CN105980067A - Solution containment during buffer layer deposition - Google Patents

Solution containment during buffer layer deposition Download PDF

Info

Publication number
CN105980067A
CN105980067A CN201480068296.9A CN201480068296A CN105980067A CN 105980067 A CN105980067 A CN 105980067A CN 201480068296 A CN201480068296 A CN 201480068296A CN 105980067 A CN105980067 A CN 105980067A
Authority
CN
China
Prior art keywords
web
supporting surface
described web
solution
substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201480068296.9A
Other languages
Chinese (zh)
Other versions
CN105980067B (en
Inventor
杰弗里·S·布里特
斯科特·奥尔布赖特
乌尔斯·朔普
沃尔特·施托斯
达伦·韦赖贝伊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Global Solar
Global Solar Energy Inc
Original Assignee
Global Solar
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US14/108,193 external-priority patent/US9252318B2/en
Application filed by Global Solar filed Critical Global Solar
Publication of CN105980067A publication Critical patent/CN105980067A/en
Application granted granted Critical
Publication of CN105980067B publication Critical patent/CN105980067B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/677Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for conveying, e.g. between different workstations
    • H01L21/67703Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for conveying, e.g. between different workstations between different workstations
    • H01L21/67706Mechanical details, e.g. roller, belt
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/677Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for conveying, e.g. between different workstations
    • H01L21/67739Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for conveying, e.g. between different workstations into and out of processing chamber
    • H01L21/6776Continuous loading and unloading into and out of a processing chamber, e.g. transporting belts within processing chambers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264Inorganic materials
    • H01L31/032Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03926Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate
    • H01L31/03928Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate including AIBIIICVI compound, e.g. CIS, CIGS deposited on metal or polymer foils
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/541CuInSe2 material PV cells

Abstract

The invention discloses improved methods and apparatus for forming thin-film layers of chalcogenide on a substrate web. Solutions containing the reactants for the chalcogenide layer may be contained substantially to the front surface of the web, controlling the boundaries of the reaction and avoiding undesired deposition of chalcogenide upon the back side of the web.

