CN113966377B - Phosphor and method for producing phosphor - Google Patents
Phosphor and method for producing phosphor Download PDFInfo
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- CN113966377B CN113966377B CN202080043958.2A CN202080043958A CN113966377B CN 113966377 B CN113966377 B CN 113966377B CN 202080043958 A CN202080043958 A CN 202080043958A CN 113966377 B CN113966377 B CN 113966377B
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
- C09K11/617—Silicates
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
- C09K11/615—Halogenides
- C09K11/616—Halogenides with alkali or alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
Abstract
The present disclosureIn one aspect, a method for producing a phosphor is provided, which comprises K 2 SiF 6 ：Mn 4+ The method for producing a phosphor of (2) comprises a step of bringing a fluoride phosphor into contact with a solution containing a potassium-containing compound, a reducing agent and a silicon compound.
Description
Technical Field
The present disclosure relates to a phosphor and a method of manufacturing the phosphor.
Background
Light Emitting Diodes (LEDs) are widely used for image display devices, backlights for displays, illumination, etc. In an image display device using an LED, an LED having a blue light emitting diode and a yellow phosphor is generally used. In recent years, there has been a demand for high color development of image display devices, and therefore, green phosphors and red phosphors have been used in combination in place of yellow phosphors. From the viewpoint of improving color rendering properties, various red phosphors have been studied.
In addition, an image display device using an LED and the like are required to have excellent moisture resistance. Therefore, a phosphor used for an LED is also required to have excellent moisture resistance. On the other hand, mn-based phosphor known as red phosphor 4+ Activated fluoride phosphors (e.g., K 2 SiF 6 ：Mn 4+ Etc.), the moisture resistance is not necessarily sufficient, and improvement of the moisture resistance of the fluoride phosphor is being studied.
For example, patent document 1 proposes a method for producing a fluoride phosphor, which is characterized by a general formula K that is activated by Mn having a valence of 4 and absorbs light on the short wavelength side of visible light to emit red light 2 [M 1-a Mn 4+ a F 6 ](wherein M is at least 1 selected from Ti, zr, hf, si, ge and Sn, and a is 0 < a < 0.2.) a method for producing a fluoride phosphor, comprising the steps of: a step of mixing a solution containing at least Mn and F, a solution containing at least K and F, and a solution containing at least Si and F to form a phosphor core represented by the general formula; and mixing the phosphor core with a solution containing a reducing agent to form an internal region of the phosphor particle having a concentration ratio of 4-valent Mn on the phosphor coreLow surface area.
Prior art literature
Patent literature
Patent document 1 Japanese patent application laid-open No. 2015-028148
Disclosure of Invention
The purpose of the present disclosure is to provide a method for producing a phosphor having excellent moisture resistance reliability. The present disclosure also aims to provide a phosphor excellent in moisture resistance reliability.
One aspect of the present disclosure provides a method for producing a phosphor containing K 2 SiF 6 ：Mn 4+ The method for producing a phosphor of (a) comprises the steps of: the fluoride phosphor is contacted with a solution comprising a potassium-containing compound, a reducing agent, and a silicon compound.
The above method for producing a fluorescent material is widely used to produce a fluorescent material having excellent moisture resistance reliability by having a step of bringing a fluoride fluorescent material into contact with a solution containing the above specific component.
The above-mentioned potassium-containing compound may contain at least 1 selected from potassium acetate, potassium nitrate and potassium hydroxide.
The reducing agent may comprise hydrogen peroxide.
The above solution may contain at least 1 selected from water and alcohol.
The silicon compounds described above may comprise the general formula: si (OR) 1 )(OR 2 )(OR 3 )(OR 4 ) A compound represented by the formula (I). In the general formula, R 1 、R 2 、R 3 And R is 4 Each independently represents a monovalent hydrocarbon group.
One aspect of the present disclosure is to provide a phosphor having a K-containing structure 2 SiF 6 ：Mn 4+ A body portion attached to the body portion and including silicon and oxygen; the ratio of silicon to potassium measured on the surface of the phosphor by X-ray photoelectron spectroscopy is 0.52 or more, and the ratio of silicon to potassium in the main body portion is lower than the ratio of silicon to potassium in the coating portion.
The phosphor has a predetermined coating portion on the surface of the main body portion, and therefore has excellent moisture resistance reliability.
The ratio of oxygen to potassium of the phosphor obtained by measurement by X-ray photoelectron spectroscopy may be 0.20 or more.
According to the present disclosure, a method for producing a phosphor excellent in moisture resistance reliability can be provided. According to the present disclosure, a phosphor excellent in moisture resistance can also be provided.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of a phosphor.
