Cyclosiloxanes and films made therefrom

Abstract

Compositions useful for depositing low dielectric constant (low-k) insulating materials into high aspect ratio gaps, trenches, vias, and other surface features of semiconductor devices by a plasma enhanced chemical vapor deposition (PECVD) process are disclosed. The compositions can include an alkoxy-functionalized cyclotrisiloxane derived from trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, or pentamethylcyclopentasiloxane. The alkoxy-functionalization can include from 1 to 10 carbon atoms. Methods of depositing the alkoxy-functionalized cyclotrisiloxane compositions by a PECVD process are also disclosed. Finally, films on a substrate including a flowable liquid or oligomer including an oligomeric or polymeric alkoxy-functionalized cyclotrisiloxane composition are disclosed.

Description

TECHNICAL FIELD

[0001] The present disclosure relates generally to cyclosiloxanes and films made therefrom, and more particularly to alkoxyl-functionalized cyclosiloxanes and films made therefrom. BACKGROUND

[0002] Semiconductor device geometries continue to decrease in size, and thus the surface density of these devices continues to increase. With this increase in density, the likelihood of electrical interference between adjacent devices, including crosstalk and parasitic capacitance, increases. To reduce the likelihood of such electrical interference, low dielectric constant (low-k) insulating materials are typically disposed in gaps, trenches, vias, and other surface features between adjacent devices.

[0003] Processes for placing these low-k insulating materials between adjacent devices include chemical vapor deposition (CVD). However, as device geometries shrink, the corresponding aspect ratios of the gaps, trenches, vias, and other surface features that need to be filled with low-k insulating materials increase. For example, current semiconductor devices typically have gaps, trenches, vias, and other features with aspect ratios greater than 5: 1 or even greater than 20: 1. Regardless, when depositing low-k materials in these high aspect ratio features with CVD, voids in the resulting films, or excessive growth of low-k insulating material known as "breadloafing," are not uncommon. Both voids and breadloafing are defects to be avoided when depositing low-k materials in high aspect ratio gaps, trenches, vias, and other surface features.

[0004] One way to address voids, breadloafing, and other defects when depositing low-k insulating materials in high aspect ratio surface features includes utilizing a process known as flowable chemical vapor deposition (FCVD). In FCVD, a low-k precursor or mixture of low-k precursor insulating materials can be introduced into a deposition chamber where it is exposed to a plasma. Exposure to the plasma induces oligomerization or polymerization of one or more of the low-k precursor materials to produce a flowable liquid or oligomer of low-k insulating material. The flowable liquid or oligomer can flow into high aspect ratio features like a liquid. The flowability of the low-k insulating material in FCVD results in fewer voids, breadloafing, or other defects in high aspect ratio surface features when compared to CVD.

[0005] Some low-k precursor insulating materials that have proven useful for depositing low-k insulating materials in high aspect ratio surface features by the FCVD process include trimethoxysiloxane (TRIMOS), triethoxysiloxane (TRIEOS), hexamethoxysiloxane (HMODS), and octamethoxysiloxane (OMOTS). See, e.g., U.S. Patent 7,943,531. Other low-k precursor materials that can be used in FCVD include cyclosiloxanes such as octamethylcyclotrisiloxane (OMTS), octamethylcyclotetrasiloxane (OMCTS), and 2,4,6,8-tetramethylcyclotetrasiloxane (TMCTS). See, e.g., U.S. Patent 7,825,038. While cyclosiloxane precursors perform well in the FCVD process, they are not without problems. For example, TMCTS can oligomerize or polymerize prior to exposure to the plasma during the FCVD process. Then, when exposed to the plasma, the oligomerized or polymerized TMCTS material can lose its ability to flow like a liquid into the high aspect ratio surface features during the FCVD process. Thus, there is a need for low-k cyclosiloxane precursor materials that exhibit less tendency to oligomerize or polymerize prior to exposure to the plasma in the FCVD process.

[0006] The present disclosure is directed to overcoming one or more of the problems set forth above, and / or other issues associated with the prior art. SUMMARY

[0007] According to one aspect of the present disclosure, a composition is disclosed. The composition can include a compound represented by Formula A, B, or C:

[0008] A

[0009] B

[0010] C

[0011] In each of the compounds shown above, R 1 is an alkoxy group having 1 to 10 carbon atoms. R 2 may be H or an alkoxy group having 1 to 10 carbon atoms. Finally, if present, R 3 may be H or an alkoxy group having 1 to 10 carbon atoms.

[0012] In one instance, R 1is an alkoxy selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, t-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl-1-pentoxy, 3-methyl-1-pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof. In this embodiment, R 2 is H, and R 3 is also H.

[0013] In another instance, R 1 is an alkoxy selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, t-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl-1-pentoxy, 3-methyl-1-pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof. In this particular embodiment, R 2is an alkoxy selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, t-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl-1-pentoxy, 3-methyl-1-pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof. In this embodiment, R 3 is H.

[0014] In other cases, R 1 is an alkoxy selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, t-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl-1-pentoxy, 3-methyl-1-pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof. In this embodiment, R 2 is H, and R 3is an alkoxy selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, t-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl-1-pentoxy, 3-methyl-1-pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof.

[0015] In another example, R 1 is an alkoxy selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, t-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl-1-pentoxy, 3-methyl-1-pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof. In this last preferred embodiment, R 2alkyl groups, and combinations thereof. In this embodiment, R1is selected from the group consisting of methyl, ethyl, 1 -propyl, isopropyl, 1 -butyl, t-butyl, s-butyl, 1 -pentyl, 2-pentyl, 3-pentyl, 2-methyl-1 -butyl, 3-methyl-1 -butyl, 2-methyl-2-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1 -propyl, 1 -hexyl, 2-hexyl, 3-hexyl, 2-methyl-1 -pentyl, 3-methyl-1 -pentyl, 4-methyl-1 -pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1 -butyl, 2,3-dimethyl-1 -butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, 2-ethyl-1 -butyl, cyclopentyl, cyclohexyl, and combinations thereof. Finally, in this embodiment, R 3 alkyl groups, and combinations thereof. In this embodiment, R1is selected from the group consisting of methyl, ethyl, 1 -propyl, isopropyl, 1 -butyl, t-butyl, s-butyl, 1 -pentyl, 2-pentyl, 3-pentyl, 2-methyl-1 -butyl, 3-methyl-1 -butyl, 2-methyl-2-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1 -propyl, 1 -hexyl, 2-hexyl, 3-hexyl, 2-methyl-1 -pentyl, 3-methyl-1 -pentyl, 4-methyl-1 -pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1 -butyl, 2,3-dimethyl-1 -butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, 2-ethyl-1 -butyl, cyclopentyl, cyclohexyl, and combinations thereof.

[0016] According to this aspect of the application, the alkoxylated cyclosiloxane compounds can generally be represented by Formula A, and the alkoxylated cyclosiloxane compounds can be selected from the group consisting of:

[0017]

[0018] According to this aspect of the application, the alkoxylated cyclosiloxane compounds can generally be represented by Formula B, and the alkoxylated cyclosiloxane compounds can be selected from the group consisting of:

[0019]

[0020]

[0021] According to this aspect of the application, the alkoxylated cyclosiloxane compounds can generally be represented by Formula C, and the alkoxylated cyclosiloxane compounds can be selected from the group consisting of:

[0022]

[0023]

[0024]

[0025] According to this same aspect of the application, the composition can comprise a mixture of these alkoxy-functionalized cyclotrisiloxane compounds. For example, the composition can comprise a mixture of compounds of Formula A and Formula B. In another instance, the mixture of compounds can comprise compounds of Formula A and Formula C. In a further instance, the mixture of compounds can comprise compounds of Formula B and Formula C. Finally, the mixture of compounds can comprise compounds of Formula A, Formula B, and Formula C.

[0026] According to a second aspect of the application, a method of depositing a silicon-containing film is disclosed. The method can include the step of placing a substrate comprising surface features in a deposition chamber of a CVD apparatus, such as a plasma-enhanced CVD apparatus (PECVD). The method can additionally include introducing two or more molecules of an alkoxy-functionalized cyclotrisiloxane compound represented by Formula A, B, or C below into the deposition chamber:

[0027] A

[0028] B

[0029] C

[0030] In each of the above compounds, R 1 may be H or an alkoxy group having 1 to 10 carbon atoms. Finally, if present, R 2 may be H or an alkoxy group having 1 to 10 carbon atoms. Finally, if present, R 3 may be H or an alkoxy group having 1 to 10 carbon atoms.

[0031] The two or more molecules of the alkoxy-functionalized cyclotrisiloxane compound represented by Formula A, B, or C can then be exposed to a plasma in the deposition chamber. This exposure to the plasma can induce a reaction between the two or more molecules and thus produce a flowable liquid or oligomer made from the two or more molecules of the alkoxy-functionalized cyclotrisiloxane compound represented by Formula A, B, or C. This flowable liquid or oligomer can allow for at least partial filling of the surface features of the substrate and thus produce a silicon-containing film.

[0032] In one embodiment, the method of depositing a silicon-containing film can further include wherein the introducing step further comprises introducing an inert gas into the deposition chamber, wherein the inert gas is selected from the group consisting of helium, argon, xenon, and mixtures thereof. The plasma in the exposing step can be an in-situ plasma, and atoms of the inert gas can not be incorporated into the molecule- made flowable liquid or oligomer from the two or more alkoxy-functional cyclotrisiloxane compounds represented by Formula A, B, or C upon exposure to the in-situ plasma in the deposition chamber, thereby producing a silicon-containing film comprising silicon and carbon.

[0033] In another embodiment of the method, the introducing step can further comprise introducing a nitrogen source into the deposition chamber, wherein the nitrogen source can be selected from the group consisting of N2, ammonia, NF3, organic amines, and mixtures thereof. In this embodiment, the plasma in the exposing step can be an in-situ plasma, and nitrogen atoms of the nitrogen source can be incorporated into the molecule-made flowable liquid or oligomer from the two or more alkoxy-functional cyclotrisiloxane compounds represented by Formula A, B, or C upon exposure to the in-situ plasma in the deposition chamber, thereby producing a silicon-containing film comprising silicon, carbon, and nitrogen.

[0034] In a further embodiment of the method, the introducing step can further comprise introducing an oxygen source selected from the group consisting of water, oxygen, ozone, nitric oxide, nitrous oxide, carbon monoxide, carbon dioxide, and combinations thereof, and the plasma in the exposing step can be an in-situ plasma. In this embodiment, oxygen atoms of the oxygen source can be incorporated into the molecule-made flowable liquid or oligomer from the two or more alkoxy-functional cyclotrisiloxane compounds represented by Formula A, B, or C upon exposure to the in-situ plasma in the deposition chamber, thereby producing a silicon-containing film comprising silicon, carbon, and oxygen.

