EP3727706A1 - Corps solides de polymère plasma, en particulier couche de polymère plasma avec formation de réseau d'hydrocarbures, leur utilisation et procédé de production de ceux-ci - Google Patents

Corps solides de polymère plasma, en particulier couche de polymère plasma avec formation de réseau d'hydrocarbures, leur utilisation et procédé de production de ceux-ci

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Publication number
EP3727706A1
EP3727706A1 EP18826575.5A EP18826575A EP3727706A1 EP 3727706 A1 EP3727706 A1 EP 3727706A1 EP 18826575 A EP18826575 A EP 18826575A EP 3727706 A1 EP3727706 A1 EP 3727706A1
Authority
EP
European Patent Office
Prior art keywords
plasma polymer
plasma
layer
polymer layer
solid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18826575.5A
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German (de)
English (en)
Inventor
Klaus-Dieter Vissing
Thorben BRENNER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Application filed by Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP3727706A1 publication Critical patent/EP3727706A1/fr
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2518/00—Other type of polymers
    • B05D2518/10—Silicon-containing polymers

Definitions

  • Plasma polymer solid in particular plasma polymer layer with hydrocarbon network formation, their use and process for their preparation
  • the invention relates to a plasma polymer solid, in particular a plasma polymer layer, wherein the lower limit of the modulus of elasticity of the solid or the layer is determined by a specific function, which applies to certain areas of the modulus and determined by means of certain C / O molar ratios XPS.
  • the invention further relates to the use of a corresponding plasma polymer solid or a plasma polymer layer and a process for their preparation.
  • Plasma polymers Thin films can be used not only as a dry release layer on forming tools, but also for equipping utility articles or machine parts in order to facilitate or facilitate their cleaning. Of particular interest are such properties for sensor products, sanitary ware products, food and pharmaceutical processing articles, as well as e.g. for shaping tools.
  • DE 100 34 737 discloses a process for producing a permanent mold release layer by plasma polymerization.
  • the coating is characterized by its gradient structure.
  • DE 102006018491 A1 discloses a flexible plasma polymer product with a PDMS-like layer structure and thus a soft and relatively sensitive product.
  • a concrete layer composition is claimed.
  • Information on the determination of the hydrogen content is not provided, as well as no information on the crosslinking situation or density determination is included.
  • there are general information on density and hydrogen content For the density of a range of 0.9 - 1 is 15 g / cm 3 specified. From this the expert concludes on a rather weakly networked layer system.
  • the H / C ratio ranges from 2.25 to 3 to 1.
  • information on the shift of the Si 2p peak in the XPS spectrum can be found. This value provides information about the close bond conditions of the silicon. Strong shift from PDMS is an indication of a high number of Si-O bonds.
  • the mechanical properties are described as elastic and crack-free extensible up to 50%. This is another indication that the coating is soft and could be referred to as a plasma polymer PDMS.
  • the total external leak rate should be less than 1% of the amount of oxygen fed to the process, as well as to ensure that the internal leak is kept small by residual water. A value for the total leak rate is not found.
  • the power required for the process is about 7.25 W / sccm. It is kept small in order to be able to achieve the mechanical properties of the layer and to ensure that the working regime moves in the vicinity of the precursor excess.
  • WO2015044247 A1 discloses a further development with regard to the mechanical properties. It describes a plasma polymer solid, which can be used primarily as a release layer in a mold.
  • the plasma-polymer solid is characterized by a high modulus of elasticity, the modulus of elasticity being dependent on the C / O ratio.
  • the surface energy and, as a consequence, the polar fraction thereof are low, but also clearly dependent on the modulus of elasticity.
  • the starting point is that the hardness of plasma polymer layers is influenced by the ratio of oxygen to organosilicon precursors in the plasma process and, as a result, the ratio of oxygen to carbon in the coating.
  • the teaching of this document is that it is possible, with a ratio of organosilicon precursor to oxygen of 2 to 1 by the variation of the power to increase the modulus of elasticity or the hardness without taking too much influence on the surface energy.
  • this circumstance can be recognized by the fact that the maximum position of the Si2p peak shifts to higher energy levels with increasing modulus of elasticity. This is a clear indication of a more pronounced Si-O network.
  • the total leak rate is given as less than 0.3 mbar l / s. This corresponds to a limit value of 17.75 sccm and is thus about 50% of the amount of oxygen supplied in the example.
  • the power required for the process can be deduced from the examples with values from 10.5 W / sccm.
  • the crosslinking network of organosilicon PE-CVD layers is a Si-O network which can be continuously modified starting from a PDMS-like layer so that an amorphous SiO 2 film is formed at the end.
  • a Si-O network which can be continuously modified starting from a PDMS-like layer so that an amorphous SiO 2 film is formed at the end.
  • more and more oxygen is incorporated into the coating and, in turn, hydrocarbons are removed.
  • silicon atoms which have two oxygen atoms in the immediate vicinity (secondary Si, PDMS) over an increasing number of tertiary and quaternary Si compound (3 or 4 oxygen atoms in the immediate vicinity) towards coatings with purely quaternary Si compounds ( S1O2).
  • the increased incorporation of oxygen into the network is achieved either by an increased supply of oxygen (in particular with a constant total amount of gas) and / or by increasing the plasma power, so that a stronger fragmentation takes place and the oxygen supply can be used by the silicon. If the surface energy and, with it, the polar content increases, then the easy-to-clean properties or the separation capacity are gradually lost because soiling or, in general, materials which come into contact with the surface increasingly adhere to the surface polarity.
