JP2009175083A - Radiological image detecting device and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To enhance lag (image lag properties) of radiological image detector, while fully inhibiting the generation of dark current which is due to irradiation of backlight to the radiological image detector. <P>SOLUTION: In the radiological image detecting device which is equipped with a bias electrode 1, bias voltage is applied; a radiological image detector where a photoconducting layer 4 generating charge, in response to irradiation of the electromagnetic wave carrying radioactive ray imagery for recording use, a substrate-side charge transporting layer 5 for transporting the charge generated in the photoconducting layer 4; and an active matrix substrate 6, on which a plurality of charge collection electrodes collecting charge generated in the photoconducting layer 4 are laminated in the order; and a light-irradiating means 20 for irradiating light to the radiological image detector, during the period of irradiating of electromagnetic waves for recording use; the substrate-side charge transport layer 5 is formed to contain Sb<SB>x</SB>S<SB>(100-x)</SB>, and while having a layer where x satisfying a condition 41≤x≤60 as a part, to exhibit a composition distribution x varying in the direction of film thickness. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a radiological image detection apparatus including a radiographic image detector that records a radiographic image by generating a charge upon irradiation of a recording electromagnetic wave carrying a radiographic image and accumulating the charge. In particular, the present invention relates to a radiological image detection apparatus provided with a light irradiation means for irradiating light during irradiation of electromagnetic waves for recording onto the radiological image detector.

  2. Description of the Related Art Conventionally, in the medical field and the like, various radiological image detectors that record a radiographic image related to a subject by irradiation with radiation that has passed through the subject have been proposed and put into practical use.

  As the radiation image detector, for example, there is a radiation image detector using amorphous selenium that generates charges upon irradiation of radiation, and a so-called TFT reading type is proposed as such a radiation image detector. .

  As a TFT reading type radiographic image detector, for example, a bias electrode to which a bias voltage is applied, a photoconductive layer that generates charges when irradiated with radiation, and a charge collector that collects charges generated in the photoconductive layer An active matrix substrate in which a plurality of pixels having a storage capacitor for storing the charge collected by the electrode and the charge collecting electrode and a TFT switch for reading out the charge stored in the storage capacitor is arranged in a two-dimensional manner is stacked. Things have been proposed.

  When a radiographic image is recorded on the above-described TFT reading type radiographic image detector, first, a positive voltage is applied to the bias electrode of the radiographic image detector by the voltage source, and the object is transmitted. The radiation carrying the radiographic image of the subject is irradiated from the bias electrode side of the radiographic image detector.

  The radiation applied to the radiation image detector passes through the bias electrode and is applied to the photoconductive layer. Then, a charge pair is generated in the photoconductive layer by the irradiation of the radiation, and the negative charge is combined with the positive charge charged on the bias electrode and disappears, and the positive charge is latent image charge as each latent image charge on each active matrix substrate. A radiation image is recorded by being collected by each charge collecting electrode of the pixel and accumulated in each storage capacitor.

  Then, the TFT switch of the active matrix substrate is turned on in response to the control signal output from the gate driver, the charge stored in the storage capacitor is read out, and the charge signal is detected by the charge amplifier to produce a radiographic image. The corresponding image signal is read.

  Here, in the radiation image detector using the active matrix substrate as described above, the space between the charge collecting electrodes divided for each pixel is not provided with an electrode or the like for discharging charges, so that radiation irradiation is performed. The electric charges generated by the are likely to accumulate in the space. As a result, the electric field formed in the photoconductive layer is distorted by the application of the bias electrode, causing a problem that the sensitive area in the photoconductive layer changes and the sensitivity varies. In addition, when reading out the charge signal after the incidence of radiation stops, the charges accumulated in the space area between the charge collecting electrodes are gradually swept out and output as an afterimage, resulting in a deterioration of the lag (afterimage characteristics). There is.

  In view of this, a radiation image detection apparatus has been proposed in which a light source for irradiating a backlight from the active matrix substrate side of the radiation image detector is provided (see, for example, Patent Document 1). By irradiating the radiation image detector with a backlight by the above light source during irradiation of the radiation image detector, charges can be accumulated in advance in the space between the charge collecting electrodes, whereby the photoconductive layer It is possible to distort the electric field formed in advance. Therefore, the charges generated by the radiation irradiation move along the pre-distorted electric field without collecting in the space, and are collected by the charge collecting electrode. That is, the variation in the sensitive area of the photoconductive layer as described above can be suppressed, and the sensitivity variation can be suppressed. Further, by continuing the backlight irradiation even after the radiation is stopped, it is possible to prevent the charges accumulated in the space region between the charge collecting electrodes from being gradually swept out and resulting in an afterimage output.

Patent Document 1 proposes a radiation image detector in which an intermediate layer made of Sb ₂ S ₃ is provided between a photoconductive layer and an active matrix substrate. By providing this intermediate layer, it is possible to reduce the amount of irradiation of the backlight into the photoconductive layer, thereby suppressing dark current generated in the photoconductive layer.
JP 2004-146769 A

However, the intermediate layer made of Sb ₂ S ₃ cannot sufficiently absorb the backlight, and the generation of dark current due to the irradiation of light into the photoconductive layer has also been a problem.

Further, when an intermediate layer made of Sb ₂ S ₃ is provided between the active matrix substrate and the photoconductive layer as in the radiation image detector described in Patent Document 1, the active matrix substrate and Sb ₂ S ₃ Since the adhesion is not so good, the layer provided on the active matrix substrate may be peeled off.

Moreover, since the intermediate layer made of Sb ₂ S ₃ captures holes generated in the photoconductive layer, there is a problem that the lag is not so good.

  In view of the above circumstances, the present invention provides a radiological image detection apparatus including a radiological image detector capable of improving dark current characteristics, adhesion, and lag, and a method for manufacturing the radiological image detector. Objective.

The radiation image detection apparatus of the present invention includes a bias electrode to which a bias voltage is applied, a photoconductive layer that generates a charge upon irradiation of a recording electromagnetic wave carrying a radiation image, and a charge generated in the photoconductive layer. A radiation image detector in which a substrate-side charge transport layer to be transported and an active matrix substrate on which a large number of charge collecting electrodes for collecting charges generated in the photoconductive layer are arranged in this order, and a light to the radiation image detector In the radiation image detection apparatus including the light irradiation unit for irradiation, the substrate-side charge transport layer includes Sb _x S _(100-x) , and a part of the layer satisfies x ≦ 41 ≦ x ≦ 60. And x has a composition distribution that varies in the film thickness direction.

In the radiation image detector of the present invention, the composition of at least the vicinity of the interface with the photoconductive layer and the vicinity of the interface with the active matrix substrate in the substrate-side charge transport layer is Sb _x S _(100−x) (20 ≦ x ≦ 39).

In addition, the composition of at least the vicinity of the interface with the active matrix substrate in the substrate-side charge transport layer can be Sb _x S _(100−x) (20 ≦ x ≦ 39).

In addition, the composition of at least the vicinity of the interface with the photoconductive layer in the substrate-side charge transport layer can be Sb _x S _(100−x) (20 ≦ x ≦ 39).

  Further, the change of x in the substrate-side charge transport layer can be made gradually.

Further, a bias electrode side charge transport layer may be further provided between the bias electrode and the photoconductive layer, and the bias electrode side charge transport layer may include Sb _y S _(100−y) (y ≧ 41).

  Further, an organic polymer layer containing a hole blocking material can be further provided between the bias electrode side charge transport layer and the photoconductive layer.

Further, as the hole blocking material, at least one carbon cluster selected from carbon nanotubes, fullerene C ₆₀ , fullerene C ₇₀ , fullerene oxide, or derivatives thereof can be used.

