CN111106224A - High-performance white light LED device and preparation method thereof - Google Patents
High-performance white light LED device and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-performance white light LED device, which comprises a blue light LED chip, a red fluorescent film and a blue-green fluorescent transparent polycrystalline ceramic plate, wherein the blue-green fluorescent transparent polycrystalline ceramic plate is provided with a two-dimensional photonic crystal layer from bottom to top; wherein the red fluorescent film is selected from Eu2+Doped SrLiAl3N4The material of the fluorescent powder and the blue-green fluorescent transparent polycrystalline ceramic plate is Ce3+Doping SrLa2Si2O8The fluorescent powder and the two-dimensional photonic crystal layer are made of SiNx. The invention respectively prepares the blue-green and red fluorescent powder materials with high performance into a transparent polycrystalline ceramic plate and a film, and further adds a two-dimensional photonic crystal layer on the surface of the transparent polycrystalline ceramic plate, under the excitation of a blue LEDThe white LED has the advantages of effectively improving the luminous efficiency and the color rendering index of the white LED and reducing the correlated color temperature.
Description
Technical Field
The invention belongs to the technical field of LED illumination, and particularly relates to a high-performance white light LED device and a preparation method thereof.
Background
White light LED is known as the fourth generation illumination source with the best application prospect in the 21 st century because of its advantages of small size, low energy consumption, high efficiency, fast response, long service life, and no pollution. With the continuous development of society, the application range of the LED is continuously expanded, and the LED is rapidly becoming the first choice light source in the general illumination field. The technical approach of realizing white light by LED is mainly fluorescence conversion method, for example, the most widely used mode in commerce is to use blue LED chip to excite yellow phosphor YAG: Ce3+Although the method has simple preparation process, high luminous efficiency and mature production technology, the obtained white light has poor color rendering property and higher correlated color temperature due to the lack of red light components, thereby limiting the further development and use of the white light. At present, the preparation technology of an LED chip is mature, and the performance of fluorescent powder is the key point for determining the performance of a white light LED device, so that the development of a novel fluorescent powder material with excellent performance to prepare a white light LED with high efficiency and high brightness is a difficult problem which is urgently needed to be solved at present.
Besides, the packaging of the phosphor powder and the LED chip also has problems to be solved. The organic resin and phosphor powder particles are mixed, and then the mixture is coated on the surface of the LED chip, which mainly has the following disadvantages: 1) due to poor light and heat stability of the organic resin, the white light LED is easy to degrade, age, yellow and the like under long-term heat radiation and illumination, so that the white light LED has the problems of reduced luminous efficiency, light color shift, reduced reliability and the like; 2) in the cup-shaped structure LED packaging system, the fluorescent powder mainly exists in a powder form, and the light emitting efficiency and the quantum efficiency of the white light LED are reduced due to the existence of higher light reflection and scattering loss. Therefore, reducing the amount of organic resin used and improving the form of the phosphor have been the main research directions for solving the above problems.
Disclosure of Invention
The invention mainly aims to provide a high-performance white light LED device aiming at the defects in the prior art, wherein a high-performance blue-green fluorescent powder material and a high-performance red fluorescent powder material are respectively made into a transparent polycrystalline ceramic plate and a thin film, and a two-dimensional photonic crystal layer is further additionally arranged on the upper surface of the transparent polycrystalline ceramic plate, so that the high-performance white light LED device shows excellent luminous performance under the excitation of a blue light LED.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a high-performance white light LED device comprises a blue light LED chip, a red fluorescent film and a blue-green fluorescent transparent polycrystalline ceramic plate, wherein the blue-green fluorescent transparent polycrystalline ceramic plate is provided with a two-dimensional photonic crystal layer from bottom to top; wherein the red fluorescent film is selected from Eu2+Doped SrLiAl3N4The material of the fluorescent powder and the blue-green fluorescent transparent polycrystalline ceramic plate is Ce3+Doping SrLa2Si2O8The fluorescent powder and the two-dimensional photonic crystal layer are made of SiNx, and the surface of the fluorescent powder has a pore array structure.
