KR20200039827A - Selective in-situ cleaning of high-K films from processing chamber using reactive gas precursor - Google Patents

Abstract

In one implementation, a method for cleaning a processing chamber is provided. The method includes introducing a reactive species into the processing chamber, the processing chamber having residual high-k dielectric material formed on one or more inner surfaces of the processing chamber. The reactive species is formed from a halogen-containing gas mixture, and the one or more inner surfaces include at least one surface with a coating material formed thereon. The method further includes reacting the reactive species with the residual high-k dielectric material to form a volatile product. The method further includes removing volatile products from the processing chamber. The removal rate of residual high-k dielectric material exceeds the removal rate of the coating material. The high-k dielectric material is selected from zirconium dioxide (ZrO ₂ ) and hafnium dioxide (HfO ₂ ). The coating material includes a compound selected from alumina (Al ₂ O ₃ ), yttrium-containing compounds and combinations thereof.

Description

Selective in-situ cleaning of high-K films from processing chamber using reactive gas precursor

[0001] The implementations described herein generally relate to methods and apparatus for in-situ removal of unwanted deposition buildups from one or more internal surfaces of a substrate-processing chamber.

[0002] Display devices have been widely used in various electronic applications, such as TVs, monitors, mobile phones, MP3 players, e-book readers, personal digital assistants (PDAs), and the like. Display devices are generally designed to create an image by filling the gap between two substrates (eg, pixel electrode and common electrode) and applying an electric field to a liquid crystal having an anisotropic dielectric constant that controls the strength of the dielectric field. do. By adjusting the amount of light transmitted through the substrates, light and image intensity, quality and power consumption can be efficiently controlled.

[0003] Various different display devices, such as active matrix liquid crystal display (AMLCD) or active matrix organic light emitting diode (AMOLED) can be used as light sources for the display. In the manufacture of display devices, electronic devices with high electron mobility, low leakage current and high breakdown voltage allow a wider pixel area for light transmission and circuit integration, resulting in a brighter display, higher overall electrical efficiency, faster It will result in response times and higher resolution displays. The low film qualities of the material layers formed in the device, such as impurities or dielectric layers with low film densities, often lead to poor device electrical performance and short service life of the devices. Thus, a stable and reliable method for forming and integrating film layers in TFT and OLED devices has low film leakage and high yield for use in manufacturing electronic devices with lower threshold voltage shifts and improved overall performance. It becomes important to provide a device structure with voltage.

[0004] In particular, interfacial management between the metal electrode layer and nearby insulating materials becomes important because improper material selection of the interface between the metal electrode layer and nearby insulating materials adversely causes unwanted elements to diffuse into adjacent materials. This is because it can ultimately lead to current shorts, current leakage or device failures. In addition, insulating materials with different higher dielectric constants often provide different electrical performance, such as providing different capacitances to device structures. Not only does the choice of materials of insulating materials affect the electrical performance of the device, but also the incompatibility of the materials of insulating materials to the electrodes can also cause film structure peeling, poor interfacial adhesion or interfacial material diffusion. Device, which can ultimately lead to device failures and low product yields.

[0005] In some devices, capacitors (eg, a dielectric layer is disposed between two electrodes) are often utilized and formed to store charges when the display devices are in operation. The formed capacitor needs to have a high capacitance for display devices. The capacitance can be adjusted by changing the dielectric material and dimensions of the dielectric layer formed between the electrodes, and / or the thickness of the dielectric layer. For example, when the dielectric layer is replaced with a material having a higher dielectric constant (eg, zirconium oxide), the capacitance of the capacitor will also increase.

[0006] As the resolution requirements for display devices become more and more challenging, for example, as display resolution exceeds 2,000 pixels per inch (PPI), display devices have a limited area to form capacitors to increase electrical performance. . Therefore, it has become important to keep the capacitors formed in the display devices in a limited position with a relatively small area. It has been found that higher high constant (“high-k”) dielectric materials (eg, zirconium oxide and hafnium oxide) enable higher resolution display devices. However, deposition of high-k dielectric materials is not limited to a substrate, and often forms a residual film throughout the interior of the processing chamber. Such unwanted residual deposition often creates particles and flakes in the chamber, causing drift of process conditions, which affects process reproducibility and uniformity.

[0007] Chambers to remove residual film residues from the interior surfaces of the processing chamber, including process kits, eg showerheads, etc., to achieve high chamber availability while reducing cost of ownership for production and maintaining membrane quality Cleaning is performed. Unfortunately, the most well-known cleaning techniques, such as fluorine-containing plasmas, are unable to remove high-k dielectric materials, or are too harsh to damage chamber components. Thus, viable in-situ cleaning techniques for high-k dielectric materials are not currently available. Currently, zirconium oxide is removed from the processing chambers using ex-situ cleaning processes, in which the production is stopped, the processing chamber is opened, and the chamber parts are cleaned And removed using wet-cleaning processes.

[0008] Therefore, a need exists for methods for in-situ removal of unwanted high-k dielectric material deposits from substrate-processing chambers.

[0009] Implementations described herein generally relate to methods and apparatus for in-situ removal of unwanted deposition buildups from one or more internal surfaces of a substrate-processing chamber. In one implementation, a method for cleaning a processing chamber is provided. The method includes introducing a reactive species into the processing chamber, the processing chamber having residual high-k dielectric material formed on one or more inner surfaces of the processing chamber. Reactive species are formed from halogen-containing gas mixtures. The one or more inner surfaces include at least one stainless steel surface. The method further includes reacting the reactive species with the residual high-k dielectric material to form a volatile product. The method further includes removing volatile products from the processing chamber. The removal rate of residual high-k dielectric material exceeds that of stainless steel. The high-k dielectric material is selected from zirconium dioxide (ZrO ₂ ) and hafnium dioxide (HfO ₂ ).

[0010] In another implementation, a method for cleaning a processing chamber is provided. The method includes depositing a high-k dielectric material on a substrate disposed in the substrate-processing chamber and one or more inner surfaces of the processing chamber. The method further includes transferring the substrate out of the substrate-processing chamber. The method further includes introducing a reactive species into the processing chamber, the processing chamber having a residual high-k dielectric material formed on one or more inner surfaces of the processing chamber. The reactive species is formed from a halogen-containing gas mixture, and the one or more inner surfaces include at least one surface and at least one stainless steel surface with a coating material formed thereon. The method further includes reacting the reactive species with the residual high-k dielectric material to form a volatile product. The method further includes removing volatile products from the processing chamber, wherein the removal rate of residual high-k dielectric material exceeds the removal rate of the coating material and the removal rate of stainless steel. The high-k dielectric material is selected from zirconium dioxide (ZrO ₂ ) and hafnium dioxide (HfO ₂ ). The coating material includes a compound selected from alumina (Al ₂ O ₃ ), yttrium-containing compounds and combinations thereof.

[0011] In another implementation, a method for cleaning a processing chamber is provided. The method includes flowing a halogen-containing cleaning gas mixture into a remote plasma source fluidly coupled to the processing chamber. The method further includes forming reactive species from the halogen-containing cleaning gas mixture. The method further includes transporting the reactive species into the processing chamber. The processing chamber has a residual high-k dielectric material formed on one or more interior surfaces of the processing chamber. The one or more inner surfaces include at least one surface and at least one stainless steel surface having a coating material formed thereon. The method further includes allowing the reactive species to react with the residual high-k dielectric material to form a gaseous product. The method further includes purging the gaseous product out of the processing chamber. The high-k dielectric material is selected from zirconium dioxide (ZrO ₂ ) and hafnium dioxide (HfO ₂ ). The coating material includes a compound selected from alumina (Al ₂ O ₃ ), yttrium-containing compounds and combinations thereof.

