JP4492779B2 - X-ray diffraction method and neutron diffraction method - Google Patents
X-ray diffraction method and neutron diffraction method Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明はＸ線もしくは中性子線回折方法に関し、さらに詳しくは試料における空間的な逆格子点を測定するためのＸ線もしくは中性子線回折方法に関する。
【０００２】
【従来の技術】
薄膜において、様々な目的の特性向上のために配向性の制御が行なわれる。しかしながら、基板の状態、膜の特性、組成、成膜条件の変動等により膜構造の乱れ、異相の出現が生じやすくなる。このような薄膜等における表面の特性を評価するに際して、その配向性を把握するために空間的な逆格子点を測定することが多い。逆格子は三次元空間の中の点の配列であり、結晶格子（実格子）の一組の格子面（ｈｋｌ）が、逆格子の空間では、座標ｈｋｌの一点で表される。そして、（１）逆格子点Ｐに対応する一組の結晶面（ｈｋｌ）はブラッグの法則にしたがって入射Ｘ線を反射する。（２）回折Ｘ線の方向は逆空間内に描かれた反射球の中心点Ｃから反射球の表面上の点Ｐに向かい、回折Ｘ線の方向と一次Ｘ線の方向の間の角度は２θである。ここで上記反射球は一次Ｘ線の方向（すなわち入射および投下Ｘ線の方向）の単位ベクトルｓ０が、一つの直径に平行となるように、半径１／λ（λはＸ線の波長）の球を描いたものである。結晶（したがって結晶格子）が一つの回転軸のまわりを回転するとき、逆格子は原点Ｏ（透過Ｘ線が反射球から出てくる点）を通り結晶の回転軸に平行な軸のまわりに同じ角度だけ回転して、反射球を通り抜ける。この反射球の中に含まれる逆格子点はすべて回折点として記録される可能性を持つ。膜構造の複雑化に伴いその表面の特性を評価するために、このような逆格子点の測定が利用されることが多くなっている。しかしながら、粉末Ｘ線回折計によると、測定面に平行な面間隔の測定（薄膜では配向面のみの情報）には適するが、逆格子空間マップの測定には不向きである。電子線回折法が用いられることも多いが、電子線の利用は超高真空の測定環境を必要とし、試料も非常に限定される。したがって、空気中において非破壊で試料を評価しうる方法が望まれ、その１つとして４つの可動軸を有し、これらを走査することにより、多岐にわたる測定が可能な薄膜材料結晶性解析Ｘ線回折装置（Ｍａｔｅｒｉａｌｓ Ｒｅｓｅａｒｃｈ Ｄｉｆｆｒａｃｔｏｍｅｔｅｒ ：ＭＲＤ）が知られており、逆格子空間マップ測定機能も有する。
【０００３】
このＭＲＤにおいては、４つの可動な軸（ω、２θ、ψおよびφ軸）を組合わせて走査して、逆格子空間マップを作成することができる。しかし、この方法ではφ軸の回転は低速回転であり、しかも低角度（試料の影で測定できない）に難があるがψ軸よりも精度の高いωシフトが利用されていることと相俟って、基板および膜の構造が既知であり、しかも相互の格子軸が実質的に平行でないと評価しにくい難点がある。したがって、基板に平行な配向面の強度が弱かったり、消滅則などで出ない相が出現した場合、その存在を見落とす可能性があり、全空間の逆格子点マップを得ることは困難である。
【０００４】
【発明が解決しようとする課題】
そこで、本発明者は、薄膜等における空間的な逆格子を見落とすことなく非破壊で測定し得、未知相の同定や双晶の存在確認も可能としうるＸ線もしくは中性子線回折方法を見出すべく検討を行ない本発明に到達した。
【０００５】
【課題を解決するための手段】
すなわち、本発明の要旨は、
（１）試料における逆格子点をＸ線回折方法により測定する際に、入射Ｘ線と回折Ｘ線のなす角度である２θ軸、入射Ｘ線と試料のなす角度であるω軸、Ｘ線の入射方向に対して垂直方向のあおり角であるψ軸ならびに試料の面内回転角であるφ＊軸からなる４つの可動軸を備えたＸ線回折を用い、
２θ軸とω軸をカップリングさせて一定の角度区間を走査し、ついでψ軸をシフトして再び２θ軸とω軸をカップリングさせながら一定の角度区間を走査することを最大で角度９０度まで繰返すことにより逆格子点を測定し、ならびに
この測定中にφ＊軸を高速回転させることを特徴とするＸ線回折方法、
（２）試料における逆格子点をＸ線回折方法により測定する際に、入射Ｘ線と回折Ｘ線のなす角度である２θ軸、入射Ｘ線と試料のなす角度であるω軸、Ｘ線の入射方向に対して垂直方向のあおり角であるψ軸ならびに試料の面内回転角であるφ＊軸からなる４つの可動軸を備えたＸ線回折を用い、
２θ軸とω軸をカップリングさせて一定の角度区間を走査し、ついでω軸をシフトして再び２θ軸とω軸をカップリングさせながら一定の角度区間を走査することを最大で角度９０度まで繰返すことにより逆格子点を測定し、ならびに
この測定中にφ＊軸を高速回転させることを特徴とするＸ線回折方法、
