1. A shield device for repelling microorganisms from the surface of an optical window in seawater, comprising: the protector is used for covering and establishes on optical window, the protector includes glass substrate, first functional layer and second functional layer, wherein:

the glass substrate with high light transmittance is used for supporting the first functional layer and the second functional layer;

the first functional layer is uniformly coated on the surface of the glass substrate and is made of a high-light-transmission material;

the second functional layer is arranged on the surface of the first functional layer far away from the glass substrate, and the second functional layer or the first functional layer is used for receiving an excitation signal from the optical window and, after receiving the excitation signal:

the first functional layer or the second functional layer repels adhered microorganisms; or the like, or, alternatively,

the first functional layer and the second functional layer repel adhering microbes.

2. The shielding device of claim 1, wherein: the first functional layer is a semiconductor two-dimensional material, and the second functional layer is an electrode distributed on the surface of the semiconductor two-dimensional material; the excitation signal is excitation light;

and the semiconductor two-dimensional material and the electrode generate current after receiving the exciting light, so that attached microorganisms are expelled.

3. The shielding device of claim 1, wherein: the first functional layer is made of piezoelectric materials, the second functional layer is made of interdigital electrodes, the excitation signal is a voltage signal, and after the interdigital electrodes receive the voltage signal, the interdigital electrodes apply voltage to the piezoelectric materials; the piezoelectric material generates mechanical vibration and releases sound waves, thereby repelling attached microorganisms.

4. The shielding device of claim 3, wherein: the piezoelectric material is polyvinylidene fluoride; or the like, or, alternatively,

the piezoelectric material is gallium nitride, and the excitation signal further comprises ultraviolet light.

5. A method for manufacturing a protective device is characterized in that,

step 1: soaking a glass slide by using acid, alkali or hydrogen peroxide, or bombarding the glass slide by using oxygen plasma to hydrophilize the glass slide, wherein the hydrophilized glass slide is used as a glass substrate;

step 2: transferring the copper-based graphene film to the surface of the glass substrate to form a first functional layer;

and step 3: manufacturing an electrode on the surface of the first functional layer by utilizing a photoetching technology, throwing photoresist on the surface of the first functional layer, curing, soaking and cleaning the exposed electrode pattern by using a developing solution, and plating gold to obtain the electrode;

and 4, step 4: and dissolving the photoresist to prepare the protective device.

6. The method of manufacturing a guard according to claim 5,

in the step 2, a layer of polymethyl methacrylate film is coated on the surface of the copper-based graphene film in a spin mode, then the copper-based graphene film is corroded in a ferric chloride solution, washed for multiple times and dried, then the polymethyl methacrylate film is pasted on a glass sheet, the polymethyl methacrylate is dissolved and washed by acetone, and then the copper-based graphene film is dried, so that the copper-based graphene film is transferred to the surface of the glass substrate to form the first functional layer.

7. The method of manufacturing a guard according to claim 5,

in the step 2, the copper-based graphene film is placed in a ferric chloride solution for corrosion, then the copper-based graphene film is fished out by the glass substrate, and the copper-based graphene film is transferred to the surface of the glass substrate to form a first functional layer after being dried.

8. A method for manufacturing a protective device is characterized in that,

step 1: soaking a glass slide by using acid, alkali or hydrogen peroxide, or bombarding the glass slide by using oxygen plasma to hydrophilize the glass slide, wherein the hydrophilized glass slide is used as a glass substrate;

step 2: depositing or spin-coating a piezoelectric material on the surface of the glass substrate to form a first functional layer;

and step 3: manufacturing an electrode on the surface of the first functional layer by utilizing a photoetching technology: throwing photoresist on the surface of the first functional layer, curing, exposing electrode patterns, soaking and cleaning with a developing solution, and plating gold to obtain the electrode;

and 4, step 4: and dissolving the photoresist to prepare the protective device.

9. The method of manufacturing a shielding device according to claim 8,

in the step 2, the piezoelectric material is gallium nitride, and is deposited on the surface of the glass substrate by adopting an organic metal chemical vapor deposition method to form the first functional layer; or the like, or, alternatively,

in the step 2, the piezoelectric material is polyvinylidene fluoride, and the first functional layer is formed on the surface of the glass substrate by adopting a spin-coating drying mode.

