Metal oxyfluoride film forming method

Abstract

Methods of forming a metal oxyfluoride film are provided. A substrate is placed in an atomic layer deposition (ALD) chamber having a processing zone. A zirconium-containing gas, a zirconium precursor gas (e.g., tris(dimethylamino) cyclopentadienyl zirconium), an oxygen-containing gas, a fluorine-containing gas, and a yttrium precursor (e.g., tris(butylcyclopentadienyl) yttrium gas) are flowed to the processing zone, wherein a metal oxyfluoride film, such as a yttrium zirconium oxyfluoride film, is formed.

Description

Technical Field

[0001] Embodiments of this disclosure generally relate to methods for forming metal fluoride films. In particular, embodiments of this disclosure relate to components for coating substrate processing chambers with metal fluoride films. Background Technology

[0002] As part of the processes used to manufacture electronic devices such as semiconductor devices, flat panel display devices, and organic light-emitting diode (OLED) devices in substrate processing chambers, these devices are manufactured through multiple manufacturing processes that produce structures of ever-decreasing size. Some manufacturing processes, such as plasma etching and plasma cleaning processes, expose the substrate and chamber to a plasma stream. Plasma can be highly corrosive and can corrode the processing chamber and other surfaces exposed to it. Therefore, it is generally desirable to coat chamber surfaces, chamber components, and chamber tooling with a fluorinated coating to protect these parts of the chamber from corrosion or degradation. Without a fluorinated coating, plasma during substrate processing (e.g., halide plasma) can corrode these parts of the substrate processing chamber. Corrosion of chamber surfaces, chamber components, and chamber tooling can have detrimental effects on electronic devices manufactured in the substrate processing chamber, such as negatively impacting product yield, chamber uptime, and customer costs.

[0003] Current methods for forming fluorinated oxide films use materials such as HF pyridine and fluorine, which do not provide precise control over the properties of the fluorinated coating. Therefore, there is a need for improved methods for forming fluorinated oxide films, particularly on the chamber surfaces, chamber components, and chamber tools of substrate processing chambers. Summary of the Invention

[0004] One or more embodiments of this disclosure relate to a method for forming a yttrium zirconium oxyfluoride film, the method comprising: placing a substrate in an atomic layer deposition (ALD) chamber including a processing zone; pulse-flowing a yttrium precursor gas into the processing zone; pulse-flowing an alternating fluorine precursor gas and an oxygen-containing gas into the processing zone to form a yttrium-oxy-fluorine layer on the substrate; pulse-flowing a zirconium precursor gas into the processing zone; and pulse-flowing an alternating fluorine precursor gas and an oxygen-containing gas into the processing zone to form the yttrium zirconium oxyfluoride film on the substrate.

[0005] Another embodiment relates to a method for forming a yttrium zirconium oxyfluoride film on a substrate, the method comprising: pulsed flow of a yttrium precursor gas through the substrate, the substrate being selected from the group consisting of: a portion of a substrate processing chamber, a substrate processing chamber component, and a substrate processing chamber surface; pulsed flow of alternating pulses of a fluorine-containing gas and an oxygen-containing gas through the substrate to form a yttrium-oxygen-fluorine layer on the substrate; pulsed flow of a zirconium precursor gas through the substrate; and pulsed flow of alternating pulses of a fluorine-containing gas and an oxygen-containing gas through the substrate to form the yttrium zirconium oxyfluoride film on the substrate.

