Composition for germanium seed layer and method of use thereof

Abstract

This invention relates to precursors and methods for (a) forming silicon-containing films and (b) functionalizing a substrate surface to form a germanium seed layer suitable for depositing Ge films. In one aspect, precursors of Formula I and / or Formula II as described herein are provided.

Description

Background Technology

[0001] This invention relates to organosilicon compounds that can be used to deposit silicon-containing films and generate vinyl-functionalized surfaces suitable for producing germanium seed layers, which facilitates the growth of high-quality reduced or metallic germanium films on solid substrate surfaces. The invention also relates to methods of using these compounds.

[0002] This document describes novel organoamino-vinylsilane and organoamino-allylsilane precursor compounds, compositions comprising the thereof, and methods for depositing silicon-containing films, such as, but not limited to, silicon oxide, silicon oxynitride, silicon oxycarbonitride, or carbon-doped silicon oxide, by thermal atomic layer deposition (ALD) or plasma-enhanced atomic layer deposition (PEALD) processes or combinations thereof. More specifically, this document describes compositions and methods for forming stoichiometric or non-stoichiometric silicon-containing films or materials at one or more deposition temperatures of about 600 °C or lower (including, for example, about 25 °C to about 350 °C), wherein the resulting film is end-capped with vinyl functional groups and is suitable for forming a germanium seed layer.

[0003] One long-standing problem with plasma-enhanced chemical vapor deposition (PECVD) or thermochemical vapor deposition (CVD) of germane and digerane on dielectric substrates such as silicon oxide is that the reactivity of germane compounds with the hydroxyl groups on the substrate surface is much less than the reactivity of the Ge-H bond breakdown during Ge-Ge bond formation. This reactivity mismatch results in the formation of germanium islands on the substrate instead of a smooth film. To overcome this "island effect" or "island growth" (which leads to high levels of surface roughness in the resulting germanium film), it is necessary to initially lay a smooth seed layer on the surface, providing a smooth starting surface and allowing for subsequent uniform growth of the germanium film. However, growing this seed layer on the dielectric substrate surface using typical PECVD or CVD germanium precursors still suffers from typical CVD drawbacks, such as thickness control, low selectivity of the dielectric surface, non-self-limiting reactivity, and low conformality.

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

[0005] Publication No. EP1464724A2 discloses a chemical vapor deposition method with formula MX suitable for silicon and germanium films. a H b (NR 1 R 2 ) c R 3 d R 4 e Silicon- and germanium-containing precursors.

[0006] Famá, S et al., Appl. Phys. Lett. 2002, 81, 586, describe the epitaxial growth of germanium on silicon for the purpose of fabricating pin photodetectors, which first involves depositing a thin Ge / Si buffer layer with GeH4 by chemical vapor deposition at 350 °C, followed by chemical vapor deposition of a thicker germanium film at 600 °C.

[0007] Hair, ML et al., Phys. Chem. 1969, 73, 2372 reported the functionalization of silicon dioxide with chlorosilanes, which occurred at a satisfactory rate in the gas phase between 300 and 400 °C compared with methoxysilanes (100-200 °C).

[0008] Miao, QJ et al., Catal. Commun. 2003, 4, 637, describe the treatment of fumed silica in toluene under reflux for 48 hours with vinyltriethoxysilane, followed by reaction with water for another 48 hours to functionalize the surface with vinyl.

[0009] Zapilko, C. et al. J. Am. Chem. Soc. 2006, 128, 16266 describes the functionalization of periodic mesoporous silica by treating it at 109 °C for 15 hours with a vinyl-substituted trimethylsilylamine from toluene using chloropropyl dimethylsilyl and vinyl dimethylsilyl.

[0010] US Patent No. 8,460,753B2 describes a precursor and method for depositing silicon dioxide or silicon oxide films by ALD or CVD, wherein the precursor is a precursor having the formula R 1 n R 2 m Si(NR 3 R 4 ) 4-n-m aminovinylsilanes and having the formula (R 1 R 2 SiNR 3 ) p Cyclic silazanes, wherein R 1 It is alkenyl or aromatic, for example, vinyl, allyl and phenyl.

[0011] US Publication No. 20150275355A1 describes the use of formula R 1 n Si(NR 2 R 3 ) m H 4-m-n The precursors, more specifically, compositions and methods for forming silicon oxide films using organic amino-methylsilane precursors.

[0012] US Publication No. 20090162973A1 describes the use of a GeR-type... x 1 (NR 2 R 3 ) (4-X) The method involves depositing a germanium film or a germanium antimony telluride film on a substrate using a germanium-containing precursor, wherein the method involves exposing the substrate to the germanium-containing precursor alone or in combination with an oxidizing gas or a reducing gas.

[0013] US Publication No. 20110036289A1 describes a method for depositing a germanium seed layer on a hydrogen-treated silicon substrate by CVD using a GeH4 precursor at low temperature, followed by the subsequent growth of an n-doped or p-doped germanium epitaxial film using the GeH4 precursor at elevated temperatures in the presence of phosphine or diborane, respectively.

[0014] US Publication No. 20110084308A1 discloses a method for selectively growing high-quality strained or strain-relaxed Ge on a patterned Si substrate. The method involves first growing a silicon-germanium buffer layer by CVD using Si2H6 and GeH4 precursors at 350-400 °C, then growing a Ge seed layer by CVD using GeH4 precursors at 350-400 °C, and then growing a Ge epitaxial film by CVD using GeH4 precursors at 550-600 °C.

[0015] U.S. Publications 20130230975A1 and 20140331928A1 both describe the formation of a germanium seed layer on a substrate using an aminogermanium-based gas, followed by the growth of a germanium thin film using a germanium-based gas.

[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 dielectric substrate surfaces.

[0018] Compared to existing technologies, the seed layer precursor of this invention utilizes a silane-amine functional group as an anchoring group to attach vinyl or allyl groups to the surface. This chemistry transforms the hydroxyl-rich surface into a vinyl or allyl-rich surface. Then, germanane or digermanane, or another germanium precursor having at least one Ge-H bond, is introduced into the reaction chamber and reacts with the vinyl and / or allyl groups in a hydrogermylation reaction to form carbon-bonded methylgermanyl or digermanyl groups on the surface. The resulting germanium film deposited using the germanium precursor grows immediately on this germanyl-rich surface without forming islands. Summary of the Invention

[0019] This document describes silicon precursors of the organoamino-vinylsilane and organoamino-allylsilane families comprising at least one vinyl or allyl group and at least one organic amino anchoring group, compositions comprising them, and methods for depositing silicon-containing films and forming monolayer films comprising silicon and vinyl groups, which can facilitate the formation of seed layers suitable for depositing metal thin films, particularly germanium thin films. Furthermore, this document describes compositions comprising organoamino-vinylsilane or organoamino-allylsilane that are substantially free of at least one impurity substance selected from organic amines, alcohols, halides, higher molecular weight substances, and trace metals. The compositions may additionally contain a solvent. This document also discloses methods for forming films or coatings comprising silicon and vinyl groups on objects to be processed, such as semiconductor wafers.

[0020] In one embodiment of the method described herein, a film containing silicon and vinyl groups is deposited onto a substrate in a deposition chamber using an organic amino-vinylsilane or organic amino-allylsilane precursor, under conditions suitable for forming a vinyl end-capping layer suitable for growing a germanium seed layer and subsequently a high-quality germanium film.

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

[0022] a. Provide a substrate in the reactor;

[0023] b. Introduce at least one precursor represented by formula I and / or II into the reactor;

[0024]

[0025] Where R 1 Selected from straight or branched chains C1 to C 10 Alkyl, straight-chain or branched C3 to C4 10 Alkenyl, straight-chain or branched C3 to C 10 alkynyl group, C3 to C 10 cycloalkyl and C6 to C 10 Aryl; R 2 Selected from hydrogen, straight-chain or branched C1 to C2. 10 Alkyl, straight-chain or branched C2 to C6 alkenyl, straight-chain or branched C3 to C6 ynyl, C3 to C 10 cycloalkyl and C6 to C 10 Aryl; R 3 and R 4 Each is independently selected from hydrogen, straight-chain or branched C1-C 10 Alkyl, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C3-C6 alkynyl, C3-C 10 cycloalkyl, C6-C 10 Aryl, C1-C 10Straight-chain, cyclic, or branched alkoxy groups, such as organic amino groups (NR) as defined above. 1 R 2 ) and halogens selected from Cl, Br and I;

[0026] c. Purge the reactor with purging gas;

[0027] d. Introduce at least one germanium precursor containing at least one Ge-H bond at a certain temperature so that the substrate is coated with at least one germanium monolayer;

[0028] e. Purge the reactor with purging gas;

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

[0030] g. Optionally, the reactor may be purged with a purging gas;

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

[0032] In one embodiment of the method described herein, germanium precursors having at least one Ge-H group include, but are not limited to, trichlorogermanane (ClGeH), germanane (GeH4), ethylgermanane (Ge2H6), and tert-butylgermanane (...). t One or more of BuGeH3), phenylgermanane, sec-butylgermanane, isobutylgermanane, and benzylgermanane.