Detailed Description
Embodiments of the present disclosure will be described below with reference to the drawings, as the case may be. However, the following embodiments are examples for illustrating the present disclosure, and the gist thereof is not intended to limit the present disclosure to the following. The positional relationship between the upper, lower, left, right, etc. is based on the schematic representation unless otherwise specified. Further, the dimensional ratios of the elements are not limited to the ratios illustrated in the drawings.
The materials exemplified in the present specification may be used singly or in combination of 1 or 2 or more, unless otherwise specified. When a plurality of substances corresponding to the respective components in the composition are present, the content of the respective components in the composition is the total amount of the plurality of substances present in the composition unless otherwise specified.
One embodiment of the method for producing a phosphor is a phosphor containing K 2 SiF 6 ：Mn 4+ The method for producing a phosphor of (a) comprises the steps of: the fluoride phosphor is contacted with a solution comprising a potassium-containing compound, a reducing agent, and a silicon compound.
According to the above method for producing a phosphor, a phosphor having a K-containing structure can be produced 2 SiF 6 ：Mn 4+ A body part attached to the surface of the body part, and a coating part containing silicon and oxygen. The phosphor produced has a coating portion on at least a part of the surface of the fluoride phosphor, and therefore has excellent moisture resistance reliability. The moisture-proof reliability in the present specification means that the following examples are described in the present specificationThe internal quantum efficiency maintenance rate obtained by measurement was used as an index for evaluating the performance.
The step of bringing the fluoride phosphor into contact with the solution may be, for example, a method of dispersing the fluoride phosphor in the solution or a method of spraying the solution on the fluoride phosphor. In the above step, the order of blending the fluoride fluorescent material, the potassium-containing compound, the reducing agent, and the silicon compound can be appropriately adjusted. That is, the fluoride phosphor and the silicon compound may be added to a solution containing a potassium-containing compound and a reducing agent, or the silicon compound may be added to a solution containing a potassium-containing compound and a reducing agent after the fluoride phosphor is added.
In the case where the step of bringing the fluoride fluorescent material into contact with the solution is a method of adding the fluoride fluorescent material and the silicon compound to a solution containing a compound containing potassium and a reducing agent, it is preferable that the step is performed for a predetermined period of time while stirring the solution. For example, the above step is preferably a step of adding a fluoride phosphor and a silicon compound to a solution containing a potassium-containing compound and a reducing agent, stirring for about 1 minute to 72 hours, and then standing for about 1 to 30 minutes to obtain a phosphor. The stirring time can be adjusted according to the pH of the solution, the kind and the amount of the silicon compound to be blended, and the like. The stirring time is preferably 3 to 24 hours from the viewpoints of reactivity and productivity. The phosphor obtained in the step of bringing the fluoride phosphor into contact with the solution may be subjected to solid-liquid separation and recovery by filtration, centrifugation, decantation, or the like, for example.
The fluoride phosphor may be K 2 SiF 6 The fluoride represented, and a part of the 4-valent element sites are replaced with manganese. In the fluoride phosphor, some of its constituent elements, that is, potassium (K), silicon (Si), fluorine (F), and manganese (Mn), may be replaced with other elements, or may be replaced with elements having different valence numbers, so that some of the elements in the crystal are deficient. The other element may be, for example, at least one selected from sodium (Na), germanium (Ge), titanium (Ti), and oxygen (O).
The fluoride phosphor may be commercially available, or a phosphor prepared separately may be used. That is, the above-described method for producing a fluorescent material may further include a step of producing a fluoride fluorescent material. The above-mentioned method for producing a fluorescent material may further include a step of washing, a step of drying, a step of classifying the produced fluorescent material, and the like, in addition to the step of producing the fluorescent material.
The step of preparing the fluoride phosphor may be, for example, a step of preparing a fluoride phosphor by dissolving a compound serving as a potassium source, a compound serving as a silicon source, a compound serving as a fluorine source, a compound serving as a manganese source, or the like in hydrofluoric acid or an aqueous fluosilicic acid solution, heating the solution, and evaporating the solution to dryness; the method may further include a step of cooling the solution to precipitate a fluoride phosphor to prepare a fluoride phosphor; alternatively, the method may be a step of adding a poor solvent for the fluoride phosphor to the solution to reduce the solubility of the fluoride phosphor, and precipitating the fluoride phosphor to prepare the fluoride phosphor.
