JP2009037023A - Manufacturing method of diffraction grating - Google Patents
Manufacturing method of diffraction grating Download PDFInfo
- Publication number
- JP2009037023A JP2009037023A JP2007201570A JP2007201570A JP2009037023A JP 2009037023 A JP2009037023 A JP 2009037023A JP 2007201570 A JP2007201570 A JP 2007201570A JP 2007201570 A JP2007201570 A JP 2007201570A JP 2009037023 A JP2009037023 A JP 2009037023A
- Authority
- JP
- Japan
- Prior art keywords
- ray
- photosensitive resin
- resin layer
- diffraction grating
- absorbing metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
本発明は、Ｘ線タルボ干渉計に用いられる回折格子（位相型回折格子及び／又は振幅型回折格子）の製造方法に関する。 The present invention relates to a method of manufacturing a diffraction grating (phase type diffraction grating and / or amplitude type diffraction grating) used in an X-ray Talbot interferometer.
Ｘ線透視装置は例えば医療用画像診断技術に関して広く用いられているが、被写体によるＸ線吸収の大小によって画像のコントラストを形成する原理であるために、血液、血管壁やそのまわりの軟組織についてはＸ線吸収係数が殆ど等しく、十分なコントラストを得難いという問題がある。長い時間を掛けて撮像すればある程度のコントラストを得ることはできるが、Ｘ線の照射線量が増大し、患者の負担を増大させるという問題がある。また、例えば画像中の血管のコントラストを強調するためにヨウ素などの造影物質を注射する方法も考えられるが、これも患者の負担を増大させてしまい、また検査コストも増大してしまう。 X-ray fluoroscopy devices are widely used for medical image diagnostic techniques, for example. However, because of the principle of forming an image contrast by the magnitude of X-ray absorption by a subject, blood, blood vessel walls and surrounding soft tissues There is a problem that X-ray absorption coefficients are almost equal and it is difficult to obtain a sufficient contrast. A certain amount of contrast can be obtained if imaging is performed for a long time, but there is a problem that the dose of X-rays increases and the burden on the patient increases. In addition, for example, a method of injecting a contrast material such as iodine in order to enhance the contrast of blood vessels in the image is conceivable, but this also increases the burden on the patient and increases the examination cost.
一方、例えばＸ線干渉計を利用する手法のように、Ｘ線を波として把握し、被写体中を波が伝わる速さの違いをコントラスト形成に利用する位相コントラスト法も知られている。即ち、被写体を透過することによるＸ線の位相シフトを検出する手法である。この位相コントラスト法は、Ｘ線の吸収に頼る方法に比べて約１０００倍の感度改善が実現でき、付随してＸ線照射量を例えば１／１００〜１／１０００に軽減できるという利点がある。また、空間分解能を向上させるという観点からも、上記の感度の改善は極めて好ましい効果をもたらすといえる。 On the other hand, there is also known a phase contrast method that grasps X-rays as a wave and uses a difference in the speed at which the wave is transmitted through a subject for contrast formation, such as a method using an X-ray interferometer. In other words, this is a method for detecting a phase shift of X-rays due to transmission through a subject. This phase contrast method has an advantage that sensitivity can be improved by about 1000 times compared with a method that relies on absorption of X-rays, and the X-ray irradiation dose can be reduced to, for example, 1/100 to 1/1000. In addition, from the viewpoint of improving the spatial resolution, it can be said that the above improvement in sensitivity brings a very favorable effect.
本願の発明者はＸ線干渉計を利用して画像診断を行うことの有用性を早くから見出しており、例えば特許文献１においては、マッハツェンダー型のＸ線干渉計を構成し、このＸ線ビームパス中に被検査部位を配置し、得られたＸ線干渉図形のモアレ像を解析することで、被写体による位相シフトの分布を示す画像を得ることができると提案している。このような構成によれば、Ｘ線を用いて、血管や血液分布を無造影で、あるいは、重元素を含まない物質注入により容易に可視化できるとする。 The inventor of the present application has found the usefulness of performing an image diagnosis using an X-ray interferometer from an early stage. For example, in Patent Document 1, a Mach-Zehnder type X-ray interferometer is configured, and this X-ray beam path It is proposed that an image showing a phase shift distribution by a subject can be obtained by arranging a region to be inspected and analyzing a moire image of the obtained X-ray interferogram. According to such a configuration, it is assumed that blood vessels and blood distribution can be easily visualized by using X-rays without contrast or by injecting a substance not containing heavy elements.
本発明者はＸ線干渉計を利用して画像診断する方法を研究してきたが、例えば非特許文献においては、Ｘ線干渉計のＸ線供給源の大きさが大きい為に生ずる２枚の回折格子を通過するＸ線の半影効果（Ｐｅｎａｍｂｒａ ｅｆｆｅｃｔ）を改善する方法が提案されているが構成が複雑で実用化に課題が残る。 The present inventor has studied a method of diagnosing an image using an X-ray interferometer. For example, in the non-patent literature, the diffraction of two sheets caused by the size of the X-ray source of the X-ray interferometer is large. A method for improving the penumbra effect of X-rays passing through the lattice has been proposed, but the configuration is complicated and there remains a problem in practical use.
また、特許文献２では、この回折格子の作製方法として、Ｘ線光あるいは紫外光による光学リソグラフィによってレジストからなる構造体を作製し、その後、金電気メッキ法によってＸ線吸収金属部を作製するという方法を用いている。この方法は、加工精度の点から、レジスト材料の影響を大きく受け、精度の高いものを作ることが困難である。上述の比特許文献１においては、直接プラズマエッチング法によってシリコン基板に溝部を作製し、その後、この溝部に金メッキあるいはスパッタ法によってＸ線吸収金属部を作るという手法が用いられている。この方法はシリコン材料自体が導電体であるため、金メッキ法によってＸ線吸収金属部を作製するときに、シリコン材料に一度絶縁層を作製すると共に溝の底部に銅、チタンなどの金属シード層を作製することが必要である。この手法は、プロセスが非常に多く、複雑であるという点とＸ線吸収体である金の厚みを高くすることが困難（現在では幅２〜３μｍ高さ１５μｍぐらいまでのものが可能）であり、感度向上のためにはもっとこの厚みを高くする必要がある。 Further, in Patent Document 2, as a method for producing this diffraction grating, a structure made of a resist is produced by optical lithography using X-ray light or ultraviolet light, and thereafter an X-ray absorbing metal part is produced by gold electroplating. The method is used. This method is greatly affected by the resist material from the viewpoint of processing accuracy, and it is difficult to make a highly accurate one. In the above-mentioned Comparative Document 1, a method is used in which a groove is formed in a silicon substrate by direct plasma etching, and then an X-ray absorbing metal portion is formed in the groove by gold plating or sputtering. In this method, since the silicon material itself is a conductor, when an X-ray absorbing metal part is produced by a gold plating method, an insulating layer is once produced on the silicon material and a metal seed layer such as copper or titanium is formed on the bottom of the groove. It is necessary to produce. This method is very complicated and complicated, and it is difficult to increase the thickness of gold as an X-ray absorber (currently, it is possible to have a width of 2 to 3 μm and a height of about 15 μm). In order to improve sensitivity, it is necessary to increase this thickness.
ここで近年、高輝度Ｘ線が得られる大規模設備（例えば、わが国のＳＰｒｉｎｇ８等）の利用等、可干渉で高輝度なＸ線を得られる環境が整備されるにつれて、空間的に可干渉な光源と２枚の回折格子を用いて入射波面の勾配を検出する構成のタルボ干渉計をＸ線分野に適用することが研究されている。 Here, in recent years, as an environment capable of obtaining coherent and high-intensity X-rays, such as the use of large-scale facilities (for example, SPring 8 in Japan) that can obtain high-intensity X-rays, spatial coherence is achieved. It has been studied to apply a Talbot interferometer configured to detect the gradient of an incident wavefront using a light source and two diffraction gratings in the X-ray field.
このタルボ干渉計は、簡素な光学系で実現できること等、種々の優位性が指摘されるところであるが、このＸ線タルボ干渉計を良好に機能させ得る上記２枚の回折格子を安定的に製造する方法については、加工上の特別な技術が必要になり、未だ確立されていないのが実情である。 Although this Talbot interferometer can be realized with a simple optical system, various advantages are pointed out. However, the two diffraction gratings that allow this X-ray Talbot interferometer to function well can be manufactured stably. As for the method to do this, a special technique in processing is required, and the actual situation is not established yet.
本発明の解決しようとする課題は以上の如くであり、次に、この課題を解決するための手段とその効果を説明する。 The problems to be solved by the present invention are as described above. Next, means for solving the problems and the effects thereof will be described.
本発明の観点によれば、以下のような、Ｘ線タルボ干渉計に用いられる回折格子の製造方法が提供される。紫外線透過型基板の表面に所定のパターンでＸ線吸収金属部が形成された回折格子を準備し、紫外線透過型基板及びＸ線吸収金属部の表面に紫外線感光樹脂層を形成して、光学リソグラフィー法により、Ｘ線吸収金属部を光学リソグラフィーマスクとして紫外線透過型基板の裏面から紫外線を照射して、Ｘ線吸収金属部に対応する紫外線感光樹脂層を現像により除去し、そして、電鋳法により、Ｘ線吸収金属部に電圧を印加して紫外線感光樹脂層が除去された部分にＸ線吸収金属部を積層させる。 According to an aspect of the present invention, the following method for manufacturing a diffraction grating used for an X-ray Talbot interferometer is provided. Prepare a diffraction grating having an X-ray absorbing metal part formed in a predetermined pattern on the surface of an ultraviolet transmissive substrate, form an ultraviolet photosensitive resin layer on the surface of the ultraviolet transmissive substrate and the X-ray absorbing metal part, and perform optical lithography. By using the X-ray absorbing metal part as an optical lithography mask, ultraviolet rays are irradiated from the back surface of the ultraviolet transmissive substrate, and the ultraviolet photosensitive resin layer corresponding to the X-ray absorbing metal part is removed by development. Then, a voltage is applied to the X-ray absorbing metal part, and the X-ray absorbing metal part is laminated on the part where the ultraviolet photosensitive resin layer is removed.
これにより、Ｘ線吸収金属部を光学リソグラフィーマスクとして利用した、光学リソグラフィー法によりアスペクト比の大きな加工を十分な精度をもって行うことができる。また、電鋳法の際に、Ｘ線吸収金属部に電圧を印加するため、正確に当該Ｘ線吸収金属部を埋め込むことができる。 Thereby, processing with a large aspect ratio can be performed with sufficient accuracy by an optical lithography method using the X-ray absorbing metal portion as an optical lithography mask. In addition, since a voltage is applied to the X-ray absorbing metal part during electroforming, the X-ray absorbing metal part can be accurately embedded.
上記回折格子の製造方法においては、好ましくは、紫外線透過型基板の表面に金属シード層を形成し、その金属シード層の表面に紫外線感光樹脂層を形成して、光学リソグラフィー法により、金属シード層の表面に形成された紫外線感光樹脂層に光学リソグラフィーマスクを用いたパターニングを行って現像により紫外線感光樹脂層を除去し、そして、電鋳法により、金属シード層に電圧を印加して当該紫外線感光樹脂層が除去された部分にＸ線吸収金属部を形成し、Ｘ線吸収金属部が形成された部分以外の部分に対応する紫外線感光樹脂層及び金属シード層を除去した後、紫外線透過型基板及びＸ線吸収金属部の表面に紫外線感光樹脂層を形成して、光学リソグラフィー法により、Ｘ線吸収金属部を光学リソグラフィーマスクとして紫外線透過型基板の裏面から紫外線を照射して、Ｘ線吸収金属部に対応する紫外線感光樹脂層を現像により除去し、そして、電鋳法により、金属シード層を介してＸ線吸収金属部に電圧を印加して紫外線感光樹脂層が除去された部分にＸ線吸収金属部を積層させる。 In the manufacturing method of the diffraction grating, preferably, a metal seed layer is formed on the surface of the ultraviolet transmissive substrate, an ultraviolet photosensitive resin layer is formed on the surface of the metal seed layer, and the metal seed layer is formed by an optical lithography method. The ultraviolet photosensitive resin layer formed on the surface of the substrate is patterned using an optical lithography mask, the ultraviolet photosensitive resin layer is removed by development, and a voltage is applied to the metal seed layer by electroforming to apply the ultraviolet photosensitive resin layer. An X-ray absorbing metal portion is formed in the portion where the resin layer is removed, and after removing the UV photosensitive resin layer and the metal seed layer corresponding to the portion other than the portion where the X-ray absorbing metal portion is formed, an ultraviolet transmitting substrate Then, an ultraviolet photosensitive resin layer is formed on the surface of the X-ray absorbing metal part, and an ultraviolet ray is used with the X-ray absorbing metal part as an optical lithography mask by an optical lithography method. Ultraviolet rays are irradiated from the back surface of the overmolded substrate, the ultraviolet photosensitive resin layer corresponding to the X-ray absorbing metal part is removed by development, and a voltage is applied to the X-ray absorbing metal part through the metal seed layer by electroforming. Is applied, and the X-ray absorbing metal part is laminated on the part where the ultraviolet photosensitive resin layer is removed.
