CN104694882A - Substrate film coating process method - Google Patents
Substrate film coating process method Download PDFInfo
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- CN104694882A CN104694882A CN201510120972.9A CN201510120972A CN104694882A CN 104694882 A CN104694882 A CN 104694882A CN 201510120972 A CN201510120972 A CN 201510120972A CN 104694882 A CN104694882 A CN 104694882A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910004613 CdTe Inorganic materials 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
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- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 19
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- Physical Vapour Deposition (AREA)
Abstract
The invention provides a substrate film coating process method, in particular to a coating film for a glass substrate for manufacturing a solar cell. The method comprises the steps that the upper side and lower side of a moving substrate which penetrates a heating cavity and a coating cavity are heated with different intensity, so as to improve the coating temperature, but the glass substrate cannot be operated due to softening. Equipment is applicable to implementing the method and has a heating cavity and a coating cavity with an independent heating system and an independent transfer system.
Description
Technical field
The present invention relates to the method for the plated film in slab-shaped substrate and equipment, in particular for the plated film of the glass substrate that solar cell manufactures
Background technology
In the energy generation in future, solar cell will play important role.At present, especially thin-film solar cells has advantage in following, namely less materials consumption and be applicable to industrialization produce.Cadmium telluride (CdTe) based thin film solar cell is suitable for the first-selection as efficient thin-film solar cell of future generation.The energy gap of CdTe material is 1.45eV, is therefore suitable for especially absorbing sunlight, and then can obtain high efficiency by CdTe thin film solar cell.Usually applied as the top level structure with Cadmium Sulfide (CdS) by CdTe, so that the pn knot needed for manufacturing, this pn knot is made up of the CdTe layer of p-type and the CdS layer of N-shaped.In the case, CdS act as form to a certain extent, and from visible ray, absorb only sub-fraction, and rest part is absorbed through CdS layer arrival CdTe layer, produces the current carrier forming photovoltage.
In the manufacture of CdTe based thin film solar cell, usually glass is used as substrate.From substrate, then sink to the bottom rete in the following order, that is, front electrode layer, n-CdS layer, p-CdTe layer, dorsum electrode layer.At present, transparent energy conductive oxide (TCO, transparent conductive oxide) use front electrode layer, wherein, usually uses the stannic oxide (ITO) of indium doping.Known TCO is in addition the stannic oxide (FTO) of Fluorin doped or the zinc oxide (AZO) of aluminium doping.Below the manufacture of front electrode layer is not probed in detail.
Metal level is used as back of the body motor layer, wherein, in order to improve the stability of solar cell and in order to the adaptive CdTe layer in ohm ground, partly add extra layer.
When below relating to substrate, the following is prerequisite, the necessary preparation work namely on substrate, as front electrode layer plated film, clean and cut open the steps such as light and complete.
When speaking of substrate temperature, refer to the surface temperature of downside, namely point to downwards, typically refer to TCO plated film side.Surface temperature on the downside of this, as the temperature of upside, is determined by temperature sensor non-contactly.Professional and technical personnel is well known that the other materials of these materials and equipment is transferred to one or more material processing facility individually or together with the material be connected in before or after equipment, this material processing facility when considering whole process, completes the control of each individual facilities based on these materials.Be controlled according to method of the present invention.
Fact proved, close spaced sublimation (CSS) method is particularly suitable for depositing CdS and CdTe.At this, starting material, such as highly purified CdTe particle in a reservoir, are especially suitable for the high temperature being heated to about 600 DEG C to 770 DEG C in this evaporator crucible, to distil or to evaporate material to be deposited, wherein, substrate is directed through above evaporation source with very little spacing.At this, the spacing between Coating Materials source and substrate is only several millimeter to several centimetres.Such as resistance heating element or infrared radiating element may be used for heating evaporation crucible.Plated film usually occurs in vacuum chamber, 10
-4carry out in the residual gas pressure of mbar to 10mbar, wherein, can be necessary before this by rare gas element, as nitrogen or argon cleaning plated film chamber.When plated film, if use traditional soda-lime glass, substrate itself typically has the temperature of 480 DEG C to 550 DEG C.Arrive the depositing temperature in actual plated film chamber at glass substrate before, the transport process through one or more heating chamber is reached this depositing temperature by glass substrate.In theory for high-level efficiency, high substrate temperature is Worth Expecting, this is because observe following situation, namely under the substrate temperature of 575 DEG C, efficiency significantly declines.Certainly in very high substrate temperature situation, only have corresponding costliness, resistant to elevated temperatures glass substrate can use.In a word, the characteristic of the method is the high deposition rate of several μm/min.
Substrate through the motion in heating chamber and/or plated film chamber be by means of the roller be arranged on axle based on transfer system realize.Also learnt by W003/054975A2 with continuous print transmission shaft, the transfer system that is used in the solar cell be made up of silicon, certainly, transmission shaft does not arrange extra roller, thus relatively little solar cell is placed on transmission shaft with its whole plane.During heat treatment process, in stove, also use this transmission shaft.Manufacture for large-area solar modules for being obtained rete by deposition material from below, this transmission shaft is not suitable for because in the case substrate evaporation side or evaporation side whole plane ground be coupling tactile, rete can be caused thus to suffer damage.
