Multi-nozzle device for printing photoelectric functional film and method for printing photoelectric functional film

Abstract

The invention discloses multi-nozzle equipment for printing a photoelectric functional film and a method for printing the photoelectric functional film, the equipment comprises a liquid supply tank, a spray gun module, an electric field generation module and a substrate, the interior of the liquid supply tank is divided into a plurality of independent liquid storage cabins through partition plates, and the independent liquid storage cabins are used for storing different solutions; the spray gun module comprises a plurality of sprayers, the number of the sprayers is the same as that of the liquid storage cabins, and the sprayers are arranged at the bottoms of the liquid storage cabins in a one-to-one correspondence mode and used for evenly spraying different solutions on the base; and the electric field generation module is used for electrifying the liquid supply tank, so that solution drops sprayed by the spray head are electrified, a uniform electric field is generated in a spraying area, and the deposition of the drops is guided. The equipment can avoid the coffee ring effect in the film preparation process, solve the splashing problem, simplify the preparation process and improve the film quality.

Description

Technical Field

[0001] This application relates to the technical fields of spraying and thin film preparation, and particularly to an apparatus for printing optoelectronic functional thin films with multiple nozzles and a method for printing optoelectronic functional thin films. Background Art

[0002] Optoelectronic functional thin films are thin film materials with optoelectronic properties and are applied in the fields of optoelectronic devices, energy, display technology, etc. Perovskite thin films are optoelectronic functional thin film materials with a perovskite crystal structure and have been widely applied in the fields of solar cells, display devices, and photodetectors in recent years due to their excellent optoelectronic properties. Currently, the preparation methods of perovskite thin films mainly include the one-step method and the two-step method: the one-step method has a simple process, but there are problems such as poor film uniformity and obvious coffee ring effect; although the two-step method can improve the film quality, the process is complex and it is difficult to achieve large-area preparation.

[0003] The following problems often occur in the process of preparing thin films, especially perovskite thin films, with existing spraying equipment: 1. Coffee ring effect: When the liquid evaporates, solid particles or components redeposit on the edge of the liquid film, resulting in a higher concentration at the edge of the coating than in the central part, forming a ring structure; 2. Splashing problem: The coating splashes or spills onto non-target areas, causing material waste and environmental pollution; 3. Complex process: The traditional two-step method requires step-by-step deposition of metal halides and organic halides, and the process steps are cumbersome, making it difficult to achieve efficient and large-area preparation.

[0004] In the prior art, the coffee ring effect and the splashing problem have not been effectively solved, and the process complexity of the two-step method limits the large-scale preparation of optoelectronic functional thin films, especially the industrial application of large-area perovskite thin films. Summary of the Invention

[0005] Objective: To overcome the deficiencies in the prior art, the present invention provides an apparatus for printing optoelectronic functional thin films with multiple nozzles and a method for printing optoelectronic functional thin films, which solves the coffee ring effect and the splashing problem in the process of thin film preparation, simplifies the process, and improves the preparation efficiency.

[0006] Technical Solution: To solve the above technical problems, the technical solution adopted by the present invention is as follows:

[0007] In a first aspect, the present application provides an apparatus for printing optoelectronic functional thin films with multiple nozzles, including: A liquid supply tank, a spray gun module, an electric field generation module, and a substrate, The interior of the liquid supply tank is divided into multiple independent liquid storage compartments by partitions for storing different solutions; The spray gun module includes a plurality of spray heads, the number of which is the same as that of the liquid storage tanks, and they are all correspondingly arranged at the bottom of each liquid storage tank for uniformly spraying different solutions on the substrate respectively; By adjusting the spraying parameters, the main spray head sprays the main solution, and the adjacent spray heads spray other solutions, so that the liquid film evaporates uniformly, avoiding too high concentration at the edges; The electric field generation module is used to energize the liquid supply tank, so that the solution droplets ejected from the spray heads are charged, and a uniform electric field is generated in the spraying area. The electric field force is used to guide the charged droplets to deposit towards the target area, reducing droplet splashing; the electric field generation module adjusts the electric field intensity and direction through the control system to ensure accurate droplet deposition.

