KR20050113186A - Apparatus and method for depositing large area coatings on planar surfaces - Google Patents

Abstract

The present invention provides an apparatus 200 for depositing a single coating material 232 on a large area plane 234 using an array 210 of multiple plasma sources 212 and co-reactant gas injectors 220, and It is about a method. Apparatus 200 includes one or more arrays 210 of a plurality of plasma sources 212 and a co-reactant gas injector 220, wherein each of the plurality of plasma sources 212 comprises a cathode 214, an anode. 216, and an inlet 218 for a non-reactive plasma source gas disposed in the plasma chamber 202, wherein the injector 220 is located in a deposition chamber 204 including a substrate 230. The co-reactant gas injector 220 provides a uniform flow of one or more reactant gases to a plurality of plasma sources 212 where a plurality of plasmas are generated via a single delivery system. One or more reactant gases react with a plurality of plasmas to form a uniform coating 232 on the substrate 230.

Description

FIELD AND METHOD FOR DEPOSITING LARGE AREA COATINGS ON PLANAR SURFACES

The present invention relates to an apparatus and a method for depositing a uniform coating on a plane. More specifically, the present invention relates to a method and apparatus for depositing a uniform coating on a plane using multiple plasma sources. More specifically, the present invention relates to a method and apparatus for depositing a uniform coating on a plane by injecting reactant gas through a conventional injection system into a plurality of plasmas generated by a plurality of expanded thermal plasma sources.

The plasma source can deposit various coatings such as transparent wear resistant coatings, transparent UV-filtration coatings, and multilayer coating packages at high deposition rates on the substrate. In this deposition process, the reactant gas interacts with the plasma to form species deposited on the substrate. Individual plasma sources, such as expanded thermal plasma (also referred to herein as "ETP" sources), may be used to uniformly coat areas having a diameter of about 10-15 cm.

Arrays of multiple plasma sources can be used to coat larger substrate areas. Such large area coating operations typically deal with depositing the coating on a macro flat surface or planar surface. To achieve a uniform coating in this plane, multiple plasma sources can be spaced in a two-dimensional pattern, such as a linear or zigzag array.

When multiple plasma sources are used to coat large areas, reactant gases are typically provided to each plasma source by separate delivery systems. That is, each plasma source has a separate reactant gas source required for separate flow control. However, when the scaling plasma deposition technique is used to coat surfaces with larger dimensions, the use of separate reactant sources and flow control agents can cause large changes in the coating process and result in a reduction in coating uniformity. In addition, as the number of plasma sources used in the coating process increases, the cost of having each plasma source with separate delivery systems and flow control becomes significantly significant.

Arrays of multiple plasma sources, where each plasma source has a separate reactant gas injector system, cannot uniformly coat large planes and are uneconomical. Accordingly, what is needed is a method and apparatus for uniformly coating a large area flat substrate using multiple plasma sources.

Summary of the Invention

The present invention meets these and other requirements by providing both methods and apparatus for depositing uniform coatings in large area planes using arrays of multiple plasma sources and conventional precursor- or reactant gas-injectors. . By providing reactant gas (es) to multiple plasma sources via a single delivery system, a uniform flow of reactant gas into each of the multiple plasmas can be easily maintained.

Accordingly, a first aspect of the invention provides an apparatus for depositing a uniform coating on the plane of a substrate. The apparatus comprises one or more arrays of a plurality of plasma sources for generating a plurality of plasmas, each of the plurality of plasma sources comprising an inlet for a non-reactive plasma source gas disposed in a cathode, an anode and a plasma chamber; A deposition chamber containing a substrate, wherein the deposition chamber is in fluid communication with the plasma chamber, the plasma chamber is maintained at a first predetermined pressure, and the deposition chamber is a second predetermined pressure less than the first predetermined pressure. Is maintained); And one or more co-reactant gas injectors disposed in the deposition chamber providing one or more reactant gases of uniform flow rate to each of the plurality of plasmas.

A second aspect of the present invention provides a co-reactant gas injector that injects one or more reactant gases of uniform flow into a plurality of plasmas generated by an array of plasma sources. The co-reactant gas injector includes a reactant gas inlet including a tubular-walled structure having an interior space from which one or more reactant gases are supplied from a reactant gas source; A plurality of first orifices adjacent to the first plasma, wherein each of the plurality of first orifices extends from the inner space through the tubular-wall structure to the outer surface of the reactant gas inlet and the plurality of first orifices Reactant gas is oriented from the interior space through the first plurality of orifices to the first plasma at a first flow rate); And a plurality of second orifices adjacent to the second plasma, wherein each of the plurality of second orifices extends from the inner space through the tubular-wall structure to the outer surface of the reactant gas inlet, the plurality of second orifices being one And the reactant gas above are oriented from the interior space through a plurality of second orifices to the second plasma at a second flow rate substantially the same as the first flow rate.

