Method for forming metal oxyfluoride films

Abstract

A method for forming a metal oxyfluoride film is provided. A substrate is placed in an atomic layer deposition (ALD) chamber having a processing region. Flows of a zirconium-containing gas, a zirconium precursor gas (e.g., tris(dimethylamino)cyclopentadienyl zirconium), an oxygen-containing gas, a fluorine-containing gas, and an yttrium precursor gas (e.g., tris(butylcyclopentadienyl)yttrium) are delivered to the processing region to form a metal oxyfluoride film (e.g., yttrium zirconium oxyfluoride film).

Description

[Technical Field]

[0001] <0001> Embodiments of the present disclosure generally relate to methods for forming a metal oxyfluoride film. In particular, embodiments of the present disclosure relate to coating components of a substrate processing chamber with a metal oxyfluoride film. [Background Art]

[0002] <0002> As part of the process of manufacturing electronic devices, such as semiconductor devices, flat panel display devices, and organic light emitting diode (OLED) devices in a substrate processing chamber, devices are manufactured through various manufacturing steps, and structures are being miniaturized more than ever before. In some manufacturing processes, such as plasma etching and plasma cleaning processes, the substrate and the chamber are exposed to a plasma flow. Plasma can be highly corrosive, and processing chambers and other surfaces exposed to the plasma can be corroded. Accordingly, it is often desirable to coat chamber surfaces, chamber components, and chamber tools with a fluoride coating to protect these portions of the chamber from corrosion or degradation. Without a fluoride coating, plasma, such as halogenated plasma, can corrode these portions of the substrate processing chamber during substrate processing. Corrosion of chamber surfaces, chamber components, and chamber tools can adversely affect electronic devices manufactured in the substrate processing chamber, and can for example negatively impact product yield, chamber uptime, and customer costs.

[0003] <0003> Current methods for forming oxyfluoride films use materials such as HF-pyridine and fluorine, but these do not allow accurate control of the properties of the fluorinated coating. Accordingly, there is a need for improved methods of forming oxyfluoride films, particularly improved methods of forming oxyfluoride films on chamber surfaces, chamber components, and chamber tools of a substrate processing chamber. [Summary of Invention]

[0004]

[0004] One or more embodiments of this disclosure are directed to the following methods: A method for forming a yttrium zirconium oxyfluoride film, comprising: placing a substrate in an atomic layer deposition (ALD) chamber including a processing region; passing a pulse of yttrium precursor gas through the processing region; alternately passing pulses of fluorine precursor gas and oxygen-containing gas to form a yttrium-oxygen-fluorine-containing layer on the substrate; passing a pulse of zirconium precursor gas through the processing region; and alternately passing pulses of fluorine precursor gas and oxygen-containing gas through the processing region to form a yttrium zirconium oxyfluoride film on the substrate.

[0005]

[0005] Another embodiment is directed to the following method: A method for forming a yttrium zirconium oxyfluoride film on a substrate, comprising: passing pulses of yttrium precursor gas across a substrate selected from the group consisting of a part of a substrate processing chamber, components of a substrate processing chamber, and the surface of a substrate processing chamber; alternately passing pulses of fluorine-containing gas and pulses of oxygen-containing gas across the substrate to form a yttrium-oxygen-fluorine-containing layer on the substrate; passing pulses of zirconium precursor gas across the substrate; and alternately passing pulses of fluorine-containing gas and pulses of oxygen-containing gas across the substrate to form a yttrium zirconium oxyfluoride film on the substrate.

[0006]

[0006] Another embodiment is directed to the following method: A method for forming a yttrium zirconium oxyfluoride film on a substrate, comprising: passing pulses of Y(CpBut)3 gas across a substrate selected from the group consisting of a part of a substrate processing chamber, components of a substrate processing chamber, and the surface of a substrate processing chamber; alternately passing pulses of hexafluoroacetylacetonate gas and pulses of an oxygen-containing gas across the substrate to form a yttrium-oxygen-fluorine-containing layer on the substrate; passing pulses of tris(dimethylamino)cyclopentadienylzirconium (CpZr(NMe2)3) gas across the substrate; and alternately passing pulses of NF3 gas and pulses of an oxygen-containing gas across the substrate to form a yttrium zirconium oxyfluoride film on the substrate. [Brief explanation of the drawing]

[0007] [Figure 1] A schematic diagram of an atomic layer deposition chamber according to one embodiment is shown. [Figure 2] A flowchart illustrating the operation of a method for forming a metal oxyfluoride film according to a specific, non-limiting embodiment is shown. [Figure 3] This is a flowchart illustrating the operation of a method for forming a metal oxyfluoride film according to a specific, non-limiting embodiment. [Modes for carrying out the invention]

[0008]

[0010] Before describing some exemplary embodiments of this disclosure, it should be understood that this disclosure is not limited to the configuration or process details described below. Other embodiments of this disclosure are possible and can be implemented or performed in a variety of ways.

