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WO2013030088A1 - Dispositif et procédé de revêtement d'un substrat - Google Patents

Dispositif et procédé de revêtement d'un substrat Download PDF

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Publication number
WO2013030088A1
WO2013030088A1 PCT/EP2012/066424 EP2012066424W WO2013030088A1 WO 2013030088 A1 WO2013030088 A1 WO 2013030088A1 EP 2012066424 W EP2012066424 W EP 2012066424W WO 2013030088 A1 WO2013030088 A1 WO 2013030088A1
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WO
WIPO (PCT)
Prior art keywords
substrate
mass flow
coating
coating material
temperature
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.)
Ceased
Application number
PCT/EP2012/066424
Other languages
German (de)
English (en)
Inventor
Dieter Schmid
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.)
Dsetec & Co KG GmbH
Original Assignee
Dsetec & Co KG GmbH
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 DE102011053049A external-priority patent/DE102011053049A1/de
Priority claimed from DE102011053050A external-priority patent/DE102011053050A1/de
Application filed by Dsetec & Co KG GmbH filed Critical Dsetec & Co KG GmbH
Priority to EP12750595.6A priority Critical patent/EP2748839A1/fr
Publication of WO2013030088A1 publication Critical patent/WO2013030088A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0623—Sulfides, selenides or tellurides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02614—Transformation of metal, e.g. oxidation, nitridation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02623—Liquid deposition
    • H01L21/02625—Liquid deposition using melted materials

Definitions

  • the invention relates to a device and a method for coating a substrate according to the preambles of the independent claims.
  • chalcogens such as selenium or sulfur
  • a substrate deposited on a metallic precursor layer (precursor layer) with metals such as copper, indium, gallium, aluminum, zinc, tin diffuse and to react.
  • Various methods are known for applying the chalcogens. The de
  • Semiconductor formed which is not doped by foreign elements, but via vacancies of the chalcogens and / or reversed occupied lattice sites of the metals in the semiconductor grid formed.
  • the density of vacancies and thus essential properties of the semiconducting material can be controlled by the activity of the chalcogens.
  • Such reactions between chalcogen and metal can occur not only in vacuum but also under atmospheric conditions and usually take place in an oven with a more or less complete reaction space.
  • a substrate with applied precursor layers and selenium or sulfur is heated to temperatures around 500 ° C and maintained at elevated temperature during the reaction.
  • Substrate temperature selected so that the partial pressure of selenium or sulfur over the substrate is always lower than its vapor pressure at the current substrate temperature.
  • the partial pressure is over the temperature of Selential. Sulfur source set.
  • DE 10 2009 01 1 496 describes a process for the production of chalcogen semiconductors for photovoltaic applications, which is carried out at atmospheric pressure, in which in a sequential process on a metallic precursor layer selenium from a mixture of carrier gas and selenium vapor at room temperature in solid phase deposited and then exposed to sequentially increasing temperatures and melted. The excess chalcogen is returned to the deposition process along with the carrier gas.
  • the object of the invention is to provide a fast, efficient and precise method for coating a substrate with chalcogen.
  • Another object is to provide a device suitable for this purpose.
  • the invention relates to a coating apparatus for producing chalcogen semiconductors for photovoltaic applications, comprising a process area in which a substrate for coating with a chalcogen-containing coating material is at least temporarily stored at a substrate position, and comprising a material source for the coating material and comprising a conveying device with which the coating material can be conducted in a mass flow from the material source at least to the substrate position. It is proposed that the coating device is set up in such a way that the coating material condenses on the substrate by means of vapor-phase condensation in a liquid phase.
  • the coating system can be designed such that the coating material can be brought into contact, optionally in a liquid phase or in a gas phase, with the substrate. Due to the fact that the coating material reaches the substrate in a liquid phase, advantageously a high chemical activity, in particular of chalcogens in the liquid phase, can be achieved.
  • a high chemical activity in particular of chalcogens in the liquid phase
  • the properties of the semiconductor formed can be adjusted in a targeted manner via the number of vacancies.
  • the activity can be actively influenced. It can also be specified specifically, which reaction path is taken in the formation of layers, namely whether a solid-liquid phase reaction or a solid-state gas-phase reaction takes place.
  • a substrate temperature in a predetermined range can be adjusted in a targeted manner by the vapor phase condensation.
