Boron-containing precursors for ALD deposition of boron nitride films

Abstract

A boron-containing precursor having the structure of Formula I: B (NR1R2) nX3-n (I) wherein R1 is selected from a linear C1 to C10 alkyl group, a branched C3 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C1 to C6 dialkylamino group, an electron withdrawing group, and a C4 to C10 aryl group; r2 is selected from hydrogen, a linear C1 to C10 alkyl group, a branched C3 to C10 alkyl group, a linear or branched C3 to C6 alkenyl group, a linear or branched C3 to C6 alkynyl group, a C1 to C6 dialkylamino group, a C6 to C10 aryl group, a linear or branched C1 to C6 fluorinated alkyl group, an electron withdrawing group, and a C4 to C10 aryl group; x is Cl, Br, I or F; and n = 1 or 2 wherein R1 and R2 are optionally linked together to form a ring selected from a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring, and wherein R1 and R2 may be the same or different moieties. A deposition method is also disclosed.

Description

Background Art

[0001] Exemplary embodiments of the present invention relate to compositions and methods for forming boron-containing films. More specifically, compounds and compositions and methods containing the same are described herein for forming stoichiometric or non-stoichiometric boron-containing films or materials or boron-doped silicon-containing films at one or more deposition temperatures.

[0002] Example technologies that can utilize the high quality ALD boron nitride layers disclosed herein include insulating layers in MISFETs (metal-insulator-semiconductor field effect transistors), interconnect caps (such as copper) to help prevent power loss, reduce resistivity, and prevent interconnect failures caused by power overloads. Other applications include finFETs, DRAMs, flash memories, etc. Additional applications include as an interfacial layer of amorphous or crystalline BN deposited prior to dielectric deposition in MOSFET (metal-oxide-semiconductor FET) device structures to prevent matrix diffusion into high-k materials, thereby producing devices with a lower density of interfacial traps (Dit). To date, boron precursors, such as haloboranes (e.g., BCl3), trialkylboranes, or boron alkoxide precursors, have been used for boron doped films.

[0003] Haloborane compounds, such as BCl3 and BBr3, are used to deposit boron nitride films by ALD, however, there are concerns about residual halides in the film, which can adversely affect electrical properties. It is also known that aminoborane compounds, such as (Me2N)3B, can be used to deposit boron nitride films by ALD, however, while these films can be deposited using N2 PEALD processes, the step coverage performance of N2-based PEALD processes is poor. To date, it has not been possible to deposit boron nitride films from aminoborane precursors using NH3-based PEALD processes at temperatures below 500°C.

[0004] Another problem with prior art boron nitrite precursors in ALD is poor deposition at the bottom of features, which often results in voids in the gap fill process. The gap fill process is a very important stage of semiconductor manufacturing as it is used to fill high aspect ratio gaps (or features) with insulating or conductive materials. For example, shallow trench isolation, inter-metal dielectric layers, passivation layers, dummy gates, etc. With shrinking device geometries (e.g., critical dimensions <20nm) and shrinking thermal budgets, void-free filling of high aspect ratio spaces (e.g., AR>10:1) becomes increasingly difficult due to limitations of conventional deposition processes.

[0005] Most deposition methods - including the boron nitrate deposition process - deposit more material on the top area or walls of the trench than on the bottom area of ​​the structure. This method typically forms a mushroom-shaped film profile. As a result, the top portion of the high aspect ratio structure sometimes pinches off prematurely, leaving a seam / void in the lower portion of the structure. This problem is more prevalent in small features.

[0006] Therefore, there is a need in the art for a precursor that can deposit boron nitrite by ALD in a bottom-up process in very small aspect ratio features. Summary of the invention

[0007] The present invention meets this need. Boron nitride films can be deposited from mixed haloaminoborane precursors (such as, for example, B(NMe2)2Br) using an NH3 and N2 based PEALD process. Unexpectedly, the inventors found that films deposited using NH3 and N2 PEALD and precursors (such as, for example, B(NMe2)2Br) are thicker at the bottom than at the top and sides of high aspect ratio patterned features, and this "bottom-up" deposition is very unusual for any type of PEALD deposition.

[0008] In one aspect, the present invention provides a boron-containing precursor having the structure of Formula I:

[0009] B(NR 1 R 2 ) n X 3-n (I)

[0010] Where R 1 Selected from straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C 10 Alkenyl, straight or branched C3 to C 10 Alkynyl, C1 to C6 dialkylamino, electron withdrawing groups and C4 to C 10 Aryl; R 2 Selected from hydrogen, straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C6 alkenyl, linear or branched C3 to C6 alkynyl, C1 to C6 dialkylamino, C6 to C 10 Aryl, linear or branched C1 to C6 fluorinated alkyl, electron withdrawing group and C4 to C 10 Aryl; X is Cl, Br, I or F; and n = 1 or 2, wherein R 1 and R 2 are optionally linked together to form a ring selected from a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring, and wherein R 1 and R2 It can be the same part or different parts.

[0011] In another aspect, the present invention provides a composition comprising: (a) at least one compound having the structure of Formula I:

[0012] B(NR 1 R 2 ) n X 3-n (I)

[0013] Where R 1 Selected from straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C 10 Alkenyl, straight or branched C3 to C 10 Alkynyl, C1 to C6 dialkylamino, electron withdrawing groups and C4 to C 10 Aryl; R 2 Selected from hydrogen, straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C6 alkenyl, linear or branched C3 to C6 alkynyl, C1 to C6 dialkylamino, C6 to C 10 Aryl, linear or branched C1 to C6 fluorinated alkyl, electron withdrawing group and C4 to C 10 Aryl; X is Cl, Br, I or F; and n = 1 or 2, wherein R 1 and R 2 are optionally linked together to form a ring selected from a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring, and wherein R 1 and R 2 can be the same moiety or different moieties; and (b) a solvent, wherein the solvent has a boiling point, and wherein the difference between the boiling point of the solvent and the boiling point of the at least one boron-containing precursor is 40° C. or less.

[0014] In yet another aspect, the present invention provides a method for depositing a boron-containing film onto at least one surface of a substrate, comprising the steps of: a. providing a substrate in a reactor; b. forming a boron-containing film on the surface in a deposition process selected from chemical vapor deposition and atomic layer deposition processes using a boron-containing precursor selected from a compound having a structure of Formula I:

[0015] B(NR 1 R 2 ) n X 3-n (I)

[0016] Where R 1 Selected from straight chain C1 to C 10Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C 10 Alkenyl, straight or branched C3 to C 10 Alkynyl, C1 to C6 dialkylamino, electron withdrawing groups and C4 to C 10 Aryl; R 2 Selected from hydrogen, straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C6 alkenyl, linear or branched C3 to C6 alkynyl, C1 to C6 dialkylamino, C6 to C 10 Aryl, linear or branched C1 to C6 fluorinated alkyl, electron withdrawing group and C4 to C 10 Aryl; X is Cl, Br, I or F; and n = 1 or 2, wherein R 1 and R 2 are optionally linked together to form a ring selected from a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring, and wherein R 1 and R 2 It can be the same part or different parts; c. purging the reactor with a purge gas; d. providing a nitrogen-containing source to deposit a film on at least one surface; e. purging the reactor with a purge gas; f. optionally introducing at least one silicon-containing source into the reactor; g. if necessary, purging the reactor with a purge gas after step f; h. providing a nitrogen-containing source to deposit a film on at least one surface; and i. purging the reactor with a purge gas, wherein steps b to i are repeated until a film of the desired thickness is obtained.

[0017] The embodiments of the present invention may be used alone or in combination with each other. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 is a graph showing the film thickness obtained after 100 PEALD cycles at 350°C using various BDMABB exposure times;

[0019] Figure 2 is a plot of BN film thickness versus PEALD cycle number to determine the growth rate of boron nitride using BDMABB and N2 plasma;

[0020] Figures 3A to 3D is a TEM image of a 17:1 aspect ratio trench with BN deposited using 600 PEALD cycles using BDMABB and N2 plasma, showing the film thickness at 4 locations along the trench (top, middle 1, middle 2, and bottom);

[0021] Figure 4 is a plot of BN film thickness versus PEALD cycle number to determine the boron nitride growth rate using BDMABB and NH3 plasma;

[0022] Figures 5A to 4 D is a TEM image of a 17:1 aspect ratio trench with BN deposited using 500 PEALD cycles using BDMABB and NH3 plasma, showing the film thickness at 4 locations along the trench (top, middle 1, middle 2, and bottom);

[0023] Figure 6 TEM image of BN film deposited on patterned features (AR 5:1, 0.12 μm wide) using BDMABB and N2 in a PEALD process;

[0024] Figure 7 is a TEM image of a BN film deposited on a patterned feature (AR 5:1, 0.12 μm wide) using BDMABB and NH3 in a PEALD process;

[0025] Figures 8A to 8E TEM image of BDMABB deposited using NH3 PEALD process at 350°C, 200W NH3 plasma for 5 seconds, 3 seconds BDMABB pulse, Figures 8B to 8E They are Fig. 8A A magnified image of the features circled and labeled as top, MID1, MID2, and bottom in FIG. 1 ; and

[0026] Figures 9A to 9E TEM image of BDMABB deposited using N2PEALD process at 350°C, 200W N2 plasma for 5 seconds, 3 seconds BDMABB pulse, Figures 9B to 9E They are Fig.9A A magnified image of the features circled and labeled as top, MID1, MID2, and bottom. DETAILED DESCRIPTION

[0027] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.