これにより、Ｘ線吸収金属部を光学リソグラフィーマスクとして利用した、光学リソグラフィー法によりアスペクト比の大きな加工を十分な精度をもって行うことができる。また、電鋳法の際に、金属シード層又はＸ線吸収金属部に電圧を印加するため、正確に当該Ｘ線吸収金属部を埋め込むことができる。 Thereby, processing with a large aspect ratio can be performed with sufficient accuracy by an optical lithography method using the X-ray absorbing metal portion as an optical lithography mask. Moreover, since a voltage is applied to the metal seed layer or the X-ray absorbing metal part during the electroforming, the X-ray absorbing metal part can be accurately embedded.
上記回折格子の製造方法においては、好ましくは、光学リソグラフィー法により、Ｘ線吸収金属部を光学リソグラフィーマスクとして紫外線透過型基板の裏面から紫外線を照射して、Ｘ線吸収金属部に対応する紫外線感光樹脂層を現像により除去し、そして、電鋳法により、Ｘ線吸収金属部に電圧を印加して紫外線感光樹脂層が除去された部分にＸ線吸収金属部をさらに積層させる工程を所定回数繰り返すことにより、Ｘ線吸収金属部のスリット幅と厚みとのアスペクト比を１対５以上とする。 In the above-described diffraction grating manufacturing method, preferably, an ultraviolet sensitization corresponding to the X-ray absorbing metal portion is performed by irradiating ultraviolet rays from the back surface of the UV transmissive substrate by using an optical lithography method with the X-ray absorbing metal portion as an optical lithography mask. The process of removing the resin layer by development and applying a voltage to the X-ray absorbing metal part by electroforming to further laminate the X-ray absorbing metal part on the part from which the ultraviolet photosensitive resin layer has been removed is repeated a predetermined number of times. Thus, the aspect ratio between the slit width and the thickness of the X-ray absorbing metal part is set to 1: 5 or more.
これにより、上記した工程を所定回数繰り返すだけで、アスペクト比の大きい加工を必要とする振幅型回折格子を製造することができる。 Thus, an amplitude type diffraction grating that requires processing with a large aspect ratio can be manufactured by simply repeating the above-described steps a predetermined number of times.
また、本発明の観点によれば、以下のような、Ｘ線タルボ干渉計に用いられる回折格子の製造方法が提供される。紫外線透過型基板の表面に金属シード層を形成し、その金属シード層の表面に紫外線感光樹脂層を形成して、光学リソグラフィー法により、金属シード層の表面に形成された紫外線感光樹脂層に光学リソグラフィーマスクを用いたパターニングを行って現像により紫外線感光樹脂層を除去し、そして、電鋳法により、金属シード層に電圧を印加して当該紫外線感光樹脂層が除去された部分にＸ線吸収金属部を形成し、Ｘ線吸収金属部が形成された部分以外の部分に対応する紫外線感光樹脂層及び金属シード層を除去する。 Moreover, according to the viewpoint of this invention, the manufacturing method of the diffraction grating used for an X-ray Talbot interferometer as follows is provided. A metal seed layer is formed on the surface of the ultraviolet transmissive substrate, an ultraviolet photosensitive resin layer is formed on the surface of the metal seed layer, and an optical lithography is applied to the ultraviolet photosensitive resin layer formed on the surface of the metal seed layer. Patterning using a lithography mask is performed, the ultraviolet photosensitive resin layer is removed by development, and an X-ray absorbing metal is applied to the portion where the ultraviolet photosensitive resin layer is removed by applying a voltage to the metal seed layer by electroforming. The ultraviolet-sensitive resin layer and the metal seed layer corresponding to the portion other than the portion where the X-ray absorbing metal portion is formed are removed.
これにより、厚みが小さくても良い（アスペクト比が例えば１以下の加工で十分な）位相型回折格子においては、コストや工数の少ない製造方法を採用して製造コストを低減することができる。また、電鋳法の際に、金属シード層に電圧を印加するため、正確に当該Ｘ線吸収金属部を埋め込むことができる。 Thereby, in the phase type diffraction grating which may have a small thickness (a processing with an aspect ratio of, for example, 1 or less), the manufacturing cost can be reduced by adopting a manufacturing method with less cost and man-hours. In addition, since a voltage is applied to the metal seed layer during the electroforming method, the X-ray absorbing metal portion can be accurately embedded.
上記回折格子の製造方法においては、好ましくは、紫外線透過型基板は、ガラス、石英ガラス、水晶等の紫外線を透過できる比較的大きな面積を高精度に鏡面加工の可能な基板材料である。 In the above-described diffraction grating manufacturing method, the ultraviolet transmissive substrate is preferably a substrate material that can be mirror-finished with high accuracy over a relatively large area that can transmit ultraviolet rays, such as glass, quartz glass, and quartz.
また、本発明の観点によれば、以下のような、Ｘ線タルボ干渉計に用いられる回折格子の製造方法が提供される。Ｘ線透過型基板の表面に所定のパターンでＸ線吸収金属部が形成された回折格子を準備し、Ｘ線透過型基板及びＸ線吸収金属部の表面にＸ線感光樹脂層を形成して、Ｘ線リソグラフィー法により、Ｘ線吸収金属部をＸ線リソグラフィーマスクとしてＸ線透過型基板の裏面からＸ線を照射して、Ｘ線吸収金属部に対応するＸ線感光樹脂層を現像により除去し、そして、電鋳法により、Ｘ線吸収金属部に電圧を印加してＸ線感光樹脂層が除去された部分にＸ線吸収金属部を積層させる。 Moreover, according to the viewpoint of this invention, the manufacturing method of the diffraction grating used for an X-ray Talbot interferometer as follows is provided. Prepare a diffraction grating having an X-ray absorbing metal portion formed in a predetermined pattern on the surface of the X-ray transmitting substrate, and form an X-ray photosensitive resin layer on the surface of the X-ray transmitting substrate and the X-ray absorbing metal portion. Using an X-ray lithography method, the X-ray absorbing metal part is used as an X-ray lithography mask, X-rays are irradiated from the back surface of the X-ray transmission type substrate, and the X-ray photosensitive resin layer corresponding to the X-ray absorbing metal part is removed by development. The voltage is applied to the X-ray absorbing metal portion by electroforming, and the X-ray absorbing metal portion is laminated on the portion where the X-ray photosensitive resin layer is removed.
これにより、Ｘ線吸収金属部をＸ線リソグラフィーマスクとして利用した、Ｘ線リソグラフィー法によりアスペクト比の大きな加工を十分な精度をもって行うことができる。また、電鋳法の際に、Ｘ線吸収金属部に電圧を印加するため、正確に当該Ｘ線吸収金属部を埋め込むことができる。 Thereby, processing with a large aspect ratio can be performed with sufficient accuracy by the X-ray lithography method using the X-ray absorbing metal portion as an X-ray lithography mask. In addition, since a voltage is applied to the X-ray absorbing metal part during electroforming, the X-ray absorbing metal part can be accurately embedded.
上記回折格子の製造方法においては、好ましくは、Ｘ線透過型基板の表面に金属シード層を形成し、その金属シード層の表面にＸ線感光樹脂層を形成して、Ｘ線リソグラフィー法により、金属シード層の表面に形成されたＸ線感光樹脂層にＸ線リソグラフィーマスクを用いたパターニングを行って現像によりＸ線感光樹脂層を除去し、そして、電鋳法により、金属シード層に電圧を印加して当該Ｘ線感光樹脂層が除去された部分にＸ線吸収金属部を形成した後、Ｘ線感光樹脂層及びＸ線吸収金属部の表面にＸ線感光樹脂層を形成して、Ｘ線リソグラフィー法により、Ｘ線吸収金属部をＸ線リソグラフィーマスクとしてＸ線透過型基板の裏面からＸ線を照射して、Ｘ線吸収金属部に対応するＸ線感光樹脂層を現像により除去し、そして、電鋳法により、金属シード層もしくはＸ線吸収金属部に電圧を印加してＸ線感光樹脂層が除去された部分にＸ線吸収金属部を積層させる。 In the diffraction grating manufacturing method, preferably, a metal seed layer is formed on the surface of the X-ray transmissive substrate, an X-ray photosensitive resin layer is formed on the surface of the metal seed layer, and an X-ray lithography method is performed. The X-ray photosensitive resin layer formed on the surface of the metal seed layer is patterned using an X-ray lithography mask, the X-ray photosensitive resin layer is removed by development, and a voltage is applied to the metal seed layer by electroforming. An X-ray absorbing metal part is formed on the portion where the X-ray photosensitive resin layer is removed by application, and then an X-ray photosensitive resin layer is formed on the surfaces of the X-ray photosensitive resin layer and the X-ray absorbing metal part. The X-ray absorbing metal part is used as an X-ray lithography mask by X-ray lithography to irradiate X-rays from the back surface of the X-ray transmission type substrate, and the X-ray photosensitive resin layer corresponding to the X-ray absorbing metal part is removed by development. And electroforming More, to stack X-ray absorbing metal portion in the portion in which the X-ray photosensitive resin layer by applying a voltage to the metal seed layer or X-ray absorbing metal part has been removed.
これにより、Ｘ線吸収金属部をＸ線リソグラフィーマスクとして利用した、Ｘ線リソグラフィー法によりアスペクト比の大きな加工を十分な精度をもって行うことができる。また、電鋳法の際に、金属シード層もしくはＸ線吸収金属部に電圧を印加するため、正確に当該Ｘ線吸収金属部を埋め込むことができる。 Thereby, processing with a large aspect ratio can be performed with sufficient accuracy by the X-ray lithography method using the X-ray absorbing metal portion as an X-ray lithography mask. In addition, since a voltage is applied to the metal seed layer or the X-ray absorbing metal part during the electroforming, the X-ray absorbing metal part can be accurately embedded.
上記回折格子の製造方法においては、好ましくは、Ｘ線リソグラフィー法により、Ｘ線吸収金属部をＸ線リソグラフィーマスクとしてＸ線透過型基板の裏面からＸ線を照射して、Ｘ線吸収金属部に対応するＸ線感光樹脂層を現像により除去し、そして、電鋳法により、金属シード層もしくはＸ線吸収金属部に電圧を印加してＸ線感光樹脂層が除去された部分にＸ線吸収金属部をさらに積層させる工程を所定回数繰り返すことにより、Ｘ線吸収金属部のスリット幅と厚みとのアスペクト比を１対５以上とする。 In the manufacturing method of the diffraction grating, preferably, the X-ray absorption metal part is irradiated with X-rays from the back surface of the X-ray transmission type substrate using the X-ray absorption metal part as an X-ray lithography mask by the X-ray lithography method. The corresponding X-ray photosensitive resin layer is removed by development, and a voltage is applied to the metal seed layer or the X-ray absorbing metal portion by electroforming to apply the X-ray absorbing metal to the portion where the X-ray photosensitive resin layer is removed. By repeating the step of further laminating the portions a predetermined number of times, the aspect ratio between the slit width and the thickness of the X-ray absorbing metal portion is set to 1: 5 or more.
これにより、上記した工程を所定回数繰り返すだけで、アスペクト比の大きい加工を必要とする振幅型回折格子を製造することができる。 Thus, an amplitude type diffraction grating that requires processing with a large aspect ratio can be manufactured by simply repeating the above-described steps a predetermined number of times.
