WO2008038642A1

WO2008038642A1 - Sample analyzing method, and analyzing apparatus

Info

Publication number: WO2008038642A1
Application number: PCT/JP2007/068612
Authority: WO
Inventors: Toshiyuki Kato; Yukari Matsuo; Tohru Kobayashi; Mizuki Nishimura; Jun Kawai; Yoshihide Hayashizaki
Original assignee: Riken
Priority date: 2006-09-27
Filing date: 2007-09-26
Publication date: 2008-04-03

Abstract

Monoatomic ions in a plasma generated from a sample by a laser abrasion according to an ultrashort pulse laser irradiation are highly efficiently introduced for mass spectrometry. The sample is ionized into the monoatoms by irradiating it with one pulse of the ultrashort pulse laser so that the elements of the whole mass region are analyzed by a time-of-flight mass spectrometer (30). An ion acceleration electrode (23) has its mesh hole diameter set smaller than the Debye length of the plasma which has been generated by the ultrashort pulse laser abrasion ionization.

Description

Specification

Sample analysis method and analyzer

Technical field

[0001] The present invention relates to a sample analysis method and apparatus for a micro region using laser ablation and mass spectrometry.

Background art

[0002] Analyzes are performed by irradiating a polymer to be analyzed with an ultrashort pulse laser beam such as a femtosecond laser and ablating it to atomize the polymer into constituent elements and at the same time ionize and analyze the ionized constituent elements The method is described in Japanese Patent No. 3640387 and Japanese Patent Application Laid-Open No. 2004-212215. Since ions generated by femtosecond laser irradiation have high kinetic energy and jump out around the normal direction of the sample surface, a method for mass analysis of the emitted ions from a direction parallel to the sample surface is Roland Hergenroder, et al ., Femtosecond Laser Aolation elemental Mass Spectrometry, Mass spectro metry Reviews 25 (2006) 551—572! /, (Ma Vanja Margetic, et al., "Application of Femtosecond Laser Ablation Time-of Flight Mass Spectrometry to In-Depth Multilayr analysis ", Analytical Chemistry 75 (2003) 3435-3439. Also, eni chi Watanaoe, et al., Improvement or resonant laser ablation mass spectrometry usi ng high-repetition-rate and short-pulse tunable laser. system, Spectrochemica Acta Part B 58 (2003) 1163-1169 describes that, among ions and neutral atoms generated by femtosecond laser irradiation, ions are removed by methods such as electric field, and only neutral atoms are ionized again. And how to analyze is described. The ionization again, typically nanosecond laser resonance wavelength is used.

Patent Document 1: Japanese Patent No. 3640387

Patent Document 2: Japanese Patent Application Laid-Open No. 2004-212215

Non-Patent Document 1: Mass Spectrometry Reviews 25 (2006) 551-572

Non-Patent Document 2: Analytical Chemistry 75 (2003) 3435-3439

Non-Patent Document 3: Spectrochemica Acta Part B 58 (2003) 1163-1169 Disclosure of the invention

Problems to be solved by the invention

[0003] In the case of laser ablation of a sample by irradiation with an ultrashort pulse laser beam such as a femtosecond laser, ions generated from the sample form a plasma together with electrons, and control by an external electric field becomes difficult. In addition, there is a problem that control is difficult because the kinetic energy of ions jumping out of the sample is large. Mass analysis is possible if only ions with low kinetic energy are taken into the mass spectrometer from the direction parallel to the sample surface. 1S Most of the generated ions are difficult to observe and analysis efficiency is very high. It ’s bad. The method of ionizing only neutral atoms requires a device for ionization again, and the ionization efficiency of the sample is poor because it undergoes a two-stage process of neutral atom generation from the sample and its ionization. In addition, when resonance ionization using laser light of a specific wavelength is used again as an ionization technique, it is impossible to comprehensively analyze all elements in the entire mass region.

[0004] The present invention provides a method and apparatus capable of mass spectrometry by taking in monoatomic ions or molecular ions in plasma generated by laser ablation by irradiation with ultrashort pulse laser light such as a femtosecond laser with high efficiency. The purpose is to provide. Means for solving the problem

[0005] In the present invention, a sample is monoatomically ionized by irradiating one pulse of an ultrashort pulse laser such as a femtosecond laser, and elemental analysis or mass analysis of the entire mass region is performed with a time-of-flight mass analyzer. By performing femtosecond laser ablation ionization under the condition that all ions in the plasma generated on the sample surface can be accelerated by an electric field, elemental analysis or mass analysis can be performed with a mass analyzer located in the normal direction of the sample surface. I made it. As a result, the detection efficiency of ions atomized has improved, and local analysis of trace samples and microregion samples has become possible. The present invention can be applied to solid, liquid, and powder samples.

