Zinc-sensitized double-bond rare earth europium light conversion agent and modified POE light conversion adhesive film thereof

Abstract

The invention belongs to the technical field of rare earth complexes, and relates to a zinc-sensitized double-bond rare earth europium light conversion agent and a modified POE light conversion adhesive film thereof. The invention discloses a zinc-sensitized double-bond rare earth europium light conversion agent, which comprises a zinc-sensitized double-bond rare earth europium complex, the complex takes rare earth europium as a central ion, a part of europium ions are replaced by zinc ions, and 2-thiophenoyl trifluoroacetone TTA, acrylic acid AA and triphenylphosphine oxide TPPO are taken as ligands; the zinc-sensitized double-bond rare earth europium complex has reactive double bonds. The invention further discloses a modified POE light conversion adhesive film containing the zinc-sensitized double-bond rare earth europium light conversion agent. Zinc ions are introduced into the zinc-sensitized double-bond rare earth europium light conversion agent, energy level matching of the complex is optimized, effective transfer of energy from a ligand to europium ions is promoted, and the fluorescence intensity and luminous efficiency of the complex are remarkably improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of rare earth complexes, and relates to a zinc-sensitized double-bond rare earth europium light conversion agent and a modified POE light conversion film thereof. Background Art

[0002] Although rare earth europium complexes have excellent luminescent properties, they still face some challenges in practical applications, such as the need to improve luminescence efficiency, insufficient stability, and high cost. Doping with base metal ions can effectively solve these problems. The doping of base metal ions can enhance the fluorescence intensity of europium complexes, thereby improving their luminescence efficiency.

[0003] Among many base metals, zinc (Zn) can be one of the ideal doping metals for rare earth europium complexes due to its unique chemical and physical properties. Research shows that the doping of ions can optimize the energy level matching of complexes and promote the effective transfer of energy from ligands to Eu3+. Summary of the Invention

[0004] The object of the present invention is to address the above-mentioned problems existing in the prior art, and propose a zinc-sensitized double-bond rare earth europium light conversion agent with reactive double bonds, which uses europium ions and zinc ions as central ions, and 2-thiophenecarbonyltrifluoroacetone (TTA), acrylic acid (AA), and triphenylphosphine oxide (TPPO) as ligands.

[0005] One object of the present invention is achieved by the following technical solutions:

[0006] A zinc-sensitized double-bond rare earth europium light conversion agent, comprising a zinc-sensitized double-bond rare earth europium complex, which uses rare earth europium as the central ion, and part of the europium ions are replaced by zinc ions, and uses 2-thiophenecarbonyltrifluoroacetone (TTA), acrylic acid (AA), and triphenylphosphine oxide (TPPO) as ligands;

[0007] The zinc-sensitized double-bond rare earth europium complex has reactive double bonds.

[0008] Preferably, the molar ratio of the europium ions to the zinc ions is (0.5 - 9):(9.5 - 1).

[0009] More preferably, the molar ratio of the europium ions to the zinc ions is 9:1.

[0010] Preferably, the molar ratio of 2-thiophenecarbonyltrifluoroacetone (TTA), acrylic acid (AA), and triphenylphosphine oxide (TPPO) is (1.1 - 5):1:(1.1 - 5).

[0011] More preferably, the molar ratio of 2-thiophenecarbonyltrifluoroacetone (TTA), acrylic acid (AA), and triphenylphosphine oxide (TPPO) is (1.8 - 2.2):1:(1.8 - 2.2).

[0012] More preferably, the molar ratio of 2 - thenoyltrifluoroacetone (TTA), acrylic acid (AA), and triphenylphosphine oxide (TPPO) is 2:1:2.

[0013] Preferably, the molar ratio of the total metal ions of europium ions and zinc ions to 2 - thenoyltrifluoroacetone (TTA), acrylic acid (AA), and triphenylphosphine oxide (TPPO) is (0.8 - 1.2):(1.1 - 5):1:(1.1 - 5).

