Compositions, methods, and systems for forming silicon containing films

Abstract

The present disclosure relates to silicon precursor compositions that are particularly suitable for forming silicon containing films using vapor deposition methods. The silicon precursors comprise at least one silylphosphanyl group. In certain embodiments, the silicon precursors comprise two or more silylphosphanyl groups that are positioned around a central linking unit (e.g., an atom or group of atoms). Also disclosed herein are methods for forming the silicon precursor compositions and vapor deposition methods and systems for forming silicon containing films using the compositions. In particular, the disclosed silicon precursor compositions are useful for forming silicon nitride films.

Description

COMPOSITIONS, METHODS, AND SYSTEMS FOR FORMINGSILICON CONTAINING FILMSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This Application claims the benefit of U.S. Provisional Application 63 / 610,434 filed on December 15, 2023, U.S. Provisional Application 63 / 560,233 filed on March 1, 2024, U.S. Provisional Application 63 / 560,276 filed on March 1, 2024, and U.S. Provisional Application 63 / 560,303 filed on March 1, 2024, the entire contents of each of which are incorporated herein by reference.FIELD

[0002] The present disclosure generally relates to the field of semiconductor processing methods and systems. In particular, silicon precursor compositions that are suitable for forming silicon containing films and methods of making said compositions and methods and systems for using said compositions are disclosed.BACKGROUND

[0003] As semiconductor device dimensions continue to scale, there is a need in the art for silicon containing layers that have improved material properties, such as high conformality, low leakage rates, a low dielectric constant, and good wet etch resistance. Furthermore, such silicon containing layers must be able to be formed using vapor deposition methods that provide precise thickness control at temperatures that are consistent with the fabrication of device structures and, in some applications, while maintaining a high growth per cycle (GPC). In particular, deposition processes that produce high quality silicon nitride films at lower temperatures are of high interest.

[0004] Atomic layer deposition (ALD) is a vapor deposition method that generally relies on controlled surface reactions of chemical reactants that are sequentially introduced into a reaction chamber comprising a substrate. Because the reactions with the surface are generally self-limiting, ALD provides for precise control over the film thickness and conformal coverage of the substrate can be obtained. ALD methods for depositing silicon nitride films are known; however, several limitations remain. For example, thermal ALD methods for forming silicon nitride generally require the use of high temperatures (e.g., about 600°C to 800°C) to promote the various surface reaction. Plasma enhanced ALD methods may be performed at lower temperatures; however, silicon nitride films formed using such methods generally suffer from poor film quality and / or low conformality.

[0005] The selection of the chemical precursor(s) that are used in ALD methods can greatly influence both the deposition process conditions and the material properties of the resulting layer. A variety of precursors for silicon deposition are known in the art, including halogenated silanes (e.g., SiC’h. SiFFCU, SiHCh, Si2Cle, SiFFE, etc.), silanes (e.g., SiFL, Si(SiH3)4, SiH(CH3)3, etc.), aminosilanes (e.g., BTBAS, 3DMAS, DSBAS, BDEAS, DIPAS, etc.), and silylamines (e.g., N(SiH3)3, etc.), among others, each with their own benefits and drawbacks. Finding improved silicon precursors for ALD processes is an ongoing effort. In this regard, the present disclosure relates to new silicon precursor compositions and methods of making said precursor compositions and methods and systems for using said precursor compositions to deposit silicon containing films that meet many of the above listed requirements.

[0006] Any discussion, including discussion of problems and solutions, set forth in this section has been included in this disclosure solely for the purpose of providing a context for the present disclosure. Such discussion should not be taken as an admission that any of the information was known at the time the invention was made or otherwise constitutes prior art.SUMMARY

[0007] This summary introduces a selection of concepts in a simplified form, which may be described in further detail below. This summary is not intended to necessarily identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0008] The present disclosure relates to silicon precursor compositions and to methods for forming said compositions as well as methods and systems for forming silicon containing films using said compositions using a vapor deposition process. The silicon precursor compositions comprise a silicon precursor that comprise at least one silylphosphanyl group, typically at least two silylphosphanyl groups. In certain embodiments, the compositions comprise a silicon precursor that comprises two or more silylphosphanyl groups that are bonded to a central linking group (e.g., an atom or a group of atoms).

[0009] An aspect of the present disclosure relates to silicon precursor compositions. The silicon precursor compositions may comprise a silicon precursor that has a structure according to general Formula (1), general Formula (2), or general Formula (3):ARm[PZn(SiQ3)2-n]4-m (1)[( Q Si)2-nZnP] 3 -mRmA-PZn SiQs) l-n-ARm[PZn(SiQ3)2-n] 3-m (2)[(QsSi)2 -nZnP]3 -mRmA-ARm[PZn(SiQ3)2-n]3-m (3) wherein: n is an integer having a value of 0 or 1; m is an integer having a value of 0, 1, or 2;A is a silicon atom (Si) or a carbon atom (C);P is a phosphorous atom that is bonded to A by a P-A bond;Si is a silicon atom that is bonded to P by an Si-P bond;R is a substituent that is bonded to A by an A-R bond, each R is independently selected from the group consisting of a hydrogen, a hydrocarbyl group, a silyl group, an alkoxy group, and an amino group;Z is a substituent that is bonded to P by a P-Z bond, each Z is independently selected from the group consisting of a hydrocarbyl group, an alkoxy group, and an amino group; andQ is a substituent that is bonded to Si by a Si-Q bond, each Q is independently selected from the group consisting of a hydrogen, a hydrocarbyl group, an alkoxy group, and an amino group.

[0010] In some embodiments, the A group of the silicon precursor is a silicon atom.

[0011] In some embodiments, the A group of the silicon precursor is a carbon atom.

[0012] In some embodiments, the integer m is 2.

[0013] In some embodiments, the integer m is 1.

[0014] In some embodiments, the integer m is 0.

[0015] In some embodiments, the integer n is 0.

[0016] In some embodiments, each of the Q substituents of the silicon precursor is independently selected from the group consisting of a hydrogen atom and a hydrocarbyl group. The hydrocarbyl group may be an alkyl group.

[0017] In some embodiments, each of the R substituents of the silicon precursor, if present, is independently selected from the group consisting of a hydrogen atom, a silyl group, and a hydrocarbyl group. The hydrocarbyl group may be an alkyl group.

[0018] In some embodiments, each of the Z substituents of the silicon precursor, if present, is an independently selected hydrocarbyl group. The hydrocarbyl group may be an alkyl group.

[0019] In some embodiments, the silicon precursor is free of carbon.

[0020] In some embodiments, the silicon precursor has a structure according to general Formula (1). In some of these embodiments, n=0 and the silicon precursor has a structure according to a Formula (la): ARm[P(SiQ3)2]4-m. Further, in some of these embodiments, the R substituents are selected from a hydrogen atom, a silyl group, and a hydrocarbyl group, wherein the hydrocarbyl group may be an alkyl group; and the Q substituents are selected from a hydrogen atom and a hydrocarbyl group, wherein the hydrocarbyl group may be an alkyl group.

[0021] In some embodiments, the silicon precursor is selected from the group consisting of SiH2(P(SiH3)2)2, SiHMe(P(SiH3)2)2, SiMe2(P(SiH3)2)2, SiH(SiH3)(P(SiH3)2)2, Si(SiH3)2(P(SiH3)2)2, SiH2(P(SiMe3)2)2, SiHMe(P(SiMe3)2)2, SiMe2(P(SiMe3)2)2, SiH(SiH3)(P(SiMe3)2)2, Si(SiH3)2(P(SiMe3)2)2, SiH2(P(SiEt3)2)2, SiHMe(P(SiEt3)2)2, SiMe2(P(SiEt3)2)2, SiH(SiH3)(P(SiEt3)2)2,Si(SiH3)2(P(SiEt3)2)2, SiH2(PMe(SiH3))2, SiHMe(PMe(SiH3))2, SiMe2(PMe(SiH3))2, SiH(SiH3)(PMe(SiH3))2, Si(SiH3)2(PMe(SiH3))2, SiH2(PMe(SiMe3))2, SiHMe(PMe(SiMe3))2, SiMe2(PMe(SiMe3))2, SiH(SiH3)(PMe(SiMe3))2, Si(SiH3)2(PMe(SiMe3))2, SiH2(PMe(SiEt3))2, SiHMe(PMe(SiEt3))2, SiMe2(PMe(SiEt3))2, SiH(SiH3)(PMe(SiEt3))2, Si(SiH3)2(PMe(SiEt3))2, SiH(P(SiH3)2)3, SiMe(P(SiH3)2)3, Si(SiH3)(P(SiH3)2)3, SiH(P(SiMe3)2)3, SiMe(P(SiMe3)2)3, Si(SiH3)(P(SiMe3)2)3, SiH(P(SiEt3)2)3, SiMe(P(SiEt3)2)3, Si(SiH3)(P(SiEt3)2)3, SiH(PMe(SiH3))3, SiMe(PMe(SiH3))3, Si(SiH3)(PMe(SiH3))3, SiH(PMe(SiMe3))3, SiMe(PMe(SiMe3))3, Si(SiH3)(PMe(SiMe3))3, SiH(PMe(SiEt3))3, SiMe(PMe(SiEt3))3, Si(SiH3)(PMe(SiEt3))3, Si(P(SiH3)2)4, Si(P(SiMe3)2)4, Si(P(SiEt3)2)4, Si(PMe(SiH3))4, Si(PMe(SiMe3))4, Si(PMe(SiEt3))4, and combinations thereof.

[0022] In some embodiments, the silicon precursor is selected from the group consisting of CH2(P(SiH3)2)2, CHMe(P(SiH3)2)2, CMe2(P(SiH3)2)2, CH2(P(SiMe3)2)2, CHMe(P(SiMe3)2)2, CMe2(P(SiMe3)2)2, CH2(P(SiEt3)2)2, CHMe(P(SiEt3)2)2, CMe2(P(SiEt3)2)2, CH2(PMe(SiH3))2, CHMe(PMe(SiH3))2, CMe2(PMe(SiH3))2, CH2(PMe(SiMe3))2, CHMe(PMe(SiMe3))2, CMe2(PMe(SiMe3))2, CH2(PMe(SiEt3))2, CHMe(PMe(SiEt3))2, CMe2(PMe(SiEt3))2, CH(P(SiH3)2)3, CMe(P(SiH3)2)3, CH(P(SiMe3)2)3, CMe(P(SiMe3)2)3, CH(P(SiEt3)2)3, CMe(P(SiEt3)2)3,CH(PMe(SiH3))3, CMe(PMe(SiH3))3, CH(PMe(SiMe3))3, CMe(PMe(SiMe3))3, CH(PMe(SiEt3))3, CMe(PMe(SiEt3))3, C(P(SiH3)2)4, C(P(SiMe3)2)4, C(P(SiEt3)2)4, C(PMe(SiH3))4, C(PMe(SiMe3))4, C(PMe(SiEt3))4, and combinations thereof.

[0023] In some embodiments, the silicon precursor has a structure according to general Formula (2). In some of these embodiments, n=0 and the silicon precursor has a structure according to a Formula (2a): [(Q3Si)2P]3.mRmA-P(SiQ3)-ARm[P(SiQ3)2]3.m. Further, in some of these embodiments, the R substituents, if present, are selected from a hydrogen atom, a silyl group, and a hydrocarbyl group, wherein the hydrocarbyl group may be an alkyl group; and the Q substituents are selected from a hydrogen atom and a hydrocarbyl group, wherein the hydrocarbyl group may be an alkyl group.

[0024] In some embodiments, the silicon precursor is selected from the group consisting of (H3Si)2P- SiH2-P(SiH3)-SiH2-P(SiH3)2, (H3Si)2P-SiH(Me)-P(SiH3)-SiH(Me)-P(SiH3)2, (H3Si)2P-Si(Me)2- P(SiH3)-Si(Me)2-P(SiH3)2, (Me3Si)2P-SiH2-P(SiMe3)-SiH2-P(SiMe3)2, (Me3Si)2P-SiH(Me)- P(SiMe3)-SiH(Me)-P(SiMe3)2, (Me3Si)2P-Si(Me)2-P(SiMe3)-Si(Me)2-P(SiMe3)2, (H3Si)(Me)P-SiH2- P(Me)-SiH2-P(Me)(SiH3), (H3Si)(Me)P-SiH(Me)-P(Me)-SiH(Me)-P(Me)(SiH3), (H3Si)(Me)P- Si(Me)2-P(Me)-Si(Me)2-P(Me)(SiH3), (Me3Si)(Me)P-SiH2-P(Me)-SiH2-P(Me)(SiMe3), (Me3Si)(Me)P- SiH(Me)-P(Me)-SiH(Me)-P(Me)(SiMe3), (Me3Si)(Me)P-Si(Me)2-P(Me)-Si(Me)2-P(Me)(SiMe3), and combinations thereof.

[0025] In some embodiments, the silicon precursor is selected from the group consisting of (H3Si)2P- CH2-P(SiH3)-CH2-P(SiH3)2, (H3Si)2P-CH(Me)-P(SiH3)- CH(Me)-P(SiH3)2, (H3Si)2P-C(Me2)-P(SiH3)- C(Me2)-P(SiH3)2, (Me3Si)2P-CH2-P(SiMe3)-CH2-P(SiMe3)2, (Me3Si)2P-CH(Me)-P(SiMe3)- CH(Me)-P(SiMe3)2, (Me3Si)2P-C(Me2)-P(SiMe3)-C(Me2)-P(SiMe3)2, (H3Si)(Me)P-CH2-P(Me)-CH2-P(Me)(SiH3), (H3Si)(Me)P-CH(Me)-P(Me)-CH(Me)-P(Me)(SiH3), (H3Si)(Me)P-C(Me2)-P(Me)- C(Me2)-P(Me)(SiH3), (Me3Si)(Me)P-CH2-P(Me)-CH2-P(Me)(SiMe3), (Me3Si)(Me)P-CH(Me)-P(Me)- CH(Me)-P(Me)(SiMe3), (Me3Si)(Me)P-C(Me2)-P(Me)-C(Me2)-P(Me)(SiMe3), and combinations thereof.

[0026] In some embodiments, the silicon precursor has a structure according to general Formula (3). In some of these embodiments, n=0 and the silicon precursor has a structure according to a Formula (3a): [(Q3Si)2P]3.mRmA-ARm[P(SiQ3)2]3.m. Further, in some of these embodiments, the R substituents, if present, are selected from a hydrogen atom; a silyl group; and a hydrocarbyl group, wherein the hydrocarbyl group may be an alkyl group; and the Q substituents are selected from a hydrogen atom and a hydrocarbyl group, wherein the hydrocarbyl group may be an alkyl group.

[0027] In some embodiments, the silicon precursor is selected from the group consisting of[SIH2(P(SIH3)2)]2, [SiHMe(P(SiH3)2)]2, [SiMe2(P(SiH3)2)]2, [SIH(SIH3)(P(SIH3))]2,[SI(SIH3)2(P(SIH3))]2, [SiH2(P(SiMe3)2)]2, [SiHMe(P(SiMe3)2)]2, [SiMe2(P(SiMe3)2)]2,[SiH(SiH3)(P(SiMe3)2)]2, [Si(SiH3)2(P(SiMe3)2)]2, [SiH2(P(SiEt3)2)]2, [SiHMe(P(SiEt3)2)]2,[SiMe2(P(SiEt3)2)]2, [SiH(SiH3)(P(SiEt3)2)]2, [Si(SiH3)2(P(SiEt3)2)]2, [SiH2(PMe(SiH3))]2,[SiHMe(PMe(SiH3))]2, [SiMe2(PMe(SiH3))]2, [SiH(SiH3)(PMe(SiH3))]2, [Si(SiH3)2(PMe(SiH3))]2, [SiH2(PMe(SiMe3))]2, [SiHMe(PMe(SiMe3))]2, [SiMe2(PMe(SiMe3))]2, [SiH(SiH3)(PMe(SiMe3))]2[Si(SiH3)2(PMe(SiMe3))]2, [SiH2(PMe(SiEt3))]2, [SiHMe(PMe(SiEt3))]2, [SiMe2(PMe(SiEt3))]2, [SiH(SiH3)(PMe(SiEt3))]2, [Si(SiH3)2(PMe(SiEt3))]2, [SiH(P(SiH3)2)2]2, [SiMe(P(SiH3)2)2]2,[SI(SIH3)(P(SIH3)2)2]2, [SiH(P(SiMe3)2)2]2, [SiMe(P(SiMe3)2)2]2, [Si(SiH3)(P(SiMe3)2)2]2,[SiH(P(SiEt3)2)2]2, [SiMe(P(SiEt3)2)2]2, [Si(SiH3)(P(SiEt3)2)2]2, [SiH(PMe(SiH3))2]2,[SiMe(PMe(SiH3))2]2, [Si(SiH3)(PMe(SiH3))2]2, [SiH(PMe(SiMe3))2]2, [SiMe(PMe(SiMe3))2]2, [Si(SiH3)(PMe(SiMe3))2]2, [SiH(PMe(SiEt3))2]2, [SiMe(PMe(SiEt3))2]2, [Si(SiH3)(PMe(SiEt3))2]2, [SI(P(SIH3)2)3]2, [Si(P(SiMe3)2)3]2, [Si(P(SiEt3)2)3]2, [Si(PMe(SiH3))3]2, [Si(PMe(SiMe3))3]2,[Si(PMe(SiEt3))3]2, and combinations thereof.

[0028] In some embodiments, the silicon precursor is selected from the group consisting of [CH2(P(SiH3)2)]2, [CHMe(P(SiH3)2)]2, [CMe2(P(SiH3)2)]2, [CH2(P(SiMe3)2)]2, [CHMe(P(SiMe3)2)]2, [CMe2(P(SiMe3)2)]2, [CH2(P(SiEt3)2)]2, [CHMe(P(SiEt3)2)]2, [CMe2(P(SiEt3)2)]2, [CH2(PMe(SiH3))]2, [CHMe(PMe(SiH3))]2, [CMe2(PMe(SiH3))]2, [CH2(PMe(SiMe3))]2, [CHMe(PMe(SiMe3))]2, [CMe2(PMe(SiMe3))]2, [CH2(PMe(SiEt3))]2, [CHMe(PMe(SiEt3))]2, [CMe2(PMe(SiEt3))]2, [CH(P(SIH3)2)2]2, [CMe(P(SiH3)2)2]2, [C(SIH3)(P(SIH3)2)2]2, [CH(P(SiMe3)2)2]2, [CMe(P(SiMe3)2)2]2, [CH(P(SiEt3)2)2]2, [CMe(P(SiEt3)2)2]2, [CH(PMe(SiH3))2]2, [CMe(PMe(SiH3))2]2,[CH(PMe(SiMe3))2]2, [CMe(PMe(SiMe3))2]2, [CH(PMe(SiEt3))2]2, [CMe(PMe(SiEt3))2]2, [C(P(SIH3)2)3]2, [C(P(SiMe3)2)3]2, [C(P(SiEt3)2)3]2, [C(PMe(SiH3))3]2, [C(PMe(SiMe3))3]2,[C(PMe(SiEt3))3]2, and combinations thereof.

[0029] In some embodiments, the silicon precursor has a structure according to any one of those structures shown in FIG. 4A and FIG. 4B.

[0030] In some embodiments, the silicon precursor composition has a purity of about 95 wt % or more of the silicon precursor. The silicon precursor composition may have a purity of about 95 wt % or more, or about 97 wt % or more, or about 98 wt % or more, or about 99 wt % or more, or about 99.5 wt % or more, or about 99.9 wt % or more.

[0031] Another aspect of the present disclosure relates to methods for forming the silicon precursor composition described in any of the above paragraphs. In some embodiments, the method comprises contacting a silylphosphine reactant with an alkyl lithium compound to form a lithium silylphosphine compound, then contacting the lithium silylphosphine compound with a linking compound to form a composition comprising the silicon precursor.

[0032] In some embodiments, the silicon precursor is a first silicon precursor, and the method further comprises contacting the first silicon precursor with a halosilane reactant to form a second silicon precursor.

[0033] Another aspect of the present disclosure relates to a vapor delivery vessel comprising the silicon precursor composition described in any of the above related paragraphs. The vapor delivery vessel comprises an outer wall that encloses a cavity for storing the silicon precursor composition and a gas outlet for allowing a vapor of the silicon precursor to exit the cavity.

[0034] In some embodiments, the vapor delivery vessel further comprises a carrier gas inlet and a carrier gas conduit comprising a distal portion comprising an end opening that extends into the cavity. The carrier gas conduit and the end opening may extend into the silicon precursor composition for passing a carrier gas through the silicon precursor composition. Alternatively, the carrier gas conduit and the end opening may extend into a headspace of the cavity above the silicon precursor composition for passing a carrier gas over the silicon precursor composition.

[0035] In some embodiments, the vapor delivery vessel further comprises a probe member. The probe member may comprise a level sensor.

[0036] In some embodiments, the outer wall and the cavity of the vapor delivery vessel are formed from stainless steel.