[0035] In another embodiment of the method, the plasma in the exposing step can be a remote plasma comprising an inert gas, and the inert gas can be selected from the group consisting of helium, argon, xenon, and mixtures thereof. In this embodiment, atoms of the inert gas can not be incorporated into the molecule-made flowable liquid or oligomer from the two or more alkoxy-functional cyclotrisiloxane compounds represented by Formula A, B, or C upon exposure to the remote plasma in the deposition chamber, thereby producing a silicon-containing film comprising silicon and carbon.

[0036] This embodiment of the method described in this aspect of the application can additionally include wherein the plasma in the exposing step can be a remote plasma comprising a nitrogen source, and the nitrogen source can be selected from the group consisting of N2, ammonia, NF3, organic amines, and mixtures thereof. In this embodiment, nitrogen atoms of the nitrogen source can be incorporated into the molecule-made flowable liquid or oligomer from the two or more alkoxy-functional cyclotrisiloxane compounds represented by Formula A, B, or C upon exposure to the remote plasma in the deposition chamber, thereby producing a silicon-containing film comprising silicon, carbon, and nitrogen.

[0037] In this second aspect of the application, the method can further comprise wherein the plasma in the exposing step is a remote plasma comprising an oxygen source. The oxygen source can be selected from the group consisting of water, oxygen, ozone, nitric oxide, nitrous oxide, carbon monoxide, carbon dioxide, and combinations thereof. In this embodiment, oxygen atoms of the oxygen source can be incorporated into the flowable liquid or oligomer made from the molecules of the two or more oligomeric or polymeric alkoxyl-functionalized cyclosiloxane compounds represented by Formula A, B, or C after exposure to the remote plasma in the deposition chamber. In this case, a silicon-containing film comprising silicon, carbon, and oxygen can be produced.

[0038] In the method, a pretreatment can be performed in a pretreatment step prior to placing the substrate in the deposition chamber, and the pretreatment step can be selected from the group consisting of a plasma treatment, a thermal treatment, a chemical treatment, exposure to ultraviolet light, exposure to an electron beam, and combinations thereof.

[0039] The method can further comprise a post-treatment in a post-treatment step. The post-treatment can be selected from the group consisting of ultraviolet curing of the silicon-containing film, plasma annealing of the silicon-containing film, infrared treatment of the silicon-containing film, thermal annealing of the silicon-containing film in a non-oxidizing environment, thermal annealing of the silicon-containing film in an oxidizing environment, and combinations thereof, thereby densifying the silicon-containing film.

[0040] According to a third aspect of the present disclosure, a film on a substrate is disclosed. The film can comprise a flowable liquid or oligomer comprising molecules of two or more oligomeric or polymeric alkoxyl-functionalized cyclosiloxane compounds represented by Formula A, B, or C:

[0041] A

[0042] B

[0043] C

[0044] In each of the compounds shown above, R 1 is H or an alkoxy group having 1-10 carbon atoms. R 2 may be H or an alkoxy group having 1-10 carbon atoms. Finally, if present, R 3 may be H or an alkoxy group having 1-10 carbon atoms. BRIEF DESCRIPTION OF DRAWINGS

[0045] Figure 1 is an SEM photo of a patterned wafer having a 2-ethoxy-2,4,6,8-tetramethylcyclotetrasiloxane silicon-containing film deposited according to Working Example 21, with the as-deposited film thermally annealed in a non-oxidizing atmosphere and then UV cured.

[0046] Figure 2is another SEM photo of a patterned wafer with a 2-ethoxy-2,4,6,8-tetramethylcyclotetrasiloxane silicon-containing film deposited according to Working Example 21, with the as-deposited film thermally annealed in a non-oxidizing atmosphere and UV cured.

[0047] Figure 3 is an SEM photo of a differently sized pattern wafer with a 2-ethoxy-2,4,6,8-tetramethylcyclotetrasiloxane silicon-containing film deposited according to Working Example 22, with the as-deposited film thermally annealed in an oxidizing atmosphere and UV cured.

[0048] Figure 4 is an SEM photo of a 2-isopropoxy-2,4,6,8-tetramethylcyclotetrasiloxane silicon-containing film deposited according to Working Example 23 without thermal annealing or UV curing of the as-deposited film.

[0049] Figure 5 is an SEM photo of a 2-isopropoxy-2,4,6,8-tetramethylcyclotetrasiloxane silicon-containing film deposited according to Working Example 23, with the as-deposited film thermally annealed in a non-oxidizing atmosphere and UV cured.

[0050] Figure 6 is a graph depicting the electrical breakdown of films produced with 2-ethoxy-2,4,6,8-tetramethylcyclotetrasiloxane versus the electrical breakdown of films produced with 2-isopropoxy-2,4,6,8-tetramethylcyclotetrasiloxane. DETAILED DESCRIPTION

[0051] Various aspects of the disclosure will now be described with reference to the figures and tables disclosed herein, if applicable, like reference numbers indicate like elements. As noted above, while the cyclosiloxane precursors perform well in the FCVD process, they are not without problems. For example, TMCTS can oligomerize or polymerize prior to exposure to the plasma in the FCVD process. Then, when exposed to the plasma, the oligomerized or polymerized TMCTS material can lose some of its ability to flow into high aspect ratio surface features like a liquid. Thus, Applicant investigated ways to reduce the potential for oligomerization or polymerization of the low-k cyclosiloxane precursor material prior to exposure to the plasma in the FCVD process.

[0052] To this end, Applicant investigated the cationic ring-opening polymerization amplification reaction of TMCTS and 2-ethoxy-2,4,6,8-tetramethylcyclotetrasiloxane. As depicted below, Applicant believes that TMCTS oligomerizes or polymerizes at least through the following cationic ring-opening sequence: (1)

[0054] (2)

[0056] (3)

[0058] (4)

[0060]

[0061] As described above in step (1) of the sequence, the applicants believe that the oxygen atom of the first TMCTS molecule is protonated. Subsequently, in step (2) of the sequence, the first TMCTS molecule with the protonated oxygen atom is stabilized by coordination with the oxygen atom of a second TMCTS molecule. A charge transfer occurs between the protonated oxygen atom of the first TMCTS molecule and the coordinating oxygen atom of the second TMCTS, resulting in ring opening of the first TMCTS molecule, as depicted in step (3) of the above sequence. Finally, in step (4) of the sequence shown above, a charge transfer occurs within the second TMCTS molecule, resulting in ring opening of the second TMCTS molecule, thus producing a TMCTS oligomer, which can then further oligomerize with nearby TMCTS molecules and can ultimately polymerize with additional TMCTS molecules. The applicants believe that 2-ethoxy-2,4,6,8-tetramethylcyclotetrasiloxane undergoes a similar cationic ring opening sequence.

[0062] Surprisingly, the applicants have learned through computer modeling of the above-described cationic ring opening sequence that 2-ethoxy-2,4,6,8-tetramethylcyclotetrasiloxane is more thermally stable than TMCTS. Thus, the applicants believe that 2-ethoxy-2,4,6,8-tetramethylcyclotetrasiloxane is more thermally stable than TMCTS. As a result, the applicants believe that functionalizing at least one silicon atom of an alkoxyl-functionalized cyclotetrasiloxane precursor material, such as TMCTS, results in higher thermal stability of the precursor, thereby reducing any tendency of the precursor to oligomerize or polymerize prior to exposure to the plasma in an FCVD process as compared to TMCTS.

[0063] Accordingly, in a first aspect of the present invention, novel and nonobvious compositions are disclosed herein comprising alkoxyl-functionalized cyclotetrasiloxane compounds that can be used as precursors in an FCVD process. The compounds disclosed herein include those depicted by the following Formulas A, B, or C:

[0064] A

[0065] B

[0066] C

[0067] In each of the above compounds, R 1 is an alkoxy group having 1-10 carbon atoms. R2 can be H or an alkoxy group having 1 to 10 carbon atoms. Finally, if present, R 3 It may be H or an alkoxy group having 1 to 10 carbon atoms.

[0068] For clarity, in the formulas depicted above and described throughout the specification, the term "alkoxy" refers to an -OR group, wherein R contains 1 to 10 carbon atoms. For example, in one embodiment, the alkoxy group can be selected from 1-heptyloxy, 1-octyloxy, 1-nonyloxy, and 1-decyloxy. In a more preferred embodiment, the alkoxy group is selected from methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, tert-butoxy, sec-butoxy, 1-pentyloxy, 2-pentyloxy, 3-pentyloxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexyloxy, 2-hexyloxy, 3-hexyloxy, 2-methyl-1-pentyloxy, 3-pentyloxy, -methyl-1-pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentyloxy, cyclohexyloxy, and combinations thereof.

[0069] Based on the description immediately above, in a preferred embodiment, a composition is disclosed, which comprises an alkoxy-functionalized cyclosiloxane compound represented by the above formula A, B or C, wherein R 1 is an alkoxy group selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, tert-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexyloxy, 2-hexyloxy, 3-hexyloxy, 2-methyl-1-pentoxy, 3-methyl -1-pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof. In this embodiment, R 2 is H, and R 3 Also H.

[0070] In another preferred embodiment, a composition is disclosed comprising an alkoxy functionalized cyclosiloxane compound, wherein R 1 is an alkoxy selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, t-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexyloxy, 2-hexyloxy, 3-hexyloxy, 2-methyl-1-pentoxy, 3-methyl-1-pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof. In this particular embodiment, R 2 is an alkoxy selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, t-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexyloxy, 2-hexyloxy, 3-hexyloxy, 2-methyl-1-pentoxy, 3-methyl-1-pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof. In this embodiment, R 3 is H.

[0071] In another preferred embodiment, a composition is disclosed comprising an alkoxy functionalized cyclosiloxane compound, wherein R 1is an alkoxy selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, t-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexyloxy, 2-hexyloxy, 3-hexyloxy, 2-methyl-1-pentoxy, 3-methyl-1-pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof. In this preferred embodiment, R 2 is H, and R 3 is an alkoxy selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, t-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexyloxy, 2-hexyloxy, 3-hexyloxy, 2-methyl-1-pentoxy, 3-methyl-1-pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof.

[0072] In a final preferred embodiment, a composition is disclosed comprising an alkoxy-functionalized cyclosiloxane compound, wherein R 1is an alkoxy selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, t-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl-1-pentoxy, 3-methyl-1-pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof. In this last preferred embodiment, R 2 is an alkoxy selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, t-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl-1-pentoxy, 3-methyl-1-pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof. Finally, in this embodiment, R 3 is an alkoxy selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, t-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl-1-pentoxy, 3-methyl-1-pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof.