[0033] As a step in this method, according to one embodiment, an organoamino-vinylsilane precursor of Formula I and / or an organoamino-allylsilane precursor of Formula II, along with an oxygen-containing source, is used to deposit a film containing silicon and oxygen onto a substrate under conditions for forming a silicon oxide or carbon-doped silicon oxide film. As a step in this method, according to another embodiment, an organoamino-vinylsilane precursor of Formula I and / or an organoamino-allylsilane precursor of Formula II, along with a nitrogen-containing source, is used to deposit a film containing silicon and nitrogen onto a substrate under conditions for forming a silicon nitride, carbon-doped silicon nitride, silicon oxynitride, or silicon oxycarbonitride film. In a further embodiment, the organoamino-vinylsilane precursor of Formula I and / or the organoamino-allylsilane precursor of Formula II is used as a dopant for a metal-containing film (e.g., but not limited to, a metal oxide film or a metal nitride film).

[0034] In some embodiments of the above method, steps d and h can be performed at the same temperature, or step d can be performed at a temperature lower than that of step h to avoid or limit 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 temperature higher than that of step h. In other embodiments, the temperature is increased after step d so that at least one germanium monolayer (referred to as the seed layer) is thermally annealed or annealed during optional hydrogen or hydrogen plasma treatment before subsequent germanium CVD film deposition in step g. In yet another embodiment, at least one germanium precursor containing at least one Ge-H bond is the same as the germanium CVD precursor. In other embodiments, at least one germanium precursor containing at least one Ge-H bond is not the same as the germanium CVD precursor.

[0035] In another aspect, a method is provided for functionalizing the surface of a solid substrate (e.g., but not limited to, silicon dioxide, aluminum oxide, metal oxide, silicon wafer, dielectric film, or metal surface) with vinyl and / or allyl groups, the method comprising the steps of:

[0036] a. Providing the substrate in the reactor;

[0037] b. Introducing at least one organic amino-vinyl silane precursor, represented by Formula I, comprising at least one vinyl group attached to at least one silicon atom and at least one organic amino anchoring group, or at least one organic amino-allyl silane precursor, represented by Formula II, comprising at least one allyl group attached to at least one silicon atom and at least one organic amino anchoring group, into the reactor; and

[0038] c. Remove residual organic amino-vinylsilane or organic amino-allylsilane from the substrate using solvent and / or purge gas.

[0039] In some embodiments, the organic amino-vinylsilane and / or organic amino-allylsilane precursors disclosed herein can be introduced into a solid substrate in a pure liquid manner, as a solution in a solvent, or as a vapor phase with or without a carrier gas at a temperature ranging from 0°C to 500°C. Attached Figure Description

[0040] Figure 1 It is a flowchart depicting a general scheme in which an organic amino-vinylsilane precursor having Formula I (or alternatively Formula II) as disclosed herein is used to (a) functionalize the substrate surface with vinyl to make it suitable for (b) forming a germanium seed layer by hydrogenation reaction with a germanium precursor containing at least one Ge-H bond, thereby allowing (c) subsequent growth of a smooth and uniform germanium film on top of the seed layer using at least one ALD or CVD Ge precursor. Detailed Implementation

[0041] This document discloses silicon precursor compounds and methods for using them to deposit silicon-containing films and to functionalize substrate surfaces for subsequent processing (including, but not limited to, germanium film deposition).

[0042] A specific method for forming a germanium seed layer includes the following steps:

[0043] a. Provide a substrate in the reactor;

[0044] b. Introduce at least one organic amino-vinyl silane precursor represented by Formula I, comprising at least one vinyl group attached to at least one silicon atom and at least one organic amino anchoring group, or at least one organic amino-allyl silane precursor represented by Formula II, comprising at least one allyl group attached to at least one silicon atom and at least one organic amino anchoring group, into the reactor.

[0045]

[0046] Where R 1 Selected from straight or branched chains C1 to C 10 Alkyl, straight-chain or branched C3 to C4 10 Alkenyl, straight-chain or branched C3 to C 10 alkynyl group, C3 to C 10 cycloalkyl and C6 to C 10 Aryl; R 2 Selected from hydrogen, straight-chain or branched C1 to C2. 10 Alkyl, straight-chain or branched C2 to C6 alkenyl, straight-chain or branched C3 to C6 ynyl, C3 to C 10 cycloalkyl and C6 to C 10 Aryl; R 3 and R 4 Each is independently selected from hydrogen, straight-chain or branched C1-C 10 Alkyl, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C3-C6 alkynyl, C3-C 10 cycloalkyl, C6-C 10 Aryl, C1-C 10 Straight-chain, cyclic, or branched alkoxy groups, such as organic amino groups (NR) as defined above. 1 R 2 ) and halogens selected from Cl, Br and I;

[0047] c. Purge the reactor with purging gas;

[0048] d. Introduce at least one germanium precursor containing at least one Ge-H bond at a certain temperature so that the substrate is coated with at least one germanium monolayer;

[0049] e. Purge the reactor with purging gas;

[0050] f. Optionally introduce a hydrogen or hydrogen plasma source;

[0051] g. Optionally, the reactor is purged with a purging gas; and

[0052] h. Introduce the same or different germanium precursor as in step d at a temperature suitable for growing a germanium-containing film of the desired thickness.

[0053] In some implementations, R 1 and R 2 They are the same. In other implementations, R 1 and R 2 They are different. In some implementations, R 3 and R 4 They are the same. In other implementations, R 3 and R 4 They are different.

[0054] In some preferred embodiments, R 3 and R 4 It is independently selected from hydrogen, methyl, vinyl and allyl.

[0055] The organoamino-vinylsilane and organoamino-allylsilane precursors described herein are used to form monolayer films containing silicon plus vinyl and / or allyl groups, as well as stoichiometric and non-stoichiometric silicon-containing films, such as, but not limited to, amorphous silicon, crystalline silicon, silicon oxide, carbon-doped silicon oxide, silicon carbide, silicon nitride, silicon oxynitride, and silicon carbonitride. These precursors can also be used, for example, as dopants for metal-containing films. The organoamino-vinylsilane and organoamino-allylsilane precursors used in semiconductor processes are typically high-purity volatile liquid chemicals that are vaporized and delivered as a gas into a deposition chamber or reactor to deposit silicon-containing films via CVD or ALD processes for semiconductor devices; however, they can also be introduced into the substrate in a liquid phase (pure or with a solvent). The precursor materials used for deposition are selected based on the desired final silicon-containing material or film. For example, the precursor material may be selected based on its elemental content, stoichiometric ratio of elements, and / or the resulting silicon-containing film or coating formed under CVD. Precursor materials can also be selected for various other properties, such as cost, relatively low toxicity, handling characteristics, ability to remain liquid at room temperature, volatility, molecular weight, thermal stability, and / or other considerations. In some embodiments, the precursors described herein can be delivered to the reactor system by a variety of means, preferably using a pressurized stainless steel vessel fitted with suitable valves and fittings, to allow delivery of liquid or vapor phase precursors to the deposition chamber or reactor.

[0056] Another specific method for forming a germanium seed layer includes the following steps:

[0057] a. Provide a substrate in the reactor;

[0058] b. Introduce at least one organic amino-vinyl silane precursor represented by Formula I, comprising at least one vinyl group attached to at least one silicon atom and at least one organic amino anchoring group, or at least one organic amino-allyl silane precursor represented by Formula II, comprising at least one allyl group attached to at least one silicon atom and at least one organic amino anchoring group, into the reactor.

