For fabricating a plasma polymer coating of the atmospheric pressure plasma method

Mode of execution

For deposition plasma polymer layer

According to the present invention 1st in the method of claim 1 of the present invention defined in the general part. The preferred embodiment is dependent claims 2 to 7 and 26 and features 2 to 15 and 45 to 53 of the theme.

According to the present invention 1st in the atmospheric pressure plasma method is characterized in that the metal deposit on the substrate in the plasma polymer layer.

Atmospheric pressure plasma

Also known as the AD plasma or atmospheric pressure plasma of "atmospheric pressure plasma" means as follows plasma, that is, at this moment the pressure almost equal to atmospheric pressure. C. the and others in the "atmospheric pressure plasma: recalling" (SpectrochimicaActa Part B: Atomic Spectroscopy, 2006, article 2 - 30 page) illustrates an overview of the atmospheric pressure plasma.

In the atmospheric pressure plasma polymer layer deposited on a metal substrate surface to allow the method of the invention is very simple and cheap to implement, because does not need to low-voltage device such as like the low-pressure chamber, a vacuum pump, the vacuum valve and the like, and reduces the burden on the process control of the craft.

The performance of the plasma polymer layer depends mainly on the deposition conditions. The atmospheric pressure plasma deposition of polymer layers containing only in the use of oxygen and nitrogen-containing coating precursor compound of oxygen and nitrogen. With the ambient atmosphere through the re-reaction, in the low-pressure deposition of the plasma polymer layer can also prove that the immediately preceding a small amount on the surface of the . But concentration is lower than the plasma polymer layer is deposited under the circumstances of the atmospheric pressure. In addition, observed at atmospheric nitrogen enters into the plasma polymer layer. In the low-pressure deposition of the plasma polymer layer, nitrogen access only in the use of nitrogen as the process gas at a time and in general compared with atmospheric pressure plasma polymer layer deposition of less extent. Because of the plasma polymer layer in the oxygen and nitrogen-containing functional group contribute to its reactive and reflects the role, so the atmospheric pressure plasma process is advantageous.

According to the present invention in the 1st in the method of producing the electrode is means atmospheric pressure plasma component, at least for the time being used as the starting point or the discharge wire. In the method of the invention may be employed in the same material or different materials of the plurality of electrodes. Discharge is preferably such arc discharge.

In principle, in the plasma in the plasma region and relaxation is divided into active plasma region.

Active plasma zone generally refers to such a plasma of the body region, which is located in the following volume, the volume defined by the electrode, voltage is applied between the electrodes, thereby generating plasma. In the active plasma zone with free electron and ion.

Relaxation plasma region is located outside the defined by the activation of the electrode. Plasma relaxation area is also referred to as "afterglow" area. In the relaxation does not exist in the plasma area or only a small quantity of the free electron and ion, but is activation of atom or molecule. Therefore, relaxation the plasma area outside the region is located inside the discharge, the discharge is preferably electric arc or types of arc discharge. The invention in the sense of such arc discharge is for example as follows arc, beyond its long-term lighting, for example like pulse arc. In other words, in this terminology used "arc" can also cover cannot be long-term lighting of the arc if the pulse arc. In the plasma in the spray nozzle, atmospheric pressure plasma relaxation area is in the area of the outflow-side active area (i.e. close to the plasma nozzle outlet of the beginning of the electrode).

According to the present invention carried out in the 1st in the method of the coating precursor compound into the relaxation of the plasma in the region.

The process gas

Nitrogen gas or synthesis gas according to the present invention is used as the process gas, in order to maximize the plasma nozzle is not oxygen-containing atmosphere, thereby the basic prohibition of the coating precursor compound combustion and too strong fragmented. The invention in the sense of synthesis gas means a reduction function by the nitrogen or argon and hydrogen of the gas mixture. The process gas is fed into the through the pipeline for generating an atmospheric pressure plasma device in particular plasma nozzle. In order to further reduce the relaxation in the oxygen concentration of the plasma area, preferably also around the plasma nozzle export by inert gas generation coated jet.

Plasma nozzle

In the method of the invention in the plasma is preferably plasma jet. Plasma jet can be generated by the plasma nozzle. In the atmospheric pressure plasma in this method is preferably generated by the atmospheric pressure plasma nozzle. The basic structure of the plasma nozzle such as the following with reference to Figure 1 described in detail. Plasma nozzle 6 has an electrically conductive shell 21, the shell preferably is strip-shaped, in particular in the shape of a tubular form. The shell forms the process gas flows through the nozzle channel 22. In the nozzle channel preferably is coaxially set on the electrode 23. The dielectric material of the tube 24 such as the ceramic tube is loaded into the nozzle channel 22 in. By means of the high-frequency generator 25, the electrode between the shell and the load voltage. The process gas 20 via the pipeline 26 is input nozzle channel, preferably in such a manner that the exact said, it to spiral flow through the channel. This process gas flow can be through the screw mechanism 27 to obtain. In this, it may be provided with a plurality of holes in the plate.

In the atmospheric pressure plasma nozzle in operation, plasma discharge 28 such as the type of arc discharge self-intermediate electrode 23 basic along the tip of the nozzle channel 22 to the axial line of the pair of electrodes 29, like the casing of the electrolytic 21 ground. Therefore, plasma jet 40 direct the nozzle outlet 30 below injection. As a result, the plasma nozzle in operation of the nozzle opening is below the "flame" more than forty generated plasma jet. In principle, in the method of the invention may be employed in any of the plasma nozzle. Preferably adopt the Plasmatreat Company (Germany shi tan haagen) Plasma of System.

Atmospheric pressure plasma of relaxation area may also be referred to as afterglow area and located outside the defined limit by the electrode.

Therefore in Figure 1 in, plasma jet 40 of relaxation area is located at the outlet of the nozzle 30 and the substrate 1 between.

In a particularly preferred embodiment the plasma nozzle, includes the following components:

To form a process gas flowing through the shell of the nozzle channel, the nozzle channel arranged in the electrode, counter electrode, for the electrode and the counter electrode is close to the voltage between the left outlet of the shell in order to form the plasma jet of the high-frequency generator, the electrodes and the outlet of the nozzle channel is arranged between the inner and having a grid structure in the coating nozzle head, and is used for the evaporation of the at least one organic coating precursor compound is fed into the nozzle head in the plasma relaxation in the region of the plasma jet in the mechanism.