[0009]

[0011] As used herein and in the appended claims, the term “substrate” refers to the surface or portion of a surface on which the process acts. It will also be understood by those skilled in the art that, unless the context explicitly indicates otherwise, a reference to a substrate may refer to only a portion of a substrate. Furthermore, a reference to depositing on a substrate may mean both a bare substrate and a substrate having one or more films or features deposited or formed thereon.

[0010]

[0012] In addition to forming a film directly on the surface of the substrate itself, any of the film processing steps disclosed in this disclosure may also be performed on an underlying layer formed on the substrate, as disclosed in more detail below, and the term “substrate surface” is intended to include such an underlying layer as the context indicates. For example, if a film / layer, or partial film / layer, is deposited on the substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate surface. In certain embodiments, the substrate includes a portion of a substrate processing chamber, a substrate processing chamber component, or the substrate processing chamber surface. In some particular embodiments, the substrate processing chamber, a substrate processing chamber component, or the substrate processing chamber surface includes aluminum, an aluminum alloy, and / or anodized aluminum alloy. The term “on” indicates that there is direct contact between elements. The term “directly on” indicates that there is direct contact between elements without an intervening element.

[0011]

[0013] One or more embodiments of this disclosure are directed to methods for forming fluorinated metal films and metal oxyfluoride films. Controllable self-terminating fluorination methods have been found to be achievable according to one or more embodiments of the methods described herein. Some embodiments involve atomic layer deposition (ALD) processes. In some embodiments, the Y to Zr ratio and the O to F ratio can be adjusted or controlled very easily and precisely. One or more embodiments of the methods described herein provide a much simpler method for forming metal oxyfluoride films using hexafluoroacetylacetonate (HHFAC) with oxygen or ozone plasma for fluorination and NF3 alone for fluorination. According to the embodiments of the fluorination methods described herein, it has been found that atomic-scale control of fluorination, which was previously thought to be impossible by other methods, can be achieved. One or more embodiments of the methods described herein provide a simpler method for fluorinating metals (e.g., Y and Zr) and metal oxides (e.g., YO and ZrO) compared to conventional fluorination methods, such as those utilizing HF-pyridine and fluorine. In one or more embodiments, the metal oxyfluoride film is amorphous. In other embodiments, the metal oxyfluoride film is crystalline. In some embodiments, the metal oxyfluoride film includes a film that is partially amorphous and partially crystalline.

[0012]

[0014] Embodiments of the methods described herein can be used to control the oxygen-to-fluorine ratio in oxyoxyfluoride compounds with atomic precision. The embodiments of the fluorination methods are self-terminating and offer greater controllability than thermal fluorination methods.

[0013]

[0015] In certain embodiments, a yttrium zirconium oxyoxyfluoride film is formed on the substrate surface, particularly on a portion of the substrate processing chamber. Embodiments of this method include depositing a metal oxide-containing layer on a substrate using an atomic layer deposition (ALD) process, depositing a metal-fluorine layer on the metal oxide-containing layer using an activated fluorination process, depositing the metal oxide-containing layer, and repeating the deposit of the metal oxide-containing layer until a metal oxyoxyfluoride film of a predetermined thickness is formed.

[0014]

[0016] Figure 1 is a schematic diagram of an atomic layer deposition (ALD) chamber 100. The chambers described herein are exemplary embodiments of chambers and other chambers (including chambers from other manufacturers) and should be understood to be usable, or modified, for achieving aspects of the herein disclosure, such as method 200 for forming a metal oxyfluoride film 300.

[0015]

[0017] The ALD chamber 100 includes a chamber body 101. The chamber body includes a body portion 102, a lid portion 104, and a support assembly 112. A gas inlet 108 and a gas outlet 110 are located between the body portion 102 and the lid portion 104 of the chamber body 101. The support assembly 112 is located at least partially within the body portion 102 of the chamber body 101. The support assembly 112 includes a pedestal 114 that is movable within the chamber body 101 by a stem 116. The pedestal 114 includes a support surface 118 configured to support a substrate 130 (described in further detail herein). The stem 116 penetrates the chamber body 101 and is connected to a lift system (not shown) that moves the pedestal 114 between a processing position (as shown) and a transport position. The transport position facilitates the transport of the substrate 130 through an opening 120 formed in the side wall of the body portion 102 to provide access to the interior of the ALD chamber 100.