[0037] Another aspect of the present disclosure relates to methods for forming silicon containing films using the silicon precursor composition described in any of the above related paragraphs. The method comprises providing a substrate in a reaction space and exposing a surface of the substrate to a vapor of the silicon precursor composition. In some embodiments, the surface of the substrate is additionally exposed a co-reactant.

[0038] In some embodiments, the method for forming a silicon containing film comprises providing a substrate in a reaction space and performing one or more deposition cycles of a cyclic deposition process comprising exposing a surface of the substrate to one of the silicon precursor composition and a coreactant, then exposing the surface of the substrate to the other of the silicon precursor composition and the co-reactant, thereby forming a silicon containing film on the surface of the substrate. The surface of the substrate may be exposed to the silicon precursor composition, then to the co-reactant. Additionally,or alternatively, the surface of the substrate may be exposed to the co-reactant, then to the silicon precursor composition. The cyclical deposition process can include one or more of an ALD process and a cyclical CVD process.

[0039] In some embodiments, the reaction space is purged after one or more of the exposing of the surface of the substrate to the silicon precursor composition and the exposing of the surface of the substrate to the co-reactant.

[0040] In some embodiments, the step of exposing the surface of the substrate to a co-reactant comprises forming a plasma either in the reaction space or upstream of the reaction space.

[0041] In some embodiments, the co-reactant comprises one or more of a nitrogen plasma species, an oxygen plasma species, a carbon plasma species, a hydrogen plasma species, and a noble gas plasma species.

[0042] In some embodiments, the co-reactant comprises a nitrogen plasma species. In some embodiments, the co-reactant comprises one or more of activated nitrogen (N2), activated ammonia (NH3), nitrogen atoms (N), and NH and NH2 radicals.

[0043] In some embodiments, the co-reactant comprises an oxygen plasma species. In some embodiments, the co-reactant comprises one or more of atomic oxygen (O), excited diatomic oxygen (e.g., singlet oxygen (’02)), ozone (O3), hydroxyl radical (OH), peroxyl radical (e.g., HO2), and nitric oxide (NO).

[0044] In some embodiments, the method further comprises maintaining a temperature of the substrate at a set temperature of at least about 100 °C and no more than about 500 °C. The temperature of the substrate may be maintained at a set temperature of at least about 100 °C and no more than about 400 °C, or at least about 100 °C and no more than about 300 °C, or at least about 100 °C and no more than about 250 °C.

[0045] Another aspect of the present disclosure relates to systems for forming a silicon containing film using the silicon precursor composition described in any of the above related paragraphs, further using the methods for forming a silicon containing film described in any of the above related paragraphs. The system may be a semiconductor processing apparatus that comprises a reaction space for accommodating a substrate and a means for exposing the substrate to the silicon precursor composition. The semiconductor processing apparatus may further comprise a means for exposing the substrate to a co-reactant and optionally a means for purging the reaction space after one or both of the exposing steps.

[0046] In some embodiments, the semiconductor processing apparatus comprises: a reaction space for accommodating a substrate; a silicon precursor source for providing a vapor of the silicon precursor composition in gas communication via a silicon precursor source valve with the reaction space; a coreactant source for providing a reactant gas and / or a co-reactant in gas communication via a co-reactant source valve with the reaction space; a plasma unit comprising a plasma generator; and a controller operably connected to the silicon precursor source valve, the co-reactant source valve, and the plasmagenerator. The controller may be configured and programmed to control, supplying the silicon precursor composition vapor into the reaction space, supplying the reactant gas and / or co-reactant into the reaction space, and activating the plasma generator. The controller may be programmed to repeat the various process steps n time to deposit a silicon containing film on the surface of the substrate. In some embodiments, the silicon precursor source is a vapor delivery vessel that comprises the silicon precursor composition.

[0047] Another aspect of the present disclosure relates to a silicon containing film formed using the silicon precursor composition described in any of the above related paragraphs. Further, the silicon containing film may be formed using the methods and the systems described in any of the above related paragraphs. The silicon containing film comprises a layer of a material that comprises silicon. In some embodiments, the layer of the material further comprises one or more of nitrogen, oxygen, and carbon.

[0048] In some embodiments, the silicon containing film comprises a material that is selected from the group consisting of silicon nitride, silicon oxide, silicon carbide, silicon oxynitride, silicon oxycarbide, silicon carbon nitride, silicon carbon oxynitride, polysilicon, crystalline silicon, and amorphous silicon.

[0049] In some embodiments, the silicon containing film comprises a material that comprises silicon and nitrogen. The silicon containing film may comprise silicon nitride. The silicon containing film may consist of or consist essentially of silicon nitride.

[0050] In some embodiments, the silicon containing film has a phosphorous content of no more than about 20 at %. In some embodiments, the phosphorous content of the silicon containing film is no more than about 10 at %, or no more than about 5 at %, or no more than about 4 at %, or no more than about 3 at %, or no more than about 2 at %, or no more than about 1 at %.

[0051] In some embodiments, the silicon containing film has a carbon content of no more than about 20 at %. In some embodiments, the carbon content of the silicon containing film is no more than about 10 at %, or no more than about 5 at %, or no more than about 4 at %, or no more than about 3 at %, or no more than about 2 at %, or no more than about 1 at %.

[0052] In some embodiments, the silicon containing film has a GPC of about 0.3 to about 2.5 A / cycle. The GPC of the silicon containing film may be between about 0.5 to about 2.5 A / cycle, or between about 0.5 to about 2.0 A / cycle, or between about 0.5 to about 1.5 A / cycle.

[0053] In some embodiments, the silicon containing film has a wet etch rate of less than 2.5 nm / min in 1.5% dilute hydrofluoric acid. In some embodiments, the silicon containing film has a wet etch rate of less than 1.5 nm / min in 1.5% dilute hydrofluoric acid.

[0054] In some embodiments, the silicon containing film has a step coverage of about 90% more and less than about 110%. In some embodiments, the silicon containing film has a step coverage of about 95% or more and less than about 105%.

[0055] These and other embodiments will become readily apparent to those skilled in the art from the following detailed description of certain embodiments and with further reference to the attached figures. These embodiments or components thereof may be combined, or they may be applied separate fromeach other, as applicable, unless otherwise noted. The invention is not limited to any particular embodiments disclosed.BRIEF DESCRIPTION OF DRAWINGS

[0056] The accompanying drawings constitute part of the specification. The drawings are included to provide a further understanding of the disclosure, and together with the description explain certain principles of the disclosure. The drawings illustrate exemplary embodiments of how the disclosure can be made and used and are not to be construed as limiting the disclosure to only the illustrated and described examples. It will be appreciated that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. The illustrations presented herein are not meant to be actual views of any particular material, structure, or device, but are merely idealized representations that are used to describe embodiments of the disclosure. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help improve understanding of illustrated embodiments of the present disclosure . Further features and advantages will become apparent from the following, more detailed, description of various aspects, embodiments, and configurations of the disclosure, as illustrated by the drawings referenced below.

[0057] FIG. 1 shows embodiments of silicon precursor structures according to general Formula (1): structure (a) has an m=2 and n=l; structure (b) has an m=2 and n=0; structure (c) has an m=l and n=l; structure (d) has an m=l and n=0; structure (e) has an m=0 and n=l; and structure (f) has an m=0 and n=0.

[0058] FIG. 2 shows embodiments of silicon precursor structures according to general Formula (2): structure (a) has an m=2 and n=l; structure (b) has an m=2 and n=0; structure (c) has an m=l and n=l; structure (d) has an m=l and n=0; structure (e) has an m=0 and n=l; and structure (f) has an m=0 and n=0.

[0059] FIG. 3 shows embodiments of silicon precursor structures according to general Formula (3): structure (a) has an m=2 and n=l; structure (b) has an m=2 and n=0; structure (c) has an m=l and n=l; structure (d) has an m=l and n=0; structure (e) has an m=0 and n=l; and structure (f) has an m=0 and n=0.

[0060] FIGS. 4A and 4B shows exemplary silicon precursor structures according to Formula (la) (see structures (a)-(d) and (i)-(l)), Formula (2a) (see structures (e), (f), (m) and (n)), and Formula (3a) (see structures (g), (h), (o), and (p)).

[0061] FIG. 5 shows an embodiment of a synthetic route for forming silicon precursors having a structure according to Formula (la).

[0062] FIG. 6 shows an embodiment of a synthetic route for forming silicon precursors having a structure according to Formula (3 a).

[0063] FIG. 7 shows an embodiment of a synthetic route for forming silicon precursors having a structure according to Formula (2a).

[0064] FIG. 8 shows another embodiment of a synthetic route for forming certain silicon precursors having a structure according to Formula (la) and Formula (3a).

[0065] FIG. 9 is a process flow diagram of a cycle deposition process for forming a silicon containing fdm according to an embodiment of the present disclosure. Optional steps are shown by the dashed lines.

[0066] FIG. 10 is a perspective view of an exemplary vapor delivery vessel according to an embodiment of the present disclosure.

[0067] FIG. 11 is a perspective view of exemplary vapor delivery vessel according to another embodiment of the present disclosure. The inset shows a plan view of the top portion of the vessel.

[0068] FIG. 12 is a schematic presentation of a semiconductor processing apparatus according to an embodiment of the present disclosure.

[0069] FIGS. 13A and 13B shows the NMR spectroscopy results confirming the formation of (SiMe3)2P-CH2-P(SiMe3)2 in Example 1. An 'HNMR spectrum (<7S-toluene, 400 MHz, 298 K) is shown in FIG. 13A and a31P NMR spectrum (<7S-toluene, 163 MHz, 298 K) is shown in FIG. 13B.

[0070] FIGS. 14A and 14B shows the NMR spectroscopy results confirming the formation of (SiHAP- CH2-P(SiH3)2 in Example 2. An 'H NMR spectrum (<7S-toluene, 400 MHz, 298 K) is shown in FIG. 14A and a31P NMR spectrum (<7S-toluene, 163 MHz, 298 K) is shown in FIG. 14B.

[0071] FIGS. 15A and 15B shows the NMR spectroscopy results confirming the formation of (SiMe3)2P-SiH2-P(SiMe3)2 in Example 3. An 'H NMR spectrum (<7S-toluene, 400 MHz, 298 K) is shown in FIG. 15A and a31P NMR spectrum (<7S-toluene, 163 MHz, 298 K) is shown in FIG. 15B.DETAILED DESCRIPTION

[0072] The description of embodiments of compositions, methods, and systems provided below is merely exemplary and is intended for purposes of illustration only. The following description is not intended to limit the scope of the disclosure or the claims. Moreover, recitation of multiple embodiments having indicated features is not intended to exclude other embodiments having additional features or other embodiments incorporating different combinations of the stated features. Unless otherwise noted, the exemplary embodiments or components thereof may be combined or may be applied separate from each other. The headings provided herein, if any, are for convenience only and do not necessarily affect the scope or meaning of the claimed invention.

[0073] Definitions

[0074] As used herein, “atomic layer deposition”, abbreviated as “ALD”, refers to a vapor deposition process in which deposition cycles, such as a plurality of consecutive deposition cycles, are conductedin a reaction space (i.e., one or more reaction chambers). Generally, in ALD processes, during each deposition cycle, a precursor is introduced into a reaction space and is adsorbed onto a substrate surface, which may include a previously deposited material from a previous ALD cycle or other materials, forming maximally one monolayer of the precursor that does not readily react with additional excess precursor (i.e., a self-limiting reaction). Thereafter, in some cases, another precursor or a reactant may be introduced into the reaction space to convert the chemisorbed precursor to the desired material on the substrate surface. Other reaction steps may be included in the deposition cycle. ALD may occur by a thermal process (thermal ALD), where the reaction(s) are promoted by increasing the temperature of the substrate relevant to ambient temperature; and / or by a plasma enhanced process (PE-ALD), where the reaction(s) are promoted through the use of energetic plasma species. ALD, as used herein, may also be meant to include processes designated by related terms, such as chemical vapor atomic layer deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas source MBE, or organometallic MBE, and chemical beam epitaxy when performed with alternating pulses of reactants.

[0075] As used herein, “chemical vapor deposition”, abbreviated as “CVD”, refers to a vapor deposition process in which a film is deposited on a substrate by exposing its surface to one or more gaseous precursors and reactants, which react and / or decompose on the substrate surface to form the film. The precursors and / or reactants can be provided simultaneously to the reaction space, or in partially or completely separated pulses. In some embodiments, the precursors and / or reactants are provided until a layer having a desired thickness is deposited. In some embodiments, a cyclic CVD process can be used with multiple cycles to deposit a thin film having a desired thickness. In cyclic CVD processes, the precursors and / or reactants may be provided to the reaction space in pulses that do not overlap, or that partially or completely overlap. CVD may occur by a thermal process (thermal CVD), where the reaction(s) are promoted by increasing the temperature of the substrate relevant to ambient temperature; or by a plasma enhanced process (PE-CVD), where the reaction(s) are promoted through the use of energetic plasma species.

[0076] As used herein, a “cyclic deposition process” refers to a method or a process comprising sequentially introducing precursors and / or reactants into a reaction space to deposit a layer or a film on or over a substrate and includes processing techniques such as ALD, cyclical CVD, and hybrid cyclical deposition processes that include an ALD component and a cyclical CVD component. In preferred embodiments, a cyclic deposition process as disclosed herein refers to an ALD process.

[0077] As used herein, a “film” or “layer”, which may be used interchangeably, refers to a continuous, substantially continuous, or non-continuous material that extends in a direction perpendicular to a thickness direction to cover at least a portion of a surface. A film may be positioned on a lateral surface and / or on a sidewall of recessed features of a surface. A film can include two-dimensional materials, three-dimensional materials, nanoparticles, partial or full molecular layers, partial or full atomic layers, and / or clusters of atoms or molecules. A film may be built up from one or more non -discernablemonolayers or sub-monolayers to produce a uniform or a substantially uniform material, wherein the number of monolayers or sub-monolayers influences the thickness of the film.

[0078] As used herein, a “gas” refers to a state of mater consisting of atoms or molecules that have neither a defined volume nor shape. A gas includes vaporized solid and / or liquid and may be referred to as a vapor. A gas may be constituted by a single gas or a mixture of gases, depending on the context.

[0079] As used herein, a “hydrocarbyl group” refers to a chemical functional group that is derived from a hydrocarbon less one hydrogen. Hydrocarbyl groups include, but are not limited to, alkyl groups (an alkane less one hydrogen atom represented by a general formula CnH2n+i for linear or branched structures or CnH2n for cyclic structures, where n is an integer that is typically from 1 to 10, more typically from 1 to 4); alkenyl groups (an alkene less one hydrogen atom), alkynyl groups (an alkyne less one hydrogen atom); and aryl groups (an aromatic hydrocarbon less one hydrogen atom).

[0080] As used herein, a "plasma" refers to an ionized gas comprising of roughly equal numbers of negatively and positively charged species, generally electrons and ions. Excited and reactive species are also contained within the plasma, such as, for example, atoms and radicals, metastable atoms and molecules, and photons. A plasma discharge requires an externally imposed electric or magnetic field to ionize a gas. Plasma generation schemes and geometries, include, but are not limited to, capacitively coupled plasmas (CCPs), inductively coupled plasmas (ICPs), and RF -hollow cathode (HC) plasmas, which differ in their production of excited and reactive species and, as a result, they can provide very different fluxes of the various species.

[0081] As used herein, a “precursor” refers to a compound that participates in a chemical reaction to form another compound or element, wherein a portion of the precursor (an element or group within the precursor) is incorporated into the compound or element that results from the chemical reaction. The compound or element that results from the chemical reaction may be a layer and / or a film that is formed on a surface of a substrate.

[0082] As used herein, the term “purge” may refer to a procedure in which vapor phase precursors, reactants, and / or vapor phase byproducts are removed from a substrate surface for example by evacuating the reaction space with a vacuum pump and / or by replacing the gas inside a reaction space with an inert or substantially inert gas such as argon or nitrogen.

[0083] As used herein, a “reactant” refers to a compound that participates in a chemical reaction to form another compound or element. In some instances, a reactant is a precursor. In other instances, the compound or element that results from the chemical reaction does not contain a portion, or a significant portion, of the reactant (an element or group within the reactant) and therefore the reactant is not a precursor. In some instances, a reactant is referred to as a co-reactant.

[0084] As used herein, “silicon carbide” or “SiC” refers to a material that comprises silicon and carbon. In some embodiments, silicon carbide refers to a material that comprises Si-C bonds. In some embodiments, silicon carbide may not comprise significant proportions of elements other than silicon and carbon. Silicon carbide may be represented by the formula SiC. In some embodiments, the siliconcarbide comprises SiC. In some embodiments, the silicon carbide may consist of or consist essentially of SiC. Silicon carbide need not necessarily be a stoichiometric composition. An amount of silicon can range from 5% to 50%; an amount of carbon can range from about 50% to about 95%. In some embodiments, SiC films may comprise one or more elements in addition to silicon and carbon, such as, for example, hydrogen, oxygen, and / or nitrogen.

[0085] As used herein, “silicon carbonitride” or “SixCyNz” or “SiCN” refers to a material that comprises silicon, carbon, and nitrogen. Unless stated otherwise, SiCN is not intended to limit, restrict, or define the bonding or chemical state, for example, the oxidation state of any of Si, C, N, and / or any other element in the film. In some embodiments, silicon carbonitride comprises Si-N bonds and / or Si- C bonds. Silicon carbonitride may be represented by the formula SixCyNz. In some embodiments, the silicon carbonitride may comprise more Si-N bonds than Si-C bonds, for example, a ratio of Si-N bonds to Si-C bonds may be from about 1: 10 to about 10: 1. In some embodiments, the silicon carbonitride films may comprise from about 0.1% to about 50% carbon on an atomic basis. In some embodiments, the silicon carbonitride may comprise from about 0.1% to about 40%, or from about 0.5% to about 30%, or from about 1% to about 30%, or from about 5% to about 20% carbon on an atomic basis. In some embodiments, the silicon carbonitride may comprise from about 0.1% to about 70% nitrogen on an atomic basis. In some embodiments, the silicon carbonitride may comprise from about 10% to about 70%, or from about 15% to about 50%, or from about 20% to about 40% nitrogen on an atomic basis. In some embodiments, the silicon carbonitride may comprise about 0.1% to about 50% silicon on an atomic basis. In some embodiments, the silicon carbonitride may comprise from about 10% to about 50%, or from about 15% to about 40%, or from about 20% to about 35% silicon on an atomic basis. In some cases, the silicon carbonitride may include other elements, such as hydrogen or oxygen. The silicon carbonitride may comprise silicon carbide and silicon nitride.

[0086] As used herein, “silicon nitride” or “SixNy” or “SiN” refers to a material that comprises silicon and nitrogen. In some embodiments, silicon nitride refers to a material that comprises Si-N bonds. In some embodiments, silicon nitride may not comprise significant proportions of elements other than silicon and nitrogen. In some embodiments, an amount of silicon may range from about 1% to about 80% or range from about 5% to about 70%, or from about 10% to about 50% on an atomic basis. In some embodiments, an amount of nitrogen may range from about 20% to about 99% or range from about 30% to about 95%, or from about 50% to about 90% on an atomic basis. Silicon nitride may be represented by the formula SisN^ In some embodiments, the silicon nitride comprises Sis In some embodiments, the silicon nitride may consist of, or consists essentially of Sis In some cases, the silicon nitride may not comprise stoichiometric silicon nitride. In some cases, the silicon nitride may include other elements, such as, for example, carbon, oxygen, and / or hydrogen.

[0087] As used herein, “silicon oxide” or “SiOx” refers to a material that comprises silicon and oxygen. In some embodiments, silicon oxide refers to a material that comprises Si-0 bonds. In some embodiments, an amount of silicon may range from about 1% to about 95% or range from about 5% toabout 70%, or from about 10% to about 50%, or from about 15% to about 35% on an atomic basis. In some embodiments, an amount of oxygen may range from about 5% to about 99% or range from about 30% to about 95%, or from about 50% to about 90%, or from about 65% to about 85% on an atomic basis. Silicon oxide may be represented by the formula SiOx, where x can be between 0 and 2. In some embodiments, silicon oxide may not comprise significant proportions of elements other than silicon and oxygen. Silicon oxide may be represented by the formula Si O2. In some embodiments, the silicon oxide comprises SiCh. In some embodiments, the silicon oxide may consist of or consist essentially of SiC>2. In some cases, the silicon oxide may not comprise stoichiometric silicon oxide. In some cases, the silicon oxide can include other elements, such as, for example, carbon, nitrogen, and / or hydrogen.

