比利时专利BE1021288B1 IMPROVED WAYS TO GENERATE PLASMA IN CONTINUOUS POWER MANAGEMENT FOR LOW PRESSURE PLASMA PROCESSES

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专利摘要:
The present invention describes a method consisting of the following steps: introducing a substrate containing a surface to be coated on into a low pressure reaction chamber; exposing the surface to a plasma in the reaction chamber for a certain treatment time; ensuring stable ignition of the plasma by applying a power, characterized by the fact that the power input is strictly higher than zero Watt (0 W) during the treatment time and consists of at least a lower limit of the power and at least an upper limit of the power power, strictly greater than the lower limit, whereby a substrate is obtained with a coating on a surface. The present invention further describes an apparatus for treating a substrate with a low pressure plasma process and a substrate so treated.
公开号:BE1021288B1
申请号:E2014/0177
申请日:2014-03-14
公开日:2015-10-20
发明作者:Filip Legein；Marc Sercu；Eva Rogge
申请人:Europlasma Nv；
IPC主号:

专利说明:

Improved ways to generate plasma in continuous power mode for low pressure plasma processes
Technical domain
The present invention is situated in the technical domain of deposition of coatings on substrates, in particular wherein a plasma polymeric coating is deposited at continuously applied powers and at low pressure.
BACKGROUND OF THE INVENTION
Low pressure plasma processes are a well-known technique, developed since the early 1980s for cleaning and activating small components in the electronics sector. Since then, technology has evolved continuously and new processes and new applications have been developed.
One of these new processes is the deposition of coatings on surfaces to add functionalities to the substrates, such as better wetting, scratch resistance, liquid repellency, and much more. Examples of surfaces on which a coating can be deposited via plasma deposition are polymers, textiles, fabrics, metals and alloys, paper, composites, ceramic materials, as well as specific products made from these materials or made from combinations of these materials.
For example, Yasuda describes the use of hydrocarbons and perfluorocarbons to deposit water-repellent coatings via plasma processes (Journal of Polymer Science, vol. 15, pp. 81-97 and pp. 2411-2425 (1977)). EP0049884 describes a process for depositing fluoroalkyl acrylate polymers on a surface via low pressure plasma polymerization of precursor monomers. WO2004067614 describes a method of depositing a liquid-repellent coating on an open cell structure, wherein the coating is deposited throughout the structure so that the coating is deposited not only on the external surface but also on the internal surfaces. US2012107901 describes a four-step process to provide medical devices with better adhesion with biomolecules.
As is well known in the art, low pressure plasma processes can be performed in a closed system at reduced pressure. In the most simplified form, such processes consist of 5 steps: - Evacuation of the chamber to achieve low pressure; - Introduction of a reaction gas or reaction gases; - Applying an electromagnetic field within the plasma chamber to generate an advantageous plasma; - Switching off the plasma generation after a sufficient time; and - Aerating the chamber until atmospheric pressure is reached, after which the treated substrates can be taken out of the chamber.
Plasma is formed when an electromagnetic field is applied within the plasma chamber. This is done by applying a power to the device that generates the electromagnetic field. In a capacitive plasma device, electrodes are placed in the plasma chamber. Some electrodes are grounded, and the power is applied to the other electrodes, for example, radio frequency electrodes. In an inductive plasma device, a conductive coil is wound around the plasma chamber, and the power is applied to the coil.
The prior art describes two ways of applying a power to obtain a plasma. These two ways can be used for both a capacitive and an inductive device.
A first way is to use continuous wave plasma, where the power is set to a certain value substantially higher than 0 W, and where this constant power is maintained continuously throughout the entire process time. For example. the power must be kept constant at 50 W during a total process time of 10 minutes.
A second machine is by using a pulsed plasma, where the power is applied in a repetitive sequence with short on-times and long off-times, whereby the power is condensed into higher peak powers (on-time), so that during short on times the power is substantially higher than 0 W. During the off times the power falls back to 0 W, which means that no power is applied during the off times.
The duration of the intervals at which the plasma is on or off can be varied to obtain the best process results for a given chemistry and device. In general, the best results are obtained with very short on-times, which give sharp power peaks, combined with longer off-times.
To obtain more complex functionalities, for example liquid-repellent coatings with a surface energy that is so low that the coatings repel water and / or oil, or for example functionalization processes to apply long-term hydrophilic properties to a substrate, different types of precursors are used . A limited degree of water and / or oil repellency comes with (often gaseous) precursors that have a relatively simple molecular structure. For example, WO2004067614 describes the use of unsaturated and saturated perfluorocarbons, such as C 2 F 6, C 3 F 6 and C 3 F 8. When a surface is to be rendered hydrophilic, a temporary hydrophilic effect can be obtained with simple gaseous precursors or mixtures thereof, such as e.g. oxygen and argon. Other functionalities can also be obtained or improved or reduced, such as oil repellency (oleophobic effect), oil attractiveness (oleophilic), friction, anti-stick, cohesion properties, adhesion properties with specific materials, etc.
If the hydrophilic properties are to be maintained for a prolonged to permanent period, more complex precursors (gaseous, liquid or solid) are required. If a higher degree of liquid repellency is required, for example better water and / or oil repellency, complex molecules are often used. These molecules typically consist of different functional groups, such as groups that ensure good adhesion to the substrate and that provide cross-linking, and groups that promote repellency. During the process it is essential that the correct functional groups are made reactive. For example, molecules used to apply liquid-repellent properties to a substrate must be deposited in a manner that keeps the functional group that provides the repellent properties of the coating as intact as possible so that the best performing coatings are obtained.
It is known from the prior art that for complex precursors the average applied power at which the low pressure plasma process takes place must be low in order to keep the functional group of the precursor molecule intact, as described in e.g. "Pulsed Plasma Polymerization of Perfluorocyclohexane" , by Hynes et al, Macromolecules Vol 29, pp 4220-4225, 1996 (freely translated: "Pulsed plasma polymerization of perfluorocyclohexane"). The prior art method of generating a plasma, as described herein, is not always sufficient to ensure continuous ignition of the plasma, since the required low average power may be too low to maintain with commercially available generators, which can prevent a good and stable inflammation of the plasma.
The applicant has noted that both with a continuous wave power and with a pulsed power it is not always possible to maintain a stable inflammation of the plasma. This can lead to inferior treatment or quality of the coating.
In particular, when optimum functionalities are to be obtained with a continuous wave plasma, a very low value of power is required. The applicant has discovered that such low values lead to unstable plasma inflammation, in particular for plasma chambers of smaller volumes, e.g. up to 500 I.
This problem of unstable plasma inflammation can also occur in pulsed plasma processes and devices, since the applied power is reduced to zero (0) watts during a certain off time.
Another limitation of pulsed plasma processes is the low speed of treatment or deposition, which can be less than 50% of the speed of the corresponding continuous wave plasma processes, especially for short treatment times. However, it is clear that for treatment of substrates on a large scale or with a large turnover, the speed of the treatment or the deposition must be as high as possible, and therefore the duration of the treatment, as short as possible. Therefore, pulsed processes are usually not preferred for large-scale plasma treatments, e.g. mass production.
The applicant has discovered that the above mentioned problems typically occur in smaller systems, e.g. with a chamber volume of up to 500 l, such as e.g. used for depositing coatings on electronic components and / or devices, garments, complex 3D objects, and much more.
Summary of the invention
The applicant has developed various ways of applying a low average power in a continuous manner whereby the ignition of the plasma is guaranteed so that a stable plasma is present in the chamber.
