CN113713975B - Four-electrode electrostatic spray printing device and film preparation method - Google Patents

Four-electrode electrostatic spray printing device and film preparation method Download PDF

Info

Publication number
CN113713975B
CN113713975B CN202110866502.2A CN202110866502A CN113713975B CN 113713975 B CN113713975 B CN 113713975B CN 202110866502 A CN202110866502 A CN 202110866502A CN 113713975 B CN113713975 B CN 113713975B
Authority
CN
China
Prior art keywords
electrode
electrostatic spray
spray printing
substrate
needle
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110866502.2A
Other languages
Chinese (zh)
Other versions
CN113713975A (en
Inventor
常凯
于博洋
赵新彦
邓巍巍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Southwest University of Science and Technology
Original Assignee
Southwest University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Southwest University of Science and Technology filed Critical Southwest University of Science and Technology
Priority to CN202110866502.2A priority Critical patent/CN113713975B/en
Publication of CN113713975A publication Critical patent/CN113713975A/en
Application granted granted Critical
Publication of CN113713975B publication Critical patent/CN113713975B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
    • B05B5/025—Discharge apparatus, e.g. electrostatic spray guns
    • B05B5/053—Arrangements for supplying power, e.g. charging power
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
    • B05B5/025—Discharge apparatus, e.g. electrostatic spray guns
    • B05B5/053—Arrangements for supplying power, e.g. charging power
    • B05B5/0533—Electrodes specially adapted therefor; Arrangements of electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field

Abstract

The invention discloses a four-electrode electrostatic spray printing device and a film preparation method, wherein the printing device comprises an active liquid supply system, an external high-voltage system and a three-dimensional moving platform, the external high-voltage system comprises a high-voltage power supply and a four-electrode structure electrically connected with the high-voltage power supply, and the four-electrode structure comprises a fixed frame, a needle head arranged in the middle of the fixed frame and four electrode columns arranged at four ends of the fixed frame; the active liquid supply system includes a syringe in communication with the needle, and a syringe pump in communication with the syringe. Based on the printing device, the shape of the fog spots is regulated and controlled through the interference of an external electric field, the round fog spots are compressed into the strip-shaped fog spots, the density of liquid drops in a unit area is increased, holes formed by dispersion of the liquid drops due to coulomb force are reduced, the shape of the film can be optimized, and the performance of the photoelectric device can be effectively improved through the photoelectric film prepared by the method.

