High temperature coatings for preclean and etching equipment and related methods - Patents.com

Abstract

To provide a coating for a semiconductor film pre-cleaning and etching apparatus and a method of forming the same.SOLUTION: In a semiconductor film pre-cleaning apparatus 100, at least one of a wafer holder, a susceptor 120, a reaction chamber 110, a gas transfer path 160, a gas distributor 140, a gas manifold 150, or a remote plasma unit 170 includes coatings of a first layer and a second layer. At least one of the coatings of the first layer or the second layer is formed by atomic layer deposition (ALD). The coatings of the first layer and the second layer contain different materials.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates generally to an apparatus and associated methods for performing a pre-clean or etching process on a semiconductor wafer. More specifically, the present disclosure relates to a coating for components in the apparatus formed by an atomic layer deposition (ALD) process. The coating offers the advantages of effectively delivering hydrogen and fluorine radicals formed by a remote plasma unit to the wafer surface in a single apparatus, or separately in a dual apparatus, covering high aspect ratio features on critical components, and being able to operate at high temperature conditions with metal-free and particle-free performance. [Background technology]

[0002] Coatings are used on components in semiconductor film manufacturing equipment to avoid particle generation that may adversely affect the films formed on semiconductor wafers. These coatings are particularly found in equipment that may undergo pre-clean or etching processes. Coatings may include metals and ceramics, such as nickel, aluminum oxide, yttrium oxide, zirconium oxide, magnesium oxide, or calcium oxide. The pre-clean or etching processes may include chemicals or plasmas that may react with the components underneath the coating. Thus, the coating acts as a protective barrier for the components.

[0003] However, these conventional coatings have several problems. First, hydrogen radicals exhibit very high recombination rates in some coatings, e.g., nickel, that are commonly used as protective barriers in fluorine radical environments. The amount of hydrogen radicals delivered to the wafer is limited, so the equipment cannot achieve carbon removal functionality.

[0004] Second, it is a big challenge for conventional coatings to address both oxide removal and carbon removal in one tool using reactive fluorine and hydrogen, respectively. Fluorine, hydrogen, and coating materials can react with one chemical process to another, generating particles. To mitigate this issue, a seasoning step or dummy wafers may be required, which reduces throughput.

[0005] Third, certain coatings may not be able to withstand environments with temperatures exceeding 150°C. Because many preclean / etch processes can exceed temperatures of 150°C, these coatings may prove detrimental for use at high temperatures due to physical and chemical decomposition of the coating during the process. For example, plasma sprayed Y2O3 coatings will crack when heated to approximately 150°C, causing particle generation. Aluminum metal problems occur with wafers with anodized, PEO, and ALD Al2O3 coatings in reactive fluorine and reactive hydrogen chemical environments above 150°C.

[0006] Fourth, it can be difficult to uniformly apply coatings to parts with high aspect ratio features. For example, coatings applied by plasma spray processes may not be able to cover the high aspect holes of showerheads and gas distribution tunnels. Uncovered substrates can result in particle generation that can adversely affect films formed on semiconductor wafers.

[0007] As a result, in a system that delivers both reactive fluorine and reactive hydrogen species, it is desirable to have an ex-situ or in-situ coating that can efficiently deliver hydrogen radicals to the wafer while withstanding higher temperatures and harsh chemical environments, and that is applied with a uniform thickness and does not generate metals / particles when exposed to higher temperatures and harsh chemical environments. Summary of the Invention

[0008] This Summary is provided to introduce a selection of concepts in a simplified form. These concepts are described in more detail below in the Detailed Description of the Disclosure. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0009] According to at least one embodiment, a semiconductor film pre-clean / etch apparatus includes: a reaction chamber; a wafer holder within the reaction chamber configured to hold a semiconductor wafer; a gas delivery path configured to ensure gas delivery to the reaction chamber and uniform mixing of at least two gases; a gas distribution device for distributing gas across the semiconductor wafer; a gas manifold that assists in the delivery of hydrogen radicals to the wafer edge; and a remote plasma unit for converting a first gas provided by a first gas source into a radical gas, wherein at least one of the wafer holder, the reaction chamber, the gas delivery path, the gas distribution device, the gas manifold, or the remote plasma unit includes a coating of a first layer and a second layer, wherein at least one of the first layer or the second layer of the coating is formed by atomic layer deposition (ALD), and the first layer and the second layer include different materials.

