Compositions comprising 1, 1, 1, 4, 4, 4-hexafluoro-2-butyne

Abstract

The present disclosure relates to compositions comprising 1, 1, 1, 4, 4, 4-hexafluoro-2-butyne, which can be used as reaction intermediates, cleaning agents, and etching gases.

Description

Technical Field

[0001] This invention relates to compositions comprising fluorobutyne, particularly hexafluoro-2-butyne. These compositions, for example, provide improved results in etching compositions and as reaction intermediates. Background Technology

[0002] Increased public awareness of the environmental impacts of fossil fuel extraction, transportation, and use is driving new forms of environmental sustainability through regulations and reductions in atmospheric CO2 equivalent emissions. In particular, new environmental regulations for refrigerants have compelled the refrigeration and air conditioning industry to seek new refrigerants with low global warming potential (GWP). For both existing and new applications in thermal management (such as refrigerants and cleaning / etching applications), alternative compounds and compositions with low GWP and ozone depletion potential (ODP) will need to comply with these new regulations.

[0003] Hexafluoro-2-butyne was also disclosed as an intermediate in the production of Z-1,1,1,4,4,4-hexafluoro-2-butene (HFO-Z-1336mzz or more simply, 1336mzzZ). Z-1,1,1,4,4,4-hexafluoro-2-butene can be used as a refrigerant, heat transfer fluid, foam expander, power circulation working fluid, and other applications. It was also advantageously found that 1336mzzZ has a low global warming potential (GWP) of 32.

[0004] Methods for preparing 1336mzzZ are disclosed, for example, in WO 2015 / 120250 A1, WO2014 / 052695 A1, US2013 / 0158304 A1, CN 103193586, CN 106008147, and CN106966856 (Seabisker case, red). For example, WO 2015 / 120250 A1 discloses that 1336mzzZ can be prepared starting from CFC-113a (1,1,1-trichloro-2,2,2-trifluoroethane). For example, US2013 / 0158304 A1 discloses that 1336mzzZ can be prepared starting from hexachlorobutadiene (CCl2=CCl-Cl=CCl2). Both methods produce hexafluoro-2-butyne as an intermediate.

[0005] Hexafluoro-2-butyne has been disclosed for use in compositions for etching and cleaning applications, such as in US2002 / 0197761. Advantageously, hexafluoro-2-butyne has been found to have a low global warming potential (GWP) of 2.

[0006] It has been found that the hexafluoro-2-butyne produced in the methods disclosed above contains compounds that adversely affect the performance of downstream methods and equipment in the manufacture of 1336mzzZ, as well as in etching and cleaning applications. In particular, when hexafluoro-2-butyne is used as an intermediate in the manufacture of 1336mzzZ, chlorinated compounds can generate HCl. Furthermore, chlorinated compounds can cause undesirable substrate degradation in cleaning and etching applications because they can be more corrosive than hexafluoro-2-butyne.

[0007] This invention solves these problems. Summary of the Invention

[0008] It has been found that the compositions containing hexafluoro-2-butyne disclosed herein provide improved results regarding the use of such compositions in the manufacture of 1336mzzZ and improved performance in etching and cleaning applications.

[0009] In one embodiment of the invention, a composition is provided comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123, and 1122 in a total not exceeding 0.5% (mol%). The composition comprising hexafluoro-2-butyne may comprise one or more of 113, 122, 123, and 1122 in a total not exceeding 0.2%, or not exceeding 0.1%, or not exceeding 0.05%, or not exceeding 0.01%. The composition may comprise PFBY and 113. The composition may comprise PFBY and 122. The composition may comprise PFBY and 123. The composition may comprise PFBY and 1122.

[0010] In one embodiment, the composition further comprises one or more additional compounds selected from the group consisting of HFC-23, HFC-41, HCFC-132b, HCFC-142b, HFC-143a, HFC-152a, trifluoropropyne, HFC-263fb, HFC-356mff, HCFO-1122, HCFO-Z-1326mxz, HCFO-E-1326mxz, HFO-1327mz, HFO-E-1336mzz, and trifluoroacetone. The one or more additional compounds may be present in an amount not exceeding 0.5%, 0.1%, or 0.01%.

[0011] Compositions containing hexafluoro-2-butyne (PFBY) contain at least 95% PFBY, or at least 98% PFBY, or at least 99% PFBY, or at least 99.5% PFBY, and preferably more than 99.8% PFBY.

[0012] In one embodiment, the composition provided herein can be used as an intermediate in chemical processes, such as for the production of Z-HFO-1336mzz (Z-1,1,1,4,4,4-hexafluoro-2-butene-Z, 1336mzzZ, or Z-CF3CH=CHCF3). The method involves contacting a composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123, and 1122 in total not exceeding 0.5% (mol%) with hydrogen to produce Z-CF3CH=CHCF3. Due to the low concentrations of components 113, 122, 123, and 1122 in PFBY, the method for producing Z-CF3CH=CHCF3 is more efficient, resulting in higher yields, less corrosion, and improved catalyst lifetime.

[0013] In one embodiment, the compositions provided herein can be used for cleaning and etching applications.

[0014] In one embodiment, a gas mixture suitable for etching is provided, the gas mixture comprising oxygen and a composition comprising one or more of 1,1,1,4,4,4-hexafluoro-2-butyne and 113, 122, 123 and 1122 in total not more than 0.5%, preferably not more than 0.2%, more preferably not more than 0.1%, even more preferably not more than 0.05%, and even more preferably not more than 0.01%. The composition containing 1,1,1,4,4,4-hexafluoro-2-butyne and not more than 0.5% preferably contains at least 99% 1,1,1,4,4,4-hexafluoro-2-butyne, more preferably at least 99.5% 1,1,1,4,4,4-hexafluoro-2-butyne, even more preferably at least 99.8% 1,1,1,4,4,4-hexafluoro-2-butyne, and most preferably at least 99.9% 1,1,1,4,4,4-hexafluoro-2-butyne.

[0015] In one embodiment, a gas mixture suitable for etching is provided, the gas mixture comprising oxygen and a composition comprising at least 99.8% of 1,1,1,4,4,4-hexafluoro-2-butyne and a total of no more than 0.2% of one or more of 113, 122, 123, and 1122. In one embodiment, a gas mixture suitable for etching is provided, the gas mixture comprising oxygen and a composition comprising at least 99.9% of 1,1,1,4,4,4-hexafluoro-2-butyne and a total of no more than 0.1% of one or more of 113, 122, 123, and 1122. In one embodiment, a gas mixture suitable for etching is provided, the gas mixture comprising oxygen and a composition comprising at least 99.9% of 1,1,1,4,4,4-hexafluoro-2-butyne and a total of no more than 0.1% of one or more of 113, 122, 123, and 1122.

[0016] In one embodiment, the etching gas mixture further comprises a carrier gas. The carrier gas may be selected from He, Ar, or N2. In one embodiment, the molar ratio of oxygen to the composition comprising PFBY is at least about 1:1.

[0017] In one embodiment, the etching gas mixture further comprises a second etching gas, wherein the second etching gas is a fluorinated compound, SF6, or NF3. In one embodiment, the second etching gas is selected from the group consisting of tetrafluoromethane, hexafluoroethane, octafluoropropane, perfluorotetrahydrofuran, hexafluorobutadiene, and octafluorocyclobutane.

[0018] In one embodiment, a method of operating a semiconductor manufacturing processing chamber is provided, the method comprising etching a film on a semiconductor using an etching gas mixture comprising oxygen and a composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne and one or more of 113, 122, 123 and 1122 in total not exceeding 0.5%.

[0019] In one embodiment, the method of operating a semiconductor manufacturing processing chamber, the step of etching a film further includes transferring a photomask to a semiconductor to create a masking surface and an exposed surface; forming a plasma of the etching gas mixture; and exposing the exposed surface of the semiconductor to the plasma to remove a portion of the exposed surface of the semiconductor to form an etched surface of the semiconductor.

