Composition for a germanium seed layer and method of using the same for a germanium seed layer

Abstract

(a) a precursor and method for functionalizing a substrate surface to form a silicon-containing film and (b) to produce a germanium seed layer suitable for deposition of a Ge film. In one embodiment, a precursor of Formula I and / or a precursor of Formula II described herein are provided.

Description

Technology Field

[0001] The present invention relates to an organosilicon compound that can be used to generate a vinyl functionalized surface suitable for depositing a silicon-containing film and for producing a germanium seed layer advantageous for growing a high-quality reduced or metallic germanium film on a solid substrate surface. The present invention also relates to a method of using said compound.

[0002] Novel organoamino-vinylsilane and organoamino-allylsilane precursor compounds and compositions and methods comprising the same are described herein for depositing silicon-containing films, such as silicon oxide, silicon oxynitride, silicon oxycarbonitride, or carbon-doped silicon oxide, non-limitingly via a thermal atomic layer deposition (ALD) or plasma-enhanced atomic layer deposition (PEALD) process, or a combination thereof. More specifically, compositions and methods for forming stoichiometric or non-stoichiometric silicon-containing films or materials are described herein at one or more deposition temperatures of about 600°C or less, including, for example, about 25°C to about 350°C, wherein the films produced are terminated with vinyl functional groups and are suitable for forming germanium seed layers. Background Technology

[0003] One of the long-standing problems with plasma-enhanced chemical vapor deposition (PECVD) or thermochemical vapor deposition (CVD) of germanium films on dielectric substrates, such as silicon oxide, using germane and degerman is that the reactivity of germane compounds with substrate surface hydroxyl groups is much lower than the reactivity of Ge-H bond decomposition during Ge-Ge bond formation. The result of this reactivity mismatch is the formation of germanium mass islands on the substrate instead of a smooth film. To overcome this "island effect" or "island growth," which causes a high level of surface roughness in the resulting germanium film, it is necessary to lay a smooth seed layer on the surface initially. This provides a smooth starting surface and enables the subsequent germanium film to grow uniformly. However, the growth of this seed layer using conventional PECVD or CVD germanium precursors on dielectric substrate surfaces still presents problems with the conventional disadvantages of CVD, such as thickness control, low selectivity for the dielectric surface, non-self-limiting reactivity, and poor fit.

[0004] Examples of known precursors and methods are disclosed in the following publications, patents, and patent applications.

[0005] Publication No. EP1464724A2 describes a chemical formula MX suitable for the chemical vapor deposition of silicon and germanium films. a H b (NR 1 R 2 ) c R 3 d R 4 e A silicon- and germanium-containing precursor having is disclosed.

[0006] literature[ ]silver p - i - nEpitaxial growth of germanium on silicon is described in which a thin Ge / Si buffer layer of GeH4 is first deposited by chemical vapor deposition at 350°C and then by chemical vapor deposition of a thicker germanium film at 600°C for the purpose of fabricating a photodetector.

[0007] literature[ ] reports the functionalization of silica into chlorosilane occurring in the gas phase at a satisfactory rate of 300-400°C compared to methoxysilane (100-200°C).

[0008] literature[ ] describes the reaction with water for an additional 48 hours after treatment of fumed silica with vinyltriethoxysilane in toluene under reflux conditions for 48 hours to functionalize the surface with vinyl groups.

[0009] literature[ ] describes the functionalization of cyclic mesoporous silica into chloropropyldimethylsilyl groups and vinyldimethylsilyl groups by treating it with vinyl-substituted trisilylamine in toluene at 109°C for 15 hours.

[0010] U.S. Patent No. 8,460,753 B2 describes a precursor and a method for depositing silicon dioxide or silicon oxide films by ALD or CVD, wherein the precursor is of the formula R 1 n R 2 m Si(NR 3 R 4 ) 4-n-m Aminovinylsilane having and chemical formula (R 1 R 2 SiNR 3 ) p It is a cyclic silazane having, where R 1 It is an alkenyl or aromatic, such as vinyl, allyl, and phenyl.

[0011] U.S. Publication No. 20150275355 A1 is the chemical formula R 1n Si(NR 2 R 3 ) m H 4-m-n A composition and method for forming a silicon oxide film using a precursor having, more specifically using an organoamino-methylsilane precursor, are described.

[0012] U.S. Publication No. 20090162973 A1 is the chemical formula GeR x 1 (NR 2 R 3 ) (4-x) Depositing a germanium film or a germanium antimony telluride film on a substrate using a germanium-containing precursor having the above method involves exposing the substrate to the germanium-containing precursor alone or to the oxidizing gas or reducing gas together.

[0013] U.S. Publication No. 20110036289 A1 describes a method of depositing a germanium seed layer on a hydrogen-treated silicon substrate via CVD using a GeH4 precursor at low temperature, and subsequently growing an n-doped or p-doped germanium epitaxial film using a GeH4 precursor at high temperature in the presence of phosphine or diborane, respectively.

[0014] U.S. Publication No. 20110084308 A1 discloses a method for selectively growing high-quality strained or strain-relaxed Ge on a patterned Si substrate, which first at 350-400°C S i2 It involves the growth of a silicon-germanium buffer layer via CVD using H6 and GeH4 precursors, followed by the growth of a Ge seed layer via CVD using GeH4 precursors at 350-400°C, and then the growth of a Ge epitaxy film via CVD using GeH4 precursors at 550-600°C.

[0015] Both U.S. Publication No. 20130230975 A1 and No. 20140331928 A1 describe the growth of a germanium thin film using a germanium gas after the use of an aminogermanic gas to form a germanium seed layer on the substrate.

[0016] The disclosures of previously identified patents and patent applications are incorporated herein by reference.

[0017] There is still a need in the art for precursors and methods for depositing smooth, high-quality reduced or metallic germanium films on the surface of a dielectric substrate.

[0018] Unlike the prior art, the seed layer precursor disclosed herein utilizes a silicon-amine functional group as an anchor group to link vinyl or allyl groups to the surface. This chemistry converts a hydroxyl-rich surface into a vinyl or allyl-rich surface. Subsequently, a germane or digermane or other germanium precursor having at least one Ge-H bond is introduced into the chamber and reacts with the vinyl and / or allyl groups in a hydrogermylation reaction to form carbon-bonded germane or digermane groups on the surface. The resulting germanium film deposited using the germanium precursor will grow immediately on this germane-rich surface without forming islands.

[0019] Silicon precursors of the class of organamino-vinylsilanes and organamino-allylsilanes comprising at least one vinyl or allyl group and at least one organamino anchor group, compositions comprising the same, and methods of using the same to deposit silicon-containing films as well as to form monolayer films comprising silicon and vinyl groups are disclosed herein, which can facilitate the formation of suitable seed layers for the deposition of metallic thin films, particularly germanium thin films. Additionally, compositions comprising organamino-vinylsilanes or organamino-allylsilanes that substantially do not contain at least one impurity species selected from organic amines, alcohols, halides, high molecular weight species, and trace metals are disclosed herein. The compositions may further comprise a solvent. Additionally, methods for forming a film or coating comprising silicon and vinyl groups on an object to be processed, such as a semiconductor wafer, are disclosed herein.

[0020] In one embodiment of the method described herein, a film containing silicon and vinyl groups is deposited on a substrate using an organamino-vinylsilane or organamino-allylsilane precursor in a deposition chamber under conditions for producing a germanium seed layer and a vinyl-terminated layer suitable for growing a high-quality germanium film thereafter.

[0021] More specifically, the above objectives and other objectives are achieved by a method for forming a germanium seed layer comprising the following steps:

[0022] a. A step of providing a substrate to a reactor;

[0023] b. A step of introducing at least one precursor represented by the following chemical formulas I and / or II into a reactor;

[0024]

[0025] In the above equation, R 1 It is linear or branched C1 to C 10 Alkyl groups, linear or branched C3 to C10 Alkenyl group, linear or branched C3 to C 10 alkynyl group, C3 to C 10 Cyclic alkyl group, and C6 to C 10 Selected from the group consisting of aryls; R 2 is hydrogen, linear or branched C1 to C 10 Alkyl group, linear or branched C2 to C6 alkenyl group, linear or branched C3 to C6 alkenyl group, C3 to C 10 Cyclic alkyl group, and C6 to C 10 Selected from the group consisting of aryls; R 3 and R 4 Each independently hydrogen, linear or branched C1 to C 10 Alkyl group, linear or branched C2 to C6 alkenyl group, linear or branched C3 to C6 alkenyl group, C3 to C 10 Cyclic alkyl group, C6 to C 10 Aryl group, C1 to C 10 Linear, cyclic, or branched alkoxy groups, the organoamino groups defined above (NR 1 R 2 Selected from the group consisting of halides selected from the group consisting of ), and Cl, Br, and I;

[0026] c. Step of purging the reactor with purge gas;

[0027] d. A step of introducing at least one germanium precursor comprising at least one Ge-H bond at a temperature such that the substrate is coated with at least one monolayer of germanium;

[0028] e. Step of purging the reactor with purge gas;

[0029] f. Optionally introducing a hydrogen or hydrogen plasma source;

[0030] g. Optionally, a step of purging the reactor with purge gas;

[0031] h. A step of introducing the same or different germanium precursor as in step d at a temperature suitable for growing a germanium-containing film having a desired thickness.

[0032] In one embodiment of the method described herein, the germanium precursor having at least one Ge-H group is, but is not limited to, trichlorogermane (Cl3GeH), germane (GeH4), digermane (Ge2H6), tert-butylgermane ( t It includes one or more of BuGeH3), phenylgerman, sec-butylgerman, iso-butylgerman, and benzylgerman. As in the step in the method according to one embodiment, a film containing silicon and oxygen is deposited on a substrate using an organamino-vinylsilane precursor of Formula I and / or an organamino-allylsilane precursor of Formula II and an oxygen-containing source under conditions for producing a silicon oxide or carbon-doped silicon oxide film on the substrate. As in the step in the method according to another embodiment, a film containing silicon and nitrogen is deposited on a substrate using an organamino-vinylsilane precursor of Formula I and / or an organamino-allylsilane precursor of Formula II and a nitrogen-containing source to produce a silicon nitride, carbon-doped silicon nitride, silicon oxynitride, or silicon oxycarbonitride film on the substrate. In further embodiments, an organamino-vinylsilane precursor according to Formula I and / or an organamino-allylsilane precursor of Formula II is used as a dopant for a metal-containing film, e.g., a metal oxide film or a metal nitride film, but not limited to.

