CN109935701B - Composite membrane and preparation method and application thereof - Google Patents
Composite membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a composite membrane and a preparation method and application thereof, wherein the method comprises the following steps: providing fullerol, mixing the fullerol with a silane coupling agent, and dehydrating to obtain fullerene modified by the silane coupling agent; providing a zero-dimensional wide band gap nanoparticle solution; providing a substrate, and depositing a zero-dimensional wide band gap nanoparticle solution on the substrate to form a first thin film; and depositing an alkaline fullerene solution modified by the silane coupling agent on the first film to form a second film, and combining a surface metal element in the zero-dimensional wide-band-gap nano-particles on the surface of the first film with an amino group or a mercapto group in the silane coupling agent in the fullerene on the surface of the second film at a combined interface of the first film and the second film to prepare the composite film. The method is simple to operate and easy to repeat, and can effectively reduce the junction potential barrier between the zero-dimensional wide-band-gap nano particles, so that the electric conduction and photoelectric response rate of the composite film is improved.
Description
Technical Field
The invention relates to the technical field of ultraviolet sensing devices, in particular to a composite film and a preparation method and application thereof.
Background
Ultraviolet (UV) sensors have a wide range of requirements in the industrial and scientific fields, such as: the method has wide application value in the fields of ultraviolet detection, high-temperature flame detection, missile flame plume detection, optical switching, optical communication and the like.
In the development process of materials of the ultraviolet sensor, the wide bandgap semiconductor material is a material such as zinc oxide, zinc sulfide and the like which meets the premise of the ultraviolet sensor. In the process of developing materials of the ultraviolet sensor, the one-dimensional nano material is found to have better electron transport property and larger specific surface area such as: zinc oxide nanowires, zinc oxide nanorods, and zinc oxide nanobelts; one-dimensional materials such as zinc sulfide nanowires, zinc sulfide nanorods, zinc sulfide nanobelts, and the like are widely used in UV sensors.
However, in the UV sensor prepared by using the above one-dimensional material, the photoelectric response time usually takes several seconds to several minutes or even several hundred minutes because the photocurrent switching rate is slower in the adsorption and desorption process of oxygen generated on the surface when using the above one-dimensional material. In the prior art, zero-dimensional nano materials (such as zinc oxide nano particles, zinc sulfide nano particles and the like) with large specific surface area are used for improving the oxygen adsorption and desorption rates so as to further improve the photocurrent switching rate; although the sensitivity of the sensor is improved to a certain extent by using the zero-dimensional nanoparticles to prepare the UV sensor, a junction barrier is easily formed between the zero-dimensional nanoparticles, and the junction barrier can block electron transmission to further influence the conductivity of a particle film and the photoelectric response rate of the sensor.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, an object of the present invention is to provide a composite film, a method for preparing the same, and an application thereof, which aim to solve the problem that junction barriers are easily formed between the existing zero-dimensional nanomaterials, and the junction barriers can hinder electron transport, thereby affecting the conductivity of the particle film and the photoelectric response rate of the sensor.
The technical scheme of the invention is as follows:
a method of making a composite membrane, comprising the steps of:
providing fullerol, mixing the fullerol with a silane coupling agent, and dehydrating to obtain fullerene modified by the silane coupling agent, wherein the general formula of the silane coupling agent is YSiX3Wherein X is alkoxy, Y is a non-hydrolyzable group, and the end of the carbon chain in Y contains an amino substituent or a mercapto substituent;
providing a zero-dimensional wide band gap nanoparticle solution;
providing a substrate, and depositing a zero-dimensional wide band gap nanoparticle solution on the substrate to form a first thin film;
and depositing an alkaline fullerene solution modified by the silane coupling agent on the first film to form a second film, and combining a surface metal element in the zero-dimensional wide-band-gap nano-particles on the surface of the first film with an amino group or a mercapto group in the silane coupling agent in the fullerene on the surface of the second film at a combined interface of the first film and the second film to prepare the composite film.
