Hydrophobic conductive film, preparation method therefor, and use thereof

Abstract

A hydrophobic conductive film (10), a preparation method therefor, and a use thereof, relating to the technical field of semiconductor preparation. The method comprises the following steps: 1) performing a pre-zincation treatment on a surface of a substrate (20), and forming a saturated zinc atom layer (11); 2) alternately feeding a zinc precursor and an oxygen precursor into a reaction chamber and introducing an inert gas for purging, and growing a zinc oxide film layer (12) on a surface of the saturated zinc atom layer (11); 3) performing a post-zincation treatment on the zinc oxide film layer (12) to form a zincated transition layer (13); 4) performing a fluorination post-treatment on the zincated transition layer (13) and forming a zinc fluoride surface layer (14). The prepared hydrophobic conductive film (10) has the characteristics of strong hydrophobicity, good adhesion to the substrate, high film reliability, good film density, precise and controllable thickness, good film uniformity, high step coverage, and high optical transmittance. Compared with microstructures, the hydrophobic conductive film has greater stability, is compatible with various semiconductor packaging processes, effectively resists environmental interference, and can be applied in various hydrophobic scenarios.

Description

A hydrophobic conductive film and its preparation method and application Technical Field

[0001] The present application belongs to the field of semiconductor preparation technology, and specifically relates to a hydrophobic conductive film and its preparation method and application. Background Art

[0002] A hydrophobic surface refers to a surface with a water contact angle greater than 90°. Hydrophobic surfaces have many excellent properties, such as waterproof and antifreeze, antibacterial and self-cleaning, corrosion resistance, and oil-water separation, and have potential application value in many fields.

[0003] Traditional methods for preparing hydrophobic surfaces include sol-gel method, microstructure processing, etc., but they have the following problems: 1) The sol-gel method of film formation usually uses dipping method and spin coating method. The uniformity of the thin films prepared by these two methods is poor, and the film needs to be dried or baked after formation, which can easily cause cracking or deformation of the film, and the film-base bonding is poor and easy to fall off. 2) When preparing hydrophobic surfaces through microstructure processing, semiconductor processes such as photolithography and etching are usually required, which have high requirements for equipment precision (line width, conformality, etc.). Due to the need for hydrophobicity, the microstructure surface cannot be encapsulated / protected, so it is extremely easy to be damaged in most application scenarios and cannot maintain high reliability. For some special optical devices, the surface micro-nanostructure will affect the optical performance of the device. 3) The hydrophobic film is deposited using chemical vapor deposition (CVD) and atomic layer deposition (ALD) technology, but the hydrophobicity is poor and cannot be realized in most hydrophobic application scenarios.

[0004] Summary of the Invention

[0005] In response to the above-mentioned problems existing in the prior art, the first technical problem to be solved by the present invention is to provide a method for preparing a hydrophobic conductive film; the second technical problem to be solved by the present invention is to provide a hydrophobic conductive film prepared by this method; the third technical problem to be solved by the present invention is to provide an application of the hydrophobic conductive film.

[0006] In order to solve the above problems, the present invention provides the following technical solutions:

[0007] In a first aspect, a method for preparing a hydrophobic conductive film comprises the following steps:

[0008] 1) performing zincation pretreatment on the substrate surface in a vacuum and high-temperature reaction chamber to form a zinc atom saturated layer;

[0009] 2) alternately introducing a zinc precursor and an oxygen precursor into the reaction chamber and purging with an inert gas to grow a zinc oxide thin film on the surface of the zinc atom saturated layer;

[0010] 3) performing zinc post-treatment on the zinc oxide film layer to form a zinc transition layer;

[0011] 4) The zinc transition layer is subjected to fluorination post-treatment to form a zinc fluoride surface layer.

[0012] In one embodiment of the present application, in step 1), the temperature of the reaction chamber is raised to 100-300° C., and a vacuum pump is used to maintain the reaction chamber in a vacuum state, and the substrate is placed in the reaction chamber.

[0013] In one embodiment of the present application, in step 1), the pressure of the reaction chamber is maintained in a vacuum state of 0 to 5 torr.

[0014] In one embodiment of the present application, in step 1), the substrate is first preheated in the reaction chamber to reach the desired reaction temperature.

[0015] In one embodiment of the present application, in step 1), the zincation pre-treatment includes circulating the zinc precursor into the reaction chamber through an inert gas multiple times.

[0016] In one embodiment of the present application, in step 1), when the substrate surface is pre-treated for zincification, the temperature of the zinc precursor is 10-30°C, and an inert gas with a flow rate of 10-100 sccm, such as N2, is introduced into the precursor as a carrier gas, with a pulse time of 5-20 s and a purge time of 10-20 s. The process is repeated for 30-50 cycles.

[0017] In one embodiment of the present application, in step 1), when the substrate surface is pre-treated for zincification, the temperature of the zinc precursor is 10 to 30°C, and an inert gas with a flow rate of 10 to 100 sccm, such as N2, is introduced into the precursor as a carrier gas. The pulse time is 10 to 20 seconds, the purge time is 10 to 15 seconds, and the process is repeated for 30 to 40 cycles.

