Apparatus and method for selectively etching silicon oxide films

Abstract

Apparatuses and methods for selectively etching specific layers are disclosed. The apparatuses and methods are designed to maintain an etch rate of specific layers while maintaining unetched layers intact. A gas mixture can flow onto a substrate, for example, in individual cycles with an oxide layer and an oxynitride layer as etched layers and a nitride layer as a non-etched layer. In the above example, the resulting gas mixture reacts with the specific layers, resulting in etching the oxide layer and the oxynitride layer while maintaining the nitride layer.

Description

Technical Field

[0001] This disclosure generally relates to an apparatus for processing semiconductor wafers. More specifically, this disclosure relates to apparatus and methods for selectively etching specific films (such as silicon oxide) on a semiconductor wafer while keeping another film intact. Background Technology

[0002] In the process of forming semiconductor devices, multiple films may be formed. For example, silicon nitride and silicon oxide films can be deposited on a patterned wafer.

[0003] Some applications may require a patterned wafer with a specific film (such as silicon nitride) while simultaneously removing another film. These may include logic and memory applications. In these cases, failure to remove one film (such as silicon oxide) can lead to device failure. Additionally, the process of removing the silicon oxide film may cause the silicon nitride film to thin, become damaged, or be removed, thereby reducing the device's ability to store charge, which may prove critical for performance in applications such as memory.

[0004] As a result, there is a need for devices and methods that can selectively etch a particular film onto another film. Summary of the Invention

[0005] According to at least one embodiment of the present invention, a method for selectively etching a film (e.g., a film for forming a semiconductor device) deposited on a substrate is disclosed. The method includes: providing a substrate in a reaction chamber of a semiconductor processing device, wherein the substrate has an oxide layer, a nitride layer, and an oxynitride layer; performing a first etching process, wherein the first etching process includes flowing a hydrogen precursor gas, a fluorine precursor gas, and an inert gas onto the substrate; performing a second etching process, wherein the second etching process includes flowing a hydrogen precursor gas, a fluorine precursor gas, and an inert gas onto the substrate; wherein the first etching process is repeated a predetermined number of times, and the first etching process removes the oxynitride layer from the substrate while maintaining the nitride layer substantially intact; and wherein the second etching process is repeated a predetermined number of times, and the second etching process removes the oxide layer from the substrate while maintaining the nitride layer substantially intact.

[0006] According to at least one embodiment of the present invention, a system for selectively etching a film disposed on a substrate is disclosed. The system includes: a reaction chamber configured to hold and process the substrate, wherein the substrate has an oxide layer, a nitride layer, and an oxynitride layer; a fluorine precursor source configured to provide a fluorine precursor gas, the fluorine precursor gas comprising at least one of: nitrogen trifluoride (NF3); carbon tetrafluoride (CF4); sulfur hexafluoride (SF6); hydrogen fluoride (HF); hydrofluoric acid (HF) with water vapor; or fluorine gas (F2); and a hydrogen precursor source configured to provide a hydrogen precursor gas, the hydrogen precursor gas comprising... The method comprises at least one of the following: ammonia (NH3); hydrazine (N2H4); urea (NH2CONH2); or hydrogen (H2); and an inert gas source configured to provide an inert gas, wherein the inert gas comprises at least one of the following: argon; krypton; helium; xenon; or nitrogen; wherein a gaseous mixture of the fluorine precursor gas, the hydrogen precursor gas, and the inert gas is flowed onto the substrate to etch the oxide layer and the oxynitride layer during the etching process while keeping the nitride layer intact.

[0007] This summary is provided to present the selected concepts in a simplified form. These concepts are further described in detail in the following detailed description of exemplary embodiments of this disclosure. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter. Attached Figure Description

[0008] These and other features, aspects, and advantages of the invention disclosed herein are described below with reference to the accompanying drawings of certain embodiments, which are intended to illustrate and not limit the invention.

[0009] Figure 1A-1D This is a cross-sectional view of a semiconductor device according to at least one embodiment of the present invention.

[0010] Figure 2 This is a flowchart of a method for selectively etching a film according to at least one embodiment of the present invention.

[0011] Figure 3 This is a schematic diagram of a semiconductor processing system according to at least one embodiment of the present invention.

[0012] Figure 4 This is a schematic diagram of a semiconductor processing system according to at least one embodiment of the present invention.

