WO2019200934A1 - 一种复相荧光陶瓷及其制备方法 - Google Patents

一种复相荧光陶瓷及其制备方法 Download PDF

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WO2019200934A1
WO2019200934A1 PCT/CN2018/118825 CN2018118825W WO2019200934A1 WO 2019200934 A1 WO2019200934 A1 WO 2019200934A1 CN 2018118825 W CN2018118825 W CN 2018118825W WO 2019200934 A1 WO2019200934 A1 WO 2019200934A1
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aluminum
phosphor
phase
aluminum nitride
fluorescent ceramic
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French (fr)
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田梓峰
周萌
许颜正
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深圳光峰科技股份有限公司
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    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/581—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on aluminium nitride
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/3865—Aluminium nitrides
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    • C04B2235/9646—Optical properties

Definitions

  • the invention relates to a multiphase fluorescent ceramic having high thermal conductivity, high density and high luminous efficiency and a preparation method thereof.
  • a technique of exciting a luminescent material by using a light source such as a laser diode (LD) or a light-emitting diode (LED) to obtain a predetermined monochromatic light or a multi-color light is widely used in the fields of illumination light sources, projection displays, and the like.
  • a light source such as a laser diode (LD) or a light-emitting diode (LED)
  • the power of the blue LD or blue LED excitation light source is higher and higher, so the performance requirements for the luminescent material are also higher and higher.
  • the luminescent properties of the luminescent materials are required to be good, and on the other hand, the mechanical properties and thermal conductivity of the luminescent materials are required to be better.
  • silica gel encapsulates phosphor or fluorescent glass is far from meeting the requirements of high-power source excitation.
  • Ceramics are widely used in high-power source excitation because of their higher mechanical properties and thermal conductivity than silica gel and glass. Especially high power LD light sources.
  • Blu-ray LD has many advantages as an excitation light source: (1) There is no “sudden efficiency drop” phenomenon, so the light source cost can be reduced by increasing the light output intensity of a single chip; (2) Near monochromaticity, which can be matched according to the LD output wavelength. The phosphor is used to achieve high conversion efficiency; (3) the volume is smaller, the brightness is higher, and the terminal illuminating body is easier to design; (4) has better controllability, including adjustable light color and controllable time space.
  • Blu-ray LD may be the best source of excitation for high-intensity light sources. Compared with blue LEDs, the blue LD light source has a smaller spot size and higher power, and its spot has a higher optical power density, which has higher requirements on the mechanical properties and thermal conductivity of the luminescent ceramic.
  • common fluorescent ceramics are generally divided into two types: one is a pure phase luminescent ceramic (ie, a single-phase luminescent ceramic), such as YAG:Ce or LuAG:Ce ceramic, and the ceramic phase and the luminescent phase are in the same phase and can Sintered into a ceramic with higher transparency, but the thermal conductivity of YAG:Ce or LuAG:Ce ceramics is lower.
  • the other is a multiphase luminescent ceramic such as Al 2 O 3 &YAG:Ce ceramic or AlN&YAG:Ce ceramic, etc., the bonding phase is Al 2 O 3 or AlN, and the luminescent phase is YAG:Ce phosphor.
  • Al 2 O 3 &YAG Ce ceramics have high mechanical strength but low thermal conductivity, while AlN&YAG:Ce ceramics have high thermal conductivity.
  • the thermal expansion coefficient of AlN in AlN&YAG:Ce ceramics is 4.6 ⁇ 10 -6 /K, and the thermal expansion coefficient of YAG:Ce is 8.0 ⁇ 10 -6 /K, and the thermal expansion coefficients of the two are quite different, resulting in the sintering of multiphase ceramics.
  • AlN&YAG: Ce has a large thermal stress, so its density is low and mechanical strength is poor.
  • one problem to be solved is to develop a luminescent ceramic having both high thermal conductivity and high density and good mechanical strength, which can be adapted to the illumination of high power blue LD or LED light source. Claim.
  • the present invention aims to provide a novel multiphase fluorescent ceramic which has both high thermal conductivity, high density and good mechanical strength. Highly efficient luminescent ceramics.
  • the present invention also aims to provide a novel method for preparing a multiphase fluorescent ceramic to prepare a multiphase fluorescent ceramic having the above properties.
  • a multiphase fluorescent ceramic comprising: an aluminum nitride phase as a matrix phase, a phosphor uniformly distributed in the matrix phase, and the nitridation An aluminum oxynitride phase between the aluminum phase and the phosphor, wherein the aluminum nitride phase and the phosphor are separated from each other via the aluminum oxynitride phase.
  • the aluminum oxynitride phase is coated on the surface of the phosphor and/or the aluminum nitride phase.
  • the aluminum oxynitride phase is formed by reacting an aluminum salt coated on the surface of the phosphor or the aluminum nitride phase with the aluminum nitride during sintering of the multiphase fluorescent ceramic .
  • the phosphor is a YAG:Ce phosphor or a LuAG:Ce phosphor.
  • the aluminum oxynitride phase has a thickness of 0.05 to 1 um.
  • the phosphor accounts for 20 to 80% of the total volume of the multiphase fluorescent ceramic.
  • the phosphor has a particle size of 1 to 30 um.
  • the aluminum nitride phase has a particle size of 0.2 to 10 um.
  • a method of preparing a multiphase fluorescent ceramic comprising the steps of: S1: coating a surface of a phosphor or an aluminum nitride powder with a layer of aluminum salt, The particle size of the phosphor is 1 to 30 um and the particle size of the aluminum nitride powder is 0.05 to 1 um; S2: the coated product prepared in S1 and the aluminum nitride powder or phosphor particles And the auxiliary agent and the solvent are uniformly mixed by ball milling to obtain a mixed slurry containing the raw materials; S3: drying the mixed slurry prepared in S2 and dry-pressing, and then obtaining the green body by isostatic pressing, and Desalination treatment of the green body to obtain a ceramic body; S4: sintering the ceramic body prepared in S3 to obtain a multiphase fluorescent ceramic containing a phosphor, an aluminum oxynitride phase and an aluminum nitride phase .
  • step S5 is further included: post-processing the multiphase fluorescent ceramic prepared in S4, which includes a thinning treatment and a polishing treatment.
  • coating a layer of aluminum salt on the surface of the phosphor or aluminum nitride powder is achieved by using a method of coprecipitation using an aluminum-containing compound and a precipitant in phosphor or nitriding.
  • the surface of the aluminum powder is coated with a layer of aluminum salt.
  • the multiphase fluorescent ceramic prepared according to the multiphase fluorescent ceramic of the present invention and the preparation method of the multiphase fluorescent ceramic according to the present invention has high thermal conductivity, high density and good mechanical strength.
  • Figure 1 is a schematic illustration of a multiphase fluorescent ceramic in accordance with the present invention.
  • FIG. 2 is a flow chart showing a method of preparing a multiphase fluorescent ceramic according to Embodiment 1 of the present invention.
  • Figure 3 is a flow chart showing another method of preparing a multiphase fluorescent ceramic according to Embodiment 3 of the present invention.
  • the multiphase fluorescent ceramic comprises a phosphor 1, an aluminum oxynitride phase 2, and an aluminum nitride phase 3.
  • the aluminum nitride phase 3 is a matrix phase, and the phosphor 1 is uniformly distributed in the matrix phase.
  • the aluminum oxynitride phase 2 is located between the phosphor 1 and the aluminum nitride phase 3.
  • the aluminum oxynitride phase 2 may be coated on the outer surface of the phosphor 1.
  • the aluminum oxynitride phase 2 may also be coated on the surface of the aluminum nitride phase 3.
  • the phosphor 1 and the aluminum nitride phase 3 can be separated from each other via the aluminum oxynitride phase 2. That is, the aluminum oxynitride phase 2 can be bonded to the phosphor 1 and the aluminum nitride phase 3 at the phase interface, respectively, and the phosphor 1 and the aluminum nitride phase 3 are not in direct contact, that is, the phosphor 1 and There is no phase interface between the aluminum nitride phases 3.
