Patent Description:
In particular, the present invention relates to roll-to roll vapor deposition system with linear evaporation sources usable for vapor deposition of In, Ga and Cu for controlled material coating of large flexible substrates in vacuum using the roll-to-roll process for the production of thin films of CIGS (Cu(ln,Ga)Se2, copper indium gallium di selenide).

The deposition of thin films of CIGS (CulnGaSe2, copper indium gallium di selenide) onto a flexible substrate is an important process step in the industrial manufacturing of solar panels and photovoltaic cells, which convert solar energy into electrical energy basing on the specific physical properties of said CIGS thin film.

In the following, CIGS thin film means a CIGS film exhibiting a thickness between <NUM> and <NUM> micrometers, most preferably between <NUM> and <NUM> micrometers.

Coating of objects using thermal evaporation requires a crucible to heat up and vaporize material that deposits itself onto a substrate. The deposition usually takes place within a vacuum chamber, thereby imposing spatial and physical constraints. Space may be especially constrained in the case of roll-to-roll deposition where the roll-to-roll mechanism must be contained within a desirably small vacuum chamber. Physical constraints are also strong in the case of coevaporation using multiple adjacent sources operating at different regulated temperatures to deposit material with a desired distribution and thickness onto a moving substrate.

A source for vapor deposition of material onto a roll-to-roll web ordinarily comprises: an elongated crucible that contains the material to be vaporized, at least one electrical heating element to direct the vaporized material flux onto the nearby moving web substrate. Several evaporation sources, also known as evaporation boats, may be arranged parallel to each other to deposit larger quantities of material and/or different materials onto the moving substrate.

It is often necessary to regulate the flux of material leaving the crucible to achieve a controlled deposition thickness and composition along the length and the width of the moving substrate. The flux of material and its distribution is related to the crucible's temperature distribution and also to the distribution and shape of the openings that let the evaporated material flow out of the crucible. The temperature distribution within a crucible is ordinarily spatially non-uniform, and therefore related to the electrical power delivered to the heating elements at various locations within the evaporation source's assembly. <CIT> (also published as <CIT>) describes an apparatus for thermal evaporation in vacuum chambers comprising a container that itself comprises a metal tube extending across the container in the path of flow of the vapor to the openings structure, said metal tube being traversed by an electric resistance heater. European patent application <CIT> (also published as <CIT>) describes an arrangement for vaporizing materials comprising three heating circuits, two of which are provided to regulate the longitudinal distribution of temperature by independently and externally heating two halves of the crucible's vaporizer tube. Japanese patent application <CIT> (also published as <CIT>) describes a crucible divided into a plurality of independently heated regions located under the crucible's lower surface. <CIT> discloses a method for the deposition of a CIGS thin-film on a web with a roll-to-roll vapor deposition system comprising a vacuum deposition chamber enclosing three sets of linear evaporation sources, filled with In, Ga, Cu or Se. <CIT> discloses adjusting the deposition rate of evaporation sources during deposition of a CIGS film. TW201122128 discloses a linear evaporation source apparatus comprising an elongated horizontal crucible, a heater, and a plurality of nozzles on a face of a lid of the apparatus that is parallel to the longest centerline of the crucible, some of the nozzles being oriented orthogonally to the surface of the lid.

A problem in the field of thermal vapor deposition relates to the regulation of the thickness distribution and composition of the material layers deposited on a substrate using evaporation sources. This problem is especially acute with large substrates. It is therefore an object of the current invention to provide an evaporation source that enables spatial and time regulation of material deposited on a moving substrate such as a roll-to-roll web substrate.

Another problem in the field of thermal vapor deposition relates to the limited volume of the vacuum chambers where evaporation takes place, thereby imposing spatial constraints on the size of the sources used, the energy they consume and radiate, and their influence on the reliability of the entire vacuum deposition system. It is therefore a further object of the current invention to provide an evaporation source that is compact but whose design can readily be lengthened by a person ordinarily skilled in the art, can be combined into an array of sources, and enables fast regulation of material deposition with the benefits of low energy consumption, increased longevity, and reduced costs.

A further problem in the field of thermal vapor deposition relates to the efficiency of the deposition with respect to evaporated material consumption and especially to the changes in efficiency as the level within the evaporation source of material to be evaporated changes. It is therefore also a further object of the current invention to provide an evaporation source that consumes less material and energy than conventional evaporation sources to achieve a uniform deposition and to provide an evaporation source that can adapt to changes within the evaporation source of the level of material to be evaporated.

Yet a further problem in the field of thermal vapor deposition relates to the undesired deposition of material droplets, also known as spitting, onto the substrate. It is therefore yet a further object of the current invention to provide an evaporation source that reduces or prevents problems associated with spitting or projection of material droplets.

Also, a further problem in the field of thermal vapor deposition during long deposition cycles relates to the falling of material flakes or other particles into the evaporation source. It is therefore also an object of the current invention to provide an evaporation source that prevents problems associated with falling material flakes.

