Composition containing organosilane compounds, methods of manufacturing thin films and thin film-coated substrates, transfer method, thin film-coated substrate, and article

Abstract

A composition containing a specific silane compound may avoid blockage in pipes due to deposits during industrial processes. The composition includes a silane compound having formula (I). A content of the silane compound, as calculated from the area percentage in gas chromatography, is 99.0% or more, and the composition contains additional specific silane compounds at specific concentrations. In formula (I), R1 to R4 represent the same or different hydrocarbon groups having 1 to 10 carbon atoms, a and b represent the same or different integers of 0 to 3, a + b is an integer of 5 or less, and R5 represents a hydrocarbon group with 1 to 6 carbon atoms.

Description

Attorney Docket No. 688243.0168 / 149WO TITLE OF THE INVENTION

[0001] Composition Containing Organosilane Compounds, Methods of Manufacturing Thin Films and Thin Film-Coated Substrates, Transfer Method, Thin Film-Coated Substrate, and Article CROSS-REFERENCE TO RELATED APPLICATION

[0002] This application claims priority to U.S. Provisional Application No. 63 / 779,584, filed March 28, 2025 and U.S. Provisional Application No. 63 / 872,630, filed on August 29, 2025, the disclosures of which are herein incorporated by reference in their entireties.TECHNICAL FIELD

[0003] Aspects of the disclosure relate to a composition containing organosilane compounds. This disclosure also relates to a composition containing specific proportions of organosilane compounds having specific structures for use in applications such as semiconductor materials. This disclosure also relates to a method of manufacturing thin films using the composition containing the organosilane compounds. Further aspects of the disclosure relate to a method of manufacturing thin film-coated substrates and to thin film-coated substrates formed from the composition containing the organosilane compounds. This disclosure also relates to a method of transferring the composition containing the organosilane compounds and to an article in which the composition containing the organosilane compounds is contained in a sealed container.BACKGROUND OF THE INVENTION BACKGROUND ART

[0004] In recent years, as the degree of integration and miniaturization of semiconductor integrated circuits has progressed, problems such as a decrease in signal transmission speed in wiring and an increase in power consumption have become more serious, and high performance of insulating films used in each step of semiconductor manufacturing is required. In particular, in the case of forming thin structures or complex structures in semiconductor materials, or when a very thin interlayer insulating film is required, it is important to form a high-performance film that satisfies the necessary properties (such as dielectric constant and mechanical strength) for each purpose by film formation in deposition conditions such as CVD (Chemical Vapor Deposition) or ADD (Atomic Layer Deposition).Atorney Docket No. 688243.0168 / 149WO

[0005] Therefore, in addition to the conventionally used insulating film material SiCh (dielectric constant 4.0) that uses a material such as tetraethoxysilane (TEOS) as its precursor, high-performance insulating films using precursors consisting of organosilane compounds with different structures and compositions have been proposed. For example, U.S. Patent Application Publication No. 2006 / 0165891 discloses a CVD method for forming a film containing Si, C, O, and H atoms (SiCOH) with a lower dielectric constant (k). This method describes the use of precursors containing specific chemical structures, such as Si-CEk-Si or Si-CEE, to introduce these structures into the insulating film, thereby making it possible to form a low-dielectric constant film.

[0006] On the other hand, a method for synthesizing these precursors with specific structures at the high purity levels required for semiconductor applications has been reported. For example, U.S. Patent Application Publication No. 2011 / 0082309 and U.S. Patent Application Publication No. 2009 / 0299086 describe a manufacturing method for synthesizing compounds (XsSi-R-SiXs) with a specific Si-CFE-Si structure at high purity in high efficiency.SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION

[0007] However, in response to the recent demands for further miniaturization and cost reduction of insulating film precursors, industrial-scale production of insulating films requires performance and quality control that may withstand industrial production. Specifically, when using precursors that have high-boiling points and are highly reactive, especially those containing multiple silicon atoms and multiple reactive substituents within the precursor molecule, the evaporated precursor may become deposited on the walls of the pipes during the industrial process. As the deposition progresses, the pipes may become clogged, leading to production stoppages. Avoiding such clogging in industrial processes has been a major challenge in achieving stable industrial production.

[0008] In light of this background, there has been a need for a precursor that could form a high-performance insulating film while avoiding clogging in pipes and other industrial processes.MEANS FOR SOLVING THE PROBLEM

[0009] In their efforts to solve the aforementioned problems, the inventors have discovered that, by reducing the content of specific silane compounds that are impurities in relation to the given silane compound, these problems may be solved.Attorney Docket No. 688243.0168 / 149WO

[0010] In other words, the present invention has the following aspects:(1)A composition comprising a silane compound 1 having formula (1), wherein, as calculated from area percentages in gas chromatography, a content of the silane compound 1 is 99.0% or higher, a content of a silane compound 2 having formula (2), is less than 0.05%, a content of a silane compound 3 having formula (3) is less than 0.80%, and a content of a silane compound 5 having formula (5) is less than 0.05%:wherein R1to R4represent the same or different hydrocarbon groups having 1 to 10 carbon atoms, a and b represent the same or different integers of 0 to 3, a + b is an integer of 5 or less, and R5represents a hydrocarbon group with 1 to 6 carbon atoms;wherein c and d represent the same or different integers of 0 to 3, the sum of c and d is greater than the sum of a and b in formula (1);Ol Vz o!(OR7 / 3-a' (OR9l3-b'wherein R6to R9represent the same or different hydrocarbon groups having 1 to 10 carbon atoms, and a’ and b’ represent the same or different integers from 0 to 3;Attorney Docket No. 688243.0168 / 149WO (R15)g(R17)b (R20)m (R22)nSi - R19- Si - O - Si - R24- Si(OR’% (OR,8)2.h(OR21)2.m(OR23)3,nV^ / wherein R15to R18and R20to R23represent the same or different hydrocarbon groups having 1 to 10 carbon atoms, g and n represent the same or different integers of 0 to 3, h and m represent the same or different integers of 0 to 2, and R19and R24represent the same or different hydrocarbon groups having 1 to 6 carbon atoms.(2) The composition of (1) wherein the content of the silane compound 3 is less than 0.05%.(3) The composition of (1) or (2) wherein the content of the silane compound 2 is less than 0.01%. (4) The composition of any one of (1) to (3), further comprising a silane compound 4 having formula (4), wherein a content of the silane compound 4, as calculated from an area percentage in gas chromatography, is greater than 0% and 0.30% or less:(OR11)3-e (OR13)2-fwherein R10to R13represent the same or different hydrocarbon groups with 1 to 10 carbon atoms, e is an integer of 0 to 3, f is an integer of 0 to 2, and R14represents a hydrocarbon group with 1 to 6 carbon atoms.(5) The composition of any of (1) to (4), wherein a metal content is 30 mass ppb or less for each metal element.(6) The composition of any of (1) to (5), wherein a halogen content is 10 mass ppm or less for each halogen atom.(7) The composition of any of (1) to (6), wherein the composition is substantially free of solvent. (8) The composition of any one of (1) to (7) wherein the composition is used for chemical vapor deposition (CVD) or atomic layer deposition (ALD).(9) A method for manufacturing a thin film, comprising forming a thin film by chemical vapor deposition (CVD) or atomic layer deposition (ALD) using the composition of any one of (1) to (8). (10) A method for manufacturing a thin film, comprising spin coating a thin film using theAttorney Docket No. 688243.0168 / 149WO composition of any one of (1) to (8).(11) A transfer method comprising vaporizing the composition of any one of (1) to (8) and transporting the vaporized composition through a pipeline.(12) An article containing a composition of any one of (1) to (8) in a sealed container having one or more pipelines.(13) The article of (12), wherein the sealed container is a metal pressure vessel.(14) A method for manufacturing a thin film on a substrate, comprising vaporizing the composition of any one of (1) to (8), introducing the vaporized composition into a reaction chamber, and forming a thin film on a substrate in the reaction chamber using the vaporized composition.(15) The method for manufacturing of (14), wherein the composition is vaporized by an injection method.(16) The method for manufacturing of (14) or (15), wherein the composition is vaporized without introducing a carrier gas into the precursor liquid.(17) A thin film on a substrate obtained by the manufacturing method of any one of (14) to (16). (18) The thin film on a substrate of (17), wherein an in-plane uniformity is within ±5% and a hardness is 1 GPa or more.(19) The method for manufacturing a thin film of (9), wherein an in-plane uniformity of the thin film is within ±5% and a hardness is 1 GPa or more.EFFECT OF THE INVENTION

[0011] The composition of the present disclosure, which contains a specific Silane compound 1 as the main component with a high degree of purity, avoids blockage in industrial processes due to deposits in the piping, such as clogging of the piping due to the adhesion of volatile precursors. By reducing the content of specific silane compounds, industrially stable production is enabled.BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Fig. 1 is a schematic sectional view of a CVD precursor supply container that may be used in one embodiment of the present disclosure.

[0013] Fig. 2 is a FID chart of Composition E-2 before decomposition in Comparative Example 1-2.

[0014] Fig. 3 is a FID chart of Composition E-2 after decomposition in Comparative Example 1-2.Attorney Docket No. 688243.0168 / 149WO

[0015] Fig. 4 is Table 1 from the Examples showing a summary of silane compositions according to aspects of the disclosure.

[0016] Fig. 5 is Table 4 from the Examples showing a summary of silane compositions according to aspects of the disclosure.DETAILED DESCRIPTION OF THE INVENTION

[0017] The present invention will be described below based on the examples of embodiments for carrying out the invention. However, the present invention is not limited to the examples of embodiments that will be described below.

[0018] Furthermore, in this specification, when “X to Y” (where X and Y are arbitrary numbers) is expressed, unless otherwise specified, this includes the meaning of “at least X to at most Y” as well as the meaning of “preferably greater than X” or “preferably less than Y.”

[0019] In addition, when “X or more” (where X is an arbitrary number) or “Y or less” (where Y is an arbitrary number) is expressed, this includes the meaning of “preferably greater than X” or “preferably less than Y .”

[0020] Furthermore, “X and / or Y (where X and Y are arbitrary components)” means at least one of X and Y, and may mean three possibilities: only X, only Y, or both X and Y.

[0021] Regarding the numerical ranges described step-by-step in this document, the upper or lower limit of a given stage’s numerical range may be freely combined with the upper or lower limit of another stage’s numerical range. Additionally, in the numerical ranges described in this document, the upper or lower limit of the numerical range may be replaced with the values shown in the example of embodiment.

[0022] Unless otherwise stated, any numerical value referring to weight percentages, temperatures, flow rates, pressures, etc. (but not GC area percentages) is to be understood as being modified in all instances by the term “about.” Thus, a numerical value typically includes ± 10% of the recited value. For example, the recitation of a temperature such as “10°C” or “about 10°C” includes 9°C and 11°C and all temperatures there between.

[0023] All numerical ranges expressed in this disclosure expressly encompass all possible subranges, all individual numerical values within that range, including integers within such ranges and fractions and decimal amounts of the values unless the context clearly indicates otherwise.

[0024] Below, the composition containing organosilane compounds according to one example of an embodiment of the disclosure (hereinafter referred to as “the composition”) will be describedAtorney Docket No. 688243.0168 / 149WO in detail. The composition may be used, for example, as a raw material (precursor) for chemical vapor deposition (CVD) or atomic layer deposition (ALD). In this composition, the content of components other than Silane compounds 1, 2, 3, 4, and 5 described below is preferably 10% or less by weight relative to the total weight of the composition, and more preferably 5% or less by weight. In this composition, the total content of the components of Silane compounds 1, 2, 3, 4, and 5 described below is preferably 90% or more by weight relative to the total weight of the composition, and more preferably 95% or more by weight.Organosilane Compounds

[0025] Silane compound 1, an organosilane compound according to the present disclosure, may be used as a precursor for CVD or ALD, together with steam, oxygen, ozone, or oxidizing agents such as hydrogen peroxide, or together with reducing agents such as hydrogen or ammonia in order to adjust the oxidation process and control the growth characteristics of the film. In this case, the necessary performance as an interlayer insulating film may be exhibited as a result of the appropriate reactions and cross-linking primarily by the alkoxy groups within Silane compound 1.Silane compound 1

[0026] The main component of this composition, Silane compound 1, has formula (1):(R’)a (R3)b15Si - R - S!i(OR2)3-a (OR4)3-b

[0027] In formula (1), R1to R4represent the same or different hydrocarbon groups having 1 to 10 carbon atoms, a and b represent the same or different integers of 0 to 3, a + b is an integer of 5 or less, and R5represents a hydrocarbon group with 1 to 6 carbon atoms. Silane compound 1 has active groups such as OR2or OR4as shown in formula (1), which provide the desired performance.

