Target for ultraviolet light generation, electron beam-excited ultraviolet light source, and production method for target for ultraviolet light generation
09728393 · 2017-08-08
Assignee
Inventors
- Yoshinori Honda (Hamamatsu, JP)
- Hiroyuki Taketomi (Hamamatsu, JP)
- Fumitsugu Fukuyo (Hamamatsu, JP)
- Koji Kawai (Hamamatsu, JP)
- Hidetsugu Takaoka (Hamamatsu, JP)
- Takashi Suzuki (Hamamatsu, JP)
Cpc classification
H01J63/06
ELECTRICITY
International classification
H01J63/06
ELECTRICITY
B05D5/06
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A target for ultraviolet light generation comprises a substrate adapted to transmit ultraviolet light therethrough and a light-emitting layer disposed on the substrate and generating ultraviolet light UV in response to an electron beam. The light-emitting layer includes a powdery or granular rare-earth-containing aluminum garnet crystal doped with an activator. The light-emitting layer has an ultraviolet light emission peak wavelength of 300 nm or shorter.
Claims
1. A target for ultraviolet light generation comprising: a substrate adapted to transmit ultraviolet light therethrough; and a light-emitting layer disposed on the substrate and generating ultraviolet light in response to an electron beam; wherein the light-emitting layer includes a powdery or granular rare-earth-containing aluminum garnet crystal doped with an activator, the light-emitting layer having an ultraviolet light emission peak wavelength of 300 nm or shorter.
2. A target for ultraviolet light generation according to claim 1, wherein the rare-earth-containing aluminum garnet crystal has a surface covered with a melted crystal layer resolidified after being melted by heat treatment.
3. A target for ultraviolet light generation according to claim 2, wherein the melted crystal layer fuses the rare-earth-containing aluminum garnet crystals to each other and to the substrate.
4. A target for ultraviolet light generation according to claim 1, wherein the activator is a rare-earth element.
5. A target for ultraviolet light generation according to claim 1, wherein the rare-earth-containing aluminum garnet crystal is LuAG, the activator being at least one of Sc, La, and Bi.
6. A target for ultraviolet light generation according to claim 1, wherein the rare-earth-containing aluminum garnet crystal is YAG, the activator being at least one of Sc and La.
7. A target for ultraviolet light generation according to claim 1, wherein the light-emitting layer has a thickness of at least 0.5 μm but not more than 30 μm.
8. A target for ultraviolet light generation according to claim 1, wherein the rare-earth-containing aluminum garnet crystal has a median diameter of at least 0.5 μm but not more than 30 μm.
9. A target for ultraviolet light generation according to claim 1, wherein the substrate is constituted by sapphire, silica, or rock crystal.
10. An electron-beam-excited ultraviolet light source comprising: the target for ultraviolet light generation according to claim 1; and an electron source providing the target with the electron beam.
11. A method for manufacturing a target for ultraviolet light generation, the method comprising depositing a powdery or granular rare-earth-containing aluminum garnet crystal, doped with an activator, having an ultraviolet light emission peak wavelength of 300 nm or shorter on a substrate adapted to transmit ultraviolet light therethrough and heat-treating the rare-earth-containing aluminum garnet crystal, so as to melt and then resolidify a surface of the rare-earth-containing aluminum garnet crystal to form a melted crystal layer.
12. A method for manufacturing a target according to claim 11, wherein the heat-treatment temperature is at least 1400° C. but not higher than 2000° C.
Description
BRIEF DESCRIPTION OF DRAWINGS
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)
(14)
(15)
(16)
(17)
(18)
(19)
(20)
(21)
(22)
(23)
(24)
(25)
(26)
(27)
(28)
(29)
(30)
DESCRIPTION OF EMBODIMENTS
(31) In the following, embodiments of the target for ultraviolet light generation, electron-beam-excited ultraviolet light source, and method for manufacturing a target for ultraviolet light generation in accordance with one aspect of the present invention will be explained in detail with reference to the drawings. In the explanation of the drawings, the same constituents will be referred to with the same signs while omitting their overlapping descriptions.