[0018] In one embodiment of the present application, in step 1), during zincation pretreatment of the substrate surface, the temperature of the zinc precursor is 22° C., and an inert gas, such as N 2 , is introduced into the precursor as a carrier gas at 40 sccm with a pulse time of 10 seconds and a purge time of 15 seconds. This process is repeated for 40 cycles. The zinc precursor is selected from Zn(DMP) 2 , ZnCl 2 , ZnMe 2 , ZnEt 2 , or derivatives thereof.

[0019] In one embodiment of the present application, zincation pre-treatment is performed on the substrate surface to increase the adsorption saturation of the first atomic layer to reach a state of supersaturation of zinc atoms.

[0020] In one embodiment of the present application, in step 2), a periodic atomic layer deposition process is used to prepare the zinc oxide thin film.

[0021] In one embodiment of the present application, in step 2), when the zinc oxide thin film is prepared by a periodic atomic layer deposition process, three preparation methods are included: DI-H2O-ALD, O2-Plasma-ALD or O3-ALD.

[0022] In one embodiment of the present application, in step 2), a zinc precursor using an inert gas as a carrier gas and an oxygen precursor using an inert gas as a carrier gas are alternately introduced into the surface of the zinc atom saturated layer, and an inert gas is introduced between the alternately introduced zinc precursor and oxygen precursor for purging.

[0023] In one embodiment of the present application, in step 2), a zinc precursor using an inert gas as a carrier gas is sequentially introduced into the surface of the zinc atom saturated layer, followed by an oxygen precursor using an inert gas as a carrier gas, and the introduction is performed alternately until a zinc oxide film of a specified thickness is grown.

[0024] In one embodiment of the present application, in step 2), an oxygen precursor with an inert gas as a carrier gas is sequentially introduced into the surface of the zinc atom saturated layer, followed by a zinc precursor with an inert gas as a carrier gas, and the introduction is alternated until a zinc oxide film of a specified thickness is grown.

[0025] In one embodiment of the present application, in step 2), 10 to 200 sccm of inert gas is introduced to remove excess zinc precursor or oxygen precursor for a time of 1 to 20 seconds.

[0026] In one embodiment of the present application, in step 2), the inert gas may be selected from nitrogen and argon.

[0027] In one embodiment of the present application, in step 2), the zinc precursor is selected from one of Zn(DMP)2, ZnCl2, ZnMe2, ZnEt2 or their derivatives.

[0028] In one embodiment of the present application, in step 2), an inert gas and a zinc precursor are introduced into the reaction chamber, and then the excess zinc precursor is purged with the inert gas and pumped out by a vacuum pump.

[0029] In one embodiment of the present application, in step 2), an inert gas such as N2 is used as a carrier gas, and a zinc precursor such as ZnEt2, Zn(DMP)2, ZnCl2 or ZnMe2 is introduced into the reaction chamber with a set pulse duration of 0.1 to 2s. The temperature of the zinc precursor is 10 to 30°C, and the zinc precursor is purged with an inert gas for 5 to 25s, and the reaction chamber is evacuated by a vacuum pump.

[0030] In one embodiment of the present application, in step 2), an inert gas such as N2 is used as a carrier gas, and a zinc precursor such as ZnEt2, Zn(DMP)2, ZnCl2 or ZnMe2 is introduced into the reaction chamber with a set pulse duration of 0.1 to 1 s. The temperature of the zinc precursor is 10 to 30°C, and the zinc precursor is purged with an inert gas for 5 to 15 s, and the reaction chamber is evacuated by a vacuum pump.

[0031] In one embodiment of the present application, in step 2), an inert gas such as N2 is used as a carrier gas, and a zinc precursor such as ZnEt2, Zn(DMP)2, ZnCl2 or ZnMe2 is introduced into the reaction chamber with a set pulse duration of 0.3s. The temperature of the zinc precursor is 22°C, and the zinc precursor is purged with an inert gas for 10s, and the reaction chamber is evacuated by a vacuum pump.

[0032] The user can adaptively adjust the introduction parameters according to the specific zinc precursor such as its derivatives introduced.

[0033] In one embodiment of the present application, in step 2), the oxygen precursor is selected from one of DI-H2O, O2-Plasma or O3.

[0034] In one embodiment of the present application, in step 2), when the oxygen precursor is DI-H2O, the temperature of DI-H2O is maintained at 10-30°C, and the pulse time of DI-H2O is 0.1-2s.

[0035] In one embodiment of the present application, in step 2), when the oxygen precursor is DI-H2O, DI-H2O is introduced into the reaction chamber, so that the substrate is exposed to the atmosphere of the zinc precursor and then DI-H2O, and ZnO is generated through chemical reaction. Then, an inert auxiliary gas is used to purge and remove excess side reactants, and the gas is evacuated by a vacuum pump to form a first layer of hydrophobic conductive film.

[0036] In one embodiment of the present application, after forming the first layer of hydrophobic conductive film, a zinc oxide monolayer of a fixed thickness is continuously deposited until a zinc oxide thin film layer is formed.

[0037] In one embodiment of the present application, in step 2), when the oxygen precursor is O2-Plasma, the flow rate of O2-Plasma is 100-200 sccm, and the pulse time of O2-Plasma is 5-15 s.

[0038] In one embodiment of the present application, in step 2), when the oxygen precursor is O2-Plasma, ionized O2-Plasma is introduced into the reaction chamber, so that the substrate is exposed to the atmosphere of the zinc precursor and then the O2-Plasma, and ZnO is generated through chemical reactions. Then, an inert auxiliary gas is used to purge and remove excess side reactants, and the gas is pumped out by a vacuum pump to form a first layer of hydrophobic conductive film.

