JP5164145B2 - Secondary ion mass spectrometer - Google Patents

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JP5164145B2
JP5164145B2 JP2007300440A JP2007300440A JP5164145B2 JP 5164145 B2 JP5164145 B2 JP 5164145B2 JP 2007300440 A JP2007300440 A JP 2007300440A JP 2007300440 A JP2007300440 A JP 2007300440A JP 5164145 B2 JP5164145 B2 JP 5164145B2
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JP2009128045A (en
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幸雄 藤原
秀彦 野中
直昭 齋藤
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National Institute of Advanced Industrial Science and Technology AIST
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本発明は、分析試料を真空中に搬入し、イオンビームを分析試料に照射することにより発生した２次イオンの質量分析を行う方法、いわゆる「二次イオン質量分析法（Secondary Ion Mass Spectrometry：SIMS）」及びＳＩＭＳ装置に関する。   The present invention is a method for carrying out mass analysis of secondary ions generated by carrying an analysis sample into a vacuum and irradiating the analysis sample with an ion beam, so-called “Secondary Ion Mass Spectrometry (SIMS)”. ) "And SIMS device.

二次イオン質量分析（ＳＩＭＳ）は、真空中において、一次イオンビームを分析試料（有機物、バイオメディカル試料等）に照射し、分析試料表面から放出される二次イオンを質量分析することにより、分析試料の分子構造等に関する情報を得ることを目的する分析手法である。   In secondary ion mass spectrometry (SIMS), analysis is performed by irradiating an analysis sample (organic matter, biomedical sample, etc.) with a primary ion beam in a vacuum and mass analyzing the secondary ions released from the surface of the analysis sample. This is an analysis method that aims to obtain information on the molecular structure of a sample.

従来は、一次イオンビームとしてAr+など原子イオンが用いられてきたが、近年、一次イオンビームとしてクラスターイオンビームを用いることで有機材料やバイオメディカル試料等の高感度分析が可能であることが判明し、Au3 +やC60 +などのクラスターイオンを用いたSIMS分析が注目を集めている（例えば、非特許文献１参照）。 Conventionally, atomic ions such as Ar + have been used as the primary ion beam, but in recent years it has been found that high-sensitivity analysis of organic materials and biomedical samples is possible by using a cluster ion beam as the primary ion beam. However, SIMS analysis using cluster ions such as Au 3 + and C 60 + has attracted attention (see, for example, Non-Patent Document 1).

なお、分析試料表面から放出された二次イオンの質量分析法としては、検出効率が高く、検出可能な質量範囲が広いという利点を有することから、飛行時間型（Time-of-Flight：TOF）質量分析を用いたTOF-SIMSが広く用いられている。
N. Winograd, “The Magic of Cluster SIMS”,Analytical Chemistry, April 1 (2005) p 143 A. T. Iwanami, Yujing Liu, M. Okazaki, M. Nojima, T. Sakamoto, M. Owari, “Handling of the ice protective film for potential use in the 3D microscale analysis of biological samples”, v 38 (2006) p 1658. I. S. Gilmore and M. P. Seah, “Electron flood gun damage in the analysis of polymers and organic in time-of-flight SIMS”, Applied Surface Science, vol 187 (2002) p 89. As a method of mass spectrometry of secondary ions released from the surface of the analysis sample, it has the advantages of high detection efficiency and a wide detectable mass range, so time-of-flight (TOF) TOF-SIMS using mass spectrometry is widely used.
N. Winograd, “The Magic of Cluster SIMS”, Analytical Chemistry, April 1 (2005) p 143 A. T. Iwanami, Yujing Liu, M. Okazaki, M. Nojima, T. Sakamoto, M. Owari, “Handling of the ice protective film for potential use in the 3D microscale analysis of biological samples”, v 38 (2006) p 1658 . IS Gilmore and MP Seah, “Electron flood gun damage in the analysis of polymers and organic in time-of-flight SIMS”, Applied Surface Science, vol 187 (2002) p 89.

