Method for preparing silicon-rich silicon nitride films

Abstract

In summary, the present invention provides a method for depositing silicon nitride films on microelectronic device substrates. The method utilizes a precursor and a co-reactant selected from halosilane compounds, compounds of formula R2NH, aminosilanes and hydrogen. The silicon nitride films thus formed have an increased silicon fraction while providing a uniform thickness film, i.e., high conformality, even in high aspect ratio 3D NAND structures.

Description

[Technical field]

[0001] The present invention relates generally to a method for depositing a silicon-rich nitride film on a microelectronic device substrate.

[0002] Priority claim This document claims priority to U.S. Provisional Patent Application No. 63 / 316,956, filed March 4, 2022. The priority document is incorporated herein by reference for all purposes. [Background technology]

[0003] Silicon nitride is commonly used in the fabrication of integrated circuits. For example, it is often used as an insulating material in the manufacture of various microelectronic devices such as memory cells, logic devices, and memory arrays. In particular, silicon nitride is used as a charge trapping layer in 3D NAND structures. Silicon nitride has a general empirical formula of Si3N4, but for any given deposited film, this composition may vary, and for certain applications, silicon-rich silicon nitride films are desirable. Current methods utilize hexachlorodisilane (HCDS) precursors and ammonia co-reactant as silicon and nitrogen sources. These HCDS / ammonia methods can provide the desired silicon-rich stoichiometry, but the deposited silicon nitride films lack the desired conformality. Atomic layer deposition (ALD) and pulsed chemical vapor deposition (CVD) methods utilizing HCDS / ammonia can provide films with good conformality, but cannot provide the desired silicon:nitrogen stoichiometric ratio. Therefore, a method capable of producing uniformly thick (i.e., highly conformal) films with silicon:nitrogen composition>1 in high aspect 3D NAND structures is highly desirable. Summary of the Invention

[0004] In summary, the present invention provides a method for depositing silicon nitride films on microelectronic device substrates. The method utilizes a precursor and a co-reactant selected from a halosilane compound, a compound of formula R2NH, an aminosilane, and hydrogen. The silicon nitride film so formed has an increased stoichiometric percentage of silicon while providing a uniform thickness film, i.e., high conformality, even in high aspect ratio 3D NAND structures. [Brief description of the drawings]

[0005] [Figure 1] 1 is a plot of growth rate per cycle (GPC) in angstroms per cycle versus hexachlorodisilane (HCDS) pulse time (see Example 1). The circular data points represent a HCDS / NH3 pulse sequence. The triangular data points represent a HCDS / (4DMAS+H2) / NH3 pulse sequence. The diamond data points represent a HCDS / 4DMAS / NH3 pulse sequence. The square data points represent a HCDS / 4DMAS / (NH3+H2) pulse sequence. [Diagram 2] 1 is a plot of ellipsometry (SE) thickness in Angstroms versus etch time in minutes for various pulse sequences (see Example 2). Triangular points relate to thermal oxide. Circle points relate to HCDS / NH3 pulse sequence. Diamond points relate to HCDS / (4DMAS)+H2) / NH3 pulse sequence. Square points relate to HCDS / 4DMAS / (NH3+H2) pulse sequence. [Diagram 3] 1 shows the atomic concentrations of silicon, nitrogen, oxygen, chlorine and carbon at various depths (in nanometers) in the film (see Example 3). [Figure 4] 1 shows the atomic concentrations of silicon, nitrogen, oxygen, chlorine and carbon at various depths (in nanometers) in the film (see Example 3). [Diagram 5]1 is a plot of growth rate per cycle (GPC) in angstroms per cycle versus HCDS pulse time in seconds. Square data points represent HCDS / 4DMAS / (NH3+H2) pulse sequence. Diamond data points represent HCDS / (NH3+H2) pulse sequence. Circle data points represent HCDS / NH3 pulse sequence. (See Example 4). [Figure 6] 1 shows the atomic concentrations of silicon, nitrogen, oxygen, chlorine and carbon at various depths (in nanometers) in the film (see Example 5). [Figure 7] 1 shows the atomic concentrations of silicon, nitrogen, oxygen, chlorine and carbon at various depths (in nanometers) in the film (see Example 5). [Figure 8] 1 is a plot of SE thickness in Angstroms versus etch time in minutes. The triangular points represent thermally oxidized reference films. The circular points relate to films obtained from a HCDS / 4DMAS pulse sequence at 600° C. (see Example 7). [Figure 9] 1 is a plot of SE thickness in Angstroms versus etch time in minutes. The triangular points represent thermally oxidized reference films. The circular points represent films prepared from a HCDS / 4DMAS pulse sequence at 570° C. (see Example 7). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise. As used in this specification and the appended claims, the term "or" is generally used in its sense including "and / or" unless the content clearly dictates otherwise.