[0033] In a specific embodiment of the above method, steps d and h may be performed at the same temperature, or step d may be performed at a lower temperature than step h to avoid or limit the CVD of the germanium film in step d until a sufficient Ge seed layer is formed. In some embodiments, step d is performed at a higher temperature than step h. In other embodiments, the temperature is increased after step d or before the deposition of the subsequent germanium CVD film in step g in an optional hydrogen or hydrogen plasma treatment process to thermally anneale at least one monolayer of germanium known as the seed layer. In yet another embodiment, at least one germanium precursor containing at least one Ge-H bond is identical to the germanium CVD precursor. In other embodiments, at least one germanium precursor containing at least one Ge-H bond is not identical to the germanium CVD precursor.

[0034] In another embodiment, a method for functionalizing the surface of a solid substrate, such as but not limited to silica, alumina, metal oxide, silicon wafer, dielectric thin film, or a metal surface having vinyl and / or allyl groups, is provided, said method comprising the following steps:

[0035] a. A step of providing a substrate to a reactor;

[0036] b. introducing into a reactor at least one organoamino-vinylsilane precursor comprising at least one vinyl group and at least one organoamino anchor group connected to at least one silicon atom represented by the following chemical formula I, and / or at least one organoamino-allylsilane precursor comprising at least one allyl group and at least one organoamino anchor group connected to at least one silicon atom represented by the following chemical formula II; and

[0037] c. A step of removing residual organamino-vinylsilane or organamino-allylsilane from the substrate with a solvent and / or purge gas.

[0038] In some embodiments, the organamino-vinylsilane and / or organamino-allylsilane precursors disclosed herein may be introduced into a solid substrate as a pure liquid, as a solution in a solvent, or in a gaseous phase with or without a carrier gas at a temperature in the range of 0°C to 500°C. Brief explanation of the drawing

[0039] FIG. 1 is a flowchart illustrating a general reaction scheme in which an organamino-vinylsilane precursor having Formula I (or alternatively Formula II) disclosed herein is used to (a) functionalize a substrate surface with vinyl groups, which makes it suitable for (b) forming a germanium seed layer through a hydrogermylation reaction with a germanium precursor comprising at least one Ge-H bond, and (c) enabling the subsequent growth of a smooth and uniform germanium film on the upper surface of the seed layer using at least one ALD or CVD Ge precursor. Specific details for implementing the invention

[0040] A method of using the same for functionalizing a substrate surface for subsequent processing, including the deposition of silicon precursor compounds and silicon-containing films, as well as, but not limited to, the deposition of germanium films, is disclosed herein.

[0041] A specific method for forming a germanium seed layer includes the following steps:

[0042] a. A step of providing a substrate to a reactor;

[0043] b. introducing into a reactor at least one organoamino-vinylsilane precursor comprising at least one vinyl group and at least one organoamino anchor group connected to at least one silicon atom represented by the following chemical formula I, and / or at least one organoamino-allylsilane precursor comprising at least one allyl group and at least one organoamino anchor group connected to at least one silicon atom represented by the following chemical formula II;

[0044]

[0045] In the above equation, R 1 It is linear or branched C1 to C 10 Alkyl groups, linear or branched C3 to C 10 Alkenyl group, linear or branched C3 to C 10 alkynyl group, C3 to C 10 Cyclic alkyl group, and C6 to C 10 Selected from the group consisting of aryls; R 2 is hydrogen, linear or branched C1 to C 10 Alkyl group, linear or branched C2 to C6 alkenyl group, linear or branched C3 to C6 alkenyl group, C3 to C 10 Cyclic alkyl group, and C6 to C 10 Selected from the group consisting of aryls; R 3 and R 4 Each independently hydrogen, linear or branched C1 to C 10 Alkyl group, linear or branched C2 to C6 alkenyl group, linear or branched C3 to C6 alkenyl group, C3 to C 10 Cyclic alkyl group, C6 to C 10 Aryl group, C1 to C 10 Linear, cyclic, or branched alkoxy groups, the organoamino groups defined above (NR 1 R 2 Selected from the group consisting of halides selected from the group consisting of ), and Cl, Br, and I;

[0046] c. Step of purging the reactor with purge gas;

[0047] d. A step of introducing at least one germanium precursor comprising at least one Ge-H bond at a temperature such that the substrate is coated with at least one monolayer of germanium;

[0048] e. Step of purging the reactor with purge gas;

[0049] f. Optionally introducing a hydrogen or hydrogen plasma source;

[0050] g. Optionally, a step of purging the reactor with purge gas;

[0051] h. A step of introducing the same or different germanium precursor as in step d at a temperature suitable for growing a germanium-containing film having a desired thickness.

[0052] In some implementations, R 1 and R 2 is identical. In another implementation, R 1 and R 2 is different. In some implementations, R 3 and R 4 is identical. In another implementation, R 3 and R 4 is different.

[0053] In some preferred embodiments, R 3 and R 4 It is independently selected from the group consisting of hydrogen, methyl, vinyl, and allyl.

[0054] The organamino-vinylsilane and organamino-allylsilane precursors described herein are used to form monolayer films containing silicon + vinyl and / or allyl groups, as well as, to a non-limiting extent, stoichiometric and non-stoichiometric silicon-containing films such as amorphous silicon, crystalline silicon, silicon oxide, carbon-doped silicon oxide, silicon oxynitride, silicon oxynitride, and silicon oxycarbonitride. These precursors may also be used, for example, as dopants for metal-containing films. Organamino-vinylsilane and organamino-allylsilane precursors used in semiconductor processing are typically high-purity volatile liquid chemicals that are evaporated and delivered as gas to a deposition chamber or reactor to deposit silicon-containing films on a semiconductor device via a CVD or ALD process; however, they may also be introduced into the substrate in a liquid phase (pure or with a solvent). The choice of precursor material for deposition depends on the desired silicon-containing material or film produced. For example, the precursor material may be selected for its content of chemical components, its stoichiometric ratio of chemical components, and / or for the silicon-containing film or coating produced under CVD. The precursor material may also be selected for various other characteristics, such as cost, relatively low toxicity, handling characteristics, ability to maintain a liquid phase at room temperature, volatility, molecular weight, thermal stability, and / or other considerations. In a specific embodiment, the precursor described herein may be delivered to a reactor system by any number of means using a pressurizable stainless steel vessel equipped with suitable valves and fittings that enable the liquid or gaseous precursor to be delivered to a deposition chamber or reactor.

[0055] Another specific method for forming a germanium seed layer includes the following steps:

[0056] a. A step of providing a substrate to a reactor;

[0057] b. introducing into a reactor at least one organoamino-vinylsilane precursor comprising at least one vinyl group and at least one organoamino anchor group connected to at least one silicon atom represented by the following chemical formula I, and / or at least one organoamino-allylsilane precursor comprising at least one allyl group and at least one organoamino anchor group connected to at least one silicon atom represented by the following chemical formula II;

[0058]

[0059] In the above equation, R 1 It is linear or branched C1 to C 10 Alkyl groups, linear or branched C3 to C 10 Alkenyl group, linear or branched C3 to C 10 alkynyl group, C3 to C 10 Cyclic alkyl group, and C6 to C 10 Selected from the group consisting of aryls; R 2 is hydrogen, linear or branched C1 to C 10 Alkyl group, linear or branched C2 to C6 alkenyl group, linear or branched C3 to C6 alkenyl group, C3 to C 10 Cyclic alkyl group, and C6 to C 10 Selected from the group consisting of aryls; R 3 and R 4 Each independently hydrogen, linear or branched C1 to C 10 Alkyl group, linear or branched C2 to C6 alkenyl group, linear or branched C3 to C6 alkenyl group, C3 to C 10 Cyclic alkyl group, C6 to C 10 Aryl group, C1 to C 10 Linear, cyclic, or branched alkoxy groups, the organoamino groups defined above (NR 1 R 2 Selected from the group consisting of halides selected from the group consisting of ), and Cl, Br, and I;

[0060] c. Step of purging the reactor with purge gas;

[0061] d. Step of introducing an oxygen-containing source;

[0062] e. Step of purging the reactor with purge gas;

[0063] f. A step of reintroducing the organoamino-vinylsilane or organoamino-allylsilane precursor described above;

[0064] g. Step of purging the reactor with purge gas;

[0065] h. A step of introducing at least one germanium precursor comprising at least one Ge-H bond at a temperature such that the substrate is coated with at least one monolayer of germanium;

[0066] i. Step of purging the reactor with purge gas;

[0067] j. Optionally introducing a hydrogen or hydrogen plasma source;

[0068] k. Optionally, a step of purging the reactor with purge gas;

[0069] l. A step of introducing the same or different germanium precursor as in step d at a temperature suitable for growing a germanium-containing film having a desired thickness, wherein steps b to e are repeated until a silicon-containing film of the desired thickness is deposited before the deposition of a germanium seed layer and a subsequent germanium-containing film.

[0070] In some implementations, R 1 and R 2 is identical. In another implementation, R 1 and R 2 is different. In some implementations, R 3 and R 4 is identical. In another implementation, R 3 and R 4 is different.

[0071] In some preferred embodiments, R 3 and R 4 It is independently selected from the group consisting of hydrogen, methyl, vinyl, and allyl.

[0072] A silicon-containing film deposited using the organamino-vinylsilane and / or organamino-allylsilane precursors described herein, which are either a single layer or larger than a single layer, serves as a suitable substrate for a reaction with a germanium precursor containing at least one Ge-H bond. Without being bound by theory, when the surface of the substrate reacts with the organamino-vinylsilane and / or organamino-allylsilane precursors described herein, it is believed to be functionalized into vinyl and / or allyl groups, or more specifically vinylsilyl and / or allylsilyl groups. Each of these groups can subsequently undergo a hydrogermylation reaction with the Ge-H bonds of the germanium precursor molecules to fix germanium atoms or germane groups on the surface where available vinyl and / or allyl groups are present. In this reaction, the vinyl and / or allyl groups are converted into ethylene, ethylidene, propylene, or methylethylene linkers between the Si and Ge atoms. When the surface of a substrate is uniformly coated with germanium, it is primed for the deposition of a Ge film by ALD, PEALD, CVD, cyclic CVD, or PECVD processes in most cases at high temperatures, but in some cases at the same temperature. In some embodiments, the germanium fixed on the surface is primarily -GeH x (x = 0, 1, 2, 3) To create a terminalized surface, it must be reduced to a reducing gas, such as hydrogen or hydrogen plasma, without limitation.

