Erasable organic-inorganic hybrid patterned film prepared by molecular layer deposition

Abstract

The invention discloses an erasable organic-inorganic hybrid patterned film prepared by molecular layer deposition, which is characterized in that a high-precision and uniform hybrid photoresist film is formed on the surface of a substrate by alternately depositing an inorganic precursor and an organic ligand, and the method comprises the following specific steps of: by adopting an MLD (Multilayer Ligand Discharge) technology, performing vacuum deposition, air source switching and a circulating purging process, and forming an erasable organic-inorganic hybrid patterned film on the surface of the substrate, thereby obtaining the erasable organic-inorganic hybrid patterned film. Film components and thickness are accurately controlled; carrying out patterning exposure on the film by utilizing ultraviolet lithography or electron beams; pattern erasing and rewriting can be realized through heating and re-exposure; and a 0.01% oxalic acid solution is used for developing. The obtained film has ultra-low roughness (RMS 0.12 nm), high resolution-electron beam exposure can at least achieve 50 nm line width and excellent etching resistance, and the problems that a traditional photoresist film is uneven in thickness, low in sensitivity and high in trial and error cost are effectively solved; the method simplifies the process flow, is suitable for deep ultraviolet and extreme ultraviolet lithography processes, and has important application prospects in semiconductor device manufacturing.

Description

Technical Field

[0001] The present invention relates to the technical field of semiconductor manufacturing materials, and particularly to an erasable organic-inorganic hybrid patterned thin film prepared by atomic layer deposition. Background Art

[0002] With the continuous improvement of the integration degree of semiconductor devices, lithography technology, as the core process of chip manufacturing, its precision and efficiency directly determine the performance and cost of integrated circuits. Photoresist, as the key material in the lithography process, transfers the mask pattern to the silicon wafer surface through a photochemical reaction, and then forms a nanoscale circuit structure. Traditional photoresists are mostly prepared by solution mixing methods, such as chemically amplified photoresists (CAR), which improve sensitivity through photoacid-catalyzed reactions. However, they still face significant challenges in deep ultraviolet (DUV) and more advanced extreme ultraviolet (EUV) lithography processes: on the one hand, traditional methods have limited control over the molecular structure of photoresists, resulting in insufficient film thickness uniformity, limited resolution, and weak etching resistance during the plasma etching process; on the other hand, chemically amplified resists rely on the photoacid diffusion mechanism, which easily leads to an increase in line width roughness (LWR) and is difficult to meet the requirements of sub-10nm nodes. More critically, the exposure process of traditional photoresists is based on irreversible photochemical reactions (such as covalent bond cleavage or crosslinking). Once the exposure is completed, their molecular structure is permanently changed and cannot be restored to the initial state by physical or chemical means. This irreversibility leads to the inability to correct exposure errors and a very high material waste rate, especially in complex mask verification or scientific research trial-and-error scenarios where the cost is difficult to control.

[0003] The present invention provides an erasable organic-inorganic hybrid patterned thin film prepared by atomic layer deposition. By alternately introducing inorganic metal precursors and organic ligands, an erasable patterned organic-inorganic hybrid thin film is self-assembled on the substrate surface. This method makes full use of the self-limiting reaction characteristics of atomic layer deposition (ALD) technology to achieve precise control of film thickness and composition ratio. By optimizing the precursor pulse time and cycle number, the sensitivity and etching resistance of the thin film can be significantly improved, while avoiding the complex steps of post-exposure baking (PEB) in traditional processes. In particular, this thin film can be pattern-exposed and can be erased by heating, having broad application prospects and research value. Summary of the Invention

[0004] The object of the present invention is to provide an erasable organic-inorganic hybrid patterned thin film prepared by atomic layer deposition, a novel erasable organic-inorganic hybrid patterned thin film, which has potential application value in enhancing the resolution, sensitivity, reducing roughness, and lowering costs of photoresists.

[0005] The object of the present invention is achieved by the following technical solutions: An erasable organic-inorganic hybrid patterned film prepared by atomic layer deposition, and the atomic layer deposition preparation includes the following steps: S1. Place a substrate on the base of the reaction chamber (105) of the vapor deposition process. Load an inorganic metal precursor and an organic ligand into the first precursor bottle (101) and the second precursor bottle (102) respectively. Open the first nitrogen pressure reducing valve (201) to 0.55 MPa and the second nitrogen pressure reducing valve (202) to 0.14 MPa, which are used as power gas and carrier gas. Turn on the vacuum pump (302), evacuate the system to vacuum and heat the first precursor bottle (101), the second precursor bottle (102), the reaction chamber, the inlet pipeline and the outlet pipeline. After opening the first precursor manual valve (103) and the second precursor manual valve (104), enter the following cycle: Open the first solenoid valve (203) to allow the inorganic metal precursor to enter the reaction chamber and deposit, close the first solenoid valve (203) and open the stop valve (301) to purge the excess gas; Open the second solenoid valve (204) to allow the organic ligand to enter the reaction chamber and deposit, close the second solenoid valve (204) and open the stop valve (301) to purge the excess gas; After repeating the cycle multiple times, a positive photoresist film is deposited on the surface of the substrate; S2. Pattern and expose the positive photoresist film deposited on the surface of the substrate with an ultraviolet lithography machine or an electron beam. S3. Place the patterned film on top of a hot plate and heat it for 1 - 5 minutes to erase the pattern, and then repeat the pattern exposure of the film. S4. Put the exposed photoresist film sample into the developer for 30 seconds, then quickly put the sample into ultrapure water or isopropanol for infiltration for 10 seconds, and then use a high-pressure nitrogen gun to dry the surface of the sample to form a pattern.

[0006] Preferably, the molar ratio of the inorganic metal precursor to the organic ligand is 1:1 - 5.

[0007] More preferably, the molar ratio of the inorganic metal precursor to the organic ligand is 1:1, 1:3, 1:5.

[0008] Preferably, the inorganic metal precursor is selected from at least one of hafnium tetrakis(dimethylamino) (TDMAHf) and tin tetrakis(dimethylamino); the organic ligand is selected from at least one of maleic anhydride (MAH) and maleic acid.

[0009] Preferably, in step S1, evacuate the system to vacuum and heat the first precursor bottle (101) to 75 - 85 °C, the second precursor bottle (102) to 85 - 95 °C, the reaction chamber (105) to 115 - 125 °C, the inlet pipeline to 115 - 125 °C, and the outlet pipeline to 95 - 105 °C.

[0010] Preferably, in step S2, the light source wavelength of the ultraviolet lithography machine is 254 nm, and the exposure dose is 600 MJ.

[0011] Preferably, in step S2, the beam current of the electron beam is 100 pA, and the exposure dose is 400 μC.

[0012] Preferably, in step S3, the heating temperature for erasing the pattern of the positive photoresist film is 50 - 150 °C.

[0013] Preferably, in step S4, the developer is an oxalic acid solution with a mass fraction of 0.01%.

[0014] Due to the application of the above technical solution, the present invention has the following beneficial effects compared with the prior art: 1. The erasable organic-inorganic hybrid patterned film prepared by molecular layer deposition of the present invention forms an erasable patterned organic-inorganic hybrid film by self-assembly on the surface of a semiconductor substrate through the alternating introduction of inorganic metal precursors and organic ligands; this method makes full use of the self-limiting reaction characteristics of the molecular layer deposition (MLD) technology to achieve precise control of the film thickness and composition ratio; by optimizing the precursor pulse time and cycle number, the sensitivity and etching resistance of the film can be significantly improved; 2. The film thickness of the erasable organic-inorganic hybrid patterned film prepared by molecular layer deposition of the present invention is precisely controllable and the surface flatness is extremely high. The surface roughness (RMS) is only 0.12 nanometers. After exposure, there is no need for the complex step of post-exposure baking (PEB). Electron beam exposure can achieve high-resolution patterns with a period of 100 nm and a line width of 50 nm. This film can be patterned and exposed, and the pattern can be erased by heating. The present invention can be patterned after exposure and is heating-reversible, having broad application prospects and research and development value. Description of the Drawings

[0015] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings required for use in the description of the specific embodiments or the prior art. Obviously, some of the following drawings are embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0016] Figure 1 It is a schematic diagram of the molecular layer deposition device in Embodiment 1 of the present invention; Figure 2 It is a schematic diagram of the molecular layer deposition mechanism of TDMAHf and MAH in Embodiment 1 of the present invention; Figure 3 It is the film obtained by cycling 100 times in Embodiment 1 of the present invention; Figure 4It is the AFM characterization diagram of the thin film obtained by cycling 100 times in Example 1 of the present invention; Figure 5 It is the optical microscope diagram of the exposed and patterned thin film in Example 1 of the present invention; Figure 6 It is the optical microscope diagram of the patterning, erasing and rewriting process with TDMAHf:MAH = 1:5 in Example 1 of the present invention; Figure 7 It is the optical microscope diagram of the patterning, erasing and rewriting process with TDMAHf:MAH = 1:3 in Example 2 of the present invention; Figure 8 It is the optical microscope diagram of the patterning, erasing and rewriting process with TDMAHf:MAH = 1:1 in Example 3 of the present invention; Figure 9 It is the optical microscope diagram after DUV exposure and development in Example 4 of the present invention; Figure 10 It is the infrared spectrum diagram of the photoresist thin film before and after exposure in Example 4 of the present invention; Figure 11 It is the schematic diagram of the exposure mechanism in Example 4 of the present invention; Figure 12 It is the SEM diagram after electron beam exposure and development in Example 5 of the present invention; Among them, in the appendix Figure 1 : 101 - Precursor bottle 1; 102 - Precursor bottle 2; 103 - Precursor manual valve 1; 104 - Precursor manual valve 2; 105 - Reaction chamber; 201 - Nitrogen pressure reducing valve 1; 202 - Nitrogen pressure reducing valve 2; 203 - Solenoid valve 1; 204 - Solenoid valve 2; 301 - Stop valve; 302 - Vacuum pump. Detailed implementation manners

[0017] In order to have a clearer understanding of the technical features, purposes and effects of the present invention, the specific implementation manners are described in detail below.

[0018] The present invention will be further described below in conjunction with the embodiments, but the present invention is not limited to the following embodiments. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific uses. The implementation conditions not specified are the conventional conditions in this industry. The technical features involved in each implementation manner of the present invention can be combined with each other as long as they do not conflict with each other.

[0019] Example 1 See the appendix Figure 1 - Appendix Figure 6 , this example provides an erasable organic-inorganic hybrid patterned thin film prepared by atomic layer deposition, and the atomic layer deposition preparation includes the following steps: S1. Place a substrate on the pedestal of the reaction chamber 105 in the chemical vapor deposition process. Load the TDMAHf precursor and the MAH organic ligand into the first precursor bottle 101 and the second precursor bottle 102 respectively. The molar ratio of the inorganic metal precursor to the organic ligand is 1:5. Open the first nitrogen pressure reducing valve 201 to 0.55 MPa and the second nitrogen pressure reducing valve 202 to 0.14 MPa, which are used as power gas and carrier gas. Turn on the vacuum pump 302, evacuate the system to vacuum and heat the first precursor bottle 101 to 80 °C, the second precursor bottle 102 to 90 °C, the reaction chamber 105 to 120 °C, the inlet pipeline to 120 °C, and the outlet pipeline to 100 °C. After opening the first precursor manual valve 103 and the second precursor manual valve 104, enter the following cycle: Open the solenoid valve 203 to allow the inorganic metal precursor to enter the reaction chamber and deposit, then close the solenoid valve 203 and open the stop valve 301 to purge the excess gas. Open the solenoid valve 204 to allow the organic ligand to enter the reaction chamber and deposit, then close the solenoid valve 204 and open the stop valve 301 to purge the excess gas. After circulating 100 times, deposit a positive photoresist film on the surface of the substrate. The specific deposition sequence is MAH dose 1.0 s / dwell 30 s / exhaust 30 s / TDMAHf dose 0.2 s / dwell 20 s / exhaust 20 s. The deposition mechanism is as shown in the appendix Figure 2 as shown, and after the deposition is completed, the film as shown in the appendix Figure 3 is obtained. The AFM characterization diagram of the film is as shown in the appendix Figure 4 as shown; S2. Use an ultraviolet lithography machine to press the positive photoresist film with a thickness of 45 nm deposited on the substrate surface tightly against the mask. The light source wavelength of the ultraviolet lithography machine is 254 nm. Set the exposure dose to 600 mJ and then perform patterned exposure on the sample. The optical microscope image after exposure is as shown in the appendix Figure 5 as shown; S3. Place the patterned film on a hot plate and heat it at 50 °C for 1 min. The pattern disappears. Place the film again and adsorb it on the sample stage of the deep ultraviolet lithography machine, and control it to be tightly against the mask. Set the exposure dose to 600 mJ and then perform new patterned exposure on the sample. The optical microscope images of this process are as shown in the appendix Figure 6 as shown; S4. Immerse the exposed photoresist film sample in a 0.01% oxalic acid solution for 30 seconds, then quickly immerse the sample in ultrapure water or isopropyl alcohol for 10 seconds, and then use a high-pressure nitrogen gun to dry the surface of the sample to form a pattern.

[0020] Example 2 Refer to the appendix Figure 7 . This example provides an erasable organic-inorganic hybrid patterned film prepared by molecular layer deposition. The molecular layer deposition preparation includes the following steps: S1. Place a substrate on the pedestal in the reaction chamber of the chemical vapor deposition process. Load the TDMAHf precursor and the MAH organic ligand into the first precursor bottle and the second precursor bottle respectively. The molar ratio of the inorganic metal precursor to the organic ligand is 1:3. Open the first nitrogen pressure reducing valve to 0.55 MPa and the second nitrogen pressure reducing valve to 0.14 MPa, which are used as power gas and carrier gas. Turn on the vacuum pump, evacuate the system to vacuum and heat the first precursor bottle to 80 °C, the second precursor bottle to 90 °C, the reaction chamber to 120 °C, the inlet pipeline to 120 °C, and the outlet pipeline to 100 °C. After opening the first precursor manual valve and the second precursor manual valve, enter the following cycle: Open the first solenoid valve to allow the inorganic metal precursor to enter the reaction chamber and deposit, close the first solenoid valve and open the stop valve to purge the excess gas; Open the second solenoid valve to allow the organic ligand to enter the reaction chamber and deposit, close the second solenoid valve and open the stop valve to purge the excess gas. After circulating 100 times, a positive photoresist film is deposited on the surface of the substrate. The specific deposition sequence is MAH dose 0.6 s / hold 30 s / exhaust 30 s / TDMAHf dose 0.2 s / hold 20 s / exhaust 20 s; S2. Use an ultraviolet lithography machine to control the positive photoresist film with a thickness of 42 nm deposited on the substrate to be close to the mask. The light source wavelength of the ultraviolet lithography machine is 254 nm. Set the exposure dose to 600 mJ and perform patterned exposure on the sample; S3. Place the patterned film on a hot plate and heat it at 100 °C for 1 min and at 150 °C for 3 min, and the pattern disappears. Place the film back on and adsorb it on the sample stage of the deep ultraviolet lithography machine, and control it to be close to the mask. Set the exposure dose to 600 mJ and perform new patterned exposure on the sample. The optical microscope image of this process is as shown in the appendix Figure 7 as follows; S4. Immerse the exposed photoresist film sample in a 0.01% oxalic acid solution for 30 seconds, then quickly immerse the sample in ultrapure water or isopropyl alcohol for 10 seconds, and then use a high-pressure nitrogen gun to blow dry the surface of the sample to form a pattern.

[0021] Example 3 See appendix Figure 8 , this example provides an erasable organic-inorganic hybrid patterned film prepared by atomic layer deposition. The atomic layer deposition preparation includes the following steps: S1. Place a substrate on the pedestal in the reaction chamber of the chemical vapor deposition process. Load the TDMAHf precursor and the MAH organic ligand into the first precursor bottle and the second precursor bottle respectively. The molar ratio of the inorganic metal precursor to the organic ligand is 1:1. Open the first nitrogen pressure reducing valve to 0.55 MPa and the second nitrogen pressure reducing valve to 0.14 MPa, which are used as power gas and carrier gas. Turn on the vacuum pump, evacuate the system to vacuum and heat the first precursor bottle to 80 °C, the second precursor bottle to 90 °C, the reaction chamber to 120 °C, the inlet pipeline to 120 °C, and the outlet pipeline to 100 °C. After opening the first precursor manual valve and the second precursor manual valve, enter the following cycle: Open the first solenoid valve to allow the inorganic metal precursor to enter the reaction chamber and deposit, close the first solenoid valve and open the stop valve to purge the excess gas; Open the second solenoid valve to allow the organic ligand to enter the reaction chamber and deposit, close the second solenoid valve and open the stop valve to purge the excess gas. After circulating 100 times, a positive photoresist film is deposited on the surface of the substrate. The specific deposition sequence is MAH dose 0.2 s / dwell 30 s / exhaust 30 s / TDMAHf dose 0.2 s / dwell 20 s / exhaust 20 s; S2. Use an ultraviolet lithography machine to control the positive photoresist film with a thickness of 40 nm deposited on the substrate to be close to the mask. The light source wavelength of the ultraviolet lithography machine is 254 nm. Set the exposure dose to 600 mJ and then perform patterned exposure on the sample; S3. Place the patterned film on a hot plate and heat it at 150 °C for 5 min. The pattern disappears. Place the film again and adsorb it on the sample stage of the deep ultraviolet lithography machine, and control it to be close to the mask. Set the exposure dose to 600 mJ and then perform new patterned exposure on the sample; The optical microscope image of this process is as shown in the appendix Figure 8 as shown; S4. Immerse the exposed photoresist film sample in a 0.01% oxalic acid solution for 30 seconds, then quickly immerse the sample in ultrapure water or isopropyl alcohol for 10 seconds, and then use a high-pressure nitrogen gun to dry the surface of the sample to form a pattern.

[0022] Example 4 See appendix Figure 9 - appendix Figure 11 This example provides an erasable organic-inorganic hybrid patterned film prepared by atomic layer deposition. The atomic layer deposition preparation includes the following steps: S1. Place a substrate on the pedestal in the reaction chamber of the chemical vapor deposition process. Load the TDMAHf precursor and the MAH organic ligand into the first precursor bottle and the second precursor bottle respectively. The molar ratio of the inorganic metal precursor to the organic ligand is 1:5. Open the first nitrogen pressure regulator to 0.55 MPa and the second nitrogen pressure regulator to 0.14 MPa, which are used as power gas and carrier gas. Turn on the vacuum pump, evacuate the system to vacuum, and heat the first precursor bottle to 80 °C, the second precursor bottle to 90 °C, the reaction chamber to 120 °C, the inlet pipeline to 120 °C, and the outlet pipeline to 100 °C. After opening the first precursor manual valve and the second precursor manual valve, enter the following cycle: Open the first solenoid valve to allow the inorganic metal precursor to enter the reaction chamber and deposit, close the first solenoid valve and open the stop valve to purge the excess gas; Open the second solenoid valve to allow the organic ligand to enter the reaction chamber and deposit, close the second solenoid valve and open the stop valve to purge the excess gas. After running the cycle 100 times, a positive photoresist film is deposited on the surface of the substrate. S2. Use an ultraviolet lithography machine to press the positive photoresist film with a thickness of 40 nm deposited on the substrate surface tightly against the mask. The light source wavelength of the ultraviolet lithography machine is 254 nm. After setting the exposure dose to 600 mJ, perform patterned exposure on the sample. S3. Place the patterned film on a hot plate and heat it at 50 °C for 1 minute, and the pattern disappears. S4. Immerse the exposed photoresist film sample in a 0.01% oxalic acid solution for 30 seconds, then quickly immerse the sample in ultrapure water or isopropyl alcohol for 10 seconds, and then use a high-pressure nitrogen gun to dry the surface of the sample to form a pattern. Observe the exposed and developed sample with an optical microscope, as shown in the appendix Figure 9 shown; The FTIR images of the sample before and after exposure in this example are shown in the appendix Figure 10 shown, and the exposure mechanism is shown in the appendix Figure 11 shown.

[0023] Example 5 See the appendix Figure 12 In this example, a erasable organic-inorganic hybrid patterned film prepared by atomic layer deposition is provided. The atomic layer deposition preparation includes the following steps: S1. Place a substrate on the pedestal in the reaction chamber of the chemical vapor deposition process. Load the TDMAHf precursor and the MAH organic ligand into the first precursor bottle and the second precursor bottle respectively. The molar ratio of the inorganic metal precursor to the organic ligand is 1:5. Open the first nitrogen pressure reducing valve to 0.55 MPa and the second nitrogen pressure reducing valve to 0.14 MPa, which are used as power gas and carrier gas. Turn on the vacuum pump, evacuate the system to vacuum, and heat the first precursor bottle to 80 °C, the second precursor bottle to 90 °C, the reaction chamber to 120 °C, the inlet pipeline to 120 °C, and the outlet pipeline to 100 °C. After opening the first precursor manual valve and the second precursor manual valve, enter the following cycle: Open the first solenoid valve to allow the inorganic metal precursor to enter the reaction chamber and deposit, close the first solenoid valve and open the stop valve to purge the excess gas; Open the second solenoid valve to allow the organic ligand to enter the reaction chamber and deposit, close the second solenoid valve and open the stop valve to purge the excess gas. After circulating 100 times, a positive photoresist film is deposited on the surface of the substrate. S2. Expose the positive photoresist film with a thickness of 45 nm deposited on the surface of the substrate using an electron beam. Set the exposure dose to 400 μC and the beam current to 50 pA to perform patterned exposure on the sample. S3. Place the patterned film on a hot plate and heat it at 50 °C for 1 minute, and the pattern disappears. S4. Put the exposed photoresist film sample into a 0.01% oxalic acid solution for 30 seconds, then quickly put the sample into ultrapure water or isopropyl alcohol for infiltration for 10 seconds, and then use a high-pressure nitrogen gun to blow dry the surface of the sample to form a pattern. Observe the exposed and developed sample using a scanning electron microscope, and the resolution is at least 50 nm, as shown in the attached Figure 12 figure.

[0024] Comparative Example 1 In this comparative example, a film with a ratio of tetradimethylamino to methacrylic acid of 1:3 was deposited using chemical vapor deposition, with a thickness of 40 nm. After exposure at 254 nm with 600 mJ, no pattern was observed under optical microscopy, and the exposure could not be reversed by heating at 150 °C for 5 minutes.

[0025] Comparative Example 2 In this comparative example, a film with a ratio of tetradimethylamino to isobutyric acid of 1:3 was deposited using chemical vapor deposition, with a thickness of 40 nm. After exposure at 254 nm with 600 mJ, no pattern was observed under optical microscopy, and the exposure could not be reversed by heating at 150 °C for 5 minutes.

[0026] In summary, for the erasable organic-inorganic hybrid patterned thin film prepared by atomic layer deposition in the present invention, by alternately introducing inorganic metal precursors and organic ligands, an erasable patterned organic-inorganic hybrid thin film is self-assembled on the surface of a semiconductor substrate; this method makes full use of the self-limiting reaction characteristics of atomic layer deposition (ALD) technology to achieve precise control of film thickness and composition ratio; by optimizing the precursor pulse time and cycle number, the sensitivity and etching resistance of the thin film can be significantly improved; the film thickness of the erasable organic-inorganic hybrid patterned thin film prepared by atomic layer deposition in the present invention is precisely controllable and the surface flatness is extremely high, the surface roughness (RMS) is only 0.12 nm, and there is no need for the complex step of post-exposure baking (PEB). High-resolution patterns with a period of 100 nm and a line width of 50 nm can be achieved by electron beam lithography. This thin film can be pattern-exposed and the pattern can be erased by heating. The present invention can be patterned after exposure and is reversible by heating, and has broad application prospects and research and development value.

