JP2003051586A - X-ray photoelectric converter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an X-ray photoelectric converter that is high in S/N and excellent in durability. SOLUTION: This X-ray photoelectric converter 10 has an electric charge collecting electrode 2, an undercoat layer 3 arranged on the electrode 2, and an X-ray photoconductive layer 4 arranged on the layer 3. This converter 10 also has an upper electrode 5 arranged on the layer 4. Since the undercoat layer 3 contains a silicon compound produced by hydrolyzing a silane coupling agent as the main component and, consequently, is durable against physical shocks, the durability of this X-ray photoelectric converter is improved as a whole. In addition, the converter 10 having the undercoat layer 3 also has a high S/N.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to the technical field of an electric field application type X-ray photoelectric converter having an undercoat layer provided between an X-ray photoconductive layer and an electrode.

[0002]

2. Description of the Related Art Techniques for converting X-rays into electric signals and digitizing and processing the extracted charges have begun to be widely used for industrial and medical purposes. The present inventors have studied an X-ray photoelectric converter provided with an X-ray photoconductive layer between parallel electrodes as an X-ray photoelectric converter for converting and extracting X-rays into an electric signal. The current value (noise) when an electric field is applied to the line photoelectric converter is large, and the ratio of the current value (signal) and noise (S / N ratio) when the X-ray photoelectric converter to which an electric field is applied is irradiated with X-rays. ) Has become smaller. Further, they are weak against external energy, such as cracking or discoloration due to environmental temperature change, discharge breakdown when a high electric field is applied, and weak peeling strength.

[0003]

DISCLOSURE OF THE INVENTION The present invention is to improve the S / N ratio of an electric field application type X-ray photoelectric converter.
The purpose is to show high durability against external energy.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have found that a thermosetting silicon compound formed by hydrolysis is formed under the X-ray photoconductive layer, that is, between the charge collecting electrode and the X-ray photoconductive layer. It has been found that the above problems can be solved by providing an undercoat layer containing the above.

The invention according to claim 1 made on the basis of the above knowledge, the charge collecting electrode, the X-ray photoconductive layer arranged on the charge collecting electrode, and the X-ray photoconductive layer are arranged. An X-ray photoelectric converter having an upper electrode, and a latent image is formed in the photoconductive layer when an X-ray is irradiated while a voltage is applied between the charge collecting electrode and the upper electrode. An undercoat layer is disposed between the charge collecting electrode and the X-ray photoconductive layer, and the undercoat layer contains a silicon compound produced by hydrolysis and dehydration condensation of a silane coupling agent. It is an X-ray photoelectric converter characterized by having a main component. The invention according to claim 2 is the X-ray photoelectric converter according to claim 1, wherein the silane coupling agent is an epoxysilane compound and an alkoxyalkylsilane compound.
It is an X-ray photoelectric converter characterized by containing an aminosilane compound. The invention according to claim 3 is the X-ray photoelectric converter according to claim 2, wherein the epoxysilane compound is one or both of the silane compounds represented by the following general formulas (1) and (2). An X-ray photoelectric converter characterized by containing the silane compound of.

[0006]

[Chemical 6]

(In the general formula (1), R ¹ is an alkylene group having 6 or less carbon atoms. R ² and R ³ are each 4 carbon atoms.
It is the following alkyl groups. R ⁴ is a substituent of either an alkyl group having 4 or less carbon atoms or an alkoxy group having 4 or less carbon atoms. )

[0008]

[Chemical 7]

(In the general formula (2), R ⁵ is an alkylene group having 6 or less carbon atoms. R ⁶ and R ⁷ are each 4 carbon atoms.
It is the following alkyl groups. R ⁸ is a substituent of either an alkyl group having 4 or less carbon atoms or an alkoxy group having 4 or less carbon atoms. The invention according to claim 4 is the X-ray photoelectric converter according to claim 2, wherein the alkoxyalkylsilane compound contains a silane compound represented by the following general formula (3). It is a line photoelectric converter.