[0014] More preferably, the molar ratio of the total metal ions of europium ions and zinc ions to 2 - thenoyltrifluoroacetone (TTA), acrylic acid (AA), and triphenylphosphine oxide (TPPO) is 1:(1.8 - 2.2):1:(1.8 - 2.2).

[0015] Preferably, the zinc - sensitized double - bond rare - earth europium complex uses europium ions and zinc ions as central ions and 2 - thenoyltrifluoroacetone (TTA), acrylic acid (AA), and triphenylphosphine oxide (TPPO) as ligands;

[0016] The molar ratio of europium ions to zinc ions is 9:1.

[0017] Preferably, the structural formula of the zinc - sensitized double - bond rare - earth europium complex is as follows in formula (1):

[0018]

[0019] Preferably, the preparation method of the zinc - sensitized double - bond rare - earth europium light - conversion agent includes:

[0020] After adding TTA, AA, and TPPO to the mixed alcohol solution of ZnCl2 and EuCl3, carry out a constant - temperature water - bath stirring and reflux reaction at 50 - 90 °C for 1 - 12 h, adjust the pH to 6 - 7 until precipitation occurs, then let it stand, filter, and wash to obtain the zinc - sensitized double - bond rare - earth europium light - conversion agent.

[0021] More preferably, the molar ratio of Zn 2+ , Eu 3+ , TTA, AA, and TPPO is 0.1:0.9:2:1:2.

[0022] More preferably, the mixed alcohol solution of ZnCl2 and EuCl3 is prepared by mixing the ZnCl2 alcohol solution and the EuCl3 alcohol solution;

[0023] The ZnCl2 alcohol solution is prepared by dissolving ZnO in hydrochloric acid solution and then mixing it with ethanol solution;

[0024] The EuCl3 alcohol solution is prepared by dissolving Eu2O3 in hydrochloric acid solution and then mixing it with ethanol solution.

[0025] Preferably, the zinc-sensitized double-bonded rare earth europium photoluminescent agent has a fluorescence quantum yield > 96% under 380 nm excitation.

[0026] More preferably, the zinc-sensitized double-bonded rare earth europium photoluminescent agent has a fluorescence quantum yield > 99% under 380 nm excitation.

[0027] The second object of the present invention is achieved by the following technical solutions:

[0028] A modified POE photoluminescent film, which comprises 0.1 - 5 wt% of a zinc-sensitized double-bonded rare earth europium photoluminescent agent.

[0029] Preferably, the addition amount of the zinc-sensitized double-bonded rare earth europium photoluminescent agent in the modified POE photoluminescent film is 0.25 - 1.0 wt%.

[0030] More preferably, the addition amount of the zinc-sensitized double-bonded rare earth europium photoluminescent agent in the modified POE photoluminescent film is 0.75 wt%.

[0031] Preferably, the preparation method of the modified POE photoluminescent film includes: dissolving POE and the zinc-sensitized double-bonded rare earth europium photoluminescent agent in an organic solvent, heating and stirring, and then coating to form a film to obtain the modified POE photoluminescent film.

[0032] Preferably, the mass ratio of POE to the zinc-sensitized double-bonded rare earth europium photoluminescent agent is (99.75 - 99):(0.25 - 1.0).

[0033] Preferably, the modified POE photoluminescent film further comprises an auxiliary agent.

[0034] More preferably, the auxiliary agent includes one or more of an antioxidant, an ultraviolet absorber, an antistatic agent, a surfactant, a light stabilizer, and a heat stabilizer.

[0035] Preferably, the film thickness of the modified POE photoluminescent film is 10 - 1000 μm.

[0036] Preferably, the light transmittance of the modified POE photoluminescent film > 91%.

[0037] Preferably, the water vapor transmission rate of the modified POE photoluminescent film < 10%.

