Patent Application
20200230643
So as to realize a thin layer on a substrate, which effectively bars permeation, as of water molecules, towards and onto the substrate, such a permeation-barrier layer must be a layer of an inorganic material
In the frame of the present description and claims, we understand under the term “substrate” a workpiece generically. The substrate may comprise material which is sensitive to temperature e.g. above 150° C. or lower. The substrate may have a plate-like shape. The substrate may be an electric device and may comprise printed circuit board material as an example of thermally sensitive material.
Organic material layers, e.g. of a polymer, e.g. most of the plasma-polymerized layers, have not sufficient sealing effect or necessitate large layer thicknesses to become effectively permeation-barring. With plasma enhanced CVD (PECVD), dense inorganic layers may be realized, often either at high temperatures e.g. above 150° C. and/or by the use of dangerous gases e.g. of silane.
Purely inorganic material layers have the drawback that they are brittle and that their temperature coefficient of expansion is not adapted to that of the starting substrate. Thereby already small increases of the temperature may lead to cracks of the inorganic material layer or to an impairment of adherence of the inorganic material layer to the starting substrate.
We understand under the term “starting substrate” a substrate as defined above, which is yet untreated or not enough treated for barring permeation.
It is one object of the present invention to provide a substrate, which is permeation-protected, thereby avoiding the drawbacks as addressed above. This is achieved by a substrate comprising a starting substrate and a permeation-barrier layer system. The permeation-barrier layer system comprises a polymer material layer system, which latter comprises at least one plasma-polymerized polymer-material-containing layer and resides directly on the starting substrate. The permeation-barrier layer system further comprises an inorganic material layer system comprising at least one PVD-deposited or at least one ALD deposited inorganic-material-containing layer, deposited directly on the polymer material layer system.
If we address the starting substrate with SS, the polymer material layer system with PP and the deposited inorganic material layer system with PVD/ALD, the minimal structure of the substrate is thus SS-PP-PVD/ALD.
The polymer material layer system thereby provides for good adherence of the PVD/ALD deposited layer system with respect to the starting substrate and seals possibly occurring cracks in the inorganic material layer system.
In one embodiment of the substrate according to the invention, the substrate further comprises at least one further polymer layer system—which comprises at least on further polymer-material-containing layer, which may be plasma-polymerized or not—and which is directly deposited on the PVD/ALD deposited inorganic material layer system. Thus, the structure becomes:
If no further layer systems are provided, the further polymer material layer system provides for at least a part of that surface of the substrate, which is exposed to ambient or which is to be further treated.
In spite of the fact that already the polymer material layer system between the starting substrate and the PVD/ADL deposited, inorganic material layer system may suffice, in most cases the further or a further polymer material layer system is applied as the outermost layer system which, additionally to sealing cracks in the inorganic material layer system, is moisture- or liquid-repellant.
In one embodiment, the starting substrate itself comprises one or more than one starting substrate layers, and the polymer material layer system with at least one plasma-polymerized polymer-material-containing layer is deposited directly on the outermost of the addressed starting substrate layers.
In one embodiment of the substrate according to the invention, the starting substrate may be characterized by at least one of the following features:
In one embodiment of the substrate according to the invention, it comprises at least one further permeation-barrier layer system, which comprises a polymer material layer system—comprising at least one polymer-material-containing layer—and an inorganic material layer system, which comprises at least one PVD- or ALD-deposited inorganic-material-containing layer—and stapled in the indicated sequence on the one PVD/ALD-deposited inorganic material layer system. There results in fact a structure:
SS-PP-PVD/ALD-PP-PVD/ALD- . . . (PP).
Thus, there results, departing from the starting substrate SS, a polymer material layer system PP, directly upon the polymer material layer system an inorganic material layer system PVD/ALD, directly upon such inorganic material layer system, a polymer material layer system PP and directly upon the just addressed polymer material layer system again an inorganic material layer system PVD/ALD. This layer system sequence may be continued at the substrate according to the present invention depending upon the respective thicknesses of the addressed layer systems and barrier accuracy to be achieved. Again, in a good embodiment the outermost layer is a layer of a polymer material layer system (PP).
Thus, and in one embodiment of the substrate according to the invention, it comprises more than one of the permeation-barrier layer systems, stapled one upon the other.
In one embodiment of the substrate according to the invention, at least one inorganic-material-containing layer contains or is of silicon oxide.
In one embodiment of the substrate according to the invention it comprises at least one specifically applied interface between a polymer-material-containing layer and an inorganic-material-containing layer. The interface comprises polymer material of the polymer-material-containing layer as well as inorganic material of the inorganic-material-containing layer, which in an embodiment, is PVD- or ALD-deposited. Thus, the material of the addressed specifically manufactured interface becomes a so-called ormocer (organically modified ceramics). In one embodiment a complete layer and not just an interface may be of an ormocer.
