Alkyl And Aryl Heteroleptic Bismuth Precursors For Bismuth Oxide Containing Thin Films

The disclosed and claimed subject matter relates to bismuth precursors of the formula Bi(Ra)x(Ar)3-x where x=1 or 2 and the use thereof as precursors for deposition of metal-containing films.

BACKGROUND

Field

The disclosed and claimed subject matter relates to bismuth precursors of the formula Bi(Ra)x(Ar)3-xwhere x=1 or 2 and the use thereof as precursors for deposition of bismuth-containing films.

Related Art

Metal-containing films are used in semiconductor and electronics applications. Chemical Vapor Deposition (CVD) and Atomic Layer Deposition (ALD) have been applied as the main deposition techniques for producing thin films for semiconductor devices. These methods enable the achievement of conformal films (metal, metal oxide, metal nitride, metal silicide, and the like) through chemical reactions of metal-containing compounds (precursors). The chemical reactions occur on surfaces which may include metals, metal oxides, metal nitrides, metal silicides, and other surfaces. In CVD and ALD, the precursor molecule plays a critical role in achieving high quality films with high conformality and low impurities. The temperature of the substrate in CVD and ALD processes is an important consideration in selecting a precursor molecule. Higher substrate temperatures, in the range of 150 to 500 degrees Celsius (° C.), promote a higher film growth rate. The preferred precursor molecules must be stable in this temperature range. The preferred precursor is capable of being delivered to the reaction vessel in a liquid phase. Liquid phase delivery of precursors generally provides a more uniform delivery of the precursor to the reaction vessel than solid phase precursors.

CVD and ALD processes are increasingly used as they have the advantages of enhanced compositional control, high film uniformity, and effective control of doping. Moreover, CVD and ALD processes provide excellent conformal step coverage on highly non-planar geometries associated with modern microelectronic devices.

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 chamber. The precursors react and/or decompose on the substrate surface creating a thin film of deposited material. Plasma can be used to assist in reaction of a precursor or for improvement of material properties. 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 of many parameters such as temperature, pressure, gas flow volumes and uniformity, chemical depletion effects, and time.

ALD is a chemical 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 separated during the reaction. 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 chamber. A second precursor or co-reactant 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. Plasma may be used to assist with reaction of a precursor or co-reactant or for improvement in materials quality. This cycle is repeated to create a film of desired thickness.

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 capacitor electrodes, gate electrodes, adhesive diffusion barriers and integrated circuits.

Trimethyl bismuth (BiMe3) and triphenyl bismuth (BiPh3) are volatile, homoleptic bismuth compounds with some degree of utility as ALD precursors. Despite this, they are not practical options for ALD applications. Among other things, trimethyl bismuth is difficult to purify and deliver in a safe manner. SeeAdv. Mater. Opt. Electron.,10, 193 (2000);Integr. Ferroelectr.,45, 215 (2002). Trimethyl bismuth is also a pyrophoric liquid that has been stabilized with dioxane to prevent explosion when used as a bismuth source in MOCVD applications. While trimethyl bismuth and triethylbismuth were used for MOCVD applications, there are not practical options for atomic layer deposition due to very low thermal stability. See Chem. Vap. Deposition, 19, 61-67 (2013). While triphenyl bismuth has good thermal stability and it was used for atomic layer deposition, triphenyl bismuth is a solid with very low vapor pressure. See Thin Solid Films, 622, 65-70 (2017) andChem. Vap. Deposition,6, 139-145 (2000). These disadvantages are problematic for high volume manufacturing of semiconductor devices and therefore preclude their use in applications that require a high degree of control over conformality and precursor flux.

Aside from homoleptic alkyl and aryl compounds for consideration as bismuth precursors, other bismuth compounds are known for use in ALD in a limited capacity as illustrated inFIG.1. SeeCoord. Chem. Rev.,251, 974-1006 (2007);Coord. Chem. Rev.,257, 3297-3322 (2013);Organomet. Chem.,42, 1-53 (2019). For example, bismuth tris(2,2,6,6-tetramethyl-3,5-heptanedionate) has a high molecular weight and requires a high source temperature for precursor delivery. This precursor has a narrow ALD window of 275-300° C. At lower deposition temperatures precursor condensation was observed while at higher temperatures the growth rate per cycle diminished. SeeJ. Phys. Chem. C,116, 3449-3456 (2012)).

Bismuth alkoxides compounds are relatively easy to prepare and are volatile. ALD of Bi2O3employing a bismuth alkoxide precursor was demonstrated on substrates heated below 200° C. However, at temperatures above 200° C., and specifically closer to 300° C., it is unlikely that bismuth alkoxides would be suitable for ALD of Bi2O3due to a high rate of thermal decomposition. SeeJ. Vac. Sci. Technol. A.,32(1), 01A113 (2014).

Bismuth compounds containing silicon are problematic for ozone-ALD processes. It has been shown that the precursors tris(hexamethyldisilazane)bismuth and tris(trimethylsilylmethyl)bismuth deposit bismuth silicate thin films in ozone-based ALD. SeeChem. Vap. Deposition,11, 362-367 (2005).

Uses of bismuth compounds are also described in: Thin Solid Films, 622, 65-70 (2017); U.S. Pat. Nos. 5,902,639; 7,618,681; 6,916,944; 10,186,570; and U.S. Patent Application Publication No. 2010/0279011. None of these or the above references describe viable ALD of Bi2O3by via processes employing heteroleptic bismuth precursors with aryl and alkyl precursors as disclosed and claimed herein.