[0088] As used herein, “silicon oxycarbide” or “SiOxCy” or “SiOC” refers to a material that comprises silicon, oxygen, and carbon. Unless stated otherwise, SiOC is not intended to limit, restrict, or define the bonding or chemical state, for example, the oxidation state of any of Si, O, C, and / or any other element in the film. In some embodiments, the SizOxCycomprises Si-C bonds and / or Si-0 bonds. In some embodiments, the SiOC may comprise Si-C bonds and Si-0 bonds and may not comprise Si-N bonds. In some embodiments, the SiOC may comprise more Si-0 bonds than Si-C bonds, for example, a ratio of Si-0 bonds to Si-C bonds may be from about 1: 10 to about 10: 1. In some embodiments, the SiOC may comprise from about 0.1% to about 50% carbon on an atomic basis. In some embodiments, the SiOC may comprise from about 0.1% to about 40%, or from about 0.5% to about 30%, or from about 1% to about 30%, or from about 5% to about 20% carbon on an atomic basis. In some embodiments, the SiOC may comprise from about 0.1% to about 70% oxygen on an atomic basis. In some embodiments, the SiOC may comprise from about 10% to about 70%, or from about 15 % to about 50%, or from about 20% to about 40% oxygen on an atomic basis. In some embodiments, the SiOC may comprise about 0.1% to about 50% silicon on an atomic basis. In some embodiments, the SiOC films may comprise from about 10% to about 50%, or from about 15% to about 40%, or from about 20% to about 35% silicon on an atomic basis. In some embodiments, silicon oxycarbide can be represented by the chemical formula SizOxCy, where z can range from about 0 to about 2, x can range from about 0 to about 2, and y can range from about 0 to about 5.

[0089] As used herein, “silicon oxycarbonitride” or “SizOxCyNw” or “SiOCN” refers to a material that comprises silicon, oxygen, nitrogen, and carbon. Unless stated otherwise, SiOCN is not intended to limit, restrict, or define the bonding or chemical state, for example, the oxidation state of any of Si, O, C, N and / or any other element in the material. In some embodiments, SiOCN is material that can be represented by the chemical formula SizOxCyNw, where z can range from about 0 to about 2, x can range from about 0 to about 2, y can range from about 0 to about 2, and w can range from about 0 to about 2.

[0090] As used herein, “silicon oxynitride” or “SiOxNy” or “SiON” refers to a material that comprises silicon, oxygen, and nitrogen. Unless stated otherwise, SiOxNyis not intended to limit, restrict, or define the bonding or chemical state, for example, the oxidation state of any of Si, O, N and / or any other element in the material. In some embodiments, the silicon oxynitride comprises Si-0 bonds and / or Si-N bonds. In some embodiments, the SiON may comprise more Si-0 bonds than Si-N bonds, for example, a ratio of Si-0 bonds to Si-N bonds may be from about 1: 10 to about 10: 1. In some embodiments, the SiON may comprise from about 0.1% to about 80%, or from about 0.5% to about 70%, or from about 1% to about 50%, or from about 5% to about 30% nitrogen on an atomic basis. In some embodiments, the SiON may comprise from about 0.1% to about 70% oxygen on an atomic basis. In some embodiments, the SiON may comprise from about 10% to about 70%, or from about 15% to about 50%, or from about 20% to about 40% oxygen on an atomic basis. In some embodiments, the SiON may comprise about 0.1% to about 50% silicon on an atomic basis. In some embodiments, the SiON fdms may comprise from about 10% to about 50%, or from about 15% to about 40%, or from about 20% to about 35% silicon on an atomic basis. In some embodiments, SiOxNyis material that can be represented by the chemical formula SiOxNy, where x can range from about 0 to about 2 and y can range from about 0 to about 2. The silicon oxynitride may comprise silicon oxide and silicon nitride.

[0091] As used herein, a “substrate” refers to an underlying material or materials that may be used to form, or upon which, a device, a circuit, a material, or a material layer may be formed. The substrate may be continuous or non-continuous; rigid or flexible; solid or porous; and combinations thereof. The substrate may be in any form, such as, for example, a powder, a sheet, a plate, or a workpiece . Substrates in the form a sheet may extend beyond the bounds of a process / reaction chamber where a deposition process occurs and, in some cases, move through the chamber such that the process continues until the end of the substrate is reached. Substrates in the form of a plate may include wafers in various shapes and sizes. Substrates may be made from semiconductor materials, including, for example, silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, and silicon carbide. A substrate can include one or more layers overlying a bulk material, for example the substrate may include nitrides, for example TiN, oxides, insulating materials, dielectric materials, conductive materials, metals, such as tungsten, ruthenium, molybdenum, cobalt, aluminum, or copper, or other metallic materials, crystalline materials, epitaxial, heteroepitaxial, and / or single crystal materials. The substrate can include various topologies, such as, for example, gaps, recesses, lines, trenches, vias, holes, or spaces between elevated portions, such as fins, and the like formed within or on at least a portion of a layer of the substrate.

[0092] As used herein, “step coverage” refers to the growth rate of a layer on a distal end surface of a recess, divided by the growth rate of that layer on a proximal end surface of the recess, expressed as a percentage. Step coverage provides a measure of the conformity of a layer.

[0093] As used herein, a “vapor delivery vessel” refers to a vessel that is suitable for or configured for vapor delivery of a substance that is contained within the vessel. The vapor delivery vessel comprises an outer wall that encloses a cavity for storing and / or holding the substance and a fluid outlet for allowing a vapor of the substance to exit the cavity. The substance contained within the cavity may be a composition that is suitable for vapor deposition or etch methods. For example, the substance contained within the cavity may comprise one or more precursors, one or more reactants, one or moreetchants, or one or more surface treatment agents, as applicable. The substance contained within the cavity may be a homogeneous or heterogenous mixture. The substance contained within the cavity may be in a solid form, a liquid form, a gaseous form, or a combination thereof. The vapor delivery vessel may be a vapor draw vessel, a carrier gas vessel, a double walled vessel, a sublimation vessel, and / or other configuration.

[0094] As used herein, a “wet etch rate”, abbreviated as “WER”, refers to the rate of material loss when said material is exposed to a liquid etchant. For example, the WER may refer to the loss of material from a layer, which may be determined by measuring the decrease in a thickness of the layer as a function of time. In some embodiments, the WER may be measured by exposing the layer to dilute hydrofluoric acid (dHF).

[0095] Articles “a” or “an” refer to a species or a genus including multiple species, depending on the context. As such, the terms “a / an”, “one or more”, and “at least one” can be used interchangeably herein.

[0096] The terms “comprising”, “including”, and “having” are open ended and do not exclude the presence of other elements or components, unless the context clearly indicates otherwise. Comprising, including, and having can be used interchangeably and include the meaning of “consisting of’. The phrase “consisting of’, however, indicates that no other features or components are present other than those mentioned, unless the context clearly indicates otherwise.

[0097] The term “about” as applied to a value generally refers to a range of numbers that is considered to be equivalent to the recited value (e.g., having the same function or result). In some instances, the term “about” may include numbers that are rounded to the nearest significant figure.

[0098] The term “essentially” as applied to a composition, a method, a system, or a structure generally means that the additional components do not substantially modify the properties, characteristics, and / or function of the composition, the method, the system, or the structure.

[0099] The term “substantially” as applied to a composition, a method, a system, or a structure generally refers to a proportion of a value, a property, a characteristic, or the like, or conversely a lack thereof, that is at least about 70%, or at least about 80%, or at least about 90%, or at least about 95%, or at least about 97%, or at least about 98%, or at least about 99%, or at least about 99.5%, or at least about 99.9%, or more, or any proportion between about 70% and about 100%. In some embodiments, the term “substantially” means a proportion of about 90%, or about 95%, or about 97%, or about 98%, or about 99%, or about 99.5%, or about 99.9%.

[0100] The terms “on” or “over” may be used to describe a relative location relationship. For example, an element, a fdm, or a layer may be directly positioned on or over and physically contacting at least a portion another element, fdm, or layer; or, alternatively, an element, a fdm, or a layer may be on or over another element, fdm or layer but have one or more interposed elements, fdms, or layers therebetween. Therefore, unless the term “directly” is separately used, the terms “on” or “over” will be construed to be a relative concept. Similar to this, it will be understood that the terms “under”, “underlying”, or “below” describe a relative location relationship and should be construed to be relative concepts.

[0101] The terms “at least one”, “one or more”, and “and / or” are open-ended expressions that are both conjunctive and disjunctive in operation. For example, each of the expressions “at least one of A, B, and C”, “at least one of A, B, or C”, “one or more of A, B, and C”, “one or more of A, B, or C”, and “A, B, and / or C” means A alone, B alone, C alone, A and B together, A and C together, B and C together, or A, B, and C together. When each one of A, B, and C in the above expressions refers to an element, such as X, Y, and Z, or class of elements, such as Xi-Xn, Yi-Ym, and Zi-Z0, the phrase is intended to refer to a single element selected from X, Y, and Z, a combination of elements selected from the same class (e.g., Xi and X2) as well as a combination of elements selected from two or more classes (e.g., Y 1 and Zi ) .

[0102] It should be understood that every numerical range given throughout this disclosure is deemed to include the upper and the lower end points, and each and every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein. By way of example, the phrase “from about 2 to about 4” or “from 2 to 4” includes 2 and 4 and the whole number and / or integer ranges from about 2 to about 3, from about 3 to about 4, and each possible range based on real (e.g., irrational and / or rational) numbers, such as from about 2.1 to about 3.9, from about 2. 1 to about 3.4, and so on.

[0103] The standard abbreviations of the elements in the periodic table are used herein. For example, “P” refers to phosphorous, “Si” refers to silicon, “H” refers to hydrogen, “C” refers to carbon, and “N” refers to nitrogen, and “Li” refers to lithium. Additionally, in certain places throughout the disclosure, the following abbreviations of groups are used: “Me” stands for methyl (-CH3); “Et” stands for ethyl (- CH2CH3); “nPr” stands for n-propyl (-CH2CH2CH3); “iPr” stands for iso-propyl (-CH(CH3)2); “nBu” stands for n-butyl (-CH2CH2CH2CH3); “sBu” stands for sec-butyl (-CF^CFDCFLCFL), “iBu” stands for iso-butyl (-CFLCF^CFDCFL), “tBu” stands for tert-butyl (-CXC’ILF)- “Cp” stands for cyclopentadienyl (-C5H5), and “Ph” stands for phenyl (-C„H ).

[0104] In certain places throughout the disclosure, a chemical compound, a functional group of a chemical compound, or a substituent or ligand may be referred to by a chemical name (e.g., an IUPAC name or a common name), a molecular formula which may be abbreviated, or both. Additionally, or alternatively, a chemical compound may be shown by a structure which may be provided in stick form or partial stick form and may omit hydrogen atoms. In cases where there is a conflict between the chemical name and / or the molecular formula and / or the structure, and the identity of the chemical compound, the functional group, or the substituent or ligand cannot be unambiguously ascertained by one of skill in the art, then the structure shall prevail, followed by the molecular formula, then the chemical name.

[0105] In this disclosure, any defined meanings do not necessarily exclude ordinary and customary meanings, in some embodiments.

[0106] Description

[0107] Disclosed herein are silicon precursor compositions that are suitable for forming silicon containing films using a vapor deposition process such as CVD and / or ALD. The compositions comprise a silicon precursor that comprises at least one silylphosphanyl group. In certain embodiments, the compositions comprise a silicon precursor that comprises two or more silylphosphanyl groups that are positioned around a central linking unit (e.g., an atom or group of atoms). In some embodiments, the compositions comprise a silicon precursor that has at least one P-Si-P or P-C-P bond arrangement. In some embodiments, the compositions comprise a silicon precursor that has at least one Si-P-Si-P-Si or Si-P-C-P-Si bond arrangement. Also disclosed herein are methods for making the silicon precursor compositions as well as vapor deposition methods and systems for forming silicon containing films using said compositions.

[0108] There is a need in the art for silicon containing material layers that have improved properties, such as, for example, high conformality, low leakage rates, a low dielectric constant, and good wet etch resistance. Furthermore, such silicon containing layers must be able to be formed using vapor deposition methods that provide precise thickness control at temperatures that are consistent with the fabrication of device structures, typically no more than 500°C, while, for some applications, also having a high growth per cycle (GPC). The selection of chemical precursor(s) used in vapor deposition methods, can greatly influence both the deposition process conditions and the material properties of the resulting layer. In this regard, the inventors of the present disclosure have designed a new class of silicon precursors that meet many of the above listed requirements. In particular, the high Si content of the disclosed silicon precursors may beneficially contribute to a high GPC and a high conformality of the resulting silicon containing layers.

[0109] As used herein, a “silicon containing film” or a “silicon containing layer”, which may be used interchangeably, refers to a layer of a material that comprises silicon and includes, but is not limited to, material layers comprising silicon nitride, silicon oxide, silicon carbide, silicon oxynitride, silicon oxycarbide, silicon carbon nitride, silicon carbon oxynitride, polysilicon, crystalline silicon, and amorphous silicon. In some embodiments, the silicon containing film is selected from silicon nitride, silicon carbide, silicon oxide, and combinations and mixtures thereof.

[0110] In some embodiments, the silicon containing film further comprises phosphorous. In some of these embodiments, a phosphorous content of the silicon containing film is no more than about 20 at %, or no more than about 15 at %, or no more than about 10 at %, no more than about 5 at %, or no more than about 4 at %, or no more than about 3 at %, or no more than about 2 at %, or no more than about 1 at %, or no more than about 0.5 at %, or no more than about 0.1 at %. In some embodiments, the silicon containing film is free of or substantially free of phosphorous. In some embodiments, the silicon containing film further comprises hydrogen. In some of these embodiments, a hydrogen content of the silicon containing film is no more than about 20 at %, or no more than about 15 at %, or no more than about 10 at %, or no more than about 5 at %, or no more than about 4 at %, or no more than about 3 at %, or no more than about 2 at %, or no more than about 1 at %, or no more than about 0.5 at %, orno more than about 0.1 at %. In some embodiments, the silicon containing film further comprises halogen(s). In some of these embodiments, a halogen content of the silicon containing film is no more than about 20 at %, or no more than about 15 at %, or no more than about 10 at %, no more than about 5 at %, or no more than about 4 at %, or no more than about 3 at %, or no more than about 2 at %, or no more than about 1 at %, or no more than about 0.5 at %, or no more than about 0. 1 at %. In some embodiments, the silicon containing film is free of or substantially free of halogens. In some embodiments, the silicon containing film further comprises carbon. In some of these embodiments, a carbon content of the silicon containing film is no more than about 20 at %, or no more than about 15 at %, or no more than about 10 at %, no more than about 5 at %, or no more than about 4 at %, no more than about 3 at %, no more than about 2 at %, or no more than about 1 at %, or no more than about 0.5 at %, or no more than about 0.1 at %. In some embodiments, the silicon containing film is free of or substantially free of carbon.

[0111] In certain embodiments, the silicon containing film comprises silicon nitride. In some of these embodiments, the silicon containing film is a silicon nitride rich film. In some of these embodiments, the silicon containing film comprises silicon carbon nitride. In some of these embodiments, the silicon containing film comprises silicon oxynitride. In some of these embodiments, the silicon containing film consists of or consist essentially of silicon nitride. In some of these embodiments, the silicon nitride containing film has a phosphorous content of no more than about 20 at %, or no more than about 15 at %, or no more than about 10 at %, or no more than about 5 at %, or no more than about 4 at %, or no more than about 3 at %, or no more than about 2 at %, no more than about 1 at %, or no more than about 0.5 at %, or no more than about 0. 1 at %. In some of these embodiments, the silicon nitride containing film has a halogen content of no more than about 20 at %, or no more than about 15 at %, or no more than about 10 at %, or no more than about 5 at %, or no more than about 4 at %, or no more than about 3 at %, or no more than about 2 at %, or no more than about 1 at %, or no more than about 0.5 at %, or no more than about 0.1 at %. In some of these embodiments, the silicon nitride containing film has a carbon content of no more than about 20 at %, or no more than about 15 at %, or no more than about 10 at %, no more than about 5 at %, or no more than about 4 at %, or no more than about 3 at %, or no more than about 2 at %, no more than about 1 at %, or no more than about 0.5 at %, or no more than about 0. 1 at %.

[0112] Silicon Precursors

[0113] An aspect of the present disclosure relates to silicon precursors that are particularly suitable for forming silicon containing films and to composition comprising said silicon precursors. The silicon precursors comprise at least one silylphosphanyl group. In some embodiments, the silicon precursors comprise two or more silylphosphanyl groups. A silylphosphanyl group comprises a P-Si bond and may be represented by a P-SiQs, wherein Q is a substituent that is independently selected from the group consisting of a hydrogen atom, a hydrocarbyl group, an alkoxy group, and an amino group. In some ofthese embodiments, Q is independently selected from a hydrogen and a hydrocarbyl group, preferably the hydrocarbyl group is an alkyl group, typically a C1-C4 alkyl group.

[0114] In some embodiments, the silicon precursors disclosed herein have a structure according to a general Formula (0), a general Formula (1), a general Formula (2), or a general Formula (3):PZm(SiQ3)3-m(0)ARm[PZn(SiQ3)2-n]4-m (1)[( Qs Si)2 -nZnP] 3 -mRmA-PZn(SiQ3) l-n-ARm[PZn(SiQ3)2-n] 3-m (2)[(QsSi)2 -nZnP]3 -mRmA-ARm[PZn(SiQ3)2-n]3-m (3) wherein: n is an integer having a value of 0 or 1; m is an integer having a value of 0, 1, or 2; A is a silicon atom (Si) or a carbon atom (C); P is a phosphorous atom; Si is a silicon atom;R is a substituent that is bonded to A by an A-R bond, each R is independently selected from the group consisting of a hydrogen, a hydrocarbyl group, a silyl group, an alkoxy group, and an amino group;Z is a substituent that is bonded to P by a P-Z bond, each Z is independently selected from the group consisting of a hydrocarbyl group, an alkoxy group, and an amino group; andQ is a substituent that is bonded to Si by a Si-Q bond, each Q is independently selected from the group consisting of hydrogen, a hydrocarbyl group, an alkoxy group, and an amino group.

[0115] In some of these embodiments, each Z, if present, is preferably a hydrocarbyl group; and each Q is preferably selected from a hydrogen and a hydrocarbyl group. In these embodiments, a hydrocarbyl group may be an alkyl group, typically a C1-C4 alkyl group. Further, in some embodiments, the integer n is 0.

[0116] General Formula (0)

[0117] In some embodiments, the silicon precursor has a structure according to a general Formula (0): PZm(SiQ3)3-m(0) wherein: m is an integer having a value of 0, 1, or 2;P is a phosphorous atom;Si is a silicon atom that is bonded to P by an Si-P bond;Z is a substituent that is bonded to P by a P-Z bond, each Z is independently selected from the group consisting of a hydrocarbyl group, an alkoxy group, and an amino group; andQ is a substituent that is bonded to Si by a Si-Q bond, each Q is independently selected from the group consisting of hydrogen, a hydrocarbyl group, an alkoxy group, and an amino group.

[0118] In some of these embodiments, each Z, if present, is preferably a hydrocarbyl group; and each Q is preferably selected from a hydrogen and a hydrocarbyl group. In these embodiments, a hydrocarbyl group may be an alkyl group, typically a C1-C4 alkyl group.

[0119] In some preferred embodiments, the integer m in the general Formula (0) is 0 and the silicon precursor has a structure according to general Formula (0a):P(SIQ3)3(0a) wherein P, Si, and Q are defined above. In some of these embodiments, each Q is preferably selected from a hydrogen and a hydrocarbyl group, wherein the hydrocarbyl group may be an alkyl group, typically a C1-C4 alkyl group.

[0120] Exemplary silicon precursors according to general Formula (0), include, but are not limited to, trisilylphosphine (P(SiH3)3), tris(trimethylsilyl)phosphine (P(SiMe3)3), tris(triethylsilyl)phosphine (P(SiEt3)3), silylphosphine (PH2(SiH3)), disilylphosphine (PH(SiH3)2), trimethylsilylphosphine (PH2(SiMe3)), bis(trimethylsilyl)phosphine (PH(SiMe3)2), triethylsilylphosphine (PFElSiEts)). bis(triethylsilyl)phosphine (PH(SiEt3)2), dimethylsilylphosphine (PMe2(SiH3)), methyldisilylphosphine (PMe(SiH3)2), dimethyl(trimethylsilyl)phosphine (PMe2(SiMe3)), methylbis(trimethylsilyl)phosphine PMe(SiMe3)2), and the like.

[0121] General Formula (1)

[0122] In some embodiments, the silicon precursor has a structure according to general Formula (1): ARm[PZn(SiQ3)2-n]4-m (1) wherein: n is an integer having a value of 0 or 1; m is an integer having a value of 0, 1, or 2;A is a silicon atom (Si) or a carbon atom (C);P is a phosphorous atom that is bonded to A by a P-A bond;Si is a silicon atom that is bonded to P by an Si-P bond;R is a substituent that is bonded to A by an A-R bond, each R is independently selected from the group consisting of a hydrogen, a hydrocarbyl group, a silyl group, an alkoxy group, and an amino group;Z is a substituent that is bonded to P by a P-Z bond, each Z is independently selected from the group consisting of a hydrocarbyl group, an alkoxy group, and an amino group; andQ is a substituent that is bonded to Si by a Si-Q bond, each Q is independently selected from the group consisting of hydrogen, a hydrocarbyl group, an alkoxy group, and an amino group.