[0059]

[0060] Where R 1 Selected from straight or branched chains C1 to C 10 Alkyl, straight-chain or branched C3 to C4 10 Alkenyl, straight-chain or branched C3 to C 10 alkynyl group, C3 to C 10 cycloalkyl and C6 to C 10 Aryl; R 2 Selected from hydrogen, straight-chain or branched C1 to C2. 10 Alkyl, straight-chain or branched C2 to C6 alkenyl, straight-chain or branched C3 to C6 ynyl, C3 to C 10 cycloalkyl and C6 to C 10 Aryl; R 3 and R 4 Each is independently selected from hydrogen, straight-chain or branched C1-C 10 Alkyl, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C3-C6 alkynyl, C3-C 10 cycloalkyl, C6-C 10 Aryl, C1-C 10 Straight-chain, cyclic, or branched alkoxy groups, such as organic amino groups (NR) as defined above. 1 R 2 ) and halogens selected from Cl, Br and I;

[0061] c. Purge the reactor with purging gas;

[0062] d. Introduce an oxygen source;

[0063] e. Purge the reactor with purging gas;

[0064] f. Introduce the above-mentioned organic amino-vinylsilane or organic amino-allylsilane precursors;

[0065] g. Purge the reactor with a purging gas;

[0066] h. Introduce at least one germanium precursor containing at least one Ge-H bond at a certain temperature so that the substrate is coated with at least one germanium monolayer;

[0067] i. Purge the reactor with purge gas;

[0068] j. Optionally introduce a hydrogen or hydrogen plasma source;

[0069] k. Optionally, the reactor is purged with a purging gas; and

[0070] l. Introduce the same or different germanium precursor as in step d at a temperature suitable for growing a germanium-containing film of the desired thickness;

[0071] Steps b through e are repeated until a silicon-containing film of the desired thickness is deposited before depositing the germanium seed layer and the subsequent germanium-containing film.

[0072] In some implementations, R 1 and R 2 They are the same. In other implementations, R 1 and R 2 They are different. In some implementations, R 3 and R 4 They are the same. In other implementations, R 3 and R 4 They are different.

[0073] In some preferred embodiments, R 3 and R 4 It is independently selected from hydrogen, methyl, vinyl and allyl.

[0074] Silicon-containing films deposited using the organoamino-vinylsilane and / or organoamino-allylsilane precursors described herein, whether single monolayers or multiple monolayers, can be used as substrates suitable for reaction with germanium precursors containing at least one Ge-H bond. Without being bound by theory, it is believed that when the surface of the substrate reacts with the organoamino-vinylsilane and / or organoamino-allylsilane precursors described herein, it becomes functionalized with vinyl and / or allyl groups, or more specifically, vinylsilyl and / or allylsilyl groups. These groups can then each undergo a hydrogengermanization reaction with the Ge-H bond of the germanium precursor molecule, thus anchoring germanium atoms or germanyl groups at any position on the surface where available vinyl and / or allyl groups are present. The vinyl and / or allyl groups in this reaction are converted into ethylene, ethylidene, propylene, or methylethylene linkers between the Si and Ge atoms. Once the substrate surface is uniformly coated with germanium alkyl groups, it becomes ready for deposition of Ge films via ALD, PEALD, CVD, cyclic CVD, or PECVD processes, in most cases at elevated temperatures, but in some cases at the same temperatures. In some embodiments, the germanium alkyl groups anchored to the surface must first be reduced with a reducing gas (e.g., but not limited to, hydrogen or hydrogen plasma) to produce -GeH. x (x = 0, 1, 2, 3) The surface of the end cap.

[0075] Exemplary germanium precursors containing at least one Ge-H bond include, but are not limited to, trichlorogermanane (Cl3GeH), germanane (GeH4), diethylgermanane (Ge2H6), and tert-butylgermanane (...). t One or more of BuGeH3), phenylgermanane, sec-butylgermanane, isobutylgermanane, and benzylgermanane.

[0076] Figure 1 A general scheme is described in which an organoamino-vinylsilane precursor of Formula I, as disclosed herein, is used to (a) functionalize a substrate surface with vinyl groups, making it suitable for (b) forming a germanium seed layer by a hydrogenation reaction with a germanium precursor containing at least one Ge-H bond, thereby allowing (c) subsequent growth of a smooth and uniform germanium film on top of the seed layer using at least one ALD or CVD Ge precursor. Schemes of the same type are applied in which… Figure 1 Step (a) uses an organic amino-allyl silane precursor having Formula II as disclosed herein, except that the substrate is functionalized with an allyl group instead of a vinyl group.

[0077] It is believed that when the substrate is uniformly treated with the organoamino-vinylsilane and / or organoamino-allylsilane precursors disclosed herein, it will be more likely to be affected by GeH. xWhen (x = 0, 1, 2, 3) groups are uniformly capped, they serve as a seed layer, allowing for the subsequent growth of amorphous or crystalline germanium films with very low inhomogeneity and low levels of surface roughness. The resulting smooth and uniform Ge film is believed to be achieved by eliminating the “island growth” phenomenon known to those skilled in the art at the beginning of Ge film deposition. By converting non-reactive organic, dielectric, metallic, or any other non-reactive surface into a reactive surface functionalized with germanium atoms or germanium alkyl groups, one can begin depositing a Ge film without the formation of “islands” on the surface. This smooth, conformal initial layer is characteristic of high-quality germanium seed layers.

[0078] The organic amino-vinylsilane and organic amino-allylsilane precursors described herein exhibit a balance of reactivity and stability, making them ideally suited as CVD or ALD precursors in microelectronic device fabrication processes. Regarding reactivity, the organic amino-vinylsilanes and / or organic amino-allylsilanes of this invention have at least one organic amino group (NR... 1 R 2 This facilitates the reaction of organic amino-vinylsilane and / or organic amino-allylsilane precursors with hydroxyl surfaces during the ALD process. While the hydroxyl surfaces most commonly referred to in this invention are dielectric surfaces, such as silicon oxide, silicon nitride, silicon (with a natural oxide), metal oxides, metal nitrides, or metals (with a natural oxide), other materials that may contain surface hydroxyl groups, such as organic polymers, siloxanes, resins, plastics, beads, adsorbents, amorphous carbon, activated carbon, minerals, organic matter, containers, and textiles, are also contemplated to be reactive with at least one organic amino group on the organic amino-vinylsilane and / or organic amino-allylsilane precursors described herein.

[0079] The organic amino anchoring groups in the organic amino-vinylsilane and organic amino-allylsilane precursors described herein are expected to offer advantages over chloro-vinylsilanes, alkoxy-vinylsilanes, vinyldisilazanes, chloro-allylsilanes, alkoxy-allylsilanes, and allyl-disilazane precursors in terms of reaction with -OH-terminated surfaces, especially at low temperatures and in the gas phase. For example, treatment of a substrate with triethoxyvinylsilane at a certain temperature results in little or no vinyl functionalization of the substrate surface, while treatment with an organic amino-vinylsilane at the same temperature provides a much higher level of functionalization. Similarly, treatment of a substrate with triethoxyallylsilane at a certain temperature results in little or no allyl functionalization of the substrate surface, while treatment with an organic amino-allylsilane at the same temperature provides a much higher level of functionalization. This makes organic amino-vinylsilanes and organic amino-allylsilanes of Formula I and Formula II advantageous as surface modifiers for purposes other than subsequent deposition of germanium films. Examples of current processes that can benefit from the high saturation of surface vinyl and / or allyl groups include, but are not limited to, (a) immobilizing substances such as catalysts, ion-exchange functional groups, adsorbents, or metal scavengers onto a solid support; (b) improving the hydrophobicity of a substrate; (c) altering the optical properties or refractive index of a substrate used for display applications; and / or (d) providing crosslinking sites for better adhesion after a subsequent UV / thermal annealing of the coating.

