CN111066121B - Selective in situ cleaning of high dielectric constant films from process chambers using reactive gas precursors - Google Patents

Abstract

In one embodiment, a method for cleaning a process chamber is provided. The method includes introducing a reactive species into a process chamber having a residual high-k dielectric material formed on one or more interior surfaces of the process chamber. The reactive species are formed from a halogen-containing gas mixture, and the one or more interior surfaces include at least one surface having a coating material formed thereon. The method further includes reacting the residual high-k dielectric material with a reactive species to form a volatile product. The method further includes removing volatile products from the processing chamber. The residual high-k dielectric material has a removal rate greater than the removal rate of the coating material. The high-k dielectric material is selected from zirconium dioxide (ZrO) ₂ ) And hafnium oxide (HfO) ₂ ). The coating material comprises a material selected from the group consisting of alumina (Al ₂ O ₃ ) A yttrium-containing compound, and combinations of the two.

Description

Selective in-situ cleaning of high dielectric constants from processing chambers using reactive gas precursors Number of films

Technical field

Embodiments described herein generally relate to methods and apparatus for in-situ removal of unwanted deposition buildup from one or more interior surfaces of a substrate processing chamber.

Background technique

Display devices have been widely used in various electronic applications, such as televisions (TVs), monitors, mobile phones, MP3 players, e-book readers, personal digital assistants (personal digital assistants; PDAs), and similar applications. Display devices are typically designed to produce images by applying an electric field to liquid crystals that fill the gap between two substrates (eg, a pixel electrode and a common electrode) and have an anisotropic dielectric constant that controls the dielectric field strength. . By adjusting the amount of light transmitted through the substrate, light and image intensity, quality and power consumption can be effectively controlled.

Various display devices, such as active matrix liquid crystal displays (AMLCDs) or active matrix organic lightemitting diodes (AMOLEDs), can be used as the light source for the display. In the manufacture of display devices, electronic devices with high electron mobility, low leakage current, and high breakdown voltage will allow more pixel area for light transmission and circuit integration, resulting in brighter displays, higher Overall electrical efficiency, faster response times and higher resolution displays. Low film quality of material layers formed in a device, such as dielectric layers with impurities or low film density, often results in poor electrical performance of the device and short device life. Therefore, for use in fabricating electronic devices with lower threshold voltage shifts and improved overall performance, there is a need for forming and integrating film layers within TFT and OLED devices to provide device structures with low film leakage and high breakdown voltage. Stable and reliable methods become critical.

In particular, because improper material selection for the interface between the metal electrode layer and the nearby insulating material may adversely lead to the diffusion of undesirable elements into the adjacent material, which may ultimately lead to current short circuits, current leakage, or device failure. Interface management between the metal electrode layer and nearby insulating materials becomes critical. Additionally, insulating materials with different higher dielectric constants often provide different electrical properties, such as different capacitances in device structures. The material selection of the insulating material not only affects the electrical performance of the device, but incompatibility between the material of the insulating material and the electrodes can also lead to film structure peeling, poor interface adhesion, or interface material diffusion, which can ultimately lead to device failure and low performance. Product yield.

In some devices, a capacitor (eg, a dielectric layer placed between two electrodes) is typically utilized and formed to store electrical charge when the display device is in operation. The formed capacitor is required to have high capacitance for display devices. The capacitance can be adjusted by changing the dielectric material and size of the dielectric layer formed between the electrodes and/or the thickness of the dielectric layer. For example, when the dielectric layer is replaced by a material with a higher dielectric constant (eg, zirconium oxide), the capacitance of the capacitor will also increase.

As resolution requirements for display devices become increasingly challenging (e.g., display resolutions greater than 2,000 pixels per inch (PPI)), display devices have features for forming capacitors to increase electrical performance. Limited area. Therefore, it has become critical to maintain the capacitor formed in the display device in a limited location with a relatively small area. Higher dielectric constant ("high-k") dielectric materials (eg, zirconium oxide and hafnium oxide) have been discovered to enable higher resolution display devices. However, the deposition of high-k dielectric material is not limited to the substrate and often forms residual films throughout the interior of the processing chamber. This undesirable residual deposition can often create particles and flakes within the chamber, causing drift in process conditions, thus affecting process repeatability and uniformity.

To achieve high chamber availability while reducing the cost of ownership of production and maintaining film quality, chamber cleaning is performed to remove residual film residue from the interior surfaces of the process chamber (including process accessories, e.g., showerheads, etc.). Unfortunately, most known cleaning techniques such as fluorine-containing plasma are either incapable of removing high-k dielectric materials or are so harsh that they damage chamber components. Therefore, there are currently no feasible in-situ cleaning techniques for high-k dielectric materials. Currently, zirconia is removed from processing chambers using an ex-situ cleaning process in which production is stopped, the processing chamber is opened and chamber components are removed for cleaning and cleaned using a wet cleaning process.

Accordingly, a need exists for a method for in-situ removal of unwanted deposits of high-k dielectric material from substrate processing chambers.

Contents of the invention

Embodiments described herein generally relate to methods and apparatus for in-situ removal of unwanted deposition buildup from one or more interior surfaces of a substrate processing chamber. In one embodiment, a method for cleaning a processing chamber is provided. The method includes introducing a reactive species into a processing chamber having residual high-k dielectric material formed on one or more interior surfaces of the processing chamber. Reactive species are formed from halogen-containing gas mixtures. The one or more interior surfaces include at least one stainless steel surface. The method further includes reacting residual high-k dielectric material with a reactive species 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 is greater than the removal rate of stainless steel. The high-k dielectric material is selected from zirconium dioxide (ZrO ₂ ) and hafnium dioxide (HfO ₂ ).

In another embodiment, a method for cleaning a processing chamber is provided. The method includes depositing a high-k dielectric material on one or more interior surfaces of a processing chamber and a substrate disposed in the substrate processing chamber. The method further includes transporting the substrate out of the substrate processing chamber. The method further includes introducing a reactive species into the processing chamber having residual high-k dielectric material formed on one or more interior surfaces of the processing chamber . The reactive species is formed from the halogen-containing gas mixture, and the one or more interior surfaces include at least one stainless steel surface and at least one surface having a coating material formed thereon. The method further includes reacting residual high-k dielectric material with a reactive species to form a volatile product. The method further includes removing volatile products from the processing chamber, wherein the residual high-k dielectric material is removed at a rate greater than the removal rate of the coating material and the 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 aluminum oxide (Al ₂ O ₃ ), yttrium-containing compounds, and a combination of the above two.

In yet another embodiment, 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 a processing chamber. The method further includes forming a reactive species from the halogen-containing cleaning gas mixture. The method further includes delivering the reactive species into the processing chamber. The processing chamber has residual high-k dielectric material formed on one or more interior surfaces of the processing chamber. The one or more interior surfaces include at least one stainless steel surface and 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 gaseous products from 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 aluminum oxide (Al ₂ O ₃ ), yttrium-containing compounds, and a combination of the above two.

