Preparation of fluorescent film for laser illumination by free sintering technique

Abstract

A non-sintering technique is used to prepare a fluorescent thin film for laser lighting. This fluorescent film comprises a 0.5–2 mm thick aluminum substrate with a visible light reflectance greater than 95%, and a 100–500 μm thick emitting layer on the aluminum substrate. The emitting layer is obtained by mixing a fluorescent material and a fixative at 40–80 °C using a non-sintering technique. Under blue light excitation at 450 nm, the light emitted by the emitting layer mixes with unabsorbed blue light to produce white light with a color temperature range of 3000 K–4500 K and an Ra value of 90–98. The fluorescent thin film for laser lighting prepared by this invention has a simple overall structure and a convenient preparation process; the nitride red fluorescent material is not sintered, thus greatly preserving its luminescent properties; and the preparation process does not use water, which would decompose the nitride red fluorescent material; the fluorescent film is directly coupled to a highly thermally conductive aluminum plate, thereby enabling the fluorescent film to be used in laser lighting.

Description

Technical Field

[0001] This invention relates to the field of lighting technology, and more particularly to a sinter-free technique for preparing fluorescent thin films for laser lighting and their applications. Background Technology

[0002] As a new generation of lighting technology, laser lighting features high power and high brightness, and has been widely used in automotive headlights, aviation and marine lighting, military flashlights, laser cinemas, and laser televisions. Currently, as disclosed in Patent Document 1 (Wang Dajian, Song Weiwei, Mao Zhiyong, Li Guanghao, Sun Tao, Lu Zhijuan, A High-Efficiency Laser Lighting Remote Fluorescent Coating and Its Application, ZL201410609545.2), the blue light emitted by a laser diode (most commonly blue-light-emitting laser diodes) is partially absorbed by a yellow fluorescent material to produce yellow light emission. The unabsorbed blue light is scattered by the fluorescent material particles and mixed with the yellow light emitted by the fluorescent material to form white light. The advantages of using a laser diode to excite the fluorescent material to produce white light are lower energy consumption, higher luminous efficiency, and no "efficiency drop" problem compared to LEDs; the laser source is more stable, the manufacturing process is simpler, the cost is lower, and it is easier for industrial production.

[0003] Clearly, fluorescent materials play a crucial role in laser lighting technology. They convert the color of light and ultimately determine key performance parameters such as luminous efficiency, luminous intensity, color reproduction, and lifespan of the device. YAG:Ce(Y3Al5O) 12 YAG:Ce is currently the most widely used yellow fluorescent material. Therefore, how to encapsulate fluorescent materials (represented by YAG:Ce) into laser lighting devices has become a technology of great interest in this field. Non-patent literature 1 (Yixing Cao, Wei Chen, Yunjia Du, Gaojin Qi, Thebano Santos, Guoqi Zhang, Jiajie Fan, Luminous performances characterization of YAG:Ce) 3+A laser illumination encapsulation scheme using YAG:Ce phosphor material and silicone is disclosed in *Photonics Journal*, 2022, 14:1-1. It should be noted that lasers have strong collimation, concentrated beams, and high energy density; while silicone, being an organic material, has poor thermal conductivity and heat dissipation, and is not resistant to high temperatures. Therefore, when laser light irradiates silicone (even at a laser power of only 0.68W), carbonization and ablation damage occur on the silicone surface, affecting the luminescence performance of the phosphor material and ultimately leading to the failure of the entire light source device. Clearly, the YAG:Ce phosphor material + silicone encapsulation method is unsuitable for laser illumination.

[0004] To improve the laser resistance of laser lighting devices, patent document 2 (Zhang Shizhong, Glass Fluorescent Ceramics and Their Preparation Method and Wavelength Conversion Device, CN115893987A) discloses a laser lighting encapsulation scheme based on fluorescent glass. The manufacturing steps of the fluorescent glass include: 1. Weighing fluorescent material (YAG:Ce), glass encapsulation body, and pore-forming agent particles according to their mass fractions, adding organic solvent, and ball milling to obtain a mixed slurry; 2. Placing the mixed slurry in a drying oven to obtain a dried mixed powder; cold isostatically pressing to form a glass fluorescent ceramic green body; 3. Sintering the glass fluorescent ceramic green body at a temperature of 600–1300℃ for 0.5–2 hours to obtain fluorescent glass. It should be noted that the laser resistance of fluorescent glass is significantly improved compared to silicone, but the manufacturing process of fluorescent glass inevitably involves a sintering process.

[0005] However, the thermal conductivity of glass is obviously inferior to that of ceramics. Furthermore, patent document 3 (Wang Hong, Ye Yong, Zhang Pande, Li Dongsheng, Zeng Qingbing, Wang Sheng, Li Chunhui, Ultrafine Ceramic Phosphor for Obtaining High-Lumen Laser Illumination and its Preparation Method, CN113024242A) discloses an ultrafine ceramic phosphor for obtaining high-brightness laser illumination. The chemical composition of this ceramic phosphor is (Ce... x Re y Y 1-x-y )3Al5O 12Re can be one or more of Lu, Tb, Gd, and Ga, where x and y range from 0.005 to 0.05 and 0 to 0.25, respectively. Due to the high thermal conductivity and structural stability of fluorescent ceramics, the luminous flux can reach over 3000 lm when excited by a single laser module (8 blue lasers converged), which can meet the requirements of high-brightness laser lighting applications. However, it should be noted that, similar to the manufacturing process of fluorescent glass, the manufacturing process of fluorescent ceramics inevitably involves a sintering process, and the sintering temperature is usually higher than that required for the manufacturing of fluorescent glass (often exceeding 1400℃).

[0006] Because the initial products of fluorescent glass or fluorescent ceramics are relatively thick (fluorescent glass or fluorescent ceramics need to be thinned and polished before use), patent document 4 (Jie Rongjun, Zheng Peng, Zhou Tianliang, A reflective blue laser lighting component, CN109703120A) further discloses a laser lighting packaging scheme based on fluorescent glass thin film. Its general principle is: (YAG:Ce) fluorescent material and glass powder are co-fired in thin film form on a high thermal conductivity substrate (e.g., sapphire or AlN) to form an integrated composite material. Its technical advantage lies in inheriting the relatively easy sintering of glass materials, while the overall thermal conductivity of the device is close to that of ceramics. Therefore, fluorescent glass thin film is currently a widely used laser lighting packaging method. However, it should be noted that the manufacturing process of fluorescent glass thin film still involves a sintering process. It's just that because the film is thinner, its sintering time is shorter (e.g., 30 minutes), which is shorter than the sintering time of fluorescent glass or fluorescent ceramics.

[0007] As can be seen from the publicly available documents above, using blue laser + (represented by YAG:Ce) yellow fluorescent material can indeed achieve white light output in laser lighting devices. However, as Non-Patent Literature 2 (Yun Mou, Yang Peng, Xinzhong Wang, Jiaxin Liu, Jiuzhou Zhao, Ziliang Hao, Zikang Yu, Qing Wang, Jianming Xu, Unique sandwich and microstructure design of phosphor-in-glass film for highbrightness laser-driven white lighting, Journal of the European Ceramic Society, 2024, 44:2408-2417) suggests, the color temperature of the white light source obtained by using YAG:Ce yellow fluorescent material + blue laser is too high (usually greater than 6500K), and the color rendering index is too low (usually less than 65). Laser lighting devices encapsulated with yellow fluorescent material + blue laser cannot be used in places such as museums and cinemas where the light source color quality requirements are extremely high.

[0008] Therefore, the color temperature of the white light output by laser lighting devices should be reduced to improve their color rendering index. Adding red fluorescent materials can lower the color temperature and improve color rendering. For example, patent document 5 (Li Dongsheng, Zhang Pande, Wang Hong, Ye Yong, Feng Shaowei, Zhu Ning, Li Chunhui, Zhu Jinchao, A fluorescent ceramic for laser lighting with a core-shell structure and its preparation method, CN111285685A) discloses a fluorescent ceramic for laser lighting, whose chemical composition is: (Ce x Y 1-x )3Al5O 12 Where x takes values ​​in the range of 0.001 ≤ x ≤ 0.03; and the chemical composition is: (Eu y Y 1-y )3Al5O 12 Where y takes values ​​in the range of 0.0005 ≤ y ≤ 0.04. Since (Eu... y Y 1-y )3Al5O 12 (This red fluorescent material) can emit red light, combined with (Ce) x Y 1-x )3Al5O 12 (YAG:Ce yellow fluorescent material) can effectively solve the problems of high color temperature and low color rendering caused by insufficient red light in laser lighting products.