[0028] The following detailed description only provides preferred exemplary embodiments and is not intended to limit the scope, applicability or configuration of the present invention. On the contrary, the following detailed description of the preferred exemplary embodiments will provide a feasible description of the preferred exemplary embodiments for implementing the present invention to those skilled in the art. Various changes may be made to the function and arrangement of the elements without departing from the spirit and scope of the present invention as set forth in the appended claims.

[0029] The use of the terms "a" and "an" and "the" and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.

[0030] In the context of describing the present invention (especially in the context of the following claims), recess and feature are used interchangeably and both refer to vias, gaps or areas between fins in a semiconductor substrate.

[0031] As used herein and in the claims, the terms "comprising," "comprises," "including," and "includes" are inclusive or open-ended and do not exclude additional, unrecited elements, composition components, or method steps. Thus, these terms encompass the more restrictive terms "consisting essentially of" and "consisting of." Unless otherwise indicated, all values ​​provided herein are inclusive up to and including the endpoints given, and the values ​​of ingredients or components of the compositions are expressed as weight percents of each ingredient in the composition.

[0032] Unless otherwise specified herein or clearly contradictory to the context, all methods described herein can be performed in any suitable order. Unless otherwise specified, the use of any and all examples or exemplary language (e.g., "such as") provided herein is intended only to better illustrate the present invention without limiting the scope of the present invention. Any language in the specification should not be interpreted as indicating that any unclaimed element is essential to the practice of the present invention.

[0033] Preferred embodiments of the present invention are described herein, including the best mode known to the inventor for implementing the present invention. After reading the foregoing description, changes in those preferred embodiments may become apparent to those of ordinary skill in the art. The inventor expects that a skilled technician will appropriately adopt these changes, and the inventor intends to implement the present invention in a manner different from that specifically described herein. Therefore, the present invention includes all modifications and equivalents allowed by applicable law of the subject matter listed in the appended claims. In addition, unless otherwise specified herein or clearly contradictory to the context, the present invention encompasses any combination of the above-mentioned elements in all possible variations thereof.

[0034] For ease of reference, "microelectronic device" corresponds to semiconductor substrates, flat panel displays, phase change memory devices, solar panels, and other products including solar cell devices, photovoltaic devices, and microelectromechanical systems (MEMS), which are manufactured for microelectronics, integrated circuits, energy harvesting, or computer chip applications. It should be understood that the terms "microelectronic device," "microelectronic substrate," and "microelectronic device structure" are not meant to be limiting in any way and include any substrate or structure that will ultimately become a microelectronic device or microelectronic assembly. Microelectronic devices may be patterned, blanket, control, and / or test devices.

[0035] "Substantially free" is defined herein as less than 2 weight percent, preferably less than 1 weight percent, more preferably less than 0.5 weight percent, and most preferably less than 0.1 weight percent. "Substantially free" also includes 0.0 weight percent. The term "free" means 0.0 weight percent.

[0036] As used herein, "about" is intended to correspond to ±5% of the stated value.

[0037] "Substantially free" is defined herein as less than 2 wt%, preferably less than 1 wt%, more preferably less than 0.5 wt%, even more preferably less than 0.1 wt%. The term "free" is defined herein as 0 wt%.

[0038] As used herein, the term "halo" refers to a halogen group, and includes, but is not limited to, fluoro, chloro, bromo, and iodo.

[0039] As described more fully below, the compositions of the present invention may be embodied in a wide variety of specific formulations.

[0040] In all such compositions wherein specific components of the composition are discussed with reference to weight percent ranges that include a lower limit of zero, it is understood that such components may or may not be present in various embodiments of the composition, and where such components are present, they may be present in concentrations as low as 0.001 weight percent, based on the total weight of the composition in which such components are used.

[0041] Described herein are compositions and methods involving forming stoichiometric or non-stoichiometric boron-containing films or materials, such as but not limited to silicon oxide, carbon-doped silicon oxide films, silicon oxynitride, carbon-doped silicon oxynitride films, or combinations thereof, at one or more temperatures from room temperature (e.g., about 25° C.) to about 1000° C., or from room temperature to about 400° C., or from room temperature to about 300° C., or from room temperature to about 200° C., or from room temperature to about 100° C. The films described herein are deposited in a deposition process such as a chemical vapor deposition (CVD) process, an atomic layer deposition (ALD), or an ALD-like process, such as but not limited to a plasma-enhanced ALD or a plasma-enhanced cyclic chemical vapor deposition process (CCVD).

[0042] In one aspect, the present invention provides a boron-containing precursor having the structure of Formula I:

[0043] B(NR 1 R 2 ) n X 3-n (I)

[0044] Where R 1 Selected from straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C 10 Alkenyl, straight or branched C3 to C 10 Alkynyl, C1 to C6 dialkylamino, electron withdrawing groups and C4 to C 10 Aryl; R 2 Selected from hydrogen, straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C6 alkenyl, linear or branched C3 to C6 alkynyl, C1 to C6 dialkylamino, C6 to C 10 Aryl, linear or branched C1 to C6 fluorinated alkyl, electron withdrawing group and C4 to C 10 Aryl; X is Cl, Br, I or F; and n = 1 or 2, wherein R 1 and R 2 are optionally linked together to form a ring selected from a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring, and wherein R 1 and R 2 It can be the same part or different parts.

[0045] In certain embodiments of Formula I, R 1 and R 2 In a specific embodiment, R 1 and R 2 is selected from a linear or branched C3 to C6 alkyl group and connected to form a cyclic ring. As understood by those skilled in the art, in R 1 and R 2 When connected together to form a ring, R 1 Included for connecting R 2 In some embodiments, the ring structure may be unsaturated, such as, for example, a cyclic alkyl ring, or saturated, such as an aryl ring. In addition, in some embodiments, the ring structure may be substituted or unsubstituted by one or more atoms or groups. Exemplary cyclic ring groups include, but are not limited to, pyrrolidinyl, piperidino and 2,6-dimethylpiperidino.

[0046] In an alternative embodiment of Formula I, R 1 and R 2 are not connected together to form a ring. In other embodiments, R 1 and R 2 are different; X is Cl, Br, I or F, and n=1 or 2. In certain preferred embodiments of Formula I, R 1 and R 2 It is a bulky alkyl group, such as isopropyl, tert-butyl, and tert-pentyl.

[0047] In the above formula and throughout the specification, the term "alkyl" means a straight or branched functional group having 1 to 10 or 1 to 6 carbon atoms. Exemplary straight chain alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl. Exemplary branched alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, tert-pentyl, isohexyl, and neohexyl. In certain embodiments, the alkyl may have one or more functional groups connected thereto, such as, but not limited to, an alkoxy, a dialkylamino, or a combination thereof connected thereto. In other embodiments, the alkyl does not have one or more functional groups connected thereto. The hydrocarbon group may be saturated, or alternatively, unsaturated. The alkyl may also be substituted or have one or more heteroatoms (such as halogen or O) or be unsubstituted.

[0048] In the above formula and throughout the specification, the term "cycloalkyl" refers to a cyclic functional group having 4 to 10 carbon atoms. Exemplary cycloalkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

[0049] In the above formulae and throughout the specification, the term "alkenyl" denotes a group having one or more carbon-carbon double bonds and having from 2 to 10 or from 2 to 10 or from 2 to 6 carbon atoms.

[0050] In the above formulae and throughout the specification, the term "alkynyl" denotes a group having one or more carbon-carbon triple bonds and having from 3 to 10 or from 2 to 10 or from 2 to 6 carbon atoms.

[0051] In the above formula and throughout the specification, the term "aryl" refers to an aromatic cyclic functional group having 4 to 10 carbon atoms, 5 to 10 carbon atoms, or 6 to 10 carbon atoms. Exemplary aryl groups include, but are not limited to, phenyl, benzyl, chlorobenzyl, tolyl, o-xylyl, 1,2,3-triazolyl, pyrrolyl and furanyl, pyridazinyl, pyrimidinyl, pyrazinyl and imidazolyl.