[0007] The term "about" generally refers to a range of numbers that are considered equivalent to the recited value (e.g., having the same function or result). In many cases, the term "about" can include numbers that are rounded to the nearest significant figure.

[0008] Numeric ranges expressed using endpoints include all numbers subsumed within that range (eg, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0009] In a first aspect, the present invention provides a method for depositing a silicon nitride film on a microelectronic device substrate, comprising: Under deposition conditions: a. Halosilane compounds, b. an aminosilane, and optionally c. A compound of the formula R2NH, where each R is independently hydrogen or a C1-C4 alkyl group in combination with hydrogen. The method includes contacting a precursor compound with a continuous pulse comprising a pulse sequence comprising:

[0010] In a second aspect, the present invention provides a method for depositing a silicon nitride film on a microelectronic device substrate, comprising: Under deposition conditions: a. a halosilane compound, and b. A compound of the formula R2NH, where each R is independently hydrogen or a C1-C4 alkyl group in combination with hydrogen. The method includes contacting a precursor compound with a continuous pulse comprising a pulse sequence comprising:

[0011] In the above embodiment, the aminosilane compound is a nitrogen precursor compound that contains at least one silicon atom and at least one alkylamino group. Exemplary aminosilane compounds include those having the formula TIFF2025508534000002.tif37170Tetrakis(dimethylamino)silane (CAS number 1624-01-7); TIFF2025508534000003.tif42170TIFF2025508534000004.tif42170TIFF2025508534000005.tif25170(Hexakis(ethylamino)disilane) (CAS number 532980-53-3); and the compound of formula: TIFF2025508534000006.tif241701,2-Dichloro-N,N,N',N',N'',N'',N''',N'''-octaethyl-1,1,2,2-disilanetetraamine "EACDS" (CAS number 151625-20-6) is included as a compound.

[0012] In the above aspect, the halosilane compound is a silicon precursor compound that contains one or two silicon atoms and at least one halogen atom, such as chlorine, bromine or iodine. In certain embodiments, the halosilane compound is selected from chlorosilane, iodosilane, diiodosilane and hexachlorodisilane.

[0013] Compounds of formula R2NH include ammonia, dimethylamine, diethylamine, etc. In one embodiment, the compound of formula R2NH is ammonia.