[0006] Another embodiment relates to a method for forming a yttrium zirconium oxyfluoride film on a substrate, the method comprising: pulsed flow of a Y(CpBut)3 gas through the substrate, the substrate being selected from the group consisting of: a portion of a substrate processing chamber, a substrate processing chamber component, and a substrate processing chamber surface; pulsed flow of an alternating pulse of a hexafluoroacetylacetone gas and an oxygen-containing gas through the substrate to form a yttrium-oxy-fluorine layer on the substrate; pulsed flow of a tris(dimethylamino)cyclopentadienylzirconium (CpZr(NMe2)3) gas through the substrate; and pulsed flow of an alternating pulse of an NF3 gas and an oxygen-containing gas through the substrate to form a yttrium zirconium oxyfluoride film on the substrate. Attached Figure Description

[0007] Figure 1 This is a schematic diagram of an atomic layer deposition chamber according to an embodiment;

[0008] Figure 2 This is a flowchart illustrating the operation of a method for forming a metal fluoride film according to a specific non-limiting embodiment; and

[0009] Figure 3 This is a flowchart illustrating the operation of a method for forming a metal fluoride film according to a specific non-limiting embodiment. Detailed Implementation

[0010] Before describing several exemplary embodiments of this disclosure, it will be understood that this disclosure is not limited to the details of the construction or processing steps set forth in the following description. This disclosure can have other embodiments and be practiced or carried out in various ways.

[0011] As used in this specification and the appended claims, the term "substrate" refers to the surface or portion of the surface on which a process is performed. Those skilled in the art will also understand that, unless the context clearly indicates otherwise, reference to substrate may also refer only to a portion of the substrate. Additionally, reference to deposition on a substrate may mean both a bare substrate and a substrate on which one or more films or features are deposited or formed.

[0012] In addition to forming the 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 underlayer formed on the substrate, as disclosed in more detail below, and the term "substrate surface" is intended to include such an underlayer as indicated by the context. Thus, for example, where a film / layer or a portion thereof has already been deposited on the substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate surface. In specific embodiments, the substrate includes a portion of a substrate processing chamber, a substrate processing chamber component, or a substrate processing chamber surface. In some specific embodiments, the substrate processing chamber, substrate processing chamber component, or substrate processing chamber surface comprises aluminum, aluminum alloys, and / or anodized aluminum alloys. The term "on" indicates direct contact between elements. The term "directly on" indicates direct contact between elements without intervening elements.

[0013] One or more embodiments of this disclosure relate to methods for forming fluorinated metal films and methods for forming metal fluoride oxide films. It has been determined that one or more embodiments of the methods described herein enable controllable, self-limiting fluorination methods. Some embodiments include atomic layer deposition (ALD) processes. In some embodiments, the Y / Zr ratio and O / F ratio can be precisely tuned or adjusted very easily. One or more embodiments of the methods described herein provide easier methods for fluorination using hexafluoroacetylacetone (HHFAC) with oxygen or ozone plasma and for fluorination using NF3 itself to form metal fluoride oxide films. It has been determined that embodiments of the fluorination methods described herein enable atomic-level control of fluorination, which was previously considered impossible by other methods. One or more embodiments of the methods described herein provide easier methods 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 fluoride oxide film is amorphous. In other embodiments, the metal fluoride oxide film is crystalline. In some embodiments, the metal fluoride film comprises partially amorphous and partially crystalline films.

[0014] The embodiments described herein can be used to control the oxygen-to-fluorine ratio in fluorinated oxides with atomic precision. The fluorination methods are self-limiting and offer greater control than thermal fluorination methods.

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

[0016] Figure 1 This is a schematic diagram of an atomic layer deposition (ALD) chamber 100. It will be understood that the chambers described in this disclosure are exemplary embodiments of chambers, and other chambers, including chambers from other manufacturers, may be used in conjunction with or modified to implement aspects of this disclosure, such as the method 200 for forming a metal fluoride film 300.

[0017] ALD chamber 100 includes a chamber body 101. The chamber body includes a main portion 102, a cover portion 104, and a support assembly 112. A gas inlet 108 and a gas outlet 110 are disposed between the main portion 102 and the cover portion 104 of the chamber body 101. The support assembly 112 is at least partially disposed within the main portion 102 of the chamber body 101. The support assembly 106 includes a base 114 movably disposed in the chamber body 101 by means of a stem 116. The base 114 includes a support surface 118, which is described in further detail herein, and is configured to support a substrate 130. The stem 116 extends through the chamber body 101 and is connected to a lifting system (not shown) that moves the base 114 between a processing position (as shown) and a transfer position. The transfer position facilitates the transfer of the substrate 130 through an opening 120 formed in the sidewall of the main portion 102 to provide access to the interior of the ALD chamber 100.