  • the multiphase fluorescent ceramic of the present invention comprises a matrix phase and a luminescent phase, wherein the matrix phase (i.e., the ceramic phase) is an aluminum nitride and an aluminum oxynitride phase, and the luminescent phase is a phosphor phase.
  • the phosphor may be, for example, a YAG:Ce phosphor or a LuAG:Ce phosphor, and the phosphor may have a particle diameter of 1 to 30 um.
  • the phosphor is sintered by surface-coated aluminum salt and aluminum nitride to form a multiphase fluorescent ceramic comprising an aluminum nitride phase, an aluminum oxynitride phase and a phosphor, wherein the thickness of the aluminum oxynitride phase on the surface of the phosphor is 0.05 ⁇ 1um to avoid the thickness is too thin to completely cover the phosphor particles and the manufacturing process is difficult, and also avoid the thickness is too thick to cause a decrease in light transmittance and affect the light-emitting efficiency of the phosphor particles.
  • the phosphor may account for 20 to 80% of the total volume of the multiphase fluorescent ceramic.
  • the structure of the multiphase fluorescent ceramic of the present invention is YAG:Ce-AlON-AlN or LuAG:Ce-AlON-AlN, and the luminescent phase is YAG: Ce or LuAG: Ce, the matrix phase is AlN and AlON.
  • the aluminum oxynitride phase (AlON) is located between the phosphor (YAG: Ce or LuAG: Ce) and the aluminum nitride phase (AlN) and between the phosphor and the aluminum nitride phase
  • AlON aluminum oxynitride phase
  • AlN aluminum nitride phase
  • the aluminum oxynitride phase is formed by reacting an aluminum salt coated on the surface of the phosphor or aluminum nitride powder with an aluminum nitride binder phase during sintering, which ensures the aluminum oxynitride phase and nitrogen. Since the aluminum alloy phase has sufficient bonding strength, and since the compatibility between the aluminum oxynitride and the aluminum nitride is good, the phase interface between the aluminum oxynitride phase and the aluminum nitride phase can be sintered and dense.
  • the thermal expansion coefficient of the YAG phosphor is 8.0 ⁇ 10 -6 /K, which is almost the same, so the aluminum oxynitride phase during the sintering process There is no thermal stress between the phosphors, the density of sintering is high, and the mechanical strength is good. Therefore, the problem of poor bonding between AlN and YAG:Ce in the AlN&YAG:Ce ceramics in the prior art is solved.
  • the aluminum oxynitride phase is a cubic system, and its presence does not affect the transparency and luminous efficiency of the ceramic.
  • the multiphase fluorescent ceramic of the present invention also has high thermal conductivity due to the presence of AlN. Accordingly, the present invention provides a fluorescent ceramic having high thermal conductivity, high density, good mechanical strength, and high luminous efficiency, which is illuminated by a high-power excitation light source such as a blue LD or a blue LED. It can efficiently illuminate and realize high-intensity illumination source, thereby further improving the brightness of illumination and projection light source, and thus can meet the illumination requirements of high-power excitation light sources such as high-power blue LD or LED light source.
  • a high-power excitation light source such as a blue LD or a blue LED.
  • the above multiphase fluorescent ceramics in the present invention can be produced by a production method including the following steps.
  • S1 coating a surface of the phosphor (or aluminum nitride powder) with a layer of aluminum salt, the phosphor having a particle size of 1 to 30 um and the aluminum nitride powder having a particle size of 0.05 ⁇ 1um.
  • a layer of aluminum salt is coated on the surface of the phosphor or aluminum nitride powder by a method of coprecipitation using an aluminum-containing compound and a precipitating agent.
  • S2 The coated product prepared in S1 is uniformly ball-milled with aluminum nitride powder (or phosphor), an auxiliary agent and a solvent to obtain a mixed slurry containing these raw materials. Specifically, a phosphor (or aluminum nitride powder) coated with an aluminum salt on the surface prepared in S1 is uniformly mixed with an aluminum nitride powder (or phosphor), an auxiliary agent, and a solvent to obtain a ball mill.
  • aluminum nitride powder or phosphor
  • a solvent to obtain a ball mill.
  • a phosphor or aluminum nitride powder coated with a layer of aluminum salt, aluminum nitride powder (or phosphor), and a mixed slurry of an auxiliary agent and a solvent
  • the auxiliary agent may include a sintering aid, a dispersing agent, etc.
  • the sintering aid may be Y 2 O 3 or MgO, the sintering aid may have a particle diameter of 0.02 to 1 um, and the sintering aid accounts for a phosphor (or aluminum nitride powder) coated with a layer of aluminum salt, and nitrided.
  • the total mass of the aluminum powder (or phosphor) and the sintering aid is 0.01 to 4.
  • S4 Sintering the ceramic body prepared in S3 to obtain a multiphase fluorescent ceramic comprising a phosphor, an aluminum oxynitride phase, and an aluminum nitride phase.
  • the ceramic bad body prepared in S3 is placed in a sintering furnace for sintering, and after completion of sintering, a composite phase fluorescent ceramic containing a phosphor, an aluminum oxynitride phase, and an aluminum nitride phase is obtained, wherein the sintering method may be Hot pressing, air pressure, vacuum, hot isostatic pressing or discharging plasma.
  • S5 post-treating the multiphase fluorescent ceramic prepared in S4, the post-treatment including a thinning treatment and a polishing treatment.
  • the phosphor or aluminum nitride powder
  • aluminum salt or aluminum nitride powder
  • aluminum nitride powder or The phosphor is mixed and sintered, and the aluminum salt can be first reacted to form alumina during the sintering process, and then reacted with aluminum nitride to form an aluminum oxynitride phase between the phosphor and the aluminum nitride phase, thereby ensuring nitrogen.
  • the alumina phase is interposed between the phosphor and the aluminum nitride phase and the phosphor and the aluminum nitride phase are not in direct contact with each other.
  • the phosphor is combined with the aluminum nitride phase through the aluminum oxynitride.
  • the phosphor is combined with the aluminum nitride phase through the aluminum oxynitride.
  • the sintering density at the phase interface between the aluminum oxynitride phase and the aluminum nitride phase is high, and since the aluminum oxynitride phase passes through the aluminum salt and nitrogen The aluminum phase reacts, so the bond strength between the aluminum oxynitride phase and the aluminum nitride phase is relatively large.
  • the thermal expansion coefficients of the aluminum oxynitride and the phosphor are substantially the same, there is no thermal stress between the aluminum oxynitride and the phosphor, and the compaction can be performed to obtain a multiphase ceramic having a relatively high mechanical strength.
  • the present invention solves the problem that the thermal expansion coefficient of aluminum nitride and the thermal expansion coefficient of the phosphor greatly differs, and the composite ceramics of aluminum nitride and phosphor, AlN&YAG:Ce, have higher thermal stress, lower density, and mechanical Poor strength problem.
  • the AlN&YAG:Ce multiphase fluorescent ceramic has high thermal conductivity, and therefore, the present invention produces a luminescent ceramic having high thermal conductivity and good mechanical strength, which is
  • a high-power excitation light source such as a blue LD or a blue LED
  • it can efficiently emit light and realize a high-intensity illumination source, thereby further improving the brightness of the illumination and the projection light source, and thus can adapt to the illumination requirements of the high-power blue LD or the LED light source.
  • FIG. 2 is a flow chart showing a method of preparing a multiphase fluorescent ceramic according to Embodiment 1 of the present invention.
  • a high-purity aluminum nitride, a commercial YAG:Ce phosphor, and aluminum nitrate are used as raw materials to prepare a multiphase fluorescent ceramic, wherein polyvinyl butyral (PVB) is used as a binder, and Adding dispersants, sintering aids, etc.
  • PVB polyvinyl butyral
  • the first step S1 is performed to coat the surface of the YAG:Ce phosphor powder with a layer of aluminum salt: a surface of the commercial YAG:Ce phosphor powder is coated with a layer of aluminum by coprecipitation.