[0073] Next, in a more preferred embodiment of this aspect of the application, a composition is disclosed wherein the alkoxyl-functional cyclosiloxane compound is generally represented by Formula A, and the alkoxyl-functional cyclosiloxane compound is selected from the group consisting of:

[0074]

[0075]

[0076] In another more preferred embodiment of this aspect of the application, a composition is disclosed wherein the alkoxyl-functional cyclosiloxane compound is generally represented by Formula B, and the alkoxyl-functional cyclosiloxane compound is selected from the group consisting of:

[0077]

[0078]

[0079]

[0080] Finally, in a further more preferred embodiment of this aspect of the application, a composition is disclosed wherein the alkoxyl-functional cyclosiloxane compound is generally represented by Formula C, and the alkoxyl-functional cyclosiloxane compound is selected from the group consisting of:

[0081]

[0082]

[0083] Applicants contemplate that in some instances, a composition comprising a mixture of alkoxyl-functional cyclosiloxane compounds represented by Formula A, B, or C can be preferred over a composition comprising only one alkoxyl-functional cyclosiloxane compound represented by Formula A, B, or C. The mixture of alkoxyl-functional cyclosiloxane compounds may, for example, comprise a mixture of compounds of Formula A and Formula B. In another instance, the mixture of compounds can comprise compounds of Formula A and Formula C. In a further instance, the mixture of compounds can comprise compounds of Formula B and Formula C. Finally, the mixture of compounds can comprise compounds of Formula A, Formula B, and Formula C.

[0084] Next, the alkoxy-functionalized cyclotrisiloxane compounds having the formula A, B, or C shown or described above can be produced, for example, by a reaction between a cyclotrisiloxane and an alcohol. In this reaction, the hydrogen atoms attached to the silicon atoms of the cyclotrisiloxane can be replaced by alkoxy groups corresponding to the alcohol having 1-10 carbon atoms used in the reaction. In some embodiments, a catalyst can be used to increase the rate at which the reaction occurs. In certain embodiments, the reaction is carried out in a mixture of the cyclotrisiloxane, the alcohol of interest, and additionally in the presence of a catalyst as a solution in a solvent. While not intended to be limiting, the cyclotrisiloxane reactant can include 2,4,6-trimethylcyclotrisiloxane (TRIMCTS), 2,4,6,8-tetramethylcyclotetrasiloxane (TMCTS), and 2,4,6,8,10-pentamethylcyclopentasiloxane (PM CPS), as demonstrated above. While not depicted in the present application, other cyclotrisiloxane reactants (e.g., 2,4,6,8,10,12-hexamethylcyclohexasiloxane) are certainly within the scope of the present disclosure.

[0085] The alcohol reactant has 1-10 carbon atoms. In certain embodiments, the alcohol is selected from the group consisting of 1-heptanol, 1-octanol, 1-nonanol, and 1-decanol. In preferred embodiments of this aspect of the disclosure, the alcohol comprises 1-6 carbon atoms, and the alcohol is selected from the group consisting of methanol, ethanol, 1-propanol, isopropanol, 1-butanol, t-butanol, sec-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 2-methyl-3-butanol, 2,2-dimethyl-1-propanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2,2-dimethyl-1-butanol, 2,3-dimethyl-1-butanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, cyclopentanol, cyclohexanol, and combinations thereof.

[0086] The catalyst used in the process of making the alkoxy-functionalized cyclotrisiloxanes disclosed herein is a catalyst that facilitates the formation of silicon-oxygen bonds. Exemplary catalysts that can be used with the processes disclosed herein include, but are not limited to, halide-free main group, transition metal, lanthanide, and actinide catalysts such as the following: 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene, 2,2'-bipyridine, phenanthroline, B(C6F5)3, BR3(R = linear, branched, or cyclic C1to C 10 alkyl, C5to C 10 aryl, or C1to C 10 alkoxy), AlR3(R = linear, branched, or cyclic C1to C 10alkyl, C5to C 10 aryl or C1to C 10 alkoxy), (C5H5)2TiR2(R = alkyl, H, alkoxy, organoamino, carbosilyl), (C5H5)2Ti(OAr)2[Ar = (2,6- i Pr)2C6H3)], (C5H5)2Ti(SiHRR')PMe3(wherein R, R' are each independently selected from H, Me, Ph), TiMe2(dmpe)2(dmpe = 1,2-bis(dimethylphosphino)ethane), bis(benzene)chromium(O), Cr(CO)6, Mn2(CO) 12 , Fe(CO)5, Fe3(CO) 12 , (C5H5)Fe(CO)2Me, Co2(CO)8, Ni(II) acetate, nickel(II) acetylacetonate, Ni(cyclooctadiene)2, [(dippe)Ni(p-H)]2(dippe = 1,2-bis(diisopropylphosphino)ethane), (R-indenyl)Ni(PR'3)Me (R = 1- i Pr, 1-SiMe3, 1,3-(SiMe3)2; R' = Me, Ph), [{Ni(p-CH2:CHSiMe2)2O}2{p-(p-CH2:CHSiMe2)2O}], Cu(I) acetate, CuH, [tris(4,4-dimethyl-2-oxazolinato)phenylborate]ZnH, (C5H5)2ZrR2(R = alkyl, H, alkoxy, organoamino, carbosilyl), Ru3(CO) 12 , [(Et3P)Ru(2,6-diindylthiol)] [B[3,5-(CF3)2C6H3]4], [(C5Me5)Ru(R3P) x (NCMe) 3-x ] + (wherein R is selected from linear, branched or cyclic C1to C 10 alkyl and C5to C 10 aryl; x = 0, 1, 2, 3), Rh6(CO) 16 , tris(triphenylphosphine)rhodium(I) carbonyl hydride, Rh2H2(CO)2(dppm)2(dppm = bis(diphenylphosphino)methane), Rh2(p-SiRH)2(CO)2(dppm)2(R = Ph, Et, C6H 13Pd / C, tris(dibenzylideneacetone)dipalladium(0), tetrakis(triphenylphosphine)palladium(0), Pd(II) acetate, (C5H5)2SmH, (C5Me5)2SmH, (THF)2Yb[N(SiMe3)2]2, (NHC)Yb(N(SiMe3)2)2[NHC = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene)], Yb(η 2 - Ph2CNPh)(hmpa)3(hmpa = hexamethylphosphoramide), W(CO)6, Re2(CO) 10 , Os3(CO) 12 , Ir4(CO) 12 , (acetylacetonate)dicarbonyliridium(I), Ir(Me)2(C5Me5)L (L = PMe3, PPh3), [Ir(cyclooctadiene)OMe]2, PtO2(Adams's catalyst), platinum on carbon (Pt / C), ruthenium on carbon (Ru / C), ruthenium on alumina, palladium on carbon, nickel on carbon, osmium on carbon, platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane (Karstedt's catalyst), bis(tri-tert-butylphosphine)platinum(0), Pt(cyclooctadiene)2, [(Me3Si)2N]3U][BPh4], [(Et2N)3U][BPh4], and other halide-free M n+ complexes (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, U; n = 0, 1, 2, 3, 4, 5, 6).

[0087] The catalysts listed above, as well as pure noble metals such as ruthenium, platinum, palladium, rhodium, and osmium, can also be fixed on a support. The support can be a solid with a high surface area. Typical support materials include, but are not limited to, alumina, MgO, zeolite, carbon, monolithic cordierite, diatomaceous earth, silica gel, silica / alumina, ZrO, TiO 2 and metal organic frameworks (MOFs). Preferred supports are carbon (e.g., platinum-carbon, palladium-carbon, carbon-supported rhodium, carbon-supported ruthenium), alumina, silica and MgO. The metal loading of the catalyst is in the range of about 0.01 wt % to about 50 wt %. The preferred range is about 0.5 wt % to about 20 wt %. The more preferred range is about 0.5 wt % to about 10 wt %. Catalysts that require activation can be activated by many known methods. Heating the catalyst under vacuum is a preferred method. The catalyst can be activated in the reaction vessel before being added to the reaction vessel or before adding the reactants. The catalyst may contain a co-catalyst. Co-catalyst is a substance that is not a catalyst itself, but when mixed with an active catalyst in small amounts, improves their efficiency (activity and / or selectivity). Co-catalysts are typically metals such as Mn, Ce, Mo, Li, Re, Ga, Cu, Ru, Pd, Rh, Ir, Fe, Ni, Pt, Cr, Cu and Au, and / or their oxides. They can be added separately to the reactor vessel, or they can be a part of the catalyst itself. For example, Ru / Mn / C (ruthenium carbon promoted by manganese) or Pt / CeO2 / Ir / SiO2 (platinum silicon oxide promoted by ceria and iridium). Some co-catalysts themselves can serve as catalysts, but they are used in combination with the primary catalyst to improve the activity of the primary catalyst. Catalyst can be used as a co-catalyst for other catalysts. In this context, catalyst can be referred to as bimetallic (or polymetallic) catalyst. For example, Ru / Rh / C can be referred to as ruthenium carbon promoted by ruthenium and rhodium bimetallic catalyst or rhodium on carbon. Active catalyst is the material that serves as catalyst in a specific chemical reaction.

[0088] The molar ratio of catalyst to cyclosiloxane in the reaction mixture ranges from 0.1-1, 0.05-1, 0.01-1, 0.005-1, 0.001-1, 0.0005-1, 0.0001-1, 0.00005-1 or 0.00001-1.

[0089] In some embodiments, the reaction mixture comprising the cyclotrisiloxane, alcohol, and catalyst can additionally comprise an anhydrous solvent. Exemplary solvents can include, but are not limited to, linear, branched, cyclic, or polyether (e.g., tetrahydrofuran (THF), diethyl ether, diethylene glycol dimethyl ether, and / or tetraethylene glycol dimethyl ether); linear, branched, or cyclic alkanes, alkenes, aromatics, and halogenated hydrocarbons (e.g., pentanes, hexanes, toluene, and dichloromethane). The choice of one or more solvents, if added, can be influenced by its compatibility with the reagents contained in the reaction mixture, solubility of the catalyst, and / or the method of isolation of the selected intermediate and / or final product. In other embodiments, the reaction mixture does not comprise a solvent.

[0090] In the reactions described herein, the reaction between the cyclotrisiloxane and alcohol occurs at one or more temperatures ranging from about 0 °C to about 200 °C, preferably 0 °C to about 100 °C. Exemplary temperatures for the reaction include ranges having any one or more of the following endpoints: 0 °C, 10 °C, 20 °C, 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, or 100 °C. Suitable temperature ranges for the reaction can be dictated by the physical properties of the reagents and optional solvent. Examples of particular reaction temperature ranges include, but are not limited to, 0 °C to 80 °C, or 0 °C to 30 °C.

[0091] In certain embodiments of the reactions described herein, the reaction can be at a pressure ranging from about 1 to about 115 psia or about 15 to about 45 psia. In some embodiments where the cyclotrisiloxane is a liquid at ambient conditions, the reaction is conducted at atmospheric pressure. In some embodiments where the cyclotrisiloxane is a gas at ambient conditions, the reaction is conducted at 15 psia or greater.