If the power is applied continuously, the applicant means that the power never falls back to 0 W during the entire duration of the plasma treatment step. Only when the process is finished and the end is reached, the power is turned off and thus reduced to 0 W. , to switch off the plasma so that the room can be aerated. The application of a minimum power higher than 0 W during the total treatment time ensures stable inflammation of the plasma. It should be noted that when the power is reduced to 0 W, as is always the case during pulsed plasma processes, the inflammation of the plasma can be interrupted. Such interruptions can lead to undesirable properties of the treated substrate, e.g. incomplete, thinner or non-uniform coatings.
Therefore, the present invention describes a method, preferably a method for depositing coatings, which comprises the following steps: - Introduction of a substrate, which has a surface to be treated, in a low pressure reaction chamber, the treatment preferably a deposition of is a coating;
Exposing the surface to a plasma during a treatment time in the reaction chamber; - Ensuring stable inflammation of the plasma by applying a power,
The power is characterized in that it is continuously higher, and preferably substantially higher, than 0 W during the treatment time, and wherein there is at least one lower limit, at least one upper limit strictly higher than the lower limit, and optionally at least one intermediate limit (or intermediate limit) ), strictly higher than the lower limit and strictly lower than the upper limit, wherein a substrate is provided with a treated surface, the treatment preferably being the deposition of a cover layer.
A further aspect of the invention describes an apparatus, preferably a deposition apparatus, which contains a reaction chamber for low pressure treatments, preferably deposition, of one or more surfaces of a substrate by exposing it to a plasma, and further contains means for igniting a plasma in the reaction chamber or in a plasma production chamber, which can be brought into rapid communication with the reaction chamber, and furthermore also comprises means for applying a power to the means for igniting a plasma , wherein the applied power is continuously strictly higher, preferably substantially higher, than 0 (zero) W during the treatment time, and comprises at least one lower limit, and at least one upper limit strictly higher than the lower limit, and optionally at least one intermediate limit that is strictly higher than the lower limit and strictly lower than the upper limit.
In a further aspect, the invention comprises a substrate having one or more surfaces that have been treated, preferably a deposition of a coating, with a method or apparatus as described in this description and claims.
In preferred embodiments of the invention, the power is applied in so-called "burst mode", in a sinusoidal way, in "repeated burst mode", such as "repeated burst mode" with square shape or rectangular shape, or in triangular manner, such as regular triangular mode or irregular triangular mode, or at super positions of the foregoing.
Brief description of the figures
Figure 1 shows a schematic representation of a first embodiment of the applied power, known from the state of the art, wherein the power is applied via a continuous wave plasma wherein the value of the power is kept constant during the entire duration of the deposition process;
Figure 2 shows a schematic representation of a second embodiment of the applied power, known from the prior art, wherein the power is applied via a pulsed plasma (on-off); and Figures 3-7 show schematic representations of continuous power embodiments according to the present invention, which will be described in further detail.
Detailed description of the invention
As used herein, the following terms have the following meanings: "A," "an," and "an" as used herein refer to both the singular and the plural unless the context clearly dictates otherwise. For example "a compartment" refers to one or more compartments. "Approximately" as used herein refers to a measurable value such as a parameter, an amount, a duration, and so on, and is used to include variations of +/- 20%, more preferably +/- 10% or less, even more preferably +/- 5% or less, more preferably +/- 1% or less, and even more preferably +/- 0.1% or less relative to the specified value, to the extent such variations are applicable to be performed in the present invention. However, it is to be understood that the value to which "approximately" refers is specifically mentioned. "Include", "comprising" and "includes" as used herein are synonyms for "containing", "containing", "contains", and "consist of", "consisting of", "consists of" and are inclusive terms which specify the presence of what follows, e.g. a component, and do not exclude the presence of additional, non-listed components, aspects, elements, members, parts or steps, known in the professional knowledge or stated herein.
The numerical intervals listed by end values contain all values and fractions within that range, as well as the stated end values.
The term "weight%" (weight percentage), throughout the document, unless otherwise stated, refers to the relative weight of the respective component based on the total weight of the formulation.
The term "strictly higher" or "strictly lower" as used herein when comparing amounts or values means that equality between the values is excluded, more preferably that the amounts or values differ by more than noise.
The terms "substantially higher" or "substantially wider" in relation to a first power value, such as an applied power, a limit power, a threshold value, or a given power value, when compared to a second power value, means that the first power value is higher than the second power value as is apparent to a person skilled in the art of low pressure plasma generation. The first power value can therefore preferably be higher than the second power value with at least 0.1 W, more preferably with 0.2 W, even more preferably with 0.5 W, even more preferably with 1 W, even more preferably with 2 W or even 5 W, most preferably with at least 10 W .
Similarly, the terms "substantially lower" or "substantially narrower" in relation to a first power value compared to a second power value mean that the first power value is lower than the second power value as is apparent to a person skilled in the plasma field generation at low pressure. The first power value can therefore preferably be lower than the second power value with at least 0.1 W, more preferably with 0.2 W, even more preferably with 0.5 W, even more preferably with 1 W, even more preferably with 2 W or even 5 W, most preferably with at least 10 W .
By the terms "stable plasma inflammation", "stable inflammation" or "stable plasma" as used herein is meant that during normal use a minimal amount or flow of ionized molecules is present all the time.
By the term "time average", "time average", or "average over time" as used herein in relation to an amount, is meant the average of this amount over a given time period, the average preferably being calculated by the integrated amount over divide that period by the length of the period.
By the term "burst mode" as used herein is meant a way of applying the power, the power being higher for a certain time than a predetermined upper "burst" threshold value, after which the power is reduced to below a predetermined lower "burst" threshold, but continuous (ie all the time) is higher than a lower limit, strictly higher than 0 W and preferably substantially higher than 0 W, for the remainder of the process duration.
By the term "sinusoidal mode" as used herein is meant a way of applying power, wherein the power is sinusoidally varied between at least an upper limit and at least an lower limit, both substantially higher than 0 W, and optionally with the amplitude of the sinusoidal varying power is modulated.
By the term "repeated burst mode" as used herein is meant a way of applying power, wherein at least a lower limit, strictly higher than 0 W, preferably substantially higher than 0 W, is applied (continuously) all the time, and wherein the power is increased at repeated time intervals above a predetermined upper limit or optionally above an intermediate limit.
By the term "triangular mode" as used herein is meant a manner of applying the power wherein the power is varied in a linear manner between at least an upper limit, at least an lower limit, and optionally at least an intermediate limit, all strictly, and at preferably substantial, higher than 0 W.
In a preferred embodiment, the power input comprises at least one additional intermediate power limit, strictly higher than, and preferably substantially higher, than said lower limit, and strictly lower, and preferably substantially lower, than said upper limit.
In a preferred embodiment the power is all the time (continuously in time) strictly higher than 0.1 W, preferably strictly higher than 0.2 W, more preferably strictly higher than 0.5 W, even more preferably strictly higher than 1 W, even more preferably strictly higher than 2 W, more preferably strictly higher than 5 W, preferably strictly higher than 10 W during the treatment period.
