A blue light proof indoor organic photovoltaic device structure and a preparation method thereof

Abstract

The present application relates to a kind of indoor organic photovoltaic device structures of blue light prevention and preparation method thereof, including substrate, anode, hole transport layer, active layer, electron transport layer and cathode sequentially grown from bottom to top;PC is added in active layer 71 BM.The present application selects PC 71 BM as the third element material, balances the light absorption of IOPV to LED spectrum, reduces the proportion of blue light in transmission spectrum while improving the performance of the device.

Description

Technical Field

[0001] This invention relates to a structure and preparation method of an indoor organic photovoltaic device for blue light protection, belonging to the technical field of organic photovoltaic device preparation. Background Technology

[0002] With the development of Internet of Things (IoT) technology, an increasing number of low-power electronic products are being integrated into the IoT. Statistics show that approximately 50 billion IoT devices were in use in 2020, most of which are located indoors. Faced with such a large number of off-grid devices, relying on periodically replacing dry-cell batteries for power is neither environmentally friendly nor intelligent. Indoor organic photovoltaics (IOPV) is a strong candidate for powering these off-grid devices. It can continuously power these low-power electronic devices by collecting light energy from indoor lighting, and its lightweight and flexible characteristics allow for integration into many devices. Currently, research on indoor organic photovoltaics is progressing rapidly, with single-junction efficiency exceeding 31%. However, indoor light intensity is only one-thousandth of sunlight intensity, and for power output targets in the hundreds of microwatts range, the only way to achieve this is by increasing the battery area. Whether large-area IOPV will affect human eye health requires further research.

[0003] The high efficiency of existing IOPV is mainly achieved by absorbing red light in the 600-700nm range of the LED spectrum. This greatly increases the proportion of residual blue light in the spectrum, which greatly increases the risk of blue light damage to the human eye. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a structure for an indoor organic photovoltaic device that blocks blue light;

[0005] This invention selects PC, which has a strong absorption effect on blue light. 71 BM, as a tertiary material, balances the light absorption of the LED spectrum by IOPV and reduces the proportion of blue light in the transmission spectrum.

[0006] The present invention also provides a method for preparing the above-mentioned blue light blocking indoor organic photovoltaic device structure.

[0007] Terminology Explanation:

[0008] PC 71 BM is a polymer photovoltaic material with the molecular formula [6,6]-Phenyl-C71-butyric acidmethyl ester, which is mainly used as the acceptor material for organic solar cells.

[0009] PM6 is a polymer photovoltaic material with the molecular formula Poly[(2,6-(4,8-bis(5-(2-ethylhexyl-3-fluoro)thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'-c:4',5'-c']dithiophene-4,8-dione)], primarily used as a donor material in organic solar cells.

[0010] PBDB-T is a polymer photovoltaic material with the molecular formula Poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'-c:4',5'-c']dithiophene-4,8-dione)], primarily used as a donor material in organic solar cells.

[0011] PTB7-Th is a polymer photovoltaic material with the molecular formula Poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b']dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl)], mainly used as a donor material for organic solar cells.

[0012] J52 is a polymer photovoltaic material with the molecular formula Poly[[5,6-difluoro-2-(2-hexyldecyl)-2H-benzotriazole-4,7-diyl]-2,5-thiophenediyl[4,8-bis[5-(2-ethylhexyl)-2-thienyl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl]-2,5-thiophenediyl]. It is mainly used as a donor material for organic solar cells.

[0013] Y6 is a polymer photovoltaic material with the molecular formula 2,2'-((2Z,2'Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2",3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile, primarily used as the acceptor material in organic solar cells.

[0014] BTP-eC9 is a polymer photovoltaic material with the molecular formula 2,2'-[[12,13-Bis(2-butyloctyl)-12,13-dihydro-3,9-dinonylbisthieno[2”,3”:4',5']thieno[2',3':4,5]pyrrolo[3,2-e:2',3'-g][2,1,3]benzothiadiazole-2,10-diyl]bis[methylidyne(5,6-chloro-3-oxo-1H-indene-2,1(3H)-diylidene)]]bis[propanedinitrile]. It is mainly used as the acceptor material for organic solar cells.

[0015] ITIC is a polymer photovoltaic material with the molecular formula 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene, primarily used as the acceptor material in organic solar cells.