[0010]

[Chemical 8]

(In the general formula (3), each of R ^{9 to} R ¹² is a substituent of either an alkyl group having 8 or less carbon atoms or an alkoxy group having 8 or less carbon atoms.) Is an X-ray photoelectric converter according to claim 2, wherein the aminosilane compound contains one or both of the silane compounds represented by the following general formulas (4) and (5). It is an X-ray photoelectric converter characterized in that.

[0012]

[Chemical 9]

(In the general formula (4), R ¹³ is an alkylene group having 6 or less carbon atoms, R ¹⁴ and R ¹⁵ are each an alkyl group having 4 or less carbon atoms, and R ¹⁶ is 4 or less carbon atoms. It is a substituent of either an alkyl group or an alkoxy group having 4 or less carbon atoms.)

[0014]

[Chemical 10]

(In the above general formula (5), R ¹⁷ is an alkylene group having 6 or less carbon atoms. R ¹⁸ is 2 or more carbon atoms and 4 carbon atoms.
The following are alkylene groups. R ¹⁹ and R ²⁰ are each an alkyl group having 4 or less carbon atoms. R ²¹ is a substituent of either an alkyl group having 4 or less carbon atoms or an alkoxy group having 4 or less carbon atoms. ) Each of the substituents constituting R ^{1 to} R ²¹ in the general formulas (1) to (4) has a linear structure or a branched structure. In addition, R ² , R ³ and R in the above general formulas (1) to (4)
⁶ , R ⁷ , R ^{9 to} R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁹ , and R ²⁰ are each independently a substituent.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the electric field application type X-ray photoelectric converter of the present invention are shown below, but the present invention is not limited thereto. As shown in FIG. 1, the electric field application type X-ray photoelectric converter 10 of the present invention is provided with a charge collecting electrode 2 on a glass substrate 1, and a thermosetting generated by hydrolyzing a silane coupling agent thereon. An undercoat layer 3 containing a conductive silicon compound,
The X-ray photoconductive layer 4 is provided on the undercoat layer 3, and the upper electrode 5 is provided on the X-ray photoconductive layer 4.

As another example, as in the X-ray photoelectric converter 20 shown in FIG. 2, the charge transport layer 6 may be provided on the undercoat layer 3, and the X-ray photoelectric converter shown in FIG. Like 30
The charge transport layer 6 may be provided on the X-ray photoconductive layer 4. Further, like the X-ray photoelectric converter 40 shown in FIG. 4, the protective layer 7 may be provided on the upper electrode 5. Furthermore, like the X-ray photoelectric converter 50 shown in FIG.
An overcoat layer 8 may be provided on the above.

Although not shown in the drawing, the charge transport layer, the protective layer and the overcoat layer may be provided at the same time. The undercoat layer of the present invention contains a thermosetting silicon compound produced by hydrolyzing a silane coupling agent.

The silane coupling agent has a hydrolyzable substituent such as an alkoxy group or a halogen group and a substituent such as a vinyl group, an epoxy group or an amino group, which easily reacts with an organic substance.

When the silane coupling agent is hydrolyzed,
A thermosetting silicon compound that has a siloxane structure of Si-O-Si bond through dehydration condensation reaction, has high electrical resistance, and has high adhesive strength even in different materials regardless of inorganic or organic. To form. The siloxane structure formed by the dehydration condensation reaction has a linear structure,
It may have a branched structure or a network structure.

The silane coupling agent is at least one epoxysilane compound selected from the following group A:
It is preferable for the object of the present invention to have at least one alkoxyalkylsilane compound selected from the following group B and at least one aminosilane compound selected from the following group C.

Group A: An epoxysilane compound represented by the following general formula (1) or general formula (2).

[0023]

[Chemical 11]

(In the general formula (1), R ¹ is an alkylene group having 6 or less carbon atoms. R ² and R ³ are each 4 carbon atoms.
It is the following alkyl groups. R ⁴ is a substituent of either an alkyl group having 4 or less carbon atoms or an alkoxy group having 4 or less carbon atoms. )

[0025]

[Chemical 12]

(In the general formula (2), R ⁵ is an alkylene group having 6 or less carbon atoms. R ⁶ and R ⁷ are each 4 carbon atoms.
It is the following alkyl groups. R ⁸ is a substituent of either an alkyl group having 4 or less carbon atoms or an alkoxy group having 4 or less carbon atoms. ) Group B: an alkoxyalkylsilane compound represented by the following general formula (3).