[0020] In one embodiment, the method of operating a semiconductor manufacturing processing chamber further includes the steps of: forming a second etching gas; activating the second etching gas to form a second plasma; and depositing the second plasma on the etching surface to form a polymer layer on the etched surface of the semiconductor, wherein the second etching gas is a fluorinated compound, SF6, or NF3.

[0021] The surface deposits can be selected from the group consisting of: silicon oxide, gallium nitride, silicon nitride, silicon oxynitride, silicon carbonitride, tungsten nitride, titanium nitride, and tantalum nitride.

[0022] In one embodiment, the step of forming plasma by etching gas is performed in a remote chamber or in a processing chamber.

[0023] In one embodiment, the molar ratio of oxygen to the composition containing PFBY is at least about 1:1.

[0024] In any embodiment of the method of operating a semiconductor manufacturing processing chamber, the pressure in the processing chamber does not exceed 30 Torr.

[0025] In one embodiment of any method in the operation of a semiconductor manufacturing processing chamber, the pressure in the remote chamber is from 0.5 Torr to 50 Torr.

[0026] In one embodiment, a method for removing surface deposits from a surface in a processing chamber is provided, the method comprising: activating a gas mixture comprising oxygen and a composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne and one or more of 113, 122, 123, and 1122 in total not exceeding 0.5%, wherein the molar percentage of PFBY in the gas mixture is from about 5% to about 99%; and contacting the activated gas mixture with the surface deposits, thereby removing at least some of the deposits. In one embodiment, the processing chamber is the interior of a deposition chamber for manufacturing electronic devices. Detailed Implementation

[0027] As used herein, the terms “comprising,” “including,” “having,” or any other variations thereof are intended to cover non-exclusive inclusion. For example, a composition, process, method, article of manufacture, or apparatus that includes a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such composition, process, method, article of manufacture, or apparatus. Furthermore, unless expressly stated otherwise, “or” refers to an inclusive or non-exclusive or. For example, conditions A or B satisfy one of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0028] The transitional phrase "composed of..." does not include any unspecified elements, steps, or components. If in a claim, it will not include protection for materials other than those described, except for impurities typically associated with them. When the phrase "composed of..." appears in a clause of the body of a claim, rather than immediately following the preamble, it only limits the elements described in that clause; other elements as a whole are not excluded from the claim.

[0029] The transitional phrase "consistently composed of..." is used to define compositions or methods that include materials, steps, features, components, or elements in addition to those disclosed in the literature, provided that these additionally included materials, steps, features, components, or elements do not significantly affect one or more essential and novel features of the invention protected by the claims, particularly the mode of action for achieving the desired results of any of the methods of the invention. The term "consistently composed of..." occupies an intermediate position between "comprising" and "composed of...".

[0030] Where the applicant has defined the invention or a part thereof using open-ended terms such as “comprising”, it should be readily understood (unless otherwise stated) that the description should be interpreted as also including inventions using terms such as “substantially composed of” or “composed of”.

[0031] Furthermore, the terms "an" or "a" are used to describe the elements and components described herein. This is for convenience only and to give a general meaning to the scope of the invention. This description should be understood to include one or at least one, and the singular includes the plural, unless it is obvious that it means otherwise.

[0032] As used herein, the term “about” is intended to account for variations due to experimental error (e.g., adding or subtracting approximately 10% of the indicated value). Unless otherwise expressly stated, all measurements reported herein should be understood to be modified by the term “about,” whether or not the term is explicitly used.

[0033] When quantities, concentrations, or other values ​​or parameters are given as a list of ranges, preferred ranges, or preferred upper and / or preferred lower limits, it should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred range value and any lower or preferred range value, regardless of whether the range is disclosed individually. Wherever a numerical range is given herein, the range is intended to include its endpoints, as well as all integers and fractions within that range, unless otherwise indicated.

[0034] As used herein, the term "compound" refers to all stereoisomers, geometric isomers, tautomers, and isotopes that include the structure or chemical substance described. Unless otherwise stated, compounds identified herein by name or structure as a particular tautomer are intended to include other tautomers.

[0035] As used in this article, the term "catalyst" refers to a substance that accelerates a chemical reaction but is not consumed by the reaction; therefore, it can be recovered without undergoing a chemical change at the end of the reaction. Composition

[0036] The compositions comprising 1,1,1,4,4,4-hexafluoro-2-butyne disclosed herein can be used as starting materials and / or intermediates for the manufacture of usable molecules. While not intended to be limiting, the compositions are illustrated herein as being suitable for the manufacture of 1336mzzZ.

[0037] The compositions containing 1,1,1,4,4,4-hexafluoro-2-butyne disclosed herein are also suitable for cleaning and / or etching applications as components of oxygen-containing gas mixtures. These gas mixtures are suitable for cleaning substrates and processing chambers used in the manufacture of electronic components, including semiconductor materials.

[0038] Table 1 provides a list of compounds that may be present in the compositions disclosed herein.

[0039]

[0040] This invention provides a composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123, and 1122 in a total not exceeding 0.5% (mol%). It should be understood that “0.5%” is equivalent to 5000 ppm, and “0.1%” is equivalent to 1000 ppm, and so on. For the purposes of this document, all amounts expressed as percentages “%” reflect molar percentages.

[0041] In one embodiment, the composition comprises one or more of 113, 122, 123, and 1122 in a total of no more than 0.5% (mol%). In another embodiment, the composition comprises one or more of 113, 122, 123, and 1122 in a total of no more than 0.2% (mol%). In another embodiment, the composition comprises one or more of 113, 122, 123, and 1122 in a total of no more than 0.1% (mol%). In another embodiment, the composition comprises one or more of 113, 122, 123, and 1122 in a total of no more than 0.05% (mol%). In yet another embodiment, the composition comprises one or more of 113, 122, 123, and 1122 in a total of no more than 0.01% (mol%).

[0042] In one embodiment, the composition comprises PFBY and 113, wherein 113 is present in an amount of less than 0.5%, or less than 0.2%, or less than 0.1%, or less than 0.05%, or less than 0.01%. In one embodiment, the composition comprises PFBY and 122, wherein 122 is present in an amount of less than 0.5%, or less than 0.2%, or less than 0.1%, or less than 0.05%, or less than 0.01%. In one embodiment, the composition comprises PFBY and 1122, wherein 1122 is present in an amount of less than 0.5%, or less than 0.2%, or less than 0.1%, or less than 0.05%, or less than 0.01%.

[0043] In one embodiment, the composition containing PFBY comprises 113 and 122, wherein the total amount of 113 and 122 is less than 0.5%, or less than 0.2%, or less than 0.1%, or less than 0.05%, or less than 0.01%. In one embodiment, the composition containing PFBY comprises 113 and 123, wherein the total amount of 113 and 123 is less than 0.5%, or less than 0.2%, or less than 0.1%, or less than 0.05%, or less than 0.01%. In one embodiment, the composition containing PFBY comprises 113 and 1122, wherein the total amount of 113 and 1122 is less than 0.5%, or less than 0.2%, or less than 0.1%, or less than 0.05%, or less than 0.01%. In one embodiment, the composition containing PFBY comprises 122 and 123, wherein the total amount of 122 and 123 is less than 0.5%, or less than 0.2%, or less than 0.1%, or less than 0.05%, or less than 0.01%. In one embodiment, the composition containing PFBY comprises 122 and 1122, wherein the total amount of 122 and 1122 is less than 0.5%, or less than 0.2%, or less than 0.1%, or less than 0.05%, or less than 0.01%. In one embodiment, the composition containing PFBY comprises 123 and 1122, wherein the total amount of 123 and 1122 is less than 0.5%, or less than 0.2%, or less than 0.1%, or less than 0.05%, or less than 0.01%.

