CN111066121A - Selective in-situ cleaning of high dielectric constant films from processing chambers using reactive gas precursors - Google Patents

Abstract

Translated fromChinese

在一个实施方式中，提供一种用于清洁处理腔室的方法。所述方法包含将反应性物种引入具有残余的高介电常数介电材料的处理腔室中，所述残余的高介电常数介电材料形成在处理腔室的一个或多个内表面上。反应性物种由含卤素气体混合物形成，并且一个或多个内表面包括具有涂层材料形成在其上的至少一个表面。所述方法进一步包含使残余的高介电常数介电材料与反应性物种反应以形成挥发性产物。所述方法进一步包含从处理腔室去除挥发性产物。所述残余的高介电常数介电材料的去除速率大于涂层材料的去除速率。高介电常数介电材料选自二氧化锆(ZrO₂)和二氧化铪(HfO₂)。涂层材料包括选自氧化铝(Al₂O₃)、含钇化合物和上述两者的组合的化合物。

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. The reactive species are 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 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 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 (ZrO₂ ) and hafnium dioxide (HfO₂ ). The coating material includes a compound selected from the group consisting of aluminum oxide (Al₂ O₃ ), yttrium-containing compounds, and combinations of the two.

Description

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

Technical Field

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

Background

Display devices have been widely used for various electronic applications such as Televisions (TVs), monitors, mobile phones, MP3 players, electronic book readers, Personal Digital Assistants (PDAs), and the like. Display devices are generally designed to produce images by applying an electric field to liquid crystals that fill a gap between two substrates (e.g., a pixel electrode and a common electrode) and have an anisotropic dielectric constant that controls the strength of the dielectric field. 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 an Active Matrix Liquid Crystal Display (AMLCD) or an Active Matrix Organic Light Emitting Diode (AMOLED), may be used as a light source of 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 and circuit integration for light transmission, resulting in brighter displays, higher overall electrical efficiency, faster response times, and higher resolution displays. The low film quality of material layers formed in the device, such as dielectric layers having impurities or low film density, often results in poor electrical performance of the device and a short lifetime of the device. Therefore, stable and reliable methods for forming and integrating film layers within TFT and OLED devices to provide device structures with low film leakage and high breakdown voltage become critical for manufacturing electronic devices with lower threshold voltage shifts and improved overall performance.

In particular, the management of the interface between the metal electrode layer and the nearby insulating material becomes critical, since improper material selection of the interface between the metal electrode layer and the nearby insulating material may disadvantageously cause diffusion of undesired elements into neighboring materials, which may ultimately lead to current shorts, current leakage, or device failure. In addition, insulating materials with different higher dielectric constants typically provide different electrical properties, such as providing different capacitances in the device structure. Not only does the material selection of the insulating material affect 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 product yield.

In some devices, a capacitor (e.g., a dielectric layer placed between two electrodes) is typically utilized and formed to store charge when the display device is in operation. The formed capacitor needs to have a high capacitance for the display device. The capacitance can be adjusted by varying 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 (e.g., zirconia), the capacitance of the capacitor will also increase.

As the resolution requirements for display devices become increasingly challenging (e.g., display resolutions greater than 2,000 Pixels Per Inch (PPI)), display devices have limited area for forming capacitors to increase electrical performance. Therefore, it has become critical to keep the capacitors formed in the display device in a limited location with a relatively small area. Higher dielectric constant ("high-k") dielectric materials (e.g., zirconium oxide and hafnium oxide) have been found to enable higher resolution display devices. However, the deposition of high dielectric constant dielectric materials is not limited to substrates and typically forms a residual film 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 ownership costs of production and maintaining film quality, chamber cleaning is performed to remove residual film residues from the interior surfaces of the processing chamber, including process kit parts, e.g., showerhead, etc. Unfortunately, most known cleaning techniques, such as fluorine-containing plasmas, are either not capable of removing high dielectric constant dielectric materials or are so harsh as to damage chamber components. Thus, no in-situ cleaning technique for high-k dielectric materials is currently available. Currently, zirconia is removed from a processing chamber 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.

Therefore, there is a need for a method of removing unwanted high-k dielectric material deposits in-situ from a substrate processing chamber.

Disclosure of Invention

Embodiments described herein generally relate to methods for in-situ removal of unwanted deposition build-up from one or more interior surfaces of a substrate processing chamberAnd an apparatus. In one embodiment, a method for cleaning a processing chamber is provided. The method includes introducing a reactive species into a processing chamber having a residual high-permittivity dielectric material formed on one or more interior surfaces of the processing chamber. The reactive species are formed from a halogen-containing gas mixture. The one or more inner surfaces comprise at least one stainless steel surface. The method further comprises reacting the residual high dielectric constant dielectric material with a reactive species to form a volatile product. The method further comprises removing volatile products from the processing chamber. The removal rate (removalrate) of the residual high-k dielectric material is greater than the removal rate of stainless steel. The high dielectric constant dielectric material is selected from zirconium dioxide (ZrO)₂) And hafnium oxide (HfO)₂)。

In another embodiment, a method for cleaning a processing chamber is provided. The method includes depositing a high dielectric constant dielectric material on one or more interior surfaces of a process chamber and a substrate disposed in a 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 having residual high-permittivity dielectric material formed on one or more interior surfaces of the processing chamber. The reactive species are formed from a halogen-containing gas mixture, and the one or more internal surfaces include at least one stainless steel surface and at least one surface having a coating material formed thereon. The method further comprises reacting the residual high dielectric constant dielectric material with a reactive species to form a volatile product. The method further comprises removing volatile products from the processing chamber, wherein a removal rate of the residual high-k dielectric material is greater than a removal rate of the coating material and a removal rate of the stainless steel. The high dielectric constant 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)₂O₃) Yttrium-containing compounds, and combinations of the foregoing.

In yet another embodimentIn one aspect, 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 comprises forming reactive species from the halogen containing cleaning gas mixture. The method further includes delivering a reactive species into the processing chamber. The process chamber has a residual high dielectric constant dielectric material formed on one or more interior surfaces of the process 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 the gaseous product from the processing chamber. The high dielectric constant 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)₂O₃) Yttrium-containing compounds, and combinations of the foregoing.

In another embodiment, a method for cleaning a processing chamber is provided. The method comprises introducing a reactive species into the atmosphere having residual ZrO-containing₂In the processing chamber of the film, the residual ZrO-containing₂The film is formed on one or more interior surfaces of the process chamber. Reactive species from BCl₃Is formed and one or more of the inner surfaces includes at least one exposed Al₂O₃A surface. The method further comprises reacting the residual ZrO-containing₂The membrane reacts with the reactive species to form volatile products. The method further comprises removing volatile products from the processing chamber, wherein residual ZrO-containing products₂The film removal rate is greater than Al₂O₃The removal rate of (c).

