WO2010140426A1 - 積層型ZnO系単結晶シンチレータおよびその製造方法 - Google Patents
積層型ZnO系単結晶シンチレータおよびその製造方法 Download PDFInfo
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- G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
- G01T1/16—Measuring radiation intensity
- G01T1/20—Measuring radiation intensity with scintillation detectors
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Definitions
- the present invention relates to a laminated ZnO single crystal used as a scintillator in a scintillation detector.
- FIG. 1 A typical scintillation detector configuration is shown in FIG. 1, when radiation enters the scintillation detector 100, fluorescence corresponding to the radiation incident on the scintillator crystal 110 is generated, and the radiation is detected by detecting this light with a photomultiplier tube or a semiconductor detector 120. Can do.
- a TOF (Time of Flight) method has been proposed as a candidate for the next generation scintillator device, and studies are proceeding mainly on fluorides.
- time resolution it is possible to improve resolution as the fluorescence lifetime is shorter, and BaF 2 has been considered to be closest to ideal.
- BaF 2 has a small light emission amount and a short emission wavelength, an expensive photomultiplier tube (PMT) having a quartz window is required, and a general-purpose PMT cannot be used.
- the scintillator fluorescence lifetime is short alternative to BaF 2, exciton emission scintillators wide bandgap compound semiconductor has been proposed. If a compound semiconductor such as ZnO or CdS is used as a scintillator, the fluorescence lifetime is short and the emission wavelength is 370 nm, so that a general-purpose PMT or semiconductor detector can be used.
- passive measuring devices emit light when radiation is detected in real time and can be converted into electrical signals, they can be used for early detection and quick response to radioactive contamination.
- the fluorescence lifetime is short, the emission wavelength is 370 to 380 nm, and a general-purpose PMT or semiconductor detector can be used.
- the fluorescence lifetime by X-ray excitation is as short as 0.11 nsec to 0.82 nsec.
- the scintillator materials described in these documents are polycrystalline. In the case of a polycrystal, there are cases where the emission intensity varies depending on the orientation of the microcrystals and the spatial resolution depends on the particle size. For high spatial resolution and efficient scintillator light emission, the scintillator is preferably a single crystal.
- Patent Document 2 International Publication No. 2007/094785, Non-Patent Document 2; Nuclear Instruments. and Methods in Physics Research A505 (2003) 82-84).
- the fluorescence lifetime is 0.6 nsec in the In-doped ZnO single crystal.
- the scintillator materials described in these documents are manufactured by the “High pressure-directing-melting-technique” method. In this method, high pressure and high temperature are required, the crystal growth cost is high, and a single crystal portion and a polycrystalline portion are mixed, so that the same defects as the polycrystalline body exist.
- Patent Document 3 International Publication No. 2005/114256 pamphlet, non-patent document. 3; New Administrative Agency for New Energy and Industrial Technology, 2005 Research Results Report “Development of ultra-high-speed scintillator single crystal materials for practical TOF detectors”).
- a hydrothermal synthesis method using a Pt internal autoclave is adopted as a ZnO single crystal growth method.
- this growth method is used, a large group III-doped ZnO single crystal having high crystallinity can be grown.
- the exciton light emission scintillator using ZnO or the like has a problem that the amount of light emission is small due to self-absorption. That is, in the exciton emission wavelength region, the crystal itself becomes an absorber, and thus the amount of scintillator emission is small particularly in a transmission type scintillator device.
- the amount of light emitted from the ZnO-based exciton light-emitting scintillator was only about 10 to 15% of Bi 4 Ge 3 O 12 (BGO), which is a general scintillator (Non-Patent Document 4; High Energy News Vol) 21 No. 2 41-50 2002).
- high-quality ZnO single crystals can be grown by using vapor phase growth methods such as laser pulse deposition (PLD), MBE, and MOCVD.
- the vapor deposition method has a low film formation rate and is 1 ⁇ m or more.
- the penetration depth is about 5 to 50 ⁇ m for an ⁇ -ray or an electron beam, and a sufficient thickness to block the ⁇ -ray or the electron beam with only a ZnO single crystal can be obtained in a short time by the vapor phase growth method. It had problems that could not grow.
- the present inventors have applied for a laminated body containing a ZnO-based semiconductor containing Mg (Patent Document 4; Japanese Patent Laid-Open No. 2008-230906).
- Patent Document 4 Japanese Patent Laid-Open No. 2008-230906
- ZnO-based single crystal laminates having different band gaps can be manufactured.
- the inventors of the present invention manufactured a ZnO-based semiconductor laminate having different band gaps, and formed a layer with a small band gap to a thickness that allows ionizing radiation such as ⁇ rays and electron beams to penetrate, thereby reducing the amount of light emission.
- the inventors have found that it can be greatly increased, and have reached the present invention.
- a stack of ZnO-based semiconductors having different band gaps is manufactured, and a light emission amount is reduced by making a layer having a small band gap into which ionizing radiation such as ⁇ rays and electron beams can penetrate. It is possible to provide a stacked ZnO-based single crystal scintillator greatly increased and a method for manufacturing the same.
- FIG. 1 shows a typical scintillation detector configuration.
- FIG. 2 shows a typical LPE (Liquid Phase Epitaxial: LPE) growth furnace used in the third to fifth embodiments of the present invention.
- FIG. 3 is a configuration diagram of the LPE growth furnace used in the examples.
- LPE Liquid Phase Epitaxial: LPE
- a compound semiconductor such as ZnO generates exciton light emission corresponding to the band gap when irradiated with ionizing radiation such as ⁇ -rays or electron beams.
