Title of Invention

AN APPARATUS AND METHOD FOR HEAT-TREATING ALTEAST ONE MATERIAL BEING PROCESSED

Abstract The invention relates to an apparatus for heat-treating at least one material being processed in a heat- treatment space of a heat-treatment container under a specific process-gas atmosphere of at least one process gas, characterized in that the heat-treatment container in a heat-treatment chamber is arranged at a distance from the heat-treatment chamber, so that there is an intermediate space between the heat-treatment container and the heat-treatment chamber, and there is a means for producing in the intermediate space a further gas atmosphere of a further gas, different from the process-gas atmosphere.
Full Text Description
Apparatus and method for heat-treating at least one
material being processed
The invention relates to an apparatus for heat-treating
at least one material being processed in a heat-
treatment space of a heat-treatment container under a
specific process-gas atmosphere of at least one process
gas. An apparatus of this type is known for example
from EP 0 662 247 Bl. In addition to the apparatus, a
method for heat-treating a material being processed is
presented.
The material being processed known from EP 0 662 247 Bl
is a multilayered element which is produced by applying
a functional layer to a supporting layer (substrate).
In order that the functional layer and/or the
supporting layer have a desired physical (electrical,
mechanical, etc.) and/or chemical property, processing
of the material being processed or the layer and/or the
supporting layer will be carried out. The processing
comprises heat-treating the material being processed in
the presence of a gas (process gas).
For the heat treatment, the material being processed is
arranged in a closed heat-treatment container made of
graphite. During the heat treatment, the material
being processed is exposed to a process gas with
gaseous selenium. During the heat treatment, the
material being processed takes up an amount of energy,
with a partial amount of the amount of energy being
supplied to each layer. The heat treatment takes
place, for example, at a heating-up rate of 10°C/s. A
halogen lamp is used as the energy source of the amount
of energy. With the halogen lamp, the heat-treatment
container made of graphite is irradiated with an
electromagnetic radiation, and consequently the heat-

treatment container is heated up. Graphite has a high
absorptivity for the electromagnetic radiation in the
spectral range of the halogen lamp. The amount of
energy absorbed by the graphite is supplied to the
material being processed by heat radiation and/or heat
conduction. The heat-treatment container consequently
acts as a secondary energy source or as an energy
transmitter.
Graphite has a high emissivity and a high thermal
conductivity. When the material being processed lies
on a base of the heat-treatment container, on an
underside of the material being processed the amount of
energy is supplied substantially by heat conduction.
An upper side of the material being processed is
supplied with an amount of energy by heat radiation,
heat conduction and convection.
The larger the material being processed (the larger the
surface area thereof), the more varied the materials
used in the material being processed (for example
greatly differing coefficient of thermal expansion,
different absorptivity for the amount of energy etc.)
and the higher a heat-treatment rate (heating-up rate,
cooling-down rate) , the more difficult it is to control
a temperature homogeneity or temperature inhomogeneity
in the material being processed. The temperature
inhomogeneity may lead to mechanical stress in the
material being processed, and consequently to
destruction of the material being processed.
A problem which arises from the cited prior art is use
of, or occurrence of, toxic and/or corrosive gases in
heat treatment (for example H2Se) .
The object of the invention is to demonstrate how safe
and reliable heat treatment can be carried out even in
the presence of toxic and/or corrosive gases.

To achieve the object, an apparatus is specified for
heat-treating at least one material being processed in
a heat-treatment space of a heat-treatment container
under a specific process-gas atmosphere of at least one
process gas. The apparatus is characterized in that
the heat-treatment container in a heat-treatment
chamber is arranged at a distance from the heat-
treatment chamber, so that there is an intermediate
space between the heat-treatment container and the
heat-treatment chamber, and there is a means for
producing in the intermediate space a further gas
atmosphere of a further gas, different from the
process-gas atmosphere.
The gas atmosphere (which can be set) is distinguished,
for example, by a defined partial pressure of a gas or
gas mixture (for example air) . It is also conceivable
for the gas atmosph-ere to be a vacuum.
The intermediate space acts virtually as a buffer. The
buffer helps to avoid process gas from being discharged
into the surrounding area (atmosphere). For this
purpose, in a special configuration, the intermediate
space encloses the heat-treatment space.
The means for producing the further gas atmosphere is,
for example, a gas cylinder, which is in connection
with the intermediate space via one or more openings.
In a special configuration, the heat-treatment space
and the intermediate space are connected to each other
in such a way that a pressure gradient can be set
between the heat-treatment space and the intermediate
space.
Purging gas history
In a further configuration of the invention, there is
at least one heat-treatment unit, with an energy source

for making the material being processed take up an
amount of energy.
The energy source is, for example, a flat bank of
heaters, which is formed by a heater array. The heater
array comprises, for example, bar-shaped halogen lamps
or heating bars arranged parallel to one another. Each
halogen lamp may in this case be arranged in a shroud
for protection from exposure to the (corrosive) process
gas. An energy source of this type sends electro-
magnetic radiation, in particular in the form of
infrared radiation (thermal radiation, intensity
maximum at a wavelength between 1 m and 2 |j.m) . An
energy source in the form of a resistance heating
element, which .emits thermal radiation, is also
conceivable. An element of this type has, for example,
graphite, silicon carbide and/or a metal alloy such as
nickel chromium. Additionally conceivable is any
electromagnetic radiation (microwaves, UV light) which
can lead to a heating-up of the material being
processed. In addition, heat conduction and convection
are also conceivable for the heat treatment.
In a further configuration of the invention, the heat-
treatment unit has at least one means for cooling the
material being processed. This is accompanied by the
advantage that a process sequence comprising various
method stages, with at least one heating-up phase and
cooling-down phase, can be carried out with the aid of
the same apparatus. The means for cooling is, in
particular, a cooling gas and/or a cooling liquid. The
cooling takes place with the aid of the cooling gas by
convection, with, for example, a cooling gas that is
cooler in comparison with the material being processed
being directed past the material being processed. The
cooling may also take place by heat conduction, with
the material being processed being in contact with a
cooling element with a corresponding coefficient of
thermal conductivity. It is conceivable for the