The invention's features advantageously solve several problems in the field of thermal vapor deposition, namely:.

Embodiments of the invention will now be described by way of example, with reference to the accompanying drawings, in which:.

The exemplary embodiments presented in this disclosure show the roll-to roll vapor deposition system with at least three sets of at least three evaporation sources, the evaporation source comprising a crucible, itself comprising at least three heating elements, at least one of which is contained within said crucible. The crucible is ordinarily closed by a lid. The heating element located within the crucible is positioned close to the top of the crucible and close to nozzle orifices present either in the lid or near the top of one of the crucible's long walls. Said nozzles may be shaped/oriented so as to direct the vapor flux in a desired direction. This proximity of the inner heating element to the nozzles ensures firstly that the heating elements block the line of sight from outside the evaporation source through the nozzles towards the material to be evaporated, and secondly that the nozzles are heated.

Someone skilled in the art will appreciate that the scales of the various components represented in the figures have been changed to improve clarity. Furthermore, the number and areas of components in the figures can be scaled up. However, the crucible will preferably keep approximately its illustrated configuration and proportions where the crucible is an elongated hollow body of rectangular or trapezoidal cross-section having a substantially flat bottom, a substantially flat top which is larger than the bottom, substantially flat side walls that may be, in the case of a trapezoidal cross-section, slightly inclined outwardly from the bottom to the top, as shown, and relatively small substantially flat rectangular or trapezoidal end walls. The crucible length is normally at least <NUM> times and preferably at least <NUM> times or even <NUM> times longer than its outer width at the top.

<FIG> present a first embodiment with three longitudinally-aligned coaxial heating rods.

<FIG> shows an embodiment of an evaporation source <NUM> comprising an elongated generally rectangular crucible <NUM> and a heater assembly <NUM> composed of three axially aligned heating rods <NUM>, <NUM>, <NUM>. Heater assembly <NUM> is supported at each end by passing through a support hole in each short face of crucible <NUM> and positioned close to the crucible's opening or top so that there is no contact between said heater assembly and molten material <NUM> to be evaporated present at the bottom of crucible <NUM> during ordinary operation. Heating rods <NUM>, <NUM>, and <NUM> are powered via pairs of insulated contacts <NUM>, <NUM>, <NUM>, <NUM>, and <NUM>, <NUM>, respectively. Evaporation source <NUM> comprises at least three temperature sensors <NUM>, <NUM>, <NUM> positioned against or, as shown in <FIG>, inside the thickness of, the lower surface of crucible <NUM>. Each temperature sensor <NUM>, <NUM>, <NUM> preferably extends so as to provide temperature of the material to be evaporated at a position situated under the mid-length of each heating rod <NUM>, <NUM>, <NUM> of heater assembly <NUM>, respectively.

<FIG> shows a preferred embodiment of the evaporation source <NUM> of <FIG> where crucible <NUM> is closed by lid <NUM>. Crucible <NUM> and lid <NUM> are ordinarily made of a refractory material for example primarily containing alumina (Al<NUM>O<NUM>), silica, boron nitride, graphite, molybdenum, tantalum, or tungsten. Lid <NUM> comprises at least one nozzle <NUM> positioned over heater assembly <NUM>. Lid <NUM> preferably comprises a plurality of nozzles <NUM> wherein no nozzle <NUM> provides a line of sight from outside crucible <NUM> to the surface of the material to be evaporated contained within crucible <NUM>. Furthermore, although the nozzles <NUM> may ordinarily be designed so as to direct the evaporated flux orthogonally to the surface of lid <NUM>, in this embodiment the nozzles are inclined, as shown in the cross-section of <FIG>. Although the channel of nozzles <NUM> is represented as being divergent, someone ordinarily skilled in the art may choose to design a different channel such as straight, convergent, convergent-divergent, differently divergent, and/or as an elongated slit so as to advantageously shape the pattern of material deposition onto the substrate. The cross-section of an embodiment with convergent-divergent nozzles is presented in <FIG>. Furthermore, although <FIG> presents one row of uniformly distributed nozzles <NUM>, it is also possible to have a non-uniform distribution of nozzles <NUM>, as presented in <FIG>.

