CN104628265B - A kind of multilayer wide spectrum hydrophobic type solar cell anti-reflection film and preparation method thereof - Google Patents
A kind of multilayer wide spectrum hydrophobic type solar cell anti-reflection film and preparation method thereof Download PDFInfo
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Abstract
A kind of preparation method of multilayer wide spectrum hydrophobic type solar cell anti-reflection film, including：Prepare TiO2Colloidal sol and SiO2‑TiO2Complex sol；Hydrophobic SiO is prepared by presoma of MTES2Sol precursor, prepares Nano-meter SiO_22Colloidal sol, by hydrophobic SiO2Sol precursor and Nano-meter SiO_22Colloidal sol obtains a hydrophobic SiO after being mixed according to volume ratio for 1: 1.5~92Colloidal sol；One substrate is provided, SiO is used2‑TiO2Complex sol obtains SiO in substrate surface plated film2‑TiO2Laminated film；Use TiO2Colloidal sol is in SiO2‑TiO2Plated film on laminated film, obtains TiO2/TiO2‑SiO2Duplicature；And use hydrophobic SiO2Colloidal sol is in TiO2/SiO2‑TiO2Plated film on duplicature.The present invention also provides a kind of solar cell anti-reflection film and packaging glass of solar cell and solar cell with the anti-reflection film.
Description
Technical field
The present invention relates to anti-reflection technical field of membrane, more particularly to a kind of multilayer wide spectrum hydrophobic type solar cell anti-reflection film
And preparation method thereof.
Background technology
Anti-reflection film, also known as antireflective coating, are widely used in solar cell, and flat-panel monitor, optics etc. is led
Domain.For solar cell surface packaged glass protective layer, wherein the refractive index of glass is 1.52 or so, and air refraction is 1,
This causes the sunshine that sunshine irradiation is up to 8% to be on the glass surface reflected, and in the encapsulation glass of solar cell
Anti-reflection film is plated on glass can effectively reduce the loss of incident light.The impurity such as steam and other dust suspended in air
Easily the transmission of sunshine can further be reduced by being attached to glass surface, therefore this requires the anti-reflection film of battery surface to possess
Resistance to environment, self-cleaning function.Common anti-reflection film includes monofilm and multilayer film two types.Prepare in the prior art anti-reflection
In the method for film, sol-gal process is because equipment is simple, with low cost, be not required to specific vacuum environment under normal temperature and pressure can just grasp
Make, and be widely used.
Silica (the SiO that single layer anti reflective coating is mainly prepared using base catalysis tetraethyl orthosilicate (TEOS)2) sol filming
It is prepared from, anti-reflection film is the SiO in colloidal sol2Little particle is formed in substrate accumulation, and the big refractive index of film porosity is low.Film exists
Transmitance is up to 100% on single wavelength, but its anti-reflection wavelength band is very small, is simply passed through at specific a certain wavelength
Rate is high, and its all band transmitance is all very small and film crocking resistance is excessively poor, and service life is short, limits answering for its reality
With.And the SiO prepared by acid/base composite catalyzing2Though film film crocking resistance is significantly improved, it is in visible ray
Interval anti-reflection scope is small, and film easily absorbs the moisture and suspended particulate of surrounding environment and cause its optical intolerant to environment
The decline of energy.
In the prior art, the anti-reflection film of multi-layer film structure turns into the focus of research.For example, the resistance to ring in order to improve anti-reflection film
The circumstances of border poor performance, proposes the SiO for using and being prepared with acid catalysis in the prior art2As internal layer, with acid catalysis TTIP (titaniums
Sour four butyl esters) TiO for preparing2Film as outer layer SiO2-TiO2Bilayer film, the film is due to outer layer TiO2Photocatalytic effect
Film is decomposed the organic matter of surrounding environment and is reached self-cleaning effects, but be due to high index of refraction TiO2As outer
Layer, duplicature passes through only 95% or so in the average of 300~800nm intervals.
