Volatile strontium and barium formamidinate precursors for depositon of metal oxide thin films

Abstract

The disclosed and claimed subject matter relates to strontium and barium precursors, their synthesis and their use in methods for depositing films containing strontium and / or barium.

Description

Application Docket No. P24-211-SEC-WO01VOLATILE STRONTIUM AND BARIUM FORMAMIDINATE PRECURSORS FOR DEPOSITON OF METAL OXIDE THIN FILMSCROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to United States Provisional Application number 63 / 723,694, filed on November 22, 2024, the entire contents of which are incorporated by reference.BACKGROUNDField

[0002] The disclosed and claimed subject matter relates to strontium and barium precursors, their synthesis and their use in methods for depositing films containing strontium and / or barium.Related Art

[0003] Thin films, and in particular thin metal-containing films, have a variety of important applications, such as in nanotechnology and the fabrication of semiconductor devices. Examples of such applications include high-refractive index optical coatings, corrosionprotection coatings, photocatalytic self-cleaning glass coatings, biocompatible coatings, dielectric capacitor layers and gate dielectric insulating films in field-effect transistors (FETs), capacitor electrodes, gate electrodes, adhesive diffusion barriers, EUV photoresist patterning materials, hard mask, transparent conducting electrodes, and integrated circuits.

[0004] Various precursors may be used to form metal-containing thin films, and a variety of deposition techniques can be employed. Such techniques include reactive sputtering, ion-assisted deposition, sol-gel deposition, chemical vapor deposition (CVD) (also known as metalorganic CVD or MOCVD), and atomic layer deposition (ALD) (also known as atomic layer epitaxy). CVD and ALD processes are increasingly used as they have the advantages of enhanced compositional control, high film uniformity, and effective control of doping.

[0005] CVD is a chemical process whereby precursors are used to form a thin film on a substrate surface. In a typical CVD process, the precursors are passed over the surface of a substrate (e.g., a wafer) in a low pressure or ambient pressure reaction reactor. The precursors react and / or decompose on the substrate surface creating a thin film of deposited material. Volatile by-products are removed by gas flow through the reaction chamber. The deposited film thickness can be difficult to control because it depends on coordination ofApplication Docket No. P24-211-SEC-WO01 many parameters such as temperature, pressure, gas flow volumes and uniformity, chemical depletion effects, and time.

[0006] ALD is also a method for the deposition of thin films. It is a self-limiting, sequential, unique film growth technique based on surface reactions that can provide precise thickness control and deposit conformal thin films of materials provided by precursors onto surfaces substrates of varying compositions. In ALD, the precursors are admitted separately during the reaction, resulting in a reaction sequence. The first precursor is passed over the substrate surface producing a monolayer on the substrate surface. Any excess unreacted precursor is pumped out of the reaction reactor. A second precursor is then passed over the substrate surface and reacts with the first precursor, forming a second monolayer of film over the first-formed monolayer of film on the substrate surface. This cycle is repeated to create a film of desired thickness.

[0007] However, the continual decrease in the size of microelectronic components, such as semi-conductor devices, presents several technical challenges and has increased the need for improved thin film technologies. In particular, microelectronic components may include features on or in a substrate, which require filling, e.g., to form a conductive pathway or to form interconnections. Filling such features, especially in smaller and smaller microelectronic components, can be challenging because the features can become increasingly thin or narrow. Consequently, a complete filling of the feature, e.g., via ALD, would require infinitely long cycle times as the thickness of the feature approaches zero. Moreover, once the thickness of the feature becomes narrower than the size of a molecule of a precursor, the feature cannot be completely filled. As a result, a hollow seam can remain in a middle portion of the feature when ALD is performed. The presence of such hollow seams within a feature is undesirable because they can lead to failure of the device. Accordingly, there exists significant interest in the development of thin film deposition methods, particularly ALD methods that can selectively grow a film on one or more substrates and achieve improved filling of a feature on or in a substrate, including depositing a metal-containing film in a manner which substantially fills a feature without any voids.

[0008] CVD and ALD are specifically attractive for fabricating conformal metal containing films on substrates, such as silicon, silicon oxide, metal nitride, metal oxide and other metal-containing layers, using these metal-containing precursors. As noted above, in theseApplication Docket No. P24-211-SEC-WO01 techniques, a vapor of a volatile metal complex is introduced into a process reactor where it contacts the surface of a silicon wafer whereupon a chemical reaction occurs that deposits a thin film of pure metal or a metal compound. C VD occurs if the precursor reacts at the wafer surface either thermally or with a reagent added simultaneously into tire process reactor and the film growth occurs in a steady state deposition. CVD can be applied in a continuous or pulsed mode to achieve the desired film thickness. In ALD, the precursor is chemisorbed onto the wafer as a self-saturating monolayer, excess unreacted precursor is purged away with an inert gas such as argon, then excess reagent is added which reacts with the monolayer of chemisorbed precursor to form metal or a metal compound. Excess reagent is then purged away with inert gas. This cycle can then be repeated multiple times to build up the metal or metal compound to a desired thickness with atomic precision since the chemisorption of precursor and reagent are self-limiting. ALD provides the deposition of ultra-thin yet continuous metal containing films with precise control of thickness, uniformity and conformality of material films grown to evenly coat deeply etched and highly convoluted structures such as interconnect vias and trenches. Thus, ALD is typically preferred for deposition of thin films on features with high aspect ratio.

[0009] Suitable metal precursors for ALD include those which are thermally stable to preclude any thermal decomposition but activation for initial chemisorption and yet are chemically reactive towards added reagent. Additionally, it is important that the metal precursors are monomeric for maximum volatility, thermally stable and of high purity to ensure clean evaporation leaving only traces of involatile residue. It is also desirable that the precursors are liquid at room temperature.

[0010] For example. Group 2 metals like strontium (Sr) and barium (Ba) are especially attractive because of its applications in the deposition of strontium and barium containing thin films, such as: strontium titanate (STO) and barium strontium titanate oxide (BST) using chemical vapor deposition (CVD) and atomic layer deposition (ALD) for advanced memory devices manufacture. Tirus, there is a strong need for strontium and barium precursors with high thermal stability and volatility. However, developing such precursors is often challenged by the formation of highly associated or polymeric structures of limited volatility because of the large ionic radius of strontium +2 and barium +2 ions (1.27 A and 1.43 A), which require bulky and thermally stable ligands to allow monomeric or dimeric complexes to be isolated.