[0012] In another implementation, a method for cleaning a processing chamber is provided. The method includes introducing a reactive species into the processing chamber, the processing chamber having a residual ZrO ₂ containing film formed on one or more inner surfaces of the processing chamber. The reactive species is formed of BCl ₃ and the one or more inner surfaces include at least one exposed Al ₂ O ₃ surface. The method further includes reacting the reactive species with the residual ZrO ₂ containing film to form a volatile product. The method further includes removing volatile products from the processing chamber, wherein the removal rate of the residual ZrO ₂ containing film exceeds the removal rate of Al ₂ O ₃ .

[0013] In another implementation, a method for cleaning a processing chamber is provided. The method includes depositing a ZrO ₂ containing film on one or more internal surfaces of the processing chamber and a substrate disposed in the substrate-processing chamber. The method further includes transferring the substrate out of the substrate-processing chamber. The method further includes introducing a reactive species into the processing chamber, the processing chamber having a residual ZrO ₂ containing film formed on one or more inner surfaces of the processing chamber. The reactive species is formed of BCl ₃ and the one or more inner surfaces include at least one exposed Al ₂ O ₃ surface. The method further includes reacting the reactive species with the residual ZrO ₂ containing film to form a volatile product. The method further includes removing volatile products from the processing chamber, wherein the removal rate of the residual ZrO ₂ containing film exceeds the removal rate of Al ₂ O ₃ .

[0014] In another implementation, a method for cleaning a processing chamber is provided. The method includes flowing a boron trichloride (BCl ₃ ) containing cleaning gas mixture into a remote plasma source fluidly coupled to the processing chamber. The method further includes forming reactive species from the BCl ₃ containing cleaning gas mixture. The method further includes transporting the reactive species into the processing chamber. The processing chamber has a residual ZrO ₂ containing film formed on one or more inner surfaces of the processing chamber, and the one or more inner surfaces include at least one exposed Al ₂ O ₃ surface. The method further includes allowing the reactive species to react with the residual ZrO ₂ containing film to form gaseous zirconium chloride. The method further includes purging the gaseous zirconium chloride out of the processing chamber.

[0015] In another implementation, a method for cleaning a processing chamber is provided. The method includes introducing a reactive species into the processing chamber, the processing chamber having residual high-k dielectric material formed on one or more inner surfaces of the processing chamber. The reactive species is formed from a halogen-containing gas mixture, and the one or more inner surfaces include at least one surface with a coating material formed thereon. The method further includes reacting the reactive species with the residual high-k dielectric material to form a volatile product. The method further includes removing volatile products from the processing chamber. The removal rate of residual high-k dielectric material exceeds the removal rate of the coating material. The high-k dielectric material is selected from zirconium dioxide (ZrO ₂ ) and hafnium dioxide (HfO ₂ ). The coating material includes a compound selected from alumina (Al ₂ O ₃ ), yttrium-containing compounds and combinations thereof.

[0016] In another implementation, a method for cleaning a processing chamber is provided. The method includes depositing a high-k dielectric material on a substrate disposed in the substrate-processing chamber and one or more inner surfaces of the processing chamber. The method further includes transferring the substrate out of the substrate-processing chamber. The method further includes introducing a reactive species into the processing chamber, the processing chamber having a residual high-k dielectric material formed on one or more inner surfaces of the processing chamber. The reactive species is formed from a halogen-containing gas mixture, and the one or more inner surfaces include at least one surface with a coating material formed thereon. The method further includes reacting the reactive species with the residual high-k dielectric material to form a volatile product. The method further includes removing volatile products from the processing chamber. The removal rate of residual high-k dielectric material exceeds the removal rate of the coating material. The high-k dielectric material is selected from zirconium dioxide (ZrO ₂ ) and hafnium dioxide (HfO ₂ ). The coating material includes a compound selected from alumina (Al ₂ O ₃ ), yttrium-containing compounds and combinations thereof.

[0017] In another implementation, a method for cleaning a processing chamber is provided. The method includes flowing a halogen-containing cleaning gas mixture into a remote plasma source fluidly coupled to the processing chamber. The method further includes forming reactive species from the halogen-containing cleaning gas mixture. The method further includes transporting the reactive species into the processing chamber. The processing chamber has a residual high-k dielectric material formed on one or more interior surfaces of the processing chamber. The one or more inner surfaces include at least one surface having a coating material formed thereon. The method further includes allowing the reactive species to react with the residual high-k dielectric material to form a gaseous product. The method further includes purging the gaseous product out of the processing chamber. The high-k dielectric material is selected from zirconium dioxide (ZrO ₂ ) and hafnium dioxide (HfO ₂ ). The coating material includes a compound selected from alumina (Al ₂ O ₃ ), yttrium-containing compounds and combinations thereof.

In a manner in which the above-mentioned features of the present disclosure can be understood in detail, a more specific description of implementations summarized above may be made by reference to implementations, some of which are illustrated in the accompanying drawings. do. It should be noted, however, that the accompanying drawings illustrate only typical implementations of the present disclosure and therefore should not be regarded as limiting the scope of the present disclosure, which may allow other equally valid implementations. Because there is.
1A shows a cross-sectional view of a processing chamber that may benefit from cleaning processes, in accordance with one or more implementations of the present disclosure;
1B shows a cross-sectional view of the processing chamber of FIG. 1A, with residual high-k dielectric materials formed on one or more inner surfaces, which can be removed using one or more implementations of the present disclosure;
[0021] FIG. 2 shows a process flow diagram of one implementation of a method that can be used to remove high-k dielectric materials from a processing chamber; And
[0022] FIG. 3 shows a process flow diagram of another implementation of a method that can be used to remove high-k dielectric materials from a processing chamber.
To facilitate understanding, the same reference numerals have been used, where possible, to denote the same elements common to the figures. It is contemplated that elements and features of one implementation may be beneficially incorporated into other implementations without further recitation.

[0024] The following disclosure describes techniques for in-situ removal of residual high-k dielectric materials from a substrate-processing chamber. Specific details are set forth in the following description and drawings to provide a thorough understanding of various implementations of the present disclosure. Other details describing well-known structures and systems often associated with plasma cleaning are not presented in the following disclosure to avoid unnecessarily obscuring the description of various implementations.

[0025] Many of the details, dimensions, angles and other features shown in the figures are illustrative only for specific implementations. Accordingly, other implementations may have other details, components, dimensions, angles and features without departing from the spirit or scope of the present disclosure. In addition, additional implementations of the present disclosure may be practiced without the various details described below.

[0026] The implementations described herein will be described below with reference to a high-k dielectric deposition process that can be performed using any suitable thin film deposition system. One example of such a system is an AKT-90K PECVD system suitable for substrates of substrate size 3000 mm x 3000 mm or more commercially available from Applied Materials, Inc. of Santa Clara, California. Another example of such a system is the AKT-25K PECVD system or AKT-25K ALD system suitable for substrates of substrate size 1850 mm x 1500 mm or larger, commercially available from Applied Materials, Inc. of Santa Clara, California. Other tools that can perform high-k dielectric deposition processes can also be adapted to benefit from the implementations described herein. In addition, any system that enables the high-k dielectric deposition processes described herein can be advantageously used. The apparatus described herein is exemplary and should not be understood or interpreted as limiting the scope of the implementations described herein.

[0027] Implementations of the present disclosure generally relate to in-situ removal of high-k dielectric materials, such as ZrO ₂ and HfO ₂ , from processing chambers. Processing chambers include, but are not limited to, PECVD, ALD or other processing chambers utilized in the fabrication of high-resolution display back-plane TFT circuits. ZrO ₂ and HfO ₂ are high-k dielectric materials currently used to enable high-resolution display devices, such as Virtual Reality (VR) devices, in the semiconductor industry and potentially in the flat panel display industry. High-k materials such as ZrO ₂ and HfO ₂ are important to enable high-resolution display devices (eg “pixels per inch (PPI)”> 2000). Currently, in order to increase the resolution, as the entire pixel area is subtracted, the area of the storage capacitor in the pixel circuit needs to be reduced. To achieve the same capacitance, current dielectric layers used in storage capacitors (e.g., SiN, dielectric constant (k) ~ 7) are high-k dielectric materials, such as ZrO ₂ and k>k>20> It is being replaced by HfO ₂ with 25. One factor for enabling high-k dielectric materials in display applications is efficient removal of residual high-k dielectric materials from the processing chamber to reduce particles and improve yield.