SUMMARY

The disclosed and claimed subject matter relates to bismuth precursors of the formula Bi(Ra)x(Ar)3-xwhere x=1 or 2 and the use thereof as precursors for deposition of bismuth oxide thin films under high through-put process parameters. Additionally, the process parameters are compatible with current state of the art methods for depositing high quality metal oxide thin films in semiconductor manufacturing. Therefore, mixed metal oxide thin films are achievable with the invented method and compositions. When two or more processes are compatible, both processes can be run consecutively on a single piece of equipment without requiring downtime to switch between parameters (e.g., changing the substrate temperature). High through-put process parameters for atomic layer deposition target a short cycle time. The precursor compositions of this invention enable high precursor flux, short precursor purge times, self-limiting growth behavior at substrate temperatures between about 200° C. and about 400° C. and, in some embodiments, the use of ozone as the second precursor.

In one embodiment, the disclosed and claimed subject matter pertains to heteroleptic bismuth compounds of the formula Bi(Ra)x(Ar)3-xwhere(i) x=1 or 2,(ii) each Rais independently one of an unsubstituted linear C1-C6alkyl group, a linear C1-C6alkyl group substituted with one or more halogen, a linear C1-C6alkyl group substituted with an amino group, an unsubstituted branched C3-C6alkyl group, a branched C3-C6alkyl group substituted with one or more halogen, a branched C3-C6alkyl group substituted with an amino group, an unsubstituted amine, a substituted amine, and —Si(CH3)3and(iii) each Ar is independently one of a C3-C8unsubstituted aromatic group, a C3-C8aromatic group substituted with one or more halogen, a C3-C8aromatic group substituted with an amino group, a 5-member heterocyclic ring and 6-member heterocyclic ring.
It has been shown that bismuth compounds so formulated have advantageous thermal stability and vapor pressure for atomic layer deposition processes in the manufacturing of semiconductor devices.

In one aspect of the above embodiment, each Ar is independently one of:

where each of R1-R12is independently H or Ra. In a more specific embodiment, each of R1-R12is independently H, an unsubstituted linear C1-C6alkyl group and an unsubstituted branched C3-C6alkyl group.

In another embodiment, the disclosed and claimed subject matter includes the use of the above-described heteroleptic bismuth compounds in ALD deposition processes.

DETAILED DESCRIPTION

Embodiments of the disclosed and claimed subject matter are described herein, including the best mode known to the inventors for carrying out the disclosed and claimed subject matter. Variations of those embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the disclosed and claimed subject matter to be practiced otherwise than as specifically described herein. Accordingly, the disclosed and claimed subject matter includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the disclosed and claimed subject matter unless otherwise indicated herein or otherwise clearly contradicted by context.

For ease of reference, “microelectronic device” or “semiconductor device” corresponds to semiconductor wafers having integrated circuits, memory, and other electronic structures fabricated thereon, and flat panel displays, phase change memory devices, solar panels and other products including solar substrates, photovoltaics, and microelectromechanical systems (MEMS), manufactured for use in microelectronic, integrated circuit, or computer chip applications. Solar substrates include, but are not limited to, silicon, amorphous silicon, polycrystalline silicon, monocrystalline silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide on gallium. The solar substrates may be doped or undoped. It is to be understood that the term “microelectronic device” or “semiconductor device” is not meant to be limiting in any way and includes any substrate that will eventually become a microelectronic device or microelectronic assembly.

As defined herein, the term “barrier material” corresponds to any material used in the art to seal the metal lines, e.g., copper interconnects, to minimize the diffusion of said metal, e.g., copper, into the dielectric material. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, and other refractory metals and their nitrides and silicides.

“Substantially free” is defined herein as less than 0.001 wt. %. “Substantially free” also includes 0.000 wt. %. The term “free of” means 0.000 wt. %. As used herein, “about” or “approximately” are intended to correspond to within ±5% of the stated value.

In all such compositions, wherein specific components of the composition are discussed in reference to weight percentage (or “weight %”) ranges including a zero lower limit, it will be understood that such components may be present or absent in various specific embodiments of the composition, and that in instances where such components are present, they may be present at concentrations as low as 0.001 weight percent, based on the total weight of the composition in which such components are employed. Note all percentages of the components are weight percentages and are based on the total weight of the composition, that is, 100%. Any reference to “one or more” or “at least one” includes “two or more” and “three or more” and so on.

Where applicable, all weight percents unless otherwise indicated are “neat” meaning that they do not include the aqueous solution in which they are present when added to the composition. For example, “neat” refers to the weight % amount of an undiluted acid or other material (i.e., the inclusion 100 g of 85% phosphoric acid constitutes 85 g of the acid and 15 grams of diluent).

Moreover, when referring to the compositions described herein in terms of weight %, it is understood that in no event shall the weight % of all components, including non-essential components, such as impurities, add to more than 100 weight %. In compositions “consisting essentially of” recited components, such components may add up to 100 weight % of the composition or may add up to less than 100 weight %. Where the components add up to less than 100 weight %, such composition may include some small amounts of a non-essential contaminants or impurities. For example, in one such embodiment, the formulation can contain 2% by weight or less of impurities. In another embodiment, the formulation can contain 1% by weight or less than of impurities. In a further embodiment, the formulation can contain 0.05% by weight or less than of impurities. In other such embodiments, the constituents can form at least 90 wt %, more preferably at least 95 wt %, more preferably at least 99 wt %, more preferably at least 99.5 wt %, most preferably at least 99.9 wt %, of the composition, and can include other ingredients that do not material affect the performance of the composition. Otherwise, if no significant non-essential impurity component is present, it is understood that the composition of all essential constituent components will essentially add up to 100 weight %.

