Patent Grant
10535503
This application is a 35 U.S.C. § 371 National Phase Entry Application from PCT/US2014/068858, filed Dec. 5, 2014, designating the United States. This application is related to PCT International Application Ser. No. PCT/US2014/068919 titled “Plasma Source Utilizing a Macro-Particle Reduction Coating and Method of Using a Plasma Source Utilizing a Macro-Particle Reduction Coating for Deposition of Thin Film Coatings and Modification of Surfaces,” the disclosure of which is incorporated herein by reference.
The present invention relates to a plasma source for the surface treatment and/or coating of large substrates. More particularly the present invention relates to a linear plasma source for plasma enhanced chemical vapor deposition and for plasma surface treatment, in particular a plasma source based on a hollow cathode type discharge.
Various plasma sources are disclosed in the prior art for the deposition of thin films and chemical modification of surfaces.
When large substrates are to be treated, these plasma sources typically are linear ionic sources like the one disclosed by Madocks in U.S. Pat. No. 7,411,352. This plasma source is based on a magnetron discharge and produces a linear beam of ions or, by combining several sources, multiple parallel beams of ions directed towards the substrate surface. Madocks discloses that for coating purposes a coating precursor can be provided outside of the plasma sources. The plasma extends essentially only along one dimension, i.e. the length of plasma source. The width of the ion beam is limited by the pressure inside the process chamber which restricts the mean free path length. When a substrate is conveyed beneath this plasma source the contact time is therefore relatively short. Thus the number of plasma sources will have to be multiplied when for example the treatment duration of the substrate with the plasma needs to be increased. Furthermore a coating precursor injected next to the plasma source has limited opportunity to interact with the plasma beam. This results in relatively low deposition yield and increases the risk of soiling the coater with precursor that has not been able to react with the substrate surface.
Madocks also discloses that sputtering of the electrode material occurs and that the sputtered material redeposits and thus remains within the source. Sputtering of the electrode material however results in reduced lifetime of the electrodes. The redeposition of the sputtered material may also lead to blockage of the nozzles of the plasma source, making a uniform substrate treatment or coating impossible. Furthermore, the sputtered electrode material may condense and/or react further, leading to the formation of debris that either block the source's nozzles or fall on the substrate creating defects. These nozzles are made up by one of the plasma source's electrodes. The electrode is thus exposed to the coating process atmosphere in the vacuum chamber and therefore prone to soiling from the injected coating precursor.
Furthermore the magnetron discharge based source disclosed by Madocks requires magnets. Magnets are sensitive to high temperatures, these sources therefore cannot be run at high temperatures and need to be cooled by active or passive means. The presence of these magnets as well as the necessary presence of shunts lead to a complex and thus expensive assembly.
This source also produces a relatively low density of free electrons compared to plasma sources based on hollow cathode discharge. For coating purposes, the electrons of the plasma serve to ionize the coating precursor. Therefore the coating efficiency is low when a magnetron plasma based source such as disclosed by Madocks is used.
Jung discloses in EP0727508 A1 a hollow cathode linear plasma source based on two parallel electrodes. The plasma extends essentially only along one dimension, i.e. the length of plasma source, forming a narrow plasma beam. Jung discloses that in order to avoid sputtering of the electrode material a stream of inert gas has to be injected parallel to the electrodes. The injection of an inert gas parallel to the electrodes however leads to a reduction of the yield of reactive ions and therefore reduced treatment efficiency or coating yield.
One of the major problem with these kinds of high deposition rate sources is the fact that the walls of the plasma sources become quickly soiled by reacting prematurely with precursors that flow through the plasma. Due to this problem, the use of this process in industry is quite limited and requires frequent cleaning cycle which limits the throughput of the production line.
Another drawback of these high deposition rate sources is that it is difficult to confine the precursor to the substrate surface after it leaves the plasma source. As a consequence a significant portion of the precursor cannot be used to form a coating on the substrate. This leads to reduced coating yield and to soiling of the coater with the transformation of the precursor on surfaces surrounding the plasma source.
Thus there remains a need in the large area surface treatment and large area coating field for a simple plasma source that can provide a uniform plasma of considerable length that can treat and/or coat large substrates with high efficiency and low amount of soiling and of defects.
In an aspect of the invention there is provided a linear plasma source useful for the deposition of thin films on large substrates and for the plasma treatment of the surfaces of large substrates. Plasma treatment is meant to encompass e.g. surface activation, surface cleaning as well as surface etching.
In an aspect of the present invention there is provided a hollow cathode based plasma source with a very wide linear plasma.
In an aspect of the present invention there is provided a plasma source that is able to form a uniform wide linear plasma.