[0028] Typically, deposition of high-k dielectric materials is not limited to a substrate, but forms a residual film throughout the chamber. This residual film can lead to particle formation, reduced uniformity and clogging of the gas inlet, leading to yield loss and increased cost of ownership. One method for removing unwanted residual film on the chamber wall or other chamber components is to periodically disassemble the chamber after several deposition cycles and remove the films with solution or solvent. Disassembly of the chamber, cleaning of the components and re-assembly of the chamber take considerable time and significantly affect the uptime of the tool. Another approach is to apply plasma to promote excitation and / or dissociation of reactive gases by application of radio frequency (RF) energy. Plasma contains highly reactive species that react with unwanted residual materials and etch these unwanted residual materials. For example, NF ₃ plasma is widely used in the display industry to remove SiO _x and SiN _x films from processing chambers. However, NF ₃ plasma often cannot etch residual high-k dielectric materials.

[0029] Implementations of the present disclosure include both a chamber cleaning process and a modification of current hardware materials. Some implementations of the present disclosure effectively remove residual high-k dielectric materials from the processing chamber by introducing reactive species formed from a halogen-containing gas mixture into the processing chamber and reacting with the residual high-k dielectric material. The reactive species can be generated as an in-situ plasma (eg, formed inside a processing chamber) or an ex-situ plasma (eg, formed through a remote plasma source). The generation of plasma may include, but is not limited to, inductive-coupled plasma (ICP), capacitive-coupled plasma (CCP), remote plasma source (RPS) or microwave plasma. Not).

[0030] In some implementations of the present disclosure, residual hi- is generated by flowing a halogen-containing gas mixture into a processing chamber, and then exciting and / or dissociating the halogen-containing gas mixture to form a plasma in the processing chamber. k Dielectric materials are removed. The excited free radicals from the halogen-containing gas mixture etch residual high-k dielectric materials from the chamber body. The plasma of the halogen-containing gas mixture etches the high-k dielectric material and aluminum, but typically does not etch or minimally etch the coating material (eg, Al ₂ O ₃ ), unless additional bias is applied. . Thus, in some implementations of the present disclosure, a thin coating material protects the aluminum chamber components during the cleaning process. The coating material can be applied using any suitable process. In some implementations, the coating material is applied by a surface anodization process, plasma spray coating process or thermal spray coating process. If it is necessary to remove the coating material, an additional bias can be applied to the plasma of the halogen-containing gas mixture during the process to enable etching of the coating material. Thus, a halogen-containing gas mixture can be used to selectively remove the high-k dielectric material for the coating material or both the high-k dielectric material and the coating material, depending on the plasma conditions.

1A shows a cross-sectional view of a substrate-processing chamber 100 that may benefit from cleaning processes, in accordance with one or more implementations of the present disclosure. 1B shows a cross-sectional view of the substrate-processing chamber 100 of FIG. 1A with a residual film formed on one or more internal surfaces, which can be removed using one or more implementations of the present disclosure. The substrate-processing chamber 100 can be used to perform CVD, plasma enhanced-CVD (PE-CVD), pulsed-CVD, ALD, PE-ALD, metal-organic chemical vapor deposition (MOCVD), or combinations thereof. have. In some implementations, the substrate-processing chamber can be configured to deposit a high-k dielectric layer, such as ZrO ₂ or HfO ₂ . In some implementations, the substrate-processing chamber 100 is a large area substrate for use in the fabrication of photovoltaic cells for liquid crystal displays (LCDs), flat panel displays, organic light emitting diodes (OLEDs) or solar cell arrays. It is configured to process the substrate 102 using plasma when forming structures and devices on the substrate 102 (hereinafter, the substrate 102).

The substrate-processing chamber 100 generally includes sidewalls 142, a bottom wall 104 and a lid assembly 112, which defines a process volume 106. In one implementation, the lead assembly 112 is generally made of aluminum. The lead assembly 112 can be anodized to form a layer of Al ₂ O ₃ on the surface of the lead assembly 112. In another implementation, the lead assembly 112 is made of stainless steel, nickel-iron alloys (eg, Invar, a nickel-iron alloy known as 64FeNi), or other materials compatible with plasma processing. Sidewalls 142 and bottom wall 104 may be fabricated from a single mass of aluminum, stainless steel, nickel-iron alloys (eg, Invar, a nickel-iron alloy known as 64FeNi) or other materials compatible with plasma processing. You can. Side walls 142 and bottom wall 104 may be anodized to form a coating material on the surface of lead assembly 112. In some implementations, if a coating material is present, the coating material can be formed by an anodizing process, plasma spray process, or thermal spray process. The coating material may include a compound selected from alumina (Al ₂ O ₃ ), yttrium-containing compounds, and combinations thereof. The side walls 142 and the bottom wall 104 may be electrically grounded.

The gas distribution plate 110 and the substrate support assembly 130 are disposed within the process volume 106. Each of the gas distribution plate 110 and / or substrate support assembly 130 is made of aluminum, stainless steel, nickel-iron alloys (eg, Invar, a nickel-iron alloy known as 64FeNi) or other materials compatible with plasma processing. Can be manufactured independently. In one implementation, the substrate support assembly comprises stainless steel. In one implementation, the gas distribution plate 110 comprises stainless steel, and the substrate support assembly comprises alumina (Al ₂ O ₃ ), yttrium-containing compounds, or combinations thereof. The process volume 106 is accessed through a slit valve opening 108 formed through the side walls 142 so that the substrate 102 can be transferred into and out of the substrate-processing chamber 100.

[0034] The substrate support assembly 130 includes a substrate-receiving surface 132 for supporting the substrate 102 on top. The substrate support assembly 130 generally includes an electrically conductive body supported by a stem 134 extending through the bottom wall 104. The stem 134 couples the substrate support assembly 130 to the lift system 136, which lifts and lowers the substrate support assembly 130 between the substrate transfer position and the substrate processing position. A shadow frame 133 may be disposed over the periphery of the substrate 102 during processing to prevent deposition on the edge of the substrate 102. The lift pins 138 are movably disposed through the substrate support assembly 130 and are adapted to space the substrate 102 from the substrate-receiving surface 132. Substrate support assembly 130 may also include heating and / or cooling elements 139 utilized to maintain substrate support assembly 130 at a predetermined temperature. Substrate support assembly 130 may also include ground straps 131 for providing an RF return path around the periphery of substrate support assembly 130. In one implementation, the substrate support assembly 130 has a coating disposed thereon.

The gas distribution plate 110, at its periphery, is coupled to the lid assembly 112 or sidewalls 142 of the substrate-processing chamber 100 by the suspension 114. In one particular implementation, the gas distribution plate 110 is made of aluminum. The surface of the gas distribution plate 110 may be anodized to form a coating material (eg, Al ₂ O ₃ ) on the surface of the gas distribution plate 110. In one implementation, the surface of the gas distribution plate 110 has a yttrium-containing coating (Y ₂ O ₃ ) disposed thereon. The coating material may be formed on the surface of the gas distribution plate 110 by anodizing, plasma spraying process or thermal spraying process. The gas distribution plate 110 can also control the straightness / curvature of the gas distribution plate 110 and / or lead assembly 112 by one or more center supports 116 to help prevent sag. ). The gas distribution plate 110 can have different configurations with different dimensions. In an exemplary implementation, gas distribution plate 110 has a quadrilateral planar shape. The gas distribution plate 110 has a downstream surface 150, which downstream surface 150 has a plurality of apertures 111 formed through the gas distribution plate 110, on the substrate support assembly 130 It faces the upper surface 118 of the placed substrate 102. The apertures 111 can have different shapes, numbers, densities, dimensions and distributions across the gas distribution plate 110. In one implementation, the diameter of the apertures 111 can be selected from about 0.01 inches to about 1 inch.

