Self-assembled monolayers as sacrificial capping layers

Abstract

A substrate processing method includes providing a substrate including a metal surface and a dielectric material surface, selectively forming a sacrificial capping layer including a self-assembled monolayer on the metal surface, removing the sacrificial capping layer to restore the metal surface, and treating the restored metal surface and the dielectric material surface. The sacrificial capping layer can be used to prevent diffusion of the metal into the dielectric material and to prevent oxidation and contamination of the metal surface while awaiting further processing of the substrate.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 62 / 946,243, filed December 10, 2019, and entitled “Self-Assembled Monolayers as Sacrificial Capping Layers,” the disclosure of which is expressly incorporated by reference in its entirety herein.

[0002] The present invention relates to semiconductor processing and semiconductor processing systems, and more particularly to a method for forming self-assembled monolayers as sacrificial capping layers to protect exposed materials during semiconductor processing. [Background technology]

[0003] Many metals easily diffuse into dielectric materials under thermal and / or electrical stress, which results in dielectric breakdown. In semiconductor devices, copper (Cu) metal is used as a conductor for interconnects to lower the electrical resistance within the device. To prevent metal diffusion, the Cu metal deposited in a recessed feature is surrounded by one or more diffusion barrier layers on the side and bottom surfaces of the recessed feature. The Cu metal fill into the recessed feature is often followed by a chemical mechanical polishing (CMP) process to remove excess Cu metal relative to adjacent dielectric materials and planarize the Cu metal in the recessed feature. After the CMP process, a capping layer may be deposited on the planarized Cu metal. Although Ta / TaN or CoWP capping layers have been used, the process of selectively depositing a metal capping layer on the Cu metal and subsequently removing the metal capping layer is problematic and may affect the reliability of the Cu metal interconnect. Additionally, dielectric capping layers and dielectric etch stop layers (e.g., SiN, SiC, SiCN, and SiCO) have been used, but are difficult to selectively deposit on the Cu metal surface. Summary of the Invention [Means for solving the problem]

[0004] A substrate processing method is described that selectively deposits a sacrificial capping layer onto a metal surface to prevent diffusion of the metal into dielectric materials and to prevent oxidation and contamination of the metal surface while awaiting further processing of the substrate. The sacrificial capping layer can then be removed to provide a clean metal surface for further processing of the substrate.

[0005] According to one embodiment, a method for processing a substrate includes providing a substrate comprising a metal surface and a dielectric material surface, selectively forming a sacrificial capping layer comprising a self-assembled monolayer on the metal surface, removing the sacrificial capping layer to restore the metal surface, and treating the restored metal surface and the dielectric material surface.

[0006] Selectively forming a sacrificial capping layer on a metal surface can include dispensing a chemical solution onto the substrate while rotating the substrate, the chemical solution can include a compound including a carbon group, a binding group bonded to the carbon group, an end group bonded to the carbon group opposite the binding group, and a solvent solution, and annealing the substrate after dispensing the chemical solution onto the substrate.

[0007] A more detailed understanding of the embodiments of the present invention and many of the attendant advantages thereof will be readily apparent by reference to the following detailed description, particularly when considered in conjunction with the accompanying drawings. [Brief description of the drawings]

[0008] [Figure 1] FIG. 1 illustrates an exemplary embodiment of a spin-coating processing system, including a cross-sectional view of a coating module of the spin-coating processing system. [Diagram 2] FIG. 1 is a diagram of a representative embodiment of a group of a self-assembled monolayer. [Figure 3A] 1 is a schematic cross-sectional view of a method for processing a substrate according to one embodiment of the present invention; [Figure 3B]1 is a schematic cross-sectional view of a method for processing a substrate according to one embodiment of the present invention; [Figure 3C] 1 is a schematic cross-sectional view of a method for processing a substrate according to one embodiment of the present invention; [Figure 3D] 1 is a schematic cross-sectional view of a method for processing a substrate according to one embodiment of the present invention; DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] A method of processing a substrate is described. The substrate may include any material or structure of a device, particularly a semiconductor device or other electronic device, and may be a base substrate structure, such as a semiconductor substrate, or a layer, such as a thin film, on or over the base substrate structure. Thus, the substrate is not intended to be limited to any particular base structure, lower layer, or upper layer, patterned or unpatterned, but rather is intended to include any such layer or base structure and any combination of layers and / or base structures. Although the following description may refer to a particular type of substrate, this description is for illustrative purposes only and not for limiting purposes. The substrate may include a circular substrate (wafer) having a diameter of at least 150 mm, 200 mm, 300 mm, or 450 mm.