[0013] It will be understood that the elements in the accompanying drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some elements in the figures may be enlarged relative to other elements to aid in understanding the embodiments illustrated in this disclosure. Detailed Implementation

[0014] Although certain embodiments and examples are disclosed below, those skilled in the art will understand that the invention extends beyond the specific disclosed embodiments and / or uses of the invention and their obvious modifications and equivalents. Therefore, it is intended that the scope of the disclosed invention should not be limited to the specific disclosed embodiments described below.

[0015] The illustrations presented herein are not intended to be actual views of any particular material, structure, or device, but are merely idealized representations used to describe embodiments of this disclosure.

[0016] Various embodiments relate to cleaning processes for removing silicon oxide, germanium oxide, or metal oxide materials from exposed surfaces of a substrate. Embodiments may also be used with at least one of: silicon; metals in elemental form; alloys of various metals; oxides associated with alloys of various metals; silicon; or germanium. It will be understood that the resulting clean surface will allow for the formation of high-quality semiconductor layers, such as epitaxially grown silicon.

[0017] Figure 1A A semiconductor device 100 is shown before undergoing a cleaning process. The semiconductor device 100 includes a substrate 110; an intermediate layer 120; a nitride layer 130; and an oxide layer 140. The substrate 110 may include at least one of silicon or silicon-germanium. The intermediate layer 120 may include a dielectric layer, such as silicon nitride, silicon carbonitride, or silicon boron nitride. The intermediate layer 120 may also include other materials, such as silicon carbide or silicon carbide oxide. The nitride layer 130 may include silicon nitride or a metal nitride, such as aluminum nitride. The oxide layer 140 may include at least one of the following: silicon oxide; germanium oxide; aluminum oxide; cobalt oxide; or, for example, tungsten oxide.

[0018] For example, the layer can be formed by epitaxial deposition, chemical vapor deposition (CVD), atomic layer deposition (ALD), plasma-enhanced atomic layer deposition (PEALD), or plasma-enhanced chemical vapor deposition (PECVD). It is desirable that the cleaning process completely removes or eliminates the target thickness of the oxide layer 140, while maintaining the integrity of the nitride layer 130, the intermediate layer 120, and the substrate 110. Such a result... Figure 1D As shown in the image.

[0019] Figure 1B The semiconductor device 100 is shown after a period of time in the reaction chamber. This period can be between the initial deposition of the nitride layer 130 and the etching step of the oxide layer 140. This period is unavoidable due to the complexities involved in manufacturing integrated circuits. During this period, the semiconductor device 100 is exposed to the environment surrounding the reaction chamber.

[0020] Semiconductor device 100 is exposed to the surrounding environment, causing oxidation of nitride layer 130, thereby forming oxynitride layer 150. The longer the oxidation occurs, the thicker oxynitride layer 150 may become. Compared to keeping the nitride layer unoxidized, the oxynitride layer 150 results in greater loss of nitride layer 130.

[0021] Protecting the nitride layer 130 is ideal because it can be a critical part of an integrated circuit, or it can be a mask layer used to protect another layer on a patterned substrate. The presence of the oxynitride layer 150 may prove problematic because its removal is facilitated by an autocatalytic reaction promoted by byproduct water (H2O) molecules formed on the substrate surface. If etching is not stopped after removing the oxynitride layer 150, the presence of these water molecules can lead to undesirable etching of the nitride layer 130. Therefore, the etching step of the oxynitride layer 150 can be stopped, and a baking step can be used to remove the byproduct water (H2O) molecules in order to preserve the nitride layer 130.

[0022] Figure 1C The semiconductor device 100 is shown after a first etch process cycle. Ideally, the first etch process cycle removes all of the oxynitride layer 150 and a portion of the oxide layer 130. It can be demonstrated that a portion of the nitride layer 130 is also removed, but the removal of the nitride layer 130 is expected to be limited.

[0023] Figure 1D The semiconductor device 100 is shown after a second etch process cycle. The second etch process cycle ideally removes the remaining portion of the oxide layer 130. Furthermore, it can be demonstrated that a portion of the nitride layer 130 is removed, but the removal of the nitride layer 130 is expected to be limited.

[0024] Figure 2 An etching process 200 is shown, which may include: (1) a step 210 of providing a substrate in a reaction chamber; (2) a step 220 of a first etching process; (3) an optional light baking step 230; (4) a step 250 of a second etching process; (5) an optional light baking step 260; and (6) a step 280 of performing additional treatment on the substrate.

