Beta-sialon phosphor, light-emitting member, and light-emitting device

Abstract

This beta-sialon phosphor contains europium in a solid solution, and is configured such that, in a spectrum of the beta-sialon phosphor as determined by FT-IR, the absorbance of the spectrum is converted to a KM value by the Coubella-Mongolian function, and when the KM value at a wavenumber of 3050 cm-1 is E, the KM value at a wavenumber of 3330 cm-1 is F, and the KM value at a wavenumber of 3500 cm-1 is G, the absorbance of the spectrum is calculated by the KM value at the wavenumber of 3500 cm-1. E, F and G satisfy 1.8 < F / E and 1.8 > G / E.

Description

Technical Field

[0001] This invention relates to a β-type silon phosphor, a light-emitting component, and a light-emitting device. Background Technology

[0002] Various developments have been made to date regarding β-type silon phosphors. One such technology is described, for example, in known patent document 1.

[0003] Patent Document 1, including claims 1, paragraph 0009, and Example 6, describes a method for manufacturing a β-type silane phosphor. This method involves mixing a first heat-treated product obtained by heat-treating a composition containing silicon nitride with an aqueous sodium hydroxide solution, performing a first hot alkaline treatment at 70°C for 3 hours in an atmosphere, and further performing a second hot alkaline treatment at 200°C in a nitrogen atmosphere for 2 hours. The silicon nitride comprises aluminum, oxygen atoms, and europium. Furthermore, in paragraph 0051 of Patent Document 1, the first temperature for the heating of the first hot alkaline treatment is described as 50°C or higher and 150°C or lower.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2017-110206 Summary of the Invention

[0007] However, the inventors' research has shown that there is room for improvement in the reliability of LED brightness when the LED is powered on (continuously lit) in a high temperature and high humidity environment, in the β-type silon phosphor obtained by the manufacturing method described in Patent Document 1.

[0008] The inventors conducted further research and the results are as follows:

[0009] It is believed that the presence ratio of Si-OH groups in the functional groups on the surface of β-type silon phosphors can be stably evaluated by using the KM value, which is obtained by converting the absorbance of FT-IR spectra through the Kubelka-Monk function.

[0010] Discovery, as an indicator, can be utilized

[0011] Having at least one of the following indicators (P1) and (P2), or

[0012] It has at least one of the following indicators (Q1) to (Q6).

[0013] (P1) E, F, and G satisfy 1.8 < F / E and 1.8 > G / E

[0014] (P2) E, F, and H satisfy 1.8 < F / E and 2.0 > H / E

[0015] (Q1) A and B satisfy 0.31 > B / A

[0016] (Q2) A and C satisfy 0.44 > C / A

[0017] (Q3) A and D satisfy 0.21 > D / A

[0018] (Q4) L, A, and C satisfy 1.4 < A / L and 0.81 > C / L

[0019] (Q5) L, A, and M satisfy 1.4 < A / L and 0.67 > M / L

[0020] (Q6) L, A, E, F satisfy 0.94> ((A / L) / (F / E))

[0021] Specifically, in the spectrum of the β-type silon phosphor obtained by FT-IR before 1000 hours of exposure at 85°C and 85% humidity, the absorbance of the spectrum was converted to KM values ​​using the Kuberka-Monk function, and the wavenumber was set to 3050 cm⁻¹. -1 Set the KM value to E and the wavenumber to 3330cm. -1 Set the KM value to F, and set the wave number to 3500cm. -1 Set the KM value to G, and set the wavenumber to 3530cm. -1 The KM value is set to H.

[0022] After 1000 hours of exposure at 85°C and 85% humidity, the absorbance of the β-type silon phosphor obtained by FT-IR was converted to KM values ​​using the Kuberka-Monk function, and the wavenumber was set to 3330 cm⁻¹. -1 Set the KM value to A, and set the wavenumber to 3550cm. -1 Set the KM value to B, and set the wave number to 3500cm. -1 Set the KM value to C, and set the wave number to 3600cm. -1 Set the KM value to D, and set the wavenumber to 3050cm. -1 Set the KM value to L, and set the wavenumber to 3530cm. -1 The KM value is set to M.

[0023] Further in-depth research revealed that by appropriately controlling the numerical range of each index, the reliability of LED brightness during LED power-on (continuous lighting) tests under high temperature and high humidity conditions using β-type silron phosphors can be improved, thus completing the invention of this application.

[0024] According to one aspect of the present invention, the following β-type silon phosphor, light-emitting component, and light-emitting device can be provided.

[0025] 1. A β-type silron phosphor, wherein europium is dissolved in its solid solution,

[0026] In the spectrum of this β-type silon phosphor obtained by FT-IR, the absorbance of the spectrum was converted to KM value using the Kuberka-Monk function, and the wavenumber was set to 3050 cm⁻¹. -1 Set the KM value to E and the wavenumber to 3330cm. -1 Set the KM value to F, and set the wave number to 3500cm. -1 Set the KM value to G, and set the wavenumber to 3530cm. -1 When the KM value is set to H,

[0027] It has at least one of the following (P1) and (P2):

[0028] (P1) E, F, and G satisfy 1.8 < F / E and 1.8 > G / E

[0029] (P2) E, F, and H satisfy 1.8 < F / E and 2.0 > H / E.

[0030] 2. A β-type silron phosphor, wherein europium is dissolved in its solid solution,

[0031] After 1000 hours of exposure at 85°C and 85% humidity, the absorbance of the β-type silon phosphor obtained by FT-IR was converted to KM values ​​using the Kuberka-Monk function, and the wavenumber was set to 3330 cm⁻¹. -1 Set the KM value to A, and set the wavenumber to 3550cm. -1 Set the KM value to B, and set the wave number to 3500cm. -1 Set the KM value to C, and set the wave number to 3600cm. -1 Set the KM value to D, and set the wavenumber to 3050cm. -1 Set the KM value to L, and set the wavenumber to 3530cm. -1 The KM value is set to M.

[0032] Before 1000 hours of exposure at 85°C and 85% humidity, the absorbance of the β-type silon phosphor, obtained by FT-IR, was converted to KM values ​​using the Kuberka-Monk function, and the wavenumber was set to 3050 cm⁻¹. -1 Set the KM value to E and the wavenumber to 3330cm. -1 When the KM value is set to F,

[0033] Having at least one of the following (Q1) to (Q6),

[0034] (Q1) A and B satisfy 0.31 > B / A

[0035] (Q2) A and C satisfy 0.44 > C / A

[0036] (Q3) A and D satisfy 0.21 > D / A

[0037] (Q4) L, A, and C satisfy 1.4 < A / L and 0.81 > C / L

[0038] (Q5) L, A, and M satisfy 1.4 < A / L and 0.67 > M / L

[0039] (Q6) L, A, E, and F satisfy 0.94> ((A / L) / (F / E)).

[0040] 3. The β-type silon phosphor according to 1. or 2, wherein,

[0041] In the surface composition of this β-type silon phosphor, the fluorine content is less than 0.4 atom.

[0042] 4. The β-type silon phosphor according to any one of 1 to 3, wherein the boron content in the surface composition of the β-type silon phosphor is less than 0.5 atom.

[0043] 5. A light-emitting component, comprising:

[0044] Light-emitting elements; and

[0045] A wavelength converter that converts light emitted from the light-emitting element to emit light.

[0046] The wavelength converter has any one of the β-type silon phosphors described in 1 to 4.

[0047] 6. A light-emitting device comprising the light-emitting component described in 5.

[0048] According to the present invention, a β-type silron phosphor with excellent reliability of LED brightness when the LED is powered on (continuously lit) in a high temperature and high humidity environment, a light-emitting component using the β-type silron phosphor, and a light-emitting device are provided. Attached Figure Description

[0049] Figure 1 This is a schematic cross-sectional view showing the structure of an LED package used in a reliability test.

[0050] Figure 2 The image shows the FT-IR spectrum of a β-type silon phosphor before exposure to 85°C and 85% humidity for 1000 hours at a wavenumber of 3050 cm⁻¹. -1 The KM value normalized spectrum.

[0051] Figure 3The image shows the FT-IR spectrum of a β-type silon phosphor before exposure to 85°C and 85% humidity for 1000 hours at a wavenumber of 3050 cm⁻¹. -1 The KM value normalized spectrum.

[0052] Figure 4 The image shows the FT-IR spectrum of a β-type silon phosphor before exposure to 85°C and 85% humidity for 1000 hours at a wavenumber of 3050 cm⁻¹. -1 The KM value normalized spectrum.

[0053] Figure 5 The image shows the FT-IR spectrum of a β-type silon phosphor prior to 1000 hours of exposure at 85°C and 85% humidity, at a wavenumber of 3330 cm⁻¹. -1 The KM value normalized spectrum.

[0054] Figure 6 The image shows the FT-IR spectrum of a β-type silon phosphor prior to 1000 hours of exposure at 85°C and 85% humidity, at a wavenumber of 3330 cm⁻¹. -1 The KM value normalized spectrum.

[0055] Figure 7 The image shows the FT-IR spectrum of a β-type silon phosphor prior to 1000 hours of exposure at 85°C and 85% humidity, at a wavenumber of 3330 cm⁻¹. -1 The KM value normalized spectrum.

[0056] Figure 8 The image shows the FT-IR spectrum of a β-type silon phosphor before it was exposed to 85°C and 85% humidity for 1000 hours.

[0057] Figure 9 The image shows the FT-IR spectrum of a β-type silon phosphor before it was exposed to 85°C and 85% humidity for 1000 hours.

[0058] Figure 10 The image shows the FT-IR spectrum of a β-type silon phosphor before it was exposed to 85°C and 85% humidity for 1000 hours.

[0059] Figure 11 The image shows the FT-IR spectrum of a β-type silon phosphor after 1000 hours of exposure at 85°C and 85% humidity, at a wavenumber of 3050 cm⁻¹. -1 The KM value normalized spectrum.

