DE3541721C2 - - Google Patents

Description

The invention relates to a method for producing thin and thereby hole-free electrically conductive polymer layers on any shaped substrates.

The production of thin (down to the 10 nm range) but closed polymer layers by polymerization with low-temperature plasmas, hereinafter also referred to as "plasmas", is known. However, the polymer layers obtained are generally good insulators (see, for example, A. Bradley and JP Hammes, J. Electrochem. Soc. 110 (1), pp. 15-22, 1963), which is why their usability as dielectrics in capacitors has been extensively investigated ( Federal Ministerial Research Technological Research Area Technological Research Development BMFT-FB T 76-66, 1976; see M. Gazicki and H. Yasuda, Plasma Chem. Plasma Proc. 3 (3), pp. 279-327, 1983). Exceptions known to date are layers of acrylonitrile polymerized in low-temperature plasma, which were subsequently made conductive by annealing at relatively high temperatures (T. Hirai and O. Nakada, Jap. J. Appl. Phys. 7 (2), 112-121, 1968) and layers produced from low-temperature plasma polymerized organic amines, organic silicon compounds and free-radically polymerizable unsaturated and aromatic compounds with antistatic properties (DE 32 30 204 A1). Conductive layers could also be obtained if almost pure, hard carbon layers were deposited from hydrocarbons, for example from CH ₄ with small additions of B ₂ H ₆ by microwave low-temperature plasma (N. Fujimori, T. Imai and A. Doi, Proc. 5th Int. Conf. Ion Plasma Ass. Techn. (IPAT 85), 1985, ed. H. Oechsner, pp. 307-311). In general, however, conductive polymer layers were only obtained if a considerable proportion of metal particles were embedded in the polymer layer, for example by decomposition and polymerization of organometallic compounds in low-temperature plasma (E. Kny, LL Levenson, WJ James and RA Auerbach, J. Vac Sci. Technol. 16 (2), pp. 359-362, 1979) or by simultaneous sputtering of a metal and polymerization of fluorocarbons in low-temperature plasma (E. Kay, Proc. 5th Int. Conf. Ion Plasma Ass. Techn. ( IPAT 85), 1985, ed. H. Oechsner, p. 258).

The previously found, in a conventional way (not by means of Plasma) produced, electrically conductive, organic polymers, mostly doped polyenes, polyaromatics or charge transfer com plexes can currently not be in the form of thinner (<1µm) hole-free layers can be applied to substrates. In addition they are usually thermal and exposed to air not stable enough. Conventional, per se non-conductive polymers, which by admixing considerable Amounts of an electrically conductive filler such as carbon black or Silver were made conductive. A disadvantage of such dispersions is that their conductivity controls only within relatively narrow limits can be.

The object of the present invention is a method for the production of thin, hole-free, electrically conductive poly to create layers that have no electrically conductive filler contain materials such as carbon or metals and their electrical Conductivity can be varied within a wide range. The The process is said to further improve thermal and air stability lity of the polymer layers.

According to the invention this object is achieved in that a geeig nice, gaseous monomer or monomer mixture by a low temperature plasma is polymerized and that at the same time a Dotie The growing polymer layer takes place. It was surprising found that by means of plasma flexible, elastic polymer layers can be produced that are electrically conductive without that they contain embedded metal particles and their electrical Conductivity can be varied over several orders of magnitude can. According to the invention, this is a suitable gaseous Monomer or monomer mixture, mixed with or without auxiliary gas, using low-temperature plasma with a suitable choice of parameters Pressure, power density, substrate temperature, gas flow rate polymerized in such a way that a polymer layer with a high content of conjugated double bonds. Here becomes a gaseous doping at the same time as the polymerization medium let into the reactor and into the growing polymer layer stored. The polymer layer is advantageously  for stabilization against oxygen and moisture afterwards treated with radical scavengers.