[0038] The third object of the present invention is achieved by the following technical solutions:

[0039] A crystalline silicon cell, which comprises a modified POE photoluminescent film.

[0040] Compared with the prior art, the present invention has the following beneficial effects:

[0041] 1. The zinc-sensitized double-bond rare-earth europium light converter of the present invention uses europium ions and zinc ions as central ions, and 2-thenoyltrifluoroacetone (TTA), acrylic acid (AA), and triphenylphosphine oxide (TPPO) as ligands, and has reactive double bonds.

[0042] 2. Introducing zinc ions into the zinc-sensitized double-bond rare-earth europium light converter of the present invention improves the thermal stability and chemical stability of the complex, enabling it to maintain good performance even in complex environments such as high temperature, high humidity, and light.

[0043] 3. Introducing zinc ions into the zinc-sensitized double-bond rare-earth europium light converter of the present invention optimizes the energy level matching of the complex, promotes the effective transfer of energy from the ligand to the europium ion, and significantly improves the fluorescence intensity and luminescence efficiency of the complex.

[0044] 4. The fluorescence quantum yield of the zinc-sensitized double-bond rare-earth europium light converter of the present invention exceeds 99% under the optimal excitation of 380 nm.

[0045] 5. The modified POE light conversion film made of the zinc-sensitized double-bond rare-earth europium light converter of the present invention has a high light transmittance, which is beneficial to expanding its application in crystalline silicon cells. Brief Description of the Drawings

[0046] Figure 1 It is the infrared spectra of the zinc-sensitized double-bond rare-earth europium complexes Zn-ETAT of Examples 1-3 of the present invention and ETAT of Comparative Example 1.

[0047] Figure 2 It is the XPS diagrams of the zinc-sensitized double-bond rare-earth europium complexes Zn-ETAT of Examples 1-3 of the present invention and ETAT of Comparative Example 1.

[0048] Figure 3 It is the 3D fluorescence spectra (a, b, c, d), PL diagrams (a1, b1, c1, d1), and QY diagrams (a2, b2, c2, d2) of the zinc-sensitized double-bond rare-earth europium complexes Zn-ETAT of Examples 1-3 of the present invention and ETAT of Comparative Example 1.

[0049] Figure 4 It is the absorption intensity diagrams of the zinc-sensitized double-bond rare-earth europium complexes of Example 1 of the present invention and Comparative Example 2 in the ultraviolet region (a) and the red light region (b); the absorption intensity diagrams of the zinc-sensitized double-bond rare-earth europium complexes of Example 1 and Comparative Example 3 in the ultraviolet region (c) and the red light region (d).

[0050] Figure 5 It is the absorption intensity diagrams of the zinc-sensitized double-bond rare-earth europium complexes of Example 1 of the present invention and Comparative Example 4 in the ultraviolet region (a) and the red light region (b).

[0051] Figure 6This is the PL diagram of the modified POE light conversion film for Application Examples 1-4 and Application Comparative Example 4 of the present invention.

[0052] Figure 7 This is the water vapor transmission rate (a) and water contact angle (b) of the modified POE light conversion film for Application Examples 1-4 and Application Comparative Examples 1-4 of the present invention.

[0053] Figure 8 This is the TG / DTG curve (a) of Zn-ETAT (1:9) in Example 1 of the present invention, and the TG (b), DTG (c) and MCC curve (d) of the modified POE light conversion film and pure POE film for Application Examples 1-4.

[0054] Figure 9 This is the transmittance comparison diagram of the modified POE light conversion film for Application Comparative Example 5 and Application Example 4 of the present invention.

[0055] Figure 10 This is the summary diagram (f) of the IV and efficiency improvement of the Si-sc cell before and after encapsulation with the modified POE light conversion film (b-e) and pure POE film (a) for Application Examples 1-4 of the present invention. Detailed Description of the Invention

[0056] The technical solutions of the present invention will be further described and illustrated below through specific examples. It should be understood that the specific examples described herein are only used to help understand the present invention and are not used for specific limitations of the present invention.