Description

Four-electrode electrostatic spray printing device and film preparation method
Technical Field
The invention relates to the technical field of photoelectric devices, in particular to a four-electrode electrostatic spray printing device and a film preparation method.
Background
In order to meet the requirement of industrial production, developing a production process suitable for continuously preparing a large-area photoelectric functional film is one of the key challenges in the field of photoelectric devices. Among them, spray coating technology is attracting increasing attention as a non-contact method based on droplets because it has the potential to achieve conformal deposition, and compatibility with substrate curvature and roughness is good.
The most challenging problems faced by spray coating methods to produce high performance photovoltaic functional films are coffee ring effect and needle defects. For the electrostatic spraying method, under the action of an external electric field, droplets repel each other due to coulomb force, so that the distance between the droplets deposited on a substrate is large, and in the process of forming a film by connecting the droplets, because the evaporation time of the droplets is short and new droplets are difficult to wait for falling to the vicinity of the droplets, a plurality of needle defects exist in the film, which is one of the main problems in the preparation of high-quality photoelectric devices by the electrostatic spraying method at present.
Thus, there is still a need for improvement and development of the prior art.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention provides a four-electrode electrostatic spray printing apparatus and a film preparation method, and aims to solve the problems of needle defects and coffee ring effect in the film preparation process by the conventional electrostatic spray method.
In order to achieve the purpose, the invention adopts the following scheme:
a four-electrode electrostatic spray printing device comprises an active liquid supply system, an external high-voltage system and a three-dimensional moving platform, wherein the external high-voltage system comprises a high-voltage power supply and a four-electrode structure electrically connected with the high-voltage power supply, and the four-electrode structure comprises a fixing frame, a needle head arranged in the middle of the cross-shaped fixing frame and four electrode columns arranged at four ends of the fixing frame; the active liquid supply system comprises an injector communicated with the needle head and a syringe pump communicated with the injector; the three-dimensional moving platform is used for generating relative motion between the needle head and the substrate on which the prepared film is placed.
The four-electrode electrostatic spray printing device is characterized in that the fixing frame is a cross-shaped fixing frame.
The four-electrode electrostatic spray printing device is characterized in that the cross-shaped fixing frame comprises a first support and a second support which are perpendicular to each other, the needle head is arranged at a vertical crossing position of the first support and the second support, the first support is provided with two first electrodes taking the vertical crossing position as a symmetrical point, and the second support is provided with two second electrodes taking the vertical crossing position as a symmetrical point.
The four-electrode electrostatic spray printing device is characterized in that the horizontal distance between the two first electrodes and the needle head is 5-30mm; the horizontal distance between the two second electrodes and the needle is 5-30mm.
The four-electrode electrostatic spray printing device is characterized in that a high-voltage wiring of the high-voltage power supply is connected with the two first electrodes, and two grounding wirings of the high-voltage power supply are respectively connected with the substrate and the two second electrodes.
The four-electrode electrostatic spray printing device is characterized in that the first electrode and the second electrode are both cylindrical.
The four-electrode electrostatic spray printing device comprises a three-dimensional moving platform, a needle head and a four-electrode electrostatic spray printing head, wherein the three-dimensional moving platform comprises a fixed column which is used for fixing the injection pump and can move in the Z-axis direction, and a substrate which is positioned below the needle head and can move in the X-axis direction and the Y-axis direction.
A film preparation method of a four-electrode electrostatic spray printing device comprises the following steps:
storing the prepared printing solution in an injector, and communicating the injector with a needle head;
setting the flow rate of a syringe pump, turning on the syringe pump, and pushing out the printing solution in the syringe through the syringe pump;
starting a high-voltage power supply, and increasing the voltage until the long-strip-shaped fog spots below the needle head are observed;
and placing the substrate on a substrate, and setting the moving speed of the substrate to enable the three-dimensional moving platform to move according to a preset route to finish film printing.
The film preparation method based on the four-electrode electrostatic spray printing device is characterized in that the moving speed of the substrate is 0.01-10 mm/s.
The film preparation method based on the four-electrode electrostatic spray printing device is characterized in that the length-width ratio of the long-strip-shaped fog spots is 2.
Has the beneficial effects that: compared with the prior art, the film preparation method based on the four-electrode electrostatic spraying device provided by the invention has the advantages that the flying track of the charged liquid drops is restrained by the external electric field near the needle head through the external high-voltage system, the circular fog spots are compressed into the long-strip-shaped fog spots, and the length-width ratio of the fog spots is increased from 1 to 8 or even larger from 1. Under the fog spots with large length-width ratio, the average distance between the liquid drops is reduced, and the density of the liquid drops is greatly increased under the condition of the same evaporation time of the liquid drops, so that the fusion probability among the liquid drops is improved, and the needle defects of the film are reduced. Meanwhile, the thickness and the quality of the deposited film can be controlled by regulating and controlling the movement path of the substrate, and compared with the common electrostatic spraying, the performance of the photoelectric device is effectively improved.
