JPWO2008152889A1 - Photoelectric conversion element manufacturing method, image sensor, and radiation image detector - Google Patents
Photoelectric conversion element manufacturing method, image sensor, and radiation image detector Download PDFInfo
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- JPWO2008152889A1 JPWO2008152889A1 JP2009519203A JP2009519203A JPWO2008152889A1 JP WO2008152889 A1 JPWO2008152889 A1 JP WO2008152889A1 JP 2009519203 A JP2009519203 A JP 2009519203A JP 2009519203 A JP2009519203 A JP 2009519203A JP WO2008152889 A1 JPWO2008152889 A1 JP WO2008152889A1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
- G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
- G01T1/16—Measuring radiation intensity
- G01T1/24—Measuring radiation intensity with semiconductor detectors
- G01T1/241—Electrode arrangements, e.g. continuous or parallel strips or the like
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
- H04N23/00—Cameras or camera modules comprising electronic image sensors; Control thereof
- H04N23/80—Camera processing pipelines; Components thereof
- H04N23/81—Camera processing pipelines; Components thereof for suppressing or minimising disturbance in the image signal generation
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14643—Photodiode arrays; MOS imagers
- H01L27/14658—X-ray, gamma-ray or corpuscular radiation imagers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
- H10K39/30—Devices controlled by radiation
- H10K39/32—Organic image sensors
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
- H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/114—Poly-phenylenevinylene; Derivatives thereof
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/211—Fullerenes, e.g. C60
- H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
本発明は、有機材料を用いながら暗電流の少ない光電変換素子、光電変換素子の製造方法、イメージセンサおよび放射線画像検出器を提供する。かかる光電変換素子は、支持基板の上に透明電極と、透明電極を透過した光を吸収し電荷分離を行う有機半導体からなる光電変換層と、光電変換層を挟んで透明電極と反対側に設けられた対電極と、を有する光電変換素子であって、光電変換層と対電極の間に電極酸化膜を有する。The present invention provides a photoelectric conversion element having a low dark current while using an organic material, a method for manufacturing the photoelectric conversion element, an image sensor, and a radiation image detector. Such a photoelectric conversion element is provided on a support substrate on the opposite side of the transparent electrode with a transparent electrode, a photoelectric conversion layer made of an organic semiconductor that absorbs light transmitted through the transparent electrode and performs charge separation, and sandwiching the photoelectric conversion layer A counter electrode having an electrode oxide film between the photoelectric conversion layer and the counter electrode.
Description
光電変換素子、光電変換素子の製造方法、イメージセンサおよび放射線画像検出器に関する。 The present invention relates to a photoelectric conversion element, a method for manufacturing a photoelectric conversion element, an image sensor, and a radiation image detector.
グレッツェルらは酸化チタンなどの透明電極上に光電変換機能を有する有機色素の膜を形成することにより、アモルファスシリコン光電変換素子に近い性能を有する色素増感型光電変換素子（グレッツェルセル）を報告している（非特許文献１参照。）。 Gretzel et al. Reported a dye-sensitized photoelectric conversion element (Gretzel cell) that has a performance similar to that of an amorphous silicon photoelectric conversion element by forming a film of an organic dye having a photoelectric conversion function on a transparent electrode such as titanium oxide. (See Non-Patent Document 1).
また、近年、ナノテクノロジーの手法を用いて、フラーレンを有する単分子膜を用いた色素増感型光電変換素子についても報告されている（例えば、特許文献１、２参照。）。 In recent years, a dye-sensitized photoelectric conversion element using a monomolecular film having fullerene has also been reported using a nanotechnology technique (see, for example, Patent Documents 1 and 2).
これら色素増感型光電変換素子は、対電極との電気的接合を液体レドックス電解質によって行う湿式太陽電池であるため、長期にわたって使用すると電解液の枯渇により光電変換機能が著しく低下してしまい、光電変換素子として機能しなくなってしまうことが懸念される。また電解液を用いない有機材料による光電変換素子として、透明電極と対電極との間に電子供与体と電子受容体を混合した層を形成したバルクヘテロ接合型光電変換素子、あるいは透明電極と対電極との間に電子供与体層と電子受容体層を挟んだヘテロ接合型（積層型）光電変換素子が提案されている（特許文献３参照。）。 Since these dye-sensitized photoelectric conversion elements are wet solar cells that are electrically connected to the counter electrode using a liquid redox electrolyte, the photoelectric conversion function is significantly reduced due to depletion of the electrolyte when used over a long period of time. There is concern that it will no longer function as a conversion element. In addition, as a photoelectric conversion element using an organic material that does not use an electrolyte, a bulk heterojunction photoelectric conversion element in which a layer in which an electron donor and an electron acceptor are mixed is formed between a transparent electrode and a counter electrode, or a transparent electrode and a counter electrode A heterojunction type (stacked type) photoelectric conversion element has been proposed in which an electron donor layer and an electron acceptor layer are sandwiched between them (see Patent Document 3).
これらの光電変換素子の動作原理は、光励起により電子供与体（あるいは電子供与体層）から電子受容体（あるいは電子受容体層）への電子の移動により正孔と電子が発生し、内部電界により正孔は電子供与体間（あるいは電子供与体層）を通り一方の電極に運ばれ、電子は電子受容体間（あるいは電子受容体層）を通りもう一方の電極へ運ばれ、光電流が観測されるというものである。しかしながら、前者の透明電極と対電極との間に電子供与体と電子受容体を一様に混合した層を形成した光電変換素子では、電子受容体と電子供与体が均一に混在しているため、電荷分離後により発生した電子と正孔が電荷輸送中に再結合し易く、これが光電変換効率を下げる要因となっている。また後者の透明電極と対電極との間に電子供与体層と電子受容体層を挟んだ光電変換素子では、電子供与体層と電子受容体層の界面でのみ、電荷分離を行うため、電荷発生量が非常に少なく、光電変換効率が低い。 The operation principle of these photoelectric conversion elements is that holes and electrons are generated by the movement of electrons from the electron donor (or electron donor layer) to the electron acceptor (or electron acceptor layer) by photoexcitation, and are generated by an internal electric field. Holes are transported between electron donors (or electron donor layer) to one electrode, electrons are transported between electron acceptors (or electron acceptor layer) to the other electrode, and photocurrent is observed It is to be done. However, in the former photoelectric conversion element in which the layer in which the electron donor and the electron acceptor are uniformly mixed is formed between the transparent electrode and the counter electrode, the electron acceptor and the electron donor are uniformly mixed. Electrons and holes generated after charge separation are likely to recombine during charge transport, which is a factor in reducing photoelectric conversion efficiency. In the photoelectric conversion element in which the electron donor layer and the electron acceptor layer are sandwiched between the transparent electrode and the counter electrode, charge separation is performed only at the interface between the electron donor layer and the electron acceptor layer. The amount of generation is very small and the photoelectric conversion efficiency is low.
次に前記光電変換素子を応用したＸ線画像検出器について説明する。アモルファスシリコン光電変換素子は、太陽電池や複写機の感光ドラムとしての応用以外に、フラットパネル型の放射線ディテクタ（ＦＰＤ）として医療分野でも応用されている。また有機材料による光電変換素子においても、ＦＰＤへの応用が提案されている（特許文献４参照。）。 Next, an X-ray image detector to which the photoelectric conversion element is applied will be described. Amorphous silicon photoelectric conversion elements are applied in the medical field as flat panel radiation detectors (FPDs) in addition to application as photosensitive drums for solar cells and copying machines. Moreover, application to FPD has also been proposed for photoelectric conversion elements made of organic materials (see Patent Document 4).
ＦＰＤとはデジタル式Ｘ線画像検出器の一種で、放射線画像をデジタル信号として読み出し、放射線写真フィルム（レントゲンフィルムなど）を用いずに、パソコンなどのモニターで診断することができるといったシステムである。ＦＰＤには、光電変換素子がＸ線を直接吸収し光電変換するもの（直接型ＦＰＤ）と、蛍光体によってＸ線を蛍光に変換し、その蛍光を光電変換素子が吸収して光電変換するもの（間接型ＦＰＤ）があり、前記アモルファスシリコン光電変換素子や有機材料による光電変換素子は、後者の間接型ＦＰＤに用いられる。 FPD is a kind of digital X-ray image detector, and is a system that reads out a radiographic image as a digital signal and can make a diagnosis on a monitor such as a personal computer without using a radiographic film (such as an X-ray film). In FPD, a photoelectric conversion element absorbs X-rays directly and performs photoelectric conversion (direct FPD), and a fluorescent substance converts X-rays into fluorescence, and the photoelectric conversion element absorbs the fluorescence and performs photoelectric conversion. (Indirect type FPD), and the amorphous silicon photoelectric conversion element and the organic material photoelectric conversion element are used for the latter indirect type FPD.
アモルファスシリコン光電変換素子を用いた間接型ＦＰＤの利点は、従来のアナログシステムに匹敵するほどの高画質の画像が得られることであるが、アモルファスシリコン光電変換素子は、アモルファスシリコンなどの無機半導体物質を薄膜トランジスタ（ＴＦＴ）上に微細加工する必要があり、非常に高度な技術と設備を要するため、製品価格が非常に上昇してしまうという問題がある。 The advantage of the indirect FPD using the amorphous silicon photoelectric conversion element is that a high-quality image comparable to the conventional analog system can be obtained. The amorphous silicon photoelectric conversion element is an inorganic semiconductor material such as amorphous silicon. Is required to be finely processed on a thin film transistor (TFT), which requires very advanced technology and equipment, resulting in a problem that the product price is extremely increased.
一方、有機材料を用いた光電変換素子は、有機物を用いるため加工が非常に容易であり、製品価格が非常に安くなるといった利点があり、近年注目されている。
しかしながら、有機材料を用いた光電変換素子はアモルファスシリコン光電変換素子と比べて暗電流が多く、より高画質の画像を得るためには暗電流を低減する必要がある。 However, a photoelectric conversion element using an organic material has more dark current than an amorphous silicon photoelectric conversion element, and it is necessary to reduce the dark current in order to obtain a higher quality image.
本発明は、上記課題に鑑みてなされたものであって、有機材料を用いながら暗電流の少ない光電変換素子、光電変換素子の製造方法、イメージセンサおよび放射線画像検出器を提供することを目的とする。 The present invention has been made in view of the above problems, and an object thereof is to provide a photoelectric conversion element having a low dark current while using an organic material, a method for manufacturing the photoelectric conversion element, an image sensor, and a radiation image detector. To do.
上記目的は、下記の１乃至７のいずれか１項に記載の発明によって達成される。 The above object is achieved by the invention described in any one of 1 to 7 below.