[0009] As reported in Non-Patent Literature 3 (Tang Ye, Fu Renli, Cao Bing, Zhang Pengfei, Yang Fang, Research on Red Phosphor Material System and Luminescent Performance for White LEDs Excited by Blue Light, Journal of Nanjing University of Aeronautics and Astronautics, 2016, 48:58-66), there are various red phosphor materials that can produce red light emission. However, as Patent Document 6 (Chen Lei, Zhang Zhao, Zhao Erlong, Deng Xiaorong, Chen Xiuling, Fermi, Liu Yanfang, A Method for Synthesizing LED Nitride Red Phosphors Using Metal Oxide Raw Materials, CN104946250A) states that the best red phosphors are nitrides Sr2Si5N8:Eu and CaAlSiN3:Eu. However, for Sr2Si5N8:Eu, non-patent literature 4 (Xiong Yang, Xue-Jing Xing, Yi-Fan Liu, Chun-Hong Mu, HaoVan Bui, Zhong-Wei Zhang, Simeon Agathopoulos, Xin Xu, Liang-Jun Yin, A new thermal degradation mechanism of red Sr2Si5N8:Eu phosphor: From the view of microstructural evolution, Optical Materials, 2021, 121:111506) suggests that its luminescence intensity cannot be restored to its initial level after heating (for example, when the temperature of Sr2Si5N8:Eu is raised to 125℃ and then cooled to room temperature, the luminescence intensity will decrease compared to the initial value, and 125℃ is a temperature easily reached by laser lighting devices). Therefore, CaAlSiN3:Eu may be the most practical and suitable red phosphor material for laser lighting.

[0010] Therefore, introducing the nitride red phosphor CaAlSiN3:Eu into the existing encapsulation method of (YAG:Ce) yellow phosphor material + blue laser will help to manufacture laser lighting devices with higher color temperature and color rendering index. For this purpose, examples include YAG:Ce fluorescent glass, as described in Non-Patent Literature 5 (R.Wang, MYWang, G.Li, JHZhang, YJZhang, H.Lin, EYBPun, DSLi, Red-emitting improvement of CaAlSiN3:Eu). 2+The paper "Phosphorus-in-glass: Insight into the effect of atmospheric pressure preparation on photoluminescence properties and thermal degradation," Journal of Luminescence, 2020, 225:117390, suggests that during the process of making the nitride red fluorescent material CaAlSiN3:Eu into fluorescent glass (high-temperature molten glass), the oxides in the molten glass have an corrosive effect on the fluorescent material, thus causing a certain degree of decrease in its luminescence performance. For example, YAG:Ce fluorescent ceramics, as described in Non-Patent Literature 6 (Shuxing Li, Qiangqiang Zhu, Le Wang, Daiming Tang, Yujin Cho, Xuejian Liu, Naoto Hirosaki, Toshiyuki Nishimura, Takashi Sekiguchi, Zhengren Huang, Rong-Jun Xie, CaAlSiN3:Eu...),... 2+Translucent ceramic: a promising robust and efficient red color converter for solid state laser displays and lighting, Journal of Materials Chemistry C, 4:8197-8205) argues that the sintering process of CaAlSiN3:Eu into ceramics requires the use of graphite molds, graphite paper, and carbon felt, inevitably resulting in a certain degree of carbon contamination in the sample, leading to a decrease in its quantum efficiency. Simultaneously, the sintering aids used during the sintering process can oxidize nitride red fluorescent materials (such as YAG:Ce fluorescent glass films) during high-temperature sintering. Non-patent literature 7 (Jian Xu, Yang Yang, Ziquan Guo, Baofu Hu, Jian Wang, Baoli Du, Bingguo Liu, Haipeng Ji, Carsten Dam-Hansen, Ole B. Jensen, Design of a CaAlSiN3:Eu / glass composite film: Facile synthesis, high saturation-threshold and application in high-power laser lighting, Journal of the European...) CeramicSociety, 2020, 40:4704) suggests that the internal quantum efficiency of the red fluorescent glass film prepared by sintering CaAlSiN3:Eu fluorescent material with a glass precursor at 510℃ is 79%, which is 10% lower than that of the original fluorescent material.

[0011] Clearly, sintering is an unavoidable process in the fabrication of fluorescent glass, fluorescent ceramics, or fluorescent glass films, and this process inevitably reduces the luminescence intensity / quantum efficiency of CaAlSiN3:Eu. Therefore, to obtain laser lighting devices for applications with higher requirements for colorimetric indices, such as museums and cinemas, sintering of nitride red fluorescent materials must be avoided during the packaging process.

[0012] Therefore, obtaining a sintering-free process for encapsulating nitride red fluorescent materials would help solve the above problems. Patent document 7 (Sun Renjuan, Li Zhenhuan, Guan Yanhua, Ge Zhi, Chen Xihao, Cui Kai, Ge Yuning, Zhuang Peizhi, Zhang Hongzhi, Li Yonghao, Fan Yingnan, Ran Yao, Dou Liuyang, Bu Linglai, A self-luminous curbstone based on solid waste and its preparation method, CN113638285A) discloses a self-luminous curbstone based on solid waste. The luminescent stone comprises the following components by weight: 15-25 parts epoxy resin, 6-10 parts curing agent, 90-225 parts waste glass sand, and 10-35 parts colored phosphor. It should be noted that although this method can obtain a solid luminescent material without a sintering process, the large amount of organic matter (epoxy resin) used makes it difficult to achieve laser lighting based on this technology.

[0013] Furthermore, Patent Document 8 (Jiang Xiaoping, A light-transmitting and self-luminous integrated concrete and its preparation method and application, CN110526633A) discloses a self-luminous concrete. Its main raw materials include: cement, fly ash, adhesive powder, silica fume, sand, luminescent stone, luminescent powder, cellulose, diatomaceous earth, water-repellent agent, admixture, expanding agent, fiber, pigment, optical fiber, and water. In this method, the combined use of luminescent stone and luminescent powder can achieve good energy storage and luminescence effects. Further, Patent Document 9 (Zhao Su, Wang Qian, Tian Zhongxin, Fu Erkang, A preparation method for energy-storing luminescent concrete, CN102964098A) discloses a preparation method for energy-storing luminescent concrete. Its raw materials include (by mass ratio): 2%–8% fluorescent powder, 18% white cement, 27% standard sand, 39%–47% gravel, and 8% water. Both of these disclosed technologies are based on cement curing technology and belong to a non-sintering process, but water must be used in the cement curing process. However, as in non-patent literature 8 (Baotong Guo, Minzhen Wen, Hongyu Tang, Sergey Lishik, Xuejun Fan, Guoqi Zhang, Jiajie Fan, Revealing The Degradation Mechanism of (SrCa)AlSiN3:Eu 2+(Phosphor Aged Under Thermal-Moisture-Sulfur Conditions: A Combined Experimental and Ab initio Study, Laser & Photonics Reviews, 2024, 2300838) This study found that the water resistance of CaAlSiN3:Eu fluorescent materials is not ideal. Under water (and at certain temperatures), they are prone to decomposition and loss of luminescence. Therefore, although cement can be easily processed into thin films, the fluorescent films obtained by mixing CaAlSiN3:Eu nitride red fluorescent materials with cement and other materials and then curing (without sintering) cannot effectively maintain their luminescence properties due to the decomposition effect of water (an essential component for cement curing) on ​​the CaAlSiN3:Eu nitride red fluorescent materials. In other words, CaAlSiN3:Eu nitride red fluorescent films produced using cement curing (without sintering) processes cannot be used in laser lighting applications.

[0014] Furthermore, according to the technical solution disclosed in Patent Document 10 (Li Zhenxing, Multi-colored Luminous Inlay Architectural Finish and Construction Technology, CN1179496A), it should be possible to use water glass and CaAlSiN3:Eu nitride red fluorescent material to make fluorescent films (the water glass curing process is also non-sintering); however, Patent Document 11 (Wang Lige, Zhang Fan, Wang Enze, Zhang Zhengquan, Li Liangfeng, Zhou Yongsheng, Chen Qi, Yang Liu, A Water-resistant Curing Agent for Water Glass Adhesive, CN103937415B) argues that water glass has poor water resistance because it contains highly absorbent alkali metal oxides and water-soluble sodium silicate in the hardened material. Therefore, it is clear that the technical solution based on water glass and CaAlSiN3:Eu nitride red fluorescent material to make fluorescent films is not suitable for laser lighting technology.

[0015] In conclusion, existing literature shows that if we want to achieve laser lighting technology applications for occasions with high requirements for color index, such as museums and cinemas, it is difficult to maintain the luminescence performance (quantum efficiency) of CaAlSiN3:Eu nitride red phosphor material as the red light source, regardless of whether a sintering-free process is used. Summary of the Invention

[0016] The primary objective of this invention is to provide a sinter-free technique for preparing fluorescent thin films for laser illumination.