[0123] FIG. 1 shows embodiments of structures according to general Formula (1) for varying m and n combinations. In some of these embodiments, the silicon precursor comprises two silylphosphanyl groups bonded to the A group (e.g., see structures (a) and (b) in FIG. 1, where m=2 and where n=l and n=0 respectively). In some other of these embodiments, the silicon precursor comprises three silylphosphanyl groups bonded to the A group (e.g., see structures (c) and (d) in FIG. 1, where m=l and where n=l and n=0 respectively). In some other of these embodiments, the silicon precursor comprises four silylphosphanyl groups bonded to the A group (e.g., see structures (e) and (f) in FIG. 1, where m=0 and where n=l and n=0 respectively).

[0124] In some of these embodiments, the A group of the silicon precursor is a silicon atom. In some other of these embodiments, the A group of the silicon precursor is a carbon atom. In some of these embodiments, the R group of the silicon precursor, if present, is independently selected from the group consisting of a hydrogen atom; a hydrocarbyl group, typically an alkyl group such as a methyl group (Me) and an ethyl group (Et); and a silyl group, typically silyl (SiH3) or trimethylsilyl (Si(Me)s). In some of these embodiments, the Z group of the silicon precursor, if present, is an independently selected hydrocarbyl group, typically an alkyl group such as a methyl group (Me) and an ethyl group (Et). In some of these embodiments, the Q group of the silicon precursor is independently selected from the group consisting of a hydrogen atom and a hydrocarbyl group, typically an alkyl group such as a methyl group (Me) and an ethyl group (Et).

[0125] In some preferred embodiments, the integer n in the general Formula (1) is 0 and the silicon precursor has a structure according to general Formula (la):ARm[P(SiQ3)2]4-m (la) wherein m, A, P, Si, R, and Q are defined above. Silicon precursor structures according to general Formula (la) are shown by structures (b), (d), and (f) in FIG. 1. In some of these embodiments, the R group of the silicon precursor, if present, is independently selected from the group consisting of a hydrogen atom; a hydrocarbyl group, typically an alkyl group such as a methyl group (Me) and an ethyl group (Et); and a silyl group, typically silyl (SiH3) or trimethylsilyl (Si(Me)3); and the Q group of the silicon precursor is independently selected from the group consisting of a hydrogen atom and a hydrocarbyl group, typically an alkyl group such as a methyl group (Me) and an ethyl group (Et).

[0126] Exemplary silicon precursors according to general Formula (1), where A is a silicon atom (Si) and m=2 include, but are not limited to, SiH2(P(SiH3)2)2, SiHMe(P(SiH3)2)2, SiMe2(P(SiH3)2)2, SiH(SiH3)(P(SiH3)2)2, Si(SiH3)2(P(SiH3)2)2, SiH2(P(SiMe3)2)2, SiHMe(P(SiMe3)2)2, SiMe2(P(SiMe3)2)2, SiH(SiH3)(P(SiMe3)2)2, Si(SiH3)2(P(SiMe3)2)2, SiH2(P(SiEt3)2)2, SiHMe(P(SiEt3)2)2, SiMe2(P(SiEt3)2)2, SiH(SiH3)(P(SiEt3)2)2, Si(SiH3)2(P(SiEt3)2)2, SiH2(PMe(SiH3))2, SiHMe(PMe(SiH3))2,SiMe2(PMe(SiH3))2, SiH(SiH3)(PMe(SiH3))2, Si(SiH3)2(PMe(SiH3))2, SiH2(PMe(SiMe3))2,SiHMe(PMe(SiMe3))2, SiMe2(PMe(SiMe3))2, SiH(SiH3)(PMe(SiMe3))2, Si(SiH3)2(PMe(SiMe3))2, SiH2(PMe(SiEt3))2, SiHMe(PMe(SiEt3))2, SiMe2(PMe(SiEt3))2, SiH(SiH3)(PMe(SiEt3))2, Si(SiH3)2(PMe(SiEt3))2, and the like. Exemplary silicon precursors according to general Formula (1),where A is a silicon atom (Si) and m=l include, but are not limited to, SiH(P(SiHs)2)3, SiMe(P(SiHs)2)3, Si(SiH3)(P(SiH3)2)3, SiH(P(SiMe3)2)3, SiMe(P(SiMe3)2)3, Si(SiH3)(P(SiMe3)2)3, SiH(P(SiEt3)2)3, SiMe(P(SiEt3)2)3, Si(SiH3)(P(SiEt3)2)3, SiH(PMe(SiH3))3, SiMe(PMe(SiH3))3, Si(SiH3)(PMe(SiH3))3, SiH(PMe(SiMe3))3, SiMe(PMe(SiMe3))3, Si(SiH3)(PMe(SiMe3))3, SiH(PMe(SiEt3))3, SiMe(PMe(SiEt3))3, Si(SiH3)(PMe(SiEt3))3, and the like. Exemplary silicon precursors according to general Formula (1), where A is a silicon atom (Si) and m=0 include, but are not limited to, Si(P(SiH3)2)4, Si(P(SiMe3)2)4, Si(P(SiEt3)2)4, Si(PMe(SiH3))4, Si(PMe(SiMe3))4, Si(PMe(SiEt3))4, and the like. In some embodiments, the silicon precursor having a structure according to general Formula (1) is selected from the group consisting of bis(disilylphosphanyl)silane (SiFE^SiFEEh), bis(bis(trimethylsilyl)phosphanyl)silane (SiH2(P(SiMe3)2)2), tris(disilylphosphanyl)silane (SiH(P(SiH3)2)3), and tris(bis(trimethylsilyl)phosphanyl)silane (SiH(P(SiMe3)2)3), shown in FIG. 4A by structures (a) -(d).

[0127] Exemplary silicon precursors according to general Formula (1), where A is a carbon atom (C) and m=2 include, but are not limited to, CH2(P(SiH3)2)2, CHMe(P(SiH3)2)2, CMe2(P(SiH3)2)2, CH2(P(SiMe3)2)2, CHMe(P(SiMe3)2)2, CMe2(P(SiMe3)2)2, CH2(P(SiEt3)2)2, CHMe(P(SiEt3)2)2, CMe2(P(SiEt3)2)2, CH2(PMe(SiH3))2, CHMe(PMe(SiH3))2, CMe2(PMe(SiH3))2, CH2(PMe(SiMe3))2, CHMe(PMe(SiMe3))2, CMe2(PMe(SiMe3))2, CH2(PMe(SiEt3))2, CHMe(PMe(SiEt3))2, CMe2(PMe(SiEt3))2, and the like. Exemplary silicon precursors according to general Formula (1), where A is a carbon atom (C) and m=l include, but are not limited to, CH(P(SiH3)2)3, CMe(P(SiH3)2)3, CH(P(SiMe3)2)3, CMe(P(SiMe3)2)3, CH(P(SiEt3)2)3, CMe(P(SiEt3)2)3, CH(PMe(SiH3))3,CMe(PMe(SiH3))3, CH(PMe(SiMe3))3, CMe(PMe(SiMe3))3, CH(PMe(SiEt3))3, CMe(PMe(SiEt3))3, and the like. Exemplary silicon precursors according to general Formula (1), where A is a carbon atom (C) and m=0 include, but are not limited to, C(P(SiH3)2)4, C(P(SiMe3)3)4, C(P(SiEt3)3)4, C(PMe(SiH3))4, C(PMe(SiMe3))4, C(PMe(SiEt3))4, and the like. In some embodiments, the silicon precursor having a structure according to general Formula (1) is selected from the group consisting of bis(disilylphosphanyl)methane (CH2(P(SiH3)2)2), bis(bis(trimethylsilyl)phosphanyl) methane (CH2(P(SiMe3)2)2), tris(disilylphosphanyl)methane (CH(P(SiH3)2)3), and tris(bis(trimethylsilyl)phosphanyl)methane (CH(P(SiMe3)2)3), shown in FIG. 4B by structures (i)-(l).

[0128] General Formula (2),

[0129] In some embodiments, the silicon precursor has a structure according to general Formula (2): [ (Qs Si)2-nZnP] 3 -mRmA-PZn(SiQ3) l-n-ARm[PZn(SiQ3)2-n] 3-m (2) wherein: n is an integer having a value of 0 or 1; m is an integer having a value of 0, 1, or 2;A is a silicon atom (Si) or a carbon atom (C);P is a phosphorous atom that is bonded to A by a P-A bond; Si is a silicon atom that is bonded to P by an Si-P bond;R is a substituent that is bonded to A by an A-R bond, each R is independently selected from the group consisting of a hydrogen, a hydrocarbyl group, a silyl group, an alkoxy group, and an amino group;Z is a substituent that is bonded to P by a P-Z bond, each Z is independently selected from the group consisting of a hydrocarbyl group, an alkoxy group, and an amino group; andQ is a substituent that is bonded to Si by a Si-Q bond, each Q is independently selected from the group consisting of hydrogen, a hydrocarbyl group, an alkoxy group, and an amino group.

[0130] FIG. 2 shows embodiment of structures according to general Formula (2) for varying m and n combinations. In some of these embodiments, the silicon precursor comprises two silylphosphanyl groups, each A group being bonded to one silylphosphanyl group (e.g., see structure (a) in FIG. 2, where m=2 and where n=l). In some of these embodiments, the silicon precursor comprises three silylphosphanyl groups, each A group being bonded to two silylphosphanyl groups (e.g., see structure (b) in FIG. 2, where m=2 and where n=0). In some of these embodiments, the silicon precursor comprises four silylphosphanyl groups, each A group being bonded to two silylphosphanyl groups (e.g., see structure (c) in FIG. 2, where m=l and where n=l). In some of these embodiments, the silicon precursor comprises five silylphosphanyl groups, each A group being bonded to three silylphosphanyl groups (e.g., see structure (d) in FIG. 2, where m=l and where n=0). In some of these embodiments, the silicon precursor comprises six silylphosphanyl groups, each A group being bonded to three silylphosphanyl groups (e.g., see structure (e) in FIG. 2, where m=0 and where n=l). In some of these embodiments, the silicon precursor comprises seven silylphosphanyl groups, each A group being bonded to four silylphosphanyl groups (e.g., see structure (f) in FIG. 2, where m=0 and where n=0).

[0131] In some of these embodiments, each A group of the silicon precursor is a silicon atom. In some other of these embodiments, each A group of the silicon precursor is a carbon atom. In some of these embodiments, the R group of the silicon precursor, if present, is independently selected from the group consisting of a hydrogen atom; a hydrocarbyl group, typically an alkyl group such as a methyl group (Me) and an ethyl group (Et); and a silyl group, typically silyl (SiH3) or trimethylsilyl (Si(Me)s). In some of these embodiments, the Z group of the silicon precursor, if present, is an independently selected hydrocarbyl group, typically an alkyl group such as a methyl group (Me) and an ethyl group (Et). In some of these embodiments, the Q group of the silicon precursor is independently selected from the group consisting of a hydrogen atom and a hydrocarbyl group, typically an alkyl group such as a methyl group (Me) and an ethyl group (Et).

[0132] In some preferred embodiments, the integer n in the general Formula 2 is 0 and the silicon precursor has a structure according to general Formula (2a): [(Q3Si)2P]3-mARm-P(SiQ3)-ARm[P(SiQ3)2]3-m(2a)wherein m, A, P, Si, R, and Q are defined above. Silicon precursor structures according to Formula (2a) are shown by structures (b), (d), and (f) in FIG. 2. In some of these embodiments, the R group of the silicon precursor, if present, is independently selected from the group consisting of a hydrogen atom; a hydrocarbyl group, typically an alkyl group such as a methyl group (Me) and an ethyl group (Et); and a silyl group, typically silyl (Si H ) or trimethylsilyl (Si(Me)s); and the Q group of the silicon precursor is independently selected from the group consisting of a hydrogen atom and a hydrocarbyl group, typically an alkyl group such as a methyl group (Me) and an ethyl group (Et).

[0133] Exemplary silicon precursors according to general Formula (2), where each A is a silicon atom (Si) and m=2 include, but are not limited to (H3Si)2P-SiH2-P(SiH3)-SiH2-P(SiH3)2, (H3Si)2P-SiH(Me)- P(SiH3)-SiH(Me)-P(SiH3)2, (H3Si)2P-Si(Me)2-P(SiH3)-Si(Me)2-P(SiH3)2, (Me3Si)2P-SiH2-P(SiMe3)- SiH2-P(SiMe3)2, (Me3Si)2P-SiH(Me)-P(SiMe3)-SiH(Me)-P(SiMe3)2, (Me3Si)2P-Si(Me)2-P(SiMe3)- Si(Me)2-P(SiMe3)2, (H3Si)(Me)P-SiH2-P(Me)-SiH2-P(Me)(SiH3), (H3Si)(Me)P-SiH(Me)-P(Me)- SiH(Me)-P(Me)(SiH3), (H3Si)(Me)P-Si(Me)2-P(Me)-Si(Me)2-P(Me)(SiH3), (Me3Si)(Me)P-SiH2- P(Me)-SiH2-P(Me)(SiMe3), (Me3Si)(Me)P-SiH(Me)-P(Me)-SiH(Me)-P(Me)(SiMe3), (Me3Si)(Me)P- Si(Me)2-P(Me)-Si(Me)2-P(Me)(SiMe3), and the like. Exemplary silicon precursors according to general Formula (2), where each A is a silicon atom (Si) and m=l include, but are not limited to [(H3Si)2P]2SiH- P(SiH3)-SiH[P(SiH3)2]2, [(H3Si)2P]2Si(Me)-P(SiH3)-Si(Me)[P(SiH3)2]2, [(Me3Si)2P]2SiH-P(SiMe3)- SiH[P(SiMe3)2]2, [(Me3Si)2P]2Si(Me)-P(SiMe3)-Si(Me)[P(SiMe3)2]2, [(H3Si)(Me)P]2SiH-P(Me)- SiH[P(Me)(SiH3)]2, [(H3Si)(Me)P]2Si(Me)-P(Me)-Si(Me)[P(Me)(SiH3)]2, [(Me3Si)(Me)P]2SiH-P(Me)- SiH[P(Me)(SiMe3)]2, [(Me3Si)(Me)P]2Si(Me)-P(Me)-Si(Me)[P(Me)(SiMe3)]2, and the like. Exemplary silicon precursors according to general Formula (2), where each A is a silicon atom (Si) and m=0 include, but are not limited to [(H3Si)2P]3Si-P(SiH3)-Si[P(SiH3)2]3, [(Me3Si)2P]3Si-P(SiMe3)- Si[P(SiMe3)2]3, [(H3Si)(Me)P]3Si-P(Me)-Si[P(Me)(SiH3)]3, [(Me3Si)(Me)P]3Si-P(Me)-Si[P(Me)(SiMe3)]3, and the like. In some embodiments, the silicon precursor having a structure according to general Formula (2) is selected from the group consisting of (H3Si)2P-SiH2-P(SiH3)-SiH2- P(SiH3)2and (Me3Si)2P-SiH2-P(SiMe3)-SiH2-P(SiMe3)2, shown in FIG. 4A by structures (e) and (f).

[0134] Exemplary silicon precursors according to general Formula (2), where each A is a carbon atom (C) and m=2 include, but are not limited to (H3Si)2P-CH2-P(SiH3)-CH2-P(SiH3)2, (H3Si)2P-CH(Me)- P(SiH3)-CH(Me)-P(SiH3)2, (H3Si)2P-C(Me2)-P(SiH3)-C(Me2)-P(SiH3)2, (Me3Si)2P-CH2-P(SiMe3)- CH2-P(SiMe3)2, (Me3Si)2P-CH(Me)-P(SiMe3)-CH(Me)-P(SiMe3)2, (Me3Si)2P-C(Me2)-P(SiMe3)- C(Me2)-P(SiMe3)2, (H3Si)(Me)P-CH2-P(Me)-CH2-P(Me)(SiH3), (H3Si)(Me)P-CH(Me)-P(Me)- CH(Me)-P(Me)(SiH3), (H3Si)(Me)P-C(Me2)-P(Me)-C(Me2)-P(Me)(SiH3), (Me3Si)(Me)P-CH2-P(Me)- CH2-P(Me)(SiMe3), (Me3Si)(Me)P-CH(Me)-P(Me)-CH(Me)-P(Me)(SiMe3), (Me3Si)(Me)P-C(Me2)- P(Me)-C(Me2)-P(Me)(SiMe3), and the like. Exemplary silicon precursors according to general Formula (2), where each A is a carbon atom (C) and m=l include, but are not limited to [(H3Si)2P]2-CH-P(SiH3)- CH-[P(SiH3)2]2, [(H3Si)2P]2-C(Me)-P(SiH3)-C(Me)-[P(SiH3)2]2, [(Me3Si)2P]2-CH-P(SiMe3)-CH- [P(SiMe3)2]2, [(Me3Si)2P]2-C(Me)-P(SiMe3)-C(Me)-[P(SiMe3)2]2, [(H3Si)(Me)P]2-CH-P(Me)-CH-[P(Me)(SiH3)]2, [(H3Si)(Me)P]2-C(Me)-P(Me)-C(Me)-[P(Me)(SiH3)]2, [(Me3Si)(Me)P]2-CH-P(Me)- CH-[P(Me)(SiMe3)]2, [(Me3Si)(Me)P]2-C(Me)-P(Me)-C(Me)-[P(Me)(SiMe3)]2, and the like. Exemplary silicon precursors according to general Formula (2), where each A is a carbon atom (C) and m=0 include, but are not limited to [(H3Si)2P]3C-P(SiH3)-C[P(SiH3)2]3, [(Me3Si)2P]3C-P(SiMe3)-C [P(SiMe3)2]3, [(H3Si)(Me)P]3C-P(Me)-C[P(Me)(SiH3)]3, [(Me3Si)(Me)P]3C-P(Me)-C[P(Me)(SiMe3)]3, and the like. In some embodiments, the silicon precursor having a structure according to general Formula (2) is selected from the group consisting of (H3Si)2P-CH2-P(SiH3)-CH2-P(SiH3)2and (Me3Si)2P-CH2-P(SiMe3)-SiH2-P(SiMe3)2, shown in FIG. 4B by structures (m) and (n).

[0135] General Formula (3)

[0136] In some embodiments, the silicon precursor has a structure according to general Formula (3): [(Q3Si)2.nZnP]3-mRmA-ARm[PZn(SiQ3)2.n]3-m. (3) wherein: n is an integer having a value of 0 or 1; m is an integer having a value of 0, 1, or 2;A is a silicon atom (Si) or a carbon atom (C);P is a phosphorous atom that is bonded to A by a P-A bond;Si is a silicon atom that is bonded to P by an Si-P bond;R is a substituent that is bonded to A by an A-R bond, each R is independently selected from the group consisting of a hydrogen, a hydrocarbyl group, a silyl group, an alkoxy group, and an amino group;Z is a substituent that is bonded to P by a P-Z bond, each Z is independently selected from the group consisting of a hydrocarbyl group, an alkoxy group, and an amino group; andQ is a substituent that is bonded to Si by a Si-Q bond, each Q is independently selected from the group consisting of hydrogen, a hydrocarbyl group, an alkoxy group, and an amino group.Note that general Formula (3) may also be expressed as [ARm[PZn(SiQ3)2.n]3-m]2, which is equivalent to [(Q3Si)2.nZnP]3-mRmA-ARm[PZn(SiQ3)2.n]3-m.

[0137] FIG. 3 shows embodiments of structures according to general Formula (3) for varying m and n combinations. In some of these embodiments, the silicon precursor comprises two silylphosphanyl groups, each A group bonded to one of the silylphosphanyl groups (e.g., see structures (a) and (b) in FIG. 3, where m=2 and where n=l and n=0 respectively). In some of these embodiments, the silicon precursor comprises four silylphosphanyl groups, each A group bonded to two of the silylphosphanyl groups (e.g., see structures (c) and (d) in FIG. 3, where m=l and where n=l and n=0 respectively). In some of these embodiments, the silicon precursor comprises six silylphosphanyl groups, each A group bonded to three of the silylphosphanyl groups (e.g., see structures (e) and (f) in FIG. 3, where m=0 and where n=l and n=0 respectively).

[0138] In some of these embodiments, each A group of the silicon precursor is a silicon atom and the silicon precursor comprises an Si-Si bond. In some of these embodiments, each A group of the silicon precursor is a carbon atom and the silicon precursor comprises a C-C bond. In some of these embodiments, the R group of the silicon precursor, if present, is independently selected from the group consisting of a hydrogen atom; a hydrocarbyl group, typically an alkyl group such as a methyl group (Me), and an ethyl group (Et); and a silyl group, typically silyl (SiH3) or trimethylsilyl (Si(Me)s). In some of these embodiments, the Z group of the silicon precursor, if present, is an independently selected hydrocarbyl group, typically an alkyl group such as a methyl group (Me) and an ethyl group (Et). In some of these embodiments, the Q group of the silicon precursor is independently selected from the group consisting of a hydrogen atom and a hydrocarbyl group, typically an alkyl group such as a methyl group (Me) and an ethyl group (Et).