[0018] In the processing position, the base 114 of the support assembly 112 contacts the main body portion 102 to form a processing region 122 defined by the support surface 118, the upper surface of the main body portion 102, and the lower surface of the cover portion 104. When the support assembly 112 contacts the main body portion 102 in the processing position to form the processing region 122, the gas inlet 108 and the gas outlet 110 are in fluid communication with the processing region 122. In this way, gas is supplied to the processing region 122 through the gas inlet 108. The substrate 130 is adjacent to the processing region 122. Gas flows through the substrate 130 in the processing region 122 and is discharged 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 electrodes 128 of the cover portion 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 electrodes 128 to generate plasma from the gas in the processing region 122. The base 114 is grounded or can be used as a cathode when connected to the plasma source 126 to generate a capacitive electric field between the lower surface of the cover portion 104 and the base 114, thereby accelerating the plasma species toward the substrate 130.

[0019] Figure 2This is a flowchart illustrating the operation of a method 200 for forming a metal fluoride film on a substrate according to a specific, non-limiting embodiment showing a specific precursor. In a particular embodiment, the metal fluoride film is a yttrium zirconium fluoride (YZrOF) film. In operation 201, a pulse of a yttrium precursor (e.g., tris(butylcyclopentadienyl)yttrium (Y(CpBut)3) precursor) is introduced into the ALD chamber 100. In one or more embodiments, other suitable yttrium precursors include complexes having the general formula YR1R2R3, wherein R1, R2, and R3 are independently selected from halides, carbonyl groups, cyclopentadienes, amines, acetylacetone (acac), hexafluoroacetylacetone (hfac), amideates, or diazadienes. Other non-limiting examples of yttrium precursors include tris(N,N''-diisopropylformamidinium)yttrium(III), tris(ethylcyclopentadienyl)yttrium, tris[N,N-bis(trimethylsilane)amide]yttrium(III), tris[N,N-bis(trimethylsilane)amide]yttrium(III), tris(butylcyclopentadienyl)yttrium, tris(cyclopentadienyl)yttrium, tris(methylcyclopentadienyl)yttrium, tris(n-propylcyclopentadienyl)yttrium, tris(2,2,6,6-tetramethyl-3,5-heptanedionyl)yttrium(III), and tris(2,2,6,6-tetramethyl-3,5-heptanedionyl)yttrium(III) triethylene glycol dimethyl ether adduct (Tris(2,2,6,6-tetramethyl-3,5-heptanedionyl)yttrium(III)). Yttrium(III) acetylacetonate, yttrium(III) chloride, and yttrium(III) hexafluoroacetylacetonate. The substrate 130 can be a chamber component, a chamber tool, a chamber, and a chamber main frame. The substrate can be made of aluminum and / or anodized aluminum. Method 200 in some embodiments includes transferring the substrate into the ALD chamber 100 and placing the substrate on the base 114.