[0016]

[0018] At the processing position, the pedestal 114 of the support assembly 112 contacts the main body 102 to form a processing region 122 defined by the support surface 118, the upper surface of the main body 102, and the lower surface of the lid 104. When the support assembly 112 at the processing position contacts the main body 102 to form the processing region 122, the gas inlet 108 and gas outlet 110 are in fluid communication with the processing region 122. In this way, gas is introduced into the processing region 122 through the gas inlet 108. The substrate 130 is adjacent to the processing region 122. The gas flows through the processing region 122 across the substrate 130 and is exhausted by the pump 124 through the gas outlet 110. A source, such as a plasma source 126 (e.g., a radio frequency (RF) source or a microwave source), is coupled to the electrode 128 of the lid 104. In some embodiments, the plasma source 126 includes a microwave source, or a combination of an RF source and a microwave source. The plasma source 126 supplies power to the electrode 128 to facilitate the generation of plasma from the gas in the processing area 122. The pedestal 114 is either grounded or can function as a cathode when connected to the plasma source 126, generating a capacitive electric field between the lower surface of the lid 104 and the pedestal 114 to accelerate the plasma species toward the substrate 130.

[0017]

[0019] Figure 2 is a flow chart illustrating the operation of method 200 for forming a metal oxyfluoride film on a substrate according to a specific, non-limiting embodiment showing a particular precursor. In a particular embodiment, the metal oxyfluoride film is a yttrium zirconium oxyfluoride (YZrOF) film. In operation 201, a pulse of a yttrium precursor, for example, a pulse of a tris(butylcyclopentadienyl)yttrium (Y(CpBut)3) precursor, is flowed into the ALD chamber 100. In one or more embodiments, other suitable yttrium precursors include a complex with the general formula YR1R2R3, where R1, R2, and R3 are independently selected from halides, carbonyls, cyclopentadienes, amines, acac, hfac, amidinates, or diazadienes. Other non-limiting examples of yttrium precursors include tris(N,N''-di-i-propylformamidinato)yttrium(III), tris(ethylcyclopentadienyl)yttrium, tris[N,N-bis(trimethylsilyl)amide]yttrium(III), tris[N,N-bis(trimethylsilyl)amide]yttrium(III), tris(butylcyclopentadienyl)yttrium, tris(cyclopentadienyl)yttrium, and tris(methylcyclo This includes yttrium(pentadienyl)yttrium, tris(n-propylcyclopentadienyl)yttrium, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)yttrium(III), tris(2,2,6,6-tetramethyl-3,5-heptanedionato)yttrium(III) triglyceride, yttrium(III) acetylacetonate hydrate, yttrium(III) chloride, and yttrium(III) hexafluoroacetylacetonate. The substrate 130 may be a chamber component, a chamber tool, a chamber, and a chamber main frame. The substrate may be made of aluminum and / or anodized aluminum. Method 200 in some embodiments includes transporting the substrate into the ALD chamber 100 and placing the substrate on the pedestal 114.

[0018]

[0020] In one embodiment (which can be combined with other embodiments described herein), the method includes introducing a flow or pulse of a yttrium precursor, such as tris(butylcyclopentadienyl)yttrium gas, into a processing area 122. The tris(butylcyclopentadienyl)yttrium gas is introduced as a gas or gas pulse flowing across the processing area 122 through a gas inlet 108, and the gas or gas pulse flows across the substrate 130, forming a yttrium-containing layer on the substrate 130. Next, a flow or pulse of oxygen-containing gas is introduced as a gas or gas pulse across the processing area 122 through the gas inlet 108, and the gas or gas pulse flows across the substrate. In one embodiment (which can be combined with other embodiments described herein), the oxygen-containing gas includes one or more of H2O, O3, or O2. In certain embodiments, the oxygen-containing gas includes H2O. In other embodiments, the oxygen-containing gas includes O3 or O2. In operation 202, after an oxygen-containing gas is flowed over the substrate 130, a fluorine precursor, such as NF3 gas, is introduced as a gas or gas pulse flowing over the processing area 122 through the gas inlet 108, and the gas or gas pulse flows over the substrate 130, forming a yttrium-oxygen-fluorine-containing layer on the substrate 130. In some embodiments, the fluorine precursor comprises at least one organofluorine reagent. In one or more embodiments, the fluorine precursor is selected from hexafluoroacetylacetone, pivaloyltrifluoroacetone, trifluoroacetylacetone, valeryltrifluoroacetone, benzoyltrifluoroacetone, tetrafluoropropanol (TFP), 1,1,1,2-tetrafluoroethane (HFC-134), and HF-pyridine. In one embodiment (combinable with other embodiments described herein), the fluorine precursor comprises at least one fluorinated gas. Examples of fluorinated gases include, but are not limited to, at least one of gaseous HF, nitrogen trifluoride (NF3), phosphorus pentafluoride (PF5), or sulfur hexafluoride (SF6).

