JP7156566B2 - scintillator structure - Google Patents

Description

The present invention relates to a scintillator structure and its manufacturing method, and for example, to a technique effectively applied to a scintillator structure having a plurality of cells each containing a resin and a phosphor and its manufacturing method.

Japanese Patent Application Laid-Open No. 100391/1988 (Patent Document 1) describes a technique related to a phosphor molded body in which a powder phosphor and an epoxy resin are mixed.

Japanese Patent Laying-Open No. 2-17489 (Patent Document 2) describes a technique related to phosphors used in radiation detectors.

JP-A-63-100391 JP-A-2-17489

A scintillator is a substance that absorbs the energy of radiation and emits visible light when exposed to radiation such as X-rays and gamma rays. This scintillator is commercialized as a scintillator structure containing a scintillator and a reflective material, and an X-ray detector that combines the scintillator structure and a photoelectric conversion element such as a photodiode is used for medical equipment such as X-ray CT, It is used in analysis equipment, non-destructive inspection equipment using radiation, radiation leakage inspection equipment, etc.

For example, scintillators use ceramics made of gadolinium oxysulfide (Gd ₂ O ₂ S). Here, in this specification, gadolinium oxysulfide will be referred to as "GOS". Strictly speaking, gadolinium oxysulfide itself hardly emits light, and gadolinium oxysulfide contains praseodymium, terbium, or the like to emit light. For this reason, the term "GOS" is used in this specification to imply a substance (phosphor) that emits light by containing praseodymium, terbium, or the like in gadolinium oxysulfide itself. However, when it is necessary to explicitly indicate that gadolinium oxysulfide itself contains praseodymium, terbium, etc., it may be expressed as "GOS" containing praseodymium or "GOS" containing terbium.

Further, when the scintillator is composed of a single "GOS", the "GOS" is composed of ceramic. On the other hand, as will be described later, it is also under study to construct the scintillator from a mixture of "GOS" and resin, and in this case, "GOS" is composed of powder. Therefore, in this specification, when there is no need to specify ceramic and powder, the term "GOS" is simply used. In contrast, when it is necessary to specify the ceramic, it is referred to as a "GOS" ceramic. On the other hand, when it is necessary to specify the powder, it will be referred to as "GOS" powder.

This “GOS” has the advantage of having a higher visible light emission output than cadmium tungstate (CdWO ₄ ), but the manufacturing cost is high.

For this reason, the use of a mixture of "GOS" powder and resin as a scintillator has been investigated in order to reduce the manufacturing cost of the scintillator structure.

However, the present inventor has newly discovered that the use of a mixture of "GOS" powder and resin leaves room for improvement in terms of adhesion between the scintillator and the reflector. Therefore, when a mixture of "GOS" powder and resin is used as a scintillator, it is desired to ensure adhesion between the scintillator and the reflective material.

A scintillator structure in one embodiment comprises a plurality of cells and a reflective material covering the plurality of cells. Here, each of the plurality of cells contains resin and phosphor, and the phosphor contains gadolinium oxysulfide. The breaking strength of the interface between each of the plurality of cells and the reflector is 900 gf or more.

According to one embodiment, the adhesion between the scintillator and the reflector can be ensured.

It is a figure which shows an X-ray detector typically. FIG. 10 is a diagram for explaining a cause of a decrease in light emission output in “resin GOS”; 4 is a graph showing the relationship between cell thickness and light output. 4 is a graph showing the relationship between the density of cells themselves and the light output. It is a graph which shows the afterglow characteristic of "CWO." 4 is a graph showing afterglow characteristics of "third resin GOS". 4 is a graph showing afterglow characteristics of "first resin GOS". 4 is a flow chart for explaining the flow of a manufacturing process for a scintillator structure; It is a figure which shows typically the process from a dicing process to a reflector coating process. Graph showing the results of evaluating the wettability to epoxy resin by comparing the contact angle when epoxy resin is dropped on the surface of "resin GOS" after various surface treatments are applied to the surface of "resin GOS". is. It is a figure explaining the wettability improvement by a titanium oxide liquid immersion process. (a) is a cross-sectional view schematically showing a manufacturing process of a sample to be evaluated by a bending test, and (b) is a top view schematically showing a manufacturing process of a sample to be evaluated by a bending test. (a) is a cross-sectional view showing the state of the bending test, and (b) is a top view showing the state of the bending test. (a) is a table showing the conditions of the surface treatment applied to the scintillator structure before forming the samples, and (b) shows the conditions for the samples corresponding to "Condition 1" to "Condition 8". It is a graph showing the breaking strength measured by conducting a bending test.

In principle, the same members are denoted by the same reference numerals throughout the drawings for describing the embodiments, and repeated description thereof will be omitted. In order to make the drawing easier to understand, even a plan view may be hatched.

<Overview of X-ray detector>
FIG. 1 is a diagram schematically showing an X-ray detector.

In FIG. 1, an X-ray detector 100 has a scintillator structure 10 and a light receiving element 20 . The scintillator structure 10 is composed of a scintillator 11 that generates visible light from X-rays incident on the X-ray detector 100 and a reflector 12 that covers the scintillator 11 . On the other hand, the light receiving element 20 has a function of generating current from visible light generated by the scintillator 11, and is composed of a photoelectric conversion element represented by a photodiode, for example.