In one embodiment of the substrate according to the invention, at least a part of the surface of the substrate is a surface of a polymer-material-containing layer. Thus, the structure may be shown as:
SS-PP-PVD/ALD- . . . PP.
In one embodiment of the substrate according to the invention, at least one or more than one or even all of the polymer-material-containing layers are plasma-polymerized layers.
In one embodiment of the substrate according to the invention, the plasma-polymerized polymer-material-containing layer or more than one, or all of the polymer-material-containing layers are polymerized from at least one of at least one gaseous and from at least one liquid material.
In one embodiment of the substrate according to the invention, at least one polymer-material-containing layer contains carbon. In one embodiment the at least one plasma-polymerized polymer-material-containing layer contains carbon.
It is to be understood that, if more than one polymer-material-containing layer is provided, such layers may be polymerized differently, some from a gaseous material, some from such a liquid material, respectively, and/or from different gaseous materials and/or from different liquid materials.
In one embodiment of the substrate according to the invention at least one polymer-material-containing layer contains silicon. Thereby and in one embodiment, the one plasma-polymerized polymer-material containing layer contains silicon.
One embodiment of the substrate according to the invention comprises a polymer-material-containing layer, in one embodiment a plasma-polymerized polymer-material-containing layer, deposited from at least one of tetramethylsilane (TMS), hexamethyldisiloxan (HMDS(O)), hexamethyldisilazan (HMDS(N)), tetraethylorthosilan (TEOS), acetylene, ethylene, possibly a mixture of at least two of these materials.
Silicon containing liquids as tetramethylsilane (TMS), hexamethyldisiloxan (HMDS(O)), hexamethyldisilazan (HMDS(N)), tetraethylorthosilan (TEOS) etc. are easy to handle and lead to layers with characteristics between silicon and cross-linked networks similarly to that of fused silica.
Hydrocarbons such as C2H2, C2H4 etc. as gases or as liquids form cross-link networks similarly to that of diamond-like carbon (DLC), which generically has good barrier effect.
In a further embodiment of the substrate according to the invention, at least one or more than or all inorganic-material-containing layers are of at least one material selected from the group: Silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, titanium oxide, titanium nitride, tantalum oxide, tantalum nitride, hafnium oxide or respective oxynitrides or a mixture thereof.
Please note that especially if at least some or even all the inorganic-material-containing layers are deposited especially by PVD rather than by PECVD, deposition may depart from a well-defined solid material, be it the material of a sputtering target or a solid material to be evaporated. Even for ALD deposition, the precursor gas may result from sublimation of a well-defined solid material.
In one embodiment of the substrate according to the invention, at least one or more than one or all inorganic-material-containing layers are deposited by sputtering.
In one embodiment of the substrate according to the present invention, at least one or more than one or all inorganic-material-containing layers are deposited by evaporation, in a good embodiment by electron-beam evaporation. By making use of electron-beam evaporation, materials with high melting temperatures, such as silicon oxide, may be evaporated. Some of these layers may be deposited by sputtering, some by evaporating.
In one embodiment of the substrate according to the present invention, at least one, or more than one, or all inorganic-material-containing layers are deposited by ALD.
In one embodiment of the substrate according to the present invention, at least one, or more than one, or all inorganic-material-containing layers are deposited by plasma-enhanced ALD(PEALD).
Thereby the reactive gas is activated with the help of a plasma.
In one embodiment of the substrate according to the present invention, the at least one, or more than one, or all inorganic-material-containing layers are deposited in a first step by means of a precursor gas and in a remotely performed subsequent step by means of a reactive gas.
In one embodiment of the substrate according to the present invention, the at least one, or more than one, or all inorganic-material-containing layers are deposited in a first step and in a deposition area by means of a precursor gas and in a subsequent step, performed in this deposition area, by means of a reactive gas.
In one embodiment of the substrate according to the present invention, the at least one, or more than one, or all inorganic-material-containing layers are deposited with a precursor gas containing silicon and/or a metal and with a reactive gas.
In one embodiment of the substrate according to the present invention the at least one, or more than one, or all inorganic-material-containing layers are deposited with a precursor gas containing at least one of silicon, aluminum, titanium, tantalum, hafnium.
In one embodiment of the substrate according to the present invention the at least one, or more than one, or all inorganic-material-containing layers are deposited with a precursor gas and with a reactive gas, the reactive gas containing at least one of oxygen and of nitrogen.