また、本発明の観点によれば、以下のような、Ｘ線タルボ干渉計に用いられる回折格子の製造方法が提供される。Ｘ線透過型基板の表面に金属シード層を形成し、その金属シード層の表面にＸ線感光樹脂層を形成して、Ｘ線リソグラフィー法により、金属シード層の表面に形成されたＸ線感光樹脂層にＸ線リソグラフィーマスクを用いたパターニングを行って現像によりＸ線感光樹脂層を除去し、そして、電鋳法により、金属シード層に電圧を印加して当該Ｘ線感光樹脂層が除去された部分にＸ線吸収金属部を形成する。 Moreover, according to the viewpoint of this invention, the manufacturing method of the diffraction grating used for an X-ray Talbot interferometer as follows is provided. A metal seed layer is formed on the surface of the X-ray transmissive substrate, an X-ray photosensitive resin layer is formed on the surface of the metal seed layer, and an X-ray photosensitive formed on the surface of the metal seed layer by an X-ray lithography method. The resin layer is patterned using an X-ray lithography mask, the X-ray photosensitive resin layer is removed by development, and the X-ray photosensitive resin layer is removed by applying a voltage to the metal seed layer by electroforming. An X-ray absorbing metal part is formed in the part.
これにより、厚みが小さくても良い（アスペクト比が例えば１以下の加工で十分な）位相型回折格子においては、コストや工数の少ない製造方法を採用して製造コストを低減することができる。また、電鋳法の際に、金属シード層に電圧を印加するため、正確に当該Ｘ線吸収金属部を埋め込むことができる。 Thereby, in the phase type diffraction grating which may have a small thickness (a processing with an aspect ratio of, for example, 1 or less), the manufacturing cost can be reduced by adopting a manufacturing method with less cost and man-hours. In addition, since a voltage is applied to the metal seed layer during the electroforming method, the X-ray absorbing metal portion can be accurately embedded.
上記回折格子の製造方法においては、好ましくは、Ｘ線透過型基板は、シリコン、ガラス、石英ガラス、アルミナ等のＸ線を透過できる比較的大きな面積を高精度に鏡面加工の可能な基板材料である。 In the above-described diffraction grating manufacturing method, preferably, the X-ray transmissive substrate is a substrate material that can mirror-process a relatively large area that can transmit X-rays such as silicon, glass, quartz glass, and alumina with high accuracy. is there.
上記回折格子の製造方法においては、好ましくは、現像により紫外線感光樹脂層を除去する工程又はＸ線感光樹脂層を除去する工程において、紫外線感光樹脂層又はＸ線感光樹脂層の未感光部分を除去して乾燥させる際に、臨界乾燥条件下で乾燥させる。 In the manufacturing method of the diffraction grating, preferably, in the step of removing the ultraviolet photosensitive resin layer by development or the step of removing the X-ray photosensitive resin layer, the unexposed portion of the ultraviolet photosensitive resin layer or the X-ray photosensitive resin layer is removed. When drying, it is dried under critical drying conditions.
上記した、臨界の意味は水の分子間の引力と運動エネルギーとが釣り合う点である。したがって、温度と圧力とを共に臨界以上にすると分子の運動エネルギーが分子間引力より大きくなり物質は液体とも気体とも異なる特殊な状態をとる。この状態を超臨界流体と呼び表面張力を持たない流体となるので３次元構造体の隣の樹脂のスリット同士でスティッキングを起こさない乾燥方法が可能となる。 The above critical meaning is that the attractive force between water molecules and the kinetic energy are balanced. Therefore, when both the temperature and the pressure are made higher than the criticality, the kinetic energy of the molecule becomes larger than the intermolecular attractive force, and the substance takes a special state different from the liquid or the gas. This state is called a supercritical fluid and does not have surface tension. Therefore, a drying method that does not cause sticking between the slits of the resin adjacent to the three-dimensional structure becomes possible.
上記回折格子の製造方法においては、好ましくは、現像により紫外線感光樹脂層を除去する工程又はＸ線感光樹脂層を除去する工程において、紫外線感光樹脂層又はＸ線感光樹脂層の未感光部分を水洗い洗浄により除去した後に、Ｏ２アッシング洗浄により当該水洗い洗浄では取りきれなかった未感光樹脂を酸化させて灰に置換することにより当該未感光樹脂を取り除く。 In the manufacturing method of the diffraction grating, preferably, in the step of removing the ultraviolet photosensitive resin layer by development or the step of removing the X-ray photosensitive resin layer, the unphotosensitized portion of the ultraviolet photosensitive resin layer or the X-ray photosensitive resin layer is washed with water. After removing by washing, the unphotosensitized resin that could not be removed by washing with water by O 2 ashing is oxidized and replaced with ash to remove the unphotosensitive resin.
これにより、感光した樹脂を酸化燃焼させて灰に置換して容易に取り除く事を可能としてメッキ液との不必要な化学反応の発生を防ぎＸ線吸収金属部の析出積層をスリット形状通りに正確に埋め込むことができる。 This makes it possible to easily remove the exposed resin by oxidizing and burning it, replacing it with ash, preventing unnecessary chemical reaction with the plating solution, and accurately depositing the deposited layer of the X-ray absorbing metal part according to the slit shape. Can be embedded in.
上記回折格子の製造方法においては、好ましくは、電鋳法により、紫外線感光樹脂層又はＸ線感光樹脂層が除去された部分にＸ線吸収金属部を形成する工程において、金属シード層への電圧の印加を一旦中断して、紫外線感光樹脂層又はＸ線感光樹脂層が除去された部分からメッキ溶液を流出させるポンピング工程を複数回繰り返す。 In the diffraction grating manufacturing method, preferably, in the step of forming the X-ray absorbing metal portion in the portion where the ultraviolet photosensitive resin layer or the X-ray photosensitive resin layer is removed by electroforming, the voltage applied to the metal seed layer Is temporarily interrupted, and the pumping step of allowing the plating solution to flow out from the portion where the ultraviolet photosensitive resin layer or the X-ray photosensitive resin layer is removed is repeated a plurality of times.
これにより、ヘルムホルツ電気二重層の発生を防ぎＸ線吸収金属部の析出積層を樹脂のスリット形状の隙間に正確に埋め込むことができる。 Thereby, generation | occurrence | production of a Helmholtz electric double layer can be prevented and the deposition lamination | stacking of a X-ray absorption metal part can be correctly embedded in the slit-shaped clearance gap of resin.
上記回折格子の製造方法においては、好ましくは、電鋳法により、紫外線感光樹脂層又はＸ線感光樹脂層が除去された部分にＸ線吸収金属部を形成する工程において、金属シード層に流れるメッキ電流を短時間極性反転するパルス波形とする。 In the above-described diffraction grating manufacturing method, the plating that flows through the metal seed layer in the step of forming the X-ray absorbing metal portion in the portion from which the ultraviolet photosensitive resin layer or the X-ray photosensitive resin layer has been removed is preferably performed by electroforming. Use a pulse waveform that reverses the polarity of the current for a short time.
これにより、ヘルムホルツ電気二重層の発生を防ぎメッキ層の積層を樹脂のスリット形状の隙間に正確に埋め込むことができる。 Thereby, generation | occurrence | production of a Helmholtz electric double layer can be prevented and lamination | stacking of a plating layer can be correctly embedded in the slit-shaped clearance gap of resin.
上記回折格子の製造方法においては、好ましくは、Ｘ線吸収金属部は、白金、金、銀、プラチナ、チタンの内から選択された一つ又は二つ以上の組み合わせよりなる。 In the method for manufacturing a diffraction grating, preferably, the X-ray absorbing metal part is made of one or a combination of two or more selected from platinum, gold, silver, platinum, and titanium.
上記回折格子の製造方法においては、好ましくは、Ｘ線吸収金属部は、２μｍ以上１０μｍ以下のスリット幅を有するとともに、２μｍ以上１０μｍの間隔を隔ててストライプ状に形成されている。 In the method for manufacturing a diffraction grating, preferably, the X-ray absorbing metal part has a slit width of 2 μm or more and 10 μm or less and is formed in a stripe shape with an interval of 2 μm or more and 10 μm.
上記回折格子の製造方法においては、好ましくは、金属シード層は、クロム、銅、金、アルミニウム、チタンの内から選択された一つ又は二つ以上の組み合わせよりなる。 In the method for manufacturing a diffraction grating, preferably, the metal seed layer is made of one or a combination of two or more selected from chromium, copper, gold, aluminum, and titanium.
以下、本発明を具体化した実施形態を図面に基づいて説明する。 DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments embodying the present invention will be described below with reference to the drawings.
（第１実施形態）
図１は、本発明に関わるＸ線タルボ干渉計概念示した図である。図２（ａ）はＸ線タルボ干渉計で得られるタルボ干渉像の例を示す図、図２（ｂ）は縞走査法により得られる微分位相像を示す図、図２（ｃ）はＸ線位相型ＣＴの例を示す図である。図３は、位相型回折格子構造概念図であり、図４は、振幅型回折格子構造概念図である。
(First embodiment)
FIG. 1 is a view showing the concept of an X-ray Talbot interferometer according to the present invention. 2A is a diagram showing an example of a Talbot interference image obtained by an X-ray Talbot interferometer, FIG. 2B is a diagram showing a differential phase image obtained by a fringe scanning method, and FIG. 2C is an X-ray. It is a figure which shows the example of phase type CT. FIG. 3 is a conceptual diagram of a phase type diffraction grating structure, and FIG. 4 is a conceptual diagram of an amplitude type diffraction grating structure.
先ず、本発明の方法で製造される回折格子が使用されるＸ線タルボ干渉計の光学系について、図１を参照しながら説明する。このＸ線タルボ干渉計では、１枚目の回折格子（位相型回折格子）１０と２枚目の回折格子（振幅型回折格子）２０とを特定の距離だけ離して平行に配置し、観察したい試料２を位相型回折格子１０の前に配置する。２枚の回折格子１０及び２０のそれぞれは、Ｘ線を吸収するｙ方向に細長いＸ線吸収金属部１１及び２１（図３及び図４参照）を、ｘ方向に周期的に並べて配置した構成となっている。 First, an optical system of an X-ray Talbot interferometer using a diffraction grating manufactured by the method of the present invention will be described with reference to FIG. In this X-ray Talbot interferometer, the first diffraction grating (phase-type diffraction grating) 10 and the second diffraction grating (amplitude-type diffraction grating) 20 are arranged in parallel at a specific distance to be observed. The sample 2 is disposed in front of the phase type diffraction grating 10. Each of the two diffraction gratings 10 and 20 has a configuration in which X-ray absorbing metal portions 11 and 21 (see FIGS. 3 and 4) elongated in the y direction that absorb X-rays are periodically arranged in the x direction. It has become.
ここで、回折格子１０及び２０の周期が波長に比べて十分に大きいとき、位相型回折格子１０を通過した後の光は、回折角が非常に小さくなるために、回折された多数の光が重なり合って干渉する。そして、各回折光の位相が揃う条件を満たすような距離だけ離れた位置において、位相型回折格子１０の透過直後と同じパターン、即ち自己像が干渉の結果として現れる（タルボ効果）。 Here, when the period of the diffraction gratings 10 and 20 is sufficiently larger than the wavelength, the light after passing through the phase-type diffraction grating 10 has a very small diffraction angle. Overlapping and interfering. The same pattern as that immediately after transmission through the phase-type diffraction grating 10, that is, a self-image, appears as a result of interference (Talbot effect) at positions separated by a distance that satisfies the condition that the phases of the diffracted lights are aligned.
次に、試料２を位相型回折格子１０の前に配置したときの自己像に着目すると、干渉する各回折光は試料２の内部において僅かに異なる光路を通過しているため、そのときの位相差によって干渉縞の様子が変化する。従って、この変形した自己像の位置に前記の振幅型回折格子２０を重ねることによって、いわゆるモアレ縞の画像（タルボ干渉像）Ｇを取得でき、この画像Ｇにおいては微分位相が等高線のように現れることになる（図２の（ａ）を参照）。なお、図２の（ａ）は、直径１．２ｍｍのプラスチック球を試料２として採用した際のタルボ干渉像である。 Next, paying attention to the self-image when the sample 2 is placed in front of the phase-type diffraction grating 10, each interfering diffracted light passes through a slightly different optical path inside the sample 2. The appearance of interference fringes changes depending on the phase difference. Therefore, by superimposing the amplitude diffraction grating 20 on the position of the deformed self-image, a so-called moire fringe image (Talbot interference image) G can be obtained. In this image G, the differential phase appears as a contour line. (Refer to FIG. 2A). 2A is a Talbot interference image when a plastic sphere having a diameter of 1.2 mm is used as the sample 2. FIG.