  • This novel networking is independent of the existing Si-O network.
  • the additional crosslinking takes place via hydrocarbon bridges, primarily via CH2-CH2 bridges.
  • the overall Si-crosslinking level can be controlled independently of the Si-0 network and controlled by the power coupled into the plasma during deposition. It can be achieved a total degree of crosslinking of over 75%, as it is otherwise only achieved by a polar reference material such as polymethylsilsesquioxane.
  • This secondary crosslinking mechanism surprisingly provides for a significant increase in the E-modulus without having to incorporate additional oxygen into the layered network. Due to the additional crosslinking, the density of the coating increases significantly. It can reach values greater than 1.2 g / cm 3 and depends on the degree of crosslinking and thus on the coupled-in plasma power.
  • the coating Due to this novel network structure of the coating not only the E-modulus increases strongly, but the coating has a lower density than non inventive layers of the same modulus of elasticity, which essentially have only one Si-O network. Accordingly, with the same Si-O network, the layers according to the invention have a higher density than those of the prior art, which have no crosslinking via hydrocarbon bridges. Furthermore, the refractive index increases. Furthermore, it can be observed that the surface energy increases, but with only a very, very moderate increase in the polar fraction, since hardly any more OH groups or other polar groups are generated. Due to the increase in density, however, the disperse fraction of the surface energy increases: More molecules are available for the interaction with the test liquid.
  • the region of the feature window according to the invention is shown in FIG. 1 as a non-hatched region (1).
  • the hatched area (2) does not represent feature combinations according to the invention.
  • the significance of the features of the article according to the invention is only indirectly apparent to the person skilled in the art, therefore further explanations should be given here: it is surprising that the novel crosslinking mechanism allows the coatings according to the invention to to adjust the modulus of elasticity almost independently of the C / O ratio.
  • the surface energy and its polar content can be kept surprisingly small (Fig. 2 + 3).
  • Fig. 2 + 3 the high hardness of the layers / solids, it is possible to produce largely non-polar coatings. This is a significant advance over the prior art, especially if one additionally takes into account the position of the Si 2p peak maximum, which is now largely independent of the modulus of elasticity.
  • the position of the Si 2p peak provides information about the oxygen-containing near-bond conditions at the Si atom within the plasma polymer layer, which contains information about the Si-O network generated in the layer.
  • Low levels of Si 2p pollution indicate a low-oxygen Si environment. If it increases, the Si-O network is increasingly formed up to a Si0 2 -like network.
  • the formation of the Si-O network is dependent solely on the ratio of the organosilicon precursor to oxygen and, at the same time, hydrocarbon bridges form a second independent network. The latter manifests itself in a high C / O ratio and consequently low surface energy with very low polar contents.
  • the feature profile of the present invention shows that the layer properties are by no means based solely on the material composition, but are also essentially due to the nature of the layer crosslinking (and thus by the plasma polymerization conditions).
  • the C / O ratio and, parallel to this, the polar component of the surface energy in plasma-polymer layers have a significant influence on the surface properties (hydrophilicity, hydrophobicity) and, at the same time, the modulus of elasticity is largely independent of this.
  • Preferred according to the invention is a plasma polymer solid according to the invention, in particular a plasma polymer layer according to the invention, the maximum of the Si 2p peak at 102.5-102.8 eV being measured on the surface of the layer by XPS.
  • the complete overall atomic composition of the plasma polymer coating is determined by XPS (ESCA) spectroscopy and microelement analysis.
  • XPS XPS
  • FTIR spectroscopy
  • XPS spectroscopy must be operated at a high energy resolution to allow peak fitting of the Si 2p peak.
  • the four energy states of silicon for different oxygen states are conventionally fitted and evaluated.
  • the layers of the invention are characterized by a high content of secondary Si compounds. For definition and determination see Measurement Example 6.
  • the novel approach according to the invention also makes it possible to specifically influence the Si-C network so that layers are produced, which at a given C-0 ratio have a high modulus of elasticity without suffering any loss in terms of the polar component of the surface energy, or of the surface energy in general.
  • the relatively high modulus of elasticity is desirable to ensure a mechanical load capacity.
  • the surface energy and the polar fraction of the surface energy are determined according to Measurement Example 4.
  • FIG. 2 illustrates as a hatched area (1) the feature window due to the equations (3) and (4) as an E modulus versus surface energy.
  • the areas (2) do not represent preferred feature combinations.
  • FIG. 3 illustrates as hatched area (1) that by the equations (2) and (2a) conditional feature window E modulus against maximum polar portion of the surface energy.
  • a plasma-polymer solid or a plasma-polymer layer which has a density in the range from 0.8 to 1.6 g / cm 3 , preferably between 1..0 and 1.5 g / cm 3 .
  • the density is determined according to measurement example 5.
  • a plasma polymer layer in particular for use as an easy-to-clean layer or as a release layer is a plasma polymer layer, wherein the layer has a layer thickness of 5 nm to 20 pm, preferably 200 nm to 10 pm and more preferably 400 nm to 5 pm. With these layer thicknesses, production-related surface roughness can be covered particularly well.
  • a plasma polymer solid according to the invention in particular a plasma polymer layer according to one of the preceding claims, is preferred according to the invention, wherein the molar ratio H: C 2.0-3.0 is preferably 2.0-2.8, more preferably 2.2-2 , 7, measured by microelemental analysis.
  • the microelement analysis is performed in case of doubt, as described in Example 3.
  • the preferred H: C ratio for the solids or layers according to the invention makes possible a Si-C network which is preferred in the context of the invention, since salts which are not saturated by hydrogen are available for other (network-forming) bonds.
