CN109935701A - A kind of composite membrane and the preparation method and application thereof - Google Patents
A kind of composite membrane and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention discloses a kind of composite membrane and the preparation method and application thereof, and method is dehydrated after mixing the Fullerol with silane coupling agent, obtains the fullerene that silane coupling agent is modified comprising steps of provide Fullerol；Zero dimension broad-band gap nanoparticles solution is provided；Substrate is provided, on the substrate by zero dimension broad-band gap nanoparticles solution deposition, forms the first film；The fullerene alkaline solution modified containing the silane coupling agent is deposited on the first film, form the second film, and at the combination interface of the first film and the second film, make the surface metal element in the zero dimension broad-band gap nano particle on the first film surface in conjunction with the amino or sulfydryl in the silane coupling agent in the fullerene for being located at the second film surface, the composite membrane is prepared.The method of the present invention is easy to operate, is easy to repeat, and can effectively reduce the junction barrier between zero dimension broad-band gap nano particle, to improve the conduction and photoelectric respone rate of composite membrane.
Description
Technical field
The present invention relates to ultraviolet transducing device technical fields more particularly to a kind of composite membrane and the preparation method and application thereof.
Background technique
Ultraviolet (UV) sensor has extensive demand in industry and scientific domain, such as: ultraviolet light detection, high temp fire
Flame, the detection of guided missile flame plumage and the fields such as photoswitch and optic communication suffer from more wide application value.
During the developing material of Ultraviolet sensor, semiconductor material with wide forbidden band is to meet the premise of Ultraviolet sensor such as
The materials such as zinc oxide, zinc sulphide.Find that monodimension nanometer material has preferable electricity during the developing material of Ultraviolet sensor
Sub- transmission characteristic and biggish specific surface area be such as: zinc oxide nanowire, zinc oxide nano rod, zinc oxide nano-belt；Zinc sulphide is received
The one-dimensional materials such as rice noodles, zinc sulfide nano stick, zinc sulfide nano-belt are widely used in UV sensor.
However the UV sensor of above-mentioned one-dimensional material preparation is utilized, the photoelectric respone time usually requires several seconds to a few minutes very
To several hundred minutes, because photoelectric current switching rate surface when using above-mentioned one-dimensional material generates the adsorption and desorption process of oxygen
Relatively slowly.It is nano material (such as Zinc oxide nanoparticle, zinc sulphide using the biggish zero dimension of specific surface area in existing technology
Nano particle etc.) Lai Tigao oxygen adsorption and desorption rate further improves photoelectric current switching rate；Utilize receiving for zero dimension
Although rice grain, which prepares UV sensor to a certain extent, improves the sensitivity of sensor, between the nano material of zero dimension
Junction barrier easy to form, junction barrier can hinder electron-transport and then influence the conduction of membrana granulosa and the photoelectric respone speed of sensor
Rate.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of composite membrane and preparation method thereof with answer
With, it is intended to junction barrier easy to form between the nano material of existing zero dimension is solved, junction barrier can hinder electron-transport and then influence
The problem of conduction and the photoelectric respone rate of sensor of membrana granulosa.
Technical scheme is as follows:
A kind of preparation method of composite membrane, wherein comprising steps of
Fullerol is provided, is dehydrated after the Fullerol is mixed with silane coupling agent, the fullerene of silane coupling agent modification is obtained,
The general formula of the silane coupling agent is YSiX3, wherein X is alkoxy, and Y is non-hydrolytic group, and carbochain end is contained amino and taken in Y
Dai Ji or mercapto substituent；
Zero dimension broad-band gap nanoparticles solution is provided；
Substrate is provided, on the substrate by zero dimension broad-band gap nanoparticles solution deposition, forms the first film；
The fullerene alkaline solution modified containing the silane coupling agent is deposited on the first film, forms the second film, and
At the combination interface of the first film and the second film, make in the zero dimension broad-band gap nano particle on the first film surface
Surface metal element be located at the second film surface fullerene in silane coupling agent in amino or sulfydryl combine, prepare
Obtain the composite membrane.
The preparation method of the composite membrane, wherein the general formula of the Fullerol is Cm(OH)n, wherein 28≤m≤104,
16≤n≤60, n < m.