[0010] In accordance with at least one embodiment, a method of forming a coating for a semiconductor film preclean / etch apparatus includes preparing a first surface to be coated, cleaning the first surface, depositing a first coating layer on the first surface by an atomic layer deposition (ALD) technique, depositing a second coating layer on the first coating layer to form a multi-layer coating, optionally repeating the steps of forming the first coating layer and forming the second coating layer, and performing a post-coating treatment on the composite coating, wherein the first coating layer comprises a different material than the second coating layer, and the semiconductor film deposition apparatus includes a wafer holder, a reaction chamber, a gas delivery path, a gas distribution system, a gas manifold, and a remote plasma unit, and the composite coating is disposed on at least one of the reaction chamber, the gas delivery path, the gas distribution system, the gas manifold, or the remote plasma unit. [Brief description of the drawings]

[0011] These and other features, aspects, and advantages of the inventions disclosed herein are described below with reference to drawings of certain specific embodiments, which are intended to be illustrative and not limiting of the invention.

[0012] [Figure 1] FIG. 1 is a cross-sectional view of a semiconductor film pre-clean apparatus with ex-situ coating in accordance with at least one embodiment of the present invention.

[0013] [Diagram 2] FIG. 2 is a cross-sectional view of a semiconductor film pre-clean apparatus with in-situ coating in accordance with at least one embodiment of the present invention.

[0014] [Diagram 3] 3A and 3B are cross-sectional views of example components including an enclosed space and a remote plasma unit, in accordance with at least one embodiment of the present invention.

[0015] [Figure 4] 4A and 4B are cross-sectional views of a component comprising a high aspect ratio feature, a gas distribution system, or a showerhead in accordance with at least one embodiment of the present invention.

[0016] [Diagram 5] FIG. 5 is a cross-sectional view of a component including a coating arrangement in accordance with at least one embodiment of the present invention.

[0017] [Figure 6] FIG. 6 is a cross-sectional view of a component including a coating arrangement in accordance with at least one embodiment of the present invention.

[0018] [Figure 7] FIG. 7 is a cross-sectional view of a component including a coating arrangement in accordance with at least one embodiment of the present invention.

[0019] [Figure 8] FIG. 8 is a flow chart illustrating an in-situ coating method in accordance with at least one embodiment of the present invention.

[0020] It will be appreciated that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale, for example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help improve understanding of the illustrated embodiments of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] Although several embodiments and examples are disclosed below, it will be understood by those skilled in the art that the present invention extends beyond the specifically disclosed embodiments and / or applications of the present invention, as well as obvious modifications and equivalents thereof. Therefore, it is not intended that the scope of the disclosed invention should be limited by the specifically disclosed embodiments described below.

[0022] The figures shown herein are not meant to be actual illustrations of any particular materials, structures or devices, but merely idealized representations used to describe embodiments of the present disclosure.

[0023] The term "atomic layer deposition" (ALD) as used herein can refer to a vapor deposition process in which a deposition cycle, preferably multiple consecutive deposition cycles, are performed in a process chamber. Typically, during each cycle, a precursor is chemisorbed to the deposition surface (e.g., the surface of a substrate or a surface of a previously deposited underlayer, such as a material deposited using a previous ALD cycle) to form a monolayer or submonolayer that does not readily react with additional precursors (i.e., a self-limiting reaction). If necessary, a reactant (e.g., another precursor or reactant gas) can then be introduced into the process chamber for use in converting the chemisorbed precursor to the desired material on the deposition surface. Typically, this reactant can further react with the precursor. Additionally, a purge step can be utilized during each cycle to remove excess precursor from the process chamber after conversion of the chemisorbed precursor and / or to remove excess reactants and / or reaction by-products from the process chamber. Additionally, the term "atomic layer deposition" as used herein is also meant to include processes indicated by related terms, such as, for example, "chemical vapor deposition atomic layer deposition," "atomic layer epitaxy" (ALE), molecular beam epitaxy (MBE), gas source MBE, or metalorganic MBE, as well as chemical beam epitaxy when performed with alternating pulses of precursor compositions, reactive gases, and purge (e.g., inert carrier) gases.