[0036] Gas source 120 is applied to lead assembly 112 to provide gas to process volume 106 through lead assembly 112 and then through apertures 111 formed in gas distribution plate 110. It is coupled. A vacuum pump 109 is coupled to the substrate-processing chamber 100 to maintain the gas in the process volume 106 at a predetermined pressure.

[0037] The first power source 122 is coupled to the lead assembly 112 and / or gas distribution plate 110. The first power source 122 is between the gas distribution plate 110 and the substrate support assembly 130 so that plasma can be generated from gases present between the gas distribution plate 110 and the substrate support assembly 130. Provides power to generate an electric field. The lead assembly 112 and / or gas distribution plate 110 electrode can be coupled to the first power source 122 through an optional filter, which can be an impedance matching circuit. The first power source 122 may be DC power, pulsed DC power, RF bias power, pulsed RF source or bias power, or a combination thereof. In one implementation, the first power source 122 is RF bias power.

[0038] In one implementation, the first power source 122 is an RF power source. In one implementation, the first power source 122 can be operated to provide RF power at a frequency of 0.3 MHz to about 14 MHz, such as about 13.56 MHz. The first power source 122 can generate RF power from about 10 watts to about 20,000 watts (eg, from about 10 watts to about 5000 watts; from about 300 watts to about 1500 watts; or from about 500 watts to about 1000 watts). have.

[0039] RF power supplied to the gas distribution plate 110 by the first power source 122 can excite gases disposed in the process volume 106 between the substrate support assembly 130 and the gas distribution plate 110. , The substrate support assembly 130 may be grounded. The substrate support assembly 130 can be made of metals or other similar electrically conductive materials. In one implementation, at least a portion of the substrate support assembly 130 may be covered with an electrically insulating coating. The coating may be a dielectric material, such as oxides, silicon nitride, silicon dioxide, aluminum oxide, aluminum dioxide, tantalum pentoxide, silicon carbide, polyimide and yttrium-containing compounds, among others. Alternatively, the substrate-receiving surface 132 of the substrate support assembly 130 may be free of coating or anodization.

[0040] Electrodes (not shown), which may be bias electrodes and / or electrostatic chucking electrodes, may be coupled to the substrate support assembly 130. In one implementation, the electrode is positioned on the body of the substrate support assembly 130. The electrode can be coupled to the second power source 160 through an optional filter, which can be an impedance matching circuit. The second power source 160 can be used to set additional bias by setting an additional potential from the plasma to the substrate 102. Although there is already a built-in potential from the plasma to the substrate 102 even without the second power source 160, the second power source 160 is biased to provide more ion bombardment to enhance the etch / clean effect. It is believed to increase. The second power source 160 may be DC power, pulsed DC power, RF bias power, pulsed RF source or bias power, or a combination thereof.

[0041] In one implementation, the second power source 160 is a DC bias source. DC bias power can be supplied at a frequency of 300 kHz from about 10 watts to about 3000 watts (eg, about 10 watts to about 1000 watts; or about 10 watts to about 100 watts). In one implementation, the DC bias power can be pulsed with a duty cycle of about 10% to about 95% at an RF frequency of about 500 Hz to about 10 kHz. Without being bound by theory, it is believed that DC bias establishes a bias between the plasma and the substrate support, so that ions in the plasma impact the substrate support to improve the etching effect.

[0042] In one implementation, the second power source 160 is RF bias power. RF bias power can be supplied at a frequency of 300 kHz from about 0 watts to about 1000 watts (eg, about 10 watts to about 100 watts). In one implementation, the RF bias power can be pulsed with a duty cycle of about 10% to about 95% at an RF frequency of about 500 Hz to about 10 kHz.

[0043] In one implementation, a spacing gradient between the substrate-receiving surface 132 and the edges and corners of the gas distribution plate 110 and consequently between the gas distribution plate 110 and the top surface 118 of the substrate 102. As defined, the edges of the downstream surface 150 of the gas distribution plate 110 can be curved. The shape of the downstream surface 150 can be selected to meet specific process requirements. For example, the shape of the downstream surface 150 can be convex, planar, concave, or other suitable shape. Therefore, the edge-to-corner spacing gradient can be utilized to tune the film property uniformity across the edge of the substrate to correct the property non-uniformity of the films disposed at the corners of the substrate. Additionally, edge-to-center spacing can also be controlled, so that film property distribution uniformity can be controlled between the center and edge of the substrate. In one implementation, the curvature of the gas distribution plate 110 is such that the central portion of the edge of the gas distribution plate 110 is farther away from the upper surface 118 of the substrate 102 than the corners of the gas distribution plate 110. Concave edges can be used. In another implementation, the curved convex edge of the gas distribution plate 110 is such that the corners of the gas distribution plate 110 are spaced further away from the upper surface 118 of the substrate 102 than the edges of the gas distribution plate 110. Can be used.

[0044] A remote plasma source 124, such as an inductively coupled remote plasma source, can also be coupled between the gas source and the gas distribution plate 110. Between processing the substrates, a halogen-containing cleaning gas mixture can be energized at a remote plasma source 124 to remotely provide a plasma utilized to clean chamber components. The halogen-containing cleaning gas mixture entering the process volume 106 can be further excited by the RF power provided to the gas distribution plate 110 by the first power source 122. While gas source 120 is coupled to lead assembly 112 through remote plasma source 124, it should be understood that in some implementations, gas source 120 is coupled directly to lead assembly.

[0045] In one implementation, the substrate 102 that can be processed in the substrate-processing chamber 100 can have a surface area of 10,000 cm 2 or more, such as 25,000 cm 2 or more, such as about 55,000 cm 2 or more. It is understood that after processing, the substrate can be cut to form other smaller devices.

[0046] In one implementation, the heating and / or cooling elements 139 are less than or equal to about 600 ° C during cleaning (about 10 ° C to about 300 ° C; about 200 ° C to about 300 ° C; about 10 ° C to about 50 ° C; or about 10 ° C) To 30 ° C.).

[0047] During cleaning, the nominal spacing between the gas distribution plate 110 and the top surface 118 of the substrate 102 disposed on the substrate-receiving surface 132 is generally 400 mils to about 1,200 mils, such as 400 mils To about 800 mils, or other distances to obtain demanding deposition results. In one implementation, if the gas distribution plate 110 has a concave downstream surface, the spacing between the substrate-receiving surface 132 and the central portion of the edge of the gas distribution plate 110 is about 400 mils to about 1,400 mils, The spacing between the substrate-receiving surface 132 and the corners of the gas distribution plate 110 is about 300 mils to about 1,200 mils.