In addition, also proposed a kind of SiO in the prior art2/TiO2/SiO2-TiO2The anti-reflection film of three-decker, this is anti-reflection
Film is with acid catalysis SiO2It is used as outer layer, TiO2As intermediate layer, TiO2-SiO2Laminated film is as internal layer, and anti-reflection film is in 400-
800nm scopes theory mean transmissivity is up to 98%.Meanwhile, to overcome anti-reflection film easily to absorb moisture and the suspension of surrounding environment
Grain and cause its optical property decline shortcoming, it is necessary to be initially formed SiO2/TiO2/SiO2-TiO2The initial configuration of trilamellar membrane,
Hydrophobically modified processing is carried out to the initial configuration again, typically handled using HMDS (HMDS) and alcohol mixed solvent
After at least 48 hours, make SiO2/TiO2/SiO2-TiO2Trilamellar membrane possesses hydrophobic performance, the contact of relatively untreated anti-reflection film
Angle brings up to 95.5 ° by 37.8 °.In existing SiO2/TiO2/SiO2-TiO2In the preparation method of trilamellar membrane, the SiO2/TiO2/
SiO2-TiO2Long, technical process is cumbersome for trilamellar membrane hydrophobically modified processing procedure activity time, and hydrophobicity is not fine, and
This hydrophobic treatment step can cause SiO2/TiO2/SiO2-TiO2Trilamellar membrane transmitance has declined.
The content of the invention
Therefore, to overcome disadvantages mentioned above, the present invention provide a kind of multilayer wide spectrum hydrophobic type solar cell anti-reflection film and
Its preparation method.
A kind of preparation method of multilayer wide spectrum hydrophobicity solar cell anti-reflection film, it comprises the following steps：Prepare
TiO2Colloidal sol and TiO2-SiO2Complex sol；It is that presoma prepares hydrophobic SiO with MTES (MTES)2It is molten
Glue presoma, prepares Nano-meter SiO_22Colloidal sol, by hydrophobic SiO2Sol precursor and Nano-meter SiO_22Colloidal sol is 1 according to volume ratio:
A hydrophobic SiO is obtained after 1.5~9 mixing2Colloidal sol；One substrate is provided, the TiO is used2-SiO2Complex sol is in substrate table
Face plated film, obtains TiO2-SiO2Laminated film；Use the TiO2Colloidal sol is in TiO2-SiO2Plated film on laminated film, obtains TiO2/
TiO2-SiO2Duplicature；And use the hydrophobic SiO2Colloidal sol is in TiO2/TiO2-SiO2Plated film on duplicature, is formed
SiO2/TiO2/SiO2-TiO2Three slice width spectrum hydrophobic type anti-reflection films.
Multilayer wide spectrum hydrophobicity solar cell anti-reflection film prepared by a kind of above-mentioned preparation method, wherein SiO2The folding of film
It is 1.44 to penetrate rate, and thickness is 96nm；TiO2The refractive index of film is 2.2, and thickness is 127nm；TiO2-SiO2The refractive index of film is
1.7, thickness is 72nm.
A kind of packaging glass of solar cell, including substrate, at least one surface of the substrate are provided with above-mentioned multilayer
Wide spectrum hydrophobicity solar cell anti-reflection film.
A kind of solar cell, the solar cell includes above-mentioned packaging glass of solar cell.
Relative to prior art, the preparation side of multilayer wide spectrum hydrophobic type solar cell anti-reflection film provided by the present invention
In method, hydrophobic outermost layer SiO is directly prepared2Film, without again to whole SiO2/TiO2/TiO2-SiO2Three-decker it is anti-reflection
Film carries out hydrophobicity processing, and SiO will not be influenceed because of hydrophobic treatment step2/TiO2/SiO2-TiO2The increasing of three-decker
The performance of permeable membrane, and shorten whole SiO2/TiO2/TiO2-SiO2The system of three slice width spectrum hydrophobic type solar cell anti-reflection films
The standby cycle.And, due to positioned at outermost SiO2Film has hydrophobicity, and the moisture and suspended particulate of surrounding environment are difficult absorption and existed
The surface of anti-reflection film, the light transmittance of anti-reflection film is higher.Meanwhile, the multilayer wide spectrum hydrophobic type solar energy prepared by this method
Battery has more preferable hydrophobic performance.
