TW201906003A - Selective deposition of metal films - Google Patents

Abstract

The metal layer may be selectively deposited on one surface of the substrate with respect to the second surface of the substrate. In some embodiments, the metal layer is selectively deposited on the first metal surface with respect to the second surface including silicon. In some specific examples, the reaction chamber in which selective deposition occurs may be passivated as appropriate before the selective deposition process is performed. In some specific examples, selectivities of greater than about 50% or even about 90% are achieved.

Description

Selective deposition of metal thin films

This application is filed in U.S. Application No. 15 / 177,198 filed on June 8, 2016 and named `` SELECTIVE DEPOSITION OF METALLIC FILMS '' and filed on June 8, 2016 and named `` REACTION CHAMBER PASSIVATION AND SELECTIVE DEPOSITION OF METALLIC FILMS ", part of US Application No. 15/177195, which is a continuation of the application, and is consistent with the US filed on December 9, 2011 Provisional Application No. 61 / 569,142 with priority of US Application No. 13 filed on December 7, 2012 and entitled "SELECTIVE FORMATION OF METALLIC FILMS ON METALLIC SURFACES" No. / 708,863, whose disclosure is hereby incorporated by reference in its entirety.

This application relates generally to the field of semiconductor manufacturing.

Integrated circuits are currently manufactured by a sophisticated process in which each material layer is sequentially constructed on a semiconductor substrate in a predetermined configuration.

Meeting the ever-increasing electromigration (EM; electromigration) requirements in copper interconnects has become increasingly difficult, as Morse's law has evolved, resulting in smaller devices. As the line size shrinks, the critical gap size of the EM fault will also decrease, resulting in a sharp reduction in the mean time between failures. Significant improvements in EM resistance are needed to achieve continuous scaling.

The interface between the dielectric diffusion barrier and the metal material has been demonstrated as the main path for metal material diffusion and the weakest link to resist EM failure. The implementation of selective metal covers is challenging because it is difficult to achieve good selectivity on metal surfaces compared to dielectric surfaces. Methods for selective deposition of metal films that can be used in this context to reduce electromigration are disclosed herein.

The selective deposition of tungsten advantageously reduces the need for complex patterning steps during semiconductor device manufacturing. However, mild surface treatments, such as heat treatment or free radical treatment, are generally preferred to provide the desired surface terminations for selective deposition. Such surface treatments may not adequately prepare the desired surface for selective deposition, resulting in a loss of selectivity.

According to some aspects, a process for selectively depositing a film on a first metal surface of the same substrate with respect to a second dielectric surface of the substrate is described. In some specific examples, the process may include performing a first metal surface treatment process. The first metal surface treatment process includes removing a surface layer from the first metal surface of the substrate, so that the second dielectric surface does not pass through the surface. The first metal surface treatment process provides a large number of new surface groups or ligands; and a film is selectively deposited on the substrate with a selectivity greater than about 50% relative to the second dielectric surface of the substrate On the first metal surface.

In some specific examples, the first metal surface treatment process includes exposing at least the first metal surface of the substrate to a plasma generated by a gas. In some specific examples, the first metal surface treatment process includes exposing the first metal surface of the substrate and the second dielectric surface of the substrate to a plasma generated by a gas. In some specific examples, the first metal surface treatment process further includes reducing and / or removing the metal oxide layer existing on the first metal surface of the substrate. In some specific examples, the removed surface layer includes an organic material. In some specific examples, the removed surface layer includes a passivation layer. In some specific examples, the removed surface layer includes benzotriazole (BTA). In some specific examples, the gas includes carbolic acid. In some specific examples, the gas includes formic acid (HCOOH) and H ₂ . In some specific examples, the gases include HCOOH, NH ₃ and H ₂ . In some embodiments, the gas is provided by a carrier gas including a noble gas. In some specific examples, the temperature of the substrate during the first metal surface treatment process is about 300 ° C. In some specific examples, the first metal surface treatment process includes exposing at least the first metal surface of the substrate to the plasma for about 1 second to about 10 minutes. In some specific examples, the plasma is generated by supplying radio frequency power (RF power) of about 10W to about 3000W to the gas. In some specific examples, the frequency of the RF power is about 1 MHz to about 10 GHz. In some specific examples, the pressure of the plasma generating gas is about 1 Pa to about 5000 Pa. In some embodiments, the selectively deposited film includes tungsten. In some specific examples, the first metal surface includes copper or cobalt. In some specific examples, the second dielectric surface includes silicon.

In some aspects, a process for selectively depositing a film on a first metal surface of the same substrate relative to a second dielectric surface of the substrate is described. In some specific examples, the process may include performing a first metal surface treatment process including exposing at least the first metal surface of the substrate to a plasma generated by a gas including HCOOH. The surface layer is removed from the first metal surface of the substrate; and a film is selectively deposited on the first metal surface of the substrate with a selectivity greater than about 50% relative to the second dielectric surface of the substrate.

In some aspects, presented herein is a process for selectively depositing a film on a substrate including a first metal surface and a second surface including silicon. In some specific examples, the process may include: passivating a reaction chamber in which a selective deposition process is to be performed; subjecting the substrate to a first surface treatment process, the first surface treatment process including exposing the substrate to a plasma; After the first surface treatment process, one or more selective deposition cycles are performed in the reaction chamber, and each cycle includes contacting the substrate with a first precursor including silicon or boron, relative to a first precursor including silicon. Two surfaces and selectively forming a layer of a first material including Si or B on a first metal surface; and exposing the first material to a second precursor including a metal on the first metal surface The first material is converted into a second metal material. In some specific examples, a second metal material is deposited on the first metal surface of the substrate with a selectivity greater than about 50% relative to the second surface including silicon.

In some specific examples, the first metal surface includes copper. In some specific examples, the first metal surface includes cobalt. In some specific examples, the second surface including silicon includes SiO ₂ . In some specific examples, the second metal material includes tungsten. In some specific examples, passivating the reaction chamber includes depositing a passivation layer on a surface in the reaction chamber, which surfaces may be exposed to the first precursor or the second precursor during one or more selective deposition cycles. Body. In some embodiments, the passivation layer is formed by a vapor deposition process. In some specific examples, the passivation layer is formed by a plasma enhanced chemical vapor deposition (PECVD) process. In some specific examples, the passivation layer is formed by a plasma enhanced atomic layer deposition (PEALD) process. In some specific examples, the passivation layer is formed by guiding the first gas phase silicon precursor and the second gas phase nitrogen precursor into the reaction chamber, and the plasma exists in the reaction chamber. In some specific examples, the passivation layer is formed by alternately and sequentially exposing the reaction chambers to a first precursor including disilane and an atomic nitrogen, nitrogen radical or nitrogen plasma and atomic hydrogen, hydrogen radical or hydrogen Formed in the second precursor of the plasma.

In some specific examples, the passivation layer includes SiN. In some embodiments, the plasma is produced from ethanol. In some specific examples, the plasma is generated from NH ₃ and H ₂ . In some specific examples, the first precursor includes silane. In some specific examples, the first precursor includes disilane. In some specific examples, the second precursor includes a metal halide. In some specific examples, the second precursor includes WF6. In some specific examples, the process further includes subjecting the substrate to a second surface treatment process before subjecting the substrate to a first surface treatment process. In some specific examples, the second surface treatment process includes exposing the substrate to a treatment reactant, wherein the treatment reactant deactivates the second surface. In some specific examples, a second metal material is deposited on the first metal surface of the substrate with a selectivity greater than about 90% relative to the second surface including silicon.

In some specific examples, a method for selectively depositing a metal film on a metal or metal material while avoiding deposition on a silicon-containing material such as silicon dioxide is disclosed. For example, a metal film can be deposited on copper for final substrate processing. In some specific examples, a metal film is deposited on an integrated circuit workpiece, which includes a copper wire in a silicon-containing material.

In some such applications, the selective deposition methods disclosed herein can be used to deposit materials onto copper, thereby reducing copper electromigration. In some embodiments, the selective deposition is on a copper metal layer rather than on a silicon-containing material on the substrate. Deposition on silicon-containing materials is undesirable in these applications because it may reduce the effective dielectric value.

In some specific examples, the process flow described herein is used to selectively deposit metal on micron-scale (or smaller) features during the fabrication of integrated circuits. In some specific examples, the feature size may be less than 100 micrometers, less than 1 micrometer, or less than 200 nm. In the case where W is selectively deposited on Cu for interconnection applications, in some specific examples, the feature size / line width may be less than 1 micron, less than 200 nm, less than 100 nm, or even less than 50 nm. Of course, those skilled in the art will recognize that with the disclosed method, selective deposition on larger features and in other contexts is possible.

In some embodiments, selective deposition can avoid additional processing steps, thereby saving time and reducing the costs associated with processing the substrate. For example, for small sizes, lithography will be extremely expensive in the future. With 8 or more Cu metallization layers in the wafer, the time and cost savings that can be achieved using selective deposition are magnified because of savings for each area of copper metallization during substrate processing Time. Moreover, the methods disclosed herein can eliminate the need for diffusion barriers and other processing steps.

In some specific examples, a process for removing one or more surface layers from a first metal surface of a substrate is disclosed. In some specific examples, the surface layer removal process may remove the surface layer existing on the first metal surface of the substrate. For example, the surface layer removal process may remove the surface layer existing on the first surface of the substrate in order to achieve or enhance the selective deposition performed thereon. In some specific examples, the removed surface layer may include an organic material layer. That is, in some specific examples, the surface layer removal process can remove any organic material existing on the first metal surface. For example, the surface layer removal process may remove the organic passivation layer existing on the first metal surface. For example, the surface layer removal process can remove a benzotriazole (BTA) passivation layer from a copper surface of an integrated circuit workpiece. In some specific examples, the surface layer removal process may remove any organic and / or hydrocarbon layers that may be present on the first metal surface.

In some specific examples, the surface layer removal process can restore the surface layer or a part of the surface layer existing on the first metal surface of the substrate. In some specific examples, the surface layer removal process may reduce and / or remove any oxide surface layer present on the first metal surface. In some specific examples, the surface layer removal process can reduce and / or remove any native oxide layer that may be present on the first metal surface. In some specific examples, the surface layer removal process may provide active sites on the first metal surface, for example, by reducing and / or removing the surface layer or a part of the surface layer existing on the first metal surface. In some specific examples, the oxide layer may be partially removed by a surface layer removal process and the remaining material including the oxide layer may be reduced. That is, in some specific examples, a part of the oxide layer may be removed by the surface layer removal process, and any remaining oxide layer may be reduced by the surface layer removal process. In some specific examples, substantially all of the oxide surface layer can be removed by a surface layer removal process. In some specific examples, substantially all of the oxide surface layer can be reduced by a surface layer removal process.

As used herein, the term reduction may refer to the chemical conversion of an oxide material into its non-oxide form. That is, when a metal oxide material is reduced, it is chemically converted into a metal of the metal oxide. For example, a copper oxide layer may be present on the first metal surface including copper, and the removal of the surface layer may reduce the copper oxide layer so that it is converted into metallic copper. In some specific examples, the surface layer may include both an organic surface layer and an oxide layer below the organic surface layer. In some specific examples where the first metal surface may include a surface layer including an organic surface layer and an oxide layer below the organic surface layer, the surface layer removal process may remove the organic surface layer and may also reduce the oxide layer and / Or remove it to provide a clean first metal surface.

In some specific examples, the first metal surface of the substrate is subjected to a surface layer removal process. The surface layer removal process includes exposing the substrate to a plasma generated by a gas. In some specific examples, the surface layer removal process may include exposing at least the first surface to the plasma. In some specific examples, the surface layer removal may include exposing the first surface and the second surface of the substrate to a plasma. Such a surface layer removal process may, for example, remove a passivation layer present on a first metal surface, such as a Cu surface. Such surface layer removal processes may also, for example, reduce the oxide layer and / or remove it from the first metal surface, such as reducing the copper oxide layer and / or remove it from the Cu surface

In some embodiments, a plasma generated from a gas including one or more organic compounds may be used in the surface layer removal process. In some specific examples, a plasma generated from a gas including a compound as described herein can be used in a surface layer removal process. In some specific examples, a plasma generated from a gas including formic acid (HCOOH) can be used in the surface layer removal process. In some specific examples, a plasma generated from a gas including carbonic acid can be used in a surface layer removal process. In some specific examples, a plasma generated from a gas including HCOOH and NH ₃ can be used in a surface layer removal process. In some specific examples, a plasma generated from a gas including HCOOH and H ₂ may be used in a surface layer removal process.

In some specific examples, a plasma generated from a gas including HCOOH, NH ₃ and H ₂ may be used in a surface layer removal process. In some specific examples, the plasma may be generated from a gas including HCOOH, NH ₃ and H ₂ , where the ratio of HCOOH: NH ₃ : H ₂ is about 1: 1: 1 to about 1: 1: 20 or about 1: 1 : 9 to about 1: 1: 19. In some specific examples, the ratio of HCOOH: NH ₃ : H ₂ is about 1: 1: 19. Advantageously, exposing the first metal surface of the substrate to a plasma generated by gases including HCOOH, NH ₃ and H ₂ may remove any passivation material present on the first metal surface, and may also cause Any primary oxide material on the first metal surface is reduced and / or removed. In addition, the surface removal process including exposing the substrate to a plasma generated by a gas including HCOOH, NH ₃ and H ₂ may not provide any additional or new surface to a second surface, such as the second dielectric surface of the substrate Group or ligand. In this way, processes such as surface layer removal can be used to prepare a first metal surface of a substrate (such as an integrated circuit workpiece) for deposition thereon without the need to provide a shielded or protected layer over other surfaces of the substrate Or, there is no need to further process the second surface of the substrate to passivate the second surface for thin film deposition, for example. Such surface layer removal processes can therefore simplify and / or reduce the number of processing steps necessary in the selective deposition and / or integrated circuit manufacturing process.

FIG. 1 is a flowchart generally illustrating a process 10 for selectively depositing a metal film on a first metal surface of a substrate relative to a second silicon-containing surface. In some specific examples, the process may include an optional reaction chamber passivation step 11 prior to the selective deposition step 14 in order to achieve selective deposition, improve selectivity, and / or lose selectivity during the selective deposition process Previously increased the number of consecutive cycles. In some embodiments, the reaction chamber passivation step 11 can increase the number of consecutive cycles to achieve a desired level of selectivity. Optionally, the reaction chamber passivation step 11 may include providing a passivation material or a passivation layer on the chamber surface and other parts that may be exposed to the precursor or reactants during the selective deposition step 14. The reaction chamber passivation step 11 may limit or prevent the deposition of metallic materials on the chamber surface during the subsequent selective deposition step 14, thereby reducing or eliminating the amount of reaction byproducts generated by the selective deposition step 14. In some specific examples, the reaction chamber passivation step 11 can reduce the contamination of the substrate during the selective deposition step 14, so as to achieve selective deposition or increase selectivity.

In some specific examples, the passivation layer may include, for example, SiN. In some specific examples, the passivation layer may include a metal oxide and may be formed by, for example, oxidizing a metal material present on a surface of the chamber. In some specific examples, the passivation layer may not be pure metal or pure silicon.

