Selective PEALD of oxide on dielectric

Abstract

The name of the present invention is selective PEALD of oxides on dielectrics. The present application provides a method for selectively depositing an oxide film on a dielectric surface of a substrate relative to a metal surface. The method may include at least one plasma enhanced atomic layer deposition (PEALD) cycle, which includes contacting the substrate with a first precursor and a second plasma reactant containing oxygen and a species to be included in the oxide, such as a metal or silicon, alternating and sequentially. In some embodiments, the second plasma reactant comprises a plasma formed in a reactant gas that does not contain oxygen. In some embodiments, the second plasma reactant comprises a plasma generated in a gas containing hydrogen.

Description

[0001] This application is a divisional application. The application date of the original application is May 3, 2018, the application number is 201880032200.1, and the name of the invention is “Selective PEALD of Oxide on Dielectric”. Technical Field

[0002] The present disclosure relates generally to the field of semiconductor device fabrication and, more particularly, to selective plasma enhanced atomic layer deposition (PEALD) of oxide films. Background Art

[0003] In the semiconductor industry, there is an increasing need for selective processes. For example, it may be desirable to grow a film on one surface but not on a second, different surface. The two different surfaces may include different materials, such as a metal and a dielectric. A good selective process can reduce the number of process steps, saving time and money. Summary of the invention

[0004] The present application relates to the selective deposition of oxides on substrates by plasma enhanced atomic layer deposition (PEALD). The oxides may include, for example, SiO 2 , SiOC, SiOCN or metal oxide. In some embodiments, the oxide comprises both metal and silicon. In some embodiments, the oxide is selectively deposited on the dielectric surface of the substrate. In some embodiments, the PEALD process does not utilize oxygen plasma or other reactive oxygen species. Therefore, in some embodiments, one of the reactants comprises reactive species from a plasma generated in a gas that does not contain oxygen.

[0005] In some embodiments, a PEALD process for selectively depositing an oxide on a dielectric surface of a substrate includes providing a substrate comprising a first dielectric surface and a second different surface, such as a metal surface. At least one deposition cycle is performed, the at least one deposition cycle comprising contacting the substrate with a first precursor and a second reactant, which comprise oxygen and a component of an oxide, such as silicon or a metal, alternatingly and sequentially. In some embodiments, the second reactant comprises a reactive species from a plasma generated in a gas that does not comprise oxygen. For example, the second reactant may comprise hydrogen plasma. The hydrogen plasma may be generated in a gas comprising H 2The second reactant reacts with the first precursor adsorbed on the substrate surface to selectively form an oxide on the first dielectric surface relative to the second metal surface. In some embodiments, the second reactant also reacts with the metal surface to reduce metal oxides that may be present on the metal surface. The second reactant can also remove OH groups that may be present on the metal surface. The deposition cycle can be repeated two or more times to form an oxide of a desired thickness on the dielectric surface. In some embodiments, the second reactant is first provided to react with the surface of the substrate: or react with the dielectric surface, at which time it can play a role in conditioning the surface for subsequent deposition, or react with the adsorbed first reactant from the previous deposition cycle.

[0006] In some embodiments, the dielectric surface comprises SiO 2 In some embodiments, the dielectric surface comprises a low-k material. The metallic surface may comprise, for example, Co, W, TiN, Cu, or Ta.

[0007] In some embodiments, the selectively deposited oxide comprises SiO 2 , SiOC or SiOCN. In some embodiments, the oxide is a metal oxide, such as titanium oxide. In some embodiments, the oxide is any metal oxide that can be deposited from an oxygen-containing precursor. In some embodiments, the selectively deposited oxide comprises a mixture of two or more oxides. In some embodiments, the deposited oxide comprises a mixture of two or more metal oxides. In some embodiments, the deposited oxide comprises a mixture of silicon oxide and one or more metal oxides. In some embodiments, an oxide comprising metal and silicon, such as SiTiOx, is deposited. In some embodiments, a silicate is deposited.

[0008] In some embodiments, the first precursor is a silicon precursor, such as 3-methoxypropyltrimethoxysilane (MPTMS). In some embodiments, the first precursor is MPTMS and the second reactant comprises a hydrogen plasma. In some embodiments, the first precursor is a metal precursor.

[0009] In some embodiments, the metal surface comprises a passivation layer, such as an organic material. Before starting the selective oxide deposition, the organic passivation layer can be selectively deposited on the metal surface relative to the dielectric surface. In some embodiments, the passivation layer on the metal surface is etched by the second reactant during the oxide deposition cycle.

[0010] In some embodiments, a method for depositing a silicon oxide film selectively on a dielectric surface of a substrate relative to a metal surface is provided. The method can be a PEALD method, which includes a deposition cycle, wherein the substrate is contacted alternately and sequentially with a first reactant comprising silicon and oxygen and a second plasma reactant that does not contain oxygen species. In some embodiments, the second plasma reactant comprises a plasma generated in a gas that does not contain oxygen. In some embodiments, the second plasma reactant comprises a plasma generated in a gas that contains hydrogen but does not contain oxygen. Species of the first reactant comprising silicon and oxygen are adsorbed on the dielectric surface and react with the second plasma reactant to form silicon oxide. In some embodiments, the second plasma reactant comprises a hydrogen plasma. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 Schematic diagram of some embodiments in which an oxide film is selectively deposited on a SiO surface relative to a metal surface. 2 On SiOC deposited on SiO 2 During the above process, the metal surface can be reduced simultaneously. SiOC can be deposited by MPTMS and hydrogen plasma.

[0012] Figure 2A and 2B Illustrated is the selectivity between W and Cu for the MPTMS process at 125 and 200° C. The Y axis is atomic %.

[0013] Figure 3 The H generated by using a power of 67 W is shown. 2 Plasma PEALD process, selective deposition of SiOC on low-k surfaces relative to Cu surfaces.

[0014] Figure 4 The H generated at a power of 300 W is shown in FIG. 2 Plasma PEALD process, selective deposition of SiOC on low-k surfaces relative to Cu surfaces.

[0015] Figure 5A Graph showing the refractive index (RI) of TiO(CN) films deposited with titanium(IV) isopropoxide using different plasma reactants.

[0016] Figure 5B Graphs showing the growth rate per cycle for TiO(CN) films deposited with titanium(IV) isopropoxide using different plasma reactants. DETAILED DESCRIPTION

[0017] As will be apparent to the skilled artisan, oxide films such as silicon oxycarbide (SiOC) films have widespread application, for example, in integrated circuit fabrication.

[0018] According to some embodiments of the present disclosure, various dielectric films (particularly oxide films), precursors, and methods for depositing such films are provided.

[0019] In some embodiments, oxide films, such as dielectric films such as SiO 2 , SiOC or other SiO-based dielectric films or metal oxide films are selectively deposited on the substrate by a plasma enhanced atomic layer deposition (PEALD) process. In some embodiments, the oxide film is selectively deposited on a first dielectric surface of the substrate relative to a second different metal or metallic surface of the substrate by a PEALD process. For example, SiO 2 PEALD can be used to selectively deposit SiO 2 On the surface. Figure 1 Schematic diagrams showing some embodiments in which an oxide film is selectively deposited on a SiO surface relative to a metal surface. 2 superior.

[0020] According to some embodiments, the oxide film is selectively deposited using a PEALD process that includes contacting the substrate with a first precursor and a plasma reactant, such as a plasma generated in a gas comprising hydrogen. For example, the PEALD process may include contacting the substrate with a first precursor comprising silicon and oxygen and a plasma reactant, such as a plasma generated in a gas comprising Ar and H. 2 (referred to herein as Ar / H 2 The first precursor may contain oxygen and one or more elements to be included in the oxide, such as metal or silicon. The oxide film grows on the first surface, such as a dielectric surface. Growth occurs less or does not occur on the second surface, such as a metal or metallic surface. The plasma reactant in the PEALD process can be used for two functions. First, it can act as a reactant in the deposition process, where it reacts with the precursor previously adsorbed on the dielectric surface to form the desired oxide on the surface. Second, the plasma acts on the metal surface to reduce or inhibit the formation of oxides on the surface. Growth on the second metal surface can be inhibited, for example, by reducing the metal oxide on the metal surface (if any) and / or by removing oxygen from the metal surface, such as by removing OH groups and / or metal-oxygen bridges from the metal surface. The plasma will not remove oxygen (such as OH groups and / or metal-oxygen bridges) as easily as from the first dielectric surface, such as a silicon oxide dielectric surface. The first precursor therefore preferentially reacts and chemically adsorbs to the dielectric surface containing a larger OH-group concentration relative to the reduced metal surface with fewer OH-groups. As a result, the oxide is selectively deposited on the first dielectric surface relative to the second metal or metallic surface.

[0021] In some embodiments, a substrate including a first surface on which a dielectric material needs to be deposited and a second surface such as a metal surface on which a dielectric material needs to be deposited is contacted alternately and sequentially with precursors and plasma reactants containing oxygen and one or more elements to be included in the deposited material. In some embodiments, the plasma reactant comprises a plasma generated in a gas that does not contain oxygen. In some embodiments, the plasma reactant does not contain oxygen species. In some embodiments, in addition to the first reactant, a reactant containing oxygen species is not used. In some embodiments, the plasma reactant comprises a plasma generated in a gas containing hydrogen. Precursors and plasma containing oxygen can be provided in pulses, each pulse being separated by a purge, in which excess reactants and reaction byproducts (if any) are removed from the reaction space.

[0022] In some embodiments, the deposition process begins with a plasma pulse, and the reaction sequence or deposition cycle may be repeated a desired number of times (A):

[0023] A x(RF / Purge / Precursor / Purge)

[0024] In some embodiments, a deposition cycle begins with a precursor pulse followed by a plasma pulse.

[0025] In some embodiments, a reduction plasma step may be provided prior to starting a deposition cycle. The reduction plasma step may be longer than the time of exposure to the plasma reactants in the deposition cycle. In some embodiments, the reduction plasma step is included at one or more time intervals in the deposition process. In some embodiments, the reduction plasma step is included before two or more deposition cycles. In some embodiments, the reduction plasma step is included before each deposition cycle.

[0026] The plasma in the longer reduction step may be the same as the plasma used in the deposition cycle, or may be different. This reduction plasma step may reduce substantially all of the metal oxide from the metal surface and ensure that substantially all of the OH groups or metal oxide bridges are removed from the metal surface:

[0027] (Long Pulse / High Power RF) + A x (RF / Purge / Precursor / Purge)

[0028] By optimizing the plasma and other process conditions, the reducing power can be adjusted so that the desired selectivity level is obtained. In some embodiments, the process conditions such as plasma power can be adjusted so that growth does not occur significantly on the metal surface, or even does not occur at all. In some embodiments, the plasma power can also be used to adjust the k value and wet etch resistance of the deposited oxide film.

[0029] In some embodiments, the plasma used in the deposition cycle and / or for the reducing plasma step is hydrogen-based. For example, the plasma can be in a gas comprising hydrogen, such as in H 2 In the air, H 2 In a mixture with an inert gas such as Ar or in a mixture containing H 2 In some embodiments, the plasma is nitrogen-based, or contains nitrogen species. For example, the plasma can be generated in a gas containing nitrogen, such as a gas containing N 2 of gas, or N 2 In some embodiments, the plasma is generated in a mixture with an inert gas such as Ar. In some embodiments, the plasma does not contain oxygen species. In some embodiments, the plasma is generated in a gas or gas mixture that does not contain oxygen. However, in some embodiments, the plasma can be generated in a gas containing oxygen, or can additionally contain excited oxygen species. In some embodiments, the plasma does not contain nitrogen species. In some embodiments, plasma gases with more reducing power are preferred. In some embodiments, an inert gas can be used alone to generate the plasma. Therefore, in some embodiments, the plasma is generated in an inert gas such as Ar gas without any other components.