cooling element to be an enclosure of the heat-
treatment unit with a hollow space through which the
cooling gas or the cooling liquid can be directed.
In a further configuration, at least one of the energy
sources is arranged in a shroud which is at least
partially transparent to the electromagnetic radiation
of the energy source. For example, the shroud consists
of quartz glass. The shroud is preferably vacuum-
tight. With the aid of the shroud, the energy source
can be protected from contact with a process gas. A
further advantage of this configuration is that the
energy source can be easily exchanged.
In a special configuration, the shroud of the energy
source has an optical filter for the electromagnetic
radiation of the energy source. In this way, the
optical property (absorptivity and transmissivity) of
the shroud can be influenced in a specifically
selective way.
In a special configuration, at least one of the heat-
treatment units has at least one transparent element,
which has a specific absorption and a specific
transmission for at least one of the electromagnetic
radiations and which is arranged in the radiation field
of the electromagnetic radiation between the energy
source of the electromagnetic radiation and one of the
materials being processed. The special advantage of
the transparent element, in particular when heat-
treating a multilayered element, is presented further
below in connection with the configuration of the heat-
treatment unit.
In a special configuration, the shroud of the energy
source, the heat-treatment container, the heat-
treatment chamber, the transparent element and/or a
reflective element have a material which is inert with
respect to the gas. In particular, the material is

selected from the group comprising glass, quartz glass,
fused quartz, ceramic, glass ceramic and/or metal.
These materials are inert, i.e. unreactive, with
respect to a large number of process gases. Moreover,
some materials, such as quartz glass or glass ceramic,
have a low coefficient of thermal expansion. This is
particularly important in the case of an apparatus
which is made up of component parts of various
materials. Within a permissible tolerance, one
dimension of a component part can change. This ensures
that the apparatus is not destroyed during the heat
treatment on account of mechanical stress, i.e. is
preserved. What is more, it makes it more easily
possible to keep a check on a gas atmosphere. A
possible gap of a component part or between the
component parts of the apparatus scarcely changes
during the heat treatment as a result of the low
coefficient of thermal expansion of its component
parts. An additional advantage results from use of a
machinable material (for example machinable ceramic,
glass ceramic or machinable fused quartz).
It is described below how it is ensured by various
configurations of the heat-treatment unit that
materials being processed of a large surface area, in
particular multilayer bodies with an unsymmetrical
sequence of layers, can be heat-treated while
controlling a temperature homogeneity of the material
being processed.
The material being processed of the heat-treatment unit
is, for example, a multilayered element which has a
first layer and at least one second layer. The heat
treatment takes place by an amount of energy being
taken up by the multilayered element, with a first
partial amount of the amount of energy being taken up
by the first layer and a second partial amount of the
amount of energy being taken up by the second layer.
The heat-treatment unit, which has at least one energy

source of the amount of energy, is characterized in
that the first layer is arranged between a first energy
source and the second layer and the second layer is
arranged between a second energy source and the first
layer. At least one of the energy sources has an
emission of a specific electromagnetic radiation with a
radiation field, and at least one of the layers has a
specific absorption for this electromagnetic radiation
and is arranged in the radiation field. In addition,
at least one transparent element, which has a specific
transmission and a specific absorption for the
electromagnetic radiation, is arranged in the radiation
field between the energy source with the radiation
field and the layer which has the absorption of the
electromagnetic radiation and is arranged in the
radiation field.
The transparent element helps to heat up the layers of
the multilayered element individually, i.e. to control,
regulate and/or preset in a specifically selective way
the partial amount of the amount of energy which the
layer takes up. For example, an amount of energy is
determined during the heat treatment with the aid of a
control loop (see below). It is also conceivable for a
presetting of the energy sources (for example energy
density, type of energy, etc.) to be sufficient without
an additional control loop. Individual heating-up of
the layers of the multilayered element is possible even
in the case of very high heating-up rates of from l°C/s
to, for example, 100°C/s and more. The individual
heating-up succeeds in keeping a mechanical stresses
and a deformation of the multilayered element thereby
caused under certain circumstances as small as possible
during the heat treatment.
The basis for this is the transparent element, which is
optically partially transmitting (semitransparent).
The transmission, which for a specific wavelength lies
between 0.1 and 0.9, for example, allows the

electromagnetic radiation described above to pass
through the transparent element onto a layer. The
layer can take up a corresponding amount of energy or
partial amount of the amount of energy which is
directly emitted by the energy source.
The transparent element also has a certain absorption
for the electromagnetic radiation. The energy which is
thereby taken up may be emitted to a surrounding area
in the form of heat radiation and/or heat conduction.
In a special configuration, the apparatus for heat-
treating a multilayered element has a transparent
element which radiates and/or conducts heat in the
direction of the multilayered element through the
absorption of the electromagnetic radiation. In this
way it is possible to heat-treat a layer by heat
radiation and/or heat conduction.
It is also conceivable for a first layer of the
multilayered element, which transmits the heat
radiation, to be heat-treated substantially only by
heat conduction, while a second layer of the same
multilayered element is heat-treated substantially by
the heat radiation from the same transparent element.
A first layer with a corresponding transmission is, for
example, a layer of glass. If electromagnetic
radiation of an energy source and/or a transparent
element comes into contact with the glass element, a
small proportion of the radiation (approximately 4%) is
reflected. Most of the radiation (> 90%) passes
through the glass more or less unhindered and then
impinges on a second layer of the multilayered element.
This radiation can be absorbed there and leads to an
amount of energy being taken up by the second layer.
The glass layer cannot be heat-treated sufficiently
quickly by radiation or heat radiation at a very high
heating-up rate. By contrast, relatively quick heat
treatment can be achieved by heat conduction if the
transparent element is able to take up a partial amount

of the amount of energy and transit it to the glass
layer.

The case in which the transparent element itself is a

layer of the multilayered element is also conceivable.

The transparent element can take up a partial amount of

the amount of energy through absorption of part of the

electromagnetic radiation and can pass on a further

partial amount of the amount of energy by transmission,

for take-up by a further layer.