[0039] In one embodiment of the present application, after forming the first layer of hydrophobic conductive film, a zinc oxide monolayer of a fixed thickness is continuously deposited until a zinc oxide thin film layer is formed.

[0040] In one embodiment of the present application, in step 2), when the oxygen precursor is O3, the flow rate of O3 is 100-300 sccm, and the pulse time of O3 is 2-10 s.

[0041] In one embodiment of the present application, in step 2), when the oxygen precursor is O3, O3 is introduced into the reaction chamber, so that the substrate is exposed to the atmosphere of the zinc precursor and then O3, and ZnO is generated through chemical reaction. Then, an inert auxiliary gas is used to blow away excess side reactants, and the gas is pumped out by a vacuum pump to form a first layer of hydrophobic conductive film.

[0042] In one embodiment of the present application, after forming the first layer of hydrophobic conductive film, a zinc oxide monolayer of a fixed thickness is continuously deposited until a zinc oxide thin film layer is formed.

[0043] In one embodiment of the present application, a zinc oxide thin film layer is accumulated layer by layer on the surface of the substrate using a zinc precursor and deionized water DI-H2O / oxygen plasma O2-Plasma / ozone O3 under the coordinated action of source temperature, chamber temperature, chamber pressure and the flow rate of carrier gas in each pipeline.

[0044] In one embodiment of the present application, in step 3), during the zincation post-treatment, the zinc precursor is introduced through the first carrier gas, the temperature of the zinc precursor is 10-30°C, the pulse time of the zinc precursor is 0.1-1s, the number of cycles is 10-30 cycles, and the flow rate of the first carrier gas is 10-100 sccm.

[0045] In one embodiment of the present application, in step 3), during the zincation post-treatment, the zinc precursor is introduced through the first carrier gas, the temperature of the zinc precursor is 24° C., the pulse time of the zinc precursor is 0.3 s, the number of cycles is 20 cycles, and the flow rate of the first carrier gas is 30 sccm.

[0046] In one embodiment of the present application, in step 3), the first carrier gas is an inert gas, which can be selected from nitrogen or argon.

[0047] In one embodiment of the present application, in step 3), the prepared zinc oxide thin film layer is subjected to zincification post-treatment, which can effectively increase the surface roughness of the last atomic layer of ZnO, form a fluorinated transition layer, and increase the adhesion of the fluorinated layer.

[0048] In one embodiment of the present application, in step 4), during the fluorination post-treatment, the fluorine precursor is introduced through a second carrier gas, the flow rate of the second carrier gas is 10 to 100 sccm, the pulse time of the fluorine precursor is 0.1 to 2 s, and the number of cycles is 20 to 40 cycles.

[0049] In one embodiment of the present application, in step 4), during the fluorination post-treatment, the fluorine precursor is introduced through a second carrier gas, the flow rate of the second carrier gas is 30 to 100 sccm, the pulse time of the fluorine precursor is 0.5 to 2 s, and the number of cycles is 30 to 40 cycles.

[0050] In one embodiment of the present application, in step 4), during the fluorination post-treatment, the fluorine precursor is introduced through a second carrier gas, the flow rate of the second carrier gas is 60 sccm, the pulse time of the fluorine precursor is 1 s, and the number of cycles is 40 cycles.

[0051] In one embodiment of the present application, in step 4), the fluorine precursor includes TIF4 or a derivative thereof.

[0052] In one embodiment of the present application, in step 4), the second carrier gas is an inert gas, which can be selected from nitrogen or argon.

[0053] In a second aspect of one embodiment of the present application, a hydrophobic conductive film prepared by the above method comprises, from bottom to top, a zinc atom saturated layer, a zinc oxide film layer, a zinc transition layer and a zinc fluoride surface layer.

[0054] In one embodiment of the present application, the thickness of the hydrophobic conductive film is 5 to 50 nm.

[0055] In one embodiment of the present application, the thickness of the hydrophobic conductive film is 10 to 40 nm.

[0056] In one embodiment of the present application, the thickness of the hydrophobic conductive film is 40 nm.

[0057] In one embodiment of the present application, the hydrophobic conductive film is a hydrophobic conductive film with a thickness of 40 nm and made of O3 as an oxygen precursor.

[0058] In a third aspect, a composite substrate includes a substrate and a hydrophobic conductive film composited on a surface of the substrate.

[0059] In a fourth aspect, the use of the hydrophobic conductive film or the composite substrate in the preparation of electronic components also falls within the protection scope of the present invention.