The preparation method of the composite membrane, wherein 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)3With SH (CH2)3Si
(OC2H5)3One of.
The preparation method of the composite membrane, wherein in the step of being dehydrated after mixing the Fullerol with silane coupling agent, press
The Fullerol and the molar ratio of the silane coupling agent are 1mmol:(15 ~ 20mmol), by the Fullerol and the silane
Coupling agent is dehydrated after being mixed.
The preparation method of the composite membrane, wherein the zero dimension broad-band gap in the zero dimension broad-band gap nanoparticles solution
Nano particle is selected from one of Zinc oxide nanoparticle, zine sulfide nano particles and gallium nitride nano particle.
The preparation method of the composite membrane, wherein the zero dimension broad-band gap in the zero dimension broad-band gap nanoparticles solution
The bandgap range of nano particle is 3 ~ 4ev.
The preparation method of the composite membrane, wherein in the zero dimension broad-band gap nanoparticles solution, the zero dimension broadband
The concentration of gap nano particle is 20 ~ 40mg/mL.
The preparation method of the composite membrane, wherein the zero dimension broad-band gap nanoparticles solution is deposited on the base
On plate, formed the first film the step of include: by the zero dimension broad-band gap nanoparticles solution deposition on the substrate, 50
Under the conditions of ~ 80 DEG C, 30 ~ 60min is made annealing treatment, forms the first film on the substrate.
The preparation method of the composite membrane, wherein deposition is modified containing the silane coupling agent on the first film
Fullerene alkaline solution, form the second film, and in the interface of the first film and the second film, make to be located at first thin
Surface metal element in the zero dimension broad-band gap nano particle of film surface and the silane in the fullerene of the second film surface
The step of amino or sulfydryl in coupling agent combine includes: that will contain the silane coupling agent modification by the way of electrophoretic deposition
Fullerene alkaline solution be deposited on the first film surface, under the conditions of 80 ~ 150 DEG C, be heat-treated 30 ~ 60min, described
Stacking forms the second film on the first film.
A kind of composite membrane, wherein including the first film, the material of the first film includes zero dimension broad-band gap nanometer
Grain；
It further include the second film that stacking is formed in one surface of the first film, the material of second film includes silane idol
Join the fullerene of agent modification, the general formula of the silane coupling agent is YSiX3, wherein X is alkoxy, and Y is non-hydrolytic group, in Y
Contain amino-substituent or mercapto substituent in carbochain end；
In the interface of the first film and the second film, in the zero dimension broad-band gap nano particle on the first film surface
Surface metal element is in conjunction with the amino or sulfydryl in the silane coupling agent in the fullerene for being located at the second film surface.
The composite membrane, wherein the zero dimension broad-band gap nano particle is selected from Zinc oxide nanoparticle, zinc sulfide nano
One of particle and gallium nitride nano particle.
The composite membrane, wherein the first film with a thickness of 5 ~ 15nm.
The composite membrane, wherein second film with a thickness of 0.1 ~ 0.5nm.
A kind of application of composite membrane, wherein composite membrane of the present invention is used as the photoresponsive layer in Ultraviolet sensor.
The utility model has the advantages that the present invention can effectively reduce the knot between zero dimension broad-band gap nano particle by the above method
Potential barrier, to improve the electric conductivity and photoelectric respone rate of composite membrane.
Detailed description of the invention
Fig. 1 is the structural schematic diagram at the composite membrane combination interface of the embodiment of the present invention.
Specific embodiment
The present invention provides a kind of composite membrane and the preparation method and application thereof, to make the purpose of the present invention, technical solution and effect
Fruit is clearer, clear, and the present invention is described in more detail below.It should be appreciated that specific embodiment described herein is only
Only to explain the present invention, it is not intended to limit the present invention.
The present invention provides a kind of preparation method of composite membrane, wherein comprising steps of
Fullerol is provided, is dehydrated after the Fullerol is mixed with silane coupling agent, the fullerene of silane coupling agent modification is obtained,
The general formula of the silane coupling agent is YSiX3, wherein X is alkoxy, and Y is non-hydrolytic group, and carbochain end is contained amino and taken in Y
Dai Ji or mercapto substituent；
Zero dimension broad-band gap nanoparticles solution is provided；
Substrate is provided, on the substrate by zero dimension broad-band gap nanoparticles solution deposition, forms the first film；
The fullerene alkaline solution modified containing the silane coupling agent is deposited on the first film, forms the second film, and
At the combination interface of the first film and the second film, make in the zero dimension broad-band gap nano particle on the first film surface
Surface metal element be located at the second film surface fullerene in silane coupling agent in amino or sulfydryl combine, prepare
Obtain the composite membrane.