Examples of the compound serving as a potassium source include potassium hydrofluoride (e.g., KHF 2 Etc.) and potassium fluoride (e.g., KF, etc.), etc. Examples of the compound to be a silicon source include silicon dioxide (SiO 2 ) Hydrogen silicon fluoride (H) 2 SiF 6 ) And potassium silicofluoride (K) 2 SiF 6 ) Etc. Hydrofluoric acid and aqueous hydrofluoric acid solutions dissolve compounds that are potassium sources and become fluorine sources. When an aqueous hydrofluoric acid solution is used, the concentration of hydrofluoric acid may be, for example, 40 to 70 mass%. When hydrofluoric acid is used, the means for treating it is preferably made of a chemically stable fluororesin. By using a fluororesin tool or the like, the mixing of impurities can be suppressed.
The compound serving as the manganese source may contain, for example, a compound capable of supplying manganese having a valence of +7 or less, preferably a compound capable of supplying manganese having a valence of +4 or less, more preferably a compound capable of supplying manganese having a valence of +4, and still more preferably a compound capable of supplying manganese having a valence of +4. The manganese source compound preferably contains a compound which is easily dissolved in a solvent such as hydrofluoric acid to form MnF in an aqueous solution 6 2- Ionic compoundMore preferably in the general formula K 2 SiF 6 K representing manganese of +4 valence in solid solution in fluoride crystal 2 MnF 6 Further preferably K 2 MnF 6 。
The particle size of the fluoride phosphor can be adjusted according to the use of the phosphor to be produced, and the like. The volume median particle diameter (D50) of the fluoride phosphor may be, for example, 5 to 30. Mu.m, 10 to 30. Mu.m, 20 to 30. Mu.m, or 25 to 30. Mu.m. By setting the volume median particle diameter (D50) of the fluoride phosphor to 30 μm or less, it is possible to suppress clogging of the mixture of the phosphor and the resin in the filling nozzle in the production of an LED element or the like. The volume median particle diameter (D50) of the fluoride fluorescent material may be, for example, 0.1 to 5 μm or 1 to 5 μm in addition to the larger volume median particle diameter (D50). The volume median particle diameter (D50) in the present specification means a particle diameter defined by the volume of the particle according to JIS Z8825: 2013, a cumulative distribution curve of a volume standard measured by a laser diffraction/scattering method.
The solution in contact with the fluoride phosphor contains a compound containing potassium, a reducing agent, and a silicon compound. The potassium-containing compound, the reducing agent and the silicon compound may be partially or completely dispersed in a solution, or may be completely dissolved or ionized.
The potassium-containing compound may be a compound that increases the concentration of potassium (K) in a solution that is in contact with the fluoride phosphor. By including the potassium-containing compound in the solution, dissolution of the fluoride phosphor when the fluoride phosphor is in contact with the solution and disintegration of the crystal structure or the like of the fluoride phosphor can be suppressed. The potassium-containing compound preferably contains at least 1 selected from potassium acetate, potassium nitrate and potassium hydroxide, more preferably contains potassium acetate.
The reducing agent may be a compound capable of reducing manganese contained in the fluoride phosphor in the step of bringing the fluoride phosphor into contact with the solution. The fluoride phosphor is partially hydrolyzed by contact with water, atmospheric moisture, or the like, and a colored compound (e.g., a black compound) containing manganese is formed on the surface of the fluoride phosphor. If such a colored compound is formed, there is a possibility that the optical characteristics of the fluoride phosphor or the above-mentioned phosphor may be lowered. Therefore, it is desirable to treat the fluoride phosphor without using water. In contrast, in the method for producing a phosphor according to the present disclosure, the solution contains the reducing agent, whereby formation of a colored compound can be suppressed, and a phosphor excellent in optical characteristics can be produced even when water is used in the solvent.
The reducing agent is a compound different from the silicon compound, preferably a compound containing no silicon. The reducing agent may comprise at least 1 selected from compounds that generate hydroxyl radicals. Examples of the compound generating a hydroxyl radical include hydrogen peroxide. The reducing agent preferably contains hydrogen peroxide, more preferably hydrogen peroxide. The hydrogen peroxide can reduce manganese having a valence of 4 or less while suppressing the influence on the fluoride phosphor itself.
The silicon compound is a compound containing oxygen and silicon, and is a compound capable of forming a coating portion on at least a part of the surface of the fluoride phosphor. The silicon compound may comprise, for example, a general formula: si (OR) 1 )(OR 2 )(OR 3 )(OR 4 ) A compound represented by the formula (I). In the general formula, R 1 、R 2 、R 3 And R is 4 Each independently represents a monovalent hydrocarbon group. Here, R is 1 、R 2 、R 3 And R is 4 May be the same or different. The monovalent hydrocarbon group may be, for example, an alkyl group having 1 to 12 carbon atoms. The alkyl group may be, for example, a linear alkyl group such as methyl, ethyl, propyl, butyl, or pentyl. R is R 1 、R 2 、R 3 And R is 4 The reactivity of the silicon compound can be adjusted, and the adjustment can be performed according to the concentration of the fluoride fluorescent material contained in the solution, the temperature and pH of the solution, and the like.