（３）試料における逆格子点を中性子線回折方法により測定する際に、入射中性子線と回折中性子線のなす角度である２θ軸、入射中性子線と試料のなす角度であるω軸、中性子線の入射方向に対して垂直方向のあおり角であるψ軸ならびに試料の面内回転角であるφ＊軸からなる４つの可動軸を備えた中性子線回折を用い、
２θ軸とω軸をカップリングさせて一定の角度区間を走査し、ついでψ軸をシフトして再び２θ軸とω軸をカップリングさせながら一定の角度区間を走査することを最大で角度９０度まで繰返すことにより逆格子点を測定し、ならびに
この測定中にφ＊軸を高速回転させることを特徴とする中性子線回折方法、ならびに
（４）試料における逆格子点を中性子線回折方法により測定する際に、入射中性子線と回折中性子線のなす角度である２θ軸、入射中性子線と試料のなす角度であるω軸、中性子線の入射方向に対して垂直方向のあおり角であるψ軸ならびに試料の面内回転角であるφ＊軸からなる４つの可動軸を備えた中性子線回折を用い、
２θ軸とω軸をカップリングさせて一定の角度区間を走査し、ついでω軸をシフトして再び２θ軸とω軸をカップリングさせながら一定の角度区間を走査することを最大で角度９０度まで繰返すことにより逆格子点を測定し、ならびに
この測定中にφ＊軸を高速回転させることを特徴とする中性子線回折方法、にある。
【０００６】
【発明の実施の形態】
以下、本発明を詳細に説明する。
【０００７】
まず、本発明においては、試料における空間的な逆格子点が測定されるが、試料としては薄膜、積層、単結晶等のバルク試料をそのままの状態（非破壊）で使用しうる。
【０００８】
本発明においては４つの可動軸を有するＸ線回折装置が使用される。この４つの可動軸は、入射Ｘ線と回折Ｘ線のなす角度である２θ軸、入射Ｘ線と試料のなす角度であるω軸、Ｘ線の入射方向に対して垂直方向のあおり角であるψ軸ならびに試料の面内回転角であるφ＊軸からなる。３次元空間の逆格子点を測定するためには、３つの軸を走査する必要がある。本発明においては、好適には２θ軸とω軸をカップリングさせて一定の角度区間を走査し、ついでψ軸をシフトして再び２θ軸とω軸をカップリングさせながら一定の角度区間を走査することを最大で角度９０度まで繰返すことにより逆格子点を測定し、この測定中にはφ＊軸を高速回転させる。
【０００９】
このように２θ軸とω軸をカップリングさせながら走査させるとき、２θ軸がメインの軸となる２θ／ω、およびω軸がメインとなるω／２θの組合せが可能であるが、前者が好適である。上述のように、一定の角度区間の走査が終了した後に、ψ軸をシフトし、再び２θとωの走査を行なう。ψ軸のシフト角度は試料の種類、回折装置の種類、操作条件等を考慮して全空間における逆格子を収集できるように適宜選択されるが、通常１〜５度程度から選択される。ψ軸をシフトしての再走査は最大で角度９０度まで繰返されるが、目的により適宜その角度を選定しうる。
【００１０】
本発明においては、この測定中に、φ＊軸を高速回転させることが必要であるが、これはφ＊軸の高速回転は全空間における逆格子を収集できるような回転であることを意味する。たとえば、ステップ走査の場合、２θ軸（もしくはω軸）の１ステップ（たとえば、０．０１〜１度。０．０１〜１度／秒程度で）毎に１回転以上回転するようにして、格子点を見落とすことがないようにすることを目的とする。また、連続走査の場合にも、ステップ走査に相当するような回転速度が選ばれ、格子点を見落とすことがないようにする。このため、たとえば上記のＭＲＤのような市販装置を使用する場合には、φ軸はこのような高速回転（たとえば６０〜１８００ｒｐｍ）は不可能である（高々数ｒｐｍであり、通常の走査では２θ軸もしくはω軸の１ステップ毎に１回転以上回転することはできない）ので、試料ステージ上に新たに高速回転できるφ＊軸回転ステージを設ける必要がある（既設のφ軸は使用されない）。さらに、本発明においては、検出器の前にψ軸方向の分離を向上させるためにスリットを設け、ψ軸方向の発散を低減し、ピークの測定位置精度を高めるのが好適である。このような点から、スリットは横方向の拡散を抑える縦スリットが好適であり、その開き角度は通常０．１〜３度程度から選ばれる。
【００１１】
本発明においては上記のように、一定の角度区間の走査が終了した後に、ψ軸をシフトさせていくのが好適であるが、目的によっては（たとえば低角における逆格子点のデータを重視しなくてもよい場合）、ψ軸のシフトに代えて従来のようなω軸のシフトによってもよい。
【００１２】
Ｘ線に代えて中性子線を用いる場合は、線源として加速器によりパルス的に発生される中性子線、または原子炉で発生される定常的な中性子線を利用しうる。これらの線源から得られる熱中性子線の強度は性能のよいＸ線管から得られるビームより低いが、上記のＸ線回折の場合と同様に、上記の構成により中性子線回折（中性子回折）を実施しうる。
【００１３】
次に図面により本発明をさらに詳細に説明する。
【００１４】
