KR102234260B1 - Selective deposition of metallic films - Google Patents

Abstract

Metal-based layers may be selectively deposited on one surface of the substrate relative to the second surface of the substrate. In some embodiments, the metallic layers are selectively deposited on a first metallic surface relative to a second surface comprising silicon. In some embodiments, the reaction chamber in which the selective deposition process is performed may be selectively passivated before performing the selective deposition process. In some embodiments, a selectivity of greater than about 50% or even about 90% is achieved.

Description

Selective deposition of metal-based films{SELECTIVE DEPOSITION OF METALLIC FILMS}

Cross-reference of related applications

This application was filed on June 8, 2016 under the title of "Selective Deposition of Metallic Films", filed on June 8, 2016 under the title of US Application No. 15/177,198, and "Reaction Chamber Protection and Selective Deposition of Metallic Films." 2012 under the title "Selective Deposition of Metallic Films on Metallic Surfaces", which is a continuation in part of filed US Application No. 15/177195 and claims priority to US Provisional Application No. 61/569,142 filed December 9, 2011. No. 13/708,863, filed December 7, 2014, the entire disclosure of which is hereby incorporated herein by reference.

This application relates generally to the field of semiconductor manufacturing.

Currently, integrated circuits are manufactured by sophisticated processes in which various layers of material are sequentially constructed in a predetermined arrangement on a substrate.

As Moore's Law advances and devices become smaller and smaller, it becomes more difficult to meet the ever-increasing field-movement (EM) demands in copper wiring. As the wiring dimensions are reduced, the critical size of the void for EM failure is also reduced, so that the average time to failure is drastically reduced. Significant improvement in EM resistance is needed in order to be able to continue scaling.

The interface between the dielectric diffusion barrier and the metallic material has been shown to be the main path for metallic material diffusion and the weakest link in preventing EM failure. Implementation of a selective metal cap has been a challenging task as it is difficult to achieve good selectivity for a metal-based surface to a dielectric surface. Methods for selective deposition of metal-based films that can be used in this situation to reduce field transfer are disclosed herein.

The selective deposition of tungsten advantageously reduces the need for complex patterning steps during semiconductor device fabrication. However, subtle surface treatments, such as thermal or radical treatments, are generally preferred to provide the desired surface end for selective deposition. Such surface treatment may lead to loss of selectivity due to inadequate preparation of the surface required for selective deposition.

In some aspects, methods are described for selectively depositing a film on a first metallic surface of the same substrate relative to a second dielectric surface of the substrate. In some embodiments, the method includes performing a first metal-based surface treatment process, and the first metal-based surface treatment process includes a significant amount of new surface groups or ligands being added by the first metal-based surface treatment process. Removing a surface layer from the first metallic surface of the substrate such that it is not provided on the second dielectric surface; And selectively depositing a film with a selectivity greater than about 50% on the first metallic surface of the substrate relative to the second dielectric surface of the substrate.

In some embodiments, the first metallic surface treatment process includes exposing at least the first metallic surface of the substrate to a plasma generated from a gas. In some embodiments, the first metallic surface treatment process includes exposing the first metallic surface of the substrate and the second dielectric surface of the substrate to a plasma generated from the gas. In some embodiments, the first metal-based surface treatment process further includes reducing and/reducing or removing a metal oxide layer present on the first metal-based surface of the substrate. In some embodiments, the removed surface layer comprises an organic material. In some embodiments, the removed surface layer comprises a protective layer. In some embodiments, the removed surface layer comprises benzotriazole (BTA). In some embodiments, the gas comprises phenolic acid. In some embodiments, the gas comprises formic acid (HCOOH) and H ₂ . In some embodiments, the gas comprises HCOOH, NH ₃ , and H ₂ . In some embodiments, the gas is provided by a carrier gas comprising a noble gas. In some embodiments, the temperature of the substrate is about 300° C. during the first metal-based surface treatment process. In some embodiments, the first metallic surface treatment process includes exposing at least the first metallic surface of the substrate to the plasma for about 1 second to about 10 minutes. In some implementations, the plasma is generated by supplying RF power of about 10W to about 3000W to the gas. In some implementations, the frequency of the RF power is between about 1 MHz and about 10 GHz. In some embodiments, the pressure of the gas at which the plasma is generated is about 1 Pa to about 5000 Pa. In some embodiments, the selectively deposited film comprises tungsten. In some embodiments, the first metallic surface comprises copper or cobalt. In some embodiments, the second dielectric surface comprises silicon.

In some aspects, methods are described for selectively depositing a film on a first metallic surface of the same substrate relative to a second dielectric surface of the substrate. In some embodiments, the method includes performing a first metal-based surface treatment process, and the first metal-based surface treatment process comprises at least the first metal-based of the substrate in plasma generated from a gas containing HCOOH. Removing a surface layer from the first metallic surface of the substrate by exposing the surface; And selectively depositing a film with a selectivity greater than about 50% on the first metallic surface of the substrate relative to the second dielectric surface of the substrate.

In some aspects, methods are provided herein for selectively depositing a film on a substrate comprising a first metal-based surface and a silicon-containing second surface. In some embodiments, the methods include passivating a reaction chamber in which a selective deposition process is to be performed, exposing the substrate to plasma, undergoing a first surface treatment process on the substrate, the first surface After the treatment process, the step of performing one or more selective deposition cycles in the reaction chamber, each cycle contacting the substrate with a first precursor containing silicon or boron to be relative to a second surface containing silicon. Selectively forming a layer of a first material comprising Si or B on a first metallic surface and exposing the first material to a second precursor comprising a metal, thereby exposing the first material on the first metallic surface to a second Including conversion to metallic materials. In some embodiments, the second metallic material is deposited with a selectivity greater than about 50% on the first metallic surface of the substrate relative to the second surface comprising silicon.

In some embodiments, the first metallic surface comprises copper. In some embodiments, the first metallic surface comprises cobalt. In some embodiments, the second surface comprising silicon comprises SiO ₂ . In some embodiments, the second metallic material comprises tungsten. In some embodiments, passivating the reaction chamber comprises depositing a passivation layer on surfaces in the reaction chamber that may be exposed to the first or second precursor during the one or more selective deposition cycles. . In some embodiments, the passivation layer is formed by a vapor deposition process. In some embodiments, the passivation layer is formed by a plasma enhanced chemical vapor deposition (PECVD) process. In some embodiments, the passivation layer is formed by a plasma enhanced atomic layer deposition (PEALD) process. In some embodiments, the passivation layer is formed by guiding the first vapor phase silicon precursor and the second vapor phase nitrogen precursor to a reaction chamber in which plasma is present. In some embodiments, the passivation layer alternates the reaction chamber with a first precursor containing disilane and a second precursor containing a nitrogen atom, a nitrogen radical, or a nitrogen plasma and a hydrogen atom, a hydrogen radical, or a hydrogen plasma. , Is formed by sequentially exposing.

In some embodiments, the passivation layer comprises SiN. In some embodiments, the plasma is generated from ethanol. In some embodiments, the plasma is generated from _{NH 3} and H _2. In some embodiments, the first precursor comprises silane. In some embodiments, the first precursor comprises disilane. In some embodiments, the second precursor comprises a metal halide. In some embodiments, the second precursor comprises WF6. In some embodiments, the method further includes subjecting the substrate to a second surface treatment process before the substrate undergoes a first surface treatment process. In some embodiments, the second surface treatment process includes exposing the substrate to a treatment reactant, and the treatment reactant passivates the second surface. In some embodiments, the second metallic material is deposited with a selectivity greater than about 90% on the first metallic surface of the substrate relative to the second surface comprising silicon.

1 is a flow chart schematically illustrating a method for selectively depositing a metal film on a first metal-based surface relative to a second silicon-containing surface.
2A is a schematic diagram of an exemplary substrate including a first metal-based surface having a metal oxide layer and a passivation layer disposed thereon, and a second dielectric surface.
FIG. 2B is a schematic diagram of the exemplary substrate of FIG. 5A after undergoing a surface treatment process and a method for selectively depositing a metal film on a first metal-based surface as described herein in accordance with some embodiments.
3 is a flow diagram illustrating a method for selectively depositing a metal film on a first metal-based surface relative to a second silicon-containing surface according to certain embodiments.
4 is a flow diagram illustrating a method for selectively depositing a metal film on a first metal-based surface relative to a second silicon-containing surface according to certain other embodiments.
5 is a flow chart schematically illustrating a method for passivating a reaction chamber prior to performing an optional deposition process in the reaction chamber.
6A is a scan showing the deposition of a blanket of W on a substrate including a first Cu surface and a second low dielectric constant (k) surface and _{subjected to a surface treatment process including exposing the substrate to plasma generated from H 2} This is an electron micrograph.
Figure 6b is a blanket deposition of W on a substrate that includes a first Cu surface and a second low dielectric constant (k) surface and has undergone a surface treatment process including exposing the substrate to plasma generated from _{H 2} and N ₂ It is a scanning electron micrograph showing.
6C is a scan showing the deposition of a blanket of W on a substrate including a first Cu surface and a second low dielectric constant (k) surface and _{subjected to a surface treatment process including exposing the substrate to plasma generated from NH 3} This is an electron micrograph.
6D is a blanket deposition of W on a substrate including a first Cu surface and a second low dielectric constant (k) surface and subjected to a surface treatment process including exposing the substrate to plasma generated from _{NH 3} and H ₂ It is a scanning electron micrograph showing.
7 is a first Cu surface of the substrate relative to the second low dielectric constant (k) surface of the substrate subjected to a surface treatment process including exposing the substrate to plasma generated from HCOOH, NH ₃ , and H ₂ Is a scanning electron micrograph showing the selective deposition of W in.

In some implementations, methods are disclosed for selectively depositing a metal film on a metal or metal materials while avoiding deposition on a silicon containing material, such as silicon dioxide. For example, a metal film may be deposited over copper for the end of the wiring board treatment. In some implementations, metal films are deposited with a silicon-containing material on an integrated circuit workpiece including copper interconnects.

In some such applications, the selective deposition method disclosed herein can be used to deposit material over copper, thereby reducing the field migration of copper. In some implementations, the selective deposition is for the copper metal layer and not the silicon containing material on the substrate. In these applications, deposition on a silicon containing material is undesirable because it can reduce the effective dielectric constant value.

In some implementations, the method flow described herein is used to selectively deposit metal on micron scale (or smaller) features during fabrication of an integrated circuit. In some implementations, the feature size can be less than 100 microns, less than 1 micron, or less than 200 nm. In the case of selectively depositing W over Cu for applications in wiring, in some implementations, the feature size/line width can be less than 1 micrometer, less than 200 nm, less than 100 nm, and even 50 nm. Of course, one of ordinary skill in the art will recognize that larger features and selective deposition in other situations are possible using the disclosed methods.

In some implementations, selective deposition can save time and reduce the cost associated with processing the substrate by avoiding additional processing steps. For example, lithography for small dimensions will be very expensive in the future. When 8 or more layers of Cu metallization are performed on a chip, time is saved for each region of copper metallization during substrate processing, and thus time and cost savings that can be achieved using selective deposition are expanded. In addition, the method disclosed herein can eliminate the need for a diffusion barrier and other processing steps.

In some implementations, methods are disclosed for removing a surface layer or layers from a first metallic surface of a substrate. In some embodiments, the method of removing the surface layer may remove the surface layer present on the first metallic surface of the substrate. For example, the method of removing the surface layer may remove the surface layer present on the first surface to enable or improve selective deposition on the first surface of the substrate. In some embodiments, the removed surface layer may include a layer made of an organic material. That is, in some embodiments, the method of removing the surface layer may remove any organic material present on the first metallic surface. For example, the method of removing the surface layer may remove the organic passivation layer present on the first metal-based surface. For example, the surface layer removal method may remove benzotriazole (BTA) from a copper surface of an integrated circuit workpiece. In some embodiments, the method of removing the surface layer may remove any organic and/or hydrocarbon layer that may exist on the first metal-based surface.

In some embodiments, the method of removing the surface layer may remove the surface layer or a part of the surface layer existing on the first metallic surface of the substrate. In some embodiments, the method of removing the surface layer may reduce/reduce or remove any oxide surface layer present on the first metal-based surface. In some embodiments, the method of removing the surface layer may reduce/reduce or remove any natural oxide layer that may exist on the first metal-based surface. In some embodiments, the method of removing the surface layer may provide active sites on the first metallic surface, for example by reducing and/reducing or removing a surface layer or a portion of the surface layer present on the first metallic surface. In some embodiments, the oxide layer may be partially removed, and the remaining material including the oxide layer may be reduced by the surface layer removal method. That is, in some embodiments, a part of the oxide layer may be removed by the surface layer removal method, whereas any remaining oxide layer may be reduced by the surface layer removal method. In some embodiments, all of the oxide surface layer may be substantially removed by the surface layer removal method. In some embodiments, all of the oxide surface layer may be substantially reduced by the method of removing the surface layer.

As used herein, the term “reduced” may refer to that the oxide material is chemically converted to its non-oxide form. That is, when the metal oxide material is reduced, the metal oxide material is chemically converted to the metal of the metal oxide. For example, a copper oxide layer may be present on a first metal-based surface comprising copper and removal of the surface layer may reduce the copper oxide layer such that the copper oxide is converted to metallic copper. In some embodiments, the surface layer may include both an organic surface layer and an oxide layer underlying the organic surface layer. In some embodiments, in which the first metal-based surface may include an organic surface layer and a surface layer including an oxide layer disposed under the organic surface layer, the method of removing the surface layer may remove the organic surface layer and further reduce the oxide layer. By reducing and/or removing, a smooth first metallic surface can be provided.