In a preferred embodiment, the plasma consists of one or more monomers that can be polymerized via radical polymerization, condensation polymerization, addition polymerization, stepwise polymerization, or polymerization via chain length growth, and optionally the plasma consists of one or more carrier molecules, or a mixture thereof consisting of at least one monomer that can be polymerized.
In a preferred embodiment, the power is applied in burst mode, sinusoidally, in repeated burst mode, such as repeated burst mode with square or rectangular shape, or triangularly, such as in regular triangular fashion or irregular triangular fashion, or via super positions of previous methods of application.
In one embodiment of the invention, the lower limit of power is 10 to 90% of the upper limit, preferably the lower limit is 20 to 80% of the upper limit.
In a preferred embodiment, the power is applied in burst mode, wherein an upper limit of the power, substantially higher than 0 W, is applied for a given period, after which the power is returned to a lower limit, substantially higher than 0 W, for the remaining duration of treatment.
In a preferred embodiment, the power is applied sinusoidally, wherein the power is sinusoidally varied between at least an upper limit of the power and at least a lower limit of the power, both substantially higher than 0 W, and optionally varying the amplitude of the sinusoidal power is modulated.
In a preferred embodiment, the power is applied in repeated burst mode, wherein at least a lower power limit, strictly substantially higher than 0 W, is continuously applied and the power is increased at regular time intervals to the upper limit or to an intermediate limit of the power, wherein the intermediate limit is 20 to 95%, preferably 30 to 80% of the upper limit of the power.
In a preferred embodiment, the power is varied in a triangular manner between at least one lower limit, at least one upper limit and optionally at least one intermediate limit, all substantially higher than 0 W, and wherein the power is varied in a linear manner, preferably with the intermediate value of the power is 20 to 95%, more preferably 30 to 80% of the upper limit of the power.
In a preferred embodiment, the upper limit of the power is applied each time for a duration between 100 ms and 5000 ms, and / or the lower limit is each time applied for a duration between 500 ms and 30000 ms, and / or the intermediate limit of the power applied for a duration between 100 ms and 5000 ms.
In a preferred embodiment, a sequence of changing the power between an upper limit and a lower limit is continuously repeated during the treatment duration.
In a preferred embodiment, after applying the upper limit of the power and after applying the lower limit of the power, a sequence of changing the power between an intermediate limit and a lower limit is continuously repeated during the treatment period.
In a preferred embodiment, a sequence wherein the power is changed between an upper limit and a lower limit, followed by x times change between an intermediate limit and a lower limit, is continuously repeated during the total plasma process time, where x is at least 1, e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more.
In a preferred embodiment, the power is applied as a superposition of at least two of the following power modes, including burst mode, sinusoidal mode, repeated burst mode, and triangular mode.
In a preferred embodiment, the substrate being treated may consist of polymers, metal, glass, ceramic materials, paper or composites consisting of at least two materials just mentioned. Thus, a substitute may, for example, consist of fiberglass or flax fiber-reinforced plastics as used in the automotive sector, or may consist of, for example, a combination of conductive (e.g., metallic) and insulating (e.g., ceramic or polymeric) materials, such as printing boards. In a particular embodiment, the composite structure may consist of at least two polymeric, such as flax fiber-reinforced polyamide or polymer-reinforced polymers, e.g. polypropylene reinforced polypropylene.
Referring to the accompanying figures, further embodiments of the present invention are described below.
Referring to Figure 1, the power is applied via a continuous wave at a constant continuous wave power Pc, as indicated by line 100. The average power is thus Pc, and is selected depending on the design of the device, the dimensions and the volume of the device, and of the monomer or monomers used.
Preferably, the continuous wave power Pc, when placed in a chamber with a volume of 490 l, is about 5 to 1000 W, preferably about 5 to 500 W, more preferably 10 to 250 W, e.g. 15 to 200 W, such as 20 to 150 W, such as 25 to 100 W, e.g. 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, or 25 W.
Referring to Figure 2, the power is applied in a pulsed manner. In pulsed processes, the power of the process is bundled together in peak power Pp, represented by line 200, which are applied during an on-time Ton. During every other moment of the process, referred to as the off-time Toff, no power is applied. This means that after every on-time Ton, at which the peak power Pp is applied, the power falls back to 0 W for a time duration Toff. After this, the peak power Pp is re-applied for a time period Ton. This on-off sequence is repeated throughout the entire process time. The duration at which the peak power is applied, Ton, is typically short, while Toff is typically longer.
The pulse frequency is calculated via formula (I) and the switching time via formula (II):
(I) (II)
The frequency and the switching time, or the Ton and Toff, can be selected in such a way that a low average power Pavg is obtained according to formula (III):
(ONION)
The optimum frequency and switching time depend on the monomer precursor or monomer precursors used, and on the dimensions and design of the low pressure plasma chamber, as described in various documents, e.g. in:
Yasuda, H. and Hsu, T., Some Aspects of Plasma Polymerization Investigated by Pulsed R.F. Discharge, Journal of Polymer Science: Polymer Chemistry Edition, vol. 15, 81-97 (1977)
Yasuda, H., Hsu, T., Some Aspects of Plasma Polymerization or Fluorine-Containing Organic Compounds, Journal of Polymer Science: Polymer Chemistry Edition, vol. 15, 2411-2425 (1977)
Panchalingam V., Poon, Bryan, Hsiao-Hwei Huo, Savage, Charles R., Timmons, Richard B. and Eberhart Robert C., Molecular surface tailoring or biomaterials via pulsed RF plasma discharges, J. Biomater, Sei. Polymer Edn, Vol. 5, No.1 / 2, 1993, 131-145
Panchalingam V., Chen, X., Huo, H-H., Savage, C.R., Timmons, R.B. and Eberhart R.C., Pulsed Plasma Discharge Polymer Coatings, ASAIO Journal, 1993, M305-M309
Hynes, A.M, Shenton, M.J. and Badyal, J. P. S., Plasma Polymerization of Trifluoromethyl-Substituted Perfluorocyclohexane Monomers,
Macromolecules 1996, 29, 18-21
Hynes, A.M, Shenton, M.J. and Badyal, J.P.S., Pulsed Plasma Polymerization of Perfluorocyclohexane, Macromolecules 1996, 29, 4220-4225 Jenn-Hann Wang, Jin-Jian Chen and Timmons, Richard B., Plasma Synthesis or a Novel CF3-Dominated Fluorocarbon Film, Chem. Mater. 1996, 2212-2214
Jonhston, Erika E. and Ratner, Buddy D., Surface characterization or plasma deposited organic thin films, Journal of Electron Spectroscopy and Related Phenomena 81, 1996, 303-317
Limb, Scott J., Gleason, Karen K., Edell, David J. and Gleason, Edward F., Flexible fluorocarbon wire coatings by pulsed plasma enhanced Chemical vapor deposition, J. Vac. Sei. Technol. A15 (4), Jul / Aug 1997, 1814-1818 US patent 5,876,753
The applicant has found that when the power is applied in a pulsed manner, the pulse frequency can be between 100 Hz and 10 kHz with a switching duration of about 0.05 to 50, so that the best results in terms of functionality such as hydrophobic and / or oleophobic, or hydrophilic would be obtained.
When the power is pulsed applied in a 490 L large plasma chamber, the peak power Pp applied is preferably about 5 to 5000 W, more preferably about 50 to 2500 W, even more preferably about 75 to 1500 W, e.g. 100 to 1000 W, e.g. 125 to 750 W, such as 150 to 700 W, e.g. 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 175, or 150 W.
Referring to Figures 3A to 3D, an embodiment for first inventive continuous power mode is described, to which the applicant refers as the "burst mode". The power is applied in a continuous manner whereby an initial upper limit of the power, Pb, is applied, indicated by lines 300, 310, 320 and 330. After a certain period of time Tb, which is determined by the system and the monomer or monomers, whether or not combined with one or more carrier gases, that are used, the power is reduced from the initial upper limit to a second lower limit Pf, substantially higher than 0 W and indicated by lines 301, 311, 321 and 331, which are continuous is applied for the remainder of the process time to maintain plasma inflammation in this way.
When the power is applied to a plasma chamber of 490 l content, the initial upper limit Pb is preferably about 5 to 5000 W, more preferably about 20 to 2500 W, even more preferably about 25 to 1500 W, e.g. 30 to 1000 W, e.g. 40 to 750 W, take 50 to 700 W, e.g. 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 175, 150, 125, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, or 50 W.
