CN107337356A - A kind of preparation method of polytetrafluoroethylene (PTFE) and the compound antireflective film of alumina atom layer - Google Patents
A kind of preparation method of polytetrafluoroethylene (PTFE) and the compound antireflective film of alumina atom layer Download PDFInfo
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- CN107337356A CN107337356A CN201710508231.7A CN201710508231A CN107337356A CN 107337356 A CN107337356 A CN 107337356A CN 201710508231 A CN201710508231 A CN 201710508231A CN 107337356 A CN107337356 A CN 107337356A
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- layer
- polytetrafluoroethylene
- ptfe
- alumina
- film
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Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/73—Anti-reflective coatings with specific characteristics
- C03C2217/734—Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/152—Deposition methods from the vapour phase by cvd
Abstract
A kind of preparation method of polytetrafluoroethylene (PTFE) and the compound antireflective film of alumina atom layer, this method uses electron beam evaporation methods first, one layer of dense polytetrafluoroethylene layer is deposited in transparent or semitransparent substrate, then redeposited porous Teflon nanometer rods layer, obtains double-deck poly tetrafluoroethylene；The double-deck poly tetrafluoroethylene of acquisition is put into atomic layer deposition apparatus again, deposits one layer of alumina-coated layer.Research finds that the composite membrane is respectively provided with splendid anti-reflection effect to the multi-angle incident light in visible-range；Simultaneously because the surface nature and chemical stability of the special hydrophobic oleophobic of polytetrafluoroethylene (PTFE) so that the antireflective film has good automatically cleaning effect and fabulous biocompatibility；In addition, alumina atom layer can keep uniform very small thickness, sample surfaces can be covered comprehensively.In the case where meeting the requirement of anti-reflection of film, the mechanical strength of film can be also improved, meets the application request of the surface such as optics, photonic device, colour filter anti-reflection.
Description
Technical field
The present invention relates to the preparation side of a kind of double-deck polytetrafluoroethylene (PTFE) and the compound automatically cleaning antireflective film of alumina atom layer
Method, belong to nano material and optical anti-reflection technical field of film preparation.
Background technology
Anti-reflection film is also referred to as antireflective film, because the light that can effectively reduce material surface reflects, increases the transmission capacity of light,
It is a kind of extremely wide thin-film material of application, has been widely used in all kinds of optical lens, photoelectric device, digital information and has shown
Antireflection antireflecting coating needed for device, dielectric film, electric thin, optoelectronic film, colour filter, optical recorder etc..Yet with
In actual application, most of antireflective film surface is prepared by inorganic matters such as silica, hafnium oxide more, and film can not be held
Tension, pressure, bending etc. are compared with large deformation, while these inorganic matters are mostly hydrophilic nmature, and poor with anthropochemistry compatibility, environment
The washing away of middle steam, grease, organic pollution, dust etc. are contaminated material surface, so as to reduce in the absorption of film surface
The anti-reflective and stability of antireflective film, and high polymer material is with its unique ductility and efficient, inexpensive manufacturing process, spy
The surface nature and chemical stability of different hydrophobic oleophobic so that high polymer material is expected to large-scale application in antireflective film field.
Traditional macromolecule membrane is prepared using the chemical method such as collosol and gel, the uncontrollable film thickness of this method and
The homogeneity of surface topography, so that the also refractive index of uncontrollable film, therefore the effect of the anti-reflection of film can not ensure；Separately
Outside, during preparing macromolecule membrane using chemical method, the pollution of thin film composition and the corrosion of substrate are easily caused.
Therefore need to develop new macromolecule anti-reflection membrane preparation technology, make in homogenization control macromolecule membrane anti-reflection
With while, also to prevent the pollution of thin film composition in preparation process and the corrosion of substrate.
The content of the invention
It is an object of the invention to provide the preparation method of a kind of polytetrafluoroethylene (PTFE) and the compound antireflective film of alumina atom layer, make
Not only technique is simple for it, and prepared antireflective film is respectively provided with splendid subtract for the multi-angle incident light in visible-range
Anti- anti-reflection effect, and in the case where meeting the requirement of anti-reflection of film, can also improve the mechanical strength of film.
In order to achieve the above object, the technical solution adopted by the present invention is：
The preparation method of a kind of polytetrafluoroethylene (PTFE) and the compound antireflective film of alumina atom layer, it is characterised in that this method includes
Following steps：
1) electron beam evaporation methods are utilized, angle of deposit is first set as 0 °, are deposited in transparent or semitransparent substrate
The dense polytetrafluoroethylene layer that one layer of reflectivity is 1.30~1.50；
2) angle of deposit is set as 80 °, then deposits one layer of reflectivity on the dense polytetrafluoroethylene layer of acquisition and be
1.15~1.25 porous Teflon nanometer rods layer, obtains double-deck poly tetrafluoroethylene；
3) the double-deck poly tetrafluoroethylene of acquisition is put into atomic layer deposition apparatus, cycle-index is arranged to 5~15, sinks
One layer of alumina-coated layer of product；
Preferably, the sedimentation rate of electron beam evaporation plating described in step 1) isAtomic layer deposition flow stream in step 3)
Measure 10~20SCCM；6~7nm of thickness of alumina-coated layer.