上記のタルボ干渉像Ｇを観察するだけでは上記微分位相を定量的に取得することは困難であるが、縞の位相を人為的に変化させたときの干渉縞の変化を解析することによって、微分位相を決定することができる（縞走査法）。例えば、図１において２枚の回折格子１０及び２０の相対位置関係をｘ方向にずらすことでモアレ縞の位相を変化させながら複数のタルボ干渉像Ｇを取得して解析することにより、図２（ｂ）に示すような定量的な微分位相像を得ることができる。また、この画像を単純に積分処理すれば、位相像そのものを得ることもできる。 It is difficult to obtain the differential phase quantitatively only by observing the Talbot interference image G. However, by analyzing the change of the interference fringe when the fringe phase is artificially changed, the differential phase is obtained. The phase can be determined (stripe scanning method). For example, by acquiring and analyzing a plurality of Talbot interference images G while changing the phase of moire fringes by shifting the relative positional relationship between the two diffraction gratings 10 and 20 in FIG. 1 in FIG. A quantitative differential phase image as shown in b) can be obtained. If this image is simply integrated, the phase image itself can be obtained.
更に、試料２に対して多数の投影方向から前記の図２（ｂ）に示すような微分位相像を取得し、これを積分することで位相像とし、多数の投影方向からの位相像を合成することで、図２（ｃ）に示すように、位相型Ｘ線ＣＴ（コンピュータ断層撮影）を行うことも可能である。図２（ｃ）では、試料２としてのプラスチック球をコンピュータ上で仮想的に１／８だけ切り取った断面が示されており、試料２としてのプラスチック球の形成時に生じたと思われる内部の泡の様子も明確に観察することができる。 Further, a differential phase image as shown in FIG. 2B is acquired from a number of projection directions with respect to the sample 2, and this is integrated to obtain a phase image, which is synthesized from a number of projection directions. Thus, as shown in FIG. 2C, phase X-ray CT (computer tomography) can be performed. FIG. 2 (c) shows a cross section of the plastic sphere as the sample 2 virtually cut by 1/8 on the computer, and the internal bubbles that may have occurred during the formation of the plastic sphere as the sample 2 are shown. The situation can also be observed clearly.
Ｘ線タルボ干渉計は、図１のように試料２の後に回折格子１０及び２０を２枚配置するだけという簡素な光学系であり、また、結晶のような繊細な光学素子を用いないため、精密な光学素子調整や高い安定性をそれほど必要としないという特徴を有している。また、モアレ縞として強度を検出するので、空間分解能の高い検出器を必ずしも必要としない点でも有利である。更には、タルボ干渉計は原理的に小さな光源を必要とするが単色性はそれほど必要でなく、球面波のような発散光も使用できるので、巨大な設備を必要とする前記シンクロトロン放射光以外のＸ線源を利用できる余地があり、装置の小型化に貢献して病院などでの実用化に道を拓くものとして期待されている。 The X-ray Talbot interferometer is a simple optical system in which only two diffraction gratings 10 and 20 are arranged after the sample 2 as shown in FIG. 1, and since a delicate optical element such as a crystal is not used, It has the feature that precise optical element adjustment and high stability are not so necessary. In addition, since the intensity is detected as moire fringes, it is advantageous in that a detector with high spatial resolution is not necessarily required. In addition, the Talbot interferometer requires a small light source in principle, but not so much monochromaticity, and divergent light such as spherical waves can be used. The X-ray source can be used, and it is expected that it will contribute to the miniaturization of the apparatus and open the way to practical use in hospitals.
なお、上記のように有用性が指摘されるＸ線タルボ干渉計であるが、一般にＸ線は物質による吸収が非常に小さく、位相変化もそれほど大きくないため、上記の回折格子１０及び２０は、可視光領域のタルボ干渉計のそれよりも製造が困難である。また当然ながら、タルボ干渉計を機能させるには、Ｘ線の可干渉距離よりも回折格子１０及び２０の各Ｘ線吸収金属部１１（図３参照）及び２１（図４参照）の周期を小さくする必要があり、１０μｍ以下、望ましくは５μｍ程度とする必要がある。 In addition, although it is an X-ray Talbot interferometer whose usefulness is pointed out as described above, since X-rays are generally very small in absorption by a substance and phase change is not so large, the diffraction gratings 10 and 20 described above are It is more difficult to manufacture than a Talbot interferometer in the visible light region. Of course, in order to make the Talbot interferometer function, the period of each X-ray absorbing metal portion 11 (see FIG. 3) and 21 (see FIG. 4) of the diffraction gratings 10 and 20 is made smaller than the coherence distance of X-rays. Therefore, it is necessary to set the thickness to 10 μm or less, preferably about 5 μm.
そして、いわゆる分数タルボ効果による自己像は、位相型回折格子１０の位相シフト量がπ／２になるときに、最も高いコントラストが得られるという性質がある。そして、位相シフト量がπ／２を実現するのに必要な位相型回折格子１０の厚さを本願の発明者が試算したところ、波長が０．７Å〜１．１Åの場合で、位相型回折格子１０のＸ線吸収金属部１１としてＸ線吸収能の高い金を材料として用いた場合、位相型回折格子１０では１μｍ〜１０μｍとなった。 The self-image due to the so-called fractional Talbot effect has the property that the highest contrast is obtained when the phase shift amount of the phase-type diffraction grating 10 is π / 2. Then, when the inventors of the present application calculated the thickness of the phase-type diffraction grating 10 necessary for realizing the phase shift amount of π / 2, the phase-type diffraction was obtained when the wavelength was 0.7 to 1.1 mm. When gold having a high X-ray absorption capability was used as the material as the X-ray absorbing metal portion 11 of the grating 10, the phase diffraction grating 10 had a thickness of 1 μm to 10 μm.
一方、振幅型回折格子２０については、タルボ干渉計で得られるモアレ縞の可視性の向上という観点からは振幅型回折格子２０の強度透過率を小さくすることが重要であり、例えば強度透過率１％を実現できる程度のＸ線吸収を得られれば理想的である。この点、例えば強度透過率１％を実現するのに必要な振幅型回折格子２０の厚さを本願の発明者が同様に試算したところ、金を材料として用いたとしても、波長が０．７Å〜１．１Åの場合で１０μｍ〜１００μｍの厚みが必要になるとの結果が得られた。 On the other hand, with respect to the amplitude type diffraction grating 20, it is important to reduce the intensity transmittance of the amplitude type diffraction grating 20 from the viewpoint of improving the visibility of the moire fringes obtained by the Talbot interferometer. It is ideal if X-ray absorption of a level that can achieve% is obtained. In this regard, for example, when the inventor of the present application similarly calculated the thickness of the amplitude type diffraction grating 20 necessary for realizing an intensity transmittance of 1%, even if gold was used as a material, the wavelength was 0.7 mm. The result that the thickness of 10 micrometers-100 micrometers was needed in the case of -1.1 mm was obtained.
従って、Ｘ線タルボ干渉計を実現するにあたっては、そのような２枚の回折格子１０及び２０、特に、極めて大きいアスペクト比（例えば、５以上）が要求される振幅型回折格子２０を製造できるか否かが重要な鍵となっている。 Therefore, in realizing an X-ray Talbot interferometer, can such two diffraction gratings 10 and 20 be manufactured, in particular, an amplitude type diffraction grating 20 that requires a very large aspect ratio (for example, 5 or more)? No is an important key.
以上の課題を解決すべく、本願の発明者は鋭意研究を重ね、以下に説明するような位相型回折格子１０及び振幅型回折格子２０の製造方法を提案するに至ったものである。以下、それぞれについて詳細に説明する。 In order to solve the above problems, the inventor of the present application has made extensive studies and has proposed a method of manufacturing the phase type diffraction grating 10 and the amplitude type diffraction grating 20 as described below. Hereinafter, each will be described in detail.
先ず、図３及び図４を参照して、２つの回折格子１０及び２０の具体的な構成を説明する。図３に示す位相型回折格子１０は、例えば厚さ約１５０μｍのガラス基板Ｂの一方側面に一体的に形成されている。この位相型回折格子１０は、ガラス基板Ｂ上に等間隔で多数並べて設けられた細長い前記Ｘ線吸収金属部１１を有している。Ｘ線吸収金属部１１のそれぞれは、Ｘ線吸収能に優れた金を素材としており、そのガラス基板Ｂから突出する厚みｔ１（位相型回折格子１０の厚みに相当する）は、何れのＸ線吸収金属部１１においても互いに等しくなっており、１μｍ以上５μｍ以下としている。Ｘ線吸収金属部１１とＸ線吸収金属部１１との間は、単なる空間になっている。 First, a specific configuration of the two diffraction gratings 10 and 20 will be described with reference to FIGS. The phase type diffraction grating 10 shown in FIG. 3 is integrally formed on one side surface of a glass substrate B having a thickness of about 150 μm, for example. The phase-type diffraction grating 10 has the elongated X-ray absorbing metal portion 11 provided on the glass substrate B in a large number at equal intervals. Each of the X-ray absorbing metal portions 11 is made of gold having excellent X-ray absorption ability, and the thickness t1 (corresponding to the thickness of the phase type diffraction grating 10) protruding from the glass substrate B is any X-ray. The absorption metal part 11 is also equal to each other, and is 1 μm or more and 5 μm or less. The space between the X-ray absorbing metal part 11 and the X-ray absorbing metal part 11 is merely a space.
複数のＸ線吸収金属部１１の幅ｗ１は互いに等しく構成されており、その幅ｗ１は、２μｍ以上１０μｍ以下とされている。また、Ｘ線吸収金属部１１の周期ｄ１も、２μｍ以上１０μｍ以下とされている。 The widths w1 of the plurality of X-ray absorbing metal portions 11 are configured to be equal to each other, and the width w1 is 2 μm or more and 10 μm or less. Further, the period d1 of the X-ray absorbing metal part 11 is also set to 2 μm or more and 10 μm or less.
一方、図４に示す振幅型回折格子２０は、前記の位相型回折格子１０を厚み方向（Ｘ線の光軸方向）に引き伸ばしたものに相当する。具体的には、振幅型回折格子２０のそれぞれのＸ線吸収金属部２１は、小幅で細長くかつ大きな厚みを有する形状としており、これが幅方向に等間隔で多数並べて設けられている。Ｘ線吸収金属部２１のそれぞれは、前記位相型回折格子１０と同様にＸ線吸収能に優れた金を素材としており、その厚みｔ２（振幅型回折格子２０の厚みに相当する）は、２０μｍ以上３００μｍ以下としている。Ｘ線吸収金属部２１とＸ線吸収金属部２１との間には、樹脂部材２２がサンドイッチ状に介在されている。言い換えれば、Ｘ線吸収金属部２１と樹脂部材２２とが交互に重ねられて接合された構成となっている。なお、隣り合うＸ線吸収金属部２１及び２１の間には、樹脂部材２２に代えて、酸化ケイ素からなる保持部材が介在されていても良い。 On the other hand, the amplitude type diffraction grating 20 shown in FIG. 4 corresponds to the phase type diffraction grating 10 extended in the thickness direction (X-ray optical axis direction). Specifically, each X-ray absorbing metal portion 21 of the amplitude type diffraction grating 20 has a small width, an elongated shape, and a large thickness, and a large number of the X-ray absorption metal portions 21 are arranged at equal intervals in the width direction. Each of the X-ray absorbing metal portions 21 is made of gold having an excellent X-ray absorption capability like the phase type diffraction grating 10 and has a thickness t2 (corresponding to the thickness of the amplitude type diffraction grating 20) of 20 μm. The thickness is 300 μm or less. Between the X-ray absorbing metal part 21 and the X-ray absorbing metal part 21, a resin member 22 is interposed in a sandwich shape. In other words, the X-ray absorbing metal part 21 and the resin member 22 are alternately stacked and joined. Note that a holding member made of silicon oxide may be interposed between the adjacent X-ray absorbing metal portions 21 and 21 instead of the resin member 22.