In one embodiment of the substrate according to the present invention, the permeation-barrier layer system is a permeation-barrier layer system for water molecules.
In one embodiment of the substrate according to the invention, the permeation-barrier layer system is transparent for visible light.
In one embodiment of the substrate according to the invention, the permeation-barrier layer system is electrically isolating from the surface of the substrate to the surface of the starting substrate.
In one embodiment of the substrate according to the invention, at least one layer of the permeation-barrier layer system is electrically isolating.
Two or more embodiments of the substrate according to the invention and as addressed may be realized in combination, unless being in mutual contradiction.
The present invention is further directed to a layer deposition apparatus which comprises:
One embodiment of the layer deposition apparatus according to the invention comprises at least one cooling station.
In one embodiment of the layer deposition apparatus according to the invention at least one inorganic material layer deposition station comprises at least one ALD layer deposition chamber comprising a gas supply arrangement operationally and controllably flow-connected to at least a precursor reservoir containing a precursor and to a reactive gas reservoir containing a reactive gas.
In one embodiment of the layer deposition apparatus according to the invention at least one inorganic material layer deposition station comprises at least two ALD layer deposition chambers, one of the at least two ALD layer deposition chambers comprising a gas supply arrangement operationally and controllably connected to a precursor reservoir containing a precursor, the other of said ALD deposition chambers comprising a gas supply arrangement operationally and controllably flow-connected to a reaction gas reservoir, containing a reactive gas.
In one embodiment of the layer deposition apparatus according to the invention, a precursor gas from said precursor reservoir contains at least one of silicon and of a metal.
In one embodiment of the layer deposition apparatus according to the invention, the metal is at least one of aluminum, tantalum, titanium, hafnium.
In one embodiment of the layer deposition apparatus according to the invention the reactive gas contains at least one of oxygen and of nitrogen.
In one embodiment of the layer deposition apparatus according to the invention at least one inorganic material layer deposition station comprises at least one ALD layer deposition chamber, this ALD layer deposition chamber comprises a laser source, a gas supply arrangement operationally flow-connected to at least a precursor reservoir containing a precursor and to a reactive gas reservoir containing a reactive gas.
In one embodiment of the layer deposition apparatus according to the invention at least one inorganic material layer deposition station comprises at least two ALD layer deposition chambers, one of said at least two ALD layer deposition chambers comprising a gas supply arrangement operationally connected to a precursor reservoir containing a precursor, the other of said ALD deposition chambers comprising a laser source and a gas supply arrangement operationally connected to a reaction gas reservoir, containing a reactive gas.
In one embodiment of the layer deposition apparatus according to the invention at least one inorganic material layer deposition station comprises at least one PVD layer deposition chamber.
In one embodiment of the layer deposition apparatus according to the invention the PVD layer deposition chamber is a sputter layer deposition chamber.
In one embodiment of the layer deposition apparatus according to the invention the PVD layer deposition chamber is an evaporation chamber, in one embodiment an electron-beam evaporation chamber.
In one embodiment of the layer deposition apparatus according to the invention the PVD layer deposition chamber has a solid material source of at least one metal or metal alloy or of an oxide or of a nitride or of an oxynitride of such metal or metal alloy.
In one embodiment of the layer deposition apparatus according to the invention at least one inorganic material layer deposition station and at least one polymer deposition station are distant from each other and the substrate carrier is controllably movable from one of these stations to the next one of these stations, preferably in a vacuum environment.
In one embodiment of the layer deposition apparatus according to the invention at least one PVD layer deposition chamber and/or at least one ALD layer deposition chamber and/or at least one cooling chamber comprises a controllably sealable—for layer deposition operation—and openable—for substrate handling-deposition space, and a pumping port abutting in said controllably sealable and openable deposition space.
In one embodiment of the layer deposition apparatus according to the invention at least one plasma-polymerizing chamber with a feed-line system for monomer feeding and with a plasma source comprises a for layer deposition operation controllably sealable and for substrate handling openable deposition space and a pumping port abutting in said controllably sealable and openable deposition space.
In one embodiment of the layer deposition apparatus according to the invention at least one inorganic material layer deposition station and at least one polymer deposition station perform layer deposition in a common deposition area.
One embodiment of the layer deposition apparatus according to the invention comprises along a linear or along a generically curved or along a circular movement path of the substrate carrier, a sequence of more than one pair of an inorganic material layer deposition station and of a polymer deposition station.
One embodiment of the layer deposition apparatus according to the invention comprises along a linear or along a generically curved or along a circular movement path of the substrate carrier, a sequence of an inorganic material layer deposition station and of a polymer deposition station directly subsequent the inorganic material layer deposition station just addressed.