[0060] Compared with the prior art, the present invention has the following beneficial effects:

[0061] (1) The present invention discloses a method for forming a ZnO hydrophobic conductive film on a substrate based on an atomic layer deposition (ALD) process. First, the substrate is subjected to zincation pretreatment to effectively increase the adsorption saturation of the first atomic layer, thereby increasing the heterogeneity of the ZnO film generated by the reaction and increasing the hydrophobicity of the ZnO film. Then, by rationally utilizing zinc precursors and deionized water (DI-H2O) / oxygen plasma (O2-Plasma) / ozone (O3), under the coordinated effects of source temperature, cavity temperature, cavity pressure and the flow of carrier gases in each pipeline, a zinc oxide film of a desired precise thickness is accumulated layer by layer on the surface of the substrate. The prepared zinc oxide film is further subjected to the conditions of the above conditions. The film is subjected to zincation post-treatment, which effectively increases the surface roughness of the last atomic layer of ZnO and forms a fluorinated transition layer, which not only effectively improves the hydrophobicity of the ZnO film, but also helps to improve the fluorination degree of the ZnO film after subsequent fluorination post-treatment and increase the adhesion of the fluorinated layer; finally, surface fluorination post-treatment is performed. Unlike traditional chemical fluorination reactions, this application uses ALD to perform surface fluorination treatment, and performs fluorine substitution reaction on the supersaturated Zn atoms on the surface, which effectively increases the hydrophobicity of the sample surface; at the same time, the formed film layer has a smaller band gap, making it easier for electrons in the valence band to jump to the conduction band, thereby having better conductivity.

[0062] (2) The hydrophobic conductive film prepared in the present application is produced based on the ALD method. The ZnO film prepared by this method has the characteristics of strong hydrophobicity, good film-base bonding (not easy to fall off), high film reliability (no warping, cracking or deformation), good film density, precise and controllable thickness, good film uniformity, high step coverage, and high optical transmittance (small extinction coefficient k). Compared with microstructures, it has stronger stability, is compatible with various semiconductor packaging processes, effectively resists environmental interference, can be applied to a variety of hydrophobic scenarios without affecting the optical performance of the device. For precision devices with water-free process requirements, O2-Plasma-ALD and / or O3-ALD processes can be used for processing. BRIEF DESCRIPTION OF THE DRAWINGS

[0063] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following is a brief introduction to the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are 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.

[0064] FIG1 is a schematic structural diagram of the hydrophobic conductive film prepared in this application;

[0065] FIG2 is a schematic structural diagram of the composite substrate prepared in this application;

[0066] FIG3 is a schematic diagram of a contact angle test of the hydrophobic conductive film prepared in Example 2;

[0067] FIG4 is a schematic diagram of a contact angle test of the hydrophobic conductive film prepared in Example 3;

[0068] FIG5 is a schematic diagram of a contact angle test of the hydrophobic conductive film prepared in Example 4;

[0069] FIG6 is a schematic diagram showing contact angle measurements of hydrophobic conductive films of different thicknesses obtained in Example 2;

[0070] FIG7 is a schematic diagram showing contact angle measurements of hydrophobic conductive films of different thicknesses obtained in Example 3;

[0071] FIG8 is a schematic diagram of contact angle testing of hydrophobic conductive films of different thicknesses prepared in Example 4. DETAILED DESCRIPTION

[0072] The following will be combined with the drawings in the embodiments of this application to clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the embodiments described are only part of the embodiments of this application, not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without making creative efforts are within the scope of protection of this application.

[0073] As used herein, "ranges" are defined in terms of lower and upper limits. A given range is defined by selecting a lower limit and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive and may be combined arbitrarily, i.e., any lower limit may be combined with any upper limit to form a range.

[0074] Example 1

[0075] A method for forming a ZnO hydrophobic conductive thin film on a substrate based on an atomic layer deposition (ALD) process:

[0076] First, the reaction chamber is raised to 100-200°C; then the substrate is placed in the reaction chamber and preheated for 100-1000 seconds to heat the substrate to the reaction temperature; the substrate is pre-treated for zincification, the zinc precursor is maintained at a temperature of 10-30°C, and an inert gas with 10-100 sccm is introduced into the precursor as a carrier gas, with a pulse time of 5-20 seconds and a purge time of 10-20 seconds. The process is repeated for 30-50 cycles. Then, an inert gas is used as a carrier gas to introduce a zinc precursor into the reaction chamber with a set pulse duration of 0.1 to 2 seconds, and the zinc precursor is purged with an inert gas for 5 to 25 seconds, and the reaction chamber is evacuated by a vacuum pump; deionized water (DI-H2O) or O2-Plasma (power 500 to 1500W) or O3 precursor is continued to be introduced into the reaction chamber to form Thermal ZnO or PE-ZnO or O3-ZnO, and then an inert gas is used to purge and remove excess side reactants, and the reaction chamber is evacuated by a vacuum pump to form the first layer of zinc oxide film; finally, a zinc oxide film layer is obtained by periodic growth. Next, the prepared zinc oxide film is subjected to zincification post-treatment, the zinc precursor is maintained at a temperature of 10 to 30°C, and an inert gas with a flow rate of 10 to 100 sccm is introduced into the precursor as a carrier gas with a pulse time of 0.1 to 1 second, and 10 to 30 cycles are repeated. Finally, the ZnO film that has completed the zincation treatment is subjected to fluorination post-treatment, and a fluorine precursor is introduced into the precursor through 10 to 100 sccm of inert gas as a carrier gas, with a pulse time of 0.1 to 2 seconds, and repeated 20 to 40 cycles to obtain a hydrophobic conductive film.

[0077] The inert gas may be selected from nitrogen and argon. The zinc precursor may be selected from Zn(DMP)2, ZnCl2, ZnMe2, ZnEt2 or derivatives thereof.