  • Salt YAG: Ce phosphor a surface of the commercial YAG:Ce phosphor powder is coated with a layer of aluminum by coprecipitation.
  • Salt YAG: Ce phosphor Specifically, an appropriate amount of commercial YAG:Ce phosphor powder having a particle size of 1 to 30 um and aluminum nitrate (AlNO 3 ) are dissolved in an aqueous solution, and a precipitating agent is added while stirring, and the precipitating agent may be ammonia water or an ammonium salt (such as carbonic acid).
  • a person skilled in the art can select any suitable aluminum-containing compound as a raw material, and select a suitable deposition agent according to the kind of the aluminum-containing compound raw material selected to achieve the purpose of coating a surface of the YAG:Ce phosphor powder with a layer of aluminum salt.
  • a suitable deposition agent according to the kind of the aluminum-containing compound raw material selected to achieve the purpose of coating a surface of the YAG:Ce phosphor powder with a layer of aluminum salt.
  • sodium metaaluminate NaAlO 2
  • HCl dilute hydrochloric acid
  • the present invention is not limited thereto and can be coated on the surface of the YAG:Ce phosphor.
  • Any method of a layer of aluminum salt can be used, such as spray drying.
  • the aluminum salt herein is the most general aluminum-containing compound, and includes, for example, aluminum hydroxide (Al(OH) 3 ), aluminum nitrate (AlNO 3 ), aluminum sulfate (Al 2 (SO 4 ) 3 ), and the like.
  • sodium aluminate (NaAlO 2) and potassium aluminate (KAlO 2) such as partial aluminate.
  • the second step S2 is performed to carry out the mixing: the aluminum nitride powder having a particle size of 0.05 to 1 um, the YAG:Ce phosphor powder coated with an aluminum salt on the surface obtained in S1, the solvent and the particle size are a sintering aid Y 2 O 3 or MgO of 0.02 to 1 um is uniformly mixed and ball milled for a period of time, for example, 6 to 24 hours, to obtain a mixed slurry of aluminum nitride and the above-mentioned YAG:Ce phosphor coated with a layer of aluminum salt, wherein The sintering aid accounts for 0.01 to 4% of the total mass of the aluminum nitride, the YAG:Ce phosphor coated with a layer of aluminum salt and the sintering aid.
  • the third step S3 is performed to perform the green body molding: the mixed slurry obtained in S2 is dried in an oven, and then ground and sieved to avoid powder agglomeration and adversely affect the sintering of the ceramic, and then at 10-20 MPa.
  • the ceramic powder obtained above is dry-formed under dry pressing pressure, and then obtained by isostatic pressing at an isostatic pressure of 200 to 300 MPa to obtain a green body, and the green body is subjected to degreasing treatment to obtain a ceramic green body.
  • the degreasing temperature of the green body is 800-1000 ° C, and the degreasing time is 2-6 h.
  • the fourth step S4 is performed to perform ceramic sintering: the ceramic body obtained in S3 is sintered in a vacuum atmosphere furnace at a sintering temperature of 1600 to 1800 ° C, the atmosphere is nitrogen, and the sintering time is 6 to 12 hours, and the cooling is performed. Thereafter, a multiphase fluorescent ceramic comprising a phosphor, an aluminum oxynitride phase and an aluminum nitride phase having the structure shown in Fig. 1 was obtained.
  • a fifth step S5 is performed to perform ceramic post-treatment: the multiphase fluorescent ceramic obtained in S4 is subjected to post-treatment including thinning and polishing treatment.
  • the thickness of the aluminum oxynitride phase coated on the surface of the obtained phosphor is 0.05 um to 1 um to enable complete coating of the phosphor and good light transmittance. It can be understood that when the thickness of the aluminum oxynitride is thin, the aluminum oxynitride phase may not completely cover the phosphor, and there may be a case where the aluminum nitride phase is in direct contact with the phosphor, resulting in preparation. The sintering density of the multiphase fluorescent ceramics is not good enough. It can also be understood that when the thickness of the aluminum oxynitride is thick, the light transmittance is lowered, which affects the light-emitting efficiency of the phosphor.
  • the preparation of a suitable thickness of aluminum oxynitride is important to the present invention.
  • the thickness of the aluminum oxynitride phase coated on the surface of the phosphor can be controlled by adjusting the concentration of the precipitation solution or repeating the precipitation process in S1 (ie, the aluminum salt coating process).
  • the first step S1 can be performed by the following process to obtain a desired thickness of the aluminum oxynitride phase, and an appropriate amount of commercial YAG:Ce phosphor powder and aluminum nitrate having a particle size of 1 to 30 um are dispersed in the aqueous solution.
  • the precipitating agent is added while stirring, and the precipitating agent may be ammonia water or an ammonium salt (such as ammonium hydrogencarbonate), and fully reacted to obtain a suspension of YAG:Ce phosphor powder coated with a layer of aluminum salt (ie, aluminum hydroxide);
  • the suspension of YAG:Ce phosphor coated with a layer of aluminum salt is washed with deionized water until the pH is neutral and dried to obtain YAG:Ce phosphor particles coated with a layer of aluminum salt;
  • the YAG:Ce phosphor of the layer aluminum salt is again dispersed in the aqueous solution with aluminum nitrate, and the precipitant is added with stirring, and after fully reacting, the aluminum salt layer of the YAG:Ce phosphor powder is coated again with an aluminum salt (ie, , aluminum hydroxide), and after washing and drying, phosphor particles having a surface coated with more aluminum salt are obtained.
  • the aluminum salt coating process is repeated once by way of example, the aluminum salt coating process may be repeated several times depending on the concentration of the precipitant used.
  • the aluminum salt of the desired thickness is used to obtain the desired thickness of the aluminum oxynitride phase.
  • YAG:Ce phosphor powder and nitriding having a large difference in thermal expansion coefficient can be avoided.
  • the direct contact of aluminum is caused by the presence of aluminum salts.
  • the aluminum salt is first chemically reacted to form alumina, and then reacted with aluminum nitride to form aluminum oxynitride.
  • the resulting aluminum oxynitride can be sintered densely with YAG:Ce phosphor, overcoming the YAG:Ce phosphor.
  • the problem of poor density due to sintering with aluminum nitride results in a composite fluorescent ceramic having improved mechanical strength.
  • the sintering mode of the ceramic was changed as compared with the first embodiment, and the other aspects were the same as those in the first embodiment.
  • discharge plasma sintering is selected, that is, the ceramic powder is placed in a graphite mold, and sintered at a pressure of 5 to 40 MPa and a sintering temperature of 1600 to 1800 °C.
  • the main advantage of the spark plasma sintering method is that the sintering temperature can be lowered and the sintering time can be shortened to prevent excessive grain growth and reduce the mechanical strength of the ceramic.
  • the ceramic obtained by the sintering method needs to be annealed in a nitrogen atmosphere at a later stage. This embodiment is suitable for applications where the mechanical strength of the ceramic is relatively high, and thus provides an alternative to the present invention.
  • Fig. 3 is a flow chart showing another method of preparing a multiphase fluorescent ceramic according to Embodiment 3 of the present invention.
  • a high-purity aluminum nitride, a commercial YAG:Ce phosphor, and aluminum nitrate are used as raw materials to prepare a multiphase fluorescent ceramic, wherein PVB is selected as a binder, and A dispersant, a sintering aid, or the like can be added.
  • the specific preparation method is as follows.
  • the first step S1 is performed, and in the embodiment 1 and the embodiment 2, the surface of the YAG:Ce phosphor is coated with a layer of aluminum salt.
  • the surface of the aluminum nitride powder is coated with a layer.
  • Aluminum salt A layer of aluminum salt was coated on the surface of the aluminum nitride powder by a coprecipitation method, and the coprecipitation method was the same as in Example 1. Specifically, an appropriate amount of aluminum nitride powder having a particle size of 0.05 to 1 um and aluminum nitrate are dissolved in an aqueous solution, and a precipitating agent is added while stirring, and the precipitating agent may be ammonia water or an ammonium salt (such as ammonium hydrogencarbonate).
