EP2875874A1 - Low and medium pressure plasma method for surface coating by supplying precursor without carrier gas - Google Patents

Abstract

The present invention relates to a method for coating at least one surface of a two- or three-dimensional body, a device for coating at least one surface of a two- or three-dimensional body, the coated surface per se and the use of a carrier gas-free introduction of a liquid, at least one precursor compound containing Medium in a coating chamber.

Description

The present invention relates to a method for coating at least one surface of a two- or three-dimensional body, a device for coating at least one surface of a two- or three-dimensional body, the coated surface per se and the use of a carrier gas-free introduction of a liquid, at least one precursor compound containing Medium in a coating chamber.

In the prior art precursor compounds in low and / or medium pressure plasmas, optionally after a vaporization step, the plasma discharge gaseous, partially using a carrier gas supplied. The optionally required evaporation of the precursor compound is usually carried out outside the reactor by heating.

In plasma coating processes conducted at a pressure greater than 600 mmHg (about 800 mbar), the precursor compounds are usually supplied as a spray to a (sheet) discharge. These are often suspensions, the precursor compounds being introduced into the reaction chamber in powder form by means of a carrier gas, water and / or a plasma stream ( Zotov et al., Journal of Membrane Science, 2013, 442, 119-123 ). In this way, for example, fluoropolymers, such as polyvinylidene fluoride, ethylene chlorotrifluoroethylene, perfluoroalkoxyalkane and perfluoroethylene propylene coatings are applied ( Leivo et al., Progress in Organic Coatings, 2004, 49, 69-73 ).

In the prior art, low and / or medium pressure plasma processes, which are used for coating surfaces, rely on gas and / or vapor precursor compound addition. Since the precursor compounds must be introduced in large quantities in some coating processes, but have a very low vapor pressure, this represents a significant technical disadvantage in terms of process technology. There is as yet no method and / or apparatus in the prior art which are suitable for this, liquid media in a coating chamber, preferably in large quantities, to bring, wherein the coating chamber has a pressure of less than 1 bar, without causing an evaporation of the liquid medium must be carried out.

It is therefore an object of the present invention, in particular to overcome the disadvantages mentioned above, in particular to provide a method and / or apparatus, wherein high Separation rates of a precursor compound, in particular a monomer or an organometallic compound, can be achieved without the precursor compound has to be brought into the gaseous state. In particular, it should be ensured that homogeneous coatings of temperature-stable substances, in particular polymers, in particular together with noble metal ions, can be produced in a deposition process.

The technical problem underlying the invention is solved by the technical teaching of the independent claims.

1. a) Bereitstellen eines flüssigen, mindestens eine Vorläuferverbindung enthaltenden Mediums,
2. b) Bereitstellen einer Beschichtungskammer, die einen zu beschichtenden zwei- oder dreidimensionalen Körper und eine Plasmaerzeugungsvorrichtung aufweist, wobei in der Beschichtungskammer ein Druck von weniger als 1 bar vorliegt,
3. c) Einbringen des flüssigen, mindestens eine Vorläuferverbindung enthaltenden Mediums ohne Trägergas mittels einer Düse in die Beschichtungskammer,
4. d) Aktivieren der mindestens einen Vorläuferverbindung und/oder von mindestens einer Oberfläche des zwei- oder dreidimensionalen Körpers mittels eines durch die Plasmaerzeugungsvorrichtung erzeugten Niedertemperaturplasmas,
5. e) Abscheiden der mindestens einen, bevorzugt aktivierten, Vorläuferverbindung auf mindestens einer, bevorzugt aktivierten, Oberfläche des zwei- oder dreidimensionalen Körpers, und
6. f) Erhalten einer Beschichtung auf der mindestens einen Oberfläche eines zwei- oder dreidimensionalen Körpers.

In particular, the present invention relates to a method for coating at least one surface of a two- or three-dimensional body, the method comprising the following steps:

1. a) providing a liquid medium containing at least one precursor compound,
2. b) providing a coating chamber having a two- or three-dimensional body to be coated and a plasma generating device, wherein a pressure of less than 1 bar is present in the coating chamber,
3. c) introduction of the liquid medium containing at least one precursor compound without carrier gas by means of a nozzle into the coating chamber,
4. d) activating the at least one precursor compound and / or at least one surface of the two- or three-dimensional body by means of a low-temperature plasma generated by the plasma-generating device,
5. e) depositing the at least one, preferably activated, precursor compound on at least one, preferably activated, surface of the two- or three-dimensional body, and
6. f) obtaining a coating on the at least one surface of a two- or three-dimensional body.

Surprisingly, the process according to the invention enables very high deposition rates and also a high material throughput of the at least one, preferably activated, precursor compound. The coating is also carried out at a pressure of less than 1 bar, preferably less than 600 mbar, preferably less than 1 mbar, whereby preferably unwanted side reactions, preferably the agglomeration of the at least one precursor compound, reduced, preferably excluded. Due to the method according to the invention, it is possible in particular to produce coatings having glassy, ceramic-like, ceramic or metal-oxide layers with a high deposition rate. Likewise, monomers, oligomers or polymers can be used in process engineering easily apply to the at least one surface of the two- or three-dimensional body.

It is likewise possible with the process according to the invention to provide polymers with additional functional groups which otherwise have to be incorporated into the coating in a complicated manner in further, preferably subsequent, process steps. For example, it is possible with the method according to the invention to apply monomers, in particular acrylic acid monomers, together with noble metal ions, preferably silver ions. In the prior art co-application of monomers with silver ions has not been possible. The silver ions would have had to be added to the polymeric coating either by co-sputtering or by wet-chemical process steps.

In addition, it is surprisingly possible with the method according to the invention to produce homogeneous, defect-free and very smooth coatings on the surface of the two- or three-dimensional body.

In particular, by eliminating the carrier gas, the at least one precursor compound can be introduced into the coating chamber without unnecessary additional loading of the vacuum pumps, which are used to generate the pressure of less than 1 bar.

Preferably, step d) is performed before step e). Alternatively, step d) is preferably carried out after step e). Preferably, step d) is carried out both before and after step e).

Preferably, in step d), the at least one precursor compound is first activated by means of the low-temperature plasma generated by the plasma generation device, and then the at least one activated precursor compound is deposited in step e) on at least one non-activated surface of the two- or three-dimensional body.

Alternatively, preferably in step d), the at least one precursor compound and the at least one surface of the two- or three-dimensional body are activated by means of the low-temperature plasma generated by the plasma generating device and then the at least one activated precursor compound in step e) on the at least one activated surface of the two- or three-dimensional body deposited.

Alternatively, preferably in step d), the at least one surface of the two- or three-dimensional body is activated by means of the low-temperature plasma generated by the plasma generating device, and then the at least one non-activated Precursor compound in step e) deposited on the at least one activated surface of the two- or three-dimensional body. Preferably, the at least one non-activated precursor compound deposited on the at least one activated surface of the two- or three-dimensional body is subsequently activated according to step d) by means of a low-temperature plasma generated by the plasma generation device.

Alternatively, preferably in step e), the at least one non-activated precursor compound is deposited on the at least one non-activated surface of the two- or three-dimensional body and then in step d) the at least one non-activated precursor compound and / or the at least one non activated surface of the two- or three-dimensional body according to step d) is activated by means of a low-temperature plasma generated by the plasma generating device.

