Method for regulating and controlling hydrophilicity of metal oxide film layer, composite film layer and application

Abstract

The invention provides a method for regulating and controlling the hydrophilicity of a metal oxide film layer, a composite film and application, the hydrophilicity of the metal oxide film layer is regulated and controlled by depositing an organic metal compound film layer, and the method specifically comprises the following steps: depositing the organic metal compound film layer on a substrate; depositing a metal oxide film layer on the surface of the organic metal compound film layer; the organic metal compound film layer is obtained through molecular layer deposition. According to the invention, the organic metal compound film layer is deposited on the lower layer of the metal oxide film layer to regulate and control the hydrophilicity of the metal oxide film layer, and the addition of the organic metal compound film layer can especially improve the hydrophilicity of the metal oxide film layer. Furthermore, the hydrophilic performance of the metal oxide film layer can be further optimized by regulating and controlling the deposition temperature and thickness of the organic metal compound film layer and the thickness of the metal oxide film layer.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional thin films, and in particular relates to a method for regulating the hydrophilicity of a metal oxide film layer, a composite film layer and applications. Background Art

[0002] The contact angle of a liquid on the surface of a solid material is an important parameter to measure the wettability of the liquid on the surface of the material. If the test liquid is deionized water, when the contact angle of deionized water on the surface of the solid material is less than 90°, the solid surface is hydrophilic, that is, the liquid is easier to wet the solid, and the smaller the angle, the better the wettability; if the contact angle is greater than 90°, the solid surface is hydrophobic, that is, the liquid is not easy to wet the solid and is easy to move on the surface, and the larger the angle, the better the hydrophobicity.

[0003] In many fields, the contact angle of the coating has a direct impact on the performance of the device. For example, in the field of solar cells, the self-cleaning ability of the battery panel is improved by developing hydrophobic coatings, that is, high contact angle materials. Specifically, when rain falls on the panel, the water droplets will roll off, taking away dust and other pollutants, reducing the surface energy of the battery panel and also reducing maintenance costs. Another example is in the field of medical devices. Evenly attaching a hydrophilic coating on the surface of medical devices can reduce the friction resistance generated when contacting with human tissue, reduce the damage to blood vessels and cavity tissues caused by the intervention of medical devices, and reduce the inflammation caused.

[0004] Currently, mature methods used for contact angle adjustment include: using different plasmas, using different plasma RF power sources to process the film surface, photolithography to form specific nanoscale microstructures on the film surface, or coating specific materials.

[0005] The problems faced by the above-mentioned method of adjusting the contact angle of the film layer include: when plasma chemically treating the surface of the film layer, it is necessary to consider whether the underlying material of the device can withstand the plasma bombardment treatment; when photolithography forms a specific nanoscale structure on the surface of the film layer, it is also necessary to consider whether the underlying material can withstand the structure of this band without being destroyed, as well as the cost of photolithography equipment in advanced processes; when coating a specific material, due to the limitations of the physical properties of the material itself, a single material cannot achieve the purpose of adjustable contact angle, and it is difficult to achieve precise control of the thickness of the film layer through coating, which affects the overall performance of the device. Summary of the invention

[0006] The purpose of the present invention is to provide a method for adjusting the contact angle of a metal oxide film layer. The method of the present invention can achieve precise control of the contact angle of the hydrophilicity of a single material film layer, and has obvious advantages in market applications compared to other methods of adjusting film materials, adding end groups, changing growth methods, etc.

[0007] The present invention provides a method for regulating the hydrophilicity of a metal oxide film layer, wherein the hydrophilicity of the metal oxide film layer is regulated by first depositing an organic metal compound film layer, and specifically comprises:

[0008] Depositing an organic metal compound film layer on a substrate, and then depositing a metal oxide film layer on the surface of the organic metal compound film layer;

[0009] The organic metal compound film layer is obtained by molecular layer deposition.

[0010] Preferably, the metal oxide film layer is obtained by atomic layer deposition, specifically comprising:

[0011] a) placing a substrate with an organic metal compound film layer deposited thereon in a reaction chamber, introducing an organic metal precursor with a pulse time of t1;

[0012] b) Pass protective gas to purge for time t2;

[0013] c) introducing oxygen source, pulse time t3;

[0014] d) Pass protective gas to purge for time t4;

[0015] Step a) to step d) constitute one cycle, and the metal oxide film layer can be obtained by performing multiple cycles.

[0016] Preferably, the atomic layer deposition temperature is 10 to 350° C.;

[0017] The t1 is 0.5 to 10 s, t2 is 5 to 100 s, t3 is 0.5 to 10 s, t4 is 5 to 180 s; and the number of cycles is 10 to 200.

[0018] Preferably, the metal in the organometallic precursor includes one or more of aluminum, zinc, tin, titanium, hafnium, zirconium and nickel;

[0019] The protective gas includes nitrogen and / or argon; the oxygen source includes water vapor and / or ozone.

[0020] Preferably, the method for regulating the hydrophilicity of the metal oxide film layer further comprises:

[0021] The hydrophilicity of the metal oxide film layer is regulated by regulating the film thickness of the metal oxide, and the thickness of the metal oxide film layer is 1 to 30 nm.

[0022] Preferably, the organometallic compound film layer is obtained according to the following molecular layer deposition steps:

[0023] A) placing the substrate in a reaction chamber and introducing an organometallic precursor with a pulse time of T1;

[0024] B) Pass protective gas to purge for T2 time;

[0025] C) introducing an oxidative organic precursor, with a pulse time of T3;

[0026] D) Pass protective gas to purge for T4 time;

[0027] Step A) to step D) constitute one cycle, and the organic metal compound film layer can be obtained by performing multiple cycles.

[0028] Preferably, the temperature of the molecular layer deposition is 60-300° C.; T1 is 0.5-10 s, T2 is 5-100 s, T3 is 0.5-10 s, and T4 is 5-180 s; and the number of cycles is 1-2000 times.

[0029] Preferably, the metal in the organometallic precursor includes one or more of aluminum, zinc, tin, titanium, hafnium, zirconium and nickel;

[0030] The protective gas includes nitrogen and / or argon;

[0031] The oxidative organic precursor includes C1-C5 alcohol.