[0028] The number of carbon atoms in R1to R4is typically 1 to 10, considering the deposition rate in CVD or ALD, but 1 to 6 carbons is preferred from the viewpoint of mechanical properties after film formation, and 1 to 2 carbons is further preferred from the viewpoint of deposition rate.Atorney Docket No. 688243.0168 / 149WO

[0029] R1to R4may be, for example, alkyl groups such as, without limitation, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, cyclopentyl, or cyclohexyl; aromatic hydrocarbon groups such as phenyl, tolyl, or benzyl; or alkenyl groups such as vinyl, 1-propenyl, allyl, or 3-butenyl. From the viewpoint of the mechanical properties after film formation, methyl, ethyl, vinyl, propyl, allyl, isopropyl, butyl, isobutyl, sec-butyl, and t-butyl groups are preferred, while from the viewpoint of film formation speed, alkyl groups with 1 to 4 carbon atoms such as methyl, ethyl, propyl, and isopropyl are more preferred. It is even more preferable to use methyl, ethyl, and propyl groups, with methyl groups being particularly preferred.

[0030] R1to R4may all be the same or different from each other, but from the viewpoint of the ease of manufacturing Silane compound 1, it is preferable for R1and R3to be the same, and for R2and R4to be the same, and it is particularly preferable for R1to R4to all be the same.

[0031] Because the decomposition reactivity tends to increase when the hydrocarbon groups R2and R4are methyl groups, these substituents are preferable when the composition is used for injection type CVD or ALD methods.

[0032] Examples of R5include, for example, saturated hydrocarbon groups such as a methylene group, ethylene group, propylene group, butylene group, and aromatic hydrocarbon groups such as a phenylene group. A saturated hydrocarbon group containing 1 to 2 carbon atoms, that is, a methylene group or an ethylene group, is more preferable, and a methylene group is particularly preferable.

[0033] In formula (1), a and b are integers ranging from 0 to 3, and may be the same or different. From the viewpoint of film deposition rate and mechanical properties (hardness, elastic modulus, etc.) after film deposition, it is preferable that a and b are the same or different integers ranging from 0 to 2. From the viewpoint of the balance between a low dielectric constant and mechanical properties, it is preferable for both a and b to be 2 or 1, and it is particularly preferable for both to be 1. When a and b are both 3, there are no active groups, and it may be difficult to form chemical bonds with adjacent molecules. Therefore, it is preferable that at least one of a and b is less than 3, and that a + b is an integer of 5 or less. As a + b, it is preferable that the integer ranges from 0 to 4, and it is even more preferable for the integer to range from 2 to 4. From the viewpoint of the film deposition rate and mechanical properties (hardness, elastic modulus, etc.) after film deposition, it is preferable that a = b.Atorney Docket No. 688243.0168 / 149WO

[0034] The molecular weight of Silane compound 1 is preferably 160 or more, more preferably 170 or more, and even more preferably 180 or more. Further, it is preferable for the molecular weight to be 400 or less, even more preferable for it to be 300 or less, and further preferable for it to be 250 or less. If the molecular weight of Silane compound 1 is equal to or greater than the lower limit noted above, it tends to have a moderate vapor pressure that is easy to handle as a precursor for CVD or ALD, thereby improving the thermal stability. If the molecular weight of Silane compound 1 is below the upper limit, it tends to have sufficient volatility to reach the substrate in CVD or ALD. The lower and upper limits of the molecular weight of Silane compound 1 may be arbitrarily combined, for example, 160 to 400, 170 to 300, or 180 to 250.Silane compound 2

[0035] In some embodiments, Silane compound 2 having formula (2) may exhibit undesirable decomposition behavior, leading to blockage of piping within the apparatus such as CVD or ALD, due to the residual impurities in the composition.(R')C (R3)dSi - R5- SifoR2)3.c(OR4)3-d' ' (2)

[0036] In formula (2), c and d represent the same or different integers of 0 to 3, the sum of c and d is greater than the sum of a and b in formula (1), and R1to R5are as defined in formula (1) and may be the same possible and preferred groups as described above.

[0037] From the viewpoint of balancing film deposition rate and mechanical strength, as well as to ensure uniform mixing, it is preferable for the sum of c and d to be greater than the sum of a and b in formula (1). From the viewpoint of film deposition rate, it is preferable for c and d to be the same or different integers from 0 to 2, and it is particularly preferable that c is 2 and d is 1, or c is 1 and d is 2.

[0038] Also, it is preferable that a and b in formula (1) are the same or different integers from 0 to 2, and that c and d in formula (2) are the same or different integers from 0 to 2.

[0039] From the standpoint of enabling uniform vaporization together with Silane compound 1, the molecular weight of Silane compound 2 is preferably 160 or more, more preferably 170 orAtorney Docket No. 688243.0168 / 149WO more, and even more preferably 180 or more. Further, the molecular weight should be 400 or less, although 300 or less is more preferable, and 250 or less is even more preferable. If the molecular weight of Silane compound 2 is equal to or greater than the lower limit noted above, it tends to effectively achieve the desired effects described herein. The lower and upper limits of the molecular weight of Silane compound 2 may be arbitrarily combined, for example, 160 to 400, 170 to 300, or 180 to 250. On the other hand, because Silane compound 2 may become a factor that leads to blockage of the piping, there may be instances in which it is preferable for the molecular weight of Silane compound 2 to exceed 400 from the viewpoint of ensuring that it is not vaporized together with Silane compound 1.

[0040] The difference between the molecular weight of Silane compound 1 and the molecular weight of Silane compound 2 is preferably 40 or less from the viewpoint of uniform film formation, more preferably 30 or less, and particularly preferably 20 or less. On the other hand, because Silane compound 2 may become a factor that leads to blockage of the piping, there may be instances in which it is preferable for the difference in the molecular weight of Silane compound 1 and Silane compound 2 to exceed 40 from the viewpoint of ensuring that it is not vaporized together with Silane compound 1.Silane compound 3

[0041] In some embodiments, Silane compound 3 having formula (3) may exhibit undesirable decomposition behavior, leading to blockage of piping within the apparatus such as CVD, due to its presence as a residual impurity within Silane compound 1.(R6k> (Rs)b'vl kz wl(OR7H-a' (OR9')W' (3)

[0042] In formula (3), R6to R9represent the same or different hydrocarbon groups having 1 to 10 carbon atoms, and a’ and b’ represent the same or different integers from 0 to 3. R6to R9may be the same as the hydrocarbon groups R1to R4in Silane compound 1.

[0043] Further, a’ and b’ represent the same or different integers from 0 to 3, and from the viewpoint of film formation speed, a’ and b’ are preferably the same or different integers from 0 to 2. From the viewpoint of uniform mixing between Silane compound 1 and Silane compound 3, it isAtorney Docket No. 688243.0168 / 149WO preferable that a = a’ and b = b’. From the viewpoint of the film deposition rate and mechanical properties after film deposition, it is preferable that a’ = b’.

[0044] The molecular weight of Silane compound 3 is preferably 170 or more, more preferably 180 or more, and even more preferably 190 or more. Further, it is preferable for the molecular weight to be 400 or less, although it is even more preferable for it to be 300 or less, and further preferable for it to be 260 or less. If the molecular weight of Silane compound 3 is equal to or greater than the lower limit noted above and less than the upper limit noted above, it tends to effectively achieve the desired effects described herein. The lower and upper limits of the molecular weight of Silane compound 3 may be arbitrarily combined, for example, 170 to 400, 180 to 300, or 190 to 260. On the other hand, because Silane compound 3 may become a factor that leads to blockage of the piping, there may be instances in which it is preferable for the molecular weight of Silane compound 3 to exceed 400 from the viewpoint of ensuring that it is not vaporized together with Silane compound 1.

[0045] The difference between the molecular weight of Silane compound 1 and the molecular weight of Silane compound 3 is preferably 30 or less from the viewpoint of uniform film formation, more preferably 20 or less, and particularly preferably 10 or less. On the other hand, because Silane compound 3 may become a factor that leads to blockage of the piping, there may be instances in which it is preferable for the difference in the molecular weight of Silane compound 1 and Silane compound 3 to exceed 30 from the viewpoint of ensuring that it is not vaporized together with Silane compound 1.Mechanism for the generation of Silane compound 2 and Silane compound 3

[0046] There are no particular restrictions on the synthesis method for Silane compound 1, but exemplary methods are those described in U.S. Patent Application Publication No. 2011 / 0082309 and U.S. Patent Application Publication No. 2009 / 0299086. One example is the method of coupling a silane compound as shown in formula (11) (here, chloromethylmethyl (isopropoxy) silane) with another silane compound (here, methyltrimethoxysilane) through a Grignard reaction as described in U.S. Patent Application Publication No. 2009 / 0299086. In formula (11), Me represents a methyl group, iPr represents an isopropyl group, MeOH represents methanol, and p-TsOna represents p-toluenesulfonic acid sodium.Attorney Docket No. 688243.0168 / 149WO

[0047] When performing this type of reaction, there is the possibility of the generation of: (A) by-products caused by impurities in the starting compounds, and (B) by-products generated due to side reactions.Me .. Me Me Me | Mg | MeSi(OMe)3| | iPrO— Si— CH2— Cl - ► iPr 0— Si— CH2— MgCI iPr O— Si— CH2— Si— OMe I IOiPr OiPr OiPr OMe Me Me MeOH | | — — — - ► MeO— Si— CH2— Si— OMe (11) p-TsONa |2|OMe OMe

[0048] As an example of (A), due to the influence of dimethyldimethoxysilane contained within the methyltrimethoxysilane, the following compound (12) (corresponding to Silane compound 2) may be generated as an impurity.Me MeI IMeO— Si — CH2— Si— MeI I OMe OMe(12)

[0049] As an example of (B), when methyltrimethoxysilane molecules condense with each other, the following compound (13) (corresponding to Silane compound 3) may be generated as an impurity.Me Me Me MeI I I IMeO— Si— OMe + MeO— Si— OMe - > MeO— Si— O— Si— OMeI I I I OMe OMe OMe OMe(13)

[0050] The mechanism for the generation of Silane compound 2 and Silane compound 3 depends on the synthesis method for Silane compound 1 and / or the types of impurities contained in the raw materials and so is not limited to the above-noted examples. In general, as the molecular weight and structure of Silane compound 1 and Silane compound 2 or Silane compound 3 become closer, the boiling points similarly become closer or the compounds form an azeotropic mixture, making separation and purification by distillation, etc., difficult.Attorney Docket No. 688243.0168 / 149WOSilane compound 4

[0051] In one embodiment, Silane compound 4 having formula (4) may exhibit undesirable decomposition behavior, leading to blockage of piping within the apparatus such as CVD, due to its presence as a residual impurity within Silane compound 1. Silane compound 4 is presumed to be generated when Silane compound 1 reacts with an active species such as water, causing partial hydrolysis of the alkoxy group.(R1°)e (R12)fSi - 1^14 - gj - QU(OR”)3 e(OR13)2-f(4)

[0052] In formula (4), R10to R13represent the same or different hydrocarbon groups having 1 to 10 carbon atoms, e is an integer of 0 to 3, f is an integer of 0 to 2, and R14represents a hydrocarbon group with 1 to 6 carbon atoms. R10to R13and R14may be the same R groups as those described above for Silane compound 1.

[0053] The molecular weight of Silane compound 4 is preferably 170 or more, more preferably 180 or more, and even more preferably 190 or more. Further, it is preferable for the molecular weight to be 400 or less, although it is even more preferable for it to be 300 or less, and further preferable for it to be 250 or less. If the molecular weight of Silane compound 4 is equal to or greater than the lower limit noted above and less than the upper limit noted above, it tends to effectively achieve the desired effects described herein .The lower and upper limits of the molecular weight of Silane compound 4 may be arbitrarily combined, for example, 170 to 400, 180 to 300, or 190 to 250. The difference between the molecular weight of Silane compound 1 and the molecular weight of Silane compound 4 is preferably 40 or less from the viewpoint of uniform film formation, more preferably 30 or less, and particularly preferably 20 or less.Silane compound 5

[0054] In one embodiment, Silane compound 5 having formula (5) may exhibit undesirable decomposition behavior, leading to blockage of piping within the apparatus such as CVD, due to its presence as a residual impurity within Silane compound 1. Silane compound 5 is presumed to be generated by the dehydration and condensation of the two OH groups of Silane compound 4.Attorney Docket No. 688243.0168 / 149WO (R15)g(R17)b (R20)m (R22)nSi - R19- Si - O - Si - R24- Si(OR’% (OR,8)2.h(OR21)2.m(OR23)3,nV^ /

[0055] In formula (5), R15to R18and R20to R23represent the same or different hydrocarbon groups having 1 to 10 carbon atoms, g and n represent the same or different integers of 0 to 3, h and m represent the same or different integers of 0 to 2, and R19and R24represent the same or different hydrocarbon groups having 1 to 6 carbon atoms.

[0056] For R15to R18and R20to R23, and R19and R24, the same R groups as those described above for Silane compound 1 may be used.

