CN115483359A - Perovskite thin film deposition process - Google Patents

Abstract

The application relates to a perovskite thin film deposition process, which comprises the steps of arranging a row of initial base layers and a plurality of rows of synchronous base layers, and coating a first initial base layer by using coating equipment; coating the first synchronous base layer of the adjacent row after the first initial base layer is coated, and simultaneously conveying the first initial base layer and performing vacuum flash evaporation; when the first initial base layer is subjected to vacuum flash evaporation, the first synchronous base layer in each row is coated, and then the second initial base layer is coated and repeated continuously; after the vacuum flash evaporation of the second initial base layer is finished, coating the synchronous base layer of the second base layer in each row, then coating a third initial base layer, and simultaneously annealing the first initial base layer; when the third initial base layer is coated, the first initial base layer is annealed, then the third synchronous base layer and the first synchronous base layer in the adjacent row are coated and annealed continuously, and the overall efficiency of perovskite thin film deposition is improved.

Description

A kind of perovskite film deposition process

technical field

The present application relates to the field of solar cell manufacturing, in particular to a perovskite film deposition process.

Background technique

In solar cells, the perovskite heterojunction tandem cell uses the heterojunction thin-film cell as the bottom cell, and then coats the perovskite cell on the bottom cell as the top cell, so that the top cell and the bottom cell can absorb light in different bands. Light, so it has extremely high conversion efficiency, which belongs to an important direction for the development of solar cells. One of the important steps in the manufacture of perovskite heterojunction laminated cells is to form a uniform perovskite film layer on the bottom cell from the perovskite raw material solution.

The existing deposition method suitable for large-area perovskite film layer formation is the flat plate deposition method, that is, the bottom cell moves forward as the base layer through the coating die, and an opening is set at the bottom of the coating die to extrude the perovskite raw material onto the base layer Solution, the base layer forms a perovskite wet film on the surface during the forward process, that is, coating, then vacuum flashes to remove the solvent, and finally anneals to form a perovskite film on the bottom battery base layer.

In view of the above-mentioned related technologies, the conveyor belt generally drives each base layer to move forward, but the conveyor belt stops moving during vacuum flashing, so that the subsequent base layer cannot be coated or annealed while the previous base layer is still being vacuum flashed. processing, which reduces the overall efficiency of perovskite film deposition.

Contents of the invention

In order to improve the overall efficiency of perovskite film deposition, the present application provides a perovskite film deposition process.

A perovskite film deposition process provided by the present application adopts the following technical scheme.

A perovskite film deposition process specifically includes the following steps.

Step 1. Set up a row of initial base layers and several rows of simultaneous base layers, and use coating equipment to coat the first initial base layer;

Step 2. After the coating of the first initial base layer is completed, the first synchronous base layer in the adjacent row is coated, and the first initial base layer is conveyed and vacuum flashed at the same time;

Step 3. When the vacuum flash evaporation of the first initial base layer is completed, the coating of the first synchronous base layer in each row is completed, and then the second initial base layer is coated, and the process is repeated continuously;

Step 4. After the vacuum flash evaporation of the second initial base layer is completed, the coating of the second simultaneous base layer in each row has been completed, and then the coating of the third initial base layer is carried out, and the first initial base layer is simultaneously coated. annealing;

Step 5. When the coating of the third initial base layer is completed, the annealing of the first initial base layer is completed, and then the coating of the third synchronous base layer in an adjacent row and the annealing of the first synchronous base layer are performed, and the process is repeated continuously.

By adopting the above technical scheme, when the vacuum flashing of an initial base layer is performed, the corresponding row of initial base layers can no longer be conveyed. At this time, the coating equipment coats an adjacent row of synchronous base layers to reduce coating The idle time of the equipment, and the annealing time is limited to be consistent with the coating time, so that the coating and annealing on two initial base layers in the same row or two synchronous base layers in the same row can start and end synchronously, In order to better control the overall process time of the perovskite film and improve the forming efficiency of the overall perovskite film.

Optionally, the coating equipment includes a chassis, a number of conveyor belts that are arranged in the chassis and drive a row of initial base layers and several rows of synchronous base layers to move one by one, set in the chassis and perform perovskite wet film coating on the base layers Cloth coating die, and a die moving device that is installed in the cabinet and drives the coating die to move along the width direction of the conveyor belt.