A third aspect of the invention provides an apparatus for depositing a uniform coating on the plane of a substrate. The apparatus comprises one or more arrays of multiple plasma sources for generating multiple plasmas, wherein the one or more multiple plasma sources are expanded thermal plasma sources, each of the plurality of plasma sources being disposed in a cathode, an anode and a plasma chamber. An inlet for a non-reactive plasma source gas); A deposition chamber containing a substrate, wherein the deposition chamber is in fluid communication with the plasma chamber, the plasma chamber is maintained at a first predetermined pressure, and the deposition chamber is a second predetermined pressure less than the first predetermined pressure. Is maintained at); And one or more co-reactant gas injectors disposed in the deposition chamber that inject a uniform flow of one or more reactant gases into each of the plurality of plasmas. The cavity reactant gas injector may comprise a reactant gas inlet including a tubular-wall structure having an interior space from which reactant gas is supplied from one or more reactant gas sources; A plurality of first orifices adjacent to the first plasma, wherein each of the plurality of first orifices extends from the inner space through the tubular-wall structure to the outer surface of the reactant gas inlet and the plurality of first orifices From and through a plurality of first orifices, directed to the first plasma at a first flow rate); And a plurality of second orifices adjacent to the second plasma, wherein each of the plurality of first orifices extends from the inner space through the tubular-wall structure to the outer surface of the at least one reactant gas inlet and the plurality of second orifices Reactant gas is oriented from the interior space through a plurality of second orifices and directed to the second plasma at a second flow rate substantially the same as the first flow rate.

A fourth aspect of the invention provides a method of depositing a uniform coating on the plane of a substrate. The method includes providing a substrate having a plane to the deposition chamber; Evacuating the deposition chamber at a pre-determined deposition pressure; Generating a plurality of plasmas from one or more arrays of the plurality of plasma sources; Each of the plurality of plasmas through the one or more co-reactant gas injectors, such that the first flow rate of the one or more reactant gases directed to the first plasma is substantially the same as the second flow rate of the one or more reactant gases directed to the second plasma Injecting into; Flowing one or more reactant gases and a plurality of plasmas toward the substrate into the deposition chamber; And reacting the one or more reactant gases with the plurality of plasmas to form a coating on the plane of the substrate.

A fifth aspect of the present invention provides a method for treating a single reactant gas in a plurality of plasma sources such that the first flow rate of at least one reactant gas directed to the first plasma is substantially the same as the second flow rate of at least one reactant gas directed to the second plasma. Provided is a method of implanting into a plurality of plasmas generated by an array. The method comprises supplying one or more reactant gases from a reactant gas source to a co-reactant gas injector; Passing one or more reactant gases through a first plurality of orifices in a cavity reactant gas injector adjacent to the first plasma, wherein the first plurality of orifices directs the one or more reactant gases to the first plasma at a first predetermined flow rate. Oriented to); And passing the one or more reactant gases through a second plurality of orifices adjacent to the second plasma, wherein the second plurality of orifices is provided such that the one or more reactant gases in the co-reactant gas injector is substantially equal to the first predetermined flow rate. 2 is directed to the second plasma at a predetermined predetermined flow rate.

A sixth aspect of the invention provides a substrate having a uniform coating deposited on a planar surface, wherein the uniform coating provides a substrate having a surface to the deposition chamber, wherein the deposition chamber is one of a plurality of plasma sources. In fluid communication with the at least one array, the at least one plurality of plasma sources being an expanded thermal plasma source having an inlet for a non-reactive plasma source gas disposed in the cathode, anode and plasma chamber, the plasma chamber in fluid communication with the deposition chamber); Evacuating the deposition chamber at a predetermined deposition pressure less than the first predetermined pressure, and evacuating the plasma chamber at the first predetermined pressure; Generating a plurality of plasmas in a plurality of plasma sources and flowing the plurality of plasmas into the deposition chamber; One or more reactant gases when the plurality of plasma flows into the deposition chamber such that the first flow rate of the one or more reactant gases directed to the first plasma is substantially the same as the second flow rate of the one or more reactant gases directed to the second plasma Injecting each of the plurality of plasmas through a co-reactant gas injector; Flowing one or more reactant gases and a plurality of plasmas toward the substrate into the deposition chamber; And reacting the one or more reactant gases with the plurality of plasmas to form a coating on the plane of the substrate.

These and other aspects, advantages, and salient features of the present invention will become apparent from the following detailed description, the accompanying drawings, and the appended claims.

1 is a schematic representation of an apparatus for depositing a uniform coating in a macroscopic plane using an array of expanded thermal plasmas, wherein reactant gas is provided to each plasma source by a separate reactant gas injector.

2 is a schematic representation of the device of the present invention for depositing a uniform coating on the macroscopic plane using an array of expanded thermal plasma sources.

3 is a schematic representation showing a top view and a cross-sectional view of a co-reactant gas injector of the present invention.

