltage corrected according to the current value obtained during the deterioration determination. The applied voltage is a voltage applied to each of the objects to which the voltage is applied.

[0171] In the configuration shown in the sixth embodiment described above, ions N are deflected in the direction opposite to the ion introduction direction (the direction of the mass analysis unit 200) during the period when there is no peak 500 in the chromatogram (reference numeral 510 in FIG. 15). As described above, reference numeral 510 corresponds to the period during which the components to be analyzed are not eluted. This makes it possible to improve the robustness of the mass spectrometer 1.

[0172] [Seventh embodiment] (Third current A3 is measured) Next, a seventh embodiment of the present invention will be described with reference to Figures 16 and 17. In the seventh embodiment, a third current A3 flowing between the counter electrode 131 and the correction electrode 110 is acquired.

[0173] Fig. 16 is a diagram showing the configuration of an ion source system 10 according to the seventh embodiment. For simplicity, in Fig. 16, the same components as those in Fig. 2 are denoted by the same reference numerals, and only the differences from Fig. 2 will be described.

[0174] The ion source system 10 shown in FIG. 16 has a configuration similar to that of the ion source system 10 shown in FIG.

[0175] In addition to the first current value and the second current value, the ion source system 10 acquires the current value of a third current A3 flowing between the counter electrode 131 and the correction electrode 110. The third current A3 is a current caused by discharge occurring between the counter electrode 131 and the correction electrode 110.

[0176] The third current A3 is obtained in the following procedure. First, the control device 400 stops the application of voltage to the capillary 121 by the first power supply 301. This stops the discharge between the capillary 121 and the counter electrode 131 and between the capillary 121 and the correction electrode 110. Then, at least one of the application of voltage to the correction electrode 110 by the third power supply 303 and the application of voltage to the counter electrode 131 by the second power supply 302 is continued.

[0177] Thereafter, the control device 400 acquires a current value from the first current measuring unit 141 and acquires a current value from the second current measuring unit 142. The current value acquired from the first current measuring unit 141 is designated as "a21," and the current value acquired from the second current measuring unit 142 is designated as "a22."

[0178] On the other hand, the voltage value of the voltage applied to the second power supply 302 is known. If the resistance value of the electric wire between the second power supply 302 and the counter electrode 131 is also known, the current value between the second power supply 302 and the counter electrode 131 is also known. The current value between the second power supply 302 and the counter electrode 131 is assumed to be "a11."

[0179] The voltage value of the voltage applied to the third power supply 303 is known. If the resistance value of the electric wire between the third power supply 303 and the correction electrode 110 is also known, the current value between the third power supply 303 and the correction electrode 110 is also known. The current value between the third power supply 303 and the correction electrode 110 is assumed to be "a12."

[0180] Then, the control device 400 obtains the current value of the third current A3 (third current value) by calculating "(a11+a12)-(a21+a22)." Note that the method for obtaining (calculating) the third current value is not limited to the method described in this embodiment.

[0181] Furthermore, although the above-described method of acquiring the third current value involves acquiring current values ​​from both the first current measuring unit 141 and the second current measuring unit 142, it is also possible to acquire the current value from either one of them. Furthermore, the control device 400 may calculate the current value of the third current A3 based on the current value measured by the first current measuring unit 141 in a state where a voltage is applied only to the correction electrode 110. Alternatively, the control device 400 may calculate the current value of the third current A3 based on the current value measured by the second current measuring unit 142 in a state where a voltage is applied only to the counter electrode 131.

[0182] (Deterioration judgment) FIG. 17 is a diagram showing a deterioration determination table in the seventh embodiment.

[0183] 17, "G1" indicates the first graph G1 (see FIG. 5A), "G2" indicates the second graph G2 (see FIG. 5B), and "G3" indicates the third graph G3 (see FIG. 20B). The third graph G3 is a graph showing the relationship between the third current A3 and the voltages applied to the counter electrode 131 and the correction electrode 110.

[0184] The control device 400 performs the determination in steps S111, S112, and S121 in Fig. 6 according to the deterioration determination table. Such determination is easy for a person skilled in the art, so a flowchart for determining deterioration will be omitted.

[0185] Basically, if one of the target objects is degraded, the rate of change of the two graphs flowing between the target objects including the degraded target object will be large. In other words, a result in which the rate of change of any two graphs is small cannot occur, so the result in which the rate of change of any two graphs is small will be excluded from the explanation.

[0186] 16, when the capillary 121 is deteriorated, the rate of change in the first graph G1 and the second graph G2 increases. When the counter electrode 131 is deteriorated, the rate of change in the first graph G1 and the third graph G3 increases. When the correction electrode 110 is deteriorated, the rate of change in the second graph G2 and the third graph G3 increases.

[0187] In this way, when the rate of change of a graph increases, two or more graphs always change. That is, the phenomenon in which the rate of change of any two graphs is small, in other words, only one of the first graph G1 to the third graph G3 is large, does not occur. Therefore, in the seventh embodiment, the result in which the rate of change of any two graphs is small, that is, the rate of change of only one graph is large, will not be explained.

[0188] First, if the change rates of all of the first graph G1 to the third graph G3 are small, the control device 400 determines that none of the application objects have deteriorated (reference numeral 801 in FIG. 17). If the change rates of the second graph G2 and the third graph G3 are large, the control device 400 determines that the correction electrode 110 has deteriorated (reference numeral 802 in FIG. 17). If the change rates of the first graph G1 and the third graph G3 are large, the control device 400 determines that the counter electrode 131 has deteriorated (reference numeral 803 in FIG. 17). If the change rates of the first graph G1 and the second graph G2 are large, the control device 400 determines that the capillary 121 has deteriorated (reference numeral 804 in FIG. 17). If the change rates of all of the first graph G1 to the third graph G3 are large, the control device 400 determines that there is a possibility that any two or more application objects have deteriorated (reference numeral 805 in FIG. 17). The phrase "any two or more application targets are deteriorated" means that any two or more of the capillary 121, the counter electrode 131, and the correction electrode 110 are deteriorated.