The lower limit is preferably about 10 to 90% of the power of the upper limit, more preferably 20 to 80% of the power of the upper limit, for example 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, or 20%.
When the power is applied to a plasma chamber of 490 l capacity, the lower limit of power, Pf, is preferably about 5 to 1000 W, more preferably about 5 to 500 W, even more preferably about 10 to 250 W, e.g. 15 to 200 W take 20 to 150 W, such as 25 to 100 W, e.g. 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, or 25 W.
For example, if the initial upper limit is 100 W and the lower power limit is 30% of this upper limit, then the lower power limit is set at 30 W.
For example, if the initial upper limit is 80 W and the lower power limit is 50% of this upper limit, then the lower power limit is set at 40 W.
The decrease in the power from Pb to Pf occurs over a period of time Td. In the schematic representations of Figures 3A and 3B, Td is substantially higher than 0 seconds. However, in some cases, it is preferable to take Td very close to 0s, as shown in Figures 3C and 3D.
The optimum values for Pb, Pf, Tb and Td depend on the monomer precursor or precursors used, and on the dimensions and design of the low pressure plasma device.
The time period Tb during which the initial upper limit Pb is applied depends on the monomer or monomers, optionally combined with one or more carrier molecules that are used, and on the electrode configuration that is used, and is preferably between 200 ms and 30000 ms, more preferably between 250 ms and 25000 ms, even more preferably between 500 ms and 20000 ms, for example between 1000 ms and 10000 ms, such as 10000, 9500, 9000, 8500, 8000, 7500, 7000, 6500, 6000, 5500, 5000, 4500, 4000, 3500, 3000, 2500, 2000, 1900, 1800, 1700, 1600, 1500, 1400, 1300, 1200, 1100, or 1000 ms.
The time period Td during which the power is lowered from Pb to Pf is preferably between 1 ps and 5000 ms, more preferably between 1 ps and 2500 ms. In a preferred embodiment Td is kept as low as possible, preferably lower than 500 ps, more preferably lower than 200 ps, even more preferably lower than 100 ps, even more preferably lower than 50 ps, for example lower than 20 ps, take lower than 10 ps , preferably lower than 5 ps, e.g. as illustrated by Figures 3C and 3D.
In another embodiment, the duration Td is longer than 50 ms, preferably longer than 100 ms, even more preferably longer than 200 ms, for example longer than 500 ms, even more preferably longer than 1000 ms.
Defining the correct power values results in a low average power, combined with improved plasma ignition and improved plasma stability. This clearly results in better quality and uniformity of the coating.
Figure 4 shows a schematic representation of a second inventive embodiment in which the power is applied continuously. The power is applied in a sinusoidal manner with a period Tt. The power varies continuously during the process, but never falls back to 0 W, so this embodiment is considered a continuous power mode that differs substantially from pulsed plasma. The power varies around an average power value Pa, substantially higher than 0 W, and is half the time duration of period Tt, time duration Th (Th is V2 of Tt), higher than the average value Pa, with a maximum power Ph, and is half the duration of period Tt, duration T1 (Ti is Vi of Tt), lower than the average value Pa, with a minimum power Pi, substantially higher than 0 W. The power is constantly varied around the average value Pa, and reaches its maximum after Ά of the period Tt and its minimum after 3A of the period Tt. This variation of the power as a function of time within one period is continuously repeated during the total duration of the low pressure plasma process. The difference in absolute value between Ph and Pa is the amplitude of the sinusoidal power mode, and is equal to the difference in absolute value between Pi and Pa.
The average power Pa is preferably more than 50% of the maximum power Ph so that the minimum power Pi is substantially higher than 0 W so as to maintain the plasma ignition. The minimum power Pi is calculated with the formulas IV and V, provided that the values of Pa and Ph are known, where Pa can be calculated based on the value for Ph and a percentage z of more than 50%: PI = Pa- (Ph - Pa) (IV) or PI - (2 * z - 1) * Ph (V)
For example, with a maximum power of 500 W and an average power equal to 60% of the maximum power (z = 0.6), the average power equals 300 W and the minimum power equals 100 W.
When the power is applied to a plasma chamber of 490 l capacity, the maximum power Ph is preferably about 5 to 5000 W, more preferably about 10 to 2500 W, even more preferably about 25 to 1500 W, e.g. 50 to 1000 W, e.g. 75 to 750 W, take 100 to 700 W, eg 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 190, 180, 175, 170, 160, 150, 140, 130, 125, 120, 110, or 100 W.
Referring to Figures 5A and 5D, a third inventive embodiment is described, wherein the power is applied in a manner to which the applicant refers as the "repeated burst mode". The applied power is varied in a repetitive sequence between at least one lower limit P1 (indicated by lines 500, 510, 520 and 530, respectively) and at least one upper limit P2 (indicated by lines 501, 511, 521 and 531, respectively), both substantially higher than 0 W (Figures 5A and 5B). An intermediate value of the power P3 can optionally be applied for a specific period of time (Figures 5C and 5D, indicated by lines 522 and 532, respectively). Since P1 and P2 are substantially higher than 0 W, P3 will also be substantially higher than 0 W.
Referring to Figures 5A and 5B, the upper limit of the power, P1, is applied at the start of the process, for a period of time T1. After T1, the power is lowered to a lower limit of the power, P2, substantially higher than 0 W. P2 is held for a time T2. After this, the power is increased to P1, re-applied for a time period T1. After this, the power is again reduced to T2, again applied for a time period T2. This repetitive sequence, where P2 is fired at regular intervals to P1, is repeated for the entire duration of the plasma process, hence the name "repeated burst mode".
In the case where time periods T1 and T2 are equal, the "repeated burst mode" is a square wave function. In the case where T1 is smaller than T2, the "repeated burst mode" is a rectangular wave function.
The sequence of the power can be schematically represented as (P1 -> P2) n, where n is calculated according to the following formula:
(VI)
Referring to Figure 5C, the upper limit of the power, P1, is applied at the start of the low pressure plasma treatment for a time period T1. After T1, the power is lowered to a lower limit of the power, P2, substantially higher than 0 W. P2 is applied for a period of time T2. After this, the power is increased to an intermediate value of the power, P3, substantially higher than 0 W, which is held for a period of time T3. After this, the power is lowered back to the lower limit P2, which is maintained for a period of time T2. After this, the power is increased again to P3 for a time duration T3. This repetitive sequence, wherein the power P2 is fired at regular intervals to an intermediate value P3, is then repeated for the remaining duration of the plasma process, hence the name "repeated burst mode."
In the case where T1, T2 and T3 are equal, the "repeated burst mode" represents a square wave function. In the case where not all three times T1, T2 and T3 are the same, e.g. when T1 and T2 are equal and shorter than T3, the "repeated burst mode" represents a rectangular wave function.
The sequence of the power can be represented schematically as P1 - ((P2 -> P3)) m, where m is calculated according to the following formula:
(VII)
Referring to Figure 5D, the upper limit of the power P1 is applied at the beginning of the low pressure plasma process for a period of time T1. After this, the power is lowered to a lower limit of the power P2, substantially higher than 0 W. P2 is held for a period of time T2. After this, the power is increased (or boosted) to an intermediate value of the power, P3, substantially higher than 0 W, which is held for a time period T3. After this, the power is again lowered to the lower limit of the power, P2, which is again applied for a period of time T2 iy. After this, the power is varied between P3 (for a duration T3) and P2 (for a duration T2) for a certain number of times, noted as x. For example, X is from 0 to 9. Figure 5D is a schematic representation of x equal to 2.
This repetitive sequence P1 - P2 - P3 - P2 - (P3 - P2) x, with x from 0 to 9, is considered a "repeated burst cycle". This "repeated burst cycle" is repeated for the total duration of the low pressure plasma process, hence the name "repeated burst mode". The number of "repeated burst cycles", y, can be calculated using the following formula:
(VIII)
In the case where T1, T2 and T3 are equal, the "repeated burst mode" represents a square wave function. In the case where not all three times T1, T2 and T3 are the same, e.g. when T1 and T2 are equal and shorter than T3, the "repeated burst mode" represents a rectangular wave function.