図１は、本発明において用いられるＸ線回折計の試料ステージ部分の概略図であり、試料ステージ上に新たにφ＊軸回転ステージ（高速タイプ：回転速度６０〜１８００ｒｐｍ）が設けられている。そして検出器の前には単孔（クロス）スリットが設けられている（開き角：０．２５°）（図示せず）。
【００１５】
図２は、本発明において逆格子空間を測定するために、φ＊軸を高速回転（６００ｒｐｍ）させながら２θ／ω走査し（１ステップを０．０２度（０．５秒）として、ψ軸をシフト（２度づつ）させて全空間的な逆格子点を収集する様子を示すものである（２θ／ω−ψ−φ＊走査）。図３の（ｂ）および（ｃ）は、水溶液より析出したＣａ３Ｃｕ２（Ｃｌ１−ｘＢｒｘ）層状結晶（テトラゴナル、ａ＝０．３７４ｎｍ，ｃ＝２．６６８ｎｍ）を上記の条件で走査して逆格子点を測定(実施例１)して得られたマップを示す。図３の（ａ）は同一試料について得られたバルクＸ線回折図形を示す。ただし、矢印は図３の（ｂ）に示す走査マップより予測されるピーク位置を示す（粉末Ｘ線回折図形で確認された）。図３の（ｃ）は全空間の逆格子点を２次元マップとして重畳した逆格子空間マップを示し、縦軸は逆格子ユニットＱｙ ＊／ｒｌｕ、そして横軸は逆格子ユニットＱｘ ＊／ｒｌｕである。
実施例２
測定試料はＫｒＦエキシマレーザーを用いたプラズマレーザー堆積（ＰＬＤ）法でＳｉ（００１）基板上に成膜したＭＡ／ＣｅＯ２／ＹＳＺ薄膜（ＭＡ：Ａｌ２Ｏ３添加ＭｇＯ）とインダクション・カップリング・プラズマ（ＩＣＰ）フラッシュ蒸発法によりＭｇＯ（００１）基板上に成膜したＹＳＺ薄膜を用いた。実施例１と同様にしてＭＡ／ＣｅＯ２／ＹＳＺ薄膜およびＳｉ基板の逆格子点を測定したところ、Ａｌ２Ｏ３を２モル％添加したＭｇＯ膜には通常のＸ線回折（ＸＲＤ）で観察される（００１）、（１０１）、（１１１）配向以外に新たに（３１１）配向のドメインが存在していることがわかった。
【００１６】
【発明の効果】
本発明によれば、薄膜等における空間的な逆格子を見落とすことなく非破壊で測定し得、未知相の固定や双晶の存在確認も可能としうるＸ線もしくは中性子線回折方法が提供される。すなわち、本発明によれば、結晶、薄膜試料等をバルクの状態のままで２次元マッピング測定でき、得られる逆格子を用いて、・未知層の同定が可能 ・極点図形測定を得るための有用な情報が得られ、・格子の歪み等が直接読み取れる ・結晶方位の揺らぎ等の立体的な解析がマッピングにより容易になる。
【図面の簡単な説明】
【図１】本発明において用いられるＸ線回折計の試料ステージ部分の概略図。
【図２】本発明において逆格子空間を測定する１態様を示す。
【図３】（ａ）はＣａ３Ｃｕ２（Ｃｌ１−ｘＢｒｘ）層状結晶について得られたバルクＸ線回折図形を示す。（ｂ）および（ｃ）は、同一結晶の逆格子点を測定(実施例１)して得られたマップを示す。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an X-ray or neutron diffraction method, and more particularly to an X-ray or neutron diffraction method for measuring a spatial reciprocal lattice point in a sample.
[0002]
[Prior art]
In a thin film, the orientation is controlled to improve various target characteristics. However, the structure of the substrate, the characteristics of the film, the composition, the fluctuation of the film forming conditions, etc. tend to cause the disorder of the film structure and the appearance of different phases. In evaluating the surface characteristics of such a thin film or the like, spatial reciprocal lattice points are often measured in order to grasp the orientation. A reciprocal lattice is an array of points in a three-dimensional space, and a set of lattice planes (hkl) of a crystal lattice (real lattice) is represented by one point of coordinates hkl in the space