Parylene coating for detection probe and preparation method thereof

Abstract

The invention relates to the technical field of vapor deposition, in particular to a parylene coating for a detection probe and a preparation method of the parylene coating. Treating the substrate with a silane coupling agent; depositing a coating film on the base material to form a first coating film layer; depositing a coating film on the first coating film layer to form a second coating film layer; plasma treatment is carried out on the second coating layer, and then deposition coating is carried out to form a third coating layer; wherein the first film coating layer, the second film coating layer and the third film coating layer are parylene film layers; the thickness of the second coating layer is at least 1.5 microns, and the thickness of the second coating layer is larger than the height of the micro-nano structure after plasma treatment. According to the preparation method, the two parylene film layers are formed by depositing and coating the base material, the plasma treatment is performed on the second parylene film layer, and the third parylene film layer is formed by coating after the plasma treatment, so that the coating has high hydrophobicity and high stability, and is excellent in environmental corrosion resistance; therefore, the service life of the probe using the coating is prolonged.

Description

Technical Field

[0001] The present invention relates to the field of vapor deposition technology, and more particularly, to a parylene coating for a detection probe and a method for preparing the same. Background Art

[0002] Parylene coatings are often used to prepare or protect the probes of detection devices due to their properties such as homogeneous conformal protection and biocompatibility. However, the application environment can seriously affect the service life of the detection probe. For example, for the probe of a medical imaging ultrasound detection device, during use, the surface of the probe often needs to be immersed in a coupling agent, which is mostly an aqueous polymer gel preparation. When the probe is immersed in this aqueous polymer gel preparation for a long time, it is easy to cause the outer silicone substrate of the probe to expand and fail, thereby affecting the piezoelectric ceramics and other important sensitive components inside the probe, resulting in inaccurate or ineffective detection of the probe.

[0003] In view of this, the inventors of the present disclosure provide a parylene coating with good hydrophobicity and stability, which has properties such as moisture resistance, water vapor resistance, environmental corrosion resistance, and non-dusting, and can be applied to detection probes used in various environments, improving the detection accuracy, stability, cleanliness of the probe, and extending the service life of the probe. Summary of the Invention

[0004] The purpose of the present invention is to provide a parylene coating for a detection probe and a method for preparing the same. The preparation method forms two parylene film layers by vapor deposition coating on a substrate, performs plasma treatment on the second parylene film layer with a thickness of at least 1.5 μm, and coats again after the plasma treatment to form a third parylene film layer, so that the parylene coating for the detection probe has high hydrophobicity and high stability, especially environmental corrosion resistance and non-dusting properties, thereby improving the detection accuracy, stability of the medical probe with this coating, and extending the service life of the probe.

[0005] The present invention is implemented as follows:

[0006] In a first aspect, the present invention provides a method for preparing a parylene coating for a detection probe, including:

[0007] Clean the substrate;

[0008] Treat the substrate with a silane coupling agent;

[0009] Perform a first deposition coating on the substrate to form a first coating layer;

[0010] Perform a second deposition coating on the first coating layer to form a second coating layer;

[0011] Perform plasma treatment on the second coating layer, and,

[0012] After plasma treatment, a third deposition coating is performed to form a third coating layer; wherein:

[0013] The first coating layer, the second coating layer, and the third coating layer are all parylene film layers;

[0014] The thickness of the second coating layer is at least 1.5 μm, and the thickness of the second coating layer is greater than the height of the micro-nano structure after plasma treatment.

[0015] In an alternative embodiment, the height of the micro-nano structure after plasma treatment is at least 0.01 μm.

[0016] In an alternative embodiment, the thickness of the second coating layer is 2 - 10 μm.

[0017] In an alternative embodiment, the thickness of the third coating layer is at least 0.05 μm.

[0018] In an alternative embodiment, the cleaning liquid used in the cleaning step includes at least one of alcohol-based cleaning liquids and water-based cleaning agents; the cleaning method includes circulating the cleaning liquid at a temperature of 40 - 80°C for cleaning; the cleaning time is 10 min - 60 min.

[0019] In an alternative embodiment, the volume concentration of the silane coupling agent is 0.1 - 10%.

[0020] In an alternative embodiment, the raw materials used in the plasma treatment step are fluorinated gas and oxygen.

[0021] In an alternative embodiment, the fluorinated gas is selected from at least one of sulfur hexafluoride and hexafluoropropylene.

[0022] In an alternative embodiment, the power of the plasma treatment is 30 - 300 W / layer electrode, the flow rate of oxygen is 30 - 200 sccm, and the flow rate of the fluorinated gas is 30 - 200 sccm.

[0023] In an alternative embodiment, the time of the plasma treatment is 10 - 200 min.

[0024] In an alternative embodiment, the thickness of the first coating layer is 1 - 100 μm.

[0025] In an alternative embodiment, it further includes:

[0026] When the humidity of the probe's usage environment ≤ 30%, the thickness of the first coating layer is 2 - 10 μm, and the thickness of the third coating layer is at least 0.1 μm;

[0027] When the humidity of the probe's operating environment is > 30% and ≤ 80%, the thickness of the first coating layer is 15 - 20 μm, and the thickness of the third coating layer is at least 0.08 μm;

[0028] When the probe's operating environment is immersion in a water-containing liquid, the thickness of the first coating layer is greater than or equal to 30 μm, and the thickness of the third coating layer is at least 0.05 μm.

[0029] In an alternative embodiment, when the probe's operating environment is long-term immersion in a water-containing liquid or a salt spray environment, the thickness of the first coating layer is greater than or equal to 50 μm.

[0030] In a second aspect, the present invention also provides a parylene coating for a detection probe, which is prepared by the aforementioned method for preparing a parylene coating for a detection probe.