[0011] The most common ligands to stabilize strontium and barium precursors areApplication Docket No. P24-211-SEC-WO01 substituted b-diketones and substituted cyclopentadiene. Strontium and barium 0-diketonate precursors have relatively strong metal-oxygen bonds and weak intra-ligand bonds resulting in low ALD reactivity and high levels of carbon incorporation during film growth. Although strontium and barium cyclopentadienyl precursors have relatively weak metal-carbon bonds and strong intra-ligand bonds resulting in high ALD reactivity and low levels of carbon incorporation, such precursors like strontium bis(tri-tert-butylcyclopentadienyl) and barium bis(tri-tert-butylcyclopentadienyl), as benchmark ALD precursors for deposition of STO and BST films, have high residue >10% after evaporation based thermogravimetric analysis (TGA). Strontium and barium 2,4,5-Tri-tert-butylimidazolyl precursors have low residues 3- 4%, but the ligand is expensive and thus limits such precursors for commercialization. All these reasons promote us to explore other strontium / barium precursors for STO and BST.

[0012] Metal acetamidinate complexes are generally known as precursors for the deposition of metal-containing films via ALD and CVD. For example, US Patent Number 7.557,229 generally discloses the use of volatile metal acetamidinate precursors for ALD applications. The examples disclose complexes with various transition metals, main group metals and lanthanide metals like Cu, Ag, Au, Ir, Co, Fe, Ni, Mn, Ru, Zn, Ti, V, Cr, Eu, Mg, Ca, La, Pr, Y, Sc, Nb, Ta, Rh, Al, Ga, In, Bi, wherein the acetamidinate ligands are substituted with iso-propyl, sec-butyl and / or tert-butyl groups. However, no examples with strontium and barium precursors are disclosed in this patent. Although the authors claimed strontium bis(N, N’-di-tert-butylacetamidinate) was isolated from the reaction between SrCL and lithium N, N’-di-tert-butylacetamidinate, the product was characterized as lithium N, N’- di-tert-butylacetamidinate salt not strontium bis(N, N’-di-tert-butylacetamidinate).

[0013] US Patent Number 9,029,189 describes the synthesis of strontium bis(N, N’- di-tert-butylacetamidinate) precursor through one step redox reaction between activate strontium metal in the presence of ammonia. However, the precursor is not a suitable candidate for STO and BST due to its low volatility and high residue of 30% after evaporation.

[0014] The authors in Angew. Chem. Ini. Ed., 55, 10228-10233 (2016) describes the synthesis of homoleptic dimeric bis(N,N’-diisopropylformamidinato)calcium(II) precursors using same synthetic method. This precursor shows excellent volatility and highly thermal stability for CaO and CaS thin films. Although the authors indicated the synthetic procedure may be applicable to dimeric bis(N,N’-diisopropylformamidinato)Sr or Ba precursors basedApplication Docket No. P24-211-SEC-WO01 on the reactions of Sr and Ba metal with HN(SiMe?)2 to form Sr[N(SiMe3)2]2(THF)2 or Ba[N(SiMe3)2h(THF)2 in the presence of ammonia, until now, no one isolated and characterized bis(N, N’-diisopropylformamidinato)strontium(II) and barium(II) precursors and nobody deposited SrO or BaO using these precursors.

[0015] Known attempts to synthesize strontium and barium bis(N, N’-di-tert- butylacetamidinate precursors involved metal activation, liquid ammonia, synthesis of N, N’-di-tert-butylacetamidine. However, the strontium and barium formamidinate precursors disclosed herein have not been described. Here we described a new method using MI2 instead of M to make strontium and barium formamidinate precursors without M and NH3 involvement. The precursors disclosed herein are exceptional in their volatility (<0.5% residue) and thermal stability (>375 °C) under conditions of vaporization. Surprisingly, Sr2(iPr2FAMD)4 is a liquid at evaporation temperature with a melting point of 97 °C. This makes them highly effective as precursors for STO and BST film growth and any other applications which require volatile sources of strontium and barium.SUMMARY

[0016] In one embodiment, the disclosed and claimed subject matter relates to the disclosed and claimed subject matter relates to strontium and barium precursors, their synthesis and their use in methods for depositing films containing strontium and / or barium.

[0017] In one embodiment, the disclosed and claimed subject matter relates to methods of using the strontium and barium precursors in method(s) for depositing strontium- containing and / or barium-containing films.

[0018] In another embodiment, the disclosed and claimed subject matter relates to strontium-containing and / or barium-containing films deposited using the strontium and barium precursors.

[0019] This summary section does not specify every embodiment and / or incrementally novel aspect of the disclosed and claimed subject matter. Instead, this summary only provides a preliminary discussion of different embodiments and corresponding points of novelty over conventional techniques and the known art. For additional details and / or possible perspectives of the disclosed and claimed subject matter and embodiments, the reader is directed to the Detailed Description section andApplication Docket No. P24-211-SEC-WO01 corresponding figures of the disclosure as further discussed below.

[0020] The order of discussion of the different steps described herein has been presented for clarity’s sake. In general, the steps disclosed herein can be performed in any suitable order. Additionally, although each of the different features, techniques, configurations, etc. disclosed herein may be discussed in different places of this disclosure, it is intended that each of the concepts can be executed independently of each other or in combination with each other as appropriate. Accordingly, the disclosed and claimed subject matter can be embodied and viewed in many different ways.BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The accompanying drawings, which are included to provide a further understanding of the disclosed subject matter and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosed subject matter and together with the description serve to explain the principles of the disclosed subject matter. In the drawings:

[0022] FIG. 1 illustrates the TGA of Sr2(iPr2FAMD)4;

[0023] FIG. 2 illustrates the DSC of Sr2(iPr2FAMD)4;

[0024] FIG. 3 illustrates the TGA of Ba2(iPr2FAMD)4;

[0025] FIG. 4 illustrates the DSC of Ba2(iPr2FAMD)4;

[0026] FIG 5 illustrates the vapor pressure of Sr2(iPr2FAMD)4;

[0027] FIG 6 illustrates the vapor pressure of Ba2<iPr2FAMD)4;

[0028] FIG.7 illustrates the dependence of SrO deposition rate on Sr2(iPr2FAMD)4 pulse time for ozone-based process and saturation behavior indicative of ALD process;

[0029] FIG. 8 illustrates the dependence of ALD rate vs. wafer temperature for Sr2(iPr2FAMD)4 / ozone thermal ALD, suggesting stable ALD rate at least between 200 °C and 350 °C;

[0030] FIG. 9 illustrates the dependence of SrO deposition rate on O2 pulse time for oxygen-based process and saturation behavior indicative of ALD process;

[0031] FIG. 10 illustrates the dependence of SrO deposition rate on FLO pulse time for water-based process and saturation behavior indicative of ALD process;

[0032] FIG. 11 illustrates the dependence of BaO deposition rate on Ba2(iPr2FAMD)4 pulse time for ozone-based process and saturation behavior indicative of ALD process;Application Docket No. P24-211-SEC-WO01

[0033] FIG. 12 illustrates the dependence of BaO deposition rate on O3 pulse time for ozone-based process and saturation behavior indicative of ALD process; and

[0034] FIG. 13 illustrates the dependence of BaO deposition rate on O2 pulse time for oxygen-based process and saturation behavior indicative of ALD process.DEFINITIONS

[0035] Unless otherwise stated, the following terms used in the specification and claims shall have the following meanings for this application.

