JP2013167584A - Specific surface area measurement method and device for thin-film sample - Google Patents
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本発明は、基材上に特定元素を含有する薄膜が設けられている薄膜試料の当該薄膜における特定元素の単位質量当たりの表面積を測定する方法及び装置に関する。 The present invention relates to a method and an apparatus for measuring a surface area per unit mass of a specific element in a thin film sample in which a thin film containing a specific element is provided on a substrate.
粉末の比表面積については従来よりＢＥＴ法によって測定されている。ＢＥＴ法以外では、例えば、特許文献１に被測定物のＸ線散乱積分強度から比表面積を測定する方法が記載されている。この方法では、小角Ｘ線散乱曲線の始点から終点までの散乱角度についての積分値であるＸ線散乱積分強度と、被測定物の比表面積とがほぼ比例関係にあることを利用している。その被測定物の形態に関しては、粉末単独だけに限定されず、複合体中に含有される粉末、例えば粉末と樹脂の複合体、粉末と液体の複合体のように、粉末と他のＸ線透過性の材料とが複合化されたものでもよいとされている。 The specific surface area of the powder has been conventionally measured by the BET method. In addition to the BET method, for example, Patent Document 1 describes a method for measuring the specific surface area from the X-ray scattering integrated intensity of an object to be measured. This method utilizes the fact that the X-ray scattering integrated intensity, which is an integrated value for the scattering angle from the start point to the end point of the small-angle X-ray scattering curve, and the specific surface area of the object to be measured are approximately proportional. The form of the object to be measured is not limited to the powder alone, but the powder and other X-rays such as the powder contained in the composite, for example, the composite of powder and resin, the composite of powder and liquid. It is said that a composite with a permeable material may be used.
特許文献１に記載された比表面積測定方法は粉末を対象としており、基材に例えば金属が担持されて薄膜状になっている場合、その薄膜における金属の単位質量当たりの表面積を求めることはできない。また、金属や非金属の蒸着膜についても、その蒸着膜における金属や非金属の単位質量当たりの表面積を求める手法も未だ確立されていない。 The specific surface area measurement method described in Patent Document 1 is intended for powders, and when a metal is supported on a base material to form a thin film, the surface area per unit mass of the metal in the thin film cannot be obtained. . In addition, regarding a metal or nonmetal vapor-deposited film, a method for determining the surface area per unit mass of the metal or nonmetal in the vapor-deposited film has not yet been established.
例えば、自動車の排ガス触媒では貴金属の使用量を減らすために、貴金属をナノ粒子化し、さらに、実際の使用条件下での粒子の凝集を防ぐために、適切な担体を選ぶことが重要である。このような条件下での触媒の性能を議論するためには、貴金属が担体に担持されている状態での貴金属の比表面積に関する情報が重要であるが、これまでそのような比表面積の測定法は存在しない。 For example, in an automobile exhaust gas catalyst, in order to reduce the amount of noble metal used, it is important to make the noble metal into nanoparticles and to select an appropriate carrier in order to prevent particle aggregation under actual use conditions. In order to discuss the performance of the catalyst under such conditions, information on the specific surface area of the noble metal with the noble metal supported on the support is important. Does not exist.
このため、触媒や電池の電極材料等の性能評価には、例えば、基材に担持する前の粉末試料について得られた比表面積が用いられることがあるが、粉末状態での表面積と、基材に担持された状態での表面積とは、必ずしも対応しない。さらに、粉末を基材に担持して薄膜にしたときの表面積は、粉末の担持方法によって異なるのが通常である。 For this reason, for example, the specific surface area obtained for the powder sample before being supported on the base material may be used for the performance evaluation of the catalyst and the electrode material of the battery. It does not necessarily correspond to the surface area in the state of being supported on the surface. Furthermore, the surface area when the powder is supported on the base material to form a thin film usually varies depending on the method of supporting the powder.
そこで、本発明は、基材上で薄膜になった状態の該薄膜が含有する特定元素の単位質量当たりの表面積を精度良く測定することができるようにする。 Therefore, the present invention makes it possible to accurately measure the surface area per unit mass of the specific element contained in the thin film in the state of being thin on the substrate.
本発明は、上記課題を解決するために、薄膜にＸ線を照射した際に該薄膜から放出される電子及び蛍光Ｘ線を利用して、その薄膜が含有する特定元素の単位質量当たりの表面積を求めるようにした。 In order to solve the above-mentioned problems, the present invention utilizes the electrons and fluorescent X-rays emitted from the thin film when the thin film is irradiated with X-rays, and uses the surface area per unit mass of the specific element contained in the thin film. I asked for.
ここに提示する薄膜試料の比表面積測定方法は、基材上に特定元素を含有する薄膜が設けられている薄膜試料の当該薄膜における特定元素の単位質量当たりの表面積である比表面積を測定する方法であって、
上記特定元素の吸収端前後のエネルギーのＸ線を上記薄膜に照射するＸ線照射ステップと、
上記Ｘ線が照射された試料から放出された電子及び蛍光Ｘ線をそれぞれ検出する検出ステップと、
上記電子の放出量に基いてＸ線照射領域の上記特定元素の表面積Ｓに比例する電子収量Ｉｃを得る電子収量検出ステップと、
上記蛍光Ｘ線の放出量に基いてＸ線照射領域内の上記特定元素の量Ｍに比例する蛍光Ｘ線収量Ｉｆを得る蛍光Ｘ線収量検出ステップと、
上記電子収量Ｉｃと上記蛍光Ｘ線収量Ｉｆとに基いて、上記薄膜の上記特定元素に係る比表面積ＳＡを算出する処理ステップとを備えていることを特徴とする。
The specific surface area measuring method of the thin film sample presented here is a method of measuring the specific surface area, which is the surface area per unit mass of the specific element in the thin film of the thin film sample in which the thin film containing the specific element is provided on the substrate Because
An X-ray irradiation step of irradiating the thin film with X-rays of energy before and after the absorption edge of the specific element;
A detection step of detecting electrons and fluorescent X-rays emitted from the sample irradiated with the X-rays;
An electron yield detection step for obtaining an electron yield Ic proportional to the surface area S of the specific element in the X-ray irradiation region based on the electron emission amount;
A fluorescent X-ray yield detection step for obtaining a fluorescent X-ray yield If which is proportional to the amount M of the specific element in the X-ray irradiation region based on the emission amount of the fluorescent X-ray;
And a processing step of calculating a specific surface area SA related to the specific element of the thin film based on the electron yield Ic and the fluorescent X-ray yield If.
また、ここに提示する薄膜試料の比表面積測定装置は、基材上に特定元素を含有する薄膜が設けられている薄膜試料の当該薄膜における特定元素の単位質量当たりの表面積である比表面積を測定する装置であって、
上記特定元素の吸収端前後のエネルギーのＸ線を上記薄膜に照射するＸ線照射部と、
上記Ｘ線照射部によるＸ線が照射された試料から放出された電子を検出する電子検出部と、
上記Ｘ線照射部によるＸ線が照射された試料から放出された蛍光Ｘ線を検出する蛍光Ｘ線検出部と、
上記電子検出部で検出された電子放出量に基いて、Ｘ線照射領域の上記特定元素の表面積Ｓに比例する電子収量Ｉｃを得る電子収量検出部と、
上記蛍光Ｘ線検出部で検出された蛍光Ｘ線放出量に基いて、Ｘ線照射領域内の上記特定元素の量Ｍに比例する蛍光Ｘ線収量Ｉｆを得る蛍光Ｘ線収量検出部と、
上記電子収量検出部で検出された電子収量Ｉｃと、上記蛍光Ｘ線収量検出部で検出された蛍光Ｘ線収量Ｉｆとに基いて、上記薄膜における上記特定元素に係る比表面積ＳＡを算出する処理部とを備えていることを特徴とする。
In addition, the specific surface area measuring device for thin film samples presented here measures the specific surface area, which is the surface area per unit mass of the specific element in the thin film, where the thin film containing the specific element is provided on the substrate. A device that performs
An X-ray irradiation unit that irradiates the thin film with X-rays of energy before and after the absorption edge of the specific element;
An electron detection unit for detecting electrons emitted from the sample irradiated with X-rays by the X-ray irradiation unit;
A fluorescent X-ray detection unit for detecting fluorescent X-rays emitted from a sample irradiated with X-rays by the X-ray irradiation unit;
An electron yield detector that obtains an electron yield Ic that is proportional to the surface area S of the specific element in the X-ray irradiation region based on the amount of electron emission detected by the electron detector;
A fluorescent X-ray yield detector that obtains a fluorescent X-ray yield If proportional to the amount M of the specific element in the X-ray irradiation region based on the amount of fluorescent X-ray emission detected by the fluorescent X-ray detector;
Processing for calculating the specific surface area SA related to the specific element in the thin film based on the electron yield Ic detected by the electron yield detector and the fluorescent X-ray yield If detected by the fluorescent X-ray yield detector. And a portion.
すなわち、試料に特定元素の吸収端前後のエネルギーのＸ線を照射すると、特定元素がＸ線を吸収することにより、そのＸ線の吸収量に比例した量の光電子及びオージェ電子を放出するとともに、そのＸ線の吸収量に比例した量の蛍光Ｘ線を放出する。 That is, when the sample is irradiated with X-rays having energy before and after the absorption edge of the specific element, the specific element absorbs X-rays, thereby emitting photoelectrons and Auger electrons in proportion to the amount of X-ray absorption, An amount of fluorescent X-rays proportional to the amount of X-ray absorption is emitted.