[0078] FIG1 shows a schematic structural diagram of a hydrophobic conductive film 10 prepared in the present application, which includes, from bottom to top, a zinc atom saturated layer 11 , a zinc oxide film layer 12 , a zincated transition layer 13 and a zinc fluoride surface layer 14 .

[0079] Figure 2 shows a schematic structural diagram of the composite substrate prepared in the present application, which includes a substrate 20 and a hydrophobic conductive film 10 composited on the surface of the substrate. The hydrophobic conductive film 10 includes a zinc atom saturated layer 11, a zinc oxide film layer 12, a zinc transition layer 13 and a zinc fluoride surface layer 14.

[0080] Example 2

[0081] A method for forming a ZnO hydrophobic conductive thin film on a substrate based on an atomic layer deposition (ALD) process:

[0082] First, the reaction chamber is raised to 200°C; then the substrate is placed in the reaction chamber and preheated for 600s to heat the substrate to the reaction temperature; the substrate is pre-treated for zincification, the zinc precursor is maintained at a temperature of 22°C, and 40sccm of inert gas N2 is introduced into the precursor as a carrier gas with a pulse time of 10s and a purge time of 15s. This process is repeated 40 times. Then, using N2 as a carrier gas, the zinc precursor ZnEt2 is introduced into the reaction chamber with a set pulse length of 0.3s, and the zinc precursor is purged with N2 for 10s. The reaction chamber is then evacuated by a vacuum pump; deionized water (DI-H2O) precursor is continued to be introduced into the reaction chamber to form Thermal ZnO, and then N2 is used to purge to remove excess side reactants, and the reaction chamber is evacuated by a vacuum pump to form the first layer of zinc oxide film; finally, a zinc oxide film layer is obtained through periodic growth. The prepared zinc oxide film then underwent a zincification post-treatment. The zinc precursor was maintained at 24°C and an inert gas was introduced into the precursor at 30 sccm as a carrier gas with a pulse duration of 0.3 seconds. This was repeated for 20 cycles. Finally, the zincified ZnO film underwent a fluorination post-treatment. The fluorine precursor, TiF4, was introduced into the precursor with a 60 sccm inert gas as a carrier gas with a pulse duration of 1 second. This was repeated for 40 cycles to produce a hydrophobic conductive film.

[0083] Example 3

[0084] A method for forming a ZnO hydrophobic conductive thin film on a substrate based on an atomic layer deposition (ALD) process:

[0085] First, the reaction chamber is raised to 200°C; then the substrate is placed in the reaction chamber and preheated for 600s to heat the substrate to the reaction temperature; the substrate is pre-treated for zincification, the zinc precursor is maintained at a temperature of 22°C, and 40sccm of inert gas N2 is introduced into the precursor as a carrier gas, with a pulse time of 10s and a purge time of 15s. This process is repeated 40 times. Then, using N2 as a carrier gas, the zinc precursor ZnEt2 is introduced into the reaction chamber with a set pulse duration of 0.3s, and the zinc precursor is purged with N2 for a purge time of 10s, and the reaction chamber is evacuated by a vacuum pump; O2-Plasma (power 500-1500W) is continued to be introduced into the reaction chamber with a set pulse duration (8-12s), and Ar is purged for 10s. The excess reaction gas is evacuated by a vacuum pump to form the first layer of PE-ZnO film; finally, a zinc oxide film layer is obtained by periodic growth. The prepared zinc oxide film then underwent a zincification post-treatment. The zinc precursor was maintained at 24°C and an inert gas was introduced into the precursor at 30 sccm as a carrier gas with a pulse duration of 0.3 seconds. This was repeated for 20 cycles. Finally, the zincified ZnO film underwent a fluorination post-treatment. The fluorine precursor, TiF4, was introduced into the precursor with a 60 sccm inert gas as a carrier gas with a pulse duration of 1 second. This was repeated for 40 cycles to produce a hydrophobic conductive film.

[0086] Example 4

[0087] A method for forming a ZnO hydrophobic conductive thin film on a substrate based on an atomic layer deposition (ALD) process:

[0088] First, the reaction chamber is heated to 200°C; then the substrate is placed in the reaction chamber and preheated for 600s to heat the substrate to the reaction temperature; the substrate is pre-treated for zincification, the zinc precursor is maintained at a temperature of 22°C, and 40sccm of inert gas N2 is introduced into the precursor as a carrier gas, with a pulse time of 10s and a purge time of 15s. This process is repeated 40 times. Then, using N2 as a carrier gas, the zinc precursor ZnEt2 is introduced into the reaction chamber with a set pulse duration of 0.3s, and the zinc precursor is purged with N2 for a purge time of 10s, and the reaction chamber is evacuated by a vacuum pump; O3 (power 60%, O3-flow rate 150-200sccm) is continued to be introduced into the reaction chamber with a set pulse duration (2-8s), and N2 is purged for 10s. The excess reaction gas is evacuated by a vacuum pump to form the first layer of O3-ZnO thin film; finally, a zinc oxide thin film layer is obtained by periodic growth. The prepared zinc oxide film then underwent a zincification post-treatment. The zinc precursor was maintained at 24°C and an inert gas was introduced into the precursor at 30 sccm as a carrier gas with a pulse duration of 0.3 seconds. This was repeated for 20 cycles. Finally, the zincified ZnO film underwent a fluorination post-treatment. The fluorine precursor, TiF4, was introduced into the precursor with a 60 sccm inert gas as a carrier gas with a pulse duration of 1 second. This was repeated for 40 cycles to produce a hydrophobic conductive film.