In yet another embodiment, a method for cleaning a processing chamber is provided. The method includes depositing ZrO-containing deposits on one or more interior surfaces of a process chamber and a substrate disposed in a substrate processing chamber₂And (3) a membrane. The method further includes transferring the substrate out of the substrate processing chamber. The method further comprises introducing a reactive species into the substrate having residual ZrO-containing species₂In the processing chamber of the film, the residual ZrO-containing₂The film is formed on one or more interior surfaces of the process chamber. Reactive species from BCl₃Is formed and one or more of the inner surfaces includes at least one exposed Al₂O₃A surface. The method further comprises reacting residual ZrO-containing₂The membrane reacts with the reactive species to form volatile products. The method further comprises removing volatile products from the processing chamber, wherein residual ZrO-containing is present₂The film removal rate is greater than Al₂O₃The removal rate of (c).

In another embodiment, a method for cleaning a processing chamber is provided. The method comprises adding boron trichloride (BCl)₃) The cleaning gas mixture flows into a remote plasma source fluidly coupled to the processing chamber. The method further comprises the step of purifying the BCl-containing polypeptide by using BCl₃The cleaning gas mixture forms reactive species. The method further includes delivering a reactive species into the processing chamber. The process chamber has residual ZrO-containing formed on one or more interior surfaces of the process chamber₂The film, and the one or more inner surfaces include at least one exposed Al₂O₃A surface. The method further comprises allowing the reactive species to react with residual ZrO-containing species₂The film reacts 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 a residual high-permittivity dielectric material formed on one or more interior surfaces of the processing chamber. The reactive species are 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 comprises reacting the residual high dielectric constant dielectric material with a reactive species to form a volatile product. The method further comprises removing volatile products from the processing chamber. The residual high-k dielectric material is removed at a rate greater than the removal rate of the coating material. The high dielectric constant 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)₂O₃) Yttrium-containing compounds, and combinations of the foregoing.

In another embodiment, a method for cleaning a processing chamber is provided. The method includes depositing a high dielectric constant dielectric material on one or more interior surfaces of a process chamber and a substrate disposed in a 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 having residual high-permittivity dielectric material formed on one or more interior surfaces of the processing chamber. The reactive species are 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 comprises reacting the residual high dielectric constant dielectric material with a reactive species to form a volatile product. The method further comprises 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 dielectric constant 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)₂O₃) Yttrium-containing compounds, and combinations of the foregoing.

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 comprises forming reactive species from the halogen containing cleaning gas mixture. The method further includes delivering a reactive species into the processing chamber. The process chamber has a residual high dielectric constant dielectric material formed on one or more interior surfaces of the process chamber. The one or more interior surfaces include at least one surface having a coating material formed thereon. The method further comprises allowing the reactive species to react with the residual high-k dielectric material to form a dielectric layerA gaseous product is formed. The method further includes purging the gaseous product from the processing chamber. The high dielectric constant 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)₂O₃) Yttrium-containing compounds, and combinations of the foregoing.

Drawings

So that the manner in which the above recited features of the present disclosure can be understood in detail, a more particular description of the embodiments, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended 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.

FIG. 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;

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

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

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

To facilitate understanding, identical reference numerals have been used, where possible, to designate identical elements that are common to the figures. It is contemplated that elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation.

Detailed Description

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 figures to provide a thorough understanding of various embodiments of the disclosure. Additional details describing well-known structures and systems typically associated with plasma cleaning will not be set forth in the following disclosure to avoid unnecessarily obscuring the description of the various embodiments.

Much of the details, dimensions, angles, and other features shown in the drawings are merely illustrative of particular embodiments. Accordingly, other embodiments may have other details, components, dimensions, angles, and features without departing from the spirit or scope of the disclosure. Furthermore, further 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. One example of such a system is an AKT-90K PECVD system suitable for substrates having substrate dimensions of 3000mm by 3000mm or larger, which is commercially available from Applied Materials, Inc. (Applied Materials Inc.) of Santa Clara, Calif. (Santa Clara, Calif.). Another example of such a system is an AKT-25K PECVD system or AKT-25KALD system suitable for substrates having dimensions of 1850mm by 1500mm or larger, which are commercially available from Applied Materials, Inc. of Santa Clara, California. Other tools capable of performing high-k dielectric deposition processes may also be suitable to benefit from the embodiments described herein. Additionally, any system capable of implementing the high-k dielectric deposition process described herein may be used to advantage. The device descriptions described herein are illustrative and should not be interpreted or otherwise construed as limiting the scope of the embodiments described herein.

Embodiments of the present disclosure generally relate to in-situ removal of, for example, ZrO from a processing chamber₂And HfO₂The high dielectric constant dielectric material of (1). Processing chambers include, but are not limited to, PECVD, ALD, or other processing chambers for fabricating high resolution display backplane TFT circuits. ZrO (ZrO)₂And HfO₂Are 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)) Device) is formed. Such as ZrO₂And HfO₂Are particularly critical for achieving high resolution display devices (e.g., pixel per inch ("PPI") > 2000). Currently, as the entire pixel area is reduced to increase the resolution, the area of the storage capacitor needs to be reduced in the pixel circuit. To achieve the same capacitance, the current dielectric layer (e.g., SiN, dielectric constant (k) -7) used in the storage capacitor is being replaced by a high-dielectric constant dielectric material, such as ZrO with k > 20₂And HfO with k > 25₂. One factor for achieving high-k dielectric materials in display applications is the efficient removal of residual high-k dielectric material from the processing chamber to reduce particles and improve yield.

In general, the deposition of high dielectric constant dielectric materials is not limited to substrates and forms residual films throughout the chamber. This residual film can lead to particle formation, reduced uniformity, and plugged gas inlets, resulting in yield loss and increased cost of ownership. One way to remove unwanted residual films 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 the components, and reassembling the chamber can take a significant amount of time and significantly impact the usable time of the tool. Another method is to apply plasma by applying Radio Frequency (RF) energy to promote excitation and/or dissociation of the reactive gas. The plasma includes highly reactive species that react with and etch unwanted residual materials. For example, NF₃Plasma is widely used in the display industry to remove SiO from process chambers_xAnd SiN_xAnd (3) a membrane. However, NF₃The plasma is generally unable to etch the remaining high-k dielectric material.

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-permittivity dielectric material from a processing chamber by introducing reactive species formed from a halogen-containing gas mixture into the processing chamber to react with the residual high-permittivity dielectric material. The reactive species may be generated as an in-situ plasma (e.g., formed inside the processing chamber) or an ex-situ plasma (e.g., formed via a remote plasma source). The plasma may be generated by, but is not limited to, inductively-coupled plasma (ICP), capacitively-coupled plasma (CCP), Remote Plasma Source (RPS), or microwave plasma.

In some embodiments of the present disclosure, residual high-k dielectric material is removed 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. The excited radicals from the halogen-containing gas mixture etch residual high dielectric constant dielectric material from the chamber body. Plasma of the halogen-containing gas mixture etches the high dielectric constant dielectric material and aluminum if no additional bias is applied, but generally does not etch or minimally etches the coating material (e.g., Al)₂O₃). Thus, 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 the coating material must be removed, an additional bias voltage may be applied to the plasma of the halogen-containing gas mixture during the process to facilitate etching of the coating material. Thus, depending on the plasma conditions, the halogen-containing gas mixture may be used to selectively remove the high-k dielectric material relative to the coating material, or to remove both the high-k dielectric material and the coating material.