In another preferred embodiment, the housing itself is arranged in the channel of the nozzle relative to the electrode to the electrode.

In the sense of the present invention high-frequency is in the 100 Hz to 1 MHz, preferably 1 to 100 kHz, more preferably 10 to 40 kHz is within range of the frequency. Therefore, according to the invention can use the high-frequency generator within this frequency range operation.

In another preferred embodiment, the multi-part type coating nozzle head, it includes for blocking the electric arc or types of arc discharge into the lower portion of the coating spray nozzle head in the mechanism. According to the invention can be used, including such a mechanism of the multi-part type coating nozzle head such as in Figure 2 and Figure 5 is shown in and as described below.

For blocking the electric arc or arc discharge into such mechanism is the following mechanism, it shielded electric arc or types of arc discharge. For blocking the electric arc or through such arc discharge into the mechanism, can be basic-blocking plasma of part of the main potential, in particular activated electric arc (plasma active active area). For blocking the electric arc or arc discharge into such mechanism preferably with the multi-part type coating to the inside of the nozzle head to form together with the shielding member, more preferably form a Faraday cage. The invention in the sense of the shield is as follows mechanism, it has at least 50 dB, preferably at least 70 dB, more preferably at least 110 dB of attenuation. A common attenuation measurement method such as is standard IEEE - STD299.1 - 2013.

With the grid structure in the coating of the nozzle head in the final report BMBF item of "plasma jet coated to improve the printed circuit board and the OLED reliability the applicability of the basic research" (paragraph 25 page) are outlined. Through the internal grid structure, coating of the nozzle head can be basic-blocking plasma potential of the main components, in particular the active arc (plasma active active area). Different from the common plasma nozzle, the coating nozzle head allows the direct in the plasma nozzle head at will or in the heat-sensitive organic coating precursor compound into the basic potential-free relaxation in a plasma. Therefore, in the with the adoption of the grid structure in the coating nozzle head can be obtained under the condition that the organic coating precursor compound in the plasma jet in the activation of the basic non-destructive and efficient.

According to the invention can preferably be used in the grid structure with the nozzle head of an embodiment as shown in Figure 2 schematic is shown. In this are shown, nozzle head 60 by an inner 70 and outer part 80 a. The inside 70 with inner grid structure at the exit 100. The inner grid structure 100 has a plurality of openings or holes. The inside 70 interception arc. Arc therefore preferably is kept in the activity in the active region, the active plasma zone. Outer part 80 with the inside 70 together form around the gap 90, evaporation of such as gaseous coating precursor compound 120 is sent into this around the gap in the body and then directly in the grid structure 100 below and enter into the plasma relaxation area 110. Then, containing activated coating precursor compound gas nozzle outlet 30 away from the nozzle head 60. The vertical plasma jet 40 direct the nozzle outlet 30 below injection.

In this another aspect of the invention, the formed by the inner part and outer part of the multi-part type coating nozzle head. The multi-part type coating nozzle head 60 of an embodiment as shown in Figure 5 in schematic is shown. The inside 70 in the lower end of the outlet. The outlet of the electric arc or with intercept such arc discharge internal structure 200. Electric arc or types of arc discharge by the preferred keeping in active in the active region, namely in the inside 70 above the active plasma zone. Outer part 80 with the inside 70 together form a surrounding gap 90, evaporation such as gaseous coating precursor compound 120 is sent into this gap, the inner part of the subsequently directly below (downstream) enters into the plasma relaxation area 110.

Then, containing activated coating precursor compound gas nozzle outlet 30 away from the nozzle head 60. The vertical plasma jet 40 direct the nozzle outlet 30 below injection. In the nozzle head in the nozzle head is divided by 70 and outer part 80 to form a volume 90 also known as the input area. The inner portion 70 at the lower end of the outlet is thus is to input area 90 of the transition.

In the nozzle head 60 is divided into 70 (outlet) at the lower end of the inner structure 200 is used for blocking the electric arc or types of arc discharge into the input area 90 of the mechanism. The mechanism can be basic-blocking plasma or activated potential major components or the average potential major components, thus in the input area 90 within the nozzle head 60 there are basic in potential-free relaxation of plasma. This allows the organic coating precursor compound in nozzle head 60 in the plasma jet 40 in the activation of the basic non-destructive and efficient.

In a preferred embodiment, the nozzle head is divided into 70 the inner part with the 70 at the outlet of the electric arc or intercept such arc discharge internal structure 200 is formed with a shield, more preferably the Faraday cage. The invention in the sense of the shield is as follows mechanism, it has at least 50 dB, preferably at least 70 dB, more preferably at least 110 dB of attenuation. Common for determining attenuation measurement method such as is standard IEEE - STD299.1 - 2013.

In the nozzle head 60 is divided into 70 at the outlet of the electric arc or as for blocking such arc discharge into the input area 90 of the mechanism internal structure 200 can be the inner grid structure as described above, the pore structure that with a plurality of openings or holes of the structure, preferably through the edge is divided into 70 outlet of constrictions or insulator. If the interception arc or arc discharge is such the structure of the insulator such as aluminum oxide, is discharge in the nozzle head in the region of the upper part of the insulator. The insulator includes at least one hole, plasma jet through the hole can be run out to the input area. The insulator also can be the gas. Therefore, through the downwardly-extending nozzle head to cause the coating precursor compound into the location far away from the discharge region, thus the electric arc or types of arc discharge cannot reach into the location. This can also be so to do, in the lower part of the sleeved on the nozzle head of one of the tube, and the impurities in the tail end of the tube. In this case, can play the role of the insulating gas volume in the inside of the larger 70 between the with the outer end of the tube.