[0057] Unless otherwise specified, the raw materials used in the embodiments of the present invention are all commonly used raw materials in the art, and the methods used in the embodiments are all conventional methods in the art.

[0058] Example 1

[0059] Weigh 0.01 mol of ZnO and 0.01 mol of Eu2O3 respectively and dissolve them in 2M hydrochloric acid solution, and make up the volume to 100 mL with ethanol solution to obtain 0.1 mol / L ZnCl2 solution and 0.1 mol / L EuCl3 solution. Weigh 0.01 mol of AA, TPPO, and TTA respectively and mix them with ethanol solution to prepare 0.1 mol / L ligand solution. According to Zn 2+ 、Eu 3+, with a molar ratio of TTA, AA, TPPO of 0.1:0.9:2:1:2, weigh 0.1 mol / L ZnCl₂ solution and EuCl₃ solution into a round-bottom flask. While stirring, gradually add 20 ml of TTA solution, 10 ml of AA solution, and 20 ml of TPPO solution drop by drop, then add 50 ml of ethanol solution. Stir and reflux in a 70 °C constant temperature water bath for 4 h. Adjust the pH value to 6 - 7 until precipitation occurs, let it stand for 24 h, filter, wash, dry to constant weight to obtain zinc-sensitized double-bond rare-earth europium complex, denoted as Zn-ETAT(1:9).

[0060] In this example, the structural formula of the zinc-sensitized double-bond rare-earth europium complex is Zn-Eu(TAA)₂(AA)(TPPO)₂.

[0061] Example 2

[0062] Weigh 0.01 mol ZnO and 0.01 mol Eu₂O₃ and dissolve them in 2M hydrochloric acid solution, add ethanol solution to make up the volume to 100 mL to obtain 0.1 mol / L ZnCl₂ solution and 0.1 mol / L EuCl₃ solution. Weigh 0.01 mol of AA, TPPO, and TTA respectively and mix them with ethanol solution to prepare 0.1 mol / L ligand solution. According to the molar ratio of Zn 2+ 、Eu 3+ 、TTA, AA, TPPO of 0.5:0.5:2:1:2, weigh 0.1 mol / L ZnCl₂ solution and EuCl₃ solution into a round-bottom flask. While stirring, gradually add 20 ml of TTA solution, 10 ml of AA solution, and 20 ml of TPPO solution drop by drop, then add 50 ml of ethanol solution. Stir and reflux in a 70 °C constant temperature water bath for 4 h. Adjust the pH value to 6 - 7 until precipitation occurs, let it stand for 24 h, filter, wash, dry to constant weight to obtain zinc-sensitized double-bond rare-earth europium complex, denoted as Zn-ETAT(5:5).

[0063] Example 3

[0064] Weigh 0.01 mol ZnO and 0.01 mol Eu₂O₃ and dissolve them in 2M hydrochloric acid solution, add ethanol solution to make up the volume to 100 mL to obtain 0.1 mol / L ZnCl₂ solution and 0.1 mol / L EuCl₃ solution. Weigh 0.01 mol of AA, TPPO, and TTA respectively and mix them with ethanol solution to prepare 0.1 mol / L ligand solution. According to the molar ratio of Zn 2+ 、Eu 3+、The molar ratio of TTA, AA, TPPO is 0.9:0.1:2:1:2. Weigh 0.1 mol / L ZnCl2 solution and EuCl3 solution into a round-bottom flask. While stirring, gradually add 20 ml of TTA solution, 10 ml of AA solution, and 20 ml of TPPO solution. Then add 50 ml of ethanol solution. Stir and reflux in a 70 °C constant temperature water bath for 4 h. Adjust the pH value to 6 - 7 until precipitation occurs. Let it stand for 24 h, filter, wash, dry to constant weight to obtain zinc-sensitized double-bond rare-earth europium complex, denoted as Zn-ETAT(9:1).