[0024] As used herein, the term "chemical vapor deposition" (CVD) can refer to any process in which a substrate is exposed to one or more volatile precursors that react and / or decompose on the substrate surface to produce a desired deposit.

[0025] 1 illustrates a semiconductor film pre-clean apparatus 100 with ex situ coating in accordance with at least one embodiment of the present invention. The semiconductor film pre-clean apparatus 100 includes a reaction chamber housing 110, a wafer holder or susceptor 120 configured to hold a semiconductor wafer 130, a gas distribution apparatus 140, a gas manifold 150, a gas delivery path 160, a remote plasma unit 170, a first gas source 180, a second gas source 190A, a third gas source 190B, and a fourth gas source 190C.

[0026] The remote plasma unit 170 converts the gas supplied by the first gas source 180 into a radical gas. An example of the radical gas is a gas that is used to remove a film, such as silicon oxide (SiO x ) or silicon germanium oxide (SiGeO x Fluorine radical gas used to remove carbon dioxide, etc., may be mentioned. To remove films such as silicon oxide or silicon germanium oxide, the second gas source 190A may supply a dilution gas or a reaction gas to the semiconductor wafer 130 along with the gas from the first gas source 180. The third gas source 190B may supply a gas that is activated by the remote plasma unit 170 to form hydrogen radical gas during the carbon removal process. The fourth gas source 190C may supply an inert gas that assists in ignition of the remote plasma unit 170 and may supply radicals to the wafer 130. The gas delivery path 160 ensures that a uniform mixture of gases from the first gas source 180 and the second gas source 190A is supplied to the reaction chamber 110. The gas distribution system or showerhead 140 distributes the gases uniformly across the surface of the semiconductor wafer 130. The gas manifold 150 may efficiently supply the radical gas generated from the third gas source 190B to the wafer edge to help improve the uniformity of the carbon removal.

[0027] 2 illustrates a semiconductor film pre-clean apparatus 200 with in-situ coating according to an embodiment of the present invention. The semiconductor film pre-clean apparatus 200 includes a reaction chamber housing 110, a wafer holder or susceptor 120 configured to hold a semiconductor wafer 130, a gas distribution apparatus 140, a gas manifold 150, a gas delivery path 160, a remote plasma unit 170, a first gas source 180, a second gas source 190A, a third gas source 190B, a fourth gas source 190C, a plurality of precursor sources 195A-195D, and a fifth gas source 195E.

[0028] Similar to the ex-situ coating apparatus 100, the in-situ coating apparatus 200 may add precursor and purge gas sources to enable in-situ coating capabilities. For example, a composite or dual-layer coating with ALD deposited alumina (Al2O3) and ALD deposited yttrium oxide (YO3), the in-situ coating apparatus 200 may include a trimethylaluminum (TMA) source 195A and a water (HO) source 195B for in-situ ALD deposited alumina coating. For in-situ ALD deposited yttrium oxide (as described in U.S. Pat. No. 7,351,658, which is incorporated herein by reference), the in-situ coating apparatus 200 may include an yttrium gas source 195C (e.g., Y(thd), CP3Y, or (CpCH3)3Y) and an oxygen gas source 195D (e.g., oxygen, ozone, a mixture of ozone and oxygen, or HO). Additionally, a purge gas source 195E may be connected upstream of the precursor gas sources (195A-195D) to remove excess precursor or precursor by-products after conversion of the chemisorbed precursor.

[0029] Several types of component structures may be beneficial in terms of coating methods. One type of structure is a component with an enclosed space, e.g., a remote plasma unit where radical gas is first generated. Due to plasma bombardment and corrosive chemical environments, remote plasma units may require coating. However, typical coating methods may be problematic or infeasible. For example, particles generated in typical RPU coatings, e.g., anodization and PEO, can migrate between the carbon removal and oxide removal processes. Plasma spraying cannot be coated due to the enclosed space and small gas inlet / outlet. Figures 3A and 3B show a representative remote plasma unit 300. The remote plasma unit 300 includes a body 310, a gas inlet 320, an RF generator 330, a gas outlet 340, and a coating 350. The coating 350 covers the inner walls of the body 310. Other parts of the remote plasma unit 300 may be covered with the coating 350. The coating 350 may be a ceramic coating, such as aluminum oxide (Al2O3), yttrium oxide (Y2O3), yttrium fluoride (YF3), yttrium oxide fluoride (YO x F y ), aluminum fluoride (AlF3), scandium oxide (Sc2O3), hafnium oxide (HfO2), lanthanum oxide (La2O3), samarium oxide (Sm2O3), gadolinium oxide (Gd2O3), erbium oxide (Er2O3), zirconium oxide (ZrO2), cerium oxide (CeO2), or any combination thereof.