[0036] For purposes of this invention and the claims hereto, the numbering scheme for the Periodic Table Groups is according to the IUPAC Periodic Table of Elements.

[0037] The term “and / or” as used in a phrase such as “A and / or B” herein is intended to include “A and B,” “A or B,” “A” and “B.”

[0038] The terms “substituent,” “radical,” “group” and “moiety” may be used interchangeably.

[0039] As used herein, the terms “metal-containing complex” (or more simply, “complex”) and “precursor” are used interchangeably and refer to metal-containing molecule or compound which can be used to prepare a metal-containing film by a vapor deposition process such as, for example, ALD or CVD. The metal-containing complex may be deposited on, adsorbed to, decomposed on, delivered to, and / or passed over a substrate or surface thereof, as to form a metal-containing film.

[0040] As used herein, the term “metal-containing film” includes not only an elemental metal film as more fully defined below, but also a film which includes a metal along with one or more elements, for example in form of a metal oxide film, metal nitride film, metal silicide film, a metal carbide film and the like. As used herein, the terms “elemental metal film” and “pure metal film” are used interchangeably and refer to a film which consists of, or consists essentially of, pure metal. For example, the elemental metal film may include 100% pure metal, or the elemental metal film may include at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, at least about 99%, at least about 99.9%, or at least about 99.99% pure metal along with one or more impurities. Unless context dictates otherwise, the term “metal film” shall be interpreted to mean an elemental metal film.Application Docket No. P24-211-SEC-WO01

[0041] As used herein, the term “vapor deposition process” is used to refer to any type of vapor deposition technique, including but not limited to, CVD and ALD. In various embodiments, CVD may take the form of conventional (i.e., continuous flow) CVD, liquid injection CVD, or photo-assisted CVD. CVD may also take the form of a pulsed technique, i.e., pulsed CVD. ALD is used to form a metal-containing film by vaporizing and / or passing at least one metal complex disclosed herein over a substrate surface. For conventional ALD processes see, for example, George S. M., et al. J. Phys. Chem., 100, 13121-13131 (1996). In other embodiments, ALD may take the form of conventional (i.e., pulsed injection) ALD, liquid injection ALD, photo-assisted ALD, plasma-assisted ALD, or plasma-enhanced ALD. The term “vapor deposition process” further includes various vapor deposition techniques described in Chemical Vapour Deposition: Precursors, Processes, and Applications; Jones, A. C.; Hitchman, M. L., Eds. The Royal Society of Chemistry: Cambridge, Chapter 1, pp. 1-36 (2009).

[0042] Throughout the description, the term “ALD or ALD-like” refers to a process including, but not limited to, the following processes: a) each reactant including the strontium and / or barium precursor and reactive gas is introduced sequentially into a reactor such as a single wafer ALD reactor, semi-batch ALD reactor, or batch furnace ALD reactor; b) each reactant is exposed to a substrate by moving or rotating the substrate to different sections of the reactor and each section is separated by inert gas curtain, i.e., spatial ALD reactor or roll to roll ALD reactor. The ALD-like is defined herein as a cyclic CVD process that provides a high conformal metal-containing film on a substrate as shown by having at least one of the following: percentage of non-uniformity of about 5% or less as measured by ellipsometry, a deposition rate of 1 A or greater per cycle or a combination thereof.

[0043] As used herein, the term “feature” refers to an opening in a substrate which may be defined by one or more sidewalls, a bottom surface, and upper corners. In various aspects, the feature may be a via, a trench, contact, dual damascene, etc.

[0044] As used herein, the terms “selective growth,” “selectively grown” and “selectively grows” may be used synonymously and refer to film growth on at least a portion of a first substrate and no substantial film growth on a remaining portion of the first substrate as well as more film growth on at least a portion of the first substrate compared to film growth on a remaining portion of the first substrate. For example, selective growthApplication Docket No. P24-211-SEC-WO01 may include growth of a film on a lower portion of a feature while less film growth or no film growth may occur in an upper portion of that feature or outside that feature. With respect to more than one substrate, the terms “selective growth” “selectively grown” and “selectively grows” also encompass film growth on a first substrate and substantially no film growth on a second substrate (or a third substrate, or fourth substrate or a fifth substrate, etc.) as well as more film growth on the first substrate than on the second substrate (or a third substrate, or fourth substrate or a fifth substrate, etc.).

[0045] As used herein, the terms "about" and “approximately” are each intended to correspond to ± 5% of the stated value.

[0046] “Halo” or “halide” refers to a halogen (e.g., F, Cl, Br and I).

[0047] ‘Strontium-containing film” refers to strontium oxide or a film including strontium which can be employed as material in semi-conductor or display device fabrication process.

[0048] “Barium-containing film” refers to barium oxide or a film including barium oxide which can be employed as material in semi-conductor or display device fabrication process.

[0049] The section headings used herein are for organizational purposes and are not to be construed as limiting the subject matter described. All documents, or portions of documents, cited in this application, including, but not limited to. patents, patent applications, articles, books, and treatises, are hereby expressly incorporated herein by reference in their entirety for any purpose. In the event that any of the incorporated literature and similar materials defines a term in a manner that contradicts the definition of that term in this application, this application controls.DETAILED DESCRIPTION

[0050] It is to be understood that both the foregoing general description and the following detailed description are illustrative and explanatory, and are not restrictive of the subject matter, as claimed. The objects, features, advantages and ideas of the disclosed subject matter will be apparent to those skilled in the art from the description provided in the specification, and the disclosed subject matter will be readily practicable by those skilled in the art on the basis of the description appearing herein. The description of anyApplication Docket No. P24-211-SEC-WO01“preferred embodiments” and / or the examples which show preferred modes for practicing the disclosed subject matter are included for the purpose of explanation and are not intended to limit the scope of the claims.

[0051] It will also be apparent to those skilled in the art that various modifications may be made in how the disclosed subject matter is practiced based on described aspects in the specification without departing from the spirit and scope of the disclosed subject matter disclosed herein.

[0052] In the below-described embodiments directed to methods or processes, it is understood that in some embodiments the steps of the methods may be performed in a variety of orders, may be performed sequentially or concurrently (e.g., during at least a portion of another step), and any combination thereof. The respective step of supplying the precursors and the nitrogen-containing source gases may be performed by varying the duration of the time for supplying them to change the stoichiometric composition of the resulting dielectric film.Strontium and Barium Precursors

[0053] In one embodiment, the disclosed and claimed subject matter relates to the disclosed and claimed subject matter relates to strontium and barium precursors of the Formula (I):where (i) M = Sr or Ba, (ii) R= an isopropyl group (“iPr”) or a tert-butyl group (“tBu”) and (iii) n = 1-4.