<FIG> shows a cross-section of an embodiment of evaporation source <NUM> of <FIG> with molten material to be evaporated <NUM> at the bottom of crucible <NUM> occupying typically up to about <NUM>-<NUM>% or up to <NUM>% of the crucible's depth without touching any heating element. Lid <NUM> closes crucible <NUM>. The crucible is ordinarily able to contain an amount of molten material to be evaporated enabling the coating of <NUM> meters to <NUM> meters of substrate. Heater assembly <NUM>, represented in this cross-section by the centermost or principal heating rod <NUM>, is placed close to nozzles <NUM> so that no line of sight is established from outside crucible <NUM> to the surface of molten material <NUM>. Molten material <NUM> is typically a metal such as copper, indium, gallium, selenium, zinc, tin, gold, chrome, antimony, sodium, magnesium, aluminium, germanium, nickel, silver, cadmium, lead or other materials to be evaporated with a boiling point from <NUM> degrees Celsius to <NUM> degrees Celsius. Temperature sensor <NUM> is also present in the cross-section of the crucible bottom. Hole <NUM> serves in this embodiment as a channel for temperature sensor <NUM> in case there is a need to measure temperatures closer to the mid-length of crucible <NUM>. <FIG> illustrates how the channel of nozzle <NUM> may be designed so as to direct the evaporated flux at an angle that is not orthogonal to the plane of lid <NUM>. The angle at which nozzle <NUM> is oriented will ordinarily be between +<NUM>° and +<NUM>° with respect to the plane onto which nozzle <NUM> is fitted, in the present case the plane of lid <NUM>. <FIG> also shows how crucible <NUM> and lid <NUM> are provided with respective extended lips <NUM>, <NUM> at the perimeter where they are in contact. The pair of lips <NUM>, <NUM> acts as a circumferential joint which may also channel the vapor flux of material <NUM> that may leak through the pair of lips <NUM>, <NUM> between crucible <NUM> and lid <NUM>. Said lips <NUM>, <NUM> help reduce the amount of material that may deposit on an optional heat shield assembly presented in <FIG>.

<FIG> shows the preferred embodiment of evaporation source <NUM> of <FIG> surrounded by heat shields comprising lid heat shield assembly <NUM> and crucible heat shield assembly <NUM>. Said heat shield assemblies <NUM>, <NUM> are detailed in the cross-section of <FIG> therefore only shows the outer layer of the heat shield assemblies <NUM>, <NUM> comprising lid outer shield <NUM> placed on lid <NUM> but leaving clearance for nozzles <NUM>, and crucible outer shield <NUM> wrapped around crucible <NUM> till the edges of lid <NUM>. Said heat shields advantageously reduce radiation of heat away from the evaporation source, thereby reducing energy consumption and furthermore reducing the amount of heat radiated towards the substrate onto which the material is deposited, and/or towards adjacent components such as other evaporation sources and/or the evaporation source's supporting infrastructure.

<FIG> shows a cross-section detailing the heat shield assemblies <NUM>, <NUM> of the preferred embodiment of evaporation source <NUM> of <FIG>. As in <FIG>, evaporation source <NUM> contains molten material to be evaporated <NUM> heated by heater assembly <NUM> within crucible <NUM> closed by lid <NUM>. Crucible <NUM> also comprises temperature sensor <NUM> and temperature sensor channel <NUM>. Said heat shield assemblies <NUM>, <NUM> comprise at least one shielding layer and are represented in this figure by a three-layer shield assembly. Someone ordinarily skilled in the art will infer that the number, size, thickness, and spacing of shields may be varied. Lid heat shield assembly <NUM> comprises inner shield <NUM>, middle shield <NUM>, and outer shield <NUM>. Crucible heat shield assembly <NUM> comprises inner shield <NUM>, middle shields <NUM>, and outer shield <NUM>. A better thermal shielding is usually obtained by providing some separation between shields <NUM>, <NUM>, <NUM> and <NUM>, <NUM>, <NUM> so that their surfaces do not contact each other. Inner and outer shields <NUM>, <NUM>, <NUM>, <NUM> are ordinarily made of high-temperature resistant material such as molybdenum, tantalum, tungsten, niobium, rhenium, or titanium. Middle shields <NUM>, <NUM> are ordinarily made of a refractory material for example primarily containing alumina (Al<NUM>O<NUM>), silica, boron nitride, or felt made of carbon or graphite.

<FIG> present perspective views of a second embodiment with three coaxial axially-aligned heating coils.

<FIG> shows an assembly of three axially aligned electrical heating coils <NUM>, <NUM>, <NUM>. The central heating coil <NUM> is powered at each of its extremities via extended insulated contacts <NUM>, <NUM>. Insulated contacts <NUM>, <NUM> are located close to the common axis of heating coils <NUM>, <NUM>, <NUM> and extend in a direction parallel to said common axis. Heating coil <NUM> is located at one of the extremities of heating coil <NUM> and surrounds insulated contact <NUM>. Heating coil <NUM> is located at the other extremity of heating coil <NUM> and surrounds insulated contact <NUM>. Heating coils <NUM> and <NUM> are powered via insulated contacts <NUM>, <NUM> and <NUM>, <NUM>, respectively. Heating coils <NUM>, <NUM>, <NUM> may be of the same or different lengths, the same or different diameters, and have the same or different and non-uniform numbers of turns per unit length. In the preferred illustrated example, the central heating coil <NUM> is longer than the end heating coils <NUM>, <NUM>, all coils having approximately the same diameter.

