CN107043223A - A kind of orderly straight-line groove micro-structural multilayer film glass and preparation method thereof - Google Patents

A kind of orderly straight-line groove micro-structural multilayer film glass and preparation method thereof Download PDF

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CN107043223A
CN107043223A CN201710067661.XA CN201710067661A CN107043223A CN 107043223 A CN107043223 A CN 107043223A CN 201710067661 A CN201710067661 A CN 201710067661A CN 107043223 A CN107043223 A CN 107043223A
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preparation
line groove
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multilayer film
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CN107043223B (en
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李晓瑜
崔海宁
程绪信
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Zhaoqing University
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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
    • C03C17/36—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 being a metal
    • C03C17/3602—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 being a metal the metal being present as a layer
    • C03C17/3649—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 being a metal the metal being present as a layer made of metals other than silver
    • 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
    • C03C17/36—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 being a metal
    • C03C17/3602—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 being a metal the metal being present as a layer
    • C03C17/3615—Coatings of the type glass/metal/other inorganic layers, at least one layer being non-metallic
    • 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
    • C03C17/36—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 being a metal
    • C03C17/3602—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 being a metal the metal being present as a layer
    • C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

The invention belongs to special glass material processing technical field, it is related to a kind of orderly straight-line groove micro-structural multilayer film glass and preparation method thereof；Straight-line groove microstructure film glass pane surface is arranged alternately ZrO2Step and corresponding channel bottom, ZrO2The preparation that continues successively of step and channel bottom upper surface has metal layer A l, Cu2O layers and ZnO layer three-layer thin-film；Preparation method comprises the following steps：1st, ZrO is prepared2Step and channel bottom；2nd, metal Al layer is prepared；3rd, Cu is prepared2O layers；4th, ZnO layer is prepared；The effects such as present invention has heat-insulating and energy-saving, photocatalysis, decoration.Such as its heat-insulating and energy-saving, which is embodied in multilayer film and microflute, can obstruct infrared emanation, and visible light-transmissive can be allowed again；Its photocatalysis can be decomposed into organic matter of the absorption on surface water and carbon dioxide, and straight line micro groove structure is effectively the residue of degraded together as natural rainwater, gravity and wind wash away totally.

Description

A kind of orderly straight-line groove micro-structural multilayer film glass and preparation method thereof
Technical field
The invention belongs to special glass material processing technical field, it is related to a kind of orderly straight-line groove micro-structural multilayer film Glass and preparation method thereof.
Background technology
With the aggravation reduced increasingly with environmental pollution of globalization petroleum-based energy, effectively using cold in solar control room Heat, photocatalysis makes organic matter dirt be rapidly decomposed into inorganic matter into ecological circulation and realize self-cleaning of building glass etc. Turn into one of outlet of sustainable development.But, major part architectural glazings use simple glass, coloured glass at present Or double glazing (framework is folded up between two sheet glass and is sealed), though it has certain effect to building energy conservation and comfortably, and it is full The foot not demand of people.In addition, also a kind of more popular technical method-pad pasting or plating i.e. on common monolithic glass Film, can also admirably achieve that certain summer is heat-insulated, Winter protection purpose.The product of hot topic is also low in the world in recent years Emission coated monolithic glass (abbreviation LowE glass) and following glass product-electrochomeric glass of a class new development.They All Shortcomings in terms of energy-saving efficiency and cost performance.Chinese utility model patent application 200420083199.0 discloses one Low radiation coated glass is planted, it is compounded with five film layers：Metal oxide film layer, metal or alloy barrier layer, argent, metal Or alloy barrier layer, metal oxide film layer.The composite glass structure uses too many noble metal and alloy, and cost is high.