[0057] Silane compound 4 and Silane compound 5 may be intentionally added, but Silane compound 4 also may be generated during the storage of Silane compound 1 due to hydrolysis, and Silane compound 5 may also be generated by the dimerization of Silane compound 4. The molecular weight of Silane compound 5 is preferably 250 or more, more preferably 300 or more, and even more preferably 350 or more. Further, it is preferable for the molecular weight to be 700 or less, although it is even more preferable for it to be 600 or less, and further preferable for it to be 500 or less. If the molecular weight of Silane compound 5 is equal to or greater than the lower limit noted above and less than the upper limit noted above, it tends to effectively achieve the desired effects described herein. The lower and upper limits of the molecular weight of Silane compound 5 may be arbitrarily combined, for example, 250 to 700, 300 to 600, or 350 to 500. On the other hand, because Silane compound 5 may become a factor that leads to blockage of the piping, there may be instances in which it is preferable for the molecular weight of Silane compound 5 to exceed 700 from the viewpoint of ensuring that it is not vaporized together with Silane compound 1.Composition Embodiments

[0058] The contents (%) of the silane compounds in the composition may be quantified with high sensitivity and accuracy by separating the composition using gas chromatography and using a Flame Ionization Detector (FID) as the detector. For example, detection of 0.01% is also possible. If no peak for each silane compound is detected by this analytical method, the content of the corresponding silane compound may be concluded to be less than 0.01%. If there is a desire to set the detection limit to less than 0.01%, it is also possible to further lower the detection limit byAtorney Docket No. 688243.0168 / 149WO increasing the concentration of the sample being analyzed or by increasing the sensitivity of the detector.

[0059] This composition may be used as a precursor for CVD or ALD, and preferably does not contain any solvent, that is, it is substantially free of solvent. When the composition does not contain any solvent, it will be possible to analyze the composition directly using the above-noted gas chromatography without any prior treatment. Note that ‘substantially free of solvent’ means that the content of solvent in the composition when converted from the area percentage in gas chromatography is less than 0.01%.

[0060] As an example, first, the area of each peak in the chart obtained using FID (see Fig. 2 and Fig. 3, for example) is calculated. At that time, it is possible to identify the chemical structure of the compound corresponding to each peak by using a separate method such as mass spectrometry. Next, the content is calculated as a percentage by taking the total sum of the area integration values of the peaks of all of the compounds containing the silane atoms that were observed as the denominator, and using the area integration value of the peak of the target silane compound as the numerator.

[0061] According to this calculation method, only the compounds containing silane atoms are subject to the calculation of the content percentage (%), and solvents, additives, and impurities that do not contain silane atoms are not subject to this calculation.

[0062] Moreover, because the sensitivity of FID varies depending on the compound in the above-mentioned quantification method based on the area ratio, it does not result in a strict assay. However, amongst compounds with similar chemical structures, the sensitivity factor values of the detector may be estimated to be close. Therefore, in the present disclosure, the area ratio obtained by the detector (FID as an example) for each compound separated by gas chromatography is defined as the quantitative ratio of the compound.

[0063] The content of Silane compound 1 within this composition, as calculated from the area percentage in gas chromatography, should be 99.0% or more. From the viewpoint of uniform film quality after film formation, a content of 99.5% or more is more preferable, while a content of 99.7% or more is even more preferable, and from the viewpoint of preventing clogging of the piping, a content of 99.9% or more is even more preferable, while a content of 99.95% or more is even more preferable, a content of 99.99% or more is further preferable, a content of 99.5% or more is more particularly preferable, and 100% is especially preferable.Atorney Docket No. 688243.0168 / 149WO

[0064] The content of Silane compound 2 within this composition, as calculated from the area percentage in gas chromatography, should be less than 0.05% from the standpoint of preventing the clogging of the piping due to excessive decomposition, although a content of less than 0.04% is preferable, a content of less than 0.20% is even more preferable, a content of less than 0.01% is further preferable, and it is particularly preferable for the content to be 0%.

[0065] The content of Silane compound 3 within this composition, as calculated from the area percentage in gas chromatography, should be less than 0.80% from the standpoint of preventing the clogging of the piping due to excessive decomposition, although a content of less than 0.50% is preferable, a content of less than 0.30% is even more preferable, a content of less than 0.20% or less is even more preferable, a content of less than 0.05% is even more preferable, a content of less than 0.01% is further preferable, and it is particularly preferable for the content to be 0%.

[0066] Moreover, a composition containing both Silane compound 3 and Silane compound 2 is more likely to decompose than a composition containing only Silane compound 2. Therefore, when Silane compound 2 and Silane compound 3 are both present within the composition, excessive decomposition of the composition may occur and the piping may be blocked even if Silane compound 2 and Silane compound 3 are present in smaller amounts compared to a composition in which only one of these compounds is present. Therefore, when the composition contains Silane compound 1, Silane compound 2, and Silane compound 3, the contents of Silane compound 2 and Silane compound 3 within the composition, as calculated from the area percentage by gas chromatography, should each be less than 0.05%. It is even more preferable for each content to be less than 0.02%, and it is further preferable for each content to be less than 0.01%. It is particularly preferable for the content of each of Silane compound 2 and Silane compound 3 in this composition, calculated from the area percentage in gas chromatography, to be 0%.

[0067] The content of Silane compound 5 within this composition, as calculated from the area percentage in gas chromatography, should be less than 0.05%, although a content of less than 0.10% or less is more preferred. It is particularly preferable for the content to be 0%.

[0068] Within this composition, Silane compound 4 is not a necessary component. However, Silane compound 4 is an intermediate that necessarily occurs when Silane compound 1 is reacted via CVD or ALD, and it may be present within a certain range because it will not obstruct the effects described herein. More specifically, Silane compound 4 in this composition, as calculated from the area percentage in gas chromatography, may be present in an amount exceeding 0%, although 0.03% or more is acceptable, and there are instances in which 0.05% or more isAtorney Docket No. 688243.0168 / 149WO acceptable, while there are also instances in which 0.06% or more is acceptable. On the other hand, in order to suppress the tendency for Silane compound 4 to dimerize and form Silane compound 5, the upper limit should be 0.30% or less, although 0.20% or less is even more preferable, and 0.10% or less is particularly preferable. The lower and upper limits of the content of Silane compound 4 within this compositions may be arbitrarily combined. For example, when this composition includes Silane compound 4, the content may be more than 0.0% and 0.30% or less, 0.03 to 0.30%, 0.03 to 0.20%, 0.05 to 0.30%, 0.05 to 0.20%, or 0.03 to 0.10%.

[0069] If the composition contains Silane compound 2, Silane compound 3, and Silane compound 5 within the above-noted ranges, the reactivity of the composition with other gases within the apparatus such as CVD will be uniform in time and space, so it will be possible to set a wide range of conditions for forming a film on the substrate without depositing decomposition products of the silane compounds in the piping or the like. On the other hand, if the composition contains Silane compound 2, Silane compound 3, and Silane compound 5 in amounts which are in excess of the above-noted range, it becomes difficult or impossible to set conditions for forming a film on the substrate without depositing decomposition products of the silane compounds in the piping or the like due to the fact that the reactivity with other gases such as other gases triggered by Silane compound 2, Silane compound 3, and Silane compound 5 will increase in a non-uniform manner both temporally and spatially.Method of purifying the composition containing Silane compound 1

[0070] There are no particular restrictions on the purification method for the composition containing Silane compound 1, but distillation is preferable from the standpoint that it is a purification method that may deal with high purification efficiency and high productivity, in addition to the fact that organosilane compounds are unstable in relation to water. In order to separate Silane compound 1 from the crude product, which also contains Silane compounds 2 and 3 that boast similar molecular weights, it is preferable to use a distillation column with a high number of theoretical plates and to perform vacuum distillation with a controlled reflux ratio.

[0071] Distillation purification is more challenging when the molecular weight difference between Silane compound 1 and the target silane compound is small, especially when it is 40 or less, and even more so when it is 30 or less, or 20 or less. In such cases, higher purification efficiency is required. For example, if Silane compound 1 is Silane compound 1 A (molecular weight 224) having formula (1 A), Silane compound 2 is Silane compound 2A (molecular weightAttorney Docket No. 688243.0168 / 149WO 208) having formula (2A), and Silane compound 3 is Silane compound 3 A (molecular weight 226) having formula (3 A), the molecular weight difference between Silane compound 1 A and Silane compound 2A, as well as between Silane compound 1 A and Silane compound 3A, is 16 or less. Moreover, their molecular structures are also very similar, consisting of Si-O, Si-C, and O-C bonds. Therefore, high-efficiency distillation separation is necessary.

[0072] In order to achieve high purification efficiency in distillation separation, methods such as increasing the theoretical number of stages in the distillation column and increasing the reflux ratio may be employed.

[0073] The theoretical number of stages in the distillation column should be 5 or more, although 8 or more is preferable, 10 or more is even more preferable, 15 or more is further preferable, and 20 or more is particularly preferable. On the other hand, if the theoretical number of stages in the distillation column is too high, productivity decreases, which may become a problem when scaling up or industrializing the processes, so the theoretical number of stages in the distillation column should be 50 or less, although 40 or less is preferable, 30 or less is even more preferable, and 25 or less is particularly preferable. The lower and upper limits of the theoretical number of stages in the distillation column may be arbitrarily combined, for example, 5 to 50, 8 to 40, 10 to 30, 15 to 25, or 20 to 25 stages.

[0074] The reflux ratio during distillation is calculated using a formula of the distillation time (seconds) / reflux time (seconds). Examples of the specific method for controlling the reflux ratioAtorney Docket No. 688243.0168 / 149WO during distillation include, for example, installing an automatic fractionation head controlled by a reflux ratio timer on top of the distillation column, and controlling it by setting the distillation time (seconds) and reflux time (seconds). From the viewpoint of improving the purification efficiency, a higher reflux ratio is better, but there is a tendency for productivity to decrease. Therefore, from the viewpoint of achieving industrially efficient productivity, when separating a specific impurity, it is preferable to set a high reflux ratio in order to increase the separation efficiency, and after the separation of that impurity is completed, to lower the reflux ratio to increase the distillate yield. From the standpoint of facilitating the separation of impurities that are difficult to separate, such as impurities with a difference relative to the molecular weight of Silane compound 1 that is 40 or less, the reflux ratio during distillation should be 0.1 or more, although 0.3 or more is preferable, and 0.5 or more is even more preferable. On the other hand, from the viewpoint of distillation productivity, the reflux ratio during distillation should be 10 or less, although 5 or less is preferable, and 3 or less is even more preferable. The lower and upper limits of the reflux rate during distillation may be freely combined, such as 0.1 to 10, 0.3 to 5, or 0.5 to 3.

[0075] The distillation column having the above-mentioned theoretical number of stages may be of any type, such as a tray-type distillation column or a packing-type distillation column, but a packing-type distillation column is preferred from the viewpoint of high separation efficiency per unit height, and a distillation column packed with SUS packing is preferable for adsorbing and separating trace halogen impurities and metal impurities, as will be described later.Metal impurities

[0076] The metal content in this composition refers to the content of metal and / or metalloid elements contained as impurities in the composition, and may be expressed in units such as mass%, mass ppm, and mass ppb. There are no particular restrictions on the target metal elements, but examples include Ag, Al, Au, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hf, In, K, Li, Mg, Mn, Mo, Na, Ni, Pb, W, Zn, Zr, and Sn. In particular, in cutting-edge fine semiconductor processes (such as fabrication of fine wiring with a width of less than 100 nm or EUV lithography systems), trace metal impurities in semiconductor materials are likely to cause pattern defects, short circuits or corrosion of metal wiring, increased out-gassing, and other issues, which may lead to a decline in performance and yield. Therefore, stricter control is required.

[0077] The metal content in this composition is preferably 10 mass ppm or less for each metal, although 1 mass ppm or less is more preferable, 100 mass ppb or less is even more preferable, 50Atorney Docket No. 688243.0168 / 149WO mass ppb or less is even more preferable, 30 mass ppb or less is particularly preferable, and 10 mass ppb or less is especially preferable. In particular, for cutting-edge fine semiconductor processes (such as fabrication of fine wiring with a width of less than 100 nm or EUV lithography systems), the metal content in this composition should be 10 mass ppb or less for each metal, although 5 mass ppb or less is preferable, and 1 mass ppb or less is even more preferable.Measurement of the metal content

[0078] There are no particular restrictions on the method of measuring the metal content, but it is preferable for the method to have a lower limit for the detection sensitivity of 10 mass ppb or less, or more preferably 1 mass ppb or less, for each metal element. Specific methods include those shown in the examples, and these measurements are typically carried out using a combination of pretreatment methods and analytical methods, such as those described below.