1B shows a cross-sectional view of the substrate-processing chamber 100 of FIG. 1A with the substrate 102 removed. 1B provides an example of a substrate-processing chamber 100 suitable for performing chamber cleaning using an internal energy source, such as an in-situ plasma, or an external energy source, respectively. In FIG. 1B, a halogen-containing gas mixture () into the process volume 106 with a residual film 180 to be removed during the cleaning process (eg, a high-k dielectric material, such as ZrO ₂ , Y ₂ O ₃ or HfO ₂ ) 170) (shown as solid arrows in FIG. 1B). As shown in FIG. 1B, the residual film 180 is applied on at least a portion of the exposed surface in the substrate-processing chamber 100, in particular, the gas distribution plate 110, the substrate support assembly 130, and the shadow frame ( 133). The halogen-containing gas mixture 170 is an energy source that generates reactive species 190, such as chlorine radicals, fluorine radicals, bromine radicals, hydrogen radicals and combinations thereof, such as a first power source (122), a second power source 160 or a remote plasma source 124. Reactive species 190 react with residual film 180 to form volatile products. Volatile products are removed from the substrate-processing chamber 100. At least one inner surface of the substrate-processing chamber 100 (eg, gas distribution plate 110, substrate support assembly 130, shadow frame 133, sidewalls 142, etc.) is formed on at least one. Of coating material (eg, exposed Al ₂ O ₃ film or exposed yttrium-containing films). The one or more interior surfaces can include aluminum, stainless steel, nickel-iron alloys (eg, Invar or 64FeNi), or other materials compatible with plasma processing. In implementations, when reactive species 190 are formed ex-situ (eg, via remote plasma), reactive species can be delivered into process volume 106.

[0049] FIG. 2 shows a process flow diagram of one implementation of a method 200 that can be used to remove high-k dielectric materials from a substrate-processing chamber. The substrate-processing chamber may be similar to the substrate-processing chamber 100 shown in FIGS. 1A and 1B. In operation 210, a high-k dielectric material is deposited over the substrate disposed in the substrate-processing chamber. During the deposition of the high-k dielectric material over the substrate, the high-k dielectric material includes chamber components of the substrate-processing chamber (eg, gas distribution plate, substrate support assembly, shadow frame, side walls, etc.), It can be deposited on the inner surfaces. The interior surfaces can include aluminum, stainless steel, nickel-iron alloys (eg, Invar or 64FeNi), or other materials compatible with plasma processing. Any suitable high-k dielectric material can be deposited in the substrate-processing chamber. In one implementation, the high-k dielectric material is selected from zirconium oxide (ZrO ₂ ), hafnium oxide (HfO ₂ ), aluminum oxide (Al ₂ O ₃ ), and combinations thereof. In one implementation, a high-k dielectric material is doped. In one implementation, the doped high-k dielectric material is an aluminum-doped zirconium oxide containing material.

High-k dielectric materials include, for example, chemical vapor deposition (CVD) processes, plasma-enhanced chemical vapor deposition (PECVD) processes, atomic layer deposition (ALD) processes, metal-organic chemical vapor deposition (MOCVD) processes, and It can be deposited using a physical vapor deposition (PVD) process. In some implementations, at least some of the chamber components are made of aluminum. In some implementations, at least some of the chamber components have a coating disposed thereon. In some implementations, the coating comprises a compound selected from alumina (Al ₂ O ₃ ), yttrium-containing compounds, and combinations thereof. In one embodiment, the yttrium-containing compound is yttrium oxide (Y ₂ O ₃ ), yttrium oxide fluoride (YOF), yttrium chlorate (Y (ClO ₃ ) ₃ ), yttrium (III) fluoride (YF ₃ ), yttrium (III) chloride (YCl ₃ ), yttria-stabilized zirconia (YSZ) and combinations thereof. In some implementations, the chamber components have no coating disposed thereon and are thus “coating-free”.

[0051] In operation 220, the substrate is transferred out of the substrate-processing chamber. In some implementations, the substrate remains in the substrate-processing chamber during the cleaning process.

[0052] In operation 230, reactive species are introduced into the substrate-processing chamber. Reactive species can be generated utilizing plasma. The plasma can be generated in-situ, or the plasma can be generated in-situ (eg, remotely). Suitable plasma generation techniques and sources, such as inductive-coupled plasma (ICP), capacitive-coupled plasma (CCP), remote plasma source (RPS) or microwave plasma generation techniques can be utilized to form reactive species. In some implementations, reactive species are formed in-situ through an in-situ plasma process. In some implementations, reactive species are formed ex-situ through a remote plasma source and enter the substrate-processing chamber.

In one implementation, reactive species can be produced by flowing a halogen-containing cleaning gas mixture into process volume 106. In one implementation, the halogen-containing cleaning gas mixture comprises a halogen-containing gas. In one implementation, the halogen-containing gas is selected from chlorine-containing gas, hydrogen bromide (HBr) gas, and combinations thereof. In one implementation, the chlorine-containing gas is selected from BCl ₃ and Cl ₂ . In one embodiment, the halogen-containing gas is selected from BCl ₃ , Cl ₂ , HBr, NF ₃ and combinations thereof. In one embodiment, the halogen-containing cleaning gas mixture comprises BCl ₃ and NF ₃ . In one implementation, the halogen-containing cleaning gas mixture comprises BCl ₃ and Cl ₂ . In one implementation, the halogen-containing gas mixture further comprises a carbon-containing gas. In one embodiment, the carbon-containing gas is selected from CO ₂ , CH ₄ , CHF ₃ , CH ₂ F ₂ , CH ₃ F, CF ₄ and combinations thereof. In one implementation, the halogen-containing gas mixture further comprises a diluent gas. The diluent gas can be selected from helium, argon and combinations thereof. In some implementations, halogen-containing gas and carbon-containing gas are separately introduced into process volume 106.

In one implementation, the halogen-containing cleaning gas mixture comprises at least one of CO ₂ , CH ₄ , CHF ₃ , CH ₂ F ₂ , CH ₃ F, CF ₄ and combinations thereof, and BCl ₃ . In another embodiment, the halogen-containing cleaning gas mixture comprises at least one of CO ₂ , CH ₄ , CHF ₃ , CH ₂ F ₂ , CH ₃ F, CF ₄ and combinations thereof, and Cl ₂ . In another embodiment, the halogen-containing cleaning gas mixture comprises at least one of CO ₂ , CH ₄ , CHF ₃ , CH ₂ F ₂ , CH ₃ F and combinations thereof, and HBr. In another embodiment, the halogen-containing cleaning gas mixture comprises at least one of CO ₂ , CH _4, CHF ₃ , CH ₂ F ₂ , CH ₃ F, CF ₄ and combinations thereof, and NF ₃ . In another embodiment, the halogen-containing cleaning gas mixture comprises at least one of CO ₂ , CH ₄ , CHF ₃ , CH ₂ F ₂ , CH ₃ F, CF ₄ and combinations thereof, and BCl ₃ , NF ₃ . In another embodiment, the halogen-containing cleaning gas mixture comprises at least one of CO ₂ , CH ₄ , CHF ₃ , CH ₂ F ₂ , CH ₃ F, CF ₄ and combinations thereof, and BCl ₃ , Cl ₂ .

[0055] In one implementation, the halogen-containing cleaning gas mixture is exposed to an RF source and / or bias power. The RF source and / or bias power energizes the halogen-containing cleaning gas mixture in process volume 106 so that the plasma can be maintained. In one implementation, the first power source 122 can be operated to provide RF power at a frequency of 0.3 MHz to about 14 MHz, such as about 13.56 MHz. The first power source 122 can generate RF power from about 10 watts to about 5000 watts (eg, about 300 watts to about 1500 watts; about 500 watts to about 1000 watts).

[0056] In some implementations, in addition to the RF source power, RF bias power can also be utilized during the cleaning process to assist in dissociating the cleaning gas mixture to form a plasma. RF bias can be provided by the second power source 160. In one implementation, the first power source 122 can be operated to provide RF power at a frequency of 0.3 MHz to about 14 MHz, such as about 13.56 MHz. The RF bias power can be supplied at a frequency of 300 kHz from about 0 watts to about 1000 watts (eg, about 10 watts to about 100 watts). In one implementation, the RF bias power can be pulsed with a duty cycle of about 10% to about 95% at an RF frequency of about 500 Hz to about 10 kHz. In some implementations, when this additional bias is applied, the coating material (eg, Al ₂ O ₃ ) is removed along with the residual high-k dielectric material. Without being bound by theory, DC bias is believed to set a potential difference between the plasma and the substrate to improve etching.

