CN113921724A

CN113921724A - Method for preparing perovskite thin film in two steps, device and preparation method thereof, and perovskite battery

Info

Publication number: CN113921724A
Application number: CN202111154811.3A
Authority: CN
Inventors: 李明洁; 吴俊杰; 王雪戈
Original assignee: Wuxi Utmolight Technology Co Ltd
Current assignee: Wuxi Utmolight Technology Co Ltd
Priority date: 2021-09-29
Filing date: 2021-09-29
Publication date: 2022-01-11

Abstract

The invention provides a method for preparing a perovskite thin film in two steps, a device thereof, a preparation method and a perovskite battery, wherein the method comprises the following steps: preparing a first charge transport layer on the surface of a substrate, depositing an inorganic precursor layer on the surface of the first charge transport layer by adopting a near space sublimation method or a gas phase transport method, then coating an organic precursor solution on the surface of the inorganic precursor, and reacting the inorganic precursor layer with the organic precursor solution to form the perovskite thin film after annealing treatment. The perovskite thin film prepared by the method can be independent of the flatness of the substrate, and large-area and uniform perovskite thin films can be prepared on textured substrates and substrates with certain roughness.

Description

Method for preparing perovskite thin film in two steps, device and preparation method thereof, and perovskite battery

Technical Field

The invention belongs to the technical field of perovskite batteries, and relates to a method for preparing a perovskite thin film in two steps, a device and a preparation method thereof, and a perovskite battery.

Background

Solar energy is an inexhaustible novel clean energy, namely a perovskite batteryThe perovskite battery is a novel perovskite battery, the perovskite battery receives a great deal of attention due to the constantly refreshed conversion efficiency, and the research on industrialization is continuously carried out. The perovskite type perovskite battery has high visible light absorption, simple film forming process and fast photoelectric conversion efficiency, so the perovskite type perovskite battery is concerned all over the world. The general structural formula of the photovoltaic perovskite material can be written as ABX₃Wherein, the A site is a positively charged organic group (such as methylamine group and formamidine group) or cation (such as cesium ion and rubidium ion), the B site is lead or tin ion, and the X site is halogen ion (such as chlorine ion, bromine ion and iodine ion). The industrialization of perovskite batteries firstly needs to solve the technical problem of uniformly preparing a perovskite film layer in a large area.

At present, a plurality of methods for preparing the perovskite solar cell are available, such as a spin coating method, a vacuum method, a blade coating method, a spraying method and the like. These methods can be roughly classified into a solution method in which a perovskite precursor material is completely dissolved in an organic solvent such as N, N-Dimethylformamide (DMF) or Dimethylsulfoxide (DMSO), and a perovskite film layer is prepared by spin coating, blade coating, spray coating, slit-die coating, or the like; the vacuum method is to directly prepare the precursor material of the perovskite on a substrate in a vacuum state by a thermal evaporation method, a sputtering method, a close space sublimation method (CSS), a gas phase transport method (VTD) and the like, and no solvent is involved in the whole process. Solution processes are difficult to achieve complete coverage on rough or defective substrates and are therefore not suitable for producing uniform film layers on textured and non-planar substrates. The vacuum method can deposit perovskite film layers on substrates with different roughness or morphology in a shape-preserving manner, but the traditional vacuum evaporation method is not easy to accurately control the proportion of each component, the utilization rate of precursor materials is low, the production beat is slow, and the energy consumption is high.

The preparation of large-area perovskite thin films by adopting a vacuum and solution two-step method is only reported. The near-space sublimation and gas-phase transportation method is a film preparation method with wide use value, the near-space sublimation method has the advantages of high deposition rate, high material utilization rate, energy saving and the like, the gas-phase transportation method has the advantages of accurately regulating and controlling precursor components, can realize continuous feeding, and is a preparation method with industrial prospect. The solution coating method is attracting attention because of its low requirement for process equipment and easy industrialization.

CN103346018A proposes a method for preparing perovskite film layer by solid-liquid reaction two-step method, i.e. forming an inorganic precursor layer in the first step, and then soaking the inorganic precursor layer in an organic solution containing AI material in the second step to obtain ABI₃Perovskite membranous layer of structure. In the second step of the scheme, the inorganic precursor layer is soaked in the organic solution, so that the material utilization rate is low, and along with the increase of the soaking times, the concentration of the organic solution is reduced and easy to pollute, and the industrial production is not facilitated. In addition, the discharge amount of organic waste liquid is increased, which is not favorable for environmental protection and increases the cost.

The prior art for preparing perovskite film layers has mainly focused on solution processes and vacuum evaporation processes. Because the solution has fluidity, if the perovskite film layer is prepared on the textured substrate or the uneven substrate with larger roughness by adopting a solution method, a thin film layer or even a film layer with holes is formed on the top of the textured surface or the particle bulges, and further the prepared perovskite film layer has a large number of pinholes or holes. Therefore, the solution method is only suitable for preparing a small-area perovskite battery by a spin coating method or preparing a small perovskite component on a substrate with a small area by blade coating or slit-die coating (Slot-die), but is not suitable for preparing uniform perovskite thin films on textured substrates and uneven substrates. In addition, in the process of preparing the perovskite film layer by the solution method, a solvent is introduced, so that the processes of adding the solvent and removing the solvent are added in the production, and the volatilization of a large amount of the solvent causes environmental pollution, so that the green production is not easy to realize. The vacuum evaporation method is not easy to accurately control the proportion of each component, and is not easy to continuously feed, the utilization rate of precursor materials is low, the production beat is slow, and the energy consumption is high.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a method for preparing a perovskite thin film in two steps, a device thereof, a preparation method and a perovskite battery.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a vacuum solution two-step method for preparing a perovskite thin film, wherein the method comprises:

preparing a first charge transport layer on the surface of a substrate, depositing an inorganic precursor layer on the surface of the first charge transport layer by adopting a near space sublimation method or a gas phase transport method, then coating an organic precursor solution on the surface of the inorganic precursor, and reacting the inorganic precursor layer with the organic precursor solution to form the perovskite thin film after annealing treatment.

The invention provides a method for preparing a perovskite thin film in a large area by a vacuum-solution two-step method, which is suitable for various perovskite material systems such as MALI (MAPbI) and is characterized in that a doped inorganic precursor layer is prepared by a near-space sublimation method or a gas phase transport method, and then an organic component is prepared by coating an organic precursor solution to form a perovskite film layer₃)、FALI(FAPbI₃) And binary or ternary doped perovskite thin films. Compared with the full solution method, the perovskite thin film prepared by the method does not depend on the flatness of the substrate, and large-area and uniform perovskite thin films can be prepared on textured substrates and substrates with certain roughness. Compared with the perovskite film prepared by the full vacuum method, the method can realize continuous feeding, is more beneficial to continuous production, and is easier to accurately control the content ratio of each component in each organic precursor solution by adopting the solution method in the second step.

It should be noted that, in addition to the improvement on the preparation process, the invention greatly improves the structure of the equipment supported by the process, including independently designing the near-space sublimation device, the gas-phase transport device and the heating and annealing device, and can design the matching number of each device according to the production beat, thereby improving the flexibility and the utilization rate of the equipment.

As a preferred technical solution of the present invention, the substrate includes a conductive glass substrate or a textured substrate;

preferably, the material of the first charge transport layer includes any one of cuprous thiocyanate, cuprous iodide, cuprous oxide, nickel oxide, vanadium pentoxide, molybdenum trioxide, 22'77' -tetrakis [ NN-bis (4-methoxyphenyl) amino ] -99' -spirobifluorene, poly (3-hexylthiophene-2, 5-diyl), poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ], poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), titanium dioxide, tin dioxide, fullerene, bathocuproine, zinc oxide, or [6,6] -phenyl-C61-butyric acid isopropyl ester.

Preferably, the first charge transport layer is prepared by an evaporation method, a sputtering method, a chemical bath deposition method, a precursor solution spin coating method, a precursor solution blade coating method, or a slit coating method.

Preferably, the first charge transport layer has a thickness of 0.1 to 50nm, and may be, for example, 0.1nm, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm or 50nm, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

In a preferred embodiment of the present invention, the close space sublimation is performed in a close space sublimation apparatus including a sublimation source containing an inorganic precursor, and the temperature of the sublimation source is controlled to be 80 to 1000 ℃, for example, 80 ℃, 100 ℃, 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃ or 1000 ℃, but the present invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.

Preferably, the gas transport method is performed in a gas transport apparatus, the gas transport apparatus includes an evaporation boat containing an inorganic precursor, and the temperature of the evaporation boat is controlled to be 60 to 300 ℃, for example, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 240 ℃, 260 ℃, 280 ℃ or 300 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

Preferably, a substrate carrier is arranged in the near space sublimation device and the gas phase conveying device, and the substrate carrier horizontally moves in the near space sublimation device and the gas phase conveying device, so that the substrate is conveyed to the next process.

Preferably, the temperature of the substrate stage is controlled to 20 to 300 ℃, and may be, for example, 20 ℃, 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, 240 ℃, 260 ℃, 280 ℃ or 300 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range of values are also applicable.

In a preferred embodiment of the present invention, the material of the inorganic precursor layer includes a lead-containing inorganic precursor.

Preferably, the lead-containing inorganic precursor comprises PbI₂、PbBr₂Or PbCl₂Any one or a combination of at least two of them.

Preferably, the material of the inorganic precursor layer further comprises a cesium-containing inorganic precursor.

Preferably, the cesium-containing inorganic precursor includes any one of CsI, CsBr, or CsCl, or a combination of at least two thereof.

Preferably, the thickness of the inorganic precursor layer is 100 to 600nm, and may be, for example, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm or 600nm, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.