[0030] In some embodiments, a plasma, such as a hydrogen-containing plasma, may be generated by applying an RF power of about 5 W to about 5000 W, 10 W to about 2000 W, about 20 W to about 1000 W, about 30 W to 500 W, or about 50 W to about 200 W. In some embodiments, the RF power density may be about 0.02 W / cm 2 To about 2.0W / cm 2 , or about 0.05W / cm 2 To about 1.5W / cm 2 RF power can be applied to the second reactant flowing during the plasma contact time, continuously flowing through the reaction chamber, and / or flowing through a remote plasma generator. Thus, in some embodiments, the plasma is generated in situ, while in other embodiments, the plasma is generated remotely. In some embodiments, a showerhead reactor is utilized and the plasma is generated between a pedestal (on which the substrate is located) and a showerhead plate.

[0031] In some embodiments, a SiOC film is deposited. In some embodiments, an oxide other than SiOC is deposited. In some embodiments, the oxide comprises an oxygen-philic element. For example, oxides that can be deposited by the methods disclosed herein include SiOCN, SiOSC, TiO 2 、Al 2 O 3 , Nb 2 O 5 、 2 O5 and SiO 2 Likewise, in some embodiments, a precursor is employed that contains both oxygen and a second element desired in the oxide, such as a metal or silicon.

[0032] Unless otherwise indicated, if a surface is referred to herein as a metal surface, it may be a metal surface or a metallic surface. In some embodiments, a metal surface or a metal-containing surface may comprise a metal, a metal oxide, and / or a mixture thereof. In some embodiments, a metal surface or a metal-containing surface may comprise surface oxidation. In some embodiments, the metal or metal-containing surface of the metal or metal-containing material is conductive with or without surface oxidation. In some embodiments, the metal or metal-containing surface comprises one or more transition metals. In some embodiments, the metal or metal-containing surface comprises one or more of Al, Cu, Co, Ni, W, Nb, and Fe. In some embodiments, the metal or metallic surface comprises Cu. In some embodiments, the metal or metallic surface comprises one or more noble metals such as Ru. In some embodiments, the metal or metal-containing surface comprises a conductive metal oxide, nitride, carbide, boride, or a combination thereof. For example, the metal or metallic surface may comprise RuO x , NbC x , NbB x 、NiO x 、CoO x 、NbO x and WNC x In some embodiments, the substrate may include metal nitrides, including but not limited to TiN and / or TaN. In some embodiments, the metal surface may include metal carbides, including but not limited to TiC and / or TaC. In some embodiments, the metal surface may include metal chalcogenides, including but not limited to MoS 2 , Sb 2 Te 3 In some embodiments, the metal surface is a Tin surface. In some embodiments, the metal surface is a W surface.

[0033] In some embodiments, the metal surface may include Zn, Fe, Mn, or Mo.

[0034] In some embodiments, the metal surface comprises Co, W, TiN, Ta, or Cu.

[0035] In some embodiments, the dielectric surface can be, for example, a silicon oxide surface such as SiO 2 Surface. In some embodiments, the dielectric surface can be a low-k surface.

[0036] In some embodiments, a passivation layer, such as an organic layer, may be present on the substrate, such as on a metal surface, prior to deposition. In some embodiments, the passivation layer is present on the metal surface but not on the dielectric surface.

[0037] In some embodiments, a passivation layer may be deposited on the metal surface prior to selectively depositing an oxide on the dielectric surface. For example, in some embodiments, a passivation layer may be selectively deposited on a metal layer. The selective deposition of a passivation layer may be performed, for example, as described below and as described in U.S. Patent Application No. 15 / 170,769 or U.S. Patent Application No. 15 / 486,124, each of which is incorporated herein by reference.

[0038] In some embodiments, a passivation layer may be present on both the metal surface and the dielectric surface prior to deposition. In some embodiments, the passivation layer over the metal surface is thicker than the passivation layer over the dielectric surface.

[0039] The plasma reactants used in the plasma treatment during the deposition process or prior to the deposition process can etch the passivation layer such that the passivation layer is completely etched away from the dielectric surface on which it is desired to be deposited, while some of the passivation layer remains on the metal surface. The selectivity of the deposition process on the dielectric surface relative to the metal surface (including the passivation layer) can thus be achieved or enhanced. In some embodiments, etching of the passivation layer occurs during the selective deposition of the oxide, such as by the activity of the plasma reactants.

[0040] In some embodiments, a passivation layer over the metal surface may be supplemented during the deposition process to achieve better selectivity when depositing thicker films.

[0041] If the passivation layer is not present, or is completely removed, the plasma can be used as described above to keep the metal metallic and remove OH- groups and / or metal oxides, so that the oxide is selectively deposited on dielectric surfaces such as SiO2 relative to metal or metallic surfaces. 2 or low-k surfaces.

[0042] As mentioned above, in some embodiments, the substrate may include an organic passivation layer. In some embodiments where the substrate includes an organic material, the reaction temperature of the PEALD process may be less than about 200° C. In some such embodiments, the reaction temperature may be less than about 150° C., less than about 100° C., less than about 75° C., or less than about 50° C. The deposition temperature in the absence of a passivation layer is described below.

[0043] In some embodiments, a substrate such as a semiconductor workpiece on which deposition is to be performed is loaded into a reaction space or reactor. The reactor can be part of a cluster tool in which various different methods in the integrated circuit formation process are performed. In some embodiments, a flow-type reactor is utilized. In some embodiments, a nozzle-type reactor is utilized. In some embodiments, a space-separated reactor is utilized. In some embodiments, a single-wafer ALD reactor capable of mass production is used. In other embodiments, a batch reactor containing multiple substrates is used. For embodiments using an intermittent ALD reactor, the number of substrates is in the range of 10 to 200, in the range of 50 to 150, or in the range of 100 to 130.

[0044] Examples of suitable reactors that may be used include commercially available equipment such as Reactor, Reactor; Reactor - such as 2000 and 3000; Reactor and 400 series reactors, which are available from ASM America, Inc. (Phoenix, Arizona) and ASM Europe BV (Almere, The Netherlands). Other commercially available reactors include those from ASM Japan KK (Tokyo, Japan) under the trade name Reactors for XP and XP8.

[0045] In some embodiments, if desired, the exposed surface of the workpiece may be pretreated to provide reaction sites for the first stage reaction of the ALD process. In some embodiments, no separate pretreatment step is required. In some embodiments, the substrate is pretreated to provide the desired surface termination. In some embodiments, the substrate is pretreated with a plasma.

[0046] Selectivity

[0047] Selectivity can be given as a percentage calculated as follows: [(deposition on the first surface) - (deposition on the second surface)] / (deposition on the first surface). Deposition can be measured using any of a variety of methods. In some embodiments, deposition can be given as a measured thickness of the deposited material. In some embodiments, deposition can be given as a measured amount of deposited material.

[0048] In some embodiments, the selectivity is greater than about 10%, greater than about 50%, greater than about 75%, greater than about 85%, greater than about 90%, greater than about 93%, greater than about 95%, greater than about 98%, greater than about 99%, or even greater than about 99.5%. In the embodiments described herein, the selectivity can vary with the duration or thickness of the deposition.

[0049] In some embodiments, deposition of the oxide occurs only on the first dielectric surface and not on the second metallic surface. In some embodiments, deposition on the first surface of the substrate has a selectivity of at least about 80% relative to the second surface of the substrate, which may be sufficiently selective for some specific applications. In some embodiments, deposition on the first surface of the substrate has a selectivity of at least about 50% relative to the second surface of the substrate, which may be sufficiently selective for some specific applications. In some embodiments, deposition on the first surface of the substrate has a selectivity of at least about 10% relative to the second surface of the substrate, which may be sufficiently selective for some specific applications.

[0050] Selective deposition of passivation layers

[0051] In some embodiments, the passivation layer is selectively deposited on the first metal or metallic surface of the substrate relative to the second dielectric surface to promote or enhance the subsequent selective deposition of oxide on the dielectric surface relative to the metal surface as described herein. In the selective deposition of the passivation layer, in some embodiments, the first organic reactant is vaporized to form a first reactant vapor. The vaporized reactant can be a liquid or solid under standard temperature and pressure conditions (room temperature and atmospheric pressure). In some embodiments, the vaporized reactant comprises an organic precursor, such as an amine, such as a diamine, such as 1,6-diaminohexane (DAH), or another organic precursor, such as a dianhydride, such as pyromellitic dianhydride (PMDA). The substrate is then exposed to the first reactant vapor and an organic film is selectively deposited. The method may include additional steps and may be repeated. For example, as described below, in some embodiments, two reactants are used to selectively deposit a passivation layer on a metal surface relative to a dielectric surface.

[0052] In some embodiments, the organic film comprises a polymer. In some embodiments, the deposited polymer is a polyimide. In some embodiments, the deposited polymer is a polyamide. Other examples of deposited polymers include dimers, trimers, polyurethanes, polythioureas, polyesters, polyimines, other polymer forms, or mixtures of the above materials.

[0053] In some embodiments, a substrate comprising a first conductive surface, such as a metal or metallic surface, and a second dielectric surface is provided and exposed to a first gas-phase reactant and a second gas-phase reactant, alternatingly and sequentially in a deposition cycle.

[0054] In some embodiments, the first precursor exposure time is from about 0.01 seconds to about 60 seconds, from about 0.05 seconds to about 30 seconds, from about 0.1 seconds to about 10 seconds, or from about 0.2 seconds to about 5 seconds. One skilled in the art can easily determine the optimal exposure time based on the specific circumstances. In some embodiments where a batch reactor may be used, an exposure time greater than 60 seconds may be used.

[0055] In some embodiments, the second precursor exposure time is from about 0.01 seconds to about 60 seconds, from about 0.05 seconds to about 30 seconds, from about 0.1 seconds to about 10 seconds, or from about 0.2 seconds to about 5 seconds. One skilled in the art can easily determine the optimal exposure time based on the specific circumstances. In some embodiments where a batch reactor may be used, an exposure time greater than 60 seconds may be used.

[0056] In some embodiments, the deposition cycle may be repeated until an organic film of a desired thickness is selectively deposited on the metal surface.

[0057] The above process can use a variety of reactants. For example, in some embodiments, the first precursor or reactant is an organic reactant such as a diamine, for example, 1,6-diaminohexane (DAH), or any other monomer having two reactive groups.

[0058] In some embodiments, the second reactant or precursor is also an organic reactant capable of reacting with the adsorbed species of the first reactant under the deposition conditions. For example, the second reactant can be an anhydride, such as furan-2,5-dione (maleic anhydride), or more particularly a dianhydride, such as pyromellitic dianhydride (PMDA), or any other monomer having two reactive groups that will react with the first reactant.

[0059] In some embodiments, the substrate is contacted with the first precursor before contacting with the second precursor. Thus, in some embodiments, the substrate is contacted with an amine such as a diamine, for example 1,6-diaminohexane (DAH) before contacting with another precursor. However, in some embodiments, the substrate may be contacted with the second precursor before contacting with the first precursor. Thus, in some embodiments, the substrate is contacted with an anhydride such as furan-2,5-dione (maleic anhydride) or more particularly a dianhydride such as pyromellitic dianhydride (PMDA) before contacting with another precursor.

[0060] Although the above process begins with contacting the substrate with a first vapor precursor, in other embodiments, the process may begin with contacting the substrate with a second vapor precursor. The skilled artisan will appreciate that contacting the substrate with the first precursor and the second precursor is interchangeable in the processes described herein.