One embodiment of the layer deposition apparatus according to the invention comprises a cooling station directly succeeding an inorganic material layer deposition station.
One embodiment of the layer deposition apparatus according to the invention is a vacuum apparatus comprising at least one input load lock and at least one output load lock or at least one bidirectional input/output load lock.
In one embodiment of the layer deposition apparatus according to the invention, at least one inorganic material layer deposition station and at least one polymer deposition station are layer depositing into a common deposition area and the control unit is constructed to intermittently enable/disable the addressed stations.
In one embodiment of the layer deposition apparatus according to the invention at least one inorganic material layer deposition station and at least one polymer deposition station are depositing into mutually distant areas and the control unit is constructed to control a movement of the substrate carrier between said areas.
One embodiment of the layer deposition apparatus according to the invention is constructed to enable deposition by both an inorganic material layer deposition station and a polymer deposition station simultaneously in a common deposition area during a controlled transition time span.
In one embodiment of the layer deposition apparatus according to the invention the feed-line system is in controlled flow communication with a reservoir containing a liquid or a gaseous monomer material.
In one embodiment of the layer deposition apparatus according to the invention the feed-line system is in controlled flow communication with a reservoir containing a material comprising carbon.
In one embodiment of the layer deposition apparatus according to the invention the feed-line system is in controlled flow communication with a reservoir containing a material comprising silicon.
In one embodiment of the layer deposition apparatus according to the invention, the feed-line system is in controlled flow communication with a reservoir containing at least one of tetramethylsilane (TMS), hexamethyldisiloxan (HMDS(O)), hexamethyldisilazan (HMDS(N)), tetraethylorthosilan (TEOS), acetylene, ethylene.
In one embodiment of the layer deposition apparatus according to the invention the substrate carrier is constructed to simultaneously carry more than one substrate and/or more than one starting substrate.
In one embodiment of the layer deposition apparatus according to the invention all polymerizing chambers are plasma-polymerizing chambers.
One embodiment of the layer deposition apparatus according to the invention has at least one of the following features:
As addressed the vacuum layer deposition apparatus may comprise at least one cooling station.
Such cooling station is e.g. provided to cool down substrates just after having been subjected to the or to an inorganic material layer deposition station, especially with a PVD layer deposition chamber, or directly between being exposed to one inorganic material layer deposition station and before being subsequently exposed to a next inorganic material layer deposition station.
As was addressed at least one inorganic material layer deposition station and at least one polymer material deposition station, comprise, respectively, mutually distant, for deposition mutually sealed and separately pumped vacuum treatment chambers. The substrate carrier is controllably movable from one of the addressed stations to the next, thereby and in a good embodiment, in a vacuum environment.
Such an embodiment may e.g. comprise a rotatable disc-shaped or ring-shaped substrate carrier constructed to carry a multitude of single substrates along its periphery and from one station to the next station. Thereby, a yet untreated starting substrate is first subjected to the vacuum plasma-polymerizing station (PPS) and then subsequently to the inorganic material layer depositing station PVD/ALDS.
The sequence of stations along the moving path of the substrate carrier, which may be linear, curved or circular, becomes, in a minimum configuration:
If, as addressed above cooling of the substrate is to be provided, the station structure becomes, addressing the cooling station by CS:
or
Subsequently, the substrate considered may be transported to a further polymer material depositing station and then subsequently and, if desired, to one or more than one further inorganic material depositing station and polymer material depositing stations, terminating the overall station sequence, in a good approach, always by a polymer-material depositing station.
One or more than one or all polymer material depositing stations may be plasma-polymerizing stations, in some cases, some or all plasma-polymerizing stations may be replaced by polymerizing stations not making use of vacuum plasma.
Thus, the following sequence of stations prevails:
PPS-PVD/ALDS-PPS-n*(PVD/ALDS-PPS-PVD/ALDS . . . )-PPS (n≥0).
If cooling is necessary with respect to all PVD/ALDS, then the sequence becomes:
PPS-PVD/ALDS-CS-PPS-n*(PVD/ALDS-CS-PPS-PVD/ALDS . . . )-PPS (n≥0).
As was addressed, the inorganic material depositing station and the polymer material depositing station, constructed e.g. as a vacuum plasma-polymerizing station, are provided in a common vacuum treatment chamber.
A batch processing system may be considered in which e.g. a carrier calotte for a multitude of substrates to be simultaneously treated is exposed to inorganic material deposition as well as to polymer material deposition.