FIG. 4 is a plot comparing the thickness profile of amorphous silicon hydride (a-SiC: H) deposited using the co-reactant gas injector and the individual gas injector of the present invention, wherein the reactant gas is vinyltrimethylsilane (VTMS). )to be.

FIG. 5 is a plot of the thickness profile of a-SiC: H coating material obtained with an array of ETP sources, wherein the octamethylcyclotetrasiloxane (D4) reactant gas is formed by the co-reactant gas injector ring of the present invention. Provided to the array.

6 shows amorphous silicon hydride oxycarbide (a-SiO _x C _y :) deposited on a polycarbonate substrate from a mixture of D4 and oxygen (O ₂ ) using a single co-reactant injector and multiple co-reactant injectors of the present invention. It is a plot comparing the thickness profile of H).

In the following description, like reference numerals refer to like or corresponding parts throughout the several views shown in the drawings. Also, terms such as "upper", "lower", "outward", "inward" and the like are convenience words and are not to be considered as limiting terms.

In general, with reference to the drawings, in particular FIG. 1, it will be understood that the description is for the purpose of describing preferred embodiments of the invention but is not intended to be limited thereto. An apparatus 100 for depositing a uniform coating on a macroscopic plane-or flat surface-using an array 110 comprising a plurality of expanded thermal plasma sources 112 is schematically illustrated in FIG. 1. The apparatus 100 shown in FIG. 1 is described in US Patent Application No. 09 / 681,820, "Apparatus and Method for Large Area Chemical Vapor Deposition Using Expanding Thermal Plasma Generators" by Barry Lee-Mean Yang, et al., And US Patent Application No. 09 / 683,148 to Marc Schaepkens, "Apparatus and Method for Depositing Large Area Coatings on Non-Planar Surfaces," all of which are incorporated herein by reference in their entirety. Each of the plurality of ETP sources 112 is supplied with one or more reactant gases (not shown) that react with the generated ETP to form a coating on the surface of the substrate. One or more reactant gases are supplied to each of the plurality of ETP sources 112 at the same flow rate through separate reactant gas injectors 120. One or more reactant gases react in the plasma generated by each of the plurality of ETP sources 112 to obtain species from which a coating is formed.

When multiple plasma sources are used to coat large areas, the reactant gas is supplied to each plasma source by a separate delivery system. That is, each plasma source has a separate reactant gas source required for separate flow control. A separate reactant gas injector 120 is typically supplied to each of the plurality of ETP sources 112 as shown in FIG. 1. In the embodiment shown in FIG. 1, one or more reactant gases pass into each plasma generated by each of the plurality of ETP sources 112 through separate ring injectors 120, shown in top and cross-sectional views in FIG. 1. . Each of the one or more reactant gases is fed from a separate reactant gas source 126 to a separate ring injector 120, and a separate flow controller 124 is provided from each of the respective reactant gas sources 126 to each of the individual ring injectors 120. The flow of the reactant gas above is controlled. Alternatively, individual nozzles (not shown) may be replaced for individual ring injectors 120.

When using scaling plasma deposition techniques to coat surfaces with larger dimensions, the use of individual ring injectors 120, individual reactive sources 126, and flow controllers 124 may have significant variability in the coating process. This can reduce the uniformity of the coating. In addition, as the number of plasma sources used in the coating process increases, the cost of having each plasma source with separate delivery systems and flow control becomes significantly significant.

In general, it is desirable to produce coatings having a uniform profile of one or more selected properties across the entire coated surface. Such properties include, but are not limited to, coating thickness, wear resistance, radiation absorption, and radiation reflection. Each profile of these properties in a coating deposited by a single plasma source, such as an ETP source, has a Gaussian distribution about the axis of the plasma source. The size and shape of the Gaussian distribution will depend in part on the temperature of the plasma and also depends on the flow rate of one or more reactant gases into the plasma and the power used to generate the plasma. For plasmas generated at substantially the same flow rate and at the same power of one or more reactant gases into each of the multiple plasmas, the uniform profile of the desired coating properties across the plane results in the Gaussian distribution generated by the individual plasma sources. It can be obtained by arranging a plurality of plasma sources in an array that are intended to overlap.

An apparatus 200 for depositing a uniform coating on an uneven surface according to the present invention is shown in FIG. 2. Apparatus 200 includes one or more arrays 210 of multiple plasma sources 212. The device may include as many arrays as are practical and necessary for coating uneven surfaces. Similarly, each array 210 may include a number of plasma sources 212 as actual or desired. In an embodiment, the plurality of plasma sources 212 includes one or more ETP plasma sources. Although FIG. 2 presents a single array 210, multiple arrays 210 with six plasma sources 212, one or more arrays 210 with more than six plasma sources 212 are also described herein. It is considered to be within the scope. Array 210 may include, for example, up to about 12 plasma sources 212. Array 210 may be a linear array or a two-dimensional array, such as, but not limited to, a staggered array, a zigzag array, a grid and a polygon (eg, triangle, hexagon, octagon, etc.) of plasma source 212. .