[0079] As the pretreatment method, it is preferable to recover the metal elements from the composition to be analyzed with a high recovery rate, high precision, and high reproducibility. Examples of such methods include combustion absorption and acid decomposition methods. As the analytical method, in order to achieve the detection sensitivity mentioned above, methods such as quantification by ion chromatography (IC) or inductively-coupled plasma mass spectrometry (ICP-MASS) may be used. By appropriately combining these pretreatment and analytical methods, it is possible to analyze the metal content within the composition.Methods for Reducing Metal Elements

[0080] Methods for reducing metal elements in the composition include (1) reducing metal elements derived from raw materials, (2) removing metal elements by purifying the composition, and (3) reducing the contamination of metal elements from the equipment or environment that is used. Each method will be explained below.(1) Method of reducing metal elements derived from raw materials

[0081] While it is possible to use raw materials containing metals in their structure to form Silane compound 1, it is preferable to use raw materials with low levels of metal elements other than those present within the structure. More specifically, the content of each metal element other than in the structure of the raw material should be less than 1% by weight, although 0.5% by weight or less is more preferable, 0.1% by weight or less is even more preferable, and 0.01% by weight orAtorney Docket No. 688243.0168 / 149WO less is even more preferable. A level of 10 mass ppm or less is even more preferable, while 1 mass ppm or less is even more preferable, 100 mass ppb or less is further preferable, and 10 mass ppb or less is particularly preferable. Particularly in applications when the composition is a film-forming material for cutting-edge semiconductor processes, it is preferable to control the content of metals other than those contained within the structure of the raw material in order to more stably manufacture a homogeneous material, and it is preferable for this content to be 10 mass ppb or less, and more preferably, 1 mass ppb or less.(2) Method of removing metal elements by purifying the composition.

[0082] The method of reducing metal elements within the composition by purification may be carried out by combining various purification methods. Examples of this method include filtering insoluble matter, liquid separation (using ultrapure water, etc.), column chromatography, removal using reagents or chelating agents, adsorption onto resins, and distillation purification. On the other hand, when silane compounds show reactivity towards water or functional groups, the purification methods for these compounds are limited, and distillation purification is preferable. In the case of distillation purification, a distillation method using a distillation column may be applied. However, a distillation column using SUS structured packing is preferable because trace metal impurities are efficiently adsorbed onto the SUS structured packing, promoting separation. On the other hand, in order to reduce the metal components that may leach out from the SUS during distillation, it is preferable to remove the initial fraction in a short time at a low reflux ratio, and then to set the reflux ratio to obtain the main fraction for obtaining high-purity silane compounds.(3) Method to reduce the contamination of metal elements from the equipment (devices, containers, etc.) or the environment that is used

[0083] When removing metal components in distillation, it is necessary to prevent the contamination of metals from the equipment used for distillation. Silane compounds, which become liquid and gaseous at high temperatures during distillation, may leach metal components or may cause metal leaching due to the oxidation-reduction properties of silane compounds, which may corrode metal equipment. Therefore, more careful attention should be paid to metal leaching and contamination from the equipment and apparatus used as compared to the distillation of ordinary organic compounds. When using SUS equipment, it is preferable to use SUS with high corrosionAtorney Docket No. 688243.0168 / 149WO resistance or SUS with surface corrosion-resistant treatment. More specifically, SUS 316 and SUS 304 are preferred, and materials with corrosion-resistant surface treatment are even more preferable. When using SUS or glass equipment and apparatus, it is preferable to perform reflux washing with a solvent containing alcohol (such as methanol, ethanol, or isopropanol) under sufficient reflux conditions. It is particularly preferable to use SUS equipment, and when using such equipment, it is even more preferable to remove a wider range of impurities, including lipophilic and hydrophilic metal impurities, by combining cleaning with alcohol solvents with cleaning with other non-protonic organic solvents (such as acetone, heptane, or toluene, etc.). It is also preferable for the container used to fill the obtained silane compound to be a well-cleaned container, and it is particularly preferable that the container is cleaned and dried with ultrapure water.

[0084] In addition, metal atoms may be introduced from the environment, such as from the human body, protective gloves, or the atmosphere. In order to prevent these impurities, it is preferable to fill the silane compound directly into the container without exposing it to the atmosphere after distillation. It is also preferable to conduct manufacturing under conditions in which metal elements are reduced, such as within a clean room where the distillation equipment is located.Halogen impurities

[0085] The halogen content in this composition refers to the content of halogen atoms (F, Cl, Br, I) in all of the silane compounds contained in this composition, and this content may be expressed in units such as mass %, mass ppm, or mass ppb. In particular, in cutting-edge fine semiconductor processes (such as fabrication of fine wiring with a width of less than 100 nm or EUV lithography systems), trace halogen impurities in semiconductor materials are likely to cause pattern defects, short circuits or corrosion of metal wiring, degradation of the substrate surface, and other issues, which may lead to a decline in performance and yield. Therefore, stricter control is required. Regarding the structure of compounds containing halogen atoms that may be introduced, various structures such as organic halogen compounds (compounds with C-halogen bonds) and inorganic halogen compounds (compounds with metal-halogen bonds) may be considered.However, even regarding the clogging of the pipework, which is a specific challenge in this composition, the presence of silane compounds containing Si-halogen bonds may be particularly problematic because contact with trace amounts of water or oxygen may cause the decomposition of Silane compound 1, generating acid or halogen anions that will accelerate polymerization. More1Atorney Docket No. 688243.0168 / 149WO specifically, silane compounds containing Si-halogen bonds exhibit properties similar to those of non-halogenated silane compounds in terms of stability, reactivity, volatility (boiling point), melting point, and solubility in organic solvents, and are often difficult to separate from silane compounds. In other words, even with the halogen reduction techniques that have been implemented in conventional similar semiconductor materials (such as film-forming materials using organic compounds or polymers), it may be difficult to remove these compounds. Even if the high purity of silane compounds and low content of metals other than silane is achieved, the halogen content may not be reduced to the desired level because trace amounts of silane compounds containing Si-halogen bonds may not be removed.

[0086] The content of each halogen atom (fluorine atom (F), chlorine atom (Cl), bromine atom (Br), iodine atom (I)) within the composition is preferably 100 mass ppm or less, although 50 mass ppm or less is more preferable, 30 mass ppm or less is even more preferable, 10 mass ppm or less is further preferable, 9 mass ppm or less is even more preferable, and 5 mass ppm or less is particularly preferable for each halogen atom. In particular, for use in the most advanced fine semiconductor processes (such as fabrication of fine wiring with a width of less than 100 nm or EUV lithography systems), 10 mass ppm or less is preferred, 9 mass ppm or less is more preferred, 5 mass ppm or less is further preferred, and 3 mass ppm or less is particularly preferred.

[0087] Particularly with regard to chlorine atoms, there is a high risk of contamination from the raw materials, equipment, and devices used in the production of Silane compound 1. Chlorine atoms may cause corrosion of semiconductor process equipment, increased out-gassing, pattern defects, short circuits, and corrosion of metal wiring. Therefore, it is preferable to reduce halogen atoms, especially chlorine atoms, to a lower level. From this standpoint, the chlorine atom content that may be detected within this composition is preferably 10 mass ppm or less, although 9 mass ppm or less is more preferable, 7 mass ppm or less is even more preferable, 5 mass ppm or less is even more preferable, 4 mass ppm or less is particularly preferable, and 3 mass ppm or less is especially preferable.Measurement of the halogen content

[0088] There are no particular restrictions on the method of measuring the halogen content, but it is preferable for the method to have a lower limit for the detection sensitivity of 3 mass ppm or less, more preferably 1 mass ppm, for each halogen atom. Specific methods include those shown in the examples, and these measurements are typically carried out using a combination of pretreatmentAtorney Docket No. 688243.0168 / 149WO methods and analytical methods, such as those described below. In particular, in terms of the detection of trace amounts (at the 10 mass ppm level, for example) of volatile silane compounds containing Si-halogen bonds, it may be difficult to separate these compounds from other components for detection using conventional methods such as gas chromatography, which are typically used for purity analysis of silane compounds. Additionally, the detection sensitivity of halogen-containing compounds (because the sensitivity in FID detectors, for instance, is derived from carbon and hydrogen atoms) may be insufficient to detect trace components. Furthermore, when using methods for trace metal analysis or elemental analysis (targeting elements other than halogens, such as carbon, nitrogen, or oxygen), it may be difficult to achieve the appropriate trace detection due to insufficient recovery of the target halogen-containing components during the pretreatment, decomposition, or absorption processes.

[0089] As the pretreatment method, it is preferable to recover the halogen atoms from the composition to be analyzed with a high recovery rate, high precision, and high reproducibility. Examples of such methods include combustion absorption and acid decomposition methods. As the analytical method, in order to achieve the detection sensitivity mentioned above, methods such as quantification by ion chromatography (IC) or inductively-coupled plasma mass spectrometry (ICP-MASS) may be used. By appropriately combining these pretreatment and analytical methods, it is possible to analyze the halogen content within the composition. In particular, in order to properly detect and quantify trace halogen components originating from volatile silane compounds, including the aforementioned Si-halogen bonds, it is preferable to use the combustion absorption method, combining the appropriate treatment and absorption methods. Under the appropriate conditions for the measurement of the halogen content, it is preferable to have a lower limit for the detection sensitivity of 10 mass ppm or less, or more preferably 1 mass ppm, for each halogen atom.Methods for reducing the halogen content

[0090] Methods for reducing the halogen content in this composition include: (1) reducing halogen impurities derived from raw materials, (2) removing halogen impurities by purifying compositions containing silane compounds, and (3) reducing the contamination of halogen impurities from the equipment or environment that is used. Each method will be explained below.Atorney Docket No. 688243.0168 / 149WO (1) Method for reducing halogen impurities derived from raw materials

[0091] While it is possible to use raw materials containing halogen in their structure to form the silane compounds, it is preferable to use raw materials with low levels of halogen elements other than those present within the structure. More specifically, the content of each halogen element other than in the structure of the raw material should be less than 1% by weight, although 0.5% by weight or less is more preferable, 0.1% by weight or less is even more preferable, and 0.01% by weight or less is even more preferable. Further, a content of 10 mass ppm or less is even more preferable, and a content of 5 mass ppm or less is particularly preferable. Especially in applications as the filmforming material for cutting-edge semiconductor processes, it is preferable to control the content of halogen other than those contained within the structure that may be included in the raw material in order to stably manufacture a homogeneous material, and it is preferable for this content to be 10 mass ppm or less, and more preferably 5 mass ppm or less. In addition, in the final step to obtain the silane compounds, it is preferable to avoid using raw materials that could become halogen impurities (such as compounds with Si-halogen bonds) and that are difficult to separate in the subsequent purification process.(2) Method for removing halogen impurities by purifying a composition containing silane compounds

[0092] Methods for reducing halogen elements in compositions containing silane compounds through purification include various purification methods such as filtering insoluble matter, liquid separation (using ultrapure water, etc.), column chromatography, removal using reagents or chelating agents, adsorption onto resins, and distillation purification. On the other hand, when silane compounds show reactivity towards water or functional groups, the purification methods for these compounds are limited, and distillation purification is preferable. In the case of distillation purification, a distillation method using a distillation column may be applied. In particular, a distillation column using SUS structured packing is preferable because trace halogen impurities (in particular, impurities having an Si-halogen bond, and compounds that may easily react with or attach to the SUS surface) are efficiently adsorbed onto the SUS structured packing, promoting separation. Additionally, in order to efficiently remove halogen impurities during distillation, it is preferable to remove the initial fraction containing low-boiling-point halogen impurities, and then to set the reflux ratio to remove halogen impurities with similar boiling points to obtain a high-purity silane compound.Atorney Docket No. 688243.0168 / 149WO (3) Method of reducing the contamination of halogen impurities from the equipment (devices, containers, etc.) or the environment that is used

[0093] When removing halogen components during distillation, it is necessary to prevent the contamination of halogens from the equipment used for distillation. In particular, silane compounds that become liquid and gaseous at high temperatures during distillation (especially those with highly reactive Si-halogen bonds) may leach out halogen components contained in the equipment (glass or SUS), requiring more attention to be paid to the leaching and contamination of halogen components from the equipment and devices used than is required in the distillation of ordinary organic compounds. When using SUS equipment, it is preferable to use SUS with high corrosion resistance or SUS with surface corrosion-resistant treatment. More specifically, SUS 316 and SUS 304 are preferred. Materials with corrosion-resistant surface treatments are even more preferable. When using SUS or glass equipment and apparatus, it is preferable to perform reflux washing with a solvent containing alcohol (such as methanol, ethanol, or isopropanol) under sufficient reflux conditions. It is particularly preferable to use SUS equipment, and when using such equipment, it is even more preferable to remove a wider range of impurities, including lipophilic and hydrophilic halogen impurities, by combining cleaning with alcohol solvents with cleaning with other non-protonic organic solvents (such as acetone, heptane, or toluene, etc.). It is also preferable for the container used to fill the obtained silane compound to be a well-cleaned container, and it is particularly preferable that the container is cleaned and dried with ultrapure water. In addition, halogen impurities may be introduced from the environment, such as from the human body, protective gloves, or the atmosphere. In order to prevent these impurities, it is preferable to fill the silane compound directly into the container without exposing it to the atmosphere after distillation. It is also preferable to conduct manufacturing under conditions in which halogen has been reduced, such as within a clean room where the distillation equipment is located.Method of storing the composition containing Silane compound 1

[0094] In order to maintain the high purity of this composition, it is preferable to use a well-sealed container, fill it with an inert gas (such as nitrogen or argon), and store it in a state to ensure that no air and water from the atmosphere may enter. In terms of the specific impact, if, for instance, the composition is stored at room temperature for an extended period of time (such as one month or longer) in a state in which air or water may enter, the above-noted Silane compounds 4 or 5 may be generated as by-products. Additionally, by using a properly sealed container made of theAtorney Docket No. 688243.0168 / 149WO appropriate material, it will be possible to suppress the incorporation of trace metal impurities or halogen impurities from the atmosphere. As a result, it will be possible to prevent the incorporation of the aforementioned trace halogen impurities and metal impurities, and to perform storage while maintaining a low content of these impurities. As for the specific containers for storage, the containers listed in the description of the sealed container described below are preferable.Thin film manufacturing method

[0095] Thin films may be formed by applying a coating using this composition as a precursor.