The preparation method of the composite membrane, wherein the general formula of the fullerol is Cm(OH)nWherein m is more than or equal to 28 and less than or equal to 104, n is more than or equal to 16 and less than or equal to 60, n<m。
The preparation method of the composite membrane comprises the step of selecting the silane coupling agent from NH2(CH2)3Si（OCH3）3、NH2(CH2)3Si（OC2H5）3、NH2(CH2)2NH(CH2)3Si（OCH3）3、NH2(CH2)2NH(CH2)3Si（OC2H5）3And SH (CH)2)3Si（OC2H5）3One kind of (1).
The preparation method of the composite film comprises the following steps of mixing the fullerol and the silane coupling agent and then dehydrating, wherein the molar ratio of the fullerol to the silane coupling agent is 1 mmol: (15-20 mmol), and mixing the fullerol with the silane coupling agent and then dehydrating.
The preparation method of the composite film comprises the step of preparing a zero-dimensional wide band gap nanoparticle solution, wherein the zero-dimensional wide band gap nanoparticle in the zero-dimensional wide band gap nanoparticle solution is selected from one of zinc oxide nanoparticles, zinc sulfide nanoparticles and gallium nitride nanoparticles.
The preparation method of the composite film comprises the step of preparing a zero-dimensional wide band gap nanoparticle solution, wherein the band gap range of zero-dimensional wide band gap nanoparticles in the zero-dimensional wide band gap nanoparticle solution is 3-4 eV.
The preparation method of the composite membrane is characterized in that in the zero-dimensional wide-band-gap nanoparticle solution, the concentration of the zero-dimensional wide-band-gap nanoparticles is 20-40 mg/mL.
The preparation method of the composite film comprises the following steps of depositing the zero-dimensional wide band gap nanoparticle solution on the substrate to form a first film: and depositing the zero-dimensional wide band gap nanoparticle solution on the substrate, and annealing for 30-60 min at 50-80 ℃ to form a first film on the substrate.
The method for preparing the composite film, wherein the step of depositing an alkaline solution containing the fullerene modified by the silane coupling agent on the first film to form a second film, and bonding the surface metal element in the zero-dimensional wide band gap nanoparticle on the surface of the first film with the amino group or the mercapto group in the silane coupling agent in the fullerene on the surface of the second film at the interface between the first film and the second film comprises: and depositing a fullerene alkaline solution modified by the silane coupling agent on the surface of the first film by adopting an electrophoretic deposition mode, carrying out heat treatment for 30-60 min at the temperature of 80-150 ℃, and laminating the first film to form a second film.
A composite film comprising a first thin film of a material comprising zero-dimensional wide bandgap nanoparticles;
the material of the second film comprises fullerene modified by silane coupling agent, and the general formula of the silane coupling agent is YSiX3Wherein X is alkoxy, Y is a non-hydrolyzable group, and the end of the carbon chain in Y contains an amino substituent or a mercapto substituent;
at the interface of the first and second films, the surface metal element in the zero-dimensional wide band gap nanoparticle at the surface of the first film is bonded to the amino group or the mercapto group in the silane coupling agent in the fullerene at the surface of the second film.
The composite film, wherein the zero-dimensional wide band gap nanoparticles are selected from one of zinc oxide nanoparticles, zinc sulfide nanoparticles and gallium nitride nanoparticles.
The composite film is characterized in that the thickness of the first film is 5-15 nm.
The composite film is characterized in that the thickness of the second film is 0.1-0.5 nm.
Use of a composite film according to the invention as a photo-responsive layer in an ultraviolet sensor.
Has the advantages that: by the method, the junction potential barrier between the zero-dimensional wide band gap nano particles can be effectively reduced, so that the conductivity and the photoelectric response rate of the composite film are improved.
Drawings
FIG. 1 is a schematic structural diagram of a composite membrane bonding interface according to an embodiment of the present invention.
Detailed Description
The invention provides a composite membrane and a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of a composite membrane, which comprises the following steps:
providing fullerol, mixing the fullerol with a silane coupling agent, and dehydrating to obtain fullerene modified by the silane coupling agent, wherein the general formula of the silane coupling agent is YSiX3Wherein X is alkoxy, Y is a non-hydrolyzable group, and the end of the carbon chain in Y contains an amino substituent or a mercapto substituent;
providing a zero-dimensional wide band gap nanoparticle solution;
providing a substrate, and depositing a zero-dimensional wide band gap nanoparticle solution on the substrate to form a first thin film;
and depositing an alkaline fullerene solution modified by the silane coupling agent on the first film to form a second film, and combining a surface metal element in the zero-dimensional wide-band-gap nano-particles on the surface of the first film with an amino group or a mercapto group in the silane coupling agent in the fullerene on the surface of the second film at a combined interface of the first film and the second film to prepare the composite film.