[0008] Among them, the substrate is grounded.

[0009] In some embodiments, the multi-nozzle device for printing optoelectronic functional thin films further includes a substrate heating module. The substrate heating module includes a heating resistance wire, a voltage-output type temperature controller, and a solid-state relay. The heating resistance wire is arranged in the substrate, and the voltage-output type temperature controller and the solid-state relay are used together to control the substrate temperature, which is used to complete the heating and annealing operations during the thin film printing process.

[0010] Among them, the voltage-output type temperature controller is used to detect the temperature and output a control signal, and the solid-state relay is used to control the on-off of the power supply of the heating resistance wire; the substrate heating module can linearly regulate the substrate temperature, further optimize the evaporation behavior of the liquid film, complete the annealing operation during the thin film printing process, and suppress the coffee ring effect.

[0011] In some embodiments, the fluid flow rate range of the spray heads in the spray gun module is 0 - 100 μL / min.

[0012] In some embodiments, the spraying speed of the spray heads in the spray gun module is 1 - 100 μL / min.

[0013] In some embodiments, the liquid supply pressure of the multi-nozzle device for printing optoelectronic functional thin films is 1 - 1000 kPa, and the pressure of the spray heads in the spray gun module is 0.1 - 0.3 MPa.

[0014] In some embodiments, the distance between the spray gun module and the substrate is adjustable, and the distance adjustment range is 5 - 100 mm.

[0015] In some embodiments, the planar movement range of the spray gun module is 1 - 300 mm.

[0016] In some embodiments, the electric field generation module generates direct current, and the generated voltage range is -10000 - +10000 V.

[0017] In some embodiments, the method for arranging the thermal resistance wires in the substrate is as follows: First, use thermal simulation to reasonably distribute the positions of the thermal resistance wires in the substrate, and then embed the thermal resistance wires in the substrate according to the positions obtained from the simulation.

[0018] In some embodiments, the heating temperature range of the substrate heating module is 25 - 200 °C.

[0019] In a second aspect, the present application provides a method for printing an optoelectronic functional thin film, using the device for printing an optoelectronic functional thin film with multiple nozzles as described in the first aspect. The method includes: S1. Respectively load the metal halide solution and the organic halide solution into different liquid storage compartments of the device for printing an optoelectronic functional thin film with multiple nozzles; S2. Turn on the electric field generation module and set the electric field strength and direction; S3. Start the spray gun module, first spray the metal halide solution, let it stand, then spray the organic halide solution, let it stand, so that the two solutions react on the substrate; during the spraying process, keep the substrate heated; S4. Adjust the substrate temperature and perform annealing treatment. Beneficial effects

[0020] 1. Solve the coffee ring effect: Through the collaborative spraying of multiple spray guns, adjusting the spraying parameters, and controlling the evaporation rate, uniform evaporation of the liquid film is achieved, avoiding the coffee ring effect.

[0021] 2. Solve the splashing problem: By energizing the liquid supply tank, the droplets ejected from the nozzle are charged, and the electric field is used to guide the droplets to deposit towards the target area, reducing splashing and improving the material utilization rate and the quality of the thin film.

[0022] 3. Combine the two-step method for one-step deposition of optoelectronic functional thin films: By spraying the metal halide and organic halide solutions respectively with multiple spray guns, one-step deposition is achieved, simplifying the process and improving the quality of the thin film.

[0023] The optoelectronic functional thin film manufactured using the device disclosed in the present invention has the advantages of good uniformity, high material utilization rate, simple process, and suitability for large-area preparation. The device and method of the present invention can be widely applied to fields such as solar cells, display devices, and photodetectors. Description of the drawings

[0024] In order to more clearly illustrate the technical solutions in the embodiments of the present disclosure or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the following drawings are only some embodiments of the present disclosure. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0025] Figure 1Schematic structural diagram of the device for printing optoelectronic functional thin films with multiple nozzles in the embodiments of the present invention;

[0026] Figure 2 Schematic diagram of the movement direction of droplets under the action of an electric field in the embodiments of the present invention;

[0027] Figure 3 J-V curve of the two-step spraying of perovskite thin films in the embodiments of the present invention.