- the band gap of ZnO alone is about 3.30 eV.
- Exciton emission itself is almost absorbed by ZnO itself and hardly transmitted to the opposite side of the surface irradiated with ionizing radiation. Therefore, the amount of light emitted from the scintillator is basically only the scintillator light in which the long wavelength component of the exciton light is transmitted to the opposite side of the irradiation surface, and the light amount of the exciton light emission type scintillator is relatively small. It will be.
- the present invention is not limited to this principle, the amount of scintillator emission is increased by relaxing this self-absorption.
- the first embodiment of the present invention is a laminated body of two or more layers of ZnO-based mixed crystals (Zn 1-xy Mg x Cd y ) O having different band gaps, and a ZnO-based mixed crystal having a smaller band gap.
- the layered ZnO-based single crystal, wherein the layer has an irradiation surface of ionizing radiation, has a thickness of 5 ⁇ m to 50 ⁇ m, and 0 ⁇ x ⁇ 0.145 and 0 ⁇ y ⁇ 0.07 It is a scintillator.
- the band gap can be controlled from 3.30 to 3.54 eV by making a mixed crystal of Zn and Mg as filed by the present inventors.
- the band gap can be controlled from 3.00 to 3.30 eV by making a mixed crystal of Zn and Cd (Non-patent Document 5; Appl. Phys. Lett. 78 1237 (2001)). Therefore, two or more layers of ZnO-based mixed crystal (Zn 1-xy Mg x Cd y ) O having different band gaps are formed, and ionizing radiation is emitted from the surface (irradiation surface) of the layer having a smaller band gap.
- Irradiation and irradiation with ionizing radiation Zn 1-xy Mg x Cd y
- the thickness of the O layer is set to 5 ⁇ m to 50 ⁇ m where ionizing radiation can penetrate, so that the ionizing radiation is absorbed by the layer having a small band gap and the scintillator Convert to light.
- the second and subsequent layers counted from the layer irradiated with ionizing radiation have a larger band gap than the layer where the scintillator light is generated (first layer), so that more scintillator light can be transmitted.
- the thickness of the layer irradiated with ionizing radiation is 5 ⁇ m to 50 ⁇ m, preferably 10 ⁇ m to 45 ⁇ m, and preferably 20 ⁇ m to 40 ⁇ m. If the thickness of the layer irradiated with ionizing radiation is less than 5 ⁇ m, the ionizing radiation penetrates to the second layer (or subsequent layers), and a part of the ionizing radiation generates scintillator light after the second layer. Become. However, since the scintillator light generated in the second and subsequent layers has a wavelength corresponding to the band gap of each layer in the second and subsequent layers, self-absorption occurs and the total light emission amount decreases, which is not preferable.
- the thickness of the layer irradiated with ionizing radiation exceeds 50 ⁇ m, all of the ionizing radiation is absorbed in the first layer, but the generated scintillator light travels through the first layer, so that self-absorption eventually occurs. Is not preferable.
- the number of laminated ZnO-based mixed crystal (Zn 1-xy Mg x Cd y ) O can be selected from three or more layers.
- the layers are laminated in order from the layer with the smallest band gap. Is preferable from the viewpoint of increasing the light emission amount.
- the equilibrium solid solution amount of MgO with respect to ZnO is 0 ⁇ x ⁇ 0.145.
- x exceeds 0.145, an MgO single phase precipitates, which is not preferable.
- the equilibrium solid solution amount of CdO with respect to ZnO is 0 ⁇ y ⁇ 0.07. If y exceeds 0.07, a CdO single phase precipitates, which is not preferable.
- a hydrothermally synthesized ZnO single crystal substrate supplied with high quality and large area is used as a seed crystal substrate, and a (Zn, Mg) O mixed crystal having a larger band gap than ZnO is grown on the substrate as a thick film. Then, by etching or polishing the hydrothermally synthesized ZnO single crystal used for the substrate, it is possible to manufacture ZnO single crystal laminates having different target band gaps.
- a (Zn, Cd) O mixed crystal having a smaller band gap than ZnO is grown on a hydrothermally synthesized ZnO single crystal substrate, and then the (Zn, Cd) O layer is etched or polished to a desired thickness. ZnO-based single crystal laminates having different target band gaps can be manufactured.
- Examples of the ionizing radiation applied to the laminated ZnO single crystal scintillator include ⁇ rays, ⁇ rays, electron beams, X rays, neutron rays, and the like.
- the second embodiment of the present invention is the multilayer ZnO-based single crystal scintillator containing one or more selected from the group consisting of Al, Ga, In, H, F, and lanthanoid.
- ZnO-based single crystals have n-type crystal defects such as interstitial zinc and oxygen vacancies, and when these crystal defects are irradiated with ionizing radiation such as ⁇ rays and electron beams, they are attenuated in the wavelength range of 450 to 600 nm. Luminescence with a long lifetime occurs. Such long-wavelength emission has a disadvantage that it impairs the stability of the radiation detection discrimination function because of its long fluorescence lifetime.
- an exciton-emitting ZnO single crystal that emits less light at 450 to 600 nm is manufactured. Can do. Only exciton luminescence, which has a short fluorescence lifetime when excited by ionizing radiation such as ⁇ -rays and electron beams, is dominant, and the emission component with a long fluorescence lifetime is reduced, enabling the radiation detection discrimination function to be stabilized. .
- the ZnO single crystal scintillator obtained in this embodiment can be applied to high-speed detectors such as ⁇ rays and electron beams.