[0044] In one embodiment, the composition comprising PFBY includes 113, 122, and 123, wherein the total amount of 113, 122, and 123 is less than 0.5%, or less than 0.2%, or less than 0.1%, or less than 0.05%, or less than 0.01%. In one embodiment, the composition comprises PFBY, 122, and 1122, wherein the total amount of 113, 122, and 1122 is less than 0.5%, or less than 0.2%, or less than 0.1%, or less than 0.05%, or less than 0.01%. In one embodiment, the composition comprises PFBY, 122, 123, and 1122, wherein the total amount of 122, 123, and 1122 is less than 0.5%, or less than 0.2%, or less than 0.1%, or less than 0.05%, or less than 0.01%.

[0045] In one embodiment, the composition comprises PFBY, 113, 122, 123 and 1122, wherein the total amount of 113, 122, 123 and 1122 is less than 0.5%, or less than 0.2%, or less than 0.1%, or less than 0.05%, or less than 0.01%.

[0046] In one embodiment, the composition further comprises one or more additional compounds selected from the group consisting of: HFC-23, HFC-41, HCFC-132b, HCFC-142b, HFC-143a, HFC-152a, trifluoropropyne, HFC-263fb, HFC-356mff, HCFO-1122, HCFO-Z-1326mxz, HCFO-E-1326mxz, HFO-1327mz, HFO-E-1336mzz, and trifluoroacetone. The additional compounds may be present in amounts not exceeding 0.5%, 0.1%, or 0.01%.

[0047] In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123, and 1122 in a total not exceeding 0.5% (mol%) further comprises HFC-23. In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123, and 1122 in a total not exceeding 0.5% (mol%) further comprises HFC-41. In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123, and 1122 in a total not exceeding 0.5% (mol%) further comprises HCFC-132b. In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123, and 1122 in a total not exceeding 0.5% (mol%) further comprises CFC-142b. In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123, and 1122 in a total not exceeding 0.5% (mol%) further comprises HFC-143a. In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123, and 1122 in a total not exceeding 0.5% (mol%) further comprises HFC-152a. In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123, and 1122 in a total not exceeding 0.5% (mol%) further comprises trifluoropropyne. In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123, and 1122 in a total not exceeding 0.5% (mol%) further comprises HFC-263fb. In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123, and 1122 in a total not exceeding 0.5% (mol%) further comprises HFC-356mff. In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123 and 1122 in total not more than 0.5% (mol%) further comprises HCFO-1122.In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123, and 1122 in a total not exceeding 0.5% (mol%) further comprises HCFO-Z-1326mxz. In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123, and 1122 in a total not exceeding 0.5% (mol%) further comprises HCFO-E-1326mxz. In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123, and 1122 in a total not exceeding 0.5% (mol%) further comprises HFO-1327mz. In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123, and 1122 in total not exceeding 0.5% (mol%) further comprises HFO-E-1336mzz. In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123, and 1122 in total not exceeding 0.5% (mol%) further comprises trifluoroacetone.

[0048] In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123 and 1122 in total not more than 0.5% (mol%) further comprises HCFO-Z-1326mxz and HCFO-E-1326mxz.

[0049] In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123 and 1122 in total not more than 0.5% (mol%) further comprises HCFO-Z-1326mxz, HCFO-E-1326mxz and HFO-1327mz.

[0050] In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123 and 1122 in total not more than 0.5% (mol%) further comprises HCFO-1122, HCFO-Z-1326mxz and HCFO-E-1326mxz.

[0051] In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123 and 1122 in total not more than 0.5% (mol%) further comprises HCFO-1122, HCFO-Z-1326mxz, HCFO-E-1326mxz and HFO-1327mz. method

[0052] The present invention provides compositions that can be used as intermediates for the production of fluoroolefins (particularly 1336mzzZ). Preparation of 1,1,1,4,4,4-hexafluoro-2-butyne

[0053] The compositions provided herein can be prepared by the following methods.

[0054] One step (a) includes providing a composition comprising 113a and a total of no more than 0.5% of one or more of 113, 122, 123 and 1122, or a total of no more than 0.2% of one or more of 113, 122, 123 and 1122, a total of 0.1% of one or more of 113, 122, 123 and 1122, or a total of 0.05% of one or more of 113, 122, 123 and 1122, or a total of 0.01% of one or more of 113, 122, 123 and 1122.

[0055] The method further includes step (b): contacting the composition containing 113a with hydrogen in the presence of the catalyst in step (b) to produce a first product mixture containing 1316mxx and at least one of 113, 122, 123 and 1122, wherein the composition containing 113a contains a total of less than 0.5% of one or more of 113, 122, 123 and 1122.

[0056] The catalyst in step (b) contains a transition metal. The transition metal may be selected from ruthenium, rhodium, palladium, and platinum. The catalyst in step (b) may contain a support. The support may be selected from silicon carbide (SiC), tungsten carbide (WC), and alumina.

[0057] Typical reaction conditions for step (b) are as follows. The reaction can be carried out at temperatures ranging from 90°C to 200°C. The reaction pressure in step (b) is typically in the range of 80 psig to 200 psig (0.55 MPa to 1.38 MPa). Step (b) can be carried out with a contact time ranging from 30 seconds to 100 seconds (30 s to 100 s), such as a contact time of 70 seconds (70 s).

[0058] In some embodiments, the composition comprising 113a in step (b) comprises 113. In some embodiments, the composition comprising 113a in step (b) comprises 122. In some embodiments, the composition comprising 113a in step (b) comprises 123. In some embodiments, the composition comprising 113a in step (b) comprises 1122.

[0059] In some embodiments, the composition comprising 113a in step (b) comprises 113 and 122. In some embodiments, the composition comprising 113a in step (b) comprises 113 and 123. In some embodiments, the composition comprising 113a in step (b) comprises 113 and 1122. In some embodiments, the composition comprising 113a in step (b) comprises 122 and 123. In some embodiments, the composition comprising 113a in step (b) comprises 122 and 1122. In some embodiments, the composition comprising 113a in step (b) comprises 123 and 1122. In some embodiments, the composition comprising 113a in step (b) comprises 113, 122, 123, and 1122.

[0060] In some embodiments, the composition comprising 113a and one or more of 113, 122, 123, and 1122 in steps (a) and (b) further comprises one or more of 112, 112a, 114, 114a, 115, 215ba, 216, 316, 318, and PCE in total not exceeding 0.5%. In some embodiments, the composition comprising 113a and one or more of 113, 122, 123, and 1122 in step (a) or (b) further comprises one or more of 111, 214cb, CHCl2CCl3, and CCl3CCl3 in total not exceeding 0.5%. In some embodiments, the composition comprising 113a and one or more of 113, 122, 123 and 1122 in step (a) or step (b) comprises one or more of 112, 112a, 113, 114a and 318 in total not more than 0.5%.

[0061] The method further includes step (c): purifying a first product mixture comprising 1316mxx and at least one of 113, 122, 123 and 1122 by fractionation of not less than 1:1 or 2:1 or 3:1, to provide a composition comprising 1316mxx and one or more of 113, 122, 123 and 1122 in total not more than 0.5%.

[0062] This step (c) is typically performed at a pressure of 200 psig or lower, or 150 psig (1.03 MPa) or lower, or 80 psig (0.55 MPa) or lower, which is within the range of ambient pressure up to 200 psig (1.38 MPa).

