# US 2018/0022993 A1 · Fluoride phosphor composite, method of manufacturing fluoride phosphor composite, white light emitting apparatus, display apparatus, lighting device, and electronic device > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2018/0022993 A1 - Document ID: US20180022993A1 - Status: Published application - Kind: A1 - Application number: 15/719,724 - Filed: 2017-09-29 - Published: 2018-01-25 - Earliest claimed: 2014-12-09 - Assignees: Samsung Electronics Co., Ltd. - Applicants: Samsung Electronics Co., Ltd. - Inventors: Ji Ho YOU; In Hyung LEE; Tae Hoon KIM; Jong Won PARK; Chul Soo YOON; Chi Woo LEE - Web page: https://patentgrep.com/patent/US20180022993A1 ## CPC - C09K 11/617: {Silicates} - C09K 11/025: {non-luminescent particle coatings or suspension media} - C09K 11/57: containing manganese or rhenium - C09K 11/61: containing fluorine, chlorine, bromine, iodine or unspecified halogen elements - Y02B 20/00: Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps - C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE - Y02B: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS ## Abstract There is provided a fluoride phosphor composite including: fluoride phosphor core particles that may be expressed by the empirical formula AxMFy:Mn4+, wherein A may be at least one selected from the group consisting of Li, Na, K, Rb, and Cs, M may be at least one selected from the group consisting of Si, Ti, Zr, Hf, Ge, and Sn, the composition ratio (x) of A may satisfy 2≦x≦3, the composition ratio (y) of F may satisfy 4≦y≦7, each fluoride phosphor composite particle may be coated with a Mn-free fluoride coating. The Mn-free fluoride coating may have a thickness less than or equal to 35% of the size of each fluoride phosphor composite particle. ## Claims ### Claim at position 1 1-51. (canceled) ### Claim 52 A method for preparing fluoride phosphor composite particles, the method comprising: preparing a hydrofluoric (HF) solution having a first source material containing M and a fluoride containing Mn4+; introducing a second source material containing A to the HF solution to form fluoride phosphor core particles expressed by an empirical formula of AxMfy:Mn4+, wherein one of the first and second source materials remains after the fluoride phosphor core particles are formed; and additionally introducing the other of the first and second source materials to the HF solution with the fluoride phosphor core particles formed therein, to coat the fluoride phosphor core particles with an Mn-free fluoride shell, wherein M is at least one selected from the group consisting of Si, Ti, Zr, Hf, Ge, and Sn, A is at least one selected from the group consisting of Li, Na, K, Rb, and Cs, the composition ratio (x) of A satisfies 2≦x≦3, and the composition ratio (y) of F satisfies 4≦y≦7. ### Claim 53 (depends on 52) The method of claim 52, further comprising: collecting the fluoride phosphor composite particles coated with the Mn-free fluoride shell; and introducing the fluoride phosphor composite particles and an organic material to a solvent to coat a surface of the Mn-free fluoride shell with the organic material. ### Claim 54 (depends on 53) The method of claim 53, wherein the solvent is acetone, and the organic material includes a hydrophobic organic material that can be physically adsorbed on a surface of each fluoride phosphor composite particle. ### Claim 55 (depends on 53) The method of claim 53, wherein a mole ratio of the organic material to the fluoride phosphor composite particles ranges from 1 to 4. ### Claim 56 (depends on 53) The method of claim 53, further comprising: cleaning the fluoride phosphor composite particles between the collecting of the fluoride phosphor composite particles and the coating of the surface of the fluoride shell with the organic material. ### Claim 57 (depends on 53) The method of claim 53, further comprising: cleaning the fluoride phosphor composite particles coated with the organic material, wherein the cleaning is performed two or fewer times. ### Claim 58 (depends on 52) The method of claim 52, wherein the preparing of the HF solution includes: introducing a first source material containing M to a HF solution; and introducing a fluoride containing Mn4+ to the HF solution including the first source material. ### Claim 59 (depends on 52) The method of claim 52, wherein the Mn4+-contained fluoride includes a manganese fluoride having a composition of AxMnFy. ### Claim 60 (depends on 52) The method of claim 52, wherein the first source material includes at least one selected from the group consisting of HxMFy, AxMFy, and MO2. ### Claim 61 (depends on 60) The method of claim 60, wherein the second source material includes AHF2. ### Claim 62 (depends on 61) The method of claim 61, wherein after the fluoride phosphor core particles are formed, the second source material remains, and the coating of the fluoride phosphor core particles with the Mn-free fluoride shell includes introducing the first source material. ### Claim 63 (depends on 52) The method of claim 52, wherein the Mn-free fluoride shell includes a fluoride expressed by an empirical formula of AxMFy. ### Claim 64 A method for preparing fluoride phosphor composite particles, the method comprising: preparing a hydrofluoric (HF) solution by mixing a first source material containing M and a fluoride containing Mn4+; introducing a second source material containing A to the HF solution to form fluoride phosphor core particles expressed by an empirical formula of AxMfy:Mn4+; cleaning the fluoride phosphor core particles; and introducing the fluoride phosphor core particles and an organic material to a solvent to coat the fluoride phosphor core particles with the organic material, wherein M is at least one selected from the group consisting of Si, Ti, Zr, Hf, Ge, and Sn, A is at least one selected from the group consisting of Li, Na, K, Rb, and Cs, a composition ratio (x) of A satisfies 2≦x≦3, and a composition ratio (y) of F satisfies 4≦y≦7. ### Claim 65 (depends on 64) The method of claim 64, wherein the organic material includes a hydrophobic organic material physically adsorbed on surfaces of the fluoride phosphor core particles. ### Claim 66 (depends on 65) The method of claim 65, wherein the organic material includes an organic compound having at least one functional group among a carboxyl group (—COOH) and an amine group (—NH2) and having 4 to 18 carbon atoms. ### Claim 67 (depends on 64) The method of claim 64, wherein the cleaning is performed two or fewer times. ### Claim 68 A method for preparing fluoride phosphor composite particles, the method comprising: preparing a hydrofluoric (HF) solution having a first source material containing M and a fluoride containing Mn4+; introducing a second source material containing A to the HF solution to form fluoride phosphor core particles expressed by an empirical formula of AxMfy:Mn4+, wherein one of the first and second source materials remains after the fluoride phosphor core particles are formed; additionally introducing the other of the first and second source materials to the HF solution with the fluoride phosphor core particles formed therein, to coat the fluoride phosphor core particles with an Mn-free fluoride shell, cleaning the fluoride phosphor core particles with the Mn-free fluoride shell; and introducing the fluoride phosphor core particles with the Mn-free fluoride shell and an organic material to a solvent to coat the fluoride phosphor core particles with the organic material, wherein M is at least one selected from the group consisting of Si, Ti, Zr, Hf, Ge, and Sn, A is at least one selected from the group consisting of Li, Na, K, Rb, and Cs, a composition ratio (x) of A satisfies 2≦x≦3, and a composition ratio (y) of F satisfies 4≦y≦7. ### Claim 69 (depends on 68) The method of claim 68, wherein the Mn4+-contained fluoride includes a manganese fluoride having a composition of AxMnFy and the Mn-free fluoride shell includes a fluoride expressed by an empirical formula of AxMFy. ### Claim 70 (depends on 69) The method of claim 69, wherein the second source material includes AHF2. ### Claim 71 (depends on 68) The method of claim 68, wherein after the fluoride phosphor core particles are formed, the second source material remains, and the coating of the fluoride phosphor core particles with the Mn-free fluoride shell includes introducing the first source material.