In the prior art, junction barrier easy to form between the nano material of zero dimension, junction barrier can hinder electron-transport in turn
Influence the conduction of membrana granulosa and the photoelectric respone rate of sensor.In order to solve the above problems existing in the present technology, of the invention
It mainly thes improvement is that: being prepared using the characteristic of fullerene, silane coupling agent and zero dimension broad-band gap nano particle three
Composite membrane.Specifically: Fullerol is surface modified first with silane coupling agent, obtains the fowler of silane coupling agent modification
Then alkene is deposited zero dimension broad-band gap nano particle to obtain the first film, finally be deposited on the first film silane coupled
The fullerene of agent modification, obtains the second film, in the interface of the first film and the second film, is located at the first film surface
Zero dimension broad-band gap nano particle in surface metal element be located at the second film surface fullerene in silane coupling agent
In amino or sulfydryl combine, form the composite membrane.The composite membrane being prepared is used as the light in Ultraviolet sensor
Response layer.Compared with existing, the present invention can effectively reduce the junction barrier between zero dimension broad-band gap nano particle, to improve
The electric conductivity and photoelectric respone rate of composite membrane.In addition, the method for the present invention is easy to operate, it is easy to repeat.
Fullerene has excellent characteristics of electrical conductivity, so as to carry out charge transmission, while fullerene and zero dimension very well
Broad-band gap nano particle can generate Ohmic contact when being contacted, Schottky junction barrier be reduced, to improve charge in fowler
Conduction between alkene and zero dimension broad-band gap nano particle.
Silane coupling agent is to have the function of molecular bridge first, can connect zero dimension broad-band gap nano particle with fullerene
Get up and realize crosslinking, will form Ohmic contact between the fullerene and zero dimension broad-band gap nano particle after being followed by crosslinked, thus
Effectively reduce the junction barrier between fullerene and zero dimension broad-band gap nano particle.
Fullerol is the derivative of fullerene, is to introduce hydroxyl on the carbon of fullerene by chemical method to obtain.It closes
Different at method difference, reaction condition, the number of the hydroxyl of introducing will be different.In one embodiment of the present invention
In, the Fullerol is to be refined to obtain to fullerene using Conventional catalytic alkaline process.The general formula of Fullerol of the present invention is
Cm(OH)n, wherein 28≤m≤104,16≤n≤60, and n < m.Such as it can be using Conventional catalytic alkaline process to C28, C60, C70,
C76, C78, C82, C84, C88, C90, C96, C100Or C104Equal fullerenes are refined to obtain.In order to have Fullerol compared with good dissolving
Property, the range of hydroxyl (- OH) number is C according to the most preferred Fullerol of general formula generally at (50% < n/m < 70%)60(OH)36。
The type of silane coupling agent has very much, and in one embodiment, the silane coupling agent of use can be led to classical
Formula YSiX3It indicates, in formula, X is hydrolysising group, and preferred X is alkoxy, and Y is non-hydrolytic group, and carbochain end must contain in Y
There is amino (- NH2) or sulfydryl (- SH).Amino and sulfydryl can be carried out with the metallic element of zero dimension broad-band gap nano grain surface
Good bonding, the hydrolysising group X between the hydroxyl of Fullerol for carrying out dehydration, to realize to fullerene
Surface modification obtains the fullerene-based material modified through silane coupling agent.Fullerene has superior electrical conductivity, due to Fullerol surface
Hydroxyl after silane coupling agent is modified formation-Si-O group show elecrtonegativity to the good electric conductivity (electronics of fullerene itself
Donor) influence is smaller, therefore modified fullerene inherits the good electric conductivity of fullerene.