[0017] The fluorescent film for laser illumination prepared by the non-sintering technology comprises a metallic aluminum plate substrate with a visible light reflectance greater than 95% and a thickness of 0.5–2 mm, and a light-emitting layer (on the metallic aluminum plate substrate) with a thickness of 100–500 μm. The light-emitting layer is obtained by non-sintering technology after uniformly mixing fluorescent materials and fixatives under air atmosphere at a temperature of 40–80 °C. The fluorescent materials contained in the light-emitting layer are two or more of the following: cyan fluorescent materials, green fluorescent materials, yellow fluorescent materials, orange fluorescent materials, and red fluorescent materials, wherein yellow fluorescent materials and red fluorescent materials are essential. Preferably, in the fluorescent film, the thickness of the metallic aluminum plate substrate is 1 mm, and the thickness of the light-emitting layer is 300 μm.

[0018] A second objective of this invention is to provide a method for preparing fluorescent thin films for laser illumination using a sinter-free technique. The preparation method includes:

[0019] a) Weigh out BaSi2O2N2:Eu cyan fluorescent material, β-SiAlON:Eu green fluorescent material, and Y3Al5O according to a mass ratio of (0~25):(0~25):(40~80):(0~25):(15~25). 12 Ce yellow fluorescent material, Y4Ba2[Si9ON 16 Two or more of O:Eu orange fluorescent material and CaAlSiN3:Eu red fluorescent material (of which yellow fluorescent material and red fluorescent material are required) are mixed evenly to obtain mixed fluorescent material X;

[0020] b) The mixed fluorescent material X obtained in step a) is mixed with a fixative having a chemical composition of aluminum dihydrogen phosphate (30%–60% by mass), alumina sol (20%–40% by mass), and methanol (20%–30% by mass) in a mass ratio of 1:0.5–1:0.7 to obtain slurry Z;

[0021] c) The slurry Z obtained in step b) is coated onto one side of a metal aluminum plate substrate using either a casting method or a doctor blade method, with a coating thickness of 100–500 μm. After drying at 40–80°C in air for 1 hour, a fluorescent film prepared using a non-sintering technique, intended for laser lighting applications, is obtained, comprising a metal aluminum plate substrate with a visible light reflectivity greater than 95% and a light-emitting layer (on the metal aluminum plate substrate).

[0022] The present invention also provides a reflective structure laser lighting device, which includes a 450nm blue laser diode and a fluorescent thin film for laser lighting prepared based on a sinter-free technology placed opposite it; the light generated by the light-emitting layer in the fluorescent thin film when excited by the 450nm blue laser and the blue light not absorbed by the light-emitting layer are combined to produce white light with a color temperature range of 3000K to 4500K and a color rendering index (Ra) of 90 to 98.

[0023] Compared with the prior art, the beneficial effects achieved by the technical solution of this invention are:

[0024] This invention provides a fluorescent thin film for laser illumination prepared using a sinter-free technique. The fluorescent thin film comprises a metallic aluminum substrate with a thickness of 0.5–2 mm and a visible light reflectance greater than 95%, and a light-emitting layer (on the metallic aluminum substrate) with a thickness of 100–500 μm. The light-emitting layer is obtained by uniformly mixing fluorescent materials and a fixative under air conditions at a temperature of 40–80 °C using a sinter-free technique. Under blue light excitation at 450 nm, the light emitted by the light-emitting layer mixes with unabsorbed blue light to produce white light with a color temperature range of 3000 K–4500 K and a color rendering index (Ra) of 90–98. Compared with existing technologies, the fluorescent thin film for laser lighting prepared by the non-sintering technology involved in this invention has a simple overall structure and a simple preparation process; the nitride red fluorescent material does not undergo any sintering process, and the luminescence performance of the fluorescent material is maintained to a great extent; and the preparation process does not use water, which would cause the nitride red fluorescent material to decompose; the fluorescent thin film is directly coupled to a highly thermally conductive aluminum plate, thereby enabling the fluorescent thin film (prepared by the non-sintering technology) to be used for laser lighting. Attached Figure Description

[0025] Figure 1 This is the spectrum obtained in Comparative Example 1 of the present invention;

[0026] Figure 2 The spectrum obtained in Embodiment 1 of the present invention;

[0027] Figure 3 The spectrum obtained in Example 9 of this invention;

[0028] Figure 4 This is a schematic diagram of the structure of the laser illumination device of the present invention. Detailed Implementation

[0029] To make the technical problems, technical solutions and beneficial effects of the present invention clearer and more understandable, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0030] The specific steps of the method for preparing the fluorescent thin film are as follows:

[0031] a) Weigh out two or more of the following fluorescent materials in proportion: cyan, green, yellow, orange, and red (yellow and red fluorescent materials are required), mix them evenly, and obtain mixed fluorescent material X.

[0032] b) Mix the mixed fluorescent material X obtained in step a) with the fixative in a certain proportion to obtain slurry Z;

[0033] c) The slurry Z obtained in step b) is coated onto one side of the aluminum plate substrate with a coating thickness of 100-500 μm. After drying at 40-80°C in air for 1 hour, a fluorescent film prepared by non-sintering technology, which is intended for laser lighting applications and consists of an aluminum plate substrate with a visible light reflectance greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0034] Other specific conditions include:

[0035] In step a), the mass ratio of cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material is (0-25):(0-25):(40-80):(0-25):(15-25).

[0036] In step b), the mass ratio of the mixed fluorescent material X to the fixative is 1:0.5 to 1:0.7. In some embodiments provided by the present invention, the preferred ratio is 1:0.6.

[0037] In step c), the coating method is either casting or blade coating. In some embodiments provided by the present invention, the coating method is preferably blade coating.

[0038] In step c), the drying temperature is 40-80°C, the atmosphere is air, and the drying time is 1 hour. In some embodiments provided by the present invention, the drying temperature is preferably 60°C.

[0039] Multiple experiments revealed that after the Z-slurry is coated as the luminescent layer and then dried, the thickness of the luminescent layer decreases. Typically, the thickness of the target luminescent layer multiplied by 1.2 equals the thickness of the Z-slurry coating as the luminescent layer. That is, if a luminescent layer thickness of 100 μm is desired, the thickness of the Z-slurry coating should be 100 μm × 1.2 = 120 μm.

[0040] Therefore, in some embodiments provided by the present invention, the thickness of the aluminum plate substrate is 1 mm, the thickness of the Z slurry coating is 120 μm, and the mass ratio of the cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material, and red fluorescent material is (0):(0):(80):(0):(20); in some embodiments provided by the present invention, the thickness of the aluminum plate substrate is 1 mm, the thickness of the Z slurry coating is 240 μm, and the mass ratio of the cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material, and red fluorescent material is (0):(0):(80):(0):(20). The mass ratio of fluorescent material, orange fluorescent material, and red fluorescent material is (0):(0):(80):(0):(20); In some embodiments provided by the present invention, the thickness of the aluminum plate substrate is 1 mm, the thickness of the Z slurry coating is 360 μm, and the mass ratio of cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material, and red fluorescent material is (0):(0):(80):(0):(20); In some embodiments provided by the present invention, the thickness of the aluminum plate substrate is 1 mm, the thickness of the Z slurry coating is 480 μm, and the mass ratio of cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material, and red fluorescent material is (0):(0):(80):(0):(20); The mass ratio of the fluorescent materials (cyan, green, yellow, orange, and red) is (0):(0):(80):(0):(15); In some embodiments provided by this invention, the thickness of the aluminum plate substrate is 1 mm, the thickness of the Z slurry coating is 600 μm, and the mass ratio of the fluorescent materials (cyan, green, yellow, orange, and red) is (0):(0):(80):(0):(25); In some embodiments provided by this invention In the embodiments, the thickness of the aluminum plate substrate is 1 mm, the thickness of the Z slurry coating is 360 μm, and the mass ratio of the cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material is (5):(0):(80):(0):(20); In some embodiments provided by the present invention, the thickness of the aluminum plate substrate is 1 mm, the thickness of the Z slurry coating is 360 μm, and the mass ratio of the cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material is (15):(0):(80):(0):(20);In some embodiments provided by the present invention, the thickness of the aluminum plate substrate is 1 mm, the thickness of the Z slurry coating is 360 μm, and the mass ratio of cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material is (0):(5):(80):(0):(20); In some embodiments provided by the present invention, the thickness of the aluminum plate substrate is 1 mm, the thickness of the Z slurry coating is 360 μm, and the mass ratio of cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material is (0):(15):(80):(0):(20); In some embodiments provided by the present invention, the thickness of the aluminum plate substrate is 1 mm The thickness of the Z-slurry coating is 360 μm, and the mass ratio of cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material is (0):(0):(80):(5):(20); In some embodiments provided by the present invention, the thickness of the aluminum plate substrate is 1 mm, the thickness of the Z-slurry coating is 360 μm, and the mass ratio of cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material is (0):(0):(80):(15):(20); In some embodiments provided by the present invention, the thickness of the aluminum plate substrate is 1 mm, the thickness of the Z-slurry coating is 360 μm, and the mass ratio of cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material is (0):(0):(80):(15):(20); The mass ratio of the materials, yellow fluorescent material, orange fluorescent material, and red fluorescent material is (5):(5):(80):(5):(20); In some embodiments provided by the present invention, the thickness of the aluminum plate substrate is 1 mm, the thickness of the Z slurry coating is 360 μm, and the mass ratio of the cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material, and red fluorescent material is (5):(5):(80):(15):(20); In some embodiments provided by the present invention, the thickness of the aluminum plate substrate is 1 mm, the thickness of the Z slurry coating is 360 μm, and the mass ratio of the cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material, and red fluorescent material is (5):(5):(80):(15):(20); The thickness of the aluminum plate substrate is 1 mm, the thickness of the Z slurry coating is 360 μm, and the mass ratio of the cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material is (5):(15):(80):(15):(20); In some embodiments provided by the present invention, the thickness of the aluminum plate substrate is 1 mm, the thickness of the Z slurry coating is 360 μm, and the mass ratio of the cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material is (15):(5):(80):(5):(20);In some embodiments provided by the present invention, the thickness of the aluminum plate substrate is 1 mm, the thickness of the Z slurry coating is 360 μm, and the mass ratio of cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material is (15):(5):(80):(15):(20); In some embodiments provided by the present invention, the thickness of the aluminum plate substrate is 1 mm, the thickness of the Z slurry coating is 360 μm, and the mass ratio of cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material is (15):(15):(80):(5):(20); In this invention In some embodiments provided by the present invention, the thickness of the aluminum plate substrate is 1 mm, the thickness of the Z slurry coating is 360 μm, and the mass ratio of cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material is (15):(15):(80):(15):(20); In other embodiments provided by the present invention, the thickness of the aluminum plate substrate is 1.5 mm, the thickness of the Z slurry coating is 360 μm, and the mass ratio of cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material is (18):(12):(69):(16):(15).