of the reciprocal lattice. (1) A set of crystal planes (hkl) corresponding to the reciprocal lattice point P reflects incident X-rays according to Bragg's law. (2) The direction of the diffracted X-ray is directed from the center point C of the reflecting sphere drawn in the inverse space to the point P on the surface of the reflecting sphere, and the angle between the direction of the diffracted X-ray and the direction of the primary X-ray is 2θ. Here, the reflection sphere has a radius 1 / λ (λ is the wavelength of the X-ray) so that the unit vector s 0 in the direction of the primary X-ray (that is, the direction of the incident and dropped X-rays) is parallel to one diameter. The sphere is drawn. When the crystal (and hence the crystal lattice) rotates about one axis of rotation, the reciprocal lattice passes through the origin O (the point where transmitted X-rays emerge from the reflecting sphere) and is the same around an axis parallel to the crystal's axis of rotation. Rotate the angle and pass through the reflective sphere. All reciprocal lattice points included in the reflection sphere have a possibility of being recorded as diffraction points. As the film structure becomes complicated, the measurement of such reciprocal lattice points is often used to evaluate the surface characteristics. However, according to the powder X-ray diffractometer, it is suitable for measurement of a plane interval parallel to the measurement surface (information on only the orientation surface in the thin film), but is not suitable for measurement of a reciprocal lattice space map. Although electron beam diffraction is often used, the use of electron beams requires an ultra-high vacuum measurement environment, and the number of samples is very limited. Therefore, a method capable of evaluating a sample in the air in a non-destructive manner is desired. One of them is a thin film material crystallinity analysis X-ray which has four movable axes and can perform various measurements by scanning these. A diffraction device (Materials Research Diffractometer: MRD) is known, and also has a reciprocal lattice space map measurement function.