In some embodiments, the first metallic surface of the substrate is subjected to a surface layer removal method including exposing the substrate to plasma generated from gas. In some embodiments, the method of removing the surface layer may include exposing at least the first surface to the plasma. In some embodiments, the method of removing the surface layer may include exposing the first surface and the second surface of the substrate to the plasma. For example, this method of removing the surface layer may remove the passivation layer present on the first metal-based surface, for example, the Cu surface. For example, such a surface layer removal method can reduce and/or remove the oxide layer from the first metal-based surface, such as reducing/reducing or removing the copper oxide layer from the Cu surface.

In some embodiments, plasma generated from a gas containing one or more organic compounds may be used in the surface layer removal method. In some embodiments, plasma generated from a gas comprising a compound described herein may be used in the surface layer removal method. In some embodiments, plasma generated from a gas containing formic acid (HCOOH) may be used in the method of removing the surface layer. In some embodiments, plasma generated from a gas containing carbolic acid may be used in the method of removing the surface layer. In some embodiments, _{plasma generated from a gas including HCOOH and NH 3} may be used in the method of removing the surface layer. In some embodiments, _{plasma generated from a gas including HCOOH and H 2} may be used in the method of removing the surface layer.

In some embodiments, _{plasma generated from a gas including HCOOH, NH 3} , and H ₂ may be used in the surface layer removal method. In some embodiments, the plasma can be generated from a gas comprising _{HCOOH, NH 3} and H _{2 , wherein the ratio of HCOOH to NH 3} to H ₂ is from about 1:1:5 to about 1:1:20, Or from about 1:1:9 to about 1:1:19. In some embodiments, _{the ratio of HCOOH to NH 3} to H ₂ is about 1:1:19. Advantageously, exposing the first metallic surface of the substrate to _{a plasma generated from a gas comprising HCOOH, NH 3} , and H ₂ can remove any passivation material present on the first metallic surface and In addition, it is possible to reduce/reduce or remove any natural oxide material present on the first metal-based surface. In addition, a _{method of removing a surface layer comprising exposing the substrate to a plasma generated from a gas comprising HCOOH, NH 3} , and H ₂ may include any additional or new surface groups or ligands on a second surface, such as a second surface of the substrate. 2 May not be provided on the dielectric surface. In this way, for example, a method of removing a surface layer can be used for deposition on a first metallic surface of a substrate, such as an integrated circuit workpiece, without the need to provide a masking or protective layer on the other surfaces of the substrate, or It can be used to prepare the first metallic surface of the substrate without the need for further treatment of the second surface, such as passivating the second surface against thin film deposition. Accordingly, such a surface layer removal method can simplify and/or reduce the number of processing steps required in a selective deposition and/or integrated circuit manufacturing method.

1 is a flow diagram schematically illustrating a method 10 for selectively depositing a metal film on a first metal-based surface relative to a second silicon-containing surface. In some embodiments, the method prior to the selective deposition step 14 to enable selective deposition before the selectivity disappears during the selective deposition method, improve selectivity, and/or reduce the number of successive cycles. An optional reaction chamber passivation step 11 may be included. In some implementations, the reaction chamber passivation step 11 can increase the number of successive cycles at which the desired level of selectivity is achieved. The optional reaction chamber passivation step 11 may include providing a passivation material or passivation layer on locations other than the chamber surfaces that may be exposed to a precursor or reactant during the selective deposition step 14. The reaction chamber passivation step 11 will reduce or eliminate the amount of reactive by-products generated by the selective deposition step 14 by limiting or preventing the deposition of metallic material on the chamber surface during the subsequent selective deposition step 14. I can. In some implementations, the reaction chamber passivation step 11 may reduce contamination of the substrate during the selective deposition step 14, which in turn may enable selective deposition or increase selectivity.

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

Selective deposition using the methods described herein does not require treatment of a silicon containing material that blocks deposition thereon. As a result, in some embodiments, the second surface comprising silicon is a self-assembled monolayer that will prevent the actual top surface of the second dielectric surface from being exposed to the chemicals of the deposition methods described herein. It does not contain a passivation layer or blocking layer such as monolayer, SAM). Thus, in some embodiments, the film is selectively deposited over the first metal surface on a substrate that has not been subjected to a treatment designed to prevent deposition of a film on the second silicon containing surface, such as a blocking treatment or a passivation treatment. That is, in some embodiments, selective deposition may be made even if deposition is blocked by a blocking layer or a passivation layer on the second surface comprising silicon. Instead, the deposition conditions are selected so that the selective deposition method is achieved without the need to pretreat the second surface comprising silicon prior to deposition.

In some implementations, the second silicon-containing layer can be exposed to a treatment designed to treat the first surface. For example, in some implementations, it is desirable to passivate the first metal surface, and the silicon-containing second surface may be exposed to the same passivation treatment as the first metal surface. For example, in the case of Cu, both the first Cu surface and the silicon-containing second surface may be exposed to benzotriazole (BTA) or other passivating chemicals. However, prior to the first surface treatment to remove the passivation layer from the metal surface, no specific additional treatment or exposure to the silicon-containing second surface (except for exposure that may be received during sample transfer) is made at all. Does not. In particular, it is not necessary to perform any treatment designed to block deposition of the film on the silicon-containing second surface.

In some embodiments, upon selective deposition of the film, the second dielectric surface contains only surface groups naturally occurring in the low dielectric constant (k) material, and has a significant amount not naturally present in the low dielectric constant material itself. It does not contain functional groups or ligands. In some implementations, no active treatment of the second dielectric surface is performed after the first surface treatment that will add surface groups to the second dielectric surface. In some implementations, the second dielectric surface includes only surface groups naturally occurring in low dielectric constant materials, including groups that may have formed during transport of the substrate in air, for example.

However, in some implementations, the second silicon-containing surface can be selectively treated in step 12. In some implementations, the silicon-containing surface can be treated in step 12 by reducing the amount of material deposited on the silicon-containing surface, such as passivating the silicon-containing surface, to improve the selectivity of the deposition process. In some implementations, processing step 12 is intended to restore the silicon-containing layer and not block deposition over the silicon-containing layer. In some embodiments, treating the second silicone-containing surface in step 12 may include contacting the second surface with a treatment chemical, e.g., the silicone-containing second surface is trimale(dimethylamino ) May come into contact with treatment chemicals including silanes. In some implementations, the substrate may be degassed at or before the beginning of step 12, for example to remove any moisture from the substrate surface or within the silicon containing material.

In some implementations, the substrate surface is cleaned or treated in step 13 prior to starting the optional deposition step 14. In some implementations, the first surface treatment step 13 may include exposing the substrate to a plasma, such as a plasma generated from a gas comprising _{HCOOH, NH 3} , and H _2. In some embodiments, the first surface treatment step 13 may include a process for removing a surface layer from the first metallic surface described herein. In some implementations, the first surface treatment step 13 may include exposing the substrate to a vapor treatment chemical, such as formic acid. In some embodiments, the first surface treatment step 13 may reduce and/or remove the surface layer from the first metallic surface. In some embodiments, the first surface treatment step 13 may reduce and/reduce or remove any natural oxides that may exist on the first metallic surface. In some embodiments, the natural oxide may still be present on the first surface after the first surface treatment step 13. In some embodiments, the first surface treatment step 13 may remove any surface layer, such as an organic and/or hydrocarbon surface layer that may be present on the first metallic surface. In some embodiments, the first surface treatment step 13 may remove the organic or hydrocarbon surface layer and reduce/reduce or remove the oxide layer from the first metal-based surface. In some implementations, the first surface treatment step 13 can provide an active site on the first metallic-based surface. In some implementations, the substrate may be degassed at or before the beginning of step 13, for example to remove any moisture from the substrate surface or within the silicon containing material. In some embodiments, the first surface treatment step 13 may not substantially damage or degrade the second surface, e.g., the first surface treatment step 13 may have a significant effect on the second surface. It may not provide or form positive new surface groups or ligands.

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

The substrate can include various types of materials. When manufacturing integrated circuits, substrates generally contain many thin films with varying chemical and physical properties. For example and without limitation, the substrate may include a silicon containing layer and a metal layer. In some implementations, the substrate can include metal carbide. In some embodiments, the substrate can include a conductive oxide.

Preferably, the substrate has a first surface comprising a metal, referred to herein as a first metal surface or a first metal-based surface. In some embodiments, the first surface is essentially an elemental metal, such as Cu or Co. In some embodiments, the first surface comprises a metal nitride. In some embodiments, the first surface comprises a transition metal. The transition metal may be selected from the following group: Ti, V, Cr, Mn, Nb, Mo, Ru, Rh, Pd, Ag, Au, Hf, Ta, W, Re, Os, Ir and Pt. In some embodiments, the first surface preferably comprises copper. In some embodiments, the first surface comprises cobalt. In some implementations, the first surface comprises tungsten. In some implementations, the first surface may include a natural oxide of a metal, for example, the first surface may include tungsten oxide. In some implementations, the first surface can include a seam, gap, or space, and the selective deposition process closes or substantially fills the seam, gap, or space of the first surface. In some embodiments, the first surface comprises a noble metal. The noble metal can be selected from the group of: Au, Pt, Ir, Pd, Os, Ag, Re, Rh, and Ru.

In some implementations, the second surface is a dielectric surface. In some embodiments, the second surface is a silicon-containing surface referred to herein as a second silicon-containing surface or a second surface comprising silicon. In some embodiments, the silicon-containing surface comprises, for example, SiO ₂ . In some embodiments, the second surface may include silicon oxide, silicon nitride, silicon carbide, silicon oxynitride, silicon dioxide, or mixtures thereof. In some embodiments, the material comprising the second surface is a porous material. In some embodiments, the porous material includes pores that are connected to each other, while in other embodiments, the pores are not connected to each other. In some embodiments, the second surface comprises a low dielectric constant (k) material defined as an insulator having a dielectric constant value of less than about 4.0. In some embodiments, the dielectric constant values of low k materials are 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 an organosilicate surface, such as a silicon containing surface having organic surface groups such _{as -CH x surface groups.} In some embodiments, the second surface can include SiOCH.

If the precursors used in the methods used herein are present in the gas phase prior to delivery to the reaction chamber and contacting the substrate surface, these precursors may be solid, liquid or gaseous materials under standard conditions (room temperature and atmospheric pressure). Plasma conditions can also be used. Thus, in some implementations the plasma may be formed from vapor phase reactants or precursors. “Pulsing” the vaporized precursor onto the substrate means that the precursor vapor is delivered into the chamber for a limited time. Typically, the pulsing time is about 0.05 to 10 seconds. However, depending on the substrate type and its surface area, the pulsing time can be much longer than 10 seconds. The pulsed time may be in minutes depending on the case. In some cases ensuring complete saturation of the reactions, the precursor may have been supplied in multiple short pulses rather than in one long pulse.

The mass flow rate of the precursor can also be determined by a person skilled in the art. In one embodiment, for deposition on a 300 mm wafer, the flow rate of the precursors is preferably limited up to about 1 to 2000 sccm. In some embodiments, the flow rate may be from about 50 sccm to about 1500 sccm, from about 100 sccm to about 1000 sccm, or from about 200 sccm to about 500 sccm.

The pressure in the reaction chamber is generally about 0.01 to about 50 mbar. In some embodiments, the pressure is from about 0.1 mbar to about 20 mbar or from about 1 mbar to about 10 mbar. However, as can be readily determined by a person skilled in the art, in some cases the pressure will be above or below this range.

chamber passivation

Referring back to FIG. 1, in some implementations, it may be desirable that the reaction chamber or chambers in which the selective deposition method is to be performed are passivated in step 11 before selectively depositing the metal-based film in step 14. In some implementations, the reaction chamber passivation step 11 enables selective deposition before the selectivity disappears during a selective deposition method, such as a metal-based film selective deposition method as described herein, improves selectivity, And/or it is possible to increase the number of consecutive cycles.

In some embodiments, a selective deposition method for selectively depositing a film on a first surface, such as a metal-based surface of a substrate relative to a second surface, such as a silicon-containing surface, generates reactive by-products that can quickly damage the second surface. I can make it. Reactive by-products can provide active sites on the second surface, which in turn loses selectivity. In some implementations, undesired deposition can occur on the reaction chamber surface to increase the amount of reactive by-products throughout the selective deposition process, where the deposition occurs primarily on the substrate. Passivating these chamber surfaces against deposition to reduce the amount of unwanted deposition on the chamber surface, e.g. the inner surface of the reaction chamber, and consequently to reduce the amount of reactive by-products generated by the selective deposition process. It is desirable to do it.

For example, in some embodiments, the selective deposition process of W can produce a reactive by-product having the _{formula SiF x (x is 1-4).} In some embodiments where the reactive chamber is not passivated, unwanted W deposition can occur at the chamber surface, producing an _{undesirable amount of SiF x by-product.} In some embodiments in which the reactive chamber is passivated, the W deposition may be predominantly on the first surface of the substrate and not or to a lesser extent on the undesired chamber surface, so that the reaction chamber is relatively selective to the non-passivated W deposition process. This can lead to a reduction in the amount of _{SiF x by-} products generated during the deposition process.

