The present invention relates to a plasma system having a high-frequency inductively coupled plasma jet source and a method of producing a functional coating on a substrate.
Applying functional coatings to substrates is a widely used method of imparting desired properties to the surfaces of workpieces and/or components. A conventional method of producing such functional layers is by plasma coating in a medium-high or high vacuum, which requires complex evacuation techniques and yields relatively low coating rates. Therefore, this method is time-intensive and expensive.
Thermal plasmas in particular which allow high coating rates in the range of mm/h to be achieved are suitable for coating substrates in the atmospheric and subatmospheric pressure range. Of the thermal plasma sources, the high-frequency inductively coupled plasma jet source (HF-ICP jet source) is especially promising, such as that known from E. Pfender and C. H. Chang “Plasma Spray Jets and Plasma Particulate Interaction: Modeling and Experiments,” Convention Volume of the 6th Workshop on Plasma Technology, Technical University of Illmenau, 1998. Furthermore, German Published Patent Application No. 199 58 474 has proposed a method of producing functional layers by using such a plasma jet source.
The advantages of the HF-ICP jet source include the range of operating pressures in the source, usually extending from 50 mbar to 1 bar or more, and also the great variety of materials that may be used and deposited with such a plasma jet source. In particular, due to the fact that the starting materials are introduced axially into the very hot plasma jet, hard substances having a very high melting point may also be used. Another advantage of the HF-ICP jet source is that it works without electrodes, i.e., contamination of the layers produced by the jet source electrode material are prevented.
One disadvantage of the known HF-ICP jet sources and plasma systems using such plasma jet sources is the high temperatures in the plasma jet of several thousand degrees Celsius to which the substrate that is to be coated is also exposed. To this extent, the choice of usable substrates is considerably restricted.
An object of the present invention is to provide a plasma system having an HF inductively coupled plasma jet source and a method implementable therewith for producing a functional coating on a substrate, so that the thermal load on the substrate in producing the functional coating is greatly reduced in comparison with the related art.
The plasma system according to the present invention and the method according to the present invention for producing a functional coating on a substrate by varying the plasma intensity over time have the advantage over the related art that the temperature to which the substrate is exposed may be reduced to less than half in comparison with the related art.
It is also advantageous that using the plasma system according to the present invention, the advantages of a high-rate deposition method taking place in the atmospheric or near-atmospheric pressure range are combined with a reduction in substrate temperature and a change in the chemical processes in the plasma thus produced.
It is advantageous in particular that the method according to the present invention is not a high-vacuum method, so that complex equipment for producing such a high vacuum is not necessary.
It is also advantageous that the method according to the present invention may also be used with virtually all industrially relevant substrate materials such as steel and, as the case may be, also polymers, and at the same time a wide selection of materials and/or compositions of the coating to be produced, e.g., including insulating materials such as ceramics or sintered metals, is also available.
In addition, due to the periodic change in intensity of the plasma jet, preferably to such an extent that the plasma jet is extinguished between intensity peaks, there is regularly a chemical and/or physical disequilibrium state in the plasma jet, which permits promising approaches for production of previously unknown layer systems, e.g., ceramic layers or layer systems.
In particular, the aforementioned disequilibrium states, which occur mainly on igniting and extinguishing the plasma, constitute a considerable portion of the total time during which the plasma jet acts on the substrate, given suitable pulsation of the plasma jet over time, so that chemical processes taking place in these disequilibrium states become a dominant factor for the entire deposition of functional coatings using such a plasma system and/or plasma jet source.
It is thus particularly advantageous if, in addition to a plasma jet whose intensity varies periodically, the substrate being coated is situated on a substrate electrode which receives a voltage which is in phase opposition or is varied, preferably pulsed, over time in correlation with the change in intensity of the plasma jet.
Another advantageous embodiment of the present invention provides for the supply of gas and/or precursor material to the plasma, i.e., the plasma jet, to be correlated in time, in particular synchronized, with the varying intensity of the plasma jet.
Finally, it is advantageous if, at least temporarily during the production of the functional layer, the greatest possible pressure gradient is produced between the inside of the chamber and the plasma generating space, causing an acceleration of particles contained in the plasma jet onto the substrate. In this way, even deeper cavities in the surface of the substrate are better reached by the plasma and there is improved adhesion of the functional layer to the substrate.
a through 3h show the plasma jet, whose intensity varies as a function of time.
