Reflux quantitative combined atmosphere annealing device and method

Abstract

The invention discloses a reflux quantitative combined atmosphere annealing device and method, and belongs to the technical field of thin film material preparation. The device can inject organic gas into the organic steam humidifier, and the organic gas is mixed with original gas in the gas mixer to obtain mixed gas meeting set conditions; the mixed gas is blown out towards the film supporting platform through a gas spray gun, and meanwhile the film supporting platform is heated by a heater; in the system, linear purging and linear annealing are linked, and the purging area and the heated area of the film are always consistent, so that the organic atmosphere is fully utilized. According to the device, the problem of poor repeatability caused by non-quantitative doping atmosphere and non-uniform atmosphere diffusion is avoided, the working environment of the whole system is room pressure normal temperature, the problem of atmosphere leakage of a high-pressure organic gas cylinder is avoided, and the experiment safety risk is reduced.

Description

Technical Field

[0001] The invention belongs to the field of thin film material preparation in the fields of semiconductor photoelectricity, photoelectrochemistry, electrocatalysis, etc., and specifically relates to a reflux quantitative combined atmosphere annealing device and method. Background Art

[0002] In the preparation of the entire battery device, the quality of the perovskite light-absorbing layer usually determines the efficiency and stability of the entire device. The soft lattice characteristics make perovskite more tolerant to defects than traditional inorganic semiconductors, making perovskite an ideal material for preparing optoelectronic devices by solution method. However, the perovskite liquid film prepared by spin coating is very sensitive during the annealing and crystallization process. Changes in external temperature and atmosphere can easily lead to uneven film quality, and repeatability is difficult to improve; even if the annealing operation is performed in a glove box, the atmosphere in the box is difficult to control.

[0003] Some literatures show that adding some molecules of different polarities at different stages in the preparation of perovskite layers will significantly affect the quality of thin film crystals: for example, in the synthesis of hybrid perovskite films, antisolvent engineering is a relatively common synthesis method, which is to assist nucleation in advance by dropping organic solutions with poor polarity during spin coating, thereby achieving the purpose of improving crystal quality. However, the error of artificial antisolvent dropping (drip time, drip height, and drop amount uncertainty) brings many uncertain factors to the film quality. In addition, there are also studies showing that adding a trace amount of organic atmosphere during the perovskite annealing process will also assist the perovskite in better crystallization and film formation, but many studies on the participation of organic atmosphere in annealing are only qualitative analysis (for example, dropping a few drops of organic solvent on the heating table, relying on the solvent evaporation to diffuse to the film surface to participate in annealing), and the optimal concentration of the atmosphere is still unknown. In addition, whether the atmosphere diffuses uniformly to the film surface, the error of each drop (drop location), and the airflow caused by the circulation in the glove box greatly reduce the repeatability of the experimental results. Summary of the invention

[0004] The purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art and provide a reflux quantitative combined atmosphere annealing device and method to solve the problem in the prior art that it is difficult to accurately control the annealing atmosphere during the perovskite annealing process, it is difficult to control the experimental accuracy during the experimental process, and thus it is difficult to control the quality of the perovskite film.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] A reflux quantitative combined atmosphere annealing device comprises a gas cylinder, the gas output pipeline of the gas cylinder is divided into a first type of gas pipeline and a second type of gas pipeline, the first type of gas pipeline is connected to a gas mixer, the second type of gas pipeline is connected to the gas mixer after passing through an organic steam humidifier, and the outlet of the gas mixer is connected to an atmosphere bin;

[0007] A film support platform is provided in the annealing atmosphere chamber, and a second air inlet and an air outlet are respectively opened on both sides of the film support platform; a gas spray gun is provided on the film support platform, and a gas conduit is connected to the upper end of the gas spray gun, and a heater is provided at the lower end of the film support platform; the gas conduit and the heater are both slidably connected to the atmosphere chamber;

[0008] The inlet of the gas conduit is connected to the outlet of the gas mixer, and two arc surfaces are arranged on both sides of the air outlet of the gas spray gun, the arc of the arc surface close to the second air inlet is smaller than the arc of the arc surface close to the air outlet, the centers of the two arc surfaces are close to the air outlet, and the lower ends of the two arc surfaces form an air outlet;

[0009] The outlet of the gas lance and the inner end of the heater are in the same vertical plane;

[0010] The second air inlet is communicated with the gas cylinder.