The headings employed herein are not intended to be limiting; rather, they are included for organizational purposes only.

EXEMPLARY EMBODIMENTS

As noted above, the disclosed and claimed subject matter pertains to heteroleptic bismuth compounds for use as ALD precursors.

Disclosed and Claimed Heteroleptic Bismuth Precursors

In one embodiment, the disclosed and claimed subject matter pertains to heteroleptic bismuth compounds of the formula Bi(Ra)x(Ar)3-xwhere(i) x=1 or 2,(ii) each Rais independently one of an unsubstituted linear C1-C6alkyl group, a linear C1-C6alkyl group substituted with one or more halogen, a linear C1-C6alkyl group substituted with an amino group, an unsubstituted branched C3-C6alkyl group, a branched C3-C6alkyl group substituted with one or more halogen, a branched C3-C6alkyl group substituted with an amino group, an unsubstituted amine, a substituted amine, and —Si(CH3)3and(iii) each Ar is independently one of a C3-C8unsubstituted aromatic group, a C3-C8aromatic group substituted with one or more halogen, a C3-C8aromatic group substituted with an amino group, a 5-member heterocyclic ring and 6-member heterocyclic ring and(iv) the precursor does not include:

It has been shown that bismuth compounds so formulated have advantageous thermal stability and vapor pressure for atomic layer deposition processes in the manufacturing of semiconductor devices.

As noted above, each Rais independently one of an unsubstituted linear C1-C6alkyl group, a linear C1-C6alkyl group substituted with one or more halogen, a linear C1-C6alkyl group substituted with an amino group, an unsubstituted branched C3-C6alkyl group, a branched C3-C6alkyl group substituted with one or more halogen, a branched C3-C6alkyl group substituted with an amino group, an unsubstituted amine, a substituted amine, and —Si(CH3)3.

In one embodiment, Rais an unsubstituted linear C1-C6alkyl group. In one aspect of this embodiment, Rais a methyl group. In one aspect of this embodiment, Rais an ethyl group. In one aspect of this embodiment, Rais a propyl group. In one aspect of this embodiment, Rais a butyl group. In one aspect of this embodiment, Rais a pentyl group. In one aspect of this embodiment, Rais a hexyl group.

In one embodiment, Rais a substituted linear C1-C6alkyl group substituted with one or more halogen. In one aspect of this embodiment, Rais a methyl group substituted with one or more halogen. In one aspect of this embodiment, Rais an ethyl group substituted with one or more halogen. In one aspect of this embodiment, Rais a propyl group substituted with one or more halogen. In one aspect of this embodiment, Rais a butyl group substituted with one or more halogen. In one aspect of this embodiment, Rais a pentyl group substituted with one or more halogen. In one aspect of this embodiment, Rais a hexyl group substituted with one or more halogen. In one aspect of this embodiment, the one or more halogen includes fluorine. In one aspect of this embodiment, the one or more halogen includes chlorine. In one aspect of this embodiment, the one or more halogen includes bromine. In one aspect of this embodiment, the one or more halogen includes iodine.

In one embodiment, Rais a substituted linear C1-C6alkyl group substituted with an amino group. In one aspect of this embodiment, Rais a methyl group substituted with an amino group. In one aspect of this embodiment, Rais an ethyl group substituted with an amino group. In one aspect of this embodiment, Rais a propyl group substituted with an amino group. In one aspect of this embodiment, Rais a butyl group substituted with an amino group. In one aspect of this embodiment, Rais a pentyl group substituted with an amino group. In one aspect of this embodiment, Rais a hexyl group substituted with an amino group.

In one embodiment, Rais an unsubstituted branched C3-C6alkyl group. In one aspect of this embodiment, Rais an iso-propyl group. In one aspect of this embodiment, Rais an iso-butyl group. In one aspect of this embodiment, Rais a sec-butyl group. In one aspect of this embodiment, Rais a tert-butyl group. In one aspect of this embodiment, Rais branched pentyl group for example neo-pentyl, sec-pentyl or tert-pentyl. In one aspect of this embodiment, Rais a neopentyl group. In one aspect of this embodiment, Rais a branched hexyl group.

In one embodiment, Rais a substituted branched C3-C6alkyl group substituted with one or more halogen. In one aspect of this embodiment, Rais an iso-propyl group substituted with one or more halogen. In one aspect of this embodiment, Rais an iso-butyl group substituted with one or more halogen. In one aspect of this embodiment, Rais a sec-butyl group substituted with one or more halogen. In one aspect of this embodiment, Rais a tert-butyl group substituted with one or more halogen. In one aspect of this embodiment, Rais branched pentyl group substituted with one or more halogen. In one aspect of this embodiment, Rais a neopentyl group substituted with one or more halogen. In one aspect of this embodiment, Rais a branched hexyl group substituted with one or more halogen. In one aspect of this embodiment, the with one or more halogen includes fluorine. In one aspect of this embodiment, the with one or more halogen includes chlorine. In one aspect of this embodiment, the with one or more halogen includes bromine. In one aspect of this embodiment, the with one or more halogen includes iodine.

In one embodiment, Rais a substituted branched C3-C6alkyl group substituted with an amino group. In one aspect of this embodiment, Rais an iso-propyl group substituted with an amino group. In one aspect of this embodiment, Rais an iso-butyl group substituted with an amino group. In one aspect of this embodiment, Rais a sec-butyl group substituted with an amino group. In one aspect of this embodiment, Rais a tert-butyl group substituted with an amino group. In one aspect of this embodiment, Rais branched pentyl group substituted with an amino group. In one aspect of this embodiment, Rais a neopentyl group substituted with an amino group. In one aspect of this embodiment, Rais a branched hexyl group substituted with an amino group.

