Method and device for recycling reaction residues of atomic layer deposition metal sulfides

Abstract

The present invention discloses a method and apparatus for recycling reaction residues from atomic layer deposition of metal sulfides, relating to the field of micro-nano manufacturing technology. The method addresses the problem of recycling harmful reaction residues during the atomic layer deposition of metal sulfides. The method comprises a pneumatic valve V3, a condensation absorption device, a dissolution absorption device I, a drying device I, a vacuum pump, a pneumatic valve V5, a gas storage device I, a pneumatic valve V7, and a pressure reducing valve V11, which are sequentially connected to form a processing circuit I for recovering and treating metal source reaction residues from the atomic layer deposition of metal sulfides. A pneumatic valve V4, a dissolution absorption device II, a drying device II, a vacuum pump, a pneumatic valve V6, a gas storage device II, a pneumatic valve V8, and a pressure reducing valve V22, which are sequentially connected to form a processing circuit II for recovering and treating hydrogen sulfide source reaction residues from the atomic layer deposition of metal sulfides.

Description

Technical Field

[0001] The present invention relates to the field of micro-nano manufacturing technology, and in particular to a method and device for recycling reaction residues used for atomic layer deposition of metal sulfides. Background Art

[0002] Layered transition metal sulfides (such as molybdenum disulfide, niobium disulfide, and tantalum disulfide) possess excellent mechanical, electrical, optical, and catalytic properties, and hold significant application value in hydrodesulfurization catalysis, photovoltaic cells, photocatalysis, nanotribology, lithium batteries, and dry lubrication. Consequently, the application of atomic layer deposition (ALD) metal sulfides has garnered extensive attention and research in recent years. However, these studies primarily address the challenges of reactive deposition processes and equipment, while a lack of appropriate devices and methods for the treatment of harmful reaction residues remains.

[0003] For example, since the atomic layer deposition process is a continuous reaction process, there will be many residual reactants and residues after the reaction that need to be discharged. The reaction residues of atomic layer deposition of metal sulfide are composed of toxic hydrogen sulfide, hydrochloric acid that is easy to corrode pipelines, expensive metal halides, carrier gas and other components. If these substances are discharged directly into the atmosphere without treatment, on the one hand, it will seriously pollute the environment. On the other hand, since these reaction residues are expensive, direct discharge will cause a waste of resources. Therefore, the existing atomic layer deposition metal sulfide process technology is mainly suitable for laboratory preparation. In terms of large-scale, industrial production applications, the problem of exhaust gas residue treatment needs to be solved.

[0004] However, the existing tail gas residue treatment technology can only achieve the filtration of a single or part of the reaction residue, but cannot achieve the treatment and recycling of all the reaction residues. Specifically, the traditional tail gas residue treatment scheme is mainly achieved by filtering, condensing and adsorption devices. For example: in the scheme [CN110975433A], the reaction tail gas is treated by using an activated carbon felt filter and a condensation method. However, the reactants corresponding to this recovery method are relatively single and cannot be used for the treatment of multiple mixed reaction residues of atomic layer deposition metal sulfide; for example: in the schemes [CN 204684937 U] and [CN201840964 U], an adsorption device is used to filter the reaction residues. The main principle of this scheme is to equip the gas outlet with a substance with adsorption function to adsorb the residues, thereby reducing the emission of reaction residues. However, this filtering device has poor stability and low efficiency, and cannot achieve the recycling of reactants.

[0005] Therefore, how to solve the problem of treating harmful reaction residues such as hydrogen sulfide, hydrochloric acid, and metal halides during the atomic layer deposition of metal sulfides and realize the recycling of the residues has become a problem that needs to be studied. Summary of the Invention

[0006] The embodiments of the present invention provide a method and apparatus for recycling reaction residues of atomic layer deposition of metal sulfides, which solve the problem of recycling harmful reaction residues in the process of atomic layer deposition of metal sulfides.

[0007] To achieve the above objectives, the embodiments of the present invention adopt the following technical solutions:

[0008] In a first aspect, an embodiment of the present invention provides a method comprising:

[0009] Step S1, during the atomic layer deposition process of metal sulfide, when the pneumatic valve V1 (23) is opened and the metal source (24) is fed into the reaction chamber (2) for reaction, under the control of the computer, PLC and electromagnetic reversing valve, the pneumatic valve V3 (5) and the pneumatic valve V5 (14) are opened, and the pneumatic valve V4 (6), the pneumatic valve V6 (16), the pneumatic valve V7 (4) and the pneumatic valve V8 (18) are closed, and the metal halide, hydrochloric acid HCl and the carrier gas, which are the residues of the metal source reaction, enter the processing line I for recovery treatment.