[0063] The composition provided by purifying a mixture of first products comprising 1316mxx and at least one of 113, 122, 123, and 1122 by fractionation in step (c) using a reflux ratio of not less than 1:1, 2:1, or 3:1 comprises 1316mxx and one or more of 113, 122, 123, and 1122 in total not more than 0.5%. The composition provided in step (c) may comprise Z-1316mxx or E-1316mxx, or a mixture of Z-1316mxx and E-1316mxx. When the composition provided in step (c) comprises a mixture of Z-1316mxx and E-1316mxx, the ratio of Z-1316mxx to E-1316mxx (Z / E) is in the range of 1:99, or 5:95, or 10:90, or 15:85, or 20:80, or 25:75, or 30:70, or 35:65, or 40:60, or 45:55, or 50:50, or 55:45, or 60:40, or 65:35, or 70:30, or 75:25, or 80:20, or 85:15, or 90:10, or 95:5, or 99:1. The ratio of Z-1316mxx to E-1316mxx (Z / E) is preferably within the range of 10:90, or 15:85, or 20:80, or 25:75, or 30:70, or 35:65, or 40:60, or 45:55, or 50:50, or 55:45, or 60:40, or 65:35, or 70:30, or 75:25, or 80:20, or 85:15, or 90:10. More preferably, the ratio of Z-1316mxx to E-1316mxx (Z / E) is within the range of 65, or 40:60, or 45:55, 50:50, or 55:45, or 60:40, or 65:35.

[0064] In step (c), when purifying a first product mixture comprising 1316mxx and at least one of 113, 122, 123, and 1122 by fractionation with a reflux ratio of not less than 1:1, 2:1, or 3:1, the first product mixture fed to this step may contain a total of more than 0.5%, or more than 0.2%, or more than 0.1%, or more than 0.05%, or more than 0.01% of one or more of 113, 122, 123, and 1122. Purification step (c) provides a composition comprising 1316mxx and a total of not more than 0.5%, or not more than 0.2%, or not more than 0.1%, or not more than 0.05%, or not more than 0.01% of one or more of 113, 122, 123, and 1122.

[0065] In one embodiment, the reflux ratio is at least 1:1. In one embodiment, the reflux ratio is at least 2:1. In one embodiment, the reflux ratio is at least 3:1.

[0066] In one embodiment of step (c) of purifying a first product mixture comprising at least one of 1316mxx and 113, 122, 123 and 1122 by fractionation using a reflux ratio of not less than 1:1, 2:1 or 3:1, the first product mixture comprises a total of more than 0.1% of one or more of 113, 122, 123 and 1122 to provide a composition comprising 1316mxx and a total of not more than 0.1%, or not more than 0.05%, or not more than 0.01% of one or more of 113, 122, 123 and 1122.

[0067] In one embodiment of step (c), the purification of a first product mixture comprising at least one of 1316mxx and 113, 122, 123, and 1122 is carried out by fractionation with a reflux ratio of not less than 1:1, wherein the first product mixture comprises a total of more than 0.1% of one or more of 113, 122, 123, and 1122. In another embodiment of step (c), the purification of a first product mixture comprising at least one of 1316mxx and 113, 122, 123, and 1122 is carried out by fractionation with a reflux ratio of not less than 2:1, wherein the first product mixture comprises a total of more than 0.1% of one or more of 113, 122, 123, and 1122. In one embodiment, the first product mixture is purified by fractionation using a reflux ratio of not less than 3:1, comprising at least one of 1316mxx and 113, 122, 123 and 1122, wherein the first product mixture comprises a total of more than 0.05% of one or more of 113, 122, 123 and 1122.

[0068] In one embodiment, the first product mixture comprising at least one of 1316mxx and 113, 122, 123 and 1122 is purified by fractionation using a reflux ratio of not less than 1:1, 2:1 or 3:1, wherein the first product mixture comprises a total of more than 0.05% of one or more of 113, 122, 123 and 1122 to provide a composition comprising 1316mxx and a total of not more than 0.05% or not more than 0.01% of one or more of 113, 122, 123 and 1122.

[0069] The method further includes step (d): contacting the composition containing 1316mxx with hydrogen in the presence of a catalyst selected from the group consisting of carbon-supported copper, carbon-supported nickel, carbon-supported copper and nickel, and carbon-supported copper and palladium, to produce a second product mixture containing 1326mxx and at least one of 113, 122, 123, and 1122, wherein the composition containing 1316mxx contains a total of less than 0.5% of one or more of 113, 122, 123, and 1122. The composition containing 1316mxx used in step (d) may contain a total of less than 0.2% of one or more of 113, 122, 123, and 1122. The composition containing 1316mxx used in step (d) may contain a total of less than 0.1% of one or more of 113, 122, 123, and 1122. The composition containing 1316mxx used in step (d) may contain one or more of 113, 122, 123, and 1122 in total less than 0.05%. The composition containing 1316mxx used in step (d) may contain one or more of 113, 122, 123, and 1122 in total less than 0.01%. Additional compounds may be present in the composition containing 1316mxx used in step (d) as described above.

[0070] In one embodiment, the composition containing 1316mxx used in step (d) comprises 113, 122, 123, and 1122. In one embodiment, the composition containing 1316mxx used in step (d) comprises 113, 122, and 123. In one embodiment, the composition containing 1316mxx used in step (d) comprises 113, 122, and 1122. In one embodiment, the composition containing 1316mxx used in step (d) comprises 122, 123, and 1122. In one embodiment, the composition containing 1316mxx used in step (d) comprises 113 and 122. In one embodiment, the composition containing 1316mxx used in step (d) comprises 113 and 123. In one embodiment, the composition containing 1316mxx used in step (d) comprises 113 and 1122. In one embodiment, the composition containing 1316mxx used in step (d) comprises 122 and 123. In one embodiment, the composition containing 1316mxx used in step (d) comprises 122 and 1122. In one embodiment, the composition containing 1316mxx used in step (d) comprises 123 and 1122. In one embodiment, the composition containing 1316mxx used in step (d) comprises 113. In one embodiment, the composition containing 1316mxx used in step (d) comprises 122. In one embodiment, the composition containing 1316mxx used in step (d) comprises 123. In one embodiment, the composition containing 1316mxx used in step (d) comprises 1122.

[0071] Step (d) is typically performed at temperatures ranging from 150°C to 250°C and pressures ranging from 80 psig to 300 psig (0.55 MPa to 2.07 MPa). The contact time is typically between 50 and 200 seconds.

[0072] The second product mixture containing 1326mxz produced in step (d) may contain a total of more than 0.5% of one or more of 113, 122, 123 and 1122, or a total of more than 0.2% of one or more of 113, 122, 123 and 1122, or a total of more than 0.1% of one or more of 113, 122, 123 and 1122.

[0073] The method further includes step (e): purifying the second product mixture containing 1326 mgxz by fractionation using a reflux ratio of not less than 1:1, 2:1, or 3:1 to provide a composition containing 1326 mgxz and one or more of 113, 122, 123, and 1122 in total not more than 0.5%.

[0074] The second product mixture may contain one or more of 113, 122, 123, and 1122 in total amounts greater than 0.5%, or greater than 0.2%, or greater than 0.1%, or greater than 0.05%, or greater than 0.01%. Purification of the second product mixture provides a composition comprising 1326mxz and one or more of 113, 122, 123, and 1122 in total amounts not exceeding 0.5%, or not exceeding 0.2%, or not exceeding 0.1%, or not exceeding 0.05%, or not exceeding 0.01%.

[0075] In one embodiment, the reflux ratio of step (e) is at least 1:1. In one embodiment, the reflux ratio of step (e) is at least 2:1. In one embodiment, the reflux ratio of step (e) is at least 3:1.

[0076] In one embodiment of step (e) for purifying a second product mixture comprising at least one of 1326mxz and 113, 122, 123, and 1122 by fractionation using a reflux ratio of not less than 1:1, the second product mixture comprises a total of more than 0.1% of one or more of 113, 122, 123, and 1122. In one embodiment of step (e) for purifying a second product mixture comprising at least one of 1326mxz and 113, 122, 123, and 1122 by fractionation using a reflux ratio of not less than 2:1, the second product mixture comprises a total of more than 0.1% of one or more of 113, 122, 123, and 1122. In one embodiment of step (e) for purifying a second product mixture comprising at least one of 1326mxz and 113, 122, 123 and 1122 by fractionation with a reflux ratio of not less than 3:1, the second product mixture comprises a total of more than 0.1% of one or more of 113, 122, 123 and 1122.