光電子及びオージェ電子は、脱出深度が浅いことが知られており、試料表面部の特定元素から放出される。そのため、電子収量Ｉｃは、式（１）で表されるように、Ｘ線照射領域の特定元素の表面積Ｓに比例したものになる。一方、蛍光Ｘ線は、脱出深度が深いことが知られており、試料表面から内部にわたって存在する特定元素から放出される。そのため、蛍光Ｘ線収量Ｉｆは、式（２）で表されるように、Ｘ線照射領域内に存在する特定元素量Ｍに比例したものになる。本発明は、上記電子収量Ｉｃ及び蛍光Ｘ線収量Ｉｆに式（１），（２）の比例関係を有することに着目し、この電子収量Ｉｃ及び蛍光Ｘ線収量Ｉｆに基いて特定元素に係る比表面積ＳＡを得るようにしたものである。 Photoelectrons and Auger electrons are known to have a shallow escape depth and are emitted from specific elements on the surface of the sample. Therefore, the electron yield Ic is proportional to the surface area S of the specific element in the X-ray irradiation region, as represented by the formula (1). On the other hand, fluorescent X-rays are known to have a deep escape depth, and are emitted from specific elements existing from the sample surface to the inside. Therefore, the fluorescent X-ray yield If is proportional to the specific element amount M present in the X-ray irradiation region, as represented by the formula (2). The present invention pays attention to the fact that the electron yield Ic and the fluorescent X-ray yield If have a proportional relationship of the formulas (1) and (2). The specific surface area SA is obtained.
Ｉｃ＝α・Ｓ …（１）
Ｉｃ；電子収量（Ｘ線吸収強度）
α；放出電子の検出に関する装置定数（ｍ−２）
Ｓ；特定元素の表面積（ｍ２）
Ｉｆ＝β・Ｍ …（２）
Ｍ＝Ｓ０・ρ・ｄ
Ｉｆ；蛍光Ｘ線収量（Ｘ線吸収強度）
β；蛍光Ｘ線の検出に関する装置定数（ｇ−１）
Ｓ０;Ｘ線照射面積（ｍ２）
ρ；特定元素の密度（ｇ・ｍ−３）
ｄ；膜厚（ｍ）
Ic = α · S (1)
Ic: Electron yield (X-ray absorption intensity)
α: Device constant for detection of emitted electrons (m −2 )
S: Surface area of specific element (m 2 )
If = β · M (2)
M = S 0 · ρ · d
If; fluorescent X-ray yield (X-ray absorption intensity)
β: Apparatus constant for detection of fluorescent X-rays (g −1 )
S 0 ; X-ray irradiation area (m 2 )
ρ: density of a specific element (g · m −3 )
d: Film thickness (m)
上記装置定数α，βは、検出立体角、検出器の感度、測定条件等によって決まる定数である。 The apparatus constants α and β are constants determined by the detection solid angle, the sensitivity of the detector, the measurement conditions, and the like.
比表面積ＳＡは式（３）で表される。すなわち、電子収量Ｉｃ及び蛍光Ｘ線収量Ｉｆと装置定数α，βとから特定元素の単位質量当たりの表面積が得られる。 The specific surface area SA is represented by the formula (3). That is, the surface area per unit mass of the specific element is obtained from the electron yield Ic, the fluorescent X-ray yield If, and the device constants α and β.
ＳＡ＝Ｓ／Ｍ＝(Ｉｃ／Ｉｆ)・(β／α) …（３） SA = S / M = (Ic / If) · (β / α) (3)
上記装置定数α，βは次の方法で求めることができる。すなわち、基材上の薄膜の特定元素量Ｍ及び特定元素の表面積Ｓが既知である標準試料を準備する。この標準試料について、上記Ｘ線照射ステップ、上記検出ステップ、上記電子収量検出ステップ及び上記蛍光Ｘ線収量検出ステップにより、電子収量Ｉｃ及び蛍光Ｘ線収量Ｉｆを得る。上記標準試料に係る電子収量Ｉｃと表面積Ｓとに基いて装置定数α＝Ｉｃ／Ｓを求め、蛍光Ｘ線収量Ｉｆと特定元素量Ｍとに基いて装置定数β＝Ｉｆ／Ｍを求める。 The device constants α and β can be obtained by the following method. That is, a standard sample in which the specific element amount M of the thin film on the substrate and the surface area S of the specific element are known is prepared. With respect to this standard sample, the electron yield Ic and the fluorescent X-ray yield If are obtained by the X-ray irradiation step, the detection step, the electron yield detection step, and the fluorescent X-ray yield detection step. The apparatus constant α = Ic / S is determined based on the electron yield Ic and the surface area S of the standard sample, and the apparatus constant β = If / M is determined based on the fluorescent X-ray yield If and the specific element amount M.
ここに、「特定元素を含有する薄膜」は、微視的観察において、膜材が基板表面で連続的に広がった連続膜に限らず、膜材が隙間を存して分散しているものを含む。その薄膜は、金属のような特定元素よりなる膜材で形成されている場合に限らず、合金や化合物のような特定元素を含む膜材で形成されていてもよく、或いは特定元素よりなる膜材と他の元素よりなる膜材との複合膜であってもよい。 Here, the “thin film containing a specific element” is not limited to a continuous film in which the film material continuously spreads on the surface of the substrate in microscopic observation, but the film material is dispersed with a gap. Including. The thin film is not limited to a film material made of a specific element such as a metal, but may be formed of a film material containing a specific element such as an alloy or a compound, or a film made of a specific element. A composite film of a material and a film material made of another element may be used.
上記電子収量検出部、上記蛍光Ｘ線収量検出部及び上記処理部に関する好ましい態様は次のとおりである。 The preferred embodiments relating to the electron yield detection unit, the fluorescent X-ray yield detection unit, and the processing unit are as follows.
上記電子収量検出部は、上記電子検出部で検出された電子放出量に基いてＸ線の吸収係数に関するＸ線吸収スペクトルを得る電子収量スペクトル検出部と、該電子収量スペクトル検出部で検出したＸ線吸収スペクトルを数値化して、式（１）で表されるＸ線照射領域の上記特定元素の表面積Ｓに比例する電子収量Ｉｃを得る電子収量スペクトル数値化部とを備える。 The electron yield detector includes an electron yield spectrum detector that obtains an X-ray absorption spectrum related to an X-ray absorption coefficient based on the amount of electron emission detected by the electron detector, and an X detected by the electron yield spectrum detector. An electron yield spectrum quantification unit that digitizes the linear absorption spectrum and obtains an electron yield Ic proportional to the surface area S of the specific element in the X-ray irradiation region represented by the formula (1).
上記蛍光Ｘ線収量検出部は、上記蛍光Ｘ線検出部で検出された蛍光Ｘ線放出量に基いてＸ線の吸収係数に関するＸ線吸収スペクトルを得る蛍光Ｘ線収量スペクトル検出部と、該蛍光Ｘ線収量スペクトル検出部で検出したＸ線吸収スペクトルを数値化して、式（２）で表されるＸ線照射領域内の特定元素量Ｍに比例する蛍光Ｘ線収量Ｉｆを得る蛍光Ｘ線収量スペクトル数値化部とを備える。 The fluorescent X-ray yield detection unit includes a fluorescent X-ray yield spectrum detection unit that obtains an X-ray absorption spectrum related to an X-ray absorption coefficient based on the amount of fluorescent X-ray emission detected by the fluorescent X-ray detection unit; Fluorescent X-ray yield to obtain a fluorescent X-ray yield If proportional to the specific element amount M in the X-ray irradiation region represented by the formula (2) by digitizing the X-ray absorption spectrum detected by the X-ray yield spectrum detector A spectrum digitizing unit.
上記処理部は、上記電子の検出に関する装置定数αに対する上記蛍光Ｘ線の検出に関する装置定数βの比を装置定数比β／αとして記憶する記憶部を有し、上記電子収量スペクトル数値化部で数値化された電子収量Ｉｃと、上記蛍光Ｘ線収量スペクトル数値化部で数値化された蛍光Ｘ線収量Ｉｆと、上記記憶部の装置定数比β／αとに基いて、式（３）によって上記特定元素に係る比表面積ＳＡを算出する。 The processing unit includes a storage unit that stores a ratio of the device constant β related to the detection of the fluorescent X-rays to the device constant α related to the detection of the electrons as a device constant ratio β / α. Based on the digitized electron yield Ic, the fluorescent X-ray yield If digitized by the fluorescent X-ray yield spectrum digitizing unit, and the device constant ratio β / α of the storage unit, The specific surface area SA related to the specific element is calculated.
また、上記電子収量検出部が上記電子収量スペクトル検出部及び電子収量スペクトル数値化部を備え、上記蛍光Ｘ線収量検出部が上記蛍光Ｘ線収量スペクトル検出部及び蛍光Ｘ線収量スペクトル数値化部を備えるケースにおいて、上記処理部の別の好ましい態様は次のとおりである。 The electron yield detection unit includes the electron yield spectrum detection unit and the electron yield spectrum digitization unit, and the fluorescent X-ray yield detection unit includes the fluorescent X-ray yield spectrum detection unit and the fluorescent X-ray yield spectrum digitization unit. In the case of providing, another preferable aspect of the processing unit is as follows.