[0061] In some embodiments, different reactants can be used to tune film properties. For example, 4,4'-oxydiphenylamine or 1,4-diaminobenzene can be used instead of 1,6-diaminohexane to deposit polyimide films to obtain a more rigid structure with more aromaticity and improved dry etch resistance.

[0062] In some embodiments, the reactants do not contain metal atoms. In some embodiments, the reactants do not contain semimetal atoms. In some embodiments, one of the reactants contains metal or semimetal atoms. In some embodiments, the reactants contain carbon and hydrogen and one or more of the following elements: N, O, S, P or halogens such as Cl or F. In some embodiments, the first reactant may contain, for example, adipoyl chloride (AC).

[0063] The deposition conditions of the passivation layer may vary with the selected reactants and may be optimized when selected. In some embodiments, the reaction temperature may be selected from a range of about 80°C to about 250°C. In some embodiments, such as where the selectively deposited organic film comprises polyimide, the reaction temperature may be selected from a range of about 170°C to about 210°C. In some embodiments, such as where the selectively deposited organic film comprises polyamide, the reaction temperature may be selected from a range of about 80°C to about 150°C. In some embodiments where the selectively deposited organic film comprises polyimide, the reaction temperature may be higher than about 160°C, 180°C, 190°C, 200°C or 210°C. In some embodiments where the selectively deposited organic film comprises polyamide, the reaction temperature may be higher than about 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C or 150°C.

[0064] In some embodiments, the selectively deposited or formed organic film does not contain metal atoms. In some embodiments, the selectively deposited or formed organic film does not contain semi-metal atoms. In some embodiments, the selectively deposited or formed organic film contains metal or semi-metal atoms. In some embodiments, the selectively deposited or formed organic film contains carbon and hydrogen and one or more of the following elements: N, O, S or P.

[0065] In some embodiments, the reactants used in the selective deposition to form the organic passivation layer may have the general formula:

[0066] (1) R 1 (NH 2 ) 2

[0067] Where R 1 Can be the aliphatic carbon chain comprising 1-5 carbon atom, 2-5 carbon atom, 2-4 carbon atom, 5 or less carbon atoms, 4 or less carbon atoms, 3 or less carbon atoms or 2 carbon atoms.In some embodiments, the bond between the carbon atoms in reactant or precursor can be single bond, double bond, triple bond or some combination thereof.Therefore, in some embodiments, reactant can comprise two amino groups.In some embodiments, the amino group of reactant can occupy one or two terminal positions on aliphatic carbon chain.However, in some embodiments, the amino group of reactant can not occupy any terminal position on aliphatic carbon chain.In some embodiments, reactant can comprise diamine. In some embodiments, the reactants may include an organic precursor selected from 1,2-diaminoethane (1), 1,3-diaminopropane (1), 1,4-diaminobutane (1), 1,5-diaminopentane (1), 1,2-diaminopropane (1), 2,3-butanediamine, 2,2-dimethyl-1,3-propylenediamine (1).

[0068] In some embodiments, the reactants in the selective deposition process for forming the organic passivation layer may have the general formula:

[0069] (2) R 2 (COCl) 2

[0070] Where R 2 Can be an aliphatic carbon chain comprising 1-3 carbon atoms, 2-3 carbon atoms or 3 or less carbon atoms. In some embodiments, the bond between the carbon atoms in the reactant or precursor can be a single bond, a double bond, a triple bond or some combination thereof. In some embodiments, the reactant can comprise a chloride. In some embodiments, the reactant can comprise a diacyl chloride. In some embodiments, the reactant can comprise an organic precursor selected from oxalyl chloride (I), malonyl chloride and fumaryl chloride.

[0071] In some embodiments, the reactant comprises an organic precursor selected from 1,4-diisocyanatobutane or 1,4-diisocyanatobenzene. In some embodiments, the reactant comprises an organic precursor selected from terephthaloyl dichloride, alkyl dichlorides such as adipic dichloride, suberyl dichloride, azelayl dichloride, sebacoyl dichloride or terephthaloyl dichloride. In some embodiments, the reactant comprises an organic precursor selected from 1,4-diisothiocyanatobenzene or terephthalaldehyde. In some embodiments, the vaporized reactant may also be a diamine, such as 1,4-diaminobenzene, decane-1,10-diamine, 4-nitrobenzene-1,3-diamine, 4,4'-oxydiphenylamine or ethylenediamine. In some embodiments, the reactant may be bis(2-hydroxyethyl)terephthalate. In some embodiments, the reactant may be a carboxylic acid, such as an alkyl-, alkenyl-, alkadienyl-dicarboxylic acid or tricarboxylic acid, such as oxalic acid, malonic acid, succinic acid, glutaric acid or propane-1,2,3-tricarboxylic acid. In some embodiments, the reactant may be an aromatic carboxylic acid or a dicarboxylic acid, such as benzoic acid, benzene-1,2-dicarboxylic acid, benzene-1,4-dicarboxylic acid or benzene-1,3-dicarboxylic acid. In some embodiments, the reactant may include one or more OH-groups bonded to a hydrocarbon. In some embodiments, the reactant may be selected from diols, triols, aminophenols such as 4-aminophenol, benzene-1,4-diol or benzene-1,3,5-triol. In some embodiments, the reactant may be 8-quinolinol. In some embodiments, the reactant may include alkenyl chlorosilanes, such as alkenyl trichlorosilanes, such as 7-octenyl trichlorosilane.

[0072] After selectively depositing an organic passivation layer on the metal surface, an oxide may be deposited selectively on the dielectric surface relative to the metal surface as described herein.

[0073] Deposition of SiOC and SiOCN

[0074] As mentioned above, in some embodiments, SiOC is selectively deposited on dielectric surfaces relative to metal or metallic surfaces. SiOC can be deposited, for example, as described herein or as described in US Patent Application No. 15 / 588,026, which is incorporated herein by reference.

[0075] In some embodiments, SiOCN is deposited selectively on dielectric surfaces relative to metal or metallic surfaces. SiOCN can be deposited, for example, as described herein or as described in US Patent Application Nos. 14 / 939,984 or 15 / 342,943, each of which is incorporated herein by reference.

[0076] In some embodiments, the SiOSC is selectively deposited on a dielectric surface relative to a metal or metallic surface. The SiOSC can be deposited, for example, as described herein or as described in US Patent Application No. 62 / 502,118, which is incorporated herein by reference.

[0077] For convenience and simplicity, the chemical formula of silicon oxycarbide films is generally referred to herein as SiOC. As used herein, SiOC is not intended to limit, constrain, or define bonding or chemical states, such as the oxidation state of any of Si, O, C, and / or any other elements in the film. Further, in some embodiments, the SiOC film may include one or more elements other than Si, O, and C. For example, in some embodiments, a SiOCN film containing about 0% to about 10% nitrogen on an atomic basis (at%) may be deposited. In some embodiments, a SiOSC film containing about 0 to about 20% sulfur on an atomic basis may be deposited.

[0078] In some embodiments, SiOC may include about 0% to about 30% carbon by atom. In some embodiments, SiOC films may include about 0% to about 70% oxygen by atom. In some embodiments, SiOC films may include about 0% to about 50% silicon by atom.

[0079] For simplicity, unless otherwise indicated, all atomic percentage (i.e., at%) values ​​provided herein do not include hydrogen because it is difficult to accurately analyze hydrogen in a quantitative manner. However, in some embodiments, if it is possible to analyze hydrogen with reasonable accuracy, the hydrogen content of the film is less than about 20 at%, less than about 10 at%, or less than about 5 at%. In some embodiments, the deposited SiOC film may include up to about 70% oxygen by atom (at%). In some embodiments, the SiOC film may include about 10% to about 70%, about 15% to about 50%, or about 20% to about 40% oxygen by atom. In some embodiments, the SiOC film may include at least about 20%, about 40%, or about 50% oxygen by atom.

[0080] In some embodiments, the deposited SiOC film may contain up to about 40% carbon on an atomic basis (at%). In some embodiments, the SiOC film may contain about 0.1% to about 40%, about 0.5% to about 40%, about 1% to about 30%, or about 5% to about 20% carbon on an atomic basis. In some embodiments, the SiOC film may contain at least about 1%, about 10%, or about 20% carbon on an atomic basis.

[0081] In some embodiments, the deposited SiOC film may contain up to about 50% silicon on an atomic basis (at%). In some embodiments, the SiOC film may contain about 10% to about 50%, about 15% to about 40%, or about 20% to about 35% silicon on an atomic basis. In some embodiments, the SiOC film may contain at least about 15%, about 20%, about 25%, or about 30% silicon on an atomic basis.

[0082] In some embodiments, the deposited SiOC film may contain up to about 40% sulfur on an atomic basis (at%). In some embodiments, the SiOC film may contain about 0.01% to about 40%, about 0.1% to about 40%, about 0.5% to about 30%, or about 1% to about 20% sulfur on an atomic basis. In some embodiments, the SiOC film may contain at least about 1%, about 10%, or about 20% sulfur on an atomic basis. In some embodiments, the deposited SiOC film does not contain appreciable amounts of nitrogen. However, in some embodiments, a SiOC film containing nitrogen is deposited. In some embodiments, the deposited SiOC film contains less than about 30 at%, less than about 20 at%, less than about 15 at%, less than about 10 at%, less than about 5 at% nitrogen, less than about 1% nitrogen, or less than about 0.1 at% nitrogen. In some embodiments, the SiOC film does not contain nitrogen.

[0083] As discussed above, in some embodiments, the SiOC film may include Si-C bonds and / or Si-O bonds. In some embodiments, the SiOC film may additionally include Si-N bonds. In some embodiments, the SiOC film may additionally include Si-S bonds. In some embodiments, the SiOC film may include Si-C bonds and Si-O bonds and may not contain Si-N bonds. In some embodiments, the SiOC film may include Si-N bonds and Si-O bonds and may not contain Si-C bonds. In some embodiments, the SiOC film may include Si-N bonds and Si-C bonds and may not contain Si-O bonds. In some embodiments, the SiOC film may include Si-S bonds, Si-C bonds, and Si-O bonds and may not contain Si-N bonds. In some embodiments, the SiOC film may include Si-S bonds, Si-C bonds, and Si-O bonds and may not contain Si-N bonds. In some embodiments, the SiOC film may include Si-S bonds and Si-C bonds and may not contain Si-O bonds. In some embodiments, the SiOC film may include Si-S bonds and Si-O bonds and may not contain Si-C bonds. In some embodiments, the SiOC film may include more Si-O bonds than Si-C bonds, for example, the ratio of Si-O bonds to Si-C bonds may be about 1: 1 to about 10: 1. In some embodiments, the deposited SiOC film may include one or more of SiN, SiO, SiC, SiCN, SiON, SiOSC, SiSC, SiOS, and / or SiOC.

[0084] In some embodiments, a plasma enhanced ALD (PEALD) process is used to deposit the SiOC film. As mentioned above, in some embodiments, the PEALD process does not include an oxygen plasma or a plasma containing oxygen species. In short, a substrate or workpiece is placed in a reaction chamber and subjected to alternating repeated surface reactions. In some embodiments, a SiOC film is formed by repeating a self-limiting ALD cycle. In some embodiments, to form a SiOC film, each ALD cycle includes at least two different stages. The contact of the reactant with the substrate and the removal from the substrate can be regarded as one stage.

[0085] In the first stage, a gas phase first reactant containing silicon contacts the substrate and forms no more than about one monolayer on the dielectric surface. Such reactants are also referred to herein as "silicon precursors," "silicon-containing precursors," or "silicon reactants" and may be, for example, (3-aminopropyl)trimethoxysilane (APTMS), bis(triethoxysilyl)ethane (BTESE), or 3-methoxypropyltrimethoxysilane (MPTMS). In some embodiments, the first reactant contains both silicon and oxygen.