そして、複数のＸ線吸収金属部２１は幅ｗ２が互いに等しく構成されており、その幅は、２μｍ以上１０μｍ以下とされている。また、Ｘ線吸収金属部２１の周期（幅）ｄ２も、２μｍ以上１０μｍ以下とされている。 The plurality of X-ray absorbing metal portions 21 are configured to have the same width w2, and the width is 2 μm or more and 10 μm or less. Further, the period (width) d2 of the X-ray absorbing metal portion 21 is also set to 2 μm or more and 10 μm or less.
以上の構成により、図１のＸ線タルボ干渉計において、振幅型回折格子２０の直後の位置で正確なモアレ縞のタルボ干渉像Ｇを確実に得ることができる。更に、位相型回折格子１０においては、それをＸ線が通過する際の位相シフト量をπ／２とするのに十分な厚みとできる。また、振幅型回折格子２０では、モアレ縞の可視性が良好な低い透過強度率を実現するのに十分な厚みとできる。従って、鮮明なモアレ縞が得られ、信頼性及び精度の高いＸ線タルボ干渉計を実現できる。 With the above configuration, in the X-ray Talbot interferometer of FIG. 1, an accurate moire fringe Talbot interference image G can be reliably obtained at a position immediately after the amplitude type diffraction grating 20. Furthermore, the phase type diffraction grating 10 can have a thickness sufficient to set the phase shift amount when X-rays pass through it to π / 2. Further, the amplitude type diffraction grating 20 can have a thickness sufficient to realize a low transmission intensity ratio with good visibility of moire fringes. Therefore, clear moire fringes can be obtained, and an X-ray Talbot interferometer with high reliability and accuracy can be realized.
〔位相型回折格子の製造方法〕
図５〜図７は、光学リソグラフィーを用いた位相型回折格子及び振幅型回折格子の製造方法を説明するための図である。次に、前記位相型回折格子１０の製造方法について、図５及び図６を参照して説明する。まず、図５（ａ）に示すように、前述のガラス基板Ｂの一側の面に図５（ｂ）に示す金属シード層４１（例えばクロム金属）をスパッタリングで形成させ、図５（ｃ）に示す感光性樹脂（例えば、ポリビニルアルコール樹脂）３１を塗布する一方、これをパターン露光するための位相型回折格子用の光学リソグラフィーマスク（光学マスク）３４を用意する。この光学マスク３４としては、適宜のガラス基板３２の一側の面にクロムや酸化クロムによりパターン３３を薄膜状に形成したものを用いることができる。
[Method of manufacturing phase-type diffraction grating]
5 to 7 are diagrams for explaining a method of manufacturing a phase type diffraction grating and an amplitude type diffraction grating using optical lithography. Next, a method for manufacturing the phase type diffraction grating 10 will be described with reference to FIGS. First, as shown in FIG. 5 (a), a metal seed layer 41 (for example, chromium metal) shown in FIG. 5 (b) is formed on one surface of the glass substrate B by sputtering, and FIG. 5 (c). An optical lithography mask (optical mask) 34 for a phase-type diffraction grating for pattern exposure of the photosensitive resin (for example, polyvinyl alcohol resin) 31 shown in FIG. As this optical mask 34, an appropriate glass substrate 32 having a pattern 33 formed in a thin film shape on one side surface of chromium or chromium oxide can be used.
次に、図５（ｄ）に示すように、光源として紫外線供給源を用い、前記光学マスク３４のパターン３３を、ガラス基板Ｂ上の紫外線感光性樹脂３１に対して正確に転写する。そして、図６（ｅ）の現像工程で、紫外線感光性樹脂３１の未感光紫外線感光性樹脂を選択的に除去し、図６（ｆ）の金メッキ工程により、前記紫外線感光性樹脂３１が除去された部分にＸ線吸収金属部１１を形成する。更に、図６（ｇ）のように、前述の紫外線感光硬化樹脂３１及びその紫外線感光硬化樹脂３１に対応する金属シード層４１を除去する。以上の工程により、位相型回折格子１０を製造することができる。 Next, as shown in FIG. 5D, an ultraviolet supply source is used as a light source, and the pattern 33 of the optical mask 34 is accurately transferred to the ultraviolet photosensitive resin 31 on the glass substrate B. 6E, the unphotosensitive ultraviolet photosensitive resin 31 of the ultraviolet photosensitive resin 31 is selectively removed, and the ultraviolet photosensitive resin 31 is removed by the gold plating process of FIG. 6F. The X-ray absorbing metal part 11 is formed in the part. Further, as shown in FIG. 6G, the aforementioned ultraviolet photosensitive curable resin 31 and the metal seed layer 41 corresponding to the ultraviolet photosensitive curable resin 31 are removed. The phase type diffraction grating 10 can be manufactured through the above steps.
〔振幅型回折格子の製造方法〕
次に、振幅型回折格子２０の製造方法について、図６（ｈ）及び図７を参照して説明する。
[Amplitude diffraction grating manufacturing method]
Next, a manufacturing method of the amplitude type diffraction grating 20 will be described with reference to FIG.
振幅型回折格子２０は、図６（ｇ）に示した位相型回折格子１０のＸ線吸収金属部１１を利用して製造することができる。 The amplitude type diffraction grating 20 can be manufactured by using the X-ray absorbing metal portion 11 of the phase type diffraction grating 10 shown in FIG.
まず、図６（ｈ）に示すように、位相型回折格子１０のＸ線吸収金属部１１が形成されたガラス基板Ｂの表面に紫外線感光性樹脂（例えば、ポリビニールアルコール樹脂）３１を、例えばロールコートやスピンコート等を用いて塗布する。 First, as shown in FIG. 6 (h), an ultraviolet photosensitive resin (for example, polyvinyl alcohol resin) 31 is applied to the surface of the glass substrate B on which the X-ray absorbing metal portion 11 of the phase type diffraction grating 10 is formed. Apply using roll coat or spin coat.
次に、図７（ｉ）に示すように、光源として紫外線を用い、Ｘ線吸収金属部１１が形成されたガラス基板Ｂの裏面から紫外線５０を照射して、光学リソグラフィーを行い、当該Ｘ線吸収金属部１１を光学リソグラフィーマスクとして利用することで、Ｘ線吸収金属部１１に対応する部分を除く部分に対応する紫外線感光性樹脂３１を感光硬化させる。 Next, as shown in FIG. 7 (i), ultraviolet light is used as a light source, ultraviolet light 50 is irradiated from the back surface of the glass substrate B on which the X-ray absorbing metal portion 11 is formed, optical lithography is performed, and the X-ray is emitted. By using the absorbing metal portion 11 as an optical lithography mask, the ultraviolet photosensitive resin 31 corresponding to the portion other than the portion corresponding to the X-ray absorbing metal portion 11 is photocured.
図７（ｊ）に示すように、Ｘ線吸収金属部１１に対応した未感光紫外線感光性樹脂を現像により取り除く。 As shown in FIG. 7J, the non-photosensitive ultraviolet photosensitive resin corresponding to the X-ray absorbing metal portion 11 is removed by development.
図７（ｋ）に示すように、Ｘ線吸収金属部１１に金属シード層４１を介して電圧を印加して、上記した金メッキ工程により、前記紫外線感光性樹脂３１が除去された部分にＸ線吸収金属部２１を形成する。 As shown in FIG. 7 (k), a voltage is applied to the X-ray absorbing metal part 11 through the metal seed layer 41, and the X-ray is applied to the portion where the ultraviolet photosensitive resin 31 is removed by the gold plating process. Absorbing metal part 21 is formed.
Ｘ線吸収金属部２１を光学リソグラフィーマスクとして利用して、図６（ｈ）及び図７（ｉ）〜図７（ｋ）の工程を繰り返す事でＸ線吸収金属部２１の金メッキを必要回数析出積層させてアスペクト比の高い振幅型回折格子２０（図８参照）を製造することができる。 By using the X-ray absorbing metal part 21 as an optical lithography mask, the steps of FIGS. 6H and 7I to 7K are repeated to deposit gold plating of the X-ray absorbing metal part 21 as many times as necessary. The amplitude type diffraction grating 20 (see FIG. 8) having a high aspect ratio can be manufactured by laminating.
以上に示すように、厚みが小さくても良い（アスペクト比が例えば１以下の加工で十分な）位相型回折格子１０においては、図５及び図６に示すようなコストや工数の少ない製造方法を採用して製造コストを低減する一方で、厚みの大きな（アスペクト比が例えば５以上の加工が要求される）振幅型回折格子２０においては、Ｘ線吸収金属部２１を光学リソグラフィーマスクとして利用した、いわゆる光学リソグラフィーによりアスペクト比の大きな加工を十分な精度をもって行うことができる。 As described above, in the phase-type diffraction grating 10 that may have a small thickness (a processing with an aspect ratio of, for example, 1 or less), a manufacturing method with a low cost and man-hours as shown in FIGS. In the amplitude type diffraction grating 20 having a large thickness (requiring processing with an aspect ratio of 5 or more, for example), the X-ray absorbing metal portion 21 is used as an optical lithography mask while adopting and reducing the manufacturing cost. Processing with a large aspect ratio can be performed with sufficient accuracy by so-called optical lithography.
図６（ｅ）に示す紫外線感光硬化型樹脂の現像乾燥を行こなう工程では、微細加工に成る程スリット間の間隔が狭まり図９（ａ）に示すように水の表面張力で３次元構造体の隣のスリット同士でスティッキングを起こしてしまうケースが増えてくる。この対策法として、図１０に示す水の超臨界点を超えた高温高圧の条件下における乾燥が効果的である。図１０における臨界点の意味は水の分子間の引力と運動エネルギーとが釣り合う点であり、温度と圧力とを共に臨界点以上にすると分子の運動エネルギーが分子間引力より大きくなり物質は液体とも気体とも異なる特殊な状態をとる。この状態を超臨界流体と呼び表面張力を持たない流体となるので３次元構造体の隣の樹脂のスリット同士でスティッキングを起こさない乾燥方法が可能となる。 In the process of developing and drying the ultraviolet photosensitive curable resin shown in FIG. 6 (e), the interval between the slits becomes narrower as fine processing is performed, and the three-dimensional structure is formed by the surface tension of water as shown in FIG. 9 (a). There are more cases where sticking occurs between the slits next to the body. As a countermeasure, drying under high temperature and high pressure conditions exceeding the supercritical point of water shown in FIG. 10 is effective. The meaning of the critical point in FIG. 10 is that the attractive force and kinetic energy between the water molecules are balanced. If both the temperature and the pressure are made higher than the critical point, the kinetic energy of the molecule becomes larger than the intermolecular attractive force, It takes a special state different from gas. This state is called a supercritical fluid and does not have surface tension. Therefore, a drying method that does not cause sticking between the slits of the resin adjacent to the three-dimensional structure becomes possible.
本実施形態としてチャンバーの温度を４０℃に保ち、不燃性ガスの二酸化炭素を３０分間５０ｍｌ／分でパージして２０分間で０ｍｌ／分にテーパーオフした後、チャンバー内圧を１２ＭＰａに加圧３０分保持し、２０分間かけて８ＭＰａに減圧し、更に１６０分間で０ＭＰａに減圧して乾燥して制作した回折格子の実施例を図９（ｂ）に示す。 In this embodiment, the temperature of the chamber is kept at 40 ° C., carbon dioxide as a nonflammable gas is purged at 50 ml / min for 30 minutes, tapered off to 0 ml / min for 20 minutes, and then the chamber internal pressure is increased to 12 MPa for 30 minutes. FIG. 9B shows an example of a diffraction grating produced by holding, reducing the pressure to 8 MPa over 20 minutes, and further reducing the pressure to 0 MPa over 160 minutes and drying.
