PLASMA DIFFUSER

专利摘要:
Plasma diffuser Excerpt 5 The present invention relates to a method to at least partially prevent the discoloration of a substrate due to a plasma deposition process, wherein the plasma is diffused before and / or during deposition of the plasma on the substrate in order to obtain a topcoat. The present invention also relates to a plasma deposition apparatus that includes a plasma diffuser 10 to homogenize a plasma density around a substrate to be treated. 2014/0436
公开号:BE1021300B1
申请号:E2014/0436
申请日:2014-06-06
公开日:2015-10-26
发明作者:Filip Legein；Guy Feys；Eva Rogge
申请人:Europlasma Nv；
IPC主号:

专利说明:

Plasma diffuser
Technical domain
The present invention relates to improved ways of depositing plasma coatings on substrates that are sensitive to color changes, preferably by means of. plasma polymerization and preferably at reduced pressure.
Background
Plasma coatings, and low pressure plasma coatings in particular, are widely used today to add functionalities to materials such as hydrophilic, hydrophobic, oleophobic, scratch-resistant properties and / or barrier coatings. On some substrates, in particular dark substrates, such as black, gray, dark blue, dark green, or dark purple substrates, but also substrates that have a highly glossy surface or a low surface roughness (e.g., smooth or polished surfaces), it is an undesirable phenomenon that these substrates tend to darken in color after treatment. Sometimes a rainbow-like discoloration becomes visible.
In cases where the substrate is a material or object used per se by the end customer, it is undesirable that this color change, whether it is a darkening or the appearance of a rainbow effect, becomes visible to the end user.
To solve this problem, the applicant has invented a so-called "plasma diffuser", which allows the deposition of nano coatings with a large reduction to even the absence of discoloration while at the same time not negatively influencing the properties of the substrate. This invention makes it possible to treat products both at the end of the production process and during manufacture.
The applicant has found that the effect of discoloration is strongest with halogen-containing coatings, such as fluorine-containing coatings that are used to obtain hydrophobic and oleophobic properties on substrates. The effect is most pronounced on black, dark blue, dark green and dark gray surfaces. The effect is also pronounced on highly glossy, highly reflective surfaces and also on surfaces that have a rather smooth surface at the macroscopic level, such as flat plastic parts, such as the housing of electronic devices, or cloths or clothing made of textile.
The applicant has noticed that discoloration is more pronounced for so-called "batch" processes, in which the substrates are coated in a static manner. For example, in static processes, pieces of textiles and clothing are hung in a fixed vertical position, or plastic parts and electronics are provided with a coating in a horizontally positioned system with drawers.
At the start of the development of plasma processes, the systems used were limited in volume, for example less than 10 liters, even less than 5 liters or less than 1 liter. Such small systems are designed primarily for use in the semiconductor industry, with good plasma uniformity and good plasma density distribution due to the limited dimensions of the system and thanks to well-controllable process parameters. The design of the systems was optimized and often complex, in order to handle small and / or limited quantities of products with great precision. Discoloration was not a problem in this type of device since the pieces to be treated and the system are both small.
Yasuda, H. and Hsu, T. describe the use of a cylindrical glass chamber of 4 mm diameter and 10 cm long, with a chamber volume of 1.26 cm 3, or 0.00126 I ("Some aspects of Plasma Polymerization Investigated by Pulsed RF Discharge", Journal of Polymer Science: Polymer Chemistry Edition, vol. 15, 81-97 (1977), and "Some Aspects of Plasma Polymerization of Fluorine-Containing Organic Compounds," Journal of Polymer Science: Polymer Chemistry Edition, vol. 15, 2411- 2425 (1977)).
Panchalingam V. et al. Describe the use of a cylindrical glass chamber of 10 cm diameter and 30.5 cm long, with a chamber volume of approximately 2.4 liters ("Pulsed Plasma Discharge Polymer Coatings", ASAIO Journal, 1993, M305-309).
Hynes, AM et al. Describe the use of a cylindrical glass chamber of 5 cm in diameter and a volume of 490 cm 3 (0.49 liters) ("Plasma Polymerization of Trifluoromethyl-substituted Perfluorocycloheane Monomers", Macromolecules 1996, 29, 18-21, and "Pulsed Plasma Polymerization of Perfluorocyclohexane", Macromolecules 1996, 29, 4220-4225). For example, US Patent 4,737,379 (Energy Conversion Devices Ine.) Describes a small plasma device consisting of a tubular chamber or tank, used to deposit hard alloys, free of hydrogen, in the form of a coating, for example for passivation purposes, on e.g. semiconductors. US Patent 4,686,113 (Fairchild Semiconductor Corporation) describes a plasma device consisting of a quartz tube as a chamber for inductively coating silicon substrates, used for example in semiconductor applications. GB Patent application 2,220,006 (Philips Electronic Associated) describes the use of a plasma device to deposit coatings on substrates, e.g. semiconductor substrates, or to etch substrates. The description states that the electrodes are approximately 15 cm x 15 cm, and that the substrates treated in the examples have a diameter of 100 mm, indicating a small system for handling small objects.
Other examples of chambers used under reduced pressure are chambers for "Atomic Layer Deposition" (ALD). These processes are very complex, and various professional documents deal with the design of ALD vacuum chambers in order to guarantee a good process. These systems typically have a limited volume since larger systems lead to less easily controllable process parameters and thus to less efficient treatments. For example, US Patent Application 2009 / 255,470 (Beneq Oy) describes an ALD reactor to treat small objects according to an ALD process, the design being chosen such that the monomer enters the chamber along all chamber walls to optimize gas distribution in the chamber. Page 3 mentions a chamber with an inside diameter of 230 mm, to treat one or more silicon pieces with a diameter of 200 mm. US Patent 4,389,973 (Oy Lohja AB) describes several complex systems for an ALD reactor to optimize the process and the resulting coating. The process uses gas phase diffusion barriers to separate the individual reaction steps from the ALD process. The system is, like others, designed to handle a limited number of pieces with limited dimensions. US Patent application 2010 / 166,955 (Cambridge NanoTech Ine.) Describes a system that consists of one or more rectangular reaction chambers that are placed vertically one above the other, whereby one substrate per reaction chamber is treated. Typical chamber volumes are 20 liters, and are used to deposit thin coatings on substrates for use in LCDs, via ALD (atomic layer deposition) or ALE (atomic layer epitaxy). The design of the chamber is optimized to have a substantially uniform flow direction and speed. It is a complex design and both the dimensions of the substrates that can be treated and the flow-through are limited.
The present invention is related to reaction chambers, for example for plasma processes, which have a larger volume so that multiple products can be treated in a single process. This makes it possible to have a high flow in combination with an excellent quality of treatment. The present invention contributes to the improvement of the uniformity of the processes in terms of visual aspects, while at the same time the other characteristics of the treatment, e.g. depositing a plasma coating. Today, one of the critical parameters to implement a technology is the flow, the number of pieces that can be handled in one day, in one week, one month or one year. Larger systems were developed to meet this, in various market segments. Small R & D systems of less than 1 liter were scaled up to systems of a few hundred to thousands of liters, thanks to extensive research. For example, the applicant has developed "batch" systems of 500 liters - in which e.g. up to 300 smartphones can be handled in a single process - and even larger, up to 10,000 liters for roll-to-roll systems used to deposit coatings on textile rolls.
The main challenge for these systems on a production scale is how the plasma density or the plasma intensity can be evenly and uniformly distributed over the fully available space. It is generally known that the plasma uniformity and plasma distribution of such large systems is less than with small R & D systems. Research has been done to optimize uniformity, but it is very difficult or even impossible to have a 100% uniform plasma distribution due to the fact that there are several components of the device in the room: pump openings, gas inlets, drawers / hangers , electrodes, etc.
Consequently, discoloration on substrates that are dark and / or highly glossy and / or smooth occurred due to non-uniform plasma in the chamber. Optimization of the process parameters did not provide a solution for this discoloration. Discoloration limits the applications and markets where plasma processes can be used as added value to products. The use of plasma coatings is particularly limited for use on finished products since these products are intended for direct sale to the consumer. And consumers are of course not inclined to buy products that have discolouration, such as a non-homogeneous color or a rainbow-like appearance.
Examples of finished products where the use of plasma coatings can be limited due to discoloration problems are electronic devices in the retail market, e.g. smartphones, mobile phones, tablets, personal digital aids (personal digital assistants - PDAs), navigation systems, speakers, headphones, earphones, etc. Other examples are textiles for clothing, such as sports clothing and outdoor clothing, shoes and accessories, and shoes, clothing and accessories for use as personal protective equipment - in medical applications, cleanroom, and for firefighters, police, postmen, etc.