[0080] Some precursors may have boiling points too high to vaporize and be delivered to the reactor for film deposition on a substrate. Therefore, it is preferable to select precursors with smaller organic amino groups and smaller R-groups to provide boiling points of 250°C or lower, preferably 200°C or lower. The presence of two or more organic amino groups can significantly increase the boiling point; precursors with higher relative boiling points require delivery containers and lines to be heated to or above the precursor's boiling point under a specified vacuum to prevent condensation or particle formation in the container, line, or both. Regarding stability, other precursors may form silanes (SiH4) or disilanes (Si2H6) upon degradation. Silanes are flammable at room temperature or can spontaneously combust, leading to safety and operational issues. Furthermore, the formation of silanes or disilanes and other byproducts reduces the purity level of the precursor, and for reliable semiconductor manufacturing, even a small change in chemical purity of 1-2% may be considered unacceptable. In some embodiments, the organoamino-vinylsilane and / or organoamino-allylsilane precursors of formula I and / or II described herein contain 2% or less by weight, or 1% or less by weight, or 0.5% or less by weight of impurities (e.g., free organic amines, alcohols, chlorosilanes, halides, or higher molecular weight disproportionation products) after storage for 6 months or longer, or 1 year or longer, indicating that they are storage stable. Certain organoamino-vinylsilane and / or organoamino-allylsilane precursors having Si-H groups (at least R in formula I and / or II) 3 and R 4 One of them (hydrogen) may be readily degraded via polymerization through intermolecular hydrogenation-silanization reactions. That is, if R in formula I and / or II 1 To R 4 If the size of the group does not provide sufficient steric protection, a reaction can 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 the deposition process, and can be catalyzed by trace impurities. Therefore, it is important to remove as many impurities as possible from the organoamino-vinylsilane precursor that can be used as a hydrosilylation / polymerization catalyst. Furthermore, careful selection of R is necessary. 1 To R 4 The groups allow organic amino-vinylsilanes and / or organic amino-allylsilanes to readily react with the substrate surface under desired conditions, while maintaining the inherent stability of the precursors.

[0081] In some preferred embodiments, R in formula I and / or II 3 and R 4 All are organic amino groups. In other preferred embodiments, R in formula I and / or II... 3 and R 4All are methyl groups. In other preferred embodiments, R in formula I and / or II... 1-4 All are methyl groups. In other preferred embodiments, R in formula I and / or II... 3 and R 4 All are vinyl. In other preferred embodiments, R in formula I and / or II 3 and R 4 All are allyl. In other preferred embodiments, in Formula I, R 3 It is an organic amino group, R 4 It is vinyl. In other preferred embodiments, in Formula II, R 3 It is an organic amino group, R 4 It is allyl. In other preferred embodiments, in formula I, R 3 It is methyl, R 4 It is vinyl. In other preferred embodiments, in Formula II, R 3 It is methyl, R 4 It is allyl.

[0082] In some implementations, for example, for depositing silicon oxide or silicon nitride or other silicon-containing films using ALD, ALD-like, PEALD, or CCVD deposition methods, the organoamino-vinylsilane and organoamino-allylsilane precursors described herein are capable of depositing high-density materials at relatively low deposition temperatures, such as 1000°C or lower, 800°C or lower, 700°C or lower, 500°C or lower, or 400°C or lower, 300°C or lower, 200°C or lower, 100°C or lower, or 50°C or lower.

[0083] In one embodiment, a composition for forming a silicon-containing film is described herein, comprising: an organic amino-vinylsilane having formula I and / or an organic amino-allylsilane having formula II, and a solvent.

[0084] Not intended to be bound by any particular theory, the compositions described herein are believed to offer one or more advantages compared to existing silicon precursors such as TEOS, BDEAS, and SiCl4. These advantages include: better utilization of organoamino-vinylsilanes and / or organoamino-allylsilanes in semiconductor processes; better stability during long-term storage; cleaner vaporization via flash evaporation; and / or a more stable overall direct liquid injection (DLI) chemical vapor deposition process, thereby allowing the deposition of higher quality silicon-containing films, and further allowing for superior subsequent Ge film deposition. The weight percentage of organoamino-vinylsilanes and / or organoamino-allylsilanes in the compositions can range from 1% to 99%, with the balance being solvent, wherein the solvent does not react with the organoamino-vinylsilanes and / or organoamino-allylsilanes and has a similar boiling point to the organoamino-vinylsilanes and / or organoamino-allylsilanes. Regarding the latter, the boiling point difference between the organic amino-vinylsilane and / or organic amino-allylsilane in the composition and the solvent is 40°C or lower, more preferably 20°C or lower, or 10°C or lower.

[0085] In some embodiments, it is advantageous to use the organoamino-vinylsilane and / or organoamino-allylsilane precursors described in this invention to deposit silicon-containing films, such as, but not limited to, silicon, silicon carbide, silicon nitride, carbon-doped silicon nitride, silicon oxide, silicon oxynitride, carbon-doped silicon oxynitride, and carbon-doped silicon oxide, provided that a metal film such as a germanium film is subsequently deposited on the silicon-containing film. Without intending to be bound by any particular theory, it is believed that when the final step of such a Si-containing film deposition process is the exposure of the organoamino-vinylsilane and / or organoamino-allylsilane precursor, the resulting silicon-containing film is far more likely to form a uniform Ge seed layer, and thus subsequently grow a smooth, conformal Ge film. In some cases, the overall composition, physical properties, and electrical properties of the Si-containing films described herein can also be achieved using various other silicon precursors and deposition methods known in the art. However, these films still require functionalization with the organoamino-vinylsilane and / or organoamino-allylsilane precursors described herein before the deposition of a reduction or metallic germanium film to ensure that these germanium films have the same high quality. Therefore, it is clear that using a single silicon precursor, such as an organoamino-vinylsilane or an organoamino-allylsilane as described herein, for the deposition of silicon-containing films and the functionalization of these films with vinyl and / or allyl groups for subsequent Ge film growth would be far more advantageous than using two different silicon precursors.

[0086] In some embodiments, the substituent R in Formula I and / or Formula II 1 and R 2 They can be connected together to form a ring structure. As those skilled in the art will understand, when R 1 and R 2 When connected together to form a loop, R1 Includes connection to R 2 The bonds are either cyclic or non-cyclic. In these embodiments, the ring structure can be unsaturated, such as a cyclic alkyl ring, or saturated, such as an aryl ring. Similarly, R in Formula I and / or Formula II... 3 and R 4 They can be linked together to form a ring structure. Furthermore, in these embodiments, the ring structure can be substituted or unsubstituted. Exemplary cyclic groups include, but are not limited to, pyrrolyl, 2-methylpyrrolyl, 2,5-dimethylpyrrolyl, piperidinyl, 2,6-dimethylpiperidinyl, pyrrolyl, and imidazolyl. However, in other embodiments, the substituent R... 1 and R 2 Not connected. In other implementations, R... 3 and R 4 Not connected.

[0087] Throughout this formula and the specification, the term "alkyl" refers to a straight-chain or branched functional group having 1 to 10 or 1 to 6 carbon atoms. Exemplary alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, isohexyl, and neohexyl. In some embodiments, the alkyl group may have one or more functional groups attached thereto, such as, but not limited to, alkoxy, dialkylamino, or combinations thereof. In other embodiments, the alkyl group does not have one or more functional groups attached thereto.

[0088] In this formula and throughout the specification, the term "cycloalkyl" refers to a cyclic functional group having 3 to 10, 4 to 10, or 5 to 10 carbon atoms. Exemplary cycloalkyl groups include, but are not limited to, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

[0089] In this formula and throughout the specification, the term "aryl" refers to 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.

[0090] In this formula and throughout the specification, the term "alkenyl" means a group having one or more carbon-carbon double bonds and having 3 to 10, 3 to 6, or 3 to 4 carbon atoms. Exemplary alkenyl groups include, but are not limited to, vinyl and allyl.

[0091] In this formula and throughout the specification, the term "alkynyl" refers to a group having one or more carbon-carbon triple bonds and having 3 to 10, 3 to 6, or 3 to 4 carbon atoms.

[0092] Throughout this formula and the entire specification, the term "organic amino" means a group having at least one alkyl or additionally hydrocarbon group attached to a nitrogen atom and having 1 to 10, 2 to 6, or 2 to 4 carbon atoms. Exemplary organic amino groups include, but are not limited to, methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, sec-butylamino, tert-butylamino, cyclopentylamino, cyclohexylamino, phenylamino, dimethylamino, N-ethylmethylamino, diethylamino, and diisopropylamino.

[0093] Throughout this formula and the specification, the term "dialkylamino" refers to a group having two alkyl groups attached to a nitrogen atom, wherein each alkyl group has, 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-n-propylamino, di-isopropylamino, di-n-butylamino, di-isobutylamino, di-sec-butylamino, and di-tert-butylamino.

[0094] In some embodiments, one or more of the alkyl, alkenyl, alkynyl, or aryl groups in Formulas I and II may be substituted or have one or more atoms or groups substituted, for example, by replacing hydrogen atoms. Exemplary substituents include, but are not limited to, oxygen, sulfur, halogen atoms (e.g., F, Cl, I, or Br), nitrogen, and phosphorus.

[0095] In some embodiments, at least one organic amino-vinylsilane precursor of Formula I and / or at least one organic amino-allylsilane precursor of Formula II have one or more substituents containing oxygen or nitrogen atoms.