In a preferred embodiment of the present invention, the coating method is slit coating or knife coating.

Preferably, the coating speed is 5 to 50mm/s, for example, 5mm/s, 10mm/s, 15mm/s, 20mm/s, 25mm/s, 30mm/s, 35mm/s, 40mm/s, 45mm/s or 50mm/s, but is not limited to the values listed, and other values not listed in the range of values are also applicable.

Preferably, the coating process is carried out in a coating apparatus.

Preferably, the amount of the liquid to be injected by the coating device is 5 to 500. mu.L/s, and may be, for example, 5. mu.L/s, 10. mu.L/s, 100. mu.L/s, 150. mu.L/s, 200. mu.L/s, 250. mu.L/s, 300. mu.L/s, 350. mu.L/s, 400. mu.L/s, 450. mu.L/s or 500. mu.L/s, but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are also applicable.

Preferably, the slit height of the coating device is 10 to 200 μm, 10 μm, 20 μm, 40 μm, 60 μm, 80 μm, 100 μm, 120 μm, 140 μm, 160 μm or 180 μm, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

Preferably, the air knife wind pressure of the coating device is 0.01 to 0.1MPa, for example, 0.01MPa, 0.02MPa, 0.03MPa, 0.04MPa, 0.05MPa, 0.06MPa, 0.07MPa, 0.08MPa, 0.09MPa or 0.1MPa, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.

As a preferred technical solution of the present invention, the organic precursor solution includes a precursor solute and a solvent.

Preferably, the precursor solute comprises a combination of at least two of iodomethylamine, iodoformamidine, bromomethylamine, bromoformamidine, chloromethylamine, or chloroformamidine.

Preferably, the precursor solutes comprise a first solute selected from iodomethylamine or iodoformamidine, a second solute selected from bromomethylamine or bromoformamidine, and a third solute selected from chloromethylamine or chloroformamidine.

Preferably, the mass ratio of the first solute to the second solute to the third solute is (50-99): 1-50, and may be, for example, 50:1:1, 60:10:10, 70:20:20, 80:30:30, 90:40:40, or 99:50:50, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.

Preferably, the solvent comprises a combination of at least two of N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, ethylene glycol methyl ether, lutidine N-oxide, N-propanol, isopropanol, t-butanol, N-butanol, 2-pentanol, 1, 2-propanediol, N-hexane, ethyl acetate, chlorobenzene, diethyl ether, acetonitrile, ethanol, or methanol.

Preferably, the solvent includes a first solvent, a second solvent, and a third solvent.

The first solvent is selected from any one of ethylene glycol monomethyl ether, n-propanol, isopropanol, ethanol or methanol.

The second solvent is selected from any one of tert-butyl alcohol, n-butyl alcohol, 2-amyl alcohol, 1, 2-propylene glycol, n-hexane, ethyl acetate, chlorobenzene, diethyl ether or acetonitrile.

The third solvent is any one of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, ethylene glycol monomethyl ether or dimethyl pyridine N-oxide.

Preferably, the concentration of the organic precursor solution is 0.1 to 1.5mol/L, and may be, for example, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1.0mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, or 1.5mol/L, but is not limited to the recited values, and other values not recited in the numerical ranges are also applicable.

The invention is characterized in that the invention carries out special design on the types and the contents of all components in the organic precursor solution, adopts the compounding of various solvents and various solutes, and prepares the uniform, smooth, black and bright perovskite film layer with no holes and no stripes.

As a preferable technical solution of the present invention, the annealing treatment is performed in a heating annealing apparatus, the heating annealing apparatus includes a heating chamber, a conveying device is disposed in the heating chamber, the substrate is placed on the conveying device and conveyed from one end of the heating chamber to the other end of the heating chamber, and the inside of the heating chamber is divided into a low-temperature heat-preserving section, a high-temperature heat-preserving section, and a cooling section along a conveying direction of the substrate.

Preferably, the temperature of the low-temperature holding section is 50 to 120 ℃, and may be, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.

Preferably, the heating temperature of the high-temperature holding section is 100 to 180 ℃, and may be, for example, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 180 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

Preferably, the substrate is cooled to room temperature in the cooling section by air cooling.

Preferably, the annealing time is 10-60 min, such as 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.

Preferably, the substrate is transported at a speed of 0.1 to 3m/min, such as 0.1m/min, 0.5m/min, 1m/min, 1.5m/min, 2m/min, 2.5m/min or 3m/min, but not limited to the recited values, and other values not recited in this range are equally applicable.

Preferably, an annealing preparation chamber and an annealing sheet discharging chamber which are communicated with the subject and the object are respectively arranged at two ends of the heating chamber, the substrate conveyed in the previous process is conveyed into the heating chamber through the annealing preparation chamber, and the substrate is conveyed out through the annealing sheet discharging chamber after the annealing treatment is finished.

In a second aspect, the present invention provides a close space sublimation apparatus for carrying out the close space sublimation method of the first aspect.

The near space sublimation device comprises a near space sublimation chamber, a first substrate carrying table which moves horizontally is arranged in the near space sublimation chamber, the deposition side of the substrate is placed on the first substrate carrying table downwards, at least one sublimation source which is arranged side by side along the conveying direction of the substrate is arranged on the bottom layer in the near space sublimation chamber, and the sublimation source is a linear sublimation source or a surface sublimation source.

The line sublimation source comprises a sublimation source box with a strip-shaped groove-shaped structure, an inorganic precursor is arranged at the bottom of the sublimation source box, a built-in cover plate is arranged in a middle layer area of the sublimation source box, a slit with adjustable width is formed in the built-in cover plate, a detachable top cover plate is arranged at the opening of the sublimation source box in a covering mode, an opening is formed in the top cover plate, and inorganic precursor gas formed by sublimation of the inorganic precursor sequentially penetrates through the slit of the built-in cover plate and the opening of the top cover plate and then is deposited on the surface of the substrate.

According to the invention, the sublimation source box consists of a built-in cover plate (a first-stage cover plate) and a top cover plate (a second-stage cover plate) which are arranged in two stages, a specific gas path arrangement is arranged in the sublimation source box, the built-in cover plate is provided with a slit with adjustable width, the vapor pressure and the evaporation speed of an inorganic precursor can be adjusted, and meanwhile, the vapor of the inorganic precursor can be mixed uniformly. Meanwhile, the sublimation source box also has a continuous feeding function, and continuous production can be realized.

The opening mode on the top cover plate can be adjusted at will, and the top cover plate with different opening modes can be selected for use, so that various gas circuit arrangement schemes can be combined, the risk of uneven coating of the equipment is reduced, great flexibility is provided, a certain combination scheme can be found, and the film layer is distributed most evenly on a large area.

It should be noted that: (1) the top cover plate is formed by splicing two cover plates optionally, and the two cover plates are fixedly connected through a cover plate bracket; (2) the cover plate (including the built-in cover plate and the top cover plate) of the sublimation source box comprises but is not limited to graphite, and can also be made of metal and alloy materials with high-temperature-resistant and corrosion-resistant coatings; (3) the first substrate carrying platform is a substrate support with a hollow structure, the deposition film layer of the substrate can be placed face down, and the first substrate carrying platform is connected with the transmission device and can drive the substrate to be transmitted among the chambers.

As a preferred technical solution of the present invention, the close-space sublimation apparatus further includes a first preparation chamber and a first sheet discharge chamber respectively butted with two ends of the close-space sublimation chamber, the substrate transferred by the previous step is transferred from the first preparation chamber to the close-space sublimation chamber, and is discharged from the first sheet discharge chamber after sublimation deposition.

It should be noted that the chamber shapes of the near-space sublimation chamber, the first preparation chamber and the first sheet outlet chamber in the present invention include, but are not limited to, a cubic shape, and may be all possible geometric shapes such as a cylindrical shape, a spherical shape, a conical shape, and the like. The inner spaces of the first preparation chamber and the first sheet outlet chamber are small, so that the chambers are conveniently and quickly pumped to a low vacuum state, and before the substrate enters the first preparation chamber, a film can be coated on the back surface (non-deposition surface) of the substrate or a baffle can be covered on the back surface to prevent inorganic or organic precursors from being deposited on the back surface of the substrate.

Preferably, the side wall of the first preparation chamber, the side wall of the near-space sublimation chamber and the side wall of the first sheet outlet chamber are all provided with first air exhaust ports, the first air exhaust ports are externally connected with a vacuum pump, and the first preparation chamber, the near-space sublimation chamber and the first sheet outlet chamber are correspondingly vacuumized through the first air exhaust ports.

Preferably, the first temperature control device is arranged at the joint of the first preparation chamber and the close space sublimation chamber and at the joint of the close space sublimation chamber and the first sheet outlet chamber.

In the invention, the first temperature control device has a water cooling function, can cool the conveying pipeline (the joint of the first preparation chamber and the near-space sublimation chamber and the joint of the near-space sublimation chamber and the first sheet outlet chamber), can condense inorganic precursor gas in the near-space sublimation chamber on the pipe wall when the first control valve is opened, and can prevent the first preparation chamber and the first sheet outlet chamber from being polluted.

Preferably, the inlet end of the first preparation chamber, the butt joint of the first preparation chamber and the near-space sublimation chamber, the butt joint of the near-space sublimation chamber and the first sheet outlet chamber, and the outlet end of the first sheet outlet chamber are all provided with a first control valve.

Each first control valve controls the communication of each chamber, and all the first control valves can be of baffle structures with controllable opening angles, can also be arranged in specific gas paths with controllable flow, and can be arranged and communicated in a single-path or multi-path array mode.

Preferably, an online component detection feedback module is further arranged inside the near-space sublimation chamber.

