CN102584019B - Equipment and method for plating glass antireflective film through chemical vapor deposition process - Google Patents
Equipment and method for plating glass antireflective film through chemical vapor deposition process Download PDFInfo
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- CN102584019B CN102584019B CN201210021320.6A CN201210021320A CN102584019B CN 102584019 B CN102584019 B CN 102584019B CN 201210021320 A CN201210021320 A CN 201210021320A CN 102584019 B CN102584019 B CN 102584019B
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Abstract
Aiming at the defects that the energy consumption is high when the glass antireflective film is plated, and the glass rejection rate is high because the edge thickness of cut-to-length glass is thin in the prior art, the invention provides equipment and method for plating a glass antireflective film through a chemical vapor deposition process. The equipment comprises an antireflective film raw material supply device, an antireflective film liquid-phase raw material vaporization device, a waste gas treatment device, a film plating device and a thermostat, wherein the antireflective film liquid-phase raw material vaporization device is provided with vaporization chambers; the film plating device is provided with nozzles and waste gas discharge channels; the antireflective film raw material supply device is communicated with the vaporization chambers of the vaporization device; the vaporization chambers are communicated with the nozzles of the film plating device through tubes; and the waste gas discharge channels are communicated with the waste gas treatment device through tubes. According to the method provided by the invention, the glass antireflective film is plated after glass is molded but before annealed. The glass antireflective film plated by adopting the equipment and the method has the advantages of high film quality, low energy consumption and large production scale.
Description
Technical field
The present invention relates to the Apparatus and method for that chemical vapor deposition method is coated with glass antireflective coating, particularly relate to the Apparatus and method for that is coated with online glass antireflective coating with chemical vapor deposition method.
Background technology
Antireflective coating claims again anti-reflection film, and its major function is the reflected light that reduces or eliminates the optical surfaces such as lens, prism, plane mirror, glass, thereby increases the light transmission capacity of these elements, reduces or eliminates the stray light of system.
In solar cell member of all categories, all be unable to do without upper strata and be subject to light cover-plate glass material, it is the ultra-clear glasses cover plate that covers solar cell surface and allow sunlight to enter photocell generating semiconductor material to protect again photocell itself.As everyone knows, light wave can produce refraction and reflex in the time of the dielectric surface by different refractivity, and for solar cell, luminous reflectance is disadvantageous, can make luminous energy scatter and disappear and can not fully be utilized because reflecting.Through calculating and measuring, luminous reflectance factor when light wave process cover-plate glass list surface is that 4%, two surface is exactly 8%.Glass production enterprise can effectively have been controlled frit iron-holder at present, makes the absorptivity of photovoltaic cell cover-plate glass more much lower than common building glass, and light transmission rate approaches 92%.Therefore the luminous reflectance factoies that reduce the two surfaces of cover-plate glass be improve solar-energy photo-voltaic cell namely PV cell power generation efficiency important by way of.Experiment shows, the raising of the minimizing of light reflection of glass surface rate and PV battery unit surface generated energy is proportional.Glass industry generally adopts and is coated with antireflective coating at glass surface and reduces glass surface to reflection of light rate.
The plating method of the photovoltaic glass antireflective coating of at present widespread use has three kinds of off-line vacuum magnetic-control sputtering methods, normal temperature wet processing, off-line CVD technique, and they have respectively following features:
Off-line vacuum magnetic-control sputtering method is coated with glass antireflective coating: in the space of high vacuum, the glass of wash clean is sent in the middle of DC high voltage electric field, vacuum chamber passes into a small amount of Ar gas, the metal oxide of selecting on request or nonmetal oxide material are as cathode targets, high-voltage electric field is by ar atmo ionization high-speed impact cathode targets, target material can be launched glass surface and be combined with glass surface molecular linkage at a high speed with molecularity, has so just formed coated glass.If target material specific refractory power is proper and film thickness is suitable, just can obtain anti-reflective effect.
This technique can be manufactured MULTILAYER COMPOSITE antireflection film, and shortcoming is: rete firmness is low, and reflectance coating is difficult to keep for a long time antireflective effect outdoor; Facility investment is large; Manufacturing cost is high.
Off-line wet production glass with reflection reducing coating: off-line wet process technique is divided into three kinds of gel methods, spraying method, roll printing method.
Gel method is exactly that the glass of wash clean is immersed in antireflective coating raw material coagulant liquid, then, through oven dry, tempering two procedures, forms two-sided antireflective coating at glass surface;
Spraying method is exactly the glass surface that antireflective coating material solution is evenly ejected into wash clean by spray gun, then through oven dry, tempering two procedures, forms antireflection film at glass surface;
Roll printing method is exactly the glass surface that by accurate rubber roll, antireflective coating material solution is evenly coated to wash clean, makes glass possess antireflective effect thereby then form antireflection film through oven dry, tempering two procedures at glass surface.
Above three kinds of techniques are all to complete under normal temperature wet method condition, the antireflective coating raw material using is at present all organosilicon material substantially, organic substance decomposing in manufacturing processed, make thin-film material form molecular level hole, therefore the product of producing is porous silicon oxide membrane, film firmness, intensity, stability is all very undesirable, affected by microcosmic vesicular structure, when product export, anti-reflective effect still can, but making after PV battery component, than being easier to be subject to environmental pollution impact, a large amount of dirts enter Micro porosity, the light transmission rate of cover-plate glass is declined, the unit surface generated energy that even can make this subassembly product is lower than the PV battery component of plated film not.Above-mentioned three kinds of techniques anti-reflection film solution used all adopts the mixture of organosilicon, ethanol, ammoniacal liquor etc. in addition, and environment is caused to certain pollution.Course of processing energy consumption is relatively high.
Off-line CVD technique: off-line CVD explained hereafter photovoltaic anti-reflection film glass is the technology that developed recently gets up, this technique has effectively been improved the rete defect of the product existence of vacuum magnetic-control sputtering method and wet method coating process.This technique be glass processing enterprise in cold working process--a set of off-line CVD coating film production line has been installed between annealing furnace, it is conventionally by reheating--CVD plated film--, and annealing device forms again, be that ultrawhite cotton ginning glass is through cutting, edging, clean, after dry, enter off-line CVD coating film production line, glass is reheated 650 ° of C, glass passes through from CVD plated film device below afterwards, CVD plated film device is to high temp glass jet surface plated film mixing raw material gas, chemical feedstocks gas at high temperature decomposes generation inorganic oxide molecule deposition to glass surface, form certain thickness anti-reflection coated glass product.