Brief description of the drawings
Fig. 1 is the solar cell package glass with multilayer wide spectrum hydrophobic type anti-reflection film in an embodiment of the present invention
The structural representation of glass.
Fig. 2 by Fig. 1 packaged glass provided section stereoscan photograph.
Fig. 3 contrasts collection of illustrative plates for the light transmission rate of the packaging glass of solar cell in simple glass and Fig. 1.
Fig. 4 be an embodiment of the present invention in multilayer wide spectrum hydrophobic type anti-reflection film preparation method flow chart.
Fig. 5 is TiO2Sol precursor is relative to TiO2Sol precursor and SiO2The percentage of the gross mass of sol precursor
Content and SiO2-TiO2The graph of a relation of the refractive index of film.
Fig. 6 is Nano-meter SiO_22SiO in colloidal sol2Grain size distribution.
Fig. 7 is hydrophobicity SiO2Sol precursor is relative to Nano-meter SiO_22The volume ratio of colloidal sol and multilayer wide spectrum hydrophobic type
The hydrophobic graph of a relation on anti-reflection film surface.
Fig. 8 is the atomic force microscopy according to multilayer wide spectrum hydrophobic type anti-reflection film surface made from the preparation method in Fig. 4
Mirror (AFM) photo.
Main element symbol description
Substrate 10
Anti-reflection film 20
SiO2-TiO2Film 21
TiO2Film 22
SiO2Film 23
Following embodiment will further illustrate the present invention with reference to above-mentioned accompanying drawing.
Embodiment
Fig. 1 is referred to, is the packaging glass of solar cell 100 with anti-reflection film 20 in an embodiment of the present invention
Structural representation, the anti-reflection film 20 is a kind of multilayer wide spectrum hydrophobic type anti-reflection film.In the present embodiment, the anti-reflection film 20
For SiO2/TiO2/SiO2-TiO2The wide spectrum hydrophobic type anti-reflection film of three-decker.
At least one surface of the substrate of glass 10 is provided with the anti-reflection film 20, in the present embodiment, in glass base
The anti-reflection film 20 is equipped with two relative surfaces at bottom 10.In other embodiments, the substrate of glass 10 can also
Using the transparent material of other high transmittances.
The anti-reflection film 20 includes the SiO set gradually along light incident direction2Film 23, a TiO2The SiO of film 22 and one2-
TiO221 3 layers of film is layered on top of each other to be formed.Wherein, SiO2-TiO2The laminating substrate of glass 10 of film 21 surface is set, hydrophobicity SiO2Film
23 are located at outermost layer, TiO2Film 22 is arranged at SiO2-TiO2Film 21 and hydrophobicity SiO2Between film 23.
The thickness and refractive index of each film layer of the anti-reflection film 20 can be calculated by Film Design software.In this reality
Apply in mode, anti-reflection film 20 is the SiO by using the structure of TFCcal Film Design software Computer Aided Designs λ/4- λ/2- λ/42/
TiO2/SiO2-TiO2Three slice width spectrum hydrophobic type anti-reflection films.The SiO of the structure of this λ/4- λ/2- λ/42/TiO2/SiO2-TiO2Three
Slice width spectrum hydrophobic type anti-reflection film has the anti-reflection property of good wide spectrum, and mean transmissivity is high in visible-range, in 400-
800nm scope mean transmissivities can reach up to 98%.
Fig. 2 is refer to, in the present embodiment, the SiO of anti-reflection film 202The refractive index of film 23 is 1.44, and thickness is 96nm；
Middle half wave layer is TiO2The refractive index of film 22 is 2.2, and thickness is 127nm；The SiO of innermost layer2-TiO2The refractive index of film 21 is
1.7, thickness is 72nm.
Fig. 3 is referred to, is the packaging glass of solar cell 100 with anti-reflection film 20 in simple glass and present embodiment
Light transmission rate contrast collection of illustrative plates.With no coating SiO2/TiO2/SiO2-TiO2The glass phase of three slice width spectrum hydrophobic type anti-reflection films
Than being provided with SiO in present embodiment2/TiO2/SiO2-TiO2The packaged glass of three slice width spectrum hydrophobic type anti-reflection films 20
100 mean transmissivity in visible-range is significantly improved, i.e. with the good anti-reflection property of wide spectrum.