[0057] In some implementations, the plasma can be formed by capacitive or inductive means, and can be energized by coupling RF power to a halogen-containing cleaning gas mixture. The RF power can be dual-frequency RF power with high and low frequency components. RF power is typically applied at a power level of about 50 W to about 2,500 W, which can be all high-frequency RF power, for example at a frequency of about 13.56 MHz, or with high-frequency power, for example at a frequency of about 300 kHz. It can be a mix of low frequency power.

[0058] In some implementations, when reactive species are formed ex-situ, the halogen-containing cleaning gas mixture flows into a remote plasma source fluidly coupled to the substrate-processing chamber. The halogen-containing cleaning gas mixture comprises a halogen-containing gas, optionally, a carbon-containing gas, and, optionally, a dilution gas. In some implementations, the optional dilution gas can function as a carrier gas. In some implementations, an optional diluent gas can extend the life of the radical species and increase the density. In some implementations, the halogen-containing gas flows into a remote plasma source, and other process gases (eg, carbon-containing gases) are delivered individually to the chamber.

[0059] The remote plasma source can be an inductively coupled plasma source. The remote plasma source receives the halogen-containing cleaning gas mixture and forms plasma in the halogen-containing cleaning gas mixture, which causes dissociation of the halogen-containing cleaning gas mixture to form reactive species. Reactive species can include chlorine radicals, bromine radicals, fluorine radicals and combinations thereof. The remote plasma source provides high efficiency dissociation of the halogen-containing cleaning gas mixture.

[0060] In some implementations, the remote plasma is initiated with an initial flow of argon or similar inert gas before introducing the halogen-containing cleaning gas mixture into the remote plasma chamber.

[0061] The halogen-containing cleaning gas mixture can be flowed into the substrate-processing chamber at a flow rate of about 100 sccm to about 20,000 sccm. In some implementations, the halogen-containing cleaning gas mixture flows into the substrate-processing chamber at a flow rate between about 500 sccm and about 4,000 sccm. In some implementations, the halogen-containing cleaning gas mixture flows into the substrate-processing chamber at a flow rate of about 1,000 sccm.

[0062] In one implementation, the pressure in the substrate-processing chamber is between about 10 mTorr and about 300 Torr. In one implementation, the pressure in the substrate-processing chamber is from about 10 mTorr to about 5 Torr, such as about 20 mTorr.

[0063] In some implementations, the remote plasma is initiated with an initial flow of argon or similar inert gas, before introducing the halogen-containing gas mixture into the remote plasma source. Then, as the halogen-containing gas mixture is introduced into the remote plasma chamber, the flow rate of argon is reduced. By way of example, the remote plasma can be initiated with a flow of 3,000 sccm of argon, which is 1,000 as the halogen-containing gas mixture enters the remote plasma chamber at an initial flow rate of 1,000 sccm and then increases to a flow of 1,500 sccm. It is gradually reduced to sccm and then to 500 sccm.

[0064] In some implementations, the cleaning process is performed at room temperature. In some implementations, the substrate support pedestal is heated to a temperature of about 600 ° C or less, such as about 10 ° C to about 200 ° C, or about 10 ° C to about 50 ° C, such as about 10 ° C to 30 ° C. Controlling the temperature can be used to control the removal / etching rate of deposits containing high-k dielectric materials. As the chamber temperature increases, the removal rate can increase.

[0065] Reactive species formed from the halogen-containing cleaning gas mixture are carried to a substrate-processing chamber. In one embodiment, reactive species include halogen radicals. In one embodiment, reactive species include chlorine radicals. In one embodiment, reactive species include chlorine radicals and fluorine radicals. In one embodiment, reactive species include bromine radicals. In one embodiment, reactive species include bromine radicals and hydrogen radicals.

[0066] In operation 240, reactive species react with deposits containing high-k dielectric material to form a gaseous volatile product. In some implementations, the removal rate of deposits containing residual high-k dielectric material exceeds the removal rate of coating material coating at least some of the chamber components. In some implementations, the removal rate of residual high-k dielectric containing deposits exceeds 200 kPa / min (eg, from about 200 kPa / min to about 400 kPa / min; from about 220 kPa / min to about 300 kPa / min; Or about 240 kPa / min to about 300 kPa / min). In some implementations, reacting reactive species and residual high-k dielectric containing deposits to form a volatile product is a bias-free process. In some implementations where no additional bias is applied, the removal rate of the coating material is less than 50 kPa / min (eg, from about 0 kPa / min to about 50 kPa / min; from about 0 kPa / min to about 10 kPa / min) , Or 0 km / min). In some implementations where no additional bias is applied, the removal rate of the coating material is minimal or very slow removal rate (eg, less than 50 kPa / min; less than 40 kPa / min; less than 30 kPa / min; 20 kPa / Less than minutes; less than 20 kPa / min; less than 10 kPa / min; or less than 5 kPa / min).

[0067] Optionally, in operation 250, the gaseous volatile product is purged out of the substrate-processing chamber. By flowing the purge gas into the substrate-processing chamber, the substrate-processing chamber can be actively purged. In addition or alternatively to introducing a purge gas, the substrate-processing chamber can be depressurized to remove any residual cleaning gas as well as any byproducts from the substrate-processing chamber. By evacuating the substrate-processing chamber, the substrate-processing chamber can be purged. The time-duration of the purge process should generally be long enough to remove volatile products from the substrate-processing chamber. The time-period of purge gas flow should generally be long enough to remove volatile products from the interior surfaces of the chamber, including chamber components.

[0068] In operation 260, at least one of operation 230, operation 240, and operation 250 is repeated until the selected cleaning end point is achieved. It should be understood that several cleaning cycles can be applied with an optional purge process performed between these cleaning cycles.

[0069] In some implementations, the method 200 further includes removing the coating material (if present) from the substrate-processing chamber. The coating material is removed by applying additional bias while forming the reactive species and / or reacting the coating material with the reactive species to form a second volatile product. The second volatile product can be removed from the substrate-processing chamber.

3 shows a process flow diagram of one implementation of a method 200 that can be used to remove high-k materials from a substrate-processing chamber. The substrate-processing chamber may be similar to the substrate-processing chamber 100 shown in FIGS. 1A and 1B. In operation 310, a layer containing zirconium oxide (ZrO ₂ ) is deposited over the substrate disposed in the substrate-processing chamber. During the deposition of the zirconium oxide containing layer on the substrate, zirconium oxide and / or zirconium oxide containing compounds are used to remove the chamber components of the substrate-processing chamber (eg, gas distribution plate, substrate support assembly, shadow frame, side walls, etc.). Including, it can be deposited on the inner surfaces. The zirconium oxide containing layer can be an aluminum-doped zirconium oxide containing layer. Zirconium oxide containing layers include, for example, chemical vapor deposition (CVD) processes, plasma-enhanced chemical vapor deposition (PECVD) processes, chambers, atomic layer deposition (ALD) processes, metal-organic chemical vapor deposition (MOCVD) and physical (PVD) vapor deposition) process. The one or more interior surfaces / chamber components may include aluminum, stainless steel, nickel-iron alloys (eg, Invar or 64FeNi), or other materials compatible with plasma processing. In some implementations, at least some of the chamber components are made of aluminum. In some implementations, at least some of the chamber components have a layer of alumina (Al ₂ O ₃ ) disposed thereon. In some implementations, at least some of the chamber components are made of stainless steel.

[0071] In operation 320, the substrate is transferred out of the substrate-processing chamber. In some implementations, the substrate remains in the substrate-processing chamber during the cleaning process.