[0014] In certain embodiments, the pulse sequence is selected from the following: a. Hexachlorodisilane / purge / tetrakis(dimethylamino)silane / purge / (NH3+H2) / purge b. Hexachlorodisilane / purge / (tetrakis(dimethylamino)silane + H2) / purge / NH3 / purge c. Hexachlorodisilane / purge / Tetrakis(dimethylamino)silane / purge / NH3 / purge d. Chlorosilane / purge / tetrakis(dimethylamino)silane / purge / (NH3+H2) / purge e. Chlorosilane / purge / (tetrakis(dimethylamino)silane + H2) / purge / NH3 / purge f. Chlorosilane / purge / Tetrakis(dimethylamino)silane / purge / NH3 / purge g. Iodosilane / purge / Tetrakis(dimethylamino)silane / purge / (NH3+H2) / purge h. Iodosilane / purge / (tetrakis(dimethylamino)silane + H2) / purge / NH3 / purge i. Iodosilane / purge / Tetrakis(dimethylamino)silane / purge / NH3 / purge j. Diiodosilane / purge / Tetrakis(dimethylamino)silane / purge / (NH3+H2) / purge k. Diiodosilane / purge / (tetrakis(dimethylamino)silane + H2) / purge / NH3 / purge l. Diiodosilane / purge / Tetrakis(dimethylamino)silane / purge / NH3 / purge m.Hexachlorodisilane / purge / TTCDS / purge / (NH3+H2) / purge n.Hexachlorodisilane / purge / TTCDS+H2) / purge / NH3 / purge o.Hexachlorodisilane / purge / TTCDS / purge / NH3 / purge p.Chlorosilane / purge / TTCDS / purge / (NH3+H2) / purge q. Chlorosilane / purge / TTCDS+H2) / purge / NH3 / purge r.Chlorosilane / purge / TTCDS / purge / NH3 / purge s.Iodosilane / purge / TTCDS / purge / (NH3+H2) / purge t. Iodosilane / purge / TTCDS+H2) / purge / NH3 / purge u.Iodosilane / purge / TTCDS / purge / NH3 / purge v. Diiodosilane / purge / TTCDS / purge / (NH3+H2) / purge w. Diiodosilane / purge / TTCDS+H2) / purge / NH3 / purge x. Diiodosilane / purge / Hexachlorodisilane / purge / Tetrakis(dimethylamino)silane / purge / (NH3+H2) / purge y. Hexachlorodisilane / purge / EACDS / purge / (NH3+H2) / purge z. Hexachlorodisilane / purge / EACDS+H2) / purge / NH3 / purge aa.Hexachlorodisilane / purge / EACDS / purge / NH3 / purge bb. Chlorosilane / purge / EACDS / purge / (NH3+H2) / purge cc. Chlorosilane / purge / EACDS+H2) / purge / NH3 / purge dd. Chlorosilanes / purge / EACDS / purge / NH3 / purge ee. Iodosilane / purge / EACDS / purge / (NH3+H2) / purge ff. Iodosilane / purge / EACDS+H2) / purge / NH3 / purge gg.Iodosilane / purge / EACDS / purge / NH3 / purge hh. Diiodosilane / purge / EACDS / purge / (NH3+H2) / purge ii. Diiodosilane / purge / EACDS+H2) / purge / NH3 / purge jj. Diiodosilane / purge / EACDS / purge / NH3 / purge / NH3 / Purge

[0015] The method of the present invention allows for the deposition of highly conformal silicon nitride films with an enhanced silicon fraction, i.e., a greater silicon fraction than the typical Si3N4 stoichiometric ratio (on a molar basis). In certain embodiments, the silicon to nitrogen ratio in such films is greater than 3:4. In other embodiments, the silicon:nitrogen ratio is greater than 1:1, for example 1.04:1 or 1.12:1 (in other words, 1.12 parts silicon to 1 part nitride).

[0016] Moreover, the methods of the present invention enable the deposition of such silicon nitride films with high conformality, e.g., step coverage of at least about 92%, at least about 93%, at least about 94%, or at least about 95% on trench structures having an aspect ratio of about 12. Step coverage is calculated as the film thickness at the bottom of the trench divided by the film thickness at the top of the trench.

[0017] As discussed above, the methods of the present invention allow for the deposition of silicon nitride films with enhanced or increased silicon percentage while having excellent conformality, thus allowing for easy deposition on high aspect ratio microelectronic devices. Thus, in another aspect, the present invention provides a microelectronic device structure having a silicon nitride film thereon, the microelectronic device structure having at least one substructure with an aspect ratio greater than about 10, the silicon nitride film having at least about 95% conformality and a silicon to nitride ratio of at least about 1.04:1 to about 1.12:1. In certain embodiments, the devices have an aspect ratio of about 10 to about 500, and in other embodiments, an aspect ratio of about 50 to about 200.

[0018] In certain embodiments, the deposition conditions referred to herein include reaction conditions known as chemical vapor deposition, pulsed chemical vapor deposition, and atomic layer deposition. In the case of pulsed chemical vapor deposition, a series of alternating pulses of precursor composition and co-reactant, with or without intermediate (inert gas) purge steps, can be utilized to build film thickness to a desired endpoint.