[0019]

[0021] In some embodiments of operations 201 and 202, tris(butylcyclopentadienyl)yttrium gas is pulsed at least once, and in some embodiments more than once (e.g., 2 to 5 times), followed by an oxygen-containing gas pulse, and then an NF3 gas pulse. This pulse sequence is repeated N times in step 203 to yield a tuned and precisely controlled yttrium fluoride concentration in the membrane. In one or more embodiments, N is an integer in the range of 1 to 100, 1 to 50, 1 to 30, 1 to 20, 1 to 10, 1 to 5, 1 to 4, 1 to 3, or 1 to 2.

[0020]

[0022] In operations 204 and 205, a second set of gas flow or gas pulses is introduced into the processing area 122. In operation 204, a flow or pulse of zirconium precursor gas, such as tris(dimethylamino)cyclopentadienylzirconium (CpZr(NMe2)3), is introduced through the gas inlet 108 as a gas or gas pulse flowing across the processing area 122, and the gas or gas pulse flows across the substrate 130. Subsequently, in operation 205, a flow or pulse of oxygen-containing gas is introduced through the gas inlet 108 as a gas or gas pulse flowing across the processing area 122, and the gas or gas pulse flows across the substrate. In one embodiment (combinable with other embodiments described herein), the oxygen-containing gas includes one or more of H2O, O3, or O2. In certain embodiments, the oxygen-containing gas includes H2O. In other embodiments, the oxygen-containing gas includes O3 or O2.

[0021]

[0023] In some embodiments, a second set of gas pulses includes at least one pulse of tris(dimethylamino)cyclopentadienylzirconium (CpZr(NMe2)3), followed by a pulse of O3 or O2, and then a pulse of NF3. In one or more embodiments, this second set of pulses may be repeated M times depending on the desired zirconium fluoride concentration in the YZrOF film. In one or more embodiments, M is an integer in the range of 1 to 100, 1 to 50, 1 to 30, 1 to 20, 1 to 10, 1 to 5, 1 to 4, 1 to 3, or 1 to 2. In operation 307, operations 301 to 306 are repeated a sufficient number of times until a metal oxyfluoride film of a predetermined or target thickness is formed on the substrate 130.

[0022]

[0024] In a particular embodiment of Method 300, which includes a first set of gas pulses and a second set of gas pulses, the pulse time ranges from 3 milliseconds to 60 minutes, 3 milliseconds to 50 minutes, 3 milliseconds to 40 minutes, 3 milliseconds to 30 minutes, 3 milliseconds to 20 minutes, 3 milliseconds to 10 minutes, 3 milliseconds to 5 minutes, 3 milliseconds to 3 minutes, 3 milliseconds to 2 minutes, 3 milliseconds to 1 minute, 3 milliseconds to 50 seconds, 3 milliseconds to 40 seconds, 3 milliseconds to 30 seconds, 3 milliseconds to 20 seconds, 3 milliseconds to 10 seconds, or 3 milliseconds to 5 seconds, depending on the surface area of ​​the substrate to be coated. In one or more embodiments, an oxygen-containing precursor flowing across the processing area 122 flows across the substrate 130 and is activated into a plasma to form oxygen radicals. In another embodiment (combinable with other embodiments described herein), the oxygen radicals may be formed by a remote plasma source that brings the oxygen radicals to the processing area 122. In embodiments in which the oxygen radicals are formed, the oxygen radicals react to deposit a layer of oxygen on the substrate 130. According to one or more embodiments, film growth occurs by self-terminating and saturating chemical reactions of a gaseous precursor on the surface of the substrate 130. The gaseous precursor is introduced alternately onto the substrate and separated by an inert gas (e.g., nitrogen) purge. In one or more embodiments, the introduction of the purge gas flow into the processing area 122 is performed for a period ranging from about 1 millisecond to about 1000 seconds to purge the processing area 122.

[0023]

[0025] According to one or more embodiments, the predetermined or target Y to Zr ratio is controlled by the number of times the first set of gas pulses is repeated N times in operation 203, and the number of times the second set of gas pulses is repeated M times in operation 206. In the embodiments shown herein, a pulse of yttrium precursor (e.g., Y(CpBut)3) or a pulse of zirconium precursor (e.g., tris(dimethylamino)cyclopentadienyl zirconium (CpZr(NMe2)3)) may be flowed before flowing an oxidant pulse (H2O, O2 or O3). In one or more embodiments, the number of pulses of the yttrium precursor and the zirconium precursor before flowing the oxidant pulse (H2O, O2 or O3) is adjusted to obtain improved nucleation on the surface of the substrate 130. However, the present disclosure is not limited to a specific number of pulses of each gas, and in some embodiments, one pulse of yttrium precursor (e.g., Y(CpBut)3) and one pulse of zirconium precursor (e.g., tris(dimethylamino)cyclopentadienyl zirconium (CpZr(NMe2)3)) may be utilized. According to one or more embodiments, other suitable precursors include tetrakis(ethylmethylamino)zirconium(IV), tetrakis(ethylmethylamino)zirconium(IV), tetrakis(dimethylamino)zirconium(IV), tetrakis(dimethylamino)zirconium(IV), tetrakis(dimethylamino)zirconium(IV), tetrakis(diethylamino)zirconium, dimethylbis(t-butylcyclopentadienyl)zirconium, bis(pentamethylcyclopentadienyl)dimethylzirconium(IV), bis(cyclopentadienyl)dimethylzirconium, bis(methylcyclopentadienyl)(methyl)(methoxy)zirconium(IV), and tetrakis(dimethylamino)zirconium(IV).