In one embodiment, Rais an unsubstituted amine.

In one embodiment, Rais a substituted amine.

In one embodiment, Rais —Si(CH3)3.

In some embodiments, the Rahas a structure described in Table 1:

The Rasubstituents are not limited to those exemplified in Table 1.

Ar Substituents

As noted above, each Ar is independently one of a C3-C8unsubstituted aromatic group, a C3-C8aromatic group substituted with one or more halogen, a C3-C8aromatic group substituted with an amino group, a 5-member heterocyclic ring and 6-member heterocyclic ring.

In one embodiment, each Ar is independently one of:

where each of R1-R12is independently H or Ra. In a more specific embodiment, each of R1-R12is independently H. In a more specific embodiment, each of R1-R12is independently Ra. In a more specific embodiment, each of R1-R12is independently the same Ra. In a more specific embodiment, each of R1-R12is an unsubstituted linear C1-C6alkyl group. In a more specific embodiment, each of R1-R12is an unsubstituted branched C3-C6alkyl group.

In one embodiment, each Ar is:

where each of R1-R5is independently H or Ra. In a more specific embodiment, each of R1-R5is independently H. In a more specific embodiment, each of R1-R5is independently Ra. In a more specific embodiment, each of R1-R5is independently the same Ra. In a more specific embodiment, each of R1-R5is an unsubstituted linear C1-C6alkyl group. In a more specific embodiment, each of R1-R5is an unsubstituted branched C3-C6alkyl group.

In one embodiment, each Ar is:

where each of R6-R9is independently H or Ra. In a more specific embodiment, each of R6-R9is independently H. In a more specific embodiment, each of R6-R9is independently Ra. In a more specific embodiment, each of R6-R9is independently the same Ra. In a more specific embodiment, each of R6-R9is an unsubstituted linear C1-C6alkyl group. In a more specific embodiment, each of R6-R9is an unsubstituted branched C3-C6alkyl group.

In one embodiment, each Ar is:

where each of R10-R12is independently H or Ra. In a more specific embodiment, each of R10-R12is independently H. In a more specific embodiment, each of R10-R12is independently Ra. In a more specific embodiment, each of R10-R12is independently the same Ra. In a more specific embodiment, each of R10-R12is an unsubstituted linear C1-C6alkyl group. In a more specific embodiment, each of R10-R12is an unsubstituted branched C3-C6alkyl group.

In some embodiments, the Ar has a structure as illustrated in Table 2:

The Ar substituents are not limited to those exemplified in Table 2.

In one aspect of this embodiment, the heteroleptic bismuth compound is “BiPhNp2” having the following structure:

In this embodiment, in the formula Bi(Ra)x(Ar)3-x, x=2, each Rais a neo-pentyl group and Ar is a phenyl group.

In one aspect of this embodiment, the heteroleptic bismuth compound is “BiPyr2Me” having the following structure:

wherein x=1, Rais a methyl group and each Ar is

In one aspect of this embodiment, the heteroleptic bismuth compound is “BiPyrNp2” having the following structure:

wherein x=2, Rais a neo-pentyl group and Ar is

In one aspect of this embodiment, the heteroleptic bismuth compound is “BiImid2Me” having the following structure or the isomer of the following structure:

wherein x=1, Rais a methyl group and each Ar is N

In one aspect of this embodiment, the heteroleptic bismuth compound is “BiImidMe2” having one of the following structure or the isomers of the following structures:

Method of Use

The disclosed and claimed subject matter further includes the use of a heteroleptic bismuth compound of formula Bi(Ra)x(Ar)3-xwhere(i) x=1 or 2,(ii) each Rais independently one of an unsubstituted linear C1-C6alkyl group, a linear C1-C6alkyl group substituted with one or more halogen, a linear C1-C6alkyl group substituted with an amino group, an unsubstituted branched C3-C6alkyl group, a branched C3-C6alkyl group substituted with one or more halogen, a branched C3-C6alkyl group substituted with an amino group, an unsubstituted amine, a substituted amine, and —Si(CH3)3and(iii) each Ar is independently one of a C3-C8unsubstituted aromatic group, a C3-C8aromatic group substituted with one or more halogen, a C3-C8aromatic group substituted with an amino group, a 5-member heterocyclic ring and 6-member heterocyclic ring
to deposit bismuth containing films using any chemical vapor deposition process known to those of skill in the art. As used herein, the term “chemical vapor deposition process” refers to any process wherein a substrate is exposed to one or more volatile precursors, which react and/or decompose on the substrate surface to produce the desired deposition.

In one embodiment, the method includes the use of heteroleptic bismuth compound to deposit bismuth containing films using an atomic layer deposition process (ALD). As used herein, the term “atomic layer deposition process” or ALD refers to a self-limiting (e.g., the amount of film material deposited in each reaction cycle is constant), sequential surface chemistry that deposits films of materials onto substrates of varying compositions. Although the precursors, reagents and sources used herein may be sometimes described as “gaseous,” it is understood that the precursors can be either liquid or solid which are transported with or without an inert gas into the reactor via direct vaporization, bubbling or sublimation. In some case, the vaporized precursors can pass through a plasma generator. The term “reactor” as used herein, includes without limitation, reaction chamber, reaction vessel or deposition chamber.