In the prior art, junction barriers are easily formed between zero-dimensional nano materials, and the junction barriers can block electron transmission to further influence the conductivity of the particle film and the photoelectric response rate of the sensor. In order to solve the problems in the prior art, the invention mainly improves the following steps: the composite membrane is prepared by utilizing the characteristics of fullerene, a silane coupling agent and zero-dimensional wide-band-gap nano-particles. The method specifically comprises the following steps: firstly, carrying out surface modification on fullerol by using a silane coupling agent to obtain fullerene modified by the silane coupling agent, then depositing zero-dimensional wide-band-gap nano-particles to obtain a first film, and finally depositing the fullerene modified by the silane coupling agent on the first film to obtain a second film, wherein at the interface of the first film and the second film, a surface metal element in the zero-dimensional wide-band-gap nano-particles on the surface of the first film is combined with an amino group or a sulfhydryl group in the silane coupling agent in the fullerene on the surface of the second film to form the composite film. The prepared composite film is used as a photoresponse layer in an ultraviolet sensor. Compared with the prior art, the method can effectively reduce the junction potential barrier between the zero-dimensional wide band gap nano particles, thereby improving the conductivity and the photoelectric response rate of the composite film. In addition, the method is simple to operate and easy to repeat.
The fullerene has excellent electric conduction characteristics, so that charge transmission can be well carried out, ohmic contact can be generated when the fullerene is in contact with the zero-dimensional wide band gap nano-particles, the Schottky junction potential barrier is reduced, and the conduction of charges between the fullerene and the zero-dimensional wide band gap nano-particles is improved.
The silane coupling agent has the function of a molecular bridge, can connect the zero-dimensional wide band gap nano-particles with the fullerene to realize crosslinking, and then ohmic contact can be formed between the crosslinked fullerene and the zero-dimensional wide band gap nano-particles, so that the junction barrier between the fullerene and the zero-dimensional wide band gap nano-particles is effectively reduced.
Fullerol is a derivative of fullerene, and is obtained by chemically introducing hydroxyl groups into fullerene carbons. The number of the introduced hydroxyl groups will be different due to different synthesis methods and different reaction conditions. In one embodiment of the present invention, the fullerene alcohol is obtained by alcoholizing fullerene by a conventional catalytic base method. The general formula of the fullerol is Cm(OH)nWherein m is more than or equal to 28 and less than or equal to 104, and n is more than or equal to 16N is less than or equal to 60, and n<And m is selected. For example, C can be prepared by conventional catalytic alkaline process28，C60，C70，C76，C78，C82，C84，C88，C90，C96，C100Or C104And carrying out alcoholization on the fullerene. In order to achieve better solubility of the fullerol, the number of hydroxyl groups (-OH) is generally in the range (50%)<n/m<70%) the most preferred fullerol according to formula is C60(OH)36。
The silane coupling agent may be of a wide variety and in one embodiment may be used in the classical formula YSiX3Wherein X is a hydrolyzable group, preferably X is an alkoxy group, Y is a non-hydrolyzable group, and the terminal of the carbon chain in Y must contain an amino group (-NH)2) Or a mercapto group (-SH). The amino and the sulfhydryl can be well bonded with metal elements on the surface of the zero-dimensional wide-band-gap nano-particles, and the hydrolytic group X is used for carrying out dehydration reaction with the hydroxyl of the fullerene alcohol, so that the surface modification of the fullerene is realized, and the fullerene material modified by the silane coupling agent is obtained. The fullerene has excellent conductivity, and the modified fullerene inherits the good conductivity of the fullerene because the hydroxyl on the surface of the fullerene alcohol is modified by the silane coupling agent to form-Si-O group which shows electronegativity and has little influence on the good conductivity (electron donor) of the fullerene.
