Spatial atomic layer deposition system, atomic layer deposition process using same, and composite film
By setting up multiple metal and oxygen source input tubes in the spatial isolation atomic layer deposition system, the preparation of multi-layer films is achieved, solving the problems of single film layers and poor component regulation in the prior art, and improving the film quality and the performance of solar cell modules.
Patent Information
- Application Number
- CN202411654723.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-19
- Publication Date
- 2025-03-14
AI Technical Summary
The existing spatial isolation atomic layer deposition technology has only a single reaction source channel, resulting in a single film layer prepared, which has poor regulatory properties of film components, and is not suitable for the preparation of composite film layers.
Different films are prepared by setting up multiple metal input tubes and multiple oxygen source input tubes to achieve selective deposition or deposition mixing of metal source and oxygen source. At the same time, the entire preparation process does not require the substrate to be taken out of the cavity, which improves the quality and deposition efficiency of the film.
The preparation of multi-film layers in a smaller mobile space is achieved, which improves the atomic layer deposition efficiency, improves the thin film structure and characteristics, and improves the conductivity and photoelectric conversion efficiency of solar cell modules.
Smart Images
Figure CN119615112A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of solar cell components, and in particular to a spatial atomic layer deposition system, an atomic layer deposition process using the same, and a composite film. Background Art
[0002] Atomic layer deposition (ALD) is a technique capable of depositing a wide range of thin film materials from the gas phase. ALD shows great promise in emerging semiconductor and energy conversion technologies. Based on a continuous, self-limiting reaction, ALD offers excellent conformality on high aspect ratio structures, thickness control at the angstrom level, and tunable film composition. With these advantages, ALD has become a powerful tool for many industrial and research applications.
[0003] Atomic layer deposition technology is divided into "space-isolated atomic layer deposition" and "time-isolated atomic layer deposition" technologies. The method of space-isolated atomic layer deposition is to move the sample between different positions and expose it to different precursors at each position. Time-isolated atomic layer deposition is to fix the wafer and alternately introduce and remove precursors in the chamber.
[0004] Spatially isolated atomic layer deposition technology is usually used in production lines that need to control the production rhythm to improve production efficiency. Its limitation is that it only has a single reaction source channel. Therefore, the thin film layer prepared by the existing spatially isolated atomic layer deposition equipment is single and the film component controllability is poor, which is not suitable for the preparation of composite thin film layers. Summary of the invention
[0005] In view of the deficiencies of the prior art, the present invention provides a spatial atomic layer deposition system, an atomic layer deposition process using the same, and a composite film. The present invention can realize the selective deposition of metal sources and oxygen sources or the preparation of different films after the deposition is mixed by setting multiple metal input tubes and multiple oxygen source input tubes. At the same time, the substrate does not need to be taken out of the cavity during the entire preparation process, which improves the quality of the prepared film. The coordination of multiple metal source input tubes and oxygen source input tubes can realize the preparation of multiple film layers in a smaller mobile space, improve the deposition efficiency of the atomic layer, and also improve the structure of the deposited atomic layer film, and regulate the film properties to improve the conductivity and photoelectric conversion efficiency of the solar cell module.
[0006] The technical solution of the present invention is as follows:
[0007] The first aspect of the present invention protects a spatial atomic layer deposition system, including a plate reaction chamber 1, a nitrogen inlet pipe 11, a nitrogen exhaust pipe 12, a metal source inlet pipe group 13, and an oxygen source inlet pipe group 14; the plate reaction chamber 1 is connected to a plurality of nitrogen inlet pipes 11 and a plurality of nitrogen exhaust pipes 12 along its own length direction; the nitrogen exhaust pipe 12 is arranged between adjacent nitrogen inlet pipes 11, and at least two nitrogen exhaust pipes 12 are arranged between the nitrogen inlet pipes 11; the plate reaction chamber 1 is also cross-arranged with a metal source inlet pipe group 13 and an oxygen source inlet pipe group 14 in sequence along its own length direction, the metal source inlet pipe group 13 and the oxygen source inlet pipe group 14 are both connected to the plate reaction chamber 1, and the metal source inlet pipe group 13 is arranged between adjacent nitrogen exhaust pipes 12; the oxygen source inlet pipe group 14 adjacent to a metal source inlet pipe group 13 is located between adjacent nitrogen exhaust pipes 12.
[0008] Preferably, the metal source input tube group 13 includes a plurality of metal source input tubes 130 spaced apart from each other; and the oxygen source input tube group 14 includes a plurality of oxygen source input tubes 140 spaced apart from each other.
[0009] Preferably, the metal source input pipe group 13 includes at least two metal source input pipes 130, and the metal source input pipes 130 are arranged in the length direction of the plate reaction chamber 1 and communicated with the plate reaction chamber 1; the oxygen source input pipe group 14 includes at least two oxygen source input pipes 140, and the oxygen source input pipes 140 are arranged in the length direction of the plate reaction chamber 1 and communicated with the plate reaction chamber 1.
[0010] Preferably, the metal source input tube group 13 includes a metal source input tube A131 and a metal source input tube B132, and the metal source input tube A131 and the metal source input tube B132 input the same or different metal sources; the oxygen source input tube group 14 includes an oxygen source input tube A141 and an oxygen source input tube B142, and the oxygen source input tube A141 and the oxygen source input tube B142 input the same or different oxygen sources.
[0011] Preferably, the metal source input by the metal source input pipe A131 is TDMASn, and the metal source input by the metal source input pipe B132 is DEZ; the oxygen source input by the oxygen source input pipe A141 is H2O, and the oxygen source input by the oxygen source input pipe B142 is O3.
[0012] Preferably, a single metal source input pipe 130 is provided with a first solenoid valve and a first pulse valve, and the flow rate of the metal source input into the plate-type reaction chamber 1 is controlled by the first solenoid valve; a single oxygen source input pipe 140 is provided with a second solenoid valve and a second pulse valve, and the flow rate of the oxygen source input into the plate-type reaction chamber 1 is controlled by the second solenoid valve.
[0013] The second aspect of the present invention protects an atomic layer deposition process performed using the spatial atomic layer deposition system described in the first aspect, the atomic layer deposition process comprising the following steps:
[0014] S1-1, set the metal source input by the metal source input pipe A131 to TDMASn, and the metal source input by the metal source input pipe B132 to DEZ; the oxygen source input by the oxygen source input pipe A141 to H2O, and the solenoid valve of the oxygen source input pipe B142 is closed.