In the above scheme, the Eu2+Doped SrLiAl3N4The stoichiometric formula of the phosphor is Sr1-xLiAl3N4:xEu2+，0.01≤x≤0.08；Ce3+Doping SrLa2Si2O8Has the stoichiometric formula SrLa2-ySi2S8:yCe3+，0.01≤y≤0.09。
In the scheme, the red fluorescent film is prepared by weighing Sr according to the stoichiometric ratio3N2、Li3N, AlN and EuN as main raw materials, ball milling, calcining in protective atmosphere to obtain fluorescent powder, mixing with organosilicon, coating, and drying.
In the scheme, the ball milling time is 1.5-2.5 h.
In the scheme, the roasting temperature is 1050 ℃ and 1150 ℃, and the time is 4-6 h.
In the scheme, the mass ratio of the red fluorescent powder to the organic silicon resin is 1 (0.5-2).
In the scheme, the drying temperature is 150-200 ℃, and the time is 40-60 min.
In the scheme, the thickness of the red fluorescent film is 0.01-0.03 mm.
Preferably, when x is 0.06 (optimum doping concentration), the phosphor has a chemical formula of Sr0.94LiAl3N4:0.06Eu2+The red emission intensity of the phosphor is at a maximum.
In the above scheme, the blue-green fluorescent transparent polycrystalline ceramic plate is prepared by weighing La according to stoichiometric ratio2S3、SrS、Ce2S3And Si and S powder are taken as main raw materials and are sequentially subjected to ball milling, vacuum sintering, forming pressing, secondary vacuum sintering and thermal etching treatment to form the silicon-based alloy.
In the scheme, the ball milling time is 1.5-2.5 h.
In the above scheme, the vacuum degree adopted by the vacuum sintering is less than or equal to 1 × 10-3The Torr is at 1000-1100 ℃ for 6-8 h; the vacuum degree adopted by the secondary vacuum sintering is less than or equal to 1 multiplied by 10-3The sintering temperature is 1050 ℃ and 1150 ℃, and the sintering time is 4-6 h.
Preferably, when y is 0.05 (the optimal doping concentration), the chemical formula of the phosphor is SrLa1.95Si2S8:0.05Ce3+The blue-green emission intensity of the phosphor is at a maximum.
In the scheme, the thermal etching treatment temperature is 1000-1100 ℃, and the time is 1.5-2.5 h.
According to the scheme, the SiNx film layer is deposited on the surface of the blue-green fluorescent transparent polycrystalline ceramic plate by using a plasma enhanced chemical vapor deposition method, then the single-layer polystyrene nanospheres are coated on the surface of the blue-green fluorescent transparent polycrystalline ceramic plate, the particle size of the polystyrene nanospheres is reduced by using a reactive ion etching process, then the Cr metal mask layer is deposited, finally the polystyrene nanospheres (the ultrasonic treatment time in chloroform is 10-30min) and the Cr metal mask layer (the reactive ion etching process) are sequentially removed, and namely a two-dimensional photonic crystal layer with a pore array structure on the surface is obtained on the blue-green fluorescent transparent polycrystalline ceramic plate.
In the above scheme, theThe deposition conditions of the plasma enhanced chemical vapor deposition method are as follows: the substrate temperature is 300-350 ℃, the pressure in the reaction chamber is 90-110Pa, and SiH4/H2Gas flow rate ratio of 0.02-0.04, SiH4/N2The gas flow ratio is 0.1-1.
In the scheme, the thickness of the SiNx film layer is 350-450nm, and the particle size of nanospheres of the single-layer polystyrene nanospheres is 300-600 nm; and the particle size of the nanospheres is reduced to 200-300nm after the reactive ion etching process.
In the scheme, the thickness of the Cr metal mask layer is 20-30 nm.
In the scheme, the blue light LED chip, the red fluorescent film and the blue-green fluorescent transparent polycrystalline ceramic plate which is additionally provided with the two-dimensional photonic crystal layer are packaged in the cup-shaped LED device.
The preparation method of the high-performance white light LED device comprises the following steps:
1) respectively preparing a red fluorescent thin film and a blue-green fluorescent transparent polycrystalline ceramic plate, preparing a two-dimensional photonic crystal layer by adopting a SiNx material, and additionally arranging the two-dimensional photonic crystal layer on the surface of the blue-green fluorescent transparent polycrystalline ceramic plate;
2) and a blue light LED chip, a red fluorescent film and a blue-green fluorescent transparent polycrystalline ceramic plate additionally provided with a two-dimensional photonic crystal layer are sequentially arranged in the white light LED system mounting groove from bottom to top and then packaged in a cup-shaped LED device.