In the invention, the online component detection feedback module is connected with the sublimation source to form a closed loop system, the online component detection feedback module feeds back the component monitoring data of the inorganic precursor layer to the temperature control system of the sublimation source, when a certain component is too much, the sublimation source can be cooled, and when a certain component is too little, the sublimation source can be heated, so that each component meets the set requirements.

Preferably, a first pressure regulating port is formed in the wall of the near-space sublimation chamber, and a first pressure regulating valve is arranged on the first pressure regulating port.

According to the invention, the working gas is supplied into the near-space sublimation chamber or discharged from the near-space sublimation chamber through the first pressure adjusting port, so that the pressure in the near-space sublimation chamber is adjusted, and the selectable working gas is inert gas such as nitrogen or argon. And a pressure monitor is optionally arranged in the near-space sublimation chamber and can monitor the air pressure in the cavity in real time.

As a preferred technical solution of the present invention, the first substrate stage is a rotating structure with a changeable tilt angle.

Preferably, the first substrate stage rotates with a center as a rotation point.

Preferably, the inclination angle of the first substrate stage is 0 to 45 °, and may be, for example, 5 °, 10 °, 15 °, 20 °, 25 °, 30 °, 35 °, 40 °, or 45 °, but is not limited to the listed values, and other values not listed in the numerical range are also applicable.

The invention realizes the adjustable substrate angle of the substrate and controllable chamber pressure through the inclination of the first substrate carrying platform, and the preparation of the inorganic precursor layer by the vacuum method can precisely regulate and control the deposition angle, deposition speed and other process parameters of the inorganic precursor, so that the inorganic precursor layer has proper porosity, and is favorable for reacting with an organic precursor solution to form a high-quality perovskite crystal film.

As a preferable technical scheme of the invention, the interior of the sublimation source box is divided into a first temperature zone, a second temperature zone and a third temperature zone along the conveying direction of the substrate, and the temperatures of the first temperature zone and the third temperature zone are higher than that of the second temperature zone.

The sublimation source is divided into three temperature zones with different temperature ranges, independent temperature control can be carried out, and the temperature of the first temperature zone and the third temperature zone is required to be higher than that of the second temperature zone, so that the uniformity of the deposited film layer is ensured.

As a preferable technical scheme of the invention, the surface sublimation source comprises a sublimation disc, and an inorganic precursor is placed in the sublimation disc.

Preferably, the inorganic precursors are arranged in the planar sublimation source according to a zigzag shape, a zigzag shape or an array.

In the invention, when the sublimation source is a surface sublimation source, the inorganic precursors can be arranged according to a Chinese character hui shape, a Chinese character mi shape or an array, so that the uniformity of a sublimation film layer is ensured. Of course, the present invention is not limited to the three arrangements defined above, and other arrangements and derivative distributions can be used in the present invention.

The working principle of the near space sublimation device provided by the invention comprises the following steps:

the substrate containing the first charge transport layer enters a first substrate carrying platform of the close-space sublimation device, after the substrate enters a first preparation chamber, a first control valve is closed, the first preparation chamber is vacuumized, after the first preparation chamber is vacuumized to a certain vacuum degree, a first control valve between the first preparation chamber and a close-space sublimation chamber is opened, the substrate enters the close-space sublimation chamber and starts an inorganic precursor layer, the deposition thickness range of the inorganic precursor layer is 100-600 nm, the temperature range of a sublimation source is 80-1000 ℃, and the temperature of the first substrate carrying platform is set to be 20-300 ℃.

And precisely regulating and controlling the inclination angle of the first substrate carrying platform, the temperature of the sublimation source and the first substrate carrying platform and the pressure of each chamber according to the material system and the thickness range of the deposited inorganic precursor. And simultaneously depositing the lead-containing inorganic precursor and the cesium-containing inorganic precursor, and controlling sublimation rates of the lead-containing inorganic precursor and the cesium-containing inorganic precursor by regulating and controlling the temperature of sublimation sources of the lead-containing inorganic precursor and the cesium-containing inorganic precursor so as to regulate and control the deposition ratio of lead and cesium. In the deposition process, the first sheet outlet chamber is pumped to a low vacuum state, after deposition is finished, the first control valves of the near space sublimation chamber and the first sheet outlet chamber are opened, and after the substrate enters the first sheet outlet chamber, the first control valve between the near space sublimation chamber and the first sheet outlet chamber is closed.

In a third aspect, the present invention provides a gas phase transport apparatus for performing the gas phase transport method of the first aspect;

the vapor transport device comprises a vapor deposition chamber, a second substrate carrying table capable of moving horizontally is arranged in the vapor deposition chamber, and the substrate is placed on the second substrate carrying table; the bottom of the vapor deposition chamber is in butt joint with a vapor transport chamber, at least one evaporation boat is arranged in the vapor transport chamber side by side along the horizontal direction, and pressure concentration sensors are arranged in the vapor deposition chamber and the vapor transport chamber.

The invention is provided with pressure concentration sensors in the vapor deposition chamber and the vapor transport chamber, and can monitor the air pressure and the gas concentration in the cavity in real time.

As a preferred technical solution of the present invention, two ends of the vapor deposition chamber are respectively butted with the second preparation chamber and the second sheet discharge chamber, the substrate transferred through the previous process is sent into the vapor deposition chamber from the second preparation chamber, and the substrate is sent out from the second sheet discharge chamber after sublimation deposition.

It should be noted that the chamber shapes of the vapor deposition chamber, the vapor transport chamber, the second preparation chamber and the second sheet discharge chamber in the present invention include, but are not limited to, a cubic shape, and may be all possible geometric shapes such as a cylindrical shape, a spherical shape, a conical shape, and the like. The inner spaces of the second preparation chamber and the second sheet outlet chamber are small, so that the chambers are favorably and quickly pumped to a low vacuum state, and before the substrate enters the second preparation chamber, a film can be coated on the back surface (non-deposition surface) of the substrate or a baffle can be covered on the back surface of the substrate, so that inorganic or organic precursors are prevented from being deposited on the back surface of the substrate.

The vapor deposition chamber and the vapor transport chamber have a chamber baking function, when the equipment runs for a period of time, some inorganic precursors can be attached to the inner wall, the chamber baking function is started to continuously heat the inner wall of the chamber (the heating range is 25-500 ℃), the inorganic precursors attached to the inner wall of the chamber can be evaporated, the purpose of cleaning the chamber is further achieved, and waste gas is discharged through the pumping hole.

Preferably, the sidewall of the second preparation chamber, the sidewall of the vapor deposition chamber, and the sidewall of the second wafer discharge chamber are all provided with a second pumping hole, the second pumping hole is externally connected with a vacuum pump, and the second preparation chamber, the vapor deposition chamber, and the second wafer discharge chamber are correspondingly pumped by the second pumping hole.

Preferably, the joint of the second preparation chamber and the vapor deposition chamber and the joint of the vapor deposition chamber and the second sheet discharging chamber are provided with second temperature control devices.

In the invention, the second temperature control device has a water-cooling function, can cool the conveying pipeline (the joint of the second preparation chamber and the vapor deposition chamber and the joint of the vapor deposition chamber and the second wafer discharging chamber), can condense inorganic precursor gas in the vapor deposition chamber on the pipe wall when the second control valve is opened, and prevents the second preparation chamber and the second wafer discharging chamber from being polluted.

Preferably, the inlet end of the second preparation chamber, the joint of the second preparation chamber and the vapor deposition chamber, the joint of the vapor deposition chamber and the second sheet outlet chamber, the joint of the vapor deposition chamber and the vapor transport chamber, and the outlet end of the second sheet outlet chamber are all provided with second control valves.

Preferably, the walls of the vapor deposition chamber and the vapor transport chamber are provided with second pressure regulating ports, and the second pressure regulating ports are provided with second pressure regulating valves.

According to the invention, working gas is supplemented into or discharged from the vapor deposition chamber and/or the vapor transport chamber through the second pressure regulating port, so that the pressure in the vapor deposition chamber and/or the vapor transport chamber is regulated, and the optional working gas is inert gas such as nitrogen or argon. And pressure monitors are optionally arranged in the vapor deposition chamber and the vapor transport chamber, so that the air pressure in the cavity can be monitored in real time.

As a preferred technical solution of the present invention, the second substrate stage is a rotation structure with a changeable tilt angle.

Preferably, the second substrate stage rotates with a center as a rotation point.

Preferably, the inclination angle of the second substrate stage is 0 to 45 °, and may be, for example, 5 °, 10 °, 15 °, 20 °, 25 °, 30 °, 35 °, 40 °, or 45 °, but is not limited to the listed values, and other values not listed in the numerical range are also applicable.

Preferably, a stage baffle plate is arranged at the bottom of the second substrate stage.

The invention realizes the adjustable substrate angle of the substrate and controllable chamber pressure through the inclination of the second substrate carrying platform, and the preparation of the inorganic precursor layer by the vacuum method can precisely regulate and control the deposition angle, deposition speed and other process parameters of the inorganic precursor, so that the inorganic precursor layer has proper porosity, and is favorable for reacting with the organic precursor solution to form the high-quality perovskite crystal film. And a stage baffle plate is arranged in a range of 1-5 cm below the second substrate stage, and the stage baffle plate can completely shield, completely expose or partially expose the second substrate stage.

The working principle of the gas phase conveying device provided by the invention comprises the following steps:

the substrate containing the first charge transport layer enters a second substrate carrying platform of the gas phase conveying device, after the substrate enters a second preparation chamber, a second control valve is closed, the second preparation chamber is vacuumized, after the second preparation chamber is vacuumized to a certain vacuum degree, a second control valve between the second preparation chamber and or a gas phase deposition chamber is opened, the substrate starts to deposit an inorganic precursor layer after entering the gas phase deposition chamber, the deposition thickness range of the inorganic precursor layer is 100-600 nm, the temperature of an evaporation boat is controlled to be 60-300 ℃, and the temperature of the second substrate carrying platform is set to be 20-300 ℃.