[0006] Conventionally, in femtosecond laser ablation, a high-density plasma is generated, so that a forward electric field cannot be applied to the plasma due to the electric field shielding effect of plasma, and mass spectrometry cannot be performed in this technical field. Although common sense, the present invention has been completed by overcoming this common sense. The invention's effect

[0007] According to the present invention, it becomes possible to perform mass analysis or elemental analysis of a very small amount of sample efficiently and with high sensitivity with a simple apparatus configuration.

Brief Description of Drawings

[0008] FIG. 1 is a schematic diagram showing a configuration example of a microregion trace element analyzer according to the present invention.

FIG. 2 is an enlarged schematic view of a femtosecond laser ablation ion source according to the present invention.

FIG. 3A is a diagram showing an example of a mass spectrum measured by the apparatus of the present invention.

FIG. 3B is a diagram showing an example of a mass spectrum measured by the apparatus of the present invention.

FIG. 4A is a diagram showing an example of a mass spectrum measured by the apparatus of the present invention.

FIG. 4B is a diagram showing an example of a mass spectrum measured by the apparatus of the present invention.

FIG. 4C is a diagram showing an example of a mass spectrum measured by the apparatus of the present invention.

FIG. 4D is a diagram showing an example of a mass spectrum measured by the apparatus of the present invention.

Explanation of symbols

[0009] 10: Femtosecond laser generator

11: Nonlinear optical element

12 ： Mechanical double shutter

15: Laser power attenuation device

16: MgF window

2

17: Focusing lens

18: 1 pulse femtosecond laser light

20: Femtosecond laser abrasion: Sun source

21: XY stage

22: Sample mount

23: Ion acceleration electrode

25: Vacuum container

30: Reflection time-of-flight mass spectrometer

31: Ion reflection electrode

32: Ion detector BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described with reference to the drawings.

FIG. 1 is a schematic diagram showing a configuration example of a microregion trace element analyzer according to the present invention.

This apparatus includes a femtosecond laser generator 10, an XY stage 21, a sample mount 22 held on the XY stage 21, and an ion acceleration electrode 23 that is arranged in parallel with the sample mount 22 and generates an accelerating electric field between the sample mount 23 And a reflective time-of-flight mass analyzer 30. The XY stage 21, the sample mount 22, and the ion acceleration electrode 23 constitute a femtosecond laser single abrasion ion source section 20. A femtosecond laser ablation ion source unit 20, an ion reflection electrode 31 and an ion detector 32 that constitute a reflection time-of-flight (TOF) mass analyzer 30 are arranged in a vacuum vessel 25.

[0012] If the sample to be analyzed is solid, it is fixed to the sample mount 22 as it is and placed on the XY stage 21. In the case of a liquid sample, the sample mount 22 made of a silicon substrate or the like is applied and dried, and then the sample mount 22 is placed on the XY stage 21. Also, if the sample is powder, wipe it onto the sample mount, or apply it to the sample mount with solvent and dry it, then place the sample mount on the XY stage 21.

[0013] A laser pulse emitted from the femtosecond laser generator 10 is converted into a double wave by a non-linear optical element 11 such as a BiBO crystal and then cut out by one pulse by a mechanical shutter 12. The 1-pulse femtosecond laser beam 18 becomes an appropriate laser power by a laser power attenuator 15 such as an ND filter, passes through the MgF window 16 of the vacuum vessel 25, and is focused by the focusing lens 17, on the XY stage 21. Sample mount

2

Irradiate the sample surface held by The focusing lens 17 may be in a vacuum or in the atmosphere. The photodiode 13 detects and monitors a small part of the laser pulse reflected by the half mirror 14.

[0014] The allowable conditions of the laser pulse irradiated to the sample surface are that the wavelength is controlled to the entire range, the pulse width is 10 ⁴ femtoseconds or less, and 1 pulse. A group of ions originating from a sample atomized by laser ablation by femtosecond laser irradiation is accelerated by an accelerating electric field formed between the sample mount 22 and an electrode 23 placed in parallel therewith. Introduced into 30 and mass analyzed. FIG. 2 is an enlarged schematic view of a femtosecond laser ablation ion source section according to the present invention. Here, a case where the ion acceleration electrode is a mesh electrode will be described. When a sample is irradiated with a femtosecond laser and ablated, the sample is atomized into constituent elements and simultaneously ionized (monoatomic ionization), and the generated monoatomic ions generate plasma together with electrons to form a surrounding solid substance. A sheath layer on which an external electric field acts is formed between them. The width of the sheath layer, that is, the length of the device, which is the distance that the external electric field can penetrate into the plasma, is

D

It is expressed by a formula.