［課題１］二次イオン質量分析（SIMS）においては、分析試料は、真空容器中に搬入され、真空中において分析が行われる。このため、水を含有するバイオメディカル試料等のSIMS分析においては、分析試料中の水分の気化による分析試料の乾燥や凍結が発生し、バイオメディカル試料を「生のまま」分析することが難しく、大きな課題となっている（例えば、非特許文献２を参照）。   [Problem 1] In secondary ion mass spectrometry (SIMS), an analysis sample is carried into a vacuum vessel and analyzed in a vacuum. For this reason, in SIMS analysis of biomedical samples containing water, the analysis sample is dried or frozen due to vaporization of water in the analysis sample, making it difficult to analyze the biomedical sample "as is" This is a big problem (for example, see Non-Patent Document 2).

［課題２］また、電気絶縁性の分析試料の場合には、イオンビーム照射に起因する分析試料の帯電（チャージアップ）が問題となるため、電荷中和が必要不可欠となる。一般的には、分析試料に電子シャワーを照射し、分析試料の帯電（チャージアップ）を抑制する手法がとられることが多いが、この電子シャワーによって分析試料が損傷してしまうという問題がある（例えば、非特許文献３を参照）。   [Problem 2] Further, in the case of an electrically insulating analysis sample, charging of the analysis sample due to ion beam irradiation (charge-up) becomes a problem, so charge neutralization is indispensable. In general, a technique of irradiating an analysis sample with an electron shower to suppress charging (charge-up) of the analysis sample is often employed, but there is a problem that the analysis sample is damaged by the electron shower ( For example, see Non-Patent Document 3.)

［課題３］また、放出された二次イオンを質量分析するための飛行時間型質量分析法（TOF-MS）においては、イオンの飛行時間（ｔ）を測定し、その結果を質量電荷比（ｍ／ｚ）に変換する必要があるが、各ＳＩＭＳ装置毎および測定条件毎に異なる固有のパラメータが存在するため、なんらかの方法で補正する必要がある。   [Problem 3] In addition, in time-of-flight mass spectrometry (TOF-MS) for mass spectrometry of released secondary ions, the time of flight (t) of ions is measured, and the result is obtained as a mass-to-charge ratio ( m / z). However, since there are different unique parameters for each SIMS apparatus and for each measurement condition, it is necessary to correct by some method.

具体的には、下記（式１）のような関係式が飛行時間型質量分析法（TOF-MS）においては成立するが、各装置毎の寸法や使用電圧などの動作条件に依存するパラメータＣ１とＣ２が存在するため、なんらかの手法を用いて校正することが必要となる。
ｍ／ｚ＝Ｃ１（ｔ−Ｃ２）２ （１）
なお、（式1）において、ｍはイオンの質量、ｚはイオンの電荷である。Ｃ１は飛行時間から質量電荷比への変換係数であり、原理的には装置寸法と使用する電位で決まる定数であるが、装置寸法変化や電位の再現性などの影響が含まれるため校正すべきパラメータとなる。Ｃ２は測定用の電気回路や信号ケーブル等の影響を補正し、測定された飛行時間の値を真の飛行時間に修正する項である。 Specifically, the following relational expression (Equation 1) is established in time-of-flight mass spectrometry (TOF-MS), but the parameter C depends on the operating conditions such as dimensions and operating voltage for each device. since 1 and C 2 is present, it is necessary to calibrate using any technique.
m / z = C 1 (t -C 2) 2 (1)
In (Expression 1), m is the mass of the ion, and z is the charge of the ion. C 1 is a conversion coefficient from the time of flight to the mass-to-charge ratio. In principle, it is a constant determined by the device dimensions and the potential to be used. Parameter. C 2 is a term for correcting the influence of the measurement electric circuit, signal cable, etc., and correcting the measured flight time value to the true flight time.