And precisely regulating and controlling the inclination angle of the second substrate carrying platform, the temperatures of the evaporation boat and the second substrate carrying platform and the pressure of each chamber according to the material system and the thickness range of the deposited inorganic precursor. And simultaneously depositing the lead-containing inorganic precursor and the cesium-containing inorganic precursor, and controlling sublimation rates of the lead-containing inorganic precursor and the cesium-containing inorganic precursor by regulating and controlling the temperature of sublimation sources of the lead-containing inorganic precursor and the cesium-containing inorganic precursor so as to regulate and control the deposition ratio of lead and cesium. In the deposition process, the second wafer outlet chamber is pumped to a low vacuum state, after deposition is finished, the second control valves of the near vapor deposition chamber and the second wafer outlet chamber are opened, and after the substrate enters the second wafer outlet chamber, the second control valve between the vapor deposition chamber and the second wafer outlet chamber is closed.

In a fourth aspect, the present invention provides a process for the preparation of a perovskite battery, the process comprising the process of the first aspect; the preparation method also comprises the following steps:

and sequentially preparing a second charge transmission layer and a back electrode on the surface of the perovskite thin film to obtain the perovskite battery.

As a preferable technical solution of the present invention, the method for preparing the second charge transport layer includes an evaporation method, a sputtering method, a precursor solution spin coating method, a precursor solution blade coating method, or a slit coating method.

Preferably, the thickness of the second charge transport layer is 5 to 50nm, and may be, for example, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm or 50nm, but is not limited to the enumerated values, and other values not enumerated within the range are also applicable.

Preferably, the back electrode comprises a metal back electrode or a transparent back electrode.

Preferably, the metal material used for the metal back electrode comprises any one or a combination of at least two of silver, copper, gold, aluminum, molybdenum or chromium.

Preferably, the thickness of the metal back electrode is 40 to 100nm, and may be, for example, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm or 100nm, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.

Preferably, the electrode material adopted by the transparent back electrode comprises any one or a combination of at least two of tin-doped indium oxide, fluorine-doped tin oxide and zinc oxide.

Preferably, the thickness of the transparent back electrode is 50 to 100nm, for example, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm or 100nm, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.

In a fifth aspect, the invention provides a perovskite battery prepared by the preparation method of the fourth aspect, wherein the perovskite battery comprises a substrate, a first charge transport layer, a perovskite thin film, a second charge transport layer and a back electrode which are sequentially stacked.

Compared with the prior art, the invention has the beneficial effects that:

Drawings

FIG. 1 is a schematic structural view of a close-space sublimation apparatus provided in an embodiment of the invention;

FIG. 2 is a schematic structural diagram of a line sublimation source provided in accordance with an embodiment of the present invention;

FIG. 3 is a schematic structural diagram of a flour sublimation source provided in an embodiment of the invention;

FIG. 4 is a schematic structural diagram of a facelift source according to an embodiment of the present invention;

FIG. 5 is a schematic structural diagram of a gas phase transport apparatus provided in accordance with an embodiment of the present invention;

FIG. 6 is a schematic structural diagram of a thermal annealing apparatus according to an embodiment of the present invention;

fig. 7 is a schematic structural diagram of a perovskite battery provided in an embodiment of the present invention.

Wherein, 1-a close space sublimation chamber; 2-a first preparation chamber; 3-a first sheet outlet chamber; 4-a first substrate stage; 5-sublimation source; 6-an online component detection feedback module; 7-a first extraction opening; 8-a first control valve; 9-a first pressure regulating valve; 10-a pressure monitor; 11-a first temperature control device; 12-a vapor deposition chamber; 13-a second preparation chamber; 14-a second sheet outlet chamber; 15-a gas phase transport chamber; 16-stage baffle plate; 17-a second substrate stage; 18-pressure concentration sensor; 19-a second pressure regulating valve; 20-a second extraction opening; 21-a second temperature control device; 22-a second control valve; 23-evaporation boat; 24-a sublimation source cartridge; 25-an inorganic precursor; 26-built-in cover plate; 27-a top cover plate; 28-cover plate support; 29-a heating chamber; 30-annealing preparation chamber; 31-annealing out of the wafer chamber; 32-a transfer device; 33-low temperature heat preservation section; 34-high temperature heat preservation section; 35-cooling section; 36-a sublimation tray; 37-a substrate; 38-a first charge transport layer; 39-perovskite thin film; 40-a second charge transport layer; 41-back electrode.

Detailed Description

It is to be understood that in the description of the present invention, the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be taken as limiting the present invention. Furthermore, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.

It should be noted that, in the description of the present invention, unless otherwise explicitly specified or limited, the terms "disposed," "connected" and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.

The technical solution of the present invention is further explained by the following embodiments.

In a specific embodiment, the present invention provides a near space sublimation apparatus, as shown in fig. 1, the near space sublimation apparatus includes a near space sublimation chamber 1, a first substrate stage 4 moving horizontally is arranged inside the near space sublimation chamber 1, a deposition side of a substrate 37 is placed on the first substrate stage 4 downward, at least one sublimation source 5 arranged side by side along a conveying direction of the substrate 37 is arranged on a bottom layer inside the near space sublimation chamber 1, and the sublimation source 5 is a line sublimation source or a surface sublimation source.

As shown in fig. 2, the sublimation source includes a sublimation source box 24 having a strip-shaped groove-shaped structure, an inorganic precursor 25 is disposed at the bottom of the sublimation source box 24, a built-in cover plate 26 is disposed in a middle layer region of the sublimation source box 24, a slit with an adjustable width is disposed on the built-in cover plate 26, a detachable top cover plate 27 is covered at an opening of the sublimation source box 24, an opening is disposed on the top cover plate 27, and the inorganic precursor 25 formed by sublimation of the inorganic precursor 25 sequentially passes through the slit of the built-in cover plate 26 and the opening of the top cover plate 27 and is deposited on the surface of a substrate 37.

In the present invention, the sublimation source cartridge 24 is composed of a built-in cover plate 26 (first-stage cover plate) and a top cover plate 27 (second-stage cover plate), and has a specific gas path arrangement inside, and the built-in cover plate 26 has a slit with adjustable width, so that the vapor pressure and evaporation rate of the inorganic precursor 25 can be adjusted, and the vapor of the inorganic precursor 25 can be mixed sufficiently and uniformly. Meanwhile, the sublimation source box 24 also has a continuous feeding function, and continuous production can be realized.

The opening mode on the top cover plate 27 can be adjusted at will, and the top cover plate 27 with different opening modes can be selected for use, so that various gas circuit arrangement schemes can be combined, the risk of uneven coating of the equipment is reduced, great flexibility is provided, a certain combination scheme can be found, and the film layer is distributed most evenly on a large area.

It should be noted that: (1) the top cover plate 27 in the invention can be formed by splicing two cover plates, and the two cover plates are fixedly connected through a cover plate bracket 28; (2) the cover plate (including the built-in cover plate 26 and the top cover plate 27) of the sublimation source box 24 includes, but is not limited to, graphite, and may be made of metal and alloy with a high-temperature-resistant corrosion-resistant coating; (3) the first substrate stage 4 is a substrate support with a hollow structure, so that the deposition film surface of the substrate 37 can be placed downwards, and the first substrate stage 4 is connected with a transmission device and can drive the substrate 37 to be transmitted among all chambers.

Further, the close space sublimation device further comprises a first preparation chamber 2 and a first piece outlet chamber 3 which are respectively butted with two ends of the close space sublimation chamber 1, the substrate 37 conveyed by the previous process is conveyed into the close space sublimation chamber 1 through the first preparation chamber 2, and the substrate is conveyed out of the first piece outlet chamber 3 after sublimation deposition.

It should be noted that the chamber shapes of the near-space sublimation chamber 1, the first preparation chamber 2 and the first sheet outlet chamber 3 in the present invention include, but are not limited to, a cubic shape, and may be all possible geometric shapes such as a cylindrical shape, a spherical shape, a conical shape, etc. The inner spaces of the first preparation chamber 2 and the first sheet outlet chamber 3 are small, which is beneficial to quickly pumping the chambers to a low vacuum state, and before the substrate 37 enters the first preparation chamber 2, a film can be coated on the back surface (non-deposition surface) of the substrate 37 or a baffle plate is covered on the back surface, so that inorganic or organic precursors are prevented from being deposited on the back surface of the substrate 37.

Further, first extraction opening 7 has all been seted up on the lateral wall of first preparation cavity 2, the lateral wall of near-space sublimation room 1 and the lateral wall of first piece cavity 3, the external vacuum pump of first extraction opening 7 carries out the evacuation to corresponding first preparation cavity 2, near-space sublimation room 1 and first piece cavity 3 through first extraction opening 7. The butt joint of the first preparation chamber 2 and the close space sublimation chamber 1 and the butt joint of the close space sublimation chamber 1 and the first sheet outlet chamber 3 are both provided with a first temperature control device 11.

In the invention, the first temperature control device 11 has a water cooling function, can cool the transfer pipeline (the joint between the first preparation chamber 2 and the near-space sublimation chamber 1 and the joint between the near-space sublimation chamber 1 and the first sheet outlet chamber 3), can condense the inorganic precursor 25 gas in the near-space sublimation chamber 1 on the pipe wall when the first control valve 8 is opened, and can prevent the first preparation chamber 2 and the first sheet outlet chamber 3 from being polluted.

