JP4635722B2 - Quadrupole electrode unit, electrode structure and manufacturing method thereof - Google Patents

Description

  The present invention relates to a quadrupole electrode unit used in a quadrupole mass spectrometer, an electrode structure constituting the electrode unit, and a method for manufacturing the same.

(Conventional technology)
Mass spectrometers can analyze substances with high accuracy and quantitatively, so they can analyze pollutants in the atmosphere (VOC, dioxins, SOx, NOx, etc.) and harmful components (nitrogen compounds, dioxins in water or soil). Etc.) are widely used. The mass spectrometer is usually used in combination with a gas chromatograph (gas chromatograph) in the case of atmospheric gas analysis, and is used in combination with a liquid chromatograph (liquid chromatograph) in the case of component analysis in water or soil. However, since these analyzers are large and heavy, they cannot be easily carried, and are usually installed in laboratories. For this reason, there is a concern that the reliability of the analysis is lowered, for example, the sampling sample is deteriorated in the process of bringing the sample sampled in the field back to the place where the analyzer is installed.

  Under these circumstances, technology development to make the analyzer itself “portable” that can be carried to the field is being promoted all over the world. Currently, with regard to gas chromatography and liquid chromatography, small wafer-sized devices have been developed using semiconductor process technology and are now on the market. In recent years, a pollutant monitoring system concept has been proposed that further reduces the size of the analyzer to a chip size and connects these chips via a network to identify the distribution status of pollutants and the source of pollutants in a wide area. Yes. In order to realize such a concept, it is necessary to achieve both high accuracy and miniaturization of the analyzer.

  FIG. 1 is a schematic perspective view showing a configuration of a main part of a conventional quadrupole mass spectrometer. The quadrupole mass spectrometer 11 includes an ionization unit 12 that ionizes gas molecules incident on the apparatus, a quadrupole electrode 13 that selectively separates the ionized gas according to its mass, and an ionized gas that has passed through the quadrupole electrode 13. And a power supply 15 for applying a high-frequency voltage to the quadrupole electrode 13.

  The quadrupole electrode 13 for performing mass spectrometry is composed of four parallel rod-like electrode elements 16 which are connected in parallel as shown in FIG. 1, and a DC voltage and an AC voltage are superimposed on each of them. Apply what you did. That is, assuming that the DC voltage is U and the AC voltage is V (t) = Vmax · cos (2πft), in the example of FIG. 1, a voltage of U + Vmax · cos (2πft) is applied to the pair of electrodes 16 facing left and right. Then, a voltage of −U−Vmax · cos (2πft) is applied to the pair of electrodes 16 that are vertically opposed to each other. However, Vmax is the maximum value of AC voltage, f is the frequency of AC voltage, and t is time. Due to such electrode arrangement and applied voltage, the electric field in the quadrupole electrode 13 becomes a hyperbolic electric field.

  The electrode 16 constituting the quadrupole electrode 13 is ideally manufactured so that the cross section has a hyperbolic shape, but most of the electrodes are approximated in a circular shape due to difficulty in manufacturing. The optimum design for approximating the hyperbolic electric field with the electrode 16 having a circular cross section is R = 1.148 ro. As shown in FIG. 2, R is the radius (electrode diameter) of the electrode element 16, and ro is the minimum radius from the central axis of the quadrupole electrode 13 to the electrode element 16.

  The principle of mass spectrometry using the quadrupole electrode 13 is as follows. However, the z-axis is taken in a direction parallel to the axial direction of each electrode element 16, the x-axis is taken in a direction connecting a pair of opposed electrode elements 16 in a cross section perpendicular to the axial direction of the electrode element 16, and the other opposing face The y axis is taken in the direction connecting the electrodes 16. The gas ionized by the ionization unit 12 that is an ion source enters the quadrupole electrode 13. Incident ions are subjected to forces in the x-axis direction and the y-axis direction by the electric field formed in the quadrupole electrode 13 while traveling in the z-axis direction parallel to the quadrupole electrode 13. When a voltage obtained by superimposing a DC voltage U and an AC voltage V (t) = Vmax · cos (2πft) is applied to the four electrodes 16, the quadrupole electrode 13 is connected by both voltages U and V (t). The ratio M / Z of the mass number M of ions that can pass through and the valence number Z of ions is determined. When the electric field is adjusted to select certain types of ions, if the ions deviate from the central axis of the quadrupole electrode 13, a force to pull back to the central axis acts. By such an action, incident ions pass through the quadrupole electrode 13 while drawing a spiral trajectory. On the other hand, when other types of ions deviate from the central axis of the quadrupole electrode 13, the amplitude in the direction orthogonal to the z-axis direction is increased and finally captured by the electrode 16.

The resolution ΔM of the ion mass number measurement by the quadrupole electrode 13 can be evaluated by the following equation (1). Here, Kz represents the kinetic energy of ions in the z direction, f represents the frequency of the alternating voltage applied to the electrode 16, and L represents the length of the electrode 16.

On the other hand, the maximum value Vmax of the alternating voltage V (t) applied to the electrode 16 can be evaluated by the following equation (2). Here, Mmax represents the maximum mass number of ions to be detected.

  From these equations, it can be seen that the applied voltage can be reduced by reducing the size of the electrode element 16 (electrode diameter R and electrode length L). On the other hand, when the size of the electrode 16 is reduced, the resolution of the mass spectrometer 11 is lowered. As shown in FIG. 2, the conventional electrode element 16 has an electrode diameter R = 2.5 mm (accordingly, ro = 2.177 mm) and an electrode length L = 10 cm. For example, the maximum mass number Mmax = 100 amu. Then, the maximum applied voltage Vmax is about 1.1 kV. However, the AC frequency f is 4 MHz. The resolution ΔM is about 0.05 amu.

  For example, in the mass spectrometer described in Patent Document 1 (Japanese Patent Application Laid-Open No. 11-503557), a glass fiber coated with a metal material is used as an ultrafine electrode, and four electrodes are formed by a semiconductor process. A quadrupole electrode having a diameter of 0.5 mm is manufactured with high precision positioning. In this case, the maximum applied voltage can be 20 V or less. However, when the electrode length is shortened by the same ratio as the electrode diameter, the resolution becomes 5 amu or less and the analysis accuracy deteriorates. In order to make the resolution within 1 amu, the electrode length needs to be 20 mm or more. Thus, in order to ensure the resolution above a certain level, a certain length of electrode length is required, which makes it difficult to miniaturize the electrode beyond the current level.

  Patent Document 2 (Japanese Patent Laid-Open No. 8-148087) discloses a manufacturing technique for improving resolution by producing an electrode having a hyperbolic section. In this method, an electrode having a high dimensional accuracy is manufactured by an electroforming technique using a mold having a groove whose cross section is recessed along a hyperbola.

  However, in the mass spectrometer described in the above-mentioned Patent Document 1, an electrode is formed by utilizing glass fiber, and a commercially available glass fiber itself is used. In general, the diameter of glass fiber can be reduced by stretching molten glass. However, it is difficult to control the cross-sectional shape, and when the electrode is miniaturized, the shape accuracy of the electrode cannot be obtained. In particular, it is difficult to form a long electrode with a uniform cross-sectional shape.