[0010] FIG. 1 shows a spin-coating processing system 100 for dispensing chemicals onto a substrate 102 using a coating module 104 in fluid communication with a liquid delivery system 106 capable of dispensing one or more liquid chemicals. The system 100 may also include a gas delivery system 108 that may provide gas to the coating module 104, which may be removed via an exhaust system 110. A liquid drain (not shown) may be incorporated into the exhaust system to remove liquid from the coating module 104. The system 100 may also include an anneal module 112 that may bake or apply optical radiation to the substrate 102 after the chemicals have been dispensed. A controller 114 may be used to control the components of the system 100 using an electrical communication network that may send and receive computer-executable instructions or electrical signals between the components of the system 100. The controller 114 may include one or more computer processors 116 and a memory 118, which may store computer-executable instructions that may be executed by the computer processor or other logic / processing device. The controller 114 can store process components 136 that can include recipes or process condition routines that can be implemented by controlling or directing the components of the system 100 to obtain specific conditions within the coating module 104 and / or annealing module 112. Communication between the components can be implemented by processing and electrical communication techniques known to those skilled in the art, as represented by dashed line 120.

[0011] The computer processor 116 may include one or more processing cores and may be configured to access (at least in part) and execute computer-readable instructions stored in one or more memories. The one or more computer processors 116 may include, but are not limited to, a central processing unit (CPU), a digital signal processor (DSP), a reduced instruction set computer (RISC), a complex instruction set computer (CISC), a microprocessor, a microcontroller, a field programmable gate array (FPGA), or any combination thereof. The computer processor 116 may also include a chipset (not shown) for controlling communication between components of the system 100. In certain embodiments, the computer processor may be based on the Intel™ architecture or the ARM™ architecture, and the processor and chipset may be from the family of Intel™ processors and chipsets. The one or more computer processors may also include one or more application specific integrated circuits (ASICs) or application specific standard products (ASSPs) for handling specific data processing functions or tasks.

[0012] The memory 118 may include one or more non-transitory computer readable storage media ("CRSM"). In some embodiments, the one or more memories may include non-transitory media such as random access memory ("RAM"), flash RAM, magnetic media, optical media, solid state media, etc. The one or more memories may be volatile (in that information is retained while power is applied) or non-volatile (in that information is retained even when power is not applied). Additional embodiments may also be provided as a computer program product including a non-transitory machine readable signal (in compressed or uncompressed format). Examples of machine readable signals include, but are not limited to, signals conveyed by the Internet or other networks. For example, distribution of software over the Internet may include a non-transitory machine readable signal. Additionally, the memory may store an operating system including a number of computer executable instructions, which may be implemented by the processor to perform various tasks to operate the system 100.

[0013] FIG. 1 also includes a representative diagram 122 of one embodiment of a coating module 104 capable of dispensing chemicals onto the substrate 102. The system 100 can be used to dispense one or more liquid chemicals that can be dispersed across the substrate 102 by either rotating the substrate 102, translating the substrate 102, or rotating or translating the position of the liquid dispenser. The liquid dispensers 124, 126 disposed on the substrate 102 can be moved across or around any location on or adjacent the substrate 102 using a positioning mechanism 128. In the embodiment of FIG. 1, the positioning mechanism 128 can move back and forth in a horizontal and / or vertical plane, as indicated by the arrow adjacent the positioning mechanism 128. The positioning mechanism 128 can also be rotated around a vertical axis 130 of the positioning mechanism 128. The positioning mechanism 128 can dispense chemicals to individual locations across the substrate 102, or chemicals can be dispensed as the positioning mechanism 128 moves across the substrate 102. The chemicals may be disposed on the substrate in a continuous or non-continuous manner: the chemicals may be dispensed one at a time in multiple passes across the substrate 102, or the chemicals may be dispensed at the same location but at different times.