[0032] Preferably, the thickness of the organic metal compound film layer is 5 to 200 nm.

[0033] Preferably, the contact angle of the metal oxide film layer is 0 to 20°.

[0034] Preferably, the substrate is made of a hard substrate or a flexible substrate.

[0035] The invention provides a composite membrane layer with adjustable hydrophilicity, which is prepared according to the preparation method described above.

[0036] The present invention provides the method as described above or the application of the composite membrane layer as described above in the field of hydrogen production by electrolysis of water.

[0037] Preferably, the diaphragm used in hydrogen production by water electrolysis is used as a substrate, and an organic zinc film layer and a zinc oxide film layer are sequentially deposited on the surface of the diaphragm using the method described above.

[0038] Preferably, the material of the diaphragm is polyphenylene sulfide, polysulfone, polyetheretherketone, polytetrafluoroethylene or polytetrafluoroethylene modified asbestos.

[0039] The present invention provides the method as described above or the use of the composite film layer as described above in the field of medical devices.

[0040] Preferably, the method described above is used to sequentially deposit an organic aluminum film layer and an aluminum oxide film layer on the surface of the medical device.

[0041] Preferably, the medical device is made of metal, polymer, rubber material or cellulose material.

[0042] The present invention provides the use of the method or the composite membrane layer as described above in the biological field, and the biological field includes biosensors and / or artificial joints.

[0043] Preferably, the method described above is used to sequentially deposit an organic zinc film layer and a zinc oxide film layer on the surface of the biosensor.

[0044] Preferably, the method described above is used to sequentially deposit an organic aluminum film layer and an aluminum oxide film layer on the surface of the artificial joint.

[0045] The present invention provides a method for regulating the hydrophilicity of a metal oxide film layer, wherein the hydrophilicity of the metal oxide film layer is regulated by first depositing an organic metal compound film layer, specifically comprising: depositing an organic metal compound film layer on a substrate, and then depositing a metal oxide film layer on the surface of the organic metal compound film layer; the organic metal compound film layer is obtained by molecular layer deposition. The present invention regulates the hydrophilicity of the metal oxide film layer by depositing an organic metal compound film layer on the lower layer of the metal oxide film layer, and the addition of the organic metal compound film layer can especially improve the hydrophilicity of the metal oxide film layer.

[0046] Furthermore, by adjusting the deposition temperature and thickness of the organic metal compound film layer and the thickness of the metal oxide film layer, the hydrophilicity of the metal oxide film layer can be further optimized. According to the experimental results, the method of the present invention can adjust the contact angle of the metal oxide film layer to 0-20°.

[0047] Furthermore, when the metal precursor used in molecular layer deposition and the metal precursor used in atomic layer deposition are precursors of the same metal, the composite film layer has better bonding strength, mechanical properties and other properties than the composite film layer prepared using precursors of different metals.

[0048] The method of the present invention is suitable for low-temperature deposition, and is not only suitable for hard substrates such as silicon and metal, but also for flexible substrates such as organic polymers. Therefore, the method of the present invention has a wide range of applications, such as being applied to the field of hydrogen production by electrolysis of water, especially to the surface of a polyphenylene sulfide diaphragm, to improve the hydrophilicity of the polyphenylene sulfide diaphragm, and to reduce the surface resistance and power loss of the diaphragm; being applied to the field of medical devices, especially to the surface of interventional medical devices, to reduce the friction resistance generated when in contact with human tissue, and to reduce tissue damage and inflammation; being applied to the biological field, such as biosensors and artificial joints, to improve the anti-fouling ability of biosensors, enhance the reliability and stability of biosensors, and to improve the lubricity of artificial joints, reduce the friction coefficient, avoid joint wear, and increase the service life. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.

[0050] Figure 1 A schematic diagram of molecular layer deposition of an organic metal compound film layer in one embodiment of the present invention;

[0051] Figure 2 Schematic diagram of molecular layer deposition of an organometallic compound film layer in another embodiment of the present invention. DETAILED DESCRIPTION

[0052] The present invention provides a method for regulating the hydrophilicity of a metal oxide film layer, wherein the hydrophilicity of the metal oxide film layer is regulated by first depositing an organic metal compound film layer, and specifically comprises:

[0053] Depositing an organic metal compound film layer on a substrate, and then depositing a metal oxide film layer on the surface of the organic metal compound film layer;

[0054] The organic metal compound film layer is obtained by molecular layer deposition.

[0055] The present invention adjusts the contact angle of the metal oxide film layer by adding an organic metal compound film layer under the metal oxide film layer. Experimental results show that after adding the organic metal compound film layer, the contact angle of the metal oxide surface is significantly reduced, that is, the hydrophilicity is increased. Further, according to the research of the present invention, the contact angle of the metal oxide film layer can be optimized and adjusted by adjusting the deposition temperature of the organic metal compound film layer and the thickness of the organic metal compound film layer.

[0056] Specifically, the reaction principle of organometallic compounds at different temperatures is as follows Figures 1-2 As shown, when the deposition temperature of the molecular layer deposition organic metal compound is greater than 200°C, the precursor reaction mechanism is as follows Figure 1 As shown; when the deposition temperature is less than 200 ° C, the precursor reaction mechanism appears Figure 2 The reaction shown, and Figure 1 and Figure 2 The two modes coexist, tending to Figure 2 The trend described. Figures 1-2Here, M represents a metal element, O represents an oxygen element, and n represents the number of carbon atoms, which is greater than or equal to 2 and is a positive integer. Therefore, different deposition temperatures of the organometallic compound lead to different reaction principles of the organometallic compound MxCyOz during the deposition process, which further leads to different atomic ratios x, y, and z, different nano-level roughness of the film surface, and different nano-level atomic structures of the organometallic compound, thereby achieving contact angle regulation of the organometallic compound.

