Rhythmic deposition production method and equipment for perovskite thin film

1 . A rhythmic deposition production method of a perovskite thin film, comprising the following process:

depositing a precursor AX material onto a substrate pre-coated with a precursor BX 2 film containing a perovskite precursor BX 2 material in a deposition reaction chamber;

suspending the deposition after a period of time such that the precursor AX material deposited on a surface of the precursor BX 2 film has sufficient time to diffuse into the precursor BX 2 thin film so as to form a perovskite ABX 3 crystal;

after a period of suspension, the deposition is performed again, such that the deposition and suspension processes are alternately repeated rhythmically and the AX material enters the BX 2 film to react with the BX 2 material, so as to obtain an ABX 3 perovskite crystal without BX 2 material residual or with AX material surplus, wherein the deposition duration and the suspension duration are preset, and the rhythmic deposition process is ended after a perovskite ABX 3 film with a set thickness is obtained;

wherein the precursor BX 2 material is a metal halide material, the precursor AX material is an organic halide powder material, A is a monovalent cation selected from the group consisting of methylamino CH 3 NH 3 + , ethylamino CH 3 CH 2 NH 3 + , formamidino CH(NH 2 ) 2 + , acetamidino CH 3 C(NH 2 ) 2 + , Na + , K + , Rb + and Cs + , B is a divalent metal cation selected from the group consisting of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth and polonium, X is a monovalent anion selected from the group consisting of iodine, bromine, chlorine and astatine, and a deposition amount of the precursor AX material deposited in each deposition is 1/n of a total deposition amount required to form a complete perovskite thin film, and wherein the 1/n of the total deposition amount is allowed to fully react before a next deposition, and n refers to a number of unit deposition working positions.

2 . The method of claim 1 , wherein the prepared perovskite ABX 3 film has a thickness of 100 nm to 1000 nm.

3 . The method of claim 1 , wherein the deposition and suspension processes are performed in a vacuum environment with a vacuum degree of 1 Pa to 50000 Pa.

4 . The rhythmic deposition production method of claim 1 , wherein the precursor AX material is evaporated at a temperature of 80° C. to 300° C.

5 . A rhythmic deposition production equipment of a perovskite thin film, comprising

a deposition reaction chamber, wherein, the deposition reaction chamber comprises two functional regions comprising a deposition functional region and a reaction functional region, the deposition functional region comprises one or more deposition segments, the deposition segments comprise at least one unit deposition working position, an evaporation source is disposed inside each unit deposition working position, and the evaporation source is configured to receive a precursor AX material; the reaction functional region comprises one or more reaction segments, the reaction segments comprise at least one unit reaction working position, an evaporation source is not disposed inside each unit reaction working position, the deposition segments are spaced apart from the reaction segments, the deposition reaction chamber is in communication with a vacuum pump through a pipe, and a heating apparatus is further disposed inside the deposition reaction chamber to heat a to-be-deposited substrate pre-coated with a precursor BX 2 thin film containing a perovskite precursor BX 2 material;

wherein the precursor BX 2 material is a metal halide material, the precursor AX material powder is an organic halide powder material, A is a monovalent cation selected from the group consisting of methylamino CH 3 NH 3 + , ethylamino CH 3 CH 2 NH 3 + , formamidino CH(NH 2 ) 2 + , acetamidino CH 3 C(NH 2 ) 2 + , Na + , K + , Rb + and Cs + , B is a divalent metal cation selected from the group consisting of lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth and polonium, X is a monovalent anion selected from the group consisting of iodine, bromine, chlorine and astatine, and a deposition amount of the precursor AX material deposited in each deposition is 1/n of a total deposition amount required to form a complete perovskite thin film, and wherein the 1/n of the total deposition amount is allowed to fully react before a next deposition, and n refers to a number of unit deposition working positions.

6 . The equipment of claim 5 , further comprising a transport apparatus for transporting the to-be-deposited substrate, a load chamber, a heating chamber, an unload chamber, and a control system, the load chamber and the heating chamber are sequentially disposed at a front portion of the deposition reaction chamber, the unload chamber is disposed at a rear portion of the deposition reaction chamber, the transport apparatus is in communication with the load chamber, the heating chamber, the deposition reaction chamber and the unload chamber respectively, a thin film detection apparatus is disposed at some of the unit reaction working position, the thin film detection apparatus comprises at least one of an imaging detection system, an ultraviolet visible light spectrometric detection system (UV-vis), a photoluminescent detection system (PL), and an X-ray diffraction system (XRD), the control system is configured to feedback-control an operation of an evaporation source in the one or more deposition segments located downstream of the thin film detection apparatus based on a signal acquired by the thin film detection apparatus, a double-opening baffle plate is disposed at an opening of the evaporation source of a rear section of the deposition reaction chamber, and to feedback-control the operation of the evaporation source, the control system is further configured to:

control, by a software, the opening of the evaporation source of a subsequent deposition segment to open or close based on a deviation value between state information of a current to-be-deposited substrate and state information of standard substrate and control a reaction process of the perovskite thin film.

7 . The equipment of claim 5 , wherein the evaporation source comprises an evaporation crucible with an opening facing upward, the evaporation crucible comprises a heat insulation layer disposed outside, a heating layer disposed in middle and a heat conducting layer disposed inside, and the heating layer is provided with a heating power line connected with an external power supply interface.

8 . The equipment of claim 5 , wherein the unit deposition working positions have a length of L di =v*t d /n, and unit reaction working positions have a length of L ri =V*t r /m, wherein,

v is a moving speed of the to-be-deposited substrate,

t d is a deposition time required to form a perovskite film, t r is a reaction time required to form a perovskite film, and t d :t r =1:0.5 to 1:100, and

m refers to a number of the unit reaction working positions.

9 . The equipment of claim 8 , wherein lengths of the deposition segments and the reaction segments of the deposition reaction chamber sequentially decrease respectively along a direction of front and rear sections of the deposition reaction chamber.

10 . A method of depositing a perovskite film on a substrate by using the rhythmic deposition production equipment according to claim 5 , comprising the following steps:

at step 1, adding a precursor AX material to the evaporation source of each unit deposition working position in the deposition reaction chamber, and adjusting a vacuum degree of the deposition reaction chamber and starting the heating apparatus;

at step 2, placing a to-be-deposited substrate pre-coated with a precursor BX 2 film containing a perovskite precursor BX 2 material into the deposition reaction chamber, and enabling the to-be-deposited substrate to sequentially go through the deposition segments and the reaction segments, and obtaining a perovskite ABX 3 film generated by reaction on the substrate.

11 . The equipment of claim 6 , wherein the transport apparatus comprises rollers driven by a servo motor, the to-be-deposited substrate is conveyed by the rollers, and the to-be-deposited substrate is placed with a deposition surface facing down on a support roll of the rollers.

12 . The equipment of claim 11 , wherein

the evaporation source is a detachable evaporation source;

an evaporation source mounting groove is disposed between every two of the rollers; and

some of the evaporation source mounting grooves are selectively mounted with the evaporation source to form the deposition segments while other evaporation source mounting grooves are not mounted with the evaporation source to form the reaction segments, so as to flexibly construct production lines with different rhythmic disposal.

13 . The equipment of claim 9 , wherein the deposition segments and the reaction segments are alternately disposed in two forms, and the two forms include:

a first form, wherein a length of the reaction segments is unchanged and a length of the deposition segments decreases; or

a second form, wherein the length of the deposition segments is unchanged, and the length of the reaction segments increases.