[0016] BTA3 is a polymer photovoltaic material with the molecular formula 2,2'-((5Z,5'Z)-5,5'-((7,7'-(4,4,9,9-tetrakis(4-hexylphenyl)-4,9-dihydro-s-indaceno[1,2-b:5,6-b']dithiophene-2,7-diyl)bis(2-octyl-2H-benzo[d][1,2,3]triazole-7,4-diyl))bis(methanylylidene))bis(3-ethyl-4-oxothiazolidine-5,2-diylidene))dimalononitrile, primarily used as the acceptor material in organic solar cells.

[0017] IEICO-4F is a polymer photovoltaic material with the molecular formula 2,2'-((2Z,2'Z)-(((4,4,9,9-tetrakis(4-hexylphenyl)-4,9-dihydro-sindaceno[1,2-b:5,6-b']dithiophene-2,7-diyl)bis(4-((2-ethylhexyl)oxy)thiophene-5,2-diyl))bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile, primarily used as the acceptor material in organic solar cells.

[0018] IT-M is a polymer photovoltaic material with the molecular formula 3,9-bis(2-methylene-((3-(1,1-dicyanomethylene)-6 / 7-methyl)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene, primarily used as the acceptor material in organic solar cells.

[0019] PEDOT:PSS is a polymer photovoltaic material with the molecular formula Poly(3,4-ethylenedioxythiophene):Poly(styrene sulfonate). It is mainly used as a hole transport layer material in organic solar cells.

[0020] PDIN is a polymer photovoltaic material with the molecular formula N,N'-Bis[3-(dimethylamino)propyl]perylene-3,4,9,10-tetracarboxylic diimide. It is mainly used as an electron transport layer material in organic solar cells.

[0021] UV: UV irradiation treatment cleans the ITO surface and optimizes its work function.

[0022] The technical solution of this invention is as follows:

[0023] A blue light blocking indoor organic photovoltaic device structure includes a substrate, an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode, grown sequentially from bottom to top; PC is added to the active layer. 71 BM.

[0024] According to a preferred embodiment of the present invention, the active layer is made of a receptor, PC. 71 The mass ratio of BM to receptor is 0-30%.

[0025] According to a preferred embodiment of the present invention, the acceptor is any one of six binary material systems: PM6:Y6, PM6:BTP-eC9, PBDB-T:ITIC, PBDB-T:BTA3, PTB7-Th:IEICO-4F, and J52:IT-M.

[0026] According to preferred embodiments of the present invention, the mass ratio of PM6 to Y6 in PM6:Y6 is 1:1.2; the mass ratio of PM6 to BTP-eC9 in PM6:BTP-eC9 is 1:1.2; the mass ratio of PBDB-T to ITIC in PBDB-T:ITIC is 1:1; the mass ratio of PBDB-T to BTA3 in PBDB-T:BTA3 is 1:1; the mass ratio of PTB7-Th to IEICO-4F in PTB7-Th:IEICO-4F is 1:1.5; and the mass ratio of J52 to IT-M in J52:IT-M is 1:1.

[0027] According to a preferred embodiment of the present invention, the substrate is a glass substrate, the anode is a transparent conductive film, the hole transport layer is made of PEDOT:PSS, the electron transport layer is made of PDIN, and the cathode is a top metal electrode.

[0028] The above-mentioned method for fabricating an indoor organic photovoltaic device structure that blocks blue light includes:

[0029] A hole transport layer was prepared by spin-coating on a conductive glass surface;

[0030] An active layer is prepared by spin-coating an active layer material onto a hole transport layer under a nitrogen atmosphere.

[0031] An electron transport layer was prepared by spin-coating the surface of the active layer.

[0032] A cathode is fabricated on an electron transport layer under vacuum conditions, thus obtaining the desired cathode.

[0033] PC is added to the active layer material. 71 BM.

[0034] According to a preferred embodiment of the present invention, the active layer is prepared by spin-coating an active layer material onto a hole transport layer under a nitrogen atmosphere, comprising:

[0035] Under a nitrogen atmosphere, the active layer material was spin-coated onto the hole transport layer at a speed of 3000 rpm for 50 seconds, followed by annealing at 100°C for 10 minutes.

[0036] According to a preferred embodiment of the present invention, the conductive glass is ITO conductive glass; before preparing the hole transport layer, the following operations are performed:

[0037] The ITO conductive glass was ultrasonically cleaned sequentially with cleaning agent, deionized water, acetone, anhydrous ethanol and isopropanol, dried with nitrogen gas, and then treated with UV for 15 minutes.