Sufficiently volatile are generally usable according to the invention Monomers that under the influence of plasmas to form polymers react high content of conjugated double bonds, in particular their monomers from the following groups:

• 1. Unsaturated, advantageously highly unsaturated, aliphatic Connections such as Ether, propyne, butyne (1), butyne (2), Butene- (1) -in- (3), allen, acrylonitrile, cyanoacetylene, dicyanoace tylen and tetracyanoethylene,
• 2. Alicyclic, advantageously highly unsaturated compounds such as. Cyclopropene, vinylcyclopropane, cyclopentadiene and cyclo octatetraen,
• 3. Aromatic and heteroaromatic compounds such as e.g. Benzene, Biphenyl, naphthalene, pyridine, bipyridyl, diazines, thiophene, Furan, quinoline, isoquinoline, pyrrole, diazole, thiazole, oxazole, Pyridazole and imidazole,
• 4. Aromatic and heteroaromatic compounds with unsaturated Substituents such as Styrene, phenylacetylene, stilbene, divinyl benzene, benzonitrile and terephthalic acid dinitrile,
• 5. Compounds which polymerize by the action of plasmas with elimination to give layers with highly conjugated double bond systems, for example compounds of the following general types:
  • a) ArE _x , preferably Ar-E or ArE ₂ , Ar is a single or multiple, preferably doubly substituted aromatic or heteroaromatic ring system, for example a benzene, pyridine, pyrrole, thiophene or furan system and the substituent E is one Low temperature plasma easily eliminable group such as: -SO ₂ R, -COOR (with R = alkyl or aryl), advantageously an aldehyde, carboxy or anhydride group. Compounds of this type which can advantageously be used according to the invention are, for example, benzaldehyde, phthalic acid, phthalic anhydride, terephthalic acid, terephthalic aldehyde and thiophene-3,4-dialdehyde.
  • b) E-Ar-EE-Ar-E or Ar-EE-Ar, where Ar and E are as defined in a), and EE is a group which can be easily eliminated or split by low-temperature plasma, such as, for example, -N = N -, -CO-. -SS-, -SO ₂ - or -S-. Connections of this type which can advantageously be used according to the invention are, for example, azobenzene and thianthrene.
  • c) Unsaturated alicyclic systems in which an easily eliminable group, advantageously a carbonyl or anhydride group, is part of the ring: for example 1,4-naphthoquinone, 1,2-naphthoquinone, 2,6-naphthoquinone or advantageously 1,4- Benzo quinone, 1,2-benzoquinone, cyclopentadienone, maleic anhydride and glutaric anhydride.
  • d) R- (CH = CX-) _n R with R equal to -H, an ethynyl, vinyl or other unsaturated hydrocarbon radical (two radicals R can be closed to form a ring system) or a cyano group and X is chlorine, bromine or Iodine. An example of a compound of this type which can advantageously be used is 2-chloroacrylonitrile.

Substituted compounds of 1 to 1 are also suitable 5. groups listed as monomers.

The conductivity of the polymer layers can be influenced via the substituents. So it is known that electron-donating substituents (eg -OCH ₃ ) on benzene rings, which are part of the polymer chain, increase the conductivity, while electron-withdrawing substituents on benzene rings (eg -NO ₂ ) or vinyl double bonds (eg -CN), the Part of the polymer chain are those that reduce conductivity (G. Koßmehl, Ber. Bunsenges. Phys. Chem. 83, 417-426, 1979).

Dopants known according to the invention, such as I ₂ , AsF ₅ , SbCl ₅ , Br ₂ , PCl ₅ , SiF ₄ , ICN and SO ₃ and other suitable compounds which are sufficiently volatile, can be used as dopants.

For certain configurations of the method according to the invention, it is advantageous to additionally add a non-polymerizing gas as auxiliary gas, for example in order to increase the pressure in the gas phase or to favor elimination reactions. For example, noble gases, O ₂ , H ₂ , N ₂ O, CO, CO ₂ , H ₂ O, H ₂ S, CS ₂ , SO ₂ , N ₂ , NH ₃ , N ₂ H ₄ , PH ₃ and others, non-polymerizing compounds with sufficient volatility are used under the conditions of a low-temperature plasma.