[0027]

[Chemical 13]

(In the general formula (3), each of R ^{9 to} R ¹² is a substituent of either an alkyl group having 8 or less carbon atoms or an alkoxy group having 8 or less carbon atoms.) Group C: An aminosilane compound represented by the general formula (4) or the following general formula (5).

[0029]

[Chemical 14]

(In the general formula (4), R ¹³ is an alkylene group having 6 or less carbon atoms, R ¹⁴ and R ¹⁵ are each an alkyl group having 4 or less carbon atoms, and R ¹⁶ is 4 or less carbon atoms. It is a substituent of either an alkyl group or an alkoxy group having 4 or less carbon atoms.)

[0031]

[Chemical 15]

(In the general formula (5), R ¹⁷ is an alkylene group having 6 or less carbon atoms. R ¹⁸ is 2 or more carbon atoms and 4 carbon atoms.
The following are alkylene groups. R ¹⁹ and R ²⁰ are each an alkyl group having 4 or less carbon atoms. R ²¹ is a substituent of either an alkyl group having 4 or less carbon atoms or an alkoxy group having 4 or less carbon atoms. ) Specific examples of the epoxysilane compound constituting the group A include β-glycidoxyethylpropyltripropoxysilane, β-glycidoxyethylpropyltributoxysilane, γ-glycidoxyethylpropyltrimethoxysilane, γ- There are glycidoxyethylpropyltriethoxysilane, γ-glycidoxyethylpropyltriproxysilane, γ-glycidoxyethylpropyltributoxysilane and the like.

Specific examples of the alkoxyalkylsilane compound constituting the group B include monomethyltrimethoxysilane, dimethyldimethoxysilane, monomethyltriethoxysilane, dimethyldiethoxysilane, monoethyltrimethoxysilane, diethyldimethoxysilane and monoethyltriethylsilane. Examples include ethoxysilane, diethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

Specific examples of the aminosilane compound constituting the group C include aminomethyltrimethoxysilane, aminomethyltriethoxysilane, aminomethyltripropoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane and aminopropyltributoxy. Examples include silane and N-β-aminoethyl-γ-aminopropyltrimethoxysilane.

Although some silane coupling agents are hydrolyzed only in the presence of a catalyst, the silane coupling agents having the silane compounds of groups A, B and C are catalysts for hydrolysis. It is not necessary to add, and the hydrolysis reaction can be advanced only by adding pure water to the mixture of silane coupling agents and stirring. In that case,
The hydrolysis time is very short and preferred. For the hydrolysis, acids such as hydrochloric acid, sulfuric acid, acetic acid and salts thereof may be used as a catalyst.

The composition ratio required for hydrolysis is as follows:
It is preferable to use 2 parts by volume or more and 10 parts by volume or less of the silane coupling agent selected from the groups B and C, respectively, and further use 1 part by volume or more and 6 parts by volume or less of water. These A
After selecting and mixing one or more kinds of silane coupling agents from groups C to C, water is added to carry out hydrolysis.
Vigorous stirring when water is added can accelerate the progress of the hydrolysis reaction.

If desired, an organic solvent may be added immediately after the completion of hydrolysis to adjust the concentration of hydrolysis. As the organic solvent to be added, hydrophilic ones are preferable, and methanol, ethanol, propanol, dioxane, methyl cellosolve, ethyl cellosolve and the like can be used.
The addition amount of these organic solvents is preferably 50 parts by volume or more and 300 parts by volume or less.

A solution (coating solution for forming an undercoat layer) after hydrolysis or addition of an organic solvent is applied onto the charge collecting electrode and cured by heating to form an undercoat layer containing a thermosetting silicon compound. The heating temperature is preferably 50 ° C. or higher and 150 ° C. or lower, and the heating time is preferably 0.5 hour or longer and 100 hours or shorter.