[0010] In step S2, the metal halide in the metal source reaction residue is condensed and recovered through the condensation absorption device (7), the hydrochloric acid HCl is neutralized and absorbed through the dissolution absorption device I (10), and the remaining carrier gas is dried and filtered through the drying device I (11).

[0011] Step S3, the carrier gas after drying and filtration is stored in the gas storage device I (15) through the vacuum pump (13) for recycling.

[0012] Step S4, during the atomic layer deposition process of metal sulfide, when the pneumatic valve V1 (23) is closed, the pneumatic valve V2 (20) is opened, and the hydrogen sulfide source (21) is fed into the reaction chamber (2) for reaction, under the control of the computer, PLC and electromagnetic reversing valve, the pneumatic valve V3 (5) and the pneumatic valve V5 (14) are closed, and the pneumatic valve V4 (6) and the pneumatic valve V6 (16) are opened, and the hydrogen sulfide source reaction residues, hydrogen sulfide, hydrochloric acid HCl, and carrier gas, enter the processing line II for recovery treatment.

[0013] In step S5, the hydrochloric acid HCl in the hydrogen sulfide source reaction residue reacts with the solution in the dissolving and absorbing device II (9) under heating by the heating device (8) to generate hydrogen sulfide, which is filtered and absorbed. The remaining hydrogen sulfide and carrier gas are passed through the drying device II (12) for drying and filtration.

[0014] In step S6, the hydrogen sulfide and carrier gas after drying and filtration are stored in the gas storage device II (17) through the vacuum pump (13) and can be reused in the subsequent atomic layer deposition process.

[0015] Step S7, when it is necessary to use the carrier gas in the gas storage device I (15), open the pneumatic valve V7 (4), set the output pressure of the pressure reducing valve V11 (3) according to the pressure of the metal source path during the atomic layer deposition process, and transport the carrier gas in the gas storage device I (15) to the metal source path for reuse; when it is necessary to use the hydrogen sulfide and carrier gas in the gas storage device II (17), set the output pressure of the pressure reducing valve V22 (19) according to the pressure of the hydrogen sulfide source path during the atomic layer deposition process, and transport the hydrogen sulfide and carrier gas in the gas storage device II (17) to the hydrogen sulfide source path for reuse.

[0016] After the above steps, the reaction residues of the metal source and hydrogen sulfide source of the atomic layer deposition metal sulfide are respectively passed through processing lines I and II for green recycling treatment.

[0017] In a second aspect, an embodiment of the present invention provides a device comprising:

[0018] The components of the device include: pneumatic valve V3 (5), pneumatic valve V4 (6), pneumatic valve V5 (14), pneumatic valve V6 (16), pneumatic valve V7 (4), pneumatic valve V8 (18), condensation absorption device (7), dissolution absorption device I (10), dissolution absorption device II (9), heating device (8), drying device I (11), drying device II (12), vacuum pump (13), gas storage device I (15), gas storage device II (17), pressure reducing valve V11 (3) and pressure reducing valve V22 (19);

[0019] Among them, the pneumatic valve V3 (5), the condensation absorption device (7), the dissolution absorption device I (10), the drying device I (11), the vacuum pump (13), the pneumatic valve V5 (14), the gas storage device I (15), the pneumatic valve V7 (4), and the pressure reducing valve V11 (3) are connected in sequence through the gas transmission pipe to form a processing line I;

[0020] The pneumatic valve V4 (6), the dissolving and absorbing device II (9), the drying device II (12), the vacuum pump (13), the pneumatic valve V6 (16), the gas storage device II (17), the pneumatic valve V8 (18), and the pressure reducing valve V22 (19) are connected in sequence through the gas transmission pipe to form a processing line II;

[0021] The pneumatic valve V3 (5) of the processing line I and the pneumatic valve V4 (6) of the processing line II are both connected to the reaction chamber (2) through the gas pipeline. The reaction chamber (2) is equipped with a PT pressure gauge (1).