Preferably, the silane coupling agent is selected from γ-aminopropyltrimethoxysilane (molecular formula NH2(CH2)3Si
(OCH3)3, referred to as KH-540), gamma-aminopropyl-triethoxy-silane (molecular formula NH2(CH2)3Si(OC2H5)3, referred to as
KH-550), N- (β-aminoethyl)-gamma-aminopropyl-triethoxy-silane (molecular formula NH2(CH2)2NH(CH2)3Si(OC2H5)3,
Referred to as KH-791), N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane (molecular formula NH2(CH2)2NH(CH2)3Si
(OCH3)3, referred to as KH-792) and gamma-mercaptopropyltriethoxysilane (molecular formula be SH (CH2)3Si(OC2H5)3, referred to as
One of KH-580) etc..Still more preferably, the silane coupling agent is selected from KH-540 or KH-580.
In a preferred embodiment, the step of dehydration, includes: after the Fullerol being mixed with silane coupling agent
The Fullerol and silane coupling agent are mixed in methanol or ethyl alcohol equal solvent, carry out being stirred at room temperature 30 under atmospheric environment ~
60min obtains the fullerene of silane coupling agent modification.
It is C with Fullerol60(OH)36Citing, by silane coupling agent and Fullerol C60(OH)36The process being dehydrated after mixing is such as
Under:
YSiX3 +3H2OYSi(OH)3+3HX
12YSi(OH)3+ C60(OH)36 (YSiO3)12C60 + 36H2O
It should be noted that the moisture in above-mentioned hydrolytic process comes from atmosphere.
In a preferred embodiment, it in the step of being dehydrated after the Fullerol being mixed with silane coupling agent, presses
The Fullerol and the molar ratio of the silane coupling agent are 1mmol:(15 ~ 20mmol), by the Fullerol and the silane
It is dehydrated after coupling agent mixing.This is because the very few modification of silane coupling agent is insufficient, silane coupling agent and silane excessively will cause
Mutually winding influences subsequent use between coupling agent.
In a preferred embodiment, the zero dimension broad-band gap nanometer in the zero dimension broad-band gap nanoparticles solution
One of grain-by-grain seed selection autoxidation zinc nanoparticles, zine sulfide nano particles and gallium nitride nano particle.Zero dimension of the present invention is wide
Band gap nano particle is prepared as the prior art, and details are not described herein.
In a preferred embodiment, in the zero dimension broad-band gap nanoparticles solution, the zero dimension broad-band gap is received
The concentration of rice grain is 20 ~ 40mg/mL.Preferably, the solvent in the zero dimension broad-band gap nanoparticles solution be selected from ethyl alcohol and
One or both of methanol.
In a preferred embodiment, the zero dimension broad-band gap nanometer in the zero dimension broad-band gap nanoparticles solution
The bandgap range of grain is 3 ~ 4ev, and it is the reason for preparing Ultraviolet sensor that the material of the bandgap range, which has preferable exciton bind energy,
Think material.
In a preferred embodiment, in the fullerene alkaline solution of the silane coupling agent modification, the silane
The concentration of the fullerene of coupling agent modification is 1 ~ 5mg/mL.Preferably, the solvent in the fullerene of the silane coupling agent modification
Selected from ethyl alcohol, methanol, hexamethylene and connection one of hexamethylene or a variety of.Such solvent can be good at repairing silane coupling agent
The fullerene of decorations is dispersed, while again will not be molten to the zero dimension broad-band gap nano particle solid film (the first film) formed
Solution.
In a preferred embodiment, substrate is provided, the zero dimension broad-band gap nanoparticles solution is deposited on institute
State on substrate, formed the first film the step of include: under atmospheric environment, using solwution method (as print or coating method) will
The zero dimension broad-band gap nanoparticles solution deposition on the substrate, under the conditions of 50 ~ 80 DEG C, makes annealing treatment 30 ~ 60min,
The first film is formed on the substrate.