[0027] The above-described embodiments merely represent several implementation manners of the present invention, and the description thereof is relatively specific and detailed, but should not be construed as a limitation on the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention patent shall be subject to the appended claims.

Claims

1. An erasable organic-inorganic hybrid patterned film prepared by molecular layer deposition, characterized in that: The molecular layer deposition preparation comprises the following steps: S1. Place a substrate on the base of a reaction chamber (105) of a vapor deposition process, and load an inorganic metal precursor and an organic ligand into precursor bottle one (101) and precursor bottle two (102) respectively; open nitrogen pressure reducing valve one (201) to 0.55 MPa and nitrogen pressure reducing valve two (202) to 0.14 MPa, which are used as power gas and carrier gas; start the vacuum pump (302), evacuate the system to vacuum, and heat precursor bottle one (101) and precursor bottle two (102), the reaction chamber, the air inlet pipe, and the air outlet pipe; After opening the precursor manual valve 1 (103) and the precursor manual valve 2 (104), the following cycle is entered: the solenoid valve 1 (203) is opened to allow the inorganic metal precursor to enter the reaction chamber and be deposited, the solenoid valve 1 (203) is closed and the stop valve (301) is opened to purge the excess gas; the solenoid valve 2 (204) is opened to allow the organic ligand to enter the reaction chamber and be deposited, the solenoid valve 2 (204) is closed and the stop valve (301) is opened to purge the excess gas; after multiple cycles, a positive photoresist film is deposited on the substrate surface; S2, patterning and exposing the positive photoresist film deposited on the surface of the substrate using an ultraviolet lithography machine or an electron beam; S3, placing the patterned film on top of a heating plate and heating for 1 to 5 minutes to erase the pattern, and then repeatedly performing patterned exposure on the film; S4, placing the exposed photoresist film sample in a developer for 30 seconds, then quickly placing the sample in ultrapure water or isopropanol for 10 seconds, and then using a high-pressure nitrogen gun to blow dry the sample surface to form a pattern; Wherein, the inorganic metal precursor is selected from at least one of tetrakis(dimethylamino)hafnium and tetrakis(dimethylamino)tin; and the organic ligand is selected from at least one of maleic anhydride and maleic acid.

2. The erasable organic-inorganic hybrid patterned film prepared by molecular layer deposition according to claim 1, characterized in that: In step S1, the system is evacuated to a vacuum and the precursor bottle 1 (101) is heated to 75-85°C, the precursor bottle 2 (102) is heated to 85-95°C, the reaction chamber (105) is heated to 115-125°C, the air inlet pipe is heated to 115-125°C, and the air outlet pipe is heated to 95-105°C.

3. The erasable organic-inorganic hybrid patterned film prepared by molecular layer deposition according to claim 1, characterized in that: In step S2, the wavelength of the light source of the ultraviolet lithography machine is 254nm, and the exposure dose is 600MJ.

4. The erasable organic-inorganic hybrid patterned film prepared by molecular layer deposition according to claim 1, characterized in that: In step S2, the beam current of the electron beam is 100 pA, and the exposure dose is 400 μC.

5. The erasable organic-inorganic hybrid patterned film prepared by molecular layer deposition according to claim 1, characterized in that: In step S3, the heating temperature of heating the positive photoresist film to erase the pattern is 50-150°C.

6. The erasable organic-inorganic hybrid patterned film prepared by molecular layer deposition according to claim 1, characterized in that: In step S4, the developer is an oxalic acid solution with a mass fraction of 0.01%.

7. The erasable organic-inorganic hybrid patterned film prepared by molecular layer deposition according to claim 1, characterized in that: The molar ratio of the inorganic metal precursor to the organic ligand is 1:1-5.

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