Preferably, the silane coupling agent is selected from gamma-aminopropyltrimethoxysilane (formula NH)2(CH2)3Si（OCH3）3KH-540 for short), and gamma-aminopropyltriethoxysilane (molecular formula NH)2(CH2)3Si（OC2H5）3KH-550 for short), N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane (NH in molecular formula)2(CH2)2NH(CH2)3Si（OC2H5）3KH-791) and N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane (NH)2(CH2)2NH(CH2)3Si（OCH3）3Abbreviated as KH-792) and gamma-mercaptopropyltriethoxysilane (molecular formula SH (CH)2)3Si（OC2H5）3Abbreviated as KH-580), and the like. Still further preferably, the silane coupling agent is selected from KH-540 or KH-580.
In a preferred embodiment, the step of dehydrating after mixing the fullerol with the silane coupling agent comprises: and mixing the fullerol and the silane coupling agent in a solvent such as methanol or ethanol, and stirring at room temperature for 30-60 min in an atmospheric environment to obtain the fullerene modified by the silane coupling agent.
With fullerol as C60(OH)36For example, a silane coupling agent is mixed with a fullerol C60(OH)36The dehydration process after mixing was as follows:
YSiX3 +3H2O
YSi(OH)3+3HX
12YSi(OH)3+ C60(OH)36 
(YSiO3)12C60 + 36H2O
the water in the hydrolysis is from the atmosphere.
In a preferred embodiment, in the step of mixing the fullerol with the silane coupling agent and then dehydrating, the ratio of the molar ratio of the fullerol to the silane coupling agent is 1 mmol: (15-20 mmol), and dehydrating after mixing the fullerol with the silane coupling agent. This is because too little silane coupling agent is not sufficiently modified, and too much silane coupling agent causes entanglement between the silane coupling agent and the silane coupling agent, which affects subsequent use.
In a preferred embodiment, the zero-dimensional wide band gap nanoparticles in the zero-dimensional wide band gap nanoparticle solution are selected from one of zinc oxide nanoparticles, zinc sulfide nanoparticles, and gallium nitride nanoparticles. The preparation of the zero-dimensional wide band gap nanoparticles of the present invention is prior art and will not be described herein.
In a preferred embodiment, the concentration of the zero-dimensional wide band gap nanoparticles in the zero-dimensional wide band gap nanoparticle solution is 20-40 mg/mL. Preferably, the solvent in the zero-dimensional wide band gap nanoparticle solution is selected from one or two of ethanol and methanol.
In a preferred embodiment, the band gap range of the zero-dimensional wide band gap nanoparticles in the zero-dimensional wide band gap nanoparticle solution is 3-4 eV, and the material in the band gap range has better exciton binding energy, and is an ideal material for preparing the ultraviolet sensor.
In a preferred embodiment, in the silane coupling agent modified fullerene alkaline solution, the concentration of the silane coupling agent modified fullerene is 1 to 5 mg/mL. Preferably, the solvent in the fullerene modified by the silane coupling agent is selected from one or more of ethanol, methanol, cyclohexane and bicyclohexane. The solvent can well disperse fullerene modified by the silane coupling agent, and meanwhile, the formed zero-dimensional wide-band-gap nanoparticle solid film (first film) cannot be dissolved.
In a preferred embodiment, providing a substrate, depositing the zero-dimensional wide bandgap nanoparticle solution on the substrate, and forming a first thin film comprises: and depositing the zero-dimensional wide band gap nanoparticle solution on the substrate by a solution method (such as a printing or coating method) in an atmospheric environment, and annealing at 50-80 ℃ for 30-60 min to form a first thin film on the substrate.
In a preferred embodiment, the step of depositing an alkaline solution of fullerene containing the silane coupling agent modification on the first thin film to form a second thin film, and bonding the surface metal element in the zero-dimensional wide bandgap nanoparticle on the surface of the first thin film to the amino group or the mercapto group in the silane coupling agent in the fullerene on the surface of the second thin film at the interface between the first thin film and the second thin film comprises: vertically placing the substrate deposited with the first film in a fullerene alkaline solution modified by the silane coupling agent, slowly depositing the fullerene alkaline solution modified by the silane coupling agent on the surface of the first film by utilizing an electrophoresis technology, taking out the substrate after deposition, carrying out heat treatment for 30-60 min at the temperature of 80-150 ℃, and laminating the first film to form a second film. The purpose of the heat treatment is to enable the silane coupling agent to form a bond with the zero-dimensional wide band gap nano-particles, so as to realize cross-linking. The method adopts an electrodeposition mode for film formation of fullerene modified by a silane coupling agent, and mainly considers that an effective means for reducing junction barrier is that the effect is poor by adopting a printing or coating mode, the fullerene and zero-dimensional wide-band-gap nano particles can not be fully formed into a tiled layer of composite film, and effective composite crosslinking can be well realized between the fullerene and the zero-dimensional wide-band-gap nano particles by adopting the electrodeposition mode because the fullerene particles are smaller.