  • the substrate temperature can be homogenized on the substrate surface by the vapor phase condensation. In cold areas, more coating material condenses, so that more condensation heat is introduced there, while in warmer surface areas less condensation takes place and less heat of condensation is introduced into the condensing coating material.
  • a dew point of the coating material provided at the substrate position may be adjustable, in particular controllable.
  • an adjusting device can be provided for this purpose with which a dew point of the coating material provided at the substrate position can be adjusted.
  • a concentration and / or quantity of the coating material provided at the substrate position may be adjustable, in particular controllable. The combination of dew point control and vapor phase condensation is particularly advantageous.
  • the substrate position may be formed as a stationary position in the process area or may be non-stationary formed over a range, such as in the manner of a conveyor belt, which transports the substrate through the process area.
  • the process area then corresponds to a continuous furnace with a transport device for one or more substrates.
  • the substrate may itself be formed as a belt which is transported through the oven.
  • the band can be made of metal or plastic, for example.
  • the process area and the material source can be arranged in a common housing. Excess coating material not used in the process area can be routed out of the process area back to the material source and reused. Losses of coating material can be practically limited to the inflow and outfeed of substrates, which expediently these losses can be further minimized by suitable condensation traps or the like.
  • the material source provides the coating material so that it can enter the process area.
  • the material source may be a container with a melt of coating material from which the coating material is evaporated, and / or it may comprise a flash evaporator, and / or it may comprise a circulating belt consisting of a
  • the adjusting device can be designed to provide a degree of saturation of the mass flow of coating material.
  • the availability of the coating material can be set defined on the substrate on the degree of saturation hereby.
  • the saturation level can be defined to a desired value of 0% to 100%.
  • the adjusting device in a flow path of the mass flow between the material source and the
  • the coating material from a material source that is independent of the setting device for the amount and / or concentration of the coating material on the substrate or in the process area.
  • the material source may be virtually unregulated, while the concentration and / or amount of the coating material may be adjusted or regulated independently with high accuracy.
  • the adjusting device may comprise a cooling device for cooling the mass flow.
  • the cooling device allows targeted removal of coating material from the mass flow. Due to the temperature of the cooling device, the amount and / or concentration of the coating material in the mass flow can be reproducibly changed.
  • a dew point of the coating material can be adjusted in the mass flow, in particular regulated.
  • the temperature of the cooling device is adjustable, eg adjustable or controllable.
  • the cooling device may comprise a channel system whose walls can be cooled with a cooling medium.
  • the cooling device may comprise a separating body, such as a plate, which is arranged between a cooler and a heater of the cooling device.
  • the adjusting device may comprise a heating device for heating the mass flow.
  • the heating device can be arranged downstream of the cooling device. By the heater, the mass flow, regardless of the amount and / or concentration of the coating material in
  • Mass flow can be adjusted to a suitable temperature for a reaction in the substrate area.
  • the amount and / or concentration can in particular be selected completely independently of a wall temperature in an environment of the substrate position.
  • the adjusting device may comprise a dew point control of the mass flow.
  • the dew point of the coating material can be regulated.
  • the dew point temperature or dew point is the temperature at which a state of equilibrium of condensing and evaporating liquid is established on a substrate (in the presence of moisture).
  • the dew point temperature is the temperature at which a condensation of the liquid is beginning.
  • one hundred percent saturation of the coating material after the cooling device of the adjustment device can be achieved.
  • the dew point of the mass flow in particular a mixture of carrier gas and coating material, it can be predetermined up to what substrate temperature the coating material can condense on the substrate so that an advantageous liquid-solid reaction of the constituents on the surface of the substrate can take place .
  • the coating material is evaporated in the material source, for example, and absorbs non-sensible heat. If the coating material condenses on the substrate, the heat of vaporization expended for evaporation is released again in the form of a heat of condensation equal in magnitude.
  • energy is transferred directly to the substrate surface through the condensation of the coating material on the substrate surface via heat of condensation, whereby on the one hand any temperature inhomogeneities can be compensated, on the other hand an optimization of the substrate temperature at least on the substrate surface is possible.
  • a dew point sensor can join the cooling device of the adjusting device particularly favorably.
  • the dew point sensor may have a glossy or reflective surface. The surface can be over
  • Temperature control system be temperature variable. On the one hand, this allows the setting of a temperature gradient along the surface. On the other hand, the surface can be adjusted homogeneously to a predetermined temperature. The reflectance of the surface can be evaluated and used to detect the dew point. About the reflectance, the cooling device can be controlled. The combination of cooling device, which determines the temperature of the mass flow, and dew point sensor thus allows an exact control of the amount and / or concentration of the coating material in the mass flow.
  • a conveying device in particular a circulating device, can be provided in order to move the mass flow from the material source at least to the substrate position.
  • the conveyor may be provided downstream of the substrate position.
  • two conveyors e.g. Fans, be provided, one of which is arranged before and after the reaction space.
  • the one conveyor sucks, the other pushes the mass flow.
  • Several conveyors may also be provided, e.g. at the output of the dew point controller and the subsequent heating device as well as at the connection channel between process area and
  • the conveyor advantageously ensures that coating material is present in sufficient quantity above the substrate position.
  • a rotor is provided in a connection channel between the process area and the material source, which is driven from the outside and influences the amount of circulating mass flow.
  • Shaft and rotor blades are preferably formed of a chemically inert material.
  • a circulation can also take place via a plurality of connection channels between the process area and the material source, it being possible for a rotor to be provided in several or all connection channels.
  • Conveyor determines the supply of coating material on the substrate surface.
  • the conveyor can be controlled or controlled.
  • a heating device can be arranged downstream of the substrate position and upstream of the material source in a flow path of the mass flow. This can be a condensation of the coating material on the way back to avoid material source. Losses of coating material can be reduced.
  • the mass flow may comprise a carrier gas.
  • the carrier gas is an inert gas, in particular nitrogen or the like.
  • a heating device can be provided for the substrate.
  • the substrate may be adjusted to a suitable temperature substantially independently of the temperature of the mass flow.
  • the temperature of the substrate surface may be below the dew point of the mass flow or coating material in the mass flow.
  • the coating material then condenses directly on the substrate surface.
  • the amount of condensate can be adjusted in particular by controlling the amount and / or concentration of the coating material at the substrate position, in particular via a dew point control.
  • An additional or alternative favorable control parameter is the substrate temperature during introduction into the process area itself.
  • the reaction between the coating material, eg chalcogen, and any precursor layer, eg a layer with one or more of Cu, In, Ga, Al, Zn, Sn can be influenced, in particular controlled, via the substrate temperature.
  • the duration of the solid state liquid phase reaction between liquid (condensed) coating material and solid precursor material on the substrate can be precisely defined by the one or more control parameters. If appropriate, the reaction of the solid-liquid phase reaction can be converted into a solid-state gas-phase reaction.
  • the substrate can still dwell in the process area. If the substrate temperature is high enough, a further condensation or recondensation of coating material can be effectively prevented.
  • the invention is further based on a method for producing chalcogen semiconductors for photovoltaic applications in a process area of a coating apparatus, in which process area at least temporarily a substrate for coating with a chalcogen-containing coating material is stored at a substrate position. The coating material is in a
  • Mass flow passed from a material source to the substrate position.
  • the coating material condenses on the substrate by means of vapor-phase condensation in a liquid phase.
  • adjusted and / or regulated concentration and / or amount of the coating material and / or the degree of saturation of the mass flow of coating material can be specifically specified which reaction path is taken in the film formation, namely whether a solid-liquid phase reaction or a solid-state gas-phase reaction takes place.
  • the amount and / or concentration and / or the degree of saturation of the coating material can in particular be selected completely independently of a wall temperature in an environment of the substrate position, by regulating the amount and / or concentration via a feedback signal.
  • An undesirable condensation of excess coating material on walls or any exhaust system of the process area can be avoided or at least reduced by suitably selecting the process parameters. This can interruptions of coating processes for maintenance, in particular for the removal of parasitic deposits of the coating material can be reduced.
  • the invention is particularly suitable for the preparation of semiconductors having Group 16 elements (also known as chalcogenes such as selenium or sulfur) and elements of Groups 11 and 13, especially copper, aluminum, indium, gallium.
  • Group 16 elements also known as chalcogenes such as selenium or sulfur
  • the names of the groups refer to the current IUPAC nomenclature.
  • Group 1 corresponds to the former CAS group IB (copper group), group 13 of the former CAS group INA (boron group) and group 16 of the former CAS group VIA (oxygen group).
  • Such semiconductors are also known by the term chalcopyrite semiconductor.
  • the invention is also suitable for the production of kesterite semiconductors such as Cu (Zn, Sn) Se, S, in which elements of group 13, in particular indium and gallium, by elements of groups 12 and 14, in particular zinc and tin, are replaced ,
  • the density of the group 16 elements in the lattice of the semiconductor to be formed can be specifically adjusted and in particular regulated by their availability and chemical activity in the reaction of the individual components to the semiconducting material.
  • the availability of the group 16 elements can advantageously also be adjusted in a targeted manner over the time course of the reaction between the constituents.
  • the substrate temperature can be homogenized on the substrate surface by the vapor phase condensation. In cold areas, more coating material condenses, so that more condensation heat is introduced there, while in warmer surface areas less condensation takes place and less heat of condensation is introduced into the condensing coating material. This is particularly advantageous for large area substrates, particularly in the fabrication of chalcogen semiconductors for photovoltaic applications in which the electrical properties are highly dependent on the local substrate temperature in the fabrication of the semiconductors.
  • the amount of coating material provided on the substrate can be adjusted by a speed of the mass flow.
  • the conveyor can be used and controlled or regulated accordingly.
  • Apparatus and methods are particularly suitable for the production of CIGS semiconductors for photovoltaic applications.
  • Fig. 1 shows an embodiment of a favorable coating device according to the invention
  • Fig. 2 shows an embodiment of an advantageous adjusting device according to the
  • FIG. 3a, 3b different views of a favorable embodiment of a
  • FIG. 1 shows a schematic illustration of an exemplary embodiment of a favorable coating apparatus 100 for producing chalcogen semiconductors for photovoltaic applications.
  • the coating apparatus 100 comprises a process area 10, in which at least temporarily a substrate 20 for coating with a chalcogen-containing coating material 60 is mounted on a substrate position 22, and a material source 50 for the coating material 60 and a conveyor 40, with which the coating material 60 in a mass flow 62 can be conducted from the material source 50 at least to the substrate position 22.
  • the coating device 100 is set up such that the coating material 60 condenses on the substrate 20 by means of vapor-phase condensation in a liquid phase.
  • a dew point of the coating material provided at the substrate position may be adjustable, in particular controllable.
  • the coating material 60 in the following description is a chalcogen, especially selenium and / or sulfur, which reacts with one or more metals such as copper, indium, gallium, aluminum, zinc, tin to form a CIGS semiconductor.
  • metals such as copper, indium, gallium, aluminum, zinc, tin to form a CIGS semiconductor.
  • other substances may be provided.
  • kesterite compounds such as Cu (Zn, Sn) Se, S instead of chalcopyrite, with ZnSn replacing the expensive Ga and In.
  • the coating apparatus 100 has a housing 16 with an inner space 18 which is subdivided into different areas 18a, 18b, 18c, 18d.
  • the preferably heatable material source 50 is arranged, in which a coating material 60 is provided.
  • the coating material 60 is delivered from the material source 50 into the mass flow 62 passing through the various regions 18a-18d.
  • the mass flow 62 is in particular a mixture of an inert carrier gas 64 and the coating material 60.
  • an adjustment device 70 is arranged, with which a quantity and / or a concentration of the coating material 60 in the mass flow 62 can be set or regulated, which can be provided at a substrate position 22.
  • a process area 10 is arranged with the substrate position 22, on which a substrate 20 is mounted.
  • the substrate 20 is simplified for a single substrate or a plurality of substrates.
  • the substrate may be made of glass, metal, semiconductor, plastic or the like.
  • the substrate position 22 may be stationary or have a transport device with which the substrate 20 is moved through the process area 10, eg a conveyor belt.
  • the substrate 20 may itself be a tape (eg steel, titanium or a plastic such as polyimide). Then the tape is coated directly and sent through the process area.
  • the substrate 20 may in particular be coated with a further component, also referred to in this context as a precursor layer.
  • the precursor layer may in particular be one or more layers of, for example, copper, gallium, indium.
  • PVD Physical Vapor Deposition
  • CVD Chemical Vapor Deposition
  • Another method for applying the precursor layers may be screen printing, for example.
  • the materials to be applied for example one or more of Cu, Ga, In, Al, Zn, Sn, dispersed in a solvent (eg resin or complex organic compounds), for example in the form of nanoparticles, applied to the substrate and then dried, to completely remove the solvent again.
  • a coating by means of cathode sputtering is advantageous.
  • the substrate position 22 is provided with a heating device 30, with which a desired substrate temperature of the substrate 20 can be set. Furthermore, a tempering device 32 can be provided with which the process area 10 or further areas of the housing 16 can be tempered. The tempering device 32 may also alternatively or additionally project over the substrate region and be used for surface heating.
  • the conveyor 40 is arranged, for example a circulation device for circulating the mass flow 62 in the housing 16, e.g. a rotor.
  • a heater 34 is arranged, which can heat the mass flow 62 to a temperature which prevents condensation of the coating material 60 from the mass flow 62 between the heater 34 and material source 50. An almost complete recycling of the coating material 60 in the mass flow 62 to the material source 50 succeeds.
  • the interior space 18 may be bounded by an inner wall 14, so that the areas 18a-18d may be practically formed as interconnected channels.
  • an oxygen-free atmosphere can be set in the interior 18.
  • the coating of the substrate 20 with coating material 60 can be carried out at atmospheric or quasi-atmospheric pressure conditions, in particular in a pressure range between pressure range between 1 mbar and 1500 mbar, for example between 500 mbar and 1500 mbar.
  • the material source 50 may be a container in which the coating material 60 is liquefied and vaporized. It is also conceivable, the coating material
  • the housing 16 may be surrounded by a further housing 12, which encloses the individual areas 18a-18d of the inner space 18 and tempering devices 32.
  • a lock device (not shown) may be provided for introducing and removing the substrate 20 into the interior 18.
  • a suitable condensation device (not shown) to a loss of mass flow 62 from the
  • FIG. 2 shows a schematic representation of the adjusting device 70 of FIG. 1.
  • the adjusting device 70 serves to provide a degree of saturation of the mass flow 62 of coating material 60. This includes the
  • Setting device 70 a (for example, controllable) cooling device 72 for cooling the mass flow 62.
  • a saturation level of 100% can be adjusted.
  • a targeted lower saturation level can be set.
  • a heating device 74 for heating the mass flow 62 is arranged in the adjustment device 70. With the heater 74, the temperature of the mass flow 62 can be adjusted independently of the saturation degree of the mass flow 62.
  • the cooling device 72 may be a channel or channel system whose walls are cooled.
  • thermalization of the saturated mass flow e.g., selenium vapor
  • the cooling of the channel walls can e.g. take place through holes located in the channel walls, which are traversed by a cooling medium (gas or liquid).
  • the adjustment of the temperature can be done by the amount and / or temperature of the medium.
  • a uniform cooling of the mass flow 62 can take place by means of suitable homogenization zones in the cooling device 72. These may e.g. be realized by a sequence of narrow and wide channel zones.
  • Compression of the mass flow 62 is spatially homogenized and about a temperature compensation in the mass flow 62 causes.
  • cooling to a fixed temperature can also take place (for example by means of water cooling) and a subsequent heating device can be regulated.
  • the cooling device 72 (“dew point regulator”) can, in a favorable embodiment, which is shown in FIGS. 3a and 3b, consist of a separating body, in particular a plate 72a, for example of a graphite plate which has a large number of webs or channels K and therefore
  • This plate 72a (“dew-point element”) is cooled from one side by a cooler 72b, while the other is heated by a heater 72c.
  • the temperature of the cooling device 72 and the plate 72a within a small tolerance to about 5-10 ° precisely adjustable and adjustable. Condensed selenium (or sulfur) may drip off and flow back into the material source 50 tank.
  • the final temperature of the mass flow 62 emerging from the adjusting device 70 (FIG. 1) is then set in a defined manner by the ratio of fixed cooling and adjustable heating.
  • the heater 74 now heats the defined gas mixture of the mass flow 62 (FIG. 1) with a defined dew point, which, however, does not change the dew point. If the mass flow 62 hits a surface, the dew point that has been set in the cooling device 72 applies.
  • the adjusting device 70 is a dew point control of the mass flow 62.
  • a dew point sensor 80 may be provided, which is explained in more detail in Figure 4.
  • the dew point sensor 80 has a carrier 82 with a glossy or reflective surface 84.
  • the surface 84 can be temperature-variable via a tempering system 86; in particular, a temperature gradient along the surface 84 can be set. Alternatively, surface 84 may be at a constant temperature. The reflectance of the surface 84 can be evaluated and used to detect the
  • Dew point can be used.
  • the reflectance can be determined, for example, from an intensity of a laser beam L_o reflected at the surface 84 in comparison with the intensity of an incident laser beam L_i. If the surface 84 is covered with more or less condensed coating material 60, the intensity of the reflected laser beam L_o changes accordingly.
  • the cooling device 72 ( Figure 2) can be controlled.
  • the combination of cooling device 72, which determines the temperature of the mass flow 62 (FIG. 1), and dew point sensor 80 thus permits exact regulation of the amount and / or concentration of the coating material 60 in the mass flow 62.
  • the dew point sensor 80 advantageously also allows a control, which is not absolutely necessary. If the control option is missing, the dew point is only set.
  • the dew point control makes it possible to keep the process area 10 in FIG. 1 in a controllable ratio of coating material 60 and carrier gas 64 at all times.
  • the concentration of coating material 60 for example selenium and / or sulfur, is controlled in a controlled manner. This also applies to the temperature of the mass flow 62.
  • the prior art always work with an excess of selenium and / or sulfur with corresponding losses of these materials to a to achieve sufficient electrical quality of the semiconductor to be formed by the reaction.
  • the controllable equilibrium can be used to specify whether the reaction of the coating material 60 takes place with the precursor layer as a solid-state vapor-phase reaction or as a solid-state gas-phase reaction. This can be optionally set.
  • the concentration of the coating material 60 in the Mass flow 62 are regulated down so far that an uncontrolled condensation of the coating material 60 can be avoided on the surface of the newly formed semiconductor. Aftertreatment of the surface is therefore not necessary.
  • the entire process area 10 may be kept free of condensate of the coating material 60. A complex cleaning of the inner walls can be omitted.
  • two material sources 50 can be provided with two separate adjustment devices 70, which are arranged, for example, in separate regions of the interior 18. Concentration and / or amount of the respective material in the respective mass flow 62 can be adjusted, in particular regulated, by the separate adjusting devices 70.
  • the deposition of the coating material 60 can be carried out in particular sequentially. It is advantageously achieved, on the one hand, that the mass flow 62 with a defined degree of saturation of the coating material 60 as well as the temperature and concentration of the coating material 60 are exactly adjusted or regulated. The equilibrium in the process area 10 is ensured, regardless of other properties of the process area 10, such as wall temperature.
  • equilibrium means that the temperature of the mass flow 62 in the process area 10 and the concentration of the coating material 60 are defined.
  • the course of the reaction can be controlled.
  • the absolute amount of the coating material 60 and thus the equilibrium can be influenced.
  • chalcogen vapor for example at a temperature of at least 500 ° C.
  • a saturated chalcogen vapor for example at a temperature of at least 500 ° C.
  • a carrier gas 64 such as nitrogen
  • a residual oxygen content is usefully as low as possible, preferably below 100 ppm, preferably below 50 ppm.
  • the mass flow 62 is fed to the cooling device 72 of the adjustment device 70, which may optionally be adjustable in its temperature.
  • a substrate 20 with a precursor layer, for example of the metals copper, indium, gallium is arranged at its substrate position 22, wherein a lock device for introducing and / or discharging the Substrate is not shown.
  • the substrate 20 has a suitable substrate temperature, preferably below the dew point.
  • the mass flow 62 in the heating device 74 can be heated to the process temperature, regardless of the amount of chalcogen and the chalcogen concentration, and adapted to the process requirements.
  • the properties of the mass flow 62 with respect to the condensation behavior of the chalcogen is determined exclusively in the cooling device 72. If the mass flow 62 flows over an area with a temperature below the dew point, the chalcogen condenses on the surface. The difference between the substrate temperature and the set dew point determines the deposition rate of the coating material 60, ie the chalcogen.
  • Cu 2 Se leads to the formation of larger CIGS crystallites and to material with more favorable electrical properties.
  • metallic precursor with chalcogen to CIGS the formation of cheap Cu 2 Se can not be enforced by working with about copper excess, since the content of copper in the precursor is inevitably fixed and is present in deficit, based on a stoichiometric compound Cu (In, Ga) (S, Se) 2 .
  • Infiltration temperature range of the substrate 20 (initial temperature for the vapor phase condensation in the reaction space): 250 ° C ... 470 ° C
  • Temperature of the cooling device 72 400 ° C ... 520 ° C
  • Temperature of tempering device 32 > 500 ° C; always greater than the dew point temperature of the heater 34:> 500 ° C.
  • Temperature of the material source 50 > 500 ° C, especially> 600 ° C; preferred: around

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  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
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  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne un dispositif de revêtement (100) pour la fabrication de semi-conducteurs en chalcogène pour des applications photovoltaïques, comprenant une zone de processus (10) dans laquelle un substrat (20) destiné à être revêtu d'un matériau de revêtement (60) contenant du chalcogène est monté au moins temporairement dans une position (22), une source de matériau (50) pour le matériau de revêtement (60), et un dispositif de transport (40) permettant de conduire le matériau de revêtement (60) dans un flux de matière (62) de la source de matériau (50) au moins jusqu'à la position (22) du substrat. Le dispositif de revêtement (100) est conçu de telle sorte que le matériau de revêtement (60) est condensé dans une phase liquide sur le substrat (20) au moyen d'une condensation en phase vapeur. L'invention concerne en outre un procédé de fabrication de semi-conducteurs en chalcogène pour des applications photovoltaïques.
PCT/EP2012/066424 2011-08-26 2012-08-23 Dispositif et procédé de revêtement d'un substrat Ceased WO2013030088A1 (fr)

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DE102011053049A DE102011053049A1 (de) 2011-08-26 2011-08-26 Vorrichtung und Verfahren zur Beschichtung eines Substrats
DE102011053050A DE102011053050A1 (de) 2011-08-26 2011-08-26 Vorrichtung und Verfahren zur Beschichtung eines Substrats
DE102011053050.9 2011-08-26
DE102011053049.5 2011-08-26

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WO2013030088A1 true WO2013030088A1 (fr) 2013-03-07

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5772431A (en) 1995-05-22 1998-06-30 Yazaki Corporation Thin-film solar cell manufacturing apparatus and manufacturing method
DE69425255T2 (de) 1993-04-12 2001-03-15 Midwest Research Institute, Kansas City DÜNNE SCHICHT VON Cu (In,Ga)Se 2 MIT VERBESSERTER QUALITÄT DURCH DAMPFPHASENREKRISTALLISATION FÜR HALBLEITERVORRICHTUNGEN
EP2144296A1 (fr) 2008-06-20 2010-01-13 Volker Probst Procédé de fabrication d'une couche semi-conductrice
US20100028533A1 (en) * 2008-03-04 2010-02-04 Brent Bollman Methods and Devices for Processing a Precursor Layer in a Group VIA Environment
DE102009011496A1 (de) 2009-03-06 2010-09-16 Centrotherm Photovoltaics Ag Verfahren und Vorrichtung zur thermischen Umsetzung metallischer Precursorschichten in halbleitende Schichten mit Chalkogenrückgewinnung
US20100255660A1 (en) 2009-04-07 2010-10-07 Applied Materials, Inc. Sulfurization or selenization in molten (liquid) state for the photovoltaic applications
US20110081487A1 (en) * 2009-03-04 2011-04-07 Brent Bollman Methods and devices for processing a precursor layer in a group via environment

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69425255T2 (de) 1993-04-12 2001-03-15 Midwest Research Institute, Kansas City DÜNNE SCHICHT VON Cu (In,Ga)Se 2 MIT VERBESSERTER QUALITÄT DURCH DAMPFPHASENREKRISTALLISATION FÜR HALBLEITERVORRICHTUNGEN
US5772431A (en) 1995-05-22 1998-06-30 Yazaki Corporation Thin-film solar cell manufacturing apparatus and manufacturing method
US20100028533A1 (en) * 2008-03-04 2010-02-04 Brent Bollman Methods and Devices for Processing a Precursor Layer in a Group VIA Environment
EP2144296A1 (fr) 2008-06-20 2010-01-13 Volker Probst Procédé de fabrication d'une couche semi-conductrice
US20110081487A1 (en) * 2009-03-04 2011-04-07 Brent Bollman Methods and devices for processing a precursor layer in a group via environment
DE102009011496A1 (de) 2009-03-06 2010-09-16 Centrotherm Photovoltaics Ag Verfahren und Vorrichtung zur thermischen Umsetzung metallischer Precursorschichten in halbleitende Schichten mit Chalkogenrückgewinnung
US20100255660A1 (en) 2009-04-07 2010-10-07 Applied Materials, Inc. Sulfurization or selenization in molten (liquid) state for the photovoltaic applications

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