The deposition of the plasma polymer layer

The following reaction steps can lead to the deposition of the plasma polymer layer:

In the 1st step, is sent into the plasma relaxation area in the organic coating precursor compound molecule is plasma activation. In the nitrogen atmosphere of organic coating precursor compound into the plasma relaxation area in this has resulted in the activation of the coating precursor compound, without over-strong molecular crushing. In addition, into the plasma relaxation area can reduce undesirable crushing molecular oxidation into carbon monoxide or carbon dioxide. In the plasma relaxation area in some nitrogen atmosphere also reduces the oxidation. The organic coating precursor compound of activating molecules can be in the gas phase reaction with other particles. In the is fed to the surface of the substrate after the adsorption on the surface of the substrate. Activating molecules can be further on the substrate surface with the adjacent particle reaction, thereby appearing a plasma polymer layer. Through the gas phase particle collision or particle collision can realize the additional activation of the surface of the substrate.

In order to obtain the desired plasma polymer layer, the scope of the invention proved advantageously adopts the pulse discharge, its main power consumption in 50 to 4000 watts, preferably 100 to 2000 watts, particularly preferably 150 to 1500 W.

The metal substrate

The invention in the sense of the metal substrate in particular as follows solid, its main (namely>50 weight %) containing metal, preferably containing at least 90 weight %, more preferably at least 95 weight %, more in particular at least 99% of the weight of the metal of the solid. This/these metal can also be in the form of a metal alloy. The metal substrate is preferably a metal film. The metal base material and in particular to metal film in particular is preferably made of copper, silver, iron, nickel, cobalt and aluminum. The most preferred metal substrate is aluminum and copper film. The metal coating and in particular aluminum and copper film preferably by rolling or electrolytic manufacturing. The surface of the metal substrate can be in the plasma polymer layer prior to said deposition by the plasma cleaning or chemical cleaning. Therefore, in the metal on the surface of substrate can be by means such as west scale solvent such as isopropyl alcohol is removed. In addition, the metal substrate surface such as by chemical pre-treatment (such as pickling) or plasma pre-treatment is placed in order to better binding to the reactive state to be deposited on the plasma polymer layer.

The organic coating precursor compound

Because as stated above in the method of the invention can be to basically into the organic coating precursor compound, so the performance of the plasma polymer layer in the organic coating depends on the choice of the precursor compound.

Unexpectedly has been observed, according to the method of the invention the deposition of the plasma polymer layer to a certain extent in the preserved in organic coating precursor compound containing the functional group of the (see examples). This has caused according to the method of the invention the plasma deposition of a layer of chemical remaining reactive or potential reactive. Assuming that the functional group reactive to the remaining plasma polymer layer of good adhesion.

Unexpectedly has been observed, according to the method of the invention the deposition of the plasma polymer layer in the presence of double bonds in the conjugated double bond, such as by means of the infrared spectrum wider demonstrated (see Figure 3 and Figure 4). Wave number in 1640 - 1680 cm^-1 Within the scope of the band can be correspondent to the C=C double bond. The general, non-conjugated C=C double bond with IR can be shown to be weaker. In addition, the conjugated double bond the band usually toward the lower wave number (cm^-1 ). In the 3300, 1700 and 1050 cm^-1 Within the scope of the plasma polymer layer band that exist in the . In 2940, 1410 and 1340 cm^-1 The lower presents obvious C - H - vibration that had been deposited organic plasma polymer layer and is coated precursor compounds in the relaxation in the plasma and the direction of the crushing difference, because in this retained precursor compound under the same vibration, even if there are very weak.

Infrared spectrum measurement by means of the hereinafter referred to as the infrared reflection-absorption spectroscopy IRRAS sample technology to carry out. IRRAS is used for thin film non-destructive of the brominated sample technology and is completely the reflection infrared spectroscopy of a mixed form.

Plasma polymer layer by Brooker Company of infrared spectrum "Equinox55" type IR spectrometer to measure. In this, the measuring method in the IRRAS 32° angle reflection and 700 - 4000 cm^-1 The wave number of the cases to 32 scan mode application with 600 nanometers of PVD copper plating of copper on the wafer. The invention in the sense of PVD copper is characterized in that the depositing copper physical vapor deposition (physical vapor deposition PVD).

The organic coating precursor compound of the infrared spectrum can be by means of the ATR spectroscopy in liquid phase measurement. ATR (attenuated total reflectance) - spectroscopy is infrared spectroscopy measurement method, it is also suitable for the liquid sample.

It is assumed that the active material attached to the surface of the metal substrate of the plasma polymer layer on the unexpected high durability due to the plasma polymer layer suitable coefficient of thermal expansion. A conjugated double bond is with alternating double bonds and single-key system. Only has one double bond or has a plurality of double bond but wherein there is more than one double bond or single bond in the system between the known as non-conjugated or separated.

Supposes states double bond has caused the stated layer of higher conductivity and then the electrode in the of low contact resistance. It is also assumed that the states the duplet bond because of its high chemical reactivity contribute to the invention plasma polymer layer of good adhesion.

According to the following unexpected discovery, according to the method of the invention that the deposition of the plasma polymer layer nakayasu leave organic coating precursor compound of a part of the functional group, so also can utilize the comprises a double bond and a conjugated π electron system coating precursor compound.

The organic coating precursor compound selected in , the group is composed of ring-shaped polymers functionalized hydrocarbon and having at least one functional group of a hydrocarbon compound. The at least one functional group is one of the following groups: hydroxyl, carbonyl, carboxyl, amino, carbon - carbon multi-multiple bonds, carbon - nitrogen multi-multiple bonds and nitrogen - nitrogen multi-multiple bonds.

According to one aspect of the invention, with at least one functional group of the hydrocarbon is provided with at least one functional group of the non-ring hydrocarbon compound, the functional group is selected from C - C double bond, triple bond Tcn C - C and carbonyl, or has at least one functional group of the annular hydrocarbon, the tube can be selected from the group C - C double bond, triple bond Tcn C - C, carbonyl, hydroxyl and amino.

Selected from C - C double bond, triple bond Tcn C - C, carbonyl, hydroxyl and amino functional group of the at least one annular hydrocarbon can be aromatic or non-aromatic compound, and is preferably a non-aromatic compound, more preferably has at least two C - C double bond and/or cyclic non-aromatic compound.

For example, annular non-aromatic compound can be a by-product, phellandrene, limonene, terpene or quinone.