[0031] The present invention includes the following beneficial effects:

[0032] The method for preparing a parylene coating for a detection probe provided by an embodiment of the present invention includes: cleaning the substrate; treating the substrate with a silane coupling agent; performing a first deposition coating on the substrate to form a first coating layer; performing a second deposition coating on the first coating layer to form a second coating layer; performing plasma treatment on the second coating layer; performing a third deposition coating after the plasma treatment to form a third coating layer; the first coating layer, the second coating layer, and the third coating layer are all parylene film layers, and the thickness of the second coating layer is at least 1.5 μm. In this way, the integrity of the first coating layer can be ensured by using the second coating layer with a thickness greater than the height of the micro-nano structure, so as to improve the adverse effects on the stability of the parylene film layer caused by subsequent plasma hydrophobic treatment, and improve the stability and corrosion resistance; in addition, plasma treatment on the second coating layer can form nano-scale, lotus-leaf-like fine convex microstructures on the surface of the parylene film layer, thereby forming good hydrophobicity; that is, the preparation method of the present invention deposits and coats two parylene film layers on the substrate and performs plasma treatment on the second parylene film layer. On the one hand, the probe with the parylene coating for a detection probe has high hydrophobicity, and on the other hand, the first coating layer is isolated and protected by the second coating layer to ensure the integrity of the first coating layer and ensure that the coating has good environmental corrosion resistance; at the same time, the third coating layer can also be used to protect and fix the film structure after plasma treatment. Description of the Drawings

[0033] To more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required for use in the embodiments. It should be understood that the following drawings only show certain embodiments of the present invention and should not be regarded as limiting the scope. For those of ordinary skill in the art, without creative efforts, other related drawings can also be obtained based on these drawings.

[0034] Figure 1 Schematic diagram for defining the height of the micro-nano structure in the present invention;

[0035] Figure 2 Microscopic structure diagram for high-precision detection scanning of the parylene coating of the detection probe in Embodiment 1 of the present invention;

[0036] Figure 3 Microscopic structure diagram for high-precision detection scanning of the parylene coating of the detection probe in Embodiment 3 of the present invention;

[0037] Figure 4 Microscopic structure diagram for high-precision detection scanning of the parylene coating of the detection probe in Embodiment 4 of the present invention;

[0038] Figure 5 Photo of the adhesion force detection of the treated substrate in Embodiment 1 of Experimental Example 1 of the present invention;

[0039] Figure 6 Photo of the adhesion force detection of the treated substrate in Embodiment 3 of Experimental Example 1 of the present invention;

[0040] Figure 7 Photo of the appearance detection of the treated substrate in Embodiment 1 of Experimental Example 1 of the present invention;

[0041] Figure 8 Microscopic detection result diagram of the treated substrate and the uncoated substrate in Embodiment 1 of Experimental Example 2 of the present invention;

[0042] Figure 9 Hydrophilic and hydrophobic detection result diagram of the treated substrate in Embodiment 1 and the conventional parylene film in Experimental Example 3 of the present invention;

[0043] Figure 10 Microscopic diagrams of the treated substrate in Embodiment 1, the conventional parylene film and the untreated substrate at 3× and 200× in Experimental Example 4 of the present invention;

[0044] Figure 11 Hydrophilic and hydrophobic detection result diagram of the treated substrate in Embodiment 1, the conventional parylene film and the untreated substrate in Experimental Example 4 of the present invention;

[0045] Figure 12SEM images of the treated substrate in Example 1 of Experimental Example 5 of the present invention and a conventional parylene film;

[0046] Figure 13 Microstructural diagram of high-precision detection scanning of a conventional parylene film in Experimental Example 6 of the present invention;

[0047] Figure 14 Results of soaking the treated substrate in Example 1, a conventional parylene film, and an untreated substrate with plasma water in Experimental Example 7 of the present invention;

[0048] Figure 15 Results of soaking the treated substrate in Example 1, a conventional parylene film, and an untreated substrate with PBS solution in Experimental Example 8 of the present invention;

[0049] Figure 16 Storage result diagram of Experimental Example 10 of the present invention. Detailed implementation mode

[0050] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. For those not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. For reagents or instruments without indicating the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0051] The present invention provides a method for preparing a parylene coating for a detection probe, including: cleaning the substrate; treating the substrate with a silane coupling agent; performing a first deposition coating on the substrate to form a first coating layer; performing a second deposition coating on the first coating layer to form a second coating layer; and performing plasma treatment on the second coating layer; wherein, both the first coating layer and the second coating layer are parylene film layers.

[0052] The thickness of the second coating layer is at least 1.5 μm, and the thickness of the second coating layer is greater than the height of the micro-nano structure left after plasma treatment, that is, the plasma treatment does not penetrate the second coating layer, and the first coating layer is not plasma-treated.

[0053] The parylene film layer is a single-molecule polymer. By the step of depositing to form the second coating layer, the protective performance of the film layer can be improved, and the second coating layer with a thickness greater than the height of the micro-nano structure is used to ensure

[0054] The integrity of the first coating layer is improved to mitigate the adverse effects of subsequent plasma treatment on the parylene film layer. That is, the second coating layer can ensure the integrity of the first coating layer to improve the adverse effects on the stability of the parylene film layer caused by subsequent plasma hydrophobic treatment, thereby enhancing the stability and corrosion resistance of the coating. Additionally, plasma treatment on the second coating layer can form nano-scale, lotus leaf-like fine convex microstructures on the surface of the parylene film layer, thus achieving good hydrophobicity. That is, this preparation method deposits two parylene film layers on the substrate through coating and performs plasma treatment on the second parylene film layer, enabling the medical probe with the parylene coating for the detection probe to have biocompatibility while enhancing its hydrophobicity, thereby improving the detection accuracy and stability of the medical probe. Moreover, the second coating layer is used to isolate and protect the first coating layer to ensure the integrity of the first coating layer, ensuring that the coating and the probe using this coating have good environmental corrosion resistance and extending the service life of the medical probe.