- the third embodiment of the present invention is a laminated body of two or more layers of ZnO-based mixed crystals (Zn 1-xy Mg x Cd y ) O having different band gaps, and a ZnO-based mixed crystal having a smaller band gap.
- a laminated ZnO-based single crystal scintillator characterized in that the layer has an irradiation surface for ionizing radiation, has a thickness of 5 ⁇ m to 50 ⁇ m, and 0 ⁇ x ⁇ 0.145 and 0 ⁇ y ⁇ 0.07
- at least one layer of the laminate is directly brought into contact with a mixture / melt of ZnO, MgO and CdO as a solute and PbO and Bi 2 O 3 as a solvent, thereby bringing the substrate into contact with ZnO.
- a method for producing a stacked ZnO-based single crystal scintillator characterized in that it is produced by a liquid phase epitaxial growth method in which a mixed crystal (Zn 1-xy Mg x Cd y ) O is grown on a substrate .
- ZnO-based mixed crystal (Zn 1-xy Mg x Cd y ) O that precipitates in the supersaturated melt is grown on the substrate by the LPE method so that two or more layers of ZnO having different band gaps are formed. This is a method for producing a laminated body of a mixed crystal (Zn 1-xy Mg x Cd y ) O.
- the LPE method close to thermal equilibrium growth is used as the crystal growth method, and PbO and Bi 2 O 3 which are fluxes composed of elements having a large ionic radius that are difficult to be incorporated into the ZnO crystal are used.
- PbO and Bi 2 O 3 which are fluxes composed of elements having a large ionic radius that are difficult to be incorporated into the ZnO crystal are used.
- a high-quality ZnO single crystal with few impurities mixed in the crystal can be produced.
- a high-quality ZnO single crystal with reduced contamination of fluorine impurities can be produced.
- the laminated body of ZnO-based mixed crystal (Zn 1-xy Mg x Cd y ) O having two or more different band gaps obtained in this embodiment is applied to a detector such as a high-speed ⁇ -ray or electron beam. The amount of light emission can be increased.
- PbO or Bi 2 O 3 single solvent the liquid phase growth temperature becomes high, and therefore a mixed solvent of PbO and Bi 2 O 3 having the above mixing ratio is preferable.
- the “solute converted to only ZnO” is [ZnO (mol)] / ([ZnO (mol)] + [PbO (mol)] + [Bi 2 O 3 (mol)]).
- the fourth embodiment of the present invention is a laminated body of two or more layers of ZnO-based mixed crystals (Zn 1-xy Mg x Cd y ) O having different band gaps, and a ZnO-based mixed crystal having a smaller band gap.
- a laminated ZnO-based single crystal scintillator characterized in that the layer has an irradiation surface for ionizing radiation, has a thickness of 5 ⁇ m to 50 ⁇ m, and 0 ⁇ x ⁇ 0.145 and 0 ⁇ y ⁇ 0.07
- at least one layer of the laminate is directly brought into contact with a mixture / melt of ZnO, MgO and CdO as a solute and PbF 2 and PbO as a solvent, thereby obtaining a ZnO-based mixed material.
- a method for producing a stacked ZnO-based single crystal scintillator characterized by being produced by a liquid phase epitaxial growth method in which crystal (Zn 1-xy Mg x Cd y ) O is grown on a substrate.
- ZnO-based mixed crystal (Zn 1-xy Mg x Cd y ) O that precipitates in the supersaturated melt is grown on the substrate by the LPE method, and two or more ZnO-based mixed crystals having different band gaps are grown. This is a method for producing a crystal (Zn 1-xy Mg x Cd y ) O laminate.
- the mixing ratio of the solvent is within the above range, the evaporation amount of the solvent PbF 2 and PbO can be suppressed, and as a result, the fluctuation of the solute concentration is reduced, so that a ZnO-based mixed crystal single crystal is stably grown. be able to.
- ZnO-based mixed crystal (Zn 1-x-y Mg x Cd y) O ZnO-based mixed crystal having a composition different from the said ZnO-based mixed crystal as the substrate (Zn 1-x- y Mg x Cd y ) O is grown to produce a laminated body, and then the thickness of the ZnO-based mixed crystal layer having a smaller band gap is set to 5 ⁇ m to 50 ⁇ m by polishing or etching. This is a method for producing a ZnO-based single crystal scintillator.
- a hydrothermally synthesized ZnO single crystal substrate is used as a seed crystal substrate, and a (Zn, Mg) O mixed crystal having a larger band gap than that of ZnO is grown on the substrate as a thick film.
- a (Zn, Mg) O mixed crystal having a larger band gap than that of ZnO is grown on the substrate as a thick film.
- the hydrothermal synthesis substrate has a problem that light emission with a long fluorescence lifetime occurs in the range of 450 to 600 nm in the case of excitation using ⁇ rays or electron beams. Therefore, first, a (Zn 1-xy Mg x Cd y ) O layer is formed on the hydrothermal synthesis substrate by the method described in the first embodiment, and the hydrothermal synthesis substrate used for LPE growth is further etched. Alternatively, after complete removal by polishing, another (Zn 1-xy Mg x Cd y ) O layer having a different band gap may be formed using the LPE growth film as a substrate. At this time, the layer on which ionizing radiation such as ⁇ -rays or electron beams is incident can be doped with a group III element or a lanthanoid element to suppress generation of a long-wavelength light emitting component.