[0014] The substrate 102 may be secured to a rotating chuck 132 that supports the substrate 102 and may rotate the substrate 102 during chemical delivery. The substrate 102 may rotate about a rotation axis 134 at a speed of up to 2200 revolutions per minute (rpm). Chemical delivery may occur before, during, and / or after the substrate 102 begins to rotate.

[0015] Before or after the chemicals are dispensed, the substrate 102 may be processed in an annealing module 112, which may heat the substrate 102 to remove moisture from the substrate 102 before the chemicals are dispensed or to process a film deposited on the substrate 102 by the coating module 104. The annealing module 112 may include, but is not limited to, a resistive heating element (not shown) that transfers heat to the substrate 102 by conduction. In another embodiment, the annealing module 112 may include a radiation source (not shown) that exposes the substrate 102 to radiation. The radiation source may include, but is not limited to, an ultraviolet (UV) source (not shown). The annealing module 112 may also heat the substrate 102 via convection by receiving heated gas from the gas delivery system 108. The annealing module 112 may also treat the substrate 102 with a gas that is relatively inert to the substrate 102 or the deposited film to prevent chemical reactions with the ambient or surrounding environment (e.g., oxygen, moisture, etc.). The gas may also be used to remove outgassed gases or fluids from the deposited film during the annealing process. The outgassed chemicals may be removed by an exhaust system 110 that removes gases from the anneal module 112.

[0016] FIG. 2 is a diagram of a representative embodiment of a group of self-assembled monolayers (SAMs) 200 that may be formed on a substrate 102. SAMs are commonly known as surface modifiers and adhesion layers. The SAM 200 shown in FIG. 2 is intended for the purpose of illustrating the components of the SAM 200. In application, the SAM 200 may be used with multiple SAMs 200 systematically arranged on the substrate 102. In brief, the multiple SAMs 200 may form a three-dimensional crystalline or semi-crystalline structure on the surface of the substrate 102. The SAM 200 may have a thickness of less than 1 nm. The SAM 200 may include a compound that includes an end group 202, a chain group 204, and a linking group 206. These groups may form the building blocks of the SAM 200, and the interaction between these groups and the substrate 102 may form a three-dimensional structure. Molecular self-assembly can result from van der Waals interactions, hydrophobic interactions, and / or a combination of molecule-substrate interactions that spontaneously form highly ordered low-dimensional structures on the substrate 102 or an overlying film (not shown).

[0017] In general, the binding groups 206 may be bonded or chemisorbed to the substrate 102. The binding groups 206 may be chemically attracted to the substrate 102 or to a film or layer on the substrate 102, such as a metal layer. However, the end groups 202 and the chain groups 204 may not be bonded or chemisorbed to the substrate 102, or at least may not be bonded in the same manner as the binding groups 206. The chain groups 204 and the end groups 202 may assemble with themselves, as shown in FIG. 2. As a result of this selective assembly, the SAM 200 may appear to stand with the binding groups 206 immobilized on the substrate 102 and the end groups 202 and the chain groups 206 tethered to the substrate 102 via the binding groups 206.