[0092] In certain embodiments, one or more reagents can be introduced to the reaction mixture as a liquid or as a vapor. In embodiments where one or more reactants are added as a vapor, a non-reactive gas such as nitrogen or an inert gas can be used as a carrier gas to deliver the vapor to the reaction mixture. In embodiments where one or more reagents are added as a liquid, the reagent can be added neat or, alternatively, can be diluted with a solvent.

[0093] The crude mixture comprising the alkoxy-functional cyclotrisiloxane compound of Formula A, B, or C, catalyst, and potentially residual cyclotrisiloxane, alcohol, and solvent can require a separation process. Examples of suitable separation processes include, but are not limited to, distillation, evaporation, membrane separation, filtration, vapor phase transfer, extraction, fractionation using a reverse phase column, and combinations thereof.

[0094] Synthesis of alkoxy-functional cyclotrisiloxanes

[0095] Working Example 1 - Synthesis of 2-methoxy-2,4,6,8-tetramethylcyclotrisiloxane

[0096] To 1 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial was added 0.25 mL of methanol directly followed by the addition of a catalytic amount of Ru3(CO) 12 The reaction mixture was allowed to sit for a length of 16 hours after which it was sampled and subjected to GC-MS to confirm the formation of the desired product. GC-MS showed the following peaks: m / z = 270 (M+), 255 (M-15), 239, 225, 209, 193, 179, 165, 148, 135, 119, 105, 89, 75, 59,

[0097] Working Example 2 - Synthesis of 2-ethoxy-2,4,6,8-tetramethylcyclotetrasiloxane

[0098] To 1 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial was added 0.25 mL of ethanol directly followed by the addition of a catalytic amount of Ru3(CO) 12 The reaction mixture was allowed to sit for a length of 16 hours after which it was sampled and subjected to GC-MS to confirm the formation of the desired product. GC-MS showed the following peaks: m / z = 284 (M+), 269 (M-15), 253, 239, 223, 209, 193, 179, 165, 149, 135, 119, 105, 89, 73, 59,

[0099] Working Example 3 - Synthesis of 2-n-propoxy-2,4,6,8-tetramethylcyclotetrasiloxane

[0100] To 1 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial was added 0.25 mL of 1-propanol directly followed by the addition of a catalytic amount of Ru3(CO) 12 The reaction mixture was allowed to sit for a length of 16 hours after which it was sampled and subjected to GC-MS to confirm the formation of the desired product. GC-MS showed the following peaks: m / z = 298 (M+), 283 (M-15), 269, 253, 239, 223, 209, 193, 179, 165, 149, 135, 119, 103, 89, 75, 59, 43.

[0101] Working Example 4 - Synthesis of 2-isopropoxy-2,4,6,8-tetramethylcyclotetrasiloxane

[0102] To 1 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial was added 0.25 mL of 2-propanol directly followed by the addition of a catalytic amount of Ru3(CO) 12of THF. The reaction mixture was allowed to stand for a length of 16 hours, then sampled and subjected to GC-MS to confirm the formation of the desired product. GC-MS showed the following peaks: m / z = 312 (M+), 297 (M-15), 269, 253, 239, 223, 209, 193, 179, 165, 149, 135, 119, 105, 89, 75, 57, 41.

[0103] Working Example 5 - Synthesis of 2-n-butoxy-2,4,6,8-tetramethylcyclotetrasiloxane

[0104] To 1 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial was added directly 0.25 mL of 1 -butanol, followed by a catalytic amount of Ru3(CO) 12 of THF. The reaction mixture was allowed to stand for a length of 16 hours, then sampled and subjected to GC-MS to confirm the formation of the desired product. GC-MS showed the following peaks: m / z = 312 (M+), 297 (M-15), 269, 253, 239, 223, 209, 193, 179, 165, 149, 135, 119, 105, 89, 75, 57, 41.

[0105] Working Example 6 - Synthesis of 2-sec-butoxy-2,4,6,8-tetramethylcyclotetrasiloxane

[0106] To 1 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial was added directly 0.25 mL of 2-butanol, followed by a catalytic amount of Ru3(CO) 12 of THF. The reaction mixture was allowed to stand for a length of 16 hours, then sampled and subjected to GC-MS to confirm the formation of the desired product. GC-MS showed the following peaks: m / z = 312 (M+), 297 (M-15), 269, 253, 239, 223, 209, 193, 179, 165, 149, 135, 119, 105, 89, 75, 57, 41.

[0107] Working Example 7 - Synthesis of 2-t-butoxy-2,4,6,8-tetramethylcyclotetrasiloxane

[0108] To 1 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial was added directly 0.25 mL of t-butanol, followed by a catalytic amount of Ru3(CO) 12of THF. The reaction mixture was allowed to stand for a length of 16 hours, then sampled and subjected to GC-MS to confirm the formation of the desired product. GC-MS showed the following peaks: m / z = 326 (M+), 311 (M-15), 297, 253, 239, 223, 209, 193, 179, 165, 149, 135, 119, 105, 89, 71, 57, 43.

[0109] Working Example 8 - Synthesis of 2-tert-pentyl-2,4,6,8-tetramethylcyclotetrasiloxane

[0110] To 1 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial was added directly 0.25 mL of tert-pentanol, followed by a catalytic amount of Ru3(CO) 12 of THF. The reaction mixture was allowed to stand for a length of 16 hours, then sampled and subjected to GC-MS to confirm the formation of the desired product. GC-MS showed the following peaks: m / z = 326 (M+), 311 (M-15), 297, 253, 239, 223, 209, 193, 179, 165, 149, 135, 119, 105, 89, 71, 57, 43.

[0111] Working Example 9 - Synthesis of 2-cyclopentyloxy-2,4,6,8-tetramethylcyclotetrasiloxane

[0112] To 1 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial was added directly 0.25 mL of cyclopentanol, followed by a catalytic amount of Ru3(CO) 12 of THF. The reaction mixture was allowed to stand for a length of 16 hours, then sampled and subjected to GC-MS to confirm the formation of the desired product. GC-MS showed the following peaks: m / z = 326 (M+), 311 (M-15), 297, 253, 239, 223, 209, 193, 179, 165, 149, 135, 119, 105, 89, 71, 57, 43.

[0113] Working Example 10 - Synthesis of 2-cyclohexyloxy-2,4,6,8-tetramethylcyclotetrasiloxane

[0114] To 1 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial was added directly 0.25 mL of cyclohexanol, followed by a catalytic amount of Ru3(CO) 12of THF. The reaction mixture was allowed to stand for a length of 16 hours, then sampled and subjected to GC-MS to confirm the formation of the desired product. GC-MS showed the following peaks: m / z = 338 (M+), 323 (M-15), 309, 295, 281, 253, 239, 223, 209, 193, 179, 165, 149, 135, 119, 103, 83, 69, 55, 41.

[0115] Working Example 11 - Synthesis of 2,4-Dimethoxy-2,4,6,8-tetramethylcyclotetrasiloxane or 2,6-Dimethoxy-2,4,6,8-tetramethylcyclotetrasiloxane

[0116] To 1 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial was added directly 0.25 mL of methanol, followed by a catalytic amount of Ru3(CO) 12 of THF. The reaction mixture was allowed to stand for a length of 16 hours, then sampled and subjected to GC-MS to confirm the formation of the desired product. GC-MS showed the following peaks: m / z = 300 (M+), 285 (M-15), 269, 253, 239, 225, 209, 193, 179, 165, 149, 133, 119, 105, 89, 73, 59, 45.

[0117] Working Example 12 - Synthesis of 2,4-Diethoxy-2,4,6,8-tetramethylcyclotetrasiloxane or 2,6-Diethoxy-2,4,6,8-tetramethylcyclotetrasiloxane

[0118] To 1 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial was added directly 0.25 mL of ethanol, followed by a catalytic amount of Ru3(CO) 12 of THF. The reaction mixture was allowed to stand for a length of 16 hours, then sampled and subjected to GC-MS to confirm the formation of the desired product. GC-MS showed the following peaks: m / z = 300 (M+), 285 (M-15), 269, 253, 239, 225, 209, 193, 179, 165, 149, 133, 119, 105, 89, 73, 59, 45.

[0119] Working Example 13 - Synthesis of 2,4-Di-n-propoxy-2,4,6,8-tetramethylcyclotetrasiloxane or 2,6-Di-n-propoxy-2,4,6,8-tetramethylcyclotetrasiloxane

[0120] To 1 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial was added directly 0.25 mL of 1-propanol, followed by a catalytic amount of Ru3(CO) 12mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial followed by a catalytic amount of a THF solution of Ru3(CO)12. The reaction mixture was allowed to stand for a length of 16 hours, then sampled and subjected to GC-MS to confirm the formation of the desired product. GC-MS showed the following peaks: m / z = 356 (M+), 341 (M-15), 327, 311, 297, 283, 269, 253, 239, 223, 209, 193, 179, 165, 149, 134, 119, 104, 89, 75, 59, 43.

[0121] Working Example 14 - Synthesis of 2,4-di-isopropoxy-2,4,6,8-tetramethylcyclotetrasiloxane or 2,6-di-isopropoxy-2,4,6,8-tetramethylcyclotetrasiloxane

[0122] To 1 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial was added 0.25 mL of 2-propanol directly followed by a catalytic amount of a THF solution of Ru3(CO) 12 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial followed by a catalytic amount of a THF solution of Ru3(CO)12. The reaction mixture was allowed to stand for a length of 16 hours, then sampled and subjected to GC-MS to confirm the formation of the desired product. GC-MS showed the following peaks: m / z = 356 (M+), 341 (M-15), 327, 311, 297, 283, 269, 253, 239, 223, 209, 193, 179, 165, 149, 134, 119, 104, 89, 75, 59, 43.

[0123] Working Example 15 - Synthesis of 2,4-di-n-butoxy-2,4,6,8-tetramethylcyclotetrasiloxane or 2,6-di-n-butoxy-2,4,6,8-tetramethylcyclotetrasiloxane

[0124] To 1 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial was added 0.25 mL of 1-butanol directly followed by a catalytic amount of a THF solution of Ru3(CO) 12 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial followed by a catalytic amount of a THF solution of Ru3(CO)12. The reaction mixture was allowed to stand for a length of 16 hours, then sampled and subjected to GC-MS to confirm the formation of the desired product. GC-MS showed the following peaks: m / z = 356 (M+), 341 (M-15), 327, 311, 297, 283, 269, 253, 239, 223, 209, 193, 179, 165, 149, 134, 119, 104, 89, 75, 59, 43.

[0125] Working Example 16 - Synthesis of 2,4-di-sec-butoxy-2,4,6,8-tetramethylcyclotetrasiloxane or 2,6-di-sec-butoxy-2,4,6,8-tetramethylcyclotetrasiloxane

[0126] To 1 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial was added 0.25 mL of 2-butanol directly followed by the addition of a catalytic amount of Ru3(CO) 12 The reaction mixture was allowed to stand for a length of 16 hours, then sampled and subjected to GC-MS to confirm the formation of the desired product. GC-MS showed the following peaks: m / z = 384 (M+), 369 (M-15), 355, 343, 325, 313, 299, 283, 269, 253, 239, 223, 209, 193, 179, 165, 149, 135, 119, 104, 89, 75, 57, 41.

