Multilayer silicon nitride membrane

Abstract

A method of depositing a multi-layer silicon nitride film includes placing a substrate in a first reactor and depositing a first silicon nitride film, a second silicon nitride film, and a third silicon nitride film on at least a portion of a surface of the substrate using a sequence of deposition methods by alternating between either (i) plasma enhanced atomic layer deposition (PEALD) or plasma enhanced cyclic chemical vapor deposition (PECCVD), and (ii) PECVD, as described herein, and at least one silicon precursor compound having at least three Si-N bonds and at least three SiH groups, represented by formulas A-C, as described herein, which together form a multi-layer silicon nitride film.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This patent application claims priority to U.S. Provisional Application No. 63 / 279,623, filed November 15, 2021, which is incorporated herein by reference in its entirety. [Background technology]

[0002] Silicon nitride is often used as an insulator and passivation / gas barrier in the manufacture of integrated circuits and display devices, to electrically isolate different structures, or as an etching mask in bulk micromachining. As a passivation layer for microchips, silicon nitride is superior to silicon dioxide because it is a significantly better diffusion barrier to water molecules and sodium ions, two major causes of corrosion and instability in microelectronics. Silicon nitride is also used as a dielectric between polysilicon layers of capacitors in analog chips.

[0003] Deposition of conformal, stoichiometric, and non-stoichiometric silicon nitride films at low temperatures, e.g., below about 500° C., or below about 400° C., that meet one or more criteria for being considered high quality films has been a long-standing industry challenge. There are several applications in the semiconductor field, e.g., advanced patterning and spacers, that require high quality films. A silicon nitride film is considered to be a "high quality" film compared to other silicon nitride films if it has a density of 2.0 grams per cubic centimeter (g / cc) and / or a low wet etch rate (measured in dilute hydrofluoric acid (HF)). In these or other embodiments, the refractive index of the silicon nitride film must be 1.8 or greater.

[0004] Bang, S.H. et al., "SiO Deposited by Inductively Coupled Plasma Chemical Vapor Deposition" x N y"Effect of Radio Frequency Power and Gas Ratio on the Barrier Properties of the Films," Thin Solid Films 669, p.108-113 (2019) describes SiO deposited at a low temperature of -23 °C using inductively coupled plasma chemical vapor deposition (ICP-CVD). x N y Barrier films have been disclosed in which isolated, nearly spherical nanoparticles without agglomeration were observed. Such non-agglomerated, nearly spherical nanoparticles produced dense films with improved barrier properties. However, severely agglomerated nanoparticles produced very porous films with reduced barrier properties.

[0005] Cho, SK et al., "Structure and gas barrier properties of hydrogenated silicon nitride prepared by roll-to-roll microwave plasma enhanced chemical vapor deposition," Vacuum 188, p. 110167 (2021) describes the development of hydrogenated amorphous silicon nitride films (a-SiN x It has been disclosed that SiH acts as a barrier layer to prevent the diffusion of water vapor and other gases into electronic devices. 4 The film, produced under enriched conditions (R<2.75), was oxidized to silicon oxynitride (SiO x N y ), the properties of which are similar to those of silicon nitride (SiN x It was found that the gas barrier properties were affected by both the film and the density of Si-H bonds. x The compressive and tensile stresses of the :H film depend on the value of R, and excellent mechanical stability and moisture barrier properties are obtained when R is 2.75 to 3.00.

[0006] US Patent No. 8,592,328 discloses a method for producing silicon nitride (SiN) films. One embodiment relates to the deposition of chlorine (Cl)-free conformal SiN films. In some embodiments, the SiN films are Cl-free and carbon (C)-free. Other embodiments relate to methods for adjusting the stress and / or wet etch rate of conformal SiN films. Other embodiments relate to methods for low temperature deposition of high quality conformal SiN films. In some embodiments, the methods include using trisilylamine (TSA) as a silicon-containing precursor.

[0007] Jang, W. et al., "Temperature Dependence of Silicon Nitride Deposited by Remote Plasma Atomic Layer Deposition," Physica Status Solidi (A) Applications and Materials Science 211, p. 2166 (2014), describes the deposition of trisilylamine (TSA) and ammonia (NH 3 The characteristics of silicon nitride thin films deposited by remote plasma atomic layer deposition (RPALD) at low temperatures using a .) plasma are disclosed. SiN deposited at 250-350 °C x The thin film is focused for analysis. x All of the films were nearly stoichiometric, regardless of deposition temperature. With increasing deposition temperature, the RI increased while the hydrogen content decreased. The defect density also changed at higher deposition temperatures, with the SiN x All trap densities increased due to the low hydrogen content in the films. SiN deposited by RPALD x The film characteristics could be controlled to tune the defect density for charge trapping flash memory applications by varying the deposition temperature.

[0008] US Patent No. 8,129,291, US Patent No. 8,173,554 and US Patent No. 8,415,259 disclose a method for forming a dielectric film having Si-N bonds on a semiconductor substrate by plasma enhanced atomic layer deposition (PEALD). The method includes introducing a nitrogen-containing reactive gas and a hydrogen-containing reactive gas and a noble gas into a reaction space in which a semiconductor substrate is disposed, introducing a hydrogen-containing silicon precursor into the reaction space in a pulse having a duration of less than 1.0 seconds into which the reactive gas and the noble gas are introduced, exiting the plasma in a pulse having a duration of less than 1.0 seconds immediately after the silicon precursor is stopped, and maintaining the reactive gas and the noble gas as a purge having a duration of less than 2.0 seconds.

[0009] Lee, WJ et al., "Novel Plasma Enhanced Chemical Vapor Deposition of Highly Conformal SiN Films and Their Barrier Properties," Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurements, and Phenomena, 36(2), p.022201 (2018), discloses a plasma enhanced chemical vapor deposition technique for producing highly conformal silicon nitride (SiN) films and a study of their barrier properties. TSA is used as the main precursor and is introduced in a 0.3 second pulse into the reaction chamber while the plasma is excited. The deposited SiN films show good conformality (91%) and an aspect ratio of about 4.2 (70 nm width and 300 nm depth). The growth rate of the film was 2.0 Å / cycle. The k value and leakage current are 7.1-6.66 and 1.0 × 10, respectively, at a charge of 1 MV in the temperature range of 200-400 °C. -8 A / cm 2 The wet etch rates of the SiN deposit at 200 and 400 °C were 32.1 and 11.1 nm / min, respectively. The wet etch rates of this film were 100% with a dilute hydrogen fluoride (HF) solution (H 2The properties of the SiN films were evaluated in a 100:1 mixture of 1,2-dichloroethane (HO) and 1,2-dichloroethane (HF) at 200°C and 400°C. The 5.0-nm-thick SiN films deposited at 200°C and 400°C showed excellent ability to prevent moisture ingress. By modifying the Si precursor delivery method, the coverage of this process was improved to the level of plasma-enhanced atomic layer deposition, and the moisture barrier properties were maintained even at thicknesses below 10 nm.