Description

Solution containment during buffer layer deposition
Cross-Reference to Related Applications
The application is the U.S. Patent Application Serial Number 12/397,863 submitted on March 4th, 2009 Part continues, and this patent application is according to United States code 35 the 119th article and foreign country applicatory and the world The U.S. Provisional Patent Application Serial No. 61/068,458 of legal requiremnt submission on March 5th, 2008 Priority, each application is passed through to quote to be all incorporated into hereby.
Background
The field of photovoltaics is usually directed to convert sunlight directly into the multilamellar material of DC electrical power Material.The fundamental mechanism of this conversion is awarded Nobel Prize in physics gold by Einstein at him Photovoltage (or photoelectricity) effect the most correctly described in 1905 academic scientific papers.In the U.S., Photovoltage (PV) device is generically referred to as solaode.Solaode is configured generally to The cooperation sandwich of p-type and n-type semiconductor, wherein n-type semiconductor is (in sandwich On one " side ") show the excess of electronics, and p-type semiconductor material (another " side " in sandwich On) show hole excess, the shortage of the most each expression electronics.P-n between the two materials Near Jie, the valency electron from n-layer moves in the adjacent hole in p-type layer, in solar-electricity Pond is internal produces little electric imbalance.This causes the electric field in the adjacent domain of knot.
When in incident photon is by the electron excitation in battery to conduction band, the electronics excited is from quasiconductor Atom be released, be produced from by electron hole pair.Because that, p-n junction is neighbouring knot Producing electric field in region, the electron hole pair produced by this way near knot is tended to separate and remote Mobile from knot, electronics is towards N-shaped side shifting and hole towards the p-type side shifting of knot.This is at battery Middle generation total electrical charge is uneven so that if external conductive path is arranged between the both sides of battery, then Electronics will return to p-type side along external path from N-shaped side shifting, produce electric current.It practice, can lead to Cross and guide the grid of the part covering surface to come the surface from N-shaped side or neighbouring collection electronics, with Time still allow for being substantial access to battery by incident photon.
When the electrical contact of suitable location is included and battery (or a series of battery) is merged into closing electricity Time in road, such photovoltaic junction is configured to work PV device.As independent device, single Conventional solaode is not enough to power to major applications.As result, solaode is the most logical Cross and will be connected to after another battery before a battery be arranged in PV module or " string ", Thus the voltage electric of independent battery is in series added together.Typically, fairly large number of battery series connection Connect to realize voltage available.Thus then the DC electric current produced can be fed by inverter, its In it is converted into AC electric current under suitable frequency, it is selected to coupling and is supplied by normal grid The frequency of AC electric current.In the U.S., this frequency is 60 hertz (Hz), and other country of major part AC power under 50Hz or 60Hz is provided.
A certain types of solaode for commercial use development is " thin film " PV battery. Comparing with other type of PV battery such as crystalline silicon PV cells, Thin film PV cells needs less Light absorbing material creates working battery, and therefore can reduce processing cost.PV based on thin film electricity Pond is also by former used in the thin film industry being widely used in protectiveness, dicoration and functional coating The deposition technique of exhibition provides the cost of improvement.The common examples of low cost commercial film product is included in The coating of the permeable water on food Package based on polymer, the ornamental painting on building glass Layer, low-launch-rate thermal control coating on house and commercial glass and the scraping on glasses and anti-reflective Penetrate coating.Use or amendment technology of development in these other fields allows to sink at PV battery thin film Reduction in the development cost of long-pending technology.
Additionally, hull cell, especially with copper and indium diselenide, copper and indium aluminum diselenide or copper and indium The efficiency close to 20% shown by those hull cells of the sunlight absorber layers of gallium diselenide, its ratio Must go up or exceed the efficiency of maximally effective crystalline silicon.Particularly, copper and indium gallium diselenide (CIGS) is Stable, there is hypotoxicity, and be the thinnest film, need in work PV battery less than two The thickness of micron.As result, so far, CIGS seems to show high-performance, low cost Thin film PV product and thus to permeate a large amount of GENERATION MARKET maximum likelihood.
Thin film PV material can be deposited on rigid glass substrate or in flexible substrates.Substrate of glass is relative Inexpensively, it is generally of the thermal coefficient of expansion relatively closely mated with CIGS or other absorber layers, And allow the use of vacuum deposition system.But, such rigid basement suffers various shortcoming, such as To the needs of sizable floor space of processing equipment and be short in needed material, special heavy duty commanding apparatus, High possibility that substrate ruptures, due to the weight of glass and the shipment cost of increase that is delicate and that cause Difficulty in an installation.As result, the use of substrate of glass is to large volume, high yield, multilamellar Film material with function the most photronic business manufacture is not optimal.
On the contrary, the roll-to-roll process of thin film flexible substrate allow compact, less expensive vacuum system and The use of the no special equipment other thin film industry developed.Thin flexibility based on PV battery Base material is also shown quickly heating and cooling and (causes the relatively high toleration of big thermal gradient Rupturing or the low probability of fault during processing), need relatively low shipment cost and show ratio The installation easiness that battery based on rigid basement is bigger.
The certain types of N-type semiconductor material that can use in Thin film PV cells is in the field of chemistry In be referred to as chalcogenide.Chalcogenide be by least one chalcogen ion and at least another sun The chemical compound of electricity element such as metal composition.The most such as special for all purposes This is by quoting in the U.S. Patent number 6,537,845 of the McCandless that is merged in the disclosure et al. Describe the thin film forming chalcogenide.But, formed and there is expectation thickness and uniformity chalcogenide Thing film maintains challenge technically, and improvement is needs.
Historically, the formation of one or more thin film chalcogenide buffer layers is often through relatively low The cyclic process of effect continues, and this cyclic process includes to be heated to rising containing the substrate in water container Temperature, adds slaine and mixes in slaine, and then adding the component containing chalcogen also Component containing chalcogen mixes.At the specified temperature after the stipulated time, reaction completes, Substrate is removed, and the solution used is sent to refuse and processes, and the solution containing reactant is applied to Web, and container be cleaned by for next react.Additionally, the solution containing reactant is coated to web Existing method generally result in chalcogenide on expectation (" front " or " top ") surface of web with And also another (" afterwards " or " end ") surface of web at least some of on deposition, need At least one cleaning step removes material from rear surface.This generally uses acid solution and completes, acid Solution must be controlled and be removed completely avoid the damage to expectation thin layer and avoid modestly The long-term corrosion problem activated by the existence of residual acid.
Additionally, when reactant solution arrives the dorsal part of substrate, because whole substrate is immersed in reactant In the bath of solution or because the solution of the top side being coated to substrate is the most fully contained on top side, move May be very except all too much chalcogenide formed on the back of substrate and/or any heating element heater Difficult or impossible.This can affect the hot quantity at the top arriving substrate.Such as, in the downside of substrate The chalcogenide of upper accumulation can affect thermal capacity and the thermal conductivity thereof of substrate, and gather on the heaters Chalcogenide can affect emissivity and/or the thermal conductivity of heater.Additionally, these whole in substrate of impact Can be heterogeneous on individual width.
On any heating element heater on the downside of substrate and/or on that side being arranged in substrate Such undesirable chalcogenide deposition may result in the base reservoir temperature controlled sorrily and has not Being correspondingly formed of the chalcogenide buffer layer of the desired feature wanted.Such as, if arriving the top table of substrate The quantity of the heat in face reduces owing to the chalcogenide under substrate is formed, then this may result at top table The formation of the thinnest chalcogenide buffer layer on face.Similarly, if arriving substrate The quantity of the heat of top surface is uneven, then owing to the uneven chalcogenide under substrate is formed This may result in the formation of chalcogenide buffer layer the most heterogeneous on the top.These Effect is likely to be due to the unpredictable and uncontrolled chalcogenide under substrate and is formed and be difficult to Control.
It is known in the art during roll-to-roll in substrate web, deposits chalcogenide layer example As by hanging web edge on vertical rails from above, to raise the transverse edge of substrate web molten to improve Liquid is contained.But, this generally results in the undesirable buckling force in web, makes to maintain deposition The flatness of the expected degree in district is difficult to.Meanwhile, former system uses hold-down mechanism such as One or more wheels keep web to contact with underlying surfaces such as conduction heaters.But, this Produce hot localised points in substrate, cause the undesirable inhomogeneities in chalcogenide.In ability It is also known that longitudinally tilt whole web to control the degree of depth of the reactant solution in web in territory.So And, these existing systems do not provide the multiple slope adjustment in the various parts of crystallizing field, and therefore Enough control to solution deep and corresponding chalcogenide thickness may not be provided.For all above-mentioned Reason, before contain substrate by chalcogenide reactant or the method for improvement of top surface and dress It is desirable for putting.