[0060] Figure 12The image shows the FT-IR spectrum of a β-type silon phosphor after 1000 hours of exposure at 85°C and 85% humidity, at a wavenumber of 3050 cm⁻¹. -1 The KM value normalized spectrum.

[0061] Figure 13 The image shows the FT-IR spectrum of a β-type silon phosphor after 1000 hours of exposure at 85°C and 85% humidity, at a wavenumber of 3050 cm⁻¹. -1 The KM value normalized spectrum.

[0062] Figure 14 The image shows the FT-IR spectrum of a β-type silon phosphor after 1000 hours of exposure at 85°C and 85% humidity, at a wavenumber of 3330 cm⁻¹. -1 The KM value normalized spectrum.

[0063] Figure 15 The image shows the FT-IR spectrum of a β-type silon phosphor after 1000 hours of exposure at 85°C and 85% humidity, at a wavenumber of 3330 cm⁻¹. -1 The KM value normalized spectrum.

[0064] Figure 16 The image shows the FT-IR spectrum of a β-type silon phosphor after 1000 hours of exposure at 85°C and 85% humidity, at a wavenumber of 3330 cm⁻¹. -1 The KM value normalized spectrum.

[0065] Figure 17 The figure shows the FT-IR spectrum of a β-type silon phosphor after 1000 hours of exposure at 85°C and 85% humidity.

[0066] Figure 18 The figure shows the FT-IR spectrum of a β-type silon phosphor after 1000 hours of exposure at 85°C and 85% humidity.

[0067] Figure 19 The figure shows the FT-IR spectrum of a β-type silon phosphor after 1000 hours of exposure at 85°C and 85% humidity. Detailed Implementation

[0068] An overview of the β-type silon phosphor of this embodiment will be provided.

[0069] (This implementation method P)

[0070] The β-type silron phosphor in the first example of this embodiment P is a β-type silron phosphor with europium dissolved in it, and its structure is as follows:

[0071] In the spectrum of this β-type silon phosphor obtained by FT-IR, the absorbance of the spectrum was converted to KM value using the Kuberka-Monk function, and the wavenumber was set to 3050 cm⁻¹. -1 Set the KM value to E and the wavenumber to 3330cm. -1 Set the KM value to F, and set the wave number to 3500cm. -1 When the KM value is set to G,

[0072] E, F, and G satisfy 1.8 < F / E and 1.8 > G / E.

[0073] Furthermore, the β-type silron phosphor in the second example of this embodiment P is a β-type silron phosphor with europium dissolved in it, and its configuration is as follows:

[0074] In the spectrum of this β-type silon phosphor obtained by FT-IR, the absorbance of the spectrum was converted to KM value using the Kuberka-Monk function, and the wavenumber was set to 3050 cm⁻¹. -1 Set the KM value to E and the wavenumber to 3330cm. -1 Set the KM value to F, and set the wavenumber to 3530cm. -1 When the KM value is set to H,

[0075] E, F, and H satisfy 1.8 < F / E and 2.0 > H / E.

[0076] According to the inventors' insights, it has been discovered that the surface stability of a β-type silon phosphor can be evaluated under high temperature and high humidity conditions when an LED is powered on (continuously lit) based on the infrared absorption spectrum of the β-type silon phosphor obtained by FT-IR.

[0077] Specifically, in the infrared absorption spectrum, 3330 cm⁻¹ -1 Indicates NH group, 3500cm -1 Indicates Si-OH group, 3530cm -1 This represents a Si-OH group. Therefore, 3330cm -1 The KM value (F) is relatively large and 3500cm -1 The KM value (G) is relatively small and / or 3330 cm -1 The KM value (F) is relatively large and 3530cm -1 A relatively small KM value (H) indicates a low proportion of Si-OH groups present in the functional groups on the surface of the β-type silon phosphor.

[0078] While the detailed mechanism is not yet fully understood, it is speculated that during the manufacturing process of a light-emitting device equipped with a β-type silron phosphor, or during the use of such a device, even if the phosphor is exposed to moisture, changes in the surface state are suppressed when the proportion of Si-OH groups on the surface of the β-type silron phosphor is low. Therefore, changes in the luminescent characteristics of the LED originating from the β-type silron phosphor can be suppressed, thus improving the reliability of the light-emitting device. Furthermore, if there are many Si-OH groups, the amount of adsorbed water based on hydrogen bonds increases. During LED power-on (lighting) reliability tests in high-temperature and high-humidity environments, the adsorbed water may detach or vaporize due to heat emitted from the LED, or the OH groups of the Si-OH groups may detach or vaporize as water due to heat. This creates gaps at the interface between the phosphor and the resin sealing the phosphor, making light easily reflected and scattered, and hindering the absorption of excitation light from the phosphor, thus reducing LED brightness. Alternatively, since the phosphor is usually placed near the LED chip, there is also a concern that the aforementioned adsorbed water and water originating from the detachment and vaporization of Si-OH groups may accelerate the degradation of the LED chip itself. When the presence ratio of Si-OH groups is low, it is possible to suppress the variation in luminescence characteristics of LEDs derived from β-type silon phosphors.

[0079] Furthermore, in this embodiment P, the FT-IR spectrum of the β-type silon phosphor is the KM-converted FT-IR spectrum obtained by Kubelka-Monk function conversion. For each wavenumber, the values ​​are expressed using the 3050 cm⁻¹ peak, which represents the valley portion with low absorption. -1 Standardization was performed, that is, F / E and G / E were used as the primary indicators and F / E and H / E were used as the secondary indicators. This enabled the evaluation of the surface stability of β-type silron phosphors under high temperature and high humidity conditions when LEDs were powered on (continuously lit).

[0080] The lower limit of F / E is greater than 1.8, preferably 1.9 or higher, and more preferably 2.1 or higher. This improves the reliability of LED brightness when the LED is powered on (continuously lit) in high temperature and high humidity environments.

[0081] There is no specific limit to the upper limit of F / E; it can be below 6.0 or below 4.0.

[0082] In the β-type silon phosphor of the first example described above, the upper limit of G / E is less than 1.8, preferably less than 1.4, and more preferably less than 1.1. This improves the reliability of LED brightness when the LED is powered on (continuously lit) in high temperature and high humidity environments.

[0083] There is no particular limitation on the lower limit of G / E; it can be above 0.05 or above 0.1.

[0084] In the β-type silane phosphor of the second example described above, the upper limit of H / E is less than 1.8, preferably less than 1.19, and more preferably less than 1.16. This improves the reliability of LED brightness when the LED is powered on (continuously lit) in high temperature and high humidity environments.

[0085] There is no particular limitation on the lower limit of H / E; it can be above 0.05 or above 0.1.

[0086] In this embodiment P, for example, the F / E, G / E, and H / E can be controlled by appropriately selecting the types or proportions of the components contained in the β-type silon phosphor, the preparation method of the β-type silon phosphor, etc. Among these, as elements for setting the F / E, G / E, and H / E to the desired numerical range, examples include alkaline treatment of the β-type silon phosphor, especially alkaline treatment by heating in a state where there is substantially no water on the surface of the β-type silon phosphor, and appropriate water washing or decantation treatment.

[0087] (This implementation method Q)

[0088] In this embodiment, the β-type silon phosphor Q is a β-type silon phosphor with europium dissolved in it.

[0089] The infrared absorption spectrum of a sample exposed to β-type silon phosphor at 85°C and 85% humidity for 1000 hours was obtained by FT-IR. The absorbance of this infrared absorption spectrum was converted to KM values ​​using the Kubelka-Monk function, and the wavenumber was set to 3330 cm⁻¹. -1 Set the KM value to A, and set the wave number to 3500cm. -1 Set the KM value to C, and set the wavenumber to 3550cm. -1 Set the KM value to B, and set the wavenumber to 3600cm. -1 Set the KM value to D, and set the wavenumber to 3050cm. -1 Set the KM value to L, and set the wavenumber to 3530cm. -1 The KM value was set as M. Furthermore, using samples exposed to 85°C and 85% humidity for 1000 hours, the infrared absorption spectrum was obtained via FT-IR. The absorbance of this infrared absorption spectrum was converted to a KM value using the Kubelka-Monk function, with a wavenumber of 3330 cm⁻¹. -1 Set the KM value to F, and set the wavenumber to 3050cm. -1 The KM value is set to E.

[0090] In the β-type silon phosphor of this embodiment Q, the KM value of the standardized specified wavenumber obtained by the FT-IR spectrum after such KM conversion satisfies at least one of the conditions (Q1) to (Q6) described later.

[0091] In addition, for samples exposed to 85°C and 85% humidity for 1000 hours, they were placed in an environment of 15°C to 30°C and 45% to 85% humidity for 1 hour after exposure, and then placed in polyethylene bottles (rigid bottles) for storage. They were taken out of the polyethylene bottles for various measurements, analyses and evaluations.

[0092] (Q1) The β-type silon phosphor is composed of A and B, which satisfy 0.31 > B / A.

[0093] (Q2) The β-type silon phosphor is composed of A and C satisfying 0.44 > C / A.

[0094] (Q3) The β-type silon phosphor is composed of A and D satisfying 0.21 > D / A.

[0095] (Q4) The β-type silon fluorophore is composed of L, A, and C satisfying 1.4 < A / L and 0.81 > C / L.

[0096] (Q5) The β-type silon fluorophore is composed of L, A, and M such that 1.4 < A / L and 0.67 > M / L.

[0097] (Q6) The β-type silon fluorophore is composed of L, A, F, and E, satisfying 0.94 > ((A / L) / (F / E)).