Transparent or semitransparent substrate of the present invention includes quartz plate, BK7, SF5, LAK14, FTO and sends Simon Rex glass
Any of glass, their refractive index is between 1.45~1.95.
Antireflective film prepared by the present invention has the technique effect of advantages below and high-lighting：1. by controlling electronic beam current
Size, prepare the macromolecule membrane that pattern is homogeneous, thickness is controllable；2. by two layers of refractive index of substrate deposit in gradient
The film of change, along with the ductility that polytetrafluoroethylene (PTFE) is excellent, make film anti-reflective in the range of visible light full spectrum
Can be more excellent than inorganic thin film；3. self-cleaning property：Because high polymer material specific strength is high, not soluble in water, wear-resisting, self-lubricating etc. is good
Good mechanochemistry property, anti-reflection film prepared therefrom in actual use will not be by environment steam, dust granule
Pollution and reduce the anti-reflective of film；4. high stability：In the case where not influenceing material antireflection rate, pass through atomic layer
Deposition technique coated aluminum oxide atomic layer in porous Teflon nanometer rods, the alumina atom layer can keep uniformly minimum
Thickness, and sample surfaces are covered comprehensively, so as to effectively improve the failure intensity of film.
Brief description of the drawings
Fig. 1 is that the section of the double-deck polytetrafluoroethylene (PTFE) of the present invention and the compound automatically cleaning antireflective film of alumina atom layer is illustrated
Figure.
Wherein：1- substrates；2- dense polytetrafluoroethylene layers；3- porous Teflon nanometer rods layers；4- alumina atoms
Layer.
Fig. 2 is the scanning electron microscope (SEM) photograph of polytetrafluoroethylene (PTFE) of the present invention and the compound antireflective film of alumina atom layer.
Fig. 3 is polytetrafluoroethylene (PTFE) of the present invention and the experiment value of the Normal incidence reflectance rate of the compound antireflective film of alumina atom layer
With calculated value.
Wherein：Ds is represented and is utilized optical software, calculates the Normal incidence reflectance rate in the BK7 deposition on glass antireflective film；
De is represented according to optical software result of calculation, and the Normal incidence reflectance for depositing the antireflective film is tested using electron beam evaporation equipment
Rate.
Fig. 4 be polytetrafluoroethylene (PTFE) of the present invention and the compound antireflective film of alumina atom layer visible ray incidence angles degree,
Three-dimensional reflection rate under different wave length.
Fig. 5 be polytetrafluoroethylene (PTFE) of the present invention reflectivity vertical with the room temperature of the compound antireflective film of alumina atom layer with it is uncoated
The vertical reflectivity of room temperature of the double-deck polytetrafluoroethylene (PTFE) automatically cleaning antireflective film of alumina atom layer.
Fig. 6 is that polytetrafluoroethylene (PTFE) of the present invention and the compound antireflective film of alumina atom layer are vertical after 100 DEG C of annealings
Straight reflectivity reflectivity vertical with the room temperature of the double-deck polytetrafluoroethylene (PTFE) automatically cleaning antireflective film of uncoated alumina atom layer.
Fig. 7 is that polytetrafluoroethylene (PTFE) of the present invention and the compound antireflective film of alumina atom layer are vertical after 200 DEG C of annealings
Straight reflectivity reflectivity vertical with the room temperature of the double-deck polytetrafluoroethylene (PTFE) automatically cleaning antireflective film of uncoated alumina atom layer.
Embodiment
The present invention is described further with reference to the accompanying drawings and examples and explains.
The preparation method of polytetrafluoroethylene (PTFE) provided by the invention and the compound antireflective film of alumina atom layer, first with
The thickness and refractive index of TFCalc optical software simulated dual-layer polytetrafluoroethylene (PTFE) antireflective films, find and optimize anti-reflection parameter；Then,
Calculated according to simulation, using electron beam evaporation methods, angle of deposit is first set as 0 °, sunk in transparent or semitransparent substrate
The dense polytetrafluoroethylene layer that one layer of reflectivity of product is 1.30~1.50；Angle of deposit is set as 80 ° afterwards, then in acquisition
The porous Teflon nanometer rods layer that one layer of reflectivity is 1.15~1.25 is deposited on dense polytetrafluoroethylene layer, is reflected
The double-deck poly tetrafluoroethylene that rate is successively decreased；Above-mentioned electron beam deposition speed isThen by the double-deck polytetrafluoroethyl-ne of acquisition
Alkene is put into atomic layer deposition apparatus, and ald 10~20SCCM of flow, cycle-index is arranged to 5~15, aoxidized
Aluminium clad.