Selective deposition using the methods described herein does not require processing the silicon-containing layer to prevent deposition thereon. Therefore, in some specific examples, the second surface including silicon does not include a passivation layer or a barrier layer, such as a self-assembled monolayer (SAM), which will prevent the actual top surface of the second dielectric surface from being exposed to Chemicals in the deposition process described in this article. Therefore, in some specific examples, a film is selectively deposited on a first metal surface on a substrate that has not undergone a treatment designed to prevent the film from being deposited on the second silicon-containing surface, such as a barrier treatment or passivation deal with. That is, in some specific examples, although the blocking layer or the passivation layer does not block the deposition on the second surface including silicon, selective deposition can still be obtained. In practice, the deposition conditions are selected so that the selective deposition process will be performed without the need to pre-treat the second surface including silicon before deposition.

In some embodiments, the second silicon-containing layer may be exposed to a process designed to treat the first surface. For example, in some specific examples, it is desirable to passivate the first metal surface, and the second surface including silicon may be exposed to the same passivation process as the first metal surface. For example, in the case of Cu, both the first Cu surface and the second surface including silicon can be exposed to benzotriazole (BTA) or another passivation chemical. However, prior to the first surface treatment step to remove the passivation layer from the metal surface, no specific further treatment or exposure (except for treatments or exposures acceptable during sample transport) is performed on the second surface including silicon. In detail, it is not necessary to perform a process designed to block the deposition of the film on the second surface including silicon.

In some specific examples, when the film is selectively deposited, the second dielectric surface includes only surface groups naturally occurring in the low-k material, and does not include a large number of functional groups that are not naturally present in the low-k material itself Or ligand. In some specific examples, after the first surface treatment that adds surface groups to the second dielectric surface, the active treatment of the second dielectric surface is not performed. In some specific examples, the second dielectric surface includes only surface groups naturally occurring in the low-k material, such surface groups including, for example, their surface groups that may be formed during transport of the substrate in air.

However, in some specific examples, the second silicon-containing surface may be treated as appropriate at step 12. In some examples, the silicon-containing surface may be processed at step 12 to enhance the selectivity of the deposition process by reducing the amount of material deposited on the silicon-containing surface (eg, by passivating the silicon-containing surface). In some specific examples, the processing step 12 is intended to restore the silicon-containing layer without blocking the deposition on the silicon-containing layer. In some specific examples, the second silicon-containing surface treatment at step 12 may include contacting the second surface with a processing chemical. For example, the second surface including silicon may be contacted with a trimethyl (dimethylamino) silane. Handling of chemicals. In some specific examples, the substrate may be outgassed at the beginning of step 12 or before step 12 to remove, for example, any moisture from the surface of the substrate or inside the silicon-containing material.

In some specific examples, the substrate surface is cleaned or treated at step 13 before the selective deposition step 14 is started. In some specific examples, the first surface treatment step 13 may include exposing the substrate to a plasma, such as a plasma generated from a gas including HCOOH, NH ₃ and H ₂ . In some specific examples, the first surface treatment step 13 may include a process for removing the surface layer from the first metal surface as described herein. In some specific examples, the first surface treatment step 13 may include exposing the substrate to a gas-phase treatment chemical, such as formic acid. In some specific examples, the first surface treatment step 13 can reduce and / or remove the surface layer from the first metal surface. In some specific examples, the first surface treatment step 13 may reduce and / or remove any native oxides that may be present on the first metal surface. However, in some specific examples, the native oxide may still exist on the first surface after the first surface treatment step 13. In some specific examples, the first surface treatment step 13 may remove any surface layer that may exist on the first metal surface, such as an organic surface layer or a hydrocarbon surface layer. In some specific examples, the first surface treatment step 13 can remove the organic surface layer or the hydrocarbon surface layer, and can also reduce the oxide layer and / or remove it from the first metal surface. In some specific examples, the first surface treatment step 13 may provide an active site on the first metal surface. In some specific examples, the substrate may be degassed at the beginning of step 13 or before step 13 to remove, for example, any moisture from the surface of the substrate or inside the silicon-containing material. In some specific examples, the first surface treatment step 13 may not substantially damage or degrade the second surface. For example, the first surface treatment step 13 may not provide or form a large number of new surface groups or compounds on the second surface. Bit body.

In some embodiments, step 14 of the selective deposition process includes selectively depositing a film on a substrate including a first metal surface and a second surface including silicon using a plurality of deposition cycles. The cycle includes: contacting a substrate with a first precursor including silicon or boron to selectively form a layer of a first material including Si or B over a first metal surface relative to a second surface including silicon; and by The first material is converted into a second metal material by exposing the substrate to a second precursor including a metal. The selective deposition step 14 involves forming a larger amount of material on the first metal surface relative to the second surface including silicon. The selectivity can be expressed as a ratio of a combined amount of a material formed on the first surface to a material formed on the first surface and the second surface. For example, if the process deposits 10 nm of W on a first copper surface and 1 nm of W on a second silicon oxide surface, the process will be considered to be 90% selective. Preferably, the selectivity of the method disclosed herein is higher than about 80%, more preferably higher than 90%, even more preferably higher than 95%, and most preferably about 100%. In some cases, the selectivity is at least about 80%, which may be sufficient for some specific applications. In some cases, the selectivity is at least about 50%, which may be sufficient for some specific applications. In some embodiments, the material is deposited at step 14 using multiple deposition cycles. In some embodiments, the selectively deposited film is a metal layer. The metal layer may be an elemental metal. In some specific examples, the metal layer may include additional elements such as Si, B, N, and / or dopants. Therefore, in some specific examples, the metal layer is a metal nitride or a metal silicide. As used herein, "metallic" indicates that the film, reactant, or other material includes one or more metals.

The substrate may include various types of materials. When manufacturing integrated circuits, the substrate usually includes several thin films with different chemical substances and physical properties. For example and without limitation, the substrate may include a silicon-containing layer and a metal layer. In some specific examples, the substrate may include a metal carbide. In some specific examples, the substrate may include a conductive oxide.

Preferably, the substrate has a first surface including a metal, referred to herein as a first metal surface / first metallic surface. In some specific examples, the first surface is substantially an elemental metal, such as Cu or Co. In some specific examples, the first surface includes a metal nitride. In some specific examples, the first surface includes a transition metal. The transition metal may be selected from the group: Ti, V, Cr, Mn, Nb, Mo, Ru, Rh, Pd, Ag, Au, Hf, Ta, W, Re, Os, Ir, and Pt. In some specific examples, the first surface preferably includes copper. In some specific examples, the first surface includes cobalt. In some specific examples, the first surface includes tungsten. In some specific examples, the first surface may include a native oxide of a metal. For example, the first surface may include tungsten oxide. In some specific examples, the first surface may include a seam, a gap, or a space, and the seam, a gap, or a space of the first surface closed or substantially filled by the selective deposition process. In some specific examples, the first surface includes a noble metal. The noble metal may be selected from the group: Au, Pt, Ir, Pd, Os, Ag, Re, Rh, and Ru.

In some specific examples, the second surface is a dielectric surface. In some specific examples, the second surface is a silicon-containing surface, referred to herein as a second silicon-containing surface or a second surface including silicon. In some specific examples, the silicon-containing surface includes, for example, SiO ₂ . In some specific examples, the second surface may include silicon oxide, silicon nitride, silicon carbide, silicon oxynitride, silicon dioxide, or a mixture thereof. In some specific examples, the material constituting the second surface is a porous material. In some embodiments, the porous material contains pores connected to each other, while in other embodiments, the pores are not connected to each other. In some specific examples, the second surface includes a low-k material, which is defined as an insulator having a dielectric value below about 4.0. In some specific examples, the dielectric value of the low-k material is less than about 3.5, less than about 3.0, less than about 2.5, and less than about 2.3. In some embodiments, the second surface may comprise the surface of an organic silicate, such as an organic surface groups, such as -CH _x silicon-containing surface groups of the surface. In some specific examples, the second surface may include SiOCH.

The precursors used in the process disclosed herein can be solid, liquid, or gaseous materials under standard conditions (room temperature and atmospheric pressure), provided that the precursors are guided into the reaction chamber and contact the substrate surface Previously in the gas phase. Plasma conditions can also be used. Therefore, in some embodiments, the plasma may be formed from a gas phase reactant or a precursor. "Pulsing" a gasified precursor onto a substrate means directing precursor vapor into the chamber for a limited period of time. Generally, the pulse time is about 0.05 to 10 seconds. However, depending on the type of substrate and its surface area, the pulse time can be even higher than 10 seconds. In some cases, the pulse time may be on the order of minutes. In some cases, to ensure complete saturation of the reaction, the precursor may be supplied in multiple shorter pulses rather than in one longer pulse.

The precursor mass flow rate can also be determined by those skilled in the art. In a specific example, for deposition on a 300 mm wafer, the flow rate of the precursor is preferably between about 1 sccm and 2000 sccm and is not limited thereto. In some specific examples, the flow rate may be between about 50 sccm and about 1500 sccm, between about 100 sccm and about 1000 sccm, or between about 200 sccm and about 500 sccm.

The pressure in the reaction chamber is usually from about 0.01 mbar to about 50 mbar. In some specific examples, the pressure may be between about 0.1 mbar and about 20 mbar, and between about 1 mbar and about 10 mbar. However, in some cases, the pressure will be above or below this range, as can be easily determined by those skilled in the art. Chamber passivation

Referring again to FIG. 1, in some specific examples, it may be desirable to passivate one or more reaction chambers in which a selective deposition process is performed before selectively depositing the metal film at step 14. In some embodiments, the reaction chamber passivation step 11 may achieve selective deposition, improve selectivity, and / or before loss of selectivity during a selective deposition process (e.g., a metal film selective deposition process as described herein). Increase the number of cycles.

In some specific examples, a selective deposition process for selectively depositing a film on a first surface (e.g., a metal surface) of a substrate relative to a second surface (e.g., a silicon-containing surface) may produce a second substrate that may quickly damage Surface reaction byproducts. Reaction by-products can provide active sites on the second surface, causing a loss of selectivity. In some specific examples, unwanted deposition may be performed on the surface of the reaction chamber, thereby causing an increase in the amount of reaction byproducts in the reaction chamber during the selective deposition process where the deposition is performed primarily on the substrate. In order to reduce the amount of undesired deposition on the chamber surface (such as the interior surface of the reaction chamber) and thus the amount of reaction byproducts generated by the selective deposition process, it is desirable to passivate such chamber surfaces against deposition.

For example, in some specific examples, the W selective deposition process can produce reaction by-products with the formula SiF _x , where x = 1-4. In some specific examples where the reaction chamber has not been passivated, undesired W deposition can be performed on the chamber surface, thereby generating an undesirable amount of SiF _{x by} -products. In some specific examples in which the reaction chamber has been passivated, W deposition may be performed mainly on the first surface of the substrate, and may not be performed or may be performed to a lesser extent on the surface of the undesired chamber, thereby resulting in a relative In the W selective deposition process in which the reaction chamber has not been passivated, the amount of SiF _{x by} -products generated during the selective deposition process is reduced.

In some specific examples, when there is no wafer or substrate in the reaction chamber, the reaction chamber passivation step 11 is performed. Therefore, in some specific examples, the substrate (such as a substrate including the first metal surface and the second silicon-containing surface) is not subjected to the reaction chamber passivation step 11. In some specific examples, the substrate may be subjected to other processing before, during or after the reaction chamber passivation step 11.

In some specific examples, the reaction chamber passivation step 11 may be repeated after the selective deposition process has been performed at step 14. In some specific examples, the reaction chamber passivation step 11 may be repeated after each, two, three, or more than three selective deposition steps 14 have been performed. For example, in some specific examples, the reaction chamber may be repeated after every 1, 5, 10, 20, 50, or more than 50 substrates (such as wafers) have been subjected to the selective deposition step 14. Passivation step 11. In some specific examples, the reaction chamber passivation step 11 may be repeated after a certain number of cycles of the selective deposition step 14 have been performed. In some specific examples, the reaction chamber passivation step 11 may be repeated after every 50, 100, 150, or more than 150 selective deposition cycles. In some specific examples, during the reaction chamber passivation step 11, one or more substrates may remain in the reaction chamber, or may not be present in the reaction chamber.

In some specific examples, the reaction chamber passivation step 11 may include providing a passivation layer or passivation material on the chamber surface and other surfaces that may be exposed to the precursor or reactants during the selective deposition step 14. In some embodiments, a passivation material is deposited or formed on the interior surface of the reaction chamber, the chamber showerhead, and / or can be exposed to the precursor or any other chamber component in the reaction during the selective deposition step 14 . In some embodiments, the passivation material can be deposited on any surface in the reaction chamber, and any surface is not a substrate that needs to be selectively deposited. In some embodiments, the passivation material is a different material from the material selectively deposited in step 14. In some specific examples, the deposition process used to deposit the passivation layer may not be a selective deposition process.

In some embodiments, the passivation of the reaction chamber 11 can increase the number of consecutive cycles in which the desired level of selectivity of the selective deposition process 14 is maintained. In some specific examples, the reaction chamber passivation process 11 may increase the number of consecutive cycles in which the desired level of selectivity of the selective deposition process 14 is maintained, compared to a reaction chamber that has not been subjected to any reaction chamber passivation process 11 by more than about 50%. In some specific examples, the reaction chamber passivation process 11 may increase the number of consecutive cycles in which the desired level of selectivity of the selective deposition process 14 is maintained, compared to a reaction chamber that has not been subjected to any reaction chamber passivation process 11 by more than about 75%, greater than about 100%, greater than about 200%, greater than about 400%, or greater than about 900%. In some specific examples, the reaction chamber passivation process 11 may increase the number of consecutive cycles in which the desired level of selectivity of the selective deposition process 14 is maintained, compared to a reaction chamber that has not been subjected to any reaction chamber passivation process 11 by more than about 20 times.

In some specific examples, the reaction chamber passivation process 11 can increase the number of consecutive cycles in which the desired level of selectivity of the selective deposition process 14 is maintained, and the reaction chamber passivation process 11 can be repeated after the desired number of cycles to allow An additional continuous cycle in which the desired level of selectivity of the selective deposition process 14 is maintained. That is, the reaction chamber passivation process 11 may be performed after a desired number of consecutive cycles and before the selectivity of the selective deposition process has been reduced below a desired level in order to allow the desired selectivity level of the selective deposition process to be maintained therein Extra continuous loop. The reaction chamber passivation 11 may be repeated any number of times after a desired number of consecutive cycles of the selective deposition process in order to maintain the desired selectivity level of the selective deposition process 14.

In some specific examples, one or more previously deposited passivation layers may be etched or at least partially removed from an inner surface of the reaction chamber before a subsequent passivation layer is deposited via the reaction chamber passivation process 11. In some specific examples, one or more previous deposits may be etched after the reaction chamber has been subjected to the reaction chamber passivation process 11 two or more times, five or more times, five or more times, or ten or more times. The passivation layer or the internal surface of the reaction chamber at least partially removes the previously deposited passivation layer. In some specific examples, etching or layer removal is not performed between two or more than two, five or more than five or ten or more than ten reaction chamber passivation processes. In some specific examples, the reaction chamber may then be subjected to the reaction chamber passivation process 11 after one or more previously deposited passivation layers have been etched or the previously deposited passivation layers have been at least partially removed from the inner surface of the reaction chamber.