Further, the inlet end of the first preparation chamber 2, the butt joint of the first preparation chamber 2 and the close space sublimation chamber 1, the butt joint of the close space sublimation chamber 1 and the first sheet outlet chamber 3, and the outlet end of the first sheet outlet chamber 3 are all provided with a first control valve 8. Each first control valve 8 controls the communication of each chamber, and all first control valves 8 can be baffle structures with controllable opening angles, can also be arranged in specific air paths with controllable flow, and can be arranged and communicated in a single-path or multi-path array mode.

Further, an online component detection feedback module 6 is arranged inside the close space sublimation chamber 1. The online component detection feedback module 6 is connected with the sublimation source 5 to form a set of closed loop system, the online component detection feedback module 6 feeds back the data of the component monitoring of the inorganic precursor layer to the temperature control system of the sublimation source 5, when a certain component is too much, the sublimation source 5 can be cooled, and when a certain component is too little, the sublimation source 5 can be heated, so that the components meet the set requirements.

Furthermore, a first pressure regulating port is formed in the wall of the near-space sublimation chamber 1, and a first pressure regulating valve 9 is arranged on the first pressure regulating port. Working gas is supplemented into the near space sublimation chamber 1 or the working gas is discharged through the first pressure regulating port, so that the pressure in the near space sublimation chamber 1 is regulated, and the selectable working gas is nitrogen or inert gas such as argon. A pressure monitor 10 is optionally arranged in the near-space sublimation chamber 1, and can monitor the air pressure in the cavity in real time.

Further, the first substrate stage 4 is a rotation structure with a changeable inclination angle, the first substrate stage 4 rotates with the center as a rotation point, and the inclination angle of the first substrate stage 4 is 0-4 °. The substrate angle of the substrate can be adjusted through the inclination of the first substrate carrying platform 4, the pressure of the chamber can be controlled, the process parameters such as the deposition angle, the deposition speed and the like of the inorganic precursor layer prepared by a vacuum method can be precisely regulated and controlled, so that the inorganic precursor layer has proper porosity, and the reaction with an organic precursor solution is facilitated to form a high-quality perovskite crystal film.

Further, the inside of the sublimation source cartridge 24 is divided into a first temperature zone, a second temperature zone and a third temperature zone along the conveyance direction of the substrate 37, and independent temperature control is possible, the first temperature zone and the third temperature zone being higher in temperature than the second temperature zone. Thereby ensuring the uniformity of the deposited film.

Further, as shown in fig. 3 and 4, the surface sublimation source includes a sublimation tray 36, and the inorganic precursor 25 is placed in the sublimation tray 36. Optionally, the inorganic precursors 25 are arranged in a zigzag pattern (as shown in fig. 3), a zigzag pattern or an array (as shown in fig. 4) in the planar sublimation source.

In the present invention, when the sublimation source 5 is a surface sublimation source, the inorganic precursors 25 may be arranged in a zigzag, or array configuration, thereby ensuring uniformity of the sublimation film layer. Of course, the present invention is not limited to the three arrangements defined above, and other arrangements and derivative distributions can be used in the present invention.

the substrate 37 containing the first charge transport layer 38 enters the first substrate carrying platform 4 of the close-space sublimation device, after the substrate 37 enters the first preparation chamber 2, the first control valve 8 is closed, the first preparation chamber 2 is vacuumized, after the first preparation chamber is vacuumized to a certain vacuum degree, the first control valve 8 between the first preparation chamber 2 and the close-space sublimation chamber 1 is opened, the substrate 37 enters the close-space sublimation chamber 1 and then starts to form an inorganic precursor layer, the deposition thickness range of the inorganic precursor layer is 100-600 nm, the temperature range of the sublimation source 5 is 80-1000 ℃, and the temperature of the first substrate carrying platform 4 is set to be 20-300 ℃.

The tilt angle of the first substrate stage 4, the temperatures of the sublimation source 5 and the first substrate stage 4, and the pressures of the respective chambers are precisely controlled according to the material system and the thickness range of the deposited inorganic precursor 25. And simultaneously depositing the lead-containing inorganic precursor and the cesium-containing inorganic precursor, and controlling the sublimation rates of the lead-containing inorganic precursor and the cesium-containing inorganic precursor by regulating the temperature of the sublimation sources 5, thereby regulating the deposition ratio of lead and cesium. In the deposition process, the first sheet outlet chamber 3 is pumped to a low vacuum state, after the deposition is finished, the first control valves 8 of the near space sublimation chamber 1 and the first sheet outlet chamber 3 are opened, and after the substrate 37 enters the first sheet outlet chamber 3, the first control valve 8 between the near space sublimation chamber 1 and the first sheet outlet chamber 3 is closed.

In another embodiment, the present invention provides a vapor transport apparatus, as shown in fig. 5, comprising a vapor deposition chamber 12, a second substrate stage 17 horizontally movable being provided inside the vapor deposition chamber 12, the substrate 37 being placed on the second substrate stage 17; the bottom of the vapor deposition chamber 12 is butted with a vapor transport chamber 15, at least one evaporation boat 23 is arranged in the vapor transport chamber 15 side by side along the horizontal direction, and pressure concentration sensors 18 are arranged in the vapor deposition chamber 12 and the vapor transport chamber 15.

According to the invention, the pressure concentration sensors 18 are arranged in the vapor deposition chamber 12 and the vapor transport chamber 15, so that the air pressure and the gas concentration in the chamber can be monitored in real time.

Furthermore, two ends of the vapor deposition chamber 12 are respectively abutted to the second preparation chamber 13 and the second sheet outlet chamber 14, the substrate 37 conveyed by the previous process is conveyed into the vapor deposition chamber 12 from the second preparation chamber 13, and is conveyed out from the second sheet outlet chamber 14 after sublimation deposition.

It should be noted that the chamber shapes of the vapor deposition chamber 12, the vapor transport chamber 15, the second preparation chamber 13 and the second ejection chamber 14 in the present invention include, but are not limited to, a cubic shape, and may be all possible geometric shapes such as a cylindrical shape, a spherical shape, a conical shape, and the like. The small internal space of the second preparation chamber 13 and the second sheet outlet chamber 14 is beneficial to quickly pumping the chambers to a low vacuum state, and before the substrate 37 enters the second preparation chamber 13, a film can be coated or a baffle can be covered on the back surface (non-deposition surface) of the substrate 37, so as to prevent the inorganic or organic precursor from being deposited on the back surface of the substrate 37.

It should be noted that the vapor deposition chamber 12 and the vapor transport chamber 15 in the present invention also have a chamber baking function, when the apparatus operates for a period of time, some inorganic precursors may adhere to the inner wall, and the chamber baking function is turned on to continuously heat the inner wall of the chamber (the heating range is 25 to 500 ℃), so that the inorganic precursors 25 adhering to the inner wall of the chamber may be evaporated out, thereby achieving the purpose of cleaning the chamber, and the exhaust gas is exhausted through the exhaust opening.

Further, a second pumping hole 20 is formed in each of the sidewall of the second preparation chamber 13, the sidewall of the vapor deposition chamber 12, and the sidewall of the second wafer discharging chamber 14, the second pumping hole 20 is externally connected to a vacuum pump, and the second preparation chamber 13, the vapor deposition chamber 12, and the second wafer discharging chamber 14 are pumped to vacuum through the second pumping hole 20. And a second temperature control device 21 is arranged at the joint of the second preparation chamber 13 and the vapor deposition chamber 12 and the joint of the vapor deposition chamber 12 and the second sheet outlet chamber 14.

In the present invention, the second temperature control device 21 has a water-cooling function, and can cool the transfer pipeline (the joint between the second preparation chamber 13 and the vapor deposition chamber 12, and the joint between the vapor deposition chamber 12 and the second wafer discharge chamber 14), so that the inorganic precursor 25 gas in the vapor deposition chamber 12 can be condensed on the pipe wall when the second control valve 22 is opened, thereby preventing the second preparation chamber 13 and the second wafer discharge chamber 14 from being contaminated.

Further, a second control valve 22 is arranged at the inlet end of the second preparation chamber 13, the joint of the second preparation chamber 13 and the vapor deposition chamber 12, the joint of the vapor deposition chamber 12 and the second sheet outlet chamber 14, the joint of the vapor deposition chamber 12 and the vapor transport chamber 15, and the outlet end of the second sheet outlet chamber 14.

Further, the walls of the vapor deposition chamber 12 and the vapor transport chamber 15 are provided with a second pressure regulating port, and a second pressure regulating valve 19 is arranged at the second pressure regulating port. And supplying working gas into the vapor deposition chamber 12 and/or the vapor transport chamber 15 or discharging the working gas through the second pressure regulating port, so as to regulate the pressure in the vapor deposition chamber 12 and/or the vapor transport chamber 15, wherein the optional working gas is inert gas such as nitrogen or argon. Pressure monitors are optionally arranged in the vapor deposition chamber 12 and the vapor transport chamber 15, and the pressure in the chambers can be monitored in real time.

Further, the second substrate stage 17 is a rotary structure with a changeable tilt angle. The second substrate stage 17 rotates with the center as a rotation point, the inclination angle of the second substrate stage 17 is 0-45 °, and a stage baffle 16 is arranged at the bottom of the second substrate stage 17.