The silicon compound may be, for example, tetraalkyl orthosilicate. Examples of the tetraalkyl orthosilicate include tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS), and tetrapropyl orthosilicate (TPOS). The silicon compound preferably contains tetraethyl orthosilicate, more preferably tetraethyl orthosilicate. Tetraethyl orthosilicate is readily available and the reaction can be easily controlled.
The above solution may contain other components in addition to the potassium-containing compound, the reducing agent and the silicon compound. The other components may include, for example, solvents such as water, pH adjusters, surfactants, and the like.
The solvent may contain, for example, at least 1 selected from water and alcohol. Although it is desirable to dispense with the use of water in the treatment of the fluoride phosphor, as described above, in the method for producing a phosphor of the present disclosure, since the above-described solution contains a reducing agent, water may be used. In addition, by adding water to the solution, the reaction of the silicon compound can be further promoted. The solvent is preferably a mixed solvent containing water and alcohol, more preferably a mixed solvent of water and alcohol. By adding water and alcohol to the solution, a phosphor having more excellent moisture resistance reliability can be produced. The alcohol may be, for example, a linear alcohol having 1 to 5 carbon atoms. More specifically, the alcohol may comprise at least 1 selected from methanol, ethanol, and propanol. In the case of the mixed solvent, the content of methanol may be, for example, 10 mass% or more, 15 mass% or more, or 30 mass% or more, and 60 mass% or less, or 50 mass% or less, based on the total amount of the mixed solvent. In the case of the mixed solvent, the content of methanol may be adjusted within the above-mentioned range, and may be, for example, 10 to 60 mass%, 10 to 50 mass%, or 15 to 50 mass% based on the total amount of the mixed solvent.
Examples of the pH adjuster include acetic acid, hydrochloric acid, ammonia, and ammonium acetate. By containing the pH adjuster in the solution, the reaction rate of the silicon compound can be easily adjusted. The pH adjustor preferably comprises acetic acid.
The surfactant is, for example, a cationic surfactant or the like. The cationic surfactant may be, for example, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, polyvinylpyrrolidone, or the like. By containing the surfactant in the above solution, the surface state of the phosphor can be easily adjusted, and a phosphor having more excellent moisture resistance reliability can be produced.
The content of the potassium-containing compound in the solution may be, for example, 1 part by mass or more, 4 parts by mass or more, 10 parts by mass or more, or 13 parts by mass or more based on 100 parts by mass of the fluoride phosphor. The content of the potassium-containing compound in the solution may be, for example, 30 parts by mass or less or 25 parts by mass or less based on 100 parts by mass of the fluoride phosphor. The content of the potassium-containing compound in the solution may be adjusted within the above-described range, and for example, may be 1 to 30 parts by mass, 1 to 25 parts by mass, 4 to 25 parts by mass, 10 to 25 parts by mass, or 13 to 25 parts by mass based on 100 parts by mass of the fluoride phosphor.
The content of the reducing agent in the solution may be adjusted according to the total amount of manganese contained in the fluoride phosphor. The content of the reducing agent in the solution is preferably 100 parts by mass or more based on the total amount of manganese contained in the fluoride phosphor. The upper limit of the content of the reducing agent in the solution is not particularly limited, and may be, for example, 3000 parts by mass or less or 1500 parts by mass or less. The content of the reducing agent in the solution may be adjusted within the above-mentioned range, and may be, for example, 100 to 3000 parts by mass or 100 to 1500 parts by mass.
The content of the silicon compound in the solution may be adjusted according to the volume median particle diameter (D50) of the fluoride phosphor, the temperature and pH of the solution, and the like. The content of the silicon compound in the solution may be, for example, 0.02 to 3.0mol per 100.0 parts by mass of the fluoride fluorescent material (D50:5 μm), and the content of the silicon compound in the solution may be, for example, 0.004 to 0.3mol per 100.0 parts by mass of the fluoride fluorescent material (D50:30 μm). By setting the content of the silicon compound to the above lower limit value or more, the moisture resistance reliability of the obtained phosphor can be further improved. By setting the silicon compound content to the above upper limit or less, the obtained phosphor can have both moisture resistance reliability and luminescence characteristics at a further high level.