The plasma causing the polymerization can be used according to the invention can be generated by various forms of electrical discharge:

• 1. DC voltage or low frequency (up to approx. 100 kHz) glow charge:
  The usable pressure ranges from approx. 1 Pa to 1000 Pa, the voltages to be applied are typically 50-5000 V. The electrodes are located inside the reactor. According to the invention, the power density in the low-temperature plasma should be in the range from 0.001 to 0.5 W / cm ³ .
• 2. High frequency glow discharge:
  The use of high-frequency voltages in the range from 0.1 to 100 MHz, usually 13.56 MHz, makes it possible, when using a reactor made of an electrically insulating material (for example glass or ceramic), to dispense with internal electrodes and the energy with external ones Electrodes or an external coil to transfer. However, electrodes lying inside the reactor can also be used, for example in the case of a reactor consisting of metal. The usable pressure range is 1 to 1000 Pa, the power density in the plasma should be in the range of 0.001 to 0.5 W / cm ³ .
• 3. Microwave discharge:
  When using special reactors (eg according to US PS 40 49 940) frequencies in the range from 0.1 to 1000 kHz can be used. In this way, plasmas with high electron densities can be generated, as a result of which high deposition rates can be achieved. The usable pressure range is between 10 ² Pa and approx. 10 ⁵ Pa (1 atm), the power density should be between 0.001 and 0.5 W / cm ³ .
• 4. Corona discharge:
  Corona systems which can be operated at pressures of 10 Pa to 2 × 10 ⁵ Pa (2 atm) are particularly suitable for coating sheet-like or plate-shaped objects. The frequency of the applied voltage can be selected from a DC voltage to a high frequency, but is usually 10 to 40 kHz. The voltage is up to 20 kV depending on the pressure and electrode spacing.
• 5. Independent glow discharge:
  To maintain the discharge, electrons are supplied to them, usually through a hot cathode. This increases the usable print area. A commercially available plant with a volume of approximately 7 m ³ which can be used advantageously for the invention preferably works in the range from 0.065 Pa to 13 Pa pressure, 400 to 800 V discharge voltage and current densities of 0.1 to 0.5 mA / cm ^2nd

Setting the reaction parameters:

• - Mixing ratio of monomer or monomers, dopants and possibly auxiliary gas
• - gas flow rate
• - Print
• - Electrical power transferred to the plasma
• - temperature of the substrates
• - Placement of the substrates in the reactor
• - Arrangement of the inlet openings for monomer or monomers and Dopant in the reactor
• - response time

depends on the chosen form of electrical discharge, the or the monomers used and the dopant (s) as well as the desired chemical, electrical and other physical properties of the polymer layer to be applied. In general, the conductivity increases with the degree of doping Surface temperature of the substrates and performance. Unless the substrates are at temperatures during coating were heated from 150 ° C and higher, it is advantageous to substrates coated according to the invention under vacuum at temperature annealing up to 400 ° C for between 5 minutes and 5 hours. This temperature treatment can reduce the number of in the polymer layer existing radical sites that oxygen and air Adversely affect the stability of the polymer layers, drastically be lowered (EP 01 32 686 A1).

An advantageous further development of the invention is treatment of the deposited polymer layers with radical scavengers. Herewith are compounds that are caused by chemical reaction trap reactive radicals, i.e. can render ineffective.  

Compounds which are themselves radicals, for example NO, or those which disintegrate into radicals under the action of light, heat or plasmas are preferably used as radical scavengers. These include, in particular, the so-called telogens (OA Neumüller, "Römpps Chemielexikon", 7th edition, vol. 6, p. 3487, Stuttgart 1977). Examples of telogens that can be used advantageously are:
CCl ₄ , CHCl ₃ , C ₆ H ₅ -CCl ₃ , H ₃ C-CCl ₃ , CCl ₃ -CCl ₃ , CCl ₃ Br, CFCl ₃ , CBr ₄ , CHBr ₃ , CCL ₃ I, CCl ₃ Br, CF ₃ I, CF ₃ CCl ₂ I, SF ₅ Cl, ClCN, C ₂ H ₅ I, CH ₃ SH, Cl ₂ , HBr and SiCl ₃ H.

Unless they are already in the form of free radicals, the free radical scavengers are advantageously annealed at up to 400 ° C. and / or a plasma at a pressure in the range from 0.65 Pa to 650 Pa and a power density of 0.001 to 0.1 W / cm ³ activated.