<FIG> shows said assembly of <FIG> optionally complemented with electrical insulators <NUM>, <NUM> in the form of rings or discs positioned between heating coils <NUM>, <NUM>, <NUM>. Electrical insulators <NUM>, <NUM> are ordinarily made of a refractory non-electrically conducting material for example primarily containing alumina, silica, zirconia toughened alumina, steatite, or mullite.

<FIG> shows heater assembly <NUM> where said assembly of <FIG> is inserted into electrically insulating heater tube <NUM>. Heater tube <NUM> is ordinarily made of a refractory, non-electrically conducting material for example primarily containing alumina, silica, zirconia toughened alumina, steatite, or mullite.

<FIG> shows an embodiment of an evaporation source <NUM> comprising a crucible <NUM>, ordinarily an elongated container of trapezoidal cross-section made of refractory material, and a heater assembly <NUM> aligned with the crucible's long centerline and passing through corresponding holes in each trapezoid short side. Heater tube <NUM> is positioned close to the crucible's opening or top so that the material to be evaporated, also called a melt, remains at the crucible's bottom and below heater tube <NUM> during ordinary operation. Evaporation source <NUM> further comprises at least three temperature sensors <NUM>, <NUM>, <NUM>, such as thermocouples, positioned against the part of crucible <NUM> containing said melt. Temperature sensors <NUM>, <NUM>, <NUM> are preferably positioned within dedicated channels inside the thickness of the crucible's lower surface and extend so as to provide temperature of the melt region situated preferably under the mid-length of each heating coil <NUM>, <NUM>, <NUM> of heater assembly <NUM>, respectively.

<FIG> shows a preferred embodiment of the evaporation source <NUM> of <FIG> closed by lid <NUM>. Lid <NUM> comprises at least one nozzle <NUM>, for example as illustrated a line of nozzles distributed along the length of crucible <NUM>, positioned over heating tube <NUM> and such that no nozzle <NUM> provides a line of sight from outside crucible <NUM> to the surface of said melt.

<FIG> present perspective views of a third embodiment with three principal parallel heating rods and two external side-end heaters.

<FIG> shows an alternate embodiment of an evaporation source <NUM> comprising a crucible <NUM> that comprises a heater assembly <NUM> comprising three parallel heating rods <NUM>, <NUM>, <NUM> positioned side-by-side along the length of crucible <NUM>. Heating rods <NUM>, <NUM>, <NUM> are supported at each end by passing through electrically insulating support holes <NUM>, <NUM> in each short face of crucible <NUM> and positioned close to the opening or top of crucible <NUM> so that there is no contact between said heating rods and the liquid melt present at the bottom of crucible <NUM> during ordinary operation. Heating rods <NUM>, <NUM>, <NUM> are electrically connected in parallel so as to represent a single heating element and powered via insulated contacts <NUM>, <NUM>. Someone ordinarily skilled in the art will infer that heating rods <NUM>, <NUM>, <NUM> may also be connected in series or any combination of parallel and series, or that the number of heating rods positioned within crucible <NUM> and close to its top may be increased. Heating assembly <NUM> further comprises side heaters <NUM> and <NUM> that are mounted outside crucible <NUM> against each short face and powered by contacts <NUM>, <NUM> and <NUM>, <NUM>, respectively. It is understood that if the crucible <NUM> is surrounded by heat shields as in <FIG>, the side heaters <NUM> and <NUM> will be located inside the heat shields. Similarly to crucibles <NUM> of embodiments presented in <FIG> and <FIG>, crucible <NUM> comprises at least three temperature sensors <NUM>, <NUM>, <NUM> positioned against, or inside the thickness of, the lower surface of crucible <NUM>. Temperature sensor <NUM> preferably extends till the mid-length of heating rods <NUM>, <NUM>, <NUM>. Temperature sensors <NUM>, <NUM> preferably extend at most one third of the length of heating rods <NUM>, <NUM>, <NUM>.

<FIG> shows the embodiment of evaporation source <NUM> of <FIG> closed by lid <NUM>. Lid <NUM> comprises at least one nozzle <NUM>, for example as illustrated a line of nozzles distributed along the length of lid <NUM>, positioned over heater assembly <NUM> and such that no nozzle <NUM> provides a line of sight from outside crucible <NUM> to the surface of the melt within said crucible.

<FIG> shows an alternative embodiment of evaporation source <NUM> of <FIG> where lid <NUM> comprises <NUM> rows of, in this example fifteen, nozzles <NUM> distributed along the length of the lid, positioned over heating rods <NUM>, <NUM>, <NUM> and such that no nozzle <NUM> provides a line of sight from outside crucible <NUM> to the surface of the melt within said crucible.

<FIG> present perspective and cross-sectional views of fourth and fifth embodiments where nozzles are located on the side of the source. Said fourth and fifth embodiments are designed for evaporation deposition tasks where the substrate is located or moves along the side of the evaporation source, such as in roll-to-roll coating of flexible substrates.