The method for producing a fluorescent material may include, in addition to the step of bringing the fluoride fluorescent material into contact with the solution, a step of heating the fluorescent material, a step of pulverizing the fluorescent material, and the like. The step of heating the phosphor is a step of heating the phosphor obtained by bringing the fluoride phosphor into contact with the solution to reduce the content of the solvent or the like. The step of heating the phosphor may be, for example, a drying step. The temperature of the heating treatment in the drying step may be set as the drying temperature, and the time of the heating treatment in the drying step may be set as the drying time. The temperature of the heat treatment may be, for example, 250℃or less, 200℃or less, 150℃or less, or 100℃or less, or 60℃or more, or 80℃or more. By setting the heat treatment temperature to the above upper limit value or less, a decrease in the moisture resistance reliability of the obtained phosphor can be suppressed. The temperature of the heat treatment may be adjusted within the above range, and may be, for example, 60 to 250 ℃, 60 to 200 ℃, 60 to 150 ℃, 60 to 100 ℃, or 80 to 100 ℃. The time of the heat treatment may be, for example, 1 minute to 24 hours, and is preferably 2 to 10 hours from the viewpoints of the moisture reduction rate of the phosphor, the productivity, and the like.
One embodiment of the present disclosure is a phosphor having a K-containing structure 2 SiF 6 ：Mn 4+ A body portion attached to the body portion and including silicon and oxygen; the ratio of silicon to potassium measured on the surface of the phosphor by X-ray photoelectron spectroscopy is 0.52 or more, and the ratio of silicon to potassium in the main body portion is lower than the ratio of silicon to potassium in the coating portion.
Fig. 1 is a schematic cross-sectional view showing an example of a phosphor. The phosphor 10 includes a main body 2 and a coating 4 provided on a surface 2a of the main body 2. In fig. 1, the coating portion 4 is shown as an example of an aggregate of the attachments 4a attached to the surface 2a of the main body portion 2, but the coating portion 4 may be a layer (for example, a layer in which a plurality of attachments 4a are integrally formed) uniformly provided on the surface 2a of the main body portion 2. In fig. 1, the coating portion 4 is shown as an example of coating the entire surface of the main body portion 2, but at least a part of the surface of the main body portion 2 may be coated.
The ratio of silicon to potassium (Si/K) measured on the surface of the phosphor 10 by X-ray photoelectron spectroscopy may be 0.52 or more, 0.55 or more, 0.60 or more, 0.70 or more, or 0.80 or more. By setting the silicon to potassium ratio in the surface of the phosphor 10 to 0.52 or more, the phosphor 10 is excellent in moisture resistance reliability. The ratio of silicon to potassium (Si/K) obtained by measuring the surface of the phosphor 10 by X-ray photoelectron spectroscopy may be, for example, 2.5 or less or 1.25 or less. By setting the silicon to potassium ratio of the phosphor 10 to 2.5 or less, the phosphor 10 can maintain good optical characteristics. The ratio (Si/K) of silicon to potassium measured on the surface of the phosphor 10 by the X-ray photoelectron spectroscopy may be adjusted within the above-described range, and may be, for example, 0.52 to 2.5, 0.55 to 2.5, 0.60 to 2.5, 0.70 to 2.5, 0.80 to 2.5, or 0.8 to 1.25. The above-mentioned ratio of silicon to potassium is a value calculated using the ratio of potassium to silicon obtained from the result of the composition analysis of the phosphor 10 measured by the X-ray photoelectron spectroscopy. Measurement by X-ray photoelectron spectroscopy in the present specification was performed under the conditions described in examples described below.
The ratio (O/K) of oxygen to potassium, which is measured on the surface of the phosphor 10 by X-ray photoelectron spectroscopy, may be, for example, 0.20 or more, 0.30 or more, 0.50 or more, 0.70 or more, or 0.80. The ratio (O/K) of oxygen to potassium, which is measured on the surface of the phosphor 10 by X-ray photoelectron spectroscopy, may be, for example, 4.0 or less or 1.5 or less. By setting the ratio of oxygen to potassium of the phosphor 10 to 4.0 or less, the phosphor 10 can maintain good optical characteristics. The ratio (O/K) of oxygen to potassium measured on the surface of the phosphor 10 by the X-ray photoelectron spectroscopy may be adjusted within the above-described range, and may be, for example, 0.20 to 4.0, 0.30 to 4.0, 0.50 to 4.0, 0.70 to 4.0, 0.80 to 4.0, 0.70 to 1.5, or 0.80 to 4.0.