Drawings
Fig. 1 is a schematic structural diagram of a four-electrode electrostatic spray printing apparatus provided by the present invention.
Fig. 2 is an enlarged schematic view of a four-electrode structure in the four-electrode electrostatic spray printing apparatus of fig. 1.
Fig. 3 is a flowchart of a method for preparing a thin film based on a four-electrode electrostatic spray printing apparatus according to the present invention.
Fig. 4 is a structure of an organic solar cell device manufactured by the present invention and a molecular structural formula of an organic photoelectric material used in examples 1 to 3.
FIG. 5 is a comparison graph of spot shape and film topography for ES (general electrostatic spray) and QES (four electrode electrostatic spray) printing.
FIG. 6 is a current-voltage curve of ES and QES on an ITO substrate to prepare an active layer device in example 1.
Fig. 7 is a current-voltage curve of ES and QES fabricated active layer devices on PET flexible substrates in example 2.
FIG. 8 is a current-voltage curve of a device in example 3 in which the active layer and the interfacial layer are simultaneously prepared using ES or QES, respectively.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1 and 2, the present invention provides a four-electrode electrostatic spray printing apparatus, as shown in the figure, including an active liquid supply system, an external high voltage system and a three-dimensional moving platform, where the external high voltage system includes a high voltage power supply and a four-electrode structure 10 electrically connected to the high voltage power supply, the four-electrode structure 10 includes a cross-shaped fixing frame 11, a needle 12 disposed in the middle of the cross-shaped fixing frame, and four electrode posts 13 disposed at four ends of the cross-shaped fixing frame 11; the active liquid supply system comprises a syringe 21 communicated with the needle 12 and a syringe pump 22 communicated with the syringe 21; the three-dimensional moving platform comprises a fixed column 31 which is used for fixing the injection pump 22 and can move in the Z-axis direction, and a base plate 32 which is positioned below the needle head 12 and can move in the X-axis direction and the Y-axis direction.
In this embodiment, as shown in fig. 2, the cross-shaped fixing frame 11 includes a first frame 111 and a second frame 112 perpendicular to each other, the needle 12 is disposed at a perpendicular crossing portion 113 of the first frame 111 and the second frame 112, two first electrodes 131 are disposed on the first frame 111, with the perpendicular crossing portion 113 being a symmetry point, and two second electrodes 132 are disposed on the second frame 112, with the perpendicular crossing portion 113 being a symmetry point. In this embodiment, the vertical intersection 113 is further provided with a socket 114, and the socket 114 is used for mounting the syringe 21, so that the syringe 21 is communicated with the needle 12.
In this embodiment, by turning on a high-voltage power supply, an electric field is generated near the needle through four electrode columns arranged at four ends of the cross-shaped fixing frame 11, so that the flight trajectory of charged droplets flowing out of the needle can be constrained, and a circular fog spot is compressed into a long-strip fog spot, and the length-width ratio of the fog spot is increased from 1 to 8. Under the fog spots with large length-width ratio, the average distance between the liquid drops is reduced, and the density of the liquid drops is greatly increased under the condition of the same evaporation time of the liquid drops, so that the fusion probability among the liquid drops is improved, and the needle defects of the film are reduced. Meanwhile, the thickness and the quality of the deposited film can be controlled by regulating and controlling the movement path of the substrate, and compared with the common electrostatic spraying, the performance of the photoelectric device is effectively improved.
In some embodiments, the two first electrodes are at a horizontal distance of 5-30mm from the needle; the horizontal distance between the two second electrodes and the needle is 5-30mm. By way of example, the two first electrodes are both 20mm horizontally away from the needle, and the two second electrodes are also both 20mm horizontally away from the needle. As shown in fig. 2, the high voltage connection of the high voltage power supply is connected to the two first electrodes, and the two ground connections of the high voltage power supply are respectively connected to the substrate and the two second electrodes. Specifically, the high-voltage connection of the high-voltage power supply is a live wire, is connected to the two first electrodes and is connected in advance through a metal wire, so that only one of the electrodes needs to be connected when the live wire is connected; the high-voltage power supply grounding wires are two, one high-voltage power supply grounding wire is used for connecting the substrate (the movable three-dimensional platform), and the other high-voltage power supply grounding wire is used for connecting the two second electrodes; principle of changing length-width ratio of fog spots: the droplets generated by electrostatic spraying are positively charged and are attracted and collected by the substrate (grounded) under the action of an electric field, under the four-electrode device, one pair of first electrodes connected with a positive high voltage play a role in compressing the electric field to restrain the flight trajectory of the droplets, and the other pair of grounded second electrodes play a role in stretching the electric field to attract the droplets, transversely compress and longitudinally stretch, so that the shape of the fog spots is changed from a circle to an ellipse.
In some embodiments, the first and second electrodes are both cylindrical and both the first and second electrodes are metal electrodes.