- a vapor phase growth method and a liquid phase growth method As a method for growing a ZnO single crystal, a vapor phase growth method and a liquid phase growth method have been used roughly.
- a vapor phase growth method chemical vapor transport method (see Japanese Patent Application Laid-Open No. 2004-131301), molecular beam epitaxy or metal organic vapor phase growth method (see Japanese Patent Application Laid-Open No. 2004-84001), sublimation method (Japanese Patent Application Laid-Open No. Hei 5). -70286, etc.) have been used, but there were many dislocations and defects, and the crystal quality was insufficient.
- the liquid phase growth method has the advantage that it is easier to manufacture high quality crystals than the vapor phase growth method because crystal growth proceeds in principle in thermal equilibrium.
- ZnO has a high melting point of about 1975 ° C. and easily evaporates, it has been difficult to grow a ZnO single crystal using the Czochralski method employed in silicon single crystals and the like. Therefore, as a method for growing the ZnO single crystal, the target substance is dissolved in a suitable solvent, the mixed solution is cooled to a saturated state, and the target substance is grown from the melt.
- a flux method, a floating zone method, a top seed solution growth (TSSG) method, a solution pulling method, an LPE growth method, and the like have been used.
- a liquid phase epitaxial method As a single crystal growth method of ZnO-based mixed crystal (Zn 1-xy Mg x Cd y ) O in the present invention, a liquid phase epitaxial method (LPE method), a flux method, a TSSG method, a solution pulling method, or the like is used. be able to.
- LPE method liquid phase epitaxial method
- a flux method As a method for growing ZnO-based mixed crystal (Zn 1-xy Mg x Cd y ) O, a relatively low cost and large area growth is possible.
- an LPE method that easily forms a functional layer structure is preferable.
- a ZnO-based mixed crystal (Zn 1-xy Mg x Cd y ) O single crystal is obtained using a ZnO single crystal produced by a hydrothermal synthesis method that has high crystallinity and can easily obtain a large-area substrate.
- a method (liquid phase homoepitaxial growth method) of growing the layer by the LPE method is suitable.
- FIG. 1 A typical LPE growth furnace used in the third to fifth embodiments of the present invention is shown in FIG.
- a platinum crucible 4 for melting a raw material and storing it as a melt is placed on a crucible base 9 made of mullite (alumina + silica).
- mullite alumina + silica
- three-stage side heaters (upper heater 1, central heater 2, lower heater 3) for heating and melting the raw material in the platinum crucible 4 are provided. .
- the outputs of the heaters are controlled independently, and the heating amount for the melt is adjusted independently.
- a mullite-made core tube 11 is provided between the heater and the inner wall of the manufacturing furnace, and a mullite-made furnace lid 12 is provided above the core tube 11.
- a pulling mechanism is provided above the platinum crucible 4.
- a pulling shaft 5 made of alumina is fixed to the pulling mechanism, and a substrate holder 6 and a substrate 7 fixed by the holder are provided at the tip thereof.
- a mechanism for rotating the shaft is provided on the upper portion of the pull-up shaft 5.
- alumina and mullite have been exclusively used for the crucible base 9, the core tube 11, the pull-up shaft 5 and the furnace lid 12 in the members constituting the LPE furnace. Therefore, in the temperature range of 700 to 1100 ° C., which is the LPE growth temperature and the raw material melting temperature, the Al component is volatilized from the alumina and mullite furnace materials, dissolved in the solvent, and mixed in the ZnO single crystal thin film. it is conceivable that.
- control of the group III doping amount is important. It is desirable to control the doping amount of the group III by the charged composition. Therefore, mixing the Al impurities into the LPE-grown ZnO single crystal thin film can be reduced by making the furnace material constituting the LPE furnace a non-Al material.
- a ZnO furnace material is optimal, but considering that it is not commercially available, MgO is suitable as a material that does not function as a carrier even when mixed in a ZnO thin film.
- a quartz furnace material is also preferable.
- calcium, silica, ZrO 2 and zircon (ZrO 2 + SiO 2 ), SiC, Si 3 N 4 and the like can be used.
- ZnO-based mixed crystal (Zn 1-xy Mg x Cd y ) O is used by using an LPE growth furnace composed of MgO and / or quartz as a non-Al-based furnace material. Manufacturing. And a crucible base for placing the crucible on the crucible, a core tube provided so as to surround the outer periphery of the crucible base, a furnace lid provided on the top of the core tube for opening and closing the furnace, and A mode in which a pulling shaft for raising and lowering the seed crystal or the substrate is provided, and these members are independently made of MgO or quartz is also preferable.
- ⁇ Other requirements suitable for the present invention control of LPE growth temperature, adjusting the solvent viscosity
- the third component include B 2 O 3 , P 2 O 5 , V 2 O 5 , MoO 3 , WO 3 , SiO 2 , MgO, and BaO.
- the solvent of the fourth embodiment of the present invention the Bi 2 O 3 as the third component may be added.
- the substrate used in the third to fifth embodiments of the present invention is not particularly limited as long as it has a crystal structure similar to ZnO and the grown thin film and the substrate do not react with each other.
- Preferably used for example, sapphire, LiGaO 2, LiAlO 2, LiNbO 3, LiTaO 3, ZnO or the like can be mentioned.
- the target single crystal in the present invention is ZnO, ZnO having a high degree of lattice matching between the substrate and the grown crystal is optimal.
- FIG. 1 The block diagram of the LPE growth furnace used in the Example is shown in FIG.
- a platinum crucible 4 for melting a raw material and storing it as a melt is provided on a crucible base 9 '.