Above-mentioned patent and other products do not possess the energy-conservation for making glass and light radiation and are in through characteristic with extraneous ring Border automatically can micro adjustment change function, i.e., replace feelings without making windowpane realize in day/night, fine day/cloudy day The function of light transmission features change under shape；They are also without glass pane more important function-glass automatic cleaning action.Close In automatically cleaning and its light-catalysed general principle, the TiO of semiconductor material with wide forbidden band is used as2, its photoelectricity/photocatalysis characteristic grinds Study carefully always individual focus.Magazine《J.Phys.D:Appl.Phys.》43rd phase (P.035301) in 2010 reports and utilizes TiO2 Nanocrystalline porous film does application of electrode in Photoelectrochemistry and obtains photoelectric transformation efficiency and brought up to from 1 ﹪ 7.9 more than ﹪ achievement.Magazine《Applied Surface Science》The 20th phase (P.8451) report of volume 257 in 2011 TiO2Photocatalytic degradation in terms of research, describe in this article and study TiO using lightinduced adsorption2Automatically cleaning and anti- Bacterium characteristic.With typical catalysis material TiO2The metal oxide for having similar characteristics also has ZnO, magazine《Thin Solid Films》496th phase (P.89-94) in 2006 is reported in ZnO and In2O3Doping and multiphase phase diagram theory in terms of some Deeply thin young work, particularly ZnO conduction/photoelectricity/photocatalysis research is even more to receive much attention, and this, which is mainly ZnO, not only has There is a basic performance of above-mentioned excellent material, and it is its aboundresources, cheap, nontoxic, and the space further researched and developed is very big.
In terms of inexpensive photoelectricity, photocatalysis, it is all good candidate material to have many metal oxides, and the present invention is used Titanium oxide (ZnO) and cuprous oxide (Cu2O) being mainly it not only has the basic performance of the materials such as photoelectricity, photocatalysis, and it Aboundresources, cheap, nontoxic, the space further researched and developed is very big.
At present, the decorative effect of rich and honour golden yellow color is all also not equipped with market and document, with photoelectricity, photocatalysis The functions such as self-cleaning, with low-E energy-saving effect, with just energy is automatic with outer without using extra automatically controlled sensor-based system The light radiation of boundary's light intensity and micro change glass passes through " the straight-line groove microstructure film glass " of characteristic, its structure, prepares Method and efficiency and all different with conventional traditional product and production method.
The content of the invention
The present invention solves and overcome above-mentioned problem, and one is provided using physics and chemically composited preparation method Plant orderly straight-line groove micro-structural multilayer film glass and preparation method thereof.
The present invention adopts the following technical scheme that realization, is described with reference to the drawings as follows：
A kind of orderly straight-line groove micro-structural multilayer film glass, including straight-line groove microstructure film glass plate 1, the straight-line groove is micro- The surface of structural membrane glass plate 1 is arranged alternately ZrO2Step 2 and corresponding channel bottom 3, ZrO2Step 2 and channel bottom 3 The upper surface preparation that continues successively has metal layer A l, Cu2O layers 5 and the three-layer thin-film of ZnO layer 6.
The straight-line groove microstructure film glass plate 1 is flat board, and the area of straight-line groove microstructure film glass plate 1 is in 1- Between 58000 square centimeters；The ZrO2The cycle of the upright projection plane of step 2 and channel bottom 3 is at 700-3000 nanometers Between.
The preparation method of described a kind of orderly straight-line groove micro-structural multilayer film glass, it is characterised in that including following step Suddenly：
Step 1, preparation ZrO2Step and channel bottom；
Step 2, preparation metal layer A l；
Step 3, preparation Cu2O layers；
Step 4, preparation ZnO layer.
ZrO is prepared described in technical scheme steps 12Step 2 and channel bottom 3 are comprised the following steps that：
1) it is equipped with ZrO2Precursor liquid；The ZrO2Precursor liquid proportioning be four butanol zirconiums：Benzoylacetone：Absolute ethyl alcohol= 1：0.8：28；
2) ZrO is prepared on clean glass plate using vertical czochralski method2Film；
3) using the ZrO in double laser beams interference effects face on a glass2On film, ZrO is obtained2Step 2 and trench bottom Portion 3, obtains the glass plate with ZrO2 steps 2 and channel bottom 3.
Comprising the following steps that for metal layer A l is prepared in technical scheme steps 2：
1) dc physics magnetically controlled sputter method deposited metals are used above in the glass plate with ZrO2 steps and channel bottom Layer Al；
2) in dc physics magnetron sputtering processes, institute deposited metal layer Al target material (source material) is from high-purity Al gold Category, Sputtering power density is chosen to be 31W/cm2, the sputtering pressure of Ar gas is chosen to be 1.2Pa, and the back end vacuum of vacuum chamber is selected For 10-3Pa, base station heating-up temperature is chosen to be 200 degree；
Metal layer A l film thicknesses are between 20-200 nanometers.