[0086] In the second stage, a second reactant comprising reactive species contacts the substrate and can convert adsorbed silicon to SiOC on the dielectric surface. As discussed above, in some embodiments, the second reactant comprises a hydrogen plasma, such as H 2 / Ar plasma, nitrogen plasma and / or plasma generated in an inert gas.

[0087] In some embodiments, the second reactant comprises hydrogen radicals, hydrogen atoms and / or hydrogen plasma. The second reactant may comprise other species that are not hydrogen precursors. In some embodiments, the second reactant may comprise nitrogen plasma, nitrogen radicals or atomic nitrogen in one form or another. In some embodiments, the second reactant may comprise species from an inert gas such as He, Ne, Ar, Kr or Xe, for example in the form of free radicals, in plasma form or in elemental form. These reactive species from rare gases may not necessarily add material to the deposited film, but may contribute to film growth and contribute to the formation and ignition of plasma in some cases.

[0088] In some embodiments, the gas used to form the plasma may flow continuously throughout the deposition process but may only be activated intermittently.

[0089] In some embodiments, the gas used to form the plasma does not contain oxygen. In some embodiments, the adsorbed silicon precursor does not come into contact with the reactive species generated by the plasma from the oxygen. In some embodiments, the second reactant comprising the reactive species is generated in a gas that does not contain oxygen. For example, in some embodiments, the second reactant may include a plasma generated in a gas that does not contain oxygen. In some embodiments, the second reactant may be generated in a gas that contains less than about 1 atomic % (at %) oxygen, less than about 0.1 at % oxygen, less than about 0.01 at % oxygen, or less than about 0.001 at % oxygen.

[0090] In some embodiments, the gas used to form the plasma does not contain nitrogen. In some embodiments, the adsorbed silicon precursor does not come into contact with the reactive species generated by the plasma from the nitrogen. In some embodiments, the second reactant containing the reactive species is generated in a gas that does not contain nitrogen. For example, in some embodiments, the second reactant can include a plasma generated in a gas that does not contain nitrogen.

[0091] However, in some embodiments, the gas used to form the plasma may include nitrogen. In some other embodiments, the second reactant may include nitrogen radicals, nitrogen atoms, and / or nitrogen plasma. In some embodiments, the second reactant may be generated in a gas comprising less than about 25 atomic % (at%) nitrogen, less than about 20 at% nitrogen, less than about 15 at% nitrogen, less than about 10 at% nitrogen, less than about 5 at% nitrogen, less than about 1 at% nitrogen, less than about 0.1 at% nitrogen, less than about 0.01 at% nitrogen, or less than about 0.001 at% nitrogen. In some embodiments, the second reactant may be generated in a gas comprising hydrogen and nitrogen, for example, the second reactant may include H 2 and N 2 In some embodiments, the second reactant may have less than about 20%, less than about 10%, or less than about 5% N 2 With H 2 Ratio (N 2 / H 2 ) is generated in the gas.

[0092] In some embodiments, the gas used to form the plasma does not contain nitrogen or oxygen. In some embodiments, the adsorbed silicon precursor does not come into contact with reactive species generated by the plasma from nitrogen or oxygen. In some embodiments, the second reactant comprising reactive species is generated in a gas that does not contain nitrogen or oxygen. For example, in some embodiments, the second reactant can include a plasma generated in a gas that does not contain nitrogen or oxygen.

[0093] Additional stages can be added and stages can be removed as needed to adjust the composition of the final film selectively deposited on the dielectric surface.

[0094] In some embodiments for depositing SiOC films, one or more deposition cycles are initiated by contacting the substrate with a silicon precursor, followed by a second plasma reactant. In other embodiments, deposition may be initiated by contacting the substrate with a second plasma reactant, followed by a silicon precursor.

[0095] Excess reactants and reaction byproducts (if any) are removed from the vicinity of the substrate, particularly from the substrate surface, between the reactant contact stages. In some embodiments, excess reactants and reaction byproducts (if any) are removed from the substrate surface by, for example, purging the reaction chamber between the reactant contact stages, for example, by purging with an inert gas. The flow rate and contact time of each reactant are adjustable, as are the removal steps, so that the quality and various properties of the film can be controlled.

[0096] In some embodiments, gas is continuously provided to the reaction chamber during each deposition cycle or during the entire PEALD process, and reactive species are provided by generating plasma in the reaction chamber or in the gas upstream of the reaction chamber. In some embodiments, the gas comprises hydrogen. In some embodiments, the gas comprises nitrogen. In some embodiments, the gas may include an inert gas, such as helium or argon. The flowing gas may also be used as a purge gas and / or a second reactant (or reactive species) of the first reactant.

[0097] The deposition cycle is repeated until a SiOC film having a desired thickness is obtained on the dielectric surface. In some embodiments, deposition parameters, such as precursor flow rate, contact time, removal time, and / or the reactants themselves, can be varied during one or more deposition cycles during the PEALD process to obtain a film having desired properties.

[0098] In some embodiments, the surface of the substrate is contacted with the reactant. In some embodiments, a pulse of the reactant is provided to the reaction space containing the substrate. The term "pulse" may be understood to include supplying the reactant to the reaction chamber for a predetermined amount of time. The term "pulse" does not limit the length or duration of the pulse, and the pulse may be any length of time. In some embodiments, the substrate is moved to the reaction space containing the reactant. In some embodiments, the substrate is subsequently moved from the reaction space containing the first reactant to a second different reaction space containing the second reactant.

[0099] In some embodiments, the substrate is first contacted with a silicon reactant. After initial surface termination, if necessary or desired, the substrate is contacted with a first silicon reactant. According to some embodiments, the first reactant pulse comprises a carrier gas flow and a volatile silicon species reactive with a dielectric surface, such as APTMS or MPTMS. Accordingly, the silicon species adsorbs onto the dielectric surface.

[0100] In some embodiments, the silicon reactant is in contact with the surface for about 0.05 seconds to about 5.0 seconds, about 0.1 seconds to about 3 seconds, or about 0.2 seconds to about 1.0 seconds. One skilled in the art can readily determine the optimal contact time based on the particular situation.

[0101] After allowing about one molecular layer of silicon-containing species to adsorb on the substrate surface for a sufficient time, remove excess first silicon reactants and reaction byproducts (if any) from the substrate surface. In some embodiments, removing excess reactants and reaction byproducts (if any) may include purging the reaction chamber. In some embodiments, the reaction chamber may be purged in the following manner: stop the flow of the first reactant while continuing to flow a carrier gas or purge gas for a sufficient time to diffuse or purge excess reactants and reactant byproducts (if any) in the reaction space. In some embodiments, purge excess first precursors with the aid of an inert gas such as nitrogen or argon. In some embodiments, the substrate may be moved from the reaction space containing the first reactant to a second different reaction space. In some embodiments, removing the first reactant lasts for about 0.1 seconds to about 10 seconds, about 0.3 seconds to about 5 seconds, or about 0.3 seconds to about 1 second. The contact and removal of silicon reactants may be considered to be the first stage or silicon stage of the PEALD cycle.

[0102] In the second stage, a second reactant comprising a reactive species such as hydrogen plasma is provided to the workpiece. The plasma may be generated in the reaction chamber or in a remote plasma generator and provided to the reaction chamber. For example, the hydrogen plasma may be formed by generating a plasma in hydrogen in the reaction chamber or upstream of the reaction chamber, such as by causing hydrogen (H 2 ) flows through a remote plasma generator.

[0103] In some embodiments, in flowing H 2 In some embodiments, H 2 The flow rate may be from about 0.1 to about 0.4 slpm. As mentioned above, in some embodiments, an inert gas such as Ar may also be introduced. In some embodiments, the Ar co-flow may be, for example, about 2 slpm.

[0104] In some embodiments, H is supplied to the reaction chamber before the plasma is ignited or hydrogen atoms or radicals are formed. 2 In some embodiments, H2 It is continuously supplied to the reaction chamber and generates or supplies hydrogen-containing plasma, atoms or radicals when needed.

[0105] In some embodiments, in flowing N 2 In some embodiments, N 2 The flow rate may be from about 0.1 to about 0.4 slpm. As mentioned above, in some embodiments, an inert gas such as Ar may also be introduced. In some embodiments, the Ar co-flow may be, for example, about 2 slpm.

[0106] In some embodiments, N is supplied to the reaction chamber before the plasma is ignited or hydrogen atoms or radicals are formed. 2 In some embodiments, N is continuously supplied to the reaction chamber. 2 and generates or supplies nitrogen-containing plasma, atoms or free radicals when necessary.

[0107] Typically, for example, the second reactant comprising hydrogen plasma contacts the substrate for about 0.1 second to about 10 seconds. In some embodiments, the second reactant (for example, hydrogen-containing plasma) contacts the substrate for about 0.1 second to about 10 seconds, 0.5 second to about 5 seconds, or 0.5 second to about 2.0 seconds. However, depending on the reactor type, substrate type, and surface area thereof, the second reactant contact time can even be longer than about 10 seconds. In some embodiments, the contact time can be minute-level. Those skilled in the art can easily determine the optimal contact time based on specific circumstances.

[0108] In some embodiments, the second reactant is provided in two or more different pulses without introducing another reactant between any two or more pulses. For example, in some embodiments, a plasma such as a hydrogen-containing plasma is provided in two or more sequential pulses without introducing a Si precursor between sequential pulses. In some embodiments, during the provision of the plasma, two or more sequential plasma pulses are generated by providing a plasma discharge for a first time period; extinguishing the plasma discharge for a second time period, such as from about 0.1 seconds to about 10 seconds, from about 0.5 seconds to about 5 seconds, or from about 1.0 seconds to about 4.0 seconds; and before introducing another precursor or before a removal step, such as before a Si precursor or a purge step, re-stimulating the plasma discharge for a third time period. Additional plasma pulses may be introduced in the same manner. In some embodiments, the plasma is ignited for an equivalent time period in each pulse.

[0109] In some embodiments, a plasma, such as a plasma containing hydrogen or nitrogen, can be generated by applying an RF power of about 10 W to about 5000 W, about 10 W to about 2000 W, about 50 W to about 1000 W, about 300 W to about 500 W, about 100 W to about 500 W, or about 30 W to about 100 W in some embodiments. In some embodiments, the plasma power used to generate the nitrogen-containing plasma can be about 10 W to about 5000 W, about 50 W to about 1,500 W, about 70 W to about 1200 W, about 80 W to about 1,000 W, about 10 W to about 500 W, or about 300 W to about 500 W. In some embodiments, the RF power density can be about 0.02 W / cm 2 To about 2.0W / cm 2 , or about 0.05W / cm 2 To about 1.5W / cm 2 . RF power can be applied to the second reactant that flows during the plasma contact time, flows continuously through the reaction chamber, and / or flows through the remote plasma generator. Thus, in some embodiments, the plasma is generated in situ, while in other embodiments, the plasma is generated remotely. In some embodiments, a showerhead reactor is utilized and the plasma is generated between a pedestal (on which the substrate is located) and a showerhead plate. In some embodiments, the distance between the pedestal and the showerhead plate is about 0.1 cm to about 20 cm, about 0.5 cm to about 5 cm, or about 0.8 cm to about 3.0 cm.

[0110] After a time sufficient for the previously adsorbed molecular layer to be fully saturated with and react with the plasma pulse, any excess reactants and reaction byproducts are removed from the substrate surface.