[0139] In some preferred embodiments, the integer n in the general Formula (3) is 0 and the silicon precursor has a structure according to general Formula (3a):[(Q3Si)2P]3-mRmA-ARm[P(SiQ3)2]3-m. (3a) wherein m, A, P, Si, R, and Q are defined above. Note that general Formula (3a) may also be expressed as [ARm[P(SiQ3)2]3-m]2, which is equivalent to [(Q3Si)2P]3-mRmA-ARm[P(SiQ3)2]3-m. Silicon precursor structures according to Formula (3a) are shown by structures (b), (d), and (f) in FIG. 3. In some of these embodiments, the R group of the silicon precursor, if present, is independently selected from the group consisting of a hydrogen atom; a hydrocarbyl group, typically an alkyl group such as a methyl group (Me), and an ethyl group (Et); and a silyl group, typically silyl (SiH ) or trimethylsilyl (Si(Me)3); and the Q group of the silicon precursor is independently selected from the group consisting of a hydrogen atom and a hydrocarbyl group, typically an alkyl group such as a methyl group (Me) and an ethyl group (Et).

[0140] Exemplary silicon precursors according to general Formula (3), where each A is a silicon atom (Si) and m=2 include, but are not limited to, [SiH2(P(SiH3)2)]2, [SiHMe(P(SiH3)2)]2, [SiMe2(P(SiH3)2)]2, [SiH(SiH3)(P(SiH3))]2, [Si(SiH3)2(P(SiH3))]2, [SiH2(P(SiMe3)2)]2, [SiHMe(P(SiMe3)2)]2,[SiMe2(P(SiMe3)2)]2, [SiH(SiH3)(P(SiMe3)2)]2, [Si(SiH3)2(P(SiMe3)2)]2, [SiH2(P(SiEt3)2)]2,[SiHMe(P(SiEt3)2)]2, [SiMe2(P(SiEt3)2)]2, [SiH(SiH3)(P(SiEt3)2)]2, [Si(SiH3)2(P(SiEt3)2)]2,[SiH2(PMe(SiH3))]2, [SiHMe(PMe(SiH3))]2, [SiMe2(PMe(SiH3))]2, [SiH(SiH3)(PMe(SiH3))]2, [Si(SiH3)2(PMe(SiH3))]2, [SiH2(PMe(SiMe3))]2, [SiHMe(PMe(SiMe3))]2, [SiMe2(PMe(SiMe3))]2, [SiH(SiH3)(PMe(SiMe3))]2[Si(SiH3)2(PMe(SiMe3))]2, [SiH2(PMe(SiEt3))]2, [SiHMe(PMe(SiEt3))]2, [SiMe2(PMe(SiEt3))]2, [SiH(SiH3)(PMe(SiEt3))]2, [Si(SiH3)2(PMe(SiEt3))]2, and the like. Exemplary silicon precursors according to general Formula (3), where each A is a silicon atom (Si) and m=l include, but are not limited to, [SiH(P(SiH3)2)2]2, [SiMe(P(SiH3)2)2]2, [Si(SiH3)(P(SiH3)2)2]2, [SiH(P(SiMe3)2)2]2, [SiMe(P(SiMe3)2)2]2, [Si(SiH3)(P(SiMe3)2)2]2, [SiH(P(SiEt3)2)2]2,[SiMe(P(SiEt3)2)2]2, [Si(SiH3)(P(SiEt3)2)2]2, [SiH(PMe(SiH3))2]2, [SiMe(PMe(SiH3))2]2,[Si(SiH3)(PMe(SiH3))2]2, [SiH(PMe(SiMe3))2]2, [SiMe(PMe(SiMe3))2]2, [Si(SiH3)(PMe(SiMe3))2]2,[SiH(PMe(SiEts))2]2, [SiMe(PMe(SiEt3))2h, [Si(SiH3)(PMe(SiEt3))2]2, and the like. Exemplary silicon precursors according to general Formula (3), where each A is a silicon atom (Si) and m=0 include, but are not limited to, [Si(P(SiH3)2)3]2, [Si(P(SiMe3)2)3]2, [Si(P(SiEt3)2)3]2, [Si(PMe(SiH3))3]2, [Si(PMe(SiMe3))3]2, [Si(PMe(SiEt3))3h, and the like. In some embodiments, the silicon precursor having a structure according to general Formula (3) is selected from the group consisting of bis(bis(silyl)phosphino)disilane ([SiH2(P(SiH3)2)]2) and bis(bis(trimethylsilyl)phosphino)disilane ([SiH2(P(SiMe3)2)]2), shown in FIG. 4A by structures (g) and (h).

[0141] Exemplary silicon precursors according to general Formula (3), where each A is a carbon atom (C) and m=2 include, but are not limited to, [CH2(P(SiH3)2)]2, [CHMe(P(SiH3)2)]2, [CMe2(P(SiH3)2)]2, [CH2(P(SiMe3)2)]2, [CHMe(P(SiMe3)2)]2, [CMe2(P(SiMe3)2)]2, [CH2(P(SiEt3)2)]2, [CHMe(P(SiEt3)2)]2, [CMe2(P(SiEt3)2)]2, [CH2(PMe(SiH3))]2, [CHMe(PMe(SiH3))]2, [CMe2(PMe(SiH3))]2,[CH2(PMe(SiMe3))]2, [CHMe(PMe(SiMe3))]2, [CMe2(PMe(SiMe3))]2, [CH2(PMe(SiEt3))]2, [CHMe(PMe(SiEt3))]2, [CMe2(PMe(SiEt3))]2, and the like. Exemplary silicon precursors according to general Formula (3), where each A is a carbon atom (C) and m=l include, but are not limited to, [CH(P(SIH3)2)2]2, [CMe(P(SiH3)2)2]2, [C(SIH3)(P(SIH3)2)2]2, [CH(P(SiMe3)2)2]2, [CMe(P(SiMe3)2)2]2, [CH(P(SiEt3)2)2]2, [CMe(P(SiEt3)2)2]2, [CH(PMe(SiH3))2]2, [CMe(PMe(SiH3))2]2,[CH(PMe(SiMe3))2]2, [CMe(PMe(SiMe3))2]2, [CH(PMe(SiEt3))2]2, [CMe(PMe(SiEt3))2]2, and the like. Exemplary silicon precursors according to general Formula (3), where each A is a carbon atom (C) and m=0 include, but are not limited to, [C(P(SiH3)2)3]2, [C(P(SiMe3)2)3]2, [C(P(SiEt3)2)3h, [C(PMe(SiH3))3]2, [C(PMe(SiMe3))3]2, [C(PMe(SiEt3))3]2, and the like. In some embodiments, the silicon precursor having a structure according to general Formula (3) is selected from the group consisting of bis(bis(silyl)phosphino)ethane ([CFE P SilE^h) and bis(bis(trimethylsilyl)phosphino)ethane ([CH2(P(SiMe3)2)]2), shown in FIG. 4B by structures (o) and (P).

[0142] Silicon Precursor Compositions

[0143] The silicon precursor compositions disclosed herein (e.g., compositions comprising a silicon precursor having a structure according to general Formula (0), general Formula (1), general Formula (2), or general Formula (3) discussed above) are suitable for forming silicon containing films using a vapor deposition method. Hence, the silicon precursor composition should have suitable properties for thin film applications. For instance, the silicon precursor should have a sufficient vapor pressure (e.g., a vapor pressure of between about 1-20 torr at temperature ranging from 25 °C to 200 °C) and thermal stability over the temperature range of the deposition process. By selectively choosing the substituent groups on the silicon precursor, the vapor pressure, thermostability, and other features may be tuned.

[0144] The silicon precursor composition should also have a purity that is suitable for forming silicon containing films that have good electrical properties. In this context, the impurities in the silicon precursor composition may end up in the resulting silicon containing film. Additionally, the presence of impurities in the silicon precursor composition may lead to process drift due to differing vaporpressures and evaporation rates of various components of the silicon precursor composition. Impurities in the silicon precursor composition may be due to unreacted reactants and reaction byproducts, from the synthesis method. In some embodiments, the silicon precursor composition comprises at least about 90 wt % of the silicon precursor, or at least about 95 wt % of the silicon precursor, or at least about 97 wt % of the silicon precursor, or at least about 98 wt % of the silicon precursor, or at least about 99 wt % of the silicon precursor, or at least about 99.5 wt % of the silicon precursor, or at least about 99.9 wt % of the silicon precursor, or at least about 99.99 wt % of the silicon precursor, or at least about 99.999 wt % of the silicon precursor. In some embodiments, the silicon precursor composition consists of or consists essentially of the silicon precursor. In some embodiments, an amount of impurities in the composition is less than about 10 wt %, or less than about 5 wt %, or less than about 3 wt %, or less than about 2 wt %, or less than about 1 wt %, or less than about 0.5 wt %, or less than about 0.1 wt %, or less than about 0.05 wt %, or less than about 0.01 wt %, or less than about 0.005 wt %, or less than about 0.001 wt %. In some embodiments, an amount of oxygen containing impurities in the silicon precursor composition is no more than about 5 wt %, or no more than about 4 wt %, or no more than about 3 wt %, or no more than about 2 wt %, or no more than about 1 wt %, or no more than about 0.5 wt %, or no more than about 0. 1 wt %, or no more than about 100 ppm, or no more than about 10 ppm. In some embodiments, an amount of carbon containing impurities in the silicon precursor composition is no more than about 10 wt %, or no more than about 5 wt %, or no more than about 4 wt %, or no more than about 3 wt %, or no more than about 2 wt %, or no more than about 1 wt %, or no more than about 0.5 wt %, or no more than about 0. 1 wt %, or no more than about 100 ppm, or no more than about 10 ppm. In some embodiments, an amount of halogen containing impurities in the silicon precursor composition is no more than about 5 wt %, or no more than about 4 wt %, or no more than about 3 wt %, or no more than about 2 wt %, or no more than about 1 wt %, or no more than about 0.5 wt %, or no more than about 0.1 wt %, or no more than about 100 ppm, or no more than about 10 ppm. In some embodiments, an amount of metal impurities in the silicon precursor composition is no more than about 1 wt %, or no more than about 0.1 wt %, or no more than about 100 ppm, or no more than about 10 ppm, or no more than about 1 ppm, or no more than about 100 ppb, or no more than about 10 ppb. The required purity of the silicon precursor composition depends upon the specific thin film application. For example, epitaxial processes generally require very high purity precursor compositions. In some embodiments, the silicon precursor composition has a purity of about 99 wt % or more, or about 99.5 wt % or more, or about 99.9 wt % or more, or about 99.99 wt % or more, or even about 99.999 wt % or more. For other applications, the purity requirement may be more relaxed, which provides cost benefits for the application. In some embodiments, the silicon precursor composition has a purity of about 95 wt % or more, or about 97 wt % or more, or about 98 wt % or more, or about 99 wt % or more. In some embodiments, the silicon precursor composition has a purity that is between about 95 wt % and about 99.9 wt %, or between about 97 wt % and about 99.9 wt %, or between about 98 wt % and about 99.9wt %, or between about 99 wt % and about 99.9 wt %, or between about 97 wt % and about 99.5 wt %, or between about 97 wt % and about 99 wt %.

[0145] Synthesis of Silicon Precursor Compositions

[0146] The disclosed silicon precursor compositions comprising a silicon precursor having a structure according to general Formula (0), general Formula (1), general Formula (2), or general Formula (3) may be formed using a variety of methods known in the art. In certain embodiments, the disclosed silicon precursor compositions comprising a silicon precursor having a structure according to general Formula (1), general Formula (2), or general Formula (3) may be formed by coupling two or more silylphosphine reactants together using a one-step synthetic route, or a two-step synthetic route, or a three -step synthetic route.

[0147] In some embodiments, the method for forming the disclosed silicon precursor compositions comprises forming a silicon precursor by contacting a silylphosphine reactant with an alkyl lithium compound to form a lithium silylphosphine compound, then contacting the lithium silylphosphine compound with a linking compound to form a composition comprising the silicon precursor. In some instances, the starting silylphosphine reactant is commercially available. For example, tris(trimethylsilyl)phosphine (P(SiMcA) is available in a range of assays, including >95% from Millipore Sigma and >98% from American Elements. Where the starting silylphosphine reactant is not commercially available, it may be readily obtained using synthetic methods reported in the literature.

[0148] The step of contacting the silylphosphine reactant with the alkyl lithium compound preferably involves mixing equimolar amounts of the two compounds with one another. The mixing may occur in a solution. For example, the silylphosphine reactant may be provided in a solution and / or the alkyl lithium reactant may be provided in a solution. The two compounds may be contacted by adding the alkyl lithium compound, to a solution comprising the silylphosphine reactant, or conversely by adding the silylphosphine reactant to a solution comprising the alkyl lithium compound. The contacting step may occur through dropwise addition of one solution into the other solution, or it may occur by mixing the two solutions together all at once. The solution(s) may comprise one or more solvents, which may be chosen based on one or more of the volatility of the solvent, the solubilities of the reactants, and the insolubility of the resulting lithium silylphosphine compound, among other factors. The contacting step may occur in an oxygen free environment and using anhydrous solvents. Suitable solvents include, but are not limited to, tetrahydrofuran (THF), diethyl ether, dimethyl sulfoxide (DMSO), ethyl acetate, pentane, hexane, heptane, toluene, and the like. The contacting step may occur at room temperature (18°C - 25°C), at an elevated temperature, at a reduced temperature, or a combination thereof. In some embodiments, the temperature during the contacting step is maintained at a reduced temperature, typically at a temperature of about 0°C or more to less than room temperature. The contacting step may occur over the course of minutes to hours to days, depending upon the temperature during the reaction, the specific reactants chosen, the concentration of the reactants in the solution, among other factors.The products may optionally be separated using a variety of methods known in the art. For example, unreacted reactant(s) and co-product(s) along with the solvent may be evaporated by heating and / or by applying a vacuum to the product mixture, effectively isolating the lithium silylphosphine compound. Additionally, or alternatively, the lithium silylphosphine compound may be fdtered from the product mixture. Additional purification steps may optionally be performed to further isolated the lithium silylphosphine compound.

[0149] The step of contacting the lithium silylphosphine compound with the linking compound involves mixing the two compounds with one another. The molar ratio of the lithium silylphosphine compound and the linking compound may vary depending upon the structure of the targeted silicon precursor, and hence the structure of the linking compound. The linking compound generally comprises at least one halogen atom (X). In some embodiments the reaction is performed under stochiometric conditions. In other embodiments, the lithium silylphosphine compound is provided in stochiometric excess to help drive the reaction towards the desired products. The mixing may occur in a solution. For example, the lithium silylphosphine compound may be provided in solution and / or the linking compound may be provided in a solution. The two compounds may be contacted by adding the lithium silylphosphine compound to a solution comprising the linking compound, or conversely by adding the linking compound to a solution comprising the lithium silylphosphine compound. The contacting step may occur through dropwise addition of one solution into another solution, or it may occur by mixing the two solutions together all at once. The solution(s) may comprise one or more solvents, which may be chosen based on one or more of the solubilities of the reactants, volatility, and the insolubility of the lithium halide co-product (LiX), among other factors. The contacting step may occur in an oxygen free environment and using anhydrous solvents. Suitable solvents include, but are not limited to, tetrahydrofuran (THF), diethyl ether, dimethyl sulfoxide (DMSO), ethyl acetate, pentane, hexane, heptane, toluene, and the like. The contacting step may occur at about room temperature (18°C - 25°C), at an elevated temperature, at a reduced temperature, or a combination thereof. In some embodiments, the temperature during the contacting step is maintained at room temperature. The contacting step may occur over the course of minutes to hours to days, depending upon the temperature during the reaction, the specific reactants chosen, the concentration of the reactants in the solution, among other factors. The products may be separated using a variety of methods known in the art. For example, the LiX coproduct may be filtered from the solution and the solvent may be evaporated to concentrate the silicon precursor product. The silicon precursor may be further separated using distillation, extraction, precipitation, or other methods known in the art.

[0150] Example reactions for forming a silicon precursor composition comprising a silicon precursor having a structure according to Formula (la) are shown in FIG. 5. The reactions shown are balanced but in practice they may not occur under stoichiometric conditions. The silylphosphine reactant (I) may have a general structure of PfSiQs);. where Q is a substituent group, each Q is independently selected from the group consisting of hydrogen, a hydrocarbyl group, an alkoxy group, and an amino group,preferably Q is selected from a hydrogen atom and a hydrocarbyl group such as an alkyl group. Example silylphosphine reactants (I) include, but are not limited to, P(Si H,),. PlSiMcs);. and P( Si Et, ), . The alkyl lithium compound (II) has a general structure of R’Li, where Li is a lithium atom and R’ is an alkyl group, typically a C1-C4 alkyl group. Example alkyl lithium compounds (II) include, but are not limited to, methyllithium (MeLi), ethyllithium (EtLi), iso-propyllithium (iPrLi), n-butyllithium (nBuLi), secbutyllithium (sBuLi), and tert-butyllithium (tBuLi), each of which is commercially available. In the first step (Eq. 1), the silylphosphine reactant (I) is contacted with the alkyl lithium compound (II) to form a lithium silylphosphine compound (III). The lithium silylphosphine compound (III) may optionally be isolated from the reaction mixture and subjected to the second reaction step (Eq. 2) where the lithium silylphosphine compound (III) is contacted with a linking compound (V) to form the silicon precursors (VI) having a structure according to Formula (la) and a lithium halide salt (LiX) co-product (VII). Alternatively, the linking compound (V) is added directly to the first step reaction mixture, without separating the lithium silylphosphine compound (III) first. The silicon precursor (VI) may be isolated from the reaction mixture and optionally subjected to one or more further purification steps.

[0151] In FIG, 5, Eq. 2 is shown for the formation of various silicon precursor (VI) structures depending upon the structure of the linking compound (V). The linking compound (V) may have a general structure of ARm4-m, where m is an integer having a value of 0, 1, or 2; A is a carbon (C) atom or a silicon (Si) atom; R is a substituent that is bonded to A by an A-R bond, each R being independently selected from the group consisting of a hydrogen, a hydrocarbyl group, a silyl group, an alkoxy group, and an amino group, preferably R is selected from a hydrogen, a hydrocarbyl group, and a silyl group; and X is a halogen atom, bonded to A by an A-X bond, each X being selected from the group consisting of chlorine (Cl), bromine (Br), or iodine (I). Example linking compounds (V) having the general structure of ARmX4-minclude, but are not limited to, diiodosilane (SiFEL), trichlorosilane (SiHCF). tetrachlorosilane (SiCL), tetrabromosilane (SiBr^), dichlorodimethylsilane (CHsS^CHsjCh), trichloromethylsilane (CHNiCE). diiodomethane (CH2I2), triiodomethane (CHE), tetraiodomethane (CI4), 2,2-diiodopropane (CH3CI2CH3), dibromomethane (CEfcB ), tribromomethane (CHBn). tetrabromomethane (CBr4), 1,1 -dibromoethane (CH CHB ). dichloromethane (CH2Q2), trichloromethane (CHCI3), tetrachloromethane (CCI4), 1,1 -dichloroethane (CH3CHCI2), 2,2- dichloropropane (CH3CCI2CH3), and 1,1,1 -trichloroethane (CH3CCI3), each of which is commercially available. As shown, the specific structure of the silicon precursor (VI) can be varied by selecting silylphosphine reactants with certain Q substituents and halogenated linking compounds (V) with varying numbers of halogen substituents.

[0152] Example reactions for forming silicon precursor compositions comprising a silicon precursor having a structure according to Formula (3a) are shown in FIG. 6. Note that, the reaction sequence to form a silicon precursor having a structure according to general Formula (3a) is similar to the reaction sequence to form a silicon precursor having a structure according to general Formula (la), discussed above, except the structure of the linking compound differs. The step of contacting the silylphosphinereactant (I) and the alkyl lithium compound (II) to form a lithium silylphosphine compound (III) (shown in Eq. 1) is discussed above. The lithium silylphosphine compound (III) optionally may be isolated from the reaction mixture and subjected to the second reaction step (Eq. 3) where the lithium silylphosphine compound (III) is contacted with a halogenated linking compound (V) to form the silicon precursor (VI) having a structure according to Formula (3a) and a lithium halide salt (LiX) co-product (VII). Alternatively, the linking compound (V) is added to the first step reaction mixture without separating the lithium silylphosphine compound (III) first. The silicon precursor (VI) may be isolated from the reaction mixture and optionally subjected to one or more further purification steps.