[0073] Exemplary germanium precursors comprising at least one Ge-H bond are, but are not limited to, trichlorogermane (Cl3GeH), germane (GeH4), digermane (Ge2H6), and tert-butylgermane ( tIt includes one or more of BuGeH3), phenylgerman, sec-butylgerman, iso-butylgerman, and benzylgerman.

[0074] FIG. 1 illustrates a general reaction scheme in which an organamino-vinylsilane precursor having Formula I disclosed herein is used to (a) functionalize a substrate surface with vinyl groups, which makes it suitable for (b) forming a germanium seed layer through a hydrogermylation reaction with a germanium precursor containing at least one Ge-H bond, and (c) enabling the subsequent growth of a smooth and uniform germanium film on the upper surface of the seed layer using at least one ALD or CVD Ge precursor. The same type of reaction scheme is applied to the method used in step (a) of FIG. 1, except that an organamino-allylsilane precursor having Formula II disclosed herein is functionalized with allyl groups instead of vinyl groups.

[0075] -GeH as a result of the material being uniformly treated with the organamino-vinylsilane and / or organamino-allylsilane precursors disclosed herein x When uniformly terminated with (x = 0, 1, 2, 3) groups, it is believed to serve as a seed layer, which enables the subsequent growth of an amorphous or crystalline germanium film having very low non-uniformity and a low level of surface roughness. The resulting smooth and uniform Ge film is believed to be made possible by eliminating the phenomenon known to those skilled in the art as "island growth" during the initial stages of Ge film deposition. By converting a non-reactive organic, dielectric, metallic, or any other non-reactive surface into a reactive surface functionalized with germanium atoms or germane groups, the deposition of a Ge film can be initiated without the formation of "islands" on the surface. This smooth conformal initial layer features a high-quality germanium seed layer.

[0076] The organamino-vinylsilane and organamino-allylsilane precursors described herein exhibit a balance of reactivity and stability that makes them ideally suitable as CVD or ALD precursors in microelectronic device manufacturing processes. With respect to reactivity, the organamino-vinylsilane and / or organamino-allylsilane in the present invention comprises at least one organamino group (NR) that assists the organamino-vinylsilane and / or organamino-allylsilane precursor in reacting with a hydroxyl surface during the ALD process. 1 R 2 ...has ) ...most often referred to in the present invention, the hydroxyl surface is a dielectric surface such as silicon oxide, silicon nitride, silicon (including natural oxides), metal oxides, metal nitrides, or metals (including natural oxides), but other materials that may include surface hydroxyl groups, such as organic polymers, silicon, resins, plastics, beads, adsorbents, amorphous carbon, activated carbon, minerals, organic materials, containers, and textiles, are also expected to be reactive to at least one organoamino group on the organoamino-vinylsilane and / or organoamino-allylsilane precursors described herein.

[0077] The organoamino anchor groups in the organoamino-vinylsilane and organoamino-allylsilane precursors described herein are expected to provide advantages for chloro-vinylsilane, alkoxy-vinylsilane, vinyldisilazane, chloro-allylsilane, alkoxy-allylsilane, and allyl-disilazane precursors, particularly in relation to reactions with -OH-terminated surfaces at low temperatures and in the gas phase. For example, treatment of a substrate with triethoxyvinylsilane at a specific temperature may functionalize or not functionalize the substrate surface with vinyl groups, whereas treatment of the substrate with organoamino-vinylsilane at the same temperature may provide a much higher level of functionalization. Similarly, treatment of a substrate with triethoxyallylsilane at a specific temperature may functionalize or not functionalize the substrate surface with allyl groups, while treatment of the substrate with organoamino-allylsilane at the same temperature may provide a much higher level of functionalization. This makes organamino-vinylsilanes and organamino-allylsilanes having chemical formulas I and II advantageous as surface modifiers for purposes other than the subsequent deposition of germanium films. Examples of the process that may be advantageous due to high saturation of surface vinyl and / or allyl groups include, but are not limited to, (a) immobilization of species such as catalysts, ion exchange functional groups, adsorbents, or metal removers on a solid support; (b) increase in the hydrophobicity of the substrate; (c) change in the optical properties or refractive index of the substrate for display applications; and / or (d) provision of cross-linking sites for better adhesion after UV / thermal annealing of a subsequent coating.

[0078] Certain precursors have boiling points that are too high, which may cause them to vaporize and fail to be delivered to the reactor to deposit a film on the substrate; thus, it is desirable to select smaller R-groups as well as smaller organic amino groups to provide precursors having a boiling point of 250°C or lower, preferably 200°C or lower. Having two or more organic amino groups can significantly increase the boiling point; precursors with relatively higher boiling points require that the delivery vessel and line be heated above the boiling point of the precursor under a given vacuum to prevent particle formation or condensation in the vessel, line, or both. Regarding stability, other precursors may form silane (SiH4) or disilane (Si2H6) as they decompose. Silanes are flammable at room temperature or may combust spontaneously, which presents safety and handling issues. Furthermore, the formation of silane or disilane and other byproducts lowers the purity level of the precursor, and a change of as little as 1-2% in chemical purity may be considered unacceptable for reliable semiconductor manufacturing. In certain embodiments, the organamino-vinylsilane and / or organamino-allylsilane precursors having Formula I and / or II described herein contain impurities (e.g., free organicamines, alcohols, chlorosilanes, halides, or high molecular weight disproportionation products) in an amount of 2 wt% or less, or 1 wt% or less, or 0.5 wt% or less, after being stored for a period of at least 6 months or at least 1 year, exhibiting storage stability. Si-H groups (R in Formula I and / or II) 3 and R 4 Certain organoamino-vinylsilane and / or organoamino-allylsilane precursors having at least one of) may be susceptible to degradation by polymerization via intermolecular hydrosilylation reactions. That is, R in Formula I and / or II 1 to R 4If the group size does not provide sufficient steric protection, the reaction may occur between the Si-H group of one molecule and the vinyl and / or allyl group of another molecule. This hydrosilylation reaction can occur slowly or spontaneously under storage conditions, during purification (e.g., distillation), or during deposition processes, and may be catalyzed by trace impurities. Therefore, it is important to remove organamino-vinylsilane precursors, such as various impurities that can act as potential hydrosilylation / polymerization catalysts. Furthermore, R is required to facilitate the reaction of organamino-vinylsilane and / or organamino-allylsilane with the substrate surface under desired conditions while preserving the inherent stability of the precursor. 1 to R 4 Careful selection of energy is required.

[0079] In a specific preferred embodiment, R in Formula I and / or II 3 and R 4 Both are organoamino groups. In another preferred embodiment, R in formula I and / or II 3 and R 4 Both are methyl groups. In another preferred embodiment, R in formula I and / or II 1-4 All are methyl groups. In another preferred embodiment, R in Formula I and / or II 3 and R 4 Both are vinyl groups. In another preferred embodiment, R in Formula I and / or II 3 and R 4 Both are allyl groups. In another preferred embodiment, R in formula I 3 is an organic amino group, and R 4 is a vinyl group. In another preferred embodiment, R in Formula II 3 is an organic amino group, and R 4 is an allyl group. In another preferred embodiment, R in formula I3 is a methyl group, and R 4 is a vinyl group. In another preferred embodiment, R in Formula II 3 is a methyl group, and R 4 is an announcement.

[0080] In certain embodiments, for depositing silicon oxide or silicon nitride or other silicon-containing films using, for example, an ALD, ALD-like, PEALD, or CCVD deposition method, the organamino-vinylsilane and organamino-allylsilane precursors described herein can deposit high-density materials at relatively low deposition temperatures, for example, 1000°C or less, 800°C or less, 700°C or less, 500°C or less, or 400°C or less, 300°C or less, 200°C or less, 100°C or less, or 50°C or less.

[0081] In one embodiment, a composition for a silicon-containing film comprising an organamino-vinylsilane having Formula I and / or an organamino-allylsilane having Formula II as described herein and a solvent(s) is described herein.

[0082] Without being intended to be bound by any particular theory, the compositions described herein are believed to provide one or more advantages compared to existing silicon precursors such as TEOS, BDEAS, and SiCl4. These advantages include: better use of organamino-vinylsilane and / or organamino-allylsilane in semiconductor processes, better stability over long-term storage, cleaner evaporation by flash evaporation, and / or a more stable direct liquid injection (DLI) chemical vapor deposition process overall, which enables the deposition of high-quality silicon-containing films and also enables superior subsequent Ge film deposition. The weight percentage of organamino-vinylsilane and / or organamino-allylsilane in the composition may be in the range of 1 to 99%, and the remainder is solvent(s), wherein the solvent(s) do not react with organamino-vinylsilane and / or organamino-allylsilane and have a boiling point similar to that of organamino-vinylsilane and / or organamino-allylsilane. In relation to the latter, the difference between the boiling points of the organamino-vinylsilane and / or organamino-allylsilane and the solvent(s) in the composition is 40°C or less, more preferably 20°C or less, or 10°C or less.

[0083] In some embodiments, if a metallic film, such as a germanium film, is subsequently deposited on a silicon-containing film, it is advantageous to deposit a silicon-containing film, such as silicon, silicon carbide, silicon nitride, carbon-doped silicon nitride, silicon oxide, silicon oxynitride, carbon-doped silicon oxynitride, and carbon-doped silicon oxide, using the organamino-vinylsilane and / or organamino-allylsilane precursors described in the present invention, without being bound by any particular theory, if the final step of this Si-containing film deposition process is exposure to the organamino-vinylsilane and / or organamino-allylsilane precursors, the resulting Si-containing film is considered to be much more sensitive to the formation of a uniform Ge seed layer and the subsequent growth of a smooth conformal Ge film. In some cases, the bulk composition, physical properties, and electrical properties of the Si-containing film described herein can also be achieved using various other silicon precursors and deposition methods known in the prior art. However, this film will still require functionalization with the organamino-vinylsilane and / or organamino-allylsilane precursors described herein prior to the deposition of the reduced or metallic germanium film so that this germanium film becomes of the same high quality. Therefore, it is evident that using a single silicon precursor, such as the organamino-vinylsilane or organamino-allylsilane described herein, to perform both the deposition of the silicon-containing film and the functionalization of this film into vinyl and / or allyl groups for subsequent Ge film growth is much more advantageous than using two different silicon precursors.