1. a) Bereitstellen eines flüssigen, mindestens eine Vorläuferverbindung enthaltenden Mediums,
2. b) Bereitstellen einer Beschichtungskammer, die einen zu beschichtenden zwei- oder dreidimensionalen Körper und eine Plasmaerzeugungsvorrichtung aufweist, wobei der zu beschichtende zwei- oder dreidimensionale Körper mindestens eine Oberfläche aufweist, die beschichtet werden soll, wobei in der Beschichtungskammer ein Druck von weniger als 1 bar, bevorzugt von weniger als 600 mbar, bevorzugt von weniger als 1 mbar, vorliegt,
3. c) Einbringen, bevorzugt Einleiten, des flüssigen, mindestens eine Vorläuferverbindung enthaltenden Mediums ohne Trägergas mittels einer Düse in die Beschichtungskammer, sodass sich das flüssige, mindestens eine Vorläuferverbindung enthaltende Medium in der Beschichtungskammer fein verteilt, bevorzugt in Form von Tröpfchen, wobei mindestens 90% aller Tröpfchen einen Durchmesser von 100 µm oder weniger aufweisen,
4. d) Aktivieren der mindestens einen Vorläuferverbindung und/oder der mindestens einer Oberfläche des zwei- oder dreidimensionalen Körpers mittels eines durch die Plasmaerzeugungsvorrichtung erzeugte Niedertemperaturplasmas, sodass zumindest ein Teil der in die Beschichtungskammer eingebrachten Vorläuferverbindung und/oder der mindestens einer Oberfläche des zwei- oder dreidimensionalen Körpers aktiviert wird,
5. e) Abscheiden der mindestens einen, bevorzugten aktivierten, Vorläuferverbindung auf mindestens einer, bevorzugt aktivierten, Oberfläche des zwei- oder dreidimensionalen Körpers, sodass sich eine polymere, polymerartige, glasartige, keramikartige, keramische oder metalloxidische Beschichtung daraus ausbildet, und
6. f) Erhalten einer polymeren, polymerartigen, glasartigen, keramikartigen, keramischen oder metalloxidischen Beschichtung auf der mindestens einen Oberfläche eines zwei- oder dreidimensionalen Körpers.

According to the invention, therefore, a method is preferably provided for coating at least one surface of a two- or three-dimensional body, the method comprising the following steps:

1. a) providing a liquid medium containing at least one precursor compound,
2. b) providing a coating chamber having a two- or three-dimensional body to be coated and a plasma generating device, wherein the two- or three-dimensional body to be coated has at least one surface to be coated, wherein in the coating chamber, a pressure of less than 1 bar , preferably of less than 600 mbar, preferably less than 1 mbar, is present,
3. c) introduction, preferably introduction, of the liquid medium containing at least one precursor compound without carrier gas into the coating chamber by means of a nozzle so that the liquid medium containing at least one precursor compound is finely distributed in the coating chamber, preferably in the form of droplets, whereby at least 90% all droplets have a diameter of 100 μm or less,
4. d) activating the at least one precursor compound and / or the at least one surface of the two- or three-dimensional body by means of a low-temperature plasma generated by the plasma generating device, so that at least a portion of the introduced into the coating chamber precursor compound and / or the at least one surface of the two- or three-dimensional Body is activated,
5. e) depositing the at least one, preferably activated, precursor compound on at least one, preferably activated, surface of the two- or three-dimensional body to form a polymeric, polymer, glassy, ceramic, ceramic or metal oxide coating therefrom, and
6. f) obtaining a polymeric, polymer, glassy, ceramic, ceramic or metal oxide coating on the at least one surface of a two- or three-dimensional body.

The term "two-dimensional body" is understood in a three-dimensional space with the spatial axes x, y and z a body with the spatial dimensions x ', y' and z 'along the spatial axes, the spatial dimensions of x' and y 'clearly greater than the spatial extent z 'are, preferably by a factor of 5, preferably by a factor of 10, preferably by a factor of 50, preferably by a factor of 100, preferably by a factor of 1000. The term "two-dimensional body" accordingly means that a certain spatial extension takes place in each of the three spatial axes.

The term "liquid medium" is understood to mean a medium which can be introduced into the coating chamber via a nozzle. The liquid medium therefore has a certain viscosity at 25 ° C, preferably a viscosity of 100 mPa · s (millipascal second) or less, preferably 10 mPa · s or less, preferably 5 mPa · s or less, preferably 1 mPa · s or less at 25 ° C. In addition to the at least one precursor compound, the liquid medium preferably contains a solvent, preferably an organic solvent and / or water. The solvent preferably serves to reduce the viscosity of the at least one precursor compound to such an extent that it can be introduced into the coating chamber via the inserted nozzle. Preferably, the solvent has a lower viscosity than the at least one precursor compound. Preferably, the solvent used is also a precursor compound in the context of the present invention. The liquid medium preferably comprises a mixture of at least two precursor compounds, preferably consisting thereof, wherein the mixture has at least one precursor compound and at least one solvent which can be used as precursor compound, preferably consisting thereof. The liquid medium preferably comprises a mixture of two precursor compounds, preferably consisting thereof, wherein the mixture has, preferably consists of, a precursor compound and a solvent which can be used as precursor compound. The liquid medium preferably consists of the at least one precursor compound.

Preferably, the solvent is an organic solvent which is preferably a protic or aprotic solvent. The organic solvent is preferably selected from the group consisting of hydrocarbons, acetone, acetonitrile, alcohols, tert-butyl methyl ether, Benzyl alcohol, chloroform, dibutyl ether, diethylene glycol, diethyl ether, diiodomethane, dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, ethyl acetate, ethanol, ethylene glycol, ethylene glycol dimethyl ester and formamide. The hydrocarbons are preferably selected from halogenated, preferably perhalogenated, hydrocarbons and unsubstituted hydrocarbons, preferably from toluene, pentane, cyclohexane, n-hexane and heptane, which are optionally halogenated or perhalogenated, wherein the halogen is preferably selected from fluorine, chlorine and Mixtures thereof. The alcohols are preferably methanol, ethanol, propanol, butanol and pentanol. Preferably, the solvents do not separate on the surface to be coated. Preferably, these solvents evaporate due to their vapor pressure and are therefore not precipitated.

Preferably, at least 90% by weight, preferably at least 95% by weight, of the at least one precursor compound does not enter the gas phase under the conditions prevailing during the process for coating at least one surface of a two- or three-dimensional body in the coating chamber. The solvent preferably passes under these conditions to at least 20% by weight, preferably to at least 50% by weight, into the gas phase.

The solvents preferably have a boiling point (at 1013 mbar and in pure substance) of less than 80 ° C., preferably of less than 70 ° C. The precursor compounds preferably have a boiling point (at 1013 mbar and in pure substance) of more than 80 ° C., preferably more than 90 ° C.

Preferred solvents for the purposes of the invention are therefore acetone, acetonitrile, benzene, tert-butyl methyl ether, chloroform, cyclohexane, diethyl ether, ethyl acetate, ethanol, ethylene dichloride, hexane, 2-propanol, methanol, 2-methyl-2-propanol, methylene chloride , Methyl ethyl ketone, pentane, carbon disulfide, carbon tetrachloride and tetrahydrofuran understood.