By adopting the above technical scheme, several conveyor belts drive a row of initial base layers and several rows of synchronous base layers for sequential transmission, and the coating die head cooperates with reciprocating movement along the width direction of the conveyor belt for intermittent coating and vacuum flashing treatment , so that the overall perovskite film forming efficiency is improved.

Optionally, the die moving device includes a set of synchronous wheels that are rotatably connected to the chassis, a synchronous belt that is connected to a set of synchronous wheels, a belt block that is fixedly connected to the synchronous belt and drives the coating die to move synchronously, and The synchronous wheel motor is arranged on the case and makes the synchronous wheel rotate, and the guide bar is arranged on the case and used for the sheathing and sliding of the belt block.

By adopting the above technical solution, the synchronous wheel motor is connected to the external power supply to make the synchronous wheel rotate, so that the synchronous belt can be driven, and under the action of the guide bar, the belt block can drive the coating die to move quickly and stably, so as to reduce the The time it takes for the coating die to move from directly over one conveyor to directly over the other.

Optionally, the belt block is provided with a vertical adjustment cylinder, and the power rod of the vertical adjustment cylinder is fixedly connected with a vertical adjustment block for connecting the coating die to make the coating die move vertically, and the belt block is provided with a penetrating and sliding connection The directional rod of the vertical adjustment block.

By adopting the above technical scheme, the vertical adjustment cylinder can adjust the distance between the coating die head and the base layer, so that when the coating die head needs maintenance and overhaul, it can be kept away from the conveyor belt for easy disassembly, and it can also be used for different thickness base layers or It is the perovskite film layer with different thicknesses that can be adjusted within a certain range.

Optionally, the coating die head includes a top cover detachably connected to the vertical adjustment block, a raw material box detachably connected to the top cover, a piston plate that is slidably connected to the inside of the raw material box and sends the perovskite solution out of the raw material box , the gas port that is set in the raw material box and feeds gas to make the piston plate move, the discharge one-way valve that is set at the discharge port of the raw material box and allows the perovskite solution to only be sent out from the raw material box, and the one-way valve that is set at the inlet of the raw material box At the feed port, the perovskite solution can only enter the feed one-way valve in the raw material box, and the height of the piston plate is higher than the height of the discharge check valve or the feed check valve.

By adopting the above technical scheme, when the piston plate moves towards the outlet of the raw material box, the perovskite solution can be sent out through the outlet check valve and the outlet of the raw material box. At this time, due to the existence of the feed check valve, the calcium The titanium ore solution will not be sent out through the feed port of the raw material box. When the piston plate is far away from the discharge port of the raw material box, the external perovskite solution enters the raw material box through the feed check valve, and due to the existence of the discharge check valve , so that the external air will not enter the raw material box, so that the raw material box can be discharged stably.

Optionally, several discharge one-way valves are arranged along the width direction of the conveyor belt.

By adopting the above technical scheme, when the piston plate sends the perovskite solution out of the raw material box, it can send the perovskite solution to the outlet of the raw material box through several discharge check valves, so that the outlet of the raw material box can be more efficient. Send out the perovskite raw material evenly.

Optionally, one side of the outlet of the raw material box is provided with a height-limiting blade for further controlling the thickness of the perovskite wet film, and the two ends of the raw material box are provided with ends that are close to the side of the base layer and absorb excess perovskite solution. The end suction block is attached to the end face of the height-limiting blade, and the side of the height-limiting blade near the outlet of the raw material box is provided with a blade suction block for sucking excess perovskite solution.

By adopting the above-mentioned technical scheme, an appropriate amount of perovskite solution can be sent out from the raw material box, and then a perovskite wet film with uniform thickness can be obtained by the height-limiting blade, and the end suction block can be used from the initial base layer or Simultaneously sucking the perovskite solution falling from both sides of the base layer, the blade suction block can suck the excessive perovskite solution on the side of the height-limited blade facing the raw material box, so that the excess perovskite solution can be recycled and reused.

Optionally, the air inlet of the end suction block is inclined and its height is lower than the upper surface of the initial base layer or the synchronous base layer, and the inclined lower end of the air inlet of the end suction block is close to the initial base layer or the synchronous base layer.