The scintillator 11 has a function of absorbing X-rays and generating visible light, and is composed of phosphor 11a and resin 11b. Here, in this specification, the material obtained by mixing the "GOS" powder constituting the phosphor 11a and the resin 11b is sometimes called "resin GOS". That is, the scintillator 11 in this embodiment is made of "resin GOS". The phosphor 11a is gadolinium oxysulfide containing praseodymium, terbium, or the like, and the resin 11b is, for example, an epoxy resin. Moreover, the reflector 12 is made of an epoxy resin containing titanium oxide.

The X-ray detector configured in this manner operates as follows.

That is, when X-rays are incident on the scintillator 11 of the scintillator structure 10, electrons in the phosphors 11a forming the scintillator 11 receive the energy of the X-rays and transition from the ground state to the excited state. The electrons in the excited state then transition to the ground state. At this time, visible light corresponding to the energy difference between the excited state and the ground state is emitted. By such a mechanism, the scintillator 11 absorbs X-rays and generates visible light.

A part of the visible light emitted from the scintillator 11 is directly incident on the light receiving element 20, and the other part of the visible light emitted by the scintillator 11 is emitted from the scintillator. The light is focused on the light receiving element 20 while being repeatedly reflected by the reflector 12 covering the light receiving element 11 .

Subsequently, when visible light is incident on the light receiving element 20 composed of, for example, a photodiode, electrons of the semiconductor material constituting the photodiode are excited from the valence band to the conduction band by the energy of the visible light. As a result, a current due to electrons excited in the conduction band flows through the photodiode. An X-ray image is acquired based on the current output from the photodiode. Thus, the X-ray detector 100 can acquire an X-ray image.

<Reason for adopting “Resin GOS”>
As described above, "resin GOS" is used as the scintillator 11 in this embodiment. The reason for this will be explained below.

For example, cadmium tungstate (hereinafter referred to as “CWO”) is used as the scintillator 11 constituting the scintillator structure 10, and this “CWO” contains cadmium, which is a substance subject to the RoHS Directive/REACH Regulation. include. For this reason, "GOS" ceramic has been used as the scintillator 11 instead of "CWO" containing cadmium. This "GOS" ceramic has an advantage over "CWO" in that it has a higher emission output of visible light, but has a disadvantage in that the manufacturing cost is higher.

Therefore, from the viewpoint of reducing the manufacturing cost, it is being considered to adopt "resin GOS", which is a mixture of resin such as epoxy resin and "GOS" powder, instead of "GOS" ceramic as the scintillator 11. there is That is, there is a movement to use "resin GOS", which is cheaper than "GOS" ceramic, for the scintillator 11 in order to suppress the increase in manufacturing cost due to "GOS" ceramic.

However, the "resin GOS" has a lower light emission output than the "GOS" ceramic, and it is desired to secure the light emission output even when the "resin GOS" is used as the scintillator 11 .

<Factor of decrease in light output>
First, the cause of the decrease in the light output of the "resin GOS" will be described.

<< 1st cause >>
"Resin GOS" is composed of, for example, a mixture of resin such as epoxy resin and "GOS" powder. Both the epoxy resin and the "GOS" powder are transparent to visible light. In this regard, the translucency of epoxy resin is higher than that of "GOS". Therefore, the translucency of the "resin GOS" is higher than that of the "GOS" ceramic. Therefore, as a result of the translucency of "resin GOS" being higher than that of "GOS", at first glance, the luminous output of scintillator 11 using "resin GOS" is lower than that of scintillator 11 using "GOS" ceramic. It is thought that it will be higher than the luminous output.

However, in reality, the luminous output of the scintillator 11 using the "resin GOS" is lower than the luminous output of the scintillator 11 using the "GOS" ceramic.

This is because "resin GOS" uses "GOS" powder, and as a result, the total surface area of "GOS" powder constituting "resin GOS" is larger than the total surface area of "GOS" ceramic. presumably due to this. That is, in the "resin GOS", since a large amount of "GOS" powder is present in the epoxy resin, the light emitted by the "GOS" powder is emitted from the "GOS" powder into the epoxy resin. Even if the light is emitted, it then undergoes multiple scattering on the surface of the "GOS" powder, which exists in large quantities, and light absorption occurs on the surface of the "GOS" powder each time it scatters. As a result, since the "resin GOS" absorbs more light than the "GOS" ceramic, the light emission output of the scintillator 11 using the "resin GOS" is higher than that of the scintillator 11 using the "GOS" ceramic. likely to be higher. This is presumed to be the primary reason for the decrease in light output in the "resin GOS".