Summary of the invention
The applicant has surprisingly discovered a way to largely reduce the discoloration, and in some cases to completely avoid it. The reduction in discoloration becomes possible through the use of a so-called "plasma diffuser", wherein a "diffuser" material (or a diffusing material) is placed in the space between the products or objects and at least the electrode or electrodes, for example the or each radio frequency (RF) electrode. The diffusing material spreads the plasma, leading to a more uniform and homogeneous distribution, and surprisingly to a reduction in the discoloration.
The present invention thus describes a method to at least partially avoid discoloration of a substrate by a plasma deposition process, by dispersing the plasma before and / or during deposition of the plasma on the substrate.
In one embodiment, the substrate is pretreated during plasma pretreatment, wherein this plasma is dispersed before and / or during reaction of the plasma with the substrate, wherein the substrate is preferably cleaned, activated and / or etched.
The present invention thus further comprises a method of pre-treating a substrate during a plasma pre-treatment, preferably prior to a method of depositing a plasma coating on a substrate, wherein the pre-treatment plasma is spread before and / or during reaction of the plasma with the substrate, wherein the substrate is preferably cleaned, activated and / or etched.
The present invention also further comprises a plasma apparatus for depositing coatings, suitable for, and preferably designed to, implement a method according to the present invention. To this end, the present invention comprises a plasma device for deposition to deposit a plasma coating on a substrate, preferably at reduced pressure and preferably a plasma polymerization coating, the device comprising a plasma chamber comprising a grounded (M) electrode, a radio frequency (RF) electrode and a plasma diffuser for homogenizing a plasma distribution close to the substrate, the plasma diffuser preferably being placed between the electrodes.
The present invention further describes a plasma diffuser suitable for, and preferably designed for use in, a plasma deposition apparatus of the present invention, the use of an apparatus of the present invention to perform a method of the present invention, and a product, which preferably contains a textile material, treated according to a method and / or with an apparatus according to the present invention.
In one embodiment, the plasma contains monomers and the cover layer is preferably a polymeric cover layer.
In one embodiment, the plasma is generated at reduced pressure, preferably at a pressure lower than atmospheric pressure, more preferably lower than 1000 mTorr and / or preferably higher than 5 mTorr.
In one embodiment, the plasma is dispersed by a plasma diffusing material, preferably comprising the steps of removing, placing, replacing and / or repositioning the diffusing material.
In one embodiment, the performance of the coating is not affected in terms of oil repellency, spray test and washability.
In one embodiment, a coating is deposited on a substrate in a plasma apparatus for coatings, consisting of a plasma chamber containing a grounded (M) electrode, a radio frequency (RF) electrode, and a plasma diffuser preferably consisting of one or more plasma diffusing materials placed between the electrodes to homogenize the plasma density around a substrate to reduce discoloration after treatment, wherein the plasma diffusing materials are preferably in the form of a sheet, wherein the sheet may be flat, curved or pleated.
In one embodiment, one or a combination of the following features is present:
Plasma diffusing material is placed between the substrate or substrates on which a cover layer is to be deposited, and the radiofrequency electrode;
Plasma diffusing material is placed between the substrate or substrates on which a cover layer is to be deposited, and the grounded electrode; Plasma diffusing material is placed between the substrate or substrates on which a cover layer is to be deposited, and the grounded electrode, and between the substrate or substrates on which a cover layer is to be deposited, and the radio frequency electrode;
Plasma diffusing material is placed at the level of at least one additional side of the substrate, this side being parallel to a wall of the plasma chamber so that a beam-shaped plasma diffuser is obtained; and / or
A sheet of plasma diffusing material is wound in a cylindrical manner around the substrate or substrates on which a cover layer is to be deposited. In one embodiment, the plasma diffusion is performed in a selective manner, such as by adding or removing plasma diffusing material at certain locations to reduce or increase the plasma density there.
In one embodiment, the plasma diffuser comprises a plasma diffuser material that is placed in the plasma chamber, the plasma diffuser material preferably being in the form of a sheet.
In one embodiment, the plasma diffusing material consists of an open cell polymer structure, such as a non-woven fabric, a fabric, a knit, a membrane, a film or a film; and / or an open cell metal structure, such as a mesh or grid structure.
In one embodiment, the plasma diffuser is placed in the chamber without the use of a frame or the support of a frame.
In one embodiment, the plasma diffuser includes means for opening, such as a zipper, buttons, Velcro, or adhesive tape.
The applicant has further discovered that the use of a plasma diffuser is still limited to one plasma chamber, or to a set of plasma processes or low pressure plasma processes. The plasma diffuser can be used in smaller systems, but is particularly suitable for larger systems where the plasma distribution in the plasma chamber is less uniform.
The plasma diffuser can be used for a wide range of process parameters, making the plasma diffuser usable in a large number of processes, systems and substrates. Examples of process parameters are - without imposing restrictions:
Lower and higher monomer rates, e.g. from 1 sccm to 500 sccm, such as 5 sccm to 150 sccm;
Power applied to pulsed or continuous mode, e.g. when applied in pulsed mode, the pulsation frequency can be selected between 100 Hz and 10 kHz, with a switching duration of about 0.05 to 50%, the optimum parameters depending on the monomer used;
Lower and higher basic pressure and working pressure, e.g. a base pressure of 5 m Torr to 200 m Torr and an operating pressure of 10 m Torr to 500 m Torr;
Short and long processes, e.g. from 5 seconds to 120 minutes.
A person skilled in the art would not use the plasma diffuser to solve the problem of discoloration, as he would expect the performance of the coatings to decrease because the plasma diffuser to some extent shields exposure of the products to the plasma. If a reduction in performance - thickness of the coating, oil repellency, water contact angle, spray test, washability, etc. - is to be expected, the plasma diffuser will not be used as it is important to maintain the performance and at the same time resolve the discoloration .
The applicant has surprisingly discovered that despite the distribution of the plasma in the plasma room, the performance of the plasma treatment, such as - in the case of water and / or oil-repellent coatings - the degree of oil repellency, water contact angle and washability, is maintained at the same level . This is an unexpected advantage of the plasma diffuser, since a person skilled in the art would expect the opposite, namely a decrease in performance due to a certain degree of shielding caused by the plasma diffusing material between at least the RF electrode or electrodes and the products to be treated to place.
Brief description of the drawings
Figures 1A-1H illustrate embodiments according to the present invention wherein diffusing material is placed between a radio frequency (RF) electrode and the substrate to be treated or the substrates to be treated and / or a drawer in which the substrate or substrates can be placed.
Figures 2A - 2H illustrate embodiments according to the present invention wherein diffusing material is placed between a grounded (M) electrode and the substrate to be treated or the substrates to be treated and / or a drawer in which the substrate or substrates can be placed.
Figures 3A - 3J illustrate embodiments according to the present invention wherein diffusing material is placed between a radio frequency (RF) electrode and the substrate to be treated or the substrates to be treated and / or a drawer in which the substrate or substrates can be placed, and consequently, simultaneously or alternatively, between a grounded (M) electrode and the substrate to be treated or the substrates to be treated and / or a drawer into which the substrate or substrates can be placed.
Figures 4A - 4F illustrate embodiments according to the present invention wherein diffusing material is placed at least partially between the electrodes and the substrate to be treated or the substrates to be treated and / or a drawer into which the substrate or substrates can be placed, and wherein the electrodes are placed in a horizontal and substantially parallel set-up are placed, and wherein the diffusing material is further placed at least partially around the substrate and / or the drawer in a direction that is substantially perpendicular to the electrodes. Figures 5A - 5C illustrate embodiments according to the present invention wherein diffusing material is placed at least partially between the electrodes and the substrate to be treated or the substrates to be treated, and wherein the electrodes are placed in a vertical and substantially parallel set-up, and wherein the diffusing material furthermore is placed at least partially around the substrate in a direction that is substantially perpendicular to the electrodes. Figures 6A - 6D illustrate embodiments according to the present invention wherein diffusing material is disposed at least partially around the electrodes and the substrate to be treated or the substrates to be treated and / or a drawer into which the substrate or substrates can be placed, in a cylindrical manner. Figures 7A - 7B illustrate embodiments according to the present invention wherein diffusing material is placed in a spherical manner at least partially around the electrodes and the substrate to be treated or the substrates to be treated and / or a drawer in which the substrate or substrates can be placed. Figures 8 - 9B illustrate embodiments of 3D plasma diffusers according to the present invention with a shape other than beam or cylindrical shape, which can be used when they are considered more suitable.