[0052] In the above formula and throughout the specification, the term "amino" means a radical derived from a radical having the formula HNR 2 R 3The organic amino group of the organic amine has 1 to 10 carbon atoms. Exemplary amino groups include, but are not limited to, secondary amino groups derived from secondary amines, such as dimethylamino (Me2N-), diethylamino (Et2N-), ethylmethylamino (EtMeN-), diisopropylamino ( i Pr2N-); primary amino groups derived from primary amines, such as methylamino (MeNH-), ethylamine (EtNH-), isopropylamino ( i PrNH-), sec-butylamino ( s BuNH-), tert-butylamino ( t BuNH-).

[0053] Examples of the boron-containing precursor having a chemical structure represented by Formula I include bis(dimethylamino)chloroborane, bis(dimethylamino)bromoborane, bis(dimethylamino)iodoborane, bis(diethylamino)chloroborane, bis(diethylamino)bromoborane, bis(diethylamino)iodoborane, bis(ethylmethylamino)chloroborane, bis(ethylmethylamino)bromoborane, bis(ethylmethylamino)iodoborane, (diisopropylamino)dichloroborane, (diisopropylamino)dibromoborane, (diisopropylamino)diiodoborane, (pyrrolidinyl)chloroborane, (pyrrolidinyl)bromo ... Borane, (2,6-dimethyl-piperidino)dichloroborane, (2,6-dimethyl-piperidino)dibromoborane and (2,6-dimethyl-piperidino)diiodoborane. Preferred boron-containing precursors are bis(dimethylamino)bromoborane or bis(ethylmethylamino)bromoborane.

[0054] In some embodiments, the boron-containing precursor represented by Formula I is at least one selected from the following: in some embodiments, bis(ethylmethylamino)chloroborane, bis(ethylmethylamino)bromoborane, bis(ethylmethylamino)iodoborane; (2-methyl-pyrrolidinyl)chloroborane, (2-methyl-pyrrolidinyl)bromoborane, (2-methyl-pyrrolidinyl)iodoborane, (2,5-dimethyl-pyrrolidinyl)chloroborane, (2,5-dimethyl-pyrrolidinyl)bromoborane and (2,5-dimethyl-pyrrolidinyl)iodoborane.

[0055] In other embodiments, the boron-containing precursor represented by Formula I is at least one selected from the following:

[0056]

[0057] During the manufacture of electronic devices such as integrated circuits, features or depressions such as gaps between fins, grooves or regions can be generated on the substrate surface. Depending on the specific application, the filling features or depressions can take a variety of forms. Typical depression filling processes may have disadvantages, including the formation of voids in the depressions. When the filling material forms a compaction near the top of the depression before the depression is completely filled, gaps and seams may be formed. Such gaps and seams may damage the isolation of devices on the integrated circuit and their overall structural integrity. Unexpectedly, the inventors have found that according to the method described below, using both NH3 and N2 PEALD, the film deposited using a boron-containing precursor represented by Formula I (e.g., bis(dimethylamino)bromoborane (BDMABB)) is thicker at the bottom than the top and sides of the high aspect ratio patterned features. This "bottom-up" deposition is very uncommon for any type of PEALD deposition and can potentially be used for gap filling applications in semiconductor device manufacturing. Without being bound by theory, it is believed that the byproduct during PEALD deposition is HX, such as HBr or HCl, which can potentially etch the as-deposited silicon nitride on the sidewalls of features (e.g., vias or trenches), and therefore, the silicon nitride growth rate is higher on the bottom surface than on the sidewalls, thereby unexpectedly enabling bottom-up filling. Bottom-up deposition is observed for high aspect ratio features, where the aspect ratio is defined as the depth of the feature divided by the width of the feature, such as 5:1 or higher, 8:1 or higher, 10:1 or higher, 20:1 or higher, 30:1 or higher, 40:1 or higher, 40:1 or higher, 50:1 or higher, 60:1 or higher, 80:1 or higher, and 100:1 or higher. Alternatively, bottom-up deposition is observed for high aspect ratio features, where the aspect ratio is defined as the depth of the feature divided by the width of the feature, such as 5:1 to 100:1, 8:1 to 100:1, 10:1 to 100:1, 20:1 to 100:1, 30:1 to 100:1, 40:1 to 100:1, 40:1 to 100:1, 50:1 to 100:1, 60:1 to 100:1, and 80:1 to 100:1.

[0058] Therefore, in one aspect, the present invention provides a method for depositing a boron-containing film (e.g., a boron nitrite film) in a high aspect ratio feature from the bottom up, such that the growth rate of the film on the bottom surface of the high aspect ratio feature is higher than the growth rate on the sidewall surface. The method comprises the following steps:

[0059] a. providing a substrate in a reactor;

[0060] b. introducing into the reactor at least one boron-containing precursor represented by formula I:

[0061] B(NR 1 R 2 ) n X3-n (I)

[0062] Where R 1 Selected from straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C 10 Alkenyl, straight or branched C3 to C 10 Alkynyl, C1 to C6 dialkylamino, electron withdrawing groups and C4 to C 10 Aryl; R 2 Selected from hydrogen, straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C6 alkenyl, linear or branched C3 to C6 alkynyl, C1 to C6 dialkylamino, C6 to C 10 Aryl, linear or branched C1 to C6 fluorinated alkyl, electron withdrawing group and C4 to C 10 Aryl; X is Cl, Br, I or F; and n = 1 or 2, wherein R 1 and R 2 are optionally linked together to form a ring selected from a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring, and wherein R 1 and R 2 It can be the same part or different parts;

[0063] c. purging the reactor with a purge gas;

[0064] d. providing a nitrogen-containing plasma source to deposit a film onto at least one surface; and

[0065] e. purging the reactor with a purge gas,

[0066] Steps b to e are repeated until a film of desired thickness is obtained.

[0067] In a specific embodiment, the deposition step is performed at one or more temperatures in the range of about room temperature to about 1000° C., or room temperature to about 400° C., or room temperature to about 300° C., or room temperature to about 200° C., or room temperature to about 100° C. Preferred nitrogen-containing sources may be selected from N2 plasma, ammonia plasma, and N2 plasma / ammonia plasma.

[0068] In another aspect, a composition is disclosed, comprising: (a) at least one compound having the structure of Formula I:

[0069] B(NR 1 R 2 ) n X 3-n (I)

[0070] Where R 1Selected from straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C 10 Alkenyl, straight or branched C3 to C 10 Alkynyl, C1 to C6 dialkylamino, electron withdrawing groups and C4 to C 10 Aryl; R 2 Selected from hydrogen, straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C6 alkenyl, linear or branched C3 to C6 alkynyl, C1 to C6 dialkylamino, C6 to C 10 Aryl, linear or branched C1 to C6 fluorinated alkyl, electron withdrawing group and C4 to C 10 Aryl; X is Cl, Br, I or F; and n = 1 or 2, wherein R 1 and R 2 are optionally linked together to form a ring selected from a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring, and wherein R 1 and R 2 can be the same moiety or different moieties; and (b) a solvent, wherein the solvent has a boiling point, and wherein the difference between the boiling point of the solvent and the boiling point of the at least one boron-containing precursor is 40° C. or less.

[0071] In certain embodiments of the compositions described herein, exemplary solvents may include, but are not limited to, ethers, tertiary amines, alkyl hydrocarbons, aromatic hydrocarbons, tertiary amino ethers, and combinations thereof. In certain embodiments, the difference between the boiling point of the organoaminodisilane and the boiling point of the solvent is 40° C. or less. It is believed that some solvents may help stabilize the organoaminoborane in the liquid phase or even the gas phase during storage or delivery.

[0072] In another aspect, a method for forming a boron-containing film on at least one surface of a substrate is provided, comprising: providing at least one surface of the substrate in a reaction chamber; and forming the boron-containing film on the at least one surface by a deposition process selected from a chemical vapor deposition process and an atomic layer deposition process using a boron-containing precursor represented by Formula I:

[0073] B(NR 1 R 2 ) n X 3-n (I)

[0074] Where R 1 Selected from straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C 10 Alkenyl, straight or branched C3 to C 10Alkynyl, C1 to C6 dialkylamino, electron withdrawing groups and C4 to C 10 Aryl; R 2 Selected from hydrogen, straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C6 alkenyl, linear or branched C3 to C6 alkynyl, C1 to C6 dialkylamino, C6 to C 10 Aryl, linear or branched C1 to C6 fluorinated alkyl, electron withdrawing group and C4 to C 10 Aryl; X is Cl, Br, I or F; and n = 1 or 2, wherein R 1 and R 2 are optionally linked together to form a ring selected from a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring, and wherein R 1 and R 2 It can be the same part or different parts.