In some specific examples, the passivation of the reaction chamber 11 can increase the duration for which the desired selectivity level of the selective deposition process 14 is maintained. In some specific examples, the reaction chamber passivation process 11 can increase the duration of maintaining the desired selectivity level of the selective deposition process 14 compared to a reaction chamber that has not undergone any reaction chamber passivation process 11 by more than about 50. %, Greater than about 75%, greater than about 100%, greater than about 200%, greater than about 400%, or greater than about 900%. In some specific examples, the reaction chamber passivation process 11 can increase the duration of maintaining the desired selectivity level of the selective deposition process 14 compared to the reaction chamber that has not been subjected to any reaction chamber passivation process 11 by more than about 20 Times.

In some specific examples, the passivation of the reaction chamber 11 can increase the number of substrates (eg, wafers) targeted to maintain the desired selectivity level of the selective deposition process 14. That is, the reaction chamber passivation 11 can increase the number of wafers that can be selectively deposited, while maintaining a desired level of selectivity. In some specific examples, the reaction chamber passivation process 11 may increase the number of substrates targeted for maintaining the desired level of selectivity of the selective deposition process 14 compared to the number of reaction chambers that have not yet undergone any reaction chamber passivation process 11 2 times, greater than about 5 times, greater than about 10 times, greater than about 20 times, or greater than about 50 times.

In some embodiments, the reaction chamber passivation process 11 can increase the number of deposition cycles that can be performed in the reaction chamber before maintenance is needed. In some specific examples, the reaction chamber passivation process 11 can increase the number of deposition cycles that can be performed in the reaction chamber before maintenance is required compared to a reaction chamber that has not been subjected to any reaction chamber passivation process 11 by more than about 50%, greater than about 75%, greater than about 100%, greater than about 200%, greater than about 400%, greater than about 900%, or greater than about 20 times.

In some embodiments, during the selective deposition process, materials may be deposited on the inner surface of the reaction chamber. This deposited material can be layered and interfere with selective deposition, or it can provide reactive sites so that an undesirably large number of undesirable reaction by-products can be generated during the selective deposition process. Therefore, it may be necessary to periodically remove the deposited material from the inner surface of the reaction chamber. In some specific examples, the reaction chamber passivation process 11 can increase the number of deposition cycles that can be performed in the reaction chamber before etching (eg, in-situ etching) must be performed to obtain or maintain a desired level of selectivity. In some specific examples, the reaction chamber passivation process 11 enables the number of deposition cycles that can be performed in the reaction chamber before etching (e.g., in-situ etching) must be performed to obtain or maintain a desired level of selectivity compared to The reaction chamber that has undergone any reaction chamber passivation process 11 increases by more than about 50%, more than about 75%, more than about 100%, more than about 200%, more than about 400%, more than about 900%, or more than about 20 times.

In some embodiments, the passivation layer deposited or formed during the reaction chamber passivation step 11 may include SiN. In some specific examples, the passivation layer may include silicon oxide, silicon nitride, silicon carbide, silicon oxynitride, or a mixture thereof. In some specific examples, the passivation layer may include a metal oxide. In some specific examples, the passivation layer may include any material other than pure metal or pure silicon. In some specific examples, the passivation layer is not a self-assembled monolayer (SAM) or a similar layer whose molecules are similar to the molecules used to form the SAM.

In some specific examples, the passivation layer may be deposited or formed at step 11 by a vapor deposition process. In some embodiments, the deposition process used to form the passivation layer may include a chemically driven vapor deposition process. That is, the deposition process used to form the passivation layer is a vapor deposition process that depends on one or more chemical reactions of the precursor, and is not a physical vapor deposition process. For example, the deposition process used to form or deposit the passivation layer may be a chemical vapor deposition (CVD) process or an atomic layer deposition (ALD) process. In some specific examples, the passivation layer may be formed by a plasma enhanced ALD (PEALD) process or a plasma enhanced CVD (PECVD) process.

In some specific examples, the deposition process for forming a passivation layer may include between 1 and 10,000 deposition cycles, between 5 and 5,000 deposition cycles, between 10 and 2,500 Between 10 or 50 deposition cycles. In some specific examples, the thickness of the passivation layer may be about 1 nm to about 1000 nm, about 5 nm to about 500 nm, about 10 nm to about 250 nm, or about 40 nm to about 150 nm. However, in some specific examples, it may be applicable to make the thickness of the passivation layer less than 1 nm. In some specific examples, the thickness of the passivation layer may be less than about 200 nm, less than about 100 nm, less than about 50 nm, and less than about 25 nm.

In some specific examples, the deposition process for forming the passivation layer may include an ALD type process, which includes one or more deposition cycles, and the deposition cycle includes alternately and sequentially exposing the surface of the reaction chamber to the first gas phase precursor And the second gas phase precursor, or the surface of the reaction chamber and the first gas phase precursor and the second gas phase precursor are alternately and sequentially contacted. In some specific examples, the first gas phase precursor and reaction by-products (if present) may be used to expose the surface of the reaction chamber to the second gas phase precursor or contact the surface of the reaction chamber with the second gas phase precursor. Removed from the reaction chamber before. In some specific examples, the second gas phase precursor and any reaction byproducts may be similar before the surface of the reaction chamber is subsequently exposed to the first gas phase precursor or the surface of the reaction chamber is brought into contact with the first gas phase precursor. Ground is removed from the reaction chamber.

In some specific examples, the deposition process for forming the passivation layer may include a CVD-type process, wherein the first gas phase precursor and the second gas phase precursor are guided into the reaction chamber at the same time or in overlapping pulses, wherein these The precursor reacts and / or decomposes on the surface of the chamber to form a passivation layer.

In some specific examples, the deposition process for forming the passivation layer may include a PECVD type process, in which the first gas phase precursor and the second gas phase precursor are guided into the reaction chamber in a simultaneous or overlapping pulse, and wherein A slurry is produced in the reaction chamber. The precursor reacts and / or decomposes in the plasma and / or on the surface of the chamber to form a passivation layer. In some embodiments, a plasma may be generated at a distal end and introduced into a reaction chamber.

In some specific examples, the deposition process for forming a passivation layer including SiN may be a PECVD process. In some specific examples, the PECVD deposition process may use a gas phase silicon precursor and a gas phase nitrogen precursor. In some embodiments, the silicon precursor and the nitrogen precursor may be provided into the reaction chamber together or in overlapping pulses. In some specific examples, a plasma is generated in the reaction chamber and the silicon precursor and the nitrogen precursor react and / or decompose to form a SiN passivation layer on the surface of the chamber. In some embodiments, a plasma may be generated at a distal end and introduced into a reaction chamber.

In some embodiments, a deposition process for forming a passivation layer including silicon (such as SiN) may utilize a silicon precursor and one or more additional precursors, such as a nitrogen precursor. In some specific examples, a deposition process for forming a passivation layer may utilize a nitrogen precursor. In some specific examples, the silicon precursor used in the passivation layer deposition process may include a silane, such as a silane, a disilane, or a trisilane. In some specific examples, the nitrogen precursor may be atomic nitrogen, a nitrogen radical, a nitrogen plasma, or a combination thereof. In some specific examples, the nitrogen precursor may further include atomic hydrogen, a hydrogen radical, a hydrogen plasma, or a combination thereof. In some embodiments, the nitrogen precursor may include a plasma generated from N ₂ . In some embodiments, the nitrogen precursor may include a plasma generated from N ₂ and H ₂ . In some embodiments, the nitrogen precursor may include a plasma generated from N ₂ and a rare gas such as argon. In some specific examples, the nitrogen precursor may include a plasma generated from N ₂ , H ₂ and a rare gas such as argon. In some specific examples, the silicon precursor and the nitrogen precursor may be separately provided into the reaction chamber in an ALD type reaction, or the silicon precursor and the nitrogen precursor may be provided together or in overlapping pulses to the reaction chamber in a CVD reaction. Reaction chamber.

In some specific examples, a deposition process for forming a passivation layer (for example, a passivation layer including silicon and nitrogen, such as SiN) may include one or more deposition cycles, and the deposition cycle includes alternately and sequentially exposing the reaction chamber surface In the first gas phase precursor, the second gas phase precursor, and the third gas phase precursor or alternate the surface of the reaction chamber with the first gas phase precursor, the second gas phase precursor, and the third gas phase precursor And contact them sequentially. In some specific examples, the first gas phase precursor may include silane; the second gas phase precursor may include metal halide; and the third gas phase precursor may include amine silane. In some specific examples, the first gas-phase precursor may include disilane; the second gas-phase precursor may include WF ₆ ; and the third gas-phase precursor may include trimethyl (dimethylamino) silane.

The terms first, second, and third precursors are used herein for reference only, and those skilled in the art will understand that the deposition cycle may expose the reaction chamber surface to the first, second, or third gas phase precursors Either start. In some specific examples, the first gas phase precursor may contact the substrate before the second or third gas phase precursor. In some specific examples, the second gas phase precursor may contact the substrate after the first gas phase precursor and before the third gas phase precursor. In some specific examples, the third gas phase precursor may contact the substrate after both the first and second gas phase precursors. In some specific examples, the order of the first, second, and third gas phase precursors may be different. In some specific examples, two, three, or more than three precursors may be provided together or at least partially overlapped pulses, regardless of being referred to as a first precursor, a second precursor, a third precursor, and the like. . In addition, the reaction chamber surface can be brought into contact with the gas phase precursors alternately and sequentially in any order as determined by those skilled in the art. For example, chamber surfaces may be brought into contact with a third gas phase precursor before they are brought into contact with a second gas phase precursor in a given deposition cycle.

In some specific examples, the passivation layer deposition process using the first, second and third gas phase precursors may include one or more deposition cycles, three or more deposition cycles, five or more than five Deposition cycles or ten or more deposition cycles, 25 or more deposition cycles, and in some cases, less than or equal to 50 deposition cycles may be included.

In some specific examples, the passivation layer deposited by the passivation layer deposition process using the first, second, and third vapor phase precursors is after each selective deposition process 14 or after each selective deposition process 14 has been subjected to it. A substrate (such as a wafer) is then deposited. That is, after the selective deposition process, the substrate may be removed from the reaction chamber, and an additional passivation layer may be deposited by the passivation layer deposition process. In some embodiments, an additional passivation layer is deposited by the passivation layer deposition process after each substrate that has been subjected to the selective deposition process.

In some specific examples, the passivation layer deposited by the passivation layer deposition process using the first, second, and third vapor phase precursors is more than every two substrates and more than every four that have been subjected to the selective deposition process 14. Substrates are deposited after more than every nine substrates or more than every 19 substrates.

In some specific examples, the deposition process for forming the passivation layer may be performed at a reaction chamber pressure and temperature similar to or the same as the reaction chamber of the selective deposition process as described herein. In some specific examples, the flow rate of the gas phase precursor used in the passivation layer deposition process may be similar to or the same as the precursor flow rate used in the selective deposition process as described herein.

In some embodiments, the passivation layer may be deposited at a temperature of less than about 400 ° C. In some embodiments, the passivation layer may be deposited at a temperature of less than about 250 ° C. In some embodiments, the passivation layer may be deposited at a temperature of less than about 150 ° C. In some embodiments, the passivation layer may be deposited at a temperature of less than about 100 ° C.

In some specific examples, the passivation layer may be deposited at, for example, about 20 ° C to about 250 ° C, about 30 ° C to about 200 ° C, or about 40 ° C to 150 ° C. In some embodiments, the passivation layer can be deposited at a temperature about the same as the temperature at which the subsequent selective deposition process can be performed.

In some specific examples, the surface of the chamber where the passivation layer is deposited may be cleaned as appropriate before the passivation layer is deposited. In some embodiments, the chamber surfaces can be cleaned by exposing the chamber surfaces to a plasma. For example, in some embodiments, it may comprise a reaction chamber by exposure to free radicals comprising fluorine, (such as NF-based radical of ₃₎ to clean the reaction chamber.

In some embodiments, the metal oxide passivation layer may be formed by a vapor deposition process (eg, an ALD, CVD, PEALD, or PECVD process). In some specific examples, the deposition process for forming a passivation layer may include between 1 and 10,000 deposition cycles, between 5 and 5,000 deposition cycles, between 10 and 2,500 Between 10 or 50 deposition cycles.

In some specific examples, the passivation layer may include a metal oxide. In some specific examples, the passivation layer may include a transition metal oxide. In some specific examples, the passivation layer may include, for example, tantalum oxide (Ta ₂ O ₅ ), titanium oxide (TiO ₂ ), niobium oxide (Nb ₂ O ₅ ), zirconium oxide (ZrO ₂ ), hafnium oxide (HfO ₂ ), Tungsten oxide (WO _x ), molybdenum oxide (MoO _x ), or vanadium oxide (VO _x ). In some specific examples, a passivation layer including a transition metal oxide may be formed by a deposition process including one or more deposition cycles including alternating and sequential exposure of the reaction chamber surface to the first gas phase In the precursor and the second gas phase precursor, the surface of the reaction chamber is brought into contact with the first gas phase precursor and the second gas phase precursor. In some specific examples, the deposition process may be an ALD, CVD, PEALD, or PECVD process. In some specific examples, the first gas phase precursor may include a transition metal. In some specific examples, the first gas phase precursor may include a metal halide or an organometallic compound. In some specific examples, the second gas phase precursor may include oxygen. In some specific examples, the second gas-phase precursor may be an oxygen reactant or an oxygen source. In some specific examples, the second gas phase precursor may include O ₃ , H ₂ O, H ₂ O ₂ , an oxygen atom, an oxygen plasma, an oxygen radical, or a combination thereof.

In some specific examples, the passivation layer including Al ₂ O ₃ may be formed by a deposition process including one or more deposition cycles, which include alternately and sequentially exposing the surface of the reaction chamber to a first A gas phase precursor and a second gas phase precursor including oxygen or alternately and sequentially contact the reaction chamber surface with the first gas phase precursor and the second gas phase precursor. In some specific examples, the first gas phase precursor including aluminum may include an organometallic compound including aluminum, such as trimethylaluminum (TMA). In some specific examples, the second gas phase precursor including oxygen may include O ₃ , H ₂ O, H ₂ O ₂ , an oxygen atom, an oxygen plasma, an oxygen radical, or a combination thereof. In addition, in some specific examples, the first and second gas phase precursors may be provided in any order that can be easily determined by those skilled in the art. In some embodiments, the first and second gas phase precursors may be provided together or at least partially in overlapping pulses, such as in a CVD process.

In some embodiments, the metal material may be deposited or formed on the surface of the chamber by a vapor deposition process (eg, by a chemical vapor deposition (CVD) or atomic layer deposition (ALD) process). In some specific examples, the metallic material may include antimony, such as elemental antimony. In some specific examples, the passivation layer may be formed by a plasma enhanced ALD (PEALD) process. In some specific examples, the deposition process for forming a passivation layer may include between 1 and 10,000 deposition cycles, between 5 and 5,000 deposition cycles, between 10 and 2,500 Between 10 or 50 deposition cycles.