As a precursor compound are preferably benzonitrile, 1-butanol, 2-butanol, chlorobenzene, diethylene glycol, dimethylacetamide, dimethylformamide, dimethylsulfoxide, 1,4-dioxane, glacial acetic acid, glacial acetic acid, ethylene glycol, ethylene glycol, ethylene glycol, formamide, substituted and unsubstituted alkanes having at least 6C Atoms, substituted and unsubstituted alkenes having at least 6 C atoms, substituted and unsubstituted alkynes having at least 6 C atoms, 3-methyl-1-butanol, 2-methyl-2-propanol, N-methyl-2 pyrrolidone, N-methylformamide, nitrobenzene, piperidine, propylene carbonate, pyridine, toluene and triethylene glycol dimethyl ether. Alternatively or additionally preferred are the precursor compounds selected from monomers having double bonds, preferably from acrylates, styrenes and fluoroethenes, as well as organometallic compounds, preferably silanes and siloxanes, which are preferably stable up to a temperature of 200 ° C. The metals of the organometallic compounds are preferably rare earth metals, transition metals, silicon, aluminum, gallium, indium, tin, bismuth or mixtures thereof. Preferably, the liquid medium is a solution. The liquid medium is preferably free of suspended particles and / or particulate constituents and / or suspendible constituents and / or solids and / or powders and / or turbid substances. The liquid medium preferably consists of the at least one precursor compound.

The term "precursor compound" is understood to mean a compound which serves as starting compound for the coating to be produced. The precursor compounds according to the invention are preferably characterized in that they are activatable compounds which can be introduced into a coating chamber via a nozzle and can be converted into a polymeric, polymer-like and / or hard material coating. Preferably, the precursor compound is soluble in a solvent. The precursor compounds according to the invention are preferably polymerizable monomers and / or oligomers and organometallic complexes. The monomers preferably have a polymerizable double bond and / or polymerizable functional groups. The polymerisable functional groups preferably have at least one heteroatom, preferably oxygen, nitrogen and sulfur. The precursor compounds according to the invention can be activated, in particular by thermal, electronic and / or rotational excitation and / or by chemical reaction, preferably to radicals, ions or fragments. As the precursor compounds, monomers such as acrylic acid, acrylate, methacrylate, methacrylic acid, hexamethyldisiloxane, polydimethylsiloxane, tetramethyldisiloxane or oligomers thereof may preferably be used. Alternatively, preferred precursors may be glycols, preferably ethylene glycol, diethylene glycol or ethylene glycol dimethyl ester. If glycols are used as precursor compounds, they are not considered as solvents.

The term "oligomers" means compounds which have a plurality of identical units, also called monomers, preferably consist thereof, the units repeating two to ten times, preferably four to eight times.

The term "activatable" is understood to mean that the at least one precursor compound can be brought into a state whereby these activated molecules of the at least one precursor compound can react with activated and / or non-activated, preferably ground-state molecules of the at least one precursor compound, in particular to polymer-like or polymeric compounds. Without the activation according to the invention, it is not possible that the at least one precursor compound can be chemically reacted under the conditions present during the performance of the process according to the invention or according to the invention, in particular to form an oligomer or a polymeric or polymer-like compound.

The term "activation" is preferably understood to mean a treatment which is selected from plasma-chemical treatment, treatment with charge carriers, treatment with radiation and several of them. Accordingly, activation of the at least one precursor compound or of the at least one surface of the two- or three-dimensional body can preferably be effected by ions, radicals, electrons, in particular high-energy electrons, or electromagnetic radiation. Preferably, the molecules of the at least one precursor compound or the at least one surface of the two- or three-dimensional body can be activated by different activation possibilities, preferably selected from the group consisting of ions, radicals, electrons, preferably high-energy electrons, and electromagnetic radiation. By activating the at least one precursor compound and / or the at least one surface of the two- or three-dimensional body, the molecules of the at least one precursor compound are crosslinked with one another and / or with the at least one, preferably activated, surface of the two- or three-dimensional body.

In a preferred embodiment of the present invention, the at least one surface of the two- or three-dimensional body is also activatable. Thus, both the at least one precursor compound and the at least one surface of the two- or three-dimensional body are preferably activatable.

In step d), the at least one precursor compound and / or the at least one surface of the two- or three-dimensional body is activated by means of the low-temperature plasma generated by the plasma generating device such that they are preferably activated or non-activated molecules of the at least one precursor compound or with the activated or non-activated surface of the two- or three-dimensional body. During activation, reactive free-radical and / or reactive ionic and / or reactive free-radical-ionic structures preferably form in the molecules of the at least one precursor compound and / or on the at least one surface of the two- or three-dimensional body. By activating the at least one precursor compound, a covalent linking of the activated molecules of the at least one precursor compound with the activated or non-activated surface of the two- or three-dimensional body and / or with other activated or non-activated molecules of the at least one precursor compound preferably takes place. By activating the at least one surface of the two-dimensional or three-dimensional body, preference is given to a covalent linkage with activated and / or non-activated molecules of the at least one precursor compound.

The term "without carrier gas" is understood to mean that the introduction of the liquid medium containing at least one precursor compound takes place without carrier gas. This means that no gas is introduced together with the liquid medium via the nozzle in the coating chamber. Of course, the preferably finely distributed present, liquid medium after entering the coating chamber either partially evaporate, preferably in the range of Low-temperature plasma, or be transported by means of a carrier gas after or during the low-temperature plasma treatment to be coated at least one surface of the two- or three-dimensional body. According to the invention, the term "without carrier gas" is understood in particular to mean that the migrating drops or droplets transported through the nozzle do not have to be sheared off by a gas, in particular the carrier gas.

The term "low-temperature plasma" is understood to mean a plasma, the temperature of the neutral particles and ions produced by the plasma-generating device being significantly lower than the temperature of the electrons. In particular, a low-temperature plasma is present when the neutral particles and the ions of the plasma have a temperature of less than 200 ° C., preferably less than 120 ° C., and the electrons generated have a temperature of more than 5000 ° C., preferably more than 9000 ° C., exhibit.

The term "nozzle" is understood to mean a device whereby the flow velocity of the liquid medium is increased. In particular, the nozzle increases the flow rate of the liquid medium through a tapered shape. Preferably, the outlet opening of the nozzle is smaller than the inlet opening in the nozzle.

It is crucial for the present invention that the at least one precursor compound according to step c) is introduced into the coating chamber in liquid form by means of a nozzle. Accordingly, the aggregation state of the at least one precursor compound or the medium containing at least one precursor compound should be liquid immediately prior to atomization by means of the nozzle. Accordingly, it is possible to use a precursor compound present in gaseous form under normal conditions (p = 1013 mbar and T = 20 ° C.) if it is used under the process conditions according to the invention or preferred according to the invention, ie. H. may be present dissolved at a corresponding pressure and temperature, in liquefied form or in a liquid medium. The same applies to solid under normal conditions precursor compounds, which may be present under the inventive or inventively preferred process conditions in liquid form or dissolved in a liquid medium.

The present invention relates, in a preferred embodiment, to a process wherein the liquid medium containing the at least one precursor compound is introduced in the form of droplets into the coating chamber, wherein at least 90% of all droplets have a diameter of 100 μm or less. Preferably, at least 90% of all droplets have a diameter of 50 μm or less, preferably 30 μm or less, preferably 20 μm or less.