[0084] In certain embodiments, substituent R in formulas I and / or II. 1 and R 2 They can be connected together to form a ring structure. As understood by those skilled in the art, R 1 and R 2 ring R 1The cases where they are connected together to form are R 2 It will include a bond for connection to and the reverse thereof. In this embodiment, the ring structure may be unsaturated, such as a cyclic alkyl ring, or saturated, such as an allyl ring. In a similar manner, R in Formula I and / or II 3 and R 4 They can be connected together to form a ring structure. Additionally, in this embodiment, the ring structure may or may not be substituted. Exemplary annular rings are, without limitation, pyrrolidino , 2-methylpyrrolidino, 2,5-dimethylpyrrolidin, It includes piperidino, 2,6-dimethylpiperidino, pyrrolyl, and imidazolyl groups. In other embodiments, however, substituent R 1 and R 2 is not connected. In another implementation, R 3 and R 4 is not connected.

[0085] In the chemical formula and throughout the detailed description, the term “alkyl” means a linear or branched functional group having 1 to 10 or 1 to 6 carbon atoms. Exemplary alkyl groups include, but not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-pentyl, tert-pentyl, hexyl, iso-hexyl, and neo-hexyl. In certain embodiments, the alkyl group may have one or more functional groups attached thereto, such as an alkoxy group, a dialkylamino group, or a combination thereof, without limitation. In other embodiments, the alkyl group does not have one or more functional groups attached thereto.

[0086] In the chemical formula and throughout the detailed description, the term “cyclic alkyl” means a cyclic functional group having 3 to 10 or 4 to 10 carbon atoms or 5 to 10 carbon atoms. Exemplary cyclic alkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

[0087] In the chemical formula and throughout the detailed description, the term “allyl” means an aromatic cyclic functional group having 5 to 12 carbon atoms or 6 to 10 carbon atoms. Exemplary aryl groups include, but are not limited to, phenyl, benzyl, chlorobenzyl, tolyl, and o-xylyl.

[0088] In the chemical formula and throughout the detailed description, the term “alkenyl group” means a group having one or more carbon-carbon double bonds and having 3 to 10 or 3 to 6 or 3 to 4 carbon atoms. Exemplary alkenyl groups include, but are not limited to, vinyl and allyl.

[0089] In the chemical formula and throughout the detailed description, the term “alkynyl group” means a group having one or more carbon-carbon triple bonds and having 3 to 10 or 3 to 6 or 3 to 4 carbon atoms.

[0090] In the chemical formula and throughout the detailed description, the term “organoamino group” means a group having at least one alkyl or otherwise hydrocarbon group attached to a nitrogen atom and having 1 to 10 or 2 to 6 or 2 to 4 carbon atoms. Exemplary organicamino groups include, but are not limited to, methylamino, ethylamino, normal-propylamine, iso-propylamino, normal-butylamino, iso-butylamino, sec-butylamino, tert-butylamino, cyclopentylamino, cyclohexylamino, phenylamino, dimethylamino, N-ethylmethylamino, diethylamino, and di-iso-propylamino.

[0091] In the chemical formula and throughout the detailed description, the term “dialkylamino group” means a group having two alkyl groups attached to a nitrogen atom, each alkyl group having, for example, 1 to 10, 2 to 6, or 2 to 4 carbon atoms. Exemplary dialkylamino groups include, but are not limited to, dimethylamino, diethylamino, ethylmethylamino, di-normal-propylamine, di-iso-propylamino, di-normal-butylamino, di-iso-butylamino, di-sec-butylamino, and di-tert-butylamino.

[0092] In certain embodiments, one or more of the alkyl groups, alkenyl groups, alkynyl groups, or aryl groups in Formulas I and II may be substituted or may have one or more substituted atoms or groups of atoms, for example, in place of a hydrogen atom. Exemplary substituents include, but are not limited to, oxygen, sulfur, halogen atoms (e.g., F, Cl, I, or Br), nitrogen, and phosphorus.

[0093] In a specific embodiment, at least one organamino-vinylsilane precursor having Formula I and / or at least one organamino-allylsilane precursor having Formula II has one or more substituents comprising an oxygen or nitrogen atom.

[0094] The unique structure of the precursors of formulas I and II described herein is believed to enable the deposition of silicon-containing films and / or surface functionalization of solid substrates at temperatures of 1000°C or lower, 700°C or lower, 500°C or lower, 400°C or lower, 300°C or lower, 200°C or lower, 100°C or lower, or 25°C or lower.

[0095] Table 1 lists examples of silicon precursors having at least one vinyl group and at least one organoamino anchor group connected to at least one silicon atom according to Chemical Formula I.

[0096] [Table 1] Exemplary organoamino-vinylsilane precursors.

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106] Table 2 lists examples of silicon precursors having at least one vinyl group and at least one organoamino anchor group connected to at least one silicon atom according to Chemical Formula II.

[0107] [Table 2] Exemplary organoamino-allylsilane precursors.

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117] The organamino-vinylsilane and / or organamino-allylsilane precursor according to the present invention and the composition comprising the organamino-vinylsilane and / or organamino-allylsilane precursor according to the present invention preferably do not substantially contain organic amines or halide ions. As used herein, the term "substantially not containing" in relation to halide ions (or halides), such as chlorides and fluorides, bromides, and iodides, for example, means less than 5 ppm (by weight), preferably less than 3 ppm, more preferably less than 1 ppm, and most preferably 0 ppm. As used herein, the term "not containing" in relation to halide ions or other impurities means 0 ppm. Chlorides are known to act as decomposition catalysts for organamino-vinylsilanes and organamino-allylsilanes. Significant levels of chlorides in the final product can cause the organamino-vinylsilane and / or organamino-allylsilane precursors to decompose. The gradual degradation of organoamino-vinylsilanes and / or organoamino-allylsilanes can directly affect film deposition or surface functionalization processes, making it difficult for semiconductor manufacturers to meet film specifications. Furthermore, storage life or stability is negatively affected by the higher degradation rates of organoamino-vinylsilanes and / or organoamino-allylsilanes, making it difficult to guarantee a storage life of 1–2 years. Therefore, the accelerated degradation of organoamino-vinylsilanes and / or organoamino-allylsilanes presents safety and performance concerns related to the formation of these flammable and / or combustible gaseous byproducts: Organic amines are non-limitingly C1 to C 10 Includes organic amines and organodiamines. Silicon precursor compounds having chemical formulas I and II are preferably Li + , Na + , K + , Mg 2+ , Ca 2+ , Al 3+, Fe 2+ , Fe 2+ , Fe 3+ , Ni 2+ , Cr 3+ It does not substantially contain metal ions such as those. As used herein, the term “substantially not containing” relating to volatile Ru or Pt complexes from Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr, precious metals, such as ruthenium or platinum catalysts used in synthesis, means less than 5 ppm (by weight), preferably less than 3 ppm, more preferably less than 1 ppm, most preferably 0.1 ppm, as measured by ICP-MS or other analytical methods for measuring trace metals.

[0118] The method used to form a silicon-containing film or coating is a deposition process. Examples of suitable deposition processes for the method disclosed herein include, but are not limited to, cyclic chemical vapor deposition (CCVD), metal-organic CVD (MOCVD), thermochemical vapor deposition, plasma-enhanced chemical vapor deposition ("PECVD"), high-density PECVD, photon-assisted CVD, plasma-photon-assisted ("PPECVD"), cryogenic chemical vapor deposition, chemical-assisted vapor deposition, hot-filament chemical vapor deposition, CVD of liquid polymer precursors, deposition from supercritical fluids, and low-energy CVD (LECVD). In certain embodiments, the metal-containing film is deposited via an atomic layer deposition (ALD), plasma-enhanced ALD (PEALD), or plasma-enhanced cyclic CVD (PECCVD) process. As used herein, the term "chemical vapor deposition process" refers to any process in which a substrate is exposed to one or more volatile precursors that react and / or decompose on the substrate surface to produce a desired deposition. As used herein, the term “atomic layer deposition process” refers to a self-limiting (e.g., constant amount of film material deposited in each reaction cycle), sequential surface chemistry for depositing a film of material onto a substrate of varying composition. Although precursors, reagents, and sources used herein are sometimes described as “gases,” it is understood that precursors may be liquids or solids, which are transported to a reactor via direct evaporation, bubbling, or sublimation with or without the use of an inert gas. In some cases, the evaporated precursor may pass through a plasma generator. In one embodiment, a silicon-containing film is deposited using an ALD process. In another embodiment, a silicon-containing film is deposited using a CCVD process. In a further embodiment, a silicon-containing film is deposited using a thermal CVD process. As used herein, the term “reactor” includes, but is not limited to, a reaction chamber or a deposition chamber.

[0119] In certain embodiments, the method disclosed herein avoids pre-reaction of precursors by using an ALD or CCVD method that separates the precursors before and / or during introduction into a reactor. In this regard, deposition techniques, such as ALD or CCVD processes, are used to deposit silicon-containing films. In one embodiment, the film is deposited via an ALD process by alternatively exposing the substrate surface to one or more silicon-containing precursors, oxygen-containing sources, nitrogen-containing sources, or other precursors or reagents. Film growth proceeds through self-limiting control of surface reactions, pulse lengths of each precursor or reagent, and deposition temperatures. However, if the surface of the substrate becomes saturated, film growth is stopped.

[0120] In certain embodiments, the method described herein further comprises one or more additional silicon-containing precursors other than the organamino-vinylsilane and / or organamino-allylsilane precursors having the formulas I and / or II. Examples of additional silicon-containing precursors are, but are not limited to, monoaminosilanes (e.g., di-iso-propylaminosilane, di-sec-butylaminosilane, phenylmethylaminosilane; organosilicon compounds such as trisilylamine (TSA); monoaminosilanes (di-iso-propylaminosilane, di-sec-butylaminosilane, phenylmethylaminosilane); siloxanes (e.g., hexamethyldisiloxane (HMDSO) and dimethylsiloxane (DMSO), and hexachlorodisiloxane (HCDSO)); organosilanes (e.g., methylsilane, dimethylsilane, diethylsilane, vinyltrimethylsilane, trimethylsilane, tetramethylsilane, ethylsilane, disylmethane, 2,4-disilapentane, 1,4-disilabutane, 2,5-disilahexane, 2,2-disylpropane, 1,3,5-trisilacyclohexane and fluorinated derivatives of these compounds); phenyl-containing organosilicon compounds (e.g., dimethylphenylsilane and diphenylmethylsilane); oxygen-containing organosilicon compounds, e.g., dimethyldimethoxysilane; 1,3,5,7-tetramethylcyclotetrasiloxane; 1,1,3,3-tetramethyldisiloxane; 1,3,5,7-tetrasila-4-oxo-heptane; 2,4,6,8-tetrasila-3,7-dioxo-nonane; 2,2-dimethyl-2,4,6,8-tetrasila-3,7-dioxo-nonane; octamethylcyclotetrasiloxane; [1,3,5,7,9]-pentamethylcyclopentasiloxane; 1,3,5,7-tetrasila-2,6-dioxo-cyclooctane; It includes hexamethylcyclotrisiloxane; 1,3-dimethyldisiloxane; 1,3,5,7,9-pentamethylcyclopentasiloxane; hexamethoxydisiloxane; and fluorinated derivatives of these compounds.