[0077] The conditions for step (e) are the same as those for step (c). That is, step (e) is typically performed at a pressure of 200 psig or lower, or 150 psig (1.03 MPa) or lower, or 80 psig (0.55 MPa) or lower, which is within the range of ambient pressure up to 200 psig (1.38 MPa).

[0078] The method further includes step (f): contacting a composition comprising 1326mxz and one or more of 113, 122, 123, and 1122 in total not exceeding 0.5% with an alkali metal hydroxide in an alkaline aqueous solution to produce a third product mixture comprising hexafluoro-2-butyne. The composition comprising 1326mxz used in step (f) may comprise one or more of 113, 122, 123, and 1122 in total less than 0.2%. The composition comprising 1326mxz used in step (f) may comprise one or more of 113, 122, 123, and 1122 in total less than 0.1%. The composition comprising 1326mxz used in step (f) may comprise one or more of 113, 122, 123, and 1122 in total less than 0.05%. The composition containing 1326mxz used in step (f) may contain less than 0.01% of one or more of 113, 122, 123, and 1122. Additional compounds may be present in the composition containing 1326mxz used in step (d) as described above.

[0079] In one embodiment, the composition containing 1326mxz used in step (f) comprises 113, 122, 123, and 1122. In one embodiment, the composition containing 1326mxz used in step (f) comprises 113, 122, and 123. In one embodiment, the composition containing 1326mxz used in step (f) comprises 113, 122, and 1122. In one embodiment, the composition containing 1326mxz used in step (f) comprises 122, 123, and 1122. In one embodiment, the composition containing 1326mxz used in step (f) comprises 113 and 122. In one embodiment, the composition containing 1326mxz used in step (f) comprises 113 and 123. In one embodiment, the composition containing 1326mxz used in step (f) comprises 113 and 1122. In one embodiment, the composition containing 1326mxz used in step (f) comprises 122 and 123. In one embodiment, the composition containing 1326mxz used in step (f) comprises 122 and 1122. In one embodiment, the composition containing 1326mxz used in step (f) comprises 123 and 1122. In one embodiment, the composition containing 1326mxz used in step (f) comprises 113. In one embodiment, the composition containing 1326mxz used in step (f) comprises 122. In one embodiment, the composition containing 1326mxz used in step (f) comprises 123. In one embodiment, the composition containing 1326mxz used in step (f) comprises 1122.

[0080] Typical reaction conditions for step (f) are as follows: temperature from 150°C to 250°C, pressure from 80 psig to 300 psig (0.55 MPa to 2.07 MPa), and contact time from 50 seconds to 200 seconds.

[0081] The method further includes step (g): purifying a third product mixture containing hexafluoro-2-butyne (PFBY) by fractionation with a reflux ratio of not less than 1:1, 2:1, or 3:1 to provide a composition containing PFBY and one or more of 113, 122, 123, and 1122 in total not more than 0.5%, or not more than 0.2%, or not more than 0.1%, or not more than 0.05%, or not more than 0.01%.

[0082] The third product mixture may contain one or more of 113, 122, 123, and 1122 in total amounts greater than 0.5%, or greater than 0.2%, or greater than 0.1%, or greater than 0.05%, or greater than 0.01%. Purification of the third product mixture provides a composition comprising PFBY and one or more of 113, 122, 123, and 1122 in total amounts not exceeding 0.5%, or not exceeding 0.2%, or not exceeding 0.1%, or not exceeding 0.05%, or not exceeding 0.01%.

[0083] In one embodiment, the reflux ratio of step (g) is at least 1:1. In one embodiment, the reflux ratio of step (g) is at least 2:1. In one embodiment, the reflux ratio of step (g) is at least 3:1.

[0084] In one embodiment of step (g) of purifying a mixture of third products comprising at least one of PFBY and 113, 122, 123, and 1122 by fractionation with a reflux ratio of not less than 1:1, the third product mixture comprises one or more of 113, 122, 123, and 1122 in total greater than 0.5%, or greater than 0.2%, or greater than 0.1%, or greater than 0.05%, or greater than 0.01%. In one embodiment of step (g) of purifying a mixture of third products comprising at least one of PFBY and 113, 122, 123, and 1122 by fractionation with a reflux ratio of not less than 2:1, the third product mixture comprises one or more of 113, 122, 123, and 1122 in total greater than 0.5%, or greater than 0.2%, or greater than 0.1%, or greater than 0.05%, or greater than 0.01%. In one embodiment, the third product mixture is purified by fractionation using a reflux ratio of not less than 3:1, wherein the third product mixture contains one or more of 113, 122, 123 and 1122 in total amounts greater than 0.5%, or greater than 0.2%, or greater than 0.1%, or greater than 0.05%, or greater than 0.01%.

[0085] The conditions for step (g) are the same as those for step (c). That is, step (g) is typically performed at a pressure of 200 psig or lower, or 150 psig (1.03 MPa) or lower, or 80 psig (0.55 MPa) or lower, i.e., an ambient pressure of up to 200 psig (1.38 MPa).

[0086] The product from the purified third product mixture in step (g) can provide the compositions disclosed herein. Preparation of HFO-Z-1,1,1,4,4,4-hexafluoro-2-butene (1336mzzZ)

[0087] The compositions disclosed herein can be further used to produce a product mixture containing 1336 mzzz.

[0088] In the method for producing 1336mzzZ, there is a step (h): contacting a composition comprising hexafluoro-2-butyne as described herein with a Lindlar catalyst or a palladium catalyst further comprising a lanthanide element or silver in the presence of hydrogen to produce a fourth product mixture comprising 1336mzzZ, the composition comprising one or more of 113, 122, 123 and 1122 in total not more than 0.5%, or not more than 0.2%, or not more than 0.1%, or not more than 0.05%, or not more than 0.01%.

[0089] The composition containing PFBY used in step (h) may contain one or more of 113, 122, 123, and 1122 in total less than 0.2%. The composition containing PFBY used in step (h) may contain one or more of 113, 122, 123, and 1122 in total less than 0.1%. The composition used in step (h) may contain one or more of 113, 122, 123, and 1122 in total less than 0.05%. The composition containing PFBY used in step (h) may contain one or more of 113, 122, 123, and 1122 in total less than 0.01%.

[0090] In one embodiment, the PFBY-containing composition used in step (h) comprises 113, 122, 123, and 1122. In one embodiment, the PFBY-containing composition used in step (h) comprises 113, 122, and 123. In one embodiment, the PFBY-containing composition used in step (h) comprises 113, 122, and 1122. In one embodiment, the PFBY-containing composition used in step (h) comprises 122, 123, and 1122. In one embodiment, the PFBY-containing composition used in step (h) comprises 113 and 122. In one embodiment, the PFBY-containing composition used in step (h) comprises 113 and 123. In one embodiment, the PFBY-containing composition used in step (h) comprises 113 and 1122. In one embodiment, the PFBY-containing composition used in step (h) comprises 122 and 123. In one embodiment, the PFBY-containing composition used in step (h) comprises 122 and 1122. In one embodiment, the composition containing 1326mxz used in step (f) comprises 123 and 1122. In one embodiment, the composition containing PFBY used in step (h) comprises 113. In one embodiment, the composition containing PFBY used in step (h) comprises 122. In one embodiment, the composition containing PFBY used in step (h) comprises 123. In one embodiment, the composition containing PFBY used in step (h) comprises 1122.

[0091] Typical reaction conditions for step (h) are as follows: temperature in the range of 30°C to 60°C, and pressure in the range of atmospheric pressure to 50 psig (atmospheric pressure to 0.34 MPa). Residence time in the range of 0.5 hours to 5 hours.

[0092] By using steps (a) to (h) of the method disclosed herein, a fourth product containing 1336 mZZ generated in step (h) can be produced in high purity with fewer byproducts and less product yield loss. Therefore, the purification of the fourth product containing 1336 mZZ is simplified. application

[0093] The PFBY-containing compositions disclosed herein can be used in semiconductor manufacturing applications, such as etching semiconductors, and as a cleaning gas for removing surface deposits in CVD and PECVD chambers. In one embodiment, PFBY can be used to replace hexachlorobutadiene in etching applications.