[0065] Example 4

[0066] Weigh ZnCl2 and EuCl3 respectively and add ethanol solution to obtain 0.1 mol / L ZnCl2 solution and 0.1 mol / L EuCl3 solution. Weigh 0.01 mol of AA, TPPO, and TTA respectively and mix with ethanol solution to prepare 0.1 mol / L ligand solution. According to the molar ratio of Zn 2+ 、Eu 3+ 、TTA, AA, TPPO being 0.05:0.95:2:1:2, weigh 0.1 mol / L ZnCl2 solution and EuCl3 solution into a round-bottom flask. While stirring, gradually add 20 ml of TTA solution, 10 ml of AA solution, and 20 ml of TPPO solution. Then add 50 ml of ethanol solution. Stir and reflux in a 70 °C constant temperature water bath for 4 h. Adjust the pH value to 6 - 7 until precipitation occurs. Let it stand for 24 h, filter, wash, dry to constant weight to obtain zinc-sensitized double-bond rare-earth europium complex, denoted as Zn-ETAT(0.5:9.5).

[0067] In this example, the fluorescence quantum yield of the zinc-sensitized double-bond rare-earth europium complex obtained at the optimal excitation wavelength of 380 nm is 70.62%.

[0068] Comparative Example 1

[0069] Weigh 0.01 mol Eu2O3 and dissolve it in 2 M hydrochloric acid solution. Add ethanol solution to make the volume up to 100 mL to obtain 0.1 mol / L EuCl3 solution. Weigh 0.01 mol of AA, TPPO, and TTA respectively and mix with ethanol solution to prepare 0.1 mol / L ligand solution. Mix according to the molar ratio of Eu 3+ 、TTA, AA, TPPO being 1:2:1:2. Stir and reflux in a 70 °C constant temperature water bath for 4 h. Adjust the pH value to 6 - 7 until precipitation occurs. Let it stand for 24 h, filter, wash, dry to constant weight to obtain double-bond rare-earth europium complex, denoted as ETAT.

[0070] According to Figure 1From the infrared spectra, it can be seen that the infrared positions of ETAT and Zn-ETAT(1:9), Zn-ETAT(5:5), and Zn-ETAT(9:1) are basically the same. However, after doping with Zn, the C=O double bond shifts from 1610 cm -1 to 1641 cm -1 .

[0071] According to Figure 2 the XPS spectra, compared with Zn-ETAT, the XPS peak position of Eu in ETAT shifts 0.4 eV to the left. This is because when Zn is doped into the complex, charge transfer may occur. At the same time, the elemental ratios of Zn and Eu are accurately determined, and the measurement results are basically consistent with the addition amounts.

[0072] According to Figure 3 the 3D fluorescence spectra, PL spectra, and QY spectra, it can be seen that the emission characteristic peaks do not change, indicating that after Zn doping, the doped ions and rare earth ions coexist in the form of "mixed ligands"; the optimal excitation wavelength for all four is 380 nm, and the fluorescence quantum yields obtained from the optimal excitation are 80.53%, 99.17%, 66.39%, and 50.06% respectively.

[0073] Comparative Example 2

[0074] Weigh 0.01 mol of ZnO and 0.01 mol of Eu2O3 and dissolve them in 2 M hydrochloric acid solution. Add ethanol solution to make the volume up to 100 mL to obtain 0.1 mol / L ZnCl2 solution and 0.1 mol / L EuCl3 solution. Weigh 0.01 mol of TPPO and TTA respectively and mix them with ethanol solution to prepare 0.1 mol / L ligand solution. Mix them according to the molar ratio of Zn 2+ , Eu 3+ , TTA, and TPPO of 0.1:0.9:3:2. Stir and reflux the mixture in a 70°C constant temperature water bath for 4 h. Adjust the pH value to 6 - 7 until precipitation occurs. Let it stand for 24 h, filter, wash, dry, and weigh to obtain the zinc-sensitized double-bond rare earth europium complex, denoted as Zn-Eu(TAA)3(TPPO)2.