Cu is prepared described in technical scheme steps 32O layers comprise the following steps that：
1) colloid chemistry reaction is carried out in reactive tank using copper ions solution I and sodium citrate solution II；
2) " the glass/ZrO to be deposited that completion step 2 is obtained during the course of the reaction2/ Al " is { since glass surface It is followed successively by ZrO2[have ZrO2 steps 2 and channel bottom 3], Al layers } substrate is put into the chemical solution in reactive tank；Carry simultaneously Chemical reaction is controlled to prepare Cu for ultrasonic energy2O films, ultrasonic wave is chosen to be 15-75 khz frequencies and 45-250 watts defeated Go out power, reaction temperature is controlled in 40-75 DEG C of scope；
Cu2O layers of thickness is between 20-500 nanometers.
The copper ions solution I is allocated in technical scheme is:- the 1.3mol/L of copper sulphate 0.7, sodium ascorbate 0.3- 0.8mol/L；The preferred 1mol/L of copper sulphate, the preferred 0.5mol/L of sodium ascorbate；
Allocating the sodium citrate solution II is:Sodium citrate, 0.03-0.08mol/L；The preferred 0.05mol/ of sodium citrate L；
Comprising the following steps that for ZnO layer 6 is prepared described in technical scheme steps 4：
1) by completing " the glass/ZrO that step 3 is obtained2/Al/Cu2O " (is followed successively by ZrO since glass surface2,Al Layer, Cu2O layers) substrate is used above rf physics magnetically controlled sputter methods and prepares oxide skin(coating) ZnO；
2) in rf physics magnetron sputtering processes, institute deposited oxide layer ZnO target material (source material) selects high-purity ZnO Ceramics, Sputtering power density is chosen to be 56W/cm2, Ar and O2The sputter gas air pressure of gas is chosen to be 2.0Pa, the back end of vacuum chamber Vacuum is chosen to be 10-3Pa, base station heating-up temperature is chosen to be 300 degree；The thickness of ZnO layer 6 is between 20-900 nanometers.Most " glass/ZrO is obtained afterwards2/Al/Cu2O/ZnO " (is followed successively by ZrO since glass surface2, Al layers, Cu2O layers, ZnO layer).
The present invention mainly make use of a variety of physical and chemical principles --- (i) photoresistance and photocatalytic effect； (ii) composite principle of material；(iii) straight-line groove microstructure design；(iv) low emissivity material.
(i) photoresistance and photocatalytic effect
ZnO absorption band gap Eg is 3.30eV semi-conducting materials, can good match solar spectrum visible region and to visible Light has extraordinary transmissivity, and the characteristics such as good photoelectric characteristic and photocatalysis can be obtained with good photoelectric effect. It is well known that similar oxide semiconductor also has Cu2O, its energy gap Eg are 2.20eV, it may have above-mentioned nearly all Good physical chemistry and the characteristic such as photoelectric characteristic and photocatalysis.The good main table of photoelectric conversion characteristic of above-mentioned two kinds of materials It is now the carrier increase in membrane material when on sensitive its surface of sunlight irradiation；So as to ZnO and Cu2O film glass is conductive Characteristic changes with strong and weak change of incident light, and this will produce and heat-insulated effect is realized to the prevention of infrared emanation；Light is urged Changing characteristic can make film glass be used for photocatalytic degradation organic dirt and realize automatic cleaning action.
(ii) composite principle of material
According to band theory and crystallographic knowledge, the energy gap of general semiconductor is narrower, and the electronics of filled band is easy to Excited and enter conduction band, while hole is left in filled band, in the presence of external electric field, the sky in electronics and filled band in conduction band Cave all may participate in conduction.This just explain well why above-mentioned Cu2O/ZnO bilayer membrane materials have good physical chemistry Characteristic and composite effect.In the case of two kinds of metal oxide composites of the present invention, because Cu2O/ZnO two layer interfaces have There are different energy gap Eg sizes and carrier potential, therefore under photon h ν irradiation, oxide semiconductor Cu2Swashed in O The light induced electron of hair can be moved on another oxide semiconductor ZnO conduction band；Be excited in the ZnO hole of generation can be migrated Onto CdS valence band.It is all these to promote efficiently separating for respective light induced electron and hole, improve the semiconductor light of the two Electrical effect and the self-cleaning net effect for ultimately resulting in good photocatalytic effect.