The substrate angle of the substrate can be adjusted through the inclination of the second substrate carrying platform 17, the pressure of the chamber can be controlled, the process parameters such as the deposition angle, the deposition speed and the like of the inorganic precursor layer prepared by a vacuum method can be precisely regulated and controlled, so that the inorganic precursor layer has proper porosity, and the reaction with an organic precursor solution is facilitated to form a high-quality perovskite crystal film. A stage baffle 16 is arranged within a range of 1-5 cm below the second substrate stage 17, and the stage baffle 16 can completely shield, completely expose or partially expose the second substrate stage 17.

a substrate 37 containing a first charge transport layer 38 enters a second substrate carrying platform 17 of a gas phase conveying device, after the substrate 37 enters a second preparation chamber 13, a second control valve 22 is closed, the second preparation chamber 13 is vacuumized, after the substrate is vacuumized to a certain vacuum degree, the second control valve 22 between the second preparation chamber 13 and a gas phase deposition chamber 12 is opened, the substrate 37 enters the gas phase deposition chamber 12 and starts to deposit an inorganic precursor layer, the deposition thickness range of the inorganic precursor layer is 100-600 nm, the temperature of an evaporation boat 23 is controlled to be 60-300 ℃, and the temperature of the second substrate carrying platform 17 is set to be 20-300 ℃.

The tilt angle of the second substrate stage 17, the temperatures of the evaporation boat 23 and the second substrate stage 17, and the pressures of the respective chambers are precisely controlled according to the material system and the thickness range of the deposited inorganic precursor 25. And simultaneously depositing the lead-containing inorganic precursor 25 and the cesium-containing inorganic precursor 25, and controlling the sublimation rates of the lead-containing inorganic precursor and the cesium-containing inorganic precursor by regulating the temperature of the sublimation source 5, thereby regulating the deposition ratio of lead and cesium. During the deposition process, the second wafer discharging chamber 14 is already pumped to a low vacuum state, after the deposition is completed, the second control valve 22 of the near-vapor deposition chamber 12 and the second wafer discharging chamber 14 is opened, and after the substrate 37 enters the second wafer discharging chamber 14, the second control valve 22 between the vapor deposition chamber 12 and the second wafer discharging chamber 14 is closed.

In another embodiment, the present invention provides an annealing heating apparatus, as shown in fig. 6, comprising a heating chamber 29, wherein a conveying device 32 is disposed in the heating chamber 29, the substrate 37 is placed on the conveying device 32 and conveyed from one end to the other end of the heating chamber 29, and the inside of the heating chamber 29 is divided into a low temperature holding section 33, a high temperature holding section 34 and a cooling section 35 along the conveying direction of the substrate 37.

An annealing preparation chamber 30 and an annealing sheet outlet chamber 31 which are communicated with the host and the object are respectively arranged at two ends of the heating chamber 29, the substrate 37 conveyed in the previous process is conveyed into the heating chamber 29 through the annealing preparation chamber 30, and the substrate is conveyed out through the annealing sheet outlet chamber 31 after the annealing treatment is finished.

In another embodiment, the present invention provides a method for preparing a perovskite battery, wherein the devices used in the method are the devices provided in the above embodiments, and the method specifically comprises the following steps:

(1) preparing a first charge transport layer 38 on a conductive glass substrate 37 or a textured substrate 37

Preparing a first charge transport layer 38 with a thickness of 0.1-50 nm on the conductive glass substrate 37 or the textured substrate 37 by an evaporation method, a sputtering method, a chemical bath deposition method, a precursor solution spin-coating method, a precursor solution blade method or a slit coating method, wherein the first charge transport layer 38 is made of cuprous thiocyanate, cuprous iodide, cuprous oxide, nickel oxide, vanadium pentoxide, molybdenum trioxide, 22'77' -tetrakis [ NN-bis (4-methoxyphenyl) amino ] -99' -spirobifluorene, poly (3-hexylthiophene-2, 5-diyl), poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ], poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), titanium dioxide, tin dioxide, fullerene, bathocuproine, zinc oxide or [ 6], any one of 6] -phenyl-C61-butyric acid isopropyl ester;

(2) preparation of perovskite thin film 39

(2.1) depositing an inorganic precursor layer on the surface of the first charge transport layer 38 by using the close space sublimation apparatus (shown in fig. 1) provided by the embodiment, the process comprises:

the substrate 37 containing the first charge transport layer 38 enters the first substrate carrying stage 4 of the close-space sublimation device, after the substrate 37 enters the first preparation chamber 2, the first control valve 8 is closed, the first preparation chamber 2 is vacuumized, and after the first preparation chamber 2 is vacuumized to a certain vacuum degree, the first control valve 8 between the first preparation chamber 2 and the close-space sublimation chamber 1 is opened, the substrate 37 enters the close-space sublimation chamber 1, and an inorganic precursor 25 (including a lead-containing inorganic precursor and a cesium-containing inorganic precursor, wherein the lead-containing inorganic precursor includes PbI₂、PbBr₂Or PbCl₂Any one or a combination of at least two of the above, the cesium-containing inorganic precursor includes any one or a combination of at least two of CsI, CsBr or CsCl), the inorganic precursor 25 is sublimated and then deposited on the surface of the first charge transport layer 38 to form an inorganic precursor layer, the deposition thickness of the inorganic precursor layer is 100-600 nm, the temperature of the sublimation source 5 is 80-1000 ℃, and the temperature of the first substrate stage 4 is 20-300 ℃;

in the deposition process, the first sheet outlet chamber 3 is pumped to a low vacuum state, after the deposition is finished, the first control valves 8 of the near space sublimation chamber 1 and the first sheet outlet chamber 3 are opened, and after the substrate 37 enters the first sheet outlet chamber 3, the first control valve 8 between the near space sublimation chamber 1 and the first sheet outlet chamber 3 is closed;

(2.2) conveying the substrate 37 into a coating device, and coating an organic precursor solution on the surface of the inorganic precursor layer, wherein the organic precursor solution comprises a precursor solute and a solvent; the precursor solute comprises a first solute, a second solute and a third solute, wherein the first solute is selected from iodomethylamine or iodoformamidine, the second solute is selected from bromomethylamine or bromoformamidine, the third solute is selected from chloromethylamine or chloromethylamidine, and the mass ratio of the first solute to the second solute to the third solute is (50-99): 1-50); the solvent comprises a first solvent, a second solvent and a third solvent, wherein the first solvent is any one of ethylene glycol monomethyl ether, n-propanol, isopropanol, ethanol or methanol; the second solvent is selected from any one of tert-butyl alcohol, n-butyl alcohol, 2-amyl alcohol, 1, 2-propylene glycol, n-hexane, ethyl acetate, chlorobenzene, diethyl ether or acetonitrile; the third solvent is selected from any one of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, ethylene glycol monomethyl ether or dimethyl pyridine N-oxide, and the mass ratio of the first solvent to the second solvent to the third solvent is (50-99.99): 0.01-50); the total concentration of the organic precursor solution is 0.1-1.5 mol/L, and the coating parameters of the coating device are adjusted, wherein the coating parameters comprise: the coating speed is 5-50 mm/s, the liquid injection amount is 5-500 mu L/s, the slit height is 10-200 mu m, and the air pressure of an air knife is 0.01-0.1 MPa;

(2.3) after coating, conveying the substrate 37 into a heating annealing device (as shown in fig. 6), conveying the substrate 37 from one end of the heating annealing device to the other end of the heating annealing device under the drive of a conveying device 32, and sequentially passing through a low-temperature heat preservation section 33, a high-temperature heat preservation section 34 and a cooling section 35 in the conveying process, wherein the temperature of the low-temperature heat preservation section 33 is 50-120 ℃, the heating temperature of the high-temperature heat preservation section 34 is 100-180 ℃, and the substrate 37 is cooled to room temperature in the cooling section 35 through air cooling; the total time of the whole conveying process is 10-60 min, and the conveying speed is 0.1-3 m/min; after heating and annealing, the inorganic precursor layer and the organic precursor solution react to form the perovskite thin film 39, and the reaction mechanism is as follows:

PbI₂+MAI→MAPbI₃

PbI₂+FAI→FAPbI₃

PbI₂+MAI+FAI→MA_xFA_(1-x)PbI₃

PbI₂+FAI+MABr+MACl→MA_xFA_(1-x)PbI_yBr_zCl_(3-y-z-x)

PbI₂+CsI+FAI+MABr+MACl→MA_xFA_yCs_(1-x-y)PbI_mBr_nCl_(3-m-n)

wherein step (2.1) can be replaced by the following step (2.1'):

(2.1') depositing an inorganic precursor layer on the surface of the first charge transport layer 38 using a vapor transport device (as shown in fig. 5) provided in an embodiment, the process comprising:

the substrate 37 containing the first charge transport layer 38 enters the second substrate stage 17 of the vapor transport device and the substrate37 into the second preparation chamber 13, the second control valve 22 is closed, the second preparation chamber 13 is vacuumized, after the second preparation chamber 13 is vacuumized to a certain vacuum degree, the second control valve 22 between the second preparation chamber 13 and the vapor deposition chamber 12 is opened, the substrate 37 enters the vapor deposition chamber 12, and the evaporation boat 23 in the vapor transport chamber 15 contains inorganic precursors 25 (including lead-containing inorganic precursors including PbI and cesium-containing inorganic precursors including PbI)₂、PbBr₂Or PbCl₂Any one or a combination of at least two of the above, the cesium-containing inorganic precursor includes any one or a combination of at least two of CsI, CsBr or CsCl), the inorganic precursor 25 is evaporated and then deposited on the surface of the first charge transport layer 38 to form an inorganic precursor layer, the deposition thickness of the inorganic precursor layer is 100-600 nm, the temperature of the evaporation boat 23 is 60-300 ℃, and the temperature of the second substrate stage 17 is 20-300 ℃;

during the deposition process, the second wafer discharging chamber 14 is already pumped to a low vacuum state, after the deposition is completed, the second control valve 22 of the near-vapor deposition chamber 12 and the second wafer discharging chamber 14 is opened, and after the substrate 37 enters the second wafer discharging chamber 14, the second control valve 22 between the vapor deposition chamber 12 and the second wafer discharging chamber 14 is closed.