  • Preferred according to the invention is a plasma polymer solid according to the invention, in particular a plasma polymer layer, the molar ratios on the surface of the layer being measured by means of XPS C: 0 1, 3 - 2.5 and / or
  • a plasma polymer solid according to the invention in particular a plasma polymer layer according to the invention, where the following applies to the molar amounts on the surface of the layer measured by XPS:
  • Preferred according to the invention is a plasma polymer solid according to the invention, in particular a plasma polymer layer according to the invention, wherein the Si H band can be recognized in the FTIR spectrum at about 2165 cm -1. This band is an indication of good crosslinking by means of additional hydrocarbon bridges.
  • Preferred according to the invention is a plasma polymer solid according to the invention, in particular a plasma polymer layer according to the invention, wherein the total silicon cross-linking degree is between 50 and 85%, preferably between 55 and 80%, and at the same time the silicon cross-linking via hydrocarbon bonds between 5 and 50%, preferably between 5 and 30%, based on the total number of silicon atoms contained.
  • the overall degree of silicon crosslinking or the degree of silicon crosslinking via carbon bridges is determined in case of doubt as described in Example 6. These degrees of crosslinking make it possible in a special way to achieve the positive layer properties of the plasma-polymer solids or plasma-polymer layers according to the invention.
  • a plasma polymer solid according to the invention in particular a plasma polymer layer according to the invention, wherein the density measured by the SAW method is between 0.8 and 1, 6 g / cm 3 , preferably between 1, 0 and 1, 5 g / cm 3 .
  • the density is determined as described in Example 5.
  • the person skilled in the art will preferably observe some or all of the procedural instructions in DE 102013219331 and / or observe one or more or all of the following measures, namely that the total leakage rate ⁇ 0.1 mbar l / s, preferably ⁇ 0.075 mbar l / s is;
  • the ratio of total leakage rate to the fed 0 2 flow is ⁇ 0.12, preferably ⁇ 0.09, more preferably ⁇ 0.07;
  • the flow ratio of organosilicon precursor to oxygen is> 1, preferably> 1.25;
  • the selected organosilicon precursor has a CH3 / S1 ratio of> 2.7, preferably> 3 and at the same time its O / Si ratio based on the total amount of gas ⁇ 1, 5, preferably ⁇ 1, 1; - If possible, the selected organosilicon precursor does not have silazane compounds;
  • the electrodes are formed so that no exposed electrode edges are present, so that the plasma discharge in the entire space is visually uniform and equally strong;
  • the system is designed to be large-volume such that a.) the sample arranged on the electrode can have at least 15 cm, preferably 20 to 25 cm distance from the next wall and b.) the clear distance of the chamber walls at least 50 cm is;
  • the determination of the self-bias can first be used. It should be noted that preferably the self-bias is not changed by other measures (additional investments of DC or AC voltages). Since commercial matchboxes usually only display the amount of self-bias, it is preferable to make sure by control measurements that no self-bias voltage> + 10 V is generated during the plasma discharge.
  • a self-bias is in the range of -25 to +10 volts, more preferably in the range of -10 to 0 volts.
  • the determination of the bias can be carried out either directly by measuring with a high-voltage probe and oscilloscope directly at the electrode, whereby the safety measures are to be observed when dealing with RF transmitters, or by measurement by means of a multimeter within the range of the control electronics of the corresponding matchbox, if the connections of the DC measuring unit are accessible.
  • the signal picked up at the DC measuring unit is generally correct in sign but does not correspond in magnitude to the true self-bias value. If the self-bias is very low, the plasma potential for layer formation in a capacitively coupled high-frequency plasma is of crucial importance.
  • the conductivity of the plasma and its contact with the electrodes results in a voltage drop across the electrode surfaces (both at the ground electrode and at the RF electrode).
  • the absolute size of the plasma potential depends on various variables, such as the pressure, the gas mixture, the total gas flow and the power.
  • the geometric symmetry of the discharge can be measured by measuring the plasma potential (the plasma potential is a voltage between the plasma and the surface, for example, it can be determined with a Langmuir probe, see, for example, RSC Adv., 2013 , 3, 13540-13557.). If the plasma potential follows a pure sinusoidal signal, there is a geometrically symmetrical discharge. Deviation from the sine indicates asymmetric discharge.
  • the surface layers in front of the HF electrode and the ground electrode behave differently in time.
  • the expert follows depends inter alia on the actual plasma system used. It is preferred to take at least three, more preferably at least five, and particularly preferably all of these measures in order to arrive at a plasma polymer solid according to the invention or a plasma polymer layer according to the invention. Preferably, the method is to be performed so that a zero bias is ensured. Preference is given to a homogenized gas extraction, z. As described in the thesis "Design and Evaluation of gas supply system, electrodes and Gasabsaugungssystemen for low-pressure plasma chambers", Gustavo Simiema de Freitas Barbosa, University of Bremen), and a uniform Precursorgaszu arrangement. This aspect becomes more important the larger the plant is built.
  • PE polyethylene
  • PTFE polytetrafluoroethylene
  • similar fluorine-containing insulating materials are preferred to avoid, at least for the areas exposed to the plasma and / or
  • the total leak rate is determined according to the pressure rise method over a period of at least 1 hour.
  • HMDSO has proven to be a particularly suitable precursor, but it is also possible to use a large number of further alternative precursors.
  • Preferred alternative precursors are selected from the list consisting of octamethyltrisiloxane, decamethylcyclopentasiloxane, tetramethylsilane (TMS), hexamethyldisilane.