In the prior art, there is in plate shaped substrate the width of the 600mm perpendicular to delivery direction, typical shaftless supporting, and only move on the roller of outside.Larger width is not suitable for the use of common soda-lime glass substrate.Preferably glass is used as substrate.Glass is counted as having full-bodied especially liquid at room temperature usually.Correspondingly, neither one is melt temperature point significantly, but viscosity raises with work temperature and declines.Therefore, in order to the temperature spot that the softening introducing describing glass is different, the numerical value of described temperature spot equals dynamic viscosity index (denary logarithm) and defines.
Hereinafter use transition point Tg, this transition point has the viscosity index of 12.0.This transition point is in the limited proportionality scope in the viscosity index interval with 12.0-13.4.The numerical value of Tg is all in about 550 DEG C-555 DEG C (typical float glass numerical value is in the interval of 540 DEG C-560 DEG C) in used glass.The standard of this transition temperature has following Temperature numerical, and when this Temperature numerical, the dynamic viscosity of substrate reaches transition point.Hereinafter, the interval (transition temperature is interval) of transition temperature is described below temperature range, is in the interval of 12.0 to 13.4 at this temperature range medium viscosity index.
Under the high temperature conditions, be near transition temperature (at about 540 DEG C-560 DEG C, depending on glass types), because plastic deformation appears in the VISCOUS FLOW of glass, and this VISCOUS FLOW is irreversible, therefore should keep little as far as possible.The glass substrate of low transition temperature is also have same reason, if namely substrate only moves on the roller of outside, then substrate can not in higher than the temperature of about 520 DEG C plated film.
Summary of the invention
Therefore, from above-described technical barrier, following innovative technology is proposed, namely introduce a kind of method and a kind of equipment for be limited to hardly glass substrate width, with plated film at the temperature of CSS method in transition temperature interval.
Accompanying drawing explanation
By reference to the accompanying drawings, by detailed description hereafter, above-mentioned and other feature and advantage of the present invention more clearly can be understood, wherein:
Fig. 1 shows the cross section through plated film chamber, and this cross section orthogonal distributes in delivery direction, wherein substrate) be bearing on the outside roller of axle; Between the roller of outside, substrate is by inner side roll support; Axle is bearing in the bearing of axle near its end;
Fig. 2 shows through plated film chamber and along the vertical cross-section of delivery direction, axle belongs to transfer system, the position of the container of band Coating Materials is furnished with at those, the between centers of axle is obviously greater than the between centers of plated film chamber center, and three axles (2) are arranged relative to each other with very little interval there;
Fig. 3 shows the 3-D view of the removing plated film chamber upper cover in plated film chamber, the upper part of inner chamber is also removed, the container with Coating Materials is shown between multiple axle, relative to the comparatively Large space can finding out the axle between plated film container compared with Small Distance between multiple axles directly placed side by side of plated film chamber center, substrate enters in plated film chamber through conveying seam, and by transmission shaft, substrate motion is passed plated film chamber, through the second conveying seam, substrate leaves again plated film chamber;
Fig. 4 shows the axle of the temperature range being used in below substrate transfer temperature, axle only has an inner side roller between the roller of outside, and the gap ratio of the guiding shaft shoulder of outside roller is less when the temperature range of the transition temperature close to substrate or the axle in this temperature range;
Fig. 5 shows the intercept A of the axle of Fig. 4, in this intercept, shaft end is shown, and the supporting surface of the guiding shaft shoulder and outside roller is shown, the guiding angle of the shaft shoulder and the angle of supporting surface are determined as shown in the cross section of the axis through axle;
Fig. 6 shows the 3D view of heating chamber without its upper part, in this heating chamber, multiple axle is with pitch arrangement same relative to each other, under axle, heating unit is shown, substrate enters in heating chamber through conveying seam, and by roller, substrate motion is passed heating chamber, then substrate leaves again this heating chamber through the second conveying seam;
Fig. 7 shows the cross section through heating chamber, and this cross-section parallel is in delivery direction, and the transfer system of heating chamber has axle, and for all adjacent axles, axle their spacing relative to each other is identical;
Fig. 8 shows through the cross section of heating chamber perpendicular to delivery direction, axle has each inner side roller between two outside rollers, axle outside inner chamber, supported on its end, lower plane of reflection and upper plane of reflection reflect the thermal radiation of heating system on orientation substrate, can find out, plane of reflection drawn down sides, so that also can by the lateral edges of heat radiation to substrate; And
Fig. 9 function shown as temperature provides the viscosity characteristics of glass substrate, can find out transition temperature, in this transition temperature, reach the viscosity index of 12.0.
[main element nomenclature]
1 substrate
2 plated film chambeies
3 heating chambers
10 with the container of CdS or CdTe
The transfer system in 20 plated film chambeies
The axle of the transfer system in 21 plated film chambeies
The shaft end of the axle of the transfer system in 21 plated film chambeies
The bearing of the axle of the transfer system in 212 plated film chambeies
The outside roller of the axle of the transfer system in 213 plated film chambeies
The conically supporting surface of the outside roller of the axle in 2131 plated film chambeies
The guiding shaft shoulder of the inclination of the outside roller of the axle in 2132 plated film chambeies
The inner side roller of the axle of the transfer system in 214 plated film chambeies
The conveying seam in 22 plated film chambeies
Transfer system in 30 heating chambers
The axle of the transfer system in 31 heating chambers
The shaft end of the axle of the transfer system of 311 heating chambers
The bearing of the axle of the transfer system of 312 heating chambers
The conically supporting surface of the outside roller of the axle in 3131 heating chambers
The guiding shaft shoulder of the outside roller of the axle in 3132 heating chambers
The outside roller of the axle of the transfer system of 313 heating chambers
The inner side roller of the axle of the transfer system of 314 heating chambers
The conveying seam of 32 heating chambers
For the heating unit of the heating system on the downside of substrate in 33 heating chambers
The plane of reflection of the heating system on the downside of in the of 331
For the heating unit of the heating system on the upside of substrate in 34 heating chambers
The plane of reflection of the heating system on the upside of in the of 341
The inner chamber of 35 heating chambers
L guides the spacing of the shaft shoulder
The angle of the supporting surface of roller outside a
B guides the angle of the shaft shoulder
The spacing of not arranging the axle in the region of container of d application chamber
The spacing of the axle in dd heating chamber
The spacing being furnished with the axle in the region of container of D application chamber
Embodiment
See the accompanying drawing of the specific embodiment of the invention, hereafter in more detail the present invention will be described.But the present invention can realize in many different forms, and should not be construed as by the restriction in the embodiment of this proposition.On the contrary, it is abundant and complete open in order to reach for proposing these embodiments, and makes those skilled in the art understand scope of the present invention completely.
Description describe in detail according to the embodiment of the present invention according to the present invention, substrate is heated in the transition temperature interval of substrate in the sequence of heating chamber or heating chamber.Equal, or be heated close to transition temperature, the upside of substrate is heated to the temperature lower than downside, ensure that the camber arch of substrate is lifted thus, even if this camber arch lifts the operability that also can ensure that substrate in higher than the temperature of transition temperature.By the substrate film coating be so heated.Preferred use CdS and/or CdTe as Coating Materials, but also can consider material copper, indium and gallium to be used for CIS solar modules or CIGS solar modules, and material copper, zinc, tin and sulphur can be considered to be used for CZTS solar modules.
During with the plated film of CSS method, substrate is on plated film container as described.Therefore fastening for substrate can not be set in the vertical direction of plated film container, this is because interference plated film is even formed in an undesired manner by plated film by this fastening.On this position, substrate to have higher than the temperature of transition temperature curved too consumingly hanging down because of it, and coating can accumulation unevenly.
According to the present invention, can avoid the problems referred to above by with under type, the downside by substrate is compared upside and is heated to higher temperature.Thus, expand more strongly than upper substrate side in the hypocoxa side be heated strongly, thus make to produce internal stress in a substrate, and this internal stress is to having bent restraining effect.
The preferred rectangle of shape of substrate.In other preferred implementations, substrate is in foursquare.When the multiple support of substrate, in plated film container front and rear, the camber arch of the downward sensing of substrate is propped up, and accessible support width is enough, to cross over container width when tolerable flexure.
The transition temperature of substrate depends on used material.Preferably traditional soda-lime glass is used as substrate, and the transition temperature of soda-lime glass is between 540 DEG C to 560 DEG C.
When plated film, the downside temperature of soda-lime glass substrate is greater than 520 DEG C, and is preferably between 540 DEG C and 570 DEG C, and particularly preferably in about 550 DEG C.
The temperature difference between the downside of soda-lime glass substrate and upside is preferably at least 2K to 4K, continues preferred 5K to 8K, and particularly preferably about 6K.The research of soda-lime glass substrate shows: when support width is no more than about 300mm to 400mm, preferred 350mm freely, under typical process condition, the deformation of (process lasts 10min, process temperature 550 DEG C, thickness of glass are about 3.2mm) glass substrate does not surmount tolerable yardstick.
This favourable way makes to become possibility as follows, namely between the both sides of substrate, before occurrence temperature balance, completes the processing step performed in the temperature in transition temperature interval because of thermal conduction.
After coating process, cooled lentamente by substrate, this is necessary, to avoid the stress in substrate.When Slow cooling, the attachment of rete on substrate through evaporation is not also destroyed.
In a preferred embodiment, during the plated film of rete, average substrate temperature (have between the upside and downside of substrate according to the temperature difference of the present invention) is in the transition temperature interval of substrate, and is cooled to below transition temperature interval after rete plated film.Next this substrate is heated once again, and set up between upside and downside according to the temperature difference of the present invention.Carry out next step plating steps subsequently.
During plated film, by substrate guided through the container with Coating Materials.This container has following temperature, and this temperature is higher than the temperature of the downside of substrate.Due to the thermal conduction in substrate, although comparatively slow, occur through whole substrate until being heated of the back side.Stress in substrate can weaken thus.But in order to maintain according to the temperature difference of the present invention, therefore must between containers substrate be cooled.For this reason, produce the thermograde through substrate consciously, thus make to continue on the downside of substrate to remain on the technological temperature for rete necessity, and can not superheated.This comprises regulating according to equipment of the present invention and its or controlling to reach of inner chamber (passage) by heating system.The adjustment of heating system depends on substrate thermal conduction to upside from downside.Preferred container along delivery direction in couples, one by one, and according to container between arrange with keeping Large space.This spacing is preferably about 385mm.When container keeps large distance, being cooled to by substrate is possible under transition temperature.Before next plating steps, average substrate temperature must be heated on transition temperature according to heating means of the present invention.Then, along with the temperature equilibrium of the part of upside and downside, the operability that substrate was lifted and then lost to camber arch is also lost.This to need by intergrade between cooling and being again heated rebuild.
In this method, transfer system is employed.In this transfer system, substrate places on roller.There is injured coating film area in the part placed of substrate.Plated film is imperfect or be disturbed because of a series of mechanical factor in the region.This area damages solar cell functional normally, therefore must get rid of.This otherwise realize in the following way, the defective film layer be about in the region is reasonably played a minor role by mechanical scratching, laser, sandblasting or polishing until substrate remove, occur in the following way, separate and then isolation from unimpaired coating film area by injured coating film area.This plays a minor role preferably by laser and reaches.
In order to perform according to method of the present invention, preferably by one or more heating chambers that substrate rises through temperature, until reach the necessary technological temperature for plated film.Until substrate surmounts transition temperature, namely lower than the interval of 540 DEG C, reasonably moved on the transfer system with two outside rollers and several inner sides roller (preferably with an inner side roller when substrate width at 1200mm) by substrate.At this, inner side roller is the roller of supporting substrate, and these rollers are arranged on common axle with these outer roller between two outside rollers.In last heating chamber before plated film, substrate reaches the interval of transition temperature, and the axle of transfer system preferably has other inner side roller (when the substrate width of 1200mm preferred three inner side rollers altogether).The upper side and lower side of substrate is heated with being used in the heating system varying strength of the upper side and lower side.This adjustment separated preferably by the heating system for the upper side and lower side or control are carried out.Upside temperature and downside temperature monitor preferably by temperature tactility apparatus (preferred noncontact temperature sensor).Substrate is camber arch slightly, and can entered by heating chamber without crossing over impacting in the transition in plated film chamber subsequently thus, or arrives on plated film container without other support components in plated film chamber.
The method is preferred for manufacturing CdS/CdTe thin-film solar cells.
During plated film, the vertical spacing of the distillation/container for evaporation of substrate and deposition material, preferably approximately 3mm to 50mm, particularly preferably 5mm to 20mm.In CSS method, this spacing should keep as small as possible.In the art, the spacing being less than 5mm is described.At this, first plate CdS rete, next plating CdTe rete.Correspondingly, first substrate moves on the evaporator crucible that CdS raw material is housed, and next moves on the evaporator crucible that CdTe raw material is housed.And the rete of this bi-material preferably directly carries out successively in a procedure.
In other preferred implementation, rete adopts CdS raw material to make row in a plated film chamber, and in the second plated film chamber, adopts CdTe raw material to carry out subsequently.Under some circumstances in preferred design, the cooling of substrate is implemented between two plating steps.This intercooling carries out in one or more heating chamber be arranged between plated film chamber.Separating by two plating steps, advantageously, higher substrate rate of advance becomes possibility, wherein, intercooled step causes: substrate can not soften too consumingly and can rebuild with described type and mode by heating the camber arch of stabilization to lift once again.
Next, substrate is through the one or more heating chambers as cooling zone work, in this one or more heating chamber, substrate can first preferably cool lentamente, after dropping to the temperature between about 400 DEG C from 500 DEG C (different according to glass types), then can cool more quickly.
That and for example implements in the prior art described by beginning is such, and plated film preferably carries out in a vacuum, but at a higher pressure even under normal pressure in theory plated film be also possible.
Be preferred for the plated film as hypocoxa according to method of the present invention, these substrates have the width larger than 600mm width as transmission limit.Correspondingly can by plate shaped substrate with width G reatT.GreaT.GT 700mm, preferably > 1000mm plated film, particularly preferably apply with the width of about 1200mm.But the coating of the substrate of almost any width can be considered in principle, as long as the unsupported width between two rollers does not exceed opposing substrate and the acceptable yardstick of technological temperature.
Hereafter in detail the equipment according to the embodiment of the present invention will be described.
According to the present invention, it is heating under vacuum chamber that equipment at least has a device, and this heating chamber can irrelevantly control with at least two each other or regulate the heating system in inner chamber.The upside of at least one heating system heats substrate, and the downside of at least one heating system heats substrate.Each heating system has one or more heating unit.Heating system adjusts as follows, that is, make the downside of substrate have higher temperature than upside.In addition this equipment has: at least one is configured to vacuum chamber equally, and along the plated film chamber after delivery direction is arranged in heating chamber; And for substrate through heating chamber to the transfer system in plated film chamber; With the transfer system through plated film chamber for substrate.Two transfer systems all have multiple parallel, axially spaced-apart, along delivery direction one by one and perpendicular to the array axis arranged of this delivery direction ground.The transfer rate of substrate in transfer system preferably between 0.5m/s and 5m/s, particularly preferably between 1m/s and 4m/s and continue particularly preferably between 1.5m/s and 3m/s.
The heating chamber being embodied as vacuum chamber has inner chamber, the good interval of inwall of this inner chamber and heating chamber.The outside of inner chamber is provided preferably with Heat-insulation device.What inwardly then follow is the inwall of heating system and inner chamber.Namely heating system is arranged between lagging material and inwall.This realizes the heating power uniformly distributing of the heat release of heating system in the following way, namely the inwall of inner chamber forms passage, heat by heating system radiation is diffusely assigned on substrate by this passage, and in fact works as the indirect heating apparatus to substrate.Adopt the disrupter of heating power, prevent heating system to the heat direct radiation on the wall of heating chamber.Transfer system is through inner chamber and whole heating chamber, and this transfer system has multiple for making the axle of substrate motion, and these axles run through guiding through wall and supported outside inner chamber.
Material as the inwall for inner chamber preferably uses metal, such as molybdenum (or molybdenum alloy).Other preferred implementations arrange quartz or C-base composte material.
Surface temperature on the downside of substrate preferably detects via temperature sensor non-contactly.In a preferred embodiment, temperature sensor is arranged in outside heating chamber, and passes through the Temperature numerical of keyhole detection substrate, and these apertures extend through total.Heating system design is reasonable, adjustable.Other information (such as entering sheet speed and substrate position) of data detected by temperature sensor and equipment are detected equally, and be transferred to central data processing system, this central data processing system implements the control of equipment, does not elaborate at this to this.Heating system has one or more heating coil, and these heating coils are preferably configured as resistive heating device.At this, these heating coils individually or marshalling ground, with sleeve-shaped, in a zigzag, meander shape or with the other system of laying of being generally acknowledged by prior art arrange between the axles.The each heating coil these heating coils can organized into groups regulates with regard to its temperature uniquely.Upper and lower in heating system, the reflector exceeding position of preferred arrangements side direction bending, these reflectors are to the heat of orientation substrate reflected radiation.Even be also heated together by the side seamed edge exceeding position substrate of side direction.By means of only the suitable manipulation according to layout of the present invention and heating system of heating system and inner chamber, below possible, namely substrate from below plated film and by the less heating on the upside of glass or even cooling keep the technological temperature that requires of glass under side place.For this reason, upper heating system preferably produces the temperature of about low 10K than lower heating system.
Multiple axles of transfer system are along delivery direction one by one and axially compartment of terrain and arranging perpendicular to delivery direction relative to each other.At this, these axles are flatly arranged, wherein, preferably along delivery direction, do not occur or only occur very little deviation (preferred <3%) in the sequence of axle.
Preferably adopt sleeve pipe to be drawn by inner chamber on these axles, and supported outside this inner chamber.The driving of axle is also preferably arranged in by outside the inner chamber that heats, but in a vacuum.Drive the direct mechanical preferentially using axle to connect to carry out, such as adopt motor, the transmission mechanism of this motor or chain device are directly connected at least one shaft end.In inner chamber, between sleeve pipe and relatively these sleeve pipe tight spacings ground, every axle is furnished with two outside rollers.Between the roller of outside, be respectively furnished with roller inside at least one.Outside roller is used for substrate conically supporting surface, and this supporting surface has the diameter increased with going to immediate shaft end.Preferred outside roller is equipped with the guiding shaft shoulder of inclination.Those temperature axles be on transition temperature on the downside of its place's substrate preferably have two or more inner sides roller.Preferably the outside roller of these axles locates to have larger guiding shaft shoulder spacing compared with axle that temperature on the downside of substrate is under transition temperature with those at it.
Because substrate is transmitted on multiple roller, so must avoid as follows, namely in slab-shaped substrate along the seamed edge before delivery direction, curvedly when reaching next axle hanging down, and to be impacted when being transitioned on next axle.This may cause the infringement of seamed edge.This phenomenon by with under type reply, that is, can reduce the spacing of axle.But problem is, when the space then provided between diaxon is no longer enough to necessary built-in part, such as evaporator crucible provides space.Even if when substrate is transitioned into another chamber from a chamber, be also necessary as follows, namely cross over larger between centers with seamed edge before substrate without strong curved vertical mode.
In order to address this problem, by suitable control or adjustment heating system, the downside of substrate is heated more consumingly than upside.Very little between upside from downside slightly temperature contrast cause the different thermal expansion of both sides to cause the elastic bending of substrate.This causes the edge of substrate higher than center.Meanwhile, substrate bears gravity.When base plate supports is on the outside roller only arranged in edge, gravity causes the bending of substrate, the bending identical direction that this bending sensing causes with heating power.Described two processes strengthen mutually thus.If but, except the support in edge by outside roller, also be added with the support at thin plate center of one or more inner sides roller, then cause the support of thin plate on the roller of inner side, the heating power upwards of substrate edges curves through the gravity pointed to downwards and offsets at least in part, thus makes caused overall bending reduction.
Plated film chamber is also vacuum chamber, and plated film chamber has the inner chamber for heating power uniformly distributing.Through the transfer system in whole plated film chamber, from the base plate glass that leading portion heating chamber or application chamber receive, be delivered on the transfer system of heating chamber or the application chamber be connected in below.By in the transport process of inner chamber, by substrate thin plate plated film on its underside.In container (evaporator crucible) that Coating Materials (preferred CdS or CdTe) is arranged in heating, that be open upwards, be directed through with very little spacing at these evaporator crucible upper substrates.Directly over container, preferably do not arrange transfer roller, so as to avoid or reduce as possible transfer roller by plated film.Therefore, have at least several axial ratio to play the situation in heating chamber in transfer system, there is larger spacing relative to each other.Because substrate passes plated film chamber with the temperature in transition temperature interval, the structure of axle, corresponding to the structure of the axle of the transfer system in heating chamber, possesses multiple inner sides roller and locates to possess larger guiding shaft shoulder spacing compared with axle that substrate temperature is in below transition temperature with those at it.Only on transfer system, heating system is provided with in plated film chamber.Because vessel temp is apparently higher than temperature on the downside of substrate, so also obtain the heating effect on the downside of substrate therefrom.The temperature of substrate must be starkly lower than the temperature in container certainly, so that the deposition of material that is that reach evaporation on the downside of substrate or that distil.In the embodiment transmitted, in plated film chamber, detected the temperature of the upper side and lower side of substrate by temperature sensor.
Temperature sensor in heating chamber and plated film chamber preferably works non-contactly, and the radiation (such as high temperature sensor) being preferably based on surface detects the temperature of substrate surface.
Substrate is delivered to the transfer system of following chamber by conveying seam from the transfer system in a chamber, and by these conveying seams, these chambeies are connected to each other.Pressure lockage only occurs by taking out in last chamber to be transported to by substrate in the first chamber.
The transmission shaft of transfer system is preferably made up of quartz-ceramics (Fused Silica).The characteristic of this material is, even if heat conduction also considerably less in high temperature have high mechanical rigid.Single roller can be processed by the in the radial direction selectivity reduction of the axle in cylinder shape by the region outside roller preferably by process of lapping.At this, be enough as follows, namely roller just slightly, preferably exceeds actual transmission shaft with being less than 10mm.By the quartz-ceramics preferably using thermal conduction little, be possible as follows, be namely provided with stainless copper cover to the may of transmission shaft on both sides.Transmission shaft is guided within the bearing by these stainless copper covers, wherein, drives and preferably carry out via gear mechanism in side.The expansion of the transmission shaft be made up of quartz-ceramics when high temperature is very little and can therefore be left in the basket.
According to the present invention, inner side roller is also arranged on same transmission shaft transverse to the outside roller in the straight line of substrate delivery direction as being in.Preferably arrange along the follow one another inner side roller of following of delivery direction in the mode of alignment.Making in kind of situation, whole rollers is all processed by transmission shaft.This occurs preferably by polishing, turning or other working methods according to prior art.When outside roller is seated on continuous print transmission shaft, easy motion reaches largely, thus also inner side roller can be arranged on one or more specific axle or the twelve Earthly Branches support guiding inner side roller that can float on axle, and without the need to driving dynamic for inner roller subband.
In a preferred embodiment, only have several transmission shaft to be driven, to make substrate travel forward, and the transmission shaft of the roller arranged in addition just serves the support of substrate.
Preferably in the sequence in heating chamber and plated film chamber, load following transfer system, these transfer systems only have two kinds of preferred reel structure modes:
Concerning wherein temperature close to transition temperature or being in transition temperature interval region, axle possesses multiple inner sides roller and larger guiding shaft shoulder spacing.Guiding shaft shoulder spacing is preferably 1205mm to 1207mm, particularly preferably 1206mm, and therefore the sideshake of base plate glass is advantageously limited in about ± l mm.
Concerning wherein temperature is in the region under transition temperature, axle possesses consistent guiding shaft shoulder spacing (preferred 1205mm) and preferably only has one (preferably placed in the middle) inner side roller.The sideshake of base plate glass is defined to native 2.5mm in the interval of 25 DEG C to about 500 DEG C.If substrate width requires that other support, then the number of inner side roller can be more.Number so for the inner side roller of the axle in the temperature range on softening temperature improves equally.
Use only two kinds of makes of axle, due to the raising of the batch production number of packages of often kind of make, advantageously leads to obvious cost advantage.
By with under type, namely outside roller is arranged on continuous print axle with sufficiently high resistance to torsion, and outside roller always synchronously runs, thus makes no longer to cause out slippage (Schlupf) due to the transfer path of different lengths.
The conically supporting surface of outside roller preferably has in cross section from the angle of 0.3 ° to 6 °, particularly preferably from the angle of 0.6 ° to 4 ° and in addition particularly preferably from the angle of 1 ° to 2 °.Thus, substrate entered the operation of roller noise low peace and stability degree was high more.The guiding shaft shoulder of preferred outside roller has inclination, and this inclination causes the side direction guide of substrate, and does not cause excessive edge stress, and excessive edge stress may cause seamed edge to damage.Guiding the shaft shoulder the angle in the cross section of axle moderately between 120 ° and 150 °, preferably 130 ° with 142 ° with and particularly preferably 139 °.
In the preferred implementation that outside roller is alternative, the guiding shaft shoulder is not set, and the guiding roller that be directed through side direction of substrate in transfer system is implemented, supported under the guiding roller elastic stage of these side direction, and when substrate seamed edge laterally offsets from delivery direction, the guiding roller of these side direction produces the counterpressure of guide function.
Particularly advantageously, this equipment can be used for processing cheap soda-lime glass, and this soda-lime glass has relatively low softening temperature.Obviously, also this equipment can be applied to the plated film of other unconventional glass substrate, such as, for having higher durothermic glass.As long as load the inner side roller of corresponding number with the spacing be applicable to, be then possible as follows, by substrate with almost any width ground plated film.Correspondingly also can use such as 1200mm width and larger width glass substrate.