A first radiation image detector manufacturing method of the present invention includes a bias electrode to which a bias voltage is applied, a photoconductive layer that generates a charge upon irradiation of a recording electromagnetic wave carrying a radiation image, and a photoconductive Method of manufacturing radiation image detector in which substrate-side charge transport layer for transporting charges generated in layer and active matrix substrate in which a large number of charge collecting electrodes for collecting charges generated in photoconductive layer are arranged in this order , Sb _x S _(100-x) (x ≧ 41) and Sb _y S _(100-y) (y <41) are heated independently to form a substrate-side charge transport layer by vapor deposition. It is characterized by filming.

A second radiation image detector manufacturing method of the present invention includes a bias electrode to which a bias voltage is applied, a photoconductive layer that generates a charge upon irradiation of a recording electromagnetic wave carrying a radiation image, and a photoconductive layer. Method of manufacturing radiation image detector in which substrate-side charge transport layer for transporting charges generated in layer and active matrix substrate in which a large number of charge collecting electrodes for collecting charges generated in photoconductive layer are arranged in this order In this method, vapor deposition is performed while heating Sb _x S _(100−x) (x <41) to a constant temperature higher than its melting point by 20 ° C. or more, thereby forming a substrate-side charge transport layer by vapor deposition. It is characterized by filming.

A third radiation image detector manufacturing method of the present invention includes a bias electrode to which a bias voltage is applied, a photoconductive layer that generates a charge upon irradiation with a recording electromagnetic wave carrying a radiation image, and a photoconductive layer. Method of manufacturing radiation image detector in which substrate-side charge transport layer for transporting charges generated in layer and active matrix substrate in which a large number of charge collecting electrodes for collecting charges generated in photoconductive layer are arranged in this order In this case, Sb _x S _(100−x) (x <41) is gradually heated to a predetermined temperature that is 20 ° C. or more higher than its melting point, and vapor deposition is started before the predetermined temperature is _reached. A substrate-side charge transport layer is formed by a deposition method.

  A fourth radiation image detector manufacturing method according to the present invention includes a bias electrode to which a bias voltage is applied, a photoconductive layer that generates a charge upon irradiation with a recording electromagnetic wave carrying a radiation image, and a photoconductive layer. Method of manufacturing radiation image detector in which substrate-side charge transport layer for transporting charges generated in layer and active matrix substrate in which a large number of charge collecting electrodes for collecting charges generated in photoconductive layer are arranged in this order The method is characterized in that Sb and S are heated independently, and the substrate-side charge transport layer is formed by vapor deposition.

According to the radiographic image detection apparatus of the present invention, a radiographic image comprising a radiographic image detector and a light irradiation means for irradiating the radiographic image detector with light during irradiation of electromagnetic waves for recording onto the radiographic image detector In the detection apparatus, the substrate-side charge transport layer of the radiation image detector includes Sb _x S _(100-x) , and x partially includes a layer satisfying 41 ≦ x ≦ 60, and x is a film thickness direction. In this case, the absorption wavelength of the substrate-side charge transport layer is increased by including a layer in which x is 41 ≦ x ≦ 60, and the light emitted from the light irradiation means is partly described above. By sufficiently absorbing by this layer, it is possible to sufficiently suppress the light from being irradiated to the inside of the photoconductive layer and to further suppress the generation of dark current. In addition, for example, when the composition distribution is such that a portion where x ≦ 39 exists, hole trap sites contained in the bulk of the substrate-side charge transport layer can be reduced, and thus the photoconductive layer is generated. Hole trapping can be reduced and lag can be improved.

In the radiological image detector of the present invention, the composition of at least the vicinity of the interface with the photoconductive layer and the vicinity of the interface with the active matrix substrate in the substrate-side charge transport layer is Sb _x S _(100−x) (20 ≦ x When ≦ 39), the trapping of holes generated in the photoconductive layer can be reduced, the lag can be improved, and the adhesion between the substrate-side charge transport layer and the active matrix substrate can be improved. Can be made.

Further, when the composition of at least the interface between the substrate-side charge transport layer and the active matrix substrate is Sb _x S _(100−x) (20 ≦ x ≦ 39), the active matrix substrate and the substrate-side charge transport layer The difference in the coefficient of linear thermal expansion between the substrate and the substrate can be improved even when there is a change in temperature during vapor deposition or working process.

Further, when the composition of at least the interface with the photoconductive layer in the substrate-side charge transport layer is Sb _x S _(100−x) (20 ≦ x ≦ 39), the holes generated in the photoconductive layer Capture can be reduced and lag can be improved.

In addition, when a bias electrode side charge transport layer is further provided between the bias electrode and the photoconductive layer, and the bias electrode side charge transport layer includes Sb _y S _(100−y) (y ≧ 41) Since the number of electron trap sites contained in the bulk of the bias electrode side charge transport layer can be reduced, the electron transport property of the bias electrode side charge transport layer can be improved, so that it is trapped in the photoconductive layer in bulk. Thus, it is possible to more efficiently sweep out the charged charges to the bias electrode, and it is possible to improve the long-term lag characteristics described later.

  Further, when an organic polymer layer containing a hole blocking material is further provided between the bias electrode side charge transport layer and the photoconductive layer, defects on the interface on the bias electrode side of the photoconductive layer are reduced. Therefore, the charge trapped by the defect can be reduced, and the characteristics of the short-term lag described later can be improved.

According to the first method for manufacturing a radiographic image detector of the present invention, a bias electrode to which a bias voltage is applied, a photoconductive layer that generates a charge upon irradiation with a recording electromagnetic wave carrying a radiographic image, A radiation image detector in which a substrate-side charge transport layer that transports charges generated in the photoconductive layer and an active matrix substrate in which a large number of charge collection electrodes that collect charges generated in the photoconductive layer are arranged in this order are stacked. In the manufacturing method, Sb _x S _(100-x) (x ≧ 41) and Sb _y S _(100-y) (y <41) are heated independently, and the substrate-side charge transport layer is formed by vapor deposition. Thus, a layer having a higher Sb composition ratio than the stoichiometric composition can be easily formed at an arbitrary position of the substrate-side charge transport layer.

According to the second method for manufacturing a radiographic image detector of the present invention, a bias electrode to which a bias voltage is applied, a photoconductive layer that generates a charge upon irradiation with a recording electromagnetic wave carrying a radiographic image, A radiation image detector in which a substrate-side charge transport layer that transports charges generated in the photoconductive layer and an active matrix substrate in which a large number of charge collection electrodes that collect charges generated in the photoconductive layer are arranged in this order are stacked. In the manufacturing method, vapor deposition is performed while heating Sb _x S _(100−x) (x <41) to a constant temperature higher than the melting point by 20 ° C. Thus, S can be gradually scattered in a vacuum so that it is not included in the substrate-side charge transport layer, and the substrate-side charge transport layer can have a gradient composition. . For example, when a substrate-side charge transport layer is formed on an active matrix substrate, a composition distribution can be formed such that the Sb ratio gradually increases toward the photoconductive layer side.

A third radiation image detector manufacturing method of the present invention includes a bias electrode to which a bias voltage is applied, a photoconductive layer that generates a charge upon irradiation with a recording electromagnetic wave carrying a radiation image, and a photoconductive layer. Method of manufacturing radiation image detector in which substrate-side charge transport layer for transporting charges generated in layer and active matrix substrate in which a large number of charge collecting electrodes for collecting charges generated in photoconductive layer are arranged in this order In this case, Sb _x S _(100−x) (x <41) is gradually heated to a predetermined temperature that is 20 ° C. or more higher than its melting point, and vapor deposition is started before the predetermined temperature is _reached. Since the substrate-side charge transporting layer is formed by the deposition method, S is gradually scattered in a vacuum so that the substrate-side charge transporting layer is transported in the same manner as in the method for manufacturing the second radiation image detector described above. The substrate-side charge transport layer can have a gradient composition. For example, when a substrate-side charge transport layer is formed on an active matrix substrate, a composition distribution can be formed such that the Sb ratio gradually increases toward the photoconductive layer side. Further, there is an advantage that the composition distribution can be controlled more easily than the manufacturing method of the second radiation image detector.