[0010] US Patent Application Publication No. 2017 / 0088684 discloses a gas barrier laminate with excellent gas barrier properties and flex resistance. The gas barrier laminate includes a substrate having a base material and a modification-promoting layer, and a gas barrier layer formed on the modification-promoting layer side of the substrate. The gas barrier laminate has a modification-promoting layer with an elastic modulus of <30 GPa and a gas barrier strength of ≦1.0 g / (m2) at a substrate temperature of 40° C. and a relative humidity of 90%. 2 The gas barrier layer has a water vapor permeability of 100-150%. This gas barrier layer is formed by carrying out a modification process on the surface of a layer containing a polysilazane compound that is formed on the modification-promoting layer side of the substrate.

[0011] Yun, SJ et al., "Water vapor transmission rate property of SiNx thin films prepared by low temperature (<100°C) linear plasma enhanced chemical vapor deposition." Vacuum 148, p.33-40 (2018) discloses an in-line system with a linear PECVD source that can be used at low temperatures for thin film encapsulation of flexible organic light-emitting diode displays. This in-line system can be used to coat moving substrates, can improve productivity better than cluster systems with typical PECVD sources, and can produce SiNx films with excellent water vapor barrier properties. x A film can be formed.

[0012] U.S. Pat. No. 1,031,6407 discloses compositions and methods of using same for forming silicon-containing films or materials, such as, but not limited to, silicon oxide, silicon nitride, silicon oxynitride, carbon-doped silicon nitride, or carbon-doped silicon oxide films, using a single deposition process, such as plasma-enhanced atomic layer deposition (PEALD) or plasma-enhanced cyclic chemical vapor deposition (PECCVD). Summary of the Invention [Problem to be solved by the invention]

[0013] There is a need in the art to provide thin, gas barrier silicon nitride materials. In particular, there is a need for a low temperature (e.g., processing temperature of about 500° C. or less, preferably 300° C. or less, more preferably 200° C. or less, and most preferably 100° C. or less) method for depositing conformal, high quality, silicon nitride films that have one or more of the following characteristics compared to other silicon nitride films using other deposition methods or precursors: a refractive index of 1.8 or greater, a low wet etch rate of 1 Å / sec or less (measured in dilute hydrogen fluoride (HF)), a 5.0×10 -5 g / m 2 ·Days or less, 5.0×10 -4 g / m 2 · days or less, or 5.0 x 10 -3 g / m 2 · Water Vapor Transmission Rate (WVTR) and combinations thereof. [Means for solving the problem]

[0014] Described herein is a method for forming a stoichiometric or non-stoichiometric multi-layer silicon nitride film, such as a multi-layer silicon nitride, as a gas barrier in a semiconductor device. According to an exemplary embodiment, the method for depositing a multi-layer silicon nitride film uses a combination of deposition methods and includes depositing at least a first silicon nitride film, a second silicon nitride film, and a third silicon nitride film on at least a portion of a substrate surface in a sequence of alternating deposition methods between (1) either plasma enhanced atomic layer deposition (PEALD) or plasma enhanced cyclic chemical vapor deposition (PECCVD) and (2) plasma enhanced chemical vapor deposition (PECVD), which together form a multi-layer silicon nitride film, and the PEALD or PECCVD deposition method (1) includes the following steps a to e, which are repeated until a desired thickness of silicon nitride is obtained. a. placing a substrate in a first reactor. b. in a reactor, reacting at least three SiN bonds and at least three SiH bonds under conditions sufficient to react on at least a portion of the surface to provide a chemisorbed layer; 3 introducing at least one silicon precursor represented by formulae A-C having a group; [ka] In the formula, R is independently hydrogen, linear C 1 ~C 10 Alkyl group, branched C 3 ~C 10 Alkyl group, linear or branched C 3 ~C 12 Alkenyl group, linear or branched C 3 ~C 12 Alkenyl group, linear or branched C 3 ~C 12 Alkynyl group, C 4 ~C 10 Cyclic alkyl groups, and C 6 ~C 10 aryl groups. c. purging the reactor with a purge gas. d. introducing a first plasma-containing source into the reactor to react with at least a portion of the chemisorption layer and provide at least one reaction site where the plasma is about 0.01 to about 1.5 W / cm 2 The process is generated at power densities in the range of e. optionally purging the reactor with an inert gas; and the PECVD deposition method (2) includes the following steps f through g. f. placing the substrate in a second reactor. g. introducing into the reactor at least one silicon precursor represented by Structures A-C, and a second plasma-containing source to form silicon nitride, wherein the plasma is from about 0.01 to about 1.5 W / cm 2 The power densities are generated in the range of DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Deposition of conformal, stoichiometric and non-stoichiometric silicon nitride films at low temperatures (e.g., 500° C. or less, or 400° C. or less, or 200° C. or less, or 100° C. or less) that meet one or more criteria to be considered a high quality film has been a long-standing industry challenge. Throughout this description, the term "silicon nitride" as used herein refers to a film comprising silicon and nitrogen selected from the group consisting of stoichiometric or non-stoichiometric silicon nitrides and mixtures thereof. A silicon nitride film is considered to be "high quality" if it has one or more of the following characteristics: density of 2.0 grams per cubic centimeter (g / cc) or more, low wet etch rate of 1 Å / sec or less (measured in dilute hydrofluoric acid (HF)), and combinations thereof. In these or other embodiments, the refractive index of the silicon nitride film should be 1.8 or more.

[0016] Throughout this description, the term "alkyl" refers to a straight or branched functional group having 1 to 10 carbon atoms. Exemplary alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl groups. Exemplary branched alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, sec-pentyl, tert-pentyl, isohexyl, sec-hexyl, tert-hexyl, and neohexyl. In certain embodiments, the alkyl groups can have one or more functional groups attached thereto, such as, but not limited to, an alkoxy group, a dialkylamino group, or a combination thereof attached thereto. In other embodiments, the alkyl groups do not have one or more functional groups attached thereto. These alkyl groups can be saturated or unsaturated.