In some embodiments, the metal material may be subsequently oxidized to form a metal oxide passivation layer. In some embodiments, the metal material may be oxidized by exposing the metal material to an oxygen reactant. In some specific examples, the oxygen reactant may include oxygen, an oxygen atom, an oxygen radical, an oxygen plasma, or a combination thereof. For example, in some specific examples, the oxygen reactant may include O ₃ , H ₂ O, H ₂ O ₂ , an oxygen atom, an oxygen plasma, an oxygen radical, or a combination thereof. In some embodiments, the metal material may be subjected to an oxidation process that includes at least one step of exposing the metal material to an oxidant or an oxygen reactant. In some embodiments, the oxidation process may include exposing the metallic material to two or more oxidants or oxygen reactants in two or more steps. In some specific examples, two or more than two oxidants or oxygen reactants may be different oxidants or oxygen reactants. In some embodiments, two or more exposure steps may be separated by a purification or oxidant removal step. In some embodiments, exposing a metal material to more than one oxidant or oxygen reactant may desirably produce a greater amount of oxidation of the metal material than when exposed to one oxidant or oxygen reactant.

In some embodiments, the passivation layer may be formed on the chamber surface by oxidizing a metal material that has been deposited on the chamber surface during a previous deposition process. In some specific examples in which the selective deposition step 14 has been previously performed in the reaction chamber, the reaction chamber passivation step 11 may include oxidizing any metallic material deposited on the surface of the chamber during the selective deposition step 14 to form Metal oxide passivation layer. In some embodiments, the metal material may be oxidized by exposing the metal material to an oxygen precursor. In some specific examples, the oxygen precursor may include oxygen, an oxygen atom, an oxygen radical, an oxygen plasma, or a combination thereof.

For example, W deposited on the chamber surface during a previous W selective deposition process may be oxidized to form a chamber passivation layer. In some embodiments, the metal material is deposited on the surface of the chamber by a deposition process that is not used to deposit the material on a substrate or a wafer in the reaction chamber. Silicon-containing surface treatment

As shown in FIG. 1 and in some specific examples, the silicon-containing material that is deposited thereon may be processed at step 12 to avoid deposition thereon. For example, in some embodiments, the silicon-containing material may be processed after the surface is cleaned and before deposition. In some embodiments, the silicon-containing surface can be treated by reducing the amount of material deposited on the silicon-containing surface (eg, by passivating the silicon-containing surface) to enhance the selectivity of the deposition process. In some embodiments, the process is intended to restore the silicon-containing layer without blocking the deposition on the silicon-containing layer.

In some specific examples, the silicon-containing surface is a low-k surface that has been degassed to remove moisture absorbed from the atmosphere.

In some embodiments, the processing of the silicon-containing material is a dielectric recovery step. Different kinds of silicon-containing material recovery steps can be performed before selective deposition and after the surface has been cleaned (if implemented).

In some embodiments, the silicon-containing surface is treated by contacting the silicon-containing surface with one or more silanes, such as disilane. In some specific examples, the silicon-containing surface is treated with trimethylchlorosilane (CH ₃ ) ₃ SiCl (TMCS) or other types of alkyl halosilanes having the formula R _3-x SiX _x , where x Is 1 to 3 and each R can be independently selected as a C1-C5 hydrocarbon such as methyl, ethyl, propyl or butyl, preferably methyl, and X is a halide group, preferably a chloride group. US Patent No. 6,391,785 discloses various surface modifications and treatments, and is incorporated herein in its entirety. In some specific examples, any of the surface modifications or treatments disclosed in US Patent No. 6,391,785 can be used in the methods disclosed herein.

In some embodiments, the silicon-containing surface is contacted with, for example, trimethyl (dimethylamino) silane. In some specific examples, the silicon-containing surface is contacted with an alkylaminosilane having the formula (R ^I ) ₃ Si (NR ^II R ^III ), where R ^I is a linear or branched C1-C5 alkyl or linear Or branched C1-C4 alkyl, R ^II is straight or branched C1-C5 alkyl, straight or branched C1-C4 alkyl, or hydrogen, and R ^III is straight or branched C1-C5 alkyl Or straight or branched C1-C4 alkyl.

In some specific examples, a silicon-containing surface is contacted with a silane having the general formula (R ^I ) ₃ SiA, wherein R ^I is a linear or branched C1-C5 alkyl group or a linear or branched C1-C4 alkyl group, And A is any ligand that can react with the silicon-containing surface. That is, the silane is bonded to the surface through the ligand A, or the ligand A forms a bond with the surface, but then the ligand A can be transferred away from the surface and / or the silane.

In some specific examples, the repair chemical is selected from the silane family and has the chemical formula Si _n H _{2n + 2} (n is equal to or greater than 1), or is selected from the cyclic silane family and has the chemical formula Si _n H _2n (n is equal to or larger than 3). In some specific examples, the recovery chemical is a silicon source, which includes a silane, a disilane, or a trisilane. In some specific examples, the silane is disilane Si ₂ H ₆ or trisilane Si ₃ H ₈ . In some specific examples, the silicon source may be selected from a silane compound having the formula: SiH _x L _y , where L is a ligand selected from the group consisting of: alkyl, alkenyl, alkynyl, alkoxide And amines. In some cases, L is a ligand selected from the following halide groups: F, Cl, Br, and I.

In some embodiments, the substrate is exposed to one or more recovery chemicals (such as Si ₂ H ₆ or TMCS) at a temperature of about room temperature to about 150 ° C or about 40 ° C to about 130 ° C before selective deposition. ) And a silicon-containing surface recovery step is performed. In some embodiments, the silicon-containing surface recovery step can be performed at a temperature of up to about 400 ° C, about 25 ° C to about 300 ° C, or 30 ° C to about 250 ° C. In some specific examples, a recovery chemical (such as Si ₂ H ₆ ) is provided into the reaction chamber at a flow rate of about 5 sccm to 100 sccm or about 30 sccm to 60 sccm. In some specific examples, the recovery chemical is provided into the reaction chamber for about 1 s to 20 s or about 1 s to 10 s. In some embodiments, a recovery chemical, such as TMCS, is provided in a pulse. About 1 to 20 or about 1 to 10 pulses can be provided, for example, with a pulse and purification time of about 1 to 10 seconds. In some embodiments, the silicon-containing surface recovery step can be performed in a second separate reaction chamber separate from the reaction chamber in which deposition can be performed.

Although this step is referred to as a surface recovery step and the chemical used is referred to as a recovery chemical, these labels are used herein for simplicity and do not imply a specific recovery function. Therefore, in some specific cases, the processing and / or chemicals may be insufficient or even partially restore the silicon-containing surface.

If the silicon-containing surface is damaged, it can also be recovered by performing a surface recovery step after the selective deposition step.

Some silicon-containing materials may have a porous structure. To avoid diffusion, etching, and other undesirable processes, the pores can be sealed or capped with protective groups before starting the deposition process. Therefore, in some embodiments, the porous silicon-containing material can be treated to seal or cap the pores with a protective group before starting selective deposition. In some embodiments, the porous silicon-containing material is processed before the metal reactant is provided.

In some specific examples, the pores can be sealed by forming Si (R ^I ) ₃ groups on the silicon-containing surface, where R ^I can be a linear or branched C1-C5 alkyl or a linear or branched C1 -C4 alkyl. In some specific examples, the pores are sealed by silylation on a silicon-containing surface (such as a low-k or SiO ₂ surface), that is, forming a -Si (CH ₃ ) ₃ group. Etching can be partially avoided by silylation before introducing metal fluorides or other reactants. Silaneization can also be used to block these pores to prevent reactants from penetrating into the silicon-containing material. In some specific examples, silylation is achieved by reacting a silicon compound (such as Cl-Si (CH ₃ ) ₃ ) with the surface of a silicon-containing material terminated by Si-OH: Si-OH + Cl-Si (CH ₃ ) _3- > Si-O-Si (CH ₃ ) ₃ + HCl. Therefore, in some specific examples, an appropriate surface termination state is formed before the silicon compound is provided. It is also possible to use silicon compounds with longer carbons containing ligands.

A method for sealing the pores is disclosed, for example, in US Patent No. 6,759,325. The disclosure of the sealing method in US Patent No. 6,759,325 is hereby incorporated by reference in its entirety.

In some specific examples, the organic layer can be formed on the silicon-containing material by ALD before deposition to block the pores and make the silicon-containing surface more resistant to metal fluoride.

In some specific cases where the selectivity is imperfect or requires higher selectivity, the surface may be treated after selective deposition, such as using isotropic selective metal etching, to remove material from the surface of the insulator without Material is completely removed from the metal surface. For example, HCl vapor or wet etching can be used. First metal surface treatment

In some specific examples, the substrate may be subjected to a process for removing a surface layer from a metal surface as described herein. For example, as described above, a substrate including at least one first metal surface may be subjected to a process of removing a surface layer therefrom as described herein before selectively depositing a thin film thereon. In some specific examples, the substrate may be subjected to a process for removing a surface layer from a first metal surface of the substrate in a reaction chamber that has been passivated as described herein. However, in some other specific examples, the substrate may be subjected to a process for removing a surface layer from a first metal surface of the substrate in a reaction chamber that has not been passivated.

As shown in FIG. 1 and according to some specific examples, the substrate surface may be cleaned or treated at step 13 as appropriate. For example, for a specific example when the first material is copper, the copper surface may be cleaned or reduced so that pure elemental copper is on the surface of the substrate. In some specific examples, the first surface treatment process may include a surface layer removal process as described above. For example, the first surface treatment process can remove the surface layer existing on the first surface of the substrate in order to achieve or enhance the selective deposition performed thereon. In some specific examples, the removed surface layer may include an organic material layer. That is, in some specific examples, the first surface treatment process can remove any organic material existing on the first metal surface. For example, the first surface treatment process can remove the organic passivation layer existing on the first metal surface. For example, the first surface treatment process can remove a benzotriazole (BTA) passivation layer from a copper surface. In some specific examples, the first surface treatment process may remove any organic layer and / or hydrocarbon layer that may be present on the first metal surface.

In some specific examples, the first surface treatment process can reduce the surface layer or a part of the surface layer existing on the first metal surface of the substrate. In some specific examples, the first surface treatment process can reduce and / or remove any oxide surface layer present on the first metal surface. In some specific examples, the first surface treatment process can reduce and / or remove any native oxides that may be present on the first metal surface. In some specific examples, the first surface treatment process may provide active sites on the first metal surface, such as by reducing and / or removing a surface layer or a portion of the surface layer present on the first metal surface. In some specific examples, the oxide layer can be partially removed by the first surface treatment process and the remaining material including the oxide layer can be reduced. That is, in some specific examples, part of the oxide layer can be removed by the first surface treatment process, and any remaining oxide layer can be reduced by the first surface treatment process. In some specific examples, substantially all of the oxide surface layer can be removed by a first surface treatment process. In some specific examples, substantially all of the oxide surface layer can be reduced by a first surface treatment process.

As used herein, the term reduction may refer to the chemical conversion of an oxide material into its non-oxide form. That is, when a metal oxide material is reduced, it is chemically converted into a metal of the metal oxide. For example, a copper oxide layer may be present on a first metal surface including copper, and the first surface treatment process may reduce the copper oxide layer so that it is converted into metallic copper. In some specific examples, the surface layer may include both an organic surface layer and an oxide layer below the organic surface layer. In some specific examples where the first metal surface may include a surface layer including an organic surface layer and an oxide layer below the organic surface layer, the first surface treatment process may remove the organic surface layer and may also reduce the oxide layer and And / or remove it to provide a clean first metal surface.

The first surface treatment process may be performed in any of a variety of methods (for example, using a chemical such as citric acid or using a plasma). For example, the substrate surface may be cleaned or treated using a plasma generated by a gas, such as a gas including hydrogen, including H ₂ , NH _3, and / or other component gases. In some specific examples, HCl treatment is used as the first surface treatment method. In some specific examples, the first surface treatment process includes exposing the substrate to a treatment reactant, such as formic acid. Other first surface treatment methods are also possible. The specific first surface treatment method to be used in any particular case can be selected based on a variety of factors, such as materials and deposition conditions, including, for example, the type of material on the substrate surface.

In some cases, a first material (such as copper) that requires selective deposition thereon is passivated. This passivation may be the result of intentional processing of the substrate to form a passivation layer; or it may be caused by processing conditions, such as exposure to oxygen during transport of the substrate.

The surface of the substrate can be passivated, for example, before being transferred from one reaction space to another. In some specific examples, any one of a number of known passivation chemicals can be used to passivate the surface of the first material for oxidation in the air. In some specific cases where selective deposition on Cu is required, the surface of Cu can be passivated, for example, with BTA. This passivation can be removed using the first surface treatment method described herein.

In some specific examples, the first surface treatment process includes exposing the substrate to a treatment reactant. In some specific examples, the treatment reactant is a gas-phase organic reactant. In some specific examples, the treatment reactant may contain at least one alcohol group and may be preferably selected from the group consisting of a primary alcohol, a secondary alcohol, a tertiary alcohol, a polyol, a cyclic alcohol, an aromatic alcohol, and Other derivatives of alcohols.

Preferred primary alcohols have an -OH group attached to a carbon atom bonded to another carbon atom, especially a primary alcohol according to formula (I):

R ¹ -OH (I)

Wherein R ¹ is a linear or branched C ₁ -C ₂₀ alkyl or alkenyl group, preferably methyl, ethyl, propyl, butyl, pentyl or hexyl. Examples of preferred primary alcohols include methanol, ethanol, propanol, butanol, 2-methylpropanol, and 2-methylbutanol.

Preferred secondary alcohols have an -OH group attached to a carbon atom bonded to two other carbon atoms. In detail, the preferred second alcohol has the general formula (II):

OH

R ¹ -CH-R ¹ (II)

Wherein each R ^{1 is} independently selected from the group of linear or branched C ₁ -C ₂₀ alkyl and alkenyl groups, preferably selected from methyl, ethyl, propyl, butyl, pentyl or hexyl. Examples of preferred secondary alcohols include 2-propanol and 2-butanol.

Preferred tertiary alcohols have an -OH group attached to a carbon atom bonded to three other carbon atoms. In detail, preferred tertiary alcohols have the general formula (III):

OH

R ¹ -CR ¹ (III)

R ¹

Wherein each R ^{1 is} independently selected from the group of linear or branched C ₁ -C ₂₀ alkyl and alkenyl groups, preferably selected from methyl, ethyl, propyl, butyl, pentyl or hexyl. An example of a preferred tertiary alcohol is tertiary butanol.

Preferred polyols, such as diols and triols, have primary, secondary and / or tertiary alcohol groups as described above. Examples of preferred polyols are ethylene glycol and glycerol.

Preferably, the cyclic alcohol has an -OH group attached to at least one carbon atom which is itself part of a ring having 1 to 10 carbon atoms, more preferably 5 to 6 carbon atoms.

Preferred aromatic alcohols have at least one -OH group attached to a carbon atom in a benzene ring or side chain.