[0024]

[0026] Referring next to FIG. 3, there is illustrated another embodiment for forming a metal oxyfluoride film on a substrate 130 in accordance with a specific, non-limiting embodiment showing specific precursors. In certain embodiments, the metal oxyfluoride film is an yttrium zirconium oxyfluoride (YZrOF) film. In operation 301, a pulse of a tris(butylcyclopentadienyl)yttrium (Y(CpBut)3) precursor is flowed into an ALD chamber 100. The substrate 130 can be a chamber component, a chamber tool, a chamber, and a chamber mainframe. The substrate can be made of aluminum and / or anodized aluminum. The method 200 of some embodiments includes transferring the substrate into the ALD chamber 100 and placing the substrate onto the pedestal 114.

[0025]

[0027] In one embodiment (combinable with other embodiments described herein), the method comprises introducing a flow or pulse of an yttrium precursor, e.g., tris(butylcyclopentadienyl)yttrium gas, into a processing region 122. The tris(butylcyclopentadienyl)yttrium gas is introduced through a gas inlet 108 as a gas or a pulse of gas that flows across the processing region 122, and the gas or pulse of gas flows across the substrate 130 and forms an yttrium-containing layer on the substrate 130. According to one or more embodiments, other suitable precursors include tetrakis(ethylmethylamino)zirconium (IV), tetrakis(ethylmethylamino)zirconium (IV), tetrakis(dimethylamino)zirconium (IV), tetrakis(dimethylamino)zirconium (IV), tetrakis(dimethylamino)zirconium (IV), dimethylbis(t-butylcyclopentadienyl)zirconium, bis(pentamethylcyclopentadienyl)dimethylzirconium (IV), bis(cyclopentadienyl)dimethylzirconium, bis(methylcyclopentadienyl)(methyl)(methoxy)zirconium (IV), and tetrakis(dimethylamino)zirconium (IV).

[0026]

[0028] Next, a flow or pulse of oxygen-containing gas is introduced through the gas inlet 108 as a gas or gas pulse that flows across the processing area 122, and the gas or gas pulse flows across the substrate. In one embodiment (which can be combined with other embodiments described herein), the oxygen-containing gas includes one or more of H2O, O3, or O2. In a particular embodiment, the oxygen-containing gas includes H2O. In another embodiment, the oxygen-containing gas includes O3 or O2. In operation 302, after the oxygen-containing gas has flowed across the substrate 130, a fluorine precursor, such as hexafluoroacetylacetonate (HHFAC) gas, is introduced through the gas inlet 108 as a gas or gas pulse that flows across the processing area 122, and the gas or gas pulse flows across the substrate 130, forming a yttrium-oxygen-fluorine-containing layer on the substrate 130.

[0027]

[0029] In some embodiments of operations 301 and 302, tris(butylcyclopentadienyl)yttrium gas is pulsed, followed by one oxygen-containing gas pulse, and then one HHFAC pulse. This pulse sequence is repeated N times in step 303 to yield a regulated and precisely controlled yttrium fluoride concentration in the membrane. In one or more embodiments, N is an integer in the range of 1 to 100, 1 to 50, 1 to 30, 1 to 20, 1 to 10, 1 to 5, 1 to 4, 1 to 3, or 1 to 2.

[0028]

[0030] In operations 304 and 305, a second set of gas flow or gas pulses is introduced into the processing area 122. In operation 304, a flow or pulse of zirconium precursor gas, such as tris(dimethylamino)cyclopentadienylzirconium (CpZr(NMe2)3), is introduced through the gas inlet 108 as a gas or gas pulse flowing across the processing area 122, and the gas or gas pulse flows across the substrate 130. In operation 305, a flow or pulse of oxygen-containing gas is introduced through the gas inlet 108 as a gas or gas pulse flowing across the processing area 122, and the gas or gas pulse flows across the substrate. In one embodiment (combinable with other embodiments described herein), the oxygen-containing gas includes one or more of H2O, O3, or O2. In certain embodiments, the oxygen-containing gas includes H2O. In other embodiments, the oxygen-containing gas includes O3 or O2.