[0017] As used throughout this description, the term "cyclic alkyl" refers to a cyclic functional group having 3 to 10 carbon atoms. Exemplary cyclic alkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

[0018] Throughout this description, the term "alkenyl group" denotes a group having one or more carbon-carbon double bonds and 2 to 10 or 2 to 6 carbon atoms.

[0019] Throughout this description, the terms "dialkylamino", "alkylamino" or "organoamino" refer to groups having two alkyl groups attached to the nitrogen atom or one alkyl group attached to the nitrogen atom and having 1-10, or 2-6, or 2-4 carbon atoms. Examples include, but are not limited to, HNMe, HNBu. t , NMe 2 , NMeEt, NEt 2 , and NPr i 2 Examples include:

[0020] As used throughout this description, the term "aryl" refers to an aromatic cyclic functional group having 4 to 10 carbon atoms, 5 to 10 carbon atoms, or 6 to 10 carbon atoms. Exemplary aryl groups include phenyl, 1-phenylethyl (Ph(Me)CH-), 1-phenyl-1-methyl-ethyl (Ph(Me)CH-). 2 C-), benzyl, chlorobenzyl, tolyl, o-xylyl, 1,2,3-triazolyl, pyrrolyl, and furanyl.

[0021] Throughout this description, the term "heteroatom functional group" refers to a linear or branched C 1 -C 2 -O 3 -C 1 -O 3 ... 1 ~C 20 Hydrocarbons, cyclic C 6 ~C 20 represents a hydrocarbon. Exemplary heteroatom functional groups include, but are not limited to, alkoxy, organoamino, cyano, thio, silyl, ether, keto, ester, or halogenated groups or combinations thereof.

[0022] Throughout this description, the term "water vapor transmission rate (WVTR)" refers to the rate at which water molecules permeate a barrier layer and is expressed in g / m 2 / day(g / m 2 -Days).

[0023] Throughout this description, the term "multilayer silicon nitride film" refers to three or more layers of silicon nitride deposited by alternating between (1) plasma enhanced atomic layer deposition (PEALD) or plasma enhanced cyclic chemical vapor deposition (PECCVD), and (2) PECVD.

[0024] In one embodiment of the presently disclosed and claimed subject matter, the present invention relates to a method for depositing a multi-layer silicon nitride by plasma enhanced atomic layer deposition (PEALD) or a combination of plasma enhanced cyclic chemical vapor deposition (PECCVD) and plasma enhanced chemical vapor deposition (PECVD) using one or more of the following silicon precursors: [ka] In the formula, R is hydrogen, linear C 1 ~C 10 Alkyl group, branched C 3 ~C 10 Alkyl group, C 3 ~C 10 Cyclic alkyl groups, C 3 ~C 10 Heterocyclic groups, C 3 ~C 10 Alkenyl group, C 3 ~C 10 Alkynyl groups, and C 4 ~C 10 aryl groups.

[0025] In one embodiment, a method is provided for forming a multi-layer silicon nitride film by a combination of (1) plasma enhanced atomic layer deposition (PEALD) or plasma enhanced cyclic chemical vapor deposition (PECCVD) and (2) plasma enhanced chemical vapor deposition (PECVD). According to this embodiment, the multi-layer silicon nitride comprises a PEALD or PECCVD silicon nitride / PECVD silicon nitride / PEALD or PECCVD silicon nitride film. The steps of the method are described below.

[0026] (1): The PEALD or PECCVD method includes the following steps a to e. a. Providing a substrate in a reactor. b. In a reactor, there are provided at least three Si—N bonds and at least three SiH 3 Introducing at least one silicon precursor having a group. [ka] In the formula, R is hydrogen, linear C 1 ~C 10 Alkyl group, branched C 3 ~C 10 Alkyl group, C 3 ~C 10 Cyclic alkyl groups, C 3 ~C 10 Heterocyclic groups, C 3 ~C 10 Alkenyl group, C 3 ~C 10 Alkynyl groups, and C 4 ~C 10 An aryl group is selected and at least one silicon precursor is reacted on at least a portion of the surface of the substrate to provide a chemisorbed layer. c. purging the reactor with a purge gas. d. introducing a plasma-containing source into the reactor to react with at least a portion of the chemisorption layer and provide at least one reaction site where the plasma is at about 0.01 to about 1.5 W / cm 2 The process is generated at power densities in the range of e. Optionally, purging the reactor with an inert gas. Here, steps b-e are repeated until the desired thickness of the silicon nitride film is obtained. A flow of argon, noble gas and / or other inert gas can be used as a carrier gas to assist in the delivery of at least one silicon precursor to the reaction chamber during the precursor pulse. In certain embodiments, the process pressure of the reaction chamber is about 2 Torr or less. In other embodiments, the process pressure of the reaction chamber is about 10 Torr or less. In certain embodiments of the method, a hydrogen-containing plasma can be inserted before step d to assist in removing hydrocarbons generated from the reaction between silicon and the surface. The hydrogen-containing plasma is selected from the group consisting of hydrogen plasma, hydrogen / helium, hydrogen / argon plasma, hydrogen / neon plasma and mixtures thereof. In some embodiments, the plasma-containing source can be introduced into the reactor in the form of at least one nitrogen source and / or can be incidentally present in other precursors used in the deposition process. Suitable nitrogen-containing source gases include, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen plasma, nitrogen / hydrogen, nitrogen / helium, nitrogen / argon plasma, ammonia plasma, nitrogen / ammonia plasma, ammonia / helium plasma, ammonia / argon plasma, ammonia / nitrogen plasma, NF 3 In another embodiment, the plasma is selected from the group consisting of a hydrogen plasma, a helium plasma, a neon plasma, an argon plasma, a xenon plasma, a hydrogen / helium plasma, a hydrogen / argon plasma, and mixtures thereof.

[0027] (2) The PECVD method includes the following steps a to b. a. providing a substrate having silicon nitride prepared by PEALD from step (1) in a reactor; b. At least three Si-N bonds and at least three SiH bonds, represented by the structure 3 at least one silicon precursor having a group; [ka] In the formula, R is hydrogen, linear C 1 ~C 10 Alkyl group, branched C 3 ~C 10 Alkyl group, C 3 ~C 10 Cyclic alkyl groups, C 3 ~C 10 Heterocyclic groups, C 3 ~C 10 Alkenyl group, C 3 ~C 10 Alkynyl groups, and C 4 ~C 10 aryl groups, and a nitrogen source are simultaneously introduced into the reactor under a direct plasma to form silicon nitride, where the plasma has an electric field of about 0.01 to about 1.5 W / cm 2 Suitable nitrogen-containing source gases can include, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen / hydrogen, nitrogen / helium, and mixtures thereof.