Said (YSiO)3)12C60The chemical reaction formula for binding with the zero-dimensional wide band gap nanoparticle is: (with Y being NH)2(CH2)3M is an example of a metal element in a zero-dimensional wide bandgap nanoparticle
（NH2(CH2)3SiO3)12C60+12M+12OH- 
（MNH(CH2)3SiO3)12C60 +12H2O
（MNH(CH2)3SiO3)12C60The corresponding structure is shown in fig. 1.
The reaction process needs to be carried out under an alkaline condition, the preferable pH value range is 8-10, the crosslinking effect is influenced because the reaction is too fast due to too high pH value, and the reaction rate is slower due to too low pH value. More preferably, the required alkaline condition is adjusted by an alkaline substance such as tetramethylammonium hydroxide or tetramethylammonium hydroxide pentahydrate. Still more preferably, the desired alkaline conditions are adjusted using tetramethylammonium hydroxide.
In a preferred embodiment, the thickness of the first film is 5-15 nm, and the zero-dimensional wide-band-gap nanoparticles in the thickness range are substantially zero-dimensional wide-band-gap nanoparticles with only one or two layers, so that fullerene crosslinking is facilitated.
In a preferred embodiment, the thickness of the second thin film is 0.1-0.5 nm, in the thickness range, the fullerene is completely paved on the zero-dimensional wide-band-gap nanoparticle solid-state film (the first thin film), so that the fullerene and the zero-dimensional wide-band-gap nanoparticle are crosslinked, and the light absorption of the composite film is influenced by the excessively thick thickness.
The invention also provides a composite film, which comprises a first film, wherein the material of the first film comprises zero-dimensional wide band gap nano-particles;
the material of the second film comprises fullerene modified by silane coupling agent, and the general formula of the silane coupling agent is YSiX3Wherein X is alkoxy, Y is a non-hydrolyzable group, and the end of the carbon chain in Y contains an amino substituent or a mercapto substituent;
at the interface of the first and second films, the surface metal element in the zero-dimensional wide band gap nanoparticle at the surface of the first film is bonded to the amino group or the mercapto group in the silane coupling agent in the fullerene at the surface of the second film.
The invention also provides the application of the composite film, wherein the composite film is used as a photoresponsive layer in an Ultraviolet (UV) sensor. The composite film is used as a photoresponsive layer, and can effectively improve the conductivity and photoresponse rate of the ultraviolet sensor. After the composite film is combined with the electrode, the conductivity and the photoresponse rate of the ultraviolet sensor can be greatly improved.
The present invention will be described in detail below with reference to examples.
This example uses zinc oxide nanoparticles, C60The preparation of the composite membrane by taking gamma-aminopropyl trimethoxy silane (KH-540) as a main raw material is described in detail.