[0029]

[0031] In some embodiments, a second set of gas pulses includes at least one pulse of a zirconium precursor (e.g., tris(dimethylamino)cyclopentadienylzirconium (CpZr(NMe2)3)), followed by one pulse of O3 or O2, and then one pulse of a fluorine precursor (e.g., HHFAC). According to one or more embodiments, this second set of pulses may be repeated M times depending on the desired zirconium fluoride concentration in the YZrOF film. According to one or more embodiments, other suitable precursors include tetrakis(ethylmethylamino)zirconium(IV), tetrakis(ethylmethylamino)zirconium(IV), tetrakis(dimethylamino)zirconium(IV), tetrakis(dimethylamino)zirconium(IV), tetrakis(dimethylamino)zirconium This includes M(IV), tetrakis(diethylamino)zirconium, dimethylbis(t-butylcyclopentadienyl)zirconium, bis(pentamethylcyclopentadienyl)dimethylzirconium(IV), bis(cyclopentadienyl)dimethylzirconium, bis(methylcyclopentadienyl)(methyl)(methoxy)zirconium(IV), and tetrakis(dimethylamino)zirconium(IV). In one or more embodiments, M is an integer in the range of 1 to 100, 1 to 50, 1 to 30, 1 to 20, 1 to 10, 1 to 5, 1 to 4, 1 to 3, or 1 to 2. In operation 207, operations 201 to 206 are repeated a sufficient number of times until a metal oxyfluoride film having a predetermined or target thickness, such as a yttrium zirconium oxyfluoride film, is formed on the substrate 130.

[0030]

[0032] In a particular embodiment of Method 200, in which the gas comprises a first set of gas pulses and a second set of gas pulses, the pulse time ranges from 3 milliseconds to 60 minutes, 3 milliseconds to 50 minutes, 3 milliseconds to 40 minutes, 3 milliseconds to 30 minutes, 3 milliseconds to 20 minutes, 3 milliseconds to 10 minutes, 3 milliseconds to 5 minutes, 3 milliseconds to 3 minutes, 3 milliseconds to 2 minutes, 3 milliseconds to 1 minute, 3 milliseconds to 50 seconds, 3 milliseconds to 40 seconds, 3 milliseconds to 30 seconds, 3 milliseconds to 20 seconds, 3 milliseconds to 10 seconds, or 3 milliseconds to 5 seconds, depending on the surface area of ​​the substrate to be coated. In one or more embodiments, an oxygen-containing precursor flowing across the processing area 122 flows across the substrate 130 and is activated into a plasma to form oxygen radicals. In another embodiment (combinable with other embodiments described herein), the oxygen radicals may be formed in a remote plasma source that provides the oxygen radicals to the processing area 122. In embodiments in which oxygen radicals are formed, the oxygen radicals react to deposit a layer of oxygen on the substrate 130. According to one or more embodiments, film growth is achieved by self-terminating and saturating chemical reactions of a gaseous precursor on the surface of the substrate 130. The gaseous precursor is introduced alternately onto the substrate and separated by an inert gas (e.g., nitrogen) purge. In one or more embodiments, the introduction of the purge gas flow into the processing area 122 is performed for a period ranging from about 1 millisecond to about 1000 seconds to purge the processing area 122.

[0031]

[0033] According to one or more embodiments, a predetermined or target Y-to-Zr ratio is controlled by the number of times a first set of gas pulses is repeated N times in operation 303 and the number of times a second set of gas pulses is repeated M times in operation 306. In the illustrated embodiment, at least one yttrium precursor (e.g., Y(CpBut)3) pulse or at least one zirconium precursor (e.g., tris(dimethylamino)cyclopentadienylzirconium (CpZr(NMe2)3) pulse) is prepared before the oxidizer pulse (H2O, O2, or O3) is applied to obtain improved nucleation on the surface of the substrate 130. However, the disclosure is not limited to a specific number of pulses for each gas, and in some embodiments, one Y(CpBut)3 pulse and one tris(dimethylamino)cyclopentadienylzirconium (CpZr(NMe2)3) pulse may be used.