In one embodiment, the heteroleptic bismuth compound used in the disclosed and claimed methods to deposit bismuth containing films includes, consist essentially of or consists of the disclosed and claimed heteroleptic bismuth precursors Bi(Ra)x(Ar)3-xdescribed above in the section “Disclosed and Claimed Heteroleptic Bismuth Precursors.” In one aspect of this embodiment, the heteroleptic bismuth precursor includes, consists essentially of or consists of BiPhNp2. In one aspect of this embodiment, the heteroleptic bismuth precursor includes, consists essentially of or consists of BiPyr2Me. In one aspect of this embodiment, the heteroleptic bismuth precursor includes, consists essentially of or consists of BiPyrNp2. In one aspect of this embodiment, the heteroleptic bismuth precursor includes, consists essentially of or consists of BiImid2Me. In one aspect of this embodiment, the heteroleptic bismuth precursor includes, consists essentially of or consists of BiImidMe2.

In another embodiment, the heteroleptic bismuth compound used in the disclosed and claimed methods to deposit bismuth containing films includes, consist essentially of or consists of having a heteroleptic bismuth precursor of formula Bi(Ra)x(Ar)3-xwhere x=1, Rais a methyl group and each Ar is a phenyl group (“BiPh2Me”):

The precursor BiPh2Me, but not its use in a deposition process, is described in Organometallics, 20(3), 586-589 (2001) andChem. Ber.,118, 1031-1038 (1985).

In another embodiment, the heteroleptic bismuth compound used in the disclosed and claimed methods to deposit bismuth containing films includes, consist essentially of or consists of having a heteroleptic bismuth precursor of formula Bi(Ra)x(Ar)3-xwhere x=2, each Rais a methyl group and Ar is a phenyl group (“BiPhMe2”):

The precursor BiPhMe2, but not its use in a deposition process, is described inZ. Naturforsch., B, 40, 1476 (1985).

In another embodiment, the heteroleptic bismuth compound used in the disclosed and claimed methods to deposit bismuth containing films includes, consist essentially of or consists of having a heteroleptic bismuth precursor of formula Bi(Ra)x(Ar)3-xwhere x=1, Ra is neo-pentyl group and each Ar is a phenyl group (“BiPh2Np”):

The precursor BiPh2Np, but not its use in a deposition process, is described in Organometallics, 22 (14), 2929-2924 (2003).

In another embodiment, the heteroleptic bismuth compound used in the disclosed and claimed methods to deposit bismuth containing films includes, consist essentially of or consists of having a heteroleptic bismuth precursor of formula Bi(Ra)x(Ar)3-xdescribed above.

Chemical vapor deposition processes in which the disclosed and claimed precursors can be utilized include, but are not limited to, those used for the manufacture of semiconductor type microelectronic devices such as ALD and plasma enhanced ALD (PEALD). This, in one embodiment, for example, the metal-containing film is deposited using an ALD process. In another embodiment, for example, the metal-containing film is deposited using a plasma enhanced ALD (PEALD) process.

In such deposition methods and processes an oxidizing agent can be utilized. The oxidizing agent is typically introduced in gaseous form. Examples of suitable oxidizing agents include, but are not limited to, oxygen gas, water vapor, ozone, oxygen plasma, or mixtures thereof.

The deposition methods and processes may also involve one or more purge gases. The purge gas, which is used to purge away unconsumed reactants and/or reaction byproducts, is an inert gas that does not react with the precursors. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N2), helium (He), neon, and mixtures thereof. For example, a purge gas such as Ar is supplied into the reactor at a flow rate ranging from about 10 to about 2000 sccm for about 0.1 to 10000 seconds, thereby purging the unreacted material and any byproduct that may remain in the reactor.

The deposition methods and processes require that energy be applied to the at least one of the precursors, oxidizing agent, other precursors or combination thereof to induce reaction and to form the metal-containing film or coating on the substrate. Such energy can be provided by, but not limited to, thermal, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-ray, e-beam, photon, remote plasma methods, and combinations thereof. In some processes, a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface. When utilizing plasma, the plasma-generated process may include a direct plasma-generated process in which plasma is directly generated in the reactor, or alternatively a remote plasma-generated process in which plasma is generated outside of the reactor and supplied into the reactor.

When utilized in such deposition methods and processes suitable precursors-such as those presently disclosed and claimed—may be delivered to the reaction chamber such as an ALD reactor in a variety of ways. In some instances, a liquid delivery system may be utilized. In other instances, a combined liquid delivery and flash vaporization process unit may be employed, such as, for example, the turbo vaporizer manufactured by MSP Corporation of Shoreview, MN, to enable low volatility materials to be volumetrically delivered, which leads to reproducible transport and deposition without thermal decomposition of the precursor. The precursor compositions described herein can be effectively used as source reagents via direct liquid injection (DLI) to provide a vapor stream of these metal precursors into an ALD reactor.

When used in these deposition methods and processes, the disclosed and claimed precursors can be combined with and 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 precursors include, but are not limited to, toluene, mesitylene, cumene (isopropylbenzene), p-cymene (4-isopropyl toluene), 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decahydronaphthalene (decalin). The disclosed and claimed precursors can also be stored and used in stainless steel containers. In certain embodiments, the hydrocarbon solvent is a high boiling point solvent or has a boiling point of 100 degrees Celsius or greater. The disclosed and claimed precursors can also be mixed with other suitable metal precursors, and the mixture used to deliver both metals simultaneously for the growth of a binary metal-containing films.

A flow of argon and/or other gas may be employed as a carrier gas to help deliver a vapor containing at least one of the disclosed and claimed precursors to the reaction chamber during the precursor pulsing. When delivering the precursors, the reaction chamber process pressure is between 1 and 50 torr, preferably between 5 and 20 torr.

Substrate temperature can be an important process variable in the deposition of high-quality metal-containing films. Typical substrate temperatures range from about 150° C. to about 550° C. Higher temperatures can promote higher film growth rates.

