CN115572946A

CN115572946A - Perovskite preparation method and preparation equipment and photoelectric converter

Info

Publication number: CN115572946A
Application number: CN202211130242.3A
Authority: CN
Inventors: 刘德涛; 王硕; 辛凯; 刘云峰
Original assignee: Huawei Digital Power Technologies Co Ltd
Current assignee: Huawei Digital Power Technologies Co Ltd
Priority date: 2022-09-16
Filing date: 2022-09-16
Publication date: 2023-01-06

Abstract

The application provides a perovskite preparation method, perovskite preparation equipment and a photoelectric converter, and relates to the technical field of photoelectricity. In the embodiment of the application, through the stepwise reaction and the selection of the precursor, an intermediate can be generated based on the halogenation reaction, and then the intermediate is subjected to cation replacement based on the replacement reaction to obtain the perovskite, and as the organic matter, the organic salt and the ammonium halide can have higher saturated vapor pressure at lower temperature, the reaction temperature can be reduced, the reaction time of the perovskite can be shortened, and the preparation efficiency of the perovskite can be improved.

Description

Perovskite preparation method and preparation equipment and photoelectric converter

Technical Field

The application relates to the field of photoelectric technology, in particular to a perovskite preparation method, perovskite preparation equipment and a photoelectric converter.

Background

The perovskite has the chemical general formula ABX ₃ A is +1, A ⁺ May be selected from CH ₃ NH ₃ ⁺ (may be abbreviated as MA) ⁺ )、H ₂ C(＝NH)NH ₂ ⁺ (can be simplified)Written as FA ⁺ )、Cs ⁺ 、Rb ⁺ Etc., B is +2, B ²⁺ May be selected from Pb ²⁺ 、Sn ²⁺ Etc., X is-1 valent, X ^- May be selected from Cl ^- 、Br ^- 、I ^- Plasma halide ions of MAPbI ₃ Is one of the most classical perovskites.

When perovskite is prepared, a vapor deposition method is usually adopted for preparation, but the existing vapor deposition method adopts higher temperature which is at least above 400 ℃, the high temperature increases the requirements on the material and the structure of equipment, and increases the manufacturing cost of the equipment; in addition, the reaction time required by the current vapor deposition method is long when the perovskite is prepared, so that the preparation efficiency of the perovskite is reduced.

Therefore, how to reduce the perovskite preparation temperature and improve the perovskite preparation efficiency is a technical problem to be urgently solved by those skilled in the art.

Disclosure of Invention

The application provides a preparation method and preparation equipment of perovskite and a photoelectric converter, which are used for reducing the preparation temperature of perovskite, shortening the reaction time of perovskite and improving the preparation efficiency of perovskite.

In a first aspect, an embodiment of the present application provides a perovskite preparation apparatus, which may include:

the reaction chamber can provide a reaction space for preparing perovskite, and has a heating function, so that the reaction chamber can maintain the vapor form of a precursor;

the evaporators are connected with the reaction cavity and have a heating function, so that the evaporators can heat stored precursors into corresponding steam; wherein the perovskite has a chemical formula of ABX ₃ In this case, the precursor may include: b-containing organic substances (which can be regarded as a first type of substances), ammonium halides (which can be regarded as a second type of substances) and A-containing organic salts (which can be regarded as a third type of substances), wherein the three types of substances can be respectively stored in different evaporators; to illustrate, if different substances are stored in the same evaporator, the heating function of the evaporator is turned on in order to obtainDuring evaporation, different substances in the evaporator may react with each other, which may adversely affect the production of perovskite, and may not allow perovskite to be obtained, or may not allow perovskite to be obtained with high purity and high yield, so that different precursors may need to be stored in different evaporators.

Also, in the present embodiment, when a plurality of first and/or third types of substances are required in the production of perovskite, different substances are required to be stored in different evaporators.

Wherein, for the B-containing organic matter, B can be selected from at least one of Pb, sn, and the like; for A-containing organic salts, A may be selected from Rb, cs, CH ₃ NH ₃ And H ₂ C(＝NH)NH ₂ Etc., i.e., a may be a metal or an organic group; for the general chemical formula NH ₄ As the ammonium halide of X, X may be at least one selected from the group consisting of I, br, cl and F.

Therefore, the evaporator can heat the precursor stored in the evaporator to obtain corresponding steam, the evaporator is connected with the reaction cavity, the corresponding steam can be introduced into the reaction cavity after being obtained, the reaction cavity can enable the precursor entering the reaction cavity to maintain the form of the steam, so that the steam containing the B organic matter and the steam of the ammonium halide are subjected to halogenation reaction, the generated intermediate is subjected to replacement reaction with the steam containing the A organic salt, and the perovskite can be generated.

Because the precursor does not contain inorganic salt, the halogenation reaction and the replacement reaction can be carried out at lower temperature, and precursor vapor with high concentration can be obtained when the vacuum degree in the reaction cavity is lower; therefore, the preparation process has low requirements on the preparation equipment, so that the reaction cavity does not need to bear higher temperature and high vacuum degree, the manufacturing difficulty of the reaction cavity is reduced, the manufacturing difficulty of the preparation equipment is further reduced, the manufacturing cost of the preparation equipment is also reduced, the problem of overhigh energy consumption caused by high temperature can be solved, and the energy conservation is realized.

In the embodiment of the present invention, the material of the reaction chamber may include, but is not limited to, quartz or stainless steel, and may be any material that can have a certain hardness and can withstand a certain temperature and a certain vacuum degree, and is not limited herein; also, the shape of the reaction chamber may include, but is not limited to: square or cylindrical, etc., and may be designed according to practical needs, and is not limited herein.

In the embodiment of the present application, the surface of the reaction chamber may be provided with a heating coil or an infrared heating device to realize a heating function; in addition, the temperature in the reaction cavity can be controlled between 150 ℃ and 300 ℃ to maintain the shape of steam, and the effective operation of the preparation process is ensured.

In the embodiment of the present application, the reaction chamber may have disposed therein:

a sample stage, which can be used for placing a substrate; for example, the substrate may be placed on a sample stage, and when a halogenation reaction occurs, the generated intermediate is deposited on the surface of the substrate in the form of a thin film, and after the replacement reaction is completed, the intermediate may be converted into perovskite, so that a perovskite thin film may be produced on the surface of the substrate; the sample stage can be arranged at the bottom of the reaction cavity, so that steam can be easily deposited on the surface of the substrate under the action of gravity, and the perovskite thin film can be easily manufactured; in addition, the sample stage can have a heating function, and the temperature can be controlled to be 70-300 ℃ so as to ensure that the preparation process is smoothly and effectively carried out;

the sprayer is positioned above the sample table and at the top of the reaction chamber, and can be provided with a plurality of spraying channels, and the spraying channels are isolated from each other and are not communicated; and each evaporator is respectively connected with different spraying channels, so that steam generated in the corresponding evaporator is introduced into the reaction cavity through the different spraying channels, the steam cannot be contacted with each other before entering the reaction cavity, namely the steam enters the reaction cavity through different transmission paths, and adverse effects on the generation of the perovskite are avoided.

Therefore, the sample table and the sprayer are arranged, so that the sprayer can be positioned above the sample table, steam can be uniformly diffused downwards under the action of gravity, the uniformity of halogenation reaction and replacement reaction can be improved, uniform perovskite thin films can be manufactured on the surfaces of substrates (not limited to the substrates, but also the surfaces of any substances needing to manufacture the perovskite thin films), and the quality of the perovskite thin films is improved.

In this application embodiment, be provided with first pipeline between reaction chamber and evaporimeter, when the evaporimeter was provided with N (N is the integer that is greater than or equal to 3) and is individual, first pipeline also is provided with N, and evaporimeter and first pipeline one-to-one are connected for every evaporimeter all is connected with the reaction chamber through a first pipeline, realizes that each evaporimeter passes through different first pipeline connection reaction chamber, so that the steam that produces in each evaporimeter can let in to the reaction chamber through the first pipeline of connection.

Therefore, the vapor can be prevented from contacting each other when a plurality of evaporators introduce vapor into the reaction cavity through the same first pipeline, and the effective proceeding of halogenation reaction and replacement reaction is ensured, so that the perovskite with high purity is obtained.

In addition, in the embodiment of the present application, the first pipe may have flexibility and a certain length, so that the first pipe may be bent into various shapes according to actual needs; therefore, the arrangement of the first pipeline can be facilitated, the distance between the evaporator and the reaction cavity can be further pulled, and the flexibility of the arrangement position of the evaporator and the flexibility of the arrangement of the first pipeline are improved.

In this application embodiment, the surface of first pipeline has the heater to avoid vapour to take place the condensation in first pipeline and can't get into in the reaction chamber, and then avoid causing the adverse effect to the preparation of perovskite.