[0028] Step (3): The PEALD or PECCVD method includes the following steps: a. providing a substrate having silicon nitride prepared by PECVD from step (2) in a reactor; b. At least three Si-N bonds and at least three SiH bonds represented by the structure 3 introducing at least one silicon precursor having a group; [ka] In the formula, R is hydrogen, linear C 1 ~C 10 Alkyl group, branched C 3 ~C 10 Alkyl group, C 3 ~C 10 Cyclic alkyl groups, C 3 ~C 10 Heterocyclic groups, C 3 ~C 10 Alkenyl group, C3 ~C 10 Alkynyl groups, and C 4 ~C 10 aryl groups, and reacting at least one silicon precursor on at least a portion of the surface of the substrate to provide a chemisorbed layer; c. purging the reactor with a purge gas; d. introducing a plasma containing source into the reactor to react with at least a portion of the chemisorbed layer and provide at least one reaction site, the plasma being from about 0.01 to about 1.5 W / cm 2 and e. optionally purging the reactor with an inert gas; Here, steps b to e are repeated until a desired thickness of the silicon nitride film is obtained.

[0029] In another aspect, a method for forming a multi-layer silicon nitride film by a combination of plasma enhanced atomic layer deposition and plasma enhanced cyclic chemical vapor deposition is provided, the multi-layer silicon nitride including a PECVD silicon nitride / PEALD or PECCVD silicon nitride / PECVD silicon nitride film, the method including steps (1)-(3) as follows:

[0030] Step (1): The PECVD method includes the following steps. a. providing a substrate in a reactor; and b. At least three Si-N bonds and at least three SiH bonds, represented by the structure 3 at least one silicon precursor having a group; [ka] In the formula, R is hydrogen, linear C 1 ~C 10 Alkyl group, branched C 3 ~C 10 Alkyl group, C 3 ~C 10 Cyclic alkyl groups, C 3 ~C 10Heterocyclic groups, C 3 ~C 10 Alkenyl group, C 3 ~C 10 Alkynyl groups, and C 4 ~C 10 aryl groups, and a nitrogen source are simultaneously introduced into the reactor under a direct plasma to form silicon nitride, the plasma having a flow rate of about 0.01 to about 1.5 W / cm 2 Suitable nitrogen-containing source gases can include, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen / hydrogen, nitrogen / helium, and mixtures thereof.

[0031] Step (2): PEALD or PECCVD includes the following steps: a. providing a substrate having silicon nitride prepared by PECVD from step (1) in a reactor; b. At least three Si-N bonds and at least three SiH bonds, represented by the structure 3 introducing at least one silicon precursor having a group into a reactor; [ka] In the formula, R is hydrogen, linear C 1 ~C 10 Alkyl group, branched C 3 ~C 10 Alkyl group, C 3 ~C 10 Cyclic alkyl groups, C 3 ~C 10 Heterocyclic groups, C 3 ~C 10 Alkenyl group, C 3 ~C 10 Alkynyl groups, and C 4 ~C 10 aryl groups, and reacting the at least one silicon precursor on at least a portion of a surface of the substrate to provide a chemisorbed layer; c. purging the reactor with a purge gas; d. introducing a plasma containing source into the reactor to react with at least a portion of the chemisorbed layer to provide at least one reaction site, the plasma having a density of about 0.01 to about 1.5 W / cm 2 and e. optionally purging the reactive group with an inert gas; Here, steps b-e are repeated until the desired thickness of the silicon nitride film is obtained. A flow of argon gas, noble gas and / or other inert gas can be used as a carrier gas to assist in the delivery of at least one silicon precursor vapor to the reaction chamber during the precursor pulse. In certain embodiments, the process pressure of the reaction chamber is about 2 Torr or less. In other embodiments, the process pressure of the reaction chamber is about 10 Torr or less. In certain embodiments of the method, a hydrogen-containing plasma can be inserted before step d to assist in removing hydrocarbons generated from the reaction between silicon and the surface. The hydrogen-containing plasma is selected from the group consisting of hydrogen plasma, hydrogen / helium, hydrogen / argon plasma, hydrogen / neon plasma and mixtures thereof. In some embodiments, the plasma-containing source can be introduced into the reactor in the form of at least one nitrogen source and / or can be incidentally present in other precursors used in the deposition process. Suitable nitrogen-containing source gases include, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen plasma, nitrogen / hydrogen, nitrogen / helium, nitrogen / argon plasma, ammonia plasma, nitrogen / ammonia plasma, ammonia / helium plasma, ammonia / argon plasma, ammonia / nitrogen plasma, NF 3 In another embodiment, the plasma is selected from the group consisting of a hydrogen plasma, a helium plasma, a neon plasma, an argon plasma, a xenon plasma, a hydrogen / helium plasma, a hydrogen / argon plasma, and mixtures thereof.

[0032] Step (3): The PECVD method includes the following steps. a. providing a substrate having silicon nitride prepared by PEALD or PECCVD from step (2) in a reactor; b. At least three Si-N bonds and at least three SiH bonds, represented by the structure 3 At least one silicon precursor having a group, [ka] In the formula, R is hydrogen, linear C 1 ~C 10 Alkyl group, branched C 3 ~C 10 Alkyl group, C 3 ~C 10 Cyclic alkyl groups, C 3 ~C 10 Heterocyclic groups, C 3 ~C 10 Alkenyl group, C 3 ~C 10 Alkynyl groups, and C 4 ~C 10 aryl groups, Then, a nitrogen source is simultaneously introduced into the reactor under direct plasma to form silicon nitride, where the plasma has a flow rate of about 0.01 to about 1.5 W / cm 2 Suitable nitrogen-containing source gases can include, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen / hydrogen, nitrogen / helium, and mixtures thereof.

[0033] The thickness of the PEALD silicon nitride in the present invention is about 20-400 Å, about 20-200 Å, or about 40-200 Å, or about 50-200 Å, or about 50-150 Å, or about 80-200 Å, or about 100-200 Å. The thickness of the PECVD silicon nitride in the present invention is about 200-10,000 Å, about 200-1000 Å, or about 300-1000 Å, or about 400-1000 Å, or about 500-1000 Å, or about 600-1000 Å. The total thickness of the multilayer silicon nitride is about 400-30,000 Å, about 400-10,000 Å, about 400-8,000 Å, about 400-7,000 Å, about 400-6,000 Å, about 400-5,000 Å, about 400-2,500 Å, or about 400-2,400 Å, or about 400-2,200 Å, or about 400-2,000 Å, about 400-1,000 Å, or about 400-900 Å, or about 400-700 Å.