[0028] In the figure: 1 liquid supply tank, 2 spray gun module, 3 electric field generation module, 4 substrate, 5 charged droplet. Detailed implementation manners

[0029] The following will clearly and completely describe the technical solutions in the embodiments in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. The description of at least one exemplary embodiment below is actually only illustrative and in no way limits the present invention and its application or use.

[0030] Unless otherwise specifically stated, the relative arrangements of components and steps, numerical expressions and values set forth in these embodiments do not limit the scope of the present invention. At the same time, it should be understood that for the convenience of description, the dimensions of each part shown in the drawings are not drawn according to the actual proportional relationship. Technologies, methods and devices known to those of ordinary skill in the relevant art may not be discussed in detail, but where appropriate, the technologies, methods and devices should be regarded as part of the authorization specification. In all the examples shown and discussed here, any specific value should be interpreted as merely exemplary and not as a limitation. Therefore, other examples of the exemplary embodiments may also include different values. It should be noted that: like reference numerals and letters denote like items in the following drawings, and thus, once an item is defined in one drawing, it does not need to be further discussed in subsequent drawings.

[0031] Embodiment 1:

[0032] This embodiment provides a device for printing optoelectronic functional thin films with multiple nozzles, as Figure 1 shown, including: a liquid supply tank 1, a spray gun module 2, an electric field generation module 3 and a substrate 4, the interior of the liquid supply tank 1 is divided into multiple independent liquid storage compartments by partitions for storing different solutions; the spray gun module 2 includes multiple nozzles, the number of which is the same as the number of liquid storage compartments, and they are all correspondingly arranged at the bottom of each liquid storage compartment for uniformly spraying different solutions on the substrate 4; By adjusting the spraying parameters, the main nozzle sprays the main solution, and the adjacent nozzles spray other solutions, so that the liquid film evaporates uniformly, avoiding too high concentration at the edges; The electric field generation module 3 includes a 220V power supply, a micro high-voltage power supply module and a transformer. The micro high-voltage power supply module converts low-voltage direct current into high-voltage direct current and further boosts the voltage through the transformer for energizing the liquid supply tank 1.

[0033] The solution droplets ejected from the nozzles are charged, that is, Figure 2 the charged droplets 5 in, and a uniform electric field is generated in the spraying area. The electric field force is used to guide the charged droplets to deposit towards the target area, reducing droplet splashing; the electric field generation module 3 adjusts the electric field strength and direction through the control system to ensure accurate droplet deposition.

[0034] In some embodiments, the multi-nozzle device for printing optoelectronic functional thin films further includes a substrate heating module (not shown in the figure). The substrate heating module includes a heating resistance wire, a voltage-output type temperature controller and a solid-state relay. The heating resistance wire is arranged in the substrate 4, and the voltage-output type temperature controller and the solid-state relay are used in combination to control the temperature of the substrate 4, for performing heating and annealing operations during the thin film printing process.

[0035] Among them, the voltage-output type temperature controller is used to detect the temperature and output a control signal, and the solid-state relay is used to control the on-off of the power supply of the heating resistance wire; the substrate heating module can achieve linear regulation of the temperature of the substrate 4, further optimize the evaporation behavior of the liquid film, complete the annealing operation during the thin film printing process, and suppress the coffee ring effect.

[0036] In some embodiments, first, the positions of the heating resistance wires are reasonably distributed in the thermal simulation substrate 4, and the heating resistance wires are embedded in the substrate 4 according to the simulated positions.

[0037] In some embodiments, the fluid flow rate range of the nozzles in the spray gun module 2 is 0 - 100 μL / min.

[0038] In some embodiments, the spraying speed of the nozzles in the spray gun module 2 is 1 - 100 μL / min.

[0039] In some embodiments, the liquid supply pressure of the multi-nozzle device for printing optoelectronic functional thin films is 1 - 1000 kPa, and the nozzle pressure in the spray gun module 2 is 0.1 - 0.3 MPa.

[0040] In some embodiments, the distance between the spray gun module 2 and the substrate 4 is adjustable, and the distance adjustment range is 5 - 100 mm.