[0015] The substrate is moved to the bottom of the metal source input tube B132. The metal source input tube B132 pulses the first precursor DEZ to expose it to the substrate surface and chemically adsorbs DEZ on the substrate surface. The nitrogen input tube 11 adjacent to the metal source input tube B132 inputs nitrogen into the plate reaction chamber 1. The nitrogen exhaust pipe 12 adjacent to the metal source input tube B132 draws the nitrogen in the plate reaction chamber 1 and the remaining unreacted first precursor DEZ out of the plate reaction chamber 1.
[0016] S1-2, the substrate continues to move to the bottom of the oxygen source input tube A141, the oxygen source input tube A141 pulses the second precursor H2O, the DEZ adsorbed on the surface of the substrate reacts chemically with H2O to obtain a ZnO film, the nitrogen input tube 11 adjacent to the oxygen source input tube A141 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the oxygen source input tube A141 extracts the nitrogen in the plate reaction chamber 1 and the remaining unreacted second precursor H2O out of the plate reaction chamber 1.
[0017] S1-3, repeat steps S1-1 to S1-2 0-18 times in a loop.
[0018] S1-4, move the substrate to the bottom of the metal source input tube A131, the metal source input tube A131 pulses the third precursor TDMASn on the substrate surface, and chemically adsorbs TDMASn on the substrate surface, the nitrogen input tube 11 adjacent to the metal source input tube A131 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the metal source input tube A131 extracts the nitrogen in the plate reaction chamber 1 and the remaining unreacted third precursor TDMASn from the plate reaction chamber 1.
[0019] S1-5, the substrate is moved to the bottom of the oxygen source input tube A141, and the oxygen source input tube A141 pulses the second precursor H2O, and the TDMASn adsorbed on the surface of the substrate reacts chemically with H2O to obtain SnO xThe film, the nitrogen input pipe 11 adjacent to the oxygen source input pipe A141 inputs nitrogen into the plate-type reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the oxygen source input pipe A141 extracts the nitrogen and the remaining unreacted second precursor H2O in the plate-type reaction chamber 1 out of the plate-type reaction chamber 1.
[0020] S1-6, repeating steps S1-4 to S1-5 10-100 times, and then atomic layer deposition can be performed on the substrate to obtain a multilayer ZnO / SnO x Composite film of membrane layer.
[0021] The third aspect of the present invention provides a composite film prepared by the atomic layer deposition process described in the second aspect, wherein the composite film comprises a multilayer ZnO / SnO x film layer, and the ZnO / SnO x The film layer includes at least one ZnO layer.
[0022] A fourth aspect of the present invention provides an atomic layer deposition process performed by the spatial atomic layer deposition system described in the first aspect, wherein the atomic layer deposition process may further include the following steps:
[0023] S2-1, set the metal source input by the metal source input tube A131 to TDMASn, and the metal source input by the metal source input tube B132 to DEZ; the oxygen source input by the oxygen source input tube A141 to H2O, and the oxygen source input by the oxygen source input tube B142 to O3, move the substrate to the bottom of the metal source input tube B132, the metal source input tube B132 pulses the first precursor DEZ to expose the substrate surface, and at the same time chemically adsorbs the first precursor DEZ on the substrate surface, the nitrogen input tube 11 adjacent to the metal source input tube B132 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the metal source input tube B132 extracts the nitrogen in the plate reaction chamber 1 and the remaining unreacted first precursor DEZ out of the plate reaction chamber 1.
[0024] S2-2, the substrate continues to move to below the oxygen source input tube A141, the oxygen source input tube A141 pulses the second precursor H2O, the second precursor DEZ adsorbed on the surface of the substrate reacts with H2O to obtain a ZnO film, the nitrogen input tube 11 adjacent to the oxygen source input tube A141 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the oxygen source input tube A141 extracts the nitrogen in the plate reaction chamber 1 and the remaining unreacted second precursor H2O from the plate reaction chamber 1.
[0025] S2-3, repeat S2-1 to S2-2 operations 0-18 times.
[0026] S2-4, move the substrate to the bottom of the metal source input tube A131, the metal source input tube A131 pulses the third precursor TDMASn on the substrate surface, and chemically adsorbs the third precursor TDMASn on the substrate surface, the nitrogen input tube 11 adjacent to the metal source input tube A131 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the metal source input tube A131 extracts the nitrogen in the plate reaction chamber 1 and the remaining unreacted third precursor TDMASn from the plate reaction chamber 1.
[0027] S2-5, the substrate continues to move to the bottom of the oxygen source input tube A141, the oxygen source input tube A141 pulses the second precursor H2O, and the TDMASn adsorbed on the substrate surface reacts with the second precursor H2O to obtain SnO x The film, the nitrogen input pipe 11 adjacent to the oxygen source input pipe A141 inputs nitrogen into the plate-type reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the oxygen source input pipe A141 extracts the nitrogen and the remaining unreacted second precursor H2O in the plate-type reaction chamber 1 out of the plate-type reaction chamber 1.
[0028] S2-6, the substrate moves to the bottom of the metal source input tube A131, the metal source input tube A131 pulses the third precursor TDMASn on the substrate surface, and chemically adsorbs TDMASn on the substrate surface, the nitrogen input tube 11 adjacent to the metal source input tube A131 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the metal source input tube A131 extracts the nitrogen in the plate reaction chamber 1 and the remaining unreacted third precursor TDMASn from the plate reaction chamber 1.
[0029] S2-7, the substrate moves to under the oxygen source input tube B142, the oxygen source input tube B142 pulses the fourth precursor O3, the TDMASn adsorbed on the surface of the substrate reacts with the fourth precursor O3 to obtain a SnO2 thin film, the nitrogen input tube 11 adjacent to the oxygen source input tube B142 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the oxygen source input tube B142 extracts the nitrogen in the plate reaction chamber 1 and the remaining unreacted fourth precursor O3 from the plate reaction chamber 1.
[0030] S2-8, repeating steps S2-3 to S2-7 7-70 times, and then atomic layer deposition of ZnO / SnO on the substrate can be achieved. x / SnO2 multilayer composite film.
[0031] Another aspect of the present invention also protects a multilayer composite film prepared by the atomic layer deposition process described in the fourth aspect, wherein the multilayer composite film comprises ZnO layers, SnO layers repeatedly stacked on the surface of a substrate. xlayer and SnO2 layer, the number of repetitions is 7-70 times, wherein the ZnO layer includes at least one layer of ZnO.
[0032] The beneficial technical effects of the present invention are:
[0033] The spatial atomic layer deposition system of the present invention can realize the selective deposition of metal source and oxygen source or the preparation of different thin films after the deposition mixture by improving the metal input pipeline and the oxygen source input pipeline. At the same time, the substrate does not need to be taken out of the cavity during the entire preparation process, which improves the quality of the prepared thin film; the coordination of multiple metal source input pipes and oxygen source input pipes can realize the preparation of multiple film layers in a smaller moving space, improve the deposition efficiency of the atomic layer, realize the preparation of composite thin films with various structures, and help improve and optimize the deposited atomic layer film structure, regulate the film characteristics, and improve the conductivity and photoelectric conversion efficiency of solar cell modules.