[0055] The deposition thickness of the second coating layer is at least 1.5 μm. For example: 1.5 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, etc., and no specific limitation is made here. The second coating layer with a certain thickness can enhance the protection performance for the first coating layer, ensure the integrity of the first coating layer, effectively mitigate the adverse effects of subsequent plasma treatment on the first coating layer, and improve the corrosion resistance.

[0056] Optionally, the step of the second deposition coating can be carried out by using an automated vacuum deposition system (equipment) for coating treatment, and the raw materials used include at least one of parylene C powder, N powder, F powder, and HT powder.

[0057] Optionally, the thickness of the second coating layer is 2 - 10 μm. For example: 2 μm, 4 μm, 8 μm, 10 μm, etc., and no specific limitation is made here. Controlling the second coating layer not to be too thick can avoid adverse effects on the detection effect of the probe; at the same time, controlling the second coating layer not to be too thin can ensure the protection of the first coating layer by the second coating layer, ensure the good protection effect of the crosslinked bottom film structure on the probe, and improve the corrosion resistance.

[0058] Please refer to Figure 1, the thickness of the second coating layer is greater than the height of the micro-nano structure after plasma treatment; where 1 is the substrate for coating, 2 is the first coating layer, 3 is the second coating layer, and d represents the height of the micro-nano structure after plasma treatment. That is, the height of the micro-nano structure refers to the distance between the surface of the micro-nano structure and the top surface of the first coating layer. That is, the thickness of the remaining part of the second coating layer 3 after partial removal by plasma treatment. In this way, the integrity of the first coating layer can be ensured by using the second coating layer with a thickness greater than the height of the micro-nano structure, so as to improve the adverse effects on the stability of the parylene film layer caused by subsequent plasma hydrophobic treatment, and to improve the stability and corrosion resistance. That is, micro-nano structures of a certain height can build better hydrophobic ability.

[0059] Optionally, the height of the micro-nano structure after plasma treatment is at least 0.01 μm (for example: 0.01 μm, 0.05 μm, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 8 μm, etc., which are not specifically limited here). In this way, on the one hand, a good hydrophobic effect is ensured, and on the other hand, the thickness range of the plasma treatment is ensured not to exceed the thickness range of the second coating layer to ensure the integrity of the first coating layer.

[0060] It should be noted that the above-mentioned substrate can refer to the medical probe itself, or a silicone sheet or a copper-plated metal sheet sleeved outside the medical probe, etc., which are not specifically limited here.

[0061] The preparation method further includes: performing a third deposition coating after plasma treatment to form a third coating layer, and the third coating layer is a parylene film layer. In this way, the third coating layer can also be used to protect and fix the film structure after plasma treatment. This structure in which the hydrophobic structure and the underlying parylene film layer cooperate together strengthens the protection and hydrophobic performance of the overall film layer.

[0062] Optionally, the step of the third deposition coating can be carried out by using an automated vacuum deposition system (equipment), and the raw materials used for the deposition coating include parylene C powder, N powder, F powder, and HT powder.

[0063] Optionally, the raw material for the third deposition coating can be selected from parylene F powder or C powder.

[0064] Optionally, the thickness of the third coating layer is at least 0.05 μm, for example: 0.05 μm, 0.06 μm, 0.08 μm, 0.1 μm, 0.2 μm, 0.5 μm, 0.6 μm, 1 μm, 2 μm, 3 μm, etc., which are not specifically limited here. In this way, the underlying film structure treated by plasma can be stably fixed, that is, the stability of the fixing effect of the third coating layer on the underlying film structure treated by plasma is ensured.

[0065] Optionally, the coating thickness of the third coating layer can be 0.05 - 0.6 μm, for example: 0.05 μm, 0.06 μm, 0.08 μm, 0.1 μm, 0.2 μm, 0.5 μm, 0.6 μm, etc., and no specific limitation is made here. A thinner third coating layer can, on the one hand, stably fix the underlying film structure of the plasma treatment, that is, ensure the stability of the fixing effect of the third coating layer on the underlying film structure of the plasma treatment, and on the other hand, prevent the third coating layer from being too thick and ensure better hydrophobicity.

[0066] Optionally, the cleaning liquid used for cleaning the substrate includes at least one of alcohol-based cleaning liquids (such as isopropyl alcohol or ethanol) and water-based cleaning agents (such as Henkel's 5058).

[0067] Optionally, the cleaning method includes circulating the cleaning liquid at a temperature of 40 - 80 °C (such as: 40 °C, 42 °C, 45 °C, 47 °C, 50 °C, 53 °C, 55 °C, 58 °C, 60 °C, 62 °C, 65 °C, 68 °C, 70 °C, 72 °C, 75 °C, 78 °C, 80 °C, etc., and no specific limitation is made here) for cleaning; the cleaning time is 10 min - 60 min (such as: 10 min, 20 min, 30 min, 40 min, 50 min, 60 min, etc., and no specific limitation is made here). In this way, the cleaning cleanliness can be ensured, which is beneficial to improving the bonding strength between the subsequent materials and the substrate.

[0068] Of course, in some embodiments, a static and non-flowing immersion cleaning method of the cleaning liquid can be adopted, and no specific limitation is made here.

[0069] Optionally, after cleaning, the substrate is taken out and drained of the cleaning liquid on the surface, and the surface of the substrate is dried, for example: drying treatment is carried out using a vacuum high-temperature oven, and the drying temperature and time are not specifically limited as long as the cleaning liquid on the substrate surface can be dried; exemplary, the drying temperature can be 40 - 250 °C (such as: 40 °C, 80 °C, 150 °C, 170 °C, 190 °C, 210 °C, 230 °C, 250 °C, etc., and no specific limitation is made here), and the time can be 1 - 9 h (such as: 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, etc., and no specific limitation is made here).