[0096] It is believed that the unique structures of the precursors of Formulas I and II described herein allow for 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.

[0097] Table 1 lists examples of silicon precursors according to Formula I having at least one vinyl group and at least one organic amino anchoring group attached to at least one silicon atom.

[0098] Table 1. Exemplary organic amino-vinylsilane precursors.

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107] Table 2 lists examples of silicon precursors according to Formula II having at least one allyl group and at least one organic amino anchoring group attached to at least one silicon atom.

[0108] Table 2. Exemplary organic aminoallyl silane precursors.

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117] The organic amino-vinylsilane and / or organic amino-allylsilane precursors according to the invention and compositions comprising the organic amino-vinylsilane and / or organic amino-allylsilane precursors according to the invention are preferably substantially free of organic amines or halide ions. As used herein, the term "substantially free" means less than 5 ppm (by weight), preferably less than 3 ppm, more preferably less than 1 ppm, and most preferably 0 ppm when referring to halide ions (or halides) such as chlorides and fluorides, bromides and iodides. As used herein, the term "free" means 0 ppm when referring to halide ions or other impurities. Chlorides are known to be used as decomposition catalysts for organic amino-vinylsilanes and organic amino-allylsilanes. Significant levels of chloride in the final product can lead to degradation of organic amino-vinylsilanes and / or organic amino-allylsilane precursors. The gradual degradation of organic amino-vinylsilanes and / or organic amino-allylsilanes can directly affect film deposition processes or surface functionalization treatments, making it difficult for semiconductor manufacturers to meet film standards. Furthermore, the high degradation rate of organic amino-vinylsilanes and / or organic amino-allylsilanes negatively impacts shelf life and stability, making it difficult to guarantee a shelf life of 1-2 years. Therefore, the accelerated decomposition of organic amino-vinylsilanes and / or organic amino-allylsilanes exhibits characteristics related to these flammable and / or spontaneously combustible gaseous byproducts (organic amines, including but not limited to C1 to C4 hydroxylamines). 10 Safety and performance issues related to the formation of organic amines and organodiamines. Silicon precursor compounds having formulas I and II are preferably substantially free of metal ions, for example, Li. + Na + K + Mg 2+ Ca 2+ Al 3+ Fe 2+ Fe 2+ Fe 3+ Ni 2+ Cr 3+ As used herein, when referring to Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr, or noble metals such as volatile Ru or Pt complexes from ruthenium or platinum catalysts used in the synthesis, the term "substantially free" means less than 5 ppm (by weight), preferably less than 3 ppm, more preferably less than 1 ppm, and most preferably 0.1 ppm, as measured by ICP-MS or other analytical methods for measuring trace metals.

[0118] Methods for forming silicon-containing films or coatings include deposition processes. Examples of suitable deposition processes for the methods disclosed herein include, but are not limited to, cyclic CVD (CCVD), MOCVD (metal-organic CVD), thermochemical vapor deposition, plasma-enhanced chemical vapor deposition (“PECVD”), high-density PECVD, photon-assisted CVD, plasma-photon-assisted (“PPECVD”), low-temperature chemical vapor deposition, chemical-assisted vapor deposition, hot-filament chemical vapor deposition, CVD of liquid polymer precursors, deposition by supercritical fluids, and low-energy CVD (LECVD). In some embodiments, metal-containing films are deposited via atomic layer deposition (ALD), plasma-enhanced ALD (PEALD), or plasma-enhanced cyclic CVD (PECCVD) processes. 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 the desired deposition. As used herein, the term "atomic layer deposition process" refers to a self-limiting (e.g., the amount of film material deposited is constant in each reaction cycle) and continuous surface chemistry of depositing a film of material onto a substrate of varying compositions. Although precursors, reagents, and sources used herein may sometimes be described as "gaseous," it should be understood that precursors may be liquids or solids, transported to the reactor by direct vaporization, bubbling, or sublimation, with or without an inert gas. In some cases, vaporized precursors may be transported via 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 yet another embodiment, a silicon-containing film is deposited using a thermal CVD process. The term "reactor" as used herein includes, but is not limited to, a reaction chamber or a deposition chamber.

[0119] In some embodiments, the methods disclosed herein avoid precursor pre-reaction by using ALD or CCVD methods that separate the precursors before and / or during introduction into the reactor. For this purpose, 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 alternately exposing the substrate surface to one or more of a silicon-containing precursor, an oxygen-containing source, a nitrogen-containing source, or other precursors or reagents. Film growth is controlled by self-limiting surface reactions, the pulse length of each precursor or reagent, and the deposition temperature. However, film growth ceases once the substrate surface is saturated.

[0120] In some embodiments, the methods described herein also include one or more additional silicon-containing precursors other than the organic amino-vinylsilane and / or organic amino-allylsilane precursors having formula I and / or II described above. Other examples of silicon-containing precursors include, but are not limited to, monoaminosilanes (e.g., diisopropylaminosilane, disec-butylaminosilane, phenylmethylaminosilane; organosilicon compounds, e.g., trimethylsilylamine (TSA); monoaminosilanes (diisopropylaminosilane, disec-butylaminosilane, phenylmethylaminosilane); siloxanes (e.g., hexamethyldisiloxane (HMDSO) and dimethylsiloxane (DMSO), and hexachlorodisiloxane (HCDSO)); organosilicones (e.g., methylsilane, dimethylsilane, diethylsilane, vinyltrimethylsilane, trimethylsilane, tetramethylsilane, ethylsilane, dimethylsilylmethane, 2,4-disilazane, 1,4-disilazane, 2,5-disilazane, 2,2-dimethylsilylpropane, 1,3,5-trisilazane, and fluorinated compounds thereof). (derivatives); 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-di... Methyl-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; hexamethylcyclotrisiloxane; 1,3-dimethyldisiloxane; 1,3,5,7,9-pentamethylcyclopentasiloxane; hexamethoxydisiloxane and fluorinated derivatives of these compounds.

[0121] In some embodiments, depending on the deposition method, one or more silicon-containing precursors may be introduced into the reactor in a predetermined molar amount, or from about 0.1 to about 1000 micromoles. In this or other embodiments, the silicon-containing and / or organoamino-vinylsilane and / or organoamino-allylsilane precursors are introduced into the reactor for a predetermined time period. In some embodiments, this time period is in the range of about 0.001 to about 500 seconds.

[0122] In some embodiments, the silicon-containing film deposited using the methods described herein is formed in the presence of oxygen using an oxygen-containing source, reagent, or oxygen-containing precursor. The oxygen-containing source may be introduced into the reactor in the form of at least one oxygen-containing source and / or incidentally present in other precursors used in the deposition process. Suitable oxygen-containing source gases 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 some embodiments, the oxygen-containing source is introduced into the reactor at a flow rate in the range of about 1 to about 2000 standard cubic centimeters (sccm) or about 1 to about 1000 sccm. The oxygen-containing source may be introduced for a time in the range of about 0.1 to about 100 seconds. In a particular embodiment, the oxygen-containing source comprises water having a temperature of 10°C or higher. In embodiments where the film is deposited via ALD or cyclic CVD processes, the precursor pulse may have a pulse duration greater than 0.01 seconds, and the oxygen source pulse may have a pulse duration less than 0.01 seconds, while the water pulse may have a pulse duration less than 0.01 seconds. In yet another embodiment, the purge duration between pulses may be as low as 0 seconds or continuous pulses without purge during this period. The oxygen source or reagent is provided in an amount of molecules at a ratio less than 1:1 relative to the silicon precursor, such that at least some carbon is retained in the in-situ deposited silicon-containing film.

[0123] In some embodiments, the silicon-containing membrane comprises silicon and nitrogen. In these embodiments, the silicon-containing membrane deposited using the methods 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 source gases may include, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and mixtures thereof. In some embodiments, the nitrogen-containing source comprises an ammonia plasma or hydrogen / nitrogen plasma source gas, which is introduced into the reactor at a flow rate in the range of about 1 to about 2000 standard cubic centimeters (sccm) or about 1 to about 1000 sccm. The nitrogen-containing source may be introduced for a time in the range of about 0.1 to about 100 seconds. In embodiments in which the membrane is deposited by an ALD or cyclic CVD process, the precursor pulse may have a pulse duration greater than 0.01 seconds, and the nitrogen-containing source may have a pulse duration less than 0.01 seconds, while the water pulse duration may have a pulse duration less than 0.01 seconds. In yet another implementation, the purge duration between pulses can be as low as 0 seconds or continuous pulses without purge during the period.