In a preferred embodiment, the present invention relates to a process wherein the liquid medium containing the at least one precursor compound is present in an antechamber of the nozzle, wherein a pressure of more than 0.5 bar is present in the prechamber and the liquid which is at least a precursor compound-containing medium is preferably introduced by opening a valve in the coating chamber by means of the nozzle.

According to the invention, the nozzle is mounted on or in the coating chamber such that it allows the liquid medium to enter the coating chamber. Preferably, the nozzle is enclosed in a gas-tight manner by the coating chamber, so that the liquid medium can be introduced into the coating chamber solely through the at least one, preferably exactly one, opening of the nozzle.

Preferably, the prechamber of the nozzle is in contact with the nozzle in such a way that the liquid medium containing the at least one precursor compound can pass from the prechamber, preferably through a line, to the nozzle. Preferably, there is at least one closable valve between the antechamber, preferably an antechamber which can be pressurized, and the nozzle. In a preferred method of the present invention, the liquid liquid medium containing the at least one precursor compound is introduced into the pre-chamber of the nozzle. Subsequently, the pressure is preferably increased by introducing, preferably pressing, gas, in particular inert gas, to at least 0.5 bar, preferably 1.5 bar, preferably at least 2 bar, preferably at least 5 bar, preferably at least 7 bar, when the valve is closed. Subsequently, the valve between the antechamber of the nozzle and the nozzle is preferably at least partially, preferably completely open, so that the liquid medium is introduced from the pre-chamber through the valve and the nozzle into the coating chamber, in particular in the form of droplets, wherein at least 90% of all Droplets have a diameter of 100 microns or less. In this procedure, a pressure difference of more than 1 bar, preferably more than 2 bar, preferably more than 4 bar, preferably more than 5 bar, preferably more than 6 bar, preferably more than 8 bar, is preferably present in this procedure. The pressure difference results from the difference between the pressure which is present in the pre-chamber of the nozzle, preferably immediately before opening the valve, and the pressure which is present in the coating chamber, preferably immediately before introduction of the liquid medium. Preferably, the nozzle is referred to with antechamber as a nozzle device. Preferably, the nozzle device additionally comprises a conduit and a closable valve, which are arranged and designed as described above.

The nozzle is preferably suitable for introducing finely distributed droplets of the liquid medium into the coating chamber, the pressure in the coating chamber being less than 1 bar, preferably less than 600 mbar, preferably less than 1 mbar. Preferably, the nozzle used according to the invention is suitable for allowing high shear forces to act on the liquid medium. The generation of high shear forces occurs in particular by ultrasound, high pressure and / or by strong turbulence. A variety of known in the art nozzles does not have a corresponding suitability. Most of the nozzles known in the art can be used alone Atmospheric pressure or a higher pressure to generate liquids in the form of finely divided droplets, in particular in the form of a spray. In conventional nozzles known in the prior art, the required shearing forces for shearing the droplets without a corresponding back pressure, that is a pressure of 1 bar or more, can not be generated. Accordingly, these nozzles known in the art require a gas stream, in particular a carrier gas stream, if these nozzles are used under pressure conditions of less than 1 bar, in particular less than 600 mbar, preferably less than 1 mbar.

The nozzle used according to the invention makes it possible in particular to provide a uniform droplet size distribution, in particular at least 90% of the droplets, preferably at least 99% of the droplets, have a diameter of less than 30 μm, preferably 10 to 30 μm. In particular, at least 90%, preferably at least 99%, of all droplets produced by the nozzle have a diameter, wherein the smallest diameter of these droplets differs from the largest diameter of these droplets by a maximum of 10 μm, preferably by a maximum of 5 μm, preferably by a maximum of 2 μm ,

The deposition rate in the method according to the invention or preferred according to the invention is preferably 50 to 100 nm (layer thickness) per second, preferably 60 to 70 nm per second. The layer thickness is determined by the usual in the prior art Elipsometrie method.

Preferably, the nozzle according to the invention is a nozzle having a vortex chamber.

Preferably, the nozzle has an inlet opening for the liquid medium, a vortex chamber and an outlet opening for the liquid medium, the nozzle preferably being produced by an etching process. The etching process results in smooth, flowing transitions, which leads to an increased turbulence and thus to a homogeneous droplet distribution. In addition, this vortex effectively allows a vortex in the vortex chamber and the generation of the spray on the exit of the liquid medium from the outlet opening. The vortex chamber preferably has a shape in which the liquid medium can move toward the middle of the vortex chamber. The outlet opening is located in the middle of the vortex chamber, so that the liquid medium to be sprayed can leave the vortex chamber in a conical thin film, which atomises to fine droplets immediately after leaving the outlet opening.

The nozzle used according to the invention also has feed slots. These feed slots are preferably arranged non-radially and extend into the vortex chamber, so that via these feed slots, preferably only thereby, the liquid medium enters the vortex chamber. The non-radial arrangement of the feed slots extending into the swirl chamber directs the liquid medium into the swirl chamber to create a swirling motion.

Also, the nozzle used in the present invention preferably has a feed ring concentrically around the swirl chamber, the non-radial feed slots connecting the feed ring to the swirl chamber.

Preferably, the nozzle has a disk, a disk holder and an inlet piece. The disc has a flat top and a flat bottom. The disk holder is preferably circular. The diameter of the disc is preferably substantially the same, preferably equal to the inner diameter of the holder. Together with the inlet piece, the disc and the holder form a cylindrical nozzle which has an outlet opening in the center of the cylindrical nozzle device. In the bottom of the disc, a vortex chamber, inlet slots and a feed ring are formed. The vortex chamber has a shell shape and is formed in the center of the disc. The term "shell shape" is to be understood that the vortex chamber is round and that the sides of the vortex chamber with a substantially vertical, preferably vertical outer wall and a substantially horizontal, preferably horizontal inner wall, are slightly curved. The exit opening extends through the top of the disc to the center of the vortex chamber.

The vortex chamber preferably has a diameter of 1 to 3 mm, preferably of 1.5 mm, at the widest point. At the lowest point, the vortex chamber preferably has an extension of 0.1 to 0.5 mm, more preferably of 0.33 mm. The ratio between the diameter of the vortex chamber and the diameter of the spray opening, also referred to as the outlet opening, is preferably in a range from 2: 1 to 10: 1, preferably 2: 1 to 5: 1.

The length of the outlet opening, that is to say the extent from the vortex chamber to the upper side of the disk, is preferably 0.1 to 5 mm, preferably 0.15 mm. The ratio of length to diameter of the outlet opening is 1: 3 or less.

The diameter of the outlet opening is preferably in the range of 0.05 to 2.50 mm

To induce eddy current in the swirl chamber, the inlet slots in the disk are formed to extend non-radially from the swirl chamber. Preferably, each slot extends in the same direction of rotation so that turbulence in the vortex chamber is effected in the same direction.

The vortex chamber and the feed slots are surrounded by a feed ring. The feed ring has a circular outer wall and a circular inner wall which are interrupted by the slots. The ring preferably has the shape of a trough with rounded walls. Also preferably, the ring has the same depth as the slots and the adjacent part of the vortex chamber.

The inlet piece is preferably a flat disc having one or more inlet passages extending through that disc. The inlet passages communicate with the feed ring. They allow the liquid medium passes through the inlet piece, in particular through the inlet passages to the feed ring. In a preferred embodiment, therefore, the liquid medium first flows through the inlet passages into the feed ring. Subsequently, the liquid medium leaves the feed ring via the non-radially arranged feed slots, towards the vortex chamber. The vortex chamber generates high shear forces, whereby the liquid medium leaves this vortex chamber via the outlet opening in the form of a thin jet and after exiting in the form of finely divided mist, preferably in the form of finely divided droplets, wherein at least 90% of all droplets have a diameter of 100 have μm or less.