In this application embodiment, when being provided with the sprinkler in the reaction chamber, the spraying channel in the sprinkler can be provided with N, and spraying channel and first pipeline one-to-one are connected for each first pipeline is connected with the spraying channel of difference respectively, thereby, the vapour that produces in each evaporimeter can successively enter into the reaction chamber through the first pipeline that corresponds and spraying channel, can avoid each vapour to meet, contact in first pipeline and spraying channel simultaneously, guarantee halogenating reaction and effective going on of replacement reaction.

Certainly, when no sprayer is arranged in the reaction cavity, the top of the reaction cavity can be provided with N through holes, and each through hole is correspondingly connected with each first pipeline one by one, so that steam transmitted by the first pipelines can directly enter the reaction cavity through the corresponding through holes; therefore, the structure of the reaction cavity can be simplified, the manufacturing difficulty of the reaction cavity is reduced, and the manufacturing cost of the reaction cavity and even the manufacturing equipment is reduced.

In the embodiment of the application, each first pipeline is provided with one first control valve, the first control valves are arranged in one-to-one correspondence with the first pipelines, and when any one first control valve is opened, the first pipeline connected with the first control valve is in a conducting state, so that the first pipeline can communicate the connected evaporator with the reactor; when any first control valve is closed, the first pipeline connected with the first control valve is in a non-conducting state, so that the evaporator and the reactor connected with the first pipeline are not communicated.

So, through the setting of first control valve, can control the quantity of the vapour and the kind of vapour of letting in to the reaction chamber, realize the control to the reaction of going on in the reaction chamber, and then realize controlling the preparation thickness of perovskite film to satisfy the needs of different application scenarios, expand the range of application of perovskite.

In this embodiment, each evaporator may further be correspondingly provided with a second pipeline, the second pipelines are connected with the evaporators in a one-to-one correspondence manner, and each second pipeline is connected with the carrier gas supply device, so that each evaporator is connected with the carrier gas supply device through the corresponding second pipeline.

Wherein, the carrier gas provided by the carrier gas providing device may include, but is not limited to: nitrogen, inert gases or reactive gases, which may include, but are not limited to: argon or helium, etc., and the reaction gas may include, but is not limited to: ammonia gas, halogen gas, oxygen gas, or the like.

So, the carrier gas that carrier gas provides the device can let in to the evaporimeter that corresponds respectively through each second pipeline, precursor in the evaporimeter is when the vapour is converted into, the carrier gas can be as drive power, it enters into the reaction chamber to drive vapour, thereby can improve the transmission of vapour in first pipeline, make vapour can be easier, smoothly, enter into the reaction chamber fast, avoid partial vapour to stop in first pipeline and can't get into the waste that causes the precursor in the reaction chamber, improve the utilization ratio of precursor, reduce the cost of manufacture of perovskite, and can also accelerate reaction rate, improve the preparation efficiency of perovskite.

In the embodiment of the application, each second pipeline may be correspondingly provided with one second control valve, and the second pipelines and the second control valves are connected in a one-to-one correspondence manner; when any one second control valve is opened, a second pipeline connected with the second control valve is in a conducting state, so that the second pipeline can communicate the connected evaporator with the carrier gas supply device; when any one of the second control valves is closed, the second pipe connected with the second control valve is in a non-conducting state, so that the evaporator connected with the second pipe is not communicated with the carrier gas supply device.

So, through the setting of second control valve, can control whether to let in the carrier gas to the evaporimeter to and the volume of the carrier gas that control lets in, and then can control the drive power of carrier gas to the vapour that produces in the evaporimeter, the volume of the vapour that control lets in to the reaction chamber realizes the control to the reaction of going on in the reaction chamber, and then realizes controlling the preparation thickness of perovskite film, in order to satisfy the needs of different application scenarios, expands the range of application of perovskite.

In the embodiment of the application, before introducing the vapor into the reaction cavity, the reaction cavity needs to be vacuumized to increase the vacuum degree in the reaction cavity, so as to improve the concentration of the vapor in the reaction cavity; at this time, a third pipeline may be disposed between the carrier gas providing device and the reaction chamber, so that the carrier gas providing device may be directly connected to the reaction chamber through the third pipeline; when the reaction cavity is vacuumized, the carrier gas supply device can introduce carrier gas into the reaction cavity through the third pipeline.

Therefore, impurities in the reaction cavity can be reduced, and the influence of the impurities on halogenation reaction and replacement reaction is avoided, so that the purity of the perovskite is improved; moreover, the problem that gas flows back into the reaction cavity during vacuumizing can be avoided, and the vacuumizing efficiency is improved.

In this embodiment, a third control valve may be disposed on the third pipeline, and when the reaction chamber is vacuumized, the third control valve may be opened to enable the third pipeline to be in a conducting state, the third pipeline may communicate the carrier gas supply device with the reaction chamber, and the carrier gas is introduced into the reaction chamber during the vacuuming process; when the vacuumizing is finished, the third control valve can be closed, so that the third pipeline is in a non-conducting state, and the carrier gas supply device is not communicated with the reaction cavity so as to stop introducing the carrier gas into the reaction cavity.

Therefore, the third control valve can control the on-off of the third pipeline, and further control whether the carrier gas supply device is communicated with the reaction cavity or not, so that when the carrier gas is introduced into the reaction cavity is controlled, and the perovskite preparation is effectively carried out.

In the embodiment of the application, the first control valve, the second control valve and the third control valve can be opened and closed under the control of the controller, and the controller can control the first control valve, the second control valve and the third control valve according to a preset preparation program, so that the smooth proceeding of the preparation process is ensured.

In an embodiment of the present application, the preparation apparatus may further include: the mechanical pump is connected with the reaction cavity, and the mechanical pump can vacuumize the reaction cavity, so that the reaction cavity can reach a certain vacuum degree, a precursor can reach higher vapor concentration, and the perovskite preparation process is guaranteed to be effectively carried out.

In a second aspect, the embodiment of the present application further provides a method for preparing a perovskite, in which a B-containing organic substance, an a-containing organic salt, and ammonium halide are used as precursors;

the specific preparation process comprises the following steps: b-containing organic vapor and ammonium halide (chemical formula can be expressed as NH) ₄ X) the steam firstly undergoes halogenation reaction to generate NH ₄ BX ₃ An intermediate of (1); the intermediate is steamed with organic salt containing AGas displacement reaction, i.e. A in vapor containing A organic salt ⁺ By replacement of NH in intermediates ₄ ⁺ So as to obtain the compound with the chemical general formula ABX ₃ The perovskite is prepared.

Wherein, for the B-containing organic matter, B can be selected from at least one of Pb, sn, and the like; for A-containing organic salts, A may be selected from Rb, cs, CH ₃ NH ₃ And H ₂ C(＝NH)NH ₂ Etc., i.e., a may be a metal or an organic group; for the chemical formula NH ₄ As the ammonium halide of X, X may be at least one selected from the group consisting of I, br, cl and F.

Based on this, the preparation method comprises the following characteristics:

firstly, when inorganic salt such as metal halide is used as a precursor, high temperature or high vacuum degree is needed to obtain inorganic salt vapor; in the embodiment of the application, an inorganic salt is not adopted, but an organic matter, an organic salt and ammonium halide are adopted as precursors, so that corresponding steam can be obtained only at a lower temperature, the reaction temperature for preparing perovskite can be reduced, the requirement on preparation equipment is further reduced, the manufacturing cost of the preparation equipment is reduced, and energy can be saved.

Secondly, the preparation process comprises two steps, wherein in the first step, halogenation reaction is carried out to generate an intermediate, and in the second step, perovskite is obtained through the displacement reaction of the intermediate and organic salt steam containing A; in the preparation process, the intermediate can effectively improve the generation speed of the perovskite and improve the preparation efficiency of the perovskite; and the existence of the intermediate can improve the crystallization degree of the perovskite to a certain extent, so that the prepared perovskite has better performance.

Therefore, by the stepwise reaction and the selection of the precursor, an intermediate can be generated based on the halogenation reaction, and then the intermediate is subjected to cation substitution based on the substitution reaction to obtain the perovskite, and since the organic substance, the organic salt and the ammonium halide can have a higher saturated vapor pressure at a lower temperature, the reaction temperature can be lowered, the reaction time of the perovskite can be shortened, and the production efficiency of the perovskite can be improved.

In the embodiment of the application, because the precursor comprises the organic matter, the organic salt and the ammonium halide, and does not comprise the inorganic salt, the organic matter vapor, the organic salt vapor and the ammonium halide vapor can be obtained at the temperature of less than or equal to 300 ℃ without high temperature during the halogenation reaction and the replacement reaction so as to carry out the halogenation reaction and the replacement reaction, so that the halogenation reaction and the replacement reaction can be carried out at the temperature of less than or equal to 300 ℃, the reaction temperature is effectively reduced, the requirement on preparation equipment is reduced, and energy can be saved.

Also, in the embodiment of the present application, since the organic matter, the organic salt, and the ammonium halide may have a higher vapor concentration at a low degree of vacuum, when the degree of vacuum in the reaction chamber is low, for example, the degree of vacuum of the reaction chamber is 10Pa to 10Pa ⁴ Pa, the vapor of the corresponding substance can be obtained to carry out halogenation reaction and replacement reaction, thereby effectively reducing the requirement of vacuum degree and reducing the requirement on preparation equipment.