By adopting the above technical scheme, while the end suction block absorbs excess perovskite, the air inlet of the end suction block will not directly face the upper surface of the initial base layer or the synchronous base layer, so that the end The suction block will not suck the side part of the perovskite wet film, so that the perovskite wet film can be better kept uniform.

Optionally, the bottom of the height limiting blade is inclined and the inclined bottom end is close to the raw material box, the air inlet of the blade suction block is inclined and the inclined bottom end faces the inclined upper surface of the height limiting blade.

By adopting the above technical scheme, the excess perovskite solution will flow to the inclined upper surface of the height-limiting blade when passing through the height-limiting blade, and then the perovskite on the upper surface of the height-limiting blade will be tilted by the air inlet of the blade suction block. The raw material is sucked away, so that the blade suction block is not easy to suck up the perovskite solution too much, so that the perovskite wet film is more uniform.

Optionally, the raw material box is rotatably connected with a vertical adjustment lead screw threadedly connected to the height-limiting blade, the raw material box is provided with a lead screw motor that drives the vertical adjustment screw to rotate, and the raw material box is fixedly connected with a set of height-limiting blades and Sliding stabilizer bar.

By adopting the above technical solution, the lead screw motor is connected to the external power supply, so that the vertical adjustment lead screw rotates, so that the height-limiting blade can move stably in the vertical direction, so that when the thickness of the perovskite film is slightly changed, there is no need to move the vertical Fine-tuning the stroke by adjusting the cylinder can more conveniently adjust the thickness of the perovskite film adaptively.

In summary, the present application includes at least one of the following beneficial effects:

1. To reduce the idle time of the coating equipment, and limit the annealing time to be consistent with the coating time, so that the overall process time of the perovskite film can be better controlled, and the forming efficiency of the overall perovskite film can be improved;

2. The raw material box can send out an appropriate amount of perovskite solution, and then a perovskite wet film with uniform thickness can be obtained by the height-limiting blade, and the end suction block can drop from both sides of the initial base layer or the synchronous base layer The perovskite solution is inhaled, and the blade suction block can suck the excess perovskite solution on the side of the height-limited blade facing the raw material box, so that the excess perovskite solution can be recycled and reused.

Description of drawings

Fig. 1 is a sectional view of the side of the chassis of the present application to show a schematic structural diagram of the interior of the chassis;

Fig. 2 is the structural representation of coating die head;

Fig. 3 is a schematic cross-sectional structure diagram of one end of the raw material box, an end suction block and a blade suction block;

Fig. 4 is an enlarged view of A in Fig. 3 .

Explanation of reference signs: 1. Chassis; 2. Conveyor belt; 3. Coating die head; 31. Valve plate; 32. Air port; 33. Outer wall plate; 34. Wheel plate; 4. Die head moving device; 41. Raw material box ; 42, piston plate; 43, discharge one-way valve; 44, feed one-way valve; 45, height limit blade; 46, end suction block; 47, blade suction block; 48, vertical adjustment screw; 49, 5, synchronous wheel; 51, synchronous belt; 52, belt block; 53, synchronous wheel motor; 54, guide rod; 55, vertical adjustment cylinder; 56, vertical adjustment block; 57, orientation rod; 58, wire Bar motor; 59, top cover.

detailed description

The application will be described in further detail below in conjunction with the accompanying drawings.

The embodiment of the present application discloses a perovskite film deposition process, which specifically includes the following steps.

Step 1. Set up a row of initial base layers and several rows of simultaneous base layers, and use coating equipment to coat the first initial base layer;

Step 2. After the coating of the first initial base layer is completed, the first synchronous base layer in the adjacent row is coated, and the first initial base layer is conveyed and vacuum flashed at the same time;

Step 3. When the vacuum flash evaporation of the first initial base layer is completed, the coating of the first synchronous base layer in each row is completed, and then the second initial base layer is coated, and the process is repeated continuously;

Step 4. After the vacuum flash evaporation of the second initial base layer is completed, the coating of the second simultaneous base layer in each row has been completed, and then the coating of the third initial base layer is carried out, and the first initial base layer is simultaneously coated. annealing;

Step 5. When the coating of the third initial base layer is completed, the annealing of the first initial base layer is completed, and then the coating of the third synchronous base layer in an adjacent row and the annealing of the first synchronous base layer are performed, and the process is repeated continuously.