1. Fullerol C60(OH)36The preparation method comprises the following steps:
1) then, 10mL (20mmol/mL) of NaOH solution was added to the flask, and 0.5mL (10%) of tetrabutylammonium hydroxide TBAH solution was added dropwise. 12mL of a solution containing 20mg of C was added dropwise with vigorous stirring60Then 1mL (30%) of H was added dropwise2O2Continuously stirring the solution for reaction for 2 hours;
2) and standing, wherein the reaction mixture is divided into two layers, the upper layer is a colorless organic phase, and the lower layer is a brownish black aqueous phase. Separating, filtering to remove water phase insoluble substances to obtain a brownish black solution;
3) adding methanol, separating out precipitate (earthy yellow), and centrifuging to remove methanol; dissolving the precipitate with water, adding methanol to precipitate, repeating the above steps for 3 times until NaOH and TBAH are completely removed. Vacuum drying the obtained precipitate at room temperature, dissolving in water, standing, and hydrolyzing for 24 hr. Adding methanol to precipitate, centrifuging to remove methanol, washing precipitate with methanol for 2 times, and vacuum drying the obtained solid at room temperature to obtain brown black product, i.e. fullerol C60(OH)36。
2. Silane coupling agent modified fullerene C60The preparation method comprises the following steps:
1) 0.02mmol of the prepared fullerol C is taken60(OH)36Dispersing 0.3mmol of gamma-aminopropyl trimethoxy silane (KH-540) in 5mL of ethanol solution, and stirring at room temperature for 40min for full reaction;
2) adding a precipitant to the solution, and centrifuging at high speed to obtain fullerene (i.e., (NH) modified with silane coupling agent2(CH2)3SiO3)12C60) (NH) of the obtained2(CH2)3SiO3)12C60Drying under vacuum at room temperature.
3. The preparation method of the zinc oxide nano-particles comprises the following steps:
1) dispersing 2mmol of zinc acetate in 5mL of dimethyl sulfoxide (DMSO), dispersing 0.5mmol of hydrated tetramethylammonium hydroxide in 5mL of ethanol, mixing the two mixed solutions, and stirring for 60 min;
2) 15mL of heptane was added to the mixture, and the mixture was centrifuged to precipitate, and then the obtained zinc oxide nanoparticles were vacuum-dried.
4. The preparation method of the composite membrane comprises the following steps:
1) dispersing 40mg of the prepared zinc oxide nano particles in 2mL of ethanol for later use;
2) dispersing 10mg of the prepared fullerene modified by the silane coupling agent into 10mL of cyclohexane, and dropwise adding tetramethylammonium hydroxide into the solution to adjust the pH value of the solution to 9 for later use;
3) preparing a layer of zinc oxide solid film (first film) on a transparent conductive substrate by using the zinc oxide nanoparticle solution prepared in the step 1) in a printing mode, and then annealing at the temperature of 60 ℃ for 50min to obtain the zinc oxide solid film;
4) vertically placing the conductive substrate with the zinc oxide solid film in the solution obtained in the step 2), applying a positive voltage to the zinc oxide solid film, depositing for a period of time to obtain fullerene with the thickness of 1nm, taking out, and performing heat treatment at 120 ℃ for 40min to finally obtain the composite film.
5. The preparation method of the ultraviolet sensor comprises the following steps:
the same procedure as described above was used to prepare the photo-responsive layer in the uv sensor.
In summary, the invention provides a composite film, a preparation method and an application thereof. According to the preparation method, firstly, a silane coupling agent is used for carrying out surface modification on fullerol to obtain fullerene modified by the silane coupling agent, then zero-dimensional wide-band-gap nano particles are deposited to obtain a first film, finally, the fullerene modified by the silane coupling agent is deposited on the first film to obtain a second film, and at the interface of the first film and the second film, surface metal elements in the zero-dimensional wide-band-gap nano particles on the surface of the first film are combined with amino or sulfydryl in the silane coupling agent in the fullerene on the surface of the second film to form the composite film. After the composite film is combined with the electrode, the conductivity and the photoresponse rate of the ultraviolet sensor can be greatly improved.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (12)
1. A preparation method of a composite film for an ultraviolet sensor is characterized by comprising the following steps:
providing fullerol, mixing the fullerol with a silane coupling agent, and dehydrating to obtain fullerene modified by the silane coupling agent, wherein the general formula of the silane coupling agent is YSiX3Wherein X is alkoxy, Y is a non-hydrolyzable group, and the end of the carbon chain in Y contains an amino substituent or a mercapto substituent; the silane coupling agent is selected from NH2(CH2)3Si（OCH3）3、NH2(CH2)3Si（OC2H5）3、NH2(CH2)2NH(CH2)3Si（OCH3）3、NH2(CH2)2NH(CH2)3Si（OC2H5）3And SH (CH)2)3Si（OC2H5）3One of (1);
providing a zero-dimensional wide band gap nanoparticle solution; the zero-dimensional wide band gap nanoparticles in the zero-dimensional wide band gap nanoparticle solution are selected from one of zinc oxide nanoparticles, zinc sulfide nanoparticles and gallium nitride nanoparticles;
providing a substrate, and depositing a zero-dimensional wide band gap nanoparticle solution on the substrate to form a first thin film;
and depositing a fullerene alkaline solution modified by the silane coupling agent on the first film to form a second film, and combining a surface metal element in the zero-dimensional wide-band-gap nano-particles on the surface of the first film with an amino group or a mercapto group in the silane coupling agent in the fullerene on the surface of the second film at a combined interface of the first film and the second film to prepare the composite film for the ultraviolet sensor.