[0098] According to the inventors' insights, it has been discovered that the surface stability of a β-type silon phosphor can be evaluated under high temperature and high humidity conditions when an LED is powered on (continuously lit) based on the infrared absorption spectrum of the β-type silon phosphor obtained by FT-IR.

[0099] Specifically, in the infrared absorption spectrum, 3500 cm⁻¹ -1 Indicates Si-OH group, 3550cm -1 Indicates Si-OH group, 3600cm -1 This indicates a Si-OH group. Therefore, it includes wavenumbers of 3550 cm⁻¹. -1 KM value (B), wavenumber 3500cm -1 KM value (C) and wavenumber 3600cm -1 A small KM value (D) in any one of the groups indicates a low proportion of Si-OH groups present in the functional groups on the surface of the β-type silon phosphor.

[0100] Furthermore, in the infrared absorption spectrum, 3330 cm⁻¹ -1 Indicates NH group, 3500cm -1 Indicates Si-OH group, 3530cm -1 This indicates a Si-OH group. Therefore, the wavenumber is 3330 cm⁻¹. -1The KM value (A) is relatively large and the wavenumber is 3500 cm⁻¹ -1 The KM value (C) is relatively small and / or the wavenumber is 3330 cm⁻¹. -1 The KM value (A) is relatively large and the wavenumber is 3530cm. -1 A relatively small KM value (M) indicates a low proportion of Si-OH groups present in the functional groups on the surface of the β-type silon phosphor.

[0101] While the detailed mechanism is not yet fully understood, it is speculated that during the manufacturing process of a light-emitting device equipped with a β-type silron phosphor, or during the use of such a device, even if the phosphor is exposed to moisture, changes in the surface state are suppressed when the proportion of Si-OH groups on the surface of the β-type silron phosphor is low. Therefore, changes in the luminescent characteristics of the LED originating from the β-type silron phosphor can be suppressed, thus improving the reliability of the light-emitting device. Furthermore, if there are many Si-OH groups, the amount of adsorbed water based on hydrogen bonds increases. During LED power-on (lighting) reliability tests in high-temperature and high-humidity environments, the adsorbed water may detach or vaporize due to heat emitted from the LED, or the OH groups of the Si-OH groups may detach or vaporize as water due to heat. This creates gaps at the interface between the phosphor and the resin sealing the phosphor, making light easily reflected and scattered, and hindering the absorption of excitation light from the phosphor, thus reducing LED brightness. Alternatively, since the phosphor is usually placed near the LED chip, there is also a concern that the aforementioned adsorbed water and water originating from the detachment and vaporization of Si-OH groups may accelerate the degradation of the LED chip itself. When the presence ratio of Si-OH groups is low, it is possible to suppress the variation in luminescence characteristics of LEDs derived from β-type silon phosphors.

[0102] Furthermore, compared to before 1000 hours of exposure at 85°C and 85% humidity, after exposure at 3050cm... -1 The standardized value represents the wavenumber of the NH group, 3330 cm⁻¹. -1 The decrease in the KM value indicates that there were more NH groups and fewer Si-OH groups on the surface before exposure.

[0103] Furthermore, in this embodiment Q, the FT-IR spectrum of the β-type silon phosphor after 1000 hours of exposure at 85°C and 85% humidity was obtained using the KM-converted FT-IR spectrum obtained by Kubelka-Monk function conversion. The values ​​for each wavenumber were obtained using the wavenumber 3330 cm⁻¹, which represents the NH group. -1 The KM value (A) is a standardized index, using B / A, C / A, or D / A, and is represented by the wavenumber 3050 cm⁻¹, which indicates the valley portion with less absorbed components. -1The value (L) is a standardized index, using A / L and C / L, and / or A / L and M / L, as the FT-IR spectrum of the β-type silon phosphor before exposure at a wavenumber of 3050 cm⁻¹. -1 The value (E) is a standardized index, using F / E ((A / L) / (F / E)), which allows for good reproducibility evaluation of the surface stability of β-type silon phosphors under high temperature and high humidity conditions when LEDs are powered on (continuously lit).

[0104] In the first example of the β-type silon phosphor, the upper limit of the B / A ratio is less than 0.31, preferably less than 0.29, and more preferably less than 0.27. This improves the reliability of LED brightness when the LED is powered on (continuously lit) in high-temperature and high-humidity environments.

[0105] Furthermore, there is no particular limitation on the lower limit of B / A; it can be above 0.05 or above 0.10.

[0106] In the second example of the β-type silon phosphor, the upper limit of the C / A ratio is less than 0.44, preferably less than 0.40, and more preferably less than 0.37. This improves the reliability of LED brightness when the LED is powered on (continuously lit) in high-temperature and high-humidity environments.

[0107] Furthermore, there is no particular limitation on the lower limit of C / A; it can be above 0.05 or above 0.10.

[0108] In the third example of the β-type silon phosphor, the upper limit of the D / A ratio is less than 0.21, preferably less than 0.20, and more preferably less than 0.19. This improves the reliability of LED brightness when the LED is powered on (continuously lit) in high-temperature and high-humidity environments.

[0109] Furthermore, there is no particular limitation on the lower limit of D / A; it can be above 0.01 or above 0.05.

[0110] In the β-type silon phosphors of the fourth or fifth example, the lower limit of A / L is greater than 1.4, preferably 1.45 or more, and more preferably 1.50 or more. This improves the reliability of LED brightness when the LED is powered on (continuously lit) in high-temperature and high-humidity environments.

[0111] Furthermore, there is no specific upper limit for A / L; it can be below 4.0 or below 3.0.

[0112] In the fourth example of the β-type silon phosphor, the upper limit of the C / L ratio is less than 0.81, preferably less than 0.79, and more preferably less than 0.76. This improves the reliability of LED brightness when the LED is powered on (continuously lit) in high-temperature and high-humidity environments.

[0113] Furthermore, there is no specific limit to the lower limit of C / L; it can be above 0.05 or above 0.10.

[0114] In the fifth example of the β-type silon phosphor, the upper limit of M / L is less than 0.67, preferably less than 0.64, and more preferably less than 0.61. This improves the reliability of LED brightness when the LED is powered on (continuously lit) in high temperature and high humidity environments.

[0115] There is no particular limit to the lower limit of M / L; it can be above 0.01 or above 0.05.

[0116] In the β-type silon phosphor of the sixth example, the upper limit of ((A / L) / (F / E)) is less than 0.94, preferably less than 0.91, and more preferably less than 0.89. This improves the reliability of LED brightness when the LED is powered on (continuously lit) in high temperature and high humidity environments.

[0117] There is no particular limit to the lower limit of M / L; it can be above 0.01 or above 0.05.

[0118] In this embodiment Q, for example, by appropriately selecting the types or proportions of each component contained in the β-type silon phosphor, the preparation method of the β-type silon phosphor, etc., the above-mentioned B / A, C / A, D / A, A / L, C / L, M / L, and ((A / L) / (F / E)) can be controlled. Among these, as elements for setting the above-mentioned B / A, C / A, D / A, A / L, C / L, M / L, and ((A / L) / (F / E)) to the desired numerical range, examples include alkaline treatment of the β-type silon phosphor, especially alkaline treatment by heating in a state where there is substantially no water on the surface of the β-type silon phosphor, appropriate water washing treatment or decantation treatment, etc.

[0119] The β-type silon phosphor of this embodiment will be described in detail below.

[0120] The β-type silon phosphor of this embodiment is extremely useful as a phosphor for light sources such as Light Emitting Diodes (LEDs).

[0121] For example, β-type silon phosphors can absorb blue light in the wavelength range of 420 nm to 480 nm and emit light with a peak wavelength in the range of greater than 480 nm and less than 800 nm.

[0122] There are no particular limitations on β-type silon phosphors as long as they can be used as phosphors; they are composed of europium-activated β-type silon with europium dissolved in solid solution.

[0123] Europium-activated β-type silron phosphors are made from general formula Si 6-zAL z O z N 8-z Eu 2+ (0<z≤4.2) represents this.

[0124] In general formula Si 6-z AL z O z N 8-z Eu 2+ In this study, there are no particular limitations on the z-value and the europium content, but the z-value is preferably greater than 0 and less than 4.2. From the viewpoint of further improving the luminescence intensity of europium-activated β-type silron phosphor, it is preferable to have a z-value of 0.002 or more and less than 1.0.

[0125] Furthermore, the europium content in the europium-activated β-type silon phosphor is preferably 0.1% by mass or more and 2.0% by mass or less.

[0126] The upper limit of the (D90-D10) / D50 ratio of the β-type silon phosphor powder can be, for example, 2.00 or less, 1.50 or less, 1.00 or less, 0.90 or less, or 0.80 or less. On the other hand, the lower limit of the (D90-D10) / D50 ratio of the β-type silon phosphor powder can be, for example, 0.50 or more, 0.60 or more, or 0.70 or more.

[0127] The upper limit of the D10 of the β-type silon phosphor powder can be, for example, 16 μm or less, 14 μm or less, 12 μm or less, 10 μm or less, or 8 μm or less. On the other hand, the lower limit of the D10 of the β-type silon phosphor powder can be, for example, 1 μm or more, 5 μm or more, or 7 μm or more.

[0128] The upper limit of the D50 of the β-type silon phosphor powder can be, for example, 40 μm or less, 30 μm or less, 20 μm or less, or 12 μm or less. On the other hand, the lower limit of the D50 of the β-type silon phosphor powder can be, for example, 5 μm or more, 8 μm or more, or 10 μm or more.

[0129] The upper limit of the D90 of the β-type silon phosphor powder can be, for example, 60 μm or less, 40 μm or less, 30 μm or less, or 25 μm or less. On the other hand, the lower limit of the D90 of the β-type silon phosphor powder can be, for example, 15 μm or more, 18 μm or more, or 21 μm or more.