With reference to Fig. 1, the coating equipment comprises the cabinet 1 that is placed on the ground, and several conveyor belts 2 of equal height are arranged side by side in the cabinet 1, and all conveyor belts 2 are applied to conveying a row of initial base layers and all synchronous base layers one by one, the present embodiment The quantity of middle conveyer belt 2 can be selected two for use. The cabinet 1 is provided with corresponding pulleys and motors to drive two conveyor belts 2 for transmission. The coating die head 3 that can coat the initial base layer or the synchronous base layer on the conveyor belt 2 is installed in the cabinet 1, and the coating die head 3 can only coat one initial base layer or a synchronous base layer at a time, so as to realize A cycle of coating an initial base layer followed by a simultaneous base layer.

With reference to Fig. 1, the die head moving device 4 that drives coating die head 3 to move along the width direction of conveyer belt 2 is installed in the cabinet 1, and die head moving device 4 comprises the wheel plate 34 integrally formed on the inner top surface of the cabinet 1, the wheel plate 34 The vertical side is rotatably connected with two synchronous wheels 5, the side of the wheel plate 34 away from the synchronous wheel 5 is fixedly connected with a synchronous wheel motor 53, and the output shaft of the synchronous wheel motor 53 is coaxially fixedly connected to a synchronous wheel 5, two synchronous wheels 5 The transmission is connected with the same synchronous belt 51, the length direction of the synchronous belt 51 is consistent with the width direction of the conveyor belt 2, the bottom surface of the synchronous belt 51 is fixedly connected with a belt block 52, and the inner wall of the cabinet 1 is fixedly connected with two guide rods 54, and the belt block 52 is connected along the synchronous The belt 51 is sheathed in the length direction and is slidably connected to two guide rods 54 . The bottom surface of the band block 52 is fixedly connected with a vertical adjustment cylinder 55, and the bottom end of the vertical adjustment cylinder 55 power rod is fixedly connected with a vertical adjustment block 56, and the bottom surface of the belt block 52 is fixedly connected with two orientation rods 57, and the vertical adjustment block 56 top is along the vertical direction It is sheathed and slidably connected to the bottom ends of the two orientation rods 57, so that the position of the coating die head 3 can be adjusted in the horizontal and vertical directions.

Referring to Fig. 2 and Fig. 3, the coating die head 3 comprises the top cover 59 that is detachably connected to the bottom surface of the vertical adjustment block 56 by screws, the bottom surface of the top cover 59 is detachably connected with the raw material box 41 by screw sealing, and the bottom surface of the raw material box 41 is opened The discharge port for the perovskite solution in the raw material box 41 is sent out. The length direction of the discharge port of the raw material box 41 is consistent with the width direction of the conveyor belt 2. The same vertical side of the raw material box 41 is provided with the discharge port. The feed port of the raw material box 41 is connected to an external hose (not shown in the figure) so that the raw material box 41 can be replenished with perovskite solution. The inner wall of the raw material box 41 is closely slidably connected with a horizontal piston plate 42 along the vertical direction. The vertical side of the raw material box 41 with the feed opening is provided with an air port 32. The air port 32 is located above the piston plate 42, and the air port 32 is connected to the outside. The hose (not shown in the figure) is used to send or extract inert gas into the space above the piston plate 42 where the raw material box 41 is located, so as to drive the piston plate 42 to move vertically. below.

With reference to Fig. 2 and Fig. 3, coating die head 3 also comprises the feeding check valve 44 that is fixedly connected to the position where raw material box 41 is provided with feed inlet, and feeding check valve 44 makes perovskite raw material can only enter into In the raw material box 41, a horizontal valve plate 31 is integrally formed on the inner wall of the bottom of the raw material box 41. The valve plate 31 divides the raw material box 41 into upper and lower spaces. The valve plate 31 is fixedly connected with a discharge check valve 43. Material one-way valve 43 is evenly distributed several along the length direction of the discharge port of raw material box 41, and material discharge one-way valve 43 makes perovskite solution can only flow from top to bottom, so that calcium can be released when piston plate 42 moves down. The titanium ore solution is extruded from the feed opening of the raw material box 41, and the perovskite solution can enter from the feed opening of the raw material box 41 when the piston plate 42 moves up.