[0054] In one embodiment, the precursor has Formula1. In one aspect of this embodiment, M = Sr. In another aspect of this embodiment, M= Ba.

[0055] In one embodiment, the precursor has Formula (1-2):Application Docket No. P24-211-SEC-WO01one aspect of this embodiment, M= Sr. In another aspect of this embodiment, M= Ba.

[0056] In one embodiment, the precursor has Formula3. In one aspect of this embodiment, M = Sr. In another aspect of this embodiment, M= Ba.

[0057] In one embodiment, the precursor has Formula4. In one aspect of this embodiment, M = Sr. In another aspect of this embodiment, M= Ba.

[0058] In one embodiment, the compound of Formula (I) is Si‘2(iPr2FAMD)4.

[0059] In one embodiment, the compound of Formula (I) is Ba2(iPr2FAMD)4.

[0060] In one embodiment, the precursor has Formula1 . In one aspect of this embodiment, M = Sr. In another aspect of this embodiment, M= Ba.

[0061] In one embodiment, the precursor has Formula (1-6):one aspect of this embodiment, M =Sr. In another aspect of this embodiment, M= Ba.Application Docket No. P24-211-SEC-WO01

[0062] In one embodiment, the precursor has Formula3. In one aspect of this embodiment, M = Sr. In another aspect of this embodiment, M= Ba.

[0063] In one embodiment, the precursor has Formula4. In one aspect of this embodiment, M = Sr. In another aspect of this embodiment, M= Ba.

[0064] In one embodiment, the compound of Formula (I) is Sr2(tBu2FAMD)4.

[0065] In one embodiment, the compound of Formula (I) is Ba2(tBu2FAMD)4.Compositions of Strontium and Barium Precursors

[0066] In one aspect of this embodiment, the disclosed and claimed subject matter relates to compositions that include, consist essentially of or consist of (a) one or more of the strontium precursors or barium precursors of Formula (I) described above and (b) one or more solvents.

[0067] In one embodiment, the compound of Formula (I) is Sr2(iPr2FAMD)4.

[0068] In one embodiment, the compound of Formula (I) is Ba2(iPr2FAMD)4.

[0069] In one embodiment, the compound of Formula (I) is Si'2(tBu2FAMD)4.

[0070] In one embodiment, the compound of Formula (I) is Ba2(tBu2FAMD)4.

[0071] The compositions of the disclosed and claimed subject matter further include (b) one or more solvent(s). Suitable solvents include hydrocarbon solvents which are particularly desirable due to their ability to be dried to sub-ppm levels of water. Exemplary hydrocarbon solvents that can be used in the compositions include, but are not limited to, toluene, mesitylene, cumene (iso-propylbenzene), p-cymene (4-iso-propyl toluene), 1,3-di- iso-propylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, decahydronaphthalene (decalin) and combinations thereof. In certain embodiments, the hydrocarbon solvent is a high boiling point solvent or has a boiling point of 100 °C or greater.Methods of Depositions

[0072] In another embodiment, the above-described strontium and barium precursors and / or compositions thereof are used in method(s) for depositing strontium-Application Docket No. P24-211-SEC-WO01 containing and / or barium-containing films on a substrate.

[0073] In one embodiment, the method for depositing the disclosed and claimed strontium precursors and / or barium precursors on a substrate includes the steps of:(i) introducing into a deposition chamber one or more of the strontium precursors or barium precursors as a vapor with an inert carrier gas (e.g., argon);(ii) purging with an inert gas to remove any unsorbed precursor (e.g., using an Ar purge time of about 30 seconds to about 45 seconds);(iii) introducing one or more oxygen source or nitrogen source into the deposition chamber (e.g., using a pulse time of about 0.5 seconds of H2O or about 1 second of O3 or O2); and(iv) purging with an inert gas to remove any unreacted oxygen source or nitrogen source (e.g., using an Ar purge time of about 30 seconds to about 45 seconds).

[0074] hi one exemplary embodiment, a strontium precursor was embodiment is heated to about 175 °C, and its vapor was provided by supplying 30 seem Ar bubble flow to the reaction chamber at about 200°C to about 450 °C with the pressure of about 2 Torr. Oxygen sources like O3, 02, H2O were pulsed to the reaction chamber. The cycle was repeated 100 times.

[0075] In another exemplary embodiment, a barium precursor was embodiment is heated to about 175 °C, and its vapor was provided by supplying 30 seem Ar bubble flow to the reaction chamber at about 200 °C to about 350 °C with the pressure of about 2 Torr. Oxygen sources like O3, O2, H2O were pulsed to the reaction chamber. The cycle was repeated 100 times.Step (i) Delivery of Strontium Precursor and / or Barium Precursor

[0076] As noted above, step (i) of the disclosed and claimed methods includes introducing one or more of the strontium precursors or barium precursors as a vapor with an inert carrier gas carrier.

[0077] In one embodiment, the strontium precursor or barium precursor is heated to a temperature of about 100 °C to about 200 °C. In one embodiment, the strontium precursor or barium precursor is heated to a temperature of about 150 °C to about 200 °C. In one embodiment, the strontium precursor or barium precursor is heated to a temperature of about 100 °C. In one embodiment, the strontium precursor or barium precursor is heated to a temperature of about 125 °C. In one embodiment, the strontium precursor or barium precursorApplication Docket No. P24-211-SEC-WO01 is heated to a temperature of about 150 °C. In one embodiment, the strontium precursor or barium precursor is heated to a temperature of about 175 °C. In one embodiment, the strontium precursor or barium precursor is heated to a temperature of about 200 °C.

[0078] In one embodiment, the strontium precursor or barium precursor vapor pulse time is from about 0.1 seconds to about 3 seconds. In another embodiment, the strontium precursor or barium precursor vapor pulse time is from about 0.3 seconds to about 3 seconds. In another embodiment, the strontium precursor or barium precursor vapor pulse time is about 0.1 second. In another embodiment, the strontium precursor or barium precursor vapor pulse time is about 0.25 second. In another embodiment, the strontium precursor or barium precursor vapor pulse time is about 0.5 second. In another embodiment, the strontium precursor or barium precursor vapor pulse time is about 1 second. In another embodiment, the strontium precursor or barium precursor vapor pulse time is about 1.5 seconds. In another embodiment, the strontium precursor or barium precursor vapor pulse time is about 2 seconds. In yet another embodiment, the strontium precursor or barium precursor vapor pulse time is longer than 2 seconds depending on the volume / design of the reactor chamber.