[0032]

[0034] According to one or more embodiments, the ability to control the corrosion resistance and applications of the metal oxyfluoride film is provided by controlling the O:F ratio and the atomic percentage of oxygen. In some embodiments, the O:F ratio is in the range of 1:100 to 100:1, for example, less than 1:1 and less than 1:6. In some embodiments, the atomic percentage of oxygen is 1 to 98%, for example, 1 to 90%, 1 to 80%, 1 to 70%, 1 to 60%, 1 to 50%, 1 to 40%, 1 to 30%, 1 to 20%, or 1 to 0%. In one embodiment, the film has an atomic percentage of oxygen such that the metal oxyfluoride film contains 0.01 to 5% oxygen, i.e., the atomic percentage of oxygen for the metal oxyfluoride film is 1 to 5%. In another embodiment, the metal oxyfluoride film contains an oxygen content of 0.01 to 2%, i.e., the atomic percentage of oxygen in the metal oxyfluoride film is 0.01 to 2%. In one or more embodiments, the atomic percentage of fluorine is 1 to 99%, for example, 1 to 98%, e.g., 1 to 90%, 1 to 80%, 1 to 70%, 1 to 60%, 1 to 50%, 1 to 40%, 1 to 30%, 1 to 20%, 1 to 0%. In one embodiment, the film has an atomic percentage of fluorine such that the metal oxyfluoride film contains a fluorine content of 0.01 to 5%, i.e., the atomic percentage of fluorine in the metal oxyfluoride film is 1 to 5%. In another embodiment, the metal oxyfluoride film contains a fluorine content of 0.01 to 2%, i.e., the atomic percentage of fluorine in the metal oxyfluoride film is 0.01 to 2%.

[0033]

[0035] In one or more embodiments, the temperature within the processing region 122 is in the range of about 150°C to 500°C during method 200 or method 300, and the pressure within the processing region 122 is in the range of about 0.01 mbar to 100 mbar. In one embodiment, the O:F ratio and the atomic percentage of oxygen are controlled by the temperature within the processing region 122.

[0034]

[0036] By utilizing exemplary embodiments of the methods described herein, precise atomic control of metal oxyfluoride films is achieved. According to an embodiment of Method 300, HHFAC replaces Y(CpBut)3 ligands on the substrate surface with fluorinated acetylacetonate (ACAC) groups. A pulse of oxygen gas, e.g., O3, generates fluorinated species such as HF in situ after HHFAC, thereby promoting film fluorination. A similar phenomenon occurs with alternating pulses of tris(dimethylamino)cyclopentadienylzirconium (CpZr(NMe2)3), HHFAC, and an oxygen precursor (e.g., O3). In embodiments utilizing HHFAC, the oxygen precursor (e.g., O3) functions as an activator. It has been found that using HHFAC results in increased fluorine in the film compared to films formed using NF3.

[0035]

[0037] Throughout this specification, any reference to “one embodiment,” “a particular embodiment,” “one or more embodiments,” or “embodiments” means that a particular feature, structure, material, or property described in relation to an embodiment is included in at least one embodiment of this disclosure. Therefore, the appearance of phrases such as “in one or more embodiments,” “a particular embodiment,” “in one embodiment,” or “in an embodiment” in various places throughout this specification does not necessarily refer to the same embodiment of this disclosure. Furthermore, particular features, structures, materials, or properties can be combined in any suitable manner in one or more embodiments.

[0036]

[0038] While the disclosures herein have been described with reference to specific embodiments, it will be understood by those skilled in the art that the embodiments described are merely illustrative of the principles and applications of the disclosure. It will also be apparent to those skilled in the art that various modifications and changes are possible to the methods and apparatus of the disclosure without departing from the spirit and scope of the disclosure. Thus, the disclosure may include modifications and variations that fall within the scope of the appended claims and their equivalents.

Claims

1. A method for forming a yttrium zirconium oxyfluoride film, The substrate is placed inside the atomic layer deposition (ALD) chamber, which includes the processing area. A pulse of Y(CpBut)3 gas is passed through the aforementioned processing area. A yttrium-oxygen-fluorine-containing layer is formed on the substrate by alternately passing pulses of hexafluoroacetylacetonate gas and pulses of a first oxygen-containing gas through the processing region. The process involves passing a pulse of zirconium precursor gas through the processing area, and A yttrium zirconium oxyfluoride film is formed on the substrate by alternately passing pulses of a fluorine precursor gas and a second oxygen-containing gas through the processing region. Methods that include...

2. The method according to claim 1, wherein the substrate is selected from the group consisting of a part of a substrate processing chamber, a substrate processing chamber component, and the surface of a substrate processing chamber.

3. The fluorine precursor gas, NF ３ , phosphorus pentafluoride (PF ５ ), HF gas, and sulfur hexafluoride (SF ６ The method according to claim 1, selected from the group consisting of ).

4. The method according to claim 2, wherein the fluorine precursor gas is selected from the group consisting of hexafluoroacetylacetonate, pivaloyltrifluoroacetone, trifluoroacetylacetone, valeryltrifluoroacetone, benzoyltrifluoroacetone, tetrafluoropropanol (TFP), 1,1,1,2-tetrafluoroethane (HFC-134), and HF-pyridine.