[0070] Optionally, the drying time can be 3 - 5 h, for example: 3 h, 4 h, 5 h, etc., and no specific limitation is made here.

[0071] Optionally, the methods of treating the cleaned and dried substrate with a silane coupling agent include, but are not limited to, immersion, coating, brushing or spraying; treating the substrate with a silane coupling agent can improve the bonding force of the subsequent coating treatment.

[0072] Optionally, the silane coupling agent includes but is not limited to γ-methacryloxypropyltrimethoxysilane, tetraethyl orthosilicate, etc.; the volume concentration of the silane coupling agent is 0.1-10%, for example: 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc., and no specific limitation is made here.

[0073] Optionally, after being treated with the silane coupling agent, the substrate is taken out, the surface is drained, and then a drying treatment is carried out. The treatment methods include but are not limited to air drying and drying in a vacuum high-temperature oven, etc. The temperature and time of drying are not limited, as long as the silane coupling agent on the surface of the substrate can be dried.

[0074] Optionally, the step of the first deposition coating can be carried out by using an automated vacuum deposition system (equipment) for coating treatment. The raw materials include at least one of parylene C powder, N powder, F powder, and HT powder. The deposition thickness of the first coating layer is 1-100 μm, for example: 1 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, etc., and no specific limitation is made here. The first coating layer with a certain thickness can ensure the protection effect on the substrate.

[0075] Optionally, the thickness of the first coating layer is 4-30 μm, for example: 4 μm, 8 μm, 10 μm, 13 μm, 15 μm, 18 μm, 20 μm, 22 μm, 25 μm, 27 μm, 30 μm, etc., and no specific limitation is made here. Controlling the first coating layer not to be too thick can avoid having an adverse effect on the detection effect of the probe; at the same time, controlling the first coating layer not to be too thin can ensure the protection effect of the first coating layer on the probe.

[0076] Optionally, when the humidity of the probe's usage environment ≤ 30%, the thickness of the first coating layer is 2 - 10 μm (for example: 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, etc., not specifically limited here), and the thickness of the third coating layer is at least 0.1 μm (for example: 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, etc., not specifically limited here); when the humidity of the probe's usage environment > 30% and ≤ 80%, the thickness of the first coating layer is 15 - 20 μm (for example: 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, etc., not specifically limited here), and the thickness of the third coating layer is at least 0.08 μm (for example: 0.08 μm, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, etc., not specifically limited here); when the probe's usage environment is immersion in a water-containing liquid, the thickness of the first coating layer ≥ 30 μm (for example: 30 μm, 31 μm, 32 μm, 33 μm, 34 μm, 35 μm, etc., not specifically limited here), and the thickness of the third coating layer is at least 0.05 μm (for example: 0.05 μm, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, etc., not specifically limited here). In this way, it can ensure that the parylene coating for the detection probe can adapt to different humidity environments, that is, it can ensure good corrosion resistance of the parylene coating for the detection probe in different humidity environments.

[0077] Furthermore, when the probe's usage environment is long-term immersion in a water-containing liquid or usage in an environment with salt spray, etc., the thickness of the first coating layer is greater than or equal to 50 μm (for example: 50 μm, 51 μm, 52 μm, 53 μm, 54 μm, 55 μm, etc., not specifically limited here).

[0078] Optionally, the raw materials used for plasma treatment include fluorinated gas and oxygen. The fluorinated gas can be sulfur hexafluoride (SF6) or hexafluoropropene, etc. The plasma treatment time is 10 - 200 min, for example: 10 min, 20 min, 50 min, 80 min, 100 min, 120 min, 150 min, 170 min, 200 min, etc., not specifically limited here. By controlling a certain plasma treatment time, it can ensure the formation of a good hydrophobic structure on the surface of the second coating layer, and at the same time, it will not damage the second coating layer and the structure between it and the first coating layer, that is, it can ensure that the bottom film structure maintains a good protective effect.

[0079] Optionally, the power of the plasma treatment is 30 - 300 W per layer of electrode (e.g., 30 W per layer of electrode, 40 W per layer of electrode, 50 W per layer of electrode, 60 W per layer of electrode, 70 W per layer of electrode, 80 W per layer of electrode, 90 W per layer of electrode, 100 W per layer, 200 W per layer, 300 W per layer of electrode, etc., which are not specifically limited herein), the flow rate of oxygen is 30 - 200 sccm (e.g., 30 sccm, 40 sccm, 50 sccm, 60 sccm, 80 sccm, 100 sccm, 120 sccm, 150 sccm, 170 sccm, 200 sccm, etc., which are not specifically limited herein), and the flow rate of the fluorinated gas is 30 - 200 sccm (e.g., 30 sccm, 40 sccm, 50 sccm, 60 sccm, 80 sccm, 100 sccm, 120 sccm, 150 sccm, 170 sccm, 200 sccm, etc., which are not specifically limited herein).

[0080] It should be noted that the above "W per layer of electrode" means: the power evenly distributed on each layer of electrode plate in the plasma ionization device.

[0081] Optionally, the time of the plasma treatment is 20 - 90 min, e.g., 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, etc., which are not specifically limited herein. Optimizing the time of the plasma treatment can ensure good hydrophobicity while ensuring good strength of the bottom film, thereby effectively protecting the probe.

[0082] The features and properties of the present invention will be further described in detail below in conjunction with examples and comparative examples.

[0083] Example 1

[0084] Clean the substrate. The cleaning agent is a water-based cleaning agent (5058 from Henkel). The cleaning method is to make the cleaning agent circulate at a temperature of 40 °C, and the cleaning time is 10 min; dry for 5 h.