Country

IT

X _D = aA— [m]

V n

n: electron density [ιι ³ ]

T _e : electron temperature [e V]

a = 7.4 5 X 1 O ³

In the present invention, by reducing the irradiation diameter of the femtosecond laser and irradiating with the laser power density corresponding to the combination of the sample and the substrate material, the device length λ of the abrasion plasma is changed to the mesh hole diameter of the ion acceleration electrode. Make it larger than (radius). Ion acceleration

D

When the electrode mesh interval is d and the mesh hole diameter is d / 2, femtosecond laser ablation ionization is performed under the conditions that satisfy the following equation.

[0017] λ> d / 2… hi)

D

When this conditional expression (1) is satisfied, the electric field formed between the sample mount and the ion accelerating electrode penetrates into the plasma sheath having a Debye length, and all the ions in the plasma are accelerated by the electric field. Therefore, analysis of product ions becomes possible by TOF mass spectrometry with forward electric field acceleration. If conditional expression (1) is not satisfied, the generated high-density neutral plasma cannot be uniformly accelerated by the accelerating electric field. As deviating from the conditional expression (1), ions that cannot be time converged by the time-of-flight mass analyzer and ions are increased and the mass spectrum is disturbed, so that ions cannot be identified. Therefore, in the case of conditions that do not deviate too much from conditional expression (1), the time-converged ion peak may be identified in the background of ions that have not time-converged. By the way, conventional femtosecond laser ablation As for the conditions of the laser, the laser spot size is about 120 πι φ, the laser power is 220 〃 J, and the resulting device plasma length is estimated to be less than 20 m, and the mesh electrode hole diameter is 500 m. The accelerating electrode was not in a state that could satisfy the conditional expression (1).

[0018] According to the present invention, all the ions in the plasma generated by femtosecond laser ablation, which was impossible in the past, can be accelerated and analyzed by time-of-flight mass spectrometry. It is presumed that the electron density in the plasma was decreased by reducing the total number of ions while maintaining the same ion emission angle distribution by reducing the power. On the other hand, the problem of the present invention can also be solved by using a fine mesh of the eyes and a large mesh for the electrode.

[0019] That is, in the present invention, the ion generated by the abrasion is obtained by reducing the irradiation laser energy level and reducing the laser spot size while ensuring the peak energy at which plasma is generated by the laser abrasion. The plasma density was reduced by decreasing the number of plasmas, and the plasma sheath on which the external electric field acts was increased accordingly. In other words, the sample was subjected to laser ablation using a femtosecond laser having a laser power sufficient to generate a plasma having a sufficiently long Debye length and to generate single atom ionization.

Thus, according to the present invention, ions derived from a sample can be detected with high detection efficiency. In addition, the local range of the sample can be analyzed by laser pinpoint irradiation. Typically, it is possible to analyze a small amount of sample contained in a minute region having a diameter of, for example, about 15 m. In the case of a solution sample, it is possible to analyze a small amount of sample that falls within a range of, for example, a diameter of 15 m when applied after drying.

[0021] Note that instead of the mesh electrode, an electrode having another shape such as a grid type or a pinhole type and having an ion passage hole may be used. At this time, the dimension corresponding to the mesh interval d in the conditional expression (1) is the grid interval in the case of the grid electrode, and the pinhole diameter in the case of the pinhole electrode.

[0022] In order to realize the method of the present invention, the laser power needs to be smaller than 200 J per pulse. As the laser power of one pulse increases, the plasma density increases. As a result, the external electric field is shielded. For example, it can be said that ions could be identified even with a laser power of 110 J (Experiment 1 described later). In addition, the ablation plasma generated with 220 J laser power has already become a high density neutral plasma! /, And since it could not be accelerated by applying a forward electric field, the laser power should be lower than that. There is a need . Therefore, the upper limit of the laser power for realizing the method of the present invention is 200 J.

[0023] With regard to the laser condensing size, this technique can be applied even when the laser fluence is typically a force that can use lj / cm ² is approximately 0.1 lj / cm ² . If the laser power is assumed to be about 200 J, the laser size at that time will be several hundreds of micrometer diameters. Therefore, the laser condensing size should be less than lmm in diameter! /.