In the embodiment of the present application, since the precursor includes: the organic salt containing A, the organic matter containing B and the ammonium halide, so when the organic salt vapor containing A, the organic matter vapor containing B and the ammonium halide vapor are introduced into the reaction cavity, the introduction sequence of the vapors can comprise the following two types:

mode 1:

introducing organic matter steam containing B and ammonium halide steam into a reaction cavity to perform halogenation reaction on the organic matter steam containing B and the ammonium halide steam to obtain an intermediate; wherein, in order to ensure the complete conversion of the vapor of the organic matter containing B and avoid the residue of the organic matter containing B, the vapor amount of the ammonium halide vapor can be controlled to be larger than that of the vapor of the organic matter containing B;

introducing organic salt steam containing A into the reaction cavity, so that the organic salt steam containing A and the intermediate undergo a displacement reaction to obtain perovskite; wherein, in order to ensure the complete conversion of the intermediate and avoid the residue of the intermediate, the vapor amount of the vapor containing the organic salt A can be controlled to be larger than that of the vapor containing the organic salt B. This is due to: the chemical formula of the intermediate is NH ₄ BX ₃ If the intermediate contains B, all B in the intermediate comes from the vapor of the B-containing organic matter, so the amount of the intermediate is equivalent to that of the B-containing organic matter; when the vapor amount of the vapor containing the organic salt A is larger than that of the vapor containing the organic salt B, the amount of the vapor containing the organic salt A in the reaction chamber is considered to be larger than that of the intermediate, so that when a large amount of the vapor containing the organic salt A is introduced, the vapor containing the organic salt A can be used for ensuring that the vapor containing the organic salt A is larger than that of the intermediate ⁺ Is greater than NH in the intermediate ₄ ⁺ At a concentration of NH ₄ ⁺ Is completely replaced by A ⁺ Thereby obtaining the compound with the chemical general formula ABX ₃ The perovskite of (a).

Mode 2:

simultaneously introducing organic salt vapor containing A, organic salt vapor containing B and ammonium halide vapor into the reaction cavity;

it is noted that even though three kinds of vapor are simultaneously introduced, the organic vapor containing B and the ammonium halide vapor are firstly subjected to halogenation reaction to generate an intermediate, and then the intermediate is subjected to displacement reaction with the organic salt vapor containing A to generate perovskite.

Wherein, in order to ensure the complete conversion of the steam containing the organic matter B and the intermediate and avoid the residue of the organic matter B and the intermediate, the steam quantity of the ammonium halide steam and the steam quantity of the organic salt A can be controlled to be larger than the steam quantity of the organic matter B.

In summary, in practical cases, the perovskite can be obtained by either the above-described mode 1 or mode 2, and the specific mode can be selected according to practical needs, and is not limited herein; however, it should be noted that, regardless of the above mode 1 or mode 2, the vapor amount of the ammonium halide vapor and the vapor amount of the organic salt vapor containing a need to be greater than the vapor amount of the organic salt vapor containing B, so as to ensure the complete conversion of the organic salt vapor containing B and the intermediate, avoid the residue of the organic salt containing B and the intermediate, and improve the purity and yield of the perovskite.

In the embodiment of the present application, when the vapor amounts of the three kinds of vapor are set, it may be set as follows: the vapor amount of the ammonium halide vapor and the vapor amount of the A-containing organic salt vapor are both 1.5 times to 100 times of the vapor amount of the B-containing organic salt vapor, so that the vapor amount of the ammonium halide vapor and the vapor amount of the A-containing organic salt vapor are both larger than the vapor amount of the B-containing organic salt vapor, the B-containing organic salt vapor and the intermediate are completely converted, the residual of the B-containing organic salt and the intermediate is avoided, and the purity and the yield of the perovskite are improved.

In the examples of the present application, for the B-containing organic substance, it may be selected from: bis [ bis- (trimethylsilyl) amide]Lead (which may be abbreviated as Pb (btsa) ₂ ) And lead bis (2,2,6,6-tetramethyl-3,5-pimelic acid) (which may be abbreviated as Pb (tmhd) ₂ ) Bis (3-N, N-dimethyl-2-methyl-2-propoxide) lead (which may be abbreviated as Pb (DMAMP) ₂ ) Lead acetate, bis [ bis- (trimethylsilyl) amide]Stannous (may be abbreviated Sn (btsa) ₂ ) And stannous bis (2,2,6,6-tetramethyl-3,5-pimelic acid) (may be abbreviated as Sn (tmhd) ₂ ) Bis (3-N, N-dimethyl-2-methyl-2-propoxide) stannous (may be abbreviated as Sn (DMAMP) ₂ ) At least one of stannous acetate; of course, when selecting the organic material containing B, the selection is not limited to the above-mentioned examples, and other organic materials containing B may be selected, and the selection is not limited thereto.

In the examples of the present application, for the a-containing organic salt, it may be selected from: cesium tert-butoxide (may be abbreviated as CsOtBu), cesium acetate (may be abbreviated as CsAc), rubidium tert-butoxide (may be abbreviated as RbOtBu), rubidium acetate (may be abbreviated as RbAc), CH ₃ NH ₃ SCN (which may be abbreviated as MASCN), FH ₂ C(＝NH)NH ₂ SCN (may be abbreviated as FASCN), CH ₃ NH ₃ CH ₃ COO (may be abbreviated as MACH) ₃ COO)、H ₂ C(＝NH)NH ₂ CH ₃ COO (may be abbreviated FACH) ₃ COO); of course, the selection of the organic salt containing a is not limited to the above-mentioned examples, and other organic salts containing a may be selected, and is not limited thereto.

In the embodiment of the present application, for the organic matter containing B, if the solid organic matter containing B is converted into the gaseous organic matter containing B (i.e. organic matter vapor containing B), the solid organic matter containing B may be heated to 100 ℃ to 250 ℃; for the A-containing organic salt, if the solid A-containing organic salt is converted to a gaseous A-containing organic salt (i.e., A-containing organic salt vapor), the solid A-containing organic salt can be heated to 100 ℃ to 300 ℃; for ammonium halides, if the ammonium halide in solid form is converted to gaseous ammonium halide (i.e., ammonium halide vapor), the ammonium halide in solid form can be heated to 100 ℃ to 250 ℃.

Therefore, when the B-containing organic matter, the A-containing organic salt and the ammonium halide are used as precursors to prepare the perovskite, the heating temperature of the precursors can be controlled to be 100-300 ℃; in addition, in order to ensure that the organic matter vapor containing B, the organic salt vapor containing A and the ammonium halide vapor can carry out halogenation reaction and replacement reaction, the temperature of the reaction cavity is kept within 300 ℃. Thus, in the embodiment of the application, the preparation temperature of the perovskite (which may include the heating temperature of the precursor and the holding temperature of the reaction chamber) is effectively reduced, and thus the requirement on the preparation equipment may be reduced, which is beneficial to reducing the manufacturing cost of the preparation equipment.

In the embodiment of the application, in order to accelerate the transmission speed of the vapor generated in the evaporator to the reaction cavity and improve the reaction efficiency, the carrier gas can be utilized to enable the ammonium halide vapor, the vapor containing the organic salt A and the vapor containing the organic salt B to quickly enter the reaction cavity under the driving of the carrier gas, so as to improve the concentration of each vapor in the reaction cavity, thereby realizing the quick implementation of the halogenation reaction and the replacement reaction and improving the preparation efficiency of the perovskite; furthermore, the waste of the precursor caused by the fact that part of the vapor stays in the vapor transmission channel (such as but not limited to the first pipeline mentioned in the above) and cannot enter the reaction chamber can be avoided, and the utilization rate of the precursor can be improved.

Before introducing steam into the reaction cavity, the reaction cavity needs to be vacuumized to increase the vacuum degree in the reaction cavity, so that the concentration of the steam in the reaction cavity is improved; at this time, when the reaction chamber is evacuated, a carrier gas may be introduced into the reaction chamber. Therefore, impurities in the reaction cavity can be reduced, and the influence of the impurities on halogenation reaction and replacement reaction is avoided, so that the purity of the perovskite is improved; moreover, the problem that gas flows back into the reaction cavity during vacuumizing can be avoided, and the vacuumizing efficiency is improved.

In the present embodiment, the carrier gas may include, but is not limited to: nitrogen, inert gases or reactive gases, which may include, but are not limited to: argon or helium, etc., and the reaction gas may include, but is not limited to: ammonia gas, halogen gas, oxygen gas, or the like.

In a third aspect, embodiments of the present application further provide a photoelectric converter, which may include: the perovskite thin film is arranged on the substrate;

the perovskite thin film is prepared by the above preparation method as provided in the examples of the present application, or by the above preparation apparatus as provided in the examples of the present application.