[0003]
In this MRD, a reciprocal lattice space map can be created by scanning a combination of four movable axes (ω, 2θ, ψ, and φ axes). However, in this method, the rotation of the φ-axis is a low-speed rotation, and it is difficult to make a low angle (cannot be measured by the shadow of the sample), but this is coupled with the fact that the ω-shift is more accurate than the ψ-axis. Thus, it is difficult to evaluate the structure of the substrate and the film if they are known and their lattice axes are not substantially parallel to each other. Therefore, when the strength of the orientation plane parallel to the substrate is weak or a phase that does not appear due to the extinction rule appears, the presence of the phase may be overlooked, and it is difficult to obtain a reciprocal lattice point map of the entire space.
[0004]
[Problems to be solved by the invention]
Therefore, the present inventor should find an X-ray or neutron diffraction method capable of performing nondestructive measurement without overlooking a spatial reciprocal lattice in a thin film or the like, and capable of identifying an unknown phase and confirming the existence of twins. The present invention has been reached through investigation.
[0005]
[Means for Solving the Problems]
That is, the gist of the present invention is as follows.
(1) When measuring the reciprocal lattice point in the sample by the X-ray diffraction method, the 2θ axis that is the angle between the incident X-ray and the diffracted X-ray, the ω axis that is the angle between the incident X-ray and the sample, Using X-ray diffraction having four movable axes consisting of a ψ axis that is a tilt angle perpendicular to the incident direction and a φ * axis that is an in-plane rotation angle of the sample,
Coupling the 2θ axis and the ω axis to scan a certain angle interval, and then shifting the ψ axis to scan the constant angle interval while coupling the 2θ axis and the ω axis again to a maximum angle of 90 degrees. X-ray diffraction method characterized by measuring the reciprocal lattice point by repeating the process until the φ * axis is rotated at high speed during the measurement,
(2) When measuring the reciprocal lattice point in the sample by the X-ray diffraction method, the 2θ axis that is the angle formed by the incident X-ray and the diffracted X-ray, the ω axis that is the angle formed by the incident X-ray and the sample, Using X-ray diffraction having four movable axes consisting of a ψ axis that is a tilt angle perpendicular to the incident direction and a φ * axis that is an in-plane rotation angle of the sample,
Coupling the 2θ axis and the ω axis to scan a certain angle section, and then shifting the ω axis to scan the constant angle section while coupling the 2θ axis and the ω axis again to a maximum angle of 90 degrees. X-ray diffraction method characterized by measuring the reciprocal lattice point by repeating the process until the φ * axis is rotated at high speed during the measurement,
(3) When measuring the reciprocal lattice point in the sample by the neutron diffraction method, the 2θ axis that is the angle between the incident neutron beam and the diffracted neutron beam, the ω axis that is the angle between the incident neutron beam and the sample, Using neutron diffraction with four movable axes consisting of the ψ axis that is the tilt angle perpendicular to the incident direction and the φ * axis that is the in-plane rotation angle of the sample,
Coupling the 2θ axis and the ω axis to scan a certain angle interval, and then shifting the ψ axis to scan the constant angle interval while coupling the 2θ axis and the ω axis again to a maximum angle of 90 degrees. The neutron diffraction method is characterized in that the reciprocal lattice point is measured by repeating the above and the φ * axis is rotated at high speed during the measurement, and (4) the reciprocal lattice point in the sample is measured by the neutron diffraction method. The 2θ axis that is the angle between the incident neutron beam and the diffracted neutron beam, the ω axis that is the angle between the incident neutron beam and the sample, the ψ axis that is the tilt angle perpendicular to the incident direction of the neutron beam, and the sample Using neutron diffraction with four movable axes consisting of φ * axes that are the in-plane rotation angles of
Coupling the 2θ axis and the ω axis to scan a certain angle section, and then shifting the ω axis to scan the constant angle section while coupling the 2θ axis and the ω axis again to a maximum angle of 90 degrees. The neutron diffraction method is characterized in that the reciprocal lattice point is measured by repeating the process until the φ * axis is rotated at high speed during the measurement.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0007]
First, in the present invention, a spatial reciprocal lattice point in a sample is measured. As a sample, a bulk sample such as a thin film, a laminate, or a single crystal can be used as it is (non-destructive).