[0189] The above determination will be explained in detail with reference to FIG.

[0190] Reference numeral 801 indicates a case where the rate of change of the first graph G1 (see FIG. 5A) is smaller than a predetermined value, the rate of change of the second graph G2 (see FIG. 5B) is smaller than a predetermined value, and the rate of change of the third graph G3 (see FIG. 20B) is smaller than a predetermined value. Hereinafter, the rate of change of the first graph G1 is the rate of change with respect to the first reference graph (graph G11 in FIG. 5A). Similarly, the rate of change of the second graph G2 is the rate of change with respect to the second reference graph (graph G21 in FIG. 5B). And the rate of change of the third graph G3 is the rate of change with respect to the third reference graph (graph G31 in FIG. 20B). In such a case, the control device 400 determines that none of the capillary 121, the counter electrode 131, and the correction electrode 110 has deteriorated. Incidentally, the third reference graph is the third graph G3 in a case where neither the counter electrode 131 nor the correction electrode 110 has deteriorated.

[0191] Reference numeral 802 indicates a case where the rate of change of the first graph G1 is smaller than a predetermined value, the rate of change of the second graph G2 is larger than a predetermined value, and the amount of change of the third graph G3 is larger than a predetermined value. In such a case, the control device 400 determines that the correction electrode 110 has deteriorated.

[0192] Reference numeral 803 represents a case where the rate of change of the first graph G1 is greater than a predetermined value, the rate of change of the second graph G2 is less than a predetermined value, and the rate of change of the third graph G3 is greater than a predetermined value. In such a case, the control device 400 determines that the counter electrode 131 has deteriorated.

[0193] Reference numeral 804 indicates a case where the rate of change of the first graph G1 is greater than a predetermined value, the rate of change of the second graph G2 is greater than a predetermined value, and the rate of change of the third graph G3 is less than a predetermined value. In such a case, the control device 400 determines that the capillary 121 is deteriorated.

[0194] Reference numeral 805 indicates a case where the rate of change of the first graph G1 is greater than a predetermined value, the rate of change of the second graph G2 is greater than a predetermined value, and the rate of change of the third graph G3 is greater than a predetermined value. In such a case, the control device 400 determines that two or more of the capillary 121, the counter electrode 131, and the correction electrode 110 have deteriorated.

[0195] In the seventh embodiment, as in the second embodiment, the position of the correction electrode 110 may be moved between the time of deterioration determination and the time of sample analysis. With this configuration, the correction electrode 110 is basically not contaminated, and the control device 400 can determine at 805 that the capillary 121 and the counter electrode 131 have deteriorated.

[0196] Also in the seventh embodiment, corrected voltages "V1" to "V3" are applied, similar to steps S141 to S151 in the flowchart of FIG. 6. Steps S141 to S151 correspond to the case where all of the change rates of the first graph G1 to the third graph G3 are equal to or less than the threshold. Furthermore, if at least one of the change rates of the first graph G1 to the third graph G3 is greater than the threshold, the control device 400 proceeds to the process of outputting an alert in step S142 of FIG. 6. Incidentally, this threshold may be a value different from the determination threshold in FIG. 17.

[0197] In the seventh embodiment, the control device 400 determines whether or not there is deterioration in the capillary 121, the counter electrode 131, and the correction electrode 110. The determination (deterioration determination) is made based on the rate of change of the first graph G1, the rate of change of the second graph G2, and the rate of change of the third graph G3.

[0198] According to the configuration of the seventh embodiment described above, the third current A3 is acquired, thereby improving the accuracy of determining whether the application object has deteriorated.

[0199] [Eighth embodiment] (having deflection electrodes 150 and further having correction electrodes 110) An eighth embodiment of the present invention will now be described with reference to Figures 18 to 21. In the eighth embodiment, an ion source system 10d and a mass spectrometer 1 will be described, in which a correction electrode 110 is provided and a deflection electrode 150 is provided separately from the correction electrode 110.

[0200] (Ion source 100d) Fig. 18 is a diagram showing the configuration of an ion source 100d according to the eighth embodiment. For simplicity, in Fig. 18, the same components as those in Fig. 2 are denoted by the same reference numerals, and only differences from Fig. 2 will be described. Fig. 19 is a schematic diagram of an ion source system 10d according to the eighth embodiment.

[0201] Fig. 18 is a view looking in the direction of the counter electrode 131 from the position of the capillary 121. In Fig. 19, components similar to those in Fig. 2 are omitted as appropriate to avoid complication. Incidentally, Fig. 19 is a view of the ion source system 10d as viewed from the Y-axis direction in Fig. 18. In Fig. 19, the positions of the components are not shown accurately.

[0202] 18 and 19, a correction electrode 110 is provided, and a deflection electrode 150 for deflecting ions N is installed separately from the correction electrode 110. The deflection electrode 150 is installed in a space (ion source chamber 160) in which the correction electrode 110 is installed.