[0034] It is believed that the combination of the PEALD and PECVD processes may provide a better gas barrier because the PEALD or PECVD may be able to seal any tiny pores or cracks that are produced from the PECVD silicon nitride.

[0035] In certain embodiments, the methods disclosed herein avoid pre-reaction of precursors by using ALD or CCVD methods that separate precursors before and / or during introduction into the reactor. In this regard, deposition techniques, such as ALD or CCVD processes, are used to deposit silicon-containing films. In one embodiment, the film is deposited by a combination of PEALD process and PECVD in a typical single-wafer ALD reactor, semi-batch ALD reactor, or batch furnace ALD reactor. In another embodiment, the film is deposited by a combination of PEALD process and PECVD in a typical group-configured apparatus that includes a PEALD reactor and a PECVD reactor. In another embodiment, each reactant, including a silicon wire body and a reactive gas, is exposed to the substrate by moving or rotating the substrate to different sections of the reactor, and each section is separated by a curtain of inert gas, i.e., a spatial ALD reactor, or a roll-to-roll ALD reactor.

[0036] Without being bound by theory, it is believed that in Formulas A-C, three or more Si-N bonds and, optionally, three or more Si-H 3 It is believed that the silicon precursor compound having the group is more reactive to at least a portion of the substrate surface, and thus fixes more silicon fragments on the surface during the deposition process. This in turn improves the growth rate of the film and provides better surface coverage of the substrate, including surface features, such as but not limited to holes, trenches, and / or vias, thereby allowing the deposition of conformal silicon nitride or other silicon-containing films on the surface. An example of a compound of formulas A-C is bis(disilylamino)silane (also known as N,N'-disilyltrisilazane). An example of a compound of formula IIC is tris(ethylsilyl)amine. In the embodiment where the silicon precursor compound is tris(ethylsilyl)amine, it is believed that ethylene acts as a leaving group in the deposition process, thereby generating additional Si reactive sites while simultaneously reducing the Si-H content in the precursor.

[0037] As mentioned above, the methods used to form the silicon-containing materials and films described herein use a combination of deposition processes. Examples of suitable deposition processes for the methods disclosed herein include, but are not limited to, plasma-enhanced ALD (PEALD) or plasma-enhanced cyclic CVD (PECCVD) processes. As used herein, the term "chemical vapor deposition process" refers to any process in which a substrate is exposed to one or more volatile precursors that react and / or decompose on the substrate surface to produce a desired deposit. As used herein, the term "atomic layer deposition process" refers to a self-limiting (e.g., the amount of film material deposited in each reaction cycle is constant), sequential surface chemistry that deposits silicon-containing films of materials of various compositions on a substrate. Although the precursors, chemicals, and sources used herein are often described as "gaseous," it is understood that the precursors can be either liquids or solids that are transported into the reactor by direct evaporation, bubbling, or sublimation, with or without an inert gas. In some cases, the evaporated precursors can be passed through a plasma generator. In one embodiment, the silicon nitride film is deposited using a plasma-enhanced ALD process. In another embodiment, the silicon nitride film is deposited using a plasma-enhanced CCVD process. The term "reactor" as used herein includes, but is not limited to, a reaction chamber or a deposition chamber. ALD-like or PECCVD process is defined herein as a cyclic CVD process, and provides a highly conformal silicon nitride film, such as silicon nitride or silicon carbonitride, on a substrate, as shown by at least one of the following: a non-conformity percentage of about 5% or less as measured by ellipsometer, a deposition rate of 1 Å or more per cycle, or a combination thereof.

[0038] The silicon precursor compounds having formulas A-C can be delivered to the reaction chamber, such as a PEALD or PECVD reactor, in a variety of ways. In one embodiment, a liquid delivery system can be used. In another embodiment, a combined liquid delivery and flash evaporation process device, such as a turbo evaporator manufactured by MSP Corporation of Shoreview, Minnesota, can be used to allow low volatility materials to be metered in, which results in reproducible transport and deposition without thermal decomposition of the precursor. In the liquid delivery mode, the precursors described herein can be delivered in the form of a neat liquid or can be used in a solvent formulation or composition that includes a solvent. Thus, in certain embodiments, the precursor formulation can include a solvent component with suitable characteristics as desired and advantageous in a given end use to form a film on a substrate.

[0039] In one embodiment of the method disclosed herein, a substrate having a surface with a silicon-containing film or material deposited on at least a portion of the surface is placed in a deposition chamber of a reactor. The temperature of the substrate can be controlled to be lower than the walls of the reactor. The substrate temperature is maintained at a temperature between about room temperature (e.g., 20°C) and about 500°C. Other ranges of substrate temperatures have one or more of the following endpoints: 20, 50, 75, 80, 90, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, and 500°C. Exemplary temperature ranges include 20-475°C, 100-400°C, or 175-350°C. Exemplary lower temperature ranges include 20-200°C, 20-100°C, 20-90°C, and 20-80°C. In some embodiments, the substrate temperature for PEALD or PECVD is the same. In some embodiments, the substrate temperature for PEALD or PECVD can be different. In some embodiments, the PEALD or PECVD processes are performed in the same deposition chamber. In other embodiments, the PEALD or PECVD processes can be performed in different deposition chambers.

[0040] Depending on the deposition method, in certain embodiments, one or more silicon-containing precursor compounds can be introduced into the reactor at a molar volume, or from about 0.1 to about 1000 micromoles. In this or other embodiments, the silicon precursor or silicon precursors including Formulae A-C and the solvent can be introduced into the reactor for a predetermined time interval. In certain embodiments, for either PEALD / PECCVD or PECVD deposition, the time interval ranges from about 0.001 to about 500 seconds, however, they can be carried out at the same or different temperatures.