[0096] The average thickness of the thin film is preferably 500 nm or less. To deal with fine structures, a thickness of 300 nm or less is preferable, 200 nm or less is more preferable, and 100 nm or less is particularly preferable. The lower limit of the average thickness of the thin film is preferably 10 nm or more, although 20 nm or more is more preferable, and 30 nm or more is particularly preferable. The lower and upper limits of the average thickness of the thin film may be arbitrarily combined, for example, 10 to 500 nm, 20 to 300 nm, 20 to 200 nm, or 30 to 100 nm.

[0097] The average thickness of the thin film may be measured using methods such as spectroscopic ellipsometry, X-ray reflectivity (XRR), or transmission electron microscopy (TEM). In particular, spectroscopic ellipsometry is non-destructive and highly accurate, making it suitable for measuring thin film thicknesses of 500 nm or less. Moreover, it is preferable to have a high inplane uniformity of the thin film thickness. For example, in the in-plane thickness uniformity described in the examples below, a value of ±5% or less is preferable, while 3% or less is more preferable, and 1% or less is even more preferable. In particular, when using the plasma CVD or ALD described below, higher film thickness uniformity is required when continuously forming a uniform film using an injection method or the like. For use as a semiconductor insulating film that may withstand post-deposition processes (such as CMP or wiring formation processes), the hardness of the thin film should be 1.0 GPa or greater, although 1.5 GPa or more is even more preferable, 2.0 GPa or greater is preferable, and 25 GPa or more is even more preferable. As for the complex modulus of elasticity, 10 GPa or more is preferable, 20 GPa or more is more preferable, and 30 GPa or more is even more preferable.

[0098] As a coating method, a dry method may be used, a wet method may be used, or a combination thereof may be used.Atorney Docket No. 688243.0168 / 149WO

[0099] Examples of dry methods include, for example, physical vapor deposition (PVD) and chemical vapor deposition (CVD).

[0100] Examples of wet methods include, for example, spin coating, spray coating, dip coating, knife-edge coating, and printing methods (for example, ink-jet printing and screen printing). In the case of a wet method, it is preferable to form a thin film by spin coating using the composition.

[0101] The coating may be performed once or multiple times. For example, multiple spin coatings may be performed using a wet method, or multiple chemical vapor deposition (CVD) processes may be performed using a dry method. Additionally, spin coating using a wet method may be followed by chemical vapor deposition using a dry method in order to achieve the desired final coating thickness. Additionally, heat treatment may be applied after each coating step or after multiple coating steps.

[0102] The physical vapor deposition (PVD) methods that may be used for forming films of this composition using a dry method include vacuum deposition and sputtering. Chemical vapor deposition (CVD) methods include thermal CVD, plasma CVD, and photo-CVD, as well as atomic layer deposition (ALD). In the case of a dry method, it is preferable to form a thin film using CVD or ALD with this composition.

[0103] Plasma CVD (PECVD) is particularly suitable because it allows for film formation at low temperatures, boasts a high deposition rate, and may uniformly coat uneven surfaces. PECVD is a method that uses plasma to promote chemical reactions and deposit thin films on substrates, and this method is widely used in semiconductor manufacturing and optical device production. In this method, a reaction gas is introduced into a vacuum chamber, and plasma is generated using a high-frequency power supply or similar device. The active species within the plasma (such as radicals and ions) promote chemical reactions, and thin films are formed on the substrate surface. The deposition rate and film quality will depend on factors such as the plasma density and energy, substrate temperature, and gas flow rate.

[0104] The reaction gases that may be used in PECVD include silane (SiEL), methane (CEL), nitrous oxide (N2O), oxygen (O2), nitrogen (N2), ammonia (NH3), and carbon tetrafluoride (CF4). Amongst these, oxygen is preferred for the purposes of this disclosure.

[0105] When depositing films using PECVD, the boiling point of the composition and the weight loss may be used as indicators of achieving uniform films. These parameters may beAtorney Docket No. 688243.0168 / 149WO measured using differential thermal analysis (DTA) and thermogravimetric analysis (TGA) simultaneously, such as with a differential thermal gravimetric analyzer. In this case, in order to ensure uniform film formation, it is preferable for the DTA curve to show simple behavior with a single endothermic peak, at which point the weight decreases by 100%.Methods for transporting the composition

[0106] As a method for transporting the composition, an example is a method that involves vaporizing the composition and then transporting the vaporized composition through a pipeline.

[0107] By vaporizing the composition, introducing the vaporized composition into the reaction chamber, and forming a thin film on a substrate in the reaction chamber, a substrate with a thin film may be manufactured.

[0108] For example, when forming a thin film using a remote plasma CVD apparatus, the reaction chamber is composed of a plasma generation space and a substrate processing space. After vaporizing the liquid precursor composition of the present invention, the vaporized gas is introduced into the substrate processing space via the plasma generation space, and a thin film is formed on the substrate in the substrate processing space. The following describes the details of an example of the process for the transfer and vaporization of the liquid precursor composition.

[0109] First, the liquid precursor is contained in a sealed supply container (sealed vessel), and the sealed container is heated to a predetermined temperature in order to increase the vapor pressure of the precursor. The heating temperature may be appropriately set according to the physical properties of the precursor, but generally, a range of 30°C to 100°C is preferred. A carrier gas (such as nitrogen or argon) is introduced into the sealed container, and the precursor is vaporized as the carrier gas passes through the liquid surface. When vaporizing the precursor, it is preferable to use reduced pressure conditions in order to increase the vapor pressure. More specifically, in order to sufficiently increase the vapor pressure, the upper limit of pressure should be 10 kPa or less, although 5 kPa or less is preferable, 3 kPa or less is even more preferable, and 1 kPa or less is particularly preferable.

[0110] The vaporized precursor is transferred from the sealed container to the reaction chamber of the remote plasma CVD apparatus via heated piping. At this time, the piping must be heated throughout its entire length in order to prevent recondensation of the vaporized gas. The heating temperature should be maintained above the boiling point of the precursor and within a range thatAtorney Docket No. 688243.0168 / 149WO prevents thermal decomposition, such as for example, in the range of 50°C to 150°C. As the heating means, heater tapejacket heater, or heating chamber may be used, and it is preferable to apply PID (Parameters from Proportional and Integral and Derivative) controllers for temperature control.

[0111] There are no particular restrictions on the method and apparatus for vaporizing the precursor as long as the precursor vapor may be stably supplied to the CVD or ALD apparatus (the chamber part in which the film deposition is performed) at an appropriate flow rate and vapor pressure. However, for industrial-scale production, it is preferable to use an injection-type vaporization system that may stably vaporize a sufficient amount of precursor. More specifically, the injection method refers to a continuous vaporization process that may be carried out using the following transfer and vaporization apparatus:

[0112] Liquid transfer apparatus: A system that continuously supplies the liquid precursor to the vaporization apparatus in a state in which the flow rate is appropriately controlled by a transfer device (suction and pressurization), flow meter, and flow control devices such as valves.

[0113] Vaporization apparatus: A device that introduces liquid into a chamber under the appropriate reduced pressure and / or heating conditions for vaporization of the liquid.

[0114] Gas transfer apparatus: A device that supplies the gas that was generated to the CVD or ALD apparatus at an appropriately controlled flow rate without re-liquefying the gas. In particular, in order to enhance industrial productivity and economics, and to obtain a higher concentration of precursor vapor, it is preferable to carry out these continuous injection-type vaporization operations without using diluent gases such as other carrier gases during vaporization.

[0115] More specifically, when no carrier gas is introduced into the composition when it is in a liquid state during evaporation during evaporation, it is necessary to conduct the evaporation operation under more severe conditions such as a higher temperature and higher vacuum compared to when a carrier gas is introduced. Because high concentrations of the precursor vapor are generated even after evaporation, it is preferable to use a precursor that boasts higher stability. Moreover, the risk of blockage due to precursor decomposition is higher when the precursor is continuously introduced into the vaporization device and the evaporation operation is continuously carried out under high temperature and high vacuum conditions without a carrier gas. In the injection method, any blockage or other trouble in the liquid transfer apparatus, vaporization apparatus, or gas transfer apparatus may become a major problem. Furthermore, for industrialAtorney Docket No. 688243.0168 / 149WO production using vaporization with the injection method, which requires strict productivity and operational stability, it is necessary to ensure that there is no blockage even after long-term operation without any accumulation of minute blockages, under a wide range of vaporization conditions (process window).

[0116] For example, stainless steel (such as SUS316L) that boasts excellent heat resistance and corrosion resistance may be used for the material of the piping. Furthermore, it is preferable to apply electrolytic polishing to the inside of the piping, which reduces the surface roughness and may to some extent inhibit the adsorption, decomposition, or formation of deposits of the precursor. Depending on the chemical properties of the precursor, it is also possible to apply an inner lining made of fluoropolymer such as polytetrafluoroethylene (PTFE).Pipeline blockage

[0117] In the above-noted transfer process, blockage may occur within the pipeline, which may significantly affect the stability of the film-forming process and the productivity of the substrate. Generally, the main causes of such blockage are as follows:

[0118] (1) The vaporized precursor may recondense in the pipeline due to a temperature drop, and may precipitate as droplets or a solid. In particular, if there is a region in which heating is insufficient in one part of the pipeline (a so-called cold spot), the precursor will condense in that region and deposits will accumulate over long-term operation, ultimately significantly reducing the cross-sectional area of the pipeline.

[0119] (2) If the precursor is overheated in the pipeline, thermal decomposition will proceed, and solid by-products (such as carbonaceous residue, metal oxide, or nitride, etc.) will be generated as decomposition products. These by-products are prone to adhere to the inner wall of the pipeline, and deposition will be promoted, especially in areas with low flow velocity, which causes blockage.

[0120] (3) During transportation, solid products may form when trace components (such as oxygen, water, acid, base, metal, or halogen, etc.) remaining in the carrier gas or piping react with the precursor. The reaction between these impurities and the precursor may be accelerated, especially under high temperature conditions, generating insoluble deposits within the piping.

[0121] (4) In some cases, a solid film may form when precursor molecules adsorb to the inner wall of the piping and become concentrated, polymerized, and precipitated due to long-term operation. In particular, when the roughness of the inner surface of the piping is significant or theAttorney Docket No. 688243.0168 / 149WO inner surface treatment is insufficient, adsorption is promoted, and the growth rate of the solid film increases.

[0122] (5) As a structural factor of the piping, in areas with bends, branches, or sudden changes in cross-sectional area, the flow velocity may locally decrease, forming areas where vaporized gas stagnates. In these stagnant areas, the condensation and reaction of the precursor may proceed locally, potentially becoming the initial growth point for deposits.

[0123] (6) If foreign substances are mixed into the supply system or carrier gas system, they may accumulate within the piping, causing blockages. In particular, this may be caused by filter degradation, poor maintenance, or the entrainment of sediment within the supply container.

