Low pressure nanocrystallization apparatus

Abstract

The present application provides a low-pressure nanocrystallization device, which comprises a cavity, a plurality of gas inlet devices, a plurality of flow distribution plates, a suction device and a substrate. The gas inlet devices provide a gas into the cavity in a gas inlet direction. The flow distribution plates have a plurality of openings, the opening area of the flow distribution plate closer to the gas inlet device is smaller, and the opening positions of two adjacent flow distribution plates mapped by the gas inlet direction do not overlap. The substrate can carry a body to be crystallized. When the gas enters the cavity, it passes through a plurality of flow distribution plates, so that the pressure of the gas when it contacts the body to be crystallized is smaller and more uniform, and finally the gas is sucked out by the suction device to the outside.

Description

TECHNICAL FIELD

[0001] The present application relates to a crystallization device, in particular to a low-pressure nanocrystallization device using a perovskite precursor solution solvent for a substitution anti-solvent process. BACKGROUND

[0002] Since Professor Miyasaka of Japan proposed methylammonium lead iodide (MAPbI3) as the light-absorbing layer of a solar cell in 2009, the efficiency of perovskite solar cells has progressed rapidly, and the single-junction efficiency has reached nearly 26%, which is comparable to the power generation efficiency of conventional silicon solar cells, and the production cost is only 1 / 3 of that of conventional silicon solar cells. It is currently the most competitive solar technology, and one of the biggest challenges for its industrialization is stable and uniform crystallization on a large area.

[0003] The perovskite precursor solution solute is a compound with strong ionic force, which needs to be mixed with a specific ratio of aprotic polar solvent to dissolve the solute, and the precursor solution solute and the solvent undergo polycondensation-nucleation crystallization, which has a decisive influence on the final thin film crystallization quality. Most of the known processes published use highly volatile ionic solvents, and a strong air knife is used to blow gas under normal pressure to promote the volatilization of the solvent and the crystallization of the perovskite. This process has good perovskite thin film crystallization quality and fast production speed, but it requires the use of complex ratio solvents and perovskite ion solution additives, which increases the complexity of the process and the instability of the perovskite precursor solution storage. In order to dry the film under normal pressure, the main solvent uses toxic and carcinogenic substances such as dimethylformamide (DMF), acetonitrile (ACN), or 2-methoxyethanol (2-ME). In addition, in order to make the perovskite crystallization complete, a small-scale experiment often uses an anti-solvent process, i.e. dropping an anti-solvent (solutes are insoluble in anti-solvents) of the precursor solution on the wet film to make the solutes crystallize, which requires very accurate dropping time and is difficult to achieve on a large area process. In addition, in the perovskite process, the commonly used anti-solvents are volatile and toxic gases such as ethoxyethane, toluene, chlorobenzene (CB), etc., which may cause health problems for users.

[0004] Chemical vapor deposition (CVD) injects various gas reactants to react on a substrate, and the products formed are deposited on the substrate. In a CVD machine, a plate is placed to block the gas pipeline outlet holes so that the gas flows to the holes on the plate, which has a larger area than the inlet pipeline. The reactants diffuse to the substrate by concentration gradient, and the substrate must be a distance away from the plate to avoid the initial non-uniform concentration. Therefore, this process requires a high cavity, which causes waste of reactants.

[0005] Atomic layer deposition (ALD) is similar to CVD. The machine injects various gas reactants in sequence. Due to the characteristics of the substrate, gas molecules will only deposit one layer on the substrate. Therefore, as long as the gas concentration is still within the operating range, non-uniform concentration will not cause non-uniform film thickness. In order to make the reactants reach the substrate surface faster, a flow divider is installed near the gas outlet. However, a single layer flow divider is not suitable for larger area processes because the output of the flow divider far from the gas outlet is still not allocated enough gas flow. Therefore, how to develop an innovative structure with more ideal practicality to solve the above problems is the goal and direction of related industries. SUMMARY

[0006] The purpose of the present application is to provide a low-pressure nanocrystallization device with multiple flow plates near the gas inlet side in a cavity. Each flow plate has multiple holes. The farther the flow plate is from the gas inlet pipe, the larger the hole area. This slows down the entry of fluid, so when the fluid contacts a crystallization body, the pressure is smaller and more uniform, achieving the effect of large-area and uniform gas processing.