A preferred treatment reactant containing at least one aldehyde group (-CHO) is selected from the group consisting of a compound having the general formula (V), an alkanedialdehyde compound having the general formula (VI), and other aldehydes. derivative.

Therefore, in a specific example, the preferred treatment reactant is an aldehyde having the general formula (V):

R ³ -CHO (V)

Wherein R ³ is selected from the group consisting of hydrogen and linear or branched C ₁ -C ₂₀ , and is preferably selected from methyl, ethyl, propyl, butyl, pentyl or hexyl. More preferably, R ³ is selected from the group consisting of methyl or ethyl. Examples of preferred compounds according to formula (V) are formaldehyde, acetaldehyde and butyraldehyde.

In another specific example, the preferred treatment reactant is an aldehyde having the general formula (VI):

OHC-R ⁴ -CHO (VI)

Wherein R ⁴ is a linear or branched C ₁ -C ₂₀ saturated or unsaturated hydrocarbon. Alternatively, the aldehyde groups may be directly bonded to each other (R ^{4 is} not present).

Preferred treatment reactants containing at least one -COOH group are preferably selected from the group consisting of compounds of the general formula (VII), polycarboxylic acids and other derivatives of carboxylic acids.

Therefore, in a specific example, the preferred treatment reactant is a carboxylic acid having the general formula (VII):

R ⁵ -COOH (VII)

Wherein R ⁵ is hydrogen or straight or branched C ₁ -C ₂₀ alkyl or alkenyl, preferably methyl, ethyl, propyl, butyl, pentyl or hexyl, more preferably methyl or ethyl . In some specific examples, R ⁵ is a linear or branched C ₁ -C ₃ alkyl or alkenyl group. Examples of preferred compounds according to formula (VII) are formic acid, propionic acid and acetic acid, most preferably formic acid (HCOOH).

In some specific examples, the first surface treatment process is a process described in US Patent Application No. 14/628799 entitled "REMOVAL OF SURFACE PASSIVATION", which is hereby incorporated by reference in its entirety. Ways merge.

In some specific examples, the first metal surface of the substrate is subjected to a first surface treatment process. The first surface treatment process includes exposing the substrate to a plasma generated by a gas. In some specific examples, the first surface treatment process may include exposing at least the first surface to a plasma. In some specific examples, the first surface treatment process may include exposing the first surface and the second surface to a plasma. Such a first surface treatment process may, for example, remove a passivation layer present on a first metal surface, such as a Cu surface. Such a first surface treatment process may also reduce or remove the oxide layer from the first metal surface, such as reducing the copper oxide layer or removing it from the Cu surface.

In some embodiments, the first surface treatment process includes exposing the substrate to a plasma generated by a gas. In some embodiments, the plasma may be generated from a gas consisting of Ar alone. In some specific examples, a plasma containing Ar and H is used in the first surface treatment process. In some specific examples, a plasma containing Ar, H, and N is used in the first surface treatment process. It may be noted that instead of Ar, other noble gases such as He, Ne, Kr or Xe may be used in substantially the same conditions. In some embodiments, more than one type of plasma can be used. For example, one or more of a plasma containing Ar, a plasma containing Ar and H, and a plasma containing Ar, H, and N may be provided. That is, in some embodiments, the plasma may be generated from a gas including one or more Ar, H, and / or N-containing gases. In some specific examples, Ar or another rare gas may be used as a carrier gas for generating a component gas of the plasma. For example, in some specific examples where plasma is generated from a gas including H ₂ , Ar may be used as a carrier gas for H ₂ . Therefore, in some specific examples, the plasma generated by a gas including H ₂ and a carrier gas may include an H plasma and an Ar plasma.

In some specific examples, a plasma generated from a gas including H ₂ may be used in the first surface treatment process. In some embodiments, a plasma generated from a gas including ethanol may be used in the first surface treatment process. In some embodiments, a plasma generated from a gas including H ₂ and ethanol can be used in the first surface treatment process. In some specific examples where the first metal surface is a Cu surface, a plasma generated from a gas including H ₂ , ethanol, or H ₂ and ethanol is preferably used in the first surface treatment process.

In some embodiments, a plasma generated from a gas including NH ₃ can be used in the first surface treatment process. In some specific examples, a plasma generated from a gas including NH ₃ and H ₂ may be used in the first surface treatment process. For example, in some specific examples in which the first metal surface is a Co surface, a plasma generated by a gas including NH ₃ and H ₂ is used in the first surface treatment process. In some specific examples, the plasma may be composed of NH ₃ and H ₂ gas generation, wherein the ratio of NH ₃ to H ₂ is from about 1: 100 to about 1: 1, preferably from about 1: 5 to about 1:20. In some specific examples, the ratio of NH ₃ to H ₂ may be about 1:19, about 1: 9, or about 1: 5.

In some embodiments, a plasma generated from a gas including one or more organic compounds may be used in the first surface treatment process. In some specific examples, a plasma generated from a gas including a compound according to formula (I) to formula (VII) above may be used in the first surface treatment process. In some specific examples, a plasma generated from a gas including formic acid (HCOOH) may be used in the first surface treatment process. In some embodiments, a plasma generated from a gas including carbolic acid may be used in the first surface treatment process. In some specific examples, a plasma generated from a gas including HCOOH and NH ₃ may be used in the first surface treatment process. In some specific examples, a plasma generated from a gas including HCOOH and H ₂ may be used in the first surface treatment process.

In some specific examples, a plasma generated from a gas including HCOOH, NH ₃ and H ₂ may be used in the first surface treatment process. In some specific examples, the plasma may be generated from a gas including HCOOH, NH ₃ and H ₂ , wherein the ratio of HCOOH to NH ₃ to H ₂ is about 1: 1: 1 to about 1: 1: 20 or about 1: 1 : 9 to about 1: 1: 19. In some specific examples, the ratio of HCOOH to NH ₃ to H ₂ is about 1: 1: 19.

In some specific examples, the first surface treatment process may include exposing the substrate to the first treatment reactant and then to the second treatment reactant. In some specific examples, the first treatment reactant may include O ₃ , atomic oxygen, oxygen radical, or oxygen plasma. In some specific examples, the second treatment reactant may include atomic hydrogen, a hydrogen radical, or a hydrogen plasma. In some embodiments, the first processing reactant may be removed from the reaction chamber before the second processing reactant is introduced. In some specific examples, exposure to the first processing reactant may be performed in the first reaction chamber, and exposure of the substrate to the second processing reactant may be performed in the second reaction chamber.

In some specific examples, the first treatment reactant may remove any organic passivation layer or hydrocarbons that may be present on the first metal surface, and the second treatment reactant may remove the oxide layer and / Or restore it. For example, in some specific examples where the first metal surface is a Co surface, a naturally occurring hydrocarbon layer can be removed from the Co surface by exposure to O ₃ , and subsequent exposure to H radicals can cause the presence of Co The cobalt oxide layer on the surface is reduced.

In some specific examples using an Ar-containing plasma, Ar may be provided, for example, about 1 sccm to about 3000 sccm, more preferably about 300 sccm to about 1500 sccm, and most preferably about 1000 sccm to about 1300 sccm. In some embodiments the use of a plasma containing H may be provided, for example from about 1 sccm to about 500 sccm, more preferably from about 10 sccm to about 200 sccm and most preferably from about 30 sccm to about 100 sccm of H _2. In some embodiments use of the N-containing plasma, for example from about from about 1 sccm to about 500 sccm, more preferably from about 5 sccm to about 200 sccm and most preferably from about 5 sccm to about 30 sccm N ₂ or provided NH ₃ . Similar conditions can be applied to other types of plasma, such as ethanol or O-containing plasma. In some specific examples using a plasma generated from a gas including HCOOH, the gas may be provided at a flow rate of about 1 sccm to about 3000 sccm.

In some specific examples where the plasma is generated from a gas including HCOOH, NH ₃ and H ₂ , the gas may be provided at a flow rate of about 1 sccm to about 3000 sccm. In some specific examples where the plasma is generated from a gas including HCOOH, NH ₃ and H ₂ , the gas may be provided at a flow rate of about 1000 sccm. In some specific examples, the flow rates discussed herein do not include the flow rate of any carrier gas that can be used to provide a plasma-generating gas.

In some specific examples, the plasma may be less than about 3000 watts, such as about 1 W to about 3000 W, about 1 W to about 1500 W, about 1 W to 1000 W, about 1 W to about 500 W, or about 1 W to Power generation of about 200 W or less. In some specific examples, the frequency of the RF power used to generate the plasma may be about 1 MHz to about 10 GHz, about 10 MHz to about 1 GHz, or about 100 MHz to about 500 MHz.

In some specific examples, the plasma is provided or the reactant is maintained for less than about 200 s, such as about 180 s or less than 180 s, about 60 s or less than 60 s or about 30 s or less than 30 s. However, in some specific examples, the first surface treatment process may include exposing the substrate to a plasma or a treatment reactant for up to 10 minutes or longer. For example, in some specific examples, the substrate is exposed to the plasma or the processing reactant for about 1 second to about 10 minutes, about 5 seconds to about 5 minutes, about 10 seconds to about 1 minute, or about 15 seconds to About 30 seconds. In some specific examples, the substrate is exposed to the plasma or processing reaction for about 5 seconds to about 30 seconds.

In some embodiments, exposing the substrate to the plasma or reactant may be continuous or may be split into several pulses. The number of necessary pulses is determined by the length of each of the pulses used to achieve the required total exposure time as determined by those skilled in the art.

The temperature during the surface treatment may be, for example, about room temperature to about 400 ° C, about 100 ° C to about 400 ° C, about 100 ° C to about 300 ° C, 100 ° C to about 200 ° C, or about 100 ° C to about 130 ° C. In some specific examples, the substrate temperature during the first surface treatment may be about 150 ° C. In some embodiments, the substrate may be subjected to outgassing to remove, for example, moisture from the surface of the substrate inside the silicon-containing material. In some specific examples, the substrate may be degassed before being subjected to the first surface treatment process. In some specific examples, the pressure of the plasma generating gas in the first surface treatment process may be about 1 Pa to about 5000 Pa, about 10 Pa to about 3000 Pa, about 50 Pa to about 1000 Pa, and about 150 Pa to About 500 Pa or about 350 Pa.

In some specific examples, the conditions for the first surface treatment process are selected so that etching on the second surface can be avoided or minimized. That is, in some specific examples, the first surface treatment process does not substantially damage or deteriorate the second surface. As used herein with reference to a second surface, the term damage or degradation may refer to a change to the second surface that may reduce the selectivity of a selective deposition process, such as the process described herein. For example, in a selective deposition process for depositing a film on a first surface relative to a second surface, compared to a second surface that has not been damaged or deteriorated, Particles of more material or deposited material may be deposited thereon. Therefore, after a selective deposition process for depositing a film on a first surface relative to a second surface as described herein, the presence of the deposited material on the second surface may indicate a damaged or deteriorated first. Two surfaces. In some specific examples, the first surface treatment process does not reduce or eliminate the selectivity of the selective deposition process compared to a similar selective deposition process that does not include the first surface treatment process. In some specific examples, a large number of new surface groups or ligands are not formed or adsorbed on the second surface by the first surface treatment process sufficient to reduce the selectivity of the selective deposition process. In some examples, the first surface treatment process does not significantly change the amount of material deposited on the second surface of the substrate by the selective deposition process compared to a similar selective deposition process that does not include the first surface treatment process. .

The schematic diagram of the example substrate 20 including the first metal surface 21 and the second dielectric surface 22 before the first surface treatment process is illustrated in FIG. 2A according to some specific examples. The first metal surface 21 includes a metal oxide layer 23 disposed thereon, such as a native metal oxide layer formed naturally by exposure to the surrounding environment. The first metal surface 21 also includes an organic layer 25, such as an organic passivation layer, such as a BTA layer, disposed over the metal oxide layer 23.

As described herein and according to some specific examples, the substrate 20 may then undergo a first surface treatment process. For example, the substrate 20 and thus the first metal surface 21 and the second dielectric surface 22 may be exposed to a plasma generated by a gas, such as a gas including HCOOH, H ₂ and NH ₃ . As shown in FIG. 2B, the first surface treatment process may remove the organic layer 25 from the first metal surface 21. The first surface treatment process can also remove the metal oxide layer 23 from the first metal surface 21 and / or reduce it, thereby leaving a clean first metal surface 21. In addition, as shown in FIG. 2B, the second dielectric surface is not damaged or deteriorated by the first surface treatment process, and does not include a large number of new or additional surface groups and / or ligands. Selective deposition of a first precursor

In some specific examples, the first precursor is provided on the substrate so that a layer is selectively formed on the first metal surface of the substrate with respect to the second silicon-containing surface of the substrate. In some embodiments, the first precursor preferably includes silicon or boron. In some specific examples, a Si layer or a B layer having a thickness of 0.05 nm to 4 nm is formed on the metal surface of the substrate. In some specific examples, a Si layer or a B layer having a thickness of 0.1 nm to 2 nm is formed on the metal surface of the substrate. In some specific examples, Si or B less than 1 nm can be used. Without being bound by theory, compared to the reactivity of the second surface, the metal surface of the substrate can catalyze or assist the adsorption or decomposition of the first precursor. In some embodiments, the formation of silicon or boron on the metal surface is self-limiting so that at most one monolayer is formed when exposed to the reactant. In some specific examples, silicon or boron source chemicals can decompose on copper or metal surfaces.

In some specific examples, the silicon source chemical is selected from the silane family Si _n H _{2n + 2} (n is equal to or greater than 1) or the cyclic silane family Si _n H _2n (n is equal to or greater than 3). In some specific examples, the silicon source includes silane or disilane. Most preferably, the silane is disilane Si ₂ H ₆ or trisilane Si ₃ H ₈ . In some specific examples, the silicon source may be selected from a silane compound having the formula: SiH _x L _y , where L is a ligand selected from the group consisting of: alkyl, alkenyl, alkynyl, alkoxide And amines. In some cases, L is a ligand selected from the following halide groups: F, Cl, Br, and I.

In some specific examples, the first precursor includes boron. In some specific examples, the first precursor is diborane (B ₂ H ₆ ). Diborane has similar properties to some silane-based compounds. For example, the decomposition temperature of diborane is lower than that of disilane, but the thermal stability is similar to that of tricore.

Other precursors including boron can also be used. The availability of a large number of boron compounds makes it possible to select boron compounds having the desired characteristics. Furthermore, it is possible to use more than one boron compound. Preferably, one or more of the following boron compounds are used:

Borane according to formula I or formula II.

B _n H _{n + x} , (I)

Wherein n is an integer from 1 to 10, preferably from 2 to 6, and x is an even integer, preferably from 4, 6, or 8.

B _n H _m (II)

Where n is an integer of 1 to 10, preferably 2 to 6, and m is an integer of 1 to 10, preferably 2 to 6, different from n.

The above borane of Formula I, examples include nested formula - borane _{(B n H n + 4)} , spider formula - borane (B _n H _{n + 6)} and open net formula - borane (B _n H _{n + 8} ). In borane of formula II in accordance with the formula examples include - borane (B _n H _m). In addition, a borane complex such as (CH ₃ CH ₂ ) ₃ N-BH ₃ can be used.