[0057] Specifically, in molecular layer deposition, organic metal compound film layers of different growth thicknesses affect the surface roughness of the film layers. When the film thickness is small, the top end groups of the compounds on the film surface are relatively upright. When the film thickness is thicker, the top end groups will be tilted, thereby increasing the surface roughness. Increased roughness will increase hydrophilicity, thereby achieving control of the contact angle of organic metal compounds.

[0058] In the present invention, the organometallic compound film layer is prepared by molecular layer deposition (MLD), and the specific steps are as follows:

[0059] A) placing the substrate in a reaction chamber and introducing an organometallic precursor with a pulse time of T1;

[0060] B) Pass protective gas to purge for T2 time;

[0061] C) introducing an oxidative organic precursor, with a pulse time of T3;

[0062] D) Pass protective gas to purge for T4 time;

[0063] Step A) to step D) constitute one cycle, and the organic metal compound film layer can be obtained by performing multiple cycles.

[0064] In the present invention, the substrate is not particularly limited and can be a hard substrate or a flexible substrate, and can be selected according to application requirements, such as semiconductor materials such as single crystal silicon, metals, organic polymers, etc.

[0065] In the present invention, the metal in the organometallic precursor preferably includes one or more of aluminum, zinc, tin, titanium, hafnium, zirconium and nickel, and the organometallic precursor is preferably one or more of trimethylaluminum, diethylzinc, titanium tetrachloride, tetrakis(ethylmethylamino)hafnium, tetrakis(ethylmethylamino)zirconium, tetrakis(dimethylamino)tin and bis(dimethylamino-2-methyl-2-butoxy)nickel; the oxidizing organic precursor is preferably a C1-C5 alcohol, more preferably one or more of ethylene glycol, glycerol and n-butanol; the protective gas is preferably nitrogen and / or argon.

[0066] In the present invention, the temperature of the molecular layer deposition is preferably 60 to 300°C, more preferably 80 to 250°C, and most preferably 100 to 200°C, such as 60°C, 80°C, 100°C, 120°C, 140°C, 150°C, 160°C, 180°C, 200°C, 220°C, 240°C, 250°C, 260°C, 280°C, 300°C, preferably with any of the above values ​​as the upper or lower limit of the range; T1 is preferably 0.5 to 10s, more preferably 1 to 8 s, such as 0.5s, 1s, 2s, 3s, 4s, 5s, 6s, 7s, 8s, 9s, 10s, preferably a range value with any of the above values ​​as the upper or lower limit; T2 is preferably 5 to 100s, more preferably 10 to 80s, such as 5s, 10s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 100s, preferably a range value with any of the above values ​​as the upper or lower limit; T3 is 0.5 to 10s, more preferably 3 to 8 s, such as 0.5s, 1s, 2s, 3s, 4s, 5s, 6s, 7s, 8s, 9s, 10s, preferably a range value with any of the above values ​​as the upper or lower limit; T4 is preferably 5 to 180s, more preferably 20 to 150s, such as 5s, 10s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 100s, 110s, 120s, 130s, 140s, 150s, 160s, 170s, 180s s, preferably a range value with the above arbitrary numerical value as the upper or lower limit; the number of cycles is preferably 1 to 2000 times, more preferably 50 to 1500 times, most preferably 100 to 1000 times, such as 1 time, 50 times, 100 times, 150 times, 200 times, 250 times, 300 times, 400 times, 500 times, 600 times, 700 times, 800 times, 900 times, 1000 times, 1500 times, 2000 times, preferably a range value with the above arbitrary numerical value as the upper or lower limit.

[0067] In the present invention, the thickness of the organic metal compound film layer is preferably 5 to 200 nm.

[0068] After the organic metal compound film layer is obtained by molecular layer deposition, the present invention uses atomic layer deposition (ALD) to deposit a metal oxide film layer on the surface of the organic metal compound film layer. The specific steps are as follows:

[0069] a) placing a substrate with an organic metal compound film layer deposited thereon in a reaction chamber, introducing an organic metal precursor with a pulse time of t1;

[0070] b) Pass protective gas to purge for time t2;

[0071] c) introducing oxygen source, pulse time t3;

[0072] d) Pass protective gas to purge for time t4;

[0073] Step a) to step d) constitute one cycle, and the metal oxide film layer can be obtained by performing multiple cycles.

[0074] In the present invention, the organometallic precursor is preferably one or more of trimethylaluminum, diethylzinc, titanium tetrachloride, tetrakis(ethylamino)hafnium, tetrakis(ethylamino)zirconium, tetrakis(dimethylamino)tin and bis(dimethylamino-2-methyl-2-butoxy)nickel; the protective gas is preferably nitrogen and / or argon; the oxygen source is preferably water vapor and / or ozone, more preferably water vapor. The use of water vapor does not increase the burden on the equipment on the one hand, and on the other hand, water vapor has better three-dimensional shape retention. The t1 is 0.5-10s, more preferably 1-8s, such as 0.5s, 1s, 2s, 3s, 4s, 5s, 6s, 7s, 8s, 9s, 10s, preferably a range value with any of the above values ​​as the upper or lower limit; t2 is 5-100s, more preferably 10-80s, such as 5s, 10s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 100s, preferably a range value with any of the above values ​​as the upper or lower limit; t3 is 0.5-10s, more preferably 3-8s, such as 0.5s, 1s, 2s, 3s, 4s, 5s, 6s, 7s, 8s, 9s, 10s, preferably a range value with any of the above values ​​as the upper or lower limit; t4 is 5-180s, more preferably 10-180s, such as 10s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 100s, preferably a range value with any of the above values ​​as the upper or lower limit; The duration of the cycle is preferably 20 to 150 s, such as 5 s, 10 s, 20 s, 30 s, 40 s, 50 s, 60 s, 70 s, 80 s, 90 s, 100 s, 110 s, 120 s, 130 s, 140 s, 150 s, 160 s, 170 s, 180 s, and the duration of the cycle is preferably 10 to 200 times, more preferably 50 to 180 times, such as 10 times, 20 times, 30 times, 40 times, 50 times, 60 times, 70 times, 80 times, 90 times, 100 times, 110 times, 120 times, 130 times, 140 times, 150 times, 160 times, 170 times, 180 times, 190 times, 200 times, and the duration of the cycle is preferably 10 to 200 times, more preferably 50 to 180 times, such as 10 times, 20 times, 30 times, 40 times, 50 times, 60 times, 70 times, 80 times, 90 times, 100 times, 110 times, 120 times, 130 times, 140 times, 150 times, 160 times, 170 times, 180 times, 190 times, 200 times, and the duration of the cycle is preferably 10 to 200 times,