１．少なくとも支持基板上に、透明電極と、
有機半導体からなる光電変換層と、
前記光電変換層を挟んで前記透明電極と反対側に設けられた対電極と、
を有する光電変換素子において、
前記対電極は電極酸化膜を有し、該電極酸化膜を挟んで前記光電変換層と接することを特徴とする光電変換素子。1. A transparent electrode at least on a support substrate;
A photoelectric conversion layer made of an organic semiconductor;
A counter electrode provided on the opposite side of the transparent electrode across the photoelectric conversion layer;
In a photoelectric conversion element having
The counter electrode has an electrode oxide film, and is in contact with the photoelectric conversion layer with the electrode oxide film interposed therebetween.
２．前記電極酸化膜の厚みは１〜８ｎｍであることを特徴とする前記１に記載の光電変換素子。 2. 2. The photoelectric conversion element as described in 1 above, wherein the electrode oxide film has a thickness of 1 to 8 nm.
３．前記１または２に記載の光電変換素子を製造する光電変換素子の製造方法において、
前記支持基板の上に前記透明電極を形成する工程と、
前記透明電極の上に前記光電変換層を形成する工程と、
前記光電変換層の上に前記対電極を形成する工程と、
前記支持基板を一定時間加熱するアニール処理工程と、
を有し、
前記光電変換層の上に前記対電極を形成する工程の後、前記アニール処理工程を行うことにより前記電極酸化膜を形成することを特徴とする光電変換素子の製造方法。3. In the manufacturing method of the photoelectric conversion element which manufactures the photoelectric conversion element of said 1 or 2,
Forming the transparent electrode on the support substrate;
Forming the photoelectric conversion layer on the transparent electrode;
Forming the counter electrode on the photoelectric conversion layer;
An annealing treatment step of heating the support substrate for a predetermined time;
Have
A method for producing a photoelectric conversion element, wherein the electrode oxide film is formed by performing the annealing treatment step after the step of forming the counter electrode on the photoelectric conversion layer.
４．前記アニール処理工程は、５０℃〜１５０℃の温度範囲で加熱することを特徴とする３に記載の光電変換素子の製造方法。 4). 4. The method for manufacturing a photoelectric conversion element according to 3, wherein the annealing step is performed in a temperature range of 50 ° C. to 150 ° C.
５．前記透明電極の上に前記光電変換層を形成する工程は、
溶媒に有機半導体材料を溶解または分散させて有機半導体溶液を作製する第１工程と、
前記有機半導体溶液を塗布する第２工程と、
塗布した前記有機半導体溶液を一定時間加熱して乾燥させる第３工程と、
を含み、
前記第１工程、前記第２工程、前記第３工程のうち少なくとも一つの工程を、酸素を含む雰囲気下で行うことを特徴とする前記３または４に記載の光電変換素子の製造方法。5). The step of forming the photoelectric conversion layer on the transparent electrode,
A first step of preparing an organic semiconductor solution by dissolving or dispersing an organic semiconductor material in a solvent;
A second step of applying the organic semiconductor solution;
A third step of heating and drying the applied organic semiconductor solution for a predetermined time;
Including
5. The method for producing a photoelectric conversion element according to 3 or 4, wherein at least one of the first step, the second step, and the third step is performed in an atmosphere containing oxygen.
６．前記１または２に記載の光電変換素子を含む画素が、支持基板の上にマトリクス状に複数形成されていることを特徴とするイメージセンサ。 6). 3. An image sensor comprising a plurality of pixels including the photoelectric conversion element according to 1 or 2 formed in a matrix on a support substrate.
７．前記６に記載のイメージセンサと、
放射線を可視光に変換する蛍光体からなるシンチレータ層と、を有し、
前記シンチレータ層は、前記イメージセンサの前記画素に前記可視光が入射するように配設されていることを特徴とする放射線画像検出器。7). The image sensor according to 6;
A scintillator layer made of a phosphor that converts radiation into visible light,
The radiation image detector, wherein the scintillator layer is disposed so that the visible light is incident on the pixels of the image sensor.
本発明によれば、対電極は、対電極の表面に形成した電極酸化膜を挟んで光電変換層と接するので、暗電流の少ない光電変換素子、光電変換素子の製造方法、イメージセンサおよび放射線画像検出器を提供することができる。 According to the present invention, since the counter electrode is in contact with the photoelectric conversion layer with the electrode oxide film formed on the surface of the counter electrode interposed therebetween, the photoelectric conversion element with a small dark current, the method for manufacturing the photoelectric conversion element, the image sensor, and the radiation image A detector can be provided.
１ 支持基板
２ ゲート電極
５ 活性層
７ ゲート絶縁層
８ ソース
９ ドレイン
２０ イメージセンサ
２２ 放射線画像検出器
４０ 筐体
１００ 透明電極
１０１ 光電変換層
１０２ 上部電極
１０３ 保護膜
１０４ 正孔輸送層
１０５ 電極酸化膜
１１２ パッシベーション層
１３１ シンチレータ
１３３ 保護膜DESCRIPTION OF SYMBOLS 1 Support substrate 2 Gate electrode 5 Active layer 7 Gate insulating layer 8 Source 9 Drain 20 Image sensor 22 Radiation image detector 40 Case 100 Transparent electrode 101 Photoelectric conversion layer 102 Upper electrode 103 Protective film 104 Hole transport layer 105 Electrode oxide film 112 Passivation layer 131 Scintillator 133 Protective film
以下、本発明の実施形態を図１を用いて詳細に説明する。 Hereinafter, an embodiment of the present invention will be described in detail with reference to FIG.
図１は、本発明の実施形態に係わるバルクヘテロ接合型の光電変換素子の製造工程を説明するための支持基板の断面図である。 FIG. 1 is a cross-sectional view of a support substrate for explaining a manufacturing process of a bulk heterojunction photoelectric conversion element according to an embodiment of the present invention.
図１（１−ａ）、図１（２−ａ）、図１（３−ａ）、図１（４−ａ）は、支持基板１を上面から見た平面図である。図１（１−ｂ）、図１（２−ｂ）、図１（３−ｂ）、図１（４−ｂ）は、それぞれ支持基板１を図１（１−ａ）、図１（２−ａ）、図１（３−ａ）、図１（４−ａ）の断面Ａ−Ａ’で切断した断面図である。 1 (1-a), FIG. 1 (2-a), FIG. 1 (3-a), and FIG. 1 (4-a) are plan views of the support substrate 1 as viewed from above. 1 (1-b), FIG. 1 (2-b), FIG. 1 (3-b), and FIG. 1 (4-b) show the supporting substrate 1 in FIG. 1 (1-a) and FIG. It is sectional drawing cut | disconnected by the cross section AA 'of -a), FIG. 1 (3-a), and FIG. 1 (4-a).
図１（４−ａ）、図１（４−ｂ）は本発明の光電変換素子８１の断面構成を示している。図１の１は透明な絶縁性の支持基板、１００はＩＴＯ、ＳｎＯ2等の透明導電性材料からなる透明電極、１０４は有機材料からなる正孔輸送層、１０１は有機半導体材料からなる光電変換層、１０２はアルミなど金属材料からなる対電極、である。また、図１（４−ｂ）に示すように、光電変換層１０１と接する対電極１０２の間に対電極１０２の表面を酸化した電極酸化膜１０５が形成されている。FIG. 1 (4-a) and FIG. 1 (4-b) show a cross-sectional configuration of the photoelectric conversion element 81 of the present invention. In FIG. 1, 1 is a transparent insulating support substrate, 100 is a transparent electrode made of a transparent conductive material such as ITO or SnO 2 , 104 is a hole transport layer made of an organic material, and 101 is a photoelectric conversion made of an organic semiconductor material. A layer 102 is a counter electrode made of a metal material such as aluminum. As shown in FIG. 1 (4-b), an electrode oxide film 105 is formed between the counter electrode 102 in contact with the photoelectric conversion layer 101 by oxidizing the surface of the counter electrode 102.
図１（４−ｂ）の矢印Ｌは光電変換素子８１に入射する光束の方向を示している。 An arrow L in FIG. 1 (4-b) indicates the direction of the light beam incident on the photoelectric conversion element 81.
本発明に係る光電変換素子８１の製造方法の一例として、次の工程Ｓ１〜Ｓ５を説明する。
Ｓ１・・・・・透明電極１００を形成する工程。
Ｓ２・・・・・正孔輸送層１０４を形成する工程。
Ｓ３・・・・・光電変換層１０１を形成する工程。As an example of the manufacturing method of the photoelectric conversion element 81 according to the present invention, the following steps S1 to S5 will be described.
S1... The step of forming the transparent electrode 100.
S2 Step for forming the hole transport layer 104.
S3: A step of forming the photoelectric conversion layer 101.
Ｓ３−１・・・溶媒に有機半導体材料を溶解または分散させ有機半導体溶液を作製する第１工程。 S3-1: A first step of preparing an organic semiconductor solution by dissolving or dispersing an organic semiconductor material in a solvent.
Ｓ３−２・・・有機半導体溶液を塗布する第２工程。 S3-2: Second step of applying an organic semiconductor solution.
Ｓ３−３・・・塗布した有機半導体溶液を一定時間加熱して乾燥させる第３工程。
Ｓ４・・・・対電極１０２を形成する工程。
Ｓ５・・・・アニール処理工程。S3-3 A third step of drying the applied organic semiconductor solution by heating for a certain time.
S4... Step of forming the counter electrode 102.
S5... Annealing process.
以下、各工程について順に説明する。 Hereinafter, each process is demonstrated in order.
Ｓ１・・・・・透明電極１００を形成する工程。 S1... The step of forming the transparent electrode 100.
図１（１−ａ）、図１（１−ｂ）に示すように、支持基板１上に透明電極１００を形成する。本発明において、支持基板１は透明な絶縁性の材料であれば特に材料を限定されない。例えば低融点ガラスやＰＥＮ、ＰＥＳ、ＰＣ、ＴＡＣなどのフィルム基板を用いることができる。 As shown in FIG. 1 (1-a) and FIG. 1 (1-b), a transparent electrode 100 is formed on the support substrate 1. In the present invention, the support substrate 1 is not particularly limited as long as it is a transparent insulating material. For example, a low-melting glass or a film substrate such as PEN, PES, PC, or TAC can be used.
透明電極１００とは、光電変換される光を透過する電極を言い、好ましくは３００〜８００ｎｍの光を透過する電極である。材料としては、例えば、インジウムチンオキシド（ＩＴＯ）、ＳｎＯ2、ＺｎＯ等の透明導電性金属酸化物、金、銀、白金などの金属薄膜、導電性高分子を用いることが好ましいが、これに限定されるものではない。The transparent electrode 100 refers to an electrode that transmits light to be photoelectrically converted, and is preferably an electrode that transmits light of 300 to 800 nm. As the material, for example, it is preferable to use transparent conductive metal oxides such as indium tin oxide (ITO), SnO 2 and ZnO, metal thin films such as gold, silver and platinum, and conductive polymers. Is not to be done.