  In addition, the above-mentioned Patent Document 2 discloses a technique for controlling the cross-sectional shape of the electrode to a hyperbolic shape with high accuracy. However, the manufactured electrode is assembled by screwing, and the electrode is miniaturized. Is not considered.

  In addition, the difficulty common to the above two methods is that even if a minute electrode can be produced, it becomes difficult to handle the electrode as the electrode diameter becomes minute, and even if extreme care is taken, the electrode is damaged. It is difficult to prevent deformation.

  Furthermore, as another problem, there is a case where mass production and cost are not studied in the above method. In order to use it as a pollutant monitoring system, it is necessary to supply a large number of chips at low cost. Although the method disclosed in Patent Document 1 can be used for research purposes, it is necessary to position and fix the electrodes one by one on the silicon substrate with high accuracy, and is not suitable for mass production. Moreover, the electroforming technique proposed in Patent Document 2 is based on the principle of electrical deposition, and it takes a lot of time to manufacture one electrode. For example, even when an electrode having a thickness of 100 μm is manufactured, it takes about half a day.

Japanese Patent Laid-Open No. 11-503557 JP-A-8-148087

  The present invention has been made in view of the technical problems as described above, and an object of the present invention is to provide a quadrupole electrode unit for a mass spectrometer capable of miniaturizing and improving the accuracy of an electrode element and its The object is to provide an electrode structure. Another object of the present invention is to provide a method of manufacturing an electrode structure for a mass spectrometer capable of mass production and cost reduction.

A quadrupole electrode unit according to the present invention is a quadrupole electrode unit for generating an electric field potential in a quadrupole mass spectrometer, and includes a support portion and an electrode element having at least a surface made of a conductive material. In addition , four electrode elements are arranged in a quadrupole by combining a plurality of electrode structures in which the shape component part of the electrode element and the support part are integrally formed of the same material .

In the quadrupole electrode unit according to the present invention, the electrode element constituting the quadrupole electrode is finely formed because the shape component part of the electrode element is integrally formed on the support part of the electrode structure by the same material. Even if the length becomes longer or the length becomes longer, the electrode is less likely to be deformed or damaged. Therefore, even when the electrode is miniaturized, it is easy to handle the case of combining the electrodes into a quadrupole electrode unit or incorporating the quadrupole electrode unit into a mass spectrometer. The unit can be miniaturized and the accuracy and reliability of the quadrupole electrode unit can be improved.

  In an embodiment of the quadrupole electrode unit according to the present invention, the electrode structure is one in which one electrode element is formed on the surface of the support portion, and the four electrode structures are combined by combining the four electrode structures. The four electrodes are arranged in a quadrupole so as to be substantially parallel to each other. According to this embodiment, since one electrode element is provided in one electrode structure, the design and manufacture of the electrode structure are facilitated.

  The electrode structure in another embodiment of the quadrupole electrode unit according to the present invention is one in which the two electrode elements are formed on the surface of the support portion, and the two electrode structures are combined. The four electrodes are arranged in a quadrupole so as to be substantially parallel to each other. According to this embodiment, since two electrode elements are provided in one electrode structure, the number of parts of the quadrupole electrode unit can be reduced, and the cost can be reduced.

  In another embodiment of the quadrupole electrode unit according to the present invention, a spacer for keeping a distance between the electrode elements at a predetermined distance is interposed between the electrode structures. According to such an embodiment, since the electrode structures can be positioned automatically, the positioning process of the electrode structures can be simplified.

  In another embodiment of the quadrupole electrode unit according to the present invention, the ion incident side is maintained while maintaining a constant ratio between the sectional area of the electrode element and the sectional area of the ion passage region formed between the electrode elements. The electrode is formed so that the intensity of the electric field formed at the center of the ion passage region gradually increases from the ion incident side toward the ion emission side by gradually reducing the cross-sectional area of the electrode element from the ion incident side toward the ion emission side. A child is constituted. According to such an embodiment, a large number of ions can be taken into the ion passage area opening on the wide ion incident side, and ions can be spatially concentrated in the ion passage area opening on the ion emission side.

The electrode structure according to the present invention is an electrode structure used in the quadrupole electrode unit according to the present invention, and includes a support portion and an electrode element having at least a surface made of a conductive material. The shape component part and the support part are integrally formed of the same material .

In the electrode structure according to the present invention, since the shape component part of the electrode is integrally formed on the support portion with the same material , the electrode constituting the quadrupole electrode becomes finer or its length. Even if the length of the electrode is increased, the electrode is not easily deformed or damaged. Therefore, even when the electrode is miniaturized, it is easy to handle when the electrode structure is combined into a quadrupole electrode unit, or when the electrode structure is incorporated into the mass spectrometer. It is possible to reduce the size of the object and improve the accuracy and reliability of the electrode structure.

In an embodiment of the electrode assembly according to the present invention, the electrode in the form of a rod is integrated with the support portion. This support portion is preferably formed of a conductive material. According to this embodiment, since the electrode element can be integrated with the support portion, the electrode structure can be easily manufactured.

Another embodiment of the electrode structure according to the present invention is such that a rod-shaped protrusion which is a shape constituting part of the electrode element is integrally formed on the support portion, and a film-like conductive film is formed on the surface of the protrusion. The electrode is formed by forming a conductive material . It is desirable that the support portion and the protrusion are formed of an insulating material. According to this embodiment, the support portion and the electrode can be formed of different materials. Therefore, for example, mass production is possible by forming the support portion into a predetermined shape with a synthetic resin or the like.

  The electrode element in yet another embodiment of the electrode element structure according to the present invention has a circular arc or hyperbolic surface in a cross section perpendicular to the length direction. According to this embodiment, since the surface of the cross section of the electrode has an arc shape or a hyperbola shape, a good quadrupole field can be generated between the four electrodes arranged in the quadrupole. .

  Yet another embodiment of the electrode structure according to the present invention is characterized in that the cross-sectional area of the electrode is uniform over its length direction. According to such an embodiment, the shape of the electrode is simplified and the manufacture is facilitated.

  In yet another embodiment of the electrode assembly according to the present invention, the cross-sectional area of the electrode assembly gradually decreases from one end to the other end. According to this embodiment, when a plurality of on-electrode structures are arranged so that the four electrodes are arranged in a quadrupole arrangement, a large number of ions are taken into the ion passage area opening on the wide ion incident side, It is possible to concentrate ions spatially at the exit side ion passage area opening.

The first manufacturing method of the electrode structure according to the present invention manufactures an electrode structure in which an electrode element for generating an electric field potential and a support portion are integrally formed of a conductive material in a quadrupole mass spectrometer. For forming a mold having a groove whose cross section perpendicular to the length direction has an arc shape or a hyperbolic shape, and forming the support portion by the mold using an electroforming method. by the groove at the same time it is characterized in that the Denkyokuko and a step of integrally molded with the support portion.