[0018] The SAM 200 can be used in a variety of applications, and the composition of these groups, i.e., building blocks, can vary depending on the desired structure and type of substrate 102. According to one embodiment, the linking group 206 can be any reactive element that can bond or chemically react with a desired material layer, e.g., a metal layer, on the substrate 102 and only weakly bond to a different material, e.g., a dielectric material. In the case of a metal layer, in some examples, the linking group 206 can include a thiol, silane, or phosphonate. The chain group 204 can include a chain of carbon atoms that can be connected or bonded together. Although FIG. 2 shows one group of the SAM 200, the chain group 204 can be bonded with adjacent chain groups that can form a larger SAM structure (not shown). The chain groups 204 can be C groups that can be bonded together to form a three-dimensional structure of the SAM 200 across the surface of the substrate 102. x H y The end groups 202 can be assembled onto the chain groups 204 and can be selected based on the application of the SAM 200. An example of a SAM 200 is 1-octadecanethiol (CH3(CH2) 16 perfluorodecanethiol (CF3(CF2)7CH2CH2SH), perfluorodecyltrichlorosilane (CF3(CF2)7CH2CH2SiCl3), perfluorodecanethiol (CF3(CF2)7CH2CH2SH), chlorodecyldimethylsilane (CH3(CH2)8CH2Si(CH3)2Cl) and tertbutyl(chloro)dimethylsilane ((CH3)3CSi(Cl)(CH3)2)).

[0019] According to one embodiment, the substrate 102 has metal wiring formed in a dielectric material, and the metal wiring is at least partially exposed. Some embodiments of the present invention describe a method for selectively forming a sacrificial capping layer including a self-assembled monolayer on a metal surface, and the sacrificial capping layer can be used to prevent metal diffusion into the dielectric material and oxidation of the exposed metal surface, thereby enabling the substrate 102 to be processed without being restricted by Q time. Here, "Q time" refers to a time limit set for a time interval after the substrate 102 is, for example, dry etched, to prevent oxidation of the metal wiring exposed by dry etching before further processing of the substrate 102. When setting the Q time, time management is required to comply with the Q time. Therefore, there is a risk that productivity may decrease due to an increase in processing time. Furthermore, if the set Q time is short, line management becomes difficult. Also, productivity may decrease due to the complexity of line management.

[0020] 3A-3D show a schematic diagram of a method for using a self-assembled monolayer as a sacrificial capping layer according to an embodiment of the present invention. In the schematic cross-sectional view in FIG. 3A, a substrate 3 is patterned to include a recessed feature in a dielectric material 300, the recessed feature including a barrier / liner layer 302 surrounding metal 304 on the sidewalls and bottom of the recessed feature. The substrate 3 includes an exposed metal surface 303 and an exposed dielectric material surface 301. In one example, the metal surface 303 may include a metal selected from the group consisting of Cu, Al, Ta, Ti, W, Ru, Co, Ni, and Mo. In one example, the dielectric material surface includes silicon. In another example, the dielectric material surface includes SiO2 or a low-k material.

[0021] The exemplary substrate 3 is planarized with a metal surface 303 and a dielectric material surface 301 in the same horizontal plane. The planarization may utilize a CMP process, followed by a cleaning process to remove any impurities and oxides from the surface of the substrate 3. In some examples, the substrate 3 may include a Cu metal surface 303 and a SiO2 or low-k surface 301. In one example, a wet cleaning process using an aqueous citric acid solution may be used to remove oxidized Cu metal from the Cu metal surface 303. In another example, the cleaning process may include a dry cleaning process.

[0022] The time between the cleaning process and further processing of the substrate 3 following the cleaning process needs to be short to avoid diffusion of Cu metal from Cu metal 304 to the dielectric material 300 along the top of the substrate 3 and to avoid oxidation of the Cu metal surface 303 due to exposure to oxygen-containing background gases. In one example, the further processing may include selectively depositing a dielectric film on the dielectric material surface 301 by gas-phase exposure, and a clean, unoxidized Cu metal surface 303 is required to achieve the required deposition selectivity between the dielectric material surface 301 and the Cu metal surface 303. Selective deposition of a dielectric film on the dielectric material surface 301 may be used to form a fully self-aligned via (FSAV) on the Cu metal surface 303.

