CN102584019A - 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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- CN102584019A CN102584019A CN2012100213206A CN201210021320A CN102584019A CN 102584019 A CN102584019 A CN 102584019A CN 2012100213206 A CN2012100213206 A CN 2012100213206A CN 201210021320 A CN201210021320 A CN 201210021320A CN 102584019 A CN102584019 A CN 102584019A
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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 the glass antireflective coating, particularly relate to the online Apparatus and method for that is coated with the glass antireflective coating of chemical vapor deposition method.
Background technology
Antireflective coating is claimed anti-reflection film again, and its major function is the reflected light that reduces or eliminates 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 the upper strata and receive light cover-plate glass material, it is to cover solar cell surface to allow sunshine to get into the ultra-clear glasses cover plate that sensitive cell generating semiconductor material can be protected sensitive cell itself again.As everyone knows, light wave can produce refraction and reflex when the dielectric surface through different refractivity, and for solar cell, luminous reflectance is disadvantageous, can make luminous energy scatter and disappear and can not fully be utilized because of reflecting.Through calculating and measuring, the luminous reflectance factor during light wave process cover-plate glass list surface is that 4%, two surface is exactly 8%.At present glass production enterprise effective feed glass raw material iron-holder makes that the absorptivity of photovoltaic cell cover-plate glass is more much lower with glass than common building, and light transmission rate is near 92%.Therefore the luminous reflectance factoies that reduce the two surfaces of cover-plate glass be improve solar-energy photo-voltaic cell just PV cell power generation efficient important by way of.Experiment shows that the raising of the minimizing of glass surface luminous reflectance factor and PV battery unit surface generated energy is proportional.Glass industry generally is employed in glass surface and is coated with antireflective coating and reduces glass surface to the reflection of light rate.
The plating method of the photovoltaic glass antireflective coating of widespread use at present has three kinds of off-line vacuum magnetic-control sputtering methods, normal temperature wet processing, off-line CVD technology, and they have following characteristics respectively:
Off-line vacuum magnetic-control sputtering method is coated with the glass antireflective coating: in the space of high vacuum; Send into the glass of wash clean in the middle of the dc high voltage electric field; Vakuumkammer feeds a spot of Ar gas, and MOX of selecting on request or nonmetal oxide material are as cathode targets, and high-voltage electric field is with ar atmo ionization and high-speed impact cathode targets; Target material can be launched glass surface at a high speed and combines with the glass surface molecular linkage with molecularity, has so just formed coated glass.If the target material specific refractory power is proper and film thickness is suitable, just can obtain anti-reflective effect.
This technology can be made the MULTILAYER COMPOSITE antireflection film, and shortcoming is: the rete firmness is low, and reflectance coating is difficult to keep the antireflective effect for a long time outdoor; Facility investment is big; Manufacturing cost is high.
Off-line wet production anti-reflection film glass: the off-line wet process technique is divided into three kinds of gel methods, spraying method, roll printing method.
Gel method is exactly to immerse the glass of wash clean in the antireflective coating raw material coagulant liquid, through oven dry, tempering two procedures, forms two-sided antireflective coating at glass surface then;
Spraying method is exactly evenly to be ejected into the glass surface of wash clean to the antireflective coating material solution through spray gun, then through oven dry, tempering two procedures, forms antireflection film at glass surface;
Roll printing method is exactly through accurate rubber roll the antireflective coating material solution evenly to be coated to the glass surface of wash clean, thereby makes glass possess antireflective effect through oven dry, tempering two procedures at glass surface formation antireflection film then.
More than three kinds of technologies all be under normal temperature wet method condition, to accomplish, present employed antireflective coating raw material all is an organosilicon material basically, organism decomposes in the manufacturing processed; Make thin-film material form the molecular level hole, the product of therefore producing is a porous silicon oxide membrane, and film firmness, intensity, stability are all very undesirable; Influenced by the microcosmic vesicular structure, during product export anti-reflective effect still can, but after processing the PV battery component; Than being easier to receive the environmental pollution influence; A large amount of dirts get into the microcosmic hole, the light transmission rate of cover-plate glass is descended, even can make the unit surface generated energy of this subassembly product be lower than the not PV battery component of plated film.The used anti-reflection film solution of above-mentioned in addition three kinds of technologies all adopts the mixture of organosilicon, ethanol, ammoniacal liquor etc., and environment is caused certain pollution.Course of processing energy consumption is higher relatively.
Off-line CVD technology: off-line CVD explained hereafter photovoltaic anti-reflection film glass is the technology that developed recently gets up, and this technology has effectively been improved the rete defective of the product existence of vacuum magnetic-control sputtering method and wet method coating process.This technology be glass processing enterprise in the cold working process--a cover off-line CVD coating film production line has been installed between the annealing furnace; It is usually by reheat--CVD plated film--, and annealing device is formed again; Be that ultrawhite cotton ginning glass gets into off-line CVD coating film production line through cutting, edging, cleaning, dry back; Glass is reheated 650 ° of C, and glass passes through from CVD plated film device below afterwards, and 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, forms certain thickness antireflective coated glass product.
This production technique has following weak point: the one, and energy input is bigger, 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 receives glass quality to influence greatly instability.Frit from former factory dispatch from the factory the back surface can receive pollution in various degree, like the isolated material performance to the influence of original sheet glass quality, the influence of glass storage environment, the influence of glass storage time length etc.The bonding strength of glass and plated film rete can descend and the quality instability.The 3rd, the glass coating process can form the thin partially defective of thickness, the colour-difference that with the naked eye just can see this technology limit portion and middle portion in scale glass edge portion.This defective is that technology is limit inevitably; Because being a slice a slice when getting into off-line coated device, passes through below the plated film device scale original sheet glass; And the glass both sides also can form gap space between sheet and the sheet and in the glass run process; The irregular variation of coating raw material flow can be caused in these glass slits, causes glass edge portion rete attenuate.To impact scope excessive if control improper meeting, thereby produce a large amount of waste products.The new photovoltaic anti-reflection film glass standard of formulating of country allows limit portion incidence less than 7mm.
Summary of the invention
It is big to the objective of the invention is when being coated with the glass antireflective coating in the prior art energy consumption; Scale glass edge portion thickness is as thin as the deficiency that makes the 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 the plated film device and the thermostat of nozzle and waste discharge gas passage; Said antireflective coating raw feed materials device is communicated with the vaporizing chamber pipe of said vapourizing unit; Described vaporizing chamber is communicated with the blast tube of said plated film device, and said waste discharge gas passage is communicated with said emission-control equipment pipe;
Said vapourizing unit also comprises the housing of sealing and carries the vapour feeding mechanism; Said vaporizing chamber is a tornadotron, and it is fixedly installed in the said housing, and said tornadotron is heated by said thermostat; One end of said tornadotron is connected with a year vapour steam inlet pipe; The other end of said tornadotron is connected with the liquid phase feed feed-pipe, and vaporization raw material extraction line is connected with said tornadotron, in said tornadotron, is provided with swirler-; Said swirler-is a screw shaft, the parallel axes setting of the axis of said screw shaft and said tornadotron;
Said thermostat is the deep fat thermostat; Be provided with the defeated heat space of heat supply oil circulation between said housing and said tornadotron, the hot oil outlet of hot oil inlet and the hot oil outlet of said housing through setting it on and said deep fat thermostat and hot oil inlet is corresponding is connected;
Said nozzle is communicated with said vaporizing chamber pipe through antireflective coating raw material collecting pipe; Said waste discharge gas passage is communicated with the emission-control equipment pipe through the waste gas collecting pipe; Described nozzle and waste discharge gas passage are formed by spacer pieces at interval, and described nozzle and waste discharge gas channel parallel are crisscross arranged;
Said thermostat is the deep fat thermostat, and described spacer pieces is provided with the constant temperature oil pipe, and the oil-in of constant temperature oil pipe and oil outlet thereof are communicated with the oil outlet and the oil-in respective tube thereof of described deep fat thermostat respectively;
The both sides of said each nozzle are provided with a waste discharge gas passage respectively;
Said plated film device is provided with the nozzle stationary installation, and said nozzle stationary installation is by nozzle plate and hang beam and form, and said nozzle plate is fixedly connected with the said beam of hanging through suspender member, and said spacer pieces is fixedly connected with said nozzle plate;
With nozzle and the corresponding through hole that is provided with of waste discharge gas passage, said nozzle is connected with said antireflective coating raw material collecting pipe through said through hole on described nozzle plate, and said waste discharge gas passage is connected with said waste gas collecting pipe through said 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 said 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.
A kind of chemical vapor deposition method is coated with the method for glass antireflective coating, behind glass ware forming, annealing before be coated with the glass antireflective coating;
The described glass antireflective coating that is coated with comprises the steps:
A, join, feeding: the antireflective coating raw material in proportion, through transferpump pressurization back entering vapourizing unit;
B, liquid phase antireflective coating feed vaporization: liquid phase reflectance coating raw material is vaporized by vapourizing unit and is formed vapour phase antireflective coating raw material;
C, deposition: vapour phase antireflective coating raw material gets into the plated film device; Spray 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 high temperature rapid heating is decomposed, accomplish being coated with of glass surface antireflection film;
In described step B; Adopt described vapourizing unit; Be delivered into said vaporizing chamber by liquid phase antireflective coating raw material from an end of said tornadotron, carrier gas enters in the said tornadotron from the opposite direction that liquid phase antireflective coating raw material gets into, by said carrier gas carry said liquid phase antireflective coating raw material along the spiral of said swirler-in order rotation throw to said tornadotron internal surface; And form thin liquid layer at said tornadotron internal surface, accomplish vaporescence by the thin liquid layer of said tornadotron heating evaporation;
In the described steps A, its pressure of described pressurization is smaller or equal to 1Mpa;
Among the described step B, the speed when said liquid phase antireflective coating raw material is carried is 0.3-0.4m/s;
Said liquid phase antireflective coating raw material is tetraethyl orthosilicate or silicon tetrachloride, deionized water and catalyzer, and described gas raw material is an air;
The vaporization temperature of said 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 a triethyl phosphate, and consumption is 0.6 Kg/hr-2.5 Kg/hr, and the glass pull speed is 240 m/hr-480m/hr;
Said liquid phase antireflective coating raw material is tetraethyl orthosilicate or silicon tetrachloride, deionized water and catalyzer; The consumption of described tetraethyl orthosilicate or silicon tetrachloride is 8.5Kg/hr-22 Kg/hr; Described deionized water consumption is 0.5 Kg/hr-1.5 Kg/hr, and described catalyzer is a triethyl phosphate, and consumption is 0.6 Kg/hr-2.5 Kg/hr; Described gas raw material is an air; Described air flow quantity is 50 Kg/hr-200 Kg/hr, and described carrier gas is a nitrogen, and its consumption is 80 Kg/hr-240 Kg/hr; The glass pull speed is 240 m/hr-480m/hr;
Among the described step C, the temperature of described hot glass ribbon is 600 ° of C-750 ° C;
Among the described step C, described hot glass ribbon pyritous temperature is 640 ° of C-680 ° C;
Described glass is the sheet glass that rolling process or horizontal sheet process make.
The equipment that chemical vapor deposition method of the present invention is coated with the glass antireflective coating can directly be coated with the glass antireflective coating on the high temp glass band of moulding just, need not glass is heated once more, so but save energy is raised the efficiency the quality of raising rete.
Chemical deposition of the present invention is coated with glass antireflective coating method, before the glass ware forming after annealing, directly hot glass ribbon is coated with antireflective coating, need not glass is heated once more, has following advantage:
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 that is coated with is high: tensile strength reaches 83MPa; Hardness reaches Mohs' hardness 7.
The glass coating surface does not have the 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.From table 1, can find out, the antireflective coating that adopts the inventive method to be coated with, its thickness evenness and printing opacity homogeneity all are 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 big.
Because the process that adopts the inventive method to be coated with the glass antireflective coating is accomplished before the glass ware forming after annealing; Glass still is under the condition of high temperature during plated film; Need not once more glass to be heated; Need not to vacuumize, therefore compare and reduced the work in-process baking operation, reduced power consumption significantly with the off-line wet method for the equipment that is coated with antireflective coating; Compare with the vacuum magnetic-control sputtering method, reduced vacuumizing energy consumption, reduced power consumption significantly.Compare with above-mentioned technology, the inventive method unit consumption of energy reduces more than 50% on year-on-year basis.
Table 2 is made energy consumption and day output and the employing the inventive method manufacturing antireflective coating glass energy consumption and the day output contrast table of antireflective coating glass for adopting existing method.Unit consumption of energy is meant the full process energy consumption of making every square metre of antireflective coating glass in table 2.
Table 2
3, anti-reflection rate increases obviously, the performance of enterprises and obvious social benefit.
No matter be individual layer or double-layer reflection-decreasing film glass, single face is coated with that the anti-reflection rate of glass is 2.9%-3.0% behind the antireflective coating, and the anti-reflection rate of glass is 5.9%-6.0% behind the double coated antireflective coating.Testing data is as shown in table 3.
Table 3
Reduction along with PV cover-plate glass luminous reflectance factor; Transmittance improves on year-on-year basis, and the generating efficiency of solar cell also improves on year-on-year basis, so just can under the condition that obtains same generated energy, reduce the usage quantity of cover-plate glass, silicon chip semi-conductor electricity generation material, battery base plate Fluroplast-4 material and EVA film significantly; Can practice thrift great deal of raw materials; Reduce the cost of enterprise, not only can improve the profit of enterprise, and help the effective utilization and the saving of the energy.Simultaneously also can practice thrift a large amount of installing spaces.
Description of drawings
Fig. 1 is coated with the device structure synoptic diagram of glass antireflective coating for chemical vapor deposition method of the present invention;
Fig. 2 is coated with the plated film device example structure synoptic diagram of the equipment of glass antireflective coating for chemical vapor deposition method of the present invention;
Fig. 3 is coated with the equipment thermostat example structure synoptic diagram of glass antireflective coating for chemical vapor deposition method of the present invention;
Fig. 4 is coated with the vapourizing unit example structure synoptic diagram of glass antireflective coating for chemical vapor deposition method of the present invention;
Fig. 5 is coated with glass antireflective coating technical process embodiment synoptic diagram for chemical vapor deposition method of the present invention;
Fig. 6 obtains synoptic diagram for glass antireflective coating membrane uniformity check point.
Description of reference numerals
1 - steady beam 2 - exhaust manifolds 3 - antireflection coating materials manifolds 4 - hanging pieces 5 - hanging beams 6 - nozzle plate 7 - spacer blocks 8 - nozzle 9 - thermostat tubing 10 - zero-emission channel 11 - antireflection coating material feeding device 12 - hot oil thermostat 13 - dry air supply device 14 - carrier gas supply device? ? 15 - exhaust gas treatment device 16 - power plant 17 - coater 18 - glass with 19 - vaporization device 20 - electrical control devices 21 - oil heater 22 - oil cooling device 24 - antireflection coating material feed pipe 25 - on the head 26 - hot oil exports 27 - housing 28 - carrier gas into the trachea 29 lower head 30 - cyclone 31 - hot oil imports 32 - cyclone 33 - first orifice 34 - second orifice 35 - vapor phase antireflection coating raw materials exports ? 36 - transmission of heat space ? 37 - detection point 38 - temperature sensing devices .
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is elaborated.
As shown in Figure 1; The equipment that the present invention is coated with the 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 discharge gas path 10, emission-control equipment 15 and MCC PWR PLT 16, DCS electrical control gear 20 that power is provided 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 the waste discharge gas path 10 pipe UNICOM of emission-control equipment 15 and plated film device 17 with nozzle 8 pipes of plated film device 17.
Shown in Fig. 2 and 3; In the present invention; Plated film device 17 preferred following structures: the plated film device is made up of nozzle 8, waste discharge gas path 10 and nozzle stationary installation; Nozzle 8 and waste discharge gas path 10 are staggered; Can be being staggered of a nozzle 8 and one or two waste discharge gas path 10, also can be being staggered of a plurality of nozzles 8 and a plurality of waste discharge gas path 10s, and the plated film device of the staggered structure of a nozzle 8 and one or two waste discharge gas path 10 is applicable to being coated with of single-glass antireflective coating; A plurality of nozzles 8 are applicable to the staggered plated film device of a plurality of waste discharge gas path 10s and are coated with the single or multiple lift antireflective coating, feed the glass antireflective coating that different raw materials just can be produced the multilayer film structure for 8 li at different nozzles during use.In the present invention, nozzle 8 is formed by spacer pieces 7 with waste discharge gas path 10 at interval, can simplify plated film device 17 structures like this, reduces the cost of plated film device.One waste discharge gas path 10 preferably is set respectively in the both sides of nozzle 8, and so more isostatic is removed the complex waste gas that coating process forms, and can widen the plated film district simultaneously, makes raw material availability increase substantially.The nozzle stationary installation is by the nozzle plate 6 of static jet 8 and hang beam 5 and form, nozzle plate 6 through suspender member 4 with hang beam 5 and be connected, hang beam 5 and be fixed on the 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, and hangs beam 5 and is fixedly connected; Like this, plated film device 17 can be made things convenient for, stably be fixed on the frame.
By the outlet pipe of antireflective coating raw material collecting pipe 3 connection nozzles 8 and vapourizing unit 19, connect the inlet pipe of waste discharge gas path 10s and emission-control equipment 15 by waste gas collecting pipe 2.
For making nozzle 8 and waste discharge gas path 10 keep good thermostability, make plated film device 17 steady operation at high temperature, the equipment that the present invention is coated with the 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 that is provided with in the spacer pieces 7 of oil heater, oil cooler and plated film device is formed closed circuit oil circulating system.Adopt the deep fat thermostat 12 of this structure; Under the control of electrical control gear, can form the interlocking working order when oil heater and oil cooler work; That is: oil heater work when system starts; Oil heater and oil cooler co-operation during plated film guarantee that system's homothermic reduces the electrisity consumption of oil heater simultaneously.
Shown in Fig. 3 and 4; In the equipment of the present invention, the plated film device can be provided with one, also two or more can be set; When need carry out the double coated antireflective coating to glass; Need the glass ribbon lower surface before being positioned at annealing furnace to increase a plated film device 17, be glass ribbon 18 lower surface plated films, thereby obtain two-sided antireflective coating glass.Two-sided antireflective coating glass has higher antireflective effect.From table 3, can find out, about the anti-reflection rate of two-sided antireflective coating glass is doubled than the anti-reflection rate of single face antireflective coating glass.
In order to improve the working efficiency of vapourizing unit among the present invention, it is more thorough that liquid phase antireflective coating feed vaporization is got, and the present invention has done further improvement to vapourizing unit 19; It comprises the housing 27 of the sealing that is made up of upper cover 25 and lower cover 29 and cylindrical shell, in housing, is provided with the vaporizing chamber that is made up of tornadotron 32, first orifice plate 33 and second orifice plate 34, and second orifice plate 34 is arranged on the bottom of tornadotron 32 and is fixedly connected with housing; First orifice plate 33 is arranged on the top of tornadotron 32 and is fixedly connected with housing, and tornadotron can be single, also can be a plurality ofly to be arranged in the vaporizing chamber side by side; In tornadotron, be provided with swirler-; Swirler-be shaped as a screw shaft, this screw shaft can be a tubular shaft, also can be solid shaft; It can be multi-head spiral; Also can be the single head spiral, it in tornadotron with the equidirectional setting of the 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, hot oil inlet 31 and hot oil outlet 26 respectively be connected corresponding of oil export of deep fat thermostat 12 with oil inlet.27 of tornadotron 32 and housings are provided with the defeated heat space 36 that supplies the constant temperature flow of hot, supply the constant temperature deep fat to flow to hot oil outlet 26 from hot oil inlet 31, and tornadotron is carried out thermostatically heating.End at tornadotron 32 is provided with antireflective coating material feeding tube 24; At its other end carrier gas inlet pipe 28 is set; The purpose that is provided with like this is that the antireflective coating raw material of liquid phase is flowed in the tornadotron 32, to obtain best mass-and heat-transfer effect from the opposite direction that carrier gas gets into.Vapour phase antireflective coating material outlet 35 is preferably disposed on the upper end of housing.On first orifice plate and 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 through the corresponding through hole that is provided with on first orifice plate 33 or second orifice plate 34 respectively.
The principle of work of this vaporizer is following: carrier gas gets in the tornadotron 32 from bottom to top or from top to bottom; Do rotation in order along the spiral of swirler-30 and form the rotation carrier gas; Liquid phase antireflective coating raw material gets in the tornadotron 32 from the opposite direction of carrier gas; Rotated carrier gas immediately and carry and throw to tornadotron 32 internal surfaces, and formed thin liquid layer at tornadotron 32 internal surfaces.The constant temperature deep fat that is positioned at tornadotron 32 outsides is with tornadotron 32 thermostatically heating; When the temperature of liquid phase antireflective coating raw material is heated above the boiling point of itself; Liquid phase antireflective coating raw material promptly evenly, rapid evaporation, and with carrier gas 23 uniform mixing, form the air-flow that composition is even, velocity of evaporation is stable; Accomplish the vaporescence of liquid phase antireflective coating raw material, equidirectionally go out tornadotron from what liquid phase antireflective coating raw material got into tornadotron through the antireflective coating raw material of vaporization.
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 the miniaturized material carburetor; The saving non-ferrous metal consumes; Reduce manufacturing cost.
Below being that to be coated with antireflective coating be that example is carried out the description of detail to the method that the present invention is coated with the glass antireflective coating to photovoltaic sheet glass producing on the photovoltaic flat glass production line:
As shown in Figure 5; For the method that adopts chemical deposition of the present invention to be coated with the glass antireflective coating is made the technology of photovoltaic sheet glass antireflective coating, it is after the fusing compression moulding of molten cellar for storing things obtains hot glass ribbon, before annealing for hot glass ribbon, to be coated with glass antireflective coating with chemical deposition at frit on the photovoltaic glass production line.Frit is prepared burden, is founded in this process, moulding and annealing all can adopt existing photovoltaic flat glass production process, and the process that is coated with the glass antireflective coating comprises the steps:
A, join, feeding: various antireflective coating raw materials via after the antireflective coating raw feed materials device pressurization in proportion dispensing go into vapourizing unit;
B, liquid phase antireflective coating feed vaporization: liquid phase antireflective coating raw material is by vapourizing unit vaporization formation vapour phase antireflective coating raw material;
C, deposition: vapour phase antireflective coating raw material sprays to hot glass ribbon surface by the nozzle of plated film device; In hot glass ribbon surface flow, in antireflective coating raw material flow process, vapour pyrolysis chemical reaction takes place in the antireflective coating raw material under hot glass ribbon high temperature; The oxide products of reaction and the crystalline network ordered arrangement of hot glass surface fuse; Form the polycrystalline state thin-film body, do not have sedimentary residual product to flow to waste discharge gas path 10, and extracted out by emission-control equipment 15 through waste gas collecting pipe 2.In said process, decomposition reaction takes place and will decompose the oxidate that produces to form glass antireflective coating rete to hot glass ribbon surface in the slit of glass antireflective coating raw material between plated film device 17 and hot glass ribbon 18 surfaces of rapid heating.
In the above-mentioned process that is coated with the glass antireflective coating; Liquid phase antireflective coating raw material is preferably tetraethyl orthosilicate or silicon tetrachloride; Gas raw material is the exsiccant air; Liquid phase antireflective coating raw material flow rate is 0.3-0.4m/s, and pressure is smaller or equal to 1Mpa, and liquid phase antireflective coating feed vaporization temperature is 140-150 ° of C; Glass temperature is 600 ° of C-750 ° C in the plated film district, plated film district glass temperature with cotton ginning after the internal water temperature and the flow of glass ribbon snub pulley control.
For making liquid phase antireflective coating feed vaporization more thorough; In vaporescence, liquid phase antireflective coating raw material is carried with carrier gas; The opposite direction that carrier gas is got into by liquid phase antireflective coating raw material gets in the tornadotron; Carry liquid phase antireflective coating raw material by carrier gas and throw to tornadotron 32 internal surfaces, and form thin liquid layer, accomplish vaporescences by tornadotron 32 heating at tornadotron 32 internal surfaces along the orderly rotation of the spiral of swirler-.Carrier gas can be a kind of in rare gas elementes such as hydrogen, helium, nitrogen, argon or the carbonic acid gas, and nitrogen is as carrier gas.Carrier gas and air all have the effect of regulating air speed.
Adopt the inventive method to be coated with the glass antireflective coating; It is behind the glass ware forming, before the annealing, when glass ribbon is in the condition of high temperature, accurate blended glass antireflective coating raw material is ejected into hot glass ribbon surface through CVD plated film device, and the antireflective coating raw material is met heat the reactant that chemical reaction forms aerosol state is immediately taken place; Reactant directly is deposited on fresh hot glass ribbon surface; Combine with the spatial grid structure chemical bond of hot glass surface, form stable chemical performance, bonding strength is superpower, molecular arrangement is orderly crystalline structure film on hot glass ribbon surface, because in this process; The antireflective coating raw material is met the reactant of thermogenetic chemical reaction formation aerosol state and is closed the formation chemical bonded refractory with the spatial grid structure of hot glass surface and amounts to consubstantiality; Therefore the rete stability is good and stable high, and the crystalline structure ordering is good, and uniform crystal particles property is good; The surface does not form organism and decomposes the hole that vaporization stays, and 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; The green production of realization system, described emission-control equipment is connected to form by waste gas combustion furnace, fly-ash separator and washing tower successively, is discharged in the atmosphere by the waste gas of induced draft fan with the washing tower washing.
The plating method of glass antireflective coating of the present invention is applicable to the online antireflective coating that is coated with of sheet glass, can be on horizontal rolling process technology the online antireflective coating that is coated with, also can be used for the online antireflective coating that is coated with of other horizontal withdrawal method glass production process.
Be that example is elaborated to be coated with antireflective coating below at photovoltaic ultrawhite cotton ginning glass surface.
Embodiment 1
Glass ribbon width 2400mm, the glass ribbon pull speed is 280m/hr,
The frit of preparation obtains the high-viscosity glass liquid of 1100 ° of C after fusing, clarification, 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 the glass antireflective coating with chemical vapor deposition method carries out plated film; Used antireflective coating main raw material is tetraethyl orthosilicate, deionized water and air, and the 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 sent in the tornadotron 32 of vapourizing unit after feed device A, B, C pressurization respectively in proportion; The nitrogen and the air of 14 supplies of carrier gas feeding mechanism enter in the tornadotron from the opposite direction that liquid phase antireflective coating raw material gets into 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 by the tornadotron that is heated to 140 ° of C by thermostatical oil 32 heating; Obtain vapour phase antireflective coating raw material and mix with carrier gas through carburation by evaporation, vapour phase antireflective coating raw material flows out tornadotron from the equidirectional that liquid phase antireflective coating raw material gets into, and is entered into the nozzle 8 of plated film device by antireflective coating raw material collecting pipe through exsiccant air and vapour phase antireflective coating raw material; Spray to the hot glass ribbon surface that temperature is 665 ° of C by nozzle 8; Vapour pyrolysis chemical reaction takes place in the antireflective coating raw material under hot glass ribbon high temperature, the crystalline network ordered arrangement of the oxide products of reaction and hot glass surface fuses, formation of deposits polycrystalline state thin-film body; There is not sedimentary residual product to flow to waste discharge gas path 10; And pass through waste gas collecting pipe 2 and extracted out by emission-control equipment 15, accomplish the process that is coated with of glass antireflective coating, the glass ribbon that has plated antireflective coating gets into the annealing furnace cooling; Cut into the size that needs on request, packing makes finished product antireflective coated glass afterwards.
Embodiment 2
The glass ribbon width is 2400mm, and pull speed is 255m/hr, 680 ° of C of plated film district glass ribbon temperature, and the 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 got in the plated film device nozzle 32 by the dry air feeding mechanism.
All the other are with embodiment 1.
Embodiment 3
The glass ribbon width is 2400mm, and pull speed is 245m/hr, 640 ° of C of plated film district glass ribbon temperature.The antireflective coating raw material uses positive 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, and air is in the equidirectional entering tornadotron 32 that gets into liquid phase antireflective coating raw material.
All the other are with embodiment 1.
The glass ribbon width is 3300mm, and pull speed is 480m/hr, 670 ° of C of plated film district glass ribbon temperature.The 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, and flow 240Kg/hr, air feed hot glass ribbon surface, plated film district.
All the other are with embodiment 1.
Table 4 is each embodiment parameter list.Not shown unit is (Kg/hr) in the table
Antireflective coating measured result such as table 5 that online CVD technology single-surface single-layer is coated with:
Table 5
| ? | Do not have plated film front glass transmitance (%) | Glass transmitance (%) behind the 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 |
| Embodiment 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 |
| |
90.53 | 93.49 | 2.96 | 123 | 1.7 | 0.15 |
The quality product of online CVD explained hereafter photovoltaic anti-reflection film glass receives the kinds of processes condition influence, and the processing condition that wherein have the greatest impact are plated film district temperature.Data in the table 6 are at same antireflective coating raw material flow rate, subtract the contrast of prepared glass antireflective coating rete parameters under the pleurodiaphragmatic in terspace materials flow amount of penetrating, antireflective coating material temperature, appointed condition of the same race, the same glass speed of travel, the different plated film district temperature.
Table 6
From table 6, can draw to draw a conclusion:
Film deposition speed raises with temperature and accelerates, and explain that the raw material pyrolysis rate improves with temperature to accelerate, and makes the sedimentation velocity quickening.
The rete crystal grain diameter raises with temperature and diminishes.Be illustrated as crystalline substance and speed up, crystal seed quantity gathers way faster than crystalline growth velocity.This extremely has directive significance for holding crystalline structure, size and then a control film performance.
Raw material availability raises with temperature and improves.Thereby therefore should under the prerequisite that the film quality parameter can be satisfied the demand, suitably improve plated film district temperature and improve reaction zone temperature,, thereby reduce cost so that improve utilization ratio of raw materials.
The crystalline film sedimentation velocity is fast more, and the rete firmness can decrease, and not quite all can satisfy industrial needs but change.
Used test set is following in test of the present invention:
Transmittance test set: day island proper Tianjin 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 Instr Ltd. washability determinator;
Resistance to chemical attack experimental installation: the Central Asia, the Wuxi YWX/Q-016 of environmental test equipment ltd type salt-fog test machine;
The ultraviolet resistance testing installation: Shanghai is crowd's electronics technology SHA-PV-SM of ltd photovoltaic module ultraviolet experimental pretreatment machine still;
Pencil hardness test appearance: make 1000g pencil hardness meter according to the GB/T6739-1996 standard design.
Table 7: antireflective coating technical data that the inventive method was coated with and national standard contrast table
Experimental value (%)=(T
Before the eff experiment-T
After the eff test)/T
Before the eff experiment
Can be as drawing a conclusion from above data: the antireflective coating of online CVD technology manufacturing belongs to rower A level product, and more than important detection index very desirable.
Membrane uniformity adopts following detection method:
In the length of side is 1 meter on glass; Draw diagonal lines and obtain central point; Draw round as radius with 1/4 of catercorner length; The intersection point that intersects 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=(the detected value maximum difference/each point averages of 9 points) * 100%.
Claims (21)
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 vaporizing chamber antireflective coating liquid phase feed vapourizing unit (19), emission-control equipment (15), be provided with the plated film device (17) and the thermostat of nozzle (8) and waste discharge gas passage (10); Said antireflective coating raw feed materials device (11) is communicated with the vaporizing chamber pipe of said vapourizing unit (19); Described vaporizing chamber is communicated with nozzle (8) pipe of said plated film device (17), and said waste discharge gas passage (10) is communicated with said emission-control equipment (15) pipe.
2. chemical vapor deposition method as claimed in claim 1 is coated with the equipment of glass antireflective coating; It is characterized in that said vapourizing unit (19) also comprises the housing (27) and the carrier gas feeding mechanism (14) of sealing, said vaporizing chamber is tornadotron (32); It is fixedly installed in the said housing (27); Said tornadotron (32) is heated by said thermostat, and an end of said tornadotron (32) is connected with carrier gas inlet pipe (28), and the other end of said tornadotron (32) is connected with liquid phase feed feed-pipe (24); Vaporization raw material extraction line (35) is connected with said tornadotron; In said tornadotron (32), be provided with swirler-(30), said swirler-(30) is a screw shaft, the parallel axes setting of the axis of said screw shaft and said tornadotron.
3. eddy flow dry type evaporator as claimed in claim 2; It is characterized in that; Said thermostat is deep fat thermostat (12); Be provided with the defeated heat space (36) of heat supply oil circulation between said housing (27) and said tornadotron (32), the hot oil outlet of hot oil inlet (31) and the hot oil outlet (26) of said housing (27) through setting on it and said deep fat thermostat and hot oil inlet is corresponding is connected.
4. chemical vapor deposition method as claimed in claim 2 is coated with the equipment of glass antireflective coating; It is characterized in that; Said nozzle (8) is communicated with said vaporizing chamber pipe through antireflective coating raw material collecting pipe (3); Said waste discharge gas passage (10) is communicated with emission-control equipment (15) pipe through waste gas collecting pipe (2); It is characterized in that: described nozzle (8) and waste discharge gas passage (10) are formed by spacer pieces (7) at interval, and described nozzle (8) and waste discharge gas passage (10) are parallel to be crisscross arranged.
5. chemical vapor deposition method as claimed in claim 4 is coated with the equipment of glass antireflective coating; It is characterized in that; Said thermostat is deep fat thermostat (12); Described spacer pieces (7) is provided with constant temperature oil pipe (9), and the oil-in of constant temperature oil pipe (9) and oil outlet thereof are communicated with the oil outlet and the oil-in respective tube thereof of described deep fat thermostat (12) respectively.