[0072] In operation 330, reactive species are introduced into the substrate-processing chamber. Reactive species can be generated utilizing plasma generated in-situ, or plasma can be generated ex-situ (eg, remotely). Suitable plasma generation techniques, such as inductive-coupled plasma (ICP), capacitive-coupled plasma (CCP), remote plasma source (RPS) or microwave plasma generation techniques can be utilized to form reactive species. In some implementations, reactive species are formed in-situ through an in-situ plasma process. In some implementations, reactive species are formed ex-situ through a remote plasma source.

In one implementation, reactive species can be produced by flowing a cleaning gas mixture into process volume 106. In one implementation, the cleaning gas mixture comprises BCl ₃ , and optionally a dilution gas. The dilution gas can be an inert gas selected from helium, argon or combinations thereof. The cleaning gas mixture is exposed to the RF source and / or bias power. The RF source and / or bias power energizes the cleaning gas mixture in process volume 106 so that the plasma can be maintained. In one implementation, the first power source 122 can be operated to provide RF power at a frequency of 0.3 MHz to about 14 MHz, such as about 13.56 MHz. The first power source 122 can generate RF power from about 10 watts to about 5000 watts (eg, about 300 watts to about 1500 watts; about 500 watts to about 1000 watts).

[0074] In some implementations, in addition to the RF source power, RF bias power can also be utilized during the cleaning process to assist in dissociating the cleaning gas mixture to form a plasma. RF bias can be provided by the second power source 160. In one implementation, the first power source 122 can be operated to provide RF power at a frequency of 0.3 MHz to about 14 MHz, such as about 13.56 MHz. The RF bias power can be supplied at a frequency of 300 kHz from about 0 watts to about 1000 watts (eg, about 10 watts to about 100 watts). In one implementation, the RF bias power can be pulsed with a duty cycle of about 10% to about 95% at an RF frequency of about 500 Hz to about 10 kHz. In some implementations, when this additional bias is applied, Al ₂ O ₃ is removed along with the residual ZrO ₂ containing film.

[0075] In some implementations, in addition to RF source power, DC bias power can also be utilized during the cleaning process to help dissociate the cleaning gas mixture to form a plasma. DC bias can be provided by the second power source 160. In one implementation, the first power source 122 can be operated to provide RF power at a frequency of 0.3 MHz to about 14 MHz, such as about 13.56 MHz. The second power source 160 is operated to provide DC bias power at a frequency of 300 kHz from about 10 watts to about 3000 watts (eg, about 10 watts to about 1000 watts; or about 10 watts to about 100 watts). You can. In one implementation, the DC bias power can be pulsed with a duty cycle of about 10% to about 95% at a frequency of about 500 Hz to about 10 kHz. Without being bound by theory, DC bias is believed to set a potential difference between the plasma and the substrate to improve etching.

[0076] In some implementations, the plasma can be formed by capacitive or inductive means, and can be energized by coupling RF power to the cleaning gas mixture. The RF power can be dual-frequency RF power with high and low frequency components. RF power is typically applied at a power level of about 50 W to about 2,500 W, which can be all high-frequency RF power, for example, at a frequency of about 13.56 MHz, or with high-frequency power, for example, at a frequency of about 300 kHz. It can be a mix of low frequency power.

In some implementations, when reactive species are formed ex-situ, the BCl ₃ containing gas mixture flows into a remote plasma source fluidly coupled to the substrate-processing chamber. The gas mixture containing BCl ₃ comprises BCl ₃ , and optionally an inert gas. In some implementations, the optional inert gas can function as a carrier gas. In some implementations, an optional inert gas can extend the life of the radical species and increase the density. In some implementations, the BCl ₃ containing gas mixture flows into a remote plasma source and other process gases are delivered individually to the chamber. The optional inert gas can be selected from the group consisting of helium, argon or combinations thereof.

[0078] The remote plasma source may be an inductively coupled plasma source. A remote plasma source, and receives a gas mixture containing BCl _3, and forming a plasma from a gas mixture containing BCl _3, which causes the dissociation of BCl ₃ containing gas mixture to form a reactive species. Reactive species can include chlorine radicals. Remote plasma sources provide high efficiency dissociation of gas mixtures containing BCl ₃ .

[0079] In some implementations, the remote plasma is initiated with an initial flow of argon or similar inert gas, prior to introducing the BCl ₃ containing gas mixture into the remote plasma chamber.

The gas mixture containing BCl ₃ can be flowed into the substrate-processing chamber at a flow rate of about 100 sccm to about 10,000 sccm. In some implementations, the BCl ₃ containing gas mixture flows into the substrate-processing chamber at a flow rate between about 500 sccm and about 4,000 sccm. In some implementations, the BCl ₃ containing gas mixture flows into the substrate-processing chamber at a flow rate of about 1,000 sccm.

[0081] The pressure in the substrate-processing chamber can be from about 10 mTorr to about 300 Torr. The pressure in the substrate-processing chamber can be from 10 mTorr to about 5 Torr, such as about 20 mTorr.

[0082] In some implementations, the remote plasma is initiated with an initial flow of argon or similar inert gas, prior to introducing BCl ₃ into the remote plasma source. Then, as BCl ₃ flows into the remote plasma chamber, the flow rate of argon is reduced. As an example, the remote plasma can be initiated with a flow of 3,000 sccm of argon, which increases to 1,000 sccm, as BCl ₃ enters the remote plasma chamber at an initial flow rate of 1,000 sccm and then increases to a flow of 1,500 sccm. Then it is gradually reduced to 500 sccm.

[0083] In some implementations, the cleaning process is performed at room temperature. In some implementations, the substrate support pedestal is heated to a temperature of about 600 ° C or less, such as about 10 ° C to about 200 ° C, or about 10 ° C to about 50 ° C, such as about 10 ° C to 30 ° C. Controlling the temperature can be used to control the removal / etching rate of high-k dielectric material deposits. As the chamber temperature increases, the removal rate can increase.

Reactive species formed from the BCl ₃ gas mixture are carried to a substrate-processing chamber. Reactive species include chlorine radicals.

[0085] In operation 340, reactive species react with the zirconium oxide containing deposits to form a gaseous volatile product. Volatile products include zirconium tetrachloride (ZrCl ₄ ). In some implementations, the removal rate of the residual ZrO ₂ containing film exceeds the removal rate of Al ₂ O ₃ coating at least some of the aluminum chamber components. In some implementations, the removal rate of the residual ZrO ₂ containing film exceeds 200 Pa / min (eg, from about 200 Pa / min to about 400 Pa / min; from about 220 Pa / min to about 300 Pa / min; or about 240 Å / min to about 300 Å / min). In some implementations, reacting the reactive species with a residual ZrO ₂ containing film to form a volatile product is a bias-free process. In some implementations where no additional bias is applied, the Al ₂ O ₃ removal rate is less than 50 kV / min (eg, from about 0 kV / min to about 50 kV / min; from about 0 kV / min to about 10 kV / min). Minute, or 0 km / min).

[0086] Optionally, in operation 350, the gaseous volatile product is purged out of the substrate-processing chamber. By flowing the purge gas into the substrate-processing chamber, the substrate-processing chamber can be actively purged. In addition or alternatively to introducing a purge gas, the substrate-processing chamber can be depressurized to remove any residual cleaning gas as well as any byproducts from the substrate-processing chamber. By evacuating the substrate-processing chamber, the substrate-processing chamber can be purged. The time-duration of the purge process should generally be long enough to remove volatile products from the substrate-processing chamber. The time-period of purge gas flow should generally be long enough to remove volatile products from the interior surfaces of the chamber, including chamber components.

[0087] In operation 360, at least one of operation 330, operation 340, and operation 350 is repeated until the selected cleaning end point is achieved. It should be understood that several cleaning cycles can be applied with an optional purge process performed between these cleaning cycles.

In some implementations, the method 300 further includes removing the Al ₂ O ₃ containing film (if present) from the substrate-processing chamber. Al ₂ O ₃ is removed by applying additional bias while forming the reactive species and / or reacting the Al ₂ O ₃ containing film with the reactive species to form a second volatile product. The second volatile product can be removed from the substrate-processing chamber.