[0124] The deposition methods disclosed herein may involve one or more purge gases. The purge gas used to purge and remove unconsumed reactants and / or reaction byproducts is an inert gas that does not react with the precursors. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N2), helium (He), neon, hydrogen (H2), and mixtures thereof. In some 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 material and any byproducts that may remain in the reactor.

[0125] The corresponding steps of supplying precursors, oxygen-containing sources, nitrogen-containing sources, and / or other precursors, source gases, and / or reagents can be carried out by changing their supply time to alter the stoichiometric composition of the resulting silicon-containing film.

[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 combinations thereof to initiate a reaction and form a silicon-containing film or coating on a substrate. Such energy can be provided by, but is not limited to, thermal, plasma, pulsed plasma, helical wave plasma, high-density plasma, inductively coupled plasma, X-ray, electron beam, photon, remote plasma methods, and combinations thereof. In some embodiments, a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface. In embodiments where plasma deposition is involved, the plasma generation process can include a direct plasma generation process in which plasma is directly generated in a reactor, or alternatively, a remote plasma generation process in which plasma is generated outside the reactor and supplied to the reactor.

[0127] Organic amino-vinylsilane and / or organic amino-allylsilane precursors, other silicon-containing precursors, and / or germanium precursors can be delivered to the reaction chamber, such as a CVD or ALD reactor, in various ways. In one embodiment, a liquid delivery system may be utilized. In alternative embodiments, a combination of liquid delivery and flash vaporization process units, such as a turbovaporizer manufactured, for example, by MSP Corporation of Shaughnessy, Minnesota, may be employed to enable the quantitative delivery of low-volatility materials, resulting in reproducible transport and deposition without thermal decomposition of the precursor. In the liquid delivery mode, the precursors described herein may be delivered in pure liquid form, or alternatively, in a solvent formulation or composition containing them. Thus, in some embodiments, the precursor formulation may include a solvent component having suitable properties that are likely desired and advantageous in a given end-use application to form a film on a substrate.

[0128] For embodiments in which a solvent and an organoamino-vinylsilane and / or organoamino-allylsilane precursor of formula I and / or II as described herein are used, the selected solvent or mixture thereof does not react with the organoamino-vinylsilane and / or organoamino-allylsilane. The amount of solvent in the composition, by weight percentage, ranges from 0.5% to 99.5% by weight or from 10% to 75% by weight. In this or other embodiments, the solvent has a boiling point (bp) similar to that of the precursor of formula I and / or II, or the difference between the bp of the solvent and the bp of the precursor of formula I or II is 40°C or lower, 30°C or lower, 20°C or lower, or 10°C. Optionally, the difference in boiling point is within the range of any one or more of the following endpoints: 0°C, 10°C, 20°C, 30°C, or 40°C. Examples of suitable ranges for the bp difference include, but are not limited to, 0 to 40°C, 20 to 30°C, or 10 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., benzyl nitrile), 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, this document describes a container for depositing silicon-containing films comprising one or more organoamino-vinylsilane and / or organoamino-allylsilane precursors of formula I or II. In one particular embodiment, the container comprises at least one pressurized vessel (preferably stainless steel) fitted with suitable valves and fittings to allow delivery of one or more precursors to a reactor for CVD or ALD processes. In this or other embodiments, organoamino-vinylsilane and / or organoamino-allylsilane precursors of formula I and / or II are provided in a pressurized vessel made of stainless steel, and the precursors have a purity of 98% by weight or greater or 99.5% by weight or greater, suitable for most semiconductor applications. In some embodiments, such containers may also have means for mixing the precursors with one or more additional precursors (if desired). In these or other embodiments, the contents of the container may be premixed with additional precursors. Optionally, organic amino-vinylsilane and / or organic amino-allylsilane precursors and / or other precursors may be maintained in separate containers or in a single container with a separation device for keeping the organic amino-vinylsilane and / or organic amino-allylsilane precursors and other precursors separate during storage.

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

[0131] In some embodiments, the gas line connecting the precursor tank to the reaction chamber is heated to one or more temperatures, depending on process requirements, and the container having an organic amino-vinylsilane and / or organic amino-allylsilane precursor of formula I and / or II as described herein is maintained at one or more temperatures for bubbling. In other embodiments, a solution containing at least one silicon-containing precursor of the formula described herein is injected into a vaporizer maintained at one or more temperatures for direct liquid injection.

[0132] Argon and / or other gas streams can be used as carrier gases to help deliver the vapor of at least one organic amino-vinylsilane and / or organic amino-allylsilane precursor into the reaction chamber during precursor pulses. In some embodiments, the reaction chamber process pressure is about 10 Torr or less. In other embodiments, the reaction chamber process pressure is about 5 Torr or less.

[0133] For multi-component silicon-containing membranes, other precursors such as silicon-containing precursors, nitrogen-containing precursors, reducing agents, or other reagents can be alternately introduced into the reaction chamber.

[0134] In one embodiment of the method described herein, a thermal ALD process and hydrogen-containing plasma deposition of silicon oxide or carbon-doped silicon oxide films with a carbon content ranging from 0 atomic% to 20 atomic% are used to improve film performance. In this embodiment, the method includes:

[0135] a. Place one or more substrates containing surface features in a reactor, heat the reactor to one or more temperatures in the range of ambient temperature to about 550°C, and optionally maintain the reactor at a pressure of 100 Torr or less;

[0136] b. Introduce at least one organic amino-vinyl silane and / or organic amino-allyl silane precursor, represented by formula I and / or II, comprising at least one vinyl and / or allyl group and at least one organic amino anchoring group attached to at least one silicon atom, into the reactor.

[0137] c. The reactor is purged with an inert gas to remove unreacted silicon precursors and form a composition comprising the purging gas and the silicon precursors;

[0138] d. Providing an oxygen-containing source to the reactor to react with the surface, thereby forming a silicon- and oxygen-containing film;

[0139] g. Purging with an inert gas to remove reaction byproducts;

[0140] f. Repeat steps b to e to provide the desired thickness of silicon oxide or carbon-doped silicon oxide;

[0141] In this or other embodiments, the UV exposure step can be performed during film deposition or once deposition is complete. In another embodiment, organic amino-vinylsilanes and / or organic amino-allylsilanes as described herein can be used to deposit silicon- and nitrogen-containing films, such as silicon nitride or silicon carbonitride, using the same steps as described above (except that a nitrogen-containing source is used instead of an oxygen-containing source).

[0142] In one embodiment, the substrate includes at least one feature, wherein the feature includes patterned trenches having an aspect ratio of 1:9 or higher and / or an opening of 180 nm or less.

[0143] In embodiments where the membrane is treated with plasma, the plasma source is selected from hydrogen plasma, plasma containing hydrogen and helium, and plasma containing hydrogen and argon. Hydrogen plasma reduces the dielectric constant of the membrane and improves its resistance to damage from subsequent plasma ashing processes, while still maintaining the overall carbon content almost unchanged.

[0144] Throughout this specification, the term "ALD or ALD sample" refers to processes including, but not limited to, those that: a) sequentially introduce each reactant, comprising a silicon precursor and a reactive gas, into a reactor, such as a single-wafer ALD reactor, a half-batch ALD reactor, or a batch furnace ALD reactor; b) expose each reactant, comprising a silicon precursor and a reactive gas, to a substrate by moving or rotating the substrate to different sections of the reactor, with each section separated by an inert gas curtain (i.e., a space ALD reactor or a roll-to-roll ALD reactor).

[0145] Throughout this specification, the term "ashing" refers to the process of removing photoresist or carbon hard masks in semiconductor manufacturing processes using plasma containing an oxygen source (e.g., O2 / inert gas plasma, O2 plasma, CO2 plasma, CO plasma, H2 / O2 plasma, or combinations thereof).

[0146] Throughout this specification, the term "damage resistance" refers to membrane properties after oxygen ashing. Good or high damage resistance is defined as membrane properties after oxygen ashing that include: a membrane dielectric constant below 4.5; and a total carbon content (in membranes exceeding a certain threshold). The depth is within 5 atoms before ashing; through the vicinity of the film surface (less than) Depth) and membrane bulk (greater than) The observed difference in HF etching rate between depths was less than [a certain value]. The membrane is damaged.