Its concrete operation step is as follows：
1) at room temperature, transparent or semitransparent substrate is fixed on the sample stage of electron beam evaporation deposition machine；Using poly-
Tetrafluoroethene is deposition material, and electron beam equipment vacuum is evacuated into 3 × 10-4Pa；The transparent or semitransparent substrate includes stone
English piece, BK7, SF5, LAK14, FTO and any of Simon Rex glass is sent, their refractive index is between 1.45~1.95.
2) angle of deposit is set as 0 °, the fine and close polytetrafluoroethyl-ne that one layer of reflectivity is 1.30~1.50 is deposited in substrate
Alkene layer；
3) angle of deposit is set as 80 °, on the dense polytetrafluoroethylene layer obtained by step 2), redeposited one layer anti-
Penetrate the porous Teflon nanometer rods layer that rate is 1.15~1.25；
4) the double-deck polytetrafluoroethylene (PTFE) of acquisition is put into atomic layer deposition apparatus, cycle-index is arranged to 5~15, obtains thick
Spend for 6~7nm alumina-coated layers.
Embodiment 1
1) thickness using double-deck polytetrafluoroethylene (PTFE) antireflective film in TFCalc optical softwares simulation BK7 substrate of glass and refraction
Rate, find and optimize anti-reflection parameter, its light normal-incidence reflection rate at reference wavelength 550nm is down to 0；Wherein BK7 glass
The reflectivity of glass is 4.267%, and refractive index is 1.45~1.95；
2) the double-deck polytetrafluoroethyl-ne film that refractive index is progressively successively decreased is deposited in substrate successively.Comprise the following steps that：
1. clean BK7 substrate of glass is fixed on the sample stage of electron beam evaporation deposition machine；
2. at room temperature, using polytetrafluoroethylene (PTFE) as deposition material, the chamber of electron beam evaporation deposition machine is evacuated to vacuum
Spend for electron beam equipment vacuum is evacuated into 3 × 10-4Pa；
3. angle of deposit is set as 0 °, deposit that one layer of reflectivity is 1.30~1.50 in BK7 substrates fine and close poly- four
PVF layer；
4. angle of deposit is set as into 80 °, on the dense polytetrafluoroethylene layer by 3. obtaining, one layer of reflectivity of deposition is
1.15~1.25, porous Teflon nanometer rods layer；
5. the double-deck polytetrafluoroethylene (PTFE) of acquisition is put into atomic layer deposition apparatus, cycle-index is arranged to 5~15, obtains thick
Spend for 6~7nm alumina-coated layers.
3) Fig. 1, Fig. 2 are combined, the refractive index of laminated film is from dense polytetrafluoroethylene layer to porous Teflon nanometer
Rod layer gradually reduces.
Substrate light normal-incidence reflection rate at reference wavelength 550nm is down to from 4.267% as seen from Figure 3 connects
0 is bordering on, and experimental result is consistent with analog result.As shown in table 1：Wherein ds is represented using optical software calculating in BK7 glass
The Normal incidence reflectance rate of the compound antireflective film deposited on glass；De is represented according to optical software result of calculation, utilizes electron beam
The Normal incidence reflectance rate of the compound antireflective film of evaporation equipment experiment deposition.
Meanwhile our light that also analyze when different wave length enter the reflection of the compound antireflective film from incidence angles degree
Rate.Such as Fig. 4, in whole visible-range and in the case that incident angle is different, reflectivity of BK7 substrate of glass is higher than 4%,
The antireflective film can make the average reflectance of substrate be less than 1%, it was demonstrated that the excellent anti-reflection effect of the compound antireflective film.
4) in order to illustrate that the laminated film has excellent self-cleaning property and temperature stability, by itself and uncoated aluminum oxide
The double-deck polytetrafluoroethylene (PTFE) automatically cleaning antireflective film of atomic layer has carried out Experimental comparison：
Specific experiment is：The laminated film is made annealing treatment in 100 DEG C, 200 DEG C respectively, measurement film is to visible ray
Reflectivity and film borderline failure intensity.
A. after 100 DEG C of annealings, the laminated film is almost unchanged to the reflectivity of visible ray, but through 200 DEG C of annealing
After processing, the reflectivity of the double-deck polytetrafluoroethylene (PTFE) automatically cleaning antireflective film of the laminated film and uncoated alumina atom layer is less
Matching, illustrates that the temperature in use of the laminated film does not allow more than 200 DEG C.