[0127] Working Example 17 - Synthesis of 2,4-Di-t-butoxy-2,4,6,8-tetramethylcyclotetrasiloxane or 2,6-Di-t-butoxy-2,4,6,8-tetramethylcyclotetrasiloxane

[0128] To 1 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial was added 0.25 mL of t-butyl alcohol directly followed by the addition of a catalytic amount of Ru3(CO) 12 The reaction mixture was allowed to stand for a length of 16 hours, then sampled and subjected to GC-MS to confirm the formation of the desired product. GC-MS showed the following peaks: m / z = 384 (M+), 369 (M-15), 354, 343, 327, 313, 297, 281, 269, 253, 239, 223, 209, 193, 179, 165, 148, 135, 119, 103, 89, 75, 57, 41.

[0129] Working Example 18 - Synthesis of 2,4-Di-t-pentoxy-2,4,6,8-tetramethylcyclotetrasiloxane or 2,6-Di-t-pentoxy-2,4,6,8-tetramethylcyclotetrasiloxane

[0130] To 1 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial was added 0.25 mL of t-pentyl alcohol directly followed by the addition of a catalytic amount of Ru3(CO) 12 The reaction mixture was allowed to stand for a length of 16 hours, then sampled and subjected to GC-MS to confirm the formation of the desired product. GC-MS showed the following peaks: m / z = 412 (M+), 397 (M-15), 383, 367, 341, 327, 313, 297, 283, 269, 253, 239, 223, 209, 193, 179, 165, 148, 135, 119, 104, 89, 71, 57, 43

[0131] Working Example 19 - Synthesis of 2,4-dicyclopentyloxy-2,4,6,8- tetramethylcyclotetrasiloxane or 2,6-dicyclopentyloxy-2,4,6,8- tetramethylcyclotetrasiloxane

[0132] To 1 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial was added 0.25 mL of cyclohexanol directly followed by the addition of a catalytic amount of Ru3(CO) 12 The reaction mixture was allowed to stand for a length of 16 hours, after which it was sampled and subjected to GC-MS to confirm the formation of the desired product. The GC-MS showed the following peaks: m / z = 436 (M+), 421 (M-15), 407, 393, 379, 353, 339, 323, 309, 283, 269, 253, 239, 223, 209, 193, 179, 165, 147, 126, 111, 97, 83, 69, 55, 41.

[0133] Working Example 20 - Synthesis of 2,4-dicyclopentyloxy-2,4,6,8- tetramethylcyclotetrasiloxane or 2,6-dicyclopentyloxy-2,4,6,8- tetramethylcyclotetrasiloxane

[0134] To 1 mL of 2,4,6,8-tetramethylcyclotetrasiloxane in a 4 mL vial was added 0.25 mL of cyclohexanol directly followed by the addition of a catalytic amount of Ru3(CO) 12 The reaction mixture was allowed to stand for a length of 16 hours, after which it was sampled and subjected to GC-MS to confirm the formation of the desired product. The GC-MS showed the following peaks: m / z = 436 (M+), 421 (M-15), 407, 393, 379, 353, 339, 323, 309, 283, 269, 253, 239, 223, 209, 193, 179, 165, 147, 126, 111, 97, 83, 69, 55, 41.

[0135] Industrial Utility

[0136] In operation, the alkoxy-functionalized cyclotrisiloxanes described and depicted above can be used in a number of industrial applications, including but not limited to their use as insulating materials deposited in high aspect ratio gaps, trenches, vias, and other surface features between adjacent semiconductor devices. Accordingly, in a second aspect of the application disclosed herein, a method of depositing a silicon-containing film with the alkoxy-functionalized cyclotrisiloxanes described and depicted above is disclosed. In this method, a substrate comprising surface features can be placed in a deposition chamber of a CVD apparatus, such as a PECVD apparatus.

[0137] In certain embodiments of this aspect of the application, the surface features have a width of 100 μm or less, a width of 1 μm or less, or a width of 0.5 μm. In this or other embodiments, the aspect ratio (depth to width) of the surface features, if present, is 0.1 : 1 or greater, or 1 : 1 or greater, or 10: 1 or greater, or 20: 1 or greater, or 40: 1 or greater.

[0138] The substrate can be a single crystal silicon wafer, a silicon carbide wafer, an aluminum oxide (sapphire) wafer, a glass flake, a metal foil, an organic polymer film, or can be a three-dimensional article of polymer, glass, silicon, or metal. The substrate can be coated with various materials known in the art, including films of silicon oxide, silicon nitride, amorphous carbon, silicon oxycarbide, silicon oxynitride, silicon carbide, gallium arsenide, gallium nitride, etc. These coatings can completely coat the substrate, can be multiple layers of various materials, and can be partially etched to expose underlying layers of material. The surface can also have photoresist material on it that has been exposed in a pattern and developed to partially coat the substrate.

[0139] The temperature of the substrate can be controlled to be less than the walls of the deposition chamber. The substrate temperature is maintained at a temperature less than 100°C, preferably at a temperature less than 80°C, and most preferably at a temperature less than 60°C, and greater than -30°C. Preferred exemplary substrate temperatures of the present application are -30°C to 0°C, 0°C to 20°C, 10°C to 30°C, 20°C to 40°C, 30°C to 60°C, 40°C to 80°C, 50°C to 100°C.

[0140] In certain embodiments, the pressure of the deposition chamber is less than atmospheric pressure or 750 Torr (10 5 Pascals (Pa)) or less, or 100 Torr (13332 Pa) or less. In other embodiments, the pressure of the deposition chamber is maintained in a range from about 0.1 Torr (13 Pa) to about 10 Torr (1333 Pa). In preferred embodiments, the pressure of the deposition chamber is maintained in a range from about 2 Torr (266 Pa) to about 5 Torr (667 Pa).

[0141] In this method, two or more molecules of an alkoxyl-functionalized cyclotrisiloxane compound represented by the following Formula A, B, or C can be introduced into the deposition chamber:

[0142] A

[0143] B

[0144] C

[0145] In each of the compounds shown above, R 1 is an alkyl group having 1-10 carbon atoms. R 2may be H or an alkoxy group having 1 to 10 carbon atoms. Finally, if present, R 3 may be H or an alkoxy group having 1 to 10 carbon atoms.

[0146] In a preferred embodiment of the method, R 1 is an alkoxy group selected from the group consisting of methoxy, ethoxy, 1 -propoxy, isopropoxy, 1 -butoxy, t-butoxy, sec-butoxy, 1 -pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl- 1 -butoxy, 3-methyl- 1 -butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl- 1 -propoxy, 1 -hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl- 1 -pentoxy, 3-methyl- 1 -pentoxy, 4-methyl- 1 -pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl- 1 -butoxy, 2,3-dimethyl- 1 -butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl- 1 -butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof. In this embodiment, R 2 is H, and R 3 is also H.

[0147] In a further preferred embodiment of the method, R 1 is an alkoxy group selected from the group consisting of methoxy, ethoxy, 1 -propoxy, isopropoxy, 1 -butoxy, t-butoxy, sec-butoxy, 1 -pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl- 1 -butoxy, 3-methyl- 1 -butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl- 1 -propoxy, 1 -hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl- 1 -pentoxy, 3-methyl- 1 -pentoxy, 4-methyl- 1 -pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl- 1 -butoxy, 2,3-dimethyl- 1 -butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl- 1 -butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof. In this particular embodiment, R 2is an alkoxy selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, t-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl-1-pentoxy, 3-methyl-1-pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof. In this preferred embodiment, R 3 is H.

[0148] In another preferred embodiment of the method, R 1 is an alkoxy selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, t-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl-1-pentoxy, 3-methyl-1-pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof. In this preferred embodiment, R 2 is H, and R 3is an alkoxy selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, t-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl-1-pentoxy, 3-methyl-1-pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof.

[0149] In a final preferred embodiment of the process, R 1 is an alkoxy selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, t-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl-1-pentoxy, 3-methyl-1-pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof. In this final embodiment, R 2is an alkoxy selected from the group consisting of methoxy, ethoxy, 1 -propoxy, isopropoxy, 1 -butoxy, t-butoxy, sec-butoxy, 1 -pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl- 1 -butoxy, 3-methyl- 1 -butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl- 1 -propoxy, 1 -hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl- 1 -pentoxy, 3-methyl- 1 -pentoxy, 4-methyl- 1 -pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl- 1 -butoxy, 2,3-dimethyl- 1 -butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl- 1 -butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof. Finally, in this embodiment, R 3 is an alkoxy selected from the group consisting of methoxy, ethoxy, 1 -propoxy, isopropoxy, 1 -butoxy, t-butoxy, sec-butoxy, 1 -pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl- 1 -butoxy, 3-methyl- 1 -butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl- 1 -propoxy, 1 -hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl- 1 -pentoxy, 3-methyl- 1 -pentoxy, 4-methyl- 1 -pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl- 1 -butoxy, 2,3-dimethyl- 1 -butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl- 1 -butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof.

[0150] Next, in a more preferred embodiment of the method, the alkoxy-functionalized cyclosiloxane compound is generally represented by Formula A, and the alkoxy-functionalized cyclosiloxane compound is selected from the group consisting of:

[0151]

[0152] In another more preferred embodiment of the method, the alkoxy-functionalized cyclosiloxane compound is generally represented by Formula B, and the alkoxy-functionalized cyclosiloxane compound is selected from the group consisting of:

[0153]

[0154]

[0155] Finally, in another more preferred embodiment of the method, the alkoxyl-functionalized cyclosiloxane compound is generally represented by Formula C, and the alkoxyl-functionalized cyclosiloxane compound is selected from the group consisting of:

[0156]

[0157]

[0158]

[0159] Applicants also contemplate that in some cases of the method, a mixture of two or more alkoxyl-functionalized cyclosiloxane molecules represented by Formula A, B, or C can be preferred over only one alkoxyl-functionalized cyclosiloxane compound represented by Formula A, B, or C. The mixture of two or more alkoxyl-functionalized cyclosiloxane molecules can, for example, comprise a mixture of molecules of Formula A and Formula B. In another case, the mixture can comprise molecules of Formula A and Formula C. In yet another case, the mixture can comprise two or more molecules of Formula B and Formula C. Finally, the two or more molecules can comprise compounds of Formula A, Formula B, and Formula C.

[0160] The molecules of the two or more alkoxyl-functionalized cyclosiloxane compounds represented by Formula A, B, or C can be exposed to a plasma in the deposition chamber. This exposure to the plasma can induce a reaction between the two or more molecules and thus produce a flowable liquid or oligomer prepared from the two or more molecules of alkoxyl-functionalized cyclosiloxane compounds represented by Formula A, B, or C. This flowable liquid or oligomer can then at least partially fill the surface features of the substrate and thus produce a silicon-containing film.