The "repeated burst mode" can be seen as a continuous method of applying the power to a lower limit (substantially higher than 0 W), whereby the plasma is regularly fired at at least an upper limit of the power and optionally at least an intermediate value of the ability to maintain plasma inflammation in this way. This embodiment clearly differs from the pulsed mode since the power never falls back to 0 W. during the entire process.
The applicant has surprisingly discovered that the inventive methods of applying a continuous power, as described herein with reference to Figures 5A to 5D, wherein the plasma is fired at regular intervals, the ignition of the plasma and the stability of the plasma during the deposition process improves, since the plasma remains fully and uniformly inflamed.
The time intervals T1, T2 and optionally T3, and the values for the power P1, P2 and optional P3, are determined by the system (dimensions and design) and the monomer or monomers, optionally combined with one or more carrier molecules, which are used .
When the power is applied to a plasma chamber of 490 l capacity, the upper limit of the power, PI, is preferably about 5 to 5000 W, more preferably about 10 to 2500 W, even more preferably about 25 to 1500 W, e.g. 50 to 1000 W, for example 75 to 750 W, take 150 to 700 W, e.g. 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 190, 180, 175, 170, 160, 150, 140, 130, 125, 120, 110, 100, 95, 90, 85, 80, or 75 W.
Preferably, the lower power limit, P2, is about 10 to 90% of the upper limit P1, more preferably about 20 to 80% of the upper limit, for example 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, or 20%.
When the power is applied to a plasma chamber of 490 l capacity, the lower limit of power, P2, is preferably about 5 to 1000 W, more preferably about 5 to 500 W, even more preferably about 10 to 250 W, e.g. 15 to 200 W, take 20 to 150 W, such as 25 to 100 W, eg 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, or 25 W.
Preferably, the intermediate value of power, P3, is about 20 to 95% of the upper limit P1, more preferably about 30 to 80% of the upper limit, for example 80, 75, 70, 65, 60, 55, 50, 45, 40 35 or 30%. For all embodiments, the intermediate power value P3 is always higher than the lower limit of the power, P2.
When the power is applied to a plasma chamber of 490 l capacity, the intermediate value of the power, P3, is preferably about 5 to 1000 W, more preferably about 10 to 500 W, even more preferably about 15 to 250 W, e.g. up to 200 W, take 25 to 150 W, such as 50 to 100 W, e.g. 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, or 50 W.
For example, if the upper limit of the power, P1, equals 500 W and the lower limit of the power, P2, equals 10% of P1, then P2 equals 50 W.
For example, if the upper limit of the power, P1, is 100 W and the lower limit of the power, P2, is 30% of P1 and the intermediate value of the power, P3, is 50% of P1, then P2 is equal to 30 W and P3 is equal to 50 W.
T1 is preferably between 100 ms and 5000 ms, more preferably between 200 ms and 4000 ms, even more preferably between 500 ms and 2500 ms, e.g. 2500, 2400, 2300, 2250, 2200, 2100, 2000, 1900, 1800, 1750, 1700 , 1600, 1500, 1400, 1300, 1250, 1200, 1100, 1000, 950, 900, 850, 800, 750, 700, 650, 600, 550, or 500 ms.
The "repeated burst mode" is specifically chosen because the applications have discovered that this method of applying power yields coatings with improved oil repellency properties, and also leads to better plasma ignition and stabilization, while also is better than pulsed plasma in terms of the deposition rate, ie the rate at which a coating is deposited on a substrate. T2 is preferably between 500 ms and 30000 ms, more preferably between 750 ms and 20000 ms, even more preferably between 1000 ms and 15000 ms, for example 15000, 14500, 14000, 13500, 13000, 12500, 12000, 11500, 11000, 10500, 10000 , 9750, 9500, 9250, 9000, 8750, 8500, 8250, 8000, 7750, 7500, 7250, 7000, 6750, 6500, 6250, 6000, 5750, 5500, 5250, 5000, 4750, 4500, 4250, 4000, 3750 3500, 3250, 3000, 2750, 2500, 2250, 2000, 1900, 1800, 1750, 1700, 1600, 1500, 1400, 1300, 1250, 1200, 1100, or 1000 ms. T3 is preferably between 100 ms and 5000 ms, more preferably between 200 ms and 4000 ms, even more preferably between 500 ms and 2500 ms, e.g. 2500, 2400, 2300, 2250, 2200, 2100, 2000, 1900, 1800, 1750, 1700 , 1600, 1500, 1400, 1300, 1250, 1200, 1100, 1000, 950, 900, 850, 800, 750, 700, 650, 600, 550, or 500 ms.
Figures 6A to 6C show schematic representations of a fourth inventive embodiment for applying a power in a continuous manner, the power being applied in a triangular manner. The power is constantly varied during the total plasma process time and is always equal to or higher than a minimum power Pm, which is substantially higher than 0 W.
Referring to Figure 6A, an upper power limit, Pu, substantially higher than 0 W, is applied at the start of the process, as indicated by line 600. This upper limit Pu is lowered to a lower power limit, Pm, substantially higher than 0 W, as indicated by line 601. After this, the power is again increased to Pu, and again reduced to Pm. This sequence of raising and lowering is constantly repeated for the entire process duration of the low pressure plasma process.
The time required to return the power of Pu to Pm is indicated by Tm. The time to increase the power from Pm to Pu is indicated by Tu. The speed of the power and the lowering of the power is constant, i.e. the course is linear. The slope of the lines in Figure 6A can be calculated using the following formulas:
(IX) (X)
In the case where Tm and Tu are equal, the triangular mode is a regular triangular mode. If Tm and Tu are not equal, the triangular mode is an irregular triangular mode.
Referring to Figure 6B, an upper limit of power, Pu, substantially higher than 0 W, as indicated by line 610, is applied at the start of the low pressure plasma process. This upper limit Pu is then lowered to a lower limit of the power, Pm, substantially higher than 0 W, as indicated by line 611. After this, the power is increased to an intermediate value of the power, Pi, substantially higher than 0 W, such as indicated by line 612, and then lowered again to the lower limit Pm. After this, the power is again increased to the intermediate value Pi, and again lowered to the lower limit Pm. This sequence of increasing and decreasing the power between Pm and Pi is then repeated for the remaining duration of the plasma process.
The time required to lower the power from Pu to Pm is denoted by Tum. The time required to reduce the power from Pi to Pm is indicated by Tim. The time required to increase the power from Pm to Pi is indicated by Tmi. The speed of the power and the lowering of the power is constant, i.e. the course is linear. The slope of the lines in Figure 6B can be calculated using the following formulas:
(XI) (XII)
(XIII)
Referring to Figure 6C, an upper power limit, Pu, substantially higher than 0 W, as indicated by line 620, is applied at the start of the low pressure plasma process. This upper limit Pu is then lowered to a lower limit of the power, Pm, substantially higher than 0 W, as indicated by line 621. After this, the power is increased to an intermediate value of the power, Pi, substantially higher than 0 W, as indicated with line 622, after which the power is again reduced to the lower limit Pm. After this, the power is varied between Pm and Pi for a certain number of times, noted as q. For example, Q is from 0 to 9. Figure 6C gives a schematic representation where q is 2.
This repetitive sequence Pu - Pm - Pi - Pm - (Pi - Pm) q, with q equal to 0 to 9, is considered one "triangular fashion cycle". This triangular mode cycle is now repeated for the total duration of the low pressure plasma process.
The time required to lower the power from Pu to Pm is denoted by Tum. The time required to reduce the power from Pi to Pm is indicated by Tim. The time required to increase the power from Pm to Pi is indicated by Tmi. The time required to increase the power from Pm to Pu is indicated by Tmu. The speed of the power and the lowering of the power is constant, i.e. the course is linear. The slope of the lines in Figure 6C can be calculated using the following formulas:
(XIV) (XV) (xvi) (XVII)
The applicant has surprisingly discovered that the inventive ways of applying a continuous power, as described herein with reference to Figures 6A to 6C, improves the ignition of the plasma and the stability of the plasma during the deposition process, since the plasma is complete and uniform remains inflamed.
The times Tm, Tu, and optionally Tum, Tmu, Tim and Tmi, as well as the power values Pu, Pm and optional Pi, are determined by the system (dimensions and design) and the monomer or monomers, whether or not combined with one or multiple carrier molecules that are used.
When the power is applied to a plasma chamber of 490 l capacity, the upper limit of power, Pu, is preferably about 5 to 5000 W, more preferably about 10 to 2500 W, even more preferably about 25 to 1500 W, e.g. 50 to 1000 W, for example 75 to 750 W, take 150 to 700 W, e.g. 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 190, 180, 175, 170, 160, 150, 140, 130, 125, 120, 110, 100, 95, 90, 85, 80, or 75 W.
The lower power limit, Pm, is preferably about 10 to 90% of the upper limit Pu, more preferably 20 to 80% of the upper limit, for example 80, 75, 70, 65, 60, 55, 50, 45, 40, 35 , 30, 25, or 20%.