The ratio of silicon to potassium (Si/K) in the body portion 2 is lower than the ratio of silicon to potassium in the coating portion 4. The silicon to potassium ratio of the main body 2 is derived from the silicon to potassium ratio of the fluoride phosphor. For K 2 SiF 6 In this case, the value is theoretically 0.5, which varies depending on the production conditions, but is generally 0.4 to 0.5.
The internal quantum efficiency of the phosphor 10 may be 80% or more, for example. After the phosphor 10 is exposed to a high-temperature and high-humidity environment (the exposure test is performed under the conditions of 60 ℃ C. And 90% RH for 25 hours), the internal quantum efficiency can be maintained at 70% or more. The internal quantum efficiency of the phosphor 10 can be sufficiently maintained at the initial internal quantum efficiency after the above-described test of exposure to a high-temperature and high-humidity environment. The retention rate of the internal quantum efficiency after the test with respect to the internal quantum efficiency before the test exposed to the high-temperature and high-humidity environment may be, for example, 90% or more, 93% or more, or 95% or more, and the humidity resistance reliability is excellent.
The above description has been given for some embodiments, and the description is applicable to the common configuration. The present disclosure is not limited to the above embodiments.
Examples
The present disclosure will be described in more detail with reference to examples and comparative examples, but the present disclosure is not limited to the following examples.
Example 1
[KMF(K 2 MnF 6 ) Is prepared from]
800mL of hydrofluoric acid (concentration: 40 mass%) was weighed into a 2000 mL-capacity fluorine resin beaker, and 260.00g of potassium hydrogen fluoride powder (manufactured by Kanto chemical Co., ltd.) and 12.00g of potassium permanganate powder (manufactured by Kanto chemical Co., ltd.) were dissolved therein to prepare an aqueous hydrofluoric acid solution. While stirring the obtained aqueous hydrofluoric acid solution with a magnetic stirrer, 8mL of hydrogen peroxide solution (concentration: 30% by mass) was added dropwise. When the amount of the hydrogen peroxide solution added exceeded a certain amount, the yellow powder started to precipitate, confirming that the color of the solution in the beaker changed from purple.
After the solution was discolored, the solution was stirred again for a while, and then stirring was stopped to precipitate a powder. After precipitation of the powder precipitate, the supernatant was removed, and methanol (manufactured by Kanto chemical Co., ltd.) was added to the beaker, and the solution was stirred. Thereafter, the stirring of the solution was stopped to reprecipitate the precipitated powder, the supernatant was removed, and methanol was added again and stirred. The above operation was repeated until the solution in the beaker became neutral. After the solution in the beaker becomes neutral, the precipitated powder is precipitated again and led throughFiltering to recover the precipitated powder. The recovered precipitated powder was dried to remove methanol. Thus, 19.00g of K was obtained 2 MnF 6 And (3) powder. K (K) 2 MnF 6 The preparation of the powder is carried out at normal temperature.
[ fluoride phosphor: KSF (K) 2 SiF 6 ) Is prepared from]
Using K prepared as described above 2 MnF 6 The powder KSF was prepared as follows. First, 200mL of hydrofluoric acid (concentration: 55 mass%, manufactured by villa-chemifa) was weighed into a beaker made of a fluororesin having a capacity of 500mL, and 25.6g of potassium hydrogen fluoride powder (manufactured by Fuji film and Wako pure chemical industries, ltd.) was dissolved therein, to thereby prepare an aqueous hydrofluoric acid solution. While stirring the obtained aqueous hydrofluoric acid solution, 6.9g of silica powder (trade name: FB-50R, manufactured by Denka Co., ltd.) and 1.2g of the above K were added 2 MnF 6 And (3) powder. Visual confirmation that when the silica powder was added to the solution, the formation of yellow powder (in K 2 SiF 6 ：Mn 4+ A compound represented by the formula (I). When the silica powder was added to the solution, the solution temperature increased due to the heat of dissolution, and after about 3 minutes from the start of the addition of the silica powder, the highest temperature was reached, after which the solution temperature was lowered to normal temperature. This is thought to be due to completion of dissolution of the silica powder.
After the silica powder was completely dissolved, the solution was stirred continuously for a while to complete the precipitation of yellow powder. The stirring was stopped, and the solution was allowed to stand, whereby a yellow powder was precipitated. Thereafter, the supernatant was removed, and the yellow powder was washed with hydrofluoric acid (produced by villa Chemifa) and methanol (produced by kanto chemical). After washing, the yellow powder was recovered by filtration. After drying the yellow powder thus recovered, it was classified by a nylon sieve having a mesh size of 75 μm, and 20.3g of yellow powdery KSF (fluoride phosphor) was obtained as a powder passing through the sieve. The volume median particle diameter (D50) of the KSF was 28. Mu.m.