[0011] A further improvement of the present invention is:

[0012] Preferably, the lower end of the second air inlet and the upper surface of the membrane supporting platform are in the same plane.

[0013] Preferably, the gas spray gun is a plate-shaped structure, and the lower air outlet of the gas spray gun is inclined toward the air outlet.

[0014] Preferably, a guide rail is provided in the atmosphere chamber, and the guide rail is slidably connected to the gas conduit; and the heater is slidably connected to the atmosphere chamber via a screw structure.

[0015] Preferably, the organic vapor humidifier comprises a shell, a liquid chamber and a support platform are arranged in the shell, an organic vapor humidification column is arrayed between the liquid chamber and the support platform, and the upper end of the organic vapor humidification column is inserted into the liquid chamber;

[0016] A first air inlet and an air outlet are respectively arranged on both sides of the shell.

[0017] Preferably, both the first type of gas pipeline and the second type of gas pipeline are provided with float flowmeters.

[0018] Preferably, a tee is provided at the inlet of the gas mixer, and the first type of gas pipeline and the second type of gas pipeline are respectively connected to the inlet of the tee.

[0019] Preferably, a gas heat exchanger is provided between the gas mixer and the atmosphere chamber.

[0020] Preferably, the inlet portion of the gas conduit and the outer end of the heater are connected by a connecting rod.

[0021] An annealing method based on the above-mentioned reflux quantitative combined atmosphere annealing device, placing a film to be heat-treated on a film support platform;

[0022] The gas cylinder inputs the gas into the first type of gas pipeline and the second type of gas pipeline respectively. The gas in the second type of gas pipeline carries the organic gas after being processed by the organic steam humidifier; the first type of gas pipeline and the second type of gas pipeline enter the gas conduit after being mixed in the gas mixer; the flow rates of the first type of gas pipeline and the second type of gas pipeline are adjusted to adjust the mixing ratio of the two types of gases in the gas mixer;

[0023] The gas conduit blows the mixed gas toward the film support platform through the gas spray gun, the second air inlet blows air toward the film support platform, and the heater heats the film support platform;

[0024] During heat treatment, the gas lance and heater move synchronously.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] The present invention discloses a reflux quantitative combined atmosphere annealing device and method. The device outputs two types of gas pipelines from a gas cylinder. After one type of gas pipeline is injected with organic gas through an organic steam humidifier, it is mixed with the original gas in a gas mixer to obtain a mixed gas that meets the set conditions; the mixed gas is blown toward a film support platform through a gas spray gun, and the heater heats the film support platform at the same time; the structure can evenly mix multiple gas sources (organic and inorganic) as annealing atmospheres, and each atmosphere is quantitatively controllable, so as to achieve film annealing under a specified atmosphere, and the trace atmosphere is quantitative. During the heating process, while the gas spray gun sprays the mixed gas, the second air inlet blows air to the film surface at the same time. Because the air outlet part is designed as a curved surface, the air outlet is inclined toward the air outlet direction, but exhausts toward the heated surface. In this system, the linear atmosphere purge is linked with the linear annealing, and the film is always purged and heated. The atmosphere will be fully utilized under this experimental condition. Different from the traditional heating platform that heats the entire battery at the same time, the film heating process in this mode is directional and slow, and matches the atmosphere purge process. In addition, the device does not require manual operation throughout the process, avoiding the problem of poor film quality due to uneven doping atmosphere and uneven atmosphere diffusion. In addition, this film annealing process is more suitable for assembly line operation. The film annealing process can be stabilized through the control of the connecting rod, so that the uniformity and repeatability of the film are improved. The working environment of the whole system is room pressure and normal temperature. There is no problem of atmosphere leakage in the high-pressure organic gas cylinder, which reduces the safety risk of the experiment.

[0027] Furthermore, the second gas inlet and the upper surface of the film support platform are in the same plane, so that the gas output from the second gas inlet can be directed between the gas spray gun and the atmosphere chamber.

[0028] Furthermore, the gas spray gun is a plate-shaped structure, so that the synchronous blowing can span the entire width of the film.

[0029] Furthermore, the organic atmosphere of the present invention is adsorbed on the liquid adsorbent through an organic solvent, so that part of the gas can be adsorbed when the gas passes through, and at the same time, the amount of organic gas adsorbed in the gas can be controlled by controlling the temperature and the saturated vapor pressure of the organic atmosphere.