[0022] The metal source (24) is connected to the reaction chamber (2) via a pneumatic valve V1 (23), and the hydrogen sulfide source (21) is connected to the reaction chamber (2) via a pneumatic valve V2 (20).

[0023] The method and apparatus for recycling reaction residues from atomic layer deposition of metal sulfides, provided in embodiments of the present invention, address the problem of recycling harmful reaction residues such as hydrogen sulfide, hydrochloric acid, and metal halides during the atomic layer deposition of metal sulfides. The apparatus of this embodiment has a relatively simple structure and is easy to implement, thereby avoiding environmental pollution. Furthermore, by enabling the reuse of expensive resources, the cost of atomic layer deposition of metal sulfides is significantly reduced, thereby promoting the industrialization and large-scale development and application of atomic layer deposition equipment and process technologies. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0025] Figure 1 、 2 A schematic diagram of the device structure provided by an embodiment of the present invention;

[0026] Figure 3 、 4 Schematic diagram of two possible method flow charts provided by embodiments of the present invention;

[0027] Figure 5 、 6 This is a schematic diagram of a specific process in practical application provided by an embodiment of the present invention. DETAILED DESCRIPTION

[0028] To enable those skilled in the art to better understand the technical solutions of the present invention, the present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments. The embodiments of the present invention will be described in detail below, with examples of the embodiments illustrated in the accompanying drawings. Throughout, identical or similar reference numerals represent identical or similar elements or elements having identical or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and intended only to explain the present invention and are not to be construed as limiting the present invention. Those skilled in the art will appreciate that, unless otherwise stated, the singular forms "a," "an," "said," and "the" used herein may also include the plural forms. It should be further understood that the term "comprising" as used in the description of the present invention refers to the presence of the stated features, integers, steps, operations, elements, and / or components, but does not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof. It should be understood that when an element is referred to as being "connected" or "coupled" to another element, it may be directly connected or coupled to the other element, or intervening elements may be present. Furthermore, "connected" or "coupled" as used herein may include wireless connections or couplings. The term "and / or" as used herein includes any and all combinations of one or more associated listed items. It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by those skilled in the art in the art to which the present invention belongs. It should also be understood that terms such as those defined in general dictionaries should be understood to have meanings consistent with their meanings in the context of the prior art, and will not be interpreted in an idealized or overly formal sense unless defined as such herein.

[0029] The embodiment of the present invention provides a method for recycling reaction residues for atomic layer deposition of metal sulfides, the method comprising: steps S1 to S3 performed on processing line I, and steps S4 to S6 performed on processing line II; in practical applications, such as Figure 3 As shown, the steps S1 to S3 on the processing line I can be executed first, and then the steps S4 to S6 on the processing line II can be executed, that is, the steps S1-S6 are executed in sequence. Figure 4 As shown, only the process on one of the processing line I and the processing line II is executed.

[0030] Among them, the pneumatic valve V3 (5), the condensation absorption device (7), the dissolution absorption device I (10), the drying device I (11), the vacuum pump (13), the pneumatic valve V5 (14), the gas storage device I (15), the pneumatic valve V7 (4), and the pressure reducing valve V11 (3) are connected in sequence through the gas transmission pipe to form the processing line I; the pneumatic valve V4 (6), the dissolution absorption device II (9), the drying device II (12), the vacuum pump (13), the pneumatic valve V6 (16), the gas storage device II (17), the pneumatic valve V8 (18), and the pressure reducing valve V22 (19) are connected in sequence through the gas transmission pipe to form the processing line II. The pneumatic valve V3 (5), the pneumatic valve V4 (6), the pneumatic valve V5 (14), the pneumatic valve V6 (16), the pneumatic valve V7 (4), and the pneumatic valve V8 (18) are all connected to the electromagnetic reversing valve, such as Figure 2 As shown, the solenoid reversing valve controls the opening and closing of multiple pneumatic valves. The solenoid reversing valve is connected to a programmable logic controller (PLC). A computer controls the PLC, which in turn controls the solenoid reversing valve. The valve is opened and closed according to the process sequence during the atomic layer deposition process, allowing the metal source reaction residues and hydrogen sulfide source reaction residues of the atomic layer deposition metal sulfide to enter processing lines I and II for recovery.