透明電極１００の膜厚ｔ１はシンチレータ１３１の発光する光を７０％以上透過するよう５００ｎｍ以下が望ましい。一方、透明電極１００の導電性を確保するため１０ｎｍ以上の厚みは必要である。したがって、透明電極１００の膜厚ｔ１は１０ｎｍ≦ｔ１≦５００ｎｍにすることが望ましい。 The film thickness t1 of the transparent electrode 100 is desirably 500 nm or less so as to transmit 70% or more of the light emitted from the scintillator 131. On the other hand, a thickness of 10 nm or more is necessary to ensure the conductivity of the transparent electrode 100. Therefore, the film thickness t1 of the transparent electrode 100 is desirably 10 nm ≦ t1 ≦ 500 nm.
また、ＩＴＯ、ＩＺＯ、ＳｎＯ、ＺｎＯなどの透明電極を用いることもできる。製造方法は、目的の形状にパターニングすることのできるマスク蒸着法、フォトリソグラフィー法、各種印刷法が利用できる。 A transparent electrode such as ITO, IZO, SnO, or ZnO can also be used. As a manufacturing method, a mask vapor deposition method, a photolithography method, and various printing methods that can be patterned into a target shape can be used.
Ｓ２・・・・・正孔輸送層１０４を形成する工程。 S2 Step for forming the hole transport layer 104.
例えば、ＰＥＤＯＴ／ＰＳＳ（ポリ（３，４−エチレンジオキシチオフェン）−ポリスチレンスルホネート）などの有機導電材料を材料として、スピンコート法を用いて支持基板１上に形成する。その後、オーブンで加熱し乾燥させる。 For example, an organic conductive material such as PEDOT / PSS (poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate) is used as a material and is formed on the support substrate 1 using a spin coating method. Thereafter, it is heated in an oven and dried.
Ｓ３・・・・・光電変換層１０１を形成する工程。 S3: A step of forming the photoelectric conversion layer 101.
例えば、電子受容性有機材料と電子供与性有機材料とを有機溶媒に溶解した溶液を工程Ｓ２までの処理を終えた支持基板１の所望の領域に、スピンコート法などを用いて塗布し、乾燥させてバルクヘテロ型の光電変換層１０１を形成する。 For example, a solution in which an electron-accepting organic material and an electron-donating organic material are dissolved in an organic solvent is applied to a desired region of the support substrate 1 that has been subjected to the process up to step S2 using a spin coating method or the like, and then dried. Thus, the bulk hetero photoelectric conversion layer 101 is formed.
本工程は詳しくは以下の工程Ｓ３−１、Ｓ３−２、Ｓ３−３からなる。 Specifically, this step includes the following steps S3-1, S3-2, and S3-3.
Ｓ３−１・・・溶媒に有機半導体材料を溶解または分散させ有機半導体溶液を作製する第１工程。 S3-1: A first step of preparing an organic semiconductor solution by dissolving or dispersing an organic semiconductor material in a solvent.
例えば、電子受容性有機材料としてＰＣＢＭ（ブチリックアシッドメチルエステル）、電子供与性有機材料としてＰ３ＨＴ（ポリ−３−ヘキシルチオフェン）を質量比７：３の割合でクロロベンゼン溶液に溶解または分散させ有機半導体溶液を作製する。 For example, PCBM (butyric acid methyl ester) as an electron-accepting organic material and P3HT (poly-3-hexylthiophene) as an electron-donating organic material are dissolved or dispersed in a chlorobenzene solution at a mass ratio of 7: 3 to form an organic semiconductor. Make a solution.
Ｓ３−２・・・有機半導体溶液を塗布する第２工程。 S3-2: Second step of applying an organic semiconductor solution.
例えば、スピンコート、インクジェット法などを用いて有機半導体溶液を正孔輸送層１０４の上に塗布する。 For example, an organic semiconductor solution is applied onto the hole transport layer 104 by spin coating, an inkjet method, or the like.
Ｓ３−３・・・塗布した有機半導体溶液を一定時間加熱して乾燥させる第３工程。 S3-3 A third step of drying the applied organic semiconductor solution by heating for a certain time.
例えば、支持基板１を１００℃のオーブンで３０分加熱して有機半導体溶液を乾燥させ７０ｎｍの光電変換層１０１を形成する。 For example, the support substrate 1 is heated in an oven at 100 ° C. for 30 minutes to dry the organic semiconductor solution to form the 70 nm photoelectric conversion layer 101.
これらの工程Ｓ３−１、Ｓ３−２、Ｓ３−３のうち少なくとも１つの工程は、後の工程で形成する対電極１０２の光電変換層１０１と接する面に電極酸化膜１０５が形成されるように、大気下など酸素を含有する雰囲気下で行うことが望ましい。 At least one of these steps S3-1, S3-2, and S3-3 is performed so that the electrode oxide film 105 is formed on the surface of the counter electrode 102 that is to be formed in a later step and in contact with the photoelectric conversion layer 101. It is desirable to perform in an atmosphere containing oxygen, such as in the air.
なお、電子受容性有機材料と電子供与性有機材料は、これらの例に限定されるものではなく、例えば特開２００５−３２７９３号公報に開示されている各種材料を用いることができる。また、本実施形態では平坦化と正孔を輸送する目的で正孔輸送層１０４を形成する例を説明したが、必ずしも必須ではなく正孔輸送層１０４を形成しない光電変換素子にも本発明を適用できる。 The electron-accepting organic material and the electron-donating organic material are not limited to these examples, and various materials disclosed in, for example, Japanese Patent Application Laid-Open No. 2005-32793 can be used. In this embodiment, an example in which the hole transport layer 104 is formed for the purpose of flattening and transporting holes has been described. However, the present invention is not necessarily essential and the present invention is also applied to a photoelectric conversion element that does not form the hole transport layer 104. Applicable.
さらに、本発明の適用はバルクヘテロ型の光電変換層に限定されるものではなく、例えば特開２００５−３２７９３号公報に開示されている電子受容性有機材料からなる層と電子供与性有機材料からなる層を積層したスタック型の光電変換層を形成しても良い。 Furthermore, the application of the present invention is not limited to the bulk hetero type photoelectric conversion layer, and includes, for example, a layer made of an electron-accepting organic material and an electron-donating organic material disclosed in JP-A-2005-32793. A stacked photoelectric conversion layer in which layers are stacked may be formed.
Ｓ４・・・・対電極１０２を形成する工程。 S4... Step of forming the counter electrode 102.
光電変換層１０１の上に対電極１０２を形成する。対電極１０２は、メタルマスクを用いて、例えばＡｌ、Ａｇ、Ａｕ、Ｐｔなどの金属材料を蒸着して形成する。 A counter electrode 102 is formed over the photoelectric conversion layer 101. The counter electrode 102 is formed by evaporating a metal material such as Al, Ag, Au, or Pt using a metal mask.
Ｓ５・・・・アニール処理工程。 S5... Annealing process.
次に、大気下など酸素を含有する雰囲気下で、Ｓ４までの工程を終えた支持基板１を５０℃〜１５０℃の温度範囲で３０分加熱し、アニール処理を行う。このことにより、対電極１０２の光電変換層１０１に接する面の酸化を促進し、電極酸化膜１０５を形成することができる。 Next, in an atmosphere containing oxygen such as the air, the support substrate 1 that has completed the steps up to S4 is heated in a temperature range of 50 ° C. to 150 ° C. for 30 minutes to perform an annealing treatment. As a result, the oxidation of the surface of the counter electrode 102 in contact with the photoelectric conversion layer 101 can be promoted, and the electrode oxide film 105 can be formed.
アニール処理の温度が高いほど電極酸化膜１０５は厚くなるが、暗電流が低下するとともに光電流も低下する。後の実施例で説明するように１５０℃を超す温度では光電流の低下が大きくなり、Ｓ／Ｎの点から望ましくない。一方、アニール処理の温度が低いと電極酸化膜１０５は薄くなる。５０℃未満では電極酸化膜１０５の厚みが測定できないほど薄くなり、暗電流を低減する効果が得られない。５０℃〜１５０℃の温度範囲では、光電変換素子８１の光電流はほとんど低下せずに暗電流を低減する電極酸化膜１０５を形成できるので、光電変換素子８１の信号出力のＳ／Ｎを改善することができる。 The higher the annealing temperature, the thicker the electrode oxide film 105 is, but the dark current is lowered and the photocurrent is also lowered. As will be described later, the photocurrent decreases greatly at temperatures exceeding 150 ° C., which is not desirable from the viewpoint of S / N. On the other hand, when the annealing temperature is low, the electrode oxide film 105 becomes thin. If it is less than 50 ° C., the thickness of the electrode oxide film 105 becomes so thin that it cannot be measured, and the effect of reducing dark current cannot be obtained. In the temperature range of 50 ° C. to 150 ° C., the photocurrent of the photoelectric conversion element 81 hardly decreases, and the electrode oxide film 105 that reduces the dark current can be formed. Therefore, the S / N of the signal output of the photoelectric conversion element 81 is improved. can do.
これまでの工程で透明電極１００、正孔輸送層１０４、光電変換層１０１、電極酸化膜１０５、対電極１０２から構成される光電変換素子８１が作製できた。 The photoelectric conversion element 81 including the transparent electrode 100, the hole transport layer 104, the photoelectric conversion layer 101, the electrode oxide film 105, and the counter electrode 102 can be manufactured through the steps so far.
この後、上部電極１０２の上層に保護膜として、例えばポリイミドをスピンコート法で形成する。 Thereafter, for example, polyimide is formed as a protective film on the upper layer of the upper electrode 102 by spin coating.
以上で光電変換素子８１の製造工程は終了である。 The manufacturing process of the photoelectric conversion element 81 is thus completed.
次に、透明な支持基板の上にシンチレータを形成し、その上に２次元マトリックス状に読み出し用薄膜トランジスタ（以下、薄膜トランジスタはＴＦＴと称する。）とバルクヘテロ接合型の光電変換素子を形成したイメージセンサを有する放射線画像検出器について説明する。 Next, an image sensor in which a scintillator is formed on a transparent support substrate and a reading thin film transistor (hereinafter referred to as a thin film transistor is referred to as a TFT) and a bulk heterojunction photoelectric conversion element are formed on the scintillator. A radiation image detector having the above will be described.
図２は、本発明の実施形態に係わる放射線画像検出器２２の構造の一例を示す説明図である。 FIG. 2 is an explanatory diagram showing an example of the structure of the radiation image detector 22 according to the embodiment of the present invention.