In an aspect of the present invention there is provided a plasma source with a low rate of electrode cavity surface sputtering.
In an aspect of the present invention there is provided a plasma source with a high density of free electrons.
In an aspect of the present invention there is provided a method of forming a large area coating using a uniform wide linear plasma.
These aspects as well as other aspects of the invention will be clarified in the detailed description of particular embodiments of the invention with reference to the drawings of the figures, wherein:
Hollow cathode plasma source is taken to mean a plasma forming device typically described as two cavities alternating between positive (anode) and negative potential (cathode) with a 180° phase shift. In the cathode cavity electrons are oscillating between negative electric fields of the cavity and are thereby confined.
Plasma is taken to mean an electrically conductive gaseous medium comprising both free electrons and positive ions.
Reactant gas is taken to mean oxygen and/or nitrogen. It is often desirable to deposit on a surface compounds which may not be chemically available from the precursor gas alone. Often, reactant gases such as oxygen or nitrogen are added to the chemical vapor deposition (CVD) process to form oxides or nitrides. Other reactant gases may comprise fluorine, chlorine, other halogens or hydrogen. A reactant gas may be differentiated from a precursor gas by the fact that even when energized or chemically decomposed, condensable molecular entities are not formed. Generally, reactant gases or reactant gas fragments cannot by themselves grow a solid deposition but they can react and become chemically incorporated into a solid deposition derived from precursor gases or other solid deposition sources. Preferred reactants are O2, N2, NH3, CH4, N2O, H2.
Precursor is taken to mean a gas or a liquid, selected according to its vapor pressure, in molecular form containing a chemical element or elements to be condensed into a solid coating. The elements to be condensed from the precursor may include metals, transition metals, boron, carbon, silicon germanium and/or selenium. Generally, a precursor molecule is unreactive or not prone to attaching on a surface until energized, partially decomposed, or fully decomposed by an energy source, whereupon a chemical fragment of the precursor containing the desired chemical element for coating becomes chemically able to bond to or condense upon a surface in a solid form. The condensed portion of the precursor compound may be primarily a pure element, a mixture of elements, a compound derived from the precursor compound constituents or a mixture of compounds. Preferred precursor gas are inorganic compounds such as: SiH4, N(SiH3)3, TMDSO, HMDSO, TTIP, . . . or any other that contain appropriate metal to deposit oxide, nitride or oxynitride films such as: SiO2, SixNy, ZrO2, TiO2, Al2O3, AlN, SnO2, ZnO, etc. . . . and mixtures of one or more of these materials, such as SiOxNy, SixAlyNz.
Substrate is taken to mean either a small area or large area item to be coated or have its surface chemically modified by this invention. Substrate referred to herein can be comprised of glass, plastic, metal, inorganic materials, organic materials or any other material that has a surface to be coated or modified.
AC power or AC power source is taken to mean electric power from an alternating source wherein the voltage is changing at some frequency in a manner that is sinusoidal, square wave, pulsed or according to some other waveform. Voltage variations are often from negative to positive. When in bipolar form, power output delivered by two leads is generally about 180 degrees out of phase.
Secondary electron or secondary electron current is taken to mean electron emission from a solid surface as a result of bombardment of that surface by a particle and the current that is created as a result, respectively.
Dark space is taken to mean a narrow zone or area around an electrode whereby plasma current is very low. Generally, two oppositely charged plasma electrodes or a plasma electrode and a ground potential conductor spaced apart by the dark space distance will exhibit substantially no current flow between them.
The construction material for the electrodes must be sufficiently electrically conductive so that electrons can be emitted from the electrode surfaces and so that they can carry the necessary electrical current to sustain the discharge. Electrode materials comprise metals, metal alloys, metal compounds, carbon, carbon compounds, ceramics, or semiconductors. Most commonly used materials are metals, metal alloys or graphitic carbon.
Electrode materials may be selected for particular electron emission properties. They may comprise materials with low work function or with high secondary emission coefficients which allow lower operating voltages and increased electron current.
The electron emitting surfaces may comprise metal, metal-based, metalloid, metalloid-based or carbon-based coatings deposited on the electrodes. These coatings may comprise materials with low work function or with high secondary emission coefficients which allow lower operating voltages and increased electron current.
Almost any gas may be used as plasma forming gas. Most commonly the plasma forming gas comprises He, Ne, Ar, Kr, Xe, O2, N2, H2, NH3 or mixtures on any of these gases. The gas flow rate is generally comprised between 0.5 sccm and 10 sccm per linear mm of cavity length.
