Plate-type atomic deposition apparatus and atomic deposition process using same

Abstract

The invention relates to the technical field of solar cell modules, in particular to plate-type atomic deposition equipment and an atomic deposition process using the atomic deposition equipment. The plate-type atomic deposition equipment comprises a plate-type reaction chamber, wherein an inert gas isolation assembly, a metal source input pipe group and an oxygen source input pipe group are arranged on the plate-type reaction chamber; each of the metal source input pipe group and the oxygen source input pipe group comprises an input main pipe and an input branch pipe communicated with the input main pipe, the metal source input pipe group and the oxygen source input pipe group are arranged between the adjacent inert gas isolation assemblies, and the metal source input pipe group and the oxygen source input pipe group are not arranged between the adjacent inert gas isolation assemblies at the same time. According to the plate-type atomic deposition equipment containing the metal source input tube group and the oxygen source input tube group, mixed input and reaction of a metal source and an oxygen source can be achieved, preparation of a multi-component composite film is achieved, meanwhile, the deposition efficiency of an atomic layer and a deposited atomic layer film structure are improved, and the conductivity and the photoelectric conversion efficiency of a solar cell module are improved.

Description

Technical Field

[0001] The invention belongs to the technical field of solar cell components, and in particular relates to a plate-type atomic deposition device and an atomic deposition process using the atomic deposition device. Background Art

[0002] Plate-type atomic layer deposition technology, also known as spatial atomic layer deposition technology, is a technology that can deposit various thin film materials from the gas phase, making atomic layer deposition technology show great prospects in emerging semiconductor and energy conversion technologies. Based on continuous self-limiting reactions, plate-type atomic layer deposition technology ALD provides excellent conformality on high aspect ratio structures, angstrom-level thickness control and adjustable film composition, and 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] See also Figure 4 The existing plate-type atomic deposition equipment includes a plate-type reaction chamber 1, on which a plurality of mutually spaced inert gas isolation components 10 are arranged; the plate-type reaction chamber 1 is also provided with a plurality of metal source input pipes 2 for inputting metal source gas, and the metal source input pipes 2 are located between adjacent inert gas isolation components 10; the plate-type reaction chamber 1 is also provided with a plurality of oxygen source input pipes 3 for inputting oxygen source gas, and the oxygen source input pipes 3 are located between adjacent inert gas isolation components and the oxygen source input pipes 3 are located between adjacent metal source input pipes 2. The above-mentioned plate-type atomic deposition equipment performs spatially isolated atomic layer deposition, and is usually used in production lines that need to control the production rhythm to improve production efficiency. The limitation is that there is only a single reaction source channel. Therefore, the thin film layer prepared by the existing plate-type atomic deposition equipment is single, and the controllability of the film components 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 plate-type atomic deposition device and an atomic deposition process using the atomic deposition device. The present invention improves the input pipelines of the metal source and the oxygen source. The metal source is input through the branch pipe and mixed in the main pipe, and then enters the plate-type reaction chamber. Each branch pipe inputs the same or different metal sources. Similarly, the oxygen source also uses the main pipe and the branch pipe to achieve the mixed input of the same or different oxygen sources. The mixed metal source and the mixed oxygen source are deposited in sequence, and the preparation of the mixed film layer is achieved without removing the substrate. The deficiencies of the film layer prepared by a single reaction source of the existing equipment are overcome, and the control of the film layer is further improved by setting solenoid valves on the branch pipe and the main pipe, which provides the possibility of preparing more film layers with different properties.

[0006] The technical solution of the present invention is as follows:

[0007] The first aspect of the present invention protects a plate-type atomic deposition device, comprising a reaction chamber 1, wherein the plate-type reaction chamber 1 is provided with a plurality of mutually spaced inert gas isolation assemblies 10 along its length direction; the inert gas isolation assembly 10 comprises a nitrogen inlet pipe 11 and a nitrogen exhaust pipe 12 connected to the plate-type reaction chamber 1, and is characterized in that the plate-type atomic deposition device also comprises a plurality of metal source inlet pipe groups 4 and a plurality of oxygen source inlet pipe groups 5; a single metal source inlet pipe group 4 and a single oxygen source inlet pipe group 5 are alternately distributed in sequence along the length direction of the plate-type reaction chamber 1, and are connected to the plate-type reaction chamber; the single metal source inlet pipe group 4 is arranged between adjacent inert gas isolation assemblies 10, the single oxygen source inlet pipe group 5 is arranged between adjacent inert gas isolation assemblies 10, and each The metal source input pipe group 4 and the oxygen source input pipe group 5 are not simultaneously arranged between adjacent inert gas isolation assemblies 10; a single metal source input pipe group 4 comprises a metal source input main pipe 41 and a plurality of metal source input branch pipes 42 connected to the metal source input main pipe 41; one end of the metal source input main pipe 41 is connected to the plate-type reaction chamber 1, and the other end is connected to the metal source input branch pipe 42; each of the metal source input branch pipes 42 inputs the same or different metal sources; a single oxygen source input pipe group 5 comprises an oxygen source input main pipe 51 and a plurality of oxygen source input branch pipes 52 connected to the oxygen source input main pipe 51; one end of the oxygen source input main pipe 51 is connected to the plate-type reaction chamber 1, and the other end is connected to the oxygen source input branch pipe 52; each of the oxygen source input branch pipes 52 inputs the same or different oxygen sources.