In another embodiment, a method for cleaning a processing chamber is provided. The method includes introducing a reactive species into a processing chamber having a residual _{ZrO2 -} containing film formed on one or more interior surfaces of the processing chamber. The reactive species is formed from _BCl3 and the one or more inner surfaces include at least _one exposed _Al2O3 surface. The method further includes reacting the residual _ZrO2- containing film with a reactive species to form a volatile product. The method further includes removing volatile products from the processing chamber, wherein the removal rate of the residual _ZrO2- containing film is greater than the removal rate of _{the Al2O3} .

In yet another embodiment, a method for cleaning a processing chamber is provided. The method includes depositing a _ZrO2 -containing film on one or more interior surfaces of a processing chamber and on a substrate disposed in the substrate processing chamber. The method further includes transporting the substrate out of the substrate processing chamber. The method further includes introducing a reactive species into the processing chamber having a residual _{ZrO2 -} containing film formed on one or more interior surfaces of the processing chamber. The reactive species is formed from _BCl3 and the one or more inner surfaces include at least _one exposed _Al2O3 surface. The method further includes reacting the residual _ZrO2- containing film with a reactive species to form a volatile product. The method further includes removing volatile products from the processing chamber, wherein the removal rate of the residual _ZrO2- containing film is greater than _the removal rate of _Al2O3 .

In another embodiment, 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 a processing chamber. The method further includes forming a reactive species from the BCl ₃ -containing clean gas mixture. The method further includes delivering the reactive species into the processing chamber. The processing chamber has a residual _ZrO2- containing film formed on one or more interior surfaces of the processing chamber, and the one or more interior surfaces include at least _one exposed _Al2O3 surface. The method further includes allowing the reactive species to react with the residual _ZrO2- containing film to form gaseous zirconium chloride. The method further includes purging gaseous zirconium chloride from the processing chamber.

In yet another embodiment, a method for cleaning a processing chamber is provided. The method includes introducing a reactive species into a processing chamber having residual high-k dielectric material formed on one or more interior surfaces of the processing chamber. The reactive species is formed from the halogen-containing gas mixture, and the one or more interior surfaces include at least one surface having a coating material formed thereon. The method further includes reacting residual high-k dielectric material with a reactive species to form a volatile product. The method further includes removing volatile products from the processing chamber. The removal rate of the residual high-k dielectric material is greater than 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 aluminum oxide (Al ₂ O ₃ ), yttrium-containing compounds, and a combination of the above two.

In another embodiment, a method for cleaning a processing chamber is provided. The method includes depositing a high-k dielectric material on one or more interior surfaces of a processing chamber and a substrate disposed in the substrate processing chamber. The method further includes transporting the substrate out of the substrate processing chamber. The method further includes introducing a reactive species into the processing chamber having residual high-k dielectric material formed on one or more interior surfaces of the processing chamber . The reactive species is formed from the halogen-containing gas mixture, and the one or more interior surfaces include at least one surface having a coating material formed thereon. The method further includes reacting residual high-k dielectric material with a reactive species to form a volatile product. The method further includes removing volatile products from the processing chamber. The removal rate of the residual high-k dielectric material is greater than 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 aluminum oxide (Al ₂ O ₃ ), yttrium-containing compounds, and a combination of the above two.

In yet another embodiment, 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 a processing chamber. The method further includes forming a reactive species from the halogen-containing cleaning gas mixture. The method further includes delivering the reactive species into the processing chamber. The processing chamber has residual high-k dielectric material formed on one or more interior surfaces of the processing chamber. The one or more interior 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 gaseous products from 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 aluminum oxide (Al ₂ O ₃ ), yttrium-containing compounds, and a combination of the above two.

Description of the drawings

For a detailed understanding of the manner in which the above-described features of the disclosure may be described, reference may be made to the more specific description of the embodiments briefly summarized above, some embodiments of which are illustrated in the accompanying drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this disclosure and are therefore not to be considered limiting of its scope, for the disclosure may admit to other equally effective embodiments.

1A illustrates a cross-sectional view of a processing chamber that may benefit from a cleaning process in accordance with one or more embodiments of the present disclosure;

1B shows a cross-sectional view of the processing chamber of FIG. 1A with residual high-k dielectric material formed on one or more interior surfaces that may be removed using one or more embodiments of the present disclosure; and

2 illustrates a process flow diagram of one embodiment of a method that may be used to remove high-k dielectric material from a processing chamber; and

3 illustrates a process flow diagram of another embodiment of a method that may be used to remove high-k dielectric material from a processing chamber.

To facilitate understanding, the same reference numbers have been used wherever possible to refer to the same elements common to the drawings. It is contemplated that elements and features of one embodiment may be beneficially incorporated into other embodiments without further recitation.

Detailed ways

The following disclosure describes techniques for in-situ removal of residual high-k dielectric material from a substrate processing chamber. Certain details are set forth in the following description and drawings to provide a thorough understanding of the various embodiments of the disclosure. Other details describing well-known structures and systems commonly associated with plasma cleaning will not be set forth in the following disclosure to avoid unnecessarily obscuring the description of the various embodiments.

Most of the details, dimensions, angles and other features shown in the drawings are merely illustrative of specific embodiments. Accordingly, other embodiments may have other details, components, dimensions, angles, and features without departing from the spirit or scope of the disclosure. Furthermore, additional embodiments of the disclosure may be practiced without several of the details described below.

Embodiments described herein will be described below with reference to a high-k dielectric deposition process that may be performed using any suitable thin film deposition system. An example of such a system is the AKT-90K PECVD system suitable for substrate sizes of 3000 mm x 3000 mm or larger, available from Applied Materials, Inc., Santa Clara, California. (Applied Materials). Another example of such a system is the AKT-25K PECVD system or the AKT-25KALD system suitable for substrates with a substrate size of 1850 mm x 1500 mm or larger, which are commercially available from Applied Materials, Inc., Santa Clara, California. . Other tools capable of performing high-k dielectric deposition processes may also be adapted to benefit from the embodiments described herein. Additionally, any system capable of implementing the high-k dielectric deposition processes described herein may benefit. The device descriptions described herein are illustrative and should not be construed or stated as limiting the scope of the embodiments described herein.

Embodiments of the present disclosure generally relate to the in-situ removal of high-k dielectric materials such as _ZrO and _HfO from a processing chamber. Processing chambers include, but are not limited to, PECVD, ALD, or other processing chambers used to fabricate high-resolution display backplane TFT circuits. ZrO ₂ and HfO ₂ are high-k dielectric materials currently used in the semiconductor industry, and potentially in the flat panel display industry to enable high-resolution display devices, such as virtual reality (VR) devices. High dielectric constant materials such as _ZrO2 and _HfO2 are particularly critical for achieving high resolution display devices (eg, pixels per inch ("PPI") >2000). Currently, as the entire pixel area shrinks to increase resolution, there is a need to reduce the area of the storage capacitor in the pixel circuit. To achieve the same capacitance, current dielectric layers used in storage capacitors (e.g., SiN, dielectric constant (k) ~ 7) are being replaced by high-k dielectric materials that Such as ZrO ₂ with k>20 and HfO ₂ with k>25. One factor for implementing high-k dielectric materials in display applications is the efficient removal of residual high-k dielectric materials from the processing chamber to reduce particles and improve yield.