[0025] Step 240 of the first etching process can be repeated to perform the first etching process 220 and optional light baking 230 again. The first etching process 220, optional light baking 230, and the first etching process repetition step 240 together constitute a first etching process cycle. The first etching process repetition step 240 can be performed multiple times. Similarly, step 270 of the second etching process can be repeated to perform the second etching process 250 and optional light baking 260 again. The second etching process 250, optional light baking 260, and second etching process repetition step 270 together constitute a second etching process cycle. The second etching process repetition step 270 can also be performed multiple times.

[0026] Step 210 can be performed in a reaction chamber used for epitaxial deposition, chemical vapor deposition (CVD), atomic layer deposition (ALD), plasma-enhanced atomic layer deposition (PEALD), or plasma-enhanced chemical vapor deposition (PECVD). Step 210 can also be performed in a vertical furnace. The deposition step can be performed after the substrate arrives in the reaction chamber and before the first etching process 220, thereby depositing a film on the substrate. For example, the deposition step can result in the formation of a nitride layer 130 or an oxide layer 140 on the substrate.

[0027] For the removal of oxide layer 140 and oxynitride layer 150, the first etching process 220 may include introducing a combination of gases into the reaction chamber. The combination of gases may include fluorine gas, hydrogen gas, and inert gas. The combination of gases may include activated or radical forms of the gases listed above. Fluorine gas may include at least one of the following: nitrogen trifluoride (NF3); carbon tetrafluoride (CF4); sulfur hexafluoride (SF6); hydrogen fluoride (HF); hydrofluoric acid with water vapor (HF); or fluorine gas (F2). Inert gas may include at least one of the following: argon (Ar); krypton (Kr); helium (He); xenon (Xe); or nitrogen (N2). Hydrogen gas may include at least one of the following: ammonia (NH3); hydrazine (N2H4); urea (NH2CONH2); hydrogen (H2); alcohols, such as methanol, ethanol, propanol, or isopropanol; acidic gases, such as formic acid (HCOOH), acetic acid (CH3COOH), or acidic anhydrides; or mixtures thereof.

[0028] In one embodiment of the invention, the fluorine gas and the inert gas can be activated by a remote plasma unit (RPU) before being combined with the hydrogen gas. In another embodiment of the invention, the fluorine gas, the inert gas, and the hydrogen gas can be combined in a gas manifold before flowing into the reaction chamber.

[0029] The first etching process 220 may have settings that facilitate the removal of the oxynitride layer 150. For example, the reaction chamber may be set to a temperature range of -20°C to 150°C, 0°C to 100°C, or 5°C to 65°C. The duration of the first etching process 220 may be 1 to 30 seconds, 3 to 20 seconds, or 3 to 10 seconds. During the first etching process 220, the pressure in the reaction chamber may be 0.1 to 600 Torr, 0.5 to 50 Torr, or 0.5 to 4 Torr.

[0030] A light baking step (optional) 230 may be performed after the first etching process 220. The first etching process 220 may result in the formation of reaction byproducts that need to be removed. For example, water (H2O) molecules may form on the surface of the substrate during the first etching process 220. The light baking step 230 will remove H2O molecules that may potentially interfere with subsequent processing steps.

[0031] During the light baking step 230, an inert gas may flow into the reaction chamber. The inert gas may include at least one of the following: argon (Ar); krypton (Kr); helium (He); xenon (Xe); or nitrogen (N2). Additionally, the reaction chamber may be configured with a temperature range of 50°C to 400°C, 75°C to 300°C, or 90°C to 250°C. The duration of the light baking step 230 may be 5 to 120 seconds, 10 to 60 seconds, or 10 to 30 seconds.

[0032] To remove the oxide layer 140 while maintaining the integrity of the nitride layer 130, the second etching process 250 may include introducing a combination of gases into the reaction chamber. The combination of gases may include fluorine gas, hydrogen gas, and an inert gas. The combination of gases may include activated or radical forms of the gases listed above. The fluorine gas may include at least one of the following: nitrogen trifluoride (NF3); carbon tetrafluoride (CF4); sulfur hexafluoride (SF6); hydrogen fluoride (HF); hydrofluoric acid with water vapor (HF); or fluorine gas (F2). The inert gas may include at least one of the following: argon (Ar); krypton (Kr); helium (He); xenon (Xe); or nitrogen (N2). Hydrogen gas may include at least one of the following: ammonia (NH3); hydrazine (N2H4); urea (NH2CONH2); hydrogen (H2); alcohols, such as methanol, ethanol, propanol or isopropanol; acidic gases, such as formic acid (HCOOH), acetic acid (CH3COOH) or acidic anhydrides; or mixtures thereof.

[0033] In one embodiment of the invention, the fluorine gas and the inert gas can be activated by a remote plasma unit (RPU) before being combined with the hydrogen gas. In another embodiment of the invention, the fluorine gas, the inert gas, and the hydrogen gas can be combined in a gas manifold before flowing into the reaction chamber.

[0034] The second etching process 250 may have settings that promote the removal of the oxide layer 140. For example, the reaction chamber may be set to a temperature range of -20°C to 150°C, 0°C to 100°C, or 5°C to 65°C. The duration of the second etching process 250 may be 5 to 120 seconds, 5 to 60 seconds, or 5 to 30 seconds. The duration of the second etching process 250 may be longer than that of the first etching process 220 in order to result in a greater etching rate of the desired film (in this case, the oxide film 140). During the second etching process 250, the pressure in the reaction chamber may be 0.1 to 600 Torr, 0.5 to 50 Torr, or 0.5 to 4 Torr.

[0035] A light baking step (optional) 260 may be performed after the second etching process 250. The second etching process 250 may result in the formation of reaction byproducts that need to be removed. During the second etching process 250, water (H2O) molecules are not expected to form on the surface of the substrate; however, other byproducts, such as non-catalytic reaction byproducts, may form. The light baking step 260 will remove these byproducts (and any water molecules that may be present) that could potentially interfere with subsequent processing steps.

[0036] During the light baking step 260, an inert gas may flow into the reaction chamber. The inert gas may include at least one of the following: argon (Ar); krypton (Kr); helium (He); xenon (Xe); or nitrogen (N2). Additionally, the reaction chamber may be configured with a temperature range of 50°C to 400°C, 75°C to 300°C, or 90°C to 250°C. The duration of the light baking step 260 may be 5 to 120 seconds, 10 to 60 seconds, or 10 to 30 seconds.

[0037] The first etching process repeat step 240 can be repeated a different number of times compared to the second etching process repeat step 270. This may be because it is necessary to remove oxynitride layer 150 and oxide layer 140 of different thicknesses from the substrate. By separating the first etching process repeat step 240 from the second etching process repeat step 270, greater selectivity in etching oxide layer 140 over nitride layer 130 can be achieved. For example, the etching process according to at least one embodiment of the invention can achieve an etching ratio greater than 8:1, greater than 16:1, or greater than 40:1 (etching oxide layer: etching nitride layer).

[0038] According to another embodiment of the invention, when it is necessary to remove an oxide layer 140 of a certain thickness for a specific application, the selectivity of the etching process can be limited in a manner that minimizes the removal of the nitride layer 130. The etching process according to the invention can reduce the loss in the nitride layer 130 by a percentage greater than 20%, greater than 50%, or greater than 80% relative to the entire oxynitride layer 150 and nitride layer.

[0039] After step 270 of the second etching process is completed, the substrate may undergo further processing in step 280 for performing additional processing. Additional processing step 280 may include deposition processes such as epitaxial deposition, chemical vapor deposition (CVD), atomic layer deposition (ALD), plasma-enhanced atomic layer deposition (PEALD), or plasma-enhanced chemical vapor deposition (PECVD). Alternatively, additional processing step 280 may include different etching processes to potentially remove different materials; for example, different etching processes may be used to remove carbon-containing layers.

[0040] According to at least one embodiment of the present invention, Figure 3 A substrate processing system 300 is disclosed. The substrate processing system 300 includes: a reaction chamber 310; a remote plasma unit 320; a fluorine precursor source 330A; an inert gas source 330B; a hydrogen precursor source 330C; a channel 340 disposed between the remote plasma unit 320 and the reaction chamber 310; and a plurality of gas lines 350A-350C connecting the gas sources 330A-330C to the remote plasma unit 320 and the channel 340.

[0041] The reaction chamber 310 includes: a substrate holder 310A configured to hold a substrate to be processed; and a spray head 310B for distributing gas onto the substrate. The substrate holder 310A may have the ability to control its temperature between different portions. A fluorine precursor source 330A and an inert gas source 330B provide the gas activated by the remote plasma unit 320. The remote plasma unit 320 may be manufactured by MKS Instruments, Inc. or Advanced Energy Industries, Inc.

[0042] According to at least one embodiment of the present invention, Figure 4 A substrate processing system 400 is disclosed. The substrate processing system 400 includes: a reaction chamber 410; a gas manifold 420; a fluorine precursor source 430A; a hydrogen precursor source 430B; an inert gas source 430C; a channel 440 disposed between the gas manifold 420 and the reaction chamber 410; and a plurality of gas lines 450A-450C connecting the gas sources 430A-430C to the gas manifold 420.

[0043] The reaction chamber 410 includes: a substrate holder 410A configured to hold a substrate to be processed; and a spray head 410B for distributing gas onto the substrate. A gas manifold 420 receives gases from different sources 430A-430C and mixes them before they enter the reaction chamber 410. The substrate holder 410A may have the ability to control its temperature between different sections.

[0044] In an exemplary process according to at least one embodiment of the present invention, a substrate may have a silicon oxide film and a silicon nitride film deposited thereon. The silicon nitride film may be a critical portion of an integrated circuit or a mask layer to protect another layer on a patterned substrate. During processing steps, the top of the silicon nitride layer may be exposed to the surrounding environment, thereby converting a portion of the silicon nitride layer into a silicon oxynitride layer. The process according to at least one embodiment of the present invention can be used to remove the silicon oxide layer and the silicon oxynitride layer, while keeping the silicon nitride layer intact.

[0045] The specific embodiments shown and described are illustrative of the invention and its best mode, and are not intended to limit the scope of these aspects and embodiments in any way or otherwise. In fact, for the sake of brevity, conventional manufacturing, connection, fabrication, and other functional aspects of the system may not be described in detail. Furthermore, the connecting lines shown in the various figures are intended to represent exemplary functional relationships and / or physical connections between the various elements. Many alternative or additional functional relationships or physical connections may exist in actual systems, and / or may not exist in some embodiments.

[0046] It should be understood that the configurations and / or methods described herein are exemplary in nature, and these specific embodiments or examples should not be considered limiting, as many variations are possible. The specific routines or methods described herein may represent one or more of any number of processing strategies. Therefore, the various actions shown may be performed in the order shown, in a different order, or in some cases may be omitted.

[0047] The subject matter of this disclosure includes all novel and non-obvious combinations and sub-combinations of the various processes, systems and configurations disclosed herein, as well as any and all equivalents thereof.

Claims

1. A method for selectively etching a film disposed on a substrate, the method comprising: A substrate is provided in the reaction chamber of a semiconductor processing device, wherein the substrate has an oxide layer, a nitride layer and an oxynitride layer; Perform a first etching process, wherein the first etching process includes flowing hydrogen precursor gas, fluorine precursor gas and inert gas onto the substrate; Perform a second etching process, wherein the second etching process includes flowing hydrogen precursor gas, fluorine precursor gas and inert gas onto the substrate; The first etching process is repeated a predetermined number of times, and the first etching process removes the entire portion of the oxide nitride layer and a portion of the oxide layer from the substrate while keeping the nitride layer substantially intact; and The second etching process is repeated a predetermined number of times, and the second etching process removes the remaining portion of the oxide layer from the substrate while keeping the nitride layer substantially intact.

2. The method according to claim 1, wherein, The first etching process also includes performing a baking step on the substrate.

3. The method according to claim 1, wherein, The second etching process also includes performing a baking step on the substrate.

4. The method according to claim 1, wherein, The hydrogen precursor gas includes at least one of the following: ammonia (NH3); hydrazine (N2H4); or urea (NH2CONH2).

5. The method according to claim 1, wherein, The fluorine precursor gas includes at least one of the following: nitrogen trifluoride (NF3); carbon tetrafluoride (CF4); sulfur hexafluoride (SF6); hydrogen fluoride (HF); or fluorine (F2).

6. The method according to claim 1, wherein, The hydrogen precursor gas includes at least one of the following: hydrogen (H2); hydrogen chloride (HCl); water (H2O); alcohol; acidic gas or a mixture of the above.

7. The method according to claim 6, wherein, The alcohols include methanol, ethanol, propanol, or isopropanol.

8. The method according to claim 6, wherein, The acidic gases include formic acid (HCOOH), acetic acid (CH3COOH), or acidic anhydrides.

9. The method according to claim 1, wherein, The oxide layer includes at least one of the following: silicon oxide; germanium oxide; aluminum oxide; cobalt oxide; tungsten oxide.

10. The method according to claim 9, wherein, The oxide layer contains silicon, germanium, aluminum, cobalt, or tungsten.

11. The method according to claim 1, wherein, The nitride layer includes at least one of the following: silicon nitride; metal nitride.

12. The method according to claim 11, wherein, The metal nitrides include aluminum nitride.

13. The method according to claim 1, wherein, The inert gas includes at least one of the following: argon; krypton; helium; xenon; or nitrogen.

14. The method according to claim 1, wherein, The duration of the first etching process ranges from 1 to 30 seconds.

15. The method according to claim 14, wherein, The duration of the first etching process ranges from 3 to 20 seconds.

16. The method of claim 14, wherein, The duration of the first etching process ranges from 3 to 10 seconds.

17. The method according to claim 1, wherein, The temperature range of the first etching process is between -20°C and 150°C.

18. The method according to claim 17, wherein, The temperature range of the first etching process is between 0°C and 100°C.

19. The method according to claim 17, wherein, The temperature range for the first etching process is between 5°C and 65°C.

20. The method according to claim 1, wherein, The pressure range for the first etching process is between 0.1 and 600 Torr.

21. The method according to claim 20, wherein, The pressure range for the first etching process is between 0.5 and 50 Torr.

22. The method according to claim 20, wherein, The pressure range for the first etching process is between 0.5 and 4 Torr.

23. The method according to claim 1, wherein, The duration of the second etching process ranges from 5 to 120 seconds.

24. The method according to claim 23, wherein, The duration of the second etching process is between 5 and 60 seconds.

25. The method according to claim 23, wherein, The duration of the second etching process is between 5 and 30 seconds.

26. The method according to claim 1, wherein, The temperature range for the second etching process is between -20°C and 150°C.

27. The method according to claim 26, wherein, The temperature range for the second etching process is between 0°C and 100°C.

28. The method according to claim 26, wherein, The temperature range for the second etching process is between 5°C and 65°C.

29. The method according to claim 1, wherein, The pressure range for the second etching process is between 0.1 and 600 Torr.

30. The method according to claim 29, wherein, The pressure range for the second etching process is between 0.5 and 50 Torr.

31. The method according to claim 29, wherein, The pressure range for the second etching process is between 0.5 and 4 Torr.

32. A system for selectively etching a film disposed on a substrate, the system comprising: A reaction chamber configured to hold and process a substrate having an oxide layer, a nitride layer, and an oxynitride layer; A fluorine precursor source configured to provide a fluorine precursor gas, said fluorine precursor gas comprising at least one of the following: nitrogen trifluoride (NF3); carbon tetrafluoride (CF4); sulfur hexafluoride (SF6); hydrogen fluoride (HF); or fluorine gas (F2). A hydrogen precursor source configured to provide a hydrogen precursor gas, said hydrogen precursor gas comprising at least one of the following: ammonia (NH3); hydrazine (N2H4); urea (NH2CONH2); hydrogen (H2); alcohol; acidic gas; or a mixture thereof; and An inert gas source configured to provide an inert gas, wherein the inert gas includes at least one of the following: argon; krypton; helium; xenon; or nitrogen; In this process, a gaseous mixture of the fluorine precursor gas, hydrogen precursor gas, and inert gas is flowed onto the substrate to etch the oxide layer and the oxynitride layer according to claim 1, while maintaining the integrity of the nitride layer.

33. The system according to claim 32, wherein, The alcohols include methanol, ethanol, propanol, or isopropanol.

34. The system according to claim 32, wherein, The acidic gases include formic acid (HCOOH), acetic acid (CH3COOH), or acidic anhydrides.

35. The system of claim 34, further comprising: A remote plasma unit configured to provide free radicals of the fluorine precursor gas and the inert gas.

36. The system of claim 34, further comprising: A gas manifold configured to mix the fluorine precursor gas, hydrogen precursor gas, and inert gas.

37. The system according to claim 34, wherein, The oxide layer includes at least one of the following: silicon oxide; germanium oxide; aluminum oxide; cobalt oxide; tungsten oxide.

38. The system according to claim 34, wherein, The oxide layer contains silicon, germanium, aluminum, cobalt, or tungsten.

39. The system according to claim 34, wherein, The nitride layer includes at least one of the following: silicon nitride; metal nitride.

40. The system according to claim 39, wherein, The metal nitrides include aluminum nitride.

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