[0085] Immerse in a silane coupling agent (γ-methacryloxypropyltrimethoxysilane). The volume concentration of the silane coupling agent is 10%; dry.

[0086] Use a vacuum deposition system to deposit a film twice to form a first coating layer and a second coating layer respectively; the raw material for film deposition is parylene C powder.

[0087] Perform plasma treatment with oxygen and sulfur hexafluoride gas. The power of the plasma treatment is 50 W per layer of electrode, the flow rate of oxygen is 100 sccm, the flow rate of the fluorinated gas is 100 sccm, and the treatment time is 70 min.

[0088] After the plasma treatment, the vacuum deposition system is used again for coating to form a third coating layer; the coating raw material is parylene C powder, and the micro-structure is as follows Figure 2 。

[0089] According to Figure 2 it can be seen that a micro-scale hydrophobic structure with nano-scale fine protrusions similar to lotus leaves is formed on the surface of the substrate.

[0090] The thicknesses of the first coating layer, the second coating layer and the third coating layer and the height of the micro-nano structure are shown in Table 1.

[0091] Example 2 is similar to Example 1, the difference is that: the thicknesses of the first, second and third coating layers are different, specifically refer to Table 1.

[0092] Example 3

[0093] Clean the substrate, the cleaning agent is ethanol, the cleaning method is to make the cleaning agent circulate at a temperature of 80 °C, the cleaning time is 60 min; dry for 3 h.

[0094] Immerse in a silane coupling agent (tetraethyl orthosilicate), the volume concentration of the silane coupling agent is 0.1%; dry.

[0095] Use the vacuum deposition system for secondary coating to form the first coating layer and the second coating layer respectively; the coating raw material is parylene F powder.

[0096] Perform plasma treatment with oxygen and sulfur hexafluoride gas, the power of the plasma treatment is 30 W / layer electrode, the flow rate of oxygen is 60 sccm, the flow rate of the fluorinated gas is 60 sccm, and the treatment time is 90 min.

[0097] After the plasma treatment, the vacuum deposition system is used again for coating to form a third coating layer; the coating raw material is parylene F powder, and the micro-structure is as follows Figure 3 。

[0098] According to Figure 3 it can be seen that a micro-scale hydrophobic structure with nano-scale fine protrusions similar to lotus leaves is formed on the surface of the substrate.

[0099] The thicknesses of the first coating layer, the second coating layer and the third coating layer and the height of the micro-nano structure are shown in Table 1.

[0100] Example 4

[0101] Clean the substrate, the cleaning agent is ethanol, the cleaning method is to make the cleaning agent circulate at a temperature of 60 °C, the cleaning time is 30 min; dry for 2 h.

[0102] Immerse in a silane coupling agent (tetraethyl orthosilicate), the volume concentration of the silane coupling agent is 5%; dry.

[0103] Use a vacuum deposition system for secondary coating to form a first coating layer and a second coating layer respectively; the raw material for coating is parylene F powder.

[0104] Perform plasma treatment with oxygen and sulfur hexafluoride gases. The power of the plasma treatment is 30 W / layer electrode, the flow rate of oxygen is 30 sccm, the flow rate of the fluorinated gas is 30 sccm, and the treatment time is 150 min.

[0105] After the plasma treatment, use the vacuum deposition system for coating treatment again to form a third coating layer; the raw material for coating is parylene F powder, and the micro-structure is as follows Figure 4 .

[0106] According to Figure 4 it can be seen that a micro-hydrophobic structure with nano-scale fine protrusions similar to lotus leaves is formed on the surface of the substrate.

[0107] The thicknesses of the first coating layer, the second coating layer, the third coating layer and the height of the micro-nano structure are shown in Table 1.

[0108] The processes of Examples 5-7 are similar to those of Example 1, the difference lies in the thicknesses of the first coating layer, the second coating layer and the third coating layer, which are specifically shown in Table 1.

[0109] Example 8

[0110] Example 8 is similar to Example 1, the difference lies in that: the plasma treatment time is 20 min, the thicknesses of the first coating layer, the second coating layer and the third coating layer are shown in Table 1; other processes refer to Example 1.

[0111] Example 9

[0112] Example 9 is similar to Example 1, the difference lies in that: the plasma treatment time is 10 min, the thicknesses of the first coating layer, the second coating layer and the third coating layer are shown in Table 1; other processes refer to Example 1.

[0113] Example 10

[0114] Example 10 is similar to Example 1, the difference lies in that: the thicknesses of the first coating layer, the second coating layer and the third coating layer are specifically shown in Table 1; other processes refer to Example 1.

[0115] The processes of Examples 11-16 are similar to those of Example 1, the difference lies in that: the thicknesses of the first coating layer, the second coating layer and the third coating layer are specifically shown in Table 1.

[0116] Comparative Example 1 is similar to Example 2, the difference lies in that: only the first coating layer is deposited, the coating layer thickness is specifically referred to Table 1, and plasma treatment is not performed.

[0117] Comparative Example 2 is similar to Example 2, except that: only the first and third coating layers are deposited, and the specific thicknesses are referred to Table 1; plasma treatment is performed on the first coating layer.

[0118] Comparative Example 3 is similar to Example 2, except that: only the first coating layer is deposited, and the specific thickness is referred to Table 1; plasma treatment is performed on the first coating layer.

[0119] The processes of Comparative Examples 4 and 6 are similar to those of Example 1, except for the thicknesses of the first, second, and third coating layers and the height of the micro-nano structure (see Table 1 for the thickness data and the height of the micro-nano structure), the power of the plasma treatment is 150 W / layer electrode, the flow rate of oxygen is 60 sccm, the flow rate of the fluorinated gas is 60 sccm, and the treatment time is 180 min.