[0041] The multilayer silicon-containing film deposited using the method described herein is formed in the presence of a nitrogen-containing source. The nitrogen-containing source can be introduced into the reactor in the form of at least one nitrogen-containing source and / or can be present incidentally in other precursors used in the deposition process. Suitable nitrogen-containing source gases include, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen-containing plasma, nitrogen and hydrogen-containing plasma, nitrogen and helium-containing plasma, nitrogen and argon-containing plasma, ammonia plasma, nitrogen and ammonia-containing plasma, ammonia and helium-containing plasma, ammonia and argon-containing plasma, NF 3Examples of suitable plasmas include plasma, organic amine plasma, and mixtures thereof. In other embodiments, the plasma is selected from the group consisting of hydrogen plasma, helium plasma, neon plasma, argon plasma, xenon plasma, hydrogen / helium plasma, hydrogen / argon plasma, and mixtures thereof. In one particular embodiment, the nitrogen-containing source is substantially free of hydrogen (e.g., contains less than 2% by weight (wt.%)) to avoid introducing additional hydrogen into the final silicon nitride film, and is selected from the group consisting of nitrogen plasma, nitrogen / helium, and nitrogen / argon plasma. In other embodiments, the nitrogen-containing source is selected from monoalkylhydrazine and dialkylhydrazine. For silicon carbonitride deposition, the nitrogen-containing source can be selected from the group consisting of organic amine plasma, such as methylamine plasma, dimethylamine plasma, trimethylamine plasma, ethylamine plasma, diethylamine plasma, trimethylamine plasma, and ethylenediamine plasma. Throughout this specification, the term "organic amine" as used herein refers to an organic compound having at least one nitrogen atom. Examples of organic amines include, but are not limited to, methylamine, ethylamine, propylamine, isopropylamine, tert-butylamine, sec-butylamine, tert-amylamine, ethylenediamine, dimethylamine, trimethylamine, diethylamine, pyrrole, 2,6-dimethylpiperidine, di-n-propylamine, di-isopropylamine, ethylmethylamine, N-methylaniline, pyridine, and triethylamine. Similarly, as used herein and throughout this specification, the term "organoamino group" refers to an organic group consisting of at least one nitrogen atom derived from a secondary or primary organic amine as described above. An "organoamino group" refers to an -NH 2 In some embodiments, the plasma is generated in situ, while in other embodiments, the plasma can be provided remotely by a plasma generator.

[0042] In certain embodiments, the nitrogen-containing source is introduced into the reactor at a flow rate of about 2000 square cubic centimeters (sccm) or in a range of about 1 to about 1000 sccm. The nitrogen-containing source can be introduced for a time period ranging from about 0.1 to about 100 seconds. In embodiments where the film is deposited by an ALD or cyclic CVD process, the pulse of precursor can have a pulse duration of more than 0.01 seconds and the nitrogen-containing source can have a pulse duration of less than 0.01 seconds. In yet other embodiments, the purge duration between pulses can be as short as 0 seconds or pulsed continuously with no purge between them.

[0043] In certain embodiments, the reactor temperature in the introducing step is one or more temperatures ranging from about room temperature (e.g., 20° C.) to about 500° C. Other ranges of substrate temperatures have one or more of the following endpoints: 20, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, and 500° C. Exemplary preferred temperature ranges include the following: 20-200° C., 20-100° C., 20-90° C., and 20-80° C.

[0044] Energy is applied to at least one precursor compound, nitrogen-containing source, oxygen-containing source, other chemicals, or combinations thereof to induce a reaction and form a silicon-containing film or coating or chemisorbed layer on at least a portion of the substrate. Such energy can be provided by, but is not limited to, thermal, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, x-ray, e-beam, photon, remote plasma methods, and combinations thereof. In certain embodiments, a second RF frequency source can be used to modify the plasma characteristics at the substrate surface. In embodiments where the deposition includes a plasma, the process in which the plasma is generated can include a direct plasma generation process in which the plasma is generated directly in the reactor, or a remote plasma generation process in which the plasma is generated outside the reactor and fed into the reactor. In certain embodiments of the methods described herein, the plasma is generated in situ at a power of about 0.01 to about 1.5 W / cm. 2 The power densities are generated in the range of

[0045] The deposition methods disclosed herein may include one or more purge gases. Purge gases used to purge unconsumed reactants and / or reaction by-products include inert gases that do not react with the precursors. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N 2 ), helium (He), neon, hydrogen (H 2 ) and mixtures thereof. In certain embodiments, the purge gas is fed into the reactor at a flow rate ranging from about 10 to about 2000 sccm for about 0.1 to 1000 seconds, thereby purging the reactor of unreacted materials and any by-products that may remain.

[0046] Each step of supplying the precursor, oxygen-containing source, nitrogen-containing source, and / or other precursor, source gas, and / or chemical can be performed by varying the time of supplying them to change the stoichiometric composition of the resulting film or material. A flow of argon and / or other gas can be used as a carrier gas to help supply the vapor of at least one precursor compound to the reaction chamber during the precursor pulsing. In certain embodiments, the process pressure of the reaction chamber is about 10 Torr or less, 5 Torr or less, 2 Torr or less, 1 Torr or less.

[0047] In one form of the combined PEALD or PECCVD and PECVD methods described herein, the substrate is heated on a heater stage in the reaction chamber and first exposed to the precursor compound to allow the compound to be chemically adsorbed on the surface of the substrate. The excess precursor compound that was not absorbed is purged from the process chamber with a purge gas, such as nitrogen, argon, or other inert gas. After sufficient purging, a nitrogen-containing source can be introduced into the reaction chamber to react with the absorbed surface, followed by another gas purge to remove the reaction by-products from the chamber. The process cycle can be repeated until the desired film thickness is obtained. In another embodiment, purging under vacuum can be used to remove the excess precursor that was not absorbed from the process chamber, and after sufficient evacuation under pumping, a nitrogen-containing source can be introduced into the reaction chamber to react with the absorbed surface, followed by another purge with pumping to remove the reaction by-products from the chamber. In yet another embodiment, the precursor compound and the nitrogen-containing source can be flowed in parallel into the reaction chamber to react on the substrate surface to deposit silicon nitride. In certain embodiments of cyclic CVD, a purge step is not used.

[0048] In this or other embodiments, it is understood that the steps of the methods described herein can be performed in various orders, sequentially or simultaneously (e.g., between at least some of the other steps), and any combination thereof. Each step of supplying the precursor and the nitrogen-containing source gas can be performed by varying the duration of time for supplying them to change the stoichiometric composition of the resulting silicon-containing film.

[0049] In accordance with the present invention, three or more Si-N bonds represented by formulas A-C, and optionally three or more Si-H 3 The compositions comprising the precursors described herein having a silicon group, as well as the silicon precursors thereof, are preferably substantially free of halide ions, such as chloride, or metal ions, such as Al. As used herein, the term "substantially free" means that it is free of halide ions (or halides), such as chloride and fluoride, bromide, iodide, Al, 3+ Ion, Fe 2+ , Fe 3+ , Ni 2+ , Cr 3+ In the case of silicon precursors, the concentration of chloride in the silicon precursors is less than 5 ppm (by weight), preferably less than 3 ppm, and more preferably less than 1 ppm, and most preferably 0 ppm. Chloride or metal ions are known to act as decomposition catalysts for silicon precursors. Eventually, significant levels of chloride in the product can cause the silicon precursors to decompose. The gradual decomposition of silicon precursors can directly affect the film deposition process, making it difficult for semiconductor manufacturers to meet film specifications. Furthermore, the shelf life or stability is adversely affected by the faster decomposition rate of silicon precursors, making it difficult to guarantee a shelf life of 1 to 2 years.