[0020] In one embodiment that can be combined with other embodiments described herein, the method includes introducing a stream or pulse of a yttrium precursor (e.g., tris(butylcyclopentadienyl)yttrium gas) into processing zone 122. Tris(butylcyclopentadienyl)yttrium gas is introduced as a flowing gas or gas pulse through gas inlet 108 and across processing zone 122, flowing over substrate 130 and forming a yttrium-containing layer on substrate 130. Next, a stream or pulse of oxygen-containing gas is introduced as a flowing gas or gas pulse through gas inlet 108 and across processing zone 122, flowing over substrate. In one embodiment that can be combined with other embodiments described herein, the oxygen-containing gas includes one or more of H2O, O3, or O2. In a specific embodiment, the oxygen-containing gas includes H2O. In other embodiments, the oxygen-containing gas includes O3 or O2. In operation 202, after oxygen-containing gas flows through substrate 130, a fluorine precursor (e.g., NF3 gas) is introduced as a flowing gas or gas pulse through gas inlet 108 and across processing zone 122, flowing through substrate 130 and forming a yttrium-oxy-fluorine layer on substrate 130. In some embodiments, the fluorine precursor comprises at least one organic fluorine reagent. In one or more embodiments, the fluorine precursor is selected from hexafluoroacetylacetone, neopentanoyltrifluoroacetone, trifluoroacetylacetone, pentyltrifluoroacetone, benzoyltrifluoroacetone, tetrafluoropropanol (TFP), 1,1,1,2-tetrafluoroethane (HFC-134), and HF pyridine. In embodiments that may be combined 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).

[0021] In some embodiments, during operations 201 and 202, at least one pulse of tris(butylcyclopentadienyl)yttrium gas is performed, and in some embodiments, more than one (e.g., 2 to 5) pulses are performed, followed by an oxygen-containing gas pulse, and then an NF3 gas pulse. In step 203, this pulse sequence is repeated N times to provide an adjusted 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.

[0022] In operations 204 and 205, a second set of gas flows or gas pulses are provided to processing zone 122. In operation 204, a flow or pulse of zirconium precursor gas (e.g., tris(dimethylamino)cyclopentadienyl zirconium (CpZr(NMe2)3)) is introduced as a flowing gas or gas pulse through gas inlet 108 and across processing zone 122, flowing over substrate 130. In operation 205, a flow or pulse of oxygen-containing gas is then introduced as a flowing gas or gas pulse through gas inlet 108 and across processing zone 122, flowing over substrate. In one embodiment, which may be combined with other embodiments described herein, the oxygen-containing gas includes one or more of H2O, O3, or O2. In a specific embodiment, the oxygen-containing gas includes H2O. In other embodiments, the oxygen-containing gas includes O3 or O2.

[0023] In some embodiments, the second set of gas pulses comprises at least one pulse of tris(dimethylamino)cyclopentadienylzirconium (CpZr(NMe2)3), followed by an O3 or O2 pulse, and then an NF3 pulse. This second set of pulses according to one or more embodiments 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 fluoride oxide film having a predetermined or target film thickness is formed on the substrate 130.

[0024] In a specific embodiment of method 300, in which the gas includes a first set of gas pulses and a second set of gas pulses, the pulse duration ranges from three milliseconds to 60 minutes, three milliseconds to 50 minutes, three milliseconds to 40 minutes, three milliseconds to 30 minutes, three milliseconds to 20 minutes, three milliseconds to 10 minutes, three milliseconds to 5 minutes, three milliseconds to 3 minutes, three milliseconds to 2 minutes, three milliseconds to 1 minute, three milliseconds to 50 seconds, three milliseconds to 40 seconds, three milliseconds to 30 seconds, three milliseconds to 20 seconds, three milliseconds to 10 seconds, or three milliseconds to 5 seconds, depending on the surface area of ​​the substrate being coated. In one or more embodiments, oxygen-containing precursors flowing through processing zone 122 flow through substrate 130 and are activated into plasma to form oxygen radicals. In another embodiment, which may be combined with other embodiments described herein, oxygen radicals may be formed in a remote plasma source that provides oxygen radicals to processing zone 122. In embodiments where oxygen radicals are formed, the oxygen radicals react with substrate 130 and deposit an oxygen layer on substrate 130. According to one or more embodiments, film growth occurs via a self-limiting and saturation chemical reaction of a gas precursor on the surface of substrate 130. The gas precursor is alternately introduced onto the substrate and separated by purification with an inert gas (e.g., nitrogen). In one or more embodiments, a stream of purified gas is directed to processing zone 122 for a period ranging from about 1 millisecond to about 1000 seconds to purify processing zone 122.