If the inorganic material layer deposition station and the polymer material deposition station are mutually distant from each other either in a common vacuum treatment chamber or in separate, separately pumped treatment chambers, the control unit controls timing of the movement of the substrate carrier and possibly enabling/disabling the stations and thus of substrate exposure to the respective deposition effects.
One embodiment of layer deposition system comprises more than one pair or more than a pair of PVD layer deposition stations and polymerizing stations.
If the layer deposition apparatus is a vacuum apparatus and thus comprises respective input/output load locks all treatment and transport chambers or stations including possibly provided cooling stations are vacuum stations.
In that at least one PVD layer deposition chamber and/or at least one ALD layer deposition chamber comprises a—for deposition operation—controllably sealable and—for substrate handling—openable deposition space, and a pumping port abutting in the controllably sealable and openable deposition space and/or in that at least one plasma-polymerizing chamber with a feed-line system for monomer feeding and with a plasma source comprises a—for layer deposition operation—controllably sealable and—for substrate handling—openable deposition space and a pumping port abutting in the controllably sealable and openable deposition space mutual cross contamination of the respective deposition spaces is practically excluded.
The activating of the reactive gas in the ALD thus exploiting a PEALD deposition process significantly reduces processing time.
Please note, that in some cases of exploiting ALD, thereby also of PEALD, it might be necessary to expose the substrate first to a processing step in a reactive gas atmosphere, e.g. in an oxidizing atmosphere, so as to improve adherence of the layer subsequently deposited by ALD thereby, in an embodiment, by PEALD.
If not in contradiction, two or more embodiments of the apparatus according to the invention may be combined.
The present invention is further directed to a method of providing a permeation-barrier system on a starting substrate or of manufacturing a substrate which is provided with a surface permeation-barrier layer system. The method comprises
One variant of the method according to the invention comprises vacuum plasma-polymerizing the or at least one polymer-material-containing layer being deposited.
In one variant of the method according to the invention establishing the permeation-seal comprises plasma enhanced ALD.
In one variant of the method according to the invention, at least one layer is deposited to form from an electrically isolating layer.
In one variant of the method according to the invention, the permeation-barrier layer system is deposited to be transparent for visible light.
In one variant of the method according to the invention, the temperature at the starting substrate during the depositions does not exceed a predetermined value, does, in one variant, not exceed at most 150° C.
One variant of the method according to the invention comprises depositing a further polymer material layer system, comprising at least one polymer-material containing layer, directly on the inorganic material layer system.
One variant of the method according to the invention comprises vacuum plasma-polymerizing material of more than one polymer-material-containing layers.
One variant of the method according to the invention comprises repeating the steps a) and b).
One variant of the method according to the invention comprises depositing a further polymer material layer system, comprising at least one polymer-material-containing layer, directly on the last-deposited inorganic material layer system.
One variant of the method according to the invention comprises cooling the substrate after or during at least one of depositing an inorganic material layer system.
One variant of the method according to the invention comprises depositing an inorganic-material-containing layer of silicon oxide.
One variant of the method according to the invention comprises depositing in a controlled manner at least one material interface between depositing a polymer-material-containing layer and depositing an inorganic-material-containing layer, the interface being of a material which comprises polymer material of the deposited polymer-material-containing layer as well as inorganic material of the inorganic-material-containing layer.
One variant of the method according to the invention comprises depositing at least one polymer-material-containing layer from a gaseous or a liquid material.
One variant of the method according to the invention comprises depositing at least one polymer-material-containing layer from a material containing carbon.
One variant of the method according to the invention comprises depositing at least one polymer-material-containing layer from a material containing silicon.
One variant of the method according to the invention comprises depositing at least one polymer-material-containing layer from one of tetramethylsilane (TMS), hexamethyldisiloxan (HMDS(O)), hexamethyldisilazan (HMDS(N)), tetraethylorthosilan (TEOS), acetylene, ethylene.
One variant of the method according to the invention comprises depositing at least one inorganic-material-containing layer comprising or consisting of at least one of silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, titanium oxide, titanium nitride, tantalum oxide, tantalum nitride, hafnium oxide or of a respective oxynitride.
One variant of the method according to the invention comprises depositing at least one inorganic-material-containing layer by sputtering or by evaporation or by electron beam evaporation or by ALD or by plasma enhanced ALD.
One variant of the method according to the invention comprises depositing at least one inorganic-material-containing layer by ALD in an ALD deposition chamber and feeding a precursor gas and a reactive gas to said ALD deposition chamber.
One variant of the method according to the invention comprises depositing at least one inorganic-material-containing layer by ALD in at least two subsequent ALD deposition chambers and feeding a precursor gas to the first of the at least two ALD deposition chambers and feeding a reactive gas to the second of the at least two subsequent ALD deposition chambers.