In a preferred embodiment, the fowler modified containing the silane coupling agent is deposited on the first film
Alkene alkaline solution forms the second film, and in the interface of the first film and the second film, makes to be located at the first film surface
Zero dimension broad-band gap nano particle in surface metal element be located at the second film surface fullerene in silane coupling agent
In amino or sulfydryl in conjunction with the step of include: that the substrate for being deposited with the first film is placed on vertically containing the silane coupling agent
In the fullerene alkaline solution of modification, using electrophoretic techniques by the fullerene alkaline solution modified containing the silane coupling agent slowly
Be deposited on the first film surface, substrate is taken out after deposition, under the conditions of 80 ~ 150 DEG C, heat treatment 30 ~
60min, stacking forms the second film on the first film.The purpose of the heat treatment is to enable silane coupling agent
It is formed and is bonded between zero dimension broad-band gap nano particle, realize crosslinking.The present invention forms a film to the fullerene that silane coupling agent is modified
By the way of electro-deposition, mainly it is in view of reducing the effective means of junction barrier, the effect by the way of printing or coating
It is bad, it cannot sufficiently realize that fullerene and zero dimension broad-band gap nano particle form one layer of composite membrane of tiling, due to fullerene
Grain is smaller to can be good at making realization between fullerene and zero dimension broad-band gap nano particle effective by the way of electro-deposition
Composite crosslinking.
(the YSiO3)12C60Chemical equation in conjunction with zero dimension broad-band gap nano particle are as follows: (be NH with Y2
(CH2)3, M is the metallic element citing in zero dimension broad-band gap nano particle)
(NH2(CH2)3SiO3)12C60+12M+12OH- (MNH (CH2)3SiO3)12C60 +12H2O
(MNH (CH2)3SiO3)12C60Corresponding structure is as shown in Figure 1.
The above-mentioned reaction process of the present invention needs to carry out under alkaline condition, preferred pH value range between 8 ~ 10 because
The excessively high too fast influence cross-linking effect of reaction of pH value, the too low reaction rate of pH value are slower.It is further preferred that alkali required for described
Property condition be to be adjusted using tetramethylammonium hydroxide, the five hydration alkaline matters such as tetramethylammonium hydroxide.It is further excellent
Choosing, the required alkaline condition is adjusted using tetramethylammonium hydroxide.
In a preferred embodiment, the first film with a thickness of 5 ~ 15nm, the zero dimension of the thickness range is wide
Band gap nano particle is substantially the zero dimension broad-band gap nano particle of only one or two layers, is conducive to the crosslinking of fullerene.
In a preferred embodiment, second film with a thickness of 0.1 ~ 0.5nm, in the thickness range fowler
Alkene is completely spread out on zero dimension broad-band gap nano particle solid film (the first film), realizes fullerene and zero dimension broad-band gap nanometer
Crosslinking between particle, the blocked up light absorption that will will affect composite membrane of thickness.
The present invention also provides a kind of composite membranes, wherein including the first film, the material of the first film includes that zero dimension is wide
Band gap nano particle；
It further include the second film that stacking is formed in one surface of the first film, the material of second film includes silane idol
Join the fullerene of agent modification, the general formula of the silane coupling agent is YSiX3, wherein X is alkoxy, and Y is non-hydrolytic group, in Y
Contain amino-substituent or mercapto substituent in carbochain end；
In the interface of the first film and the second film, in the zero dimension broad-band gap nano particle on the first film surface
Surface metal element is in conjunction with the amino or sulfydryl in the silane coupling agent in the fullerene for being located at the second film surface.
The present invention also provides a kind of applications of composite membrane, wherein passes composite membrane of the present invention as ultraviolet (UV)
Photoresponsive layer in sensor.The composite membrane is used as photoresponsive layer, can be effectively improved the conductivity and light of Ultraviolet sensor
The speed of response.Using composite membrane of the present invention in conjunction with electrode after, the conductivity and light of Ultraviolet sensor can be greatly improved
The speed of response.
Below by embodiment, the present invention is described in detail.
The present embodiment is to utilize Zinc oxide nanoparticle, C60, γ-aminopropyltrimethoxysilane (KH-540) be main former
Material describes in detail for preparing composite membrane.