Referring to Fig. 3, the vertical side of the raw material box 41 is integrally formed with an outer wall plate 33, the upper surface of the outer wall plate 33 is fixedly connected with a lead screw motor 58, and the output shaft of the lead screw motor 58 is coaxially fixedly connected with a vertical vertical adjustment lead screw 48. , the bottom end of the vertical adjustment screw 48 is threaded and connected with the limited height blade 45, the length direction of the height limit blade 45 is consistent with the length direction of the discharge port of the raw material box 41, and the bottom of the height limit blade 45 is close to the initial base layer or the synchronous base layer On the upper surface, the initial base layer or the synchronous base layer first passes through the outlet of the raw material box 41 and then passes through the height-limiting blade 45, so that when the raw material box 41 releases a relatively large amount of perovskite solution, the thickness of the perovskite wet film obtains a uniform thickness. For control, the upper surface of the height-limiting blade 45 is sheathed along the vertical direction and is slidably connected with a stabilizing rod 49 , and the upper end of the stabilizing rod 49 is fixedly connected to the lower surface of the outer wall plate 33 .

Referring to Fig. 3 and Fig. 4, the bottom end of the height-limiting blade 45 is inclined, and the inclined bottom end of the height-limiting blade 45 is closer to the raw material box 41 than the inclined upper end, and the angle between the inclined bottom end of the height-limiting blade 45 and the conveyor belt can be The limit is less than 30 degrees, so that excess perovskite solution can flow more smoothly to the inclined upper surface of the height-limiting blade 45 . The height-limiting blade 45 vertical faces are fixedly connected with a blade suction block 47, and the blade suction block 47 lower surface offers an air inlet that is inclined, and the blade suction block 47 air inlet length direction is consistent with the height-limiting blade 45 length directions, and the blade suction The inclined bottom end of the air inlet of the block 47 faces the inclined upper surface of the height-limiting blade 45, and the blade suction block 47 communicates with an external negative pressure air pump through a hose (not shown in the figure) so that the blade suction block 47 can hold the height-limiting blade 45 The excess perovskite solution on the inclined upper surface is sucked away in time.

With reference to Fig. 4, the bottom of both ends of the raw material box 41 in the length direction is fixedly connected with an end suction block 46, and the bottom of the vertical side of the two end suction blocks 46 is similar to an air inlet, and the end suction block 46 passes through the hose. (not shown in the figure) Connect with an external negative pressure air pump to suck away the perovskite solution flowing from the upper surface of the initial base layer or the synchronous base layer to the side. The air inlet of the end suction block 46 is inclined, and the two end suction blocks The inclined bottom of the air inlet of 46 is close to each other, so that the peripheral part of the perovskite wet film is not easy to be sucked away directly. The two end suction blocks 46 are attached to the two ends in the length direction of the inclined bottom of the height-limiting blade 45 one by one, and the length of the two end suction blocks 46 is greater than the furthest distance between the height-limiting blade 45 and the raw material box 41 , so that the end suction block 46 can more fully absorb excess perovskite solution.

The implementation principle of a perovskite thin film deposition process in the embodiment of the present application is: the coating die head 3 repeats the coating of an initial base layer and a synchronous base layer in sequence, so that the idle time of the coating die head 3 is reduced, which is helpful Improve the forming efficiency of the overall perovskite film.

All of the above are preferred embodiments of the application, and are not intended to limit the protection scope of the application. Therefore, all equivalent changes made according to the structure, shape, and principle of the application should be covered by the protection scope of the application. Inside.

Claims (10)

1. A perovskite thin film deposition process, characterized by: the method specifically comprises the following steps:

step 1, setting a row of initial base layers and a plurality of rows of synchronous base layers, and coating a first initial base layer by using coating equipment;

step 2, coating the first synchronous base layer of the adjacent row after the first initial base layer is coated, and simultaneously conveying the first initial base layer and performing vacuum flash evaporation;

step 3, when the first initial base layer is subjected to vacuum flash evaporation, the first synchronous base layer in each row is coated, and then the second initial base layer is coated and repeated continuously;

step 4, after the vacuum flash evaporation of the second initial base layer is finished, coating the synchronous base layer of the second base layer in each row, then coating a third initial base layer, and simultaneously annealing the first initial base layer;

and 5, when the coating of the third initial base layer is finished, the annealing of the first initial base layer is finished, and then the coating of the third synchronous base layer and the annealing of the first synchronous base layer in the adjacent row are carried out and repeated continuously.