This production technique has following weak point: the one, and energy input is larger, and off-line CVD filming equipment reheats glass can consume a large amount of electric energy, and approximately every square metre of 3.2mm glass increases power consumption 4.2 KWhr; The 2nd, rete is affected greatly by glass quality, unstable.Frit can be subject to pollution in various degree from the Yuan Pian factory rear surface of dispatching from the factory, as the impact of isolated material performance on original sheet glass quality, impact, the impact of glass storage time length etc. of glass storage environment.The bonding strength of glass and plated film rete can decline and quality unstable.The 3rd, glass coating process can form the partially thin defect of thickness, the colour-difference that with the naked eye just can see this technique edges portion and middle portion in scale glass edge portion.This defect is that technique is limit inevitably, because scale original sheet glass is to pass through one by one below plated film device in the time entering off-line coated device, and glass both sides also can form gap space between sheet and sheet and in glass run process, the irregular variation of coating raw material flow can be caused in these glass gaps, causes glass edge portion rete attenuate.If control improper meeting, to impact scope excessive, thereby produce a large amount of waste products.The new photovoltaic anti-reflection film glass standard of formulating of country allows limit portion range of influence to be less than 7mm.
Summary of the invention
The object of the invention is when being coated with glass antireflective coating in prior art energy consumption large, scale glass edge portion thickness is as thin as the deficiency that makes glass scrap rate high partially, provide a kind of energy consumption low, the chemical vapor deposition method that can coat uniform glass antireflective coating is coated with the Apparatus and method for of glass antireflective coating.
In order to realize above-mentioned technical purpose, technical scheme of the present invention is:
A kind of chemical vapor deposition method is coated with the equipment of glass antireflective coating, comprise antireflective coating raw feed materials device, be provided with vaporizing chamber antireflective coating liquid phase feed vapourizing unit, emission-control equipment, be provided with plated film device and the thermostat of nozzle and waste air passage, described antireflective coating raw feed materials device is communicated with the vaporizing chamber pipe of described vapourizing unit, described vaporizing chamber is communicated with the blast tube of described plated film device, and described waste air passage is communicated with described emission-control equipment pipe;
Described vapourizing unit also comprises the housing of sealing and carries vapour feeding mechanism, described vaporizing chamber is tornadotron, it is fixedly installed in described housing, described tornadotron is heated by described thermostat, one end of described tornadotron is connected with a year vapour steam inlet pipe, the other end of described tornadotron is connected with liquid phase feed feed-pipe, vaporization raw material discharge nozzle is connected with described tornadotron, in described tornadotron, be provided with swirler, described swirler is screw shaft, and the axis of described screw shaft and the axis of described tornadotron be arranged in parallel;
Described thermostat is deep fat thermostat, between described housing and described tornadotron, be provided with the defeated heat space for deep fat circulation, the hot oil outlet of the hot oil inlet of described housing by setting it on and hot oil outlet and described deep fat thermostat and hot oil inlet is corresponding is connected;
Described nozzle is communicated with described vaporizing chamber pipe by antireflective coating raw material collecting pipe, described waste air passage is communicated with emission-control equipment pipe by waste gas collecting pipe, described nozzle and waste air passage are formed by spacer pieces interval, and described nozzle and waste air channel parallel are crisscross arranged;
Described thermostat is deep fat thermostat, is provided with constant temperature oil pipe on described spacer pieces, and the oil-in of constant temperature oil pipe and oil outlet thereof are communicated with oil outlet and the oil-in respective tube thereof of described deep fat thermostat respectively;
The both sides of described each nozzle arrange respectively a waste air passage;
Described plated film device is provided with nozzle stationary installation, and described nozzle stationary installation is made up of nozzle plate and hanging beam, and described nozzle plate is fixedly connected with described hanging beam by suspender member, and described spacer pieces is fixedly connected with described nozzle plate;
Be provided with through hole corresponding to nozzle and waste air passage on described nozzle plate, described nozzle is connected with described antireflective coating raw material collecting pipe by described through hole, and described waste air passage is connected with described waste gas collecting pipe by described through hole;
Described deep fat thermostat is composed in series by oil heater, oil cooler and the pipeline that connects the two, the oil export of described oil heater is the oil export of deep fat thermostat, the oil-in of oil cooler is the oil inlet of permanent oily deep fat device, and oil heater, oil cooler are respectively arranged with temperature sensing device and are electrically connected with electrical control gear.
