JP2732669B2 - Surface analysis method of insulator sample by X-ray photoelectron spectroscopy - Google Patents
Surface analysis method of insulator sample by X-ray photoelectron spectroscopyInfo
- Publication number
- JP2732669B2 JP2732669B2 JP1163351A JP16335189A JP2732669B2 JP 2732669 B2 JP2732669 B2 JP 2732669B2 JP 1163351 A JP1163351 A JP 1163351A JP 16335189 A JP16335189 A JP 16335189A JP 2732669 B2 JP2732669 B2 JP 2732669B2
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- Japan
- Prior art keywords
- sample
- ray photoelectron
- analysis
- insulator
- photoelectron spectrometer
- Prior art date
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Description
【発明の詳細な説明】 発明の技術分野 本発明は、単色型スモールスポットＸ線光電子分光装
置による絶縁物試料の表面分析法に関する。Description: TECHNICAL FIELD The present invention relates to a method for analyzing the surface of an insulator sample using a monochromatic small spot X-ray photoelectron spectrometer.
発明の技術的背景 Ｘ線光電子分光法は、Ｘ線を絶縁物に照射した際に放
出される光電式について、エネルギー分析を行なう電子
分光法の一種であり、表面分析に広く利用されてる。こ
のＸ線光電子分光法で用いられる装置には、Ｘ線モノク
ロメータを具備していない非単色型Ｘ線光電子分光装置
とＸ線モノクロメータを具備している単色型Ｘ線光電子
分光装置とがあり、単色型Ｘ線光電子分光装置は、さら
に試料表面の広範囲部分にＸ線を照射する単色型Ｘ線光
電子分光装置と、試料表面の微小部分にＸ線を照射する
単色型スモールスポットＸ線光電子分光装置とに分類さ
れる。TECHNICAL BACKGROUND OF THE INVENTION X-ray photoelectron spectroscopy is a type of electron spectroscopy for performing energy analysis on a photoelectric system emitted when an insulator is irradiated with X-rays, and is widely used for surface analysis. Devices used in this X-ray photoelectron spectroscopy include a non-monochromatic X-ray photoelectron spectrometer without an X-ray monochromator and a monochromatic X-ray photoelectron spectrometer with an X-ray monochromator. The monochromatic X-ray photoelectron spectrometer further includes a monochromatic X-ray photoelectron spectrometer that irradiates a wide area of the sample surface with X-rays, and a monochromatic small spot X-ray photoelectron spectrometer that irradiates X-rays to a minute portion of the sample surface. Devices are classified.
この単色型スモールスポットＸ線光電子分光装置は、
第１図に示すように、電子銃１より電子線をアノード２
に照射してＸ線を発生させ、このＸ線を単色化用湾曲分
光結晶３で受けて絶縁物試料４表面に、中和用電子銃５
による電子線照射をしながらＸ線をスモールスポットし
て高真空下にある絶縁物試料４表面から放出される電子
の運動エネルギーを測定して絶縁物試料表面の分析を行
なう仕組みになっている。This monochromatic small spot X-ray photoelectron spectrometer is
As shown in FIG. 1, an electron beam is emitted from an electron gun 1 to an anode 2.
To generate X-rays. The X-rays are received by the monochromatizing curved dispersive crystal 3 and are applied to the surface of the insulator sample 4 by the neutralizing electron gun 5.
X-rays are small-spotted while irradiating an electron beam by the method described above, and the kinetic energy of electrons emitted from the surface of the insulator sample 4 under a high vacuum is measured to analyze the surface of the insulator sample.
ところで、単色型スモールスポットＸ線光電子分光装
置を用いて従来の方法で、たとえばポリマー基板上にY2
O3層、さらにこの層の上にSiO2層が設けられている三層
積層板の試料表面に存在するSiあるいはＯの分析を行な
うと、第４図、第７図に示すように、ピークがブロード
なスペクトル図が得られ、正確な分析ができないという
問題点があった。By the way, using a single-color type small spot X-ray photoelectron spectrometer in a conventional method, for example, Y 2
Analysis of Si or O present on the sample surface of the three-layer laminate having the O 3 layer and the SiO 2 layer provided on this layer, as shown in FIG. 4 and FIG. However, there was a problem that a broad spectrum diagram was obtained and accurate analysis was not possible.