[0050] The compositions according to the present invention that are substantially free of halides can be obtained by (1) reducing or eliminating chloride sources during chemical synthesis and / or (2) implementing an effective purification process that removes chloride from the raw product so that the final purified product is substantially free of chloride. The chloride source can be reduced during synthesis by using chemicals that do not contain halides, such as chlorodisilanes, bromodisilanes, or iodosilanes, thereby avoiding the generation of by-products that contain halide ions. Furthermore, the aforementioned chemicals should be substantially free of halide impurities, so that the resulting raw product is substantially free of chloride impurities. Similarly, the synthesis should not use halide-based solvents, catalysts, or solvents that contain unacceptably high levels of halide impurities. The raw product can also be treated by various purification processes to render the final product substantially free of halides, such as chloride. Such methods are well described in the art and can include, but are not limited to, purification processes, such as distillation or adsorption. Distillation is commonly used to separate impurities from the desired product by taking advantage of differences in boiling points. Adsorption can also be used to effect separation by taking advantage of the specific adsorption properties of the components, thereby rendering the final product substantially free of halides. Adsorbents, such as the commercially available MgO-Al 2 O 3 The mixture can be used to remove halides, such as chloride.

[0051] In those embodiments relating to compositions comprising a solvent and precursors having formulas A-C described herein, the selected solvent or mixtures thereof do not react with the silicon precursor. The amount of the solvent by weight percent in the composition ranges from 0.5% to 99.5% by weight, or from 10% to 75% by weight. In this or other embodiments, the solvent has a boiling point (bp) similar to the bp of the silicon precursors of formulas A-C, or the difference between the bp of the solvent and the bp of the silicon precursors of formulas A-C is 40° C. or less, 30° C. or less, or 20° C. or less, 10° C. or less, or 5° C. or less. Alternatively, the difference between the boiling points ranges by any one or more of the following endpoints: 0, 10, 20, 30, or 40° C. Examples of suitable ranges of difference in bpd include, but are not limited to, 0 to 40° C., 20° C. to 30° C., or 10° C. to 30° C. Examples of suitable solvents in the composition include, but are not limited to, ethers (e.g., 1,4-dioxane, dibutyl ether), tertiary amines (e.g., pyridine, 1-methylpiperidine, 1-ethylpiperidine, N,N'-dimethylpiperazine, N,N,N',N'-tetramethylethylenediamine), nitriles (e.g., benzonitrile), alkyl hydrocarbons (e.g., octane, nonane, dodecane, ethylcyclohexane), aromatic hydrocarbons (e.g., toluene, mesitylene), tertiary amino ethers (e.g., bis(2-dimethylaminoethyl) ether), or mixtures thereof. Some non-limiting examples include, but are not limited to, a composition comprising bis(disilylamino)silane (bp about 135° C.) and octane (bp 125-126° C.), a composition comprising bis(disilylamino)silane (bp about 135° C.) and ethylcyclohexane (bp 130-132° C.), a composition comprising bis(disilylamino)silane (bp about 135° C.) and cyclooctane (bp 149° C.), and a composition comprising bis(disilylamino)silane (bp about 135° C.) and toluene (bp 115° C.).

[0052] As previously mentioned, the methods described herein can be used to deposit a silicon nitride film on at least a portion of a substrate. Examples of suitable substrates include, but are not limited to, silicon, SiO 2 , Si 3 N 4 , OSG, FSGd, silicon carbide, hydrogenated silicon carbide, silicon nitride, hydrogenated silicon nitride, silicon carbonitride, hydrogenated silicon carbonitride, boron nitride, anti-reflective coatings, photoresists, flexible substrates such as IGZO, organic polymers, porous organic and inorganic materials, metals such as copper and aluminum, and diffusion barrier layers such as, but not limited to, TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN. These films are compatible with a variety of subsequent processing steps, such as chemical mechanical planarization (CMP) and anisotropic etching processes.

[0053] The deposited films have applications including, but not limited to, computer chips, optical devices, magnetic information storage devices, coatings on supporting materials or substrates, microelectromechanical systems (MEMS), nanoelectromechanical systems, thin film transistors (TFTs), light emitting diodes (LEDs), organic light emitting diodes (OLEDs), IGZO, and liquid crystal displays (LCDs).

[0054] The following examples illustrate methods for depositing the silicon-containing materials or films described herein and are not intended to be limiting in any way. EXAMPLES

[0055] In the following examples, unless otherwise noted, properties were obtained from sample films deposited on medium resistivity (1-10 Ω-cm, p-type) single crystal silicon wafer substrates. All film depositions were performed using a CN-1 reactor with a showerhead design or a cross-flow type CN-1 reactor without plasma, with a direct plasma at 13.56 MHz. In typical process conditions, the chamber pressure was fixed at a pressure ranging from about 1 to about 5 Torr, unless otherwise noted. An additional inert gas was used to maintain the chamber pressure. The silicon precursor was delivered using vapor aspirate (i.e., no argon was used). Typical RF power used was 125 W over the electrode area of ​​a 200 mm wafer, with a 0.7 W / cm2. 2 A power density of 1000 nm was applied. Film deposition included the steps listed in Tables 1 and 2 for PEALD and PECVD, respectively. Steps 1-4 in Table 1 constitute one PEALD cycle and were repeated a total of 300 times, unless otherwise noted, to obtain the desired film thickness. [Table 1] [Table 2]

[0056] The reactive index (RI) of the deposited films was measured using an ellipsometer. The film non-uniformity was calculated using the standard equation: % non-uniformity = ((maximum thickness - minimum thickness) (2 x average (avg) thickness)). The film structure and composition were analyzed using Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The film density was measured by X-ray reflectometry (XRR).

[0057] Water Vapor Transmission Rate (WVTR) was measured using a RutaPerm device. RutaPerm uses the total pressure method to measure permeability. A pressure difference is created between the two sides of the test sample. This pressure difference is the driving force for permeation. Gas or vapor permeates along the pressure gradient. This permeation process consists of two basic steps: dissolution into the sample and diffusion through the sample. The pressure increase on the lower pressure side (downstream) is detected by a pressure sensor. From the measured pressure increase per unit time, a computer program calculates the permeation rate, which in the case of water vapor is often referred to as WVTR. The units of WVTR are usually g / m 2 Expressed in days. Oven temperature and relative humidity are usually used at fixed values.