[0007] To achieve the above purpose, the present application provides a low-pressure nanocrystallization device, which includes a cavity, multiple gas inlet devices, a first flow plate, a second flow plate, an extraction device, and a substrate. The cavity has a first side and a second side. The gas inlet device is connected to the first side to provide a gas into the cavity. The first flow plate is located in the cavity and adjacent to the first side. The first flow plate also includes multiple first openings, and the first openings have a first area. The second flow plate is located in the cavity and adjacent to the first flow plate away from the first side. The second flow plate is a distance away from the first flow plate. The second flow plate also includes multiple second openings, and the second openings have a second area, which is larger than the first area. The extraction device is connected to the second side to extract the gas in the cavity to the outside. The substrate is located in the cavity and adjacent to the second side. The outer edge of the substrate is a distance away from the inner wall of the cavity, and the substrate can carry a crystallization body.

[0008] wherein the intake device is mapped to the first baffle plate position without the first aperture in the gas entry direction, and the first aperture is mapped to the second baffle plate position without the second aperture in the gas entry direction, so that when the gas enters the cavity, it sequentially passes through the first baffle plate, the first aperture, the second baffle plate, the second aperture to the crystallization body, and the gas is drawn by the extraction device along the gap to the outside.

[0009] In a preferred embodiment of the present application, the low-pressure nanocrystallization device further comprises a heating device located in the cavity and abutting against the substrate. The heating device can heat or maintain the substrate to a temperature.

[0010] In a preferred embodiment of the present application, the first aperture and the second aperture are circular in shape, the first aperture has a radius of 0.5 mm to 1.5 mm, and the second aperture has a radius of 1.5 mm to 2.5 mm.

[0011] In a preferred embodiment of the present application, the first distance is 0.2 mm to 3.0 mm.

[0012] In a preferred embodiment of the present application, the outer periphery of the first baffle plate is connected to the inner wall of the cavity, and the outer periphery of the second baffle plate is connected to the inner wall of the cavity.

[0013] In a preferred embodiment of the present application, the low-pressure nanocrystallization device further comprises a third baffle plate located in the cavity and adjacent to the second baffle plate away from the first side. The third baffle plate is separated from the second baffle plate by a second distance. The third baffle plate further comprises a plurality of third apertures, the third apertures have a third area, the third area is greater than the second area, and the second aperture is mapped to the third baffle plate position without the third aperture in the gas entry direction. The third aperture is circular in shape, and the third aperture has a radius of 2.5 mm to 3.5 mm. The outer periphery of the third baffle plate is connected to the inner wall of the cavity, and the second distance is 0.2 mm to 3.0 mm.

[0014] In a preferred embodiment of the present application, the crystallization body is located on the substrate by spin coating, blade coating, slot coating, or spraying means.

[0015] In a preferred embodiment of the present application, the crystalline body is a perovskite thin film. The perovskite thin film is formed on the substrate by spin coating, blade coating, slot-die coating or spray coating of a perovskite precursor solution. The perovskite thin film can be subjected to a post-treatment process on the substrate. The post-treatment process can be a recrystallization process or a passivation process. BRIEF DESCRIPTION OF DRAWINGS

[0016] In order to make the above and other objects, features, characteristics and advantages of the present application more comprehensible, the following will briefly describe the preferred embodiments with the accompanying drawings:

[0017] Figure 1 FIG. 1 is a schematic diagram of a side view of a low-pressure nanocrystallization device according to a first preferred embodiment of the present application.

[0018] Figure 2 FIG. 2 is a schematic diagram of an arrangement of a plurality of flow distribution plates according to a first preferred embodiment of the present application.

[0019] Figure 3 FIG. 3 is a schematic diagram of a side view of a low-pressure nanocrystallization device according to a second preferred embodiment of the present application.

[0020] Figure 4 FIG. 4 is a schematic diagram of an arrangement of a plurality of flow distribution plates according to a second preferred embodiment of the present application.