[0031] Step S1, during the atomic layer deposition of metal sulfide, if the processing line I is selected, the pneumatic valve V1 (23) is opened to allow the metal source (24) to be fed into the reaction chamber (2), and under the control of the computer, PLC and electromagnetic reversing valve, the pneumatic valve V3 (5) and the pneumatic valve V5 (14) are opened, and the pneumatic valve V4 (6), the pneumatic valve V6 (16), the pneumatic valve V7 (4) and the pneumatic valve V8 (18) are closed, so that the metal source reaction residue, hydrochloric acid HCl and the carrier gas enter the processing line I for recovery treatment;

[0032] Step S2, condensing and recovering the metal halide in the metal source reaction residue by the condensation absorption device (7), neutralizing and absorbing the hydrochloric acid HCl by the dissolution absorption device I (10), and drying and filtering the remaining carrier gas by the drying device I (11);

[0033] Step S3, the carrier gas after drying and filtration is pumped into the gas storage device I (15) through the vacuum pump (13) for storage and recycling;

[0034] Step S4, if the treatment line II is selected, the pneumatic valve V1 (23) is closed and the pneumatic valve V2 (20) is opened so that the hydrogen sulfide source (21) is fed into the reaction chamber (2). Under the control of the computer, PLC and electromagnetic reversing valve, at the same time, the pneumatic valve V3 (5) and the pneumatic valve V5 (14) are closed, and the pneumatic valve V4 (6) and the pneumatic valve V6 (16) are opened, so that the hydrogen sulfide source reaction residue, hydrochloric acid HCl and the carrier gas enter the treatment line II for recovery treatment;

[0035] Step S5, hydrochloric acid HCl reacts with the solution in the dissolving and absorbing device II (9) under heating by the heating device (8) to generate hydrogen sulfide; then, the hydrogen sulfide and the carrier gas are dried by the drying device II (12);

[0036] In step S6, the hydrogen sulfide and carrier gas after drying and filtration are pumped into the gas storage device II (17) via the vacuum pump (13) for storage, and can be reused in the subsequent atomic layer deposition process.

[0037] Furthermore, when it is necessary to use the carrier gas in the gas storage device I (15), the pneumatic valve V7 (4) is opened, and the output pressure of the pressure reducing valve V11 (3) is set according to the pressure of the metal source path during the atomic layer deposition process, and the carrier gas in the gas storage device I (15) is transported to the metal source path for reuse; when it is necessary to use the hydrogen sulfide and carrier gas in the gas storage device II (17), the output pressure of the pressure reducing valve V22 (19) is set according to the pressure of the hydrogen sulfide source path during the atomic layer deposition process, and the hydrogen sulfide and carrier gas in the gas storage device II (17) are transported to the hydrogen sulfide source path for reuse.

[0038] In a preferred embodiment, in step S1, the temperature of the condensation absorption device (7) is controlled at [50°C, 200°C].

[0039] In a preferred embodiment, in step S5, the temperature of the heating device (8) is controlled at [30°C, 150°C].

[0040] In practical applications, this embodiment can be used for green treatment of the reaction residues of atomic layer deposition of metal sulfides, combined with Figure 1 and Figure 2 , the specific process flow is as follows Figure 5 As shown, including:

[0041] Step S101, during the atomic layer deposition process of metal sulfide, when the pneumatic valve V1 (23) is opened and the metal source (24) is fed into the reaction chamber (2) for reaction, under the control of the computer, PLC and electromagnetic reversing valve, the pneumatic valve V3 (5) and the pneumatic valve V5 (14) are opened, and the pneumatic valve V4 (6), the pneumatic valve V6 (16), the pneumatic valve V7 (4) and the pneumatic valve V8 (18) are closed, and the metal halide, hydrochloric acid HCl and the carrier gas, which are the residues of the metal source reaction, enter the processing line I for recovery processing.

[0042] In step S102, the metal halide in the metal source reaction residue is condensed and recovered through the condensation absorption device (7) and can be reused in the subsequent atomic layer deposition process. The hydrochloric acid HCl is neutralized and absorbed by the NaOH solution in the dissolving absorption device I (10). The remaining carrier gas is dried and filtered through the soda lime in the drying device I (11).

[0043] Step S103, the carrier gas after drying and filtration is stored in the gas storage device I (15) through the vacuum pump (13) for recycling.

[0044] Step S104, during the atomic layer deposition process of metal sulfide, when the pneumatic valve V1 (23) is closed, the pneumatic valve V2 (20) is opened, and the hydrogen sulfide source (21) is fed into the reaction chamber (2) for reaction, under the control of the computer, PLC and electromagnetic reversing valve, the pneumatic valve V3 (5) and the pneumatic valve V5 (14) are closed, and the pneumatic valve V4 (6) and the pneumatic valve V6 (16) are opened, and the hydrogen sulfide source reaction residues, hydrogen sulfide, hydrochloric acid HCl, and carrier gas, enter the processing line II for recovery processing.

[0045] In step S105, the hydrochloric acid HCl in the hydrogen sulfide source reaction residue reacts with the NaS2 and NaHS solutions in the dissolving and absorbing device II (9) under heating by the heating device (8) to generate hydrogen sulfide, which is filtered and absorbed. The remaining hydrogen sulfide and carrier gas are dried and filtered through phosphorus pentoxide in the drying device II (12).

[0046] In step S106, the hydrogen sulfide and carrier gas after drying and filtration are stored in the gas storage device II (17) through the vacuum pump (13) and can be reused in the subsequent atomic layer deposition process.

[0047] Step S107, when it is necessary to use the carrier gas in the gas storage device I (15), open the pneumatic valve V7 (4), set the output pressure of the pressure reducing valve V11 (3) according to the pressure of the metal source path during the atomic layer deposition process, and transport the carrier gas in the gas storage device I (15) to the metal source path for reuse; when it is necessary to use the hydrogen sulfide and carrier gas in the gas storage device II (17), set the output pressure of the pressure reducing valve V22 (19) according to the pressure of the hydrogen sulfide source path during the atomic layer deposition process, and transport the hydrogen sulfide and carrier gas in the gas storage device II (17) to the hydrogen sulfide source path for reuse.

[0048] After the above steps, the reaction residues of the metal source and hydrogen sulfide source of the atomic layer deposition metal sulfide are respectively passed through processing lines I and II for green recycling treatment. On the one hand, environmental pollution is avoided. On the other hand, due to the reuse of expensive sources, the cost of atomic layer deposition metal sulfide is greatly reduced, and it can be used for large-scale, industrial production and application.

[0049] In practical applications, this embodiment can also be used for green treatment of the reaction residues of atomic layer deposition of metal sulfide NbS2. Specifically, nitrogen is used as the carrier gas, niobium chloride is used as the metal source, and hydrogen sulfide is used as the sulfur source. The reaction residues are niobium chloride, hydrochloric acid HCL, hydrogen sulfide, and nitrogen. Figure 1 and Figure 2 , the specific process flow can be further refined, such as Figure 6 As shown, including:

[0050] Step S201, during the atomic layer deposition process of NbS2, when the pneumatic valve V1 (23) is opened and the metal source niobium chloride (24) is fed into the reaction chamber (2) for reaction, under the control of the computer, PLC and electromagnetic reversing valve, the pneumatic valve V3 (5) and the pneumatic valve V5 (14) are opened, and the pneumatic valve V4 (6), the pneumatic valve V6 (16), the pneumatic valve V7 (4) and the pneumatic valve V8 (18) are closed, and the niobium chloride reaction residues, niobium chloride, hydrochloric acid HCl and carrier gas, enter the processing line I for recovery treatment.

[0051] In step S202, niobium chloride is condensed and recovered through the condensation absorption device (7) and can be reused in the subsequent atomic layer deposition process. Hydrochloric acid HCl is neutralized and absorbed by the NaOH solution in the dissolving absorption device I (10). The remaining carrier gas is dried and filtered through the soda lime in the drying device I (11). The condensation absorption device (7) ensures that the niobium chloride is condensed and the hydrochloric acid HCl passes smoothly. According to their physical properties, the condensation temperature is set to 110 degrees Celsius.

[0052] Step S203, the carrier gas after drying and filtration is stored in the gas storage device I (15) through the vacuum pump (13) for recycling.

[0053] Step S204, during the atomic layer deposition process of NbS2, when the pneumatic valve V1 (23) is closed, the pneumatic valve V2 (20) is opened, and the hydrogen sulfide source (21) is fed into the reaction chamber (2) for reaction, under the control of the computer, PLC and electromagnetic reversing valve, the pneumatic valve V3 (5) and the pneumatic valve V5 (14) are closed, and the pneumatic valve V4 (6) and the pneumatic valve V6 (16) are opened, and the hydrogen sulfide source reaction residues, hydrogen sulfide, hydrochloric acid HCl, and carrier gas, enter the processing line II for recovery processing.

[0054] In step S205, the hydrochloric acid HCl in the hydrogen sulfide source reaction residue reacts with the NaS2 and NaHS solutions in the dissolving and absorbing device II (9) under heating by the heating device (8) (heating temperature is 65 degrees Celsius) to generate hydrogen sulfide, which is filtered and absorbed. The remaining hydrogen sulfide and carrier gas are dried and filtered through phosphorus pentoxide in the drying device II (12).

[0055] In step S206, the hydrogen sulfide and carrier gas after drying and filtration are stored in the gas storage device II (17) through the vacuum pump (13) and can be reused in the subsequent atomic layer deposition process.

[0056] Step S207, when it is necessary to use the carrier gas in the gas storage device I (15), open the pneumatic valve V7 (4), set the output pressure of the pressure reducing valve V11 (3) according to the pressure of the niobium chloride source path during the atomic layer deposition process, and transport the carrier gas in the gas storage device I (15) to the niobium chloride source path for reuse; when it is necessary to use the hydrogen sulfide and carrier gas in the gas storage device II (17), set the output pressure of the pressure reducing valve V22 (19) according to the pressure of the hydrogen sulfide source path during the atomic layer deposition process, and transport the hydrogen sulfide and carrier gas in the gas storage device II (17) to the hydrogen sulfide source path for reuse.

[0057] After the above steps, the reaction residues of the niobium chloride source and hydrogen sulfide source for atomic layer deposition of NbS2 are respectively recycled through processing lines I and II for green treatment. On the one hand, environmental pollution is avoided. On the other hand, waste is avoided due to the reuse of expensive niobium chloride source and hydrogen sulfide source, which greatly reduces the cost of atomic layer deposition of metal sulfides and enables large-scale, industrialized production and application.

[0058] This embodiment also provides a device for recycling reaction residues of atomic layer deposition metal sulfides, the components of which include: pneumatic valve V3 (5), pneumatic valve V4 (6), pneumatic valve V5 (14), pneumatic valve V6 (16), pneumatic valve V7 (4), pneumatic valve V8 (18), condensation absorption device (7), dissolution absorption device I (10), dissolution absorption device II (9), heating device (8), drying device I (11), drying device II (12), vacuum pump (13), gas storage device I (15), gas storage device II (17), pressure reducing valve V11 (3) and pressure reducing valve V22 (19); wherein, the condensation absorption device (7) is used for condensing and recovering precious metal halides. The dissolution absorption device I (10) is used for absorbing hydrochloric acid HCl. The drying device I (11) is used for drying the carrier gas in the metal source reaction residue. The vacuum pump (13) is used for maintaining the vacuum degree in the system and ensuring the flow of the carrier gas and source material. The gas storage device I (15) is used to store the dried carrier gas. The pressure reducing valve V11 (3) reduces the pressure of the carrier gas in the gas storage device I (15) and passes it into the metal source path for reuse. The dissolution and absorption device II (9) is used to filter and absorb the hydrochloric acid HCl in the hydrogen sulfide source reaction residue. The external heating device (8) can set the heating temperature. The drying device II (12) is used to dry the hydrogen sulfide and carrier gas in the hydrogen sulfide source reaction residue. The gas storage device II (17) is used to store the dried hydrogen sulfide and carrier gas. The pressure reducing valve V22 (19) reduces the pressure of the hydrogen sulfide and carrier gas in the gas storage device II (17) and passes it into the hydrogen sulfide source path for reuse. Pneumatic valve V3 (5), pneumatic valve V4 (6), pneumatic valve V5 (14), pneumatic valve V6 (16), pneumatic valve V7 (4), and pneumatic valve V8 (18) are controlled by a computer, a PLC, and an electromagnetic reversing valve, and are opened and closed according to the process sequence during the atomic layer deposition process to ensure that the metal source reaction residues and hydrogen sulfide source reaction residues of the atomic layer deposition metal sulfide can enter the processing lines I and II respectively for recovery and processing.

