CN119384203A - A reflux quantitative combined atmosphere annealing device and method - Google Patents
A reflux quantitative combined atmosphere annealing device and method Download PDFInfo
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- CN119384203A CN119384203A CN202411469937.3A CN202411469937A CN119384203A CN 119384203 A CN119384203 A CN 119384203A CN 202411469937 A CN202411469937 A CN 202411469937A CN 119384203 A CN119384203 A CN 119384203A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
- H10K71/441—Thermal treatment, e.g. annealing in the presence of a solvent vapour in the presence of solvent vapors, e.g. solvent vapour annealing
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/811—Controlling the atmosphere during processing
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Abstract
本发明公开了一种回流定量的组合气氛退火装置和方法，属于薄膜材料制备技术领域。该装置能够在气体中注入有机蒸汽加湿器注入有机气体，在气体混合器中和原气体混合，获得满足设定条件混合气体；混合气体通过气体喷枪朝向薄膜支撑平台吹出，同时加热器对薄膜支撑平台加热；该系统中线性吹扫与线性退火联动，薄膜被吹扫与被加热的区域始终是一致的，使得有机气氛被充分利用。该装置，避免了因掺杂气氛不定量、气氛扩散不均匀而导致可重复性差的问题，整套系统的工作环境为室压常温，避免了高压有机气瓶的气氛泄露问题，降低了实验安全风险。
The present invention discloses a reflux quantitative combined atmosphere annealing device and method, belonging to the technical field of thin film material preparation. The device can inject organic gas into the gas through an organic steam humidifier, mix it with the original gas in a gas mixer, and obtain a mixed gas that meets the set conditions; the mixed gas is blown toward the film support platform through a gas spray gun, and the heater heats the film support platform at the same time; in this system, linear purging and linear annealing are linked, and the purged and heated areas of the film are always consistent, so that the organic atmosphere is fully utilized. The device avoids the problem of poor repeatability caused by uncertain doping atmosphere and uneven atmosphere diffusion. The working environment of the whole system is room pressure and normal temperature, which avoids the problem of atmosphere leakage of high-pressure organic gas cylinders and reduces the safety risk of experiments.
Description
Technical Field
The invention belongs to the field of film material preparation in the fields of semiconductor photoelectricity, photoelectrochemistry, electrocatalysis and the like, and particularly relates to a reflux quantitative combined atmosphere annealing device and method.
Background
In the fabrication of an overall battery device, the quality of the perovskite light absorbing layer generally determines the efficiency and stability of the overall device. The soft lattice property makes perovskite have larger tolerance to defects than traditional inorganic semiconductors, so that perovskite becomes an ideal material for preparing photoelectric devices by a solution method. However, the perovskite liquid film prepared by the spin coating method is very sensitive in the annealing crystallization process, the quality of the film is uneven due to the change of the external temperature and the atmosphere, the repeatability is difficult to improve, and even if the annealing operation is performed in a glove box, the atmosphere in the box is difficult to control.
Some documents show that adding molecules with different polarities at different stages in the preparation process of a perovskite layer can obviously influence the quality of a thin film crystal, for example, in the synthesis process of a hybrid perovskite thin film, antisolvent engineering is a common synthesis means, and the aim of improving the crystal quality is fulfilled by dropwise adding an organic solution with poorer polarity in the spin coating process to assist in nucleation in advance. However, errors of artificial anti-solvent dripping (uncertainty of dripping time, dripping height and dripping amount) bring about a plurality of uncertainty factors to film quality, besides, researches show that adding trace organic atmosphere in the perovskite annealing process can assist perovskite to form better crystallization film, but researches of adding a plurality of organic atmospheres into annealing are only qualitative analysis (such as dripping a plurality of organic solvents on a heating table and diffusing to the film surface to participate in annealing by virtue of solvent evaporation), the optimal concentration of the atmosphere is unknown, and in addition, whether the atmosphere diffuses to the film surface uniformly, errors of the quantity of each dripping (dripping position) and air flow influence caused by internal circulation of a glove box are greatly reduced, so that repeatability of experimental results is greatly reduced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a reflux quantitative combined atmosphere annealing device and method, so as to solve the problems that the annealing atmosphere is difficult to control accurately in the perovskite annealing process, the experimental precision is difficult to control in the experimental process, and the quality of a perovskite film is difficult to control in the prior art.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
The combined atmosphere annealing device comprises a gas cylinder, wherein a 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 with a gas mixer, the second type of gas pipeline is communicated to the gas mixer after passing through an organic steam humidifier, and an outlet of the gas mixer is communicated with an atmosphere bin;
A film supporting platform is arranged in the annealing atmosphere bin, and a second air inlet and an air outlet are respectively formed in two sides of the film supporting platform in the atmosphere bin; the film supporting platform is provided with a gas spray gun, the upper end of the gas spray gun is communicated with a gas conduit, and the lower end of the film supporting platform is provided with a heater;
The inlet of the gas conduit is communicated with the outlet of the gas mixer, two cambered surfaces are arranged on two sides of the air outlet part of the gas spray gun, the radian of the cambered surface close to the second air inlet is smaller than that of the cambered surface close to the air outlet, the centers of the two cambered surfaces are close to the air outlet, and the lower ends of the two cambered surfaces form an air outlet;
the outlet of the gas spray gun and the inner end of the heater are positioned on the same vertical plane;
the second air inlet is communicated with the air bottle.
The invention further improves that:
Preferably, the lower end of the second air inlet and the upper surface of the film supporting platform are on the same plane.
Preferably, the gas spray gun is of a plate-shaped structure, and an air outlet at the lower end of the gas spray gun is inclined towards the air outlet.
Preferably, the atmosphere chamber is provided with a guide rail which is in sliding connection with the gas conduit, and the heater is in sliding connection with the atmosphere chamber through a screw structure.
Preferably, the organic vapor humidifier comprises a shell, wherein a liquid chamber and a supporting table are arranged in the shell, organic vapor humidifying columns are arranged between the liquid chamber and the supporting table in an array mode, and the upper ends of the organic vapor humidifying columns are inserted into the liquid chamber;
The two sides of the shell are respectively provided with a first air inlet and an air outlet.
Preferably, the first-type gas pipeline and the second-type gas pipeline are provided with float flowmeters.
Preferably, a tee joint is arranged at the inlet of the gas mixer, and the first-type gas pipeline and the second-type gas pipeline are respectively communicated with the inlet of the tee joint.
Preferably, a gas heat exchanger is arranged between the gas mixer and the atmosphere bin.
Preferably, the inlet portion of the gas conduit and the outer end of the heater are connected by a connecting rod.
An annealing method based on the combined atmosphere annealing device for quantitative backflow comprises the steps of placing a film to be heat treated on a film supporting platform;
The gas cylinder respectively inputs gas into a first-class gas pipeline and a second-class gas pipeline, and the gas in the second-class gas pipeline carries organic gas after being processed by the organic steam humidifier;
The gas duct blows out the mixed gas towards the film supporting platform through the gas spray gun, the second gas inlet blows out towards the film supporting platform, and the heater heats the film supporting platform;
During the heat treatment, the gas spray gun and the heater move synchronously.
Compared with the prior art, the invention has the following beneficial effects:
The invention discloses a reflux quantitative combined atmosphere annealing device and method, wherein two types of gas pipelines are output from a gas cylinder, one type of gas pipeline is mixed with raw gas in a gas mixer after organic gas is injected through an organic steam humidifier, the mixed gas meeting set conditions is blown out towards a film supporting platform through a gas spray gun and is heated by a heater, multiple gas sources (organic and inorganic) can be uniformly mixed to be used as annealing atmosphere, each atmosphere is quantitatively controllable, film annealing under specified atmosphere is realized, and trace atmosphere is quantificational. In the heating process, the gas spray gun sprays mixed gas, and simultaneously the second air inlet blows air to the surface of the film, and because the air outlet part is designed to be a cambered surface, the air outlet is inclined towards the direction of the air outlet, but exhausts air towards the heated surface. In the system, the linear purging and the linear annealing of the atmosphere are linked, the purged and heated areas of the film are consistent all the time, and the atmosphere is fully utilized under the experimental condition. Unlike conventional heating stations that heat the entire cell simultaneously, the film heating process in this manner is directional and slow and matches the atmosphere purging process. In addition, the device does not need manual operation in the whole process, and the problem of poor film quality caused by non-quantitative doping atmosphere and non-uniform atmosphere diffusion is avoided. In addition, the film annealing process is more suitable for assembly line operation, and can stabilize the film annealing process through the control of the connecting rod, so that the uniformity and the repeatability of the film are improved. The working environment of the whole system is room pressure and normal temperature, the problem of atmosphere leakage of a high-pressure organic gas cylinder is avoided, and the experimental safety risk is reduced.
Further, the second air inlet and the upper surface of the film supporting platform are on the same plane, so that the air output by the second air inlet can face between the air spray gun and the atmosphere bin.
Further, the gas lance is of a plate-like configuration so that simultaneous purging can span the entire width of the film.
Further, the organic atmosphere of the present invention is adsorbed on the liquid adsorbent by the organic solvent, so that a part of the gas can be adsorbed when the gas passes through, and at the same time, the amount of the adsorbed organic gas in the gas can be controlled by controlling the saturated vapor pressure of the organic atmosphere by controlling the temperature.
Furthermore, the organic gas can be added into the gas through the organic steam humidifier, and the production cost of using the high-pressure gas bottle can be saved aiming at an organic source (which is not easy to prepare into the high-pressure gas bottle) with a higher boiling point.
Drawings
FIG. 1 is a system block diagram of the present invention;
fig. 2 is a cross-sectional view of an organic vapor humidifier of the present invention;
FIG. 3 is a perspective view of an atmosphere cartridge of the present invention;
FIG. 4 is a two-dimensional side view of an atmosphere cartridge of the present invention;
FIG. 5 is a simulated flow diagram of gas without a second gas inlet blowing;
FIG. 6 is a simulated graph of gas flow during blowing in accordance with the present invention;
The device comprises a gas cylinder, a first-class gas pipeline, a second-class gas pipeline, a 4-class gas mixer, a 5-class shell, a 6-class liquid inlet, a 7-class first gas inlet, a 8-class support table, a 9-class liquid outlet, a 10-class organic vapor humidifying column, a 11-class gas outlet, a 12-class liquid chamber, a 13-class three-way, a 14-class float flowmeter, a 15-class atmosphere bin, a 16-class gas heat exchanger, a 17-class screw structure, a 18-class film support platform, a 19-class second gas inlet, a 20-class guide rail, a 21-class gas spray gun, a 22-class gas guide pipe, a 23-class connecting rod, a 24-class heater, a 25-class gas outlet, a 26-class groove, a 27-class organic vapor humidifier, a 28-class air outlet part, a 29-class air outlet, a 30-class other gas source, a 31-class flow regulating valve;
Detailed Description
The invention is described in further detail below with reference to the attached drawing figures:
In the description of the present invention, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," "outer," and the like are merely for convenience of description and to simplify the description of the present invention, but rather to indicate or imply that the apparatus or elements being referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present invention, the terms "first," "second," "third," are used for descriptive purposes only and should not be construed as indicating or implying relative importance, and furthermore, the terms "mounted," "connected," or "coupled" should be construed broadly, for example, as being fixedly connected or as being detachably connected, or as being indirectly connected through intermediaries, or as being in communication with the inside of two elements unless otherwise specifically stated or defined. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
The invention discloses a reflux quantitative combined atmosphere annealing device which is mainly divided into four parts, wherein the main air source part (usually inert gas N2 or air, air supplied by an air pump or a high-pressure air bottle), the organic vapor humidifying part (used for carrying other trace organic gases), the gas mixing part (used for determining the final required flow) and the purging annealing part (used for annealing crystallization of a film in the link) are sequentially and respectively arranged according to the trend of an air path.
The device comprises a gas cylinder 1, wherein the gas cylinder 1 is provided with two types of pipelines for outputting gas, namely a first type gas pipeline 2 and a second type gas pipeline 3, the first type gas pipeline 2 is directly connected with a gas mixer 4, and the second type gas pipeline 3 enters the gas mixer 4 after passing through an organic steam humidifier 27. The outlet of the gas mixer 4 is connected with an atmosphere chamber 15, and the atmosphere chamber 15 is simultaneously connected with the gas cylinder 1. The gas cylinder 1 is usually provided with inert gas N 2 or air, and is supplied with air by an air pump or a high-pressure gas cylinder, and an outlet in the gas cylinder 1 can be provided with the air pump according to requirements.
The first-type gas pipeline 2 and the second-type gas pipeline are both provided with the flow regulating valve 31, and the flow on the two pipelines can be regulated through the flow regulating valve 31, so that the volume of each gas entering the gas mixer 4 is regulated, namely the mixing proportion of the two paths of gases is regulated.
In some embodiments of the present invention, as shown in fig. 2, the schematic structure of the organic vapor humidifier 27 is shown in fig. 2, the organic vapor humidifier 27 is used for inputting into the second type gas pipeline 3, the organic vapor humidifier 27 includes a housing 5, a support stand 8 and a liquid chamber 12 are disposed in the housing 5, the liquid chamber 12 is disposed at an upper end inside the gas mixer 4, the support stand 8 is disposed at a lower end inside the housing 5, a cavity structure is disposed inside the liquid chamber 12 and is used for carrying the organic solvent, a rectangular array of organic vapor humidification columns 10 is disposed on the support stand 8, and an upper end of the organic vapor humidification column 10 is inserted into the liquid chamber 12, and the inserted height is greater than a height of the liquid in the liquid chamber 12. The liquid chamber 12 is in the upper part of the organic vapor humidification column 10 to better wet the column under the force of solvent gravity.
The organic vapor humidifying column 10 is matched with different organic vapor humidifying columns 10 according to different organic solvents, so that the organic vapor humidifying column has a large specific surface area structure, has strong wettability to organic vapor and cannot react with the organic vapor.
It should be understood that fig. 2 is an embodiment of the organic vapor humidifier 27 of the present invention, and in practical application, the organic vapor humidifier 27 can have other structures, as long as the conditions of carrying organic gas in vapor and humidifying the organic vapor to saturation can be satisfied, and the organic vapor humidifying column 10 in the dashed line box in fig. 2 can be replaced by other structures.
The device utilizes the physical property parameters of the organic steam to quantify the content of the organic atmosphere by controlling the temperature. The organic solvent enters the liquid chamber 12 through the liquid inlet 6, passes through the organic vapor humidifying column 10, and is adsorbed on the organic vapor humidifying column 10. The organic vapor humidifying column 10 has a large specific surface area and a small air flow resistance, and is mainly aimed at, when the air flows to the end of the channel, saturating the organic gas carried by the air (i.e. the air pressure reaches the saturated vapor pressure), and controlling the inside of the organic vapor humidifying column when the air can not be inhaled into the organic atmosphere any more. The gas enters the interior of the housing 5 through the first gas inlet 7, passes through the organic vapor humidifying column 10, and then flows out of the gas outlet 11. The liquid chamber 12 is provided with a sealing structure at the contact of the organic vapor humidifying column 10 and the liquid chamber 12 to prevent liquid from leaking from the chamber directly into the channel interior. The organic solvent infiltrates the organic vapor humidifying column 10 and permeates downwards by means of gravity and capillary action, so that the whole column is completely kept in an infiltrated state, and the adsorption saturation state is reached as soon as possible when the gas circulates. The design advantage of this structure lies in along with the liquid reduces, still can make the adsorption column keep the infiltration state for a long time, guarantees the adsorption quantity of gas.
Furthermore, the saturated vapor pressure of the gas is calculated from the formula:
ln(P1/P2)＝(ΔHvap/R)((1/T2)-(1/T1)) (1)
In equation 1, ΔH vap is the vaporization enthalpy of the liquid, R is the ideal gas constant, namely 8.314J/(K. Mol), T 1、P1 is the known temperature and the corresponding known vapor pressure at that temperature, and T 2 is the actual temperature. From this, it is clear that temperature is a major factor determining vapor pressure.
It should be noted that the component does not have a heating source, i.e., the temperature of the air flow T 2 at the inlet and the outlet is the same, and is room temperature. The heating is not performed because the gas flow is heated and then discharged from the gas outlet 11, the temperature of the external pipe is lower than that of the gas flow, and the saturated vapor pressure of the output pipe doped with the organic gas is lowered, and the supersaturated vapor is liquefied at this time, thereby blocking the gas pipe.
In addition, design supporting bench 8 upper surface into the low angle slope structure (left low right high in the drawing), the height of gas vent 7 side is higher than the height of first air inlet 7, prevents that the liquid that the drip got off from building up in the passageway bottom, influences the adsorption effect of air current, has seted up vertical downward leakage fluid dram 9 on the casing 5 for unnecessary liquid can flow in along the slope and then flow out through leakage fluid dram 9, and supporting bench 8 and the bottom of casing 5 have the clearance, makes for certain buffer space of liquid.
The gas processed by the organic steam humidifier 27 contains organic gas, and in normal cases, the organic gas in the gas path can be saturated, and the organic gas in the second gas path 3 can be diluted by subsequently adjusting the mixing ratio of the first gas path 2 and the second gas path 3, so that the content of the organic gas in the final gas is controlled, and the gas ratio and atmosphere input into the atmosphere bin 15 can meet the requirements.
Referring to fig. 1,3 and 4, a cavity is arranged in an atmosphere chamber 15, a film supporting platform 18 is arranged in the cavity, grooves 26 are formed in the film supporting platform 18, two opposite side walls of the film supporting platform 18 are respectively provided with a second air inlet 19 and an air outlet 25, the lower end of the second air inlet 19 is coplanar with the film supporting platform 18, a screw structure 17 is arranged below the film supporting platform 18, one end of the screw structure 17 is connected with the side wall of the atmosphere chamber 15, the other end of the screw structure is connected with a heater 24, the heater 24 and the lower side wall of the film supporting platform 18 are connected with the bottom of the atmosphere chamber 15 in a sliding manner, the heater 24 can move below the film supporting platform 18 to heat the film supporting platform 18, the outer end of the heater 24 is connected with a gas conduit 22 through a connecting rod 23, the input end of the gas conduit 22 and the output end of the gas mixer 4 are communicated, the gas conduit 22 is parallel to the moving direction of the heater 24, the side wall of the gas conduit 25 is inserted into the atmosphere chamber 15, one end of the gas conduit 22 is connected with the side wall of the atmosphere chamber 15, the other end of the gas conduit 22 is connected with the side wall of the atmosphere chamber 15, the bottom of the heater 24 is connected with the lower side wall of the atmosphere chamber 24, the bottom of the atmosphere chamber is connected with the bottom of the atmosphere chamber 21, two arc surfaces of the gas conduit 21 are close to the two arc surfaces of the air inlet and two arc surfaces of the gas gun 20 are arranged at two arc surfaces of the two arc surfaces 20 are close to the two arc surfaces 20, two arc surfaces of the two arc surfaces are arranged at two sides of the two arc surfaces of the arc surfaces 20 are close to the two arc surfaces 20, and two arc surfaces are arranged, two arc surfaces are close to the two arc surfaces 20, and two arc surfaces are positioned at two sides of the two arc surfaces are close to the two sides and two arc surfaces are close to the two arc surfaces and 20 are positioned and the two side and 20.
In some embodiments of the present invention, the gas conduit 22 is connected to the heater 24 via a connecting rod 23, and the material of the connecting rod 23 is a thermal insulator to avoid heating the gas conduit 22.
In some embodiments of the present invention, the first type of gas line and the second type of gas line can each be provided with a plurality of gas lines in parallel, as the case may be, and each gas line is provided with a float flow meter 14. The air pump can provide a stable outlet air pressure, and the float flow meter 14 can measure the flow rate as reliable when the inlet and outlet air pressure is constant according to the Bernoulli principle. In the case of an outdoor environment, a pressure relief valve is added to ensure the inlet pressure of the float flow meter 14 while a cylinder is fitted.
In some embodiments of the invention, the first type gas line 2 and the second type gas line 3 are mixed by means of a tee 13 before entering the gas mixer 4, in which tee 13 the gases in the two lines of the first type gas line 2 and the second type gas line 3 are premixed and then enter the inlet section of the gas mixer 4. The gas mixer enters from the inlet end, and the inside of the gas mixer is provided with staggered baffles, so that different gases can be fully and uniformly mixed and discharged from the outlet section.
In some embodiments of the invention, a gas heat exchanger 16 is provided in the communication line between the gas mixer 4 and the atmosphere chamber 15 to control the inlet mixture temperature of the gas conduit 22.
In some embodiments of the invention, the gas mixer 4 can be supplied with other types of gases, determined by the type of gas required for purging, other sources 30 in the figures.
The working process of the device is as follows:
The gas bottle 1 inputs gas into a first type gas pipeline 2 and a second type gas pipeline 3 respectively, the gas in the second type gas pipeline 3 carries the organic gas after being processed by an organic steam humidifier 27, the carrying quantity 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 by a gas mixer 4, the mixed gas flow output by the gas mixer 4 is connected to a gas conduit 22 and a gas gun spray gun 21 through a gas heat exchanger 16, and finally the mixed gas flow is purged to the surface of a 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 and the air outlet 29 of the gas spray gun 21 are arranged on the same vertical plane with the inner end of the heater 24, so that the heating and atmosphere of the film are synchronous, and the film can be subjected to the action of the mixed gas when growing. The inner end of the heater 24 is connected with the spiral structure 17, and the motor controls the propulsion step length to control the moving speed of the spiral structure 17 and the gas guide tube 22. The film support platform 18 is internally provided with grooves 26 for securing the film to avoid changing the position of the film during the atmosphere purging process. The thinner the thickness of the platform is, the better the high-efficiency heat conduction is ensured. It is noted that the direction of the air flow emitted by the air tap forms a certain angle with the film, and the effect of the air tap is shown in fig. 5, namely, a negative pressure area is formed at the left side of the nozzle during purging, and the negative pressure acts to enable the atmosphere inside the box body to move towards the nozzle (blue arrow), so that the unheated film is prevented from being influenced by doping atmosphere due to diffusion of the atmosphere (yellow arrow). The air inlet 3 is also provided by an air pump, as shown in fig. 6, air enters from the air inlet and is horizontally blown to the tuyere, the air pump atmosphere replaces the atmosphere in the box to protect the film of the unannealed part, and meanwhile, the temperature of the air flow is lower, so that the influence of the heat source caused by heat conduction is weakened in the flowing process.
The growth of the film is microscopic and sensitive, the traditional air gun purging process is to wait for the completion of the purging of the whole glass and then to carry out annealing operation, and the part of the film which is purged first can experience more complicated atmosphere disturbance before annealing, thus being easy to cause uneven overall quality of the film. According to the invention, the organic atmosphere effect is maximized through the linkage of blowing and annealing, and the additional air path arrangement can also ensure that the crystallized part is not interfered by the external atmosphere, so that the problems of uneven film quality and poor repeatability are avoided to a certain extent. The film annealing process is a crystallization process accompanied by solvent evaporation, and the main function of the gas purging is to make the precursor solution (commonly called wet film) on the film reach a supersaturation state rapidly, at this time, most of the solvent in the wet film is volatilized along with the high-pressure gas, and a large number of nucleation sites are formed in the wet film, and these nucleation sites can help the film form a high-quality ordered crystal structure in the next high-temperature annealing stage. During the process, the introduction of trace organic steam can affect the volatilization rate of the wet film, and the selection of proper atmosphere can effectively regulate the mass transmission of the whole film nucleation crystallization process, and on the other hand, during the organic steam treatment, the dissolution characteristic of the steam to the wet film can cause the film to have repeated dissolution/recrystallization process. The crystallization process is the process by which the system gradually reaches a steady state, while the dissolution process makes the system more active. It follows that the introduction of the organic solvent affects both the mass transport and the energy transfer of the system. The proposal of the atmosphere control annealing device not only ensures that the processing parameters, namely the temperature, the flow rate and the processing time, can be easily controlled, but also optimizes the whole annealing process and improves the crystal quality. In addition, the film annealing process is more suitable for assembly line operation, and the film annealing process can be stabilized through the control of the connecting rod, so that the uniformity and the repeatability of the film are improved.
The invention has the following characteristics
(1) The organic gas content is quantitatively controlled by dynamic balance of saturated vapor pressure of an organic source in the closed container and flow of a controllable inert atmosphere (N 2).
(2) The humidifying component with large specific surface area in the channel is fully infiltrated under the combined action of capillary force and gravity, and the solvent on the surface is accelerated to volatilize and reach the saturation of solvent vapor rapidly when the gas flows through the humidifying component.
(3) In order to ensure that the gas is absorbed to saturation, the steam is subjected to a condensation treatment (lower than the gas temperature) in advance in the pipeline before entering the gas mixer, the pipeline temperature is manually controlled by the refrigerating equipment, and the condensed gas flows back to the vapor pressure saturation device.
(3) The annealing mode is a linear push type annealing (heating stage push type annealing), that is, the heating stage starts to contact from one end of the film (the film starts to be heated from one end) until the film advances to the other end of the film.
(4) The pushing type heat table is connected with the air knife through a connecting rod, so that the air knife and the heat table act on the same position of the film.
(5) The curved shape of the air tap makes the jet air flow form an acute angle with the film.
(6) The other N 2 air flow is provided by an air pump and is horizontally blown in from the other end of the annealing device (the other end of the film) to prevent the unheated film from being influenced by the doping atmosphere due to the diffusion of the atmosphere, and the air flow is low in temperature and is used for reducing the effect of heat diffusion as much as possible.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
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| US20130026152A1 (en) * | 2010-02-23 | 2013-01-31 | Mitsuhiro Suzuki | Pressurizing-type lamp annealing device, method for producing thin film, and method for using pressurizing-type lamp annealing device |
| CN115224204A (en) * | 2022-07-21 | 2022-10-21 | 华电重工股份有限公司 | A kind of perovskite film and its preparation method and device |
| CN218868608U (en) * | 2022-07-29 | 2023-04-14 | 昆山协鑫光电材料有限公司 | Air knife assembly for high-temperature annealing of large-area perovskite films |
| CN218831237U (en) * | 2022-10-21 | 2023-04-07 | 华碧新能源技术研究(苏州)有限公司 | Auxiliary film forming device for perovskite solar cell |
| CN219288080U (en) * | 2023-02-22 | 2023-06-30 | 中国华能集团清洁能源技术研究院有限公司 | A perovskite thin film annealing control device |
| CN118073215A (en) * | 2024-01-09 | 2024-05-24 | 复旦大学宁波研究院 | An in-situ annealing multifunctional testing system |
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