[0021] Figure 5 FIG. 5 is a schematic diagram of a pressure distribution of a substrate without flow distribution plates in a low-pressure nanocrystallization device according to the present application.

[0022] Figure 6 FIG. 6 is a schematic diagram of a pressure distribution of a substrate with two flow distribution plates in a low-pressure nanocrystallization device according to the present application.

[0023] Figure 7 FIG. 7 is a schematic diagram of a perovskite thin film formed with one flow distribution plate in a low-pressure nanocrystallization device according to the present application.

[0024] Figure 8 FIG. 8 is a schematic diagram of a perovskite thin film formed with three flow distribution plates in a low-pressure nanocrystallization device according to the present application.

[0025] In accordance with common practice the various features and elements described with reference to the drawings can not be drawn to scale, but are drawn as is deemed best for the purposes of illustration and description. Identical or similar elements and / or components are denoted by the same or similar reference numbers throughout the several views.

[0026] LIST OF SYMBOLS

[0027] 1: cavity

[0028] 11: first side

[0029] 12: second side

[0030] 2: gas inlet device

[0031] 3: first flow divider

[0032] 31: first aperture

[0033] 4: second flow divider

[0034] 41: second aperture

[0035] 5: extraction device

[0036] 6: substrate

[0037] 61: body to be crystallized

[0038] 7: third flow divider

[0039] 71: third aperture

[0040] 8: heating device

[0041] 9: gas

[0042] R1: first aperture radius

[0043] R2: second aperture radius

[0044] R3: third aperture radius

[0045] S: gap

[0046] D1: first distance

[0047] D2: second distance DETAILED DESCRIPTION

[0048] To facilitate the examiner's further understanding and knowledge of the purpose, shape, configuration, device features and their effects of the present invention, embodiments are described in detail below in conjunction with the drawings.

[0049] The following disclosure provides different embodiments or examples to build different features of the provided subject matter. The specific examples of the components described below and the arrangement are for the purpose of simplifying the disclosure, and the purpose is not to constitute a limitation; the size and shape of the elements are also not limited by the disclosed range or values, but can depend on the process conditions or required characteristics of the elements. For example, the technical features of the present invention are described using cross-sectional views, which are idealized embodiment schematic diagrams. Therefore, it is foreseeable that the shapes of the drawings will be different due to manufacturing processes and tolerances, and should not be limited thereby.

[0050] Moreover, the use of relative terms such as "below," "lower," "below" and "higher" are intended to facilitate a description of the relationships for the elements or features illustrated in the drawings; in addition, the spatial relative terms include different directions of the elements in use or operation, in addition to the directions depicted in the drawings.

[0051] Referring to Figure 1 and Figure 2 , which are schematic diagrams of a side view cross-sectional structure of a first preferred embodiment of a low-pressure nanocrystal device and a schematic diagram of a three-dimensional structure arrangement of a plurality of flow distribution plates. The present application provides a low-pressure nanocrystal device, which comprises a cavity 1, a plurality of gas inlet devices 2, a first flow distribution plate 3, a second flow distribution plate 4, an extraction device 5, and a substrate 6. The cavity 1 has a first side 11 and a second side 12. The gas inlet device 2 is connected to the first side 11 and can provide a gas 9 into the cavity 1, and the gas 9 can be any gas. The first flow distribution plate 3 is located in the cavity 1 and adjacent to the first side 11, and the first flow distribution plate 3 further comprises a plurality of first openings 31, and the first openings 31 have a first area. The first openings 31 are circular in shape, and the radius R1 of the first openings 31 is between 0.5 mm and 1.5 mm, of course, the shape of the first openings 31 is not limited to circular, but can also be square, rectangular, triangular, etc., in fact, any shape is possible.

[0052] The second flow distribution plate 4 is located in the cavity 1 and adjacent to the first flow distribution plate 3 away from the first side 11, and the second flow distribution plate 4 is separated from the first flow distribution plate 3 by a first distance D1, and the second flow distribution plate 4 further comprises a plurality of second openings 41, and the second openings 41 have a second area, and the second area is greater than the first area. The second openings 41 are circular in shape, and the radius R2 of the second openings 41 is between 1.5 mm and 2.5 mm, and the first distance D1 is between 0.2 mm and 3.0 mm. In the preferred embodiment of the present application, the outer periphery of the first flow distribution plate 3 is connected to the inner wall of the cavity 1, and the outer periphery of the second flow distribution plate 4 is connected to the inner wall of the cavity 1.