[0075] In another aspect, a method of forming a boron oxide or boron oxycarbide film by an atomic layer deposition process or an ALD-like process is provided, the method comprising the steps of:

[0076] a. providing a substrate in a reactor;

[0077] b. introducing into the reactor at least one boron-containing precursor represented by formula I:

[0078] B(NR 1 R 2 ) n X 3-n (I)

[0079] Where R 1 Selected from straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C 10 Alkenyl, straight or branched C3 to C 10 Alkynyl, C1 to C6 dialkylamino, electron withdrawing groups and C4 to C 10 Aryl; R 2 Selected from hydrogen, straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C6 alkenyl, linear or branched C3 to C6 alkynyl, C1 to C6 dialkylamino, C6 to C 10 Aryl, linear or branched C1 to C6 fluorinated alkyl, electron withdrawing group and C4 to C 10 Aryl; X is Cl, Br, I or F; and n = 1 or 2, wherein R 1 and R 2are optionally linked together to form a ring selected from a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring, and wherein R 1 and R 2 It can be the same part or different parts;

[0080] c. purging the reactor with a purge gas;

[0081] d. providing a nitrogen-containing source to deposit a film onto at least one surface; and

[0082] e. purging the reactor with a purge gas,

[0083] Steps b to e are repeated until a film of desired thickness is obtained.

[0084] In a particular embodiment, the depositing step is performed at one or more temperatures ranging from about room temperature to about 1000°C, or room temperature to about 400°C, or room temperature to about 300°C, or room temperature to about 200°C, or room temperature to about 100°C.

[0085] In another aspect, a method for forming a boron-doped silicon oxide or boron-doped silicon oxycarbide film by an atomic layer deposition process or an ALD-like process is provided, the method comprising the following steps:

[0086] a. providing a substrate in a reactor;

[0087] b. introducing into the reactor at least one boron-containing precursor represented by formula I:

[0088] B(NR 1 R 2 ) n X 3-n (I)

[0089] Where R 1 Selected from straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C 10 Alkenyl, straight or branched C3 to C 10 Alkynyl, C1 to C6 dialkylamino, electron withdrawing groups and C4 to C 10 Aryl; R 2 Selected from hydrogen, straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C6 alkenyl, linear or branched C3 to C6 alkynyl, C1 to C6 dialkylamino, C6 to C 10 Aryl, linear or branched C1 to C6 fluorinated alkyl, electron withdrawing group and C4 to C 10 Aryl; X is Cl, Br, I or F; and n = 1 or 2, wherein R 1 and R2 are optionally linked together to form a ring selected from a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring, and wherein R 1 and R 2 It can be the same part or different parts;

[0090] c. purging the reactor with a purge gas;

[0091] d. providing a nitrogen-containing source to deposit a film onto at least one surface;

[0092] e. purging the reactor with a purge gas;

[0093] f. introducing at least one silicon-containing source into the reactor;

[0094] g. Purge the reactor with a purge gas;

[0095] h. providing an oxygen-containing source to deposit a film onto at least one surface; and

[0096] i. purging the reactor with a purge gas,

[0097] wherein steps b to i are repeated until a film of desired thickness is obtained. In some embodiments, steps b to e are repeated, and then steps f to i are repeated, to deposit a nanolaminated layer composed of boron oxide and silicon oxide. In other embodiments, steps f to i may be performed and repeated, and then steps b to e may be repeated. For a nanolaminated body, the thickness of silicon oxide may be to to to to to In the range of to to to to to In a specific embodiment, the depositing step is performed at one or more temperatures in the range of about room temperature to about 1000°C, or room temperature to about 400°C, or room temperature to about 300°C, or room temperature to about 200°C, or room temperature to about 100°C. In another specific embodiment, when a silicon-containing source having at least one SiH3 group is used, such as diisopropylaminosilane, di-sec-butylaminosilane, diisopropylaminodisilane, di-sec-butylaminodisilane, the depositing step is performed at a temperature below 400°C.

[0098] In yet another aspect, a method of forming a boron nitride, boron carbonitride or boron carbon oxynitride film by an atomic layer deposition process or an ALD-like process is provided, the method comprising the steps of:

[0099] a. providing a substrate in a reactor;

[0100] b. introducing into the reactor at least one boron-containing precursor represented by formula I:

[0101] B(NR 1 R 2 ) n X 3-n (I)

[0102] Where R 1 Selected from straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C 10 Alkenyl, straight or branched C3 to C 10 Alkynyl, C1 to C6 dialkylamino, electron withdrawing groups and C4 to C 10 Aryl; R 2 Selected from hydrogen, straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C6 alkenyl, linear or branched C3 to C6 alkynyl, C1 to C6 dialkylamino, C6 to C 10 Aryl, linear or branched C1 to C6 fluorinated alkyl, electron withdrawing group and C4 to C 10 Aryl; X is Cl, Br, I or F; and n = 1 or 2, wherein R 1 and R 2 are optionally linked together to form a ring selected from a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring, and wherein R 1 and R 2 It can be the same part or different parts;

[0103] c. purging the reactor with a purge gas;

[0104] d. providing a nitrogen-containing source to deposit a film onto at least one surface; and

[0105] e. purging the reactor with a purge gas;

[0106] Steps b to e are repeated until a film of desired thickness is obtained. In a specific embodiment, the deposition step is performed at one or more temperatures in the range of about room temperature to about 1000°C, or room temperature to about 400°C, or room temperature to about 300°C, or room temperature to about 200°C, or room temperature to about 100°C.

[0107] In another aspect, a method for forming a boron-doped silicon nitride, a boron-doped silicon carbonitride, or a boron-doped silicon oxycarbonitride film by an atomic layer deposition process or an ALD-like process is provided, the method comprising the following steps:

[0108] a. providing a substrate in a reactor;

[0109] b. introducing into the reactor at least one boron-containing precursor represented by formula I:

[0110] B(NR 1 R 2 ) n X 3-n (I)

[0111] Where R 1 Selected from straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C 10 Alkenyl, straight or branched C3 to C 10 Alkynyl, C1 to C6 dialkylamino, electron withdrawing groups and C4 to C 10 Aryl; R 2 Selected from hydrogen, straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C6 alkenyl, linear or branched C3 to C6 alkynyl, C1 to C6 dialkylamino, C6 to C 10 Aryl, linear or branched C1 to C6 fluorinated alkyl, electron withdrawing group and C4 to C 10 Aryl; X is Cl, Br, I or F; and n = 1 or 2, wherein R 1 and R 2 are optionally linked together to form a ring selected from a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring, and wherein R 1 and R 2 It can be the same part or different parts;

[0112] c. purging the reactor with a purge gas;

[0113] d. providing a nitrogen-containing source to deposit a film onto at least one surface;

[0114] e. purging the reactor with a purge gas;

[0115] f. introducing at least one silicon-containing source into the reactor;

[0116] g. Purge the reactor with a purge gas;

[0117] h. providing a nitrogen-containing source to deposit a film onto at least one surface; and

[0118] i. purging the reactor with a purge gas,

[0119] Steps b to g are repeated until a film of the desired thickness is obtained. In some embodiments, steps b to e are repeated, and then steps f to i are repeated, to deposit a nanolaminate layer composed of boron nitride and silicon nitride. In other embodiments, steps f to i may be performed and repeated first, and then steps b to e may be repeated. For a nanolaminate, the thickness of the silicon nitride may be to to to to to In the range of to to to to to In a specific embodiment, the depositing step is performed at one or more temperatures in the range of about room temperature to about 1000°C, or room temperature to about 400°C, or room temperature to about 300°C, or room temperature to about 200°C, or room temperature to about 100°C. In another specific embodiment, when a silicon-containing source having at least one SiH3 group is used, such as diisopropylaminosilane, di-sec-butylaminosilane, diisopropylaminodisilane, di-sec-butylaminodisilane, the depositing step is performed at a temperature below 400°C.