すなわち、上記処理部は、上記電子の検出に関する装置定数α及び上記蛍光Ｘ線の検出に関する装置定数βを記憶する記憶部を有し、上記電子収量スペクトル数値化部で数値化された電子収量Ｉｃと上記記憶部の電子の検出に関する装置定数αとに基いてＸ線照射領域の上記特定元素の表面積Ｓを算出し、上記蛍光Ｘ線収量スペクトル数値化部で数値化された蛍光Ｘ線収量Ｉｆと上記記憶部の蛍光Ｘ線の検出に関する装置定数βとに基いてＸ線照射領域内の上記特定元素量Ｍを算出し、上記特定元素の表面積Ｓと上記特定元素量Ｍとに基いて該特定元素に係る比表面積ＳＡを算出する。 That is, the processing unit includes a storage unit that stores an apparatus constant α related to the detection of the electrons and an apparatus constant β related to the detection of the fluorescent X-ray, and the electron yield Ic quantified by the electron yield spectrum quantification unit. The surface area S of the specific element in the X-ray irradiation region is calculated based on the device constant α relating to the detection of electrons in the storage unit, and the fluorescent X-ray yield If quantified by the fluorescent X-ray yield spectrum digitizing unit. And the specific element amount M in the X-ray irradiation region based on the apparatus constant β relating to the detection of fluorescent X-rays in the storage unit, and based on the surface area S of the specific element and the specific element amount M The specific surface area SA related to the specific element is calculated.
本発明によれば、特定元素の吸収端前後のＸ線を基材上の薄膜に照射することによって、Ｘ線照射領域の上記特定元素の表面積Ｓに比例する電子収量Ｉｃと、Ｘ線照射領域内の上記特定元素の量Ｍに比例する蛍光Ｘ線収量Ｉｆとを求め、この電子収量Ｉｃと蛍光Ｘ線収量Ｉｆとに基いて、上記薄膜の上記特定元素に係る比表面積ＳＡを算出するようにしたから、基材上で薄膜になった状態での特定元素の比表面積に関する情報を得ることができ、触媒、電池の電極等の表面における特定元素の化学的、物理的ないしは電気的な性能評価に有利になる。 According to the present invention, by irradiating the thin film on the substrate with X-rays before and after the absorption edge of the specific element, the electron yield Ic proportional to the surface area S of the specific element in the X-ray irradiation region, and the X-ray irradiation region A fluorescent X-ray yield If proportional to the amount M of the specific element is obtained, and a specific surface area SA related to the specific element of the thin film is calculated based on the electron yield Ic and the fluorescent X-ray yield If. Therefore, it is possible to obtain information on the specific surface area of a specific element in the state of a thin film on a substrate, and the chemical, physical or electrical performance of the specific element on the surface of a catalyst, battery electrode, etc. It becomes advantageous for evaluation.
以下、本発明を実施するための形態を図面に基づいて説明する。以下の好ましい実施形態の説明は、本質的に例示に過ぎず、本発明、その適用物或いはその用途を制限することを意図するものではない。 Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. The following description of the preferred embodiments is merely exemplary in nature and is not intended to limit the invention, its application, or its use.
＜比表面積測定装置＞
薄膜試料の比表面積測定方法に用いる装置について説明する。ここに、薄膜試料は、基材上に特定元素を含有する薄膜が設けられたものである。
<Specific surface area measuring device>
The apparatus used for the specific surface area measuring method of a thin film sample is demonstrated. Here, the thin film sample is obtained by providing a thin film containing a specific element on a base material.
図１は、本発明の実施形態に係る薄膜試料の比表面積測定装置１の概略構造を示す。この比表面積測定装置１は、転換電子収量法と蛍光Ｘ線収量法とを利用して薄膜試料の比表面積を測定する装置（ＸＡＦＳ分析装置）である。 FIG. 1 shows a schematic structure of a specific surface area measuring apparatus 1 for a thin film sample according to an embodiment of the present invention. The specific surface area measuring apparatus 1 is an apparatus (XAFS analyzer) that measures the specific surface area of a thin film sample using a conversion electron yield method and a fluorescent X-ray yield method.
比表面積測定装置１は試料（薄膜試料）Ｗを収容するチャンバー２を備えている。チャンバー２には試料ホルダ３が配設されている。試料ホルダ３は、その上部に試料Ｗを保持するとともに、この保持状態で試料Ｗの上面を任意の傾斜角度に設定可能に構成されている。試料ホルダ３には、保持した試料Ｗを１００ＭΩ以上で電気的に絶縁する絶縁構造が設けられている。試料ホルダ３に固定された試料Ｗには、導線４を介して電子検出部としての微小電流検出器５が接続されている。微小電流検出器５は試料ＷにＸ線を照射した際に放出される光電子及びオージェ電子を検出することが可能な高感度のものである。上記絶縁構造により試料Ｗを電気的に絶縁しておくことで、この微小電流検出器５での検出精度が十分に確保できるようになっている。微小電流検出器５による検出信号はコンピュータ１０に入力されるようになっている。 The specific surface area measuring apparatus 1 includes a chamber 2 that accommodates a sample (thin film sample) W. A sample holder 3 is disposed in the chamber 2. The sample holder 3 is configured so that the sample W is held on the upper part thereof, and the upper surface of the sample W can be set to an arbitrary inclination angle in this held state. The sample holder 3 is provided with an insulating structure for electrically insulating the held sample W at 100 MΩ or more. A minute current detector 5 as an electron detector is connected to the sample W fixed to the sample holder 3 via a lead wire 4. The minute current detector 5 has a high sensitivity capable of detecting photoelectrons and Auger electrons emitted when the sample W is irradiated with X-rays. By sufficiently insulating the sample W with the insulating structure, sufficient detection accuracy can be secured with the minute current detector 5. A detection signal from the minute current detector 5 is input to the computer 10.
上記チャンバー２の上方には高真空Ｘ線導波管１１が、Ｘ線の出射口を下方へ向けて配設されている。Ｘ線導波管１１は、Ｘ線が透過する分光器１２を備えている。分光器１２はコンピュータ１０の分光器制御部１３に接続されており、分光器１２により出射口から出射されるＸ線のエネルギー（波長）が変えられるようになっている。これらＸ線導波管１１及び分光器制御部１３によりＸ線照射部１４が構成されている。尚、この明細書では、Ｘ線の波長により決定されるフォトン１個が持つエネルギーをＸ線のエネルギーと呼ぶこととする。分光器制御器１３によってＸ線のエネルギーを制御することにより、エネルギーが約１０００ｅＶ〜約３０００ｅＶの間のＸ線、いわゆる軟Ｘ線をＸ線導波管１１から出射することができる。 A high vacuum X-ray waveguide 11 is disposed above the chamber 2 with the X-ray exit opening facing downward. The X-ray waveguide 11 includes a spectrometer 12 that transmits X-rays. The spectrometer 12 is connected to the spectrometer controller 13 of the computer 10 so that the energy (wavelength) of X-rays emitted from the emission port can be changed by the spectrometer 12. These X-ray waveguide 11 and spectroscope control unit 13 constitute an X-ray irradiation unit 14. In this specification, the energy of one photon determined by the X-ray wavelength is referred to as X-ray energy. By controlling the energy of X-rays by the spectroscope controller 13, X-rays whose energy is between about 1000 eV and about 3000 eV, so-called soft X-rays, can be emitted from the X-ray waveguide 11.
上記チャンバー２の上壁には、ベリリウムで構成されたベリリウム薄膜１５がチャンバー２内外を仕切るように配設されている。上記Ｘ線導波管１１は、その出射口がベリリウム薄膜１５の上面に対向するように位置付けられていて、出射口から出射されたＸ線がベリリウム薄膜１５を透過して試料Ｗの上面に照射されるようになっている。図示しないが、ベリリウム薄膜１５とチャンバー２上壁との間にはＯリング等のシール材が配設されている。同様に、ベリリウム薄膜１５と上記Ｘ線導波管１１の出射口周縁との間にもシール材が配設されている。 A beryllium thin film 15 made of beryllium is disposed on the upper wall of the chamber 2 so as to partition the inside and outside of the chamber 2. The X-ray waveguide 11 is positioned so that the exit port faces the upper surface of the beryllium thin film 15, and X-rays emitted from the exit port pass through the beryllium thin film 15 and irradiate the upper surface of the sample W. It has come to be. Although not shown, a sealing material such as an O-ring is disposed between the beryllium thin film 15 and the upper wall of the chamber 2. Similarly, a sealing material is also disposed between the beryllium thin film 15 and the peripheral edge of the X-ray waveguide 11.
上記チャンバー２には、図外の真空ポンプに接続された真空導入管１８と、チャンバー２内にヘリウムガスを導入するガス導入管１９とが接続されている。真空導入管１８によりチャンバー２内の真空引きを行なった後、ガス導入管１９からヘリウムガスを導入することで、チャンバー２内がヘリウムガスで満たされる。このようにチャンバー２内をヘリウムガスで満たすことにより、チャンバー２内の圧力を常圧にしながら、Ｘ線の散乱を抑制することが可能となる。また、真空導入管１８による真空引きの度合いや、ガス導入管１９によるヘリウムガスの導入量等により、チャンバー２内の圧力を調整することが可能である。ガス導入管１９からは、ヘリウムガス以外でＸ線の散乱を抑制するガスを導入するようにしてもよい。 A vacuum introduction pipe 18 connected to a vacuum pump (not shown) and a gas introduction pipe 19 for introducing helium gas into the chamber 2 are connected to the chamber 2. After evacuating the chamber 2 with the vacuum introduction tube 18, the chamber 2 is filled with helium gas by introducing helium gas from the gas introduction tube 19. By filling the chamber 2 with helium gas in this way, X-ray scattering can be suppressed while the pressure in the chamber 2 is kept at normal pressure. Further, the pressure in the chamber 2 can be adjusted by the degree of evacuation by the vacuum introduction pipe 18 or the amount of helium gas introduced by the gas introduction pipe 19. A gas that suppresses X-ray scattering other than helium gas may be introduced from the gas introduction pipe 19.