In a special configuration of the heat-treatment unit,
one layer of the multilayered element is a supporting
layer for at least one further layer of the
multilayered element. The multilayered element has, in
particular, an unsymmetrical sequence of layers. For
example, the multilayered element comprises a
supporting layer which is coated on one side.
Individual layers of the multilayered element may also
be arranged next to one another.
In a special configuration, one layer of the
multilayered element has a material which is selected
from the group comprising glass, glass ceramic,
ceramic, metal and/or plastic. Temperature-resistant
plastic, such as Teflon, comes into consideration in
particular as the plastic. One layer is, for example,
a metal foil. The metal foil may also act as a
supporting layer.
The partial amount of the amount of energy which is
taken up by a layer depends, for example, on the
absorptivity, emissivity and/or reflectivity of the
layer. It also depends, however, on the type of energy
source and on the way in which the amount of energy is
transmitted to the multilayered element or to a layer
of the multilayered element.

One of the energy sources of the heat-treatment unit
is, for example, an energy source of thermal energy.
The layer may be supplied with the thermal energy
directly. Heat radiation, heat conduction and/or
convection come into consideration here. In the case
of heat radiation, the energy source may itself be a
source of heat radiation. The heat radiation is, for
example, electromagnetic radiation in the wavelength
range between 0.7 and 4.5 µm. The corresponding layer
is arranged in the radiation field of the energy
source. The layer is impinged by the electromagnetic
radiation of the energy source and at least partially
absorbs the electromagnetic radiation.
It is also possible, however, for a layer to be
supplied with any desired energy, which is converted
into thermal energy in the layer. For example, a layer
is irradiated with high-energy UV light, which the
layer absorbs. Absorption of a high-energy light
quantum causes a molecule of the layer or the entire
layer to become electronically excited. Energy which
is thereby taken up can be converted into thermal
energy.
In addition to heat radiation and heat conduction, it
is also possible for a layer or the entire element to
be heat-treated by convection. In this case, a gas
with a specific energy is directed past the layer, with
the gas releasing the energy to the layer. Gas
directed past may at the same time act as process gas.
Moreover, a layer can also be cooled by heat conduction
and/or convection. In this case, negative thermal
energy is supplied to the layer. In this way, it is
also possible to control the amounts of energy or the
partial amounts of the amounts of energy and, for
example, additionally influence the mechanical stresses
in the multilayered element.

In a special configuration, there is an energy
transmitter for the transmission of the amount of
energy to the multilayered element. The energy
transmitter acts as a secondary energy source. The
energy transmitter absorbs, for example,
electromagnetic radiation of a primary energy source,
for example a halogen lamp, from a higher energy band
and converts this electromagnetic radiation into heat
radiation, which is absorbed by the layer.
The indirect and/or direct surronding area of the
multilayered element may act as the energy transmitter
during the heat treatment. It is conceivable for an
energy transmitter to be arranged with the multilayered
element for heat treatment in an interior space of a
heat-treatment container. The energy transmitter may
also be arranged outside the container, for example on
a wall of the heat-treatment container or at a distance
from the heat-treatment container. It is conceivable
for the energy transmitter to be a coating of the heat-
treatment container. The energy transmitter is, for
example, a graphite film. It is even possible for the
heat-treatment container itself to assume the function
of an energy transmitter. A function of this type is
provided, for example, in the case of a heat-treatment
container made of graphite. Finally, the transparent
element is nothing other than an energy transmitter.
Similarly, in the case of energy transmission by
convection, a gas acts as an energy transmitter.
An amount of energy which is taken up by the
multilayered element may differ not only from layer to
layer but also within a layer. For example, during the
heat treatment, an edge effect occurs in the
multilayered element or in a layer of a multilayered
element. An edge region of the layer is at a different
temperature than an inner region of the layer. A
lateral temperature gradient is established during the
heat treatment. This takes place, for example,


whenever a radiation field of the energy source is
inhomogeneous. In this case, an energy density of the
radiation field on a surface area to which the
radiation is radiated is not identical everywhere. A
lateral temperature; inhomogeneity may also be
established when the radiation field is homogeneous, if
a greater amount of jenergy per unit volume is absorbed
on account of the j larger absorbing area per unit
volume. To compensate for the temperature gradient, it
is possible, for example, to use an energy source which
comprises a multiplicity of subunits. Each subunit may
be actuated separately, and in this way each amount of
energy supplied from a subunit to a layer can be set
separately. An example of an energy source of this
type is an array or matrix of individual heating
elements. An example of a heating element is a halogen
lamp. The array or matrix can also be used to
establish a lateral temperature gradient in the layer.
In this way, it would be possible, for example, to
produce permanent or transient deformation of the
layered element in a specifically selective way. An
array or matrix is of great advantage in particular for
the heat treatment of a multilayered element in which
layers lie next to one another.
With respect to the energy source, it is advantageous
if the energy source or the energy sources operate in a
continuous mode. It is also conceivable, however, for
the energy sources to make the amount of energy or the
partial amounts of the amount of energy available to
the layers in a cyclical and/or pulsed mode. An energy
source of this type is, for example, an energy source
with pulsed electromagnetic radiation. In this way, an
amount of energy can be supplied to the layers at the
same time or within a temporal sequence (for example
alternately).