[0147] In some embodiments, the organoamino-vinylsilane and / or organoamino-allylsilane precursors of 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, ALD or CVD processes, such as those described herein using metal alkoxides, metal amides, or volatile organometallic precursors, are used to deposit the metal-containing films. Examples of suitable metal alkoxide precursors that can be used with the methods disclosed herein include, but are not limited to, group 3 to 6 metal alkoxides, group 3 to 6 metal complexes having alkoxy and alkyl-substituted cyclopentadienyl ligands, group 3 to 6 metal complexes having alkoxy and alkyl-substituted pyrroleyl ligands, group 3 to 6 metal complexes having alkoxy and diketone ligands; and group 3-6 metal complexes having alkoxy and ketone ester ligands. Examples of suitable metal amide precursors that can be used with the methods disclosed herein include, but are not limited to, tetra(dimethylamino)zirconium (TDMAZ), tetra(diethylamino)zirconium (TDEAZ), tetra(ethylmethylamino)zirconium (TEMAZ), tetra(dimethylamino)hafnium (TDMAH), tetra(diethylamino)hafnium (TDEAH) and tetra(ethylmethylamino)hafnium (TEMAH), tetra(dimethylamino)titanium (TDMAT), tetra(diethylamino)titanium (TDEAT), tetra(ethylmethylamino)titanium (TEMAT), tert-butyliminotris(diethylamino)tantalum (TBTDET), and tert-butyliminotris(dimethylamino)tantalum (TBTD). MT), tert-butyliminotris(ethylmethylamino)tantalum (TBTEMT), ethyliminotris(diethylamino)tantalum (EITDET), ethyliminotris(dimethylamino)tantalum (EITDMT), ethyliminotris(ethylmethylamino)tantalum (EITEMT), tert-pentyliminotris(dimethylamino)tantalum (TAIMAT), tert-pentyliminotris(diethylamino)tantalum, penta(dimethylamino)tantalum, tert-pentyliminotris(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, cyclopentadienyl or alkylcyclopentadienyl Group 3 metals. The exemplary group 3 to 6 metals mentioned herein 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 some embodiments, the resulting silicon-containing film or coating may be exposed to post-deposition treatments, such as, but not limited to, plasma treatment, chemical treatment, ultraviolet exposure, electron beam exposure and / or other treatments, to achieve one or more properties of the film.

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

[0150] As previously stated, the methods described herein can be used to deposit silicon-containing films 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, antireflective coatings, photoresists, flexible substrates, organic polymers, porous organic and inorganic materials, metals such as copper and aluminum, and diffusion barrier layers, such as, but not limited to, TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN. The films are compatible with a variety of subsequent process steps, such as chemical mechanical planarization (CMP) and anisotropic etching processes.

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

[0152] The methods described herein provide high-quality films including 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" refers to films exhibiting one or more of the following characteristics: a density of about 2.1 g / cc or higher, 2.2 g / cc or higher, or 2.25 g / cc or higher; as measured in a dilute HF (0.5 wt% dHF) acid solution with an HF to water ratio of 1:100. or lower or lower or lower or lower or lower or lower or lower Or even lower wet etching rates, up to approximately 1e-8 A / cm at rates up to 6 MV / cm. 2 Or even lower leakage current; such as approximately 5e20 at / cc or lower hydrogen impurities as measured by SIMS; very low inhomogeneity, low levels of surface roughness, and their combination. Regarding the etching rate, thermally grown silicon oxide films exhibit [specific characteristics] in 0.5 wt% HF. The etching rate.

[0153] In some embodiments, one or more silicon precursors having Formula I and Formula II described herein can be used to form silicon and oxygen-containing films that are solid and non-porous or substantially non-porous.

[0154] The following examples illustrate the methods described herein for preparing organoamino-vinylsilane and / or organoamino-allylsilane precursors, depositing silicon-containing films, forming vinyl-functionalized and / or allyl-functionalized surfaces, and generating germanium seed layers, and are not intended to limit them in any way.

[0155] Example

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

[0157] Under nitrogen protection, in a 3-liter, three-necked round-bottom flask equipped with a mechanical stirrer and a reflux condenser, a solution of ethylamine in THF (800 mL, 2.0 M, 1.60 mol) was added through a sleeve to a solution of triethylamine (175 g, 1.73 mol) in hexane (1 L). The combined solution was cooled to -20 °C and stirred. At -20 °C, a solution of trichlorovinylsilane (80.0 g, 0.495 mol) in hexane (80 g) was added dropwise to the mixture over 2 hours. The resulting white slurry was warmed to room temperature and stirred for another 2 hours. The white solid was removed by filtration through a glass frit, and the solvent was removed by vacuum distillation (20 Torr) at room temperature. The concentrated crude liquid was purified by vacuum distillation (1 Torr / 45 °C) to give 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. Treating silicone with tri(ethylamino)vinylsilane.

[0159] Under nitrogen protection, 0.5g of Davasil silica gel was added. TM Grade 645, 60-100 mesh A 50% by weight solution of tris(ethylamino)vinylsilane in THF was stirred at 80°C for 2 hours. The liquid phase was decanted, and the solid was washed several times with hot THF before vacuum drying. Untreated and treated silica gels were analyzed by FTIR spectroscopy using KBr pellets. The 3741 cm⁻¹ region corresponding to the separated surface Si-OH groups was not detected in the FTIR spectrum of the treated silica gel, unlike the FTIR spectrum of the untreated silica gel. -1 The treated silica gel exhibited the following novel peaks in its FTIR spectrum: 3418 (NH), 3062 (vinylCH), 3021 (vinylCH), 2968 (vinylCH), 2935 (ethylCH), and 2876 (ethylCH). This indicates that the surface of the silica gel was functionalized with vinyl and ethylamino groups at relatively low temperatures and for a short period of time after treatment with tris(ethylamino)vinylsilane.

[0160] Example 3. Reaction of triethoxyvinylsilane with tert-butylgermanane.

[0161] A 1:1 molar mixture of approximately 1 mL of triethoxyvinylsilane and tert-butylgermanane was sealed in a 9.5 mL stainless steel cell equipped with an internal pressure sensor and thermocouple. The sample was heated to 250 °C and held isothermally for 1 hour. No significant pressure increase was detected, but a mild exothermic thermal event was observed with a temperature increase of approximately 212 °C. The mixture was analyzed by GC and GC-MS after cooling back to room temperature. The 1,1-addition and 1,2-addition hydrogengermanium products 1-triethoxysilyl-1-(tert-butylgermanium)ethane (minor) and 1-triethoxysilyl-2-(tert-butylgermanium)ethane (major) were detected according to the following mass peaks: (minor) m / z = 324(M+), 308, 280, 266, 238, 222, 210, 194, 179, 163, 147, 135, 119, 101, 89, 79, 57, 41; (major) m / z = 324(M+), 308, 280, 268, 238, 222, 211, 193, 181, 163, 149, 135, 119, 103, 91, 79, 57, 41. This demonstrates that, in the absence of a catalyst, Ge-H bonds in precursors, such as germanane, digermanane, and tert-butylgermanane, can react with Si-vinyl groups between 200 and 250 °C. This supports a scheme for forming a Ge-seed layer on a SiO2 substrate by first functionalizing the surface with vinyl groups and then reacting it with germanane or digermanane to form a Ge-H-terminated surface prior to germanium CVD growth.

[0162] Although this disclosure has been described with reference to certain preferred embodiments, those skilled in the art will understand that various changes can be made and elements can be substituted with equivalents without departing from the scope of the invention. Furthermore, many modifications can be made to adapt particular situations or materials to the teachings of the invention without departing from the basic scope of the invention. Therefore, it is intended that the invention be limited to the specific embodiments, but rather that the invention encompass all embodiments falling within the scope of the appended claims.

Claims

1. A method for forming a germanium-containing film on at least one surface of a substrate by a deposition process, the method comprising: At least one surface of the substrate is provided in the reaction chamber, the substrate having exposed surface hydroxyl groups; Introduce into the reaction chamber at least one organic amino-vinyl silane precursor represented by Formula I, comprising at least one vinyl group attached to at least one silicon atom and at least one organic amino anchoring group, or at least one organic amino-allyl silane precursor represented by Formula II, comprising at least one allyl group attached to at least one silicon atom and at least one organic amino anchoring group: Where R 1 Selected from straight or branched chains C1 to C 10 Alkyl, straight-chain or branched C3 to C4 10 Alkenyl, straight-chain or branched C3 to C 10 alkynyl group, C3 to C 10 cycloalkyl and C6 to C 10 Aryl; R 2 Selected from hydrogen, straight-chain or branched C1 to C2. 10 Alkyl, straight-chain or branched C2 to C6 alkenyl, straight-chain or branched C3 to C6 ynyl, C3 to C 10 cycloalkyl and C6 to C 10 Aryl; R 3 and R 4 Each is independently selected from hydrogen, straight-chain or branched C1-C 10 Alkyl, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C3-C6 alkynyl, C3-C 10 cycloalkyl, C6-C 10 Aryl, C1-C 10 Straight-chain, cyclic, or branched alkoxy groups, such as organic amino groups (NR) as defined above. 1 R 2 ) and halogens selected from Cl, Br and I; The reaction chamber was purged with purging gas; At least one first germanium-containing precursor containing at least one Ge-H bond is introduced into the reaction chamber; The reaction chamber was purged with purging gas; At least one second germanium-containing precursor, which is the same as or different from the first germanium-containing precursor, is introduced into the reaction chamber.