1, Fullerol C60(OH)36Preparation method, comprising the following steps:
1) NaOH solution of 10mL (20mmol/mL), is added in flask, 0.5mL (10%) tetrabutylammonium hydroxide TBAH is added dropwise
Solution.With vigorous stirring, 12mL is added dropwise and contains 20mg C60Toluene solution, then the H of 1mL (30%) is added dropwise2O2Solution,
Continue to be stirred to react 2 hours；
2) it, stands, reaction mixture is divided into two layers, and upper layer is colourless organic phase, and lower layer is the water phase of brownish black.Liquid separation point
From being filtered to remove water phase insoluble matter, obtain dark brown solution；
3) methanol, is added, precipitating (khaki) is precipitated, is centrifuged off methanol；Add water to dissolve precipitating, adds methanol and be allowed to heavy
It forms sediment, 3 times repeatedly, until NaOH and TBAH are washed away completely.By gained precipitating room temperature vacuum drying, it is dissolved in water, places hydrolysis
24h.Add methanol to make Precipitation, is centrifuged off methanol, again with methanol washing precipitating 2 times, vacuum is dry at room temperature for obtained solid
It is dry, obtain brownish black product, i.e. Fullerol C60(OH)36。
2, the fullerene C of silane coupling agent modification60Preparation method, comprising the following steps:
1) the above-mentioned Fullerol C prepared of 0.02mmol, is taken60(OH)36With the γ-aminopropyltrimethoxysilane of 0.3mmol
(KH-540) it is dispersed in the ethanol solution of 5 mL simultaneously, stirring at normal temperature 40min reacts it sufficiently；
2) precipitating reagent, is added into solution to be centrifuged at a high speed, and obtains the fullerene (i.e. (NH of silane coupling agent modification2
(CH2)3SiO3)12C60), by obtained (NH2(CH2)3SiO3)12C60It is dried in vacuo at room temperature.
3, the preparation method of Zinc oxide nanoparticle, comprising the following steps:
1) it, takes the zinc acetate of 2mmol to be dispersed in the dimethyl sulfoxide (DMSO) of 5mL, takes the hydration tetramethyl hydrogen-oxygen of 0.5mmol
Change ammonium to be dispersed in the ethyl alcohol of 5mL, two kinds of mixed liquors are then mixed and stirred for 60min；
2) 15mL heptane, is added in Xiang Shangshu mixed liquor, precipitating is centrifuged, then to obtained Zinc oxide nanoparticle
Carry out vacuum drying treatment.
4, the preparation method of composite membrane, comprising the following steps:
1) the above-mentioned Zinc oxide nanoparticle prepared of 40mg, is taken to be dispersed in the ethyl alcohol of 2mL, it is spare；
2) fullerene of the above-mentioned silane coupling agent modification prepared of 10mg, is taken to be dispersed in the hexamethylene of 10mL, and to solution
The middle pH value that tetramethylammonium hydroxide adjusting solution is added dropwise is spare to 9；
3), by it is above-mentioned 1) in the Zinc oxide nanoparticle solution for preparing made in transparent conductive substrates by the way of printing
Standby one layer of zinc oxide solid film (the first film), then uses 60 DEG C of annealing 50min, obtains the zinc oxide solid film；
4), the conductive substrates for being prepared with zinc oxide solid film are vertically disposed in the solution in step 2, to zinc oxide solid-state
Film adds a positive voltage, obtains the fullerene with a thickness of 1nm after depositing a period of time, using 120 DEG C of heat treatments after taking-up
Composite membrane is finally prepared in 40min.
5, the preparation method of Ultraviolet sensor, comprising the following steps:
Photoresponsive layer in Ultraviolet sensor is prepared using above-mentioned same step.
In conclusion a kind of composite membrane provided by the invention and the preparation method and application thereof.The invention firstly uses silane
Coupling agent is surface modified Fullerol, the fullerene of silane coupling agent modification is obtained, then by zero dimension broad-band gap nanometer
Grain is deposited to obtain the first film, and the fullerene of silane coupling agent modification is finally deposited on the first film, it is thin to obtain second
Film, in the interface of the first film and the second film, in the zero dimension broad-band gap nano particle on the first film surface
Surface metal element forms institute in conjunction with the amino or sulfydryl in the silane coupling agent in the fullerene for being located at the second film surface
State composite membrane.Using composite membrane of the present invention in conjunction with electrode after, the conductivity and light of Ultraviolet sensor can be greatly improved
The speed of response.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (14)
1. a kind of preparation method of composite membrane, which is characterized in that comprising steps of
Fullerol is provided, is dehydrated after the Fullerol is mixed with silane coupling agent, the fullerene of silane coupling agent modification is obtained,
The general formula of the silane coupling agent is YSiX3, wherein X is alkoxy, and Y is non-hydrolytic group, and carbochain end is contained amino and taken in Y
Dai Ji or mercapto substituent；
Zero dimension broad-band gap nanoparticles solution is provided；
Substrate is provided, on the substrate by zero dimension broad-band gap nanoparticles solution deposition, forms the first film；
The fullerene alkaline solution modified containing the silane coupling agent is deposited on the first film, forms the second film, and
At the combination interface of the first film and the second film, make in the zero dimension broad-band gap nano particle on the first film surface
Surface metal element be located at the second film surface fullerene in silane coupling agent in amino or sulfydryl combine, prepare
Obtain the composite membrane.