Typically, the deposition of high-k dielectric material is not limited to the substrate and forms a residual film throughout the chamber. This residual film can lead to particle formation, reduced uniformity, and gas inlet plugging, resulting in yield loss and increased cost of ownership. One way to remove unwanted residual film on the chamber walls or other chamber components is to periodically disassemble the chamber after several deposition cycles and remove the film with a solution or solvent. Disassembling the chamber, cleaning components, and reassembling the chamber can take a significant amount of time and significantly affect the tool's usable time. Another approach is to apply plasma by applying radio frequency (RF) energy to promote excitation and/or dissociation of reactive gases. The plasma includes highly reactive species that react with and etch unwanted residual materials. For example, NF _plasma is widely used in the display industry to remove _SiO and _SiN films from processing chambers. However, _NF3 plasmas are generally unable to etch residual high-k dielectric materials.

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

In some embodiments of the present disclosure, residual high-dielectric constant media is removed by flowing a halogen-containing gas mixture into a processing chamber and subsequently exciting and/or dissociating the halogen-containing gas mixture to form a plasma in the processing chamber. electrical materials. Excited free radicals from the halogen-containing gas mixture etch residual high-k dielectric material from the chamber body. If no additional bias is applied, the plasma containing the halogen gas mixture etches high-k dielectric materials and aluminum, but typically does not or minimally etch coating materials (eg, Al ₂ O ₃ ). Therefore, in some embodiments of the present disclosure, the thin coating material protects the aluminum chamber components during the cleaning process. The coating material may be applied using any suitable process. In some embodiments, the coating material is applied by a surface anodization process, a plasma spray process, or a thermal spray process. If coating material must be removed, an additional bias voltage may be applied to the plasma containing the halogen gas mixture during the process to promote etching of the coating material. Thus, depending on the plasma conditions, the halogen-containing gas mixture can be used to selectively remove high-k dielectric materials relative to coating materials, or remove both high-k dielectric materials and coating materials.

1A illustrates a cross-sectional view of a substrate processing chamber 100 that may benefit from a cleaning process in accordance with one or more embodiments of the present disclosure. Figure IB shows a cross-sectional view of the substrate processing chamber 100 of Figure IA with residual film formed on one or more interior surfaces that may be removed using one or more embodiments of the present disclosure. The substrate processing chamber 100 may be used to perform CVD, plasma enhanced-CVD (PE-CVD), pulsed CVD, ALD, PE-ALD, metal-organic chemical vapor deposition (MOCVD), or A combination of the above. In some embodiments, the substrate processing chamber may be configured to deposit a high-k dielectric layer, such as ZrO ₂ or HfO ₂ . In some embodiments, the substrate processing chamber 100 is configured to form structures and devices on a large area substrate 102 (hereinafter substrate 102 ) for use in fabricating liquid crystal displays (LCDs), flat panel displays, organic light emitting diodes (OLEDs) Or a photovoltaic cell in a solar cell array, the substrate 102 is treated with plasma.

Substrate processing chamber 100 generally includes side walls 142, bottom wall 104, and lid assembly 112, which define a process volume 106. In one embodiment, cover assembly 112 is generally composed of aluminum. Cover assembly 112 may be anodized to form an Al ₂ O ₃ layer on the surface of cover assembly 112 . In another embodiment, the cover assembly 112 is made from stainless steel, a nickel-iron alloy (eg, Invar, a nickel-iron alloy known as 64FeNi), or other materials that are compatible with plasma processing. The side walls 142 and the bottom wall 104 may be made from a solid block of aluminum, stainless steel, a nickel-iron alloy (eg, Invar, a nickel-iron alloy known as 64FeNi), or other materials that are compatible with plasma processing. Sidewalls 142 and bottom wall 104 may be anodized to form a coating material on the surface of cover assembly 112 . In some embodiments, where a coating material is present, the coating material may be formed by an anodizing process, a plasma spray process, or a thermal spray process. The coating material may include compounds selected from aluminum oxide (Al ₂ O ₃ ), yttrium-containing compounds, and combinations of the above. Side wall 142 and bottom wall 104 may be electrically grounded.

Gas distribution plate 110 and substrate support assembly 130 are disposed within process volume 106 . The gas distribution plate 110 and/or the substrate support assembly 130 may each be independently constructed of aluminum, stainless steel, a nickel-iron alloy (eg, Invar, a nickel-iron alloy known as 64FeNi), or other materials compatible with plasma processing. material. In one embodiment, the substrate support assembly includes stainless steel. In one embodiment, the gas distribution plate 110 includes stainless steel and the substrate support assembly includes alumina (Al ₂ O ₃ ), an yttrium-containing compound, and a combination thereof. Access to the process volume 106 is through a slit valve opening 108 formed through the sidewall 142 so that substrates 102 can be transferred into and out of the substrate processing chamber 100 .

The substrate support assembly 130 includes a substrate receiving surface 132 for supporting the substrate 102 thereon. Substrate support assembly 130 generally includes a conductive body supported by stems 134 that extend through bottom wall 104 . Rod 134 couples substrate support assembly 130 to a lift system 136 that raises and lowers substrate support assembly 130 between substrate transfer and processing positions. A shadow frame 133 may be placed over the perimeter of the substrate 102 during processing to prevent deposition on the edges of the substrate 102 . Lift pin 138 is movably disposed through substrate support assembly 130 and is adapted to space substrate 102 from substrate receiving surface 132 . The substrate support assembly 130 may also include heating and/or cooling elements 139 for maintaining the substrate support assembly 130 at a selected temperature. The substrate support assembly 130 may also include a groundingstrap 131 to provide a radio frequency return path around the perimeter of the substrate support assembly 130 . In one embodiment, substrate support assembly 130 has a coating disposed thereon.

The gas distribution plate 110 is coupled at its periphery to the lid assembly 112 or sidewall 142 of the substrate processing chamber 100 by a suspension 114 . In a specific embodiment, 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 embodiment, the surface of the gas distribution plate 110 has an yttrium-containing coating (Y ₂ O ₃ ) disposed thereon. The coating material may be formed on the surface of the gas distribution plate 110 through anodization, plasma spraying process or thermal spraying process. The gas distribution plate 110 may also be coupled to the cover assembly 112 via one or more center supports 116 to help prevent the gas distribution plate 110 from sagging and/or control the flatness/curvature of the gas distribution plate 110 . The gas distribution plate 110 may have different configurations with different sizes. In the exemplary embodiment, the gas distribution plate 110 has a quadrangular plan shape. The gas distribution plate 110 has a downstream surface 150 having a plurality of holes 111 formed therethrough and facing an upper surface 118 of the substrate 102 disposed on the substrate support assembly 130 . The holes 111 may have different shapes, numbers, densities, sizes and distributions across the gas distribution plate 110 . In one embodiment, the diameter of hole 111 may be selected between about 0.01 inches and about 1 inch.

Gas source 120 is coupled to cover assembly 112 to provide gas to process volume 106 through cover assembly 112 and subsequently through holes 111 formed in gas distribution plate 110 . A vacuum pump 109 is coupled to the substrate processing chamber 100 to maintain the gas in the process volume 106 at a selected pressure.