The following properties of the energy source of
electromagnetic radiation are particularly
advantageous:
• The energy source has a homogeneous radiation field.
• A spectral intensity distribution of the energy
source partially overlaps a spectral absorption of
the layer, of the transparent element and/or of any
heat-treatment container that may be present (see
below).
• The energy source is corrosion-resistant and/or
corrosion-protected in the presence of a process gas.
• The energy source has a high energy density, which is
sufficient to allow a mass of the multilayered
element (and, if appropriate, that of a heat-
treatment container) to be heated up at a heating-up
rate of over l°C/s.
In a special configuration, the transparent element of
the apparatus has at least one spacer, against which
the multilayered element bears in order for a laterally
homogeneous amount of energy to be taken up by the
multilayered element. For example, the layer by means
of which the multilayered element rests on the
transparent element or the spacer is primarily heat-
treated by homogeneous heat radiation. In this form,
the spacer preferably has a material which has a low
absorption for the electromagnetic radiation. A spacer
projects, for example, beyond a surface of the
transparent element by a few µm to mm.
The layer resting on the spacers may also be primarily
heat-treated by heat conduction. For this purpose, the
spacers have, for example, a thermal conductivity which
is necessary to achieve a corresponding heat-treatment
rate. For energy transmission by heat conduction, it
is also conceivable for the spacer to have a high
absorption for an electromagnetic radiation of an

energy source, with the electromagnetic radiation being
additionally converted into thermal energy.
In particular, the transparent element has a
multiplicity of spacers. With a multiplicity of
spacers which are arranged uniformly and in contact
between the layer of the multilayered element and the
transparent element, it is additionally possible to
achieve homogenization of the lateral temperature
distribution.
In a special configuration, the transparent element
and/or the spacer has a material which is selected from
the group comprising glass and/or glass ceramic. Glass
ceramic has various advantages:
• It can be used for heat treatment in a wide
temperature range from, for example, 0°C to, for
example, 700°C. Glass ceramic has, for example, a
softening point which lies above the temperature
range.
• It has a very low coefficient of thermal expansion.
It is resistant to thermal shocks and is free of
distortion in the abovementioned temperature range of
heat treatment.
• It is chemically inert with respect to a large number
of chemicals and has low permeability for these
chemicals. A chemical of this type is, for example,
the process gas to which a layer or the entire
multilayered element is exposed during the heat
treatment.
• It is optically partially transmissive in the
spectral range of many energy sources for
electromagnetic radiation, in particular in a
wavelength range in which a radiation density of the
energy sources is high. A radiation source of this
type is, for example, a halogen lamp with a high
radiation density of between 0.1 and 4.5 |µm.

Glass, in particular quartz glass, are likewise
conceivable as a material for the transparent element.
The advantage of glass is that it can be used at high
temperatures of up to 1200°C. These materials exhibit
a high transmission and low absorption in the spectral
range of an energy source in the form of a halogen
lamp. The light passes through the transparent element
substantially unhindered and reaches a layer with a
corresponding absorption for the electromagnetic
radiation, the layer taking up an amount of energy and
being heated. The transparent element is scarcely
heated by the radiation.
In one process application it is possible for material
of the heated layer to evaporate and be deposited on a
relatively cold surface of the transparent element. To
prevent this, it is possible to ensure that the
transparent element is heated to a necessary
temperature during the heat treatment. This is
achieved by transmitting an amount of energy to the
transparent element by heat conduction and/or
convection. Electromagnetic radiation which the
transparent element absorbs is also conceivable. It is
conceivable for the transparent element to have a
coating which absorbs a certain part of the
electromagnetic radiation. The energy taken up as a
result can be passed on to the transparent element made
of glass or quartz glass. In this form, the
transparent element, comprising the glass element with
the coating, is optically partially transmissive and
can be used to transmit energy to the multilayered
element both by heat radiation and by heat conduction.
In a special configuration, at least one layer of the
multilayered element is in contact with a process gas.
It is also conceivable for the entire multilayered
element to be exposed to the process gas. An inert gas
(molecular nitrogen or noble gas) comes into
consideration for example as the process gas. The


process gas does not react with a material of the
layer. However, a process gas which does react with a
material of the layer is also conceivable. Under the
action of the process gases, the functional layer
forms. For example, the process gas has an oxidizing
or reducing effect on a material of the layer.
Possible process gases for this are oxygen, chlorine,
hydrogen, elemental selenium, sulfur or a hydride. It
may also be an etching process gases such as HCL or the
like. Further examples of the process gas are H2S and
H2Se, which are used in the production of a thin-film
solar cell (see below) . Finally, all gases or gas
mixtures which react with a material of a layer in a
corresponding way are conceivable.
It is advantageous if the layer is exposed to a defined
process-gas atmosphere. The defined process-gas
atmosphere comprises, for example, a partial pressure
of the process gas or gases during the heat treatment.
It is also conceivable, for example, for a layer or the
multilayered element to be in contact with a vacuum for
heat treatment.
A defined process-gas atmosphere can be achieved, for
example, by directing the process gas past the layer at
a specific velocity. In this case, a process gas with
various partial pressures can act on the layer in the
course of the heat treatment. It is also conceivable
for various process gases to be successively in contact
with the layer of the layered element.
Preferably, at least the layer which is in contact with
the process gas is enclosed. This is achieved, for
example, by sheathing the layer, it being possible for
the sheathing to be secured to the supporting layer.
The sheathing is filled with the process gas before or
during the heat treatment. The process gas is in this
case concentrated on a surface of the layer of which
the properties are to be influenced by the process gas.


In this way it is possible to prevent a surrounding
area from being contaminated by the process gas. This
is important in particular when using a corrosive
and/or toxic process gas. Furthermore, it is possible
to operate with a stoichiometric amount of process gas
necessary for conversion of the layer. There is no
unnecessary consumption of process gas.
In a special configuration of the invention, the
multilayered element is arranged in a heat-treatment
container. In this case, at least one container wall
of the heat-treatment container has a transparent
element. The heat-treatment container has the
advantage that it automatically forms the sheathing of
the layer or the entire multilayered element. The
sheathing does not need to be secured to the
multilayered element. In the case of a closable heat-
treatment container, the process-gas atmosphere can be
set in a specifically selective and easy way. For
example, the heat-treatment container offers a
sufficiently large volume for the process gas required
during the heat treatment. If the heat treatment
requires a homogeneous and reproducible distribution of
the process gas over a layer, a gas discharge from the
heat-treatment container can also be set in a
specifically selective way. This may be necessary, for
example, whenever the heat treatment is carried out at
a very high heating-up rate. In this case, the process
gas expands. If the heat-treatment container does not
withstand the gas pressure thereby occurring, the heat-
treatment container is deformed or even destroyed.
However, deformation should be prevented, for example,
if the multilayered element rests on the base of the
heat-treatment container. Deformation of the heat-
treatment container may lead to a lateral temperature
inhomogeneity in the multilayered element.
Moreover, the heat-treatment container may be a means
for transporting the multilayered element during heat