Preferably, the nozzle is a nozzle according to the Figures 3 to 6 of DE 694 29 354 T2 and the associated figure description. An appropriate disclosure content is referred to herein. The disclosure of the Figures 3 to 6 of DE 694 29 354 T2 and the associated figure description is included in the disclosure of the present invention.

In a preferred embodiment, the present invention relates to a process wherein the liquid medium containing at least one precursor compound is atomized by means of ultrasound and introduced through the nozzle into the coating chamber.

In this preferred embodiment, the liquid medium is first fed to an ultrasonic atomizing device, in particular from the manufacturer Sonozap, before it is introduced, in particular introduced, through the nozzle into the coating chamber in atomized form. The ultrasonic atomizing device has in particular a piezoceramic connected to a current source, whereby the liquid medium is atomized. By the Ultraschallzerstäubungsvorrichtung the liquid medium is preferably converted into droplets.

In a preferred embodiment, the liquid medium containing the at least one precursor compound is atomized by means of ultrasound. In this case, the liquid medium is introduced into the nozzle by means of a conduit, the nozzle preferably comprising titanium, stainless steel or a fluoropolymer, preferably consisting thereof. A piezoceramic, which is also preferably present in the nozzle, converts the current generated by a current source into mechanical vibrations. The vibrations preferably extend as far as the tip of the nozzle, that is, as far as the nozzle outlet, where they are thrown back towards the piezoceramic, producing standing waves. By these standing waves is preferably a pumping action, whereby the liquid medium is drawn towards the center of the nozzle. The liquid medium is passed through the nozzle by means of a conduit which ends at the outlet opening. The piezoelectric ceramic which is also preferably present in the nozzle and which contains the Ultrasound generated, is preferably attached to the liquid medium conducting line. The line is vibrated by the generated ultrasound, in particular by the generated standing waves of the ultrasound, whereby the liquid medium is atomized into finely distributed droplets after exiting the outlet opening.

Alternatively, the ultrasound can also be generated by compressed air, also referred to as compressed air. In this ultrasonic atomizing device, the line conducting the liquid medium preferably adjoins a compressed air line, preferably being enclosed by it. Through the compressed air line flows to generate ultrasound the compressed air, which sets the liquid medium conducting line in ultrasonic vibration, these vibrations atomizes the liquid medium.

Preferably, the liquid containing at least one precursor compound medium is not atomized by ultrasound. Preference is therefore given to the introduction of the liquid, the at least one precursor compound-containing medium free from atomization by means of ultrasound. The liquid medium containing the at least one precursor compound is preferably introduced into the coating chamber without the generation of vibrations. The liquid containing the at least one precursor compound is preferably introduced into the coating chamber without the aid of a piezoceramic and / or mechanical vibrations. Preferably, the nozzle device, preferably the nozzle, preferably a vortex chamber having a nozzle, free of a device for generating vibrations, preferably mechanical vibrations, preferably ultrasound. Preferably, the nozzle device, preferably the nozzle, preferably a vortex chamber having a nozzle, free of a piezoceramic. Preferably, the nozzle device, preferably the nozzle, preferably a vortex chamber having a nozzle, free from a compressed air line, whereby the liquid medium conducting line can be placed in ultrasonic vibrations. Preferably, the nozzle, preferably the nozzle having a vortex chamber, is not an ultrasonic nozzle. The nozzle, preferably the nozzle having a swirl chamber, is preferably a nozzle that is free of ultrasonic atomization.

In a preferred embodiment, the present invention relates to a process wherein a pressure of less than 800 mbar, preferably less than 600 mbar, preferably less than 400 mbar, preferably less than 100 mbar, is preferred in the coating chamber, preferably immediately before introducing the liquid medium less than 50 mbar, preferably less than 1 mbar, preferably less than 0.1 mbar is present.

In a preferred embodiment, the present invention relates to a process wherein the low-temperature plasma has a maximum temperature of 200 ° C., preferably not more than 150 ° C., preferably not more than 120 ° C., preferably not more than 100 ° C., preferably not more than 60 ° C. (in each case based on the neutral particles and / or the ions of the plasma).

The present invention relates, in a preferred embodiment, to a method wherein the low-temperature plasma is generated by capacitive or inductive coupling, microwaves, direct current or dielectrically impeded discharge. The low-temperature plasma is preferably produced by capacitive or inductive coupling, microwaves or direct current when there is a pressure of 100 mbar or less in the coating chamber. These plasmas are also called volume plasmas. Preferably, the low-temperature plasma is generated by dielectrically impeded discharge when a pressure of more than 100 mbar is present in the coating chamber. This plasma is also referred to as near-surface plasma.

The introduction of the liquid medium containing at least one precursor compound according to step c) preferably takes place by means of an ultrasonic nozzle into the coating chamber, the ultrasonic nozzle having a frequency of at least 30 kHz, preferably at least 60 kHz, preferably at least 100 kHz, preferably at least 130 kHz, is operated.

In step c), the liquid medium containing at least one precursor compound is preferably introduced into the coating chamber at a temperature of from -50.degree. C. to 300.degree. C., preferably from -20.degree. C. to 100.degree. C., preferably from 0 to 50.degree. Preferably, the medium has a temperature of -50 ° C to 300 ° C, preferably from -20 ° C to 100 ° C, preferably 0 to 50 ° C, before it is brought into contact with the nozzle, preferably the ultrasonic nozzle , is preferably atomized, wherein the ultrasonic nozzle is preferably operated at a frequency of at least 30 kHz, preferably at least 60 kHz, preferably at least 100 kHz, preferably of at least 130 kHz.

Alternatively or additionally, the liquid medium containing at least one precursor compound has a viscosity of at least 10 mPa · s, preferably of at least 30 mPa · s, preferably of at least 50 mPa · s, preferably of at least 70 mPa · s, preferably of at least 100 mPa · S, preferably from 30 mPa · s to 200 mPa · s, preferably from 50 mPa · s to 150 mPa · s before it is preferably brought into contact with the nozzle, preferably the ultrasonic nozzle, is preferably atomized, wherein the Ultrasonic nozzle preferably with a frequency of at least 30 kHz, preferably at least 60 kHz, preferably at least 100 kHz, preferably of at least 130 kHz, is operated. Advantageously, with an ultrasonic nozzle which is operated at a frequency of at least 30 kHz, preferably at least 60 kHz, preferably at least 100 kHz, preferably of at least 130 kHz, a highly viscous medium, preferably having a viscosity of at least 10 mPa · s, preferably at least 30 mPa.s, preferably at least 50 mPa.s, preferably at least 70 mPa.s, preferably at least 100 mPa.s, preferably from 30 mPa.s to 200 mPa.s, preferably 50 mPa.s. to 150 mPa · s in the coating chamber, preferably finely divided and in large quantities, introduced.