  A fourth radiation image detector manufacturing method according to the present invention includes a bias electrode to which a bias voltage is applied, a photoconductive layer that generates a charge upon irradiation with a recording electromagnetic wave carrying a radiation image, and a photoconductive layer. Method of manufacturing radiation image detector in which substrate-side charge transport layer for transporting charges generated in layer and active matrix substrate in which a large number of charge collecting electrodes for collecting charges generated in photoconductive layer are arranged in this order In this case, Sb and S were heated independently, and the substrate-side charge transport layer was formed by the vapor deposition method. Therefore, the composition ratio of Sb was chemically changed at an arbitrary position of the substrate-side charge transport layer. A layer higher than the stoichiometric composition can be easily formed.

  Hereinafter, an embodiment of a radiation image detection apparatus of the present invention will be described with reference to the drawings. The radiological image detection apparatus of the present embodiment includes a so-called TFT reading type radiological image detector. FIG. 1 is a cross-sectional view showing a schematic configuration of the radiological image detection apparatus of the present embodiment.

  The radiological image detection apparatus according to the present embodiment generates a charge by irradiation of radiation and records a radiographic image by accumulating the charge, and during irradiation of the radiation image detector 10 with radiation. A planar light source 20 for irradiating the radiation image detector 10 with light is provided.

  The radiation image detector 10 includes a bias electrode 1 to which a bias voltage is applied, a first charge transport layer 2, an organic polymer layer 3, and light that generates charges upon irradiation with radiation carrying a radiation image. A conductive layer 4; a second charge transport layer 5 that transports charges generated in the photoconductive layer 4; and a charge collection electrode that collects charges generated in the photoconductive layer and passed through the second charge transport layer 5. A plurality of active matrix substrates 6 arranged in this order are stacked in this order.

  The bias electrode 1 is formed of a low-resistance conductive material such as Au or Al.

The first charge transport layer 2 is formed of a material containing antimony sulfide. And the composition ratio of the antimony sulfide is Sb _y S _100-y (41 ≦ y). Y is more preferably 42 ≦ y ≦ 60.

The organic polymer layer 3 is formed by adding a hole blocking material to an organic polymer material. As the organic polymer material, for example, polycarbonate can be used. As the hole blocking material, at least one carbon cluster selected from carbon nanotubes, fullerene C ₆₀ , fullerene C ₇₀ , fullerene oxide, or derivatives thereof can be used.

The photoconductive layer 4 has electromagnetic wave conductivity, and generates charges inside the layer when irradiated with radiation. As the material for the photoconductive layer 4, for _example, it can be used _{a-Se, HgI 2, PbI} 2, CdS, CdSe, CdTe, a BiI ₃ or the like. In particular, it is desirable to use an a-Se film having a film thickness of 100 to 1000 μm mainly composed of selenium.

The second charge transport layer 5 is made of a material containing Sb _x S _(100-x) . The second charge transport layer 5 has a layer in which x satisfies 41 ≦ x ≦ 60 in part and has a composition distribution in which x varies in the film thickness direction. More specifically, the second charge transport layer 5 has a composition distribution as shown in FIGS. Note that the vertical axis in FIG. 3 indicates the size of x in Sb _x S _(100−x) , and the horizontal axis indicates the film thickness of the second charge transport layer 5. That is, for example, in FIG. 3 a, x gradually decreases from the vicinity of the center in the film thickness direction of the second charge transport layer 5 toward the vicinity of the interface with the active matrix substrate 6 and the vicinity of the interface with the photoconductive layer 4. Specifically, the composition in the vicinity of the center is Sb _x S _(100−x) (41 ≦ x ≦ 60), the vicinity of the interface with the active matrix substrate 6 and the photoconductive layer. 4 shows a composition distribution in which the composition in the vicinity of the interface with S4 is Sb _x S _(100−x) (20 ≦ x ≦ 39). FIG. 3 b shows a composition distribution in which x gradually increases from the vicinity of the interface with the photoconductive layer 4 toward the vicinity of the interface with the active matrix substrate 6 in the film thickness direction of the second charge transport layer 5. Specifically, the composition near the interface with the active matrix substrate 6 is Sb _x S _(100−x) (41 ≦ x ≦ 60), and the composition near the center is Sb _x S _{(100−x). )} (X = 40), and the composition distribution in the vicinity of the interface with the photoconductive layer 4 is Sb _x S _(100−x) (20 ≦ x ≦ 39). 3c shows a composition distribution in which x gradually increases from the vicinity of the interface with the active matrix substrate 6 toward the vicinity of the interface with the photoconductive layer 4 in the film thickness direction of the second charge transport layer 5. It indicates, specifically, the composition in the vicinity of the interface between the photoconductive layer 4 is _{Sb x S (100-x)} (41 ≦ x ≦ 60), the composition of the central vicinity the composition near the center Sb _x S _(100−x) (x = 40), showing a composition distribution in which the composition in the vicinity of the interface with the active matrix substrate 6 is Sb _x S _(100−x) (20 ≦ x ≦ 39). . FIG. 3 shows a composition distribution in which x gradually changes in the film thickness direction. However, the composition distribution is not limited to such a composition distribution. For example, a composition distribution in which x changes stepwise in the film thickness direction. May be adopted. The second charge transport layer 5 may be formed from one layer or may be formed from a plurality of layers. The thickness of the second charge transport layer 5 is desirably 0.5 μm or more. More preferably, it is about 2 μm.

  FIG. 2 shows a plan view of the active matrix substrate 6. In detail, as shown in FIG. 2, the active matrix substrate 6 includes a charge collection electrode 61 that collects charges generated in the photoconductive layer 4, a storage capacitor 62 that stores charges collected by the charge collection electrode 61, and a storage. A large number of pixels 60 each including a TFT switch 63 for reading out the electric charge accumulated in the capacitor 62 are arranged in a two-dimensional manner. A large number of scanning wirings 65 for turning on / off the TFT switch 63 of each pixel 60 and a large number of data wirings 66 for reading out the charges accumulated in the storage capacitor 62 are provided in a grid pattern. A read circuit 70 comprising an amplifier for detecting signal charges flowing out to the data line 66 is connected to the end of the data line 66, and a control signal for turning on / off the TFT switch 63 is connected to the scanning line 65. An output gate driver 80 is connected.

  The material of the charge collection electrode 61 in the active matrix substrate 6 is not particularly limited as long as it is a conductive material, but is preferably an electrode that transmits visible light. For example, ITO or IZO can be used.

  The planar light source 20 is a surface-mounted light emitting diode having a central emission wavelength of about 525 nm. As shown in FIG. 1, the planar light source 20 may be provided separately from the radiation image detector 10 or may be attached to the active matrix substrate 6 with a transparent adhesive. The planar light source 20 is capable of uniformly irradiating light on the active matrix substrate side of the photoconductive layer 4 through the active matrix substrate 6 during radiation irradiation of the radiation image detector 10. The active matrix substrate 6 and the adhesive are transparent to the wavelength of light emitted from the planar light source 20.

According to the radiological image detection apparatus of the above embodiment, the second charge transport layer 5 of the radiological image detector 10 includes Sb _x S _(100−x) , and a layer where x satisfies 41 ≦ x ≦ 60. Since x has a composition distribution in which x varies in the film thickness direction, the light emitted from the planar light source 20 is sufficiently absorbed by the partial layer, so that the light Irradiation to the inside of the conductive layer 4 can be sufficiently suppressed, and generation of dark current can be further suppressed. For example, when the composition distribution is such that there is a portion where x ≦ 39, the trapping of holes generated in the photoconductive layer 4 can be reduced, and the lag can be improved.