放射線画像検出器２２は、イメージセンサ２０、ゲートドライバＩＣ６、読み出しＩＣ８７、制御回路３０、メモリ部３１、操作部３２、表示部３３、電源部３４、コネクタ３５、筐体４０を有している。イメージセンサ２０は、照射された放射線の強度に応じて蓄積された電気エネルギーを生成するものであり、生成された電気エネルギーはゲートドライバＩＣ６により読み出され、読み出しＩＣ８７により画像信号として出力される。出力された画像信号は、書き換え可能な読み出し専用メモリ（例えばフラッシュメモリ）等を用いてメモリ部３１に記憶される。また放射線画像検出器２２の動作は、制御回路３０で制御され、操作部３２により動作が切り替えられる。 The radiation image detector 22 includes an image sensor 20, a gate driver IC 6, a readout IC 87, a control circuit 30, a memory unit 31, an operation unit 32, a display unit 33, a power supply unit 34, a connector 35, and a housing 40. The image sensor 20 generates accumulated electrical energy according to the intensity of irradiated radiation, and the generated electrical energy is read by the gate driver IC 6 and output as an image signal by the read IC 87. The output image signal is stored in the memory unit 31 using a rewritable read-only memory (for example, a flash memory) or the like. The operation of the radiation image detector 22 is controlled by the control circuit 30, and the operation is switched by the operation unit 32.
表示部３３は、画像の撮影準備が完了したことと、メモリ部３１に所定量の画像信号が書き込まれたことを示すものであり、また電源部３４は、イメージセンサ２０を駆動して画像信号を得るために必要とされる電力を供給するものであり、コネクタ３５は、放射線画像検出器２２と画像処理部５１間で通信を行うためのものである。筐体４０の内部やゲートドライバＩＣ６、読み出しＩＣ８７、制御回路３０、メモリ部３１等は、図示していない放射線遮蔽部材で覆われている。放射線遮蔽部材により筐体４０の内部で放射線の散乱、各回路へ放射線照射が防止される。 The display unit 33 indicates that image preparation has been completed and that a predetermined amount of image signal has been written in the memory unit 31. The power supply unit 34 drives the image sensor 20 to output the image signal. The connector 35 is used to perform communication between the radiation image detector 22 and the image processing unit 51. The inside of the housing 40, the gate driver IC 6, the reading IC 87, the control circuit 30, the memory unit 31, and the like are covered with a radiation shielding member (not shown). The radiation shielding member prevents scattering of radiation inside the housing 40 and irradiation of radiation to each circuit.
また筐体４０としては、外部からの衝撃に耐え、かつ質量ができるだけ軽い素材、例えば、アルミニウムあるいはその合金であることが好ましい。筐体４０の放射線入射面側は、放射線を透過し易い非金属例えばカーボン繊維などを用いて構成する。また、放射線入射面とは逆である背面側においては、放射線が放射線画像検出器２２を透過してしまうことを防ぐ目的、あるいは放射線画像検出器２２を構成する素材が放射線を吸収することで生ずる２次放射線からの影響を防ぐために、放射線を効果的に吸収する材料、例えば鉛板などを用いることは好ましい実施態様である。 The housing 40 is preferably made of a material that can withstand external impacts and has the smallest possible mass, such as aluminum or an alloy thereof. The radiation incident surface side of the housing 40 is configured using a non-metal that easily transmits radiation, such as carbon fiber. Further, on the back side opposite to the radiation incident surface, it is generated for the purpose of preventing the radiation from being transmitted through the radiation image detector 22 or by the material constituting the radiation image detector 22 absorbing the radiation. In order to prevent the influence from secondary radiation, it is a preferred embodiment to use a material that effectively absorbs radiation, such as a lead plate.
次に、図３を用いてイメージセンサ２０の回路動作について説明する。 Next, the circuit operation of the image sensor 20 will be described with reference to FIG.
図３（ａ）において、８１は光電変換素子、８２は読み出し用のＴＦＴであり、読み出し用のＴＦＴ８２のソースはソースバス４ａ，４ｂ，・・・４ｃへ接続され、ドレインは光電変換素子８１のカソードに接続され、ゲートはゲートバス３ａ，３ｂ，・・・３ｃへ接続されている。光電変換素子８１のアノードはバイアス線５に接続され、バイアス線５はバイアス電源８に接続され、負のバイアス電圧が印加されている。ゲートバス３ａ，３ｂ，・・・３ｃは、それぞれゲートドライバＩＣ６の出力端子Ｇ1，Ｇ2，・・・ＧNに接続され、ソースバス４ａ，４ｂ，・・・４ｃは、それぞれ読み出しＩＣ８７の出力端子Ｓ1，Ｓ2，・・・ＳMに接続されている。このイメージセンサ２０は、光電変換素子８１および読み出し用のＴＦＴ８２のそれぞれ１個の組み合わせで１つの画素を形成し、合わせてＮ行×Ｍ列の画素を有している。3A, 81 is a photoelectric conversion element, 82 is a readout TFT, the source of the readout TFT 82 is connected to the source buses 4a, 4b,... 4c, and the drain of the photoelectric conversion element 81. Connected to the cathode, the gate is connected to the gate buses 3a, 3b,... 3c. The anode of the photoelectric conversion element 81 is connected to the bias line 5, the bias line 5 is connected to the bias power supply 8, and a negative bias voltage is applied. Gate bus 3a, 3b, · · · 3c, the output terminal G 1, G 2 each gate driver IC 6, is connected to the · · · G N, source bus 4a, 4b, · · · 4c are respectively read IC87 Connected to the output terminals S 1 , S 2 ,... S M. In the image sensor 20, one pixel is formed by one combination of the photoelectric conversion element 81 and the readout TFT 82, and a total of N rows × M columns of pixels is formed.
図３には図示せぬシンチレータ層１３１は、放射線を変換した可視光がこれらの各画素に入射するように配設されている。シンチレータ層１３１については後に詳しく説明する。 The scintillator layer 131 (not shown in FIG. 3) is arranged so that visible light converted from radiation enters each of these pixels. The scintillator layer 131 will be described in detail later.
ゲートドライバＩＣ６はその出力端子Ｇ1，Ｇ2，・・・ＧNにゲートバス３ａ，３ｂ，・・・３ｃが接続されており、正の電圧を順に出力しゲートバス３ａ，３ｂ，・・・３ｃを走査する。読み出しＩＣ８７はその出力端子Ｓ1，Ｓ2，・・・ＳMにソースバス４ａ，４ｂ，・・・４ｃが接続されており、正の電圧を出力する。また、読み出しＩＣ８７の出力端子Ｓ1，Ｓ2，・・・ＳMには、それぞれ電荷−電圧変換回路を備えており、ソースバス４ａ，４ｂ，・・・４ｃに流れ出した電荷の量を電圧に変換する機能を有している。An output terminal G 1 gate driver IC6 is, G 2, ··· G N to the gate bus 3a, 3b, · · · 3c are connected to output a positive voltage to forward gate bus 3a, 3b, · · Scan 3c. Reading IC87 its output terminal S 1, S 2, ··· S M to the source bus 4a, 4b, and · · · 4c is connected, outputs a positive voltage. Further, the output terminals S 1 , S 2 ,... S M of the readout IC 87 are each provided with a charge-voltage conversion circuit, and the amount of charge flowing out to the source buses 4a, 4b,. It has the function to convert to.
放射線画像検出器２２の動作を、図３（ａ）に示す回路図、及び図３（ｂ）に示すタイミングチャートを用いて説明する。図３（ｂ）で１１，１２，１３は、それぞれゲートドライバＩＣ６の出力端子Ｇ1，Ｇ2，・・・ＧNの電圧を示す。ゲートバス３ａ，３ｂ，・・・３ｃがハイになるとそのゲート線に接続されているＴＦＴ８２がすべてオン状態となる。The operation of the radiation image detector 22 will be described with reference to a circuit diagram shown in FIG. 3A and a timing chart shown in FIG. In FIG. 3 (b) 11, 12, 13, the output terminal G 1, G 2 each gate driver IC 6, showing the voltage · · · G N. When the gate buses 3a, 3b,... 3c become high, all the TFTs 82 connected to the gate lines are turned on.
このとき、読み出しＩＣ８７の出力端子Ｓ1，Ｓ2，・・・ＳMからは正の電圧がソースバス４ａ，４ｂ，・・・４ｃに出力されているため、オンしたＴＦＴ８２に接続されている光電変換素子８１は逆バイアスされ、光電変換素子８１の容量には電荷が充電される。At this time, since positive voltages are output from the output terminals S 1 , S 2 ,... S M of the readout IC 87 to the source buses 4a, 4b,. The photoelectric conversion element 81 is reverse-biased, and the capacitance of the photoelectric conversion element 81 is charged.
このとき光電変換素子８１に流れ込む充電電流、すなわち読み出しＩＣ８７の出力端子Ｓ1，Ｓ2，・・・ＳMからソースバス４ａ，４ｂ，・・・４ｃに流れ込む電荷は、読み出しＩＣ８７で電荷−電圧変換され、電圧として読み出される。ゲートバス３ａ，３ｂ，・・・３ｃがロウになると、そのゲート線に接続されているＴＦＴ８２はすべてオフし、そのＴＦＴ８２に接続されている光電変換素子８１の充電された電荷は保持される。The charging current flowing into the photoelectric conversion element 81 at this time, that is, the output terminal S 1, S 2 read IC87, ··· S M from the source bus 4a, 4b, charges flowing into the · · · 4c, the charge in the read IC87 - Voltage Converted and read as voltage. When the gate buses 3a, 3b,... 3c become low, all the TFTs 82 connected to the gate lines are turned off, and the charged electric charges of the photoelectric conversion elements 81 connected to the TFTs 82 are retained.
図３（ｂ）で初期化走査と示された期間は、放射線像の撮影に備えて、すべての光電変換素子８１を充電するための走査期間である。図３（ｂ）の１４は放射線の曝射を示し、ハイになっている期間が放射線の曝射が行われている期間を示す。図３（ｂ）に示すように、放射線の曝射は、放射線画像検出器２２の初期化走査の終了後に行われる。放射線が曝射されると、放射線の照射を受けたシンチレータ１３１が蛍光を発し、この蛍光を受光した光電変換素子８１は、その中で電子−ホール対が発生し、充電されていた電荷を放電する。このため、光電変換素子８１に充電されていた電荷は、受光量に応じて発生した電子−ホール対の分だけ減少する。 A period indicated as initialization scanning in FIG. 3B is a scanning period for charging all the photoelectric conversion elements 81 in preparation for radiographic imaging. In FIG. 3B, reference numeral 14 indicates radiation exposure, and a high period indicates a period during which radiation exposure is performed. As shown in FIG. 3B, the radiation exposure is performed after the initialization scan of the radiation image detector 22 is completed. When the radiation is exposed, the scintillator 131 that has received the radiation emits fluorescence, and the photoelectric conversion element 81 that has received the fluorescence generates electron-hole pairs therein, and discharges the charged charges. To do. For this reason, the charge charged in the photoelectric conversion element 81 decreases by the amount of electron-hole pairs generated according to the amount of received light.