In the embodiments of the present application, the photoelectric converter may include, but is not limited to: a solar cell, a photodetector and a light emitting diode;

when the photoelectric converter is a solar cell, the photoelectric converter further includes: the electronic device comprises a first electrode layer, an electron transport layer, a hole transport layer and a second electrode layer, wherein the first electrode layer and the electron transport layer are positioned between a substrate and a perovskite thin film, and the hole transport layer and the second electrode layer are sequentially arranged on the perovskite thin film; the first electrode layer is located between the substrate and the electron transport layer. The perovskite absorbs light to generate electron-hole pairs, electrons and holes move to the electron transport layer and the hole transport layer respectively under the action of an internal electric field, and finally reach the first electrode layer and the second electrode layer respectively to generate current, so that conversion from light energy to electric energy is realized.

When the photoelectric converter is a photoelectric detector, the structure of the photoelectric converter is similar to that of a solar cell, and a first electrode layer, an electron transport layer, a perovskite thin film, a hole transport layer and a second electrode layer are sequentially arranged on a substrate; the difference lies in that: the electric energy converted by the solar cell can supply power for electric equipment, and the electric energy converted by the photoelectric detector can be used as a sensing signal for analysis and processing so as to determine the detection sensitivity of the photoelectric detector to light with certain wavelength or light with certain wavelength.

When the photoelectric converter is a light emitting diode, the photoelectric converter further includes: an anode positioned between the substrate and the perovskite thin film, and a cathode positioned on the perovskite thin film. Electric signals are respectively input through the anode and the cathode, electrons in the perovskite in the ground state absorb the energy and jump to the excited state under the excitation of the electric signals, the electrons in the excited state jump back to the ground state again due to the instability of the excited state, and the generated energy is emitted outwards in the form of photons when the electrons jump from the excited state to the ground state due to the fact that the energy level of the excited state is higher than that of the ground state, and therefore light emission is achieved.

Of course, in the embodiments of the present application, the photoelectric converter may also be other devices that operate based on the photoelectric effect and employ perovskite, and is not limited herein.

Drawings

FIG. 1 is a schematic diagram of a perovskite preparation process provided in an embodiment of the present application;

FIG. 2 is a schematic structural diagram of a manufacturing apparatus provided in an embodiment of the present application;

FIG. 3 is a schematic structural view of the manufacturing apparatus corresponding to FIG. 2 from a different perspective;

FIG. 4 is a schematic structural diagram of another manufacturing apparatus provided in an embodiment of the present application;

FIG. 5 is a cross-sectional view of a sprinkler provided in accordance with an embodiment of the present application;

fig. 6 is a schematic structural diagram of a photoelectric converter according to an embodiment of the present application;

FIG. 7 is a schematic structural diagram of a perovskite solar cell provided in an embodiment of the present application;

fig. 8 is a schematic structural diagram of a crystalline silicon perovskite tandem cell provided in an embodiment of the present application.

Reference numerals:

10-reaction chamber, 11-sample stage, 12-sprayer, 12 a-spraying channel, 12 b-spraying hole, 20-evaporator, 31-first pipeline, 32-second pipeline, 33-third pipeline, 41-first control valve, 42-second control valve, 43-third control valve, m 1-substrate, m 2-carrier gas supply device, m 3-mechanical pump, m 4-heterogeneous crystalline silicon cell, G0-perovskite film, G1-first electrode layer, G2-electron transport layer, G3-hole transport layer, G4-second electrode layer.

Detailed Description

In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be described in further detail with reference to the accompanying drawings.

It should be noted that the same reference numerals in the drawings of the present application denote the same or similar structures, and thus, a repetitive description thereof will be omitted. The words used in this application to describe positions and orientations are provided by way of example in the drawings and can be changed as desired and are intended to be encompassed by the present application. The drawings of the present application are for illustrating relative positional relationships only and do not represent true scale.

The embodiment of the application provides a perovskite preparation method, perovskite preparation equipment and a photoelectric converter. The prepared perovskite can be applied to a photoelectric converter, and the photoelectric converter can be but is not limited to: photoelectric detectors, solar cells, light emitting diodes and the like which are manufactured by applying the photoelectric effect. When the photoelectric converter is a solar cell, the photoelectric converter can be applied to power generation equipment, so that the power generation equipment has a power generation function and provides electric energy for electric equipment; when the photoelectric converter is a photoelectric detector, the photoelectric converter can be applied to any equipment needing a detection function to realize the detection of signals; when the photoelectric converter is a light emitting diode, the photoelectric converter can be applied to any device requiring a light emitting diode, such as but not limited to a display, to realize the function of emitting light.

In the current technology, when the perovskite is prepared by a vapor deposition method, a specific preparation method may include: multi-source simultaneous evaporation, multi-source sequential evaporation, multi-step vacuum vapor deposition, and vapor transport methods; wherein:

the multi-source simultaneous evaporation specifically includes: inorganic salt and organic salt are taken as precursors, the precursors are respectively put into different evaporation crucibles, the inorganic salt and the organic salt are heated under certain vacuum degree to form corresponding vapor, and the vapor is condensed on a substrate and reacts to form perovskite;

the multi-source sequential evaporation specifically comprises: inorganic salt and organic salt are taken as precursors, firstly inorganic salt is deposited on a substrate, and then organic salt is continuously deposited to form perovskite;

the multi-step vacuum vapor deposition specifically includes: inorganic salt and organic salt are taken as precursors, firstly, a chamber with high vacuum degree is adopted to evaporate the inorganic salt, and then, the substrate is transferred to a chamber with lower vacuum degree to evaporate the organic salt to form perovskite;

the vapor transmission method specifically includes: taking inorganic salt and organic salt as precursors, heating the inorganic salt and the organic salt alternately and sequentially, and depositing the inorganic salt and the organic salt alternately on a substrate to form perovskite.

The preparation methods all adopt inorganic salt as one precursor, because the inorganic salt has the characteristic of low saturated vapor pressure, in order to generate enough amount of vapor to realize the deposition of the film, the vacuum degree needs to be improved to a high vacuum condition or the heating temperature of the inorganic salt needs to be improved to a high temperature of more than 400 ℃, the high vacuum degree and the high temperature both increase the requirements on the material and the structure of the equipment, the manufacturing cost of the equipment is increased, and meanwhile, the problem of increasing the reaction time can be caused when the inorganic salt film is deposited firstly and then the organic salt is introduced for reaction.

Based on this, the embodiment of the application provides a preparation method, preparation equipment and photoelectric converter of perovskite, can reduce the preparation temperature of perovskite, shorten the reaction time of perovskite, improve the preparation efficiency of perovskite.

The embodiment of the application provides a preparation method of perovskite, which adopts B-containing organic matter, A-containing organic salt and ammonium halide as precursors;

with reference to the schematic diagram of the perovskite manufacturing process shown in fig. 1, the specific manufacturing process includes: b-containing organic matter (including bivalent B and organic group) vapor and ammonium halide (chemical formula can be expressed as NH) ₄ X) the steam firstly undergoes halogenation reaction to generate NH ₄ BX ₃ The intermediate of (1); the intermediate and the vapor containing A organic salt have a displacement reaction, namely A in the vapor containing A organic salt ⁺ By replacement of NH in intermediates ₄ ⁺ Thereby obtaining the compound with the chemical general formula ABX ₃ The perovskite is prepared.

Wherein for compounds containing BIn the organic matter, B may be at least one selected from Pb, sn, and the like; for organic salts containing A, A may be selected from Rb, cs, CH ₃ NH ₃ And H ₂ C(＝NH)NH ₂ Etc., i.e., a may be a metal or an organic group; for the general chemical formula NH ₄ As the ammonium halide of X, X may be at least one selected from the group consisting of I, br, cl and F.

Based on this, the preparation method comprises the following characteristics:

firstly, when inorganic salt such as metal halide is used as a precursor, high temperature or high vacuum degree is needed to obtain inorganic salt vapor; in the embodiment of the application, an inorganic salt is not adopted, but an organic substance, an organic salt and ammonium halide are adopted as precursors, so that corresponding steam can be obtained only at a lower temperature, the reaction temperature for preparing the perovskite can be reduced, the requirement on preparation equipment is further reduced, the manufacturing cost of the preparation equipment is reduced, and energy can be saved.

Secondly, the preparation process comprises two steps, wherein in the first step, halogenation reaction is carried out to generate an intermediate, and in the second step, the intermediate and the organic salt vapor containing A are subjected to displacement reaction to obtain perovskite; in the preparation process, the intermediate can effectively improve the generation speed of the perovskite and improve the preparation efficiency of the perovskite; and the existence of the intermediate can improve the crystallization degree of the perovskite to a certain extent, so that the prepared perovskite has better performance.

Therefore, by the stepwise reaction and the selection of the precursor, an intermediate can be generated based on the halogenation reaction, and then the intermediate is subjected to cation substitution based on the substitution reaction to obtain the perovskite, and since the organic substance, the organic salt and the ammonium halide can have higher saturated vapor pressure at a lower temperature, the reaction temperature can be reduced, the reaction time of the perovskite can be shortened, and the preparation efficiency of the perovskite can be improved.