本発明者らは、上記のような問題点を解決すべく鋭意
研究し、単色型スモールスポットＸ線光電子分光装置の
試料室内に不活性ガスを導入して不活性ガス圧を１×10
-8〜１×10-6Torrの範囲内に維持し、中和用電子銃によ
絶縁物試料表面に電子線を照射して表面分析したとこ
ろ、ピークの狭いスペクトル図が得られ、正確な表面分
析ができることを見出し、本発明を完成するに至った。The present inventors have intensively studied to solve the above problems, and introduced an inert gas into the sample chamber of the monochromatic small spot X-ray photoelectron spectrometer to reduce the inert gas pressure to 1 × 10 5
-8 to 1 × 10 -6 Torr, and the surface of the insulator sample was irradiated with an electron beam by an electron gun for neutralization, and the surface was analyzed. The inventors have found that surface analysis can be performed, and have completed the present invention.
発明の目的 本発明は、上記のような従来技術に伴う問題点を解決
しようとするものであって、単色型スモールスポットＸ
線光電子分光装置による絶縁物試料表面の正確な表面分
析を可能にする分析法を提供することを目的としてい
る。An object of the present invention is to solve the problems associated with the prior art as described above.
It is an object of the present invention to provide an analysis method that enables accurate surface analysis of the surface of an insulating sample by a line photoelectron spectrometer.
発明の概要 本発明に係るＸ線光電子分光装置による絶縁物試料の
表面分析法は、単色型スモールスポットＸ線光電子分光
装置による絶縁物試料の表面分析の際に、試料室内に不
活性ガスを導入して不活性ガス圧を１×10-8〜１×10-6
Torrの範囲内に維持し、中和用電子銃により絶縁物試料
表面に電式線を照射することを特徴としている。SUMMARY OF THE INVENTION The surface analysis method for an insulator sample using an X-ray photoelectron spectrometer according to the present invention is such that an inert gas is introduced into a sample chamber during the surface analysis of an insulator sample using a monochromatic small spot X-ray photoelectron spectrometer. To make the inert gas pressure 1 × 10 -8 to 1 × 10 -6
It is maintained within the Torr range, and the surface of the insulator sample is irradiated with electric wires by a neutralizing electron gun.
発明の具体的説明 以下、本発明に係るＸ線光電子分光装置による絶縁物
試料の表面分析法について具体的に説明する。DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a method for analyzing the surface of an insulator sample using an X-ray photoelectron spectrometer according to the present invention will be specifically described.
なお本発明における試料の表面分析は、たとえば試料
表面の元素の種類、元素組成の分析、あるいは試料表面
の元素の原子価、元素の化合結合状態、元素の存在状態
の分析、あるいは電子状態等の分析を含む。The surface analysis of the sample in the present invention includes, for example, the analysis of the type and element composition of the element on the sample surface, or the analysis of the valence of the element on the sample surface, the combined state of the element, the presence of the element, or the electronic state. Including analysis.
本発明で用いられるＸ線光電子分光装置は、上述した
モノクロメータを具備する単色型スモールスポットＸ線
光電子分光装置である。The X-ray photoelectron spectrometer used in the present invention is a monochromatic small spot X-ray photoelectron spectrometer equipped with the above-described monochromator.
本発明では、上記のような単色型スモールスポットＸ
線光電子分光装置を用いて絶縁物試料表面の分析を行な
う際に、絶縁物試料がセットされている試料室内に不活
性ガスを導入して不活性ガス圧を１×10-8〜１×10-6To
rrの範囲内に維持する。In the present invention, the single-color type small spot X as described above is used.
When analyzing the surface of an insulator sample using a line photoelectron spectrometer, an inert gas is introduced into the sample chamber in which the insulator sample is set to increase the inert gas pressure from 1 × 10 −8 to 1 × 10 8. -6 To
Keep within rr.
本発明で用いられる不活性ガスとしては、具体的に
は、ヘリウム（He）、ネオン（Ne）、アルゴン（Ar）、
クリプトン（Kr）およびキセノン（Xe）の希ガス、窒素
ガス（N2）などが挙げられる。中でもアルゴンが好まし
く用いられる。As the inert gas used in the present invention, specifically, helium (He), neon (Ne), argon (Ar),
Noble gases of krypton (Kr) and xenon (Xe), nitrogen gas (N 2 ), and the like can be given. Among them, argon is preferably used.