[0120] In embodiments of the method wherein a silicon-containing source is used, the silicon-containing source includes, but is not limited to, trisilylamine (TSA), bis(dimethylsilylamino)silane, bis(tert-butylamino)silane (BTBAS), bis(dimethylamino)silane, bis(diethylamino)silane, bis(ethylmethylamino)silane, tris(dimethylamino)silane, tris(ethylmethylamino)silane, tetrakis(dimethylamino)silane, diisopropylaminosilane, di-sec-butylaminosilane, di-tert-butylaminosilane, 2,6-dimethylpiperidinosilane, 2,2,6,6-tetramethylpiperidinosilane, cyclohexylisopropylaminosilane, phenylmethylaminosilane, phenylethylaminodisilane, dicyclohexylaminosilane, diisopropylaminodisil ... di-sec-butylaminosilane, di-tert-butylaminosilane, di-sec-butylaminosilane, di-tert-butylaminosilane, di-sec-butylaminosilane, di-tert-butylaminosilane, di-sec-butylaminosilane, di-tert-butylaminosilane, di-sec-butylaminosilane, di-tert-butylaminosilane, di-sec-butylaminosilane, di-tert-butylaminosilane, di-sec-butylaminosilane, di-sec- sec-Butylaminodisilane, di-tert-butylaminodisilane, 2,6-dimethylpiperidinodisilane, 2,2,6,6-tetramethylpiperidinodisilane, cyclohexylisopropylaminodisilane, phenylmethylaminodisilane, phenylethylaminodisilane, dicyclohexylaminodisilane, dimethylaminotrimethylsilane, dimethylaminotrimethylsilane, diisopropylaminotrimethylsilane, piperidinotrimethylsilane, 2,6-dimethylpiperidinotrimethylsilane, di-sec-butylaminotrimethylsilane, isopropylsec-butylaminotrimethylsilane, tert-butylaminotrimethylsilane, isopropylaminotrimethylsilane, diethylaminodimethylsilane, dimethylaminodimethylsilane, diisopropylaminodimethylsilane, piperidinodimethylsilane, 2 ,6-dimethylpiperidinodimethylsilane, di-sec-butylaminodimethylsilane, isopropyl-sec-butylaminodimethylsilane, tert-butylaminodimethylsilane, isopropylaminodimethylsilane, tert-amylaminodimethylaminosilane, bis(dimethylamino)methylsilane, bis(diethylamino)methylsilane, bis(diisopropylamino)methylsilane, bis(isopropyl-sec-butylamino)methylsilane, bis(2,6-dimethylpiperidino)methylsilane, bis(isopropylamino)methylsilane, bis(tert-butylamino)methylsilane, bis(sec-butylamino)methylsilane, bis(tert-amylamino)methylsilane, diisopropylaminodisilane and di-sec-butylaminodisilane, diisopropylaminotrisilylamine, diethylaminotrisilylamine, Isopropylaminotrisilylamine and cyclohexylmethylaminotrisilylamine, 2-dimethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-diethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-ethylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-isopropylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-dimethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-diethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-isopropylamino-2,4,4,6,6,8,88-heptamethylcyclotetrasiloxane, 2-dimethylamino-2,4,6-trimethylcyclotrisiloxane, 2-diethylamino-2,4,6-trimethylcyclotrisiloxane, 2-ethylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-isopropylamino-2,4,6-trimethylcyclotrisiloxane, 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane and 2-isopropylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane and 2-cyclohexylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane.

[0121] Deposition methods disclosed herein may involve one or more purge gases. The purge gas used to purge unconsumed reactants and / or reaction byproducts is an inert gas that does not react with the precursor. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N2), helium (He), neon, hydrogen (H2) and mixtures thereof. In certain embodiments, a purge gas (such as Ar) is supplied to the reactor at a flow rate in the range of about 10 to about 2000 sccm for about 0.1 to 1000 seconds to purge unreacted materials and any byproducts that may remain in the reactor.

[0122] In certain embodiments, the boron oxide, boron oxide silicon or boron-doped silicon oxycarbide film deposited using the methods described herein is formed in the presence of an oxygen-containing source, such as ozone, water (H2O) (e.g., deionized water, purified water and / or distilled water), oxygen (O2), ozone plasma, oxygen plasma, NO, N2O, NO2, carbon monoxide (CO), carbon dioxide (CO2) and combinations thereof. The oxygen-containing source gas may be provided by an in-situ or remote plasma generator to provide an oxygen-containing plasma source including oxygen, such as oxygen plasma, oxygen / argon plasma, oxygen / helium plasma, ozone plasma, water plasma, nitrous oxide plasma or carbon dioxide plasma.

[0123] In some embodiments, the boron-containing film includes boron, silicon and nitrogen to provide boron nitride, boron-doped silicon nitride or boron-doped carbon silicon nitride film. In these embodiments, the boron-containing film deposited using the method described herein is formed in the presence of a nitrogen-containing source. The nitrogen-containing source can be introduced into the reactor in the form of at least one nitrogen source and / or can be incidentally present in other precursors used in the deposition process. Suitable nitrogen-containing source gases can include, for example, ammonia, hydrazine, monoalkyl hydrazine (e.g., methyl hydrazine, tert-butyl hydrazine), dialkyl hydrazine (e.g., 1,1-dimethyl hydrazine, 1,2-dimethyl hydrazine), organic amine (e.g., methylamine, dimethylamine, ethylamine, diethylamine, tert-butylamine), organic amine plasma, nitrogen, nitrogen plasma, nitrogen / hydrogen, nitrogen / helium, nitrogen / argon plasma, ammonia plasma, ammonia / helium plasma, ammonia / argon plasma, ammonia / nitrogen plasma, NF3, NF3 plasma and mixtures thereof.

[0124] In certain embodiments, the boron-containing film comprises a boron content ranging from 0.5% to 50%, preferably 1% to 20%, as measured by XPS, and can be selected from boron oxide, boron nitride, boron carbonitride, boron-doped silicon oxide, boron-doped silicon oxycarbide, boron-doped silicon oxynitride, boron-doped silicon nitride, and boron-doped silicon carbonitride that can be used in the manufacture of semiconductor processes, such as solid diffusion layers for producing FinFETs.

[0125] The respective steps of supplying the boron-containing precursor, the oxygen source, and / or other precursors, source gases, and / or reagents may be performed by varying the time at which they are supplied to change the stoichiometric composition of the resulting film.

[0126] Energy is applied to at least one of the precursor, the oxygen-containing source, or a combination thereof to induce a reaction and form a film or coating on the substrate. Such energy may be provided by, but is not limited to, heat, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, X-rays, electron beams, photons, remote plasma methods, and combinations thereof. In certain embodiments, a secondary RF frequency source may be used to change the plasma characteristics at the substrate surface. In embodiments where the deposition involves plasma, the plasma generation process may include a direct plasma generation process, in which the plasma is generated directly in the reactor, or alternatively, a remote plasma generation process, in which the plasma is generated outside the reactor and supplied to the reactor.

[0127] At least one precursor can be delivered to the reaction chamber in a variety of ways, such as a plasma enhanced cyclic CVD or PEALD reactor or an intermittent furnace reactor. In one embodiment, a liquid delivery system can be used. In alternative embodiments, a combined liquid delivery and flash process unit can be used, such as a turbo evaporator manufactured by MSP Corporation of Shoreview, MN, to enable quantitative delivery of low volatility materials, which results in repeatable delivery and deposition without thermal decomposition of the precursor. In liquid delivery formulations, the precursors described herein can be delivered in neat liquid form, or alternatively, can be used in solvent formulations or compositions comprising the same. Therefore, in certain embodiments, the precursor formulation can include a solvent component with suitable properties, such as may be desired and advantageous in a given end-use application, to form a film on a substrate.

[0128] For those embodiments in which the precursors described herein are used in a composition comprising a solvent and at least one boron-containing precursor and optionally a silicon-containing precursor described herein, the selected solvent or mixture thereof does not react with the boron-containing precursor. The amount of solvent in the composition by weight percentage is in the range of 0.5 wt % to 99.5 wt % or 10 wt % to 75 wt %. In this or other embodiments, the boiling point (bp) of the solvent is similar to the bp of the precursor, or the difference between the bp of the solvent and the bp of the precursor is 40°C or less, 30°C or less, or 20°C or less, or 10°C or less. Alternatively, the difference between the boiling points is within the range of any one or more of the following endpoints: 0, 10, 20, 30 or 40°C. Examples of suitable ranges of boiling point differences include, but are not limited to, 0 to 40°C, 20°C to 30°C, or 10°C to 30°C. Examples of suitable solvents in the composition include, but are not limited to, ethers (e.g., 1,4-dioxane, dibutyl ether), tertiary amines (e.g., pyridine, 1-methylpiperidine, 1-ethylpiperidine, N,N'-dimethylpiperazine, N,N,N',N'-tetramethylethylenediamine), nitriles (e.g., benzonitrile), alkanes (e.g., octane, nonane, dodecane, ethylcyclohexane), aromatic hydrocarbons (e.g., toluene, mesitylene), tertiary amino ethers (e.g., bis(2-dimethylaminoethyl) ether), or mixtures thereof.

[0129] As previously described, the purity level of the boron-containing precursor is sufficiently high to be acceptable enough for reliable semiconductor manufacturing. In certain embodiments, the precursors described herein contain less than 2% by weight, or less than 1% by weight, or less than 0.5% by weight of one or more of the following impurities: free amines, free halides or halide ions, and higher molecular weight species. The higher purity levels of the precursors described herein can be obtained by one or more of the following methods: purification, adsorption, and / or distillation.

[0130] In one embodiment of the methods described herein, a plasma enhanced cyclic deposition process such as PEALD-like or PEALD may be used, where the deposition is performed using precursors and oxygen-containing or nitrogen-containing sources. A PEALD-like process is defined as a plasma enhanced cyclic CVD process, but still provides highly conformal boron-containing films.

[0131] In certain embodiments, the gas line connecting the precursor tank to the reaction chamber is heated to one or more temperatures according to the process requirements, and the container of the precursor is maintained at one or more temperatures for bubbling. In other embodiments, the solution containing the precursor is injected into a vaporizer maintained at one or more temperatures for direct liquid injection.