[0124] As described above, the causes of piping blockages involve a combination of thermal, chemical, structural, and operational factors, and comprehensive control of these factors is essential for achieving a stable film-forming process. In a composition containing Silane compound 1, if Silane compound 2 and / or Silane compound 3 and / or Silane compound 5 are present in an amount exceeding a certain level, the above (3) is likely to occur, and furthermore, the mechanism leading to blockage by other factors is accelerated.Method for manufacturing thin film-coated substrates

[0125] The precursor that was transferred to the reaction chamber of a CVD or ALD apparatus according to the above-described method will form a thin film on the substrate under conditions such as plasma, heat, or reaction with other gases. In particular, plasma CVD (PECVD) and plasma ALD (PEALD) methods using plasma are preferably used to form high-performance insulating films with high productivity. Moreover, when forming a film, it is possible to form a higher performance film by combining the heating conditions and other reaction gas mixing conditions. The specific conditions for film formation are not particularly limited and may be established arbitrarily, depending on the scale and configuration of the apparatus, the desired film quality, and productivity. For example, in the case of a plasma CVD device for 4-inch substrates, the plasma output (W) should be at least 10 W, although 30 W or more is more preferable, and 50 W or more is even more preferable. The heating temperature of the chamber should be at least 20°C, although a temperature of 50°C is preferable, and 100°C or more is even more preferable. The upper limit should be 800°C or less, although 600°C or less is preferable, and 400°C or less is even more preferable. Although it is not necessary to use a reactive mixed gas other than the precursor, it is possible to form a higher performance film by using a mixed gas with oxygen or the like. Moreover,Attorney Docket No. 688243.0168 / 149WO under conditions of high power plasma, high temperature, and high reactivity gas, the reactivity of the precursor is expected to increase, and the film quality and productivity are expected to improve, but depending on the nature of the precursor that is used, the risk of blockage may increase. In particular, during industrial production in which there is an emphasis on productivity and film quality stability, it is preferable to be able to deposit a film continuously under stable conditions without causing blockages or other problems, even when the deposition conditions are varied to conditions that are prone to blockage.Evaluation of the reactivity of this composition

[0126] The alkoxy groups bonded to the silane atoms, which are the active sites in the silane compounds contained in this composition, will react with reactive species derived from reactive gases such as the oxygen within CVD (PECVD) or ALD equipment to form a partially cross-linked structure represented by Si-O-Si bonds. As a result, this composition functions suitably as an insulating film. On the other hand, as mentioned above, reactions with trace active species (such as oxygen or water, etc.) remaining in the carrier gas or in the piping could lead to solidification or adhesion within the pipework, eventually leading to blockage of the piping.

[0127] In this context, the reactivity of this composition with water (where the Si-alkoxy group decomposes to form a Si-OH group) is adopted as an indicator for a test method to model the reactivity of this composition with oxygen-derived reactive species. Therefore, the reactivity of this composition in CVD (PECVD) or ALD equipment may be reasonably assessed based on the degree of decomposition after mixing the composition with water.

[0128] More specifically, after mixing 1 mass part of this composition with 0.5 mass parts of water at room temperature and stirring for 15 minutes to produce a uniform solution, the mixture was then separated by gas chromatography, and the extent of the reaction was estimated from the chart area of the detector. In this case, the percentage of the total chart area of the reaction products with water, including silane atoms, divided by the total chart area of all of the compounds containing silane atoms, is defined as the decomposition rate and is used as an indicator of the reactivity.

[0129] From the viewpoint of obtaining sufficient reactivity in this composition and improving productivity during film formation, the degree of decomposition should be 0.05% or more, although 0.10% or more is even more preferable, 0.15% or more is even more preferable, 0.20% or more is even more preferable, and 0.25% or more is most preferred. On the other hand, in view of reducingAtorney Docket No. 688243.0168 / 149WO the risk of in-machine contamination, pipe internal adhesion, and even pipe blockage caused by side reactions occurring during the adhesion of the inner wall of deposition machines such as CVD machines, the decomposition rate should be 10% or less, although 5.0% or less is even more preferable, 1.0% or less is even more preferable, and 0.50% or less is most preferred. The lower and upper limits of the decomposition rate may be freely combined, such as 0.05 to 10%, 0.10 to 5.0%, 0.15 to 1.0%, 0.20 to 1.0%, or 0.25 to 0.50%.Evaluation of the stability of this composition under reduced pressure conditions

[0130] In relation to the above-noted reactivity evaluation, by evaluating the stability under reduced pressure, it is possible to evaluate the stability of this composition within equipment or containers for volatilization under reduced pressure, and within piping, valves, and CVD or ALD equipment. More specifically, it is possible to evaluate the stability of the liquid, in a state of changing from liquid state to the gas phase, and in the gas phase under reduced pressure, making it possible to conduct a relative evaluation of the risks such as solid deposition or blockage in piping. As a specific method, for example, it is possible to evaluate the stability by confirming the state of the apparatus or solution when mixing 1 mass part of this composition and 0.15 mass parts of water at 40°C and under reduced pressure of 0.5 kPa. If the stability of this composition is high, there is no deposition or adhesion of solids in the container or piping used for volatilization, whereas if the stability is low, there may be deposition or adhesion of solids in the container or piping used for volatilization. By comparing these conditions and times, it is possible to estimate the risk of blockage in places such as the vaporization apparatus, piping, valves, and CVD or ALD apparatus.Containers and sealed articles containing this composition

[0131] One embodiment of the present disclosure relates to an article in which the composition is contained within a sealed container having one or more pipes. It is preferable that the sealed container is made of metal. It is also preferable that the sealed container is a pressure vessel. It is more preferable that the sealed container is a metal pressure vessel.

[0132] This composition may be primarily used as a precursor in CVD and ALD equipment. Generally, the precursors used in these devices are supplied in liquid or gaseous form, and it is necessary to maintain stability and purity during the process. Therefore, dedicated sealed containers are used to properly store these substances in a sealed manner. Additionally, the junction betweenAtorney Docket No. 688243.0168 / 149WO the sealed container and the piping system for accurately transferring the precursor to the reaction device is also critical.

[0133] The above-mentioned sealed container is preferably configured to satisfy the following requirements:

[0134] (1) Chemical stability: The container should preferably be made of a material with high chemical resistance in order to prevent the precursor from reacting with the container material. For example, stainless steel or polymer materials may be used. Additionally, a special coating may be applied to the inner surface of the container in order to improve the chemical stability of the precursor.

[0135] (2) Sealing properties: The container must have a highly sealed structure to prevent leakage of the precursor and contamination from external substances. In particular, for liquid precursors with low vapor pressure, a design with members that minimize vapor leakage is preferred.

[0136] (3) Supply performance: In processes such as CVD and ALD, it is preferable for the container to have one or more pipes to ensure the stable and accurate supply of the precursor. Also, it is preferable to provide the appropriate valves or pipe junctions. An integrated design of the container and piping is preferable because it improves the efficiency of handling the precursor. By vaporizing the precursor through bubbling or baking, and then stably transferring the vaporized precursor to the reaction apparatus, it will be possible to uniformly and evenly deposit the precursor onto the substrate within the reaction apparatus.

[0137] (4) Safety: Because this involves the handling high-pressure gases or volatile liquids, it is preferable that the container is a pressure vessel designed to withstand pressure. Also, it is preferable for the container to be provided with a safety mechanism that envisions leakage or breakage.

[0138] The preferred design pressure for pressure vessels is between 5 MPa and 0.2 MPa, although 3 MPa to 0.8 MPa is preferable, and 2 MPa to 0.9 MPa is even more preferable. As for the volume of a general pressure vessel, it is preferably 10 L to 50 mL, although 5 L to 100 mL is preferable, and 3 L to 100 mL is even more preferable. As for the sealing properties of the pressure vessel required during depressurization (airtightness at vacuum and achievable vacuum degree as required by ASTM Standard D4991 or the like), it is preferable for it to be 10 torr or less, although 5 torr or less is preferable, 1 torr or less is even more preferable, and 0.1 torr or less is most preferable.Attorney Docket No. 688243.0168 / 149WO

[0139] Fig. 1 shows a longitudinal sectional view of the entire precursor container, which consists of container body 1 and lid body 2, as an example of a sealed container for accommodating the precursor composition of the present invention. Various components, such as liquid level sensor 3 (not shown in the fig) and liquid discharge piping 4 and liquid injection piping 5, are mounted on lid body 2. It is preferable for the multiple pipes and valves necessary for liquid injection, liquid discharge, gas insertion, and exhaust to be connected in this way. It is also preferable to replace the lid body with a lid body without holes for attaching various components when storing and transporting.

[0140] Although the precursor used in this embodiment needs to be heated to vaporize it, when the heating of the precursor is done using container body 1 itself, it is usually done by performing heating from the bottom of container body 1 using a heater or similar device. Therefore, it is preferable for this precursor container to have a structure that heats the bottom of container body 1 using a heat source, or for it to be used together with a heat source.

[0141] When transferring the precursor to the reaction apparatus side, if this precursor container is a bubbling container, a gas may be inserted from the outside to perform bubbling, which may cause the vapor pressure to decrease due to the loss of the heat of vaporization, or the supply amount may change due to changes in pressure. Therefore, by having at least the inner side wall be a vacuum insulation structure, it will be possible to minimize heat dissipation to the extent that is possible.

[0142] An outlet may also be provided at the very bottom of this precursor container. By providing an outlet, sufficient cleaning may be performed even if there is a remaining amount of precursor. Depending on the precursor used, there is a risk of scaling inside the container during cleaning. In such cases, it is preferable to clean the inside with an acidic aqueous solution containing nitric acid or hydrofluoric acid once every few cleaning operations. However, because there is a risk of metal leaching due to nitric acid or hydrofluoric acid, it is necessary to perform a final cleaning with ultrapure water (preferably with a resistivity equivalent to 18 MQ cm), and it is preferable to have an outlet at the bottom for this purpose. This outlet allows for the circulation of ultrapure water inside the container and prevents the container from dissolving due to overflow of the ultrapure water containing the acidic aqueous solution, as well as preventing re-contamination from external or surface metal contamination.

[0143] The material of container body 1 and lid body 2 may be stainless steel, for example, but for smooth finishing, an austenitic stainless steel, which is an iron-based alloy, is preferable. MoreAtorney Docket No. 688243.0168 / 149WO preferably, the material should be SUS 316 or SUS 304, and even more preferably, the material should be vacuum double-melted SUS 316L. Depending on the precursor, there may be a concern about reaction or corrosion with the metal constituting the container. To avoid this, it is preferable to perform electropolishing on the inner surface of the container (the part in contact with the silane compound). As a result, it will be possible to provide a sealed container that is optimal for use as the CVD or ADD precursor supply container, and that is capable of being heated, maintaining temperature, producing minimal chemical residues, cleaning without charging, and reuse.

[0144] Moreover, because there is a concern about metal leaching, especially with acidic aqueous solutions that may be used during cleaning, it is preferable to select SUS 316L, which is an austenitic stainless steel that has undergone vacuum double melting in order to minimize trace metal content, as the metal for the inner surface of container body 1 and lid body 2. In addition, it is preferable to minimize metal leaching by performing electrolytic polishing.EXAMPLES

[0145] The invention will be further illustrated by the following examples, but the invention is not limited to these examples unless it exceeds the scope of the invention. Here, the term “part” in the examples refers to the mass unless otherwise specified.

[0146] Silane compound 1 may be synthesized, for example, by the method described in U.S. Patent Application Publication No. 2009 / 0299086, and may be further distilled by the well-known method to obtain Silane compound 1 with a certain degree of purity. Silane compound 2 and Silane compound 3 are primarily obtained as by-products during the synthesis of Silane compound 1. On the other hand, Silane compound 2 may also be synthesized separately using the method described in U.S. Patent Application Publication No. 2009 / 0299086. Silane compound 3 may be procured from companies such as Angene or Arctom, for example, and may be further distilled by known methods as needed to obtain Silane compound 3 with a certain degree of purity. The composition obtained as one of the fractions during distillation, containing Silane compound 1 and Silane compound 2 and / or Silane compound 3, and the composition obtained by mixing the respective pure products of Silane compound 1, Silane compound 2, and / or Silane compound 3 are equivalent in terms of the reactivity evaluation of the present application if the mixing ratios are identical.of Embodiment 1-1Atorney Docket No. 688243.0168 / 149WO

[0147] Silane compound 1 A having formula (1 A) was synthesized using the above-mentioned well-known method, and after obtaining the crude product containing Silane compound 1 A, further distillation purification was performed using the method described below.

