Patent Grant
11728119
The present disclosure relates to a photocathode and a method for manufacturing a photocathode.
For example, a photocathode is constituted to include a photoelectric conversion layer on one surface side of a translucent substrate. In photocathodes, it is desired to perform linear detection covering a wide range from a very small quantity of light to a large quantity of light, that is, improve cathode linearity characteristics. Cathode linearity characteristics denote linearity when a cathode output current increases and decreases in proportion to increase and decrease of the quantity of incident light. In order to improve the cathode linearity characteristics, it is necessary to appropriately supply charges to a photoelectric conversion layer.
Regarding such technical problems, for example, a technique of providing an optically transparent conductive layer as a base between a translucent substrate and a photoelectric conversion layer to reduce a surface resistance of the photoelectric conversion layer has been researched. For example, in the photocathode described in Patent Literature 1, a constitution in which an intermediate layer made of graphite, carbon nanotubes, or the like is provided between a translucent substrate and a photoelectric conversion layer is disclosed.
Such a photocathode described above has diverse uses such as for a photoelectric tube, an image amplifier, a streak tube, and the like, in addition to a photomultiplier tube. Characteristics required for a photocathode vary widely in accordance with the use of an application target. For this reason, a technology in which a photocathode having desired characteristics can be easily obtained even when an optically transparent conductive layer is provided as a base between a translucent substrate and a photoelectric conversion layer has been desired.
The present disclosure has been made in order to solve the foregoing problems, and an object thereof is to provide a photocathode in which desired characteristics can be easily obtained even when an optically transparent conductive layer is provided as a base between a translucent substrate and a photoelectric conversion layer.
A photocathode according to an aspect of the present disclosure includes a translucent substrate having one surface on which light is incident and the other surface emitting the light incident through the one surface, a photoelectric conversion layer provided on the other surface of the translucent substrate and convert the light emitted through the other surface into photoelectrons, and an optically transparent conductive layer provided between the translucent substrate and the photoelectric conversion layer. The optically transparent conductive layer is formed of a constituent material including carbon. A Raman spectrum of the constituent material has a peak of a D1 band, a peak of a G band, a peak of a 2D1 band, and a peak of a (D1+G) band.
In this photocathode, the optically transparent conductive layer provided between the translucent substrate and the photoelectric conversion layer includes carbon as a constituent material, and the Raman spectrum of the constituent material has four peaks in the D1 band, the G band, the 2D1 band, and the (D1+G) band. In an optically transparent conductive layer formed of a constituent material having such a Raman spectrum, microscopically, it is conceivable that regions having different bonding states of carbon atoms are mixed so that optical transparency or an electrical resistance value varies depending on a disposition state of each region. Therefore, in this photocathode, optical transparency and electrical conductivity of the optically transparent conductive layer can be adjusted by adjusting the thickness of the optically transparent conductive layer, and thus desired characteristics can be easily obtained even when the optically transparent conductive layer is provided as a base between the translucent substrate and the photoelectric conversion layer.
A smallest value of a Raman intensity between the peak of the D1 band and the peak of the G band may be higher than a base value of a Raman intensity between the peak of the G band and the peak of the 2D1 band. In a photocathode including an optically transparent conductive layer having such a Raman spectrum, the foregoing constitution in which regions having different bonding states of carbon atoms are mixed can be more easily obtained, and adjustment of optical transparency and electrical conductivity is further facilitated.
A Raman intensity in the peak of the D1 band may be higher than a Raman intensity in the peak of the G band. In a photocathode including an optically transparent conductive layer having such a Raman spectrum, since the thickness of the optically transparent conductive layer is reduced, a photocathode having excellent optical transparency can be obtained.
A Raman intensity in the peak of the D1 band may be lower than the Raman intensity in the peak of the G band. In a photocathode including an optically transparent conductive layer having such a Raman spectrum, since the thickness of the optically transparent conductive layer is increased, adjustment of optical transparency and electrical conductivity is further facilitated.
A method for manufacturing a photocathode according to another aspect of the present disclosure is a method for manufacturing a photocathode, in which the foregoing photocathode is manufactured. The method for manufacturing a photocathode includes a step of disposing a translucent substrate inside a vapor deposition device, a step of forming an optically transparent conductive layer by introducing gas including carbon into the vapor deposition device and performing vapor deposition of a constituent material including carbon on the translucent substrate, and a step of forming a photoelectric conversion layer on the optically transparent conductive layer.
In this method for manufacturing a photocathode, an optically transparent conductive layer is formed on a translucent substrate through vapor deposition using gas including carbon. According to such a technique, in contrast to a technique in which a separately formed optically transparent conductive layer is transferred onto the translucent substrate, an optically transparent conductive layer can be easily formed through a step of simply performing vapor deposition using the vapor deposition device. In addition, the thickness of the optically transparent conductive layer can be easily adjusted by adjusting a vapor deposition time using the vapor deposition device, and thus desired characteristics can be easily obtained even when an optically transparent conductive layer is provided as a base between a translucent substrate and a photoelectric conversion layer.
A vapor deposition time for the constituent material may be 60 minutes or shorter. In this case, an optically transparent conductive layer having each of the peaks as described above can be favorably obtained.
According to the present disclosure, it is possible to easily obtain desired characteristics even when an optically transparent conductive layer is provided as a base between a translucent substrate and a photoelectric conversion layer.
Hereinafter, with reference to the drawings, preferred embodiments of a photocathode and a method for manufacturing a photocathode according to aspects of the present disclosure will be described in detail.
[Constitution of Photomultiplier Tube]
The photocathode 4 is a part performing photoelectric conversion of the incident light L due to a photoelectric effect and discharges photoelectrons toward the electron multiplier portion 3. The photocathode 4 is constituted to include a translucent substrate 21, a photoelectric conversion layer 24, and an optically transparent conductive layer 22 therebetween. For example, the photocathode 4 is joined to the side tube portion 5 by means of a joint member 23. However, regarding the photoelectric conversion layer 24, it is also formed on a part of an inner wall surface of the side tube portion 5. Details of the photocathode 4 will be described below.
The side tube portion 5 includes a first side tube portion 8 which mainly covers the electron multiplier portion 3 and a second side tube portion 9 which mainly covers the stein 6. An outward flange portion 8a is provided at a base end of the first side tube portion 8, and an inward flange portion 13 is provided at a tip of the first side tube portion 8. An outward flange portion 9a having the same diameter as a flange portion 8a is provided in the second side tube portion 9. The first side tube portion 8 and the second side tube portion 9 are firmly bonded to each other by airtightly joining the flange portions 8a and 9a to each other.
The electron multiplier portion 3 has a focusing electrode 10, dynodes 11, and an anode 12. The focusing electrode 10 is a flat plate-shaped electrode which is disposed between the photocathode 4 and the dynodes 11, focuses photoelectrons discharged from the photocathode 4 on the dynodes 11, and introduces the focused photoelectrons. The dynodes 11 are thin plate-shaped electrodes which have many electron multiplier holes and are disposed in a plurality of stages from the photocathode 4 side to the stein 6 side. The anode 12 is a flat plate-shaped electrode which takes out electrons multiplied by the electron multiplier portion 3 as an output signal. For example, the anode 12 is disposed in a stage one before the dynode 11 in the last stage.
When a predetermined voltage is applied to the electron multiplier portion 3 and the anode 12 via the stein pins 7, the photoelectric conversion layer 24 and the focusing electrode 10 have the same potential, and the potential in each stage of the dynodes 11 gradually increases from the photocathode 4 side toward the stein 6 side. When the incident light L is incident on the photoelectric conversion layer 24 from the translucent substrate 21 in this state, the incident light L is subjected to photoelectric conversion, and photoelectrons are discharged into the casing 2. Discharged photoelectrons are focused on the dynode 11 in the first stage by the focusing electrode 10 and are sequentially subjected to secondary electron multiplication by the dynodes 11 in each stage thereafter. A secondary electron group is discharged from the dynode 11 in the last stage. The secondary electron group is guided to the anode 12 and is output to the outside via the stein pins 7 (anode pins) connected to the anode 12.
In the embodiment, the photomultiplier tube 1 to which the photocathode 4 is applied has been described as an example, but the photocathode according to the present disclosure is not limited to a photomultiplier tube, which may be replaced by other electron tubes such as a photoelectric tube, an image amplifier, and a streak tube.
[Constitution of Photocathode]
For example, the translucent substrate 21 is formed of a glass material such as quartz glass or a crystalline material such as MgF2 into a disk shape and causes the incident light L to be incident inside the casing 2. The translucent substrate 21 has one surface 21a on which the incident light L is incident, and the other surface 21b which faces the one surface 21a and emits the incident light L toward the electron multiplier portion 3. The translucent substrate 21 is airtightly fixed to the inward flange portion 13 provided at the end of the side tube portion 5 by means of the joint member 23 on an outer surface side of the casing 2.
The optically transparent conductive layer 22 is a base layer of the photoelectric conversion layer 24 with respect to the translucent substrate 21 and is formed of a constituent material C including carbon (refer to
For example, the joint member 23 is made of an electrically conductive material such as aluminum. The joint member 23 is disposed such that a gap between a circumferential edge portion of the translucent substrate 21 and a circumferential edge portion of the optically transparent conductive layer 22, and the flange portion 13 is filled therewith. The joint member 23 serves as a practical fixing member with respect to the side tube portion 5 of the photocathode 4 and electrically connects the optically transparent conductive layer 22 to the side tube portion 5.
For example, the photoelectric conversion layer 24 is a multi-alkali photoelectric surface having a sensitivity to an infrared region. For example, the photoelectric conversion layer 24 is constituted to contain antimony (Sb), potassium (K), cesium (Cs), and the like. The photoelectric conversion layer 24 converts the incident light L which has been incident thereon through the translucent substrate 21 and the optically transparent conductive layer 22 into photoelectrons and emits converted photoelectrons toward the electron multiplier portion 3. The photoelectric conversion layer 24 is provided to cover an inner surface 13a of the flange portion 13 and a region exposed from the flange portion 13 on the other surface 22b of the optically transparent conductive layer 22 and to come into contact with inner circumferential edge portions of the joint member 23 and the flange portion 13.
[Constitution of Optically Transparent Conductive Layer]
Next, the foregoing optically transparent conductive layer 22 will be described in more detail.
In the optically transparent conductive layer 22, in addition to the regions G, as deformation regions 31, block-shaped parts 31a in which graphene structures remain, layer-shaped film structure flake boundaries 31b, opening parts 31c which are not covered by the constituent material C and through which the translucent substrate 21 is exposed, and the like are randomly present. In the block-shaped parts 31a, for example, graphene structures are present as certain blocks. In the layer-shaped film structure flake boundaries 31b which are discontinuous parts, for example, defects are formed due to torsion or segmentation of carbon bonding, and the opening parts 31c are formed due to torsion or segmentation thereof. The incident light L is transmitted mainly through the regions G and the opening parts 31c. In the present embodiment, particularly, optical transparency can be remarkably improved by including the opening parts 31c which have not been present in graphene structures in the related art. In the following description, for the sake convenience, a substance in the foregoing state will be referred to as “glassy carbon”.
In the present embodiment, the optically transparent conductive layer 22 is formed in the translucent substrate 21 by performing vapor deposition of glassy carbon in the translucent substrate 21 using a carbon supply material. For example, a vapor deposition time for glassy carbon is 60 minutes or shorter. The vapor deposition time for glassy carbon may be 30 minutes or shorter or may be 10 minutes or shorter. Generally, more opening parts 31c are observed as the vapor deposition time becomes shorter, and the surface area of the presence of the opening parts 31c also tends to increase. In this case, optical transparency is improved, and electrical conductivity is degraded. On the other hand, when the vapor deposition time becomes longer and growth of the two-dimensional layer-shaped films proceeds, the number of opening parts 31c decreases, and the surface area of the presence of the opening parts 31c tends to decrease. In this case, optical transparency is degraded, and electrical conductivity is improved. The states of the optically transparent conductive layer 22 illustrated in
In addition, the surface area of the presence of the regions G within a plane when the optically transparent conductive layer 22 is viewed in a thickness direction (a direction in which the one surface 22a and the other surface 22b are connected to each other) increases as the thickness of the optically transparent conductive layer 22 increases, and it decreases as the thickness of the optically transparent conductive layer 22 decreases. This denotes that the surface area of the presence of the opening parts 31c within a plane when the optically transparent conductive layer 22 is viewed in the thickness direction increases as the thickness of the optically transparent conductive layer 22 decreases, and it decreases as the thickness of the optically transparent conductive layer 22 increases. Therefore, it is ascertained that electrical conductivity and optical transparency have a trade-off relationship with respect to the thickness of the optically transparent conductive layer 22. As the thickness of the optically transparent conductive layer 22 increases, electrical conductivity of the optically transparent conductive layer 22 increases and optical transparency thereof decreases, and as the thickness of the optically transparent conductive layer 22 decreases, electrical conductivity of the optically transparent conductive layer 22 decreases and optical transparency thereof increases.
A Raman spectrum is a spectrum obtained by Raman spectroscopy, electron energy loss spectroscopy, or the like and is used for state analysis of a substance. A peak intensity of a Raman spectrum is an index for expressing polarizability and a state of orientation, and wave number information is an index for expressing a composition. In addition, a peak ratio is an index for expressing a relative ratio of each substance, a full width at half maximum of a peak is an index for expressing crystallinity or a defect/dope, and a peak shift is an index for expressing distortion, stress, a temperature, or the like.
The 2D1 band is a band derived from double scattering of a six-membered ring. A peak P3 of the 2D1 band corresponds to a 2 harmonic overtone of the D1 band and has strong frequency dependence with respect to excitation light as a result of a double resonance process in which a wave number vector of a phonon and an electron band structure are associated with each other. Similar to the peak P2 of the G band, the peak P3 of the 2D1 band tends to be broadened in accordance with increase in the number of layers. The (D1+G) band is a band derived from double scattering of the D1 band and the G band. A peak P4 of the (D1+G) band is positioned on a higher wave number side than the peak P3 of the 2D1 band and tends to be broadened in accordance with increase in the number of layers.
A range of presence of the peak in each band depends on an excitation wavelength of the Raman spectrum. For example, the D1 band is positioned within a range of 1,580 to 1,600 cm−1, and the G band is positioned within a range of 1,580 to 1,600 cm−1. For example, the 2D1 band is positioned within a range of 2,700 to 2,750 cm−1, and the (D1+G) band is positioned within a range of 2,930 to 3,000 cm−1. In the example of
As illustrated in
In the Raman spectra of glassy carbon, the peak P1 of the D1 band and the peak P2 of the G band appear more prominently than the peak P3 of the 2D1 band and the peak P4 of the (D1+G) band. As the vapor deposition time for forming glassy carbon becomes longer (the thickness of the optically transparent conductive layer 22 increases), the magnitude relationship between the peak intensity of the peak P1 of the D1 band and the peak intensity of the peak P2 of the G band gradually changes.
In the example of
The peak P3 of the 2D1 band and the peak P4 of the (D1+G) band are gradually broadened as the vapor deposition time for forming glassy carbon becomes longer, and the peak intensities thereof are also gradually degraded. The magnitude relationship between the peak intensity of the peak P3 of the 2D1 band and, the peak intensity of the peak P4 of the (D1+G) band does not change regardless of the vapor deposition time. In the example of
In addition, as illustrated in
[Method for Manufacturing Photocathode]
When the photocathode 4 having the constitution described above is manufactured, first, the translucent substrate 21 is prepared. For example, the translucent substrate 21 is washed using acetone and ethanol and is rinsed with water thereafter. Next, as illustrated in
Subsequently, carrier gas is introduced into the vapor deposition device 51 at a flow rate of approximately 180 sccm, the pressure is raised to approximately 10 Torr, and the temperature is raised to approximately 1,000° C. After the pressure and the temperature inside the vapor deposition device 51 are made stable, a carbon supply raw material which is a basic material of the constituent material C is introduced into the vapor deposition device 51 through a shower head 53 at a flow rate of approximately 1 sccm. Thereafter, the carbon supply raw material is kept on being supplied for approximately 10 minutes to 60 minutes, and glassy carbon is caused to grow on the other surface 21b of the translucent substrate 21 with a desired thickness. After glassy carbon having a desired thickness is caused to grow, supply of a carbon supply raw material is stopped, and the glassy carbon is cooled to room temperature by natural cooling. Accordingly, the optically transparent conductive layer 22 is formed on the other surface 21b of the translucent substrate 21.
Next, the translucent substrate 21 having the optically transparent conductive layer 22 formed therein is taken out from the vapor deposition device 51, and the optically transparent conductive layer 22 in the circumferential edge portion on the other surface 21b of the translucent substrate 21 is selectively removed. When the optically transparent conductive layer 22 is removed, for example, plasma irradiation of the optically transparent conductive layer 22 is performed in a state in which a circular mask having a smaller diameter than the translucent substrate 21 is disposed in a central part of the optically transparent conductive layer 22. Accordingly, in the optically transparent conductive layer 22, parts exposed through the mask are removed. As illustrated in
Subsequently, as illustrated in
In addition, on the inner surface 13a of the flange portion 13 and the other surface 22b of the optically transparent conductive layer 22, antimony is subjected to vapor deposition with respect to each of regions exposed through the flange portion 13, the joint member 23, and the inner circumferential edge portion of the flange portion 13. Thereafter, as illustrated in
[Operational Effects]
As described above, in the photocathode 4, the optically transparent conductive layer 22 provided between the translucent substrate 21 and the photoelectric conversion layer 24 includes carbon as the constituent material C, and the Raman spectrum of the constituent material C has four peaks in the D1 band, the G band, the 2D1 band, and the (D1+G) band. In the optically transparent conductive layer 22 formed of the constituent material C having such a Raman spectrum, microscopically, for example, it is conceivable that the block-shaped parts 31a in which the lattice structure of carbon atoms is retained, the layer-shaped film structure flake boundaries 31b in which the lattice structure of carbon atoms has a defect such as torsion or segmentation, and the like are mixed, and optical transparency or an electrical resistance value varies due to the state in which each of the deformation regions 31 is disposed. Therefore, in this photocathode 4, optical transparency and electrical conductivity of the optically transparent conductive layer 22 can be adjusted by adjusting the thickness of the optically transparent conductive layer 22, and even when the optically transparent conductive layer 22 is provided as a base between the translucent substrate 21 and the photoelectric conversion layer 24, desired characteristics can be easily obtained.
In the present embodiment, the smallest value R1 of the Raman intensity between the peak P1 of the D1 band and the peak P2 of the G band is larger than the base value R2 of the Raman intensity between the peak P2 of the G band and the peak P3 of the 2D1 band. In the optically transparent conductive layer 22 having such Raman spectra, a constitution in which the deformation regions 31 described above are mixed can be more easily obtained, and adjustment of optical transparency and electrical conductivity is further facilitated.
In the present embodiment, when the vapor deposition time for the constituent material C is relatively short, the Raman intensity in the peak P1 of the D1 band is higher than the Raman intensity in the peak P2 of the G band. In the photocathode 4 including the optically transparent conductive layer 22 having such Raman spectra, since the thickness of the optically transparent conductive layer 22 is decreased, the photocathode 4 having excellent optical transparency can be obtained. On the other hand, when the vapor deposition time for the constituent material C is relatively long, the Raman intensity in the peak P1 of the D1 band is lower than the Raman intensity in the peak P2 of the G band. In the photocathode 4 including the optically transparent conductive layer 22 having such Raman spectra, since the thickness of the optically transparent conductive layer 22 is increased, adjustment of optical transparency and electrical conductivity is further facilitated.
In a method for manufacturing the photocathode 4 according to the present embodiment, the optically transparent conductive layer 22 is formed on the translucent substrate 21 through vapor deposition using gas including carbon. According to such a technique, in contrast to a technique in which the separately formed optically transparent conductive layer 22 is transferred onto the translucent substrate 21, the optically transparent conductive layer 22 can be easily formed through a step of simply performing vapor deposition of the constituent material C using the vapor deposition device 51. In addition, the optically transparent conductive layer 22 can be uniformly formed even when there are somewhat irregularities in the translucent substrate 21, and the stable optically transparent conductive layer 22 can be formed even when the surface area increases. In addition, the thickness or the transmittance of the optically transparent conductive layer 22 can be easily adjusted by adjusting the vapor deposition time using the vapor deposition device 51, and even when the optically transparent conductive layer 22 is provided as a base between the translucent substrate 21 and the photoelectric conversion layer 24, desired characteristics can be easily obtained.
In the present embodiment, the vapor deposition time for the constituent material C is 60 minutes or shorter. In this case, it is possible to favorably obtain the optically transparent conductive layer 22 having each of the peaks described above.
[Evaluation Test Result of Photocathode]
The present disclosure is not limited to the foregoing embodiment. For example, regarding various manufacturing conditions in the method for manufacturing a photocathode, the flow rate, the time, and the like may be arbitrarily changed in accordance with the thickness of glassy carbon desired to be formed, the kind or the concentration of carbon supply raw material, or the like. In addition, a carbon supply raw material need only be gas containing carbon and may be a material other than ethanol. Examples of other carbon supply raw materials include alcohols (for example, methanol, propanol, and butanol), hydrocarbons (methane, ethane, propane, and butane), phenols, aldehydes, and ketones. In addition, vaporized gas (including those gasified through evaporation, sublimation, or dissolution of a solvent) thereof may be used.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-088003 | May 2020 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2021/015635 | 4/15/2021 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2021/235146 | 11/25/2021 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 6298179 | Nishikawa | Oct 2001 | B1 |
| 11062890 | Yamaguchi | Jul 2021 | B1 |
| 20230011913 | Henriksen | Jan 2023 | A1 |
| Number | Date | Country |
|---|---|---|
| 105514363 | Apr 2016 | CN |
| 2001-202873 | Jul 2001 | JP |
| 2019-523522 | Aug 2019 | JP |
| WO-2015064173 | May 2015 | WO |
| WO-2017207898 | Dec 2017 | WO |
| Entry |
|---|
| International Preliminary Report on Patentability dated Dec. 1, 2022 in WO Patent Application No. PCT/JP2021/015635. |
| Number | Date | Country | |
|---|---|---|---|
| 20230187161 A1 | Jun 2023 | US |