Alternatively or additionally, the liquid medium containing at least one precursor compound has a viscosity of at most 100 mPa.s, preferably not more than 70 mPa.s, preferably not more than 50 mPa.s, preferably not more than 30 mPa.s, preferably not more than 10 mPa.s. · S, preferably from 1 mPa · s to 70 mPa · s, preferably from 1 mPa · s to 30 mPa · s before it is preferably brought into contact with the nozzle, preferably the nozzle with swirl chamber, preferably atomized ,

Alternatively or additionally, the liquid medium containing at least one precursor compound has a salt concentration of from 0.1 mmol to 50 mol, preferably from 1 mol to 30 mol, preferably from 5 to 10 mol, before it preferably by means of the nozzle, preferably the ultrasonic nozzle, is brought into contact, preferably atomized, wherein the ultrasonic nozzle is preferably operated at a frequency of at least 30 kHz, preferably at least 60 kHz, preferably at least 100 kHz, preferably of at least 130 kHz.

Alternatively or additionally, the liquid medium containing at least one precursor compound has a salt concentration of 0.1 mmol to 50 mol, preferably from 0.1 mol to 10 mol, preferably from 1 to 5 mol, before it preferably with the nozzle, preferably the Nozzle with swirl chamber is brought into contact, preferably atomized.

In step c), the liquid medium containing at least one precursor compound is preferred at a pressure of at least 5 bar, preferably at least 10 bar, preferably at least 50 bar, preferably from 5 bar to 100 bar, preferably from 10 bar to 50 bar introduced the coating chamber.

Preferably, this pressure of at least 5 bar, preferably at least 10 bar, preferably of at least 50 bar, preferably from 5 bar to 100 bar, preferably from 10 bar to 50 bar, before the medium with the nozzle, preferably the ultrasonic nozzle in contact is preferably atomized, wherein the ultrasonic nozzle is preferably operated at a frequency of at least 30 kHz, preferably at least 60 kHz, preferably at least 100 kHz, preferably of at least 130 kHz.

The present invention relates, in a preferred embodiment, to a process wherein the liquid medium comprising at least one precursor compound as precursor compound has monomers activatable by the low-temperature plasma before and / or after deposition according to step e) on the surface of the two- or three-dimensional body react to a polymeric, polymer-like or hard coating.

The liquid medium preferably has at least two different precursor compounds, preferably exactly two different precursor compounds, preferably at least three different precursor compounds, preferably exactly three precursor compounds. Prefers the liquid medium comprises monomers or oligomers, preferably monomers. Preference is given to the monomers and / or the oligomers of acrylic and / or methacrylic acid compounds. The liquid medium preferably has salts dissolved therein, preferably of metal ions, preferably noble metal ions, preferably silver ions.

The liquid medium containing at least one precursor compound preferably has insoluble, suspendible constituents with a maximum particle size of 1 μm, preferably 100 nm, preferably 10 nm. The liquid medium preferably contains, in addition to the at least one precursor compound, a solvent, preferably water, so as to adjust the viscosity of the at least one precursor compound in a targeted manner, preferably to reduce it. The liquid medium is preferably free of solvents, in particular free of further constituents. The liquid medium preferably consists of the at least one precursor compound. Preferably, the liquid medium consists of compounds containing the chemical elements selected from the group consisting of fluorine, silicon and carbon.

The liquid medium containing the at least one precursor compound is preferably free of powders, preferably metal powders, preferably more than 1 .mu.m, preferably more than 100 nm, preferably more than 10 nm.

Preferably, the activated precursor compounds are introduced into the coating chamber at a temperature which is below the boiling point of the at least one precursor compound.

Preferably, the at least one activatable precursor compound is introduced into the coating chamber at a temperature which is below the boiling point of the at least one precursor compound.

Preferably, at least one plasma process gas is present in the coating chamber, preferably this is introduced. The plasma process gas is preferably selected from argon, oxygen, nitrogen, nitric oxide and a mixture thereof, preferably oxygen.

The term "hard material coating" is understood to mean a vitreous, ceramic, ceramic-like or metal-oxide coating.

These hard material coatings can preferably be prepared so that metal-containing precursor compounds, in particular organometallic compounds which are stable up to a temperature of 200 ° C. under the process conditions according to the invention, are introduced and these compounds are preferably added to the low-temperature plasma and the process gas, preferably oxygen, get abandoned. The organometallic compounds used as precursor compounds, also referred to as organometallic complexes, are preferably trialkyl compounds of the particular metal, where the alkyl radicals may be identical or different and are preferably selected from the group consisting of methyl, ethyl, propyl and butyl, preferably methyl. Preferably, the metal of the metal-containing compound, in particular the organometallic compound selected from the group consisting of semimetal and metal, preferably titanium, aluminum and silicon.

Preferably, it is alternatively possible to produce the hard coatings such that first at least one precursor compound is deposited on the at least one surface of the two- or three-dimensional body and subsequently this coated surface, in particular by oxygen and / or temperatures of over 200 ° C, preferably from above 500 ° C, is treated.

Preference is given to using hexamethyldisiloxane, polydimethylsiloxane, tetramethyldisiloxane, fluorinated or perfluorinated compounds thereof or mixtures thereof as precursor compound. From these precursor compounds are formed by the inventive or inventively preferred method preferably polymeric or polymer-like compounds after deposition on the at least one surface of the two- or three-dimensional body. Subsequently, these polymeric or polymer-like coatings can be converted by the action of oxygen and / or high temperatures of more than 200 ° C, preferably more than 500 ° C to corresponding glassy coatings. Corresponding glassy coatings can also be obtained by using the plasma process gas oxygen during the coating process and carrying out the process at a temperature between 50 and 200 ° C., preferably 100 to 150 ° C.

1. a) Bereitstellen eines flüssigen, mindestens eine Vorläuferverbindung enthaltenden Mediums, wobei polymerisierbare Monomere und/oder Oligomere sowie metallorganische Komplexe als die mindestens eine Vorläuferverbindung eingesetzt werden, wobei die Monomere bevorzugt ausgewählt sind aus Acrylsäure, Acrylat, Methacrylat, Methacrylsäure, Hexamethyldisiloxan, Polydimethylsiloxan und Tetramethyldisiloxan, und wobei das flüssige Medium frei von Partikel mit einer Partikelgröße von mehr als 1 µm, bevorzugt mehr als 100 nm, bevorzugt mehr als 10 nm und frei von Lösungsmitteln ist,
2. b) Bereitstellen einer Beschichtungskammer, die einen zu beschichtenden zwei- oder dreidimensionalen Körper und eine Plasmaerzeugungsvorrichtung aufweist, wobei in der Beschichtungskammer ein Druck von weniger als 1 bar, bevorzugt weniger als 800 mbar, bevorzugt weniger als 600 mbar, bevorzugt weniger als 400 mbar, bevorzugt weniger als 100 mbar, bevorzugt weniger als 50 mbar, bevorzugt weniger als 1 mbar, bevorzugt weniger als 0,1 mbar vorliegt,
3. c) Einbringen des flüssigen, mindestens eine Vorläuferverbindung enthaltenden Mediums ohne Trägergas mittels einer Düse in die Beschichtungskammer in Tröpfchenform, wobei mindestens 90 % aller Tröpfchen einen Durchmesser von 100 µm oder weniger, bevorzugt von 50 µm oder weniger, bevorzugt 30 µm oder weniger, bevorzugt 20 µm oder weniger, bevorzugt 10 bis 30 µm aufweisen, wobei die Düse bevorzugt dazu geeignet, hohe Scherkräfte auf das flüssige Medium einwirken zu lassen, und wobei die Düse bevorzugt eine Eintrittsöffnung für das flüssige Medium, eine Wirbelkammer und eine Austrittsöffnung für das flüssige Medium aufweist,
4. d) Aktivieren der mindestens einen Vorläuferverbindung und/oder von mindestens einer Oberfläche des zwei- oder dreidimensionalen Körpers mittels eines durch die Plasmaerzeugungsvorrichtung erzeugten Niedertemperaturplasmas, wobei das Niedertemperaturplasma eine Temperatur von maximal 200 °C, bevorzugt maximal 150 °C, bevorzugt maximal 120 °C, bevorzugt maximal 100 °C, bevorzugt maximal 60 °C (jeweils bezogen auf die Neutralteilchen und/oder die Ionen des Plasmas) aufweist, und wobei das Niedertemperaturplasma bevorzugt durch kapazitive oder induktive Kopplung, Mikrowellen, Gleichstrom oder dielektrische behinderte Entladung erzeugt wird, und bevorzugt ein Plasmaprozessgas vorliegt, bevorzugt dieses eingeleitet wird,
5. e) Abscheiden der mindestens einen, bevorzugt aktivierten, Vorläuferverbindung oder Oligomere davon auf mindestens einer, bevorzugt aktivierten, Oberfläche des zwei- oder dreidimensionalen Körpers, sodass sich eine polymere, polymerartige, glasartige, keramikartige, keramische oder metalloxidische Beschichtung daraus ausbildet, und
6. f) Erhalten einer Beschichtung auf der mindestens einen Oberfläche eines zwei- oder dreidimensionalen Körpers.