When activated with a low-temperature plasma, other compounds can also be used which decompose into radicals under these conditions, such as N ₂ , H ₂ N-NH ₂ , I ₂ , H ₃ C-CH ₃ and H ₂ . The combination of treatment with radical scavengers with simultaneous annealing at up to 400 ° C. is particularly advantageous.

The invention has the following advantages:

• a) The electrically conductive produced according to the invention Polymer layers have the general advantages of means Low temperature plasma generated polymer layers (also: "Plasma polymers"): they are highly cross-linked, insoluble, hard and flexible, hole-free, chemical and thermal very stable.
• b) The conductivity of the polymer layer produced according to the invention can be easily determined by the choice of the monomer (s) the setting of the reaction parameters and the degree of doping control and vary within wide limits.
• c) High degrees of doping can be achieved. Because the doping medium not introduced by diffusion, but in the growing polymer layer is incorporated is its distribution homogeneous within the layer thickness.
• d) The dopant is in the dense, cross-linked polymer layer firmly enclosed and therefore only migrates at high temperatures noticeable extent.  
• e) The process is easy to control via the reaction parameters lieren. For example, the layer thickness slightly over the reaction duration down to 10 to 20 nm.
• f) In general, cheap starting substances can be used will.
• g) It can also irregularly shaped body with a uniform conductive polymer layer.
• h) The process is a "dry process" and can even at low Temperatures are operated. It can easily be used in vacuum systems, as used in semiconductor or magnetic tape production become integrated.

The method according to the invention is suitable inter alia. especially for Manufacture of chemical sensor layers and antistatic coating conditions, e.g. on magnetic tapes.

The invention is explained below using exemplary embodiments. A corresponding apparatus is shown schematically in Fig. 1. It is suitable for coating small, advantageously flat objects.

1st embodiment

A reactor with a volume of 0.9 dm ³ , consisting of glass, is charged with the objects ( 3 ), in this application example glass panes, after removal of a closure part ( 2 ) and closed again. The reactor is then evacuated by means of a vacuum pump (not shown) with a suction power of 50 dm ³ / min to a residual pressure of less than 0.26 Pa. The pressure is read with an electric vacuum measuring device ( 4 ). A (disadvantageous) backflow of hydrocarbons from the vacuum pump is suppressed with a cold trap ( 5 ) or an adsorption filter. A flow of gaseous 2-chloroacrylonitrile is regulated with the aid of a metering valve ( 6 ) in such a way that a pressure of 13.3 Pa at a gas flow rate of 1.5 cm ³ (determined by the weight loss of the 2-chloroacrylonitrile) when the pump is sucking / min (based on standard conditions). Then a valve ( 7 ) is closed and a stream of vaporous iodine is regulated in an analogous manner so that a pressure of 2.66 Pa (0.02 Torr) is established at a gas flow rate of 0.5 cm ³ (based on standard conditions) .

The valve ( 7 ) is then opened again. The glass panes are heated to 150 ° C. by pumping hot oil through an substrate thermostat ( 10 ) through a substrate support ( 11 ). Now a plasma is ignited by switching on a high-frequency generator ( 12 ) with a frequency of 13.56 MHz. The reflected power is minimized with the help of an adaptation network ( 13 ). The power transmitted to the low-temperature plasma via a coil ( 14 ) is set to 10 W. In the course of 75 minutes, a glossy black polymer layer is deposited on the glass panes. The HF generator ( 12 ) is then switched off and the supply of the hot oil through the substrate support ( 11 ) is interrupted 10 minutes later. After the substrate support has cooled, the reactor is aerated via a valve ( 15 ) and the substrates are removed.

The properties of the polymer layer vary with the position of the glass panes on the substrate support ( 11 ) relative to the coil ( 14 ). The electrical conductivity of the polymer layer, which is deposited within the coil, is in the range of 10 ^-6 ohms ^-1 cm ^-1 with a thickness of 2 microns. The ratio of iodine to carbon determined using ESCA (Electron Spectroscopy for Chemical Analysis) is approximately 0.1. When the polymer layer is heated in the ultra-high vacuum of the ESCA device, no decrease in the iodine content is found up to a temperature of 215 ° C.