[0132] Flows of argon and / or other gases may be used as carrier gases to help deliver the vapor of at least one silicon precursor to the reaction chamber during the precursor pulse. In certain embodiments, the reaction chamber process pressure is about 50 mTorr to 10 Torr. In other embodiments, the reaction chamber process pressure may be as high as 760 Torr.

[0133] In a typical PEALD or PEALD-like process (eg, PECCVD process), a substrate, such as a silicon oxide substrate, is heated on a heating stage in a reaction chamber and initially exposed to a precursor to allow chemical adsorption of the complex onto the substrate surface.

[0134] As previously described, a purge gas (e.g., argon) purges the unadsorbed excess complex from the process chamber. After sufficient purging, an oxygen source can be introduced into the reaction chamber to react with the adsorbed surface, followed by another gas purge to remove the reaction byproducts from the chamber. The process cycle can be repeated to obtain the desired film thickness. In some cases, pumping can replace purging with an inert gas, or both can be used to remove unreacted precursors.

[0135] In this or other embodiments, it should be understood that the steps of the methods described herein can be performed in a variety of orders, can be performed sequentially, can be performed simultaneously (e.g., during at least a portion of another step), and any combination thereof. The respective steps of supplying precursors and oxygen- or nitrogen-containing source gases can be performed by varying the duration of supplying them to vary the stoichiometric composition of the resulting dielectric film. In addition, the purge time after the precursor or oxygen- or nitrogen-containing step can be minimized to <0.1 s, so that the throughput can be increased.

[0136] Various commercial ALD reactors, such as single wafer, semi-batch, batch furnaces, or roll-to-roll reactors, can be used to deposit the boron-containing films or materials described herein.

[0137] Process temperatures for the methods described herein use one or more of the following temperatures as endpoints: 0, 25, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 500, 525, 550, 575, 600. Exemplary temperature ranges include, but are not limited to, the following: about 0°C to about 600°C; or about 25°C to about 500°C; or about 150°C to about 400°C; or about 25°C to about 300°C, or about 25°C to about 200°C.

[0138] As previously described, the methods described herein can be used to deposit a boron-containing film on at least a portion of a substrate. Examples of suitable substrates include, but are not limited to, silicon, SiO2, Si3N4, OSG, FSG, silicon carbide, hydrogenated silicon carbide, silicon nitride, hydrogenated silicon nitride, silicon carbonitride, hydrogenated silicon carbonitride, boron nitride, anti-reflective coatings, photoresists, germanium, germanium-containing, boron-containing, Ga / As, flexible substrates, organic polymers, porous organic and inorganic materials, metals (such as copper and aluminum), and diffusion barriers (such as but not limited to TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN). The film is compatible with a variety of subsequent processing steps, such as, for example, chemical mechanical planarization (CMP) and anisotropic etching processes.

[0139] The features and advantages are more fully shown by the illustrative embodiments discussed below.

[0140] Example

[0141] In the following examples, unless otherwise stated, the properties are obtained from sample films deposited on medium resistivity (14-17 S2-cm) single crystal silicon wafer substrates. All film depositions were performed using an ALD tool manufactured by CN-1 with a showerhead design and using a 13.56 MHz direct plasma under typical process conditions, with the chamber pressure fixed at a pressure in the range of about 1 to about 5 Torr unless otherwise stated. An additional inert gas such as argon or nitrogen was used to maintain the chamber pressure. The organoborane precursor was delivered by bubbling 50 sccm argon through the container while the container was maintained at 50°C. The typical RF power used on an electrode area of ​​200 mm wafer was 200 W to provide 0.64 W / cm 2 power density.

[0142] The refractive index (RI) and thickness of the deposited film are measured using an ellipsometer (e.g., Ellipso Technology's model Elli-SE-UaM12 at room temperature) or a transmission electron microscope (HRTEM of JEOL, model JEM-3010). Film composition is analyzed using x-ray photoelectron spectroscopy (XPS) (Thermo Fisher Scientific K-Alpha+XPS). Film crystallinity is measured by XRD using (Rigaku Corp, model SmartLab). Film surface roughness is measured by atomic force microscopy (AFM, using XE-150, Parksystems). All measurements are performed according to conventional methods.

[0143] Example 1 :PEALD Boron Nitride Films Using Bis(Dimethylamino)Bromoborane (BDMABB) and Nitrogen Plasma

[0144] The silicon wafer was loaded into a CN-1 reactor equipped with a showerhead design, which used a 13.56 MHz direct plasma and was heated to 350°C with a chamber pressure of 2 Torr. Bis(dimethylamino)bromoborane (BDMABB) was used as a boron nitride precursor and was delivered to the reaction chamber by bubbling 50 sccm of argon through a liquid maintained at 50°C. The ALD cycle consisted of the following process steps:

[0145] a. Prepare the reactor and load the wafer

[0146] Chamber pressure: 2 Torr.

[0147] b. Introducing BDMABB precursor into the reactor

[0148] Bubbling: BDMABB precursor 50 sccm Ar flow

[0149] N2 gas flow: 1000sccm

[0150] BDMABB pulse: 1 to 5 seconds

[0151] c. Purge excess precursor

[0152] N2 gas flow: 1000sccm

[0153] Purge time: 20 seconds.

[0154] d. Introducing plasma

[0155] N2 gas flow: 1000sccm

[0156] Plasma power: 200W

[0157] Plasma pulse: 5 seconds

[0158] e.Purge

[0159] N2 gas flow: 1000sccm

[0160] Purge time: 20 seconds

[0161] For the boron precursor saturation test, steps b to e were repeated for 100 cycles with 1, 2, 3, 4, and 5 s BDMABB pulses, respectively. Figure 1 As shown, it proves that BDMABB reaches ALD self-limitation at about 3 seconds. Table 1 shows the film thickness and refractive index of the films deposited when steps b to e are repeated for 100, 250, 500 and 600 cycles, respectively.

[0162] Table 1 Boron nitride thickness and refractive index of films deposited with different numbers of PEALD cycles using BDMABB and N2 plasma.

[0163]

[0164] like Figure 2 The growth rate of boron nitride is calculated from the plot of thickness versus cycle number as shown in

[0165] The film was deposited using 600 cycles for analysis. XPS analysis showed that the film contained 53.4 atomic % boron, 36.4 atomic % nitrogen, 7.0 atomic % carbon, and 3.2 atomic % oxygen (from air). The XRD diffraction pattern showed no features, indicating that the film was amorphous. AFM analysis showed that the average roughness of the film was 2.05 nm.

[0166] Boron nitride films were deposited from BDMABB onto wafers with trenches etched into silicon oxide, followed by a thin layer of silicon nitride deposited by thermal CVD to increase the aspect ratio. TEM images of trenches 0.14 microns wide by 2.38 microns deep were taken for an aspect ratio (AR) of 17. Boron nitride films were deposited using BDMABB and N2 plasma using 600 cycles of PEALD. Film thickness measurements were taken at the top of the feature (23.44 nm), the middle 1 along the sidewall (31.71 nm), the middle 2 further down the sidewall (28.32 nm), and the bottom of the feature (32.74 nm), as shown in Figure 3, which shows that the step coverage of the BN film is all above 100%, indicating that there is bottom-up feature filling.

[0167] Example 2 :PEALD Boron Nitride Film Using BDMABB and Ammonia Plasma

[0168] The silicon wafer was loaded into a CN-1 reactor equipped with a showerhead design, which used a 13.56 MHZ direct plasma and heated to 350 °C with a chamber pressure of 2 Torr. BDMABB was used as a boron precursor and was delivered to the reaction chamber by bubbling 50 sccm of argon through a liquid maintained at 50 °C. The ALD cycle consisted of the following process steps:

[0169] a. Prepare the reactor and load the wafer

[0170] Chamber pressure: 2 Torr.

[0171] b. Introducing BDMABB precursor into the reactor

[0172] Bubbling: BDMABB precursor 50 sccm Ar flow

[0173] Argon flow: 1000sccm

[0174] BDMABB pulse: 3 seconds

[0175] c. Purge excess precursor

[0176] Argon flow: 1000sccm

[0177] Purge time: 20 seconds.

[0178] d. Introducing plasma

[0179] Argon flow: 1000sccm

[0180] NH3 flow: 100sccm

[0181] Plasma power: 200W

[0182] Plasma pulse: 5 seconds

[0183] e.Purge

[0184] Argon flow: 1000sccm

[0185] Purge time: 20 seconds

[0186] Table 2 shows the film thickness and refractive index of the films deposited in the case where steps b to e were repeated for 100, 250, and 500 cycles, respectively.

[0187] Table 2 Boron nitride thickness and refractive index of films deposited with different numbers of PEALD cycles using BDMABB and NH3 plasma.