In one variant of the method according to the invention the precursor gas contains silicon or a metal.
In one variant of the method according to the invention the addressed metal is at least one of aluminum, tantalum, titanium, hafnium.
In one variant of the method according to the invention the reactive gas contains at least one of oxygen and of nitrogen.
One variant of the method according to the invention comprises depositing an inorganic-material-containing layer in at least one layer deposition space, sealing said at least one deposition space during said depositing and pumping said deposition space by means of a pump directly connected to said deposition space.
Thereby cross contamination into or from the deposition space for depositing the inorganic-material-containing layer is substantially reduced.
One variant of the method according to the invention comprises depositing a polymer-material-containing layer in a layer deposition space, sealing said deposition space during said depositing and pumping said deposition space by means of a pump directly connected to said deposition space.
Thereby cross contamination into or from the deposition space for depositing the polymer-material-containing layer is substantially reduced.
Clearly in one variant of the method according to the invention both deposition spaces, for depositing the inorganic-material-containing layer on one hand and for depositing the polymer-material-containing layer on the other hand, are respectively sealed during depositing operation and are separately pumped.
One variant of the method according to the invention comprises manufacturing the permeation barrier layer system suppressing permeation of water molecules.
One variant of the method according to the invention is performed in vacuum.
It must be noted that all embodiments of the substrate according to the invention, of the layer deposition apparatus according to the invention as well as of the method according to the invention may, respectively, be combined in any combination if not contradictory.
The invention shall now and as far as necessary for the skilled artisan, further be exemplified with the help of figures. They show:
In
In step 1 a starting substrate (before being treated according to the invention) or more than one starting substrates up to a batch of starting substrates is/are provided. In step 2 the one or more than one starting substrate is coated with a polymer-material-containing layer system PP which comprises at least one plasma-polymerized, polymer-material-containing layer. Thereby, and in a today favored embodiment, a gaseous or liquid monomer is plasma-polymerized resulting in at least one plasma-polymerized polymer layer directly deposited on the one or more than one starting substrate.
The liquid or gaseous or liquid monomer being polymerized contains carbon and, if liquid, silicon. As material to be polymerized, especially plasma-polymerized, TMS or HMDS(O) or HMDS(N) or TEOS or acetylene or ethylene may be used, whereby, if a polymer-material containing layer system with more than one polymer-material-containing layers is deposited, respectively different ones of the addressed monomers may be used one after the other or even a mixture thereof. Additionally, more than one or all of the polymer-material-containing layers may be realized by plasma-polymerization.
After deposition of the polymer-material-containing layer system, and in step 3, directly upon the polymer-material-containing layer system PP, an inorganic-material-containing layer system PVD/ALD is deposited, comprising at least one inorganic-material-containing layer. This is performed by a PVD (Physical Vapor Deposition) deposition or by an ALD (Atomic Layer Deposition) deposition. The deposited, inorganic-material-containing inorganic material layer system consists in a minimum configuration of a single inorganic-material-containing layer.
As PVD deposition methods sputtering, thereby magnetron sputtering or evaporation, may be used, thereby especially electron-beam evaporation. The respective PVD deposition method may be performed non-reactively or reactively. As an example, the inorganic material deposited in step 3 may be silicon oxide, silicon nitride, a metal oxide, a metal nitride, a metal oxynitride as e.g. aluminum oxide or aluminum nitride, titanium oxide, titanium nitride, tantalum oxide, tantalum nitride, hafnium oxide or a respective oxynitride.
If one or more than one of the inorganic-material-containing layers, or, in minimum configuration, the one inorganic-material-containing layer is deposited by ALD deposition, at least one precursor gas and at least one reactive gas are used, both fed either to one ALD treatment chamber or separately fed to subsequent ALD treatment chambers.
The reactive gas may thereby be activated by means of a plasma source resulting in plasma enhanced ALD.
The precursor gas contains, in one embodiment, at least one metal. The precursor gas may contain at least one of silicon, aluminum, tantalum, titanium, hafnium. The reactive gas may contain oxygen and/or nitrogen.
Please note that if the inorganic-material-containing layer system comprises more than one inorganic-material-containing layer, such layers may be deposited of different materials specifically, by PVD and/or ALD.
The inorganic-material-containing layer may also contain some amount of polymer-material, which in some applications, may even be desirable.
In an interface area, realized between a polymer-material-containing layer and an inorganic-material-containing layer, the material of inorganic material as well as polymer material may both be present.