Different arrangements and shapes are possible for the outlet and nozzle. Typically they are an array of holes. They may also comprise a slot or elongated orifice. A gas pressure drop exists between the hollow cathode cavities and the exterior, i.e. the vacuum chamber. Thereby a sufficiently high pressure level for sustaining a stable plasma is maintained in the cathode cavity and an outflow of the ionized gas from the cavity towards the exterior is obtained. The nozzles thus distance the electrodes from the coating process atmosphere in the vacuum chamber and therefore reduce the probability of soiling from the injected coating precursor.
The first and second hollow cathode electrodes function alternatingly as cathodes and anodes. When one electrode is electrically positive with respect to the plasma potential, the other one is electrically negative with respect to the plasma potential and this electrical polarity reverses at some frequency.
This may be obtained by using an AC power source or a pulsed DC power source. Typically the power sources supply a bipolar voltage approximately 180 degrees out of phase with an alternating polarity of the phases such that the electron current between the electrodes reverses at some frequency. The preferred voltage range is comprised between 300V and 1200V, the preferred frequency range is comprised between 10 kHz and 1 MHz, preferably between 10 kHz and 100 kHz, most preferably about 40 kHz.
The plasmas formed by the hollow cathode plasma source of this invention are non-equilibrium, non-thermal plasmas that are highly electrically conductive and that typically carry a charge of ground potential of several 10's of volts positive. The electrodes are placed in sufficient proximity to allow an electron current to flow between electrodes of opposite polarity at the operating pressure of the vacuum chamber.
The operating pressure in the vacuum chamber may be kept between 0.001 mbar and 1 mbar, typically between 0.002 mbar and 0.1 mbar, more typically between 0.007 and 0.05 mbar.
A plasma is formed in the volumes enclosed by the first and second electron emitting surfaces, plasma that extends throughout the gas containing space that lies in between the electron emitting surfaces. The plasma is made substantially uniform over its length in the substantial absence of closed circuit electron drift.
Thereby the plasma source according to the invention forms a linear plasma beam that has a high density of free electrons and that is not limited to a narrow width beneath the plasma source but rather extends in between the two hollow cathode cavities. The plasma source according to the present invention therefore allows high contact times between substrate and plasma. It also presents better opportunities for a coating precursor injected in proximity to the plasma beam to interact with it. Thereby high deposition yields and high treatment efficiencies are provided while the risk of soiling of the plasma source as well as the coater as a whole is reduced.
Furthermore the plasma source according to the invention requires no additional electrodes, acceleration grids, magnetic fields, shunts, or neutralizers. It is therefore less complex and thus less costly than other plasma sources. However, when desired for particular reasons, magnets and/or additional electrodes may be used in conjunction with the arrangement of hollow cathodes according to the present invention.
In an aspect of the invention, there are provided dimensions of certain key parameters of the hollow cathode plasma source.
The key parameters identified by the inventors are:
The inventors recognize the surprising effect of these key parameters. They have discovered that among all parameters that govern these plasma sources, these parameters in particular, either alone or in combination, have a significant impact on the density of free electrons in the plasma generated by the hollow cathode plasma source and as well as the amount of sputtering of the plasma source cavity surfaces. To achieve these effects, the inventors have discovered that these key parameters need to respect specific dimensions. The dimensions of these key parameters may be different for each hollow cathode plasma source cavity, preferably they are the same for both hollow cathode plasma source cavities.
According to an advantageous embodiment specific dimensions of these key parameters separately or in any combination lead to a reduced amount of sputtering of the cavity surfaces. The plasma source according to the invention therefore does not require the injection of an inert gas parallel to the electrodes. Therefore a high yield of reactive species is obtained leading to high treatment efficiency or coating yield. The plasma source according to the present invention therefore also limits redeposition of sputtered material inside the plasma source and its nozzles and also reduces the formation of debris. Thus the treatment or coating uniformity are improved and the amount of defects in the treatment or coating is reduced.
According to an advantageous embodiment the hollow cathode discharge based plasma source together with specific dimensions of these key parameters separately or in any combination also lead to increased density of free electrons. Therefore the treatment efficiency or coating efficiency is increased. Furthermore the more efficient usage of coating precursor leads to reduced soiling of the vacuum chamber and vacuum pumps by unreacted coating precursor.
During long duration trials of more than 100 hours it was observed that plasma sources with a rounded rectangular cavity cross section shape (
By comparing experimental results with computer simulation data, the inventors have found that the amount of sputtering of the hollow cathode cavity surfaces is related to the absorption of reactive ions on the hollow cathode cavity surfaces as determined by numerical simulation.