[0120] The processes of Comparative Examples 5 and 7 are similar to those of Example 1, except for the thicknesses of the first, second, and third coating layers and the height of the micro-nano structure (see Table 1 for the thickness data and the height of the micro-nano structure), the power of the plasma treatment is 50 W / layer electrode, the flow rate of oxygen is 100 sccm, the flow rate of the fluorinated gas is 100 sccm, and the treatment time is 70 min.

[0121] The process of Comparative Example 8 is similar to that of Example 8, except for the thicknesses of the first, second, and third coating layers and the height of the micro-nano structure (see Table 1 for the thickness data and the height of the micro-nano structure), the power of the plasma treatment is 50 W / layer electrode, the flow rate of oxygen is 100 sccm, the flow rate of the fluorinated gas is 100 sccm, and the treatment time is 70 min.

[0122] The process of Comparative Example 9 is similar to that of Example 8, except for the thicknesses of the first, second, and third coating layers and the height of the micro-nano structure (see Table 1 for the thickness data and the height of the micro-nano structure), the power of the plasma treatment is 150 W / layer electrode, the flow rate of oxygen is 60 sccm, the flow rate of the fluorinated gas is 60 sccm, and the treatment time is 180 min.

[0123] The process of Comparative Example 10 is similar to that of Example 1, except for the thicknesses of the first, second, and third coating layers and the height of the micro-nano structure (see Table 1 for the thickness data and the height of the micro-nano structure), the power of the plasma treatment is 30 W / layer electrode, the flow rate of oxygen is 30 sccm, the flow rate of the fluorinated gas is 30 sccm, and the treatment time is 60 min.

[0124] Table 1

[0125]

[0126] Experimental Example 1

[0127] The adhesion and appearance of the substrates treated in Examples 1 and 3 were detected and observed.

[0128] The adhesion detection method was the cross-cut test method, and the detection results are shown in Figure 5 and Figure 6 ; The experimental results show that the adhesion of the film layer of the substrates provided in Examples 1 and 3 reaches 5B (the highest level of adhesion that can be detected by the cross-cut test method).

[0129] Visually observe the appearance of the substrate in Example 1. There are no obvious imprints, and the film layer is intact. A photo is taken to obtain Figure 7 .

[0130] Experimental Example 2

[0131] The 3× and 200× appearance detections were carried out on the substrate treated in Example 1 and the uncoated substrate. The detection results are shown in Figure 8 .

[0132] Experimental Example 3

[0133] The hydrophilic and hydrophobic detections were carried out on the substrate treated in Example 1 and the conventional parylene film. The detection results are as Figure 9 . According to Figure 9 , it can be known that the preparation method provided by the present invention can effectively prepare a protective film layer with good hydrophobicity.

[0134] Experimental Example 4

[0135] The hydrophilic and hydrophobic detections were carried out by comparing the substrate treated in Example 1, the conventional parylene film and the untreated substrate. The detection results are as Figure 10 and Figure 11 . According to Figure 10 and Figure 11 , it can be known that the preparation method provided by the present invention can effectively prepare a protective film layer with good hydrophobicity.

[0136] Combined with Figure 8 in Experimental Example 2 Figure 10 and

[0137] in Experimental Example 4, it can be seen that the surface changes little between the coated and uncoated substrates, that is, coating does not affect the surface of the probe.

[0138] The electron microscope scanning was carried out on the substrate treated in Example 1 and the conventional parylene film. The scanning results are shown in Figure 12 . According to Figure 12 , it can be known that the surface of the protective film formed by the preparation method of the present invention has a relatively uniform convex structure, and thus has good hydrophobicity, while the conventional parylene film shows a smooth surface structure and poor hydrophobicity.

[0139] Experimental Example 6

[0140] High-precision detection was carried out on the conventional parylene film, and the results are shown in Figure 13 . Comparing Figure 2 and Figure 13 , it can be seen that the surface of the protective film formed by the preparation method of the present invention has a relatively uniform convex structure, and thus has good hydrophobicity, while the surface of the conventional parylene film has no convex structure and poor hydrophobicity.

[0141] Experimental Example 7

[0142] The substrates treated in Examples 1 and 3 (the experimental results of Example 1 are the part shown as "deionized water: 2" in the figure, and the experimental results of Example 3 are the part shown as "deionized water: 3" in the figure), the conventional parylene film (with a thickness of 7.3 μm and the experimental results are the part shown as "deionized water: 1" in the figure), and the untreated substrate (the experimental results are the part shown as "deionized water: 0" in the figure) were soaked in deionized water for 3 days, and the soaking results are shown in Figure 14 . According to Figure 14 , it can be known that compared with the substrate without the film layer, both the conventional parylene and the film layer structures of Examples 1 and 3 show protective performance; comparatively, the film layers provided by Examples 1 and 3 have more obvious protective performance than the conventional parylene film layer.

[0143] Experimental Example 8

[0144] The substrates treated in Examples 1 and 3 (the experimental results of Example 1 are the part shown as "PBS: 2" in the figure, and the experimental results of Example 3 are the part shown as "PBS: 3" in the figure), the conventional parylene film (with a thickness of 7.3 μm and the experimental results are the part shown as "PBS: 1" in the figure), and the untreated substrate (the experimental results are the part shown as "PBS: 0" in the figure) were soaked in PBS solution (the PBS formula with a pH of 7.4 for 1 L is: 0.24 g of potassium dihydrogen phosphate (KH2PO4), 1.44 of disodium hydrogen phosphate (Na2HPO4), 8.0 g of sodium chloride (NaCl), 0.2 g of potassium chloride (KCl), and add water to 1000 mL) for 3 days, and the soaking results are shown in Figure 15 . According to Figure 15 , it can be known that compared with the substrate without the film layer, both the conventional parylene and the film layer structures of Examples 1 and 3 show protective performance; comparatively, the film layers provided by Examples 1 and 3 have more obvious protective performance than the conventional parylene film layer.