[ production of phosphor ]
The KSF (fluoride phosphor) prepared as described above was prepared using a phosphor containing a potassium-containing compound,The solution of the manganese reducing agent and the silicon compound is treated, thereby preparing a phosphor. Specifically, the following is described. First, 0.14g of potassium acetate (Ack) and 1g of hydrogen peroxide solution (H 2 O 2 Concentration of: 30% by mass, manufactured by Kato chemical Co., ltd.), 6.8g (23.1 mmol) of tetraethoxysilane (TEOS, manufactured by Kato chemical Co., ltd.), 0.839g of acetic acid (AcOH), and 470g of ion-exchanged water, thereby preparing an aqueous solution. Next, 10.0g of the KSF was added, and the aqueous solution was stirred at 250rpm for 10 hours. The amount of manganese in the KSF was 0.97% by mass based on the total amount of the fluoride fluorescent material.
The solid component is precipitated by ending the stirring and standing the aqueous solution. Then, the supernatant was removed, methanol was added thereto and stirred, whereby the solid content was washed. After washing, the solid content was recovered by filtration, and the recovered solid content was dried at 100℃for 3 hours. After drying, the phosphor was classified by a nylon sieve having a mesh size of 75 μm, and 8.70g of a yellow powder was obtained as a powder passing through the sieve.
Examples 2 to 5
A phosphor was obtained in the same manner as in example 1 except that the blending ratio of each component, the treatment conditions and the drying conditions were changed as shown in table 1.
< evaluation of phosphor >)
The phosphors prepared in examples 1 to 5 were subjected to surface composition analysis and quantum efficiency evaluation by X-ray photoelectron spectroscopy in the manner described below. The same evaluation was also performed on KSF (hereinafter referred to as comparative example 1) prepared in example 1 before treatment with a solution containing a potassium-containing compound, a manganese reducing agent and a silicon compound. The results are shown in Table 2.
[ analysis of surface composition of phosphor surface by X-ray photoelectron Spectrometry ]
The ratio (atom%) of the element present on the surface of each of the phosphors prepared in examples 1 to 5 and KSF of comparative example 1 was measured by using an X-ray photoelectron spectroscopy analyzer (manufactured by Thermo Fischer Scientific Inc., trade name: K-Alpha System). Specifically, a monochromized al—kα line is used as an X-ray source to output: 36W, detection angle: 90 °, transfer energy: under conditions of 200.00eV (broad spectrum) and 50.0eV (narrow spectrum [ O1s, F1s, si2p, K2p, ca2p, cl2p, mn2p ]), the ratio of elements on the surface of the phosphor and KSF was measured in a measurement region of 400 μm×200 μm, and the ratio of silicon to potassium (Si/K) and the ratio of oxygen to potassium (O/K) were calculated. The charge neutralization was performed by discharging a current of 100. Mu.A using an electron gun.
[ evaluation of Quantum efficiency of phosphor ]
The quantum efficiencies of the phosphors prepared in examples 1 to 5 and KSF in comparative example 1 were measured using a spectrometer (trade name: MCPD-7000, manufactured by Katsukamu electronics Co., ltd.). This means the absorbance, internal quantum efficiency, and external quantum efficiency of light when the phosphor is excited with near ultraviolet light having a wavelength of 455 nm.
First, a standard reflection plate (trade name: spectralon, manufactured by Labsphere Co., ltd.) having a reflectance of 99% was provided at a side opening (10 mm) of an integrating sphere (60 mm). Monochromatic light having a wavelength of 455nm split from a light source (Xe lamp) was introduced into the integrating sphere through an optical fiber, and the spectrum of the reflected light was measured by a spectroscope. At this time, the number of photons of the excitation light (Qex) is calculated from the spectrum in the wavelength range of 450 to 465 nm.
Then, the fluorescent material was filled in a concave cuvette so that the surface thereof became smooth, and the cuvette was placed in an opening of an integrating sphere, and the monochromatic light having a wavelength of 455nm was irradiated, and the spectrum of the excited reflected light and fluorescence was measured by the spectroscope. The number of photons of excitation reflected light (Qref) and the number of photons of fluorescence (Qem) are calculated from the obtained spectral data. The number of photons of excitation light and reflected light is calculated in the same wavelength range as the number of photons of excitation light, and the number of photons of fluorescence is calculated in the range of 465 to 800 nm.