A non-circular hydrocarbon is preferably has at least one C - C triple bond Tcn and/or at least two C - C double bond of the hydrocarbon, more preferably acetylene or squalene.

According to the another aspect of the invention, organic coating precursor compound is a heterocyclic compound. Heterocyclic compound is preferably with heteroatom substituted or non-substituted 5 ring or 6 ring, heteroatom elects from the oxygen, nitrogen and sulfur group, more preferably non-aromatic compounds. More preferably tetrahydrofuran, tetrahydrothiophene, piperidine, pyrrolidine, 2, 3 - dihydrofuran, 2, 5 - dihydrofuran, 2, 3 - dihydro thiophene, 2, 5 - dihydro thiophene, 1 - pyrroline, 2 - pyrroline and 3 - pyrroline.

In a preferred embodiment, the at least one organic coating precursor compound is evaporated and the evaporation under the shape is sent into the relaxation of the plasma in the region. In a preferred embodiment, the at least one organic coating precursor compound is evaporated to gas and the form of the mixture and the inert gas is preferably nitrogen together with the relaxation is fed into the plasma in the region.

When using more than one type of organic coating when the precursor compound, they can in a preferred embodiment the form of the mixture is in common into the relaxation plasma.

When using more than one type of organic coating when the precursor compound, can be in another preferred embodiment different kinds of organic coating precursor compounds are respectively in different parts of the into the relaxation in the plasma. These organic coating precursor compound in this with the more sensitive (broken) but in the downstream is sent into the relaxation in the plasma, in order to obtain their respective organic coating precursor compound in the plasma jet in the basic non-destructive high-efficient activation. This means that, not too sensitive coating precursor compounds preferably in closer to the front (the more upstream) is introduced into a relaxation in a plasma, more sensitive coating precursor compound is preferably in the to the rear (more downstream) is sent into the.

The organic coating precursor compound is preferably a naphthenic, terpene or cyclic hydrocarbons, it contains at least one amino and/or hydroxy. The coating precursor compound more preferably limonene, cyclopentanol, cyclooctane or 1, 5 - cyclooctadiene. The organic coating precursor compound can include aromatic or conjugated π electron system.

Because the silicon-containing coating precursor compound in the atmospheric pressure plasma deposition under the condition of electric insulation of the plasma polymer layer, so that the at least one organic coating precursor compound on its total atom number preferably comprises less than 10% silicon, more preferably less than 5% of silicon. In a particularly preferred embodiment, organic coating precursor compound does not contain silicon.

Plasma polymer layer

Deposition on the metal substrate of the plasma polymer layer preferably has a conjugated multi-multiple bonds, resulting in plasma of the polymer strong conductivity, so as to cause the low contact resistance. Plasma polymer layer is preferably conjugated multi-multiple bonds carbon - carbon, carbon - nitrogen or nitrogen - nitrogen double bond or triple bond Tcn.

According to the present invention 1st of the coating can also be carried out in a plurality of coating cycle.

In order to improve the anti-aging protection, the layer can be by spraying the process between the single coating cycle is added corrosion inhibitor. Corrosion inhibitor is added to prevent the rust on the metal surface. Suitable corrosion inhibitor such as benzotriazole, tolyl triazole, benzimidazole, borax, sodium benzoate, molybdate, nitrate, nitrite, silicate, phosphate and organic phosphorus compounds and the above-mentioned compound solution and the mixture. The deposition of the plasma polymer layer can also be under DE102009048397A1 metal particle deposition carried out in combination.

Including metal substrate and plasma polymer layer of the article

According to the present invention 2nd goods in includes having the surface and on the surface of the plasma polymer layer and is characterized in that the metal substrate, the plasma polymer layer comprises a conjugated multi-multiple bonds, in particular double bond and triple bond Tcn, more in particular to a double bond. The preferred embodiment is dependent claims 10 to 13 and set of 18 to 25 and 54 of the theme.

The invention in the sense of the plasma polymer layer is in the plasma or by means of plasma deposition of a polymer layer, the polymer layer in particular has the strongly bonded through a covalent bond. According to the present invention in the 2nd goods in plasma polymer layer preferably comprises a carbon - carbon, carbon - nitrogen or nitrogen - nitrogen double bond or triple bond Tcn especially double bond.

According to the present invention 3rd goods in includes having the surface and preferably on the surface of organic plasma polymer layer and is characterized in that the metal substrate, the plasma polymer layer deposited under atmospheric pressure. The preferred embodiment is dependent claims 10 to 13 and features 18 and 20 to 25 and 54 of the theme.

The following description according to the present invention not only relates to the goods in 2nd to 3rd also according to the present invention in the preferred embodiment of the article.

Plasma polymer layer is preferably organic. Organic compound in the invention in the sense referred to as usual. In other words, it is a carbon-containing compound, in particular hydrogen bond with carbon - carbon-containing compounds. In order to obtain the conductivity of the plasma polymer layer, according to the present invention in the 2nd and 3rd in articles in the plasma polymer layer on the atomic total containing preferably less than 10% silicon, more preferably less than 5% of silicon. In a particularly preferred embodiment, plasma polymer layer is not containing silicon.

The plasma polymer layer is preferably away from the surface of the substrate which includes the functional group. In a preferred embodiment, the plasma polymer layer on the surface of the facing away from the substrate, at least 10% of the surface atoms with oxygen-containing functional group. Deposition analysis can rely on the X-ray photoelectron spectroscopy (XPS) to carry out. The recorded signal can be used for the functional groups of the XPS analysis of the fitting function and therefore is quantized.

On the one hand, high carbon content is advantageous, because carbon - carbon multi-multiple bonds is different from the oxygen place can form a conjugated double bond system, it may contribute to the plasma polymer layer of high conductivity. On the other hand, a certain amount of oxygen is advantageous, because the atom because of its high with the electronegative and forming reactive functional group may contribute to the plasma polymer layer adhesion strength. In the plasma polymer layer of carbon and oxygen in the ratio of the amount of supplies so that it is greater than 2. Plasma polymer layer composition preferably on its not hydrogen-containing total atom number comprises at least 50 and at most 90 atomic percent of carbon, at least 0 and at most 30 atomic percent oxygen, and at least 0 and at most 20 atomic percent of nitrogen.