  • a suspension of aluminum nitride powder coated with a layer of aluminum salt ie, aluminum hydroxide
  • a suspension of aluminum nitride powder coated with a layer of aluminum salt is washed with deionized water to pH.
  • an aluminum nitride powder coated with a layer of aluminum salt is obtained, wherein the particle size of the aluminum nitride powder is 0.05 to 1 um, which is smaller than the particle size of the commercial phosphor 1 to 30 um, Since the surface area is large, it is more feasible to coat the surface of the aluminum nitride powder with an aluminum salt than the aluminum salt coated on the surface of the phosphor in Example 1.
  • any suitable aluminum-containing compound may be selected as a raw material, and a suitable deposition agent is selected according to the kind of the selected aluminum-containing compound raw material to realize the aluminum nitride powder.
  • the surface is coated with a layer of aluminum salt.
  • any method other than the coprecipitation method capable of coating an aluminum salt on the surface of the aluminum nitride powder may be used in the aluminum nitride powder.
  • the surface is coated with a layer of aluminum salt, such as a spray drying method.
  • the second step S2 is performed to carry out the mixing: the aluminum nitride powder coated with a layer of aluminum salt obtained in S1, the commercial YAG:Ce phosphor powder having a particle size of 1-30 um, the solvent and the particle size are 0.02 ⁇ 1um sintering aid Y 2 O 3 or MgO is uniformly mixed by ball milling for a period of time, for example 6-24h, to obtain a mixed slurry of aluminum nitride powder coated with a layer of aluminum salt and YAG:Ce phosphor powder, wherein The sintering aid accounts for 0.01 to 4% of the total mass of the aluminum nitride powder coated with a layer of aluminum salt, the YAG:Ce phosphor and the sintering aid.
  • the third step S3 is performed to perform the green body molding: the mixed slurry obtained in S2 is dried in an oven, and then ground and sieved to avoid powder agglomeration and adversely affect the sintering of the ceramic, and then at 10-20 MPa.
  • the ceramic powder obtained above is dry-formed under dry pressing pressure, and then obtained by isostatic pressing at an isostatic pressure of 200 to 300 MPa to obtain a green body, and the green body is subjected to degreasing treatment to obtain a ceramic green body.
  • the degreasing temperature of the green body is 800-1000 ° C, and the degreasing time is 2-6 h.
  • the fourth step S4 is performed to perform ceramic sintering: the ceramic body obtained in S3 is sintered in a vacuum atmosphere furnace at a sintering temperature of 1600 to 1800 ° C, the atmosphere is nitrogen, and the sintering time is 6 to 12 hours, and the cooling is performed. Thereafter, a multiphase fluorescent ceramic comprising a phosphor, an aluminum oxynitride phase and an aluminum nitride phase having the structure shown in Fig. 1 was obtained.
  • a fifth step S5 is performed to perform ceramic post-treatment: the multiphase fluorescent ceramic obtained in S4 is post-treated, including thinning and polishing treatment.
  • the thickness of the aluminum oxynitride phase coated on the surface of the obtained aluminum nitride powder is 0.05 um to 1 um, so that complete coating of the aluminum nitride powder can be achieved and good light is obtained. Transmittance.
  • the aluminum salt coated on the surface of the aluminum nitride powder can be controlled by adjusting the concentration of the precipitation solution or repeating the precipitation process in S1 (ie, the aluminum salt coating process). The thickness is such that a desired thickness of the aluminum oxynitride phase is obtained.
  • an aluminum salt on the surface of the aluminum nitride powder and then mixing and sintering it with the YAG:Ce phosphor, it is also possible to avoid YAG:Ce phosphor and nitrogen having a large difference in thermal expansion coefficients.
  • the aluminum salt first forms alumina by chemical reaction, and then reacts with aluminum nitride to form aluminum oxynitride.
  • the formed aluminum oxynitride can be sintered and dense with YAG:Ce phosphor, which also overcomes YAG:Ce fluorescence. The problem that the powder and the aluminum nitride are sintered to cause a difference in density, thereby obtaining a multiphase fluorescent ceramic having improved mechanical strength.
  • the ceramic sintering mode can also be changed to the discharge plasma sintering described in Embodiment 2, thereby reducing the sintering temperature and shortening the sintering time, preventing the grain growth from being excessive and reducing the ceramic.
  • Mechanical strength The same applies to the case where the mechanical strength of the ceramic is relatively high.
  • the fluorescent ceramics prepared in the above Examples 1 to 3 are multiphase fluorescent ceramics, and the structure thereof can be represented as YAG:Ce-AlON-AlN, wherein the binder phase is AlN, and the particle size of the AlN raw material is 0.05 to 1 um, sintering.
  • the post-particle size ranges from 0.2 to 10 um, and the luminescent phase is YAG:Ce phosphor, and the YAG:Ce phosphor accounts for 20-80% of the total volume of the ceramic to achieve good luminescence efficiency.
  • AlON is between YAG:Ce and AlN and has a thickness of 0.05 to 1 um, thereby avoiding direct contact between YAG:Ce and AlN to overcome the multiphase ceramic AlN&YAG:Ce due to the large difference in thermal expansion coefficients.
  • the multiphase fluorescent ceramics prepared in the above Examples 1 to 3 are luminescent ceramics containing YAG:Ce phosphor powder, aluminum oxynitride phase and aluminum nitride phase, which are high in thermal conductivity and high in density. Fluorescent ceramic with good mechanical strength and high luminous efficiency, which can efficiently emit light and realize high-intensity illumination source when illuminated by high-power excitation light source such as blue LD or blue LED, thereby further improving illumination and projection light source. Brightness, therefore, can be adapted to the illumination requirements of high power blue LD or LED sources.
  • the phosphor in the above embodiment can also be replaced by LuAG:Ce phosphor, and the structure of the multiphase fluorescent ceramic thus prepared is LuAG:Ce-AlON-AlN, wherein the luminescent phase is LuAG:Ce phosphor.
  • This also achieves high thermal conductivity, high density, good mechanical strength and high luminous efficiency, and can efficiently emit light and realize high-intensity illumination light when illuminated by a high-power excitation light source such as a blue LD or a blue LED.
  • a high-power excitation light source such as a blue LD or a blue LED.
  • the present invention can be realized by the respective raw materials enumerated in the present invention, as well as the upper and lower limits of the raw materials of the present invention, the upper and lower limits of the process parameters, and the values of the intervals, and the examples are not enumerated herein; the technical essence according to the present invention is Any simple modifications or equivalent changes made to the embodiments are still within the scope of the technical solutions of the present invention.