  • Part of the invention is also the use of a layer according to the invention for improving the cleanability of an uncoated solid (easy-to-clean apply fertilize).
  • the cleaning can be carried out with solvents, aqueous cleaners and / or dry ice, with soda rays, because due to the favorable surface properties (see above) it is possible to positively influence the cleaning behavior of surfaces with the layers according to the invention.
  • Preferred cleaning agent is water and / or Sodastrahlen.
  • typical cleaners such as those used in the field of food processing. These are e.g. by their basicity, their acidity or by the use of ozone or chlorine.
  • Part of the invention is also the use of a layer according to the invention or a solid according to the invention as a release layer.
  • the layers according to the invention are mechanically particularly resistant and can therefore preferably be used for casting or injection molding processes or other particularly abrasive plastics processing processes, e.g. in pipes or on conveyor such as e.g. Snails.
  • the layers according to the invention are also suitable as release layers for other processes in which a separation of layers / solids is required.
  • Part of the invention is also a method according to the invention for producing a coating according to the invention. In particular, this method comprises the steps of a) providing a substrate, b) depositing a plasma polymer solid, in particular a plasma polymer layer on the substrate, whereby an inventive plasma polymer solid and / or a plasma polymer layer according to the invention is formed.
  • the person skilled in the art will take into account one, several or preferably all of the above-described instructions / steps / method configurations / plasma deposition apparatus configurations. Of particular importance is the selection of precursors, the amount of precursor gas, the maintenance of the distances and / or the use of a structure which implements the requirement of self-bias close to zero. Of course, the person skilled in the art will of course also take into account the area which additionally arises as electrode surface through the component to be coated, the components to be coated. It is expressly pointed out that it is very advantageous to follow the construction instructions of Gustavo Simiema de Freitas Barbosa.
  • the invention presented here makes it possible to produce plasma-polymer solids, in particular plasma-polymer layers, which have an exceptionally high C / O ratio when compared to that taught in WO 2015044247 A1 E-module feature.
  • part of the invention is a solid comprising a substrate and applied to this substrate a plasma polymer layer according to the invention.
  • the plasma-polymer layer according to the invention is also used as a corrosion protection layer, in particular in applications which require a high resistance to bases and alkalis. It can also be used in combination with layers that have particularly good barrier properties.
  • part of the invention is the use of such coatings with an E modulus of about 5 to 20 GPa, preferably with moduli of elasticity in the range of 8 to 16 GPa as scratch and abrasion protective layers, in particular for plastics and soft metals.
  • the coating serves product requirements with regard to low-energy, chemically inert and mechanically stable surface properties.
  • the plasma polymer coatings used in this example differ in their production only in the power coupled into the plasma process. Accordingly, they were prepared by means of a constant gas mixture of hexamethyldisiloxane (HMDSO) and oxygen. For HMDSO a gas flow of 92 sccm and for oxygen of 53 sccm was used. The external plasma parameters pressure (0.016 mbar), gas mixture ratio and total gas flow are kept constant for all coatings. There were five different powers from 1000W to 3400W, in the 600W distance, set. For all processes the self-bias was ⁇ -10V.
  • HMDSO hexamethyldisiloxane
  • the plasma reactor used for the preparation of the layers is a large-volume reactor of about 1.2 m 3 , which is operated with a capacitive radio frequency excitation (13.56 MHz). This is a self-made construction of the Fraunhofer IFAM, Bremen.
  • the special feature of the system used is that for many processes based on hexamethyldisiloxane (HMDSO) a self-bias close to zero is reliably achievable and a very homogenous plasma is formed throughout the free reactor space.
  • the low self-bias is determined by the geometry of the plasma system, with areas of the electrodes and the grounded surfaces being approximately equal. 4, the plasma system used is shown schematically with its most important components.
  • the figure shows a scheme of the plasma system used (the electrode forms a U, the remaining, not provided with the electrode wall represents for the plasma, the electrical mass, which is also correspondingly U-shaped).
  • the suction unit is equipped with an adjustable butterfly valve.
  • the Power is generated by the HF generator and coupled via the Matchbox in the plasma.
  • the Matchbox (17) serves to compensate for the unsteady ohmic resistance of the plasma.
  • the HF generator (19) is protected against backscattered power.
  • Self-bias is a DC voltage measured between the RF feed (15) and the grounded reactor. For this purpose, via a coil of the RF component, which is applied to the feed (15), filtered. The remaining DC component is set in relation to the grounded reactor wall.
  • the value of the self-bias largely characterizes the plasma process in addition to the process pressure and the radiated power.
  • the fast electrons have migrated to the grounded reactor surfaces.
  • the ions are accelerated toward the electrodes and impinge on the substrate with increased energy. This increases the deposition rate, but also influences the film formation.
  • the fact that plasma deposition with self-bias of almost zero volts leads to a layer deposition is due, among other things, to the plasma potential. For energetic reasons, this plasma potential must be the most positive in the equilibrium plasma, electrode and grounded wall. This results in a voltage difference of the order of typically 10V. This difference causes a net drift of the ions towards the electrode.
  • the total leak rate was determined to be 0.065 mbar l / s.
  • the pressure rise method was used over 1 h.
  • the base pressure chosen was 8 * 10 03 mbar.
  • a conditioning of the plasma system was carried out before the production of the layers. This is the process with 2200W power under the above conditions for a period of at least one hour. This conditioning ensures that all surfaces within the plasma system are already provided with a plasma polymer separation layer and that no uncontrolled contamination of the samples by preceding processes occurs.