In the radiological image detection apparatus of the above embodiment, when the composition in the vicinity of the interface with the active matrix substrate 6 in the second charge transport layer 5 is Sb _x S _(100−x) (20 ≦ x ≦ 39) In addition, the adhesion between the second charge transport layer 5 and the active matrix substrate 6 can be further improved.

Further, according to the radiation image detecting apparatus of the above embodiment, the first charge transport layer 2 provided between the biasing electrode 1 and the photoconductive layer 4, a first charge transport layer 2, Sb y _{S (100 -Y) Since} (y ≧ 41) is included, the electron transport property of the first charge transport layer 2 can be improved, and the charges trapped in the bulk in the photoconductive layer 4 can be more efficiently biased. Therefore, the long-term lag characteristics can be improved. The long-term lag is an afterimage characteristic when about 300 seconds have elapsed from the end of radiation irradiation to the radiation image detector. For example, the charge collection electrode 61 of the active matrix substrate 6 is connected to an IV amplifier, and the bias electrode With a +10 kV applied to 1, a X-ray source with a tube voltage of 80 kV and a tube current of 100 mA irradiates the radiation image detector with a pulse X-ray of 710 ms, and the current value 300 seconds after the end of the X-ray pulse irradiation It can be evaluated by detecting with an amplifier and measuring with an oscilloscope.

  Further, according to the radiation image detection apparatus of the above embodiment, since the organic polymer layer 3 containing the hole blocking material is provided between the first charge transport layer 2 and the photoconductive layer 4, Defects at the interface on the bias electrode 1 side of the conductive layer 4 can be reduced, and charges trapped by the defects can be reduced, so that the short-term lag characteristics can be improved. The short-term lag is an afterimage characteristic when about 15 seconds have elapsed from the end of radiation irradiation to the radiation image detector. For example, the charge collection electrode 61 of the active matrix substrate 6 is connected to an IV amplifier, and the bias electrode With a +10 kV applied to 1, a X-ray source with a tube voltage of 80 kV and a tube current of 100 mA irradiates the radiation image detector with a pulse X-ray of 710 ms, and the current value 15 seconds after the end of the X-ray pulse irradiation is IV It can be evaluated by detecting with an amplifier and measuring with an oscilloscope.

  Hereinafter, the Example of the radiographic image detector in the radiographic image detection apparatus of this invention is described in detail.

Example 1
A radiation image detector is prepared so that the composition distribution of the second charge transport layer 5 becomes a composition distribution as shown in FIG. 3a, and the active matrix substrate 6 and the second radiation image detector are used to produce the radiation image detector. The adhesion with the charge transport layer 5, dark current, and lag were evaluated. The specific composition and evaluation results of the second charge transport layer 5 are shown in FIG.

In FIG. 4, the value of x of Sb _x S _{(100−x) in} the vicinity of the interface of the second charge transport layer 5 with the active matrix substrate 6 and Sb _x S in the vicinity of the center of the second charge transport layer 5. The x value of _{(100−x) and} the x value of Sb _x S _{(100−x) in} the vicinity of the interface between the second charge transport layer 5 and the photoconductive layer 4 are shown. That is, the second charge transport layer 5 of the radiographic image detector of Example 1 has a composition near the interface with the active matrix substrate 6 of Sb ₃₈ S ₆₂ , and a composition near the center of the second charge transport layer 5. Is Sb ₄₅ S ₅₅ , and the composition in the vicinity of the interface with the photoconductive layer 4 is Sb ₃₈ S ₆₂ .

  In the evaluation results, ◎ indicates very good, ○ indicates good, Δ indicates not so good, and X indicates bad.

  The manufacturing method of the radiation image detector of Example 1 will be described in detail later.

Regarding the adhesion between the active matrix substrate and the second charge transport layer, the produced radiation detector was cut out on a 10 mm × 10 mm square grid, and as shown in FIG. 9A, on the uppermost bias electrode 1. 10mm × 50mm × 3mm (W × L × H) Al plate edge 10mm × 10mm square part is fixed to 10mm × 10mm square bias electrode part with epoxy adhesive, then active matrix substrate is fixed The evaluation was performed by gradually pulling the Al plate in the horizontal direction (the direction indicated by the arrow X in FIG. 9A) with the deposition surface of the active matrix substrate and determining the strength when peeling. In the evaluation results, ◎ indicates that the peel interface is a surface other than the interface between the active matrix substrate and the second charge transport layer, or the strength when peeled even if the peel interface is peeled off at the interface between the active matrix substrate and the second charge transport layer. 15kgf / 100mm ² or more, ○ indicates that the peeling interface is a surface other than the interface between the active matrix substrate and the second charge transport layer, and the strength when peeling is 10kgf / 100mm ² or more and less than 15kgf / 100mm ² ; Is the interface between the active matrix substrate and the second charge transport layer, the peel strength is 2kgf / 100mm ² or more and less than 10kgf / 100mm ² , x is the interface between the active matrix substrate and the second charge transport layer It indicates that the strength when peeled is less than 5 kgf / 100 mm ² .

  The dark current was evaluated by applying +10 kV to the bias electrode 1 with the charge collection electrode 61 of the active matrix substrate 6 connected to the IV amplifier and measuring the current detected by the IV amplifier with an oscilloscope.

  As for the lag, like the long-term lag described above, an X-ray source with a tube voltage of 80 kV and a tube current of 100 mA in a state where the charge collection electrode 61 of the active matrix substrate 6 is connected to an IV amplifier and +10 kV is applied to the bias electrode 1. The pulse X-ray of 710 ms was irradiated by the above, and the current value 300 seconds after the end of the X-ray pulse irradiation was detected by an IV amplifier and measured by an oscilloscope.

Note that the dark current and lag measurements described above were performed with the planar light source 20 irradiating the radiation image detector 10 with light having a light amount of 20 μW / mm ² .

As shown in FIG. 4, the radiological image detector of Example 1 obtained favorable results for all items of adhesion, dark current, and lag as compared with the radiographic image detector of Comparative Example 1. In the radiation image detector of Comparative Example 1, the composition of the second charge transport layer 5 is Sb ₂ S ₃ uniformly in the film thickness direction.

The reason why good results were obtained with respect to the dark current was that the composition in the vicinity of the center of the second charge transport layer 5 was Sb ₄₅ S ₅₅ , so that the transmittance of the light emitted from the planar light source 20 was lowered. This is considered to be because irradiation of light to the photoconductive layer 4 could be suppressed.

Also, the good results for the lag were obtained because the composition of the second charge transport layer 5 in the vicinity of the interface with the photoconductive layer 4 was Sb ₃₈ S ₆₂ , so that the hole in the second charge transport layer 5 This is thought to be due to a decrease in traps.

Moreover, it is considered that the good results for the adhesion were obtained because the composition of the second charge transport layer 5 in the vicinity of the interface with the active matrix substrate 6 was Sb ₃₈ S ₆₂ and the Sb ratio was reduced. .

(Example 2)
A radiographic image detector is prepared so that the composition distribution of the second charge transport layer 5 is as shown in FIG. 3b, and the active matrix substrate 6 and the second radiographic image detector are used to produce the radiographic image detector. The adhesion with the charge transport layer 5, dark current, and lag were evaluated. The specific composition and evaluation results of the second charge transport layer 5 are as shown in FIG.

In the second charge transport layer 5 of the radiation image detector of Example 2, the composition near the interface with the active matrix substrate 6 is Sb ₄₅ S ₅₅ , and the composition near the center of the second charge transport layer 5 is Sb. ₄₀ S ₆₀ , and the composition in the vicinity of the interface with the photoconductive layer 4 is Sb ₃₈ S ₆₂ .

As shown in FIG. 4, the radiographic image detector of Example 2 obtained better results for dark current and lag than the radiographic image detector of Comparative Example 1, but the adhesion was not so great. There was no improvement. The reason why the adhesiveness has not been improved so much is considered to be that the composition of the second charge transport layer 5 in the vicinity of the interface with the active matrix substrate 6 is Sb ₄₅ S ₅₅ and the ratio of Sb is increased.