<<Second cause>>
For example, as shown in FIG. 2, the scintillator structure 10 is composed of a rectangular parallelepiped scintillator 11 and a reflector 12 covering the scintillator 11 . Here, since the rectangular parallelepiped scintillator 11 is formed through processing steps such as a dicing step and a grinding step, a processed surface is formed on the surface of the rectangular parallelepiped shape. That is, the term "processed surface" refers to a surface that has been mechanically processed. Specifically, the "machined surface" includes a surface ground with a grinding wheel to increase the thickness of the workpiece, or a surface obtained by cutting the workpiece with a slicing blade for dicing. For example, in the scintillator 11 using the "resin GOS", the "processed surface" is defined as a surface where the resin is exposed and the surface where the "GOS" powder is fractured. For example, the dashed line shown in FIG. 1 schematically represents the case where the interface between the scintillator 11 and the reflector 12 is the "processed surface" in the scintillator 11 using "resin GOS". In this case, it can be seen that the "processed surface" includes a region where the resin 11b is cut and a region where the phosphor 11a ("GOS" powder) is broken. Note that the dashed lines shown in FIG. 1 are drawn for easy explanation of the configuration of the “machined surface”, and the dashed lines do not intend to shrink the scintillator 11, and the size of the scintillator 11 surrounded by the dashed lines may be the size enclosed by the solid line.

This machined surface becomes the machined deteriorated layer 30 because it receives mechanical damage due to the machining process. A “work-affected layer” is defined as a layer that becomes more susceptible to light absorption due to deterioration in light reflection characteristics compared to before mechanical processing due to mechanical damage caused by mechanical processing. be done. For example, a specific example of the "work-affected layer" is a light absorption layer formed by desulfurization of the sulfur component on the surface of the "GOS" powder.

Visible light generated by the scintillator 11 is easily absorbed by the work-affected layer 30 . That is, part of the generated visible light is absorbed by the work-affected layer 30 existing in the scintillator 11, resulting in a decrease in light emission output. In other words, the formation of the work-affected layer 30 on the surface of the scintillator 11 is one of the factors that reduce the light output from the scintillator structure 10 .

Particularly, in recent years, as shown in FIG. 2, from the viewpoint of improving the resolution of X-ray images, the scintillator 11 is divided into a plurality of cells CL corresponding to each of the plurality of photodiodes (scintillator 11 array). A reflector 12 is provided to cover the plurality of cells CL. Specifically, the top surface and four side surfaces of the cell CL are covered with a reflector 12 . On the other hand, the bottom surface of the cell CL is not covered with the reflector 12 because it needs to be in contact with the photodiode.

When the scintillator 11 is divided into a plurality of cells CL, the work-affected layer 30 is formed on the surface of each of the plurality of cells CL, so that the area of the work-affected layer 30 in the scintillator structure 10A increases. As a result, in the multi-cell type scintillator structure 10A, it is considered that the reduction in light emission output caused by the work-affected layer 30 becomes large.

The scintillator structure in the present embodiment is premised on the multi-cell scintillator structure 10A capable of improving the resolution of X-ray images. For this reason, it is considered that the deterioration of the light emission output caused by the work-affected layer 30 becomes large, so it is important to take measures to maintain the light emission output.

Here, the process-affected layer 30 is formed on the surface of the scintillator 11 regardless of whether the scintillator 11 is made of "GOS" ceramic or "resin GOS". Therefore, it is conceivable that the light emission output is lowered due to the work-affected layer 30 regardless of whether the scintillator 11 is made of "GOS" ceramic or made of "resin GOS".

Regarding this point, according to the study of the present inventors, the scintillator 11 made of "resin GOS" is more likely to reduce the emission output due to the work-affected layer 30 than the scintillator 11 made of "GOS" ceramic. It was newly discovered that the decrease becomes larger.

The reason for this will be explained below. For example, "GOS" ceramics can be subjected to heat treatment even after being singulated into cells CL. The heat treatment has the function of recovering the work-affected layer 30 formed by mechanical damage. Therefore, when the scintillator 11 is made of "GOS" ceramic, the work-affected layer 30 formed on the surface of the cell CL can be recovered by heat treatment after singulation into the cells CL. You can. As a result, when the scintillator 11 is made of "GOS" ceramic, the work-affected layer 30 is reduced by the heat treatment.

On the other hand, "resin GOS" is not ceramics, but "GOS" powder solidified with resin, and it is difficult to heat-treat it. As a result, when the scintillator 11 is made of "resin GOS", the effect of recovering the work-affected layer 30 by heat treatment cannot be obtained. In other words, unlike the "GOS" ceramic, the "resin GOS" is difficult to heat-treat and cannot restore the work-affected layer 30, which is the second cause of the decrease in the light output from the scintillator structure 10A.

From the above, when the scintillator 11 is composed of the "resin GOS", the first cause resulting from the use of the "GOS" powder and the second cause of the difficulty in recovering the work-affected layer 30 are combined. , the luminous output is lower than that of the "GOS" ceramic.

Therefore, when the "resin GOS" is used as the scintillator 11, it is inevitable that the luminescence output is essentially lower than that of the "GOS" ceramic. However, the inventor of the present invention has obtained a new finding that, when the "resin GOS" is used as the scintillator 11, the light emission output changes depending on the thickness and density of the cells CL made of the "resin GOS." In other words, according to the new knowledge found by the present inventors, it is considered that by defining the thickness and density of the cells CL, it is possible to ensure a certain level of light emission output even with the "resin GOS."

Therefore, the thickness dependence and density dependence of the light emission output will be described below.