In some embodiments, there is also provided a method for preparing a thin film based on a four-electrode electrostatic spray printing apparatus, as shown in fig. 3, comprising the steps of:
s10, storing the prepared printing solution in an injector, and communicating the injector with a needle head;
s20, setting the flow of a syringe pump, starting the syringe pump, and pushing out the printing solution in the syringe through the syringe pump;
s30, starting a high-voltage power supply, and increasing the voltage until the long-strip-shaped fog spots below the needle head are observed;
s40, placing the substrate on a substrate, and setting the moving speed of the substrate to enable the three-dimensional moving platform to move according to a preset route to finish film printing.
In the embodiment, an electric field is generated near the needle head by four electrode columns arranged at four ends of the cross-shaped fixing frame, so that the flight trajectory of charged droplets flowing out of the needle head can be restrained, the circular mist spot is compressed into a long-strip-shaped mist spot, and the length-width ratio of the mist spot is increased from 1 to 8. Under the fog spots with large length-width ratio, the average distance between the liquid drops is reduced, and the density of the liquid drops is greatly increased under the condition of the same evaporation time of the liquid drops, so that the fusion probability among the liquid drops is improved, and the needle defects of the film are reduced. Meanwhile, the thickness and the quality of the deposited film can be controlled by regulating and controlling the movement path of the substrate, and compared with the common electrostatic spraying, the performance of the photoelectric device is effectively improved.
In some embodiments, the substrate is moved at a speed of 0.01mm/s to 10mm/s, but is not limited thereto.
In some embodiments, the elongated haze has an aspect ratio of 2. By way of example, the aspect ratio of the elongated haze may be 2.
In some embodiments, the voltage of the high voltage power supply is 0-10kV, but is not limited thereto.
The following is a further explanation of the thin film preparation method based on a four-electrode electrostatic spray printing apparatus according to the present invention by way of specific examples:
example 1
Preparing an organic photoelectric film on a cleaned ITO glass substrate, ultrasonically cleaning the ITO glass substrate by detergent, deionized water, acetone and isopropanol for 15 minutes in sequence, drying the ITO glass substrate for at least 1 hour at 80 ℃, and then carrying out plasma treatment for 1min. The PEDOT: PSS was spin-coated at room temperature with a spin-coating parameter of 3000rpm 30s. The substrate was then annealed at 150 ℃ for 15 minutes on a hot plate. The substrate is then placed in a glove box to spray the organic photovoltaic solution. The organic photoelectric material solution is prepared by dissolving an electron donor material and an electron acceptor material in a mixed solvent of chloroform and chlorobenzene (volume ratio is 7. Concentration of organic photoelectric material solution used: 2.2mg/ml; the substrate moving speed was 0.2mm/s, and the flow rate of the syringe pump was set as: 20 mu L/min. In order to compare the effect of the film prepared by the common electrostatic spraying device, two films are respectively prepared by the common Electrostatic Spraying (ES) and a four-electrode-based electrostatic spraying device (QES), and the optical appearance is observed by a white light interferometer (manufacturer Zeta). As shown in fig. 5, the haze of ES is a circular haze, and the haze of QES is a long-striped haze having an aspect ratio of 8. The difference of the fog spot shapes influences the average distance between liquid drops and the fusion probability of the liquid drops, a plurality of pinhole defects exist on the film prepared by the ES on the optical topography, and no obvious pinhole defect exists on the film prepared by the QES due to the large density of the liquid drops.
After the organic photoelectric film is prepared by spraying, the substrate is placed on a hot plate for annealing for 10 minutes at 100 ℃, and after the annealing is finished, the organic photoelectric film is spin-coated with PDINO solution with the concentration of 1mg/ml and the spin-coating parameter of 3000rpm 30s. Then transferring the sample to a vacuum evaporation device for evaporation of an Ag electrode, wherein the vacuum degree during evaporation is 6 multiplied by 10 -4 Pa, ag purity 99.99%, evaporation rate
Figure BDA0003187496570000072
The active area (cathode and anode overlap) of the prepared device was 0.0425cm 2 The thickness of each layer of vacuum evaporation is detected by a quartz crystal oscillator thickness monitor. The measurement was carried out under the illumination of AM1.5G (100 mW/cm) generated by a solar simulator 2 ) The method is carried out. The current density-voltage curve was measured with Keithley 2400. The devices were not encapsulated and all testing was done in a glove box with device performance test results as shown in table 1 and fig. 6. And after the device performance test is finished, testing the External Quantum Efficiency (EQE) of different devices.
The structure of the device is glass substrate/ITO/PEDOT: PSS (40 nm)/PM 6: N3 (120 nm)/PDINO (10 nm)/Ag (100 nm).
This example compares the performance difference between PM6: N3 organic photovoltaic cells prepared by the present invention and a conventional electrostatic spray apparatus in the same structure device. Compared with the film prepared by ES, the film prepared by QES is more compact and uniform, and the organic photovoltaic cell prepared on the basis has higher photoelectric conversion efficiency. As can be seen from the device performance table, both the short circuit current density and the fill of the QES fabricated devices are significantly improved due to the reduced exciton recombination caused by the reduction of pinhole defects, while the increase in fill factor is due to the higher interface contact which improves charge transport.
TABLE 1 Performance parameters of ES and QES prepared PM6: N3 organic solar cell devices on ITO substrates
Figure BDA0003187496570000071
Figure BDA0003187496570000081