(Example 3)
A radiation image detector is prepared such that the composition distribution of the second charge transport layer 5 is the composition distribution as shown in FIG. 3c, and the active matrix substrate 6 and the second radiation image detector are used to produce the radiation image detector. The adhesion with the charge transport layer 5, dark current, and lag were evaluated. The specific composition and evaluation results of the second charge transport layer 5 are as shown in FIG.

In the second charge transport layer 5 of the radiation image detector of Example 3, the composition near the interface with the active matrix substrate 6 is Sb ₃₈ S ₆₂ , and the composition near the center of the second charge transport layer 5 is Sb. ₄₀ S ₆₀ , and the composition in the vicinity of the interface with the photoconductive layer 4 is Sb ₄₅ S ₅₅ .

As shown in FIG. 4, the radiological image detector of Example 3 had good results for all items of adhesion, dark current, and lag as compared with the radiographic image detector of Comparative Example 1. However, the characteristics of the lugs were slightly degraded as compared with the radiation image detectors of the first and second embodiments. This is presumably because the composition in the vicinity of the interface between the second charge transport layer 5 and the photoconductive layer 4 is Sb ₄₅ S ₅₅ and the ratio of Sb is increased.

  Next, an example of the manufacturing method of the radiation image detector according to the first to third embodiments will be described.

  First, the manufacturing method of the radiographic image detector of Example 1 mentioned above is demonstrated.

(Manufacturing method 1)
A second charge transport layer 5 was formed on the active matrix substrate 6 by vapor deposition. Specifically, an antimony sulfide raw material having a composition of Sb ₃₈ S ₆₂ and an antimony sulfide raw material having a composition of Sb ₄₅ S ₅₅ are placed in separate crucibles, and the two crucibles and the active matrix substrate 6 are deposited. It was arranged in the apparatus, and the inside of the apparatus was evacuated to 1 Pa.

First, by heating the crucible containing Sb ₃₈ S ₆₂ with a resistance heater, the Sb ₃₈ S ₆₂ is temporarily heated to 500 ° C. as shown in the leftmost temperature profile of FIG. And then heated to 555 ° C. At time t1 when the temperature reached 555 ° C., the shutter installed on the crucible was opened and deposition was started. Sb ₃₈ S ₆₂ heated to 555 ° C. evaporated, scattered inside the apparatus, deposited on the surface of the active matrix substrate 6, and a film of Sb ₃₈ S ₆₂ was formed on the active matrix substrate 6. Then, after the vapor deposition was started, the temperature was maintained at 555 ° C. until a time t2 when a predetermined time had elapsed, and then the shutter of the crucible containing Sb ₃₈ S ₆₂ was closed to temporarily terminate the vapor deposition of Sb ₃₈ S ₆₂ .

Next, after heating the crucible containing Sb ₄₅ S ₅₅ with a resistance heater, the Sb ₄₅ S ₅₅ is once heated to 500 ° C. as shown in the temperature profile in the center of FIG. Heated to 530 ° C. Then, at time t3 when the temperature reached 530 ° C., the shutter installed on the crucible was opened, and vapor deposition was started. _Sb 45 _{S 55} is deposited on the surface of the _Sb 38 _{S 62} layer on the active matrix substrate _6, the film of _Sb 45 _{S 55} was film. Then, after the start of deposition, after maintaining a predetermined time elapsed until time t4 530 ° _C., to complete the deposition of _Sb 45 _{S 55} closes the shutter of the crucible containing the _Sb 45 _{S 55.}

Then, _again, by heating the _{crucible Sb} 38 _{S 62} was placed by the resistance _heater, an _Sb 38 _{S 62,} as shown in the rightmost temperature profile of FIG. 5 (A), up to once 500 ° C. After heating, it was heated to 555 ° C. At time t5 when the temperature reached 555 ° C., the shutter installed on the crucible was opened, and a film of Sb ₃₈ S ₆₂ was formed again on the surface of the Sb ₄₅ S ₅₅ film on the active matrix substrate 6. Then, after the start of redeposition, the temperature was maintained at 555 ° C. until a time point t6 when a predetermined time had elapsed, and then the shutter of the crucible containing Sb ₃₈ S ₆₂ was closed to complete the deposition of Sb ₃₈ S ₆₂ .

  By forming the film as described above, it was possible to form the second charge transport layer 5 having the composition distribution as shown in FIG.

Incidentally, antimony sulfide material composition is _{Sb 45 S 55, Sb 38 S} 62 is manufactured as follows. First, an amount corresponding to a desired composition ratio of sulfur and antimony is measured, put in a glass container, further vacuumed and sealed, and the glass container is heated to the antimony melting point (630 ° C.) or higher. While melting, the mixture is stirred (15 hours or longer) to obtain a uniform composition antimony sulfide melt. Thereafter, natural cooling can produce an antimony sulfide raw material having a desired composition ratio.

  As for the composition of the second charge transport layer 5, for example, (1) a cross section of the radiation image detector is cut out, and the composition of the portion corresponding to the second charge transport layer 5 is changed to an energy dispersive X-ray analyzer. (2) A method of mapping by EDX, (2) A method of scraping a portion corresponding to the second charge transport layer 5 from a radiation image detector and measuring an average composition by X-ray fluorescence analysis (XRF), (3 ) It can be measured by a method such as a method in which the radiation image detector is peeled in the layer direction in the vicinity of the second charge transport layer 5 and measured by a thin film XRF method.

  Then, after forming the second charge transport layer 5 as described above, a Se raw material containing 10 ppm of Na is deposited by vapor deposition to form a photoconductive layer 4 made of amorphous Se having a thickness of 1000 μm. did.

It was then deposited organic polymer layer 3 containing the fullerene C _60. For fullerene C ₆₀ , nanom purple (C ₆₀ ) manufactured by Frontier Carbon Co., Ltd. was used. 3 wt% polycarbonate resin (PCz) (Iupilon PCZ-400 manufactured by Mitsubishi Gas Chemical Co., Ltd.) in o-dichlorobenzene and 30 wt% fullerene C ₆₀ dissolved in PCz to form a coating solution having a solid concentration of 1.5 wt% Was made. And after forming this solution into a film on the photoconductive layer 4 using the inkjet coating apparatus, the solvent was evaporated with the vacuum dryer and the organic polymer layer 3 with a film thickness of 0.2 micrometer was obtained.

Subsequently, the antimony sulfide raw material having a composition of Sb ₄₂ S ₅₈ is heated to 545 ° C., and the first charge transport layer 2 made of antimony sulfide having a film thickness of 0.6 μm (average composition Sb ₄₂ S ₅₈ ) is formed into an organic high layer. A region larger than the organic polymer layer 3 was formed on the molecular layer 3. The method for producing the antimony sulfide raw material having a desired composition ratio and the method for measuring the composition ratio of the first charge transport layer 2 are the same as those for the second charge transport layer 5.

  Finally, Au was deposited by vapor deposition to form a bias electrode 1 having a thickness of 0.1 μm, and the radiation image detector of Example 1 was produced.

(Manufacturing method 2)
Further, in the manufacturing method 1, each crucible is heated according to the temperature profile of FIG. 5A, and the deposition period of Sb ₄₅ S _{55 and} the deposition period of Sb ₃₈ S ₆₂ are completely separated. As shown in the temperature profile of FIG. 5B, the second charge transport layer 5 may be formed by overlapping the deposition period of Sb ₄₅ S _{55 and} the deposition period of Sb ₃₈ S ₆₂ .

Specifically, by first heating the crucible containing Sb ₃₈ S ₆₂ with a resistance heater, Sb ₃₈ S ₆₂ is shown in the leftmost temperature profile of FIG. Once heated to 500 ° C, it was heated to 555 ° C. Then, at time t1 when the temperature reached 555 ° C., the shutter installed on the crucible was opened, and vapor deposition was started.