Chemical vapor deposition method is coated with a method for glass antireflective coating, after glass ware forming, annealing before be coated with glass antireflective coating;
The described glass antireflective coating that is coated with comprises the steps:
A, join, feeding: antireflective coating raw material in proportion, enter vapourizing unit after transferpump pressurization;
B, liquid phase antireflective coating feed vaporization: liquid phase reflectance coating raw material is vaporized and formed vapour phase antireflective coating raw material by vapourizing unit;
C, deposition: vapour phase antireflective coating raw material enters plated film device, sprayed to the hot glass ribbon surface of moulding by nozzle, vapour phase antireflective coating raw material and gas raw material are deposited on hot glass ribbon surface and form glass antireflective coating rete after hot glass ribbon fast heating at high temperature decomposes, and complete being coated with of glass surface antireflection film;
In described step B, adopt described vapourizing unit, be delivered into described vaporizing chamber by liquid phase antireflective coating raw material from one end of described tornadotron, the opposite direction that carrier gas enters from liquid phase antireflective coating raw material enters in described tornadotron, carrying described liquid phase antireflective coating raw material by described carrier gas rotates and throws to described tornadotron internal surface in order along the spiral of described swirler, and form thin liquid layer at described tornadotron internal surface, complete vaporescence by the thin liquid layer of described tornadotron heating evaporation;
In described steps A, its pressure of described pressurization is for being less than or equal to 1Mpa;
In described step B, speed when described liquid phase antireflective coating raw material is carried is 0.3-0.4m/s;
Described liquid phase antireflective coating raw material is tetraethyl orthosilicate or silicon tetrachloride, deionized water and catalyzer, and described gas raw material is air;
The vaporization temperature of described liquid phase antireflective coating raw material is 140 ° of C-150 ° C;
The consumption of described liquid phase antireflective coating raw material is 8.5Kg/hr-22 Kg/hr, described deionized water consumption is 0.5 Kg/hr-1.5 Kg/hr, described air flow quantity is 50 Kg/hr-200 Kg/hr, described catalyzer is triethyl phosphate, consumption is 0.6 Kg/hr-2.5 Kg/hr, and glass pull speed is 240 m/hr-480m/hr;
Described liquid phase antireflective coating raw material is tetraethyl orthosilicate or silicon tetrachloride, deionized water and catalyzer, described tetraethyl orthosilicate or the consumption of silicon tetrachloride are 8.5Kg/hr-22 Kg/hr, described deionized water consumption is 0.5 Kg/hr-1.5 Kg/hr, described catalyzer is triethyl phosphate, consumption is 0.6 Kg/hr-2.5 Kg/hr, described gas raw material is air, described air flow quantity is 50 Kg/hr-200 Kg/hr, described carrier gas is nitrogen, and its consumption is 80 Kg/hr-240 Kg/hr; Glass pull speed is 240 m/hr-480m/hr;
In described step C, the temperature of described hot glass ribbon is 600 ° of C-750 ° C;
In described step C, the temperature of described hot glass ribbon high temperature is 640 ° of C-680 ° C;
Described glass is the sheet glass that rolling process or horizontal sheet process manufacture.
The equipment that chemical vapor deposition method of the present invention is coated with glass antireflective coating can be directly be coated with glass antireflective coating on the high temp glass band of just moulding, without glass is heated again, thus can save energy, raise the efficiency, improve the quality of rete.
Chemical deposition of the present invention is coated with glass antireflective coating method, before glass ware forming after annealing, directly hot glass ribbon is coated with to antireflective coating, and without glass is heated again, tool has the following advantages:
1, film quality is outstanding.
The glass antireflective coating that the homogeneity of the glass antireflective coating that chemical deposition of the present invention is coated with is coated with considerably beyond existing off-line wet method, vacuum magnetic-control sputtering method, off-line CVD method, and do not produce edge fault;
The rete firmness being coated with is high: tensile strength reaches 83MPa; Hardness reaches Mohs' hardness 7.
Glass coating surface is without cavity, and stain resistance is strong;
Transmittance in use stability is high.
Table 1 is the antireflective coating film performance synopsis that the inventive method and off-line wet method, vacuum magnetic-control sputtering method, off-line CVD method are coated with.As can be seen from Table 1, the antireflective coating that adopts the inventive method to be coated with, its thickness evenness and printing opacity homogeneity are all better than above-mentioned three kinds of methods, and thickness evenness and transmittance homogeneity have all obtained beyond thought technique effect.
Table 1
2,energy consumption is low, and industrial scale is large.
Because the process that adopts the inventive method to be coated with glass antireflective coating completes before glass ware forming after annealing, when plated film, glass is still under the condition of high temperature, without again glass being heated, without vacuumizing for the equipment that is coated with antireflective coating, therefore compare and reduced work in-process baking operation with off-line wet method, significantly reduced power consumption; Compared with vacuum magnetic-control sputtering method, reduce and vacuumized energy consumption, significantly reduce power consumption.Compared with above-mentioned technique, the inventive method unit consumption of energy reduces more than 50% on year-on-year basis.
Table 2 is for adopting existing method to manufacture energy consumption and day output and employing the inventive method manufacture antireflective coating glass energy consumption and the day output contrast table of antireflective coating glass.In table 2, unit consumption of energy refers to the full process energy consumption of manufacturing every square metre of antireflective coating glass.
Table 2
3, anti-reflection rate increases obviously, and the performance of enterprises and social benefit are remarkable.
No matter be individual layer or double-layer reflection-decreasing film glass, it is 2.9%-3.0% that one side is coated with the anti-reflection rate of glass after antireflective coating, and after double coated antireflective coating, the anti-reflection rate of glass is 5.9%-6.0%.Testing data is as shown in table 3.
Table 3
Along with the reduction of PV cover-plate glass luminous reflectance factor, transmittance improves on year-on-year basis, the generating efficiency of solar cell also improves on year-on-year basis, so just can under the condition that obtains same generated energy, significantly reduce the usage quantity of cover-plate glass, silicon chip semi-conductor electricity generation material, battery base plate fluoroplastics material and EVA film, can save a large amount of starting material, the cost that reduces enterprise, not only can improve the profit of enterprise, and be conducive to effective utilization and the saving of the energy.Also can save a large amount of installing spaces simultaneously.
Accompanying drawing explanation
Fig. 1 is the device structure schematic diagram that chemical vapor deposition method of the present invention is coated with glass antireflective coating;
Fig. 2 is the plated film device example structure schematic diagram of the chemical vapor deposition method of the present invention equipment that is coated with glass antireflective coating;
Fig. 3 is the equipment thermostat example structure schematic diagram that chemical vapor deposition method of the present invention is coated with glass antireflective coating;
Fig. 4 is the vapourizing unit example structure schematic diagram that chemical vapor deposition method of the present invention is coated with glass antireflective coating;
Fig. 5 is that chemical vapor deposition method of the present invention is coated with glass antireflective coating technical process embodiment schematic diagram;
Fig. 6 is that glass antireflective coating membrane uniformity check point obtains schematic diagram.
Description of reference numerals
1-stablizes the defeated heat space 37-of beam 2-waste gas collecting pipe 3-antireflective coating raw material collecting pipe 4-suspender member 5-hanging beam 6-nozzle plate 7-spacer pieces 8-nozzle 9-constant temperature oil pipe 10-waste air passage 11-antireflective coating raw feed materials device 12-deep fat thermostat 13-dry air feeding mechanism 14-carrier gas feeding mechanism 15-emission-control equipment 16-power set 17-plated film device 18-glass ribbon 19-vapourizing unit 20-electrical control gear 21-oil heater 22-oil cooler 24-antireflective coating material feeding tube 25-upper cover 26-hot oil outlet 27-housing 28-carrier gas inlet pipe 29 lower cover 30-swirler 31-hot oil inlet 32-tornadotron 33-first orifice plate 34-the second orifice plate 35-vapour phase antireflective coating material outlet 36-check point 38-temperature sensing device.