2nd embodiment

The procedure is analogous to Example 1, but as a monomer Ethyne (partial pressure: 9 Pa, flow rate: 1 cm³ / min), as dopant SbCl₅ (partial pressure: 2.7 Pa, Flow rate: 0.5 cm³ / min) was used. In addition, Argon as auxiliary gas (partial pressure: 4 Pa, flow rate: 0.5 cm³ / min) used. The substrate support is on Heated at 100 ° C. The RF power is 15 W, the duration of the plasma 30 min. Then without before ventilating the reactor for an hour 150 ° C substrate temperature with CCl₄ as telogen aftertreated.

To do this, the pump is switched off, a valve between Cold trap and reactor closed and vaporous CCl₄ from a (not shown) storage vessel in the Rekator let in.

The storage vessel contains liquid CCl₄ and is about Room temperature not heated. It will be the excess steam admitted into the reactor, whereby the partial pressure of the CCl₄ at room temperature in Reactor sets.

The layer has a thickness of approx. 1 µm and a conductivity of approx. 10 ^-1 Ohm ^-1 cm ^-1 .

The ratio Sb to carbon (determined with ESCA) is 0.13.  

3rd embodiment

The procedure is analogous to Example 1, but as a monomer Acrylonitrile (partial pressure: 13.3 Pa, flow rate: 1.5 cm³ / min), as a dopant iodine (partial pressure: 2.7 Pa, gas flow rate: approx. 0.5 cm³ / min). The temperature of the substrate support is 150 ° C, the RF power 50 W, the plasma duration 30 min.

The temperature of the substrate support is then increased to 200 ° C., the stream of acrylonitrile is interrupted, but the stream of iodine is left with simultaneous pumping. Helium is additionally let in as auxiliary gas (partial pressure: 13.3 Pa, gas flow rate: 1.3 cm³ / min), a plasma of 30 W is ignited and maintained for 20 minutes. The deposited layer has a thickness of approx. 0.5 µm and a conductivity of approx. 10 ^-5 Ohm ^-1 cm ^-1 .

4th embodiment

Analogously to Example 1, cyclooctatetraene is used as the monomer (Partial pressure: approx.6.5 Pa, flow rate: approx. 0.8 cm³ / min) together with argon (partial pressure: approx. 6.5 Pa, flow rate: approx. 0.8 cm³ / min), as Dopant SbCl₅ (partial pressure: 2.7 Pa, Flow rate: 0.5 cm³ / min) was used. The temperature of the substrate support is 100 ° C, the HF power 25 W.

After 30 minutes of plasma, the inflow of Monomers, argon and dopant interrupted and instead hydrogen (partial pressure: 133 Pa) fed.

If the temperature of the substrate support remains constant, a plasma (30 W) is ignited again and maintained for 10 minutes. The layer produced in this way is approx. 0.8 µm thick and has a conductivity of approx. 5 × 10 ^-5 Ohm ^-1 cm ^-1 .

The ratio of Sb to C is (measured with ESCA) about 0.09.  

5th embodiment 1,4-diazine

Analogous to Example 1, 1,4-diazine is used as the monomer (Partial pressure: 6.5 Pa, flow rate: 1 cm³ / min) together with helium (partial pressure: 6.5 Pa, Flow rate: 1 cm³ / min) and iodine as dopant (Partial pressure: 2.7 Pa, flow rate: approx. 0.5 cm³ / min) used. For better volatilization of 1,4-diazine the reactor, the storage vessel and the feed line the 1,4-diazine vapor to the reactor with IR lamps a wall temperature of approx. 50 ° C is heated. The temperature of the substrate support is 120 ° C, the RF power 50 W, the plasma duration 40 min.

Then the flow of diazine, iodine and the temperature of the substrate holder increased to 150 ° C and the separated Layer under flowing steam for 10 min left by C₂H₅I.

The layer is approx. 1.4 µm thick and has a conductivity of approx. 8 × 10 ^-5 Ohm ^-1 cm ^-1 with an I / C ratio (according to ESCA) of 0.12.