また本発明においては、試料室内の不活性ガス圧は１
×10-8〜１×10-6Torr、好ましくは５×10-8〜１×10-7
Torrの範囲内である。In the present invention, the inert gas pressure in the sample chamber is 1 unit.
× 10 -8 to 1 × 10 -6 Torr, preferably 5 × 10 -8 to 1 × 10 -7
Within the range of Torr.
不活性ガス圧を上記のような範囲内にして絶縁物試料
表面の分析を行なうと、ピークの狭いスペクトル図が得
られ、単色型スモールスポットＸ線光電子分光装置によ
る正確な表面分析ができる。When the surface of the insulator sample is analyzed with the inert gas pressure within the above range, a spectrum diagram having a narrow peak is obtained, and accurate surface analysis can be performed by a monochromatic small spot X-ray photoelectron spectrometer.
本発明では、上記のような不活性ガスの存在下で、中
和用電子銃により試料室内の絶縁物試料表面に電子線を
照射する。In the present invention, an electron beam is irradiated to the surface of the insulator sample in the sample chamber by the neutralizing electron gun in the presence of the inert gas as described above.
上記のような電子線照射は、従来の単色型スモールス
ポットＸ線光電子分光装置による表面分析においても必
要であった。すなわち、Ｘ線照射により絶縁物試料表面
から電子が放出されて絶縁物試料表面の陽電荷による帯
電が生じ、この陽電荷がＸ線照射による電子の放出を妨
げるため、表面分析を行なうことができない。したがっ
て、上記のような表面分析を行なう際には、陽電荷の帯
電が生じる絶縁物試料表面に電子線照射を行なって中和
する必要があった。The above-mentioned electron beam irradiation was necessary also in the surface analysis by the conventional monochromatic small spot X-ray photoelectron spectrometer. That is, electrons are emitted from the surface of the insulator sample by the X-ray irradiation, and the surface of the insulator sample is charged by positive charges. The positive charges prevent the emission of electrons by the X-ray irradiation, so that the surface analysis cannot be performed. . Therefore, when performing the above-described surface analysis, it is necessary to perform electron beam irradiation on the surface of the insulator sample where positive charge is generated to neutralize the surface.
本発明においては、上記の電子線照射における電子線
エネルギーは、従来行なわれていた電子線照射における
電子線エネルギーと同じく、通常0.1〜5000eVの範囲内
である。In the present invention, the electron beam energy in the above-described electron beam irradiation is generally in the range of 0.1 to 5000 eV, similarly to the electron beam energy in the conventional electron beam irradiation.
本発明では、上記のように、中和用電子銃による電子
線照射と不活性ガスを併用して絶縁物試料表面の帯電を
防止しているため、スペクトルのピークがブロードにな
る原因と思われる絶縁物試料表面の帯電の不均一さがな
く、ピークの狭いスペクトル図が得られる。すなわち、
本発明によれば、単色型スモールスポットＸ線光電子分
光装置による絶縁物試料表面の元素分析を正確に行なう
ことができる。In the present invention, as described above, since the charge on the surface of the insulator sample is prevented by using the electron beam irradiation with the neutralizing electron gun and the inert gas in combination, it is considered that the peak of the spectrum becomes broad. There is no non-uniform charging on the surface of the insulator sample, and a spectrum diagram with a narrow peak can be obtained. That is,
ADVANTAGE OF THE INVENTION According to this invention, the elemental analysis of the insulator sample surface by a monochrome small spot X-ray photoelectron spectroscopy apparatus can be performed accurately.
発明の効果 本発明によれば、試料室内の不活性ガス圧を特定の範
囲内に維持して絶縁物試料表面に電子線を照射して分析
するので、単色型スモールスポットＸ線光電子分光装置
によってピークの狭いスペクトル図が得られ、正確な表
面分析ができる。Effects of the Invention According to the present invention, the surface of an insulating sample is irradiated with an electron beam for analysis while maintaining the inert gas pressure in the sample chamber within a specific range, so that a monochromatic small spot X-ray photoelectron spectrometer is used. A spectrum diagram with a narrow peak is obtained, and accurate surface analysis can be performed.