Each of the plurality of plasma sources 212 includes a cathode 214, an anode 216 and a plasma source gas inlet 218 disposed within the plasma chamber 202. The plasma source gas is an inert gas such as rare gas, ie argon, helium, neon, krypton or xenon. Alternatively, other chemically non-reactive gases such as but not limited to nitrogen and hydrogen may be used as the plasma source gas. Preferably, argon is used as the plasma source gas. Plasma is generated at each of the plurality of plasma sources 212 by creating an arc between the cathode 214 and the anode 216 while introducing the plasma source gas into the arc through the plasma source gas inlet 218.

In one embodiment, the one or more plurality of plasma sources 212 is an expanding thermal plasma (also referred to herein as "ETP" later). In ETP, plasma is generated by ionizing the plasma source gas in an arc generated between one or more cathodes and anodes to generate cations and electrons. The following reaction takes place, for example, when an argon plasma is produced.

Ar → Ar ^{+ +} e ^-

The plasma then expands to high capacity at low pressure, thereby cooling the electrons and cations. In the present invention, plasma is generated in the plasma chamber 202 and is expanded into the deposition chamber 204 through the opening 206. As previously described, the deposition chamber 204 is maintained at a pressure significantly lower than the plasma chamber 202. As a result, the electrons in the ETP are so cold that they do not have enough energy to cause direct dissociation of one or more reactant gases in the ETP. Instead, one or more reactant gases introduced into the plasma may undergo charge exchange and dissociation recombination reactions with electrons in the ETP. In ETP, the cation and electron temperatures are about the same and are about 0.1 eV (about 1000 K). In other types of plasmas, the electrons have a temperature high enough to have a substantial effect on the chemical properties of the plasma. In such plasmas, the cations typically have a temperature of about 0.1 eV and the electrons have a temperature of about 1 eV or 10,000K.

The plasma chamber 202 is in fluid communication with the deposition chamber 204 through the opening 206. Deposition chamber 204 is in fluid communication with a vacuum system (not shown), which may maintain deposition chamber 204 at a lower pressure than plasma chamber 202. In one embodiment, the deposition chamber 204 is maintained at a pressure less than about 1 Torr (about 133 Pa), preferably less than about 100 millitorr (about 0.133 Pa), while the plasma chamber 202 is about 0.1 It is maintained at a pressure above atmospheric pressure (about 1.01 × 10 ⁴ Pa). The plasma chamber 202 is preferably maintained at a pressure of about 1 atmosphere (about 1.01 x 10 ⁵ Pa).

One or more co-reactant gas injectors 220 provide deposition chamber 204 for providing one or more reactant gases into each of the plurality of plasmas generated by the plurality of plasma sources 212 in the array 210 at a predetermined flow rate. Place it inside. Co-reactant gas injector 220 is shown in cross-section and top view in FIG. 3. By the reactant gas injector system 222 (FIG. 3) that includes a flow controller 224 (FIG. 3) to regulate the flow of one or more reactant gases from the reactant gas source 226 to the co-reactant gas injector 220. One or more reactant gases are provided to the co-reactant gas injector 220 from one or more reactant gas sources 226 (FIG. 3). One or more reactant gas sources 224 may be a single reactant gas source (in this case, a single flow controller 222 may be used) or a manifold (which may be mixed with various reactant gases or precursors before injection into multiple plasmas). It can be).

As the plasma enters the deposition chamber 204 through the opening 206, one through the co-reactant gas injector 220 into each of the plurality of plasmas generated by the plurality of plasma sources 212 in the array 210. The above reactant gas is provided. One or more reactant gases flow from each co-reactant gas injector 220 into each plasma at substantially the same flow rate. One or more reactant gases may comprise a mixture of reactant gases or a single reactant gas, and may be a single cavity from a single reactant gas source or separate multiple reactant gas sources 226 by separate reactant gas injector systems 222. Reactant gas injector 220 or a separate co-reactant gas injector 220.

The co-reactant gas injector 220 includes a co-injector ring 226, which is shown in cross-section and top view in FIG. 4. A separate cavity injection ring 220 may be provided for each reactant gas, or one cavity injection ring 220 may be used for injection of a mixture of reactant gases. The co-injector ring 220 is formed from a tubular-walled structure having an interior space through which one or more reactant gases are generated by a plurality of plasma sources 212 in the array 210 from the reactant gas source 226. Supplied to each of the plurality of plasmas generated. Co-reactor ring 220 may be formed from a stainless steel plumbing having a thickness of about 5/8 inch (about 15.9 mm). The cavity injector ring 220 includes a plurality of orifices (not shown) located adjacent to each of the plurality of plasmas. Each of the plurality of orifices extends through the tubular-wall structure from the inner space of the tubular-wall structure to the outer space of the cavity injector ring 220. The plurality of orifices are oriented such that one or more reactant gases pass from the interior space through the plurality of orifices and are directed to each of the plurality of plasmas. To allow insertion of the set screw with the mechanized orifice through the set screw, the cavity injector ring 220 includes threaded holes located about 0.5 inches (about 12.7 mm) apart. The orifice may have a diameter of about 0.040 inch (about 1.02 mm).