Fig. 1A illustrates a cross-sectional view of asubstrate processing chamber 100 that may benefit from a cleaning process in accordance with one or more embodiments of the present disclosure. FIG. 1B illustrates thesubstrate processing chamber 100 of FIG. 1A with residual films formed on one or more interior surfaces that may be removed using one or more embodiments of the present disclosureA cross-sectional view. Thesubstrate 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 combinations thereof. In some embodiments, the substrate processing chamber may be configured to deposit a high dielectric constant dielectric layer, such as ZrO₂Or HfO₂. In some embodiments, thesubstrate processing chamber 100 is configured to process asubstrate 102 using plasma when forming structures and devices on a large area substrate 102 (hereinafter substrate 102) for manufacturing a Liquid Crystal Display (LCD), a flat panel display, an Organic Light Emitting Diode (OLED), or a photovoltaic cell of a solar cell array.

Thesubstrate processing chamber 100 generally includessidewalls 142, abottom wall 104, and alid assembly 112, which define aprocess volume 106. In one embodiment,lid assembly 112 is generally comprised of aluminum. Thelid assembly 112 may be anodized to form Al on the surface of the lid assembly 112₂O₃And (3) a layer. In another embodiment, thelid assembly 112 is made of stainless steel, nickel-iron alloy (e.g., Invar, which is a nickel-iron alloy known as 64FeNi), or other material that is compatible with plasma processing. Theside wall 142 andbottom wall 104 may be made from an integral block of aluminum, stainless steel, nickel-iron alloy (e.g., invar, which is a nickel-iron alloy known as 64FeNi), or other material compatible with plasma processing. Thesidewalls 142 and thebottom wall 104 may be anodized to form a coating material on the surface of thelid assembly 112. In some embodiments, the coating material, where present, may be formed by an anodic oxidation process, a plasma spray process, or a thermal spray process. The coating material may comprise a material selected from the group consisting of alumina (Al)₂O₃) Yttrium-containing compounds, and combinations of the foregoing. Theside wall 142 and thebottom wall 104 may be electrically grounded.

Agas distribution plate 110 and asubstrate support assembly 130 are disposed within theprocess volume 106. Thegas distribution plate 110 and/or thesubstrate support assembly 130 may each independently be formed from aluminum, stainless steel, a nickel-iron alloy (e.g., invar, which is a nickel-iron alloy known as 64FeNi)) Or other materials compatible with plasma processing. In one embodiment, the substrate support assembly comprises stainless steel. In one embodiment, thegas distribution plate 110 comprises stainless steel and the substrate support assembly comprises aluminum oxide (Al)₂O₃) Yttrium-containing compounds, and combinations of the foregoing. Theprocess volume 106 is accessed through a slit valve opening 108 formed through thesidewall 142 so that thesubstrate 102 may be transferred into and out of thesubstrate processing chamber 100.

Thesubstrate support assembly 130 includes asubstrate receiving surface 132 for supporting thesubstrate 102 thereon. Thesubstrate support assembly 130 generally comprises a conductive body supported by a stem (stem)134 that extends through thebottom wall 104. Therods 134 couple thesubstrate support assembly 130 to alift system 136 that raises and lowers thesubstrate support assembly 130 between substrate transfer and processing positions. Ashadow frame 133 may be placed over the perimeter of thesubstrate 102 during processing to prevent deposition on the edge of thesubstrate 102. Lift pins 138 are movably disposed through thesubstrate support assembly 130 and are adapted to space thesubstrate 102 from thesubstrate receiving surface 132. Thesubstrate support assembly 130 may also include heating and/orcooling elements 139 for maintaining thesubstrate support assembly 130 at a selected temperature. Thesubstrate support assembly 130 may also include a ground strap (ground strap)131 to provide an rf return path around the perimeter of thesubstrate support assembly 130. In one embodiment, thesubstrate support assembly 130 has a coating disposed thereon.

Thegas distribution plate 110 is coupled at its periphery to alid assembly 112 orsidewall 142 of thesubstrate processing chamber 100 by a suspension (suspension) 114. In one embodiment, thegas distribution plate 110 is made of aluminum. The surface of thegas distribution plate 110 may be anodized to form a coating material (e.g., Al) on the surface of the gas distribution plate 110₂O₃). In one embodiment, the surface of thegas distribution plate 110 has a yttrium-containing coating (Y) disposed thereon₂O₃). The coating material may be formed on the surface of thegas distribution plate 110 by anodic oxidation, a plasma spray process, or a thermal spray process. Thegas distribution plate 110 may also pass through one or morecentral supports 116 are coupled to thelid assembly 112 to help prevent sagging of thegas distribution plate 110 and/or to control the flatness/curvature of thegas distribution plate 110. Thegas distribution plate 110 may have different configurations with different dimensions. In an exemplary embodiment, thegas distribution plate 110 has a quadrangular planar shape. Thegas distribution plate 110 has adownstream surface 150 having a plurality ofholes 111 formed through thegas distribution plate 110 and facing anupper surface 118 of thesubstrate 102 disposed on thesubstrate support assembly 130. Theholes 111 may have different shapes, numbers, densities, sizes, and distributions across thegas distribution plate 110. In one embodiment, the diameter of thebore 111 may be selected between about 0.01 inches and about 1 inch.

Agas source 120 is coupled to thelid assembly 112 to provide gases to theprocess volume 106 through thelid assembly 112 and subsequently through theapertures 111 formed in thegas distribution plate 110. Avacuum pump 109 is coupled to thesubstrate processing chamber 100 to maintain the gases in theprocess volume 106 at a selected pressure.

The firstelectrical power source 122 is coupled to thelid assembly 112 and/or thegas distribution plate 110. The firstelectric power source 122 provides power that generates an electric field between thegas distribution plate 110 and thesubstrate support assembly 130 so that a plasma may be generated from the gas present between thegas distribution plate 110 and thesubstrate support assembly 130. Thelid assembly 112 and/or thegas distribution plate 110 electrode may be coupled to the firstelectrical power source 122 through an optional filter, which may be an impedance matching circuit. The firstelectrical power source 122 may be a dc power source, a pulsed dc power source, a radio frequency bias power source, a pulsed radio frequency source, or a bias power source, or a combination thereof. In one embodiment, the firstelectrical power source 122 is a radio frequency bias power source.

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

Thesubstrate support assembly 130 may be grounded such that the rf power supplied by the firstelectrical power source 122 to thegas distribution plate 110 may excite gases disposed in theprocess volume 106 between thesubstrate support assembly 130 and thegas distribution plate 110. Thesubstrate support assembly 130 may be made of metal or other similar conductive material. In one embodiment, at least a portion of thesubstrate support assembly 130 may be covered with an electrically insulating coating. The coating may be a dielectric material such as an oxide, silicon nitride, silicon dioxide, aluminum oxide, aluminum dioxide, tantalum pentoxide, silicon carbide, polyimide, yttrium-containing compounds, and the like. Alternatively, thesubstrate receiving surface 132 of thesubstrate support assembly 130 may be free from coating or anodization.