本実施形態におけるガラス基板Ｂの表面の紫外線感光性樹脂３１を感光させて樹脂のパターニングを行い未感光部分の樹脂を取り除く工程において、未感光樹脂を水洗して取り除いた後に水洗では取りきれなかった不要な未感光樹脂の残留物を取り除く方法に酸素によるＯ２アッシング洗浄を行い、感光した樹脂を酸化燃焼させて灰に置換して容易に取り除く事を可能としてメッキ液との不必要な化学反応の発生を防ぎＸ線吸収金属部の析出積層をスリット形状通りに正確に埋め込むことを特徴とする回折格子の製造方法を提供している。 In the process of removing the resin in the unexposed portion by patterning the resin by exposing the ultraviolet photosensitive resin 31 on the surface of the glass substrate B in the present embodiment, the unexposed resin cannot be removed by washing with water. It performed O 2 ashing washing with oxygen to a method of removing the residue of unwanted unexposed resin, unwanted chemical reactions with the plating solution as enables easily removed that a photosensitive resin was oxidative combustion substituted with ash And a method of manufacturing a diffraction grating characterized in that the deposition layer of the X-ray absorbing metal portion is accurately embedded in the slit shape.
回折格子のＸ線吸収金属をメッキ工程で３次元構造体の樹脂のスリット溝にＸ線吸収金属を３次元構造体に隙間なく析出積層させるためには溝の内壁の未感光樹脂の残留物を取り除く酸素プラズマによるアッシング洗浄方法が近年樹脂の微細加工の技術として進められている。本発明の実施例として酸素プラズマ発生電力容量５００Ｗ、基板バイアス５０Ｗ、酸素流量５０ｓｃｃｍ、の条件で３０秒間のアッシングと３分間の休止を繰り返して未感光樹脂の残留物を取り除くことができた。 In order to deposit and laminate the X-ray absorbing metal on the three-dimensional structure without any gaps in the slit groove of the resin of the three-dimensional structure by plating the X-ray absorbing metal of the diffraction grating, the residue of the non-photosensitive resin on the inner wall of the groove An ashing cleaning method using oxygen plasma to be removed has recently been advanced as a technique for fine processing of resin. As an example of the present invention, the unphotosensitive resin residue could be removed by repeating ashing for 30 seconds and resting for 3 minutes under conditions of an oxygen plasma generation power capacity of 500 W, a substrate bias of 50 W, and an oxygen flow rate of 50 sccm.
紫外線感光硬化型樹脂の現像乾燥を行こなう工程でスティッキング防止方法を講じ、３次元構造体のスリット溝の内壁の未感光樹脂の残留物を取り除く酸素プラズマによるアッシング洗浄を行った後に３次元構造体のスリット溝に電鋳法でＸ線吸収金属を析出積層させる図１１に示す電鋳工程におけるＸ線吸収金属がメッキ電解の陰極近傍に発生するヘルムホルツ電気二重層により電界が乱される影響を改善する方法として、メッキ電流をメッキ工程の途中で中断し感光樹脂スリット空隙部のメッキ溶液をスリット空隙部から流出させるポンピングの手順を５分間程度のサイクルで繰り返す事によりヘルムホルツ電気二重層の発生を防ぎＸ線吸収金属部の析出積層を樹脂のスリット形状の隙間に正確に埋め込むことを可能とさせる。 Three-dimensional structure after ashing cleaning with oxygen plasma to remove sticky resin residue on the inner wall of slit groove of three-dimensional structure by taking anti-sticking method in the process of developing and drying UV photosensitive curable resin The X-ray absorbing metal is deposited and laminated in the slit groove of the body by electroforming. The effect of the electric field being disturbed by the Helmholtz electric double layer generated in the vicinity of the cathode of the plating electrolysis in the electroforming process shown in FIG. As an improvement method, the plating current is interrupted in the middle of the plating process, and the pumping procedure for causing the plating solution in the photosensitive resin slit gap to flow out of the slit gap is repeated in a cycle of about 5 minutes, thereby generating a Helmholtz electric double layer. It is possible to accurately embed the deposited layer of the preventing X-ray absorbing metal part in the slit-shaped gap of the resin.
図１１に示す電解メッキによる電鋳法でＸ線吸収金属を析出積層させる工程において、電鋳のＸ線吸収金属がメッキ電解の陰極近傍に発生するヘルムホルツ電気二重層により乱される影響を改善する方法として、図１２に示す、メッキ電流をパルス波形とし短時間極性反転する方法によりヘルムホルツ電気二重層の発生を防ぎメッキ層の積層を樹脂のスリット形状の隙間に正確に埋め込むことができる。 In the step of depositing and laminating X-ray absorbing metal by electroplating by electroplating shown in FIG. 11, the influence of electroformed X-ray absorbing metal being disturbed by the Helmholtz electric double layer generated near the cathode of plating electrolysis is improved. As a method, it is possible to prevent the generation of the Helmholtz electric double layer and to embed the laminated layer of the plating layer accurately in the slit-shaped gap of the resin by the method of reversing the polarity for a short time by using the plating current as a pulse waveform as shown in FIG.
（第２実施形態）
図１３〜図１６は、Ｘ線リソグラフィー法を用いた位相型回折格子及び振幅型回折格子の製造方法を説明するための図である。この第２実施形態では、上記した第１実施形態の光学リソグラフィー法を用いた位相型回折格子及び振幅型回折格子の製造方法と異なり、Ｘ線リソグラフィー法を用いた位相型回折格子及び振幅型回折格子の製造方法について説明する。なお、この第２実施形態では、Ｘ線リソグラフィー法を用いること以外は、上記した第１実施形態と同様であるので、その説明を省略する。
(Second Embodiment)
FIGS. 13 to 16 are diagrams for explaining a method of manufacturing a phase type diffraction grating and an amplitude type diffraction grating using the X-ray lithography method. In the second embodiment, unlike the manufacturing method of the phase type diffraction grating and the amplitude type diffraction grating using the optical lithography method of the first embodiment, the phase type diffraction grating and the amplitude type diffraction using the X-ray lithography method are used. A method for manufacturing the grating will be described. Note that the second embodiment is the same as the first embodiment except that the X-ray lithography method is used, and thus the description thereof is omitted.
〔位相型回折格子の製造方法〕
Ｘ線リソグラフィー法を用いた第２実施形態にかかる位相型回折格子１１０の製造方法について、図１３及び図１４を参照して説明する。まず、図１３（ａ）に示すように、前述のシリコン基板Ｃの一側の面に図１３（ｂ）に示す金属シード層１４１（例えばクロム金属）をスパッタリングで形成させ、図１３（ｃ）に示すＸ線感光性樹脂（例えば、エポキシ樹脂と感放射線性カチオン重合開始剤を溶媒に溶解させたネガ型レジスト）１３１を塗布する一方、これをパターン露光するための位相型回折格子用のＸ線リソグラフィーマスク（Ｘ線マスク）１３４を用意する。このＸ線マスク１３４としては、例えば、適宜のシリコン基板１３２の一側の面に金パターン１３３を薄膜状に形成したものを用いることができる。
[Method of manufacturing phase-type diffraction grating]
A method of manufacturing the phase type diffraction grating 110 according to the second embodiment using the X-ray lithography method will be described with reference to FIGS. First, as shown in FIG. 13A, a metal seed layer 141 (for example, chromium metal) shown in FIG. 13B is formed on one surface of the above-described silicon substrate C by sputtering, and FIG. X-ray photosensitive resin (for example, a negative resist in which an epoxy resin and a radiation-sensitive cationic polymerization initiator are dissolved in a solvent) 131 is applied, while X for a phase-type diffraction grating for pattern exposure. A line lithography mask (X-ray mask) 134 is prepared. As this X-ray mask 134, for example, a mask in which a gold pattern 133 is formed in a thin film on one surface of an appropriate silicon substrate 132 can be used.
次に、図１３（ｄ）に示すように、光源としてＸ線供給源を用い、前記Ｘ線マスク１３４の金パターン１３３を、シリコン基板Ｃ上のＸ線感光性樹脂１３１に対して正確に転写する。Ｘ線に曝された部分は感光性樹脂１３１の樹脂の分子が重合して分子量が増大して現像液に溶解しなくなる。そして、図１４（ｅ）の現像工程でＸ線感光性樹脂１３１の未感光Ｘ線感光性樹脂を選択的に除去し、図１４（ｆ）の金メッキ工程により、前記Ｘ線感光性樹脂１３１が除去された部分にＸ線吸収金属部１１１を形成する。以上の工程により、位相型回折格子１１０を製造することができる。 Next, as shown in FIG. 13D, an X-ray supply source is used as a light source, and the gold pattern 133 of the X-ray mask 134 is accurately transferred to the X-ray photosensitive resin 131 on the silicon substrate C. To do. In the portion exposed to X-rays, the resin molecules of the photosensitive resin 131 are polymerized to increase the molecular weight, so that they are not dissolved in the developer. Then, the non-photosensitive X-ray photosensitive resin of the X-ray photosensitive resin 131 is selectively removed in the developing process of FIG. 14E, and the X-ray photosensitive resin 131 is converted into a gold plating process of FIG. An X-ray absorbing metal part 111 is formed in the removed part. The phase type diffraction grating 110 can be manufactured through the above steps.
〔振幅型回折格子の製造方法〕
次に、Ｘ線リソグラフィー法を用いた第２実施形態にかかる振幅型回折格子１２０の製造方法について、図１４（ｇ）〜図１５を参照して説明する。
[Amplitude diffraction grating manufacturing method]
Next, a manufacturing method of the amplitude type diffraction grating 120 according to the second embodiment using the X-ray lithography method will be described with reference to FIGS.
振幅型回折格子１２０は、図１４（ｆ）に示した位相型回折格子１１０のＸ線吸収金属部１１１を利用して製造することができる。 The amplitude type diffraction grating 120 can be manufactured using the X-ray absorption metal part 111 of the phase type diffraction grating 110 shown in FIG.
まず、図１４（ｇ）に示すように、位相型回折格子１１０のＸ線吸収金属部１１１の表面及びＸ線感光性樹脂１３１の表面にＸ線感光性樹脂（例えば、エポキシ樹脂と感放射線性カチオン重合開始剤を溶媒に溶解させたネガ型レジスト）１３１を、例えばロールコートやスピンコート等を用いて塗布する。 First, as shown in FIG. 14G, an X-ray photosensitive resin (for example, an epoxy resin and a radiation sensitive material) is formed on the surface of the X-ray absorbing metal portion 111 and the surface of the X-ray photosensitive resin 131 of the phase type diffraction grating 110. A negative resist 131 in which a cationic polymerization initiator is dissolved in a solvent is applied using, for example, roll coating or spin coating.
次に、図１５（ｈ）に示すように、光源としてＸ線供給源を用い、Ｘ線吸収金属部１１１が構成されたシリコン基板Ｃの裏面からＸ線１５０を照射して、Ｘ線リソグラフィーを行い、当該Ｘ線吸収金属部１１１をＸ線リソグラフィーマスクとして利用することで、Ｘ線吸収金属部１１１に対応する部分を除く部分に対応するＸ線感光性樹脂１３１を感光硬化させる。 Next, as shown in FIG. 15 (h), an X-ray source is used as a light source, and X-ray lithography is performed by irradiating X-ray 150 from the back surface of the silicon substrate C on which the X-ray absorbing metal part 111 is formed. Then, by using the X-ray absorbing metal portion 111 as an X-ray lithography mask, the X-ray photosensitive resin 131 corresponding to the portion excluding the portion corresponding to the X-ray absorbing metal portion 111 is photocured.
図１５（ｉ）に示すように、Ｘ線吸収金属部１１１に対応する未感光Ｘ線感光性樹脂１３１を現像により取り除く。 As shown in FIG. 15 (i), the non-photosensitive X-ray photosensitive resin 131 corresponding to the X-ray absorbing metal portion 111 is removed by development.
図１５（ｊ）に示すように、Ｘ線吸収金属部１１１に金属シード層１４１を介して電圧を印加して、上記した金メッキ工程により、前記Ｘ線感光性樹脂１３１が除去された部分にＸ線吸収金属部１２１を形成する。 As shown in FIG. 15 (j), a voltage is applied to the X-ray absorbing metal part 111 through the metal seed layer 141, and the X-ray photosensitive resin 131 is removed from the X-ray photosensitive resin 131 by the gold plating process. The line absorbing metal part 121 is formed.
Ｘ線吸収金属部１２１をＸ線リソグラフィーマスクとして利用して、図１４（ｇ）及び図１５（ｈ）〜図１５（ｊ）の工程を繰り返す事でＸ線吸収金属部１２１の金メッキを必要回数析出積層させてアスペクト比の高い振幅型回折格子１２０（図１６参照）を製造することができる。 Using the X-ray absorbing metal part 121 as an X-ray lithography mask, the steps of FIG. 14G and FIG. 15H to FIG. The amplitude type diffraction grating 120 (see FIG. 16) having a high aspect ratio can be manufactured by deposition.