10. A method for repelling microorganisms, wherein an optical window in seawater is covered with a shield according to claim 1, wherein the microorganisms adhere to the surface of the shield,

the optical window emits an excitation signal to the guard,

the excitation signal is an excitation light signal, and the surfaces of the first functional layer and the second functional layer generate current so as to expel the microorganisms; or the like, or, alternatively,

the excitation signal is a voltage signal, and the first functional layer vibrates mechanically and releases sound waves, so that the microorganisms are expelled.

Background

In the field of marine related scientific research, marine microorganisms attached to the surface of an instrument are always difficult to solve, the marine microorganisms attached to the surface of the instrument can cause corrosion and damage of a shell, in addition, for marine optical research, the marine microorganisms can shield a signal channel when attached to an optical window, so that the optical signal transmission is seriously attenuated, even the optical signal is cut off, and therefore how to realize the microbial chasing of the surface of the instrument, particularly the surface of the optical window, is widely concerned by scientific research workers.

In order to solve the problems, an active protection mode does not exist at present, and usually the surface of an instrument/ship is coated with an isolation paint for protection, but the passive protection method has limited time efficiency, long-term maintenance and high maintenance cost.

Disclosure of Invention

The object of the present invention is at least to provide a novel shielding device, as well as a method for its manufacture and a method for repelling micro-organisms, for repelling micro-organisms from the surface of an optical window in seawater.

In order to achieve the purpose, the invention adopts the technical scheme that:

in one aspect, the present invention provides a protective device for repelling microorganisms from a surface of an optical window in seawater, the protective device being adapted to cover the optical window, the protective device comprising a glass substrate, a first functional layer, and a second functional layer, wherein:

the glass substrate with high light transmittance is used for supporting the first functional layer and the second functional layer;

the first functional layer is uniformly coated on the surface of the glass substrate and is made of a high-light-transmission material;

the second functional layer is arranged on the surface of the first functional layer far away from the glass substrate, and the second functional layer or the first functional layer is used for receiving an excitation signal from the optical window and, after receiving the excitation signal:

the first functional layer or the second functional layer repels adhered microorganisms; or the like, or, alternatively,

the first functional layer and the second functional layer repel adhering microbes.

When the protector is placed on the outer surface of the optical window in seawater, microorganisms that would have adhered to the outer surface of the optical window adhere to the outer side of the protector. Because the first functional layer and the glass substrate are both made of high-light-transmission materials, the protection device can not influence the transmission of optical signals required by the optical device corresponding to the optical window. When the attached microorganisms need to be expelled, an excitation signal is sent to the protection device through the optical window, and after the protection device receives the corresponding excitation signal, the attached microorganisms are expelled by the first functional layer or/and the second functional layer, so that the microorganisms are actively expelled.

As an optional solution, the first functional layer is a semiconductor two-dimensional material, and the second functional layer is an electrode distributed on the surface of the semiconductor two-dimensional material; the excitation signal is excitation light;

and the semiconductor two-dimensional material and the electrode generate current after receiving the exciting light, so that attached microorganisms are expelled.

In the scheme, the light transmittance of the semiconductor two-dimensional material is good, and when excitation light irradiates on the semiconductor two-dimensional material, an 'electron-hole' pair can be generated to form photocurrent under the action of external bias voltage; further, the electrodes distributed on the surface of the two-dimensional material can realize optical pump local excitation pulse current, and the optical pump local excitation pulse current and the photocurrent superposition effect realize the expulsion of attached microorganisms.

As another optional scheme, the first functional layer is a piezoelectric material, the second functional layer is an interdigital electrode, the excitation signal is a voltage signal, and after the interdigital electrode receives the voltage signal, the interdigital electrode applies a voltage to the piezoelectric material; the piezoelectric material generates mechanical vibration and releases sound waves, thereby repelling attached microorganisms.