Borane halides, especially fluoride, bromide and chloride. An example of a suitable compound is B ₂ H ₅ Br. Other examples include boron halides with high boron / halide group ratios, such as B ₂ F ₄ , B ₂ Cl ₄ and B ₂ Br ₄ . It is also possible to use a boron halide complex.

Halogenated borane according to formula III.

B _n X _n (III)

Where X is Cl or Br, and n is an integer of 4 or 8 to 12 when X is Cl, or n is an integer of 7 to 10 when X is Br.

Carborane according to formula IV.

C ₂ B _n H _{n + x} (IV)

Where n is an integer from 1 to 10, preferably from 2 to 6, and x is an even integer, preferably from 2, 4 or 6.

The examples of the carbon of formula IV comprising closed borane - carborane _{(nido- carboranes) (C 2 B} n H n + 2), nested - carborane _{(C 2 B n H n +} 4) and the spider of formula -Arachno-carboranes (C ₂ B _n H _{n + 6} ).

Amine-borane adduct according to formula V.

R ₃ NBX ₃ (V)

Wherein R is a straight or branched chain C1 to C10, preferably C1 to C4 alkyl or H, and X is a straight or branched chain C1 to C10, preferably C1 to C4 alkyl, H or halogen.

Wherein one or more of the substituents on B are aminoboranes of the amino group according to formula VI.

R ₂ N (VI)

Wherein R is a straight or branched chain C1 to C10, preferably C1 to C4 alkyl or substituted or unsubstituted aryl.

An example of a suitable aminoborane is (CH ₃ ) ₂ NB (CH ₃ ) ₂ .

Cyclic Borazyne (-BH-NH-) ₃ and its volatile derivatives.

Alkylborane or alkylborane, wherein the alkyl group is usually a straight or branched C1 to C10 alkyl group, preferably a C2 to C4 alkyl group.

In some specific examples, the first precursor includes germanium. In some specific examples, the germanium source chemical is selected from the group consisting of the germane family Ge _n H _{2n + 2} (n is equal to or greater than 1) or the cyclic germane family Ge _n H _2n (n is equal to or greater than 3). In some preferred embodiments, the germanium source includes germane GeH ₄ . In some specific examples, the germanium source may be selected from a germane compound having the formula: GeH _x L _y , where L is a ligand selected from the group consisting of: alkyl, alkenyl, alkynyl, alkoxylation And amines. In some cases, L is a ligand selected from the following halide groups: F, Cl, Br, and I. Metal source chemicals

Preferably, the second reactant includes a metal. In some specific examples, the metal is a transition metal. The transition metal may be selected from the group consisting of Ti, V, Cr, Mn, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, and Pt. In some specific examples, the second reactant includes W, Ta, Nb, Ti, Mo, or V. In some embodiments, the second reactant preferably includes tungsten.

In some specific examples, the second reactant includes a noble metal. The noble metal may be selected from the group: Au, Pt, Ir, Pd, Os, Ag, Rh, and Ru.

In some specific examples, the second reactant includes a metal halide (F, Cl, Br, I). In some preferred embodiments, the second reactant includes a transition metal halide. In some embodiments, the second reactant preferably includes fluorine. In some specific examples, the second reactant includes WF ₆ , TaF ₅ , NbF ₅ , TiF ₄ , MoF _x , and VF _x . In some specific examples, the second reactant includes WF ₆ .

The second reactant can be used to form a variety of different materials on a substrate. In some specific examples, the second reactant reacts with the first reactant on the substrate to form a metal material on the substrate. Any of the metals disclosed above with respect to the second reactant may be in a film deposited on the substrate.

In some specific examples, an elemental metal film such as a W film may be formed. In some embodiments, a metal nitride film may be formed. In some embodiments, a metal silicide film may be formed.

In some specific examples, the metal or elemental metal film is first formed by the reaction of Si or B on the substrate surface with a second reactant, and later converted into the corresponding metal silicide or metal nitride through further processing. For example, the first metal or elemental metal film may be exposed to a third reactant to convert it to a metal silicide or a metal nitride.

In some specific examples, further processing of the metal material may be performed to dope the metal material or convert the metal material into a metal nitride or a metal silicide. In some specific examples, for example, a plasma or NH ₃ treatment can be used to convert the material into the corresponding metal nitride. In some specific examples, the conductive metal material can be converted into a material with a higher resistance or into a dielectric material by using different processes and depending on the starting metal material.

In some embodiments, multiple pulses of one of the reactants may be provided before the next reactant is provided. In some embodiments, any excess reactants can be removed before the next reactant is provided. In some embodiments, the processing chamber may be purged before the next reactant is provided.

In some embodiments, a gas phase precursor may be provided into the reaction space by means of an inert carrier gas. Removing excess reactants may include evacuating some of the contents of the reaction space or purifying the reaction space with helium, nitrogen, or any other inert gas. In some embodiments, purification may include shutting off the flow of the reaction gas while continuing to flow the inert carrier gas into the reaction space. Deposition temperature

In some embodiments, the temperature is selected to promote selective deposition. If the amount of deposited material per surface area or volume on the first surface (e.g., at / cm ² or at / cm ³ ) is greater than the amount of deposited material per surface area or volume on the second surface, the deposition is substantially Defined as optional. The amount of material deposited on the surface can be determined by measuring the thickness of each layer. In some cases, due to discontinuous films, thickness measurements may not be possible. In some cases, selectivity can be determined by measuring deposited atoms per surface area or volume. As mentioned above, selectivity can be expressed as the ratio of the combined amount of the material formed on the first surface to the material formed on the first and second surfaces. Preferably, the selectivity is higher than about 70%, higher than about 80%, more preferably higher than 90%, even more preferably higher than 95%, and most preferably about 100%. In some cases, selectivities above 80% may be acceptable for certain applications. In some cases, selectivities above 50% may be acceptable for certain applications.

In some specific examples, the deposition temperature is selected such that the selectivity is higher than about 90%. In some specific examples, the deposition temperature is selected such that a selectivity of about 100% is achieved.

In some embodiments, the deposition temperature is selected so that the first precursor including silicon or boron forms a layer containing silicon or boron on the first metal surface. In some specific examples, the first precursor does not form a layer on the second surface including silicon, or less than the entire layer is formed on the second surface.

The particular temperature used may depend in part on the silicon or boron precursor selected and the first or metal and second surface or dielectric on the substrate. Preferably, the silicon or boron source is formed on a metal surface rather than a second surface including silicon to form a layer including silicon or boron. Preferably, the layer including silicon or boron is about a single layer or less. In some cases, more than a single layer of silicon or boron may be formed. In some specific examples, a silicon or boron layer having a thickness of about 0.05 nm to about 4 nm is formed on the metal surface of the substrate. In some specific examples, a silicon or boron layer having a thickness of about 0.1 nm to about 2 nm is preferably formed on the metal surface of the substrate. In some embodiments, the formation of silicon or boron on the metal surface is self-limiting. In some embodiments, a layer including silicon or boron is formed by decomposition.

In some cases, a silicon or boron layer can be formed on both metal surfaces and silicon-containing surfaces at higher temperatures. In such cases, it is better to use lower temperatures because silicon or boron can be formed on metal surfaces at lower temperatures than surfaces including silicon. Therefore, the temperature may be selected such that the silicon precursor preferentially interacts with the first surface or the metal surface relative to the second surface or the silicon-containing surface.

In some specific examples, the deposition temperature is selected to achieve a desired level of selectivity. For example, the temperature can be selected such that the adsorption of silicon or boron-containing precursors to low-k materials is limited to the amount necessary to achieve the desired level of selectivity.

The deposition temperature can be selected based on the silicon or boron source and the specific substrate surface (eg, silicon-containing surface and copper surface) used.

In some specific examples, the deposition temperature is preferably less than 200 ° C, more preferably less than about 175 ° C, more preferably less than about 150 ° C, and most preferably less than about 110 ° C. In some cases, temperatures less than about 100 ° C can be used. In some specific examples, the deposition temperature range for selective deposition exceeding 50% for selective deposition in films having a thickness (e.g., deposited W thickness) deposited using disilane and WF _{6 of} less than about 5 nm is about 30 ° C to about 200 ° C. In some specific examples, the desired uniformity and selectivity levels can be achieved using deposition temperatures ranging from about 30 ° C to about 110 ° C. In some specific examples, the desired uniformity and selectivity can be achieved using deposition temperatures ranging from about 40 ° C to about 110 ° C. In some specific examples, the desired uniformity and selectivity levels can be achieved using deposition temperatures in the range of less than about 100 ° C. In these temperature ranges, those skilled in the art can optimize the process to achieve the desired or acceptable uniformity and selectivity for films deposited using specific reactors and specific precursors.

In some specific examples, a silicon-containing precursor or a boron-containing precursor and a second metal precursor are provided at the same temperature and in the same reaction space. In some embodiments, a silicon precursor is provided at a first deposition temperature and a second metal reactant is provided at a second deposition temperature. In practice, this may mean providing a first reactant in the first reaction space and providing a second metal reactant in the second reaction space.

In some specific examples using disilane and WF ₆ to deposit tungsten on the surface of copper or cobalt, relative to a surface including silicon, a deposition temperature of about 30 ° C to about 110 ° C can be used to achieve greater than about 80%. The selectivity is preferably greater than about 90%. The deposition temperature for trisilane can be even lower than the deposition temperature for disilane. In the specific examples mentioned above, the deposited film may be, for example and without limitation, a tungsten film.

In some embodiments, the thickness of the selectively deposited film is less than about 10 nm, less than about 5 nm, about 4 nm, or less than 4 nm, or in some embodiments, about 1 nm to about 4 nm. However, in some cases, the desired selectivity level is achieved in the case where the thickness of the selectively deposited film exceeds about 10 nm, such as greater than 50%, and more preferably greater than 80%.

In some specific examples, a W film having a thickness of about 10 nm or less is selectively deposited over Co or Cu on the surface of the substrate with a selectivity greater than 50% relative to the silicon-containing material.

In some specific examples, a W film having a thickness of about 5 nm or less is selectively deposited over Cu or Co on the substrate surface with a selectivity greater than about 80% relative to the silicon-containing material.

In some specific examples, a W film having a thickness of about 3 nm or less with respect to the silicon-containing material is selectively deposited over Cu or Co on the substrate surface with a selectivity greater than about 90%.

If a lower selectivity is preferred, the temperature may be slightly higher than the temperature used to achieve a process greater than 90% selectivity.

In some specific examples, the deposition conditions and / or reactants are selected so that etching of the silicon-containing surface is avoided or minimized. For example, at higher temperatures, metal fluorides can begin to fluorinate any Si-OH groups that may be present on the second surface, and in some cases, they can etch silicon-containing surfaces. Therefore, in some specific examples, the deposition temperature is selected so that the etching of the silicon-containing surface is avoided or eliminated.

The substrate temperature during the supply of the second reactant may be the same as the temperature during the supply of the silicon or boron-containing reactant. Different temperatures can be used in other specific examples.

In a specific example in which WF _{6 is} used as the second reactant and disilane is used as the first reactant, a temperature of about 30 ° C to about 110 ° C can be used.

In some embodiments, when a second reactant is provided to increase the conversion of the metal reactant, the temperature of the substrate may be increased. For example, when TaF ₅ and NbF _{5 are} used as the second reactant, higher temperatures can be used. For example, when using TaF ₅ , the temperature can exceed about 300 ° C. When using NbF ₅ , the temperature can be higher than about 250 ° C. This can be achieved by heating the substrate using a higher reaction temperature for the second material or other means known to those skilled in the art. Exemplary Process Flow

FIG. 3 is a flowchart generally illustrating a process 30 for selectively depositing a metal film on a first metal surface of a substrate with respect to a second silicon-containing surface according to some specific examples. The one or more reaction chambers in which the selective deposition process will be performed are firstly subjected to the optional reactor passivation process at step 31 to deposit a SiN passivation layer on any chamber surface, and any chamber surface and subsequent The parts of the deposition process are directly connected. A substrate including a first metal surface (such as a Co surface) and a second surface including silicon (such as a SiO ₂ surface) is provided and degassed as appropriate. In some specific examples, the substrate may be subjected to an optional silicon-containing surface treatment at step 32, for example, to passivate the SiO ₂ surface. The substrate may then be subjected to a first surface treatment process optionally selected at step 33. As described above, in some specific examples, the first surface treatment process may include exposing the substrate to a plasma, such as a plasma generated from NH ₃ , H _2, or a combination of both.

In some specific examples, the plasma processing process 33 can reduce the first Co surface. In some specific examples, the plasma treatment process may remove the native oxide layer existing on the surface of the first Co. In some specific examples, the plasma treatment process may remove a passivation layer or a hydrocarbon layer, such as a BTA layer, that may be present on the surface of the first Co.

In some embodiments, steps 32 and 33 may be performed in one or more reaction chambers that are different from the reaction chamber that is passivated at step 31. That is, steps 32 and 33 may be performed in one or more reaction chambers different from the reaction chamber in which the subsequent selective deposition process is to be performed. In addition, in some specific examples, the reaction chamber passivation step 31 may be performed simultaneously with one or more of steps 32 and 33.

In some specific examples, after step 33 is selected as appropriate, the substrate surface is further annealed in an inert atmosphere as appropriate. The annealing is performed at a temperature higher than the temperature during the selective deposition step 35 to the selective deposition step 37 of step 32, step 33 or below. The temperature used for the annealing process is preferably about 150 ° C to about 400 ° C, about 150 ° C to about 300 ° C, or about 200 ° C to about 275 ° C, and in some cases, about 250 ° C. In some specific examples, the substrate surface may be further annealed in an NH ₃ environment as appropriate to produce an NH _x surface termination state on any cobalt oxide present on the first Co surface.

Next, at step 34, the substrate is transferred to the passivation chamber optionally at step 31, and a silicon source or boron source is provided on the substrate so that the silicon or boron-containing species is at step 35 Deposited on the Co surface. In some specific examples, the silicon source is disilane. In some specific examples, a silicon precursor can be used to form silicon on the Co surface but the deposition temperature at which the silicon does form on the SiO ₂ surface causes the disilane to selectively decompose on the Co surface relative to the SiO ₂ surface. For example, the deposition may be from about 30 ° C to about 110 ° C. In some specific examples, the silicon or boron source reacts with the Co surface in a self-limiting manner. It is believed that, compared with the formation on the SiO ₂ surface, the Co surface can promote the formation of silicon.

In some specific examples, a layer including silicon or boron having a thickness of about 0.05 nm to about 4 nm is formed on the Co surface of the substrate in each deposition cycle. In some specific examples, a layer including silicon or boron having a thickness of about 0.1 nm to about 2 nm is formed on the Co surface of the substrate in each cycle. In a preferred embodiment, the formation of a layer including silicon or boron on a metal surface is self-limiting. Therefore, a single layer including silicon or boron is formed at most in each cycle.