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

In some implementations, the reaction chamber passivation step 11 may be repeated after the selective deposition process is performed in step 14. In some implementations, the reaction chamber passivation step 11 may be repeated whenever one, two, three, or more optional deposition steps 14 have been performed. For example, in some implementations, the reaction chamber passivation step 11 may be repeated each time 1, 5, 10, 20, 50, or more substrates, such as a wafer, have undergone the optional deposition step 14. have. In some implementations, the reaction chamber passivation step 11 may be repeated after a certain number of cycles of selective deposition step 14 has been performed. In some implementations, the reaction chamber passivation step 11 may be repeated upon completion of 50, 100, 150, or more deposition cycles. In some implementations, the substrate or substrates may remain within the reaction chamber during the reaction chamber passivation step 11 or may not be present within the reaction chamber.

In some implementations, the reaction chamber passivation step 11 includes providing a passivation layer or passivation material on chamber surfaces and other surfaces that may be exposed to a precursor or reactant during the optional deposition step 14. I can. In some embodiments, the passivation material is deposited or formed on the inner surface of the reaction chamber, the chamber showerhead, and/or any other portions that may be exposed to a precursor or reactant during the optional deposition step 14. In some implementations, the passivation material may be deposited on any surface in the reaction chamber other than the substrate for which selective deposition is desired to occur. In some implementations, the passivation material is a different material than the material selectively deposited in step 14. In some implementations, the deposition method used to deposit the passivation layer may not be a selective deposition method.

In some implementations, the reaction chamber passivation 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 embodiments, the reaction chamber passivation process 11 maintains a desired level of selectivity of the selective deposition process 14 greater than about 50% compared to a reaction chamber that has not been subjected to any reaction chamber passivation process 11. It is possible to increase the number of consecutive cycles. In some embodiments, the reaction chamber passivation process 11 has a desired level of selectivity of the selective deposition process 14 greater than about 75% compared to a reaction chamber that has not been subjected to any reaction chamber passivation process 11. The number of consecutive cycles maintained by more than 100%, more than about 200%, more than about 400%, or more than about 900% can be increased. In some embodiments, the reaction chamber passivation process 11 maintains a desired level of selectivity of the selective deposition process 14 more than about 20 times as compared to a reaction chamber that has not undergone any reaction chamber passivation process 11. It is possible to increase the number of consecutive cycles.

In some embodiments, 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, and the reaction chamber passivation process 11 is a selective deposition process. The desired level of selectivity of (14) can be repeated after a desired number of cycles to allow for additional consecutive cycles to be maintained. That is, the reaction chamber passivation process 11, after a desired number of consecutive cycles, and before the selectivity of the selective deposition process is reduced to less than the desired level to allow additional continuous cycles in which the desired level of selectivity of the selective deposition process is maintained. Can be done. The reaction chamber passivation 11 may be repeated any number of times after a desired number of consecutive cycles of the selective deposition process to maintain the desired level of selectivity of the selective deposition process 14.

In some implementations, the previously deposited passivation layer or layers may be etched or at least partially removed from the inner surfaces of the reaction chamber prior to deposition of a subsequent passivation layer through the reaction chamber passivation process 11. In some embodiments, the previously deposited passivation layer or layers are etched or at least partially etched from the inner surfaces of the reaction chamber after going through the reaction chamber passivation process 11 at least two times, five times or more, or ten or more times. Can be removed. In some embodiments, no etching or layer removal is performed between two or more, five or more, or ten or more reaction chamber passivation processes. In some implementations, the reaction chamber may then undergo a reaction chamber passivation process 11 after the previously deposited passivation layer or layers have been etched or at least partially removed from the inner surfaces of the reaction chamber.

In some implementations, the reaction chamber passivation 11 can increase the duration during which the desired level of selectivity of the selective deposition process 14 is maintained. In some embodiments, the reaction chamber passivation process 11 has a desired level of selectivity of the selective deposition process 14 greater than or equal to about 50% compared to a reaction chamber that has not been subjected to any reaction chamber passivation process 11. The duration maintained by more than 75%, more than about 100%, more than about 200%, more than about 400%, or more than about 900% can be increased. In some embodiments, the reaction chamber passivation process 11 maintains a desired level of selectivity of the selective deposition process 14 more than about 20 times as compared to a reaction chamber that has not undergone any reaction chamber passivation process 11. You can increase the duration of time.

In some implementations, the reaction chamber passivation 11 can increase the number of substrates, such as wafers, for which a desired level of selectivity of the selective deposition process 14 is maintained. That is, the reaction chamber passivation 11 can increase the number of wafers on which the selective deposition process can be simultaneously performed while maintaining a desired level of selectivity. In some implementations, the reaction chamber passivation process 11 has a desired level of selectivity of the selective deposition process 14 greater than about 2 times, about 5 times compared to a reaction chamber that has not been subjected to any reaction chamber passivation process 11. The number of substrates held more than times, more than about 10 times, more than about 20 times, or more than about 50 times may be increased.

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

In some implementations, during the selective deposition process, material may be deposited on the inner surfaces of the reaction chamber. Such deposition material may peel off and impede selective deposition, or may provide reactive sites such that undesirably large amounts of unwanted reaction by-products may be generated during the selective deposition process. Thus, it may be necessary to periodically remove the deposited material from the inner surfaces of the reaction chamber. In some embodiments, the reaction chamber passivation process 11 includes the number of deposition cycles that can be performed within the reaction chamber before an etching, such as an in-situ etching, has to be performed to obtain or maintain a desired level of selectivity. Can be extended. In some embodiments, the reaction chamber passivation process 11 is greater than about 50%, greater than about 75%, greater than about 100%, greater than about 200%, compared to a reaction chamber that has not undergone any reaction chamber passivation process 11. More than about 400%, more than about 900%, or more than about 20 times to achieve or maintain the desired level of selectivity, the number of deposition cycles that can be performed in the reaction chamber before an etching, such as an in-situ etching, has to be performed. You can increase the number.

In some implementations, the passivation layer deposited or formed during the reaction chamber passivation step 11 may comprise SiN. In some embodiments, the passivation layer may include silicon oxide, silicon nitride, silicon carbide, silicon oxynitride, or mixtures thereof. In some embodiments, the passivation layer may include a metal oxide. In some embodiments, the passivation layer may comprise pure metal or any material other than pure silicon. In some embodiments, the passivation layer is not a self-organizing monolayer (SAM) or a similar layer using molecules similar to those used to form the SAM.

In some embodiments, the passivation layer may be formed or deposited by a vapor deposition process in step 11. In some embodiments, the deposition process for forming the passivation layer may include a chemically driven vapor deposition process. That is, the deposition process for forming the passivation layer is a vapor deposition process that varies according to one or more chemical reactions of the precursors, and is not a physical vapor deposition process. For example, the deposition process for forming or depositing the passivation layer may be a chemical vapor deposition (CVD) process or an atomic layer deposition (ALD) process. In some embodiments, the passivation layer may be formed by a plasma enhanced ALD (PEALD) process or a plasma enhanced CVD (PECVD) process.

In some embodiments, the deposition process for forming the passivation layer may include 1 to 10,000 deposition cycles, 5 to 5,000 deposition cycles, 10 to 2,500 deposition cycles, or 10 to 50 deposition cycles. In some embodiments, the passivation layer may have a thickness of 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 embodiments, it may be useful for the passivation layer to have a thickness of less than 1 nm. In some embodiments, the passivation layer may have a thickness of less than about 200 nm, less than about 100 nm, less than about 50 nm, less than about 25 nm.

In some embodiments, the deposition process for forming the passivation layer may include an ALD-type process including one or more deposition cycles, and the deposition cycle includes the reaction chamber surfaces in the first vapor phase precursor and the second vapor phase precursor. It includes the step of alternately, sequentially exposing. In some embodiments, if the first vapor phase precursor and reaction by-product are present, these precursors and reaction by-products may be removed from the reaction chamber prior to exposing or contacting the reaction chamber surfaces to the second vapor phase precursor. In some embodiments, the second vapor phase precursor and any reaction by-products may be removed from the reaction chamber prior to exposing or contacting the reaction chamber surfaces thereafter to the first vapor phase precursor.

In some embodiments, the deposition process for forming the passivation layer may include a CVD process, wherein the first vapor phase precursor and the second vapor phase precursor are delivered into the reaction chamber in simultaneous or overlapping pulses, and the precursors are Reacts and/or decomposes on the chamber surface to form a passivation layer.

In some embodiments, the deposition process for forming the passivation layer may include a PECVD process, wherein the first vapor phase precursor and the second vapor phase precursor are delivered into the reaction chamber in simultaneous or overlapping pulses, and vplasma is It is generated in the reaction chamber. The precursors react and/or decompose within the plasma and/or on the chamber surface to form a passivation layer. In some implementations, the plasma can be generated remotely and introduced into the reaction chamber.

In some implementations, the deposition process to form the passivation layer comprising SiN may be a PECVD process. In some implementations, the PECVD deposition process can use a vapor phase silicon precursor and a vapor phase nitrogen precursor. In some embodiments, the silicon precursor and the nitrogen precursor may be provided together or in an overlapping pulse into the reaction chamber. In some implementations, a plasma is generated within the reaction chamber and the silicon precursor and nitrogen precursor react and/or decompose to form a SiN passivation layer on the chamber surface. In some implementations, the plasma can be generated remotely and introduced into the reaction chamber.

In some implementations, the deposition process to form a passivation layer comprising silicon, such as SiN, may utilize a silicon precursor and one or more additional precursors, such as a nitrogen precursor. In some implementations, the deposition process to form the passivation layer may use a nitrogen precursor. In some embodiments, the silicon precursor used in the passivation layer deposition process may include silane, such as silane, disilane, or trisilane. In some embodiments, the nitrogen precursor may comprise atomic nitrogen, nitrogen radicals, nitrogen plasma, or combinations thereof. In some embodiments, the nitrogen precursor may further comprise atomic hydrogen, hydrogen radicals, hydrogen plasma, or combinations thereof. In some implementations, the nitrogen precursor may comprise a plasma generated from _{N 2.} In some implementations, the nitrogen precursor can include plasma generated from _{N 2} and H _2. In some implementations, the nitrogen precursor may _{include a plasma generated from N 2} and a noble gas such as argon. In some implementations, the nitrogen precursor may _{include a plasma generated from N 2} , H ₂ and a noble gas such as argon. In some embodiments, the silicon precursor and the nitrogen precursor may be separated and provided to the reaction chamber in the ALD type reaction, or may be provided to the reaction chamber together or in overlapping pulses in the CVD reaction.

In some implementations, the deposition process to form a passivation layer, such as a passivation layer comprising silicon and nitrogen, such as SiN, may include one or more deposition cycles, wherein the deposition cycle causes the reaction chamber surfaces to become a first vapor phase precursor. , Alternately and sequentially exposing the second vapor phase precursor, and the third vapor phase precursor. In some embodiments, the first vapor phase precursor can comprise silane; The second vapor phase precursor may comprise a metal halide; The third gaseous precursor may include an aminosilane. In some embodiments, the first gaseous precursor may comprise a disilane; The second vapor phase precursor may comprise WF ₆ ; The third gaseous precursor may include trimethyl(dimethylamino)silane.

The terms first, second, and third precursor are used herein by reference only, and those skilled in the art will appreciate that the deposition cycle can begin with exposing the reaction chamber surface to either the first, second, or third vapor phase precursor. I will understand. In some embodiments, the first vapor phase precursor may contact the substrate prior to the second or third vapor phase precursor. In some embodiments, the second vapor phase precursor may contact the substrate after the first vapor phase precursor and before the third vapor phase precursor. In some embodiments, the third vapor phase precursor may contact the substrate behind both the first and second vapor phase precursors. In some embodiments, the order in which the first, second, and third vapor phase precursors contact the substrate may be different. In some implementations, regardless of whether two or more precursors are referred to as a first, second, third, etc. precursor, they may be provided together or partially in overlapping pulses. In addition, the reaction chamber surfaces may alternately and sequentially contact the vapor phase precursors in any order determined by a person skilled in the art. For example, the chamber surface may be contacted with a third vapor phase precursor before the surface contacts the second vapor phase precursor in a given deposition cycle.

In some embodiments, the passivation layer deposition process using the first, second, and third vapor phase precursors may include at least one deposition cycle, at least 3 deposition cycles, at least 5 deposition cycles, or at least 10 deposition cycles, or 25 It may include more than one deposition cycle and, in some instances, no more than 50 deposition cycles.

In some embodiments, the passivation layer deposited by the passivation layer deposition process using the first, second, and third vapor phase precursors is per selective deposition process 14, or a substrate that has undergone the selective deposition process 14, such as It is deposited for each wafer. 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 implementations, an additional passivation layer is deposited by a passivation layer deposition process for each substrate that has undergone the selective deposition process.

In some embodiments, the passivation layer deposited by the passivation layer deposition process using the first, second, and third vapor phase precursors is more than 2, more than 4, more than 9, which has been subjected to the selective deposition process 14, Or deposited every more than 19 substrates.