[0053] The extraction device 5 is connected to the second side 12, and the extraction device 5 extracts the gas 9 in the cavity 1 to an external environment (not shown). The substrate 6 is located in the cavity 1 and adjacent to the second side 12, and the outer periphery of the substrate 6 is separated from the inner wall of the cavity 1 by a gap S, and the substrate 6 can carry a to-be-crystallized body 61, and the to-be-crystallized body 61 is located on the substrate 6 by spin coating, blade coating, slot coating or spraying means.

[0054] In the preferred embodiment of the present application, the crystalline body 61 is a perovskite thin film, which is formed by spin coating, doctor blade coating, slot coating or spray coating of a perovskite precursor solution on the substrate 6. Of course, the perovskite thin film can be subjected to a reprocessing procedure on the substrate 6, which is a recrystallization or a passivation procedure. The low-pressure nanocrystallization device further comprises a heating device 8, which is located in the chamber 1 and is in contact with the substrate 6. The heating device 8 can heat or maintain the substrate 6 to a temperature, so that the crystalline body 61 on the substrate 6 is maintained at an operating temperature.

[0055] Wherein the first shunt plate 3 is not provided with the first opening 31 at the position mapped by the gas 9 entering direction of the gas inlet device 2, and the second opening 41 is not provided at the position mapped by the gas 9 entering direction of the first shunt plate 3 on the second shunt plate 4, so that when the gas 9 enters the chamber 1, it sequentially passes through the first shunt plate 3, the first opening 31, the second shunt plate 4, the second opening 41 and the crystalline body 61, and the gas 9 is extracted by the extraction device 5 along the gap S to the outside. Therefore, by not providing the first opening 31 at the position mapped by the gas 9 entering direction of the first shunt plate 3 on the gas inlet device 2, the gas 9 entering the chamber 1 will first hit the first shunt plate 3 and then flow smoothly into the first openings 31. At this time, by the length of the first distance D1 and the size of the first opening 31, and by not providing the second opening 41 at the position mapped by the gas 9 entering direction of the first shunt plate 3 on the second shunt plate 4, the gas 9 will hit the second shunt plate 4 and then flow smoothly into the second openings 41. Since the second opening 41 is larger than the first opening 31, the gas 9 will slow down when it contacts the crystalline body 61, and the contact pressure will be smaller and more uniform, achieving the effect of large-area and uniform gas processing.

[0056] Please refer to Figure 3 and Figure 4As shown in the figure, it is a schematic diagram of the side view and the cross-sectional structure of the second preferred embodiment of the low-pressure nanocrystallization device of the present application, and a schematic diagram of the three-dimensional structure arrangement of the plurality of flow distribution plates. Different from the above-mentioned embodiment, the low-pressure nanocrystallization device of the present application further comprises a third flow distribution plate 7, which is located in the cavity 1 and adjacent to the side of the second flow distribution plate 4 away from the first side 11. The third flow distribution plate 7 is at a second distance D2 from the second flow distribution plate 4. The third flow distribution plate 7 further comprises a plurality of third openings 71, which have a third area. The third area is greater than the second area, and the second openings 41 are mapped to the positions of the third flow distribution plate 7 without the third openings 71 in the entering direction of the gas 9. The third openings 71 are circular in shape, and the radius R3 of the third openings 71 is between 2.5 mm and 3.5 mm. The outer edge of the third flow distribution plate 7 is connected to the inner wall of the cavity 1, and the second distance D2 is between 0.2 mm and 3.0 mm.