2. The method according to claim 1, wherein the at least one organic amino-vinylsilane precursor comprises at least one compound selected from the group consisting of: tris(methylamino)vinylsilane, tris(ethylamino)vinylsilane, tris(n-propylamino)vinylsilane, tris(isopropylamino)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, tris(pyrrolidinyl)vinylsilane, tris(piperidinyl)vinylsilane, tris(pyrrolidinyl)vinylsilane. bis(methylamino)methylvinylsilane, bis(ethylamino)methylvinylsilane, bis(n-propylamino)methylvinylsilane, bis(isopropylamino)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(pyrrolyl)methylvinylsilane, di(piperidinyl)methylvinylsilane, di(pyrrolyl)methylvinylsilane, bis(methylamino)divinylsilane, bis(ethylamino) Divinylsilane, bis(n-propylamino)divinylsilane, bis(isopropylamino)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, bis(pyrrolyl)divinylsilane, bis(piperidinyl)divinylsilane, bis(pyrrolyl)divinylsilane, (methylamino)dimethylvinylsilane, (ethylamino)dimethylvinylsilane, (n-propylamino)dimethylvinylsilane, (isopropylamino)dimethyl Vinylsilane, (sec-butylamino)dimethylvinylsilane, (tert-butylamino)dimethylvinylsilane, (dimethylamino)dimethylvinylsilane, (N-ethylmethylamino)dimethylvinylsilane, (diethylamino)dimethylvinylsilane, (N-methylcyclohexylamino)dimethylvinylsilane, (N-methylphenylamino)dimethylvinylsilane, (pyrrolyl)dimethylvinylsilane, (piperidinyl)dimethylvinylsilane, (pyrrolyl)dimethylvinylsilane, (methylamino)methyldivinylsilane, (ethylamino)methyldivinylsilane, (n-propylamino)methyldivinylsilane, (isopropylamino)methyldivinylsilane, (sec-butylamino)methyldivinylsilane(tert-butylamino)methyldivinylsilane, (dimethylamino)methyldivinylsilane, (N-ethylmethylamino)methyldivinylsilane, (diethylamino)methyldivinylsilane, (N-methylcyclohexylamino)methyldivinylsilane, (N-methylphenylamino)methyldivinylsilane, (pyrrolyl)methyldivinylsilane, (piperidinyl)methyldivinylsilane, (pyrrolyl)methyldivinylsilane, (methylamino)trivinylsilane, (ethylamino) (N-propylamino)trivinylsilane, (isopropylamino)trivinylsilane, (sec-butylamino)trivinylsilane, (tert-butylamino)trivinylsilane, (dimethylamino)trivinylsilane, (N-ethylmethylamino)trivinylsilane, (diethylamino)trivinylsilane, (N-methylcyclohexylamino)trivinylsilane, (pyrrolidinyl)methyltrivinylsilane, (piperidinyl)trivinylsilane, and (pyrrolidinyl)trivinylsilane.

3. The method according to claim 1, wherein the at least one organic amino-allyl silane precursor comprises at least one compound selected from the group consisting of: tris(methylamino)allyl silane, tris(ethylamino)allyl silane, tris(n-propylamino)allyl silane, tris(isopropylamino)allyl silane, tris(sec-butylamino)allyl silane, tris(tert-butylamino)allyl silane, tris(dimethylamino)allyl silane, tris(N-ethylmethylamino)allyl silane, tris(diethylamino)allyl silane, tris(N-methylcyclohexylamino)allyl silane, tris(N-methylphenylamino)allyl silane, tris(pyrrolidinyl)allyl silane, tris(piperidinyl)allyl silane, tris(pyrrolyl)allyl silane. bis(methylamino)methylallylsilane, bis(ethylamino)methylallylsilane, bis(n-propylamino)methylallylsilane, bis(isopropylamino)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, bis(pyrrolyl)methylallylsilane, bis(piperidinyl)methylallylsilane, bis(pyrrolyl)methylallylsilane, bis(methylamino)diallylsilane, bis(ethylamino)methylallylsilane Diallylsilane, bis(n-propylamino)diallylsilane, bis(isopropylamino)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, bis(pyrrolyl)diallylsilane, bis(piperidinyl)diallylsilane, bis(pyrrolyl)diallylsilane, (methylamino)dimethylallylsilane, (ethylamino)dimethylallylsilane, (n-propylamino)dimethylallylsilane, (isopropylamino)dimethyl Allylsilane, (sec-butylamino)dimethylallylsilane, (tert-butylamino)dimethylallylsilane, (dimethylamino)dimethylallylsilane, (N-ethylmethylamino)dimethylallylsilane, (diethylamino)dimethylallylsilane, (N-methylcyclohexylamino)dimethylallylsilane, (N-methylphenylamino)dimethylallylsilane, (pyrrolidinyl)dimethylallylsilane, (piperidinyl)dimethylallylsilane, (pyrrolidinyl)dimethylallylsilane, (methylamino)methyldiallylsilane, (ethylamino)methyldiallylsilane, (n-propylamino)methyldiallylsilane, (isopropylamino)methyldiallylsilane, (sec-butylamino)methyldiallylsilane(tert-butylamino)methyldiallylsilane, (dimethylamino)methyldiallylsilane, (N-ethylmethylamino)methyldiallylsilane, (diethylamino)methyldiallylsilane, (N-methylcyclohexylamino)methyldiallylsilane, (N-methylphenylamino)methyldiallylsilane, (pyrrolyl)methyldiallylsilane, (piperidinyl)methyldiallylsilane, (pyrrolyl)methyldiallylsilane, (methylamino)triallylsilane, (ethylamino)methyldiallylsilane, (N-propylamino)triallylsilane, (n-propylamino)triallylsilane, (isopropylamino)triallylsilane, (sec-butylamino)triallylsilane, (tert-butylamino)triallylsilane, (dimethylamino)triallylsilane, (N-ethylmethylamino)triallylsilane, (diethylamino)triallylsilane, (N-methylcyclohexylamino)triallylsilane, (pyrrolidinyl)methyltriallylsilane, (piperidinyl)triallylsilane, and (pyrrolidinyl)triallylsilane.

4. The method according to claim 1, wherein the organic amino-vinylsilane or the organic amino-allylsilane is substantially free of at least one impurity selected from the group consisting of organic amines, halide ions and metal ions.

5. The method according to claim 1, wherein the at least one germanium-containing precursor is selected from: trichlorogermanane (Cl3GeH), germanane (GeH4), diethylgermanane (Ge2H6), tert-butylgermanane (... t BuGeH3), phenylgermanane, sec-butylgermanane, isobutylgermanane, and benzylgermanane.

6. The method of claim 1, further comprising introducing a reducing gas into the reaction chamber after introducing the at least one first germanium-containing precursor.

7. The method of claim 1, wherein the at least one surface of the substrate is a silicon-containing film, and wherein the step of providing the at least one surface of the substrate in the reaction chamber comprises performing the following steps until the silicon-containing film of the desired thickness is achieved: At least one organic amino-vinylsilane or organic amino-allylsilane of Formula I and / or Formula II is introduced into the reaction chamber. The reaction chamber was purged with purging gas. An oxygen-containing source and / or a nitrogen-containing source are introduced into the reaction chamber, and The reaction chamber was purged with purging gas.

8. The method according to claim 7, wherein the nitrogen source is selected from: ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, and mixtures thereof.

9. The method according to claim 7, wherein the oxygen source is selected from: water, hydrogen peroxide, oxygen, oxygen plasma, ozone (O3), nitric oxide, nitrous oxide, nitrogen dioxide, carbon monoxide, carbon dioxide, and mixtures thereof.

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