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Abstract

提供一种新型的复相荧光陶瓷及其制备方法。该复相荧光陶瓷包括：作为基体相的氮化铝相、均匀分布在基体相中的荧光粉以及位于氮化铝相和荧光粉之间的氮氧化铝相，其中氮化铝相和荧光粉经由氮氧化铝相彼此隔开。该复相荧光陶瓷通过共沉淀法在荧光粉或氮化铝的表面包覆一层铝盐，然后对包含了表面包覆有一层铝盐的荧光粉或氮化铝与氮化铝或荧光粉的混合浆料进行烧结来制备。该复相荧光陶瓷具有高的热导率、高的致密度和良好的机械强度，可被高功率激发光源激发，如高功率蓝光LD或者蓝光LED，可以作为高亮度的照明光源，从而进一步提高照明或投影光源的亮度。

Description

一种复相荧光陶瓷及其制备方法 技术领域
本发明涉及一种具有高的热导率、高的致密度和高的发光效率的复相荧光陶瓷及其制备方法。
背景技术
目前，利用激光二极管(LD)或者发光二极管(LED)等光源激发发光材料以获得预定单色光或者多色光的技术广泛应用于照明光源、投影显示等领域。随着对光源亮度的要求越来越高，蓝光LD或者蓝光LED激发光源的功率越来越高，所以对发光材料的性能要求也越来越高。一方面要求发光材料的发光性能要好，另一方面也要求发光材料的机械性能、热导率等特性要更好。在这种情况下，硅胶封装荧光粉或者荧光玻璃的方式已远不能满足高功率光源激发的要求，陶瓷由于其机械性能和热导率均高于硅胶和玻璃而被广泛应用于高功率光源激发，特别是高功率LD光源。
蓝光LD作为激发光源具有很多优点：(1)无“效率骤降”现象，因此可以通过提高单个芯片的出光强度来降低光源成本；(2)近单色性，可根据LD输出波长匹配合适的荧光体以实现高转换效率；(3)体积更小、亮度更高，更易设计终端照明体；(4)具有更好的可控性，包括光色可调、时间空间可控等。蓝光LD可能成为高亮度光源的最佳激发光源。相比于蓝光LED，蓝光LD光源的光斑更小且功率更大，其光斑的光功率密度更大，因而对发光陶瓷的机械性能及热导率有更高的要求。
目前，常见的荧光陶瓷一般分为两种：一种是纯相发光陶瓷(即，单相发光陶瓷)，如YAG:Ce或者LuAG:Ce陶瓷，其成瓷相和发光相为同一相并且可以烧结成透明度较高的陶瓷，但是YAG:Ce或者LuAG:Ce陶瓷的热导率较低。另一种是复相发光陶瓷，如Al 2O 3&YAG:Ce陶瓷或者AlN&YAG:Ce陶瓷等，其粘接相为Al 2O 3或AlN等，发光相为YAG:Ce 荧光粉。Al 2O 3&YAG:Ce陶瓷机械强度高，但是热导率较低，而AlN&YAG:Ce陶瓷的热导率高。然而，AlN&YAG:Ce陶瓷中AlN的热膨胀系数为4.6×10 -6/K，YAG:Ce的热膨胀系数为8.0×10 -6/K，两者热膨胀系数相差较大，导致其烧结的复相陶瓷AlN&YAG:Ce热应力较大，因而其致密度较低，机械强度较差。
因此，亟待解决的一个问题是开发出一种既具有高的热导率，也具有高的致密度和良好的机械强度的发光陶瓷，所述发光陶瓷能够适应高功率蓝光LD或LED光源的发光要求。
发明内容
技术问题
有鉴于此，为了解决上述问题，本发明旨在提供一种新型的复相荧光陶瓷，所述复相荧光陶瓷是既具有高的热导率，也具有高的致密度和良好的机械强度的高效发光陶瓷。同时，本发明还旨在提供一种这种新型的复相荧光陶瓷的制备方法以制备出具有上述性能的复相荧光陶瓷。
技术方案
根据本发明的一方面，提供了一种复相荧光陶瓷，所述复相荧光陶瓷包括：作为基体相的氮化铝相、均匀分布在所述基体相中的荧光粉以及位于所述氮化铝相和所述荧光粉之间的氮氧化铝相，其中所述氮化铝相和所述荧光粉经由所述氮氧化铝相彼此隔开。
进一步地，所述氮氧化铝相包覆在所述荧光粉和/或所述氮化铝相的表面上。
进一步地，所述氮氧化铝相是在所述复相荧光陶瓷的烧结过程中通过包覆在所述荧光粉或所述氮化铝相表面的铝盐与所述氮化铝相反应生成的。
进一步地，所述荧光粉为YAG:Ce荧光粉或LuAG:Ce荧光粉。
进一步地，所述氮氧化铝相的厚度为0.05～1um。
进一步地，所述荧光粉占所述复相荧光陶瓷总体积的20～80％。
进一步地，所述荧光粉的粒径大小为1～30um。
进一步地，所述氮化铝相的粒径大小为0.2～10um。
根据本发明的另一方面，提供了一种复相荧光陶瓷的制备方法，所述方法包括以下步骤：S1：在荧光粉或氮化铝粉体的表面上包覆一层铝盐，所述荧光粉的粒径大小为1～30um并且所述氮化铝粉体的粒径大小为0.05～1um；S2：将S1中制备得到的包覆后的产物与氮化铝粉体或荧光粉颗粒、助剂和溶剂均匀混合球磨以制得包含这些原料的混合浆料；S3：将S2中制备得到的所述混合浆料干燥并干压成型，然后通过等静压压制来获得素坯，并对所述素坯进行脱脂处理以得到陶瓷坯体；S4：对S3中制备得到的所述陶瓷坯体进行烧结处理以得到包含荧光粉、氮氧化铝相和氮化铝相的复相荧光陶瓷。
进一步地，在步骤S4之后还包括步骤S5：对S4中制备得到的所述复相荧光陶瓷进行后处理，所述后处理包括减薄处理和抛光处理。
进一步地，在S1中，在荧光粉或氮化铝粉体的表面上包覆一层铝盐是通过如下方法实现的：采用共沉淀的方法使用含铝化合物和沉淀剂在荧光粉或氮化铝粉体的表面上包覆一层铝盐。
有益效果
在本发明中，根据本发明的复相荧光陶瓷以及根据本发明的复相荧光陶瓷的制备方法制备的复相荧光陶瓷是一种具有高的热导率、高的致密度和良好的机械强度的高效发光陶瓷，可被高功率蓝光LD或者蓝光LED激发，实现高亮度的照明光源，进一步提高照明或投影光源的亮度。
附图说明
附图表示本文所述的非限制性示例性实施例。本领域技术人员将要理解的是，附图中的部件不一定按比例绘制，而是用于重点说明本发明的原理。在附图中：
图1是根据本发明的复相荧光陶瓷的示意图。
图2是根据本发明实施例1的复相荧光陶瓷的制备方法的流程图。
图3是根据本发明实施例3的复相荧光陶瓷的另一种制备方法的流程图。
附图标记列表
1：荧光粉
2：氮氧化铝相
3：氮化铝相
具体实施方式
以下，参照附图更全面地说明本发明的一个或多个示例性实施例，在附图中，本领域技术人员能够容易地确定本发明的一个或多个示例性实施例。如本领域技术人员应认识到的，只要不脱离本发明的精神或范围，可以以各种不同的方式对所述示例性实施例进行修改，本发明的精神或范围不限于本文所述的示例性实施例。
现在参照附图对本发明的实施例进行详细说明。