Detailed description of the invention and preferred embodiments
The concept of the plasma diffuser is explained further in this description and in the claims, and the versatility, adaptability and ease of use are demonstrated with examples and figures.
As used herein, the following terms have the following meanings: "A," "an," and "an," as used herein, refer to both singular and plural unless the context clearly dictates otherwise. For example, "an electrode" refers to one or more electrodes, "a substrate" refers to one or more substrates, "a drawer" refers to one or more drawers. "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 design of the plasma diffuser can be chosen such that the plasma diffuser has a fixed position in the chamber for use with each batch, or such that the plasma diffuser is only placed in the chamber together with the products that benefit from the use of the plasma diffuser, e.g. by the use of a loading rack. This reduces the actions arising from the use of the plasma diffuser, so that in mass production the flow is guaranteed and is not limited by too many additional actions and loss of time.
Furthermore, the plasma diffuser can be used in a wide range of process conditions and plasma chambers. The plasma diffuser can be used, for example, in both pulsed and continuous processes, since both ways of applying the power tend to show discoloration on dark substrates such as black, gray, dark blue, dark green, dark purple substrates, but also on substrates with a highly reflective surface or a low surface roughness (eg soft-touch surfaces or polished surfaces).
Thanks to the concept of the plasma diffuser, which gives surprisingly good results, is easy to use and adaptable to the needs of the customer or the products that are treated with plasma, more applications and markets can benefit from plasma processes.
Dark and black substrates look dark or black to the human eye because the wavelengths of the incident light - daylight, direct sunlight, fluorescent light, etc. - are absorbed for the most part. Only a minimal fraction of the incident light is reflected from the surface. All substrates have a certain topology or flatness. The discoloration occurs on flat surfaces after deposition because small (nano) variations in the thickness of the coating are present. This leads to nano-roughness of the surface, which leads to a more diffuse reflection of the fraction of light that is reflected. Since the light is reflected in a non-regular diffuse manner, the different wavelengths that make up the light can break, leading to a rainbow-like discoloration.
The effect is more pronounced for longer process times, in which coatings are deposited that are generally thicker than with reduced plasma times. When the coating is thicker, the nano roughness can also be greater, which in turn can lead to a more pronounced discoloration. Therefore, in one embodiment, the coating deposited on the surface is thicker than 20 nm, more preferably thicker than 50 nm, even more preferably thicker than 100 nm.
The discoloration is also more pronounced for coatings that have a thickness comparable to the wavelength of visible light, e.g. thicknesses between one tenth of the lowest wavelength that is visible and 10 times higher than the highest wavelength that is visible. Therefore, in one embodiment, the coating deposited is thicker than 10 nm, more preferably thicker than 20 nm, more preferably thicker than 100 nm, and / or thinner than 5000 nm, more preferably thinner than 2500 nm, even more preferably thinner than 1000 nm.
The applicant has developed a so-called "plasma diffuser" that reduces the effects of uneven plasma distribution in the plasma chamber, leading to a more homogeneous plasma distribution and plasma density throughout the room. This reduces the nanoroughness of the cover layer on the substrate, which leads to a less diffuse reflection of the reflected fraction of the incident light. Consequently, the rainbow-like colors and / or other color changes can be reduced to 100% reduction.
The plasma diffuser and / or the method of the present invention can be used for all types of substrates and materials, in various shapes and sizes.
The effect of discoloration is more pronounced in large setups. For small setups, the effect of discoloration can be compensated to an acceptable portion by adjusting the process parameters and the design of the reaction chamber. However, this is not always possible in larger arrangements due to the large volume and the presence of various components in the chamber, such as electrodes, drawers, gas inlets, pump openings, etc. Therefore, in one embodiment, the method of the present invention is applied in a reaction chamber which has a volume of more than 0.1 l, more preferably more than 0.2 l, even more preferably more than 0.3 l, more preferably more than 0.4 l, or more than 0.5 l, or even more than 0.6 l, even more preferably more than 0.8 l, more than 1 l, even more preferably more than 2 l, even more preferably more than 51, even more preferably more than 10 l, and even more preferably more than 20 l.
The present invention makes it possible to treat large substrates, or several substrates at the same time, e.g. different items can be placed on a drawer in the room. Therefore, in a preferred embodiment, the substrate, the substrates, the drawer containing one or more substrates and / or the combined dimensions of all substrates have at least one dimension larger than 10 cm, more preferably greater than 20 cm, more preferably more than 30 cm.
Another effect that has been noted is that the discoloration becomes worse as the distance between the substrate and one or more electrodes diminishes. This can be attributed to small irregularities in the plasma density that can arise due to the geometry of the electrodes or narrow irregularities in this geometry or due to other effects. When the substrate is placed close to one or more electrodes, these irregularities will lead to irregularities in the thickness of the coating, and thus to increased discoloration. The use of a plasma diffuser and / or a method according to the present invention makes it possible to place the substrate close to one or more electrodes, at least partially avoiding the discoloration. This allows the use of a smaller reaction chamber to deposit a coating on a certain amount of substrates or to coat substrates of certain dimensions with a coating. This also allows treatment of a larger amount of substrates of certain dimensions in a room with given dimensions. Therefore, in one embodiment, the reaction chamber has a volume of less than 10 000 l, more preferably less than 5000 l, even more preferably less than 3000 l, even more preferably less than 2500 l.
Textiles in the form of rags or clothing that has parts in dark colors, such as outdoor, sports and leisure clothing, or technical clothing for protective clothing (PPE), for example, will not show any color change between the material with and without coating. Clothing is clothing items such as, but not limited to, jackets, pants, hats, gloves, and cardigans. Other textile products can be 3D pieces, such as shoes, laces, bags, backpacks, tents, scarves, etc.
The textile can be made from a natural, a man-made, a synthetic material, or a mixture of the foregoing. Examples of materials are, but are not limited to:
Synthetic: polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polystyrene (PS), polyphenylene sulfide (PPS), polyacrylonitrile (PAN), polyurethane (PUR), polyurea, polytetrafluoroethylene (PTFE) and expanded polytetrafluoroethylene (ePTFE) , polyester (PES) - such as polyethylene terephthalate (PET), recycled PET and polybutylene terephthalate (PBT), polyamide (PA) - such as PA6, PA66, and PA12, polyaramide, elastane (polyurethane-polyurea copolymer).
Natural and man-made: cotton, cellulose, cellulose acetate, silk, wool, etc. Mixtures: cotton / PES 50:50, PES / carbon 99: 1, recycled PES / elastane 92: 8, PA6 / elastane 80/20, etc.
The textile can be a non-woven fabric, a fabric, a knit, membranes (microfibre / nano-fiber), a film, a foil, or composites made from at least two layers of non-woven fabric, fabric, knit, membranes, film or foil, wherein the layers can be made of the same or a different textile structure. An example of such a composite is a laminate consisting of a sandwich structure of a fabric, a membrane and a base layer that can be a non-woven or woven structure. Another example of such a composite is a laminate consisting of a non-woven textile used as the base layer, and a membrane produced directly on this base layer.
Other substrates for which the use of the plasma diffuser has demonstrated benefits are 3D plastic parts, such as the housing for electronic devices such as telephones, smartphones, tablets, laptops, GPS systems, and so on, or the housing for glasses. All types of polymer used to make such plastic parts can be treated in the plasma diffuser of the present invention to greatly reduce the unwanted color change. Examples of polymers are - without being limiting: polyolefins such as polypropylene (PP) and polyethylene (PE), polyvinyl chloride (PVC), polyamides (PA), polyesters (PES), polystyrene (PS), polytetrafluoroethylene (PTFE), etc.
The plasma diffuser can also be used to avoid discoloration on electronics, such as a printed board (PCB), hearing aids, earphones, headphones, speakers, etc. The products often consist of a combination of materials such as plastics and conductive materials.
The plasma diffuser can also be used to prevent discolouration on optical components, such as lenses, mirrors, and on glass, for use in various applications such as cameras, electronic devices such as tablets and smartphones, but also in sports applications such as diving goggles, swimming goggles, compasses, timepieces, etc. Other applications are mirrors in the automotive sector, roadside, at home, etc. In particular, larger components, which are more susceptible to discoloration due to irregularities in the coating, and where discoloration such as a rainbow-like appearance is more easily visible , benefit from using a plasma diffuser during the plasma treatment.