  • Example 2 Nanoindentation of the Layers from Example 1
  • Nanoindentation is a registered intrusion into the sample material.
  • a tip in the form of a Berkovich pyramid with the force F designated in FIG. 5 by Load P, is pressed into the sample surface. Both the force and penetration of the tip are recorded. This results in a force-penetration curve, as can be seen in Fig. 5.
  • Figure 5 is a schematic representation of a force-penetration curve (see WC Oliver and GM Pharr, “Measurement of hardness and elastic modulus by instrumented indentation: Advances in understanding and refinement to methodology,” Journal of Materials Research, 2003). ,
  • the elastic modulus and the hardness can be determined. It is important in the determination of these material constants of thin layers not to exceed a maximum penetration depth of about 10% of the layer thickness, since otherwise the substrate properties will falsify the measurement result (see J. Gersten and F. Smith, The Chemistry of Materials, New York: John Wiley & Sons, Inc., 2001).
  • Equation 1 Equation 1
  • ⁇ is a geometry factor which is one for a Berkovich pyramid.
  • S is the contact stiffness which is determined via the derivative of the maximum force at maximum penetration depth, see FIG. 5.
  • the contact surface A also enters into the effective modulus of elasticity, in short the modulus of elasticity. From this effective modulus of elasticity, the E-modulus of the sample E can be calculated according to equation 2.
  • the variables indicated by i are based on the indenter and thus constants.
  • the modulus of elasticity of the plasma-polymer coatings to be investigated is within an expected value range of approximately 1 to 20 GPa, it is necessary to prepare samples with a minimum layer thickness of 2 ⁇ m. For itself thinner layers, a sample of the same composition is created with minimum layer thickness.
  • the device is a "Universal Material Tester", UMT 1 Bruker.
  • the sensor is a nanohead 2.
  • the measurement results for the layers from Example 1 are shown in FIG.
  • the E-modulus increases significantly with the supplied plasma power.
  • the reference example has an E-modulus of about 13 GPa and thus lies in the size range which is claimed for the layers according to the invention.
  • FIG. 6 shows: E modulus of the plasma polymer coatings from Example 1 as a function of the power, determined by nanoindentation with Berkovich indentor. Measuring Example 3: Microelementar and XPS analysis of the layers from Example 1
  • the microelemental analysis is a combustion taking place under defined conditions.
  • the sample powder is first dried to exclude any stored water as a source of interference. Subsequently, the combustion of the sample takes place under pure oxygen.
  • the resulting combustion gases are passed through various reagents (e.g., caustic soda), each of which exhibits a measurable response to the presence of specific gas molecules.
  • the measured quantity for determining the carbon content is the change in the electrical conductivity of caustic soda due to absorbed carbon dioxide.
  • the sample was previously burned at 1200 ° C in an oxygen stream.
  • the sample was also burned at 1050 ° C in an oxygen stream and the combustion water formed detected by IR measurement.
  • the values obtained are compared with the carbon content determined by means of XPS. In this way, the hydrogen content H z of the coating with the composition SiOxCyHz can be determined.
  • the coatings were scraped off glass slides to produce enough sample powder. For this purpose, a plurality of glass slides were distributed almost on the entire base electrode of the reactor. A layer thickness of about 2 pm was deposited on the glass slides.
  • X-ray photoelectron spectroscopy is based on the external photoeffect.
  • the process can be approximated as a three step process. First, a photon with a wavelength in the X-ray region transfers its energy to a trunk electron of the sample, whereupon it leaves its previous orbital. Then it moves through the sample to the surface. Finally, the electron exits the sample and can be detected. The photoelectrons are detected energy-selectively.
  • the kinetic energy of the electrons Ewn is measured in the photoelectron spectrometer.
  • the work function of the spectrometer cps P is almost constant and depends on the device.
  • EB F see HKS Brümmer, Fest redesign mit Eletronen, Ionen und Röntgenstrahlen, Berlin, 1980.
  • the binding energy is orbital and element dependent.
  • the chemical shift the "chemical shift”.
  • the presence of neighboring atoms has an influence on the binding energy of the core electrons of an atom.
  • oxygen atoms bonded to a silicon atom result in a shift in the binding energy of the Si atom, and the oxidation state of the silicon has changed.
  • the magnitude of the shift depends on the different electronegativities of the binding partners, as well as their number (see M. Cardona and L. Ley, "Photoemission in Solids I - General Principles," in Topics in Applied Physics Vol. 26, Springer-Verlag, 1978). Therefore, XPS is well suited for analyzing the chemical composition.
  • Table 1 shows the elemental contents of the coatings of Example 1. The values and errors given are the mean of the three measurement positions of a sample and the associated standard deviation. In addition, the position of the maximum of the Si 2p peak is indicated. It is nearly constant for the power variation. At about 103 eV, it lies between secondary and tertiary bond ratios. Only the non-inventive reference shows a significant deviation. Table 1: Elemental content from XPS measurements, averages of three measurement positions of a sample
  • FIG. 7 shows element ratios from XPS measurements normalized to silicon, data in at%.
  • Table 2 makes it clear that the oxygen to silicon content remains unchanged under the error for all five plasma outputs. Only the carbon content decreases slightly with increasing power. In comparison, the reference not according to the invention has a significantly higher O to Si ratio.
  • Table 3 shows the results of the microelement analysis and the resulting ratio of hydrogen per carbon atom.
  • Table 4 determined stoichiometry of the five plasma polymer coatings, based on silicon, combined results of XPS (Si, O, C content) and microelement analysis (H content)
  • the plasma polymer coatings according to the invention are very similar in terms of their elemental composition.