[0145] Experimental Example 9

[0146] The water vapor transmission rate test was carried out on the treated substrates in Example 2 and Comparative Examples 1, 2, and 3. The experimental method was the perspective cup weighing method (weight gain method) carried out in accordance with GB1037, and the test results are shown in Table 2.

[0147] Table 2

[0148] <![CDATA[Water vapor transmission rate of the repeating group (g / m 2 ·24h)]]> Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 1 3.10 3.52 5.89 51.90 2 3.28 3.67 6.11 53.89 3 3.25 3.39 6.23 52.83 Average value 3.21 3.53 6.08 52.88

[0149] According to Table 3, it can be seen that there is a significant difference between Example 2 and Comparative Example 1. It can be seen that the water vapor transmission rate after no plasma treatment increases compared with that after plasma treatment (that is, the water vapor transmission rate after plasma treatment decreases compared with that after no plasma treatment). There is a highly significant difference between Example 2 and Comparative Example 3. From this, it can be known that if the integrity of the first coating layer is not protected by setting the second coating layer and the plasma treatment is directly carried out on the first coating layer, the water vapor transmission rate will not only not decrease, but will increase significantly, indicating that the plasma treatment will greatly damage the integrity of the first coating layer, resulting in a significant decrease in the protection strength and stability of the parylene layer.

[0150] Specifically, according to Table 2, it can be seen that when the first parylene coating layer is treated by plasma, although a hydrophobic structure appears on the surface, the complete structure and surface inertness of the film layer have actually been damaged, thereby affecting the protective performance of the film layer. Taking the water vapor transmission rate as the characterization parameter, the water vapor transmission rate increases greatly. The data are shown in Comparative Example 3; this effect can be remedied to a certain extent by the outermost parylene film layer. The data are shown in Comparative Example 2. The water vapor transmission rate of Comparative Example 2 decreases compared with that of Comparative Example 3, but it is not enough to resist the influence of plasma treatment on the performance of the complete film layer. The data are shown in Comparative Example 1, that is, the water vapor transmission rate of Comparative Example 2 is greater than that of Comparative Example 1, indicating that the plasma treatment in Comparative Example 2 has an adverse effect on the integrity of the film layer. Therefore, in the present invention, by carrying out plasma treatment on the second parylene film coating layer and adding a third parylene film layer, it not only does not affect the formation of the hydrophobic property of the plasma, but also improves the protective performance of the overall structural film layer. The data are shown in Example 2.

[0151] Experimental Example 10

[0152] The adhesion, corrosion resistance, and waterproof performance of the treated substrates in each example and comparative example in Table 3 were detected. For the detection of corrosion resistance, each treated substrate was immersed in a brine (sodium chloride solution) with a mass concentration of 5%, and the infiltration time is shown in Table 3; for the detection of waterproof performance, each treated substrate was immersed in water for soaking, and the soaking time is shown in Table 3, and it was observed whether rust spots appeared; the results are shown in Table 3.

[0153] Table 3

[0154] Bonding strength 5wt% brine Corrosion resistance Water Waterproof performance Example 1 5B 24h Qualified Soaked in water for 3 days Qualified Example 3 5B 24h Qualified Soaked in water for 3 days Qualified Example 4 5B 24h Qualified Soaked in water for 3 days Qualified Comparative Example 4 5B 24h Poor Soaked in water for 3 days Small rust spots Comparative Example 5 5B 24h Poor Soaked in water for 3 days Small rust spots Example 5 5B 48h Qualified Soaked in water for 8 days Qualified Example 6 5B 48h Qualified Soaked in water for 8 days Qualified Example 7 5B 48h Qualified Soaked in water for 8 days Qualified Comparative Example 6 5B 48h Poor Soaked in water for 8 days Small rust spots Comparative Example 7 5B 48h Poor Soaked in water for 8 days Small rust spots Example 8 5B 96h Qualified Soaked in water for 14 days Qualified Example 9 5B 96h Qualified Soaked in water for 14 days Qualified Example 10 5B 96h Qualified Soaked in water for 14 days Qualified Comparative Example 8 5B 96h Poor Soaked in water for 14 days Small rust spots Comparative Example 9 5B 96h Poor Soaked in water for 14 days Small rust spots Example 11 5B 96h Qualified Soaked in water for 14 days Qualified Example 12 5B 96h Qualified Soaked in water for 14 days Qualified Example 13 5B 96h Qualified Soaked in water for 14 days Qualified Example 14 5B 96h Qualified Soaked in water for 14 days Qualified Example 15 5B 96h Qualified Soaked in water for 14 days Qualified Example 16 5B 96h Qualified Soaked in water for 14 days Qualified Comparative Example 10 5B 24h Poor Soaked in water for 3 days Small rust spots

[0155] According to Table 1 and Table 3, by comparing Comparative Examples 4, 6, 9 and Examples 1, 3 - 10, it can be seen that when the thicknesses of the first coating layer and the second coating layer are appropriate, if the thickness of the second coating layer is the same as the height of the micro - nano structure formed after plasma treatment (i.e., there is an area where the height of the micro - nano structure has a value of 0), the waterproofness and corrosion resistance cannot be guaranteed.

[0156] According to Table 1 and Table 3, by comparing Comparative Examples 5, 7, 8 and Examples 1, 3 - 10, it can be seen that when the thickness of the first coating layer is appropriate but the thickness of the second coating layer is inappropriate, it is easier to completely remove the second coating layer during plasma treatment, that is, the thickness of the second coating layer is the same as the height of the micro - nano structure formed after plasma treatment, which means there is an area where the height of the micro - nano structure has a value of 0, and it is even more impossible to guarantee the waterproofness and corrosion resistance.