[0203] 19, the power supply 300d includes a fourth power supply 304. A voltage "V4" is applied to the deflection electrode 150 by the fourth power supply 304. A fourth current measuring unit 144 is connected to the deflection electrode 150. One end of the fourth current measuring unit 144 is connected to the deflection electrode 150, and the other end is grounded. When a voltage is applied between the correction electrode 110 and the deflection electrode 150, a discharge occurs between the correction electrode 110 and the deflection electrode 150. A current flowing due to the discharge between the correction electrode 110 and the deflection electrode 150 is referred to as a fourth current A4.

[0204] In the eighth embodiment, in addition to the capillary 121, the counter electrode 131, and the correction electrode 110, the deflection electrode 150 is also included in the object to which the voltage is applied.

[0205] The control device 400 calculates the current value of the fourth current A4 based on the first current measurement unit 141, the second current measurement unit 142, the fourth current measurement unit 144, and the currents flowing through the first power supply 301 to the fourth power supply 304 and the object to which the voltage is applied. The currents flowing through the first power supply 301 to the fourth power supply 304 and the object to which the voltage is applied can be easily calculated from the voltages applied to the object to which the voltage is applied and the resistance values ​​of the electric wires connecting the first power supply 301 to the fourth power supply 304 and the object to which the voltage is applied. Furthermore, the current value of the fourth current A4 can be easily calculated using these current values ​​and Kirchhoff's law.

[0206] In reality, electric currents also flow between the deflection electrode 150 and the capillary 121 and between the deflection electrode 150 and the counter electrode 131 due to discharge, but these currents are not necessary in the eighth embodiment, so they are not shown or described here.

[0207] The deflection electrode 150 has the same role as the correction electrode 110 described in the third embodiment. That is, when a voltage is applied to the deflection electrode 150, the ions N are deflected in the opposite direction to the mass analysis section 200. In Fig. 18 and Fig. 19, the deflection electrode 150 and the correction electrode 110 are arranged so that their axial directions are orthogonal to each other, but the positional relationship between the deflection electrode 150 and the correction electrode 110 may be any positional relationship.

[0208] That is, the positional relationship between the correction electrode 110 and the deflection electrode 150 may be any positional relationship as long as both the correction electrode 110 and the deflection electrode 150 are present inside the ion source chamber 160. However, if the correction electrode 110 and the deflection electrode 150 are in a parallel relationship, one of them will be far from the capillary 121, so it is desirable that the correction electrode 110 and the deflection electrode 150 are not in a parallel relationship. Also, it is desirable that the tips (pointed ends) of the correction electrode 110 and the deflection electrode 150 are in a positional relationship facing each other (not necessarily facing each other), because this allows for efficient generation of an electric field.

[0209] (Experimental results) The inventors also conducted an experiment using the configuration of the ion source 100d having the deflection electrode 150 and the correction electrode 110 shown in FIG. 18. The experimental conditions were as follows: The distance Z1 from the downstream end 121a of the capillary 121 to the center of the counter electrode 131 (the center of the hole 133) was set to 25 mm. The distance Z3 from the downstream end 121a of the capillary 121 to the center of the deflection electrode 150 was set to 10 mm. The distance Y from the tip of the correction electrode 110 to the center of the capillary 121 was set to 5 mm. The distance Z2 from the downstream end 121a of the capillary 121 to the center of the correction electrode 110 was set to 10 mm. Although not shown in FIG. 18, the distance X1 from the axial center of the capillary 121 to the tip of the counter electrode 131 was set to 3 mm. Although not shown in FIG. 18, the distance from the axial center of the capillary 121 to the tip of the deflection electrode 150 was set to X3=10 mm.

[0210] 20A to 20C are diagrams showing experimental results in the eighth embodiment.

[0211] In the experiment, the current values ​​of the second current A2, the third current A3, and the fourth current A4 were measured when a voltage "V3" was applied to the correction electrode 110 by the third power supply 303. Note that no voltage was applied to the capillary 121, the counter electrode 131, or the deflection electrode 150. Note that the second current A2 is a current flowing between the capillary 121 and the correction electrode 110. Furthermore, the third current A3 is a current flowing between the counter electrode 131 and the correction electrode 110. Furthermore, as described above, the fourth current A4 is a current flowing between the correction electrode 110 and the deflection electrode 150. Hereinafter, the current value of the fourth current A4 will be referred to as the fourth current value as appropriate.

[0212] In the experiment, a contaminant (fluorine-based grease was used to simulate the contaminant) was applied to the tip of the deflection electrode 150, and the measurement results were compared for each amount of the applied contaminant. Note that the voltage and current (graphs G21a, G31, G41) when the amount of contaminant was "0 μL" in Figures 20A to 20C are the reference graphs for the second current A2 to the fourth current A4.

[0213] Figure 20A shows the second graph G2, Figure 20B shows the third graph G3, and Figure 20C shows the fourth graph G4.

[0214] The second graph G2 is a graph showing the relationship between the second current A2 and the voltage applied to the correction electrode 110. The horizontal axis of FIG. 20A represents the voltage applied to the correction electrode 110. However, the horizontal axis of FIG. 20A can also represent the voltage applied to the capillary 121, or the difference between the voltage applied to the capillary 121 and the voltage applied to the correction electrode 110, etc. In other words, the second graph G2 is a graph showing the relationship between the voltage applied to at least one of the capillary 121 and the correction electrode 110 and the second current A2.

[0215] The third graph G3 is a graph showing the relationship between the third current A3 and the voltage applied to the correction electrode 110. The horizontal axis of FIG. 20B represents the voltage applied to the correction electrode 110. However, the horizontal axis of FIG. 20B can also represent the voltage applied to the counter electrode 131, or the difference between the voltage applied to the correction electrode 110 and the voltage applied to the counter electrode 131. In other words, the third graph G3 is a graph showing the relationship between the voltage applied to at least one of the counter electrode 131 and the correction electrode 110 and the third current A3.