In view of the forgoing, those skilled in the art will recognize that the disclosed and claimed subject matter further includes the use of the disclosed and claimed precursors in chemical vapor deposition processes as follows.

In one embodiment, the disclosed and claimed subject matter includes a method for forming a bismuth-containing film on at least one surface of a substrate that includes the steps of:a. providing the substrate with the at least one surface in a reaction vessel;b. forming a bismuth-containing film on the at least one surface by a thermal atomic layer deposition (ALD) process using one or the disclosed and claimed precursors as a metal source compound for the deposition process.
In a further aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel. In a further aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel where the at least one reactant is selected from the group of water, diatomic oxygen, oxygen plasma, ozone, NO, N2O, NO2, carbon monoxide, carbon dioxide and combinations thereof. In another aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel where the at least one reactant is selected from the group of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma, and combinations thereof. In another aspect of this embodiment, the method includes introducing at least one reactant into the reaction vessel where the at least one reactant is selected from the group hydrogen, hydrogen plasma, a mixture of hydrogen and helium, a mixture of hydrogen and argon, hydrogen/helium plasma, hydrogen/argon plasma, boron-containing compounds, silicon-containing compounds and combinations thereof.

In one embodiment, the disclosed and claimed subject matter includes a method of forming a bismuth-containing film via a thermal atomic layer deposition (ALD) process or thermal ALD-like process that includes the steps of:a. providing a substrate in a reaction vessel;b. introducing into the reaction vessel one or more of the disclosed and claimed precursors;c. purging the reaction vessel with a first purge gas;d. introducing into the reaction vessel a source gas;e. purging the reaction vessel with a second purge gas;f. sequentially repeating steps b through e until a desired thickness of the bismuth-containing film is obtained.
In a further aspect of this embodiment, the source gas is one or more of an oxygen-containing source gas selected from water, diatomic oxygen, ozone, NO, N2O, NO2, carbon monoxide, carbon dioxide and combinations thereof. In another aspect of this embodiment, the source gas is one or more of a nitrogen-containing source gas selected from ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogen plasma, nitrogen/hydrogen plasma and mixture thereof. In a further aspect of this embodiment, the first and second purge gases are each independently selected from one or more of argon, nitrogen, helium, neon, and combinations thereof. In a further aspect of this embodiment, the method further includes applying energy to the one or more precursor, the source gas, the substrate, and combinations thereof, wherein the energy is one or more of thermal, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-ray, e-beam, photon, remote plasma methods and combinations thereof. In a further aspect of this embodiment, step b of the method further includes introducing into the reaction vessel the precursor using a stream of carrier gas to deliver a vapor of the precursor into the reaction vessel. In a further aspect of this embodiment, step b of the method further includes use of a solvent medium comprising one or more of toluene, mesitylene, isopropylbenzene, 4-isopropyl toluene, 1,3-diisopropylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butylcyclohexane, and decahydronaphthalene and combinations thereof.

In one aspect of this disclosure the bismuth precursors may be used to co-deposit multi-component oxide films. Multi-component oxide film may further include an oxide of one or more elements selected from magnesium, calcium, strontium, barium, aluminum, gallium, indium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten, tellurium and antimony.

In one embodiment, the disclosed and claimed subject matter includes a method of forming a bismuth-containing multi-component oxide film in a thermal atomic layer deposition (ALD) process or thermal ALD-like process that includes the steps of:a. providing a substrate in a reaction vessel;b. introducing into the reaction vessel one or more of the disclosed and claimed bismuth precursors;c. introducing into the reaction vessel one or more of the co-precursors including an element other than bismuth;d. purging the reaction vessel with a first purge gas;e. introducing into the reaction vessel a source gas;f. purging the reaction vessel with a second purge gas;g. sequentially repeating steps b through f until a desired thickness of the bismuth-containing multi-component oxide film is obtained.

In another embodiment, the disclosed and claimed subject matter includes a method of forming a bismuth-containing multi-component oxide film in a thermal atomic layer deposition (ALD) process or thermal ALD-like process that includes the steps of:a. providing a substrate in a reaction vessel;b. introducing into the reaction vessel one or more of the disclosed and claimed bismuth precursors;c. purging the reaction vessel with a first purge gas;d. introducing into the reaction vessel a source gas;e. purging the reaction vessel with a second purge gas;f. introducing into the reaction vessel one or more of the co-precursors comprising an element other than bismuth;g. purging the reaction vessel with a third purge gas;h. introducing into the reaction vessel a source gas;i. purging the reaction vessel with a fourth purge gas;j. sequentially repeating steps b through i until a desired thickness of the bismuth-containing multi-component oxide film is obtained.

The examples of the co-precursors include but are not limited to trimethylaluminum, tetrakis(dimethylamino) titanium, tetrakis(ethylmethylamino) zirconium, tetrakis(ethylmethylamino) hafnium and tris-isopropylcyclopentadienyl lanthanum.

In another embodiment bismuth-containing film is deposited directly on a substance that promotes self-limited growth, i.e., an “SLG oxide layer.” An SLG oxide layer is a thin layer of oxide (also thin film of oxide) which stimulates self-limited growth of the bismuth-containing film. The self-limited growth occurs where and when the deposition rate of the bismuth-containing film substantially drops with increasing number of cycles. Self-limited growth is desired for conformal deposition of thin films on high aspect ratio features. Without being bound by theory it is believed that self-limited growth is due to significantly lower deposition rate of bismuth-containing film on bismuth-containing film compared to deposition rate of bismuth-containing film on SLG oxide layer.