  • the ratio of oxygen and silicon is the same for all considered coatings.
  • the Si-O network is not changed by the power change. This result is unexpected and surprising in view of the hitherto known increase in the elastic modulus with increasing plasma power.
  • the chemical composition measurements are very consistent overall. This means that the results from the XPS and from the microelementaranalysis fit together very well, even though they are completely different analytical methods. The most striking feature of this is the decreasing content of carbon with increasing power. This high quality of the analyzes can be achieved only with a sufficient homogeneity and reproducibility of the plasma process.
  • the samples for the XPS measurements, as well as the micro elemental analysis come from different batches of the plasma process. Thus, there is a very high reproducibility from process to process. At the same time, the samples for the microelemental analysis were distributed almost on the entire base electrode. This also indicates a high homogeneity of the coating process within the chamber. This conclusion is based on comparison with the XPS results, which also show a decrease in carbon, but were measured on a single silicon sample. Thus, both the values averaged over the entire base area of the reactor and the position-dependent XPS measurement show the same tendency. This result can be achieved only by the modern and extensive process control, as well as by the construction of the plasma chamber itself. It was created in the entire, effective reactor space homogeneously burning plasma.
  • FIG. 8 illustrates: H: C ratio in at% from microelemental analysis
  • H: C ratio As previously described, there is a decrease in the H: C ratio with increasing plasma process performance. This means that with increasing power other structural elements must be present which produce a lower H: C ratio.
  • a linear PDMS has an H: C ratio of exactly 3.
  • a CH2 group has a ratio of 2. The resulting crosslinking structure is discussed in Example 6.
  • Equation 5 This approach for solving the free surface energy of a solid assumes that the interaction between the solid and the liquid phase a sl can be described over the geometric mean of the disperse fractions s 5 °, s 3 and polar portions s r , af. Furthermore, equation 6 applies to the surface energies or voltages of solid and liquid. Equation 6
  • the dynamic method in which the droplet is expanded from a cannula during the measurement of the contact angle, progressive contact angle measurement.
  • the static measurement method is used.
  • a defined drop volume is placed on the sample surface by means of a cannula, and then the contact angle is measured without the presence of the cannula.
  • the static measuring method was used.
  • the contact angle of 10 drops of water and diiodomethane were measured on a silicon wafer. From the mean values the measured contact angle is determined by the surface energy according to Owens-Wendt-Rabel-Kaelble.
  • the measurements were carried out with the "contact angle measuring device G2" from the company "Krüss”. For this purpose, drops with a volume of 2 mM were deposited on the sample surface and the contact angle was measured for 10 seconds at a measuring rate of one second. This process was performed at 10 different positions of a sample with two liquids each (water and diiodomethane). The samples used were coated 2-inch silicon wafers.
  • the surface energy of the reference not according to the invention is significantly increased compared with the layers according to the invention.
  • the polar portion has a significantly higher value of about 5.25 mN / m, see FIG. 9 for more details. This can be explained by the increased oxygen content of the reference compared to the coatings investigated. Since the Si-O bond is a polar bond, an increase in this structural group leads to an increased polar fraction of the surface energy.
  • FIG. 9 shows: free surface energy of the plasma polymer separation layers and the reference.
  • the density of thin layers can be determined by measuring the dispersion of surface acoustic waves, in short SAW, in coated media. Rayleigh waves are generated at the sample surface with a laser. Due to the coating, a dispersion of the propagating wave occurs.
  • the dispersion function can be fitted on a known substrate with the parameters layer thickness, density, modulus of elasticity and Poisson number. Thus, it is possible to measure non-destructively these material properties.
  • the generation of the surface acoustic wave is based on a short-term, localized warming.
  • the heating by the pulsed laser beam generates a thermal expansion on the sample surface and thus a surface acoustic wave. This wave contains a large frequency spectrum, which leads to a dispersion in the presence of a thin surface coating.
  • the phase curve of the surface wave over the frequency is shown as a measuring curve.
  • a fit procedure is performed to determine the elastic parameters of the layer.
  • Equation 7 In a homogeneous, isotropic material, the relationship in equation 7 applies to the phase velocity c of a surface acoustic wave. Equation 7
  • E is the modulus of elasticity of the homogeneous, isotropic material
  • v is the Poisson's number, which indicates the transverse contraction ratio
  • p is the density.
  • the amplitude and phase spectrum can be determined.
  • the amplitude spectrum is used to control the signal-to-noise ratio and the dispersion according to Equation 8 is calculated from the phase spectrum F (/) (see D. Schneider, S. Aktauf, S. Schulz and T. Gessner, "The current limits of the laser-acoustic test method to characterize low-k films," Microelectronic Engineering 82 (2005) 393-398, 2005).
  • / the frequency of the wave
  • parameter x describes the distance between the excitation line of the laser and the detector.
  • the indices designate two different excitation positions with the associated distances x and phase functions F (/).
  • Data processing is carried out as described in "A photoacoustic method for characterizing thin films", (Dieter Schneider, Thomas Schwarz, Surface and Coatings Technology 91 (1997) 136-146).
  • the measured dispersion curves may have different degrees of curvature depending on the material parameters, as well as the attenuation which the coating material has with respect to the surface acoustic wave.
  • the dispersion curve obtained can correspond to nearly a straight line or be curved several times.
  • the goal was to determine the density of the layer.
  • the values for the Poisson number and the layer thickness had to be determined in another way due to the small curvature of the dispersion.