6th embodiment

Analogously to Example 1, phenylacetylene (partial pressure: 66 Pa, Flow rate: 7.5 cm³ / min) as a monomer together with bromine as Dopant (partial pressure: 26.6 Pa, flow rate: 5 cm³ / min) used.

For sufficient volatilization of phenylacetylene Reactor, storage vessel and feed of the phenylacetylene to Reactor with IR lamps to a wall temperature of approx. 50 ° C heated up.

The temperature of the substrate support is raised to 150 ° C set, the RF power is 40 W, the plasma duration 20 min.

The deposited layer is post-treated at the same temperature of the substrate holder as in Example 4 with a hydrogen plasma (133 Pa partial pressure, 30 W RF power, 10 min duration). The layer produced in this way is approx. 1.1 µm thick and has a conductivity of approx. 5 × 10 ^-3 Ohm ^-1 cm ^-1 .

The ratio of bromine / carbon in the layer (determined with ESCA) is approximately 0.14.  

7th embodiment

Analogous to example 6, terephthalaldehyde (partial pressure: 13.3 Pa, flow rate: approx. 1.5 cm³ / min) as a monomer, Iodine as dopant (partial pressure: 2.7 Pa, Flow rate: approx. 0.5 cm³ / min). The Reactor, the feed line and the storage vessel of the Monomers are heated to approx. 100 ° C with IR radiators Wall temperature warmed up.

The temperature of the substrate support is 150 ° C, the RF power 40 W, the plasma duration 20 min.

The layer produced is described as in Example 6, with hydrogen plasma to reduce the Number of radical sites post-treated.

The thickness of the layer is approx. 0.9 µm, the conductivity is approx. 3 × 10 ^-4 Ohm ^-1 cm ^-1 . The iodine to carbon ratio (according to ESCA) is 0.12.

8th embodiment

Analogous to Example 2, azobenzene is used as a monomer (Partial pressure: 13.3 Pa, flow rate: approx. 1.5 cm³ / min) and SbCl₅ (partial pressure: 2.7 Pa, flow rate: 0.5 cm³ / min) used as a dopant. The reactor as well as the storage vessel and the feed line of the azobenzene to the reactor are turned on with IR lamps a wall temperature of approx. 60 ° C warmed.

The temperature of the substrate support is 130 ° C, the RF power 10 W, the plasma duration 30 min.

Then, without intermittent ventilation of the Reactor treated for one hour with CHCl₃ as a telogen.

The temperature of the substrate support is raised here Raised to 150 ° C.

The thickness of the layer produced in this way is approximately 0.9 μm, the conductivity is approximately 2 × 10 ^-4 ohms ^-1 cm ^-1 . The ratio of antimony to carbon (determined with ESCA) is 0.1.

9. Embodiment

Analogous to Example 4, maleic anhydride (partial pressure: approx. 6.5 Pa, flow rate: approx. 0.8 cm³ / min) is used together with argon (partial pressure: 6.5 Pa, flow rate: 0.8 cm³ / min) and SbCl₅ ( Partial pressure: 2.7 Pa, flow rate: 0.5 cm³ / min) used as a dopant. The reactor, the storage vessel and the feed line of the maleic anhydride are heated to a wall temperature of approximately 60 ° C. using IR lamps. The temperature of the substrate support is 100 ° C, the RF power 30 W, the plasma duration 30 minutes. Subsequently, as in Example 4 with an H₂ plasma. The thickness of the layer produced in this way is approximately 0.8 μm, and the conductivity is approximately 2 × 10 ^-5 ohms ^-1 cm ^-1 .