Embodiment
Below in conjunction with drawings and Examples, the present invention is elaborated.
As shown in Figure 1, the equipment that the present invention is coated with glass antireflective coating comprises antireflective coating raw feed materials device 11, is provided with the vapourizing unit 19 of vaporizing chamber, carrier gas feeding mechanism 14, the plated film device 17 that is provided with nozzle 8 and waste air path 10, emission-control equipment 15 and provide MCC power set 16, the DCS electrical control gear 20 of power for said apparatus.Antireflective coating raw feed materials device 11, carrier gas feeding mechanism 14, dry air feeding mechanism 13 are communicated with the vaporizing chamber pipe of vapourizing unit 19 respectively, the vaporizing chamber of vapourizing unit 19 is communicated with nozzle 8 pipes of plated film device 17, the waste air path 10 pipe UNICOM of emission-control equipment 15 and plated film device 17.
As shown in Figures 2 and 3, in the present invention, plated film device 17 is preferably as follows structure: plated film device is by nozzle 8, waste air path 10 and nozzle stationary installation composition, nozzle 8 and waste air path 10 are staggered, can be being staggered of a nozzle 8 and one or two waste air path 10, also can be being staggered of multiple nozzles 8 and multiple waste air path 10s, a nozzle 8 is applicable to being coated with of single-glass antireflective coating with the plated film device of the staggered structure of one or two waste air path 10, multiple nozzles 8 are applicable to be coated with single or multiple lift antireflective coating with the staggered plated film device of multiple waste air path 10s, when use, pass into different raw materials at 8 li, different nozzle and just can produce the glass antireflective coating that multilayer film is constructed.In the present invention, nozzle 8 and waste air path 10 are formed by spacer pieces 7 intervals, can simplify like this plated film device 17 structures, reduce the cost of plated film device.Preferably in the both sides of nozzle 8, a waste air path 10 is set respectively, the complex waste gas of removing coating process formation that like this can be more balanced, can widen plated film district simultaneously, and raw material availability is increased substantially.Nozzle stationary installation is made up of nozzle plate 6 and the hanging beam 5 of static jet 8, nozzle plate 6 is connected with hanging beam 5 by suspender member 4, hanging beam 5 is fixed in frame, in order to increase the steadiness of plated film device 17, be provided with and stablize beam 1, it is arranged on the two ends of hanging beam 5, is fixedly connected with hanging beam 5, like this, plated film device 17 can be facilitated, be stably fixed in frame.
Connected the outlet pipe of nozzle 8 and vapourizing unit 19 by antireflective coating raw material collecting pipe 3, connected the inlet pipe of waste air path 10 and emission-control equipment 15 by waste gas collecting pipe 2.
For making nozzle 8 and waste air path 10 keep good thermostability, make at high temperature steady operation of plated film device 17, the equipment that the present invention is coated with glass antireflective coating is provided with deep fat thermostat 12, and constant temperature oil pipe 9 is set in spacer pieces.Deep fat thermostat 12 of the present invention is made up of oil heater 21, oil cooler 22 and the pipeline that connects the two, oil inlet end by constant temperature oil pipe 9 is connected with the oil export of oil heater 21, the oil outlet end of constant temperature oil pipe 9 is connected with the oil-in of oil cooler 22, the oil outlet of oil cooler 22 is communicated with the oil-in pipe of oil heater, and oil heater 21, oil cooler 22 are respectively arranged with temperature sensing device 38 and are electrically connected with electrical control gear 20.Thus, the constant temperature oil pipe 9 arranging in the spacer pieces 7 of oil heater, oil cooler and plated film device forms closed circuit oil circulating system.Adopt the deep fat thermostat 12 of this structure, when oil heater and oil cooler work, under the control of electrical control gear, can form interlocking working order, that is: oil heater work when system starts, when plated film, oil heater and oil cooler are worked jointly, reduce the electrisity consumption of oil heater when guaranteeing system constant temperature.
As shown in Figures 3 and 4, in equipment of the present invention, plated film device can arrange one, two or more also can be set, in the time need carrying out double coated antireflective coating to glass, need increase a plated film device 17 at the glass ribbon lower surface being positioned at before annealing furnace, be glass ribbon 18 lower surface plated films, thereby obtain two-sided antireflective coating glass.Two-sided antireflective coating glass has higher antireflective effect.As can be seen from Table 3, about the anti-reflection rate of two-sided antireflective coating glass is doubled than the anti-reflection rate of one side antireflective coating glass.
In order to improve the working efficiency of vapourizing unit in the present invention, make liquid phase antireflective coating feed vaporization obtain more thorough, the present invention has done further improvement to vapourizing unit 19, it comprises the housing 27 of the sealing being made up of upper cover 25 and lower cover 29 and cylindrical shell, in housing, be provided with by tornadotron 32, the vaporizing chamber that the first orifice plate 33 and the second orifice plate 34 form, the second orifice plate 34 is arranged on the bottom of tornadotron 32 and is fixedly connected with housing, the first orifice plate 33 is arranged on the top of tornadotron 32 and is fixedly connected with housing, tornadotron can be single, also can be multiple being arranged on side by side in vaporizing chamber, in tornadotron, be provided with swirler, swirler be shaped as a screw shaft, this screw shaft can be tubular shaft, also can be solid shaft, it can be multi-head spiral, also can be single head spiral, it in tornadotron with the equidirectional setting of axis of tornadotron, preferably and the axis coaxle setting of tornadotron.Hot oil inlet 31 and hot oil outlet 26 are set on housing 27, and hot oil inlet 31 and hot oil outlet 26 are respectively with the oil export of deep fat thermostat 12 with oil inlet is corresponding is connected.Defeated heat space 36 for constant temp. heating oil flow is set between tornadotron 32 and housing 27, flows to hot oil outlet 26 for constant temperature deep fat from hot oil inlet 31, tornadotron is carried out to thermostatically heating.In one end of tornadotron 32, antireflective coating material feeding tube 24 is set, at its other end, carrier gas inlet pipe 28 is set, the object arranging is like this that the opposite direction that the antireflective coating raw material of liquid phase enters from carrier gas is flowed in tornadotron 32, to obtain best mass-and heat-transfer effect.Vapour phase antireflective coating material outlet 35 is preferably disposed on the upper end of housing.On the first orifice plate and the second orifice plate, be provided with through hole, antireflective coating material feeding tube, vapour phase antireflective coating material outlet 35 and carrier gas inlet pipe 28 are fixedly connected with tornadotron 32 by the corresponding through hole arranging on the first orifice plate 33 or the second orifice plate 34 respectively.