[0075] From Figure 4 (a, b), it can be seen that the absorption intensity of Zn-Eu(TAA)3(TPPO)2 in this comparative example in the ultraviolet region is 3850 a.u., and the emission intensity in the red region is 5054 a.u.; while the absorption intensity of Zn-Eu(TAA)2(AA)(TPPO)2 in Example 1 in the ultraviolet region increases to 9256 a.u., and the emission intensity in the red region is 9370 a.u. The ultraviolet absorption intensity and infrared emission intensity of Zn-Eu(TAA)3(TPPO)2 in this comparative example are both lower than those in Example 1.

[0076] Comparative Example 3

[0077] Weigh 0.01 mol of ZnO and 0.01 mol of Eu2O3 respectively and dissolve them in 2 M hydrochloric acid solution. Add ethanol solution to make the volume constant at 100 mL to obtain 0.1 mol / L ZnCl2 solution and 0.1 mol / L EuCl3 solution. Weigh 0.01 mol of AA and TPPO respectively and mix them with ethanol solution to prepare 0.1 mol / L ligand solution. According to the molar ratio of Zn 2+ , Eu 3+ , AA, and TPPO of 0.1:0.9:1:6, mix them, stir and reflux in a constant temperature water bath at 70 °C for 4 h, adjust the pH value to 6 - 7 until precipitation occurs, let it stand for 24 h, filter, wash, dry and weigh to obtain zinc-sensitized double-bond rare earth europium complex, denoted as Zn-Eu(AA)(TPPO)6.

[0078] As can be seen from Figure 4 (c, d), the absorption intensity of Zn-Eu(AA)(TPPO)6 in this comparative example in the ultraviolet region is 387 a.u., and the emission intensity in the red light is 486.9 a.u.; while the absorption intensity of Zn-Eu(TAA)2(AA)(TPPO)2 in Example 1 in the ultraviolet region is increased to 9256 a.u., and the emission intensity in the red light is 9370 a.u. The ultraviolet absorption intensity and infrared emission intensity of Zn-Eu(AA)(TPPO)6 in this comparative example are both lower than those in Example 1.

[0079] Comparative Example 4

[0080] Weigh 0.01 mol of ZnO and 0.01 mol of Eu2O3 respectively and dissolve them in 2 M hydrochloric acid solution. Add ethanol solution to make the volume constant at 100 mL to obtain 0.1 mol / L ZnCl2 solution and 0.1 mol / L EuCl3 solution. Weigh 0.01 mol of Phen and TTA respectively and mix them with ethanol solution to prepare 0.1 mol / L ligand solution. According to the molar ratio of Zn 2+ , Eu 3+ , TTA, and Phen of 0.1:0.9:3:2, mix them, stir and reflux in a constant temperature water bath at 70 °C for 4 h, adjust the pH value to 6 - 7 until precipitation occurs, let it stand for 24 h, filter, wash, dry and weigh to obtain zinc-sensitized double-bond rare earth europium complex, denoted as Zn-Eu(TAA)3(Phen)2.

[0081] As can be seen from Figure 5It can be seen that the absorption intensity of Zn-Eu(TAA)3(Phen)2 in this comparative example in the ultraviolet region is 4150 a.u., and the emission intensity in the red light is 4154 a.u. The ultraviolet absorption intensity and infrared emission intensity of Zn-Eu(TAA)3(Phen)2 in this comparative example are both lower than those of Zn-Eu(TAA)2(AA)(TPPO)2 in Example 1.

[0082] Application Example 1

[0083] Dissolve 0.005 g of the zinc-sensitized double-bond rare-earth europium complex Zn-ETAT(1:9) in Example 1 and 2 g of POE in toluene, heat and stir at 60 °C for 2 h, and then transfer to a coater to obtain a modified POE light conversion film with a film thickness of 100 μm, denoted as POE / 0.25% Zn-ETAT.