[0023] The method further includes selectively forming a sacrificial capping layer 306 comprising a self-assembled monolayer on the exposed metal surface 303 relative to the dielectric material surface 301, as shown generally in FIG. 3B. The sacrificial capping layer 306 may be formed using the spin-coating processing system 100 described in FIG. 1. A chemical solution including a SAM chemical (e.g., 1-octadecanethiol) may be dispensed onto the substrate 3 by the coating module 104. The chemical solution may further include a solvent, e.g., an organic solvent. The amount of the dispensed chemical solution should be an amount that allows at least a majority of the substrate 3 to be covered with the chemical solution. In one example, the concentration of the SAM chemical in the chemical solution may be about 5 mM or less. The substrate 3 may be rotated during application of the chemical solution, for example, at a rotation speed of about 800 rpm to about 2200 rpm.

[0024] The binding groups of the SAM chemical include reactive elements (e.g., thiol groups) that may bond or chemically react with the exposed metal surface 303 of the metal 304, but only weakly interact with the dielectric material surface 301 of the dielectric material 300. A rinsing solution (e.g., isopropyl alcohol (IPA)) may then be dispensed onto the substrate 3 by the coating module 104 to remove any excess chemical solution from the substrate 3, including the weakly bound SAM chemical from the dielectric material surface 301 of the dielectric material 300.

[0025] The substrate 3 may then be removed from the coating module 104 and sent to the annealing module 112, which may include a resistive heating element or a radiation source (e.g., UV light). In the annealing module 112, the substrate 3 may be annealed at a temperature below the desorption and decomposition temperatures of the SAM on the exposed metal surface 303. In one example, using the SAM chemical 1-octadecanethiol, the substrate 3 may be annealed at a temperature below 160° C. (decomposition temperature) for a time of about 5 minutes or less. In other embodiments, the substrate 3 may be removed from the system 100 and annealed in a separate tool (e.g., bake oven, furnace). The annealing may enable or improve the self-assembly of the SAM chemical components on the substrate 3 to form a sacrificial capping layer 306 on the exposed metal surface 303 of the metal 304. The substrate 3 may then be transferred to the coating module 104 for an additional rinse, followed by a soft bake in the annealing module 112. The soft bake may be performed at a temperature below 160° C. This sequence of steps selectively forms an ordered sacrificial capping layer 306 on the exposed metal surface 303, while leaving the dielectric material surface 301 at least substantially free of the SAM chemical.

[0026] The properties of the sacrificial capping layer 306 may include one or more of the following properties: uniform thickness distribution on the metal surface 303 within one monolayer thickness across the substrate 3 and uniform water contact angle suitable for the end groups of the SAM. The sacrificial capping layer 306 protects the metal surface 303 from adverse effects such as oxidation and metal diffusion from the metal 304 into the dielectric material 300, thereby eliminating the need to set a Q time. The absence of a need to set a Q time eliminates the need for time management in compliance with the Q time, prevents the complication of line management due to compliance with the Q time, and leads to improved productivity in device manufacturing.

[0027] Following selective formation of the sacrificial capping layer 306 on the metal surface 303, the sacrificial capping layer 306 is removed from the substrate 3, and the substrate 3 may be placed in a carrier pattern and stored prior to further processing of the substrate 3.

[0028] According to another embodiment, a sacrificial capping layer 306 may be formed on the exposed metal surface 303 by exposing the substrate 3 to a reactant gas that includes a compound capable of forming a self-aligned monolayer (e.g., 1-octadecanethiol). The reactant gas may further include an inert gas.

[0029] In one example, the substrate 3 may be transferred to the annealing module 112 and annealed at a temperature that results in the desorption of the sacrificial capping layer 306 from the substrate 3 to restore the metal surface 303 and the dielectric material surface 301 before further processing. The resulting substrate 3 is shown diagrammatically in FIG. 3C. In another example, the substrate 3 may be transferred to another processing system or another processing platform where the sacrificial capping layer 306 may be removed. Alternatively, the sacrificial capping layer 306 may be removed using gas exposure to plasma excited H2 gas and optional substrate heating. In addition to removing the sacrificial capping layer 306, the gas exposure to plasma excited H2 gas may further clean the dielectric material surface 101 without damaging the dielectric material surface 101.

[0030] According to some embodiments of the present invention, the metal surfaces and the restored metal surfaces are clean and not chemically modified. In one example, the metal surfaces and the restored metal surfaces are not oxidized.