[0094] In one embodiment of the invention, a method for removing surface deposits from the interior of a chemical vapor deposition chamber is provided. The method includes using an activated gas mixture generated by activating a gas mixture in or remotely within the chemical vapor deposition chamber, wherein the gas mixture comprises oxygen and a composition comprising PFBY and one or more of 113, 122, 123, and 1122 in total not exceeding 0.5%, or not exceeding 0.2%, or not exceeding 0.1%, or not exceeding 0.05%, or not exceeding 0.01%.

[0095] In one embodiment, the present invention provides a gas mixture suitable for cleaning and etching applications, the gas mixture having low GWP and low EHS (environmental, health, and safety) issues, such that even if unreacted gases are released, they have a reduced environmental impact. In one embodiment, a gas mixture comprising oxygen and a composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne and one or more of 113, 122, 123, and 1122 in total not more than 0.5% or not more than 0.1%.

[0096] In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne and a gas mixture comprising no more than 0.5% of one or more of 113, 122, 123 and 1122 contains at least 99.5% 1,1,1,4,4,4-hexafluoro-2-butyne.

[0097] In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne and a gas mixture comprising not more than 0.5% of one or more of 113, 122, 123 and 1122 contains at least 99.8% of 1,1,1,4,4,4-hexafluoro-2-butyne and not more than 0.2% of one or more of 113, 122, 123 and 1122.

[0098] In one embodiment, the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne and a gas mixture comprising not more than 0.5% of one or more of 113, 122, 123 and 1122 contains at least 99.9% of 1,1,1,4,4,4-hexafluoro-2-butyne and not more than 0.1% of one or more of 113, 122, 123 and 1122.

[0099] In another embodiment, a method is provided that uses a gas mixture as an etching gas, wherein the etching gas is used to etch a film on an electronic material, such as a semiconductor. In an alternative embodiment, the invention provides a method for removing deposits from a manufacturing process chamber for electronic materials using an etching gas comprising oxygen and a composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne and one or more of 113, 122, 123, and 1122 in total not more than 0.5% or not more than 0.1%.

[0100] The present invention also includes a method for cleaning material deposits in a processing chamber, the method comprising activating a gas in a remote chamber or in situ within the processing chamber, wherein the gas mixture comprises an oxygen source and a composition comprising one or more of 1,1,1,4,4,4-hexafluoro-2-butyne and a total of no more than 0.5% of 113, 122, 123, and 1122; and contacting the activated gas with a surface deposit for a time sufficient to remove the deposit. The gas mixture may be activated by an RF source with sufficient power for a sufficient time such that the gas mixture reaches a neutral temperature of about 800°K to 3,000°K to form an activated gas mixture, or alternatively, a glow discharge may be used to activate the gas, and thereafter the activated gas mixture is contacted with the surface deposit, thereby removing at least some of the surface deposit.

[0101] The etching gas mixture of claim 14, wherein the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne and a total of not more than 0.5% of one or more of 113, 122, 123 and 1122 contains at least 99.5% 1,1,1,4,4,4-hexafluoro-2-butyne.

[0102] The etching gas mixture of claim 14, comprising 1,1,1,4,4,4-hexafluoro-2-butyne and a total of no more than 0.5% of one or more of 113, 122, 123 and 1122, contains at least 99.8% of 1,1,1,4,4,4-hexafluoro-2-butyne and a total of no more than 0.2% of one or more of 113, 122, 123 and 1122.

[0103] The etching gas mixture of claim 14, comprising 1,1,1,4,4,4-hexafluoro-2-butyne and a total of no more than 0.5% of one or more of 113, 122, 123 and 1122, contains at least 99.9% of 1,1,1,4,4,4-hexafluoro-2-butyne and a total of no more than 0.1% of one or more of 113, 122, 123 and 1122.

[0104] The surface deposits removed by this invention include those materials typically deposited by chemical vapor deposition (CVD) or plasma-enhanced chemical vapor deposition (PECVD) or similar processes. Such materials include nitrogen-containing deposits, such as, but not limited to, silicon nitride, silicon oxynitride, silicon carbonitride (SiCN), silicon boron nitride (SiBN), and metal nitrides such as tungsten nitride, titanium nitride, or tantalum nitride. In one embodiment of the invention, the preferred surface deposit is silicon nitride.

[0105] In one embodiment of the invention, surface deposits are removed from a surface used to manufacture electronic materials. For example, in one embodiment, a method is provided to remove surface deposits from the inner wall of a processing chamber used to manufacture electronic devices. This processing chamber may be a CVD chamber or a PECVD chamber. Other embodiments of the invention include, but are not limited to, removing surface deposits from metals, cleaning plasma etching chambers, and removing N-containing thin films from wafers.

[0106] In one embodiment, the method of the present invention involves an activation step in which a clean gas mixture is activated in a remote chamber. Activation can be accomplished by any method that allows for the decomposition of most of the feed gas, such as radio frequency (RF) energy, direct current (DC) energy, laser irradiation, and microwave energy. One embodiment of the invention uses a transformer inductively coupled to a low-frequency RF power source, wherein the plasma has a toroidal configuration and serves as the secondary of the transformer. Using lower-frequency RF power allows for the use of a magnetic core that enhances inductive coupling relative to capacitive coupling; thus allowing energy to be transferred to the plasma more efficiently without excessive ion bombardment that limits the lifetime inside the remote plasma source chamber. Typical RF power used in the present invention has a frequency below 1000 kHz. In another embodiment of the invention, the power source is a remote microwave, inductively or capacitively coupled plasma source. In yet another embodiment of the invention, a glow discharge is used to activate the gas.

[0107] Activation of the clean gas mixture uses sufficient power and duration to form an activated gas mixture. In one embodiment of the invention, the activated gas mixture has a neutral temperature of approximately 1000 K to 3000 K. The neutral temperature of the resulting plasma depends on the power and residence time of the gas mixture in the remote chamber. Under certain power inputs and conditions, the neutral temperature will increase with increasing residence time. In one embodiment of the invention, the preferred neutral temperature of the activated gas mixture exceeds approximately 3000 K. Under appropriate conditions (considering power, gas composition, gas pressure, and gas residence time), neutral temperatures of at least approximately 1000 K to 5000 K can be achieved.

[0108] Preferably, PFBY can be blended with oxygen at an HFO / O2 ratio of 0.1-3:1.0-0.1, or with existing etching / cleaning gases, or both. Preferably, the blend is further mixed with a carrier gas (such as argon, helium, or nitrogen).

[0109] The activated gas can be formed in a separate remote chamber outside but adjacent to the processing chamber. In this invention, a remote chamber refers to a chamber other than a cleaning or processing chamber where the activated gas plasma can be generated, and a processing chamber refers to a chamber in which surface deposits are located. The remote chamber is connected to the processing chamber via conduits or other means, thereby allowing the activated gas to be transferred from the remote chamber to the processing chamber. For example, the delivery channel may include a short connecting pipe and a nozzle of the CVD / PECVD processing chamber. The remote chamber and the means for connecting the remote chamber to the processing chamber are made of materials known in the art capable of containing the activated gas mixture. For example, ceramics, aluminum, and anodized aluminum are commonly used for chamber components. Sometimes, Al2O3 is coated on the inner surface to reduce surface recombination. In other embodiments of the invention, the activated gas mixture can be formed directly in the processing chamber.