以下、本発明を実施例により説明するが、本発明は、
これら実施例に限定されるものではない。Hereinafter, the present invention will be described with reference to examples, the present invention,
It is not limited to these examples.
実施例１ 炭化水素系樹脂基板上に、Y2O3層、さらにこの層の上
にSiO2層が設けられている三層積層板の試料表面に存在
するSiO2層のケイ素（Si）について、単色型スモールス
ポットＸ線光電子分光装置［サーフェイス サイエンス
インストルメンツ（株）製、型番SSX−100］を用いて
以下の測定条件で分析を行なった。Example 1 Silicon (Si) of a SiO 2 layer present on a sample surface of a three-layer laminate in which a Y 2 O 3 layer is provided on a hydrocarbon-based resin substrate, and a SiO 2 layer is further provided on this layer The analysis was performed under the following measurement conditions using a monochromatic small spot X-ray photoelectron spectrometer [Model SSX-100 manufactured by Surface Science Instruments Co., Ltd.].
［測定条件］ Ｘ 線 径:0.3mmφ 中和電子銃：使用（2eV） 積 算：スキャンモード（４回） アルゴンガス圧:5×10-8Torr 得られたケイ素（Si）の2pスペクトルを第２図に示
す。[Measurement conditions] X-ray diameter: 0.3 mmφ Neutralizing electron gun: used (2 eV) Multiplication: scan mode (four times) Argon gas pressure: 5 × 10 -8 Torr The obtained 2p spectrum of silicon (Si) It is shown in FIG.
実施例２ 実施例１において、測定条件のアルゴンガス圧を１×
10-7Torrとした以外は、実施例１と同様にして、SiO2層
のケイ素（Si）について分析を行なった。Example 2 In Example 1, the argon gas pressure under the measurement conditions was changed to 1 ×
The analysis of silicon (Si) in the SiO 2 layer was performed in the same manner as in Example 1 except that the pressure was set to 10 −7 Torr.
得られたケイ素（Si）の2pスペクトルを第３図に示
す。FIG. 3 shows a 2p spectrum of the obtained silicon (Si).
比較例１ 実施例１において、測定条件のアルゴンガス圧を１×
10-8Torrの代わりに、試料室を高真空にして残留ガス圧
約１×10-9Torr以下とした以外は、実施例１と同様にし
て、SiO2層のケイ素（Si）について分析を行なった。Comparative Example 1 In Example 1, the argon gas pressure under the measurement conditions was 1 ×
Instead of 10 -8 Torr, the silicon (Si) of the SiO 2 layer was analyzed in the same manner as in Example 1 except that the sample chamber was set to a high vacuum and the residual gas pressure was set to about 1 × 10 -9 Torr or less. Was.
得られたケイ素（Si）の2pスペクトルを第４図に示
す。FIG. 4 shows a 2p spectrum of the obtained silicon (Si).
実施例３ 実施例１において、分析の対象を試料表面に存在する
SiO2層のケイ素（Si）の代わりに、試料表面に存在する
SiO2層の酸素（ｏ）にした以外は、実施例１と同様にし
て、分析を行なった。Example 3 In Example 1, the analysis target is present on the sample surface.
Exists on the sample surface instead of silicon (Si) in the SiO 2 layer
The analysis was performed in the same manner as in Example 1 except that oxygen (o) of the SiO 2 layer was used.
得られた酸素（ｏ）の1sスペクトルを第５図に示す。 FIG. 5 shows the obtained 1s spectrum of oxygen (o).
実施例４ 実施例１において、分析の対象を試料表面に存在する
SiO2層のケイ素（Si）の代わりに、試料表面に存在する
SiO2層の酸素（ｏ）にし、測定条件のアルゴン圧を１×
10-7Torrとした以外は、実施例１と同様にして、分析を
行なった。Example 4 In Example 1, the analysis target exists on the sample surface.
Exists on the sample surface instead of silicon (Si) in the SiO 2 layer
The oxygen (o) of the SiO 2 layer was changed to an argon pressure of 1 × for the measurement conditions.
The analysis was performed in the same manner as in Example 1 except that the pressure was changed to 10 -7 Torr.
得られた酸素（ｏ）の1sスペクトルを第６図に示す。 FIG. 6 shows the obtained 1s spectrum of oxygen (o).