Electrodes (not shown), which may be bias electrodes and/or electrostatic chucking electrodes, may be coupled to thesubstrate support assembly 130. In one embodiment, the electrodes are located in the body of thesubstrate support assembly 130. The electrodes may be coupled to the second source ofelectrical power 160 through an optional filter, which may be an impedance matching circuit. The secondelectrical power source 160 may be used to establish additional bias voltages by establishing additional potentials from the plasma to thesubstrate 102. Although there is already a built-in potential from the plasma to thesubstrate 102 even without the secondelectrical power source 160, it is believed that the secondelectrical power source 160 increases the potential to provide more ion bombardment to enhance the etching/cleaning effect. The secondelectrical power source 160 may be a dc power source, a pulsed dc power source, a radio frequency bias power source, a pulsed radio frequency source, or a bias power source, or a combination thereof.

In one embodiment, the secondelectrical power source 160 is a dc bias power source. The DC bias power supply may be supplied at a frequency of 300kHz with a power of between about 10 watts and about 3000 watts (e.g., between about 10 watts and about 1000 watts; or between about 10 watts and about 100 watts). In one embodiment, the dc bias power supply may be pulsed at a radio frequency of about 500Hz and about 10kHz with a duty cycle between about 10% to 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 secondelectrical power source 160 is a radio frequency bias power source. The rf bias power source may be supplied at a frequency of 300kHz with a power between about 0 watts and about 1000 watts (e.g., between about 10 watts and about 100 watts). In one embodiment, the rf bias power source may be pulsed at an rf frequency of about 500Hz and about 10kHz with a duty cycle between about 10% to about 95%.

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

Aremote plasma source 124, such as an inductively coupled remote plasma source, may also be coupled between the gas source and thegas distribution plate 110. Between processing substrates, the halogen-containing cleaning gas mixture may be energized (energized) in theremote plasma source 124 to remotely provide a plasma for cleaning chamber components. The halogen containing cleaning gas mixture entering theprocess volume 106 may be further excited by the rf power provided to thegas distribution plate 110 by the firstelectrical power source 122. Although thegas source 120 is coupled to thelid assembly 112 via theremote plasma source 124, it should be understood that in some embodiments, thegas source 120 is coupled directly to the lid assembly.

In one embodiment, asubstrate 102 that may be processed in thesubstrate processing chamber 100 may have a thickness of 10,000cm²Or larger, such as 25,000cm²Or greater, e.g. about 55,000cm²Or a larger surface area. It is understood that after processing, the substrate may be cut to form smaller other devices.

In one embodiment, the heating and/orcooling elements 139 may be configured to provide the following substrate support assembly temperatures during cleaning: 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; between about 10 degrees Celsius and about 50 degrees Celsius; or between about 10 degrees Celsius and 30 degrees Celsius).

The nominal spacing between theupper surface 118 of thesubstrate 102 disposed on thesubstrate receiving surface 132 and thegas distribution plate 110 during cleaning may typically vary between 400 mils (mils) and about 1,200 mils, such as between 400 mils and about 800 mils, or other distances to achieve a desired deposition result. In one embodiment, in which thegas distribution plate 110 has a concave downstream surface, the spacing between the center portion of the edge of thegas distribution plate 110 and thesubstrate receiving surface 132 is between about 400 mils and about 1400 mils, and the spacing between the corners of thegas distribution plate 110 and thesubstrate receiving surface 132 is between about 300 mils and about 1,200 mils.

Fig. 1B illustrates a cross-sectional view of thesubstrate processing chamber 100 of fig. 1A with thesubstrate 102 removed. Figure 1B provides an illustration of asubstrate 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 solid arrows in FIG. 1B) is introduced into theprocess volume 106 having a residual film 180 (e.g., such as ZrO) to be removed during the cleaning process₂、Y₂O₃Or HfO₂Such as a high dielectric constant dielectric material). As shown in FIG. 1B, aresidual film 180 is deposited on at least a portion of the exposed surfaces within thesubstrate processing chamber 100, in particularAnd is deposited on thegas distribution plate 110, thesubstrate support assembly 130, theshadow frame 133, and the like. The halogen-containinggas mixture 170 is exposed to an energy source, such as the firstelectrical power source 122, the secondelectrical power source 160, or theremote plasma source 124, thus generatingreactive species 190, such as chlorine radicals, fluorine radicals, bromine radicals, hydrogen radicals, and combinations thereof. Thereactive species 190 react with theresidual film 180 and form volatile products. The volatile products are removed from thesubstrate processing chamber 100. One or more interior surfaces of the substrate processing chamber 100 (e.g., thegas distribution plate 110, thesubstrate support assembly 130, theshadow frame 133, thesidewalls 142, etc.) have at least one coating material (e.g., exposed Al) formed thereon₂O₃Film or exposed yttrium-containing film). The one or more interior surfaces may comprise aluminum, stainless steel, nickel-iron alloy (e.g., invar or 64FeNi), or other materials compatible with plasma processing. In an embodiment, thereactive species 190 may be delivered to theprocess volume 106 with thereactive species 190 being formed ex-situ (e.g., via a remote plasma).

Figure 2 illustrates a process flow diagram of one embodiment of amethod 200 that may be used to remove a high-k dielectric material from a substrate processing chamber. The substrate processing chamber may be similar to thesubstrate processing chamber 100 shown in fig. 1A and 1B. Atoperation 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 over interior surfaces of chamber components (e.g., gas distribution plates, substrate support assemblies, shadow frames, sidewalls, etc.) including the substrate processing chamber. The inner surface may comprise aluminum, stainless steel, nickel-iron alloy (e.g., invar or 64FeNi), or other materials compatible with plasma processing. Any suitable high-k dielectric material may be deposited in the substrate processing chamber. In one embodiment, the high dielectric constant dielectric material is selected from zirconium oxide (ZrO)₂) Hafnium oxide (HfO)₂) Alumina (Al)₂O₃) And combinations of the foregoing. In one embodiment, the high-k dielectric material is doped. In thatIn one embodiment, the doped high-k dielectric material is an aluminum doped zirconium oxide containing material.

The high-k dielectric material may be deposited using, for example, a Chemical Vapor Deposition (CVD) process, a Plasma Enhanced Chemical Vapor Deposition (PECVD) process, an Atomic Layer Deposition (ALD) process, a Metal Organic Chemical Vapor Deposition (MOCVD) process, and a Physical Vapor Deposition (PVD) process. In some embodiments, at least some portions of the chamber component are comprised of aluminum. In some embodiments, at least some portions of the chamber component have a coating disposed thereon. In some embodiments, the coating comprises a material selected from the group consisting of alumina (Al)₂O₃) Yttrium-containing compounds, and combinations of the foregoing. In one embodiment, the yttrium-containing compound is selected from yttrium oxide (Y)₂O₃) 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 embodiments, the chamber component does not have a coating disposed thereon and is thus "uncoated".

Atoperation 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.