Claims (17)

1. A process for producing thin, hole-free, electrically conductive polymer layers by polymerizing suitable volatile monomers which react under the action of plasmas to give polymers with a high content of conjugated double bonds, by means of low-temperature plasma, characterized in that known, volatile dopants or Mixtures of I₂, AsF₅, SbCl₅, Br₂, PCl₅, SiF₄, ICN and SO₃ admitted into the reactor during the polymerization and thus incorporated into the growing polymer layers, the temperature of the substrates during the polymerization being between 15 ° C and 250 ° C and the layer obtained, optionally by tempering under vacuum for 5 minutes to 5 hours at temperatures from 15 ° C. to 400 ° C. or with gaseous radical scavengers in the form of radical gases or halogenated hydrocarbons or other compounds known as "telogens" at substrate temperatures in the range from 15 ° C to 400 ° C for up to 5 hours. 2. The method according to claim 1, characterized in that as Monomeric unsaturated, aliphatic or alicyclic compounds be used. 3. The method according to claim 1, characterized in that as Monomeric aromatic or heteroaromatic compounds used will. 4. The method according to claim 1, characterized in that as Monomeric aromatic or heteroaromatic compounds with unsaturated substituents can be used. 5. The method according to claim 1, characterized in that as Monomers mono- or polysubstituted aromatic or heteroaromatic compounds are used as substituents Sulfone, ester, aldehyde, carboxy, anhydride or contain other groups that are easily eliminated in plasma. 6. The method according to claim 1, characterized in that as Monomeric dinuclear aromatic or heteroaromatic compounds are used, their aromatic or heteroaromatic Ring systems by azo, sulfone, sulfido, carbonyl or other groups that can be easily eliminated in plasma or by a disulfide group or another, easily in plasma fissile group are connected. 7. The method according to claim 1, characterized in that monomers be used according to claim 6, with the particularity that the aromatic or heteroaromatic ring systems in each case at least one sulfone, ester, aldehyde, carboxy, anhydride or other groups that can be easily eliminated in plasma as Contain substituents.   8. The method according to claim 1, characterized in that as Monomers unsaturated alicyclic compounds used in which a carbonyl, sulfone, lactone, anhydride, Sulphide or other group that can be easily eliminated in plasma Is part of the alicyclic ring. 9. The method according to claim 1, characterized in that as Monomers unsaturated, chlorinated, brominated or iodinated Hydrocarbons or cyanocarbons are used will. 10. The method according to claim 1, characterized in that mixtures of the monomers listed under claims 2 to 9 used will. 11. The method according to claim 1, characterized in that the a gaseous or vaporous monomer or monomer mixture non-polymerizing auxiliary gas or a mixture of such Gases is added. 12. The method according to claim 1, characterized in that the plasma with a DC voltage or low frequency (up to about 100 KHz) - glow discharge at a voltage of 50-5000 V, a power density of 0.001 to 0.5 W / cm ³ and a pressure of 1-1000 Pa is generated. 13. The method according to claim 1, characterized in that the plasma is generated with a high-frequency glow discharge at a frequency of 0.1 to 100 MHz, a power density of 0.001 to 0.5 W / cm ³ and a pressure of 1 to 1000 Pa. 14. The method according to claim 1, characterized in that the plasma with a microwave discharge at a frequency of 0.1 to 1000 GHz, a power density of 0.001 to 0.5 W / cm ³ and a pressure of 1 to about 10 ⁵ Pa (1 atm) is generated. 15. The method according to claim 1, characterized in that the plasma with a corona discharge at a DC or low frequency voltage (up to 100 KHz) from 0.1 to 20 kV, an electrical denabstand of 1 to 10 mm and a pressure of 10 to 2 × 10 ⁵ Pa is generated. 16. The method according to claim 1, characterized in that the plasma with a dependent glow discharge using a hot cathode at a discharge voltage of 0.4 to 1 kV, current densities of 0.05 to 0.5 mA / cm ² and a pressure of 0.05 to 20 Pa is generated. 17. The method according to claim 1, characterized in that the deposited polymer layers subsequent to the polymerization with gaseous radical scavengers in the form of halogenated hydrocarbons or other compounds known as "telogens" or in the form of compounds which in low-temperature plasma into radicals decay, are treated at substrate temperatures in the range of 288 K (15 ° C) to 673 K (400 ° C), the gaseous radical scavengers using a low temperature plasma at a pressure in the range of 0.65 Pa (0.005 Torr) to 133 Pa (10 Torr) and a power density of 0.001 to 0.1 W / cm ³ can be activated.