[0110] The etching gas or etching gas mixture activated to form the activating gas comprises 1,1,1,4,4,4-hexafluoro-2-butyne (PFBY) and one or more of 113, 122, 123, and 1122 in total not exceeding 0.5%. As used herein, the etching gas or etching gas mixture is defined as a gas or gas mixture used in semiconductor manufacturing, activated to form a plasma, wherein the plasma can be used to etch the surface of a semiconductor, deposit a polymer layer on the surface of a semiconductor, or clean a processing chamber of an apparatus used in semiconductor manufacturing. When used for etching surfaces or cleaning chambers, the etching gas may also comprise an oxygen source, a nitrogen source, or an inorganic fluorine source. Typical inorganic fluorine sources include NF3 and SF6. In one embodiment of the invention, the gas mixture further comprises a fluorinated compound.

[0111] In certain nitrogen-containing blends, typical nitrogen sources include molecular nitrogen (N2) and NF3. NF3 can also serve as a nitrogen source when it is an inorganic fluorine source. Typical oxygen sources include molecular oxygen (O2). When the fluorocarbon is octafluorotetrahydrofuran or other oxygen-containing fluorocarbon, it can also be used as an oxygen source. In one embodiment of the invention, the oxygen:PFBY molar ratio is at least 0.3:1. In another embodiment of the invention, the oxygen:PFBY molar ratio is at least 0.5:1. In yet another embodiment, the oxygen:PFBY molar ratio is at least 1:1 or at least 3:1.

[0112] The gas mixture activated to form the activated gas mixture of the present invention may also contain a carrier gas. Examples of suitable carrier gases include inert gases, such as argon and helium.

[0113] In embodiments of the present invention, the temperature in the processing chamber can be from about -50°C to about 150°C during etching of the semiconductor surface or deposition of the polymer layer.

[0114] In an embodiment of the invention, the temperature in the processing chamber can be from about 50°C to about 150°C during the removal of surface deposits.

[0115] Using an Astron source, the total pressure in the remote chamber during the activation step can range from approximately 0.5 Torr to approximately 20 Torr. The total pressure in the processing chamber can range from approximately 0.5 Torr to approximately 15 Torr. For other types of remote plasma sources or in-situ plasmas, the pressure ranges differ.

[0116] The gas mixture activated to form the activated gas mixture of the present invention may also contain a carrier gas. Examples of suitable carrier gases include inert gases, such as argon and helium.

[0117] In embodiments of the present invention, the temperature in the processing chamber can be from about -50°C to about 150°C during etching of the semiconductor surface or deposition of the polymer layer.

[0118] In an embodiment of the invention, the temperature in the processing chamber can be from about 50°C to about 150°C during the removal of surface deposits.

[0119] Using an Astron source, the total pressure in the remote chamber during the activation step can range from approximately 0.5 Torr to approximately 20 Torr. The total pressure in the processing chamber can range from approximately 0.5 Torr to approximately 15 Torr. For other types of remote plasma sources or in-situ plasmas, the pressure ranges differ.

[0120] In this invention, it was discovered that the combination of oxygen and fluorobutyne results in a high etching rate for nitride films such as silicon nitride. These increases also provide a lower sensitivity of the etching rate to changes in source gas pressure, chamber pressure, and temperature.

[0121] Without further explanation, those skilled in the art should be able to make full use of the invention based on the description herein. After reading this specification, those skilled in the art will understand that other aspects and embodiments are possible without departing from the scope of the invention. Therefore, the following specific embodiments should be understood as illustrative only and not as limiting the remainder of this disclosure in any way. Example

[0122] Materials. The materials used in the preparation examples are commercially available or can be prepared by known methods. Example 1. Preparation of 1316mxx from 113a

[0123] A 1 / 2-inch OD (chromium-nickel-iron alloy) tube was filled with 2 cc (1.07 gm) of 1% Ru / SiC 1 / 8" granules. The catalyst bed temperature was raised to 120 °C and purged with hydrogen (50 sccm) for 60 min, and then purged at 250 °C for 180 min. The temperature was then lowered to 175 °C for 120 min while maintaining a hydrogen flow rate of 20 sccm. The temperature was then lowered to 160 °C, and the flow rate of CFC-113a without 122 was set to 2.31 ml / h, and the hydrogen flow rate was set to 32 sccm. The reactor effluent was analyzed hourly via online GCMS for 113a, 1316mxx, and 122. For 1316mxx containing 100 ppm of 122, the conversion was 80% and the selectivity was 80%. Example 2.1 Preparation of 326mxz

[0124] Chromium-nickel-iron alloy pipe ® (0.5-inch OD, 15-inch length, 0.34-inch wall thickness) packed with 3 cc (1.2 gm) of pickled carbon (12 to 20 mesh) of Pd / Cu. The reactor temperature was raised to 100°C for 30 minutes under a flow of N2 (30 sccm). The temperature was then increased to 200°C for one hour under a flow of H2. A mixture of the Z- and E-isomers of 1316mxx containing 50 ppm 122 (0.87 g / mL) was fed at 12 sccm H2 at 175°C and 145 psig. The contact time was 90 s. Agilent was used. ® 6890 GC / 5973 MS and Restek ® PC2618 5% Krytox ®CBK-D / 60 / 80 6m × 2mm ID 1 / 8" OD packed column (purged with 30 sccm of helium) for periodic online analysis of reactor effluent for 1316mxx, 1326mxz, and 1122. The product mixture contains 10 ppm to 25 ppm of 1122 (CHCl=CF2) and 10% to 15% of 1326mxz (a mixture of the Z and E isomers of 1326mxz). Preparation of Comparative Example 2.1326mxz

[0125] Chromium-nickel-iron alloy pipe ® (0.5-inch OD, 15-inch length, 0.34-inch wall thickness) packed with 3 cc (1.2 gm) of pickled carbon (12 to 20 mesh) of Pd / Cu. The reactor temperature was raised to 100°C for 30 minutes under a flow of N2 (30 sccm). Then the temperature was increased to 200°C for one hour under a flow of H2. 12 sccm of H2 containing 100 ppm Pd / Cu (0.87 g / mL) was fed into 1316 mg / mL at 175°C and 145 psig. The contact time was 90 s. Agilent Technologies was used. ® 6890 GC / 5973 MS and Restek ® PC2618 5% Krytox ® A CBK-D / 60 / 80 6m × 2mm ID 1 / 8" OD packed column (purged with 30 sccm of helium) was used for periodic online analysis of the reactor effluent for 1316mxx, 1326mxz, and 1122. 20 ppm to 50 ppm of 1122 (CHCl=CF2) formation and 10% to 15% of 1326mxz (a mixture of the Z and E isomers of 1326mxz) formation were observed. Example 3. Preparation of pfby

[0126] At 35°C, in Aliquat ® In the presence of 336 (0.53 g, 0.001325 mol), an aqueous solution of NaOH (12 mL, 0.12 mol) was added to a mixture of Z / E-1326mxz containing 100 ppm 1122 (20 g, 0.1 mol) and water (18 mL). After the addition, the reaction temperature was raised to 70 °C, and the reaction was monitored by gas chromatography for 1326mxz, PFBY, and 1122. The reaction was completed after 2.5 hours, and 15.0 g of the product (conversion: 100%; yield: 92%, PFBY, containing 100 ppm 1122) was collected in a dry ice trap. Example 4.1336 Preparation of mzzz

[0127] Chromium-nickel-iron alloy pipe ® (0.5-inch OD, 15-inch length, 0.34-inch wall thickness) packed with 2.6 cc (3.2 gm) of 200 ppm Al₂O₃ with Pd (12 to 20 mesh). The reactor temperature was raised to 100°C for 30 minutes under a N₂ stream (30 sccm). Then the temperature was increased to 200°C for one hour under a H₂ stream. PFBY containing 500 ppm 1122 (2 sccm) was fed together with 25.9 sccm of H₂ in N₂ (5% H₂ in N₂) at 95°C and 50 psig. The contact time was 20 s. Agilent was used. ® 6890 GC / 5973 MS and Restek ® PC2618 5% Krytox ® A CBK-D / 60 / 80 6m × 2mm ID 1 / 8" OD packed column (purged with 30 sccm of helium) was used to analyze the reactor effluent online for PFBY, 1326mxzZ, 1326mxzE, and 1336mzzZ. 10 ppm of 1326mxzZ and 1 ppm of 1326mxzE were observed, along with 26% of 1336mzzZ. Preparation of Comparative Example 4.1336 mxxz