The thickness of the plasma polymer layer is preferably less than 1 , more preferably less than 100 nm, most preferably less than 20 nanometers.

Plasma polymer layer in the layer thickness in the 10 - 100 nanometer circumstances preferably has in 2 - 50000 layer resistance of ohms, more preferably less than 35000 ohmic layer resistance, most preferably has less than 20000 ohmic layer resistance. The invention sense layer resistance of the corresponding to the impedance. The impedance is also known as the alternating current resistance. In the present invention, the impedance by means of electrochemical impedance spectroscopy in 0.01 Hz lower is determined. Electrochemical impedance spectroscopy to alternating voltage or alternating current as a function of a determined in the form of the impedance of the electrochemical system. Electrochemical impedance spectroscopy method is well known to the technical personnel and for example in Online are described in the on-line Encyclopedia (https://roempp.thieme.de/roempp4.O/do/data/RD - 09 - 00371).

Plasma polymer layer in the layer thickness in the 10 - 100 nanometer circumstances preferably has in 50 - 20000, more preferably 100 - 10000, most preferably in 150 - 5000 is within range of the dielectric constant. In the present invention, the dielectric constant by means of the electrochemical impedance spectrum in the 1 Hz to 10 kHz frequency range to determine.

According to the present invention in the 2nd and 3rd goods can be preferably by 1st in according to the present invention obtained by the method.

Electrode and a capacitor

According to the 5th aspect, this invention provides an electrode, the electrode comprises a metal substrate having a surface, on the surface of the metal substrate in the plasma polymer layer and in the plasma polymer layer facing away from the substrate on the surface of the layer containing the active material. The preferred embodiment is dependent claims 16 to 18 and the features 28 to 30 of the theme.

According to the 6th aspect, this invention relates to a capacitor, the capacitor includes a metal substrate having a surface, on the surface of the metal substrate in the plasma polymer layer and in the plasma polymer layer facing away from the substrate on the surface of the layer comprising the active material, wherein the plasma polymer layer according to the present invention in the 2nd to 4th in the at least one defined. The preferred embodiment is the features 32 to 34 of the theme.

The following description according to the present invention not only relates to the 5th aspect of the electrode, according to the present invention also relates to the use of the characteristic of the capacitor in the 6th and preferred embodiment.

The metal substrate

As the electrode or capacitor of the metal substrate, the substrate can be as described above. The metal substrate is preferably a metal film. By the copper, silver, nickel, cobalt and aluminum of the metal film is particularly preferred. The most preferred metal substrate is aluminum and copper film. For the aluminum and copper film preferably by rolling or electrolytic to manufacturing.

Plasma polymer layer

The plasma polymer layer in accordance with the according to the present invention best in 1st method to manufacture. The plasma polymer layer is preferably as this invention 2nd and 3rd defined in the plasma polymer layer.

Active material

The invention in the sense of the active material is means that the material of the electrode active material, their oxidation or reduction of storage or release ion. The preferred active material is lithium - transition metal oxide compound, for example as lithium iron phosphate (LiFePO₄ ), Lithium cobalt oxide (LiCoO₂ ), The spinel lithium manganese oxide (LiMn₂ O₄ ) Or lithium nickel cobalt manganese oxide (Li (NixCoyMnz) O₂ ). Lithium - transition metal oxide compounds can be in the reversible oxidation-reduction cycle in its reduction of reversibly ion and in the subsequent oxidation when the lithium ion is released. Lithium transition metal oxide - - compound can also be doped with other chemical elements and in particular other transition metal. The active material and more preferably is lithium nickel cobalt manganese oxide (Li (NixCoyMnz) O₂ ). In the present invention, lithium nickel cobalt manganese oxide also referred to as NCM. NCM advantageously used as battery unit or lithium ion battery cathode active material. Through the doping, compared with the lithium cobalt oxide has obtained in the charge-discharge cycle in more high thermal stability and better electrochemical characteristics.

The electrode manufacturing method and capacitor manufacturing method

According to the 7th aspect, this invention relates to manufacturing according to the present invention 5th in the method of the electrode. The method comprises the following steps: cleaning the metal surface of the substrate, the metal substrate is deposited on the surface of the plasma polymer layer, and in the plasma polymer layer facing away from the surface of the substrate is applied on the active material, characterized in that the plasma polymer layer deposited under atmospheric pressure. The preferred embodiment is dependent claims 21 and 22 and the features 36 to 38 of the theme.

According to the 8th aspect, the invention is directed to a method of manufacturing according to the present invention 6th aspects of the method of the capacitor. The method comprises the following steps: cleaning the metal surface of the substrate, the metal substrate is deposited on the surface of the plasma polymer layer, in the plasma polymer layer applied on a surface opposite to the substrate of the active material, characterized in that the plasma polymer layer deposited under atmospheric pressure. The preferred embodiment is the features 40 to 42 of the theme.

The following description according to the present invention not only relates to the 7th aspect of the method according to the present invention also relates to the 8th in the characteristic of the method and of the preferred embodiment.

Dispersion

The active material preferably in the form of dispersion conditioning in particular suspension is applied to the plasma polymer layer facing away from the surface of the substrate. In addition to the active material outer, dispersion body also can be included with an additive, solvent or adhesive. The choice of mixing and dispersion order to be made to coordinate with the electrode design. Drying of the solid component in the solvent and the binder can be added front is pre-mixed. Thus obtained dry mixture may be added after the solvent is dispersed. In another aspect of the invention in one embodiment, the composition of the solid and liquid portion may also be in the absence of the first pre-mixed dry composition under certain conditions in one step is disseminates. Dispersion conditioning can be used coating tool such as the slot nozzle, scraper, the anilox roller and to exert.

Active material

The preferred active material is lithium transition metal oxide - - compound, for example as lithium iron phosphate (LiFePO₄ ), Lithium cobalt oxide (LiCoO₂ ), The spinel lithium manganese oxide (LiMn₂ O₄ ) Or lithium nickel cobalt manganese oxide (Li (NixCoyMnz) O₂ ). The active material and more preferably is lithium nickel cobalt manganese oxide (Li (NixCoyMnz) O₂ ). The active material preferably in order to powder form to use in order to improve the dispersion.