B. before and after making annealing treatment, double-deck poly- four of borderline failure intensity than uncoated alumina atom layer of the laminated film
The borderline failure intensity of PVF automatically cleaning antireflective film is slightly lifted, and illustrating that temperature changes will not produce to the mechanical adhesion of film
Raw negative influence.Experimental result refers to table 1：
The borderline failure intensity of 1 two kinds of antireflective films of table
Embodiment 1 fully meets the technique effect of the present invention, i.e.,：
1) the homogeneous macromolecule membrane of pattern, thickness：By the size and suitable substrate cooling temperature that control electronic beam current
Degree, prepares the macromolecule membrane that pattern is homogeneous, thickness is controllable；
2) full spectrum anti-reflection：By the film changed in gradient in two layers of refractive index of substrate deposit, along with poly-
The excellent ductility of tetrafluoroethene, make film antireflective property in the range of visible light full spectrum more excellent than inorganic thin film；
3) self-cleaning property：Due to good mechanics such as high polymer material specific strength is high, not soluble in water, wear-resisting, self-lubricatings
Learn property, anti-reflection film prepared therefrom, in actual use will not by environment steam, dust granule pollution and drop
The anti-reflective of low film；
4) high stability：In the case where not influenceing material antireflection rate, the alumina atom layer of cladding can effectively improve
Diaphragm failure intensity.
Claims (4)
1. the preparation method of a kind of polytetrafluoroethylene (PTFE) and the compound antireflective film of alumina atom layer, it is characterised in that this method is included such as
Lower step：
1) electron beam evaporation methods are utilized, angle of deposit is first set as 0 °, one layer is deposited in transparent or semitransparent substrate
Reflectivity is 1.30~1.50 dense polytetrafluoroethylene layer；
2) angle of deposit is set as 80 °, then deposit on the dense polytetrafluoroethylene layer of acquisition one layer of reflectivity be 1.15~
1.25 porous Teflon nanometer rods layer, obtains double-deck poly tetrafluoroethylene；
3) the double-deck poly tetrafluoroethylene of acquisition is put into atomic layer deposition apparatus, cycle-index is arranged to 5~15, deposition one
Layer alumina-coated layer.
2. according to the preparation method of a kind of polytetrafluoroethylene (PTFE) described in claim 1 and the compound antireflective film of alumina atom layer, its
It is characterised by：The sedimentation rate of electron beam evaporation plating described in step 1) is
3. according to the preparation method of a kind of polytetrafluoroethylene (PTFE) described in claim 1 and the compound antireflective film of alumina atom layer, its
It is characterised by：10~20SCCM of atomic layer deposition flow stream amount in step 3)；6~7nm of thickness of alumina-coated layer.
A kind of 4. preparation side of the polytetrafluoroethylene (PTFE) and the compound antireflective film of alumina atom layer according to claim 1,2 or 3
Method, it is characterised in that：The transparent or semitransparent substrate includes quartz plate, BK7, SF5, LAK14, FTO and sends Simon Rex glass
Any of glass, their refractive index is between 1.45~1.95.
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| CN201710508231.7A CN107337356B (en) | 2017-06-28 | 2017-06-28 | Preparation method of polytetrafluoroethylene and aluminum oxide atomic layer composite antireflection film |
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| CN201710508231.7A CN107337356B (en) | 2017-06-28 | 2017-06-28 | Preparation method of polytetrafluoroethylene and aluminum oxide atomic layer composite antireflection film |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531469A (en) * | 2009-04-13 | 2009-09-16 | 浙江大学 | Transparent lyophobic alumina film and preparation method thereof |
| US9400343B1 (en) * | 2014-04-30 | 2016-07-26 | Magnolia Optical Technologies, Inc. | Highly durable hydrophobic antireflection structures and method of manufacturing the same |
| CN106526719A (en) * | 2017-01-09 | 2017-03-22 | 清华大学 | Homogeneous double-layer SiO2 and polytetrafluoroethylene composited self-cleaning anti-reflective film, and preparation method thereof |
-
2017
- 2017-06-28 CN CN201710508231.7A patent/CN107337356B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531469A (en) * | 2009-04-13 | 2009-09-16 | 浙江大学 | Transparent lyophobic alumina film and preparation method thereof |
| US9400343B1 (en) * | 2014-04-30 | 2016-07-26 | Magnolia Optical Technologies, Inc. | Highly durable hydrophobic antireflection structures and method of manufacturing the same |
| CN106526719A (en) * | 2017-01-09 | 2017-03-22 | 清华大学 | Homogeneous double-layer SiO2 and polytetrafluoroethylene composited self-cleaning anti-reflective film, and preparation method thereof |
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| CN107337356B (en) | 2020-05-22 |
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