[0084] Application Examples 2-4

[0085] Dissolve 0.01 g, 0.015 g, and 0.02 g of the zinc-sensitized double-bond rare-earth europium complex Zn-ETAT(1:9) in Example 1 and 2 g of POE in toluene, heat and stir at 60 °C for 2 h, and then transfer to a coater to obtain a modified POE light conversion film with a film thickness of 100 μm; denoted as POE / 0.5% Zn-ETAT, POE / 0.75% Zn-ETAT, and POE / 1.00% Zn-ETAT respectively.

[0086] Application Comparative Examples 1-4

[0087] Dissolve 0.005 g, 0.01 g, 0.015 g, and 0.02 g of ETAT in Comparative Example 1 and 2 g of POE in toluene, heat and stir at 60 °C for 2 h, and then transfer to a coater to obtain a modified POE light conversion film with a film thickness of 100 μm, denoted as POE / 0.25% ETAT, POE / 0.5% ETAT, POE / 0.75% ETAT, and POE / 1.00% ETAT respectively.

[0088] Figure 6 It is the PL diagram of the modified POE light conversion films of Application Examples 1-4 and Application Comparative Example 4. It can be seen that the absorption range of POE / (0.25%, 0.5%, 0.75%, 1.00%) Zn-ETAT at 300-400 nm is higher than that of POE / 1.00% ETAT.

[0089] Figure 7For the water vapor transmission rate (a) and water contact angle (b) of the modified POE light conversion films of Application Examples 1 to 4 and Application Comparative Examples 1 to 4, it can be seen that when the addition amount is 1 wt%, the water vapor transmission rate of the POE light conversion film in Application Comparative Example 4 is lower than that of the POE light conversion film in Application Comparative Example 1. This is because Zn-ETAT undergoes a cross-linking reaction with the POE matrix through double bonds, forming more cross-linking points. These cross-linking points increase the cross-linking density of the material, making the structure of the material more dense, thereby reducing the water vapor transmission rate. As the addition amount of Zn-ETAT increases, the water contact angle of the POE light conversion film also increases, indicating that the addition of Zn can reduce the surface hydrophilicity of POE and improve the water resistance performance.

[0090] Figure 8 TG / DTG curves (a) of Zn-ETAT (1:9) in Example 1, and TG (b), DTG (c) and MCC curves (d) of the modified POE light conversion films of Application Examples 1 to 4 and the pure POE film. According to Figure 7 and Table 1, as the addition amount of Zn-ETAT (1:9) increases, T 5％ and T max temperature increases, and the residual carbon amount also increases.

[0091] Table 1. Performance table of pure POE film and modified POE light conversion film

[0092]

[0093] Application Comparative Example 5

[0094] The zinc-sensitized double-bond rare earth europium complex Zn-Eu(TTA)3(TPPO)2 of Comparative Example 2 was made into a film according to the steps of Application Example 4.

[0095] From Figure 9 it can be seen that in the range of 500 - 800 nm, the light transmittance of POE / 1.00% Zn-Eu(TTA)3(TPPO)2 is 91%, while the light transmittance of POE / 1.00% Zn-Eu(TTA)2(AA)(TPPO)2 in Application Example 4 is increased to 92%; it shows that under the combined action of TTA, AA, and TPPO, the light conversion agent cross-links with POE, having better light transmittance.

[0096] Application Example 5

[0097] The modified POE light conversion films of Application Examples 1 to 4 were used to encapsulate crystalline silicon cells.

[0098] Figure 10Summary diagrams of the IV and efficiency improvement of Si-sc solar cell wafers before and after encapsulation with the modified POE light conversion films (b - e) and pure POE (a) of Application Examples 1 - 4, and (f). It can be seen that Zn-ETAT converts ultraviolet light into visible light, increasing the number of photons, thereby increasing the short-circuit current density of the cell. At the same time, the film reduces the reflection on the cell surface and improves the light absorption efficiency, thereby increasing the fill factor of the cell.