According to the first manufacturing method, since the electrode structure in which the electrode element is integrally formed on the support portion can be manufactured, even if the electrode element becomes fine or the length thereof becomes long, It is difficult for the electrode to be deformed or to be damaged, and handling of the electrode becomes easy. In addition, since the support portion and the electrode are produced by electroforming, it is possible to produce an electrode having a circular or hyperbolic cross section with high precision, and miniaturization of the electrode (for example, nanoscale) Production of an electrode element).

  An embodiment of the first manufacturing method of the electrode structure according to the present invention is characterized in that the mold is manufactured by a photolithography technique. In such an embodiment, since the molding die for molding the electrode structure is produced by the photolithography technique, the shape of the electrode (arc shape or hyperbolic shape) can be formed with nanometer accuracy. .

The second manufacturing method of the electrode structure according to the present invention includes a support part and an electrode element whose surface is made of a conductive material, and the shape component part of the electrode element and the support part are integrated by an insulating material. A method for producing a molded electrode structure for a quadrupole electrode unit, the step of producing a mother die having a convex part having the same shape as the electrode, and electroforming using the mother die by law, the electrode and the step of producing a mold, the same time by the grooves when molding the mold in I Ri before Symbol support portion having a groove cross section perpendicular to the arc-shaped or hyperbolic shape in the longitudinal direction A step of integrally forming a protrusion, which is a shape component of the child, with the support portion; and a step of forming the electrode by conducting the surface of the protrusion with a conductive material. Yes.

According to the second manufacturing method, since the electrode structure in which the shape component of the electrode element is integrally formed on the support portion can be manufactured, the electrode element becomes finer or the length thereof becomes longer. Even so, it is difficult for the electrode to be deformed or to be damaged, and handling of the electrode becomes easy. In addition, since it takes time to obtain a required thickness in the electroforming method, if the electrode structure is produced by the electroforming method, the production efficiency of the electrode structure may be reduced. According to the second manufacturing method, once a mold is produced by electroforming based on the mother mold, a support portion is formed by a duplication technique using the mold, and the protrusions are formed by conducting treatment. Since it is only necessary to form the electrode element only on the surface, the production efficiency of the electrode structure can be improved. Further, according to the conductive treatment, the power required for producing the electrode can be much smaller than that of the electroforming method, and the electrode can be produced at a low cost.

A third manufacturing method of an electrode structure according to the present invention includes a support portion and an electrode element whose surface is made of a conductive material, and the shape component portion of the electrode element and the support portion are integrally formed of an insulating material. A method for producing an electrode structure for a quadrupole electrode unit , wherein a mother mold in which two convex portions having the same shape as the electrode element are formed adjacent to each other, and the mother shaped by electroforming method using a mold, a step of preparing a mold having two grooves perpendicular cross section is an arc shape or hyperbolic shape in the longitudinal direction, said casting mold by Ri before Symbol support portion then simultaneously the you integrally molded with said support two adjacent projections where a shape component of the Denkyokuko by grooves process, the surface of each projection between the projection while keeping an insulating state Engineering of forming the Denkyokuko with electroconductive treatment of a conductive material It is characterized by comprising and.

According to the third manufacturing method, since the electrode structure in which the shape component of the electrode element is integrally formed on the support portion can be manufactured, the electrode element becomes finer or the length thereof becomes longer. Even so, it is difficult for the electrode to be deformed or to be damaged, and handling of the electrode becomes easy. In addition, since it takes time to obtain a required thickness in the electroforming method, if the electrode structure is produced by the electroforming method, the production efficiency of the electrode structure may be reduced. According to the second manufacturing method, once a mold is produced by electroforming based on the mother mold, a support portion is formed by a duplication technique using the mold, and the protrusions are formed by conducting treatment. Since it is only necessary to form an electrode on the surface, the production efficiency of the electrode structure can be improved. Further, according to the conductive treatment, the power required for electrode production can be much smaller than that of the electroforming method, and the electrode can be produced at low cost. Furthermore, since two electrodes can be produced at a time, the manufacturing cost for obtaining the required number of electrodes is also reduced.

  In addition, the component demonstrated above of this invention can be combined arbitrarily as much as possible.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following examples, and can be appropriately changed in design without departing from the spirit of the present invention.

  FIG. 3 is a perspective view showing the structure of the quadrupole electrode unit 21 according to the first embodiment of the present invention. FIG. 4 is a perspective view showing an electrode block 22 (electrode structure) constituting the quadrupole electrode unit 21. However, FIG.3 and FIG.4 is the figure which represented the Example of this invention typically, Comprising: The dimensional ratio of a support part and an electrode element is not represented correctly. The same applies to the drawings after FIG.

  As shown in FIG. 3, the quadrupole electrode unit 21 according to the first embodiment is composed of four minute electrode blocks 22, and rod-shaped electrode elements 23 provided at the end of the surface of each electrode block 22. Are arranged close to each other in parallel to form a quadrupole electrode. These four electrode elements 23 are arranged in quadrupoles at equal intervals vertically and horizontally, and an ion passage region 24 is formed between them. Further, the pair of diagonally opposed electrode blocks 22 are electrically connected so as to have the same potential, and between the pair of diagonally opposed electrode blocks 22 and another pair of electrode blocks 22 diagonally opposed. Is connected to a power source 26, and a DC voltage U and an AC voltage V (t) = Vmax · cos (2πft) are applied by the power source 26 in a superimposed manner. However, Vmax and f are the amplitude and frequency of an alternating voltage, and t is time.

  As shown in FIG. 4, the electrode block 22 is formed by integrally projecting a rod-shaped electrode element 23 over the entire length of an end of a support portion 25 having a rectangular parallelepiped shape. The electrode block 22 is formed in a very small size. For example, the length of the support part 25 and the electrode element 23 is L = 400 μm, the height of the support part 25 is 500 μm, and the protruding height of the electrode element 23 is d = 1 μm. It has become. The electrode 23 and the support portion 25 (that is, the entire electrode block 22) are integrally formed of a conductive material such as a metal such as Cu or Ni. Moreover, the electrode element 23 has a uniform cross-sectional shape along the length direction, and the external shape of the cross section perpendicular | vertical to a length direction is circular arc shape or a hyperbola shape.

  As shown in FIG. 3, the four electrode blocks 22 are arranged such that the electrode elements 23 are brought close to each other with a predetermined interval, and an ion passage region 24 is formed therebetween. These electrode blocks 22 are assembled by bonding the support portions 25 to each other with an insulating adhesive. Or you may assemble by fixing the support part 25 to a flame | frame etc. Even in that case, since the surface opposite to the surface on which the electrode element 23 of the support portion 25 is provided and both side surfaces are flat, each electrode block 22 is positioned with high precision and easily assembled.