[0030] The gas distribution system or showerhead 140, gas supply path 135, and gas manifold 190 are components that may be coated due to exposure to radical gases generated by the remote plasma unit 160. FIG. 4A illustrates another type of component with high aspect ratio holes, such as the gas distribution system or showerhead 140, in accordance with at least one embodiment of the present invention. The gas distribution system or showerhead 140 includes a showerhead body 410 and a number of holes 420. Gas flows through the number of holes 420 onto the semiconductor wafer 130. The number of holes 420 may be high aspect ratio features and may be different shapes, such as bevels and curves. The features may provide a large area of ​​surface that may generate particles from the bulk of the showerhead body 410.

[0031] 4B illustrates a gas distribution system or showerhead 140 incorporating a coating that prevents particle formation. A number of coatings 430 are applied to the number of holes 420. The number of coatings 430 may be a ceramic coating, such as aluminum oxide (Al2O3), yttrium oxide (Y2O3), yttrium fluoride oxide (Y2O3), or a combination of these. x F y ), yttrium fluoride (YF3), aluminum fluoride (AlF3), scandium oxide (Sc2O3), hafnium oxide (HfO2), lanthanum oxide (La2O3), samarium oxide (Sm2O3), gadolinium oxide (Gd2O3), erbium oxide (Er2O3), zirconium oxide (ZrO2), cerium oxide (CeO2), or any combination of the above. The multiple coatings 430 can also cover other parts of the showerhead body 410. Although FIGS. 4A and 4B illustrate one shape of the coating of the part, there can be more complex internal structures to which the coating can also be applied. This can include a gas delivery path 135 and a gas manifold 150 that can have holes and bends in its shape.

[0032] The coating of the part may preferably be a composite coating. Figure 5 illustrates one coating sequence 500. The coating sequence 500 comprises a part 510 to be coated. The part 510 may be made of a material including at least one of aluminum alloy, cast iron, stainless steel, Hastelloy, Inconel, nickel alloy, ceramic, ceramic coating, or metal coating. The part 510 is coated with a layer of a first coating 520, followed by a layer of a second coating 530, and the layers of the first coating 520 and the second coating 530 are repeated. At least one or both of the first coating 520 or the second coating 530 may be applied by atomic layer deposition (ALD) techniques. Advantages of using ALD techniques include the formation of sufficiently dense coatings while producing an isotropic microstructure. If only one coating is applied by ALD, the other coating may be applied by anodization, chemical vapor deposition (CVD), plasma vapor deposition (PVD), plasma spray coating, or plasma electrolytic oxidation (PEO). Repeating of layers may be done as desired or required.

[0033] The first coating 520 may be aluminum oxide (Al2O3), yttrium oxide (Y2O3), yttrium fluoride (YF3), yttrium oxide fluoride (YO x F y The second coating 530 may include one of aluminum oxide (Al2O3), yttrium oxide (YO3), yttrium fluoride (YF3), yttrium oxide fluoride (YO2), yttrium oxide (YO2), yttrium fluoride (YF3), yttrium oxide (YO2 ... x F y), aluminum fluoride (AlF3), scandium oxide (Sc2O3), hafnium oxide (HfO2), lanthanum oxide (La2O3), samarium oxide (Sm2O3), gadolinium oxide (Gd2O3), erbium oxide (Er2O3), zirconium oxide (ZrO2), or cerium oxide (CeO2). The first coating 420 and the second coating 530 ideally do not comprise the same material.