[0041] In some embodiments, the planar movement range of the spray gun module 2 is 1 - 300 mm.

[0042] In some embodiments, the electric field generation module 3 generates direct current, and the generated voltage ranges from -10000 to +10000 V.

[0043] In some embodiments, the heating temperature range of the substrate heating module is 25 - 200 °C.

[0044] Embodiment 2:

[0045] This embodiment provides a method for preparing an optoelectronic functional film using the device for printing an optoelectronic functional film with multiple nozzles as described in Embodiment 1, including: S1. Configure a metal halide solution and an organic halide solution, and respectively load the metal halide solution and the organic halide solution into different metal halide storage tanks and organic halide storage tanks of the device for printing an optoelectronic functional film with multiple nozzles; S2. Turn on the electric field generation module 3 and set the voltage, electric field strength, and electric field direction; S3. Start the spray gun module 2, first spray the metal halide solution, and let it stand to make the liquid film evenly distributed initially; then spray the organic halide solution and let it stand to make the two solutions react on the substrate 4; during the spraying process, keep the substrate 4 heated; S4. After the solutions react on the substrate 4, adjust the temperature of the substrate 4 and perform an annealing treatment.

[0046] Embodiment 3:

[0047] This embodiment provides a method for preparing a perovskite photovoltaic device. Use the device for printing an optoelectronic functional film with multiple nozzles as described in Embodiment 1 and combine it with the method for preparing an optoelectronic functional film as described in Embodiment 2 to prepare the perovskite film in the perovskite photovoltaic device.

[0048] Step 1: Substrate pretreatment

[0049] The conductive substrate is ultrasonically cleaned with glass cleaning agent, deionized water, isopropanol, acetone, and ethanol in sequence for 15 minutes. After cleaning, the substrate is placed in an oven to be dried at a temperature of 80 - 100 °C for 60 minutes. The cleaned substrate is placed in a plasma machine for treatment for 5 - 10 minutes to remove surface organic substances and improve surface performance.

[0050] In this embodiment, the material of the conductive substrate is selected from one of FTO glass, ITO glass, PEN / ITO flexible conductive substrate, or PET / ITO flexible conductive substrate.

[0051] Step 2: Preparation of the hole transport layer

[0052] Spin-coat the hole transport layer precursor solution on the surface of the conductive substrate processed in Step 1 to form a film. The rotation speed is 2500 - 3000 rpm, the spin-coating time is 20 - 40 s, and the film is annealed. The hot stage temperature is 120 - 150 °C, and the annealing time is 15 - 30 min, then a dense hole transport layer film can be obtained.

[0053] In this embodiment, the hole transport layer is made of nickel oxide nanomaterials, and the concentration of the precursor solution is 10 - 20 mg / mL.

[0054] Step 3: Preparation of the perovskite light absorption layer

[0055] Load the metal halide solution into the metal halide storage tank of the liquid supply tank 1, start the metal halide spray gun, and set the spraying parameters:

[0056] Spraying speed: 1 - 100 μL / min; nozzle pressure: 0.1 - 0.3 MPa; liquid supply pressure: 1 - 1000 kPa; distance between the nozzle and the substrate: 0.1 - 10 cm.

[0057] Start the electric field generation module 3, set the voltage to 0 - 1000 V, the electric field strength to 0 - 10000 V / m, and the direction of the electric field strength is from the nozzle perpendicular to the direction of the heated substrate 4.

[0058] In this embodiment, the metal halide solution is a PbI2 solution with a concentration of 1.0 - 1.5 M, and the solvent is DMF.

[0059] Spray the metal halide solution evenly on the substrate 4 to form a PbI2 film. After spraying, let it stand for 10 - 20 seconds to make the liquid film evenly distributed initially.

[0060] Then load the organic halide solution (CH3NH3I solution with a concentration of 0.5 - 1.0 M and the solvent is isopropanol) into the organic halide storage tank of the liquid supply tank 1, start the organic halide spray gun, and set the spraying parameters:

[0061] Spraying speed: 1 - 100 μL / min; nozzle pressure: 0.1 - 0.3 MPa; liquid supply pressure 1 - 1000 kPa; distance between the spray gun and the substrate: 0.1 - 10 cm.