_Then, in the middle of depositing _Sb 38 _{S 62,} and starts the heating by resistance heater of the crucible which is placed the _Sb 45 _{S 55.} Then, as shown in the middle temperature profile of FIG. 5 _(B), after heating to temporarily 500 ° C. The _Sb 45 _{S 55,} and heated to 530 ° C., was placed on the crucible at the time t2 became 530 ° C. The shutter was opened and deposition started.

Then, at the time t3 after starting the deposition of the Sb ₄₅ S ₅₅ film, the shutter of the crucible containing Sb ₃₈ S ₆₂ was closed, and the deposition of Sb ₃₈ S ₆₂ was once completed.

_Then, maintaining the temperature of the _Sb 45 _{S 55} to 530 ° C., in the course doing the deposition, _again, heating was initiated by the resistance heater _{crucible Sb} 38 _{S 62} was entered. Then, as shown in the rightmost temperature profile in FIG. 5 (B), Sb ₃₈ S ₆₂ is once heated to 500 ° C., then heated to 555 ° C., and placed on the crucible at time t 4 when it reaches 555 ° C. The opened shutter was opened, and deposition of Sb ₃₈ S ₆₂ was started again.

Then, at time t5 after the start of redevaporation of the Sb ₃₈ S ₆₂ film, the shutter of the crucible containing Sb ₄₅ S ₅₅ was closed, and the deposition of Sb ₄₅ S ₅₅ was completed.

At time t6 after the deposition of the Sb ₄₅ S ₅₅ film, the shutter of the crucible containing Sb ₃₈ S ₆₂ was closed, and the deposition of Sb ₃₈ S ₆₂ was completed.

  The second charge transport layer 5 having the composition distribution as shown in FIG. 3a could be formed by the film forming method as described above.

  The method for forming a layer other than the second charge transport layer 5 is the same as that of the manufacturing method 1. In addition, since the manufacturing method described below is the same as the manufacturing method 1 for the method for forming the layers other than the second charge transport layer 5, only the method for forming the second charge transport layer 5 is used. explain.

(Manufacturing method 3)
In the manufacturing method 1 and the manufacturing method 2, Sb ₃₈ S ₆₂ and Sb ₄₅ S ₅₅ are used as raw materials for the second charge transport layer 5, but Sb and S may be used as raw materials. Good.

  Specifically, first, metal antimony Sb and sulfur S were put in separate crucibles, the two crucibles and the active matrix substrate 6 were placed in a vapor deposition apparatus, and the interior of the apparatus was evacuated to 1 Pa. .

  First, by heating each of the crucible containing metal antimony and the crucible containing sulfur by a resistance heater, the metal antimony is once at 600 ° C. as shown in the temperature profile of FIG. Then heated to 640 ° C, sulfur was heated to 90 ° C and then heated to 125 ° C, and when the metal antimony was 640 ° C and sulfur was 125 ° C, the shutter installed on the crucible was opened at t1. The vapor deposition was started. And after vapor deposition start, the temperature of the crucible containing sulfur was kept constant at 125 ° C., and the temperature of the crucible containing metal antimony was gradually raised to 660 ° C. until the vapor deposition time t2. The temperature of the crucible containing sulfur remains constant at 125 ° C., and the temperature of the crucible containing metal antimony is gradually lowered to 640 ° C. until the deposition time reaches t3, and the shutter of the crucible containing metal antimony and sulfur The shutter of the crucible containing was closed to complete the deposition.

  By forming the film as described above, it was possible to form the second charge transport layer 5 having a composition distribution as shown in FIG.

  Next, the manufacturing method of the radiographic image detector of Example 2 mentioned above is demonstrated.

(Manufacturing method 4)
A second charge transport layer 5 was formed on the active matrix substrate 6 by vapor deposition. Specifically, first, an antimony sulfide raw material having a composition of Sb ₄₅ S ₅₅ and an antimony sulfide raw material having a composition of Sb ₃₈ S ₆₂ are placed in separate crucibles, and the two crucibles, the active matrix substrate 6, Was placed in a vapor deposition apparatus, and the interior of the apparatus was evacuated to 1 Pa.

Then, by first heating the crucible containing the antimony sulfide raw material Sb ₄₅ S ₅₅ with a resistance heater, Sb ₄₅ S ₅₅ is shown in the temperature profile on the left side of FIG. Once heated to 500 ° C, it was heated to 530 ° C. Then, at time t1 when the temperature reached 530 ° C., the shutter installed on the crucible was opened, and vapor deposition was started. _Sb 45 _{S 55} is deposited on the surface of the active matrix substrate 6, the film of _Sb 45 _{S 55} is a film on the active matrix substrate 6. Then, after the start of deposition, after maintaining a predetermined time elapsed until the time t2 530 ° _C., to complete the deposition of _Sb 45 _{S 55} closes the shutter of the crucible containing the _Sb 45 _{S 55.}

Next, after heating the crucible containing Sb ₃₈ S ₆₂ with a resistance heater, Sb ₃₈ S ₆₂ was once heated to 500 ° C. as shown in the temperature profile on the right side of FIG. Heated to 555 ° C. Then, at time t3 when the temperature reached 555 ° C., the shutter installed on the crucible was opened, and vapor deposition was started. _Sb 38 _{S 62} is deposited on the surface of the _Sb 45 _{S 55} layer on the active matrix substrate _6, the film of _Sb 38 _{S 62} was film. Then, after the vapor deposition was started, the temperature was maintained at 555 ° C. until a time point t4 when a predetermined time passed, and then the shutter of the crucible containing Sb ₃₈ S ₆₂ was closed to complete the vapor deposition of Sb ₃₈ S ₆₂ .

  By forming the film as described above, the second charge transport layer 5 having a composition distribution as shown in FIG. 3B could be formed.

(Manufacturing method 5)
In the manufacturing method 4, each crucible is heated according to the temperature profile of FIG. 6A, and the deposition period of Sb ₄₅ S _{55 and} the deposition period of Sb ₃₈ S ₆₂ are completely separated. As shown in the temperature profile of (B), the second charge transport layer 5 may be formed by overlapping the deposition period of Sb ₄₅ S _{55 and} the deposition period of Sb ₃₈ S ₆₂ .

Specifically, first, the crucible containing Sb ₄₅ S ₅₅ is heated by a resistance heater, so that Sb ₄₅ S ₅₅ is temporarily 500 times as shown in the temperature profile on the left side of FIG. 6B. After heating to ° C, it was heated to 530 ° C. Then, at time t1 when the temperature reached 530 ° C., the shutter installed on the crucible was opened, and vapor deposition was started.

_Then, in the middle of depositing _Sb 45 _{S 55,} and starts the heating by resistance heater of the crucible which is placed the _Sb 38 _{S 62.} Then, as shown in the temperature profile on the right side of FIG. 6 (B), Sb ₃₈ S ₆₂ was once heated to 500 ° C., then heated to 555 ° C. and placed on the crucible at time t 2 when it reached 555 ° C. The shutter was opened and deposition started.

Then, at the time t3 after starting the deposition of the Sb ₃₈ S ₆₂ film, the shutter of the crucible containing Sb ₄₅ S ₅₅ was closed, and the deposition of Sb ₄₅ S ₅₅ was completed.

Then, after the deposition of the Sb ₃₈ S ₆₂ film is started, the temperature of Sb ₃₈ S ₆₂ is maintained at 555 ° C. until time t4 when a predetermined time elapses, and then the shutter of the crucible containing Sb ₃₈ S ₆₂ is closed and Sb ₃₈ S ₆₂ is closed. The deposition of ₆₂ was completed.

  The second charge transport layer 5 having the composition distribution as shown in FIG. 3B could also be formed by the film forming method as described above.