The first electrical power source 122 is coupled to the cover assembly 112 and/or the gas distribution plate 110 . The first electrical power source 122 provides power to generate an electric field between the gas distribution plate 110 and the substrate support assembly 130 so that a plasma can be generated from the gas present between the gas distribution plate 110 and the substrate support assembly 130 . Cover assembly 112 and/or gas distribution plate 110 may be coupled to first electrical power source 122 through an optional filter, which may be an impedance matching circuit. The first electrical power source 122 may be a DC power source, a pulsed DC power source, an RF bias power source, a pulsed RF source or a bias power source, or a combination of the above. In one embodiment, first electrical power source 122 is a radio frequency bias power source.

In one embodiment, first electrical power source 122 is a radio frequency power source. In one embodiment, the first electrical power source 122 is operable to provide radio frequency power at a frequency between 0.3 MHz and about 14 MHz, such as about 13.56 MHz. The first electrical power source 122 may generate about 10 watts to about 20,000 watts (eg, between about 10 watts and about 5000 watts; between about 300 watts and about 1500 watts; or between about 500 watts and about 1000 watts) ) of RF power.

The substrate support assembly 130 may be grounded such that radio frequency power supplied to the gas distribution plate 110 by the first electrical power source 122 may energize 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 made of metal or other similar conductive materials. In one embodiment, 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, alumina, aluminum dioxide, tantalum pentoxide, silicon carbide, polyimides, yttrium-containing compounds, and the like. Alternatively, the substrate receiving surface 132 of the substrate support assembly 130 may be free of coating or anodization.

An electrode (not shown), which may be a bias electrode and/or an electrostatic adsorption electrode, may be coupled to the substrate support assembly 130 . In one embodiment, the electrodes are located in the body of substrate support assembly 130. The electrodes may be coupled to the second electrical power source 160 through an optional filter, which may be an impedance matching circuit. The second electrical power source 160 may be used to establish additional bias by establishing 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 electrical power source 160, it is believed that the second electrical power source 160 increases the potential to provide more ion bombardment to enhance the etching/cleaning effect . The second electrical power source 160 may be a DC power source, a pulsed DC power source, an RF bias power source, a pulsed RF source or a bias power source, or a combination of the above.

In one embodiment, the second electrical power source 160 is a DC bias power source. The DC bias power supply may supply between about 10 Watts and about 3000 Watts (eg, between about 10 Watts and about 1000 Watts; or between about 10 Watts and about 100 Watts) at a frequency of 300 kHz. . In one embodiment, the DC bias power supply may be pulsed at radio frequency frequencies of about 500 Hz and about 10 kHz with a duty cycle between about 10% and about 95%. Without being bound by theory, it is believed that the DC bias establishes a bias between the plasma and the substrate support such that ions in the plasma bombard the substrate support thereby enhancing the etching effect.

In one embodiment, the second electrical power source 160 is a radio frequency bias power source. The radio frequency bias power supply may supply between about 0 watts and about 1000 watts (eg, between about 10 watts and about 100 watts) at a frequency of 300 kHz. In one embodiment, the radio frequency bias power supply may be pulsed at radio frequency frequencies of about 500 Hz and about 10 kHz with a duty cycle between about 10% and about 95%.

In one embodiment, the edges of the downstream surface 150 of the gas distribution plate 110 may be curved so as to be between the edges and corners of the gas distribution plate 110 and the substrate receiving surface 132 and thus between the gas distribution plate 110 and the upper surface 118 of the substrate 102 interval gradient. The shape of downstream surface 150 may be selected to meet specific process requirements. For example, the shape of downstream surface 150 may be convex, planar, concave, or other suitable shapes. Thus, edge-to-corner spacing gradients can be used to adjust film property uniformity across the edges of the substrate, thereby correcting for property non-uniformity of films disposed in the corners of the substrate. Additionally, the edge-to-center spacing can also be controlled so that the uniformity of film property distribution between the edge and center of the substrate can be controlled. In one embodiment, a concavely curved edge of the gas distribution plate 110 may be used so that the center portion of the edge of the gas distribution plate 110 is further spaced from the upper surface 118 of the substrate 102 than the corners of the gas distribution plate 110 . In another embodiment, a convexly curved edge of the gas distribution plate 110 may be used so that the corners of the gas distribution plate 110 are further spaced from the upper surface 118 of the base plate 102 than the edges of the gas distribution plate 110 .

A remote plasma source 124 (such as an inductively coupled remote plasma source) may also be coupled between the gas source and the gas distribution plate 110 . Between processing substrates, a halogen-containing cleaning gas mixture may be energized in a remote plasma source 124 to remotely provide plasma for cleaning chamber components. The halogen-containing cleaning gas mixture entering the process volume 106 may further be excited by radio frequency power provided to the gas distribution plate 110 through the first electrical power source 122 . Although gas source 120 is coupled to cover assembly 112 via remote plasma source 124, it should be understood that in some embodiments, gas source 120 is coupled directly to the cover assembly.

In one embodiment, the substrate 102 processable in the substrate processing chamber 100 may have a surface area of 10,000 cm ² or greater, such as 25,000 cm ² or greater, for example, about 55,000 cm ² or greater. It will be appreciated that after processing, the substrate may be cut to form smaller other devices.

In one embodiment, the heating and/or cooling element 139 may be configured to provide a substrate support assembly temperature during cleaning of about 600 degrees Celsius or less (between about 10 degrees Celsius and about 300 degrees Celsius; between about 200 degrees Celsius and about 300 degrees Celsius). degrees Celsius; between about 10 degrees Celsius and about 50 degrees Celsius; or between about 10 degrees Celsius and 30 degrees Celsius).

The nominal separation between the upper surface 118 of the substrate 102 and the gas distribution plate 110 disposed on the substrate receiving surface 132 during cleaning may generally vary between 400 mils and about 1,200 mils, such as at 400 mils. vary between 1 and about 800 mils, or other distances used to obtain the desired deposition results. In one embodiment in which the gas distribution plate 110 has a concave downstream surface, the separation between a central portion of the edge of the gas distribution plate 110 and the substrate receiving surface 132 is between about 400 mils and about 1400 mils, And the spacing between the corners of the gas distribution plate 110 and the substrate receiving surface 132 is between about 300 mils and about 1,200 mils.

FIG. 1B shows a cross-sectional view of the substrate processing chamber 100 of FIG. 1A with the substrate 102 removed. Figure IB provides an illustration 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 170 (shown as a solid arrow in FIG. 1B ) is introduced into a process volume 106 with residual film 180 to be removed during the cleaning process (eg, such as ZrO ₂ , High dielectric constant dielectric materials such as Y ₂ O ₃ or HfO ₂ ). As shown in FIG. 1B , residual film 180 is deposited on at least a portion of the exposed surfaces within substrate processing chamber 100 , specifically on gas distribution plate 110 , substrate support assembly 130 , shielding frame 133 , and the like. The halogen-containing gas mixture 170 is exposed to an energy source, such as the first electrical power source 122, the second electrical power source 160, or the remote plasma source 124, thereby generating products such as chlorine radicals, fluorine radicals, bromine radicals, hydrogen radicals, and the above. A combination of reactive species 190. Reactive species 190 react with residual film 180 and form volatile products. Volatile products are removed from the substrate processing chamber 100. One or more interior surfaces of the substrate processing chamber 100 (e.g., gas distribution plate 110, substrate support assembly 130, shielding frame 133, sidewalls 142, etc.) have at least one coating material formed thereon (e.g., exposed Al ₂ O ₃ film or exposed yttrium-containing film). One or more interior surfaces may comprise aluminum, stainless steel, nickel-iron alloy (eg, Invar or 64FeNi), or other materials compatible with plasma processing. In embodiments, the reactive species 190 may be delivered to the process volume 106 where they are formed ex-situ (eg, via a remote plasma).