既知の試料（校正用試料）の測定から、パラメータＣ１とＣ２を求める手法が一般的である。正しい測定を行うためには、頻繁にパラメータＣ１とＣ２を求めて校正すべきである。測定試料の中に校正用試料を混在させ計測中に同時に校正を行う手法もあるが、一般的には計測の前後あるいはそのどちらかのみで校正を行っている。 A technique for obtaining parameters C 1 and C 2 from measurement of a known sample (calibration sample) is common. In order to make correct measurements, the parameters C 1 and C 2 should be frequently determined and calibrated. There is also a method in which a calibration sample is mixed in a measurement sample and calibration is performed simultaneously during measurement, but in general, calibration is performed before or after measurement or only one of them.

上記課題を解決するため、本発明では、分析試料を真空雰囲気とする前に、分析試料表面を「イオン液体」により被覆するものである。   In order to solve the above problems, in the present invention, the surface of the analysis sample is covered with an “ionic liquid” before the analysis sample is brought into a vacuum atmosphere.

なお、「イオン液体（Ionic Liquid）」とは、room temperature molten saltとも呼ばれるもので、室温においても液体状態である塩（えん）の総称である。イオン液体は、プラスイオンとマイナスイオンから構成されている液体状の物質であり、高い導電性を持ち、蒸気圧がほとんど無いため真空中においても蒸発せずに液体のまま存在し、熱的に安定であること等の特徴から、ここ数年、注目を集めている物質である   The “ionic liquid” is also called room temperature molten salt, and is a general term for salts that are in a liquid state even at room temperature. An ionic liquid is a liquid substance composed of positive ions and negative ions. It has high electrical conductivity and has almost no vapor pressure. It has been attracting attention in recent years due to its characteristics such as stability.

従って、分析試料を真空中に入れる前に「イオン液体」で試料表面を覆い包むことで、分析試料中の水分の気化や気化に伴う分析試料の乾燥や凍結を防止することができ、[課題１]を解決することが可能となる。   Therefore, by covering the sample surface with `` ionic liquid '' before putting the analysis sample into the vacuum, it is possible to prevent moisture evaporation in the analysis sample and drying and freezing of the analysis sample due to vaporization. 1] can be solved.

また、仮に、分析試料が電気絶縁性であったとしても、導電性の「イオン液体」の存在により、イオンビーム照射に起因する帯電（チャージアップ）の問題、すなわち[課題２]は解決される。   Further, even if the analysis sample is electrically insulating, the presence of the conductive “ionic liquid” solves the problem of charging (charge-up) caused by ion beam irradiation, that is, [Problem 2]. .

さらに、「イオン液体」は、多種多様なものが市販されており、分子量が７００以上の非常に大きな「イオン液体」も存在する。従って、既知である「イオン液体」の二次イオン質量スペクトルを用いて、TOF-SIMS測定システムにおける質量スペクトルの校正を、簡便かつ精度良く行うことが可能となり、[課題３]が解決される。   Furthermore, a wide variety of “ionic liquids” are commercially available, and there are very large “ionic liquids” having a molecular weight of 700 or more. Therefore, it is possible to easily and accurately calibrate the mass spectrum in the TOF-SIMS measurement system using the known secondary ion mass spectrum of the “ionic liquid”, and [Problem 3] is solved.

なお、分析試料を「イオン液体」により被覆する場合において、「イオン液体」の層を必要以上に厚くしないことが望ましい。一つの方法としては、スピンコート法を用いて、「イオン液体」を分析試料表面に薄く被覆することが有効である。   When the analysis sample is coated with the “ionic liquid”, it is desirable that the “ionic liquid” layer not be thicker than necessary. As one method, it is effective to thinly coat the “ionic liquid” on the surface of the analysis sample by using a spin coating method.