As the specific temperature expansion coefficient of the starting substrate is customary quite different from the temperature expansion coefficient of the at least one inorganic-material-containing layer system PVD/ALD as deposited in step 3, the polymer-material-containing layer system PP deposited in step 2 provides for good adhesion of the inorganic-material-containing layer system PVD/ALD and seals possibly occurring cracks in the brittle inorganic-material containing layer system PVD/ALD.
In some applications of the present invention the starting substrate should not be loaded with high temperatures exceeding a definite value, e.g. of 150° C. or of below. Thus, as an example, printed circuit board material, as material of the starting substrate, should not be treated at temperatures exceeding 150° C.
In such cases, deposition of the PVD/ALD system with respectively thick inorganic-material-containing layers may result, without additional measures, in thermally overloading the starting substrates by exceeding the allowed temperatures.
Therefor and in such cases, there is provided, as shown in
After the termination of step 3, possibly cooling step 4, according to
Nevertheless, in most cases, there is further applied, according to step 5 in
Nevertheless, after deposition step 5, one or more than one pairs of inorganic-material-containing layer systems—PVD/ALD—and of polymer-material-containing layer systems-PP may be deposited as addressed in
As was addressed, the step sequence as explained with the help of
For most applications of the addressed method, the overall layer system as deposited is electrically insulating considered between the outermost surface of the resulting substrate and the surface of the starting substrate, whereupon the first PP layer system is deposited. Thus e.g. at least one of the deposited layers is electrically insulating.
Further and again for frequent applications of the method, the overall stack of layers is transparent for visible light, possibly also the starting substrate.
Today the polymer-material-containing layer system PP and the inorganic-material-containing layer system PVD/ALD have a total thickness between 50 nm and 300 nm.
In the following table different process flows are exemplified performed according to the method as explained with the help of
For some material combinations it might be advisable to perform a treatment step in a reactive gas atmosphere, possibly plasma enhanced, before performing the ALD-a step, so as to improve adherence of the ALD deposited layer. This in analogy to performing the ALD-b step.
So as to minimize cross-contamination of treatments steps, at least some of the respective treatment chambers, especially chambers for PP deposition and/or for PVD deposition and/or for ALD deposition and/or for cooling are separately pumped and—during deposition-operation—sealed.
Most schematically and simplified,
In the embodiment of
The plasma-polymerizing station 8 is supplied in a controlled manner from a monomer source 201 containing a gaseous or liquid monomer material, controlled, as schematically shown, via a valve arrangement 203.
If the inorganic material deposition station 10 is a PVD deposition station, dependent whether the deposition is performed merely from a solid material source e.g. merely from a sputtering target, or is performed including reacting material from a solid material source with a reactive gas or gas mixture, the inorganic material deposition station 10 is supplied with a reactive gas or gas mixture as schematically shown at 205 PVD, controlled, as schematically shown, by a valve arrangement 207 PVD.
If the inorganic material deposition station 10 is an ALD deposition station, precursor gas is supplied in a controlled manner, as schematically shown, from a tank arrangement 209AL to the deposition station 10, via a valve arrangement 211AL. Additionally deposition, a reactive gas or gas mixture is supplied from a tank arrangement 213AL to the deposition station 10, in a controlled manner, as schematically shown by a valve arrangement 215AL.
To perform the time sequence of
This structure of the combined plasma-polymerizing PPS station and of the inorganic material deposition station PVD/ALDS is especially suited, if batches of starting substrates have to be treated, i.e. comprising a multitude of starting substrates arranged e.g. on a dome- or calotte-shaped, revolving substrate-carrier within the chamber 16. The substrates on such a carrier may additionally be rotated around a substrate central axis. Thereby, especially in this case, it might be advantageous to perform a PVD inorganic material deposition by evaporation, especially, and dependent from the solid material to be evaporated, by means of electron-beam evaporation.
A liquid or gaseous monomer material is fed into the treatment chamber 16 nearby the substrate carrier and is plasma-polymerized by means of a plasma source. The crucible material to be evaporated may be protected from polymer material by an arrangement of movable shutters during operation of the PPS station and, inversely, during operation of PVDS station, the plasma source may be protected from inorganic material deposition by respective movable shutters.
As shown in dashed lines at 26, a movable shutter arrangement may be provided to respectively protect the station 10PVD as well as the plasma source 21 during disabled cycles.