Atoperation 230, reactive species are introduced into the substrate processing chamber. The reactive species may be generated using a plasma. The plasma may be generated in situ or the plasma may be generated ex situ (e.g., remotely). Suitable plasma generation techniques and sources, such as Inductively Coupled Plasma (ICP), Capacitively Coupled Plasma (CCP), Remote Plasma Source (RPS), or microwave plasma generation techniques, may be used to form the reactive species. In some embodiments, the reactive species are formed in situ via an in situ plasma process. In some embodiments, the reactive species are formed ex situ via a remote plasma source and introduced into the substrate processing chamber.

In one embodiment, the reactive species may be generated by flowing a halogen-containing cleaning gas mixture into the process volume 106And (4) generating. In one embodiment, the halogen containing cleaning gas mixture comprises 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 thereof. In one embodiment, the chlorine-containing gas is selected from BCl₃And Cl₂. In one embodiment, the halogen-containing gas is selected from BCl₃、Cl₂、HBr、NF₃And combinations of the foregoing gases. In one embodiment, the halogen containing cleaning gas mixture includes BCl₃And NF₃. In one embodiment, the halogen containing cleaning gas mixture includes BCl₃And Cl₂. In one embodiment, the halogen-containing gas mixture further comprises a carbon-containing gas. In one embodiment, the carbon-containing gas is selected from CO₂、CH₄、CHF₃、CH₂F₂、CH₃F、CF₄And combinations of the foregoing gases. In one embodiment, the halogen-containing gas mixture further comprises a diluent gas. The diluent gas may be selected from helium, argon, and combinations of the foregoing. In some embodiments, the halogen-containing gas and the carbon-containing gas are introduced separately into theprocess volume 106.

In one embodiment, the halogen containing cleaning gas mixture includes CO₂、CH₄、CHF₃、CH₂F₂、CH₃F、CF₄And BCl and at least one of the above gases in combination₃. In another embodiment, the halogen containing cleaning gas mixture includes CO₂、CH₄、CHF₃、CH₂F₂、CH₃F、CF₄And Cl and at least one of the above gases in combination₂. In yet another embodiment, the halogen containing cleaning gas mixture includes CO₂、CH₄、CHF₃、CH₂F₂、CH₃HBr and at least one of F and combinations of the foregoing gases. In another embodiment, the halogen containing cleaning gas mixture includes CO₂、CH₄、CHF₃、CH₂F₂、CH₃F、CF₄NF and at least one of the above gases in combination₃. In yet another embodiment, the halogen containing cleaning gas mixture includes CO₂、CH₄、CHF₃、CH₂F₂、CH₃F、CF₄And BCl and at least one of the above gases in combination₃、NF₃. In another embodiment, the halogen containing cleaning gas mixture includes CO₂、CH₄、CHF₃、CH₂F₂、CH₃F、CF₄And BCl and at least one of the above gases in combination₃、Cl₂。

In one embodiment, the halogen containing cleaning gas mixture is exposed to an rf source and/or a bias power source. The rf source and/or the bias power source energizes the halogen containing cleaning gas mixture within theprocess volume 106 so that a plasma may be sustained. In one embodiment, the first source ofelectrical power 122 is operable to provide radio frequency power at a frequency between 0.3MHz and about 14MHz, such as about 13.56 MHz. The firstelectrical power source 122 may generate about 10 watts to about 5000 watts (e.g., between about 300 watts and about 1500 watts; between about 500 watts and about 1000 watts) of radio frequency power.

In some embodiments, in addition to the rf source power, an rf bias power supply may also be utilized during the cleaning process to help dissociate the cleaning gas mixture forming the plasma. The radio frequency bias may be provided by a secondelectrical power source 160. In one embodiment, the first source ofelectrical power 122 is operable to provide radio frequency power at a frequency between 0.3MHz and about 14MHz, such as about 13.56 MHz. The rf bias power source may be supplied at a frequency of 300kHz with a power between about 0 watts and about 1000 watts (e.g., between about 10 watts and about 100 watts). In one embodiment, the rf bias power source may be pulsed at an rf frequency of about 500Hz and about 10kHz with a duty cycle between about 10% to about 95%. In some embodiments, the coating material (e.g., Al) is applied with an additional bias voltage₂O₃) Along with the remaining high-k dielectric material. Without being bound by theory, it is believed that the DC bias creates a potential difference between the plasma and the substrate to enhance etching.

In some embodiments, the plasma may be formed capacitively or inductively and may be energized by coupling rf power to the halogen containing cleaning gas mixture. The radio frequency power may be dual frequency radio frequency power having a high frequency component and a low frequency component. The radio frequency power is typically applied at a power level of between about 50W and about 2500W, which may all be 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 300 kHz.

In some embodiments in which the reactive species are formed ex-situ, the halogen containing cleaning gas mixture is flowed 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 diluent gas. In some embodiments, an optional diluent gas may serve as a carrier gas. In some embodiments, the optional diluent gas may extend the lifetime of the radical species and increase the density of the radical species. In some embodiments, a halogen-containing gas is flowed into a remote plasma source and other process gases (e.g., 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, which causes the halogen containing cleaning gas mixture to dissociate to form reactive species. The reactive species may include chlorine radicals, bromine radicals, fluorine radicals, and combinations thereof. The remote plasma source provides efficient dissociation of the halogen-containing cleaning gas mixture.

In some embodiments, the remote plasma is initiated with 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 be flowed into the substrate processing chamber at a flow rate of about 100sccm to about 20,000 sccm. In some embodiments, the halogen containing cleaning gas mixture may be flowed into the substrate processing chamber at a flow rate of about 500sccm to about 4,000 sccm. In some embodiments, the halogen containing cleaning gas mixture may be flowed into the substrate processing chamber at a flow rate of about 1,000 sccm.

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

In some embodiments, the remote plasma is initiated with 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 of argon is reduced as the halogen containing gas mixture is introduced into the remote plasma chamber. As an example, the remote plasma may be initiated with argon at a flow rate of 3,000sccm, with the flow rate of argon being gradually reduced to 1,000sccm and then to 500sccm as the halogen containing gas mixture is introduced into the remote plasma chamber at an initial flow rate of 1,000sccm and then increased to 1,500 sccm.

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

Reactive species formed from the halogen containing cleaning gas mixture are delivered to the substrate processing chamber. In one embodiment, the reactive species comprises a halogen radical. In one embodiment, the reactive species comprises chlorine radicals. In one embodiment, the reactive species comprises chlorine radicals and fluorine radicals. In one embodiment, the reactive species comprises a bromine radical. In one embodiment, the reactive species comprises bromine radicals and hydrogen radicals.