(32)
(33) A target 20 for ultraviolet light generation is arranged on the lower end side within the envelope 11. The target 20 is set to the ground potential, for example, while a high negative voltage is applied from the power supply part 16 to the electron source 12. As a consequence, the target 20 is irradiated with the electron beam EB emitted from the electron source 12. The target 20 is excited in response to the electron beam EB and generates ultraviolet light UV having an ultraviolet light emission peak wavelength of 300 nm or shorter.
(34)
(35) The light-emitting layer 22 is excited in response to the electron beam EB illustrated in
(36)
(37) Here, the rare-earth-containing aluminum garnet crystal included in the light-emitting layer 22 may be any of a single crystal, a polycrystal, and their mixture. Different kinds of the rare-earth-containing aluminum garnet crystal (e.g., LuAG and YAG) may be mixed, and different kinds of activator (e.g., at least two of La, Sc, and Bi) may be mixed.
(38) As will be seen from examples to be explained later, the rare-earth-containing aluminum garnet crystal in the light-emitting layer 22 of this embodiment has a surface covered with a melted crystal layer resolidified after being melted by heat treatment. A preferred thickness of the light-emitting layer 22 is at least 0.5 μm but not more than 30 μm. A preferred median diameter of the light-emitting layer 22 is at least 0.5 μm but not more than 30 μm. The content of the activator included in the rare-earth-containing aluminum garnet crystal is preferably at least 0.05 atom % but not more than 2.0 atom %, more preferably at least 0.1 atom % but not more than 1.0 atom %.
(39) Effects obtained by this embodiment will now be explained. As will be seen from examples to be explained later, it has been found out that turning a rare-earth-containing aluminum garnet crystal into a powdery or granular form and shaping it into a film can remarkably enhance the ultraviolet light generation efficiency as compared with the case using a planar rare-earth-containing aluminum garnet crystal. Since the light-emitting layer 22 includes the powdery or granular rare-earth-containing aluminum garnet crystal doped with an activator, the target 20 of this embodiment can effectively enhance the ultraviolet light generation efficiency. Such effects seem to result from the fact that turning the rare-earth-containing aluminum garnet crystal doped with an activator into a powdery or granular form increases the reaction area between the rare-earth-containing aluminum garnet crystal and the electron beam and enhances the light extraction efficiency.
(40) Preferably, the rare-earth-containing aluminum garnet crystal has a surface covered with a melted crystal layer resolidified after being melted by heat treatment as in the target 20 in accordance with this embodiment. As will be seen from examples to be explained later, this fuses the rare-earth-containing aluminum garnet crystals to each other and the rare-earth-containing aluminum garnet crystal and the substrate 21 to each other, so as to enable the light-emitting layer 22 to attain sufficient mechanical strength without using binders, while enhancing the bonding strength between the light-emitting layer 22 and substrate 21, whereby the light-emitting layer 22 can be restrained from peeling.
(41) Since the light-emitting layer 22 of this embodiment can be formed by such a method as depositing a powdery or granular oxide crystal on the substrate 21, the target 20 having a large area can be made easily.
(42) The substrate 22 is preferably made of sapphire, silica, or rock crystal as in this embodiment. This enables the substrate 21 to transmit ultraviolet light therethrough and endure the temperature of heat treatment of the light-emitting layer 22.
(43) As in this embodiment, the rare-earth-containing aluminum garnet crystal may be LuAG, the activator being at least one of Sc, La, and Bi. Alternatively, the rare-earth-containing aluminum garnet crystal may be YAG, the activator being at least one of Sc and La. Any of these can favorably attain the light-emitting layer 22 having an ultraviolet light emission peak wavelength of 300 nm or shorter.