[0216] The fourth graph G4 is a graph showing the relationship between the fourth current A4 and the voltage applied to the correction electrode 110. The horizontal axis of FIG. 20C represents the voltage applied to the correction electrode 110. However, the horizontal axis of FIG. 20C can also represent the voltage applied to the deflection electrode 150, or the difference between the voltage applied to the correction electrode 110 and the voltage applied to the deflection electrode 150, or the like. In other words, the fourth graph G4 is a graph showing the relationship between the voltage applied to at least one of the correction electrode 110 and the deflection electrode 150 and the fourth current A4.

[0217] The results shown in FIGS. 20A to 20C were generated using the current values ​​of the second current A2, the third current A3, and the fourth current A4 obtained based on the conditions described in FIG.

[0218] 20A to 20C, graphs G21a, G31, and G41 plotted with white circles represent cases where the contamination amount is 0 μL. Graphs G22a, G32, and G42 plotted with triangles represent cases where the contamination amount is 3 μL. Graphs G23a, G33, and G43 plotted with "x" represent cases where the contamination amount is 6 μL.

[0219] In this embodiment, in order to observe changes in the graphs related to contamination (deterioration) of the deflection electrode 150, the first graph G1 (see FIG. 5A) that is unrelated to contamination of the deflection electrode 150 is omitted. In other words, the first graph G1 does not change whether the deflection electrode 150 is in a contaminated state or not.

[0220] As can be seen from the results in FIG. 20C, the fourth graph G4 decreases in accordance with the amount of contamination. This is because contamination reduces the conductivity of the surface of the deflection electrode 150, causing a decrease in the fourth current value. On the other hand, since there is no contamination on the capillary 121 or the counter electrode 131, as can be seen from FIGS. 20A and 20B, the changes in the second graph G2 and the third graph G3 are small. In other words, in the results shown in FIGS. 20A to 20C, the changes in the second graph G2 and the third graph G3 are small, while the changes in the fourth graph G4 are large. Based on these results, the control device 400 determines that deterioration of the deflection electrode 150 has occurred. Note that, because the current is unstable under low-voltage conditions, a reversal phenomenon occurs in the results shown in FIGS. 20A to 20C. Therefore, it is desirable to use the results on the high-voltage side (e.g., 6 kV or higher) to identify the location of deterioration.

[0221] Furthermore, in the eighth embodiment, the reference value stored in the measurement condition table 410 may be one point data on a reference graph. The reference graph is the graphs G21a, G31, and G41, which are graphs for a contamination amount of "0 μL." Alternatively, the reference value may be stored in the measurement condition table 410 as continuous profile data (i.e., the graphs G21a, G31, and G41 themselves) as shown in FIGS. 20A to 20C. In addition to the reference value, the measurement condition table 410 can store a threshold value used in determining deterioration, a correction value for the voltage value calculated during sample analysis, and the like.

[0222] FIG. 21 is a diagram showing a deterioration determination table in the eighth embodiment.

[0223] In FIG. 21, "G2" indicates the second graph G2 shown in FIG. 20A, "G3" indicates the third graph G3 shown in FIG. 20B, and "G4" indicates the fourth graph G4 shown in FIG. 20C.

[0224] The control device 400 performs the determination in steps S111, S112, and S121 in Fig. 6 according to the deterioration determination table. Such determination is easy for a person skilled in the art, so a flowchart for determining deterioration will be omitted.

[0225] In the eighth embodiment, the second graph G2 corresponds to the second current A2 flowing between the correction electrode 110 and the capillary 121. The third graph G3 corresponds to the third current A3 flowing between the correction electrode 110 and the counter electrode 131. The fourth graph G4 corresponds to the fourth current A4 flowing between the correction electrode 110 and the deflection electrode 150. In this way, the acquired results of the second current A2, the third current A3, and the fourth current A4 correspond to the respective current values ​​between the correction electrode 110 and an application target other than the correction electrode 110.

[0226] Furthermore, the eighth embodiment is based on the premise that the position of the correction electrode 110 changes between the time of deterioration determination and the time of sample analysis, as in the second embodiment. With this method, the possibility of deterioration of the correction electrode 110 can be ignored. Therefore, as shown in Fig. 21 , the determination results of the second graph G2 correspond one-to-one to the capillary 121, the determination results of the third graph G3 correspond one-to-one to the counter electrode 131, and the determination results of the fourth graph G4 correspond one-to-one to the deflection electrode 150.

[0227] As shown in FIG. 21, the deterioration of the capillary 121 and the counter electrode 131 can be determined even if the first current value is not acquired, and therefore the first graph G1 is omitted in the eighth embodiment.

[0228] Reference numeral 811 indicates a case where the rate of change of the second graph G2 is smaller than a predetermined value, the rate of change of the third graph G3 is smaller than a predetermined value, and the rate of change of the fourth graph G4 is smaller than a predetermined value. In such a case, the control device 400 determines that none of the capillary 121, the counter electrode 131, and the deflection electrode 150 has deteriorated. Thereafter, the rate of change of the second graph G2 is the rate of change of the second graph G2 relative to the second reference graph (graph G21a). The rate of change of the third graph G3 is the rate of change of the third graph G3 relative to the third reference graph (graph G31). And the rate of change of the fourth graph G4 is the rate of change of the fourth graph G4 relative to the fourth reference graph (graph G41). The fourth reference graph, graph G41, is the fourth graph G4 in the case where neither the correction electrode 110 nor the deflection electrode 150 has deteriorated.