Fig. 4 is referred to, is the SiO in an embodiment of the present invention2/TiO2/SiO2-TiO2Three slice width spectrum hydrophobic types increase
The preparation method of permeable membrane.Preparing above-mentioned SiO2/TiO2/SiO2-TiO2Before three slice width spectrum hydrophobic type anti-reflection films, first use
TFCcal Film Design software Computer Aided Designs go out the thickness of every tunic, then prepare SiO according still further to methods described2/TiO2/SiO2-
TiO2Three slice width spectrum hydrophobic type anti-reflection films.In the present embodiment, SiO in the anti-reflection film that prepared by the preparation method2The folding of film
It is 1.44 to penetrate rate, and thickness is 96nm；Middle half wave layer is TiO2The refractive index of film is 2.2, and thickness is 127nm；Innermost layer
SiO2-TiO2The refractive index of film is 1.7, and thickness is 72nm.
The SiO2/TiO2/SiO2-TiO2The preparation method of three slice width spectrum hydrophobic type anti-reflection films comprises the following steps：
S1：Prepare TiO2Colloidal sol and TiO2-SiO2Complex sol；
S2：It is that presoma prepares hydrophobic SiO with MTES (MTES)2Sol precursor, prepares one
The Nano-meter SiO_2 being sized2Colloidal sol, by hydrophobic SiO2Sol precursor and Nano-meter SiO_22A hydrophobicity is obtained after colloidal sol mixing
SiO2Colloidal sol；
S3：One substrate is provided, the SiO is used2-TiO2Complex sol obtains SiO in substrate surface plated film2-TiO2It is compound
Film；
S4：Use the TiO2Colloidal sol is in SiO2-TiO2Plated film on laminated film, obtains TiO2/SiO2-TiO2Duplicature；With
And
S5：Use the hydrophobic SiO2Colloidal sol is in TiO2/SiO2-TiO2Plated film on duplicature, forms SiO2/TiO2/
SiO2-TiO2Three slice width spectrum hydrophobic type anti-reflection films.
In step sl, TiO2-SiO2The preparation method of complex sol is not limited, in present embodiment, SiO2-TiO2It is compound
The preparation method of colloidal sol includes：
S11：By butyl titanate (TBOT), absolute ethyl alcohol, deionized water and concentrated hydrochloric acid according to certain mixed in molar ratio
After be stirred vigorously 1.5~3 hours and take out to obtain TiO2Sol precursor；
S12：By tetraethyl orthosilicate (TEOS), absolute ethyl alcohol, deionized water and concentrated hydrochloric acid according to certain mixed in molar ratio
After be stirred vigorously after 1.5~3 hours to obtain SiO2Sol precursor；
S13：By above-mentioned TiO2Sol precursor, SiO2After sol precursor is mixed with mass ratio 1: 1~1.5, acutely
Stir 2h or so：
S14：It is put into 30 DEG C of insulating boxs and is aged 5~8 days or so；S15：With being obtained after Kynoar membrane filtration
SiO2-TiO2Complex sol.
Fig. 5 is please combined in the lump, in step s 13, sets TiO2Sol precursor and SiO2The gross mass of sol precursor is
100, by adjusting TiO2Sol precursor weight/mass percentage composition, can adjust the SiO finally given2-TiO2The refractive index of film.