5. The zirconium precursor gas is tris(dimethylamino)cyclopentadienylzirconium (CpZr(NMe) ２ ) ３ The method according to claim 1, including )

6. The zirconium precursor gas is tris(dimethylamino)cyclopentadienylzirconium (CpZr(NMe) ２ ) ３ The method according to claim 4, including )

7. The method according to claim 1, further comprising repeating pulses of the Y(CpBut)3 gas, the hexafluoroacetylacetonate gas, the first oxygen-containing gas, the fluorine precursor gas, the second oxygen-containing gas, and the zirconium precursor gas until a predetermined film thickness is formed.

8. The method according to claim 7, wherein the ratio of the Y(CpBut)3 gas pulse to the zirconium precursor gas pulse is in the range of 1:100 to 100:

1.

9. The method according to claim 1, wherein the pulses of the Y(CpBut)3 gas, the hexafluoroacetylacetonate gas, the first oxygen-containing gas, the fluorine precursor gas, the second oxygen-containing gas, and the zirconium precursor gas are in the range of 3 milliseconds to 60 minutes.

10. The method according to claim 9, further comprising passing an inert purge gas after passing pulses of the Y(CpBut)3 gas, the hexafluoroacetylacetonate gas, the first oxygen-containing gas, the fluorine precursor gas, the second oxygen-containing gas, and the zirconium precursor gas.

11. The method according to claim 7, wherein the pulses of the Y(CpBut)3 gas, the hexafluoroacetylacetonate gas, the first oxygen-containing gas, the fluorine precursor gas, the second oxygen-containing gas, and the zirconium precursor gas are in the range of 3 milliseconds to 60 minutes.

12. The method according to claim 11, further comprising passing an inert purge gas after passing pulses of the Y(CpBut)3 gas, the hexafluoroacetylacetonate gas, the first oxygen-containing gas, the fluorine precursor gas, the second oxygen-containing gas, and the zirconium precursor gas.

13. The method according to claim 1, wherein the processing region is at a temperature in the range of 150°C to 500°C, and the processing region is at a pressure in the range of 0.01 mbar to 100 mbar.

14. A method for forming a yttrium zirconium oxyfluoride film on a substrate, A pulse of Y(CpBut)3 gas is passed over the substrate, selected from the group consisting of a part of the substrate processing chamber, components of the substrate processing chamber, and the surface of the substrate processing chamber. A yttrium-oxygen-fluorine-containing layer is formed on the substrate by alternately passing pulses of hexafluoroacetylacetonate gas and pulses of a first oxygen-containing gas across the substrate. The process involves passing a pulse of zirconium precursor gas across the substrate, and A yttrium zirconium oxyfluoride film is formed on the substrate by alternately passing pulses of a fluorine-containing gas and a second oxygen-containing gas across the substrate. Methods that include...

15. The method according to claim 14, further comprising repeating pulses of the Y(CpBut)3 gas, the hexafluoroacetylacetonate gas, the first oxygen-containing gas, the fluorine-containing gas, the second oxygen-containing gas, and the zirconium precursor gas until a predetermined film thickness is formed.

16. The method according to claim 15, wherein the ratio of the Y(CpBut)3 gas pulse to the zirconium precursor gas pulse is in the range of 1:100 to 100:

1.

17. A method for forming a yttrium zirconium oxyfluoride film on a substrate, Y(CpBut) is applied across the substrate, selected from the group consisting of a part of the substrate processing chamber, components of the substrate processing chamber, and the surface of the substrate processing chamber. ３ Sending a pulse of gas, A yttrium-oxygen-fluorine-containing layer is formed on the substrate by alternately passing pulses of hexafluoroacetylacetonate gas and pulses of a first oxygen-containing gas across the substrate. Across said substrate, tris(dimethylamino)cyclopentadienylzirconium (CpZr(NMe ２ ) ３ ) flowing a pulse of gas, and A yttrium zirconium oxyfluoride film is formed on the substrate by alternately passing pulses of a fluorine-containing gas and a second oxygen-containing gas across the substrate. Methods that include...

18. Until the predetermined film thickness is formed, Y(CpBut) ３ Gas, hexafluoroacetylacetonate gas, first oxygen-containing gas, the fluorine-containing gas, the second oxygen-containing gas, and tris(dimethylamino)cyclopentadienylzirconium (CpZr(NMe ２ ) ３ The method according to claim 17, further comprising repeating each of the gas pulses.

19. Y (CpBut) ３ Gas pulse and tris(dimethylamino)cyclopentadienylzirconium(CpZr(NMe ２ ) ３ The method according to claim 18, wherein the ratio of the gas pulse to the pulse is in the range of 1:100 to 100:1.

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