[0030] Furthermore, the present invention allows organic gas to be added to the gas through an organic steam humidifier, and for organic sources with a high boiling point (not easy to prepare into high-pressure gas cylinders), the production cost of using high-pressure gas cylinders can be saved. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 is a system structure diagram of the present invention;

[0032] Figure 2 is a cross-sectional view of an organic steam humidifier of the present invention;

[0033] Figure 3 is a three-dimensional perspective view of the atmosphere chamber of the present invention;

[0034] Figure 4 It is a two-dimensional side view of the atmosphere chamber of the present invention;

[0035] Figure 5 This is a simulation diagram of the gas flow direction when there is no second air inlet for blowing;

[0036] Figure 6 It is a gas flow simulation diagram during blowing in the present invention;

[0037] Among them: 1. gas cylinder; 2. first type of gas pipeline; 3. second type of gas pipeline; 4. gas mixer; 5. shell; 6. liquid inlet; 7. first air inlet; 8. support platform; 9. liquid discharge port; 10. organic vapor humidification column; 11. exhaust port; 12. liquid chamber; 13. three-way; 14. float flowmeter; 15. atmosphere chamber; 16. gas heat exchanger; 17. screw structure; 18. film support platform; 19. second air inlet; 20. guide rail; 21. gas spray gun; 22. gas conduit; 23. connecting rod; 24. heater; 25. air outlet; 26. groove; 27. organic vapor humidifier; 28. air outlet; 29. ​​air outlet; 30. other gas sources; 31. flow control valve; DETAILED DESCRIPTION

[0038] The present invention is further described in detail below in conjunction with the accompanying drawings:

[0039] In the description of the present invention, it should be noted that the orientations or positional relationships indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inside", "outside", etc. are based on the orientations or positional relationships shown in the drawings, and are only for the convenience of describing the present invention 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 cannot be understood as limiting the present invention; the terms "first", "second", and "third" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance; in addition, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection or a detachable connection; it can be directly connected or indirectly connected through an intermediate medium, and it can be the internal communication of two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0040] The present invention discloses a reflux quantitative combined atmosphere annealing device, which is mainly divided into four parts, which are respectively: a main gas source part (usually inert gas N2 or air, supplied by a gas pump or a high-pressure gas cylinder); an organic vapor humidification part (used to carry other trace organic gases); a gas mixing part (determines the final required flow rate); and a purge annealing part (the film is annealed and crystallized in this link).

[0041] The device includes a gas cylinder 1, which is provided with two types of pipelines for outputting gas, namely a first type of gas pipeline 2 and a second type of gas pipeline 3. The first type of gas pipeline 2 is directly connected to a gas mixer 4, and the second type of gas pipeline 3 enters the gas mixer 4 after passing through an organic vapor humidifier 27. The outlet of the gas mixer 4 is connected to an atmosphere chamber 15, and the atmosphere chamber 15 is also connected to the gas cylinder 1. The gas cylinder 1 is usually provided with inert gas N2 or air, and gas is supplied by an air pump or a high-pressure gas cylinder. The outlet of the gas cylinder 1 can be equipped with an air pump according to demand.

[0042] The first gas pipeline 2 and the second gas pipeline of the present invention are both provided with flow regulating valves 31, through which the flow rates on the two pipelines can be adjusted, thereby adjusting the volume of each gas entering the gas mixer 4, that is, adjusting the mixing ratio of the two gases.

[0043] In some embodiments of the present invention, the structural schematic diagram of the organic vapor humidifier 27 is as follows Figure 2 As shown, the organic vapor humidifier 27 is used to input into the second type of gas pipeline 3. The organic vapor humidifier 27 includes a shell 5, a support platform 8 and a liquid chamber 12 are arranged in the shell 5, the liquid chamber 12 is arranged at the upper end inside the gas mixer 4, and the support platform 8 is arranged at the lower end inside the shell 5. The liquid chamber 12 is a cavity structure inside, which is used to carry organic solvents. There are organic vapor humidification columns 10 in a rectangular array on the support platform 8. The upper ends of the organic vapor humidification columns 10 are inserted into the liquid chamber 12, and the insertion height is greater than the height of the liquid in the liquid chamber 12. The liquid chamber 12 is at the upper part of the organic vapor humidification column 10, so that the humidification column can be better moistened under the action of the gravity of the solvent.