[0008] Preferably, the metal source input branch pipe 42 includes two input branch pipes, each of which inputs the same or different metal sources.

[0009] Preferably, the oxygen source input branch pipe 52 has two input branch pipes, which respectively input the same or different metal sources.

[0010] Preferably, the number of the metal source input branch pipes 42 is two, and one of the metal source input branch pipes 42 inputs TDMASn, and the other metal source input branch pipe 42 inputs DEZ.

[0011] Preferably, the number of the oxygen source input branch pipes 52 is two, one of which is an oxygen source input branch pipe 52 for inputting H 2 O, another oxygen source input branch pipe 42 inputs O 3 .

[0012] Preferably, the metal source input main pipe 41 is provided with a first solenoid valve 411 ; and the single metal source input branch pipe 42 is provided with a first pulse valve 421 and a second solenoid valve 422 in sequence along the metal source flow direction.

[0013] Preferably, the oxygen source input main pipe 51 is provided with a third solenoid valve 511 ; the single oxygen source input branch pipe 52 is provided with a second pulse valve 521 and a fourth solenoid valve 522 in sequence along the flow direction of the metal source.

[0014] The second aspect of the present invention protects a method for an atomic layer deposition process using the plate-type atomic deposition device described in the first aspect, the method comprising the following steps:

[0015] S1: Set the metal source input by one metal source input branch pipe 42 in the metal source input pipe group 4 to be TDMASn, the metal source input by another metal source input branch pipe 42 in the metal source input pipe group 4 to be DEZ; set the oxygen source input by one oxygen source input branch pipe 52 in the oxygen source input pipe group 5 to be H 2 O, the oxygen source input by another oxygen source input branch pipe 52 in the oxygen source input pipe group 5 is O 3 The substrate is moved along the length direction of the plate-type reaction chamber 1 to the metal source input tube group 4, and the metal source input tube group 4 pulses a first precursor to expose the substrate surface, wherein the first precursor is TDMASn and / or DEZ gas, and the first precursor is chemically adsorbed on the substrate surface at the same time, and a dry nitrogen input tube 11 adjacent to the metal source input tube group 4 inputs nitrogen into the plate-type reaction chamber 1, and a nitrogen exhaust pipe 12 adjacent to the metal source input tube group 4 extracts the inert gas in the plate-type reaction chamber 1 and the remaining unreacted first precursor from the plate-type reaction chamber 1.

[0016] S2: The substrate moves along the length direction of the plate-type reaction chamber 1 to below the oxygen source input tube group 5, and the oxygen source input tube group 5 pulses the second precursor, which is H 2 O and / or O 3The first precursor adsorbed on the surface of the substrate reacts chemically with the second precursor to obtain a composite film, the dry nitrogen input pipe 11 adjacent to the oxygen source input pipe group 5 inputs nitrogen into the plate reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the oxygen source input pipe group 5 draws the nitrogen in the plate reaction chamber 1 and the remaining unreacted second precursor out of the plate reaction chamber 1.

[0017] S3: Repeat the S1-S2 operation 0-180 times in a cycle to atomically deposit a multi-layer composite film on the substrate.

[0018] Preferably, in step S1, when the first precursor is TDMASn and DEZ, the volume ratio of TDMASn to DEZ is 1:(1-19).

[0019] Preferably, in step S2, the second precursor is H 2 O and O 3 When the H 2 O and O 3 The volume ratio is 1:(0.5-4).

[0020] The third aspect of the present invention protects a composite metal film prepared by the method described in the second aspect.

[0021] The beneficial technical effects of the present invention are:

[0022] (1) The plate-type atomic deposition equipment described in the present invention is provided with pipelines for inputting a variety of metal sources and a variety of oxygen sources. At the same time, the metal source input pipe group and the oxygen source input pipe group are provided with main pipes and branch pipes, thereby realizing the direct preparation of the composite film layer, improving the deposition efficiency of the atomic layer and the structure of the deposited atomic layer film, and regulating the film properties to improve the conductivity and photoelectric conversion efficiency of the solar cell module.

[0023] (2) By further setting control valves on the main and branch pipes for metal source and oxygen source input, the control over the components of the prepared membrane layer and the performance of the prepared membrane layer is optimized, which provides the possibility for preparing more membrane layers with different properties.

[0024] (3) The atomic layer deposition process performed by the present invention using a plate-type atomic deposition device is relatively simple and easy to implement in industrial production.

[0025] (4) The present invention uses a plate-type atomic deposition device to perform an atomic layer deposition process to achieve ZnO / SnO x The prepared composite film has better conductivity, and the photoelectric performance of the solar device prepared by using the composite film is better. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1Schematic diagram of the structure of a plate-type atomic deposition device in an embodiment of the present invention.

[0027] Figure 2 for Figure 1 A partial enlarged view of point A in the middle.

[0028] Figure 3 for Figure 1 A partial enlarged view of point B in the middle.

[0029] Figure 4 It is a schematic diagram of the structure of a plate-type atomic deposition device in the prior art.

[0030] Figure 5 Schematic diagram of the structure of the composite film prepared by using a plate-type atomic deposition device in an embodiment of the present invention.