[0157] According to Table 1 and Table 3, by comparing Comparative Example 10 and Examples 1, 3 - 10, it can be seen that if the thickness of the second coating layer is less than 1.5 μm, even if the first coating layer is thick enough and the thickness of the second coating layer is higher than the height of the micro - nano structure formed after plasma treatment, the waterproofness and corrosion resistance cannot be guaranteed; the main reason is that when the thickness of the second coating layer is too thin, it is easy to cause damage to the first coating layer during plasma treatment, thereby reducing the waterproofness and corrosion resistance.

[0158] According to Examples 1, 3 - 16, it can be seen that when the thicknesses of the first coating layer and the second coating layer are appropriate and relatively thick, the thickness of the third coating layer can be appropriately reduced while still ensuring the waterproofness and corrosion resistance.

[0159] Experimental Example 11

[0160] The substrate of Example 1 that had been soaked in water for 3 days in Experimental Example 10 and the uncoated substrate of the comparative example that had been soaked in water for 3 days were placed in the same storage environment for storage. After 6 months, the changes in the substrate of Example 1 and the substrate of the comparative example were observed, and the results are as Figure 16 shown; among them, the part marked "uncoated" shows the morphology of the substrate of the comparative example just after being taken out after water immersion, the part marked "uncoated - 1" shows the morphology of the soaked substrate of the comparative example after being stored for 6 months, and "hydrophobic treatment" shows the morphology of the substrate of Example 1 after being stored for 6 months after water immersion.

[0161] According to Figure 16 it can be seen that the substrate of Example 1 had no obvious changes after 6 months, while the substrate of the comparative example had greater changes, indicating that the substrate of Example 1 has good waterproof and corrosion resistance.

[0162] In summary, the preparation method of the parylene coating for the detection probe of the present invention forms two parylene film layers by depositing a coating on a substrate, and performs plasma treatment on the second parylene film layer, so that the medical probe with the parylene coating for the detection probe has biocompatibility while improving hydrophobicity, thereby improving the detection accuracy, stability and corrosion resistance of the medical probe and prolonging the service life of the medical probe.

[0163] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A preparation method for a parylene coating of a detection probe, characterized in that, Comprising: Cleaning the substrate; Treating the substrate with a silane coupling agent; Performing a first deposition coating on the substrate to form a first coating layer; Performing a second deposition coating on the first coating layer to form a second coating layer; Performing plasma treatment on the second coating layer, and Performing a third deposition coating after the plasma treatment to form a third coating layer; wherein: The first coating layer, the second coating layer and the third coating layer are all parylene film layers; The thickness of the second coating layer is at least 1.5 μm, and the thickness of the second coating layer is greater than the height of the micro-nano structure after plasma treatment.

2. The preparation method of the parylene coating for the detection probe according to claim 1, characterized in that, The height of the micro-nano structure after plasma treatment is at least 0.01 μm.

3. The preparation method of the parylene coating for detecting the probe according to claim 1, wherein, The thickness of the second coating layer is 2 - 10 μm.

4. The preparation method of the parylene coating for the detection probe according to claim 1, characterized in that, The thickness of the third coating layer is at least 0.05 μm.

5. The preparation method of the parylene coating for the detection probe according to any one of claims 1-4, characterized in that, The cleaning liquid used in the cleaning step includes at least one of an alcohol-based cleaning liquid and a water-based cleaning agent; the cleaning method includes circulating the cleaning liquid at a temperature of 40 - 80 °C for cleaning; the cleaning time is 10 min - 60 min.

6. The preparation method of the parylene coating for the detection probe according to any one of claims 1-4, characterized in that, The volume concentration of the silane coupling agent is 0.1 - 10%.

7. The preparation method of the parylene coating for the detection probe according to any one of claims 1-4, characterized in that, The raw materials used in the plasma treatment step are fluorinated gas and oxygen.

8. The preparation method of the parylene coating for the detection probe according to claim 7, characterized in that, The fluorinated gas is selected from at least one of sulfur hexafluoride and hexafluoropropylene.

9. The preparation method of the parylene coating for the detection probe according to claim 7, characterized in that, The power of the plasma treatment is 30 - 300 W / layer electrode, the flow rate of oxygen is 30 - 200 sccm, and the flow rate of the fluorinated gas is 30 - 200 sccm.

10. The preparation method of the parylene coating for the detection probe according to claim 7, characterized in that, The time of the plasma treatment is 10 - 200 min.

11. The preparation method of the parylene coating for the detection probe according to any one of claims 1-4, characterized in that, The thickness of the first coating layer is 1 - 100 μm.

12. The preparation method of the parylene coating for the detection probe according to any one of claims 1-4, characterized in that, Also comprising: When the humidity of the use environment of the probe ≤ 30%, the thickness of the first coating layer is 2 - 10 μm, and the thickness of the third coating layer is at least 0.1 μm; When the humidity of the use environment of the probe > 30% and ≤ 80%, the thickness of the first coating layer is 15 - 20 μm, and the thickness of the third coating layer is at least 0.08 μm; When the use environment of the probe is immersion in an aqueous liquid, the thickness of the first coating layer is greater than or equal to 30 μm, and the thickness of the third coating layer is at least 0.05 μm.

13. The preparation method of the parylene coating for detecting the probe according to claim 12, wherein, When the use environment of the probe is long-term immersion in an aqueous liquid or a salt spray environment, the thickness of the first coating layer is greater than or equal to 50 μm.

14. A parylene coating for a detection probe, characterized in that, It is prepared by the preparation method of the parylene coating for detecting a probe according to any one of claims 1 - 13.

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