In the scheme, the optical window transmits a voltage signal to the interdigital electrode through a wire and the like, the interdigital electrode then transmits the received voltage signal to the piezoelectric material, the piezoelectric material can convert electric energy into mechanical energy, vibration is generated, sound waves are released, and then the attached microorganisms are expelled.

Preferably, the piezoelectric material is polyvinylidene fluoride or gallium nitride.

The maximum light transmittance of the polyvinylidene fluoride (PVDF) in the visible spectrum is 96%, and the transmission of optical signals required by the optical device corresponding to the optical window is hardly influenced.

The 280nm ultraviolet transmittance of gallium nitride is greater than 60%, when additionally penetrating through the optical window when exerting voltage to it, can be on the basis of mechanical vibration and sound wave expulsion microorganism, and the effect is exterminated to the expulsion of microorganism to the stack ultraviolet ray, further promotes.

In one aspect, the present invention provides a method of manufacturing a protective device, comprising the steps of:

step 1: soaking a glass slide by using acid, alkali or hydrogen peroxide, or bombarding the glass slide by using oxygen plasma to hydrophilize the glass slide, wherein the hydrophilized glass slide is used as a glass substrate;

step 2: transferring a copper-based graphene film (copper-based graphene (WJCS/F), wherein graphene grows on the surface of a copper foil, and a copper-based single-layer graphene film, a copper-based double-layer graphene film and a copper-based few-layer graphene film can be provided) to the surface of the glass substrate to form a first functional layer;

and step 3: manufacturing an electrode on the surface of the first functional layer by utilizing a photoetching technology, throwing photoresist on the surface of the first functional layer, curing, soaking and cleaning the exposed electrode pattern by using a developing solution, and plating gold to obtain the electrode;

and 4, step 4: and dissolving the photoresist to prepare the protective device.

In the scheme, the acid or the base for hydrophilizing the glass slide is strong acid or strong base respectively, wherein the acid can be concentrated sulfuric acid with the mass fraction being more than 70% or hydrochloric acid solution with the mass fraction being more than 35%, and the base can be sodium hydroxide solution with the mass fraction being more than 30%.

As an optional scheme, in step 2, a layer of polymethyl methacrylate (PMMA) film is spin-coated on the surface of the copper-based graphene film, and then the copper-based graphene film is corroded in a ferric chloride solution, washed and dried for many times, the PMMA film is adhered to a glass slide, and then the PMMA film is dissolved and washed by acetone and dried, so that the copper-based graphene film is transferred to the surface of the glass substrate to form the first functional layer.

The method for transferring the copper-based graphene thin film to the glass substrate comprises dry transfer (adhesive tape and mechanical stripping) and wet transfer, wherein the dry transfer is adopted as an alternative method, and the transfer process is more controllable compared with the wet transfer.

As another optional scheme, in the step 2, the copper-based graphene film is placed in a ferric trichloride solution for corrosion, then the copper-based graphene film is fished out by the glass substrate, and after drying, the copper-based graphene film is transferred to the surface of the glass substrate to form the first functional layer.

The method is wet transfer, and compared with dry transfer, the transfer process is more convenient.

In another aspect, the present invention provides a method for manufacturing a protective device, comprising the steps of:

step 1: soaking a glass slide by using acid, alkali or hydrogen peroxide, or bombarding the glass slide by using oxygen plasma to hydrophilize the glass slide, wherein the hydrophilized glass slide is used as a glass substrate;

step 2: depositing or spin-coating a piezoelectric material on the surface of the glass substrate to form a first functional layer;

and step 3: manufacturing an electrode on the surface of the first functional layer by utilizing a photoetching technology: throwing photoresist on the surface of the first functional layer, curing, exposing electrode patterns, soaking and cleaning with a developing solution, and plating gold to obtain the electrode;

and 4, step 4: and dissolving the photoresist to prepare the protective device.

In the scheme, the acid or the base for hydrophilizing the glass slide is strong acid or strong base respectively, wherein the acid can be concentrated sulfuric acid with the mass fraction being more than 70% or hydrochloric acid solution with the mass fraction being more than 35%, and the base can be sodium hydroxide solution with the mass fraction being more than 30%.