[0188]

[0189]

[0190] like Figure 4 The growth rate of boron nitride is calculated from the plot of thickness versus cycle number as shown in

[0191] The film was deposited using 500 cycles for analysis. XPS analysis showed that the film contained 56.2 atomic % boron, 38.7 atomic % nitrogen, 2.6 atomic % carbon, and 2.5 atomic % oxygen (from air). The XRD diffraction pattern showed no features, indicating that the film was amorphous. AFM analysis showed that the average roughness of the film was 0.44 nm.

[0192] Boron nitride films were deposited from BDMABB onto wafers with trenches etched into silicon oxide, followed by a thin layer of silicon nitride deposited by thermal CVD to increase the aspect ratio. TEM images of trenches 0.14 microns wide by 2.38 microns deep were taken for an aspect ratio (AR) of 17. Figure 5A The top of the feature shown (15.15 nm), as Figure 5B The middle 1 (16.11 nm) along the sidewall is shown as Figure 5C The middle 2 (15.07 nm) further down the sidewall as shown and Figure 5D Film thickness measurements were taken at the base of the features shown (14.56 nm) and revealed that the step coverage of the BN films was between 106% and 93%.

[0193] Example 3 : Analysis data of the membranes of Example 1 and Example 2

[0194] In Examples 1 and 2, BN films were deposited by PEALD using BDMABB with N2 (Example 1) and NH3 (Example 2) based plasmas as follows. The wafer temperature was 350°C, the chamber pressure was maintained at 3 Torr, the BDMABB container was heated to 50°C, 50sccm of argon was bubbled for 3 seconds to deliver the chemical, and then the reaction chamber was purged with argon for 20 seconds to remove excess BDMABB, then NH3 or N2 was flowed with argon, and 200 W plasma was impacted for 5 seconds, and then purged for another 20 seconds to remove excess N2 or NH3. The process was then repeated for a selected number of cycles. The results of the analytical analysis are summarized in Table 3 below.

[0195] Table 3. Summary of analysis of films deposited from BDMABB using N2 and NH3 PEALD processes.

[0196]

[0197] Surprisingly, TEM images of the film on the high AR patterned film show that the deposition shows some "bottom-up" filling characteristics. Bottom-up is important for depositing seamless features despite the relatively rough film. Also note that the aspect ratio of the features is only 5:1. Figure 6 TEM of a film deposited on a high AR patterned feature using N2 PEALD is shown. Although the film is relatively rough, the TEM shows significantly more film deposition at the bottom of the feature (~37nm) compared to the top (~23nm), which means there is ~160% more film (SC) at the bottom than at the top. The film deposition at the shoulder feature is ~26nm (SC = ~113%), while the film deposition in the middle is ~34nm (SC = ~148%). Figure 7 TEM of films deposited onto high AR ratio patterned features using NH3 PEALD is shown. These films are smoother and do not show as much difference in film thickness between top and bottom, but there is still a slightly thicker film at the bottom of the feature (17nm) compared to 16nm at the top of the feature (SC = ~106%).

[0198] Figures 8 and 9 are TEM images of 17:1 high aspect ratio features. Figure 8 reveals very good conformality of the NH3 PEALD film. In addition, Figure 9 reveals thick deposition at the bottom of the N2 PEALD film, with significantly more film deposition at the bottom of the feature (~33nm) compared to the top (~23nm), which means ~143% more film at the bottom than at the top (SC). The film thickness at the MID1 position was measured to be ~32nm (SC = ~139%), and the film thickness at the MID2 position was measured to be ~28nm (SC = ~122%).

[0199] Surface features with a 5:1 aspect ratio were wet etched by immersing the surface in DHF for 20 minutes. The sidewalls were etched slightly faster than the bottom: for the NH3 PEALD film, the On the bottom and for N2 PEALD films, the side On the bottom

[0200] The foregoing description is primarily for illustrative purposes. Although the present invention has been shown and described with respect to exemplary embodiments thereof, it will be appreciated by those skilled in the art that the foregoing and various other changes, omissions and additions may be made in form and detail without departing from the spirit and scope of the present invention.

Claims

1. A boron-containing precursor for depositing a boron-containing film having a structure of Formula I: B(NR 1 R 2 ) n X 3-n (I) in R 1 Selected from straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C 10 Alkenyl, straight or branched C3 to C 10 Alkynyl, C1 to C6 dialkylamino, electron withdrawing groups and C4 to C 10 Aryl; R 2 Selected from hydrogen, straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C6 alkenyl, linear or branched C3 to C6 alkynyl, C1 to C6 dialkylamino, C6 to C 10 Aryl, linear or branched C1 to C6 fluorinated alkyl, electron withdrawing group and C4 to C 10 Aryl; X is Cl, Br, I or F; and n = 1 or 2, Where R 1 and R 2 are optionally linked together to form a ring selected from a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring, and wherein R 1 and R 2 It can be the same part or different parts.

2. The boron-containing precursor of claim 1, wherein R 1 and R 2 Connect together to form an annular ring.

3. The boron-containing precursor of claim 2, wherein R 1 and R 2 are selected from linear or branched C3 to C6 alkyl groups and are connected to form the cyclic ring.

4. The boron-containing precursor of claim 1, wherein R 1 and R 2 Not connected together to form a ring.

5. The boron-containing precursor of claim 1, wherein R 1 and R 2 are different.

6. The boron-containing precursor of claim 1, wherein R 1 and R 2 are the same.

7. The boron-containing precursor of claim 1, comprising at least one precursor selected from the group consisting of bis(dimethylamino)chloroborane, bis(dimethylamino)bromoborane, bis(dimethylamino)iodoborane, bis(diethylamino)chloroborane, bis(diethylamino)bromoborane, bis(diethylamino)iodoborane, bis(ethylmethylamino)chloroborane, bis(ethylmethylamino)bromoborane, bis(ethylmethylamino)iodoborane, (diisopropylamino)dichloroborane, (diisopropylamino)dibromoborane, (diisopropylamino)dibromoborane, Borane, (2,6-dimethyl-piperidino)dichloroborane, (2,6-dimethyl-piperidino)dibromoborane, (2,6-dimethyl-piperidino)diiodoborane, (2,6-dimethyl-piperidino)dichloroborane, (2,6-dimethyl-piperidino)dibromoborane, (2,6-dimethyl-piperidino)diiodoborane.

8. The boron-containing precursor of claim 7, wherein the boron-containing precursor comprises bis(dimethylamino)bromoborane.

9. The boron-containing precursor of claim 1, comprising at least one precursor selected from the group consisting of:

10. A composition comprising: (a) at least one compound having the structure of formula I: B(NR 1 R 2 ) n X 3-n (I) in R 1 Selected from straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C 10 Alkenyl, straight or branched C3 to C 10 Alkynyl, C1 to C6 dialkylamino, electron withdrawing groups and C4 to C 10 Aryl; R 2 Selected from hydrogen, straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C6 alkenyl, linear or branched C3 to C6 alkynyl, C1 to C6 dialkylamino, C6 to C 10 Aryl, linear or branched C1 to C6 fluorinated alkyl, electron withdrawing group and C4 to C 10 Aryl; X is Cl, Br, I or F; and n = 1 or 2, Where R 1 and R 2 are optionally linked together to form a ring selected from a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring, and wherein R 1 and R 2 may be the same part or different parts; and (b) a solvent, wherein the solvent has a boiling point, and wherein the difference between the boiling point of the solvent and the boiling point of the at least one boron-containing precursor is 40° C. or less.

11. The composition of claim 10, wherein the solvent comprises at least one selected from the group consisting of ethers, tertiary amines, alkyl hydrocarbons, aromatic hydrocarbons, and tertiary amino ethers.

12. The composition of claim 10, wherein R 1 and R 2 Connect together to form an annular ring.

13. The composition of claim 12, wherein R 1 and R 2 are selected from linear or branched C3 to C6 alkyl groups and are connected to form a cyclic ring.

14. The composition of claim 10, wherein R 1 and R 2 Not connected together to form a ring.

15. The composition of claim 10, wherein R 1 and R 2 are different.

16. The composition of claim 10, wherein R 1 and R 2 are the same.

17. The composition of claim 10, comprising at least one precursor selected from the group consisting of bis(dimethylamino)chloroborane, bis(dimethylamino)bromoborane, bis(dimethylamino)iodoborane, bis(diethylamino)chloroborane, bis(diethylamino)bromoborane, bis(diethylamino)iodoborane, bis(ethylmethylamino)chloroborane, bis(ethylmethylamino)bromoborane, bis(ethylmethylamino)iodoborane, (diisopropylamino)dichloroborane, (diisopropylamino)dibromoborane, (diisopropylamino)dibromoborane, Borane, (2,6-dimethyl-piperidino)dichloroborane, (2,6-dimethyl-piperidino)dibromoborane, (2,6-dimethyl-piperidino)diiodoborane, (2,6-dimethyl-piperidino)dichloroborane, (2,6-dimethyl-piperidino)dibromoborane, (2,6-dimethyl-piperidino)diiodoborane.