<FIG> shows the fourth embodiment, which is an alternative embodiment of evaporation source <NUM> of <FIG> where crucible <NUM> has at least one of its long walls cut out so as to support an extended lid <NUM> bearing at least two faces: a top face and at least one side face. One of the side faces of lid <NUM> comprises at least one nozzle <NUM>, in this example a line of nozzles comprising a combination of circular and slit nozzles, so arranged that no nozzle <NUM> provides a line of sight from outside crucible <NUM> to the surface of the melt <NUM> within said crucible. <FIG> also shows that nozzles <NUM> are not distributed evenly along the side face of lid <NUM>.

<FIG> shows a cross-section of the embodiment of evaporation source <NUM> of <FIG>. It is conceptually similar to the cross-section of <FIG> with a crucible <NUM> containing molten material to be evaporated <NUM> at its bottom and comprising temperature sensor <NUM>, temperature sensor channel <NUM>, three parallel heating rods <NUM>, <NUM>, <NUM>, and lid <NUM> bearing nozzles <NUM>. <FIG> details how the walls of crucible <NUM> differ from that of <FIG>: the shape of crucible <NUM> is modified to support lid <NUM> bearing side-facing nozzles <NUM>. <FIG> also shows that the line of sight from outside evaporation source <NUM> through nozzles <NUM> towards the material to be evaporated <NUM> is obstructed by heating rod <NUM>. Evaporation source <NUM> also comprises extended lips <NUM>, <NUM> as a provision to reduce deposition of vaporized material <NUM> onto an optional (not presented in this figure) shield assembly <NUM> that would be conceptually similar to that presented in <FIG>.

<FIG> shows an alternative embodiment of evaporation source <NUM> of <FIG> where crucible <NUM> has a row of nozzles <NUM> close to the top of one of its side walls. In this embodiment the lid <NUM> bears no nozzles.

<FIG> shows a cross-section of the embodiment of evaporation source <NUM> of <FIG>. It is conceptually similar to the cross-section of <FIG> with a crucible <NUM> containing molten material to be evaporated <NUM> at its bottom and comprising temperature sensor <NUM>, temperature sensor channel <NUM>, three parallel heating rods <NUM>, <NUM>, <NUM>, and a lid <NUM> that bears no nozzles. In this embodiment, it is crucible <NUM> that bears convergent-divergent nozzles <NUM> close to the top of one of its side walls that runs parallel to heating rod <NUM>. <FIG> also shows that the line of sight from outside evaporation source <NUM> through nozzles <NUM> towards the material to be evaporated <NUM> is obstructed by heating rod <NUM>.

<FIG> shows a graph comparing the deposition profile, for example thickness Y of material deposited on a planar substrate, versus position X along the long axis of evaporation source <NUM>. Curve <NUM> represents the deposition profile for an evaporation source that would have only one full-length operating heating element, for example the evaporation source <NUM> of <FIG>-3D where only heating rods <NUM>, <NUM>, <NUM> would be switched on but where side heaters <NUM>, <NUM> would remain switched off. Curve <NUM> therefore represents a deposition profile with a relatively large amount deposited towards the centerline of the deposition area, whereas a comparatively lesser amount is deposited towards the edge of the deposition area. Curve <NUM> represents the deposition profile for an evaporation source according to an embodiment of this invention that would have all heating elements switched on and regulated so as to produce a more uniform deposition profile.

<FIG> present two alternative electrical circuits to power said evaporation sources.

<FIG> shows a schematic diagram of an electrical circuit to power the independently regulated electrical heating components of evaporation source <NUM> represented in <FIG>, <FIG>, <FIG>, <FIG>. Heating elements <NUM>, <NUM>, and <NUM> are powered via pairs of lines (<NUM>, <NUM>), (<NUM>, <NUM>), and (<NUM>, <NUM>) by power supplies <NUM>, <NUM>, and <NUM>, respectively.

<FIG> shows a schematic diagram of a preferred electrical circuit to power the independently regulated electrical heating components of evaporation source <NUM> represented in <FIG>, <FIG>, <FIG>, <FIG>. In order to reduce the number of electrical cables, heating components <NUM>, <NUM>, <NUM> share some common lines <NUM>, <NUM> to connect to their respective electrical power supplies <NUM>, <NUM>, <NUM>. A common line <NUM> is shared by heating elements <NUM>, <NUM> to connect to respective power supplies <NUM>, <NUM>. In the same way, line <NUM> connects resistors <NUM>, <NUM> to their respective power supplies <NUM>, <NUM>. Each end of the heating element network is supplied by unshared lines <NUM>, <NUM>. More generally, if there are N independently regulated heating components, only N+<NUM> lines are needed to connect to the power supplies.