The principle of the plasma diffuser is thus the spread of the plasma to obtain a more homogeneous, less odd plasma distribution, which leads to a more uniform treatment, which leads to less discoloration on the surface or surfaces of the substrates.
Preferably, the plasma diffuser contains a diffusing material and the plasma diffuser preferably consists of a diffusing material and optionally a frame to support the diffusing material.
In a first embodiment, the diffusing material comprises an open cell polymer structure, such as a textile structure, for example, a non-woven fabric, a fabric, a knit, a membrane, or a planar polymeric structure such as a film or a film. The polymer structure preferably has a certain openness and breathability that allows plasma to pass through the plasma diffuser in a controlled manner so as to reach the substrates on which a coating is to be deposited.
The textile structure can consist of one polymer or a combination of two or more polymers. The polymers that can be used are - without limitation: polyolefins such as polypropylene (PP) and polyethylene (PE),
Polyvinyl chloride (PVC), polyamides (PA), polyesters (PES), polystyrene (PS), polytetrafluoroethylene (PTFE), etc. Preferably, a low moisture content polymer is used, such as a polyester such as polyethylene terephthalate (PET).
In general, a regular textile structure can be used as a plasma diffuser by using routine techniques to determine the optimal setup, starting from the basic design of the plasma diffuser.
In another embodiment, the plasma diffusing material consists of a metal open cell structure, such as a metal mesh or grid. The mesh or grid can be open in structure, or denser. The mesh or grid can contain any metal, such as aluminum, steel, stainless steel, etc.
When the electrode arrangement in the plasma chamber is horizontal, the or each substrate to be treated becomes, e.g. must be coated, placed in a substantially horizontal position. The or each substrate can be placed in or on a drawer or perforated container located in a horizontal position between and parallel to the electrodes. Depending on the shape and dimensions of the substrates, the substrates can be placed in horizontal, vertical or intermediate position. This arrangement can for example be used to handle electronic devices, or electronic components, assemblies or subassemblies. The horizontal arrangement can also be used to treat textile products such as shoes, gloves, etc.
When the electrode arrangement in the plasma chamber is vertical, the or each substrate to be treated becomes, e.g. must be coated, placed in a substantially vertical position. The or each substrate can, for example, be suspended between the electrodes in the space provided for this purpose (a "slot"). They can be hung by means of clamps or hangers or other constructions that guarantee the best exposure of the surfaces to the plasma. Depending on the dimensions of the substrates and the slots, one or more substrates can be hung in one "slot". The vertical arrangement can be used, for example, to treat textile products such as clothing (sweater, jacket, t-shirt, shorts, pants, scarf), as well as pieces of textile and other textile products such as backpacks, cords, etc.
Whether a horizontal or vertical arrangement is used depends on the substrates to be treated.
The applicant has further discovered that the porosity or openness of the plasma diffusing material can have an influence on the degree of reduction of discoloration. The less open (the closer) the structure, the more the color change is reduced, as the examples will show. A less open diffuser can be obtained with a denser or thicker material, or by placing several layers on top of each other. By using multiple layers on top of each other, single layers can be used for the areas that are less sensitive to discolouration, while for the most sensitive places and double or even triple structure can be used. This gives the possibility to vary the arrangement of the plasma diffuser depending on the parts to be treated and their position in the plasma chamber.
In some embodiments, it is better not to shield the entire area. The plasma diffusing material can, for example, be dimensioned to shield only a portion of the exposed substrate or drawer surface. This is what the applications mean by a "selective plasma diffuser". Whether the entire surface or part of it is used for diffusion depends on the substrates to be treated, on the configuration of the plasma chamber, and on the process parameters and molecules that are used.
For example, in a horizontal arrangement to deposit coatings via plasma polymerization on electronic components, it may be appropriate to only shield the corners of the drawers or perforated containers, rather than shielding larger surfaces.
In some embodiments where there is a strong tendency to discolour, it may be considered to use a thicker diffusing material, or to use two layers of diffusing material together.
Furthermore, when "a piece" or "a side" is used in the description of the present invention, this is understood to mean plasma diffusing material, regardless of whether it is a single layer or several layers one above the other, and whether it is a piece of full dimensions or with limited dimensions (for selective diffusion). Furthermore, a selective plasma diffuser can not only be obtained by removing diffusing material at certain places, but also by adding diffusing material. For example, it may be appropriate to use a double layer of diffusing material in certain areas, e.g. at the corners, to further spread the plasma.
Preferably, the plasma diffuser consists of one or more plasma diffusing materials placed between the electrodes to make the plasma density more homogeneous close to substrates in order to reduce discoloration of the substrates after treatment. The plasma diffusing material is preferably in the form of a cloth, which can be flat, curved or pleated. The plasma diffuser can also contain several different materials, e.g. materials of different density or openness, which are placed at different heights or positions, e.g. for selective plasma diffusion.
In its simplest form, the plasma diffuser consists of a piece of diffusing material that is placed between the substrate or substrates and the or each electrode. This type of plasma diffuser can be seen as a 2D plasma diffuser.
Preferably, the dimensions of the 2D plasma diffuser are chosen so that they are equal to or larger than the entire surface of the substrate or the substrates or drawer such that the plasma is spread over the entire surface or over the entire drawer.
Preferably, in the case of a 2D plasma diffuser, the diffusing material is placed between the or each radiofrequency electrode and the or each substrate. Figure 1A shows a 2D-plasma diffuser in horizontal arrangement, showing only 1 drawer 101, a single radio frequency (RF) electrode 102 and a single grounded (M) electrode 103. The substrates to be treated are placed in drawer 101. The diffusing material 104 is placed between the drawer 101 and the RF electrode 102.
Figure 1B shows a horizontal arrangement consisting of twice the configuration of Figure 1A, for example for use in a large plasma chamber that allows to treat more substrates in a single process run. The substrates to be treated, e.g. on which a cover layer is to be deposited are placed in the drawers 101, which are placed between, for example, an RF electrode 102 and an M electrode 103. The diffusing material 104 is placed between each drawer 101 and RF electrode 102.
In certain embodiments, it is advisable not to place the diffusing material between each drawer 101 and each RF electrode 102, as shown in Figure IC.
Depending on the dimensions of the substrates to be treated, the diffusing material 104 can be placed on the top of the drawer 101 (Figure 1D) - for example, when the height of the substrates as they are placed in drawer 101 is not higher than the top of drawer 101 In another embodiment, the diffusing material 104 can be placed at a certain distance from drawer 101 (Figure IE). The distance between the substrates or the drawer and the diffusing material, and between the diffusing material and the RF electrode is variable and is determined in function of the performance of the coating after the process, and in function of the necessary decrease in the discoloration.
Figure 1F shows a vertical arrangement in which a substrate 111 to be treated is placed in a "slot", the slot being determined by the space between an RF electrode 112 and an M electrode 113. A diffusing material 114 becomes between the substrate 111 and the RF electrode 112 is placed.
Figure 1G shows a vertical arrangement in which the configuration of 1F is placed repeatedly in succession. Three substrates 111 to be treated are placed in the same slot, determined by RF electrode 112 and M electrode 113. A diffusing material 114 is placed between the substrates 111 and the RF electrodes 112.
In certain embodiments, it is advisable not to place the diffusing material in each slot, as shown in Figure 1H.
In another embodiment, the diffusing material is placed between the or each M electrode and the or each substrate.
Figure 2A shows a 2D plasma diffuser in a horizontal arrangement, showing only 1 drawer 201, a single radio frequency (RF) electrode 202 and a single grounded (M) electrode 203. The substrates to be treated are placed in drawer 201. The diffusing material 204 is placed between the drawer 201 and the M electrode 203.
Figure 2B shows a horizontal arrangement consisting of twice the configuration of Figure 2A, for example for use in a large plasma chamber that allows to treat more substrates in a single process run. The substrates to be treated, e.g. on which a cover layer is to be deposited are placed in the drawers 201, which are placed, for example, between an RF electrode 202 and an M electrode 203. The diffusing material 204 is placed between each drawer 201 and M electrode 203.
In certain embodiments, it is advisable not to place the diffusing material between each drawer 201 and each M electrode 203, as shown in Figure 2C.
Depending on the dimensions of the substrates to be treated, the diffusing material 204 can be placed at the bottom of the drawer 201 (Figure 2D). In another embodiment, the diffusing material 204 can be placed at a certain distance from drawer 201 (Figure 2E). The distance between the substrates or the drawer and the diffusing material, and between the diffusing material and the M electrode is variable and is determined in function of the performance of the coating after the process, and in function of the necessary decrease in the discoloration. Figure 2F shows a vertical arrangement in which a substrate 211 to be treated is placed in a "slot", the slot being determined by the space between an RF electrode 212 and an M electrode 213. A diffusing material 214 becomes between the substrate 211 and the M electrode 213 is placed.