Example 2
Preparing an organic photoelectric film on a cleaned flexible base PET, ultrasonically cleaning a PET substrate by detergent, deionized water, acetone and isopropanol for 15 minutes in sequence, drying at 80 ℃ for at least 1 hour, and then carrying out plasma treatment for 1min. The PH1000 was spin coated at room temperature with spin coating parameters of 2000rpm 30s. The substrate was then annealed on a hot plate at 80 ℃ for 15 minutes. PSS was then spin coated on PEDOT at pH1000 with spin coating parameters of 3000rpm 30s. The substrate was then annealed on a hot plate at 100 ℃ for 15 minutes. The substrate is then placed in a glove box to spray the organic photovoltaic solution. The organic photoelectric material solution is prepared by dissolving an electron donor material and an electron acceptor material in a mixed solvent of chloroform and chlorobenzene (volume ratio is 7. Concentration of organic photoelectric material solution used: 2.2mg/ml; the substrate moving speed was 0.2mm/s, and the flow rate of the syringe pump was set as: 20 μ L/min. After the organic photoelectric film is prepared by spraying, the substrate is placed on a hot plate for annealing for 10 minutes at 100 ℃, and after the annealing is finished, the organic photoelectric film is spin-coated with PDINO solution with the concentration of 1mg/ml and the spin-coating parameter of 3000rpm 30s. Then transferring the film to a vacuum evaporation instrument for evaporation of Ag electrode during evaporationDegree of vacuum of 6X 10 -4 Pa, ag purity 99.99%, evaporation rate
Figure BDA0003187496570000082
The active area (cathode and anode overlap) of the prepared device was 0.0425cm 2 The thickness of each layer of vacuum evaporation is detected by a quartz crystal oscillator thickness monitor. The measurement was carried out under the illumination of AM1.5G (100 mW/cm) generated by a solar simulator 2 ) The method is carried out. The current density-voltage curve was measured with Keithley 2400. The devices were not encapsulated and all testing was done in a glove box with device performance test results as shown in table 2 and fig. 7.
The structure of the device is PET/PH1000 (80 nm)/PEDOT: PSS (40 nm)/PM 6: N3 (120 nm)/PDINO (10 nm)/Ag (100 nm).
This example compares the difference in photoelectric properties of PM6: N3 organic photoelectric thin films prepared according to the present invention and a conventional electrostatic spraying apparatus on a flexible substrate PET. As can be seen from the device results shown in table 2, the device fabricated by QES on the flexible substrate PET resulted in an increase in the device short circuit density, fill factor, and photoelectric conversion efficiency due to the improvement in the morphology of the active layer.
TABLE 2 PM6: N3 organic solar electric device Performance parameters by ES and QES on PET substrate
Figure BDA0003187496570000091
Example 3
Preparing an organic photoelectric film on a cleaned ITO glass substrate, ultrasonically cleaning the ITO glass substrate by detergent, deionized water, acetone and isopropanol for 15 minutes in sequence, drying the ITO glass substrate for at least 1 hour at 80 ℃, and then carrying out plasma treatment for 1min. PSS was spin coated at room temperature with a spin coating parameter of 3000rpm 30s. The substrate was then annealed at 150 ℃ for 15 minutes on a hot plate. The substrate is then placed in a glove box to spray the organic photovoltaic solution. The organic photoelectric material solution is prepared by dissolving an electron donor material and an electron acceptor material in a mixed solvent of chloroform and chlorobenzene (volume ratio is 7. Concentration of organic photoelectric material solution used: 2.2mg/ml; the moving speed of the substrate is 0.2mm/s, and the flow rate of the injection pump is set as follows: 20 mu L/min.
After the organic photoelectric film is prepared by spraying, the substrate is placed on a hot plate and annealed for 10 minutes at 100 ℃, after the pre-annealing is finished, the organic photoelectric film is respectively prepared with a PDINO film by ES and QES devices, the concentration is 1mg/ml, the distance between a needle head and a substrate is 2cm, the flow rate is 8 mu L/min, and the moving speed of the substrate is 0.3mm/s. Then transferring the sample to a vacuum evaporation instrument for evaporation of Ag electrode, wherein the vacuum degree is 6 multiplied by 10 during evaporation -4 Pa, ag purity of 99.99%, evaporation rate
Figure BDA0003187496570000093
The active area (cathode and anode overlap) of the prepared device was 0.0425cm 2 The thickness of each layer of vacuum evaporation is detected by a quartz crystal oscillator thickness monitor. The measurement was carried out under the illumination of AM1.5G (100 mW/cm) generated by a solar simulator 2 ) The method is carried out. The current density-voltage curve was measured with Keithley 2400.
This example compares the difference in photoelectric properties between organic photoelectric thin films of an active layer and an interface layer on an ITO substrate, which were prepared in sequence by the present invention and a common electrostatic spray apparatus, respectively. As can be seen from the device results shown in table 3 and fig. 8, the device with QES prepared interface layer PDINO also has significant improvement in photoelectric conversion efficiency of the device compared to the ES device.
TABLE 3 ES and QES preparation of interface layer Performance parameters of organic solar devices PDINO
Figure BDA0003187496570000092
Figure BDA0003187496570000101
The embodiment can prove that the four-electrode electrostatic spray printing device is suitable for preparing various organic photoelectric functional films, and the shape of the film prepared by electrostatic spray is obviously improved compared with the shape of the film prepared by common electrostatic spray, so that the performance of a device is improved.
Furthermore, it should be understood that although the present specification describes embodiments, not every embodiment includes only a single embodiment, and such description is for clarity purposes only, and it is to be understood that all embodiments may be combined as appropriate by one of ordinary skill in the art to form other embodiments as will be apparent to those of skill in the art from the description herein.