- three-stage side heaters (upper heater 1, central heater 2, lower heater 3) for heating and melting the raw material in the platinum crucible 4. .
- the outputs of the heaters are controlled independently, and the heating amount for the melt is adjusted independently.
- a core tube 11 ′ is provided between the heater and the inner wall of the manufacturing furnace, and a furnace lid 12 ′ for opening and closing the inside of the furnace is provided above the core tube 11 ′.
- a pulling mechanism is provided above the platinum crucible 4.
- a pulling shaft 5 'made of quartz is fixed to the pulling mechanism, and a seed crystal or a substrate 7 fixed with the substrate holder 6 and the holder is provided at the tip thereof.
- a mechanism for rotating the pull-up shaft 5 ' is provided on the upper portion of the pull-up shaft 5' made of quartz.
- a thermocouple 10 for melting the raw material in the crucible is provided below the platinum crucible 4.
- the temperature of the production furnace is raised until the raw material is melted.
- the temperature is raised to 800 to 1100 ° C. and left for 2 to 3 hours to stabilize the raw material melt.
- the standing time may be shortened by stirring with a Pt stirring blade.
- an offset is applied to the three-stage heater, and the bottom of the crucible is adjusted to be several degrees higher than the melt surface.
- the substrate After adjusting the crucible bottom temperature to a seeding temperature of 700 to 950 ° C and stabilizing the melt temperature, rotate the substrate at 5 to 120 rpm and lower the pull-up shaft to bring the substrate into the melt surface. Wetted in contact with. After allowing the substrate to adjust to the melt, the temperature starts to decrease at a constant temperature or 0.025 to 1.0 ° C./hr, and the target Mg-containing (or Cd-containing) ZnO mixed single crystal is formed on the substrate surface. Grow. During the growth, the substrate is rotated at 5 to 300 rpm by the rotation of the pulling shaft, and is reversely rotated at regular intervals.
- the substrate After crystal growth over 30 minutes to 100 hours, the substrate is separated from the melt, and the melt component is separated by rotating the pulling shaft at a high speed of about 200 to 300 rpm. Thereafter, it is cooled to room temperature over 1 to 24 hours to obtain a target Mg-containing (or Cd-containing) ZnO mixed crystal single crystal thin film. Further, depending on the growth film thickness, it is possible to grow while pulling up the quartz axis with time or continuously.
- the crucible charged with the raw material was placed in the furnace shown in FIG. 3, held at a crucible bottom temperature of about 900 ° C. for 1 hour, and stirred and melted with a Pt stirring jig. Thereafter, the temperature is lowered until the bottom temperature of the crucible reaches about 808 ° C., and then contacted as a seed crystal with a ZnO single crystal substrate having a size of 10 mm ⁇ 10 mm ⁇ 0.5 mm in the + c plane orientation grown by a hydrothermal synthesis method, The substrate was grown for 48 hours at the same temperature while rotating the pulling shaft at 60 rpm. At this time, the shaft rotation direction was reversed every two minutes.
- the pulling-up shaft was raised to separate it from the melt, and the shaft was rotated at 100 rpm to shake off the melt components, and a colorless and transparent Zn 0.9 Mg 0.1 O single crystal film 250 ⁇ m was obtained. .
- the growth rate at this time was about 5.2 ⁇ m / hr.
- the band gap obtained from the PL emission wavelength of the obtained Zn 0.9 Mg 0.1 O was 3.46 eV.
- the (002) plane rocking curve half-width was 60 arcsec, confirming that the crystallinity was sufficiently high.
- the obtained Zn 0.9 Mg 0.1 O (250 ⁇ m) / hydrothermally synthesized ZnO substrate (500 ⁇ m) was lapped and polished to obtain Zn 0.9 Mg 0.1 O (220 ⁇ m) / hydrothermally synthesized ZnO. It processed into the ZnO type mixed crystal laminated body of a board
- BGO Bi 4 Ge 3 O 12
- the polishing amount on the hydrothermal synthesis substrate side is increased, and the thickness of the substrate is processed to 50 ⁇ m, 30 ⁇ m, 10 ⁇ m, 5 ⁇ m, and 3 ⁇ m (the laminates of Examples 1 to 4 and Comparative Example 2, respectively), and each time the scintillator is processed. Characteristic measurements were made.
- the amount of ⁇ -ray excited scintillator emission was measured.
- 241 Am was used as the ⁇ -ray source.
- PMT (R7600: manufactured by Hamamatsu Photonics) was used as a light receiving element, and five surfaces of the polished laminate were covered with Teflon tape so that scintillation light could be obtained from only one surface. At that time, a 1 mm square window was left for passing ⁇ -rays.
- a PMT was installed on the surface where the scintillation light was emitted, and a high voltage was applied to the PMT to amplify the signal and read out.
- the peak value was amplified by pre-amp, the waveform was adjusted by Pulse shape amp, the signal was obtained as a signal through a multi channel analyzer, and the amount of luminescence was obtained, and compared with BGO.
- the results are shown in Table 1.
- the emission amount when the ⁇ -ray is irradiated from the ZnO substrate surface of the Zn 0.9 Mg 0.1 O (220 ⁇ m) / hydrothermally synthesized ZnO substrate laminate is a ZnO substrate having a small band gap.
- the thickness of the substrate was 5 ⁇ m to 50 ⁇ m
- the light emission amount of the hydrothermal synthesis substrate alone of Comparative Example 3 exceeded the BGO ratio of 70% to 98%, and the light emission amount of the conventional ZnO scintillator could be increased.