Atoperation 240, the reactive species react with the deposit containing the high-k dielectric material to form a dielectric layerVolatile products are formed in the gaseous state. In some embodiments, the removal rate of the residual high dielectric constant dielectric material-containing deposit is greater than the removal rate of a coating material that coats at least a portion of the chamber component. In some embodiments, the removal rate of the residual high-k dielectric-containing deposition is greater than

(e.g., from about

To about

From about

To about

Or from about

To about

). In some embodiments, reacting the residual high dielectric constant dielectric-containing deposit with a reactive species to form a volatile product is a bias-free process. In some embodiments in which no additional bias is applied, the removal rate of the coating material is less than

(e.g., from about

To about

From about

To about

Or

). In some embodiments in which no additional bias is applied, the removal rate of the coating material is a minimum or very slow removal rate (e.g., lower than

Is lower than

Is lower than

Is lower than

Is lower than

Is lower than

Or below

)。

Optionally, atoperation 250, the volatile products in a gaseous state are purged from the substrate processing chamber. The substrate processing chamber may be efficiently purged by flowing a purge gas into the substrate processing chamber. Alternatively, or in addition to introducing the purge gas, the substrate processing chamber may be depressurized to remove any residual cleaning gas and any byproducts from the substrate processing chamber. The substrate processing chamber may be purged by evacuating the substrate processing chamber. The time period for the purging process should generally be long enough to remove volatile products from the substrate processing chamber. The period of time during which the purge gas is flowed should generally be long enough to remove volatile products from the interior surfaces of the chamber including the chamber components.

Atoperation 260, at least one ofoperations 230, 240, and 250 is repeated until the selected cleaning endpoint is achieved. It should be understood that several cleaning cycles may be applied, with an optional purging process being performed between cleaning cycles.

In some embodiments, themethod 200 further comprises removing the 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 the second volatile product. The second volatile product may be removed from the substrate processing chamber.

Figure 3 illustrates a process flow diagram of one embodiment of amethod 200 that may be used to remove a high dielectric constant material from a substrate processing chamber. The substrate processing chamber may be similar to thesubstrate processing chamber 100 shown in fig. 1A and 1B. Atoperation 310, zirconium oxide (ZrO) is included₂) The layer is deposited over a substrate disposed in a substrate processing chamber. During deposition of the zirconium oxide-containing layer over the substrate, zirconium oxide and/or zirconium oxide-containing compounds may be deposited over interior surfaces of chamber components (e.g., gas distribution plates, substrate support assemblies, shadow frames, sidewalls, etc.) including the substrate processing chamber. The zirconia-containing layer can be an aluminum-doped zirconia-containing layer. The zirconia-containing layer can be deposited using, for example, a Chemical Vapor Deposition (CVD) process, a Plasma Enhanced Chemical Vapor Deposition (PECVD) process, a chamber, an Atomic Layer Deposition (ALD) process, a Metal Organic Chemical Vapor Deposition (MOCVD), and a Physical Vapor Deposition (PVD) process. One or more of the interior surfaces/chamber components may comprise aluminum, stainless steel, nickel-iron alloy (e.g., invar or 64FeNi), or other materials compatible with plasma processing. In some casesIn an embodiment, at least a portion of the chamber component is comprised of aluminum. In some embodiments, at least a portion of the chamber component has aluminum oxide (Al) disposed thereon₂O₃) And (3) a layer. In some embodiments, at least a portion of the chamber component is comprised of stainless steel.

Atoperation 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.

Atoperation 330, reactive species are introduced into the substrate processing chamber. The reactive species may be generated using an in situ generated plasma or the plasma may be generated ex situ (e.g., remotely). Suitable plasma generation techniques, such as Inductively Coupled Plasma (ICP), Capacitively Coupled Plasma (CCP), Remote Plasma Source (RPS), or microwave plasma generation techniques, may be used to form the reactive species. In some embodiments, the reactive species are formed in situ via an in situ plasma process. In some embodiments, the reactive species are formed ex situ via a remote plasma source.

In one embodiment, the reactive species may be generated by flowing a cleaning gas mixture into theprocess volume 106. In one embodiment, the cleaning gas mixture comprises BCl₃And optionally a diluent gas. The diluent gas may be an inert gas selected from helium, argon, or a combination thereof. The cleaning gas mixture is exposed to a radio frequency source and/or a bias power source. The rf source and/or the bias power source energizes the cleaning gas mixture within theprocess volume 106 so that a plasma may be sustained. In one embodiment, the first source ofelectrical power 122 is operable to provide radio frequency power at a frequency between 0.3MHz and about 14MHz, such as about 13.56 MHz. The firstelectrical power source 122 may generate about 10 watts to about 5000 watts (e.g., between about 300 watts and about 1500 watts; between about 500 watts and about 1000 watts) of radio frequency power.

In some embodiments, in addition to the rf source power, an rf bias power supply may also be utilized during the cleaning process to help dissociate the cleaning gas mixture forming the plasma. The RF bias may be provided byA second source ofelectrical power 160. In one embodiment, the first source ofelectrical power 122 is operable to provide radio frequency power at a frequency between 0.3MHz and about 14MHz, such as about 13.56 MHz. The rf bias power source may be supplied at a frequency of 300kHz with a power between about 0 watts and about 1000 watts (e.g., between about 10 watts and about 100 watts). In one embodiment, the rf bias power source may be pulsed at a duty cycle between about 10% to about 95% at an rf frequency between about 500Hz and about 10 kHz. In some embodiments in which this additional bias is applied, Al₂O₃With residual ZrO-containing₂The films are removed together.

In some embodiments, in addition to the rf source power, a dc bias power supply may also be utilized during the cleaning process to help dissociate the cleaning gas mixture forming the plasma. The dc bias may be provided by the secondelectrical power source 160. In one embodiment, the first source ofelectrical power 122 is operable to provide radio frequency power at a frequency between 0.3MHz and about 14MHz, such as about 13.56 MHz. The secondelectrical power source 160 is operable to provide a dc bias power source at a frequency of 300kHz at a power of between about 10 watts and about 3000 watts (e.g., between about 10 watts and about 1000 watts; or between about 10 watts and about 100 watts). In one embodiment, the dc bias power supply may be pulsed at a frequency between about 500Hz and about 10kHz with a duty cycle between about 10% to about 95%. Without being bound by theory, it is believed that the DC bias creates a potential difference between the plasma and the substrate to enhance etching.

In some embodiments, the plasma may be formed capacitively or inductively and may be energized by coupling rf power to the cleaning gas mixture. The radio frequency power may be dual frequency radio frequency power having a high frequency component and a low frequency component. The rf power is typically applied at a power level of between about 50W and about 2,500W, which may all be high frequency rf 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 300 kHz.

In some embodiments in which the reactive species are formed ex situ, the BCl will be contained₃The gas mixture flows into a remote plasma source fluidly coupled to the substrate processing chamber. Containing BCl₃The gas mixture of (A) comprises BCl₃And optionally an inert gas. In some embodiments, an optional inert gas may serve as a carrier gas. In some embodiments, the optional inert gas may extend the lifetime of the radical species and increase the density of the radical species. In some embodiments, BCl is included, respectively₃The gas mixture flows into a remote plasma source and other process gases are delivered into the chamber. The optional inert gas may be selected from the group consisting of helium, argon, or combinations thereof.

The remote plasma source may be an inductively coupled plasma source. Remote plasma source receiving BCl-containing plasma₃Gas mixture and in the presence of BCl₃Plasma formation in the gas mixture, which results in BCl-containing₃The gas mixture dissociates to form reactive species. The reactive species may include chlorine radicals. Remote plasma source providing BCl-containing plasma₃Efficient dissociation of gas mixtures.