Preferably, the at least one precursor compound alone in the coating chamber is activated by the low-temperature plasma. Only after deposition on the at least one, preferably activated, surface of the two- or three-dimensional body does this activated at least one precursor compound react to form the polymer-like or polymeric compounds. Preferably, it is also possible that due to the prevailing pressure and the high amount of the introduced liquid medium, the at least one activated precursor compound already in smaller units, preferably to oligomers, connects, before being on the at least one, preferably activated, surface of the two - or three-dimensional body separates. In a particularly preferred embodiment of the present invention, a method is provided for coating at least one surface of a two- or three-dimensional body, the method comprising the following steps:

1. a) providing a liquid medium containing at least one precursor compound, wherein polymerizable monomers and / or oligomers and organometallic complexes are used as the at least one precursor compound, wherein the monomers are preferably selected from acrylic acid, acrylate, methacrylate, methacrylic acid, hexamethyldisiloxane, polydimethylsiloxane and tetramethyldisiloxane , and wherein the liquid medium is free of particles having a particle size of more than 1 μm, preferably more than 100 nm, preferably more than 10 nm and free of solvents,
2. b) providing a coating chamber having a two- or three-dimensional body to be coated and a plasma generating device, wherein in the coating chamber a pressure of less than 1 bar, preferably less than 800 mbar, preferably less than 600 mbar, preferably less than 400 mbar, preferably less than 100 mbar, preferably less than 50 mbar, preferably less than 1 mbar, preferably less than 0.1 mbar,
3. c) introducing the liquid containing at least one precursor compound without carrier gas by means of a nozzle in the coating chamber in droplet form, wherein at least 90% of all droplets have a diameter of 100 microns or less, preferably 50 microns or less, preferably 30 microns or less, preferably 20 microns or less, preferably 10 to 30 microns, wherein the nozzle is preferably adapted to allow high shear forces acting on the liquid medium, and wherein the nozzle preferably has an inlet opening for the liquid medium, a vortex chamber and an outlet opening for the liquid medium having,
4. d) activating the at least one precursor compound and / or at least one surface of the two- or three-dimensional body by means of a low-temperature plasma generated by the plasma generating device, wherein the low-temperature plasma has a maximum temperature of 200 ° C, preferably not more than 150 ° C, preferably not more than 120 ° C. , preferably at most 100 ° C., preferably at most 60 ° C. (in each case based on the neutral particles and / or the ions of the plasma), and wherein the low-temperature plasma is preferably generated by capacitive or inductive coupling, microwaves, direct current or dielectrically impeded discharge, and preferably a plasma process gas is present, preferably this is introduced,
5. e) depositing the at least one, preferably activated, precursor compound or oligomers thereof on at least one, preferably activated, surface of the two or three dimensional body to form a polymeric, polymer, glassy, ceramic, ceramic or metal oxide coating therefrom, and
6. f) obtaining a coating on the at least one surface of a two- or three-dimensional body.

1. i) eine Beschichtungskammer, die eine Niedertemperaturplasmaerzeugungsvorrichtung aufweist und in der ein Druck von weniger als 1 bar vorliegen kann, und
2. ii) eine Düse, die dazu geeignet ist, ein flüssiges, mindestens eine Vorläuferverbindung enthaltendes Medium ohne Trägergas in die Beschichtungskammer einzubringen, wobei in der Beschichtungskammer ein Druck von weniger als 1 bar vorliegt.

The present invention also provides an apparatus for coating at least one surface of a two- or three-dimensional body, preferably for carrying out a method according to the invention or preferred according to the invention

1. i) a coating chamber having a low-temperature plasma generating device and in which a pressure of less than 1 bar may be present, and
2. ii) a nozzle which is suitable for introducing a liquid medium containing at least one precursor compound without carrier gas into the coating chamber, wherein a pressure of less than 1 bar is present in the coating chamber.

In a preferred embodiment of the present invention, the embodiments or preferred embodiments disclosed in connection with the inventive and / or invented preferred method mutatis mutandis also apply mutatis mutandis to the coating chamber of the plasma generating device, the nozzle and the liquid medium for the device for coating at least one surface two- or three-dimensional body and the use of a carrier gas-free introduction of a liquid medium according to the present invention.

In particular, the invention also relates to a coated surface of a two- or three-dimensional body produced by a method according to the invention or preferred according to the invention.

The invention also relates to the use of a carrier gas-free introduction of a liquid medium containing at least one precursor compound into a coating chamber, the coating chamber having a pressure of less than 1 bar and a low-temperature plasma generating device for homogeneously coating at least one surface of a two- or three-dimensional body. In particular, the coating chamber has a pressure of less than 800 mbar, preferably less than 600 mbar, preferably less than 400 mbar, preferably less than 100 mbar, preferably less than 1 mbar, preferably less than 0.1 mbar. Preferably, the statements made in connection with the method according to the invention or preferred according to the invention, in particular embodiments according to the invention or inventively preferred, mutatis mutandis also apply to the use of the carrier gas-free introduction of a liquid medium.

Surprisingly, it is possible by the method according to the invention to produce homogeneous, very smooth coatings on at least one surface of the two- or three-dimensional body. Accordingly, the present method can be preferably used in thin-film technology become. Likewise, special coatings produced by the process according to the invention, in particular polymeric coatings with additives, preferably silver ions, can be used in the field of medical technology.

The term "homogeneous" means that both a uniform layer thickness of the coating is present and over the essential parts of, preferably over the entire, coated surface of the two- or three-dimensional body, a substantially material and / or structurally the same, preferably Substantially and / or structurally identical polymeric, polymer-like, ceramic-like, ceramic or metal-oxide coating.