[0121] Depending on the deposition method, in certain embodiments, one or more silicon-containing precursors may be introduced into the reactor in a predetermined molar volume, or from about 0.1 to about 1000 micromoles. In these or other embodiments, silicon-containing and / or organamino-vinylsilane and / or organamino-allylsilane precursors may be introduced into the reactor for a predetermined period. In certain embodiments, the period is in the range of about 0.001 to about 500 seconds.

[0122] In a specific embodiment, a silicon-containing film deposited using the method described herein is formed in the presence of oxygen using an oxygen-containing source, a reagent, or a precursor containing oxygen. The oxygen-containing source may be introduced into the reactor in the form of at least one oxygen-containing source and / or may be incidentally present in other precursors used in the deposition process. Suitable oxygen-containing sources may include, for example, water (H2O) (e.g., deionized water, purified water, and / or distilled water), hydrogen peroxide (H2O2), oxygen (O2), oxygen plasma, ozone (O3), NO, N2O, NO2, carbon monoxide (CO), carbon dioxide (CO2), and combinations thereof. In a specific embodiment, the oxygen-containing source comprises an oxygen-containing source gas introduced into the reactor at a flow rate ranging from about 1 to about 2000 cubic square centimeters (sccm) or about 1 to about 1000 sccm. The oxygen-containing source may be introduced for a time ranging from about 0.1 to about 100 seconds. In one specific embodiment, the oxygen-containing source comprises water having a temperature of 10°C or higher. In an embodiment where the film is deposited by an ALD or cyclic CVD process, the precursor pulse may have a pulse duration greater than 0.01 seconds, the oxygen-containing source may have a pulse duration less than 0.01 seconds, and the water pulse duration may have a pulse duration less than 0.01 seconds. In another embodiment, the pulse duration between pulses may be as low as 0 seconds, or the pulses may continue without purging in between. The oxygen-containing source or reagent is provided in a molar amount less than a 1:1 ratio with respect to the silicon precursor, thereby leaving at least some carbon in the deposited silicon-containing film.

[0123] In a specific embodiment, the silicon-containing film comprises silicon and nitrogen. In this embodiment, the silicon-containing film deposited using the method described herein is formed in the presence of a nitrogen-containing source. The nitrogen-containing source may be introduced into the reactor in the form of at least one nitrogen-containing source and / or may be incidentally present in other precursors used in the deposition process. Suitable nitrogen-containing sources may include, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and mixtures thereof. In a specific embodiment, the nitrogen-containing source comprises an ammonia plasma or hydrogen / nitrogen plasma source gas introduced into the reactor at a flow rate ranging from about 1 to about 2000 cubic square centimeters (sccm) or about 1 to about 1000 sccm. The nitrogen-containing source may be introduced for a time ranging from about 0.1 to about 100 seconds. In an embodiment where the film is deposited by an ALD or cyclic CVD process, the precursor pulse may have a pulse duration of more than 0.01 seconds, the nitrogen-containing source may have a pulse duration of less than 0.01 seconds, and the water pulse duration may have a pulse duration of less than 0.01 seconds. In another embodiment, the pulse duration between pulses may be as low as 0 seconds, or the pulses may continue without purging in between.

[0124] The deposition method disclosed herein may involve one or more purge gases. The purge gas used to purge and remove unconsumed reactants and / or reaction by-products 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 a specific embodiment, the purge gas, such as Ar, is supplied to the reactor at a flow rate ranging from about 10 to about 2000 sccm for about 0.1 to 1000 seconds, thereby purging unreacted material and any by-products that may remain in the reactor.

[0125] Each step of supplying a precursor, an oxygen-containing source, a nitrogen-containing source, and / or other precursors, source gases, and / or reagents can be performed by varying the time to supply them in order to change the stoichiometric composition of the silicon-containing film produced.

[0126] Energy is applied to at least one of a precursor, an oxygen-containing source, a nitrogen-containing source, a reducing agent, other precursors, or a combination thereof to induce a reaction and form a silicon-containing film or coating on a substrate. This energy may be provided, without limitation, by heat, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, X-rays, e-beams, photons, remote plasma methods, and combinations thereof. In certain embodiments, an auxiliary RF frequency source may be used to modify plasma properties on the substrate surface. In embodiments where deposition involves plasma, the plasma-generating process may include a direct plasma-generating process in which the plasma is generated directly in the reactor, or alternatively, a remote plasma-generating process in which the plasma is generated outside the reactor and supplied to the reactor.

[0127] Organamino-vinylsilane and / or organamino-allylsilane precursors, other silicon-containing precursors, and / or germanium precursors can be delivered in various ways to a reaction chamber, such as a CVD or ALD reactor. In one embodiment, a liquid delivery system may be used. In an alternative embodiment, a combined liquid delivery and flash evaporation process unit, such as a turbo evaporator manufactured by MSP Corporation in Shoreview, Minnesota, is used to enable volumetric delivery of low-volatility materials, which results in reproducible transport and deposition without thermal decomposition of the precursor. In the liquid delivery formulation, the precursor described herein may be delivered in a pure liquid form or, alternatively, used as a solvent formulation or composition containing it. Thus, in a specific embodiment, the precursor formulation may include solvent component(s) of suitable properties that may be desirable or advantageous in a given end-use field for forming a film on a substrate.

[0128] In the case of this embodiment, where the precursor(s) having Formula I and / or II are used in a composition comprising a solvent and the organamino-vinylsilane and / or organamino-allylsilane precursors having Formula I and / or II described herein, the selected solvent and mixtures thereof do not react with the organamino-vinylsilane and / or organamino-allylsilane. The amount of solvent in weight percentage in the composition is in the range of 0.5 wt% to 99.5% or 10 wt% to 75 wt%. In this or other embodiment, the solvent has a boiling point (bp) similar to the boiling point (bp) of the precursor having Formula I and / or II, or the difference between the bp of the solvent and the bp of the precursor having Formula I and / or II is 40°C or less, 30°C or less, 20°C or less, or 10°C. Alternatively, the difference between the boiling points is a range from any one or more of the following endpoints: 0, 10, 20, 30, or 40°C. Examples of suitable ranges of bp difference 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), alkyl hydrocarbons (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] In another embodiment, a vessel for depositing a silicon-containing film comprising one or more organamino-vinylsilane and / or organamino-allylsilane precursor(s) having formula I or II is described herein. In one specific embodiment, the vessel comprises at least one pressurizable vessel (preferably made of stainless steel) equipped with suitable valves and fittings for transferring one or more precursors to a reactor for a CVD or ALD process. In this or other embodiment, the organamino-vinylsilane and / or organamino-allylsilane precursors having formula I and / or II are provided in a pressurizable vessel made of stainless steel, and the purity of the precursor is 98 weight% or more or 99.5% or more, which is suitable for most semiconductor applications. In a specific embodiment, this vessel may also have means for mixing the precursor with one or more additional precursors, if preferred. In this or other embodiment, the contents of the vessel(s) may be pre-mixed with additional precursors. Alternatively, the organamino-vinylsilane and / or organamino-allylsilane precursor and / or other precursors may be maintained in separate containers or a single container having separation means for maintaining the organamino-vinylsilane and / or organamino-allylsilane precursor and other precursors separately during storage.

[0130] In one embodiment of the method described herein, a cyclic deposition process such as CCVD, ALD, or PEALD may be used, wherein at least one silicon-containing precursor selected from organamino-vinylsilane and / or organamino-allylsilane precursors having the chemical formula described herein and optionally a nitrogen-containing source such as, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma are used.

[0131] In a specific embodiment, a gas line connecting the precursor canister to the reaction chamber is heated to one or more temperatures according to process requirements, and a container of an organamino-vinylsilane and / or organamino-allylsilane precursor having Formula I and / or II described herein is maintained at one or more temperatures for bubbling. In another embodiment, a solution comprising at least one silicon-containing precursor having the formula described herein is injected into an evaporator maintained at one or more temperatures for direct liquid injection.

[0132] A flow of argon and / or other gas may be used as a carrier gas to assist in delivering vapor of at least one organamino-vinylsilane and / or organamino-allylsilane precursor to the reaction chamber during the precursor pulsing process. In a specific embodiment, the reaction chamber process pressure is about 10 Torr or less. In another embodiment, the reaction chamber process pressure is about 5 Torr or less.

[0133] In the case of multi-component silicon-containing films, other precursors, such as silicon-containing precursors, nitrogen-containing precursors, reducing agents, or other reagents may alternatively be introduced into the reaction chamber.

[0134] In one embodiment of the method described herein, a silicon oxide or carbon-doped silicon oxide film having a carbon content in the range of zero atomic percent to 20 atomic percent is deposited using a hydrogen-containing plasma to improve the thermal ALD process and film properties. In this embodiment, the method comprises the following:

[0135] a. A step of placing one or more substrates including surface features in a reactor, heating the reactor to one or more temperatures ranging from ambient temperature to about 550°C, and optionally maintaining the reactor at a pressure of 100 torr or less;

[0136] b. A step of introducing into a reactor at least one organamino-vinylsilane and / or organamino-allylsilane precursor comprising at least one vinyl and / or allyl group and at least one organamino anchor group connected to at least one silicon atom represented by chemical formulas I and / or II;

[0137] c. A step of purging the reactor with an inert gas to remove unreacted silicon precursors thereby, and forming a composition comprising the purge gas and silicon precursors;

[0138] d. A step of providing an oxygen-containing source to a reactor to react with the surface and form a film containing silicon and oxygen;

[0139] e. A step of removing reaction by-products by purging with an inert gas;

[0140] f. A step of repeating steps b through e to provide silicon oxide or carbon-doped silicon oxide of a desired thickness.