<FIG> shows the block diagram of a control system <NUM> to regulate the vapor deposition process. The "Desired Deposition Parameters" block <NUM> represents values set by an operator via a user interface. The "Desired Deposition Parameters" block <NUM> may include desired evaporation source temperature values but more preferably, in the context of a complete evaporation system comprising multiple evaporation sources, desired thickness and relative composition distribution of the material deposited on the substrate. The "Sensors" block <NUM> therefore represents data acquired not only from temperature sensors <NUM>, <NUM>, <NUM>, but also from other sensors that can for example measure the thickness and relative composition distribution of the material deposited on the substrate. The "Deposition System" block <NUM> represents the system that incorporates at least one evaporation source <NUM>. The "Controller" block <NUM> represents a real-time control computation that uses the difference between values set in the "Desired Deposition Parameters" block <NUM> and values acquired by the "Sensors" block <NUM> to compute commands for the "Deposition System" block <NUM>, such as commands to the electrical power supplies of heating elements <NUM>, <NUM>, <NUM>.

<FIG> show two exemplary embodiments of vapor deposition systems to illustrate how the evaporation sources are be used.

<FIG> shows a frontal cross section of a free span roll-to-roll vapor deposition system <NUM>. Vacuum deposition chamber <NUM> encloses three sets of three evaporation sources <NUM>, <NUM>, <NUM> selected from the embodiments presented in <FIG>, namely <FIG> and <FIG>. Web <NUM>, for example made of polyimide or stainless steel, departs pay-off roll <NUM> and gets coated by sets of evaporation sources <NUM>, <NUM>, <NUM> as it travels between tensioning rolls <NUM>, <NUM>, <NUM>, <NUM>, respectively, until it gets rolled-up by take-up roll <NUM>. Sets of evaporation sources <NUM> and <NUM> are staged so as to follow the slope of web <NUM>. Set of evaporation sources <NUM> is staged vertically to match the vertical path of web <NUM> between tensioning rolls <NUM> and <NUM>.

Vacuum deposition chamber <NUM> exhibits a vacuum higher than <NUM>-<NUM> Pa, preferably higher than <NUM>-<NUM> Pa, more preferably higher than <NUM>-<NUM> Pa before the start of the coating evaporation process.

In the roll-to roll vapor deposition system (<NUM>) each set (<NUM>, <NUM>, <NUM>) of evaporation sources comprises at least one evaporation source apparatus containing In, at least one evaporation source apparatus containing Ga, and at least one evaporation source apparatus containing Cu, whereby In, Ga and Cu are contained in a crucible (<NUM>) in order to be melted and evaporated.

The roll-to roll vapor deposition system (<NUM>) exhibits at least three different deposition zones (Z1, Z2, Z3) characterized by at least three different slopes and orientations (a1, a2, a3) exhibited by web (<NUM>) in respect to the ground, wherein each deposition zone (Z1, Z2, Z3) comprises a set (<NUM>, <NUM>, <NUM>) of evaporation sources positioned adjacent to the web (<NUM>) in said zone.

The roll-to roll vapor deposition system (<NUM>) exhibits at least three different deposition zones (Z1, Z2, Z3) characterized also by at least three different deposition rates and/or deposition ratios of different atoms (r1, r2, r3) realized by the sets (<NUM>, <NUM>, <NUM>) of evaporation sources, wherein each deposition zone (Z1, Z2, Z3) comprises a set (<NUM>, <NUM>, <NUM>) of evaporation sources positioned adjacent to the web (<NUM>) in said zone and tuned and configured to achieve said deposition rate and/or deposition ratio of different atoms (r1, r2, r3).

In the roll-to roll vapor deposition system (<NUM>) the at least three evaporation source apparatuses of each set of evaporation sources (<NUM>, <NUM>, <NUM>) exhibit nozzles (<NUM>) having a flux-wise axis always oriented perpendicularly to the adjacent surface of web (<NUM>), so as to direct always the evaporated flux orthogonally to the adjacent surface of the web (<NUM>).

In the roll-to roll vapor deposition system (<NUM>) said nozzles (<NUM>) are inclined, and have a flux-wise axis that is oriented at between +<NUM> degrees and +<NUM> degrees with respect to the plane supporting the base of the nozzles (<NUM>), preferably between +<NUM> and +<NUM> degrees, most preferably between +<NUM> and +<NUM> degrees, so as to direct the evaporated flux away from the orthogonal to said plane supporting said base.

In the roll-to roll vapor deposition system (<NUM>) said nozzles (<NUM>) exhibits a channel having a flux-wise axis, said channel exhibiting a length longer than its width and a divergent cross section, i.e. a cross-section along a plane containing the flux-wise axis larger at the nozzle outlet than at the nozzle inlet, so as to be configured to convey the evaporated material (<NUM>) on the largest possible surface of the adjacent thin web (<NUM>).

In the roll-to roll vapor deposition system (<NUM>) said nozzles (<NUM>) exhibit a position, a size and an inclination, so that there is no line of sight from outside the evaporation source apparatus (<NUM>) to the material to be evaporated (<NUM>) through the nozzles (<NUM>), said line of sight being obstructed by the nozzles (<NUM>).