[0031] In the figure, 1, plate reaction chamber; 10, inert gas isolation assembly; 11, nitrogen input pipe; 12, nitrogen exhaust pipe; 2, metal source input pipe; 3, oxygen source input pipe; 4, metal source input pipe group; 41, metal source input main pipe; 411, first solenoid valve; 42, metal source input branch pipe; 421, first pulse valve; 422, second solenoid valve; 5, oxygen source input pipe group; 51, oxygen source input main pipe; 511, third solenoid valve; 52, oxygen source input branch pipe; 521, second pulse valve; 522, fourth solenoid valve. DETAILED DESCRIPTION

[0032] The present invention is described in detail below in conjunction with the accompanying drawings and embodiments.

[0033] The first aspect of the present invention provides a plate-type atomic deposition device, such as Figure 1 As shown, it includes a reaction chamber 1, and the plate-type reaction chamber 1 is provided with a plurality of mutually spaced inert gas isolation assemblies 10 along its length direction; the inert gas isolation assembly 10 includes a nitrogen inlet pipe 11 and a nitrogen exhaust pipe 12 connected to the plate-type reaction chamber 1, and the inert gas isolation assembly 10 includes at least one nitrogen inlet pipe 11 and at least one nitrogen exhaust pipe 12, the nitrogen inlet pipe 11 is used to input nitrogen, and the nitrogen exhaust pipe 12 is used to exhaust.

[0034] In some embodiments of the present invention, Figure 1 As shown, the plate-type atomic deposition equipment also includes a plurality of metal source input tube groups 4 and a plurality of oxygen source input tube groups 5; a single metal source input tube group 4 and a single oxygen source input tube group 5 are alternately distributed in sequence along the length direction of the plate-type reaction chamber 1, and are connected to the plate-type reaction chamber; a single metal source input tube group 4 is arranged between adjacent inert gas isolation assemblies 10, a single oxygen source input tube group 5 is arranged between adjacent inert gas isolation assemblies 10, and a metal source input tube group 4 and an oxygen source input tube group 5 are not arranged simultaneously between each adjacent inert gas isolation assemblies 10.

[0035] In some embodiments, Figure 1 As shown, the reaction chamber 1 is sequentially provided with a nitrogen input pipe 11, a nitrogen exhaust pipe 12, a metal source input pipe group 4, a nitrogen exhaust pipe 12, a nitrogen input pipe 11, a nitrogen exhaust pipe 12, an oxygen source input pipe group 5, a nitrogen exhaust pipe 12, a nitrogen input pipe 11, a nitrogen exhaust pipe 12, a metal source input pipe group 4, a nitrogen exhaust pipe 12, a nitrogen input pipe 11, a nitrogen exhaust pipe 12, an oxygen source input pipe group 5, a nitrogen exhaust pipe 12, and a nitrogen input pipe 11 along its length direction. It can be understood that the scheme of the present invention is not limited to the above structure, and multiple groups of metal source group 4-inert gas isolation assembly 10-oxygen source input pipe group 5-inert gas isolation assembly 10 can be repeatedly provided on this basis.

[0036] In some embodiments, Figure 1 , Figure 2 As shown, a single metal source input pipe group 4 includes a metal source input main pipe 41 and a plurality of metal source input branch pipes 42 connected to the metal source input main pipe 41; one end of the metal source input main pipe 41 is connected to the plate-type reaction chamber 1, and the other end is connected to the metal source input branch pipe 42; each metal source input branch pipe 42 inputs the same or different metal sources.

[0037] In some embodiments, Figure 1 , Figure 3 As shown, a single oxygen source input pipe group 5 includes an oxygen source input main pipe 51 and a plurality of oxygen source input branch pipes 52 connected to the oxygen source input main pipe 51. One end of the oxygen source input main pipe 51 is connected to the plate-type reaction chamber 1 and the other end is connected to the oxygen source input branch pipe 52. Each oxygen source input branch pipe 52 inputs the same or different oxygen sources.

[0038] In some embodiments, Figure 2 As shown, there are two metal source input branch pipes 42, which respectively input the same or different metal sources.

[0039] In some embodiments, Figure 3 As shown, there are two oxygen source input branch pipes 52, which respectively input the same or different metal sources.

[0040] It can be understood that the present invention provides a new direction for composite film preparation by setting a main pipe and a branch pipe in both the metal source input pipe combination and the oxygen source input pipe group. Compared with setting a main pipe and a branch pipe for a single metal source, when different metal sources or oxygen sources are set in the main pipe and the branch pipe, the preparation of a composite film layer containing multiple components can be achieved at one time. Compared with a single film layer or an alternatingly distributed film layer, a composite film layer can realize a composite film structure corresponding to the actual production design of the customer, which is convenient for independent design and development of a composite film structure, and provides a new direction for the development of scientific research instruments.

[0041] In some embodiments, Figure 1 , Figure 2 As shown, there are two metal source input branch pipes 42 , and one of the metal source input branch pipes 42 inputs TDMASn, namely metal source gas 1 , and the other metal source input branch pipe 42 inputs DEZ, namely metal source gas 2 .

[0042] In some embodiments, Figure 1 , Figure 3 As shown, there are two oxygen source input branches 52, one of which is an oxygen source input branch 52 for inputting H 2 O, that is, oxygen source gas 1, and another oxygen source input branch pipe 42 inputs O 3 , that is, oxygen source gas 2.