[0044] It should be noted that the organic vapor humidification column 10 needs to be matched with different organic vapor humidification columns 10 according to different organic solvents, so that it has a large specific surface area structure, strong wettability to organic vapor, and will not react with organic vapor.

[0045] It should be understood that Figure 2 This is one of the embodiments of the organic steam humidifier 27 of the present invention. In actual application, the organic steam humidifier 27 can have other structural forms, as long as the conditions of carrying organic gas in the steam and humidifying the organic steam to saturation are met, such as Figure 2The organic steam humidification column 10 in the middle dotted frame can be replaced by other structures.

[0046] The device uses the physical parameters of organic vapor to quantify the content of organic atmosphere by controlling the temperature. The organic solvent enters the liquid chamber 12 through the liquid inlet 6, and the organic solvent passes through the organic vapor humidification column 10 and is adsorbed on the organic vapor humidification column 10. The organic vapor humidification column 10 has a large specific surface area and a small air flow resistance. Its main purpose is that when the air flow flows to the end of the channel, the organic gas carried by the gas reaches saturation (that is, the air pressure reaches the saturated vapor pressure). When the gas can no longer inhale the organic atmosphere, the internal atmosphere is controlled. The gas enters the interior of the housing 5 through the first air inlet 7, and after passing through the organic vapor humidification column 10, it flows out from the exhaust port 11. The liquid chamber 12 is provided with a sealing structure at the contact point between the organic vapor humidification column 10 and the liquid chamber 12 to prevent the liquid from leaking directly from the cavity to the inside of the channel. The organic solvent infiltrates the organic vapor humidification column 10 and penetrates downward by gravity and capillary action, so that the entire column is completely kept in an infiltrated state, so that the gas can reach the adsorption saturation state as soon as possible when it circulates. The design advantage of this structure is that as the liquid decreases, the adsorption column can remain wetted for a longer period of time, ensuring the adsorption amount of gas.

[0047] In addition, the saturated vapor pressure of a gas is calculated by this formula:

[0048] ln(P1 / P2)=(ΔH vap / R)((1 / T2)-(1 / T1)) (1)

[0049] In formula 1, ΔH vap is the vaporization enthalpy of the liquid, R is the ideal gas constant, which is 8.314 J / (K·mol), T1 and P1 are the known temperatures and the corresponding known vapor pressures at the temperatures; T2 is the actual temperature. It can be seen that temperature is the main factor determining vapor pressure.

[0050] Another point that needs to be explained is that the component does not have a heating source, that is, the airflow temperature T2 at the inlet and outlet is the same, both at room temperature. No heating treatment is performed because the airflow is discharged from the exhaust port 11 after being heated, and the temperature of the external pipeline is lower than the airflow temperature, and the saturated vapor pressure of the output pipeline doped with organic gas decreases, and the supersaturated vapor at this time liquefies, thereby blocking the gas pipeline.

[0051] In addition, the upper surface of the support platform 8 is designed to be a small-angle inclined structure (low on the left and high on the right in the figure), and the height of the exhaust port 7 side is higher than the height of the first air inlet 7 to prevent the dripping liquid from accumulating at the bottom of the channel and affecting the adsorption effect of the airflow. A vertical downward drain port 9 is provided on the shell 5, so that excess liquid will flow in along the slope and then flow out through the drain port 9. There is a gap at the bottom of the support platform 8 and the shell 5, so as to provide a certain buffer space for the liquid.

[0052] The gas treated by the organic steam humidifier 27 contains organic gas. Under normal circumstances, the organic gas in the gas path can reach saturation. By subsequently adjusting the mixing ratio of the first type of gas pipeline 2 and the second type of gas pipeline 3, the organic gas in the second type of gas pipeline 3 can be diluted, and then the content of organic gas in the final gas can be controlled, so that the gas ratio and atmosphere input into the atmosphere chamber 15 can meet the requirements.

[0053] See also Figure 1 , Figure 3 and Figure 4 A cavity is provided inside the atmosphere chamber 15, and a film support platform 18 is mounted inside the cavity. A groove 26 is provided on the film support platform 18, and a second air inlet 19 and an air outlet 25 are respectively provided on two opposite side walls of the film support platform 18, and the lower end of the second air inlet 19 is in the same plane as the film support platform 18; a screw structure 17 is provided below the film support platform 18, one end of the screw structure 17 is connected to the side wall of the atmosphere chamber 15, and the other end is connected to a heater 24, and the heater 24 and the lower side wall of the film support platform 18, the heater 24 and the bottom of the atmosphere chamber 15 are all slidably connected, so that the heater 24 can move below the film support platform 18 to heat the film support platform 18; the outer end of the heater 24 is connected to a gas conduit 22 through a connecting rod 23, and the input end of the gas conduit 22 It is connected to the output end of the gas mixer 4, and the gas conduit 22 is parallel to the moving direction of the heater 24. The gas conduit 22 is inserted into the atmosphere chamber 15 from the side wall where the gas outlet 25 is located. The gas conduit 22 is inserted into the end of the atmosphere chamber 15 and is connected to a gas spray gun 21. The gas spray gun 21 is a plate-like structure with a rectangular cavity opened inside for passing gas. The upper ends of the gas spray gun 21 are slidably connected to two guide rails 20, and the two guide rails 20 are fixedly arranged on the upper end surface inside the atmosphere chamber 15; the gas spray gun 21 is perpendicular to the gas conduit 22, and the lower end of the gas spray gun 21 is an air outlet part. Two arc surfaces are arranged on both sides of the air outlet part 28, and the arc radius near the second air inlet 19 is smaller than the arc radius near the air outlet 25. The centers of the two arc surfaces are near the air outlet 25, and the lower ends of the two arc surfaces form an air outlet 28.

[0054] In some embodiments of the present invention, the gas conduit 22 is connected to the heater 24 via a connecting rod 23. In order to prevent the gas conduit 22 from being heated, the connecting rod 23 is made of a heat insulator.

[0055] In some embodiments of the present invention, the first type of gas pipeline and the second type of gas pipeline, each type of gas pipeline can be set in parallel with multiple gas pipelines according to the situation, and each gas pipeline is provided with a float flowmeter 14. The air pump can provide a stable outlet air pressure. According to the Bernoulli principle, when the inlet and outlet air pressures are determined to be constant, the flow measured by the float flowmeter 14 is considered to be reliable. If it is an outdoor environment, it is necessary to add a pressure reducing valve while equipping the gas cylinder to ensure the inlet pressure of the float flowmeter 14.

[0056] In some embodiments of the present invention, the first type of gas pipeline 2 and the second type of gas pipeline 3 are mixed through a tee 13 before entering the gas mixer 4. In the tee 13, the gases in the first type of gas pipeline 2 and the second type of gas pipeline 3 are pre-mixed and then enter the inlet section of the gas mixer 4. The gas mixer enters from the inlet end and contains staggered baffles inside, which can allow different types of gases to be fully mixed and discharged from the outlet section.

[0057] In some embodiments of the present invention, a gas heat exchanger 16 is provided on the connecting pipeline between the gas mixer 4 and the atmosphere chamber 15 to control the inlet mixed gas temperature of the gas conduit 22 .

[0058] In some embodiments of the present invention, the gas mixer 4 can be fed with other types of gases, which are determined according to the type of gas required for purging, and are other gas sources 30 in the figure.

[0059] The working process of the above device is:

[0060] The gas cylinder 1 inputs the gas into the first type gas pipeline 2 and the second type gas pipeline 3 respectively. The gas in the second type gas pipeline 3 carries organic gas after being processed by the organic steam humidifier 27, and the amount of organic gas carried is adjusted by the temperature in the organic steam humidifier 27; after the first type gas pipeline 2 and the second type gas pipeline 3 are mixed in the gas mixer 4, the mixed gas flow output by the gas mixer 4 is connected to the gas conduit 22 and the air gun spray gun 21 through the gas heat exchanger 16 and finally purged to the surface of the film. The guide rail 20 limits the gas spray gun 21 so that the gas spray gun 21 can only move forward and backward. In addition, the position of the gas purge, the air outlet 29 of the gas spray gun 21, is set to be in the same vertical plane as the inner end of the heater 24, so that the heating of the film is synchronized with the atmosphere, so that the film can be affected by the mixed gas when it grows. The inner end of the heater 24 is connected to a spiral structure 17, and the advancement step is controlled by a motor to control the movement rate of the spiral structure 17 and the gas conduit 22. The film support platform 18 is designed with a groove 26 inside to fix the film and prevent the film from changing its position during the atmosphere purge process. The thinner the platform thickness, the better to ensure efficient heat conduction. It is worth noting that the direction of the air flow ejected by the air nozzle is at a certain angle to the film. Its function is as follows Figure 5 As shown in the figure: During the purging process, a negative pressure area will be formed on the left side of the nozzle. The negative pressure makes the atmosphere inside the box move toward the nozzle (blue arrow). This structure is to prevent the unheated film from being affected by the doped atmosphere due to the diffusion of the atmosphere (yellow arrow). The air inlet 3 is also provided by the air pump, such as Figure 6 As shown, the air flow enters from the air inlet and is blown horizontally to the air nozzle. The air pump atmosphere replaces the atmosphere in the box to protect the unannealed part of the film. At the same time, the air flow temperature is low, and the influence of the heat source through heat conduction is weakened during the flow process.

[0061] The growth of thin films is microscopic and sensitive. The traditional air gun purging process is to wait until the entire glass is purged before annealing. The part of the film that is purged first will experience more complex atmosphere disturbances before annealing, which can easily lead to uneven overall film quality. The present invention aims to maximize the effect of the organic atmosphere by linking purging and annealing. The additional gas path setting can also ensure that the crystallized part is not disturbed by the external atmosphere, which to a certain extent avoids the problems of uneven film quality and poor repeatability. The film annealing process is a crystallization process accompanied by solvent evaporation. The main function of gas purging is to make the precursor solution (commonly known as wet film) on the film quickly reach an oversaturated state. At this time, most of the solvent in the wet film has evaporated with the high-pressure gas, and a large number of nucleation sites are formed in the wet film. These nucleation sites will help the film to form a high-quality and ordered crystal structure in the next high-temperature annealing stage. During this period, the introduction of trace organic vapor will affect the volatilization rate of the wet film on the one hand. The selection of a suitable atmosphere can effectively regulate the mass transfer of the entire process of film nucleation and crystallization; on the other hand, during the organic vapor treatment, the dissolution characteristics of the vapor on the wet film may cause the film to have a repeated process of dissolution / recrystallization. The crystallization process is the process in which the system gradually reaches a stable state, while the dissolution process makes the system more active. It can be seen that the introduction of organic solvents affects both the mass transfer of the system and the energy transfer of the system. The introduction of this set of atmosphere-controlled annealing equipment not only makes it easy to control the processing parameters, namely temperature, flow rate and processing time, but most importantly, optimizes the entire annealing process and improves the crystal quality. In addition, this set of film annealing process is more suitable for assembly line operation. The film annealing process can be stabilized by controlling the connecting rod, so that the uniformity and repeatability of the film are improved.

[0062] The present invention has the following characteristics

[0063] (1) The organic gas content is quantitatively controlled by the dynamic balance between the saturated vapor pressure of the organic source and the flow of the controllable inert atmosphere (N2) in a closed container.

[0064] (2) Through the combined action of capillary and gravity, the humidifying component with a large specific surface area in the channel is completely wetted. When the gas flows through the humidifying component, the surface solvent evaporates faster and quickly reaches solvent vapor saturation.

[0065] (3) In order to ensure that the gas is absorbed to saturation, the steam is pre-condensed in the pipeline (lower than the gas temperature) before entering the gas mixer. The pipeline temperature is manually controlled by the supercooling equipment, and the condensed gas flows back to the steam pressure saturation device.

[0066] (3) The annealing method is linear push annealing (heating table push annealing), that is, the heating table starts to contact from one end of the film (the film is heated from one end) until it is pushed to the other end of the film.

[0067] (4) The push-type hot plate is connected to the air knife through a connecting rod, so that the air knife and the hot plate act on the same position of the film.

[0068] (5) The curved shape of the air nozzle makes the ejected air flow form an acute angle with the film.

[0069] (6) Another stream of N2 gas is provided by an air pump and blown horizontally from the other end of the annealing device (the other end of the film) to prevent the unheated film from being affected by the doped atmosphere due to atmosphere diffusion. At the same time, the gas flow temperature is relatively low to minimize the effect of thermal diffusion.