[0099] In summary, introducing zinc ions into the zinc-sensitized double-bond rare earth europium light conversion agent of the present invention improves the thermal stability and chemical stability of the complex, enabling it to maintain good performance even in complex environments such as high temperature, high humidity, and light exposure. Introducing zinc ions also optimizes the energy level matching of the complex, promoting the effective transfer of energy from the ligand to Eu3+, and significantly increasing the fluorescence intensity and luminescence efficiency of the complex.

[0100] All aspects, embodiments, and features of the present invention should be considered illustrative in all respects and not limiting to the present invention. The scope of the present invention is only defined by the claims. Without departing from the spirit and scope of the claimed invention, those skilled in the art will understand other embodiments, modifications, and uses.

[0101] In the preparation method of the present invention, the order of each step is not limited to the listed order. For those of ordinary skill in the art, without creative efforts, the sequential changes of each step are also within the protection scope of the present invention. In addition, two or more steps or actions can be carried out simultaneously.

[0102] Finally, it should be noted that the specific embodiments described herein are merely illustrative of the present invention and not intended to limit the implementation manners of the present invention. Those skilled in the art of the present invention can make various modifications or supplements to the described specific embodiments or use similar methods for substitution. It is not necessary and impossible to list all implementation manners here. And these obvious changes or variations derived from the essence of the present invention still fall within the protection scope of the present invention. Interpreting them as any additional limitation is contrary to the spirit of the present invention.

Claims

1. A zinc-sensitized double-bond rare earth europium light conversion agent, characterized in that, It is a zinc-sensitized double-bond rare earth europium complex. In this complex, rare earth europium serves as the central ion, and some of the europium ions are replaced by zinc ions. 2-Thenoyltrifluoroacetone (TTA), acrylic acid (AA), and triphenylphosphine oxide (TPPO) are used as ligands. The zinc-sensitized double-bond rare earth europium complex has reactive double bonds.

2. The zinc-sensitized double-bond rare earth europium light conversion agent according to claim 1, wherein The molar ratio of the europium ions to the zinc ions is (0.5 - 9):(9.5 - 1).

3. The zinc-sensitized double-bond rare-earth europium light conversion agent according to claim 1, characterized in that, The molar ratio of 2-thenoyltrifluoroacetone (TTA), acrylic acid (AA), and triphenylphosphine oxide (TPPO) is (1.1 - 5):1:(1.1 - 5).

4. The zinc-sensitized double-bond rare earth europium photoluminescent agent according to claim 1, characterized in that, The fluorescence quantum yield of the zinc-sensitized double-bond rare earth europium light conversion agent is > 96% under 380 nm excitation.

5. A modified POE light conversion film, which comprises 0.1 - 5 wt% of the zinc-sensitized double-bond rare earth europium light conversion agent according to any one of claims 1 - 4.

6. The modified POE light conversion film according to claim 5, wherein The addition amount of the zinc-sensitized double-bond rare earth europium light conversion agent in the modified POE light conversion film is 0.25 - 1.0 wt%.

7. The modified POE light conversion film according to claim 5, wherein The preparation method of the modified POE light conversion film includes: dissolving POE and the zinc-sensitized double-bond rare earth europium light conversion agent in an organic solvent, heating and stirring, and then coating to form a film to obtain the modified POE light conversion film.

8. The modified POE light conversion film according to claim 5, characterized in that, The modified POE light conversion film further includes additives.

9. The modified POE light conversion film according to claim 5, wherein The light transmittance of the modified POE light conversion film is > 91%; the water vapor transmission rate of the modified POE light conversion film is < 10%.

10. A crystalline silicon cell, which comprises the modified POE light conversion film according to any one of claims 5 - 9.

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