  Such a quadrupole electrode unit 21 is used as a quadrupole mass spectrometer (see FIG. 1) by including an ionization unit and an ion detection unit. In the mass spectrometer, a power source 26 is connected to each electrode block 22 as shown in FIG. 3, and a DC / AC superimposed voltage U + V (t) = U + Vmax · cos (from the power source 26 to the quadrupole electrode unit 21). When 2πft) is applied, a quadrupole electric field (vibration field) is generated in the ion passage region 24 between the electrodes 23. Then, when ions generated in the ionization section are sent to the ion passage area 24, only specific ions α pass through the ion passage area 24 of the quadrupole electrode unit 21 as shown in FIG. , Γ and the like are discharged from between the electrode blocks 22 to the outside. That is, as described in the conventional example, the ion α corresponding to the ratio M / Z of the ion mass number M and the ion valence Z determined by the DC voltage U and the AC voltage V (t) of the power source 26 is Then, it travels through the ion passage area 24 while drawing a spiral trajectory and passes through the quadrupole electrode unit 21. On the other hand, when other ions β, γ, etc. deviate from the central axis of the quadrupole electrode unit 21, they receive a lateral force by the electric field formed in the quadrupole electrode unit 21, and the electrode block 22 Pop out from the gap between them. Therefore, the mass of the ions can be measured from the ionic valence of the passing ions detected by the ion detector. Alternatively, only predetermined ions can be selected and passed.

  This quadrupole mass spectrometer is also used as a gas purification device. FIG. 6 is a schematic view showing a gas purification apparatus using the quadrupole electrode unit 21. In FIG. 6, reference numeral 27 is a vacuum chamber, 28 is an ionization section, 29 is an ionization electrode, 30 is an exhaust gas chamber, 31 is a purified gas storage chamber, 32 is a gas recovery pipe, and a quadrupole electrode is provided in the exhaust gas chamber 30. A unit 21 is installed. The vacuum chamber 27 and the ionization unit 28 communicate with each other, the ionization unit 28 and the purified gas storage chamber 31 are connected via the quadrupole electrode unit 21, and the exhaust gas chamber 30 and the vacuum chamber 27 are connected to the gas recovery pipe 32. Communicated by A plurality of types of mixed gases G1, G2, and G3 are held in the vacuum chamber 27, and the quadrupole electrode unit 21 is adjusted so that only the ionized gas G1 can pass therethrough.

  Accordingly, the gases G1, G2, and G3 in the vacuum chamber 27 are heated by the ionization electrode 29 in the ionization unit 28, and emit electrons (e−) to be ionized. When the ionized gases G1, G2, G3 flow through the quadrupole electrode unit 21, only the gas G1 can pass through the quadrupole electrode unit 21, so that only a specific gas G1 is present in the purified gas storage chamber 31. It accumulates separately. On the other hand, the other gases G2 and G3 are ejected from the quadrupole electrode unit 21 into the exhaust gas chamber 30 by jumping out from the gap between the electrode blocks 22, and are recovered into the vacuum chamber 27 again through the gas recovery pipe 32. The Therefore, only a specific kind of gas in the vacuum chamber 27 is separated and purified and stored in the purified gas storage chamber 31.

  For quadrupole electrodes used in mass spectrometers, etc., the applied voltage can be reduced by reducing the size of the electrode, but the resolution of the mass spectrometer decreases as the size of the electrode is reduced. To do. Therefore, in order to make the mass spectrometer portable so that it can be used at a low voltage and to achieve high accuracy, it is necessary to reduce the radius of the electrode element and increase the length of the electrode element. In this case, if the electrode 16 is a rod-like electrode 16 like the electrode 16 of the conventional example, the electrode 16 is deformed or damaged when the electrode 16 is thinned and elongated to increase the aspect ratio of the electrode 16. And handling becomes difficult. It is also difficult to assemble the quadrupole electrode by positioning the four electrode elements 16 in parallel with each other.

  On the other hand, in the case of the present invention, the electrode element 23 having a circular arc shape or a hyperbolic cross section is formed integrally with the block-shaped support portion 25, and the analysis space (ion passage region 24) of the electrode block 22 is formed. Since the region that is not involved in the formation of the electric field is formed into a block shape, the electrode element 23 is reinforced by the support portion 25, and the strength of the electrode block 22 is reduced even if the electrode element 23 is miniaturized and elongated. There is no. Further, by gripping the support portion 25, the electrode block 22 can be handled without directly touching the analysis surface (electrode 23), and handling of the electrode 23 is facilitated. Further, since the electrode element 23 can be assembled by the support portion 25, the quadrupole electrode unit 21 can be assembled with high positional accuracy. Therefore, according to the present invention, it is possible to manufacture the electrode block 22 having a small electrode 23, high strength, and easy handling, and thus a portable or portable high-precision quadrupole mass spectrometer. Etc. can be realized. Generally, the transfer accuracy by the electroforming technique is 50 nm to 100 nm. Therefore, when forming the electrode 23 using the electroforming technique, a nanometer-sized quadruple having a precise arc shape or a hyperbolic shape is used. An electrode can be formed.

  Next, an example of a manufacturing method of the quadrupole electrode unit 21 will be described with reference to FIGS. First, as shown in FIG. 7A, a photosensitive resin material is applied to the surface of a substrate 41 such as a silicon substrate or a glass substrate with a uniform thickness by a dip coating method or a spin coating method to form a resin layer 42. Form. Next, the resin layer 42 is exposed and developed using photolithography technology and patterned to form grooves 43 in the resin layer 42 so that the cross section has an arc shape or a hyperbolic shape. As a result, as shown in FIG. 7B, a resin layer 42 having a plurality of grooves 43 is formed on the substrate 41, and a molding die 44 including the substrate 41 and the resin layer 42 is produced. By forming the groove 43 in the mold 44 using the photolithography technique in this way, the distortion of the quadrupole analysis surface in the electrode 23 that is finally manufactured can be minimized.

  Next, after conducting a conductive treatment on the surface of the resin layer 42 by vapor deposition, sputtering, chemical plating, hot dipping, or the like, a metal material is deposited on the resin layer 42 by an electroforming technique to form a film. A plurality of electrode elements 23 are formed by grooves 43 on the lower surface of the electroformed film. At this time, if the thickness of the electroformed film is sufficiently thick so that the electrode element 23 is not deformed, the strength of the electroformed film (support portion 25) is improved, so that the deformation of the finally obtained electrode analysis surface is small. Therefore, highly accurate analysis becomes possible. When the electroformed film grows to a predetermined thickness, the energization is stopped and the electroforming process is terminated. When this electroformed product is peeled from the mold 44, a metal block 45 made of an electroformed product as shown in FIG. 7C is obtained. Since a plurality of electrode elements 23 are formed in the metal block 45, the metal block 45 is diced for each electrode element 23 to obtain a plurality of electrode blocks 22 having a predetermined shape. At the end of the upper surface of each electrode block 22 obtained in this way, an electrode element 23 is formed by a groove 43 as shown in FIG.

  The four electrode blocks 22 having the same shape thus obtained are arranged and fixed at predetermined positions as shown in FIG. In that case, for example, while observing an optical microscope or a scanning electron microscope, it is positioned and fixed using a micromanipulator or the like.

  In the manufacturing method as described above, since the electrode block 22 is produced by using both the electroforming method and the photolithography technique, it is possible to produce the highly accurate arc-shaped or hyperbolic electrode element 23. . In particular, since the transfer accuracy by electroforming technology is generally 50 nm to 100 nm, it is possible to form a hyperbolic shape with nanometer accuracy by the technology, and processing at the nano level can also be performed by photolithography technology. Therefore, according to the above method, it is possible to mass-produce quadrupole electrodes having nanometer-sized electrode elements 23 at low cost.