[0038] According to a preferred embodiment of the present invention, a hole transport layer is prepared by spin-coating on a conductive glass surface, comprising:

[0039] Spin-coat PEDOT:PSS onto the conductive glass surface and anneal at 150°C for 15 min.

[0040] According to a preferred embodiment of the present invention, an electron transport layer is prepared by spin-coating on the surface of the active layer, comprising:

[0041] Spin-coat a 2 mg / mL PDIN solution onto the active layer at a speed of 5000 rpm for 30 seconds.

[0042] According to a preferred embodiment of the present invention, the cathode is fabricated on the electron transport layer under vacuum conditions, comprising:

[0043] In 4x10 -4 A 100 nm Al electrode was prepared by thermal evaporation under vacuum conditions of Pa.

[0044] The beneficial effects of this invention are as follows:

[0045] This invention selects PC 71 BM, as a tertiary material, balances the light absorption of the LED spectrum by IOPV, reducing the proportion of blue light in the transmission spectrum while improving device performance. This is thanks to PC. 71 BM's absorption of blue light reduces the threat of blue light to the human eye during human-lamp interaction, providing guidance for photobiological safety precautions in the large-scale commercial application of IOPV. Attached Figure Description

[0046] Figure 1 This is a schematic diagram of the structure of the blue light blocking indoor organic photovoltaic device of the present invention;

[0047] Figure 2 For PC 71 BM added different types of PC to six different material systems at different temperatures. 71 BM addition ratio and blue light hazard efficacy K B,v Relationship diagram;

[0048] Figure 3 To add PC 71 BM and without adding PC 71 A schematic diagram comparing the performance of indoor solar cells prepared under two different conditions. Detailed Implementation

[0049] The present invention will be further defined below with reference to the accompanying drawings and embodiments, but is not limited thereto.

[0050] Example 1

[0051] A blue light blocking indoor organic photovoltaic device structure includes a substrate, an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode, grown sequentially from bottom to top; PC is added to the active layer. 71 BM. For example... Figure 1 As shown.

[0052] This invention selects PC 71 BM, as a tertiary material, balances the light absorption of the LED spectrum by IOPV, reducing the proportion of blue light in the transmission spectrum while improving device performance. Specifically, PC... 71 BM is added as a third material to heterojunction thin film materials, through PC 71 BM exhibits excellent light absorption in the 400-500nm range, with the addition of PC 71 After BM, the proportion of blue light in the transmission spectrum decreases, while the photocurrent of the device increases, resulting in higher device performance.

[0053] Example 2

[0054] The difference between the blue light blocking indoor organic photovoltaic device structure described in Example 1 and the following is:

[0055] The active layer is made of materials including receptors and PC. 71 The mass ratio of BM to receptor is 0-30%.

[0056] PC 71 The blue light hazard efficacy K was obtained by varying the ratio of BM to receptor from 0% to 30%. B,v The corresponding change, from KB,v From the perspective of PC 71 The higher the BM ratio, the better.

[0057] PM6:Y6 system in PC 71 BM addition ratio is PM6:Y6:PC 71 The device performance is optimal at BM(1:1.2:0.2), but from K... B,v From the perspective of PC 71 A higher BM ratio is better. Other material systems have not been used to fabricate specific batteries; only K is provided. B,v With PC 71 The specific amount of BM added should be considered in conjunction with the device performance requirements.

[0058] The acceptor is any one of the six binary material systems: PM6:Y6, PM6:BTP-eC9, PBDB-T:ITIC, PBDB-T:BTA3, PTB7-Th:IEICO-4F, and J52:IT-M.

[0059] The mass ratio of PM6 to Y6 in PM6:Y6 is 1:1.2; the mass ratio of PM6 to BTP-eC9 in PM6:BTP-eC9 is 1:1.2; the mass ratio of PBDB-T to ITIC in PBDB-T:ITIC is 1:1; the mass ratio of PBDB-T to BTA3 in PBDB-T:BTA3 is 1:1; the mass ratio of PTB7-Th to IEICO-4F in PTB7-Th:IEICO-4F is 1:1.5; the mass ratio of J52 to IT-M in J52:IT-M is 1:1.

[0060] The substrate is a glass substrate, the anode is a transparent conductive film, the hole transport layer is made of PEDOT:PSS, the electron transport layer is made of PDIN, and the cathode is a top metal electrode.