[0161] In this aspect of the application, the plasma of the method can be a pulsed plasma, a spiral wave plasma, a high-density plasma, an inductively coupled plasma, or a remote plasma, and combinations thereof. In certain embodiments, a secondary RF frequency source can be used to vary the plasma characteristics at the surface of the substrate. The plasma can include a direct plasma generation process, in which the plasma is generated directly in the deposition chamber (i.e., an in-situ plasma). Alternatively, the method can include a plasma that is generated outside of the deposition chamber and supplied into the deposition chamber (i.e., a remote plasma). The plasma can also include an in-situ plasma and a remote plasma that are present simultaneously or sequentially during the method of depositing a silicon-containing film described herein.

[0162] In one embodiment of the method, the introducing step further comprises introducing an inert gas into the deposition chamber. In this case, the inert gas is selected from the group consisting of helium, argon, xenon, and mixtures thereof, and the plasma in the exposing step is an in-situ plasma. In this alternative, atoms of the inert gas are not incorporated into the molecule- made flowable liquid or oligomer from the two or more alkoxy-functional cyclosiloxane compounds represented by Formula A, B, or C after exposure to the in-situ plasma in the deposition chamber, thereby producing a silicon-containing film comprising silicon and carbon.

[0163] In a further embodiment of the method, the introducing step further comprises introducing a nitrogen source into the deposition chamber, wherein the nitrogen source is selected from the group consisting of N2, ammonia, NF3, organic amines, and mixtures thereof. The plasma in the exposing step of this further embodiment of the method is an in-situ plasma, and nitrogen atoms of the nitrogen source are incorporated into the molecule-made flowable liquid or oligomer from the two or more alkoxy-functional cyclosiloxane compounds represented by Formula A, B, or C after exposure to the in-situ plasma in the deposition chamber. From this, the method can produce a silicon-containing film comprising silicon, carbon, and nitrogen.

[0164] In another alternative of the method, the introducing step further comprises introducing an oxygen source selected from the group consisting of water, oxygen, ozone, nitric oxide, nitrous oxide, carbon monoxide, carbon dioxide, and combinations thereof. The plasma in the exposing step is an in-situ plasma, and oxygen atoms of the oxygen source are incorporated into the molecule-made flowable liquid or oligomer from the two or more alkoxy-functional cyclosiloxane compounds represented by Formula A, B, or C after exposure to the in-situ plasma in the deposition chamber. The silicon-containing film produced in this case can comprise silicon, carbon, and oxygen.

[0165] In another alternative of the method disclosed herein, the plasma in the exposing step is a remote plasma comprising an inert gas. The inert gas can be selected from the group consisting of helium, argon, xenon, and mixtures thereof, and atoms of the inert gas are not incorporated into the molecule-made flowable liquid or oligomer from the two or more alkoxy-functional cyclosiloxane compounds represented by Formula A, B, or C after exposure to the remote plasma in the deposition chamber. In this case, the silicon-containing film can comprise silicon and carbon.

[0166] In another embodiment of the method disclosed herein, the plasma in the exposing step is a remote plasma comprising a nitrogen source, and the nitrogen source can be selected from the group consisting of N2, ammonia, NF3, organic amines, and mixtures thereof. In this case, nitrogen atoms of the nitrogen source are incorporated into the molecule-made flowable liquid or oligomer from the two or more alkoxy-functional cyclosiloxane compounds represented by Formula A, B, or C after exposure to the remote plasma in the deposition chamber. The silicon-containing film produced in this case can comprise silicon, carbon, and nitrogen.

[0167] In another alternative embodiment of the methods disclosed herein, the plasma in the exposing step is a remote plasma comprising an oxygen source. The oxygen source can be selected from the group consisting of water, oxygen, ozone, nitric oxide, nitrous oxide, carbon monoxide, carbon dioxide, and combinations thereof. In this particular alternative embodiment, the oxygen atoms of the oxygen source are incorporated into the flowable liquid or oligomer produced from the molecules of the two or more alkoxyl-functional cyclotrisiloxane compounds represented by Formula A, B, or C upon exposure to the remote plasma in the deposition chamber. Thus, the silicon-containing film can comprise silicon, carbon, and oxygen.

[0168] The method can additionally comprise a pre-treatment step prior to placing the substrate in the deposition chamber. The pre-treatment step can be selected from the group consisting of a plasma treatment, a thermal treatment, a chemical treatment, exposure to ultraviolet light, exposure to an electron beam, and combinations thereof. These pre-deposition treatments can be performed under an atmosphere selected from the group consisting of inert, oxidizing, and / or reducing.

[0169] The method of depositing a silicon-containing film can further comprise a post-treatment in a post-treatment step. In this step, the post-treatment can be selected from the group consisting of ultraviolet curing of the silicon-containing film, plasma annealing of the silicon-containing film, infrared treatment of the silicon-containing film, and combinations thereof, thereby densifying the silicon-containing film. The post-treatment step can further comprise post-treatment non-oxidative thermal annealing or oxidative thermal annealing, thereby densifying the silicon-containing film, either as an alternative or in combination with the post-treatment methods just listed above.

[0170] The alkoxyl-functional compounds disclosed herein can be used to provide rapid and uniform deposition of a flowable silicon-containing film. The compounds described herein can be used and deposited onto a substrate with another reactant containing water and optionally a co-solvent, a surfactant, and other additives. Dispensing or delivery of the compounds to the deposition chamber can be achieved by direct liquid injection, spraying, and the like.

[0171] Subsequently, the unreacted volatile species, including solvents and unreacted water, can be removed using an inert gas, vacuum, heat, or an external energy source (light, heat, plasma, electron beam, etc.) to promote coalescence of the film. The compounds of the present invention can be delivered to the substrate contained in the deposition chamber preferably in the gas phase, droplets, mist, fog, aerosol, sublimated solid, or combinations thereof, with water and optionally a co-solvent and other additives also added as process fluids such as gases, vapors, aerosols, mists, or combinations thereof. Preferably, the oligomeric or polymeric compounds of the present invention coalesce into a coalesced film on the surface of the substrate, which can advantageously be maintained at a temperature lower than the temperature of the chamber walls. The unreacted precursor compounds, water, and optionally co-solvents and additives can be removed by gas purging, vacuum, heating, addition of external radiation (light, plasma, electron beam, etc.) until a stable solid silicon-containing film is obtained.

[0172] In any of the above embodiments, or in an alternative embodiment, the flowable liquid or oligomer can be post-treated at one or more temperatures ranging from about 100 °C to about 1000 °C to densify at least a portion of the material. The thermal annealing treatment can be performed in an inert environment, under vacuum (<760 Torr), or in an oxygen environment.

[0173] Thus, based on the foregoing, in a third aspect of the application, a film on a substrate is disclosed. The film can comprise a flowable liquid or oligomer comprising two or more oligomeric or polymeric molecules of an alkoxy-functionalized cyclotrisiloxane compound represented by Formula A, B, or C,

[0174] A

[0175] B

[0176] C

[0177] In each of the above compounds, R 1 is H or an alkoxy group having 1 to 10 carbon atoms. R 2 may be H or an alkoxy group having 1 to 10 carbon atoms. Finally, if present, R 3 may be H or an alkoxy group having 1 to 10 carbon atoms.

[0178] In one embodiment of the film, the two or more oligomeric or polymeric molecules of the alkoxy-functionalized cyclotrisiloxane compound have R 1 may be an alkoxy group selected from the group consisting of methoxy, ethoxy, 1 -propoxy, isopropoxy, 1 -butoxy, t-butoxy, sec-butoxy, 1 -pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl- 1 -butoxy, 3-methyl- 1 -butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl- 1 -propoxy, 1 -hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl- 1 -pentoxy, 3-methyl- 1 -pentoxy, 4-methyl- 1 -pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl- 1 -butoxy, 2,3-dimethyl- 1 -butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl- 1 -butoxy, cyclopentoxy, cyclohexoxy, and combinations thereof. In this embodiment, R 2 is H, and R 3 is also H.

[0179] In another embodiment of the film, the two or more oligomeric or polymeric molecules of the alkoxy-functionalized cyclotrisiloxane compound have R1 may be an alkoxy selected from the group consisting of methoxy, ethoxy, 1 -propoxy, isopropoxy, 1 -butoxy, t-butoxy, sec-butoxy, 1 -pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl- 1 -butoxy, 3-methyl- 1 -butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl- 1 -propoxy, 1 -hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl- 1 -pentoxy, 3-methyl- 1 -pentoxy, 4-methyl- 1 -pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl- 1 -butoxy, 2,3-dimethyl- 1 -butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl- 1 -butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof. In this particular embodiment, R 2 may be an alkoxy selected from the group consisting of methoxy, ethoxy, 1 -propoxy, isopropoxy, 1 -butoxy, t-butoxy, sec-butoxy, 1 -pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl- 1 -butoxy, 3-methyl- 1 -butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl- 1 -propoxy, 1 -hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl- 1 -pentoxy, 3-methyl- 1 -pentoxy, 4-methyl- 1 -pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl- 1 -butoxy, 2,3-dimethyl- 1 -butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl- 1 -butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof. In this embodiment, R 3 is H.

[0180] In another embodiment of the film, R 1may be an alkoxy selected from the group consisting of methoxy, ethoxy, 1 -propoxy, isopropoxy, 1 -butoxy, t-butoxy, sec-butoxy, 1 -pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl- 1 -butoxy, 3-methyl- 1 -butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl- 1 -propoxy, 1 -hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl- 1 -pentoxy, 3-methyl- 1 -pentoxy, 4-methyl- 1 -pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl- 1 -butoxy, 2,3-dimethyl- 1 -butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl- 1 -butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof. In this preferred embodiment, R 2 is H, and R 3 may be an alkoxy selected from the group consisting of methoxy, ethoxy, 1 -propoxy, isopropoxy, 1 -butoxy, t-butoxy, sec-butoxy, 1 -pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl- 1 -butoxy, 3-methyl- 1 -butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl- 1 -propoxy, 1 -hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl- 1 -pentoxy, 3-methyl- 1 -pentoxy, 4-methyl- 1 -pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl- 1 -butoxy, 2,3-dimethyl- 1 -butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl- 1 -butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof.