Figure 2G shows a vertical arrangement in which the configuration of 2F is placed repeatedly in succession. Three substrates 211 to be treated are placed in the same slot, determined by RF electrode 212 and M electrode 213. A diffusing material 214 is placed between the substrates 211 and the M electrodes 213.
In certain embodiments, it is advisable not to place the diffusing material in each slot, as shown in Figure 2H.
In another embodiment, a diffusing material is placed between the or each RF electrode and the or each substrate, and between the or each M electrode and the or each substrate. Since both pieces of diffusing material are placed parallel to each other in the plasma chamber, this arrangement is still considered a 2D plasma diffuser.
Figure 3A shows a 2D plasma diffuser in horizontal arrangement, showing a single drawer 301, a single RF electrode 302, and a single M electrode 303. The substrates to be treated are placed in drawer 301. The diffusing material 304 is placed between tray 301 and RF electrode 302, and between tray 301 and M electrode 303.
Figure 3B shows a horizontal arrangement consisting of twice the configuration of Figure 3A, for example for use in a large plasma chamber that allows to treat more substrates in a single process run. The substrates to be treated, e.g. on which a cover layer is to be deposited are placed in the drawers 301, which are placed between, for example, an RF electrode 302 and an M electrode 303. The diffusing material 304 is placed between each drawer 301 and RF electrode 302, and between each drawer 301 and M electrode 303.
In certain embodiments, it is appropriate not to place the diffusing material between each drawer 301 and each RF electrode 302 and between each drawer 301 and each M electrode 303, as shown by way of example in Figure 2C. Depending on the dimensions of the substrates to be treated, the diffusing material 304 can be placed on the top of drawer 301 and on the bottom of drawer 301 (Figure 3D). In another embodiment, the diffusing material 304 can be placed on both sides at a certain distance from drawer 301 (Figure 3E). In yet another embodiment, the diffusing material can be placed on the top of drawer 301 and at a certain distance from drawer 301 in the direction of the M electrode 303 (Figure 3F). In yet another embodiment, the diffusing material 304 may be placed at a certain distance from tray 301 toward the RF electrode 302, and at the bottom of tray 301 (Figure 3G). The distance between the substrates or the drawer and the diffusing material, and between the diffusing material and the resp. RF electrode and M electrode are variable and are determined in function of the performance of the coating after the process, and in function of the necessary reduction of the discoloration.
Figure 3H shows a vertical arrangement in which a substrate 311 to be treated is placed in a "slot", the slot being determined by the space between an RF electrode 312 and an M electrode 313. A diffusing material 314 is placed between the substrate 311 and the RF electrode 312, and placed between the substrate 311 and the M electrode 313.
Figure 31 shows a vertical arrangement in which the configuration of 3 H is repetitively placed. Three substrates 311 to be treated are placed in the same slot, determined by RF electrode 312 and M electrode 313. A diffusing material 314 is placed between the substrates 311 and the RF electrodes 312, and between the substrates 311 and the M electrodes 313.
In certain embodiments, it is advisable not to place the diffusing material in each slot, as shown in Figure 3J.
The distance between the substrates and the 3D plasma diffuser is preferably 1 mm to 150 mm, more preferably between 2 mm and 100 mm, such as 5 mm to 75 mm, even more preferably between 10 mm and 50 mm, such as 50, 45, 40 , 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15 , 14, 13, 12, 11, or 10 mm.
The distance between the 2D plasma diffuser and the electrode or electrodes of the plasma chamber is preferably from 5 mm to 250 mm, more preferably from 10 mm to 200 mm, such as 15 mm to 150 mm, such as 150, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, or 15 mm. 2D plasma diffusers are easy to use but can only provide limited diffusion in certain cases. In cases where more diffusion is required, a 3D plasma diffuser can be used. 3D plasma diffuser may vary in size and number of sides, but in general at least one side of the plasma diffuser is not completely parallel to the plane of the electrodes. 3D plasma diffuser may be built around a frame, but in certain embodiments, no frame is used and the plasma diffuser consists of single diffusing material. Whether or not a frame is recommended depends on the shape, arrangement and dimensions of the plasma diffuser.
The frame is preferably a rigid or semi-rigid structure that is used as the body around which the diffusing material is placed. The frame may have some flexibility, but must be strong enough to support the plasma diffusing material without the risk of the diffuser collapsing and contacting the substrates to be treated.
The frame can be made of all materials that typically occur in a low-pressure plasma chamber, such as - without being limiting - aluminum, steel, such as stainless steel, polymers such as HDPE, PS, PP and PTFE (also known as Teflon), and combinations of the foregoing.
The frame can consist of a tubular structure, with tubes having a circular, rectangular or square cross-section. The cross-section preferably has an area of 1 cm 2 or less.
In certain horizontal embodiments, the drawer can itself act as a frame.
In the simplest embodiment, a 3D plasma diffuser can be seen as a 2D plasma diffuser with additional diffusing material added.
Figure 4A shows a plasma diffuser for a horizontal electrode arrangement. This plasma diffuser can be constructed starting from the diffuser shown in Figure 3A. The substrate to be treated or the substrates to be treated are placed on a drawer or perforated container 401, which is placed between the RF electrode 402 and the M electrode 403. A plasma diffuser 404 is positioned around drawer 401, and includes an upper side 405 between the drawer 401 and the RF electrode 402, a lower side 406 between the drawer 401 and the M electrode 403 (which is therefore identical to the diffuser of Figure 3A), and further comprises a rear side 407. The rear side 407 is perpendicular to the plane of the electrodes 402 and 403, and connects the top side 405 to the bottom side 406. The front side remains open, allowing easy loading and unloading of the substrates on drawer 401 . Sides 405 and 406 of the plasma diffuser 404 are placed at a certain distance from the drawer 401 (or the substrates) and the electrodes, and back 407 is placed at a certain distance between the drawer 401 and the rear wall of the plasma chamber. In this embodiment, a frame is used to hold the diffusing material in place.
In another embodiment, the plasma diffuser does not have a back side but a front side.
In yet another embodiment, represented by Figure 4B, the plasma diffuser 404 is repositioned around tray or perforated container 401, and both the plasma diffuser 404 and the tray 401 are placed between an RF electrode 402 and an M electrode 403. The plasma diffuser 404 has an upper side 405, a lower side 406, a rear side 407 and a front side 408. Only the left and right sides are not filled with diffusing material. This embodiment can be used to disperse the plasma away from the electrodes, while at the same time allowing the precursor molecules to enter the space between the plasma diffuser and the substrates (or trays). Sides 405 and 406 of the plasma diffuser 404 are placed at a certain distance between the drawer (or substrates) and the electrodes, side 407 can be placed at a certain distance between the drawer 401 and the back wall of the plasma chamber, and side 408 can be placed at a certain distance between the drawer 401 and the front wall of the plasma chamber. In this embodiment, a frame is used to hold the diffusing material in place.
Figure 4C shows the plasma diffuser of Figure 4B, with the left side 409 and the right side 410 now also being filled with diffusing material. The plasma diffuser now has the shape of a beam, with 6 sides (all sides) filled with diffusing material. Sides 405 and 406 of the plasma diffuser 404 are placed at a certain distance between the drawer (or substrates) and the electrodes, side 407 can be placed at a certain distance between the drawer 401 and the rear wall of the plasma chamber, side 408 can be placed on a certain distance between the drawer 401 and the front wall of the plasma chamber, side 409 can be placed at a certain distance between the drawer and the left wall of the plasma chamber, and side 410 can be placed at a certain distance between the drawer and the right wall of the plasma chamber. be placed in the plasma chamber. In this embodiment, a frame is used to hold the diffusing material in place.
For the embodiments shown in Figures 4A to 4C, the distance between the substrates placed in the plasma diffuser and the diffusing material is preferably 1 mm to 150 mm, more preferably 2 mm to 100 mm, such as 5 mm to 75 mm, even more preferably from 10 mm up to 50 mm, such as 50, 45, 40, 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20 , 19, 18, 17, 16, 15, 14, 13, 12, 11, or 10 mm.
The distance between the sides of the plasma diffuser parallel to the plane of the electrodes and the electrodes of the plasma chamber is preferably from 5 mm to 250 mm, more preferably from 10 mm to 200 mm, such as 15 mm to 150 mm, such as 150, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, or 15 mm.