[0130] In this specification, D10, D50, and D90 refer to the particle sizes that, in the volume-based particle size distribution curve determined by laser diffraction / scattering, reach 10%, 50%, and 90% of the total particle size, respectively, starting from the smallest particle size.

[0131] The particle size was determined according to the laser diffraction / scattering method described in JIS R 1629:1997 "Method for determination of particle size distribution of fine ceramic raw materials based on laser diffraction / scattering". A particle size distribution measuring device (manufactured by Microtrac BELCorp., product name: "Microtrac MT3300EXII") was used. Specifically, firstly, 0.1 g of the fluorophore to be measured was added to 100 mL of deionized water and dispersed for 3 minutes using an ultrasonic homogenizer (manufactured by NIHON SEIKI Co., Ltd., product name: "Ultrasonic Homogenizer US-150E", chip size: φ20, amplitude: 100%, oscillation frequency: 19.5 kHz, amplitude: approximately 31 μm) to prepare the sample. Then, the particle size was measured using the particle size distribution measuring device.

[0132] The surface composition of β-type silon phosphors can be obtained by X-ray photoelectron spectroscopy (XPS). The determination conditions are as follows.

[0133] Measurement apparatus: X-ray photoelectron spectroscopy analyzer (ULVAC-PHI, INCORPORATED. PHI5000 VersaProbeII).

[0134] Excitation source: Al-X-ray source (AL K Alpha)

[0135] Output: 15kV-50W

[0136] Measurement area: φ200μm

[0137] Energy: 46.95eV

[0138] Energy step size 0.05 eV

[0139] Time per step: 50ms

[0140] Number of Scans: 10

[0141] Time: 13 minutes / point

[0142] Note: Narrow Scan, the average of three measurements. Analyzed as surface composition to ensure the total of B, N, O, F, Na, Al, Si, and Eu is 100 atom% (excluding carbon).

[0143] In the surface composition of the β-type silon phosphor, the fluorine content is, for example, less than 0.4 atom%, preferably less than 0.3 atom%, and more preferably less than 0.2 atom%. The fluorine content in the surface composition can be below the detection limit.

[0144] Furthermore, in the surface composition of the β-type silon phosphor, the boron content is, for example, less than 0.5 atom%, preferably less than 0.4 atom%, and more preferably less than 0.3 atom%. The boron content in the surface composition can be below the detection limit.

[0145] In the surface composition of the β-type silon phosphor, the sodium content is, for example, less than 0.3 atom%, preferably less than 0.2 atom%, and more preferably less than 0.1 atom%. The sodium content in the surface composition can be below the detection limit.

[0146] The diffuse reflectance at 800 nm in the β-type silon phosphor is, for example, 90% or more, preferably 92% or more, and more preferably 94% or more. This enables the realization of a β-type silon phosphor with excellent optical properties. The diffuse reflectance at 500 nm is, for example, 75% or more, preferably 80% or more, and more preferably 84% or more. This also enables the realization of a β-type silon phosphor with excellent optical properties.

[0147] Next, the method for manufacturing the β-type silon phosphor of this embodiment will be described.

[0148] An example of the method for manufacturing a β-type silon phosphor according to this embodiment includes: a preparation step for preparing a β-type silon phosphor; and an alkali treatment step for performing an alkali treatment on the surface of the β-type silon phosphor.

[0149] The preparation process for the aforementioned β-type silon phosphor can be carried out using known methods, and may include at least one of the following: a calcination process involving mixing raw material powders containing silicon, aluminum, and an activating element and calcining the mixture to obtain a calcined product; and a post-treatment process involving further processing of the calcined product after the calcination process, such as crushing, grading, annealing, and acid treatment. The post-treatment processes can be performed in any order.

[0150] In addition, the alkali treatment process can be carried out after the above-mentioned grading treatment or after the acid treatment.

[0151] The calcination temperature in the calcination process is, for example, 1800°C or higher and 2100°C or lower, preferably 1850°C or higher and 2050°C or lower. By setting the calcination temperature to or above the aforementioned lower limit, the luminescence intensity can be improved. The calcination process can be performed multiple times. Furthermore, during subsequent calcinations, a portion of the raw material can be added.

[0152] The ambient temperature during the annealing process is, for example, 1100°C or higher and 1800°C or lower, preferably 1300°C or higher and 1750°C or lower. By setting the annealing temperature above or above the aforementioned lower limit, the luminescence intensity can be improved. By setting the annealing temperature below or above the aforementioned upper limit, the crystallinity can be improved, and the decrease in luminescence peak intensity can be suppressed.

[0153] The ambient gas used in the annealing process is selected from any one of the following: rare gases of Group 18 elements in the periodic table, such as argon; inactive gases such as nitrogen; hydrogen; or a mixture of hydrogen and argon.

[0154] The property-enhancing effect of the annealing process can be achieved under a wide range of ambient pressures, from depressurization to pressurization. However, pressures below 1 kPa promote the decomposition of β-type silon phosphors, and are therefore not preferred. Furthermore, by pressurizing the environment, other conditions (low temperature, shortened time) required to exhibit the annealing effect can be expanded. However, even at excessively high ambient pressures, the annealing effect reaches its peak, and special and expensive annealing equipment is required. Therefore, considering mass production, an ambient pressure of 10 MPa or less is preferred, and more preferably less than 1 MPa.

[0155] If the processing time in the annealing process is too short, the effect of improving crystallinity will be low; if it is too long, the annealing effect will reach its peak. Therefore, the processing time should be more than 1 hour and less than 24 hours, preferably more than 2 hours and less than 10 hours.

[0156] Furthermore, the manufacturing method of this embodiment may include an acid treatment step of immersing the β-type silron phosphor in an acid solution after an annealing step. This further improves the properties of the phosphor.

[0157] The acid treatment process preferably includes the following steps: immersing a β-silicon phosphor in an acid solution, separating the β-silicon phosphor and acid using a filter or the like, and washing the separated β-silicon phosphor with water. Acid treatment removes decomposition products of the β-silicon phosphor crystals generated during the annealing process, thereby improving fluorescence properties. Examples of acids used for acid treatment include monomers or mixtures of hydrofluoric acid, sulfuric acid, phosphoric acid, hydrochloric acid, or nitric acid; a mixed acid composed of hydrofluoric acid and nitric acid is preferred for removing decomposition products. The temperature of the acid solution during acid treatment can be room temperature, but to improve the effectiveness of the acid treatment, it is preferable to heat it to 50°C or higher and 90°C or lower.

[0158] In the grading process, to remove micropowder from the powder after the acid treatment process, a decantation process can be performed to remove the micropowder from the supernatant where the powder is settling after the acid treatment process. The obtained precipitate is filtered, washed with ion-exchanged water or pure water, dried, and then passed through a 250 μm mesh sieve to obtain β-type silon phosphor. An aqueous solution containing a dispersant such as Na hexametaphosphate can be used as the dispersion medium. Then, washing, filtration, drying, and sieving are preferably performed using ion-exchanged water or pure water.

[0159] Based on the above, it is possible to obtain β-type silon phosphors with activating elements dissolved in solid solution.

[0160] In addition, known processes can be added as needed. For example, post-processing such as crushing / shredding, purification, drying, sieving and grading can be performed.

[0161] The particle size adjustment process, such as screening and grading, can be carried out at any time after the calcination process, the annealing process, or the acid treatment process.

[0162] In the alkali treatment process, the β-type silon phosphor is heated to allow a solid alkaline substance to adhere to the surface.

[0163] Examples of alkaline substances include alkali metal hydroxides, alkali metal carbonates, hydroxides of Group 2 elements in the periodic table, oxides of Group 2 elements in the periodic table, and quaternary ammonium salts.

[0164] An example of an alkaline substance includes one or more substances selected from the group consisting of NaOH, KOH, LiOH, CaO, SrO, Na2CO3 and NaHCO3.

[0165] Solid alkaline substances can be alkaline substances that are solid at room temperature, or alkaline substances obtained by removing the solvent from an alkaline solution obtained by dissolving the alkaline substance in a solvent such as water and drying it at a temperature below 50°C. For example, vacuum drying can also be performed at a temperature below 50°C.

[0166] To allow a solid alkaline substance to adhere to a surface, for example, a mixture of β-type silon phosphor powder and an alkaline substance that is solid at room temperature can be used.

[0167] Furthermore, a mixed solution containing β-type silon phosphor powder, an alkaline substance, and water can be vacuum dried at a temperature below 50°C to remove water from the alkaline substance, allowing the solid alkaline substance to adhere to the surface of the β-type silon phosphor. By removing solvents such as water at a lower temperature below 50°C, the formation of Si-OH groups on the surface of the β-type silon phosphor can be suppressed.

[0168] In the alkali treatment process, a β-type silon phosphor is heated in an environment where no water is present, allowing the solid alkaline substance to adhere to its surface. "No water present" means that moisture (humidity) is allowed in the external environment of the solid alkaline substance or in hydrates contained within the solid alkaline substance.

[0169] In the alkali treatment process, the β-type silon phosphor can be heated from room temperature.

[0170] The room temperature can be set to, for example, 23°C or 25°C.

[0171] In addition, there is no particular upper limit to the heating temperature; for example, it can be below 400°C or below 450°C.

[0172] In the alkali treatment process, heating can begin from room temperature, for example at a heating rate of 0.1°C / min to 100°C / min, preferably 5°C / min to 50°C / min, and more preferably 1°C / min to 30°C / min.

[0173] In the alkali treatment process, the heating environment can be, for example, atmospheric environment, vacuum environment, rare gas environment, or inactive gas environment such as nitrogen.