The undercoat layer of the present invention can be formed by a dip coating method, a spinner method, a spray method, a Langmuir-Blodgett method, or the like. The thickness of the undercoat layer is not particularly limited, but is preferably 0.1 μm or more and 100 μm or less. Examples of the charge collection electrode of the present invention include gold, aluminum and ITO.
(Indium / tin oxide) or the like can be used.
This electrode may be formed uniformly so as to cover the X-ray irradiation region, or may be formed in a matrix shape or a stripe shape.

Further, a TFT (thin film transistor) in which a transistor is provided between the glass substrate and the charge collecting electrode may be used. As the X-ray photoconductive layer of the present invention, a material that electrically converts X-rays is used. This material includes selenium, selenium tellurium compounds, selenium arsenic compounds, cadmium sulfide,
An inorganic material such as zinc oxide or amorphous silicon can be used, and selenium or a selenium compound is preferable.

The X-ray photoconductive layer can be formed by vacuum vapor deposition, sputtering, CVD or the like, depending on the material used. The film thickness of the formed X-ray photoconductive layer also varies depending on the material used, but is formed to be about 50 μm or more and 2000 μm or less. As the upper electrode of the present invention, gold, aluminum, ITO or the like can be used.

The charge transport layer that can be used in the present invention has the effect of further reducing noise. As this material, an inorganic material such as antimony disulfide or cadmium zinc telluride can be used. Alternatively, an organic material having a charge transfer property can be used.

As the protective layer and the overcoat layer which can be used in the present invention, a thermosetting silicon compound produced by hydrolyzing the silane coupling agent of the present invention can be used.

[0044]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

Example 1 As silane coupling agents, 2.4 parts by volume of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 4.8 parts by volume of monomethyltrimethoxysilane, and γ-aminopropyltrisilane. 2.4 parts by volume of ethoxysilane was prepared, 1.2 parts by volume of water was added to these mixtures, and the mixture was vigorously stirred at room temperature to allow the hydrolysis reaction to proceed to obtain a coating liquid for forming an undercoat layer.

ITO was formed into a matrix on a glass substrate to form a charge collecting electrode, the above coating liquid for forming an undercoat layer was applied onto the charge collecting substrate, and this was heated at 100 ° C. for 5 hours to give a transparent film having a thickness of 1 μm. An undercoat layer was formed. A film thickness of 50
0 μm selenium layer (X-ray photoconductive layer), and then a film thickness of 0.
A 1 μm gold thin film (upper electrode) was formed to prepare an X-ray photoelectric converter.

Example 2 Instead of the silane coupling agent used in Example 1, 5.2 parts by volume of γ-glycidoxypropyltrimethoxysilane, 6.4 parts by volume of dimethoxydimethylsilane and N-β ( An X-ray photoelectric converter was produced in the same manner as in Example 1 except that 2.4 parts by volume of aminoamino) γ-aminopropyltrimethoxysilane was used and the amount of water added was 2.2 parts by volume.

Example 3 Instead of the silane coupling agent used in Example 1, 4.2 parts by volume of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3.8 parts by volume of dimethyldimethoxysilane were used. An X-ray photoelectric converter was manufactured in the same manner as in Example 1 except that 4.4 parts by volume of γ-aminopropyltriethoxysilane was used and the amount of water added was changed to 2.2 parts by volume.

Example 4 Instead of the silane coupling agent used in Example 1, 5.8 parts by volume of γ-glycidoxypropyltrimethoxysilane, 1.2 parts by volume of tetramethoxysilane, N-β- An X-ray photoelectric converter was produced in the same manner as in Example 1 except that 4.6 parts by volume of aminoethyl-γ-aminopropylmethyldimethoxysilane was used and the amount of water added was 3.8 parts by volume.

Example 5 Instead of the silane coupling agent used in Example 1, 2.6 parts by volume of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 4.8 parts by volume of methoxytrimethylsilane were used. , Aminomethyltrimethoxysilane was used in the same manner as in Example 1 except that 2.8 parts by volume of water was used and the amount of water added was 4.2 parts by volume.
A line photoelectric converter was produced.