Preferably, the two- or three-dimensional body is formed as a ceramic, glass or foil. The two- or three-dimensional body is preferably designed as a syringe, tooth, prosthesis, orthosis, implant, graft, bioanalysis vessel, bioculture vessel, medical device, automobile part, part of a motor, spectacle lens or lens.

Further advantageous embodiments will be apparent from the dependent claims.

Figur 1

eine vorteilhafte Ausgestaltung der vorliegenden Vorrichtung zur Beschichtung mindestens einer Oberfläche eines zwei- oder dreidimensionalen Körpers, und

Figuren 2 und 3

eine vorteilhafte Ausgestaltung einer Düse gemäß der vorliegenden Erfindung.

The present invention will be explained in more detail with reference to the present figures and the example. Show

FIG. 1

an advantageous embodiment of the present device for coating at least one surface of a two- or three-dimensional body, and

FIGS. 2 and 3

an advantageous embodiment of a nozzle according to the present invention.

FIG. 1 shows a device 1 for coating a two- or three-dimensional body, wherein the device has a coating chamber 3. The coating chamber 3 has a positioning device 5 for the two- or three-dimensional body 7 to be coated. The apparatus 1 likewise has a nozzle 9, through which the liquid medium in the form of finely distributed droplets 11 is introduced into the coating chamber 3 and preferably impinges on at least one surface of the two- or three-dimensional body 7 to be coated. The liquid medium can be introduced via the feed line 13 into an antechamber 15. The pre-chamber is either pressurized and the liquid medium is thus introduced through a not shown valve via the nozzle 9 in the coating chamber. Alternatively, in the pre-chamber 15 is a piezoceramic, which is connected to a power source, so that the nozzle 9 is placed in ultrasonic vibrations, whereby the liquid medium is atomized. Also, in the coating chamber 3, there is provided a plasma generating device 17 capable of generating a low-temperature plasma. Also shown is a gas inlet 19 provided with a valve 21. The also shown Outlet 23 serves, in particular, to evacuate the coating chamber and / or remove the undesired constituents present in the coating chamber, preferably by means of a vacuum pump (not shown).

FIG. 2 shows a disc 30 of a preferred inventively used nozzle, the bottom 31 of the disc can be seen. In the middle of the disc is a vortex chamber 33, which centered has an outlet opening 35. Also, the underside 31 of the disc 30 has a feed ring 37, from which non-radial inlet slots 39 to 42 extend to the vortex chamber 33. Also, the disc 30 has an annular peripheral wall 43 and four island surfaces 45 to 48. The annular peripheral wall 43 and the island-shaped projections 45 to 48 have the same height and form the bottom 31 of the disc 30th

FIG. 3 The nozzle 50 includes a disc 30, an inlet 53, and a disc holder 55. The disc 30 has a flat top 32 and a flat bottom 31. The disc holder 55 is preferably circular, but may be one have any shape with a flat top 57, which fits to the flat top 32 of the disc 30. The diameter of the disc 30 is approximately the same as the inner diameter of the disc holder 55. Together, the disc 30, the inlet piece 53 and the holder 55 form a cylindrical nozzle with a spray opening 35 in the center of the cylindrical nozzle unit 50. In the bottom 31 of the disc 30 are a swirl chamber 33, inlet slots 39 to 42, wherein only the inlet slots 39 and 41 can be seen, and a feed ring 37 is formed. The inlet piece 53 has two inlet passages 59 and 61, these passage openings 59 and 61 forming a passage to the feed ring 37.

Example:

Silver nitrate was added in excess to the precursor hexamethyldisiloxane (HMDSO) - that is, more silver nitrate was added than can dissolve in HMDSO - and stirred together. After stirring, a sediment formed. Subsequently, the liquid supernatant (solution) was fed to a pressurizable antechamber, which was mounted in front of a nozzle according to the invention or inventively preferred, and pressurized by means of argon. The pressure difference with respect to atmosphere was about 2 bar. In the coating chamber, a low-temperature plasma was ignited, in which the solution was injected through the nozzle. The thus activated precursor compound hexamethyldisiloxane (HMDSO) was deposited together with silver nitrate, in particular with the silver ions, on the surface to be coated, preferably a silicon wafer. The resulting coating contained about 1 atom% of silver and could be represented by choice of the plasma gas either polymer-like or as a hard material layer.

The amount of silver in the precursor compound hexamethyldisiloxane (HMDSO) can be increased by additionally using an HMDSO miscible solvent which dissolves silver nitrate better than HMDSO, and this mixture is injected through the nozzle into the coating chamber.

Claims (13)

Method for coating at least one surface of a two- or three-dimensional body, the method comprising the following steps: a) providing a liquid medium containing at least one precursor compound, b) providing a coating chamber having a two- or three-dimensional body to be coated and a plasma generating device, wherein a pressure of less than 1 bar is present in the coating chamber, c) introduction of the liquid medium containing at least one precursor compound without carrier gas by means of a nozzle into the coating chamber, d) activating the at least one precursor compound and / or at least one surface of the two- or three-dimensional body by means of a low-temperature plasma generated by the plasma-generating device, e) depositing the at least one, preferably activated, precursor compound on at least one, preferably activated, surface of the two- or three-dimensional body, and f) obtaining a coating on the at least one surface of a two- or three-dimensional body. The method of claim 1, wherein the liquid medium containing the at least one precursor compound is introduced in the form of droplets, wherein at least 90% of all droplets have a diameter of 100 μm or less. The method of claims 1 or 2, wherein the liquid, the at least one precursor compound-containing medium is present in an antechamber of the nozzle, wherein in the prechamber a pressure of more than 0.5 bar and the liquid, the at least one precursor compound containing medium Opening a valve is introduced into the coating chamber by means of the nozzle. Method according to one of the preceding claims, wherein the liquid medium containing the at least one precursor compound is atomized by means of ultrasound and is introduced through the nozzle into the coating chamber. Method according to one of the preceding claims, wherein the nozzle has a swirl chamber. Method according to one of the preceding claims, wherein the liquid medium containing the at least one precursor compound is introduced into the coating chamber without the generation of vibrations. Method according to one of the preceding claims, wherein a pressure of less than 800 mbar is present in the coating chamber. Method according to one of the preceding claims, wherein the low-temperature plasma has a maximum temperature of 200 ° C (based on the neutral particles and / or the ions of the plasma). Method according to one of the preceding claims, wherein the low-temperature plasma is generated by capacitive or inductive coupling, microwaves, direct current or dielectrically impeded discharge. Method according to one of the preceding claims, wherein the liquid containing at least one precursor compound as a precursor compound by the low-temperature plasma activatable monomers which after depositing according to step e) on the surface of the two- or three-dimensional body to a polymeric, polymer-like or hard material Coating react. Apparatus for coating at least one surface of a two- or three-dimensional body, preferably for carrying out a method according to one or more of claims 1 to 10, comprising (i) a coating chamber having a low temperature plasma generating device and in which a pressure of less than 1 bar may be present, and (Ii) a nozzle which is suitable for introducing a liquid, at least one precursor compound containing medium without carrier gas in the coating chamber, wherein in the coating chamber, a pressure of less than 1 bar is present. Coated surface of a two- or three-dimensional body produced by a method according to one or more of claims 1 to 10. The use of a carrier gas-free introduction of a liquid medium containing at least one precursor compound into a coating chamber, wherein the coating chamber has a pressure of less than 1 bar and a low-temperature plasma generating device for homogeneously coating at least one surface of a two- or three-dimensional body.

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