2. The method of claim 1, wherein the fullerol has a formula of Cm(OH)nWherein m is more than or equal to 28 and less than or equal to 104, n is more than or equal to 16 and less than or equal to 60, n<m。
3. The method of claim 1, wherein in the step of mixing the fullerol with the silane coupling agent and then dehydrating, the ratio of the fullerol to the silane coupling agent is 1 mmol: (15-20 mmol), and mixing the fullerol with the silane coupling agent and then dehydrating.
4. The method for preparing the composite film for the ultraviolet sensor according to claim 1, wherein the band gap range of the zero-dimensional wide band gap nanoparticles in the zero-dimensional wide band gap nanoparticle solution is 3-4 eV.
5. The method of claim 1, wherein the concentration of the zero-dimensional wide band gap nanoparticles in the zero-dimensional wide band gap nanoparticle solution is 20-40 mg/mL.
6. The method of claim 1, wherein the step of depositing the zero-dimensional wide band gap nanoparticle solution on the substrate to form a first thin film comprises: and depositing the zero-dimensional wide band gap nanoparticle solution on the substrate, and annealing for 30-60 min at 50-80 ℃ to form a first film on the substrate.
7. The method of claim 1, wherein the step of depositing an alkaline solution of fullerene modified with the silane coupling agent on the first thin film to form a second thin film, and bonding the surface metal element in the zero-dimensional wide band gap nanoparticle on the surface of the first thin film to the amino group or the mercapto group in the silane coupling agent in the fullerene on the surface of the second thin film at the interface between the first thin film and the second thin film comprises: and depositing a fullerene alkaline solution modified by the silane coupling agent on the surface of the first film by adopting an electrophoretic deposition mode, carrying out heat treatment for 30-60 min at the temperature of 80-150 ℃, and laminating the first film to form a second film.
8. A composite film for an ultraviolet sensor comprising a first film, the material of the first film comprising zero-dimensional wide band gap nanoparticles; the zero-dimensional wide band gap nanoparticles in the zero-dimensional wide band gap nanoparticle solution are selected from one of zinc oxide nanoparticles, zinc sulfide nanoparticles and gallium nitride nanoparticles;
the material of the second film comprises fullerene modified by silane coupling agent, and the general formula of the silane coupling agent is YSiX3Wherein X is alkoxy, Y is a non-hydrolyzable group, and the end of the carbon chain in Y contains an amino substituent or a mercapto substituent; the silane coupling agent is selected from NH2(CH2)3Si（OCH3）3、NH2(CH2)3Si（OC2H5）3、NH2(CH2)2NH(CH2)3Si（OCH3）3、NH2(CH2)2NH(CH2)3Si（OC2H5）3And SH (CH)2)3Si（OC2H5）3One of (1);
at the interface of the first and second films, the surface metal element in the zero-dimensional wide band gap nanoparticle at the surface of the first film is bonded to the amino group or the mercapto group in the silane coupling agent in the fullerene at the surface of the second film.
9. The composite film for an ultraviolet sensor according to claim 8, wherein the zero-dimensional wide band gap nanoparticles are selected from one of zinc oxide nanoparticles, zinc sulfide nanoparticles, and gallium nitride nanoparticles.
10. The composite film for an ultraviolet sensor according to claim 8, wherein the first film has a thickness of 5 to 15 nm.
11. The composite film for an ultraviolet sensor according to claim 8, wherein the second film has a thickness of 0.1 to 0.5 nm.
12. Use of a composite film for an ultraviolet sensor according to any one of claims 8 to 11 as a photo-responsive layer in an ultraviolet sensor.
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