[0057] Please refer to Figures 5 to 8 As shown in the figure, it is a schematic diagram of the gas pressure distribution of the substrate when the low-pressure nanocrystallization device of the present application does not have a flow distribution plate and when it has two flow distribution plates, and a perovskite thin film forming diagram when the low-pressure nanocrystallization device of the present application has one flow distribution plate and when it has three flow distribution plates. As shown in Figure 5 , the gas inlet device 2 is set to a pipe flow of 2 slm (slm: Standard Liter / Minute, X liters per minute under standard conditions), and the gas pressure of the extraction device 5 is set to 0 atm. The lowest point of the gas pressure on the substrate 6 is dark blue (0.015 atm), and the highest point is red (0.016 atm). The to-be-crystallized body 61 will produce defects as shown in Figure 7 , and the needle-shaped holes arranged in a lattice are very obvious. As shown in Figure 6 , the gas inlet device 2 is set to a pipe flow of 2 slm (slm: Standard Liter / Minute, X liters per minute under standard conditions), and the gas pressure of the extraction device 5 is set to 0 atm. The highest point of the gas pressure on the substrate 6 is red (0.033 atm), and the lowest point is orange (0.033 atm). The to-be-crystallized body 61 will produce a state without obvious defects as shown in Figure 8 .

[0058] The above embodiments are only used to illustrate the technical solutions of the present application and not to limit it. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced equivalently without departing from the spirit and scope of the technical solutions of the present application.

Claims

1. A low-pressure nanocrystallization device, comprising: A cavity having a corresponding first side and a second side; Multiple air intake devices are connected to the first side, and each air intake device can provide gas into the cavity; A first flow divider is located in the cavity and adjacent to the first side. The first flow divider also includes a plurality of first openings, each having a first area. A second flow divider is located in the cavity and is adjacent to the side of the first flow divider away from the first side. The second flow divider is separated from the first flow divider by a first distance. The second flow divider also includes a plurality of second openings, each second opening having a second area that is larger than the first area. A third diverter plate is located in the cavity and is adjacent to the side of the second diverter plate away from the first side. The third diverter plate is separated from the second diverter plate by a second distance. The third diverter plate also includes a plurality of third openings, each having a third area that is larger than the second area. An extraction device is connected to the second side surface, which extracts the gas in the cavity to the outside. A substrate is located in the cavity and adjacent to the second side surface. The outer edge of the substrate is separated from the inner wall of the cavity by a gap. The substrate can support a crystallizer, which is a perovskite film and a perovskite precursor solution. The air intake device, when mapped to the position of the first diverter plate in the gas entry direction, does not have the first opening; the first opening, when mapped to the position of the second diverter plate in the gas entry direction, does not have the second opening; and the second opening, when mapped to the position of the third diverter plate in the gas entry direction, does not have the third opening. When the gas enters the cavity, it passes sequentially through the first diverter plate, the first opening, the second diverter plate, the second opening, the third diverter plate, and the third opening to the crystallizer. The gas is then extracted to the outside by the extraction device along the gap.

2. The low-pressure nanocrystallization device as described in claim 1, characterized in that, The low-pressure nanocrystallization device also includes a heating device located in the cavity and attached to the substrate, which can heat or maintain the substrate to a certain temperature.

3. The low-pressure nanocrystallization device as described in claim 1, characterized in that, Both the first opening and the second opening are circular in shape. The radius of the first opening is between 0.5 mm and 1.5 mm, and the radius of the second opening is between 1.5 mm and 2.5 mm.

4. The low-pressure nanocrystallization device as described in claim 1, characterized in that, The first distance is between 0.2 mm and 3.0 mm.

5. The low-pressure nanocrystallization device as described in claim 1, characterized in that, The outer edge of the first diverter plate is in close contact with the inner wall of the cavity, and the outer edge of the second diverter plate is in close contact with the inner wall of the cavity.

6. The low-pressure nanocrystallization device as described in claim 1, characterized in that, The third opening is circular in shape and has a radius between 2.5 mm and 3.5 mm. The outer edge of the third diverter plate is in close contact with the inner wall of the cavity, and the second distance is between 0.2 mm and 3.0 mm.

7. The low-pressure nanocrystallization device as described in claim 1, characterized in that, The crystallizer is deposited on the substrate by spin coating, blade coating, slot coating or spray coating.

8. The low-pressure nanocrystallization device as described in claim 7, characterized in that, The perovskite film can be placed on the substrate and subjected to a reprocessing process, which is either recrystallization or passivation.

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