[0058] PEALD condition Substrate temperature 85 °C, chamber pressure 1 Torr, 50-300 W (main power = 150 W), N 2 = 1000 sccm, Ar[CAN] = vapor intake for precursor A, Ar[MO] = 100 sccm

[0059] PECVD conditions Substrate temperature 85-100°C, chamber pressure 1-5 Torr (main pressure = 2.5 Torr), 50-300 W (main power = 250 W), H 2 = 1000sccm, NH 3 = 10 sccm, Ar[CAN] = vapor intake for precursor A, Ar[MO] = 100 sccm

[0060] [Table 3]

[0061] As shown in Table 3, the resulting silicon nitride potentially has the following advantages over the prior art: (a) a total thickness of 2500 Å or less, 2000 Å or less, or 1000 Å or less; (b) a WVTR value of 5.0×10 -5 g / m 2 Days or less, 5.0×10 -4 g / m 2days or less, or 5.0 x 10 -3 g / m 2 (c) it is more flexible than existing single or double layer bus barriers because a thinner silicon nitride can be used to prevent gases, such as oxygen and moisture, from permeating the gas barrier; and (d) it has fewer pinholes because PEALD can potentially seal most of the pinholes generated from the PECVD process.

Claims

1. 1. A method for depositing a multi-layer silicon nitride film using a combination of deposition methods, comprising: a. placing a substrate into a first reactor; b. depositing a first silicon nitride film, a second silicon nitride film, and a third silicon nitride film on at least a portion of a surface of a substrate by a sequence of deposition methods by alternating between (1) either plasma enhanced atomic layer deposition (PEALD) or plasma enhanced cyclic chemical vapor deposition (PECCVD), and (2) PECVD, which together form a multi-layer silicon nitride film; The PEALD or PECCVD deposition method includes: (1) the following steps i to iv, which are repeated until a silicon nitride layer of a desired thickness is obtained; i. in said reactor, under conditions sufficient to react on at least a portion of the surface to provide a chemisorbed layer, at least three Si—N bonds and at least three SiH bonds represented by Formulas A through C; ３ introducing at least one silicon precursor compound having a group; [Formula 1] In the formula, R is independently hydrogen, linear C １ ~C １０ Alkyl group, branched C ３ ~C １０ Alkyl group, linear or branched C ３ ~C １２ Alkenyl group, linear or branched C ３ ~C １２ Alkenyl group, linear or branched C ３ ~C １２ Alkynyl group, C ４ ~C １０ Cyclic alkyl groups, and C ６ ~C １０ aryl groups, ii. purging the reactor with a purge gas; iii. introducing a first plasma-containing source into the reactor to react with at least a portion of the chemisorbed layer and provide at least one reaction site, the plasma having a power of about 0.01 to about 1.5 W / cm ２generated at power densities in the range iv. Optionally purging the reactor with an inert gas; and the PECVD deposition method (2) comprises the following step v: v. introducing into said reactor at least one silicon precursor represented by Structures A-C and a second plasma-containing source to form silicon nitride, said plasma having a power of about 0.01 to about 1.5 W / cm ２ generated at power densities in the range method.

2. The first plasma containing source is selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, nitrogen / helium, nitrogen / argon, nitrogen / ammonia, ammonia / helium, ammonia / argon, ammonia / nitrogen, NF ３ 2. The method of claim 1, further comprising at least one gas selected from the group consisting of organic amines, hydrogen, helium, neon, argon, xenon, hydrogen / helium, hydrogen / argon, and mixtures thereof.

3. 2. The method of claim 1, wherein the second plasma-containing source comprises at least one gas selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen / hydrogen, nitrogen / helium, and mixtures thereof.

4. The method of claim 1, wherein each silicon nitride film formed by PEALD or PECCVD has a thickness in the range of about 10 to about 200 Å.

5. The method of claim 1, wherein each silicon nitride film formed by PECVD has a thickness in the range of about 200 to about 1000 Å.

6. The method of claim 1 , wherein the at least one silicon precursor compound comprises trisilylamine.

7. The method of claim 1, wherein the at least one silicon precursor compound comprises bis(disilylamino)silane (also known as N,N'-disilyltrisilazane).

8. The method of claim 1 , wherein the at least one silicon precursor compound comprises tris(ethylsilyl)amine.

9. The method of claim 1, wherein the substrate is maintained at a temperature in the range of about 20° C. to about 500° C. during deposition of the multi-layer silicon nitride film.

10. The method of claim 9, wherein the substrate is maintained at a temperature in the range of about 20° C. to about 100° C. during deposition of the multi-layer silicon nitride film.

11. The multilayer silicon nitride film has a thickness of 5.0×10 －５ g / m ２ 2. The method of claim 1, wherein the water vapor transmission rate (WVTR) value is equal to or less than 10 days.

12. The multilayer silicon nitride film has a thickness of 5.0×10 －３ g / m ２ 2. The method of claim 1, wherein the WVTR value is less than or equal to 10 days.

13. The method of claim 1 , wherein said multi-layer silicon nitride film has a total thickness of less than or equal to 2500 Å.

14. The method of claim 1 , wherein said multi-layer silicon nitride film has a total thickness of less than 1000 Å.

15. A multi-layer silicon nitride film formed by the method of claim 1.

16. 5.0 x 10 －３ g / m ２ A multi-layer silicon nitride membrane having a WVTR value of less than or equal to 1000 nm.

17. 5.0 x 10 －５ g / m ２ 17. The multilayer silicon nitride film of claim 16 having a WVTR value of 100 days or less.

18. The multi-layer silicon nitride film of claim 16 having a thickness of less than or equal to 10,500 Å.

19. The multilayer silicon nitride film of claim 15 used as a gas barrier layer in a display device.

20. The multi-layer silicon nitride film of claim 15 further having an RI value of 1.90 or greater.

21. The method of claim 1 , wherein the 1) PEALD or PECCVD and 2) PECVD processes are performed in the same deposition chamber.

22. The method of claim 1 , wherein the 1) PEALD or PECCVD and 2) PECVD processes are performed in different deposition chambers.

23. The method of claim 1 , wherein the first plasma is generated in situ.

24. The method of claim 1 , wherein the first plasma is generated remotely.

25. The method of claim 1 , wherein the first plasma is a combination of in situ and remotely generated plasma.

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