[0148] 190 g of the crude product of Silane compound 1 A was placed in a 500 mL flask and nitrogen gas replacement was performed. Then, using a precision distillation apparatus equipped with a distillation column, an automatic fractional head, and a reflux ratio timer, vacuum distillation was performed in order to separate the fractions into the forerun, the heart, and the still bottom while controlling the reflux ratio, and after removing the low-boiling-point portion, the heart was treated as Composition D-l.Distillation apparatusDistillation column: Kiriyama Seisakusho, KIRIYAMA PAC FR64-4-10 (distillation column with SUS316 irregular packing, 20 theoretical plates, inner diameter 25 MM x packing length 500 MM) Automatic fractional head: Kiriyama Seisakusho, FR66-5-1Distillation conditionsFrl (Forerun 1) 9.1 gAt the start: External temperature 98°C, internal temperature 88°C, top temperature 70°C, reflux ratio 3.0, pressure 1.0 kPaAt the end: External temperature 98°C, internal temperature 88°C, top temperature 71 °C, reflux ratio 3.0, pressure 1.0 kPaFr2 (Forerun 2) 26.1 gAt the start: External temperature 98°C, internal temperature 88°C, top temperature 71 °C, reflux ratio 0.5, pressure 1.0 kPaAt the end: External temperature 98°C, internal temperature 89°C, top temperature 71 °C, reflux ratio 0.5, pressure 1.0 kPaFr3 (Heart) 112. 1 gAt the start: External temperature 98°C, internal temperature 89°C, top temperature 71 °C, reflux ratio 0.5, pressure 1.0 kPaAt the end: External temperature 113°C, internal temperature 108°C, top temperature 71°C, reflux ratio 0.5, pressure 1.0 kPaAtorney Docket No. 688243.0168 / 149WO

[0149] The materials that were obtained were Frl (Forerun 1) as Composition E-l, Fr2 (Forerun 2) as Composition E-6, and Fr3 (Heart) as Composition D-l (Silane compound 1 A content:99.94%). Furthermore, the content of Silane compound 4A having formula (4A) within Composition D-l was 0.06%. Because Silane compound 4A was also present at a trace amount even when precise distillation was performed, it is presumed that it was generated due to the fact that the boiling point of Silane compound 4A is very close to that of Silane compound 1 A, making it difficult to separate them by distillation, or due to the decomposition of Silane compound 1 A during or after distillation.Me MeMsO ••••••• Si C H 2 ■■■■■■■ Si Ohte ( 1 A)OMe OMeMe Ms— -OH (4AJjOMe OMeEvaluation of the reactivity of the composition

[0150] Under a N2 atmosphere, a stir bar was placed in a 30 mL flask, and 1.0 g of Composition D-l and 0.50 g of deionized water were added. The mixture was stirred at 40°C for 15 minutes (at 600 rpm) in order to obtain a uniformly dissolved mixture. The resultant mixed solution was used to perform an analysis using the following method. Approximately 25 mg was sampled from the above-noted mixture, 2.5 mL of hexane was added, and the material was mixed to prepare the solution for analysis, which was performed using a gas chromatograph (GC) under the following analytical conditions. The detection limit for the GC analysis using this method is 0.01%, and if the corresponding compound peak is not detected, it is recorded as 0.00%. The compounds corresponding to each peak in the chart obtained by the FID detector were identified by separately analyzing their structure using a mass spectrometer or NMR, etc. The GC analysis conditions were as follows:Attorney Docket No. 688243.0168 / 149WOGC analysis conditionsGC apparatus: GC-2030 gas chromatograph, Shimadzu CorporationDetector: FID detector (attached to GC-2030)Column: Agilent DB-5, 30 m x 0.25 mm cp x 0.25 pmCarrier gas: 1 mL / min (helium)GC temperature: 40°C (2 min, hold) — 40°C to 300°C (13 min, heating rate 20°C / min) — 300°C (2 min, hold)Injection volume: 1 pLInjection temperature: 200°CFID detector temperature: 250°CSplit ratio: 1 / 50

[0151] As a result of quantifying the decomposition products, the decomposition rate, which is an indicator of the reactivity of Composition D-l, was 0.44%, as shown in Table 1 in Fig. 4.Example of Embodiment 1-2

[0152] Silane compound 1 A that was manufactured in Example 1 and Silane compound 3 A having formula (3 A) with a catalog- stated purity of 98%, which was procured from Angene, were uniformly mixed such that the area ratio of the peaks in the gas chromatography was 99.50:0.50, resulting in Composition D-2.

[0153] As a result of conducting a reactivity evaluation on Composition D-2 in the same manner as Example of Embodiment 1-1, the decomposition rate, which is an indicator of the reactivity of Composition D-2, was determined to be 0.53%, as shown in Table 1.Me MeMeO —Si — O— Si — OMe (3 A)OMe OMeComparative Example 1-1

[0154] Silane compound 1 A described above and Silane compound 2 A having formula (2 A) were uniformly mixed such that the area ratio of the peaks in the gas chromatography was 99.Attorney Docket No. 688243.0168 / 149WO 50:0.50, resulting in Composition E-l. As a result of a detailed analysis, Composition-1 was determined to contain Silane compound 4A, and the actual ratio of the components was Silane compound 1 A: Silane compound 2A: Silane compound 4A = 99.46:0.50:0.04. The details of the cause of the decrease in Silane compound 4A before and after mixing are unclear, but it is presumed that decomposition of Silane compound 4A may be a factor.

[0155] The decomposition rate of Composition E-l, which was evaluated in the same manner as described in Example of embodiment 1-1, was 20%, as shown in Table 1.Me MeMeO*~ Si"™ CH g” Si” Me (2 A)OMe OMeComparative Example 1-2

[0156] Silane compound 1 A described above, Silane compound 2A, and Silane compound 3A having formula (3 A) with a catalog- stated purity of 98%, which was obtained from Angene, were uniformly mixed such that the area ratio of the peaks in the gas chromatography was 99.75:0.13:0.12, resulting in Composition E-2. The FID chart of Composition E-2 before evaluating its reactivity is shown in Fig. 2. The details of the cause of the decrease in Silane compound 4A before and after mixing are unclear, but it is presumed that decomposition of Silane compound 4A during mixing may be a factor.Ms MGMsO — S i — O — Si — OMe 3 A )OMe OMe

[0157] The decomposition rate of Composition E-2, which was evaluated in the same manner as described in Example of embodiment 1-1, was 20%, as shown in Table 1.

[0158] The FID chart of Composition E-2 after evaluating its reactivity is shown in Fig. 3. The detection times for each silane compound were as follows: Silane compound 1 A: 7.52 minutes, Silane compound 2A: 6.92 minutes, Silane compound 3 A: 6.48 minutes, hydrolysis product of Silane compound 1: 7.38 minutes. In Figs 2 and 3, the major peaks are scaled out (saturated) due toAtorney Docket No. 688243.0168 / 149WO the increased magnification in order to make the minor peaks easier to discern. However, the area ratio was calculated under conditions in which the major peaks were not scaled out.Comparative Example 1-3

[0159] Composition E-3 was obtained as Frl, which represents the first half of the forerun during distillation in the Example of Embodiment 1-1. Composition E-3 contained Silane compound 1 A, Silane compound 2A, Silane compound 3A, and Silane compound 4A. The peak area ratio of Composition E-3 in the gas chromatography was Silane compound 1 A: Silane compound 2A: Silane compound 3A: Silane compound 4A = 95.54:1.84:1.87:0.11.

[0160] The decomposition rate of Composition E-3, which was evaluated in the same manner as described in Example of Embodiment 1-1, was 45%, as shown in Table 1.Comparative Example 1-4

[0161] The above-noted Silane compound 1 A, Silane compound 2A, and Silane compound 3A were uniformly mixed such that the area ratio of the peaks in gas chromatography was 96.24:2.28:1.48, resulting in Composition E-4. As a result of a detailed analysis, the actual content ratio was as shown in Table 1. The details of the cause of the decrease in Silane compound 4A before and after mixing are unclear, but it is presumed that decomposition of Silane compound 4A during mixing may be a factor. The decomposition rate of Composition E-4, which was evaluated in the same manner as described in Example of embodiment 1-1, was 70%, as shown in Table 1.Comparative Example 1-5

[0162] The above-noted Silane compound 1 A, Silane compound 2A, and Silane compound 3A were uniformly mixed such that the area ratio of the peaks in gas chromatography was 93.62:3.07:3.31, resulting in Composition E-5. As a result of a detailed analysis, the actual content ratio was as shown in Table 1. The details of the cause of the decrease in Silane compound 4A before and after mixing are unclear, but it is presumed that decomposition of Silane compound 4A during mixing may be a factor.

[0163] The decomposition rate of Composition E-5, which was evaluated in the same manner as described in Example of embodiment 1-1, was 95%, as shown in Table 1.Attorney Docket No. 688243.0168 / 149WO Comparative Example 1-6

[0164] Composition D-l that was used in the Example of Embodiment 1-1 was stored under the following conditions for 6 months in order to obtain Composition E-6.

[0165] Storage conditions: 10 g of Composition D-l was placed into a 50 mL vial (Maruemu Corporation, 50 mL brown screw-top vial, material: brown glass, cap: PP) and stored at 15°C to 30°C without nitrogen gas sealing. During the 6-month storage period, the cap was opened and closed more than 5 times within the atmosphere.

[0166] As a result of analyzing the resultant Composition E-6 using gas chromatography, it was found that it contained Silane compound 1 A, Silane compound 4 A, and Silane compound 5 A having formula (5 A). Silane compound 1 A: Silane compound 4A: Silane compound 5A = 99.49:0.11:0.30.

[0167] The decomposition rate of Composition E-6, which was evaluated in the same manner as described in the Example of Embodiment 1-1, was 31%, as shown in Table 1. (0134)Me Me Me MBI £MeQ •-■■■ Si— CHg— OMfe (5A)OMe OMe OMe OMeComparative Example 1-7

[0168] Trimethylchlorosilane (TMSC1) was added to Composition E-6 that was obtained in Example of embodiment 1-6 in order to obtain Composition E-7 with a chlorine atom content of 10 ppm (converted to the Cl mass relative to the total mass).

[0169] The decomposition rate of Composition E-7, which was evaluated in the same manner as described for Composition D-l in Example of embodiment 1-1, was 100%, and precipitation of solids was observed. The results are shown in Table 3.

[0170] As shown in the Examples of Embodiment 1-1 and 1-2 in Table 1, for the compositions containing Silane compound 1 with a very high degree of purity and having a lower content of Silane compound 2 and / or Silane compound 3 and / or Silane compound 5 than the predetermined amount, the decomposition rate falls within a range of 1% or less, and it is believed that excessiveAtorney Docket No. 688243.0168 / 149WO reactivity to unintended reactive species in the CVD apparatus was suppressed, resulting in high stability.

[0171] The compositions of Comparative Examples 1-1 to 1-5, which have a higher content of Silane compound 2 and / or Silane compound 3 than the predetermined amount, have a high decomposition rate and may be said to have low stability in relation to unintended reactive species.

[0172] The presence of Silane compound 4 does not affect the decomposition rate if it is present in a certain amount or less.

[0173] As seen in Comparative Example 1-6, when a certain amount of Silane compound 5 is present, the decomposition rate increases.Analysis of the metal content

[0174] After adding sulfuric acid to approximately 0.35 g of Composition D-l, dry ashing was carried out using an IR furnace. Next, hydrofluoric acid was added, the material was evaporated and dried, and the residue was dissolved in dilute hydrochloric acid in order to bring the total volume up to the desired value. The metal content of Composition D-l was measured by analyzing the solution using ICP mass spectrometry (ICP-MASS method). The results are shown in Table 2.EquipmentICP-MASS analysis device: ELEMENT2, ThermoFisher ScientificDetection limit: For each element listed in Table 2, 10 mass ppb (0.01 pg / g)Attorney Docket No. 688243.0168 / 149WOTable 2: Analysis of the Metal Element Content of Composition D-lAnalysis results (massMetal PPb)Ag < 10Al < 10Au < 10Ba < 10Ca < 10Cd < 10Co < 10Cr < 10Cu < 10Fe < 10Hf < 10In < 10K < 10Li < 10Mg < 10Mn < 10Na < 10Ni < 10Pb < 10Sn < 10Ti < 10V < 10w < 10Zn < 10Measurement of the halogen content

[0175] The halogen content of Composition D-l, Composition E-6, and Composition E-7 was quantified by the following method. The results are shown in Table 3.Atorney Docket No. 688243.0168 / 149WO Pretreatment

[0176] Approximately 20 to 30 mg of the sample and approximately 0.1 g of WO3 were placed on a magnetic boat for combustion absorption, the material was combusted in a combustion absorption apparatus, and the generated gas was absorbed in approximately 10 to 15 mL of absorption liquid. The absorption liquid was quantified by separating it into F’, CF, Br, and T using the Anion-IC device described below.Method for measuring the F contentIC separation column: AS 15Eluting solvent: 20 mM NaOHEluting solvent flow rate: 1. 0 mL / minDetection mode: Electrical conductivitySuppressor: Dionex ADRS 600 (External mode)Input volume: 100 pL (using an autosampler)Method for measuring the Cl and Br contentIC separation column: AS12AEluting solvent: Na2COs 2. 7 mM, NaHCCh 0.3 mMEluting solvent flow rate: 1. 5 mL / minDetection mode: Electrical conductivitySuppressor: Dionex ADRS 600 (recycle mode)Input volume: 100 pL (using an autosampler)Method for measuring the I contentIC separation column: AS20Eluting solvent: 20 mM NaOHEluting solvent flow rate: 1. 0 mL / minDetection mode: Electrical conductivitySuppressor: Dionex ADRS 600 (External mode)Input volume: 100 pL (using an autosampler)Attorney Docket No. 688243.0168 / 149WOEquipmentCombustion absorption system: NittoSeiko Analytech, AQF-2100HIC: Thermo Fisher Scientific, ICS6000 and ICS1600Table 3: Summary of Metal Element ContentsF Cl Br I Decomposition rate Element(Mass ppm) (Mass ppm) (Mass ppm) (Mass ppm) (%)D-l <0.3 <3 3 <2 0.44E-6 <0.4 1.1 <3 <2 31E-7 <0.4 9.9 <3 <2 100

[0177] As shown in Table 2, the metal content was 10 mass ppb or less for all of the metal elements. The inequality sign (<) indicates that the value is below the detection limit.