The examples of SLG oxide may include but are not limited to aluminum oxide and titanium oxide. The thickness of SLG oxide layer is preferably <5 nm, more preferably <3 nm and more preferably <1 nm.

Examples

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

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 following examples, covers the modifications and variations of the disclosed subject matter that come within the scope of any claims and their equivalents.

Materials and Methods:

All reactions and manipulations described in the examples were conducted under a nitrogen atmosphere using an inert atmosphere glove box or standard Schlenk techniques. All chemicals were received from Millipore-Sigma.

SPECIFIC EXAMPLES

Example 1: Synthesis of BiPh2C1

BiCl3(34.23 g) was dissolved in 100 mL of tetrahydrofuran. BiPh3(28.35 g), was dissolved in 200 mL of tetrahydrofuran. The solution of BiCl3in tetrahydrofuran was added dropwise to the solution of BiPh3at −10° C. over 1.5 hours. The cloudy solution was stirred overnight at RT and filtered to remove a small amount of insoluble solid. The solvent was removed under vacuum to afford a white solid. The solid was dried under vacuum at 60° C. for 1 hour, washed with diethyl ether, and re-dried. 34.2 g of BiPh2Cl was collected, 98%.

Example 2: Synthesis and Purification of BiPh2Me

Synthesis of BiPh2Me is described inChem. Ber.,118, 1031-1038 (1985). Attempts to duplicate the procedure afforded a low purity material that was difficult to purify by vacuum distillation. Changing the reaction solvent to toluene afforded a pure material which could be purified by vacuum distillation. In theory, the heterogeneous reaction mixture in toluene separated the product from insoluble impurities. The impurities, if soluble, would catalyze product decomposition.

BiPh2C1(34.23 g, 85.9 mmol) was suspended in 250 mL of toluene and cooled to −78° C. MeLi (60 mL, 1.6M in Et2O, 96 mmol) was added dropwise via a cannula and the mixture was stirred for 18 h while warming to RT. All volatile components were removed under reduced pressure to yield a cloudy oil. The oil was extracted with portions of hexane (3×50 mL). Each portion of hexane was collected by filtration. The filtrates were combined and concentrated under reduced pressure to afford a colorless oil (30.42 g, 99%). The oil was purified by fractional vacuum distillation. The first fraction was collected at 31° C./60 mTorr as a colorless oil (3.5 g, confirmed by1H NMR as BiPhMe2. The second, main fraction was collected at 98° C./77 mTorr (25.2 g, 78%).

Example 3: Synthesis of BiPh(Np)2

BiPhCl2(37.63 g, 105.4 mmol) was suspended in 300 mL of toluene and cooled to −78° C. Neo-pentyl MgCl (209 mL, 1 M in THF, 209 mmol) was added dropwise via a cannula and the mixture was stirred for 18 h while warming to RT. A large amount of solid had formed after 18 h such that magnetic stirring was ineffective. 200 mL of THF was added to dissolve the solid. Stirring continued for 24 h. All volatile components were removed under reduced pressure to yield a light brown solid. The solid was extracted with portions of hexane (3×150 mL). Each portion of hexane was collected by filtration. The three hexane filtrates were combined and concentrated under reduced pressure the afford a colorless oil. The colorless oil was purified by vacuum distillation (41.22 g, 91.3%).

Example 4: Synthesis of BiPyr(Np)2

Synthesis of tris (N-methyl-2-pyrolyl) bismuth (BiPyr3) was synthesized via salt metathesis of bismuth trichloride and N-methyl-2-pyrollyl lithium. Analytical data fromDalton Trans.,46, 8269-8278 (2017) was used for comparison to confirm the synthesis.

BiPyr3(3.04 g, 6.77 mmol) dissolved in 50 mL of THF was added dropwise to BiCl3(4.27 g, 13.54 mmol) dissolved in 100 mL in THF. The solution was stirred for 18 h. While cooled to −78° C., Neo-pentyl MgCl (40.6 mL, 1 M in THF, 40.6 mmol) was added dropwise via a cannula. The mixture was stirred for 18 h while warming to RT. Volatile components were removed under a reduced pressure of 1 torr and mild heating of the flask to 30° C. The crude material was extracted with portions of hexane (3×50 mL). Each portion of hexane was collected by filtration. The filtrates were combined and concentrated under reduced pressure to afford a cloudy oil (8.61 g, 98%). The oil was heated to 70° C. at 60 mTorr to sublime out tris-neo-pentyl bismuth. The oil was then heated to 110° C. at 60 mTorr to distill a colorless liquid (2.17 g, 25%, b.p.=63° C./60 mTorr).

Example 5: Synthesis of Bi(Np)3

BiCl3(46.52 g, 116 mmol) was dissolved in 200 mL of THF and cooled to −78° C. Neo-pentyl MgCl (350 mL, 1 M in THF, 350 mmol) was added dropwise via a cannula and the mixture was stirred for 18 h while warming to RT. All volatile components were removed under reduced pressure (1 Torr, 30° C.) to yield a light grey solid. The solid was extracted with portions of pentane (4×200 mL). Each portion of pentane was collected by filtration, combined and then concentrated under reduced pressure (1 Torr) to afford a white solid. The solid was allowed to sublime out tris-neo-pentyl bismuth at 80° C., 100 mTorr (48 g, 96%).