2 illustrates a process flow diagram of one embodiment of a method 200 that may be used to remove high-k dielectric material from a substrate processing chamber. The substrate processing chamber may be similar to the substrate processing chamber 100 shown in Figures 1A and 1B. At operation 210, a high-k dielectric material is deposited over a substrate disposed in a substrate processing chamber. During deposition of the high-k dielectric material over the substrate, the high-k dielectric material may be deposited on chamber components including the substrate processing chamber (e.g., gas distribution plate, substrate support assembly, shadow frame, sidewalls etc.) on the inner surface. The inner surface may comprise aluminum, stainless steel, nickel-iron alloy (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 embodiment, the high-k dielectric material is selected from the group consisting of zirconium oxide (ZrO ₂ ), hafnium oxide (HfO ₂ ), aluminum oxide (Al ₂ O ₃ ), and combinations thereof. In one embodiment, the high-k dielectric material is doped. In one embodiment, the doped high-k dielectric material is an aluminum-doped zirconia-containing material.

High-k dielectric materials may be produced using, 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 physical vapor deposition (PVD) process to deposit. In some embodiments, at least some portions of the chamber components are composed of aluminum. In some embodiments, at least some portions of the chamber components have a coating disposed thereon. In some embodiments, the coating includes a compound selected from the group consisting of aluminum oxide (Al ₂ O ₃ ), yttrium-containing compounds, and combinations thereof. In one embodiment, the yttrium-containing compound is selected from the group consisting of 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 of the above. In some embodiments, the chamber components do not have a coating disposed thereon and are therefore "uncoated."

At operation 220, the substrate is transferred out of the substrate processing chamber. In some embodiments, the substrate remains in the substrate processing chamber during the cleaning process.

At operation 230, reactive species are introduced into the substrate processing chamber. Reactive species can be generated using plasma. The plasma may be generated in situ or the plasma may be generated ex situ (eg, remotely). Appropriate plasma generation techniques and sources, such as inductively coupled plasma (ICP), capacitively coupled plasma (CCP), remote plasma source (RPS), or microwave plasma generation techniques, can be used to form the reactive species. In some embodiments, reactive species are formed in situ via an in situ plasma process. In some embodiments, reactive species are formed ex situ via a remote plasma source and introduced into the substrate processing chamber.

In one embodiment, reactive species may be generated by flowing a halogen-containing cleaning gas mixture into the process volume 106 . In one embodiment, the halogen-containing cleaning gas mixture includes a halogen-containing gas. In one embodiment, the halogen-containing gas is selected from the group consisting of chlorine-containing gas, hydrogen bromide (HBr) gas, and combinations of the above gases. In one embodiment, 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 of the above gases. In one embodiment, the halogen-containing cleaning gas mixture includes BCl ₃ and NF ₃ . In one embodiment, the halogen-containing cleaning gas mixture includes BCl ₃ and Cl ₂ . In one embodiment, the halogen-containing gas mixture further includes a carbon-containing gas. In one embodiment, the carbonaceous gas is selected from _CO2 , _CH4 , _CHF3 , _{CH2F2 , CH3F} , _CF4, and combinations of the foregoing. In one embodiment, the halogen-containing gas mixture further includes a diluent gas. The dilution gas may be selected from helium, argon and combinations of the above gases. In some embodiments, halogen-containing gas and carbon-containing gas are introduced separately into process volume 106 .

In one embodiment, the halogen-containing cleaning gas mixture includes at least one of CO2 _{, CH4} , _{CHF3 , CH2F2} , _CH3F , _CF4 and combinations thereof and _BCl3 . In another embodiment, the halogen-containing cleaning gas mixture includes at least one of CO2 _{, CH4} , _{CHF3 , CH2F2} , _CH3F , _CF4 and combinations thereof and _Cl2 . In yet another embodiment, the halogen-containing cleaning gas mixture includes at least one of _CO2 , _CH4 , _CHF3 , _{CH2F2 , CH3F} and combinations thereof and HBr. In another embodiment, the halogen-containing cleaning gas mixture includes at least one of CO2 _{, CH4} , _{CHF3 , CH2F2} , _CH3F , _CF4 and combinations thereof and _NF3 . In yet another embodiment, the halogen-containing cleaning gas mixture includes at least one of CO2 _{, CH4} , _CHF3 , _{CH2F2 , CH3F} , _CF4 and combinations of the above gases and _BCl3 , _NF3 . In another embodiment, the halogen-containing cleaning gas mixture includes at least one of CO2 _{, CH4} , _CHF3 , _{CH2F2 , CH3F} , _CF4 and combinations of the above gases and _BCl3 , _Cl2 .

In one embodiment, the halogen-containing cleaning gas mixture is exposed to a radio frequency source and/or a bias power source. A radio frequency source and/or bias power source energizes the halogen-containing cleaning gas mixture within the process volume 106 so that the plasma can be maintained. In one embodiment, the first electrical power source 122 is operable to provide radio frequency power at a frequency between 0.3 MHz and about 14 MHz, such as about 13.56 MHz. The first electrical power source 122 may generate radio frequency power of about 10 watts to about 5000 watts (eg, between about 300 watts and about 1500 watts; between about 500 watts and about 1000 watts).

In some embodiments, in addition to RF source power, RF bias power may be utilized during the cleaning process to assist in dissociating the cleaning gas mixture to form a plasma. The radio frequency bias may be provided by the second electrical power source 160 . In one embodiment, the first electrical power source 122 is operable to provide radio frequency power at a frequency between 0.3 MHz and about 14 MHz, such as about 13.56 MHz. The radio frequency bias power supply may be supplied at a power of between about 0 watts and about 1000 watts (eg, between about 10 watts and about 100 watts) at a frequency of 300 kHz. In one embodiment, the radio frequency bias power supply may be pulsed at radio frequency frequencies of about 500 Hz and about 10 kHz with a duty cycle between about 10% and about 95%. In some embodiments, the coating material (eg, Al ₂ O ₃ ) is removed along with the residual high-k dielectric material with the application of an additional bias voltage. Without being bound by theory, it is believed that the DC bias establishes a potential difference between the plasma and the substrate to enhance etching.

In some embodiments, the plasma can be formed capacitively or inductively and can be energized by coupling radio frequency power to the halogen-containing cleaning gas mixture. The radio frequency power may be dual-band radio frequency power with high frequency components and low frequency components. The radio frequency power is typically applied at a power level between about 50 W and about 2500 W, which may be all high frequency radio frequency power, for example at a frequency of about 13.56 Mhz; or may be a mixture of high frequency power and low frequency power, For example at a frequency of about 300kHz.

In some embodiments in which 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 includes a halogen-containing gas, optionally a carbon-containing gas, and optionally a diluent gas. In some embodiments, an optional diluent gas may serve as a carrier gas. In some embodiments, the optional diluent gas can extend the lifetime of the radical species and increase the density of the radical species. In some embodiments, halogen-containing gas flows into the remote plasma source and other process gases (eg, carbon-containing gases) are delivered into the chamber, respectively.