[0019] In certain embodiments, the pulse time of the precursor compounds (i.e., duration of precursor exposure to the substrate) ranges from about 1 to 30 seconds. If a purge step is utilized, the duration is about 1 to 20 seconds or 1 to 30 seconds. In other embodiments, the pulse time of the co-reactant ranges from 5 to 60 seconds.

[0020] In one embodiment, the deposition conditions include a temperature in the reaction zone of about 400° C. to about 750° C., or about 500° C. to about 650° C., and a pressure of about 0.2 Torr to about 100 Torr. It should be understood that the temperature in the reaction zone is also the temperature to which the microelectronic device substrate is heated.

[0021] The desired microelectronic device substrate may be placed into the reaction zone in any suitable manner, for example, in a single wafer CVD or ALD, or in a furnace containing multiple wafers.

[0022] In one alternative, the method of the present invention can be carried out as an ALD or ALD-like method. As used herein, the term "ALD or ALD-like" refers to a method in which (i) each reactant, including a precursor composition comprising a compound described herein, co-reactant, is introduced sequentially into a reactor, such as a single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor, or (ii) each reactant is exposed to the substrate or microelectronic device surface by moving or rotating the substrate to different sections of the reactor, each section being separated by an inert gas curtain, i.e., a spatial ALD reactor or a roll-to-roll ALD reactor. In certain embodiments, the thickness of the resulting bulk ALD silicon nitride film can be from about 0.5 nm to about 40 nm.

[0023] The deposition methods disclosed herein may involve one or more purge gases. Purge gases used to purge unconsumed reactants and / or reaction by-products are inert gases that do not react with either the precursor composition or the counter reactant. Exemplary purge gases include, but are not limited to, argon, nitrogen, helium, neon, and mixtures thereof. In certain embodiments, a purge gas such as Ar is supplied to the reactor at a flow rate ranging from about 10 to about 2000 sccm for about 0.1 to 1000 seconds, thereby purging unreacted materials and any by-products that may remain within the reactor. Such purge gases may also be utilized as inert carrier gases for either or both of the precursor composition and co-reactant.

[0024] Energy is applied to the precursor composition and co-reactants in the reaction zone to induce a reaction and form a film on the microelectronic device surface. Such energy can be provided by, but is not limited to, heat, pulsed heat, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, x-ray, electron beam, photon, remote plasma methods, and combinations thereof. In certain embodiments, a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface. In embodiments where deposition involves plasma, the plasma generation method can include a direct plasma generation method where the plasma is generated directly in the reactor, or alternatively, a remote plasma generation method where the plasma is generated "remote" to the reaction zone and substrate and fed into the reactor.

[0025] In one embodiment, the vapor deposition conditions include thermal atomic layer deposition conditions. In one embodiment, the thermal atomic layer deposition conditions further include utilizing one or more periodic pulses of an ammonia plasma and / or a hydrogen plasma.

[0026] As used herein, the term "microelectronic device" corresponds to semiconductor substrates, including 3D NAND structures, flat panel displays, and microelectromechanical systems (MEMS), manufactured for use in microelectronic, integrated circuit, or computer chip applications. It is to be understood that the term "microelectronic device" is not meant to be limiting in any way and includes any substrate that will ultimately become a microelectronic device or microelectronic assembly. Such microelectronic devices include at least one substrate that can be selected from, for example, tin, SiO2, Si3N4, OSG, FSG, tin carbide, hydrogenated tin carbide, tin nitride, hydrogenated tin nitride, tin carbonitride, hydrogenated tin carbonitride, boron nitride, anti-reflective coatings, photoresists, germanium, germanium-containing, boron-containing, Ga / As, flexible substrates, porous 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. EXAMPLES

[0027] Example 1 ALD Saturation Referring to the data shown in FIG. 1, atomic layer deposition was performed on silicon coupons at 600° C. in a chamber at a pressure of 2 Torr. A 2 inch diameter showerhead was utilized on a 4 cm silicon coupon. Hexachlorodisilane (HCDS) was introduced at a temperature of 18° C. along with tetrakis(dimethylamino)silane (CAS number 1624-01-7) (4DMAS) at a temperature of 22° C. 50 cycles were performed.