Similar analysis and situation, in " Al/Cu2O " " metal/metal oxide " bed boundary, with lowest conduction band energy Level EcWith energy gap EgCu2The band structure that O oxides are combined with Al metal conductor layers can explain its photocatalytic activity Enhancing.In During Illumination, continue and come from ZnO and Cu2The light induced electron being excited inside O just moves to gold from conduction band Among category, the recombination rate of hole and electronics is eventually reduced, and improves the characteristic of photoelectricity and photochemical catalyst.
Generally, the less Cu of energy gap2O in principle can be by 400-800 of absorbing wavelength nanometer light, this just can be very well Ground absorbs visible ray and makes full use of it, still, Cu2O can not but utilize ultraviolet light well, because the electronics being wherein excited There is energy that substantial portion of energy conversion is phonon vibration without for being catalyzed it is understood that broad stopband with hole The absorption of ZnO correspondence " purple light-ultraviolet light " region spectrum frequency ranges, so by Cu2O and ZnO is compound to be can be achieved with possessing more Wide incident light response spectrum scope.
(iii) straight-line groove microstructure design
Orderly densely arranged straight-line groove micro-structural in " straight-line groove microstructure film glass " adds the surface of glass plate Product, improves the reflection characteristic of sunlight and various heat radiations., will be right according to them are designed under the influence of the dimensional effect of micro-structural The light of different spectral bands produces different transmissions, reflection, scattering；So that the micro-structural of reduced size can be to a certain extent Improve the stop to infrared band radiant light, it is ensured that the characteristic of visible transmission is realized.
It is well known that in our environment in general solar energy and various infrared sources, light source etc. for glass pane All it is angled incident light；And the micro-structural of reduced size all to produce one in the incident heat radiation light of glass surface Determine the reflection of multiple multiple angles of degree, and in straight-line groove micro-structural multiple reflections and decay；Avoiding problems due to general The mirror-reflection (i.e. normal reflection) of logical glass pane and coated glass and the reflection glare and light pollution of generation.
(iv) low emissivity material.
Due to " the ZrO coated in straight-line groove and its ledge surface2/Al/Cu2O/ZnO " is many of photoelectricity and low-radiation material Layer film, so this infrared optical heat radiation reflecting layer causes " the straight-line groove microstructure film glass " to have very low surface emissivity Rate, and it is very high to the reflectivity of infrared emanation；Visible ray can still pass through the film and glass plate simultaneously.Total effect energy Keep indoor light soft, realize that the save lighting energy, body-sensing are comfortable and healthy.
Comprehensive Design and utilization by above-mentioned four kinds of physics principles, should " straight-line groove microstructure film glass " realize as Under scene application.In summer, it can the heat radiation that sends of the outer sun of blocking portion locellus get in, indoor air-conditioning cold air is but Outdoor can not be by convection into, air-conditioning expense is saved；And it has to the visible light ray of the aerial diffusion in day and passes through characteristic well simultaneously, Save lighting expense.In the winter time, the far infrared that it effectively will distribute indoor radiating piece and indoor object is reflected back room It is interior, it is ensured that indoor heat does not scatter and disappear to outdoor.Simultaneously the visible ray of the part sun can also be allowed to get in, so as to save Warming by air conditioner and lighting expense are used.
Advantageous effects compared with prior art of the invention:
1) one kind is realized with multilayer film " ZrO2/Al/Cu2O/ZnO " and " Al/Cu2O/ZnO " is respectively peak and valley alternating Orderly densely arranged straight-line groove microstructure film glass and its manufacture method, the invention " straight-line groove microstructure film glass " has Sunshade, energy-conservation, the effect of decoration.
2) its energy-saving low-carbon be embodied in can it is heat-insulated and insulation, the sunlight of visual field spectral region can be allowed to pass through again, and Realize and save the effect that electric consumption on lighting reaches glass.