The present invention is based first on a plasma jet source 5, which is known fundamentally from E. Pfender and C. H. Chang, “Plasma Spray Jets and Plasma Particulate Interaction: Modeling and Experiments,” Convention Volume of the 6th Workshop on Plasma Technology, Technical University of Illmenau, 1998, or German Published Patent Application No. 199 58 474.
This plasma jet source 5 has a pot-shaped burner body 25 having a rear injector as an inlet 10 for supplying an injector gas 11. In addition, a first cylindrical sleeve 14 and a second cylindrical sleeve 15 are provided, a central gas 12 being supplied to the interior of first sleeve 14 through a suitable first inlet (not shown) and an enveloping gas 13 being supplied to the interior of second sleeve 15 through a suitable second inlet (not shown).
Burner body 25 also has an outlet orifice 26 in the form of a circle, for example, having a diameter of 1 cm to 10 cm, for example, in particular 3 cm on its side facing away from inlet 10, this opening being provided with an orifice restrictor 22 shaped according to the shape of plasma jet 21 to be produced. In addition, a water-cooled copper coil 17 is integrated into burner body 25 in the vicinity of outlet orifice 26 and is electrically connected to an HF generator 16.
When injector gas 11, central gas 12 and enveloping gas 13 are supplied, an electric power of 500 W to 50 kW, in particular 1 kW to 10 kW, is injected into the interior of burner body 25 at a high frequency of 0.5 MHz to 20 MHz, in particular 0.5 to 4 MHz, via coil 17 and HF generator 16, so that a plasma 21 of reactive particles emerging from outlet orifice 26 of burner body 25 in the form of a plasma jet 20 may be ignited and sustained in a plasma generating space 27. This plasma jet 20 then continues to act on a substrate 19, e.g., a piece of steel situated on a substrate carrier or a substrate electrode 18, situated opposite outlet orifice 26, e.g., at a distance of 5 cm to 50 cm.
Injector gas 11 introduced into burner body 25 through inlet 10, i.e., the injector is, for example, a precursor material for producing a functional coating on substrate 19. For example, a gas which reacts with injector gas 11 is suitable as central gas 12, which is optionally added. Enveloping gas 13, preferably argon, protects the walls of burner body 25 and also causes plasma 21 which is produced to be blown as a jet out of plasma jet source 5 through outlet orifice 26, so that it acts as a bundled or guided plasma jet 20 on substrate 19. To do so, enveloping gas 13 is introduced at a gas flow rate of 5000 sccm to 100,000 sccm (standard cubic centimeters per minute), preferably 20,000 sccm to 70,000 sccm.
The periodic variation in intensity of plasma jet 20 using electronic component 28, which may also be connected as a separate component between coil 17 and HF generator 16, takes place at a frequency of 1 Hz to 10 kHz, in particular 50 Hz to 1 kHz, between an adjustable upper limit and an adjustable lower limit of intensity. The lower limit is preferably set at zero, so that plasma jet 20 is periodically extinguished for a predefinable period of time. As an alternative, however, it is likewise possible to provide for the intensity of plasma jet 20 to be varied between the two limits given above in virtually any desired form, e.g., without plasma 21 being extinguished in the meantime. In particular, the intensity of plasma jet 20 may be varied in a rectangular, sinusoidal, sawtooth, rectangular or triangular form, optionally with a suitable offset, with respect to the resulting envelope.
For additional known details regarding the design of plasma jet source 5, as well as the methods performed with it for producing functional layers, reference is made to German Published Patent Application No. 199 58 474.
The intensity of plasma jet 20 from plasma jet source 5 and emerging from outlet orifice 26 of burner body 25 is explained with the help of
According to
In particular, due to the fact that according to
Such an expanded and accelerated plasma jet 20 in which the reactive particles present in the plasma jet may easily reach the velocity of sound or even supersonic velocity is capable of penetrating into deep cavities present on substrate 19. In addition, such an expansion of plasma jet 20 results in sudden cooling of plasma 21, which in turn further lowers the thermal load on substrate 19 and also yields chemical advantages with regard to an increase in plasma coating rate and an increase in the quality of the coating thus produced on the substrate.
In particular, the spatial separation of the processes in chamber 40 from plasma jet source 5 guarantees that plasma jet 20 may also be used in chamber 40 in a medium-high vacuum of 1 mbar without any change in the plasma mode, which is determined by plasma jet source 5.
The acceleration and expansion of plasma jet 20 in the operating mode according to
The marked pressure gradient between plasma jet source 5 and chamber 40, which aspirates the ionized gas present in plasma 21, i.e., plasma jet 20, into chamber 40 at a high velocity, also achieves the result that the two regions 30, 33 are largely separated with respect to the pressures prevailing there via outlet orifice 26.
The respective pressures are preferably selected so that the ratio of the pressure in first pressure range 30 to the pressure in second pressure area 33 is greater than 1.5, in particular greater than 3. For example, a pressure difference of more than 100 mbar between plasma generating space 27 in the interior of plasma jet source 5 and the interior of chamber 40 is maintained via a pumping device (not shown) which is connected to chamber 40.
On the whole, the acceleration and expansion of plasma jet 20 according to
Mount 32 according to
In particular, substrate generator 37 applies an electric voltage of typically 10 V to 5 kV, in particular 5 V to 300 V, at a frequency of 0 Hz to 500 MHz, in particular 1 kHz to 50 kHz to substrate electrode 18. In a preferred variant of the exemplary embodiment according to
Variants of the exemplary embodiment according to
With regard to the pressures in first pressure area 30 and second pressure area 33 according to
On the whole, a great variety of coatings may be produced on substrate materials which are of industrial relevance with the help of the exemplary embodiments described above, and substrates 19 may be either electrically conducting or electrically insulating. In particular, hard carbon layers may be produced in a low vacuum with the help of the above-mentioned plasma system and the method described here. In addition, the plasma system described here may also be used for treating the surface of substrate 19, e.g., for carbonizing, nitriding or heating it.
With regard to materials that may be introduced into plasma jet source 5 for deposition of a coating on substrate 19 within the context of the preceding examples, reference is first made to German Published Patent Application No. 199 58 474. In particular, at least one gaseous or microscale or nanoscale precursor material, a suspension of such a precursor material, or a reactive gas is supplied to plasma 21 in chamber 40 through inlet 10, which is designed as an injector, in plasma jet source 5 and/or plasma jet 20 through a feeder device (not shown here), so that it forms the functional coating in a modified form on substrate 19 or is integrated into it, in particular after undergoing a chemical reaction or a chemical activation. In addition, a carrier gas for the precursor material, in particular argon and/or a reactive gas for a chemical reaction with the precursor material, in particular oxygen, nitrogen, ammonia, a silane, acetylene, methane or hydrogen may be supplied to plasma 21 in plasma jet source 5, i.e., through the feeder device also located in chamber 40.
The precursor material is preferably an organic, organosilicon or organometallic compound which is supplied to plasma 21 and/or plasma jet 20 in a gaseous or liquid form, as microscale or nanoscale powder particles, as a liquid suspension, in particular having microscale or nanoscale particles suspended in it, or as a mixture of gaseous or liquid substances containing solids. In this way, a layer or a sequence of layers containing a metal silicide, a metal carbide, a silicon carbide, a metal oxide, a silicon oxide, a metal nitride, a silicon nitride, a metal boride, a metal sulfide, amorphous carbon, diamond-like carbon or a mixture of these materials may be produced as a functional coating on substrate 19 by using the plasma system explained here and the method explained here.
In conclusion, it should also be pointed out that HF generator 16 is preferably a tetrode generator, which makes is possible to generate plasma jet 20 with intensity modulation in a particularly simple manner as described here, so that the resulting temperature of substrate 19 is determined essentially by the average power of plasma jet 20 due to this intensity modulation. Thus, the method according to the present invention also makes it possible to use very high powers of plasma jet 20 for short periods of time without creating a thermal overload on substrate 19.
Furthermore, it is also possible for the regulation of the gases supplied to plasma jet source 5, e.g., central gas 12, injector gas 11 or enveloping gas 13 to correlate with the modulation of intensity of plasma jet 20 over time and/or the variation in the electric voltage applied to substrate electrode 18 over time.
Number | Date | Country | Kind |
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101 04 614.6-33 | Feb 2001 | DE | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/DE01/04564 | 12/5/2001 | WO | 00 | 2/9/2011 |