First Example
(44) The first example of the above-mentioned embodiment will now be explained. First, in this example, two sapphire substrates each having a diameter of 12 mm and a thickness of 2 mm were prepared. Subsequently, an La:LuAG monocrystalline substrate and an Sc:LuAG monocrystalline substrate were prepared, and these monocrystalline substrates were pulverized in a mortar, so as to turn La:LuAG and Sc:LuAG single crystals into a powdery or granular form. Then, the powdery or granular La:LuAG single crystal was deposited on one sapphire substrate by sedimentation, so as to form a light-emitting layer. The powdery or granular Sc:LuAG single crystal was deposited on the other sapphire substrate by sedimentation, so as to form another light-emitting layer. Thereafter, an organic film (nitrocellulose) was formed on these light-emitting layers, and an aluminum film was vapor-deposited on the organic film. Finally, each of the light-emitting layers was fired, so as to decompose and vaporize the organic film, thus yielding a structure in which the aluminum film was in contact with the light-emitting layer. The thickness of each light-emitting layer after firing was 10 μm.
(45)
(46) When planar La:LuAG and Sc:LuAG single crystals are irradiated with the same electron beam, the intensity at the ultraviolet light emission peak wavelength is about 0.2 (in the same unit as with
(47)
Second Example
(48) The second example of the above-mentioned embodiment will now be explained. This example will explain forming of a light-emitting layer with a binder and by heat treatment without binders.
(49) Forming of a Light-Emitting Layer with a Binder
(50) First, a sapphire substrate having a diameter of 12 mm and a thickness of 2 mm was prepared. Subsequently, a Pr:LuAG monocrystalline substrate, which was a rare-earth-containing aluminum garnet crystal doped with Pr as an activator, was prepared and pulverized in a mortar, so as to make a powdery or granular Pr:LuAG single crystal.
(51) Then, the powdery or granular Pr:LuAG single crystal, deionized water, and an aqueous potassium silicate (K.sub.2SiO.sub.3) solution and an aqueous barium acetate solution as binder materials were mixed, the mixture was applied onto the sapphire substrate, and the Pr:LuAG single crystal and binder materials were deposited on the sapphire substrate by sedimentation, so as to form a light-emitting layer. Subsequently, an organic film (nitrocellulose) was formed on the light-emitting layer, and an aluminum film was formed by vacuum vapor deposition on the organic film. Finally, the light-emitting layer was fired in the air at 350° C., so as to decompose and vaporize the organic film, thus yielding a structure in which the aluminum film was in contact with the light-emitting layer.
(52) Forming of a Light-Emitting Layer by Heat Treatment
(53) First, a sapphire substrate having a diameter of 12 mm and a thickness of 2 mm was prepared. Subsequently, four LuAG monocrystalline substrates respectively doped with Pr, Sc, La, and Bi as activators were prepared and pulverized in a mortar, so as to attain a powdery or granular form.
(54) Each of the powdery or granular LuAG single crystals containing Pr, Sc, La, and Bi as activators and a solvent (ethanol) were mixed, the resulting liquid mixture was applied onto the sapphire substrate, and then the solvent was dried. The powdery or granular single crystal was thus deposited on the sapphire substrate, so as to form a light-emitting layer. Subsequently, the light-emitting layer was heat-treated (at 1600° C.) in an atmosphere under reduced pressure. The heat treatment was performed in order to melt a surface of the powdery or granular single crystal and yield a structure in which crystal particles were fused to each other and to a surface of the sapphire substrate, thereby enhancing the adhesion of the light-emitting layer. Thereafter, an organic film (nitrocellulose) was formed on the light-emitting layer, and an aluminum film was formed by vacuum vapor deposition on the organic film. Finally, the light-emitting layer was fired in the air at 350° C., so as to decompose and vaporize the organic film, thus yielding a structure in which the aluminum film was in contact with the light-emitting layer.
(55)
(56) As illustrated in
(57) When formed by heat treatment, by contrast, the light-emitting layer contains no binder material, so that no binder material denatures and decomposes, whereby the transmittance for ultraviolet light seems to be maintained for a relatively long time. Therefore, it is desirable for the light-emitting layer to be formed by heat treatment.