[0141] In these or other embodiments, the UV exposure step may be performed during the film deposition process or when the deposition is completed. In other embodiments, a film containing silicon and nitrogen, such as silicon nitride or silicon carbonitride, may be deposited using the organamino-vinylsilane and / or organamino-allylsilane described herein in the same steps outlined above, except that a nitrogen-containing source is used instead of an oxygen-containing source.

[0142] In one embodiment, the substrate comprises at least one feature, wherein the feature comprises a pattern trench having an aspect ratio of 1:9 or greater and / or an opening of 180 nm or less.

[0143] In an embodiment where the film is treated with plasma, the plasma source is selected from the group consisting of hydrogen plasma, a plasma containing hydrogen and helium, and a plasma containing hydrogen and argon. The hydrogen plasma lowers the film dielectric constant and increases resistance to damage for the subsequent plasma ashing process while still maintaining the carbon content of the bulk with almost no change.

[0144] Throughout the detailed description, the term “ALD or ALD-like” refers, without limitation, to a process comprising the following: a) each reactant, including a silicon precursor and a reaction gas, is sequentially introduced into a reactor such as a single-wafer ALD reactor, a semi-batch ALD process, or a batch ALD reactor; and b) each reactant, including a silicon precursor and a reaction gas, is exposed to a substrate by moving or rotating the substrate to different regions of the reactor, and each region is separated by an inert gas curtain, i.e., a space ALD reactor or a roll-to-roll ALD reactor.

[0145] Throughout the detailed description, the term "ashing" refers to a process for removing photoresist or a carbon hard mask in a semiconductor manufacturing process using a plasma containing an oxygen source, such as O2 / inert gas plasma, O2 plasma, CO2 plasma, CO plasma, H2 / O2 plasma, or a combination thereof.

[0146] Throughout the detailed description, the term "damage resistance" refers to film characteristics after the oxygen ashing process. Good or high damage resistance is defined by the following film characteristics after oxygen ashing: a film dielectric constant of less than 4.5; a carbon content in the bulk (greater than 50 Å depth within the film) of within 5 atomic percent prior to ashing; and damage to the film less than 50 Å, observed as a difference in diluted HF etching rates between the surface near the film (less than 50 Å depth) and the bulk (greater than 50 Å depth).

[0147] In certain embodiments, organoamino-vinylsilane and / or organoamino-allylsilane precursors having Formula I and / or II described herein may also be used as dopants for metal-containing films, such as, but not limited to, metal oxide films or metal nitride films. In these embodiments, the metal-containing film is deposited using an ALD or CVD process, such as the process described herein, using a metal alkoxide, a metal amide, or a volatile organometallic precursor. Examples of suitable metal alkoxide precursors that may be used with the methods disclosed herein include, but not limited to, Group 3 to 6 metal alkoxides, Group 3 to 6 metal complexes having both alkoxy and alkyl-substituted cyclopentadienyl ligands, Group 3 to 6 metal complexes having both alkoxy and alkyl-substituted pyrrolyl ligands, Group 3 to 6 metal complexes having both alkoxy and diketonate ligands; and Group 3 to 6 metal complexes having both alkoxy and ketoester ligands.Examples of suitable metal amide precursors that can be used with the methods disclosed herein are, but are not limited to, tetrakis(dimethylamino)zirconium (TDMAZ), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethylamino)zirconium (TEMAZ), tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), and tetrakis(ethylmethylamino)hafnium (TEMAH), tetrakis(dimethylamino)titanium (TDMAT), tetrakis(diethylamino)titanium (TDEAT), tetrakis(ethylmethylamino)titanium (TEMAT), tert-butyliminotri(diethylamino)tantalum (TBTDET), tert-butyliminotri(dimethylamino)tantalum (TBTDMT), and tert-butyliminotri(ethylmethylamino)tantalum (TBTEMT). ethyliminotri(diethylamino)tantalum (EITDET), ethyliminotri(dimethylamino)tantalum (EITDMT), ethyliminotri(ethylmethylamino)tantalum (EITEMT), tert-amyliminotri(dimethylamino)tantalum (TAIMAT), tert-amyliminotri(diethylamino)tantalum, pentakis(dimethylamino)tantalum, tert-amyliminotri(ethylmethylamino)tantalum, bis(tert-butylimino)bis(dimethylamino)tungsten (BTBMW), bis(tert-butylimino)bis(diethylamino)tungsten, bis(tert-butylimino)bis(ethylmethylamino)tungsten, and combinations thereof. Examples of suitable organometallic precursors that can be used with the methods disclosed herein include, but are not limited to, group 3 metal cyclopentadienyls or alkyl cyclopentadienyls. Exemplary group 3 to 6 metals of the present invention include, but are not limited to, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Lu, Ti, Hf, Zr, V, Nb, Ta, Cr, Mo, and W.

[0148] In certain embodiments, the resulting silicon-containing film or coating may be exposed to post-deposition treatment, such as, but not limited to, plasma treatment, chemical treatment, exposure to ultraviolet light, exposure to electron beam, and / or other treatments that affect one or more properties of the film.

[0149] In certain embodiments, the silicon-containing film described herein has a dielectric constant of 6 or less. In these or other embodiments, the film may have a dielectric constant of about 5 or less, or about 4 or less, or about 3.5 or less. However, it is assumed that films having other dielectric constants (e.g., higher or lower) may be formed depending on the desired end use of the film. Examples of silicon-containing or silicon-containing films formed using the organamino-vinylsilane and / or organamino-allylsilane precursors and processes described herein are those with the formula Si x O y C z N v H wIt has, wherein Si is in the range of about 10% to about 40%; O is in the range of about 0% to about 65%; C is in the range of about 0% to about 75% or about 0% to about 50%; N is in the range of about 0% to about 75% or about 0% to 50%; and H is in the range of about 0% to about 50% atomic weight percentage, where x+y+z+v+w = 100 atomic weight percentage determined, for example, by XPS or other means. Another example of a silicon-containing film formed using the organamino-vinylsilane and / or organamino-allylsilane precursors and processes described herein is silicon carbonitride, wherein the carbon content is 1 atomic% to 80 atomic% as measured by XPS. In addition, another example of a silicon-containing film formed using the organamino-vinylsilane and / or organamino-allylsilane precursors and processes described herein is amorphous silicon, wherein the sum of the nitrogen and carbon contents is <10 atomic%, preferably <5 atomic%, most preferably <1 atomic% as measured by XPS.

[0150] As previously mentioned, the method described herein may be used to deposit a silicon-containing film on at least a portion of a substrate. Examples of suitable substrates include, but are not limited to, silicon, germanium-doped silicon, germanium, 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, flexible substrates, organic polymers, porous organic and inorganic materials, metals such as copper and aluminum, and diffusion barrier layers such as, but are not limited to, TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN. The film is compatible with various subsequent processing steps, such as chemical mechanical planarization (CMP) and anisotropic etching processes.

[0151] The deposited film has applications including, but not limited to, computer chips, optical devices, magnetic information storage devices, coatings on supporting materials or substrates, microelectromechanical systems (MEMS), nanoelectromechanical systems, thin-film transistors (TFTs), light-emitting diodes (LEDs), organic light-emitting diodes (OLEDs), IGZO, and liquid crystal displays (LCDs).

[0152] The method described herein provides a high-quality film comprising germanium, silicon, silicon carbide, silicon nitride, carbon-doped silicon nitride, silicon oxide, silicon oxynitride, carbon-doped silicon oxynitride, and carbon-doped silicon oxide. The term “high quality” means a film exhibiting one or more of the following characteristics: a density of about 2.1 g / cc or more, 2.2 g / cc or more, 2.25 g / cc or more; a wet etching rate of 2.5 Å / s or less, 2.0 Å / s or less, 1.5 Å / s or less, 1.0 Å / s or less, 0.5 Å / s or less, 0.1 Å / s or less, 0.05 Å / s or less, 0.01 Å / s or less, measured in a solution of HF to water diluted HF (0.5 wt% dHF) acid at a 1:100 ratio, and about 1 e-8 A / cm² or less. 2 Leakage current of up to 6 MV / cm); hydrogen impurities of about 5 e20 at / cc or less as measured by SIMS; very low non-uniformity, low level of surface roughness, and combinations thereof. Regarding etching rate, the thermally grown silicon oxide film has an etching rate of 0.5 Å / s at 0.5 wt% HF.

[0153] In certain embodiments, one or more silicon precursors having formulas I and II described herein may be used to form a solid, non-porous, and substantially pore-free film containing silicon and oxygen.

[0154] The following examples illustrate methods for preparing organamino-vinylsilane and / or organamino-allylsilane precursors, depositing silicon-containing films, producing vinyl-functionalized and / or allyl-functionalized surfaces, and producing germanium seed layers as described herein, and are not intended to be limited in any way.

[0155] Examples

[0156] Example 1. Synthesis of tris(ethylamino)vinylsilane.

[0157] Under the protection of nitrogen, a solution of ethylamine in THF (800 mL, 2.0 M, 1.60 mol) was added via a cannula to a solution of triethylamine (175 g, 1.73 mol) in hexane (1 liter) in a 3-liter three-necked round-bottom flask equipped with a mechanical stirrer and a reflux condenser. The combined solution was cooled to -20°C and stirred. To this mixture, a solution of trichlorovinylsilane (80.0 g, 0.495 mol) in hexane (80 g) was added dropwise over 2 hours at -20°C. The resulting white slurry was heated to room temperature and stirred for an additional 2 hours. The white solid was removed by filtration over a glass frit, and the solvent was removed at room temperature under reduced pressure (20 Torr). The resulting concentrated crude liquid was purified by vacuum distillation (1 Torr / 45°C) to obtain 55.4 g of tris(ethylamino)vinylsilane. The boiling point was determined to be 199°C by DSC. GC-MS analysis showed the following mass peaks: m / z = 187 (M+), 172 (M-15), 160, 143, 129, 118, 100, 86, 72, 57, 44.

[0158] Example 2. Treatment of silica gel with tris(ethylamino)vinylsilane.