[0025] According to one or more embodiments, the number of times each of 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 controls a predetermined or target Y to Zr ratio. In the illustrated embodiments, yttrium precursor (e.g., Y(CpBut)3) pulses or zirconium precursor (e.g., tris(dimethylamino)cyclopentadienylzirconium (CpZr(NMe2)3)) pulses are applied before the oxidant pulses (H2O, O2, or O3) are applied. In one or more embodiments, the number of yttrium and zirconium precursor pulses applied before the oxidant pulses (H2O, O2, or O3) are applied is adjusted to obtain improved nucleation on the surface of substrate 130. However, this disclosure is not limited to a specific number of pulses for each gas, and in some embodiments, a yttrium precursor (e.g., Y(CpBut)3) pulse and a zirconium precursor (e.g., tris(dimethylamino)cyclopentadienyl zirconium (CpZr(NMe2)3) pulse) may be used. Other suitable precursors according to one or more embodiments include tetra(ethylmethylamino)zirconium (IV), tetra(ethylmethylamino)zirconium (IV), tetra(dimethylamino)zirconium (IV), tetra(dimethylamino)zirconium (IV), tetra(dimethylamino)zirconium (IV), tetra(diethylamino)zirconium, dimethylbis(tert-butylcyclopentadienyl)zirconium, bis(pentamethylcyclopentadienyl)dimethylzirconium (IV), bis(cyclopentadienyl)dimethylzirconium, bis(methylcyclopentadienyl)(methyl)(methoxy)zirconium (IV) and tetra(dimethylamino)zirconium (IV).

[0026] Now for reference Figure 3 This illustrates another embodiment of forming a metal fluoride film on a substrate 130 according to a specific, non-limiting embodiment of a specific precursor. In a particular embodiment, the metal fluoride film is a yttrium zirconium fluoride (YZrOF) film. In operation 301, a pulse of the tris(butylcyclopentadienyl)yttrium (Y(CpBut)3) precursor is introduced into the ALD chamber 100. The substrate 130 may be a chamber component, a chamber tool, a chamber, and a chamber main frame. The substrate may be composed of aluminum and / or anodized aluminum. Method 200 of some embodiments includes conveying the substrate into the ALD chamber 100 and placing the substrate on a base 114.

[0027] In one embodiment, which may be combined with other embodiments described herein, the method includes introducing a stream or pulse of a yttrium precursor (e.g., tris(butylcyclopentadienyl)yttrium gas) into processing region 122. The tris(butylcyclopentadienyl)yttrium gas is introduced as a flowing gas or gas pulse through gas inlet 108 and across processing region 122, flowing over substrate 130 and forming a yttrium-containing layer on substrate 130. According to one or more embodiments, other suitable precursors include tetra(ethylmethylamino)zirconium (IV), tetra(ethylmethylamino)zirconium (IV), tetra(dimethylamino)zirconium (IV), tetra(dimethylamino)zirconium (IV), tetra(dimethylamino)zirconium (IV), tetra(diethylamino)zirconium, dimethylbis(tert-butylcyclopentadienyl)zirconium, bis(pentamethylcyclopentadienyl)dimethylzirconium (IV), bis(cyclopentadienyl)dimethylzirconium, bis(methylcyclopentadienyl)(methyl)(methoxy)zirconium (IV) and tetra(dimethylamino)zirconium (IV).

[0028] Next, a flow or pulse of oxygen-containing gas is introduced as a flowing gas or gas pulse through gas inlet 108 and across processing zone 122, flowing over the substrate. In one embodiment, which may be combined with other embodiments described herein, the oxygen-containing gas includes one or more of H2O, O3, or O2. In a specific embodiment, the oxygen-containing gas includes H2O. In other embodiments, the oxygen-containing gas includes O3 or O2. In operation 302, after the oxygen-containing gas flows over substrate 130, a fluorine precursor (e.g., hexafluoroacetylacetone (HHFAC) gas) is introduced as a flowing gas or gas pulse through gas inlet 108 and across processing zone 122, flowing over substrate 130 and forming a yttrium-oxygen-fluorine layer on substrate 130.