[0089] Examples:

The following non-limiting examples are provided to further illustrate the implementations described herein. However, the examples are not intended to be all-inclusive, and are not intended to limit the scope of the implementations described herein. Table 1 shows the results for a cleaning process performed according to one implementation of the present disclosure. As shown in Table 1, the inductively coupled plasma process performed with BCl ₃ and without DC bias, has a higher removal rate for ZrO ₂ , aluminum-doped ZrO ₂ and aluminum compared to Al ₂ O ₃ . . As further shown in Table 1, when DC bias is applied, the process also removes Al ₂ O ₃ .

Table 2 shows the results for a cleaning process performed according to one implementation of the present disclosure. As shown in Table 2, the capacitively coupled plasma process performed with BCl ₃ and without DC bias is ZrO ₂ , aluminum-doped ZrO ₂ and aluminum compared to Al ₂ O ₃ , stainless steel, Invar and Yttrium coatings. Has a higher removal rate.

In summary, some advantages of the present disclosure include chamber coating materials (eg, Al ₂ O ₃ and / or yttrium-containing compounds) and / or chamber materials (eg, stainless steel and / or nickel- And the ability to selectively etch residual high-k dielectric films (eg, ZrO ₂ and HfO ₂ ) with no or minimal etching of iron alloys). This selectivity can be used to protect aluminum chamber components. Aluminum chamber components are typically etched during plasma cleaning processes. We use Al ₂ O ₃ anodizing or other chamber coating materials to protect the aluminum components in the chamber, enabling preferential removal of residual high-k dielectric films without damaging the aluminum components. And discovered that this ensures the reliability and lifespan of the hardware components. Selectivity is central to enabling in-situ cleaning capability. Thus, during cleaning, residual films can be removed by a cleaning agent (eg, BCl ₃ , Cl ₂ , HBr or NF ₃ ), but the aluminum sidewalls inside the chamber and other aluminum hardware components remain intact. As mentioned above, implementations of the present disclosure clean residual high-k dielectric films using reactive plasma species from a halogen-containing gas mixture, and use aluminum coating materials on aluminum hardware components inside the chamber. And protecting hardware components. The reactive plasma species can effectively etch high-k dielectric materials and aluminum, but do not etch the coating material unless additional bias is applied. Thus, as long as aluminum is coated with a coating material (eg, Al ₂ O ₃ and / or yttrium-containing compounds), aluminum can be used as a material for hardware parts. The reactive plasma species can also etch Al ₂ O ₃ when additional bias is applied. These features make reactive plasma paper, an ideal cleaner for in-situ cleaning of high-k materials from deposition chambers.

[0093] When introducing elements of the present disclosure or exemplary aspects or implementation (s) of the present disclosure, the singular expression, “such” and “above” is intended to mean that there is one or more of the elements.

[0094] The terms "comprising", "including" and "having" are intended to be inclusive and mean that there may be additional elements other than those listed.

[0095] Although the foregoing is directed to implementations of the present disclosure, other and additional implementations of the present disclosure can be devised without departing from the basic scope of the present disclosure, and the scope of the present disclosure is defined by the following claims. Is decided.

Claims (15)

A method for cleaning a processing chamber,
Introducing reactive species into the processing chamber—residual high-k dielectric material is formed on one or more inner surfaces of the processing chamber, the one or more inner surfaces being stainless steel, nickel-iron alloy, or combinations thereof Materials selected from the group;
Reacting the reactive species with the residual high-k dielectric material to form a volatile product; And
Removing the volatile product from the processing chamber
It includes,
The removal rate of the residual high-k dielectric material exceeds the removal rate of the material of the one or more inner surfaces,
The reactive species is formed from a halogen-containing gas mixture, and
The residual high-k dielectric material is selected from zirconium dioxide (ZrO ₂ ) and hafnium dioxide (HfO ₂ ),
Method for cleaning a processing chamber. According to claim 1,
The one or more inner surfaces further include at least one surface on which a coating material is formed, and the coating material includes a compound selected from alumina (Al ₂ O ₃ ), yttrium-containing compounds, or combinations thereof. doing,
Method for cleaning a processing chamber. According to claim 2,
The yttrium-containing compound is yttrium oxide (Y ₂ O ₃ ), yttrium oxide fluoride (YOF), yttrium chlorate (Y (ClO ₃ ) ₃ ), yttrium (III) fluoride (YF ₃ ), yttrium (III) Selected from chloride (YCl ₃ ), yttria-stabilized zirconia (YSZ), or combinations thereof,
Method for cleaning a processing chamber. According to claim 1,
The halogen-containing gas mixture comprises a halogen-containing gas selected from BCl ₃ , Cl ₂ , HBr, NF ₃ or combinations thereof,
Method for cleaning a processing chamber. According to claim 4,
The halogen-containing gas mixture further comprises a carbon-containing gas,
Method for cleaning a processing chamber. The method of claim 5,
The carbon-containing gas is selected from CO ₂ , CH ₄ , CHF ₃ , CH ₂ F ₂ , CH ₃ F, CF ₄ or combinations thereof,
Method for cleaning a processing chamber. The method of claim 5,
The halogen-containing gas mixture further comprises a dilution gas selected from helium, argon or combinations thereof,
Method for cleaning a processing chamber. According to claim 1,
The halogen-containing gas mixture comprises BCl ₃ and NF ₃ ,
Method for cleaning a processing chamber. According to claim 1,
Exposing the reactive species to one or more energy sources sufficient to react the reactive species and the residual high-k dielectric material to form the volatile product.
Further comprising,
Method for cleaning a processing chamber. The method of claim 9,
The one or more energy sources are selected from capacitively-coupled plasma sources, inductively-coupled plasma sources, microwave plasma sources and remote plasma sources,
Method for cleaning a processing chamber. According to claim 1,
The pressure to react the reactive species with the residual high-k dielectric material to form the volatile product is at least about 10 mTorr to about 5 Torr,
Method for cleaning a processing chamber. According to claim 1,
The processing chamber is a plasma-enhanced chemical vapor deposition (PECVD) chamber, an atomic layer deposition (ALD) chamber, a metal-organic chemical vapor deposition (MOCVD) and a physical vapor deposition (PVD) chamber,
Method for cleaning a processing chamber. A method for cleaning a processing chamber,
Depositing a high-k dielectric material on one or more inner surfaces of a processing chamber and a substrate disposed in the processing chamber;
Transferring the substrate out of the processing chamber;
Introducing reactive species into the processing chamber—residual high-k dielectric material is formed on one or more inner surfaces of the processing chamber, the one or more inner surfaces being aluminum, stainless steel, nickel-iron alloy, or combinations thereof A material selected from the fields, wherein the one or more inner surfaces include at least one surface on which a coating material is formed;
Reacting the reactive species with the residual high-k dielectric material to form a volatile product; And
Removing the volatile product from the processing chamber
It includes,
The removal rate of the residual high-k dielectric material exceeds the removal rate of the coating material and the removal rate of the material of the one or more inner surfaces,
The high-k dielectric material is selected from zirconium dioxide (ZrO ₂ ) and hafnium dioxide (HfO ₂ ),
The reactive species is formed from a halogen-containing gas mixture, and
The coating material comprises a compound selected from alumina (Al ₂ O ₃ ), yttrium-containing compounds or combinations thereof,
Method for cleaning a processing chamber. The method of claim 13,
The removal rate of the coating material is less than 50 kPa / min,
Method for cleaning a processing chamber. The method of claim 13,
Reacting the reactive species with the residual high-k dielectric material to form the volatile product comprises reacting the reactive species and the residual high-k dielectric material with one or more energy sources sufficient to form the volatile product. Further comprising exposing the reactive species to,
Method for cleaning a processing chamber.

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