- Comparative Example 1 when the thickness on the ZnO substrate side with a small band gap exceeds 50 ⁇ m, the light emission amount was comparable to that of the hydrothermal synthesis substrate.
- Comparative Example 2 where the thickness on the ZnO substrate side having a small band gap is smaller than 5 ⁇ m, the ⁇ ray penetrates the first layer, scintillator light emission occurs in the first layer and the second layer, and the emission amount distribution has two peaks. , Energy resolution decreased.
- Examples 5 to 8 Comparative Examples 4 to 6> A ZnO-based mixed crystal laminate in which the thickness of the hydrothermally synthesized ZnO substrate was changed by the same method as in Example 1 and the amount of light emitted when irradiated with an electron beam (acceleration voltage of 10 to several thousand V) is shown. It is shown in 2.
- the emission amount when the electron beam is irradiated from the ZnO substrate surface of the Zn 0.9 Mg 0.1 O (220 ⁇ m) / hydrothermally synthesized ZnO substrate is a ZnO substrate having a small band gap.
- the thickness of the substrate was 5 ⁇ m to 50 ⁇ m
- the light emission amount of the hydrothermal synthesis substrate alone of Comparative Example 6 exceeded the BGO ratio of 80% to 101%, and the light emission amount of the conventional ZnO scintillator could be increased.
- Comparative Example 4 when the thickness on the ZnO substrate side with a small band gap exceeds 50 ⁇ m, the amount of light emission was comparable to that of the hydrothermal synthesis substrate.
- Comparative Example 5 where the thickness on the ZnO substrate side having a small band gap is smaller than 5 ⁇ m, ⁇ rays penetrate the first layer, scintillator light emission occurs in the first layer and the second layer, and the light emission amount distribution has two peaks. , Energy resolution decreased.
- Examples 9 to 13 and Comparative Example 7 By the method according to Example 1, in this example, the thicknesses of the hydrothermally synthesized ZnO substrate layer (thickness: 30 ⁇ m) and the ZnO-based mixed crystal layer (thickness: 220 ⁇ m) are not changed, and the ZnO-based material has a large band gap. Only the band gap of the mixed crystal layer was changed. Table 3 shows the composition, band gap, and emission amount of each laminate.
- Examples 14 to 17 and Comparative Example 8> By the method according to Example 1, in this example, the thicknesses of the hydrothermally synthesized ZnO substrate layer (thickness: 500 ⁇ m) and the ZnO-based mixed crystal layer (thickness: 30 ⁇ m) are not changed, and the ZnO-based material has a small band gap. Only the band gap of the mixed crystal layer was changed. Table 4 shows the composition, band gap, and emission amount of each laminate.
- Example 18 After performing LPE growth of Zn 0.9 Mg 0.1 O on a hydrothermally synthesized ZnO substrate in the same manner as in Example 1, the hydrothermally synthesized ZnO substrate was completely removed by polishing, and a single Zn 0.9 was obtained. A Mg 0.1 O thin film was obtained. Next, this was done as the substrate, the LPE growth of the Ga-doped ZnO layer was 59ppm doped with Ga 2 O 3 with respect to ZnO. Then, polished again, to obtain a laminate of the Zn 0.9 Mg 0.1 O layer (220 .mu.m) / Ga-doped ZnO layer (30 [mu] m).