From fig. 5, it can be seen that in TiO2Sol precursor weight/mass percentage composition is interior for 20%~70% interval, TiO2Sol precursor
Weight/mass percentage composition and SiO2-TiO2The refractive index of film has certain linear relationship.In present embodiment, TiO2Precursor sol
Body and SiO2The mass ratio of sol precursor is 44.65: 55.35, i.e. TiO2Sol precursor weight/mass percentage composition is
44.65%, obtained SiO2-TiO2The refractive index of film is 1.7.In present embodiment, butyl titanate, absolute ethyl alcohol, deionization
The mol ratio of water and concentrated hydrochloric acid is 1: 49.75: 3.55: 0.22, and it is stirred vigorously 2 hours when mixing；Tetraethyl orthosilicate (TEOS),
The mol ratio of absolute ethyl alcohol, deionized water and concentrated hydrochloric acid is 1: 36.83: 4.01: 0.00416, and it is small that it is stirred vigorously 2 when mixing
When；Digestion time is 7 days；Filter membrane is the Kynoar filter membrane that aperture is 0.22 micron.It is to remove using the purpose of membrane filtration
Remove SiO2-TiO2The larger particle of particle diameter in complex sol, to prevent it after film forming, larger particles effect in colloidal sol
SiO2-TiO2The performances such as refractive index, the uniformity of composite membrane.The filter membrane employed in embodiment in the present invention is aperture
For 0.22 micron of Kynoar filter membrane.
In step sl, the TiO2The preparation method of colloidal sol is not limited, in present embodiment, TiO2The preparation method of colloidal sol
Including：By butyl titanate (TBOT), absolute ethyl alcohol, deionized water and concentrated hydrochloric acid according to acutely being stirred after certain mixed in molar ratio
Mix 1.5~3 hours and take out to obtain TiO2Sol precursor；Then by above-mentioned TiO2Sol precursor is put into 30 DEG C of insulating boxs and is aged
7d or so, then with 0.22 μm of Kynoar membrane filtration.
In step s 2, hydrophobicity SiO2The preparation method of sol precursor includes：By MTES
(MTES), mutual solvent and catalyst are mixed at normal temperatures according to a certain percentage；It is stirred vigorously 1~3 hour, is aged 6~9 days.
The mutual solvent can be ethanol, acetone, ethylene glycol or isopropanol.The catalyst can be hydrochloric acid, nitric acid or sulfuric acid.
MTES, mutual solvent and catalyst molar ratio 1: 35~45: 0.005~0.015.In present embodiment, the mutual solvent is
Absolute ethyl alcohol, catalyst is concentrated hydrochloric acid, and adds appropriate amount of deionized water, wherein, MTES, absolute ethyl alcohol, concentrated hydrochloric acid and deionization
The mol ratio of water is 1: 40: 0.01: 1；After mixing, it is stirred vigorously 2 hours, is aged 7 days, obtains hydrophobicity SiO2Precursor sol
Body.Hydrophobicity SiO2In sol precursor, the methyl free radicals that MTES occurs in hydrolysis, MTES are coated on SiO2Colloidal sol
The surface of particle, makes SiO2Sol precursor has hydrophobicity.
In the present embodiment, the Nano-meter SiO_22SiO in colloidal sol2Particle size at 10~20 nanometers.Nano-meter SiO_22
The preparation method of colloidal sol includes：According to mol ratio it is 1: 70~90: 2~5 by tetraethyl orthosilicate, absolute ethyl alcohol, deionized water
Ratio is mixed, and is stirred；Adjust pH value be 8~9 between；Ageing 5~7 days, after obtain Nano-meter SiO_22Colloidal sol.Present embodiment
In, tetraethyl orthosilicate, absolute ethyl alcohol, deionized water according to mol ratio be 1: 80: 3, use ammoniacal liquor adjust reactant pH value for
8.Wherein, in Nano-meter SiO_22Colloidal sol adds hydrophobicity SiO2, it is necessary to remove Nano-meter SiO_2 before colloidal sol2Ammoniacal liquor in colloidal sol.This reality
Apply in mode, ammoniacal liquor is removed by the method being heated to reflux.That is, by Nano-meter SiO_22Colloidal sol is heated to 75~85 DEG C, this embodiment party
It is 80 DEG C in formula, by the condensing reflux of condenser pipe 10~16 hours.From fig. 6, it can be seen that according to prepared by the above method receiving
Rice SiO2SiO in colloidal sol2Particle size range it is smaller, grain diameter is than more uniform.