本発明により、以下のような効果が得られる。
（１）真空環境下におかれた分析試料中の水分の気化や気化に伴う分析試料の乾燥や凍結を防止することができ、バイオメディカル試料等を“生のまま”に近い状態において二次イオン質量分析することが可能となる。
（２）仮に、分析試料が電気絶縁性であったとしても、帯電（チャージアップ）が発生しないため、電子シャワー等の電荷中和は不要となり、電子シャワーに起因する分析試料の劣化も防止される。
（３）TOF-SIMSシステムにおける質量スペクトルの校正を測定中に同時に行うことができるので、簡便に質量精度を向上させることが可能となる。 According to the present invention, the following effects can be obtained.
(1) Evaporation of moisture in an analysis sample placed in a vacuum environment and the drying and freezing of the analysis sample accompanying vaporization can be prevented. Ion mass spectrometry can be performed.
(2) Even if the analysis sample is electrically insulative, charging (charge-up) does not occur, so there is no need for charge neutralization such as electron shower, and deterioration of the analysis sample due to electron shower is prevented. The
(3) Since mass spectrum calibration in the TOF-SIMS system can be performed simultaneously during measurement, mass accuracy can be easily improved.

以下に、図面を参照して、本発明に係る「イオン液体」を用いて被覆された分析試料ならびに二次イオン質量分析装置の構成について説明する。   Below, with reference to drawings, the structure of the analytical sample coat | covered using the "ionic liquid" which concerns on this invention, and a secondary ion mass spectrometer is demonstrated.

図１は、本発明の実施例の概略図である。基本的に、一般的な飛行時間型質量分析計を備えた二次イオン質量分析装置（TOF-SIMS）であるが、分析試料に「イオン液体」を被覆するための“前処理室”が存在することが特徴である。   FIG. 1 is a schematic diagram of an embodiment of the present invention. Basically, it is a secondary ion mass spectrometer (TOF-SIMS) equipped with a general time-of-flight mass spectrometer, but there is a “pretreatment chamber” for coating the sample with “ionic liquid”. It is a feature.

前処理室においては、大気中において「イオン液体」を用いて分析試料の被覆が行われる。その後、「イオン液体」で被覆された分析試料は、TOF-SIMS装置内部の真空環境下に搬送され、分析が実施される。   In the pretreatment chamber, the analysis sample is coated with “ionic liquid” in the atmosphere. Thereafter, the analysis sample coated with the “ionic liquid” is transported in a vacuum environment inside the TOF-SIMS apparatus, and analysis is performed.

以上のような前処理によって、分析試料表面は、「イオン液体」によってコーティングされているため、真空条件下においても分析試料中の水分の気化や乾燥は起こらない。   By the pretreatment as described above, the surface of the analysis sample is coated with the “ionic liquid”, so that the moisture in the analysis sample does not vaporize or dry even under vacuum conditions.

また、イオンビーム照射を受けても、「イオン液体」の存在により、電気導電性が確保されているため、帯電（チャージアップ）は発生しない。   Further, even when irradiated with an ion beam, charging (charge-up) does not occur because electrical conductivity is ensured by the presence of the “ionic liquid”.

ＳＩＭＳ分析の開始時には、分析試料上に存在する「イオン液体」の二次イオンが放出されるため、その結果を用いて、TOF-SIMSシステム全体の校正を行うことが可能である。   At the start of the SIMS analysis, secondary ions of the “ionic liquid” existing on the analysis sample are released, and the result can be used to calibrate the entire TOF-SIMS system.

一次イオンビーム照射を受けた表面に存在していた「イオン液体」は、スパッタリングにより取り除かれることになるため、しばらくすると、分析試料自体の二次イオンが放出されるようになり、通常の二次イオン質量分析が行われる。   Since the “ionic liquid” present on the surface that has been irradiated with the primary ion beam is removed by sputtering, after a while, secondary ions of the analysis sample itself are released, and the normal secondary Ion mass spectrometry is performed.