In some implementations, the deposition process to form the passivation layer can be performed with a reaction chamber pressure and temperature similar or equal to the selective deposition process described herein. In some embodiments, the flow rate of the vapor phase precursors used in the passivation layer deposition process may be similar or equal to the flow rate of the precursors used in the selective deposition process described herein.

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

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

In some embodiments, chamber surfaces on which the passivation layer is deposited may be selectively cleaned prior to depositing the passivation layer. In some implementations, chamber surfaces can be cleaned by exposing the chamber surfaces to a plasma. For example, in some embodiments, the reaction chamber can be cleaned by a process that includes exposing the reaction chamber to a radical comprising fluorine, such as an NF _{3 -based radical.}

In some implementations, the metal oxide passivation layer can be formed by a vapor deposition process, such as an ALD, CVD, PEALD, or PECVD process. In some embodiments, the deposition process for forming the passivation layer may include 1 to 10,000 deposition cycles, 5 to 5,000 deposition cycles, 10 to 2,500 deposition cycles, or 10 to 50 deposition cycles.

In some embodiments, the passivation layer may include a metal oxide. In some embodiments, the passivation layer may include a transition metal oxide. In some embodiments, the passivation layer is, 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 embodiments, the passivation layer comprising a transition metal oxide may be formed by a deposition process including one or more deposition cycles, wherein the deposition cycle causes the reaction chamber surfaces to be applied to the first vapor phase precursor and the second vapor phase precursor. It includes the step of alternately, sequentially exposing. In some embodiments, the deposition process may be an ALD, CVD, PEALD, or PECVD process. In some embodiments, the first vapor phase precursor may include a transition metal. In some embodiments, the first vapor phase precursor may include a metal halide or an organometallic compound. In some implementations, the second vapor phase precursor can include oxygen. In some embodiments, the second vapor phase precursor can be an oxygen reactant or an oxygen source. In some embodiments, the second vapor phase precursor may comprise 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 passivation layer comprising Al 2} O ₃ may be formed by a deposition process comprising one or more deposition cycles, wherein the deposition cycle comprises a first vapor phase precursor comprising aluminum and And alternately and sequentially exposing the second gaseous precursor containing oxygen. In some embodiments, the first vapor phase precursor comprising aluminum is an organometallic compound comprising aluminum, such as trimethylaluminum (TMA). In some embodiments, the second vapor phase precursor comprising 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. Additionally, in some embodiments, the first and second vapor phase precursors can be provided in any order, as can be readily determined by one of skill in the art. In some implementations, the first and second vapor phase precursors may be provided in pulses that overlap or at least partially overlap, such as in a CVD process.

In some implementations, the metallic material may be deposited or formed on the chamber surfaces by a vapor deposition process, such as a chemical vapor deposition (CVD) or atomic layer deposition (ALD) process. In some implementations, the metallic material can include antimony, such as elemental antimony. In some embodiments, the passivation layer may be formed by a plasma enhanced ALD (PEALD) process. In some embodiments, the deposition process for forming the passivation layer may include 1 to 10,000 deposition cycles, 5 to 5,000 deposition cycles, 10 to 2,500 deposition cycles, or 10 to 50 deposition cycles.

In some embodiments, the metal-based material may then be oxidized to form a metal oxide passivation layer. In some embodiments, the metallic material may be oxidized by exposure to an oxygen reactant. In some embodiments, the plasma can include oxygen atoms, oxygen radicals, oxygen plasmas, or combinations thereof. For example, in some embodiments, the oxygen reactant may comprise 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 metallic material may be subjected to an oxidation process including at least one step of exposing the metallic material to an oxide or oxygen reactant. In some implementations, the oxidation process can include exposing the metallic material to two or more oxide or oxygen reactants in two or more steps. In some embodiments, the two or more oxides or oxygen reactants may be different oxides or oxygen reactants. In some embodiments, the two or more exposing steps may be separated by a purge or oxide removal step. In some embodiments, exposing the metallic material to more than one oxide or oxygen reactant may preferably cause a greater amount of the metallic material to oxidize than exposure to one oxide or oxygen reactant.

In some implementations, the passivation layer may be formed over the chamber surface by oxidizing a metallic material deposited over the chamber surface during a previous deposition process. In some embodiments where the selective deposition step 14 has been previously performed within the reaction chamber, the reaction chamber passivation step 11 oxidizes any metallic material deposited on the chamber surfaces during the selective deposition step 14 It may include forming a metal oxide passivation layer. In some embodiments, the metallic material may be oxidized by exposure to an oxygen precursor. In some embodiments, the plasma can include oxygen atoms, oxygen radicals, oxygen plasmas, or combinations thereof.

For example, W deposited on the chamber surface during a previous selective deposition process of W may be oxidized to form a chamber passivation layer. In some implementations, the metallic material is deposited on the chamber surfaces by a deposition process that is not used to deposit material on a substrate or wafer within the reaction chamber.

Surface treatment containing silicon

As shown in FIG. 1, and in some implementations, a silicon-containing material may be treated in step 12 to avoid deposition thereon. For example, in some implementations, the silicon-containing material can be treated after surface cleaning and prior to deposition. In some implementations, the silicon-containing surface can be treated by reducing the amount of material deposited on the silicon-containing surface, such as by passivating the silicon-containing surface, to improve the selectivity of the deposition process. In some embodiments, the treatment is intended to restore the silicon-containing layer and not block deposition over the silicon-containing layer.

In some embodiments, the silicon-containing surface is a low dielectric constant (k) surface that has been degassed to remove absorbed moisture from the atmosphere.

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

In some embodiments, the silicon-containing surface can be treated by contacting one or more silanes, such as disilane. In some embodiments, the silicon-containing surface is _{treated with trimethylchlorosilane (CH 3} ) ₃ SiCl (TMCS) or another type of alkylhalosilane having the _{formula R 3- x} SiX _{x, where x is 1 to} 3 and each R can be independently selected to be a C1-C5 hydrocarbon, such as methyl, ethyl, propyl or butyl, preferably methyl, and X is a halide, preferably a chloride. U.S. Patent No. 6,391,785 discloses various surface modifications and treatments, which are incorporated herein in their entirety. In some embodiments, any of the surface modifications or treatments disclosed in US Pat. No. 6,391,785 can be used in the methods disclosed herein.

In some embodiments, the silicone containing surface is contacted with, for example, trimethyl(dimethylamino)silane. In some embodiments, the silicon-containing surface is contacted with an alkylaminosilane having the ^{formula (R I} ) ₃ Si(NR ^II R ^{III ), wherein R I} is a linear or branched C1-C5 alkyl group or a linear or branched C1-C4 alkyl group, R ^II is a linear or branched C1-C5 alkyl group, a linear or branched C1-C4 alkyl group, or hydrogen, and R ^III is a linear or branched C1-C5 alkyl group or a linear or branched C1-C4 It is an alkyl group.

In some embodiments, the 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 is reactive with the silicon-containing surface. That is, the silane binds to the surface through ligand A, or ligand A forms a bond with the surface, but then ligand A can migrate from the surface and/or from the silane.

In some embodiments, the recovery chemical is selected from the silane family and has the formula Si _n H _{2n +2} (n is 1 or more), or is selected from the silane family and has the formula Si _n H _2n (n is 3 or more). Have. In some embodiments, the recovery chemical is a silicon source comprising silane, disilane, or trisilane. In some embodiments, the silane is disilane Si ₂ H ₆ trisilane Si ₃ H ₈ . In some embodiments, the silicon source can be selected from silane compounds having the formula: SiH _x L _y , where L is selected from the group comprising alkyl, alkenyl, alkynyl, alkoxide, and amine. It is a ligand. In some cases, L is a ligand selected from the group of halogenated consisting of F, Cl, Br and I.

In some embodiments, the step of recovering the silicon-containing surface comprises applying the substrate 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. prior to selective deposition. It is done by exposure. In some embodiments, the silicon-containing surface recovery step may be performed at a temperature of about 400° C. or less, about 25° C. to about 300° C., or 30° C. to about 250° C. In some embodiments, a recovery chemical such as Si ₂ H ₆ is provided to the reaction chamber at a flow rate of about 5 to 100 sccm, or about 30 to 60 sccm. In some embodiments, the recovery chemical is provided to the reaction chamber for about 1 to 20 seconds or about 1 to 10 seconds. In some embodiments, a recovery chemical, such as TMCS, is provided in pulses. About 1-20 or about 1-10 pulses may be provided, for example, each having a pulse and purge time of about 1-10 seconds. In some embodiments, the step of recovering the silicon-containing surface may occur in a second reaction chamber, separate from the reaction chamber in which deposition may be performed.

This step is called the surface recovery step and the chemicals used are referred to as recovery chemicals, but these names are used herein for brevity and no special recovery function is implied. Thus, in some embodiments, the treatment and/or chemical may not completely or even partially recover the silicon-containing surface.

If the silicon-containing surface is damaged, the damaged surface may be repaired by performing a surface recovery step after optional deposition steps.

Some silicon-containing materials can have a porous structure. To avoid diffusion, etching, and other undesired processes, the pores can be sealed or terminated with a protective group before starting the deposition process. Thus, in some embodiments, the porous silicon-containing material can be treated to seal or terminate the pores with protective groups prior to starting the selective deposition process. In some embodiments, the porous silicon-containing material is treated prior to providing the metal reactant.

In some embodiments, 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 group or a linear or branched C1-C4 alkyl group. . In some embodiments, the pores are sealed by silylation, ie forming -Si(CH ₃ ) ₃ groups on a silicon containing surface, such as a low dielectric constant (k) surface or a SiO ₂ surface. Etching can be partially avoided by silylation prior to introducing the metal fluoride or other reactants. Silylation can be used to block pores to avoid penetration of the reactants into the silicon-containing surface. _{In some embodiments, silylation is achieved through the reaction of a silicon compound, such as Cl-Si(CH 3} ) ₃ , with the Si-OH terminated surface of the silicon-containing material: Si-OH + Cl-Si(CH ₃ ) ₃ -> Si-O-Si(CH ₃ ) ₃ + HCl. Thus, in some embodiments, a suitable surface end is formed prior to providing the silicone compound. In addition, the use of silicone compounds with longer carbon-containing ligands is possible.

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

In some implementations, an organic layer may be formed over the silicon-containing material by ALD prior to deposition to block the pores and make the silicon-containing surface more resistant to metal fluoride.

In some embodiments where selectivity is incomplete or higher selectivity is required, after selective deposition, the surface may be treated to remove material from the insulator surface without completely removing the material from the metallic surface, for example using isotropic selective etching. I can. For example, HCl vapor or wet etching can be used.

First metallic surface treatment

In some implementations, the substrate can be subjected to a process to remove a surface layer from a metallic surface as described herein. For example, as described above, a substrate comprising at least a first metal-based surface may be subjected to a process to remove a surface layer from the substrate as described herein prior to selectively depositing a thin film onto the substrate. In some implementations, the substrate can be subjected to a process to remove a surface layer from the first metallic surface of the substrate in a passivated reaction chamber as described herein. However, in some other implementations, the substrate may be subjected to a process to remove the surface layer from the first metallic surface of the substrate in the non-passivated reaction chamber.

As shown in FIG. 1 and according to some implementations, the substrate surface may be selectively cleaned or treated in step 13. For example, for embodiments where the first material is copper, the copper surface can be cleaned or reduced so that pure elemental copper is above the substrate surface. In some embodiments, the first surface treatment process can include a surface layer removal process as described herein. For example, the first surface treatment process may remove a surface layer present on the first surface to enable or enhance selective deposition on the first surface of the substrate. In some embodiments, the removed surface layer may include a layer made of an organic material. That is, in some embodiments, the first surface treatment process may remove any organic material present on the first metallic surface. For example, the first surface treatment process may remove the organic passivation layer present on the first metal-based surface. For example, the first surface treatment process may remove benzotriazole (BTA) from the copper surface. In some embodiments, the first surface treatment process may remove any organic and/or hydrocarbon layer that may exist on the first metallic surface.

In some embodiments, the first surface treatment process may reduce a surface layer or a part of the surface layer present on the first metallic surface of the substrate. In some embodiments, the first surface treatment process may reduce/reduce or remove any oxide surface layer present on the first metallic surface. In some embodiments, the first surface treatment process may reduce/reduce or remove any natural oxide layer that may exist on the first metal-based surface. In some embodiments, the first surface treatment process may provide active sites on the first metal-based surface, for example by reducing and/reducing or removing a surface layer or a portion of the surface layer present on the first metal-based surface. . In some embodiments, the oxide layer may be partially removed, and the remaining material including the oxide layer may be reduced by the first surface treatment process. That is, in some embodiments, a part of the oxide layer may be removed by the first surface treatment process, whereas any remaining oxide layer may be reduced by the first surface treatment process. In some embodiments, all of the oxide surface layer may be substantially removed by the first surface treatment process. In some embodiments, all of the oxide surface layer may be substantially reduced by the first surface treatment process.

As used herein, the term “reduced” may refer to that the oxide material is chemically converted to its non-oxide form. That is, when the metal oxide material is reduced, the metal oxide material is chemically converted to the metal of the metal oxide. For example, a copper oxide layer may be present on a first metal-based surface comprising copper and removal of the surface layer may reduce the copper oxide layer such that the copper oxide is converted to metallic copper. In some embodiments, the surface layer may include both an organic surface layer and an oxide layer underlying the organic surface layer. In some embodiments, in which the first metal-based surface may include an organic surface layer and a surface layer including an oxide layer disposed under the organic surface layer, the first surface treatment process may remove the organic surface layer, and also the oxide layer. By reducing/reducing or removing, a smooth first metallic surface can be provided.