treatment. The heat-treatment container has the
advantage that it is not possible, for example, to rule
out the possibility of a layer (supporting layer or
substrate) of glass breaking during the heat treatment.
In the event of such a substrate breaking, the broken
material can be easily removed from the heat-treatment
units or from the apparatus for heat treatment. This
contributes to stabilizing the heat-treatment process.
In a particular configuration, the container wall of
the heat-treatment container which has the transparent
element is a cover and/or a base of the heat-treatment
container. For example, one layer of the multilayered
element rests directly on the transparent element of
the base. As described above, the transparent element
may have spacers. The cover likewise has the
transparent element, which, for example, is not in
contact with the multilayered element or a layer of the
multilayered element. In this way, the layer of the
multilayered element which rests on the base can be
heated by heat conduction, the layer facing the cover
can be heated by heat radiation. The layer facing the
cover can easily be exposed to a process gas.
In a further configuration, the base and/or the cover
of the heat-treatment container is formed by in each
case at least one multilayered element. In this case,
the layer of the multilayered element which, for
example, is intended to come into contact with a
process gas is directed into the interior space of the
heat-treatment container. This solution is possible if
the multilayered element or the layers of the
multilayered element have a low coefficient of thermal
expansion and/or the heat-treatment rate is low. For a
high heat-treatment rate, the multilayered element
advantageously has a supporting layer with a high
coefficient of thermal conductivity. The supporting
layer is directed outward. For example, here the

supporting layer is a transparent element as described
above.
In a special configuration, the heat-treatment
container, the transparent element and/or the energy
transmitter have a material which is inert with respect
to a process gas. Moreover, it is advantageous for an
entire heat-treatment process area to be inert with
respect to the process gas used. The process area also
includes, for example, the energy source (primary
energy source).
The material is selected according to the process gas.
Glass, glass ceramic and ceramic are conceivable, for
example. A fiber-reinforced material, such as carbon-
fiber-reinforced graphite can similarly be used. A
material such as SiC, which has a high coefficient of
thermal conductivity, is also conceivable. The heat-
treatment container may consist of a metal or an alloy.
A plastic which is resistant up to a specific
temperature is similarly possible.
In addition to being chemically inert with respect to
the process gas, the following properties are of
advantage for the material of the heat-treatment
container:
• The material of the heat-treatment container is free
from distortion under the heat-treatment conditions.
It is also resistant to temperature shocks. This is
the case in particular whenever it has a low
coefficient of thermal expansion.
• The thermal softening point of the material of the
heat-treatment container lies above a maximum
temperature of the heat treatment.
• The heat-treatment container exhibits a low or
defined permeability with respect to a process gas.

In a special configuration, there is a device for
detecting a dimension of at least one physical
parameter of the apparatus and/or a heat-treatment unit
that is dependent on the heat treatment, for
controlling the first and second partial amounts of the
amount of energy.
One conceivable parameter is an absorption,
transmission and/or reflection property of a layer.
The dimension of the parameter is the value of the
parameter. For example, a wavelength of a maximum
absorption may depend on the temperature. The dimension
of the parameter would in this case be the
corresponding wavelength.
In particular, the parameter is a temperature of the
multilayered element. In this case, the dimension is a
value of the temperature. The detection of the
temperature of a layer of the multilayered element, of
the transparent element and/or of the heat-treatment
container or a wall of the heat-treatment container is
also conceivable. During the heat treatment, it is
always possible for at least one parameter of the
multilayered element and/or of a layer to be detected.
For example, the partial amount of the amount of energy
which is taken up by the layer is increased or
decreased on the basis of the detected temperature of a
layer. In this way, a temperature inhomogeneity or a
temperature gradient in the direction of the thickness
of the multilayered element can be avoided. This
temperature inhomogeneity can, however, also be
increased, should this be necessary.
For example, the device for detecting the temperature
is be a pyrometer, which is directed at the layer. The
pyrometer detects, for example, the heat radiation
which is emitted by the layer. The temperature of the
layer can be concluded on the basis of the heat
radiation. A temperature detector which is connected

to the layer and the temperature of which is controlled
by heat conduction is also conceivable.
It is also conceivable for the temperature of the layer
or of the multilayered element not to be measured
directly but indirectly. For example, a pyrometer is
directed at the heat-treatment container in which the
multilayered element is heat-treated. The temperature
of the heat-treatment container may be influenced by
the temperature of the multilayered element. The
temperature of the layer of the multilayered element is
concluded on the basis of the temperature of the heat-
treatment container. The amount of energy or the
partial amount of the amount of energy is controlled on
the basis of the measured temperature of the heat-
treatment container. For this purpose, for example, a
kind of "calibration measurement" is to be carried out
prior to the heat treatment, representing a
relationship between the measured temperature of the
heat-treatment container and the actual temperature of
the layer or of the layered element. The "calibration
measurement" indicates a desired value of the
temperature. The actual value is detected. A
comparison between the desired value and the actual
value supplies a controlled variable for controlling
the amounts of energy.
The detection (and also the control of the partial
amounts of the amount of energy) takes place in
particular with a local resolution in the direction of
the thickness of the multilayered element and with a
temporal resolution within the time frame of the heat
treatment. For example, the multilayered element is
heated up at a heat-treating rate of 25°C/s. In that
case, both the detection and the control of the partial
amounts of the amount of energy would take place so
quickly that a temperature difference between the
layers of the multilayered element during the heat