[0034] The spatial atomic layer deposition system can realize multi-layer ZnO-single-layer SnO x Preparation of composite films: multilayer ZnO-single-layer SnO x The composite film has better electrical conductivity, and the photoelectric performance of the solar device prepared by using the composite film is better.
[0035] The atomic layer deposition process used in the present invention is relatively simple, has low operating difficulty, and is easy to implement industrial production and manufacturing. BRIEF DESCRIPTION OF THE DRAWINGS
[0036] Figure 1 Schematic diagram of the overall structure of a spatial atomic layer deposition system in an embodiment of the present invention.
[0037] Figure 2 Schematic diagram of the structure of a composite film prepared by atomic layer deposition process A using a spatial atomic layer deposition system in an embodiment of the present invention.
[0038] Figure 3 Schematic diagram of the structure of a composite film prepared by atomic layer deposition process B using a spatial atomic layer deposition system in an embodiment of the present invention.
[0039] In the figure, 1. plate reaction chamber; 11. nitrogen input pipe; 12. nitrogen exhaust pipe; 13. metal source input pipe group; 130. metal source input pipe; 131. metal source input pipe A; 132. metal source input pipe B; 14. oxygen source input pipe group; 140. oxygen source input pipe; 141. oxygen source input pipe A; 142. oxygen source input pipe B. DETAILED DESCRIPTION
[0040] The present invention is described in detail below in conjunction with the accompanying drawings and embodiments.
[0041] The spatial atomic layer deposition system can realize the preparation of a single film layer, but it cannot realize the preparation of multiple layered thin films in the same system. The present invention realizes the multi-channel transportation of different oxygen sources or metal sources by improving the nitrogen input pipeline, gas output pipeline, metal source input pipeline, oxygen source input pipeline, etc. connected to the plate-type reaction chamber 1, thereby realizing the preparation of multi-layer thin films containing different substances.
[0042] The first aspect of the present invention provides a spatial atomic layer deposition system, such as Figure 1 As shown, it includes a plate-type reaction chamber 1, a nitrogen inlet pipe 11, a nitrogen exhaust pipe 12, a metal source inlet pipe group 13, and an oxygen source inlet pipe group 14; the plate-type reaction chamber 1 is connected to a plurality of nitrogen inlet pipes 11 and a plurality of nitrogen exhaust pipes 12 along its length direction. The nitrogen exhaust pipe 12 is arranged between adjacent nitrogen inlet pipes 11, and two nitrogen exhaust pipes 12 are arranged between adjacent nitrogen inlet pipes 11. The plate-type reaction chamber 1 is also cross-arranged with a metal source inlet pipe group 13 and an oxygen source inlet pipe group 14 in sequence along its length direction. The metal source input pipe group 13 and the oxygen source input pipe group 14 are both connected to the plate-type reaction chamber 1, and the metal source input pipe group 13 is arranged between adjacent nitrogen exhaust pipes 12; the oxygen source input pipe group 14 adjacent to a certain metal source input pipe group 13 is located between adjacent nitrogen exhaust pipes 12, that is, the adjacent metal source input pipe groups 13 and oxygen source input pipe groups 14 are separated by the nitrogen exhaust pipe 12, the nitrogen input pipe 11, and the nitrogen exhaust pipe 12.
[0043] In some embodiments, Figure 1 As shown, the metal source input pipe group 13 includes a plurality of metal source input pipes 130 spaced apart from each other, and the metal source input pipe group 13 includes at least two metal source input pipes 130, which are arranged in the length direction of the plate-type reaction chamber 1 and communicated with the plate-type reaction chamber 1. Preferably, the metal source input pipe group 13 includes a metal source input pipe A131 and a metal source input pipe B132. The metal source input pipe A131 and the metal source input pipe B132 can simultaneously input the same or different metal sources, or only one of the metal source input pipes A131 and the metal source input pipe B132 inputs the metal source, and the other is closed and does not input the metal source. The opening and closing of the metal source input pipe can be achieved by setting a control valve on the pipeline, and the control valve is not drawn in the schematic diagram of the present invention.
[0044] In some embodiments, Figure 1As shown, the oxygen source input pipe group 14 includes a plurality of oxygen source input pipes 140 spaced apart from each other, and the oxygen source input pipe group 14 includes at least two oxygen source input pipes 140, which are arranged in the length direction of the plate reaction chamber 1 and are connected to the plate reaction chamber 1. Preferably, the oxygen source input pipe group 14 includes an oxygen source input pipe A141 and an oxygen source input pipe B142. The oxygen source input pipe A141 and the oxygen source input pipe B142 can simultaneously input the same or different oxygen sources, or only one of the oxygen source input pipe A141 and the metal source input pipe B142 inputs the oxygen source, and the other is closed and does not input the oxygen source. The opening and closing of the oxygen source input pipe can be achieved by setting a control valve on the pipeline, and the control valve is not drawn in the schematic diagram of the present invention.
[0045] It can be understood that at least one metal source input pipe group 13 can be provided on the plate-type reaction chamber 1; at least one oxygen source input pipe group 14 can be provided on the plate-type reaction chamber 1. Figure 1 Two metal source input tube groups and two oxygen source input tube groups are set at the same time. When only one metal source input tube group and one oxygen source input tube group are set, materials and space can be saved. Different film layers can be prepared by setting different oxygen sources for each oxygen source input tube in the oxygen source input tube group, and inputting different metal sources to each input tube of the metal source input tube group, and combining reciprocating motion to achieve the preparation of different film layers in a smaller space. This process saves energy while improving production efficiency.
[0046] In some embodiments, the metal source input by the metal source input pipe A131 is TDMASn, i.e., metal source gas 1, and the metal source input by the metal source input pipe B132 is DEZ, i.e., metal source gas 2; the oxygen source input by the oxygen source input pipe A141 is H2O, i.e., oxygen source gas 1, and the oxygen source input by the oxygen source input pipe B142 is O3, i.e., metal source gas 2.
[0047] In some embodiments, a single metal source input pipe 130 is provided with a first solenoid valve and a first pulse valve (not shown in the figure), and the flow rate of the metal source input into the plate-type reaction chamber 1 is controlled by the first solenoid valve; a single oxygen source input pipe 140 is provided with a second solenoid valve and a second pulse valve, and the flow rate of the oxygen source input into the plate-type reaction chamber 1 is controlled by the second solenoid valve.