[0061] This invention will PC 71 BM was applied to six binary material systems—PM6:Y6, PM6:BTP-eC9, PBDB-T:ITIC, PBDB-T:BTA3, PTB7-Th:IEICO-4F, and J52:IT-M—to verify its universality. The impact of IOPV blue light hazard was assessed through blue light hazard effectiveness K. B,v Evaluate.

[0062] Blue light hazard efficacy K B,v Evaluation method: The transmission spectrum of the active layer heterojunction is measured to obtain the spectral power distribution function of the LED after device operation. K is then calculated using the following formula. B,v :

[0063]

[0064] In the formula, Let B(λ) be the spectral power distribution function of the light source radiation, B(λ) be the blue light hazard weighting function, V(λ) be the photoluminescence luminous efficiency function, and K be the spectral power distribution function of the light source radiation. m The maximum spectral luminous efficiency is 683 lumens per watt.

[0065] PC 71 BM is applied to 6 material systems, with PC 71 With the increase of BM addition ratio, the K of all material systems B,v All showed a monotonic decrease. Taking the 2700K as an example, when the PC... 71 When the BM addition amount is 30%, the K of PM6:BTP-eC9 (the change is most obvious) B,v It decreased by 16.21%; K of PBDB-T:BTA3 (with the smallest change) B,v It decreased by 10.19%, such as Figure 2 And as shown in Table 1. Figure 2 In the diagram, (a) represents PC. 71 BM was added to PM6:Y6 at different temperatures and with different PCs. 71 BM addition ratio and blue light hazard efficacy K B,v (a) is a diagram showing the relationship between PC and PC. 71 BM was added to PM6:BTP-eC9 at different temperatures and with different PCs. 71 BM addition ratio and blue light hazard efficacy K B,v Relationship diagram; (c) is PC 71 BM was added to PBDB-T:ITIC at different temperatures using different PCs. 71 BM addition ratio and blue light hazard efficacy K B,v Relationship diagram; (d) is PC 71 BM was added to PBDB-T:BTA3 at different temperatures and with different PCs. 71 BM addition ratio and blue light hazard efficacy K B,v Relationship diagram; (e) is PC 71 BM was added to PTB7-Th:IEICO-4F at different temperatures and with different PCs. 71 BM addition ratio and blue light hazard efficacy K B,v Relationship diagram; (f) is PC 71 BM was added to J52:IT-M at different temperatures with different PCs. 71 BM addition ratio and blue light hazard efficacy K B,v Relationship diagram;

[0066] Table 1

[0067]

[0068] Experimental results show that PC 71 The introduction of BM enables the K-type of six binary material systems. B,v All values ​​were significantly reduced, indicating that this strategy can effectively reduce the impact of blue light hazards and is not limited to one or two material systems. Furthermore, the performance of indoor solar cells based on PM6:Y6 was improved from 19.93% to 21.90%.

[0069] All material systems K B,v The decrease was greater than 10%, indicating that PC 71 The introduction of BM effectively curbed K B,v This reduces the risk of blue light hazard after the device is activated.

[0070] Based on PM6:Y6:PC 71 The performance of indoor solar cells fabricated using BM (1:1.2:0.2) was improved from 19.93% to 21.90% compared to binary devices. Figure 3 And as shown in Table 2. Figure 3 In the diagram, the horizontal axis "Voltage" refers to the open-circuit voltage, and the vertical axis "Currentdensity" refers to the short-circuit current density.

[0071] Table 2

[0072]

[0073] Example 3

[0074] The method for fabricating the blue light blocking indoor organic photovoltaic device structure described in Example 1 or 2 includes:

[0075] A hole transport layer was prepared by spin-coating on a conductive glass surface;

[0076] An active layer is prepared by spin-coating an active layer material onto a hole transport layer under a nitrogen atmosphere.

[0077] An electron transport layer was prepared by spin-coating the surface of the active layer.

[0078] A cathode is fabricated on an electron transport layer under vacuum conditions, thus obtaining the desired cathode.

[0079] PC is added to the active layer material. 71 BM.

[0080] Example 4

[0081] The difference between the fabrication method of the blue light blocking indoor organic photovoltaic device structure described in Example 3 and the method described in Example 3 is as follows:

[0082] The active layer is prepared by spin-coating an active layer material onto the hole transport layer under a nitrogen atmosphere, including: spin-coating the active layer material onto the hole transport layer under a nitrogen atmosphere at a speed of 3000 rpm for 50 s, followed by annealing at 100°C for 10 min.