以上、本発明の実施形態について図面に基づいて説明したが、具体的な構成は、これらの実施形態に限定されるものでないと考えられるべきである。本発明の範囲は、上記した実施形態の説明ではなく特許請求の範囲によって示され、さらに特許請求の範囲と均等の意味および範囲内でのすべての変更が含まれる。 As mentioned above, although embodiment of this invention was described based on drawing, it should be thought that a specific structure is not limited to these embodiment. The scope of the present invention is shown not by the above description of the embodiments but by the scope of claims for patent, and further includes all modifications within the meaning and scope equivalent to the scope of claims for patent.
例えば、上記実施形態において、Ｘ線吸収金属部を金で形成することとしたが、金に限定するものでもなく、任意の素材を用いて差し支えない。ただし、Ｘ線吸収能の優れたもの、例えば白金、金、銀、プラチナ、チタン等が好適である。 For example, in the above-described embodiment, the X-ray absorbing metal portion is formed of gold, but is not limited to gold, and any material may be used. However, those having excellent X-ray absorption ability, for example, platinum, gold, silver, platinum, titanium and the like are suitable.
また、上記実施形態において、金属シード層を例えばクロム金属で形成することとしたが、本発明はクロムに限定するものでもなく、例えば、銅、金、アルミニウム、チタンなどを用いることができる。 In the above embodiment, the metal seed layer is formed of, for example, chromium metal. However, the present invention is not limited to chromium, and for example, copper, gold, aluminum, titanium, or the like can be used.
また、第１実施形態において、紫外線透過型基板としてガラス基板を用いる例について説明したが、本発明はこれに限らず、石英ガラス、水晶等の紫外線を透過できる比較的大きな面積を高精度に鏡面加工の可能な基板材料であれば、ガラス基板に限定されない。また、第２実施形態において、Ｘ線透過型基板としてシリコン基板を用いる例について説明したが、本発明はこれに限らず、ガラス、石英ガラス、アルミナ等のＸ線を透過できる比較的大きな面積を高精度に鏡面加工の可能な基板材料であれば、シリコン基板に限定されない。 In the first embodiment, an example in which a glass substrate is used as an ultraviolet transmissive substrate has been described. However, the present invention is not limited to this, and a relatively large area capable of transmitting ultraviolet rays such as quartz glass and quartz is mirrored with high accuracy. Any substrate material that can be processed is not limited to a glass substrate. In the second embodiment, an example in which a silicon substrate is used as an X-ray transmissive substrate has been described. However, the present invention is not limited to this, and a relatively large area capable of transmitting X-rays such as glass, quartz glass, and alumina is used. The substrate material is not limited to a silicon substrate as long as the substrate material can be mirror-finished with high accuracy.
１ Ｘ線タルボ干渉計のＸ線源
２ 試料
１０，１１０ 位相型回折格子
１１，１１１ Ｘ線吸収金属部
２０，１２０ 振幅型回折格子
２１，１２１ Ｘ線吸収金属部
２２ 樹脂部材
３ 画像検出部
３１ 感光性樹脂
３２ ガラス基板
３３ パターン
３４ 光学リソグラフィーマスク
１３２ シリコン基板
１３３ 金パターン
１３４ Ｘ線リソグラフィーマスク
４１，１４１ 金属シード層
４２ 電解メッキ陽極
４３ 電解メッキ陰極
５０ 紫外線
１５０ Ｘ線
Ｂ ガラス基板
Ｃ シリコン基板
DESCRIPTION OF SYMBOLS 1 X-ray source of X-ray Talbot interferometer 2 Sample 10,110 Phase type diffraction grating 11,111 X-ray absorption metal part 20,120 Amplitude type diffraction grating 21,121 X-ray absorption metal part 22 Resin member 3 Image detection part 31 Photosensitive resin 32 Glass substrate 33 Pattern 34 Optical lithography mask 132 Silicon substrate 133 Gold pattern 134 X-ray lithography mask 41,141 Metal seed layer 42 Electrolytic plating anode 43 Electrolytic plating cathode 50 Ultraviolet ray 150 X-ray B Glass substrate C Silicon substrate
Claims (17)
紫外線透過型基板の表面に所定のパターンでＸ線吸収金属部が形成された回折格子を準備し、前記紫外線透過型基板及び前記Ｘ線吸収金属部の表面に紫外線感光樹脂層を形成して、光学リソグラフィー法により、前記Ｘ線吸収金属部を光学リソグラフィーマスクとして前記紫外線透過型基板の裏面から紫外線を照射して、前記Ｘ線吸収金属部に対応する前記紫外線感光樹脂層を現像により除去し、そして、電鋳法により、前記Ｘ線吸収金属部に電圧を印加して前記紫外線感光樹脂層が除去された部分にＸ線吸収金属部を積層させることを特徴とする、回折格子の製造方法。 A method of manufacturing a diffraction grating used in an X-ray Talbot interferometer,
Preparing a diffraction grating in which an X-ray absorbing metal part is formed in a predetermined pattern on the surface of the ultraviolet transmissive substrate, and forming an ultraviolet photosensitive resin layer on the surface of the ultraviolet transmissive substrate and the X-ray absorbing metal part; By irradiating ultraviolet rays from the back surface of the ultraviolet transmissive substrate with the X-ray absorbing metal part as an optical lithography mask by an optical lithography method, the ultraviolet photosensitive resin layer corresponding to the X-ray absorbing metal part is removed by development, Then, a method for manufacturing a diffraction grating, wherein a voltage is applied to the X-ray absorbing metal part by electroforming, and the X-ray absorbing metal part is laminated on the portion where the ultraviolet photosensitive resin layer is removed.
前記紫外線透過型基板及び前記Ｘ線吸収金属部の表面に紫外線感光樹脂層を形成して、光学リソグラフィー法により、前記Ｘ線吸収金属部を光学リソグラフィーマスクとして前記紫外線透過型基板の裏面から紫外線を照射して、前記Ｘ線吸収金属部に対応する前記紫外線感光樹脂層を現像により除去し、そして、電鋳法により、前記金属シード層を介して前記Ｘ線吸収金属部に電圧を印加して前記紫外線感光樹脂層が除去された部分にＸ線吸収金属部を積層させることを特徴とする、請求項１に記載の回折格子の製造方法。 A metal seed layer is formed on the surface of the ultraviolet transmissive substrate, an ultraviolet photosensitive resin layer is formed on the surface of the metal seed layer, and the ultraviolet photosensitive resin layer formed on the surface of the metal seed layer is formed by an optical lithography method. Patterning is performed using an optical lithography mask, the ultraviolet photosensitive resin layer is removed by development, and a voltage is applied to the metal seed layer by electroforming to apply X to the portion from which the ultraviolet photosensitive resin layer has been removed. After forming a line-absorbing metal part and removing the ultraviolet-sensitive resin layer and the metal seed layer corresponding to a part other than the part where the X-ray-absorbing metal part is formed,
An ultraviolet photosensitive resin layer is formed on the surfaces of the ultraviolet transmissive substrate and the X-ray absorbing metal portion, and ultraviolet rays are irradiated from the back surface of the ultraviolet transmissive substrate by using an optical lithography method using the X-ray absorbing metal portion as an optical lithography mask. Irradiating, the ultraviolet photosensitive resin layer corresponding to the X-ray absorbing metal part is removed by development, and a voltage is applied to the X-ray absorbing metal part through the metal seed layer by electroforming. 2. The method of manufacturing a diffraction grating according to claim 1, wherein an X-ray absorbing metal part is laminated on a portion where the ultraviolet photosensitive resin layer has been removed.
紫外線透過型基板の表面に金属シード層を形成し、その金属シード層の表面に紫外線感光樹脂層を形成して、光学リソグラフィー法により、前記金属シード層の表面に形成された紫外線感光樹脂層に光学リソグラフィーマスクを用いたパターニングを行って現像により前記紫外線感光樹脂層を除去し、そして、電鋳法により、前記金属シード層に電圧を印加して当該紫外線感光樹脂層が除去された部分にＸ線吸収金属部を形成し、前記Ｘ線吸収金属部が形成された部分以外の部分に対応する前記紫外線感光樹脂層及び前記金属シード層を除去することを特徴とする、回折格子の製造方法。 A method of manufacturing a diffraction grating used in an X-ray Talbot interferometer,
A metal seed layer is formed on the surface of the ultraviolet transmissive substrate, an ultraviolet photosensitive resin layer is formed on the surface of the metal seed layer, and the ultraviolet photosensitive resin layer formed on the surface of the metal seed layer is formed by an optical lithography method. Patterning is performed using an optical lithography mask, the ultraviolet photosensitive resin layer is removed by development, and a voltage is applied to the metal seed layer by electroforming to apply X to the portion from which the ultraviolet photosensitive resin layer has been removed. A method of manufacturing a diffraction grating, comprising forming a line-absorbing metal portion and removing the ultraviolet-sensitive resin layer and the metal seed layer corresponding to a portion other than the portion where the X-ray-absorbing metal portion is formed.
Ｘ線透過型基板の表面に所定のパターンでＸ線吸収金属部が形成された回折格子を準備し、前記Ｘ線透過型基板及び前記Ｘ線吸収金属部の表面にＸ線感光樹脂層を形成して、Ｘ線リソグラフィー法により、前記Ｘ線吸収金属部をＸ線リソグラフィーマスクとして前記Ｘ線透過型基板の裏面からＸ線を照射して、前記Ｘ線吸収金属部に対応する前記Ｘ線感光樹脂層を現像により除去し、そして、電鋳法により、前記Ｘ線吸収金属部に電圧を印加して前記Ｘ線感光樹脂層が除去された部分にＸ線吸収金属部を積層させることを特徴とする、回折格子の製造方法。 A method of manufacturing a diffraction grating used in an X-ray Talbot interferometer,
Prepare a diffraction grating having an X-ray absorbing metal portion formed in a predetermined pattern on the surface of the X-ray transmitting substrate, and form an X-ray photosensitive resin layer on the surface of the X-ray transmitting substrate and the X-ray absorbing metal portion. Then, by the X-ray lithography method, using the X-ray absorbing metal portion as an X-ray lithography mask, X-ray irradiation is performed from the back surface of the X-ray transmission type substrate, and the X-ray exposure corresponding to the X-ray absorbing metal portion is performed. The resin layer is removed by development, and a voltage is applied to the X-ray absorbing metal portion by electroforming to laminate the X-ray absorbing metal portion on the portion where the X-ray photosensitive resin layer is removed. A method for manufacturing a diffraction grating.
前記Ｘ線感光樹脂層及び前記Ｘ線吸収金属部の表面にＸ線感光樹脂層を形成して、Ｘ線リソグラフィー法により、前記Ｘ線吸収金属部をＸ線リソグラフィーマスクとして前記Ｘ線透過型基板の裏面からＸ線を照射して、前記Ｘ線吸収金属部に対応する前記Ｘ線感光樹脂層を現像により除去し、そして、電鋳法により、前記金属シード層もしくは前記Ｘ線吸収金属部に電圧を印加して前記Ｘ線感光樹脂層が除去された部分にＸ線吸収金属部を積層させることを特徴とする、請求項６に記載の回折格子の製造方法。 A metal seed layer is formed on the surface of the X-ray transmissive substrate, an X-ray photosensitive resin layer is formed on the surface of the metal seed layer, and an X-ray formed on the surface of the metal seed layer by an X-ray lithography method. The photosensitive resin layer is patterned using an X-ray lithography mask, the X-ray photosensitive resin layer is removed by development, and a voltage is applied to the metal seed layer by electroforming to apply the X-ray photosensitive resin layer. After forming the X-ray absorbing metal part in the part from which is removed,
An X-ray photosensitive resin layer is formed on the surfaces of the X-ray photosensitive resin layer and the X-ray absorbing metal portion, and the X-ray transmissive substrate is formed by using an X-ray lithography mask with the X-ray absorbing metal portion as an X-ray lithography mask. The X-ray photosensitive resin layer corresponding to the X-ray absorbing metal part is removed by development, and the metal seed layer or the X-ray absorbing metal part is applied to the metal seed layer or the X-ray absorbing metal part by electroforming. 7. The method of manufacturing a diffraction grating according to claim 6, wherein an X-ray absorbing metal portion is laminated on a portion where the X-ray photosensitive resin layer is removed by applying a voltage.