[0159] Under nitrogen protection, 0.5 g of silica gel (Davasil TMGrade 645 (60-100 mesh, 150 Å) was stirred in 5 mL of a 50 wt% solution of tris(ethylamino)vinylsilane in THF at 80°C for 2 hours. The liquid phase was decanted, and the solid was rinsed several times with hot THF before drying under vacuum. Both the untreated and treated silica gels were analyzed by FTIR spectroscopy using KBr pellets. In the FTIR spectrum of the untreated silica gel corresponding to the isolated surface Si-OH groups, 3741 cm⁻¹ was observed. -1 The sharp peak at was not detected in the FTIR spectrum of the treated silica gel. The treated silica gel exhibited the following novel peaks in the FTIR spectrum: 3418 (NH), 3062 (vinyl CH), 3021 (vinyl CH), 2968 (vinyl CH), 2935 (ethyl CH), and 2876 (ethyl CH). This indicates that the surface of the silica gel was functionalized with vinyl and ethylamino groups at a relatively low temperature within a short period after treatment with tris(ethylamino)vinylsilane.

[0160] Example 3. Reaction of triethoxyvinylsilane and tert-butylgerman.

[0161] Approximately 1 mL of a 1:1 molar mixture of triethoxyvinylsilane and tert-butylgerman was sealed in a 9.5 mL stainless steel cell equipped with an internal pressure transducer and a thermocouple. The sample was heated to 250°C and maintained isothermally for 1 hour. No significant increase in pressure was detected, but a weak exothermic thermal event was observed when the temperature increased to ~212°C. When the mixture was cooled back to room temperature, it was analyzed by GC and GC-MS. The 1,1-addition and 1,2-addition hydrogermylation products 1-triethoxysilyl-1-(tert-butylgermyl)ethane (minority) and 1-triethoxysilyl-2-(tert-butylgermyl)ethane (majority) were detected according to the following mass peaks, respectively: (minority) m / z = 324 (M+), 308, 280, 266, 238, 222, 210, 194, 179, 163, 147, 135, 119, 101, 89, 79, 57, 41; (Multiple) m / z = 324 (M+), 308, 280, 268, 238, 222, 211, 193, 181, 163, 149, 135, 119, 103, 91, 79, 57, 41. This demonstrates that Ge-H bonds in precursors, such as germane, digermane, and tert-butylgermane, can react with Si-vinyl groups between 200-250°C in the absence of a catalyst. This supports the proposal to produce a Ge-seed layer on a SiO2 substrate by first functionalizing the surface with vinyl groups and then reacting with germane or digermane to create a Ge-H terminald surface before germanium CVD growth.

[0162] Although the present disclosure is described with reference to specific preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may substitute for the components thereof without departing from the scope of the invention. Furthermore, various modifications may be made to apply the teachings of the present invention to specific situations or materials without departing from the essence thereof. Accordingly, the present invention is not limited to specific embodiments, but is intended to include all embodiments included within the scope of the appended claims.