2. the preparation method of composite membrane according to claim 1, which is characterized in that the general formula of the Fullerol is Cm
(OH)n, wherein 28≤m≤104,16≤n≤60, n < m.
3. the preparation method of composite membrane according to claim 1, which is characterized in that 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)3With SH (CH2)3Si(OC2H5)3One of.
4. the preparation method of composite membrane according to claim 1, which is characterized in that by the Fullerol and silane coupling agent
It is 1mmol:(15 ~ 20mmol by the Fullerol and the molar ratio of the silane coupling agent in the step of being dehydrated after mixing), it will
The Fullerol is dehydrated after being mixed with the silane coupling agent.
5. the preparation method of composite membrane according to claim 1, which is characterized in that the zero dimension broad-band gap nano particle is molten
Zero dimension broad-band gap nano particle in liquid is in Zinc oxide nanoparticle, zine sulfide nano particles and gallium nitride nano particle
It is a kind of.
6. the preparation method of composite membrane according to claim 1, which is characterized in that the zero dimension broad-band gap nano particle is molten
The bandgap range of zero dimension broad-band gap nano particle in liquid is 3 ~ 4ev.
7. the preparation method of composite membrane according to claim 1, which is characterized in that the zero dimension broad-band gap nano particle is molten
In liquid, the concentration of the zero dimension broad-band gap nano particle is 20 ~ 40mg/mL.
8. the preparation method of composite membrane according to claim 1, which is characterized in that by the zero dimension broad-band gap nano particle
Liquid deposition on the substrate, formed the first film the step of include: by the zero dimension broad-band gap nanoparticles solution deposit
On the substrate, under the conditions of 50 ~ 80 DEG C, 30 ~ 60min is made annealing treatment, forms the first film on the substrate.
9. the preparation method of composite membrane according to claim 1, which is characterized in that deposition contains institute on the first film
The fullerene alkaline solution of silane coupling agent modification is stated, forms the second film, and on the boundary of the first film and the second film
At face, makes the surface metal element in the zero dimension broad-band gap nano particle on the first film surface and be located at the second film surface
Fullerene in silane coupling agent in amino or sulfydryl combine the step of include: that will contain institute by the way of electrophoretic deposition
The fullerene alkaline solution for stating silane coupling agent modification is deposited on the first film surface, under the conditions of 80 ~ 150 DEG C, at heat
30 ~ 60min is managed, stacking forms the second film on the first film.
10. a kind of composite membrane, which is characterized in that including the first film, the material of the first film includes that zero dimension broad-band gap is received
Rice grain；
It further include the second film that stacking is formed in one surface of the first film, the material of second film includes silane idol
Join the fullerene of agent modification, the general formula of the silane coupling agent is YSiX3, wherein X is alkoxy, and Y is non-hydrolytic group, in Y
Contain amino-substituent or mercapto substituent in carbochain end；
In the interface of the first film and the second film, in the zero dimension broad-band gap nano particle on the first film surface
Surface metal element is in conjunction with the amino or sulfydryl in the silane coupling agent in the fullerene for being located at the second film surface.
11. composite membrane according to claim 10, which is characterized in that the zero dimension broad-band gap nano particle is selected from zinc oxide
One of nano particle, zine sulfide nano particles and gallium nitride nano particle.
12. composite membrane according to claim 10, which is characterized in that the first film with a thickness of 5 ~ 15nm.
13. composite membrane according to claim 10, which is characterized in that second film with a thickness of 0.1 ~ 0.5nm.
14. a kind of application of composite membrane, which is characterized in that be used as the described in any item composite membranes of claim 10 to 13 ultraviolet
Photoresponsive layer in sensor.
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