Wherein the saturated vapor pressure is related to temperature and the vapor concentration is related to temperature and vacuum.

mode 1:

introducing organic salt steam containing A into the reaction cavity, so that the organic salt steam containing A and the intermediate undergo a displacement reaction to obtain perovskite; wherein, in order to ensure the complete conversion of the intermediate and avoid the residue of the intermediate, the vapor amount of the vapor containing the organic salt A can be controlled to be larger than that of the vapor containing the organic salt B. This is due to: the chemical formula of the intermediate is NH ₄ BX ₃ In the case where all B contained in the intermediate is derived from the vapor of the B-containing organic compound, the amount of the intermediate corresponds to the amount of the B-containing organic compoundThe amount of (c); when the vapor amount of the vapor containing the organic salt A is larger than that of the vapor containing the organic salt B, the amount of the vapor containing the organic salt A in the reaction chamber is considered to be larger than that of the intermediate, so that when a large amount of the vapor containing the organic salt A is introduced, the vapor containing the organic salt A can be used for ensuring that the vapor containing the organic salt A is larger than that of the intermediate ⁺ Is greater than NH in the intermediate ₄ ⁺ At a concentration of NH ₄ ⁺ Is completely replaced by A ⁺ Thereby obtaining the compound with the chemical general formula ABX ₃ The perovskite of (a).

Mode 2:

In the present embodiment, the vapor amount of the vapor introduced into the reaction chamber may be understood as: the concentration of the steam in the reaction cavity after the steam enters the reaction cavity, so that the larger the steam amount of the introduced steam is, the larger the concentration of the steam in the corresponding reaction cavity is, and vice versa.

In the examples of the present application, for the B-containing organic substance, it may be selected from: bis [ bis- (trimethylsilyl) amide]Lead (which may be abbreviated as Pb (btsa) ₂ ) And lead bis (2,2,6,6-tetramethyl-3,5-pimelic acid) (which may be abbreviated as Pb (tmhd) ₂ ) Bis (3-N, N-dimethyl-2-methyl-2-propoxide) lead (which may be abbreviated as Pb (DMAMP) ₂ ) Lead acetate, bis [ bis- (trimethylsilyl) amide]Stannous (may be abbreviated Sn (btsa) ₂ ) And stannous bis (2,2,6,6-tetramethyl-3,5-pimelic acid) (may be abbreviated as Sn (tmhd) ₂ ) Bis (3-N, N-dimethyl-2-methyl-2-propoxide) stannous (may be abbreviated as Sn (DMAMP) ₂ ) At least one of stannous acetate and stannous acetate; of course, when selecting the organic material containing B, the selection is not limited to the above-mentioned examples, and other organic materials containing B may be selected, and the selection is not limited thereto.

In the examples of the present application, for the a-containing organic salt, it may be selected from: cesium tert-butoxide (may be abbreviated as CsOtBu), cesium acetate (may be abbreviated as CsAc), rubidium tert-butoxide (may be abbreviated as RbOtBu), rubidium acetate (may be abbreviated as RbAc), CH ₃ NH ₃ SCN (may be abbreviated as MASCN), FH ₂ C(＝NH)NH ₂ SCN (may be abbreviated as FASCN), CH ₃ NH ₃ CH ₃ COO (may be abbreviated as MACH) ₃ COO)、H ₂ C(＝NH)NH ₂ CH ₃ COO (may be abbreviated FACH) ₃ COO); of course, the selection of the organic salt containing a is not limited to the above-mentioned examples, and other organic salts containing a may be selected, and is not limited thereto.

In the embodiment of the application, in order to accelerate the transmission speed of the vapor generated in the evaporator to the reaction cavity and improve the reaction efficiency, the carrier gas can be utilized to enable the ammonium halide vapor, the vapor containing the organic salt A and the vapor containing the organic salt B to quickly enter the reaction cavity under the driving of the carrier gas, so as to improve the concentration of each vapor in the reaction cavity, thereby realizing the quick implementation of the halogenation reaction and the replacement reaction and improving the preparation efficiency of the perovskite; in addition, the waste of the precursor caused by the fact that part of steam stays in the steam transmission channel and cannot enter the reaction cavity can be avoided, and the utilization rate of the precursor is improved.

Based on the same technical concept, the embodiment of the application provides a perovskite manufacturing device, such as the structural schematic diagrams of the manufacturing device shown in fig. 2 and 3, and fig. 2 and 3 are the structural schematic diagrams of the manufacturing device under different viewing angles; the preparation apparatus may include:

the reaction chamber 10, the reaction chamber 10 can provide a reaction space for preparing perovskite, and the reaction chamber 10 has a heating function, so that the reaction chamber 10 can maintain the vapor form of the precursor; in fig. 2, the dotted line with arrows indicates the flow direction of the vapor, but in practical cases, the flow direction of the vapor is not limited to that shown in fig. 2, and may include any direction; in fig. 2 and 3, m1 represents a substrate, and the substrate m1 may be placed at the bottom of the reaction chamber 10 so as to produce a perovskite thin film on the surface of the substrate m1;

a plurality of evaporators 20 connected to the reaction chamber 10, each of the evaporators 20 having a heating function, so that the evaporator 20 can heat the stored precursor into corresponding vapor; wherein the perovskite has a chemical general formula of ABX ₃ The precursor may include: b-containing organic substances (which can be regarded as a first type substance), ammonium halides (which can be regarded as a second type substance), and a-containing organic salts (which can be regarded as a third type substance), which can be stored in different evaporators 20; to illustrate, if different substances are stored in the same evaporator 20, when the heating function of the evaporator 20 is turned on to obtain vapor, the different substances in the evaporator 20 may react with each other, which may adversely affect the production of perovskite, or may not obtain perovskite with high purity and high yield, so that different precursors need to be stored in different evaporators 20。

Also, in the present embodiment, when a plurality of first and/or third types of substances are required in preparing the perovskite, different substances are required to be stored in different evaporators 20; referring to fig. 3, there are shown four evaporators 20, where ammonium halide is stored in evaporator 1, cs/Rb organic salt is stored in evaporator 2, organic matter containing B is stored in evaporator 3, and MASCN is stored in evaporator 4, where Cs/Rb organic salt and MASCN both belong to organic salt containing a.

For the selection of A, B and X, see above, and not detailed here.

Because the precursor does not contain inorganic salt, the halogenation reaction and the replacement reaction can be carried out at lower temperature, and precursor vapor with higher concentration can be obtained when the vacuum degree in the reaction cavity is lower; therefore, the preparation process has low requirements on the preparation equipment, so that the reaction cavity does not need to bear higher temperature and high vacuum degree, the manufacturing difficulty of the reaction cavity is reduced, the manufacturing difficulty of the preparation equipment is further reduced, the manufacturing cost of the preparation equipment is also reduced, the problem of overhigh energy consumption caused by high temperature can be solved, and the energy conservation is realized.

In the embodiment of the present invention, the material of the reaction chamber may include, but is not limited to, quartz or stainless steel, and may be any material that can have a certain hardness and can withstand a certain temperature and a certain vacuum degree, and is not limited herein; also, the shape of the reaction chamber may include, but is not limited to: square (as shown in fig. 4) or cylindrical (as shown in the structure combining fig. 2 and fig. 3), etc., and the design may be specifically performed according to actual needs, and is not limited herein.

In the embodiment of the present application, the surface of the reaction chamber may be provided with a heating coil or an infrared heating device to realize a heating function; in addition, the temperature in the reaction chamber can be controlled to be 150 ℃ to 300 ℃ so as to maintain the form of steam and ensure the effective operation of the preparation process.

As shown in fig. 4, another schematic structural diagram of a preparation apparatus, in the embodiment of the present application, the reaction chamber 10 may further include:

a sample stage 11, the sample stage 11 being operable to receive a substrate m1; for example, the substrate m1 may be placed on the sample stage 11, and when the halogenation reaction occurs, the generated intermediate may be deposited on the surface of the substrate m1 in the form of a thin film, and after the substitution reaction is completed, the intermediate may be converted into perovskite, so that a perovskite thin film may be produced on the surface of the substrate m1; the sample stage 11 may be disposed at the bottom of the reaction chamber 10, so that the vapor may be easily deposited on the surface of the substrate m1 under the action of gravity, thereby easily manufacturing the perovskite thin film; in addition, the sample stage 11 can have a heating function, and the temperature can be controlled to be 70 ℃ to 300 ℃ so as to ensure that the preparation process is smoothly and effectively carried out;

a sprayer 12 located above the sample stage 11 and at the top of the reaction chamber 10, as shown in fig. 5, which is a cross-sectional view of the sprayer 12, the sprayer 12 may have a plurality of spraying passages 12a therein, and the spraying passages 12a are isolated from each other and not intercommunicated; moreover, each evaporator 20 is connected to a different spraying channel 12a, so that the vapor generated in the corresponding evaporator 20 is introduced into the reaction chamber 10 through the different spraying channels 12a, so that the vapors do not contact with each other before entering the reaction chamber 10, that is, the vapors enter the reaction chamber 10 through different transmission paths, respectively, and adverse effects on the perovskite generation are avoided.