(Manufacturing method 6)
In the manufacturing method 4 and the manufacturing method 5, Sb ₃₈ S ₆₂ and Sb ₄₅ S ₅₅ are used as the raw material of the second charge transport layer 5, but Sb and S may be used as the raw material. Good.

  Specifically, first, metal antimony Sb and sulfur S were put in separate crucibles, the two crucibles and the active matrix substrate 6 were placed in a vapor deposition apparatus, and the interior of the apparatus was evacuated to 1 Pa. .

  First, by heating each of the crucible containing metal antimony and the crucible containing sulfur by a resistance heater, as shown in the temperature profile of FIG. And then heated to 660 ° C., once heated to 90 ° C. and then heated to 125 ° C., and when the metal antimony reached 660 ° C. and the sulfur reached 125 ° C., the shutter installed on the crucible was opened. The vapor deposition was started. Then, after starting the vapor deposition, the temperature of the crucible containing sulfur is kept constant at 125 ° C., and the temperature of the crucible containing metal antimony is gradually lowered to 640 ° C. until the vapor deposition time reaches t 2. And the shutter of the crucible containing sulfur were closed to complete the deposition.

  By forming the film as described above, the second charge transport layer 5 having a composition distribution as shown in FIG. 3B could be formed.

  Next, the manufacturing method of the radiographic image detector of Example 3 mentioned above is demonstrated.

(Manufacturing method 7)
A second charge transport layer 5 was formed on the active matrix substrate 6 by vapor deposition. Specifically, first, an antimony sulfide raw material having a composition of Sb ₃₈ S ₆₂ was placed in a crucible, the crucible and the active matrix substrate 6 were placed in a vapor deposition apparatus, and the interior of the apparatus was evacuated to 1 Pa.

Next, by heating the crucible containing the antimony sulfide raw material which is Sb ₃₈ S ₆₂ with a resistance heater, the Sb ₃₈ S ₆₂ is once heated to 500 ° C. as shown in the temperature profile of FIG. After heating, it was heated to 570 ° C., which is 20 ° C. higher than the melting point of Sb ₃₈ S ₆₂ . And the shutter installed on the crucible was opened at the time t1 when Sb ₃₈ S ₆₂ reached 570 ° C., and vapor deposition was started. Sb ₃₈ S ₆₂ heated to 570 ° C. evaporates, scatters inside the device, and deposits on the surface of the active matrix substrate 6. At this time, S gradually scatters and does not adhere to the active matrix substrate 6. Thus, a film having a gradient composition was formed on the active matrix substrate 6 so that the proportion of the Sb composition gradually increased as the distance from the surface of the active matrix substrate 6 increased.

Then, after the vapor deposition was started, the temperature was maintained at 570 ° C. until time t2 when a predetermined time had elapsed, and then the shutter of the crucible containing Sb ₃₈ S ₆₂ was closed to complete the vapor deposition of Sb ₃₈ S ₆₂ .

  By forming the film as described above, the second charge transport layer 5 having a composition distribution as shown in FIG. 3c could be formed.

(Manufacturing method 8)
In the manufacturing method 8, the temperature of Sb ₃₈ S ₆₂ was increased from 500 ° C. to 570 ° C., and the deposition was started when the temperature of Sb ₃₈ S ₆₂ became 570 ° C., but FIG. As shown in the temperature profile, the temperature is once raised to 500 ° C., then raised to 555 ° C., and then the temperature is gradually raised to 570 ° C., and deposition is started from time t 1 when the temperature reaches 555 ° C. May be.

  By forming the film as described above, the second charge transport layer 5 having the composition distribution as shown in FIG. 3c could be formed.

(Manufacturing method 9)
In the manufacturing method 8, Sb ₃₈ S ₆₂ is used as the raw material of the second charge transport layer 5, but Sb ₃₈ S ₆₂ and Sb ₄₅ S ₅₅ may be used as the raw material.

First, by heating the crucible containing Sb ₃₈ S ₆₂ with a resistance heater, Sb ₃₈ S ₆₂ is once heated to 500 ° C. as shown in the temperature profile on the left side of FIG. And then heated to 555 ° C. Then, at time t1 when the temperature reached 555 ° C., the shutter installed on the crucible was opened, and vapor deposition was started.

Then, after the vapor deposition was started, the temperature of Sb ₃₈ S ₆₂ was maintained at 555 ° C. until time t2 when a predetermined time had elapsed, and then the shutter of the crucible containing Sb ₃₈ S ₆₂ was closed to complete the vapor deposition of Sb ₃₈ S ₆₂ .

Next, after heating the crucible containing Sb ₄₅ S ₅₅ with a resistance heater, Sb ₄₅ S ₅₅ was once heated to 500 ° C. as shown in the temperature profile on the right side of FIG. Heated to 530 ° C. Then, at time t3 when the temperature reached 530 ° C., the shutter installed on the crucible was opened, and vapor deposition was started.

Then, after the start of deposition, after maintaining a predetermined time elapsed until time t4 530 ° _C., to complete the deposition of _Sb 45 _{S 55} closes the shutter of the crucible containing the _Sb 45 _{S 55.}

  By forming the film as described above, the second charge transport layer 5 having a composition distribution as shown in FIG. 3c could be formed.

(Manufacturing method 10)
In the manufacturing method 9 described above, each crucible is heated according to the temperature profile of FIG. 7C to completely separate the deposition period of Sb ₄₅ S _{55 and} the deposition period of Sb ₃₈ S ₆₂ . As shown in the temperature profile of (A), the second charge transport layer 5 may be formed by overlapping the deposition period of Sb ₃₈ S _{62 and} the deposition period of Sb ₄₅ S ₅₅ .

Specifically, first, a crucible containing an antimony sulfide raw material that is Sb ₃₈ S ₆₂ is heated by a resistance heater, so that Sb ₃₈ S ₆₂ is shown in the temperature profile on the left side of FIG. 8A. Thus, after heating to 500 degreeC once, it heated to 555 degreeC. Then, at time t1 when the temperature reached 555 ° C., the shutter installed on the crucible was opened, and vapor deposition was started.

_Then, in the middle of depositing _Sb 38 _{S 62,} and starts the heating by resistance heater of the crucible which is placed the _Sb 45 _{S 55.} Then, as shown in the temperature profile on the right side of FIG. 8 (A), Sb ₄₅ S ₅₅ was once heated to 500 ° C., then heated to 530 ° C. and placed on the crucible at time t 2 when it reached 530 ° C. The shutter was opened and deposition started.

Then, at time t3 after starting the deposition of the Sb ₄₅ S ₅₅ film, the shutter of the crucible containing Sb ₃₈ S ₆₂ was closed, and the deposition of Sb ₃₈ S ₆₂ was completed.

Then, after the deposition of the Sb ₄₅ S ₅₅ film is started, the temperature of Sb ₄₅ S ₅₅ is maintained at 530 ° C. until a time t4 when a predetermined time has elapsed, and then the shutter of the crucible containing Sb ₄₅ S ₅₅ is closed and Sb ₄₅ S ₅₅ is closed. The deposition of ₅₅ was completed.

  The second charge transport layer 5 having the composition distribution as shown in FIG. 3c could also be formed by the film forming method as described above.

(Manufacturing method 11)
In the manufacturing method 9 and the manufacturing method 10, Sb ₃₈ S ₆₂ and Sb ₄₅ S ₅₅ are used as the raw material for the second charge transport layer 5, but Sb and S may be used as the raw material. Good.

  Specifically, first, metal antimony Sb and sulfur S were put in separate crucibles, the two crucibles and the active matrix substrate 6 were placed in a vapor deposition apparatus, and the interior of the apparatus was evacuated to 1 Pa. .