[0034] FIG. 6 illustrates a coating sequence 600 according to at least one embodiment of the present invention. The coating sequence 600 comprises a part 610 to be coated. The part 610 may be made of a material including at least one of an aluminum alloy, cast iron, stainless steel, Hastelloy, Inconel, nickel alloy, ceramic, ceramic coating, or metal coating. The part 610 is coated with a layer of a first coating 620 followed by a layer of a second coating 630. At least one or both of the first coating 620 or the second coating 630 may be applied by an atomic layer deposition (ALD) technique. If only one coating is performed by ALD, the other coating may be performed by anodization, chemical vapor deposition (CVD), plasma vapor deposition (PVD), plasma spray coating, or plasma electrolytic oxidation (PEO). The coating can extend to three or more layers of different ALD coatings (e.g., yttrium oxide and aluminum oxide) or can comprise only one layer of coating (e.g., yttrium oxide). Repeating of layers may be done as desired or required.

[0035] The first coating 620 may be aluminum oxide (Al2O3), yttrium oxide (Y2O3), yttrium fluoride (YF3), yttrium oxide fluoride (YO x F yThe second coating 630 may include one of aluminum oxide (Al2O3), yttrium oxide (YO3), yttrium fluoride oxide (Y2O3), yttrium oxide fluoride (Y2O ... x F y ), yttrium fluoride (YF3), aluminum fluoride (AlF3), scandium oxide (Sc2O3), hafnium oxide (HfO2), lanthanum oxide (La2O3), samarium oxide (Sm2O3), gadolinium oxide (Gd2O3), erbium oxide (Er2O3), zirconium oxide (ZrO2), or cerium oxide (CeO2). The first coating 620 and the second coating 630 ideally do not comprise the same material.

[0036] FIG. 7 illustrates a coating sequence 700 according to at least one embodiment of the present invention. The coating sequence 700 comprises a part 710 to be coated. The part 710 may be made of a material including at least one of an aluminum alloy, cast iron, stainless steel, Hastelloy, Inconel, nickel alloy, ceramic, ceramic coating, or metal coating. The part 710 is coated with a layer of a first coating 720, followed by a layer of a second coating 730, and a layer of a third coating 740. At least one or all of the layers of the first coating 720, the second coating 730, and the third coating 740 may be applied by atomic layer deposition (ALD) techniques. If only one coating is performed by ALD, the other coatings may be performed by anodization, chemical vapor deposition (CVD), plasma vapor deposition (PVD), plasma spray coating, or plasma electrolytic oxidation (PEO). The coating may extend to more than two layers of different ALD coatings, or may comprise only one layer of coating. Repeating layers may be performed as desired.

[0037] The first coating 720 may be aluminum oxide (Al2O3), yttrium oxide (Y2O3), yttrium fluoride (YF3), yttrium oxide fluoride (YO x F y ), aluminum fluoride (AlF3), scandium oxide (Sc2O3), hafnium oxide (HfO2), lanthanum oxide (La2O3), samarium oxide (Sm2O3), gadolinium oxide (Gd2O3), erbium oxide (Er2O3), zirconium oxide (ZrO2), or cerium oxide (CeO2). The second coating 730 may include one of aluminum oxide (Al2O3), yttrium oxide (YO3), yttrium fluoride oxide (Y2O ... x F yThe third coating 740 may include one of aluminum oxide (Al2O3), yttrium oxide (YO3), yttrium fluoride (YF3), aluminum fluoride (AlF3), scandium oxide (Sc2O3), hafnium oxide (HfO2), lanthanum oxide (La2O3), samarium oxide (Sm2O3), gadolinium oxide (Gd2O3), erbium oxide (Er2O3), zirconium oxide (ZrO2), or cerium oxide (CeO2). x F y ), yttrium fluoride (YF3), aluminum fluoride (AlF3), scandium oxide (Sc2O3), hafnium oxide (HfO2), lanthanum oxide (La2O3), samarium oxide (Sm2O3), gadolinium oxide (Gd2O3), erbium oxide (Er2O3), zirconium oxide (ZrO2), or cerium oxide (CeO2). The first coating 720, the second coating 730, and the third coating 740 ideally do not include the same material, e.g., yttrium oxide, hafnium oxide, and aluminum oxide.