[0174] The method for manufacturing β-type silon phosphors in this embodiment can be further included in a step of washing the obtained β-type silon phosphors with water after an alkaline treatment step. In the washing method, after stirring the β-type silon phosphors in ion-exchanged water or pure water for a few minutes, if left to stand, fine powder or the like floats on the water surface. Therefore, after discarding the supernatant along with the floating fine powder, the precipitate is filtered. During filtration, ion-exchanged water is added to the filter cake containing the aqueous β-type silon phosphor (precipitate), and filtration is performed to further remove alkaline substances. The operation of recovering the β-type silon phosphor is repeated. The washing can be performed two or more times. The washing is repeated until the pH of the filtrate reaches 6-8. Compared to the first washing, more fine powder or the like that floats on the water surface during the second washing is produced. It is believed that the fine powder or the like removed along with the supernatant during washing contains impurities removed from the surface of the β-type silon phosphors during alkaline treatment. If the microparticles removed by washing with water and the supernatant are analyzed, the wavenumber in the FT-IR spectrum is 3530 cm⁻¹. -1 The peak values ​​of nearby Si-OH groups are significantly higher, and B (boron) and F (fluorine) are significantly higher in the surface composition analysis by XPS.

[0175] The water used in the washing process is dried and removed by known methods.

[0176] After the alkali treatment process, post-processing such as crushing / shredding, purification, drying, sieving and grading can be carried out as needed.

[0177] [Wavelength converter, light-emitting component]

[0178] The light-emitting component of this embodiment includes: a light-emitting element; and a wavelength converter that converts light irradiated from the light-emitting element to emit light, wherein the wavelength converter has the aforementioned β-type silon phosphor.

[0179] An example of the method for manufacturing a wavelength conversion component according to this embodiment includes a step of manufacturing a wavelength conversion component using a β-type silon phosphor obtained by a method for manufacturing β-type silon phosphors.

[0180] The wavelength converter of this embodiment is a wavelength converter that converts light irradiated from a light-emitting element to emit light, and it has the aforementioned β-type silron phosphor. The wavelength converter may be composed solely of a β-type silron phosphor, or it may include a substrate in which the β-type silron phosphor is dispersed. As the substrate, known substrates can be used, such as glass, resin, and inorganic materials.

[0181] The shape of the wavelength converter is not particularly limited; it can be configured as a plate or as a sealed portion of the light-emitting element or the entire light-emitting surface.

[0182] [Light-emitting device]

[0183] The light-emitting device according to this embodiment includes a light-emitting component, which includes a light-emitting light source (light-emitting element) and the wavelength converter described above.

[0184] By combining a light source and a wavelength converter, light with high luminous intensity can be emitted.

[0185] An example of the manufacturing method of the light-emitting device in this embodiment includes a step of mounting a wavelength conversion component obtained by a wavelength conversion component manufacturing method on the light-emitting surface of a light-emitting light source.

[0186] An example of a light-emitting device is an LED package. An LED package may include a light source (LED chip), a substrate (lead frame) housing the light source, and a wavelength converter covering the light source. The LED chip can emit near-ultraviolet to blue light with wavelengths from 300nm to 500nm. The LED chip and the lead frame can be electrically connected using bonding wires. The wavelength converter can be covered with a cap made of synthetic resin.

[0187] The wavelength converters described above only need to include the aforementioned β-type silon phosphotron; other phosphotrons may also be included. Other phosphotrons may include, for example, α-type silon phosphotrons, KSF phosphotrons, CASN phosphotrons, SCASN phosphotrons, and YAG phosphotrons. These phosphotrons may be used individually or in combination of two or more.

[0188] When using the aforementioned β-type silron phosphor as a light-emitting device, as a light source, by irradiating near-ultraviolet or visible light containing wavelengths of 300 nm to 500 nm as an excitation source, it exhibits green light emission characteristics with a wavelength peak in the range of 520 nm to 560 nm. Therefore, as a light-emitting device, by combining a near-ultraviolet LED chip or a blue LED chip with a β-type silron phosphor, and one or more of a red, blue, yellow, or orange phosphor, white light can be generated.

[0189] As an example, by combining β-type silon phosphors that display green and KSF-based phosphors that display red, it is possible to appropriately use them for backlighting LEDs and the like, which are suitable for high color rendering TVs.

[0190] The embodiments of the present invention have been described above, but these are merely examples, and various structures other than those described can be used. Furthermore, the present invention is not limited to the above embodiments, and modifications and alterations within the scope of achieving the objectives of the present invention are included in the present invention.

[0191] Below are examples of reference form P.

[0192] 1. A β-type silron phosphor, which is a β-type silron phosphor with europium dissolved in it, and its structure is as follows:

[0193] In the spectrum of this β-type silon phosphor obtained by FT-IR, the absorbance of the spectrum was converted to KM value using the Kuberka-Monk function, and the wavenumber was set to 3050 cm⁻¹. -1 Set the KM value to E and the wavenumber to 3330cm. -1 Set the KM value to F, and set the wave number to 3500cm. -1 When the KM value is set to G,

[0194] E, F, and G satisfy 1.8 < F / E and 1.8 > G / E.

[0195] 2. A β-type silron phosphor, which is a β-type silron phosphor with europium dissolved in it, and its structure is as follows:

[0196] In the spectrum of this β-type silon phosphor obtained by FT-IR, the absorbance of the spectrum was converted to KM value using the Kuberka-Monk function, and the wavenumber was set to 3050 cm⁻¹. -1 Set the KM value to E and the wavenumber to 3330cm. -1 Set the KM value to F, and set the wavenumber to 3530cm. -1 When the KM value is set to H,

[0197] E, F, and H satisfy 1.8 < F / E and 2.0 > H / E.

[0198] 3. The β-type silon phosphor according to 1. has the following structure:

[0199] E, F, and G satisfy 1.8 < F / E and 1.4 > G / E.

[0200] 4. The β-type silon phosphor according to 2. has the following structure:

[0201] E, F, and H satisfy 1.8 < F / E and 1.19 > H / E.

[0202] 5. A β-type silon phosphor, which is a β-type silon phosphor with europium as described in any one of 1. to 4. dissolved in it, wherein,

[0203] In the surface composition of this β-type silon phosphor, the fluorine content is less than 0.4 atom.

[0204] 6. A β-type silane phosphor, wherein europium as described in any one of the formulations 1. to 5. is dissolved in solid solution, wherein...

[0205] In the surface composition of this β-type silon phosphor, the boron content is less than 0.5 atom.

[0206] 7. A light-emitting component, comprising: a light-emitting element; and

[0207] A wavelength converter that converts light emitted from the light-emitting element to emit light.

[0208] The wavelength converter has any one of the β-type silon phosphors described in 1 to 6.

[0209] 8. A light-emitting device comprising the light-emitting component described in 7.

[0210] Below are examples of reference form Q.

[0211] 1. A β-type silron phosphor, which is a β-type silron phosphor with europium dissolved in it, and its structure is as follows:

[0212] After 1000 hours of exposure at 85°C and 85% humidity, the absorbance of the β-type silon phosphor obtained by FT-IR was converted to KM values ​​using the Kuberka-Monk function, and the wavenumber was set to 3330 cm⁻¹. -1 Set the KM value to A, and set the wavenumber to 3550cm. -1 When the KM value is set to B,

[0213] A and B satisfy 0.31 > B / A.

[0214] 2. A β-type silron phosphor, which is a β-type silron phosphor with europium dissolved in it, and its structure is as follows:

[0215] After 1000 hours of exposure at 85°C and 85% humidity, the absorbance of the β-type silon phosphor obtained by FT-IR was converted to KM values ​​using the Kuberka-Monk function, and the wavenumber was set to 3330 cm⁻¹. -1 Set the KM value to A, and set the wave number to 3500cm. -1 When the KM value is set to C,

[0216] A and C satisfy 0.44 > C / A.

[0217] 3. A β-type silron phosphor, which is a β-type silron phosphor with europium dissolved in it, and its structure is as follows:

[0218] After 1000 hours of exposure at 85°C and 85% humidity, the absorbance of the β-type silon phosphor obtained by FT-IR was converted to KM values ​​using the Kuberka-Monk function, and the wavenumber was set to 3330 cm⁻¹. -1 Set the KM value to A, and set the wave number to 3600cm. -1 When the KM value is set to D,

[0219] A and D satisfy 0.21 > D / A.

[0220] 4. A β-type silron phosphor, wherein europium is dissolved in solid solution, and its structure is as follows:

[0221] After 1000 hours of exposure at 85°C and 85% humidity, the absorbance of the β-type silon phosphor obtained by FT-IR was converted to KM values ​​using the Kuberka-Monk function, and the wavenumber was set to 3050 cm⁻¹. -1 Set the KM value to L and the wavenumber to 3330cm. -1 Set the KM value to A, and set the wave number to 3500cm. -1 When the KM value is set to C,

[0222] L, A, and C satisfy 1.4 < A / L and 0.81 > C / L.

[0223] 5. A β-type silron phosphor, which is a β-type silron phosphor with europium dissolved in it, and its structure is as follows:

[0224] After 1000 hours of exposure at 85°C and 85% humidity, the absorbance of the β-type silon phosphor obtained by FT-IR was converted to KM values ​​using the Kuberka-Monk function, and the wavenumber was set to 3050 cm⁻¹. -1Set the KM value to L and the wavenumber to 3330cm. -1 Set the KM value to A, and set the wavenumber to 3530cm. -1 When the KM value is set to M,

[0225] L, A, and M satisfy 1.4 < A / L and 0.67 > M / L.

[0226] 6. The β-type silon phosphor according to 2. has the following structure:

[0227] A and C satisfy 0.40 > C / A.

[0228] 7. A β-type silron phosphor, wherein europium is dissolved in a β-type silron phosphor, and its structure is as follows:

[0229] After 1000 hours of exposure at 85°C and 85% humidity, the absorbance of the β-type silon phosphor obtained by FT-IR was converted to KM values ​​using the Kuberka-Monk function, and the wavenumber was set to 3050 cm⁻¹. -1 Set the KM value to L and the wavenumber to 3330cm. -1 The KM value is set to A.