[0031] In one example, the further processing may include a deposition process, which includes selectively depositing a dielectric layer 308 (e.g., SiO2) on the exposed dielectric material surface 301 in an area selective deposition (ASD) process. This is shown diagrammatically in FIG. 3D. In one example, the selective deposition includes adsorbing a metal-containing catalyst layer on the dielectric material surface and exposing the substrate to a process gas including a silanol gas at a substrate temperature of about 150° C. or less in the absence of any oxidizing agent or hydrolyzing agent to selectively deposit a SiO2 film on the dielectric material surface relative to the metal surface. The metal-containing catalyst layer may include, for example, aluminum (Al) or titanium (Ti). In one example, the metal-containing catalyst layer may be formed by exposing the substrate to AlMe3 gas. In one example, the silanol gas is selected from the group consisting of tris(tert-pentoxy)silanol, tris(tert-butoxy)silanol, and bis(tert-butoxy)(isopropoxy)silanol.

[0032] Several embodiments have been described for forming a self-assembled monolayer as a sacrificial capping layer to protect exposed materials during semiconductor processing. The above description of the embodiments of the present invention has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. This specification and the following claims include terms that are used for descriptive purposes only and should not be construed as limiting. Those skilled in the relevant art will appreciate that many modifications and variations are possible in light of the above teachings. It is therefore intended that the scope of the present invention be limited not by this detailed description, but rather by the claims appended hereto.

Claims

1. 1. A method for processing a substrate, comprising: Providing a substrate including a metal surface and a dielectric material surface; selectively forming a sacrificial capping layer comprising a self-assembled monolayer on the metal surface, the sacrificial capping layer preventing oxidation and contamination of the metal surface while awaiting further processing of the substrate; removing the sacrificial capping layer to restore the metal surface while leaving the dielectric material surface exposed; selectively depositing a dielectric film on the dielectric material surface relative to the restored metal surface after the sacrificial capping layer removal step; The method comprising:

2. The method of claim 1 , wherein the metal surface and the restored metal surface are not chemically modified.

3. The method of claim 1 , wherein the metal surface and the restored metal surface are not oxidized.

4. Selectively forming the sacrificial capping layer on the metal surface comprises: dispensing a chemical solution onto the substrate while rotating the substrate, the chemical solution including a chemical compound including a carbon group, a binding group bonded to the carbon group, and an end group bonded to the carbon group opposite the binding group, and a solvent solution; annealing the substrate after dispensing the chemical solution onto the substrate; 2. The method of claim 1, comprising:

5. 5. The method of claim 4, further comprising dispensing a rinsing solution onto the substrate to remove the chemical solution from the dielectric material surface prior to annealing the substrate.

6. 5. The method of claim 4, further comprising removing oxidized metal from the metal surface prior to selectively forming the sacrificial capping layer.

7. The method of claim 4 , wherein the binding group comprises a thiol, a silane, or a phosphonate.

8. The chemical compound is 1-octadecanethiol (CH ３ (CH ２ ) １６ CH ２ SH), perfluorodecyltrichlorosilane (CF ３ (CF ２ ) ７ CH ２ CH ２ SiCl ３ ), perfluorodecanethiol (CF ３ (CF ２ ) ７ CH ２ CH ２ SH), chlorodecyldimethylsilane (CH ３ (CH ２ ) ８ CH ２ Si(CH ３ ) ２ Cl) or tert-butyl(chloro)dimethylsilane ((CH ３ ) ３ CSi(Cl)(CH ３ ) ２ 5. The method of claim 4, comprising:

9. 2. The method of claim 1, wherein the metal surface comprises a metal selected from the group consisting of Cu, Al, Ta, Ti, W, Ru, Co, Ni, and Mo.

10. The method of claim 1 , wherein removing the sacrificial capping layer comprises annealing the substrate at a temperature that desorbs the sacrificial capping layer from the substrate.