Further, in the step 2, the piezoelectric material is gallium nitride, and the piezoelectric material is deposited on the surface of the glass substrate by a Metal Organic Chemical Vapor Deposition (MOCVD) method to form the first functional layer; or the like, or, alternatively,

in the step 2, the piezoelectric material is polyvinylidene fluoride, and the first functional layer is formed on the surface of the glass substrate by adopting a spin-coating drying mode.

In a further aspect, the present invention provides a method for repelling microorganisms, wherein a protective device as described above is covered on an optical window in seawater, and the microorganisms adhere to the surface of the protective device,

the optical window emits an excitation signal to the guard,

the excitation signal is an excitation light signal, and the surfaces of the first functional layer and the second functional layer generate current so as to expel the microorganisms; or the like, or, alternatively,

the excitation signal is a voltage signal, and the first functional layer vibrates mechanically and releases sound waves, so that the microorganisms are expelled.

Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:

a) the arrangement of the protective device can realize effective active expelling of microorganisms in the ocean attached to the protective device, thereby realizing active protection of the surface of the optical window;

b) by integrating various acoustic-optical-electrical functional materials, protection mechanisms of different ideas are provided, and meanwhile, flexible preparation of the device can be realized by regulating and controlling key parameters;

c) the manufacturing process is simple, the reliability of the device is high, and the normal work and long-acting cleanness of the optical window can be ensured.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.

Fig. 1 is a top view of a guard where the first functional layer is a piezoelectric material according to an embodiment of the present invention.

Fig. 2 is a side view of the guard where the first functional layer is a piezoelectric material according to an embodiment of the present invention.

Fig. 3 is a top view of a protective device when the first functional layer is a semiconductor two-dimensional material according to an embodiment of the present invention.

Fig. 4 is a side view of a guard where the first functional layer is a semiconductor two-dimensional material according to an embodiment of the present invention.

Wherein the reference numerals include: 1-glass substrate, 2-electrode, 21-extraction electrode, 3-piezoelectric material and 4-semiconductor two-dimensional material.

Detailed Description

In order to make the technical solutions of the present invention better understood and more clearly understood by those skilled in the art, the technical solutions of the embodiments of the present invention will be described below in detail and completely with reference to the accompanying drawings. It should be noted that the implementations not shown or described in the drawings are in a form known to those of ordinary skill in the art. Additionally, while exemplifications of parameters including particular values may be provided herein, it is to be understood that the parameters need not be exactly equal to the respective values, but may be approximated to the respective values within acceptable error margins or design constraints. It is to be understood that the described embodiments are merely exemplary of a portion of the invention and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. In addition, the terms "comprises" and "comprising," and any variations thereof, in the description and claims of this invention, are intended to cover a non-exclusive inclusion, such that a process, method, apparatus, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.

Example one

As shown in fig. 1-2, the present embodiment provides a protection device, which is used to cover an optical window (not shown) and expel microbes on the surface of the optical window (when the protection device is added), wherein the protection device comprises a glass substrate 1, a first functional layer and a second functional layer. The glass substrate 1 with high light transmittance is used for supporting the first functional layer and the second functional layer; the first functional layer is a high-transmittance material and is uniformly coated on the surface of the glass substrate 1, in the embodiment, the first functional layer is a piezoelectric material 3, specifically, polyvinylidene fluoride (PVDF), and the light transmittance of the polyvinylidene fluoride (PVDF) in a visible spectrum can reach 96%; the second functional layer is disposed on the surface of the first functional layer away from the glass substrate 1, and the second functional layer in this embodiment is an electrode 2, specifically an interdigital electrode.

The first functional layer or the second functional layer is configured to receive an excitation signal from the optical window, in this embodiment, the excitation signal is a voltage signal, and the electrode 2 is configured to receive the voltage signal and provide a voltage to the piezoelectric material 3. An extraction electrode 21 is arranged between the electrode 2 and the optical window, and the electrode 2 is electrically connected with a power supply mechanism on the optical window through the extraction electrode 21. Upon receiving the excitation signal, the first functional layer or the second functional layer repels the attached microorganisms, or the first functional layer and the second functional layer repel the attached microorganisms. In this embodiment, when it is necessary to expel the attached microorganisms, a voltage signal is generated by a power supply mechanism on the optical window, the voltage signal is transmitted to the electrode 2 through the extraction electrode 21, the electrode 2 applies a voltage to the piezoelectric material 3 after receiving the voltage signal, and then the piezoelectric material 3 generates mechanical vibration and releases sound waves, thereby expelling the attached microorganisms, thereby realizing active protection of the optical window.