[0079] In one embodiment, the strontium precursor or barium precursor vapor is separated from other precursor materials prior to and / or during the introduction to the reactor. This process avoids any premature reaction of the metal precursor with any other materials.

[0080] In another embodiment, the strontium precursor or barium precursor vapor is alternatively exposed to the substrate with other reactants (e.g., other precursors or reagents). This process enables film growth to proceed by self-limiting control of the surface reactions, the pulse length of each precursor or reagent and the deposition temperature. It should be noted, however, that film growth ceases once the surface of the substrate is saturated with strontium precursor or barium precursor vapor.

[0081] In another embodiment, a flow of argon and / or other inert gas is employed as a carrier gas to help deliver the strontium precursor or barium precursor vapor to the reaction reactor during the precursor pulsing.Step (iii) Oxygen Source or Nitrogen Source

[0082] As noted above, step (iii) of the disclosed and claimed method includes introducing one or more oxygen source or nitrogen source into the deposition chamber. The oxygen or nitrogen source provides oxygen or nitrogen to form metal oxide and metalApplication Docket No. P24-211-SEC-WO01 nitride films, respectively.Oxygen Source

[0083] In one embodiment, the oxygen source includes one or more of water plasma, ozone, oxygen, oxygen plasma, oxygen / helium plasma, oxygen / argon plasma, nitrogen oxides plasma, carbon dioxide plasma, carbon monoxide plasma, an alcohol, such as for example ethanol, isopropanol, tert-butanol and mixtures thereof for formation of strontium and / or barium oxide materials.

[0084] In one embodiment, the one or more oxygen source includes one or more of oxygen (O2), ozone (O3), nitric oxide (NO), water (H2O) vapor, hydrogen peroxide (H2O2), oxygen plasma (O*), NxOy(where x = 1 or 2 and y = 1, 2, 3 or 4) and combinations thereof. In one aspect of this embodiment, the one or more oxygen source includes oxygen. In one aspect of this embodiment, the one or more oxygen source includes ozone. In one aspect of this embodiment, the one or more oxygen source includes nitric oxide. In one aspect of this embodiment, the one or more oxygen source includes water vapor. In one aspect of this embodiment, the one or more oxygen source includes hydrogen peroxide. In one aspect of this embodiment, the one or more oxygen source includes oxygen and ozone, hi one aspect of this embodiment, the one or more oxygen source includes oxygen plasma. In one aspect of this embodiment, the one or more oxygen source includes NxOywhere x = 1 or 2 and y = 1, 2, 3 or 4. In one embodiment, the one or more oxidant is a vapor.

[0085] In one preferred embodiment, for example, the one or more oxygen source includes, consists essentially of or consists of O2. In one aspect of this embodiment, the one or more oxygen source includes O2. In one aspect of this embodiment, the one or more oxygen source consists essentially of O2. In one aspect of this embodiment, the one or more oxygen source consists of O2.

[0086] In one preferred embodiment, for example, the one or more oxygen source includes, consists essentially of or consists of O3. In one aspect of this embodiment, the one or more oxygen source includes O3. In one aspect of this embodiment, the one or more oxygen source consists essentially of O3. In one aspect of this embodiment, the one or more oxygen source consists of O3.

[0087] In one preferred embodiment, for example, the one or more oxygen source includes, consists essentially of or consists of water vapor. In one aspect of thisApplication Docket No. P24-211-SEC-WO01 embodiment, the one or more oxygen source includes water vapor. In one aspect of this embodiment, the one or more oxygen source consists essentially of water vapor. In one aspect of this embodiment, the one or more oxygen source consists of water vapor.Nitrogen Source

[0088] In one embodiment, the nitrogen source includes one or more of ammonia, hydrazine, an alkylhydrazine, an alkyl amine and combinations thereof. In one aspect of this embodiment, the nitrogen source includes ammonia. In one aspect of this embodiment, the nitrogen source includes hydrazine. In one aspect of this embodiment, the nitrogen source includes an alkylhydrazine. In one aspect of this embodiment, the nitrogen source includes an alkyl amine.

[0089] In one preferred embodiment, for example, the one or more nitrogen source includes, consists essentially of or consists of ammonia. In one aspect of this embodiment, the one or more nitrogen source includes ammonia. In one aspect of this embodiment, the one or more nitrogen source consists essentially of ammonia. In one aspect of this embodiment, the one or more nitrogen source consists of ammonia.

[0090] In one preferred embodiment, for example, the one or more nitrogen source includes, consists essentially of or consists of hydrazine. In one aspect of this embodiment, the one or more nitrogen source includes hydrazine. In one aspect of this embodiment, the one or more nitrogen source consists essentially of hydrazine. In one aspect of this embodiment, the one or more nitrogen source consists of hydrazine.Oxygen or Nitrogen Source Pulse Time

[0091] In one embodiment, the one or more oxygen source or nitrogen source pulse time varies from about 0.5 seconds to about 5 seconds. In one embodiment, for example, the one or more oxygen source or nitrogen source pulse time is about 2.5 seconds. In one embodiment, for example, the one or more oxygen source or nitrogen source pulse time is about 5 seconds. Yet, in another embodiment, the one or more oxygen source or nitrogen source pulse time is longer than 5 seconds depending on the volume / design of the reactor chamber.Steps (ii) and (iv) Purging

[0092] As noted above, steps (ii) and (iv) of the disclosed and claimed methods include purging the reactor vessel with inert gas. Purging with an inert gas removes unabsorbed excess materials and by products from the process reactor. In one embodiment,Application Docket No. P24-211-SEC-WO01 the purge gas includes argon. In another embodiment, the purge gas includes nitrogen.

[0093] In one embodiment, the purge time varies from about 1 seconds to about 90 seconds. In one embodiment, the purge time varies from about 15 seconds to about 90 seconds. In one embodiment, the purge time varies from about 15 seconds to about 60 seconds. In one embodiment, the purge time varies from about 30 seconds to about 45 seconds. In another embodiment, the purge time is about 30 seconds. In another embodiment, the purge time is about 45 seconds. In another embodiment, the purge time is about 60 seconds. In another embodiment, the purge time is about 90 seconds.

[0094] In one embodiment, the purge gas includes argon. In another embodiment, the purge gas includes nitrogen.Operating Conditions

[0095] As noted above, the disclosed and claimed strontium-containing and / or barium-containing film deposition process can be effectively conducted under very favorable ALD or ALD-like conditions.