[0089] Comparative Example 1

[0090] First, the reaction chamber is raised to 200°C; then the substrate is placed in the reaction chamber and preheated for 600 seconds to heat the substrate to the reaction temperature; using N2 as a carrier gas, the zinc precursor ZnEt2 is introduced into the reaction chamber with a set pulse duration of 0.3 seconds, and the zinc precursor is purged with N2 for 10 seconds, and the reaction chamber is evacuated by a vacuum pump; deionized water (DI-H2O) precursor is continued to be introduced into the reaction chamber to form Thermal ZnO, and then N2 is used to purge to remove excess side reactants, and the reaction chamber is evacuated by a vacuum pump to form the first layer of zinc oxide film; finally, the zinc oxide film layer is obtained through periodic growth.

[0091] Comparative Example 2

[0092] First, the reaction chamber is raised to 200°C; then the substrate is placed in the reaction chamber and preheated for 600s to heat the substrate to the reaction temperature; the substrate is pre-treated for zincification, the zinc precursor is maintained at a temperature of 22°C, and 40sccm of inert gas N2 is introduced into the precursor as a carrier gas with a pulse time of 10s and a purge time of 15s. This process is repeated 40 times. Then, using N2 as a carrier gas, the zinc precursor ZnEt2 is introduced into the reaction chamber with a set pulse length of 0.3s, and the zinc precursor is purged with N2 for 10s. The reaction chamber is then evacuated by a vacuum pump; deionized water (DI-H2O) precursor is continued to be introduced into the reaction chamber to form Thermal ZnO, and then N2 is used to purge to remove excess side reactants, and the reaction chamber is evacuated by a vacuum pump to form the first layer of zinc oxide film; finally, a zinc oxide film layer is obtained through periodic growth.

[0093] Comparative Example 3

[0094] First, the reaction chamber is raised to 200°C; then the substrate is placed in the reaction chamber and preheated for 600s to heat the substrate to the reaction temperature; the substrate is pre-treated for zincification, the zinc precursor is maintained at a temperature of 22°C, and 40sccm of inert gas N2 is introduced into the precursor as a carrier gas with a pulse time of 10s and a purge time of 15s. This process is repeated 40 times. Then, using N2 as a carrier gas, the zinc precursor ZnEt2 is introduced into the reaction chamber with a set pulse length of 0.3s, and the zinc precursor is purged with N2 for 10s. The reaction chamber is then evacuated by a vacuum pump; deionized water (DI-H2O) precursor is continued to be introduced into the reaction chamber to form Thermal ZnO, and then N2 is used to purge to remove excess side reactants, and the reaction chamber is evacuated by a vacuum pump to form the first layer of zinc oxide film; finally, a zinc oxide film layer is obtained through periodic growth. Next, the prepared zinc oxide film was subjected to zincation post-treatment, wherein the zinc precursor was maintained at a temperature of 24° C., and an inert gas with a flow rate of 30 sccm was introduced into the precursor as a carrier gas with a pulse time of 0.3 s. This cycle was repeated 20 times to obtain a zinc oxide film subjected to zincation post-treatment.

[0095] Comparative Example 4

[0096] First, the reaction chamber is raised to 200°C; then the substrate is placed in the reaction chamber and preheated for 600 seconds to heat the substrate to the reaction temperature; using N2 as a carrier gas, the zinc precursor ZnEt2 is introduced into the reaction chamber with a set pulse duration of 0.3 seconds, and the zinc precursor is purged with N2 for 10 seconds, and the reaction chamber is evacuated by a vacuum pump; O2-Plasma (power 500-1500W) is continued to be introduced into the reaction chamber with a set pulse duration (8-12 seconds), and Ar is used to purge for 10 seconds. The excess reaction gas is evacuated by a vacuum pump to form the first layer of PE-ZnO film; finally, a zinc oxide film layer is obtained through periodic growth.

[0097] Comparative Example 5

[0098] First, the reaction chamber is raised to 200°C; then the substrate is placed in the reaction chamber and preheated for 600s to heat the substrate to the reaction temperature; the substrate is pre-treated for zincification, the zinc precursor is maintained at a temperature of 22°C, and 40sccm of inert gas N2 is introduced into the precursor as a carrier gas, with a pulse time of 10s and a purge time of 15s. This process is repeated 40 times. Then, using N2 as a carrier gas, the zinc precursor ZnEt2 is introduced into the reaction chamber with a set pulse duration of 0.3s, and the zinc precursor is purged with N2 for a purge time of 10s, and the reaction chamber is evacuated by a vacuum pump; O2-Plasma (power 500-1500W) is continued to be introduced into the reaction chamber with a set pulse duration (8-12s), and Ar is purged for 10s. The excess reaction gas is evacuated by a vacuum pump to form the first layer of PE-ZnO film; finally, a zinc oxide film layer is obtained by periodic growth.