Claims (9)

1. A four-electrode electrostatic spray printing device is characterized by comprising an active liquid supply system, an additional high-voltage system and a three-dimensional moving platform, wherein the additional high-voltage system comprises a high-voltage power supply and a four-electrode structure electrically connected with the high-voltage power supply, and the four-electrode structure comprises a cross-shaped fixing frame, a needle head arranged in the middle of the cross-shaped fixing frame and four electrode columns arranged at four ends of the fixing frame; the active liquid supply system comprises an injector communicated with the needle head and a syringe pump communicated with the injector; the three-dimensional moving platform is used for generating relative motion between the needle head and the substrate on which the prepared film is placed.
2. The four-electrode electrostatic spray printing apparatus according to claim 1, wherein the cross-shaped holder includes a first holder and a second holder perpendicular to each other, the needle is disposed at a perpendicular crossing portion of the first holder and the second holder, two first electrodes are disposed on the first holder with the perpendicular crossing portion as a symmetrical point, and two second electrodes are disposed on the second holder with the perpendicular crossing portion as a symmetrical point.
3. A four-electrode electrostatic spray printing apparatus according to claim 2, wherein the two first electrodes are at a horizontal distance of 5-30mm from the needle; the horizontal distance between the two second electrodes and the needle is 5-30mm.
4. A four-electrode electrostatic spray printing apparatus according to claim 2, wherein a high voltage connection of said high voltage power supply is connected to said two first electrodes, and two ground connections of said high voltage power supply are connected to said substrate and said two second electrodes, respectively.
5. A four-electrode electrostatic spray printing apparatus according to claim 2, wherein the first electrode and the second electrode are both cylindrical.
6. The four-electrode electrostatic spray printing apparatus according to claim 1, wherein the three-dimensional moving platform comprises a fixed column for fixing the syringe pump and movable in the Z-axis direction, and a base plate located below the needle and movable in the X-axis and Y-axis directions.
7. A method for preparing a thin film based on the four-electrode electrostatic spray printing apparatus of any one of claims 1 to 6, comprising the steps of:
storing the prepared printing solution in an injector, and communicating the injector with a needle head;
setting the flow rate of a syringe pump, turning on the syringe pump, and pushing out the printing solution in the syringe through the syringe pump;
starting a high-voltage power supply, and increasing the voltage until the long-strip-shaped fog spots below the needle head are observed;
and placing the substrate on a substrate, and setting the moving speed of the substrate to enable the three-dimensional moving platform to move according to a preset route to finish film printing.
8. The method of manufacturing a thin film for a four-electrode electrostatic spray printing apparatus as claimed in claim 7, wherein the moving speed of the substrate is 0.01mm/s to 10mm/s.
9. The method for preparing the film of the four-electrode electrostatic spray printing device according to claim 7, wherein the length-width ratio of the elongated fog spots is 2.
CN202110866502.2A 2021-07-29 2021-07-29 Four-electrode electrostatic spray printing device and film preparation method Active CN113713975B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110866502.2A CN113713975B (en) 2021-07-29 2021-07-29 Four-electrode electrostatic spray printing device and film preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110866502.2A CN113713975B (en) 2021-07-29 2021-07-29 Four-electrode electrostatic spray printing device and film preparation method