Co-reactant gas injector 220 may have a different arrangement than the arrangement of the rings. For example, the co-reactant gas injector 220 may be a single bar or other topographical form, such as, but not limited to, triangular, rectangular and wavy shapes from a tubular-walled structure having multiple orifices as described above. May be formed).

In general, the flow rate through an orifice, or multiple orifices, is determined by the pressure drop ΔP across the orifice relative to the conductance of the orifice (ie, the difference in pressure inside the co-reactant gas injector and pressure in the deposition chamber 204). Proportional to the ratio.

ΔP is a constant if the overall pressure of the co-reactant gas injector 220 and the pressure of the deposition chamber 204 are relatively unchanged. The velocity of the substantially even reactant gas for each of the plurality of plasmas is then provided by providing a co-reactant gas injector 220 having the same number of orifices of the same diameter that directs one or more reactant gases into each of the plurality of plasmas. Can be achieved. Thus, for an orifice of the same size, the linear density of the orifice adjacent to the first plasma will be substantially equal to the linear density of the orifice adjacent to the second plasma. Achieving a substantially uniform flow rate when ΔP is a constant can also be achieved by matching the conductance of a plurality of orifices adjacent to each of a plurality of plasmas. Conductance can also be matched by adjusting any of the linear density, orifice diameter, or orifice length of the opiris.

In some examples, the pressure may not be globally constant at the co-reactant gas injector 220. This condition can result in an uneven flow of reactant gas into the plurality of plasmas generated by the plurality of plasma sources 212. For example, a small amount of reactant gas may be located farther from the reactant gas source 226 than the plasma source ('B' in FIG. 3) located closer to the reactant gas source 226 (in FIG. 3). May be sent to the plasma generated by " A ". Under these conditions, the flow rate of reactant gas for each of the plurality of plasmas can be equalized by modifying one or more of the orifice diameter, the linear density of the orifices, and the conductances of the plurality of orifices in the co-reactant gas injector 220. For example, the flow rate of reactant gas into the plasma generated by the plasma sources A and B may cause the co-reactant gas injector 220 near the plasma source A having a larger number of orifices than the number of orifices located near the plasma source B. It can be equalized by providing. Alternatively, the flow rate can be equalized by providing a co-reactant gas injector 220 in which the orifice near plasma source A has a higher linear density than the linear density of the orifice near plasma source B. The flow rate of the reactant gas may be equalized by providing a co-reactant gas injector 220 having an orifice near plasma source A having a diameter greater than the diameter of the orifice located near plasma source B. Finally, providing a co-reactant gas injector 220 having an orifice with lower conductance near plasma source A may be used to equalize the flow rate for the plasma generated by plasma sources A and B.

For example, in the present invention, the linear orifice density along the co-reactant gas injector ring 220 can be changed to equalize the speed by replacing a portion of the set screw with the orifice with an unmechanized orifice with a conventional set screw. . The orifice conductance can also be varied by using a set-screw extending through the set screw to the mechanized orifice.

After being injected into each of the plurality of plasmas, one or more reactant gases undergo one or more reactions within each of the plurality of plasmas. Such reactions include, but are not limited to, charge exchange reactions, separate recombination reactions, and cleavage reactions. The products of the reactions occurring in the multiple plasmas then combine to deposit the coating material 232 on the surface 234 of the substrate 230, which is contained in the deposition chamber 204. The substrate 230 is mounted stationarily on a substrate holder (not shown) or coupled to an exercise actuator (not shown), which moves the substrate 230 relative to the array 210 (or 'scans'). do').

The following examples illustrate the features and advantages provided by the present invention and are not intended to limit the present invention.

Example 1

Coatings deposited on a flat (ie, planar) polycarbonate substrate using an array of ETP sources providing a co-reactant gas injector ring of the present invention were deposited using an array of ETP sources providing individual reactant gas injectors. The present invention is experimentally supported by comparison with coating materials. Thickness profile of amorphous hydrogenated silicon carbide (hereinafter referred to herein as "a-SiC: H") coating obtained with an array of ETP sources where vinyltrimethylsilane (VTMS) precursors are delivered to nozzles of individual ETP sources Was compared to the thickness profile of the a-SiC: H coating obtained with VTMS using an array of ETP sources providing the co-reactant gas injector ring of the present invention. The thickness profile of the coating material is shown in FIG. 4. The ratio (3%) of the standard deviation of thickness to average thickness (sigma / average) located between the ETP sources for the coatings obtained using the cavity injector rings of the present invention is determined by the respective reactant gas injector for each ETP source. It was lower than the ratio (13%) of the standard deviation of the film obtained using. Thus, coatings obtained using the co-injector gas rings of the present invention showed a higher degree of uniformity than coatings obtained using individual reactant gas injectors.