By hydrophobicity SiO2Sol precursor and Nano-meter SiO_22Colloidal sol mixes 30~40 points according to certain volume ratio
Clock；It is aged after 2~3d and uses membrane filtration, obtains hydrophobic SiO2Colloidal sol.Hydrophobicity SiO2Sol precursor and Nano-meter SiO_22
Colloidal sol mixing is 1: 9~4: 6 mixing according to volume ratio, and the viscosity of resulting mixed sols is 2~5 millipascals after mixing
Second.During above-mentioned mixing, MTES and tetraethyl orthosilicate occur in being formed after hydrolysis respectively
Between product occur polycondensation so that-CH3Introduce SiO2In network structure, make SiO2With hydrophobicity.
Wherein, involved reaction equation is as follows：
Hydrolysis：
Si(OC2H5)4+4H2O→Si(OH)4+4C2H5OH
CH3Si(OC2H5)3+3H2O→CH3Si(OH)3+3C2H5OH
Polymerisation：
Si(OH)4+Si(OH)4→(HO)3Si-O-Si(OH)3+H2O
(HO)3Si-O-Si(OH)3+6Si(OH)4→((HO)3Si-O)3Si-O-Si(O-Si(OH)3)3+6H2O
Polycondensation reaction：
Si(OH)4+CH3Si(OH)3→CH3Si(OH)2OSi(OH)3+H2O
3CH3Si(OH)3+3CH3Si(OH)3→(OSi(CH3)OSi(CH3)O)3+9H2O
4CH3Si(OH)3+4CH3Si(OH)3→(OSi(CH3)OSi(CH3)O)4+12H2O
Introduce methyl (- CH3) after, SiO2The chemical formula of network structure is as follows：
Fig. 7 is please combined in the lump, it is assumed that hydrophobicity SiO2Sol precursor and Nano-meter SiO_22The volume of colloidal sol and for 100, passes through
Adjust hydrophobicity SiO2The volumn concentration of sol precursor can adjust the SiO finally obtained2/TiO2/SiO2-TiO2Three layers
The hydrophobic performance on wide spectrum hydrophobic type anti-reflection film surface.From figure 7 it can be seen that hydrophobicity SiO2The percentage composition of sol precursor
It is higher, hydrophobicity SiO2The hydrophobic performance of film is better.But, in order that SiO2/TiO2/SiO2-TiO2Three slice width spectrum hydrophobic types
The anti-reflection rate of anti-reflection film is uniform, in addition it is also necessary to pass through Nano-meter SiO_22Colloidal sol regulation outermost layer hydrophobicity SiO2The particle homogeneity of film and
Roughness.In present embodiment, it is preferable that the hydrophobicity SiO2Sol precursor and Nano-meter SiO_22The volume ratio of colloidal sol is 1:
1.5~9.
Filter membrane employed in present embodiment is the Kynoar filter membrane that aperture is 0.22 micron, hydrophobicity SiO2
Sol precursor and Nano-meter SiO_22The volume ratio of colloidal sol is 4: 6.Further, Fig. 8 is referred to, according to the system in present embodiment
The SiO that Preparation Method is obtained2/TiO2/SiO2-TiO2The roughness on three slice width spectrum hydrophobic type anti-reflection film surfaces is smaller, and particle ratio
It is more uniform.
In the present invention, due to using MTES for presoma preparation hydrophobicity SiO2In sol precursor, the preparation process,
Methyl in MTES introduces hydrophobicity SiO2In sol precursor, it is set to possess hydrophobicity, in hydrophobicity SiO2Sol precursor with
Nano-meter SiO_22After colloidal sol mixing, due to hydrophobicity SiO2The presence of methyl in sol precursor, make the colloidal sol that is obtained after mixing by
In-CH3It imported into SiO2Possesses hydrophobicity in network structure；By the hydrophobicity SiO for adjusting different proportion2Sol precursor
With Nano-meter SiO_22Mixing, while the viscosity for adjusting mixed sols makes it be more easy to film forming, because MTES hydrolyzes a large amount of of generation
Dimerization composition granule is very tiny, is filled into the SiO of base catalysis preparation2Cause that film is finer and close in film hole, mechanical performance
It is stronger and refractive index value needed for outermost layer in trilamellar membrane can be reached.