11. The surface of the dielectric material is SiO ２ or a low-k material.

12. 1. A method for processing a substrate, comprising: Providing a substrate including a metal surface and a dielectric material surface; selectively forming a sacrificial capping layer comprising a self-assembled monolayer on the metal surface, the sacrificial capping layer preventing oxidation and contamination of the metal surface while awaiting further processing of the substrate; removing the sacrificial capping layer to expose a restored metal surface while leaving the dielectric material surface exposed, and then selectively depositing a dielectric film on the dielectric material surface by vapor phase exposure; adsorbing a metal-inclusive catalyst layer on a surface of the dielectric material; In the absence of any oxidizing or hydrolyzing agent, the substrate is exposed to a process gas containing silanol gas at a substrate temperature of 150° C. or less to form SiO 2 on the dielectric material surface relative to the restored metal surface. ２ Selectively depositing a film; and The method comprising:

13. 13. The method of claim 12, wherein the silanol gas is selected from the group consisting of tris(tert-pentoxy)silanol, tris(tert-butoxy)silanol, and bis(tert-butoxy)(isopropoxy)silanol.

14. 10. The method of claim 1, further comprising removing oxidized metal from the metal surface prior to selectively forming the sacrificial capping layer.

15. Selectively forming the sacrificial capping layer on the metal surface comprises: exposing the substrate to a chemical compound comprising a carbon group, a linking group attached to the carbon group, and an end group attached to the carbon group opposite the linking group, and a reactive gas comprising an inert gas.

2. The method of claim 1, comprising:

16. 1. A method for processing a substrate, comprising: providing a substrate comprising a metal surface and a dielectric material surface, the metal surface being non-oxidized; selectively forming a sacrificial capping layer comprising a self-assembled monolayer on the metal surface, the sacrificial capping layer preventing oxidation of the metal surface; removing the sacrificial capping layer to restore the metal surface while leaving the dielectric material surface exposed; After removing the sacrificial capping layer, selectively depositing a dielectric film on the dielectric material surface by vapor phase exposure; having Selectively forming the sacrificial capping layer on the surface comprises: exposing the substrate to a chemical compound comprising a carbon group, a linking group bonded to the carbon group, and a terminal group bonded to the carbon group opposite the linking group, and a reactive gas comprising an inert gas. The method comprising:

17. Selectively forming the sacrificial capping layer on the metal surface comprises: dispensing a chemical solution onto the substrate while rotating the substrate, the chemical solution comprising a chemical compound comprising a carbon group, a binding group bonded to the carbon group, and an end group bonded to the carbon group opposite the binding group, and a solvent solution, the binding group comprising a thiol, a silane, or a phosphonate; dispensing a rinsing solution onto the substrate to remove the chemical solution from the dielectric material surface; annealing the substrate after dispensing a rinsing solution onto the substrate; 17. The method of claim 16, comprising:

18. The chemical compound is 1-octadecanethiol (CH ３ (CH ２ ) １６ CH ２ SH), perfluorodecyltrichlorosilane (CF ３ (CF ２ ) ７ CH ２ CH ２ SiCl ３ ), perfluorodecanethiol (CF ３ (CF ２ ) ７ CH ２ CH ２ SH), chlorodecyldimethylsilane (CH ３ (CH ２ ) ８ CH ２ Si(CH ３ ) ２ Cl) or tert-butyl(chloro)dimethylsilane ((CH ３ ) ３ CSi(Cl)(CH ３ ) ２ 17. The method of claim 16, comprising:

19. Selectively forming the sacrificial capping layer on the metal surface comprises: dispersing a chemical solution onto the substrate while rotating the substrate, the chemical solution including a chemical compound including a carbon group, a binding group bonded to the carbon group, and an end group bonded to the carbon group opposite the binding group, and a solvent solution; annealing the substrate after dispersing the chemical solution on the substrate; 13. The method of claim 12, comprising:

20. The method of claim 19 , wherein the binding group comprises a thiol, a silane, or a phosphonate.

21. 13. The method of claim 12, wherein the metal surface comprises a metal selected from the group consisting of Cu, Al, Ta, Ti, W, Ru, Co, Ni and Mo.

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