The distance between the sides of the plasma diffuser perpendicular to the plane of the electrodes and the walls of the plasma chamber parallel to these sides of the plasma diffuser is preferably from 5 mm to 250 mm, more preferably from 10 mm to 200 mm, such as mm to 150 mm, such as 150, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, or 15 mm. Figure 4D shows the plasma diffuser of Figure 4C, the drawer 401 being used as a frame. This is possible for substrates that have dimensions that do not exceed the dimensions of the drawer 401 (in particular the height). Consequently, the distance between the substrates in the drawer and the plasma diffuser is equal to the distance between the substrates and the drawer - in other words, there is no distance between the drawer and the diffusing material.
For substrates that are higher than the height of the drawer 401, a frame can be made that provides a certain distance between the substrates and the top side 407 of the plasma diffuser 404. For the other sides 406, 407, 408, 409 and 410 of the plasma diffuser, the drawer can be used as a frame - see Figure 4E.
Other variations can also be considered, e.g. placing the sides 409 and 410 between the drawer 401 and the side walls. The choice of whether or not to use the drawer as a frame for one or more sides depends on the substrates to be treated - shape, dimensions and composition - their positioning and also on the design of the plasma chamber and drawers.
Although it is preferable to place plasma diffusing material between the substrate / substrates and the RF electrode, in some situations, e.g. if the thickness of the cover layer is important, it is decided not to place diffusing material between the RF electrode and the substrate, but elsewhere. When electronic components, subassemblies, assemblies and devices are treated plasma, e.g. provided with a coating, it is recommended to use a horizontal arrangement where the electronic components, subassemblies, assemblies and devices are placed on a drawer or perforated container. For the deposition of a coating on such substrates, it may be advantageous not to place diffusing material between the drawers and the RF electrodes in order to guarantee a certain thickness of the coating. However, a plasma diffuser is preferably used that is only placed in certain areas, which means "selective plasma diffusion".
Figure 4F shows a schematic representation of a possible selective plasma diffuser. The plasma diffusing material is mounted in the form of a beam, without top and bottom and with a reduced diffusing surface at the height of the other four sides (left, right, front and rear). The degree of selective plasma diffusion - that is, how much diffusing material is removed - depends on the substrates to be treated, their dimensions, shape, materials and composition, the process parameters, the plasma chamber arrangement, etc. Figure 4F uses a selective plasma diffuser that is only mounted in the four corners of the drawer, in order to distribute the plasma at the four corners - where typically a higher plasma density is noted - which leads to a reduction in discoloration.
A way to facilitate the opening of the plasma diffuser can be provided for the arrangements shown schematically in Figures 4B to 4E, namely a zipper, buttons, Velcro or adhesive tape.
The plasma diffuser in the embodiments shown in Figures 4A to 4C can have a fixed position in the plasma chamber thanks to a frame that has a fixed position within the plasma chamber. Between two runs or batches, the diffuser is opened (Figures 4B to 4E), and the trays 401 can be taken out of the chamber, emptied, refilled and placed again in the plasma chamber. If the drawer is used partially or completely as a frame for the plasma diffuser, typically the plasma diffuser 404 together with the drawers 401 will be taken out of the plasma chamber between two runs / batches. After this, the treated substrates are removed from the drawer via one or more sides without diffusing material (e.g. the front of Figure 4A), or by opening the diffuser via a zipper, buttons, Velcro or adhesive tape.
Figure 5A shows a plasma diffuser for a vertical electrode arrangement. This plasma diffuser can be obtained starting from the plasma diffuser shown in Figure 3H. The substrate to be treated or the substrates 501 to be treated are placed in a slot delimited by RF electrode 502 and M electrode 503. A plasma diffuser 504 is placed around the substrate / substrates 501 and consists of a left side 505 between the substrate 501 and the RF electrode 502, a right side 506 between the substrate 501 and the M electrode 503 (which is therefore identical to the diffuser 3H), and further comprises a back side 507. The back side 507 is perpendicular to the plane of the electrodes 503 and 503 and connects the left side 405 with the right side 406. The front side remains open, allowing substrates to easily get in and out can be achieved.
Sides 505 and 506 of the plasma diffuser 504 are placed at a certain distance between the substrates and the electrodes, and side 507 is placed at a certain distance from the substrates and the back wall of the plasma chamber. In this embodiment, a frame can be used to hold the diffusing material in place, but the plasma diffuser 504 can also be attached to the top of the plasma chamber without the use of a frame being required to hold the plasma diffuser 504 in place since the diffusing material has a hanging position.
In another embodiment, the plasma diffuser does not have a back side but a front side.
In yet another embodiment, represented by Figure 5B, the plasma diffuser 504 is repositioned around the substrates 501, and both the plasma diffuser 504 and the substrates 501 are suspended between an RF electrode 502 and an M electrode 503. The plasma diffuser 504 has a left side 505, a right side 506, a rear side 507 and a front side 508. Only the top surface and the bottom surface are not filled with diffusing material. This embodiment can be used to disperse the plasma away from the electrodes, while at the same time allowing the precursor molecules to enter the space between the plasma diffuser and the substrates. Sides 505 and 506 of the plasma diffuser 504 are placed at a certain distance between the substrates 501 and the electrodes, side 507 can be placed at a certain distance between the substrates 501 and the rear wall of the plasma chamber, and side 508 can be placed at a certain distance between the substrates 501 and the front wall of the plasma chamber. In this embodiment, a frame is used to hold the diffusing material in place, but this is not necessary since the diffuser has a hanging position and thus can in itself retain its shape and position.
Figure 5C shows the plasma diffuser of Figure 5B, where now also the top 509 and the bottom 510 are filled with diffusing material. The plasma diffuser is now beam-shaped with 6 sides (all sides) filled with diffusing material. Sides 505 and 506 of the plasma diffuser 504 are placed at a certain distance between the substrates and the electrodes, side 507 is placed at a certain distance between the substrates and the back wall of the plasma chamber, side 508 is placed at a certain distance between the substrates and the front wall of the plasma chamber, side 509 is placed at a certain distance between the substrates and the top wall of the plasma chamber, and side 510 is placed at a certain distance between the substrates and the bottom wall of the plasma chamber. In this embodiment, a frame is used to hold the diffusing material in place, but this is not necessary since the diffuser has a hanging position and thus can in itself retain its shape and position.
A way to facilitate opening of the plasma diffuser can be provided for the arrangements shown schematically in Figures 5B and 5C, namely a zipper, buttons, Velcro or adhesive tape.
The plasma diffuser in the embodiments shown in Figures 5A to 5C can have a fixed position in the plasma chamber thanks to a frame that has a fixed position within the plasma chamber. Between two runs or batches, the diffuser is opened (Figures 5B and 5C), and the substrates 501 are taken out of the chamber and new substrates are hung in the plasma chamber.
In another embodiment, the plasma diffuser 504 can be positioned such that it can be removed from the plasma chamber if necessary.
For the embodiments shown in Figures 5A to 5C, the distance between the substrates placed in the plasma diffuser and the diffusing material is preferably 1 mm to 150 mm, more preferably 2 mm to 100 mm, such as 5 mm to 75 mm, even more preferably from 10 mm up to 50 mm, such as 50, 45, 40, 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20 , 19, 18, 17, 16, 15, 14, 13, 12, 11, or 10 mm.
The distance between the sides of the plasma diffuser parallel to the plane of the electrodes and the electrodes of the plasma chamber is preferably from 5 mm to 250 mm, more preferably from 10 mm to 200 mm, such as 15 mm to 150 mm, such as 150, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, or 15 mm.
The distance between the sides of the plasma diffuser perpendicular to the plane of the electrodes and the walls of the plasma chamber parallel to these sides of the plasma diffuser is preferably from 5 mm to 250 mm, more preferably from 10 mm to 200 mm, such as mm to 150 mm, such as 150, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, or 15 mm. Another form of 3D plasma diffuser is a cylindrical arrangement. A piece of diffusing material is pleated such that a tubular arrangement is obtained, for example by connecting the left side and the right side of the diffusing material together.
Figure 6A shows a cylindrical plasma diffuser 604 that can be used in horizontal arrangement around a drawer 601. A certain distance between the diffusing material 604 and the drawer 601 is maintained. The plasma diffuser 604 fits into the space between the horizontally positioned RF electrode 602 and M electrode 603. The left and right sides of the plasma diffuser are open so that precursor molecules can enter the space between the diffuser and the substrates 601 in a controlled manner. A zipper, buttons, Velcro strips or adhesive tape can be provided to easily open the plasma diffuser. The plasma diffuser is preferably mounted on a frame and can have a fixed position in the plasma chamber, or can be taken out of the plasma chamber together with the drawer after each process.