Claims

Claim 1 A method for forming a germanium-containing film on at least one surface of a substrate by a deposition process, comprising the steps of: providing at least one surface of a substrate to a reaction chamber, wherein the substrate has exposed surface hydroxyl groups; and introducing at least one organamino-vinylsilane precursor represented by the following formula I, or at least one organamino-allylsilane precursor represented by the following formula II, into the reaction chamber at a temperature of 100 °C or lower for vinyl or allyl-surface functionalization of the substrate. In the above equation, R 1 It is linear or branched C1 to C 10 Alkyl groups, linear or branched C3 to C 10 Alkenyl group, linear or branched C3 to C 10 alkynyl group, C3 to C 10 Cyclic alkyl group, and C6 to C 10 Selected from the group consisting of aryls; R 2 is hydrogen, linear or branched C1 to C 10 Alkyl group, linear or branched C2 to C6 alkenyl group, linear or branched C3 to C6 alkenyl group, C3 to C 10 Cyclic alkyl group, and C6 to C 10 Selected from the group consisting of aryls; R 3 and R 4 Each is independently hydrogen, linear or branched C1 to C 10 Alkyl group, linear or branched C2 to C6 alkenyl group, linear or branched C3 to C6 alkenyl group, C3 to C 10 Cyclic alkyl group, C6 to C 10 Aryl group, C1 to C 10 Linear, cyclic, or branched alkoxy groups, the organoamino groups defined above (NR 1 R 2 A method comprising: selecting from the group consisting of ), and halides selected from the group consisting of Cl, Br, and I; purging a reaction chamber with a purge gas; introducing at least one first germanium-containing precursor comprising at least one Ge-H bond into the reaction chamber; purging the reaction chamber with a purge gas; and introducing at least one second germanium-containing precursor identical or different from the first germanium-containing precursor into the reaction chamber. Claim 2 In claim 1, at least one organic amino-vinylsilane precursor is tris(methylamino)vinylsilane, tris(ethylamino)vinylsilane, tris(n-propylamino)vinylsilane, tris(iso-propylamino)vinylsilane, tris(sec-butylamino)vinylsilane, tris(tert-butylamino)vinylsilane, tris(dimethylamino)vinylsilane, tris(N-ethylmethylamino)vinylsilane, tris(diethylamino)vinylsilane, tris(N-methylcyclohexylamino)vinylsilane, tris(N-methylphenylamino)vinylsilane, tri(pyrrolidino)vinylsilane, tri(piperidino)vinylsilane, tri(pyrrolillyl)vinylsilane, bis(methylamino)methylvinylsilane, bis(ethylamino)methylvinylsilane, bis(n-propylamino)methylvinylsilane, Bis(iso-propylamino)methylvinylsilane, Bis(sec-butylamino)methylvinylsilane, Bis(tert-butylamino)methylvinylsilane, Bis(dimethylamino)methylvinylsilane, Bis(N-ethylmethylamino)methylvinylsilane, Bis(diethylamino)methylvinylsilane, Bis(N-methylcyclohexylamino)methylvinylsilane, Bis(N-methylphenylamino)methylvinylsilane, Di(pyrrolidino)methylvinylsilane, Di(piperidino)methylvinylsilane, Di(pyrrolyl)methylvinylsilane, Bis(methylamino)divinylsilane, Bis(ethylamino)divinylsilane, Bis(n-propylamino)divinylsilane, Bis(iso-propylamino)divinylsilane, Bis(sec-butylamino)divinylsilane, Bis(tert-butylamino)divinylsilane, Bis(dimethylamino)divinylsilane, Bis(N-ethylmethylamino)divinylsilane, Bis(diethylamino)divinylsilane, Bis(N-methylcyclohexylamino)divinylsilane, Bis(N-methylphenylamino)divinylsilane, Di(pyrrolidino)divinylsilane, Di(piperidino)divinylsilane, Di(pyrrolyl)divinylsilane, (methylamino)dimethylvinylsilane, (ethylamino)dimethylvinylsilane, (n-propylamino)dimethylvinylsilane, (iso-propylamino)dimethylvinylsilane, (sec-butylamino)dimethylvinylsilane, (tert-butylamino)dimethylvinylsilane, (dimethylamino)dimethylvinylsilane, (N-ethylmethylamino)dimethylvinylsilane, (diethylamino)dimethylvinylsilane, (N-methylcyclohexylamino)dimethylvinylsilane,(N-methylphenylamino)dimethylvinylsilane, (pyrrolidino)dimethylvinylsilane, (piperidino)dimethylvinylsilane, (pyrrolyl)dimethylvinylsilane, (methylamino)methyldivinylsilane, (ethylamino)methyldivinylsilane, (n-propylamino)methyldivinylsilane, (iso-propylamino)methyldivinylsilane, (sec-butylamino)methyldivinylsilane, (tert-butylamino)methyldivinylsilane, (dimethylamino)methyldivinylsilane, (N-ethylmethylamino)methyldivinylsilane, (diethylamino)methyldivinylsilane, (N-methylcyclohexylamino)methyldivinylsilane, (N-methylphenylamino)methyldivinylsilane, (pyrrolidino)methyldivinylsilane, (piperidino)methyldivinylsilane, (pyrrolyl)methyldivinylsilane, A method comprising at least one compound selected from the group consisting of (methylamino)trivinylsilane, (ethylamino)trivinylsilane, (n-propylamino)trivinylsilane, (iso-propylamino)trivinylsilane, (sec-butylamino)trivinylsilane, (tert-butylamino)trivinylsilane, (dimethylamino)trivinylsilane, (N-ethylmethylamino)trivinylsilane, (diethylamino)trivinylsilane, (N-methylcyclohexylamino)trivinylsilane, (pyrrolidino)methyltrivinylsilane, (piperidino)trivinylsilane, and (pyrrolill)trivinylsilane. Claim 3 In claim 1, at least one organamino-allylsilane precursor is tris(methylamino)allylsilane, tris(ethylamino)allylsilane, tris(n-propylamino)allylsilane, tris(iso-propylamino)allylsilane, tris(sec-butylamino)allylsilane, tris(tert-butylamino)allylsilane, tris(dimethylamino)allylsilane, tris(N-ethylmethylamino)allylsilane, tris(diethylamino)allylsilane, tris(N-methylcyclohexylamino)allylsilane, tris(N-methylphenylamino)allylsilane, tri(pyrrolidino)allylsilane, tri(piperidino)allylsilane, tri(pyrrolillyl)allylsilane, bis(methylamino)methylallylsilane, bis(ethylamino)methylallylsilane, bis(n-propylamino)methylallylsilane, Bis(iso-propylamino)methylallylsilane, Bis(sec-butylamino)methylallylsilane, Bis(tert-butylamino)methylallylsilane, Bis(dimethylamino)methylallylsilane, Bis(N-ethylmethylamino)methylallylsilane, Bis(diethylamino)methylallylsilane, Bis(N-methylcyclohexylamino)methylallylsilane, Bis(N-methylphenylamino)methylallylsilane, Di(pyrrolidino)methylallylsilane, Di(piperidino)methylallylsilane, Di(pyrrolil)methylallylsilane, Bis(methylamino)diallylsilane, Bis(ethylamino)diallylsilane, Bis(n-propylamino)diallylsilane, Bis(iso-propylamino)diallylsilane, Bis(sec-butylamino)diallylsilane, Bis(tert-butylamino)diallylsilane, Bis(dimethylamino)diallylsilane, Bis(N-ethylmethylamino)diallylsilane, Bis(diethylamino)diallylsilane, Bis(N-methylcyclohexylamino)diallylsilane, Bis(N-methylphenylamino)diallylsilane, Di(pyrrolidino)diallylsilane, Di(piperidino)diallylsilane, Di(pyrrolil)diallylsilane, (methylamino)dimethylallylsilane, (ethylamino)dimethylallylsilane, (n-propylamino)dimethylallylsilane, (iso-propylamino)dimethylallylsilane, (sec-butylamino)dimethylallylsilane, (tert-butylamino)dimethylallylsilane, (dimethylamino)dimethylallylsilane, (N-ethylmethylamino)dimethylallylsilane, (diethylamino)dimethylallylsilane, (N-methylcyclohexylamino)dimethylallylsilane,(N-methylphenylamino)dimethylallylsilane, (pyrrolidino)dimethylallylsilane, (piperidino)dimethylallylsilane, (pyrrolyl)dimethylallylsilane, (methylamino)methyldiallylsilane, (ethylamino)methyldiallylsilane, (n-propylamino)methyldiallylsilane, (iso-propylamino)methyldiallylsilane, (sec-butylamino)methyldiallylsilane, (tert-butylamino)methyldiallylsilane, (dimethylamino)methyldiallylsilane, (N-ethylmethylamino)methyldiallylsilane, (diethylamino)methyldiallylsilane, (N-methylcyclohexylamino)methyldiallylsilane, (N-methylphenylamino)methyldiallylsilane, (pyrrolidino)methyldiallylsilane, (piperidino)methyldiallylsilane, (pyrrolyl)methyldiallylsilane, A method comprising at least one compound selected from the group consisting of (methylamino)triallylsilane, (ethylamino)triallylsilane, (n-propylamino)triallylsilane, (iso-propylamino)triallylsilane, (sec-butylamino)triallylsilane, (tert-butylamino)triallylsilane, (dimethylamino)triallylsilane, (N-ethylmethylamino)triallylsilane, (diethylamino)triallylsilane, (N-methylcyclohexylamino)triallylsilane, (pyrrolidino)methyltriallylsilane, (piperidino)triallylsilane, and (pyrrolil)triallylsilane. Claim 4 The method of claim 1, wherein the organoamino-vinylsilane or organoamino-allylsilane substantially does not contain at least one impurity selected from the group consisting of organic amines, halide ions, and metal ions. Claim 5 In claim 1, at least one germanium-containing precursor is trichlorogermane (Cl3GeH), germane (GeH4), digermane (Ge2H6), tert-butylgermane ( t A method selected from the group consisting of BuGeH3), phenylgerman, sec-butylgerman, iso-butylgerman, and benzylgerman. Claim 6 A method according to claim 1, further comprising the step of introducing at least one first germanium-containing precursor and then introducing a reducing gas into a reaction chamber. Claim 7 The method of claim 1, wherein at least one surface of the substrate is a silicon-containing film, and the step of providing at least one surface of the substrate to a reaction chamber comprises performing the following steps until a desired thickness of the silicon-containing film is achieved: introducing at least one organamino-vinylsilane of Formula I or at least one organamino-allylsilane of Formula II into a reactor; purging the reactor with a purge gas; introducing an oxygen-containing source and / or a nitrogen-containing source into the reactor; and purging the reactor with a purge gas. Claim 8 In claim 7, the nitrogen-containing source is selected from the group consisting of ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and mixtures thereof. Claim 9 In claim 7, the oxygen-containing source is selected from the group consisting of water, hydrogen peroxide, oxygen, oxygen plasma, ozone (O3), nitric oxide, nitrous oxide, nitrogen dioxide, carbon monoxide, carbon dioxide, and mixtures thereof. Claim 10 A composition for forming a vinyl or allyl-surface-functionalized substrate comprising at least one organoamino-vinylsilane precursor represented by the following formula I, or at least one organoamino-allylsilane precursor represented by the following formula II: In the above equation, R 1 It is linear or branched C1 to C 10 Alkyl groups, linear or branched C3 to C 10 Alkenyl group, linear or branched C3 to C 10 alkynyl group, C3 to C 10 Cyclic alkyl group, and C6 to C 10 Selected from the group consisting of aryls; R 2 is hydrogen, linear or branched C1 to C 10 Alkyl group, linear or branched C2 to C6 alkenyl group, linear or branched C3 to C6 alkenyl group, C3 to C 10 Cyclic alkyl group, and C6 to C 10 Selected from the group consisting of aryls; R 3 and R 4 Each is independently hydrogen, linear or branched C1 to C 10 Alkyl group, linear or branched C2 to C6 alkenyl group, linear or branched C3 to C6 alkenyl group, C3 to C 10 Cyclic alkyl group, C6 to C 10 Aryl group, C1 to C 10 Linear, cyclic, or branched alkoxy groups, the organoamino groups defined above (NR 1 R 2 It is selected from the group of halides selected from the group consisting of ), and Cl, Br, and I. Claim 11 In claim 10, at least one organamino-vinylsilane precursor is tris(ethylamino)vinylsilane, tris(iso-propylamino)vinylsilane, tris(tert-butylamino)vinylsilane, tris(N-ethylmethylamino)vinylsilane, tris(N-methylcyclohexylamino)vinylsilane, tris(N-methylphenylamino)vinylsilane, tri(pyrrolidino)vinylsilane, tri(piperidino)vinylsilane, tri(pyrrolyl)vinylsilane, bis(ethylamino)methylvinylsilane, bis(tert-butylamino)methylvinylsilane, bis(N-methylcyclohexylamino)methylvinylsilane, bis(N-methylphenylamino)methylvinylsilane, di(pyrrolidino)methylvinylsilane, di(piperidino)methylvinylsilane, di(pyrrolyl)methylvinylsilane, Bis(ethylamino)divinylsilane, Bis(n-propylamino)divinylsilane, Bis(sec-butylamino)divinylsilane, Bis(N-ethylmethylamino)divinylsilane, Bis(diethylamino)divinylsilane, Bis(N-methylcyclohexylamino)divinylsilane, Bis(N-methylphenylamino)divinylsilane, Di(pyrrolidino)divinylsilane, Di(piperidino)divinylsilane, Di(pyrrolyl)divinylsilane, (n-propylamino)dimethylvinylsilane, (sec-butylamino)dimethylvinylsilane, (tert-butylamino)dimethylvinylsilane, (N-ethylmethylamino)dimethylvinylsilane, (N-methylcyclohexylamino)dimethylvinylsilane, (N-methylphenylamino)dimethylvinylsilane, (pyrrolidino)dimethylvinylsilane, (Piperidino)dimethylvinylsilane, (Pyrrolyl)dimethylvinylsilane, (methylamino)methyldivinylsilane, (ethylamino)methyldivinylsilane, (n-propylamino)methyldivinylsilane, (iso-propylamino)methyldivinylsilane, (sec-butylamino)methyldivinylsilane, (tert-butylamino)methyldivinylsilane, (dimethylamino)methyldivinylsilane, (N-ethylmethylamino)methyldivinylsilane, (N-methylcyclohexylamino)methyldivinylsilane, (N-methylphenylamino)methyldivinylsilane, (pyrrolidino)methyldivinylsilane, (Piperidino)methyldivinylsilane, (Pyrrolyl)methyldivinylsilane, (methylamino)trivinylsilane, (ethylamino)trivinylsilane, (n-propylamino)trivinylsilane, (iso-propylamino)trivinylsilane, (sec-butylamino)trivinylsilane,A composition comprising at least one compound selected from the group consisting of (tert-butylamino)trivinylsilane, (N-ethylmethylamino)trivinylsilane, (diethylamino)trivinylsilane, (N-methylcyclohexylamino)trivinylsilane, (pyrrolidino)methyltrivinylsilane, (piperidino)trivinylsilane, and (pyrrolil)trivinylsilane. Claim 12 In claim 10, at least one organamino-allylsilane precursor is tris(methylamino)allylsilane, tris(ethylamino)allylsilane, tris(n-propylamino)allylsilane, tris(iso-propylamino)allylsilane, tris(sec-butylamino)allylsilane, tris(tert-butylamino)allylsilane, tris(N-methylcyclohexylamino)allylsilane, tris(N-methylphenylamino)allylsilane, tri(pyrrolidino)allylsilane, tri(piperidino)allylsilane, tri(pyrrolil)allylsilane, bis(ethylamino)methylallylsilane, bis(n-propylamino)methylallylsilane, bis(sec-butylamino)methylallylsilane, bis(tert-butylamino)methylallylsilane, bis(N-methylcyclohexylamino)methylallylsilane, Bis(N-methylphenylamino)methylallylsilane, Di(pyrrolidino)methylallylsilane, Di(piperidino)methylallylsilane, Di(pyrrolyl)methylallylsilane, Bis(methylamino)diallylsilane, Bis(ethylamino)diallylsilane, Bis(n-propylamino)diallylsilane, Bis(sec-butylamino)diallylsilane, Bis(diethylamino)diallylsilane, Bis(N-methylcyclohexylamino)diallylsilane, Bis(N-methylphenylamino)diallylsilane, Di(pyrrolidino)diallylsilane, Di(piperidino)diallylsilane, Di(pyrrolyl)diallylsilane, (ethylamino)dimethylallylsilane, (n-propylamino)dimethylallylsilane, (iso-propylamino)dimethylallylsilane, (sec-butylamino)dimethylallylsilane, (tert-butylamino)dimethylallylsilane, (N-ethylmethylamino)dimethylallylsilane, (N-methylcyclohexylamino)dimethylallylsilane, (N-methylphenylamino)dimethylallylsilane, (pyrrolidino)dimethylallylsilane, (piperidino)dimethylallylsilane, (pyrrolil)dimethylallylsilane, (methylamino)methyldiallylsilane, (ethylamino)methyldiallylsilane, (n-propylamino)methyldiallylsilane, (iso-propylamino)methyldiallylsilane, (sec-butylamino)methyldiallylsilane, (tert-butylamino)methyldiallylsilane, (dimethylamino)methyldiallylsilane, (N-ethylmethylamino)methyldiallylsilane, (N-methylcyclohexylamino)methyldiallylsilane, (N-methylphenylamino)methyldiallylsilane, (Pyrrolidino)methyldiallylsilane,A composition comprising at least one compound selected from the group consisting of (piperidino)methyltriallylsilane, (pyrrolidino)methyltriallylsilane, (methylamino)triallylsilane, (ethylamino)triallylsilane, (n-propylamino)triallylsilane, (iso-propylamino)triallylsilane, (sec-butylamino)triallylsilane, (tert-butylamino)triallylsilane, (dimethylamino)triallylsilane, (N-ethylmethylamino)triallylsilane, (diethylamino)triallylsilane, (N-methylcyclohexylamino)triallylsilane, (pyrrolidino)methyltriallylsilane, (piperidino)triallylsilane, and (pyrrolidino)triallylsilane.

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