The manufacturing method of the protection device of the embodiment comprises the following steps:

step 1: soaking a glass slide by using acid, alkali or hydrogen peroxide, or bombarding the glass slide by using oxygen plasma to hydrophilize the glass slide, wherein the hydrophilized glass slide is used as a glass substrate; in this embodiment, the acid or the base is strong acid or strong base, respectively, wherein the acid may be concentrated sulfuric acid with a mass fraction of > 70% or hydrochloric acid solution with a mass fraction of > 35%, and the base may be sodium hydroxide solution with a mass fraction of > 30%.

Step 2: depositing or spin-coating a piezoelectric material on the surface of the glass substrate to form a first functional layer; in this embodiment, when the piezoelectric material 3 is polyvinylidene fluoride (PVDF), the piezoelectric material 3 is deposited on the surface of the glass substrate by using a Metal Organic Chemical Vapor Deposition (MOCVD) method to form the first functional layer;

and step 3: manufacturing an electrode on the surface of the first functional layer by utilizing a photoetching technology: throwing photoresist on the surface of the first functional layer, curing, exposing electrode patterns, soaking and cleaning with a developing solution, and plating gold to obtain the electrode;

and 4, step 4: and dissolving the photoresist to prepare the protective device.

The method for expelling microorganisms in the embodiment, wherein the optical window in the seawater is covered with the protection device, and the microorganisms are attached to the outer surface of the protection device provided by the embodiment, comprises the following steps:

the optical window emits an excitation signal to the guard,

the excitation signal is a voltage signal, the second functional layer electrode 2 applies the voltage signal to the first functional layer piezoelectric material 3, and the first functional layer mechanically vibrates and releases sound waves, thereby expelling the microorganisms.

Example two

The protection device provided by the embodiment is different from the first embodiment in that: the piezoelectric material 3 is made of gallium nitride, and the transmittance of the piezoelectric material to 280nm ultraviolet light is more than 60%. In the preparation process of the protective device, when the piezoelectric material 3 is gallium nitride, the piezoelectric material 3 forms the first functional layer on the surface of the glass substrate 1 by adopting a spin-coating drying mode.

In this embodiment, the excitation signal further includes ultraviolet light. Because the transmissivity of the gallium nitride to the 280nm ultraviolet light is greater than 60%, the method for expelling the microorganisms further can project the ultraviolet light outwards through the optical window, and then the attached microorganisms can be killed, and the effect of expelling the microorganisms is improved.

EXAMPLE III

As shown in fig. 3-4, the protection device provided in this embodiment is different from the first embodiment in that: the first functional layer is a semiconductor two-dimensional material 4, specifically adopts copper-based graphene, the second functional layer is electrodes 2 uniformly and widely distributed on the surface of the semiconductor two-dimensional material 4, the electrodes 2 can also be interdigital electrodes, and the excitation signal is excitation light.

The semiconductor two-dimensional material 4 has the characteristics of good mechanical property, lightness and thinness, capability of being directly adhered to a substrate such as silicon dioxide, silicon and the like through Van der Waals force and the like, and can be widely applied to the manufacture of photoelectric devices. Taking graphene as an example, the single-layer thickness of the graphene is only 0.33nm, the graphene has the characteristics of large optical absorption, good electric and thermal conductivity, strong thermal stability and the like, and the light transmittance of the graphene in a visible light (550nm) region can reach 97.7%, so that the graphene is a good high-transmittance electrode material.