[0043] In some embodiments, Figure 1 , Figure 2 As shown, a first electromagnetic valve 411 is disposed on the metal source input main pipe 41 ; a first pulse valve 421 and a second electromagnetic valve 422 are sequentially disposed on a single metal source input branch pipe 42 along the metal source flow direction.

[0044] In some embodiments, Figure 1 , Figure 3 As shown, the oxygen source input main pipe 51 is provided with a third solenoid valve 511 ; the single oxygen source input branch pipe 52 is provided with a second pulse valve 521 and a fourth solenoid valve 522 in sequence along the flow direction of the metal source.

[0045] It can be understood that the present invention further sets solenoid valves on the metal input main pipe and the oxygen source input main pipe, and sets pulse valves and solenoid valves on the metal input branch pipe and the oxygen source input branch pipe, so as to realize the control of the input gas source. For example, one input source can be controlled not to be input, and only one input source can be input. At this time, due to the single-side branch input, the gas flow enters the plate-type reaction chamber through the mixing tube, and the stability of the gas flow is poor. Therefore, the present invention preferably inputs gas sources into both the oxygen source input branch pipe and the metal source input branch pipe. For example, the metal source input branch pipe includes two, and both branches input the same or different metal sources.

[0046] It is understood that in the present invention, the atomic deposition device also includes other conventional components, including but not limited to a substrate moving system, a nitrogen storage container, an exhaust gas collection container, a metal source input container, an oxygen source input container, etc., and the present invention does not limit the configuration thereof. Any configuration that can achieve the purpose of the present invention is within the protection scope of the present invention.

[0047] In some embodiments of the present invention, one end of the nitrogen input pipe is connected to the plate-type reaction chamber 1, and the other end is connected to the nitrogen storage container for storing the required nitrogen. One end of the nitrogen exhaust pipe is connected to the plate-type reaction chamber 1, and the other end is connected to the exhaust collection container for collecting and processing the exhausted gas.

[0048] In some embodiments of the present invention, one end of the oxygen source input branch pipe and the metal source input branch pipe are respectively connected to the plate reaction chamber 1, and the other end is respectively connected to the oxygen source storage container and the metal source storage container, respectively providing oxygen source and metal source for the oxygen source inlet and outlet branch pipe and the metal source input branch pipe.

[0049] In some embodiments of the present invention, the movement of the substrate can be achieved by existing methods, including but not limited to motor control. The atomic deposition equipment also includes a detection control system that can detect the moving position of the substrate, and then control the input and output of nitrogen, oxygen source, metal gas source, etc. according to the moving position. The present invention does not limit the detection control system, and any detection system that can achieve the purpose of the present invention is within the scope of protection of this application, such as any existing device that can achieve movement and detection.

[0050] The second aspect of the present invention protects a method for an atomic layer deposition process using the plate-type atomic deposition device of the first aspect, the method comprising the following steps:

[0051] S1: Set the metal source input by one metal source input branch pipe 42 in the metal source input pipe group 4 to be TDMASn, the metal source input by another metal source input branch pipe 42 in the metal source input pipe group 4 to be DEZ; set the oxygen source input by one oxygen source input branch pipe 52 in the oxygen source input pipe group 5 to be H 2 O, the oxygen source input by another oxygen source input branch pipe 52 in the oxygen source input pipe group 5 is O 3 ;

[0052] The substrate is moved along the length direction of the plate-type reaction chamber 1 to the metal source input tube group 4, the metal source input tube group 4 pulses a first precursor to expose the substrate surface, the first precursor is TDMASn and / or DEZ gas, and the first precursor is chemically adsorbed on the substrate surface at the same time, a dry nitrogen input tube 11 adjacent to the metal source input tube group 4 inputs nitrogen into the plate-type reaction chamber 1, and a nitrogen exhaust pipe 12 adjacent to the metal source input tube group 4 extracts the inert gas in the plate-type reaction chamber 1 and the remaining unreacted first precursor from the plate-type reaction chamber 1;

[0053] S2: The substrate moves along the length direction of the plate-type reaction chamber 1 to the bottom of the oxygen source input tube group 5, and the oxygen source input tube group 5 pulses the second precursor, which is H 2 O and / or O 3, the first precursor adsorbed on the surface of the substrate reacts chemically with the second precursor to obtain a composite film, the dry nitrogen inlet pipe 11 adjacent to the oxygen source inlet pipe group 5 inputs nitrogen into the plate-type reaction chamber 1, and the nitrogen exhaust pipe 12 adjacent to the oxygen source inlet pipe group 5 extracts the nitrogen in the plate-type reaction chamber 1 and the remaining unreacted second precursor from the plate-type reaction chamber 1;

[0054] S3: Repeat the S1-S2 operation 0-180 times in a cycle to atomically deposit a multi-layer composite film on the substrate.

[0055] In some embodiments, in step S1, when the first precursor is TDMASn and DEZ, the volume ratio of TDMASn to DEZ is 1:1-19, including but not limited to 1:1, 1:2, 1:4, 1:6, 1:8, 1:10, 1:12, 1:14, 1:15, 1:17, 1:19, preferably, the volume ratio of TDMASn to DEZ is 1:19;

[0056] In some embodiments, in step S2, the second precursor is H 2 O and O 3 When H 2 O and O 3 The volume ratio of H is 1:0.5-4, including but not limited to 1:0.5, 1:0.8, 1:1, 1:2, 1:3, 1:4. Preferably, H 2 O and O 3 The volume ratio is 1:1.

[0057] The third aspect of the present invention provides a composite metal film prepared by the method of the second aspect.

[0058] It is understood that in the present invention, the composite metal film includes but is not limited to ZnO / SnO X / SnO 2 Thin film, ZnO / SnO X Thin film, ZnO / SnO 2 film.

[0059] The present invention will be further described below by way of examples.

[0060] Example 1

[0061] A plate-type atomic deposition device includes a plate-type reaction chamber 1, and the plate-type reaction chamber 1 is provided with a plurality of mutually spaced inert gas isolation components 10 along its length direction. The inert gas isolation components 10 include a nitrogen inlet pipe 11 and a nitrogen exhaust pipe 12 connected to the plate-type reaction chamber 1. The nitrogen exhaust pipe 12 is located between adjacent nitrogen inlet pipes 11, and two nitrogen exhaust pipes 12 are located between adjacent nitrogen inlet pipes 11.

[0062] refer to Figure 1 The plate-type reaction chamber 1 is connected with a plurality of metal source input pipe groups 4 along its length direction, and the metal source input pipe group 4 is located between adjacent inert gas isolation components 10. The plate-type reaction chamber 1 is connected with a plurality of oxygen source input pipe groups 5 along its length direction, and the oxygen source input pipe group 5 is located between adjacent inert gas isolation components 10, and the oxygen source input pipe group 5 is located between adjacent metal source input pipe groups 4, that is, the plate-type reaction chamber 1 is sequentially cross-arranged with metal source input pipe groups 4 and oxygen source input pipe groups 5 located between the inert gas isolation components 10 along its length direction.

[0063] refer to Figure 1-2 A single metal source input pipe group 4 includes a metal source input main pipe 41 and two metal source input branch pipes 42 connected to the metal source input main pipe 41. One end of the metal source input main pipe 41 is connected to the plate-type reaction chamber 1 and the other end is connected to the metal source input branch pipe 42. Of the two metal source input branch pipes, one inputs TDMASn or DEZ, and the other inputs TDMASn or DEZ.

[0064] refer to Figure 1 , Figure 3 The single oxygen source input pipe group 5 includes an oxygen source input main pipe 51 and two oxygen source input branch pipes 52 connected to the oxygen source input main pipe 51. One end of the oxygen source input main pipe 51 is connected to the plate-type reaction chamber 1 and the other end is connected to the oxygen source input branch pipe 52. One of the two oxygen source input branch pipes 52 inputs H 2 O or O 3 , another oxygen source input branch pipe inputs H 2 O or O 3 .

[0065] refer to Figure 1-2 A first electromagnetic valve 411 is disposed on the metal source input main pipe 41 ; a first pulse valve 421 and a second electromagnetic valve 422 are sequentially disposed on the single metal source input branch pipe 42 along the metal source flow direction.

[0066] refer to Figure 1 , Figure 3 A third solenoid valve 511 is disposed on the oxygen source input main pipe 51; a second pulse valve 521 and a fourth solenoid valve 522 are sequentially disposed on the single oxygen source input branch pipe 52 along the flow direction of the metal source.

[0067] Example 2

[0068] The atomic layer deposition process performed using the plate-type atomic deposition equipment of Example 1 includes the following steps:

[0069] Step 1: Set the metal source input by one metal source input branch pipe 42 in the metal source input pipe group 4 to TDMASn, the metal source input by another metal source input branch pipe 42 in the metal source input pipe group 4 to DEZ; set the oxygen source input by one oxygen source input branch pipe 52 in the oxygen source input pipe group 5 to H 2 O, the oxygen source input by another oxygen source input branch pipe 52 in the oxygen source input pipe group 5 is O 3 ; Move the substrate (ITO substrate) along the length direction of the plate reaction chamber 1, pulse nitrogen through the nitrogen input pipe in turn, and then exhaust, the substrate is moved to the bottom of the metal source input pipe group 4, the metal source input pipe group 4 pulses the first precursor to expose the substrate surface, the first precursor is TDMASn and DEZ mixed in a volume ratio of 1:9; at the same time, the first precursor is chemically adsorbed on the substrate surface, the substrate continues to move to the bottom of the nitrogen exhaust pipe 12 adjacent to the metal source input pipe group 4, exhaust the remaining unreacted gas, and then move to the bottom of the nitrogen input pipe 11, input nitrogen to clean the substrate surface, and then move to the bottom of the exhaust pipe 12 to extract the inert gas in the plate reaction chamber 1 from the plate reaction chamber 1.

[0070] Step 2: The substrate continues to move along the length direction of the plate-type reaction chamber 1 to below the oxygen source input tube group 5, and the oxygen source input tube group 5 pulses the second precursor, which is H 2 O and O 3 The first precursor adsorbed on the substrate surface reacts chemically with the second precursor to obtain ZnO / SnO x / SnO 2 The substrate then moves to the nitrogen exhaust pipe 12 adjacent to the oxygen source input pipe group 5 to discharge the remaining unreacted gas, and then moves to the bottom of the nitrogen input pipe 11 to input nitrogen to clean the surface of the substrate, and then moves to the bottom of the exhaust pipe 12 to extract the inert gas in the plate-type reaction chamber 1 from the plate-type reaction chamber 1.

[0071] Step 3: The substrate is moved back and forth in the plate-type reaction chamber 1, and steps 1 and 2 are repeated 100 times to atomically deposit multiple layers of ZnO / SnO on the substrate. x / SnO 2 film.

[0072] Example 3

[0073] An atomic layer deposition process using the plate-type atomic deposition device of Example 1 comprises the following steps:

[0074] Step 1, such as Figure 1As shown, the metal source input by the metal source input branch pipe 42 in the metal source input pipe group 4 is set to be TDMASn, and the metal source input branch pipe inputs at a flow rate of 1:1; the oxygen source input by the oxygen source input branch pipe 52 of the first oxygen source input pipe group 5 along the length direction of the plate-type reaction chamber 1 is H 2 O, the oxygen source input by the oxygen source input branch pipe 52 of the second oxygen source input pipe group 5 is O 3 , the two oxygen source input branches connected to the same main pipe are both input with oxygen source at a flow rate of 1:1. The substrate with a C60 layer on the surface is moved along the length direction of the plate-type reaction chamber 1 to the metal source input pipe group 4, and the metal source input pipe group 4 pulses the first precursor to expose the substrate surface. The first precursor is TDMASn, and the first precursor is chemically adsorbed on the substrate surface. The first precursor is obtained by mixing after inputting TDMASn through two metal source input branches at a volume ratio of 1:1. The substrate continues to move to the nitrogen exhaust pipe adjacent to the metal source input pipe group 4 to discharge the remaining unreacted gas, and then moves to the bottom of the nitrogen input pipe 11, inputs nitrogen to clean the substrate surface, and then moves to the bottom of the exhaust pipe 12 to extract the inert gas in the plate-type reaction chamber 1 from the plate-type reaction chamber 1.

[0075] Step 2: The substrate is moved along the length direction of the plate-type reaction chamber 1 to below the oxygen source input tube group 5, and the oxygen source input tube group 5 pulses the second precursor, which is H 2 O, the first precursor adsorbed on the substrate surface reacts chemically with the second precursor to obtain ZnO / SnO X Composite film, the second precursor is input through two oxygen source input branches into H 2 O is then output through the main pipe, and the flow rates of the two oxygen source input branches are the same. The substrate continues to move to the bottom of the nitrogen exhaust pipe 12 adjacent to the oxygen source input pipe group 5 to discharge the remaining unreacted gas, and then moves to the bottom of the nitrogen input pipe 11 to input nitrogen to clean the substrate surface, and then moves to the bottom of the exhaust pipe 12 to extract the inert gas in the plate-type reaction chamber 1 from the plate-type reaction chamber 1.

[0076] Step 3: The substrate moves along the length direction of the plate-type reaction chamber 1 to the next metal source input pipe group 4. The metal source input pipe group 4 pulses a third precursor to expose the substrate surface. The third precursor is TDMASn. At the same time, the third precursor is chemically adsorbed on the substrate surface. The third precursor is obtained by mixing TDMASn through two metal source input branches at a volume ratio of 1:1. The substrate continues to move to the nitrogen exhaust pipe adjacent to the metal source input pipe group 4 to discharge the remaining unreacted gas, and then moves to the bottom of the nitrogen input pipe 11 to input nitrogen to clean the substrate surface, and then moves to the bottom of the exhaust pipe 12 to extract the inert gas in the plate-type reaction chamber 1 from the plate-type reaction chamber 1.

[0077] Step 4: The substrate is moved along the length direction of the plate-type reaction chamber 1 to the bottom of the next oxygen source input tube group 5, and the oxygen source input tube group 5 pulses the fourth precursor, which is O 3 The third precursor adsorbed on the substrate surface reacts chemically with the fourth precursor to obtain SnO X Composite film, the fourth precursor is input through two oxygen source input branches. 3 After being outputted through the main pipe, the flow rates of the two oxygen source input branches are the same. The substrate continues to move to the nitrogen exhaust pipe adjacent to the metal source input pipe group 4 to exhaust the remaining unreacted gas, and then moves to the bottom of the nitrogen input pipe 11 to input nitrogen to clean the substrate surface, and then moves to the bottom of the exhaust pipe 12 to extract the inert gas in the plate-type reaction chamber 1 from the plate-type reaction chamber 1.

[0078] Step 5: Repeat steps 1 to 4 100 times to deposit SnO alternately on the substrate. x -SnO 2 film.