なお、「イオン液体」としては多種多様なものが市販されているが、例えば、以下のような物質が知られている。
(a) Trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl) phosphinate,
(C48H102O2P2 ：分子量773.27)
(b) Trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)amide,
(C34H68F6NO4PS2：分子量 764.0)
(c) Tetrabutylammonium heptadecafluorooctanesulfonate,
(C24H36F17NO3S：分子量 741.59)
(d)1-Butyl-1-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)imidazolium
hexafluorophosphate, (C15H16F19N2P：分子量 616.24 )
(e)1-Methyl-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)imidazolium
hexafluorophosphate, (C12H10F19N2P：分子量 574.16)
(f) 1-Ethyl-3-methylimidazolium bis(pentafluoroethylsulfonyl)imide,
(C10H11F10N3O4S2：分子量 491.33)
(g)N,N-Diethyl-N-methyl-N-(2-methoxyethl)ammonium
bis(trifluoromethanesulfonyl)imide, (C10H20O5N2S2F6：分子量 426.4) A wide variety of “ionic liquids” are commercially available. For example, the following substances are known.
(a) Trihexyltetradecylphosphonium bis (2,4,4-trimethylpentyl) phosphinate,
(C48H102O2P2: molecular weight 773.27)
(b) Trihexyltetradecylphosphonium bis (trifluoromethylsulfonyl) amide,
(C34H68F6NO4PS2: molecular weight 764.0)
(c) Tetrabutylammonium heptadecafluorooctanesulfonate,
(C24H36F17NO3S: molecular weight 741.59)
(d) 1-Butyl-1- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) imidazolium
hexafluorophosphate, (C15H16F19N2P: molecular weight 616.24)
(e) 1-Methyl-3- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) imidazolium
hexafluorophosphate, (C12H10F19N2P: molecular weight 574.16)
(f) 1-Ethyl-3-methylimidazolium bis (pentafluoroethylsulfonyl) imide,
(C10H11F10N3O4S2: molecular weight 491.33)
(g) N, N-Diethyl-N-methyl-N- (2-methoxyethl) ammonium
bis (trifluoromethanesulfonyl) imide, (C10H20O5N2S2F6: molecular weight 426.4)

本発明によれば、電気絶縁性の有機試料や水分を含むようなバイオメディカル試料等の二次イオン質量分析が低損傷かつ高精度で、より“生のまま”に近い条件で実施可能となる。   According to the present invention, secondary ion mass spectrometry, such as an electrically insulating organic sample or a biomedical sample containing water, can be performed with low damage and high accuracy under more “raw” conditions. .

イオン液体を分析試料に被覆するための前処理室を備えた飛行時間型二次イオン質量分析（TOF-SIMS）装置の概略図。1 is a schematic view of a time-of-flight secondary ion mass spectrometry (TOF-SIMS) apparatus equipped with a pretreatment chamber for coating an analysis sample with an ionic liquid.

Claims (2)

分析試料を真空雰囲気中に導入する前に、該分析試料表面をイオン液体により被覆する二次イオン質量分析方法において、上記分析試料を被覆しているイオン液体の二次イオン質量スペクトルを用いて、二次イオン質量分析装置全体としての質量スペクトルの校正及び補正を行うことを特徴とする二次イオン質量分析方法。 Min析試fee prior to introduction into a vacuum atmosphere, the analysis sample surface in secondary ion mass spectrometry method of coating by the ionic liquid, using a secondary ion mass spectra of ionic liquids that are covering the analytical sample A secondary ion mass spectrometry method characterized by performing calibration and correction of a mass spectrum as a whole secondary ion mass spectrometer. 分析試料を真空雰囲気中に導入する前に、該分析試料表面をイオン液体により被覆する二次イオン質量分析装置において、上記分析試料を被覆しているイオン液体の二次イオン質量スペクトルを用いて、二次イオン質量分析装置全体としての質量スペクトルの校正及び補正を行うことを特徴とする二次イオン質量分析装置。 Min析試fee prior to introduction into a vacuum atmosphere, the analysis sample surface in a secondary ion mass spectrometer for coating by the ionic liquid, using a secondary ion mass spectra of ionic liquids that are covering the analytical sample A secondary ion mass spectrometer that performs calibration and correction of the mass spectrum of the secondary ion mass spectrometer as a whole.
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