- the amount of light emitted when irradiated with ⁇ rays was 90% of the BGO ratio as in Example 1. Further, when the ⁇ -ray irradiation transmission spectrum of the laminate was measured, a long wavelength light emission component in the 450 to 600 nm region was hardly seen. From the above results, a ZnO-based laminate is formed, and the thickness of the layer irradiated with ionizing radiation such as ⁇ rays is set to 5 ⁇ m to 50 ⁇ m, so that the light emission amount when irradiated with ionizing radiation is about 90% in BGO ratio. Can be increased.
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Abstract
Description
本発明の第1の実施形態は、バンドギャップが異なる2層以上のZnO系混晶体(Zn1-x-yMgxCdy)Oの積層体であり、バンドギャップがより小さいZnO系混晶体層が、電離放射線の照射面を有しかつ5μm~50μmの厚みを有し、0≦x≦0.145、0≦y≦0.07であることを特徴とする、積層型ZnO系単結晶シンチレータである。
本発明の第2の実施形態は、Al、Ga、In、H、Fおよびランタノイドからなる群より選択される1以上を含有する、上記積層型ZnO系単結晶シンチレータである。
本発明の第3の実施形態は、バンドギャップが異なる2層以上のZnO系混晶体(Zn1-x-yMgxCdy)Oの積層体であり、バンドギャップがより小さいZnO系混晶体層が、電離放射線の照射面を有しかつ5μm~50μmの厚みを有し、0≦x≦0.145、0≦y≦0.07であることを特徴とする積層型ZnO系単結晶シンチレータの製造方法であって、前記積層体の少なくとも一層が、溶質であるZnO、MgOおよびCdOと溶媒であるPbOおよびBi2O3との混合・溶融物に、基板を直接接触させることにより、ZnO系混晶体(Zn1-x-yMgxCdy)Oを基板上に成長させる液相エピタキシャル成長法により作製されることを特徴とする、積層型ZnO系単結晶シンチレータの製造方法である。
本発明の第4の実施形態は、バンドギャップが異なる2層以上のZnO系混晶体(Zn1-x-yMgxCdy)Oの積層体であり、バンドギャップがより小さいZnO系混晶体層が、電離放射線の照射面を有しかつ5μm~50μmの厚みを有し、0≦x≦0.145、0≦y≦0.07であることを特徴とする積層型ZnO系単結晶シンチレータの製造方法であって、前記積層体の少なくとも一層が、溶質であるZnO、MgOおよびCdOと溶媒であるPbF2およびPbOとの混合・溶融物に、基板を直接接触させることにより、ZnO系混晶体(Zn1-x-yMgxCdy)Oを基板上に成長させる液相エピタキシャル成長法により作製されることを特徴とする、積層型ZnO系単結晶シンチレータの製造方法である。
本発明の第5の実施形態は、ZnO系混晶体(Zn1-x-yMgxCdy)Oを基板として該ZnO系混晶体とは異なる組成のZnO系混晶体(Zn1-x-yMgxCdy)Oを成長させることで積層体を製造した後、バンドギャップがより小さいZnO系混晶体層の厚みを研磨またはエッチングにより5μm~50μmとすることを特徴とする、上記積層型ZnO系単結晶シンチレータの製造方法である。
ZnO単結晶を成長させる方法としては、大別して気相成長法と液相成長法が用いられてきた。気相成長法としては、化学気相輸送法(特開2004-131301号公報参照)、分子線エピタキシーや有機金属気相成長法(特開2004-84001号公報参照)、昇華法(特開平5-70286号公報参照)などが用いられてきたが、転移、欠陥などが多く、結晶品質が不十分であった。
本発明の第3~5の実施形態において使用する一般的なLPE成長炉を図2に示す。LPE成長炉内には、原料を溶融し融液として収容する白金るつぼ4が、ムライト(アルミナ+シリカ)製のるつぼ台9の上に載置されている。白金るつぼ4の外側にあって側方には、白金るつぼ4内の原料を加熱して溶融する3段の側部ヒーター(上段ヒーター1、中央部ヒーター2、下段ヒーター3)が設けられている。ヒーターは、それらの出力が独立に制御され、融液に対する加熱量が独立して調整される。ヒーターと製造炉の内壁との間にムライト製の炉心管11が、炉心管11上部にはムライト製の炉蓋12が設けられている。白金るつぼ4の上方には引上げ機構が設けられている。引上げ機構にアルミナ製の引上軸5が固定され、その先端には、基板ホルダー6とホルダーで固定された基板7が設けられている。引上軸5上部には、軸を回転させる機構が設けられている
本発明の第3~5の実施形態において、ZnO溶解度やPbF2とPbOの蒸発量あるいはPbOとBi2O3の蒸発量が大きく変化しない範囲で、LPE成長温度の制御、溶媒粘性の調整を目的として、溶媒に第三成分を1種または2種以上添加することができる。例えば、第三成分としては、B2O3、P2O5、V2O5、MoO3、WO3、SiO2、MgO、BaOなどが挙げられる。また、本発明の第4の実施形態の溶媒に、第三成分としてBi2O3を添加してもよい。
実施例で用いたLPE成長炉の構成図を図3に示す。単結晶製造炉内には原料を溶融し融液として収容する白金るつぼ4がるつぼ台9’の上に設けられている。白金るつぼ4の外側にあって側方には、白金るつぼ4内の原料を加熱して溶融する3段の側部ヒーター(上段ヒーター1、中央部ヒーター2、下段ヒーター3)が設けられている。ヒーターは、それらの出力が独立に制御され、融液に対する加熱量が独立して調整される。ヒーターと製造炉の内壁との間には、炉心管11’が設けられ、炉心管11’の上部には炉内の開閉を行う炉蓋12’が設けられている。白金るつぼ4の上方には引上げ機構が設けられている。引上げ機構には石英製の引上軸5’が固定され、その先端には、基板ホルダー6とホルダーで固定された種結晶または基板7が設けられている。石英製の引上軸5’上部には、引上軸5’を回転させる機構が設けられている。白金るつぼ4の下方には、るつぼ内の原料を溶融するための熱電対10が設けられている。
以下の工程により、Zn0.9Mg0.1O単結晶を液相エピタキシャル成長法で作製した。
実施例1と同様の方法で水熱合成ZnO基板の厚みを変化させたZnO系混晶積層体を作製し、電子線(加速電圧数10~数千V)を照射したときの発光量を表2に示す。
実施例1に順ずる方法により、本実施例では水熱合成ZnO基板層(厚み:30μm)とZnO系混晶層(厚み:220μm)の各層の厚みは変化させず、バンドギャップが大きいZnO系混晶層のバンドギャップのみを変化させた。それぞれの積層体の組成、バンドギャップおよび発光量を表3に示す。
実施例1に順ずる方法により、本実施例では水熱合成ZnO基板層(厚み:500μm)とZnO系混晶層(厚み:30μm)の各層の厚みは変化させず、バンドギャップが小さいZnO系混晶層のバンドギャップのみを変化させた。それぞれの積層体の組成、バンドギャップおよび発光量を表4に示す。