In step s3, selected substrate is soda-lime glass, and the surface of the substrate is handled, and substrate is put into
TiO2-SiO2In complex sol, on vertical shockproof pulling machine with 190mm/min pull rate in substrate plated film；Then exist
Half an hour is dried in the environment of 80 DEG C；In Muffle furnace TiO is obtained with 400 DEG C of calcining 2h2-SiO2Laminated film.The processing base
The step of basal surface is：Substrate is sequentially placed into 5% detergent, acetone, ethanol and deionized water, it is each to be cleaned by ultrasonic 15 points
Clock；Substrate surface is dried up with nitrogen；Using the two-sided each cleaning of UV cleaning machines 10 minutes, vacuum drying machine is put into standby.When
So, the method that film build method involved in the present invention is not limited to the lifting plated film, can also be using other conventional at present
Film plating process, such as spin-coating method.The pull rate of the lifting plated film can be selected according to parameters such as the viscosity of colloidal sol, this
It is preferably 190mm/min in embodiment.
In step s 4, by SiO2-TiO2Laminated film immerses TiO2In colloidal sol, on vertical shockproof pulling machine with
420mm/min pull rate plated film；After being dried 30 minutes under 80 DEG C of environment；It is put into Muffle furnace and is obtained with 400 DEG C of calcining 2h
TiO2/SiO2-TiO2Duplicature.
In step s 5, by TiO2/SiO2-TiO2Duplicature immerses hydrophobic modified SiO2In colloidal sol, carried vertically shockproof
With 190mm/min pull rate plated film in machine drawing；Dried under 200 DEG C of environment after 30min；30min is calcined at 400 DEG C again to obtain
Three layers of final SiO2/TiO2/SiO2-TiO2Hydrophobic membrane that broadband is anti-reflection.
SiO provided by the present invention2/TiO2/SiO2-TiO2In the preparation method of film, hydrophobic outermost layer is directly prepared
SiO2Film, without again to whole SiO2/TiO2/SiO2-TiO2Three slice width spectrum hydrophobic type anti-reflection films carry out hydrophobicity processing, will not
Because hydrophobic treatment step influences SiO2/TiO2/SiO2-TiO2The performance of three slice width spectrum hydrophobic type anti-reflection films, and make whole
SiO2/TiO2/SiO2-TiO2The film preparation process used time is shorter.Due to positioned at outermost SiO2Film has hydrophobicity, surrounding environment
Moisture and suspended particulate be difficult absorption on the surface of anti-reflection film, the light transmittance of anti-reflection film is higher.Meanwhile, prepared by this method
The SiO gone out2/TiO2/SiO2-TiO2Three slice width spectrum hydrophobic type anti-reflection films have more preferable hydrophobic performance.
In addition, those skilled in the art can also do other changes in spirit of the invention, certainly, these are according to present invention essence
The change that god is done, should all be included within scope of the present invention.
Claims (10)
1. a kind of preparation method of multilayer wide spectrum hydrophobicity solar cell anti-reflection film, it includes：
Prepare TiO2Colloidal sol and SiO2-TiO2Complex sol；
Hydrophobic SiO is prepared by presoma of MTES2Sol precursor, prepares Nano-meter SiO_22Colloidal sol, it is described
Nano-meter SiO_22The preparation method of colloidal sol includes：By tetraethyl orthosilicate, absolute ethyl alcohol, deionized water according to mol ratio be 1：70~
90：2~5 ratio mixing, stirs；And regulation pH value is 8~9, by hydrophobic SiO2Sol precursor and Nano-meter SiO_22
Colloidal sol is 1 according to volume ratio:A hydrophobic SiO is obtained after 1.5~9 mixing2Colloidal sol；
One substrate is provided, the SiO is used2-TiO2Complex sol obtains SiO in substrate surface plated film2-TiO2Laminated film；
Using the TiO2 colloidal sols in SiO2-TiO2Plated film on laminated film, obtains TiO2/SiO2-TiO2Duplicature；And
Use the hydrophobic SiO2Colloidal sol is in TiO2/SiO2-TiO2Plated film on duplicature, forms SiO2/TiO2/SiO2-TiO2
Three slice width spectrum hydrophobic type anti-reflection films.