Example 2

The thickness profile of the a-SiC: H coating was obtained with an array of ETP sources in which the octamethylcyclotetrasiloxane (D4) reactant gas for the plasma generated by the array of ETP sources was provided by the co-reactant gas injector of the present invention. It became. The thickness profile of the deposited coating is disclosed in FIG. 5. As a result, it was demonstrated that with D4, the deposition yields a coating that is 5% (sigma / average) internal-ETP source thickness. Thus, the coating obtained by providing reactant gas D4 to the ETP-generated plasma through the co-injector gas ring of the present invention showed a high degree of uniformity.

Example 3

A coating of amorphous hydrogenated silicon oxycarbide (hereinafter referred to herein as "a-SiO _x C _y : H"), which serves as an anti-corrosion coating, was deposited from a mixture of D4 and oxygen (O ₂ ) on a polycarbonate substrate. . In one experiment, the coating was deposited by injecting both D4 and O ₂ through a single co-reactant gas injector ring. In another experiment, the coating was deposited by injecting O ₂ and D ₄ through separate co-reactant gas injector rings. Coating thickness profiles of the deposited coatings are compared in FIG. 6. In FIG. 6 the thickness profiles are statistically different, so that individual reactant gases are produced by multiple ETP plasmas in either a single co-reactant gas injector or a separate co-reactant gas injector to obtain a coating with high uniformity. It has been demonstrated that it can be provided to a plasma.

While typical embodiments have been disclosed for the purpose of illustrating the invention, the foregoing description is not intended to limit the scope of the invention. Accordingly, those skilled in the art may contemplate various modifications, adjustments, and alternatives without departing from the spirit and scope of the present invention. For example, the invention is not necessarily limited to the use of an array of multiple ETP sources, but instead the invention can be used in an array of multiple plasma sources that can be used to coat large area substrates.

Claims (44)