[0048] It is understandable that the present invention can realize the control of the flow rate of each individual metal source input pipe and oxygen source input pipe by installing a solenoid valve and a pulse valve respectively on the independent metal source input pipe and the oxygen source input pipe, and can realize the selective input of oxygen source or metal source, so as to realize the preparation of more composite film layers. At the same time, the present invention sets a plurality of adjacently distributed but independently metal source input pipes, and when the adjacent metal sources are different components, they can be opened at the same time or at different times. When opened at the same time, different mixed films can be obtained on the same surface, that is, different components of the same substrate layer can be prepared at different positions. When opened at different times, multiple groups of metal sources and oxygen sources can be alternately combined. At the same time, combined with the reciprocating movement of the substrate, the preparation time can be shortened. Compared with mixing multiple oxygen source branches, the single branch of the present invention can provide more possibilities for preparing different multi-layer composite films, while improving production efficiency.
[0049] It is understandable that the spatial atomic layer deposition system of the present invention also includes other accessories of the conventional atomic layer deposition system. For example, it also includes a metal source input container, an exhaust collection container, a nitrogen input container, an oxygen source input container, a substrate moving system, a control system coordinated with the moving system, etc. The metal source inlet and outlet containers are respectively connected to the metal source input pipeline to provide the metal source for the metal source input pipeline. The exhaust collection container is connected to the nitrogen exhaust pipe to collect the exhausted gas, and the nitrogen input container and the oxygen source input container are respectively used to provide the required nitrogen and oxygen sources.
[0050] It can be understood that the substrate of the present invention is placed on a moving platform of the substrate moving system, and the substrate moving platform can realize reciprocating movement of the substrate in the plate reaction chamber, thereby realizing repeated pulses of the metal source and / or oxygen source, thereby improving the efficiency of film preparation.
[0051] A second aspect of the present invention provides an atomic layer deposition process A performed using the spatial atomic layer deposition system of the first aspect. The atomic layer deposition process A comprises the following steps:
[0052] S1-1, set the metal source input by the metal source input tube A131 to TDMASn, and the metal source input by the metal source input tube B132 to DEZ; the oxygen source input by the oxygen source input tube A141 to H2O, close the solenoid valve of the oxygen source input tube B142, move the substrate to the bottom of the metal source input tube B132, the metal source input tube B132 pulses the first precursor DEZ to expose the substrate surface, and chemically adsorbs DEZ on the substrate surface, the dry nitrogen input tube 11 adjacent to the metal source input tube B132 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the metal source input tube B132 extracts the nitrogen in the plate reaction chamber 1 and the remaining unreacted first precursor DEZ out of the plate reaction chamber 1.
[0053] S1-2, the substrate continues to move to the bottom of the oxygen source input tube A141, the oxygen source input tube A141 pulses the second precursor H2O, the DEZ adsorbed on the surface of the substrate reacts chemically with H2O to obtain a ZnO film, the dry nitrogen input tube 11 adjacent to the oxygen source input tube A141 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the oxygen source input tube A141 extracts the nitrogen in the plate reaction chamber 1 and the remaining unreacted second precursor H2O from the plate reaction chamber 1.
[0054] S1-3, repeat steps S1-1 to S1-2 0-18 times in a loop.
[0055] S1-4, move the substrate to the bottom of the metal source input tube A131, the metal source input tube A131 pulses the third precursor TDMASn on the substrate surface, and chemically adsorbs TDMASn on the substrate surface, the dry nitrogen input tube 11 adjacent to the metal source input tube A131 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the metal source input tube A131 extracts the nitrogen in the plate reaction chamber 1 and the remaining unreacted third precursor TDMASn from the plate reaction chamber 1.
[0056] S1-5, the substrate is moved to the bottom of the oxygen source input tube A141, and the oxygen source input tube A141 pulses the second precursor H2O, and the TDMASn adsorbed on the substrate surface reacts chemically with H2O to obtain SnO x The film, the dry nitrogen input pipe 11 adjacent to the oxygen source input pipe A141 inputs nitrogen into the plate-type reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the oxygen source input pipe A141 extracts the nitrogen in the plate-type reaction chamber 1 and the remaining unreacted second precursor H2O out of the plate-type reaction chamber 1;
[0057] S1-6, repeating steps S1-4 to S1-5 10-100 times, and then atomic layer deposition can be performed on the substrate to obtain a multilayer ZnO / SnO x Composite films of membrane layers, such as Figure 2 shown.
[0058] The third aspect of the present invention provides a composite film prepared by the atomic layer deposition process of the second aspect, the composite film comprising a multilayer ZnO / SnO x film layer, and ZnO / SnO x The film layer includes at least one ZnO layer.
[0059] It can be understood that in the present invention, by opening and closing the oxygen source input tube and the metal source input tube, the ZnO / SnO xPreparation of composite thin films of membrane layers. By controlling the number of repetitions, films of different thicknesses and structures can be obtained. At the same time, since each metal source input pipe in the metal source input pipe group is controlled separately, the closure of one of them will not affect the stability of gas delivery in other metal source input pipes, thereby avoiding the influence of closing one or more pipes on the stability of gas flow in other pipes when multiple metal source inputs are realized by combining the main pipe and the branch pipe. Similarly, by setting a plurality of independent pipes in the oxygen source input pipe group, the oxygen source can be switched arbitrarily. Compared with connecting a plurality of oxygen source input branch pipes to the same main pipe, the structure of the plate-type reaction chamber connected to the main pipe makes the multiple branch pipes of the present invention more flexible, and the closure of a single pipe will not affect the stability of the pulse gas flow in other pipes.
[0060] A fourth aspect of the present invention provides an atomic layer deposition process B performed by the spatial atomic layer deposition system of the first aspect, wherein the atomic layer deposition process B comprises the following steps:
[0061] S2-1, set the metal source input by the metal source input tube A131 to TDMASn, and the metal source input by the metal source input tube B132 to DEZ; the oxygen source input by the oxygen source input tube A141 to H2O, and the oxygen source input by the oxygen source input tube B142 to O3, move the substrate to the bottom of the metal source input tube B132, the metal source input tube B132 pulses the first precursor DEZ to expose the substrate surface, and at the same time chemically adsorbs the first precursor DEZ on the substrate surface, the dry nitrogen input tube 11 adjacent to the metal source input tube B132 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the metal source input tube B132 extracts the nitrogen in the plate reaction chamber 1 and the remaining unreacted first precursor DEZ out of the plate reaction chamber 1, that is, exhausts.