  In order to assemble the quadrupole electrode unit 21 by using the four electrode blocks 22, it may be precisely assembled by using a micromanipulator or the like as described above. . In order to simplify the position adjustment, for example, a spacer may be interposed between the electrode blocks 22. FIG. 8 is an exploded perspective view showing an example, in which an insulating film 46 having a predetermined thickness is sandwiched between the upper and lower electrode blocks 22 and the left and right electrode blocks 22 as spacers. In this embodiment, since the electrode element 23 protrudes at the end of the upper surface or the lower surface of the support portion 25, the insulating film 46 sandwiched between the upper and lower electrode blocks 22 is slightly larger than twice the protrusion length d of the electrode element 23. A material having a large thickness is used. The insulating film 46 sandwiched between the left and right electrode blocks 22 is thinner than the insulating film 46 sandwiched between the upper and lower electrode blocks 22.

  FIG. 9 shows an insulating microsphere 47 (for example, glass beads or ceramic beads) having a predetermined size sandwiched between the upper and lower electrode blocks 22 and the left and right electrode blocks 22 as spacers. Also in this case, the diameter of the microsphere 47 sandwiched between the upper and lower electrode blocks 22 is slightly larger than twice the protruding length d of the electrode element 23. The diameter of the microsphere 47 sandwiched between the left and right electrode blocks 22 is smaller than the diameter of the microsphere 47 sandwiched between the upper and lower electrode blocks 22.

  In order to further improve the positioning accuracy of the electrode block 22, it is preferable to form a spacer by forming an insulating film 48 on the electrode block 22 with an insulating material as shown in FIG.

  If the spacer is sandwiched between the electrode blocks 22 in this way, the positioning can be automatically performed without observing with an optical microscope or the like. That is, the electrode block 22 sandwiched between the spacers is clamped with a vise and positioned, and fixed in that state with an adhesive, whereby the quadrupole electrode unit 21 can be completed, and the electrode blocks 22 are positioned with each other. Can be made easier.

  FIG. 11 is a perspective view showing a quadrupole electrode unit 51 according to Embodiment 2 of the present invention. Also in this embodiment, the four minute electrode blocks 22 on which the electrode elements 23 are formed are arranged in the same manner as in the first embodiment. The electrode block 22 is different in structure from the first embodiment.

  In this electrode block 22, a rod-shaped protrusion 53 is integrally formed and protruded over the entire length of the support portion 52 formed of an insulating material such as synthetic resin or ceramic. The protrusion 53 has a uniform cross-sectional shape along its length direction, and the outer shape of the cross section perpendicular to the length direction is an arc shape or a hyperbolic shape. Then, a conductor film 54 such as a metal film is formed on at least the entire surface of the protrusion 53 in the surface of the support portion 52, and the electrode 23 is formed by the conductor film 54 and the protrusion 53 formed on the surface of the protrusion 53. Forming. The power source 26 is connected to the conductor film 54 of each electrode block 22.

  According to such an embodiment, since the support portion 52 and the protrusion 53 can be formed of an insulating material such as a synthetic resin or ceramic, compared to the case of forming the metal electrode block 22 using an electroforming method. Thus, the electrode block 22 can be manufactured easily and with high accuracy. In addition, since the time required for manufacturing the electrode block 22 can be shortened, the electrode block 22 can be mass-produced.

  12A to 12C and FIGS. 13A to 13C are perspective views for explaining a method of manufacturing the quadrupole electrode unit 51 of this embodiment. First, a substrate 55 such as a glass substrate or a silicon substrate is prepared, and a photosensitive resin material is applied thereon by a dip coating method or a spin coating method to form a resin layer 56 as shown in FIG. . Next, by performing an exposure process and a development process on the resin layer 56 using a photolithography technique, a desired cross-sectionally arc-shaped or hyperbolic cross section is formed on the surface of the resin layer 56 as shown in FIG. A plurality of ridges 57 having a size are formed, and a matrix 58 including the substrate 55 and the resin layer 56 is produced.

  Next, after conducting a conductive treatment such as vapor deposition, chemical plating or hot dipping on the surface of the resin layer 56, a metal material is deposited on the resin layer 56 by using an electroforming technique to form a film. A plurality of grooves 60 are formed by ridges 57 on the lower surface of the electroformed film. When the electroformed film grows to a predetermined thickness, the energization is stopped and the electroforming process is terminated. When the electroformed product is peeled off from the mother die 58, a forming die 59 as shown in FIG. A plurality of grooves 60 are formed on the surface of the mold 59.

  When the mold 59 is thus obtained, an insulator block 61 as shown in FIG. 13A is molded using an insulating material. At this time, the protrusion 53 is transferred to the surface of the insulator block 61 as a reverse pattern of the groove 60. For the transfer method, a photopolymerization method, an injection molding method, a micromolding in capillaries method for forming a pattern by filling an insulating material in a gap between the surface plate and the mold 59, and a material that adheres to the mold 59 is a surface plate. Microtransfer molding method that forms a pattern by moving it up, Microcontact printing method, Lithographycally induced self-construction method that forms a pattern by directly deforming the surface to be processed, Laser-assisted direct imprint method, Insulator block substrate Known methods such as nanoimprint lithography and Step and flash imprint lithography, which transfer the pattern to the upper resist and then pattern the substrate by etching process, use thermal transfer and optical transfer. What is necessary is just to use suitably according to a thermal expansion coefficient, precision, etc. with materials.

  Further, as the insulating material used for the insulator block 61, various resins such as a thermoplastic resin, a thermosetting resin, and an energy ray curable resin such as an ultraviolet ray can be used. Examples include cellulose resins such as cellulose acetate butyrate and triacetyl cellulose, polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate (PET), polystyrene, polyurethane, vinyl chloride, acrylic resins, polycarbonate resins, and epoxy. Various plastics such as resins, polyamides, polyolefins, silicones (including modified silicones such as silicone polyurea), polyvinylidene chloride and other vinyl resins, polyimides, polyethersulfones, polysulfone resins, polyarylate resins, and fluorine resins However, the present invention is not necessarily limited thereto, and any glass having a high glass transition point and a smooth surface can be used.

  Next, as shown in FIG. 13B, the insulator block 61 is diced and divided into individual support portions 52. Next, as shown in FIG. 13C, a conductor film 54 is formed on the surfaces of the support portion 52 and the protrusion 53, and the electrode 23 is formed by the protrusion 53 whose surface is covered with the conductor film 54. An electrode block 22 is obtained. In order to improve the adhesion with the support portion 52, the conductor film 54 is formed, for example, by vapor-depositing 30 nm of chromium in the lower layer and 100 nm of Au in the upper layer. The conductor film 54 may be provided on the surface of the support portion 52 other than the protrusion 53. In addition, here, after the insulator block 61 is diced and divided into individual support portions 52, the conductor film 54 is formed on the support portion 52, but the order is changed and the surface of the insulator block 61 is changed. After the conductor film 54 is formed, the insulator block 61 may be diced and divided into individual electrode blocks 22.