The simulation software that was used for simulating gas flows and gas discharges is a program called PIC-MC that has been developed by the Fraunhofer-Institute for Surface Engineering and Thin Films IST, Braunschweig, Germany. The software combines the simulation of gas flows, magnetic fields and plasma. For the gas flow simulation it uses the Direct Simulation Monte Carlo (DSMC), for the magnetic field simulation it uses the Boundary Element Method (BEM) and for the plasma simulation it uses the Particle in Cell-Monte Carlo method (PIC-MC).
The simulations were made on a pseudo 2D model which is a transversal 1.016 mm thick slice of the hollow cathode plasma source. Pseudo-2D means that the slice has a small thickness and a periodic condition is applied on each plane in the transversal direction.
For the simulations many different plasma forming gasses can be used, in the following examples argon was used. In order to limit the computation time Si2H6 was chosen as coating precursor and among its possible reactions the following two were selected:
Si2H6+e−→Si2H4++2H+2e− (1)
Si2H6+e−→SiH3+SiH2+H+e− (2)
Hydrogen species were not included in the simulations.
For each given set of input parameters the simulation yields data regarding number and velocity of the different gas phase species (atoms, ions, molecules and electrons) throughout the space they occupy. From this data certain values can be calculated, such as densities and fluxes, where a flux is the rate of movement of gas phase species across a unit area (unit: mol·m−2·s−1).
Another useful calculation is the flux that is absorbed on a certain surface. Given a certain sticking coefficient of the cathode cavity material, the ion absorption on its surface can be calculated from the ion flux directed at it. By correlating experimental results with simulation data the inventors found that the formation of debris and thus the cavity surface sputtering observed on real plasma sources was related to the level of ionized plasma species absorbed by the electrodes' cavity surfaces according to the simulation model.
Low levels of ionized plasma species absorbed by the electrodes' cavity surfaces mean that the level of cavity sputtering is low and debris formation is low.
Another important quantity is the electron density generated. The electron density has a major influence on surface treatment or coating efficiency, with high electron densities leading to high surface treatment or coating efficiencies. In the present simulations the electron density was determined in the vacuum chamber on a line set at a distance of 2.54 mm from the chamber structure that supports the plasma source and averaged.
In one aspect of the invention there is provided a hollow cathode cavity transverse cross section shape.
The inventors surprisingly found that the level of ionized plasma species absorbed by the cathode cavity surfaces was reduced when the rectangular cavity cross section shape was replaced by a cross section enclosing the same surface area having a rectangular shape where at least one corner is rounded or preferably all four corners are rounded (rounded rectangular shape), or preferably having a rounded rectangular shape whose four corner radii are equal to half its width or most preferably having a circular shape.
Variations to these shapes, in particular leading to intermediary shapes, may be made without departing from the present invention. In particular these are elliptical or oval shapes or shape variations such as illustrated in
Furthermore the inventors found that the circular cavity cross section shape also improved the electron density over the rectangular shape.
In one aspect of the invention there is provided a hollow cathode cavity transverse cross section area.
According to an embodiment of the invention the cavity cross section area is comprised between 100 mm2 and 10000 mm2, preferably between 500 mm2 and 4000 mm2.
According to another embodiment of the present invention the cavity cross section area is comprised between 100 mm2 and 1000 mm2, preferably between 500 mm2 and 1000 mm2, most preferably between 500 mm2 and 750 mm2. The inventors surprisingly found that at lower cavity cross section area, electron density was increased.
According to another embodiment of the present invention the cavity cross section area is comprised between 1000 mm2 and 4000 mm2, preferably between 1500 mm2 and 4000 mm2, most preferably between 2000 mm2 and 4000 mm2. The inventors surprisingly found that at higher cross section area the level of ionized plasma species absorbed by the cathode cavity surfaces was reduced.
According to another embodiment of the present invention the cavity cross section area is comprised between 750 mm2 and 1500 mm2, preferably between 750 mm2 and 1250 mm2, most preferably around 1000 mm2. The inventors found that at an intermediate cross section area a balanced level of ionized plasma species absorbed by the cathode cavity surfaces versus electron density was obtained.
In one aspect of the invention there is provided a hollow cathode cavity distance, measured from one cavity center to the other cavity center. The center of the cavity is the geometrical center of the cavity cross section if it has a regular geometrical shape. If it has an irregular shape it is its centroid.
The inventors surprisingly found that increasing the hollow cathode cavity distance up to a certain threshold leads to a reduced level of ionized plasma species absorbed by the cathode cavity surfaces with decreased electron density. According to the invention the cavity distance is comprised between 85 mm and 160 mm, preferably between 100 mm and 145 mm, most preferably around 125 mm.
