WO2008038642A1 - Procédé d'analyse d'échantillon et appareil d'analyse - Google Patents

Procédé d'analyse d'échantillon et appareil d'analyse Download PDF

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Publication number
WO2008038642A1
WO2008038642A1 PCT/JP2007/068612 JP2007068612W WO2008038642A1 WO 2008038642 A1 WO2008038642 A1 WO 2008038642A1 JP 2007068612 W JP2007068612 W JP 2007068612W WO 2008038642 A1 WO2008038642 A1 WO 2008038642A1
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WIPO (PCT)
Prior art keywords
analysis
pulse laser
laser
ultrashort pulse
sample
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PCT/JP2007/068612
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English (en)
Japanese (ja)
Inventor
Toshiyuki Kato
Yukari Matsuo
Tohru Kobayashi
Mizuki Nishimura
Jun Kawai
Yoshihide Hayashizaki
Original Assignee
Riken
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication of WO2008038642A1 publication Critical patent/WO2008038642A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/10—Ion sources; Ion guns
    • H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
    • H01J49/161—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission using photoionisation, e.g. by laser
    • H01J49/164—Laser desorption/ionisation, e.g. matrix-assisted laser desorption/ionisation [MALDI]

Definitions

  • the present invention relates to a sample analysis method and apparatus for a micro region using laser ablation and mass spectrometry.
  • 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
  • an ultrashort pulse laser beam such as a femtosecond laser
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • an ultrashort pulse laser such as a femtosecond laser
  • elemental analysis or mass analysis can be performed with a mass analyzer located in the normal direction of the sample surface. I made it.
  • the present invention can be applied to solid, liquid, and powder samples.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the ion acceleration electrode is a mesh electrode will be described.
  • the sample 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
  • the device length ⁇ of the abrasion plasma is changed to the mesh hole diameter of the ion acceleration electrode. Make it larger than (radius).
  • conditional expression (1) 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.
  • the time-converged ion peak may be identified in the background of ions that have not time-converged.
  • conventional femtosecond laser ablation As for the conditions of the laser, the laser spot size is about 120 ⁇ ⁇ , 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).
  • 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.
  • 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.
  • 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.
  • ions derived from a sample can be detected with high detection efficiency.
  • the local range of the sample can be analyzed by laser pinpoint irradiation.
  • 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.
  • the laser power needs to be smaller than 200 J per pulse.
  • the plasma density increases.
  • the external electric field is shielded.
  • 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.
  • 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! /.
  • 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.
  • FIGS. 3A and 3B 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.
  • the device length of the laser ablation plasma can be estimated to be 20 Hm or less in the case of FIG. 3A.
  • 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.
  • the electron density was estimated to be approximately 6 X 10 9 mm 3 .
  • the electron temperature is estimated to be 10eV or less.
  • 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).
  • 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.
  • 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.
  • FIG. 4A-4D show the resulting mass spectra.
  • 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.
  • the molecule 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.
  • 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.
  • 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.
  • a picosecond laser, a nanosecond laser, or an attosecond laser can also be used.
  • 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 ⁇ m or less can be used.
  • 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).
  • 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
  • mass spectrometry is described as a molecular analysis method.
  • the present invention is not limited to this, and the present invention may be used for analysis other than mass spectrometry. .
  • the sample is fixed on the silicon substrate.
  • 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.
  • 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!
  • 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.
  • 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. .
  • the configuration of the above-described analyzer is not particularly limited.
  • 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
  • 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.
  • 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.
  • the voltage may be constantly applied or may be applied in a Norse manner.
  • 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.
  • the mesh electrode is used as the ion acceleration electrode in the above-described embodiment, the present invention is not limited to this.
  • the ion accelerating electrode any shape can be used as long as it has an opening through which ions can pass.
  • 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.
  • 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.
  • 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.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