[0041] The sinter-free technology of this invention has successfully realized fluorescent thin films for laser lighting applications.

[0042] The laser lighting device comprises at least a 450nm blue laser diode and a fluorescent thin film for laser lighting prepared using a non-sintering technology. The light-emitting port of the blue laser diode and the light-emitting layer in the fluorescent thin film are placed opposite each other. The light generated by the excitation of the 450nm blue laser in the light-emitting layer is combined with the blue light that is not absorbed by the light-emitting layer to produce white light with a color temperature range of 3000K to 4500K and a color rendering index (Ra) of 90 to 98.

[0043] To further illustrate the present invention, the following describes in detail, with reference to embodiments, a fluorescent thin film for laser illumination prepared by a sinter-free technique provided by the present invention.

[0044] All reagents used in the following comparative examples and embodiments are commercially available.

[0045] Comparative Example 1

[0046] Follow these steps to make it:

[0047] a) Weigh out the yellow fluorescent material, glycerol, acetone and low melting point glass powder in a mass ratio of 1:0.2:0.2:0.3, mix them evenly to obtain slurry Z1;

[0048] b) The slurry Z1 obtained in step a) is coated onto one side of a metal aluminum plate substrate with a thickness of 1 mm and a coating thickness of 360 μm. After sintering at 550 °C in air atmosphere for 30 min, a fluorescent film containing a metal aluminum plate substrate with a visible light reflectance greater than 95% and a light-emitting layer (on the metal aluminum plate substrate) can be obtained.

[0049] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 200.3 kPa, indicating a strong adhesion between the emitting layer and the aluminum substrate. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 17.3 W / m·K, indicating strong thermal conductivity of the fluorescent film. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because the fluorescent material did not undergo any sintering process, it did not oxidize, and its luminescence performance did not decrease; therefore, the overall quantum efficiency (of the device) was high, with a value of 85.2%. The light and color parameters of the blue laser and fluorescent thin film combination were tested using a light source photoluminescence and electroluminescence integrated testing system. Since the light-emitting layer only contains yellow fluorescent material, the color rendering index (Ra) of the white light emitted by the device is low, at 62.2; the color temperature is high, at 7733K (see Table 1 for light and color parameters). This is completely insufficient to meet the lighting requirements of places such as museums that have extremely high requirements for color rendering index and color temperature. Figure 1 This is the spectrum obtained in Comparative Example 1 of the present invention.

[0050] It is evident that the fluorescent film provided in Comparative Example 1 cannot be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0051] Comparative Example 2

[0052] Follow these steps to make it:

[0053] a) Weigh out red fluorescent material, glycerol, acetone and low melting point glass powder in a mass ratio of 1:0.2:0.2:0.3, mix them evenly to obtain slurry Z2;

[0054] b) The slurry Z2 obtained in step a) is coated onto one side of a metal aluminum plate substrate with a thickness of 1 mm and a coating thickness of 360 μm. After sintering at 550 °C in air atmosphere for 30 min, a fluorescent film containing a metal aluminum plate substrate with a visible light reflectance greater than 95% and a light-emitting layer (on the metal aluminum plate substrate) can be obtained.

[0055] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 186.1 kPa, indicating a strong adhesion between the emitting layer and the aluminum substrate. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 12.7 W / m·K, indicating strong thermal conductivity of the fluorescent film. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because the red nitride fluorescent material underwent a sintering process, and the molten glass corroded the nitride fluorescent material, the luminescence performance of the fluorescent material decreased, resulting in a low (overall) quantum efficiency of 62.7%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic electroluminescence integrated testing system. Since the light-emitting layer only contains red fluorescent material, the device does not emit white light (see Table 1 for light color parameters), which cannot meet the lighting requirements of places such as museums with extremely high requirements for color rendering index / color temperature.

[0056] It is evident that the fluorescent film provided in Comparative Example 2 cannot be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0057] Comparative Example 3

[0058] Follow these steps to make it:

[0059] a) Weigh out the yellow fluorescent material, red fluorescent material, glycerol, acetone, and low-melting-point glass powder in a mass ratio of 0.8:0.2:0.2:0.2:0.3, mix them evenly, and obtain slurry Z3;

[0060] b) The slurry Z3 obtained in step a) is coated onto one side of a metal aluminum plate substrate with a thickness of 1 mm and a coating thickness of 360 μm. After sintering at 550 °C in air atmosphere for 30 min, a fluorescent film containing a metal aluminum plate substrate with a visible light reflectance greater than 95% and a light-emitting layer (on the metal aluminum plate substrate) can be obtained.

[0061] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 144.9 kPa, indicating a strong adhesion between the emitting layer and the aluminum substrate. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 14.3 W / m·K, indicating strong thermal conductivity of the fluorescent film. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because the red nitride phosphor in the fluorescent material underwent a sintering process, and the molten glass corroded the nitride phosphor, the luminescence performance of the fluorescent material decreased, resulting in a low (overall) quantum efficiency of 71.1%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains yellow and red fluorescent materials, the color rendering index (Ra) of the white light emitted by the device is relatively high, at 86.6; the color temperature is relatively low, at 5019K (see Table 1 for light color parameters), which is close to meeting the lighting requirements of places such as museums that have extremely high requirements for color rendering index / color temperature.

[0062] It is evident that the fluorescent film provided in Comparative Example 3 can barely meet the requirements for laser lighting in venues with high color index requirements, such as museums and cinemas.

[0063] Comparative Example 4

[0064] Follow these steps to make it:

[0065] a) Weigh out yellow fluorescent material and red fluorescent material in a mass ratio of (80):(20), mix them evenly, and obtain mixed fluorescent material X4;

[0066] b) Mix the mixed fluorescent material X4 obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z4;

[0067] c) The slurry Z4 obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 60 μm. After drying at 50 °C in air for 1 h, a fluorescent film prepared by non-sintering technology is obtained, which includes a 1 mm thick aluminum plate substrate with a visible light reflectance of greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0068] The bonding force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 51.6 kPa, indicating a relatively strong bonding force. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 23.9 W / m·K, indicating good thermal conductivity. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride fluorescent material) did not undergo any sintering process, the fluorescent material did not oxidize, and the luminescence performance did not decrease. However, the fluorescent film is very thin, allowing a large amount of blue laser light to penetrate it. The fluorescent film absorbs and utilizes less blue light, therefore the overall quantum efficiency (of the device) is relatively high, at 84.9%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Due to the presence of yellow and red fluorescent materials in the emitting layer, and the fact that blue light can penetrate the fluorescent thin film and be reflected by the aluminum plate, the blue light is relatively excessive. Therefore, the color rendering index (Ra) of the white light emitted by the device is relatively high, at 83.9; the color temperature is relatively low, at 5739K (see Table 1 for detailed light color parameters), which cannot meet the lighting requirements of places such as museums that have extremely high requirements for color rendering index / color temperature.

[0069] It is evident that the fluorescent film provided in Comparative Example 4 cannot be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0070] Comparative Example 5

[0071] Follow these steps to make it:

[0072] a) Weigh out yellow fluorescent material and red fluorescent material in a mass ratio of (80):(20), mix them evenly, and obtain mixed fluorescent material X5;

[0073] b) Mix the mixed fluorescent material X5 obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z5;

[0074] c) The slurry Z5 obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 720 μm. After drying at 50 °C in air for 1 h, a fluorescent film prepared by non-sintering technology is obtained, which includes a 1 mm thick aluminum plate substrate with a visible light reflectance of greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0075] The adhesion between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer. Due to the thickness of the fluorescent film, the value was 12.1 kPa, indicating a relatively weak adhesion. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 6.9 W / m·K, indicating relatively strong thermal conductivity. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride phosphor) did not undergo any sintering process, the phosphor did not oxidize, and the luminescence performance did not decrease. Therefore, the overall quantum efficiency (of the device) was high, with a value of 84.4%. The light and color parameters of the blue laser and fluorescent film combination were tested using a light source photoluminescence and electroluminescence integrated testing system. Due to the presence of yellow and red fluorescent materials in the emitting layer and the excessive thickness of the fluorescent film, the blue laser could hardly penetrate the fluorescent film. The fluorescent film absorbed a large amount of blue light, resulting in a relatively low color rendering index (Ra) of 72.7 and a relatively low color temperature of 4032K (see Table 1 for detailed light and color parameters). This cannot meet the lighting requirements of places such as museums that have extremely high requirements for color rendering index and color temperature.

[0076] It is evident that the fluorescent film provided in Comparative Example 5 cannot be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0077] Comparative Example 6

[0078] Follow these steps to make it:

[0079] a) Weigh out yellow fluorescent material and red fluorescent material in a mass ratio of (80):(20), mix them evenly, and obtain mixed fluorescent material X6;

[0080] b) Mix the mixed fluorescent material X6 obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z6;

[0081] c) The slurry Z6 obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 360 μm. After heating at 500 °C in air for 1 h, a fluorescent film containing a luminescent layer (on the aluminum plate substrate) with a visible light reflectance greater than 95% can be obtained.

[0082] The bonding force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 48.9 kPa, indicating a strong bonding force. Therefore, heating did not significantly weaken the bonding force between the emitting layer and the aluminum substrate. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 8.2 W / m·K, indicating strong thermal conductivity. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because the red nitride fluorescent material in the fluorescent material underwent a sintering process, the luminescence performance of the fluorescent material decreased, resulting in a low (overall) quantum efficiency of 70.3%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains yellow and red fluorescent materials, the color rendering index (Ra) of the white light emitted by the device is relatively high, at 88.9; the color temperature is relatively low, at 5001K (see Table 1 for light color parameters). This can barely meet the lighting requirements of places such as museums that have extremely high requirements for color rendering index / color temperature.

[0083] It is evident that the fluorescent film provided in Comparative Example 6 can barely meet the requirements for laser lighting in venues with high colorimetric indices, such as museums and cinemas.

[0084] Example 1

[0085] Follow these steps to make it:

[0086] a) Weigh out yellow fluorescent material and red fluorescent material in a mass ratio of (80):(20), mix them evenly, and obtain mixed fluorescent material X;

[0087] b) Mix the mixed fluorescent material X obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z;

[0088] c) The slurry Z obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 120 μm. After drying at 60 °C in air for 1 h, a fluorescent film prepared by non-sintering technology for laser lighting applications is obtained, which includes a 1 mm thick aluminum plate substrate with a visible light reflectivity of greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0089] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 57.5 kPa, indicating a strong adhesion between the emitting layer and the aluminum substrate. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 20.3 W / m·K, indicating strong thermal conductivity of the fluorescent film. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride phosphor) did not undergo any sintering process, the phosphor did not oxidize, and the luminescence performance did not decrease; therefore, the overall quantum efficiency (of the device) was high, with a value of 84.2%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains yellow and red fluorescent materials, the white light emitted by the device has a high color rendering index (Ra) of 91.1 and a low color temperature of 3895K (see Table 1 for light color parameters). This fully meets the lighting requirements of places such as museums that have extremely high requirements for color rendering index and color temperature. Figure 2 This is the spectrum obtained in Embodiment 1 of the present invention.

[0090] As can be seen, the fluorescent thin film prepared by the sinter-free technology provided in Example 1 can be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0091] Example 2

[0092] Follow these steps to make it:

[0093] a) Weigh out yellow fluorescent material and red fluorescent material in a mass ratio of (80):(20), mix them evenly, and obtain mixed fluorescent material X;

[0094] b) Mix the mixed fluorescent material X obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z;

[0095] c) The slurry Z obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 240 μm. After drying at 60 °C in air for 1 h, a fluorescent film prepared by non-sintering technology for laser lighting applications is obtained, which includes a luminescent layer (on the aluminum plate substrate) with a visible light reflectance greater than 95%.

[0096] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 57.7 kPa, indicating a strong adhesion between the emitting layer and the aluminum substrate. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 18.7 W / m·K, indicating strong thermal conductivity of the fluorescent film. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride phosphor) did not undergo any sintering process, the phosphor did not oxidize, and the luminescence performance did not decrease; therefore, the overall quantum efficiency (of the device) was high, with a value of 84.1%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains yellow and red fluorescent materials, the white light emitted by the device has a high color rendering index (Ra) of 90.8 and a low color temperature of 3754K (see Table 1 for light color parameters). This fully meets the lighting requirements of places such as museums that have extremely high requirements for color rendering index and color temperature.

[0097] As can be seen, the fluorescent film prepared by the sinter-free technology provided in Example 2 can be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0098] Example 3

[0099] Follow these steps to make it:

[0100] a) Weigh out yellow fluorescent material and red fluorescent material in a mass ratio of (80):(20), mix them evenly, and obtain mixed fluorescent material X;

[0101] b) Mix the mixed fluorescent material X obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z;

[0102] c) The slurry Z obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 360 μm. After drying at 60 °C in air for 1 h, a fluorescent film prepared by non-sintering technology for laser lighting applications is obtained, which includes a 1 mm thick aluminum plate substrate with a visible light reflectance of greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0103] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 55.9 kPa, indicating a strong adhesion between the two. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 16.5 W / m·K, indicating strong thermal conductivity. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride phosphor) did not undergo any sintering process, the phosphor did not oxidize, and the luminescence performance did not decrease; therefore, the overall quantum efficiency (of the device) was high, with a value of 84.5%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains yellow and red fluorescent materials, the white light emitted by the device has a high color rendering index (Ra) of 90.5 and a low color temperature of 3422K (see Table 1 for light color parameters). This fully meets the lighting requirements of places such as museums that have extremely high requirements for color rendering index and color temperature.

[0104] As can be seen, the fluorescent thin film prepared by the sinter-free technology provided in Example 3 can be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0105] Example 4

[0106] Follow these steps to make it:

[0107] a) Weigh out yellow fluorescent material and red fluorescent material in a mass ratio of (80):(20), mix them evenly, and obtain mixed fluorescent material X;

[0108] b) Mix the mixed fluorescent material X obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z;

[0109] c) The slurry Z obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 480 μm. After drying at 60 °C in air for 1 h, a fluorescent film prepared by non-sintering technology for laser lighting applications is obtained, which includes a 1 mm thick aluminum plate substrate with a visible light reflectivity of greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0110] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 66.8 kPa, indicating a strong adhesion between the two. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 14.3 W / m·K, indicating strong thermal conductivity. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride phosphor) did not undergo any sintering process, the phosphor did not oxidize, and the luminescence performance did not decrease; therefore, the overall quantum efficiency (of the device) was high, with a value of 85.2%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains yellow and red fluorescent materials, the white light emitted by the device has a high color rendering index (Ra) of 90.2 and a low color temperature of 3317K (see Table 1 for light color parameters). This fully meets the lighting requirements of places such as museums that have extremely high requirements for color rendering index and color temperature.