<Thickness dependence of light emission output>
FIG. 3 is a graph showing the relationship between cell thickness and luminous output.

In FIG. 3, the horizontal axis indicates the thickness of the cell, and the vertical axis indicates the light emission output.

First, the "first GOS" is "GOS" to which praseodymium (Pr) and cerium (Ce) are added. On the other hand, although not shown in FIG. 3, the "second GOS" is "GOS" to which terbium (Tb) and cerium (Ce) are added.

Here, focusing on the light output of the "first GOS" and the "second GOS", the light output of the "second GOS" is higher than that of the "first GOS". In other words, the "first GOS" has a lower light emission output than the "second GOS". The luminous output shown on the vertical axis of FIG. 3 is expressed in percent, with the luminous output of the "first GOS" having a thickness of 1.3 mm being 100%.

The "second resin GOS" is a mixture of "GOS" powder consisting of "second GOS" and epoxy resin.

Both the "third resin GOS" and the "fourth resin GOS" are mixtures of the "GOS" powder composed of the "first GOS" and the epoxy resin, and the "third resin GOS" and the "fourth resin GOS" The difference is density.

Focusing on the "first GOS" curve in FIG. 3, it can be seen that the light emission output of the "first GOS" hardly depends on the thickness of the cell. On the other hand, in FIG. 3, focusing on the respective curves of the “second resin GOS” to “fourth resin GOS”, the light emission output of each of the “second resin GOS” to “fourth resin GOS” varies depending on the thickness of the cell. It turns out that it depends on

In the following, the thickness dependence of the light emission output of each of the "second resin GOS" to "fourth resin GOS" will be qualitatively described. First, in the range where the thickness is thin, the luminous output increases as the thickness increases. This can be understood from the fact that, in the range where the thickness is thin, the amount of "resin GOS" that contributes to absorbing incident X-rays and generating visible light increases as the thickness increases. When the thickness increases to a certain extent, the amount of "resin GOS" that contributes to absorbing incident X-rays and generating visible light saturates. , it is understood that the luminous output decreases as the thickness increases due to the emergence of the first and second causes described above.

<Density dependence of light emission output>
Next, density dependence of light emission output will be described.

FIG. 4 is a graph showing the relationship between the density of the cells themselves and the luminous output.

In FIG. 4, the horizontal axis indicates the density of the scintillators forming the cell, and the vertical axis indicates the light emission output. The luminous output on the vertical axis is expressed in percentage, with the luminous output of the "first GOS" having a thickness of 1.5 mm being 100%.

Here, "density" refers to the density of the entire "resin GOS". In particular, in the "resin GOS", the density of the "GOS" powder is higher than that of the epoxy resin, so the following relationship holds.

That is, a low density of "resin GOS" means a low amount of "GOS" powder and a high amount of epoxy resin. In other words, a high density of "resin GOS" means a high amount of "GOS" powder and a low amount of epoxy resin.

In FIG. 4, the density of the "first resin GOS" (comparative example) is 5.0 (g/cm ³ ), while the density of the "second resin GOS" is 4.4 (g/cm ³ ). is. That is, the density of the "second resin GOS" is lower than the density of the "first resin GOS". In other words, the density of the "first resin GOS" is higher than the density of the "second resin GOS".

As shown in FIG. 4, the lower the density, the higher the luminous output. This is because the lower density means a relatively larger amount of epoxy resin with higher translucency than the "GOS" powder, thus reducing the absorption of visible light, resulting in a higher density. It is considered that the lower the value, the higher the light emission output. In other words, a higher density means that the amount of "GOS" powder is greater than the amount of highly translucent epoxy resin, thus increasing the absorption of visible light in the "GOS" powder. As a result, it is thought that the higher the density, the lower the luminous output.

In the following, by constructing the scintillator 11 from the "resin GOS", the thickness dependence of the light emission output described above (see FIG. ) and the density dependence of the light emission output (FIG. 4), the devised points for improving the performance of the scintillator structure 10A will be described. In other words, devised points for improving the cost performance of the scintillator structure 10A will be described.

Specifically, as points of improvement for improving the performance of the scintillator structure 10A, a first point of improvement from the viewpoint of ensuring light emission output and a second point of improvement from the viewpoint of ensuring afterglow characteristics will be described. to decide.

<Viewpoint of ensuring light emission output (first ingenuity point)>
As shown in FIG. 3, looking at the thickness dependence of the light emission output of the "second resin GOS", for example, when the thickness is 0.5 mm or more and 1.8 mm or less, the thickness of the "second resin GOS" The luminous output is higher than that of the "first GOS". In other words, the "second resin GOS" formed by mixing epoxy resin with the "GOS" powder composed of the "second GOS" having a higher light emission output than the "first GOS" has a light emission output higher than that of the "second GOS". It can be seen that the light emission output can be made higher than that of the "first GOS" by setting the thickness of the cell within the range of 0.5 mm or more and 1.8 mm or less, although it is lowered. In other words, if the thickness of the cell composed of the "second resin GOS" is set in the range of 0.5 mm or more and 1.8 mm or less, the light emission output of the "second resin GOS" can be made equal to or greater than that of the "first GOS". It is possible.

Next, as shown in FIG. 4, it can be seen that the luminous output increases as the cell density decreases. In particular, by setting the density in the range of 4.4 g/cm ³ or more and less than 5.0 g/cm ³ , when the light emission output of the "first GOS" with a thickness of 1.5 mm is "100 percent", " It can be seen that a light emission output of 125 percent or more can be obtained.

From the above, it is assumed that the scintillator 11 is made of "resin GOS" obtained by mixing "GOS" powder made of "second GOS" with epoxy resin, and the thickness of the cell is set to 0.5 mm or more and 1.8 mm. By setting the density of the cell itself to the range of 4.4 g/cm ³ or more and less than 5.0 g/cm ³ , the luminous output of the "resin GOS" is equal to or higher than that of the "first GOS". Obtainable. In this way, by setting the thickness range and the density range to the ranges described above while using the "resin GOS" that can reduce the manufacturing cost, it is possible to obtain a light emission output equal to or greater than the "first GOS". of. That is, in order to secure the light output while using the "resin GOS" which can reduce the manufacturing cost, the thickness of the cell should be set in the range of 0.5 mm or more and 1.8 mm or less, and the density of the cell itself should be increased. It can be realized by setting the range of 4.4 g/cm ³ or more and less than 5.0 g/cm ³ .

<Viewpoint of securing afterglow characteristics (second device point)>
The first contrivance point mentioned above is a contrivance point from the viewpoint of ensuring the light emission output. On the other hand, the second devised point to be described below is a devised point from the viewpoint of ensuring the afterglow characteristics. That is, the performance of the scintillator structure 10A is required not only to have a large light emission output but also to have good afterglow characteristics. Therefore, first, the afterglow characteristic will be described.

The scintillator 11 forming the scintillator structure 10A is a material that generates visible light when exposed to X-rays. The mechanism by which the scintillator 11 generates visible light when exposed to X-rays is as follows. That is, when the scintillator 11 is irradiated with X-rays, electrons in the scintillator 11 receive energy from the X-rays and transition from a low-energy ground state to a high-energy excited state. Then, the electrons in the excited state transition to the ground state with low energy. At this time, most of the excited electrons immediately transition to the ground state. On the other hand, some of the excited electrons transition to the ground state after a certain amount of time has passed. After a certain amount of time has passed, the visible light generated by the transition from the excited state to the ground state of electrons becomes afterglow. In other words, afterglow is visible light that occurs when a certain amount of time elapses after the timing of the transition from the excited state to the ground state after the X-ray irradiation. A large afterglow means that the intensity of the visible light generated until a certain amount of time has passed after the irradiation of X-rays is high. In this case, the afterglow generated by the previous X-ray irradiation remains until the next X-ray irradiation, and the remaining afterglow becomes noise. For this reason, it is desirable that the afterglow is small. In other words, good afterglow characteristics mean that the afterglow is small.

Here, afterglow characteristics differ depending on the type of scintillator 11 . For example, FIG. 5 is a graph showing afterglow characteristics of "CWO", and FIG. 6 is a graph showing afterglow characteristics of "third resin GOS". FIG. 7 is a graph showing the afterglow characteristics of the "first resin GOS".

5 to 7, the vertical axis indicates the intensity of afterglow, while the horizontal axis indicates time. 5 to 7 show that the afterglow characteristic is worse as the afterglow intensity increases after the passage of time. In other words, in FIGS. 5 to 7, the smaller the afterglow intensity after the passage of time, the better the afterglow characteristics.

Focusing on this point, looking at FIGS. 5 to 7, the afterglow characteristics of FIG. 5 and the afterglow characteristics of FIG. 6 are almost the same, and the afterglow characteristics are good, while the afterglow characteristics of FIG. 7 are poor. I understand. That is, the afterglow characteristics of "CWO" shown in FIG. 5 and the afterglow characteristics of "third resin GOS" shown in FIG. 6 are both good, while the afterglow characteristics of "first resin GOS" shown in FIG. is known to be bad.

In other words, from the viewpoint of light emission output, if the above-described device point 1 is realized, "second GOS" > "second resin GOS" > "first resin GOS" > "first GOS" > "fourth resin GOS" > " There is a region where the relationship of "third resin GOS">"CWO" is established.

On the other hand, referring to FIGS. 5 to 7, from the viewpoint of afterglow characteristics, a relationship of “CWO”≈“third resin GOS”<“first resin GOS” holds.

Therefore, for example, focusing on the "first resin GOS", the "third resin GOS", and "CWO", the "first resin GOS" is the most superior from the viewpoint of light output. On the other hand, from the viewpoint of afterglow characteristics, "CWO" and "third resin GOS" are superior.

For this reason, in order to realize a "resin GOS" with excellent afterglow characteristics, it is necessary to use a "first resin GOS" or a "second resin GOS", which is obtained by mixing an epoxy resin with a "GOS" powder composed of a "second GOS". is more desirable than "GOS" powder composed of "first GOS" and epoxy resin mixed with "third resin GOS" and "fourth resin GOS". However, as shown in FIG. 3, the "third resin GOS" and the "fourth resin GOS" have lower light output than the "second resin GOS".

Therefore, it is desirable to use the "third resin GOS" or the "fourth resin GOS" to ensure the afterglow characteristics while increasing the light emission output as much as possible. Regarding this point, in FIG. 3, on the premise that the "resin GOS" obtained by mixing the "GOS" powder composed of the "first GOS" with an epoxy resin is used, the thickness of the cell is set to 0.3 mm or more and 2.5 mm or less. , and by analogy with FIG. 4, the density of the cell itself is set in the range of 4.4 g/cm ³ or more and 5.0 g/cm ³ or less. It is considered that a light emission output equal to or higher than "CWO" can be obtained. In this way, while using the "resin GOS" which can reduce the manufacturing cost and has a good afterglow characteristic, by setting the thickness range and the density range to the above-mentioned ranges, it is possible to emit light of "CWO" or more. can get the output. That is, in order to reduce the manufacturing cost and secure the light output while using the "resin GOS" with good afterglow characteristics, the thickness of the cell is set in the range of 0.3 mm or more and 2.5 mm or less, Moreover, it can be realized by setting the density of the cell itself in the range of 4.4 g/cm ³ or more and 5.0 g/cm ³ or less.

<Manufacturing method of scintillator structure>
Next, a method for manufacturing the scintillator structure 10 will be described.

FIG. 8 is a flow chart explaining the flow of the manufacturing process of the scintillator structure.

In FIG. 8, first, after weighing and mixing predetermined amounts of raw material powder and flux components (S101), this mixture is filled in a crucible and fired in an air furnace at 1300° C. to 1400° C. for 7 to 9 hours. (S102), generating "GOS" powder; Then, flux components and impurities contained in the "GOS" powder are removed by washing using hydrochloric acid and hot water (S103). Next, the "GOS" powder is impregnated with the epoxy resin by dripping the epoxy resin into the "GOS" powder (S104). Next, after curing the epoxy resin (S105), the epoxy resin not mixed with the "GOS" powder is removed (S106). Thereby, a scintillator made of "resin GOS" can be formed.

Subsequently, by dicing the substrate on which the scintillator is formed, the substrate is separated into a plurality of cells (S107). A plurality of singulated cells are rearranged (S108), and then coated with a reflective material so as to cover the plurality of cells (S109). Then, after the unnecessary portion of the scintillator structure 10A is cut (S110), the scintillator structure 10A that has passed the inspection is shipped (S111).

FIG. 9 is a diagram schematically showing the steps from the dicing step to the reflector coating step.

As shown in FIG. 9, by dicing the substrate WF on which the scintillator made of "resin GOS" is formed, the substrate WF is separated into a plurality of cells CL. Then, the plurality of singulated cells CL are rearranged in a line, for example. After that, an outer frame FR is arranged so as to enclose a plurality of cells CL rearranged in a line. Next, a reflector 12 made of, for example, an epoxy resin containing titanium oxide is applied so as to cover the plurality of cells CL arranged within the outer frame FR. After that, the outer frame FR is removed. Thus, the scintillator structure 10A is manufactured.

In FIG. 9, the line-shaped scintillator structure 10A using 1×n cells is described as an example, but the technical concept of the present embodiment is not limited to this. It can also be applied to an array-like (matrix-like) scintillator structure using n×n cells.

<Features of manufacturing method>
Next, the characteristics of the manufacturing method in this embodiment will be described.

A feature of the manufacturing method in this embodiment is that the substrate WF on which the scintillator 11 is formed is completely singulated into a plurality of cells CL by full-cut dicing, and then the plurality of singulated cells CL are reused. The scintillator structure 10A is manufactured by arranging and then coating the reflecting material 12 so as to cover the rearranged plurality of cells CL.

Thus, according to this embodiment, the spacing between cells can be freely adjusted.

For example, there is a technique of half-dicing the substrate WF on which the scintillator 11 is formed, applying the reflector 12, and then grinding the half-diced substrate WF to separate adjacent cells CL. According to this technique, since the interval between adjacent cells CL is determined by the cutting width of half dicing, it is possible to accurately determine the interval between adjacent cells CL. In other words, this technology cannot freely change the interval between the cells CL.

In this regard, for example, some users of X-ray detectors want to obtain high-definition X-ray images by arranging photodiodes, which are light-receiving elements, at high density, while others prefer to arrange photodiodes at low density. Some users want to acquire a wide range of X-ray images without high definition. In the former case, it is required to arrange the plurality of cells CL forming the scintillator structure 10A at high density corresponding to the photodiodes arranged at high density. In this case, the spacing between cells CL should be very small. For example, when the interval between cells CL is made smaller than the cutting width of half dicing, the technology using half dicing cannot cope with this. On the other hand, in the latter case as well, even if it is desired to make the interval between cells CL larger than the width of half dicing, the technology using half dicing cannot cope with this. As described above, in the technique using half dicing, since the interval between cells CL is uniformly determined by the shear width of half dicing, the interval between cells CL cannot be freely adjusted according to the user's request. .

In contrast, in the present embodiment, the substrate WF on which the scintillator 11 is formed is singulated into a plurality of cells CL by full-cut dicing instead of half dicing, and then the plurality of singulated cells CL are separated into cells CL. are rearranging. Thus, according to the present embodiment, when rearranging a plurality of cells CL, it is possible to freely set the interval between adjacent cells CL.

For this reason, according to the present embodiment, the interval between the cells CL can be made smaller or larger than the cutting width of dicing, so there is an advantage that the scintillator structure 10A can be flexibly manufactured to meet user needs. is obtained.

Furthermore, according to this embodiment, the following advantages can also be obtained. That is, in the technique using half dicing, the cells CL are finally separated by a grinding process.

Regarding this point, in the present embodiment, a plurality of cells CL are singulated by full-cut dicing. This eliminates the need for a grinding step for separating the plurality of cells CL in subsequent steps. This means that the grinding process for separating a plurality of cells CL can be reduced. As a result, the method for manufacturing the scintillator structure 10A according to the present embodiment also has the advantage of simplifying the manufacturing process.

<Viewpoint of improving adhesion (third device point)>
For example, the scintillator structure 10A, which is a finished product manufactured through the manufacturing process described above, is subjected to a constant temperature and high humidity test to ensure reliability.

Here, it was confirmed that when the scintillator structure 10A using the "resin GOS" for the scintillator 11 is subjected to the constant temperature and high humidity test, the rate of passing the constant temperature and high humidity test decreases. In this regard, the present inventors have newly discovered that the rate of passing the constant temperature and high humidity test decreases due to the decrease in the adhesion at the interface between the scintillator 11 made of "resin GOS" and the reflector 12. rice field. Therefore, in the present embodiment, from the viewpoint of improving the reliability of the scintillator structure 10A, measures are taken to improve the adhesion between the scintillator 11 made of "resin GOS" and the reflector 12. FIG. In the following, this devised point will be described.

<< new knowledge >>
First, the novel findings discovered by the inventors will be described.

The new knowledge discovered by the present inventors is that, before coating the reflecting material 12 so as to cover the scintillator 11 made of "resin GOS", if the surface of the "resin GOS" is subjected to surface treatment, the surface This is the knowledge that the adhesive force at the interface between the "resin GOS" and the reflector 12 differs depending on the type of treatment. According to the present invention, the reason for the difference in the adhesion force at the interface between the "resin GOS" and the reflecting material 12 is that the wettability of the reflecting material 12 changes depending on the type of surface treatment applied to the surface of the "resin GOS". one guesses. From this, it can be considered that the adhesive force at the interface between the "resin GOS" and the reflector 12 can be improved by applying a surface treatment that can improve the wettability with respect to the reflector 12 to the surface of the "resin GOS". That is, it is considered that the adhesive force at the interface between the “resin GOS” and the reflector 12 can be improved by forming a surface treatment layer on the surfaces of the plurality of cells CL that come into contact with the reflector 12 . For example, it is considered that adhesion can be improved by forming a surface treatment layer on at least the side surfaces and the top surface of each of the plurality of cells CL.

Therefore, wettability to epoxy resin was evaluated for various surface treatments.

FIG. 10 shows the wettability to the epoxy resin evaluated by comparing the contact angles when the epoxy resin is dropped on the surface of the "resin GOS" after various surface treatments have been applied to the surface of the "resin GOS". It is a graph which shows a result.

In FIG. 10, various surface treatments include non-treatment, IPA treatment (isopropyl alcohol treatment), titanium oxide liquid immersion treatment, and pure water cleaning treatment.

As shown in FIG. 10, it can be seen that the contact angle differs depending on the difference in surface treatment. This means that wettability varies depending on the type of surface treatment.

From the results shown in FIG. 10, it can be seen that the contact angle is the smallest when the epoxy resin is dropped on the surface of the "resin GOS" after the surface of the "resin GOS" is immersed in the titanium oxide solution. This means that the wettability to the epoxy resin is most improved by performing the titanium oxide liquid immersion treatment as the surface treatment.

Therefore, it is presumed that the adhesion strength at the interface between the "resin GOS" and the reflecting material 12 increases when the titanium oxide immersion treatment, which has the best wettability with epoxy resin, is performed. In other words, as shown in FIG. 11, when the titanium oxide immersion treatment is performed, titanium oxide adheres to the surface of the scintillator 11 made of "resin GOS", thereby improving wettability and bonding the scintillator 11 and the reflector 12 together. As a result of the increase in area, it is considered that the adhesion strength at the interface between the scintillator 11 made of "resin GOS" and the reflector 12 increases.

From the above, the points for improving the adhesion between the scintillator 11 made of "resin GOS" and the reflecting material 12 are: In contrast, the scintillator 11 is surface-treated to improve its wettability. Specifically, this ingenuity is realized by subjecting the surface of the scintillator 11 to a titanium oxide liquid immersion treatment before applying the reflecting material 12 so as to cover the scintillator 11 .

<<Verification of effect>>
In the following, before coating the reflecting material 12 so as to cover the scintillator 11 made of "resin GOS", the surface of the scintillator 11 is subjected to a titanium oxide liquid immersion treatment, so that the interface between the scintillator 11 and the reflecting material 12 is Verification results that prove that the adhesion strength is increased will be described.