The principle of work of this vaporizer is as follows: carrier gas enters in tornadotron 32 from bottom to top or from top to bottom, spiral along swirler 30 rotates to form rotation carrier gas in order, liquid phase antireflective coating raw material enters in tornadotron 32 from the opposite direction of carrier gas, rotated immediately carrier gas and carry and throw to tornadotron 32 internal surfaces, and formed thin liquid layer at tornadotron 32 internal surfaces.Be positioned at the constant temperature deep fat of tornadotron 32 outsides by tornadotron 32 thermostatically heating, in the time that the temperature of liquid phase antireflective coating raw material is heated above the boiling point of itself, liquid phase antireflective coating raw material i.e. even, rapid evaporation, and evenly mix with carrier gas 23, the air-flow that forming component is even, velocity of evaporation is stable, complete the vaporescence of liquid phase antireflective coating raw material, through vaporization antireflective coating raw material from liquid phase antireflective coating raw material enter tornadotron equidirectional go out tornadotron.
Adopt the vapourizing unit 19 of structure of the present invention, liquid phase antireflective coating raw materials evaporate is stable, and vaporization efficiency is high, has improved more than 40% than the vapourizing unit vaporization efficiency of existing same evaporation and heat-exchange area, can miniaturization material carburetor; Saving non-ferrous metal consumes; Reduce manufacturing cost.
Below to carry out the description of detail as the method that example is coated with glass antireflective coating to the present invention producing on photovoltaic flat glass production line as photovoltaic sheet glass is coated with antireflective coating:
As shown in Figure 5, for adopting chemical deposition of the present invention to be coated with the technique of the method manufacture photovoltaic sheet glass antireflective coating of glass antireflective coating, it is before the fusing compression moulding of molten cellar for storing things obtains annealing after hot glass ribbon, to hot glass ribbon, to be coated with glass antireflective coating with chemical deposition at frit on photovoltaic glass production line.In this process raw material feeding system in glass making, found, moulding and annealing all can adopt existing photovoltaic flat glass production process, the process that is coated with glass antireflective coating comprises the steps:
A, join, feeding: various antireflective coating raw materials are provided and delivered into vapourizing unit in proportion via after antireflective coating raw feed materials device pressurization;
B, liquid phase antireflective coating feed vaporization: liquid phase antireflective coating raw material forms vapour phase antireflective coating raw material by vapourizing unit vaporization;
C, deposition: vapour phase antireflective coating raw material is by the nozzle spray ribbon of hot glass surface of plated film device, in hot glass ribbon surface flow, in antireflective coating raw material flow process, under hot glass ribbon high temperature, there is vapour pyrolysis chemical reaction in antireflective coating raw material, the oxide products of reaction is connected with the crystalline network ordered arrangement of hot glass surface, form polycrystalline state thin-film body, do not have the residual product of deposition to flow to waste air path 10, and extracted out by emission-control equipment 15 by waste gas collecting pipe 2.In said process, in the slit through the glass antireflective coating raw material of rapid heating between plated film device 17 and hot glass ribbon 18 surfaces, there is decomposition reaction and will decompose the oxidate producing to form glass antireflective coating rete to hot glass ribbon surface.
In the above-mentioned process that is coated with glass antireflective coating, liquid phase antireflective coating raw material is preferably tetraethyl orthosilicate or silicon tetrachloride, gas raw material is dry air, liquid phase antireflective coating raw material flow rate is 0.3-0.4m/s, pressure is for being less than or equal to 1Mpa, and liquid phase antireflective coating feed vaporization temperature is 140-150 ° of C; In plated film district, glass temperature is 600 ° of C-750 ° C, and plated film district glass temperature is controlled with internal water temperature and the flow of glass ribbon snub pulley after cotton ginning.
For making liquid phase antireflective coating feed vaporization more thorough, in vaporescence, with carrier gas, liquid phase antireflective coating raw material is carried, the opposite direction that carrier gas is entered by liquid phase antireflective coating raw material enters in tornadotron, carrying liquid phase antireflective coating raw material by carrier gas rotates and throws to tornadotron 32 internal surfaces in order along the spiral of swirler, and form thin liquid layer at tornadotron 32 internal surfaces, heat vaporescence by tornadotron 32.Carrier gas can be the one in the rare gas elementes such as hydrogen, helium, nitrogen, argon or carbonic acid gas, and preferred nitrogen is as carrier gas.Carrier gas and air all have the effect that regulates air speed.
Adopt the inventive method to be coated with glass antireflective coating, it is after glass ware forming, before annealing, the glass antireflective coating raw material accurately mixing is ejected into hot glass ribbon surface by CVD plated film device at glass ribbon during in the condition of high temperature, immediately there is the reactant of chemical reaction formation aerosol state in antireflective coating raw material heat, reactant Direct precipitation is on fresh hot glass ribbon surface, spatial grid structure chemical bonds with hot glass surface, form stable chemical performance on hot glass ribbon surface, bonding strength is superpower, the crystalline structure film that molecular arrangement is orderly, due in this process, antireflective coating raw material is met thermogenetic chemical reaction and is formed the reactant of aerosol state and close and form chemical bonds community with the spatial grid structure of hot glass surface, therefore rete stability is good and stability is high, crystalline structure sequence is good, uniform crystal particles is good, surface does not form the organic substance decomposing hole staying of vaporizing, light scattering property is good.
In order to carry out innoxious production, the not settling that reaction produces is extracted out by emission-control equipment, further do harmless treatment, realize the green production of system, described emission-control equipment is connected to form successively by waste gas combustion furnace, fly-ash separator and washing tower, by induced draft fan, the waste gas of washing tower washing is discharged in atmosphere.
The plating method of glass antireflective coating of the present invention is applicable to sheet glass and is coated with online antireflective coating, can in horizontal rolling process technique, be coated with online antireflective coating, also can be used for other horizontal withdrawal method Improving Glass Manufacturing Processes and is coated with online antireflective coating.
Be elaborated as example to be coated with antireflective coating at photovoltaic ultrawhite cotton ginning glass surface below.
Embodiment 1
Glass ribbon width 2400mm, glass ribbon pull speed is 280m/hr,
The frit of preparation obtains the high-viscosity glass liquid of 1100 ° of C after fusing, clarification, and high-viscosity glass liquid has the texturing steel alloy pair roller of water cooling plant to be rolled moulding through one group of inside, thereby obtains the high temp glass band 18 of required thickness.The glass ribbon of moulding has in inside on the steel alloy carrying roller of water-cooled and is quickly cooled to 665 ° of C, the equipment that is coated with glass antireflective coating with chemical vapor deposition method carries out plated film, antireflective coating main raw material used is tetraethyl orthosilicate, deionized water and air, and tetraethyl orthosilicate consumption is 8.5Kg/hr; Deionized water consumption 0.5Kg/hr; Air flow quantity is 58Kg/hr; Adopt triethyl phosphate as catalyzer, consumption is 0.9Kg/hr; Nitrogen is as carrier gas, flow 97Kg/hr.The detailed process that is coated with antireflective coating is: tetraethyl orthosilicate, deionized water and catalyzer are respectively through feed device A, B, after C pressurization, send in proportion in the tornadotron 32 of vapourizing unit, the opposite direction that the nitrogen that carrier gas feeding mechanism 14 is supplied and air enter tornadotron from liquid phase antireflective coating raw material enters in tornadotron, and along the spiral of swirler 30 in order rotation throw to tornadotron 32 internal surfaces and form thin liquid layer, thin liquid layer is heated by the tornadotron 32 that is heated to 140 ° of C by thermostatical oil, obtain vapour phase antireflective coating raw material and mix with carrier gas through carburation by evaporation, the equidirectional that vapour phase antireflective coating raw material enters from liquid phase antireflective coating raw material flows out tornadotron, the air of drying and vapour phase antireflective coating raw material are entered into the nozzle 8 of plated film device by antireflective coating raw material collecting pipe, spray to by nozzle 8 the hot glass ribbon surface that temperature is 665 ° of C, under hot glass ribbon high temperature, there is vapour pyrolysis chemical reaction in antireflective coating raw material, the oxide products of reaction is connected with the crystalline network ordered arrangement of hot glass surface, formation of deposits polycrystalline state thin-film body, do not have the residual product of deposition to flow to waste air path 10, and extracted out by emission-control equipment 15 by waste gas collecting pipe 2, complete the process that is coated with of glass antireflective coating, it is cooling that the glass ribbon that has plated antireflective coating enters annealing furnace, cut on request the size needing, packing makes finished product anti-reflection coated glass afterwards.
Glass ribbon width is 2400mm, and pull speed is 255m/hr, 680 ° of C of plated film district glass ribbon temperature, and antireflective chemical feedstocks mainly uses silicon tetrachloride, consumption 12Kg/hr; Deionized water consumption 0.72Kg/hr; Catalyzer triethyl phosphate consumption is 0.67Kg/hr; Air flow quantity 78Kg/hr; Nitrogen is as carrier gas, flow 121Kg/hr, and air is directly entered in plated film device nozzle 32 by dry air feeding mechanism.
All the other are with embodiment 1.
Embodiment 3
Glass ribbon width is 2400mm, and pull speed is 245m/hr, 640 ° of C of plated film district glass ribbon temperature.Antireflective coating raw material uses tetraethyl orthosilicate, consumption 7.6Kg/hr; Deionized water consumption 0.5Kg/hr; Catalyzer triethyl phosphate consumption 0.7Kg/hr; Air flow quantity 70Kg/hr; Nitrogen is as carrier gas, and flow is 89Kg/hr, equidirectional enter tornadotron 32 in of air from entering with liquid phase antireflective coating raw material.
All the other are with embodiment 1.
Embodiment 4
Glass ribbon width is 3300mm, and pull speed is 480m/hr, 670 ° of C of plated film district glass ribbon temperature.Antireflective coating chemical feedstocks uses tetraethyl orthosilicate, consumption 22Kg/hr; Deionized water consumption 1.5Kg/hr; Catalyzer triethyl phosphate consumption 2.1Kg/hr; Air flow quantity 200Kg/hr; Nitrogen is as carrier gas, flow 240Kg/hr, and air passes into hot glass ribbon surface, plated film district.
All the other are with embodiment 1.
Table 4 is each embodiment parameter list.In table, not shown unit is (Kg/hr)
The antireflective coating measured result that online CVD technique single-surface single-layer is coated with is as table 5:
Table 5
| ? | Do not have plated film front glass transmitance (%) | Glass transmitance (%) after plated film | Anti-reflection rate (%) | Thicknesses of layers (nm) | Thicknesses of layers ununiformity (%) | Transmittance ununiformity (%) |
| Embodiment 1 | 91.9 | 94.9 | 3.0 | 126 | 2 | 0.2 |
| |
91.85 | 94.78 | 2.93 | 124 | 1.8 | 0.17 |
| Embodiment 3 | 91.86 | 94.76 | 2.90 | 119 | 1.62 | 0.19 |
| Embodiment 4 | 90.53 | 93.49 | 2.96 | 123 | 1.7 | 0.15 |
The quality product of online CVD explained hereafter photovoltaic anti-reflection film glass is affected by kinds of processes condition, and the processing condition that wherein have the greatest impact are plated film district temperature.Data in table 6 are at same antireflective coating raw material flow rate, subtract the contrast of penetrating prepared glass antireflective coating rete parameters at film material flow, antireflective coating material temperature, appointed condition of the same race, the same glass speed of travel, different plated film district temperature.
Table 6
As can be drawn from Table 6 to draw a conclusion:
Film deposition speed raises and accelerates with temperature, illustrates that raw material pyrolysis rate improves and accelerates with temperature, accelerates sedimentation velocity.