2. The perovskite thin film deposition process of claim 1, wherein: the coating equipment comprises a case (1), a plurality of conveyor belts (2) which are arranged in the case (1) and drive a row of initial base layers and a plurality of rows of synchronous base layers to move in a one-to-one correspondence manner, a coating die head (3) which is arranged in the case (1) and carries out perovskite wet film coating on the base layers, and a die head moving device (4) which is arranged in the case (1) and drives the coating die head (3) to move along the width direction of the conveyor belts (2).

3. The perovskite thin film deposition process of claim 2, wherein: the die head moving device (4) comprises a group of synchronizing wheels (5) which are rotatably connected to the case (1), a synchronous belt (51) which is in transmission connection with the group of synchronizing wheels (5), a belt block (52) which is fixedly connected to the synchronous belt (51) and drives the coating die head (3) to synchronously move, a synchronizing wheel motor (53) which is arranged on the case (1) and enables the synchronizing wheels (5) to rotate, and a guide rod (54) which is arranged on the case (1) and enables the belt block (52) to be sleeved and slide.

4. A perovskite thin film deposition process according to claim 3, wherein: the belt block (52) is provided with a vertical adjusting cylinder (55), a power rod of the vertical adjusting cylinder (55) is fixedly connected with a vertical adjusting block (56) which is used for connecting the coating die head (3) so as to vertically move the coating die head (3), and the belt block (52) is provided with an orientation rod (57) which penetrates through and is slidably connected with the vertical adjusting block (56).

5. The perovskite thin film deposition process of claim 4, wherein: coating die head (3) including can dismantle the top cap (59) of connecting in erecting accent piece (56), can dismantle raw materials box (41) of connecting in top cap (59), sliding connection is in raw materials box (41) inside and send out perovskite solution piston plate (42) of raw materials box (41), set up in raw materials box (41) and send into gas so that gas port (32) that piston plate (42) removed, locate raw materials box (41) discharge gate department and make perovskite solution can only follow raw materials box (41) interior ejection of compact check valve (43) of sending out, locate raw materials box (41) feed gate department and make perovskite solution can only enter into raw materials box (41) interior feed check valve (44), piston plate (42) height is higher than ejection of compact check valve (43) or the height of feed check valve (44).

6. The perovskite thin film deposition process of claim 5, wherein: the discharging one-way valves (43) are arranged in a plurality along the width direction of the conveyor belt (2).

7. The perovskite thin film deposition process of claim 5, wherein: former feed box (41) discharge gate one side department is equipped with limit for height blade (45) of further control perovskite wet film thickness, and former feed box (41) both ends department is equipped with and is close to basic unit's side and inhales piece (46) with the inspiratory tip of unnecessary perovskite solution, and piece (46) are inhaled in limit for height blade (45) terminal surface to the tip, and limit for height blade (45) are close to former feed box (41) discharge gate one side department and are equipped with and inhale piece (47) with the inspiratory blade of unnecessary perovskite solution.

8. The perovskite thin film deposition process of claim 7, wherein: the air inlet of the end suction block (46) is inclined and lower than the height of the upper surface of the initial base layer or the synchronous base layer, and the inclined lower end of the air inlet of the end suction block (46) is close to the initial base layer or the synchronous base layer.

9. The perovskite thin film deposition process of claim 7, wherein: height limit blade (45) bottom is slope and slope bottom and is close to in former feed box (41), and the air inlet that the piece (47) was inhaled to the blade is slope and slope bottom towards the slope upper surface in height limit blade (45).

10. The perovskite thin film deposition process of claim 7, wherein: former feed box (41) rotate be connected with threaded connection in the perpendicular lead screw (48) of transferring of limit for height blade (45), and former feed box (41) are equipped with and drive perpendicular lead screw motor (58) of transferring lead screw (48) pivoted, and former feed box (41) fixedly connected with supplies limit for height blade (45) cover to establish and gliding stabilizer (49).

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