[0128] Chromium-nickel-iron alloy pipe ® (0.5-inch OD, 15-inch length, 0.34-inch wall thickness) packed with 2.6 cc (3.2 gm) of 200 ppm Al₂O₃ with Pd (12 to 20 mesh). The reactor temperature was raised to 100°C for 30 minutes under a N₂ flow (30 sccm). Then the temperature was increased to 200°C for one hour under a H₂ flow. PFBY containing 1000 ppm 1122 (2 sccm) was fed with H₂ in 25.9 sccm N₂ (5% H₂ in N₂) at 95°C and 50 psig. The contact time was 20 s. Agilent was used. ® 6890 GC / 5973 MS and Restek ® PC2618 5% Krytox ® A CBK-D / 60 / 80 6m × 2mm ID 1 / 8" OD packed column (purged with 30 sccm of helium) was used for online analysis of the reactor effluent for PFBY, 1326mxzZ, 1326mxzE, and 1336mzzZ. 25 ppm of 1326mxzZ and 2 ppm of 1326mxzE were observed, along with 26% of 1336mzzZ.

[0129] While not wishing to be bound by theory, it is suggested that during the hydrogenation of PFBY to 1336mzzZ, 1122 present in PFBY is hydrogenated to form 152a plus HCl. Adding HCl to PFBY forms 1326mxzZ and 1326mxzE, with boiling points of 35°C and 42°C, respectively. Since the boiling point of 1336mzzZ is 33°C, the formation of 1326mxz may negatively impact product purity due to separation difficulties (close to its boiling point). Furthermore, the combination of HCl formed during PFBY hydrogenation with any unintentional moisture may lead to equipment corrosion. For these reasons, understanding the concentrations of 1122 and its precursor in the starting materials and intermediates used to produce 1336mzzZ is particularly beneficial.

Claims

1. A composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne and one or more of 113, 122, 123 and 1122 in total not exceeding 0.5%.

2. The composition of claim 1, wherein the composition comprises, in total, no more than 0.2% of one or more of 113, 122, 123 and 1122.

3. The composition of claim 1, wherein the composition comprises, in total, no more than 0.1% of one or more of 113, 122, 123 and 1122.

4. The composition of claim 1, wherein the composition comprises, in total, no more than 0.05% of one or more of 113, 122, 123 and 1122.

5. The composition of claim 1, wherein the composition comprises, in total, no more than 0.01% of one or more of 113, 122, 123 and 1122.

6. The composition according to any one of claims 1 to 5, wherein the composition comprises 113.

7. The composition according to any one of claims 1 to 5, wherein the composition comprises 122.

8. The composition according to any one of claims 1 to 5, wherein the composition comprises 123.

9. The composition according to any one of claims 1 to 5, wherein the composition comprises 1122.

10. The composition according to any one of claims 1 to 9, wherein the composition further comprises at least one of HFC-23, HFC-41, HCFC-132b, HCFC-142b, HFC-143a, HFC-152a, trifluoropropyne, HFC-263fb, HFC-356mff, HCFO-1122, HCFO-Z-1326mxz, HCFO-E-1326mxz, HFO-1327mz, HFO-E-1336mzz, and trifluoroacetone.

11. The composition of claim 10, wherein the composition comprises, in total, not more than 0.5% of one or more of HFC-23, HFC-41, HCFC-132b, HCFC-142b, HFC-143a, HFC-152a, trifluoropropyne, HFC-263fb, HFC-356mff, HCFO-1122, HCFO-Z-1326mxz, HCFO-E-1326mxz, HFO-1327mz, HFO-E-1336mzz, and trifluoroacetone.

12. The composition according to claim 11, wherein the composition comprises HCFO-Z-1326mxz, HCFO-E-1326mxz and HFO-1327mz.

13. The composition of claim 11, wherein the composition comprises HCFO-1122, HCFO-Z-1326mxz, and HCFO-E-1326mxz.

14. An etching gas mixture comprising oxygen and a composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne and one or more of 113, 122, 123 and 1122 in total not exceeding 0.5%.

15. The etching gas mixture of claim 14, wherein the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne and a total of not more than 0.5% of one or more of 113, 122, 123 and 1122 contains at least 99.5% 1,1,1,4,4,4-hexafluoro-2-butyne.

16. The etching gas mixture of claim 14, wherein the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne and a total of not more than 0.5% of one or more of 113, 122, 123 and 1122 contains at least 99.8% of 1,1,1,4,4,4-hexafluoro-2-butyne and a total of not more than 0.2% of one or more of 113, 122, 123 and 1122.

17. The etching gas mixture of claim 14, wherein the composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne and a total of not more than 0.5% of one or more of 113, 122, 123 and 1122 contains at least 99.9% of 1,1,1,4,4,4-hexafluoro-2-butyne and a total of not more than 0.1% of one or more of 113, 122, 123 and 1122.

18. The etching gas mixture according to any one of claims 14 to 17, wherein the etching gas mixture further comprises a carrier gas.

19. The etching gas mixture according to any one of claims 14 to 17, wherein the carrier gas is He, Ar or N2.

20. The etching gas mixture according to any one of claims 14 to 17, wherein the etching gas mixture further comprises a second etching gas, wherein the second etching gas is a fluorinated compound, SF6, or NF3.

21. The etching gas mixture according to claim 20, wherein the second etching gas is selected from the group consisting of tetrafluoromethane, hexafluoroethane, octafluoropropane, perfluorotetrahydrofuran, hexafluorobutadiene, and octafluorocyclobutane.

22. A method of operating a semiconductor manufacturing processing chamber, the method comprising etching a film on a semiconductor using an etching gas mixture according to any one of claims 14 to 17.

23. The method of claim 22, wherein the step of etching the film further comprises: i. Transferring a photomask onto a semiconductor to create a masking surface and an exposed surface. ii. The plasma that forms the etching gas mixture, and iii. Exposing the exposed surface of the semiconductor to the plasma to remove a portion of the exposed surface of the semiconductor to form an etched surface of the semiconductor.

24. The method of claim 23, wherein the method further comprises the following step: A second etching gas is formed; the second etching gas is activated to form a second plasma; The second plasma is deposited on the etched surface to form a polymer layer on the etched surface of the semiconductor, wherein the second etch gas is a fluorinated compound, SF6, or NF3.

25. The method of claim 23, wherein the surface deposit is selected from the group consisting of: silicon oxide, gallium nitride, silicon nitride, silicon oxynitride, silicon carbonitride, tungsten nitride, titanium nitride, and tantalum nitride.

26. The method of claim 22, wherein the step of forming plasma by the etching gas is performed in a remote chamber or in the processing chamber.

27. The method of claim 22, wherein the etching gas mixture comprises oxygen in a certain molar ratio, and the molar ratio of oxygen to PFBY is at least about 1:

1.

28. The method of claim 27, wherein the pressure in the processing chamber does not exceed 30 Torr.

29. The method of claim 27, wherein the pressure in the remote chamber is from 0.5 Torr to 50 Torr.

30. The method according to any one of claims 22 to 27, wherein the etching gas mixture replaces hexachlorobutadiene.

31. A method for removing surface deposits from a surface in a processing chamber, the method comprising: Activating a gas mixture comprising oxygen and a composition comprising 1,1,1,4,4,4-hexafluoro-2-butyne and one or more of 113, 122, 123 and 1122 in total not exceeding 0.5%, wherein the molar percentage of PFBY in the gas mixture is from about 5% to about 99%; and contacting the activated gas mixture with the surface deposit, thereby removing at least some of the deposit.

32. The method of claim 30, wherein the processing chamber is the interior of a deposition chamber for manufacturing an electronic device.

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