Publications (2)

Publication Number Publication Date
CN113713975A CN113713975A (en) 2021-11-30
CN113713975B true CN113713975B (en) 2022-10-04

Family

ID=78674300

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110866502.2A Active CN113713975B (en) 2021-07-29 2021-07-29 Four-electrode electrostatic spray printing device and film preparation method

Country Status (1)

Country Link
CN (1) CN113713975B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1277371A (en) * 1969-08-07 1972-06-14 Nippon Kogie Kogyo Company Ltd Method and apparatus for spraying liquid
CN111382495A (en) * 2018-12-28 2020-07-07 达索系统美国公司 Simulation of robotic painting for electrostatic surround application

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104723678B (en) * 2015-03-12 2017-05-24 上海交通大学 Electro hydrodynamic preparation device and method for batch micro-droplets

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1277371A (en) * 1969-08-07 1972-06-14 Nippon Kogie Kogyo Company Ltd Method and apparatus for spraying liquid
CN111382495A (en) * 2018-12-28 2020-07-07 达索系统美国公司 Simulation of robotic painting for electrostatic surround application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
《JOURNAL OF AEROSOL SCIENCE》;Li Cheng，Chang Marsha，Yang Weiwei，Madden Aaron,Deng Weiwei;《Ballpoint pen tips as robust cone-jet electrospray emitters》;20141224;第10-15页 *
《农机化研究》;廉琦，张伟;《静电喷头电极对雾滴沉积效果的影响》;20160601;第188-193页 *

Also Published As

Publication number Publication date
CN113713975A (en) 2021-11-30

Similar Documents

Publication Publication Date Title
Chen et al. Solution-processed copper nanowire flexible transparent electrodes with PEDOT: PSS as binder, protector and oxide-layer scavenger for polymer solar cells
Zheng et al. Effect of in situ annealing on the performance of spray coated polymer solar cells
CN101609870B (en) Organic solar cells and method of manufacturing the same
Kang et al. Spray-coated ZnO electron transport layer for air-stable inverted organic solar cells
JP6151275B2 (en) Patterned organic semiconductor layer
CN103906703B (en) For the method and apparatus being aligned by the nano wire of electrostatic spinning process deposition
CN101889357A (en) Method for production of an organic light emitting diode or of an organic solar cell and organic light emitting diodes or solar cells produced therewith
US9735361B2 (en) Method of making a stack of the type comprising a first electrode, an active layer, and a second electrode
CN108057590A (en) Spray coating liquor, calcium titanium ore bed and preparation method thereof, perovskite battery
Tan et al. Electrodepostied polyaniline films decorated with nano-islands: Characterization and application as anode buffer layers in solar cells
Zhao et al. Effects of Damkhöler number of evaporation on the morphology of active layer and the performance of organic heterojunction solar cells fabricated by electrospray method
CN113713975B (en) Four-electrode electrostatic spray printing device and film preparation method
CN109671845B (en) Method for improving photoelectric characteristics of flexible polymer transparent conductive film and application
KR102026428B1 (en) Forming method of high conductive polymer film including a plurality of conductive treatment
JP2014113543A (en) Thin film forming device and organic el element
JP5945379B2 (en) Method for forming organic thin film and solar cell formed using the same
CN105870343B (en) A kind of method for improving organic polymer power conversion efficiency (pce)
Zheng et al. Investigation of in situ annealing on poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonate): towards all-solution-processed inverted polymer solar cells
Zhao et al. Morphology and electrical characteristics of polymer: Fullerene films deposited by electrospray
WO2020077710A1 (en) Polymer-metal chelate cathode interface material and use thereof
CN101931053A (en) Indium tin oxide (ITO) stereo electrode, preparation method and preparation device thereof as well as preparation method of solar battery
WO2017078239A1 (en) Electron collection layer for perovskite solar cell manufactured by electrostatic spray deposition, and manufacturing method therefor
Chen et al. Inkjet printing of composite hole transport layers and bulk heterojunction structure for organic solar cells
KR101481939B1 (en) Method for manufacturing light extraction nanopatterning plate by transparent powder
CN106299134A (en) The combined solar battery of a kind of patterning and colored solar battery module thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant