WO2010100560A1 - Process and device for the thermal conversion of metallic precursor layers into semiconducting layers with chalcogen recovery - Google Patents

Process and device for the thermal conversion of metallic precursor layers into semiconducting layers with chalcogen recovery Download PDF

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Publication number
WO2010100560A1
WO2010100560A1 PCT/IB2010/000462 IB2010000462W WO2010100560A1 WO 2010100560 A1 WO2010100560 A1 WO 2010100560A1 IB 2010000462 W IB2010000462 W IB 2010000462W WO 2010100560 A1 WO2010100560 A1 WO 2010100560A1
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Prior art keywords
substrates
exhaust gas
furnace chamber
furnace
chalcogen
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PCT/IB2010/000462
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French (fr)
Inventor
Robert Michael Hartung
Immo KÖTSCHAU
Dieter Schmid
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Centrotherm Photovoltaics Ag
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Publication of WO2010100560A1 publication Critical patent/WO2010100560A1/en

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    • 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
    • C23C14/58—After-treatment
    • C23C14/5846—Reactive treatment
    • C23C14/5866—Treatment with sulfur, selenium or tellurium
    • 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
    • H01L31/00—Semiconductor 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
    • H01L31/0248—Semiconductor 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
    • H01L31/0256—Semiconductor 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
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic 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
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells

Definitions

  • the present invention relates to a process and a device for the thermal conversion of metallic precursor layers on flat substrates into semiconducting layers with chalcogen recovery.
  • the process of the invention for the production of semiconducting layers is a multi-stage process.
  • the metallic precursor layers can contain copper (Cu) , gallium (Ga) and indium (In) . They can be applied to the substrate, which may be a glass substrate with a molybdenum (Mo) layer, using known techniques such as sputtering.
  • the metallic precursor layers are transformed in a chalcogen-containing atmosphere preferably consisting of selenium and/or sulphur into semiconducting layers, preferably into a CuInGaSe (CIGS) layer, in a heating process.
  • chalcogens form solids; they vaporize at temperatures above approximately 35O 0 C.
  • Such substrates prepared with a semiconducting layer can than be further processed to solar modules.
  • a conversion of the metallic precursor layers into a semiconducting layer with a regular thickness and as homogeneous a composition as possible over the surface of the substrate are vital for good efficiency.
  • EP 0 662 247 Bl discloses a process for the production of a chalcopyrite semiconductor on a substrate, wherein the substrate prepared with metals such as copper, indium or gallium is heated in an inert process gas to a final temperature of at least 350°C at a heating rate of at least 10K/second. The final temperature is held for a time period of 10 seconds to 1 hour, during which the substrate is exposed to sulphur or selenium as components which are in excess with respect to the components copper, indium or gallium. To this end, a covering rather like an encapsulation is arranged over the stack of layers on the substrate at a distance of less than 5 mm.
  • the partial pressure of sulphur or selenium is thus greater than the partial pressure which would , be present in a stoichiomet- rically exact composition of the starting components copper, indium or gallium and sulphur.
  • a furnace segmented into regions with different temperatures suitable for a continuous process is not described.
  • the substrates prepared with at least one metallic precursor layer are heated in a furnace segmented into regions with different temperatures at approximately atmospheric pressure in a plurality of steps each to a preset temperature up to a final temperature in the range 400 0 C to 600 0 C and the final temperature is held in an atmosphere of a mixture of a carrier gas and chalcogen vapour to transform the substrates into semiconducting layers.
  • the aim of the invention is to provide a process and a device for the thermal conversion of metallic precursor layers into semiconducting layers of the best possible quality, wherein waste chalcogens are substantially reduced.
  • waste chalcogens are substantially reduced. The smaller quantities of waste result in a simplified production process and reduce costs since less chalcogen has to be employed initially.
  • the chalcogen is selenium and the carrier gas is an inert gas such as nitrogen.
  • the substrates are heated in a furnace which is segmented into several temperature regions in several steps, each to a predefinable temperature .
  • the substrates in the furnace are transported from segment to segment simultaneously and in a stepwise manner, wherein the dwell time in the individual segments is identical.
  • the dwell time can be in the range 20 to 100 seconds, preferably in the range 40 to 80 seconds, more preferably in the range 50 to 70 seconds, for example 60 seconds.
  • the substrates can be heated 1 Up in stages from ambient temperature to approximately 150 0 C, 450 0 C and 550 0 C; a final temperature of 550 0 C does not have to be exceeded.
  • the substrates can then be cooled in at least one step to ambient temperature.
  • the substrates may already have been provided with at least one chalcogen layer prior to entering the furnace.
  • the chalcogens on the substrate vaporize completely in the furnace where they are available for the transformation process.
  • the chalcogens might only partially vaporize. A partial transformation of the metallic precursor layers with the molten chalcogens might occur.
  • the chalcogen layers are preferably applied to the metallic precursor layers by sputtering the chalcogens. This may be carried out under atmospheric conditions in a continuous process .
  • a rapid vaporization of the chalcogens from the substrates may lead to variations in the density of the chalcogens along the furnace. This may then result 'in a localized under-supply of chalcogens when the final temperature is reached, which may result in a localized incomplete transformation of the metallic precursor layers into semiconducting , layers .
  • the exhaust gas recirculation of the invention can now have the positive effect of smoothing out the chalcogen concentration along the furnace.
  • a further smoothing effect and a further guarantee of a sufficiently high chalcogen concentration for thin chalcogen layers on the substrates may be ensured by supplying chalcogen vapour from a source which may also be advantageously employed when the substrates have no chalcogen layer.
  • chalcogen vapour may be introduced into the chamber of the furnace from an external source of vapour or it may be produced in the chamber of the furnace by an internal source of vapour.
  • the invention may also be characterized in that the metallic precursor layers are produced by successive sputtering of copper/gallium and indium.
  • substrates formed from glass are initially provided with a layer of molybdenum by sputtering, onto which a second layer of copper/gallium from a composite copper/gallium target and finally a third layer of indium from an indium target are sputtered under high vacuum.
  • a layer of molybdenum by sputtering, onto which a second layer of copper/gallium from a composite copper/gallium target and finally a third layer of indium from an indium target are sputtered under high vacuum.
  • coating with molybdenum is carried out in a first sputtering unit, and coating with copper/gallium and indium is carried out in a second sputtering unit.
  • heating the substrates and transformation of the metallic precursor layers are preferably carried out in the absence of oxygen and hydrogen, for example, or with as low a partial pressure of oxygen and hydrogen as possible.
  • the aim of the invention is also achieved with a device which consists of a furnace with a furnace chamber, which has an opening for bringing the substrates in and an opening for taking the substrates out, having a gas lock at the opening for bringing the substrates in, having a gas lock at the opening for taking the substrates out, having a transport means for the substrates and having an exhaust gas line for removal of a chalcogen vapour/carrier gas mixture from the furnace chamber, the device further being provided on the exhaust gas line, with a flow volume divider and/or a recycling device which allow (s) chalcogens not used in the reaction to be recirculated to the furnace chamber.
  • a recirculation line may, for example, be arranged.
  • the chalcogen used is selenium.
  • a gas lock allows the gas atmospheres on either side of an opening to be separated using suitable streams of gas without having to close off the. opening with solid doors.
  • the streams of gas on either side of the gas locks can be adjusted independently of each other.
  • the gas locks of the furnace chamber can also each consist of at least two gas curtains. Further, additional extraction may be provided between the gas curtains.
  • an inert gas such as nitrogen, for example, is used as the protective/carrier gas-
  • an inert gas such as nitrogen, for example.
  • the transport means, the opening for bringing the substrates in and the opening for taking the substrates out mean that the substrates can be brought into the furnace chamber, be transported through the furnace chamber and be taken out of the furnace chamber following conversion of the metallic precursor layers into semiconducting layers.
  • the chalcogen vapour/carrier gas mixture is introduced into the recycling device via the exhaust gas line, the exhaust gas being divided in the recycling device into two exhaust gas stream fractions by means of a flow volume divider.
  • a first exhaust gas stream fraction is fed back to the furnace chamber, preferably to the entrance to the furnace chamber.
  • the second exhaust gas stream fraction termed the residual exhaust gas, is evacuated via a residual exhaust gas line.
  • the residual exhaust gas can be filtered and then evacuated. Waste chalcogens have to be disposed of or be sent for reprocessing.
  • the flow volume divider may be linked with a recycling device or be a component of a recycling device, in which chalcogens are removed from the second exhaust gas stream fraction (residual exhaust gas) and added to the first exhaust gas stream fraction, so that the gas that is recirculated to the furnace chamber is enriched with chalcogens .
  • the residual exhaust gas that is evacuated thus has a lower concentration of chalcogens and thus there is even less waste chalcogen. At the same time, a larger proportion of the chalcogens which are introduced is used for the process.
  • the temperature of one or more of the walls in the interior of the furnace chamber, flow volume divider, recycling device, exhaust gas line and recirculation line is adjusted to and held at a temperature which is higher than the condensation temperature of the chalcogens .
  • the temperature of the walls does not have to be the same everywhere. In particular, it can vary in the furnace chamber.
  • the furnace chamber may be divided into a plurality of successive segments Sl...Sn at different temperatures.
  • the temperatures of the interior walls of the furnace chamber, flow volume divider, recycling device, exhaust gas line and recirculation line as well as in the various segments may, for example, be adjusted independently with the aid of heating and cooling systems.
  • each segment is thermally insulated from the other segments. This means that neighbouring segments can be heated to substantially different temperatures . Furthermore, the furnace chamber as a whole and/or each segment can be individually thermally insulated in order to reduce the energy required for heating the segments.
  • the walls of the furnace chamber are of graphite.
  • the transport means in the furnace segmented into a plurality of temperature regions preferably allows stepwise and simultaneous transport of all of the substrates in the furnace cham- . ber to the respective subsequent segment.
  • the dwell time for the substrates in the individual segments is identical and may, for example, be approximately 60 seconds.
  • the furnace chamber may be surrounded by a housing with an opening for bringing the substrates in and an opening for taking the substrates out.
  • the housing may, for example, be a stainless steel case.
  • the housing may have separate housing extraction and may be provided with a flush of a protective gas.
  • the housing has a separate cooling system. This means that radiated heat can be evacuated from the furnace chamber.
  • a sensor for determining the presence of a gas and/or a concentration of a gas for example an oxygen sensor and/or a HaSe sensor, may be provided in the housing.
  • the oxygen sensor enables unwanted penetration of oxygen- into the space between the. housing and the furnace chamber to be detected.
  • the H 2 Se sensor is provided for safety reasons, in order to detect hydrogen selenide should it appear and provide a timely warning.
  • Fig. 1 is a diagrammatic illustration of the device in longitudinal section
  • Fig. 2 is a section of the device, namely a gas lock as used in the illustrative example.
  • Figure 1 shows a furnace chamber 1 with an exhaust gas line 7.
  • a flow volume divider 2 and a recycling device 3 are arranged on this exhaust gas line 7, wherein the flow volume divider 2 and the recycling device 3 are combined in a module.
  • a recirculation line 8 runs back to the furnace chamber 1; it opens into the beginning of the furnace chamber 1.
  • a residual exhaust gas line 9 is connected to the recycling device 3; the residual exhaust gas is evacuated via the residual exhaust gas line 9.
  • the furnace chamber 1 is provided with an inlet and an outlet gas lock 4.
  • a transport device 10 which comprises a plurality of successively arranged transport rollers.
  • the transport device 10 serves to transport the substrates 11 through the furnace chamber 1.
  • the furnace chamber 1 is divided into several successively arranged segments which can be heated independently of each other and are thermally insulated from each other. However, for simplification, the individual segments have not been illustrated and so the furnace chamber 1 shown is somewhat shorter than would be the case in a real device, as indicated by the dashed chamber walls in the central portion.
  • Nitrogen is used as the protective/carrier gas in an illustrative process carried out in the device.
  • FIG. 2 shows an embodiment of the gas locks 4.
  • the multistage gas curtains each consist of two adjacent inlets 5 for nitrogen curtains each with gas streams directed in opposing direction directed from the top and the bottom, producing a slight overpressure in the centre of the lock region, and of an extraction point produced by means of outlets 6 arranged at the top and bottom between the two nitrogen curtains. This arrangement allows the gas streams either side of the gas curtain to be adjusted independently of each other.
  • the gas curtains allow substrates to be transported through the furnace in a continuous process at atmospheric pressure and under set residual gas conditions, in particular with the exclusion of oxygen.
  • the walls of the furnace chamber 1 are of graphite and are surrounded by a stainless steel case, not shown, which has separate extraction and a nitrogen flush.
  • different temperatures can be preset along the furnace chamber using heating and/or cooling systems.
  • the substrates 11 prepared with a copper/gallium, indium and selenium layer are brought into the furnace chamber 1 with the aid of the transport device 10 through the inlet gas lock 4.
  • the substrates 11 are transported further along the furnace chamber from segment to segment in a stepwise manner and- finally are taken out at the end of the furnace chamber 1 via the outlet gas lock 4.
  • the dwell time in each segment in an illustrative process carried out in the device is 60 seconds.
  • the selenium on the substrate 11 starts to melt; it vaporizes completely with thin chalcogen layers.
  • the selenium vapour mixes with the nitrogen to a selenium vapour/carrier gas mixture.
  • this mixture is transported inside the furnace through the furnace chamber 1 over the substrates 11 in the unit to the exhaust gas line 7 of the furnace. There is absolutely no transport in the opposite direction.
  • the chalcogens With thick chalcogen layers, the chalcogens only partially vaporize. A partial transformation of the metallic precursor layers may occur with the molten chalcogens.
  • Controlling the gas stream is made possible by the fact that the gas streams on either side of the gas locks 4 and in the exhaust gas line 7 are independently adjustable.
  • the speed of the gas stream in the furnace chamber 1 from the inlet to the furnace to the exhaust gas line 7 must then be adjusted to the speed of transport of the substrates 11, so that on reaching the reaction temperature, selenium is present in excess in order to transform the metallic precursor layers into a CIGS layer.
  • Unused selenium is evacuated via the exhaust gas line 7.
  • the exhaust gas line 7 feeds the selenium vapour/carrier gas mixture to the flow volume divider 2.
  • the exhaust gas is divided into two adjustable exhaust gas stream fractions.
  • a first exhaust gas stream fraction is recirculated via the recirculation line 8 and fed back at the beginning of- the furnace chamber 1 to the process.
  • the recycling device 3 removes a portion of the chalcogenide contained in the second exhaust gas stream fraction and enriches the first exhaust gas stream fraction with it.
  • the remaining portion of the second exhaust gas stream fraction termed the residual exhaust gas, now only contains a small fraction of chalcogenide.
  • This residual exhaust gas is filtered and evacuated via the residual exhaust gas line 9.
  • the waste chalcogen must be disposed of or reprocessing must be carried out.
  • Said recirculation results in a reduction in selenium losses, and so less selenium is used initially.

Abstract

The present invention concerns a process for the thermal conversion of metallic precursor layers on flat substrates into semiconducting layers with a recovery of chalcogen, as well as a device for carrying out the process. The aim of the invention is to provide a rapid and readily executable process for the thermal conversion of metallic precursor layers on flat substrates into semiconducting layers, as well as a device suitable for carrying out the process with as small as possible primary consumption of chalcogens. This is achieved by heating substrates in a furnace at approximately atmospheric pressure to a final temperature in the range 400°C to 6000C and transforming them into semiconducting layers in an atmosphere formed from a mixture of at least one carrier gas and chalcogen vapour, wherein chalcogen vapour not consumed in the reaction is made available to the process again via exhaust gas recirculation.

Description

Process and device for the thermal conversion of metallic precursor layers into semiconducting layers with chalcogen recovery
The present invention relates to a process and a device for the thermal conversion of metallic precursor layers on flat substrates into semiconducting layers with chalcogen recovery.
Converting sunlight into electrical energy economically and in as environmentally friendly a manner as possible requires the production of highly efficient solar cells consuming as little material and energy as possible. In this respect, thin layer solar cells, in particular solar cells based on compound semiconductors such as copper-indium-gallium-selenide (CIGS) , are showing a great deal of promise.
The process of the invention for the production of semiconducting layers is a multi-stage process. The metallic precursor layers can contain copper (Cu) , gallium (Ga) and indium (In) . They can be applied to the substrate, which may be a glass substrate with a molybdenum (Mo) layer, using known techniques such as sputtering. In a second step, the metallic precursor layers are transformed in a chalcogen-containing atmosphere preferably consisting of selenium and/or sulphur into semiconducting layers, preferably into a CuInGaSe (CIGS) layer, in a heating process. At ambient temperature, i.e. about 200C, chalcogens form solids; they vaporize at temperatures above approximately 35O0C.
Such substrates prepared with a semiconducting layer can than be further processed to solar modules. As complete as possible a conversion of the metallic precursor layers into a semiconducting layer with a regular thickness and as homogeneous a composition as possible over the surface of the substrate are vital for good efficiency.
Processes for the thermal conversion of such prepared precursor layers into semiconducting layers which are carried out under vacuum are known in the prior art. The problem with vacuum processes is the long reaction time, also known as the process time. In industrial reactions, this gives rise to problems because long process times are always associated with low productivity. One solution would be the simultaneous use of a plurality of machines, but that would incur high investment costs; another would be to speed up the processes. The prior art is silent in this regard.
Furthermore, processes for the thermal conversion of such prepared precursor layers into semiconducting layers are known in the prior art which are carried out under atmospheric conditions and with the addition of hydrogen-containing gases, for example hydrogen selenide (EP 0 318 315 A2) . The use of toxic gases such as hydrogen selenide is problematic, however.
EP 0 662 247 Bl discloses a process for the production of a chalcopyrite semiconductor on a substrate, wherein the substrate prepared with metals such as copper, indium or gallium is heated in an inert process gas to a final temperature of at least 350°C at a heating rate of at least 10K/second. The final temperature is held for a time period of 10 seconds to 1 hour, during which the substrate is exposed to sulphur or selenium as components which are in excess with respect to the components copper, indium or gallium. To this end, a covering rather like an encapsulation is arranged over the stack of layers on the substrate at a distance of less than 5 mm. The partial pressure of sulphur or selenium is thus greater than the partial pressure which would, be present in a stoichiomet- rically exact composition of the starting components copper, indium or gallium and sulphur. However, a furnace segmented into regions with different temperatures suitable for a continuous process is not described.
A simple to produce, rapid continuous process for the thermal conversion of metallic layers on any substrates to form semiconducting layers as well as a device suitable for carrying out the process are given in the post-published International patent application PCT/EP2008/007466.
This is achieved by virtue of a process wherein the substrates prepared with at least one metallic precursor layer are heated in a furnace segmented into regions with different temperatures at approximately atmospheric pressure in a plurality of steps each to a preset temperature up to a final temperature in the range 4000C to 6000C and the final temperature is held in an atmosphere of a mixture of a carrier gas and chalcogen vapour to transform the substrates into semiconducting layers.
In this manner, good semiconducting layers can be obtained at heating rates which are substantially below 10K/second.
According to the prior art, it must be ensured that on reaching the final temperature, sufficient chalcogens are available to make as complete as possible a transformation of the metallic precursor layers into semiconducting layers.
This is accomplished by using an excess of chalcogens. Excess chalcogen which is not used in the reaction is transported together with the carrier gas via an exhaust gas line of the furnace. According to the prior art, the chalcogens can be filtered out of the exhaust chalcogen vapour/carrier gas mixture, also termed the exhaust gas, and disposed of as waste. The aim of the invention is to provide a process and a device for the thermal conversion of metallic precursor layers into semiconducting layers of the best possible quality, wherein waste chalcogens are substantially reduced. The smaller quantities of waste result in a simplified production process and reduce costs since less chalcogen has to be employed initially.
This is achieved by means of a process wherein the substrates prepared with at least one metallic precursor layer are heated in a furnace at approximately atmospheric pressure to a final temperature in the range 4000C to 6000C and transformed into semiconducting layers in an atmosphere formed from a mixture of at least one carrier gas and chalcogen vapour, wherein a portion of the chalcogen vapour not consumed in the reaction is made available to the process again by means of exhaust gas recirculation.
Preferably, the chalcogen is selenium and the carrier gas is an inert gas such as nitrogen.
In a further development of the invention, the substrates are heated in a furnace which is segmented into several temperature regions in several steps, each to a predefinable temperature .
Thus, the substrates in the furnace are transported from segment to segment simultaneously and in a stepwise manner, wherein the dwell time in the individual segments is identical.
The dwell time can be in the range 20 to 100 seconds, preferably in the range 40 to 80 seconds, more preferably in the range 50 to 70 seconds, for example 60 seconds. The substrates can be heated 1Up in stages from ambient temperature to approximately 1500C, 4500C and 5500C; a final temperature of 5500C does not have to be exceeded.
The substrates can then be cooled in at least one step to ambient temperature.
In order to prepare the chalcogen vapour required for transformation of the metallic precursor layers into semiconducting layers, the substrates may already have been provided with at least one chalcogen layer prior to entering the furnace.
With thin chalcogen layers, the chalcogens on the substrate vaporize completely in the furnace where they are available for the transformation process.
With thick chalcogen layers, the chalcogens might only partially vaporize. A partial transformation of the metallic precursor layers with the molten chalcogens might occur.
The chalcogen layers are preferably applied to the metallic precursor layers by sputtering the chalcogens. This may be carried out under atmospheric conditions in a continuous process .
A rapid vaporization of the chalcogens from the substrates may lead to variations in the density of the chalcogens along the furnace. This may then result 'in a localized under-supply of chalcogens when the final temperature is reached, which may result in a localized incomplete transformation of the metallic precursor layers into semiconducting , layers . In addition to reducing the initial quantity of chalcogens used, the exhaust gas recirculation of the invention can now have the positive effect of smoothing out the chalcogen concentration along the furnace.
A further smoothing effect and a further guarantee of a sufficiently high chalcogen concentration for thin chalcogen layers on the substrates may be ensured by supplying chalcogen vapour from a source which may also be advantageously employed when the substrates have no chalcogen layer.
Consequently, alternatively or in addition to prior coating of the substrates with a chalcogen layer, chalcogen vapour may be introduced into the chamber of the furnace from an external source of vapour or it may be produced in the chamber of the furnace by an internal source of vapour.
The invention may also be characterized in that the metallic precursor layers are produced by successive sputtering of copper/gallium and indium.
To this end, substrates formed from glass, for example, are initially provided with a layer of molybdenum by sputtering, onto which a second layer of copper/gallium from a composite copper/gallium target and finally a third layer of indium from an indium target are sputtered under high vacuum. Typically, coating with molybdenum is carried out in a first sputtering unit, and coating with copper/gallium and indium is carried out in a second sputtering unit.
Further, heating the substrates and transformation of the metallic precursor layers are preferably carried out in the absence of oxygen and hydrogen, for example, or with as low a partial pressure of oxygen and hydrogen as possible. The aim of the invention is also achieved with a device which consists of a furnace with a furnace chamber,, which has an opening for bringing the substrates in and an opening for taking the substrates out, having a gas lock at the opening for bringing the substrates in, having a gas lock at the opening for taking the substrates out, having a transport means for the substrates and having an exhaust gas line for removal of a chalcogen vapour/carrier gas mixture from the furnace chamber, the device further being provided on the exhaust gas line, with a flow volume divider and/or a recycling device which allow (s) chalcogens not used in the reaction to be recirculated to the furnace chamber. To this end, between the flow volume divider and the furnace chamber, a recirculation line may, for example, be arranged.
Preferably, the chalcogen used is selenium.
A gas lock allows the gas atmospheres on either side of an opening to be separated using suitable streams of gas without having to close off the. opening with solid doors.
In a further development of the device, the streams of gas on either side of the gas locks can be adjusted independently of each other.
The gas locks of the furnace chamber can also each consist of at least two gas curtains. Further, additional extraction may be provided between the gas curtains.
Preferably, an inert gas such as nitrogen, for example, is used as the protective/carrier gas- The opening for bringing the substrates in, the opening for taking the substrates out and the gas locks mean that the device can be operated as a continuous process at a pressure close to atmospheric pressure and under set residual gas conditions, in particular with the exclusion of oxygen and hydrogen.
The transport means, the opening for bringing the substrates in and the opening for taking the substrates out mean that the substrates can be brought into the furnace chamber, be transported through the furnace chamber and be taken out of the furnace chamber following conversion of the metallic precursor layers into semiconducting layers.
In one embodiment of the invention, the chalcogen vapour/carrier gas mixture is introduced into the recycling device via the exhaust gas line, the exhaust gas being divided in the recycling device into two exhaust gas stream fractions by means of a flow volume divider. A first exhaust gas stream fraction is fed back to the furnace chamber, preferably to the entrance to the furnace chamber.
The second exhaust gas stream fraction, termed the residual exhaust gas, is evacuated via a residual exhaust gas line.
The residual exhaust gas can be filtered and then evacuated. Waste chalcogens have to be disposed of or be sent for reprocessing.
In a further embodiment of the invention, the flow volume divider may be linked with a recycling device or be a component of a recycling device, in which chalcogens are removed from the second exhaust gas stream fraction (residual exhaust gas) and added to the first exhaust gas stream fraction, so that the gas that is recirculated to the furnace chamber is enriched with chalcogens . The residual exhaust gas that is evacuated thus has a lower concentration of chalcogens and thus there is even less waste chalcogen. At the same time, a larger proportion of the chalcogens which are introduced is used for the process.
In a particular embodiment of the device, the temperature of one or more of the walls in the interior of the furnace chamber, flow volume divider, recycling device, exhaust gas line and recirculation line is adjusted to and held at a temperature which is higher than the condensation temperature of the chalcogens .
This prevents chalcogen vapour from condensing on these interior walls and sticking to them. This would lead to a loss of chalcogens and require expensive maintenance.
The temperature of the walls does not have to be the same everywhere. In particular, it can vary in the furnace chamber. The furnace chamber may be divided into a plurality of successive segments Sl...Sn at different temperatures.
The temperatures of the interior walls of the furnace chamber, flow volume divider, recycling device, exhaust gas line and recirculation line as well as in the various segments may, for example, be adjusted independently with the aid of heating and cooling systems.
In a further development of the invention, each segment is thermally insulated from the other segments. This means that neighbouring segments can be heated to substantially different temperatures . Furthermore, the furnace chamber as a whole and/or each segment can be individually thermally insulated in order to reduce the energy required for heating the segments.
In one embodiment of the invention, the walls of the furnace chamber are of graphite.
The transport means in the furnace segmented into a plurality of temperature regions preferably allows stepwise and simultaneous transport of all of the substrates in the furnace cham- . ber to the respective subsequent segment.
Because of the stepwise and simultaneous transport of the substrates from segment to segment, the dwell time for the substrates in the individual segments is identical and may, for example, be approximately 60 seconds.
In order better to exclude oxygen or hydrogen, for example, from the furnace chamber, the furnace chamber may be surrounded by a housing with an opening for bringing the substrates in and an opening for taking the substrates out.
The housing may, for example, be a stainless steel case.
Furthermore, the housing may have separate housing extraction and may be provided with a flush of a protective gas.
In one embodiment of the invention, the housing has a separate cooling system. This means that radiated heat can be evacuated from the furnace chamber.
Furthermore, a sensor for determining the presence of a gas and/or a concentration of a gas, for example an oxygen sensor and/or a HaSe sensor, may be provided in the housing. The oxygen sensor enables unwanted penetration of oxygen- into the space between the. housing and the furnace chamber to be detected.
The H2Se sensor is provided for safety reasons, in order to detect hydrogen selenide should it appear and provide a timely warning.
A device in accordance with the invention will now be described with reference to an illustrative example as follows:
Fig. 1 is a diagrammatic illustration of the device in longitudinal section; and
Fig. 2 is a section of the device, namely a gas lock as used in the illustrative example.
Figure 1 shows a furnace chamber 1 with an exhaust gas line 7. A flow volume divider 2 and a recycling device 3 are arranged on this exhaust gas line 7, wherein the flow volume divider 2 and the recycling device 3 are combined in a module. From the flow volume divider 2, a recirculation line 8 runs back to the furnace chamber 1; it opens into the beginning of the furnace chamber 1. A residual exhaust gas line 9 is connected to the recycling device 3; the residual exhaust gas is evacuated via the residual exhaust gas line 9. The furnace chamber 1 is provided with an inlet and an outlet gas lock 4.
Inside the furnace chamber 1 is a transport device 10 which comprises a plurality of successively arranged transport rollers. The transport device 10 serves to transport the substrates 11 through the furnace chamber 1. The furnace chamber 1 is divided into several successively arranged segments which can be heated independently of each other and are thermally insulated from each other. However, for simplification, the individual segments have not been illustrated and so the furnace chamber 1 shown is somewhat shorter than would be the case in a real device, as indicated by the dashed chamber walls in the central portion.
Nitrogen is used as the protective/carrier gas in an illustrative process carried out in the device.
Figure 2 shows an embodiment of the gas locks 4. The multistage gas curtains each consist of two adjacent inlets 5 for nitrogen curtains each with gas streams directed in opposing direction directed from the top and the bottom, producing a slight overpressure in the centre of the lock region, and of an extraction point produced by means of outlets 6 arranged at the top and bottom between the two nitrogen curtains. This arrangement allows the gas streams either side of the gas curtain to be adjusted independently of each other.
The gas curtains allow substrates to be transported through the furnace in a continuous process at atmospheric pressure and under set residual gas conditions, in particular with the exclusion of oxygen.
The walls of the furnace chamber 1 are of graphite and are surrounded by a stainless steel case, not shown, which has separate extraction and a nitrogen flush.
Furthermore, different temperatures can be preset along the furnace chamber using heating and/or cooling systems.
The substrates 11 prepared with a copper/gallium, indium and selenium layer are brought into the furnace chamber 1 with the aid of the transport device 10 through the inlet gas lock 4. Here, the substrates 11 are transported further along the furnace chamber from segment to segment in a stepwise manner and- finally are taken out at the end of the furnace chamber 1 via the outlet gas lock 4.
The dwell time in each segment in an illustrative process carried out in the device is 60 seconds.
At the beginning of the furnace chamber 1, the selenium on the substrate 11 starts to melt; it vaporizes completely with thin chalcogen layers. The selenium vapour mixes with the nitrogen to a selenium vapour/carrier gas mixture. By controlling the gas streams, this mixture is transported inside the furnace through the furnace chamber 1 over the substrates 11 in the unit to the exhaust gas line 7 of the furnace. There is absolutely no transport in the opposite direction.
With thick chalcogen layers, the chalcogens only partially vaporize. A partial transformation of the metallic precursor layers may occur with the molten chalcogens.
Controlling the gas stream is made possible by the fact that the gas streams on either side of the gas locks 4 and in the exhaust gas line 7 are independently adjustable. The speed of the gas stream in the furnace chamber 1 from the inlet to the furnace to the exhaust gas line 7 must then be adjusted to the speed of transport of the substrates 11, so that on reaching the reaction temperature, selenium is present in excess in order to transform the metallic precursor layers into a CIGS layer.
Unused selenium is evacuated via the exhaust gas line 7. In accordance with the invention, the exhaust gas line 7 feeds the selenium vapour/carrier gas mixture to the flow volume divider 2.
In the flow volume divider 2, the exhaust gas is divided into two adjustable exhaust gas stream fractions.
A first exhaust gas stream fraction is recirculated via the recirculation line 8 and fed back at the beginning of- the furnace chamber 1 to the process. At the same time, the recycling device 3 removes a portion of the chalcogenide contained in the second exhaust gas stream fraction and enriches the first exhaust gas stream fraction with it.
The remaining portion of the second exhaust gas stream fraction, termed the residual exhaust gas, now only contains a small fraction of chalcogenide. This residual exhaust gas is filtered and evacuated via the residual exhaust gas line 9. The waste chalcogen must be disposed of or reprocessing must be carried out.
Said recirculation results in a reduction in selenium losses, and so less selenium is used initially.
List of reference numerals
1 furnace chamber
2 flow volume divider
3 recycling device
4 gas lock
5 inlet
6 outlet
7 exhaust gas line
8 recirculation line
9 residual exhaust gas line
10 transport device
11 substrate

Claims

Claims
1. A process for the thermal conversion of metallic precursor layers on a substrate (11) into semiconducting layers, wherein the substrates (11) prepared with at least one metallic precursor layer are heated in a furnace at approximately atmospheric pressure to a final temperature in the range 400°C to 6000C and are transformed into semiconducting layers in an atmosphere formed from a mixture of at least one carrier gas and chalcogen vapour, c h a r a c t e r i z e d i n t h a t at least a portion of the chalcogen vapour not consumed in the reaction is made available to the process again by means of exhaust gas recirculation.
2. A process according to claim 1, c h a r a c t e r i z e d i n t h a t the substrates (11) are heated in a furnace segmented into several temperature regions in several steps each to a pre- definable temperature.
3. A process according to claim 2, c h a r a c t e r i z e d i n t h a t the substrates (11) in the furnace are transported simultaneously and in a stepwise manner from segment to segment, wherein the dwell time in the individual segments is identical.
4. A process according to claim 3, c h a r a c t e r i z e d i n t h a t the dwell time in each segment is in the range 20 to 100 seconds, preferably in the range 40 to 80 seconds, more preferably in the range 50 to 70 seconds.
5. A process according to one of claims 1 to 4, c h a r a c t e r i z e d i n t h a t the substrates (11) have already been provided with at least one chalcogen layer prior to being brought into the furnace .
6. A process according to one of claims 1 to 5, c h a r a c t e r i z e d i n t h a t the chalcogen vapour is introduced into the furnace chamber (1) from an external source of vapour or is produced in the furnace chamber (1) by an internal source of vapour.
7. A device for the thermal conversion of metallic precursor layers on substrates (11) into semiconducting layers, comprising a furnace chamber (1) with an opening for bringing the substrates (11) in and with an opening for taking the substrates (11) out, having a gas lock (4) at the opening for bringing the substrates (11) in and at the opening for taking the substrates (11) out, as well as a transport device (10) for the substrates (11) and an exhaust gas line
(7) for the removal of exhaust gases from the furnace chamber (1), c h a r a c t e r i z e d i n t h a t the exhaust gas line (7) furthermore has a flow volume divider (2) to divide the exhaust gas stream into two exhaust gas stream fractions and a recirculation line (8) to recir- culate a first exhaust gas stream fraction to the furnace chamber (1) .
8. A device according to claim 7, c h a r a c t e r i z e d i n t h a t the recirculation line (8) opens into the furnace chamber (1) at the beginning of the furnace chamber (1) .
9. A device according to claim 7 or claim 8, c h a r a c t e r i z e d i n t h a t the flow volume divider (2) is linked to a recycling device (3) or is a component of a recycling device (3), in which chalcogens are removed from the second exhaust gas stream fraction (residual exhaust gas) and added to the first exhaust gas stream fraction, so that the gas recirculated to the furnace chamber (1) is enriched with chalcogens.
10. A device according to one of claims 7 to 9, c h a r a c t e r i z e d i n t h a t at least one internal wall of the furnace chamber (1) and/or exhaust gas line (7) and/or flow volume divider (2) and/or recycling device (3) and/or recirculation line (8) can be heated.
11. A device according to one of claims 7 to 10, c h a r a c t e r i z e d i n t h a t the furnace chamber (1) is divided into several successive, independently temperature-controlled segments.
12. A device according to claim 11, c h a r a c t e r i z e d i n t h a t each segment is thermally insulated from the other segments .
13. A device according to one of claims 7 to 12, c h a r a c t e r i z e d i n t h a t the furnace chamber (1) as a whole and/or each individual segment is thermally insulated.
14. A device according to one of claims 7 to 13, c h a r a c t e r i z e d i n t h a t a sensor is arranged in the furnace chamber (1) to determine the presence of a gas and/or a concentration of a gas,
PCT/IB2010/000462 2009-03-06 2010-03-05 Process and device for the thermal conversion of metallic precursor layers into semiconducting layers with chalcogen recovery WO2010100560A1 (en)

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