[0029] In some embodiments, during operations 301 and 302, a pulse of tris(butylcyclopentadienyl)yttrium gas is applied, followed by a pulse of oxygen-containing gas, and then a single HHFAC pulse. In step 303, this pulse sequence is repeated N times to provide an adjusted and precisely controlled concentration of yttrium fluoride 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.

[0030] In operations 304 and 305, a second set of gas flows or gas pulses are provided to processing zone 122. In operation 304, a flow or pulse of zirconium precursor gas (e.g., tris(dimethylamino)cyclopentadienyl zirconium (CpZr(NMe2)3)) is introduced as a flowing gas or gas pulse through gas inlet 108 and across processing zone 122, flowing over substrate 130. In operation 305, a flow or pulse of oxygen-containing gas is introduced as a flowing gas or gas pulse through gas inlet 108 and across processing zone 122, flowing over substrate. In one embodiment, which may be combined with other embodiments described herein, the oxygen-containing gas includes one or more of H2O, O3, or O2. In a specific embodiment, the oxygen-containing gas includes H2O. In other embodiments, the oxygen-containing gas includes O3 or O2.

[0031] In some embodiments, the second set of gas pulses comprises at least one pulse of a zirconium precursor (e.g., tris(dimethylamino)cyclopentadienyl zirconium (CpZr(NMe2)3), followed by a single pulse of O3 or O2, and then a single pulse of a fluorine precursor (e.g., HHFAC). This second set of pulses according to one or more embodiments may be repeated M times, depending on the desired zirconium fluoride concentration in the YZrOF film. Other suitable precursors according to one or more embodiments include tetra(ethylmethylamino)zirconium (IV), tetra(ethylmethylamino)zirconium (IV), tetra(di ... Zirconium (IV), tetra(diethylamino)zirconium, dimethylbis(tert-butylcyclopentadienyl)zirconium, bis(pentamethylcyclopentadienyl)dimethylzirconium (IV), bis(cyclopentadienyl)dimethylzirconium, bis(methylcyclopentadienyl)(methyl)(methoxy)zirconium (IV), and tetra(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 fluoride film, such as a yttrium zirconium fluoride film, having a predetermined or target film thickness is formed on substrate 130.

[0032] In a specific embodiment of method 200, in which the gas includes a first set of gas pulses and a second set of gas pulses, the pulse duration ranges from three milliseconds to 60 minutes, three milliseconds to 50 minutes, three milliseconds to 40 minutes, three milliseconds to 30 minutes, three milliseconds to 20 minutes, three milliseconds to 10 minutes, three milliseconds to 5 minutes, three milliseconds to 3 minutes, three milliseconds to 2 minutes, three milliseconds to 1 minute, three milliseconds to 50 seconds, three milliseconds to 40 seconds, three milliseconds to 30 seconds, three milliseconds to 20 seconds, three milliseconds to 10 seconds, or three milliseconds to 5 seconds, depending on the surface area of ​​the substrate being coated. In one or more embodiments, oxygen-containing precursors flowing through processing zone 122 flow through substrate 130 and are activated into plasma to form oxygen radicals. In another embodiment, which may be combined with other embodiments described herein, oxygen radicals may be formed in a remote plasma source that provides oxygen radicals to processing zone 122. In embodiments where oxygen radicals are formed, the oxygen radicals react with substrate 130 and deposit an oxygen layer on substrate 130. According to one or more embodiments, film growth occurs via a self-limiting and saturation chemical reaction of a gas precursor on the surface of substrate 130. The gas precursor is alternately introduced onto the substrate and separated by purification with an inert gas (e.g., nitrogen). In one or more embodiments, a stream of purified gas is directed to processing zone 122 for a period ranging from about 1 millisecond to about 1000 seconds to purify processing zone 122.

[0033] According to one or more embodiments, the number of times each of the first set of gas pulses is repeated N times in operation 303 and the number of times the second set of gas pulses is repeated M times in operation 306 controls a predetermined or target Y to Zr ratio. 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 applied before the oxidant pulse (H2O, O2, or O3) is flowed is adjusted to obtain improved nucleation on the surface of substrate 130. However, this 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.

[0034] According to one or more embodiments, controlling the O:F ratio and the atomic percentage of oxygen provides the ability to adjust the corrosion resistance and application of the metal fluoride film. In some embodiments, the O:F ratio is in the range of 1:100 to 100:1, for example, less than 1:1, such as 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 a certain atomic percentage of oxygen such that the metal fluoride film contains 0.01% to 5% oxygen content, i.e., the atomic percentage of oxygen in the metal fluoride film is 1% to 5%. In another embodiment, the metal fluoride film contains 0.01% to 2% oxygen content, i.e., the atomic percentage of oxygen in the metal fluoride 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%, such as 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 membrane has a certain atomic percentage of fluorine such that the metal fluoride membrane contains 0.01% to 5% fluorine content, i.e., the atomic percentage of fluorine in the metal fluoride membrane is 1% to 5%. In another embodiment, the metal fluoride membrane contains 0.01% to 2% fluorine content, i.e., the atomic percentage of fluorine in the metal fluoride membrane is 0.01% to 2%.

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

[0036] The exemplary embodiments of the methods described herein provide precise atomic control over metal fluoride films. According to an embodiment of method 300, HHFAC replaces the Y(CpBut)3 ligand at the surface of the substrate with a fluorinated acetylacetone (ACAC) group. A pulse of oxygen gas (e.g., O3) following HHFAC generates fluorinated species, such as HF, in situ, which promotes fluorination of the film. A similar phenomenon occurs in 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) acts as an activator. It has been determined that using HHFAC increases the fluorine content in the film compared to films formed using NF3.

[0037] Throughout this specification, references to "one embodiment," "some embodiments," "one or more embodiments," or "embodiment" mean that a particular feature, structure, material, or characteristic described in connection with that embodiment is included in at least one embodiment of this disclosure. Therefore, the use of phrases such as "in one or more embodiments," "in some embodiments," "in one embodiment," or "in an embodiment" throughout this specification does not necessarily refer to the same embodiment of this disclosure. Furthermore, a particular feature, structure, material, or characteristic may be combined in one or more embodiments in any suitable manner.

[0038] Although the disclosure herein has been described with reference to specific embodiments, those skilled in the art will understand that the described embodiments are merely illustrative of the principles and applications of this disclosure. It will be apparent to those skilled in the art that various modifications and variations can be made to the methods and apparatus of this disclosure without departing from the spirit and scope of this disclosure. Therefore, this disclosure may include modifications and variations within the scope of the appended claims and their equivalents.

Claims

1. A method for forming a yttrium zirconium fluoride film, the method comprising: The substrate is placed in an atomic layer deposition (ALD) chamber that includes a processing area; A pulsed flow of Y(CpBut)3 gas is directed to the processing area; Alternating pulses of hexafluoroacetylacetone gas and oxygen-containing gas are applied to the processing area to form a yttrium-oxygen-fluorine layer on the substrate; A pulsed flow of zirconium precursor gas is directed to the processing zone; as well as Alternating pulses of fluorine precursor gas and oxygen-containing gas are applied to the processing area to form the yttrium fluoride zirconium film on the substrate.

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

3. The method of claim 1, wherein the zirconium precursor gas comprises tris(dimethylamino)cyclopentadienyl zirconium (CpZr(NMe2)3).

4. The method of claim 1, further comprising repeating each of the pulses of the Y(CpBut)3 gas, the hexafluoroacetylacetone gas, the oxygen-containing gas, the fluorine precursor gas, and the zirconium precursor gas until a predetermined film thickness is formed.

5. The method of claim 4, wherein the ratio of the pulse of the Y(CpBut)3 gas to the pulse of the zirconium precursor gas is in the range of 1:100 to 100:

1.

6. The method of claim 1, wherein each of the pulses of the Y(CpBut)3 gas, the hexafluoroacetylacetone gas, the oxygen-containing gas, the fluorine precursor gas, and the zirconium precursor gas is in the range of 3 milliseconds to 60 minutes.

7. The method of claim 6, further comprising flowing an inert purifying gas after each of the pulses of the Y(CpBut)3 gas, the hexafluoroacetylacetone gas, the oxygen-containing gas, the fluorine precursor gas, and the zirconium precursor gas.

8. The method of claim 4, wherein each of the pulses of the Y(CpBut)3 gas, the hexafluoroacetylacetone gas, the oxygen-containing gas, the fluorine precursor gas, and the zirconium precursor gas is in the range of 3 milliseconds to 60 minutes.

9. The method of claim 8, further comprising flowing an inert purifying gas after each of the pulses of the Y(CpBut)3 gas, the hexafluoroacetylacetone gas, the oxygen-containing gas, the fluorine precursor gas, and the zirconium precursor gas.

10. The method of claim 1, wherein the treatment zone is in a temperature range of 150°C to 500°C and the treatment zone is in a pressure range of 0.01 mbar to 100 mbar.

11. A method for forming a yttrium zirconium fluoride film on a substrate, the method comprising: A pulsed flow of Y(CpBut)3 gas is passed through the substrate, the substrate being selected from the group consisting of: a portion of a substrate processing chamber, a substrate processing chamber component, and a substrate processing chamber surface; Alternating pulses of hexafluoroacetylacetone gas and oxygen-containing gas are passed through the substrate to form a yttrium-oxygen-fluorine layer on the substrate; A pulsed flow of zirconium precursor gas is passed through the substrate; as well as The substrate is subjected to alternating pulses of fluorine-containing gas and oxygen-containing gas to form the yttrium fluoride zirconium film on the substrate.

12. The method of claim 11, further comprising repeating each of the pulses of the Y(CpBut)3 gas, the hexafluoroacetylacetone gas, the oxygen-containing gas, the fluorine-containing gas, and the zirconium precursor gas until a predetermined film thickness is formed.

13. The method of claim 12, wherein the ratio of the pulse of the Y(CpBut)3 gas to the pulse of the zirconium precursor gas is in the range of 1:100 to 100:

1.

14. A method for forming a yttrium zirconium fluoride film on a substrate, the method comprising: A pulsed flow of Y(CpBut)3 gas is passed through the substrate, the substrate being selected from the group consisting of: a portion of a substrate processing chamber, a substrate processing chamber component, and a substrate processing chamber surface; Alternating pulses of hexafluoroacetylacetone gas and oxygen-containing gas are passed through the substrate to form a yttrium-oxygen-fluorine layer on the substrate; A pulsed flow of tris(dimethylamino)cyclopentadienylzirconium (CpZr(NMe2)3) gas is passed through the substrate; and An alternating pulse flow of NF3 gas and oxygen-containing gas is passed through the substrate to form a yttrium fluoride zirconium film on the substrate.

15. The method of claim 14, further comprising repeating each of the pulses of the Y(CpBut)3 gas, the hexafluoroacetylacetone gas, the oxygen-containing gas, the NF3, and the tris(dimethylamino)cyclopentadienylzirconium (CpZr(NMe2)3) until a predetermined film thickness is formed.

16. The method of claim 15, wherein the ratio of the pulse of the Y(CpBut)3 gas to the pulse of the tris(dimethylamino)cyclopentadienylzirconium (CpZr(NMe2)3) gas is in the range of 1:100 to 100:1.

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