(3) Preparation of the second Charge transport layer 40

Preparing a second charge transport layer 40 with the thickness of 5-50 nm by adopting an evaporation method, a sputtering method, a precursor solution spin-coating method, a precursor solution blade coating method or a slit coating method;

(4) preparing a back electrode 41 to obtain the perovskite battery

The back electrode 41 is divided into a metal back electrode and a transparent back electrode. The metal back electrode comprises any one of a silver electrode (Ag), a copper electrode (Cu), a gold electrode (Au), an aluminum electrode (Al), a molybdenum electrode (Mo) or a chromium electrode (Cr), and the thickness of the metal back electrode is 40-100 nm. The preparation method of the metal back electrode adopts an evaporation method or a sputtering method. The transparent back electrode comprises tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO) or zinc oxide, the thickness of the transparent back electrode is 50-100 nm, and a sputtering method is adopted in the preparation method of the transparent back electrode.

Example 1

The invention provides a preparation method of a perovskite battery, devices adopted in the preparation method are various devices provided by the specific embodiment, and the preparation method specifically comprises the following steps:

(1) adopt the blade coating method to prepare one deck cuprous thiocyanate film on ITO conductive glass, then shift base 37 to near space sublimation device on first base microscope carrier 4, base 37 gets into behind first preparation chamber 2, first control valve 8 is closed, to first preparation chamber 2 evacuation, first preparation chamber 2 and near space sublimation room 1 between the first valve open, base 37 gets into near space sublimation room 1 after and begins the deposit inorganic precursor layer, inorganic precursor 25 on inorganic precursor layer is PbI₂300nm thick, PbI₂The temperature of the sublimation source 5 is 350 ℃, and the temperature of the first substrate carrying platform 4 is 25 ℃;

(2) coating an organic precursor solution on the surface of the inorganic precursor layer by using a coating device, wherein the precursor solutes of the organic precursor solution are FAI, MABr and MACl, the mass ratio of the FAI, the MABr and the MACl is 50:1:1, the solvent is a mixed solution of isopropanol and ethanol, the total concentration of the organic precursor solution is 0.5mol/L, and the coating process parameters of the coating device are set as follows: the coating speed is 40mm/s, the liquid injection amount is 30 mu L/s, the slit width is 60 mu m, and the air pressure of an air knife is 0.05 MPa;

(3) after coating, immediately transferring the substrate 37 to a conveying device 32 of a heating annealing device, wherein the conveying device 32 drives the substrate 37 to move from one end to the other end at a moving speed of 0.1m/min, the substrate 37 sequentially passes through a low-temperature heat preservation section 33 at 50 ℃, a high-temperature heat preservation section 34 at 100 ℃ and a cooling section 35, the substrate 37 is cooled to room temperature through air cooling in the cooling section 35, the total time of annealing treatment is 60min, and in the heating annealing process, an inorganic precursor layer and an organic precursor solution react to form a perovskite thin film 39;

(4) c60 was evaporated to a thickness of 20nm on the perovskite thin film 39, and a Cu electrode was evaporated to a thickness of 60nm to finally prepare a perovskite battery as shown in fig. 7.

The perovskite battery prepared in the embodiment is tested, and the test results are shown in table 1.

Example 2

(1) adopt the blade coating method to prepare one deck cuprous thiocyanate film on ITO conductive glass, then shift base 37 to near space sublimation device on first base microscope carrier 4, base 37 gets into behind first preparation chamber 2, first control valve 8 is closed, to first preparation chamber 2 evacuation, first preparation chamber 2 and near space sublimation room 1 between the first valve open, base 37 gets into near space sublimation room 1 after and begins the deposit inorganic precursor layer, inorganic precursor 25 on inorganic precursor layer is PbI₂And CsBr, thickness 350nm, PbI₂The temperature of the sublimation source 5 is 350 ℃, the temperature of the CsBr sublimation source 5 is 450 ℃, and the temperature of the first substrate stage 4 is set to be 25 ℃;

(2) coating an organic precursor solution on the surface of the inorganic precursor layer by using a coating device, wherein the precursor solutes of the organic precursor solution are MAI, FABr and MACl, the mass ratio of the MAI, the FABr and the MACl is 70:20:30, the solvent is a mixed solution of ethanol, n-butyl alcohol and methanol, the total concentration of the organic precursor solution is 0.6mol/L, and the coating process parameters of the coating device are set as follows: the coating speed is 45mm/s, the liquid injection amount is 40 mul/s, the slit width is 70 mu m, and the air pressure of an air knife is 0.08 MPa;

(3) after coating, immediately transferring the substrate 37 to a conveying device 32 of a heating annealing device, wherein the conveying device 32 drives the substrate 37 to move from one end to the other end at a moving speed of 1.5m/min, the substrate 37 sequentially passes through a low-temperature heat preservation section 33 at 100 ℃, a high-temperature heat preservation section 34 at 150 ℃ and a cooling section 35, the substrate 37 is cooled to room temperature through air cooling in the cooling section 35, the total time of annealing treatment is 40min, and in the heating annealing process, an inorganic precursor layer and an organic precursor solution react to form a perovskite thin film 39;

(4) PCBM with the thickness of 20nm is evaporated on the perovskite thin film 39, and then Ag electrodes with the thickness of 50nm are evaporated, and finally the perovskite battery shown in figure 7 is prepared.

Example 3

(1) preparing a layer of PTAA thin film on ITO conductive glass by adopting an evaporation method, then transferring a substrate 37 onto a second substrate carrying table 17 of a vapor transport device, closing a second control valve 22 after the substrate 37 enters a second preparation chamber 13, vacuumizing the second preparation chamber 13, opening second valves between the second preparation chamber 13 and a vapor deposition chamber 12 and between the vapor deposition chamber 12 and a vapor transport chamber 15, starting depositing an inorganic precursor layer after the substrate 37 enters the vapor deposition chamber 12, wherein an inorganic precursor 25 of the inorganic precursor layer is PbI₂And CsI, thickness 360nm, PbI₂The temperature of the evaporation boat 23 is 380 ℃, the temperature of the CsBr evaporation boat 23 is 500 ℃, and the temperature of the second substrate carrying platform 17 is 25 ℃;

(2) coating an organic precursor solution on the surface of the inorganic precursor layer by using a coating device, wherein the precursor solutes of the organic precursor solution are FAI, FABr and MACl, the mass ratio of the FAI, the FABr and the MACl is 99:50:50, the solvent is a mixed solution of ethanol, 2-butanol and tert-butanol, the total concentration of the organic precursor solution is 0.4mol/L, and the coating technological parameters of the coating device are set as follows: the coating speed is 50mm/s, the liquid injection amount is 60 mul/s, the slit width is 80 mu m, and the air pressure of an air knife is 0.05 MPa;

(3) after coating, immediately transferring the substrate 37 to a conveying device 32 of a heating annealing device, wherein the conveying device 32 drives the substrate 37 to move from one end to the other end at a moving speed of 3m/min, the substrate 37 sequentially passes through a low-temperature heat preservation section 33 at 120 ℃, a high-temperature heat preservation section 34 at 180 ℃ and a cooling section 35, the substrate 37 is cooled to room temperature in the cooling section 35 through air cooling, the total time of annealing treatment is 10min, and in the heating annealing process, an inorganic precursor layer and an organic precursor solution react to form a perovskite film 39;

(4) c60 with the thickness of 20nm is evaporated on the perovskite thin film 39, BCP with the thickness of 5nm is evaporated, and finally a Cu electrode with the thickness of 60nm is evaporated, so that the perovskite battery shown in figure 7 is finally prepared.

Comparative example 1

The invention provides a preparation method of a perovskite battery, which specifically comprises the following steps:

(1) preparing a layer of cuprous thiocyanate film on the ITO conductive glass by adopting a blade coating method;

(2) mixing inorganic precursor 25PbI₂Dissolved in methyl sulfoxide to obtain PbI with concentration of 0.5g/ml₂Solution, spin coating PbI on the surface of cuprous thiocyanate film₂Solution, heat-treating at 90 deg.C for 30min to obtain PbI₂A film;

(3) in PbI₂Coating an organic precursor solution on the surface of the film, wherein the components and the content ratio of the organic precursor solution are completely the same as those of the organic precursor solution in the step (2) in the embodiment 1, and the coating process parameters of a coating device are set to be completely the same as those of the coating process in the step (2) in the embodiment 1;

(4) repeating the step (4) for 6 times, performing heat treatment at 80 ℃ for 20min to obtain a perovskite thin film 39, evaporating C60 with the thickness of 20nm on the perovskite thin film 39, evaporating a Cu electrode with the thickness of 60nm, and finally preparing the perovskite battery shown in the figure 7.

The perovskite cell prepared in this comparative example was tested and the test results are shown in table 2.

TABLE 1

TABLE 2

By observing the appearances of the perovskite thin films 39 prepared in the example 1 and the perovskite thin film 39 prepared in the comparative example 1, the perovskite thin film 39 prepared in the example 1 is more uniform and smooth, black and bright, and the vacuum-solution two-step method after optimization is more easy to realize the uniform growth of a large-area film layer on an inorganic precursor layer.

As can be seen by comparing the test data in tables 1 and 2, the perovskite cell prepared by the vacuum-solution two-step method provided in example 1 has better performance than the two-step solution method provided in comparative example 1.