また、上記チャンバー２の側壁には、Ｘ線を照射した試料Ｗから放出される蛍光Ｘ線を検出する蛍光Ｘ線検出部としての蛍光Ｘ線検出器２０が配設されている。つまり、比表面積測定装置１は、上記チャンバー２、微小電流検出器５、Ｘ線導波管１１、真空導入管１８、ガス導入管１９、蛍光Ｘ線検出器２０及びコンピュータ１０で構成されている。 A fluorescent X-ray detector 20 as a fluorescent X-ray detector for detecting fluorescent X-rays emitted from the sample W irradiated with X-rays is disposed on the side wall of the chamber 2. That is, the specific surface area measuring apparatus 1 includes the chamber 2, the minute current detector 5, the X-ray waveguide 11, the vacuum introduction tube 18, the gas introduction tube 19, the fluorescent X-ray detector 20, and the computer 10. .
上記蛍光Ｘ線検出器２０は、Ｘ線を利用した試料分析装置に一般に用いられている周知のものである。蛍光Ｘ線検出器２０の検出部２０ａは上記チャンバー２内に臨んでおり、検出部２０ａが試料Ｗに対し進退するように構成されている。蛍光Ｘ線検出器２０には、検出信号を増幅する増幅器２１が接続され、増幅器２１で増幅された信号は上記コンピュータ１０に入力される。 The fluorescent X-ray detector 20 is a well-known one that is generally used in sample analyzers using X-rays. The detection unit 20 a of the fluorescent X-ray detector 20 faces the chamber 2, and the detection unit 20 a is configured to advance and retract with respect to the sample W. The fluorescent X-ray detector 20 is connected to an amplifier 21 that amplifies the detection signal, and the signal amplified by the amplifier 21 is input to the computer 10.
上記蛍光Ｘ線検出器２０の検出部２０ａを進退させることで、試料Ｗから放出された蛍光Ｘ線の取り込み角を適切に設定して蛍光Ｘ線の数え落としによる検出効率の低下を回避することかできる。また、上記試料ホルダ３により試料Ｗ上面の傾斜角度を変えることで、該試料Ｗから蛍光Ｘ線検出器２０へ向けて放出される蛍光Ｘ線の強度を変化させることができる。この蛍光Ｘ線の強度が最大となるように試料Ｗ上面の傾斜角度を調整することで、蛍光Ｘ線の検出が確実になる。 By advancing and retreating the detection unit 20a of the fluorescent X-ray detector 20, the capture angle of the fluorescent X-rays emitted from the sample W is appropriately set to avoid a decrease in detection efficiency due to counting off of the fluorescent X-rays. I can do it. Further, by changing the inclination angle of the upper surface of the sample W by the sample holder 3, the intensity of the fluorescent X-rays emitted from the sample W toward the fluorescent X-ray detector 20 can be changed. By adjusting the inclination angle of the upper surface of the sample W so that the intensity of the fluorescent X-ray is maximized, the detection of the fluorescent X-ray is ensured.
上記微小電流検出器５は、光電子及びオージェ電子を連続的に検出してその検出信号を上記コンピュータ１０に送る。また、蛍光Ｘ線検出器２０も同様に蛍光Ｘ線の検出信号を上記コンピュータ１０に送る。コンピュータ１０は、微小電流検出器５及び蛍光Ｘ線検出器２０から送られた連続信号を単位時間で区切って光電子及びオージェ電子の放出量と蛍光Ｘ線の放出量とをそれぞれ得るカウンタ２３を備えている。 The minute current detector 5 continuously detects photoelectrons and Auger electrons and sends detection signals to the computer 10. Similarly, the fluorescent X-ray detector 20 sends a fluorescent X-ray detection signal to the computer 10. The computer 10 includes a counter 23 that obtains the emission amount of photoelectrons and Auger electrons and the emission amount of fluorescent X-rays by dividing the continuous signals sent from the minute current detector 5 and the fluorescent X-ray detector 20 in unit time. ing.
また、分光器制御部１３は、試料Ｗの薄膜を構成する特定元素の吸収端前後のエネルギーのＸ線を薄膜に照射すべく、Ｘ線のエネルギーを予め設定された範囲（吸収端よりも低エネルギー側の所定値から吸収端よりも高エネルギー側の所定値までの範囲）内で掃引するように構成されている。上記カウンタ２３は、照射されたＸ線の各エネルギーにおける光電子及びオージェ電子の放出量と蛍光Ｘ線の放出量とを同時に検出する。これら放出量がコンピュータ１０に設けられた電子収量検出部及び蛍光Ｘ線収量検出部に送られる。 Further, the spectroscope control unit 13 sets the energy of the X-rays in a predetermined range (lower than the absorption edge) in order to irradiate the thin film with X-rays having energy before and after the absorption edge of the specific element constituting the thin film of the sample W Sweeping is performed within a range from a predetermined value on the energy side to a predetermined value on the higher energy side than the absorption edge. The counter 23 simultaneously detects the emission amount of photoelectrons and Auger electrons and the emission amount of fluorescent X-rays at each energy of irradiated X-rays. These emission amounts are sent to an electron yield detector and a fluorescent X-ray yield detector provided in the computer 10.
電子収量検出部は、微小電流検出器５によって検出される光電子及びオージェ電子の放出量に基いて、転換電子収量法によって特定元素に係る電子収量（Ｘ線吸収強度）Ｉｃを得るものであり、電子収量スペクトル検出部２５と電子収量スペクトル数値化部２７とを備えている。 The electron yield detection unit obtains the electron yield (X-ray absorption intensity) Ic related to the specific element by the conversion electron yield method based on the amount of emission of photoelectrons and Auger electrons detected by the microcurrent detector 5. An electron yield spectrum detection unit 25 and an electron yield spectrum digitization unit 27 are provided.
蛍光Ｘ線収量検出部は、蛍光Ｘ線検出器２０によって検出される蛍光Ｘ線の放出量に基いて、蛍光Ｘ線収量法によって特定元素に係る蛍光Ｘ線収量（Ｘ線吸収強度）Ｉｆを得るものであり、蛍光Ｘ線収量スペクトル検出部２６と蛍光Ｘ線収量スペクトル数値化部２８とを備えている。 The fluorescent X-ray yield detection unit calculates the fluorescent X-ray yield (X-ray absorption intensity) If related to the specific element by the fluorescent X-ray yield method based on the amount of emitted fluorescent X-rays detected by the fluorescent X-ray detector 20. And includes a fluorescent X-ray yield spectrum detector 26 and a fluorescent X-ray yield spectrum digitizer 28.
電子収量検出部の電子収量スペクトル検出部２５は、光電子及びオージェ電子の放出量と、これら電子の放出量を検出したときのＸ線のエネルギーとに基づいてＸ線吸収スペクトルを得る。すなわち、Ｘ線が照射された試料Ｗから放出される光電子及びオージェ電子の量は当該試料ＷにおけるＸ線の吸収量に比例する。そこで、上記電子収量スペクトル検出部２５では、光電子及びオージェ電子の放出量に所定の演算を行なうことで試料ＷにおけるＸ線の吸収係数を得て、この吸収係数を縦軸に取り、上記Ｘ線のエネルギーを横軸に取ることで、Ｘ線の吸収係数に関するＸ線吸収スペクトルを得るようになっている。 The electron yield spectrum detector 25 of the electron yield detector obtains an X-ray absorption spectrum based on the emission amounts of photoelectrons and Auger electrons and the energy of X-rays when these electron emission amounts are detected. That is, the amount of photoelectrons and Auger electrons emitted from the sample W irradiated with X-rays is proportional to the amount of X-ray absorption in the sample W. Therefore, the electron yield spectrum detection unit 25 obtains an X-ray absorption coefficient in the sample W by performing a predetermined calculation on the emission amounts of photoelectrons and Auger electrons, and takes the absorption coefficient on the vertical axis. The X-ray absorption spectrum related to the X-ray absorption coefficient is obtained by taking the energy of x on the horizontal axis.
蛍光Ｘ線収量検出部の蛍光Ｘ線収量スペクトル検出部２６は、蛍光Ｘ線の放出量と、この蛍光Ｘ線の放出量を検出したときのＸ線のエネルギーとに基づいてＸ線吸収スペクトルを得る。すなわち、上記光電子及びオージェ電子の場合と同様に、Ｘ線が照射された試料Ｗから放出される蛍光Ｘ線の量は試料Ｗにおいて照射Ｘ線の吸収量に比例するので、上記蛍光Ｘ線収量スペクトル検出部２６では、蛍光Ｘ線の放出量に所定の演算を行なうことで試料ＷにおけるＸ線の吸収係数を得てこの吸収係数を縦軸に取り、上記Ｘ線のエネルギーを横軸に取ることでＸ線の吸収係数に関するＸ線吸収スペクトルを得るようになっている。 The fluorescent X-ray yield spectrum detection unit 26 of the fluorescent X-ray yield detection unit calculates an X-ray absorption spectrum based on the emission amount of the fluorescent X-ray and the energy of the X-ray when the emission amount of the fluorescent X-ray is detected. obtain. That is, as in the case of the photoelectrons and Auger electrons, the amount of fluorescent X-rays emitted from the sample W irradiated with X-rays is proportional to the amount of absorbed X-rays absorbed in the sample W. In the spectrum detector 26, a predetermined calculation is performed on the amount of emitted fluorescent X-rays to obtain an X-ray absorption coefficient in the sample W, the absorption coefficient is taken on the vertical axis, and the X-ray energy is taken on the horizontal axis. Thus, an X-ray absorption spectrum related to the X-ray absorption coefficient is obtained.
上記の如く電子収量スペクトル検出部２５と蛍光Ｘ線収量スペクトル検出部２６とで検出されたＸ線吸収スペクトルは、Ｘ線の吸収係数の大きさとＸ線のエネルギーとの関係を示すものであるため、これらＸ線吸収スペクトルの振動構造がＸＡＦＳとなる。 As described above, the X-ray absorption spectrum detected by the electron yield spectrum detection unit 25 and the fluorescent X-ray yield spectrum detection unit 26 shows the relationship between the magnitude of the X-ray absorption coefficient and the X-ray energy. The vibration structure of these X-ray absorption spectra is XAFS.
Ｘ線を照射した際に放出される光電子及びオージェ電子の脱出深度は浅い。すなわち、微小電流検出器５で検出された光電子及びオージェ電子は、例えば試料Ｗの表面から約１ｎｍ〜約３ｎｍまでの間という極表面側を構成する特定元素から放出されたものである。従って、これら光電子及びオージェ電子に基づいて得られたＸ線吸収スペクトルの振動構造は、試料ＷのＸ線照射領域の特定元素の表面積Ｓに対応したものになる。 The escape depth of photoelectrons and Auger electrons emitted when irradiated with X-rays is shallow. That is, the photoelectrons and Auger electrons detected by the minute current detector 5 are emitted from a specific element constituting the extreme surface side between about 1 nm and about 3 nm from the surface of the sample W, for example. Therefore, the vibration structure of the X-ray absorption spectrum obtained based on these photoelectrons and Auger electrons corresponds to the surface area S of the specific element in the X-ray irradiation region of the sample W.
一方、蛍光Ｘ線は光電子よりも脱出深度が深い。すなわち、蛍光Ｘ線検出器２０で検出された蛍光Ｘ線は、例えば試料の表面から約１μｍ〜約３μｍまでの間に存する特定元素から放出されたものである。従って、この蛍光Ｘ線に基づいて得られたＸ線吸収スペクトルの振動構造は、試料ＷのＸ線照射領域内の特定元素量Ｍに対応したものになる。 On the other hand, fluorescent X-rays have a greater escape depth than photoelectrons. That is, the fluorescent X-rays detected by the fluorescent X-ray detector 20 are emitted from a specific element existing between about 1 μm and about 3 μm from the surface of the sample, for example. Therefore, the vibration structure of the X-ray absorption spectrum obtained based on this fluorescent X-ray corresponds to the specific element amount M in the X-ray irradiation region of the sample W.
上記電子収量スペクトル数値化部２７は、上記電子収量スペクトル検出部２５で得られたＸ線吸収スペクトルを数値化する。すなわち、電子収量スペクトル数値化部２７は、Ｘ線吸収スペクトルにおける吸収端、即ちＸ線のエネルギーがこれ以上低くなると吸収係数が急激に減少するようになる部分を１とする規格化を行なう。これにより、Ｘ線吸収スペクトルの吸収端が基準となってＸ線吸収スペクトルの強度が数値化され、特定元素に係る電子収量（Ｘ線吸収強度）Ｉｃが得られる。この電子収量Ｉｃは、式（１）で表されるように、Ｘ線照射領域の上記特定元素の表面積Ｓに比例する。 The electron yield spectrum digitizing unit 27 digitizes the X-ray absorption spectrum obtained by the electron yield spectrum detecting unit 25. In other words, the electron yield spectrum digitizing unit 27 performs normalization by setting the absorption edge in the X-ray absorption spectrum, that is, the portion where the absorption coefficient rapidly decreases as the X-ray energy further decreases to 1. Thereby, the intensity of the X-ray absorption spectrum is digitized with reference to the absorption edge of the X-ray absorption spectrum, and the electron yield (X-ray absorption intensity) Ic related to the specific element is obtained. This electron yield Ic is proportional to the surface area S of the specific element in the X-ray irradiation region, as represented by the formula (1).
Ｉｃ＝α・Ｓ …（１）
上記蛍光Ｘ線収量スペクトル数値化部２８は、蛍光Ｘ線収量スペクトル検出部２８で得られたＸ線吸収スペクトルを数値化する。すなわち、蛍光Ｘ線収量スペクトル数値化部２８は、上記電子収量スペクトル数値化部２７と同様に、Ｘ線吸収スペクトルを吸収端で規格化する。これにより、Ｘ線吸収スペクトルの吸収端が基準となってＸ線吸収スペクトルの強度が数値化され、特定元素に係る蛍光Ｘ線収量（Ｘ線吸収強度）Ｉｆが得られる。この蛍光Ｘ線収量Ｉｆは、式（２）で表されるように、Ｘ線照射領域内の特定元素量Ｍに比例する。
Ic = α · S (1)
The fluorescent X-ray yield spectrum digitizing unit 28 digitizes the X-ray absorption spectrum obtained by the fluorescent X-ray yield spectrum detecting unit 28. That is, the fluorescent X-ray yield spectrum digitizing unit 28 normalizes the X-ray absorption spectrum at the absorption edge in the same manner as the electron yield spectrum digitizing unit 27. As a result, the intensity of the X-ray absorption spectrum is digitized using the absorption edge of the X-ray absorption spectrum as a reference, and the fluorescent X-ray yield (X-ray absorption intensity) If associated with the specific element is obtained. The fluorescent X-ray yield If is proportional to the specific element amount M in the X-ray irradiation region, as represented by the formula (2).
Ｉｆ＝β・Ｍ …（２）
Ｍ＝Ｓ０・ρ・ｄ
Ｓ０;Ｘ線照射面積（ｍ２）
ρ；特定元素の密度（ｇ・ｍ−３）
ｄ；膜厚（ｍ）
If = β · M (2)
M = S 0 · ρ · d
S 0 ; X-ray irradiation area (m 2 )
ρ: density of a specific element (g · m −3 )
d: Film thickness (m)
上記コンピュータ１０には、上記電子収量スペクトル数値化部２７で得られる電子収量Ｉｃと、上記蛍光Ｘ線収量スペクトル数値化部２８で得られる蛍光Ｘ線収量Ｉｆとに基いて、試料Ｗの薄膜における特定元素の単位質量当たりの表面積、すなわち、特定元素に係る比表面積ＳＡを得る処理部２９が設けられている。 The computer 10 includes a thin film of the sample W based on the electron yield Ic obtained by the electron yield spectrum digitizing unit 27 and the fluorescent X-ray yield If obtained by the fluorescent X-ray yield spectrum digitizing unit 28. A processing unit 29 for obtaining a surface area per unit mass of the specific element, that is, a specific surface area SA related to the specific element is provided.
処理部２９は、上記電子の検出に関する装置定数αに対する上記蛍光Ｘ線の検出に関する装置定数βの比を装置定数比β／αとして記憶する記憶部３０を有し、上記電子収量Ｉｃと上記蛍光Ｘ線収量Ｉｆと上記装置定数比β／αとに基いて、式（３）によって上記特定元素に係る比表面積ＳＡを算出する。上記装置定数比β／αの求め方については後述する。 The processing unit 29 includes a storage unit 30 that stores a ratio of the device constant β related to the detection of the fluorescent X-rays to the device constant α related to the detection of the electrons as a device constant ratio β / α. The processing unit 29 stores the electron yield Ic and the fluorescence. Based on the X-ray yield If and the apparatus constant ratio β / α, the specific surface area SA related to the specific element is calculated by the equation (3). A method for obtaining the device constant ratio β / α will be described later.
ＳＡ＝Ｓ／Ｍ
＝(Ｉｃ／Ｉｆ)・(β／α)
＝Ｓ／（Ｓ０・ρ・ｄ） …（３）
SA = S / M
= (Ic / If) · (β / α)
= S / (S 0 · ρ · d) (3)
＜比表面積測定方法＞
上記比表面積測定装置１を用いた比表面積測定方法を説明する。まず、基材上に特定元素を含有する薄膜が設けられている薄膜試料Ｗをチャンバー２の試料ホルダ３に保持する。チャンバー２内の真空引きを行なった後、チャンバー２内が大気圧になるまでヘリウムガスを導入する。Ｘ線照射部１４によりＸ線を試料Ｗの薄膜面に照射する（Ｘ線照射ステップ）。このＸ線の掃引範囲は、特定元素の吸収端を含む所定エネルギー範囲とする。
<Specific surface area measurement method>
A specific surface area measuring method using the specific surface area measuring apparatus 1 will be described. First, a thin film sample W in which a thin film containing a specific element is provided on a substrate is held in a sample holder 3 of a chamber 2. After evacuating the chamber 2, helium gas is introduced until the inside of the chamber 2 reaches atmospheric pressure. The thin film surface of the sample W is irradiated by the X-ray irradiation unit 14 (X-ray irradiation step). The X-ray sweep range is a predetermined energy range including the absorption edge of the specific element.
試料Ｗから放出される光電子及びオージェ電子を微小電流検出器５で検出するとともに、試料Ｗから放出される蛍光Ｘ線を蛍光Ｘ線検出器２０で検出する（検出ステップ）。 Photoelectrons and Auger electrons emitted from the sample W are detected by the minute current detector 5, and fluorescent X-rays emitted from the sample W are detected by the fluorescent X-ray detector 20 (detection step).
微小電流検出器５で検出された電子放出量に基いて、Ｘ線照射領域の上記特定元素の表面積Ｓに比例する電子収量Ｉｃを得る（電子収量検出ステップ）。すなわち、微小電流検出器５で検出された電子の放出量に基いて、電子収量スペクトル検出部２５においてＸ線の吸収係数に関するＸ線吸収スペクトルを得る（電子収量スペクトル検出ステップ）。そして、電子収量スペクトル検出部２５で検出したＸ線吸収スペクトルを、電子収量スペクトル数値化部２７において数値化して電子収量Ｉｃを得る（電子収量スペクトル数値化ステップ）。 Based on the amount of electron emission detected by the minute current detector 5, an electron yield Ic proportional to the surface area S of the specific element in the X-ray irradiation region is obtained (electron yield detection step). That is, based on the amount of electron emission detected by the minute current detector 5, the electron yield spectrum detector 25 obtains an X-ray absorption spectrum related to the X-ray absorption coefficient (electron yield spectrum detection step). The X-ray absorption spectrum detected by the electron yield spectrum detector 25 is digitized by the electron yield spectrum digitizer 27 to obtain the electron yield Ic (electron yield spectrum digitization step).
一方、蛍光Ｘ線検出器２０で検出された蛍光Ｘ線放出量に基いて、式（２）で表されるＸ線照射領域内の上記特定元素の量Ｍに比例する蛍光Ｘ線収量Ｉｆを得る（蛍光Ｘ線収量検出ステップ）。すなわち、蛍光Ｘ線検出器２０で検出された蛍光Ｘ線放出量に基いて、蛍光Ｘ線収量スペクトル検出部２６においてＸ線の吸収係数に関するＸ線吸収スペクトルを得る（蛍光Ｘ線収量スペクトル検出ステップ）。そして、蛍光Ｘ線収量スペクトル検出部２６で検出したＸ線吸収スペクトルを、蛍光Ｘ線収量スペクトル数値化部２８において数値化して蛍光Ｘ線収量Ｉｆを得る（蛍光Ｘ線収量スペクトル数値化ステップ）。 On the other hand, based on the amount of fluorescent X-ray emission detected by the fluorescent X-ray detector 20, the fluorescent X-ray yield If proportional to the amount M of the specific element in the X-ray irradiation region represented by the formula (2) is obtained. (Fluorescent X-ray yield detection step). That is, based on the amount of X-ray emission detected by the fluorescent X-ray detector 20, an X-ray absorption spectrum relating to the X-ray absorption coefficient is obtained in the fluorescent X-ray yield spectrum detector 26 (fluorescent X-ray yield spectrum detection step). ). Then, the X-ray absorption spectrum detected by the fluorescent X-ray yield spectrum detector 26 is digitized by the fluorescent X-ray yield spectrum digitizing unit 28 to obtain the fluorescent X-ray yield If (fluorescent X-ray yield spectrum digitizing step).
電子収量スペクトル数値化部２７で得られた電子収量Ｉｃと、蛍光Ｘ線収量スペクトル数値化部２８で得られた蛍光Ｘ線収量Ｉｆと、記憶部３０の装置定数比β／αとに基いて、処理部２９において式（３）の演算を行なうことにより、上記薄膜における特定元素に係る比表面積ＳＡを算出する（処理ステップ）。 Based on the electron yield Ic obtained by the electron yield spectrum digitizing unit 27, the fluorescent X-ray yield If obtained by the fluorescent X-ray yield spectrum digitizing unit 28, and the device constant ratio β / α of the storage unit 30. Then, the specific surface area SA related to the specific element in the thin film is calculated by performing the calculation of Expression (3) in the processing unit 29 (processing step).
ここで、装置定数比β／αを求める方法を説明する。すなわち、式（３）によれば、β／α＝ＳＡ・（Ｉｆ／Ｉｃ）である。よって、比表面積ＳＡが既知の標準試料を準備し、その電子収量Ｉｃ及び蛍光Ｘ線収量Ｉｆを上記比表面積測定装置１によって求めることにより、装置定数比β／αが得られる。 Here, a method for obtaining the device constant ratio β / α will be described. That is, according to the equation (3), β / α = SA · (If / Ic). Therefore, by preparing a standard sample with a known specific surface area SA and obtaining the electron yield Ic and fluorescent X-ray yield If using the specific surface area measuring device 1, the device constant ratio β / α can be obtained.
＜実施例＞
厚さ２０μｍの銅基板にＡｇ（銀）を膜厚２．２ｎｍとなるように蒸着させた被験試料Ａと、厚さ１ｍｍのシリコン基板にＡｇを膜厚２．１ｎｍとなるように蒸着させた被験試料Ｂとを作製した。また、厚さ０．６μｍの平滑なＰＰ基板にＡｇを膜厚１４１ｎｍとなるように蒸着させた標準試料を作成した。図２は被験試料Ａの表面のＳＥＭ（走査型電子顕微鏡）写真であり、図３は被験試料Ｂの表面のＳＥＭ写真である。
<Example>
A test sample A in which Ag (silver) was vapor-deposited to a thickness of 2.2 nm on a copper substrate having a thickness of 20 μm, and Ag was vapor-deposited to a thickness of 2.1 nm on a silicon substrate having a thickness of 1 mm. Test sample B was prepared. Further, a standard sample was prepared by depositing Ag on a smooth PP substrate having a thickness of 0.6 μm so as to have a film thickness of 141 nm. 2 is an SEM (scanning electron microscope) photograph of the surface of the test sample A, and FIG. 3 is an SEM photograph of the surface of the test sample B.
次に、表１に示す条件で各試料のＡｇのＬ３殻Ｘ線吸収を測定し、吸収端前のエネルギーを３．３４ｋｅＶ、吸収端後のエネルギーを３．４０ｋｅＶとして、上記比表面積測定装置１により、蛍光Ｘ線収量法及び転換電子収量法の各方法でＸ線吸収強度を求めた。結果を表２に示す。 Next, the L 3 shell X-ray absorption of Ag of each sample was measured under the conditions shown in Table 1, the energy before the absorption edge was 3.34 keV, and the energy after the absorption edge was 3.40 keV. 1, the X-ray absorption intensity was determined by the fluorescent X-ray yield method and the conversion electron yield method. The results are shown in Table 2.
ここに、標準試料の場合、Ａｇ薄膜は膜厚が１４１ｎｍの連続膜であって、その表面は平滑に近い状態になっている。このため、Ｘ線照射領域の特定元素Ａｇの表面積Ｓは、Ｘ線照射面積（幾何学的表面積）Ｓ０に略一致する。すなわち、式（３）のＳ／Ｓを１とおくことができるから、標準試料の比表面積はＳＡ＝１／（ρ・ｄ）となる。Ａｇの密度ρを１０４９００００ｇ／ｍ３としたときの標準試料の比表面積ＳＡを表３に示す。そして、式（３）に標準試料のＳＡ、電子収量Ｉｃ及び蛍光Ｘ線収量Ｉｆを代入すると、装置定数比β／α（＝ＳＡ・（Ｉｃ／Ｉｆ））が求まる。その結果を表３に示す。この装置定数比β／αを記憶部３０に記憶させる。 Here, in the case of the standard sample, the Ag thin film is a continuous film having a film thickness of 141 nm, and the surface thereof is in a nearly smooth state. Therefore, the surface area S of a specific element Ag X-ray irradiation region substantially coincides with the X-ray irradiation area (geometric surface area) S 0. That is, since the S / S in the formula (3) can be set to 1, the specific surface area of the standard sample is SA = 1 / (ρ · d). Table 3 shows the specific surface area SA of the standard sample when the density ρ of Ag is 10490000 g / m 3 . Then, by substituting SA, electron yield Ic, and fluorescent X-ray yield If of the standard sample into equation (3), the apparatus constant ratio β / α (= SA · (Ic / If)) is obtained. The results are shown in Table 3. The device constant ratio β / α is stored in the storage unit 30.
そうして、被験試料Ａ，Ｂの比表面積ＳＡは、処理部２９により、式（３）にその電子収量Ｉｃ及び蛍光Ｘ線収量Ｉｆと表３の装置定数比β／αを代入することで求まる。その結果を表４に示す。被験試料Ａの方が被験試料Ｂよりも比表面積ＳＡが大きい。図２及び図３によれば、被験試料Ａ（図２）の方が被験試料Ｂ（図３）よりも、Ａｇの蒸着粒子が小さいから、比表面積測定装置１による測定結果（表４）はＳＥＭ観察結果と一致している。 Then, the specific surface area SA of the test samples A and B is calculated by substituting the electron yield Ic and the fluorescent X-ray yield If and the apparatus constant ratio β / α in Table 3 into the formula (3) by the processing unit 29. I want. The results are shown in Table 4. Test sample A has a larger specific surface area SA than test sample B. According to FIG.2 and FIG.3, since the test sample A (FIG. 2) has smaller vapor deposition particles of Ag than the test sample B (FIG. 3), the measurement result (Table 4) by the specific surface area measuring apparatus 1 is This is consistent with the SEM observation results.
＜別の実施形態＞
この実施形態では、装置定数α及び装置定数β各々を上記記憶部３０に記憶させる。上記処理部２９において、記憶部３０の装置定数α，βを用いて、特定元素の表面積Ｓ及び特定元素量Ｍ各々を算出して比表面積ＳＡを求める。
<Another embodiment>
In this embodiment, each of the device constant α and the device constant β is stored in the storage unit 30. In the processing unit 29, the specific surface area SA is obtained by calculating the surface area S and the specific element amount M of the specific element using the device constants α and β of the storage unit 30.
すなわち、基材上の薄膜の特定元素量Ｍ及び特定元素の表面積Ｓが既知である標準試料を準備する。この標準試料について、上記比表面積測定装置１により、上記Ｘ線照射ステップ、上記検出ステップ、上記電子収量検出ステップ及び上記蛍光Ｘ線収量検出ステップを経て、電子収量Ｉｃ及び蛍光Ｘ線収量Ｉｆを得る。この標準試料に係る電子収量Ｉｃと表面積Ｓとに基いて装置定数α＝Ｉｃ／Ｓを算出し、蛍光Ｘ線収量Ｉｆと特定元素量Ｍとに基いて装置定数β＝Ｉｆ／Ｍを算出する。この装置定数α，βを記憶部３０に保存する。 That is, a standard sample in which the specific element amount M of the thin film on the substrate and the surface area S of the specific element are known is prepared. With respect to this standard sample, the electron yield Ic and the fluorescent X-ray yield If are obtained by the specific surface area measuring device 1 through the X-ray irradiation step, the detection step, the electron yield detection step and the fluorescent X-ray yield detection step. . The device constant α = Ic / S is calculated based on the electron yield Ic and the surface area S of the standard sample, and the device constant β = If / M is calculated based on the fluorescent X-ray yield If and the specific element amount M. . The device constants α and β are stored in the storage unit 30.
標準試料として、上述の厚さ０．６μｍの平滑なＰＰ基板にＡｇを膜厚１４１ｎｍとなるように蒸着させた試料を用いる場合、特定元素Ａｇの表面積Ｓ＝Ｘ線照射面積Ｓ０とすることができる。よって、この標準試料の電子収量ＩｃとＸ線照射面積Ｓ０とに基いて装置定数α＝Ｉｃ／Ｓ０を得ることができる。また、この標準試料は特定元素量Ｍ＝Ｓ０・ρ・ｄであるから、この標準試料の蛍光Ｘ線収量Ｉｆと特定元素量Ｍとに基いて装置定数β＝Ｉｆ／Ｍを得ることができる。 When using a sample obtained by vapor-depositing Ag to a film thickness of 141 nm on the above-mentioned smooth PP substrate having a thickness of 0.6 μm as a standard sample, the surface area S of the specific element Ag should be set to X-ray irradiation area S 0. Can do. Therefore, the device constant α = Ic / S 0 can be obtained based on the electron yield Ic and the X-ray irradiation area S 0 of this standard sample. Further, since this standard sample has the specific element amount M = S 0 · ρ · d, the apparatus constant β = If / M can be obtained based on the fluorescent X-ray yield If and the specific element amount M of the standard sample. it can.
そうして、被験試料について上記電子収量スペクトル数値化部２７で得られた電子収量Ｉｃと記憶部３０の装置定数αとに基いてＸ線照射領域の特定元素の表面積Ｓを算出する。また、被験試料について上記蛍光Ｘ線収量スペクトル数値化部で得られた蛍光Ｘ線収量Ｉｆと上記記憶部３０の装置定数βとに基いてＸ線照射領域内の特定元素量Ｍを算出する。この特定元素の表面積Ｓと特定元素量Ｍとに基いて該特定元素に係る比表面積ＳＡを算出する。 Then, the surface area S of the specific element in the X-ray irradiation region is calculated based on the electron yield Ic obtained by the electron yield spectrum digitizing unit 27 and the device constant α of the storage unit 30 for the test sample. Further, the specific element amount M in the X-ray irradiation region is calculated based on the fluorescent X-ray yield If obtained by the fluorescent X-ray yield spectrum digitizing unit and the device constant β of the storage unit 30 for the test sample. Based on the surface area S and the specific element amount M of the specific element, the specific surface area SA related to the specific element is calculated.
以上のように、上記比表面積測定装置１によれば、基材上で薄膜になった状態での特定元素の比表面積に関する情報を得ることができ、触媒、電池の電極等の表面における特定元素の化学的、物理的ないしは電気的な性能評価に有利になる。 As described above, according to the specific surface area measuring apparatus 1, information on the specific surface area of a specific element in a thin film state on a substrate can be obtained, and a specific element on the surface of a catalyst, a battery electrode, or the like. It is advantageous for the chemical, physical or electrical performance evaluation.
１ ＸＡＦＳ分析装置
５ 微小電流検出器（電子検出部）
１４ Ｘ線照射部
２０ 蛍光Ｘ線検出器（蛍光Ｘ線検出部）
２５ 電子収量スペクトル検出部
２６ 蛍光Ｘ線収量スペクトル検出部
２７ 電子収量スペクトル数値化部
２８ 蛍光Ｘ線収量スペクトル数値化部
２９ 処理部
３０ 記憶部
Ｗ 試料
1 XAFS analyzer 5 Microcurrent detector (electronic detector)
14 X-ray irradiation unit 20 X-ray fluorescence detector (fluorescence X-ray detection unit)
25 Electron Yield Spectrum Detection Unit 26 Fluorescence X-ray Yield Spectrum Detection Unit 27 Electron Yield Spectrum Digitization Unit 28 Fluorescence X-ray Yield Spectrum Digitization Unit 29 Processing Unit 30 Storage Unit W Sample
Claims (4)
上記特定元素の吸収端前後のエネルギーのＸ線を上記薄膜に照射するＸ線照射ステップと、
上記Ｘ線が照射された試料から放出された電子及び蛍光Ｘ線をそれぞれ検出する検出ステップと、
上記電子の放出量に基いてＸ線照射領域の上記特定元素の表面積Ｓに比例する電子収量Ｉｃを得る電子収量検出ステップと、
上記蛍光Ｘ線の放出量に基いてＸ線照射領域内の上記特定元素の量Ｍに比例する蛍光Ｘ線収量Ｉｆを得る蛍光Ｘ線収量検出ステップと、
上記電子収量Ｉｃと上記蛍光Ｘ線収量Ｉｆとに基いて、上記薄膜における上記特定元素に係る比表面積ＳＡを算出する処理ステップとを備えていることを特徴とする薄膜試料の比表面積測定方法。 A thin film sample specific surface area measurement method for measuring a specific surface area of a thin film sample provided with a thin film containing a specific element on a substrate, the specific surface area per unit mass of the specific element in the thin film,
An X-ray irradiation step of irradiating the thin film with X-rays of energy before and after the absorption edge of the specific element;
A detection step of detecting electrons and fluorescent X-rays emitted from the sample irradiated with the X-rays;
An electron yield detection step for obtaining an electron yield Ic proportional to the surface area S of the specific element in the X-ray irradiation region based on the electron emission amount;
A fluorescent X-ray yield detection step for obtaining a fluorescent X-ray yield If which is proportional to the amount M of the specific element in the X-ray irradiation region based on the emission amount of the fluorescent X-ray;
A method for measuring a specific surface area of a thin film sample, comprising: a processing step of calculating a specific surface area SA related to the specific element in the thin film based on the electron yield Ic and the fluorescent X-ray yield If.
上記特定元素の吸収端前後のエネルギーのＸ線を上記薄膜に照射するＸ線照射部と、
上記Ｘ線照射部によるＸ線が照射された試料から放出された電子を検出する電子検出部と、
上記Ｘ線照射部によるＸ線が照射された試料から放出された蛍光Ｘ線を検出する蛍光Ｘ線検出部と、
上記電子検出部で検出された電子放出量に基いて、Ｘ線照射領域の上記特定元素の表面積Ｓに比例する電子収量Ｉｃを得る電子収量検出部と、
上記蛍光Ｘ線検出部で検出された蛍光Ｘ線放出量に基いて、Ｘ線照射領域内の上記特定元素の量Ｍに比例する蛍光Ｘ線収量Ｉｆを得る蛍光Ｘ線収量検出部と、
上記電子収量検出部で検出された電子収量Ｉｃと、上記蛍光Ｘ線収量検出部で検出された蛍光Ｘ線収量Ｉｆとに基いて、上記薄膜における上記特定元素に係る比表面積ＳＡを算出する処理部とを備えていることを特徴とする薄膜試料の比表面積測定装置。 A thin film sample specific surface area measuring apparatus for measuring a specific surface area of a thin film sample provided with a thin film containing a specific element on a substrate, the specific surface area per unit mass of the specific element in the thin film,
An X-ray irradiation unit that irradiates the thin film with X-rays of energy before and after the absorption edge of the specific element;
An electron detection unit for detecting electrons emitted from the sample irradiated with X-rays by the X-ray irradiation unit;
A fluorescent X-ray detection unit for detecting fluorescent X-rays emitted from a sample irradiated with X-rays by the X-ray irradiation unit;
An electron yield detector that obtains an electron yield Ic that is proportional to the surface area S of the specific element in the X-ray irradiation region based on the amount of electron emission detected by the electron detector;
A fluorescent X-ray yield detector that obtains a fluorescent X-ray yield If proportional to the amount M of the specific element in the X-ray irradiation region based on the amount of fluorescent X-ray emission detected by the fluorescent X-ray detector;
Processing for calculating the specific surface area SA related to the specific element in the thin film based on the electron yield Ic detected by the electron yield detector and the fluorescent X-ray yield If detected by the fluorescent X-ray yield detector. And a specific surface area measuring device for a thin film sample.
上記電子収量検出部は、上記電子検出部で検出された電子放出量に基いてＸ線の吸収係数に関するＸ線吸収スペクトルを得る電子収量スペクトル検出部と、該電子収量スペクトル検出部で検出したＸ線吸収スペクトルを数値化して、式（１）で表されるＸ線照射領域の上記特定元素の表面積Ｓに比例する電子収量Ｉｃを得る電子収量スペクトル数値化部とを備え、
Ｉｃ＝α×Ｓ …（１）
（αは上記電子の検出に関する装置定数である。）
上記蛍光Ｘ線収量検出部は、上記蛍光Ｘ線検出部で検出された蛍光Ｘ線放出量に基いてＸ線の吸収係数に関するＸ線吸収スペクトルを得る蛍光Ｘ線収量スペクトル検出部と、該蛍光Ｘ線収量スペクトル検出部で検出したＸ線吸収スペクトルを数値化して、式（２）で表されるＸ線照射領域内の特定元素量Ｍに比例する蛍光Ｘ線収量Ｉｆを得る蛍光Ｘ線収量スペクトル数値化部とを備え、
Ｉｆ＝β・Ｍ …（２）
（βは上記蛍光Ｘ線の検出に関する装置定数である。）
上記処理部は、上記電子の検出に関する装置定数αに対する上記蛍光Ｘ線の検出に関する装置定数βの比を装置定数比β／αとして記憶する記憶部を有し、上記電子収量スペクトル数値化部で数値化された電子収量Ｉｃと、上記蛍光Ｘ線収量スペクトル数値化部で数値化された蛍光Ｘ線収量Ｉｆと、上記記憶部の装置定数比β／αとに基いて、式（３）による演算によって上記特定元素に係る比表面積ＳＡを得ることを特徴とする薄膜試料の比表面積測定装置。
ＳＡ＝Ｓ／Ｍ＝(Ｉｃ／Ｉｆ)・(β／α) …（３） In claim 2,
The electron yield detector includes an electron yield spectrum detector that obtains an X-ray absorption spectrum related to an X-ray absorption coefficient based on the amount of electron emission detected by the electron detector, and an X detected by the electron yield spectrum detector. An electron yield spectrum quantification unit that digitizes a linear absorption spectrum and obtains an electron yield Ic proportional to the surface area S of the specific element in the X-ray irradiation region represented by the formula (1),
Ic = α × S (1)
(Α is an apparatus constant relating to the detection of the electrons.)
The fluorescent X-ray yield detection unit includes a fluorescent X-ray yield spectrum detection unit that obtains an X-ray absorption spectrum related to an X-ray absorption coefficient based on the amount of fluorescent X-ray emission detected by the fluorescent X-ray detection unit; Fluorescent X-ray yield to obtain a fluorescent X-ray yield If proportional to the specific element amount M in the X-ray irradiation region represented by the formula (2) by digitizing the X-ray absorption spectrum detected by the X-ray yield spectrum detector A spectrum digitizing unit,
If = β · M (2)
(Β is an apparatus constant relating to the detection of the fluorescent X-ray.)
The processing unit includes a storage unit that stores a ratio of the device constant β related to the detection of the fluorescent X-rays to the device constant α related to the detection of the electrons as a device constant ratio β / α. Based on the digitized electron yield Ic, the fluorescent X-ray yield If digitized by the fluorescent X-ray yield spectrum digitizing unit, and the device constant ratio β / α of the storage unit, the equation (3) A specific surface area measuring apparatus for a thin film sample, wherein the specific surface area SA related to the specific element is obtained by calculation.
SA = S / M = (Ic / If) · (β / α) (3)
上記電子収量検出部は、上記電子検出部で検出された電子放出量に基いてＸ線の吸収係数に関するＸ線吸収スペクトルを得る電子収量スペクトル検出部と、該電子収量スペクトル検出部で検出したＸ線吸収スペクトルを数値化して、式（１）で表されるＸ線照射領域の上記特定元素の表面積Ｓに比例する電子収量Ｉｃを得る電子収量スペクトル数値化部とを備え、
Ｉｃ＝α×Ｓ …（１）
（αは上記電子の検出に関する装置定数である。）
上記蛍光Ｘ線収量検出部は、上記蛍光Ｘ線検出部で検出された蛍光Ｘ線放出量に基いてＸ線の吸収係数に関するＸ線吸収スペクトルを得る蛍光Ｘ線収量スペクトル検出部と、該蛍光Ｘ線収量スペクトル検出部で検出したＸ線吸収スペクトルを数値化して、式（２）で表されるＸ線照射領域内の特定元素量Ｍに比例する蛍光Ｘ線収量Ｉｆを得る蛍光Ｘ線収量スペクトル数値化部とを備え、
Ｉｆ＝β・Ｍ …（２）
（βは上記蛍光Ｘ線の検出に関する装置定数である。）
上記処理部は、上記電子の検出に関する装置定数α及び上記蛍光Ｘ線の検出に関する装置定数βを記憶する記憶部を有し、上記電子収量スペクトル数値化部で数値化された電子収量Ｉｃと上記記憶部の電子の検出に関する装置定数αとに基いてＸ線照射領域の上記特定元素の表面積Ｓを算出し、上記蛍光Ｘ線収量スペクトル数値化部で数値化された蛍光Ｘ線収量Ｉｆと上記記憶部の蛍光Ｘ線の検出に関する装置定数βとに基いてＸ線照射領域内の上記特定元素量Ｍを算出し、上記特定元素の表面積Ｓと上記特定元素量Ｍとに基いて該特定元素に係る比表面積ＳＡを算出することを特徴とする薄膜試料の比表面積測定装置。 In claim 2,
The electron yield detector includes an electron yield spectrum detector that obtains an X-ray absorption spectrum related to an X-ray absorption coefficient based on the amount of electron emission detected by the electron detector, and an X detected by the electron yield spectrum detector. An electron yield spectrum quantification unit that digitizes a linear absorption spectrum and obtains an electron yield Ic proportional to the surface area S of the specific element in the X-ray irradiation region represented by the formula (1),
Ic = α × S (1)
(Α is an apparatus constant relating to the detection of the electrons.)
The fluorescent X-ray yield detection unit includes a fluorescent X-ray yield spectrum detection unit that obtains an X-ray absorption spectrum related to an X-ray absorption coefficient based on the amount of fluorescent X-ray emission detected by the fluorescent X-ray detection unit; Fluorescent X-ray yield to obtain a fluorescent X-ray yield If proportional to the specific element amount M in the X-ray irradiation region represented by the formula (2) by digitizing the X-ray absorption spectrum detected by the X-ray yield spectrum detector A spectrum digitizing unit,
If = β · M (2)
(Β is an apparatus constant relating to the detection of the fluorescent X-ray.)
The processing unit includes a storage unit that stores an apparatus constant α related to the detection of the electrons and an apparatus constant β related to the detection of the fluorescent X-ray, and the electron yield Ic quantified by the electron yield spectrum quantification unit and the above The surface area S of the specific element in the X-ray irradiation region is calculated based on the apparatus constant α relating to the detection of electrons in the storage unit, and the fluorescent X-ray yield If quantified by the fluorescent X-ray yield spectrum digitizing unit and the above-mentioned The specific element amount M in the X-ray irradiation region is calculated based on the apparatus constant β relating to the detection of fluorescent X-rays in the storage unit, and the specific element is calculated based on the surface area S of the specific element and the specific element amount M. A specific surface area measuring apparatus for a thin film sample, characterized by calculating a specific surface area SA related to the above.
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| JP2008045975A (en) * | 2006-08-14 | 2008-02-28 | Daido Steel Co Ltd | Carbon concentration distribution measuring method, and manufacturing method of carburized member using it |
| JP2008256576A (en) * | 2007-04-06 | 2008-10-23 | Denki Kagaku Kogyo Kk | Specific surface area measuring apparatus and method using the same |
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| JPS60104241A (en) * | 1983-11-11 | 1985-06-08 | Sumitomo Metal Ind Ltd | Fluorescent x-ray analysis |
| JP2005292085A (en) * | 2004-04-05 | 2005-10-20 | Japan Science & Technology Agency | Method and apparatus for analyzing sample |
| JP2008045975A (en) * | 2006-08-14 | 2008-02-28 | Daido Steel Co Ltd | Carbon concentration distribution measuring method, and manufacturing method of carburized member using it |
| JP2008256576A (en) * | 2007-04-06 | 2008-10-23 | Denki Kagaku Kogyo Kk | Specific surface area measuring apparatus and method using the same |
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