[0099] Comparative Example 6

[0100] First, the reaction chamber is raised to 200°C; then the substrate is placed in the reaction chamber and preheated for 600s to heat the substrate to the reaction temperature; the substrate is pre-treated for zincification, the zinc precursor is maintained at a temperature of 22°C, and 40sccm of inert gas N2 is introduced into the precursor as a carrier gas, with a pulse time of 10s and a purge time of 15s. This process is repeated 40 times. Then, using N2 as a carrier gas, the zinc precursor ZnEt2 is introduced into the reaction chamber with a set pulse duration of 0.3s, and the zinc precursor is purged with N2 for a purge time of 10s, and the reaction chamber is evacuated by a vacuum pump; O2-Plasma (power 500-1500W) is continued to be introduced into the reaction chamber with a set pulse duration (8-12s), and Ar is purged for 10s. The excess reaction gas is evacuated by a vacuum pump to form the first layer of PE-ZnO film; finally, a zinc oxide film layer is obtained by periodic growth. The prepared zinc oxide film was then subjected to zincification post-treatment. The zinc precursor was maintained at 24° C., and an inert gas with a flow rate of 30 sccm as a carrier gas was introduced into the precursor with a pulse time of 0.3 s. This was repeated for 20 cycles to obtain a zinc oxide film subjected to zincification post-treatment.

[0101] Comparative Example 7

[0102] First, the reaction chamber is raised to 200°C; then the substrate is placed in the reaction chamber and preheated for 600s to heat the substrate to the reaction temperature; using N2 as a carrier gas, the zinc precursor ZnEt2 is introduced into the reaction chamber with a set pulse duration of 0.3s, and the zinc precursor is purged with N2 for 10s, and the reaction chamber is evacuated by a vacuum pump; O3 (power 60%, O3-flow rate 150-200sccm) is continued to be introduced into the reaction chamber with a set pulse duration (2-8s), and N2 is used to purge for 10s. The excess reaction gas is evacuated by a vacuum pump to form the first layer of O3-ZnO thin film; finally, a zinc oxide thin film layer is obtained through periodic growth.

[0103] Comparative Example 8

[0104] First, the reaction chamber is heated to 200°C; then the substrate is placed in the reaction chamber and preheated for 600s to heat the substrate to the reaction temperature; the substrate is pre-treated for zincification, the zinc precursor is maintained at a temperature of 22°C, and 40sccm of inert gas N2 is introduced into the precursor as a carrier gas, with a pulse time of 10s and a purge time of 15s. This process is repeated 40 times. Then, using N2 as a carrier gas, the zinc precursor ZnEt2 is introduced into the reaction chamber with a set pulse duration of 0.3s, and the zinc precursor is purged with N2 for a purge time of 10s, and the reaction chamber is evacuated by a vacuum pump; O3 (power 60%, O3-flow rate 150-200sccm) is continued to be introduced into the reaction chamber with a set pulse duration (2-8s), and N2 is purged for 10s. The excess reaction gas is evacuated by a vacuum pump to form the first layer of O3-ZnO thin film; finally, a zinc oxide thin film layer is obtained by periodic growth.

[0105] Comparative Example 9

[0106] First, the reaction chamber is heated to 200°C; then the substrate is placed in the reaction chamber and preheated for 600s to heat the substrate to the reaction temperature; the substrate is pre-treated for zincification, the zinc precursor is maintained at a temperature of 22°C, and 40sccm of inert gas N2 is introduced into the precursor as a carrier gas, with a pulse time of 10s and a purge time of 15s. This process is repeated 40 times. Then, using N2 as a carrier gas, the zinc precursor ZnEt2 is introduced into the reaction chamber with a set pulse duration of 0.3s, and the zinc precursor is purged with N2 for a purge time of 10s, and the reaction chamber is evacuated by a vacuum pump; O3 (power 60%, O3-flow rate 150-200sccm) is continued to be introduced into the reaction chamber with a set pulse duration (2-8s), and N2 is purged for 10s. The excess reaction gas is evacuated by a vacuum pump to form the first layer of O3-ZnO thin film; finally, a zinc oxide thin film layer is obtained by periodic growth. The prepared zinc oxide film was then subjected to zincification post-treatment. The zinc precursor was maintained at 24° C., and an inert gas with a flow rate of 30 sccm as a carrier gas was introduced into the precursor with a pulse time of 0.3 s. This was repeated for 20 cycles to obtain a zinc oxide film subjected to zincification post-treatment.

[0107] The test results of the contact angles of the films prepared in Examples 2 to 4 and Comparative Examples 1 to 9 (films with a thickness of 40 nm were selected for testing) are shown in Table 1 below.

[0108] The contact angle is tested using the sessile drop method, which is done with an optical contact angle meter. A droplet is placed on the film sample, the image of the droplet is captured by a high-resolution camera, and the angle is then automatically measured by the software.

[0109] Table 1 Contact angles of 40 nm films obtained in different embodiments and comparative examples

[0110] Figures 3 to 5 are schematic diagrams of contact angle tests of the hydrophobic conductive films prepared in Examples 2 to 4, respectively. When the film thickness is 40 nm, the contact angles are 119.59°, 120.16°, and 122.74°, respectively.

[0111] FIG6 to FIG8 are schematic diagrams showing contact angle tests of hydrophobic conductive films of different thicknesses prepared in Examples 2 to 4, respectively. As can be seen from the figures, as the film thickness grows from 10 nm to 40 nm, its hydrophobic property becomes better.

[0112] The test results of the sheet resistance Rs and resistivity P of the thin films (40 nm) prepared in Example 4 and Comparative Example 9 are shown in Table 2 below.