Ｘ線透過型基板の表面に金属シード層を形成し、その金属シード層の表面にＸ線感光樹脂層を形成して、Ｘ線リソグラフィー法により、前記金属シード層の表面に形成されたＸ線感光樹脂層にＸ線リソグラフィーマスクを用いたパターニングを行って現像により前記Ｘ線感光樹脂層を除去し、そして、電鋳法により、前記金属シード層に電圧を印加して当該Ｘ線感光樹脂層が除去された部分にＸ線吸収金属部を形成することを特徴とする、回折格子の製造方法。 A method of manufacturing a diffraction grating used in an X-ray Talbot interferometer,
A metal seed layer is formed on the surface of the X-ray transmissive substrate, an X-ray photosensitive resin layer is formed on the surface of the metal seed layer, and an X-ray formed on the surface of the metal seed layer by an X-ray lithography method. The photosensitive resin layer is patterned using an X-ray lithography mask, the X-ray photosensitive resin layer is removed by development, and a voltage is applied to the metal seed layer by electroforming to apply the X-ray photosensitive resin layer. A method for producing a diffraction grating, wherein an X-ray absorbing metal portion is formed in a portion from which the metal is removed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007201570A JP4642818B2 (en) | 2007-08-02 | 2007-08-02 | Manufacturing method of diffraction grating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007201570A JP4642818B2 (en) | 2007-08-02 | 2007-08-02 | Manufacturing method of diffraction grating |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2009037023A true JP2009037023A (en) | 2009-02-19 |
| JP2009037023A5 JP2009037023A5 (en) | 2010-09-24 |
| JP4642818B2 JP4642818B2 (en) | 2011-03-02 |
Family
ID=40438991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007201570A Expired - Fee Related JP4642818B2 (en) | 2007-08-02 | 2007-08-02 | Manufacturing method of diffraction grating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4642818B2 (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011157622A (en) * | 2010-01-08 | 2011-08-18 | Canon Inc | Method for manufacturing microstructure |
| JP2012093332A (en) * | 2010-03-30 | 2012-05-17 | Fujifilm Corp | Grid for radiographic image taking and manufacturing method thereof |
| JP2012168397A (en) * | 2011-02-15 | 2012-09-06 | Canon Inc | Fine structure, manufacturing method thereof and imaging apparatus |
| JP2012173708A (en) * | 2011-02-24 | 2012-09-10 | Canon Inc | Method for manufacturing fine structure |
| JP2012225660A (en) * | 2011-04-15 | 2012-11-15 | Seiko Instruments Inc | Method for manufacturing phase type diffraction grating for x-ray talbot interferometer |
| JP2012247536A (en) * | 2011-05-26 | 2012-12-13 | Optnics Precision Co Ltd | Diffraction grating for x-ray interferometer and manufacturing method thereof |
| JP2013050439A (en) * | 2011-07-29 | 2013-03-14 | Canon Inc | Structure, manufacturing method thereof, and imaging apparatus using the structure |
| JP2013050432A (en) * | 2011-07-29 | 2013-03-14 | Canon Inc | Structure, manufacturing method thereof, and imaging apparatus using the structure |
| KR101306185B1 (en) | 2011-12-28 | 2013-09-17 | 단국대학교 산학협력단 | X-ray Nano-gratings of X-ray Grating Interferometer and Manufacturing Method thereof |
| JP2013536403A (en) * | 2010-06-17 | 2013-09-19 | カールスルーアー・インスティトゥート・フュア・テヒノロギー | X-ray imaging grating comprising at least two materials |
| RU2544390C2 (en) * | 2009-06-16 | 2015-03-20 | Конинклейке Филипс Электроникс Н.В. | Inclined diffraction gratings and method of making inclined diffraction gratings |
| US8999435B2 (en) * | 2009-08-31 | 2015-04-07 | Canon Kabushiki Kaisha | Process of producing grating for X-ray image pickup apparatus |
| JP2015178683A (en) * | 2010-01-08 | 2015-10-08 | キヤノン株式会社 | metal absorption grating and Talbot interferometer |
| EP2977992A1 (en) | 2014-07-24 | 2016-01-27 | Canon Kabushiki Kaisha | Structure, method for manufacturing the same, and talbot interferometer |
| US9748012B2 (en) | 2010-12-21 | 2017-08-29 | Konica Minolta, Inc. | Method for manufacturing metal grating structure, metal grating structure manufactured by the method, and X-ray imaging device using the metal grating structure |
| US10256001B2 (en) | 2011-07-27 | 2019-04-09 | Konica Minolta, Inc. | Metal grating structure for X-ray |
| JP2019055437A (en) * | 2017-09-20 | 2019-04-11 | 大日本印刷株式会社 | Manufacturing method of structure and structure |
| JP2021006780A (en) * | 2019-06-28 | 2021-01-21 | 株式会社ミツトヨ | Grating component and manufacturing method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61174502A (en) * | 1985-01-29 | 1986-08-06 | Shimadzu Corp | Optical element for soft x ray |
| JPH06192841A (en) * | 1992-12-24 | 1994-07-12 | Canon Inc | Formation of noble-metal single crystal group, applied article and its production |
-
2007
- 2007-08-02 JP JP2007201570A patent/JP4642818B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61174502A (en) * | 1985-01-29 | 1986-08-06 | Shimadzu Corp | Optical element for soft x ray |
| JPH06192841A (en) * | 1992-12-24 | 1994-07-12 | Canon Inc | Formation of noble-metal single crystal group, applied article and its production |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2544390C2 (en) * | 2009-06-16 | 2015-03-20 | Конинклейке Филипс Электроникс Н.В. | Inclined diffraction gratings and method of making inclined diffraction gratings |
| US8999435B2 (en) * | 2009-08-31 | 2015-04-07 | Canon Kabushiki Kaisha | Process of producing grating for X-ray image pickup apparatus |
| JP2011157622A (en) * | 2010-01-08 | 2011-08-18 | Canon Inc | Method for manufacturing microstructure |
| JP2015178683A (en) * | 2010-01-08 | 2015-10-08 | キヤノン株式会社 | metal absorption grating and Talbot interferometer |
| US9953734B2 (en) | 2010-01-08 | 2018-04-24 | Canon Kabushiki Kaisha | Microstructure manufacturing method |
| JP2012093332A (en) * | 2010-03-30 | 2012-05-17 | Fujifilm Corp | Grid for radiographic image taking and manufacturing method thereof |
| JP2013536403A (en) * | 2010-06-17 | 2013-09-19 | カールスルーアー・インスティトゥート・フュア・テヒノロギー | X-ray imaging grating comprising at least two materials |
| US9230703B2 (en) | 2010-06-17 | 2016-01-05 | Karlsruher Institut Fuer Technologie | Gratings for X-ray imaging, consisting of at least two materials |
| US9748012B2 (en) | 2010-12-21 | 2017-08-29 | Konica Minolta, Inc. | Method for manufacturing metal grating structure, metal grating structure manufactured by the method, and X-ray imaging device using the metal grating structure |
| JP2012168397A (en) * | 2011-02-15 | 2012-09-06 | Canon Inc | Fine structure, manufacturing method thereof and imaging apparatus |
| JP2012173708A (en) * | 2011-02-24 | 2012-09-10 | Canon Inc | Method for manufacturing fine structure |
| JP2012225660A (en) * | 2011-04-15 | 2012-11-15 | Seiko Instruments Inc | Method for manufacturing phase type diffraction grating for x-ray talbot interferometer |
| JP2012247536A (en) * | 2011-05-26 | 2012-12-13 | Optnics Precision Co Ltd | Diffraction grating for x-ray interferometer and manufacturing method thereof |
| US10256001B2 (en) | 2011-07-27 | 2019-04-09 | Konica Minolta, Inc. | Metal grating structure for X-ray |
| JP2013050439A (en) * | 2011-07-29 | 2013-03-14 | Canon Inc | Structure, manufacturing method thereof, and imaging apparatus using the structure |
| US9891327B2 (en) | 2011-07-29 | 2018-02-13 | Canon Kabushiki Kaisha | Structure, method for manufacturing the same, and image pickup apparatus including the structure |
| JP2013050432A (en) * | 2011-07-29 | 2013-03-14 | Canon Inc | Structure, manufacturing method thereof, and imaging apparatus using the structure |
| KR101306185B1 (en) | 2011-12-28 | 2013-09-17 | 단국대학교 산학협력단 | X-ray Nano-gratings of X-ray Grating Interferometer and Manufacturing Method thereof |
| EP2977992A1 (en) | 2014-07-24 | 2016-01-27 | Canon Kabushiki Kaisha | Structure, method for manufacturing the same, and talbot interferometer |
| US10045753B2 (en) * | 2014-07-24 | 2018-08-14 | Canon Kabushiki Kaisha | Structure, method for manufacturing the same, and talbot interferometer |
| EP3614398A1 (en) | 2014-07-24 | 2020-02-26 | Canon Kabushiki Kaisha | Structure, method for manufacturing the same, and talbot interferometer |
| JP2019055437A (en) * | 2017-09-20 | 2019-04-11 | 大日本印刷株式会社 | Manufacturing method of structure and structure |
| JP7059545B2 (en) | 2017-09-20 | 2022-04-26 | 大日本印刷株式会社 | Structure manufacturing method and structure |
| JP2021006780A (en) * | 2019-06-28 | 2021-01-21 | 株式会社ミツトヨ | Grating component and manufacturing method thereof |
| JP7319106B2 (en) | 2019-06-28 | 2023-08-01 | 株式会社ミツトヨ | Lattice part and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4642818B2 (en) | 2011-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4642818B2 (en) | Manufacturing method of diffraction grating | |
| JP4663742B2 (en) | Manufacturing method of diffraction grating | |
| JP2006259264A (en) | Manufacturing method for x-ray phase type diffraction grating and amplitude type diffraction grating used for x-ray talbot interferometer | |
| JP5420923B2 (en) | Manufacturing method of X-ray Talbot diffraction grating | |
| JP2009042528A (en) | Method of manufacturing diffraction grating | |
| JP5459659B2 (en) | Phase grating used for imaging X-ray phase contrast image, imaging apparatus using the phase grating, and X-ray computed tomography system | |
| US8908274B2 (en) | Microstructure manufacturing method and microstructure | |
| David et al. | Fabrication of diffraction gratings for hard X-ray phase contrast imaging | |
| US8243879B2 (en) | Source grating for X-rays, imaging apparatus for X-ray phase contrast image and X-ray computed tomography system | |
| US9036773B2 (en) | Method for X-ray phase contrast and dark-field imaging using an arrangement of gratings in planar geometry | |
| JP5660910B2 (en) | Method for manufacturing grid for radiographic imaging | |
| JP5601909B2 (en) | X-ray imaging apparatus and X-ray imaging method using the same | |
| WO2004058070A1 (en) | X-ray imaging system and imaging method | |
| JP2013536403A (en) | X-ray imaging grating comprising at least two materials | |
| JP2009195349A (en) | X-ray imaging apparatus, and x-ray source used therefor | |
| JP2012187341A (en) | X-ray imaging apparatus | |
| Takeda et al. | Differential phase X-ray imaging microscopy with X-ray Talbot interferometer | |
| TW201109851A (en) | Wavefront measuring method and device, and exposure method and device | |
| JP2016032573A (en) | Talbot interferometer, talbot interference system and fringe scanning method | |
| US9040227B2 (en) | Microstructure manufacturing method | |
| WO2013084421A1 (en) | Microstructure, and imaging apparatus having the microstructure | |
| JP2009282322A (en) | Method of manufacturing amplitude type diffraction grating | |
| WO2020007558A1 (en) | Position sensor | |
| Brose et al. | Optimized phase-shifting masks for high-resolution resist patterning by interference lithography | |
| JP2012122840A (en) | Grid for photographing radiation image, method for manufacturing the same, and radiation image photographing system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100611 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100722 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100722 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20100722 |
|
| A871 | Explanation of circumstances concerning accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A871 Effective date: 20100722 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20100722 |
|
| A975 | Report on accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A971005 Effective date: 20100827 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100914 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100928 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20101124 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20101201 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131210 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |