An erasable organic-inorganic hybrid patterned thin film prepared by atomic layer deposition

Abstract

The present invention discloses an erasable organic-inorganic hybrid patterned thin film prepared by atomic layer deposition. By alternately depositing inorganic precursors and organic ligands, a high-precision and uniform hybrid photoresist thin film is formed on the surface of a substrate. The specific steps include: adopting the MLD technology, precisely controlling the film composition and thickness through vacuum deposition, gas source switching and cyclic purge processes; patterning and exposing the thin film by ultraviolet lithography or electron beam; realizing pattern erasing and rewriting through heating and re-exposure; developing with a 0.01% oxalic acid solution. The obtained thin film has ultra-low roughness (RMS 0.12 nm), high resolution - the electron beam exposure can achieve at least a 50 nm line width, and excellent etching resistance, effectively solving the problems of uneven film thickness, low sensitivity and high trial-and-error cost of traditional photoresist. The present invention simplifies the process flow, is applicable to deep ultraviolet and extreme ultraviolet lithography processes, and has important application prospects in the manufacturing of semiconductor devices.

Description

Technical Field

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

[0002] With the continuous improvement of the integration 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, the traditional method has limited control ability 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 (MLD) 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 bake (PEB) in traditional processes. Particularly, this thin film can be pattern-exposed and the pattern can be erased by heating, having broad application prospects and research value. Summary of the Invention

[0004] The purpose 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 purpose of the present invention is achieved through the following technical solutions:

[0006] An erasable organic-inorganic hybrid patterned film prepared by atomic layer deposition, and the atomic layer deposition preparation includes the following steps:

[0007] S1. Place a substrate on the pedestal of the reaction chamber (105) of the vapor deposition process, and separately load an inorganic metal precursor and an organic ligand into the first precursor bottle (101) and the second precursor bottle (102); 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, deposit a positive photoresist film on the substrate surface;

[0008] S2. Pattern and expose the positive photoresist film deposited on the substrate surface using an ultraviolet lithography machine or an electron beam.

[0009] 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.

[0010] S4. Put the exposed photoresist film sample into the developer for 30 seconds, then quickly immerse the sample in ultrapure water or isopropanol for 10 seconds, and then use a high-pressure nitrogen gun to dry the surface of the sample to form a pattern.

[0011] Preferably, the molar ratio of the inorganic metal precursor to the organic ligand is 1:1 - 5.

[0012] More preferably, the molar ratio of the inorganic metal precursor to the organic ligand is 1:1, 1:3, 1:5.

[0013] 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.

[0014] Preferably, in step S1, the system is evacuated to a vacuum and the first precursor bottle (101) is heated to 75 - 85 °C, the second precursor bottle (102) is heated to 85 - 95 °C, the reaction chamber (105) is heated to 115 - 125 °C, the inlet pipeline is heated to 115 - 125 °C, and the outlet pipeline is heated to 95 - 105 °C.

[0015] Preferably, in step S2, the light source wavelength of the ultraviolet lithography machine is 254 nm and the exposure dose is 600 MJ.

[0016] Preferably, in step S2, the beam current of the electron beam is 100 pA and the exposure dose is 400 μC.

[0017] Preferably, in step S3, the heating temperature for erasing the pattern of the positive photoresist film is 50 - 150 °C.

[0018] Preferably, in step S4, the developer is an oxalic acid solution with a mass fraction of 0.01%.

[0019] Due to the application of the above technical solution, the present invention has the following beneficial effects compared with the prior art:

[0020] 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 alternately introducing inorganic metal precursors and organic ligands through self-assembly on the surface of a semiconductor substrate. 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.

[0021] 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 pattern-exposed and the pattern can be erased by heating. The present invention is patternable after exposure and heating-reversible, and has broad application prospects and research and development value. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] 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.

[0023] Figure 1 It is a schematic diagram of the molecular layer deposition device in Embodiment 1 of the present invention;

[0024] Figure 2 It is a schematic diagram of the molecular layer deposition mechanism of TDMAHf and MAH in Embodiment 1 of the present invention;

[0025] Figure 3 It is the thin film obtained after 100 cycles in Embodiment 1 of the present invention;

[0026] Figure 4 It is an AFM characterization diagram of the thin film obtained after 100 cycles in Embodiment 1 of the present invention;

[0027] Figure 5 It is a light microscope image of the patterned exposure of the thin film in Embodiment 1 of the present invention;

[0028] Figure 6 It is a light microscope image of the patterning and erasing / rewriting process of TDMAHf:MAH = 1:5 in Embodiment 1 of the present invention;

[0029] Figure 7 It is a light microscope image of the patterning and erasing / rewriting process of TDMAHf:MAH = 1:3 in Embodiment 2 of the present invention;

[0030] Figure 8 It is a light microscope image of the patterning and erasing / rewriting process of TDMAHf:MAH = 1:1 in Embodiment 3 of the present invention;

[0031] Figure 9 It is an optical microscope image after DUV exposure and development in Embodiment 4 of the present invention;

[0032] Figure 10 It is an infrared spectrum diagram of the photoresist thin film before and after exposure in Embodiment 4 of the present invention;

[0033] Figure 11 It is a schematic diagram of the exposure mechanism in Embodiment 4 of the present invention;

[0034] Figure 12 It is an SEM image after electron beam exposure and development in Embodiment 5 of the present invention;

[0035] Among them, in the attached Figure 1 101 - Precursor bottle one; 102 - Precursor bottle two; 103 - Precursor manual valve one; 104 - Precursor manual valve two; 105 - Reaction chamber; 201 - Nitrogen pressure reducing valve one; 202 - Nitrogen pressure reducing valve two; 203 - Solenoid valve one; 204 - Solenoid valve two; 301 - Stop valve; 302 - Vacuum pump. Detailed implementation manners

[0036] For a clearer understanding of the technical features, objectives, and effects of the present invention, the specific implementation manners are now described in detail.

[0037] The present invention will be further described below in conjunction with 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 use, and 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.

[0038] Example 1

[0039] See attached Figure 1 - attached Figure 6 , this embodiment provides an erasable organic-inorganic hybrid patterned film prepared by atomic layer deposition. The atomic layer deposition preparation includes the following steps:

[0040] S1. Place a substrate on the base of the reaction chamber 105 of the 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, 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, close the solenoid valve 204 and open the stop valve 301 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 1.0 s / hold 30 s / exhaust 30 s / TDMAHf dose 0.2 s / hold 20 s / exhaust 20 s; The deposition mechanism is as shown in attached Figure 2 shown. After the deposition is completed, the film shown in attached Figure 3 is obtained, and the AFM characterization diagram of the film is as shown in attached Figure 4 shown;

[0041] S2. Use an ultraviolet lithography machine to control the positive photoresist film with a film thickness of 45 nm deposited on the surface of the substrate to be close to the mask plate. The light source wavelength of the ultraviolet lithography machine is 254 nm, and the exposure dose is set to 600 mJ, and then pattern exposure is performed on the sample. The optical microscope image after exposure is as shown in attached Figure 5 shown;

[0042] S3. Place the patterned thin film on a hot plate and heat it at 50 °C for 1 min. The pattern disappears. Then place the thin film again and adsorb it on the sample stage of the deep ultraviolet lithography machine, and control it to be closely attached to the mask plate. Set the exposure dose to 600 mJ and then perform new patterning exposure on the sample. The optical microscope images of this process are shown in Appendix Figure 6 as follows;

[0043] S4. Immerse the exposed photoresist thin 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.

[0044] Example 2

[0045] See Appendix Figure 7 , this example provides an erasable organic-inorganic hybrid patterned thin film prepared by atomic layer deposition. The atomic layer deposition preparation includes the following steps:

[0046] S1. Place a substrate on the pedestal of the reaction chamber of the 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 thin 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;

[0047] S2. Use a ultraviolet lithography machine to control the positive photoresist thin film with a film thickness of 42 nm deposited on the surface of the substrate to be closely attached to the mask plate. The light source wavelength of the ultraviolet lithography machine is 254 nm. Set the exposure dose to 600 mJ and then perform patterning exposure on the sample.

[0048] S3. Place the patterned thin film on a heating plate and heat it at 100 °C for 1 minute and at 150 °C for 3 minutes. The pattern disappears. Then place the thin film again and adsorb it on the sample stage of a deep ultraviolet lithography machine, and control it to be close to the mask plate. Set the exposure dose to 600 mJ and then perform new patterning exposure on the sample. The optical microscope images of this process are shown in the appendix Figure 7 as follows;

[0049] S4. Immerse the exposed photoresist thin 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.

[0050] Example 3

[0051] See the appendix Figure 8 , this example provides an erasable organic-inorganic hybrid patterned thin film prepared by atomic layer deposition. The atomic layer deposition preparation includes the following steps:

[0052] S1. Place a substrate on the pedestal of the reaction chamber of the 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 thin 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;

[0053] S2. Use a ultraviolet lithography machine to control the positive photoresist thin film with a film thickness of 40 nm deposited on the surface of the substrate to be close to the mask plate. The light source wavelength of the ultraviolet lithography machine is 254 nm. Set the exposure dose to 600 mJ and then perform patterning exposure on the sample.

[0054] S3. Place the patterned film on a hot plate and heat it at 150 °C for 5 min until the pattern disappears. Then place the film again and adsorb it on the sample stage of a deep ultraviolet lithography machine, and control it to be close to the mask plate. After setting the exposure dose to 600 mJ, perform new patterning exposure on the sample. The optical microscope images of this process are shown in Appendix Figure 8 as follows;

[0055] 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.

[0056] Example 4

[0057] 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:

[0058] S1. Place a substrate on the pedestal of the reaction chamber of the 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 running the cycle 100 times, deposit a positive photoresist film on the surface of the substrate;

[0059] S2. Use a ultraviolet lithography machine to pattern the positive photoresist film with a thickness of 40 nm deposited on the surface of the substrate and control it to be close to the mask plate. The light source wavelength of the ultraviolet lithography machine is 254 nm. After setting the exposure dose to 600 mJ, perform patterning exposure on the sample;

[0060] S3. Place the patterned film on a hot plate and heat it at 50 °C for 1 min until the pattern disappears;

[0061] S4. Place the exposed photoresist thin film sample in a 0.01% oxalic acid solution for 30 seconds, then quickly immerse the sample in ultrapure water or isopropanol 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 an optical microscope, as shown in the appendix Figure 9 as shown; the FTIR images of the sample before and after exposure are shown in the appendix Figure 10 as shown, and the exposure mechanism is shown in the appendix Figure 11 as shown.

[0062] Example 5

[0063] Refer to the appendix Figure 12 . This example provides an erasable organic-inorganic hybrid patterned thin film prepared by atomic layer deposition. The atomic layer deposition preparation includes the following steps:

[0064] S1. Place a substrate on the pedestal in the reaction chamber of the 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, deposit a positive photoresist thin film on the surface of the substrate;

[0065] S2. Expose the positive photoresist thin 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;

[0066] S3. Place the patterned thin film on a hot plate and heat it at 50 °C for 1 minute, and the pattern disappears;

[0067] S4. Place the exposed photoresist thin film sample in a 0.01% oxalic acid solution for 30 seconds, then quickly immerse the sample in ultrapure water or isopropanol 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 with a resolution of at least 50 nm, as shown in the appendix Figure 12 as shown.

[0068] Comparative Example 1

[0069] This comparative example uses the vapor deposition method to deposit a thin film with a ratio of tetradimethylamino to methacrylic acid of 1:3, with a thickness of 40 nm. After exposure at 254 nm for 600 mJ, no pattern was observed under a light microscope, and the reversal of exposure could not be achieved by heating at 150 °C for 5 minutes.

[0070] Comparative Example 2

[0071] This comparative example uses the vapor deposition method to deposit a thin film with a ratio of tetradimethylamino to isobutyric acid of 1:3, with a thickness of 40 nm. After exposure at 254 nm for 600 mJ, no pattern was observed under a light microscope, and the reversal of exposure could not be achieved by heating at 150 °C for 5 minutes.

[0072] In summary, for the erasable organic-inorganic hybrid patterned thin film prepared by molecular layer deposition of the present invention, by alternately introducing an inorganic metal precursor and an organic ligand, an erasable patterned organic-inorganic hybrid thin film is self-assembled on the surface of the semiconductor substrate; 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 the number of cycles, 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 molecular layer deposition of the present invention is precisely controllable and the surface flatness is extremely high, with a surface roughness (RMS) of 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 thin film can be pattern-exposed and the pattern can be erased by heating. The present invention can be pattern-exposed after exposure and is reversible by heating, having broad application prospects and research and development value.

[0073] The above-described embodiments merely represent several implementation manners of the present invention, and their descriptions are relatively specific and detailed, but they should not be construed as limiting 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 invention patent should be subject to the appended claims.

Claims

1. A preparation method of an erasable organic-inorganic hybrid patterned film prepared by atomic layer deposition, characterized in that, The molecular layer deposition preparation includes the following steps: S1. Place a substrate on the pedestal of the reaction chamber (105) of the vapor deposition process. Load the inorganic metal precursor and the 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 substrate surface; S2. Patternwise expose the positive photoresist film deposited on the substrate surface 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 patternwise exposure of the film; S4. Immerse the exposed photoresist film sample in the developer for 30 seconds, then quickly immerse the sample in ultrapure water or isopropanol for 10 seconds, and then use a high-pressure nitrogen gun to blow dry the surface of the sample to form a pattern; Among them, the inorganic metal precursor is selected from at least one of hafnium tetrakis(dimethylamino) and tin tetrakis(dimethylamino); the organic ligand is selected from at least one of maleic anhydride and maleic acid.

2. The preparation method of an erasable organic-inorganic hybrid patterned thin film prepared by atomic layer deposition according to claim 1, characterized in that, 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.

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

4. The preparation method of an erasable organic-inorganic hybrid patterned thin film prepared by atomic 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 preparation method of an erasable organic-inorganic hybrid patterned thin film prepared by atomic layer deposition according to claim 1, characterized in that, In step S3, the heating temperature for erasing the pattern of the positive photoresist film is 50 - 150 °C.

6. The preparation method of an erasable organic-inorganic hybrid patterned thin film prepared by atomic 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 preparation method of an erasable organic-inorganic hybrid patterned thin film prepared by atomic 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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