[0230] Next, in a europium-solubilized β-type silron phosphor that had undergone 1000 hours of exposure at 85°C and 85% humidity, the spectrum of the β-type silron phosphor was determined by FT-IR. The absorbance of the spectrum was converted to KM values ​​using the Kuberka-Monk function, and the wavenumber was set to 3050 cm⁻¹. -1 Set the KM value to E and the wavenumber to 3330cm. -1 The KM value is set to F.

[0231] L, A, E, and F satisfy 0.94 > ((A / L) / (F / E)).

[0232] 8. A β-type silon phosphor, wherein europium as described in any one of 1. to 7. is dissolved in solid solution, wherein,

[0233] In the surface composition of this β-type silon phosphor, the fluorine content is less than 0.4 atom.

[0234] 9. A β-type silon phosphor, wherein europium as described in any one of the formulations 1. to 8. is dissolved in solid solution, wherein...

[0235] In the surface composition of this β-type silon phosphor, the boron content is less than 0.5 atom.

[0236] 10. A light-emitting component, comprising:

[0237] A wavelength converter that converts light emitted from the light-emitting element to emit light.

[0238] The wavelength converter has any one of the β-type silon phosphors described in 1 to 9.

[0239] 11. A light-emitting device comprising the light-emitting component described in 10.

[0240] Example

[0241] The present invention will now be described in detail with reference to the embodiments, but the present invention is not limited in any way by the description of these embodiments.

[0242] <Preparation of β-type cylon fluorophores>

[0243] [Comparative Example 1]

[0244] (1) Each raw material was weighed in a container to achieve the following weights: silicon nitride (Si3N4, SN-E10 grade manufactured by Ube Industries, Ltd.) 98.4% by mass, aluminum nitride (AlN, E grade manufactured by Tokuyam Corporation) 1.01% by mass, and europium oxide (Eu2O3, RU grade manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 0.59% by mass. The mixture was then obtained by mixing using a V-type mixer (manufactured by Tsutsui Rikikaku Equipment Co., Ltd.). The obtained mixture was then passed through a 250 μm mesh sieve to remove agglomerates, thereby obtaining a raw material composition. The agglomerates that did not pass through the sieve were pulverized, and the particle size was adjusted to pass through the sieve.

[0245] (2) 200g of the raw material composition prepared as described above was weighed into a covered cylindrical boron nitride container (manufactured by Denka Boron Nitride, a molded product with boron nitride (product name: Denka Boron Nitride N-1) as the main component, inner diameter: 10cm, height: 10cm). Then, the container was placed in an electric furnace equipped with a carbon heater and heated to 2000°C under a nitrogen atmosphere (pressure: 0.90MPaG), and heated at 2000°C for 10 hours (calcination process). After heating, the sample, which had become loosely aggregated lumps in the container, was taken out into a mortar and crushed. After crushing, it was passed through a sieve with a mesh size of 250μm to obtain a powdered first calcined body.

[0246] (3) Next, the first calcined body was filled into a cylindrical boron nitride container, and the container was placed in an electric furnace equipped with a carbon heater. The temperature was raised to 1450°C under an argon atmosphere (pressure: 0.025 MPaG), and heated at 1450°C for 5 hours (annealing process). After heating, the loosely aggregated lumps formed by the particles in the container were broken up using a mortar and passed through a 250 μm sieve to obtain powder.

[0247] (4) Next, the powder obtained in (3) was added to a mixed acid of hydrofluoric acid (concentration: 50% by mass) and nitric acid (concentration: 70% by mass) (hydrofluoric acid and nitric acid were mixed in a volume ratio of 1:1), and acid treatment was performed at 75°C with stirring for 30 minutes. After acid treatment, stirring was stopped to allow the powder to precipitate, and the supernatant and the micro powder purified by acid treatment were removed. Then, distilled water was added and stirring was performed again. Stirring was stopped to allow the powder to precipitate, and the supernatant and micro powder were removed. This operation was repeated until the pH of the aqueous solution was below 8 and the supernatant became transparent. The precipitate was filtered, dried, and passed through a sieve with a mesh size of 250 μm.

[0248] (5) Next, in order to further remove the micropowder, the powder obtained in (4) was dispersed in an aqueous solution of ion-exchanged water containing 0.05 wt% Na hexametaphosphate as the dispersion medium. After standing, a decantation process was performed to remove the micropowder in the supernatant that was precipitating. The obtained precipitate was filtered, washed with ion-exchanged water, and dried, and then passed through a sieve with a mesh size of 250 μm. The decantation operation was repeated. Then, the mixture was washed with ion-exchanged water, filtered, dried, and sieved. Thus, the europium-activated β-type silon phosphor of Comparative Example 1 was obtained.

[0249] [Comparative Example 2]

[0250] The β-type silon phosphor powder obtained in the same manner as Comparative Example 1 (5) was further added to a mixed acid (hydrofluoric acid (concentration: 50% by mass) and nitric acid (concentration: 70% by mass) at a volume ratio of 1:1, and acid treatment was performed at 75°C with stirring for 30 minutes. After acid treatment, stirring was stopped to allow the powder to precipitate, and the supernatant and the micro-powder purified by acid treatment were removed. Then, distilled water was added and stirring was performed again. Stirring was stopped to allow the powder to precipitate and the supernatant was removed. This operation was repeated until the pH of the aqueous solution was below 8 and the supernatant became clear. The precipitate was filtered, dried, and passed through a sieve with a mesh size of 250 μm to obtain the β-type silon phosphor of Comparative Example 2.

[0251] [Example 1]

[0252] Using dry powder, the powder was heated in an alumina container under atmospheric conditions from 25°C at a heating rate of 10°C / min and heated to 175°C for 1 hour (alkali treatment process), and then washed with water. The dry powder was obtained by mixing the powder of β-type silon phosphor obtained by (5) in the same manner as Comparative Example 1 with a 50% by mass sodium hydroxide aqueous solution, filtering the mixed solution, and vacuum drying the residue at 45°C.

[0253] In the water washing method, after stirring the β-type silane fluorophore in ion-exchange water for a few minutes, if left to stand, the microparticles will float to the surface. Therefore, the supernatant, along with the floating microparticles, is discarded. The precipitate is then filtered, and during filtration, ion-exchange water is added to the filter cake containing the aqueous β-type silane fluorophore (precipitate), and filtration is repeated to further remove alkaline substances. The β-type silane fluorophore recovery process is then repeated. The water washing is performed twice.

[0254] Compared to the first water wash, the second water wash produced more microparticles that floated on the surface during the initial wash. It is believed that the microparticles removed by the water wash along with the supernatant include impurities removed from the surface of the β-type silon phosphor during alkaline treatment. Analysis of the microparticles removed by the water wash along with the supernatant revealed a wavenumber of 3530 cm⁻¹ in the FT-IR spectrum. -1 The peak value of nearby Si-OH groups was significantly higher (compared to the sample of Example 1 or Comparative Example 1), and the B (boron) and F (fluorine) values ​​were significantly higher in the surface composition analysis by XPS (compared to the sample of Example 1 or Comparative Example 1).

[0255] After washing with water and drying, the sample was passed through a sieve with a mesh size of 250 μm to obtain the europium-activated β-type silon phosphor of Example 1.

[0256] [Comparative Example 3]

[0257] The powder of β-type cyron phosphor obtained by (5) in the same manner as Comparative Example 1 was further mixed with 0.5% by mass of sodium hydroxide aqueous solution, and the mixture was placed in a polyethylene container, the lid was gently closed to avoid complete sealing, and placed in a desiccator set at 70°C for 1 hour.

[0258] Then, after filtering to remove the solvent, the β-silicon phosphor is stirred in ion-exchanged water for a few minutes. The entire slurry, including the supernatant and suspended microparticles, is then filtered / recovered. During filtration, ion-exchanged water is added to the filter cake containing the aqueous β-silicon phosphor (precipitate) and filtered again to further remove alkaline substances. The operation of recovering the β-silicon phosphor is repeated. Water washing is performed twice.

[0259] After washing with water and drying, the sample was passed through a sieve with a mesh size of 250 μm, thereby obtaining the β-type silon phosphor of Comparative Example 3.

[0260] [Comparative Example 4]

[0261] The powder of β-type cyron phosphor obtained in the same manner as Comparative Example 1 (5) was further mixed in a 0.5% by mass sodium hydroxide aqueous solution. The mixture was then placed in a polyethylene container, the lid was gently closed to avoid complete sealing, and the mixture was treated in a hot water bath at 50°C for 30 minutes while being stirred with a magnetic stirrer. The mixture was then placed in a desiccator set at 105°C for 30 minutes.

[0262] Then, after filtering to remove the solvent, the β-silicon phosphor is stirred in ion-exchanged water for a few minutes. The entire slurry, including the supernatant and suspended microparticles, is then filtered / recovered. During filtration, ion-exchanged water is added to the filter cake containing the aqueous β-silicon phosphor (precipitate) and filtered again to further remove alkaline substances. The operation of recovering the β-silicon phosphor is repeated. Water washing is performed twice.

[0263] After washing with water and drying, the sample was passed through a sieve with a mesh size of 250 μm, thereby obtaining the β-type silon phosphor of Comparative Example 4.

[0264] [Comparative Example 5]

[0265] The β-type silon phosphor powder obtained by (5) in the same manner as Comparative Example 1 was mixed with a 0.5% by mass sodium hydroxide aqueous solution, and the mixture was stirred for 1 minute. After filtration to remove the solvent, the β-type silon phosphor was stirred in ion-exchanged water for a few minutes. The entire slurry, including the supernatant and suspended micropowder, was filtered / recovered. During filtration, ion-exchanged water was added to the filter cake containing water-containing β-type silon phosphor (precipitate) and filtered to further remove alkaline substances. The operation of recovering β-type silon phosphor was repeated. Water washing was performed twice.

[0266] After washing with water, the sample was vacuum dried at room temperature and passed through a sieve with a mesh size of 250 μm, thereby obtaining the β-type silon phosphor of Comparative Example 5.

[0267] [Comparative Example 6]

[0268] Each raw material was weighed in a container to make silicon nitride (Si3N4, SN-E10 grade manufactured by Ube Industries, Ltd.) 99.0% by mass, aluminum nitride (AlN, E grade manufactured by TokuyamA Corporation) 0.58% by mass, and europium oxide (Eu2O3, RU grade manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 0.42% by mass. The mixture was then mixed using a V-type mixer (manufactured by Tsutsui Rikikaku Equipment Co., Ltd.). The conditions for obtaining the mixture were changed. Otherwise, the β-type silon phosphor of Comparative Example 6 was obtained in the same manner as Comparative Example 1.

[0269] [Example 2]

[0270] Using dried powder, the mixture was heated in an alumina container under atmospheric conditions from 25°C at a heating rate of 10°C / min and then heated to 110°C for 1 hour (alkali treatment process). The powder was then washed with water. This dried powder was obtained by mixing β-type silon phosphor powder obtained in the same manner as Comparative Example 6 (5) with a 50% by mass sodium hydroxide aqueous solution, filtering the mixture, and then vacuum drying the residue at 45°C. In the water washing method, after stirring the β-type silon phosphor in ion-exchange water for a few minutes, if left to stand, the microparticles float to the surface. Therefore, the supernatant was discarded along with the floating microparticles, and the precipitate was filtered. During filtration, ion-exchange water was added to the filter cake containing the aqueous β-type silon phosphor (precipitate), and filtration was performed to further remove alkaline substances. The operation of recovering the β-type silon phosphor was repeated. The water washing was performed twice. After washing with water and drying, the sample was passed through a sieve with a mesh size of 250 μm, thereby obtaining the europium-activated β-type silon phosphor of Example 2.

[0271] [Example 3]

[0272] Using dry powder, the powder was heated in an alumina container under atmospheric conditions from 25°C at a heating rate of 10°C / min and heated to 175°C for 1 hour (alkali treatment process), and then washed with water. The dry powder was obtained by mixing the powder of β-type silon phosphor obtained by (5) in the same manner as Comparative Example 6 with a 50% by mass aqueous solution of sodium hydroxide, filtering the mixed solution, and vacuum drying the residue at 45°C.

[0273] In the water washing method, after stirring the β-type silane fluorophore in ion-exchange water for a few minutes, if left to stand, the microparticles will float to the surface. Therefore, the supernatant, along with the floating microparticles, is discarded. The precipitate is then filtered, and during filtration, ion-exchange water is added to the filter cake containing the aqueous β-type silane fluorophore (precipitate), and filtration is repeated to further remove alkaline substances. The β-type silane fluorophore recovery process is then repeated. The water washing is performed twice.

[0274] After washing with water and drying, the sample was passed through a sieve with a mesh size of 250 μm, thereby obtaining the europium-activated β-type silon phosphor of Example 3.

[0275] [Comparative Example 7]

[0276] Each raw material was weighed in a container to achieve the following proportions: silicon nitride (Si3N4, SN-E10 grade manufactured by Ube Industries, Ltd.) 96.2% by mass, aluminum nitride (AlN, E grade manufactured by TokuyamA Corporation) 2.46% by mass, alumina powder (TM-DAR grade manufactured by Taimei Chemical Industry Co., Ltd.) 0.56% by mass, and europium oxide (Eu2O3, RU grade manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 0.78% by mass. The mixture was then mixed using a V-type mixer (manufactured by Tsutsui Rikikaku Equipment Co., Ltd.). The conditions for obtaining the mixture were changed. Otherwise, the β-type silon phosphor of Comparative Example 7 was obtained in the same manner as Comparative Example 1.

[0277] [Example 4]

[0278] Using dry powder, the powder was heated in an alumina container under atmospheric conditions from 25°C at a heating rate of 10°C / min and heated to 175°C for 1 hour (alkali treatment process), and then washed with water. The dry powder was obtained by mixing the powder of β-type silon phosphor obtained by (5) in the same manner as Comparative Example 7 with a 50% by mass aqueous solution of sodium hydroxide, filtering the mixed solution, and vacuum drying the residue at 45°C.

[0279] In the water washing method, after stirring the β-type silane fluorophore in ion-exchange water for a few minutes, if left to stand, the microparticles will float to the surface. Therefore, the supernatant, along with the floating microparticles, is discarded. The precipitate is then filtered, and during filtration, ion-exchange water is added to the filter cake containing the aqueous β-type silane fluorophore (precipitate), and filtration is repeated to further remove alkaline substances. The β-type silane fluorophore recovery process is then repeated. The water washing is performed twice.

[0280] After washing with water and drying, the sample was passed through a sieve with a mesh size of 250 μm, thereby obtaining the europium-activated β-type silon phosphor of Example 4.

[0281] (FT-IR spectroscopy measurement)

[0282] The infrared absorption spectrum of the obtained β-type silon phosphor was obtained by FT-IR, and the absorbance of the spectrum was converted into KM value by Kuberca-Monk function.

[0283] Regarding the values ​​representing the Kubelka-Monk function (KM value of absorbance) and wavenumber (cm²) -1 The KM-converted spectrum of the relationship between the two was obtained by using a Spectrum One (accessory: diffuse reflectance, cumulative number 64, resolution 4cm) manufactured by PerkinElmer. -1 The results were obtained using Fourier transform infrared absorption analysis (FT-IR) with the setting set to AutoZero (normalizing the lowest value of the spectrum after KM conversion to zero).

[0284] The β-type silon fluorophore used to measure sample P was exposed to 85% humidity for 1000 hours prior.

[0285] The sample Q was measured using a β-type silon phosphor that had been exposed to 85°C and 85% humidity for 1000 hours. After the above exposure, the sample Q was placed in a polyethylene bottle (rigid bottle) for 1 hour at 15°C to 30°C and 45% to 85% humidity. Before the measurement, the sample was removed from the polyethylene bottle and its FT-IR spectrum was measured.

[0286] In addition, samples P and Q were prepared as particles using undiluted β-type silon fluorophores.

[0287] In this specification, the “Kuberka-Monk function value” is a function that converts the reflectance of a substance into an index of the substance’s inherent absorption, which can be obtained by dividing the absorption coefficient by the scattering coefficient (absorption coefficient / scattering coefficient).

[0288] In the KM-converted spectrum of sample P, the wavenumber 3050 cm⁻¹ was used. -1 Set the KM value to E, and set the wavenumber to 3330cm. -1 Set the KM value to F, and set the wavenumber to 3500cm. -1 Set the KM value to G, and set the wavenumber to 3530cm. -1 The KM value is set to H.

[0289] In the KM-converted spectrum of sample Q, the wavenumber 3330 cm⁻¹ was determined. -1 Set the KM value to A, and set the wave number to 3500cm. -1 Set the KM value to C, and set the wavenumber to 3550cm. -1Set the KM value to B, and set the wavenumber to 3600cm. -1 Set the KM value to D, and set the wavenumber to 3050cm. -1 Set the KM value to L, and set the wavenumber to 3530cm. -1 The KM value is set to M.

[0290] In the determination of sample P, 3330cm -1 Indicates NH group, 3500cm -1 Indicates Si-OH group, 3530cm -1 Indicates Si-OH group, 3050cm -1 This refers to the portion of the grain where less of the absorbed components are absorbed.

[0291] Furthermore, in the measurement of sample Q, 3330cm -1 Indicates NH group, 3500cm -1 Indicates Si-OH group, 3550cm -1 Indicates Si-OH group, 3050cm -1 This indicates the portion of the grain with lower absorption content, 3530cm -1 This indicates a Si-OH group. 3600cm -1 The absorption is very small, but there is a slight absorption originating from the Si-OH group.

[0292] In each of the embodiments and comparative examples that used the measured sample Q, the values ​​of F / E, G / E, and H / E are shown in Table 1.

[0293] In each of the examples and comparative examples that used the measured sample Q, the values ​​of B / A, C / A, D / A, A / L, C / L, M / L and ((A / L) / (F / E)) are shown in Table 1.

[0294] Figure 2 , Figure 3 and Figure 4 The FT-IR spectra of sample P, obtained from the β-type silon fluorophores obtained in each of the examples and comparative examples before exposure to 85°C and 85% humidity for 1000 hours, were measured at a wavenumber of 3050 cm⁻¹. -1 The KM value normalized spectrum.

[0295] Figure 5 , Figure 6 and Figure 7 The FT-IR spectra of sample P, obtained from the β-type silon fluorophores of each example and comparative example before exposure to 85°C and 85% humidity for 1000 hours, were measured at a wavenumber of 3330 cm⁻¹. -1 The KM value normalized spectrum.

[0296] Figure 8 , Figure 9and Figure 10 The FT-IR spectra of sample P, which was used to measure the β-type silon fluorophore obtained in each of the examples and comparative examples before exposure to 85°C and 85% humidity for 1000 hours, are given.

[0297] Figure 11 , Figure 12 , Figure 13 The FT-IR spectrum of sample Q, after being exposed to β-type silon fluorophores at 85°C and 85% humidity for 1000 hours, was obtained at a wavenumber of 3050 cm⁻¹. -1 The KM value normalized spectrum.

[0298] Figure 14 , Figure 15 , Figure 16 The FT-IR spectrum of sample Q, after being exposed to β-type silon fluorophores at 85°C and 85% humidity for 1000 hours, was obtained at a wavenumber of 3330 cm⁻¹. -1 The KM value normalized spectrum.

[0299] Figure 17 , Figure 18 , Figure 19 The FT-IR spectrum of sample Q, which was obtained after 1000 hours of exposure to β-type silon fluorophores at 85°C and 85% humidity.

[0300] (Determination of surface composition)

[0301] The surface composition of the β-type silon phosphor samples P obtained in each embodiment and comparative example before exposure to 85% humidity for 1000 hours was determined by X-ray photoelectron spectroscopy (XPS) under the following conditions.

[0302] Measurement apparatus: X-ray photoelectron spectroscopy analyzer (ULVAC-PHI, INCORPORATED. PHI5000 VersaProbeII).

[0303] Excitation source: Al-X-ray source (AL K Alpha)

[0304] Output: 15kV-50W

[0305] Measurement area: φ200μm

[0306] Energy: 46.95eV

[0307] Energy step size 0.05 eV

[0308] Time per step: 50ms

[0309] Number of Scans: 10

[0310] Time: 13 minutes / point

[0311] Note: Narrow Scan, the average of three measurements. Analyzed as surface composition to ensure the total of B, N, O, F, Na, Al, Si, and Eu is 100 atom% (excluding carbon).

[0312] [Table 1]

[0313]

[0314] [Table 2]

[0315]

[0316] [Table 3]

[0317]

[0318] The following parameters were evaluated for the obtained β-type silon phosphors.

[0319] <Particle size>

[0320] The sample P, containing β-type silon phosphors from each embodiment, was used to determine the particle size using the laser diffraction / scattering method described in JIS R 1629:1997, "Method for determining particle size distribution of fine ceramic raw materials based on laser diffraction / scattering". A particle size distribution measuring device (manufactured by Microtrac BELCorp., product name: "Microtrac MT3300EX II") was used in the determination. Specifically, firstly, 0.1 g of the phosphor to be measured was added to 100 mL of deionized water and dispersed for 3 minutes using an ultrasonic homogenizer (manufactured by NIHON SEIKI Co., Ltd., product name: "Ultrasonic Homogenizer US-150E", chip size: φ20, amplitude: 100%, oscillation frequency: 19.5 kHz, amplitude: approximately 31 μm) to prepare the sample. Then, the particle size was determined using the particle size distribution measuring device.

[0321] In the particle size distribution curves of the volume reference determined by the above laser diffraction / scattering method, the particle sizes at which the cumulative value starting from the smallest particle size reaches 10%, 50%, and 90% of the total are set as D10, D50, and D90, respectively.

[0322] <Diffuse reflectance>

[0323] The diffuse reflectance of the measurement sample P using the β-type silon phosphor of each embodiment was measured using an apparatus with an integrating sphere (ISV-469) mounted on a UV-Vis spectrophotometer (V-550) manufactured by JASCO Corporation.

[0324] Baseline correction was performed using a standard reflector (Spectralon), and a solid sample holder filled with β-type silon phosphor was set up. Diffuse reflectance was measured in the wavelength range of 500–850 nm.

[0325] The diffuse reflectance (%) at 500 nm and 800 nm was measured.

[0326] <Color Scale X>

[0327] The measurement sample P using the β-type silon phosphor of each embodiment was used to determine the chromaticity X by calculating the CIE chromaticity coordinate x-value (chromaticity X) in the XYZ color system specified in JIS Z8781-3:2016 based on spectral data in the wavelength region of the fluorescence spectrum from 465 to 780 nm, in accordance with JIS Z8724:2015. In the measurement method, the phosphor to be measured was filled into a concave cell, its surface kept smooth, and mounted into the opening of an integrating sphere. Monochromatic light at a wavelength of 455 nm, split from an Xe lamp as the light source, was introduced into the integrating sphere as excitation light for the phosphor using an optical fiber. The monochromatic light, as the excitation light, was irradiated onto the phosphor to be measured, and the fluorescence spectrum was measured. A spectrophotometer (manufactured by Otsuk Electronics Co., Ltd., product name: MCPD-7000) was used in the measurement.

[0328] <Reliability Testing>

[0329] The reliability of LED packages incorporating the obtained β-type silron phosphor was evaluated using the following methods.

[0330] LED packages were prepared according to Figure 1 The packaged component for the structure of the light-emitting device shown.

[0331] First, the electrodes on the upper surface of the LED, located at the concave bottom of the housing, were wire-bonded to the lead frame. The LED used had a peak emission wavelength of 448 nm and a chip size of 1.0 mm × 0.5 mm. Next, a β-type silane phosphor was mixed into liquid silicone resin (KER6150, manufactured by Shin-Etsu Chemica LCo., Ltd.) to achieve a phosphor concentration of 10.5 wt%, thereby obtaining a resin composition. The obtained resin composition was injected into the housing recess using a micro-injector and then allowed to stand for 15 hours at room temperature and low humidity (MAC DRY MCU-201A, manufactured by ERC Co., Ltd.), followed by curing at 150°C for 1 hour. This yielded an LED package incorporating a β-type silane phosphor.

[0332] Regarding the obtained LED package, the beam was measured and set as the initial value L0. Then, after being lit at 300mA at 85℃ and 85%RH and left for 500 hours, the beam was taken out and the beam L1 was measured when it was dried at room temperature. The reliability coefficient M (=L1 / L0×100) was calculated.

[0333] Regarding the relative comparison of the reliability coefficients of Comparative Examples 2-5 and Example 1, when the reliability coefficient M of Comparative Example 1 is set to 100.0%, the relative values ​​(%) of the reliability coefficients of Comparative Examples 2-5 and Example 1 are shown in Table 1. For example, when the reliability coefficient M of Comparative Example 1 is set to M1 and the reliability coefficient M of Example 1 is set to M2, the relative value of the reliability coefficient M of Example 1 is expressed as M2 / M1×100.

[0334] Regarding the relative comparison of the reliability coefficients of Examples 2 and 3, when the reliability coefficient M of Comparative Example 6 is set to 100.0%, the relative values ​​(%) of the reliability coefficients of Examples 2 and 3 are shown in Table 1.

[0335] Regarding the relative comparison of the reliability coefficients of Example 4, when the reliability coefficient M of Comparative Example 7 is set to 100.0%, the relative values ​​(%) of the reliability coefficients of Example 4 are shown in Table 1 and Table 2, respectively.

[0336] Compared with Comparative Examples 1 to 7, the β-type silon phosphors of Examples 1 to 4 showed excellent reliability of LED brightness when the LED was powered on (continuously lit) under high temperature and high humidity conditions.

[0337] This application asserts priority based on Japanese Patent Application No. 2023-099450, filed on June 16, 2023, and Japanese Patent Application No. 2023-099451, filed on June 16, 2023, and incorporates the entire contents of their disclosures into this case.

[0338] Symbol Explanation

[0339] 10. Light-emitting device

[0340] 20 Light-emitting elements

[0341] 30 Radiator

[0342] 40 Housing

[0343] 50 First lead frame

[0344] 60 Second lead frame

[0345] 70 joint line

[0346] 72 Joint line

[0347] 80 complex

[0348] 82 Alkali-treated fluorescent particles

[0349] 84 Sealing materials

Claims

1. A β-type silron phosphor, wherein europium is dissolved in its solid solution, In the spectrum of this β-type silon phosphor obtained by FT-IR, the absorbance of the spectrum was converted to KM value using the Kuberka-Monk function, and the wavenumber was set to 3050 cm⁻¹. -1 Set the KM value to E and the wavenumber to 3330cm. -1 Set the KM value to F, and set the wave number to 3500cm. -1 Set the KM value to G, and set the wavenumber to 3530cm. -1 When the KM value is set to H, It has at least one of the following (P1) and (P2): (P1) E, F, and G satisfy 1.8 < F / E and 1.8 > G / E. (P2) E, F, and H satisfy 1.8 < F / E and 2.0 > H / E.

2. A β-type silron phosphor, wherein europium is dissolved in its solid solution, After 1000 hours of exposure at 85°C and 85% humidity, the absorbance of the β-type silon phosphor obtained by FT-IR was converted to KM values ​​using the Kuberka-Monk function, and the wavenumber was set to 3330 cm⁻¹. -1 Set the KM value to A, and set the wavenumber to 3550cm. -1 Set the KM value to B, and set the wave number to 3500cm. -1 Set the KM value to C, and set the wave number to 3600cm. -1 Set the KM value to D, and set the wavenumber to 3050cm. -1 Set the KM value to L, and set the wavenumber to 3530cm. -1 The KM value is set to M. Before 1000 hours of exposure at 85°C and 85% humidity, the absorbance of the β-type silon phosphor, obtained by FT-IR, was converted to KM values ​​using the Kuberka-Monk function, and the wavenumber was set to 3050 cm⁻¹. -1 Set the KM value to E and the wavenumber to 3330cm. -1 When the KM value is set to F, Having at least one of the following (Q1) to (Q6), (Q1) A and B satisfy 0.31 > B / A, (Q2) A and C satisfy 0.44 > C / A, (Q3) A and D satisfy 0.21 > D / A, (Q4) L, A, and C satisfy 1.4 < A / L and 0.81 > C / L. (Q5) L, A, and M satisfy 1.4 < A / L and 0.67 > M / L. (Q6) L, A, E, and F satisfy 0.94> ((A / L) / (F / E)).

3. The β-type silon phosphor according to claim 1 or 2, wherein, In the surface composition of this β-type silon phosphor, the fluorine content is less than 0.4 atom.

4. The β-type silon phosphor according to claim 1 or 2, wherein, In the surface composition of this β-type silon phosphor, the boron content is less than 0.5 atom.

5. A light-emitting component, comprising: Light-emitting elements; and A wavelength converter that converts light emitted from the light-emitting element to emit light. The wavelength converter has the β-type silon phosphor as described in claim 1 or 2.

6. A light-emitting device comprising the light-emitting component as described in claim 5.

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