[0079] Example 4

[0080] An atomic layer deposition process using the plate-type atomic deposition device of Example 1 comprises the following steps:

[0081] Step 1, such as Figure 1 As shown, the metal source input by the metal source input branch pipe 42 in the first metal source input pipe group 4 along the length direction of the plate-type atomic deposition device is set to be DEZ, the metal source input branch pipe 42 in the second metal source input pipe group 4 is set to be TDMASn, and the metal source input branch pipe is set to be input at a flow rate of 1:1; the oxygen source input by the oxygen source input branch pipe 52 in the first oxygen source input pipe group 5 is set to be H 2 O, the oxygen source input by the oxygen source input branch pipe 52 of the second oxygen source input pipe group 5 is H 2 O, the oxygen source input branch pipe is input at a flow rate of 1:1. The substrate with a C60 layer on the surface is moved along the length direction of the plate-type reaction chamber 1 to the metal source input pipe group 4. The metal source input pipe group 4 pulses the first precursor to expose the substrate surface. The first precursor is DEZ. At the same time, the first precursor is chemically adsorbed on the substrate surface. The first precursor is obtained by mixing after inputting DEZ through two metal source input branch pipes at a volume ratio of 1:1. The substrate continues to move to the nitrogen exhaust pipe adjacent to the metal source input pipe group 4 to discharge the remaining unreacted gas, and then moves to the bottom of the nitrogen input pipe 11, inputs nitrogen to clean the substrate surface, and then moves to the bottom of the exhaust pipe 12 to extract the inert gas in the plate-type reaction chamber 1 from the plate-type reaction chamber 1.

[0082] Step 2: The substrate is moved along the length direction of the plate-type reaction chamber 1 to below the oxygen source input tube group 5, and the oxygen source input tube group 5 pulses the second precursor, which is H 2 O, the first precursor adsorbed on the substrate surface reacts chemically with the second precursor to obtain a ZnO composite film. The second precursor is input through two oxygen source input branches. 2 O is then output through the main pipe, and the flow rates of the two oxygen source input branches are the same. The substrate continues to move to the bottom of the nitrogen exhaust pipe 12 adjacent to the oxygen source input pipe group 5 to discharge the remaining unreacted gas, and then moves to the bottom of the nitrogen input pipe 11 to input nitrogen to clean the substrate surface, and then moves to the bottom of the exhaust pipe 12 to extract the inert gas in the plate-type reaction chamber 1 from the plate-type reaction chamber 1.

[0083] Step 3: Repeat steps 1 and 2 8 times.

[0084] Step 4: The substrate moves along the length direction of the plate-type reaction chamber 1 to the next metal source input pipe group 4. The metal source input pipe group 4 pulses the first precursor to expose the substrate surface. The third precursor is TDMASn. At the same time, the third precursor is chemically adsorbed on the substrate surface. The third precursor is obtained by mixing TDMASn through two metal source input branches at a volume ratio of 1:1. The substrate continues to move to the nitrogen exhaust pipe adjacent to the metal source input pipe group 4 to discharge the remaining unreacted gas, and then moves to the bottom of the nitrogen input pipe 11 to input nitrogen to clean the substrate surface, and then moves to the bottom of the exhaust pipe 12 to extract the inert gas in the plate-type reaction chamber 1 from the plate-type reaction chamber 1.

[0085] Step 5: The substrate is moved along the length direction of the plate-type reaction chamber 1 to the bottom of the next oxygen source input tube group 5, and the oxygen source input tube group 5 pulses the fourth precursor, which is H 2 O, the third precursor adsorbed on the substrate surface reacts chemically with the fourth precursor to obtain SnO X Composite film, the fourth precursor is input through two oxygen source input branches into H 2 The substrate continues to move to the nitrogen exhaust pipe adjacent to the metal source input pipe group 4 to exhaust the remaining unreacted gas, and then moves to the bottom of the nitrogen input pipe 11 to input nitrogen to clean the substrate surface, and then moves to the bottom of the exhaust pipe 12 to extract the inert gas in the plate-type reaction chamber 1 from the plate-type reaction chamber 1.

[0086] Step 6: Repeat steps 1 to 5 20 times to deposit ZnO / SnO on the substrate. x composite film).

[0087] Comparative Example 1

[0088] Same as Example 2, except that the first precursor is TDMASn and the second precursor is H 2 O.

[0089] Comparative Example 2

[0090] Same as Example 2, except that the first precursor is DEZ and the second precursor is H 2 O.

[0091] Test example:

[0092] The composite films prepared by the methods of Examples 3-4 and Comparative Examples 1-2 were used to prepare perovskite photovoltaic devices according to the existing method. The structure of the prepared perovskite photovoltaic device is: ITO / PTAA / Al 2 O 3 / Perovskite / PEAI / C 60 / composite film / Ag. The performance parameters of the obtained perovskite photovoltaic device were measured, and the results are shown in Table 1.

[0093] Table 1: Test parameters of deposited films in Examples 1-3 and Comparative Examples 1-2

[0094]

[0095] It can be seen from Table 1 that the devices containing the thin films of Examples 3-4 of the present invention have better comprehensive performance than the devices prepared by the single film layer of Comparative Examples 1-2. At the same time, the metal source or oxygen source is first mixed and then inputted in Examples 3 and 4 of the present invention, which improves the uniformity of the gas and the performance of the film layer compared with direct input. The plate-type atomic deposition equipment of the present invention can improve the deposition efficiency of the atomic layer, and can also improve the atomic layer film ZnO / SnO deposited. x / SnO 2 The structure can better match the energy levels in the perovskite device structure, and the conductivity of the solar cell module can be improved by regulating the thin film properties, which is beneficial to improving the photoelectric conversion efficiency of the perovskite device.