[0059] Among them, the pneumatic valve V3 (5), the condensation absorption device (7), the dissolution absorption device I (10), the drying device I (11), the vacuum pump (13), the pneumatic valve V5 (14), the gas storage device I (15), the pneumatic valve V7 (4), and the pressure reducing valve V11 (3) are sequentially connected through a gas pipeline to form a processing line I for recovering and processing the metal source reaction residues of the atomic layer deposition metal sulfide, including metal halide, hydrochloric acid HCl, and carrier gas (inert gas such as nitrogen N2, argon Ar, etc.);

[0060] The condensation absorption device (7) has a configurable condensation temperature and is used to condense and recover precious metal halides, which can be reused in subsequent atomic layer deposition processes, thus saving costs. The gas storage device I (15) is used to store the dried carrier gas, thus saving costs and allowing it to be reused in subsequent atomic layer deposition processes.

[0061] The pneumatic valve V4 (6), the dissolving and absorbing device II (9), the drying device II (12), the vacuum pump (13), the pneumatic valve V6 (16), the gas storage device II (17), the pneumatic valve V8 (18), and the pressure reducing valve V22 (19) are connected in sequence through a gas transmission pipe to form a processing line II for recovering and treating the hydrogen sulfide source reaction residues of the atomic layer deposition metal sulfide, including hydrogen sulfide, hydrochloric acid, and carrier gas (inert gas such as nitrogen N2, argon Ar, etc.); the gas storage device II (17) is used to store the dried hydrogen sulfide and carrier gas, saving costs, and can be reused in the subsequent atomic layer deposition process;

[0062] The pneumatic valve V3 (5) of the processing line I and the pneumatic valve V4 (6) of the processing line II are both connected to the reaction chamber (2) through the gas pipeline. The reaction chamber (2) is equipped with a PT pressure gauge (1).

[0063] The metal source (24) is connected to the reaction chamber (2) via a pneumatic valve V1 (23), and the hydrogen sulfide source (21) is connected to the reaction chamber (2) via a pneumatic valve V2 (20).

[0064] The pressure reducing valve V11 (3) is used to reduce the pressure of the carrier gas in the gas storage device I (15) and pass it into the metal source path; the pressure reducing valve V11 (3) is used to reduce the pressure of the carrier gas in the gas storage device I (15) according to the pressure of the metal source path during the atomic layer deposition process, and pass it into the metal source path for reuse. The pressure reducing valve V22 (19) is used to reduce the pressure of the hydrogen sulfide and carrier gas in the gas storage device II (17) and pass them into the hydrogen sulfide source path. The pressure reducing valve V22 (19) is used to reduce the pressure of the hydrogen sulfide and carrier gas in the gas storage device II (17) according to the pressure of the hydrogen sulfide source path during the atomic layer deposition process, and pass them into the hydrogen sulfide source path for reuse.

[0065] Specifically, a neutralization reaction solution is built into the dissolution and absorption device I (10), and the neutralization reaction solution is used to react with the hydrochloric acid HCl to neutralize the solution. The specific composition of the solution is not required, as long as it can react with the hydrochloric acid HCl to absorb the alkaline solution of the hydrochloric acid HCl. A desiccant is built into the drying device I (11), and the desiccant is used to remove the water vapor introduced from the dissolution and absorption device I (10). The drying device I (11) is used to dry the carrier gas in the metal source reaction residue and remove the water vapor introduced from the dissolution and absorption device I (10). The drying device I (11) is built into the desiccant, and the specific composition of the desiccant is not required, as long as it can dry and remove the water vapor in the carrier gas.

[0066] In the preferred embodiment, the reaction solution built into the dissolution absorption device I (10) is sodium hydroxide NaOH solution or potassium hydroxide KOH solution; the desiccant is soda lime or silica gel.

[0067] Specifically, a neutralization reaction solution is built into the dissolving and absorbing device II (9), and the neutralization reaction solution is used to react with the hydrochloric acid HCl to generate hydrogen sulfide. The solution for neutralizing and absorbing the hydrochloric acid HCl is used to filter and absorb the hydrochloric acid HCl in the hydrogen sulfide source reaction residue. The specific composition of the solution is not required. It mainly absorbs the hydrochloric acid HCl and ensures that hydrogen sulfide passes smoothly. A heating device (8) is installed outside the dissolving and absorbing device II (9). The heating temperature can be set to ensure that the NaS2 and NaHS solutions react with the hydrochloric acid HCl to generate hydrogen sulfide. It is used to dry the hydrogen sulfide and the carrier gas in the hydrogen sulfide source reaction residue. The specific composition of the desiccant is not required. It only needs to dry and remove the water vapor in the hydrogen sulfide and the carrier gas. The drying device II (12) is built with a desiccant.