3) its heat-insulated multilayer film and microflute of being embodied in can obstruct infra-red radiation.
4) being somebody's turn to do " straight-line groove microstructure film glass " just can be automatic as ambient is strong without using extra automatically controlled sensor-based system The light radiation spent and change glass passes through characteristic.
5) organic matter adsorbed on surface can also be decomposed into by being somebody's turn to do the photocatalysis of " straight-line groove microstructure film glass " Water and carbon dioxide, straight line micro groove structure effectively degraded remnants and inorganic matter together with natural rainwater, gravity and Wind washes away totally；I.e. the laminated film can make body surface have the function of self-cleaning.
6) should " straight-line groove microstructure film glass " also there is certain curtain effect, you can seen not outside daytime room with realizing To indoor people and thing, and interior is it can easily be seen that the scene of outdoor.
7) design that " the straight-line groove microstructure film glass " can be selective has light yellow, silver color and wealth and rank golden yellow etc. The color of multiple types；With making human eye comfortable and certain light transmission characteristics；Can selectivity have broken colour light splitting, Ke Yixuan The reflection (avoiding reflection glare and light pollution) and the slow reflection of realization with reduction light of selecting property, can be selective have are partly anti- Penetrate or be totally reflected the decorative effect of minute surface.
Brief description of the drawings
The present invention is further illustrated below in conjunction with the accompanying drawings：
Fig. 1 is the integrally-built front view of one embodiment of the present invention；
Fig. 2 be in Fig. 1 A-A to sectional view；
In figure：1st, straight-line groove microstructure film glass plate；2、ZrO2Step；3rd, channel bottom；4th, metal layer A l；5、Cu2O Layer；6th, ZnO layer.
Embodiment
The present invention is explained in detail below：
Embodiment one
The present embodiment is multilayer film " ZrO2/Al/Cu2O/ZnO " and " Al/Cu2O/ZnO " is respectively that peak and valley alternately has The densely arranged straight-line groove microstructure film glass of sequence, straight-line groove microstructure film glass plate 1 is 1 square centimeter of writing board shape, its peak Replace the ZrO on the surface of wave-like with paddy2The cycle of the upright projection plane of step 2 and channel bottom 3 is 700 nanometers；Gold The thickness for belonging to layer Al is 20 nanometers；Cu2O layers of thickness is 20 nanometers；The thickness of ZnO layer is 20 nanometers.
The manufacture method of orderly straight-line groove micro-structural multilayer film glass, comprises the following steps：
Step 1, preparation ZrO2Step 2 and channel bottom 3:
ZrO used2Precursor liquid proportioning be four butanol zirconiums：Benzoylacetone：Absolute ethyl alcohol=1：0.8：28, and using vertically Czochralski method prepares ZrO on clean glass plate2；Using the ZrO in double laser beams interference effect face on a glass2On, obtain Obtain ZrO2Step 2 and channel bottom 3, the ZrO2The cycle of the upright projection plane of step 2 and channel bottom 3 is 700 nanometers.
Step 2, preparation metal layer A l:
Using physics magnetically controlled sputter method in ZrO2Metal layer A l is prepared on the surface of step 2 and channel bottom 3；Metal level Al thickness control is at 20 nanometers, and target material is high-purity Al metals, and sputtering power density is 31W/cm2, the sputtering of Ar gas Air pressure is 1.2Pa, and the back end vacuum of vacuum chamber is 10-3Pa, base station heating-up temperature is 200 degree.
Step 3, preparation Cu2O layers：
Colloid chemistry reaction is carried out in reactive tank using copper ions solution I and sodium citrate solution II, was being reacted " glass/ZrO to be deposited in journey2/ Al " substrates are put into the chemical solution in reactive tank, while providing ultrasonic energy Control chemically reacts to prepare Cu2O films；Oxide Cu2O layer film thickness is controlled at 20 nanometers；Copper ions solution I is:Copper sulphate 0.7mol/L, sodium ascorbate 0.3mol/L；The sodium citrate solution II is:Sodium citrate, 0.03mol/L.The chemistry Method prepares Cu2The temperature control of solution I and solution II is at 40 DEG C during O films, and ultrasonic wave be chosen to be 15 khz frequencies with And the energy field of 45 watts of power outputs is applied in reaction solution.