Figure 6B shows the plasma diffuser of Figure 6A, where now also the left-hand side 605 and the right-hand side 606 are filled with diffusing material. Substrate drawer 601 is placed in the internal volume of the plasma diffuser 604. The plasma diffuser 604 is positioned between the RF electrode 602 and the M electrode 603. A zipper, buttons, Velcro strips or adhesive tape can be provided to easily open the plasma diffuser. The plasma diffuser is preferably mounted on a frame and can have a fixed position in the plasma chamber, or can be taken out of the plasma chamber together with the drawer after each process.
Although the cylindrical plasma diffuser can be used for a horizontal arrangement of the plasma chamber (horizontally positioned electrodes), a beam-shaped plasma diffuser is preferably used for the horizontal arrangement. The cylindrical plasma diffuser is well suited for use in vertical electrode arrangement since a piece of diffusing material can easily be wrapped around the hanging substrates.
Figure 6C shows a schematic representation of a cylindrical plasma diffuser 614 that is wrapped around one or more substrates 611, and placed within the slot defined by the vertically positioned RF electrode 612 and M electrode 613. The top and bottom of the plasma diffuser 614 are open so that precursor molecules can enter the space between the diffuser and the substrates 601 in a controlled manner. A zipper, buttons, Velcro strips or adhesive tape can be provided to easily open the plasma diffuser. The plasma diffuser can be mounted on a frame, but can also be used without a frame by attaching the diffuser to the top wall of the plasma room. The plasma diffuser 614 can have a fixed position in the plasma chamber, or can be removed from the plasma chamber together with the substrates after each process.
Figure 6D shows a schematic representation of a cylindrical plasma diffuser 614 that is wrapped around one or more substrates 611, and placed within the slot defined by the vertically positioned RF electrode 612 and M electrode 613. The top 615 and the bottom 616 of the plasma diffuser 614 are filled with diffusing material. A zipper, buttons, Velcro strips or adhesive tape can be provided to easily open the plasma diffuser. The plasma diffuser can be mounted on a frame, but can also be used without a frame by attaching the diffuser to the top wall of the plasma room. The plasma diffuser 614 can have a fixed position in the plasma chamber, or can be removed from the plasma chamber together with the substrates after each process.
For the embodiments shown schematically in Figures 6A to 6C, the distance between the substrates placed in the plasma diffuser and the diffusing material is not the same everywhere due to the curved surface of the plasma diffusing material, and is preferably 1 mm to 150 mm, more preferably 2 mm to 100 mm, such as 5 mm to 75 mm, more preferably from 10 mm to 50 mm, such as 50, 45, 40, 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, or 10 mm.
The distance between the sides of the plasma diffuser and the electrodes and / or walls of the plasma chamber is preferably from 5 mm to 250 mm, more preferably from 10 mm to 200 mm, such as 15 mm to 150 mm, such as 150, 145, 140 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, or 15 mm. Since the diffusing material has a curved shape, the distance may vary from point to point. 3D plasma diffusers with a shape other than a beam or a cylinder can also be used if they are considered more suitable. Figures 7A, 7B, 8, 9A and 9B give some schematic representations, but it is clear that variations on these forms are also considered.
Figure 7A shows a plasma diffuser 704 that is in the shape of a hemisphere. This plasma diffuser is preferably used for the horizontal arrangement, as shown in Figure 7A. The plasma diffuser 704 is placed on top of drawer 701, which is placed between RF electrode 702 and M electrode 703. Preferably a frame is used to hold the plasma diffuser in place. The underside of the drawer 701 can also be covered with diffusing material, but in some cases this is not recommended. Whether or not the underside of drawer 701 is covered depends on the arrangement, the substrates to be treated, etc.
Figure 7B shows a plasma diffuser 704 that is in the shape of a sphere around tray 701. This plasma diffuser is preferably used for the horizontal arrangement, as shown in Figure 7B. Tray 701 is placed inside the plasma diffuser 704, which in turn is placed between RF electrode 702 and M electrode 703. Preferably a frame is used to hold the plasma diffuser in place.
Referring to Figures 7A and 7B, a zipper, buttons, Velcro strips, or adhesive tape is provided to easily open the plasma diffuser. The plasma diffuser 704 is preferably withdrawn from the plasma chamber after each process, together with the drawer 701, and is then opened to remove treated substrates from the drawer 701. Tray 701 is then refilled with substrates to be treated, the plasma diffuser 704 is closed and is returned to the plasma chamber together with tray 701.
The distance between the substrates placed in the plasma diffuser and the diffusing material is not the same everywhere due to the curved surface of the plasma diffusing material, and is preferably 1 mm to 150 mm, more preferably 2 mm to 100 mm, such as 5 mm to 75 mm, more preferably from 10 mm to 50 mm, such as 50, 45, 40, 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, or 10 mm.
The distance between the plasma diffusing material and the electrodes and / or walls of the plasma chamber is not the same everywhere due to the curved surface of the plasma diffusing material, and is preferably 5 mm to 250 mm, more preferably 10 mm to 200 mm, such as mm to 150 mm, such as 150, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, or 15 mm.
Figure 8 shows a plasma diffuser 804 that has a dome shape. This plasma diffuser is preferably used for the horizontal arrangement, as shown in Figure 8. The plasma diffuser 804 is placed on top of drawer 801, which is placed between RF electrode 802 and M electrode 803. Preferably, a frame 805 is used to hold the plasma diffuser in place. The underside of the drawer 801 can also be covered with diffusing material, but in some cases this is not recommended. Whether or not the underside of drawer 801 is covered depends on the arrangement, the substrates to be treated, etc.
The distance between the substrates placed in the plasma diffuser and the diffusing material is not the same everywhere due to the curved surface of the plasma diffusing material, and is preferably 1 mm to 150 mm, more preferably 2 mm to 100 mm, such as 5 mm to 75 mm, more preferably from 10 mm to 50 mm, such as 50, 45, 40, 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, or 10 mm.
The distance between the plasma diffusing material and the electrodes and / or walls of the plasma chamber is not the same everywhere due to the curved surface of the plasma diffusing material, and is preferably 5 mm to 250 mm, more preferably 10 mm to 200 mm, such as mm to 150 mm, such as 150, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, or 15 mm.
Figures 9A and 9B show a schematic representation of a tunnel-shaped plasma diffuser 904. The radius of curvature can vary depending on the dimensions of the substrates to be treated. This plasma diffuser is preferably used for the horizontal arrangement, as shown in Figures 9A and 9B. The plasma diffuser 904 is placed on top of tray 901, which is placed between RF electrode 902 and M electrode 903. Preferably, a frame 905 is used to hold the plasma diffuser in place. The underside of the drawer 901 can also be covered with diffusing material, but in some cases this is not recommended. Whether or not the underside of drawer 901 is covered depends on the arrangement, the substrates to be treated, etc.
The distance between the substrates placed in the plasma diffuser and the diffusing material is not the same everywhere due to the curved surface of the plasma diffusing material, and is preferably 1 mm to 150 mm, more preferably 2 mm to 100 mm, such as 5 mm to 75 mm, more preferably from 10 mm to 50 mm, such as 50, 45, 40, 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, or 10 mm.
The distance between the plasma diffusing material and the electrodes and / or walls of the plasma chamber is not the same everywhere due to the curved surface of the plasma diffusing material, and is preferably 5 mm to 250 mm, more preferably 10 mm to 200 mm, such as mm to 150 mm, such as 150, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, or 15 mm.
Advantages of the present invention are: reduction, or even elimination, of undesired discoloration typically seen on dark surfaces - such as dark green, dark blue, dark gray, and black objects - or on substrates that have a high glossy surface or a low surface roughness (e.g. soft, smooth surfaces or polished surfaces); versatile arrangement of the plasma diffuser depending on the dimensions of the objects to be treated or on the required reduction of discoloration, by varying the plasma diffuser material, or the shape of the plasma diffuser, the number of sides filled with diffuser material, or the degree of diffusion (selective plasma diffusion) by using multiple layers of diffusing material or by removing diffusing material on certain pieces; no impact on the water contact angle, spray test, oil level; no impact or washability; no obligation to adjust the machine design; simple implementation in existing plasma chambers; easily manipulated by using a fixed or removable positioning in the plasma chamber, and by using fixation means that allow easy opening of the plasma diffuser.