[0075] In the present invention, the types of metal elements in the organic metal precursor used in the molecular layer deposition of the organic metal compound film layer and the organic metal precursor used in the atomic layer deposition of the metal oxide film layer can be the same or different. In an embodiment of the present invention, it is preferred to use organic metal precursors with the same type of metal elements for molecular layer deposition of the organic metal compound film layer and atomic layer deposition of the metal oxide film layer. When the same metal precursor is used for atomic layer deposition and molecular layer deposition, the bonding strength, mechanical properties and other aspects of the prepared composite film layer are better than those of the composite film layer prepared using precursors of different metals.

[0076] Further, according to the research of the present invention, when the organic metal compound film layer is determined, the contact angle of the metal oxide film layer can be further optimized and regulated by regulating the thickness of the metal oxide film layer. Specifically, under the premise that the composition and thickness of the organic metal compound film layer are constant and the metal oxide film layer is within a certain thickness range, the contact angle of the metal oxide film layer decreases as the thickness of the metal oxide film layer increases, that is, the hydrophilicity increases accordingly. According to the embodiment of the present application, when the thickness of the organic aluminum film layer is 70nm, the thickness of the aluminum oxide film layer increases from 1nm to 10nm, and the contact angle of the aluminum oxide film layer surface decreases from 29.44° to 3.92°, which has a significant effect on the hydrophilicity regulation.

[0077] The present invention also provides a composite membrane layer with adjustable hydrophilicity, which is prepared according to the preparation method described above.

[0078] The composite film layer in the present invention includes an organic metal compound film layer in contact with a substrate and a metal oxide film layer composited on the surface of the organic metal compound film layer. The composite film layer in the present invention can regulate the hydrophilicity of the metal oxide film layer by setting the organic metal compound film layer. At the same time, the hydrophilicity of the metal oxide film layer can be further regulated between 0 and 20° by controlling the process conditions of the metal oxide film layer.

[0079] The present invention also provides an application of the method described above or the composite membrane layer described above in the field of hydrogen production by electrolysis of water.

[0080] In the production of hydrogen by alkaline water electrolysis, the diaphragm used is mainly a polymer substrate, such as polyphenylene sulfide, polysulfone, polyetheretherketone, polytetrafluoroethylene or polytetrafluoroethylene modified asbestos. Polyphenylene sulfide has excellent heat resistance, good mechanical properties, corrosion resistance and good dimensional stability, and occupies more than 90% of the market share. However, polyphenylene sulfide itself has poor hydrophilicity, and bubbles are easily gathered on the surface of the diaphragm electrolyte, resulting in increased resistance and reduced efficiency of the electrolyzer. The present application applies the above-mentioned method for regulating the hydrophilicity of the metal oxide film layer to the diaphragm substrate, and the organic-inorganic hybrid membrane, such as the organic zinc + zinc oxide composite film layer, is prepared in the pores and surfaces of the polymer diaphragm by combining ALD (atomic layer deposition) and MLD (molecular layer deposition). Different process temperatures can be used for deposition according to the type of polymer diaphragm. By regulating the process temperature and deposition thickness, a hydrophilic layer with a controllable contact angle can be formed in the pores and / or on the surface of the polymer substrate, which can improve the hydrophilicity of the final product diaphragm and reduce the surface resistance of the diaphragm, thereby reducing the energy consumption of the electrolyzer and improving the electrolysis efficiency. The diaphragm has good three-dimensional shape retention performance, and has little effect on porosity while optimizing the polymer pore hydrophilicity and resistivity, which is beneficial to reducing the energy consumption of the electrolyzer. At the same time, the use of organic zinc + zinc oxide composite film can meet the resistance requirements.

[0081] Specifically, the diaphragm can be placed in a coating chamber and preheated according to the type and size of the diaphragm. First, a certain thickness of organic zinc is deposited according to the molecular layer deposition method (MLD) described above, and then a certain thickness of zinc oxide is deposited according to the atomic layer deposition method (ALD) described above to prepare a hybrid film with certain hydrophilicity and conductivity.

[0082] In the present invention, the electrolysis of water to produce hydrogen comprises electrodes, a diaphragm and an electrolyte, and the surface of the diaphragm is preferably prepared with a composite film layer on the surface of the diaphragm according to the method for regulating the hydrophilicity of the metal oxide film layer as described above.

[0083] In the present invention, the electrode includes a current collector and a catalyst coated on the surface of the current collector, which is divided into a cathode electrode and an anode electrode. The electrodes can all be electrodes commonly used in the field of alkaline water electrolysis to produce hydrogen, such as electrodes that can be commonly used precious metals, alloy electrodes or composite electrodes, the precious metal materials are usually Pt, Pd, the alloy electrodes can be nickel-based alloy electrodes such as FeNi3 and Ni3Sn2, and the composite electrodes can be nickel-based composite electrodes such as Ni-Co composite electrodes. Preferably, the electrodes are mostly coated with high-activity catalysts on pure nickel mesh and nickel foam as substrates to improve electrolysis efficiency.

[0084] In the present invention, the catalyst can be coated or disposed on the current collector surface by common methods such as hydrothermal method, electrodeposition or electroplating, and the present invention does not make special restrictions. The catalyst is divided into a cathode hydrogen evolution reaction (HER) electrocatalyst and an anode oxygen evolution reaction (OER) electrocatalyst, which are respectively disposed on the surface of the corresponding electrode current collector. The HER electrocatalyst can be a noble metal such as Pt, Pd, and / or a transition metal-based compound such as Fe, Co, Ni, Mo, W, etc., and the transition metal-based compound can be a transition metal-based sulfide, a transition metal-based phosphide, a transition metal-based carbide, and a transition metal-based nitride. The OER electrocatalyst can be one or more of a noble metal such as Ru, Rh, Ir, and its oxide, a transition metal oxide, a layered double metal hydroxide, and a transition metal sulfide, a carbide, and a nitride. In some embodiments, the OER electrocatalyst is a nickel mesh, NiCo2O4, and the HER electrocatalyst is NiMo.