  Since it takes time to obtain a desired thickness by the electroforming method, it takes time to produce the electrode block 22 in the method of producing the electrode block 22 by direct electroforming as in the first embodiment. In the manufacturing method according to Example 2, after forming a mold once by electroforming based on the mother mold, the electrode block 25 and the protrusion 53 are duplicated by resin molding or the like using the mold that is the electroformed product, Since the electrode element 23 is formed on the surface of the protrusion 53, the electroformed product need only be prepared once in advance, and the production efficiency of the electrode block 22 can be improved. Furthermore, while the electroforming method electrochemically deposits metal on the mold and grows it to a certain thickness, in the above method, the surface of the support portion 25 is simply subjected to a conductive treatment to the extent that voltage can be applied. Well, much less power is required to manufacture the electrode 23, and the manufacturing cost can be reduced.

  14A and 14B are a perspective view and a plan view showing a modification of the electrode block 22 used in the second embodiment. In this modification, the electrode element 23 is provided at a position slightly retracted from the end of the support portion 52, and the insulating region 62 is formed between the electrode element 23 and the side end face of the support portion 52. Therefore, in this modified example, by bringing the side end surfaces of the electrode blocks 22 on the insulating region 62 side into contact with each other, a predetermined interval can be provided between the electrode elements 23, and the positioning of the electrode blocks 22 can be facilitated.

  15A and 15B are a perspective view and a plan view of the electrode block 22 according to the third embodiment. FIG. 16 is a diagram showing a state in which two electrode blocks arranged side by side are opposed to each other in the vertical direction. FIG. 16A is a diagram showing an end face shape on the ion incident side, and FIG. These are figures which show the end surface shape in the ion emission side. The electrode block 22 of the third embodiment has the same structure as the electrode block 22 according to the modification of the second embodiment. The difference is that, in Example 3, the cross-sectional area of the electrode element 23 gradually decreases from the ion incident side toward the ion emitting side. For example, the end face of the electrode 23 on the ion incident side has a semicircular shape with a radius R1, as shown in FIG. Further, as shown in FIG. 16B, the end face of the electrode 23 on the ion emission side has a semicircular shape with a radius R2 (<R1), and is formed on a rectangular base 63. Yes.

When the four electrode blocks 22 are arranged horizontally and face each other as shown in FIGS. 16A and 16B, the area of the ion passage area 24 surrounded by the four electrode elements 23 is also from the ion incident side. It gradually becomes smaller toward the ion emission side. Here, it is desirable that the cross-sectional area of the electrode element 23 and the cross-sectional area of the ion passage region 24 maintain a constant ratio in an arbitrary cross section. That is, when the four electrode blocks 22 are assembled as shown in FIGS. 16A and 16B, a circular space inscribed in the four electrode elements 23 is defined as an ion passage region 24, and ions on the end surface on the ion incident side are defined. Assuming that the radius of the pass region 24 is r1 and the radius of the ion pass region 24 at the end surface on the ion emission side is r2, the above conditions are as follows.
r1 / R1 = r2 / R2

The above relationship is also established between the end surface on the ion incident side and the end surface on the ion emission side. That is, even in the middle between the ion incident side and the ion emission side, the cross section of the electrode element 23 is semicircular. However, in order to adjust the size of the ion passage region, the semicircular electrode element 23 is disposed on a rectangular base 63. If the radius of the semicircular electrode 23 is R and the radius of the ion passage region 24 in the cross section is r, regardless of the position of the cross section,
r / R = constant.

  According to the third embodiment, since the strength of the analysis electric field formed at the center in the ion passage region 24 by the electrode 23 increases from the ion incident side toward the ion emission side, a wide ion passage on the ion incident side. A large number of ions can be taken in via the region 24 and the ions can be spatially concentrated at the ion outlet.

  FIG. 17 is a perspective view showing a quadrupole electrode unit 71 according to Embodiment 4 of the present invention. FIG. 18 is a perspective view showing an electrode block 72 (electrode structure) constituting the quadrupole electrode unit 71. The quadrupole electrode unit 71 is constituted by two minute electrode blocks 72 in which two electrode elements 23 are formed.

  As shown in FIG. 18, the electrode block 72 has two rod-shaped protrusions 74 protruding at small intervals on the surface of a support portion 73 formed of an insulating material such as synthetic resin or ceramic. Yes. Each protrusion 74 has a uniform cross-sectional shape along its length direction, and the outer shape of the cross section perpendicular to the length direction is an arc or a hyperbola. Then, a conductor film 54 such as a metal film is formed on at least the entire surface of each protrusion 74 of the surface of the support portion 73, and the electrode 23 is formed by the conductor film 54 and the protrusion 74 formed on the surface of the protrusion 74. Is forming. The conductor film 54 is divided into two regions, and an insulating region 75 without the conductor film 54 is provided between the protrusions 74.

  As shown in FIG. 17, the two electrode blocks 72 are arranged vertically so that the electrode elements 23 face each other with a minute gap therebetween, and the ion passage region 24 is interposed between the four electrode elements 23. Is formed. The power source 26 is connected to each conductor film 54 of each electrode block 72.

  According to such an embodiment, since the support portion 73 and the protrusion 53 can be formed of an insulating material such as synthetic resin or ceramic, compared with the case of forming a metal electrode block using an electroforming method. The electrode block 72 can be manufactured easily and with high accuracy. Moreover, since the number of parts is reduced, the cost of the quadrupole electrode unit 71 can be reduced. Furthermore, since the time required for manufacturing the electrode block 72 can be shortened, the electrode block 72 can be mass-produced.

  FIGS. 19A to 19C and FIGS. 20A to 20C are perspective views for explaining a method of manufacturing the quadrupole electrode unit 71 of this embodiment. The quadrupole electrode unit 71 is manufactured in substantially the same manner as the quadrupole electrode unit 51 of the second embodiment. First, a substrate 55 such as a glass substrate or a silicon substrate is prepared, and as shown in FIG. 19A, a photosensitive resin material is applied thereon by a dip coating method or a spin coating method to form a resin layer 56. . Next, by performing an exposure process and a development process on the resin layer 56 using a photolithographic technique, the surface of the resin layer 56 has a desired circular arc shape or hyperbolic shape as shown in FIG. A plurality of ridges 57 having a size are formed, and a matrix 58 including the substrate 55 and the resin layer 56 is produced. Here, the ridges 57 form a pair, and the pair of ridges 57 are arranged close to each other.

  Next, after conducting a conductive treatment such as vapor deposition and plating on the surface of the resin layer 56, a metal material is deposited on the resin layer 56 using an electroforming technique to form a film. A plurality of grooves 60 are formed by ridges 57 on the lower surface of the electroformed film. When the electroformed film grows to a predetermined thickness, the energization is stopped and the electroforming process is terminated. When the electroformed product is peeled off from the mother die 58, a forming die 59 as shown in FIG. On the surface of the molding die 59, a plurality of grooves 60 are formed in pairs.