a) one or more arrays 210 of multiple plasma sources 212 for generating multiple plasmas, wherein each of the plurality of plasma sources 212 is a cathode 214, an anode 216 and a plasma chamber 202. An inlet 218 for a non-reactive plasma source gas disposed therein); b) the deposition chamber 204 containing the substrate 230, wherein the deposition chamber 204 is in fluid communication with the plasma chamber 202, and the plasma chamber 202 is maintained at a first predetermined pressure, The deposition chamber 204 is maintained at a second predetermined pressure less than the first predetermined pressure); And c) one or more co-reactant gas injectors 220 disposed in the deposition chamber 204 for providing one or more reactant gases of uniform flow rate to each of the plurality of plasmas. An apparatus 200 for depositing a uniform coating 232 on a plane 234 of a substrate 230. The method of claim 1, At least one of the plurality of plasma sources 212 is an expanded thermal plasma source. The method of claim 1, Apparatus (200) wherein one or more arrays (210) comprise one or more linear arrays of the plurality of plasma sources (212). The method of claim 1, Apparatus (200) wherein one or more arrays (210) comprise one or more two-dimensional arrays of the plurality of plasma sources (212). The method of claim 1, The apparatus 200, wherein the first predetermined pressure is at least about 0.1 atmosphere. The method of claim 5, The apparatus 200, wherein the first predetermined pressure is about 1 atmospheric pressure. The method of claim 1, The apparatus 200, wherein the second predetermined pressure is less than about 1 torr. The method of claim 1, Apparatus 200 having a second predetermined pressure less than about 100 millitorr. The method of claim 1, The apparatus 200, wherein the plasma source gas comprises one or more of argon, nitrogen, hydrogen, helium, neon, krypton, and xenon. a) a reactant gas inlet comprising a tubular-walled structure with an interior space from which at least one reactant gas is supplied from a reactant gas source; b) a plurality of first orifices 240 adjacent to the first plasma, wherein each of the plurality of first orifices 240 extends from the inner space through the tubular-wall structure to the outer surface of the reactant gas inlet, The plurality of first orifices 240 are oriented from the interior space through the plurality of first orifices and towards the first plasma at a first flow rate); And c) a plurality of second orifices 242 adjacent to the second plasma, wherein each of the plurality of second orifices 242 extends from the inner space through the tubular-wall structure to the outer surface of the reactant gas inlet, The plurality of second orifices 242 are oriented such that one or more reactant gases are passed from the interior space through the plurality of second orifices and directed to the second plasma at a second flow rate substantially the same as the first flow rate. Co-reactant gas injector 220 for injecting a uniform flow of one or more reactant gases into the plurality of plasmas generated by the array 210 of multiple plasma sources 212. The method of claim 10, The plurality of first orifices 240 includes a first predetermined number of orifices having a first linear density, and the plurality of second orifices 242 include a second predetermined number of orifices having a first linear density. Reactant injector. The method of claim 11, A reactant injector with a first predetermined number equal to the second predetermined number. The method of claim 11, A reactant injector with a first linear density equal to a second linear density. The method of claim 11, A reactant injector each of the plurality of first orifices 240 has a first conductance and each of the plurality of second orifices 242 has a second conductance equal to the first conductance. The method of claim 11, A reactant injector with a first predetermined number different from the second predetermined number. The method of claim 11, The reactant injector of each of the plurality of first orifices (240) has a first conductance, and each of the plurality of second orifices (242) has a second conductance different from the first conductance. The method of claim 11, Reactant injector comprises a injector ring comprising the array (210). a) one or more arrays 210 of multiple plasma sources 212 for generating multiple plasmas, wherein the one or more multiple plasma sources 212 are expanded thermal plasma sources, each of the plurality of plasma sources 212 A cathode 214, an anode 216 and an inlet 218 for a non-reactive plasma source gas deposited in the plasma chamber 202); b) the deposition chamber 204 containing the substrate 230, wherein the deposition chamber 204 is in fluid communication with the plasma chamber 202, and the plasma chamber 202 is maintained at a first predetermined pressure, The deposition chamber 204 is maintained at a second predetermined pressure less than the first predetermined pressure); And c) one or more co-reactant gas injectors 220 disposed in the deposition chamber 204, injecting a uniform flow of one or more reactant gases into each of the plurality of plasmas, wherein the co-reactant gas injector 220 i) a reactant gas inlet comprising a tubular-wall structure having an internal space from which the reactant gas is supplied from at least one reactant gas source; ii) a plurality of first orifices 240 adjacent to the first plasma, wherein each of the plurality of first orifices 240 extends from the inner space through the tubular-wall structure to the outer surface of the reactant gas inlet, The plurality of first orifices 240 are oriented from the interior space through the plurality of first orifices and towards the first plasma at a first flow rate); And iii) a plurality of second orifices 242 adjacent to the second plasma, wherein each of the plurality of first orifices 242 extends from the inner space through the tubular-wall structure to the outer surface of the one or more reactant gas inlets And the plurality of second orifices 242 are oriented such that the reactant gas passes from the interior space through the plurality of second orifices and directed to the second plasma at a second flow rate substantially the same as the first flow rate. Containing An apparatus 200 for depositing a uniform coating 232 on a plane 234 of a substrate 230. The method of claim 18, The plurality of first orifices 240 comprises a first predetermined number of orifices having a first linear density, and the plurality of second orifices 242 include a second predetermined number of orifices having a second linear density. Device 200. The method of claim 19, The apparatus 200, wherein the first predetermined number is the same as the second prescheduled number. The method of claim 19, The apparatus 200, wherein the first predetermined number is different from the second predetermined number. The method of claim 19, Wherein each of the plurality of first orifices (240) has a first conductance and each of the plurality of second orifices (242) has a second conductance equal to the first conductance. The method of claim 19, Wherein each of the plurality of first orifices (240) has a first conductance and each of the plurality of second orifices (242) has a second conductance different from the first conductance. The method of claim 18, At least one co-reactant gas injector (220) comprises an injector ring comprising the array (210). The method of claim 18, Apparatus (200) wherein one or