In this case, making use of evaporation for inorganic material deposition may not necessitate a cooling step as was addressed in
In opposition to the embodiment of
This embodiment structure is especially suited for single substrate treatment and the inorganic material deposition station or stations 10 is/are realized, in a good embodiment, either by respective sputtering sources or by ALD. In this case, cooling as was addressed in context with
Please note that the respective controlled supplies of gases or of liquid and the timing control unit controlling the time sequence of these supplies are not shown in
A today favored structure of the layer deposition apparatus, again realized as a vacuum layer deposition apparatus, and according to the invention, is schematically and most simplified shown in
In the structure embodiment of
Especially if inorganic layer deposition is performed by PVD, thereby especially by sputtering, provision of cooling steps and accordingly of cooling chambers or cooling stations as was addressed in context with
If the deposition of inorganic material or one of the depositions of inorganic material is performed by ALD, principally two methods are possible, as now addressed with an eye on
According to the embodiment of
According to the embodiment of
In all embodiments, where deposition of polymerized material is performed in a deposition area remote from a deposition area for depositing the inorganic material, the station 10 realized as ALDS station may be constructed according to
The generic structure of the vacuum layer deposition apparatus according to the invention and thereby also according to
One more specific apparatus structure is schematically shown in
The PPS stations 8 and the inorganic material deposition stations 10, PVD/ALDS are provided stationary along the trajectory path of the revolving substrate carrier 64. The azimuthal spacing of the stations accords with the azimuthal spacing of the substrates on the substrate carrier 64. The deposition stations 8,10 are arranged with main deposition directions B radially with respect to the axis A64. Clearly, and if necessary, one or more than one cooling stations are provided, and (not shown) an arrangement of input/output load lock. The stations of the embodiment of
In a today favored structure, the vacuum layer deposition apparatus is structured as disclosed in applicants' WO 2010/105967. The deposition steps, especially a PVD inorganic material layer deposition step, may be split in two or more than two equal deposition steps performed at respective stations, possibly with interconnected cooling stations. With respect to a general approach of process-splitting we may refer to the disclosure in applicants' WO 2010/106012.
Such a today favored vacuum layer deposition apparatus is nevertheless shown in the embodiment of
The substrates 72 are deposited on the substrate carrier 74 with substrate planes perpendicular to a rotational axis A30 of the substrate carrier 74. Aligned with the circular path of the substrates 72 on the substrate carrier 74, there are provided, as shown in
Please note that the stations 8,10 are separately pumped by pumps 79 and are mutually sealable by controllably lifting the substrates 72 by means of lift arrangements 102 from the substrate carrier 74 into engagement with sealing frames, thereby sealing the respective deposition chamber.
If the deposition of inorganic material is performed by ALD and the respective deposition station 10 is realized according to the embodiment of
With the exception of providing deposition stations according to the present invention, the WO 2010/106012 discloses a general structure of an apparatus which may be used in context with the present invention.
If it is necessary and as was addressed already in context with
In the WO 2016/091927 a cooler vacuum chamber is disclosed. The cooler chamber is schematically shown in
At such cooling station 100, the substrate 72 is lifted from the substrate carrier 74 by a lift arrangement 102 as also provided to cooperate with the deposition stations or chambers, see
If multiple pairs of polymerized-material-containing layer systems and of inorganic material containing layer system have to be deposited on the starting substrate, it might be necessary to perform the deposition of these systems more than once i.e. to repeat deposition cycle at least once. This may be performed by more than one 360° rotation of the substrate carrier 74 of
In
A starting substrate 90 may be or may not be already covered by thin layers as shown in dashed lines at 90a. The starting substrate 90 is directly covered along at least a part of its extended surface Su by a layer system PP 92 of plasma-polymerized material. The PP layer system 92 of plasma-polymerized material may be single-layered or multi-layered, whereby more than one layer of different polymerized materials may be part of the polymerized material layer system 92.
Directly on the PP layer system 92 containing polymerized material there is provided an inorganic-material-containing layer system 94 of PVD- and/or ALD-deposited inorganic material or materials. Again, the inorganic-material-containing layer system 94 may consist of a single PVD or ALD-deposited, inorganic material layer or of more than one PVD and/or ALD-deposited inorganic material layers of equal or of different inorganic materials.
In a minimum substrate configuration, the outermost layer of system 96 is a layer of polymerized material. The layer system 96 directly resides on an inorganic material layer system 94.
With an eye back on
With an eye on
Generically it might be advantageous to provide in a layer of inorganic material e.g. deposited by ALD, some amount of polymerized material.
If the overall layer system 92,94,96, etc. is to be electrically insulating this may be realized by providing one or more than one of the layers sufficiently electrically insulating.
Further all the layers applied on the starting substrate may be selected to be transparent for visible light.
| Number | Date | Country | Kind |
|---|---|---|---|
| 00977/17 | Jul 2017 | CH | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2018/068918 | 7/12/2018 | WO | 00 |