比較例２ 実施例１において、分析の対象を試料表面に存在する
SiO2層のケイ素（Si）の代わりに、試料表面の存在する
SiO2層の酸素（ｏ）にし、測定条件のアルゴンガス圧を
１×10-8Torrの代わりに、試料室を高真空にして残留ガ
ス圧約１×10-9Torr以下とした以外は、実施例１と同様
にして、分析を行なった。Comparative Example 2 In Example 1, the analysis target is present on the sample surface.
The sample surface exists instead of silicon (Si) in the SiO 2 layer
Except that the SiO 2 layer was made oxygen (o) and the argon gas pressure under the measurement conditions was changed to 1 × 10 −8 Torr, and the sample chamber was set to a high vacuum to set the residual gas pressure to about 1 × 10 −9 Torr or less. The analysis was performed as in Example 1.
得られた酸素（ｏ）の1sスペクトルを第７図に示す。 FIG. 7 shows the obtained 1s spectrum of oxygen (o).
第１図は、本発明で用いられる単色型スモールスポット
Ｘ線光電子分光装置の概略図であり、第２図、第３図お
よび第４図は、それぞ実施例１、実施例２、比較例１に
おける分析により得られたケイ素（Si）の2pスペクトル
を表わす図であり、第５図、第６図および第７図は、そ
れぞれ実施例３、実施例４、比較例１における分析によ
り得られた酸素（ｏ）の1sスペクトルを表わす図であ
る。 １……電子銃、２……アノード ３……単色化用湾曲分光結晶 ４……絶縁物試料、５……中和用電子銃FIG. 1 is a schematic view of a monochromatic small spot X-ray photoelectron spectroscopy apparatus used in the present invention, and FIGS. 2, 3 and 4 show Examples 1, 2 and Comparative Examples, respectively. FIG. 5 is a diagram showing a 2p spectrum of silicon (Si) obtained by the analysis in FIG. 1, and FIGS. 5, 6, and 7 are obtained by the analysis in Example 3, Example 4, and Comparative Example 1, respectively. FIG. 4 is a diagram showing a 1s spectrum of oxygen (o). DESCRIPTION OF SYMBOLS 1 ... Electron gun, 2 ... Anode 3 ... Bending spectral crystal for monochromaticization 4 ... Insulator sample, 5 ... Electron gun for neutralization
Claims (1)
置による絶縁物試料の表面分析の際に、試料室内に不活
性ガスを導入して不活性ガス圧を１×10-8〜１×10-6To
rrの範囲内に維持し、中和用電子銃により絶縁物試料表
面に電子線を照射することを特徴とするＸ線光電子分光
装置による絶縁物試料の表面分析法。1. An inert gas is introduced into a sample chamber and the pressure of the inert gas is set to 1 × 10 −8 to 1 × 10 − at the time of surface analysis of an insulating sample by a monochromatic small spot X-ray photoelectron spectrometer. 6 To
A method for analyzing the surface of an insulator sample using an X-ray photoelectron spectrometer, wherein the surface of the insulator sample is irradiated with an electron beam by a neutralizing electron gun while being maintained within the range of rr.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1163351A JP2732669B2 (en) | 1989-06-26 | 1989-06-26 | Surface analysis method of insulator sample by X-ray photoelectron spectroscopy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1163351A JP2732669B2 (en) | 1989-06-26 | 1989-06-26 | Surface analysis method of insulator sample by X-ray photoelectron spectroscopy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0326948A JPH0326948A (en) | 1991-02-05 |
| JP2732669B2 true JP2732669B2 (en) | 1998-03-30 |
Family
ID=15772236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1163351A Expired - Fee Related JP2732669B2 (en) | 1989-06-26 | 1989-06-26 | Surface analysis method of insulator sample by X-ray photoelectron spectroscopy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2732669B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001009597A1 (en) * | 1999-07-28 | 2001-02-08 | Microcal, Llc | Pressure perturbation calorimetry instruments and methods |
| GB2411763B (en) | 2004-03-05 | 2009-02-18 | Thermo Electron Corp | Flood gun for charge neutralization |
-
1989
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Also Published As
| Publication number | Publication date |
|---|---|
| JPH0326948A (en) | 1991-02-05 |
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