[0085] In the present invention, the electrolyte includes an electrolyte and a solvent, the solvent is usually water, the electrolyte can be commonly used sulfuric acid, sodium hydroxide, potassium hydroxide, etc., and the mass of the electrolyte can be 30-50wt% based on the total weight of the electrolyte. When direct current is passed through the electrolyte aqueous solution, the decomposed substances are completely unrelated to the original electrolyte, and the solvent water is decomposed, while the original electrolyte remains in the water.

[0086] In the present invention, since the method in this application has a wide range of adaptability to diaphragms and water electrolysis hydrogen production technologies, the electrodes, diaphragm substrates and electrolytes can all be the electrodes, diaphragm substrates and electrolytes commonly used in the field of water electrolysis hydrogen production. The above enumeration is for illustration only and cannot be understood as limiting the scope of protection of the present invention.

[0087] The present invention also provides an application of the method or the composite film layer described above in the field of medical devices.

[0088] The present invention prepares an organic-inorganic hybrid film, such as organic aluminum + aluminum oxide, on the surface of the medical device by combining the ALD (atomic layer deposition) and MLD (molecular layer deposition) methods described above. The film has high adhesion and good hydrophilicity, and exhibits extremely high wettability in a liquid environment. The film layer has low roughness and low friction, and still exhibits good wettability after being subjected to friction. The film layer performance is maintained for a long time, which is beneficial to the insertion and removal of medical devices in the human body and reduces damage to human tissues.

[0089] Specifically, the medical device can be placed in a coating chamber and preheated according to the number and size of the devices. First, a certain thickness of organic aluminum is deposited according to the molecular layer deposition method (MLD) described above, and then a certain thickness of aluminum oxide is deposited according to the atomic layer deposition method (ALD) described above to prepare a hybrid film with certain hydrophilicity and wear resistance. By adjusting the ratio of organic and inorganic components, emphasis can be placed on hydrophilicity or wear resistance. Compared with organic aluminum or other materials, aluminum oxide has higher mechanical stability. Therefore, after aluminum oxide is attached to the surface of organic aluminum, it has higher wear resistance.

[0090] In the present invention, the medical device can be an implanted device or an external device. The device can be used temporarily for a short period of time or implanted permanently for a long period of time. In certain embodiments, suitable devices are those that are commonly used to provide medical treatment and / or diagnosis for cardiac arrhythmias, heart failure, valvular diseases, vascular diseases, diabetes, neurological diseases and disorders, plastic surgery, neurosurgery, oncology, ophthalmology and ENT surgery. The medical devices involved in the present invention include but are not limited to the following equipment: stents, stent grafts, anastomotic connectors, synthetic patches, leads, electrodes, needles, wires, catheters, sensors, surgical instruments, angioplasty balls, wound drainage tubes, shunts, tubes, infusion sleeves, urethral catheters, balls, implants, blood oxygenation generators, pumps, vascular grafts, vascular access ports, heart valves, annuloplasty rings, sutures, surgical clips, surgical staples, pacemakers, implantable defibrillators, neurostimulators, plastic surgery devices, cerebrospinal fluid shunts, implantable drug pumps, vertebral cages, artificial intervertebral discs, nucleus pulposus replacement devices, ear tubes, intraocular lenses and any tubes used in minimally invasive surgery.

[0091] In the present invention, the material of the medical device can be metal such as stainless steel, titanium, aluminum, copper, etc., or polymer material such as polyester, polypropylene, polyvinyl fluoride, polymethyl methacrylate, etc., or rubber material or cellulose material, etc.

[0092] The present invention also provides an application of the method or the composite film layer described above in the biological field, wherein the biological field includes biosensors and / or artificial joints.

[0093] The present invention prepares an organic-inorganic hybrid film, such as organic zinc + zinc oxide, on the surface of a biosensor by combining the ALD (atomic layer deposition) and MLD (molecular layer deposition) methods described above. The biosensor is placed in a coating chamber, preheated according to the number and size of the sensors, and first deposits a certain thickness of organic zinc according to the molecular layer deposition method (MLD) described above, and then deposits a certain thickness of zinc oxide according to the atomic layer deposition method (ALD) described above. Selecting organic zinc + inorganic zinc here can better ensure the conductivity requirements of the biosensor. The organic-inorganic zinc composite film has the performance of low resistivity, good hydrophilicity, and is easy to form a stable hydration layer, which can resist the adsorption of biological macromolecular pollutants and improve the anti-pollution ability.

[0094] The present invention combines ALD (atomic layer deposition) and MLD (molecular layer deposition) to prepare an organic-inorganic hybrid film, such as organic aluminum + aluminum oxide, on the surface of artificial joints and other prostheses. The artificial joints or prostheses are placed in a coating cavity and preheated according to the number and size of the artificial joints or prostheses. A certain thickness of organic aluminum is first deposited according to the molecular layer deposition method (MLD) described above, and then a certain thickness of aluminum oxide is deposited according to the atomic layer deposition method (ALD) described above. Compared with organic aluminum or other materials, aluminum oxide has higher mechanical stability. Therefore, after aluminum oxide is attached to the surface of the organic aluminum, it has higher wear resistance.

[0095] In the present invention, the artificial joints are mainly divided into two categories: artificial hip joints and artificial knee joints. The artificial hip joint is mainly composed of a joint handle, an acetabulum, a ball head, and a liner, while the artificial knee joint is mainly composed of a femoral condyle, a tibial plateau, and a tibial pad. The artificial joint liner and pad are mainly made of ultra-high molecular weight polyethylene.