The remote plasma source may be an inductively coupled plasma source. The remote plasma source receives the halogen-containing cleaning gas mixture and forms a plasma in the halogen-containing cleaning gas mixture, thereby causing the halogen-containing cleaning gas mixture to dissociate to form reactive species. Reactive species may include chlorine radicals, bromine radicals, fluorine radicals, and combinations of the foregoing. Remote plasma sources provide efficient dissociation of halogen-containing clean gas mixtures.

In some embodiments, the remote plasma is initiated using an initial flow of argon or similar inert gas prior to introducing the halogen-containing cleaning gas mixture into the remote plasma chamber.

The halogen-containing cleaning gas mixture may flow into the substrate processing chamber at a flow rate of about 100 seem to about 20,000 seem. In some embodiments, the halogen-containing cleaning gas mixture may flow into the substrate processing chamber at a flow rate of about 500 seem to about 4,000 seem. In some embodiments, the halogen-containing cleaning gas mixture may flow into the substrate processing chamber at a flow rate of approximately 1,000 sccm.

In one embodiment, the pressure within the substrate processing chamber is between about 10 millitorr and about 300 millitorr. In one embodiment, the pressure within the substrate processing chamber is between about 10 millitorr and about 5 millitorr, such as about 20 millitorr.

In some embodiments, the remote plasma is initiated using an initial flow of argon or similar inert gas prior to introducing the halogen-containing gas mixture into the remote plasma source. Subsequently, the flow rate of argon gas is reduced as the halogen-containing gas mixture is introduced into the remote plasma chamber. As an example, a remote plasma may be initiated by a flow rate of argon gas of 3,000 sccm, with the flow rate of argon gas gradually reduced to 1,000 sccm and subsequently reduced to 500 sccm.

In some embodiments, the cleaning process is performed at room temperature. In some embodiments, the substrate support base is heated to a temperature of about 600 degrees Celsius or less, such as between about 10 degrees Celsius and about 200 degrees Celsius, or between about 10 degrees Celsius and about 50 degrees Celsius, such as at about 10 degrees Celsius. degrees Celsius and about 30 degrees Celsius. Controlling temperature can be used to control the removal/etch rate of deposits containing high-k dielectric materials. The removal rate can increase as the chamber temperature increases.

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

At operation 240, the reactive species reacts with the deposit containing the high-k dielectric material to form a gaseous volatile product. In some embodiments, the removal rate of residual high-k dielectric material-containing deposits is greater than the removal rate of the coating material that coats at least a portion of the chamber components. In some embodiments, the residual high-k dielectric-containing deposit is removed at a rate greater than (For example, from about/> to date From approx/> Until about/> or from approx/> Until about/> ). In some embodiments, reacting the residual high-k dielectric-containing deposit with the reactive species to form volatile products is an unbiased process. In some embodiments in which no additional bias is applied, the coating material removal rate is less than (For example, from about/> Until about/> From approx/> Until about/> or/> ). In some embodiments in which no additional bias is applied, the removal rate of coating material is a minimal or very slow removal rate (e.g., less than below/> below/> below/> below/> or below/> ).

Optionally, at operation 250, gaseous volatile products are purged from the substrate processing chamber. The substrate processing chamber can be effectively purged by flowing purge gas into the substrate processing chamber. Alternatively, or in addition to introducing purge gas, the substrate processing chamber may be depressurized to remove any residual cleaning gas as well as any by-products from the substrate processing chamber. The substrate processing chamber may be purged by emptying the substrate processing chamber. The time period of the purge process should generally be long enough to remove volatile products from the substrate processing chamber. The purge gas flow period should generally be long enough to remove volatile products from the interior surfaces of the chamber including the chamber components.

At operation 260, at least one of operations 230, 240, and 250 is repeated until the selected cleaning endpoint is achieved. It will be appreciated that several cleaning cycles may be applied, with optional purification processes performed between cleaning cycles.

In some embodiments, method 200 further includes removing coating material, if present, from the substrate processing chamber. The coating material is removed by applying an additional bias while forming the reactive species and/or while 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 illustrates a process flow diagram of one embodiment of a method 200 that may be used to remove high-k material from a substrate processing chamber. The substrate processing chamber may be similar to the substrate processing chamber 100 shown in Figures 1A and 1B. At operation 310, a zirconium oxide ( _ZrO2 )-containing layer is deposited over a substrate disposed in a substrate processing chamber. During deposition of the zirconia-containing layer over the substrate, zirconia and/or zirconia-containing compounds may be deposited on chamber components including the substrate processing chamber (e.g., gas distribution plates, substrate support assemblies, shadow frames, sidewalls, etc. ) on the inner surface. The zirconia-containing layer may be an aluminum-doped zirconia-containing layer. The zirconium oxide-containing layer may be formed using, 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), and physical vapor deposition (PVD) processes. to deposit. One or more interior surfaces/chamber components may comprise aluminum, stainless steel, nickel-iron alloy (eg, Invar or 64FeNi), or other materials compatible with plasma processing. In some embodiments, at least a portion of the chamber components are composed of aluminum. In some embodiments, at least a portion of the chamber component has an aluminum oxide (Al ₂ O ₃ ) layer disposed thereon. In some embodiments, at least a portion of the chamber components are composed of stainless steel.

At operation 320, the substrate is transferred out of the substrate processing chamber. In some embodiments, the substrate remains in the substrate processing chamber during the cleaning process.

At operation 330, reactive species are introduced into the substrate processing chamber. The reactive species may be generated using a plasma generated in situ or the plasma may be generated ex situ (eg, remotely). Appropriate plasma generation techniques such as inductively coupled plasma (ICP), capacitively coupled plasma (CCP), remote plasma source (RPS) or microwave plasma generation techniques can be used to form the reactive species. In some embodiments, reactive species are formed in situ via an in situ plasma process. In some embodiments, reactive species are formed ex situ via a remote plasma source.

In one embodiment, the reactive species may be generated by flowing a clean gas mixture into the process volume 106 . In one embodiment, the cleaning gas mixture contains BCl ₃ and optionally a diluent gas. The dilution gas may be an inert gas selected from helium, argon, or combinations thereof. The cleaning gas mixture is exposed to a radio frequency source and/or a bias power source. A radio frequency source and/or bias power source energizes the clean gas mixture within the process volume 106 so that the plasma can be maintained. In one embodiment, the first electrical power source 122 is operable to provide radio frequency power at a frequency between 0.3 MHz and about 14 MHz, such as about 13.56 MHz. The first electrical power source 122 may generate radio frequency power of about 10 watts to about 5000 watts (eg, between about 300 watts and about 1500 watts; between about 500 watts and about 1000 watts).

In some embodiments, in addition to RF source power, RF bias power may be utilized during the cleaning process to assist in dissociating the cleaning gas mixture to form a plasma. The radio frequency bias may be provided by the second electrical power source 160 . In one embodiment, the first electrical power source 122 is operable to provide radio frequency power at a frequency between 0.3 MHz and about 14 MHz, such as about 13.56 MHz. The radio frequency bias power supply may be supplied at a power of between about 0 watts and about 1000 watts (eg, between about 10 watts and about 100 watts) at a frequency of 300 kHz. In one embodiment, the radio frequency bias power supply may be pulsed at a radio frequency between about 500 Hz and about 10 kHz with a duty cycle between about 10% and about 95%. In some embodiments where this additional bias is applied, the Al ₂ O ₃ is removed along with the residual ZrO ₂ containing film.