In the above scheme, Eu in the red fluorescent thin film and the blue-green fluorescent transparent polycrystalline ceramic plate2+Doped SrLiAl3N4Phosphor and Ce3+Doping SrLa2Si2O8The mass ratio of the fluorescent powder is (5-15) to (85-95) (under the condition that the section specification in the horizontal direction is the same).
Compared with the prior art, the invention has the beneficial effects that:
1) the blue-green fluorescent powder SrLa adopted by the invention2-ySi2S8:yCe3+Has the advantages of low synthesis temperature, excellent luminescence property and the like, and the adopted blue-green (emission wavelength range of 475-The fluorescent powder is excited by a blue light LED, has excellent luminous performance under the excitation of the blue light LED, and is suitable for being used as a fluorescent powder material for a white light LED;
2) according to the invention, the blue fluorescent powder is prepared into the blue-green fluorescent transparent polycrystalline ceramic plate, so that the fluorescent powder is uniformly distributed in the transparent ceramic plate, the problem that the fluorescent powder is easy to settle in the traditional process is solved, and the uniformity of light emission is facilitated; the red fluorescent film is prepared from the red fluorescent powder, the process is simple, the thickness, the size, the shape and the fluorescent powder content of the film are convenient to control, and the high consistency of the optical performance of the LED can be ensured. The two improvement methods replace the traditional powder fluorescent powder, so that the fluorescent powder has higher light transmittance in a visible light range, and the luminous performance of the white light LED is favorably improved.
3) According to the invention, the two-dimensional photonic crystal layer structure is effectively attached to the surface of the blue-green fluorescent transparent polycrystalline ceramic plate by adopting a nanosphere photoetching process and a reactive ion etching process, so that the light-emitting efficiency of the white light LED can be greatly improved, and meanwhile, the white light LED has higher luminous efficiency and color rendering index.
Drawings
FIG. 1 is a flow chart of the present invention for preparing a blue-green fluorescent transparent polycrystalline ceramic plate with a two-dimensional photonic crystal layer added on the surface;
fig. 2 is a schematic structural diagram of the white LED device according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the following examples, the preparation method of the red fluorescent film includes the following steps:
1) according to Sr0.94LiAl3N4:0.06Eu2+Stoichiometric ratio of (3) weighing raw Material Sr3N2、Li3N, AlN and EuN, then wet ball milling for 2h by mixing it with an appropriate amount of ethanol solution using a planetary mill;
2) placing the ball-milled mixture in a molybdenum crucible, then transferring the molybdenum crucible to a graphite furnace, heating the molybdenum crucible to 1100 ℃ in a nitrogen atmosphere, roasting the molybdenum crucible for 5 hours, and cooling the molybdenum crucible to room temperature after roasting;
3) mixing the cooled sample with organic silicon resin (OE-6630A) in a mass ratio of 1:1, printing the mixture on a PEDOT: PSS layer, and then sealing the glass substrate by using an isolation layer;
4) drying the capped substrate in a drying oven at 150 ℃ for 40min to solidify the coating layer; the substrate was then transferred to a water bath by dissolving PEDOT: the PSS interlayer separates the red phosphor film from the glass substrate, and dries to finally obtain the red phosphor film (0.5cm (length) × 0.5cm (width), with the thickness varying according to the dosage requirements of different embodiments).
The preparation method of the blue-green fluorescent transparent polycrystalline ceramic plate comprises the following steps:
1) according to SrLa1.95Si2S8:0.05Ce3+Stoichiometric ratio of (A) to (B) of raw Material La2S3、SrS、Ce2S3Mixing Si and S powder with a proper amount of ethanol solution by using a planetary mill, and carrying out wet ball milling for 2 hours;
2) placing the ground mixture in a vertically placed quartz ampoule bottle, evacuating to a vacuum degree of below 1 × 10-3Torr, heating to 1050 deg.C, calcining for 7h, and slowly cooling to room temperature;
3) pressing the cooled powder into tablets in a stainless steel die (15MPa), and then further performing isostatic compaction pressing at 200 MPa;
4) heating the pressed sample to 1100 ℃ under the vacuum degree condition of less than 1 x 10 < -3 > Torr again, firing for 5h to enhance the bulk density of the sample, then carrying out surface polishing on the sample and carrying out thermal etching treatment for 2h at 1000 ℃;
5) the obtained final sample was cut into blue-green fluorescent transparent polycrystalline ceramic plates having respective sizes of 0.5cm (length) x 0.5cm (width) x 0.2mm (thickness).