[0024] Hereinafter, an example of analysis of a trace amount sample according to the present invention will be described.

[0025] [Experiment 1]

The Eu (Europium) standard solution was analyzed using the apparatus shown in FIG. The Eu standard solution used for the analysis is a europium standard solution for atomic absorption analysis manufactured by Wako Pure Chemical Industries, Ltd. Eu: l, 000 mg / L (Eu (NO) in lmol / L-HNO). A pulse with a wavelength of 800 nm and a pulse width of 120 fs emitted from a femtosecond laser generator at 500 Hz was converted into a laser beam with a wavelength of 400 nm through a BiBO crystal. A sample obtained by applying 10 L of a Eu standard solution diluted with ultrapure water on a silicon substrate and vacuum-drying the sample was irradiated with a femtosecond laser, and a mass spectrum was measured. A mesh electrode as the ion accelerating electrode 23 was placed 6 mm in front of the silicon substrate, and a voltage of 5000 V was applied between the sample mount 22 and the mesh electrode.

[0026] Here, the measurement was performed by changing the experimental conditions in two ways. The measured mass spectrum is shown in FIGS. 3A and 3B. The spectrum was obtained with a single laser pulse. Two stable isotopes of Eu can be observed by sandwiching the low mass side and the high mass side between silicon cluster ions. The experimental conditions in FIGS. 3A and 3B are as follows.

[table 1]

[0027] The device length of the laser ablation plasma can be estimated to be 20 Hm or less in the case of FIG. 3A. In estimating the device length, the laser ablation plasma is observed by the laser induced fluorescence (LIF) method, the volume of the plasma is measured, the number of atoms blown off from the ablation mark is measured, and the LIF method is used. The ionization rate was measured. As a result, the electron density was estimated to be approximately 6 X 10 ⁹ mm ³ . And the electron temperature is estimated to be 10eV or less. In the case of Fig. 3B, it can be inferred that the device length has been increased by at least 22 times since the number of blown atoms has been reduced to about 1/512. Therefore, the experiment of FIG. 3A does not satisfy the above-described conditional expression (1)! /, But the experiment of FIG. 3B is performed in a state satisfying the conditional expression (1).

[0028] As is clear from the comparison of Fig. 3A and Fig. 3B, the spectrum of Fig. 3A, which does not satisfy the conditional expression (1), has a large background due to the failure of normal time convergence. The peak of the silicon cluster cannot identify the isotope because the performance decreases. In addition, since the acceleration effect of the external electric field is affected by the plasma size, the TOF (time-of-flight) value sometimes shifted back and forth when the spectrum was observed for each laser irradiation. On the other hand, in the spectrum of Fig. 3B, which was performed in a state satisfying conditional expression (1), the ions converged cleanly in time, and the isotopes of silicon clusters can be identified. In addition, detection sensitivity was improved due to good time convergence of ions, and Eu element equivalent to lppb was detected from the irradiated region in the maximum sensitivity measurement. In addition, the TOF value for each laser irradiation was constant, and there was no blurring for each laser shot.

[0029] [Experiment 2]

Analysis of commercial cosmetics (foundation) was performed using the apparatus shown in FIG. Commercially available powder samples made of cosmetics are dissolved in benzene, and 10 L is applied to a gold-deposited quartz substrate. It was dried and solidified in the air and placed on a vacuum XY stage. A femtosecond laser generator, a laser pulse with a wavelength of 800 nm and a pulse width of 120 fs emitted at 500 Hz was converted into a laser beam with a wavelength of 400 nm through a BiBO crystal. The laser passes only one pulse, S mechanical double force, the laser power is attenuated to 2 J by the ND filter, and is focused to a laser spot size of 15 mφ on the sample surface by a focusing lens placed in a vacuum. . A mesh electrode having a mesh pore diameter of 500 m was used as the ion acceleration electrode. A voltage of 0 V was applied to the mesh electrode. At this time, the laser ablation plasma has a denomination length that is equal to or larger than the mesh hole radius as shown in Experimental Example 1, and satisfies the above conditional expression (1). Ions generated by femtosecond laser ablation were accelerated toward the surface of the sample substrate by a +5 kV voltage applied to the sample mount, and were elementally discriminated by a reflective TOF mass spectrometer.