[0178] As shown in Table 3, the halogen atom (F, Cl, Br, I) content of Composition D-l and Composition E-6 was 10 mass ppm (10 pg / g) or less. The inequality sign (<) indicates that the value is below the detection limit. In particular, Cl atoms, which are a concern due to potential contamination from raw materials, equipment, containers, or the environment, was found to be present at an extremely low content.

[0179] In this way, it was found that this composition boasts favorably low reactivity while achieving the extremely low content of metal elements and halogen atoms that is required for semiconductor materials.

[0180] On the other hand, in Composition E-7, to which trimethyl silyl chloride (TMSC1) was added as a model experiment, the decomposition rate increased from 31% to 100% when compared to Composition E-6. Based on these results, it may be inferred that the presence of a certain amount of chlorine derived from the Si-Cl bond causes decomposition to accelerate further, leading to solidification and problems such as piping blockage.Attorney Docket No. 688243.0168 / 149WO Stability test under reduced pressure conditionsExample of Embodiment 2-1- Composition D-l

[0181] A study was conducted under reduced pressure conditions using an oil bath, a 30 mL recovery flask, a cooling tube (distillation path), a vacuum trap, and a vacuum oil pump. 1.0 g of Composition D-l from the Example of Embodiment 1-1 and 0.15 g of deionized water were added to the 30 mL recovery flask. A stir bar for a magnetic stirrer was placed in the flask, and a cooling tube (cooled to 25°C with cooling water) was connected on top, after which the flask was purged with nitrogen. The solution portion of the flask was immersed in an oil bath at 40°C, and the mixture was stirred for 5 minutes (at 200 rpm) using the magnetic stirrer to ensure uniform dissolution. Then, while continuing to stir, the vacuum oil pump was used to reduce the pressure down to 0.5 kPa over approximately 1 minute, taking care not to cause sudden boiling. This state of reduced pressure to 0.5 kPa was maintained for 1 hour while continuing to stir the solution. The state of the solution and the apparatus was observed visually after the elapse of 1 hour. As a result, no solid precipitation or adhesion was observed in the solution or on the inner walls of the container (recovery flask, cooling tube), and the solution maintained its transparent state.Comparative Example 2-1- Composition E-l

[0182] Other than using Composition E-l of Comparative Example 1-1 instead of Composition D-l, the stability test under reduced pressure was carried out in the same manner was described in Example of embodiment 2-1. As a result, white to translucent solids precipitated from the solution, and similar solids adhered to the walls of the cooling tube, which was the part of the recovery flask that was not in contact with the stirred solution (corresponding to the gas phase portion).Comparative Example 2-6- Composition E-6

[0183] Other than using Composition E-6 of Comparative Example 1-6 instead of Composition D-l, the stability test under reduced pressure was carried out in the same manner was described in Example of embodiment 2-1. As a result, white to translucent solids precipitated from the solution, and similar solids adhered to the walls of the cooling tube, which was the part of the recovery flask that was not in contact with the stirred solution (corresponding to the gas phase portion). The amount of adhesion was less than that observed in Comparative Example 2-1.Atorney Docket No. 688243.0168 / 149WO

[0184] The sample from the Example of Embodiment 2-1 had high stability under the abovenoted reduced pressure conditions (equivalent to evaporation conditions in CVD), and no solids precipitated in the solution, the container, or the distillation path. On the other hand, the samples from Comparative example 2-1 and Comparative example 2-6 showed the precipitation of solids due to decomposition under the above-noted reduced pressure conditions, and solids adhered to the walls of the container and the distillation path (equivalent to the piping section in CVD). From this, it is inferred that the stability of these compositions is insufficient.Example of Embodiment 3-1

[0185] Composition D-l was used to fill a sealed container made of SUS 316 with two valves, under a nitrogen atmosphere, and the two valves were closed to seal the container. Container details: SUS container for CVD, SAMCO, TR3017S-3, capacity: 200 mL, hermetic seal (ultimate vacuum): 0.1 torr or less, pressure resistance (design pressure): 0.98 MPa, cleaned with acetone and ultrapure water prior to filling.

[0186] When using Composition D-l in the container to form a film using the plasma CVD method described below, it was possible to obtain an insulating film at a constant and easily controllable film formation rate (approximately 200 nm / 1 min). It was possible to vaporize and transport the precursor stably without introducing a carrier gas during vaporization, and no blockage of the piping was observed.Method of film formation using the CVD methodSubstrate: 3-inch P-type silicon waferCVD equipment: SAMCO, PD-10C1 liquid source plasma CVD equipmentCylinder temperature: 80°CFlow path temperature: 80°CVacuum level: 100 PaCarrier gas introduced into the precursor liquid: None. The evaporation operation was conducted without introducing or bubbling a carrier gasCarrier gas: Ar, flow rate 40 seem, mixed after evaporationChamber temperature: 200°CPlasma conditions: 75W, 13. 56 MHzFilm deposition time: 1 minAttorney Docket No. 688243.0168 / 149WOExample of Embodiment 3-2

[0187] The deposition conditions in the Example of embodiment 3-1 were changed by altering the plasma power from 75 W to 125 W in order to perform film deposition. An insulating film was obtained, and no blockage of the piping was observed.Example of Embodiment 3-3

[0188] The deposition conditions in the Example of Embodiment 3-1 were changed by altering the chamber temperature from 200°C to 300°C in order to perform film deposition. An insulating film was obtained, and no blockage of the piping was observed.Example of Embodiment 3-4

[0189] The deposition conditions in the Example of Embodiment 3-1 were modified by changing the carrier gas from Ar: flow rate 40 seem to a mixed gas of Ar: flow rate 40 seem and O2: flow rate 10 seem, after which film deposition was performed. An insulating film was obtained, and no blockage of the piping was observed.Comparative Example 3-1

[0190] When Composition E-2 that was obtained in Comparative Example 1-2 was used under the same conditions as described in the Example of Embodiment 3-1 to perform CVD film deposition, a good insulating film was obtained at a fast film deposition rate.

[0191] On the other hand, it is speculated that the blockage of the piping may be observed more frequently. This tendency is speculated to become more pronounced as the scale of the film formation apparatus becomes larger and the piping becomes longer. It is also speculated that this tendency will become more pronounced as the flow rate is increased in hopes of improving productivity, the temperature is increased, or the film formation time becomes longer as the film formation conditions that are used.Evaluation of the FilmExample of Embodiment 4-1The films obtained in the Examples of Embodiments 3-1 to 3-4 were evaluated using the followingAttorney Docket No. 688243.0168 / 149WO methods, and the results are shown in Table 4 in Fig. 5.Measurement of film thicknessMeasurement method: The film thickness was measured by performing a fitting analysis using a spectroscopic ellipsometer.Equipment: Spectroscopic ellipsometer (J. A. Woollam Inc., M2000XMeasurement wavelength: (245 to 1000 nm)Incidence angle: 68 to 75° (0.5° increments)Analysis method: The n-Cauchy model was used as a dielectric function, and a fitting analysis was performed in order to calculate the film thickness.Number of measurement points: Five points were measured from the inside to the periphery of the wafer, and the average value was taken as the film thickness. In addition, the in-plane uniformity of the film thickness (%) was calculated as {(film thickness of the point that deviated the most from the average value (nm) - average film thickness (nm)) / (average film thickness (nm)) x 100}. As a result, all of the above-noted values fell within a range of plus or minus 5% in all of the examples.Measurement of the elemental compositionMeasurement method: The elemental composition (atom%) of Si, C, and O was measured using X-ray photoelectron spectroscopy (XPS: X-ray Photoelectron Spectroscopy).Instrument: KRATOS ULTRA2X-ray source: Monochromatic Al-KaOutput: Wide spectrum: 15 kV to 75 W (5 mA), Narrow spectrum: 15 kV to 225 W (15 mA) Spectral system: Pass energy Wide spectrum: 160 eV, Narrow spectrum: 10 eVAnalysis method: Peaks corresponding to C Is, O Is, Si 2p were analyzed, and the composition (atom%) of Si, C, and O was calculated. In all of the examples of embodiment, Si, C, and O elements corresponding to the composition of the precursor that was used were detected.Measurement of the hardness and complex elastic modulusMeasurement method: The hardness (GPa) and complex elastic modulus (GPa) were measured using a nanoindenter.Instrument: Bruker TI980Atorney Docket No. 688243.0168 / 149WO Plunger: The plunger atached to the instrument (manufacturer’s number: TI-0039), Material: diamond, Shape: BerkovichMeasurement conditions: Load: 5 seconds, Hold: 2 seconds, Load release: 5 seconds, Lift height: 50 nm, Set point: 0.5 pN

[0192] In the above-noted examples of embodiment, specific forms of the present invention have been shown, but the above-noted examples are merely illustrative and should not be construed as limiting. Various modifications that are obvious to those skilled in the art may be envisioned to be within the scope of the present invention.

Claims

Attorney Docket No. 688243.0168 / 149WO CLAIMSWe claim:

1. A composition comprising a silane compound 1 having formula (1), wherein, as calculated from area percentages in gas chromatography, a content of the silane compound 1 is 99.0% or higher, a content of a silane compound 2 having formula (2) is less than 0.05%, a content of a silane compound 3 having formula (3) is less than 0.80%, and a content of a silane compound 5 having formula (5) is less than 0.05%:(R3)bI c !Si - R - Si(OR2)3-a (OR4kb(i)wherein R1to R4represent the same or different hydrocarbon groups having 1 to 10 carbon atoms, a and b represent the same or different integers of 0 to 3, a + b is an integer of 5 or less, and R5represents a hydrocarbon group having 1 to 6 carbon atoms;wherein c and d represent the same or different integers of 0 to 3, the sum of c and d is greater than the sum of a and b in formula (1);Si - O - Si(OR7)3-a’ (OR9)3-b’(3)wherein R6to R9represent the same or different hydrocarbon groups having 1 to 10 carbon atoms, and a’ and b’ represent the same or different integers from 0 to 3;Attorney Docket No. 688243.0168 / 149WO (R15)g(R17)b (R20)m(R22)nS j - p 19 - g j - o Si - R24- Si(OR’% (OR,8)2.h(OR21)2.m(OR23)3.„wherein R15to R18and R20to R23represent the same or different hydrocarbon groups having 1 to 10 carbon atoms, g and n represent the same or different integers of 0 to 3, h and m represent the same or different integers of 0 to 2, and R19and R24represent the same or different hydrocarbon groups having 1 to 6 carbon atoms.

2. The composition of claim 1, wherein the content of the silane compound 3 is less than 0.05%.

3. The composition of claim 1, wherein the content of the silane compound 2 is less than 0.01%.

4. The composition of claim 1, further comprising a silane compound 4 having formula (4), wherein a content of the silane compound 4, as calculated from an area percentage in gas chromatography, is greater than 0% and 0.30% or less:(R1°)e (R12)fg i - p 14 - g j Q |_|(OR%.e(OR13)2.f (4)wherein R10to R13represent the same or different hydrocarbon groups having 1 to 10 carbon atoms, e is an integer of 0 to 3, f is an integer of 0 to 2, and R14represents a hydrocarbon group having 1 to 6 carbon atoms.

5. The composition of claim 1, wherein a metal content is 30 mass ppb or less for each metal element.Atorney Docket No. 688243.0168 / 149WO 6. The composition of claim 1, wherein a halogen content is 10 mass ppm or less for each halogen atom.

7. The composition of claim 1, wherein the composition is substantially free of solvent.

8. A method for manufacturing a thin film, comprising forming a thin film by chemical vapor deposition (CVD) or atomic layer deposition (ALD) using the composition of claim 1.

9. A method for manufacturing a thin film, comprising spin coating a thin film using the composition of claim 1.

10. A transfer method comprising vaporizing the composition according to claim 1 andtransporting the vaporized composition through a pipeline.

11. An article containing the composition of claim 1 in a sealed container having one or more pipelines.

12. The article of claim 11, wherein the sealed container is a metal pressure vessel.

13. A method for manufacturing a thin film on a substrate, comprising vaporizing the composition of claim 1, introducing the vaporized composition into a reaction chamber, and forming a thin film on a substrate in the reaction chamber using the vaporized composition.

14. The method for manufacturing of claim 13, wherein the composition is vaporized by an injection method.

15. The method for manufacturing of claim 13 or 14, wherein the composition is vaporized without introducing a carrier gas into the composition.

16. A thin film on a substrate obtained by the manufacturing method of claim 13.Atorney Docket No. 688243.0168 / 149WO 17. The thin film on a substrate of claim 16, wherein an in-plane uniformity is within ±5% and a hardness is 1 GPa or more.

18. The method for manufacturing a thin film of claim 8, wherein an in-plane uniformity of the thin film is within ±5% and a hardness is 1 GPa or more.

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