The calendering and drying

In the method a in the preferred embodiment, the active material is applied by calendering and drying the object after further processing.

After the coating, the coated substrate can be dried. Drying for example can be the air (especially dry air) or preferably carried out in an inert gas atmosphere. Generally, the gas mixture can be chosen as is suitable for drying. Drying can be under the normal pressure condition or they may be under low pressure in the static attitude or dynamic in vacuum. During the drying, by supply of heat away from the substrate in the solvent, and the solvent can be recovered or is supplied to a heat application. Drying is preferably provided for the drier. Drying machine can in order to achieve the single temperature distribution is divided into different temperature zones. After passing through the dryer can be film cooling to the room temperature.

When the calendering, the coated substrate for example by one or more of the rotation of the roll pair is consolidated (rolls extends). Compacting can be carried out through the upper and lower. The roll pair to generate accurate prescribed line pressure, thereby can adjust the porosity of the coated substrate. For obtaining having a predetermined porosity of predetermined surface structure, a constant line pressure is important, which in turn is decided in the roller of the surface condition and round the processing precision.

After the calendering can be subjected to further drying, preferably under the condition of vacuum.

The battery unit and the lithium ion battery

According to the present invention 9th aspects, the invention relates to a battery unit, including according to the present invention in the 5th of the electrode.

The invention final aspect relates to a lithium ion secondary battery, which comprises according to the invention in the 5th of the electrode.

Battery and lithium ion battery preferably includes at least one cathode, at least one anode and the at least one electrolyte. Included in the battery and lithium ion in the accumulator according to the 5th in the electrode preferably is the cathode. The following description is used for manufacturing according to the invention of the last two aspects of the battery unit and the lithium ion battery of the embodiment. As a cathode electrode according to the 5th in the middle layer and the anode stack or wound into a single battery. In the stacking process, the electrode film in order to re-circulation mode by the anode, the separation membrane and the cathode stack. When the winding, by a separating film with, a anode with, a separating film with and a cathode with produce by the overlap of a roll of the tape. Then, so manufactured material is fed into a package placed in the filling with the electrolyte.

As the anode material, preferably graphite and similar carbon, nano silicon, lithium titanate or tin oxide. Generating lithium graphite and similar carbon is a particularly preferred anode material.

As the electrolyte, preferably dissolved lithium salt such as lithium hexafluorophosphate, lithium fluoborate four or two oxalic acid lithium borate. Dissolving at this moment in the anhydrous non-protic solvent such as ethylene carbonate, propylene carbonate, dimethyl carbonate or 1, 2 - dimethoxy ethane in. In addition, can be composed by polyvinylidene fluoride or polyvinylidene fluoride - hexafluoropropylene or lithium phosphate nitride of polymer as the electrolyte.

In the sense of the present invention cigarette ends is the following material, its space and electrically isolating the battery unit and the battery and the cathode and the anode in the unit, namely the positive and negative electrode separated. As cigarette ends, preferably adopt the microporous membrane such as a layer or layers of polymer film.

The features

The following, the invention various method embodiments of the sum up to the group.

(1) Used in the atmospheric pressure plasma deposition on the metal substrate in the plasma polymer layer, wherein the plasma passes through the between the electrodes of the discharge to produce, characterized in that at least one organic coating precursor compound is sent into the relaxation of the plasma in the plasma region and as the polymer layer is deposited on the metal substrate, wherein the nitrogen or synthesis gas is used as the process gas, and the at least one organic coating precursor compound selective , the group is composed of heterocyclic compound, annular polymers functionalized hydrocarbon and having at least one functional group of a hydrocarbon compound, the functional group selected from hydroxyl, carbonyl, carboxyl, amino, carbon - carbon multi-multiple bonds, carbon - nitrogen multi-multiple bonds and nitrogen - nitrogen multi-multiple bonds.

(2) According to the features (1) of the method, wherein the at least one kind of organic coating precursor compound in order to form the gas mixture with the inert gas is preferably nitrogen together with the relaxation is fed into the plasma in the region.

(3) According to the features (1) or (2) of the method, wherein the at least one kind of organic coating precursor compound is evaporated and in order to evaporate the shape is sent into the relaxation of the plasma in the region.

(4) According to the aforesaid features in at least one of the method, wherein the relaxation of the plasma discharge region is located outside, the discharge especially electric arc or types of arc discharge.

(5) According to the aforesaid features in at least one of the method, wherein the discharge is such arc discharge.

(6) According to the aforesaid features in at least one of the method, wherein the plasma is a plasma jet.

(7) According to the features 6 of the method, wherein the plasma jet generated by the plasma nozzle.

(8) According to the features (7) of the method, wherein the around the plasma nozzle of export by inert gas generation coated jet.

(9) According to the aforesaid features in at least one of the method, wherein the at least one kind of organic coating precursor compound on its total atom number comprises less than 10% silicon, preferably less than 5% of silicon, preferably does not contain silicon.

(10) According to aforesaid features in at least one of the method, wherein the at least one kind of organic coating precursor compound is naphthenic, terpene or cyclic hydrocarbons, it has at least one amino and/or hydroxy.

(11) According to the features (10) of the method, wherein the organic coating precursor compound is limonene, cyclopentanol, cyclooctane or 1, 5 - cyclooctadiene.

(12) According to the aforesaid features in at least one of the method, wherein the organic coating precursor compound comprises aromatic or conjugated π - su.

(13) According to at least one of the aforesaid claims a method, wherein the plasma polymer layer has conjugated multi-multiple bonds.

(14) According to the features (13) method, wherein the conjugated multi-multiple bonds is C - C, C - N or N - N double bond or triple bond Tcn.

(15) According to the features (1) to (14) in at least one of a method, in which a plasma nozzle, comprising the following components: to form a process gas flowing through the shell of the nozzle channel, the nozzle channel arranged in the electrode, the electrode, and the electrode for applying a voltage between the electrode and to leave the shell in order to form a plasma jet at the outlet of the high-frequency generator, said electrode and an outlet arranged in the channel between the nozzle of the grid structure and is provided with in the coating nozzle tip, is used for the evaporation of the at least one organic coating precursor compound is fed into the nozzle head in the plasma relaxation in the region of the plasma jet in the mechanism.