[0229] Reference numeral 812 indicates a case where the rate of change of the second graph G2 is smaller than a predetermined value, the rate of change of the third graph G3 is smaller than a predetermined value, and the rate of change of the fourth graph G4 is larger than a predetermined value. In such a case, the control device 400 determines that the deflection electrode 150 has deteriorated.

[0230] Reference numeral 813 indicates a case where the rate of change of the second graph G2 is smaller than a predetermined value, the rate of change of the third graph G3 is larger than a predetermined value, and the rate of change of the fourth graph G4 is larger than a predetermined value. In such a case, the control device 400 determines that the counter electrode 131 and the deflection electrode 150 have deteriorated.

[0231] Reference numeral 814 represents a case where the rate of change of the second graph G2 is smaller than a predetermined value, the rate of change of the third graph G3 is larger than a predetermined value, and the rate of change of the fourth graph G4 is smaller than a predetermined value. In such a case, the control device 400 determines that the counter electrode 131 has deteriorated.

[0232] Reference numeral 815 indicates a case where the rate of change of the second graph G2 is greater than a predetermined value, the rate of change of the third graph G3 is less than a predetermined value, and the rate of change of the fourth graph G4 is less than a predetermined value. In such a case, the control device 400 determines that the capillary 121 is deteriorated.

[0233] Reference numeral 816 represents a case where the rate of change of the second graph G2 is greater than a predetermined value, the rate of change of the third graph G3 is smaller than a predetermined value, and the rate of change of the fourth graph G4 is greater than a predetermined value. The control device 400 determines that the capillary 121 and the deflection electrode 150 are deteriorated.

[0234] Reference numeral 817 represents a case where the rate of change of the second graph G2 is greater than a predetermined value, the rate of change of the third graph G3 is greater than a predetermined value, and the rate of change of the fourth graph G4 is less than a predetermined value. In such a case, the control device 400 determines that the capillary 121 and the counter electrode 131 have deteriorated.

[0235] Reference numeral 818 represents a case where the rate of change of the second graph G2 is greater than a predetermined value, the rate of change of the third graph G3 is greater than a predetermined value, and the rate of change of the fourth graph G4 is greater than a predetermined value. The control device 400 determines that all of the capillary 121, the counter electrode 131, and the deflection electrode 150 are deteriorated.

[0236] As described above, in the eighth embodiment, compared to the first to seventh embodiments, not only is the accuracy of determining the deterioration state of the application object improved, but the accuracy of determination can also be improved when multiple application objects are deteriorated.

[0237] In the eighth embodiment, if all of the change rates of the second graph G2 to the fourth graph G4 are equal to or less than the threshold, the corrected voltage is applied to the application target (S141 "Yes" → S151 in FIG. 6). If at least one of the change rates of the second graph G2 to the fourth graph G4 is greater than the threshold, the control device 400 proceeds to output an alert (S141 "No" → S142 in FIG. 6).

[0238] In the configuration of the eighth embodiment described above, the correction electrode 110 is provided, and a deflection electrode 150 is provided separately from the correction electrode 110. This deflection electrode 150 deflects (reference numeral 701 in FIG. 9 ) and reversely deflects (reference numeral 702 in FIG. 14 ) the ions N. The control device 400 then determines whether or not the target object has deteriorated based on the rate of change of the second graph G2, the rate of change of the third graph G3, and the rate of change of the fourth graph G4. With this configuration, it is possible to improve the accuracy of determining whether the target object has deteriorated, and to realize an ion source system 10d and a mass spectrometer 1 that can determine the deterioration of a plurality of target objects.

[0239] [Ninth embodiment] (with gas spray pipe 122) Next, a ninth embodiment of the present invention will be described with reference to Fig. 22. In the ninth embodiment, an ion source 100e having a gas spray tube 122 around a capillary 121 will be described.

[0240] Fig. 22 is a diagram showing the configuration of an ion source system 10e according to the ninth embodiment. For simplicity, in Fig. 22, the same components as those in Fig. 2 are denoted by the same reference numerals, and only the differences from Fig. 2 will be described.

[0241] Also, in Figure 22, the power supply 300 (first power supply 301 to third power supply 303), control device 400, first current measuring unit 141, and second current measuring unit 142 are omitted from the illustration, but in reality, these devices are installed as in Figure 2.

[0242] 22 is characterized in that a spray probe 120a has a concentric gas spray tube 122 outside a capillary 121. In the ion source 100e, a spray gas 902 is introduced between the capillary 121 and the gas spray tube 122, and the spray gas 902 is sprayed from a downstream end 122a of the gas spray tube 122. In this way, the ion source 100e shown in FIG. 22 is provided with the gas spray tube 122 for circulating the spray gas 902 around the capillary 121.

[0243] In ESI ion sources, a nebulizing gas 902 is typically used depending on the flow rate of the sample solution Q. During the ion generation process using an ESI ion source, droplets of the sample solution Q repeatedly split and eventually become very fine droplets that are ionized. When the flow rate of the sample solution Q introduced into the ESI ion source is high, neutral droplets, charged droplets, and other droplets may remain as droplets that were not sufficiently finely divided during the ionization process. In such cases, vaporizing or evaporating the charged droplets improves ionization efficiency. To evaporate these charged droplets, a nebulizing gas 902 sprayed from the gas nebulizing tube 122 is used. The flow rate of the nebulizing gas 902 is approximately 0.5 to 10 L / min. An inert gas such as nitrogen or argon is typically used as the nebulizing gas 902.