[0113] A digital four-probe tester is used to test the sheet resistance and resistivity of thin films. The digital four-probe tester consists of a host computer, a test bench, a four-probe probe, and a computer. The measured data can be displayed directly by the host computer or controlled by the computer to collect test data for analysis. The test results are then statistically analyzed and displayed in a table format.

[0114] At room temperature, place the film sample on the sample stage of a four-probe tester. Manually adjust the probes and press them down onto the sample surface. After calibration, measure the sheet resistance of the film. Calculate the corresponding resistivity from the sheet resistance.

[0115] Table 2 Effect of fluorination post-treatment on the square resistance Rs and resistivity P of the film

[0116] It can be seen from the data in Table 2 that the conductivity of the film is significantly increased after fluorination treatment.

[0117] It can be seen from the data in Tables 1 and 2 that the 40 nm thin film prepared by O3 growth method and zincation pre-treatment, zincation post-treatment and fluorination post-treatment has excellent hydrophobicity and conductive properties.

[0118] It should also be noted that, in this document, relational terms such as first and second are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "include," "comprises," or any other variations thereof are intended to cover non-exclusive inclusion.

[0119] The present application has been described in detail above with reference to specific embodiments and exemplary examples. However, these descriptions should not be construed as limiting the present application. Those skilled in the art will appreciate that, without departing from the spirit and scope of the present application, various equivalent substitutions, modifications, or improvements may be made to the technical solutions and implementations of the present application, all of which fall within the scope of the present application. The scope of protection of the present application shall be determined by the appended claims.

Claims

1. A hydrophobic conductive film, characterized in that: The hydrophobic conductive film (10) comprises, from bottom to top, a zinc atom saturated layer (11), a zinc oxide film layer (12), a zinc transition layer (13) and a zinc fluoride surface layer (14).

2. A method for preparing the hydrophobic conductive film according to claim 1, characterized in that: The following steps are involved: 1) Pre-treating the substrate surface to form a zinc atom saturated layer; 2) Alternately introducing a zinc precursor and an oxygen precursor into the reaction chamber, and introducing an inert gas for purging, so as to grow a zinc oxide thin film layer on the surface of the zinc atom saturated layer; 3) performing zinc post-treatment on the zinc oxide film layer to form a zinc transition layer; 4) Post-fluorination treatment is performed on the zinc-plated transition layer to form a zinc fluoride surface layer.

3. The method for preparing a hydrophobic conductive film according to claim 2, characterized in that: In step 1), when the substrate surface is pre-treated for zincation, the temperature of the zinc precursor is 10-30° C., the pulse time of the zinc precursor is 5-20 s, and the number of cycles is 30-50 cycles.

4. The method for preparing a hydrophobic conductive film according to claim 2, characterized in that: In step 2), a zinc precursor with an inert gas as a carrier gas and an oxygen precursor with an inert gas as a carrier gas are alternately introduced into the reaction chamber, and an inert gas is introduced between the alternately introduced zinc precursor and oxygen precursor for purging, so that a zinc oxide thin film layer grows on the surface of the zinc atom saturated layer.

5. The method for preparing a hydrophobic conductive film according to claim 2 or claim 3 or claim 4, characterized in that: The zinc precursor is selected from one of Zn(DMP)2, ZnCl2, ZnMe2, ZnEt2 or their derivatives.

6. The method for preparing a hydrophobic conductive film according to claim 2, characterized in that: In step 2), the oxygen precursor is selected from one of DI-H2O, O2-Plasma or O3.

7. The method for preparing a hydrophobic conductive film according to claim 6, characterized in that: When the oxygen precursor is DI-H2O, the temperature of DI-H2O is maintained at 10-30°C, and the pulse time of DI-H2O is 0.1-2s; when the oxygen precursor is O2-Plasma, the flow rate of O2-Plasma is 100-200sccm, and the pulse time of O2-Plasma is 5-15s; when the oxygen precursor is O3, the flow rate of O3 is 100-300sccm, and the pulse time of O3 is 2-10s.

8. The method for preparing a hydrophobic conductive film according to claim 2, characterized in that: In step 3), during zincation post-treatment, the zinc precursor is introduced through the first carrier gas, the temperature of the zinc precursor is 10-30° C., the pulse time of the zinc precursor is 0.1-1 s, and the number of cycles is 10-30 cycles.

9. The method for preparing a hydrophobic conductive film according to claim 2, characterized in that: In step 4), during the fluorination post-treatment, the fluorine precursor is introduced through the second carrier gas, the pulse time of the fluorine precursor is 0.1 to 2 seconds, and the number of cycles is 20 to 40 cycles.

10. The method for preparing a hydrophobic conductive film according to claim 2, characterized in that: The thickness of the hydrophobic conductive film is 5 to 50 nm.

11. The method for preparing a hydrophobic conductive film according to claim 10, characterized in that: The thickness of the hydrophobic conductive film is 10-40 nm.

12. A composite substrate comprising the hydrophobic conductive film according to claim 1, characterized in that: The composite substrate comprises a substrate (20) and a hydrophobic conductive film (10) composited on the surface of the substrate (20).

13. Use of the hydrophobic conductive film according to claim 1 or the composite substrate according to claim 12 in the preparation of electronic components.

Images