2. the preparation method of multilayer wide spectrum hydrophobicity solar cell anti-reflection film as claimed in claim 1, it is characterised in that
The SiO2-TiO2The preparation method of complex sol includes：
Stirring obtains TiO in 1.5~3 hours after butyl titanate, absolute ethyl alcohol, deionized water and concentrated hydrochloric acid are mixed2Precursor sol
Body；
Stirring obtains SiO in 1.5~3 hours after tetraethyl orthosilicate, absolute ethyl alcohol, deionized water and concentrated hydrochloric acid are mixed2Precursor sol
Body；
By above-mentioned TiO2Sol precursor, SiO2Sol precursor is with mass ratio 1：After 1~1.5 is mixed, stirring 1.5~3 is small
When；
It is aged 5~8 days under isoperibol；And
With micropore size to obtain SiO after 0.15 micron~0.25 micron of membrane filtration2-TiO2Complex sol.
3. the preparation method of multilayer wide spectrum hydrophobicity solar cell anti-reflection film as claimed in claim 1, it is characterised in that
The TiO2The preparation method of colloidal sol includes：Stirred after butyl titanate, absolute ethyl alcohol, deionized water and concentrated hydrochloric acid are mixed
Obtain TiO within 1.5~3 hours2Sol precursor；With micropore size to obtain TiO after 0.15 micron~0.25 micron of membrane filtration2
Colloidal sol.
4. the preparation method of multilayer wide spectrum hydrophobicity solar cell anti-reflection film as claimed in claim 1, it is characterised in that
The hydrophobicity SiO2The preparation method of sol precursor includes：MTES, mutual solvent and catalyst are existed
Mixed under normal temperature；Stirring 1~3 hour；And, it is aged 6~9 days under constant temperature；Wherein, the mutual solvent is ethanol, acetone, second two
Alcohol or isopropanol；The catalyst is hydrochloric acid, nitric acid or sulfuric acid；The MTES, mutual solvent and catalyst
Molar ratio 1：35~45：0.005~0.015.
5. the preparation method of multilayer wide spectrum hydrophobicity solar cell anti-reflection film as claimed in claim 4, it is characterised in that
The Nano-meter SiO_22The preparation method of colloidal sol also includes：Ageing 5~7 days, obtains Nano-meter SiO_22Colloidal sol.
6. the preparation method of multilayer wide spectrum hydrophobicity solar cell anti-reflection film as claimed in claim 1, it is characterised in that
PH value is adjusted using ammoniacal liquor, in Nano-meter SiO_22Colloidal sol and hydrophobicity SiO2Before colloidal sol mixing, further comprise-remove ammoniacal liquor
Step, including：Nano-meter SiO_22Colloidal sol is stirred 10~16 hours using magnetic stirring apparatus under the conditions of 80 DEG C, then using condenser pipe
Condensing reflux removes the ammonia of remaining.
7. the preparation method of multilayer wide spectrum hydrophobicity solar cell anti-reflection film as claimed in claim 1, it is characterised in that
The hydrophobicity SiO2Sol precursor and Nano-meter SiO_22Colloidal sol is mixed, and the viscosity of the mixed sols obtained after mixing is 2~5
Mpas.
8. multilayer wide spectrum hydrophobicity solar cell prepared by a kind of preparation method as described in any one of claim 1~7 increases
Permeable membrane, it is characterised in that the SiO2The refractive index of film is 1.44, and thickness is 96nm；TiO2The refractive index of film is 2.2, and thickness is
127nm；SiO2-TiO2The refractive index of film is 1.7, and thickness is 72nm.
9. a kind of packaging glass of solar cell, including substrate, it is characterised in that at least one surface of the substrate set just like
Multilayer wide spectrum hydrophobicity solar energy anti-reflection film described in claim 8.
10. a kind of solar cell, it is characterised in that the solar cell includes solar cell as claimed in claim 9
Packaged glass.
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