[0096] In one embodiment the substrate (e.g., a silicon oxide, aluminum oxide (AI2O3), titanium nitride (TiN), molybdenum nitride (MoN), tungsten nitride (WN), silicon oxide (SiCh), zirconium oxide (ZrCh). amorphous carbon, silicon-containing underlayer) is heated on a heater stage in a reaction reactor that is exposed to the strontium precursor or barium precursor initially to allow the complex to chemically adsorb onto the surface of the substrate. In one embodiment, the substrate temperature is from about 25 °C to about 600 °C. In a further aspect of this embodiment, the substrate temperature is from about 25 °C to about 500 °C. In a further aspect of this embodiment, the substrate temperature is from about 25 °C to about 400 °C. A preferred substrate temperature is from 200 °C to about 450 °C. Another preferred substrate temperature is from 200 °C to about 350 °C.

[0097] In another embodiment, the reactor pressure for depositions according to the disclosed and claimed process is < about 100 torr. In another embodiment, the reactor pressure for depositions according to the disclosed and claimed process is < about 75 torr. In another embodiment, the reactor pressure for depositions according to the disclosed and claimed process is < about 50 torr. In another embodiment, the reactor pressure for depositions according to the disclosed and claimed process is < about 40 torr. In another embodiment, the reactor pressure for depositions according to the disclosed and claimedApplication Docket No. P24-211-SEC-WO01 process is < about 30 torr. In a further aspect of this embodiment, the reactor pressure is < about 20 torr. In a further aspect of this embodiment, the reactor pressure is < about 10 torr. In a further aspect of this embodiment, the reactor pressure is < about 5 torr. In a further aspect of this embodiment, the reactor pressure is < about 2 torr.Cycles and Order of Steps

[0098] In the above-described embodiments, as well as the other embodiments described herein, the described steps (e.g., (a) through (e)) define one cycle of the method. It is to be understood that a cycle can be repeated until the desired thickness of a film is obtained.

[0099] In the embodiments described herein, it is understood that the steps of the methods may be performed in a variety of orders, may be performed sequentially or concurrently (e.g., during at least a portion of another step), and any combination thereof. In addition, the respective steps of supplying the reactants and or the subsequent purges thereof may be performed by varying the duration of the time for supplying them to change film composition.Films

[0100] In another embodiment, the disclosed and claimed subject matter relates to strontium-containing and / or barium-containing films deposited using the strontium and barium precursors.

[0101] In one embodiment, the films formed by the methods described herein have trenches, vias or other topographical features with an aspect ratio of about 1 to about 60. In a further aspect of this embodiment, the aspect ratio is about 1 to about 50. In a further aspect of this embodiment, the aspect ratio is about 1 to about 40. In a further aspect of this embodiment, the aspect ratio is about 1 to about 30. In a further aspect of this embodiment, the aspect ratio is about 1 to about 20. In a further aspect of this embodiment, the aspect ratio is about 1 to about 10. In a further aspect of this embodiment, the aspect ratio is greater than about 1. In a further aspect of this embodiment, the aspect ratio is greater than about 2. In a further aspect of this embodiment, the aspect ratio is greater than about 5. In a further aspect of this embodiment, the aspect ratio is greater than about 10. In a further aspect of this embodiment, the aspect ratio is greater than about 15. In a further aspect of this embodiment, the aspect ratio is greater than about 20. In a further aspect of this embodiment, the aspect ratio is greater than about 30. In a further aspect of this embodiment, the aspect ratio is greater than about 40. In a further aspect of this embodiment, the aspect ratio is greater than about 50.Application Docket No. P24-211-SEC-WO01

[0102] The steps of the described and claimed processes may be repeated to provide a desired thickness of the strontium-containing and / or barium-containing films. The thickness of the films can range from about 10 A to about 5000 A, or about 10 A to about 1000 A, or about 10 A to about 500 A, or about 10 A to about 300 A or about 10 A to about 200 A, or about 50 A to about 1000 A, or about 50 A to about 500 A, or about 50 A to about 300 A or about 50 A to about 200 A. In one embodiment, the films formed by the methods described herein have a thickness of about 10 A to about 5000 A. In another aspect of this embodiment, the films formed by the methods described herein have a thickness of about 10 A to 1000 A. In another aspect of this embodiment, the films formed by the methods described herein have a thickness of about 10 A to 500 A. In another aspect of this embodiment, the films formed by the methods described herein have a thickness of about, 10 A to 300 A. In another aspect of this embodiment, the films formed by the methods described herein have a thickness of about, 10 A to 200 A. In another aspect of this embodiment, the films formed by the methods described herein have a thickness of about, 50 A to 1000 A. In another aspect of this embodiment, the films formed by the methods described herein have a thickness of about, 50 A to 500 A. In another aspect of this embodiment, the films formed by the methods described herein have a thickness of about, 50 A to 300 A. In another aspect of this embodiment, the films formed by the methods described herein have a thickness of about, 50 A to 200 A.

[0103] In some embodiments, the steps (i) to (iv) may be repeated to provide a desired thickness of strontium-containing and / or barium-containing films which can range from about 50 A to about 1000 A, about 50 A to about 500 A, about 50 A to about 300 A or about 50 A to about 200 A.Examples

[0104] Reference will now be made to more specific embodiments of the present disclosure and experimental results that provide support for such embodiments. The examples given below more fully illustrate the disclosed and claimed subject matter and should not be construed as limiting the disclosed subject matter in any way.

[0105] It will be apparent to those skilled in the art that various modifications and variations can be made in the disclosed subject matter and specific examples provided herein without departing from the spirit or scope of the disclosed subject matter. Thus, it is intended that the disclosed subject matter, including the descriptions provided by the followingApplication Docket No. P24-211-SEC-WO01 examples, covers the modifications and variations of the disclosed subject matter that come within the scope of any claims and their equivalents.Synthesis Examples

[0106] Example 1: Synthesis of Sr2(iPr2FAMD)4

[0107] In a 250 mL Schlenk flask, 7.48 g of N, N’ -diisopropylformamidine was dissolved in 100 mL THF followed by the slow addition of 2.33g KH while keeping the reaction temperature below 30 °C. After the KH addition, a clear solution was obtained. 10 g anhydrous Srh was slowly added to the flask while keeping the reaction temperature below 30 °C. After the addition, the mixture was allowed to cool to room temperature and was stirred at room temperature overnight. After filtration, all volatiles were removed under reduced pressure to give a white residue that was then extracted in 100 mL pentane to give a suspension. After filtration, all volatiles were removed under vacuum to give white solid as crude product. The crude product was sublimed under reduced pressure (0.1 Torr) at 150 °C to give 5.0 g off-white solid (50% yield).

[0108] Analysis: ’ H NMR (500 MHz, C6D6) 5 8.23 (d, 4H), 3.26 (d, 8H), 1.21 (d, 48H). TGA in FIG. 1: T50% = 245 °C, evaporation residue 0.41 %. DSC FIG. 2: Tmeitingpoint — 96.6 C, Tdecomposition onset — 375 °C. Vapor Pressure FIG. 5: TO.VTOIT = 180 °C.