Selon la présente invention, des ions monoatomiques dans un plasma produit à partir d'un échantillon par une abrasion de laser selon une irradiation de laser à impulsion ultracourte sont très efficacement introduits pour la spectrométrie de masse. L'échantillon est ionisé dans les monoatomes en l'irradiant avec une impulsion du laser à impulsion ultracourte de sorte que les éléments de la région de masse entière soient analysés au moyen d'un spectromètre de masse à temps de vol (30). Une électrode d'accélération d'ions (23) a son diamètre de trou de maille plus petit que la longueur de Debye du plasma qui a été produit par l'ionisation par abrasion du laser à impulsion ultracourte.
PCT/JP2007/068612 2006-09-27 2007-09-26 Procédé d'analyse d'échantillon et appareil d'analyse WO2008038642A1 (fr)

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JP2006-263153 2006-09-27

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014063585A (ja) * 2012-09-20 2014-04-10 Shimadzu Corp 真空チャンバ内におけるｘｙステージの支持構造およびレーザ脱離イオン化装置
JP2015152370A (ja) * 2014-02-13 2015-08-24 株式会社ニコン 検出装置、顕微鏡および処理装置
JP2016225108A (ja) * 2015-05-29 2016-12-28 国立研究開発法人日本原子力研究開発機構 質量分析装置、イオン照射装置
CN112730593A (zh) * 2020-11-26 2021-04-30 长春理工大学光电信息学院 一种超短脉冲激光电离有机氯农药的方法

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Publication number Priority date Publication date Assignee Title
JPH1090226A (ja) * 1996-09-11 1998-04-10 Shimadzu Corp ペプチドのアミノ酸配列決定方法
JP2003247983A (ja) * 2002-02-25 2003-09-05 Nippon Laser & Electronics Lab 標的物質質量分析システム
JP2004212215A (ja) * 2002-12-27 2004-07-29 Institute Of Physical & Chemical Research レーザーアブレーション高分子分析装置
JP2004257973A (ja) * 2003-02-27 2004-09-16 Jsr Corp 微小物の形状・構造分析方法及び装置
WO2005074003A1 (fr) * 2004-01-28 2005-08-11 Kyoto University Dispositif et pocédé d’analyse laser

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1090226A (ja) * 1996-09-11 1998-04-10 Shimadzu Corp ペプチドのアミノ酸配列決定方法
JP2003247983A (ja) * 2002-02-25 2003-09-05 Nippon Laser & Electronics Lab 標的物質質量分析システム
JP2004212215A (ja) * 2002-12-27 2004-07-29 Institute Of Physical & Chemical Research レーザーアブレーション高分子分析装置
JP2004257973A (ja) * 2003-02-27 2004-09-16 Jsr Corp 微小物の形状・構造分析方法及び装置
WO2005074003A1 (fr) * 2004-01-28 2005-08-11 Kyoto University Dispositif et pocédé d’analyse laser

Non-Patent Citations (1)

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Title
KATO T. ET AL.: "Kibanjo Shiryo ni Okeru Femtosecond to Nanosecond Laser Ablation no Hikaku", DAI 53 KAI OYO BUTSURIGAKU KANKEI RENGO KOENKAI, 22 March 2006 (2006-03-22), pages 1208 + ABSTR. NO. 25P-L-9, XP003021925 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014063585A (ja) * 2012-09-20 2014-04-10 Shimadzu Corp 真空チャンバ内におけるｘｙステージの支持構造およびレーザ脱離イオン化装置
JP2015152370A (ja) * 2014-02-13 2015-08-24 株式会社ニコン 検出装置、顕微鏡および処理装置
JP2016225108A (ja) * 2015-05-29 2016-12-28 国立研究開発法人日本原子力研究開発機構 質量分析装置、イオン照射装置
CN112730593A (zh) * 2020-11-26 2021-04-30 长春理工大学光电信息学院 一种超短脉冲激光电离有机氯农药的方法
CN112730593B (zh) * 2020-11-26 2024-01-19 长春理工大学光电信息学院 一种超短脉冲激光电离有机氯农药的方法

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