[0008]
In the present invention, an X-ray diffraction apparatus having four movable axes is used. These four movable axes are a 2θ axis that is an angle formed by incident X-rays and diffracted X-rays, an ω-axis that is an angle formed by incident X-rays and a sample, and a tilt angle perpendicular to the incident direction of the X-rays. It consists of the ψ axis and the φ * axis that is the in-plane rotation angle of the sample. In order to measure a reciprocal lattice point in a three-dimensional space, it is necessary to scan three axes. In the present invention, preferably, the 2θ axis and the ω axis are coupled to scan a fixed angle section, and then the ψ axis is shifted to scan the fixed angle section while coupling the 2θ axis to the ω axis again. The reciprocal lattice point is measured by repeating this operation up to an angle of 90 degrees, and the φ * axis is rotated at high speed during this measurement.
[0009]
When scanning is performed while coupling the 2θ axis and the ω axis as described above, a combination of 2θ / ω in which the 2θ axis is the main axis and ω / 2θ in which the ω axis is the main is possible, but the former is preferable. It is. As described above, after the scanning of a certain angle interval is completed, the ψ axis is shifted, and scanning of 2θ and ω is performed again. The shift angle of the ψ axis is appropriately selected so as to collect reciprocal lattices in the entire space in consideration of the type of sample, the type of diffractometer, operating conditions, etc., but is usually selected from about 1 to 5 degrees. The rescan by shifting the ψ axis is repeated up to an angle of 90 degrees, but the angle can be appropriately selected according to the purpose.
[0010]
In the present invention, during this measurement, it is necessary to rotate the φ * axis at a high speed, which means that the high speed rotation of the φ * axis is a rotation that can collect the reciprocal lattice in the entire space. . For example, in the case of step scanning, the lattice is rotated by one or more rotations for each step of the 2θ axis (or ω axis) (for example, 0.01 to 1 degree, about 0.01 to 1 degree / second). The purpose is to ensure that points are not overlooked. Also in the case of continuous scanning, a rotational speed corresponding to step scanning is selected so that the grid points are not overlooked. For this reason, for example, when using a commercially available apparatus such as the above-mentioned MRD, the φ axis cannot be rotated at such a high speed (for example, 60 to 1800 rpm) (at most several rpm, and 2θ in normal scanning). Therefore, it is necessary to provide a φ * axis rotation stage that can be rotated at a high speed on the sample stage (the existing φ axis is not used). Furthermore, in the present invention, it is preferable to provide a slit in front of the detector in order to improve the separation in the ψ-axis direction, reduce the divergence in the ψ-axis direction, and increase the measurement position accuracy of the peak. From this point, the slit is preferably a vertical slit that suppresses lateral diffusion, and the opening angle is usually selected from about 0.1 to 3 degrees.
[0011]
In the present invention, as described above, it is preferable to shift the ψ axis after scanning of a certain angle interval is completed. However, depending on the purpose (for example, emphasizing the data of a reciprocal lattice point at a low angle). In the case where it is not necessary, a conventional ω-axis shift may be used instead of the ψ-axis shift.
[0012]
In the case of using a neutron beam instead of the X-ray, a neutron beam generated in a pulse by an accelerator or a stationary neutron beam generated in a nuclear reactor can be used as a radiation source. Although the intensity of thermal neutrons obtained from these radiation sources is lower than the beam obtained from a high-performance X-ray tube, neutron diffraction (neutron diffraction) can be performed with the above configuration, as in the case of the above X-ray diffraction. Can be implemented.
[0013]
Next, the present invention will be described in more detail with reference to the drawings.
[0014]
FIG. 1 is a schematic diagram of a sample stage portion of an X-ray diffractometer used in the present invention, and a φ * axis rotation stage (high speed type: rotation speed: 60 to 1800 rpm) is newly provided on the sample stage. A single hole (cross) slit is provided in front of the detector (opening angle: 0.25 °) (not shown).