The first surface treatment process may be performed by any one of various methods using plasma or chemicals such as citric acid. For example, the substrate surface may be cleaned or treated using a plasma generated from a gas, such as a gas comprising hydrogen, including _{H 2} , NH _{3, and/or other constituent gases.} In some embodiments, HCl treatment is used as the first surface treatment method. In some implementations, the first surface treatment process includes exposing the substrate to a treatment reactant, such as formic acid. Other first surface treatment methods are possible. The specific first surface treatment method to be used in any particular case may be selected based on various factors such as, for example, the type of material on the substrate surface, and the material and deposition conditions.

In some cases, a first material such as copper for which a selective deposition process is desired is passivated. Passivation may be the result of intentional treatment of the substrate to form the passivation layer, or may result from exposure to oxygen during process conditions, such as transfer of the substrate.

The surface(s) of the substrate may, for example, be passivated prior to transfer from one reaction space to another. In some embodiments, the surface of the first material can be passivated against oxidation in air using any of a variety of known passivation chemistries. In some embodiments where selective deposition over Cu is desired, the Cu surface may be passivated, for example with BTA. Passivation can be removed using the first surface treatment described herein.

In some implementations, the first surface treatment process includes exposing the substrate to a treatment reactant. In some embodiments, the treatment reactant is a gaseous organic reactant. In some embodiments, the treatment reactant may comprise at least one alcohol group, preferably the group consisting of primary alcohols, secondary alcohols, tertiary alcohols, polyhydric alcohols, cyclic alcohols, aromatic alcohols, and other alcohol derivatives. Can be selected from

Preferred primary alcohols, in particular primary alcohols according to formula (I), have -OH groups attached to carbon atoms bonded to other carbon atoms:

R ¹ -OH (I)

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

Preferred secondary alcohols have an -OH group attached to a carbon atom bonded to two different carbon atoms. In particular, preferred secondary alcohols have the general formula (II):

(II)

(II)

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

Preferred tertiary alcohols have -OH groups attached to carbon atoms bonded to three different carbon atoms. In particular, preferred tertiary alcohols have the general formula (III):

(III)

(III)

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

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

Preferred cyclic alcohols have an -OH group attached to at least one carbon atom that is part of a ring of 1 to 10, more preferably 5-6 carbon atoms.

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

Preferred treatment reactants comprising at least one aldehyde group (-CHO) are selected from the group consisting of compounds having general formula (V), alkandial compounds having general formula (VI), and other derivatives of aldehydes. .

Thus, in one embodiment, a preferred treatment reactant is an aldehyde having 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 alkyl groups and alkenyl groups, preferably methyl, ethyl, propyl, butyl, pentyl or hexyl groups. 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 butylaldehyde.

In another embodiment, a preferred treatment reactant is an aldehyde having 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 are directly bonded to each other (R ⁴ has no value).

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

Thus, in one embodiment, a preferred treatment reactant is a carboxylic acid having general formula (VII):

R ⁵ -COOH (VII)

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

In some embodiments, the first surface treatment process is a process as disclosed in US patent application Ser. No. 14/628799 entitled “Removing Surface Passivation”, which is incorporated by reference in its entirety.

In some embodiments, the first metallic surface of the substrate is subjected to a first surface treatment process including exposing the substrate to plasma generated from gas. In some embodiments, the first surface treatment process may include exposing at least the first surface to the plasma. In some embodiments, the first surface treatment process may include exposing the first surface and the second surface to the plasma. For example, this first surface treatment process may remove the passivation layer present on the first metal-based surface, for example, the Cu surface. For example, this first surface treatment process may also reduce or remove the oxide layer from the first metal-based surface, such as reducing/reducing or removing the copper oxide layer from the Cu surface.

In some implementations, the first surface treatment process includes exposing the substrate to a plasma generated from a gas. In some embodiments, the plasma may be generated from a gas consisting only of Ar. In some embodiments, an Ar and H-containing plasma is used in the first surface treatment process. In some embodiments, Ar and H and N-containing plasmas are used in the first surface treatment process. It can be noted that instead of Ar, other noble gases such as He, Ne, Kr or Xe can be used under substantially the same conditions. In some implementations, more than one type of plasma may be used. For example, one or more of an Ar containing plasma, an Ar and H containing plasma, and an Ar, H and N containing plasma may be provided. That is, in some implementations, the plasma may be generated from an Ar, H, and/or N containing gas or gases. In some implementations, Ar or other noble gas may be used as a carrier gas for the component gases in which the plasma is generated. For example, in some implementations where the _{plasma is generated from a gas comprising H 2} , Ar can be used as a carrier gas for _{H 2.} Thus, in some implementations, a gas comprising H2 and a plasma generated from a carrier gas may include H-plasma and Ar-plasma.

In some embodiments, _{plasma generated from a gas containing H 2} may be used in the first surface treatment process. In some embodiments, 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 containing both H 2} and ethanol may be used in the first surface treatment process. For example, in some embodiments where the first metal-based surface is a Cu surface, _{plasma generated from a gas containing H 2} , ethanol, or H ₂ and ethanol is preferably used in the first surface treatment process.

In some embodiments, _{plasma generated from a gas containing NH 3} may be used in the first surface treatment process. In some embodiments, _{plasma generated from a gas including NH 3} and H ₂ may be used in the first surface treatment process. For example, in some embodiments where the first metallic surface is a Co surface, _{plasma generated from a gas including NH 3} and H ₂ is used in the first surface treatment process. In some embodiments, the plasma can be generated from a gas comprising _{NH 3} and H _{2 , wherein the ratio of NH 3} to H ₂ is from about 1:100 to about 1:1, preferably from about 1:5 to It is about 1:20. In some embodiments, _{the ratio of NH 3} to H ₂ can be about 1:19, about 1:9, or about 1:5.

In some embodiments, plasma generated from a gas including one or more organic compounds may be used in the first surface treatment process. In some embodiments, plasma generated from a gas containing a compound according to Formulas (I) to (VII) described above may be used in the first surface treatment process. In some embodiments, plasma generated from a gas containing formic acid (HCOOH) may be used in the first surface treatment process. In some embodiments, plasma generated from a gas containing phenol may be used in the first surface treatment process. In some embodiments, _{plasma generated from a gas including HCOOH and NH 3} may be used in the first surface treatment process. In some embodiments, _{plasma generated from a gas including HCOOH and H 2} may be used in the first surface treatment process.

In some embodiments, _{plasma generated from a gas including HCOOH, NH 3} , and H ₂ may be used in the first surface treatment process. In some embodiments, the plasma can be generated from a gas comprising _{HCOOH, NH 3} and H _{2 , wherein the ratio of HCOOH to NH 3} to H ₂ is from about 1:1:5 to about 1:1:20, Or from about 1:1:9 to about 1:1:19. In some embodiments, _{the ratio of HCOOH to NH 3} to H ₂ is about 1:1:19.

In some embodiments, the first surface treatment process includes exposing the substrate to a first reactant prior to exposure to a second treatment reactant. In some embodiments, the first treatment reactant may include O ₃ , an oxygen atom, an oxygen radical, or an oxygen plasma. In some embodiments, the second treatment reactant may comprise a hydrogen radical, a hydrogen atom, a hydrogen radical, or a hydrogen plasma. In some implementations, the first treatment reactant can be removed from the reaction chamber prior to introducing the second treatment reactant. In some implementations, exposure to the first treatment reactant may occur in the first reaction chamber and exposure of the substrate to the second treatment reactant may occur in the second reaction chamber.

In some embodiments, the first treatment reactant may remove any organic passivation layer or hydrocarbons that may be present on the first metal-based surface, whereas the second treatment reactant may remove the oxide layer on the first metal-based surface. Can be removed and/or reduced. For example, in some embodiments where the first metal-based surface is a Co surface, _{exposure to O 3} can remove a naturally occurring hydrocarbon layer from the Co surface, whereas subsequent exposure to H radicals is a Co surface. It is possible to reduce the Co oxide layer present on the phase.

In some embodiments using an Ar-containing plasma, Ar may be provided, for example, from about 1 to about 3000 sccm, more preferably from about 300 to about 1500 sccm, and most preferably from about 1000 to about 1300 sccm. In some embodiments using an Hr containing plasma, H ₂ may be provided, for example, from about 1 to about 500 sccm, more preferably from about 10 to about 200 sccm, and most preferably from about 30 to about 100 sccm. In some embodiments using an N-containing plasma, N ₂ or NH ₃ may be provided, such as about 1 to about 500 sccm, more preferably about 5 to about 200 sccm, and most preferably about 5 to about 30 sccm. have. For other types of plasmas, such as ethanol or O containing plasmas, similar conditions can be used. In some embodiments using plasma generated from a gas comprising HCOOH, the gas is provided at a flow rate of about 1 sccm to about 3000 sccm.

In some embodiments in which 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 embodiments in which plasma is generated from a gas comprising HCOOH, NH ₃ , and H ₂ , the gas may be provided at a flow rate of about 1000 sccm. In some implementations, the flow rate discussed herein does not include the flow rate of any carrier gas that can be used to provide the gas from which the plasma is generated.

In some embodiments, the plasma has an output of less than about 3000 watts, such as about 1 to about 3000 watts, about 1 to about 1500 watts, about 1 to about 1000 watts, about 1 to about 500 watts, or about 1 to about 200 watts. It can occur at the following output. In some implementations, 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 embodiments, the plasma or treatment reactant is provided for less than about 200 seconds, such as less than about 180 seconds, less than about 60 seconds, or less than about 30 seconds. However, in some embodiments, the first surface treatment process may include exposing the substrate to plasma or a treatment reactant for 10 minutes or more. For example, in some embodiments, the substrate is applied to the plasma or treatment 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. While exposed. In some embodiments, the substrate is exposed to a plasma or treatment reactant for about 5 seconds to about 30 seconds.

In some implementations, the exposure of the substrate to the plasma or reactant may be continuous or separated into multiple pulses. The number of pulses required is determined by the length of each of the pulses used to reach the required total exposure time as determined by a person skilled in the art.

The temperature during the surface treatment is, 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 implementations, the substrate temperature can be about 150° C. during the first surface treatment. In some implementations, the substrate may be degassed to remove moisture from the substrate surface inside, for example, a silicon containing material. In some implementations, the substrate may be degassed prior to undergoing the first surface treatment process. In some embodiments, the pressure of the gas generating plasma in the first surface treatment process is from about 1 Pa to about 5000 Pa, from about 10 Pa to about 3000 Pa, from about 50 Pa to about 1000 Pa, from about 150 Pa to about 150 Pa. It may be about 500 Pa, or about 350 Pa.

In some embodiments, conditions for the first surface treatment process are selected such that etching of the second surface can be avoided or minimized. That is, in some embodiments, the second surface treatment process does not substantially damage the second surface and does not degrade the quality. As used herein with reference to the second surface, the term damage or deterioration may refer to a selective deposition process, such as a modification to the second surface that may reduce the selectivity of the processes described herein. For example, in a selective deposition process for depositing a film on a first surface relative to a second surface, there is more on a damaged or degraded second surface compared to a second surface that is not damaged or degraded. The material or particles of the deposited material may be deposited. Thus, the presence of material deposited on the second surface after a selective deposition process to deposit a film on the first surface relative to the second surface as described herein may indicate a damaged or degraded second surface. In some implementations, 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 embodiments, a significant amount of new surface groups or ligands sufficient to reduce the selectivity of the selective deposition process are not formed or adsorbed on the first surface by the first surface treatment process. In some embodiments, 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. Does not.

A schematic diagram of an exemplary substrate 20 comprising a first metallic surface 21 and a second dielectric surface 22 prior to the surface treatment process is shown in FIG. 2A in accordance with some embodiments. The first metal-based surface 21 comprises a metal oxide layer 23 disposed thereon, for example a natural metal oxide formed naturally by exposure to the surrounding environment. The first metal-based surface 21 also includes an organic material layer 25 disposed over the metal oxide layer 23, for example an organic passivation layer such as BTA.

As described herein and according to some embodiments, the substrate 20 is then subjected to a first surface treatment process. For example, the substrate 20, consequently the first metallic surface 21 and the second dielectric surface 22, are exposed to a plasma generated from a gas, such as a gas comprising _{HCOOH, H 2} , and NH ₃ Can be. 2B, the first surface treatment process may remove the organic material layer 25 from the first metal-based surface 21. The first surface treatment process may also remove and/or reduce the metal oxide layer 23 from the first metallic surface 21, leaving a smooth first metallic surface 21. Additionally, as shown in FIG. 2B, the second dielectric surface is not damaged or degraded by the first surface treatment process, and does not contain significant amounts of new or additional surface groups and/or ligands.