In fig. 4, the dotted line with arrows indicates the flow direction of the vapor, but in actual cases, the flow direction of the vapor is not limited to that shown in fig. 4 and may include any direction. In fig. 5, each spraying channel 12a is connected to at least one spraying hole 12b, the steam in the spraying channel 12a can enter into the reaction chamber through the spraying hole 12b, and the number of the spraying holes 12b connected to each spraying channel 12a may be the same or different, and may be set as required, and is not limited herein.

Moreover, fig. 5 is only used for illustrating the communication relationship between the spraying channel 12a and the spraying hole 12 b; in practical applications, the distribution of the spray holes 12b connected to each spray channel 12a is not limited to that shown in fig. 5, and the spray holes 12b connected to each spray channel 12a may be more uniformly arranged, for example, but not limited to, the spray channels 12a connected to any two adjacent spray holes 12b are different. So, can make vapour to reaction chamber input more even, also more even of diffusion downwards to can improve the degree of consistency of the perovskite thin film that generates, improve the quality of perovskite thin film.

In the embodiment of the present application, as shown in fig. 4, when N (N is an integer greater than or equal to 3) first pipelines 31 are disposed between the reaction chamber 10 and the evaporators 20, N first pipelines 31 are also disposed, and the evaporators 20 and the first pipelines 31 are connected in a one-to-one correspondence manner, so that each evaporator 20 is connected to the reaction chamber 10 through one first pipeline 31, and each evaporator 20 is connected to the reaction chamber 10 through a different first pipeline 31, so that the vapor generated in each evaporator 20 can be introduced into the reaction chamber 10 through the connected first pipeline 31.

In the embodiment of the present application, as shown in fig. 4, but the spraying channels are not shown in fig. 4, when the spraying device 12 is disposed in the reaction chamber 10, N spraying channels in the spraying device 12 may be disposed, and the spraying channels are connected to the first pipes 31 in a one-to-one correspondence manner, so that each first pipe 31 is connected to a different spraying channel, respectively, and thus, the vapor generated in each evaporator 20 can enter the reaction chamber 10 through the corresponding first pipe 31 and spraying channel in sequence, and meanwhile, each vapor can be prevented from meeting and contacting in the first pipe 31 and the spraying channels, and the halogenation reaction and the replacement reaction can be effectively performed.

Of course, when no sprinkler is arranged in the reaction cavity, the top of the reaction cavity can be provided with N through holes, and each through hole is correspondingly connected with each first pipeline one by one, so that the steam transmitted by the first pipelines can directly enter the reaction cavity through the corresponding through holes; therefore, the structure of the reaction cavity can be simplified, the manufacturing difficulty of the reaction cavity is reduced, and the manufacturing cost of the reaction cavity and even the manufacturing equipment is reduced.

In the embodiment of the present application, as shown in fig. 4, one first control valve 41 is disposed on each first pipe 31, and the first control valves 41 are disposed in one-to-one correspondence with the first pipes 31, when any one of the first control valves 41 is opened, the first pipe 31 connected to the first control valve 41 is in a conducting state, so that the first pipe 31 can communicate the connected evaporator 20 with the reactor; when any one of the first control valves 41 is closed, the first pipe 31 connected to the first control valve 41 is in a non-conductive state, so that there is no communication between the evaporator 20 and the reactor connected to the first pipe 31.

For example, referring to fig. 4, taking the first pipe 31 and the first control valve 41 located at the lowermost position in fig. 4 as an example, for convenience of explanation and explanation, the first pipe 31 located at the lowermost position is referred to as a pipe 1, the first control valve 41 provided corresponding to the pipe 1 is referred to as a control valve 1, and the evaporator 20 connected to the pipe 1 is referred to as an evaporator 1; when the control valve 1 is opened, the pipeline 1 can communicate the evaporator 1 with the reaction chamber 10, so that steam generated in the evaporator 1 can enter the reaction chamber 10 through the pipeline 1; when the control valve 1 is closed, the evaporator 1 is not communicated with the reaction chamber 10, and the steam generated in the evaporator 1 cannot enter the reaction chamber 10 through the pipeline 1.

In the embodiment of the present application, as shown in fig. 4, each of the evaporators 20 may be further provided with a corresponding second pipe 32, and the second pipes 32 are connected to the evaporators 20 in a one-to-one correspondence, and each of the second pipes 32 is connected to the carrier gas supply device m2, so that each of the evaporators 20 is connected to the carrier gas supply device m2 through the corresponding second pipe 32.

Wherein, the carrier gas provided by the carrier gas providing device may include, but is not limited to: nitrogen, inert gases or reactive gases, which may include, but are not limited to: argon or helium, etc., and the reaction gases may include, but are not limited to: ammonia gas, halogen gas, oxygen gas, or the like.

In the embodiment of the present application, as shown in fig. 4, one second control valve 42 may be correspondingly disposed on each second pipeline 32, and the second pipelines 32 and the second control valves 42 are connected in a one-to-one correspondence; when any one of the second control valves 42 is opened, the second pipe 32 connected to the second control valve 42 is in a conducting state, so that the second pipe 32 can communicate the connected evaporator 20 and the carrier gas supply device m 2; when any one of the second control valves 42 is closed, the second pipe 32 connected to the second control valve 42 is in a non-conductive state, so that there is no communication between the vaporizer 20 connected to the second pipe 32 and the carrier gas supply device m 2.

For example, referring to fig. 4, taking the second conduit 32 located at the lowermost position in fig. 4 as an example, for convenience of explanation and explanation, the second conduit 32 located at the lowermost position is referred to as conduit 2, the second control valve 42 provided corresponding to the conduit 2 is referred to as control valve 2, and the evaporator 20 connected to the conduit 2 is referred to as evaporator 1; wherein, when the control valve 2 is opened, the pipeline 2 can communicate the evaporator 1 with the carrier gas providing device m2, so that the carrier gas provided by the carrier gas providing device m2 can enter into the evaporator 1 through the pipeline 2; when the control valve 2 is closed, the evaporator 1 is not communicated with the carrier gas supply device m2, and the carrier gas supplied by the carrier gas supply device m2 cannot enter the evaporator 1 through the pipe 2.

Therefore, through the arrangement of the second control valve, whether carrier gas is introduced into the evaporator or not can be controlled, the amount of the introduced carrier gas is controlled, the driving force of the carrier gas on steam generated in the evaporator can be further controlled, the amount of the steam introduced into the reaction cavity is controlled, the reaction carried out in the reaction cavity is controlled, the preparation thickness of the perovskite film is further controlled, the requirements of different application scenes are met, and the application range of the perovskite is expanded.

In the embodiment of the present application, before introducing the vapor into the reaction chamber 10, the reaction chamber 10 needs to be vacuumized to increase the vacuum degree in the reaction chamber 10, so as to improve the concentration of the vapor in the reaction chamber 10; at this time, as shown in fig. 4, a third pipe 33 may be provided between the carrier gas supplier m2 and the reaction chamber 10, so that the carrier gas supplier m2 may be directly connected to the reaction chamber 10 through the third pipe 33; when the reaction chamber 10 is evacuated, the carrier gas supplier m2 may supply the carrier gas into the reaction chamber 10 through the third pipe 33.

In the embodiment of the present application, as shown in fig. 4, a third control valve 43 may be disposed on the third pipeline 33, and when the reaction chamber 10 is vacuumized, the third control valve 43 may be opened, so that the third pipeline 33 is in a conducting state, the third pipeline 33 may communicate the carrier gas supply device m2 with the reaction chamber 10, and the carrier gas is introduced into the reaction chamber 10 during the vacuuming process; at the end of the vacuum pumping, the third control valve 43 may be closed so that the third conduit 33 is in a non-conductive state, and the carrier gas supply device m2 is not in communication with the reaction chamber 10to stop the introduction of the carrier gas into the reaction chamber 10.

In an embodiment of the present application, as shown in fig. 4, the preparation apparatus may further include: the mechanical pump m3 is connected with the reaction chamber 10, and the mechanical pump m3 can vacuumize the reaction chamber 10, so that the reaction chamber 10 can reach a certain vacuum degree, a precursor can reach a higher vapor concentration, and the perovskite preparation process is guaranteed to be effectively carried out.

The perovskite production process is explained and illustrated below with reference to specific examples.

The first embodiment is as follows: to prepare a compound of the formula MAPbI ₃ The perovskite thin film of (2) is exemplified.