(16) Article, having a surface and the plasma polymer layer on the surface of the metal substrate, characterized in that the plasma polymer layer comprises a conjugated multi-multiple bonds.

(17) Article, having a surface and the plasma polymer layer on the surface of the metal substrate, characterized in that the plasma polymer layer deposited under atmospheric pressure.

(18) According to the characteristic (16) or (17) of the article, wherein the plasma polymer layer is an organic layer.

(19) According to the features (16) or (18) of the article, wherein the conjugated multi-multiple bonds is C - C, C - N or N - N double bond or triple bond Tcn.

(20) According to the features (16) to (19) in at least one of the articles, wherein the plasma polymer layer with its total atom number related to comprise less than 10% silicon, preferably less than 5% of silicon.

(21) According to the features (20) of the article, wherein the plasma polymer layer does not contain silicon.

(22) According to the features (16) to (21) in at least one of the articles, wherein the plasma polymer layer on the surface of the facing away from the substrate, at least 10% of the surface atoms with oxygen-containing functional group.

(23) According to the features (16) to (22) at least one of the articles, wherein the plasma polymer layer in the C: O the substance is greater than 2.

(24) According to the features (16) to (23) at least one of the articles, wherein the plasma polymer layer on its not containing hydrogen component of the total atom number comprises at least 50 and at most 90 atomic percent of C, at least 0 and at most 30 atomic percent of O, and at least 0 and at most 20 atomic percent of N.

(25) According to the features (16) to (24) at least one of the articles, wherein the plasma polymer layer utilizes according to the claim 1 to 16 of the method to obtain.

(26) Article, having a surface and depositing in the plasma polymer layer on the surface of the metal substrate, wherein the plasma polymer layer utilizes according to the features (1) to (15) of the method to obtain.

(27) Electrode, comprising a metal substrate having a surface, on the surface of the metal substrate in the plasma polymer layer and in the plasma polymer layer facing away from the substrate on the surface of the layer containing the active material.

(28) According to the features (27) of the electrode, wherein the active material is lithium iron phosphate (LiFePO₄ ), Lithium cobalt oxide (LiCoO₂ ), The spinel lithium manganese oxide (LiMn₂ O₄ ) Or lithium nickel cobalt manganese oxide (Li (NixCoyMnz) O₂ ).

(29) According to the features (27) or (28) of the electrode, wherein the plasma polymer layer according to claim 1 to 16 method can be obtained.

(30) According to the features (27) or (28) of the electrode, wherein the plasma polymer layer such as claim 17 to 25 at least one of the defined.

(31) Capacitor, which comprises a metal substrate having a surface, on the surface of the metal substrate in the plasma polymer layer and in the plasma polymer layer facing away from the substrate on the surface of the layer containing the active material.

(32) According to the features (31) of the capacitor, wherein the active material is lithium iron phosphate (LiFePO₄ ), Lithium cobalt oxide (LiCoO₂ ), The spinel lithium manganese oxide (LiMn₂ O₄ ) Or lithium nickel cobalt manganese oxide (Li (NixCoyMnz) O₂ ).

(33) According to the features (31) or (32) of the capacitor, wherein the plasma polymer layer according to claim 1 to 16 in at least one of the method can be obtained.

(34) According to the features (31) or (32) of the capacitor, wherein the plasma polymer layer such as claim 17 to 25 at least one of the defined.

(35) The manufacturing according to the features (27) to (30) of at least one of electrode method, comprises the following steps: cleaning the metal surface of the substrate, the metal substrate is deposited on the surface of the plasma polymer layer, and in the plasma polymer layer facing away from the surface of the substrate is applied on the active material, characterized in that the plasma polymer layer deposited under atmospheric pressure.

(36) According to the features (35) of the method, wherein the active material in order to dispersion conditioning, in particular in the form of suspended body to exert.

(37) According to the features (35) or (36) method, wherein the active material is lithium iron phosphate (LiFePO₄ ), Lithium cobalt oxide (LiCoO₂ ), The spinel lithium manganese oxide (LiMn₂ O₄ ) Or lithium nickel cobalt manganese oxide (Li (NixCoyMnz) O₂ ).

(38) According to the features (35) to (37) at least one of the method, wherein the active material is applied by calendering and drying the object after further processing.

(39) The manufacturing according to the features (31) to (34) of at least one of the method of the capacitor, comprising the following steps: cleaning the metal surface of the substrate, the metal substrate is deposited on the surface of the plasma polymer layer, and in the plasma polymer layer facing away from the surface of the substrate is applied on the active material, characterized in that the plasma polymer layer deposited under atmospheric pressure.

(40) According to the features (39) of the method, wherein the active material in order to dispersion conditioning, in particular in the form of suspended body to exert.

(41) According to the features (39) or (40) method, wherein the active material is lithium iron phosphate (LiFePO₄ ), Lithium cobalt oxide (L1CoO₂ ), The spinel lithium manganese oxide (LiMn₂ O₄ ) Or lithium nickel cobalt manganese oxide (Li (NixCoyMnz) O₂ ).

(42) According to the features (39) to (41) at least one of the method, wherein the active material is applied by calendering and drying the object after further processing.

(43) The battery unit, it include according to the features (27) to (30) in at least one of the electrode.

(44) A lithium ion secondary battery, which comprises the features according to (27) to (30) in at least one of the electrode.

(45) According to the features (1) to (16) at least one of the method, wherein the heterocyclic compound is a elects from the oxygen, nitrogen and sulfur group heteroatom substituted or non-substituted 5 ring or 6 ring.

(46) According to the features (45) of the method, wherein the heterocyclic compound is tetrahydrofuran, tetrahydrothiophene, piperidine, pyrrolidine, 2, 3 - dihydrofuran, 2, 5 - dihydrofuran, 2, 3 - dihydro thiophene, 2, 5 - dihydro thiophene, 1 - pyrroline, 2 - pyrroline or 3 - pyrroline.