When the power is applied to a plasma chamber of 490 l capacity, the lower limit of the power, Pm, is preferably equal to about 5 to 500 W, more preferably about 10 to 250 W, e.g. 15 to 200 W, take 20 to 150 W , such as 25 to 100 W, e.g. 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, or 25 W.
The intermediate value of the power, Pi, is preferably about 20 to 95% of the upper limit Pu, more preferably 30 to 80% of the upper limit, for example 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, or 30%. For all embodiments, the intermediate value Pi is always higher than the lower limit Pm.
When the power is applied to a plasma chamber of 490 l capacity, the intermediate value of the power is preferably equal to about 5 to 1000 W, more preferably about 10 to 500 W, even more preferably about 15 to 250 W, e.g. 20 to 200 W take 25 to W, such as to W, e.g. 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, or 50 W.
For example, if the upper limit Pu is 500 W and the lower limit P m is 10% of Pu, then P m is 50 W.
For example, when the upper limit Pu equals 100 W and the lower limit P m equals 30% of Pu and the intermediate value Pi equals 50% of Pu, then P m equals 30 W and Pi equals 50 W.
Preferably, Tm, Tu, Tmu, Tim and Tmi are between 100 ms and 30000 ms, more preferably between 200 ms and 20000 ms, even more preferably between 500 ms and 15000 ms, such as between 1000 ms and 10000 ms, e.g. 10000, 9750, 9500 , 9250, 9000, 8750, 8500, 8250, 8000, 7750, 7500, 7250, 7000, 6750, 6500, 6250, 6000, 5750, 5550, 5250, 5000, 4750, 4500, 4250, 4000, 3750, 3500, 3250 3000, 2750, 2500, 2250, 2000, 1900, 1800, 1750, 1700, 1600, 1500, 1400, 1300, 1250, 1200, 1100, or 1000 ms.
The applicant has further discovered that combinations or superpositions of the aforementioned inventive embodiments of powers applied in a continuous manner may have further advantages for certain devices and chemical products used. Figure 7 shows an example in which the "repeated burst mode" of Figure 5A is combined with the triangular mode of Figure 6A. Other combinations are also possible, and the optimum configuration can be found through routine techniques to evaluate the resulting coating and to optimize the process parameters.
All individual embodiments of continuous mode have a power that is substantial than 0 W at any time during the low pressure plasma process. Consequently, all combinations and superpositions thereof also have powers that are substantially higher than 0 W at any time of the low pressure plasma process.
The radiofrequency electrode or electrodes preferably generate a high-frequency electric field at frequencies between 20 kHz and 2.45 GHz, more preferably from 40 kHz to 13.56 MHz, with 13.56 MHz being preferred.
EXAMPLES
In order for the present invention to be better understood, it is described below by means of examples which, however, do not mean limitation of the invention described above.
Example 1
The applicant has discovered in a lab arrangement that the manner in which the power is applied depends on the monomer and the device being used. This is specifically the case for acrylates and methacrylates used in low-pressure plasma deposition processes to deposit coatings on substrates to make them water and / or oil-repellent. The applications have found that perfluoro (meth) acrylates with a maximum of 6 carbon atoms in the perfluorocarbon chain result in polymeric coatings that achieve significantly better oil-repellency levels when deposited in a manner in which the power is applied continuously, including continuous power to a constant value, and the inventive continuous power modes "burst mode", sinusoidal mode, "repeated burst mode" or triangular mode, or any superposition or combinations thereof, then when deposited via pulsed mode.
On the other hand, perfluoro (meth) acrylates with 8 carbon atoms in the perfluorocarbon chain result in polymeric coatings that have similar oil repellency levels when deposited in a continuous manner, including continuous mode at a constant power value and the inventive continuous mode "burst mode" ", sinusoidal mode," repeated burst mode "or triangular mode, or any superposition or combinations thereof, and pulsed mode, although the pulsed mode, the" burst mode ", the sinusoidal mode, the" repeated burst mode "or the triangular manner, or any superposition or combinations thereof, tend to improve performance, for example in terms of thickness of the cover layer.
In this example, two monomers are deposited in a continuous manner at constant power ("Cw") and in a pulsed manner ("Pulsed"), as presented in Table 1. The test was performed in a lab set-up on a polypropylene non-woven fabric ( Eng. Nonwoven) and the performance was evaluated by means of the oil repellency test according to ISO 14419.
For the monomer containing 8 carbon atoms in the perfluorocarbon chain, an oil level is reached via pulsed plasma that is equal to slightly higher than the oil level that is achieved in a continuous manner.
Both for the acrylate and the methacrylate consisting of 6 carbon atoms in the perfluorocarbon chain, the coating obtained via continuous plasma has a significantly better performance than the coating obtained in a pulsed manner. With plasma in a continuous manner an oil repellency level of 6 is achieved, measured according to ISO 14419, at low power, e.g. 100 W in a 490 I large plasma chamber used as a lab setup, and after short process times, e.g. 2 minutes. It is disadvantageous to have high powers, e.g. 350 W, 500 W, 1000 W or more to be used in a 490 I chamber, since the monomer precursor will fragment, leading to poor coatings, e.g. without uniformity.
Table 1: Shows the oil repellency levels for processes in a continuous and pulsed manner
Example 2: Method of applying the power
As described above, it is known that for complex monomers, the average power should be low enough to prevent fragmentation of the functional group from the monomer precursor. For smaller machines, e.g. with a chamber volume of less than 1000 l, methods as described in the prior art are not always sufficient to maintain the continuous ignition of the plasma, since the necessary low average power may be too low to maintain with commercially available generators, can prevent a good and stable inflammation of the plasma.
For larger machines, e.g. with a chamber volume of 1000 I and more, the required low average power is slightly higher than for the smaller machines, due to the design of the room and the design of the electrodes. For these larger systems, it is possible in most, but not all, to maintain the necessary average power with commercially available generators.
Table 2 shows the results of lab tests performed in three smaller units, with respective volumes of 50 I, 89 I and 490 I, and in one larger machine with a volume of 3000 I. A monomer with 8 carbon atoms in the perfluorocarbon chain was deposited on a polypropylene non-woven fabric, and this in various power modes as described above. The performance was evaluated by means of the oil repellency test according to ISO 14419.
Table 2: Shows the oil repellency levels for processes performed in different continuous ways and in a pulsed manner in chambers of different volumes. The power range as used in the constant power processes is also given.
It is clear from Table 2 that for small volume chambers, the coatings deposited with a plasma in a continuous manner at a constant power, the oil repellency is lower than for coatings coated with pulsed plasma. This is caused by unstable plasma ignition because the power required is too low to be stably generated with commercially available generators. However, when the continuous mode is used whereby the power is generated in "burst mode" or "repeated burst mode", oil repellency levels are obtained that are equal to the levels achieved with pulsed plasma, and at the same time the inflammation of the plasma is strong improved. The oil repellency obtained through the "burst mode" and the "repeated burst mode" also confirm that the complex precursor molecules are not fragmented during the plasma processes.
With the coatings deposited in the large room, no difference is noted in the coatings deposited with pulsed plasma and in the three continuous modes. It is clear from Table 2 that in a continuous manner with a constant power the same oil level is now achieved as with pulsed plasma, because the required average power is high enough to be stably maintained with commercially available generators.
The applicant has also surprisingly discovered that the "burst mode", the sinusoidal mode, the "repeated burst mode", the triangular mode and any superposition thereof not only allow, in comparison with continuous mode at constant power, a better ignition of the plasma with an improved oil repellency as a result, but also have a deposition rate that is higher than that achieved with pulsed processes and that is in line with the coatings deposited with continuous mode at constant power. This leads to thicker coatings in the same time, as is clear from Table 3. The experiments were performed in a 490 I chamber for different process times. The thickness measurements were performed on an Si wafer that was placed in the same position in each process.
Table 3: Shows the thickness of the coatings for different continuous modes and pulsed mode in a 490 I chamber performed at six different deposition times