In some embodiments, in addition to RF source power, a DC bias power source may be utilized during the cleaning process to aid in the dissociation of the cleaning gas mixture forming the plasma. The DC bias voltage may be provided by the second electrical power source 160 . In one embodiment, the first electrical power source 122 is operable to provide radio frequency power at a frequency between 0.3 MHz and about 14 MHz, such as about 13.56 MHz. The second electrical power source 160 is operable at a power of between about 10 Watts and about 3000 Watts (eg, between about 10 Watts and about 1000 Watts; or between about 10 Watts and about 100 Watts) at a frequency of 300 kHz. Provides DC bias power. In one embodiment, the DC bias power supply may be pulsed at a frequency between about 500 Hz and about 10 kHz with a duty cycle between about 10% and about 95%. Without being bound by theory, it is believed that the DC bias establishes a potential difference between the plasma and the substrate to enhance etching.

In some embodiments, the plasma can be formed capacitively or inductively and can be energized by coupling radio frequency power to the cleaning gas mixture. The radio frequency power may be dual-band radio frequency power with high frequency components and low frequency components. The radio frequency power is typically applied at a power level between about 50 W and about 2,500 W, which may be all high frequency radio frequency power, such as at a frequency of about 13.56 MHz; or may be a combination of high frequency power and low frequency power. Mix, for example at a frequency of about 300kHz.

In some embodiments where reactive species are formed ex-situ, the BCl ₃ -containing gas mixture is flowed into a remote plasma source fluidly coupled to the substrate processing chamber. The BCl ₃ -containing gas mixture contains BCl ₃ and optionally an inert gas. In some embodiments, an optional inert gas may serve as a carrier gas. In some embodiments, the optional inert gas can extend the lifetime of the radical species and increase the density of the radical species. In some embodiments, a BCl ₃ -containing gas mixture flows into a remote plasma source and other process gases are delivered into the chamber, respectively. The optional inert gas may be selected from the group consisting of helium, argon, or a combination of the above gases.

The remote plasma source may be an inductively coupled plasma source. The remote plasma source receives the BCl ₃ -containing gas mixture and forms a plasma in the BCl ₃ -containing gas mixture, thus causing the BCl ₃ -containing gas mixture to dissociate to form reactive species. Reactive species may include chlorine radicals. Remote plasma sources provide efficient dissociation of _BCl- containing gas mixtures.

In some embodiments, the remote plasma is initiated using an initial flow of argon or similar inert gas prior to introducing the BCl ₃ -containing gas mixture into the remote plasma chamber.

The BCl _- containing gas mixture may flow into the substrate processing chamber at a flow rate of about 100 seem to about 10,000 seem. In some embodiments, the BCl ₃ -containing gas mixture flows into the substrate processing chamber at a flow rate from about 500 seem to about 4,000 seem. In some embodiments, the BCl _3- containing gas mixture flows into the substrate processing chamber at a flow rate of about 1,000 sccm.

The pressure within the substrate processing chamber may be between about 10 millitorr and about 300 millitorr. The pressure within the substrate processing chamber may be between 10 millitorr and about 5 millitorr, such as about 20 millitorr.

In some embodiments, the remote plasma is initiated using an initial flow of argon or similar inert gas prior to introducing _BCl into the remote plasma source. Subsequently, the flow rate of argon gas is reduced as _BCl is introduced into the remote plasma chamber. As an example, a remote plasma may be initiated by a flow rate of argon gas of _3,000 sccm, with the flow rate of argon gas gradually reduced to 1,000 sccm and subsequently reduced to 500 sccm.

In some embodiments, the cleaning process is performed at room temperature. In some embodiments, the substrate support base is heated to a temperature of about 600 degrees Celsius or less, such as between about 10 degrees Celsius and about 200 degrees Celsius, or between about 10 degrees Celsius and about 50 degrees Celsius, such as at about 10 degrees Celsius. Temperatures between degrees Celsius and 30 degrees Celsius. Controlling temperature can be used to control the removal/etch rate of high-k dielectric material deposits. The removal rate can increase as the chamber temperature increases.

Reactive species formed from the _BCl gas mixture are transported to the substrate processing chamber. Reactive species include chlorine radicals.

At operation 340, the reactive species react with the zirconia-containing deposit to form gaseous volatile products. Volatile products include zirconium tetrachloride (ZrCl ₄ ). In some embodiments, the removal rate of the residual _ZrO2- containing film is greater than the removal rate of _{the Al2O3} that coats at least _a portion of _the aluminum chamber components. In some embodiments, the removal rate of residual _ZrO2- containing film is greater than (For example, from about/> Until about/> From approx/> to date Or from about/> Until about/> ). In some embodiments, reacting the residual _ZrO2- containing film with reactive species to form volatile products is an unbiased process. In some embodiments where no additional bias is applied, the removal rate of Al ₂ O ₃ is less than (For example, from about/> Until about/> From about/> Until about/> or/> ).

Optionally, at operation 350, gaseous volatile products are purged from the substrate processing chamber. The substrate processing chamber can be effectively purged by flowing purge gas into the substrate processing chamber. Alternatively, or in addition to introducing purge gas, the substrate processing chamber may be depressurized to remove any residual cleaning gas as well as any by-products from the substrate processing chamber. The substrate processing chamber may be purged by emptying the substrate processing chamber. The time period of the purge process should generally be long enough to remove volatile products from the substrate processing chamber. The purge gas flow period should generally be long enough to remove volatile products from the interior surfaces of the chamber including the chamber components.

At operation 360, at least one of operations 330, 340, and 350 is repeated until the selected cleaning endpoint is achieved. It will be appreciated that several cleaning cycles may be applied, with optional purification processes performed between cleaning cycles.

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

Example:

The following non-limiting examples are provided to further illustrate the embodiments described herein. However, these examples are not intended to be all-inclusive and are not intended to limit the scope of the embodiments described herein. Table I shows the results of a cleaning process performed in accordance with one embodiment of the present disclosure. As shown in Table I, the inductively coupled plasma process performed with BCl ₃ and no DC bias had higher removal rates for ZrO ₂ , aluminum-doped ZrO ₂ and aluminum relative to Al ₂ O ₃ . As further shown in Table I, the process also removes Al ₂ O ₃ when a DC bias is applied.

Table I

Table II shows the results of a cleaning process performed in accordance with one embodiment of the present disclosure. As shown in Table II, the capacitively coupled plasma process performed with BCl _and no DC bias yields _better results for ZrO, aluminum-doped ZrO and yttrium coatings relative to Al ₂ O ₃ , stainless steel, Invar and _Y coatings Aluminum has a higher removal rate.