The preparation method for additionally arranging the two-dimensional photonic crystal layer on the surface of the blue-green fluorescent transparent polycrystalline ceramic plate comprises the following steps, and the preparation flow is shown in figure 1:
1) diluting Silane (SiH) with high hydrogen by plasma enhanced chemical vapor deposition4) And nitrogen (N)2) Depositing a nano SiNx film layer on the surface of the blue-green fluorescent transparent polycrystalline ceramic plate as a reaction atmosphere, wherein the deposition conditions are as follows: the substrate temperature was 320 ℃ and the pressure in the reaction chamber was 100Pa, SiH4/H2Gas flow ratio of 0.03, SiH4/N2The gas flow ratio was 0.2; the deposition thickness of the SiNx film layer is 400nm, and then a single-layer polystyrene nanosphere with the diameter of 450nm is coated on the surface of the SiNx/ceramic plate system substrate as a mask layer;
2) by using a catalyst based on O2Diluting the single-layer polystyrene nanospheres coated on the substrate by the reactive ion etching process until the diameter of the polystyrene nanospheres is reduced to 250nm, immediately transferring the polystyrene nanospheres into a thermal evaporation system, and depositing a Cr metal mask layer with the thickness of 25 nm;
3) ultrasonic treating in chloroform for 20min to remove polystyrene nanosphere to obtain Cr mask layer with two-dimensional Cr nanopore array, and performing CF-based ultrasonic treatment4The nano-hole pattern is transferred to the SiNx layer below by the reactive ion etching process;
4) and finally, removing the Cr nano-pore mask layer by using a Cr etchant to obtain the two-dimensional photonic crystal layer with the pore array structure on the surface.
Example 1
A high-performance white light LED device is shown in figure 2, and the preparation method comprises the following steps:
1) preparing a corresponding red fluorescent film (the thickness is 0.01mm) and a blue-green fluorescent transparent polycrystalline ceramic plate according to the mass ratio (the mass ratio of the blue-green fluorescent powder to the red fluorescent powder is 95:5), and additionally arranging a two-dimensional photonic crystal layer on the surface of the blue-green fluorescent transparent polycrystalline ceramic plate;
2) the installation sequence from bottom to top in the white light LED system installation groove is as follows in proper order: blue light LED chip, red fluorescence film, the transparent polycrystalline ceramic plate of bluish green fluorescence of two-dimensional photonic crystal layer is add on the surface, then encapsulates in cup type LED device.
Example 2
A high-performance white light LED device is prepared by the following steps:
1) preparing a corresponding red fluorescent film (the thickness is 0.015mm) and a blue-green fluorescent transparent polycrystalline ceramic plate according to the mass ratio (the mass ratio of the blue-green fluorescent powder to the red fluorescent powder is 92.5:7.5), and additionally arranging a two-dimensional photonic crystal layer on the surface of the blue-green fluorescent transparent polycrystalline ceramic plate;
2) the installation sequence from bottom to top in the white light LED system installation groove is as follows in proper order: blue light LED chip, red fluorescence film, the transparent polycrystalline ceramic plate of bluish green fluorescence of two-dimensional photonic crystal layer is add on the surface, then encapsulates in cup type LED device.
Example 3
A high-performance white light LED device is prepared by the following steps:
1) preparing a corresponding red fluorescent film (the thickness is 0.02mm) and a blue-green fluorescent transparent polycrystalline ceramic plate according to the mass ratio (the mass ratio of the blue-green fluorescent powder to the red fluorescent powder is 90:10), and additionally arranging a two-dimensional photonic crystal layer on the surface of the blue-green fluorescent transparent polycrystalline ceramic plate;
2) the installation sequence from bottom to top in the white light LED system installation groove is as follows in proper order: blue light LED chip, red fluorescence film, the transparent polycrystalline ceramic plate of bluish green fluorescence of two-dimensional photonic crystal layer is add on the surface, then encapsulates in cup type LED device.