放射線の曝射に続いて、図３（ｂ）に示す読み出し走査が行われる。読み出し走査の時、読み出しＩＣ８７から読み出される電荷−電圧変換された電圧は、放射線曝射の時、光電変換素子８１から放電により消滅した電荷に相当する。従って、蛍光体層に入射した放射線による画像が、電圧として二次元的に読み出すことができる。 Subsequent to the radiation exposure, readout scanning shown in FIG. 3B is performed. The charge-voltage converted voltage read from the read IC 87 during the reading scan corresponds to the charge that disappears from the photoelectric conversion element 81 due to the discharge during the radiation exposure. Therefore, an image by radiation incident on the phosphor layer can be read out two-dimensionally as a voltage.
図３（ｂ）のＴｉは積分期間を示しており、シンチレータ１３１から発生した可視光による電子−ホール対がこの期間において光電変換素子８１で積分される。従って、積分期間Ｔｉは、放射線の曝射期間および蛍光体層の発光期間を含むようにするのが好ましい。 Ti in FIG. 3B indicates an integration period, and electron-hole pairs generated by visible light generated from the scintillator 131 are integrated by the photoelectric conversion element 81 during this period. Therefore, it is preferable that the integration period Ti includes a radiation exposure period and a phosphor layer emission period.
次に、図４を用いて本発明の実施形態に係わるイメージセンサ２０の製造工程について順を追って説明する。なお、図１と同じ工程には同番号を付し、説明を省略する。 Next, the manufacturing process of the image sensor 20 according to the embodiment of the present invention will be described in order with reference to FIG. In addition, the same number is attached | subjected to the process same as FIG. 1, and description is abbreviate | omitted.
図４（ａ）〜図４（ｃ）は、支持基板１の２画素を形成する部分の断面図である。本実施形態のイメージセンサ２０では、支持基板１の上にシンチレータ１３１を形成し、さらにその上に図１で説明した光学素子８１とＴＦＴ８２を形成している。 4A to 4C are cross-sectional views of a portion of the support substrate 1 where two pixels are formed. In the image sensor 20 of this embodiment, the scintillator 131 is formed on the support substrate 1, and the optical element 81 and the TFT 82 described with reference to FIG. 1 are further formed thereon.
本発明に係るイメージセンサ２０の製造方法の実施形態として、次の工程を説明する。図１で説明した工程Ｓ１〜Ｓ５については同じ工程番号を付し、説明を省略する。
Ｐ１・・・・・シンチレータ１３１を形成する工程。
Ｐ２・・・・・保護膜１３３を形成する工程。
Ｓ１・・・・・透明電極１００を形成する工程。
Ｐ３・・・・・ゲート電極２、ソース線８ｂを形成する工程。
Ｐ４・・・・・ゲート絶縁層７を形成する工程。
Ｐ５・・・・・ソース電極８ａ、ドレイン電極９を形成する工程。
Ｐ６・・・・・活性層５を形成する工程。
Ｐ７・・・・・パッシベーション層１１２を形成する工程。
Ｓ２・・・・・正孔輸送層１０４を形成する工程。
Ｓ３・・・・・光電変換層１０１を形成する工程。As an embodiment of the method for manufacturing the image sensor 20 according to the present invention, the following steps will be described. Steps S1 to S5 described in FIG. 1 are denoted by the same step numbers and description thereof is omitted.
P1 Step for forming the scintillator 131.
P2 Step for forming the protective film 133.
S1... The step of forming the transparent electrode 100.
P3 Step for forming the gate electrode 2 and the source line 8b.
P4... The step of forming the gate insulating layer 7.
P5 Step for forming the source electrode 8a and the drain electrode 9.
P6 Step for forming the active layer 5.
P7 Step for forming the passivation layer 112.
S2 Step for forming the hole transport layer 104.
S3: A step of forming the photoelectric conversion layer 101.
Ｓ３−１・・・溶媒に有機半導体材料を溶解または分散させ有機半導体溶液を作製する第１工程。 S3-1: A first step of preparing an organic semiconductor solution by dissolving or dispersing an organic semiconductor material in a solvent.
Ｓ３−２・・・有機半導体溶液を塗布する第２工程。 S3-2: Second step of applying an organic semiconductor solution.
Ｓ３−３・・・塗布した有機半導体溶液を一定時間加熱して乾燥させる第３工程。
Ｓ４・・・・・対電極１０２を形成する工程。
Ｓ５・・・・・アニール処理工程。
Ｐ８・・・・保護膜１０３を形成する工程。S3-3 A third step of drying the applied organic semiconductor solution by heating for a certain time.
S4... The step of forming the counter electrode 102.
S5: Annealing process.
P8... Step of forming the protective film 103.
本実施形態に用いる支持基板は、放射線を透過する材料であれば特に限定されない。例えば低融点ガラスやＰＥＮ、ＰＥＳ、ＰＣ、ＴＡＣなどのフィルム基板を用いることができるが、後に形成するＴＦＴなどに不要な光が入射しないようガラスなど透明な材料は着色して光を透過しないようにすることが望ましい。 The support substrate used in the present embodiment is not particularly limited as long as it is a material that transmits radiation. For example, a low-melting glass or a film substrate such as PEN, PES, PC, or TAC can be used, but a transparent material such as glass is colored so as not to transmit light so that unnecessary light does not enter a TFT to be formed later. It is desirable to make it.
以下、各工程について順に説明する。 Hereinafter, each process is demonstrated in order.
Ｐ１・・・・・シンチレータ１３１を形成する工程。 P1 Step for forming the scintillator 131.
図４（ａ）のように、シンチレータ１３１を支持基板１の面に例えばＣｓＩを材料として蒸着法を用いて形成する。シンチレータ１３１には第１の実施形態と同様にその他の材料を用いることができる。 As shown in FIG. 4A, the scintillator 131 is formed on the surface of the supporting substrate 1 by using, for example, CsI as a material by vapor deposition. Other materials can be used for the scintillator 131 as in the first embodiment.
Ｐ２・・・・・保護膜１３３を形成する工程。 P2 Step for forming the protective film 133.
シンチレータ１３１の上層およびシンチレータ１３１の層の側面を覆うように保護膜１３３を形成する。保護膜１３３は例えばＳｉＮｘをＣＶＤ法により形成する。 A protective film 133 is formed so as to cover the upper layer of the scintillator 131 and the side surface of the layer of the scintillator 131. The protective film 133 is formed by, for example, SiNx by a CVD method.
Ｓ１・・・・・透明電極１００を形成する工程。 S1... The step of forming the transparent electrode 100.
透明電極１００を支持基板１の上に例えばスパッタ法を用いて形成する。透明電極１００の材料は図１で説明した実施形態と同様である。 The transparent electrode 100 is formed on the support substrate 1 by using, for example, a sputtering method. The material of the transparent electrode 100 is the same as that of the embodiment described in FIG.
Ｐ３・・・・・ゲート電極２、ソース線８ｂを形成する工程。 P3 Step for forming the gate electrode 2 and the source line 8b.
支持基板１の上にゲート電極２、ソース線８ｂを形成する。ゲート電極２、ソース線８ｂには各種金属薄膜を利用できる。例えばＡｌ、Ｃｒ、Ａｕ、Ａｇ等の低抵抗金属材料やこれら金属の積層構造、また、金属薄膜の耐熱性向上、支持基板への密着性向上、欠陥防止のために他の材料のドーピングしたものを用いることができる。また、ＩＴＯ、ＩＺＯ、ＳｎＯ、ＺｎＯなどの透明電極を用いることもできる。製造方法は、目的の形状にパターニングすることのできるマスク蒸着法、フォトリソグラフィー法、各種印刷法が利用できる。 A gate electrode 2 and a source line 8 b are formed on the support substrate 1. Various metal thin films can be used for the gate electrode 2 and the source line 8b. For example, low-resistance metal materials such as Al, Cr, Au, Ag, etc., and laminated structures of these metals, and those doped with other materials to improve the heat resistance of metal thin films, improve adhesion to the support substrate, and prevent defects Can be used. A transparent electrode such as ITO, IZO, SnO, or ZnO can also be used. As a manufacturing method, a mask vapor deposition method, a photolithography method, and various printing methods that can be patterned into a target shape can be used.
Ｐ４・・・・・ゲート絶縁層７を形成する工程。 P4... The step of forming the gate insulating layer 7.
図４（ｂ）に示すように、ゲート絶縁層７を形成する。 As shown in FIG. 4B, the gate insulating layer 7 is formed.
ゲート絶縁層７は、例えばスピンコート法で形成する。ゲート絶縁層７としては、特にフレキシブル性を確保するためには、アクリル系、ウレタン系、エポキシ系、ポリイミド系などの樹脂が望ましい。樹脂には、熱可塑性樹脂と熱硬化性樹脂があるが、いずれも用いることができる。また、無機膜の絶縁膜を用いることもできる。 The gate insulating layer 7 is formed by, for example, a spin coat method. As the gate insulating layer 7, an acrylic resin, urethane resin, epoxy resin, polyimide resin or the like is particularly desirable in order to ensure flexibility. The resin includes a thermoplastic resin and a thermosetting resin, and any of them can be used. Alternatively, an inorganic insulating film can be used.
Ｐ５・・・・・ソース電極８ａ、ドレイン電極９を形成する工程。 P5 Step for forming the source electrode 8a and the drain electrode 9.
ゲート絶縁層７の上に、ソース電極８ａ、ドレイン電極９を形成する。ソース電極８ａ、ドレイン電極９は、例えば、金をスパッタにより成膜することにより形成する。なお、ここでは金を例示したが、特に金に材料を限定されることなく、白金、銀、銅、アルミニウム等種々の材料を用いることができる。または、塗布材料としてＰＥＤＯＴ／ＰＳＳに代表される導電性有機材料、金属ナノ粒子を分散させた塗布材料を用いることもできる。 A source electrode 8 a and a drain electrode 9 are formed on the gate insulating layer 7. The source electrode 8a and the drain electrode 9 are formed, for example, by depositing gold by sputtering. In addition, although gold was illustrated here, various materials, such as platinum, silver, copper, and aluminum, can be used without specifically limiting the material to gold. Alternatively, a conductive organic material typified by PEDOT / PSS or a coating material in which metal nanoparticles are dispersed can be used as the coating material.
Ｐ６・・・・・活性層５を形成する工程。 P6 Step for forming the active layer 5.