[0062] In this embodiment, the organic halide solution is a CH3NH3I solution with a concentration of 0.5 - 1.0 M, and the solvent is isopropanol.

[0063] Spray the organic halide solution evenly on the PbI2 film, so that the two solutions react on the substrate 4 to form a perovskite film. After spraying, let it stand for 10 - 30 seconds to make the reaction proceed fully.

[0064] During the spraying process, turn on the substrate heating module and set the initial temperature to 20 - 30 °C. Before spraying, gradually increase the substrate temperature to 100 - 120 °C at a heating rate of 1 - 5 °C / s. Anneal at 100 - 120 °C for 20 - 30 minutes to optimize the crystallization quality of the perovskite film.

[0065] Step 4: Preparation of the electron transport layer

[0066] Spin-coat and form a thin film of the electron transport layer precursor solution on the surface of the perovskite film obtained in Step 3 at a rotation speed of 2000 - 3000 rmp for 20 - 40 s, without annealing treatment.

[0067] In this example, the electron transport layer material is PCBM with a concentration of 20 - 25 mg / mL.

[0068] Step 5: Preparation of the metal electrode

[0069] Place the prepared sample in a physical vapor deposition device for evaporation of the metal electrode.

[0070] Example 4:

[0071] This example provides a method for preparing a perovskite solar cell based on the method for preparing a perovskite photovoltaic device described in Example 3. Use the multi-nozzle printing optoelectronic functional thin film device as described in Example 1, and prepare the perovskite light absorption layer in the perovskite solar cell according to the method for preparing the optoelectronic functional thin film described in Example 2.

[0072] 1. Pretreatment of the conductive substrate: Use an ITO flexible conductive substrate as the substrate, and ultrasonically clean it with a cleaning agent, deionized water, isopropanol, acetone, and ethanol in sequence for 15 minutes. After drying, perform plasma treatment for 5 minutes.

[0073] 2. One-step method for preparing the hole transport layer: The material of the hole transport layer is nickel oxide nanoparticles with a thickness of 20 nm. The specific steps are as follows:

[0074] Prepare 5 mL of an aqueous solution of NiO x nanoparticles, and ultrasonically treat it for 30 min to fully disperse the nanoparticles. Spin-coat the nickel oxide solution on the ITO conductive substrate by the spin-coating method at a spin-coating speed of 2000 rpm for 30 s. After the spin-coating is completed, place it on a heated substrate at 120 °C and anneal for 15 min to obtain a dense nickel oxide hole transport layer.

[0075] 3. Two-step method for preparing the perovskite layer:

[0076] Dissolve PbI2 powder in DMF and heat and stir it on the heating substrate 4 at 85 °C for 1 hour to prepare a 1.3 M PbI2 precursor solution; dissolve formamidinium iodide (FAI), methylammonium bromide (MABr), and methylammonium chloride (MACl) in isopropanol according to a molar ratio of 71:11:18 to prepare a 0.5 M organic halide precursor solution; respectively load the two precursor solutions into the metal halide reservoir and the organic halide reservoir of the multi-nozzle printing optoelectronic functional thin film device.

[0077] Turn on the electric field generation module 3, set the voltage to 500 V, the electric field strength to 5000 V / m, and the direction of the electric field strength to be perpendicular to the heating substrate 4 from the nozzle.

[0078] After loading the PbI2 solution into the metal halide reservoir, set the spraying speed to 30 μL / min, the nozzle pressure to 0.3 MPa, the supply pressure to 100 kPa, and the distance between the nozzle and the substrate 4 to 7 cm. Spray the PbI2 solution evenly on the substrate to form a layer of PbI2 thin film. After spraying, let it stand for 10 - 20 seconds to make the liquid film evenly distributed initially.

[0079] Then spray the organic halide solution evenly on the PbI2 thin film, set the spraying speed to 30 μL / min, the spraying pressure to 0.3 MPa, and the distance between the spray gun and the substrate to 7 cm.

[0080] During the spraying process, keep the substrate 4 heated, and set the temperature to 70 °C.

[0081] The two solutions react on the substrate. After completion, heat the substrate 4 to 150 °C and anneal for 20 min to obtain a perovskite thin film.