权利要求:
Claims (15)
[1]
CONCLUSIONS
A method for depositing a coating, comprising the steps of: Introduction of a substrate containing a surface on which a coating must be deposited in a low pressure reaction chamber; Exposing the surface to a plasma in the reaction chamber for a certain treatment time; Ensuring a stable plasma ignition by applying a power, characterized by the fact that the power input is strictly higher than zero Watt (0 W) during the treatment time and consists of at least a lower power limit and at least an upper power limit power, strictly greater than the lower limit, whereby a substrate is obtained which has a surface on which a cover layer has been deposited.
[2]
Method of depositing a coating according to Claim 1, wherein the power input contains at least one additional intermediate value of the power, strictly greater than the lower limit and strictly lower than the upper limit.
[3]
A coating method according to any one of the preceding Claims, wherein the power input is constantly strictly higher than 0.1 W, more preferably strictly higher than 0.25 W, even more preferably strictly higher than 0.5 W, even more preferably strictly higher than 1 W, even more preferably strictly higher than 2 W, even more preferably strictly higher than 5 W during the treatment time, and even more preferably strictly higher than 10 W during the treatment time.
[4]
A coating deposition method according to any one of the preceding claims, wherein the plasma consists of one or more monomers that can be polymerized via radical polymerization, condensation polymerization, addition polymerization, stepwise polymerization, or polymerization via chain length growth, and wherein plasma optionally consists of one or more carrier molecules, or a mixture thereof that consists of at least one monomer that can be polymerized.
[5]
Method of depositing a coating according to any one of the preceding claims, wherein the power is applied in "burst mode", in a sinusoidal manner, in "repeated burst mode", such as "repeated burst mode" with square shape or with rectangular shape , or by triangular means, or by super positions of the foregoing.
[6]
A coating deposition method according to Claim 5, wherein the power is applied via a superposition of at least two of the following power modes: "burst mode", sinusoidal mode, "repeated burst mode" and triangular mode.
[7]
A coating method according to any one of the preceding claims, wherein the lower power limit is 10 to 90% of the upper power limit, and preferably is 20 to 80% of the upper limit.
[8]
Method for depositing a coating according to any one of the preceding claims, wherein the power is applied in "burst mode", wherein an upper limit of the power, substantially higher than 0 W, is applied for a specific period of time, after which the power is lowered to a lower power limit, substantially higher than 0 W, for the remaining duration of treatment.
[9]
A coating deposition method according to any of Claims 1 to 7, wherein the power is varied sinusoidally between at least an upper limit and a lower limit, both substantially higher than 0 W, and optionally the amplitude of the sinusoidally varying power is modulated; the power is applied to "repeated burst mode", wherein at least a lower limit, substantially higher than 0 W, is applied continuously and wherein the power is increased at repeated time intervals to the upper limit or to an intermediate value, the intermediate value being 20 to 95 %, preferably 30 to 80%, of the upper limit; whether the power is varied in a triangular manner between an upper limit, a lower limit and optionally an intermediate value of the power, all substantially higher than 0 W, and wherein the power is varied in a linear manner, and wherein preferably the intermediate value is 20 to 95%, more preferably 30 to 80%, is of the upper limit.
[10]
Method for depositing a coating according to any one of the preceding claims, wherein the upper limit of the power is applied for a duration between 100 ms and 5000 ms and / or wherein the lower limit of the power is applied for a duration between 500 ms each ms and 30000 ms, and / or where the optional intermediate value is applied for a duration between 100 ms and 5000 ms.
[11]
A coating deposition method according to any one of Claims 1 to 7 and 9 to 10, wherein a sequence of changing the power between an upper limit and a lower limit is continuously repeated during the entire treatment period.
[12]
A coating deposition method according to Claim 11, wherein after applying an upper limit and a lower limit, a sequence of changing the power between an intermediate value and a lower limit is continuously repeated throughout the entire treatment period.
[13]
A coating deposition method according to Claim 11 or 12, wherein the sequence of changing the power between an upper limit and a lower limit, followed by x times change between an intermediate value and a lower limit, is continuously repeated throughout the entire duration of treatment, where x is at least 1.
[14]
An apparatus for depositing a coating consisting of a low pressure plasma deposition reaction chamber on a surface of a substrate by exposure to a plasma, means for igniting a plasma in the reaction chamber or in a plasma production chamber which is in rapid communication with the reaction chamber, and means for applying a power to the plasma ignition means, the means for applying a power being configured to apply a power to the plasma ignition means, characterized by the fact that the power input is constantly strictly higher than zero Wall (0 W) during the treatment period and contains at least one lower limit, at least one upper limit strictly higher than the lower limit, and optionally at least one intermediate value - strictly higher than the lower limit and strictly lower than the upper limit -.
[15]
A substrate of which a surface comprises a coating deposited with a deposition method according to Claims 1 to 13 and / or via a deposition apparatus according to Claim 14, preferably wherein the substrate consists of polymers, metal, glass, ceramic materials, paper or composites , consisting of at least two materials selected from one or more materials from the aforementioned list.