[0028] As shown in Figure 1, the following pulse sequence was performed. a.HCDS / Purge / 4DMAS / Purge / (NH3+H2) / Purge b.HCDS / purge / (4DMAS+H2) / purge / NH3 / purge c.HCDS / Purge / 4DMAS / Purge / NH3 / Purge d.HCDS / Purge / NH3 / Purge i. Argon purge - 5 seconds ii.4DMAS installation - 2 seconds iii.NH3 introduction - 5 seconds iv.NH3 flow rate 68sccm v.H2 flow rate 118sccm

[0029] This data shows that 4DMAS pulsing and the addition of H to the HCDS / NH3ALD regime achieves saturation and higher growth rates. In this context, saturation means that the deposition rate does not change with reactant pulse time, i.e., the deposition is self-limiting.

[0030] Example 2 - Etch Rate Referring to the data shown in Figure 2, SE thickness in Angstroms is plotted against etch time in minutes for the 100:1 dilution HF etch rate test. Data sets a-d are as follows: a.HCDS / NH3 b.HCDS / (4DMAS+H2) / NH3 c.HCDS / 4DMAS / (NH3+H2) d. Thermal oxide

[0031] The wet etch rates (WER) (Å / min) of the films so produced were as follows: a.HCDS / NH3- 13.7 b.HCDS / (4DMAS+H2) / NH3- 4.0 c.HCDS / 4DMAS / (NH3+H2) - 2.6 d.Thermal oxide-21.0

[0032] The data show that the addition of 4DMAS pulses and H2 to the HCDS / NH3ALD regime reduces the wet etch rate of the resulting silicon nitride films so produced.

[0033] Example 3 - XPS Data Referring to the data shown in Figure 3, a silicon-rich film was deposited using atomic layer deposition at 600°C and 2 Torr using a pulsed regime of HCDS / 4DMAS / (NH3+H2). The data shows 47 atomic percent silicon, 45.2 atomic percent nitrogen, 1.2 atomic percent carbon, 2.9 atomic percent oxygen, and 3.7 atomic percent chlorine, with a silicon to nitrogen ratio of 1.04:1. The concentrations (atomic percentages) were plotted versus depth in nanometers.

[0034] Referring to the data shown in FIG. 4, a control film was produced under the same conditions using a HCDS / NH3 pulsed regime to provide a film having 46.5 atomic percent silicon, 48.6 atomic percent nitrogen, 0 atomic percent carbon, 1.6 atomic percent oxygen, and 3.3 atomic percent chlorine, for a silicon to nitrogen ratio of 0.96:1.

[0035] The data show that the addition of 4DMAS / H2 pulses to HCDS deposits silicon-rich silicon nitride films while simultaneously incorporating carbon.

[0036] Example 4 - Control showing saturation Referring to the data shown in FIG. 5, atomic layer deposition onto silicon coupons was carried out under the same conditions as in Example 1 using the following pulse regime: a.HCDS / Purge / 4DMAS / Purge / (NH3+H2) / Purge b.HCDS / Purge / NH3 / Purge c.HCDS / Purge / (NH3+H2) / Purge

[0037] Growth rate (Å / cycle) was plotted against HCDS pulse time in seconds. The data show that atomic layer deposition using the HCDS / (NH3+H2) regime (with or without 4DMAS) achieves saturation with a 5 second HCDS pulse.

[0038] Example 5 -NH3 / H2 Referring to the data shown in FIG. 6, a silicon nitride film was deposited using the process parameters of Example 1 while using a pulsing regime of HCDS / (NH3+H2) to provide a silicon nitride film having 48.5 atomic percent silicon, 43.2 atomic percent nitrogen, 0 atomic percent carbon, 3.6 atomic percent oxygen, and 4.7 atomic percent chlorine, with a silicon to nitrogen ratio of 1.12:1.