For the deposition of thin CIGS films on a thin web (<NUM>) with a roll-to roll vapor deposition system (<NUM>), the web (<NUM>), for example made of polymer or metal foil, departs a pay-off roll (<NUM>), gets coated with a thin CIGS film by said evaporation sources sets (<NUM>, <NUM>, <NUM>) as it travels between tensioning rolls (<NUM>, <NUM>, <NUM>, <NUM>) until it gets rolled-up by take-up roll (<NUM>).

The deposition of thin CIGS films on a thin web (<NUM>) with a roll-to roll vapor deposition system (<NUM>) comprises at least the following three different deposition stages, characterized by at least three different deposition rates and/or deposition ratios of different atoms (r1, r2, r3) realized by the at least three sets (<NUM>, <NUM>, <NUM>) of evaporation sources, each positioned in its respective deposition zone (Z1, Z2, Z3):.

During the deposition of thin CIGS films on a thin web (<NUM>) with a roll-to roll vapor deposition system (<NUM>) the at least three different deposition stages, characterized by the at least three different deposition rates and/or deposition ratios of different atoms (r1, r2, r3) realized by the at least three sets (<NUM>, <NUM>, <NUM>) of evaporation sources, each positioned in its respective deposition zone (Z1, Z2, Z3), exhibit the following deposition rates:.

<FIG> shows a cross section of a drum-based roll-to-roll vapor deposition system <NUM>. Vacuum deposition chamber <NUM> encloses four evaporation source sets <NUM>, <NUM>, <NUM>, <NUM> selected from the embodiments presented in <FIG>, namely <FIG> and <FIG>.

Only one evaporation source per set is depicted in the figure for convenience and clarity, while each set comprises actually at least <NUM> evaporation sources.

Web <NUM> departs pay-off roll <NUM>, passes tensioning rolls <NUM>, <NUM> and gets coated by evaporation source sets <NUM>, <NUM>, <NUM>, <NUM> as it is carried against deposition drum <NUM>. Web <NUM> then continues to tensioning rolls <NUM>, <NUM> until it gets rolled-up by take-up roll <NUM>. Evaporation source sets <NUM>, <NUM>, <NUM>, <NUM> are staged around deposition drum <NUM> so as to follow its curvature.

The exemplary embodiments represented in the present disclosure offer a number of advantages for vapor deposition, especially in the context of large area or roll-to-roll deposition, with respect to deposition regulation and quality as well as space and energy savings.

A first advantage results from the use of the evaporation source sets able to direct the evaporated flux in a predetermined direction along the evaporation source's length to solve the problem of uneven spatial distribution of the deposited material. Deposition with conventional crucibles ordinarily exhibits a decay of evaporated material deposition profile towards the extremities of the crucible's long axis. The decay is ordinarily compensated for a set point by supplying more heat to the crucible. The benefit of using evaporation source sets able to direct the evaporated flux in a predetermined direction is that the resulting deposition profile is more uniform at less energy expense while being easily adaptable via regulation of the independent power supplies.

Also, depletion of material in conventional evaporation sources usually results in changes in the deposition profile. The multiple evaporation source sets able to direct the evaporated flux in a predetermined direction decrease this physical effect. A further advantage of this disclosure is that the heat needed to produce a desired deposition profile and composition can be tuned as the material to be evaporated depletes within the evaporation source or as the heat shields experience changes in their properties. Independent adjustments of the heat produced by the heating elements therefore regulate the evaporation profile and composition. Furthermore, said adjustments prevent the onset of unwanted vapor flow along the crucible's long axis.

In the context of an installation within a vacuum deposition chamber where various devices such as shields or even adjacent evaporation sources installed as an array may temporarily affect a given source's thermal characteristics, the ability to continuously regulate the evaporation profile and composition is especially beneficial for vapor deposition onto large substrates, for example roll-to-roll webs <NUM> meters wide or more, or also glass substrates larger than <NUM> meters in width or length. It then becomes possible to advantageously integrate an evaporation sources feedback control function as part of an evaporation source system. Said feedback control function would at least use temperatures measured by the evaporation source's temperature sensors and possibly also measurements of the material deposited onto the substrate.

The need for compact and closely integrated arrays of evaporation sources is an incentive towards reducing the number of power lines and <FIG> therefore presents an advantageous cabling solution to electrically connect heating elements to power supplies. Furthermore, using shared power lines may, under some conditions, enable to reduce the electrical current flowing through some of the lines, thereby further simplifying the cabling between heating elements and power supplies.

An advantage of placing the heating assembly directly above the material to be evaporated is that the surface where evaporation occurs is heated first, thereby permitting a faster response of the evaporation flux to changes in temperature of the heating assembly. Energy may then be saved thanks to reduced thermal inertia of the combined heating assembly and molten material system.