(58)
(59)
(60) It is seen from
(61) The above-mentioned melted crystal layers also contribute to binding the crystal particles and the substrate to each other.
(62) It is seen from
(63) The heat treatment temperature for the light-emitting layer, which is 1600° C. in this example, is preferably at least 1400° C. and preferably not higher than 2000° C. The heat treatment temperature of at least 1400° C. makes it possible to form a melted crystal layer with a sufficient thickness on a crystal particle surface and enhance the adhesion between crystal particles and between the crystal particles and substrate, thereby effectively preventing the light-emitting layer from peeling upon electron beam irradiation. The heat treatment temperature not higher than 2000° C. can inhibit the crystal structure from changing, thereby preventing the light emission efficiency from lowering. It can also keep substrates (sapphire substrates in particular) from deforming.
(64) The effects concerning the mechanical strength mentioned above seem to be obtained likewise in rare-earth-containing aluminum garnet crystals doped with an activator similar to the Pr:LuAG single crystal, e.g., La:LuAG, Sc:LuAG, Bi:LuAG, La:YAG, and Sc:YAG single crystals.
Third Example
(65) The third example of the above-mentioned embodiment will now be explained. For studying influences of substrate materials of the target for ultraviolet light generation, a synthetic silica substrate and a sapphire substrate were prepared. As the synthetic silica substrate, a substrate having a diameter of 18.6 mm and a thickness of 1.2 mm was prepared. As the sapphire substrate, a substrate having a diameter of 18 mm and a thickness of 0.43 mm was prepared. On each of these substrates, a light-emitting layer including a powdery or granular Pr:LuAG single crystal and an aluminum film were made as in the first example.
(66)
(67) The above-mentioned effects in this example seem to be the same in rare-earth-containing aluminum garnet crystals doped with an activator similar to the Pr:LuAG single crystal, e.g., La:LuAG, Sc:LuAG, Bi:LuAG, La:YAG, and Sc:YAG single crystals.
Fourth Example
(68) The fourth example of the above-mentioned embodiment will now be explained. In this example, a target for ultraviolet light generation was made by the same method as with the first example, and an experiment concerning the relationship between the light-emitting layer thickness and the ultraviolet light peak intensity was performed. That is, powdery or granular Pr:LuAG crystals were deposited with various thicknesses so as to make light-emitting layers, the peak intensity of ultraviolet light generated upon irradiation of the light-emitting layers with an electron beam was measured, and then cross sections of the light-emitting layers were observed with SEM, so as to determine their thicknesses.
(69) Referring to
(70) The above-mentioned results in this example seem to be obtained likewise in rare-earth-containing aluminum garnet crystals doped with an activator similar to the Pr:LuAG single crystal, e.g., La:LuAG, Sc:LuAG, Bi:LuAG, La:YAG, and Sc:YAG single crystals.
Fifth Example
(71) The fifth example of the above-mentioned embodiment will now be explained. This example conducted an experiment concerning the relationship between the median diameter of a powdery or granular Pr:LuAG crystal contained in the light-emitting layer and the ultraviolet light peak intensity. That is, the powdery or granular Pr:LuAG crystal was deposited on a plurality of substrates, so as to make light-emitting layers, and the peak intensity of ultraviolet light generated upon irradiation of the light-emitting layers with an electron beam was measured. The median diameter of the Pr:LuAG crystal included in the light-emitting layer was measured with a particle size analyzer before deposition on the substrate.
(72) It is seen from
(73) The median diameter of the Pr:LuAG crystal is preferably 30 μm or less. The fact that the median diameter of the Pr:LuAG crystal is 30 μm or less can inhibit the Pr:LuAG crystal from peeling from the substrate when depositing the Pr:LuAG crystal on the substrate.
(74) The above-mentioned results in this example seem to be obtained likewise in rare-earth-containing aluminum garnet crystals doped with an activator similar to the Pr:LuAG single crystal, e.g., La:LuAG, Sc:LuAG, Bi:LuAE La:YAG, and Sc:YAG single crystals.