  • the Poisson's number was fixed at 0.17, based on the nanoindentation measurements, the layer thickness was determined by means of three-point reflectometric measurements.
  • FIG. 10 shows the mass density of the plasma polymer separation layers and the reference
  • Example 6 Determination of a Structural Model and the Degree of Crosslinking of the Layers of Example 1
  • the microelement analysis provides an indication of the ratio of CH3 to CH2 groups in the different plasma polymer coatings.
  • a chemical structural model can be created.
  • the peak fitting is used. For this purpose, assumptions are made about the existing oxidation states of the silicon. Each oxidation state has a different binding energy. Thus, the measured Si 2p peak can be decomposed into its constituents. An example of the peak fitting of the Si 2p peak is shown in FIG. The four oxidation states are expressed in different binding energies and are given in Table 5 with their binding energies and literature references.
  • Figure 11 shows: Fit example of the Si-2p peak fitted with doublets
  • FIG. 11 shows the measurement curve as well as the various fitted peaks.
  • the corrected binding energies in eV are shown on the X-axis and the intensity in counts per second (cps) on the Y-axis.
  • the quaternary silicon peak was made with one face Zero fitted and is therefore not visible in the figure.
  • the positions of the oxidation states were set to allow a comparable evaluation of all spectra.
  • FIG. 12 shows: Shares of the different oxidation states of silicon determined from the peak fitting of the Si2p, plotted against the plasma power.
  • the possible structural elements discussed in this context are basically divided into two categories, the network-forming structural groups and those which terminate with respect to the hydrocarbon bridges.
  • the discussed structural groups are shown in Table 6 and Table 7. It should be noted that the structure groups shown for the sake of simplicity were each drawn with silicon in the primary oxidation state. Each of the illustrated structural groups contains several structural elements which differ with respect to the oxidation states of the silicon. As a result of this structure of the structural elements or structure groups, the individual structural elements can later be linked via the Si-O network.
  • the terminations shown actually belong to structure group A, but carry other functional groups, such as OH, SiH or ethylene groups.
  • the structural groups classified as terminating with respect to the hydrocarbon bridges occur only in lower concentrations within the coating, they do not form the actual coating network.
  • Structure group A is pure siloxanes.
  • the structural group B has a hydrocarbon bridge. This is a methylene bridge.
  • Structure group C includes an oxymethylene bridge.
  • structural group D represents an ethylene bridge.
  • the hypothetical distribution of the oxidation states can be made by a classification into primary, secondary, ternary and quaternary structural elements. It should be noted that the structural groups B, C and D each consist of two Si atoms and therefore the proportions are to be weighted with the factors 0.5 or 2. The distribution thus found is normalized to a sum of 100% and compared with the results of the Si2p peak adaptation from the XPS data. If there is a good agreement with the distribution of the percentage of structural elements found, both with the measured atomic ratios and with the oxidation states, the composition thus found can be assumed to be the solution of this underdetermined system of equations.
  • the presented procedure scheme can be implemented in a least square optimization of the underdetermined system of equations. This makes it possible to carry out an evaluation of the structure components that is more independent of the user.
  • the implementation was implemented as a Python script. Python is a programming language that is well-suited for solving mathematical problems.
  • FIG. 14 shows the percentage of the structural groups as a function of the total number of structural elements (adaptation algorithm: minimization of the vector components of c).
  • Equation 9 c Ax - b
  • Equation 9 For optimization, the function in Equation 9 was used in each case. This is the established, transformed linear system of equations.
  • A is the coefficient matrix which describes all atomic ratios as well as the contribution of the structural elements to the oxidation states.
  • the vector b is the result vector which contains the nominal measured values from the XPS analysis.
  • the vector c To solve the problem by means of a least squares algorithm, the vector c must be passed to the algorithm. This vector or its square of sums must be minimized.
  • FIG. 13 shows the comparison of two optimization algorithms.
  • this is an algorithm which individually minimizes the components of the vector c and, on the other hand, minimizes the magnitude square of the vector c. It can be stated here that given the total number of structural elements and a number of 100 adaptations carried out with arbitrary start vectors, both algorithms show a good agreement in the context of the standard deviation formed in the case of several of the selected plasma powers.
  • the system of equations consists of 10 equations, since the proportion of OH and (Si-H) groups per coating must be specified in order to arrive at a physically meaningful result. Furthermore, there are two constraints that further constrain the fit, on the one hand limiting the terminations to a maximum of 20% of the total set of features, and on the other hand limiting the total sum of (C-O) bonds due to peak matching of the C1 s in the XPS data.
  • FIG. 15 shows: Comparison of the proportions of the different structural groups for the plasma powers used
  • the methylene bridges are formed only to a very small extent.
  • the methoxy bridges are limited by the already described boundary condition, the content of CO bonds.
  • the proportions of OH- and Si-H groups were fixed in each case on the basis of the IRRAS results and represent assumptions. The absolute proportion of these groups is not known. However, the exact value of (Si-H) and OH groups only represents an offset for the other structure groups. This means that the structure group dominating per plasma power will not change, but only all structural groups slightly changed proportions, if the setting has changed of (Si-H) - or OH content, respectively.
  • the mathematical adaptation by means of the least squares method the different crosslinking structures of the plasma polymer coatings can be estimated in compliance with the consistency criteria.
  • Table 10 The trends are summarized in Table 10. The specification of the standard deviation has been omitted here for the sake of clarity. This can be seen in FIG.
  • the mathematical adaptation is used to estimate the percentage distribution of all 32 structural elements. These structural elements have hitherto been combined to form the structural groups. Now, the percentages of the individual structural elements themselves are to be considered.