Example 6: Thermal Analyses of Heteroleptic Bismuth Precursors

Physical properties such as thermal stability and volatility are determined by the ligands in a precursor. Bismuth aryl compounds have low volatility and high thermal stability. Bismuth alkyl compounds have high volatility and low thermal stability. Heteroleptic bismuth precursors containing aryl and alkyl ligands, surprisingly, have intermediate physical properties with respect to the homoleptic compounds. Atomic layer deposition employing a heteroleptic bismuth precursor can deposit thin films of Bi2O3without the limitations imposed by low volatility and low thermal stability. Heteroleptic bismuth precursors enables atomic layer deposition of Bi2O3in a manner suitable with high volume manufacturing of semiconductor and memory devices.

FIG.2illustrates the thermal stability analysis of BiMe3, BiPh2Me, and BiPh3measured and compared their respective onsets of thermal decomposition by differential scanning calorimetry. The trend in thermal stability was dependent on the types of ligands in the compound. As shown in Table 3, BiMe3began to decompose around 170° C., BiPh2Me around 250° C. and BiPh3decomposed at temperatures near 300° C. Specifically, BiPh2Me and BiPh3began to decompose at 250° C. and 300° C., respectively.

Evaporation data for several heteroleptic bismuth compounds were collected by TGA to determine the temperature required to produce 1 Torr of vapor pressure. As shown in Table 3, the temperature was determined to be 110° C. for BiPh2Me. A range of 60-130° C. was determined for all the heteroleptic compounds. For comparison, a temperature of 175° C. was determined for BiPh3. As to vapor pressure data for BiMe3, Fluid Phase Equilibria, 360, 106-110 (2013) reports the temperature required for 1 Torr of vapor pressure to be <20° C. The 1 Torr temperature is of interest to atomic layer deposition processes as this value represent the set temperature for the precursor container in order to run the process in a reasonable manner. The precursors of this invention have 1 torr vapor pressure between 30° C. and 130° C.

Example 7: Deposition of Bismuth-Containing Films

Several bismuth precursors were tested in deposition experiments in order to deposit Bi2O3thin films. The experiments were performed in a manner consistent with ALD (i.e., the precursor and oxidant were delivered into the reaction chamber independently separated by an inert gas purge). In general, the heteroleptic bismuth precursors required reasonable container temperatures of around 100° C. to deliver a saturating pulse of gaseous precursors. This was expected due to their intermediate volatile properties compared to the homoleptic bismuth precursors. The tri (neo-pentyl) bismuth precursor is volatile and required mild container heating to produce enough vapor pressure. The container temperature for tri(phenyl) bismuth was set high at 160° C. in order to deliver an adequate amount of precursor vapor per pulse. Uniformly heating a precursor container and delivery lines to around 100° C. without cold spots is a manageable task with heating jackets and heating tape commonly used in ALD equipment.

To determine the precursor stability under the reactor settings, “Bi CVD” experiments were performed. As shown in Table 4, the precursors were pulsed into the reaction chamber (without the O3oxidant) to determine the amount of bismuth deposited due to thermal decomposition. The heteroleptic precursors deposited less than 1 Å of bismuth after 100 pulses at 280° C. and 320° C. At 400° C., di (neo-pentyl)phenylbismuth deposited 3 Å of bismuth indicating a small increase in thermal decomposition. Tri (neo-pentyl) bismuth deposited 1542 Å of bismuth at 400° C., whereas triphenyl bismuth deposited negligible amounts of bismuth at all three temperatures. These results clearly demonstrate a relationship between the number of bismuth-aryl bonds and thermal stability. Additionally, the heteroleptic bismuth precursors exhibited enough thermal stability to allow for controlled deposition of Bi2O3in a manner consistent with ALD. Growth rates for diphenyl methylbismuth and di (neo-pentyl)phenylbismuth were measured to be 0.13 Å/cycle at optimized precursor pulse times near saturation conditions. As shown inFIG.4, precursor pulse times for diphenyl-methylbismuth and di (neo-pentyl)phenylbismuth were selected to be 5 s and 2 s for near self-limiting growth behavior, according to saturation curves. Conditions inFIG.4are as follows: 280° C.; 100 cycles, 5 s O3pulse for BiPh2Me; 2 s O3pulse for BiPh (Np)2and BiNp3. Notably, tri (neo-pentyl) bismuth did not show self-limiting growth, likely due to thermal decomposition of the precursor.

Example 8: Self-limited Growth of Bi-containing Films on SLG Oxide Layer

Self-limited growth (SLG) of bismuth-containing film was demonstrated on aluminum oxide SLG oxide layer. The experiments were performed in a manner consistent with ALD (i.e., the precursor and oxidant were delivered into the reaction chamber independently separated by an inert gas purge). SLG oxide layer was deposited by trimethylaluminum/ozone thermal ALD process at 300° C. Bismuth oxide film was deposited using BiPh2Me bismuth precursor at 280° C. using the following ALD sequence: BiPh2Me/Ar purge/03/Ar purge=5 sec/43 sec/2 sec/43 sec. The number of cycles in bismuth oxide ALD process varied from 20 to 250 to determine if self-limited growth can be achieved.FIG.5shows the dependence of bismuth oxide thickness on the number of ALD cycles. The result shows that when aluminum oxide is used as SLG oxide layer self-limited growth of bismuth oxide film it can be accomplished, while no self-limited growth is observed on zirconium oxide.

It is anticipated that the disclosed and claimed methods could be used in conjunction with deposition tools commonly found at semiconductor manufacturing sites to produce molybdenum-containing layers for logic applications and other potential functions.

The foregoing description is intended primarily for purposes of illustration. Although the disclosed and claimed subject matter has been shown and described with respect to an exemplary embodiment thereof, it should be understood by those skilled in the art that the foregoing and various other changes, omissions, and additions in the form and detail thereof may be made therein without departing from the spirit and scope of the disclosed and claimed subject matter.