In some embodiments, the remote plasma is to contain BCl₃The gas mixture is initiated with an initial flow of argon or similar inert gas prior to introduction into the remote plasma chamber.

Containing BCl₃The gas mixture may be flowed into the substrate processing chamber at a flow rate of about 100sccm to about 10,000 sccm. In some embodiments, the BCl is included₃The gas mixture is flowed into the substrate processing chamber at a flow rate from about 500sccm to about 4,000 sccm. In some embodiments, the BCl is included₃The gas mixture is flowed 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 mtorr and about 300 torr. The pressure within the substrate processing chamber may be between 10 mtorr and about 5 mtorr, such as about 20 mtorr.

In some embodiments, the remote plasma is in the presence of BCl₃Initiation with an initial flow of argon or similar inert gas is used prior to introduction into the remote plasma source. Then, following BCl₃Introducing remote plasmaIn the daughter chamber, the flow of argon is reduced. As an example, the remote plasma may be initiated with 3,000sccm of argon gas, followed by BCl₃An initial flow of 1,000sccm and then increasing to 1,500sccm was introduced into the remote plasma chamber, and the flow of argon was gradually decreased to 1,000sccm and then to 500 sccm.

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

From BCl₃Reactive species formed from the gas mixture are transported to the substrate processing chamber. The reactive species comprise chlorine radicals.

Atoperation 340, the reactive species react with the zirconia-containing deposits to form gaseous volatile products. The volatile product comprises zirconium tetrachloride (ZrCl)₄). In some embodiments, residual ZrO-containing₂The film removal rate is greater than Al₂O₃Removal rate of (a), the Al₂O₃At least a portion of the aluminum chamber component is coated. In some embodiments, residual ZrO-containing₂The removal rate of the film is greater than

(e.g., from about

To about

From about

To about

Or from about

To about

). In some embodiments, the residual ZrO-containing is reacted₂The reaction of the film with the reactive species to form volatile products is a bias-free process. In some embodiments, where no additional bias is applied, Al₂O₃Has a removal rate less than

(e.g., from about

To about

From about

To about

Or

)。

Optionally, atoperation 350, the volatile products in a gaseous state are purged from the substrate processing chamber. The substrate processing chamber may be efficiently purged by flowing a purge gas into the substrate processing chamber. Alternatively, or in addition to introducing the purge gas, the substrate processing chamber may be depressurized to remove any residual cleaning gas and any byproducts from the substrate processing chamber. The substrate processing chamber may be purged by evacuating the substrate processing chamber. The time period for the purging process should generally be long enough to remove volatile products from the substrate processing chamber. The period of time during which the purge gas is flowed should generally be long enough to remove volatile products from the interior surfaces of the chamber including the chamber components.

Atoperation 360, at least one ofoperations 330, 340, and 350 is repeated until the selected cleaning endpoint is achieved. It should be understood that several cleaning cycles may be applied, with an optional purging process being performed between cleaning cycles.

In some embodiments, themethod 300 further comprises removing Al-containing from the substrate processing chamber₂O₃The membrane (if present). Al (Al)₂O₃By simultaneous and/or simultaneous formation of reactive species and/or by incorporation of Al₂O₃The film is removed with the application of an additional bias while reacting with the reactive species to form a second volatile product. The second volatile product may be removed from the substrate processing chamber.

Example (b):

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 according to one embodiment of the present disclosure. As shown in Table I, relative to Al₂O₃Using BCl₃And the inductively coupled plasma process performed without DC bias is applied to ZrO₂Aluminum-doped ZrO₂And aluminum has a higher removal rate. As further shown in Table 1, the process also removed Al when DC bias was applied₂O₃。

TABLE I

Table II shows the results of a cleaning process performed according to one embodiment of the present disclosure. As shown in table II, relative to Al₂O₃Stainless steel, invar and yttrium coatings using BCl₃And a capacitively coupled plasma process performed without a DC bias for ZrO₂Aluminum-doped ZrO₂And aluminum has a higher removal rate.

TABLE II

In summary, some benefits of the present disclosure include coating materials in non-etching or minimal etching chambers (e.g., Al)₂O₃And/or yttrium-containing compounds) and/or chamber materials (e.g., stainless steel and/or nickel-iron alloy) to selectively etch residual high-k dielectric film (e.g., ZrO)₂And HfO₂) The ability of the cell to perform. The selectivity may be used to protect aluminum chamber components. Aluminum chamber components are typically etched during a plasma cleaning process. The inventors have found that the use of Al₂O₃Anodizing or other chamber coating materials to protect the aluminum components in the chamber allows for preferential removal of residual high dielectric constant dielectric film without damaging the aluminum components, thus ensuring reliability and longevity of the hardware components. Selectivity is critical to achieving the clean-in-place function. Thus, during cleaning, the residual film can pass through the cleaning agent (e.g., BCl)₃、Cl₂HBr or NF₃) The aluminum side walls and other aluminum hardware components inside the chamber remain intact. As described above, embodiments of the present disclosure include the use of reactive plasma species of halogen-containing gas mixtures to clean residual high-permittivity dielectric films and the use of coating materials on aluminum hardware components inside the chamber to protect the aluminum hardware components. The reactive plasma species can effectively etch the high-k dielectric material and aluminum, but not the coating material, if no additional bias is applied. Therefore, as long as aluminum is coated with a material (e.g., Al)₂O₃Or yttrium-containing compounds), aluminum can be used as the material for the hardware component. The reactive plasma species may also etch Al when an additional bias is applied₂O₃. These features make reactive plasma species ideal cleaning agents for in situ cleaning of high dielectric constant materials of deposition chambers.

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

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

While the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims (15)