[0062] S2-2, the substrate continues to move to below the oxygen source input tube A141, the oxygen source input tube A141 pulses the second precursor H2O, the second precursor DEZ adsorbed on the substrate surface reacts with H2O to obtain a ZnO film, the dry nitrogen input tube 11 adjacent to the oxygen source input tube A141 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the oxygen source input tube A141 extracts the nitrogen in the plate reaction chamber 1 and the remaining unreacted second precursor H2O from the plate reaction chamber 1.
[0063] S2-3, repeat S2-1 to S2-2 operations 0-18 times.
[0064] S2-4, move the substrate to the bottom of the metal source input tube A131, the metal source input tube A131 pulses the third precursor TDMASn on the substrate surface, and chemically adsorbs the third precursor TDMASn on the substrate surface, the dry nitrogen input tube 11 adjacent to the metal source input tube A131 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the metal source input tube A131 extracts the nitrogen in the plate reaction chamber 1 and the remaining unreacted third precursor TDMASn from the plate reaction chamber 1.
[0065] S2-5, the substrate continues to move to the bottom of the oxygen source input tube A141, the oxygen source input tube A141 pulses the second precursor H2O, and the TDMASn adsorbed on the substrate surface reacts with the second precursor H2O to obtain SnO x The film, the dry nitrogen input pipe 11 adjacent to the oxygen source input pipe A141 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the oxygen source input pipe A141 extracts the nitrogen and the remaining unreacted second precursor H2O in the plate reaction chamber 1 out of the plate reaction chamber 1.
[0066] S2-6, the substrate moves to the bottom of the metal source input tube A131, the metal source input tube A131 pulses the third precursor TDMASn on the substrate surface, and chemically adsorbs TDMASn on the substrate surface at the same time, the dry nitrogen input tube 11 adjacent to the metal source input tube A131 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the metal source input tube A131 extracts the nitrogen in the plate reaction chamber 1 and the remaining unreacted third precursor TDMASn from the plate reaction chamber 1.
[0067] S2-7, the substrate moves to under the oxygen source input tube B142, the oxygen source input tube B142 pulses the fourth precursor O3, the TDMASn adsorbed on the surface of the substrate reacts with the fourth precursor O3 to obtain a SnO2 thin film, the dry nitrogen input tube 11 adjacent to the oxygen source input tube B142 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the oxygen source input tube B142 extracts the nitrogen in the plate reaction chamber 1 and the remaining unreacted fourth precursor O3 from the plate reaction chamber 1.
[0068] S2-8, repeating steps S2-3 to S2-7 70 times, and then atomic layer deposition of ZnO / SnO on the substrate can be achieved. x / SnO2 multilayer composite film, see Figure 3 .
[0069] Another aspect of the present invention also protects a multilayer composite film prepared by the atomic layer deposition process of the fourth aspect, the multilayer composite film comprising ZnO layers, SnO layers repeatedly stacked on the surface of the substrate xlayer and SnO2 layer, the number of repetitions is 7-70 times, wherein the ZnO layer includes at least one layer of ZnO.
[0070] The present invention will be further described below by way of examples.
[0071] Example 1
[0072] A spatial atomic layer deposition system includes a plate-type reaction chamber 1, a nitrogen inlet pipe 11, a nitrogen exhaust pipe 12, a metal source inlet pipe group 13, and an oxygen source inlet pipe group 14; the plate-type reaction chamber 1 is connected to a plurality of nitrogen inlet pipes 11 and a plurality of nitrogen exhaust pipes 12 along its length direction; the nitrogen exhaust pipe 12 is arranged between adjacent nitrogen inlet pipes 11, and two nitrogen exhaust pipes 12 are arranged between adjacent nitrogen inlet pipes 11. The plate-type reaction chamber 1 is also cross-arranged with a metal source input pipe group 13 and an oxygen source input pipe group 14 in sequence along its length direction. The metal source input pipe group 13 and the oxygen source input pipe group 14 are both connected to the plate-type reaction chamber 1, and the metal source input pipe group 13 is arranged between adjacent nitrogen exhaust pipes 12; the oxygen source input pipe group 14 adjacent to a certain metal source input pipe group 13 is located between adjacent nitrogen exhaust pipes 12, that is, the adjacent metal source input pipe groups 13 and oxygen source input pipe groups 14 are separated by the nitrogen exhaust pipe 12, the nitrogen input pipe 11, and the nitrogen exhaust pipe 12.
[0073] The metal source input tube group 13 includes two metal source input tubes 130, namely, a metal source input tube A131 and a metal source input tube B132. The metal source input by the metal source input tube A131 is TDMASn, and the metal source input by the metal source input tube B132 is DEZ.
[0074] The oxygen source input tube group 14 includes two oxygen source input tubes 140, namely, an oxygen source input tube A141 and an oxygen source input tube B142. The oxygen source input by the oxygen source input tube A141 is H2O, and the oxygen source input by the oxygen source input tube B142 is O3.
[0075] At the same time, the single metal source input pipe A131 and the metal source input pipe B13 are respectively provided with a first solenoid valve and a first pulse valve, and the flow rate of the metal source input to the plate-type reaction chamber 1 and whether it is opened or closed are controlled by the first solenoid valve. The single oxygen source input pipe A141 and the oxygen source input pipe B142 are respectively provided with a second solenoid valve and a second pulse valve, and the flow rate of the oxygen source input to the plate-type reaction chamber 1 is controlled by the second solenoid valve, and at least one of the oxygen source input pipes can also be opened or closed.
[0076] Example 2
[0077] An atomic layer deposition process using the spatial atomic layer deposition system of embodiment 1 includes the following steps:
[0078] Step 1, set the metal source input by the metal source input tube A131 to TDMASn, and the metal source input by the metal source input tube B132 to DEZ; the oxygen source input by the oxygen source input tube A141 is H2O, keep the oxygen source input tube B142 in a closed state, place the substrate in the plate reaction chamber 1, pass through the nitrogen input tube 11 and the nitrogen exhaust pipe 12 in sequence, after cleaning the surface impurities, move the substrate directly to the bottom of the metal source input tube B132 through the closed metal source input tube A131, the metal source input tube B132 pulses the first precursor DEZ to expose the substrate surface, and chemically adsorbs DEZ on the substrate surface; then move the substrate to the nitrogen exhaust pipe 12 once, and below the nitrogen input pipe 11 and the nitrogen exhaust pipe 12, use nitrogen to clean the substrate surface while discharging the nitrogen and the unreacted first precursor DEZ in the plate reaction chamber 1.
[0079] Step 2: The substrate moves to the bottom of the oxygen source input pipe A141, and the oxygen source input pipe A141 pulses the second precursor H2O, and the DEZ adsorbed on the substrate surface reacts with H2O to obtain a ZnO film. Then, the substrate moves to the nitrogen exhaust pipe 12, the nitrogen input pipe 11, and the bottom of the nitrogen exhaust pipe 12 in sequence through the closed oxygen source input pipe B142, and the nitrogen is used to clean the substrate surface, and the unreacted second precursor and nitrogen are discharged from the plate-type reaction chamber 1 by the nitrogen exhaust pipe 12.
[0080] Step 3, repeat step 1 and step 2 18 times;
[0081] Step four, the substrate moves to the bottom of the metal source input tube A131, the metal source input tube A131 pulses the third precursor TDMASn on the substrate surface, and chemically adsorbs TDMASn on the substrate surface; then it moves to the nitrogen exhaust pipe 12, the nitrogen input pipe 11, and the bottom of the nitrogen exhaust pipe 12 in sequence through the closed metal source input tube B132, and while nitrogen is also used to clean the substrate surface, the nitrogen exhaust pipe 12 is used to discharge the unreacted third precursor and nitrogen from the plate reaction chamber 1.
[0082] Step 5: Move the substrate to the bottom of the oxygen source input tube A141, pulse the second precursor H2O through the oxygen source input tube A141, and the TDMASn adsorbed on the substrate surface reacts with H2O to obtain SnO x film; then it moves to the nitrogen exhaust pipe 12, the nitrogen input pipe 11, and the bottom of the nitrogen exhaust pipe 12 in sequence through the closed oxygen source input pipe B142, and while nitrogen is used to clean the substrate surface, the unreacted second precursor and nitrogen are discharged from the plate-type reaction chamber 1 by using the nitrogen exhaust pipe 12.
[0083] Step 6: Repeat steps 4 to 5 10 times to deposit a multilayer ZnO / SnO layer on the substrate. x Layer composite film.
[0084] Example 3
[0085] The method is the same as Example 2, except that: in step 3, steps 1 and 2 are repeated 8 times in a cycle; and in step 6, steps 4 to 5 are repeated 20 times in a cycle.
[0086] Example 4
[0087] The method is the same as Example 2, except that: in step 3, steps 1 and 2 are repeated 3 times in a cycle; and in step 6, steps 4 to 5 are repeated 40 times in a cycle.
[0088] Example 5
[0089] The difference from Example 2 is that: in step 3, step 1 and step 2 are repeated cyclically for 0 times; in step 6, step 4 to step 5 are repeated cyclically for 100 times.
[0090] Example 6
[0091] An atomic layer deposition process using the spatial atomic layer deposition system of embodiment 1 includes the following steps:
[0092] Step 1: Set the metal source input by the metal source input pipe A131 to be TDMASn, the metal source input by the metal source input pipe B132 to be DEZ; the oxygen source input by the oxygen source input pipe A141 to be H2O, the oxygen source input by the oxygen source input pipe B142 to be O3, move the substrate to the bottom of the metal source input pipe B132, the metal source input pipe B132 pulses the first precursor DEZ to expose the substrate surface, and chemically adsorbs the first precursor DEZ on the substrate surface. The dry nitrogen input pipe 11 adjacent to the metal source input pipe B132 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the metal source input pipe B132 extracts the nitrogen in the plate reaction chamber 1 and the remaining unreacted first precursor DEZ out of the plate reaction chamber 1.
[0093] Step 2: The substrate continues to move to the bottom of the oxygen source input pipe A141, and the oxygen source input pipe A141 pulses the second precursor H2O, and the second precursor DEZ adsorbed on the substrate surface reacts with H2O to obtain a ZnO film. The dry nitrogen input pipe 11 adjacent to the oxygen source input pipe A141 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the oxygen source input pipe A141 extracts the nitrogen in the plate reaction chamber 1 and the remaining unreacted second precursor H2O out of the plate reaction chamber 1.
[0094] Step 3: Repeat steps 1 to 2 10 times.
[0095] Step 4: Move the substrate to the bottom of the metal source input tube A131, and the metal source input tube A131 pulses the third precursor TDMASn on the substrate surface, and chemically adsorbs the third precursor TDMASn on the substrate surface. The dry nitrogen input tube 11 adjacent to the metal source input tube A131 inputs nitrogen into the plate-type reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the metal source input tube A131 extracts the nitrogen in the plate-type reaction chamber 1 and the remaining unreacted third precursor TDMASn from the plate-type reaction chamber 1.
[0096] Step 5: The substrate continues to move to the bottom of the oxygen source input tube A141, and the oxygen source input tube A141 pulses the second precursor H2O. The TDMASn adsorbed on the substrate surface reacts with the second precursor H2O to obtain SnO x The dry nitrogen gas input pipe 11 adjacent to the oxygen source input pipe A141 inputs nitrogen gas into the plate-type reaction chamber 1 , and the nitrogen gas exhaust pipe 12 adjacent to the oxygen source input pipe A141 extracts the nitrogen gas and the remaining unreacted second precursor H2O in the plate-type reaction chamber 1 out of the plate-type reaction chamber 1 .
[0097] Step 6: The substrate moves to the bottom of the metal source input tube A131, and the metal source input tube A131 pulses the third precursor TDMASn on the substrate surface, and chemically adsorbs TDMASn on the substrate surface. The dry nitrogen input tube 11 adjacent to the metal source input tube A131 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the metal source input tube A131 extracts the nitrogen in the plate reaction chamber 1 and the remaining unreacted third precursor TDMASn from the plate reaction chamber 1.
[0098] Step 7: The substrate is moved to the bottom of the oxygen source input pipe B142, and the oxygen source input pipe B142 pulses the fourth precursor O3, and the TDMASn adsorbed on the surface of the substrate reacts with the fourth precursor O3 to obtain a SnO2 film. The dry nitrogen input pipe 11 adjacent to the oxygen source input pipe B142 inputs nitrogen into the plate-type reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the oxygen source input pipe B142 extracts the nitrogen in the plate-type reaction chamber 1 and the remaining unreacted fourth precursor O3 from the plate-type reaction chamber 1.
[0099] Step 8: Repeat steps 3 to 7 20 times to deposit an atomic layer containing ZnO / SnO on the substrate. x / SnO2 multilayer composite film.
[0100] Example 7
[0101] The same as Example 6, the only difference is that in step 3, Xuanhuan repeats steps 1 and 2 0 times, and in step 8, steps 3 to 7 are cyclically repeated 7 times.
[0102] Comparative Example 1
[0103] Comparative Example 1 is a comparative test for film preparation, and an atomic layer deposition process is performed using the spatial atomic layer deposition system prepared in Example 1, including the following steps:
[0104] Step 1: Set the metal source input pipe A131 to be in a closed state, and the metal source input by the metal source input pipe B132 is DEZ; the oxygen source input by the oxygen source input pipe A141 is H2O, and the oxygen source input pipe B142 is also kept in a closed state. The substrate moves to the bottom of the metal source input pipe B132, and the metal source input pipe B132 pulses the first precursor DEZ to expose the substrate surface, and chemically adsorbs DEZ on the substrate surface. The dry nitrogen input pipe 11 adjacent to the metal source input pipe B132 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the metal source input pipe B132 extracts the nitrogen in the plate reaction chamber 1 and the remaining unreacted first precursor DEZ out of the plate reaction chamber 1.
[0105] Step 2, the substrate is moved to the bottom of the oxygen source input tube A141, and the oxygen source input tube A141 pulses the second precursor H2O. The DEZ adsorbed on the surface of the substrate reacts chemically with H2O to obtain a ZnO film. The dry nitrogen input tube 11 adjacent to the oxygen source input tube A141 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the oxygen source input tube A141 extracts the nitrogen in the plate reaction chamber 1 and the remaining unreacted second precursor H2O from the plate reaction chamber 1.
[0106] Step 6: Repeat steps 1 to 5 200 times to atomically deposit a ZnO film on the substrate.
[0107] Test example:
[0108] The composite film prepared by the method of Examples 2-5 of the present invention is used to prepare a perovskite photovoltaic device (the structure of the perovskite photovoltaic device is: ITO / PTAA / Al2O3 / perovskite / PEAI / C 60 / ZnO / composite film / Ag), and at the same time, a perovskite photovoltaic device with the same structure was prepared using the ZnO thin film in Comparative Example 1, and the performance parameters of the perovskite photovoltaic devices obtained in the embodiment and the comparative example were tested. The results are shown in Table 1.
[0109] Table 1: Performance test of perovskite photovoltaic devices prepared by thin films of Examples 2-5 and Comparative Example 1
[0110]
[0111] As shown in Table 1, ZnO / SnO x The photovoltaic parameters of the perovskite photovoltaic device prepared by the composite film have been significantly improved. With the increase of the doping ratio, the PCE of the device also gradually increases. When the metal source pulse ratio is 9:1, the photovoltaic parameters of the device are optimal: the PCE can reach up to 20.2%, and the JSC and VOC can exceed 20mA / cm 2 The most obvious change is FF, which has been significantly improved compared to ZnO and can reach nearly 80%.
[0112] The above is only a preferred embodiment of the present invention, and the present invention is not limited to the above embodiments. It is understood that other improvements and changes directly derived or associated by those skilled in the art without departing from the spirit and concept of the present invention should be considered to be included in the protection scope of the present invention.
Claims
1. A spatial atomic layer deposition system, characterized in that: It comprises a plate-type reaction chamber (1), a nitrogen inlet pipe (11), a nitrogen exhaust pipe (12), a metal source inlet pipe group (13), and an oxygen source inlet pipe group (14); The plate-type reaction chamber (1) is connected to a plurality of nitrogen inlet pipes (11) and a plurality of nitrogen exhaust pipes (12) along its length direction; The nitrogen exhaust pipe (12) is arranged between adjacent nitrogen input pipes (11), and at least two nitrogen exhaust pipes (12) are arranged between the nitrogen input pipes (11); The plate-type reaction chamber (1) is further provided with the metal source input pipe group (13) and the oxygen source input pipe group (14) arranged in sequence and cross-wise along its length direction; the metal source input pipe group (13) and the oxygen source input pipe group (14) are both connected to the plate-type reaction chamber (1), and the metal source input pipe group (13) is arranged between adjacent nitrogen exhaust pipes (12); and the oxygen source input pipe group (14) adjacent to a certain metal source input pipe group (13) is located between adjacent nitrogen exhaust pipes (12).
2. The spatial atomic layer deposition system according to claim 1, characterized in that: The metal source input tube group (13) comprises a plurality of metal source input tubes (130) arranged at intervals from each other; and the oxygen source input tube group (14) comprises a plurality of oxygen source input tubes (140) arranged at intervals from each other.
3. The spatial atomic layer deposition system according to claim 2, characterized in that: The metal source input pipe group (13) comprises at least two metal source input pipes (130), wherein the metal source input pipes (130) are arranged in the length direction of the plate-type reaction chamber (1) and are in communication with the plate-type reaction chamber (1); The oxygen source input pipe group (14) comprises at least two oxygen source input pipes (140), and the oxygen source input pipes (140) are arranged in the length direction of the plate-type reaction chamber (1) and are connected to the plate-type reaction chamber (1).
4. The spatial atomic layer deposition system according to claim 1, characterized in that: The metal source input pipe group (13) comprises a metal source input pipe A (131) and a metal source input pipe B (132), wherein the metal source input pipe A (131) and the metal source input pipe B (132) input the same or different metal sources; The oxygen source input pipe group (14) comprises an oxygen source input pipe A (141) and an oxygen source input pipe B (142), wherein the oxygen source input pipe A (141) and the oxygen source input pipe B (142) input the same or different oxygen sources.
5. The spatial atomic layer deposition system according to claim 4, characterized in that: The metal source input by the metal source input pipe A (131) is TDMASn, and the metal source input by the metal source input pipe B (132) is DEZ; the oxygen source input by the oxygen source input pipe A (141) is H2O, and the oxygen source input by the oxygen source input pipe B (142) is O3.
6. The spatial atomic layer deposition system according to claim 3, characterized in that: A single metal source input pipe (130) is provided with a first solenoid valve and a first pulse valve, and the flow rate of the metal source input into the plate-type reaction chamber (1) is controlled by the first solenoid valve; a single oxygen source input pipe (140) is provided with a second solenoid valve and a second pulse valve, and the flow rate of the oxygen source input into the plate-type reaction chamber (1) is controlled by the second solenoid valve.