本发明提供了一种复相荧光陶瓷，如图1所示，该复相荧光陶瓷包括荧光粉1、氮氧化铝相2和氮化铝相3。氮化铝相3为基体相，荧光粉1均匀地分布在基体相中。氮氧化铝相2位于荧光粉1和氮化铝相3之间。具体地，氮氧化铝相2可以包覆在荧光粉1的外表面上。可选择地，氮氧化铝相2也可以包覆在氮化铝相3的表面上。换句话说，荧光粉1和氮化铝相3可以经由氮氧化铝相2彼此隔开。也就是说，氮氧化铝相2可以在相界面处分别与荧光粉1和氮化铝相3接触结合在一起，而荧光粉1和氮化铝相3不直接接触，即，荧光粉1和氮化铝相3之间不存在相界面。如上所述，本发明的复相荧光陶瓷包含基体相和发光相两相，其中基体相(即，成瓷相)为氮化铝和氮氧化铝相，发光相为荧光粉相。可选择地，荧光粉可以为如YAG:Ce荧光粉或LuAG:Ce荧光粉等，并且荧光粉的粒径可以为1～30um。荧光粉通过表面包覆的铝盐与氮化铝复合烧结而形成包含氮化铝相、氮氧化铝相以及荧光粉的复相荧光陶瓷，其中荧光粉表面的氮氧化铝相的厚度为0.05～1um以避免厚度太薄而导致不能完全包覆荧光粒以及制作工艺上的较大难度，同时也避免了厚度太 厚而导致透光率的降低并影响荧光粉颗粒的出光效率。另外，为了使所得到的复相荧光陶瓷具有良好的发光效率，荧光粉可以占复相荧光陶瓷总体积的20～80％。在采用YAG:Ce或LuAG:Ce作为本发明的荧光粉的情况下，本发明的复相荧光陶瓷的结构为YAG:Ce-AlON-AlN或者LuAG:Ce-AlON-AlN，发光相为YAG:Ce或LuAG:Ce，基体相为AlN和AlON。
在本发明的复相荧光陶瓷中，由于氮氧化铝相(AlON)位于荧光粉(YAG:Ce或LuAG:Ce)与氮化铝相(AlN)之间并且荧光粉与氮化铝相之间不直接接触(两者之间没有相界面)，所以只存在氮氧化铝相与荧光粉之间的相界面以及氮氧化铝相与氮化铝相之间的相界面。一方面，氮氧化铝相是通过在荧光粉或氮化铝粉体的表面上包覆的铝盐与氮化铝粘结相在烧结过程中反应形成的，这确保了氮氧化铝相与氮化铝相之间足够的粘结强度，同时由于氮氧化铝与氮化铝两者的相容性较好，所以氮氧化铝相与氮化铝相之间的相界面处可以烧结致密。另一方面，由于氮氧化铝的热膨胀系数为7.9×10 -6/K，YAG荧光粉的热膨胀系数为8.0×10 -6/K，两者几乎一样，所以在烧结过程中氮氧化铝相与荧光粉之间没有热应力，烧结致密度较高，机械强度较好，因此解决了现有技术中的AlN&YAG:Ce陶瓷中AlN与YAG:Ce界面结合较差的问题。此外，需要说明的是，氮氧化铝相为立方晶系，其存在不会影响陶瓷的透明度和发光效率。另外，由于AlN的存在，本发明的复相荧光陶瓷也具有高的热导率。因此，本发明提供了一种具有高的热导率、高的致密度、良好的机械强度和高的发光效率的荧光陶瓷，该发光陶瓷在被蓝光LD或者蓝光LED等高功率激发光源照射时能够高效发光并实现高亮度的照明光源，从而进一步提高照明和投影光源的亮度，因此能够适应高功率蓝光LD或LED光源等高功率激发光源的发光要求。
此外，本发明中的上述复相荧光陶瓷可以通过包括以下步骤的制备方法来制备。
S1：在荧光粉(或氮化铝粉体)的表面上包覆一层铝盐，所述荧光粉的粒径大小为1～30um并且所述氮化铝粉体的粒径大小为0.05～1um。具 体地，采用共沉淀的方法使用含铝化合物和沉淀剂在荧光粉或氮化铝粉体的表面上包覆一层铝盐。
S2：将S1中制备得到的包覆后的产物与氮化铝粉体(或荧光粉)、助剂和溶剂均匀混合球磨以制得包含这些原料的混合浆料。具体地，将S1中制备得到的表面包覆有一层铝盐的荧光粉(或氮化铝粉体)与氮化铝粉体(或荧光粉)、助剂和溶剂均匀混合球磨以制得包含包覆有一层铝盐的荧光粉(或氮化铝粉体)、氮化铝粉体(或荧光粉)以及助剂和溶剂的混合浆料，其中助剂可以包括烧结助剂和分散剂等，烧结助剂可以为Y 2O 3或者MgO，烧结助剂的粒径可以为0.02～1um，并且烧结助剂占包覆有一层铝盐的荧光粉(或氮化铝粉体)、氮化铝粉体(或荧光粉)以及烧结助剂总质量的0.01～4。
S3：将S2中制备得到的所述混合浆料干燥并干压成型，然后通过等静压压制来获得素坯，并对所述素坯进行脱脂处理以得到陶瓷坯体。具体地，将S2中制备得到的包含包覆有一层铝盐的荧光粉(或氮化铝粉体)、氮化铝粉体(或荧光粉)以及助剂和溶剂的混合浆料置于烘箱中干燥，在10～20MPa的干压压力下使其干压成型，然后在200～300MPa的等静压压力下通过等静压压制来获得素坯，其中素坯的脱脂温度可以为800～1000℃，脱脂时间可以为2～6h。
S4：对S3中制备得到的所述陶瓷坯体进行烧结处理以得到包含荧光粉、氮氧化铝相和氮化铝相的复相荧光陶瓷。具体地，将S3中制备得到的陶瓷坏体放入烧结炉内进行烧结，在烧结完成后冷却得到包含荧光粉、氮氧化铝相和氮化铝相的复相荧光陶瓷，其中烧结方式可以是热压、气压、真空、热等静压或放电等离子等。
S5：对S4中制备得到的所述复相荧光陶瓷进行后处理，所述后处理包括减薄处理和抛光处理。
如此，通过在荧光粉(或氮化铝粉体)的表面包覆一层铝盐，然后将包覆有一层铝盐的荧光粉(或氮化铝粉体)与氮化铝粉体(或荧光粉)混合并烧结，可以通过在烧结过程中使得铝盐先反应形成氧化铝，然后再与氮化铝反应而在荧光粉与氮化铝相之间形成氮氧化铝相，因此可以确保 氮氧化铝相介于荧光粉与氮化铝相之间并且荧光粉与氮化铝相彼此之间不直接接触。也就是说，荧光粉与氮化铝相通过氮氧化铝相结合在一起。换句话说，在烧结过程中，仅在氮氧化铝相与荧光粉之间以及氮氧化铝相与氮化铝相之间存在相界面，而在荧光粉与氮化铝相之间不存在相界面。由于氮氧化铝与氮化铝之间具有良好的相容性，所以氮氧化铝相与氮化铝相之间的相界面处烧结致密度高，并且由于氮氧化铝相是通过铝盐与氮化铝相反应生成的，所以氮氧化铝相与氮化铝相之间的粘结强度也比较大。另外，由于氮氧化铝与荧光粉的热膨胀系数基本相同，因此氮氧化铝与荧光粉之间没有热应力，可以烧结致密，得到机械强度比较高的复相陶瓷。换句话说，本发明解决了氮化铝的热膨胀系数与荧光粉的热膨胀系数相差较大而导致的氮化铝与荧光粉的复相陶瓷AlN&YAG:Ce热应力较大、致密度较低、机械强度较差的问题。另外，如上所述，AlN&YAG:Ce的复相荧光陶瓷具有高的热导率，因此，本发明制备出了一种具有高的热导率和良好的机械强度的发光陶瓷，该发光陶瓷在被蓝光LD或者蓝光LED等高功率激发光源照射时能够高效发光并实现高亮度的照明光源，从而进一步提高照明和投影光源的亮度，因此能够适应高功率蓝光LD或LED光源的发光要求。
下面参照具体实施例来对本发明进行详细说明。
实施例1
图2示出了根据本发明实施例1的复相荧光陶瓷的制备方法的流程图。在本实施例中，采用高纯度的氮化铝、商用YAG:Ce荧光粉及硝酸铝为原料来制备复相荧光陶瓷，其中选用聚乙烯醇缩丁醛(PVB)作为粘接剂，并且可以增选分散剂、烧结助剂等。具体制备方法如下。