Translated fromChinese

1.一种用于清洁处理腔室的方法，包含：1. A method for cleaning a processing chamber, comprising:将反应性物种引入具有残余的高介电常数介电材料的处理腔室中，所述残余的高介电常数介电材料形成在所述处理腔室的一个或多个内表面上，其中所述一个或多个内表面包含选自不锈钢、镍铁合金或上述材料的组合的材料；Introducing the reactive species into a processing chamber having residual high-k dielectric material formed on one or more interior surfaces of the processing chamber, wherein the the one or more inner surfaces comprise a material selected from stainless steel, nickel-iron alloys, or a combination of the foregoing;使所述残余的高介电常数介电材料与所述反应性物种反应以形成挥发性产物；和reacting the residual high-k dielectric material with the reactive species to form a volatile product; and从所述处理腔室去除所述挥发性产物，removing the volatile product from the processing chamber,其中所述残余的高介电常数介电材料的去除速率大于所述一个或多个内表面的材料的去除速率；wherein the removal rate of the residual high-k dielectric material is greater than the removal rate of the material of the one or more inner surfaces;其中所述反应性物种由含卤素气体混合物形成；并且wherein the reactive species is formed from a halogen-containing gas mixture; and其中所述残余的高介电常数介电材料选自二氧化锆(ZrO₂)和二氧化铪(HfO₂)。wherein the residual high-k dielectric material is selected from zirconium dioxide (ZrO₂ ) and hafnium dioxide (HfO₂ ).2.如权利要求1所述的方法，其中所述一个或多个内表面进一步包含具有涂层材料形成在其上的至少一个表面，其中所述涂层材料包含选自氧化铝(Al₂O₃)、含钇化合物或上述材料的组合的化合物。2. The method of claim 1 , wherein the one or more interior surfaces further comprise at least one surface having a coating material formed thereon, wherein the coating material comprises a material selected from the group consisting of alumina (Al₂ O₃ ), a compound containing an yttrium compound or a combination of the above materials.3.如权利要求2所述的方法，其中所述含钇化合物选自氧化钇(Y₂O₃)、氟化氧化钇(YOF)、氯酸钇(Y(ClO₃)₃)、氟化钇(III)(YF₃)、氯化钇(III)(YCl₃)、氧化钇稳定的氧化锆(YSZ)或上述各项的组合。3. The method of claim 2, wherein the yttrium-containing compound is selected from the group consisting of yttrium oxide (Y₂ O₃ ), yttrium oxide fluoride (YOF), yttrium chlorate (Y(ClO₃ )₃ ), fluoride Yttrium(_III ) (YF3), yttrium(_III ) chloride (YCl3), yttria-stabilized zirconia (YSZ), or a combination of the foregoing.4.如权利要求1所述的方法，其中所述含卤素气体混合物包含含卤素气体，所述含卤素气体选自BCl₃、Cl2、HBr、NF₃或上述气体的组合。4. The method of claim₁ , wherein the halogen-containing gas mixture comprises a halogen-containing gas selected from the group consisting of_BCl3 , Cl2, HBr, NF3, or combinations thereof.5.如权利要求4所述的方法，其中所述含卤素气体混合物进一步包含含碳气体。5. The method of claim 4, wherein the halogen-containing gas mixture further comprises a carbon-containing gas.6.如权利要求5所述的方法，其中所述含碳气体选自CO₂、CH₄、CHF₃、CH₂F₂、CH₃F、CF₄或上述气体的组合。6._The method of claim₅ , wherein the carbon_- containing gas is selected from_CO2 ,_CH4 , CHF3,_CH2F2 ,_CH3F , CF4, or combinations thereof.7.如权利要求5所述的方法，其中所述含卤素气体混合物进一步包含稀释气体，所述稀释气体选自氦气、氩气或上述气体的组合。7. The method of claim 5, wherein the halogen-containing gas mixture further comprises a diluent gas selected from the group consisting of helium, argon, or combinations thereof.8.如权利要求1所述的方法，其中所述含卤素气体混合物包含BCl₃和NF₃。8. The method of claim 1, wherein the halogen_- containing gas mixture comprises_BCl3 and NF3.9.如权利要求1所述的方法，进一步包含将所述反应性物种暴露于一个或多个能量源，所述能量源足以使所述残余的高介电常数介电材料与所述反应性物种反应并且形成所述挥发性产物。9. The method of claim 1, further comprising exposing the reactive species to one or more energy sources sufficient to render the residual high-k dielectric material reactive with the reactive species The species react and form the volatile product.10.如权利要求9所述的方法，其中所述一个或多个能量源选自电容耦合等离子体源、电感耦合等离子体源、微波等离子体源和远程等离子体源。10. The method of claim 9, wherein the one or more energy sources are selected from the group consisting of capacitively coupled plasma sources, inductively coupled plasma sources, microwave plasma sources, and remote plasma sources.11.如权利要求1所述的方法，其中使所述残余的高介电常数介电材料与所述反应性物种反应以形成所述挥发性产物的压力是在至少约10毫托与约5托之间。11. The method of claim 1, wherein the pressure at which the residual high-k dielectric material is reacted with the reactive species to form the volatile product is between at least about 10 mTorr and about 5 mTorr. between.12.如权利要求1所述的方法，其中所述处理腔室是等离子体增强化学气相沉积(PECVD)腔室、原子层沉积(ALD)腔室、金属有机化学气相沉积(MOCVD)和物理气相沉积(PVD)腔室。12. The method of claim 1, wherein the processing chamber is a plasma enhanced chemical vapor deposition (PECVD) chamber, an atomic layer deposition (ALD) chamber, metal organic chemical vapor deposition (MOCVD), and physical vapor deposition Deposition (PVD) chamber.13.一种用于清洁处理腔室的方法，包含：13. A method for cleaning a processing chamber, comprising:在处理腔室的一个或多个内表面和设置在所述处理腔室中的基板上沉积高介电常数介电材料；depositing a high-k dielectric material on one or more interior surfaces of a processing chamber and a substrate disposed in the processing chamber;将所述基板传送出所述处理腔室；conveying the substrate out of the processing chamber;将反应性物种引入具有残余的高介电常数介电材料的所述处理腔室中，所述残余的高介电常数介电材料形成在所述处理腔室的一个或多个内表面上，其中所述一个或多个内表面包含选自铝、不锈钢、镍铁合金或上述材料的组合的材料，并且所述一个或多个内表面包含具有形成在其上的涂层材料的至少一个表面；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, wherein the one or more inner surfaces comprise a material selected from aluminum, stainless steel, nickel-iron alloys, or a combination of the foregoing, and the one or more inner surfaces comprise at least one surface having a coating material formed thereon;使所述残余的高介电常数介电材料与所述反应性物种反应以形成挥发性产物；和reacting the residual high-k dielectric material with the reactive species to form a volatile product; and从所述处理腔室去除所述挥发性产物，其中所述残余的高介电常数介电材料的去除速率大于所述涂层材料的去除速率和所述一个或多个内表面的材料的去除速率，The volatile product is removed from the processing chamber, wherein the removal rate of the residual high-k dielectric material is greater than the removal rate of the coating material and the material of the one or more interior surfaces rate,其中所述高介电常数介电材料选自二氧化锆(ZrO₂)和二氧化铪(HfO₂)，wherein the high dielectric constant dielectric material is selected from zirconium dioxide (ZrO₂ ) and hafnium dioxide (HfO₂ ),其中所述反应性物种由含卤素气体混合物形成，并且wherein the reactive species is formed from a halogen-containing gas mixture, and其中所述涂层材料包括选自氧化铝(Al₂O₃)、含钇化合物或上述两者的组合的化合物。Wherein the coating material includes a compound selected from aluminum oxide (Al₂ O₃ ), a compound containing yttrium, or a combination of the two.14.如权利要求13所述的方法，其中所述涂层材料的去除速率小于

14. The method of claim 13, wherein the removal rate of the coating material is less than

15.如权利要求13所述的方法，其中使所述残余的高介电常数介电材料与所述反应性物种反应以形成所述挥发性产物进一步包含将所述反应性物种暴露于一个或多个能量源，所述能量源足以将所述残余的高介电常数介电材料与所述反应性物种反应并且形成所述挥发性产物。15. The method of claim 13, wherein reacting the residual high-k dielectric material with the reactive species to form the volatile product further comprises exposing the reactive species to one or a plurality of energy sources sufficient to react the residual high-k dielectric material with the reactive species and form the volatile product.

Images