7. An atomic layer deposition process using the spatial atomic layer deposition system according to any one of claims 1 to 6, characterized in that: The atomic layer deposition process comprises the following steps: S1-1, set the metal source input by the metal source input pipe A (131) to TDMASn, the metal source input by the metal source input pipe B (132) to DEZ; the oxygen source input by the oxygen source input pipe A (141) to H2O, and close the solenoid valve of the oxygen source input pipe B (142); The substrate is moved to below the metal source input tube B (132), the metal source input tube B (132) pulses the first precursor DEZ to expose the substrate surface, and DEZ is chemically adsorbed on the substrate surface, the nitrogen input tube (11) adjacent to the metal source input tube B (132) inputs nitrogen into the plate-type reaction chamber (1), and the nitrogen exhaust tube (12) adjacent to the metal source input tube B (132) extracts the nitrogen in the plate-type reaction chamber (1) and the remaining unreacted first precursor DEZ out of the plate-type reaction chamber (1); S1-2, the substrate continues to move to the bottom of the oxygen source input tube A (141), the oxygen source input tube A (141) pulses the second precursor H2O, the DEZ adsorbed on the surface of the substrate reacts chemically with the H2O to obtain a ZnO film, the nitrogen input tube (11) adjacent to the oxygen source input tube A (141) inputs nitrogen into the plate-type reaction chamber (1), and the nitrogen exhaust tube (12) adjacent to the oxygen source input tube A (141) extracts the nitrogen in the plate-type reaction chamber (1) and the remaining unreacted second precursor H2O from the plate-type reaction chamber (1); S1-3, repeat steps S1-1 to S1-2 0-18 times in a loop; S1-4, moving the substrate to below the metal source input tube A (131), the metal source input tube A (131) pulses the third precursor TDMASn onto the substrate surface, and chemically adsorbs TDMASn on the substrate surface, the nitrogen input tube (11) adjacent to the metal source input tube A (131) inputs nitrogen into the plate-type reaction chamber (1), and the nitrogen exhaust tube (12) adjacent to the metal source input tube A (131) extracts the nitrogen and the remaining unreacted third precursor TDMASn in the plate-type reaction chamber (1) out of the plate-type reaction chamber (1); S1-5, the substrate is moved to the bottom of the oxygen source input tube A (141), and the oxygen source input tube A (141) pulses the second precursor H2O, and the TDMASn adsorbed on the surface of the substrate reacts chemically with H2O to obtain SnO x The nitrogen input pipe (11) adjacent to the oxygen source input pipe A (141) inputs nitrogen into the plate-type reaction chamber (1), and the nitrogen exhaust pipe (12) adjacent to the oxygen source input pipe A (141) extracts the nitrogen and the remaining unreacted second precursor H2O in the plate-type reaction chamber (1) out of the plate-type reaction chamber (1); S1-6, repeating steps S1-4 to S1-5 10-100 times, and then atomic layer deposition can be performed on the substrate to obtain a multilayer ZnO / SnO x Composite film of membrane layer.
8. A composite film prepared by the atomic layer deposition process according to claim 7, characterized in that: The composite film comprises a multilayer ZnO / SnO x film layer, and the ZnO / SnO x The film layer includes at least one ZnO layer.
9. An atomic layer deposition process using the spatial atomic layer deposition system according to any one of claims 1 to 6, characterized in that: The atomic layer deposition process comprises the following steps: S2-1, set the metal source input by the metal source input pipe A (131) to TDMASn, the metal source input by the metal source input pipe B (132) to DEZ; the oxygen source input by the oxygen source input pipe A (141) to H2O, the oxygen source input by the oxygen source input pipe B (142) to O3, The substrate is moved to below the metal source input tube B (132), the metal source input tube B (132) pulses the first precursor DEZ to expose the substrate surface, and the first precursor DEZ is chemically adsorbed on the substrate surface, the nitrogen input tube (11) adjacent to the metal source input tube B (132) inputs nitrogen into the plate-type reaction chamber (1), and the nitrogen exhaust tube (12) adjacent to the metal source input tube B (132) extracts the nitrogen and the remaining unreacted first precursor DEZ in the plate-type reaction chamber (1) out of the plate-type reaction chamber (1); S2-2, the substrate continues to move to below the oxygen source input tube A (141), the oxygen source input tube A (141) pulses the second precursor H2O, the second precursor DEZ adsorbed on the substrate surface reacts with H2O to obtain a ZnO film, the nitrogen input tube (11) adjacent to the oxygen source input tube A (141) inputs nitrogen into the plate-type reaction chamber (1), and the nitrogen exhaust tube (12) adjacent to the oxygen source input tube A (141) extracts the nitrogen in the plate-type reaction chamber (1) and the remaining unreacted second precursor H2O from the plate-type reaction chamber (1); S2-3, repeat S2-1 to S2-2 operations 0-18 times; S2-4, moving the substrate to below the metal source input tube A (131), the metal source input tube A (131) pulses the third precursor TDMASn onto the substrate surface, and chemically adsorbs the third precursor TDMASn on the substrate surface, the nitrogen input tube (11) adjacent to the metal source input tube A (131) inputs nitrogen into the plate-type reaction chamber (1), and the nitrogen exhaust tube (12) adjacent to the metal source input tube A (131) extracts the nitrogen and the remaining unreacted third precursor TDMASn in the plate-type reaction chamber (1) from the plate-type reaction chamber (1); S2-5, the substrate continues to move to the bottom of the oxygen source input tube A (141), the oxygen source input tube A (141) pulses the second precursor H2O, and the TDMASn adsorbed on the surface of the substrate reacts with the second precursor H2O to obtain SnO x The nitrogen input pipe (11) adjacent to the oxygen source input pipe A (141) inputs nitrogen into the plate-type reaction chamber (1), and the nitrogen exhaust pipe (12) adjacent to the oxygen source input pipe A (141) extracts the nitrogen and the remaining unreacted second precursor H2O in the plate-type reaction chamber (1) out of the plate-type reaction chamber (1); S2-6, the substrate moves to the bottom of the metal source input tube A (131), the metal source input tube A (131) pulses the third precursor TDMASn onto the substrate surface, and chemically adsorbs TDMASn on the substrate surface, the nitrogen input tube (11) adjacent to the metal source input tube A (131) inputs nitrogen into the plate-type reaction chamber (1), and the nitrogen exhaust tube (12) adjacent to the metal source input tube A (131) extracts the nitrogen and the remaining unreacted third precursor TDMASn in the plate-type reaction chamber (1) out of the plate-type reaction chamber (1); S2-7, the substrate moves to the position below the oxygen source input tube B (142), the oxygen source input tube B (142) pulses the fourth precursor O3, TDMASn adsorbed on the surface of the substrate reacts with the fourth precursor O3 to obtain a SnO2 thin film, the nitrogen input tube (11) adjacent to the oxygen source input tube B (142) inputs nitrogen into the plate-type reaction chamber (1), and the nitrogen exhaust tube (12) adjacent to the oxygen source input tube B (142) extracts the nitrogen in the plate-type reaction chamber (1) and the remaining unreacted fourth precursor O3 from the plate-type reaction chamber (1); S2-8, repeating steps S2-3 to S2-7 70 times, and then atomic layer deposition of ZnO / SnO on the substrate can be achieved. x / SnO2 multilayer composite film.
10. A multilayer composite film prepared by the atomic layer deposition process according to claim 9, characterized in that: The multilayer composite film comprises ZnO layers, SnO x layer and SnO2 layer, the number of repetitions is 7-70 times, wherein the ZnO layer includes at least one layer of ZnO.