首先执行第一步骤S1，使YAG:Ce荧光粉表面包覆一层铝盐：采用共沉淀的方法在商用YAG:Ce荧光粉的表面上包覆一层铝盐以得到表面包覆有一层铝盐的YAG:Ce荧光粉。具体地，将适量的粒径大小为1～30um的商用YAG:Ce荧光粉和硝酸铝(AlNO 3)溶解于水溶液中，边搅拌边加入沉淀剂，沉淀剂可以是氨水或者铵盐(如碳酸氢铵)，充分反应后得到表面包覆有一层铝盐(即，氢氧化铝)的YAG:Ce荧光粉的悬浮液；将包覆有一层铝盐的YAG:Ce荧光粉的悬浮液用去离子水清洗至PH为中性并干 燥，得到表面包覆有一层铝盐的YAG:Ce荧光粉颗粒。需要说明的是，虽然这里采用硝酸铝(AlNO 3)作为原料并且采用氨水或者铵盐作为沉淀剂来在YAG:Ce荧光粉的表面上包覆一层铝盐，但是本发明不限于此，本领域技术人员可以选择任意合适的含铝化合物作为原料，并且根据所选择的含铝化合物原料的种类选择合适的沉积剂以实现在YAG:Ce荧光粉的表面上包覆一层铝盐的目的。示例性的，在其他一些实施例中，可以选用偏铝酸钠(NaAlO 2)作为原料，同时选用稀盐酸(HCl)作为沉淀剂来在YAG:Ce荧光粉的表面上包覆一层铝盐(即，氢氧化铝)。另外，需要说明的是，虽然这里采用了共沉淀法在YAG:Ce荧光粉的表面上包覆了一层铝盐，但是本发明不限于此，能够在YAG:Ce荧光粉的表面上包覆一层铝盐的任意方法都可以使用，例如喷雾干燥法等。可以理解的是，这里的铝盐为最广义的含铝化合物，例如包括氢氧化铝(Al(OH) 3)、硝酸铝(AlNO 3)、硫酸铝(Al 2(SO 4) 3)以及诸如偏铝酸钠(NaAlO 2)和偏铝酸钾(KAlO 2)等偏铝酸盐等。
然后执行第二步骤S2，进行混料：将粒径大小为0.05～1um的氮化铝粉体、S1中得到的表面包覆有一层铝盐的YAG:Ce荧光粉、溶剂及粒径大小为0.02～1um的烧结助剂Y 2O 3或者MgO均匀混合球磨一段时间，例如6～24h，制得氮化铝和上述表面包覆有一层铝盐的YAG:Ce荧光粉的混合浆料，其中烧结助剂占氮化铝、包覆有一层铝盐的YAG:Ce荧光粉与烧结助剂的总质量的0.01～4％。
接着执行第三步骤S3，进行素坯成型：将S2中得到的混合浆料置于烘箱中干燥，然后研磨、过筛以避免粉体团聚而对陶瓷烧结产生不良影响，之后在10～20MPa的干压压力下将上述得到的陶瓷粉体干压成型，然后在200～300MPa的等静压压力下通过等静压压制来获得素坯，并对该素坯进行脱脂处理以得到陶瓷坯体，其中素坯的脱脂温度为800～1000℃，脱脂时间为2～6h。
接着执行第四步骤S4，进行陶瓷烧结：将S3中得到的陶瓷坯体于真空气氛炉中在1600～1800℃的烧结温度下进行烧结处理，该气氛为氮气，烧结时间为6～12h，冷却后得到具有如图1所示的结构的包含荧光粉、氮氧化铝相和氮化铝相的复相荧光陶瓷。
最后执行第五步骤S5，进行陶瓷后处理：将S4中得到的复相荧光陶瓷进行包括减薄和抛光处理等后处理。
在本实施例中，所得到的荧光粉表面包覆的氮氧化铝相的厚度为0.05um～1um，以能够实现对荧光粉的完全包覆并且具有良好的光透过率。可以理解的是，当氮氧化铝的厚度较薄的情况下，氮氧化铝相可能不能实现对荧光粉的完全包覆，有可能出现氮化铝相与荧光粉直接接触的情况，导致所制备的复相荧光陶瓷的烧结致密度不够好。也可以理解的是，当氮氧化铝的厚度较厚的情况下，光透过率会降低，影响荧光粉的出光效率。因此，制备出合适厚度的氮氧化铝相对本发明来说很重要。需要说明的是，荧光粉表面包覆的氮氧化铝相的厚度可以通过调整沉淀溶液的浓度或者使S1中的沉淀过程(即，铝盐包覆工艺)重复进行多次等方式来控制。示例性的，第一步骤S1可以按以下过程执行以得到所需厚度的氮氧化铝相，将适量的粒径大小为1～30um的商用YAG:Ce荧光粉和硝酸铝分散于水溶液中，边搅拌边加入沉淀剂，沉淀剂可以是氨水或者铵盐(如碳酸氢铵)，充分反应后得到表面包覆有一层铝盐(即，氢氧化铝)的YAG:Ce荧光粉的悬浮液；将包覆有一层铝盐的YAG:Ce荧光粉的悬浮液用去离子水清洗至PH为中性并干燥，得到表面包覆有一层铝盐的YAG:Ce荧光粉颗粒；然后，将包覆有一层铝盐的YAG:Ce荧光粉再次和硝酸铝分散于水溶液中，边搅拌边加入沉淀剂，充分反应后在YAG:Ce荧光粉的铝盐层的基础上再次包覆一层铝盐(即，氢氧化铝)，并且在清洗并干燥之后得到表面包覆有更多铝盐的荧光粉颗粒。需要指出的是，虽然这里以举例的方式重复进行了一次铝盐包覆工艺过程，但是根据所使用的沉淀剂浓度的不同，也可以重复进行多次这种铝盐包覆工艺过程，从而得到所需厚度的铝盐，以便得到所需厚度的氮氧化铝相。
在本实施例中，通过在YAG:Ce荧光粉的表面包覆一层铝盐，然后与氮化铝粉体一起混合并烧结，可以避免热膨胀系数相差比较大的YAG:Ce荧光粉与氮化铝的直接接触，而是由铝盐介于其间。在烧结过程中，铝盐先通过化学反应生成氧化铝，然后再与氮化铝反应生成氮氧化铝，所生成的氮氧化铝可以与YAG:Ce荧光粉烧结致密，克服了YAG:Ce荧光粉与氮化铝烧结致密度差的问题，从而得到机械强度得到提高的复 相荧光陶瓷。
实施例2
与实施例1相比，在本实施例中改变了陶瓷的烧结方式，其他方面与实施例1相同。在本实施例中，选择进行放电等离子烧结，即，将陶瓷粉体装入石墨模具中，在5～40MPa的压力以及1600～1800℃的烧结温度下进行烧结。放电等离子烧结方式的主要优势在于可以降低烧结温度以及缩短烧结时间，防止晶粒生长过大而降低陶瓷的机械强度，但通过该烧结方式得到的陶瓷在后期需要在氮气氛围中进行退火处理。本实施例适用于对陶瓷的机械强度要求比较高的场合，因此为本发明提供了另一种可选方案。
实施例3
图3示出了根据本发明实施例3的复相荧光陶瓷的另一种制备方法的流程图。在本实施例中，与实施例1和2中一样，采用高纯度的氮化铝、商用YAG:Ce荧光粉及硝酸铝为原料来制备复相荧光陶瓷，其中选用PVB作为粘接剂，并且可以增选分散剂、烧结助剂等。具体制备方法如下。
首先执行第一步骤S1，与实施例1和实施例2中使YAG:Ce荧光粉的表面包覆一层铝盐不同，在本实施例中是使氮化铝粉体的表面包覆一层铝盐：同样采用共沉淀的方法在氮化铝粉体的表面上包覆一层铝盐，共沉淀方法与实施例1相同。具体地，将适量的粒径大小为0.05～1um的氮化铝粉体和硝酸铝溶解于水溶液中，边搅拌边加入沉淀剂，沉淀剂可以是氨水或者铵盐(如碳酸氢铵)，充分反应后得到表面包覆有一层铝盐(即，氢氧化铝)的氮化铝粉体的悬浮液；将包覆有一层铝盐的氮化铝粉体的悬浮液用去离子水清洗至PH为中性并干燥，得到表面包覆有一层铝盐的氮化铝粉体，其中氮化铝粉体的粒径大小为0.05～1um，比商用荧光粉的粒径1～30um更小，比表面积较大，因此与实施例1中在荧光粉表面包覆铝盐相比，在氮化铝粉体的表面包覆一层铝盐的可行性更高。与实施例1中相同，在本实施例中，也可以选择任意合适的含铝化合物作为原料，并且根据所选择的含铝化合物原料的种类选择合适的沉积剂以 实现在氮化铝粉体的表面上包覆一层铝盐的目的。同样，与实施例1中相同，在本实施例中也可以使用除了共沉淀法之外的能够在氮化铝粉体的表面上包覆一层铝盐的任意方法来在氮化铝粉体的表面上包覆一层铝盐，例如喷雾干燥法等。