It is clear to the person skilled in the art that the cavity distance is also dependent on the cavity size and on insulation, structural and cooling requirements.
In one aspect of the invention there is provided an outlet nozzle width.
In the present design the outlet nozzles are centered at the vertical line running through the center of the cavity cross section shape. The centers of each cavity cross section and of its outlet nozzle are aligned with the vertical line running through the cavity cross section's center. However variations and modifications of the outlet nozzle placement and orientation may be made without departing from the present invention.
In its basic design the outlet nozzle width is in the range of 3.5 mm to 5 mm. The inventors found that increasing the width reduced the level of ionized plasma species absorbed by the cathodes cavity surfaces and increased the electron density. When the outlet nozzle width is increased above a threshold value the electron density is strongly reduced. Probably because the pressure in the cavity cannot be maintained at a level high enough to produce a significant plasma discharge.
According to the present invention the outlet nozzle width is comprised between 1 mm and 25 mm, preferably between 3 mm and 25 mm, more preferably between 8 mm and 22 mm, more preferably between 8 mm and 12 mm, most preferably around 10 mm.
According to another embodiment of this invention two or more plasma sources can be combined to increase the surface treatment or coating duration, using a single power source in common or using multiple individual power sources.
According to another embodiment of the present invention the plasma source is used for surface treating a substrate, e.g. surface cleaning, surface refreshment, surface activation. The substrate is conveyed beneath the plasma source and exposed to the ions and electrons of the plasma that extends throughout the vacuum space in between the outlet nozzles of the plasma source.
According to another embodiment of the present invention the plasma source is used for coating a substrate.
Plasma sources with two 10 cm (plasma length) long stainless steel hollow electrodes according to the present invention were built and operated for more than 100 hours under the following conditions:
Two different cavity cross section shapes were compared, rounded rectangular and circular.
Cavity surface sputtering lead to the formation of debris particles. At 24 hour intervals the debris on the glass substrate was collected and the number of debris particles was counted. As can be seen from the table below the number of debris particles increased much more rapidly for the rounded rectangular cavity cross section shape than for the circular shape.
In examples 3 to 17 hollow cathode plasma sources were simulated.
For each key parameter a set of up to five variations was compared. In each set one variation was chosen as reference. After calculating for each variation the level of absorption of ionized plasma species on the cathode cavity surfaces as well as of the electron density, the ratio of this value to the reference's value was determined.
The following parameters are kept unchanged for all simulation examples:
Three cavity cross section shapes were simulated: rectangular, rounded rectangular and circular. The rectangular cross section was 10 mm wide and 50 mm high. The rounded rectangular shape was about 14 mm wide and 45 mm high with four rounded corners (corner radii: 7 mm). The circular cross section shape had a radius of 13 mm.
The following parameters were kept the same for examples 3 to 5:
Absorption of ionized plasma species on the cathode cavity and thus cavity sputtering and debris formation decrease when going from rectangular to rounded rectangular to circular cavity cross section shape.
Electron density and thus process efficiency increase when going from rectangular to circular cavity cross section shape.
Three cathode cavity cross section areas were simulated: 500 mm2, 1000 mm2 and 2000 mm2
The following parameters were kept the same for examples 6 to 8:
Absorption of ionized plasma species on the cathode cavity and thus cavity sputtering and debris formation decrease when cavity cross section area is higher.
Electron density and thus process efficiency increases when cavity cross section area is lower.
At around 1000 mm2 cavity cross section area a balanced level of absorption of ionized species and electron density is obtained.
Five cavity distances were simulated: 168 mm, 142 mm, 114 mm, 104 mm, and 84 mm.
The following parameters were kept the same for examples 9 to 13:
Absorption of ionized plasma species on the cathode cavity and thus cavity sputtering and debris formation decreases when cavity distance is higher.
Electron density and thus process efficiency remains good for all cavity distances tested, except the highest. An interesting balance between both ratios is obtained between 100 mm and 145 mm cavity distance.
Four nozzle widths were simulated: 5 mm, 10 mm, 20 mm, and 40 mm.
The following parameters were kept the same for examples 9 to 13:
Absorption of ionized plasma species on the cathode cavity and thus cavity sputtering and debris formation decrease when the outlet nozzle width is larger.
Electron density and thus process efficiency increases when the outlet nozzle width is larger. At very high outlet nozzle width, for example at 40 mm, the pressure difference between the inside of the cavities and the vacuum chamber cannot be held at a sufficient level for maintaining a stable plasma, leading to a very low electron density level.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2014/068858 | 12/5/2014 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2016/089424 | 6/9/2016 | WO | A |
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