[0111] In some embodiments, removing excess reactants and reaction byproducts (if any) may include purging the reaction chamber. In some embodiments, the reaction chamber can be purged in the following manner: stop the flow of the second reactant while continuing to flow the carrier gas or purge gas for enough time to diffuse or purge the excess reactants and reactant byproducts (if any) in the reaction space. In some embodiments, the second precursor is purged by means of an inert gas such as nitrogen or argon flowing in the entire PEALD cycle. In some embodiments, the substrate can be moved to different reaction spaces from the reaction space comprising the second reactant. In some embodiments, removal can be about 0.1 seconds to about 10 seconds, about 0.1 seconds to about 4 seconds or about 0.1 seconds to about 0.5 seconds. Reactive species contact and removal together are the second reactive species stage in the SiOCN atomic layer deposition cycle.

[0112] These two stages together constitute one ALD cycle, which is repeated to form a SiOC film having a desired thickness.

[0113] According to some embodiments of the present disclosure, the PEALD reaction may be carried out at a temperature in the range of about 25°C to about 700°C, about 50°C to about 600°C, about 20°C to about 200°C, about 75°C to about 450°C, or about 90°C to about 300°C. In some embodiments, the deposition temperature is about 100°C to about 200°C. In some embodiments, the optimal reactor temperature may be limited by the maximum allowable thermal budget. Therefore, in some embodiments, the reaction temperature is about 300°C to about 400°C. In some applications, the maximum temperature is around about 400°C, and therefore the PEALD process is operated at this reaction temperature.

[0114] According to some embodiments of the present disclosure, the pressure of the reaction chamber during processing is maintained at about 0.01 Torr to about 50 Torr or about 0.1 Torr to about 10 Torr. In some embodiments, the pressure of the reaction chamber is greater than about 6 Torr or about 20 Torr. In some embodiments, the SiOCN deposition process can be performed at a pressure of about 1 Torr to about 500 Torr, about 1 Torr to about 20 Torr, about 2 Torr to about 10 Torr, about 20 Torr to about 50 Torr, or about 20 Torr to about 30 Torr.

[0115] In some embodiments, the oxide deposition is performed at a pressure of about 0.1 Torr or greater, or 1 Torr or greater. In some embodiments, the pressure can be up to about 760 Torr, up to about 500 Torr, or up to about 50 Torr.

[0116] According to some embodiments, a SiOC or SiOCN thin film is selectively deposited on a dielectric surface on a substrate in a reaction space by a PEALD deposition process comprising at least one cycle, wherein the cycle comprises:

[0117] contacting the substrate with a silicon reactant such that silicon species adsorb onto a surface of the substrate;

[0118] removing excess silicon reactant and reaction byproducts (if any) from the substrate surface;

[0119] contacting the substrate with a second reactant comprising a reactive species generated by the plasma, such as a reactive species comprising hydrogen or nitrogen;

[0120] removing excess second reactant and reaction byproducts (if any) from the substrate surface; and

[0121] The contacting and removing steps are optionally repeated to form a SiOC or SiOCN film of desired thickness and composition.

[0122] A variety of different suitable Si precursors may be used in the presently disclosed PEALD processes for forming SiOC and SiOCN.

[0123] In some embodiments, at least some Si precursors suitable for depositing SiOCN by a PEALD process have the following general formula:

[0124] (1) Si(OR I ) 4-x (R II NR III R IV ) x

[0125] Where x = 1-4, R I may be independently selected alkyl groups, R II may be independently selected hydrocarbon groups, R III and R IV Can be independently selected alkyl groups and / or hydrogen. In some embodiments, R I and R II C 1 -C 3 Alkyl ligands, such as methyl, ethyl, n-propyl or isopropyl. In some embodiments, R I Can be C 1 -C 4 In some embodiments, R II Not C 3 In some embodiments, R II It is C 1 -C 2 Hydrocarbon or C 4 -C 6 In some embodiments, R II It can be an unsaturated hydrocarbon, such as a hydrocarbon containing one or more double bonds. II can be an alkyl group with one hydrogen removed. III and R IV is hydrogen. In some embodiments, R I is methyl, R II is n-propyl, R III is hydrogen, R IV is hydrogen, and x=1.

[0126] For example, a Si precursor may have the following formula (written in more detail to show bonding): I -O-) 4-x Si(-R II -NR III R IV )x, where x = 1-4, R I can be independently selected alkyl groups, R IImay be independently selected hydrocarbons, and R III and R IV It can be independently selected alkyl and / or hydrogen.

[0127] According to some embodiments, some Si precursors may have the following general formula:

[0128] (2) Si(OR I ) 4-x-y-z (R II NR III R IV ) x H y (OH) z

[0129] Where x = 1-4, y = 0-3, and z = 0-3, R I and R II may be independently selected alkyl groups, R II may be independently selected hydrocarbon groups, R III and R IV Can be independently selected alkyl groups and / or hydrogen. In some embodiments, R II It can be an unsaturated hydrocarbon, such as a hydrocarbon containing one or more double bonds. II It may be an alkyl group from which one of the hydrogen atoms is removed.

[0130] According to some embodiments, some Si precursors may have the following general formula:

[0131] (3) L n Si(OR I ) 4-x-n (R II NR III R IV ) x

[0132] Where n = 1-3, x = 0-3, R I may be independently selected alkyl groups, R II may be independently selected hydrocarbons, R III and R IV R is an independently selected alkyl group and / or hydrogen, and L is an independently selected alkyl group or halogen. II It can be an unsaturated hydrocarbon, such as a hydrocarbon containing one or more double bonds. II It may be an alkyl group from which one of the hydrogen atoms is removed.

[0133] According to some embodiments, some Si precursors may have the following general formula:

[0134] (4) L n Si(OR I ) 4-x-y-z-n (R II NR III R IV ) x H y (OH) z

[0135] Where n = 0-3, x = 1-4, y = 0-3, z = 0-3, R I may be independently selected alkyl groups, R II may be independently selected hydrocarbons, R III and R IV R is an independently selected alkyl group and / or hydrogen, and L is an independently selected alkyl group or halogen. II It can be an unsaturated hydrocarbon, such as a hydrocarbon containing one or more double bonds. II It may be an alkyl group from which one of the hydrogen atoms is removed.

[0136] According to some embodiments, some Si precursors may have the following general formula:

[0137] 5) (R I O) 4-x Si(R II -NH 2 ) x

[0138] Where x = 1-4, R I may be independently selected alkyl groups, R II Can be independently selected hydrocarbons. In some embodiments, R I and R II C 1 -C 3 Alkyl ligands, such as methyl, ethyl, n-propyl or isopropyl. In some embodiments, R I is methyl, R II is n-propyl and x=1.

[0139] In some embodiments, R II It can be an unsaturated hydrocarbon, such as a hydrocarbon containing one or more double bonds. II It may be an alkyl group from which one of the hydrogen atoms is removed.

[0140] According to some embodiments, some Si precursors may have the following general formula:

[0141] 6) (R I O) 3 Si-RII -NH 2

[0142] Among them, R I may be independently selected alkyl groups, R II The hydrocarbons may be independently selected.

[0143] In some embodiments, R I and R II C 1 -C 3 Alkyl ligands, such as methyl, ethyl, n-propyl or isopropyl. In some embodiments, R II It can be an unsaturated hydrocarbon, such as a hydrocarbon containing one or more double bonds. II It may be an alkyl group from which one of the hydrogen atoms is removed.

[0144] According to some embodiments, some Si precursors may have the following general formula:

[0145] 7) (R I O) 4-x Si(-[CH 2 ] n -NH 2 ) x

[0146] Where x = 1-4, n = 1-5, R I Can be independently selected alkyl groups. In some embodiments, R I It is C 1 -C 4 Alkyl ligands, such as methyl, ethyl, n-propyl or isopropyl. In some embodiments, R I is a methyl group, and x=1.

[0147] In some embodiments, the silicon precursor does not contain halogens. In some embodiments, the silicon precursor may contain at least one aminoalkyl ligand.

[0148] According to some embodiments, a suitable silicon precursor may include at least one carbon bonded to silicon and containing at least one NH 2 -group ligands, such as aminoalkyl ligands. According to some embodiments, suitable silicon precursors may include at least one NH bonded to silicon via carbon and containing an NH 2 A suitable silicon precursor may include at least one ligand bonded to silicon via a carbon atom and containing at least one NR III R IV-group ligand, where R III and R IV Can be independently selected alkyl groups and / or hydrogen attached to the carbon chain, such as aminoalkyl ligands. According to some embodiments, a suitable silicon precursor may include at least one ligand bonded to silicon through carbon, and in the ligand, at least one nitrogen is bonded to carbon. In addition, a ligand bonded to silicon through carbon and in which at least one nitrogen is bonded to carbon may include hydrogen bonded to nitrogen. According to some embodiments, in addition to the ligand bonded to silicon through carbon, a suitable silicon precursor may also include an alkoxy ligand, such as a methoxy, ethoxy, n-propoxy, isopropoxy or tert-butoxy ligand. According to some embodiments including some of the above formulas, a suitable silicon precursor includes a carbon chain bonded to silicon through carbon, and in which there is an amino group attached to the carbon chain, such as an alkylamino or –NH 2 In some embodiments, the carbon chain may be a C1-C6 hydrocarbon, a C2-C6 hydrocarbon or a C2-C4 hydrocarbon containing only carbon and hydrogen. In some embodiments, the carbon chain may be unsaturated and contain a double carbon-carbon bond. In some other embodiments, the carbon chain may contain other atoms except carbon and hydrogen.

[0149] A variety of different suitable Si precursors may be used in the currently disclosed PEALD process for forming SiOC. In some embodiments, a suitable Si precursor may not contain nitrogen. In some embodiments, a suitable Si precursor may contain silane.

[0150] In some embodiments, a suitable Si precursor for forming SiOC may include two Si atoms connected or bonded to at least one hydrocarbon group through at least one hydrocarbon group. In some embodiments, a suitable Si precursor may include two Si atoms connected or bonded to at least one alkyl group through at least one alkyl group. In some embodiments, a suitable Si precursor may include two Si atoms connected or bonded to at least one alkoxy group through at least one alkoxy group. In some embodiments, a suitable Si precursor may include two Si atoms connected or bonded to at least one silyl group through at least one silyl group. In some embodiments, a suitable Si precursor may include two Si atoms connected or bonded to at least one silyl ether group through at least one silyl ether group. In some embodiments, a suitable Si precursor may include at least one -SH group, wherein -SH may be bonded to an alkyl chain or a silicon atom. In some embodiments, a suitable Si precursor may include at least one thiol group. In some embodiments, a suitable Si precursor may include at least one -R-SH structure, wherein R may be C 1 -C 5Alkyl groups. In some embodiments, suitable Si precursors may contain at least one -SH group on the alkyl chain and one or more alkoxy groups bonded to the silicon atom.

[0151] In some embodiments, a suitable Si precursor may include at least one Si atom attached or bonded to one or more alkoxy groups. In some embodiments, a suitable Si precursor may include at least one Si atom attached or bonded to one or more alkyl groups. In some embodiments, a suitable Si precursor may include at least one Si atom attached or bonded to at least an alkyl group and an alkoxy group.

[0152] In some embodiments, at least some Si precursors suitable for depositing SiOC by a PEALD process may include a bridged alkoxysilane having the following general formula:

[0153] (1)(R II O) 3 Si-R I -Si(OR II ) 3

[0154] Among them, R I and R II Each of R can be an independently selected alkyl group. I and R II Each of the C 1 -C 5 Alkyl ligands such as methyl, ethyl, n-propyl, isopropyl, tert-butyl or pentyl.