活性層５の材料は有機半導体材料に限定されるものではないが、印刷、塗布などの製造方法により形成できるので有機半導体材料の方が望ましい。有機半導体材料の場合もその材料について問わない。有機高分子材料はもちろんのこと、ペンタセンなどの低分子材料も使用可能である。 The material of the active layer 5 is not limited to an organic semiconductor material, but an organic semiconductor material is more preferable because it can be formed by a manufacturing method such as printing or coating. In the case of an organic semiconductor material, it does not matter about the material. Not only organic polymer materials but also low molecular materials such as pentacene can be used.
塗布できる材料の代表例としては、ポリ（３−ヘキシルチオフェン）などのポリチオフェン類、チオフェンの６量体を基本に側鎖を有するオリゴチオフェンなどの芳香族オリゴマー類、ペンタセンに置換基を持たせ溶解性を高めたペンタセン類、フルオレンとバイチオフェンとの共重合体（Ｆ８Ｔ２）、ポリチエニレンビニレンまたはフタロシアニンなどのいかなる可溶性の半導体でも使用できる。 Typical examples of materials that can be applied include polythiophenes such as poly (3-hexylthiophene), aromatic oligomers such as oligothiophene having a side chain based on the hexamer of thiophene, and pentacene with substituents and dissolution. Any soluble semiconductor can be used, such as pentacenes with enhanced properties, a copolymer of fluorene and bithiophene (F8T2), polythienylene vinylene or phthalocyanine.
これまでのＳ３〜Ｓ６の工程で、ゲート電極２、ゲート絶縁層７、ソース電極８ａ、ドレイン電極９、活性層５から構成されるＴＦＴ８２を作製できた。 The TFT 82 composed of the gate electrode 2, the gate insulating layer 7, the source electrode 8 a, the drain electrode 9, and the active layer 5 can be manufactured through the steps S 3 to S 6 thus far.
Ｐ７・・・・・パッシベーション層１１２を形成する工程。 P7 Step for forming the passivation layer 112.
パッシベーション層１１２は、例えばポリイミドをスピンコート法により形成する。 The passivation layer 112 is formed by, for example, polyimide by spin coating.
Ｓ２・・・・・正孔輸送層１０４を形成する工程。 S2 Step for forming the hole transport layer 104.
例えば、ＰＥＤＯＴ／ＰＳＳ（ポリ（３，４−エチレンジオキシチオフェン）−ポリスチレンスルホネート）を材料としてスピンコート法を用いて支持基板１上に形成する。その後、オーブンで加熱し乾燥させる。 For example, PEDOT / PSS (poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate) is used as a material and is formed on the support substrate 1 using a spin coat method. Thereafter, it is heated in an oven and dried.
Ｓ３・・・・・光電変換層１０１を形成する工程。 S3: A step of forming the photoelectric conversion layer 101.
例えば、電子受容性有機材料と電子供与性有機材料とを有機溶媒に溶解した溶液を工程Ｓ２までの処理を終えた支持基板１の所望の領域に、スピンコート法などを用いて塗布し、乾燥させてバルクヘテロ型の光電変換層１０１を形成する。 For example, a solution in which an electron-accepting organic material and an electron-donating organic material are dissolved in an organic solvent is applied to a desired region of the support substrate 1 that has been subjected to the process up to step S2 using a spin coating method or the like, and then dried. Thus, the bulk hetero photoelectric conversion layer 101 is formed.
Ｓ３−１・・・溶媒に有機半導体材料を溶解または分散させ有機半導体溶液を作製する第１工程。 S3-1: A first step of preparing an organic semiconductor solution by dissolving or dispersing an organic semiconductor material in a solvent.
Ｓ３−２・・・有機半導体溶液を塗布する第２工程。 S3-2: Second step of applying an organic semiconductor solution.
Ｓ３−３・・・塗布した有機半導体溶液を一定時間加熱して乾燥させる第３工程。 S3-3 A third step of drying the applied organic semiconductor solution by heating for a certain time.
これらの工程Ｓ３−１、Ｓ３−２、Ｓ３−３のうち少なくとも１つの工程は、後の工程で形成する対電極１０２の光電変換層１０１と接する面に電極酸化膜１０５が形成されるように、大気下など酸素を含有する雰囲気下で行うことが望ましい。 At least one of these steps S3-1, S3-2, and S3-3 is performed so that the electrode oxide film 105 is formed on the surface of the counter electrode 102 that is to be formed in a later step and in contact with the photoelectric conversion layer 101. It is desirable to perform in an atmosphere containing oxygen, such as in the air.
Ｓ４・・・・対電極１０２を形成する工程。 S4... Step of forming the counter electrode 102.
光電変換層１０１の上に対電極１０２を形成する。対電極１０２は、メタルマスクを用いて、例えばＡｌ、Ａｇ、Ａｕ、Ｐｔなどの金属材料を蒸着して形成する。 A counter electrode 102 is formed over the photoelectric conversion layer 101. The counter electrode 102 is formed by evaporating a metal material such as Al, Ag, Au, or Pt using a metal mask.
Ｓ５・・・・アニール処理工程。 S5... Annealing process.
次に、大気下など酸素を含有する雰囲気下で、Ｓ４までの工程を終えた支持基板１を５０℃〜１５０℃の温度範囲で３０分加熱し、アニール処理を行う。 Next, in an atmosphere containing oxygen such as the air, the support substrate 1 that has completed the steps up to S4 is heated in a temperature range of 50 ° C. to 150 ° C. for 30 minutes to perform an annealing treatment.
これまでの工程で透明電極１００、正孔輸送層１０４、光電変換層１０１、電極酸化膜１０５、対電極１０２から構成される光電変換素子８１が作製できた。 The photoelectric conversion element 81 including the transparent electrode 100, the hole transport layer 104, the photoelectric conversion layer 101, the electrode oxide film 105, and the counter electrode 102 can be manufactured through the steps so far.
Ｐ８・・・・保護膜１０３を形成する工程。 P8... Step of forming the protective film 103.
対電極１０２の上層に保護膜１０３として、例えばポリイミドをスピンコート法で形成する。 For example, polyimide is formed as a protective film 103 on the counter electrode 102 by a spin coating method.
以上でイメージセンサ２０の製造工程は終了である。 This completes the manufacturing process of the image sensor 20.
このように、対電極１０２と光電変換層１０１の間に電極酸化膜１０５を有する光電変換素子８１をマトリクス状に複数形成したイメージセンサ２０を作製することができる。 Thus, the image sensor 20 in which a plurality of photoelectric conversion elements 81 each including the electrode oxide film 105 between the counter electrode 102 and the photoelectric conversion layer 101 are formed in a matrix can be manufactured.
以下、本発明の効果を確認するために行った実施例について説明するが、本発明はこれらに限定されるものではない。 Hereinafter, although the Example performed in order to confirm the effect of this invention is described, this invention is not limited to these.
［実施例１］
実施例１では、図１（４−ｂ）に示す断面の光電変換素子８１を、図１（４−ａ）のように支持基板１上に６つ作製し、それぞれの性能を確認した。また、アニール処理工程Ｓ５で加熱温度による性能の変化を確認するため、７つの支持基板１の上に加熱温度の設定だけを変えて光電変換素子８１を作製した。設定した加熱温度は２５℃、４０℃、５０℃、１００℃、１５０℃、１６０℃、１７０℃である。[Example 1]
In Example 1, six photoelectric conversion elements 81 having the cross section shown in FIG. 1 (4-b) were produced on the support substrate 1 as shown in FIG. 1 (4-a), and the performances of each were confirmed. In addition, in order to confirm the change in performance due to the heating temperature in the annealing treatment step S5, only the setting of the heating temperature was changed on the seven support substrates 1 to produce the photoelectric conversion element 81. The set heating temperatures are 25 ° C, 40 ° C, 50 ° C, 100 ° C, 150 ° C, 160 ° C, and 170 ° C.
以下、試作した各工程について順に説明する。 Hereinafter, each trial process will be described in order.
Ｓ１・・・・・透明電極１００を形成する工程。 S1... The step of forming the transparent electrode 100.
支持基板１の上に、ＩＴＯ膜をスパッタにより２００ｎｍの厚みで形成した後、フォトリソグラフィー法を用いてパターニングを行った。支持基板１には厚さ０．７ｍｍのガラスを用いた。１つの光電変換素子８１が透明電極１００から受光する部分の面積が５×５ｍｍになるようにパターニングした。 An ITO film having a thickness of 200 nm was formed on the support substrate 1 by sputtering, and then patterned using a photolithography method. For the support substrate 1, glass having a thickness of 0.7 mm was used. Patterning was performed so that the area of a portion where one photoelectric conversion element 81 received light from the transparent electrode 100 was 5 × 5 mm.
Ｓ２・・・・・正孔輸送層１０４を形成する工程。 S2 Step for forming the hole transport layer 104.
ＰＥＤＯＴ／ＰＳＳ（スタルクヴィテック社製：ＢａｙｔｒｏｎＰ）をスピンコート（回転数１０００ｒｐｍ、フィルタ径：１．２μｍ）で塗布し、支持基板１上に形成した。その後、オーブンで１００℃で３０分加熱した。正孔輸送層１０４の厚みは９０ｎｍである。 PEDOT / PSS (manufactured by Starck Vitech: BaytronP) was applied by spin coating (rotation speed: 1000 rpm, filter diameter: 1.2 μm) and formed on the support substrate 1. Thereafter, it was heated in an oven at 100 ° C. for 30 minutes. The thickness of the hole transport layer 104 is 90 nm.
Ｓ３・・・・・光電変換層１０１を形成する工程。 S3: A step of forming the photoelectric conversion layer 101.
Ｓ３−１・・・溶媒に有機半導体材料を溶解または分散させ有機半導体溶液を作製する第１工程。 S3-1: A first step of preparing an organic semiconductor solution by dissolving or dispersing an organic semiconductor material in a solvent.
大気中においてＰＣＢＭとＰ３ＨＴを質量比７：３の割合でクロロベンゼン溶液に溶解または分散させ有機半導体溶液を作製した。 PCBM and P3HT were dissolved or dispersed in a chlorobenzene solution at a mass ratio of 7: 3 in the air to prepare an organic semiconductor solution.
Ｓ３−２・・・有機半導体溶液を塗布する第２工程。 S3-2: Second step of applying an organic semiconductor solution.
大気中でスピンコート（回転数１５００ｒｐｍ、フィルタ径：０．８μｍ）を用いてＰＣＢＭとＰ３ＨＴの溶液を正孔輸送層１０４の上に塗布した。 A PCBM and P3HT solution was applied onto the hole transport layer 104 by spin coating (rotation speed: 1500 rpm, filter diameter: 0.8 μm) in the air.
Ｓ３−３・・・塗布した有機半導体溶液を一定時間加熱して乾燥させる第３工程。 S3-3 A third step of drying the applied organic semiconductor solution by heating for a certain time.