  • Si mesh number describes the number of network-forming bonds that a silicon atom has.
  • Si degree of crosslinking is 100% and the Si network number is 4.
  • the introduced Si network number is not related to a crosslinking structure, but takes into account all possible structure groups. Thus, each of the structure elements can be assigned such a Si network number.
  • a degree of crosslinking of 75% would be, for example, a structure in which each silicon atom has exactly three network-forming bonds, for example the aforementioned polymethylsilsesquioxane.
  • a degree of crosslinking of 50% corresponds to linear chains with two crosslinking bonds per silicon atom. This can be, for example, PDMS.
  • Figure 16 illustrates: degrees of crosslinking of the plasma polymer coatings as a function of power; Degree of crosslinking of the Si-O-Si network determined by the Si network number (black); Overall degree of crosslinking from distribution of the structural elements, determined by Si network number (dotted); Degree of crosslinking of the hydrocarbon network from the difference between the total degree of crosslinking and the Si-O-Si network (dashed line)
  • FIG. 16 shows the total crosslinking degree of the various plasma-polymer coatings calculated via the Si mesh number.
  • the degree of crosslinking of the Si-O-Si network was also calculated using the Si network number.
  • the proportions of different Si network numbers can be taken from the proportions of the oxidation states of the silicon.
  • the difference between these two degrees of crosslinking results in the degree of crosslinking caused by the hydrocarbon network.
  • the results obtained are based purely on empirical, mathematical experiments and do not claim to be an exact structural model. In other words, the inventors are not bound by this theory. Nevertheless, tendencies can be noted.
  • the carbon-containing crosslinking structures have to be ethylene groups rather than, for example, methylene groups.
  • the specified distributions of the structural elements or structural groups were respectively determined via the adaptation by means of a least squares algorithm. The boundary conditions already described have been complied with.
  • the fitting algorithm can not accurately map the measured values. This is especially evident in the H: C ratio.
  • the algorithm can simulate the measured values very accurately. A difference only occurs in later decimal places. Overall, this calculation of the structural groups can be a clear indication of an increasing proportion of hydrocarbon-containing crosslinks at higher plasma powers, as well as an overall increase in the overall degree of crosslinking. The increase in hydrocarbon crosslinks is consistent with the increasing overall degree of crosslinking with increasing performance and explains the increasing elastic modulus, as well as the slightly increasing mass density.
  • Reflection absorption spectroscopy in the infrared spectral range is a frequently used spectroscopic method for chemical structure analysis.
  • molecular vibrations are excited.
  • the energy at which a vibration can be excited depends on the molecule or the moiety, so a CFh group has a different oscillation frequency than a CFb group.
  • the frequency depends on the type of excited vibration.
  • a Bruker Corperation Vertex 80 / XSA with a mid-infrared radiation source, MIR (500-4000 cm A -1), and a nitrogen-cooled mercury-cadmium-telluride (MCT) detector were used.
  • the device was operated in reflection mode. This means the sample was at an angle of 45 ° irradiated and the reflected intensity measured.
  • the samples are aluminum with the plasma polymer layer to be examined.
  • An uncoated aluminum sample serves as a reference and atmospheric compensation and baseline correction are performed. Care must be taken to ensure that the samples to be compared have the same layer thickness, since the ratios of some IR bands change with different layer thicknesses.
  • Example 3 it was found that only the carbon content decreases slightly with increasing power. This can be attributed to an increase of Si-H and -OH groups by means of IRRAS measurements. These bands grow with increasing power in the absorption spectrum, see FIG. 17.
  • Figure 17 shows IRRAS measurements of the five coatings, band assignments according to J. Lambert, S. Gronert, H. Shurvell and D. Lightner, Spectroscopy - Structure Elucidation in Organic Chemistry, Pearson, 2012 and L. Smith, "Analysis of Silicones,” In Chemical Analysis Volume 41, John Wiley & Sons, 1974.
  • FIG. 18 shows: detail of the IRRAS spectrum, average spectra of the various plasma polymer coatings, L. Smith's tape assignments, "Analysis of Silicones,” in Chemical Analysis Volume 41, John Wiley & Sons , 1974.
  • the spectrum shows that the intensity of the Si (CH3) x peaks decreases with higher plasma power. This indicates a decrease in CH3 groups with increasing plasma output. Thus, indirectly, the developed structural model of Example 6 can be confirmed. Also, a slight growth of the by the Si (CH2) i, 2-Si Bond caused shoulder of the Si-O-Si peak can be observed. When coated with 3400 W plasma power, the band clearly shifts to lower wavenumbers. Thus, an increased proportion of ethylene bridges is present. Here is thus a more concrete indication of the increasing hydrocarbon cross-linking via ethylene bridges.

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Abstract

L'invention concerne un corps solide de polymère plasma, en particulier une couche de polymère plasma. La limite inférieure du module d'élasticité du corps solide ou de la couche est déterminée par une fonction déterminée, ce qui s'applique à certaines gammes du module d'élasticité et est déterminée pour certains rapports molaires C/O par XPS. L'invention concerne en outre l'utilisation d'un corps solide de polymère plasma correspondant ou d'une couche de polymère plasma correspondante, ainsi qu'un procédé de production de celui-ci.
EP18826575.5A 2017-12-22 2018-12-17 Corps solides de polymère plasma, en particulier couche de polymère plasma avec formation de réseau d'hydrocarbures, leur utilisation et procédé de production de ceux-ci Pending EP3727706A1 (fr)

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