[0096] 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 plate-type atomic deposition device, comprising a plate-type reaction chamber (1), wherein the plate-type reaction chamber (1) is provided with a plurality of mutually spaced inert gas isolation components (10) along its length direction; the inert gas isolation components (10) comprise a nitrogen inlet pipe (11) and a nitrogen exhaust pipe (12) connected to the plate-type reaction chamber (1), characterized in that: The plate-type atomic deposition device further comprises a plurality of metal source input tube groups (4) and a plurality of oxygen source input tube groups (5); a single metal source input tube group (4) and a single oxygen source input tube group (5) are alternately distributed in sequence along the length direction of the plate-type reaction chamber (1) and are connected to the plate-type reaction chamber; a single metal source input tube group (4) is arranged between adjacent inert gas isolation components (10), and a single oxygen source input tube group (5) is arranged between adjacent inert gas isolation components (10), and the metal source input tube group (4) and the oxygen source input tube group (5) are not arranged simultaneously between each adjacent inert gas isolation component (10); A single metal source input pipe group (4) comprises a metal source input main pipe (41) and a plurality of metal source input branch pipes (42) connected to the metal source input main pipe (41); one end of the metal source input main pipe (41) is connected to the plate-type reaction chamber (1), and the other end is connected to the metal source input branch pipe (42); each of the metal source input branch pipes (42) inputs the same or different metal sources; A single oxygen source input pipe group (5) comprises an oxygen source input main pipe (51) and a plurality of oxygen source input branch pipes (52) connected to the oxygen source input main pipe (51); one end of the oxygen source input main pipe (51) is connected to the plate-type reaction chamber (1), and the other end is connected to the oxygen source input branch pipe (52); each of the oxygen source input branch pipes (52) inputs the same or different oxygen sources.

2. The plate-type atomic deposition device according to claim 1, characterized in that: The metal source input branch pipes (42) are two, and the same or different metal sources are input respectively.

3. The plate-type atomic deposition device according to claim 1, characterized in that: The oxygen source input branch pipe (52) has two input branch pipes, which are respectively input with the same or different metal sources.

4. The plate-type atomic deposition device according to claim 1, characterized in that: The number of the metal source input branch pipes (42) is two, and one of the metal source input branch pipes (42) inputs TDMASn, and the other metal source input branch pipe (42) inputs DEZ.

5. The plate-type atomic deposition device according to claim 1, characterized in that: The number of the oxygen source input branch pipes (52) is two, one of which is used to input H2O, and the other is used to input O3.

6. The plate-type atomic deposition device according to claim 1, characterized in that: The metal source input main pipe (41) is provided with a first solenoid valve (411); and a single metal source input branch pipe (42) is provided with a first pulse valve (421) and a second solenoid valve (422) in sequence along the metal source flow direction.

7. The plate-type atomic deposition device according to claim 4, characterized in that: The oxygen source input main pipe (51) is provided with a third solenoid valve (511); and the single oxygen source input branch pipe (52) is provided with a second pulse valve (521) and a fourth solenoid valve (522) in sequence along the flow direction of the metal source.

8. A method for performing an atomic layer deposition process using the plate-type atomic deposition device according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: S1: setting the metal source inputted by one metal source input branch pipe (42) in the metal source input pipe group (4) to be TDMASn, and the metal source inputted by another metal source input branch pipe (42) in the metal source input pipe group (4) to be DEZ; setting the oxygen source inputted by one oxygen source input branch pipe (52) in the oxygen source input pipe group (5) to be H2O, and setting the oxygen source inputted by another oxygen source input branch pipe (52) in the oxygen source input pipe group (5) to be O3; The substrate is moved along the length direction of the plate-type reaction chamber (1) to the metal source input tube group (4), the metal source input tube group (4) pulses a first precursor to expose the substrate surface, the first precursor is TDMASn and / or DEZ gas, and the first precursor is chemically adsorbed on the substrate surface at the same time, the nitrogen input tube (11) adjacent to the metal source input tube group (4) inputs nitrogen into the plate-type reaction chamber (1), and the nitrogen exhaust tube (12) adjacent to the metal source input tube group (4) extracts the inert gas in the plate-type reaction chamber (1) and the remaining unreacted first precursor from the plate-type reaction chamber (1); S2: The substrate moves along the length direction of the plate-type reaction chamber (1) to below the oxygen source input tube group (5), the oxygen source input tube group (5) pulses a second precursor, the second precursor being H2O and / or O3, the first precursor adsorbed on the surface of the substrate reacts chemically with the second precursor to obtain a composite film, the nitrogen input tube (11) adjacent to the oxygen source input tube group (5) inputs nitrogen into the plate-type reaction chamber (1), and the nitrogen exhaust tube (12) adjacent to the oxygen source input tube group (5) extracts the nitrogen in the plate-type reaction chamber (1) and the remaining unreacted second precursor from the plate-type reaction chamber (1); S3: Repeat the S1-S2 operation 0-180 times in a cycle to atomically deposit a multi-layer composite film on the substrate.

9. The method according to claim 8, characterized in that In step S1, when the first precursor is TDMASn and DEZ, the volume ratio of TDMASn to DEZ is 1:(1-19); In step S2, when the second precursor is H2O and O3, the volume ratio of H2O to O3 is 1:(0.5-4).

10. A composite metal film prepared by the method according to any one of claims 8 to 9.

Images