  When the mold 59 is thus obtained, an insulator block 61 as shown in FIG. 20A is molded using an insulating material such as synthetic resin. At that time, projections 74 are transferred to the surface of the insulator block 61 as a reverse pattern of the groove 60. Next, as shown in FIG. 20B, the insulator block 61 is diced and divided into individual support portions 73. Next, as shown in FIG. 20C, the conductor film 54 is formed on the surface of the protrusion 74 of the support portion 73, and the electrode 23 is formed by the protrusion 74 whose surface is covered with the conductor film 54. An electrode block 72 is obtained. At this time, the two adjacent electrode elements 23 are insulated to form an insulating region 75. For this purpose, a region between the protrusions 74 on the upper surface of the support portion 73 is covered with a photoresist, and a conductor film 54 is formed on the upper surface of the support portion 73 from thereover, and then the conductive film 54 together with the photoresist is formed by a lift-off method. Can be removed. Here, the insulator block 61 is diced and divided into individual support portions 73, and then the conductor film 54 is formed on the support portion 73. However, the order is changed, and the surface of the insulator block 61 is changed. After the conductor film 54 is formed, the insulator block 61 may be diced and divided into individual electrode blocks 72.

  In this way, the quadrupole electrode unit 71 is manufactured by making the electrode block 72 having the two electrode elements 23 face each other as shown in FIG.

  In such a manufacturing method, after forming a mold once by an electroforming method based on a mother mold, the electrode block 25 and the protrusion 53 are duplicated by resin molding or the like using the mold that is the electroformed product, and the protrusion Since the electrode element 23 is formed on the surface 53, the electroformed product need only be prepared once in advance, and the production efficiency of the electrode block 22 can be improved. Furthermore, while the electroforming method electrochemically deposits metal on the mold and grows it to a certain thickness, in the above method, the surface of the support portion 25 is simply subjected to a conductive treatment to the extent that voltage can be applied. Well, much less power is required to manufacture the electrode 23, and the manufacturing cost can be reduced. Furthermore, since the two electrode elements 23 are formed in one electrode block 22, the number of parts can be reduced, which is effective for cost reduction. Moreover, since the two electrode elements 23 are kept at a predetermined distance in advance, the assembly work of the quadrupole electrode unit 71 is facilitated.

  21A and 21B are a perspective view and a front view showing a modification of the electrode block 72 used in the fourth embodiment. In this modification, the electrode element 23 is provided only on the surface of the protrusion 74.

  22A and 22B are a perspective view and a plan view of an electrode block 72 according to the fifth embodiment. The electrode block 72 of the fifth embodiment has the same structure as the electrode block 72 according to the modification of the fourth embodiment. The difference is that in Example 5, the cross-sectional area of the electrode 23 gradually decreases from the ion incident side to the ion emission side, and the area of the ion passage area 24 surrounded by the electrode 23 is also from the ion incident side. This is a point that gradually decreases toward the ion emission side.

Here again, as in the case of the third embodiment, it is desirable that the cross-sectional area of the electrode 23 and the cross-sectional area of the ion passage region 24 maintain a constant ratio in an arbitrary cross section. Therefore, when the two electrode blocks 72 are opposed to each other as shown in FIGS. 23A and 23B, the radius of the semicircular end face of the electrode 23 on the ion incident side is R1, and the electrode 23 on the ion emission side is If the radius of the semicircular end face is R2 (<R1), the radius of the ion passage area 24 at the end face on the ion incident side is r1, and the radius of the ion passage area 24 at the end face on the ion exit side is r2. Is as follows.
r1 / R1 = r2 / R2

The above relationship is also established between the end surface on the ion incident side and the end surface on the ion emission side. That is, even in the middle between the ion incident side and the ion emission side, the cross section of the electrode element 23 is semicircular. However, in order to adjust the size of the ion passage region, the semicircular electrode element 23 is arranged on a rectangular base. If the radius of the semicircular electrode 23 is R and the radius of the ion passage region 24 in the cross section is r, regardless of the position of the cross section,
r / R = constant.

  According to the fifth embodiment, since the intensity of the analysis electric field formed at the center in the ion passage region 24 by the electrode 23 increases from the ion incident side toward the ion emission side, a wide ion passage on the ion incident side. A large number of ions can be taken in via the region 24 and the ions can be spatially concentrated at the ion outlet.

  FIG. 24 is a front view showing an arrayed quadrupole electrode unit (hereinafter referred to as a quadrupole electrode array) 81 according to Embodiment 6 of the present invention. In this quadrupole electrode array 81, two electrode blocks 82 are vertically opposed to form a plurality of ion passage areas 24. Each electrode block 82 is integrally formed with a plurality of (four or more) protrusions 84 having a circular arc shape or a hyperbolic cross section on the surface of a support portion 83 made of an insulating material, and a conductor film is formed on the surface. Thus, the electrode 23 is formed. In the quadrupole electrode array 81 in which the electrode blocks 82 are opposed to each other up and down, quadrupole electrodes are formed by the four electrode elements 23 facing up and down, and an ion passage region 24 is formed between each of them. ing. Therefore, if such a quadrupole electrode array 81 is used, a large amount of ions or a plurality of types of ions can be selected at a time.

  FIG. 25 is a schematic diagram for explaining a voltage application method for the quadrupole electrode array 81. In this example, adjacent electrode elements 23 are connected by a conductive film 54 to be conducted. Then, a voltage is applied to each quadrupole electrode through a wiring path as shown in FIG. According to such a voltage application method, only one power source 26 is required.

  FIG. 26 is a schematic diagram illustrating another method of applying a voltage to the quadrupole electrode array 81. In this example, only the electrode elements 23 constituting the quadrupole electrode are connected by the wiring path as shown in FIG. 26, and the power source 26 is connected to each of them. According to such a voltage application method, voltage application conditions can be made different for each quadrupole electrode.