Step 4, preparation ZnO layer：
Using physics magnetically controlled sputter method in " glass/ZrO2/Al/Cu2O " substrate upper surfaces prepare ZnO layer.The thickness of ZnO layer Degree control is at 20 nanometers, and target material is high-purity ZnO ceramics, and radio frequency power density is 56W/cm2, Ar and O2The sputter gas gas of gas Press as 2.0Pa, the back end vacuum of vacuum chamber is 10-3Pa, base station heating-up temperature is 300 degree.
Embodiment two
The present embodiment is multilayer film " ZrO2/Al/Cu2O/ZnO " and " Al/Cu2O/ZnO " is respectively that peak and valley alternately has The densely arranged straight-line groove microstructure film glass of sequence, straight-line groove microstructure film glass plate is 1 square centimeter of writing board shape, its peak and The ZrO on the surface of paddy alternating wave-like2The cycle of the upright projection plane of step 2 and channel bottom 3 is 1800 nanometers；Metal Layer Al thickness is 100 nanometers；Cu2O layers of thickness is 100 nanometers；The thickness of ZnO layer is 500 nanometers.
The manufacture method of orderly straight-line groove micro-structural multilayer film glass, comprises the following steps：
Step 1, preparation ZrO2Step 2 and channel bottom 3:
ZrO used2Precursor liquid proportioning be four butanol zirconiums：Benzoylacetone：Absolute ethyl alcohol=1：0.8：28, and using vertically Czochralski method prepares ZrO on clean glass plate2；Using the ZrO in double laser beams interference effect face on a glass2On, obtain Obtain ZrO2Step 2 and channel bottom 3, the ZrO2The cycle of the upright projection plane of step 2 and channel bottom 3 is 1800 nanometers.
Step 2, preparation metal layer A l:
Using physics magnetically controlled sputter method in ZrO2Metal layer A l4 is prepared on the surface of step 2 and channel bottom 3；Metal Layer Al thickness control is at 100 nanometers, and target material is high-purity Al metals, and sputtering power density is 31W/cm2, Ar gas splashes Pressure of emanating is 1.2Pa, and the back end vacuum of vacuum chamber is 10-3Pa, base station heating-up temperature is 200 degree.
Step 3, preparation Cu2O layers：
Colloid chemistry reaction is carried out in reactive tank using copper ions solution I and sodium citrate solution II, was being reacted " glass/ZrO to be deposited in journey2/ Al " substrates are put into the chemical solution in reactive tank, while providing ultrasonic energy Control chemically reacts to prepare Cu2O films；Oxide skin(coating) Cu2O film thicknesses are controlled at 100 nanometers；Copper ions solution I is:Sulfuric acid Copper 1mol/L, sodium ascorbate 0.5mol/L；The sodium citrate solution II is:Sodium citrate, 0.05mol/L.The chemistry Method prepares Cu2The temperature control of solution I and solution II is at 55 DEG C during O films, and ultrasonic wave be chosen to be 45 khz frequencies with And the energy field of 150 watts of power outputs is applied in reaction solution.
Step 4, preparation ZnO layer：
Using physics magnetically controlled sputter method in " glass/ZrO2/Al/Cu2O " substrate upper surfaces prepare ZnO layer 6.ZnO layer 6 Thickness control is at 500 nanometers, and target material is high-purity ZnO ceramics, and radio frequency power density is 56W/cm2, Ar and O2The sputter gas of gas Air pressure is 2.0Pa, and the back end vacuum of vacuum chamber is 10-3Pa, base station heating-up temperature is 300 degree.
Embodiment three
The present embodiment is multilayer film " ZrO2/Al/Cu2O/ZnO " and " Al/Cu2O/ZnO " is respectively that peak and valley alternately has The densely arranged straight-line groove microstructure film glass of sequence, straight-line groove microstructure film glass plate 1 is 1 square centimeter of writing board shape, its peak Replace the ZrO on the surface of wave-like with paddy2The cycle of the upright projection plane of step 2 and channel bottom 3 is 3000 nanometers；Gold The thickness for belonging to layer Al is 200 nanometers；Cu2O layers of thickness is 500 nanometers；The thickness of ZnO layer is 900 nanometers.