[0244] To further enhance the vaporization of charged droplets, etc., a method may be used in which heated gas (not shown: maximum temperature of approximately 800°C) is sprayed from a heated gas spray pipe (not shown) provided further outside the gas spray pipe 122. The flow rate of the heated gas is approximately 0.5 to 50 L / min, and like the spray gas 902, an inert gas such as nitrogen or argon is generally used.

[0245] The nebulizing gas 902 is suitable for achieving high sensitivity under conditions where the flow rate of the sample solution Q is relatively high. However, when the flow rate of the sample solution Q is high, the amount of liquid sprayed from the capillary 121 also increases. In such a case, even when the nebulizing gas 902 or the heating gas is sprayed, charged droplets and the like may remain without evaporating. This may accelerate deterioration due to contamination of the counter electrode 131 or the correction electrode 110. In such a case, the deterioration determination of the target object shown in the first to eighth embodiments is effective. By applying the ion source system 10e shown in the first to eighth embodiments to the ion source 100e shown in FIG. 22, the deterioration state of the target object can be determined.

[0246] It is desirable that the same voltage as that applied to the capillary 121 be applied to the gas spray tube 122 by the first power supply 301 .

[0247] According to the ninth embodiment described above, it is possible to realize an ion source system 10e and a mass spectrometer 1 that can determine whether an object to be applied has deteriorated even when the flow rate of the sample solution Q is high.

[0248] [Tenth embodiment] (without counter electrode 131) Next, a tenth embodiment of the present invention will be described with reference to Fig. 23. In the tenth embodiment, an ion source system 10f will be described in which the counter electrode 131 is omitted and an electric field for ionization is generated between the capillary 121 and the introduction electrode 132.

[0249] Fig. 23 is a diagram showing an ion source system 10f according to the tenth embodiment. For simplicity, in Fig. 23, the same components as in Fig. 2 are denoted by the same reference numerals, and only the differences from Fig. 2 will be described.

[0250] Also, in Figure 23, the power supply 300 (first power supply 301 to third power supply 303), control device 400, first current measuring unit 141, and second current measuring unit 142 are omitted from the illustration, but in reality, these devices are installed as in Figure 2.

[0251] 23 does not include the counter electrode 131 (see FIG. 2). Since the counter electrode 131 is omitted from the ion source 100f, an electric field for ionization is generated between the capillary 121 and the introduction electrode 132. In other words, the electrode in the claims is the introduction electrode 132.

[0252] When the flow rate of the sample solution Q is relatively small, the counter electrode 131 may not be necessary. However, if the counter electrode 131 is omitted, the gas 901 (see FIG. 2) is not sprayed in the direction opposite to the ion traveling direction, which may accelerate deterioration due to contamination of the introduction electrode 132. Therefore, it is effective to determine the deterioration state of the object to which the voltage is applied.

[0253] By applying the ion source system 10f shown in the first to eighth embodiments to the ion source 100f shown in FIG. 23, it is possible to determine the deterioration state of the target object.

[0254] In the tenth embodiment, the introduction electrode 132 plays the same role as the counter electrode 131 described above in generating the ions N.

[0255] According to the tenth embodiment described above, since the flow rate of the sample solution Q is small, it is possible to realize an ion source system 10f and a mass spectrometer 1 that can determine whether an object to be applied has deteriorated even when the counter electrode 131 is omitted.

[0256] [Eleventh embodiment] Next, an eleventh embodiment of the present invention will be described with reference to Fig. 24. In the first to tenth embodiments, a sample analysis is performed after a deterioration determination is performed. In contrast, in the eleventh embodiment, the control device 400 performs a deterioration determination while performing a sample analysis.

[0257] Fig. 24 is a flowchart showing the procedure of a degradation determination method according to the 11th embodiment. In Fig. 24, the same steps as in Fig. 6 are given the same step numbers, and only the differences from Fig. 6 will be explained.

[0258] First, in step S101a, the control device 400 performs sample analysis while calculating the rate of change in current value for determining deterioration.

[0259] If the rate of change of the first current A1 and the second current A2 is equal to or less than the predetermined threshold value in step S141 (S141→Yes), the control device 400 corrects the voltage (S151a) and then returns the process to step S101a. Note that step S151a is a control step in the claims.

[0260] After step S134, the control device 400 returns the process to step S101a.

[0261] The eleventh embodiment is an effective method when the voltage value applied to the target electrode during degradation determination is close to the voltage value applied to the target electrode during sample analysis. The eleventh embodiment is preferably performed when there is a high probability that the target electrode has not deteriorated. A case in which there is a high probability that the target electrode has not deteriorated is, for example, when the mass spectrometer 1 or the ion source system 10 is in a brand new state. When there is a high probability that the target electrode has not deteriorated, there is a low possibility that the analytical sensitivity will fluctuate.

[0262] According to the eleventh embodiment, deterioration determination is performed while sample analysis is being performed, thereby realizing a reduction in analysis time.

[0263] In the first to eleventh embodiments, the control device 400 determines whether or not there is deterioration in the capillary 121, the electrode (the counter electrode 131 or the introduction electrode 132), and the correction electrode 110 based on at least one of the changes in the first graph G1 and the changes in the third graph G3 and the changes in the second graph G2.

[0264] In the flowchart shown in FIG. 6, after step S152, the control device 400 may calculate the degree of progress of deterioration based on the transition of the rate of change of the graphs (first graph G1 to fourth graph G4).

[0265] [Comparative Example] Next, a comparative example will be described with reference to FIGS.

[0266] FIG. 25 is a diagram showing the configuration of a typical ion source system 10g.

[0267] In FIG. 25, the same reference numerals are used to denote the items already explained in FIG. 2, and the explanation thereof will be omitted.