After the silicon or boron-containing layer is formed on the Co layer, a second reactant (such as a metal halide, such as WF ₆ ) is used to convert the layer including silicon or boron to include the second reactant at step 36. This corresponds to a layer of metal, such as tungsten. In some specific examples, WF ₆ , TaF ₅ , NbF ₅ or other compounds capable of reacting with the Si layer or the B layer are introduced on the surface of the substrate to form a metal layer or a metal silicide. In some specific examples, the silicon or boron precursor (eg, disilane) and the second reactant (eg, metal halide) pulses may be repeated at step 37 until a metal layer having a desired thickness is formed. In some specific examples, the metal layer is an elemental metal, such as W. In some specific examples, the metal layer may include other elements, such as Si, B, N, and other dopants. In some specific examples, the metal layer is further processed to form different materials. For example, a third reactant may be used to treat the elemental metal layer to form a metal nitride or a metal silicide.

The deposition cycle may be defined as providing a silicon precursor or a boron precursor and providing a second metal reactant, that is, steps 35 and 36. In some specific cases, no other reactants are provided in the sedimentation cycle. In some embodiments, the deposition cycle is repeated to form a W layer having a desired thickness. In some specific examples, a W layer having a thickness of about 0.05 nm to about 4 nm is formed in each cycle. In some specific examples, preferably, a W layer having a thickness of about 0.1 nm to about 2 nm is formed in each cycle. In some specific examples, the thickness of the W layer is about 1 nm to 2 nm. In other specific examples, the thickness of the deposited W layer is greater than about 2 nm, in some cases greater than about 30 nm, and in some cases greater than about 50 nm. In a preferred embodiment, the thickness of the layer is less than 10 nm.

In some specific examples, the deposition cycle is repeated 10 times or more. In some specific examples, the deposition cycle is repeated at least 50 times. In some specific examples, the deposition cycle is repeated about 100 times or more. The number of cycles can be selected based on the desired thickness of the W layer.

In some specific examples, no other reactants are provided except for silicon or boron precursors and second metal reactants.

In some embodiments, the material (such as cobalt) constituting the first surface is not transformed or reacted to form another compound during the selective deposition cycle.

In some specific examples, after completing one or more deposition cycles, a semi-deposition cycle may be performed at step 38. For example, a silicon precursor pulse or a boron precursor pulse may be provided or alternatively a second metal reactant may be provided. In some embodiments, a silicon precursor pulse or a boron precursor pulse is provided after one or more deposition cycles. When a silicon precursor pulse or a boron precursor pulse (or other metal reactant) is provided, the formed material can form a sacrificial layer of silicon oxide or boron oxide (or metal oxide) when exposed to air or an oxygen-containing atmosphere . The sacrificial layer prevents the metal material under the silicon oxide layer or the boron oxide layer from being oxidized when exposed to the air or oxygen-containing atmosphere outside the reactor. The formed silicon oxide layer or boron oxide layer can be removed in further processing steps, such as using a single pulse of the metal source chemistry described herein, preferably using WF ₆ , TaF ₅ , NbF ₅ , TiF ₄ , MoF _x or VF _x and better use WF ₆ .

In some specific examples, the entire process flow is performed in a single reaction chamber; for example, in a single process module. However, in other specific examples, various steps are performed in two or more reaction chambers. For example, in some specific examples, a first surface treatment and a silicon-containing surface treatment process (if used) are performed in the first reaction chamber, and selective deposition can be performed in a second different reaction chamber. In some specific examples, the second different reaction chamber may also be processed to form a passivation layer therein. If an optional thermal annealing step is required or desired, the substrate can then be transferred to a second reaction chamber where thermal annealing (if used) and selective deposition are performed. In some specific examples, an annealing step is performed in the second reaction chamber, and the substrate is transferred back to the first reaction chamber or into a third reaction chamber in which selective deposition is performed. In some specific examples, the first surface treatment and the silicon-containing surface treatment (if used) are performed in the first reaction chamber, and the selective deposition is performed in the second different reaction chamber without the first surface treatment and sedimentation. Thermal annealing step between steps. If necessary, the substrate may be cooled for a period of time before being transported. In some specific examples, the cooling is performed at a pressure ranging from vacuum to about 2 atm or about 0.1 torr to about 760 torr or about 1 torr to about 760 torr for about 0 minutes to 30 minutes, or about 0 minutes to 10 minute. For example, the substrate can be transported under vacuum or in the presence of N ₂ (and possibly some O ₂ ) at about 1 to 1000 torr.

FIG. 4 is a flowchart generally illustrating a process 40 for selectively depositing a metal film on a first metal surface of a substrate relative to a second silicon-containing surface according to certain other specific examples. Among them, one or more reaction chambers of the selective deposition process will first be subjected to a reactor passivation process optionally selected at step 41. A substrate including a first metal surface (preferably a Cu surface) and a second surface including silicon (such as a SiO ₂ surface) is provided and degassed as appropriate. In some specific examples, the substrate may be optionally subjected to a silicon-containing surface treatment at step 42, for example, to passivate the SiO ₂ surface. The substrate may then be subjected to a first surface treatment process optionally selected in step 43. As described above, in some specific examples, the surface first surface treatment process may include exposing the substrate to one or more first surface treatment reactants.

In some specific examples, the processing process 43 can reduce the first metal surface. In some specific examples, the processing process may remove the native oxide layer existing on the first metal surface. In some specific examples, the processing process may remove the passivation layer or the hydrocarbon layer that may be present on the first metal surface, for example, the processing process may remove the BTA layer that is present on the Cu surface. In some specific examples, a passivation layer (such as a BTA layer) on the Cu surface may be deposited to protect the Cu surface from oxidation during other processing steps (such as chemical mechanical planarization). However, such a passivation layer must be removed before the selective deposition process.

In some embodiments, the processing process includes exposing the substrate to a processing reactant. In some specific examples, the treatment reactant is a gas-phase organic reactant. In some specific examples, the treatment reactant may contain at least one alcohol group and may be preferably selected from the group consisting of a primary alcohol, a secondary alcohol, a tertiary alcohol, a polyol, a cyclic alcohol, an aromatic Alcohols and other derivatives of alcohols. In some embodiments, the treatment reactant may include formic acid or HCl.

For example, the temperature during the process 43 may be about room temperature to about 400 ° C, about 100 ° C to about 400 ° C, about 100 ° C to about 130 ° C, or about 30 ° C to about 110 ° C.

In some embodiments, steps 42 and 43 may be performed in one or more reaction chambers that are different from the reaction chamber that was passivated at step 41. That is, steps 42 and 43 may be performed in one or more reaction chambers different from the reaction chamber in which the subsequent selective deposition process is to be performed. In addition, in some specific examples, the reaction chamber passivation step 41 may be performed simultaneously with one or more of steps 42 and 43.

In some specific examples, after step 43 is selected as appropriate, the substrate surface is further annealed in an inert atmosphere as appropriate. The annealing is performed at a temperature higher than the temperature during the selective deposition step 45 to the selective deposition step 47 of step 42, step 43 or below. The temperature used for the annealing process is preferably about 150 ° C to about 400 ° C, about 150 ° C to about 300 ° C, or about 200 ° C to about 275 ° C, and in some cases about 250 ° C. In some specific examples, the surface of the substrate may be further annealed in an NH ₃ environment as appropriate to produce a NH _x surface termination state on a metal oxide existing on the first Cu surface.

Next, at step 44, the substrate is transferred to the passivation chamber optionally at step 41, and a silicon source or boron source is provided on the substrate so that the silicon or boron-containing species is at step 45. Deposited on Cu surface. In some specific examples, the silicon source is disilane. In some specific examples, the silicon precursor can be used to form silicon on the Cu surface but the deposition temperature at which the silicon does form on the SiO ₂ surface causes the disilane to selectively decompose on the Cu surface relative to the silicon containing surface. In some specific examples, the silicon or boron source reacts with the Cu surface in a self-limiting manner. It is believed that, compared to the formation on the SiO ₂ surface, the Cu surface can promote the formation of silicon.

In some specific examples, a layer including silicon or boron having a thickness of about 0.05 nm to about 4 nm is formed on the Cu surface of the substrate in each deposition cycle. In some specific examples, a layer including silicon or boron having a thickness of about 0.1 nm to about 2 nm is formed on the Cu surface of the substrate in each cycle. In a preferred embodiment, the formation of a layer including silicon or boron on the surface of Cu is self-limiting. Therefore, a single layer including silicon or boron is formed at most in each cycle.

After the silicon or boron-containing layer is formed on the Cu surface, a second reactant (such as a metal halide) is used to convert the layer including silicon or boron to a corresponding metal (such as Metal halide). In some specific examples, WF ₆ , TaF ₅ , NbF ₅ or other compounds capable of reacting with the Si or B layer are introduced onto the surface of the substrate to form a metal layer or a metal silicide. In some embodiments, the silicon or boron precursor (eg, disilane) and the second reactant (eg, metal halide) pulses may be repeated at step 47 until a metal layer having a desired thickness is formed. In some specific examples, the metal layer is an elemental metal, such as W. In some specific examples, the metal layer may include other elements, such as Si, B, N, and other dopants. In some specific examples, the metal layer is further processed to form different materials. For example, a third reactant may be used to treat the elemental metal layer to form a metal nitride or a metal silicide.

The deposition cycle may be defined as providing a silicon precursor or a boron precursor and providing a second metal reactant, that is, steps 45 and 46. In some specific cases, no other reactants are provided in the sedimentation cycle. In some embodiments, the deposition cycle is repeated to form a metal layer having a desired thickness. In some embodiments, a metal layer having a thickness of about 0.05 nm to about 4 nm is formed in each cycle. In some embodiments, a metal layer with a thickness of about 0.1 nm to about 2 nm is preferably formed in each cycle. In some specific examples, the thickness of the metal layer is about 1 nm to 2 nm. In other specific examples, the thickness of the deposited metal layer is higher than about 2 nm, in some cases higher than about 30 nm, and in some cases higher than about 50 nm. In a preferred embodiment, the thickness of the layer is less than 10 nm.

In some specific examples, the deposition cycle is repeated 10 times or more. In some specific examples, the deposition cycle is repeated at least 50 times. In some specific examples, the deposition cycle is repeated about 100 times or more. The number of cycles can be selected based on the desired thickness of the metal layer.

In some specific examples, no other reactants are provided except for silicon or boron precursors and second metal reactants.

In some specific examples, the material (such as copper) constituting the first surface is not transformed or reacted to form another compound during the selective deposition cycle.

In some specific examples, after completing one or more deposition cycles, a semi-deposition cycle may be performed at step 48. For example, a silicon precursor pulse or a boron precursor pulse may be provided or alternatively a second metal reactant may be provided. In some embodiments, a silicon precursor pulse or a boron precursor pulse is provided after one or more deposition cycles. When a silicon precursor pulse or a boron precursor pulse (or other metal reactant) is provided, the formed material can form a sacrificial layer of silicon oxide or boron oxide (or metal oxide) when exposed to air or an oxygen-containing atmosphere . The sacrificial layer prevents the metal material under the silicon oxide layer or the boron oxide layer from being oxidized when exposed to the air or oxygen-containing atmosphere outside the reactor. The formed silicon oxide layer or boron oxide layer can be removed in further processing steps, such as using a single pulse of the metal source chemistry described herein, preferably using WF ₆ , TaF ₅ , NbF ₅ , TiF ₄ , MoF _x or VF _x and better use WF ₆ .

In some specific examples, the entire process flow is performed in a single reaction chamber; for example, in a single process module. However, in other specific examples, various steps are performed in two or more reaction chambers. For example, in some specific examples, a first surface treatment and a silicon-containing surface treatment process (if used) are performed in the first reaction chamber, and selective deposition can be performed in a second different reaction chamber. In some specific examples, the second different reaction chamber may also be processed to form a passivation layer therein. If an optional thermal annealing step is required or desired, the substrate can then be transferred to a second reaction chamber where thermal annealing (if used) and selective deposition are performed. In some specific examples, an annealing step is performed in the second reaction chamber, and the substrate is transferred back to the first reaction chamber or into a third reaction chamber in which selective deposition is performed. In some specific examples, the first surface treatment and the silicon-containing surface treatment (if used) are performed in the first reaction chamber, and the selective deposition is performed in the second different reaction chamber without the first surface treatment and sedimentation. Thermal annealing step between steps. If necessary, the substrate may be cooled for a period of time before being transported. In some specific examples, the cooling is performed at a pressure ranging from vacuum to about 2 atm or about 0.1 torr to about 760 torr or about 1 torr to about 760 torr for about 0 minutes to 30 minutes, or about 0 minutes to 10 minute. For example, the substrate can be transported under vacuum or in the presence of N ₂ (and possibly some O ₂ ) at about 1 to 1000 torr.

FIG. 5 is a flowchart illustrating an exemplary reaction chamber passivation process 50 according to some specific examples. In some embodiments, the reaction chamber passivation process can achieve selective deposition, improve selectivity, and / or increase the number of cycles before the selectivity is lost during the selective deposition process.

A reaction chamber is provided at step 51 in which a selective deposition process (eg, a W selective deposition process) will be performed. There are no wafers or substrates in the reaction chamber. In some specific examples, the selective deposition process may be performed on one or more wafers in the reaction chamber, and then the wafer is removed at step 51 so that no wafers exist in the reaction chamber. In some specific examples, one or more wafers that will undergo a selective deposition process in the reaction chamber may undergo other processing before, during, or after the passivation process of the reaction chamber. For example, a wafer may undergo a surface first surface treatment process in a second different reaction chamber during a reaction chamber passivation process.

In some specific examples, the passivation layer is deposited or formed on the inner surface of the reaction chamber at step 52 and may be exposed to the precursor or any other part of the reactant during the selective deposition process. In some specific examples, the passivation layer is deposited or formed on the inner surface of the reaction chamber, the chamber shower head, and / or any other portion of the chamber that can be connected to the space in which the selective deposition process is to be performed. In some embodiments, the passivation layer may be deposited on any surface in the reaction chamber other than the substrate.

In some specific examples, a passivation layer (such as a layer of SiN) may be formed by a vapor deposition process (such as a PEALD process). In some specific examples, the SiN layer can be formed by a process including one or more passivation layer deposition cycles, which include alternately and sequentially exposing the reaction chambers to the first silicon precursor and the second Nitrogen precursor. The passivation layer deposition cycle may be repeated as appropriate until a SiN passivation layer having a desired thickness has been formed.

In some specific examples, the silicon precursor used in the passivation layer deposition process may include a silane, such as disilane. In some specific examples, the nitrogen precursor may be atomic nitrogen, a nitrogen radical, a nitrogen plasma, or a combination thereof. In some specific examples, the nitrogen precursor may further include atomic hydrogen, a hydrogen radical, a hydrogen plasma, or a combination thereof. In some embodiments, the nitrogen precursor may include a plasma generated from N ₂ . In some embodiments, the nitrogen precursor may include a plasma generated from N ₂ and H ₂ . In some embodiments, the nitrogen precursor may include a plasma generated from N ₂ and a rare gas such as argon. In some specific examples, the nitrogen precursor may include a plasma generated from N ₂ , H ₂ and a rare gas such as argon.

In some specific examples, after the passivation layer is formed at step 52, one or more wafers are transferred to the reaction chamber at step 53. A selective deposition process (eg, a W selective deposition process) and any other desired processes may then be performed at step 54. In some specific examples, after the selective deposition process, any one or more wafers present in the reaction chamber may then be transferred out of the reaction chamber at step 55. In some specific examples, the reaction chamber passivation process may be repeated at step 56 as appropriate. In some specific examples, one or more wafers may be transferred into the reaction chamber, and another selective deposition process may be performed again before the reaction chamber passivation process is repeated as appropriate. That is, in some specific examples, the reaction chamber passivation process may be repeated after every 1, 5, 10, 20, 50, or more than 50 wafers have been subjected to a selective deposition process. In some specific examples, the reaction chamber passivation process may be repeated after a certain number of cycles of the selective deposition process have been performed. In some specific examples, the reaction chamber passivation process may be repeated after every 50, 100, 150, or more than 150 selective deposition cycles. Examples

Provide a sample substrate having a first metal surface including Cu and a second dielectric surface including a low-k dielectric material having a dielectric constant of 3.0, and by depositing a thickness of about 1 nm to 2 nm on the first Cu surface Organic layer to passivate it. A native copper oxide layer with a thickness of about 1 nm also exists between the Cu surface and the organic layer. A substrate including only the Co surface and the primary cobalt oxide surface layer is also provided as a control.

As described herein and according to some specific examples, a sample substrate including a first Cu surface and a second dielectric surface and a control substrate including a Co surface were subjected to various first surface treatment processes in order to study the effects of such processes on subsequent execution Effects of a selective deposition process for depositing W on a first surface of a sample substrate relative to a second surface. Various first surface treatment processes include exposing the substrate to a plasma generated by various gases. Each plasma is generated by RF power of about 200 W under a pressure of about 350 Pa while exposing the substrate for about 10 seconds. The substrate temperature during each first surface treatment process is about 150 ° C.

Subjecting the first sample substrate and the control substrate to a first surface treatment process that includes exposing the substrate to electricity generated by a gas including H ₂ having a flow rate of 1000 sccm and using a rare gas as a carrier gas. In the pulp. The sample substrate and the control substrate are then subjected to a selective deposition process for selectively depositing W on the first Cu and Co surfaces relative to the second dielectric surface. A control substrate including a Co surface was included to investigate the ability of the first surface treatment process to effectively reduce and / or remove the native oxide layer present thereon.

As shown in Figure 6A, W is deposited on both the first Cu surface and the second dielectric surface. W deposition was also observed on the substrate including the Co surface, indicating that the native oxide surface layer has been effectively reduced and / or removed. Therefore, the first surface treatment process described above does not enhance the selectivity of the selective deposition process, but instead decreases the selectivity of the process. Without being bound by any theory, Xianxin's exposure to the plasma generated by H ₂ under the conditions described above damages the second dielectric surface, creating surface sites on which W deposition is achieved.

Subjecting the second sample substrate and the control substrate to a first surface treatment process including exposing the substrate to a gas generated from a gas including H ₂ and N ₂ with a flow rate of 1000 sccm and using a rare gas as a carrier gas In the plasma. The sample substrate and the control substrate are then subjected to a selective deposition process for selectively depositing W on the first Cu and Co surfaces relative to the second dielectric surface. A control substrate including a Co surface was included to investigate the ability of the first surface treatment process to effectively reduce and / or remove the native oxide layer present thereon.

As shown in Figure 6B, W is deposited on both the first Cu surface and the second dielectric surface. W deposition was also observed on the substrate including the Co surface, indicating that the native oxide surface layer has been effectively reduced and / or removed. Therefore, the first surface treatment process described above does not enhance the selectivity of the selective deposition process, but instead decreases the selectivity of the process. Without being bound by any theory, Xianxin's exposure to the plasma generated by H ₂ and N ₂ under the conditions described above damages the second dielectric surface, creating a surface position on which W deposition is achieved. point.

The third sample and control substrate were subjected to a first surface treatment process that included exposing the substrate to a plasma generated by a gas including NH ₃ with a flow rate of 1000 sccm and using a rare gas as a carrier gas. . The sample substrate and the control substrate are then subjected to a selective deposition process for selectively depositing W on the first Cu and Co surfaces relative to the second dielectric surface. A control substrate including a Co surface was included to investigate the ability of the first surface treatment process to effectively reduce and / or remove the native oxide layer present thereon.

As shown in FIG. 6C, W is deposited on both the first Cu surface and the second dielectric surface. No W deposition was observed on the substrate including the Co surface, indicating that the native oxide surface layer was not effectively reduced and / or removed. Therefore, the first surface treatment process described above does not enhance the selectivity of the selective deposition process, but instead decreases the selectivity of the process. Without being bound by any theory, Xianxin's exposure to the plasma generated by NH ₃ under the conditions described above damages the second dielectric surface, creating surface sites on which W deposition is achieved.

Subjecting the fourth sample substrate and the control substrate to a first surface treatment process including exposing the substrate to a gas generated from a gas including H ₂ and NH ₃ with a flow rate of 1000 sccm and using a rare gas as a carrier gas In the plasma. The sample substrate and the control substrate are then subjected to a selective deposition process for selectively depositing W on the first Cu and Co surfaces relative to the second dielectric surface. A control substrate including a Co surface was included to investigate the ability of the first surface treatment process to effectively reduce and / or remove the native oxide layer present thereon.

As shown in Figure 6D, W is deposited on a first Cu surface and granular W material is deposited on a second dielectric surface. No W deposition was observed on the substrate including the Co surface, indicating that the native oxide surface layer was not effectively reduced and / or removed. Therefore, the first surface treatment process described above does not enhance the selectivity of the selective deposition process, but instead decreases the selectivity of the process. Without being bound by any theory, Xianxin's exposure to the plasma generated by H ₂ and NH ₃ under the conditions described above damages the second dielectric surface, creating a surface position on which W deposition is achieved. point.

The fifth sample substrate and the control substrate were subjected to a first surface treatment process including exposing the substrate to a substrate including HCOOH, NH ₃ and H ₂ with a flow rate of 1000 sccm and using a rare gas as a carrier gas. Gas is generated in the plasma. The ratio of HCOOH to NH ₃ to H ₂ is 1: 1: 19. The sample substrate and the control substrate are then subjected to a selective deposition process for selectively depositing W on the first Cu and Co surfaces relative to the second dielectric surface. A control substrate including a Co surface was included to investigate the ability of the first surface treatment process to effectively reduce and / or remove the native oxide layer present thereon.

As shown in FIG. 7, W is selectively deposited on the first Cu surface and no W deposition is observed on the second dielectric surface, indicating that the first surface treatment enhances or achieves selective W deposition. W deposition was also observed on the substrate including the Co surface, indicating that the native oxide surface layer has been effectively reduced and / or removed. Without being bound by any theory, Xianxin's exposure to the plasma generated by HCOOH, NH ₃ and H ₂ under the conditions described above did not significantly damage the second dielectric surface while removing the organic surface layer And reducing and / or removing the native oxide from the first metal surface to enhance selective W deposition thereon.

A summary of the results of the first surface treatment process described above and the effect on selective W deposition is provided in Table 1 below. The first surface treatment process including contacting the substrate with a plasma generated by a gas including HCOOH, NH ₃ and H ₂ is the only one of the processes studied that can achieve deposition on Cu and Co surfaces while maintaining relative to the dielectric surface Selective process. Therefore, this first surface treatment process can remove the organic surface layer and reduce the native oxide layer and / or remove it from the Cu surface, and reduce the native oxide layer and / or remove it from the Co surface, while The second dielectric surface is not significantly damaged in order to maintain or enhance the selectivity of the selective W deposition process. Table 1: Results of various first surface treatment processes and a summary of the effects on the selective deposition process used to deposit W on a metal surface relative to a dielectric surface

Degree language as used herein, such as the terms "approximately", "about", "substantially" and "substantially" as used herein, means a value, quantity or characteristic close to the stated value, quantity or characteristic Still perform the desired function or achieve the desired result. For example, the terms "approximately", "about", "substantially" and "substantially" may refer to an amount that is less than or equal to 10%, less than or equal to 5%, less than or equal to 1% Within, less than or equal to 0.1%, and less than or equal to 0.01%. If the stated amount is 0 (eg, none, no), the above range may be a specific range and not within a specific% of the value. For example, within the stated amount is less than or equal to 10 weight / vol%, within the stated amount is less than or equal to 5 weight / vol%, and within the stated amount is less than or equal to 1 weight / vol%, in Within the stated amount is less than or equal to 0.1 weight / vol%, and within the stated amount is less than or equal to 0.01 weight / vol%.

For simplicity, the terms "film" and "thin film" are used herein. "Film" and "thin film" are intended to mean any continuous or discontinuous structure and material deposited by the methods disclosed herein. For example, "membrane" and "thin film" may include 2D materials, nanorods, nanotubes or nanoparticle, or even a single partial or complete molecular layer or a partial or complete atomic layer, or a Clusters. "Film" and "film" may include materials or layers that have pinholes but are still at least partially continuous.

Although certain specific examples and embodiments have been discussed, those skilled in the art should understand that the scope of the patent application of the present invention extends beyond the specific examples disclosed specifically to other alternative specific examples and / or uses and their obvious modifications and Equivalent.

10‧‧‧Process

11‧‧‧steps / reaction chamber passivation steps / reaction chamber passivation process

12‧‧‧steps / processing steps

13‧‧‧step / first surface treatment step

14‧‧‧step / selective deposition step / selective deposition process

20‧‧‧ substrate

21‧‧‧First metal surface

22‧‧‧second dielectric surface

23‧‧‧ metal oxide layer

25‧‧‧ organic layer

30‧‧‧Process

Step 31‧‧‧, reaction chamber passivation step

32‧‧‧ steps

33‧‧‧ steps, plasma treatment process

34‧‧‧step

35‧‧‧ step, selective deposition step

36‧‧‧ step, selective deposition step

37‧‧‧ step, selective deposition step

40‧‧‧Process

41‧‧‧step, passivation step of reaction chamber

42‧‧‧step

43‧‧‧ steps, processing

44‧‧‧ steps

45‧‧‧ step, selective deposition step

46‧‧‧ step, selective deposition step

47‧‧‧ step, selective deposition step

48‧‧‧ steps

50‧‧‧ Reaction chamber passivation process

51‧‧‧step

52‧‧‧step

53‧‧‧step

54‧‧‧ steps

55‧‧‧step

56‧‧‧ steps

FIG. 1 is a flowchart generally illustrating a process for selectively depositing a metal film on a first metal surface of a substrate with respect to a second silicon-containing surface.

FIG. 2A is a schematic diagram of an exemplary substrate including a first metal surface and a second dielectric surface having a metal oxide layer and a passivation layer disposed thereon.

2B is a schematic diagram of the exemplary substrate of FIG. 5A after being subjected to a surface treatment process as described herein and according to some specific examples and a process for selectively depositing a metal film on a first metal surface.

3 is a flowchart illustrating a process for selectively depositing a metal film on a first metal surface of a substrate with respect to a second silicon-containing surface according to some specific examples.

4 is a flowchart illustrating a process for selectively depositing a metal film on a first metal surface of a substrate with respect to a second silicon-containing surface according to some other specific examples.

5 is a flowchart generally illustrating a process for passivating a reaction chamber before performing the selective deposition process in the reaction chamber.

FIG. 6A is a scanning electron micrograph showing W blanket deposition on a substrate including a first Cu surface and a second low-k surface, the substrate being subjected to a surface including exposure of the substrate to a plasma generated by H ₂ Processing process.

FIG. 6B is a scanning electron micrograph showing W blanket deposition on a substrate including a first Cu surface and a second low-k surface, the substrate being subjected to a process including exposing the substrate to a plasma generated by H ₂ and N ₂ Surface treatment process.

6C is a scanning electron micrograph showing W blanket deposition on a substrate including a first Cu surface and a second low-k surface, the substrate being subjected to a surface including exposure of the substrate to a plasma generated by NH ₃ Processing process.

FIG. 6D is a scanning electron micrograph showing W blanket deposition on a substrate including a first Cu surface and a second low-k surface, the substrate being subjected to a process including exposing the substrate to a plasma generated by NH ₃ and H ₂ Surface treatment process.

FIG. 7 is a scanning electron micrograph showing a second low-k surface with respect to the substrate, W being selectively deposited on the first Cu surface of the substrate, the substrate being subjected to exposure including the substrate to HCOOH, NH ₃ and H ₂ Surface treatment process in the generated plasma.

Claims (20)

A process for selectively depositing a film on a first metal surface of the same substrate with respect to a second dielectric surface of a substrate, the process includes: performing a first metal surface treatment process, the first metal surface treatment process Including removing the surface layer from the first metal surface of the substrate so that a large number of new surface groups or ligands are not provided on the second dielectric surface by the first metal surface treatment process; and relative to the The second dielectric surface of the substrate selectively deposits a film on the first metal surface of the substrate with a selectivity greater than about 50%. The process according to item 1 of the scope of patent application, wherein the first metal surface treatment process includes exposing at least the first metal surface of the substrate to a plasma generated by a gas. The process according to item 2 of the scope of patent application, wherein the first metal surface treatment process includes exposing the first metal surface of the substrate and the second dielectric surface of the substrate to the plasma generated by the gas. in. The process according to item 1 of the patent application scope, wherein the first metal surface treatment process further comprises reducing and / or removing a metal oxide layer existing on the first metal surface of the substrate. The process as described in claim 1, wherein the removed surface layer includes an organic material. The process as described in claim 5, wherein the removed surface layer includes a passivation layer. The process according to item 6 of the application, wherein the removed surface layer includes benzotriazole (BTA). The process according to item 2 of the scope of patent application, wherein the gas includes carbolic acid. The process according to item 2 of the patent application scope, wherein the gas includes formic acid (HCOOH) and H ₂ . The process according to item 2 of the patent application scope, wherein the gas includes HCOOH, NH ₃ and H ₂ . The process as described in claim 10, wherein the gas is provided by a carrier gas including a rare gas. The process according to item 2 of the scope of patent application, wherein the temperature of the substrate during the first metal surface treatment process is about 300 ° C. The process according to item 2 of the patent application scope, wherein the first metal surface treatment process includes exposing at least the first metal surface of the substrate to the plasma for about 1 second to about 10 minutes. The process according to item 2 of the patent application scope, wherein the plasma is generated by supplying radio frequency power of about 10W to about 3000W to the gas. The process according to item 14 of the patent application scope, wherein the frequency of the RF power is about 1 MHz to about 10 GHz. The process according to item 2 of the scope of patent application, wherein the pressure of the gas generating the plasma is about 1 Pa to about 5000 Pa. The process as described in claim 1, wherein the selectively deposited film includes tungsten. The process as described in claim 1, wherein the first metal surface includes copper or cobalt. The process of claim 1, wherein the second dielectric surface includes silicon. A process for selectively depositing a film on a first metal surface of the same substrate with respect to a second dielectric surface of a substrate, the process includes: performing a first metal surface treatment process, the first metal surface treatment process Including removing a surface layer from the first metal surface of the substrate by exposing at least the first metal surface of the substrate to a plasma generated by a gas including HCOOH; and the second dielectric relative to the substrate The surface is selectively deposited on the first metal surface of the substrate with a selectivity greater than about 50%.