[0181] In another embodiment of the film, the R 1alkylthio selected from the group consisting of methylthio, ethylthio, 1 -propylthio, isopropylthio, 1 -butylthio, tert-butylthio, sec-butylthio, 1 -pentylthio, 2-pentylthio, 3-pentylthio, 2-methyl-1 -butylthio, 3-methyl-1 -butylthio, 2-methyl-2-butylthio, 2-methyl-3-butylthio, 2,2-dimethyl-1 -propylthio, 1 -hexylthio, 2-hexylthio, 3-hexylthio, 2-methyl-1 -pentylthio, 3-methyl-1 -pentylthio, 4-methyl-1 -pentylthio, 2-methyl-2-pentylthio, 3-methyl-2-pentylthio, 4-methyl-2-pentylthio, 2-methyl-3-pentylthio, 3-methyl-3-pentylthio, 2,2-dimethyl-1 -butylthio, 2,3-dimethyl-1 -butylthio, 2,3-dimethyl-2-butylthio, 3,3-dimethyl-2-butylthio, 2-ethyl-1 -butylthio, cyclopentylthio, cyclohexylthio, and combinations thereof. In this last preferred embodiment, R 2 is an alkoxy selected from the group consisting of methoxy, ethoxy, 1 -propoxy, isopropoxy, 1 -butoxy, tert-butoxy, sec-butoxy, 1 -pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1 -butoxy, 3-methyl-1 -butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1 -propoxy, 1 -hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl-1 -pentoxy, 3-methyl-1 -pentoxy, 4-methyl-1 -pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1 -butoxy, 2,3-dimethyl-1 -butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1 -butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof. Finally, in this embodiment, R 3 is an alkoxy selected from the group consisting of methoxy, ethoxy, 1 -propoxy, isopropoxy, 1 -butoxy, tert-butoxy, sec-butoxy, 1 -pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1 -butoxy, 3-methyl-1 -butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1 -propoxy, 1 -hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl-1 -pentoxy, 3-methyl-1 -pentoxy, 4-methyl-1 -pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1 -butoxy, 2,3-dimethyl-1 -butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1 -butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof.

[0182] Next, in a more preferred embodiment of the film, the two or more oligomeric or polymeric alkoxyl-functionalized cyclosiloxane compound molecules are generally represented by Formula A, and are selected from:

[0183]

[0184]

[0185] In another more preferred embodiment of the film, the two or more oligomeric or polymeric alkoxyl-functionalized cyclosiloxane compound molecules are generally represented by Formula B, and are selected from:

[0186]

[0187]

[0188]

[0189] In a further more preferred embodiment of the film, the two or more oligomeric or polymeric alkoxyl-functionalized cyclosiloxane compound molecules are generally represented by Formula C, and are selected from:

[0190]

[0191]

[0192] The alkoxyl-functionalized cyclosiloxane compounds represented by Formula A, B, or C disclosed herein can be stored, transported, and delivered in glass, plastic, or metal containers or other suitable containers known in the art.

[0193] Plastic or glass lined metal vessels or containers can also be used. Preferably, the material is stored and delivered from a gas-tight, high purity, stainless steel or nickel alloy container having an inert gas in the headspace. Most preferably, the material is stored and delivered from a sealed, high purity, stainless steel or nickel alloy container equipped with a dip tube and an outlet port in communication with the vapor space of the container; thereby allowing the product to be delivered as a liquid from the dip tube or as a vapor from the outlet port connection in communication with the vapor. In the latter case, the dip tube can optionally be used to introduce a carrier gas into the container to facilitate vaporization of the mixture. In this embodiment, the dip tube and vapor outlet port connection are equipped with high integrity, packing-free valves. While it is preferred to deliver the liquid to avoid partitioning of the components of the formulation described herein, it should be noted that the formulation of the present application is sufficiently tightly matched to the vapor pressures of the components to enable the formulation to be delivered as a vapor mixture. The stainless steel can preferably be selected from the group consisting of UNS alloy designations S31600, S31603, S30400, S30403, S31700, S31703, S31500, S31803, S32750 and S31254. The nickel alloy can preferably be selected from the group consisting of UNS alloy designations N06625, N10665, N06022, N10276 and N06007. Most preferably, the container is made of alloy S31603 or N06022, which is either uncoated, internally electropolished or internally coated with a fluoropolymer.

[0194] Deposition of alkoxyl functionalized cyclotrisiloxane films

[0195] General experimental materials and equipment for film deposition

[0196] FCVD films were deposited onto moderately resistive (8-12 ohm cm) single crystal silicon wafer substrates and Si patterned wafers. For the patterned wafers, the preferred pattern width was 20-100 nm with an aspect ratio of 5: 1 to 20: 1. Deposition was performed on an Applied Materials Precision 5000 system using a dual showerhead gasification head in a modified FCVD chamber. The chamber was equipped with direct liquid injection (DLI) delivery capability. The precursors were liquids and the delivery temperature was dependent on the boiling point of the precursor. To deposit an initially flowable silicon oxide film, typical liquid precursor flow rates ranged from about 100 to about 5000 mg / min, preferably 1000 to 2000 mg / min; chamber pressures ranged from about 0.75 to 12 Torr, preferably 2 to 5 Torr. Specifically, remote power of 0-3000 W was supplied by an MKS microwave generator at a frequency of 2.455 GHz, operating at 2-8 Torr. To densify the as-deposited flowable film, the film was thermally annealed and / or UV cured in vacuum or in an oxygen ambient at 100-1000 °C, preferably 300-400 °C, using a modified PECVD chamber. Thickness and refractive index (RI) at 632 nm were measured by a SCI reflectometer or a Woollam ellipsometer. Typical film thicknesses ranged from about 10 to about 2000 nm. Bonded specie hydrogen content (Si-H and C-H) of the silicon-based thin films were measured and analyzed by a Nicolet transmission Fourier transform infrared spectroscopy (FTIR) instrument. X-ray photoelectron spectroscopy (XPS) analysis was performed to determine the elemental composition of the films. Mercury probes were adapted for electrical property measurements, including dielectric constant, leakage current, and breakdown field. Flowability and gap fill effects on Al patterned wafers were observed by cross-sectional scanning electron microscopy (SEM) using a Hitachi S-4800 system at a resolution of 2.0 nm.

[0197] Working Example 21 - Deposition of 2-Ethoxy-2,4,6,8-tetramethylcyclotetrasiloxane with non-oxidative thermal anneal and UV cure

[0198] 2-Ethoxy-2,4,6,8-tetramethylcyclotetrasiloxane (2-ethoxy-TMCTS) was used for flowable SiOC film deposition using a remote plasma source (RPS). The 2-ethoxy-TMCTS liquid flow was 1500 mg / min, ammonia flow was 1000 seem, and chamber pressure was 4.5 Torr. Substrate temperature was 60 °C and microwave power was 3000 W. The as-deposited film was thermally annealed at 400 °C for 5 minutes in an inert ambient followed by UV cure at 400 °C for 5 minutes. The thickness and refractive index of the as-deposited film was 209.6 nm and 1.444; after inert thermal anneal, the thickness and refractive index was 206.1 nm and 1.433, indicating some loss of volatile oligomers at elevated temperature.

[0199] After inert thermal annealing, the film had a dielectric constant of 3.308, which was attributed to some water uptake from dangling bonds in the film. After UV curing, the film had about 16% shrinkage relative to the thermal annealed film, and it had a refractive index of 1.414, which indicated modification of the film by UV curing and an increase in film porosity. The dielectric constant of the UV cured film was 2.931. The elemental composition of the film for this process was 22.6% C, 5.0% N, 39.8% O, 32.7% Si.

[0200] Working Example 22 - Deposition of 2-Ethoxy-2,4,6,8-tetramethylcyclotetrasiloxane with oxidative thermal annealing and UV curing

[0201] This example involved a film that was deposited as deposited, thermal annealed in an oxygen environment, and then UV cured. Cross-sectional SEM showed good gap fill was achieved on a patterned wafer. Figure 1 and Figure 2 Good gap fill was shown. The film was thermal annealed, and UV cured. Cross-sectional SEM showed good gap fill was also achieved for Working Example 22. There was no evidence of voids in the film after UV curing. This was shown by Figure 2 .

[0202] For this process, the percent thickness shrinkage after UV curing was about 12%, and the refractive index was 1.394. The dielectric constant of the film was 2.791. The elemental composition after oxygen thermal annealing and subsequent UV curing was 16.4% C, 1.4% N, 48.9% O, 33.3% Si.

[0203] Working Example 23 - Deposition of 2-Isopropoxy-2,4,6,8-tetramethylcyclotetrasiloxane with non-oxidative thermal annealing and UV curing

[0204] An FCVD film was deposited with 2-isopropoxy-2,4,6,8-tetramethylcyclotetrasiloxane (2-isopropoxy-TMCTS) and according to the deposition process reported in Example 1. The 2-isopropoxy-TMCTS liquid flow was 1500 mg / min, the ammonia flow was 1000 seem, and the chamber pressure was 4.5 Torr. The substrate temperature was 60 °C, and the microwave power was 3000 W. The as-deposited film was thermal annealed in an inert environment at 400 °C for 5 minutes, and then UV cured at 400 °C for 5 minutes.

[0205] The as-deposited film had a thickness and refractive index of 281.4 nm and 1.386; after inert thermal annealing and UV curing, the thickness and refractive index were 188.7 nm and 1.406. The increase in the film's refractive index after UV curing indicates densification. The film had a shrinkage of about 32% after UV curing. The dielectric constant of the film after UV curing was 3.075, and the elemental composition of the film was 23.4% C, 4.9% N, 37.9% O, 33.8% Si.

[0206] Cross-section SEM indicated good gap fill was achieved on the patterned wafer. Figure 4 FIG. 2 depicts an as-deposited 2-isopropoxy-TMCTS film, and Figure 5 FIG. 3 depicts the film after thermal and UV curing. Figure 5 There was no apparent voiding evident in the UV curing process.

[0207] Working Example 24 - Deposition of 2-isopropoxy-2,4,6,8-tetramethylcyclotetrasiloxane with non-oxidizing thermal annealing and UV curing

[0208] Another embodiment included an as-deposited film that was thermal annealed in an oxygen environment at 400 °C for 5 minutes, followed by UV curing at 400 °C for 5 minutes. The percent thickness shrinkage after UV curing of this process was about 31%, and the refractive index was 1.371. The dielectric constant of this film was 2.921. The elemental composition after oxygen thermal annealing and subsequent UV curing was 19.8% C, 1.9% N, 44.5% O, 33.8% Si.

[0209] Working Example 25 - Electrical breakdown measurements of films prepared from 2-ethoxy-2,4,6,8-tetramethylcyclotetrasiloxane and 2-isopropoxy-2,4,6,8-tetramethylcyclotetrasiloxane

[0210] Flowable films were deposited with 2-isopropoxy-TMCTS and 2-ethoxy-TMCTS, and after thermal annealing and UV curing of these films, electrical breakdown measurements were made. The electrical breakdown results are shown in Figure 6 .

[0211] 2-isopropoxy-TMCTS films were thermal annealed in an oxygen environment at 400 °C and UV cured at 300 °C, and 2-ethoxy-TMCTS films were thermal annealed in an oxygen environment at 400 °C and UV cured at 300 °C.

[0212] Figure 6 The 2-isopropoxy-TMCTS and 2-ethoxy-TMCTS films in FIG. 4 had similar breakdown points at about 4.9 MV / cm, but the 2-isopropoxy-TMCTS had a slightly higher current density, which indicates a slightly higher leakage current for the 2-isopropoxy-TMCTS compared to the 2-ethoxy-TMCTS.