The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims

1. A two-step process for preparing a perovskite thin film, comprising:

2. The method of claim 1, wherein the substrate comprises a conductive glass substrate or a textured substrate;

preferably, the material of the first charge transport layer comprises any one of cuprous thiocyanate, cuprous iodide, cuprous oxide, nickel oxide, vanadium pentoxide, molybdenum trioxide, 22'77' -tetrakis [ NN-bis (4-methoxyphenyl) amino ] -99' -spirobifluorene, poly (3-hexylthiophene-2, 5-diyl), poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ], poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), titanium dioxide, tin dioxide, fullerene, bathocuproine, zinc oxide, or [6,6] -phenyl-C61-butyric acid isopropyl ester;

preferably, the first charge transport layer is prepared by an evaporation method, a sputtering method, a chemical bath deposition method, a precursor solution spin coating method, a precursor solution blade coating method or a slit coating method;

preferably, the thickness of the first charge transport layer is 0.1-50 nm.

3. The method according to claim 1 or 2, wherein the near-space sublimation method is carried out in a near-space sublimation device, the near-space sublimation device comprises a sublimation source containing an inorganic precursor, and the temperature of the sublimation source is controlled to be 80-1000 ℃;

preferably, the gas-phase transportation method is carried out in a gas-phase transportation device, the gas-phase transportation device comprises an evaporation boat containing an inorganic precursor, and the temperature of the evaporation boat is controlled to be 60-300 ℃;

preferably, a substrate carrying table is arranged inside the close space sublimation device and the gas phase conveying device, and the substrate carrying table horizontally moves in the close space sublimation device and the gas phase conveying device so as to convey the substrate to the next process;

preferably, the temperature of the substrate carrying platform is controlled to be 20-300 ℃.

4. A method according to any of claims 1-3, wherein the material of the inorganic precursor layer comprises a lead-containing inorganic precursor;

preferably, the lead-containing inorganic precursor comprises PbI₂、PbBr₂Or PbCl₂Any one or a combination of at least two of;

preferably, the material of the inorganic precursor layer further comprises a cesium-containing inorganic precursor;

preferably, the cesium-containing inorganic precursor includes any one or a combination of at least two of CsI, CsBr, or CsCl;

preferably, the thickness of the inorganic precursor layer is 100 to 600 nm.

5. The method according to any one of claims 1 to 4, wherein the coating is slot coating or blade coating;

preferably, the coating speed is 5-50 mm/s;

preferably, the coating is carried out in a coating device;

preferably, the liquid injection amount of the coating device is 5-500 mu L/s;

preferably, the slit height of the coating device is 10-200 μm;

preferably, the air knife wind pressure of the coating device is 0.01-0.1 MPa.

6. The method according to any one of claims 1 to 5, wherein the organic precursor solution comprises a precursor solute and a solvent;

preferably, the precursor solute comprises a combination of at least two of iodomethylamine, iodoformamidine, bromomethylamine, bromoformamidine, chloromethylamine, or chloroformamidine;

preferably, the precursor solutes comprise a first solute selected from iodomethylamine or iodoformamidine, a second solute selected from bromomethylamine or bromoformamidine, and a third solute selected from chloromethylamine or chloromethylamidine;

preferably, the mass ratio of the first solute to the second solute to the third solute is (50-99): 1-50);

preferably, the solvent comprises a combination of at least two of N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, ethylene glycol methyl ether, lutidine N-oxide, N-propanol, isopropanol, t-butanol, N-butanol, 2-pentanol, 1, 2-propanediol, N-hexane, ethyl acetate, chlorobenzene, diethyl ether, acetonitrile, ethanol, or methanol;

preferably, the solvent comprises a first solvent, a second solvent, and a third solvent;

the first solvent is selected from any one of ethylene glycol monomethyl ether, normal propyl alcohol, isopropyl alcohol, ethanol or methanol;

the second solvent is selected from any one of tert-butyl alcohol, n-butyl alcohol, 2-amyl alcohol, 1, 2-propylene glycol, n-hexane, ethyl acetate, chlorobenzene, diethyl ether or acetonitrile;

the third solvent is any one of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, ethylene glycol monomethyl ether or dimethyl pyridine N-oxide;

preferably, the concentration of the organic precursor solution is 0.1-1.5 mol/L.

7. The method according to any one of claims 1 to 6, wherein the annealing treatment is performed in a thermal annealing apparatus comprising a heating chamber in which a conveyor is disposed, the substrate being placed on the conveyor and conveyed from one end of the heating chamber to the other end, the heating chamber being internally divided into a low-temperature soaking section, a high-temperature soaking section, and a cooling section in a conveyance direction of the substrate;

preferably, the temperature of the low-temperature heat preservation section is 50-120 ℃;

preferably, the heating temperature of the high-temperature heat preservation section is 100-180 ℃;

preferably, the substrate is cooled to room temperature in the cooling section by air cooling;

preferably, the annealing treatment time is 10-60 min;

preferably, the conveying speed of the substrate is 0.1-3 m/min;

8. A close space sublimation apparatus, wherein the close space sublimation apparatus is used for carrying out the close space sublimation method in the method according to any one of claims 1 to 7;

the near space sublimation device comprises a near space sublimation chamber, a first substrate carrying table which moves horizontally is arranged in the near space sublimation chamber, the deposition side of the substrate is placed on the first substrate carrying table downwards, at least one sublimation source which is arranged side by side along the substrate conveying direction is arranged on the bottom layer in the near space sublimation chamber, and the sublimation source is a linear sublimation source or a surface sublimation source;

9. The near space sublimation device according to claim 8, wherein the near space sublimation device further comprises a first preparation chamber and a first sheet outlet chamber which are respectively butted with two ends of the near space sublimation chamber, the substrate conveyed by the previous process is conveyed into the near space sublimation chamber from the first preparation chamber, and the substrate is conveyed out from the first sheet outlet chamber after sublimation deposition;

preferably, the side wall of the first preparation chamber, the side wall of the near-space sublimation chamber and the side wall of the first sheet outlet chamber are all provided with first air extraction ports, the first air extraction ports are externally connected with a vacuum pump, and the first preparation chamber, the near-space sublimation chamber and the first sheet outlet chamber are correspondingly vacuumized through the first air extraction ports;

preferably, a first temperature control device is arranged at the joint of the first preparation chamber and the near-space sublimation chamber and at the joint of the near-space sublimation chamber and the first sheet outlet chamber;

preferably, the inlet end of the first preparation chamber, the joint of the first preparation chamber and the near-space sublimation chamber, the joint of the near-space sublimation chamber and the first sheet outlet chamber, and the outlet end of the first sheet outlet chamber are all provided with a first control valve;

preferably, an online component detection feedback module is further arranged inside the near-space sublimation chamber;

10. The close-space sublimation device according to claim 8 or 9, wherein the first substrate stage is a rotary structure with a changeable inclination angle;

preferably, the first substrate stage rotates with a center as a rotation point;

preferably, the inclination angle of the first substrate stage is 0 to 45 °.

11. The close-space sublimation apparatus according to any one of claims 8 to 10, wherein the inside of the sublimation source cartridge is partitioned into a first temperature zone, a second temperature zone and a third temperature zone along the substrate conveyance direction, the first temperature zone and the third temperature zone having higher temperatures than the second temperature zone.

12. The close-space sublimation device according to any one of claims 8-11, wherein the surface sublimation source comprises a sublimation tray in which an inorganic precursor is placed;

13. A gas phase transport apparatus for carrying out the gas phase transport method of any one of claims 1 to 7;

14. The vapor transport device of claim 13, wherein two ends of the vapor deposition chamber are respectively butted with the second preparation chamber and the second sheet discharge chamber, the substrate conveyed by the previous process is conveyed into the vapor deposition chamber from the second preparation chamber, and the substrate is conveyed out from the second sheet discharge chamber after sublimation deposition;

preferably, the sidewall of the second preparation chamber, the sidewall of the vapor deposition chamber, and the sidewall of the second wafer discharge chamber are respectively provided with a second pumping port, the second pumping port is externally connected with a vacuum pump, and the second preparation chamber, the vapor deposition chamber, and the second wafer discharge chamber are correspondingly pumped to vacuum through the second pumping port;

preferably, a second temperature control device is arranged at the joint of the second preparation chamber and the vapor deposition chamber and at the joint of the vapor deposition chamber and the second sheet outlet chamber;

preferably, the inlet end of the second preparation chamber, the butt joint of the second preparation chamber and the vapor deposition chamber, the butt joint of the vapor deposition chamber and the second wafer discharging chamber, and the butt joint of the vapor deposition chamber and the vapor transport chamber and the outlet end of the second wafer discharging chamber are provided with second control valves;

15. The vapor transport device of claim 13 or 14, wherein the second substrate stage is a rotary structure with changeable tilt angle;

preferably, the second substrate stage rotates with a center as a rotation point;

preferably, the inclination angle of the second substrate carrying platform is 0-45 degrees;

16. A process for the preparation of a perovskite battery, characterized in that the process comprises a process as claimed in any one of claims 1 to 7; the preparation method also comprises the following steps:

17. The production method according to claim 16, wherein a production method of the second charge transport layer includes an evaporation method, a sputtering method, a precursor solution spin coating method, a precursor solution blade method, or a slit coating method;

preferably, the thickness of the second charge transport layer is 5-50 nm;

preferably, the back electrode comprises a metal back electrode or a transparent back electrode;

preferably, the metal material adopted by the metal back electrode comprises any one or a combination of at least two of silver, copper, gold, aluminum, molybdenum or chromium;

preferably, the thickness of the metal back electrode is 40-100 nm;

preferably, the electrode material adopted by the transparent back electrode comprises any one or a combination of at least two of tin-doped indium oxide, fluorine-doped tin oxide and zinc oxide;

preferably, the thickness of the transparent back electrode is 50-100 nm.

18. A perovskite battery manufactured by the manufacturing method as set forth in claim 16 or 17, wherein the perovskite battery comprises a substrate, a first charge transport layer, a perovskite thin film, a second charge transport layer and a back electrode which are sequentially stacked.