大気中で支持基板１を１００℃のオーブンで３０分加熱して有機半導体溶液を乾燥させ７０ｎｍの光電変換層１０１を形成した。 The support substrate 1 was heated in an oven at 100 ° C. for 30 minutes in the air to dry the organic semiconductor solution, thereby forming a 70 nm photoelectric conversion layer 101.
Ｓ４・・・・対電極１０２を形成する工程。 S4... Step of forming the counter electrode 102.
メタルマスクを用いてＡｌを加熱蒸着し、厚さ５０ｎｍの所望のパターン形状になるまで蒸着を行った。 Al was heated and vapor-deposited using a metal mask, and was vapor-deposited until a desired pattern shape with a thickness of 50 nm was obtained.
Ｓ５・・・・アニール処理工程。 S5... Annealing process.
大気中で支持基板１を１００℃の温度で３０分加熱し、アニール処理を行った。 The support substrate 1 was heated at a temperature of 100 ° C. for 30 minutes in the atmosphere to perform an annealing process.
［実施例２］
実施例２では、工程Ｓ３−３の塗布した有機半導体溶液を一定時間加熱して乾燥させる第３工程と工程Ｓ５のアニール処理工程を窒素雰囲気下で行った。また、工程Ｓ５のアニール処理工程で設定した加熱温度は１００℃だけである。[Example 2]
In Example 2, the third step of drying the organic semiconductor solution applied in Step S3-3 for a predetermined time and the annealing treatment step of Step S5 were performed in a nitrogen atmosphere. Further, the heating temperature set in the annealing process in step S5 is only 100 ° C.
それ以外の工程は実施例１と全く同じ条件で光電変換素子８１を作製した。 Other processes were the same as in Example 1, and a photoelectric conversion element 81 was produced.
［実施例３］
実施例３では、工程Ｓ３−１の溶媒に有機半導体材料を溶解または分散させ有機半導体溶液を作製する第１工程において、次の材料を用いる。すなわち、電子受容性有機材料としてＰＣＢＩＢ（Ｐｈｅｎｙ Ｃ６１−ｂｕｔｙｒｉｃ ａｃｉｄ ｉ−ｂｕｔｙｌ ｅｓｔｅｒ：フロンティアカーボン社製）、電子供与性有機材料としてＭＥＨ−ＰＰＶ（ｐｏｌｙ［２−ｍｅｔｈｏｘｙ−５−（２′−ｅｔｈｙｌｈｅｘｙｌｏｘｙ）−ｐ−ｐｈｅｎｙｌｅｎｅ ｖｉｎｙｌｅｎｅ］：アルドリッチ社製）を用いた。[Example 3]
In Example 3, the following materials are used in the first step of preparing an organic semiconductor solution by dissolving or dispersing the organic semiconductor material in the solvent in Step S3-1. Specifically, PCBIB (Pheny C61-butyric acid i-butyl ester: manufactured by Frontier Carbon Co.) as an electron-accepting organic material, and MEH-PPV (poly [2-methoxy-5- (2′-ethylhexyloxy)) as an electron-donating organic material. -P-phenylene vinylene] (manufactured by Aldrich).
また、工程Ｓ５のアニール処理工程で設定した加熱温度は１００℃だけである。それ以外の工程は実施例１と全く同じ条件で光電変換素子８１を作製した。 Further, the heating temperature set in the annealing process in step S5 is only 100 ° C. Other processes were the same as in Example 1, and a photoelectric conversion element 81 was produced.
［比較例１］
比較例１では、工程Ｓ５の効果を確認するため工程Ｓ５のアニール処理工程を省いた。[Comparative Example 1]
In Comparative Example 1, the annealing process step of step S5 was omitted in order to confirm the effect of step S5.
それ以外の工程は実施例１と全く同じ条件で光電変換素子８１を作製した。 Other processes were the same as in Example 1, and a photoelectric conversion element 81 was produced.
［比較例２］
比較例２では、工程Ｓ３−１の溶媒に有機半導体材料を溶解または分散させ有機半導体溶液を作製する第１工程、工程Ｓ３−２の有機半導体溶液を塗布する第２工程、工程Ｓ３−３・・・塗布した有機半導体溶液を一定時間加熱して乾燥させる第３工程と、工程Ｓ５のアニール処理工程を窒素雰囲気下で行った。[Comparative Example 2]
In Comparative Example 2, the first step of preparing an organic semiconductor solution by dissolving or dispersing the organic semiconductor material in the solvent of Step S3-1, the second step of applying the organic semiconductor solution of Step S3-2, Step S3-3, .. The third step of drying the applied organic semiconductor solution for a certain period of time and the annealing treatment step of step S5 were performed in a nitrogen atmosphere.
また、工程Ｓ５のアニール処理工程で設定した加熱温度は１００℃だけである。それ以外の工程は実施例１と全く同じ条件で光電変換素子８１を作製した。 Further, the heating temperature set in the annealing process in step S5 is only 100 ° C. Other processes were the same as in Example 1, and a photoelectric conversion element 81 was produced.
［測定条件］
このようにして作製した実施例１〜３、比較例１、２の光電変換素子８１を以下の条件で測定した。[Measurement condition]
The photoelectric conversion elements 81 of Examples 1 to 3 and Comparative Examples 1 and 2 thus manufactured were measured under the following conditions.
支持基板１の上に形成された６つの光電変換素子８１の光照射時の電流（光電流）と光未照射時の電流（暗電流）を測定し、平均値を算出した。光電流と暗電流は図１（４−ａ）に点線で示す１０２ａの部分を測定した。光電変換素子８１に印加する電圧は、対電極１０５の電位を０Ｖとし透明電極１００の電圧を−２Ｖに設定した。 The current (photocurrent) at the time of light irradiation of the six photoelectric conversion elements 81 formed on the support substrate 1 and the current (dark current) at the time of no light irradiation were measured, and an average value was calculated. The photocurrent and dark current were measured at 102a indicated by a dotted line in FIG. The voltage applied to the photoelectric conversion element 81 was set such that the potential of the counter electrode 105 was 0V and the voltage of the transparent electrode 100 was set to -2V.
光電流を測定する条件は次の通りである。 The conditions for measuring the photocurrent are as follows.
光源：主波長５５０ｎｍのＬＥＤを用いた。 Light source: An LED having a dominant wavelength of 550 nm was used.
光量：１．６９×１０-4［Ｗ／ｃｍ2］
光入射面は図１（４−ｂ）に矢印Ｌで示す面である。Light amount: 1.69 × 10 −4 [W / cm 2 ]
The light incident surface is a surface indicated by an arrow L in FIG.
電極酸化膜１０５の厚みは、作製した実施例１〜３、比較例１、２の光電変換素子８１の断面を電界放射透過電子顕微鏡で観察し、厚みを測定した。 The thickness of the electrode oxide film 105 was measured by observing the cross sections of the produced photoelectric conversion elements 81 of Examples 1 to 3 and Comparative Examples 1 and 2 with a field emission transmission electron microscope.
［実験結果］ [Experimental result]
表１は実施例１〜３、比較例１、２の実験条件の比較表、表２は実験結果の比較表である。表２からわかるように、実施例１〜３で作製した光電変換素子８１には電極酸化膜１０５が３〜８ｎｍの厚みで形成されている。一方、比較例１、２には測定できるような厚みの電極酸化膜１０５が形成されていない。電界放射透過電子顕微鏡による厚みの測定限界は１ｎｍ未満であり、比較例１、２の厚みは１ｎｍ未満である。 Table 1 is a comparison table of experimental conditions of Examples 1 to 3 and Comparative Examples 1 and 2, and Table 2 is a comparison table of experimental results. As can be seen from Table 2, an electrode oxide film 105 having a thickness of 3 to 8 nm is formed on the photoelectric conversion element 81 produced in Examples 1 to 3. On the other hand, in Comparative Examples 1 and 2, the electrode oxide film 105 having a thickness that can be measured is not formed. The thickness measurement limit by a field emission transmission electron microscope is less than 1 nm, and the thicknesses of Comparative Examples 1 and 2 are less than 1 nm.
実施例１の暗電流は０．０５（μＡ／ｃｍ2）であり、工程Ｓ５のアニール処理を行わない比較例１の暗電流６．２（μＡ／ｃｍ2）と比べて大幅に低減されている。また、工程Ｓ５のアニール処理を行うが、工程Ｓ３−１、Ｓ３−２、Ｓ３−３、工程Ｓ５を窒素雰囲気下で行う比較例２の暗電流は２．３（μＡ／ｃｍ2）であり、比較例２との比較でも実施例１の暗電流は大幅に改善されている。なお、光電流は実施例１〜３、比較例１、２とも光電流は２６〜２９（μＡ／ｃｍ2）の範囲であり、光電変換素子８１として十分な光電流が得られた。The dark current in Example 1 is 0.05 (μA / cm 2 ), which is greatly reduced compared to the dark current 6.2 (μA / cm 2 ) in Comparative Example 1 in which the annealing process in Step S5 is not performed. Yes. Further, although the annealing process of step S5 is performed, the dark current of Comparative Example 2 in which steps S3-1, S3-2, S3-3, and step S5 are performed in a nitrogen atmosphere is 2.3 (μA / cm 2 ). In comparison with Comparative Example 2, the dark current of Example 1 is greatly improved. The photocurrents in Examples 1 to 3 and Comparative Examples 1 and 2 were in the range of 26 to 29 (μA / cm 2 ), and a sufficient photocurrent for the photoelectric conversion element 81 was obtained.
また、実施例２では工程Ｓ３−３と工程Ｓ５を窒素雰囲気中で行っているが、工程Ｓ３−１、工程Ｓ３−２を大気中で行っているので、実施例１と同等の性能が得られることが分かった。 In Example 2, Steps S3-3 and S5 are performed in a nitrogen atmosphere. However, since Steps S3-1 and S3-2 are performed in the air, the same performance as in Example 1 is obtained. I found out that
実施例３では電子受容性有機材料（表１ではＮと表記）としてＰＣＢＩＢ、電子供与性有機材料（表１ではＰと表記）としてＭＥＨ−ＰＰＶの混合溶液を用いて光電変換層１０１を形成しているが、実施例１と同等の性能が得られることが分かった。 In Example 3, a photoelectric conversion layer 101 is formed using a mixed solution of PCBH as an electron-accepting organic material (indicated as N in Table 1) and MEH-PPV as an electron-donating organic material (indicated as P in Table 1). However, it was found that the same performance as in Example 1 was obtained.
表３は実施例１の実験条件で工程Ｓ５のアニール処理の加熱温度を変えて作製した光電変換素子８１の比較表である。 Table 3 is a comparison table of photoelectric conversion elements 81 produced by changing the heating temperature of the annealing process in step S5 under the experimental conditions of Example 1.