FIG. 1 is a schematic perspective view showing a configuration of a main part of a conventional quadrupole mass spectrometer. FIGS. 2A and 2B are a front view and a side view showing the size of the quadrupole electrode unit used in the quadrupole mass spectrometer same as above. FIG. 3 is a perspective view showing the structure of the quadrupole electrode unit according to Embodiment 1 of the present invention. FIG. 4 is a perspective view showing an electrode block constituting the quadrupole electrode unit. FIG. 5 is an operation explanatory view of the quadrupole electrode unit. FIG. 6 is a schematic view showing a gas purification apparatus using the quadrupole electrode unit according to the present invention. 7A, 7B, and 7C are perspective views illustrating an example of a method for manufacturing the quadrupole electrode unit according to the first embodiment. FIG. 8 is an exploded perspective view showing a modification of the first embodiment. FIG. 9 is an exploded perspective view showing another modification of the first embodiment. FIG. 10 is an exploded perspective view showing still another modification of the first embodiment. FIG. 11 is a perspective view showing a quadrupole electrode unit according to Embodiment 2 of the present invention. 12A, 12B, and 12C are perspective views illustrating a method for manufacturing the quadrupole electrode unit according to the second embodiment. FIGS. 13A, 13B, and 13C are perspective views showing processes subsequent to FIGS. 12A to 12C. 14A and 14B are a perspective view and a plan view showing a modification of the electrode block used in the second embodiment. FIGS. 15A and 15B are a perspective view and a plan view of an electrode block according to the third embodiment. FIG. 16A shows the end face shape of the four electrode blocks facing each other on the ion incident side, and FIG. 16B shows the end face shape of the four electrode blocks facing each other on the ion emission side. FIG. FIG. 17 is a perspective view showing a quadrupole electrode unit according to Embodiment 4 of the present invention. FIG. 18 is a perspective view showing an electrode block constituting the quadrupole electrode unit of the fourth embodiment. 19A, 19B, and 19C are perspective views illustrating a method for manufacturing the quadrupole electrode unit according to the fourth embodiment. 20 (a), 20 (b), and 20 (c) are perspective views showing steps subsequent to FIGS. 19 (a) to 19 (c). FIGS. 21A and 21B are a perspective view and a plan view showing a modification of the electrode block used in the fourth embodiment. 22A and 22B are a perspective view and a plan view of an electrode block according to the fifth embodiment. FIG. 23A is a diagram showing the end face shape on the ion incident side of the two electrode blocks facing each other, and FIG. 23B is the end face shape on the ion emission side of the two electrode blocks facing each other. FIG. FIG. 24 is a front view showing a quadrupole electrode array according to Example 6 of the present invention. FIG. 25 is a schematic diagram for explaining a voltage application method for the quadrupole electrode array. FIG. 26 is a schematic diagram illustrating another voltage application method for the quadrupole electrode array.

Explanation of symbols

DESCRIPTION OF SYMBOLS 21 Quadrupole electrode unit 22 Electrode block 23 Electrode 24 Ion passage area 25 Support part 26 Power supply 27 Vacuum chamber 28 Ionization part 29 Ionization electrode 30 Exhaust gas chamber 31 Purified gas storage chamber 32 Gas recovery pipe 41 Substrate 42 Resin layer 43 Groove 44 Mold 45 Metal block 51 Quadrupole electrode unit 52 Support portion 53 Projection 54 Conductor film 55 Substrate 56 Resin layer 57 Projection 58 Mother mold 59 Mold 60 Groove 61 Insulator block 62 Insulation region 71 Quadrupole electrode unit 72 Electrode block 73 Support portion 74 Protrusion 75 Insulation region 81 Quadrupole electrode array 82 Electrode block 83 Support portion 84 Protrusion 91 Quadrupole electrode unit 92 Electrode film 93 Support portion 94 Conductive material 95 Through hole 96 Recess 97 Partition

Claims (17)

A quadrupole electrode unit for generating an electric field potential in a quadrupole mass spectrometer,
By combining a plurality of electrode structures, each of which includes a support portion and an electrode element having at least a surface made of a conductive material, and the shape component portion of the electrode element and the support portion are integrally formed of the same material , A quadrupole electrode unit in which two electrode elements are arranged in a quadrupole.   In the electrode structure, one electrode element is formed on the surface of the support portion, and by combining the four electrode structures, the four electrode elements are arranged so as to be substantially parallel to each other. The quadrupole electrode unit according to claim 1, wherein the quadrupole electrode unit is arranged in a pole.   In the electrode structure, two electrode elements are formed on the surface of the support portion, and by combining the two electrode structures, four electrode elements are arranged so that the four electrode elements are substantially parallel to each other. The quadrupole electrode unit according to claim 1, wherein the quadrupole electrode unit is arranged in a pole.   The quadrupole electrode unit according to claim 1, wherein a spacer for keeping a distance between the electrode elements at a predetermined distance is interposed between the electrode structures.   The cross-sectional area of the electrode element and the cross-sectional area of the ion passage region formed between the electrode elements are gradually reduced from the ion incident side to the ion emission side while maintaining a constant ratio. The electrode element is configured so that the intensity of an electric field formed at the center of the ion passage region gradually increases from the ion incident side toward the ion emission side. Quadrupole electrode unit. An electrode structure used for the quadrupole electrode unit according to claim 1,
An electrode body structure comprising a support portion and an electrode element having at least a surface made of a conductive material, wherein a shape component of the electrode element and the support portion are integrally formed of the same material . The electrode structure according to claim 6, wherein the rod-shaped electrode is integrated with the support portion.   The electrode structure according to claim 7, wherein the support portion is made of a conductive material. A rod-shaped protrusion which is a shape component of the electrode element is integrally formed on the support portion, and the electrode element is formed by forming a film-like conductive material on the surface of the protrusion. The electrode structure according to claim 6, wherein   The electrode structure according to claim 9, wherein the support part and the protrusion are made of an insulating material.   The electrode structure according to claim 6, wherein the electrode has a circular arc shape or a hyperbolic shape in a cross section perpendicular to the length direction thereof.   The electrode structure according to claim 6, wherein a cross-sectional area of the electrode is uniform over a length direction thereof.   7. The electrode structure according to claim 6, wherein a cross-sectional area of the electrode is gradually reduced from one end to the other end. A method for manufacturing an electrode structure in which an electrode for generating an electric field potential and a support part are integrally formed of a conductive material in a quadrupole mass spectrometer,
Producing a mold having a groove whose cross section perpendicular to the length direction has an arc shape or a hyperbolic shape; and
A step of integrally molded with the support portion of the Denkyokuko by the same time the groove when the molding the supporting portion by the mold by use of the electroforming,
The manufacturing method of the electrode structure provided with.   The method for manufacturing an electrode structure according to claim 14, wherein the mold is manufactured by a photolithography technique. An electrode structure for a quadrupole electrode unit comprising a support portion and an electrode element having a surface made of a conductive material, wherein the shape component portion of the electrode element and the support portion are integrally formed of an insulating material is manufactured. A method for
Producing a matrix having a convex portion of the same shape as the electrode;
A step of producing a molding die having a groove whose cross section perpendicular to the length direction has an arc shape or a hyperbolic shape by electroforming using the mother die;
A step to integrally forming the projection where a shape component of the Denkyokuko by the groove at the same time with the support portion when molding the mold in I Ri before Symbol support,
Forming the electrode by conducting the surface of the protrusion with a conductive material ;
The manufacturing method of the electrode structure provided with. An electrode structure for a quadrupole electrode unit comprising a support portion and an electrode element having a surface made of a conductive material, wherein the shape component portion of the electrode element and the support portion are integrally formed of an insulating material is manufactured. A method for
Producing a mother die in which two convex portions having the same shape as the electrode are formed close to each other;
A step of producing a mold having two grooves whose cross section perpendicular to the length direction has an arc shape or a hyperbolic shape by electroforming using the mother die;
A step you integrally molded with the support portion of two closely spaced projections by the same time the groove when forming the casting mold by Ri before Symbol supporting portion where a shape component of the Denkyokuko,
Forming the electrode by conducting a conductive treatment with a conductive material on the surface of each of the protrusions while maintaining an insulating state between the protrusions;
The manufacturing method of the electrode structure provided with.

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