然后执行第二步骤S2，进行混料：将S1中得到的包覆有一层铝盐的氮化铝粉体、粒径大小为1～30um的商用YAG:Ce荧光粉、溶剂及粒径大小为0.02～1um的烧结助剂Y 2O 3或者MgO均匀混合球磨一段时间，例如6～24h，制得包覆有一层铝盐的氮化铝粉体和YAG:Ce荧光粉的混合浆料，其中烧结助剂占包覆有一层铝盐的氮化铝粉体、YAG:Ce荧光粉与烧结助剂的总质量的0.01～4％。
接着执行第三步骤S3，进行素坯成型：将S2中得到的混合浆料置于烘箱中干燥，然后研磨、过筛以避免粉体团聚而对陶瓷烧结产生不良影响，之后在10～20MPa的干压压力下将上述得到的陶瓷粉体干压成型，然后在200～300MPa的等静压压力下通过等静压压制来获得素坯，并对该素坯进行脱脂处理以得到陶瓷坯体，其中素坯的脱脂温度为800～1000℃，脱脂时间为2～6h。
接着执行第四步骤S4，进行陶瓷烧结：将S3中得到的陶瓷坯体于真空气氛炉中在1600～1800℃的烧结温度下进行烧结处理，该气氛为氮气，烧结时间为6～12h，冷却后得到具有如图1所示的结构的包含荧光粉、氮氧化铝相和氮化铝相的复相荧光陶瓷。
最后执行第五步骤S5，进行陶瓷后处理：将S4中得到的复相荧光陶瓷进行后处理，包括减薄和抛光处理。
同样，在本实施例中，所得到的氮化铝粉体表面包覆的氮氧化铝相的厚度为0.05um～1um，以能够实现对氮化铝粉体的完全包覆并且具有良好的光透过率。与实施例1中一样，可以通过调整沉淀溶液的浓度或者使S1中的沉淀过程(即，铝盐包覆工艺)重复进行多次等方式来控制在氮化铝粉体表面包覆的铝盐的厚度，以便得到所需厚度的氮氧化铝相。
在本实施例中，通过在氮化铝粉体的表面包覆一层铝盐，然后与YAG:Ce荧光粉一起混合并烧结，同样可以避免热膨胀系数相差比较大的 YAG:Ce荧光粉与氮化铝的直接接触，而是由铝盐介于其间。在烧结过程中，铝盐先通过化学反应生成氧化铝，然后再与氮化铝反应生成氮氧化铝，所生成的氮氧化铝可以与YAG:Ce荧光粉烧结致密，同样克服了YAG:Ce荧光粉与氮化铝烧结致密度差的问题，从而得到机械强度得到提高的复相荧光陶瓷。
需要指出的是，在本实施例中，也可以将陶瓷烧结方式改变为实施例2中所述的放电等离子烧结，从而可以降低烧结温度及缩短烧结时间，防止晶粒生长过大而降低陶瓷的机械强度。这同样适用于对陶瓷的机械强度要求比较高的场合。
在上述实施例1～3中制备的荧光陶瓷为复相荧光陶瓷，其结构可以表示为YAG:Ce-AlON-AlN，其中粘结相为AlN，AlN原料的粒径大小为0.05～1um，烧结后粒径范围为：0.2～10um，并且发光相为YAG:Ce荧光粉，YAG:Ce荧光粉占陶瓷总体积的20～80％以达到良好的发光效率。AlON介于YAG:Ce与AlN之间并且其厚度为0.05～1um，从而避免了YAG:Ce与AlN之间的直接接触，以克服由于其热膨胀系数相差较大而导致的复相陶瓷AlN&YAG:Ce热应力较大、致密度较低、机械强度较差的问题。
在上述实施例1～3中制备的复相荧光陶瓷为包含YAG:Ce荧光粉、氮氧化铝相和氮化铝相的发光陶瓷，其是一种具有高的热导率、高的致密度、良好的机械强度和高的发光效率的荧光陶瓷，该发光陶瓷在被蓝光LD或者蓝光LED等高功率激发光源照射时能够高效发光并实现高亮度的照明光源，从而进一步提高照明和投影光源的亮度，因此能够适应高功率蓝光LD或LED光源的发光要求。
另一方面，上述实施例中的荧光粉也可以替换为LuAG:Ce荧光粉，如此制备的复相荧光陶瓷的结构为LuAG:Ce-AlON-AlN，其中发光相为LuAG:Ce荧光粉。这同样可以实现高的热导率、高的致密度、良好的机械强度和高的发光效率，在被蓝光LD或者蓝光LED等高功率激发光源照射时能够高效发光并实现高亮度的照明光源，从而进一步提高照明和投影光源的亮度，因此同样能够适应高功率蓝光LD或LED光源的发光要求。
本发明所列举的各原料，以及本发明各原料的上下限、工艺参数的上下限、区间取值都能实现本发明，在此不一一列举实施例；凡是依据本发明的技术实质对以上实施例所作的任何简单修改或等同变化，均仍属于本发明的技术方案的范围之内。

Claims (11)

  1. 一种复相荧光陶瓷，其特征在于，所述复相荧光陶瓷包括：作为基体相的氮化铝相、均匀分布在所述基体相中的荧光粉以及位于所述氮化铝相和所述荧光粉之间的氮氧化铝相，其中所述氮化铝相和所述荧光粉经由所述氮氧化铝相彼此隔开。
  2. 如权利要求1所述的复相荧光陶瓷，其特征在于，
    所述氮氧化铝相包覆在所述荧光粉和/或所述氮化铝相的表面上。
  3. 如权利要求1所述的复相荧光陶瓷，其特征在于，
    所述氮氧化铝相是在所述复相荧光陶瓷的烧结过程中通过包覆在所述荧光粉或所述氮化铝相表面的铝盐与所述氮化铝相反应生成的。
  4. 如权利要求1所述的复相荧光陶瓷，其特征在于，
    所述荧光粉为YAG:Ce荧光粉或LuAG:Ce荧光粉。
  5. 如权利要求1所述的复相荧光陶瓷，其特征在于，
    所述氮氧化铝相的厚度为0.05～1um。
  6. 如权利要求1所述的复相荧光陶瓷，其特征在于，
    所述荧光粉占所述复相荧光陶瓷总体积的20～80％。
  7. 如权利要求1所述的复相荧光陶瓷，其特征在于，
    所述荧光粉的粒径大小为1～30um。
  8. 如权利要求1所述的复相荧光陶瓷，其特征在于，
    所述氮化铝相的粒径大小为0.2～10um。
  9. 一种复相荧光陶瓷的制备方法，所述方法包括以下步骤：
    S1：在荧光粉或氮化铝粉体的表面上包覆一层铝盐，所述荧光粉的粒径大小为1～30um并且所述氮化铝粉体的粒径大小为0.05～1um；
    S2：将S1中制备得到的包覆后的产物与氮化铝粉体或荧光粉、助剂和溶剂均匀混合球磨以制得包含这些原料的混合浆料；
    S3：将S2中制备得到的所述混合浆料干燥并干压成型，然后通过等静压压制来获得素坯，并对所述素坯进行脱脂处理以得到陶瓷坯体；
    S4：对S3中制备得到的所述陶瓷坯体进行烧结处理以得到包含荧光粉、氮氧化铝相和氮化铝相的复相荧光陶瓷。
  10. 如权利要求9所述的方法，其特征在于，在步骤S4之后还包括步骤S5：对S4中制备得到的所述复相荧光陶瓷进行后处理，所述后处理包括减薄处理和抛光处理。
  11. 如权利要求9所述的方法，其特征在于，
    在S1中，在荧光粉或氮化铝粉体的表面上包覆一层铝盐是通过如下方法实现的：采用共沉淀的方法使用含铝化合物和沉淀剂在荧光粉或氮化铝粉体的表面上包覆一层铝盐。
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