[0153] In FIG. 6, Eq. 3 is shown for the formation of various silicon precursor structures (VI) depending upon the structure of the linking compound (V). The linking compound (V) may have a general structure of X3.mRmA-ARm3-m, where m is an integer having a value of 0, 1, or 2; A is a carbon (C) atom or a silicon (Si) atom; R is a substituent that is bonded to A by an A-R bond, each R being independently selected from the group consisting of a hydrogen, a hydrocarbyl group, a silyl group, an alkoxy group, and an amino group, preferably R is selected from a hydrogen, a hydrocarbyl group, and a silyl group; and X is a halogen atom, bonded to A by an A-X bond, each X being selected from the group consisting of chlorine (Cl), bromine (Br), or iodine (I). Example linking compounds having the general structure of Xs-mRmA-ARn -m include, but are not limited to, 1,2-diiodoethane (CH2ICH2I),1.2-dibromoethane (CFEBrCFEBr). 1,2-dibromopropane (CFECHBrCFEBr), 1,1,2,2-tetrabromoethane (CHBr2CHBr2), 1,2-dichloroethane (CH2CICH2CI), 1,2-dichloropropane (CH3CHCICH2CI), 1,1,1- trichloroethane (CH3CCI3), 1,1,2,2-tetrachloroethane (CHCI2CHCI2), hexachloroethane (CCI3CCI3),1.2-dichlorotetramethyldisilane (CH3Si(CH3)(Cl)Si(CH3)(Cl)CH3), l,l,2,2-tetrachloro-l,2- dimethyldisilane (CH3Si(Cl)2Si(Cl)2CH3), and hexachlorodisilane (ChSiSiCE), each of which is commercially available. As shown, the specific structure of the silicon precursor (VI) can be varied by selecting silylphosphine reactants with certain Q substituents and halogenated linking compounds (V) with varying numbers of halogen substituents. The silicon precursor (VI) may be isolated from the reaction mixture and optionally subjected to one or more further purification steps.

[0154] Example reactions for forming silicon precursor compositions comprising a silicon precursor having a structure according to Formula (2a) are shown in FIG. 7. The reactions shown are balanced but in practice they may not occur under stoichiometric conditions. The silylphosphine reactant (I) may have a general structure of PH2(SiQ3), where Q is a substituent group, selected from the group consisting of hydrogen or a hydrocarbyl group, such as an alkyl group. Example silylphosphine reactants include, but are not limited to, PH2(SiMe3) and PF^SiFE). The alkyl lithium compound (II) has a general structure of R’Li, where Li is a lithium atom and R’ is an alkyl group, typically a C1-C4 alkyl group. Example alkyl lithium compounds include, but are not limited to, methyllithium (MeLi), ethyllithium (EtLi), iso-propyllithium (iPrLi), n-butyllithium (nBuLi), sec-butyllithium (sBuLi), and tertbutyllithium (tBuLi), each of which is commercially available. In the first step (Eq. 4), the silylphosphine reactant (I) is contacted with the alkyl lithium compound (II) to form a lithiumsilylphosphine compound (III). The lithium silylphosphine compound (III) may optionally be isolated from the reaction mixture and subjected to the second reaction step (Eq. 5) where the lithium silylphosphine compound (III) is contacted with a linking compound (V) to form the silicon precursors (VI) having a structure according to Formula (2a) and a lithium halide salt (LiX) co-product (VII). Alternatively, the linking compound (V) is added to the first step reaction mixture without separating the lithium silylphosphine compound (III) first. The silicon precursor (VI) may be isolated from the reaction mixture and optionally subjected to one or more further purification steps.

[0155] In FIG. 7, Eq. 5 is shown for the formation of various silicon precursor (VI) structures depending upon the structure of the linking compound (V). The linking compound (V) may have a general structure of [(SiQ3)2P]3.mARmX, where m is an integer having a value of 0, 1, or 2; A is a carbon (C) atom or a silicon (Si) atom; R is a substituent that is bonded to A by an A-R bond, each R being independently selected from the group consisting of a hydrogen, a hydrocarbyl group, a silyl group; and X is a halogen atom, bonded to A by an A-X bond, X being selected from the group consisting of chlorine (Cl), bromine (Br), or iodine (I). Example linking compounds (V) include but are not limited to [(SiMe3)2P]Si(Me)2Cl, [(SiH3)2P]SiH2Cl, [(SiMe3)2P]C(Me)2Cl, and [(SiH3)2P]CH2Cl.

[0156] The synthetic route for forming the disclosed silicon precursors can be used to produce a variety of silicon precursor structures. However, in some instances, the method may be limited by the availability of certain structures of the silylphosphine reactant or the linking compound. In some embodiments, the silicon precursor formed via the method discussed above, and shown in any of FIG. 5, FIG. 6, and FIG. 7, is a first silicon precursor and the method further comprises performing an exchange reaction by contacting the first silicon precursor with a halosilane reactant to form a second silicon precursor, wherein the Q substituents on the first silicon precursor differ from the Q substituents on the second silicon precursor. Example halosilane reactants include, but are not limited to, chlorosilane (SiH3Cl), bromosilane (SiH3Br), iodosilane (SiH3I), trimethylchlorosilane (Si(Me)3Cl), dimethylchlorosilane (SiH(Me)2Cl), ethyldimethylchlorosilane (Si(Me)2(Et)Cl), tris(dimethylamino)chlorosilane (Si(NH2)Cl), triphenylchlorosilane (Si(Ph)Cl), each of which is commercially available. Other halosilanes are available commercially or may be obtained using synthetic methods reported in the literature. Additionally, or alternatively, in some other embodiments, the exchange reaction occurs with trifluoromethylsulfonate. An example of such an exchange reaction is the formation of SiH2(P(SiH3)2from the reaction of SiH2(P(SiMe3)2with SiH3I. Another example is the formation of CH2(P(SiH3)2from the reaction of CH2(P(SiMe3)2with SiH3I.

[0157] In certain other embodiments, the method for forming the silicon precursor composition comprising a silicon precursor having a structure according to general Formula (1) or general Formula (2) comprises catalytically coupling two silylphosphine reactants. FIG. 8 shows the formation of SiH2(P(SiH3)2)2(Eq. 6) and (H3Si)2P-SiH2-P(SiH3)-SiH2-P(SiH3)2(Eq. 7). In the reactions, a silylphoshine reactant is contacted with a catalyst to form the silicon precursor. The ratio of the formation of SiH2(P(SiH3)2)2versus (H3Si)2P-SiH2-P(SiH3)-SiH2-P(SiH3)2may be controlled by thestepwise addition of the silylphosphine reactant, where stepwise addition may favor the formation of (H3Si)2P-SiH2-P(SiH3)-SiH2-P(SiH3)2. The catalyst may comprise boron or one or more transition metals. Example boron containing catalysts include, but are not limited to, tris(pentafhiorophenyl)borane (E^CeFs^; aka, BCF), BH(CeF5)3, triphenylborane (B^eFsjs), 9- borabicyclo[3.3.1]nonane solution (BH(CsHi4); aka, 9-BBN), borane dimethyl sulfide complex (BH3S(Me)2; aka, BMS), borane-tetrahydrofuran solution (BH3 THF), BH3 NH(Me)2, BH3'N(Me)3, and the like. Example transition metal containing catalysts include, but are not limited to, platinum on carbon (Pt / C), palladium on carbon (Pd / C), dichlorotris(triphenylphosphine)ruthenium(II) (RuCl2(PPh3)3), triruthenium dodecacarbonyl (Ru3(CO)i2), chlorotris(triphenylphosphine)rhodium(I) (RhCl(PPh3)3), chlorocarbonylbis (triphenylphosphine)iridium(I) (IrCl(CO)(PPh3)2), Cp*IrMe2(PMe3), Cp*Ir(CO)2, dicobalt octacarbonyl (Co2(CO)s), Cp*2Sc-H, and the like. The desired silicon precursor may be isolated from the reaction mixture and optionally subjected to one or more further purification steps.

[0158] Vapor Depositions Methods

[0159] Another aspect of the present disclosure relates to vapor deposition methods for forming silicon containing films using the silicon precursor compositions disclosed herein (e.g., compositions comprising a silicon precursor having a structure according to general Formula (0), general Formula (1), general Formula (2), or general Formula (3) discussed above). Suitable vapor deposition methods include ALD and CVD, including epitaxial, plasma-enhanced, and thermal methods. The methods comprise providing a substrate in a reaction space (i.e., one or more reaction chambers), introducing a vapor of a silicon precursor composition to the reaction space, and exposing a surface of the substrate to the silicon precursor composition. The step of exposing the surface of the substrate to the silicon precursor composition results in the formation of an adsorbed silicon containing layer on the surface of the substrate. The adsorbed silicon containing layer may comprise the intact silicon precursor, or a portion or fragment of the silicon precursor. In some embodiments, a conversion step is employed to convert the adsorbed silicon containing layer to a targeted silicon containing fdm. In some embodiments, the surface of the substrate is additionally exposed a co-reactant to form a targeted silicon containing film.

[0160] In some embodiments, the methods for forming a silicon containing film comprises providing a substrate in a reaction space and performing one or more deposition cycles of a cyclic deposition process comprising exposing a surface of the substrate to a vapor of a silicon precursor composition and exposing the surface of the substrate to a co-reactant, thereby forming a silicon containing film on the surface of the substrate. The cyclical deposition process can include one or more of an ALD process and a cyclical CVD process. In some embodiments, the cyclic deposition process is an ALD process and the steps of exposing the surface of the substrate to the silicon precursor composition and exposing the surface of the substrate to the co-reactant occur sequentially. One or more purge steps may beperformed between the exposing steps to remove unreacted precursors and reactants and gaseous byproducts from the reaction space.

[0161] FIG. 9 shows a process flow diagram 900 of an exemplary embodiment for forming a silicon containing fdm using a cyclic deposition process. The method comprises providing a substrate in a reaction space 901 and executing one or more deposition cycles 902 of a cyclic deposition process, comprising: exposing a surface of the substrate to one of a silicon precursor composition and a coreactant 903; and exposing the surface of the substrate to the other of the silicon precursor composition and the co-reactant 905, thereby forming a silicon containing fdm on the surface of the substrate. For example, the substrate may be exposed to the silicon precursor composition, then to the co-reactant. Additionally, or alternatively, the substrate may be exposed to the co-reactant, then to the silicon precursor composition. The cyclic deposition process may optionally further comprise, purging the reaction space (904 and 906) between the exposing steps. Steps 903 and 905, with optional steps 904 and 906, make up one deposition cycle 902. The method may comprise repeating the deposition cycle 902 one or more (n) times 907 in a cyclic deposition process to increase the uniformity and / or the thickness of the silicon containing fdm on the surface of the substrate. The cyclic deposition process may be terminated 908 once the desired uniformity and / or thickness of the silicon containing fdm has been reacted.

[0162] Using the methods disclosed herein, the silicon containing fdm is deposed on a surface of a substrate. The substrate is not particularly limited and is generally described above. In some embodiments, the substrate is a semiconductor wafer or multiple semiconductor wafers. For example, the substrate may be a silicon wafer, such as a monocrystalline silicon wafer (e.g., a p-type monocrystalline silicon wafer). Alternatively, the silicon wafer may comprise silicon-germanium (SiGe). The substrate may comprise one or more material layers such as dielectric layers, insulating layers, metal layers, sacrificial layers, and so forth, in addition to the silicon containing layer. The substrate may include various topological features, such as gaps, recesses, lines, trenches, vias, holes, or spaces between elevated portions formed within or on at least a portion of a layer of the substrate. The silicon containing layer may be deposited over the entire surface of the substrate or only a portion of the substrate. The silicon containing layer may be deposited over the lateral surface(s) and / or the vertical surface(s) or sidewall(s) of various topological features if present.

[0163] In the method disclosed herein, a substrate is provided to a reaction space (i.e., one or more reaction chambers) (e.g., see 901 in FIG. 9). The reaction space is not particularly limited and may comprise one or more reaction chambers of a semiconductor processing apparatus. In some embodiments, semiconductor processing apparatus is a cluster tool. In some embodiments, a reaction chamber or reaction chambers in a flow-type reactor may be utilized. In some embodiments, a reaction chamber or reaction chambers in a showerhead-type reactor may be utilized. In some embodiments, a reaction chamber or reaction chambers in a space divided reactor may be utilized. In some embodiments, a reaction chamber or reaction chambers in a high-volume manufacturing-capable singlewafer reactor may be utilized. In other embodiments, a reaction chamber or reaction chambers in a batch reactor may be utilized. For embodiments in which a batch reactor is used, the reaction chamber may house a number of wafers, for example, the number of wafers may be in the range of 10 to 200, or 50 to 150, or even 100 to 150.

[0164] The method may further comprise, maintaining a temperature of the substrate at an elevated temperature (i.e., above room temperature). In some embodiments, the method further comprises heating the substrate to a temperature of at least about 40 °C to no more than about 600 °C. In some embodiments, the method comprises maintaining the substrate temperature from about 40 °C to about 500 °C, typically from about 100 °C to about 450 °C, or from about 100 °C to about 425 °C, or from about 100 °C to about 400 °C, or from about 100 °C to about 375 °C, or from about 100 °C to about 350 °C, or from about 100 °C to about 325 °C, or from about 100 °C to about 300 °C, or from about 100 °C to about 275 °C, or from about 100 °C to about 250 °C, or from about 200 °C to about 450 °C, or from about 200 °C to about 425 °C, or from about 200 °C to about 400 °C, or from about 200 °C to about 375 °C, or from about 200 °C to about 350 °C. In some embodiments, the method is performed while maintaining the substrate at a temperature of less than about 450 °C, or less than about 425 °C, or less than about 400 °C, or less than about 375 °C, or less than about 350 °C, or less than about 325 °C, or less than about 300 °C, or less than about 275 °C, or less than about 250 °C, or less than about 225 °C, or less than about 200 °C. In some embodiments, the method comprises maintaining the substrate temperature at about 25 °C, at about 50 °C, or at about 75 °C, or at about 100 °C, or at about 125 °C, or at about 150 °C, or at about 175 °C, or at about 200 °C, or at about 225 °C, or at about 250 °C, or at about 275 °C, or at about 300 °C, or at about 325 °C, or at about 350 °C, or at about 375 °C, or at about 400 °C, or at about 425 °C, or at about 450 °C, or at about 475 °C, or at about 500 °C. In some embodiments, where the method is performed under thermal conditions (i.e., the substrate is not exposed to a plasma species), the substrate temperature may be maintained at a temperature from about 300 °C to about 600 °C, typically from about 300 °C to about 550 °C, or from about 300 °C to about 500 °C. In other embodiments, where the substrate is exposed to plasma species, the substrate temperature may be maintained at a temperature from about 100 °C to about 500 °C, typically from about 100 °C to about 450 °C, or from about 100 °C to about 400 °C, or from about 100 °C to about 300 °C, or from about 100 °C to about 250 °C.

[0165] In addition to controlling the temperature of the substrate, the pressure inside of the reaction space may be maintained at a reduced pressure. The pressure within the reaction space may be between about 1 mTorr and about 760 Torr, or between about 0.5 Torr and about 30 Torr, such as about 10 Torr, or about 15 Torr, or about 20 Torr. In some embodiments, a pressure within the reaction space during the cyclic deposition process is less than about 500 Torr, or a pressure within the reaction chamber during the cyclic deposition process is between about 0. 1 Torr and about 500 Torr, or between about 1 Torr and about 100 Torr, or between about 1 Torr and about 20 Torr. In some embodiments, a pressurewithin the reaction chamber during the cyclic deposition process is less than about 10 Torr, less than about 50 Torr, less than about 100 Torr, or less than about 300 Torr.

[0166] In the methods disclosed herein, a vapor of the silicon precursor composition is introduced into the reaction space, and the surface of the substrate is exposed to or contacted with a the silicon precursor composition (e.g., see 903 or 905 in FIG. 9). In some embodiments, the silicon precursor composition is pulsed into the reaction space. Exposure of the substrate to the silicon precursor results in the formation of an adsorbed silicon containing layer on the surface of the substrate . The vapor of the silicon precursor composition is generally provided from a vapor delivery vessel that comprises the silicon precursor composition (e.g., see FIG. 10 and FIG. 11) and that is connected to and in fluid communication with the reaction space, typically through one or more gas lines, valves, and flow controllers. The vapor delivery vessel and the one or more gas lines, valves, and flow controllers may be heated to facilitate the flow of the silicon precursor composition vapor from the vapor delivery vessel, through the one or more gas lines, valves, and flow controllers into the reaction space. The vapor pressure of the silicon precursor will depend upon the specific chemical structure of the precursor and the temperature of the vessel may be adjusted (i.e ., heated or cooled) to provide sufficient vapor pressure (typically about 1-20 torr at temperature ranging from 25 °C to 200 °C) such that the silicon precursor composition can flow from the vapor delivery vessel into the reaction space. In some embodiments, a neat flow the silicon precursor composition vapor flows from the vapor delivery vessel through the one or more gas lines, valves, and flow controllers into the reaction space. In other embodiments, the vapor of the silicon precursor composition may be entrained in a flow of an inert carrier gas (e.g., nitrogen and / or a noble gas such as helium (He) and argon (Ar)) and introduced into the reaction space.

[0167] In some embodiments, the step of introducing the silicon precursor composition into the reaction space comprises pulsing the silicon precursor composition into the reaction space, over the substrate surface. In embodiments, where the silicon precursor composition is pulsed over the substrate, the pulse time may be between about 0.01 second and about 60 seconds, or from about 0.1 second to about 30 seconds, or from about 1 second to about 10 seconds. During the pulsing, the flow rate of the silicon precursor composition may be less than about 2000 seem, or less than about 1000 seem, or less than about 500 seem, or less than about 100 seem. The flow rate may be, for example, about 500 seem to about 1200 seem, such as about 600 seem, or about 800 seem, or about 1000 seem. The pulse time may vary according to silicon precursor in question and other process parameters (e.g., temperature, pressure, substrate, etc.), which may be independently selected to optimize the process according to the application in question.

[0168] In some embodiments of the disclosure, a conversion step is employed to convert the adsorbed silicon containing layer to a targeted silicon containing fdm. For example, in some embodiments, the surface of the substrate is contacted with a co-reactant to form the targeted silicon containing fdm (e.g., see 903 or 905 in FIG. 9). In some embodiments, the surface of the substrate is exposed to a plasma species to form the targeted silicon containing fdm. The specific conversion process will depend uponthe targeted silicon containing film. Similarly, the nature of the co-reactant will depend upon the targeted silicon containing film.

[0169] In some embodiments, the surface of the substrate is exposed to a plasma species to form the targeted silicon containing film. Plasma based methods may be preferred as such methods can generally be performed using lower temperatures. In such methods, the excess energy from the plasma species is used to promote the surface reactions. In some embodiments, the co-reactant comprises one or more excited and / or radical species that may be formed in situ in the reaction space using a direct plasma formed near the vicinity or directly above the substrate. Alternatively, the co-reactant comprising one or more excited and / or radical species may be formed using a remote plasma, either in situ in the reaction space in a location that is spatially separated from the substrate or upstream of the reaction space. In either case, the plasma may be formed using a feed gas comprising one or more of a carrier gas (inert gas) and a reactive gas. The reactive gas may be, by way of non-limiting example, oxygen (O2), ozone (O3), water (H2O), hydrogen peroxide (H2O2), an organic peroxide (ROOH, where R is an alkyl or an aryl group), nitrogen (N2), ammonia (NH3), hydrazine (N2H4), nitrous oxide (N2O), carbon dioxide (CO2), hydrogen (H2), ethylene (C2H4), acetylene (C2H2), and mixtures thereof. The carrier gas may be selected from the group consisting of nitrogen (N2), helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and mixtures thereof. The feed gas is fed into the reaction space and the plasma discharged is activated. In some embodiments, the feed gas is fed into the reaction space and the plasma discharged is pulsed (i.e., turned on and off). The power for generating the plasma can be varied in different embodiments of the disclosure. In some embodiments, the power for generating the plasma is from about 10 W to about 2,000 W, typically from about 20 W to about 1,000 W, or from about 20 W to about 500 W.

[0170] In some embodiments, the plasma may be generated from a reactive gas comprising a nitrogen compound and a nitrogen co-reactant is formed in or it is otherwise present in the plasma discharge. In some embodiments, the reactive gas comprises one or more of nitrogen (N2), a N2 / H2 mixture, ammonia (NH3), an alkyl amino (NR3, where each R is independently an H, an alkyl group, or an aryl group), hydrazine (N2H4), and a substituted hydrazine; hence, the co-reactant may comprise one or more of N2, NH3, an alkyl amino, hydrazine N2H4, a substituted hydrazine, as applicable, as well as excited species, radical species, and plasma species formed therefrom. In some embodiments, the nitrogen co-reactant comprises a nitrogen plasma species, for example, the nitrogen co-reactant may comprise one or more of activated nitrogen (N2), activated ammonia (NH3), nitrogen atoms (N), NH and NH2 radicals, and other N-H containing species created in the plasma discharge. In some embodiments, the nitrogen coreactant is a nitrogen plasma species; by way of non-limiting example, the nitrogen co-reactant may be one or more of activated nitrogen (N2), activated ammonia (NH3), nitrogen atoms (N), NH and NH2 radicals, and other N-H containing species created in the plasma discharge.