Example 6 2.4 parts by volume of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane,
Prepare 4.8 parts by volume of methyltrimethoxysilane and 2.4 parts by volume of γ-aminopropyltriethoxysilane, add 1.2 parts by volume of water to the mixture, and stir vigorously at room temperature to proceed with the hydrolysis reaction. This was used as the coating liquid for forming the overcoat layer.

In Example 1, after forming the selenium layer by vapor deposition, the above coating liquid for forming the overcoat layer was applied and heated at 40 ° C. for 24 hours to form an overcoat layer on the selenium layer. Then, an upper electrode was formed under the same conditions as in Example 1 to fabricate an X-ray photoelectric converter. This X-ray photoelectric converter has the same structure as the X-ray photoelectric converter 50 shown in FIG.

Example 7 In Example 1, after forming the undercoat layer, Sb ₂ S ₃ was formed as a charge transport layer by vapor deposition to a thickness of 5 μm. Otherwise, the selenium layer was formed on the charge transport layer under the same conditions as in Example 1, and the upper electrode was formed on the selenium layer to manufacture an X-ray photoelectric converter. This X-ray photoelectric converter has the same structure as the X-ray photoelectric converter 20 shown in FIG.

Comparative Example 1 An X-ray photoelectric film having no subbing layer was prepared by forming a 500 μm-thick selenium layer and then a 0.1 μm-thick gold thin film on a charge collection electrode having ITO matrix-formed on a glass substrate. A converter was made.

<Comparative Example 2> 100 parts by volume of polycarbonate was dissolved in 100 parts by volume of chloroform with good stirring to obtain a coating liquid for forming an undercoat layer. Next, the above-mentioned coating liquid for forming an undercoat layer was applied onto a charge collecting electrode having a matrix of ITO formed on a glass substrate, and this was heated at 100 ° C. for 5 hours to form a transparent undercoat layer having a film thickness of 1 μm. did. An X-ray photoelectric converter was produced in the same manner as in Example 1 except for the above.

Comparative Example 3 100 parts by volume of polymethylmethacrylate (PMMA) was added to 100 parts of tetrahydrofuran.
It was dissolved while stirring well in the volume part. Β-
30 parts by volume of (3,4-epoxycyclohexyl) ethyltrimethoxysilane was added and mixed well to prepare a solution, which was used as a coating liquid for forming an undercoat layer. Next, ITO on the glass substrate
The coating liquid for forming an undercoat layer was applied to the charge collecting electrode having a matrix formed thereon and heated at 100 ° C. for 5 hours to form a transparent undercoat layer having a film thickness of 1 μm. In this reaction, the polycondensation reaction due to hydrolysis did not occur. An X-ray photoelectric converter was produced in the same manner as in Example 1 except for the above.

<Comparative Example 4> CeO was used as an undercoat layer on a charge collecting electrode in which ITO was matrix-formed on a glass substrate.
₂ was formed by vacuum evaporation. Other than that, Example 1
An X-ray photoelectric converter was produced in the same manner as in.

<Evaluation> X produced in Examples and Comparative Examples
The evaluation items for the line photoelectric converter are shown below. Heat shock test Put the X-ray photoelectric converter in the constant temperature bath and check the temperature in the constant temperature bath as shown in Fig. 6.
The temperature was changed as shown in the temperature profile of 1. and this temperature change was repeated for 5 cycles to make a heat shock test.
After returning to room temperature, changes in appearance such as cracks, peeling, warpage, and discoloration were observed. The case where no change in appearance was observed was evaluated as ◯, and the case where change in appearance was observed was evaluated as x. Incidentally, FIG.
The vertical axis represents temperature (° C.), the horizontal axis represents time (hour), and one scale on the horizontal axis represents 1 hour.

Life test The X-ray photoelectric converter 10 is connected in a circuit as shown in FIG. 7 and the applied voltage is increased at 1 V / μm / h to the upper electrode 5 while the X-ray is irradiated from the X-ray irradiation direction 61. The value of the electric field at which discharge breakdown occurred was measured and used as a life test. The X-ray irradiation conditions at this time are as follows: an X-ray tube voltage of 120 kV and a dose of 18 R / mi.
n. Although the X-ray photoelectric converter shown in FIG. 1 is used in FIG. 7, the same circuit connection was made in other examples and used for the life test.