Specifically, when light is irradiated on a semiconductor two-dimensional material 4 such as graphene, an "electron-hole" pair is generated, and a photocurrent is formed under the action of an external bias voltage; further, the electrodes distributed on the surface of the two-dimensional material can realize optical pump local excitation pulse current, and the optical pump local excitation pulse current and the photocurrent superposition effect realize the expulsion of attached microorganisms. In addition, if a plurality of (two or more) low-dimensional materials are used for forming a heterojunction, namely more than two layers of different semiconductor material films are deposited on the same base in sequence, the current can be increased, and more effective expelling or killing of microorganisms can be realized.

The manufacturing method of the protection device provided by the embodiment comprises the following steps:

step 1: soaking a glass slide by using acid, alkali or hydrogen peroxide, or bombarding the glass slide by using oxygen plasma to hydrophilize the glass slide, wherein the hydrophilized glass slide is used as a glass substrate; in this embodiment, the acid or the base is strong acid or strong base, respectively, wherein the acid may be concentrated sulfuric acid with a mass fraction of > 70% or hydrochloric acid solution with a mass fraction of > 35%, and the base may be sodium hydroxide solution with a mass fraction of > 30%. The treatment method for hydrophilizing the slide glass may be only one of the above methods, or may be combined with the above methods, and the treatment method for hydrophilizing the slide glass is not limited to the above two methods, and the scope of the present invention is not limited thereto.

Step 2: transferring the copper-based graphene film to the surface of the glass substrate to form a first functional layer; the graphene of the copper-based graphene film grows on the surface of the copper foil, and the copper-based graphene film can be a copper-based single-layer graphene film or a double-layer graphene film, and can also be a few-layer graphene film, so that the protection scope of the invention is not limited by the above.

In the embodiment, a copper-based graphene film is transferred in a dry transfer mode, specifically, a layer of polymethyl methacrylate (PMMA) film is spin-coated on the surface of the copper-based graphene film, and then the PMMA film is corroded in a ferric trichloride solution, washed for many times and dried, the PMMA film is adhered to a glass sheet, and the PMMA is dissolved and washed by acetone and then dried, so that the copper-based graphene film is transferred to the surface of the glass substrate 1 to form a first functional layer. The dry transfer process is more controllable.

And step 3: manufacturing an electrode on the surface of the first functional layer by utilizing a photoetching technology, throwing photoresist on the surface of the first functional layer, curing, soaking the exposed electrode pattern into a developing solution, cleaning an exposed area, and then performing gold plating treatment to obtain the electrode;

and 4, step 4: and dissolving the photoresist to prepare the protective device.

The method for expelling microorganisms in the embodiment, wherein the optical window in the seawater is covered with the protection device, and the microorganisms are attached to the outer surface of the protection device provided by the embodiment, comprises the following steps:

the optical window emits an excitation signal to the guard,

the excitation signal is an excitation light signal which is transmitted to the semiconductor two-dimensional material 4 of the first functional layer, the semiconductor two-dimensional material 4 forms a photocurrent under the action of an external bias voltage, and the electrodes 2 distributed on the surface of the semiconductor two-dimensional material 4 generate a light pump local excitation pulse current which acts on attached microorganisms together with the photocurrent, so that the microorganisms are expelled.

Example four

The protection device provided by the embodiment is different from the third embodiment in that: the specific method of transferring the copper-based graphene film to the surface of the glass substrate 1 in step 2 of the manufacturing process of the protective device is different. Specifically, in this embodiment, a wet transfer method is used to transfer the copper-based graphene thin film, specifically, the copper-based graphene thin film is placed in a ferric trichloride solution to be corroded, then the copper-based graphene thin film is fished out by the glass substrate 1, and after drying, the copper-based graphene thin film is transferred to the surface of the glass substrate 1 to form a first functional layer. The wet transfer method is relatively convenient and simple to operate.

In conclusion, the technical scheme provided by the invention can not only realize the photoinduced effect in the protection device based on the photoelectric material, but also expel marine microorganisms through the photocurrent generated by the photoinduced effect; in addition, the material used in the invention has no obvious influence on the optical characteristics, is beneficial to long-time work of marine instruments in water, has strong and reliable feasibility, and also has the advantages of low cost and high firmness.

The above description is only for the preferred embodiment of the present invention and is not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes that can be directly or indirectly applied to other related technical fields using the contents of the present specification and the accompanying drawings are included in the scope of the present invention.