[0171] In some embodiments, the plasma may be generated from a reactive gas comprising a carbon compound and a carbon co-reactant is formed in or it is otherwise present in the plasma discharge. In some embodiments, the reactive gas comprises one or more of methane (CH4), a C2-C4 alkyl group, ethylene (C2H4), and acetylene (C2H2); hence, the plasma may comprise one or more of CH4, a C2-C4 alkyl group, C2H4, C2H2, as applicable, as well as excited species, radical species, and plasma species formed therefrom. In some embodiments, the carbon co-reactant comprises a carbon plasma species. In some embodiments, the carbon co-reactant is a carbon plasma species.

[0172] In some embodiments, the reactive gas comprises hydrogen and / or a noble gas selected from the group consisting of helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and mixtures thereof. In some embodiments, the co-reactant comprises a hydrogen plasma species. In some embodiments, the co-reactant comprises a noble gas plasma species. In these cases, the hydrogen plasma and / or noble gas plasma may be used to activate the adsorbed layer on the substrate surface. The excited species from the gases in the plasma may not necessarily contribute material to the deposited fdm but can, in some circumstances, contribute to fdm growth.

[0173] In some embodiments, the plasma may be generated from a reactive gas comprising an oxygen compound and an oxygen co-reactant is formed in or it is otherwise present in the plasma discharge. In some embodiments, the reactive gas comprises one or more of oxygen (O2), ozone (O3), water (H2O), hydrogen peroxide (H2O2), an organic peroxide, an alcohol, nitrogen dioxide (NO2), nitrous oxide (N2O), nitric oxide (NO), dinitrogen pentoxide (N2O5), pyridine oxide (C5H5NO), an amino oxide; hence, the co-reactant may comprise one or more of oxygen (O2), ozone (O3), water (H2O), hydrogen peroxide (H2O2), an organic peroxide, an alcohol, nitrogen dioxide (NO2), nitrous oxide (N2O), nitric oxide (NO), dinitrogen pentoxide (N2O5), pyridine oxide (C5H5NO), an amino oxide, as applicable, as well as excited species, radical species, and plasma species formed therefrom. In some embodiments, the oxygen co-reactant comprises an oxygen plasma species; by way of non-limiting example, the oxygen co-reactant may comprise one or more of atomic oxygen (O), excited diatomic oxygen (e.g., singlet oxygen (’02)), ozone (O3), hydroxyl radical (OH), peroxyl radical (e.g., HO2), and nitric oxide (NO). In some embodiments, the oxygen co-reactant is an oxygen plasma species, for example, the oxygen co-reactant may be one or more of atomic oxygen (O), excited diatomic oxygen (e.g., singlet oxygen (’02)), ozone (O3), hydroxyl radical (OH), peroxyl radical (e.g., HO2), and nitric oxide (NO).

[0174] In some embodiments, the surface of the substrate is exposed to the co-reactant under thermal conditions. Under thermal conditions, the reaction(s) may be promoted by increasing the temperature of the substrate relevant to ambient temperature. Generally, the temperature increase provides the energy needed for the reaction(s) to proceed in the absence of other external energy sources, such as plasma, radicals, or other forms of radiation. In other words, the reaction does not employ reactive species generated by a plasma and may therefore be referred to as “plasma-free”. Suitable nitrogen coreactants include, but are not limited, to ammonia (NH3), an alkyl amino (NR3, where each R is independently an H, an alkyl group, or an aryl group), hydrazine (N2H4), and a substituted hydrazine.Suitable oxygen co-reactants include, but are not limited, oxygen (O2), ozone (O3), water (H2O), hydrogen peroxide (H2O2), an organic peroxide (ROOH, where R is an alkyl or an aryl group), an alcohol (ROH, where R is an alkyl or an aryl group), nitrogen dioxide (NO2), nitrous oxide (N2O), nitric oxide (NO), dinitrogen pentoxide (N2O5), pyridine oxide (C5H5NO), an amino oxide (R3NO, where each R is independently an alkyl group or an aryl group, and / or two or more R groups may be bonded to one another to form a ring structure).

[0175] In some embodiments, the step of introducing the co-reactant into the reaction space comprises pulsing the co-reactant into the reaction space, over the substrate surface. Pulsing may be achieved by controlling the flow of the reactant gas and / or the co-reactant to the reaction space and / or by pulsing the plasma discharge that is used to form the co-reactant if applicable. In embodiments where the coreactant is pulsed over the substrate, the pulse time may be between about 0.01 second and about 60 seconds, or from about 0.1 second to about 30 seconds, or from about 1 second to about 10 seconds. During the pulsing, the flow rate of the reactant gas and / or the co-reactant may be less than about 2000 seem, or less than about 1000 seem, or less than about 500 seem, or less than about 100 seem. The flow rate may be, for example, about 500 seem to about 1200 seem, such as about 600 seem, or about 800 seem, or about 1000 seem. The pulse time may vary according to co-reactant in question and other process parameters (e.g., temperature, pressure, substrate, etc.), which may be independently selected to optimize the process according to the application in question.

[0176] In some embodiments, the step of providing the silicon precursor composition into the reaction space and the step of providing the co-reactant into the reaction space at least partially at overlap. For instance, in embodiments where the silicon precursor composition and the co-reactant are pulsed over the substrate, the silicon precursor composition pulse and the co-reactant pulse may at least partially overlap. In some embodiments, the introduction of the silicon precursor composition and the introduction of the co-reactant into the reaction space may be simultaneous. In some embodiments, the introduction of the silicon precursor composition and the co-reactant into the reaction space may be at least partially separate. For instance, in embodiments where the silicon precursor composition and the co-reactant are pulsed over the substrate surface, the silicon precursor pulse and the co-reactant pulse may at least be partially separated. In some embodiments, the introduction of the silicon precursor composition and the co-reactant into the reaction space may be completely separate. For instance, in embodiments where the silicon precursor composition and the co-reactant are pulsed over the substrate surface, the silicon precursor pulse composition and the co-reactant pulse may be completely separate.

[0177] In some embodiments, the reaction space is purged between the steps providing the silicon precursor composition and providing the co-reactant to the reaction space. For example, optional purging steps are shown in 904 and 906 in FIG. 9. Purging may be affected between two pulses of gases which react with each other. Purging may also be affected between two pulses of gases that do not react with each other. For example, a purge or purging may be provided between pulses of two precursors or between a precursor and a reactant. Purging may avoid or at least reduce gas-phase interactionsbetween the two gases reacting with each other. It shall be understood that a purge can be affected either in time or in space, or both. For example, in the case of temporal purges, a purge step can be used, for example, in a temporal sequence of providing a first reactant to a reaction space, providing a purge gas to the reaction space, and providing a second reactant to the reaction space, wherein the substrate on which a layer is deposited does not move. For example, in the case of spatial purges, a purge step can comprise moving a substrate from a first location to which a first reactant is continually supplied, through a purge gas curtain, to a second location to which a second reactant is continually supplied.

[0178] The various process steps may be repeated one or more times to grow a film of the silicon containing material on the surface of the substrate (e.g., see 907 in FIG. 9). The number of repeated cycles («) is not particularly limited and depends on the growth per-cycle (GPC) of silicon containing material and the targeted thickness the film. The GPC of the carbon doped silicon film may at least about 0.01 A / cycle to no more than about 10 A / cycle. In certain embodiments, the GPC may vary depending upon the exposure time of the substrate surface to the film forming composition. In some embodiments, the GPC of silicon containing material film may at least about 0.01 to no more than about 3 A / cycle, or at least about 0.05 to no more than about 3 A / cycle, or at least about 0.05 to no more than about 2.5 A / cycle, or at least about 0.05 to no more than about 2.0 A / cycle, or at least about 0.05 to no more than about 1.5 A / cycle, or at least about 0.05 A / cycle to no more than about 1 A / cycle, or at least about 0.05 A / cycle to no more than about 0.5 A / cycle, or at least about 0.1 to no more than about 3 A / cycle, or at least about 0.1 to no more than about 2.5 A / cycle, or at least about 0. 1 to no more than about 2.0 A / cycle, or at least about 0.1 to no more than about 1.5 A / cycle, or at least about 0. 1 A / cycle to no more than about 1 A / cycle, or at least about 0.5 to no more than about 3 A / cycle, or at least about 0.5 to no more than about 2.5 A / cycle, or at least about 0.5 to no more than about 2.0 A / cycle, or at least about 0.5 to no more than about 1.5 A / cycle. In some embodiments, the GPC of silicon containing film is about 0.5 A / cycle or more, or about 1 A / cycle or more, or about 1.5 A / cycle or more, or about 2 A / cycle or more. In some embodiments, the GPC of silicon containing material film is about 0.5 A / cycle, or about 1 A / cycle, or about 1.5 A / cycle, or about 2 A / cycle, or about 2.5 A / cycle. Typically for ALD processes the GPC is between about 0. 1 A / cycle and about 3 A / cycle, whereas the GPC for cyclic CVD processes can be higher depending upon the exposure time of the substrate to the film forming composition. The number of repeated cycles (n) is not particularly limited and may be between 1 and about 1,000, typically between 1 and about 500, or between 1 and about 200, or between 1 and about 100, or between 1 and about 50, or between 1 and about 10.

[0179] Vapor Deposition Systems

[0180] Another aspect of the present disclosure is related to systems for forming silicon containing films using the silicon precursor compositions (e.g., compositions comprising a silicon precursor having a structure according to general Formula (0), general Formula (1), general Formula (2), or general Formula (3) discussed above) and the methods disclosed herein. In some embodiments, the system is a semiconductor processing apparatus that comprises a reaction space (i.e., at least one reaction chamber)for accommodating a substrate. The semiconductor processing apparatus may comprise one reaction chamber, two reaction chambers, three reaction chambers, four reaction chambers, or more. In some embodiments, the semiconductor processing apparatus is a cluster tool. In some embodiments, a reaction chamber or reaction chambers in a flow-type reactor may be utilized. In some embodiments, a reaction chamber or reaction chambers in a showerhead-type reactor may be utilized. In some embodiments, a reaction chamber or reaction chambers in a space divided reactor may be utilized. In some embodiments, a reaction chamber or reaction chambers in a high-volume manufacturing-capable single wafer reactor may be utilized. In other embodiments, a reaction chamber or reaction chambers in a batch reactor may be utilized. The semiconductor processing apparatus further comprises a means for exposing the surface of the substrate to the silicon precursor disclosed herein. The semiconductor processing apparatus may further comprise a means for exposing the substrate the co-reactant and optionally a means for purging the reaction space between the exposing steps.

[0181] In embodiments, a vapor of the silicon precursor composition is introduced into the reaction space and the substrate is exposed to a vapor of the silicon precursor composition. An injector system comprising one or more gas lines, values, manifolds, and flow controllers may be used to control flow (e.g., turn off / on and adjust the flow rate) of the silicon precursor composition into the reaction space. A vapor delivery vessel comprising the silicon precursor composition may be removably coupled, either directly or indirectly through one or more intermediate vessels and / or accumulators, to the injector system. The vapor delivery vessel comprising the silicon precursor composition is configured to provide a vapor flow of the silicon precursor composition from the vapor delivery vessel to the reaction space. The vapor delivery vessel comprises an outer wall that encloses a cavity for storing and / or holding the silicon precursor composition and a gas outlet for allowing a vapor of the silicon precursor composition to exit the cavity. Typically, the outer wall and cavity of the vapor delivery vessel is formed from stainless steel (e.g., 316, 316L, 304, or 304L alloys). The vapor delivery vessel may be heated or cooled, as required, such that the vapor pressure of the silicon precursor is in a suitable range (typically about 1-20 torr at temperature ranging from 25 °C to 200 °C) for vapor delivery to the reaction space. The vapor delivery vessel may comprise a number of other design features, such that it is configured for providing a vapor flow of the silicon precursor composition from the vapor delivery vessel to the reaction space. In some embodiments, the vapor delivery vessel further comprises one or more fluid inlets or outlets, in addition to the gas outlet. For example, the one or more fluid inlets may comprise an inlet port for filling the vapor delivery vessel with the silicon precursor composition, either at the semiconductor processing apparatus site or at a remote location. Additionally, or alternatively, the one or more fluid inlets may comprise a carrier gas inlet for flowing a carrier gas into the cavity of the vapor delivery vessel. The carrier gas may be directed through a carrier gas conduit and over the surface of the silicon precursor composition and / or it may be bubbled through or otherwise passed through the silicon precursor composition. In either configuration, a vapor of the silicon precursor composition may be entrained in the carrier gas flow which exits through the gas outlet. In another example, the one ormore fluid outlets may comprise a burp valve for releasing excess pressure within the cavity. The various gas inlets and outlet may comprise one or more valves for controlling the flow in and out of the cavity. The one or more valves may be rated for high temperature (e.g., typically up to 100°C, or up to 150°C, or up to 200°C) to withstand the temperatures that may be required to deliver a sufficient vapor of the silicon precursor composition. In some embodiments, the vapor delivery vessel further comprises one or more sensors, such as one or more temperature sensors, and / or one or more pressure sensors, and / or one or more level sensors. A variety of liquid level sensors for measuring the amount of liquid silicon precursor within the cavity are known in the art, including, but not limited to, capacitive -based sensors, conductivity-based sensors, float switch level sensors, tuning fork sensors, and ultrasonic sensors. In some embodiments, the vapor delivery vessel further comprises one or more heat transfer elements, such as, for example, fins, rods, beads, and the like, to facilitate heat transfer from the walls of the vessel to the silicon precursor composition within the cavity, or vice versa. The one or more heat transfer elements may form a serpentine or radial path for holding the silicon precursor composition within the cavity and, in some cases, for directing the flow of a carrier gas over or through the silicon precursor composition. Such configurations may be particularly useful for delivering a vapor of low- volatility liquid and solid precursors. The various design features described above may be combined, as appropriate, to optimize the vapor flow from the vapor delivery vessel to the reaction space.

[0182] FIG. 10 shows a perspective view of an exemplary embodiment of a vapor delivery vessel 1000 according to the disclosure. The vapor delivery vessel 1000 comprises an outer wall 1001 that encloses an internal cavity 1002 for storing the silicon precursor composition inside of the internal cavity 1002. The vapor delivery vessel comprises a gas outlet 1004 that is coupled to and in fluid communication with a gas outlet valve 1005. The vapor delivery vessel further comprises a gas inlet 1006 that is coupled to and in fluid communication with a gas inlet valve 1007. In some embodiments, the vapor delivery vessel 1000 further comprises a gas conduit 1008 that extends into the internal cavity 1002. The gas conduit comprises a distal portion comprising an end opening that either extends into a headspace of the internal cavity 1002 for passing a carrier gas over the surface of the silicon precursor composition or that extends into the silicon precursor composition (not shown) for bubbling or otherwise passing the carrier gas through the silicon precursor composition. In certain embodiments, where the silicon precursor composition is in liquid form, the vapor delivery vessel 1000 may further optionally comprises a level sensor port 1009 and a level sensor 1010 comprising a thermocouple 1011 that extends into the internal cavity 1002 and into the liquid silicon precursor composition for measuring the amount and the temperature of the liquid silicon precursor composition that is contained within the internal cavity 1002.

[0183] FIG. 11 shows a perspective view of another exemplary embodiment of a vapor delivery vessel 1100 according to the disclosure; a plan view of the top portion of the vapor delivery vessel 1100 is shown in the inset. The vapor delivery vessel 1100 comprises a container body 1101 and a removablelid 1102 adapted to engage the container body 1101, wherein the lid 1102 comprises a gas inlet 1104 that is coupled to and in fluid communication with a gas inlet valve 1105 and a gas outlet 1106 that is coupled to and in fluid communication with a gas outlet valve 1107. The container body 1101 and the lid 1102 together define an outer wall that encloses an internal cavity 1110 for storing the silicon precursor 1111 which may be in liquid or solid form inside of the internal cavity 1110. The internal cavity 1110 comprises one or more heat transfer elements 1112 which may form a serpentine path that is configured to hold the silicon precursor composition 1111 and that defines the gas flow path from the gas inlet 1104 to the gas outlet 1106 (see arrows in the inset) for flowing a carrier gas over the surface of the silicon precursor composition.

[0184] FIG. 12 shows an exemplary embodiment of a semiconductor processing apparatus 1200 according to the present disclosure. Gaseous reactants are provided into the reaction chamber 1201 through an injector system 1202. The injector system 1202 may be configured to provide a vapor of the silicon precursor composition from a silicon precursor source 1203 (e.g., a vapor delivery vessel) that is coupled to a silicon precursor source valve 1204 and a reactant gas and / or co-reactant from a coreactant source 1205 that is coupled to a co-reactant source valve 1206. One or more of the gaseous reactants may be entrained in a carrier gas (e.g., nitrogen and / or a noble gas, such as He, Ne, Ar, Kr, Xe, and combinations thereof) provided from a carrier gas source 1207 coupled to a carrier gas source valve 1208. The injector system 1202 may further comprise one or more other gas sources (not shown), for example, for providing purge gases, feed gasses, additional carrier gases, etc., and a means for heating one or more of the sources and the corresponding valves and gas lines (not shown), if required, to facilitate the introduction of the silicon precursor composition and reactants into the reaction chamber 1201. The various gasses flow into the reaction chamber 1201 through a showerhead 1209 that is positioned directly above a susceptor 1210 on which a substrate 1211 is placed. In some embodiments, the reaction chamber 1201 further comprises one or more heating elements (not shown) that are in thermal communication with the substrate 1211 and one or more thermocouples (not shown) to measure and maintain a temperature of the substrate at a set temperature. Unreacted gasses and gaseous reaction by-products exit the reaction chamber 1201 through an exhaust line 1212 that is optionally connected to one or more vacuum pumps 1213. A plasma generator 1214 (e.g., a RF power generator or microwave power generator) is electrically connected to the showerhead 1209, allowing for the showerhead 1209 to be biased relative to the susceptor 1210 to form a plasma discharge between the two. Optionally, an ion trap (not shown) may be positioned between the showerhead 1209 and the substrate 1211 to restrict the plasma to upper portion of the reaction chamber 1201, above the ion trap. For example, an electrically grounded mesh plate may be used as an ion trap. The semiconductor processing apparatus also comprises a controller 1220 operably connected to the silicon precursor source valve 1204, the coreactant source valve 1206, and the carrier gas source 1208 valve, the plasma generator 1214, and other components (not shown). The controller 1220 is configured and programmed to independently control (e.g., turn on and off, etc.) the supply of the various gasses (e.g., the silicon precursor, the co-reactant,carrier gasses, etc.) and the plasma generator 1214, as required, to deposit a silicon containing film on a surface of the substrate 1211.

[0185] The semiconductor processing apparatus also comprises a controller 1220. The controller 1220 generally includes a device interface 1221, a processor 1222, a user interface 1223, and a memory 1224. The device interface 1221 connects the processor 1222 via a wired or wireless link to various components of the injector assembly 1202, the reaction chamber 1201, the plasma generator 1214, the exhaust source 1212, and / or and other components such as, one or more heating elements and thermal couples (not shown) for controlling the temperature of the substrate 1211. The processor 1222 is in turn operably connected to the user interface 1221, for example, to receive a user input and / or provide a user output and is in communication with the memory 1224. The memory 1224 may include a non-transitory machine-readable medium having a plurality of program modules 1225 recorded thereon that, when read by the processor 1222, cause the processor 1222 to execute certain operations. Among the operations are operations of a method for depositing a carbon-doped silicon containing film (e.g., 900, see FIG. 9) using the silicon precursor composition described above.

[0186] In some embodiments, the controller 1214 is configured and programed to perform a first operation and a second operation, among other things. In the first operation, the controller 1220 opens the silicon precursor source valve 1204 to flow a vapor of the silicon precursor composition from the silicon precursor source 1203 into the reaction chamber 1201, thereby exposing a surface of the substrate to the vapor of the silicon precursor and, after a set period of time, the controller 1220 closes the silicon precursor source valve 1204 to cease the flow of the silicon precursor composition into the reaction chamber 1201. In the second operation, the controller 1220 opens the co-reactant source valve 1206 to flow the feed gas and / or co-reactant from the co-reactant source 1205 into the reaction chamber 1201 and, after a set period of time, pulses (turn on, then off) the plasma generator 1214 thereby exposing the surface of the substrate to the co-reactant. After another set period of time, the controller 1220 closes the co-reactant source valve 1206 to cease the flow of the reactant gas and / or co-reactant into the reaction chamber 1201. In certain embodiment, the controller 1220 is programed to perform the first operation and the second operation, or vice versa, wherein at least a portion of the first operation overlaps with at least a portion of the second operation such that the flow of the silicon precursor composition vapor into the reaction chamber at least partially overlaps with the flow of the co-reactant into the reaction chamber. In certain other embodiments, the controller 1220 is programed to sequentially perform the first operation followed by the second operation, or vice versa, such that the flow of the silicon precursor composition vapor into the reaction chamber and the flow of the co-reactant into the reaction space do not overlap. The controller 1220 may be programed to repeat the first operation and the second operation (n times) to grow a silicon containing film on the surface of the substrate 1211.