加熱温度が２５℃、４０℃では形成された電極酸化膜１０５厚みは１ｎｍ未満であり、暗電流が急激に増えている。加熱温度が１６０℃、１７０℃では電極酸化膜１０５の厚みが１２ｎｍ以上になり、光電流が大きく低下している。例えば、加熱温度１００℃の場合、光電流は２７．６（μＡ／ｃｍ2）であるが、加熱温度１６０℃では光電流は１８（μＡ／ｃｍ2）であり光電流が６５％に低下している。When the heating temperature is 25 ° C. and 40 ° C., the thickness of the formed electrode oxide film 105 is less than 1 nm, and the dark current increases rapidly. When the heating temperature is 160 ° C. and 170 ° C., the thickness of the electrode oxide film 105 is 12 nm or more, and the photocurrent is greatly reduced. For example, when the heating temperature is 100 ° C., the photocurrent is 27.6 (μA / cm 2 ), but when the heating temperature is 160 ° C., the photocurrent is 18 (μA / cm 2 ), and the photocurrent decreases to 65%. ing.
加熱温度が５０℃、１００℃、１５０℃の場合は、光電流は２４〜２８（μＡ／ｃｍ2）の範囲であり、光電変換素子８１として十分な光電流が得られた。また、暗電流は加熱温度５０℃のとき０．２４（μＡ／ｃｍ2）、加熱温度１５０℃のとき０．１１（μＡ／ｃｍ2）であり、比較例１の暗電流６．２（μＡ／ｃｍ2）と比べて大幅に低減されている。加熱温度が４０℃では暗電流０．８（μＡ／ｃｍ2）であり、比較例１より暗電流は少ないが、実施例１と比べて暗電流低減の効果は少なくなっている。When the heating temperature was 50 ° C., 100 ° C., and 150 ° C., the photocurrent was in the range of 24-28 (μA / cm 2 ), and a sufficient photocurrent for the photoelectric conversion element 81 was obtained. The dark current was 0.24 (μA / cm 2 ) when the heating temperature was 50 ° C., and 0.11 (μA / cm 2 ) when the heating temperature was 150 ° C. The dark current of Comparative Example 1 was 6.2 (μA). / Cm 2 ). When the heating temperature is 40 ° C., the dark current is 0.8 (μA / cm 2 ), and the dark current is less than that of Comparative Example 1, but the effect of reducing the dark current is less than that of Example 1.
以上のように工程Ｓ５のアニール処理は５０℃〜１５０℃の温度範囲で加熱することが望ましいことが分かった。 As described above, it has been found that the annealing process in step S5 is preferably performed in a temperature range of 50 ° C to 150 ° C.
以上このように、本発明によれば、有機材料を用いながら暗電流の少ない光電変換素子、光電変換素子の製造方法、イメージセンサおよび放射線画像検出器を提供することができる。 As described above, according to the present invention, it is possible to provide a photoelectric conversion element with a small dark current while using an organic material, a method for manufacturing the photoelectric conversion element, an image sensor, and a radiation image detector.
光電変換素子の製造方法、イメージセンサおよび放射線画像検出器に関する。 The present invention relates to a method for manufacturing a photoelectric conversion element, an image sensor, and a radiation image detector.
本発明は、上記課題に鑑みてなされたものであって、有機材料を用いながら暗電流の少ない光電変換素子の製造方法、イメージセンサおよび放射線画像検出器を提供することを目的とする。 The present invention was made in view of the above problems, a method of manufacturing small have a photoelectric conversion element of the dark current while using the organic material, and an object thereof is to provide a image sensor and a radiation image detector.
上記目的は、下記の１から４のいずれか１項に記載の発明によって達成される。 The above object is achieved by the invention described in any one of 1 to 4 below.
１．光電変換素子の製造方法において、
支持基板の上に透明電極を形成する工程と、
前記透明電極の上に、溶媒に有機半導体材料を溶解または分散させた有機半導体溶液を酸素を含む雰囲気下で塗布することにより、光電変換層を形成する工程と、
前記光電変換層の上に対電極を形成する工程と、
前記支持基板を一定時間加熱するアニール処理工程と、
を備え、
前記光電変換層の上に前記対電極を形成する工程の後、前記アニール処理工程を行うことにより前記対電極の前記光電変換層と接する面に電極酸化膜を形成することを特徴とする光電変換素子の製造方法。
1. In the method for producing a photoelectric conversion element,
Forming a transparency electrode on a supporting substrate,
On the transparent electrode, a step of forming a photoelectric conversion layer by applying an organic semiconductor solution in which an organic semiconductor material is dissolved or dispersed in a solvent in an atmosphere containing oxygen ;
Forming a counter electrode on the photoelectric conversion layer;
An annealing treatment step of heating the support substrate for a predetermined time;
Equipped with a,
An electrode oxide film is formed on a surface of the counter electrode in contact with the photoelectric conversion layer by performing the annealing process after the step of forming the counter electrode on the photoelectric conversion layer. Device manufacturing method.
２．前記アニール処理工程は、５０℃〜１５０℃の温度範囲で加熱することを特徴とする前記１に記載の光電変換素子の製造方法。 2 . 2. The method for producing a photoelectric conversion element according to 1 above , wherein the annealing treatment step is performed in a temperature range of 50 ° C. to 150 ° C.
３．前記１または２に記載の製造方法によって製造された光電変換素子が、前記支持基板の上にマトリクス状に複数形成されていることを特徴とするイメージセンサ。 3 . The image sensor 1 or the photoelectric conversion element manufactured by the method according to 2, characterized in that it is more in a matrix on the supporting substrate.
４．前記３に記載のイメージセンサと、
放射線を可視光に変換する蛍光体からなるシンチレータ層と、を有し、
前記シンチレータ層は、前記イメージセンサの前記光電変換素子に前記可視光が入射するように配設されていることを特徴とする放射線画像検出器。
4). The image sensor according to 3 ;
A scintillator layer made of a phosphor that converts radiation into visible light,
The radiation image detector, wherein the scintillator layer is disposed so that the visible light is incident on the photoelectric conversion element of the image sensor.
本発明によれば、対電極は、対電極の表面に形成した電極酸化膜を挟んで光電変換層と接するので、暗電流の少ない光電変換素子の製造方法、イメージセンサおよび放射線画像検出器を提供することができる。 According to the present invention, the counter electrode, since contact with the photoelectric conversion layer across the electrode oxide film formed on the surface of the counter electrode, the method of producing less have a photoelectric conversion element of the dark current, image sensor and a radiation image detector Can be provided.
以上このように、本発明によれば、有機材料を用いながら暗電流の少ない光電変換素子の製造方法、イメージセンサおよび放射線画像検出器を提供することができる。 Above this way, according to the present invention, a method of manufacturing small it has a photoelectric conversion element of the dark current while using the organic materials, it is possible to provide an image sensor and a radiation image detector.
Claims (7)
有機半導体からなる光電変換層と、
前記光電変換層を挟んで前記透明電極と反対側に設けられた対電極と、
を有する光電変換素子において、
前記対電極は電極酸化膜を有し、該電極酸化膜を挟んで前記光電変換層と接することを特徴とする光電変換素子。A transparent electrode at least on a support substrate;
A photoelectric conversion layer made of an organic semiconductor;
A counter electrode provided on the opposite side of the transparent electrode across the photoelectric conversion layer;
In a photoelectric conversion element having
The counter electrode has an electrode oxide film, and is in contact with the photoelectric conversion layer with the electrode oxide film interposed therebetween.
前記支持基板の上に前記透明電極を形成する工程と、
前記透明電極の上に前記光電変換層を形成する工程と、
前記光電変換層の上に前記対電極を形成する工程と、
前記支持基板を一定時間加熱するアニール処理工程と、
を有し、
前記光電変換層の上に前記対電極を形成する工程の後、前記アニール処理工程を行うことにより前記電極酸化膜を形成することを特徴とする光電変換素子の製造方法。In the manufacturing method of the photoelectric conversion element which manufactures the photoelectric conversion element of Claim 1 or Claim 2,
Forming the transparent electrode on the support substrate;
Forming the photoelectric conversion layer on the transparent electrode;
Forming the counter electrode on the photoelectric conversion layer;
An annealing treatment step of heating the support substrate for a predetermined time;
Have
A method for producing a photoelectric conversion element, wherein the electrode oxide film is formed by performing the annealing treatment step after the step of forming the counter electrode on the photoelectric conversion layer.
溶媒に有機半導体材料を溶解または分散させて有機半導体溶液を作製する第１工程と、
前記有機半導体溶液を塗布する第２工程と、
塗布した前記有機半導体溶液を一定時間加熱して乾燥させる第３工程と、
を含み、
前記第１工程、前記第２工程、前記第３工程のうち少なくとも一つの工程を、酸素を含む雰囲気下で行うことを特徴とする請求の範囲第３項または第４項に記載の光電変換素子の製造方法。The step of forming the photoelectric conversion layer on the transparent electrode,
A first step of preparing an organic semiconductor solution by dissolving or dispersing an organic semiconductor material in a solvent;
A second step of applying the organic semiconductor solution;
A third step of heating and drying the applied organic semiconductor solution for a predetermined time;
Including
5. The photoelectric conversion element according to claim 3, wherein at least one of the first step, the second step, and the third step is performed in an atmosphere containing oxygen. 6. Manufacturing method.
放射線を可視光に変換する蛍光体からなるシンチレータ層と、を有し、
前記シンチレータ層は、前記イメージセンサの前記画素に前記可視光が入射するように配設されていることを特徴とする放射線画像検出器。The image sensor according to claim 6,
A scintillator layer made of a phosphor that converts radiation into visible light,
The radiation image detector, wherein the scintillator layer is disposed so that the visible light is incident on the pixels of the image sensor.
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| JP4548779B2 (en) * | 2004-01-23 | 2010-09-22 | 日本電信電話株式会社 | Organic photoelectric conversion device and organic solar cell |
| JP5040057B2 (en) * | 2004-09-03 | 2012-10-03 | コニカミノルタエムジー株式会社 | Method for manufacturing photoelectric conversion element and method for manufacturing radiation image detector |
| JP2006245073A (en) * | 2005-02-28 | 2006-09-14 | Dainippon Printing Co Ltd | Organic thin-film solar cell |
| JP4892197B2 (en) * | 2005-04-01 | 2012-03-07 | 関西パイプ工業株式会社 | Electrode substrate for dye-sensitized solar cell, photoelectrode and counter electrode for dye-sensitized solar cell, and dye-sensitized solar cell |
| WO2007029750A1 (en) * | 2005-09-06 | 2007-03-15 | Kyoto University | Organic thin film photoelectric converter and method for manufacturing same |
-
2008
- 2008-05-21 WO PCT/JP2008/059342 patent/WO2008152889A1/en active Application Filing
- 2008-05-21 JP JP2009519203A patent/JP5141685B2/en active Active
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| JP5141685B2 (en) | 2013-02-13 |
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