General introduction
Current teaching discloses the improvement of the thin layer for forming chalcogenide in substrate web Method and apparatus.According to current teaching, the solution of the reactant comprising chalcogenide layer can essence On by containment to the front surface of web, it is to avoid the chalcogenide undesirable deposition on dorsal part.
The brief description of accompanying drawing
Fig. 1 is the top view of the thin film photovoltaic battery of the aspect according to the disclosure.
Fig. 2 is the schematic side elevation of the device for forming thin layer in substrate web.
What Fig. 3 was an up that the lateral edge portion of substrate web supports simultaneously and carry web has recessed horizontal stroke Fragmentary cross-sectional view to the conveying roller of section.
What Fig. 4 was an up that the lateral edge portion of substrate web supports web simultaneously has recessed horizontal section The fragmentary cross-sectional view of horizontal lifting structure.
Fig. 5 is an up the cut-away section on the frustum of a cone supporting surface of the lateral edge portion of substrate web Figure.
Fig. 6 is arranged at the transverse edge of conveying roller and the lateral edge portion of support base web The angularly fragmentary cross-sectional view of lift structure.
Fig. 7 is arranged on the angled of the front of conveying roller the lateral edge portion of support base web The fragmentary cross-sectional view of lift structure.
Fig. 8 is the part side of the lateral edge portion of the substrate web by frustum of a cone supporting surfaced lift Elevational view, web is carried by conveying roller simultaneously.
Fig. 9 is illustrate the compressing structure that is configured to keep substrate web to contact with lower floor conveying mechanism thin The side view of joint.
Figure 10 is illustrate a pair compressing structure keeping substrate web to contact with lower floor conveying mechanism saturating View.
Figure 11 is the schematic plan view of the part for the device through crystallizing field transport substrate web, It illustrates the positioned opposite of conveying roller, lift structure and hold-down mechanism.
Figure 12 is the flow chart being depicted in substrate web the method forming thin film chalcogenide buffer layer.
Figure 13 be describe according to the aspect of current teaching for through crystallizing field transport substrate web The perspective view of another device.
Figure 14 be describe according to the aspect of current teaching for through crystallizing field transport substrate web The perspective view of another device.
Figure 15 be describe according to the aspect of current teaching for through crystallizing field transport substrate web The perspective view of another device.
Figure 16 be describe according to the aspect of current teaching for through crystallizing field transport substrate web The perspective view of another device.
Figure 17 is the profile of the line 17-17 intercepting of the device along Figure 16.
Figure 18 is to describe, according to the aspect of current teaching, film damper is deposited to flexible substrates On the flow chart of other method.
Describe in detail
I. introduce
The manufacture of fexible film PV battery can be continued by roll-to-roll process.Compare with rigid basement, The roll-to-roll process of thin flexible substrates allows relative compact, less expensive vacuum system and has been it The use of some no special equipment of its thin film industry development.Flexible base material has ratio inherently The thermal capacity that glass is lower so that the amount of the energy needed for rising high-temperature is minimized.They are also shown To quickly heating and cooling and the relatively high toleration of big thermal gradient (is caused breaking during processing Split or the low probability of fault).Additionally, once activity PV material deposits on flexible base material, Thus the no lamination battery produced and battery strings just can shipped to another facility for lamination and/or group Dress up flexibility or rigidity solar module.This policy selection reduces the cost of shipment (relative to glass The flexible substrates of weight amount) and realize the enterprise in partnership for completing and sell PV module in the whole world The establishment of industry.
One or more layers light being usually permission available being deposited in Thin film PV cells is penetrated into battery " Window layer " of inside, and also be used as n-type semiconductor material in the battery in some cases Material.Such layer is also referred to as " cushion " in PV field of batteries.When as Window layer and half During conductor, cushion ideally to expectation wave-length coverage in light should be substantially transparent, and Also show that suitable characteristic electron.Cushion also can by also function as multiple Window layer of quasiconductor such as with Form with by one layer of cadmium sulfide of one layer of cadmium zinc sulfide.Can by one or more metals such as zinc, Cadmium, lead, hydrargyrum or any metal selected from race 1b, 2b or 3a of the periodic table of elements or the group of metal Close and chalcogen such as chemical reaction between oxygen, sulfur, selenium or tellurium is formed and has desired characteristic Thin film buffer layer.Thus the compound produced is commonly referred to as chalcogenide.Solar device suitable Window or cushion parts can include such as cadmium sulfide, zinc sulfide, zinc selenide, cadmium selenide zinc, oxidation Zinc and Aska-Rid. zinc.
Fig. 1 illustrates the top view of the thin film photovoltaic battery 10 of the aspect according to the disclosure.Battery 10 be substantially planar, and usually rectangle, as described in FIG, although except rectangle Shape in addition can be more suitable for specifically applying, such as roof or other table of fancy shapes Face.Battery has top surface 12 basal surface relative with top surface 14 and includes length L, width W and the size of thickness.Length and width can be for the convenient application of battery and/or in order to during processing Convenience and be chosen, and typically in the range of several centimetres (cm) to tens of cm.Such as, long Degree can be about 100 millimeters (mm), and width can be about 210mm, although optional Other suitable size any.The edge of the width crossing over battery can be characterized as being leading edge 16 He respectively Trailing edge 18.The gross thickness of battery 10 depends on the certain layer selected for battery, and general by battery The THICKNESS CONTROL of lower substrate.Such as, the stainless steel-based end, may have about 0.025mm (25 microns) Thickness, and other layers all of battery may have about the group of 0.002mm (2 microns) or less Close thickness.
By starting with flexible substrates and then multiple thin layers of different materials being deposited to base continuously Battery 10 is created at the end.This assembling can be completed by roll-to-roll process, and thus, substrate is from pine Line roller advances to stringing roller, advances through the sequence of deposition district between the two roller.PV material Then the battery of any desired size can be cut.Base material during roll-to-roll is typically Thin, flexible, and the environment of tolerable relatively-high temperature.Suitable material includes such as high temperature polymerization Thing such as polyimides or thin metal such as rustless steel or titanium are together with other material.Continuous print layer is the most logical Cross that various process such as sputters, evaporates, vacuum moulding machine, chemical deposition and/or printing come at individually place Reason deposits in substrate in room.These layers can include molybdenum (Mo) or chromium/molybdenum (Cr/Mo) rear-face contact Layer;Material such as copper and indium diselenide, copper and indium aluminum diselenide or copper and indium gallium diselenide (CIGS) Absorber layers;Such as one layer cadmium sulfide (CdS) of one or more cushions;And serve as PV electricity Transparent conductive oxide (TCO) layer of the top electrode in pond.Additionally, generally mainly by silver (Ag) or The conductive current of certain other conducting metal structure is collected grid and is generally coated with on tco layer.
Although the precise thickness of every layer of Thin film PV cells depends on that the definite of material selects and for being formed Every layer and the application-specific process that selects, the coating of example described above material, thickness and every layer Method continues with the general sequence of every layer to suprabasil coating as follows:
Layer describes Exemplary materials Exemplary thickness Exemplary coating method
Substrate Rustless steel 25μm N/A (materials in storage)
Rear-face contact Mo 320nm Sputtering
Absorber CIGS 1700nm Evaporation
Cushion CdS 80nm Chemical deposition
Front electrode TCO 250nm Sputtering
Collect grid Ag 40μm Printing
Remainder of this disclosure focuses on the various methods for forming chalcogenide buffer layer and dress Put.
II. solution containment and web carry
This section describes for through the web of crystallizing field transport substrate material and for including cushion And/or the various reactant solutions of the chemical composition of Window layer are contained in the method in the expectation district of web And device.
According to the aspect of the disclosure, cushion can be coated to lower floor's PV battery via chemical deposition process Layer (usually bottom substrate, one or more back contact layer and absorber layers).Such as Fig. 2 institute Showing, this process relates to carrying in a longitudinal direction with 30 instructions generally through crystallizing field 34 One or more reactant solutions 36 are also assigned in crystallizing field by the web 32 of film base material Device in web.In order to react and form suitable chalcogenide, reactant solution should minimum bag Containing at least one metal and at least one chalcogen.Additionally, solution typically will comprise chemical complexing agent, Such as ammonia and deionized water (DI).
Although describe in fig. 2 system linear ground and on the direction corresponding to the longitudinal size of web Conveying web, current teaching it is contemplated within depositing the alternative of thin film buffer layer.These alternatives Including such as solution be coated to be arranged in the concave or convex web interiorly or exteriorly gone up of drum like structure with And use the horizontal web of one or more training dyke (such as container, plate or roller) to carry, training dyke Be held from web " controlled draining " distance with keep chalcogenide solution in the suitable reaction phase Period is against web.
Device 30 include generally with 40 instruction for through in longitudinal region crystallizing field transmit base The conveying mechanism of the continuous flexible web of bottom material.Conveying mechanism 40 can take various forms, such as Transmittable web supports its one or more continuous belts or a series of roller simultaneously from above or below, Web can rest on roller and be transmitted.Fig. 2 describes include support base web and carry the multiple same of it The conveying mechanism of step conveying roller 42.Roller 42 can be evenly spaced apart, as in figure 2 it is shown, or they can It is spaced unevenly other expectation element with adaptive device.In order to ensure web in consistent speed Under carried along its length through crystallizing field, roller 42 can be synchronized by any suitable method. Such as, roller all can be driven by single rotary shaft, and each roller is linked to common axis.Roller can pass through full-height tooth Wheel/screw link mechanism (not shown) or be linked to axle by other link mechanism any.In some feelings Under condition, backing roll can not rotate, but can be more properly the static cross accurately flushed Frame.In other cases, backing roll can be rotatable but not driven, in this case, Loose ends roller and/or stringing roller mechanism can drive the motion of substrate web.
In a lot of existing systems for chemically synthesizing chalcogen cushion via chemical bath, Be assigned to solution in web to generally result in cushion on top (or front) side of web in accordance with Undesirable deposition on the deposition needed and the some or all of ends (or back side) of web. This undesirable deposition may need cleaning subsequently and the possibility with acid solution The second extra cleaning step to remove for many cushions cleaned in the first cleaning step Residual acid.During the cleaning step that these are extra, it may be necessary to and be likely difficult to protect top side to delay Rush before layer and other on the top side of web thin layer of deposition from the work used in cleaning The attack of property solution.The use sacrificing protectiveness back of the body patch material or the web that maybe can reuse is examined Consider, but there is the restriction of their own and the cost of increase.
According to current teaching and as described in figure 3, the relative lateral edge portion of substrate 32 Points 44 can be by fully promoting with the hoisting mechanisms of 46 instructions generally.Hoisting mechanism 46 is configured to phase Marginal portion 44 lifting of web be enough to buffer reactant solution by the core 48 for web Substantially it is contained in the amount on the top surface of web.This can complete in various manners.Such as, such as figure Shown in 3, hoisting mechanism can include one or more conveying rollers 42 with concave edge edge portion so that carries Rise the lateral edge portion of web simply by making web by coming on the recessed horizontal section of recessed roller Complete.In such embodiment, conveying roller may be provided under consistent speed carry web and The top table of web buffering reactant solution being contained in crystallizing field or other expectation longitudinal region any Dual purpose on face.
Alternatively, the relative lateral edge portion of web can be by the elevator including Special-purpose lifting structure Structure promotes, and its main purpose is supporting web edge and contains buffering reactant solution rather than conveying width Material.Such as, as described in the diagram, Special-purpose lifting structure can include being similar to conveying roller 42 Mode substantially over web lateral dimension extend but do not play the horizontal lifting of the effect of conveying roller Structure 50.Horizontal lifting structure 50 has recessed horizontal section, so that the horizontal section of web is configured to Be enough to contain the solution of any deposition but do not rotate.Lift structure 50 can be arranged longitudinally at such as two The one or more rollers described in fig. 2 maybe can be replaced between individual conveying roller 42.
Other hoisting mechanisms a lot of are in the range of current teaching.Such as, as it is shown in figure 5, promote Web edge and may or may not be able to be rotatable by making the relative lateral edge portion of web One or more supporting surfaces 52 contact realize.In order to promote marginal portion, support surface one As will somewhat be arranged in the horizontal boundary of web.Supporting surface 52 can be approximately frustum of a cone, As described in Figure 5, or alternatively, supporting surface can be spherical, cylinder or be suitable for Other shape any in the marginal portion fully promoting and supporting web.Such as, can use have many Supporting surface in a kind of shape and/or the complicated shape with recessed geometry.At some embodiments In, the shape with inwardly or outwardly cambered surface is probably favourable.Additionally, relatively shallow slope or many Individual/slope can be less sensitive to web edge change continuously, the most still maintains holding back of reaction solution System.Do not consider its structure, supporting surface may be arranged at along web longitudinal size Anywhere, And typically will be arranged in crystallizing field interior or near.Such as, as described in fig. 8, two relative Supporting surface is to may be arranged between adjacent conveyor roller.
As described in figure 6, hoisting mechanism can include being attached to the angled of one of conveying roller 42 Marginal portion or supporting surface 52 '.Although with the elevator described in figure 3 in a lot of aspects Structure is similar to, and the mechanism described in figure 6 can have simpler structure, because angularly edge part Divide 52 ' can be manufactured dividually with cylindrical delivery roller 42.Fig. 7 describes another alternative, wherein Special-purpose lifting structure 52 " include being configured to the angled limit that promotes the lateral edge portion of substrate web Edge portion.Support in the case of surface 52 such as describe in Figure 5, lift structure 52 " the most direct It is attached to conveying roller 42, but more properly may be arranged between such as adjacent roller and by as shown in Figure 8 Individually supporting structure supporting.
It should be understood that all hoisting mechanisms described in Fig. 3-8 include being shaped as and meet substrate width The lift structure of the marginal portion promoted of material.Such as, the lift structure bag described in figures 3-4 Include the recessed lift portion at its transverse edge, and the lift structure described in fig. 5-7 include away from The substantially planar lift portion that the core of substrate web is at an angle.On the contrary, some are existing Hoisting mechanism use vertical rails or bar, it is shapeless by meeting promoted marginal portion, with lifting Basal edge.The shape making lift structure can such as provide with the form fit of the marginal portion promoted Friction in a small amount, it reduces the core distortion of web or otherwise from inclining that substantially planar degree deviates To, this causes less solution to overflow, at suprabasil solution layer evenly and the most more consistent Chalcogenide layer.
The lateral edge portion promoting web can be performed by fixed amount, and lifting can be in certain limit Lifting capacity in be adjustable.Using the Special-purpose lifting knot of the near lateral boundaries being arranged in web Structure the most respectively in Fig. 5 and 7 describe structure 52 and 52 " embodiment in, can lead to simply The height overregulating lift structure regulates to realize any desired lifting.The horizontal of web is crossed using Size extends and has in the Special-purpose lifting structure of recessed horizontal section or the embodiment of conveying roller, promotes Regulation can realize by changing the horizontal section of lift structure or roller.Such as, if recessed Special-purpose lifting Structure or recessed conveying roller are segmented in lateral dimension, and the height of the most various sections can be individually or in groups It is conditioned, until expectation horizontal section is reached the marginal portion providing web relative in web Till the desired amount of the lifting of heart part.
In order to maintain the relatively flat on the whole core of web section this be probably Sizable uniformity institute of the cushion that realization is deposited is desirable, and web can be at one or many Individual position is compacted and/or under tension.The convenient mode realizing this is to maintain web with defeated At least subset sending roller or other conveying mechanism contacts.Such as, as described in figures 9-10, web Can multiple hold-down rollers or wheel 54 (or be configured to keep web contact with conveying mechanism any other tie Structure) under pass through, the most each contact roller be configured to keep relevant to conveying roller 42 one of web A part contact.Compressing structure is such as taken turns or roller may be arranged at each marginal portion of each conveying roller Near, or as shown in Figure 10, compressing structure may be arranged in layout alternately, a contact roller cloth Put near the single marginal portion of each conveying roller.Generally, any layout of compressing structure is probably Suitable, it is assumed that structure be enough under enough pulling force keep web so that its core maintains Expect horizontal section.
In addition to applying downward power and contacting with conveying roller with holding web, compressing structure also can have Other useful features various.Such as, as described in fig .9, compressing structure can be mounted in There is the balance weight wheel 54 on the bar 56 of central pivot 58.The balance weight 60 of each structure can Be in groove 62 adjustable so that at proximal direction (towards wheel 54) upper shifting balance weight Hammer increases the wheel power against web, and reduces at distal direction (away from wheel 54) upper shifting balance weight Power against the wheel of web.Therefore adjustable downward force is provided web by this mechanism, so that The upward force skew of the hoisting mechanism in web.Alternatively, contact roller can pneumatically or by any its Its suitable mechanism provides and can control or predetermined pressure.Additionally, other structure, such as, it is arranged on solid Pressurization Tai Fulong pipe/pad on fixed structure or be arranged in the low fricting strip above and below web or torr Frame or be arranged in the Magnet under web, can be used for providing in check compaction pressure to web.
Additionally, as described in figures 9-10, the wheel of compressing structure or roller can be the most outside Be somewhat at an angle, with to web provide have relative to web core downwardly and outwardly The power of component.The outside component of power carries to web when being applied in the relative edge part office of web For lateral pull and therefore to assist in keeping the core of web smooth, this horizontal stroke being easy to again cross web To direction cushion reactant (with thus cushion itself) relatively uniform distribution.Additionally, Contact roller can be the most at an angle relative to the longitudinal size of web, any of which angle Also helpful outward force can be provided to web.Above-mentioned angle is the most all adjustable Joint, to allow the change of the horizontal section of left-to-right pulling force in web and/or web.
Figure 11 is for showing through the part of the device of crystallizing field transport substrate web (not shown) Meaning property plane graph, it illustrates the positioned opposite of conveying roller 42, lift structure 52 and hold-down mechanism 54. Although Figure 11 describes with vertical axis, the lift structure 52, Ying Li of the form on frustum of a cone supporting surface Solve, these can with various other shapes of lift structures such as in Fig. 4,6 or 7 description that A little lift structures replace.Lift structure is each can such as include recessed lift portion, center away from web Substantially planar lift portion that part is at an angle or be formed to conform to the edge of lifting of web Certain other structure of part.In order to provide the lifting of desired amount, each lift structure can have one Adjustable upright position in determining the lifting capacity of scope.As depicted in fig. 11, lift structure can be arranged Between adjacent conveyor roller 42, and the knot of each lateral edge portion office at device can be arranged to Structure pair.Alternatively, as such as described in Fig. 3 and 6, lift structure can be overall with conveying roller Ground is formed or is directly connected to conveying roller, or as described the most in the diagram, lift structure can be Substantially over substrate web lateral dimension extend application specific architecture and do not play the effect of conveying roller.
The characteristic measured by thin film buffer layer that may be in response to be formed by reactant solution performs to carry Rise one or more marginal portions of web.Such as, may be in response to the survey of the uniformity of thin film buffer layer Amount regulates the amount of the lifting on the one or both sides of web.If cushion is measured at crosses width The lateral dimension of material is arranged asymmetrically, then the amount of scalable lifting on only side, until extensive Till sizable symmetry of multiple cushion.If cushion is measured at enough symmetrical, but court The undesirably edge thick, towards the lateral dimension of web, center of the lateral dimension web does not conforms to Need thin, then the amount of scalable lifting on these both sides, until reaching the bigger of buffer layer thickness Till horizontal homogeneity, vice versa.Similarly, if measuring (or only visual inspection) and referring to Show that one or more solution does not has enough to be arrived by containment the top surface of web, the side in web can be increased Or the amount of the lifting on both sides, as to necessary to containment reactant solution.
Figure 12 be describe generally with 100 instruction Film Flow is belonged to compound buffer layer deposition to flexibility The flow chart of suprabasil method.In step 102, the web of film base material is in a longitudinal direction Carried through crystallizing field.As elucidated before, base material can include basic substrate, the most stainless The thin plate of Steel material, one or more thin layers have been deposited on this thin plate.Such as, by conduction material Expect the back contact layer of such as molybdenum structure and inhaled by the p-type semiconductor photon of material such as CIGS structure Acceptor layer may have been deposited in basic substrate.Should be understood that substrate web can include these layers, when It is when crystallizing field is carried.Web generally roll-to-roll or other similar during carried, In this case, longitudinal direction will be the direction advanced between loose ends roller and stringing roller.
It is assigned to substrate web in step 104, pregnant solution and the solution containing chalcogen On top surface.Pregnant solution comprises the known gold reacting to be formed chalcogenide with chalcogen Belong to, and therefore will be generally selected from by copper, silver, gold, zinc, cadmium, hydrargyrum, lead, boron, aluminum, gallium, indium Group with thallium composition.Solution containing chalcogen comprises the group selecting free oxygen, sulfur, selenium and tellurium to form also And to be formed, be there is expectation optics and/or electricity by known react with metal in pregnant solution The chalcogen of the chalcogenide of sub-feature.One example combinations is that cadmium is combined to produce sulfuration with sulfur Cadmium, but other chalcogenide can be suitable as cushion and/or n-type semiconductor layer.In step Before 104 or as the part of step 104, substrate web can with deionized water or certain other suitable When solution rinse.This flushing removes surface irregularity or from existing deposition process Other artifact that (such as CIGS deposition) stays, and therefore the phase of chalcogenide deposition is provided To more consistent surface.
It should be understood that pregnant solution and the solution containing chalcogen can distribute appointing in crystallizing field At what desired locations.Such as, solution can be distributed by single allotter 38, together as retouched in fig. 2 Paint, or solution can be distributed by single allotter.These allotters can separate foot in a longitudinal direction Enough distances, such as one inch or more, to allow metal in pregnant solution and first The suitable surface between the floor below the photovoltaic material in district between position and the second position Ion exchanges.This can have the electricity to the semiconductor layer (such as cigs layer) below PV battery The beneficial effect of sub-feature.Alternatively, single allotter can be in the position punishment that can substantially overlap Joining reactant solution, i.e. pregnant solution and the solution containing chalcogen can be individually dispensed, but At the lengthwise position being substantially the same in substrate web.
Additionally, pregnant solution and/or the solution containing chalcogen can be heated sufficiently to provide at The temperature of the considerable fraction of heat of the reaction that the chalcogenide in web is formed.Correspondingly, reaction One or two temperature in thing solution is typically larger than the temperature (coating at solution of the web of movement Before).Such as, pregnant solution can be heated at the temperature in the range of 55-70 degree Celsius, And before the coating of reactant solution, web can have the temperature in the range of 25-45 degree Celsius.
In step 106, the lateral edge portion of substrate web is elevated relative to the core of web, Will at least be contained in substantially on the top surface of web containing metal and the solution containing chalcogen.As The previously described, this such as can be arranged near the lateral edge portion of substrate many by hoisting mechanism Making for realizing of individual lift structure.These structures can take any suitable form, such as at Fig. 3-8 The form of middle description.Arrangements lifting structure may with the shape meeting the marginal portion promoted of substrate Being favourable, because this can prevent the localization power of the adjacent edges in substrate, it may result in web Core in buckle or other vertical inhomogeneities.
In step 108, the core of web keeps substantially planar.This can be by keeping web Selected part contacts with lower floor conveying mechanism such as lower floor's conveying roller and realizes.Such as, as at Figure 10 Middle description and recited above, keep web to contact with conveying mechanism and can include making web in multiple pressures Passing through under bearing up pulley 54, the most each wheel is configured to keep web to contact with one of conveying roller 42.As Figure 10 is described, and hold-down roller can be arranged on conveying roller in layout alternately, and can configure Basad web supply is become to have the adjustable force of downward and/or outside component.The downward component of power is used for Keep web downward at its adjacent edges, and the outside component of power is for keeping the core of web Under tension, this may result in the flatness in core more or adjustable degree. Therefore, the degree contained to regulate solution maintains the sizable of the core of substrate web simultaneously Flatness, the amount of the vertical-lift at the edge of web, is pressed downward against clamp force at the adjacent edges promoted All can be conditioned with lateral web pulling force.
Alternatively, can be by making web one or more pairs of be made up of low-friction material such as Tai Fulong Between longitudinally oriented strip, the core by realizing keeping web is smooth, and wherein bar is configured to press expectation Clamp force or pressure are applied to the district of substrate.As another alternative, Magnet can be used for executing downward force It is added in one or more districts of substrate.Such Magnet can such as be arranged in the longitudinally oriented strip under substrate On, contact with the bottom of web or distance known to a section from the bottom of web.
Figure 13 be describe generally with 200 instruction for through crystallizing field transport substrate web 202 The perspective view of another device.System 200 is generally similar to describe in fig. 11 and system described above System, because multiple conveying roller 204 is through crystallizing field transport substrate web 202, lift structure 206 simultaneously Promote the marginal portion of web with the solution being contained on the top side of web.As elucidated before, conveying Device 200 may also include of the sizable flatness in the core being configured to maintain web Individual or multiple hold-down mechanisms (not figure 13 illustrates), solution deposition is in core.
Device 200 is different from foregoing example, because lift structure 206 is non-vertically oriented Cylinder, each relative to the plane defined by the flat central portion of web around non-perpendicular at certain Under angle, the axle of orientation rotates.Because each lift structure 206 has constant radius, this is arranged The each part causing the surface of each lift structure moves with equal point-to-point speed.This can have excellent In some advantage of the frustum of a cone lift structure described the most in Figure 5, promote knot at frustum of a cone In structure, the radius of change causes the different point-to-point speeds along frusto-conical surface.Such as, it is being more than The frustum of a cone lift structure contacting web at one point can produce undesirable rubbing in web Wiping and/or shearing, it is avoided by the most cylindrical lift structure 206.
Figure 14 be describe generally with 200 instruction for through crystallizing field transport substrate web 222 The perspective view of another device.It is not used in crystallizing field the conveying roller below web to carry width Material, system 220 includes that lower floor supports surface 224, and web is slided on supporting surface 224.Surface 224 are depicted as substantially planar, but it can be given small radius in some cases, with Allow downward force by easier applying in whole crystallizing field.Surface 224 is typically by allowing web relative The low-friction material structure easily slided.
System 220 also includes marginal portion and the most actively rotation being configured to promote web Turn to carry the lift structure 226 of web.In other cases, web can be with certain other side Formula carries, such as by the rotation of the end volume in reel-to-reel system and/or by outside crystallizing field Other cylindrical rotation (web is passed through on cylinder).Lift structure 226 in fig. 14 by Being depicted as non-vertically oriented cylinder, as in fig. 13, but any suitable lift structure can Coupling apparatus 220 uses, including before in the disclosure shown in and described those devices.
Device 220 also includes being configured on expected degree protect the center deposition district of substrate web always Hold the hold-down mechanism on surface 224.In this case, hold-down mechanism includes being arranged in surface 224 Under, multiple in the chamber suitably shaped that such as formed in the structure define this surface or hole 230 Magnet 228.These chambeies or hole can be arranged, with in substrate web along the length of crystallizing field with an interval Any desired downward force of upper offer.In order to maintain sizable flatness on surface 224 and in order to limit Arriving the quantity of the fluid of Magnet, as described in fig. 14, supporting surface 224 can be formed The top surface of lower floor's supporting structure, and chamber 230 can be formed in the basal surface of supporting structure.Therefore, Magnet 228 may be arranged under surface 224 and very close to surface 224, but the thin layer of material is by Magnet From surface 224 with thus separate from substrate web 222.
Magnet 228 can such as be constructed by the material such as SmCo (SmCo) of relatively high magnetic.SmCo The most anti-demagnetization, and also can stand in device 220 and around expected from relatively high temperature and humidity. As described in fig. 14, the use of Magnet 228 may result in the degree desirably of substrate web Flatness, and hold-down mechanism need not directly contact web, such as, compression as previously depicted In the case of wheel.
Figure 15 be describe generally with 240 instruction for through thin film chemical deposition district transport substrate The perspective view of another exemplary means of web 242.Conveyer device 240 is similar in terms of major part The device 220 described in fig. 14, including underlying surfaces 244, (substrate is configured at this underlying surfaces On 244 slide), again take the lift structure 246 of angled cylindrical form and be arranged in table Magnet 248 in face 244 hole under 250.But, due to generally with 252 instruction at table The interpolation of the pattern of the removal of material formed in face 244, device 240 is different from device 220.
Generally reduce on surface from the pattern such as pattern 252 of the material removed in web table below face And the contact area between web, this reduces friction when web carries on surface.At Figure 15 The pattern 252 of middle description is included in multiple position intersection to form two groups of parallel grooves of argyle design 254、256.More generally, the contact area reduced between web and underlying surfaces provides right simultaneously Web enough support removal of material to maintain substantially planar shape in the central region It is suitable that any pattern is probably.
Figure 16 be generally with 260 instruction for through thin film chemical deposition district transport substrate web The perspective view of the another exemplary means of 262, and Figure 17 is the profile intercepted along line 17-17. Device 260 includes underlying surfaces 264 (substrate web is slided on underlying surfaces 264), and multiple recessed Groove 266 is arranged in surface 264 to reduce contact area and thus rubbing between surface and web Wipe.Include the hole 268 being configured to receive multiple Magnet 270 in surface 264 structures below, it is used Make hold-down mechanism so that substrate web keeps relatively flat against underlying surfaces.
Device 260 also includes cover layer or lid 272, and it covers crystallizing field and therefore improves at substrate width Fluid containment on the top surface of material.Additionally, lid 272 can be the most air-locked, cause at lid And little in the district between the fluid reacted in web but can the vapour pressure of increase of measurable amount Power and the downward pressure accordingly increased in substrate web.Typically, being always pressed downward against in web Power (it is the sum of reaction-ure fluid pressure and steam pressure) is monitored and controls to expected degree.Example As, total downward pressure is controlled in the range of 0.4 0.8 millibars, or is set to about 0.6 Millibar.This can be such as by controlling reaction-ure fluid height on substrate and/or by using dust discharge Floating gate regulation realizes from the steam of crystallizing field and the discharge of gas.
Lip 274 can be formed on every side of crystallizing field and under lid 272 in a device, to work as Every side of substrate was maintained in desired locations and orientation when crystallizing field moves by substrate.This type Configuration can those lift structures more foregoing than integrated other type of lift structure with Cover 272 more convenient.But, in principle, any lift structure can be by the most air-locked blanketing Lid.
There is provided the water manifold 276 of the heating being in fluid communication with groove 266, in order to groove and in substrate Lower supply water.Water in manifold 276 can be pressurized and heated to any desired degree.Correspondingly, From manifold water produce generally with 278 instruction hydrostatic supporting surfaces, its can be used for by Downward pressure in substrate web equilibrates to expected degree and/or web is heated to preferred temperature.
Supporting surface 278 is used to provide upward force can be obviously reduced at substrate 262 and underlying surfaces 264 Between friction, or the most substantially eliminate friction, if be applied in web by supporting surface 278 Total downward pressure of being controlled as approximately equal in web of upward pressure.Additionally, by controlling The temperature of the water in manifold 276, can control the temperature of substrate.In some cases, this can be ratio Use and be arranged in heater dedicated more convenient near substrate and/or temperature-controlled process accurately.
Figure 18 is to describe, according to currently instruct, thin film chalcogenide buffer layer is deposited to flexible substrate On generally with the flow chart of other method of 300 instructions.
In step 302, method 300 includes by sliding on the supporting surface in being arranged in crystallizing field The web of dynamic film base material carries this web through crystallizing field.As it was previously stated, supporting surface can Constructed so that substrate web motion on surface by low-friction material.Additionally, supporting surface can Including being configured to reduce the removal of material of the area of the contact between supporting surface and web Pattern, the most multiple grooves.
In step 304, method 300 include provide web and supporting surface at least part of between The step on hydrostatic supporting surface.Such as, water can be introduced in the thin layer on the top on supporting surface In and/or the pattern of removal of material in, to reduce further rubbing between supporting surface and substrate Wipe.Additionally, water can be heated to preferred temperature, controlled before reactant solution is introduced into provide The method of the temperature of substrate.Can be arranged to and supporting surface and/or from the material that removes of supporting surface The water manifold of pattern fluid communication performs heating, and water then can the pattern of removal of material with Circulate between the water manifold of heating or be otherwise transported to support surface.
In step 306, method 300 includes chalcogenide reactant solution is assigned to substrate web On top surface.Such as, step 306 can include sinking pregnant solution and the solution containing chalcogen Amass on the top surface of web, pregnant solution comprise from by copper, silver, gold, zinc, cadmium, hydrargyrum, The metal selected in the group of lead, boron, aluminum, gallium, indium and thallium composition, and the solution containing chalcogen Comprise the chalcogen from the group selection being made up of oxygen, sulfur, selenium and tellurium.Specifically, in certain situation Under, step 306 can include being assigned on the top surface of web the solution of the solution containing cadmium and sulfur-bearing with Form cadmium sulfide.
In step 308, method 300 includes the widthwise edge promoting web relative to the core of web Edge portion is with at least some of of the pregnant solution that is contained on the top surface of web with containing chalcogen The solution of element at least some of.As it was previously stated, this can exist by making the lateral edge portion of web By realizing on multiple angled cylinders.In some cases, these angled cylinders Body can be configured to rotate together along with the motion of web, and in other cases, angled cylinder Can be constructed by low-friction material, and can be configured to maintain fixing position of rotation when web moves.
In step 310, method 300 includes using the fixed bit being arranged under the center of web Multiple Magnet in putting are substantially planar to the core keeping web.Such as, samarium cobalt magnet can cloth Put in the chamber formed in the basal surface of supporting structure.Therefore, Magnet may be disposed to very close to top support Surface and substrate, and do not affect flatness and not unnecessary to reactant solution on supporting surface Expose.
The disclosure being set forth above can include the multiple different invention with independent utility.Although these Each in invention is disclosed in its preferred form, as disclosed herein and shown in its particular implementation Mode should not be considered in restrictive, sense, because many variations is possible.The theme bag of invention Include all novelties of various element disclosed herein, feature, function and/or characteristic and non-obvious Combination and sub-portfolio.The claim numbered below particularly points out and is considered novel and non-obvious Some combination and sub-portfolio.It is embodied in other combination and subgroup of feature, function, element and/or characteristic Invention in conjunction can be claimed from this or the application of related application CLAIM OF PRIORITY.Such power Profit require in spite of be exclusively used in different inventions or same invention and yes/no ensuing Just the scope aspect of the claim of numbering is wider, narrower, equal or different, is considered as being included In the theme of the invention of the disclosure.