more arrays (210) comprise one or more linear arrays of the plurality of plasma sources (212). The method of claim 18, Apparatus (200) wherein one or more arrays (210) comprise one or more two-dimensional arrays of the plurality of plasma sources (212). The method of claim 18, The apparatus 200, wherein the first predetermined pressure is at least about 0.1 atmosphere. The method of claim 27, The apparatus 200, wherein the first predetermined pressure is about 1 atmospheric pressure. The method of claim 18, The apparatus 200, wherein the second predetermined pressure is less than about 1 Torr. The method of claim 29, Apparatus 200 having a second predetermined pressure less than about 100 millitorr. The method of claim 18, The apparatus 200, wherein the plasma source gas comprises one or more of argon, nitrogen, hydrogen, helium, neon, krypton, and xenon. a) providing a substrate 230 having a plane 234 to the deposition chamber 204; b) evacuating deposition chamber 204 at a predetermined deposition pressure; c) generating a plurality of plasmas from one or more arrays 210 of the plurality of plasma sources 212; d) subjecting the one or more reactant gases to the one or more co-reactant gas injectors 220 such that the first flow rate of the one or more reactant gases directed to the first plasma is substantially the same as the second flow rate of the one or more reactant gases directed to the second plasma. Injecting each of the plurality of plasmas through; e) flowing one or more reactant gases and a plurality of plasmas into the deposition chamber 204 toward the substrate 230; And f) reacting the one or more reactant gases with the plurality of plasmas to form a coating 232 on the plane 234 of the substrate 230. A method of depositing a uniform coating (232) on a plane (234) of a substrate (230). The method of claim 32, At least one of the plurality of plasma sources (212) is an expanded thermal plasma source having an inlet (218) for a non-reactive plasma source gas deposited in a cathode (214), an anode (216) and a plasma chamber (202). The method of claim 33, wherein Flowing the one or more reactant gases and the plurality of plasmas toward the substrate into the deposition chamber 204 a) maintaining the deposition chamber 204 at a second predetermined pressure less than the first pressure in the plasma chamber 202; And b) expanding a plurality of plasmas from the plasma chamber (202) towards the substrate (230). The method of claim 32, Injecting the reactant gas into the plurality of plasmas a) feeding one or more reactant gases from the reactant gas source to one or more co-reactant gas injectors 220; b) passing one or more reactant gases through the first plurality of orifices in the cavity reactant gas injector 220 adjacent to the first plasma and the second plurality of orifices adjacent to the second plasma; c) directing one or more reactant gases into the first plasma at a first flow rate through the first plurality of orifices 240; d) directing the one or more reactant gases through the second plurality of orifices 242 into the second plasma at a second flow rate substantially the same as the first flow rate. How to include. 36. The method of claim 35 wherein The first plurality of orifices (240) comprises a first predetermined number of orifices and the second plurality of orifices (242) comprises a second predetermined number of orifices equal to the first predetermined number. 36. The method of claim 35 wherein The first plurality of orifices (240) comprises a first predetermined number of orifices, and the second plurality of orifices (242) comprises a second predetermined number of orifices different from the first predetermined number of orifices. 36. The method of claim 35 wherein Wherein each of the first plurality of orifices (240) has a first conductance and each of the second plurality of orifices (242) has a second conductance equal to the first conductance. 36. The method of claim 35 wherein Wherein each of the first plurality of orifices (240) has a first conductance and each of the second plurality of orifices (242) has a second conductance different from the first conductance. a) feeding one or more reactant gases from the reactant gas source to the co-reactant gas injector 220; b) passing the one or more reactant gases through the first plurality of orifices 240 in the cavity reactant gas injector 220 adjacent to the first plasma, wherein the first plurality of orifices 240 may be Oriented to direct the first plasma at a first predetermined flow rate); And c) passing one or more reactant gases through the second plurality of orifices 242 in the cavity reactant gas injector 220 adjacent to the second plasma, wherein the second plurality of orifices 242 Oriented to direct the second plasma at a second predetermined flow rate that is substantially the same as the first predetermined flow rate), Array 210 of multiple plasma sources 212 so that the first flow rate of the one or more reactant gases directed to the first plasma is substantially the same as the second flow rate of the one or more reactant gases directed to the second plasma. Injection into a plurality of plasmas generated by the method. The method of claim 40, Passing one or more reactant gases through the first plurality of orifices 240 in the co-reactant gas injector 220 includes passing one or more reactant gases through the first predetermined number of orifices, Passing the one or more reactant gases through an orifice (242) of the method comprises passing the one or more reactant gases through a second predetermined number of orifices. The method of claim 40, The first predetermined number differs from the second predetermined number. The method of claim 40, Wherein each of the first plurality of orifices (240) has a first conductance and each of the second plurality of orifices (242) has a second conductance different from the first conductance. A substrate 230 having a uniform coating 232 deposited on a plane 234, The uniform coating material a) providing a substrate 230 having a surface 234 to the deposition chamber 204, wherein the deposition chamber 204 is in fluid communication with one or more arrays 210 of multiple plasma sources 212, One or more of the plurality of plasma sources 212 is an expanded thermal plasma source having an inlet 218 for a cathode 214, an anode 216, and a non-reactive plasma source gas deposited in the plasma chamber 202, and the plasma chamber 202 ) Is in fluid communication with the deposition chamber 204; b) evacuating the deposition chamber 204 at a predetermined deposition pressure less than the first predetermined pressure, and evacuating the plasma chamber 202 at the first predetermined pressure; c) generating a plurality of plasmas in a plurality of plasma sources 212 and flowing the plurality of plasmas into the deposition chamber 204; d) one or more plasmas upon flow into deposition chamber 204 such that the first flow rate of one or more reactant gases directed to the first plasma is substantially the same as the second flow rate of one or more reactant gases directed to the second plasma Injecting reactant gas into each of the plurality of plasmas through one or more co-reactant gas injectors; e) flowing one or more reactant gases and a plurality of plasmas into the deposition chamber 204 toward the substrate 230; And f) A substrate 230 deposited by a method comprising reacting one or more reactant gases with a plurality of plasmas to form a coating 232 on a plane 234 of a substrate 230.