The manufacture method of orderly straight-line groove micro-structural multilayer film glass, comprises the following steps：
Step 1, preparation ZrO2Step 2 and channel bottom 3:
ZrO used2Precursor liquid proportioning be four butanol zirconiums：Benzoylacetone：Absolute ethyl alcohol=1：0.8：28, and using vertically Czochralski method prepares ZrO on clean glass plate2；Using the ZrO in double laser beams interference effect face on a glass2On, obtain Obtain ZrO2Step 2 and channel bottom 3, the ZrO2The cycle of the upright projection plane of step 2 and channel bottom 3 is 3000 nanometers.
Step 2, preparation metal layer A l:
Using physics magnetically controlled sputter method in ZrO2Metal layer A l4 is prepared on the surface of step 2 and channel bottom 3；Metal Layer Al thickness control is at 200 nanometers, and target material is high-purity Al metals, and sputtering power density is 31W/cm2, Ar gas splashes Pressure of emanating is 1.2Pa, and the back end vacuum of vacuum chamber is 10-3Pa, base station heating-up temperature is 200 degree.
Step 3, preparation Cu2O layers：
Colloid chemistry reaction is carried out in reactive tank using copper ions solution I and sodium citrate solution II, was being reacted " glass/ZrO to be deposited in journey2/ Al " substrates are put into the chemical solution in reactive tank, while providing ultrasonic energy Control chemically reacts to prepare Cu2O films；Oxide skin(coating) Cu2O film thicknesses are controlled at 500 nanometers；Copper ions solution I is:Sulfuric acid Copper 1.3mol/L, sodium ascorbate 0.8mol/L；The sodium citrate solution II is:Sodium citrate, 0.08mol/L.Describedization Method prepares Cu2The temperature control of solution I and solution II is chosen to be 75 khz frequencies at 75 DEG C, and ultrasonic wave during O films And the energy field of 250 watts of power outputs is applied in reaction solution.
Step 4, preparation ZnO layer：
Using physics magnetically controlled sputter method in " glass/ZrO2/Al/Cu2O " substrate upper surfaces prepare ZnO layer 6.ZnO layer 6 Thickness control is at 900 nanometers, and target material is high-purity ZnO ceramics, and radio frequency power density is 56W/cm2, Ar and O2The sputter gas of gas Air pressure is 2.0Pa, and the back end vacuum of vacuum chamber is 10-3Pa, base station heating-up temperature is 300 degree.

Claims (10)

1. a kind of orderly straight-line groove micro-structural multilayer film glass, it is characterised in that：Including straight-line groove microstructure film glass plate (1), Straight-line groove microstructure film glass plate (1) surface is arranged alternately ZrO2Step (2) and corresponding channel bottom (3), ZrO2The preparation that continues successively of step (2) and channel bottom (3) upper surface has metal layer A l (4), Cu2O layers (5) and ZnO layer (6) three Layer film.
2. a kind of orderly straight-line groove micro-structural multilayer film glass according to claim 1, it is characterised in that：
The straight-line groove microstructure film glass plate (1) is flat board, and the area of straight-line groove microstructure film glass plate (1) is in 1- Between 58000 square centimeters；
The ZrO2The cycle of the upright projection plane of step (2) and channel bottom (3) is between 700-3000 nanometers.
3. a kind of preparation method of orderly straight-line groove micro-structural multilayer film glass according to claim 1, it is characterised in that Comprise the following steps：
Step 1, preparation ZrO2Step (2) and channel bottom (3)；
Step 2, preparation metal layer A l；
Step 3, preparation Cu2O layers；
Step 4, preparation ZnO layer.
4. a kind of preparation method of orderly straight-line groove micro-structural multilayer film glass according to claim 3, it is characterised in that：
ZrO is prepared described in step 12Step (2) and channel bottom (3) are comprised the following steps that：
1) it is equipped with ZrO2Precursor liquid；The ZrO2Precursor liquid proportioning be four butanol zirconiums：Benzoylacetone：Absolute ethyl alcohol=1： 0.8：28；
2) ZrO is prepared on clean glass plate using vertical czochralski method2Film；
3) using the ZrO in double laser beams interference effects face on a glass2On film, ZrO is obtained2Step (2) and channel bottom (3) glass plate with ZrO2 steps (2) and channel bottom (3), is obtained.