Rete crystal grain diameter raises and diminishes with temperature.Be illustrated as brilliant speed and accelerate, crystal seed quantity gathers way faster than crystalline growth velocity.This is for holding crystalline structure, size and then control film performance extremely being had to directive significance.
Raw material availability raises and improves with temperature.Thereby under the prerequisite that therefore should can satisfy the demand at film quality parameter, suitably improve plated film district temperature and improve reaction zone temperature, to improve the utilization ratio of raw material, thereby reduce costs.
Crystalline film sedimentation velocity is faster, and rete firmness can decrease, and not quite all can meet industrial needs but change.
In test of the present invention, test set used is as follows:
Transmittance test set: Japanese Shimadzu UV-3150 type spectrophotometer;
Thicknesses of layers test set: GAERTNER Scientific Co. L116SF ellipsometer;
Washability testing installation: Feicheng, the Shandong Province QFS of Jia Beier Instrument Ltd. washability determinator;
Resistance to chemical attack experimental installation: the Central Asia, the Wuxi YWX/Q-016 of environmental test equipment company limited type salt mist tester;
Ultraviolet resistance testing installation: the Shanghai SHA-PV-SM of Shang Qun Electronic Science and Technology Co., Ltd. photovoltaic module ultraviolet pretreatment testing machine;
Pencil hardness test instrument: manufacture 1000g pencil hardometer according to GB/T6739-1996 standard design.
Table 7: the antireflective coating technical data that the inventive method is coated with and national standard contrast table
Experimental value (%)=(T
before eff experiment-T
after eff test)/T
before eff experiment
Can be as drawn a conclusion from above data: the antireflective coating of online CVD technique manufacture belongs to rower A level product, and above important detection index is ideal.
Membrane uniformity adopts following detection method:
1 meter on glass in the length of side, draw diagonal lines and obtain central point, draw circle using 1/4 of catercorner length as radius, the intersection point crossing with the diagonal lines of mother glass and the equal separated time of opposite side and the mid point of sample totally 9 points as the check point of antireflective coating sample, rete ununiformity=(detected value maximum difference/each point averages of 9 points) * 100%.
Claims (19)
1. a chemical vapor deposition method is coated with the equipment of glass antireflective coating, it is characterized in that, comprise antireflective coating raw feed materials device (11), be provided with the antireflective coating liquid phase feed vapourizing unit (19) of vaporizing chamber, emission-control equipment (15), be provided with plated film device (17) and the thermostat of nozzle (8) and waste air passage (10), described antireflective coating raw feed materials device (11) is communicated with the vaporizing chamber pipe of described vapourizing unit (19), described vaporizing chamber is communicated with nozzle (8) pipe of described plated film device (17), described waste air passage (10) is communicated with described emission-control equipment (15) pipe,
Described vapourizing unit (19) also comprises housing (27) and the carrier gas feeding mechanism (14) of sealing, described vaporizing chamber is tornadotron (32), it is fixedly installed in described housing (27), described tornadotron (32) is heated by described thermostat, one end of described tornadotron (32) is connected with carrier gas inlet pipe (28), the other end of described tornadotron (32) is connected with liquid phase feed feed-pipe (24), vaporization raw material discharge nozzle (35) is connected with described tornadotron, in described tornadotron (32), be provided with swirler (30), described swirler (30) is screw shaft, the axis of described screw shaft and the axis of described tornadotron be arranged in parallel,
Described nozzle (8) is communicated with described vaporizing chamber pipe by antireflective coating raw material collecting pipe (3), described waste air passage (10) is communicated with emission-control equipment (15) pipe by waste gas collecting pipe (2), described nozzle (8) and waste air passage (10) are formed by spacer pieces (7) interval, and described nozzle (8) and waste air passage (10) are parallel to be crisscross arranged.
2. chemical vapor deposition method as claimed in claim 1 is coated with the equipment of glass antireflective coating, it is characterized in that, described thermostat is deep fat thermostat (12), between described housing (27) and described tornadotron (32), be provided with the defeated heat space (36) for deep fat circulation, the hot oil outlet of the hot oil inlet (31) of described housing (27) by setting on it and hot oil outlet (26) and described deep fat thermostat and hot oil inlet is corresponding is connected.
3. chemical vapor deposition method as claimed in claim 1 is coated with the equipment of glass antireflective coating, it is characterized in that, described thermostat is deep fat thermostat (12), on described spacer pieces (7), be provided with constant temperature oil pipe (9), the oil-in of constant temperature oil pipe (9) and oil outlet thereof are communicated with oil outlet and the oil-in respective tube thereof of described deep fat thermostat (12) respectively.
4. chemical vapor deposition method as claimed in claim 1 is coated with the equipment of glass antireflective coating, it is characterized in that, the both sides of described each nozzle (8) arrange respectively the described exhaust steam passage of a row (10).
5. chemical vapor deposition method as claimed in claim 1 is coated with the equipment of glass antireflective coating, it is characterized in that, described plated film device is provided with nozzle stationary installation, described nozzle stationary installation is made up of nozzle plate (6) and hanging beam (5), described nozzle plate (6) is fixedly connected with described hanging beam (5) by suspender member (4), and described spacer pieces (7) is fixedly connected with described nozzle plate (6).
6. chemical vapor deposition method as claimed in claim 5 is coated with the equipment of glass antireflective coating, it is characterized in that, go up and nozzle (8) and the corresponding through hole that is provided with of waste air passage (10) at described nozzle plate (6), described nozzle (8) is connected with described antireflective coating raw material collecting pipe (3) by described through hole, and described waste air passage (10) is connected with described waste gas collecting pipe (2) by described through hole.
7. chemical vapor deposition method is coated with the equipment of glass antireflective coating as claimed in claim 2 or claim 3, it is characterized in that, described deep fat thermostat is composed in series by oil heater (21), oil cooler (22) and the pipeline that connects the two, the oil export of described oil heater (21) is the oil export of deep fat thermostat, the oil-in of oil cooler (22) is the oil inlet of permanent oily deep fat device, and oil heater (21), oil cooler (22) are respectively arranged with temperature sensing device and are electrically connected with electrical control gear.
8. chemical vapor deposition method is coated with a method for glass antireflective coating, it is characterized in that: adopt one of the every described chemical vapor deposition method of claim 1-7 to be coated with the equipment of glass antireflective coating, after glass ware forming, before annealing, be coated with glass antireflective coating.