[0038] Coating a part may require several steps. FIG. 8 illustrates a method 800 for performing the coating. The method 800 includes a surface preparation step 810, a cleaning step 820, a coating step 830, and a post-coating treatment step 840. The substrate preparation step 810 can include steps to ensure an optimized coating, including removing sharp edges that may cause stress on the coating, tight gap tolerances, and optimizing small hole designs to reduce localized non-uniform coating defects or Newton rings caused by precursor entrapment during ALD coating. The part can be treated by texturing, polishing, and / or electropolishing to improve coating adhesion and ensure good coating quality.

[0039] The cleaning step 820 may depend on the part being coated. The cleaning step 820 may remove surface carbon, particles, and excess metal from the part. The cleaning step 820 may include alkaline, acid, electrolytic cleaning, and / or ozone treatment steps, etc. By performing the cleaning step 820, the coating uniformity and surface coverage may be optimized.

[0040] The coating step 830 can include forming at least one coating layer by an ALD technique. The ALD technique can be performed in situ or ex situ. An exemplary method can be forming a first layer of aluminum oxide and a second layer of yttrium oxide by an ALD process (as described in U.S. Pat. No. 7,351,658, incorporated herein by reference). The thickness of the aluminum oxide on the gas distribution apparatus or showerhead can range from 1 to 10,000 nm, 10 to 2,500 nm, or 100 to 500 nm. If the yttrium oxide is deposited as a coating on the gas distribution apparatus or showerhead, the thickness of the yttrium oxide can range from 1 to 10,000 nm, 10 to 2,500 nm, or 100 to 500 nm. The thickness of the aluminum oxide on the remote plasma unit can range from 1 to 50,000 nm, 10 to 25,000 nm, or 100 to 10,000 nm. When the yttrium oxide is deposited on a remote plasma unit, the thickness of the yttrium oxide can range from 1 to 50,000 nm, from 10 to 25,000 nm, or from 100 to 10,000 nm.

[0041] Coatings formed by the above methods can be reliably used in processes operating at temperatures above 150°C. Furthermore, the aluminum oxide layer may improve the coating quality at the interface of the coated part compared to yttrium oxide. And the aluminum oxide layer may reduce the stress in the yttrium oxide layer due to thermal expansion, thereby reducing the possibility of cracking of the yttrium oxide. The aluminum oxide layer may also be efficient in preventing migration of metals, such as magnesium and sodium, to the surface.

[0042] The coating post-treatment step 840 can include improving the quality or properties of the coating. Examples include fluorinating or chlorinating the surface of the coating to better accommodate fluorine or chlorine containing environments. In addition, the coating post-treatment step 840 can include annealing the surface to remove internal stresses and defects. Furthermore, by heating to a specific temperature, binary or ternary ceramics can be achieved. For example, a composite coating of Al2O3 and Y2O3 can be transformed into yttrium aluminum garnet (YAG) or yttrium aluminum monoclinic (YAM) after high temperature treatment with a specific ratio of Al2O3 and Y2O3.

[0043] The particular embodiments shown and described are illustrative of the present invention and its best mode and are not intended to limit the scope of the other aspects and embodiments in any way. Indeed, for the sake of brevity, conventional manufacturing, association, preparation, and other functional aspects of the system may not be described in detail. Moreover, the connecting lines shown in the various figures are intended to represent example functional relationships and / or physical couplings between the various elements. Many alternative or additional functional relationships or physical connections may be present in an actual system and / or may not be present in some embodiments.

[0044] It should be understood that the configurations and / or methods described herein are exemplary in nature, and that these specific embodiments or examples are not to be construed in a limiting sense, as numerous variations are possible. The specific routines or methods described herein may represent one or more of any number of processing strategies. Thus, the various illustrated operations may be performed in the illustrated sequence, in other sequences, or may be omitted in some cases.

[0045] The subject matter of the present disclosure includes all novel and non-obvious combinations and subcombinations of the various process, system, and configurations, as well as other features, functions, operations and / or properties disclosed herein, and any and all equivalents thereof.