[0082] 4. Dissolve 20 mg of PCBM in 1 mL of chlorobenzene and spin-coat PCBM on the perovskite thin film by the spin-coating method at a spin-coating speed of 2000 rpm for 30 s.

[0083] 5. Deposit the hole-blocking layer BCP and the metal Ag electrode by thermal evaporation (vacuum degree lower than 10 -4 Pa) to obtain a perovskite solar cell. The corresponding J-V curve is as Figure 3 shown, and the parameters corresponding to the J-V curve are shown in Table 1.

[0084] Table 1 Parameters corresponding to the J-V curve of the two-step spray perovskite thin film device Open-circuit voltage (V) <![CDATA[Short-circuit current density (mA / cm 2 ).]]> Fill factor (%) Photovoltaic conversion efficiency (%) Example 4 1.06 22.16 70.74 16.56

[0085] In the description of the present application, it should be understood that the orientation or positional relationship indicated by the terms "center", "longitudinal", "transverse", "upper", "lower", "front", "rear", "left", "right", "inner", "outer", etc. is based on the orientation or positional relationship shown in the drawings, and is only used to explain the relative positional relationship and movement conditions between components in a specific posture. If this specific posture changes, the directional indication will also change accordingly. It is only for the convenience of describing the present application and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as a limitation to the present application.

[0086] In the description of the present application, unless otherwise specified, the meaning of "a plurality of" is two or more.

[0087] In the description of the present application, it should be noted that unless otherwise clearly specified and limited, the terms "mounted", "connected" and "connected" should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium, and it can be the communication inside two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the present application can be understood through specific situations.

[0088] The above are only the preferred embodiments of the present application. It should be pointed out that for those of ordinary skill in the art, without departing from the technical principle of the present application, several improvements and deformations can still be made, and these improvements and deformations should also be regarded as the protection scope of the present application.

Claims

1. An apparatus for printing an optoelectronic functional thin film with multiple nozzles, characterized in that, Comprising: A liquid supply tank, a spray gun module, an electric field generation module, and a substrate, The interior of the liquid supply tank is divided into multiple independent liquid storage compartments by partitions for storing different solutions; The spray gun module includes multiple nozzles, the number of which is the same as the number of liquid storage compartments, and they are all correspondingly arranged at the bottom of each liquid storage compartment for uniformly spraying different solutions on the substrate respectively; The electric field generation module is used to energize the liquid supply tank, so that the solution droplets ejected from the nozzles are charged, and a uniform electric field is generated in the spraying area to guide the droplet deposition.

2. The device for printing the optoelectronic functional thin film with multiple nozzles according to claim 1, wherein, The multi-nozzle device for printing optoelectronic functional thin films further includes a substrate heating module, which includes a thermal resistance wire, a voltage output type temperature controller, and a solid state relay. The thermal resistance wire is arranged in the substrate, and the voltage output type temperature controller and the solid state relay are used in combination to control the substrate temperature for performing heating and annealing operations during the thin film printing process.

3. The device for printing optoelectronic functional thin films with multiple nozzles according to claim 1, characterized in that, The fluid flow rate range of the nozzles in the spray gun module is 0 - 100 μL / min.

4. The device for printing optoelectronic functional films with multiple nozzles according to claim 1, characterized in that, The spraying speed of the nozzles in the spray gun module is 1 - 100 μL / min.

5. The device for printing optoelectronic functional thin films with multiple nozzles according to claim 1, wherein The liquid supply pressure of the multi-nozzle device for printing optoelectronic functional thin films is 1 - 1000 kPa, and the nozzle pressure in the spray gun module is 0.1 - 0.3 MPa.

6. The device for printing the optoelectronic functional thin film with multiple nozzles according to claim 1, wherein, ​ ​ 8. The apparatus for printing an optoelectronic functional thin film with multiple nozzles according to claim 2, wherein ​ 9. The device for printing optoelectronic functional thin films with multiple nozzles according to claim 2, characterized in that, ​ 10. A method for printing an optoelectronic functional thin film, characterized in that, ​ ​ ​ ​ ​

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