[0030] A mass spectrum was acquired in the entire mass region with one pulse of laser. Figures 4A-4D show the resulting mass spectra. In Figure 4A-4D, for convenience, the force S is shown as a mass vector divided into four graphs. These mass spectra were obtained from a single analysis using one pulse of laser. Also, the magnification of the vertical axis representing the amplitude in each graph is different to make the spectrum easier to see. As shown in Figures 4A-4D, this analysis can identify the following elements: H, C, N, 0, F, S, Na, Mg, Al, Si, K, Ti, Fe, Zn, Ba did it. At this time, the powder sample irradiated per pulse is equivalent to 0.3 ng.

[0031] The embodiment described above may be modified as described in the following (1) to (9).

[0032] (1) In the embodiment described above, when a molecule is abraded with an ultrashort pulse laser beam, the molecule is irradiated with one shot (one pulse) of the ultrashort pulse laser beam. However, a molecule that is not limited to this may be irradiated with a plurality of shots (multiple pulses) of ultrashort pulse laser light, and the number of shots of the ultrashort pulse laser light applied to the molecule may be appropriately selected.

[0033] It should be noted that the ultrashort pulse laser preferably has a nose time width of 1 nanosecond or less, and in particular, a laser usually referred to as a femtosecond laser of 1 femtosecond or more and 1 picosecond or less. It is appropriate to use. Its peak value output (power after passing through ND filter 15) ) Is preferably 10 kilowatts or more, particularly 1 megawatt or more and 2 gigawatts or less.

[0034] According to an experiment by the present inventor, for example, a very good result could be obtained when the pulse width was 120 femtoseconds and the peak output was 10 megawatts.

In addition to the femtosecond laser described above, a picosecond laser, a nanosecond laser, or an attosecond laser can also be used.

[0036] The wavelength of the ultrashort pulse laser beam is not particularly limited, and an arbitrary wavelength may be appropriately selected according to the analysis target. That is, as the ultrashort pulse laser beam, for example, a laser beam having a wavelength region from X-rays to far infrared rays, preferably a wavelength region of 11 μm or less can be used. Here, the wavelength region from X-rays to far infrared rays is a wavelength region that can be output by a free electron laser, for example. The wavelength region of l l ^ m or less is the wavelength region of a commercially available pulse laser (11 m or less).

[0037] (2) In the above-described embodiment, force S using a reflection-type time-of-flight mass analyzer as a mass analyzer, a quadrupole mass analyzer and an ion cyclotron type are not limited thereto. Various mass spectrometers such as Fourier transform mass spectrometer can be used

[0038] In the above-described embodiment, mass spectrometry is described as a molecular analysis method. However, the present invention is not limited to this, and the present invention may be used for analysis other than mass spectrometry. .

(3) In the above-described embodiment, the sample is fixed on the silicon substrate. However, the material of the sample substrate that supports the sample is not limited to this, and is a semiconductor or It may be a metal or an insulator. Depending on the type of sample, it may not be necessary to use a sample substrate. Here, the sample may be an inorganic substance such as a metal, a semiconductor, or an insulator, or an organic substance such as a plastic or a biopolymer, and is not limited thereto. Samples may be in the form of solids, powders, liquids or solutions, or those applied to a solid substrate, but are not limited to this!

(4) In the above-described embodiment, the ultrashort pulse laser beam for ablating the molecule and the molecule to be analyzed are moved by moving at least one of them. The analysis may be performed by ablating the molecule to be analyzed without omission or duplication using an ultrashort pulse laser beam for ablating the molecule. In other words, if a moving means for moving the sample or a moving means for moving the irradiation position of the ultrashort pulse laser light target is provided, it is particularly effective in high-speed analysis of microarray samples. .

[0041] Further, the configuration of the above-described analyzer is not particularly limited. For example, a microscope device for observing a sample, an image of the sample observed with the microscope device, and the analysis result are displayed. You may make it arrange | position with the image-analysis apparatus provided with the display part to perform.

[0042] (5) In the embodiment described above, a mesh electrode is used as the ion acceleration electrode, and the force distance in which the mesh electrode is arranged 6 mm away from the sample mount may be any number of mm. An lmm force of 10 cm is particularly preferred. In addition, although a voltage of 5000 V was applied between the sample mount and the ion accelerating electrode, the applied voltage is not particularly limited. Particularly preferred is lkV to 30 kV.

(6) In the above-described embodiment, the detailed description thereof is omitted, but the voltage may be constantly applied or may be applied in a Norse manner. In other words, the electric field may be applied to the ions existing between the electrodes! /, Or at a constant voltage! //, but the electric field may be generated by being divided in time by a no-less voltage.