Step 1, ultrasonically cleaning a substrate in sequence by adopting acetone, ethanol and deionized water, placing the substrate on a sample table, and heating the sample table to 100-150 ℃;

step 2, starting a mechanical pump to vacuumize the reaction cavity, introducing nitrogen carrier gas with the flow of about 10sccm and Pb (btsa) stored in each evaporator while vacuumizing ₂ 、NH ₄ I, heating with MASCN; wherein, the deposition condition is achieved when the vacuum degree of the reaction cavity reaches 10torr, and the heating temperature of each evaporator is 100 ℃ to 200 ℃;

in the present embodiment, the vapor amount of the precursor can be controlled by adjusting the heating temperature of the vaporizer.

Step 3, when the deposition condition is reached, pb (btsa) is carried out by using nitrogen carrier gas ₂ Steam and NH ₄ I vapor is delivered into the reaction chamber to deposit NH with a thickness of about 100nm to 200nm ₄ PbI ₃ A film;

step 4, transporting the MASCN vapor into the reaction chamber by using the nitrogen carrier gas to enable NH ₄ PbI ₃ Performing a displacement reaction with MASCN to generate MAPbI ₃ A film.

Wherein MAPbI with different thickness can be prepared by repeating the steps 3 and 4 ₃ A film.

To illustrate, in this embodiment, in addition to the introduction of Pb (btsa) in this order, the reaction mixture may be subjected to ₂ Steam, NH ₄ In addition to I steam and MASCN steam, pb (btsa) may be added at the same time ₂ Steam, NH ₄ Conveying the I steam and the MASCN steam into the reaction cavity; in order to ensure that the reaction process is Pb-free (btsa) ₂ Residual, introduced NH ₄ The I and MASCN vapors may have vapor quantities much higher than Pb (btsa) ₂ The vapor amount of the vapor.

In this example, the chemical reaction involved is as follows:

Pb(btsa) ₂ +NH ₄ I→NH ₄ PbI ₃ +NH ₄ (btsa)；

NH ₄ PbI ₃ +MASCN→MAPbI ₃ +NH ₄ SCN。

example two: to prepare the compound of formula (Cs) _x FA _y MA _1-x-y )Pb(Br _z I _1-z ) ₃ (0<x，y，z<1) The perovskite thin film of (2) is exemplified.

step 2, starting a mechanical pump to vacuumize the reaction cavity, introducing ammonia carrier gas with the flow of about 10sccm and Pb (btsa) stored in each evaporator while vacuumizing ₂ 、NH ₄ I、NH ₄ Br, csOtBu, FASCN and MASCN; wherein, the deposition condition is achieved when the vacuum degree of the reaction cavity reaches 10torr, and the heating temperature of each evaporator is 100 ℃ to 200 ℃;

and 3, when the deposition condition is achieved, carrying Pb (btsa) by using ammonia carrier gas ₂ Steam, NH ₄ I steam, NH ₄ Br vapor is delivered into the reaction chamber to deposit NH with a thickness of about 100nm to 200nm ₄ Pb(Br _z I _1-z ) ₃ A film;

step 4, conveying CsOtBu vapor, FASCN vapor and MASCN vapor into the reaction chamber by using ammonia gas carrier gas to enable NH ₄ Pb(Br _z I _1-z ) ₃ By substitution reaction with CsOtBu vapor, FASCN vapor, and MASCN vapor to produce (Cs) _x FA _y MA _1-x-y )Pb(Br _z I _1-z ) ₃ A film.

Wherein (Cs) having different thicknesses can be prepared by repeating step 3 and step 4 _x FA _y MA _1-x-y )Pb(Br _z I _1-z ) ₃ A film.

To illustrate, in this embodiment, in addition to the introduction of Pb (btsa) in this order, the reaction mixture may be subjected to ₂ Steam, NH ₄ I steam, NH ₄ In addition to Br vapor, csOtBu vapor, FASCN vapor and MASCN vapor, pb (btsa) may be simultaneously introduced ₂ Steam, NH ₄ I steam, NH ₄ Conveying Br vapor, csOtBu vapor, FASCN vapor and MASCN vapor into the reaction cavity; in order to ensure that the reaction process is Pb-free (btsa) ₂ Residual, introduced NH ₄ I steam, NH ₄ The vapor amounts of Br vapor, csOtBu vapor, FASCN vapor and MASCN vapor may be much higher than Pb (btsa) ₂ The vapor amount of the vapor.

In this example, the chemical reaction involved is as follows:

Pb(btsa) ₂ +NH ₄ I+NH ₄ Br→NH ₄ Pb(Br _z I _1-z ) ₃ +NH ₄ (btsa)；

NH ₄ Pb(Br _z I _1-z ) ₃ +MASCN+CsOtBu+FASCN→(Cs _x FA _y MA _1-x-y )Pb(Br _z I _1-z ) ₃ +NH ₄ SCN+

NH ₄ OtBu。

example three: to prepare a compound of the formula MApB _x Sn _1-x I ₃ (0<x<1) The lead-tin mixed perovskite thin film of (1) is exemplified.

step 2, starting a mechanical pump to vacuumize the reaction cavity, introducing nitrogen carrier gas with the flow of about 10sccm and Pb (btsa) stored in each evaporator while vacuumizing ₂ 、Sn(btsa) ₂ 、NH ₄ I. Heating by MASCN; wherein, the deposition condition is achieved when the vacuum degree of the reaction cavity reaches 10torr, and the heating temperature of each evaporator is 100 ℃ to 200 ℃;

step 3, when the deposition condition is reached, pb (btsa) is carried out by using nitrogen carrier gas ₂ Steam, sn (btsa) ₂ Steam, NH ₄ I vapor is delivered into the reaction chamber to deposit NH with a thickness of about 100nm to 200nm ₄ Pb _x Sn _1-x I ₃ A film;

step 4, transporting the MASCN vapor to the reaction chamber by using nitrogen carrier gas to enable NH ₄ Pb _x Sn _1-x I ₃ Performing displacement reaction with MASCN vapor to generate MAPB _x Sn _1-x I ₃ A film.

Wherein MApB with different thickness can be prepared by repeating step 3 and step 4 _x Sn _1-x I ₃ A film.

To illustrate, in this embodiment, in addition to the introduction of Pb (btsa) in this order, the reaction mixture may be subjected to ₂ Steam, sn (btsa) ₂ Steam, NH ₄ In addition to the I vapor and the MASCN vapor, pb (btsa) may be simultaneously introduced ₂ Steam, sn (btsa) ₂ Steam, NH ₄ Conveying the I steam and the MASCN steam into the reaction cavity; in order to ensure that the reaction process is Pb-free (btsa) ₂ And Sn (btsa) ₂ Residual, introduced NH ₄ The I and MASCN vapors may have vapor quantities much higher than Pb (btsa) ₂ Steam and Sn (btsa) ₂ The vapor amount of the vapor.

In this example, the chemical reaction involved is as follows:

Pb(btsa) ₂ +Sn(btsa) ₂ +NH ₄ I→NH ₄ Pb _x Sn _1-x I ₃ +NH ₄ (btsa)；

NH ₄ Pb _x Sn _1-x I ₃ +MASCN→MAPb _x Sn _1-x I ₃ +NH ₄ SCN。

example four: to prepare a chemical formula CsPbI ₃ The all-inorganic perovskite thin film of (1) is exemplified.

step 2, starting a mechanical pump to vacuumize the reaction cavity, introducing nitrogen carrier gas with the flow of about 10sccm and Pb (btsa) stored in each evaporator while vacuumizing ₂ 、NH ₄ I. CsOtBu is heated; wherein the deposition condition is achieved when the vacuum degree of the reaction chamber reaches 10torr, and the heating temperature of each evaporator is 100 ℃ to200℃；

Step 3, when the deposition condition is reached, pb (btsa) is carried out by using nitrogen carrier gas ₂ Steam, NH ₄ I vapor is delivered into the reaction chamber to deposit NH with a thickness of about 100nm to 200nm ₄ PbI ₃ A film;

step 4, conveying CsOtBu vapor into the reaction cavity by using nitrogen carrier gas to enable NH ₄ PbI ₃ Carrying out displacement reaction with CsOtBu vapor to generate CsPbI ₃ A film.

Wherein CsPbI with different thicknesses can be prepared by repeating the steps 3 and 4 ₃ A film.

To illustrate, in this embodiment, in addition to the introduction of Pb (btsa) in this order, the reaction mixture may be subjected to ₂ Steam, NH ₄ In addition to the I vapor and CsOtBu vapor, pb (btsa) may be simultaneously introduced ₂ Steam, NH ₄ Delivering I steam and CsOtBu steam to the reaction cavity; in order to ensure that the reaction process is Pb-free (btsa) ₂ Residual, introduced NH ₄ The vapor amounts of I vapor and CsOtBu vapor may be much higher than Pb (btsa) ₂ The vapor amount of the vapor.