[0155] According to some embodiments, some Si precursors may include bridged alkoxyalkylsilanes having the following general formula:

[0156] (2)R III y (OR II ) x Si-R I -Si(OR II ) x R III y

[0157] Among them, R I , R II and R III Each of R may be an independently selected alkyl group, and x+y=3. In some embodiments, R I and R II Each of the C 1 -C 5Alkyl ligands, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl or pentyl. III Can be independently selected C 1 -C 8 Alkyl ligands.

[0158] According to some embodiments, some Si precursors may include cyclic alkoxysilanes having the following general formula:

[0159] (3)(R II O) 2 Si–R I 2 –Si(OR II ) 2

[0160] Formula (3) can alternatively be represented by the following structural formula:

[0161]

[0162] Among them, R I and R II Each of R can be an independently selected alkyl group. I and R II Each of the C 1 -C 5 Alkyl ligands such as methyl, ethyl, n-propyl, isopropyl, tert-butyl or pentyl.

[0163] According to some embodiments, some Si precursors may include cyclic alkoxyalkylsilanes having the following general formula:

[0164] (4)R III y (OR II ) x Si–R I 2 -Si(OR II ) x R III y

[0165] Formula (4) can alternatively be represented by the following structural formula:

[0166]

[0167] Among them, R I , R II and R III Each of R may be an independently selected alkyl group, and x+y=2. I and R IIEach of the C 1 -C 5 Alkyl ligands, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl or pentyl. III Can be independently selected C 1 -C 8 Alkyl ligands.

[0168] According to some embodiments, some Si precursors may include linear alkoxysilanes having the following general formula:

[0169] (5)(R II O) 3 Si–(O-Si-R I 2 ) n –O-Si(OR II ) 3

[0170] Among them, R I may be independently selected alkyl groups or hydrogen, R II may be independently selected alkyl groups, and n=1-4. In some embodiments, R I and R II Each of the C 1 -C 5 Alkyl ligands, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl or pentyl. I can be hydrogen and R II Can be independently selected C 1 -C 5 Alkyl ligands.

[0171] According to some embodiments, some Si precursors may include linear alkoxysilanes having the following general formula:

[0172] (6)R III y (OR II ) x Si–(-R I -Si) n -Si(OR II ) x R III y

[0173] Among them, R I , R II and R III Each of R may be an independently selected alkyl group, x+y=2, and n may be greater than or equal to 1. In some embodiments, R I and RII Independently selected from C 1 -C 5 Alkyl ligands, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl or pentyl. III Can be independently selected C 1 -C 8 Alkyl ligands.

[0174] According to some embodiments, some Si precursors may include alkoxysilanes having the following general formula:

[0175] (7)Si(OR I ) 4

[0176] Among them, R I Can be independently selected alkyl groups. In some embodiments, R I Can be independently selected C 1 -C 5 Alkyl ligands, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl or pentyl.

[0177] According to some embodiments, some Si precursors may include alkoxyalkylsilanes having the following general formula:

[0178] (8)Si(OR I ) 4-x R II x

[0179] Among them, R I and R II Each of R may be an independently selected alkyl group, and x=1-3. I Can be independently selected C 1 -C 5 Alkyl ligands, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl or pentyl. II Can be independently selected C 1 -C 8 Alkyl ligands.

[0180] According to some embodiments, some Si precursors may include alkoxysilanes that do not include nitrogen and have the following general formula:

[0181] (9)Si(OR I ) 4-x R II x

[0182] Among them, R I may be independently selected alkyl groups, RII can be any ligand containing carbon, hydrogen and / or oxygen but not nitrogen, and x=1-3. In some embodiments, R I Can be independently selected C 1 -C 5 Alkyl ligands, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl or pentyl. II For example, alkenyl, alkynyl, phenyl, carbonyl, aldehyde, ester, ether, carboxyl, peroxy, hydroperoxy, thiol, acrylate or methacrylate ligands may be included.

[0183] According to some embodiments, some Si precursors may have the following general formula:

[0184] (10)Si(OR I ) 4-x R II x

[0185] Where x = 0-3, R I Can be independently selected C 1 -C 7 or C 1 -C 5 Alkyl ligand, R II Can be independently selected ligands consisting of carbon and / or hydrogen and / or oxygen. For example, in some embodiments, R II It may be an alkoxyalkyl group. In some embodiments, R II It can be, for example, alkenyl, alkynyl, phenyl, carbonyl, aldehyde, ester, ether, carboxyl, peroxy or hydroperoxy. In some embodiments, for example, R I is methyl, R II is a 3-methoxypropyl ligand, and x is 1.

[0186] According to some embodiments, some Si precursors may have the following general formula:

[0187] (11)(R I O) 4-x Si-(R II -OR III ) x

[0188] Where x = 0-3, R I and R II Each of these can be independently selected C 1 -C 7 or C 1 -C 5 Alkyl ligand, R IIICan be independently selected ligands consisting of carbon and / or hydrogen and / or oxygen. For example, in some embodiments, R III It can be, for example, alkenyl, alkynyl, phenyl, carbonyl, aldehyde, ester, ether, carboxyl, peroxy or hydroperoxy. In some embodiments, for example, R I , R II and R III The groups may each be independently selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl and tert-butyl.

[0189] According to some embodiments, some Si precursors may have the following general formula:

[0190] (12)Si(R I ) 4-x-y R II x R III y

[0191] Where x+y=0-4, R I is an alkoxide ligand or a halide having 1 to 5 carbon atoms, R II is any ligand containing sulfur, R III In some embodiments, R I , R II and R III Can be selected independently of each other. In some embodiments, R I May contain methoxy ligands, R II may contain 3-mercaptopropyl, x=1 and y=0. That is, in some embodiments, some Si precursors may contain Si(OCH 3 ) 3 C 3 H 6 In some embodiments, the Si precursor may include mercaptomethylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane and / or 3-mercaptopropyltriethoxysilane.

[0192] In some embodiments, the silicon precursor does not contain halogens. In some embodiments, the silicon precursor does not contain nitrogen. In some embodiments, the carbon chain can be unsaturated and contain double carbon-carbon bonds. In some other embodiments, the carbon chain can contain other atoms except carbon and hydrogen.

[0193] In some embodiments, the silicon precursor may include bis(triethoxysilyl)ethane (BTESE). In some embodiments, the silicon precursor may include 3-methoxypropyltrimethoxysilane (MPTMS or Si(OCH 3 ) 3 C 3 H 6 OCH 3 ). In some embodiments, the silicon precursor may include (3-mercaptopropyl)trimethoxysilane.

[0194] In some embodiments, during the ALD stage, more than one silicon precursor may contact the substrate surface at the same time. In some embodiments, the silicon precursor may include more than one silicon precursor described herein. In some embodiments, a first silicon precursor is used in the first ALD cycle, and a second different ALD precursor is used in a later ALD cycle. In some embodiments, multiple silicon precursors may be used during a single ALD stage, for example to optimize certain properties of the deposited film. In some embodiments, only one silicon precursor may contact the substrate during deposition. In some embodiments, there may be only one silicon precursor and one second reactant or a combination of second reactants during the deposition process. In some embodiments, there is no metal precursor during the deposition process. In some embodiments, the silicon precursor is not used as a silylating agent. In some embodiments, the deposition temperature and / or duration of the silicon precursor contact step are selected so that the silicon precursor does not decompose. In some embodiments, the silicon precursor may decompose during the silicon precursor contact step. In some embodiments, the silicon precursor does not contain halogens, such as chlorine or fluorine.

[0195] In some embodiments, the second reactant may include a compound having both N and H, such as NH 3 and N 2 H 4 、N 2 / H 2 In some embodiments, the second reactant may be at least partially composed of N 2 In some embodiments, the second reactant may be at least partially composed of H 2 and N 2 Formation, where H 2 and N 2 At a flow ratio (H) of about 100:1 to about 1:100, about 20:1 to about 1:20, about 10:1 to about 1:10, about 5:1 to about 1:5, and / or about 2:1 to about 4:1, and in some cases 1:1. 2 / N 2 ). For example, the hydrogen-containing plasma used to deposit SiOCN may use one or more ratios of N2 and H 2 to generate.

[0196] In some embodiments, the second reactant may be generated from a gas containing less than about 1 atomic % (at%) nitrogen, less than about 0.1 at % nitrogen, less than about 0.01 at % nitrogen, or less than about 0.001 at % nitrogen. In some embodiments, the second reactant does not contain N 2 NH 3 or N 2 H 4 .

[0197] Deposition of metal oxides

[0198] As mentioned above, in some embodiments, the metal oxide is selectively deposited on the dielectric surface relative to the metal or metallic surface. The metal oxide can be deposited, for example, as described herein or as described in US Patent Application No. 62 / 502,118, which is incorporated herein by reference.

[0199] In some embodiments, thin films comprising materials other than SiOC can be selectively deposited by processes as described herein. For example, in some embodiments, metal oxide films can be selectively deposited by a PEALD process that does not include an oxygen plasma or excited oxygen species, substantially as described above for SiOC and SiOCN but using a different first precursor. In these embodiments, a different metal precursor is used in place of the silicon precursor in the methods described herein. In some embodiments, titanium oxide, niobium oxide, tantalum oxide, tungsten oxide, aluminum oxide, or other metal oxide films can be selectively deposited by a PEALD process as described herein.

[0200] In some embodiments, the metal oxide film may include more than one metal oxide.The different metals may be provided from the same precursor or by two or more different metal precursors provided in one or more deposition cycles.

[0201] In some embodiments, oxide films comprising both silicon and metals may be selectively deposited as described herein by a PEALD process that does not include oxygen plasma or excited oxygen species. In some embodiments, oxides comprising both metals and silicon are selectively deposited. In some embodiments, the oxide film may comprise a mixture of metal oxides and silicon oxides. In some embodiments, the oxide film may comprise a metal silicate. For example, the film may comprise silicon oxide and one or more transition metal oxides, such as ZrO 2 , HfO 2 or TiO 2 、Al 2 O 3, lanthanide (+Sc+Y) oxides, Ta 2 O 5 or Nb 2 O 5 .

[0202] In some embodiments, a metal precursor is used along with a silicon precursor in a process as described herein. In some embodiments, a deposition cycle for depositing a metal oxide and a deposition cycle for depositing silicon oxide can be provided in a deposition process at a selected ratio to selectively deposit a film having a desired composition.

[0203] In some embodiments, the selective deposition process may include a single deposition cycle, which includes contacting the substrate with a first metal precursor, a second silicon precursor, and a third plasma reactant alternately and sequentially. The metal and silicon precursors and the third reactant can be used for the deposition of metal oxides and silicon oxides as described herein. The deposition cycle can start with providing a metal reactant, providing a silicon reactant, or providing a third reactant. As described herein, the provision of each reactant can be separated by a purge step, in which excess reactants and reaction byproducts are removed from the reaction space. In some embodiments, the ratio of the metal precursor and the silicon precursor is selected and / or adjusted to provide a mixed metal oxide film with a desired composition.

[0204] In some embodiments, the metal precursor used to deposit the metal-containing oxide film by the process described herein may include a volatile compound comprising the desired metal and oxygen. A list of exemplary metal precursors used to deposit metal oxide films by a PEALD process as described herein that does not include an oxygen plasma or excited oxygen species is provided in Table 1.