[0070] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A reflux quantitative combined atmosphere annealing device, characterized in that: The invention comprises a gas cylinder (1), wherein the gas output pipeline of the gas cylinder (1) is divided into a first type of gas pipeline (2) and a second type of gas pipeline (3), the first type of gas pipeline (2) is connected to a gas mixer (4), the second type of gas pipeline (3) is connected to the gas mixer (4) after passing through an organic steam humidifier (27), and the outlet of the gas mixer (4) is connected to an atmosphere chamber (15); A film support platform (18) is provided in the annealing atmosphere chamber (15), and the atmosphere chamber (15) is provided with a second air inlet (19) and an air outlet (25) on both sides of the film support platform (18); a gas spray gun (21) is provided on the film support platform (18), and the upper end of the gas spray gun (21) is connected to a gas conduit (22), and a heater (24) is provided at the lower end of the film support platform (18); the gas conduit (22) and the heater (24) are both slidably connected to the atmosphere chamber (15); The inlet of the gas conduit (22) is connected to the outlet of the gas mixer (4), and two arc surfaces are arranged on both sides of the air outlet portion (28) of the gas spray gun (21), the arc of the arc surface close to the second air inlet (19) is smaller than the arc of the arc surface close to the air outlet (25), the centers of the two arc surfaces are close to the air outlet (25), and the lower ends of the two arc surfaces form the air outlet (28); The outlet of the gas spray gun (21) and the inner end of the heater (24) are in the same vertical plane; The second air inlet (19) is in communication with the gas cylinder (1).

2. A reflux quantitative combined atmosphere annealing device according to claim 1, characterized in that: The lower end of the second air inlet (19) and the upper surface of the film support platform (18) are in the same plane.

3. The reflux quantitative combined atmosphere annealing device according to claim 1, characterized in that: The gas spray gun (21) is a plate-shaped structure, and the air outlet at the lower end of the gas spray gun (21) is inclined towards the air outlet (25).

4. The reflux quantitative combined atmosphere annealing device according to claim 1, characterized in that: A guide rail (20) is provided in the atmosphere chamber (15), and the guide rail (20) and the gas conduit (22) are slidably connected; the heater (24) is slidably connected to the atmosphere chamber (15) via a screw structure (17).

5. The reflux quantitative combined atmosphere annealing device according to claim 1, characterized in that: The organic vapor humidifier (27) comprises a housing (5), a liquid chamber (12) and a support platform (8) are arranged in the housing (5), an organic vapor humidification column (10) is arranged between the liquid chamber (12) and the support platform (8), and the upper end of the organic vapor humidification column (10) is inserted into the liquid chamber (12); A first air inlet (7) and an air outlet (11) are respectively provided on both sides of the housing (5).

6. The reflux quantitative combined atmosphere annealing device according to claim 1, characterized in that: Both the first-type gas pipeline (2) and the second-type gas pipeline (3) are provided with a float flowmeter (14).

7. The reflux quantitative combined atmosphere annealing device according to claim 1, characterized in that: A tee (13) is provided at the inlet of the gas mixer (4), and the first type of gas pipeline (2) and the second type of gas pipeline (3) are respectively connected to the inlet of the tee (13).

8. The reflux quantitative combined atmosphere annealing device according to claim 1, characterized in that: A gas heat exchanger (16) is provided between the gas mixer (4) and the atmosphere chamber (15).

9. The reflux quantitative combined atmosphere annealing device according to claim 1, characterized in that: The inlet portion of the gas conduit (22) and the outer end of the heater (24) are connected via a connecting rod (23).

10. An annealing method based on the reflux quantitative combined atmosphere annealing device according to claim 1, characterized in that: Placing the film to be heat-treated on a film support platform (18); The gas cylinder (1) inputs gas into the first type gas pipeline (2) and the second type gas pipeline (3) respectively. The gas in the second type gas pipeline (3) carries organic gas after being processed by the organic steam humidifier (27). The first type gas pipeline (2) and the second type gas pipeline (3) are mixed in the gas mixer (4) and enter the gas conduit (22). The flow rates of the first type gas pipeline (2) and the second type gas pipeline (3) are adjusted to adjust the mixing ratio of the two types of gases in the gas mixer (4). The gas conduit (22) blows the mixed gas toward the film support platform (18) through the gas spray gun (21), the second gas inlet (19) blows gas toward the film support platform (18), and the heater (24) heats the film support platform (18); During the heat treatment process, the gas lance (21) and the heater (24) move synchronously.

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