treatment remains below a prescribed maximum, for
example.
The temperature inhomogeneity in the direction of the
thickness may, in combination with a transient
deformation of the multilayered element, also lead to a
lateral temperature inhomogeneity in the multilayered
element. Lateral means, for example, within a layer of
the multilayered element perpendicular to the direction
of the thickness. For example, the multilayered
element rests on a base of graphite. The supply or
take-up of the amount of energy by the layer of the
multilayered element resting on the base takes place
through heat conduction. A temperature inhomogeneity
in the direction of the thickness may cause a transient
deformation of the multilayered element in the form of
bending of the multilayered element. In this case, the
contact between the multilayered element and the base
of the heat-treatment container that is necessary for
the heat conduction is partially detached. As a
consequence of this, there is a lateral temperature
inhomogeneity of the resting layer or of the
multilayered element. It is therefore particularly
advantageous if, for the detection of the parameter
(and control of the amounts of energy), there is a
local resolution not only in the direction of the
thickness but also laterally.
In a special configuration, the parameter is a
deformation of the multilayered element. The
occurrence of a temperature inhomogeneity may cause
deformation. For example, the multilayered element is
concavely curved.
The multilayered element rests on the base of, for
example, a heat-treatment container. Concave
deformation has the effect that a distance between the
resting surface and the multilayered element forms in
the edge region of the multilayered element. A laser

interferometry or laser light reflection device can be
used, for example, to detect a dimension of such a
deformation. The control of the amounts of energy
takes place on the basis of the dimension. It is
advantageous if the dimension is detected in an early
stage of the deformation and it is possible to react
quickly to it.
For an abovementioned device for detecting a dimension
of a parameter which is dependent on the heat treatment
with the aid of an optical device (for example a
laser) , it is advantageous if the layer which is to be
examined is accessible for light from the optical
device and a detection signal can be unequivocally
assigned to the parameter to be detected. The
wavelength of a laser should, for example, differ
sufficiently from the heat radiation of the
multilayered element. If the apparatus is equipped
with a heat-treatment container, it would be
advantageous if the transparent element is sufficiently
transparent to the light of the laser.
With the aid of the apparatus, it is also possible to
achieve a desired deformation of the multilayered
element. For this purpose, it may also be appropriate
to monitor the deformation during the heat treatment in
the manner described above. For example, it is
possible to produce a curved thin-film solar cell. To
achieve specifically selective deformation, the
multilayered element is, for example, laid on a
corresponding mold or mask. The mold or mask may
directly be an energy source. The multilayered element
is heated to above a softening point of the supporting
layer. As a consequence of this, the multilayered
element adopts a shape which corresponds to that of the
mask or mold. The mask is, for example, integrated in
a base of the heat-treatment container. The mask could
be, for example, the transparent element.

To achieve the object, in addition to the apparatus
there is specified a method for heat-treating a
material being processed in a heat-treatment space of a
heat-treatment container under a specific process-gas
atmosphere of a process gas. The method comprises the
following method steps: a) producing the intermediate
space between the heat-treatment container having the
heat-treatment space with the material being processed
and the heat-treatment chamber, b) producing the
process gas atmosphere in the heat-treatment space and
a gas atmosphere of a further gas in the intermediate
space and c) heat-treating the material being
processed.
The intermediate space with the further gas, for
example a purging gas, acts as a buffer, so that the
process gas which is located in the heat-treatment
space cannot reach the heat-treatment chamber, or only
in a rarefied form. Contamination or corrosion of the
heat-treatment chamber can be prevented. The selection
of the material of the heat-treatment chamber is
virtually independent of the process gas. The
intermediate space can be filled once with the purging
gas. It is also conceivable for a continuous stream of
purging gas to be passed through the intermediate
space, removing from the intermediate space process gas
possibly escaping from the stack body. A removal of
escaping process gas is also achieved by a pressure
gradient being established from the hollow space of the
stack body to the intermediate space.
In a special configuration, a specific temperature of
the heat-treatment chamber, the gas pressure in the
heat-treatment space and/or the gas pressure in the
intermediate space are set. In this case, the gas
pressure in the heat-treatment space is influenced in
particular into the gas pressure in the intermediate
space [sic].

According to a special configuration, a pressure
gradient is set between the heat-treatment space and
the intermediate space. This is achieved in particular
by the heat-treatment chamber being arranged in a
shroud.
In a further configuration, the heat treatment
comprises at least one heating-up and/or at least one
cooling-down process. In this case, it is possible in
I particular to run through a plurality of heating-up and
cooling-down phases.
According to a further material being processed, a
multilayered element with a layer and at least one
further layer is used.
In this case, a multilayered element with a layer which
has copper, indium, gallium and/or selenium is used in
particular. A supporting layer of the multilayered
element is made in particular of glass and/or metal.
In a special configuration, a process gas which is
selected from the group comprising H2S, H2Se, H2, He
and/or N2 is selected.
In particular, a further gas, which is selected from
the group comprising N2 and/or noble gas, is used.
The method is suitable in particular for producing a
photovoltaic thin-film chalcopyrite absorber of a solar
cell and/or of a solar module.
The process-gas atmosphere and the further gas
atmosphere may be produced before, during or after the
heat treatment. The materials being processed can in
this case be brought simultaneously into contact with a
plurality of process gases (gas mixture) . It is also
conceivable for the material being processed to be
brought successively into contact with different

process gases and/or purging gases. Consequently, a
variable process gas profile (temporal sequence of
different partial pressures of the process gas or
gases) is possible. In this way, it is possible, for
example, to use both oxidizing and reducing process
gases, or to introduce a dopant into the material being
processed in a specifically selective way.
In a special configuration, there is a shroud of the
heat-treatment container, so that there is a buffer
space for gas between the intermediate space and the
heat-treatment space.
In the intermediate space between the heat-treatment
chamber and the heat-treatment container, a gas
pressure of a purging gas that is greater than the gas
pressure in the buffer space is produced. For this
purpose, gas outlet openings are preferably provided in
the shroud, led to the outside for example via a
manifold pipeline through the intermediate space and
through the heat-treatment chamber, and directed there
for example into a gas disposal unit. Consequently,
the pressure prevailing in the buffer space of the
shroud is approximately the same as that in the gas
disposal unit (for example atmospheric pressure). The
effect of this arrangement can be referred to as gap
counterflow purging, which serves the purpose of
opposing the stream of process gas diffusing out of the
heat-treatment space with a counteracting stream of
inert gas at a gap of a lead-through in the shroud, for
example at an assembly gap of a component of the
shroud, with the aim of preventing condensation of
process gases on the walls of the heat-treatment
chamber or corrosion of the walls of the heat-treatment
chamber. The latter can also be achieved, moreover, by
suitable coating of the walls of the heat-treatment
chamber.