Sixth Example
(75) The sixth example of the above-mentioned embodiment will now be explained. First, in this example, a polycrystalline plate containing 0.7 atom % of Pr was made. Subsequently, this polycrystalline plate was pulverized in a mortar, so as to produce a powdery or granular Pr:LuAG polycrystal. Then, the powdery or granular Pr:LuAG polycrystal was deposited on a synthetic silica substrate by sedimentation, so as to form a light-emitting layer. Thereafter, an organic film (nitrocellulose) was formed on the light-emitting layer, and an aluminum film was vapor-deposited on the organic film. Finally, the light-emitting layer was fired, so as to decompose and vaporize the organic film, thus yielding a structure in which the aluminum film was in contact with the light-emitting layer. The thickness of the light-emitting layer after firing was 10 μm.
(76) Graph G51 in
(77) The above-mentioned results in this example seem to be obtained likewise in rare-earth-containing aluminum garnet crystals doped with an activator similar to the Pr:LuAG single crystal, e.g., La:LuAG, Sc:LuAG, Bi:LuAG, La:YAG, and Sc:YAG single crystals.
Seventh Example
(78) The seventh example of the above-mentioned embodiment will now be explained. This example performed an experiment concerning the light-emitting layer thickness and the ultraviolet light peak intensity when the powdery or granular Pr:LuAG crystal contained in the light-emitting layer had various median diameter values. That is, Pr:LuAG crystals having respective median diameters of 0.5 μm, 1.0 μm, 6.5 μm, and 30 μm were deposited, a plurality of light-emitting layers having different thicknesses were made at each median diameter, these light-emitting layers were irradiated with an electron beam, and the peak intensity of ultraviolet light generated thereby was measured. The median diameter of the Pr:LuAG crystal included in each light-emitting layer was measured with a particle size analyzer before deposition on the substrate.
(79)
(80) It is seen from
(81) As mentioned above, the decrease in light emission efficiency when the light-emitting layer becomes thicker is more remarkable as the median diameter of the Pr:LuAG crystal is smaller. This seems to result from the fact that the light-emitting layer lowers its transmittance for ultraviolet light as the number of stacked layers of Pr:LuAG crystal particles increases. At any median diameter, the light emission efficiency decreases when the thickness of the light-emitting layer becomes smaller than a certain value. This seems to result from the fact that the coverage of the substrate surface by the Pr:LuAG crystal decreases as the light-emitting layer becomes thinner. At any median diameter, the coverage at which the ultraviolet light peak intensity is the highest is 100%.
(82)
(83) The above-mentioned results in this example seem to be obtained likewise in rare-earth-containing aluminum garnet crystals doped with an activator similar to the Pr:LuAG single crystal, e.g., La:LuAG, Sc:LuAG, Bi:LuAG, La:YAG, and Sc:YAG single crystals.
(84) The target for ultraviolet light generation, electron-beam-excited ultraviolet light source, and method for manufacturing a target for ultraviolet light generation in accordance with one aspect of the present invention are not limited to the embodiment mentioned above, but can be modified in various ways. For example, the aluminum film, which is vapor-deposited on the light-emitting layer in each of the above-mentioned embodiment and examples, may be omitted. The aluminum film functions as an antistatic conductive film, for which conductive films made of materials other than aluminum may also be used.
INDUSTRIAL APPLICABILITY
(85) The target for ultraviolet light generation, electron-beam-excited ultraviolet light source, and method for manufacturing a target for ultraviolet light generation in accordance with one aspect of the present invention can enhance ultraviolet light generation efficiency.
REFERENCE SIGNS LIST
(86) 10: electron-beam-excited ultraviolet light source; 11: envelope; 12: electron source; 13: extraction electrode; 16: power supply part; 20: target for ultraviolet light generation; 21: substrate; 21a: principal surface; 21b: rear face; 22: light-emitting layer; 23: aluminum film; EB: electron beam; UV: ultraviolet light.