[0268] In a typical ion source 100g, first, a sample solution Q is introduced into a capillary 121 through piping (not shown). Then, ions N or droplets are sprayed from a downstream end 121a of the capillary 121. When the ions N are generated, a voltage is applied to the capillary 121 by a power supply 300g. This generates an electric field between the introduction electrode 132 and the capillary 121. The sample solution Q is electrostatically sprayed by this electric field.

[0269] The sample solution Q is ionized in an ion source 100g and then introduced into a mass spectrometry unit 200 that is substantially in a vacuum.

[0270] Fig. 26 is a diagram showing another configuration (ion source system 10h) of the general ion source system 10g. In Fig. 26, the same components as those in Fig. 25 are given the same reference numerals, and only the differences from Fig. 25 will be described.

[0271] In the ion source 100h shown in Fig. 26, a counter electrode 131 is disposed in front of the introduction electrode 132. Then, a gas 901 is introduced between the introduction electrode 132 and the counter electrode 131. At this time, the gas 901 is sprayed from a hole 133 provided in the counter electrode 131 in a direction opposite to the ion traveling direction. This makes it possible to prevent excessive droplets from being introduced into the mass analysis unit 200 and to improve robustness. In the configuration shown in Fig. 26, ions N are generated by an electric field generated between the capillary 121 and the counter electrode 131.

[0272] In both the configuration shown in FIG. 25 and the configuration shown in FIG. 26, ions N generated in ion sources 100g and 100h are introduced into mass analysis section 200 through holes 134 provided in introduction electrode 132 and analyzed in mass analysis section 200.

[0273] In the mass spectrometer 1, deterioration of the capillary 121, the counter electrode 131, and the introduction electrode 132 causes a decrease in sensitivity and sensitivity fluctuations, which poses problems in terms of robustness, stability, and reproducibility.

[0274] It is also important to identify which of the capillary 121, the counter electrode 131, and the introduction electrode 132 has deteriorated. However, in the ion sources 100g and 100h shown in Figures 25 and 26, it is difficult to identify which of the capillary 121, the counter electrode 131, and the introduction electrode 132 has deteriorated.

[0275] Furthermore, by monitoring the actual amount of ions, it is possible to infer that any of the capillary 121, the counter electrode 131, and the introduction electrode 132 has deteriorated. However, this reduces throughput, and it is difficult to identify which of the capillary 121, the counter electrode 131, and the introduction electrode 132 has deteriorated.

[0276] The effects of the present invention can be achieved by combining the characteristic elements of the configurations of the ion source systems 10, 10a to 10f in each of the embodiments described above. Furthermore, while the experimental results show that the measured current decreases due to contamination, in actual use, the detected current value may increase due to damage to the surface of the target object, abnormal discharge due to contamination, or electric field concentration. Therefore, in practice, it is necessary to optimize the reference value, correction value, threshold value, etc. depending on the analysis conditions, target substance, etc.

[0277] Furthermore, the above-described configurations, functions, storage device 432, etc. may be partially or entirely implemented in hardware by, for example, designing them as integrated circuits. Furthermore, as shown in Fig. 3, the above-described configurations, functions, etc. may be implemented in software by a processor such as a CPU interpreting and executing a program that implements each function. Information such as the program, table, and file that implements each function can be stored in a recording device such as memory 420 or an SSD (Solid State Drive), or in a recording medium such as an IC (Integrated Circuit) card, an SD (Secure Digital) card, or a DVD (Digital Versatile Disc).

[0278] In addition, in each embodiment, the control lines and information lines shown are those that are considered necessary for explanation, and not all control lines and information lines in the product are necessarily shown. In reality, it can be considered that almost all components are interconnected. [Explanation of symbols]

[0279] 1 Mass spectrometer 2. Liquid chromatography equipment 10, 10a~10h Ion Source System 100, 100a~100h ion source 110 Correction electrode 121 Capillary 131 Counter electrode (electrode) 132 Introducing electrode (electrode) 141 first current measurement unit 142 Second current measurement unit 144 Fourth current measurement unit 150 Deflection electrode 170 Drive unit (moving part) 200 Mass spectrometry department 300,300d,300g power supply 301 First power source 302 Second Power Supply 303 Third Power Source 304 Fourth Power Source 400 Control device (control unit) 410,410a Measurement condition table 500,501~504 Peak 510 code (while the components to be analyzed are not eluted) 701 code (ions deflected towards the electrode) 702 sign (ions deflected towards the correction electrode) 801~805,811~818 code A1 First current A2 Second current A3 Third current A4 Fourth Current G1 First graph G11 Graph (first graph, base graph) G12 Graph (first graph) G13 Graph (first graph) G2 Second graph G21, G21a graphs (second graph, base graph) G22, G22a graph (second graph) G23, G23a graph (second graph) G3 Third graph G31 Graph (third graph, base graph) G32 graph (third graph) G33 graph (third graph) G4 Fourth graph G41 Graph (4th graph, base graph) G42 graph (fourth graph) G43 graph (fourth graph) N ions PL1 Deterioration judgment mode position PL2 Sample analysis mode position Q Sample solution Z Mass Spectrometer System S111: Determine whether the rate of change of the first graph is large (determination step) S112, S121 Determine whether the rate of change of the second graph is large (determination step) S131: Determine that the capillary has deteriorated, or that the counter electrode and correction electrode have deteriorated (determination step) S132 Deterioration of the opposing electrode is judged (judgment step) S133 Correction electrode deterioration judgement (judgment step) S134: No deterioration is determined (determination step) S142 Alert (control step) S151 Correct voltage and analyze sample (control step) S151a Voltage correction (control step)