[0039] Referring to the data shown in Figure 4, a silicon nitride film was deposited using the process parameters of Example 1 while using the HCDS / NH3 pulsing regime as a comparative example. The film had 46.5 percent silicon, 48.6 atomic percent nitrogen, 0 atomic percent carbon, 1.6 atomic percent oxygen, and 3.3 atomic percent chlorine, with a silicon to nitrogen ratio of 0.96:1. This experiment shows that the NH3+H2 pulsing regime increases the silicon:nitrogen ratio without adding carbon to the film.

[0040] Example 6 - HCDS / 4DMAS Referring to the data shown in FIG. 7, a silicon nitride film was deposited using the process parameters of Example 1 while using a HCDS / 4DMAS pulsing regime to provide a film having 49.7 atomic percent silicon, 19.9 atomic percent nitrogen, 20.5 atomic percent carbon, 7.5 atomic percent oxygen, and 2.4 atomic percent chlorine, with a silicon to nitrogen ratio of 2.5:1.

[0041] Referring to the data shown in Figure 4, a silicon nitride film was deposited using the process parameters of Example 1 while using the HCDS / NH3 pulsing regime as a comparative example. The film had 46.5 atomic percent silicon, 48.6 atomic percent nitrogen, 0 atomic percent carbon, 1.6 atomic percent oxygen, and 3.3 atomic percent chlorine, with a silicon:nitrogen ratio of 0.96:1. The data shows that the pulsing regime using HCDS / 4DMAS improves the silicon to nitrogen ratio and also introduces a significant amount of carbon into the film.

[0042] Example 7 - Etch rate comparison The data shown in Figure 8 shows the wet etch rate of a 100:1 diluted HF solution on a film prepared using HCDS / 4DMAS atomic layer deposition at 600 °C, 2 Torr, and 5 second 4DMAS pulses. The data shows a bulk wet etch rate of approximately 0.4 Å / min.

[0043] The data shown in Figure 9 shows the wet etch rate of a 100:1 diluted HF solution on a film prepared using HCDS / 4DMAS atomic layer deposition at 570 °C and 2 Torr. The data shows a bulk wet etch rate of 0.36 Å / min. TIFF2025508534000007.tif52170

[0044] This data shows that the addition of tetrakis(dimethylamino)silane to the pulse sequence, and the addition of hydrogen to the conventional hexachlorodisilane / ammonia ALD method, achieves saturation, increases the silicon content (i.e., increases the silicon:nitrogen ratio), and increases the growth rate.

[0045] Aspects In a first aspect, the present invention provides a method for depositing a silicon nitride film on a microelectronic device substrate, comprising: Under deposition conditions: a. Halosilane compounds, b. an aminosilane, and optionally c. A compound of the formula R2NH, where each R is independently hydrogen or a C1-C4 alkyl group in combination with hydrogen. The method includes contacting a precursor compound with a continuous pulse comprising a pulse sequence comprising:

[0046] In a second aspect, the present invention provides a method for depositing a silicon nitride film on a microelectronic device substrate, comprising: Under deposition conditions: a. a halosilane compound, and b. A compound of the formula R2NH, where each R is independently hydrogen or a C1-C4 alkyl group in combination with hydrogen. The method includes contacting a precursor compound with a continuous pulse comprising a pulse sequence comprising:

[0047] In a third aspect, the present invention provides a method according to the first or second aspect, wherein a., b. and / or c. are followed by a purging step with an inert gas.

[0048] In a fourth aspect, the present invention provides a method according to any one of the first, second or third aspects, wherein the halosilane compound is hexachlorodisilane.

[0049] In a fifth aspect, the present invention relates to an aminosilane having the formula The method of the first or third aspect is provided, wherein the compound is a compound of TIFF2025508534000008.tif37170.

[0050] In a sixth aspect, the present invention relates to an aminosilane having the formula The method according to the first or third aspect is provided, wherein the compound is a compound of formula (I).

[0051] In a seventh aspect, the present invention relates to an aminosilane having the formula The method according to the first or third aspect is provided, wherein the compound is a compound of TIFF2025508534000010.tif41170.

[0052] In an eighth aspect, the present invention relates to an aminosilane having the formula The method of the first or third aspect is provided, wherein the compound is of formula (I).