[0109] Example 2: Synthesis of Ba2(iPr2FAMD)4

[0110] In a 250 mL Schlenk flask, 3.28 g of N, N’ -diisopropylformamidine was dissolved in 100 mL THF followed by the slow addition of 1.03 g KH while keeping the reaction temperature below 30 °C. After the KH addition, a clear solution was obtained. 5.0 g Bah was slowly added to the flask while keeping the reaction temperature below 30 °C. After addition, the mixture was allowed to cool to room temperature and was stirred at room temperature overnight. After filtration, all volatiles were removed under reduced pressure to give a white residue that was then extracted in 100 mL pentane to give a suspension. After filtration, all volatiles were removed under vacuum to give white solid as crude product. The crude product was sublimed under reduced pressure (0. ITorr) at 200 °C to give 2.5 g off-white solid (50% yield).

[0111] Analysis:1H NMR (500 MHz, CeDe) 5 8.18 (broad s, 4H), 3.29 (septets, 8H), 1.24 (d, J=6.47Hz, 48H). TGA FIG. 3: T5o% = 300 °C, evaporation residue 0.46%. DSC FIG. 4. Tmeiting point — 207°C, Tdecomposition onset — 375 °C. Vapor Pressure FIG. 6: TO.ITOH = 180 °C.Application Docket No. P24-211-SEC-WO01

[0112] Example 3: Attempt Synthesis of Ba2(Et2FAMD)4

[0113] A mixture of Bah and Na(Et2FAMD) in THF was stirred overnight at room temperature. After filtration, all volatiles were removed under vacuum to give a white solid. The solid was not soluble in pentane or hexane. The possible product was a polymer or no reaction between Bah and Na(E FAMD) occurred.

[0114] Example 4: Synthesis of Ba2(tBii2FAMD)4

[0115] In a 250 mL Schlenk flask, 60 mL of THF were added to a solid mixture of 1.54 g of KH, 7.5 g of Bah and 5.9 g of N,N-di-tertbutylcarbodiimide. The mixture was stirred for 2 days. After filtration, all volatiles were removed under reduced pressure to give a white residue that was then extracted in 200 mL pentane to give a suspension. After filtration, all volatiles were removed under vacuum to give 3.9 g of white solid as crude product. The crude product was purified by re-crystallization from pentane to give 1.0 g off-white solid Ba2(tBu2FAMD)4. TGA analysis showed clean evaporation with vapor pressure comparable to Ba2(iPr2FAMD)4.

[0116] Analysis: ‘ H NMR (500 MHz, C6D6) 8 8.47 and 8.80 (broad s, 4H), 1.26 and 1.36 (s, 72H). TGA: Tso% = 277 °C, evaporation residue 1.26%. DSC: Tmciting point = 244°C, Tdecomposiuon onset = 350 °C. Vapor Pressure: To.DTon- = 180 °C.Deposition ExamplesGeneral Procedures for Strontium Film Deposition

[0117] The Sr precursor was heated to 175 °C, and its vapor was provided by supplying 30 seem Ar bubble flow to the reaction chamber at 200-450 °C with the pressure of 2 Torr. Oxygen sources like O3, O2, H2O were pulsed to the reaction chamber and the resulting films were analyzed by XPS and SEM. The pulse cycle used was: (i) precursor pulse time was 2 seconds; (ii) 30 second Ar purge; (iii) oxygen source pulse time was 0.5 seconds for H2O (when used) and 1 second of O3 (when used) or 1 second O2 (when used); and (iv) 42 second Ar purge. The cycle was repeated 100 times.

[0118] Example 5: Strontium Containing Film Deposition by Sr2(iPr2FAMD)4 and O3

[0119] This example describes the deposition of a Sr-containing film using Sr2(iPr2FAMD)4 precursor and ozone O3. Film depositions were tested at chamber temperatures of 200 °C, 300 °C, 350 °C and 400 °C. The deposition rate ranged from 1 A to 1.5 A per cycle at 200°C to 400 °C wafer temperature. FIG. 7 shows the dependence of SrO thickness on Sr2(iPr2FAMD)4 pulse time and saturation behavior with increasing precursor pulse time.Application Docket No. P24-211-SEC-WO01Saturation behavior is indicative of ALD process. FIG. 8 shows the dependence of ALD rate vs. wafer temperature, suggesting stable ALD rate at least between 200 and 350C. This example highlights the viability of the precursor over a large ALD window which is especially advantageous when forming a combined STO film where the ALD windows are needed to overlap. Particularly advantageous for this type of precursor is the reactivity observed.

[0120] Example 6: Strontium Containing Film Deposition by Sr2(iPr2FAMD)4 and O2

[0121] This example describes the deposition of a Sr-containing film using Sr2(iPr2FAMD)4 precursor with O2. Film depositions were tested at chamber temperatures of 200 °C, 300 °C and 350 °C. FIG. 9 shows the dependence of SrO deposition rate on O2 pulse time. Saturation behavior was observed with ALD rate ~ 0.6 A / cycle under saturated conditions.

[0122] Example 7: Strontium Containing Film Deposition by Sr2(iPr2FAMD)4 and H2O

[0123] This example describes the deposition of a Sr-containing film using Sr2(iPr2FAMD)4 precursor with H2O. FIG. 10 shows the dependence of SrO deposition rate on H2O pulse time. Saturation behavior was observed with ALD rate ~ 0.8 A / cycle under saturated conditions. Film depositions were tested at chamber temperature of 200 °C, 250 °C, 300 °C and 350 °C.General Procedures for Barium Film Deposition

[0124] The Ba precursor was heated to 175 °C, and its vapor was provided by supplying 30 seem Ar bubble flow to the reaction chamber at 200-350 °C with the pressure of 2 Torr. The oxygen sources (O3, O2) or nitrogen source s (NH3) were pulsed to the reaction chamber and the resulting films were analyzed by XPS and SEM. The pulse cycle used was: (i) precursor pulse time was 45 seconds (evac-purge method); (ii) 42 second Ar purge; (iii) oxygen source or nitrogen source pulse time was 1 second; and (iv) 42 second Ar purge. The cycle was repeated 100 times.