From the three obtained photon numbers Qex, qref, and Qem, the external quantum efficiency (= Qem/Qex ×100), the absorptance (= (1-Qref/Qex) ×100), and the internal quantum efficiency (= Qem/(Qx-Qref) ×100) were calculated. The results are shown in Table 2.
Then, 3g of the phosphor prepared in examples 1 to 5 and KSF of comparative example 1 were weighed into polytetrafluoroethylene glass, respectively, and spread out in a thin manner. The surface glass was placed in a high-temperature and high-humidity apparatus (trade name: IW222, manufactured by Dai and science Co., ltd.) and the inside of the high-temperature and high-humidity apparatus was set to a temperature: 60 ℃, humidity: 90% RH. After reaching the above temperature and humidity, the temperature was maintained for 25 hours. Then, the phosphor and KSF were taken out from the high temperature and high humidity vessel. After the test of exposing the phosphor and the KSF to the high-temperature and high-humidity environment was performed in this way, the internal quantum efficiency (expressed by "internal quantum efficiency after test" in table 2) of each phosphor and KSF was measured in the same manner as described above, and the maintenance rate of the internal quantum efficiency was calculated from the following formula. The higher the maintenance rate of internal quantum efficiency was judged to be close to 100%, the higher the moisture resistance reliability of the phosphor was judged to be.
[ maintenance ratio of internal quantum efficiency (%) ] = { [ internal quantum efficiency after test ]/[ internal quantum efficiency ] } ×100
TABLE 2
Industrial applicability
According to the present disclosure, a method for producing a phosphor having excellent moisture resistance reliability can be provided. According to the present disclosure, a phosphor excellent in moisture resistance reliability can also be provided.
Symbol description
2 … main body, 4 … coating part, and 10 … fluorescent body.
Claims (6)
1. A method for producing a phosphor comprising K 2 SiF 6 ：Mn 4+ Is characterized in that the phosphor is produced by a method for producing the phosphor,
having a function of making K 2 SiF 6 ：Mn 4+ A step of contacting the fluoride phosphor of (a) with a solution containing a potassium-containing compound, a reducing agent and a silicon compound,
the content of the potassium-containing compound in the solution is 1 to 30 parts by mass based on 100 parts by mass of the fluoride phosphor.
2. The method for producing a phosphor according to claim 1, wherein the compound containing potassium contains at least 1 kind selected from potassium acetate, potassium nitrate and potassium hydroxide.
3. The method for producing a phosphor according to claim 1 or 2, wherein the reducing agent contains hydrogen peroxide.
4. The method for producing a phosphor according to claim 1 or 2, wherein the solution contains at least 1 selected from water and alcohol.
5. The method for producing a phosphor according to claim 1 or 2, wherein the silicon compound contains a general formula: si (OR) 1 )(OR 2 )(OR 3 )(OR 4 ) A compound of the formula, wherein R 1 、R 2 、R 3 And R is 4 Each independently represents a monovalent hydrocarbon group.
6. A phosphor having a fluorescent material containing K 2 SiF 6 ：Mn 4+ A body portion attached to the body portion and including silicon and oxygen,
the ratio of silicon to potassium obtained by measuring the surface of the phosphor by X-ray photoelectron spectroscopy is 0.52 or more and the ratio of oxygen to potassium is 0.20 or more,
the ratio of silicon to potassium in the body portion is lower than the ratio of silicon to potassium in the coating portion.
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| CN105038776A (en) * | 2015-06-18 | 2015-11-11 | 北京宇极科技发展有限公司 | Preparation method of Mn<4+> doped fluoride fluorescent powder material and method for surface modification of Mn<4+> doped fluoride fluorescent powder material |
| JP2016210950A (en) * | 2015-04-28 | 2016-12-15 | 株式会社ネモト・ルミマテリアル | Fluoride phosphor and production method thereof, and semiconductor light-emitting device |
| CN106318373A (en) * | 2016-07-27 | 2017-01-11 | 北京宇极科技发展有限公司 | Preparation method of manganese-doped fluoride luminescent material controllable in morphology and particle size |
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| JP5783302B2 (en) | 2013-07-03 | 2015-09-24 | 日亜化学工業株式会社 | Fluoride phosphor, light emitting device using the same, and method for producing phosphor |
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| CN105038776A (en) * | 2015-06-18 | 2015-11-11 | 北京宇极科技发展有限公司 | Preparation method of Mn<4+> doped fluoride fluorescent powder material and method for surface modification of Mn<4+> doped fluoride fluorescent powder material |
| CN106318373A (en) * | 2016-07-27 | 2017-01-11 | 北京宇极科技发展有限公司 | Preparation method of manganese-doped fluoride luminescent material controllable in morphology and particle size |
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