[0053] In a ninth aspect, the present invention relates to an aminosilane having the formula The method of the first or third aspect is provided, wherein the compound is of formula (I) TIFF2025508534000012.tif24170.

[0054] In a tenth aspect, the present invention provides a method according to any one of the first to ninth aspects, wherein the silicon nitride film comprises a silicon:nitrogen ratio of at least about 3.1:4.

[0055] In an eleventh aspect, the present invention provides a method according to any one of the first to ninth aspects, wherein the silicon nitride film comprises a silicon:nitrogen ratio of about 1:1 or greater.

[0056] In a twelfth aspect, the present invention relates to a method for treating a pulmonary artery disease, the method comprising the steps of: Hexachlorodisilane / purge / Tetrakis(dimethylamino)silane / purge / (NH3+H2) / purge The present invention provides a method according to the first or third aspect, comprising:

[0057] In a thirteenth aspect, the present invention relates to a pulse sequence comprising: Hexachlorodisilane / purge / (tetrakis(dimethylamino)silane + H2) / purge / NH3 / purge The method according to the first aspect is provided, comprising:

[0058] In a fourteenth aspect, the present invention relates to a pulse sequence comprising: Hexachlorodisilane / purge / Tetrakis(dimethylamino)silane / purge / NH3 / purge The method according to the first aspect is provided, comprising:

[0059] In a fifteenth aspect, the present invention provides a method according to the second aspect, wherein the pulse sequence comprises hexachlorodisilane / purge / (NH3+H2) / purge.

[0060] In a sixteenth aspect, the present invention provides a method according to the first aspect, wherein the pulse sequence comprises hexachlorodisilane, tetrakis(dimethylamino)silane, and a mixture of ammonia and hydrogen.

[0061] In a seventeenth aspect, the present invention provides a method according to any one of the first to sixteenth aspects, further comprising at least one pulse sequence comprising plasma ammonia or plasma hydrogen.

[0062] In an eighteenth aspect, the present invention provides a method according to any one of the first to seventeenth aspects, wherein the silicon nitride film has a conformality of at least about 95%.

[0063] In a nineteenth aspect, the present invention provides a microelectronic device structure having a silicon nitride film thereon, the microelectronic device structure having at least one substructure having an aspect ratio greater than about 10, the silicon nitride film having a conformality of at least about 95% and a silicon to nitride ratio of at least about 1.04:1 to about 1.12:1.

[0064] In a twentieth aspect, the present invention provides the device according to the nineteenth aspect, wherein the aspect ratio is from about 10 to about 500.

[0065] Having thus described several exemplary embodiments of the present disclosure, those skilled in the art will readily appreciate that still other embodiments may be made and used within the scope of the appended claims. Many advantages of the present disclosure, which are covered by this document, have been set forth in the foregoing description. It will be understood, however, that the present disclosure is in many respects merely illustrative. The scope of the present disclosure is, of course, to be defined in the language in which the appended claims are expressed.

Claims

1. 1. A method for depositing a silicon nitride film on a microelectronic device substrate, comprising: Under deposition conditions: a. a halosilane compound, b. aminosilane, and c. a group of formula R in combination with hydrogen ２ NH, wherein each R is independently hydrogen or C １ ~C ４ is an alkyl group a pulse sequence comprising:

2. 1. A method for depositing a silicon nitride film on a microelectronic device substrate, comprising: Under deposition conditions: a. a halosilane compound, and b. a group of formula R in combination with hydrogen ２ NH, wherein each R is independently hydrogen or C １ ~C ４ is an alkyl group a pulse sequence comprising:

3. 10. The method of claim 1, wherein steps a., b., and / or c. are followed by a purging step with an inert gas.

4. 2. The method of claim 1, wherein the halosilane compound is hexachlorodisilane.

5. The aminosilane has the formula The method of claim 1, wherein the compound is

6. The aminosilane has the formula The method of claim 1, wherein the compound is

7. The aminosilane has the formula The method of claim 1, wherein the compound is

8. The aminosilane has the formula The method of claim 1, wherein the compound is

9. The aminosilane has the formula The method of claim 1, wherein the compound is

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