The present invention will now be illustrated and further described with reference to the following examples. These examples are provided for reference and do not imply any limitation on the aforementioned aspects of the present invention. EXAMPLES Example 1
Example 1 demonstrates the impact of the openness of the plasma diffusing material. Three different diffusing materials were used: a non-woven fabric, a woven textile and a foil. All three of these materials were used in the same horizontal arrangement as shown in Figure 4E but with an open left and right side, which are parallel to the chamber walls where the monomer inlets are mounted. The non-woven fabric was used with a single layer and with a double layer (selective plasma diffusion). With each plasma diffuser set-up, the same plasma polymerization process was conducted in a 490 I large plasma chamber, according to Table 1:
Table 1: Process parameters according to Example 1 The data and results are shown in Table 2:
Table 2: Overview of tests performed with four different plasma I diffusing materials
It is clear from Table 2 that the decrease in discoloration is best for the denser materials (single layer non-woven -> double layer non-woven -> woven fabric -> foil), while at the same time the thickness of the deposited cover layer does not differ substantially from one plasma diffuser to the other. However, the thickness of the cover layer is lower for all four of the plasma diffusers than if no plasma diffuser was used.
The test with the single and the double layer of non-woven fabric shows that the discoloration is less if two layers are used on top of each other.
Example 2
Example 2 shows the impact of the openness of the two sides parallel to the chamber walls in which the monomer inlets are mounted. The single layer of non-woven fabric of Example 1 was used with 100% open sides, and with sides that were only open for 25%. The processes were performed according to the parameters of Table 1. The results are shown in Table 3:
Table 3: Overview of tests done with varying degrees of openness It is clear from Table 3 that fewer open sides have a positive impact on the reduction of discoloration, and that the oil level is not affected. However, the deposited coatings with the more closed plasma diffuser are less thick, which could explain the absence of discoloration. In situations where a certain oil level must be achieved, it may be considered to use this more closed plasma diffuser. However, if a combination of a minimum thickness of the cover layer and a certain reduction of the discoloration is required, it is better to use a less open diffuser where two sides are 100% open - see Example 1.
Example 3
Example 3 demonstrates the fact that the washability of the swatches is not affected by the use of the plasma diffuser. Textile samples made from 100% recycled PES, woven, were hung vertically within the plasma diffuser.
The top and bottom, which are parallel to the sides where the monomer inlets are positioned, are 100% open. A process of 5 minutes pre-treatment and 10 minutes deposition was performed on these samples, with and without the plasma diffuser. The process parameters are shown in Table 4.
Table 4: Process parameters according to Example 3
The treated textile samples were subsequently washed in accordance with ISO 15797 (2002). One complete wash cycle consists of the following steps: 1. Washing at 75 ° C with 20 g IPSO HF 234 per kilogram dry weight, without optical brightener; 2. Dry in a drying cabinet.
After one wash cycle, a spray test was performed according to ISO 9073 - section 17 and ISO 4920. After this, 4 additional wash cycles were performed and the oil level and the spray test were re-measured (values after 5 wash cycles).
It is clear from Table 5 that no difference was noticeable in the spray test results of the samples treated with and without a plasma diffuser.
Table 5: Washing results Example 4
A selective plasma diffuser according to Figure 4F was used in a 490 I plasma chamber with 5 drawers. The diffusing material, in this example Teflon, was placed in all four corners of all five drawers, over lengths of 20 cm. A second diffuser was made by placing diffusing material, again Teflon, in all four corners of all five drawers over 10 cm lengths. The process parameters are shown in Table 6. The same process was also performed without a plasma diffuser.
The purpose of this test was to see if the discoloration on PCBs (PCBs) could be reduced, and to see if the uniformity of the coating could be improved in terms of thickness. The results are in Table 7.
Table 6: Process parameters according to Example 4
It is clear from Table 7 that for all drawers, except for the fifth (lower), the StDev (%) is greatly reduced when using the plasma diffuser, indicating a better uniformity of the thickness of the coating. It should be noted that for all drawers, the thickness of the cover layer is lower if a plasma diffuser is used, as already shown in Examples 1 and 2.
Table 7: Thickness and standard deviation (%) for different arrangements

权利要求:
Claims (15)
[1]
Conclusions
A method to at least partially discolour a substrate through a plasma deposition process, by dispersing a plasma before and / or during deposition of the plasma on the substrate where a coating is deposited.
[2]
A method according to claim 1, wherein the substrate is pretreated for a pretreatment plasma, wherein the pretreatment plasma is dispersed before and / or during reaction of the pretreatment plasma with the substrate, wherein preferably the substrate is cleaned, activated and / or etched.
[3]
Method according to claim 1 or 2, wherein the plasma contains monomers and wherein the cover layer is preferably a polymeric cover layer.
[4]
A method according to any one of claims 1 to 3, wherein the plasma is supplied at low pressure, preferably at a pressure lower than atmospheric pressure, even more preferably less than 1000 mTorr and / or preferably higher than 5 mTorr.
[5]
The method according to any of claims 1 to 4, wherein the performance of the coating is not adversely affected in terms of oil repellency, spray test and washability.
[6]
The method of any one of claims 1 to 5, wherein a coating is deposited on the substrate in a plasma deposition apparatus that includes a plasma chamber containing a grounded (M) electrode, a radio frequency (RF) electrode, and a plasma diffuser, the plasma diffuser preferably consists of one or more plasma diffusing materials placed between the electrodes, to improve the homogeneity of a plasma density around the substrate, in order to reduce the discoloration of the substrate after treatment, and the plasma diffusing materials preferably lapping fabric that is flat, curved or pleated.
[7]
A method according to claim 6 wherein one or a combination of the following features is present: Plasma diffusing material is placed between the substrate or substrates, on which a coating is to be deposited, and the radio frequency electrode; Plasma diffusing material is placed between the substrate or substrates on which a cover layer is to be deposited and the grounded electrode; Plasma diffusing material is placed between the substrate or substrates on which a cover layer is to be deposited and the radio frequency electrode and between the substrate or substrates on which a cover layer is to be deposited and the grounded electrode; Plasma diffusing material is placed along at least one additional side of the substrate, parallel to a wall of the plasma chamber, to obtain a beam-shaped plasma diffuser; A piece of plasma diffusing material is wrapped around the substrate or substrates, on which a coating is to be deposited, in a cylindrical shape.
[8]
A method of pre-treating a substrate with a pretreatment prior to performing a method according to any of claims 1 to 7, wherein the pretreatment plasma is dispersed before and / or during reaction of the pretreatment plasma with the substrate, the substrate preferably being cleaned , is activated and / or etched.
[9]
A plasma deposition device suitable for, preferably constructed for, performing a method according to any one of claims 1 to 8.
[10]
A plasma deposition device for depositing a plasma coating on a substrate, preferably at low pressure and preferably a plasma polymerization coating, the device comprising a plasma chamber comprising a grounded (M) electrode, a radio frequency (RF) electrode and contains a plasma diffuser to improve the homogeneity of a plasma density around the substrate, and wherein the plasma diffuser is preferably placed between these electrodes.
[11]
The plasma deposition apparatus of claim 10, wherein the plasma diffuser consists of a plasma diffusing material that is placed in the plasma chamber, and wherein the plasma diffusing material is preferably in the form of a lap.
[12]
The plasma deposition apparatus of claim 11, wherein the plasma diffusing material is an open cell polymer structure, such as a non-woven fabric, a fabric, a knit, a membrane, a film or a film; and / or an open cell metal structure, such as a mesh or grid structure.
[13]
The plasma deposition apparatus according to any of claims 10 to 12, wherein the plasma diffuser is placed in the plasma chamber without the use of or support for a frame.
[14]
The plasma deposition device according to any of claims 10 to 13, wherein the plasma diffuser comprises means for opening, such as a zipper, buttons, Velcro strips or adhesive tape.
[15]
A plasma diffuser, suitable for and preferably constructed for use in a plasma deposition apparatus according to any one of claims 10 to 14.

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JP2017524069A|2017-08-24|

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EP2937890B1|2020-06-03|

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US20170047201A1|2017-02-16|

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WO2015162183A1|2015-10-29|

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AU2015250823A1|2016-11-10|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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EP14165491.3A|EP2937890B1|2014-04-22|2014-04-22|Plasma coating apparatus with a plasma diffuser and method preventing discolouration of a substrate|

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EP141654913|2014-04-22|

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