Peeling Test As shown in FIG. 8, a 24 mm width transparent adhesive tape 71 manufactured by Nichiban Co., Ltd. was attached to the X-ray photoelectric converter 10 of Example 1, and the angle was 45 ° with respect to the surface direction of the charge collecting electrode. It was observed whether or not the layer (formation layer) above the charge collecting electrode 2 was peeled off by peeling off the transparent adhesive tape 71 at once at the angle, and the peeling test was conducted. The case where the forming layer was not peeled off was marked with ◯, and the case where the forming layer was peeled off was marked with x.

Although the X-ray photoelectric converter of Example 1 is used in FIG. 8, the peeling test is performed by the same method in the X-ray photoelectric converters of Examples 2-7 and Comparative Examples 1-4. . Further, in Examples 1 to 7 and Comparative Examples 1 to 4, the charge collecting electrodes were formed in a matrix, but the charge collecting electrodes 2 formed uniformly on the glass substrate 1 were used for the peeling test.

When the S / N ratio X-ray photoelectric converter is connected as shown in FIG. 7 and the electric field is set to 10 V / μm, the current value when left for 10 minutes in the dark is defined as the noise current value N, The current value when the X-ray was irradiated at 18 R / min was defined as the signal current value S.
The ratio of the obtained signal current value S and noise current value N (S /
N ratio) was calculated. Table 1 shows the evaluation results of the above tests.
Shown in.

[0063]

[Table 1]

According to Table 1, the X-ray photoelectric converter provided with the subbing layer containing the thermosetting silicon compound produced by hydrolyzing the silane coupling agent was tested at ambient temperature by heat shock test. It can be seen that the environmental resistance is strong without changing the forming layer due to the change. Moreover, in the life test, even if an electric field of 20 V / μm is applied, the discharge is not destroyed,
It was found that it can withstand continuous use. Further, it can be seen that the adhesiveness is high, even withstanding peeling by the tape at the end of the forming layer in the peeling test. Furthermore, it was found that the S / N ratio was 4500 or more, which showed excellent characteristics.

Incidentally, Example 6 in which an overcoat layer made of a hydrolyzate of a silane coupling agent was provided and Example 7 in which a charge transport layer was provided below the X-ray photoconductive layer were obtained from Examples 1 to 5. The S / N ratio is further improved.

On the other hand, Comparative Example 1 in which no undercoat layer is provided
Shows that abnormalities such as cracks and cracks are seen in the heat shock test, discharge breakdown occurs at 12 V / μm in the life test, and the forming layer is peeled off in the peeling test, which is weak to external energy. It was
It was also found that the S / N ratio was very small, the noise current was large, and it could not be put to practical use.

Further, Comparative Example 3 using an undercoating layer containing a silane coupling agent but not causing a polycondensation reaction due to hydrolysis has the same result as that of Comparative Example 1. It was found that the electrical properties and the electrical properties were inferior.

Further, Comparative Example 2 provided with an undercoat layer made of polycarbonate and Comparative Example 4 provided with an undercoat layer made of CeO ₂ showed strong adhesive strength equivalent to that of the example in the peel test, In the shock test and the life test, only results comparable to those of Comparative Examples 1 and 3 were obtained, and it was found that the results were weak against changes in the operating environment and application of a high electric field.

[0069]

From the above results, the X-ray photoelectric converter of the present invention provided with an undercoat layer containing a thermosetting silicon compound produced by hydrolyzing a silane coupling agent is
It is an excellent X-ray photoelectric converter that has high durability against external energy such as temperature, electric field, and peeling, and has a high S / N ratio.

[Brief description of drawings]

FIG. 1 is a configuration diagram showing an example of an X-ray photoelectric converter of the present invention.

FIG. 2 is a configuration diagram showing another example of the X-ray photoelectric converter of the present invention.

FIG. 3 is a configuration diagram showing another example of the X-ray photoelectric converter of the present invention.