5. a kind of preparation method of orderly straight-line groove micro-structural multilayer film glass according to claim 3, it is characterised in that：
Comprising the following steps that for metal layer A l is prepared in step 2：
1) dc physics magnetically controlled sputter method deposition gold is used above in the glass plate with ZrO2 steps (2) and channel bottom (3) Belong to layer Al (4)；
2) in dc physics magnetron sputtering processes, institute deposited metal layer Al (4) target material selects high-purity Al metals, sputtering power Density is chosen to be 31W/cm2, the sputtering pressure of Ar gas is chosen to be 1.2Pa, and the back end vacuum of vacuum chamber is chosen to be 10-3Pa, base Base frame heating-up temperature is chosen to be 200 degree.
6. a kind of preparation method of orderly straight-line groove micro-structural multilayer film glass according to claim 5, it is characterised in that：
Metal layer A l (4) film thickness is between 20-200 nanometers.
7. a kind of preparation method of orderly straight-line groove micro-structural multilayer film glass according to claim 3, it is characterised in that：
Cu is prepared described in step 32O layers comprise the following steps that：
1) colloid chemistry reaction is carried out in reactive tank using copper ions solution I and sodium citrate solution II；
2) " the glass/ZrO to be deposited that completion step 2 is obtained during the course of the reaction2/ Al " substrates are put into the change in reactive tank Learn in solution；Ultrasonic energy is provided simultaneously to control chemical reaction to prepare Cu2O films, ultrasonic wave is chosen to be 15-75 kilo hertzs of frequencies Rate and 45-250 watts of power output, reaction temperature are controlled in 40-75 DEG C of scope.
8. a kind of preparation method of orderly straight-line groove micro-structural multilayer film glass according to claim 7, it is characterised in that：
The Cu2O layers of thickness is between 20-500 nanometers；
Allocating the copper ions solution I is:- the 1.3mol/L of the copper sulphate 0.7, -0.8mol/L of sodium ascorbate 0.3；Copper sulphate It is preferred that 1mol/L, the preferred 0.5mol/L of sodium ascorbate；Allocating the sodium citrate solution II is:Sodium citrate, 0.03- 0.08mol/L；The preferred 0.05mol/L of sodium citrate.
9. a kind of preparation method of orderly straight-line groove micro-structural multilayer film glass according to claim 3, it is characterised in that：
Comprising the following steps that for ZnO layer is prepared described in step 4：
1) by completing " the glass/ZrO that step 3 is obtained2/Al/Cu2Rf physics magnetically controlled sputter method systems are used above in O " substrates Standby oxide ZnO layer (6)；
2) in rf physics magnetron sputtering processes, the target material of institute's deposition oxide ZnO layer (6) is from high-purity ZnO ceramics, sputtering Power density is chosen to be 56W/cm2, Ar and O2The sputter gas air pressure of gas is chosen to be 2.0Pa, and the back end vacuum of vacuum chamber is selected For 10-3Pa, base station heating-up temperature is chosen to be 300 degree.
10. a kind of preparation method of orderly straight-line groove micro-structural multilayer film glass according to claim 9, its feature exists In：
The thickness of the ZnO layer (6) is between 20-900 nanometers.
CN201710067661.XA 2017-02-07 2017-02-07 Multilayer film glass with ordered linear groove microstructure and preparation method thereof Active CN107043223B (en)

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CN109972112A (en) * 2019-05-16 2019-07-05 郑州大学 A kind of multi-layer compound film door glass and preparation method thereof with dual function

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CN1537085A (en) * 2001-08-02 2004-10-13 3M Al2O3-rare earth oxide-ZrO2/HfO2 materials and methods of making and using the same
CN101084111A (en) * 2004-12-21 2007-12-05 康宁股份有限公司 Light polarizing products and method of making same
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CN109972112A (en) * 2019-05-16 2019-07-05 郑州大学 A kind of multi-layer compound film door glass and preparation method thereof with dual function
CN109972112B (en) * 2019-05-16 2021-03-26 郑州大学 Multi-layer composite film door and window glass with double functions and preparation method thereof

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