[0213] The above description is merely representative, and thus modifications can be made to the embodiments described herein without departing from the scope of the present disclosure. Accordingly, these modifications are intended to fall within the scope of the present disclosure and are intended to be covered by the claims that follow.

Claims

1. A composition for depositing a silicon-containing film by a flowable chemical vapor deposition process, comprising: an alkoxy-functionalized cyclosiloxane compound represented by formula A, B or C, where R 1 is an alkoxy group having 1 to 10 carbon atoms; where R 2 is H, or an alkoxy group having 1 to 10 carbon atoms; and where R 3 is H, or an alkoxy group having 1 to 10 carbon atoms.

2. The composition according to claim 1, wherein R 1 is an alkoxy group selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, tert-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexyloxy, 2-hexyloxy, 3-hexyloxy, 2-methyl-1-pentoxy, 3-methyl- 1-pentyloxy, 4-methyl-1-pentyloxy, 2-methyl-2-pentyloxy, 3-methyl-2-pentyloxy, 4-methyl-2-pentyloxy, 2-methyl-3-pentyloxy, 3-methyl-3-pentyloxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentyloxy, cyclohexyloxy, and combinations thereof, wherein R 2 is H, and R 3 It’s H.

3. The composition according to claim 1, wherein R 1 is an alkoxy group selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, tert-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexyloxy, 2-hexyloxy, 3-hexyloxy, 2-methyl-1-pentoxy, 3-methyl- 1-pentyloxy, 4-methyl-1-pentyloxy, 2-methyl-2-pentyloxy, 3-methyl-2-pentyloxy, 4-methyl-2-pentyloxy, 2-methyl-3-pentyloxy, 3-methyl-3-pentyloxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentyloxy, cyclohexyloxy, and combinations thereof, wherein R 2 is an alkoxy group selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, tert-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexyloxy, 2-hexyloxy, 3-hexyloxy, 2-methyl-1-pentoxy, 3-methyl-1 -pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof, and wherein R 3 It’s H.

4. The composition according to claim 1, wherein R 1 is an alkoxy group selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, tert-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexyloxy, 2-hexyloxy, 3-hexyloxy, 2-methyl-1-pentoxy, 3-methyl- 1-pentyloxy, 4-methyl-1-pentyloxy, 2-methyl-2-pentyloxy, 3-methyl-2-pentyloxy, 4-methyl-2-pentyloxy, 2-methyl-3-pentyloxy, 3-methyl-3-pentyloxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentyloxy, cyclohexyloxy, and combinations thereof, wherein R 2 is H, and R 3 is an alkoxy group selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, tert-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexyloxy, 2-hexyloxy, 3-hexyloxy, 2-methyl-1-pentoxy, 3-methyl -1-pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentyloxy, cyclohexyloxy, and combinations thereof.

5. The composition according to claim 1, wherein R 1 is an alkoxy group selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, tert-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexyloxy, 2-hexyloxy, 3-hexyloxy, 2-methyl-1-pentoxy, 3-methyl- 1-pentyloxy, 4-methyl-1-pentyloxy, 2-methyl-2-pentyloxy, 3-methyl-2-pentyloxy, 4-methyl-2-pentyloxy, 2-methyl-3-pentyloxy, 3-methyl-3-pentyloxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentyloxy, cyclohexyloxy, and combinations thereof, wherein R 2 is an alkoxy group selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, tert-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexyloxy, 2-hexyloxy, 3-hexyloxy, 2-methyl-1-pentoxy, 3-methyl-1 -pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentoxy, cyclohexyloxy, and combinations thereof, and wherein R 3 is an alkoxy group selected from the group consisting of methoxy, ethoxy, 1-propoxy, isopropoxy, 1-butoxy, tert-butoxy, sec-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2-methyl-1-butoxy, 3-methyl-1-butoxy, 2-methyl-2-butoxy, 2-methyl-3-butoxy, 2,2-dimethyl-1-propoxy, 1-hexyloxy, 2-hexyloxy, 3-hexyloxy, 2-methyl-1-pentoxy, 3-methyl -1-pentoxy, 4-methyl-1-pentoxy, 2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl-1-butoxy, 2,3-dimethyl-1-butoxy, 2,3-dimethyl-2-butoxy, 3,3-dimethyl-2-butoxy, 2-ethyl-1-butoxy, cyclopentyloxy, cyclohexyloxy, and combinations thereof.

6. The composition of claim 1 , wherein the alkoxy-functionalized cyclosiloxane compound is selected from the group consisting of:

7. The composition of claim 1 , wherein the alkoxy-functionalized cyclosiloxane compound is selected from the group consisting of:

8. The composition of claim 1 , wherein the alkoxy-functionalized cyclosiloxane compound is selected from the group consisting of:

9. The composition of claim 1 comprising a mixture of compounds of Formula A and Formula B.

10. The composition of claim 1 comprising a mixture of compounds of Formula A and Formula C.

11. The composition of claim 1 comprising a mixture of compounds of Formula B and Formula C.

12. The composition of claim 1 comprising a mixture of compounds of Formula A, Formula B, and Formula C.

13. A method of depositing a silicon-containing film, comprising: placing a substrate comprising surface features in a deposition chamber; introducing into the deposition chamber two or more molecules of an alkoxy-functionalized cyclosiloxane compound represented by formula A, B, or C, where R 1 is an alkoxy group having 1 to 10 carbon atoms, where R 2 is H, or an alkoxy group having 1 to 10 carbon atoms, and where R 3 is H, or an alkoxy group having 1 to 10 carbon atoms; exposing two or more molecules of the alkoxy-functionalized cyclosiloxane compound represented by Formula A, B, or C to plasma in the deposition chamber, thereby inducing a reaction between the two or more molecules and thereby producing a flowable liquid or oligomer prepared from the two or more molecules of the alkoxy-functionalized cyclosiloxane compound represented by Formula A, B, or C; The flowable liquid or oligomer is allowed to at least partially fill the surface features and thereby create the silicon-containing film.

14. The method of depositing a silicon-containing film according to claim 13, wherein the introducing step further comprises introducing an inert gas into the deposition chamber, wherein the inert gas is selected from the group consisting of helium, argon, xenon, and mixtures thereof, wherein the plasma in the exposing step is an in-situ plasma, and wherein atoms of the inert gas are not incorporated into the flowable liquid or oligomer prepared from molecules of two or more of the alkoxy-functionalized cyclosiloxane compounds represented by Formula A, B, or C by exposure to the in-situ plasma in the deposition chamber, thereby producing a silicon-containing film comprising silicon and carbon.

15. The method of depositing a silicon-containing film according to claim 13, wherein the introducing step further comprises introducing a nitrogen source into the deposition chamber, wherein the nitrogen source is selected from the group consisting of N2, ammonia, NF3, organic amines, and mixtures thereof, wherein the plasma in the exposing step is an in-situ plasma, and wherein nitrogen atoms of the nitrogen source are incorporated into the flowable liquid or oligomer prepared from molecules of two or more of the alkoxy-functionalized cyclosiloxane compounds represented by Formula A, B, or C by exposure to the in-situ plasma in the deposition chamber, thereby producing a silicon-containing film comprising silicon, carbon, and nitrogen.

16. The method of depositing a silicon-containing film according to claim 13, wherein the introducing step further comprises introducing an oxygen source selected from the group consisting of water, oxygen, ozone, nitric oxide, nitrous oxide, carbon monoxide, carbon dioxide, and combinations thereof, wherein the plasma in the exposing step is an in-situ plasma, and wherein oxygen atoms of the oxygen source are incorporated into the flowable liquid or oligomer prepared from molecules of two or more of the alkoxy-functionalized cyclosiloxane compounds represented by Formula A, B, or C by exposure to the in-situ plasma in the deposition chamber, thereby producing a silicon-containing film comprising silicon, carbon, and oxygen.

17. The method of depositing a silicon-containing film according to claim 13, wherein the plasma in the exposing step is a remote plasma comprising an inert gas, wherein the inert gas is selected from the group consisting of helium, argon, xenon, and mixtures thereof, and wherein atoms of the inert gas are not incorporated into the flowable liquid or oligomer prepared from molecules of two or more of the alkoxy-functionalized cyclosiloxane compounds represented by Formula A, B, or C after exposure to the remote plasma in the deposition chamber, thereby producing a silicon-containing film comprising silicon and carbon.

18. The method of depositing a silicon-containing film according to claim 13, wherein the plasma in the exposing step is a remote plasma comprising a nitrogen source, wherein the nitrogen source is selected from the group consisting of N2, ammonia, NF3, organic amines, and mixtures thereof, and wherein nitrogen atoms of the nitrogen source are incorporated into the flowable liquid or oligomer prepared from molecules of two or more of the alkoxy-functionalized cyclosiloxane compounds represented by Formula A, B, or C after exposure to the remote plasma in the deposition chamber, thereby producing a silicon-containing film comprising silicon, carbon, and nitrogen.

19. The method of depositing a silicon-containing film according to claim 13, wherein the plasma in the exposing step is a remote plasma comprising an oxygen source, wherein the oxygen source is selected from the group consisting of water, oxygen, ozone, nitric oxide, nitrous oxide, carbon monoxide, carbon dioxide, and combinations thereof, and wherein oxygen atoms from the oxygen source are incorporated into the flowable liquid or oligomer prepared from molecules of two or more of the alkoxy-functionalized cyclosiloxane compounds represented by Formula A, B, or C after exposure to the remote plasma in the deposition chamber, thereby producing a silicon-containing film comprising silicon, carbon, and oxygen.

20. The method of depositing a silicon-containing film according to claim 13, wherein the substrate is pretreated in a pretreatment step before being placed in the deposition chamber, and wherein the pretreatment step is selected from the group consisting of plasma treatment, thermal treatment, chemical treatment, exposure to ultraviolet light, exposure to an electron beam, and combinations thereof.

21. The method for depositing a silicon-containing film according to claim 13, further comprising a post-treatment in a post-treatment step, wherein the post-treatment is selected from the group consisting of: ultraviolet curing of the silicon-containing film, plasma annealing of the silicon-containing film, infrared treatment of the silicon-containing film, thermal annealing of the silicon-containing film in a non-oxidizing environment, thermal annealing of the silicon-containing film in an oxidizing environment, and combinations thereof, thereby densifying the silicon-containing film.

22. A film on a substrate comprising: A flowable liquid or oligomer comprising oligomeric or polymeric molecules of two or more alkoxy-functionalized cyclosiloxane compounds represented by formula A, B or C, where R 1 is an alkoxy group having 1 to 10 carbon atoms; where R 2 is H, or an alkoxy group having 1 to 10 carbon atoms; and where R 3 is H, or an alkoxy group having 1 to 10 carbon atoms.

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