FIG. 4 is a configuration diagram showing another example of the X-ray photoelectric converter of the present invention.

FIG. 5 is a configuration diagram showing another example of the X-ray photoelectric converter of the present invention.

FIG. 6 is a temperature profile showing the transition of the environmental temperature in the heat shock test.

FIG. 7: Circuit connection diagram for life test and S / N ratio measurement

FIG. 8 is a schematic diagram of a peel test.

[Explanation of symbols]

1 ... Glass substrate 2 ... Charge collection electrode 3 ... Undercoat layer 4 ... X-ray photoconductive layer 5 ... Upper electrode 6 ... Charge transport layer 7 ... Protective layer 8: Upper layer

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yoichiro Shimura             1014 Miyahara-cho, Kofu City, Yamanashi Prefecture Yamanashi Electronics             Business (72) Inventor Hideo Tsuruta             1014 Miyahara-cho, Kofu City, Yamanashi Prefecture Yamanashi Electronics             Business F term (reference) 2G088 EE01 EE30 FF02 GG21 JJ05                       JJ09 JJ32 JJ35 JJ37 LL11                       LL21                 4M118 AA10 AB01 BA05 CA15 CB05                       CB06 FB09 FB25                 5F088 AB09 BA03 BB07 CB06 CB07                       FA04 GA02 LA08

Claims (5)

[Claims] 1. A charge collection electrode, an X-ray photoconductive layer arranged on the charge collection electrode, and an upper electrode arranged on the X-ray photoconductive layer. An X-ray photoelectric converter in which a latent image is formed in the photoconductive layer when irradiated with X-rays while a voltage is applied between the charge collection electrode and the X-ray photoconductive layer. And an undercoat layer is disposed between the undercoat layer and the undercoat layer, the silane coupling agent is hydrolyzed,
An X-ray photoelectric converter comprising a silicon compound produced by dehydration condensation as a main component. 2. The X-ray photoelectric converter according to claim 1, wherein the silane coupling agent contains an epoxysilane compound, an alkoxyalkylsilane compound, and an aminosilane compound. 3. The X according to claim 2, wherein the epoxysilane compound contains one or both of the silane compounds represented by the following general formulas (1) and (2). Line photoelectric converter. [Chemical 1] (In the general formula (1), R ¹ is an alkylene group having 6 or less carbon atoms. R ² and R ³ are each an alkyl group having 4 or less carbon atoms. R ⁴ is an alkyl group having 4 or less carbon atoms or It is a substituent of either one of alkoxy groups having 4 or less carbon atoms.) (In the general formula (2), R ⁵ is an alkylene group having 6 or less carbon atoms. R ⁶ and R ⁷ are each an alkyl group having 4 or less carbon atoms. R ⁸ is an alkyl group having 4 or less carbon atoms or (Any one of the alkoxy groups having 4 or less carbon atoms.) 4. The alkoxyalkylsilane compound is
The X-ray photoelectric converter according to claim 2, further comprising a silane compound represented by the following general formula (3). [Chemical 3] (In the general formula (3), R ^{9 to} R ¹² each have 8 carbon atoms.
It is a substituent of any one of the following alkyl groups and alkoxy groups having 8 or less carbon atoms. ) 5. The X-ray photoelectric according to claim 2, wherein the aminosilane compound contains one or both of the silane compounds represented by the following general formulas (4) and (5). converter. [Chemical 4] (In the general formula (4), R ¹³ is an alkylene group having 6 or less carbon atoms. R ¹⁴ and R ¹⁵ are each an alkyl group having 4 or less carbon atoms. R ¹⁶ is an alkyl group having 4 or less carbon atoms or It is a substituent of either one of alkoxy groups having 4 or less carbon atoms.) (In the general formula (5), R ¹⁷ is an alkylene group having 6 or less carbon atoms. R ¹⁸ is an alkylene group having 2 to 4 carbon atoms. R ¹⁹ and R ²⁰ are each 4 or less carbon atoms. R ²¹ is a substituent of either an alkyl group having 4 or less carbon atoms or an alkoxy group having 4 or less carbon atoms.)