[0205] Precursor compounds Membrane material Aluminum(III) Ethoxide <![CDATA[Al 2 THE 3 ]]> Niobium(V) Ethoxide <![CDATA[Nb 2 THE 5 ]]> Tantalum(V) Ethoxide <![CDATA[Ta 2 THE 5 ]]> Titanium(IV) Ethoxide <![CDATA[TiO 2 ]]> Titanium(IV) Methanol <![CDATA[TiO 2 ]]> Titanium(IV) Isopropoxide (TTIP) TiO(CN) Pentamethylcyclopentadienyltitanium trimethoxy <![CDATA[TiO 2 ]]> W(thd)4 <![CDATA[WO x ]]>

[0206] Table 1: Precursors used for depositing metal oxide thin films

[0207] In some embodiments, the metal precursor used to deposit the metal oxide film by the processes described herein may include a volatile compound of the formula:

[0208] M(OR I ) x-y R II y

[0209] Among them, R Imay be an independently selected hydrocarbon group, and wherein M is a metal or Ge, such as a transition metal or Ge, Al, Ga, In, Sn, Pb, Bi, Sb, wherein x+y is equal to the oxidation state or the number of bonds of the metal atom, such as 3, 4, 5, or 6. In some embodiments where there are double or triple bonds to the metal atom, each double or triple bond may be counted twice or three times when determining the value of x+y.

[0210] In some embodiments, R II It can be any ligand containing carbon, hydrogen, nitrogen, halogen and / or oxygen. In some embodiments, M is a transition metal selected from the group consisting of Ti, V, Cr, Mn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Au, Hf, Ta, W, Re, Os, Ir and Pt.

[0211] In some embodiments, M is a transition metal selected from the group consisting of Cu, Fe, Co, Ni. In some embodiments, M is a transition metal selected from the group consisting of Au, Pt, Ir, Pd, Os, Ag, Re, Rh, and Ru.

[0212] In some embodiments, R I Can be independently selected C1-C5 alkyl ligands, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl or pentyl ligands. In some embodiments, R I Oxygen or nitrogen or another heteroatom may be contained.

[0213] In some embodiments, R II Ligands may include, for example, alkenyl, alkynyl, cyclic hydrocarbon, amine, alkylamine, phenyl, carbonyl, aldehyde, ester, ether, carboxyl, peroxy, hydroperoxy, thiol, acrylate or methacrylate.

[0214] In some embodiments, at least one ligand of the above formula comprises oxygen. In some embodiments, M may also be a Group 1 or 2 metal element.

[0215] In some embodiments, the metal precursor used to deposit the metal oxide film by the processes described herein may include a volatile compound of the formula:

[0216] M(OR I ) x ,

[0217] Among them, R I It can be an independently selected alkyl group, and wherein M is a metal or Ge, such as a transition metal or Ge, Al, Ga, In, Sn, Pb, Bi, Sb, and wherein x is equal to the oxidation state or the bond number of the metal atom, such as 3, 4, 5 or 6.

[0218] In some embodiments where double or triple bonds to the metal atoms are present, each double or triple bond may be counted twice or three times when determining the value of x.

[0219] In some embodiments, R I It may be an independently selected C1-C5 alkyl ligand, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl or pentyl ligand.

[0220] In some embodiments, M is a transition metal selected from the group consisting of Ti, V, Cr, Mn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Au, Hf, Ta, W, Re, Os, Ir, and Pt. In some embodiments, M is a transition metal selected from the group consisting of Cu, Fe, Co, Ni. In some embodiments, M is a transition metal selected from the group consisting of Au, Pt, Ir, Pd, Os, Ag, Re, Rh, and Ru. In some embodiments, M may be a rare earth element, such as Sc, Y, La, Ce, or Nd.

[0221] In some embodiments, the metal precursor used to deposit the metal oxide film by the process described herein may include at least one multidentate ligand, such as a bidentate ligand, for example, a betadiketone ligand (acac, thd) or another multidentate / bidentate ligand bonded to the metal atom through at least one oxygen. In some embodiments, the metal precursor used to deposit the metal oxide film by the method described herein may include a cyclic ligand, such as a cyclopentadienyl ligand.

[0222] In some embodiments, the metal precursor used to deposit the metal oxide film by the process described herein may include an alkoxide precursor or an alkoxide ligand. In some embodiments, the metal precursor used to deposit the metal oxide film by the method described herein includes at least one metal-oxygen bond. In some embodiments, the metal precursor used to deposit the metal oxide film by the method described herein does not contain a metal-oxygen bond, but contains oxygen in the ligand. In some embodiments, the metal precursor includes a metal or Ge, such as a transition metal or Ge, Al, Ga, In, Sn, Pb, Bi, Sb. In some embodiments, the metal precursor includes a Group 1 or Group 2 metal element. In some embodiments, M can be a rare earth element, such as Sc, Y, La, Ce, or Nd.

[0223] In some embodiments, the metal oxide film can be deposited on a substrate comprising a photoresist or other organic material according to the processes described herein. In some embodiments, the metal oxide film can be deposited on a substrate that might otherwise be damaged by a PEALD process involving an oxygen plasma.

[0224] In some embodiments, the metal oxide film is selectively deposited on a first surface relative to a second surface comprising a passivation layer, such as an organic passivation layer. In some embodiments, the metal oxide deposition can also be used to remove some or all of the passivation layer. For example, the metal oxide film can be selectively deposited on a first dielectric surface relative to a metal or metallic surface, wherein the metal or metallic surface can comprise a passivation layer, such as an organic passivation layer.

[0225] In some embodiments, a metal oxide film deposited according to a PEALD process as described herein may have a higher wet etch resistance than a similar metal oxide film deposited by a PEALD process including an oxygen plasma or excited oxygen species. As described herein, in some embodiments, the formation of the metal oxide film may be controlled by selecting a plasma power within a range (e.g., a range as described herein for the deposition of SiOC) in a PEALD process so as to achieve a desired step coverage and / or WERR. That is, in some embodiments, the process conditions for controlling the formation of a SiOC film as described herein may be used to control the formation of a metal oxide film.

[0226] In some embodiments, the second reactant used in the PEALD process for depositing a metal oxide thin film is the same as the second reactant described herein for the deposition of SiOC. In some embodiments, the second reactant comprises a plasma generated in a gas comprising an inert gas such as Ar. As described above, in some embodiments, the second reactant is a plasma generated in a gas that does not contain oxygen. In some embodiments, the second reactant comprises a plasma generated in Ar, a plasma generated in Ar and N 2 Plasma generated in Ar and H 2 In some embodiments, the second reactant can be selected to control the amount of a particular component of the metal oxide film, such as the amount of carbon and / or nitrogen. In addition, the plasma power can be controlled to adjust the composition of the film.

[0227] In some embodiments, a metal oxide containing titanium is deposited by a PEALD process that does not use oxygen plasma or other oxygen reactants. For example, a titanium oxide film can be deposited by a PEALD method using a combination of titanium (IV) isopropoxide (TTIP) and a non-oxygen plasma. In some embodiments, TTIP is used in the PEALD method in combination with a plasma generated in Ar, a plasma generated in a gas containing Ar and nitrogen, or a plasma generated in a gas containing Ar and hydrogen. In some embodiments, a titanium oxide film containing carbon is deposited by a PEALD method, wherein a titanium reactant such as TTIP is used in combination with a plasma generated in an inert gas (e.g., in pure Ar gas). The amount of carbon can be adjusted by changing the plasma power. In some embodiments, a titanium oxide film containing carbon and nitrogen (TiO(CN)) is deposited using a titanium reactant such as TTIP and a plasma generated in a gas containing nitrogen (e.g., in a gas containing Ar and N 2 The deposition is carried out by the PEALD method using a combination of plasma generated in a gas (gas).

[0228] Example

[0229] Using 3-methoxypropyltrimethoxysilane (MPTMS) and H 2 Experiments were performed at 200 and 125 °C in a SiOC PEALD process with Ar / Ar plasma. Natox, W and Cu were used as surfaces to study the selectivity. 25, 50 and 200 cycles were applied, after which XPS spectra were recorded. Figure 2 shows that there is more Si on W than on Cu at both temperatures. After 100 cycles at 200 °C, no Si was detected on Cu. This selectivity can also be achieved between natox and Cu.

[0230] SiOC was also deposited on a substrate containing a polyimide passivation layer on a substrate containing Cu and a low-k surface. SiOC was deposited from MPTMS and H2 plasma and formed a SiOC film with a carbon concentration of less than 10 at%. The plasma was provided for 0.5 seconds at a power of 67 or 300 watts. A pressure of 4.7 torr was used. Figure 3 and 4 As shown in , SiOC growth is observed on the low-k surface but not on the Cu surface at both power settings.

[0231] In other experiments, SiOC was deposited by PEALD from MPTMS and H2 / Ar plasma at deposition temperatures between 200°C and 300°C. 2The flow rate was 0.1 to 0.4 slpm (above 2 slpm Ar co-flow) and the plasma power was 30 to 100 W. SiOC films were deposited on silicon substrates containing chemical oxides as well as TiN and W surfaces. On silicon oxide, the process conditions can be adjusted to produce SiOC films with very low k values ​​(<3.5) and very low wet etch rates (<1 nm / min in dHF 0.7%). The minimum k value and wet etch rate were observed using a 0.2 slpm H2 flow rate and 70 W power at about 300°C. Under such conditions, the deposited SiOC layer was found to have a k value of about 4 and a wet etch rate of 1 nm / min. It was also observed that the deposition of SiOC was selective to a variety of materials, including W and TiN. After 500 cycles, the process produced less than 1 nm on W but no wet etch rates on SiO 2 A film of about 10.5 nm is formed on the surface of the substrate.

[0232] It was also observed that lower temperatures enhanced the growth of SiOC on TiN, as can be seen in Table 1 below. About 6.3 nm of SiOC was deposited on TiN with 500 cycles at 200 °C, while almost no growth was seen on TiN with 500 cycles at 300 °C. In contrast, about 6.3 nm of SiOC was deposited on TiN with 500 cycles at 200 °C. 2 About 10 nm of SiOC was deposited on the 400nm TiO2 substrate and about 5.5 nm at 300 °C.

[0233] Deposition temperature TiN Natural oxides 300℃ ~1nm / 500 cycles ~5.5nm / 500 cycles 200℃ ~6.5nm / 500 cycles ~10nm / 500 cycles

[0234] Table 2

[0235] Titanium oxide thin films were deposited in a direct plasma PEALD reactor by an oxygen-free PEALD process using titanium (IV) isopropoxide (TTIP) as a titanium precursor. TTIP was provided by a source bottle heated at 70°C. The TTIP reactant was provided alternately and sequentially with three different plasma reactants. 2 and Ar and H 2 The plasma was generated in the experiment. The deposition temperature was 200 °C. Figure 5A The refractive index of the obtained film is shown. 2 For plasma, the refractive index is very close to that of TiO 2 However, N 2 plasma and pure Ar plasma show different refractive indices, indicating different film compositions. Figure 5B The growth rates of titanium oxide films using three different plasma reactants are shown.

[0236] Table 3 below shows the composition data from RBS and XPS. Both XPS and RBS indicate that the 2Plasma deposited TiO 2 The XRD measurement showed no crystal structure. This indicated that amorphous TiO 2 The wet etch rate ratio (WERR) relative to thermal silicon oxide (TOX) in 0.5% dHF solution is about 0.5. This low WERR makes the film useful for certain patterning applications. Four-point probe resistivity measurements show that the deposited TiO 2 The film has an extremely high resistivity.

[0237] When pure Ar plasma is used as the plasma reactant, the resulting film is a carbon-rich TiOC film. The carbon content can be modified by adjusting the plasma power. 2 The plasma introduces nitrogen into the film, thereby producing a TiOCN film.