The gap counterflow purging works on the following
principle: the heat-treatment container filled with the
process gas is arranged in the shroud. It is not
possible to rule out the possibility of the process gas
5 getting into the buffer space of the shroud.
The buffer space of the shroud and the intermediate
space between the heat-treatment container and the
heat-treatment chamber are connected by gaps or
10 openings. A pressure gradient from the intermediate
space to the buffer space is built up as a result of
the choice of the gas pressures. This is achieved, for
example, by extracting the purging gas from the buffer
space by suction and/or introducing the purging gas
15 into the intermediate space and a resultant pressure
build-up with respect to the pressure of the buffer
space, which may, as described above, be in contact
with the surrounding area of the heat-treatment
apparatus. This produces a stream of purging gas from
20 the intermediate space to the buffer space. The
process gas does not reach the chamber wall of the
heat-treatment chamber. In this way, a temperature of
the heat-treatment chamber, the gas pressure of the
buffer space and/or the gas pressure of the
25 intermediate space are set in particular during the
heat treatment.
In a special configuration, a multilayered element with
a layer and at least one further layer is used as the
30 material being processed and/or further material being
processed.
In this case, the heat treatment takes place by an
amount of energy being taken up by the multilayered
35 element, with a first partial amount of the amount of
energy being taken up by the first layer and a second
partial amount of the amount of energy being taken up
by the second layer, with at least one energy source
being used for supplying the amount of energy to the

multilayered element. In this case, an apparatus
described above is used in particular. The method
steps are: arranging the multilayered element between a
first and at least one second energy source, so that
the first layer is arranged between the first energy
source and the second layer and the second layer is
arranged between the second energy source and the first
layer, with at least one energy source of a specific
electromagnetic radiation with a radiation field being
used as the energy source, and at least one of the
layers absorbing the electromagnetic radiation and
being arranged in the radiation field of the energy
source, and arranging a transparent element in the
radiation field of the energy source between the energy
source and the layer which lies in the radiation field
of the energy source and absorbs the specific
electromagnetic radiation, and heat treatment of the
multilayered element.
In a special configuration, the transparent element
absorbs a specific amount of energy and supplies the
amount of energy to the layer. In a further
configuration, detecting a dimension of a physical
parameter of the multilayered element that is dependent
on the heat treatment is carried out for controlling
the take-up of the amount of energy during the heat
treatment and controlling the first and second partial
amounts of the amount of energy. In a special
configuration, the transparent element supplies the
layer with the amount of energy by heat conduction
and/or heat radiation.
In a special configuration, a multilayered element with
a layer which has copper, indium, gallium and/or
selenium is used. In particular, a multilayered
element with a supporting layer made of glass and/or
metal is used. The supporting layer may, for its part,
have a coating (for example a metal layer on a glass
plate). A gas which is selected from the group

comprising H2S, H2Se, H2, He and N2 is used as the
process gas. The method serves in particular for
producing a photovoltaic thin-film chalcopyrite
absorber of a solar cell and/or of a solar module. In
the case of the solar module, there are a multiplicity
of individual solar cells connected in series. The
glass is preferably soda-lime glass. The corresponding
layer acts as a supporting layer. On the supporting
layer, a molybdenum layer is applied as an electrode
and, over the molybdenum layer, a functional layer is
applied, that is a copper-indium-gallium-sulfoselenide
(CIGSSe) semiconductor layer. A thickness of the
layered element, comprising the glass element and
semiconductor layer, is typically 2 to 4 mm, with a
molybdenum layer of approximately 0.5 µm and a
semiconductor layer of approximately 3 µm. The
specified range for the thickness of the multilayered
element is not to be used exclusively. A limiting
factor is a capability for producing a large substrate
which is as planar as possible, and consequently can be
processed with the described apparatus or with the
described method to form a multilayered element.
To sum up, the following advantages are obtained with
the invention:
• A material being processed can be heat-treated in any
desired process-gas atmosphere. In particular, a
toxic and/or corrosive process gas can be used.
Condensations of a process substance on the chamber
walls can be avoided.
• A heating-up and cooling-down profile can be variably
set up.
• A material being processed in the form of a
multilayered element of a large surface area with an
unsymmetrical layer structure (for example a
multilayered element with a single layer on a


supporting layer) can be heat-treated at a high heat-
treating rate of over l°C/s.
• The layers of the multilayered element may in this
case have a greatly differing coefficient of thermal
conductivity and/or greatly differing emissivity.
• A temporal and local resolution of the detection and
the control of a dimension of a parameter dependent
on the heat treatment allows heat treatment to be
conducted particularly safely. For example, it is
possible to react to a change in a property of the
material being processed (for example emissivity or
absorptivity) during the heat treatment and set the
process parameters (pressure, temperature, energy
density, etc.) to it.
• Heat treatment to near a softening point of a
supporting layer of the material being processed is
possible.
• In the case of heat treatment beyond the softening
point of the supporting layer, a permanent
deformation of the multilayered element is possible.
• A defined heat-treatment area with a defined process-
gas atmosphere can be created. Various process gases
with various partial pressure profiles can be set
simultaneously or successively before, during and/or
after the processing.
• All the method steps necessary for the processing can
be carried out with a single apparatus.
An apparatus for heat-treating a material being
processed and a corresponding method for this are
represented on the basis of several exemplary
embodiments and the associated figures. The figures


are schematic and do not represent illustrations that
are true to scale.
Figure 1 shows a cross section from the side of an
apparatus for heat-treating at least one
material being processed.
Figure 2 shows a method of heat-treating a plurality
of materials being processed.
The starting point is an apparatus 1 for heat-treating
a material being processed 33 (figure 1). The material
being processed 33 is arranged in a heat-treatment
space 16 of a heat-treatment container 11. The heat-
treatment container 11 lies in a shroud 12, so that
there is a buffer space 15 between the shroud 12 and
the heat-treatment container 11. Together with the
shroud 12, the heat-treatment container is arranged in
an evacuable heat-treatment chamber, so that there is a
distance 18 between the heat-treatment container 11 and
the heat-treatment chamber 13. The material being
processed is arranged in the container in the method
step 21, after which an appropriate process gas
atmosphere 17 and further gas atmosphere 191 are
created in the heat-treatment space 16 and in the
intermediate space 14 (and possibly in the buffer space
11) (step 22) . For producing the further gas
atmosphere, there is a closable opening 19 in the heat-
treatment chamber. The heat treatment takes place in
process step 23.