9. chemical vapor deposition method as claimed in claim 8 is coated with the method for glass antireflective coating, it is characterized in that, the described glass antireflective coating that is coated with comprises the steps:
A, join, feeding: antireflective coating raw material in proportion, enter vapourizing unit after transferpump pressurization;
B, liquid phase antireflective coating feed vaporization: liquid phase reflectance coating raw material is vaporized and formed vapour phase antireflective coating raw material by vapourizing unit;
C, deposition: vapour phase antireflective coating raw material enters plated film device, sprayed to the hot glass ribbon surface of moulding by nozzle (8), vapour phase antireflective coating raw material and gas raw material are deposited on hot glass ribbon surface and form glass antireflective coating rete after hot glass ribbon (18) fast heating at high temperature decomposes, and complete being coated with of glass surface antireflection film.
10. chemical vapor deposition method as claimed in claim 9 is coated with the method for glass antireflective coating, it is characterized in that, in described step B, adopt vapourizing unit as claimed in claim 2 (19), be delivered into described vaporizing chamber by liquid phase antireflective coating raw material from one end of described tornadotron (32), the opposite direction that carrier gas (23) enters from liquid phase antireflective coating raw material enters in described tornadotron (32), carrying described liquid phase antireflective coating raw material by described carrier gas (23) rotates and throws to described tornadotron (32) internal surface in order along the spiral of described swirler (30), and form thin liquid layer at described tornadotron (32) internal surface, complete vaporescence by the thin liquid layer of described tornadotron (32) heating evaporation.
11. chemical vapor deposition methods as described in claim 9 or 10 are coated with the method for glass antireflective coating, it is characterized in that, in described steps A, its pressure of described pressurization is for being less than or equal to 1Mpa.
12. chemical vapor deposition methods as described in claim 9 or 10 are coated with the method for glass antireflective coating, it is characterized in that, in described step B, speed when described liquid phase antireflective coating raw material is carried is 0.3-0.4m/s.
13. chemical vapor deposition methods as described in claim 9 or 10 are coated with the method for glass antireflective coating, it is characterized in that, described liquid phase antireflective coating raw material is tetraethyl orthosilicate or silicon tetrachloride, deionized water and catalyzer, and described gas raw material is air.
14. chemical vapor deposition methods as described in claim 9 or 10 are coated with the method for glass antireflective coating, it is characterized in that, the vaporization temperature of described liquid phase antireflective coating raw material is 140 ° of C-150 ° C.
15. chemical vapor deposition methods as claimed in claim 14 are coated with the method for glass antireflective coating, it is characterized in that, the consumption of described liquid phase antireflective coating raw material is 8.5Kg/hr-22 Kg/hr, described deionized water consumption is 0.5 Kg/hr-1.5 Kg/hr, described air flow quantity is 50 Kg/hr-200 Kg/hr, described catalyzer is triethyl phosphate, and consumption is 0.6 Kg/hr-2.5 Kg/hr, and glass pull speed is 240 m/hr-480m/hr.
16. chemical vapor deposition methods as claimed in claim 10 are coated with the method for glass antireflective coating, it is characterized in that, described liquid phase antireflective coating raw material is tetraethyl orthosilicate or silicon tetrachloride, deionized water and catalyzer, described tetraethyl orthosilicate or the consumption of silicon tetrachloride are 8.5Kg/hr-22 Kg/hr, described deionized water consumption is 0.5 Kg/hr-1.5 Kg/hr, described catalyzer is triethyl phosphate, consumption is 0.6 Kg/hr-2.5 Kg/hr, described gas raw material is air, described air flow quantity is 50 Kg/hr-200 Kg/hr, described carrier gas is nitrogen, its consumption is 80 Kg/hr-240 Kg/hr, glass pull speed is 240 m/hr-480m/hr.
17. chemical vapor deposition methods as claimed in claim 10 are coated with the method for glass antireflective coating, it is characterized in that, in described step C, the temperature of described hot glass ribbon is 600 ° of C-750 ° C.
18. chemical vapor deposition methods as described in claim 9 or 10 are coated with the method for glass antireflective coating, it is characterized in that, in described step C, the temperature of described hot glass ribbon high temperature is 640 ° of C-680 ° C.
19. chemical vapor deposition methods as described in claim 9 or 10 are coated with the method for glass antireflective coating, it is characterized in that, described glass is the sheet glass that rolling process or horizontal sheet process manufacture.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4394401A (en) * | 1980-08-08 | 1983-07-19 | Fujitsu Limited | Method of plasma enhanced chemical vapor deposition of phosphosilicate glass film |
| US5090985A (en) * | 1989-10-17 | 1992-02-25 | Libbey-Owens-Ford Co. | Method for preparing vaporized reactants for chemical vapor deposition |
| CN1228067A (en) * | 1996-08-13 | 1999-09-08 | 皮尔金顿公共有限公司 | Method of depositing tin oxide and titanium oxide coating on flat glass and resulting coated glass |
| CN201056539Y (en) * | 2007-06-22 | 2008-05-07 | 王百新 | Improved plated film producing device for macrotype sheet glass |
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| US4853257A (en) * | 1987-09-30 | 1989-08-01 | Ppg Industries, Inc. | Chemical vapor deposition of tin oxide on float glass in the tin bath |
| CN1093067A (en) * | 1993-04-02 | 1994-10-05 | 山东大学 | The preparation method of glass transparent insulating film and nozzle specially used |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4394401A (en) * | 1980-08-08 | 1983-07-19 | Fujitsu Limited | Method of plasma enhanced chemical vapor deposition of phosphosilicate glass film |
| US5090985A (en) * | 1989-10-17 | 1992-02-25 | Libbey-Owens-Ford Co. | Method for preparing vaporized reactants for chemical vapor deposition |
| CN1228067A (en) * | 1996-08-13 | 1999-09-08 | 皮尔金顿公共有限公司 | Method of depositing tin oxide and titanium oxide coating on flat glass and resulting coated glass |
| CN201056539Y (en) * | 2007-06-22 | 2008-05-07 | 王百新 | Improved plated film producing device for macrotype sheet glass |
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