[0125] Example 8: Barium Containing Film Deposition by Ba2(iPr2FAMD)4 and O3

[0126] This example describes the deposition of a Ba-containing film using Ba2(i- PnFAMD)4 precursor with O3. Film depositions were tested at chamber temperature of 200 °C, 250 °C, 300 °C and 350 °C. FIG. 11 shows the dependence of BaO thickness on Ba2(iPr2FAMD)4 pulse time. Saturation behavior is indicative of ALD process. LongApplication Docket No. P24-211-SEC-WO01 saturation time is likely due to low precursor flux at 175C ampoule temperature. Saturation time can be reduced with higher ampoule temperature. FIG. 12 shows the dependence of BaOx thickness on O3 pulse time. Very good saturation behavior is observed with short pulse of O3, 0.5 sec. This precursor showed better reactivity and acceptable volatility compared to Ba-Cp and Ba-imidazolate precursors for delivery to the tool towards O3.

[0127] Example 9: Barium Containing Film Deposition by Ba2(iPr2FAMD)4 and O2

[0128] This example describes the deposition of a Ba-containing film using Ba2(iPr2FAMD)4 precursor with O2. Film depositions were tested at chamber temperature of 200 °C, 300 °C and 350 °C. FIG. 13 shows the dependence of BaOx thickness on O2 pulse time. Very good saturation behavior is observed with short pulse of O2. 0.5 sec.

[0129] Example 10: Barium Containing Film Deposition by Ba2(iPr2FAMD)4 and NH3

[0130] This example describes the deposition of a Ba-containing film using Ba2(iPr2FAMD)4 precursor with NH3 with plasma. NH3saturation pulse time was 5 seconds. Ar purge time was 5 seconds. Ar bubble flow was 300 seem. Film deposition was tested at a chamber temperature of 450 °C. The deposition rate with plasma NH (57 A / cycle) was higher than that with thermal NH3 (29 A / cycle).

[0131] Although the invention has been described and illustrated with a certain degree of particularity, it is understood that the disclosure has been made only by way of example, and that numerous changes in the conditions and order of steps can be resorted to by those skilled in the art without departing from the spirit and scope of the invention.

Claims

Application Docket No. P24-211-SEC-WOOlClaimsWhat is claimed is1. A precursor comprising a compound of Formula (I):wherein (i) M = Sr or Ba, (ii) R= an isopropyl group (“iPr”) or a tert-butyl group (“tBu”) and (iii) n = 1-4.

2. The precursor of claim 1, wherein M = Sr, R= iPr and n = 1.

3. The precursor of claim 1, wherein M = Sr, R= iPr and n = 2.

4. The precursor of claim 1 , wherein M = Sr, R= iPr and n = 3.

5. The precursor of claim 1, wherein M = Sr, R= iPr and n = 4.

6. The precursor of claim 1, wherein M = Sr, R= tBu and n = 1.

7. The precursor of claim 1, wherein M = Sr, R= tBu and n = 2.

8. The precursor of claim 1, wherein M = Sr, R= tBu and n = 3.

9. The precursor of claim 1, wherein M = Sr, R= tBu and n = 4.

10. The precursor of claim 1, wherein M = Ba, R= iPr and n = 1.

11. The precursor of claim 1, wherein M = Ba, R= iPr and n = 2.

12. The precursor of claim 1, wherein M = Ba, R= iPr and n = 3.

13. The precursor of claim 1, wherein M = Ba, R= iPr and n = 4.

14. The precursor of claim 1, wherein M = Ba, R= tBu and n = 1.

15. The precursor of claim 1, wherein M = Ba, R= tBu and n = 2.

16. The precursor of claim 1, wherein M = Ba, R= tBu and n = 3.

17. The precursor of claim 1, wherein M = Ba, R= tBu and n = 4.

18. The precursor of claim 1, wherein the compound of Formula (I) is Sr2(iPr2FAMD)4.

19. The precursor of claim 1, wherein the compound of Formula (I) is Ba2(iPr2FAMD)4.

20. The precursor of claim 1, wherein the compound of Formula (I) is Sr2(tBri2FAMD)4.

21. The precursor of claim 1, wherein the compound of Formula (I) is Ba2(tBii2FAMD)4.

22. A composition comprising (a) the precursor of any of claims 1-21 and (b) one orApplication Docket No. P24-211-SEC-WO01 more solvents.

23. The composition of claim 22, wherein the one or more solvents is selected from the group of toluene, mesitylene, cumene (iso-propylbenzene), p-cymene (4-iso-propyl toluene), 1,3-di-iso-propylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n- butylcyclohexane, decahydronaphthalene (decalin) and combinations thereof.

24. A method(s) for depositing a strontium-containing and / or barium-containing films on a substrate comprising the steps of:(i) introducing into a deposition chamber one or more of the precursors of any of claims 1-21 as a vapor with an inert carrier gas;(ii) purging with an inert gas to remove any unsorbed precursor;(iii) introducing one or more oxygen source or nitrogen source into the deposition chamber and(iv) purging with an inert gas to remove any unreacted oxygen source or nitrogen source.

25. The method of claim 24, wherein step (i) comprises heating the one or more of the precursors to a temperature of about 100 °C to about 200 °C.

26. The method of claim 24, wherein step (i) comprises pulsing the vapor of the one or more of the precursors from about 0.1 seconds to about 3 seconds.

27. The method of claim 24, wherein step (ii) purging with an inert gas comprising purging from about 1 seconds to about 90 seconds.

28. The method of claim 24, wherein step (iii) comprises introducing one or more oxygen source selected from the group of oxygen (O2), ozone (O3). nitric oxide (NO), water (H2O) vapor, hydrogen peroxide (H2O2), oxygen plasma (O*), NxOy(where x = 1 or 2 and y = 1, 2, 3 or 4) and combinations thereof.

29. The method of claim 24, wherein step (iii) comprises introducing one or more nitrogen source selected from the group of ammonia, hydrazine, an alkylhydrazine, an alkyl amine and combinations thereof.

30. The method of claim 24, wherein step (iii) compromises pulsing a vapor of the one or more oxygen source or nitrogen source from about 0.5 seconds to about 5 seconds.

31. The method of claim 24, wherein step (iv) purging with an inert gas comprising purging from about 1 seconds to about 90 seconds.Application Docket No. P24-211-SEC-WO0132. The method of claim 24, wherein the substrate comprises one or more of silicon oxide, aluminum oxide (AI2O3), titanium nitride (TiN), molybdenum nitride (MoN), tungsten nitride (WN), silicon oxide (SiCh), zirconium oxide (ZrCh) and amorphous carbon.

33. The method of claim 24, wherein the substrate is heated to a temperature of about 25 °C to about 600 °C.

34. A strontium-containing and / or barium-containing film deposited using one or more precursors or compositions of any of claims 1-23.

35. A strontium-containing and / or barium-containing film deposited by the method of any of claims 24-33.

36. A strontium-containing and / or barium-containing film deposited by the method of any of claims 24-33, wherein the film has an aspect ratio of about 1 to about 60.

37. A strontium-containing and / or barium-containing film deposited by the method of any of claims 24-33, wherein the film has a thickness of about 10 A to about 5000 A

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