Furthermore, placing the heating assembly mainly within the crucible rather than outside is beneficial to reduce the evaporation source's volume. This is especially advantageous for use within vacuum deposition chambers where several evaporation sources are used within a restricted volume. For example in the context of a co-evaporation vacuum deposition chamber, it is advantageous to have evaporation sources arranged in parallel and close to each other. Also, the coaxial configuration of the heating assembly presented in the embodiments of <FIG> and <FIG> reduces the complexity of external wiring needed to power the heating elements in comparison to configurations found in prior art. Benefits of this reduction in wiring are increased overall reliability and reduction of assembly cost.

Another advantage of the evaporation source sets' design is that the crucible and its lid can feature joining lips to channel and direct vapor leaks away from heat shields. Said shields, optionally placed around the crucible and against the lid, insulate the source and therefore reduce the amount of heat radiated to adjacent objects. However, said shields may see their insulating properties diminished if material deposits onto them, hence the design of the extended joining lips to reduce the possibility of material depositing onto the shields.

Finally, placing the heating assembly directly under the lid has several combined advantages: the heating assembly blocks the line of sight between the melt within the crucible and the deposition substrate, therefore preventing detrimental spits of molten material from the crucible towards the substrate; the lid is also heated preferably to a higher temperature than the crucible by the heating assembly, therefore providing a simple way to prevent the formation of condensed material droplets that could either clog the nozzles or fall onto the heating element, thereby creating spitting, or fall further into the molten material and create internal splashes that may be detrimental to the uniformity of the deposition. Said placement of the heating assembly in effect provides a so-called "hot lip source" without requiring the addition of a lip heater. Furthermore, the embodiments presented in <FIG> show that lip heating and line of sight obstruction can be effective both when the nozzles are above or to the side of the heating assembly.

In order to depose thin CIGS films onto a flexible polymer foil (polyimide), a roll-to roll vapor deposition system (<NUM>) according to the invention was actually built for the deposition of thin CIGS films on a thin web (<NUM>), comprising a vacuum deposition chamber (<NUM>) enclosing at least three evaporation sources (<NUM>, <NUM>, <NUM>), containing respectively In, Ga and Cu, whereby web (<NUM>), made of polyimide foil, departs a pay-off roll (<NUM>) and gets coated by said evaporation sources (<NUM>, <NUM>, <NUM>) as it travels between tensioning rolls (<NUM>, <NUM>, <NUM>, <NUM>) until it gets rolled-up by take-up roll (<NUM>).

With such an equipment a <NUM> micrometer thin CIGS film has been actually deposited onto the flexible polymer substrate. According to such a method for the deposition of thin CIGS films on a thin web (<NUM>) with a roll-to roll vapor deposition system (<NUM>) according to the invention comprising a vacuum deposition chamber (<NUM>) enclosing at least three evaporation sources (<NUM>, <NUM>, <NUM>), containing respectively In, Ga and Cu, the web (<NUM>), made of polymer foil, departs a pay-off roll (<NUM>), gets coated with a thin CIGS film by said evaporation sources (<NUM>, <NUM>, <NUM>) as it travels between tensioning rolls (<NUM>, <NUM>, <NUM>, <NUM>) until it gets rolled-up by take-up roll (<NUM>).

Details of the performed process can be found in <CIT>, <CIT> and <CIT>.

Photovoltaic cells and photovoltaic modules for the conversion of solar energy into electrical energy comprising said thin CIGS film deposited on a thin web (<NUM>), specifically a polyimide foil, had been manufactured and had exhibited an efficiency between <NUM> and <NUM>%.

Claim 1:
A roll-to-roll vapor deposition system (<NUM>) suited for the deposition of thin CIGS (Cu(In,Ga)Se<NUM>, copper indium gallium di selenide) films on a thin web (<NUM>) comprising a vacuum deposition chamber (<NUM>) enclosing at least three sets (<NUM>, <NUM>, <NUM>) of evaporation sources, each set comprising at least three evaporation source apparatuses (<NUM>), whereby the web (<NUM>), for example made of polymer or metal foil, departs a pay-off roll (<NUM>) and gets coated by said evaporation sources sets (<NUM>, <NUM>, <NUM>) as it travels on a path between tensioning rolls (<NUM>, <NUM>, <NUM>, <NUM>) until it gets rolled-up by a take-up roll (<NUM>),
wherein the at least three evaporation source apparatuses (<NUM>) are linear evaporation source apparatuses (<NUM>) for atomic vapor deposition of metal atoms suited for the production of CIGS thin films comprise:
at least one elongated horizontal crucible (<NUM>) for containing, up to a given level in the crucible (<NUM>), material (<NUM>) to be melted and evaporated,
a heater assembly (<NUM>), and
a plurality of nozzles (<NUM>) that have an inclination,
wherein the plurality of nozzles (<NUM>) are on a face of the apparatus that is parallel to the longest centerline of the crucible (<NUM>), the plurality of nozzles (<NUM>) have a flux-wise axis that is oriented towards the path of the web at between +<NUM> degrees and +<NUM> degrees with respect to the plane supporting the base of the plurality of nozzles (<NUM>), so as to direct the evaporated flux in a predetermined direction.