Table II

In summary, some of the benefits of the present disclosure include no etching or minimal etching of chamber coating materials (e.g., _Al2O3 and/or yttrium-containing compounds ₎ and/or chamber materials (e.g., stainless steel and/or nickel-iron alloys) The ability to selectively etch residual high-k dielectric films (e.g., ZrO ₂ and HfO ₂ ) without any problem. The selectivity can be used to protect aluminum chamber components. Aluminum chamber components are typically etched during the plasma cleaning process. The inventors have discovered that using Al ₂ O ₃ anodizing or other chamber coating materials to protect the aluminum components in the chamber allows for preferential removal of residual high-k dielectric films without damaging the aluminum components, thus ensuring the safety of the hardware components. Reliability and longevity. Selectivity is critical to achieving clean-in-place functionality. Thus, during cleaning, residual film may be removed by cleaning agents (eg, BCl ₃ , Cl ₂ , HBr, or NF ₃ ), but the aluminum sidewalls and other aluminum hardware components inside the chamber remain intact. As discussed above, embodiments of the present disclosure include using reactive plasma species of a halogen-containing gas mixture to clean residual high-k dielectric films and using coating materials on aluminum hardware components inside the chamber to protect Aluminum hardware components. If no additional bias is applied, the reactive plasma species effectively etch high-k dielectric materials and aluminum but not coating materials. Therefore, aluminum can be used as a material for hardware components as long as it is coated with a coating material such as Al ₂ O ₃ or an yttrium-containing compound. Reactive plasma species can also etch Al ₂ O ₃ when an additional bias voltage is applied. These characteristics make reactive plasma species ideal cleaners for in-situ cleaning of high-dielectric-constant materials in deposition chambers.

When introducing elements of the present disclosure or exemplary aspects or embodiments thereof, the articles "a," "an," "the," and "said" are intended to mean Refers to the presence of one or more elements.

The terms "comprising," "including," and "having" are intended to be inclusive and mean that additional elements may be present other than the listed elements.

While the foregoing is directed to embodiments of the disclosure, other and further embodiments of the disclosure may be devised without departing from the essential scope of the disclosure, which scope is defined by the appended claims. Sure.

Claims (19)

1. A method for cleaning a process chamber, comprising:

introducing a reactive species into a process chamber having a residual high dielectric constant dielectric material formed on one or more interior surfaces of the process chamber, wherein the one or more interior surfaces comprise a stainless steel surface of at least one sidewall and at least one aluminum surface coated with a protective coating, wherein the protective coating comprises an aluminum oxide material disposed on the aluminum surface and a yttrium-containing material disposed on the aluminum oxide material;

reacting the residual high-k dielectric material with the reactive species to form a volatile product; and

removing the volatile product from the process chamber,

wherein the residual high-k dielectric material has a removal rate greater than the removal rate of material of the one or more inner surfaces;

Wherein the reactive species is formed from a halogen-containing gas mixture; and is also provided with

Wherein the residual high-k dielectric material is selected from zirconium dioxide (ZrO) ₂ ) And hafnium oxide (HfO) ₂ )。

2. The method of claim 1, wherein the yttrium-containing material is selected from yttrium oxide (Y ₂ O ₃ ) Fluorinated Yttrium Oxide (YOF), yttrium chlorate (Y (ClO) ₃ ) ₃ ) Yttrium (III) fluoride (YF) ₃ ) Yttrium (III) chloride (YCl) ₃ ) Yttria Stabilized Zirconia (YSZ) or a combination of the above.

3. The method of claim 1, wherein the halogen-containing gas mixture comprises a halogen-containing gas selected from BCl ₃ 、Cl2、HBr、NF ₃ Or a combination of the above gases.

4. The method of claim 3, wherein the halogen-containing gas mixture further comprises a carbon-containing gas.

5. The method of claim 4, wherein the carbon-containing gas is selected from the group consisting of CO ₂ 、CH ₄ 、CHF ₃ 、CH ₂ F ₂ 、CH ₃ F、CF ₄ Or a combination of the above gases.

6. The method of claim 4, wherein the halogen-containing gas mixture further comprises a diluent gas selected from helium, argon, or a combination thereof.

7. The method of claim 1, wherein the halogen-containing gas mixture comprises BCl ₃ And NF (NF) ₃ 。

8. The method of claim 1, further comprising exposing the reactive species to one or more energy sources sufficient to react the residual high dielectric constant dielectric material with the reactive species and form the volatile product.

9. The method of claim 8, wherein the one or more energy sources are selected from the group consisting of a capacitively coupled plasma source, an inductively coupled plasma source, a microwave plasma source, and a remote plasma source.

10. The method of claim 1, wherein the pressure at which the residual high-k dielectric material reacts with the reactive species to form the volatile product is between at least about 10 mtorr and about 5 torr.

11. The method of claim 1, wherein 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.

12. A method for cleaning a process chamber, comprising:

depositing a high dielectric constant dielectric material on one or more interior surfaces of a processing chamber and a substrate disposed in the processing chamber;

transferring the substrate out of the processing chamber;

introducing a reactive species into the process chamber having a residual high-k dielectric material formed on one or more interior surfaces of the process chamber, wherein the one or more interior surfaces comprise:

At least one aluminum surface coated with a protective coating comprising an alumina material disposed on the aluminum surface and a yttrium-containing material disposed on the alumina material, and

at least one stainless steel surface of at least one sidewall;

reacting the residual high-k dielectric material with the reactive species to form a volatile product; and

removing the volatile product from the processing chamber, wherein the residual high-k dielectric material has a removal rate greater than a removal rate of material of the one or more interior surfaces,

wherein the high-k dielectric material is selected from zirconium dioxide (ZrO ₂ ) And hafnium oxide (HfO) ₂ )，

Wherein the reactive species are formed from a halogen-containing gas mixture.

13. The method of claim 12, wherein the coating material has a removal rate less than

14. The method of claim 12, wherein reacting the residual high-permittivity dielectric material with the reactive species to form the volatile product further comprises exposing the reactive species to one or more energy sources sufficient to react the residual high-permittivity dielectric material with the reactive species and form the volatile product.

15. The method of claim 14, wherein the one or more energy sources are selected from the group consisting of a capacitively coupled plasma source, an inductively coupled plasma source, a microwave plasma source, and a remote plasma source.

16. The method of claim 12, wherein reacting the residual high-k dielectric material with the reactive species to form a volatile product is a bias-free process.

17. The method of claim 12, wherein no additional bias is applied in reacting the residual high-k dielectric material with the reactive species to form the volatile product.

18. The method of claim 17, further comprising:

reacting the coating material with the reactive species to form a second volatile product when an additional bias is applied; and

the second volatile product is removed from the processing chamber.

19. A method for cleaning a process chamber, comprising:

flowing a halogen-containing cleaning gas mixture into a remote plasma source fluidly coupled to the process chamber;

forming a reactive species from the halogen-containing cleaning gas mixture;

delivering the reactive species into the process chamber, wherein the process chamber has a residual high-k dielectric material formed on one or more interior surfaces of the process chamber, wherein the one or more interior surfaces comprise:

At least one aluminum surface coated with a protective coating comprising an alumina material disposed on the aluminum surface and a yttrium-containing material disposed on the alumina material, and

at least one stainless steel surface of at least one sidewall;

allowing the reactive species to react with the residual high-k dielectric material to form a gaseous product; and

purging the gaseous products from the process chamber,

wherein the residual high-k dielectric material is selected from zirconium dioxide (ZrO) ₂ ) And hafnium oxide (HfO) ₂ )。