Patent claims
1. An apparatus for heat-treating at least one
material being processed (3) in a heat-treatment
space (16) of a heat-treatment container (14) under
a specific process-gas atmosphere (17) of at least
one process gas, characterized in that
- the heat-treatment container (14) in a heat-
treatment chamber (13) is arranged at a distance
(18) from the heat-treatment chamber (13), so
that there is an intermediate space (14) between
the heat-treatment container (11) and the heat-
treatment chamber (13), and
- there is a means (19) for producing in the
intermediate space (14) a further gas atmosphere
(191) of a further gas, different from the
process-gas atmosphere (17).
2. The apparatus as claimed in claim 1, the
intermediate space enclosing the heat-treatment
space.
3. The apparatus as claimed in claim 1 or 2, the heat-
treatment space and the intermediate space being
connected to each other in such a way that a
pressure gradient can be set between the heat-
treatment space and the intermediate space.
4. The apparatus as claimed in claim 3, a shroud of
the heat-treatment space being present for
producing a buffer space for gas to establish the
pressure gradient.
5. The apparatus as claimed in one of claims 1 to 4,
there being at least one heat-treatment unit with
an energy source for receiving an amount of energy
through the material being processed.

6. A method for heat-treating a material being
processed in a heat-treatment space of a heat-
treatment container under a specific process-gas
atmosphere of a process gas, with the method steps:
a) producing the intermediate space between the
heat-treatment container having the heat-
treatment space with the material being
processed and the heat-treatment chamber,
b) producing the process gas atmosphere in the
heat-treatment space and a gas atmosphere of a
further gas in the intermediate space and
c) heat-treating the material being processed.

7. The method as claimed in claim 6, a temperature of
the heat-treatment chamber, the gas pressure in the
heat-treatment space and/or the gas pressure in the
intermediate space being set.
8. The method as claimed in claim 7, a pressure
gradient being set between the heat-treatment space
and the intermediate space.
9. The method as claimed in claim 8, the heat
treatment comprising at least one heating-up and/or
at least one cooling-down operation.
10. The method as claimed in one of claims 6 to 9, in
which a multilayered element with a layer and at
least one further layer is used as the material
being processed.
11. The method as claimed in claim 10, a multilayered
element with a layer which has copper, indium,
gallium and/or selenium being used.
12. The method as claimed in claim 10 or 11, a
multilayered element with a supporting layer made
of glass and/or metal being used.

13. The method as claimed in one of claims 6 to 12, a
process gas which is selected from the group
comprising H2S, H2Se, H2, He and/or N2 being used.
14. The method as claimed in one of claims 6 to 13, a
further gas which is selected from the group
comprising N2 and/or noble gas being used.
15. The method as claimed in one of claims 6 to 14 for
producing a photovoltaic thin-film chalcopyrite
absorber of a solar cell and/or a solar module.

The invention relates to an apparatus for heat-treating
at least one material being processed in a heat-
treatment space of a heat-treatment container under a
specific process-gas atmosphere of at least one process
gas, characterized in that the heat-treatment container
in a heat-treatment chamber is arranged at a distance
from the heat-treatment chamber, so that there is an
intermediate space between the heat-treatment container
and the heat-treatment chamber, and there is a means
for producing in the intermediate space a further gas
atmosphere of a further gas, different from the
process-gas atmosphere.

Documents:

IN-PCT-2002-495-KOL-FORM 27-1.1.pdf

IN-PCT-2002-495-KOL-FORM 27.pdf

IN-PCT-2002-495-KOL-FORM-27.pdf

in-pct-2002-495-kol-granted-abstract.pdf

in-pct-2002-495-kol-granted-assignment.pdf

in-pct-2002-495-kol-granted-claims.pdf

in-pct-2002-495-kol-granted-correspondence.pdf

in-pct-2002-495-kol-granted-description (complete).pdf

in-pct-2002-495-kol-granted-drawings.pdf

in-pct-2002-495-kol-granted-examination report.pdf

in-pct-2002-495-kol-granted-form 1.pdf

in-pct-2002-495-kol-granted-form 18.pdf

in-pct-2002-495-kol-granted-form 2.pdf

in-pct-2002-495-kol-granted-form 26.pdf

in-pct-2002-495-kol-granted-form 3.pdf

in-pct-2002-495-kol-granted-form 5.pdf

in-pct-2002-495-kol-granted-form 6.pdf

in-pct-2002-495-kol-granted-gpa.pdf

in-pct-2002-495-kol-granted-others.pdf

in-pct-2002-495-kol-granted-priority document.pdf

in-pct-2002-495-kol-granted-reply to examination report.pdf

in-pct-2002-495-kol-granted-specification.pdf

in-pct-2002-495-kol-granted-translated copy of priority document.pdf


Patent Number 228413
Indian Patent Application Number IN/PCT/2002/495/KOL
PG Journal Number 06/2009
Publication Date 06-Feb-2009
Grant Date 04-Feb-2009
Date of Filing 19-Apr-2002
Name of Patentee SHELL SOLAR GMBH
Applicant Address OTTO HAHN RING 6, 81739 MUNICH
Inventors:
# Inventor's Name Inventor's Address
1 PROBST, VOLKER, ELILANDSTR 13, 81547 MUNICH
PCT International Classification Number H01L 31/18
PCT International Application Number PCT/DE2000/03719
PCT International Filing date 2000-10-20
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 19950575.6 1999-10-20 Germany