6. chemical vapor deposition method as claimed in claim 4 is coated with the equipment of glass antireflective coating, it is characterized in that, the both sides of said each nozzle (8) are provided with a waste discharge gas passage (10) respectively.
7. chemical vapor deposition method as claimed in claim 4 is coated with the equipment of glass antireflective coating; It is characterized in that; Said plated film device is provided with the nozzle stationary installation; Said nozzle stationary installation is by nozzle plate (6) and hang beam (5) and form, and said nozzle plate (6) is fixedly connected with the said beam (5) of hanging through suspender member (4), and said spacer pieces (7) is fixedly connected with said nozzle plate (6).
8. chemical vapor deposition method as claimed in claim 7 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 discharge gas passage (10) at described nozzle plate (6); Said nozzle (8) is connected with said antireflective coating raw material collecting pipe (3) through said through hole, and said waste discharge gas passage (10) is connected with said waste gas collecting pipe (2) through said through hole.
9. be coated with the equipment of glass antireflective coating like claim 3 or 5 described chemical vapor deposition methods; 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 said 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.
10. a chemical vapor deposition method is coated with the method for glass antireflective coating, it is characterized in that: behind glass ware forming, before the annealing, be coated with the glass antireflective coating.
11. chemical vapor deposition method as claimed in claim 10 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: the antireflective coating raw material in proportion, through transferpump pressurization back entering vapourizing unit;
B, liquid phase antireflective coating feed vaporization: liquid phase reflectance coating raw material is vaporized by vapourizing unit and is formed vapour phase antireflective coating raw material;
C, deposition: vapour phase antireflective coating raw material gets into the plated film device; Spray 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) high temperature rapid heating is decomposed, accomplish being coated with of glass surface antireflection film.
12. chemical vapor deposition method as claimed in claim 11 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 said vaporizing chamber by liquid phase antireflective coating raw material from an end of said tornadotron (32), carrier gas (23) enters in the said tornadotron (32) from the opposite direction that liquid phase antireflective coating raw material gets into, by said carrier gas (23) carry said liquid phase antireflective coating raw material along the spiral of said swirler-(30) in order rotation throw to said tornadotron (32) internal surface; And form thin liquid layer at said tornadotron (32) internal surface, accomplish vaporescence by the thin liquid layer of said tornadotron (32) heating evaporation.
13. be coated with the method for glass antireflective coating like claim 11 or 12 described chemical vapor deposition methods, it is characterized in that in the described steps A, its pressure of described pressurization is smaller or equal to 1Mpa.
14. be coated with the method for glass antireflective coating like claim 11 or 12 described chemical vapor deposition methods, it is characterized in that among the described step B, the speed when said liquid phase antireflective coating raw material is carried is 0.3-0.4m/s.
15. be coated with the method for glass antireflective coating like claim 11 or 12 described chemical vapor deposition methods, it is characterized in that said liquid phase antireflective coating raw material is tetraethyl orthosilicate or silicon tetrachloride, deionized water and catalyzer, described gas raw material is an air.
16. be coated with the method for glass antireflective coating like claim 11 or 12 described chemical vapor deposition methods, it is characterized in that the vaporization temperature of said liquid phase antireflective coating raw material is 140 ° of C-150 ° C.
17. chemical vapor deposition method as claimed in claim 16 is 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 a triethyl phosphate, and consumption is 0.6 Kg/hr-2.5 Kg/hr, and the glass pull speed is 240 m/hr-480m/hr.
18. chemical vapor deposition method as claimed in claim 12 is coated with the method for glass antireflective coating, it is characterized in that, said liquid phase antireflective coating raw material is tetraethyl orthosilicate or silicon tetrachloride, deionized water and catalyzer; The consumption of described tetraethyl orthosilicate or silicon tetrachloride is 8.5Kg/hr-22 Kg/hr; Described deionized water consumption is 0.5 Kg/hr-1.5 Kg/hr, and described catalyzer is a triethyl phosphate, and consumption is 0.6 Kg/hr-2.5 Kg/hr; Described gas raw material is an air; Described air flow quantity is 50 Kg/hr-200 Kg/hr, and described carrier gas is a nitrogen, and its consumption is 80 Kg/hr-240 Kg/hr; The glass pull speed is 240 m/hr-480m/hr.
19. be coated with the method for glass antireflective coating like claim 11 or 12 described chemical vapor deposition methods, it is characterized in that among the described step C, the temperature of described hot glass ribbon is 600 ° of C-750 ° C.
20. be coated with the method for glass antireflective coating like claim 11 or 12 described chemical vapor deposition methods, it is characterized in that among the described step C, described hot glass ribbon pyritous temperature is 640 ° of C-680 ° C.
21. be coated with the method for glass antireflective coating like claim 11 or 12 described chemical vapor deposition methods, it is characterized in that described glass is the sheet glass that rolling process or horizontal sheet process make.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104556714A (en) * | 2014-12-11 | 2015-04-29 | 上海晶澳太阳能科技有限公司 | Method for preparing high-transparency coated photovoltaic glass |
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