Selective deposition

First precursor

In some implementations, a first precursor is provided to the substrate such that a layer is selectively formed on the first metal surface of the substrate relative to the second silicon containing surface of the substrate. In some embodiments, the first precursor preferably comprises silicon or boron. In some embodiments, a 0.05-4 nm thick layer of Si or B is formed on the metal surface of the substrate. In some embodiments, a 0.1-2 nm thick layer of Si or B is formed on the metal surface of the substrate. In some embodiments, a layer of less than 1 nm of Si or B may be used. Without wishing to be bound by theory, the metal surface on the substrate may promote or aid adsorption or decomposition of the first precursor relative to the reactivity of the second surface. In some embodiments, the formation of silicon or boron on the metal surface is self-limiting, such that when exposed to a reactant, it forms less than a single layer. In some implementations, the silicon or boron source chemical can decompose on a copper or metal surface.

In some embodiments, the silicon source chemical is selected from the silane family Si _n H _{2n +2} (n is 1 or more) or the cyclic silane family Si _n H _2n (n is 3 or more). In some embodiments, the silicon source comprises silane or disilane. Most preferably, the silane is disilane Si ₂ H ₆ or trisilane Si ₃ H ₈ . In some embodiments, the silicon source can be selected from silane compounds having the formula: SiH _x L _y , where L is selected from the group comprising alkyl, alkenyl, alkynyl, alkoxide, and amine. It is a ligand. In some cases, L is a ligand selected from the group of halogenated consisting of F, Cl, Br and I.

In some embodiments, the first precursor comprises boron. In some embodiments, the first precursor is diborane (B ₂ H ₆ ). Diborane has properties similar to some of the silane-based compounds. For example, diborane has a lower decomposition temperature than disilane, but similar properties to trisilane (silcore).

Other precursors containing boron can also be used. The availability of numerous boron compounds makes it possible to select those having the desired properties. Additionally, it is possible to use more than one boron compound. Preferably, one or more of the following boron compounds are used:

Borane according to Equation I or Equation II.

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

Where n is an integer of 1 to 10, preferably 2 to 6, and x is an even number, preferably 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.

Among the boranes according to Formula I, examples include nido -borane (B _n H _{n +4} ), arachno - borane (B _n H _n+6 ) and hyph - borane (B _n H _n+8 ). Among boranes according to formula II, an example is conjuncto- borane (B _n H _m ). In addition, a borane complex such as _{(CH 3} CH ₂ ) ₃ N-BH _{3 may be used.}

Borane halides, especially fluorides, borides and chlorides. An example of a suitable compound is B ₂ H ₅ Br. Another example is boron halides with high boron/halide ratios, such as B ₂ F ₄ , B ₂ Cl ₄ and B ₂ Br ₄ . It is also possible to use borane halide complexes.

Halogenoboranes according to Equation III.

B _n X _n (III)

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

Carboranes according to Formula IV

C ₂ B _n H _{n + x} (IV)

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

Examples of carborane according to formula IV include closo- carborane (C ₂ B _n H _{n +2} ), nido - carborane (C ₂ B _n H _{n +4} ) and arachno- carborane (C ₂ B _n H _{n +6} ).

Amine-borane adduct according to formula V.

R ₃ NBX ₃ (V)

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

Aminoborane in which at least one substituent on B is an amino group according to formula VI

R ₂ N (VI)

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

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

Cyclic borazine (-BH-NH-) ₃ and volatile derivatives thereof.

Alkyl boron or alkyl borane, wherein alkyl is typically linear or branched C1 to C10 alkyl, preferably C2 to C4 alkyl.

In some embodiments, the first precursor comprises germanium. In some embodiments, the germanium source chemical is selected from the germanium family Ge _n H _{2n +2} (n is 1 or more) or the cyclic germanium family Ge _n H _2n (n is 3 or more). In some preferred embodiments, the germanium source comprises germane GeH ₄ . In some embodiments, the germanium source can be selected from germanium having the following formula: GeH _x L _y , wherein L is a ligand selected from the group comprising alkyl, alkenyl, alkynyl, alkoxide, and amine. to be. In some cases, L is a ligand selected from the group of halogenated consisting of F, Cl, Br and I.

Metal source chemicals

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

In some embodiments, the second reactant comprises a noble metal. The noble metal can be selected from the group of: Au, Pt, Ir, Pd, Os, Ag, Rh, and Ru.

In some embodiments, the second reactant comprises a metal halide (F, Cl, Br, I). In some embodiments, the second reactant comprises a transition metal halide. In some embodiments, the second reactant preferably comprises fluoride. In some embodiments, the second reactant comprises _{WF 6, TaF 5, NbF 5} , TiF 4, MoF x, VF x. In some embodiments, the second reactant comprises WF ₆ .

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

In some implementations, an elemental metal film, such as a W film, may be formed. In some implementations, a metal nitride film may be formed. In some implementations, a metal silicide can be formed.

In some embodiments, a metal-based film or an elemental metal film is first formed through the reaction of a second reactant with Si or B on the substrate, and the film is then converted to the corresponding metal silicide or metal nitride through further processing. For example, the first metal-based film or the elemental metal film may be exposed to a third reactant to be converted into metal silicide or metal nitride.

In some implementations, additional treatment of the metallic material may be performed to dope the metallic material or convert the metallic material into a metallic silicide or metallic nitride. In some embodiments, for example, the material may be converted to the corresponding metal nitride through _{plasma or NH 3 -treatment.} In some implementations, the electrically conductive metallic material can be converted to a higher electrical resistivity or dielectric material by using a different treatment and depending on the starting metallic material.

In some embodiments, multiple pulses of one of the reactants may be provided before providing the next reactant. In some embodiments, any excess reactants can be removed prior to providing the next reactant. In some implementations, the process chamber can be purged prior to providing the next reactant.

In some embodiments, gaseous precursors may be provided to the reaction space with the aid of an inert carrier gas. Removing excess reactant may include discharging some contents of the reaction space or purging the reaction space with helium, nitrogen or any other inert gas. In some embodiments, purging may include blocking the flow of the reaction gas while continuously flowing the inert carrier gas into the reaction space.

Deposition temperature

In some implementations, the temperature is selected to enable selective deposition. If the amount of material deposited per unit area or unit volume on the first surface (e.g., at/cm ² or at/cm ³ ) is greater than the amount of material deposited per unit area or unit volume on the second surface, the deposition is generally Is defined as optional. The amount of material deposited on the surfaces can be determined by measuring the thickness of each layer. In some cases, thickness measurements may not be possible due to discontinuous films. In some cases, selectivity can be determined by measuring the deposited atoms per unit area or unit volume. As mentioned above, selectivity can be expressed as a ratio of the amount of material formed on the first surface to the amount of material formed on the first and second surfaces that are joined. Preferably, the selectivity is greater than about 70%, greater than about 80%, more preferably greater than 90%, even more preferably greater than 95%, and most preferably greater than about 100%. In some cases, selectivity in excess of 80% may be reasonable for certain applications. In some cases, selectivity in excess of 50% may be reasonable for certain applications.

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

In some implementations, the deposition temperature is selected such that the first precursor comprising silicon or boron forms a layer containing silicon or boron on the first metal surface. In some implementations, the first precursor does not form a layer on the second surface comprising silicon or forms less than a complete layer on the second surface.

The particular temperature used may depend in part on the silicon or boron precursor selected with the first surface or metal and the second surface or dielectric on the substrate. Preferably, the silicon or boron source forms a layer comprising silicon or boron on the first metal surface instead of the second surface comprising silicon. Preferably, the layer comprising silicon or boron is less than or equal to a single layer. In some cases, a layer made of more silicon or boron than a single layer may be formed. In some embodiments, a layer of silicon or boron having a thickness of about 0.05 nm to about 4 nm is formed on the metal surface of the substrate. In some embodiments, a layer having a thickness of about 0.1 nm to about 2 nm, preferably made of silicon or boron, is 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, the layer comprising silicon or boron is formed by decomposition.

In some cases, a layer of silicon or boron may be formed over both the metal surface and the silicon-containing surface at higher temperatures. Lower temperatures are preferred in these situations because silicon or boron can form on the metal surface at a lower temperature than the silicon-containing surface. Thus, the temperature may be selected such that the silicon precursor reacts preferentially with the first surface or metal surface relative to the silicon surface or silicon-containing surface.

In some implementations, the deposition temperature is selected to achieve a desired level of selectivity. For example, the temperature may be selected so that the adsorption of the silicon or boron containing precursor to the low dielectric constant (k) material is limited to the amount required to achieve the desired level of selectivity.

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

In some embodiments, the deposition temperature is preferably 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. may be used. In some embodiments, the deposition temperature range for selective deposition with a selectivity greater than 50% in films having a thickness less than about 5 nm (e.g., deposited W thickness) deposited using _{disilane and WF 6} Is from about 30°C to about 200°C. In some implementations, a desirable level of uniformity and selectivity can be achieved using a deposition temperature range of about 30°C to about 110°C. In some implementations, a desirable level of uniformity and selectivity can be achieved using a deposition temperature range of about 40°C to about 110°C. In some implementations, a desirable level of uniformity and selectivity can be achieved using a deposition temperature range of less than about 100°C. In these temperature ranges, one skilled in the art can optimize the process to achieve the desired or reasonable uniformity and selectivity for the deposited films using a special reactor with special precursors.

In some embodiments, the silicon or boron containing precursor and the second metal precursor are provided in the same reaction space at the same temperature. In some implementations, the 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 to a first reaction space and a second metal reactant to a second reaction space.

_{In some embodiments using disilane and depositing tungsten using WF 6} on a copper or cobalt surface, a selectivity of greater than about 80%, preferably greater than about 90%, relative to the surface comprising silicon is This can be achieved using a deposition temperature of about 30° C. to about 110° C. The deposition temperature for trisilane can be even lower than the deposition temperature for disilane. In the above mentioned implementations, the deposited film can 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, less than about 4 nm, or in some embodiments, less than about 1 nm to less than about 4 nm. However, in some cases, a desired level of selectivity, such as greater than 50%, more preferably greater than 80%, is achieved using a selectively deposited film having a thickness greater than about 10 nm.

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

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

In some implementations, a W film having a thickness of less than about 3 nm is selectively deposited over Cu or Co over a substrate having a selectivity greater than about 90% relative to the silicon containing material.

If lower selectivity is desired, the temperature may be slightly higher than the temperature for the process to achieve selectivity in excess of 90%.

In some implementations, deposition conditions and/or reactants are selected to avoid or minimize etching of the silicon-containing surface. 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 these fluorides can etch the silicon-containing surface. Thus, in some implementations, the deposition temperature is selected to avoid or eliminate etching of the silicon-containing surface.

The substrate temperature while providing the second reactant may be equal to the temperature while providing the silicon or boron containing reactant. In other implementations, different temperatures can be used.

In embodiments in which WF ₆ as the second reactant is used with disilane as the first reactant, a temperature of about 30° C. to about 110° C. may be used.

In some implementations, when providing the second reactant to increase the conversion of the metal reactant, the temperature of the substrate may be elevated. For example, when TaF ₅ and NbF ₅ are used as the second reactants, 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 exceed 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 a person skilled in the art.

Example process flow

3 is a flow diagram schematically illustrating a method 30 for selectively depositing a metal film on a first metal-based surface relative to a second silicon-containing surface in accordance with certain embodiments. The reaction chamber or chambers in which the selective deposition process is to be performed are first subjected to a selective reactor passivation process in step 31 to deposit a SiN passivation layer on arbitrary chamber surfaces directly connected to the location of the subsequent selective deposition process. A substrate comprising a first metallic surface such as a Co surface and a second surface comprising silicon such as _{SiO 2 is provided and selectively degassed.} In some implementations, the substrate may be subjected to a selective silicon-containing surface treatment to passivate a _{SiO 2 surface at step 32, for example.} Thereafter, the substrate may be subjected to a first selective surface treatment process in step 33. As described above, in some implementations, the first surface treatment process can include exposing the substrate to a plasma generated from a _{plasma, such as NH 3} , H _{2, and a combination of the two.}

In some implementations, the plasma treatment process 33 can reduce the first Co surface. In some embodiments, the plasma treatment process may remove the natural oxide layer present on the first Co surface. In some implementations, the plasma treatment process can remove a passivation layer or a hydrocarbon layer, such as a BTA layer, that may be present on the second Co surface.

In some implementations, steps 32 and 33 can be performed in a different reaction chamber or chambers than the reaction chamber passivated in step 31. That is, steps 32 and 33 may be performed in a reaction chamber or chambers different from a reaction chamber in which a subsequent selective deposition process is to be performed. In addition, in some embodiments, the reaction chamber passivation step 31 may proceed simultaneously with one or more steps 32 and 33.

In some embodiments, the substrate surface is optionally further annealed in an inert atmosphere after optional step 33. The annealing is performed at a temperature higher than steps 32, 33 or the following optional deposition steps 35-37. The temperature 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 embodiments, the substrate surface is further annealed in an _{NH 3 environment to create NH x} -surface ends for any cobalt oxide present on the first Co surface.

Next, in step 34, the substrate is transferred to the chamber selectively passivated in step 31, and a silicon or boron source is provided as the substrate, so that in step 35, silicon or boron-containing paper is deposited on the Co surface. In some embodiments, the silicon source is silane or disilane. In some embodiments, the disilane is, the silicon precursor may be selectively digested with Co on the surface relative to the SiO ₂ surface to form the silicon on a Co surface but uses the deposition temperature does not form the silicon on the SiO ₂ surface. For example, the deposition temperature may be about 30°C to about 110°C. In some embodiments, the silicon or boron source reacts with the Co surface in a self-limiting manner. It is believed that the Co surface may enable the formation of silicon relative to the formation on the _{SiO 2 surface.}

In some embodiments, a layer comprising silicon or boron and 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 embodiments, a layer comprising silicon or boron and 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 preferred embodiments, the formation of a layer comprising silicon or boron on the metal surface is self-limiting. Thus, at most a single layer, comprising silicon or boron, is formed in each cycle.

After the silicon or boron-containing layer is formed over the Co layer, in step 36 the layer containing silicon or boron is converted into a layer containing the metal from a second reactant such _{as a metal halide, e.g., WF 6 is a second reactant such as tungsten.} It is used to _{In some embodiments, WF 6} , TaF ₅ , NbF ₅ or other compounds capable of reacting with the Si or B layer are introduced to the substrate surface to form a metal-based layer or metal silicide. In some implementations, the silicon or boron precursor (eg, disilane) and second reactant (eg, metal halide) pulses may be repeated in step 37 until a metal-based layer having a desired thickness is formed. In some embodiments, the metal-based layer is an elemental metal, such as W. In some embodiments, the metal-based layer may include additional elements such as Si, B, N and other dopants. In some embodiments, the metallic layer is further processed to form a different material. For example, the elemental metal layer can be treated with a third reactant to form a metal nitride or metal silicide.

The deposition cycle can be defined as providing a silicon or boron precursor and providing the second metal reactant, i.e., steps 35 and 36. In some implementations, no other reactants are provided in the deposition cycle. In some implementations, the deposition cycle is repeated to form a W layer having a predetermined thickness. In some embodiments, a W layer having a thickness of about 0.05 nm to about 4 nm is formed in each cycle. In some embodiments, a W layer having a thickness of about 0.1 nm to about 2 nm is formed in each cycle. In some embodiments, the W layer has a thickness of about 1 to 2 nm. In other embodiments, 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 preferred embodiments, the layer has a thickness of less than 10 nm.

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

In some embodiments, no other reactant is provided other than a precursor comprising silicon or boron and a second metal reactant.

In some embodiments, the material comprising the first surface, such as cobalt, is neither transformed nor reacted to form another compound during the selective deposition cycle.

In some implementations, after one or more deposition cycles have been completed, a half deposition cycle may be performed in step 38. For example, a silicon or boron precursor pulse or alternatively a second metal reactant may be provided. In some implementations, after one or more deposition cycles, a silicon or boron precursor pulse is provided. When a silicon or boron precursor pulse (or other metal reactant) is provided, the formed material may form a sacrificial layer made of silicon oxide or boron oxide (or metal oxide) when exposed to air or an oxygen-containing atmosphere. The sacrificial layer may prevent the metal-based material under the silicon oxide or boron oxide layer from being oxidized when exposed to air or an oxygen-containing atmosphere outside the reactor. Silicon oxide or the boron oxide layer is formed, is in the additional processing step, for example, and more preferably with a metal chemicals described herein, preferably from WF _6, TaF _5, NbF _5, TiF _4, MoF _x or VF _x Can be removed with a single pulse of WF _6.

In some implementations, the entire process flow can be performed in a single reaction chamber, such as a single process module. However, in other embodiments, various steps are performed in more than one reaction chamber. For example, in some embodiments, a first surface treatment process and a silicon-containing surface treatment process (if used) are performed in a first reaction chamber, whereas a selective deposition process may be performed in a different second reaction chamber. . In some embodiments, the different second reaction chamber may also be processed to form a passivation layer therein. If an optional thermal annealing step is required or required, the substrate may then be transferred to a second reaction chamber where thermal annealing (if used) and selective deposition are performed. In some embodiments, the annealing step is performed in a first reaction chamber, and the substrate is transferred to a first reaction chamber or a third reaction chamber where selective deposition is performed. In some embodiments, the first surface treatment and the silicon-containing surface treatment (if used) are performed in a first reaction chamber, and the selective deposition is performed in a second reaction chamber that is different without a thermal annealing step between the first surface treatment and the deposition step. Performed. The substrate may be cooled for a predetermined time if necessary before being transferred. In some embodiments, cooling is performed for about 0 to 30 minutes, or about 0 to about 10 minutes at a pressure ranging from vacuum to about 2 atm, or from about 0.1 torr to about 760 torr, or from about 1 torr to about 760 torr. do. The substrate may be transferred under vacuum, for example, or in _{the presence of N 2} (and possibly some O _{2) at about 1 to 1000 torr.}

4 is a flow diagram schematically illustrating a method 40 for selectively depositing a metal film on a first metal-based surface relative to a second silicon-containing surface according to certain other embodiments. The reaction chambers or chambers in which the selective deposition process is to be performed are first subjected to a selective passivation process in step 41. A substrate comprising a first metallic surface, preferably a Cu surface and a second surface comprising silicon such as _{SiO 2 is provided and optionally degassed.} In some embodiments, the substrate may be subjected to a selective silicon-containing surface treatment in _{step 42, for example to passivate a SiO 2 surface.} Thereafter, the substrate may be subjected to a first selective surface treatment process in step 43. As described above, in some embodiments, the first surface treatment process may include exposing the substrate to one or more first surface treatment reactants.

In some embodiments, the treatment process 43 may reduce the first metallic surface. In some embodiments, the treatment process may remove the natural oxide layer present on the first metal-based surface. In some embodiments, the treatment process may remove the passivation layer or the hydrocarbon layer that may exist on the second metal-based surface, for example, the treatment process may remove the BTA layer existing on the Cu surface. . In some embodiments, a passivation layer, such as a BTA layer, on the Cu surface may have been deposited to protect the Cu surface from oxidation during other processing steps, such as chemical-mechanical planarization. However, this passivation layer must be removed prior to the selective deposition process.

In some embodiments, the treatment process includes exposing the substrate to a treatment reactant. In some embodiments, the treatment reactant is a gaseous organic reactant. In some embodiments, the treatment reactant may comprise at least one alcohol group, preferably from the group consisting of primary alcohols, secondary alcohols, tertiary alcohols, polyhydric alcohols, cyclic alcohols, aromatic alcohols, and other alcohol derivatives. Can be chosen. In some embodiments, the treatment reactant may include formic acid or HCl.

The temperature during the treatment process 43 may be, for example, 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 implementations, steps 42 and 43 can be performed in a different reaction chamber or chambers than the reaction chamber that is passivated in step 41. That is, steps 42 and 43 may be performed in a reaction chamber or chambers different from a reaction chamber in which a subsequent selective deposition process is to be performed. Further, in some embodiments, the reaction chamber passivation step 41 may proceed simultaneously with one or more steps 42 and 43.

In some embodiments, the substrate surface is optionally further annealed in an inert atmosphere after optional step 43. The annealing is performed at a temperature higher than steps 42, 43 or subsequent optional deposition steps 45-47. The temperature 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 embodiments, the substrate surface is further annealed in an _{NH 3 environment to create NH x} -surface ends for the metal oxide present on the Cu surface.

Next, in step 44, the substrate is transferred to the chamber selectively passivated in step 41, and a silicon or boron source is provided as the substrate, so that in step 45, silicon or boron-containing paper is deposited on the Cu surface. In some embodiments, the silicon source is silane or disilane. In some embodiments, the disilane can be selectively decomposed on the Cu surface relative to the silicon-containing surface using a temperature at which the silicon precursor forms silicon on the Cu surface but _{not silicon on the SiO 2 surface.} In some embodiments, the silicon or boron source reacts with the Cu surface in a self-limiting manner. It is believed that the Cu surface may enable the formation of silicon relative to the formation on the _{SiO 2 surface.}

In some embodiments, a layer comprising silicon or boron and 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 embodiments, a layer comprising silicon or boron and 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 preferred embodiments, the formation of a layer comprising silicon or boron on the Cu surface is self-limiting. Thus, at most a single layer, comprising silicon or boron, is formed in each cycle.

After the silicon or boron-containing layer is formed on Cu, in step 46, a second reactant such as a metal halide converts the layer containing silicon or boron from the second reactant, such as a metal in the metal halide, to a layer containing the metal. Is used for _{In some embodiments, WF 6} , TaF ₅ , NbF ₅ or other compounds capable of reacting with the Si or B layer are introduced to the substrate surface to form a metal-based layer or metal silicide. In some implementations, the silicon or boron precursor (eg, disilane) and second reactant (eg, metal halide) pulses may be repeated in step 47 until a metal-based layer having a desired thickness is formed. In some embodiments, the metal-based layer is an elemental metal, such as W. In some embodiments, the metal-based layer may include additional elements such as Si, B, N and other dopants. In some embodiments, the metallic layer is further processed to form a different material. For example, the elemental metal layer can be treated with a third reactant to form a metal nitride or metal silicide.

The deposition cycle can be defined as providing a silicon or boron precursor and providing the second metal reactant, i.e., steps 45 and 46. In some implementations, no other reactants are provided in the deposition cycle. In some implementations, the deposition cycle is repeated to form a metal-based layer having a predetermined thickness. In some embodiments, a metallic layer having a thickness of about 0.05 nm to about 4 nm is formed in each cycle. In some embodiments, a metal-based layer having a thickness of about 0.1 nm to about 2 nm is formed in each cycle. In some embodiments, the metallic layer has a thickness of about 1-2 nm. In other embodiments, the thickness of the deposited metallic 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 preferred embodiments, the layer has a thickness of less than 10 nm.

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

In some embodiments, no other reactant is provided other than a precursor comprising silicon or boron and a second metal reactant.

In some embodiments, the material comprising the first surface, such as copper, is neither converted nor reacted to form other compounds during the selective deposition cycle.

In some implementations, after one or more deposition cycles have been completed, a half deposition cycle may be performed in step 48. For example, a silicon or boron precursor pulse or alternatively a second metal reactant may be provided. In some implementations, after one or more deposition cycles, a silicon or boron precursor pulse is provided. When a silicon or boron precursor pulse (or other metal reactant) is provided, the formed material may form a sacrificial layer made of silicon oxide or boron oxide (or metal oxide) when exposed to air or an oxygen-containing atmosphere. The sacrificial layer may prevent the metal-based material under the silicon oxide or boron oxide layer from being oxidized when exposed to air or an oxygen-containing atmosphere outside the reactor. Silicon oxide or the boron oxide layer is formed, is in the additional processing step, for example, and more preferably with a metal chemicals described herein, preferably from WF _6, TaF _5, NbF _5, TiF _4, MoF _x or VF _x Can be removed with a single pulse of WF _6.

In some implementations, the entire process flow can be performed in a single reaction chamber, such as a single process module. However, in other embodiments, various steps are performed in more than one reaction chamber. For example, in some embodiments, a first surface treatment process and a silicon-containing surface treatment process (if used) are performed in a first reaction chamber, whereas a selective deposition process may be performed in a different second reaction chamber. . In some embodiments, the different second reaction chamber may also be processed to form a passivation layer therein. If an optional thermal annealing step is required or required, the substrate may then be transferred to a second reaction chamber where thermal annealing (if used) and selective deposition are performed. In some embodiments, the annealing step is performed in a first reaction chamber, and the substrate is transferred to a first reaction chamber or a third reaction chamber where selective deposition is performed. In some embodiments, the first surface treatment and the silicon-containing surface treatment (if used) are performed in a first reaction chamber, and the selective deposition is performed in a second reaction chamber that is different without a thermal annealing step between the first surface treatment and the deposition step. Performed. The substrate may be cooled for a predetermined time if necessary before being transferred. In some embodiments, cooling is performed for about 0 to 30 minutes, or about 0 to about 10 minutes at a pressure ranging from vacuum to about 2 atm, or from about 0.1 torr to about 760 torr, or from about 1 torr to about 760 torr. do. The substrate may be transferred under vacuum, for example, or in _{the presence of N 2} (and possibly some O _{2) at about 1 to 1000 torr.}

5 is a flow diagram schematically illustrating an exemplary reaction chamber passivation process 50 in accordance with some embodiments. In some embodiments, the reaction chamber passivation process may enable selective deposition, improve selectivity, and/or increase the number of successive cycles before the selectivity disappears during the selective deposition process.

A reaction chamber in which a selective deposition process, such as a W selective deposition process, will be performed is provided in step 51. The reaction chamber is provided without a wafer or substrate therein. In some implementations, the selective deposition process may be performed on a wafer or wafers within the reaction chamber, which is then removed in step 51 so that there are no wafers within the reaction chamber. In some implementations, the wafers or wafers to be subjected to the selective deposition process in the reaction chamber may be subjected to other treatments before, during, or after the reaction chamber passivation process. For example, during the reaction chamber passivation process, the wafer may undergo a second surface treatment process in a different second reaction chamber.

In some implementations, in step 52 the passivation layer is deposited or formed on the inner surface of the reaction chamber and on any other locations that may be exposed to the precursor or reactant during the selective deposition process. In some embodiments, the passivation material is deposited or formed on the inner surface of the reaction chamber, the chamber showerhead, and/or any other portions of the chamber that may be connected to the space in which the selective deposition process will take place. In some implementations, the passivation material may be deposited on any surface in the reaction chamber other than the substrate.

In some embodiments, the passivation layer, such as a layer of SiN, may be formed by a vapor deposition process, such as a PEALD process. In some embodiments, the SiN layer may be formed by a process including one or more passivation layer deposition cycles, wherein the deposition cycle alternately and sequentially exposes the reaction chamber to the first silicon precursor and the second nitrogen precursor. It includes the step of making. The passivation layer deposition cycle may be selectively repeated until a SiN passivation layer having a predetermined thickness is formed.

In some embodiments, the silicon precursor used in the passivation layer deposition process may include silane, such as disilane. In some embodiments, the nitrogen precursor may comprise atomic nitrogen, nitrogen radicals, nitrogen plasma, or combinations thereof. In some embodiments, the nitrogen precursor may further comprise atomic hydrogen, hydrogen radicals, hydrogen plasma, or combinations thereof. In some implementations, the nitrogen precursor may comprise a plasma generated from _{N 2.} In some implementations, the nitrogen precursor can include plasma generated from _{N 2} and H _2. In some implementations, the nitrogen precursor may _{include a plasma generated from N 2} and a noble gas such as argon. In some implementations, the nitrogen precursor may _{include a plasma generated from N 2} , H ₂ and a noble gas such as argon.

In some implementations, after formation of the passivation layer in step 52, the wafer or wafers in step 53 are transferred to the reaction chamber. Then, in step 54, a selective deposition process, such as a W selective deposition process and any other desired process, may be performed. In some implementations, after the selective deposition process, any wafer or wafers present in the reaction chamber in step 55 may then be transferred out of the reaction chamber. In some embodiments, the reaction chamber passivation process in step 56 may be optionally repeated. In some implementations, the wafer or wafers may be transferred to the reaction chamber, and before selectively repeating the reaction chamber passivation process, another selective deposition process may be performed again. That is, in some implementations, the reaction chamber passivation process may be repeated whenever 1, 5, 10, 20, 50, or more wafers have undergone the selective deposition process. In some implementations, the reaction chamber passivation process may be repeated after a specific number of cycles of the selective deposition process have been performed. In some implementations, the reaction chamber passivation process can be repeated every 50, 100, 150, or more deposition cycles complete.

Example

Sample substrates having a first metal-based surface containing Cu and a second dielectric surface containing a low dielectric constant (k) dielectric material having a dielectric constant of 3.0 were provided, and an organic material layer having a thickness of about 1 nm to 2 nm thereon The Cu surface was passivated by vapor deposition. A natural copper oxide layer having a thickness of about 1 nm was also present between the Cu surface and the organic material layer. Substrates containing only a Co surface along with a natural cobalt oxide surface layer were provided to serve as a control.

The sample substrates comprising a first Cu surface and a second dielectric surface, along with the control substrates comprising a Co surface, are the first of the sample substrates relative to the second surface, as described herein and according to some embodiments. In order to investigate the effect of these processes on the subsequent selective deposition process for depositing W on the surface, various first surface treatment processes were performed. The various first surface treatment processes included exposing the substrates to plasma generated from various gases. While the substrates were exposed for about 10 seconds, each plasma was generated through an RF output of about 200 W at a pressure of about 350 Pa. The substrate temperature during each of the first surface treatment processes was about 150°C.

The first sample and control substrates were subjected to a first surface treatment process including exposing the _{substrate to a plasma generated from a gas containing H 2} together with a rare gas serving as a carrier gas at a flow rate of 1000 sccm. Then, the sample and control substrates were subjected to a selective deposition process to selectively deposit W on the first Cu and Co surfaces relative to the second dielectric surface. A control substrate comprising a Co surface was included to investigate the ability of the first surface treatment process to effectively reduce/reduce or remove the natural oxide layer present thereon.

As shown in FIG. 6A, W was deposited on the first Cu surface and the second dielectric surface. W deposition was also observed on the substrate containing the Co surface, indicating that the natural oxide surface layer was effectively reduced/reduced or removed. Therefore, the first surface treatment process described above did not increase the selectivity of the selective deposition process, but instead reduced the selectivity of the process. Without wishing to be bound by any one theory, it is believed that _{the plasma generated from H 2} under the conditions described above damaged the second dielectric surface and created surface sites that allowed W deposition thereon.

The second sample and control substrates were subjected to a first surface treatment process comprising exposing the _{substrate to plasma generated from a gas containing H 2} and N ₂ together with a rare gas serving as a carrier gas at a flow rate of 1000 sccm. Then, the sample and control substrates were subjected to a selective deposition process to selectively deposit W on the first Cu and Co surfaces relative to the second dielectric surface. A control substrate comprising a Co surface was included to investigate the ability of the first surface treatment process to effectively reduce/reduce or remove the natural oxide layer present thereon.

As shown in FIG. 6B, W was deposited on the first Cu surface and the second dielectric surface. W deposition was also observed on the substrate containing the Co surface, indicating that the natural oxide surface layer was effectively reduced/reduced or removed. Therefore, the first surface treatment process described above did not increase the selectivity of the selective deposition process, but instead reduced the selectivity of the process. Without wishing to be bound by any one theory, it is believed that _{the plasma generated from H 2} and N ₂ under the conditions described above damaged the second dielectric surface and created surface sites that allowed W deposition thereon.

The third sample and control substrates were subjected to a first surface treatment process including exposing the _{substrate to a plasma generated from a gas containing NH 3} together with a rare gas serving as a carrier gas at a flow rate of 1000 sccm. Then, the sample and control substrates were subjected to a selective deposition process to selectively deposit W on the first Cu and Co surfaces relative to the second dielectric surface. A control substrate comprising a Co surface was included to investigate the ability of the first surface treatment process to effectively reduce/reduce or remove the natural oxide layer present thereon.

As shown in FIG. 6C, W was deposited on the first Cu surface and the second dielectric surface. W deposition was not observed on the substrate comprising the Co surface, indicating that the natural oxide surface layer was not effectively reduced/reduced or not removed. Therefore, the first surface treatment process described above did not increase the selectivity of the selective deposition process, but instead reduced the selectivity of the process. Without wishing to be bound by any one theory, it is believed that _{the plasma generated from NH 3} under the conditions described above damaged the second dielectric surface and created surface sites that allowed W deposition thereon.

The fourth sample and control substrates were subjected to a first surface treatment process including exposing the _{substrate to a plasma generated from a gas containing H 2} and NH ₃ together with a rare gas serving as a carrier gas at a flow rate of 1000 sccm. Then, the sample and control substrates were subjected to a selective deposition process to selectively deposit W on the first Cu and Co surfaces relative to the second dielectric surface. A control substrate comprising a Co surface was included to investigate the ability of the first surface treatment process to effectively reduce/reduce or remove the natural oxide layer present thereon.

As shown in Fig. 6D, W was deposited on the first Cu surface and particulate W material was deposited on the second dielectric surface. W deposition was not observed on the substrate comprising the Co surface, indicating that the natural oxide surface layer was not effectively reduced/reduced or not removed. Therefore, the first surface treatment process described above did not increase the selectivity of the selective deposition process, but instead reduced the selectivity of the process. Without wishing to be bound by any one theory, it is believed that _{the plasma generated from H 2} and NH ₃ under the conditions described above damaged the second dielectric surface and created surface sites that allowed W deposition thereon.

A first surface treatment process including exposing the substrate to plasma generated from a gas including _{HCOOH, NH 3} , and H ₂ at a flow rate of 1000 sccm for the fifth sample and the control substrates. Went through. The ratio of HCOOH to NH ₃ to H ₂ was 1:1:19. Then, the sample and control substrates were subjected to a selective deposition process to selectively deposit W on the first Cu and Co surfaces relative to the second dielectric surface. A control substrate comprising a Co surface was included to investigate the ability of the first surface treatment process to effectively reduce/reduce or remove the natural oxide layer present thereon.

As shown in Fig. 7, W was selectively deposited on the Cu surface, and W deposition was not observed on the second dielectric surface, indicating that the first surface treatment enhanced or enabled the selective W deposition. . W deposition was also observed on the substrate containing the Co surface, indicating that the natural oxide surface layer was effectively reduced/reduced or removed. Without wishing to be bound by any one theory, _{exposure to plasma generated from HCOOH, NH 3} and H ₂ under the conditions described above did not significantly damage the second dielectric surface, whereas the exposure was selective thereon. It is believed that the organic surface layer was removed from the first metal-based surface in order to improve W deposition and the natural oxide was reduced/reduced or removed.

A summary of the effects on selective W deposition and the results of the first surface treatment processes described above is provided in Table 1 below. The first surface treatment process comprising the step of contacting a substrate with a plasma generated from a gas containing HCOOH, NH ₃ , and H _{2 was able to achieve deposition on Cu and Co surfaces while maintaining relative selectivity to the dielectric surface.} It was the only process that was investigated. Therefore, this first surface treatment process was able to remove the organic material surface layer from the Cu surface, reduce/reduce or remove the natural oxide layer, and reduce/reduce or remove the natural oxide layer from the Co surface. On the other hand, in order to maintain or improve the selectivity of the selective W deposition process, the second dielectric surface was not significantly damaged.

Summary of the results for the various first surface treatment processes and the effects of selective deposition processes for depositing W on a metallic surface relative to the dielectric surface. First surface treatment plasma generation gas W deposition on Cu surface W deposition on low dielectric constant (k) surfaces W deposition on Co surface H ₂ ○ ○ ○ H ₂ /N ₂ ○ ○ ○ NH ₃ ○ ○ × NH ₃ /H ₂ ○ ○ (W particles) × HCOOH/NH ₃ /H ₂ ○ × ○

The language of degree as used herein, such as the terms “approximately”, “about”, and “substantially” as used herein refer to still performing a desired function or achieving a desired result. Represents a value, quantity, or characteristic that is close to the value, quantity, or characteristic that is specified For example, the terms "approximately", "about", "generally" and "substantially" are within 10% or less, 5% or less, 1% or less, 0.1% or less, 0.01% or less of the stated amount. It can refer to an amount that is within. If the stated amount is zero (e.g., none, not having), the range described above may be a specific range and may not be within a certain percentage of this value. For example, within 10 wt./vol.% or less of the stated amount, within 5 wt./vol.% or less of the stated amount, within 1 wt./vol.% or less of the stated amount, within the stated amount of Within 0.1 wt./vol.% or less, within 0.01 wt./vol.% or less of the stated amount.

The terms “film” and “thin film” are used herein for brevity. "Film" and "thin film" mean any continuous or non-continuous structure and material deposited by the methods disclosed herein. For example, “film” and “thin film” may include 2D materials, nanorods, nanotubes or nanoparticles or even a single part or whole molecular layer or partial or whole atomic layer or atomic and/or molecular clusters. The “film” and “thin film” may comprise a material or layer comprising pinholes, but may still be at least partially continuous.

While specific embodiments and examples have been disclosed below, those skilled in the art will understand that the scope of the claims extends beyond the specifically disclosed embodiments to alternative embodiments and/or uses of the invention and their apparent modifications and equivalents.

Claims (20)

A method for selectively depositing a film on a first metallic surface of the same substrate relative to a second dielectric surface of the substrate, comprising:
A step of performing a first surface treatment process comprising removing a surface layer from the first metal-based surface of the substrate, wherein the first metal-based surface treatment process comprises at least the first metal-based surface of the substrate using formic acid (HCOOH). Exposing to a plasma generated from the containing gas; And
And selectively depositing a film with a selectivity greater than 50% on the treated first metallic surface of the substrate relative to the second dielectric surface of the substrate. The method of claim 1, wherein the first metallic surface treatment process comprises exposing the first metallic surface of the substrate and the second dielectric surface of the substrate to the plasma generated from the gas. The method of claim 1, wherein the first metal-based surface treatment process further comprises reducing a metal oxide layer present on the first metal-based surface of the substrate. The method of claim 1, wherein the removed surface layer comprises an organic material. 5. The method of claim 4, wherein the removed surface layer comprises a passivation layer. 6. The method of claim 5, wherein the removed surface layer comprises benzotriazole (BTA). The method of claim 1, wherein the gas comprises formic acid (HCOOH) and H ₂ . The method of claim 1, wherein the gas comprises HCOOH, NH ₃ , and H ₂ . 9. The method of claim 8, wherein the gas is provided by a carrier gas comprising a noble gas. The method of claim 1, wherein the temperature of the substrate is 300° C. during the first metal-based surface treatment process. The method of claim 1, wherein the first metallic surface treatment process comprises exposing at least the first metallic surface of the substrate to a plasma for 1 second to 10 minutes. The method of claim 1, wherein the plasma is generated by supplying RF power of 10 W to 3000 W to the gas. The method of claim 12, wherein the frequency of the RF power is 1 MHz to 10 GHz. The method of claim 1, wherein the pressure of the gas at which the plasma is generated is 1 Pa to 5000 Pa. The method of claim 1 wherein the selectively deposited film comprises tungsten. The method of claim 1, wherein the first metallic surface comprises copper or cobalt. The method of claim 1 wherein the second dielectric surface comprises silicon. The method of claim 1, wherein the first metal-based surface treatment process further comprises removing a metal oxide layer present on the first metal-based surface of the substrate. A method for selectively depositing a film on a first metallic surface of the same substrate relative to a second dielectric surface of the substrate, comprising:
Performing a first metallic surface treatment process comprising removing a surface layer from the first metallic surface of the substrate by exposing at least the first metallic surface of the substrate to plasma generated from a gas containing HCOOH; And
And selectively depositing a film with a selectivity greater than 50% on the first metallic surface of the substrate relative to the second dielectric surface of the substrate.
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