(7) Although the mesh electrode is used as the ion acceleration electrode in the above-described embodiment, the present invention is not limited to this. As the ion accelerating electrode, any shape can be used as long as it has an opening through which ions can pass.

(8) In the above-described embodiment, no other electrode is disposed in the region of the forward electric field formed by the sample mount as the first electrode and the mesh electrode. However, another electrode may be arranged in the forward electric field region, and the potential gradient may be provided in multiple steps in the forward electric field region. When potential gradients are provided in multiple steps in the forward electric field region in this way, ions can be selectively accelerated by applying a voltage with a pulse, and mass resolution can be improved.

[0046] (9) The above-described embodiment and the modifications shown in the above (1) to (8) may be appropriately combined.

Claims

The scope of the claims

[1] An ionization process by irradiating an object to be analyzed with an ultra-short pulse laser beam to ablate the object to be analyzed.

Accelerating the ions generated by the ionization by applying a forward electric field in the surface normal direction of the analysis object;

And a step of performing mass analysis or elemental analysis of the accelerated ions with a mass spectrometer.

[2] The analysis method according to claim 1, wherein the analysis target is atomized into constituent atoms by the abrasion.

[3] The analysis method according to claim 1 or 2, wherein the ions obtained by the abrasion constitute a plasma, and the forward electric field is applied to the plasma to accelerate ions constituting the plasma. An analysis method characterized by that.

[4] The analysis method according to any one of claims 1 to 3, wherein the laser power of the ultrashort pulse laser is 200 J or less per pulse.

[5] The analysis method according to any one of claims 1 to 4, wherein a condensing size of the ultrashort pulse laser on the object to be analyzed is 1 mm or less in diameter.

[6] The analysis method according to any one of claims 1 to 3, wherein the laser power of the ultrashort pulse laser is 200 J or less per pulse, and the ultrashort pulse laser is collected on the object to be analyzed. An analysis method characterized in that the light size is 1 mm or less in diameter.

[7] The analysis method according to any one of claims 3 to 6, wherein the plasma passes through an electrode having an ion passage hole disposed adjacent to the analysis target and applying the forward electric field. The analysis method is characterized by comprising a sheath part which is the force of the external electric field and the area to be covered.

[8] The analysis method according to any one of claims 3 to 6, wherein the forward electric field is caused to act by an electrode having an ion passage hole disposed adjacent to the analysis target. Analysis method.

[9] The analysis method according to any one of claims 1 to 8, wherein the ultrashort pulse laser is used. One light has a pulse time width of 10 picoseconds or less.

[10] The analysis method according to any one of claims 1 to 9, wherein the analysis target is a solid.

An analysis method characterized by having a form of powder, liquid or solution, or a form in which it is applied to a solid substrate.

[11] Ultrashort pulse laser generator,

A sample holder,

An optical system that focuses the ultrashort pulse laser beam generated from the ultrashort pulse laser beam generator onto the sample held in the sample holder;

Acceleration provided with ion passage holes and adjacent to the sample holder for applying a forward electric field to the ions in the plasma generated by laser ablation caused by the ultrashort pulse laser irradiation for acceleration. Electrodes,

An analyzer comprising: a mass spectrometer for mass-analyzing ions that have passed through the acceleration electrode; and a vacuum container that accommodates the sample holder, the acceleration electrode, and the mass spectrometer.

[12] The analyzer according to claim 11, wherein the analysis target held in the sample holder by the abrasion is atomized into constituent atoms.

13. The analyzer according to claim 11 or 12, wherein the laser power of the ultrashort pulse laser is 200 J or less per pulse.

[14] The analysis device according to any one of claims 11 to 13, wherein the condensing size on the analysis object held in the sample holding part of the ultrashort pulse laser is 1 mm or less in diameter. Analytical device characterized by being.

[15] The analysis apparatus according to claim 11 or 12, wherein the laser power of the ultrashort pulse laser is 200 J or less per pulse and is held in the sample holding portion of the ultrashort pulse laser. An analyzer characterized in that the condensing size above is less than lmm in diameter.

[16] In the analyzer according to claim 11, when the plasma passes through the accelerating electrode, most of the plasma is composed of a sheath part which is a force of an external electric field and a covered area. Analysis equipment.

[17] The analyzer according to [11], wherein the ionization by the laser ablation is performed under the condition that all ions in the plasma generated on the sample surface can be accelerated by the forward electric field. .

[18] The analysis apparatus according to any one of [11] to [17], wherein the ultrashort pulse laser beam has a pulse time width of 10 picoseconds or less.