[0096] The present invention provides a method for regulating the hydrophilicity of a metal oxide film layer, wherein the hydrophilicity of the metal oxide film layer is regulated by first depositing an organic metal compound film layer, specifically comprising: depositing an organic metal compound film layer on a substrate, and then depositing a metal oxide film layer on the surface of the organic metal compound film layer; the organic metal compound film layer is obtained by molecular layer deposition. The present invention regulates the hydrophilicity of the metal oxide film layer by depositing an organic metal compound film layer on the lower layer of the metal oxide film layer, and the addition of the organic metal compound film layer can especially improve the hydrophilicity of the metal oxide film layer.

[0097] Furthermore, by adjusting the deposition temperature and thickness of the organic metal compound film layer and the thickness of the metal oxide film layer, the hydrophilicity of the metal oxide film layer can be further optimized. According to the experimental results, the method of the present invention can adjust the contact angle of the metal oxide film layer to 0-20°.

[0098] Furthermore, when the metal precursor used in molecular layer deposition and the metal precursor used in atomic layer deposition are precursors of the same metal, the composite film layer has better bonding strength, mechanical properties and other properties than the composite film layer prepared using precursors of different metals.

[0099] The method of the present invention is suitable for low-temperature deposition, and is not only suitable for hard substrates such as silicon and metal, but also for flexible substrates such as organic polymers. Therefore, the method of the present invention has a wide range of applications, such as being applied to the field of hydrogen production by electrolysis of water, especially to the surface of a polyphenylene sulfide diaphragm, to improve the hydrophilicity of the polyphenylene sulfide diaphragm, and to reduce the surface resistance and power loss of the diaphragm; being applied to the field of medical devices, especially to the surface of interventional medical devices, to reduce the friction resistance generated when in contact with human tissue, and to reduce tissue damage and inflammation; being applied to the biological field, such as biosensors and artificial joints, to improve the anti-fouling ability of biosensors, enhance the reliability and stability of biosensors, and to improve the lubricity of artificial joints, reduce the friction coefficient, avoid joint wear, and increase the service life.

[0100] In order to further illustrate the present invention, a method for adjusting the contact angle of a metal oxide film layer provided by the present invention is described in detail below in conjunction with embodiments, but it should not be construed as limiting the scope of protection of the present invention.

[0101] Example 1

[0102] The reaction chamber is preheated at 150°C for 2 hours, and the organic aluminum film layer is deposited first. The process sequence is as follows:

[0103] 1) Pass TMA (trimethylaluminum) pulse for 0.5s;

[0104] 2) Pass nitrogen gas for purging for 60 seconds;

[0105] 3) Pass EG (ethylene glycol) pulse for 1.5s;

[0106] 4) nitrogen was introduced for purging for 120 seconds;

[0107] Steps 1) to 4) constitute one cycle, and 250 cycles are performed to obtain an organic aluminum coating with a thickness of 70 nm.

[0108] Then ALD is used to deposit an aluminum oxide film. The ALD deposition temperature is 60°C. The process sequence is as follows:

[0109] 1) Apply TMA pulse for 0.5s;

[0110] 2) Pass nitrogen gas for purging for 60 seconds;

[0111] 3) Pass water pulse for 1.5s;

[0112] 4) nitrogen was introduced for purging for 120 seconds;

[0113] Steps 1 to 4 constitute one cycle, and 10 cycles are performed to form an aluminum oxide coating layer with a thickness of 1 nm, thereby obtaining a composite film layer of an organic aluminum film layer and aluminum oxide.

[0114] Example 2

[0115] The composite film layer was prepared according to the method in Example 1, except that in the preparation of the aluminum oxide film layer, 50 cycles were performed to form a 5 nm thick aluminum oxide coating layer, thereby obtaining a composite film layer of an organic aluminum film layer and aluminum oxide.

[0116] Example 3

[0117] The composite film layer was prepared according to the method in Example 1, except that in the preparation of the aluminum oxide film layer, 100 cycles were performed to form a 10 nm thick aluminum oxide coating to obtain a composite film layer of an organic aluminum film layer and aluminum oxide.

[0118] Example 4

[0119] The reaction chamber is preheated at 150°C for 2 hours, and the organic zinc film is deposited first. The process sequence is as follows:

[0120] 1) Pass DEZ (diethyl zinc) pulse for 0.5s;

[0121] 2) Pass nitrogen gas for purging for 60 seconds;

[0122] 3) Pass EG (ethylene glycol) pulse for 1.5s;

[0123] 4) Introduce nitrogen to purge for 60 seconds;

[0124] Steps 1) to 4) constitute one cycle, and 240 cycles are performed to obtain an organic zinc coating with a thickness of 70 nm.

[0125] Then ALD is used to deposit a zinc oxide film at a deposition temperature of 150°C. The process sequence is as follows:

[0126] 1) Pass DEZ (diethyl zinc) pulse for 0.5s;

[0127] 2) Pass nitrogen gas for purging for 60 seconds;

[0128] 3) Pass water pulse for 1.5s;

[0129] 4) nitrogen was introduced for purging for 120 seconds;

[0130] Steps 1 to 4 constitute one cycle, and 15 cycles are performed to obtain a 2 nm thick zinc oxide coating, thereby obtaining a composite film layer of an organic zinc film layer and zinc oxide.

[0131] Example 5

[0132] A composite film layer of an organic aluminum film layer and aluminum oxide was prepared according to the method in Example 3, except that the thickness of the organic aluminum layer was 20 nm.

[0133] Example 6

[0134] A composite film layer of an organic aluminum film layer and aluminum oxide was prepared according to the method in Example 3, except that the thickness of the organic aluminum layer was 50 nm.

[0135] Comparative Example 1

[0136] Only the method in Example 1 was used to prepare a 70 nm thick organic aluminum coating, without preparing an aluminum oxide coating.

[0137] Comparative Example 2

[0138] Only a 10 nm thick aluminum oxide coating was prepared according to the method in Example 3, without preparing an organic aluminum coating.

[0139] The contact angles of the films obtained in Examples 1 to 3 and Comparative Examples 1 to 2 were tested, and the results are shown in Table 1.