Example 4
A high-performance white light LED device is prepared by the following steps:
1) preparing a corresponding red fluorescent film (the thickness is 0.03mm) and a blue-green fluorescent transparent polycrystalline ceramic plate according to the mass ratio (the mass ratio of the blue-green fluorescent powder to the red fluorescent powder is 85:15), and additionally arranging a two-dimensional photonic crystal layer on the surface of the blue-green fluorescent transparent polycrystalline ceramic plate;
2) the installation sequence from bottom to top in the white light LED system installation groove is as follows in proper order: blue light LED chip, red fluorescence film, the transparent polycrystalline ceramic plate of bluish green fluorescence of two-dimensional photonic crystal layer is add on the surface, then encapsulates in cup type LED device.
Comparative example 1
A high-performance white light LED device is prepared by the following steps:
1) preparing a corresponding red fluorescent film (the thickness is 0.01mm) and a blue-green fluorescent transparent polycrystalline ceramic plate according to the mass ratio (the mass ratio of the blue-green fluorescent powder to the red fluorescent powder is 95: 5);
2) the installation sequence from bottom to top in the white light LED system installation groove is as follows in proper order: the blue light LED chip, the red fluorescent film and the blue-green fluorescent transparent polycrystalline ceramic plate are packaged in the cup-shaped LED device.
Comparative example 2
A high-performance white light LED device is prepared by the following steps:
1) preparing a corresponding red fluorescent film (with the thickness of 0.015mm) and a blue-green fluorescent transparent polycrystalline ceramic plate according to the mass ratio (the mass ratio of the blue-green fluorescent powder to the red fluorescent powder is 92.5: 7.5);
2) follow supreme installation order down in the white light LED system mounting groove and do in proper order: the blue light LED chip, the red fluorescent film and the blue-green fluorescent transparent polycrystalline ceramic plate are packaged in the cup-shaped LED device.
Comparative example 3
A high-performance white light LED device is prepared by the following steps:
1) preparing a corresponding red fluorescent film (the thickness is 0.02mm) and a blue-green fluorescent transparent polycrystalline ceramic plate according to the mass ratio (the mass ratio of the blue-green fluorescent powder to the red fluorescent powder is 90: 10);
2) follow supreme installation order down in the white light LED system mounting groove and do in proper order: the blue light LED chip, the red fluorescent film and the blue-green fluorescent transparent polycrystalline ceramic plate are packaged in the cup-shaped LED device.
Comparative example 4
A high-performance white light LED device is prepared by the following steps:
1) preparing a corresponding red fluorescent film (the thickness is 0.03mm) and a blue-green fluorescent transparent polycrystalline ceramic plate according to the mass ratio (the mass ratio of the blue-green fluorescent powder to the red fluorescent powder is 85: 15);
2) follow supreme installation order down in the white light LED system mounting groove and do in proper order: the blue light LED chip, the red fluorescent film and the blue-green fluorescent transparent polycrystalline ceramic plate are packaged in the cup-shaped LED device.
Testing and results analysis
The results of the test of the light emitting properties of the white light LED devices obtained in examples 1 to 4 and comparative examples 1 to 4 are shown in table 1.
Table 1 test results of luminescence properties of white LED devices obtained in examples 1 to 4 and comparative examples 1 to 4
As can be seen from the table, after the two-dimensional photonic crystal layer is added, when the mass ratio of the blue-green phosphor to the red phosphor is 90:10, the obtained white LED has excellent light emitting performance compared to other mass ratios: the luminous efficiency is 82.3lm/W, the correlated color temperature is 5431K, the color rendering index is 88, the CIE color coordinate is (0.331,0.346), the color is very close to natural light, and the LED is suitable for being used as a preferred light source in the field of illumination. In addition, as is obvious from embodiments 1-4 and comparative examples 1-4, the two-dimensional photonic crystal layer auxiliary material is additionally arranged on the surface of the blue-green fluorescent transparent polycrystalline ceramic plate, so that the luminous efficiency and the color rendering index of the white light LED can be effectively improved, and the correlated color temperature of the white light LED is reduced.