実施例1と同様に水熱合成ZnO基板上でZn0.9Mg0.1OのLPE成長を行った後、水熱合成ZnO基板を研磨で完全に除去して、単独のZn0.9Mg0.1O薄膜を得た。次に、これを基板として、ZnOに対しGa2O3を59ppmドープしたGaドープZnO層のLPE成長を行った。その後、再度研磨を施し、Zn0.9Mg0.1O層(220μm)/GaドープZnO層(30μm)の積層体を得た。
2・・・中央部ヒーター
3・・・下段ヒーター
4・・・白金るつぼ
5・・・引上軸
6・・・基板ホルダー
7・・・基板
9・・・るつぼ台
11・・・炉心管
12・・・炉蓋
Claims (9)
- バンドギャップが異なる2層以上のZnO系混晶体(Zn1-x-yMgxCdy)Oの積層体であり、バンドギャップがより小さいZnO系混晶体層が、電離放射線の照射面を有しかつ5μm~50μmの厚みを有し、0≦x≦0.145、0≦y≦0.07であることを特徴とする、積層型ZnO系単結晶シンチレータ。
- 前記電離放射線がα線であることを特徴とする、請求項1に記載する積層型ZnO系単結晶シンチレータ。
- 前記電離放射線が電子線であることを特徴とする、請求項1に記載する積層型ZnO系単結晶シンチレータ。
- Al、Ga、In、H、Fおよびランタノイドからなる群より選択される1以上を含有する、請求項1から3のいずれかに記載する積層型ZnO系単結晶シンチレータ。
- バンドギャップが異なる2層以上のZnO系混晶体(Zn1-x-yMgxCdy)Oの積層体であり、バンドギャップがより小さいZnO系混晶体層が、電離放射線の照射面を有しかつ5μm~50μmの厚みを有し、0≦x≦0.145、0≦y≦0.07であることを特徴とする積層型ZnO系単結晶シンチレータの製造方法であって、
前記積層体の少なくとも一層が、溶質であるZnO、MgOおよびCdOと溶媒であるPbOおよびBi2O3との混合・溶融物に、基板を直接接触させることにより、ZnO系混晶体(Zn1-x-yMgxCdy)Oを基板上に成長させる液相エピタキシャル成長法により作製されることを特徴とする、積層型ZnO系単結晶シンチレータの製造方法。 - 前記溶質と溶媒との混合比が、ZnOのみに換算した溶質:溶媒=5~30mol%:95~70mol%であり、溶媒であるPbOとBi2O3との混合比がPbO:Bi2O3=0.1~95mol%:99.9~5mol%である、請求項5に記載する積層型ZnO系単結晶シンチレータの製造方法。
- バンドギャップが異なる2層以上のZnO系混晶体(Zn1-x-yMgxCdy)Oの積層体であり、バンドギャップがより小さいZnO系混晶体層が、電離放射線の照射面を有しかつ5μm~50μmの厚みを有し、0≦x≦0.145、0≦y≦0.07であることを特徴とする積層型ZnO系単結晶シンチレータの製造方法であって、
前記積層体の少なくとも一層が、溶質であるZnO、MgOおよびCdOと溶媒であるPbF2およびPbOとの混合・溶融物に、基板を直接接触させることにより、ZnO系混晶体(Zn1-x-yMgxCdy)Oを基板上に成長させる液相エピタキシャル成長法により作製されることを特徴とする、積層型ZnO系単結晶シンチレータの製造方法。 - 前記溶質と溶媒との混合比が、ZnOのみに換算した溶質:溶媒=2~20mol%:98~80mol%であり、溶媒であるPbF2とPbOとの混合比がPbF2:PbO=80~20mol%:20~80mol%である、請求項7に記載する積層型ZnO系単結晶シンチレータの製造方法。
- ZnO系混晶体(Zn1-x-yMgxCdy)Oを基板として該ZnO系混晶体とは異なる組成のZnO系混晶体(Zn1-x-yMgxCdy)Oを成長させることで積層体を製造した後、バンドギャップがより小さいZnO系混晶体層の厚みを研磨またはエッチングにより5μm~50μmとすることを特徴とする、請求項5から8のいずれかに記載する積層型ZnO系単結晶シンチレータの製造方法。
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JP2004131301A (ja) | 2002-10-08 | 2004-04-30 | National Institute For Materials Science | ZnO単結晶の育成炉と単結晶育成法 |
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JP2008230906A (ja) | 2007-03-20 | 2008-10-02 | Mitsubishi Gas Chem Co Inc | Mg含有ZnO系混晶単結晶、その積層体およびそれらの製造方法 |
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JP4431925B2 (ja) * | 2000-11-30 | 2010-03-17 | 信越半導体株式会社 | 発光素子の製造方法 |
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2009
- 2009-06-04 JP JP2009135468A patent/JP2010280826A/ja not_active Withdrawn
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2010
- 2010-03-30 TW TW099109526A patent/TW201043996A/zh unknown
- 2010-04-14 WO PCT/JP2010/056671 patent/WO2010140426A1/ja active Application Filing
- 2010-04-14 CN CN201080023985XA patent/CN102449105A/zh active Pending
- 2010-04-14 US US13/321,229 patent/US20120064314A1/en not_active Abandoned
- 2010-04-14 KR KR1020117029890A patent/KR20120023090A/ko not_active Application Discontinuation
- 2010-04-14 EP EP10783212A patent/EP2439250A4/en not_active Withdrawn
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JP2008230906A (ja) | 2007-03-20 | 2008-10-02 | Mitsubishi Gas Chem Co Inc | Mg含有ZnO系混晶単結晶、その積層体およびそれらの製造方法 |
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Also Published As
Publication number | Publication date |
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KR20120023090A (ko) | 2012-03-12 |
EP2439250A4 (en) | 2013-01-02 |
US20120064314A1 (en) | 2012-03-15 |
JP2010280826A (ja) | 2010-12-16 |
EP2439250A1 (en) | 2012-04-11 |
TW201043996A (en) | 2010-12-16 |
CN102449105A (zh) | 2012-05-09 |
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