[0238] TTIP+AR plasma

[0239] Ti(%) O(％) C(％) N(％) RBS 5.6 12.5 81.9 - XPS 4.3 14.0 81.7 -

[0240] TTIP+AR&H plasma

[0241] Ti(%) O(％) C(％) N(％) RBS 35 65 - - XPS 33.9 66.1

[0242] TTIP+AR&N Plasma

[0243] Ti(%) O(％) C(％) N(％) RBS 9.6 21.5 34.2 34.7 XPS 9.2 20.8 28.9 36.1

[0244] Table 3

[0245] Those skilled in the art will appreciate that many and various modifications may be made without departing from the spirit of the present invention. The features, structures, characteristics and precursors may be combined in any suitable manner. Therefore, it should be clearly understood that the form of the present invention is merely illustrative and is not intended to limit the scope of the present invention. It is hoped that all modifications and variations fall within the scope of the present invention, as defined in the appended claims.

Claims

1. A plasma enhanced atomic layer deposition (PEALD) method for selectively depositing a metal oxide on a dielectric surface of a substrate relative to a metal surface of the substrate, the dielectric surface comprising a low-k material, the method comprising: performing at least one deposition cycle comprising contacting the substrate first with a first metal precursor and then contacting the substrate with a second reactant comprising reactive species from a plasma generated in a gas comprising hydrogen but not oxygen, The second reactant reacts with the metal surface to remove oxygen from the metal surface.

2. The method according to claim 1, wherein the metal oxide is selected from the group consisting of Al2O3, Nb2O5, Ta2O5, TiO2, TiO(CN), and WOx.

3. The method according to claim 1, wherein the first metal precursor has the formula M(OR I ) x-y R II y , where R I is a hydrocarbon, M is a metal, and R II are ligands containing carbon, hydrogen, nitrogen, halogens and / or oxygen. 4 . The method of claim 1 , wherein removing oxygen from the metal surface comprises removing OH-groups or oxygen bridges from the metal surface.

5. The method of claim 1, wherein the dielectric surface comprises SiO2.

6. The method of claim 1, wherein the second reactant is formed by generating a plasma in a gas comprising H2 and Ar.

7. The method of claim 1, further comprising contacting the substrate with a third plasma reactant prior to initiating the deposition cycle.

8. The method of claim 1, wherein the deposition cycle is repeated 2 or more times to form the metal oxide film of a desired thickness on the dielectric surface.

9. The method of claim 1, wherein the metal surface comprises Ru, Co, W, TiN, Cu, TaN, or Ta.

10. The method of claim 1, wherein the metal surface comprises a passivation layer. The method according to claim 10 , wherein the passivation layer is an organic passivation layer.

12. The method of claim 11, wherein the organic passivation layer is selectively deposited on the metal surface relative to the dielectric surface prior to initiating the first deposition cycle.

13. A method for selectively depositing a metal oxide thin film on a first surface of a substrate relative to a second surface of the substrate by a plasma enhanced atomic layer deposition (PEALD) method, wherein the second surface is different from the first surface, the method comprising: The substrate is first contacted with a first reactant and then contacted with a second reactant comprising a plasma generated in a gas comprising hydrogen but not oxygen, wherein the second reactant reacts with the metal surface to remove oxygen from the metal surface.

14. The method of claim 13, wherein the second reactant is formed by generating a plasma in a gas comprising H2 and Ar.

15. The method of claim 13, wherein the first surface is a dielectric surface.

16. The method of claim 13, wherein the second surface comprises Co, W, TiN, Cu, TaN5, or Ta.

17. The method of claim 16, wherein the second surface comprises a metal nitride surface.

18. A plasma enhanced atomic layer deposition (PEALD) method for depositing an oxide selectively on a dielectric surface of a substrate comprising a low-k material relative to a TiN surface of the substrate, the method comprising: At least one deposition cycle is performed, the at least one deposition cycle comprising alternatingly and sequentially contacting the substrate with a first precursor comprising oxygen and an oxide component and a second reactant comprising reactive species from a plasma generated in a gas comprising hydrogen but not oxygen.

19. The method according to claim 18, wherein the oxide is selected from SiOCN, SiOSC, SiO2, SiOC, Al2O3, Nb2O5, Ta2O5, TiO2, TiO(CN), WOx.

20. The method of claim 18, wherein the first precursor has the formula M(OR I ) x-y R II y , where R I is a hydrocarbon, M is a metal, and R II are ligands containing carbon, hydrogen, nitrogen, halogens and / or oxygen.

21. The method of claim 18, wherein the first precursor comprises 3-methoxypropyltrimethoxysilane (MPTMS).

22. The method of claim 18, wherein the second reactant reacts with the TiN surface to reduce any metal oxide on the surface.

23. The method of claim 18, wherein the second reactant reacts with the TiN surface to remove oxygen from the surface.

24. The method of claim 23, wherein removing oxygen from the TiN surface comprises removing OH-groups or oxygen bridges from the TiN surface.

25. The method of claim 18, wherein the dielectric surface comprises SiO2.

26. The method of claim 18, wherein the second reactant is formed by generating a plasma in a gas comprising H2 and Ar.

27. The method of claim 18, wherein the deposition cycle begins by contacting the substrate with the second reactant.

28. The method of claim 18, further comprising contacting the substrate with a third plasma reactant prior to initiating the deposition cycle.

29. The method of claim 18, wherein the deposition cycle is repeated 2 or more times to form a desired thickness of oxide on the dielectric surface.

30. The method of claim 18, wherein the TiN surface comprises a passivation layer.

31. The method of claim 30, wherein the passivation layer is an organic passivation layer.

32. The method of claim 31 , wherein the organic passivation layer is deposited selectively on the TiN surface relative to the dielectric surface prior to initiating a first deposition cycle.

33. A method for depositing an oxide film selectively on a dielectric surface of a substrate relative to a TiN surface of the substrate by a plasma enhanced atomic layer deposition (PEALD) method, the dielectric surface comprising a low-k material, the method comprising: The substrate is contacted alternately and sequentially with a first reactant and a second reactant, wherein the second reactant comprises a plasma generated in a gas comprising hydrogen but not oxygen.

34. The method of claim 33, wherein the second reactant is formed by generating a plasma in a gas comprising H2 and Ar.

35. The method of claim 33, wherein the thin film comprises an oxide.

36. The method of claim 35, wherein the oxide is selected from SiOCN, SiOSC, SiOC, SiO2, Al2O3, Nb2O5, Ta2O5, TiO2, TiO(CN), WOx.

37. A plasma enhanced atomic layer deposition (PEALD) method for depositing an oxide selectively on a dielectric surface of a substrate relative to a TiN surface, the method comprising: providing a substrate including a dielectric surface and a TiN surface, the dielectric surface comprising a low-k material; At least one deposition cycle is performed that includes alternatingly and sequentially contacting the substrate with a first silicon precursor comprising oxygen and a second reactant comprising reactive species from a plasma generated in a gas comprising hydrogen but not oxygen.

38. The method of claim 37, wherein the first silicon precursor is adsorbed on the substrate surface and the second reactant reacts with the adsorbed first silicon precursor to form an oxide selectively on the dielectric surface relative to the TiN surface.

39. The method of claim 38, wherein the second reactant also reacts with the TiN surface to reduce any metal oxide on the TiN surface.

40. The method of claim 38, wherein the second reactant further reacts with the TiN surface to remove oxygen from the TiN surface.

41. The method of claim 40, wherein removing oxygen from the TiN surface comprises removing OH-groups or oxygen bridges from the TiN surface.

42. The method of claim 37, wherein the dielectric surface comprises SiO2.

43. The method of claim 37, wherein the oxide is SiO2, SiOC or SiOCN.

44. The method of claim 37, wherein the oxide comprises metal and silicon.

45. The method of claim 37, wherein the first silicon precursor comprises 3-methoxypropyltrimethoxysilane (MPTMS).

46. ​​The method of claim 37, wherein the deposition cycle begins by contacting the substrate with the second reactant.

47. The method of claim 37, additionally comprising contacting the substrate with a third plasma reactant prior to initiating the deposition cycle.

48. The method of claim 37, wherein the deposition cycle is repeated 2 or more times to form a desired thickness of the oxide film on the dielectric surface.

49. The method of claim 37, wherein the TiN surface comprises a passivation layer.

50. The method of claim 49, wherein the passivation layer is an organic passivation layer.

51. The method of claim 50, wherein the organic passivation layer is deposited selectively on the TiN surface relative to the dielectric surface prior to initiating a first deposition cycle.

52. A method for selectively depositing a SiOC film on a dielectric surface of a substrate relative to a metal nitride surface of the substrate by a plasma enhanced atomic layer deposition (PEALD) method, the method comprising: The substrate is contacted alternately and sequentially with a first reactant comprising silicon and oxygen and a second reactant comprising a plasma generated in a gas comprising hydrogen but not oxygen.

53. The method of claim 52, wherein the second reactant is formed by generating a plasma in a gas comprising H2 and Ar.

54. The method of claim 53, wherein the metal nitride surface comprises TiN or TaN.

55. A plasma enhanced atomic layer deposition (PEALD) method for selectively depositing an oxide on a dielectric surface of a substrate, the method comprising: providing a substrate including a first dielectric surface and a second metal surface, the first dielectric surface comprising a low-k material; performing at least one deposition cycle comprising first contacting the substrate with a first silicon precursor comprising oxygen and then contacting the substrate with a second reactant comprising reactive species from a plasma generated in a gas comprising hydrogen but not oxygen; wherein the first silicon precursor is adsorbed on the substrate surface and the second reactant reacts with the adsorbed first silicon precursor to selectively form an oxide on the first dielectric surface relative to the second metal surface; and The second reactant reacts with the second metal surface to remove oxygen from the second metal surface.

56. The method of claim 55, wherein the second reactant also reacts with the second metal surface to reduce any metal oxide on the second metal surface.

57. The method of claim 55, wherein removing oxygen from the metal surface comprises removing OH-groups or oxygen bridges from the second metal surface.

58. The method of claim 55, wherein the dielectric surface comprises SiO2.

59. The method of claim 55, wherein the metal surface comprises Ru, Co, Cu, or W.

60. The method of claim 55, wherein the metal surface comprises TiN.

61. The method of claim 55, wherein the oxide is SiO2, SiOC, or SiOCN.

62. The method of claim 55, wherein the oxide comprises metal and silicon.

63. The method of claim 60, wherein the first silicon precursor comprises 3-methoxypropyltrimethoxysilane (MPTMS).

64. The method of claim 55, additionally comprising contacting the substrate with a third plasma reactant prior to initiating the deposition cycle.

65. The method of claim 55, wherein the deposition cycle is repeated 2 or more times to form an oxide film of a desired thickness on the dielectric surface.

66. The method of claim 55, wherein the metal surface comprises a passivation layer.

67. The method of claim 66, wherein the passivation layer is an organic passivation layer.

68. The method of claim 67, wherein the organic passivation layer is selectively deposited on the second metal surface relative to the dielectric surface prior to initiating the first deposition cycle.

69. The method of claim 66, wherein during each deposition cycle, the passivation layer is etched by a second plasma reactant.

70. A method for selectively depositing a SiOC film on a dielectric surface of a substrate relative to a metal surface of the substrate by a plasma enhanced atomic layer deposition (PEALD) method, the method comprising: The substrate is first contacted with a first reactant comprising silicon and oxygen, and then contacted with a second reactant comprising a plasma generated in a gas comprising hydrogen but not oxygen, wherein the second reactant reacts with the metal surface to remove oxygen from the metal surface.

71. The method of claim 70, wherein the second reactant is formed by generating a plasma in a gas comprising H2 and Ar.

72. The method of claim 71, wherein the plasma is generated using a power of 30 to 200 W.

73. The method of claim 70, wherein the plasma enhanced atomic layer deposition (PEALD) method is performed at a deposition temperature of 50 to 300°C.

74. The method of claim 70, wherein the metal surface comprises Co, Ru, Ni, W, TiN, Cu, or Ta.

Images