[0140] Table 1 Contact angle test of film layers in Examples 1 to 4 and Comparative Examples 1 to 2

[0141]

[0142] According to the data in Table 1, after the organic aluminum coating is added to Example 3, the contact angle of the composite film layer decreases from 11.22° in Comparative Example 2 to 3.92°, which proves that the hydrophilicity of the aluminum oxide film layer is significantly improved, and when aluminum oxide films of different thicknesses are plated on the organic aluminum layer of the same thickness, the aluminum oxide films show different contact angles, indicating that the hydrophilicity of the composite film layer can be controlled by adjusting the thickness of the aluminum oxide film layer.

[0143] It can be seen from the contact angles of the composite film layers prepared in Examples 3, 5 and 6 that the adjustment of the thickness of the organic aluminum film layer has a significant effect on the hydrophilicity of the composite film layer, showing a trend that as the thickness of the organic aluminum layer increases, the contact angle of the composite film layer decreases, i.e., the hydrophilicity increases. This indicates that the hydrophilicity of the composite film layer can be controlled by adjusting the thickness of the organic aluminum film layer.

[0144] Application Example 1

[0145] The reaction chamber is preheated at 150°C for 2 hours. The polyphenylene sulfide diaphragm is placed in the reaction chamber and an organic zinc film is deposited first. The process sequence is as follows:

[0146] 1) Pass DEZ (diethyl zinc) pulse for 0.5s;

[0147] 2) Pass nitrogen gas for purging for 60 seconds;

[0148] 3) Pass EG (ethylene glycol) pulse for 1.5s;

[0149] 4) Introduce nitrogen to purge for 60 seconds;

[0150] Steps 1) to 4) constitute one cycle, and 240 cycles are performed to obtain an organic zinc coating with a thickness of 70 nm.

[0151] Then ALD is used to deposit a zinc oxide film at a deposition temperature of 150°C. The process sequence is as follows:

[0152] 1) Pass DEZ (diethyl zinc) pulse for 0.5s;

[0153] 2) Pass nitrogen gas for purging for 60 seconds;

[0154] 3) Pass water pulse for 1.5s;

[0155] 4) nitrogen was introduced for purging for 120 seconds;

[0156] Steps 1 to 4 constitute one cycle, and 15 cycles are performed to obtain a zinc oxide coating layer with a thickness of 2 nm, thereby obtaining a polyphenylene sulfide diaphragm having a composite film layer of deposited organic zinc film layer and zinc oxide.

[0157] The above steps form a hydrophilic layer with a controllable contact angle inside the pores and / or on the surface of the polyphenylene sulfide diaphragm, which can improve the hydrophilicity of the final polyphenylene sulfide diaphragm and reduce the surface resistance of the diaphragm, thereby reducing the energy consumption of the electrolytic cell and improving the electrolysis efficiency. In addition, the diaphragm has good three-dimensional shape retention performance, optimizes the hydrophilicity and resistivity of the polymer pores, and has little effect on the porosity.

[0158] Application Example 2

[0159] The reaction chamber is preheated at 150°C for 2 hours, a medical catheter made of polyurethane is placed in the reaction chamber, and an organic aluminum film layer is deposited first. The process sequence is as follows:

[0160] 1) Pass TMA (trimethylaluminum) pulse for 0.5s;

[0161] 2) Introduce nitrogen to purge for 60 seconds;

[0162] 3) Pass EG (ethylene glycol) pulse for 1.5s;

[0163] 4) nitrogen was introduced for purging for 120 seconds;

[0164] Steps 1) to 4) constitute one cycle, and 250 cycles are performed to obtain an organic aluminum coating with a thickness of 70 nm.

[0165] Then ALD is used to deposit an aluminum oxide film. The ALD deposition temperature is 60°C. The process sequence is as follows:

[0166] 1) Apply TMA pulse for 0.5s;

[0167] 2) Pass nitrogen gas for purging for 60 seconds;

[0168] 3) Pass water pulse for 1.5s;

[0169] 4) nitrogen was introduced for purging for 120 seconds;

[0170] Steps 1 to 4 constitute one cycle, and 10 cycles are performed to form an aluminum oxide coating layer with a thickness of 1 nm, thereby obtaining a medical catheter having a composite film layer of deposited organic aluminum film layer and aluminum oxide.

[0171] The composite film layer has high adhesion to the medical catheter, and improves the hydrophilicity and wettability of the surface of the medical catheter, reduces the surface roughness and friction, is conducive to the insertion of the medical catheter into the human body and reduces damage to human tissue.

[0172] Application Example 3

[0173] The reaction chamber is preheated at 150°C for 2 hours. The biosensor is placed in the reaction chamber and an organic zinc film is deposited. The process sequence is as follows:

[0174] 1) Pass DEZ (diethyl zinc) pulse for 0.5s;

[0175] 2) Pass nitrogen gas for purging for 60 seconds;

[0176] 3) Pass EG (ethylene glycol) pulse for 1.5s;

[0177] 4) Introduce nitrogen to purge for 60 seconds;

[0178] Steps 1) to 4) constitute one cycle, and 240 cycles are performed to obtain an organic zinc coating with a thickness of 70 nm.

[0179] Then ALD is used to deposit a zinc oxide film at a deposition temperature of 150°C. The process sequence is as follows:

[0180] 1) Pass DEZ (diethyl zinc) pulse for 0.5s;

[0181] 2) Pass nitrogen gas for purging for 60 seconds;

[0182] 3) Pass water pulse for 1.5s;

[0183] 4) nitrogen was introduced for purging for 120 seconds;

[0184] Steps 1 to 4 constitute one cycle, and 15 cycles are performed to obtain a zinc oxide coating layer with a thickness of 2 nm, thereby obtaining a biosensor having a composite film layer of deposited organic zinc film and zinc oxide.

[0185] The composite film layer of organic zinc + inorganic zinc can not only better guarantee the conductivity requirements of the biosensor, but also has good hydrophilicity and is easy to form a stable hydration layer, which can resist the adsorption of biological macromolecular pollutants and improve the anti-fouling ability.