[0068] In the preferred solution, the reaction solution built into the dissolution absorption device II (9) is sodium disulfide NaS2 solution or sodium hydrosulfide NaHS solution; the desiccant in the drying device II (12) is phosphorus pentoxide.

[0069] Each embodiment in this specification is described in a progressive manner, and the same or similar parts between the embodiments can be referred to each other, and each embodiment focuses on the differences from other embodiments. In particular, for the device embodiment, since it is basically similar to the method embodiment, the description is relatively simple, and the relevant parts can be referred to the partial description of the method embodiment. The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited to this. Any changes or replacements that can be easily thought of by any technician familiar with this technical field within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A method for recycling reaction residues for atomic layer deposition of metal sulfides, characterized in that: The method comprises: steps S1 to S3 performed on processing line I, and steps S4 to S6 performed on processing line II; Step S1, if the treatment line I is selected, the pneumatic valve V1 (23) is opened to allow the metal source (24) to be fed into the reaction chamber (2), and at the same time, the pneumatic valve V3 (5) and the pneumatic valve V5 (14) are opened, and the pneumatic valve V4 (6), the pneumatic valve V6 (16), the pneumatic valve V7 (4) and the pneumatic valve V8 (18) are closed, so that the metal source reaction residue, hydrochloric acid HCl and the carrier gas enter the treatment line I; Step S2, condensing and recovering the metal halide in the metal source reaction residue by the condensation absorption device (7), neutralizing and absorbing the hydrochloric acid HCl by the dissolution absorption device I (10), and drying and filtering the remaining carrier gas by the drying device I (11); Step S3, the dried and filtered carrier gas is pumped into the gas storage device I (15) via the vacuum pump (13) for storage; Step S4, if the treatment line II is selected, the pneumatic valve V1 (23) is closed and the pneumatic valve V2 (20) is opened so that the hydrogen sulfide source (21) is fed into the reaction chamber (2). At the same time, the pneumatic valve V3 (5) and the pneumatic valve V5 (14) are closed, and the pneumatic valve V4 (6) and the pneumatic valve V6 (16) are opened so that the hydrogen sulfide source reaction residue, hydrochloric acid HCl and the carrier gas enter the treatment line II. Step S5, hydrochloric acid HCl reacts with the solution in the dissolving and absorbing device II (9) under heating by the heating device (8) to generate hydrogen sulfide; then, the hydrogen sulfide and the carrier gas are dried by the drying device II (12); Step S6, the hydrogen sulfide and carrier gas after drying and filtration are pumped into the gas storage device II (17) via the vacuum pump (13) for storage; The method further includes: when the carrier gas in the gas storage device I (15) needs to be used, opening the pneumatic valve V7 (4), setting the output pressure of the pressure reducing valve V11 (3) according to the pressure of the metal source path during the atomic layer deposition process, and delivering the carrier gas in the gas storage device I (15) to the metal source path; When the hydrogen sulfide and carrier gas in the gas storage device II (17) need to be used, the output pressure of the pressure reducing valve V22 (19) is set according to the pressure of the hydrogen sulfide source path during the atomic layer deposition process, and the hydrogen sulfide and carrier gas in the gas storage device II (17) are transported to the hydrogen sulfide source path; The pneumatic valve V3 (5), the condensation absorption device (7), the dissolution absorption device I (10), the drying device I (11), the vacuum pump (13), the pneumatic valve V5 (14), the gas storage device I (15), the pneumatic valve V7 (4), and the pressure reducing valve V11 (3) are connected in sequence through the gas transmission pipe to form a processing line I; The pneumatic valve V4 (6), the dissolving and absorbing device II (9), the drying device II (12), the vacuum pump (13), the pneumatic valve V6 (16), the gas storage device II (17), the pneumatic valve V8 (18), and the pressure reducing valve V22 (19) are connected in sequence through the gas transmission pipe to form a processing line II; In step S1, the temperature of the condensation absorption device (7) is controlled at [50°C, 200°C]; In step S5, the temperature of the heating device (8) is controlled at [30°C, 150°C].

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