Claims

1. A semiconductor film pre-clean / etch apparatus comprising: A reaction chamber; a wafer holder within the reaction chamber configured to hold a semiconductor wafer; a gas delivery path configured to deliver gas to the reaction chamber and ensure uniform mixing of at least two gases; a gas distribution device for dispersing gas across the semiconductor wafer; a gas manifold that assists in the delivery of hydrogen radicals to the wafer edge; a remote plasma unit for converting a first gas supplied by a first gas source into a radical gas; the gas manifold includes a first layer and a second layer coating; at least one of the wafer holder, the reaction chamber, the gas delivery path, the gas distribution device, or the remote plasma unit includes the coating of the first layer and the second layer; at least one of the first layer or the second layer of the coating is formed by atomic layer deposition (ALD); The first layer is made of aluminum oxide (Al ２ O ３ ), The second layer is made of yttrium oxide (Y ２ O ３ ).

2. The apparatus of claim 1 , wherein the first layer is on the gas distribution device, and the first layer has a thickness in the range of 1 to 10,000 nm, 10 to 2,500 nm, or 100 to 500 nm.

3. The apparatus of claim 1 , wherein the second layer is on the gas distribution device, and the thickness of the second layer is in the range of 1 to 10,000 nm, 10 to 2,500 nm, or 100 to 500 nm.

4. 2. The apparatus of claim 1, wherein the first layer is on the remote plasma unit, and the first layer has a thickness in the range of 1 to 50,000 nm, 10 to 25,000 nm, or 100 to 10,000 nm.

5. 2. The apparatus of claim 1, wherein the second layer is on the remote plasma unit, and the thickness of the second layer is in the range of 1 to 50,000 nm, 10 to 25,000 nm, or 100 to 10,000 nm.

6. The apparatus of claim 1 , wherein both the first layer and the second layer are formed by ALD.

7. 10. The apparatus of claim 1, wherein the first layer is formed by ALD and the second layer is formed by at least one of anodization, chemical vapor deposition (CVD), plasma vapor deposition (PVD), plasma spray coating, or plasma electrolytic oxidation (PEO).

8. 10. The apparatus of claim 1, wherein the first layer and the second layer form a composite coating on at least one of the wafer holder, the reaction chamber, the gas delivery path, the gas distribution system, the gas manifold, or the remote plasma unit.

9. 10. The apparatus of claim 8, wherein the formation of the composite coating is repeated several times on at least one of the wafer holder, the reaction chamber, the gas delivery path, the gas distribution device, the gas manifold, or the remote plasma unit.

10. 1. A method of forming a coating for a semiconductor film preclean / etch apparatus, comprising: Providing a first surface to be coated; cleaning the first surface; depositing a first coating layer on the first surface by atomic layer deposition (ALD) techniques; depositing a second coating layer over the first coating layer to form a multi-layer coating; and performing a post-coating treatment on the multi-layer coating, The semiconductor film pre-cleaning / etching apparatus comprises a wafer holder, a reaction chamber, a gas delivery path, a gas distribution device, a gas manifold, and a remote plasma unit; the multi-layer coating is deposited on the gas manifold; the multi-layer coating is deposited on at least one of the wafer holder, the reaction chamber, the gas delivery path, the gas distribution device, or the remote plasma unit; The first coating layer is made of aluminum oxide (Al ２ O ３ ), The second coating layer is made of yttrium oxide (Y ２ O ３ ).

11. 11. The method of claim 10, wherein depositing the second coating layer is performed by at least one of anodization, chemical vapor deposition (CVD), plasma vapor deposition (PVD), plasma spray coating, or plasma electrolytic oxidation (PEO).

12. The method of claim 10, wherein the first coating layer is on the gas distribution device, and the first coating layer has a thickness in the range of 1 to 10,000 nm, 10 to 2,500 nm, or 100 to 500 nm.

13. The method of claim 10, wherein the second coating layer is on the gas distribution device, and the thickness of the second coating layer ranges from 1 to 10,000 nm, 10 to 2,500 nm, or 100 to 500 nm.

14. 11. The method of claim 10, wherein the first coating layer is on the remote plasma unit, and the thickness of the first coating layer ranges from 1 to 50,000 nm, 10 to 25,000 nm, or 100 to 10,000 nm.

15. 11. The method of claim 10, wherein the second coating layer is on the remote plasma unit, and the thickness of the second coating layer ranges from 1 to 50,000 nm, 10 to 25,000 nm, or 100 to 10,000 nm.

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