Claims (20)

1. thin film chalcogenide buffer layer is deposited to the method in flexible substrates, including:
Come through institute by the web of slide base material on the supporting surface in being arranged in crystallizing field State crystallizing field and carry described web;
By pregnant solution and the solution deposition containing chalcogen on the top surface of described web, institute State pregnant solution to comprise from by copper, silver, gold, zinc, cadmium, hydrargyrum, lead, boron, aluminum, gallium, indium With thallium composition group in select metal, and the described solution containing chalcogen comprise from by oxygen, sulfur, The chalcogen of the group selection of selenium and tellurium composition;
The lateral edge portion of described web is promoted, with by described relative to the core of described web At least some of and at least some of essence of the described solution containing chalcogen of pregnant solution On be contained on the described top surface of described web;And
The multiple Magnet being arranged in the fixed position under the core of described web are used to protect The described core holding described web is substantially planar.
2. the method for claim 1, wherein by make described web multiple angularly By promoting the described lateral edge portion of described web on cylinder.
3. method as claimed in claim 2, wherein said angled cylindrical configuration become along with The motion of described web rotates.
4. method as claimed in claim 2, wherein said angled cylinder is by low friction material Material structure, and be configured to when described web moves maintain fixing position of rotation.
5. the method for claim 1, wherein said supporting surface includes being configured to reduce Multiple grooves of the area of the contact between described supporting surface and described web.
6. the method for claim 1, also includes providing at least portion on described supporting surface Divide the hydrostatic supporting surface between described web.
7. method as claimed in claim 6, wherein said supporting surface includes being configured to reduce Multiple grooves of the area of the contact between described supporting surface and described web, and wherein said liquid Body static(al) supporting surface is formed by the water being arranged in described groove.
8. thin film chalcogenide buffer layer is deposited to the method in flexible substrates, including:
Warp is carried out by the web of sliding film base material on the supporting surface in being arranged in crystallizing field Cross described crystallizing field and carry described web;
By pregnant solution and the solution deposition containing chalcogen on the top surface of described web, institute State pregnant solution to comprise from by copper, silver, gold, zinc, cadmium, hydrargyrum, lead, boron, aluminum, gallium, indium With thallium composition group in select metal, and the described solution containing chalcogen comprise from by oxygen, sulfur, The chalcogen of the group selection of selenium and tellurium composition;
The lateral edge portion of described web is promoted, with by described relative to the core of described web At least some of and at least some of essence of the described solution containing chalcogen of pregnant solution On be contained on the described top surface of described web;
The described core keeping described web is substantially planar;And
Hydrostatic supporting table between at least part of and described web on described supporting surface is provided Face.
9. method as claimed in claim 8, wherein said hydrostatic supporting surface includes from water Manifold is transported to the thin layer of the water in the district between described web and supporting surface.
10. method as claimed in claim 8, also includes by controlling described hydrostatic supporting table The temperature in face controls the temperature of the described web in described crystallizing field.
11. methods as claimed in claim 8, the material that wherein said supporting surface includes removing Pattern, described pattern is configured to reduce the face of the contact between described supporting surface and described web Amass, and wherein said hydrostatic supporting surface is formed by the water being arranged in described pattern.
12. methods as claimed in claim 11, wherein the described pattern of removal of material includes The multiple grooves formed in described supporting surface.
13. methods as claimed in claim 11, also include by being arranged in described pattern Water is heated to preferred temperature to control the temperature of described web.
14. methods as claimed in claim 13, wherein heat described water and include making described water in institute The described pattern of the material removed and and described pattern fluid communication heating water manifold between circulate.
Film cadmium sulfide semiconductor layer is deposited to the method in flexible substrates by 15. 1 kinds, including:
Warp is carried out by the web of sliding film base material on the supporting surface in being arranged in crystallizing field Cross described crystallizing field and carry described web;
Cadmium-containing solution and sulphur-containing solution are assigned on the top surface of described web;
The lateral edge portion of described web is promoted with by every kind relative to the core of described web The substantial portion of solution is contained on the described top surface of described web;And
Use the multiple Magnet being arranged on the fixed position under the described core of described web The described core keeping described web is substantially planar.
16. methods as claimed in claim 15, wherein by making described web multiple angled Cylinder on by promoting the described lateral edge portion of described web.
17. methods as claimed in claim 15, wherein remove the figure of material from described supporting surface Case is to reduce the area of the contact between described supporting surface and described web.
18. methods as claimed in claim 17, also include providing on described supporting surface at least Hydrostatic supporting surface between part and described web.
19. methods as claimed in claim 18, wherein said hydrostatic supporting surface is by arranging Water in the described pattern of removal of material is formed.
20. methods as claimed in claim 15, wherein said supporting surface is formed supporting knot The top surface of structure, and the chamber that wherein said magnet arrangements is formed in the basal surface of described supporting structure In.
CN201480068296.9A 2013-12-16 2014-12-15 Solution containment during buffer layer deposition Expired - Fee Related CN105980067B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US14/108,193 2013-12-16
US14/108,193 US9252318B2 (en) 2008-03-05 2013-12-16 Solution containment during buffer layer deposition
PCT/IB2014/003099 WO2015092543A2 (en) 2013-12-16 2014-12-15 Solution containment during buffer layer deposition

Publications (2)

Publication Number Publication Date
CN105980067A true CN105980067A (en) 2016-09-28
CN105980067B CN105980067B (en) 2018-08-28

Family

ID=53403833

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201480068296.9A Expired - Fee Related CN105980067B (en) 2013-12-16 2014-12-15 Solution containment during buffer layer deposition

Country Status (2)

Country Link
CN (1) CN105980067B (en)
WO (1) WO2015092543A2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110344032A (en) * 2018-04-03 2019-10-18 环球太阳能公司 For film to be deposited to the system and method in flexible substrates

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4371217A (en) * 1980-06-30 1983-02-01 Zavody Tazkeho Strojarstva, Narodni Podnik Hydrostatic sliding element
US5980110A (en) * 1998-07-10 1999-11-09 Thomson Industries, Inc. Manifold for self-compensating hydrostatic bearing with integral compensators
US20070169809A1 (en) * 2004-02-19 2007-07-26 Nanosolar, Inc. High-throughput printing of semiconductor precursor layer by use of low-melting chalcogenides
US20100086699A1 (en) * 2008-03-05 2010-04-08 Global Solar Energy, Inc. Solution containment during buffer layer deposition
TW201339447A (en) * 2011-11-25 2013-10-01 Oiles Industry Co Ltd Air slide device

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4798478A (en) * 1988-02-16 1989-01-17 Nicolet Instrument Corporation Self-aligning fluid bearing
US8062922B2 (en) * 2008-03-05 2011-11-22 Global Solar Energy, Inc. Buffer layer deposition for thin-film solar cells
US8277869B2 (en) * 2008-03-05 2012-10-02 Global Solar Energy, Inc. Heating for buffer layer deposition
WO2011143275A2 (en) * 2010-05-10 2011-11-17 Nanosolar, Inc. Thin film buffer layer solution deposition assembly

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4371217A (en) * 1980-06-30 1983-02-01 Zavody Tazkeho Strojarstva, Narodni Podnik Hydrostatic sliding element
US5980110A (en) * 1998-07-10 1999-11-09 Thomson Industries, Inc. Manifold for self-compensating hydrostatic bearing with integral compensators
US20070169809A1 (en) * 2004-02-19 2007-07-26 Nanosolar, Inc. High-throughput printing of semiconductor precursor layer by use of low-melting chalcogenides
US20100086699A1 (en) * 2008-03-05 2010-04-08 Global Solar Energy, Inc. Solution containment during buffer layer deposition
TW201339447A (en) * 2011-11-25 2013-10-01 Oiles Industry Co Ltd Air slide device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110344032A (en) * 2018-04-03 2019-10-18 环球太阳能公司 For film to be deposited to the system and method in flexible substrates

Also Published As

Publication number Publication date
CN105980067B (en) 2018-08-28
WO2015092543A3 (en) 2016-01-07
WO2015092543A2 (en) 2015-06-25

Similar Documents

Publication Publication Date Title
US9673348B2 (en) Buffer layer deposition for thin-film solar cells
US8609182B2 (en) Solution containment during buffer layer deposition
US9640705B2 (en) Feedback for buffer layer deposition
TW201513380A (en) A high efficiency stacked solar cell
US8277869B2 (en) Heating for buffer layer deposition
CN104169459B (en) Form the system of photovoltaic cell on flexible substrates
Suemasu et al. Recent Progress Toward Realization of High‐Efficiency BaSi2 Solar Cells: Thin‐Film Deposition Techniques and Passivation of Defects
KR101324292B1 (en) High efficiency solar cell and manufacturing method thereof, and solar cell manufacturing apparatus for the same
AU2019358874B2 (en) Method of forming a perovskite film for an optoelectronic device
JP2003124487A (en) Production equipment for solar cell
EP3723118B1 (en) Apparatus for immersion-based preparation of perovskite thin film, use method and application thereof
Wang et al. Double open-circuit voltage of three-dimensional ZnO/CdTe solar cells by a balancing depletion layer
US9252318B2 (en) Solution containment during buffer layer deposition
CN105980067A (en) Solution containment during buffer layer deposition
CN104241439A (en) Method for preparing cadmium telluride thin-film solar cell
Valdés et al. Electrodeposition of CuInSe2 and In2Se3 on flat and nanoporous TiO2 substrates
JP2009114481A (en) Method for forming electrodeposition film, thin film solar cell, and method for manufacturing the same
JP6635934B2 (en) Back contact type Si thin film solar cell
Balashangar et al. The effect of surface roughness of substrates on the performance of polycrystalline cadmium sulfide/cadmium telluride solar cells
CN115863476A (en) Reel-to-reel chemical spraying deposition equipment for buffer layer of copper indium gallium selenide solar cell
CN112695277A (en) Deposition heat treatment equipment for flexible copper indium gallium selenide thin-film solar cell
Salazar et al. Low cost fabrication of semiconducting materials for photovoltaic applications
KR20120074188A (en) Apparaus for manufacturing thin film and manufacturing for operating the same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180828

Termination date: 20191215