[0083] The conductive glass is ITO conductive glass. Before preparing the hole transport layer, the following operations are performed: the ITO conductive glass is ultrasonically cleaned sequentially with cleaning agent, deionized water, acetone, anhydrous ethanol and isopropanol, dried with nitrogen, and then treated with UV for 15 min.

[0084] The hole transport layer is prepared by spin coating on the surface of conductive glass, including: spin coating PEDOT:PSS on the surface of conductive glass and annealing at 150°C for 15 min.

[0085] The electron transport layer was prepared by spin-coating on the surface of the active layer, including: spin-coating a 2 mg / mL PDIN solution onto the active layer at a speed of 5000 rpm for 30 s;

[0086] Fabrication of a cathode on an electron transport layer under vacuum conditions, including: in a 4x10 -4 A 100 nm Al electrode was prepared by thermal evaporation under vacuum conditions of Pa.

Claims

1. A structure for an indoor organic photovoltaic device that blocks blue light, characterized in that, It includes, from bottom to top, a substrate, an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode; PC is added to the active layer. 71 BM; The active layer is made of a receptor, PC. 71 The mass ratio of BM to receptor is 0-30%.

2. The structure of an indoor organic photovoltaic device for preventing blue light as described in claim 1, characterized in that, The acceptor is any one of six binary material systems: PM6:Y6, PM6:BTP-eC9, PBDB-T:ITIC, PBDB-T:BTA3, PTB7-Th:IEICO-4F, and J52:IT-M.

3. The structure of an indoor organic photovoltaic device for preventing blue light as described in claim 2, characterized in that, The mass ratio of PM6 to Y6 in PM6:Y6 is 1:1.2; the mass ratio of PM6 to BTP-eC9 in PM6:BTP-eC9 is 1:1.2; the mass ratio of PBDB-T to ITIC in PBDB-T:ITIC is 1:1; the mass ratio of PBDB-T to BTA3 in PBDB-T:BTA3 is 1:1; the mass ratio of PTB7-Th to IEICO-4F in PTB7-Th:IEICO-4F is 1:1.5; the mass ratio of J52 to IT-M in J52:IT-M is 1:

1.

4. The structure of an indoor organic photovoltaic device for preventing blue light as described in claim 1, characterized in that, The substrate is a glass substrate, the anode is a transparent conductive film, the hole transport layer is made of PEDOT:PSS, the electron transport layer is made of PDIN, and the cathode is a top metal electrode.

5. The method for preparing the blue light blocking indoor organic photovoltaic device structure according to any one of claims 1-4, characterized in that, include: A hole transport layer was prepared by spin-coating on a conductive glass surface; An active layer is prepared by spin-coating an active layer material onto a hole transport layer under a nitrogen atmosphere. An electron transport layer was prepared by spin-coating the surface of the active layer. A cathode is fabricated on an electron transport layer under vacuum conditions, thus obtaining the desired cathode. PC is added to the active layer material. 71 BM.

6. The method for preparing the blue light blocking indoor organic photovoltaic device structure according to claim 5, characterized in that, Under a nitrogen atmosphere, an active layer material is spin-coated onto the hole transport layer to prepare the active layer, including: Under a nitrogen atmosphere, the active layer material was spin-coated onto the hole transport layer at a speed of 3000 rpm for 50 seconds, followed by annealing at 100°C for 10 minutes.

7. The method for preparing the blue light blocking indoor organic photovoltaic device structure according to claim 5, characterized in that, The conductive glass is ITO conductive glass; before fabricating the hole transport layer, the following operations are performed: The ITO conductive glass was ultrasonically cleaned sequentially with cleaning agent, deionized water, acetone, anhydrous ethanol and isopropanol, dried with nitrogen, and then treated with UV for 15 minutes.

8. The method for preparing the blue light blocking indoor organic photovoltaic device structure according to claim 5, characterized in that, A hole transport layer is prepared by spin-coating on a conductive glass surface, including: Spin-coat PEDOT:PSS onto the conductive glass surface and anneal at 150°C for 15 min.

9. The method for preparing the blue light blocking indoor organic photovoltaic device structure according to any one of claims 6-8, characterized in that, The electron transport layer was prepared by spin-coating on the surface of the active layer, including: spin-coating a 2 mg / mL PDIN solution onto the active layer at a speed of 5000 rpm for 30 s; Fabrication of a cathode on an electron transport layer under vacuum conditions, including: in a 4x10 -4 A 100 nm Al electrode was prepared by thermal evaporation under vacuum conditions of Pa.

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