[0111] As can be seen, the fluorescent film prepared by the sinter-free technology provided in Example 4 can be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0112] Example 5

[0113] Follow these steps to make it:

[0114] a) Weigh out yellow fluorescent material and red fluorescent material in a mass ratio of (80):(20), mix them evenly, and obtain mixed fluorescent material X;

[0115] b) Mix the mixed fluorescent material X obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z;

[0116] c) The slurry Z obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 600 μm. After drying at 60 °C in air for 1 h, a fluorescent film prepared by non-sintering technology for laser lighting applications is obtained, which includes a 1 mm thick aluminum plate substrate with a visible light reflectance of greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0117] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 58.1 kPa, indicating a strong adhesion between the two. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 11.1 W / m·K, indicating strong thermal conductivity. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride phosphor) did not undergo any sintering process, the phosphor did not oxidize, and the luminescence performance did not decrease; therefore, the overall quantum efficiency (of the device) was high, with a value of 83.9%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains yellow and red fluorescent materials, the white light emitted by the device has a high color rendering index (Ra) of 90.1 and a low color temperature of 3101K (see Table 1 for light color parameters). This fully meets the lighting requirements of places such as museums that have extremely high requirements for color rendering index and color temperature.

[0118] As can be seen, the fluorescent thin film prepared by the sinter-free technology provided in Example 5 can be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0119] Example 6

[0120] Follow these steps to make it:

[0121] a) Weigh out cyan fluorescent material, yellow fluorescent material and red fluorescent material in a mass ratio of (5):(80):(20), mix them evenly to obtain mixed fluorescent material X;

[0122] b) Mix the mixed fluorescent material X obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z;

[0123] c) The slurry Z obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 360 μm. After drying at 60 °C in air for 1 h, a fluorescent film prepared by non-sintering technology for laser lighting applications is obtained, which includes a 1 mm thick aluminum plate substrate with a visible light reflectance of greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0124] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 51.9 kPa, indicating a strong adhesion between the emitting layer and the aluminum substrate. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 15.8 W / m·K, indicating strong thermal conductivity of the fluorescent film. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride phosphor) did not undergo any sintering process, the phosphor did not oxidize, and the luminescence performance did not decrease; therefore, the overall quantum efficiency (of the device) was high, with a value of 83.8%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains cyan, yellow and red fluorescent materials, the white light emitted by the device has a high color rendering index (Ra) of 92.3 and a low color temperature of 3650K (see Table 1 for light color parameters). This fully meets the lighting requirements of places such as museums that have extremely high requirements for color rendering index and color temperature.

[0125] As can be seen, the fluorescent thin film prepared by the sinter-free technology provided in Example 6 can be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0126] Example 7

[0127] Follow these steps to make it:

[0128] a) Weigh out cyan fluorescent material, yellow fluorescent material and red fluorescent material in a mass ratio of (15):(80):(20), mix them evenly to obtain mixed fluorescent material X;

[0129] b) Mix the mixed fluorescent material X obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z;

[0130] c) The slurry Z obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 360 μm. After drying at 60 °C in air for 1 h, a fluorescent film prepared by non-sintering technology for laser lighting applications is obtained, which includes a 1 mm thick aluminum plate substrate with a visible light reflectance of greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0131] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 55.7 kPa, indicating a strong adhesion between the emitting layer and the aluminum substrate. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 16.0 W / m·K, indicating strong thermal conductivity of the fluorescent film. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride phosphor) did not undergo any sintering process, the phosphor did not oxidize, and the luminescence performance did not decrease; therefore, the overall quantum efficiency (of the device) was high, with a value of 84.4%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains cyan, yellow and red fluorescent materials, the white light emitted by the device has a high color rendering index (Ra) of 92.5 and a low color temperature of 3736K (see Table 1 for light color parameters). This fully meets the lighting requirements of places such as museums that have extremely high requirements for color rendering index and color temperature.

[0132] As can be seen, the fluorescent thin film prepared by the sinter-free technology provided in Example 7 can be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0133] Example 8

[0134] Follow these steps to make it:

[0135] a) Weigh out green fluorescent material, yellow fluorescent material and red fluorescent material in a mass ratio of (5):(80):(20), mix them evenly to obtain mixed fluorescent material X;

[0136] b) Mix the mixed fluorescent material X obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z;

[0137] c) The slurry Z obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 360 μm. After drying at 60 °C in air for 1 h, a fluorescent film prepared by non-sintering technology for laser lighting applications is obtained, which includes a 1 mm thick aluminum plate substrate with a visible light reflectance of greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0138] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 55.3 kPa, indicating a strong adhesion between the emitting layer and the aluminum substrate. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 15.1 W / m·K, indicating strong thermal conductivity of the fluorescent film. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride phosphor) did not undergo any sintering process, the phosphor did not oxidize, and the luminescence performance did not decrease; therefore, the overall quantum efficiency (of the device) was high, with a value of 85.1%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains green, yellow and red fluorescent materials, the white light emitted by the device has a high color rendering index (Ra) of 92.2 and a low color temperature of 3839K (see Table 1 for light color parameters). This fully meets the lighting requirements of places such as museums that have extremely high requirements for color rendering index and color temperature.

[0139] As can be seen, the fluorescent film prepared by the non-sintering technology provided in Example 8 can be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0140] Example 9

[0141] Follow these steps to make it:

[0142] a) Weigh out green fluorescent material, yellow fluorescent material and red fluorescent material in a mass ratio of (15):(80):(20), mix them evenly to obtain mixed fluorescent material X;

[0143] b) Mix the mixed fluorescent material X obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z;

[0144] c) The slurry Z obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 360 μm. After drying at 60 °C in air for 1 h, a fluorescent film prepared by non-sintering technology for laser lighting applications is obtained, which includes a 1 mm thick aluminum plate substrate with a visible light reflectance of greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0145] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 72.5 kPa, indicating a strong adhesion between the emitting layer and the aluminum substrate. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 15.8 W / m·K, indicating strong thermal conductivity of the fluorescent film. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride phosphor) did not undergo any sintering process, the phosphor did not oxidize, and the luminescence performance did not decrease; therefore, the overall quantum efficiency (of the device) was high, with a value of 83.8%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains green, yellow and red fluorescent materials, the white light emitted by the device has a high color rendering index (Ra) of 92.8 and a low color temperature of 4002K (see Table 1 for light color parameters). This fully meets the lighting requirements of places such as museums that have extremely high requirements for color rendering index and color temperature. Figure 3 This is the spectrum obtained in Example 9 of the present invention.

[0146] As can be seen, the fluorescent film prepared by the sinter-free technology provided in Example 9 can be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0147] Example 10

[0148] Follow these steps to make it:

[0149] a) Weigh out yellow fluorescent material, orange fluorescent material and red fluorescent material in a mass ratio of (80):(5):(20), mix them evenly to obtain mixed fluorescent material X;

[0150] b) Mix the mixed fluorescent material X obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z;

[0151] c) The slurry Z obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 360 μm. After drying at 60 °C in air for 1 h, a fluorescent film prepared by non-sintering technology for laser lighting applications is obtained, which includes a 1 mm thick aluminum plate substrate with a visible light reflectance of greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0152] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 70.3 kPa, indicating a strong adhesion between the emitting layer and the aluminum substrate. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 16.8 W / m·K, indicating strong thermal conductivity of the fluorescent film. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride phosphor) did not undergo any sintering process, the phosphor did not oxidize, and the luminescence performance did not decrease; therefore, the overall quantum efficiency (of the device) was high, with a value of 82.9%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains yellow, orange and red fluorescent materials, the white light emitted by the device has a high color rendering index (Ra) of 82.9 and a low color temperature of 3660K (see Table 1 for light color parameters). This fully meets the lighting requirements of places such as museums that have extremely high requirements for color rendering index and color temperature.

[0153] As can be seen, the fluorescent thin film prepared by the sinter-free technology provided in Example 10 can be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0154] Example 11

[0155] Follow these steps to make it:

[0156] a) Weigh out yellow fluorescent material, orange fluorescent material and red fluorescent material in a mass ratio of (80):(15):(20), mix them evenly to obtain mixed fluorescent material X;

[0157] b) Mix the mixed fluorescent material X obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z;

[0158] c) The slurry Z obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 360 μm. After drying at 60 °C in air for 1 h, a fluorescent film prepared by non-sintering technology for laser lighting applications is obtained, which includes a 1 mm thick aluminum plate substrate with a visible light reflectance of greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0159] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 65.1 kPa, indicating a strong adhesion between the two. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 14.8 W / m·K, indicating strong thermal conductivity. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride phosphor) did not undergo any sintering process, the phosphor did not oxidize, and the luminescence performance did not decrease; therefore, the overall quantum efficiency (of the device) was high, with a value of 83.7%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains yellow, orange and red fluorescent materials, the white light emitted by the device has a high color rendering index (Ra) of 91.6 and a low color temperature of 3556K (see Table 1 for light color parameters). This fully meets the lighting requirements of places such as museums that have extremely high requirements for color rendering index and color temperature.

[0160] As can be seen, the fluorescent thin film prepared by the sinter-free technology provided in Example 11 can be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0161] Example 12

[0162] Follow these steps to make it:

[0163] a) Weigh out cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material in a mass ratio of (5):(5):(80):(5):(20), mix them evenly to obtain mixed fluorescent material X;

[0164] b) Mix the mixed fluorescent material X obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z;

[0165] c) The slurry Z obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 360 μm. After drying at 60 °C in air for 1 h, a fluorescent film prepared by non-sintering technology for laser lighting applications is obtained, which includes a 1 mm thick aluminum plate substrate with a visible light reflectance of greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0166] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 65.6 kPa, indicating a strong adhesion between the emitting layer and the aluminum substrate. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 15.5 W / m·K, indicating strong thermal conductivity of the fluorescent film. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride phosphor) did not undergo any sintering process, the phosphor did not oxidize, and the luminescence performance did not decrease; therefore, the overall quantum efficiency (of the device) was high, with a value of 82.2%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains cyan, green, yellow, orange and red fluorescent materials, the white light emitted by the device has a high color rendering index (Ra) of 95.3 and a low color temperature of 4005K (see Table 1 for light color parameters). This fully meets the lighting requirements of places such as museums that have extremely high requirements for color rendering index and color temperature.

[0167] As can be seen, the fluorescent thin film prepared by the sinter-free technology provided in Example 12 can be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0168] Example 13

[0169] Follow these steps to make it:

[0170] a) Weigh out cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material in a mass ratio of (5):(5):(80):(15):(20), mix them evenly to obtain mixed fluorescent material X;

[0171] b) Mix the mixed fluorescent material X obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z;

[0172] c) The slurry Z obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 360 μm. After drying at 60 °C in air for 1 h, a fluorescent film prepared by non-sintering technology for laser lighting applications is obtained, which includes a 1 mm thick aluminum plate substrate with a visible light reflectance of greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0173] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 69.4 kPa, indicating a strong adhesion between the two. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 16.2 W / m·K, indicating strong thermal conductivity. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride phosphor) did not undergo any sintering process, the phosphor did not oxidize, and the luminescence performance did not decrease; therefore, the overall quantum efficiency (of the device) was high, with a value of 83.1%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains cyan, green, yellow, orange and red fluorescent materials, the white light emitted by the device has a high color rendering index (Ra) of 94.6 and a low color temperature of 3992K (see Table 1 for detailed light color parameters), which can fully meet the lighting needs of places such as museums with extremely high requirements for color rendering index / color temperature.

[0174] As can be seen, the fluorescent thin film prepared by the non-sintering technology provided in Example 13 can be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0175] Example 14

[0176] Follow these steps to make it:

[0177] a) Weigh out cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material in a mass ratio of (5):(15):(80):(5):(20), mix them evenly to obtain mixed fluorescent material X;

[0178] b) Mix the mixed fluorescent material X obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z;

[0179] c) The slurry Z obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 360 μm. After drying at 60 °C in air for 1 h, a fluorescent film prepared by non-sintering technology for laser lighting applications is obtained, which includes a 1 mm thick aluminum plate substrate with a visible light reflectance of greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0180] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 59.9 kPa, indicating a strong adhesion between the two. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 16.7 W / m·K, indicating strong thermal conductivity. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride phosphor) did not undergo any sintering process, the phosphor did not oxidize, and the luminescence performance did not decrease; therefore, the overall quantum efficiency (of the device) was high, with a value of 84.8%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains cyan, green, yellow, orange and red fluorescent materials, the white light emitted by the device has a high color rendering index (Ra) of 96.6 and a low color temperature of 4118K (see Table 1 for light color parameters). This fully meets the lighting requirements of places such as museums that have extremely high requirements for color rendering index and color temperature.

[0181] As can be seen, the fluorescent thin film prepared by the sinter-free technology provided in Example 14 can be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0182] Example 15

[0183] Follow these steps to make it:

[0184] a) Weigh out cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material in a mass ratio of (5):(15):(80):(15):(20), mix them evenly to obtain mixed fluorescent material X;

[0185] b) Mix the mixed fluorescent material X obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z;

[0186] c) The slurry Z obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 360 μm. After drying at 60 °C in air for 1 h, a fluorescent film prepared by non-sintering technology for laser lighting applications is obtained, which includes a 1 mm thick aluminum plate substrate with a visible light reflectance of greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0187] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 66.6 kPa, indicating a strong adhesion between the emitting layer and the aluminum substrate. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 12.5 W / m·K, indicating strong thermal conductivity of the fluorescent film. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride phosphor) did not undergo any sintering process, the phosphor did not oxidize, and the luminescence performance did not decrease; therefore, the overall quantum efficiency (of the device) was high, with a value of 85.1%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains cyan, green, yellow, orange and red fluorescent materials, the white light emitted by the device has a high color rendering index (Ra) of 95.7 and a low color temperature (see Table 1 for light color parameters), which is 4001K. This fully meets the lighting requirements of places such as museums that have extremely high requirements for color rendering index and color temperature.

[0188] As can be seen, the fluorescent thin film prepared by the sinter-free technology provided in Example 15 can be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0189] Example 16

[0190] Follow these steps to make it:

[0191] a) Weigh out cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material in a mass ratio of (15):(5):(80):(5):(20), mix them evenly to obtain mixed fluorescent material X;

[0192] b) Mix the mixed fluorescent material X obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z;

[0193] c) The slurry Z obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 360 μm. After drying at 60 °C in air for 1 h, a fluorescent film prepared by non-sintering technology for laser lighting applications is obtained, which includes a 1 mm thick aluminum plate substrate with a visible light reflectance of greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0194] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 61.4 kPa, indicating a strong adhesion between the two. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 15.6 W / m·K, indicating strong thermal conductivity. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride phosphor) did not undergo any sintering process, the phosphor did not oxidize, and the luminescence performance did not decrease; therefore, the overall quantum efficiency (of the device) was high, with a value of 83.2%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains cyan, green, yellow, orange and red fluorescent materials, the white light emitted by the device has a high color rendering index (Ra) of 94.8 and a low color temperature of 4216K (see Table 1 for light color parameters). This fully meets the lighting requirements of places such as museums that have extremely high requirements for color rendering index and color temperature.

[0195] As can be seen, the fluorescent thin film prepared by the sinter-free technology provided in Example 16 can be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0196] Example 17

[0197] Follow these steps to make it:

[0198] a) Weigh out cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material in a mass ratio of (15):(5):(80):(15):(20), mix them evenly to obtain mixed fluorescent material X;

[0199] b) Mix the mixed fluorescent material X obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z;

[0200] c) The slurry Z obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 360 μm. After drying at 60 °C in air for 1 h, a fluorescent film prepared by non-sintering technology for laser lighting applications is obtained, which includes a 1 mm thick aluminum plate substrate with a visible light reflectance of greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0201] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 63.3 kPa, indicating a strong adhesion between the two. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 16.8 W / m·K, indicating strong thermal conductivity. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride phosphor) did not undergo any sintering process, the phosphor did not oxidize, and the luminescence performance did not decrease; therefore, the overall quantum efficiency (of the device) was high, with a value of 83.3%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains cyan, green, yellow, orange and red fluorescent materials, the white light emitted by the device has a high color rendering index (Ra) of 93.7 and a low color temperature of 3827K (see Table 1 for light color parameters). This fully meets the lighting requirements of places such as museums that have extremely high requirements for color rendering index and color temperature.

[0202] As can be seen, the fluorescent thin film prepared by the non-sintering technology provided in Example 17 can be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0203] Example 18

[0204] Follow these steps to make it:

[0205] a) Weigh out cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material in a mass ratio of (15):(15):(80):(5):(20), mix them evenly to obtain mixed fluorescent material X;

[0206] b) Mix the mixed fluorescent material X obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z;

[0207] c) The slurry Z obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 360 μm. After drying at 60 °C in air for 1 h, a fluorescent film prepared by non-sintering technology for laser lighting applications is obtained, which includes a 1 mm thick aluminum plate substrate with a visible light reflectance of greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0208] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 64.9 kPa, indicating a strong adhesion between the two. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 16.6 W / m·K, indicating strong thermal conductivity. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride phosphor) did not undergo any sintering process, the phosphor did not oxidize, and the luminescence performance did not decrease; therefore, the overall quantum efficiency (of the device) was high, with a value of 84.2%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains cyan, green, yellow, orange and red fluorescent materials, the white light emitted by the device has a high color rendering index (Ra) of 96.6 and a low color temperature of 4359K (see Table 1 for detailed light color parameters), which can fully meet the lighting needs of places such as museums with extremely high requirements for color rendering index / color temperature.

[0209] As can be seen, the fluorescent film prepared by the non-sintering technology provided in Example 18 can be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0210] Example 19

[0211] Follow these steps to make it:

[0212] a) Weigh out cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material in a mass ratio of (15):(15):(80):(15):(20), mix them evenly to obtain mixed fluorescent material X;

[0213] b) Mix the mixed fluorescent material X obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z;

[0214] c) The slurry Z obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 360 μm. After drying at 60 °C in air for 1 h, a fluorescent film prepared by non-sintering technology for laser lighting applications is obtained, which includes a 1 mm thick aluminum plate substrate with a visible light reflectance of greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0215] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 61.4 kPa, indicating a strong adhesion between the two. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 15.0 W / m·K, indicating strong thermal conductivity. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride phosphor) did not undergo any sintering process, the phosphor did not oxidize, and the luminescence performance did not decrease; therefore, the overall quantum efficiency (of the device) was high, with a value of 83.7%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains cyan, green, yellow, orange and red fluorescent materials, the white light emitted by the device has a high color rendering index (Ra) of 95.2 and a low color temperature of 4333K (see Table 1 for light color parameters). This fully meets the lighting requirements of places such as museums that have extremely high requirements for color rendering index and color temperature.

[0216] As can be seen, the fluorescent thin film prepared by the sinter-free technology provided in Example 19 can be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0217] Example 20

[0218] Follow these steps to make it:

[0219] a) Weigh out cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material in a mass ratio of (18):(12):(69):(16):(15), mix them evenly to obtain mixed fluorescent material X;

[0220] b) Mix the mixed fluorescent material X obtained in step a) with the fixative at a mass ratio of 1:0.6 to obtain slurry Z;

[0221] c) The slurry Z obtained in step b) is coated onto one side of a 1 mm thick aluminum plate substrate with a coating thickness of 360 μm. After drying at 60 °C in air for 1 h, a fluorescent film prepared by non-sintering technology for laser lighting applications is obtained, which includes a 1 mm thick aluminum plate substrate with a visible light reflectance of greater than 95% and a light-emitting layer (on the aluminum plate substrate).

[0222] The adhesion force between the emitting layer and the aluminum substrate in the fluorescent film was measured using a tribometer, and the value was 60.5 kPa, indicating a strong adhesion between the two. The thermal conductivity of the fluorescent film (along the direction from the emitting layer to the aluminum substrate) was measured using a thermal conductivity meter, and the value was 14.7 W / m·K, indicating strong thermal conductivity. The fluorescent film was irradiated with a 450 nm blue laser (the laser's output port was placed opposite the emitting layer of the fluorescent film), and the quantum efficiency of the blue laser and fluorescent film assembly was measured using a quantum efficiency meter. Because all materials (especially the CaAlSiN3:Eu red nitride phosphor) did not undergo any sintering process, the phosphor did not oxidize, and the luminescence performance did not decrease; therefore, the overall quantum efficiency (of the device) was high, with a value of 83.9%. The light color parameters of the blue laser and fluorescent thin film combination were tested using a light source photochromic and electroluminescent integrated testing system. Because the light-emitting layer contains cyan, green, yellow, orange and red fluorescent materials, the white light emitted by the device has a high color rendering index (Ra) of 97.8 and a low color temperature of 4450K (see Table 1 for light color parameters). This fully meets the lighting requirements of places such as museums that have extremely high requirements for color rendering index and color temperature.

[0223] As can be seen, the fluorescent film prepared by the non-sintering technology provided in Example 20 can be applied to laser lighting for occasions with high requirements for light color index, such as museums and cinemas.

[0224] Example 21

[0225] The fluorescent film obtained in Example 20 was encapsulated with a blue laser diode with an emission wavelength of 450 nm, with the light-emitting layer in the fluorescent film placed opposite to the blue laser diode. Figure 4 A structural diagram of the laser illumination device obtained in Example 21 is provided. Reference numerals: 001: fluorescent thin film; 021: light-emitting layer; 022: aluminum substrate; 100: blue laser diode; 200: white light obtained by mixing unabsorbed blue light with light emitted from the light-emitting layer; 201: reflected light from the aluminum substrate after unabsorbed blue light penetrates the light-emitting layer; 300: blue light emitted by the blue laser diode and incident on the light-emitting layer; 301: blue light penetrating the light-emitting layer.

[0226] Table 1. Data on the light color parameters of laser illumination devices

[0227] Serial Number Quantum efficiency (%) Color temperature (K) Color rendering index (Ra) Comparative Example 1 85.2 7733 62.2 Comparative Example 2 62.7 / / Comparative Example 3 71.1 5019 86.6 Comparative Example 4 84.9 5739 83.9 Comparative Example 5 84.4 4032 72.7 Comparative Example 6 70.3 5001 88.9 Example 1 84.2 3895 91.1 Example 2 84.1 3754 90.8 Example 3 84.5 3422 90.5 Example 4 85.2 3317 90.2 Example 5 83.9 3101 90.1 Example 6 83.8 3650 92.3 Example 7 84.4 3736 92.5 Example 8 85.1 3839 92.2 Example 9 83.8 4002 92.8 Example 10 82.9 3660 92.1 Example 11 83.7 3556 91.6 Example 12 82.2 4005 95.3 Example 13 83.1 3992 94.6 Example 14 84.8 4118 96.6 Example 15 85.1 4001 95.7 Example 16 83.2 4216 94.8 Example 17 83.3 3827 93.7 Example 18 84.2 4359 96.6 Example 19 83.7 4333 95.2 Example 20 83.9 4450 97.8

[0228] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

Claims

1. A fluorescent thin film, characterized in that: The fluorescent film comprises a metallic aluminum substrate with a visible light reflectance greater than 95% and a light-emitting layer on the metallic aluminum substrate; the thickness of the metallic aluminum substrate is 0.5~2mm; the thickness of the light-emitting layer is 100~500μm; the light-emitting layer is obtained by a non-sintering technique after uniformly mixing fluorescent materials and fixatives under air atmosphere at a temperature of 40~80℃; the fluorescent materials contained in the light-emitting layer are two or more of cyan fluorescent materials, green fluorescent materials, yellow fluorescent materials, orange fluorescent materials and red fluorescent materials, of which yellow fluorescent materials and red fluorescent materials are essential; the white light produced by the light-emitting layer under blue 450nm laser excitation has a color temperature range of 3000K~4500K and a color rendering index of 90~98; wherein, by mass percentage, the chemical composition of the fixative is: aluminum dihydrogen phosphate 30%~60%, alumina sol 20%~40%, methanol 20%~30%.

2. The fluorescent thin film as described in claim 1, characterized in that: The thickness of the aluminum plate substrate is 1 mm, and the thickness of the light-emitting layer is 300 μm.

3. A fluorescent thin film as described in claim 1, characterized in that: The chemical composition of the cyan fluorescent material in the luminescent layer is BaSi2O2N2:Eu; the chemical composition of the green fluorescent material in the luminescent layer is β-SiAlON:Eu; and the chemical composition of the yellow fluorescent material in the luminescent layer is Y3Al5O2. 12 Ce; The chemical composition of the orange fluorescent material in the luminescent layer is: Y4Ba2[Si9ON] 16 O:Eu; The chemical composition of the red fluorescent material in the fluorescent material contained in the light-emitting layer is: CaAlSiN3:Eu.

4. A method for preparing a fluorescent thin film according to any one of claims 1 to 3, characterized in that, Includes the following steps: a) Weigh out two or more of the following fluorescent materials in proportion: cyan, green, yellow, orange, and red. Yellow and red fluorescent materials are required. Mix the fluorescent materials thoroughly to obtain mixed fluorescent material X. b) Mix the mixed fluorescent material X obtained in step a) with the fixative in a certain proportion to obtain slurry Z; c) Coat the slurry Z obtained in step b) onto one side of the aluminum plate substrate with a coating thickness of 100~500μm. After drying at 40~80℃ in air for 1h, a fluorescent film can be obtained.

5. The preparation method according to claim 4, characterized in that: In step a), the mass ratio of cyan fluorescent material, green fluorescent material, yellow fluorescent material, orange fluorescent material and red fluorescent material is: (0~25):(0~25):(40~80):(0~25):(15~25).

6. The preparation method according to claim 4, characterized in that: In step b), the mass ratio of the mixed fluorescent material X to the fixative is 1:0.5~0.

7.

7. The preparation method according to claim 4, characterized in that: In step c), the coating method is either casting or blade coating.

8. A laser illumination device, characterized in that: The laser illumination device comprises a blue laser diode and a fluorescent thin film as described in any one of claims 1 to 3 or a fluorescent thin film prepared by any one of claims 4 to 7.

9. The laser illumination device as described in claim 8, characterized in that: The laser illumination device has a reflective structure, and the light-emitting port of the blue laser diode is placed opposite to the light-emitting layer in the fluorescent thin film.

Images