In this example, the chemical reaction involved is as follows:

Pb(btsa) ₂ +NH ₄ I→NH ₄ PbI ₃ +NH ₄ (btsa)；

NH ₄ PbI ₃ +CsOtBu→CsPbI ₃ +NH ₄ OtBu。

example five: to produce a double perovskite heterojunction thin film, and the double perovskite comprises: has the chemical formula of MAPbI ₃ And a perovskite of the formula (Cs) _x FA _y MA _1-x-y )Pb(Br _z I _1-z ) ₃ (0<x，y，z<1) Perovskite of (c) is exemplified.

Step 1, referring to the first example, prepare a chemical formula of MAPbI on a substrate ₃ The perovskite thin film of (a);

step 2, referring to the second example, in the chemical formula MAPbI ₃ The chemical formula of the perovskite thin film surface is continuously prepared into (Cs) _x FA _y MA _1-x-y )Pb(Br _z I _1-z ) ₃ The double perovskite heterojunction thin film is obtained.

In the embodiment of the application, the chemical formula is not limited to MAPbI when designing the double perovskite heterojunction thin film ₃ And a perovskite of the formula (Cs) _x FA _y MA _1-x-y )Pb(Br _z I _1-z ) ₃ The perovskite of (2) can also be combined by adopting other types of perovskites to obtain more types of perovskite heterojunction thin films, and the manufacturing method is the same as the above and is not detailed here.

In the embodiment of the application, the two perovskite thin films can be prepared in the same preparation equipment, so that the damage to the lower thin film caused by the preparation of the upper thin film is avoided, the upper thin film and the lower thin film can be kept to have better integrity, and the heterojunction thin film has better performance.

Based on the same technical concept, embodiments of the present application provide a photoelectric converter, as shown in fig. 6, which may include: the perovskite thin film G0 is arranged on the substrate m1;

the perovskite thin film G0 is produced by the above-described production method as provided in the examples of the present application, or by the above-described production apparatus as provided in the examples of the present application.

when the photoelectric converter is a solar cell, as shown in fig. 7, the perovskite solar cell further includes: a first electrode layer G1 and an electron transport layer G2 which are positioned between the substrate m1 and the perovskite thin film G0, and a hole transport layer G3 and a second electrode layer G4 which are sequentially arranged on the perovskite thin film G0; the first electrode layer G1 is located between the substrate m1 and the electron transport layer G2. The perovskite thin film G0 absorbs light to generate electron-hole pairs, electrons and holes move to the electron transport layer G2 and the hole transport layer G3 respectively under the action of an built-in electric field, and finally reach the first electrode layer G1 and the second electrode layer G4 respectively to generate current, so that conversion from light energy to electric energy is realized.

When the photoelectric converter is a photoelectric detector, the structure of the photoelectric converter is similar to that of a solar cell, and a first electrode layer, an electron transport layer, a perovskite thin film, a hole transport layer and a second electrode layer are sequentially arranged on a substrate; the difference lies in that: the electric energy converted by the solar cell can supply power for electric equipment, and the electric energy converted by the photoelectric detector can be used as a sensing signal to be analyzed and processed so as to determine the detection sensitivity of the photoelectric detector to light with certain wavelength or light with certain wavelength.

The following will explain the preparation process of the photoelectric converter with reference to the specific examples.

The embodiment is as follows: take the preparation of a crystalline silicon perovskite laminated cell (i.e. a perovskite cell is arranged on the surface of a hetero-crystalline silicon cell, so that the hetero-crystalline silicon cell and the perovskite cell are overlapped) as an example.

Step 1, sequentially depositing a first electrode layer G1 and an electron transmission layer G2 on the textured surface of a prepared heterogeneous crystalline silicon cell m 4;

the electron transport layer can be prepared by a gas phase method or a self-assembly method.

Step 2, preparing a perovskite thin film G0 on the surface of the electron transport layer G2 by adopting the perovskite preparation process;

and 3, sequentially depositing a hole transport layer G3 and a second electrode layer G4 on the surface of the perovskite thin film G0 to obtain the prepared crystalline silicon perovskite laminated cell, as shown in FIG. 8.

The hole transport layer can be prepared by a vapor phase method (such as, but not limited to, a thermal evaporation method or an atomic layer deposition method), and both the first electrode layer and the second electrode layer can be prepared by magnetron sputtering.

While the preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all alterations and modifications as fall within the scope of the application.

It will be apparent to those skilled in the art that various changes and modifications may be made in the embodiments of the present application without departing from the spirit and scope of the embodiments of the present application. Thus, if such modifications and variations of the embodiments of the present application fall within the scope of the claims of the present application and their equivalents, the present application is also intended to encompass such modifications and variations.

Claims

1. A method of preparing a perovskite, comprising:

organic matter vapor containing B and chemical general formula of NH ₄ The ammonium halide vapor of X is halogenated, the generated intermediate and the vapor containing A are subjected to displacement reaction to generate ABX with the chemical general formula ₃ The perovskite of (a);

wherein B is at least one of Pb and Sn, A is Rb, cs and CH ₃ NH ₃ And H ₂ C(＝NH)NH ₂ X is selected from at least one of I, br, cl and F.

2. The method of claim 1, wherein the halogenation reaction and the metathesis reaction are conducted at a temperature of 300 ℃ or less.

3. The method of claim 1, wherein the reaction chamber is a reaction chamberBefore the vapor containing the organic matter B, the ammonium halide vapor and the vapor containing the organic salt A are introduced, the vacuum degree of the reaction cavity is 10Pa to 10Pa ⁴ Pa。

4. The method of claim 1, wherein the vapor amount of the ammonium halide vapor and the vapor amount of the a-containing organic salt vapor are both greater than the vapor amount of the B-containing organic salt vapor.

5. The method according to claim 4, wherein the vapor amount of the ammonium halide vapor and the vapor amount of the A-containing organic salt vapor are each 1.5 to 100 times the vapor amount of the B-containing organic salt vapor.

6. The method of claim 1, wherein a carrier gas is introduced into the reaction chamber prior to introducing the vapor into the reaction chamber.

7. The production method according to claim 6, wherein the carrier gas includes: inert gas, nitrogen, oxygen, ammonia, or halogen gas.

8. The method of any one of claims 6-7, wherein the vapor of the ammonium halide, the vapor of the organic salt containing A, and the vapor of the organic salt containing B are transported to the reaction chamber by the carrier gas.

9. The method of any one of claims 1-8, wherein the B-containing organic is selected from the group consisting of: at least one of bis [ bis- (trimethylsilyl) amide ] lead, bis (2,2,6,6-tetramethyl-3,5-pimelic acid) lead, bis (3-N, N-dimethyl-2-methyl-2-propoxide) lead, lead acetate, bis [ bis- (trimethylsilyl) amide ] stannous, bis (2,2,6,6-tetramethyl-3,5-pimelic acid) stannous, bis (3-N, N-dimethyl-2-methyl-2-propoxide) stannous and stannous acetate.

10. As in claimThe process of any one of claims 1 to 9, wherein the A-containing organic salt is selected from: cesium tert-butoxide, cesium acetate, rubidium tert-butoxide, rubidium acetate, CH ₃ NH ₃ SCN、FH ₂ C(＝NH)NH ₂ SCN、CH ₃ NH ₃ CH ₃ COO、H ₂ C(＝NH)NH ₂ CH ₃ And COO.

11. A production apparatus for carrying out the production method according to any one of claims 1 to 10, comprising:

a reaction chamber for providing a reaction space;

a plurality of evaporators connected to the reaction chamber, each of the plurality of evaporators for storing a substance and heating the stored substance.

12. The manufacturing apparatus of claim 11, further comprising: the sample stage is positioned in the reaction cavity, and the sprayer is positioned above the sample stage and is provided with a plurality of spraying channels which are isolated from each other, and each evaporator in the plurality of evaporators is respectively connected with different spraying channels.

13. The manufacturing apparatus according to claim 11 or 12, further comprising: a plurality of first conduits and a plurality of first control valves;

each of the first conduits of the plurality of first conduits, each of the first control valves of the plurality of first control valves, and each of the evaporators of the plurality of evaporators are uniformly disposed in a corresponding one-to-one relationship;

the first pipeline is used for connecting the evaporator and the reaction cavity correspondingly;

the first control valve is used for controlling whether the corresponding first pipeline is communicated or not.

14. The manufacturing apparatus of any one of claims 11 to 13, further comprising: a plurality of second conduits and a plurality of second control valves;

each second pipeline in the plurality of second pipelines and each second control valve in the plurality of second control valves are arranged in a one-to-one correspondence manner;

the second pipeline is used for connecting the corresponding evaporator and the carrier gas supply device;

the second control valve is used for controlling whether the corresponding second pipeline is communicated or not.

15. The manufacturing apparatus of any one of claims 11 to 14, further comprising: a third pipeline and a third control valve which are correspondingly arranged;

the third pipeline is used for connecting the carrier supply device and the reaction cavity;

the third control valve is used for controlling whether the third pipeline is conducted or not.

16. A photoelectric converter, comprising: the perovskite thin film is arranged on the substrate;

the perovskite thin film is prepared by the preparation method according to any one of claims 1 to 10 or the preparation device according to any one of claims 11 to 15.