  First, by heating each of the crucible containing metal antimony and the crucible containing sulfur by a resistance heater, the metal antimony is once at 600 ° C. as shown in the temperature profile of FIG. Then heated to 640 ° C, sulfur was heated to 90 ° C and then heated to 120 ° C, and when the metal antimony was 640 ° C and the sulfur was 125 ° C, the shutter installed on the crucible was opened at t1. The vapor deposition was started. After starting the deposition, the temperature of the crucible containing sulfur is kept constant at 125 ° C., and the temperature of the crucible containing metal antimony is gradually increased to 660 ° C. until the deposition time reaches t 2. Vapor deposition was completed by closing the shutter and the shutter of the crucible containing sulfur.

  By forming the film as described above, the second charge transport layer 5 having a composition distribution as shown in FIG. 3c could be formed.

  In addition, although the specific time of each of t1-t6 in description of the said manufacturing methods 1-11 was set suitably by the thickness etc. of vapor deposition, about 30 minutes were each required until completion | finish of vapor deposition.

In the above-described embodiment, a so-called direct conversion type radiation image detector that directly converts radiation into electric charges has been described. However, the present invention is not limited thereto, and radiation is once converted into light by a phosphor and the light is charged. The present invention can also be applied to a radiation image detector having a configuration similar to that of a so-called indirect conversion type radiation image detector. Note that a radiation image detector having a configuration similar to the indirect conversion type radiation image detector is more than a direct conversion type radiation image detector.
The Se layer is thinned, a light transmission type bias electrode is provided, a phosphor is provided above the bias electrode, and light from the phosphor is converted into electric charges. In the radiographic image detector configured as described above, the thickness of the photoconductive layer is about 1 to 30 μm, and the storage capacitor in the active matrix substrate may be omitted.

  In the radiation image detector of the above embodiment, an active matrix substrate in which a large number of TFT switches are arranged is used. However, the present invention is an active matrix substrate in which a large number of switching elements such as MOS switches are arranged, for example. It is applicable also to the radiographic image detector provided with.

Sectional drawing which shows one Embodiment of the radiographic image detection apparatus of this invention Plan view of the active matrix substrate of the radiation image detector shown in FIG. The figure which shows the composition distribution of the 2nd charge transport layer of the Example of the radiographic image detector in the radiographic image detection apparatus of this invention. The table | surface which shows the composition distribution and evaluation result of the 2nd electric charge transport layer of the Example and comparative example of a radiographic image detector in the radiographic image detection apparatus of this invention Temperature profile for explaining the manufacturing method of the radiation image detector according to the first embodiment of the radiation image detection apparatus of the present invention Temperature profile for explaining the manufacturing method of the radiation image detector according to the second embodiment of the radiation image detection apparatus of the present invention Temperature profile for explaining the manufacturing method of the radiation image detector according to the third embodiment of the radiation image detection apparatus of the present invention Temperature profile for explaining the manufacturing method of the radiation image detector according to the eighth embodiment of the present invention. The figure for demonstrating the evaluation method of the adhesiveness of an active matrix substrate and a 2nd electric charge transport layer

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Bias electrode 2 1st charge transport layer (bias electrode side charge transport layer)
3 Organic polymer layer 4 Photoconductive layer 5 Second charge transport layer (substrate-side charge transport layer)
6 Active matrix substrate 7 Second electrode layer 20 Planar light source (light irradiation means)
60 pixels 61 charge collection electrode 62 storage capacitor 63 TFT switch 64 scanning wiring 65 data wiring 70 readout circuit 80 gate driver

Claims (12)

A bias electrode to which a bias voltage is applied; a photoconductive layer that generates a charge upon irradiation of a recording electromagnetic wave carrying a radiation image; and a substrate-side charge transport layer that transports the charge generated in the photoconductive layer. A radiation image detector having an active matrix substrate on which a large number of charge collection electrodes for collecting charges generated in the photoconductive layer are arranged in this order, and a light irradiation means for irradiating the radiation image detector with light In a radiological image detection apparatus comprising:
The substrate-side charge transport layer contains Sb _x S _(100-x) , the x partially includes a layer satisfying 41 ≦ x ≦ 60, and the x varies in the film thickness direction. A radiation image detection apparatus having a distribution. The composition of at least the vicinity of the interface with the photoconductive layer and the vicinity of the interface with the active matrix substrate in the substrate-side charge transport layer is Sb _x S _(100−x) (20 ≦ x ≦ 39) The radiation image detection apparatus according to claim 1. The radiation image detection according to claim 1, wherein the composition of at least the interface with the active matrix substrate in the substrate-side charge transport layer is Sb _x S _(100−x) (20 ≦ x ≦ 39). apparatus. The radiation image detection according to claim 1, wherein the composition of at least the interface with the photoconductive layer in the substrate-side charge transport layer is Sb _x S _(100−x) (20 ≦ x ≦ 39). apparatus.   The radiographic image detection apparatus according to claim 1, wherein the change of x in the substrate-side charge transport layer is gradual. A bias electrode side charge transport layer provided between the bias electrode and the photoconductive layer;
6. The radiological image detection apparatus according to claim 1, wherein the bias electrode side charge transport layer includes Sb _y S _(100−y) (y ≧ 41).   The radiographic image detection apparatus according to claim 6, further comprising an organic polymer layer containing a hole blocking material provided between the bias electrode side charge transport layer and the photoconductive layer. The hole blocking material, carbon nanotubes, fullerene C _60, fullerene C _70, the radiation image detecting apparatus according to claim 7, wherein the at least one carbon cluster selected from fullerene oxide or a derivative thereof . A bias electrode to which a bias voltage is applied; a photoconductive layer that generates a charge upon irradiation of a recording electromagnetic wave carrying a radiation image; and a substrate-side charge transport layer that transports the charge generated in the photoconductive layer. In the method for manufacturing a radiation image detector, an active matrix substrate on which a large number of charge collection electrodes for collecting charges generated in the photoconductive layer are arranged in this order is laminated.
Sb _x S _(100-x) (x ≧ 41) and Sb _y S _(100-y) (y <41) are heated independently to form the substrate-side charge transport layer by vapor deposition. A method for manufacturing a radiation image detector. A bias electrode to which a bias voltage is applied; a photoconductive layer that generates a charge upon irradiation of a recording electromagnetic wave carrying a radiation image; and a substrate-side charge transport layer that transports the charge generated in the photoconductive layer. In the method for manufacturing a radiation image detector, an active matrix substrate on which a large number of charge collection electrodes for collecting charges generated in the photoconductive layer are arranged in this order is laminated.
The substrate-side charge transport layer is formed by vapor deposition by performing deposition while heating Sb _x S _(100-x) (x <41) to a constant temperature higher than the melting point by 20 ° C. or more. A method for manufacturing a radiation image detector. A bias electrode to which a bias voltage is applied; a photoconductive layer that generates a charge upon irradiation of a recording electromagnetic wave carrying a radiation image; and a substrate-side charge transport layer that transports the charge generated in the photoconductive layer. In the method for manufacturing a radiation image detector, an active matrix substrate on which a large number of charge collection electrodes for collecting charges generated in the photoconductive layer are arranged in this order is laminated.
By gradually heating Sb _x S _(100-x) (x <41) to a predetermined temperature higher than the melting point by 20 ° C. or more and starting vapor deposition before the predetermined temperature is reached, a vapor deposition method A method of manufacturing a radiation image detector, wherein the substrate-side charge transport layer is formed by: A bias electrode to which a bias voltage is applied; a photoconductive layer that generates a charge upon irradiation of a recording electromagnetic wave carrying a radiation image; and a substrate-side charge transport layer that transports the charge generated in the photoconductive layer. In the method for manufacturing a radiation image detector, an active matrix substrate on which a large number of charge collection electrodes for collecting charges generated in the photoconductive layer are arranged in this order is laminated.
A method of manufacturing a radiation image detector, comprising heating Sb and S independently and forming the substrate-side charge transport layer by vapor deposition.

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