[0187] As will be appreciated by one of skill in art, the controller may be configured and programed to perform other operations. For example, the controller 1220 may be operably connected to a purgegas source (not shown) and configured and programed to open a valve (not shown) to the purge gas source to flow a purge gas into the reaction chamber 1201 and, after a set period of time, close the valve to the purge gas. In another example, the controller 1220 may be operably connected to one or more heaters (not shown) and one or more thermocouples (not shown) and configured and programed to measure and control a temperature of the at least one heating element to maintain a temperature of the substrate 1211 at a set temperature.

[0188] Further, as will be appreciated by one of skill in art, other semiconductor processing apparatus configurations are possible. For example, other flow configurations and / or other mechanisms for housing the substrate in the reaction chamber and flowing gasses over the substrate may be utilized. In another example, in the semiconductor processing apparatus may comprise two or more reaction chambers, where the first operation occurs in a first reaction chamber and the second operation occurs in a second chamber. Additionally, other plasma generation configurations may be utilized. In some embodiments, a remote plasma unit that is positioned upstream of the reaction chamber may be used to generate a remote plasma. In other embodiments, the reactor may not comprise a plasma generator.

[0189] In some embodiments, the semiconductor processing apparatus, comprises: a reaction space for accommodating a substrate; a silicon precursor source for providing a vapor of a silicon precursor composition in gas communication via a silicon precursor source valve with the reaction space; a coreactant source for providing a reactant gas and / or co-reactant in gas communication via a co-reactant source valve with the reaction space; a plasma unit comprising a plasma generator; and a controller operably connected to the silicon precursor source valve, the co-reactant source valve, and the plasma generator. The controller may be configured and programmed to control supplying the silicon precursor composition vapor into the reaction space; and supplying the reactant gas and / or co-reactant into the reaction space and activating the plasma generator. The controller may be programmed to repeat the various process steps n time to deposit a silicon containing film on the surface of the substrate. In some embodiments, the silicon precursor source is a vapor delivery vessel that comprises the silicon precursor composition.

[0190] Select Applications.

[0191] The disclosed silicon precursor compositions and the methods and systems for using said precursor compositions for depositing silicon containing films may provide several benefits. The silicon containing films can be produced using plasma-enhanced methods, allowing for the use of lower deposition temperatures that are compatible with the fabrication of semiconductor device structures. Further, the silicon containing films may have one or more of a high growth rate (i.e., GPC), a high conformality and uniformity, and excellent wet etch resistance. It is hypothesized that these attributes are, at least in part, due to the high silicon content of the silicon precursors. The disclosed silicon precursors and the methods and systems for using said precursors are particularly useful for forming films comprising silicon nitride that may overcome many of the limitations known in the art. In some embodiments, use of the silicon precursor compositions disclosed herein in a vapor deposition processadvantageously produces a silicon containing fdm with a high GPC. In some embodiments, the silicon containing fdm has a GPC of at least about 0.3 to no more than about 3.0 A / cycle, or at least about 0.5 to no more than about 2.5 A / cycle, or at least about 0.5 to no more than about 2.0 A / cycle, or at least about 0.5 to no more than about 1.5 A / cycle. In some embodiments, the silicon containing fdm has a GPC of about 0.5 A / cycle or more. In some embodiments, the silicon containing fdm has a GPC of about 1.0 A / cycle or more. In some embodiments, the silicon containing fdm has a GPC of about 1.5 A / cycle or more. In any of these embodiments, the silicon containing fdm may comprise silicon nitride. In many applications, a high GPC is beneficial as it can reduce wafer processing times and material costs.

[0192] In some embodiments, use of the silicon precursor compositions disclosed herein in a vapor deposition process advantageously produces a silicon containing fdm with a high conformity. In some embodiments, the silicon containing fdm has a step coverage of more than about 80%. In some embodiments, the silicon containing fdm has a step coverage of about 90% or more. In some embodiments, the silicon containing fdm has a step coverage of about 95% or more. In some embodiments, the silicon containing fdm has a step coverage of about 110% or less. In some embodiments, the silicon containing fdm has a step coverage of about 105% or less. In some embodiments, the silicon containing fdm has a step coverage of about 90% or more and about 110% and less. In preferred embodiments, the silicon containing fdm has a step coverage of about 95% or more and about 105% and less. In any of these embodiments, the silicon containing fdm may comprise silicon nitride. Good step coverage and conformality are required for advanced logic and memory applications. For example, the use of silicon nitride layers as gate spacers will require fdms with a high step coverage and conformality.

[0193] In some embodiments, use of the silicon precursor compositions disclosed herein in a vapor deposition process advantageously provides a silicon containing fdm with an excellent wet etch rate. In some embodiments, the silicon containing fdm has a wet etch rate of less than 2.5 nm / min in 1.5% dilute hydrofluoric acid. In some embodiments, the silicon containing fdm has a wet etch rate of less than 1.5 nm / min in 1.5% dilute hydrofluoric acid. In any of these embodiments, the silicon containing fdm may comprise silicon nitride. The wet etch rate is a critical measure of fdm quality. Silicon nitride fdms with a high etch resistance are required for gate spacers for high-K metal gate applications.

[0194] In addition to the foregoing benefits, in some embodiments, the use of certain silicon precursor compositions disclosed herein in a vapor deposition process advantageously provides a silicon containing fdm with a low carbon content. In certain embodiments, the silicon precursor is carbon free. In some embodiments, the silicon precursor is selected from the group consisting of P(SiH3), SIH2(P(SIH3)2)2, SIH(P(SIH3)2)3, SI(P(SIH3)2)4, SIH(SIH3)(P(SIH3)2)2, Si(SiH3)2(P(SiH3)2)2, Si(SiH3)(P(SiH3)2)3, (H3Si)2P-SiH2-P(SiH3)-SiH2-(P(SiH3)2, and combinations thereof. In some embodiments, the carbon content of the silicon containing fdm may be no more than about 5 at %, or no more than about 4 at %, or no more than about 3 at %, or no more than about 2 at %, or no more thanabout 1 at %, or no more than about 0.5 at %, or no more than about 0.1 at %. In any of these embodiments, the silicon containing film may comprise silicon nitride. In certain of these applications, too high of a carbon content can lead to silicon nitride films with poor conformality.

[0195] Examples.

[0196] The following are non-limiting examples that further illustrate certain aspects and embodiments of the disclosure. The examples are not intended to be all inclusive nor should they be interpreted to limit the scope of the disclosure in any way.

[0197] Example 1: Synthesis of (SiMepjl^-CHj-l fSiMeiJj

[0198] A silicon precursor composition comprising (SiMe3)2P-CH2-P(SiMe3)2 was prepared using a two-step synthetic approach. Note that (SiMc3)3P-CH2-P(Si Mc3)3has a structure according to general Formula (1), where A=C, R=H, Q=Me, m=2, and n=0. Anhydrous solvents were utilized in the synthetic method and the solvents were deoxygenated prior to use. The synthesis was conducted in an inert environment under argon.

[0199] In the first step, LiP(SiMe3)2 is produced from the reaction of tris(trimethylsilyl)phosphine (PfSiMcs);) with methyllithium (LiCHs). An oven dried 250 mb Schlenk flask was loaded with 5.3 g (11 mmol) of P(SiMe3)3and 60 mb of tetrahydrofuran in a glove box. The flask was removed from the glove box, placed under argon, and cooled to 0 °C using an ice water bath. Next, 13 mb of 1.59 M solution of methyllithium in diethylether was added dropwise to the flask. The mixture was allowed to come to room temperature while stirring overnight. The resulting mixture was a clear solution with a slight yellow color. The mixture was placed under vacuum to remove a volatile component to yield a white solid material, EiP(SiMe3)2.

[0200] In the second step, (SiMe3)2P-CH2-P(SiMe3)2 is produced from the reaction of EiP(SiMe3)2 with dichloromethane (CHAT). EiP(SiMe3)2, produced in the first step, was dissolved in 10 mb of hexane and the solution was added dropwise to a second solution of 970 mg of dichloromethane in 50 mb of hexane. The resulting mixture appeared cloudy and was allowed to sit overnight. The reaction mixture was filtered under an argon curtain to remove a solid material from the mixture. The filtrate was placed under vacuum to remove the volatile components to yield a colorless oil. Next, the colorless oil was distilled at 105 °C under vacuum (~80 mTorr) to yield approximately 2.93 g of a colorless liquid. The identity of the colorless liquid was confirmed to be (SiMe3)2P-CH2-P(SiMe3)2 using NMR spectroscopy, produced at 71% yield.

[0201] An NMR sample was prepared in -toluene inside of a glovebox. FIG. 13A shows the ’H NMR spectrum collected at 400 MHz and 298 K, where the singlet peak at 1.88 ppm corresponds to the two hydrogen atoms of the P-CH2-P moiety and the singlet peak at 0.29 ppm corresponds to the 36 hydrogen atoms of the Si(Me3) groups. FIG. 13B shows the31P NMR spectrum collected at 163 MHz and 298 K, where the singlet peak at -167.53 ppm corresponds to the two phosphorus atoms of the P-CH2-P moiety.

[0202] Example 2: Synthesis of (SiH pjl^-CHj-lfSiH

[0203] A silicon precursor composition comprising (SiH3)2P-CH2-P(SiHs)2 was synthesized using three step synthetic approach. Note that (SiH3)2P-CH2-P(SiH3)2 has a structure according to general Formula (1), where A=C, R=H, Q=H, m=2, and n=0. Anhydrous solvents were utilized in the synthetic method and the solvents were deoxygenated prior to use. The synthesis was conducted in an inert environment under argon.

[0204] In steps one and two, (SiMe3)2P-CH2-P(SiMe3)2 is produced according to the method described in Example 1. In the third step, (SiFE^P-CFE-P SiFE^ is produced from the reaction of (SiMes P-CFE- P(SiMe3)2 with iodosilane (Si H, I). lodosilane was prepared by reacting stochiometric amounts of sublimed iodide with phenyl silane in glass pressure vessel, maintained at -30°C. lodosilane was then separated from the reaction mixture by distillation.

[0205] In the third step, a 100 m Schlenk flask was loaded with 3.00 g (8.14 mmol) of (SiMesEP- CH2-P(SiMe3)2 dissolved in approximately 20 m of toluene in a glove box. A solution of 5.27 g iodosilane (33.4 mmol) in 20 mb of toluene was added to the flask and the mixture was stirred overnight. The resulting mixture was placed under vacuum to remove a volatile component to yield a colorless oil. Next, the colorless oil was distilled in two stages, the first stage at 0 °C and the second stage at room temperature under vacuum (~50 mTorr) to yield approximately 0.826 mg of a colorless liquid. The identity of the colorless liquid was confirmed to be (SiH3)2P-CH2-P(SiH3)2 using NMR spectroscopy, produced at 51% yield.

[0206] An NMR sample was prepared in S-toluene inside of a glovebox. FIG. 14A shows the ’H NMR spectrum collected at 400 MHz and 298 K, where the singlet at 1.56 ppm corresponds to the two hydrogen atoms of the P-CH2-P moiety and the multiplet from 3.84-3.79 ppm corresponds to the 12 hydrogen atoms of the SiH3groups. FIG. 14B shows the31P NMR spectrum collected at 163 MHz and 298 K, where the singlet peak at -221.40 ppm corresponds to the two phosphorus atoms of the P-CH2-P moiety.

[0207] Example 3: Synthesis of (SiMepjl^-SiHj-l SiMeiE

[0208] A silicon precursor composition comprising (SiMe3)2P-SiH2-P(SiMe3)2 was synthesized using a two-step synthetic approach. Note that (SiMe3)2P-SiH2-P(SiMe3)2has a structure according to general Formula (1), where A=Si, R=H, Q=Me, m=2, and n=0. Anhydrous solvents were utilized in the synthetic method and the solvents were deoxygenated prior to use. The synthesis was conducted in an inert environment under argon.

[0209] In the first step, EiP(SiMe3)2 is produced from the reaction of tris(trimethylsilyl)phosphine (P(SiMe3)3) with methyllithium (Li CH;). An oven dried 100 mb Schlenk flask was loaded with 1.60 g (6.39 mmol) of P(SiMe3)3 and 20 mb of dimethylether (DME) in a glove box. The flask was removed from the glove box, placed under argon, and cooled to 0 °C using an ice water bath. Next, 2.06 mb of 3.1 M solution of Li CH, in DME was added dropwise to the flask. The mixture was allowed to cometo room temperature while stirring overnight. The resulting mixture was a clear solution with a slight yellow color. The mixture was placed under vacuum to remove a volatile component to yield a white solid material, LiP(SiMes)2.

[0210] In the second step, (SiMes P-SilT-P SiMes is produced from the reaction of LiPiSiMcA with diiodosilane (SiPhh). LiP(SiMes)2, produced in the first step, was dissolved in 20 mL of hexane / DME (80:20) the solution was cooled to -40 °C using a dry ice acetonitrile bath. A second solution of 9.79 mg diiodosilane in 20 mL of hexane was prepared and added dropwise to the LiP(SiMe3)2 in hexane / DME solution. The resulting mixture appeared cloudy and was maintained -40 °C for about three hours, then filtered under an argon curtain to remove a solid material from the mixture. The filtrate was placed under vacuum to remove the volatile components to yield a viscous colorless oil. The viscous colorless oil was dissolved in approximately 3 mL of hexane and stored in a freezer. Rod shaped crystals were grown out of the hexane solutions. The crystals were isolated by decantation and dried under vacuum to yield approximately 2.93 g of the crystals. The identity of the crystals was confirmed to be (SiMcsLP-Si L-PlSiMcsL using NMR spectroscopy, produced at 42% yield. Note that higher product yields may be obtained by allowing the reaction to sit overnight.

[0211] An NMR sample was prepared in -toluene inside of a glovebox. FIG. 15A shows the ’H NMR spectrum collected at 400 MHz and 298 K, where the triplet at 4.73 ppm corresponds to the two hydrogen atoms of the P-SiH2-P moiety and the singlet at 0.35 ppm corresponds to the 36 hydrogen atoms of the Si(Mes) groups. FIG. 15B shows the31P NMR spectrum collected at 163 MHz and 298 K, where the singlet at -274.28 ppm corresponds to the two phosphorus atoms of the P-CH2-P moiety.

[0212] Although certain embodiments and examples are disclosed herein, it will be understood by those skilled in the art that the disclosed compositions, methods, and systems, extend beyond the specifically disclosed embodiments and include all novel and nonobvious combinations and subcombinations of the various compositions, methods, and systems, as well as any and all equivalents thereof. It is to be understood that the compositions, methods, and systems described herein are exemplary in nature, and that these specific embodiments or examples are not to be considered in a limiting sense, because numerous variations are possible. The specific methods and systems described herein may represent one or more of any number of processing strategies. Thus, the various acts illustrated may be performed in the sequence illustrated, in other sequences, or omitted in some cases. Moreover, various features of the disclosure are grouped together in one or more, aspects, embodiments, and configurations for the purpose of streamlining the disclosure. The features of the aspects, embodiments, and configurations of the disclosure may be combined in alternate aspects, embodiments, and configurations other than those discussed above. The compositions, methods, and systems of the disclosure are not to be interpreted as reflecting an intention that the claimed disclosure requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed aspects, embodiments, andconfigurations. Thus, the following claims are hereby incorporated into this Detailed Description, with each claim standing on its own as a separate embodiment of the disclosure, and the features recited in the various dependent claims may be combined with one another in various combinations, as appropriate, to form other embodiment of the disclosure.

Claims

CLAIMS1. A silicon precursor composition for forming a silicon containing film, wherein the silicon precursor composition comprises a silicon precursor having a structure according to a general Formula (1) or a general Formula (2):ARm[PZn(SiQ3)2-n]4-m (1)[( Q Si)2-nZnP] 3-mRm A-PZn(SiQ3) l-n-ARm[PZn(SiQ3)2-n] 3-m (2) wherein: n is an integer having a value of 0 or 1; m is an integer having a value of 0, 1, or 2; A is a silicon atom (Si) or a carbon atom (C);P is a phosphorous atom that is bonded to A by a P-A bond; Si is a silicon atom that is bonded to P by an Si-P bond;R is a substituent that is bonded to A by an A-R bond, each R is independently selected from the group consisting of a hydrogen, a hydrocarbyl group, a silyl group, an alkoxy group, and an amino group;Z is a substituent that is bonded to P by a P-Z bond, each Z is independently selected from the group consisting of a hydrocarbyl group, an alkoxy group, and an amino group; andQ is a substituent that is bonded to Si by a Si-Q bond, each Q is independently selected from the group consisting of a hydrogen, a hydrocarbyl group, an alkoxy group, and an amino group.

2. The silicon precursor composition of claim 1, wherein A is a silicon atom.

3. The silicon precursor composition of claim 1, wherein A is a carbon atom.

4. The silicon precursor composition of claim 1, wherein the integer m is 2.

5. The silicon precursor composition of claim 1, wherein the integer m is 1.

6. The silicon precursor composition of claim 1, wherein the integer m is 0.

7. The silicon precursor composition of claim 1, wherein the integer n is 0.

8. The silicon precursor composition of claim 1, wherein the silicon precursor has a structure according to the general Formula (1).

9. The silicon composition precursor of claim 1, wherein the silicon precursor has a structure according to the general Formula (2).

10. The silicon precursor composition of claim 1, wherein each of the Q substituents is independently selected from the group consisting of a hydrogen atom and a hydrocarbyl group, wherein the hydrocarbyl group is an alkyl group.

11. The silicon precursor composition of claim 1, wherein each of the R substituents is independently selected from the group consisting of a hydrogen atom; a silyl group; and a hydrocarbyl group, wherein the hydrocarbyl group is an alkyl group.

12. The silicon precursor composition of claim 1, wherein each of the Z substituents is an independently selected hydrocarbyl group, wherein the hydrocarbyl group is an alkyl group.

13. The silicon precursor composition of claim 1, wherein the silicon precursor is free of carbon.

14. The silicon precursor composition of claim 8, wherein the silicon precursor is selected from the group consisting of SiH2(P(SiH3)2)2, SiHMe(P(SiH3)2)2, SiMe2(P(SiH3)2)2, SiH2(P(SiMe3)2)2, SiHMe(P(SiMe3)2)2, SiMe2(P(SiMe3)2)2, SiH2(P(SiEt3)2)2, SiH(P(SiH3)2)3, SiMe(P(SiH3)2)3, SiH(P(SiMe3)2)3, SiMe(P(SiMe3)2)3, SiH(P(SiEt3)2)3, SI(SIH3)2(P(SIH3)2)2, SI(P(SIH3)2)4, Si(P(SiMe3)2)4, CH2(P(SiH3)2)2, CHMe(P(SiH3)2)2, CMe2(P(SiH3)2)2, CH2(P(SiMe3)2)2, CHMe(P(SiMe3)2)2, CMe2(P(SiMe3)2)2, CH2(P(SiEt3)2)2, CH(P(SIH3)2)3, CMe(P(SiH3)2)3, CH(P(SiMe3)2)3, CMe(P(SiMe3)2)3, CH(P(SiEt3)2)3, C(P(SIH3)2)4, and C(P(SiMe3)2)4.

15. The silicon precursor composition of claim 9, wherein the silicon precursor is selected from the group consisting of (H3Si)2P-SiH2-P(SiH3)-SiH2-P(SiHs)2, (Me3Si)2P-SiH2-P(SiMe3)-SiH2-P(SiMe3)2, [(H3Si)2P]2SiH-P(SiH3)-SiH[P(SiH3)2]2, [(Me3Si)2P]2SiH-P(SiMe3)-SiH[P(SiMe3)2]2, (H3Si)2P-CH2-P(SiH3)-CH2-P(SiH3)2, (Me3Si)2P-CH2-P(SiMe3)-CH2-P(SiMe3)2, [(H3Si)2P]2-CH-P(SiH3)-CH-[P(SiH3)2]2, [(Me3Si)2P]2-CH-P(SiMe3)-CH- [P(SiMe3)2]2, and combinations thereof.

16. The silicon precursor composition of claim 1, wherein the silicon precursor composition has a purity of about 95 wt. % or more of the silicon prescursor.

17. A vapor delivery vessel comprising the silicon precursor composition of claim 1.

18. A method for depositing a silicon containing film, the method comprising: providing a substrate in a reaction space; and exposing a surface of the substrate to a vapor of the silicon precursor composition of claim 1.

19. The method of claim 18, wherein the method further comprises: exposing the surface of the substrate to a co-reactant, wherein the co-reactant comprises one or more of a nitrogen plasma species, an oxygen plasma species, a carbon plasma species, a hydrogen plasma species, and a noble gas plasma species.

20. The method of claim 18, wherein the silicon containing fdm comprises a material that is selected from the group consisting of silicon nitride, silicon oxide, silicon carbide, silicon oxynitride, silicon oxycarbide, silicon carbon nitride, silicon carbon oxynitride, polysilicon, crystalline silicon, and amorphous silicon.

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