[0015]
FIG. 2 is a diagram illustrating the measurement of the reciprocal lattice space in the present invention by performing 2θ / ω scanning while rotating the φ * axis at a high speed (600 rpm) (with one step set to 0.02 degrees (0.5 seconds), the ψ axis (2θ / ω-ψ-φ * scanning) in which all spatial reciprocal lattice points are collected by shifting (by two degrees) (b) and (c) in FIG. A reciprocal lattice point was measured by scanning the precipitated Ca 3 Cu 2 (Cl 1-x Br x ) layered crystal (tetragonal, a = 0.374 nm, c = 2.668 nm) under the above conditions (Example 1). 3A shows a bulk X-ray diffraction pattern obtained for the same sample, where the arrow indicates the peak position predicted from the scanning map shown in FIG. (Confirmed by powder X-ray diffraction pattern) (c) in FIG. A reciprocal lattice space map in which child points are superimposed as a two-dimensional map is shown, the vertical axis is the reciprocal lattice unit Q y * / rlu, and the horizontal axis is the reciprocal lattice unit Q x * / rlu.
Example 2
The measurement sample is a MA / CeO 2 / YSZ thin film (MA: Al 2 O 3 added MgO) formed on a Si (001) substrate by a plasma laser deposition (PLD) method using a KrF excimer laser and induction coupling. A YSZ thin film formed on a MgO (001) substrate by plasma (ICP) flash evaporation was used. When the reciprocal lattice points of the MA / CeO 2 / YSZ thin film and the Si substrate were measured in the same manner as in Example 1, the MgO film added with 2 mol% of Al 2 O 3 was observed by ordinary X-ray diffraction (XRD). In addition to the (001), (101), and (111) orientations, it was found that a domain of (311) orientation was newly present.
[0016]
【The invention's effect】
According to the present invention, there is provided an X-ray or neutron diffraction method capable of nondestructive measurement without overlooking a spatial reciprocal lattice in a thin film or the like, and capable of fixing an unknown phase and confirming the presence of twins. . That is, according to the present invention, two-dimensional mapping measurement can be performed on a crystal, a thin film sample or the like in a bulk state, and the obtained reciprocal lattice can be used to identify an unknown layer. Useful for obtaining a pole figure measurement.・ The lattice distortion etc. can be read directly ・ Three-dimensional analysis such as fluctuation of crystal orientation becomes easy by mapping.
[Brief description of the drawings]
FIG. 1 is a schematic view of a sample stage portion of an X-ray diffractometer used in the present invention.
FIG. 2 shows one mode of measuring reciprocal space in the present invention.
FIG. 3 (a) shows a bulk X-ray diffraction pattern obtained for a Ca 3 Cu 2 (Cl 1-x Br x ) layered crystal. (B) and (c) show maps obtained by measuring reciprocal lattice points of the same crystal (Example 1).
Claims (8)
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| JP4565202B2 (en) * | 2004-09-02 | 2010-10-20 | 独立行政法人 日本原子力研究開発機構 | Structure mapping method using neutron scattering |
| JP5164052B2 (en) | 2005-01-19 | 2013-03-13 | キヤノン株式会社 | Piezoelectric element, liquid discharge head, and liquid discharge apparatus |
| JP4121146B2 (en) | 2005-06-24 | 2008-07-23 | 株式会社リガク | Twin analyzer |
| JP4859019B2 (en) * | 2005-07-06 | 2012-01-18 | 株式会社リガク | X-ray diffractometer |
| US7874649B2 (en) | 2006-07-14 | 2011-01-25 | Canon Kabushiki Kaisha | Piezoelectric element, ink jet head and producing method for piezoelectric element |
| JP5879567B2 (en) * | 2011-10-13 | 2016-03-08 | 国立研究開発法人物質・材料研究機構 | X-ray diffraction sample rocking device, X-ray diffraction device, and X-ray diffraction pattern measurement method |
| CN110646445A (en) * | 2019-11-12 | 2020-01-03 | 中国工程物理研究院核物理与化学研究所 | Angle measuring device and using method thereof |
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