The above embodiments are merely examples for clearly illustrating the present invention and do not limit the present invention. Other variants and modifications of the invention, which are obvious to those skilled in the art and can be made on the basis of the above description, are not necessary or exhaustive for all embodiments, and are therefore within the scope of the invention.
Claims (8)
1. A high-performance white light LED device is characterized in that the high-performance white light LED device comprises a plurality of LED chips arranged in sequence from bottom to topThe blue light LED chip, the red fluorescent film and the blue-green fluorescent transparent polycrystalline ceramic plate are provided with two-dimensional photonic crystal layers on the surfaces; wherein the red fluorescent film is selected from Eu2+Doped SrLiAl3N4The material of the fluorescent powder and the blue-green fluorescent transparent polycrystalline ceramic plate is Ce3+Doping SrLa2Si2O8The fluorescent powder and the two-dimensional photonic crystal layer are made of SiNx, and the surface of the fluorescent powder has a pore array structure.
2. The high performance white LED device of claim 1, wherein the Eu is selected from the group consisting of2+Doped SrLiAl3N4The stoichiometric formula of the phosphor is Sr1-xLiAl3N4:xEu2+，0.01≤x≤0.08；Ce3+Doping SrLa2Si2O8Has the stoichiometric formula SrLa2-ySi2S8:yCe3+，0.01≤y≤0.09。
3. The high performance white LED device of claim 2, wherein said red phosphor film is Sr in stoichiometric proportions3N2、Li3N, AlN and EuN as main raw materials, ball milling, calcining in protective atmosphere to obtain fluorescent powder, mixing with organosilicon, coating, and drying.
4. The high performance white LED device of claim 2, wherein said blue-green fluorescent transparent polycrystalline ceramic plate is prepared with La weighed according to stoichiometric ratio2S3、SrS、Ce2S3And Si and S powder are taken as main raw materials and are sequentially subjected to ball milling, vacuum sintering, forming pressing, secondary vacuum sintering and thermal etching treatment to form the silicon-based alloy.
5. The high-performance white light LED device according to claim 1, wherein the blue-green fluorescent transparent polycrystalline ceramic plate with the surface additionally provided with the two-dimensional photonic crystal layer is obtained by depositing a SiNx film layer on the surface of the blue-green fluorescent transparent polycrystalline ceramic plate by using a plasma enhanced chemical vapor deposition method, coating a single layer of polystyrene nanospheres on the surface of the blue-green fluorescent transparent polycrystalline ceramic plate, reducing the particle size of the polystyrene nanospheres by using a reactive ion etching process, depositing a Cr metal mask layer, and finally removing the polystyrene nanospheres and the Cr metal mask layer in sequence, namely obtaining the two-dimensional photonic crystal layer with the pore array structure on the surface of the blue-green fluorescent transparent polycrystalline ceramic plate.
6. The high-performance white light LED device according to claim 1, wherein the blue light LED chip, the red fluorescent film and the blue-green fluorescent transparent polycrystalline ceramic plate with the two-dimensional photonic crystal layer added on the surface thereof, which are arranged in sequence, are packaged in a cup-shaped LED device.
7. The method for preparing the high-performance white light LED device as claimed in any one of claims 1 to 6, which comprises the following steps:
1) respectively preparing a red fluorescent film and a blue-green fluorescent transparent polycrystalline ceramic plate, and additionally arranging a two-dimensional photonic crystal layer on the surface of the blue-green fluorescent transparent polycrystalline ceramic plate by using a SiNx material;
2) and a blue light LED chip, a red fluorescent film and a blue-green fluorescent transparent polycrystalline ceramic plate with a two-dimensional photonic crystal layer added on the surface are sequentially arranged in the white light LED system mounting groove from bottom to top and then packaged in a cup-shaped LED device.
8. The method according to claim 7, wherein Eu is contained in the red phosphor thin film and the blue-green phosphor transparent polycrystalline ceramic plate2+Doped SrLiAl3N4Phosphor and Ce3+Doping SrLa2Si2O8The mass ratio of the fluorescent powder is (5-15) to (85-95).
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