Claims

1. an ion source; Control unit 1. An ion source system comprising: The ion source comprises: a capillary for spraying a sample solution; an electrode for generating an electric field for generating ions between the electrode and the capillary; a correction electrode disposed in a space in which the capillary and the electrode are installed; Equipped with The control unit Regarding the first graph, the second graph, and the third graph showing the relationship between voltage and current, determining whether or not the capillary, the electrode, and the correction electrode have deteriorated based on at least one of the changes in the first graph and the changes in the third graph and the changes in the second graph, and performing predetermined control; the first graph is a graph showing a relationship between a voltage applied to at least one of the capillary and the electrode, and a first current which is a current flowing between the capillary and the electrode due to discharge; the second graph is a graph showing a relationship between a voltage applied to at least one of the capillary and the correction electrode, and a second current which is a current flowing between the capillary and the correction electrode due to discharge, The third graph is a graph showing the relationship between a voltage applied to at least one of the electrode and the correction electrode, and a third current which is a current flowing between the electrode and the correction electrode due to discharge. Ion source system.

2. The control unit The presence or absence of deterioration in the capillary, the electrode, and the correction electrode is determined based on the amount of change in the first graph and the amount of change in the second graph.

10. The ion source system of claim 1.

3. The presence or absence of deterioration in the capillary, the electrode, and the correction electrode is determined based on the amount of change in the first graph, the amount of change in the second graph, and the amount of change in the third graph.

10. The ion source system of claim 1.

4. a deflection electrode for deflecting ions is installed separately from the correction electrode in a space in which the correction electrode is installed, The control unit The presence or absence of deterioration in the capillary, the electrode, and the deflection electrode is determined based on the amount of change in the second graph, the amount of change in the third graph, and the amount of change in a fourth graph which is a graph showing the relationship between a voltage applied to at least one of the correction electrode and the deflection electrode, and a fourth current which is a current flowing due to discharge between the correction electrode and the deflection electrode.

10. The ion source system of claim 1.

5. a moving unit that moves the correction electrode; The moving unit is In response to an instruction from the control unit, the distance between the correction electrode and the capillary during sample analysis is made larger than the distance between the correction electrode and the capillary during the determination.

10. The ion source system of claim 1.

6. a second power source that applies a voltage to the electrode; a third power source for applying a voltage to the correction electrode; Equipped with The control unit During sample analysis, the second power supply and the third power supply are controlled so that ions are deflected toward the electrodes.

10. The ion source system of claim 1.

7. The control unit According to the result of the determination, the voltage applied to the capillary, the electrode, and the correction electrode that are determined to be deteriorated during sample analysis is corrected as the predetermined control.

10. The ion source system of claim 1.

8. The voltage is corrected in accordance with the substance introduced into the ion source from the liquid chromatography device.

8. The ion source system of claim 7.

9. The voltage is corrected depending on the individual ion source system.

8. The ion source system of claim 7.

10. a second power source that applies a voltage to the electrode; a third power source for applying a voltage to the correction electrode; Equipped with a substance is introduced into the ion source from a liquid chromatography device; The control unit controlling the second power supply and the third power supply so that ions are deflected toward the correction electrode while no analyte components are eluted from the liquid chromatography device; 10. The ion source system of claim 1.

11. The control unit The determination is carried out in a pre-process of sample analysis.

10. The ion source system of claim 1.

12. The control unit The determination is made while the sample is being analyzed.

10. The ion source system of claim 1.

13. an ion source; a mass spectrometry unit that performs mass spectrometry on the substances ionized by the ion source; A control unit; A mass spectrometry system comprising: The ion source comprises: a capillary for spraying a sample solution; an electrode for generating an electric field for generating ions between the electrode and the capillary; a correction electrode disposed in a space in which the capillary and the electrode are installed; Equipped with The control unit Regarding the first graph, the second graph, and the third graph showing the relationship between voltage and current, determining whether or not the capillary, the electrode, and the correction electrode have deteriorated based on at least one of the changes in the first graph and the changes in the third graph and the changes in the second graph, and performing predetermined control; the first graph is a graph showing a relationship between a voltage applied to at least one of the capillary and the electrode, and a first current which is a current flowing between the capillary and the electrode due to discharge; the second graph is a graph showing a relationship between a voltage applied to at least one of the capillary and the correction electrode, and a second current which is a current flowing between the capillary and the correction electrode due to discharge, The third graph is a graph showing the relationship between a voltage applied to at least one of the electrode and the correction electrode, and a third current that is a current that flows due to discharge between the electrode and the correction electrode. Mass spectrometry system.

14. an ion source; Control unit 1. An ion source system comprising: The ion source comprises: a capillary for spraying a sample solution; an electrode for generating an electric field for generating ions between the electrode and the capillary; a correction electrode disposed in a space in which the capillary and the electrode are installed; Equipped with The control unit Regarding the first graph, the second graph, and the third graph showing the relationship between voltage and current, a determining step of determining whether or not the capillary, the electrode, and the correction electrode are deteriorated based on at least one of the changes in the first graph and the changes in the third graph and the changes in the second graph; a control step of performing predetermined control; Run the first graph is a graph showing a relationship between a voltage applied to at least one of the capillary and the electrode, and a first current which is a current flowing between the capillary and the electrode due to discharge; the second graph is a graph showing a relationship between a voltage applied to at least one of the capillary and the correction electrode, and a second current which is a current flowing between the capillary and the correction electrode due to discharge, The third graph is a graph showing the relationship between a voltage applied to at least one of the electrode and the correction electrode, and a third current which is a current flowing between the electrode and the correction electrode due to discharge. Deterioration judgment method.

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