The present inventors considered that it is possible to quantitatively compare the adhesion strength at the interface between the scintillator 11 and the reflector 12 by the breaking strength of the bending test. Since the force was evaluated, the evaluation result by this bending test will be described. Specifically, in the present embodiment, the adhesive force was evaluated by a bending test conforming to the three-point bending test specified in "JIS K7171". For example, in the figure shown in "JIS K7171", the load at which the sample breaks was measured under the conditions shown below.

Sample shape (length, thickness, width): 50mm x 6.2mm x 1.2mm
Tip radius of indenter (R ₁ ): 0.3 mm
Support base corner radius (R ₂ ): 0.3 mm
Test piece (sample) thickness (h): 6.2 mm
Test piece (sample) length (l): 50 mm
Distance between fulcrums (L): 10 mm

1. Preparation of samples FIG. 12(a) is a cross-sectional view schematically showing the preparation process of a sample to be evaluated by the bending test, and FIG. 12(b) is a schematic diagram of the preparation process of the sample to be evaluated by the bending test. is a top view shown in FIG.

As shown in FIG. 12(a), a scintillator structure 10A configured to cover a plurality of arranged scintillators 11 with a reflective material 12 is prepared, and the top surface of this scintillator structure 10A is ground. As shown in (b), a sample SP is produced by grinding two side surfaces (long sides) of the scintillator structure 10A.

Then, a constant temperature and high humidity test is performed on this sample SP. Here, a constant temperature and high humidity test is performed by immersing in hot water of 80° C. for 80 minutes. After that, the bending test is performed on the sample SP that has been subjected to the constant temperature and high humidity test.

2. Bending Test FIG. 13(a) is a cross-sectional view showing the bending test, and FIG. 13(b) is a top view showing the bending test. As shown in FIG. 13A, the tip of the indenter NL is brought into contact with the interface between the scintillator 11 and the reflective material, and as shown in FIG. It is arranged so as to be positioned at the center in the width direction.

In the bending test, an indenter NL is pressed against the sample SP from above to measure the breaking strength when the sample SP is broken. It can be said that the higher the breaking strength, the higher the adhesion at the interface between the scintillator 11 and the reflector 12 . That is, it is possible to evaluate the adhesion at the interface between the scintillator 11 and the reflector 12 based on the breaking strength measured by the bending test. The evaluation results will be described below.

The measuring device used in the bending test is composed of, for example, a driving machine (FGS-50V-L: manufactured by SHIMPO) and a tension meter (FGC-0.5: manufactured by SHIMPO). The sample used for measurement has three measurement points, and the breaking strength of the sample is evaluated by the average value of the three measurement points.

3. Evaluation Results FIG. 14 is a diagram showing the evaluation results of the bending test.

FIG. 14(a) is a table showing conditions of surface treatment applied to the scintillator structure 10A before forming the sample SP. In FIG. 14A, eight samples SP are produced by processing the scintillator structure 10A surface-treated under eight conditions. For example, "Condition 1" indicates a condition in which the reflecting material is applied after IPA treatment→titanium oxide liquid immersion treatment→pure water cleaning as the surface treatment. "Condition 2" indicates a condition in which the reflective material is applied without performing the surface treatment described above.

FIG. 14(b) is a graph showing the breaking strength measured by performing a bending test on the sample SP corresponding to each of "Condition 1" to "Condition 8". As shown in FIG. 14(b), it can be seen that the breaking strength of the sample SP subjected to the titanium oxide liquid immersion treatment as the surface treatment is high. Specifically, it can be seen that the breaking strength of the interface between the scintillator 11 and the reflector 12 is 900 gf or more in the sample SP subjected to the titanium oxide liquid immersion treatment.

From this evaluation result, before applying the reflecting material 12 so as to cover the scintillator 11 made of "resin GOS", the scintillator 11 and the reflecting material 12 were immersed in the titanium oxide liquid on the surface of the scintillator 11. It can be seen that it is supported that the adhesion force at the interface is increased.

From the viewpoint of improving the adhesion of the interface between the scintillator 11 and the reflector 12, the breaking strength of the interface is preferably 938 gf or more, more preferably 1059 gf or more, and 1182 gf or more. is desirable.

Although the invention made by the present inventor has been specifically described based on the embodiment, the invention is not limited to the above embodiment, and can be variously modified without departing from the gist of the invention. Needless to say.

REFERENCE SIGNS LIST 10 scintillator structure 10A scintillator structure 11 scintillator 11a phosphor 11b resin 20 light receiving element 30 damaged layer 100 X-ray detector CL cell FR outer frame NL indenter SP sample WF substrate

Claims (2)

multiple cells and
a reflector covering the plurality of cells;
A scintillator structure comprising:
each of the plurality of cells includes a resin and a phosphor,
The phosphor contains gadolinium oxysulfide,
The resin is an epoxy resin, the reflector contains an epoxy resin,
Breaking strength of an interface between each of the plurality of cells and the reflector is 900 gf or more .
The scintillator structure, wherein the breaking strength is measured without a light receiving element . The scintillator structure according to claim 1,
The scintillator structure, wherein each side surface of the plurality of cells is a work-affected layer.

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