(47) According to the features (1) to (16), (45) and (46) of at least one of method, wherein with at least one functional group of the hydrocarbon is provided with at least one functional group of the non-cyclic hydrocarbons, this functional group selection C - C double bond, triple bond Tcn C - C and carbonyl, or has at least one functional group of the cyclic hydrocarbon, this functional group is selected from C - C double bond, triple bond Tcn C - C, carbonyl, hydroxyl and amino.

(48) According to the features (47) method, which has at least one functional group of the ring hydrocarbon compound having at least two C - C double bond of the non-aromatic compound and/or ketone.

(49) According to the features (48) method, which has at least one functional group of the ring hydrocarbon compound is a by-product, philippine blue alkene, limonene, terpene or quinone.

(50) According to the features (47) of the method, wherein the non-cyclic hydrocarbon compound is acetylene or squalene.

(51) According to the features (1) to (16) and (45) to (49) at least one of the method, wherein the organic coating precursor compound is a heterocyclic compound or with at least one functional group of the cyclic hydrocarbon.

(52) According to the features (4) to (14) and (45) to (51) at least one of the method, wherein the use of the plasma nozzle, comprising the following components: to form a process gas flowing through the shell of the nozzle channel, the nozzle channel arranged in the electrode, counter electrode, for the electrode and the counter electrode voltage is applied between the leave the shell in order to form a plasma jet at the outlet of the high-frequency generator, in said electrodes and the outlet of the nozzle is arranged in the channel between the multi-part type coating nozzle head 60, wherein the coating nozzle with an outlet in the lower end of the head is divided into 70, outer part 80 and by the inner section 70 and outer part 80 is formed between the area of the 90 form, wherein in the inner portion 70 of the lower end of the outlet port includes as used for preventing the electric arc to enter or type of arc discharge to the input area 90 of the mechanism internal structure 200, and is used for the evaporation of the at least one organic coating precursor compound is fed into the nozzle head in the area of 90 in the plasma relaxation in the region of the plasma jet in the mechanism.

(53) According to the features (52) of the method, wherein the inner structure 200 is in the off-grid structure, inner hole structure, preferably by one edge of the inner portion 70 of the lower end of the outlet on the constrictions or insulator.

(54) According to the features (16) to (26) in at least one of the articles, wherein the plasma polymer layer in the 10 to 100 nanometer range in the case preferably has a thickness in the 2 to 50000 layer resistance of ohms, more preferably less than 35000 ohmic layer resistance of, and most preferably less than 20000 ohmic layer resistance of the, wherein the layer of resistance corresponds to an electrochemical impedance spectroscopy by means of in 0.01 Hz is measured at the impedance.

Examples

In the following, embodiments of the present invention combination.

In another example, in the use according to the present invention 1st in the method of manufacturing and to study the case according to the present invention 3rd and 4th aspects of the article.

With less than 1 micron thick layer of organic plasma polymer layer in relaxation plasma (afterglow plasma) in the atmosphere is deposited on the aluminum alloy as a substrate. For this adopts the Plasmatreat Company with the plasma nozzle atmospheric pressure plasma apparatus. The organic precursor compound (20 g/h cyclopentanol) in the evaporation under the state of 2 nL/min of nitrogen gas as the carrier gas from the outlet of the nozzle with 10 mm remote is sent into the plasma afterglow area. The moving speed of the nozzle is the velocity of movement of the nozzle relative to the substrate at this moment equal to 10 m/min. In this, can also be through the nozzle at the outlet of the nozzle by the coating of the inert gas jet. Plasma activation of the jet system through such arc discharge and in using nitrogen as the process gas (ionized gas, 29 nL/min) under the circumstances. By the substrate and deposited on plasma polymer layer of the article in the room atmosphere storage and subsequently showed that plasma characteristic of the polymer layer. The scope of the invention, unit "nL" representative . Standard liter under standard conditions corresponding to occupy the 1 liter volume of gas.

Coating the chemical composition of the X-ray photoelectron spectrum by means (XPS) (see table 1) is determined. The functional group of the XPS signal for the recording of the fitting function to analysis and therefore be quantified (table 2).

Table 1

Table 2

Table 1 shows, according to the method of the invention the deposition of the plasma polymer layer on the non-hydrogen total atomic mass comprises up to 63% of the carbon content. In addition, as high as 2.5: 1 carbon - oxygen of the organic coating that can substantially inhibit the oxidation of the precursor compound.

Table 2 shows that, according to the method of the invention the deposition plasma on the surface of the functional group having a large share quantity. Because the organic coating precursor compound comprises a hydroxy, so large share quantity hydroxyl groups and ether groups implies that in the plasma polymer layer after the deposition of the functional group has left a certain share quantity. The emergence of ether is possible because the two alcohol condensation and therefore also specified in the method of the invention in the stability of the functional group. The surface of the plasma polymer layer of functional contribute to the adhesion strength.

In another embodiment, according to the above-mentioned method, will have a 30 nanometer or 90 nanometer thick layer of organic plasma polymer layer in relaxation plasma (afterglow plasma) under the atmospheric pressure in the respectively deposited onto a as a substrate 600 nanometer thick copper layer on the wafer. As the front of the precursor compound is acetylene. The layer thickness by means of the ellipsometer at the same time on the deposited silicon wafer to determine.

So manufactured layer resistance of the layer according to the standard through the electrochemical impedance measurements to determine the, like in particular Online on-line Encyclopedia as described in (https://roempp.thieme.de/roempp4.O/do/data/RD - 09 - 00371, 2018 . 01.30 open). The measurement comprises the following respectively by the technical staff are familiar with the steps. First of all for producing plasma polymer layer to be studied as the contact medium of the conductivity of the test solution. Then carry on the absorption test and then by means of the electrochemical impedance spectroscopy test in the conductive substrate to be tested on the plasma polymer layer in the capacitance change. Followed by electrochemical impedance spectroscopy analysis in order to determine the resistance of the layer. The dielectric constant of the layer by means of ε will also be in the 1 Hz to 10 kHz frequency range determined electrochemical impedance spectrum. The results in table 3 is shown. The test of the dielectric constant of the plasma polymer layer value specified substrate with good combination of the plasma polymer layer and the shape of the curve of the measuring signal specified in the plasma polymer layer in the hole.

Table 3 (by three independent measurement value determined)