[0186] Application Example 4

[0187] The reaction chamber is preheated at 150°C for 2 hours. The artificial joint made of polyethylene is placed in the reaction chamber and the organic aluminum film layer is deposited first. The process sequence is as follows:

[0188] 1) Pass TMA (trimethylaluminum) pulse for 0.5s;

[0189] 2) Pass nitrogen gas for purging for 60 seconds;

[0190] 3) Pass EG (ethylene glycol) pulse for 1.5s;

[0191] 4) nitrogen was introduced for purging for 120 seconds;

[0192] Steps 1) to 4) constitute one cycle, and 250 cycles are performed to obtain an organic aluminum coating with a thickness of 70 nm.

[0193] Then ALD is used to deposit an aluminum oxide film. The ALD deposition temperature is 60°C. The process sequence is as follows:

[0194] 1) Apply TMA pulse for 0.5s;

[0195] 2) Pass nitrogen gas for purging for 60 seconds;

[0196] 3) Pass water pulse for 1.5s;

[0197] 4) nitrogen was introduced for purging for 120 seconds;

[0198] Steps 1 to 4 constitute one cycle, and 10 cycles are performed to form an aluminum oxide coating layer with a thickness of 1 nm, thereby obtaining an artificial joint having a composite film layer of deposited organic aluminum film layer and aluminum oxide.

[0199] The artificial joint deposited with the organic aluminum film layer + aluminum oxide composite film layer has high wear resistance, improves the lubricity of the artificial joint surface, reduces the friction coefficient of the artificial joint during movement, thereby reducing wear and increasing the service life of the artificial joint.

[0200] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for regulating the hydrophilicity of a metal oxide film, characterized in that: The hydrophilicity of the metal oxide film layer is regulated by first depositing an organic metal compound film layer, specifically including: Depositing an organic metal compound film layer on a substrate, and then depositing a metal oxide film layer on the surface of the organic metal compound film layer; The organic metal compound film layer is obtained by molecular layer deposition.

2. The method according to claim 1, characterized in that: The metal oxide film layer is obtained by atomic layer deposition, specifically comprising: a) placing a substrate with an organic metal compound film layer deposited thereon in a reaction chamber, introducing an organic metal precursor with a pulse time of t1; b) Pass protective gas to purge for time t2; c) introducing oxygen source, pulse time t3; d) Pass protective gas to purge for time t4; Step a) to step d) constitute one cycle, and the metal oxide film layer can be obtained by performing multiple cycles.

3. The method according to claim 2, characterized in that The atomic layer deposition temperature is 10 to 350° C. The t1 is 0.5 to 10 s, t2 is 5 to 100 s, t3 is 0.5 to 10 s, t4 is 5 to 180 s; and the number of cycles is 10 to 200.

4. The method according to claim 2, characterized in that: The metal in the organometallic precursor includes one or more of aluminum, zinc, tin, titanium, hafnium, zirconium and nickel; The protective gas includes nitrogen and / or argon; the oxygen source includes water vapor and / or ozone.

5. The method according to claim 1, characterized in that The method for regulating the hydrophilicity of the metal oxide film layer also includes: The hydrophilicity of the metal oxide film layer is regulated by regulating the film thickness of the metal oxide, and the thickness of the metal oxide film layer is 1 to 30 nm.

6. The method according to claim 1, characterized in that The organometallic compound film layer is obtained by the following molecular layer deposition steps: A) placing the substrate in the reaction chamber, introducing the organometallic precursor, with a pulse time of T1; B) Pass protective gas to purge for T2 time; C) introducing an oxidative organic precursor, with a pulse time of T3; D) Pass protective gas to purge for T4 time; Step A) to step D) constitute one cycle, and the organic metal compound film layer can be obtained by performing multiple cycles.

7. The method according to claim 6, characterized in that The temperature of the molecular layer deposition is 60-300° C.; T1 is 0.5-10 s, T2 is 5-100 s, T3 is 0.5-10 s, and T4 is 5-180 s; and the number of cycles is 1-2000 times.

8. The method according to claim 6, characterized in that The metal in the organometallic precursor includes one or more of aluminum, zinc, tin, titanium, hafnium, zirconium and nickel; The protective gas includes nitrogen and / or argon; The oxidative organic precursor includes C1-C5 alcohol.

9. The method according to claim 6, characterized in that The thickness of the organic metal compound film layer is 5 to 200 nm.

10. The method according to claim 1, characterized in that The contact angle of the metal oxide film layer is 0-20°.

11. The method according to claim 1, characterized in that: The material of the substrate is a hard substrate or a flexible substrate.

12. A composite membrane layer with adjustable hydrophilicity, prepared according to the preparation method according to any one of claims 1 to 11.

13. Use of the method according to any one of claims 1 to 11 or the composite membrane layer according to claim 12 in the field of hydrogen production by electrolysis of water.

14. The use according to claim 13, characterized in that Taking the diaphragm in hydrogen production by water electrolysis as the substrate, an organic zinc film layer and a zinc oxide film layer are sequentially deposited on the surface of the diaphragm by the method described in any one of claims 1 to 11.

15. The use according to claim 14, characterized in that: The material of the diaphragm is polyphenylene sulfide, polysulfone, polyetheretherketone, polytetrafluoroethylene or polytetrafluoroethylene modified asbestos.

16. Use of the method according to any one of claims 1 to 11 or the composite film layer according to claim 12 in the field of medical devices.

17. The use according to claim 16, characterized in that An organic aluminum film layer and an aluminum oxide film layer are sequentially deposited on the surface of a medical device using the method described in any one of claims 1 to 11.

18. The use according to claim 17, characterized in that The material of the medical device is metal, polymer, rubber material or cellulose material.

19. Use of the method according to any one of claims 1 to 11 or the composite film layer according to claim 12 in the biological field, wherein the biological field includes biosensors and / or artificial joints.

20. The use according to claim 19, characterized in that An organic zinc film layer and a zinc oxide film layer are sequentially deposited on the surface of the biosensor using the method described in any one of claims 1 to 11.

21. The use according to claim 19, characterized in that The method described in any one of claims 1 to 11 is used to sequentially deposit an organic aluminum film layer and an aluminum oxide film layer on the surface of an artificial joint.

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