When the coating of the preferred soda-lime glass of 3.2mm thickness and about 550 DEG C of temperature, obtaining may the free support width of about 350mm.The spacing of two rollers should be 300mm to 400mm, be preferably 350mm thus.In addition fact proved, the wide substrate of such as 1200mm is when being bearing on two outside rollers and a central roller, at roller with compared with the wide substrate of 600mm be only on two outside rollers, flexure is stronger, although free span is all respectively 600mm in both cases.Can see below this reason, namely the roller only on two outer ledges is supported, and to act as the bending line of glass substrate crossing with sea line under the angle determined, on the contrary, the bending line of the glass substrate supported by central roller extraly hereinto heart roller place must continuous distribution, and because of build-up effect, disappear in the angle of the relative level line of central roller position.Favourablely allow according to operating method of the present invention, for substrate above-mentioned and mentioned process condition, the spacing of axle usually about 230mm brings up to about 350mm.
By the reduction of curved substrate, become possibility as follows, that is, in higher than the temperature of 520 DEG C, perform plated film, preferably between 540 DEG C and 560 DEG C, particularly preferably in about 550 DEG C.
Compared with the temperature that application is lower, the efficiency depositing the solar cell that CdS/CdTe makes in the temperature of about 550 DEG C can improve.In the case, although pay following cost, namely the plated film of substrate suffers damage in the region of the running orbit of inner side roller.The CdS/CdTe layer be disturbed has the width of the <12mm in the scope of inner side roller, and has the width of the <10mm in the scope of outside roller.By the participation of roller inside other, from transition temperature, the width of the coating zone be disturbed of extra inner side roller is just only about 6mm, this is because when temperature in transformetion range, substrate guided device is very narrow as shown and " vacillate " thus, the hypokinesis of the namely side of substrate.This undermined region must remove in the framework of process steps after a while.But, the effective surface of the product caused thus be reduced by higher process temperature and the higher efficiency that causes thus is subject to overcompensate.Typically, in follow-up technique, such as by radium-shine ablation again remove with the CdS/CdTe layer in the contact area of roller.Also be possible by the delineation removing rete of sandblasting or machinery.Be separated by injured layer region preferably by two thin isolation cuttings, these two isolation cuttings run through rete, but only slightly cut in substrate.The possible width of this kind of isolation cutting is 20 μm to 100 μm.When photovoltaic property is only slightly damaged due to roller, the disposal to contact area also can be abandoned under certain condition completely.This preferably determines during the algorithm of substrate evaluation.Therefore, the Optimum Points found between acquisition high technology temperature and undesirable space wastage technically and is economically wished.
For the design example of the coating film area size be disturbed
According to exemplarily known, when performing method of the present invention according to equipment of the present invention, the interfering factors of substrate film coating be considered.
Glass substrate in plate shape has the length of such as 1600mm, the width of 1200mm and the thickness of 3.2mm.The width of preferred inner side roller is 2mm to 6mm, especially 3mm to 5mm.Roll width narrow is as far as possible favourable, this is because narrowly will keep due to the injured region of roller in this way, in this injured region, again must remove rete after a while.With regard to the region that central roller damages glass substrate, the width of for lesion area adds double guiding tolerance l by roll width
fuhr, tolwith the tolerance of dimension l of substrate
m α β, toldetermine.In order to the region that makes in the region to be damaged keeps proper, compared with the roller of outside, less inner side roller can be selected, namely the roll width of central roller or middle roller.
Such as inner side roll width is 3.0mm, and the width of supporting surface of outside roller is 5.0mm in contrast.In the case, the guiding tolerance of thin plate is ± 0.5mm and the tolerance of dimension of thin plate for ± 0.5mm when, the maximum width obtaining the battery band be damaged at roller place, inner side is thus 5mm.
If described above, send as follows and select transition temperature T
g, that is, in the interval of transition temperature, use with n
oberthe transmission shaft of individual roller, and below transition temperature, use in contrast with n
unterthe transmission shaft of individual roller, then must additionally consider because extra roller is to the infringement of rete.At T
gwhen=500 DEG C, the expansion length dL of glass substrate between 25 DEG C and 500 DEG C
25_500be about 5mm, and the expansion length dL between 25 DEG C and 550 DEG C
25_550be about 6mm.The CdTe region damaged by outside roller has following width there:
b
CdTe,auβen＝b
Rolle,auβen+dL
25_500/2+2*(l
fuhr,tol+l
Mαβ,tol)≈9.5mm
(outside roll width bRolle, au β en=5mm).
Following width is had by the CdTe region damaged with roller in extra:
b
CdTe,zwischen＝b
Rolle,innen+(dL
25_550-dL
25_500)/4+2*(l
fuhr,t。l+l
Mαβ,t。l)≈5.25mm
(middle roller width b
rolle, innen=3mm).
[embodiment]
Describe exemplary equipment subsequently, this equipment is suitable for performing according to method of the present invention.Reference numeral is with reference to the corresponding element in accompanying drawing.
First heating chamber 3, plated film chamber 2 and the second heating chamber 3 are arranged one by one.
Employ that make in plate shaped soda-lime glass, that there is the transition temperature of 550 DEG C substrate 1.On the downside of substrate 1, the tco layer as front electrode has been coated with in algorithm above.Substrate is 1200mm along the width of delivery direction when 25 DEG C.The length of substrate 1 is that 1600mm is when 25 DEG C.The mode cavetto that substrate seamed edge is polished with C shape.Substrate 1 enters the first heating chamber 3 of the temperature with 480 DEG C.This substrate moves on transfer system 30.Transfer system 30 is made up of axle 31, and this axle has the outside roller 313 of the guiding shaft shoulder 3132 that band tilts.In the cross section of the axis through axle, the inclination of the guiding shaft shoulder 3132 of each outside roller 313 is 139 °.The guiding shaft shoulder 3132 spacing is 1205mm.Substrate, at the seamed edge place parallel with delivery direction, places on the supporting surface 3131 of outside roller 313.Supporting surface 3131 has the inclination of 3 °, and has the width of 10mm.Substrate 1 is medially supported by roller 314 inside first, this inside first roller there is the width of the 3mm in supporting surface.From now on, by substrate 1 in heating chamber 3, thereon side and its on the downside of on heating, and slowly pass through this chamber motion rate of advance about at this: 1.5m/min.If substrate 1 reaches transition temperature interval, then from this point, roller 314 inside axle 31 is medially furnished with two second between roller 314 and outside roller 313 again inside first.The spacing of the present guiding shaft shoulder 3132 is 1206mm.Heating system 34 so adjusted from now on, that is, substrate 1 is when reaching the end of heating chamber 3, on its underside 6K hotter than side place thereon.This temperature difference causes internal stress, and this internal stress causes the camber arch of substrate 1, and the center of curvature of this camber arch is on substrate 1.By the support by three inner side rollers 314, this camber arch can not unhinderedly be formed downwards.Cause the rigidity reinforced of substrate 1.Due to this rigidity reinforced, substrate 1 to enter in plated film chamber 2 subsequently through the between centers of 250mm and does not collide on the first axle 21 of the transfer system 20 in plated film chamber 2.After the transition temperature interval reaching substrate 1, the transfer system 20 of application chamber 2 is corresponding with the transfer system 30 of heating chamber 3.Substrate 1 is continued to move along delivery direction.Substrate reaches the container 10 that first is equipped with CdS raw material, in this first container, is evaporated by CdS when the temperature of 680 DEG C.Substrate 1 moves in the past with the spacing of opposite edge 5mm on container 10.Container 10 is 300mm along the width of delivery direction.Because can not arrange support rollers in the region, so substrate 1 only lifts based on internal stress and camber arch cross over this spacing, this pipeline overhead lifting lifts and is caused by the temperature difference between the downside and upside of substrate 1.This external this occurs, due to the high-temperature in container 10, is significantly heated more strongly in addition downside than upside.At this, the downside of substrate 1 reaches the temperature of about 555 DEG C.After crossing the first container 10, substrate is supported by the axle 21 with two outside rollers 213 and three inner side rollers 214 again.After three with this axle 21 of the pitch arrangement of 250mm, be followed by another plated film container 10 with CdS.This plated film container is same as two plated film containers 10 that CdTe is housed of following, is striden across in the manner described.Next the substrate 1 through plated film arrives in the second heating chamber 3.Herein by substrate Slow cooling.Substrate leaves second heating chamber with about 500 DEG C of temperature.Connect after this second heating chamber but what do not describe in detail is other heating chambers, in other heating chambers multiple, substrate temperature continues to decline.After the transition temperature interval downward across glass, substrate 1 is transmitted again on the roller 31 of the guiding shaft shoulder 3132 spacing with 1205mm and on unique inner side roller 314.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that those of ordinary skill in the art just design according to the present invention can make many modifications and variations without the need to creative work.All technician in the art, all should by the determined protection domain of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (10)
1., for a method for substrate film coating, described substrate (1), in plate shaped, is characterized in that, following steps:
A) make described basal plate heated to transition temperature;
B) and a) simultaneously and/or subsequently, make the downside of described substrate than the upside of described substrate
Be heated to higher temperature; And
C) by least one Coating Materials evaporation on described substrate.
2. method according to claim 1, is characterized in that, described substrate is cooled after coating lentamente.
3. method according to claim 1 and 2, is characterized in that, makes described substrate temperature in step c) after drop under described transition temperature, and next repeated execution of steps a) to c).
4. according to the method described in claim 3, it is characterized in that, the transition temperature of described substrate is between 540 DEG C to 570 DEG C.
5. method according to claim 4, is characterized in that, described substrate is soda-lime glass.
6. method according to claim 5, is characterized in that, the temperature of the downside of described substrate is greater than 520 DEG C at coating temperature.
7. method according to claim 6, is characterized in that, the downside of described substrate is in step b) after to have than upside and exceed at least 2K's to 4K.
8. method according to claim 7, is characterized in that, described Coating Materials is CdS and/or CdTe.
9. method according to claim 8, is characterized in that, described Coating Materials is CIS or CIGS (copper, indium and/or gallium, selenium).
10., according to the method described in claim 9, it is characterized in that, described Coating Materials is CZTS (copper, zinc and/or tin, sulphur).
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| CN116083875A (en) * | 2023-01-05 | 2023-05-09 | 江苏尚孚电子有限公司 | A kind of LED aluminum substrate surface coating device and coating method thereof |
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Application publication date: 20150610 |