18. The composition of claim 17, wherein the boron-containing precursor comprises bis(dimethylamino)bromoborane.

19. The composition of claim 10, comprising at least one precursor selected from the group consisting of:

20. A method for depositing a boron-containing film onto at least one surface of a substrate having one or more features, the method comprising the steps of: a. providing the substrate in a reactor; b. forming the boron-containing film on the surface in a deposition process selected from chemical vapor deposition and atomic layer deposition processes using a boron-containing precursor selected from compounds having a structure of Formula I: B(NR 1 R 2 ) n X 3-n (I) in R 1 Selected from straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C 10 Alkenyl, straight or branched C3 to C 10 Alkynyl, C1 to C6 dialkylamino, electron withdrawing groups and C4 to C 10 Aryl; R 2 Selected from hydrogen, straight chain C1 to C 10 Alkyl, branched C3 to C 10 Alkyl, linear or branched C3 to C6 alkenyl, linear or branched C3 to C6 alkynyl, C1 to C6 dialkylamino, C6 to C 10 Aryl, linear or branched C1 to C6 fluorinated alkyl, electron withdrawing group and C4 to C 10 Aryl; X is Cl, Br, I or F; and n = 1 or 2, Where R 1 and R 2 are optionally linked together to form a ring selected from a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aliphatic ring, and wherein R 1 and R 2 It can be the same part or different parts; c. purging the reactor with a purge gas; d. providing a nitrogen-containing source to deposit the film onto the at least one surface; e. purging the reactor with a purge gas; f. optionally introducing at least one silicon-containing source into the reactor; g. If step f is performed, purging the reactor with a purge gas after step f; h. providing a nitrogen-containing source to deposit said film onto said at least one surface; and i. purging the reactor with a purge gas, Steps b to i are repeated until a film of desired thickness is obtained.

21. The method of claim 20, wherein R 1 and R 2 Connect together to form an annular ring.

22. The method of claim 21, wherein R 1 and R 2 are selected from linear or branched C3 to C6 alkyl groups and are connected to form a cyclic ring.

23. The method of claim 20, wherein R 1 and R 2 Not connected together to form a ring.

24. The method of claim 20, wherein R 1 and R 2 are different.

25. The method of claim 20, wherein R 1 and R 2 are the same.

26. The method of claim 20, wherein at least one of the boron-containing precursors is selected from the group consisting of bis(dimethylamino)chloroborane, bis(dimethylamino)bromoborane, bis(dimethylamino)iodoborane, bis(diethylamino)chloroborane, bis(diethylamino)bromoborane, bis(diethylamino)iodoborane, bis(ethylmethylamino)chloroborane, bis(ethylmethylamino)bromoborane, bis(ethylmethylamino)iodoborane, (diisopropylamino)dichloroborane, (diisopropylamino)dibromoborane, (diisopropylamino)dichloroborane, Borane, (pyrrolidinyl) diiodoborane, (pyrrolidinyl) chloroborane, (pyrrolidinyl) bromoborane, (pyrrolidinyl) iodoborane, (2-methyl-pyrrolidinyl) chloroborane, (2-methyl-pyrrolidinyl) bromoborane, (2-methyl-pyrrolidinyl) iodoborane, (piperidino) chloroborane, (piperidino) bromoborane, (piperidino) iodoborane, (2,6-dimethyl-piperidino) dichloroborane, (2,6-dimethyl-piperidino) dibromoborane and (2,6-dimethyl-piperidino) diiodoborane.

27. The method of claim 26, wherein the boron-containing precursor comprises bis(dimethylamino)bromoborane.

28. The method of claim 20, wherein steps f and g are performed and the at least one silicon-containing source is selected from the group consisting of trisilylamine (TSA), bis(dimethylsilylamino)silane, bis(tert-butylamino)silane (BTBAS), bis(dimethylamino)silane, bis(diethylamino)silane, bis(ethylmethylamino)silane, tris(dimethylamino)silane, tris(ethylmethylamino)silane, tetrakis(dimethylamino)silane, diisopropylaminosilane, di-sec-butylaminosilane, di-tert-butylaminosilane, 2,6-dimethylpiperidinosilane, 2,2,6,6-tetramethylpiperidinosilane, cyclohexylisopropylaminosilane, phenylmethylaminosilane, phenylethylaminodisilane, dicyclohexylaminosilane, diisopropyl ... Propylaminodisilane, di-sec-butylaminodisilane, di-tert-butylaminodisilane, 2,6-dimethylpiperidinodisilane, 2,2,6,6-tetramethylpiperidinodisilane, cyclohexylisopropylaminodisilane, phenylmethylaminodisilane, phenylethylaminodisilane, dicyclohexylaminodisilane, dimethylaminotrimethylsilane, dimethylaminotrimethylsilane, diisopropylaminotrimethylsilane, piperidinotrimethylsilane, 2,6-dimethylpiperidinotrimethylsilane, di-sec-butylaminotrimethylsilane, isopropylsec-butylaminotrimethylsilane, tert-butylaminotrimethylsilane, isopropylaminotrimethylsilane, diethylaminodimethylsilane, dimethylaminodimethylsilane, diisopropylaminodimethylsilane, piperidinotrimethylsilane tert-butylaminodimethylsilane, bis(dimethylamino)methylsilane, bis(diethylamino)methylsilane, bis(diisopropylamino)methylsilane, bis(isopropyl sec-butylamino)methylsilane, bis(2,6-dimethylpiperidino)methylsilane, bis(isopropylamino)methylsilane, bis(tert-butylamino)methylsilane, bis(sec-butylamino)methylsilane, bis(tert-amylamino)methylsilane, diisopropylaminodisilane and di-sec-butylaminodisilane, diisopropylaminotrisilylamine, diethylamino Trimethylsilylamine, isopropylaminotrimethylsilylamine and cyclohexylmethylaminotrisilylamine, 2-dimethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-diethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-ethylmethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-isopropylamino-2,4,4,6,6-pentamethylcyclotrisiloxane, 2-dimethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-diethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane, 2-isopropylamino-2,4,4,6,6-pentamethylcyclotetrasiloxane6,6,8,8-heptamethylcyclotetrasiloxane, 2-dimethylamino-2,4,6-trimethylcyclotrisiloxane, 2-diethylamino-2,4,6-trimethylcyclotrisiloxane, 2-ethylmethylamino-2,4,6-trimethylcyclotrisiloxane, 2-isopropylamino-2,4,6-trimethylcyclotrisiloxane, 2-dimethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-diethylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-ethylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane and 2-isopropylamino-2,4,6,8-tetramethylcyclotetrasiloxane, 2-pyrrolidinyl-2,4,6,8-tetramethylcyclotetrasiloxane and 2-cyclohexylmethylamino-2,4,6,8-tetramethylcyclotetrasiloxane.

29. The boron-containing precursor of claim 1, which is selected from bis(ethylmethylamino)chloroborane, bis(ethylmethylamino)bromoborane, bis(ethylmethylamino)iodoborane; (2-methyl-pyrrolidinyl)chloroborane, (2-methyl-pyrrolidinyl)bromoborane, (2-methyl-pyrrolidinyl)iodoborane, (2,5-dimethyl-pyrrolidinyl)chloroborane, (2,5-dimethyl-pyrrolidinyl)bromoborane and (2,5-dimethyl-pyrrolidinyl)iodoborane.

30. The composition of claim 10, wherein the at least one compound having the structure of Formula I is selected from at least one of bis(ethylmethylamino)chloroborane, bis(ethylmethylamino)bromoborane, bis(ethylmethylamino)iodoborane; (2-methyl-pyrrolidinyl)chloroborane, (2-methyl-pyrrolidinyl)bromoborane, (2-methyl-pyrrolidinyl)iodoborane, (2,5-dimethyl-pyrrolidinyl)chloroborane, (2,5-dimethyl-pyrrolidinyl)bromoborane and (2,5-dimethyl-pyrrolidinyl)iodoborane.

31. The method of claim 20, wherein the boron-containing precursor is at least one selected from the group consisting of bis(ethylmethylamino)chloroborane, bis(ethylmethylamino)bromoborane, bis(ethylmethylamino)iodoborane; (2-methyl-pyrrolidinyl)chloroborane, (2-methyl-pyrrolidinyl)bromoborane, (2-methyl-pyrrolidinyl)iodoborane, (2,5-dimethyl-pyrrolidinyl)chloroborane, (2,5-dimethyl-pyrrolidinyl)bromoborane and (2,5-dimethyl-pyrrolidinyl)iodoborane.

32. The method of claim 20, wherein the substrate surface comprises at least one or more features having a bottom surface and at least one sidewall surface, and wherein the film is formed with a higher growth rate on the bottom surface than on the at least one sidewall surface.

33. The method of claim 20, wherein the nitrogen-containing source is selected from N2 and NH3.

Images