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引用文献:

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

US4405692A|1981-12-04|1983-09-20|Hughes Aircraft Company|Moisture-protected alkali halide infrared windows|

WO1999004911A1|1997-07-28|1999-02-04|Massachusetts Institute Of Technology|Pyrolytic chemical vapor deposition of silicone films|

US20030215652A1|2001-06-04|2003-11-20|O'connor Paul J.|Transmission barrier layer for polymers and containers|

WO2003082483A1|2002-03-28|2003-10-09|Plasso Technology Limited|Preparation of coatings through plasma polymerization|

WO2011089009A1|2010-01-22|2011-07-28|Europlasma Nv|Method for the application of a conformal nanocoating by means of a low pressure plasma process|

EP2422887A1|2010-08-27|2012-02-29|Oticon A/S|A method of coating a surface with a water and oil repellant polymer layer|

US4382985A|1980-10-11|1983-05-10|Daikin Kogyo Co., Ltd.|Process for forming film of fluoroalkyl acrylate polymer on substrate and process for preparing patterned resist from the film|

EP0533044B1|1991-09-20|1999-12-29|Balzers Aktiengesellschaft|Process and apparatus for the protective coating of substrates|

US5355832A|1992-12-15|1994-10-18|Advanced Surface Technology, Inc.|Polymerization reactor|

JP3148910B2|1993-09-01|2001-03-26|日本真空技術株式会社|Plasma CVD film forming method|

US6794301B2|1995-10-13|2004-09-21|Mattson Technology, Inc.|Pulsed plasma processing of semiconductor substrates|

AU2003303816B2|2003-01-30|2006-11-02|Europlasma|Method for providing a coating on the surfaces of a product with an open cell structure throughout its structure and use of such a method|

US8114465B2|2007-04-02|2012-02-14|Ension, Inc.|Process for preparing a substrate coated with a biomolecule|

US9123509B2|2007-06-29|2015-09-01|Varian Semiconductor Equipment Associates, Inc.|Techniques for plasma processing a substrate|

JP2010238881A|2009-03-31|2010-10-21|Tokyo Electron Ltd|Plasma processing apparatus and plasma processing method|

CN102905839B|2010-03-30|2016-03-09|Imra美国公司|Based on the materials processing apparatus and method of laser|

JP5172928B2|2010-09-30|2013-03-27|株式会社東芝|Substrate processing method and substrate processing apparatus|

DK2457670T3|2010-11-30|2017-09-25|Oticon As|Method and apparatus for low pressure plasma induced coating|

GB2489761B|2011-09-07|2015-03-04|Europlasma Nv|Surface coatings|

US10157729B2|2012-02-22|2018-12-18|Lam Research Corporation|Soft pulsing|

GB2510213A|2012-08-13|2014-07-30|Europlasma Nv|Forming a protective polymer coating on a component|

WO2014056966A1|2012-10-09|2014-04-17|Europlasma Nv|Surface coatings|GB201403558D0|2014-02-28|2014-04-16|P2I Ltd|Coating|

EP3307835B1|2015-06-09|2019-05-08|P2i Ltd|Coatings|

EP3680029A1|2019-01-09|2020-07-15|Europlasma nv|A plasma polymerisation method for coating a substrate with a polymer|

法律状态:

优先权:

申请号 | 申请日 | 专利标题

EP131876237|2013-10-07|

EP13187623|2013-10-07|

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