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• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/08—Materials not undergoing a change of physical state when used
  • C09K5/10—Liquid materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/04—Apparatus for manufacture or treatment
  • H10P72/0431—Apparatus for thermal treatment
  • H10P72/0434—Apparatus for thermal treatment mainly by convection

Definitions

• the provided apparatus and methods relate to hydrofluorocarbonate fluids and their use as heat transfer fluids.
• heat transfer fluid that is inert, has a high dielectric strength, has low toxicity, has good environmental properties, and has good heat transfer properties over a wide temperature range.
• Other applications require precise temperature control and thus the heat transfer fluid is required to be a single phase over the entire process temperature range and the heat transfer fluid properties are required to be predictable, i.e., the composition remains relatively constant so that the viscosity, boiling point, etc., can be predicted so that a precise temperature can be maintained and so that the equipment can be appropriately designed.
• the semiconductor industry there are numerous devices or processes that require a heat transfer fluid having select properties.
• the heat transfer fluid may be used to remove heat, add heat, or maintain a temperature.
• heat transfer fluids that are inert, have high dielectric strength, low electrical conductivity, chemical inertness, thermal stability, effective heat transfer, are liquid over a wide temperature range, have good heat transfer properties over a wide range of temperatures, and also have shorter atmospheric lifetimes, and therefore have a lower global warming potential, than existing heat transfer fluids.
• an apparatus for heat transfer that includes a device and a mechanism for transferring heat to or from the device, the mechanism comprising a heat transfer fluid, wherein the heat transfer fluid comprises a partially fluorinated carbonate.
• a method is provided for transferring heat that includes providing a device and providing a mechanism for transferring heat to or from the device, the mechanism comprising a heat transfer fluid, wherein the heat transfer fluid comprises a partially fluorinated carbonate.
• catenated heteroatom refers to an atom other than carbon (for example, oxygen, nitrogen, or sulfur) that is bonded to carbon atoms in a carbon chain so as to form a carbon-heteroatom-carbon chain;
• flash point refers to a temperature above which a chemical species will spontaneously ignite and is defined in this disclosure by ASTM D-3278-96 e-1 "Flash Point of Liquids by Small Scale Closed-Cup Apparatus";
• inert refers to chemical compositions that are generally not chemically reactive under normal conditions of use; "partially fluorinated” refers to fluoroalkyl, fluoroalkylene, or fluorocarbon groups that have at least one carbon-bonded hydrogen atom; and
• perfluoro- (for example, in reference to a group or moiety, such as in the case of "perfluoroalkylene” or “perfluoroalkyl” or “perfluorocarbon") or “perfluorinated” means completely fluorinated such that, except as may be otherwise indicated, there are no carbon-bonded hydrogen atoms replaceable with fluorine.
• the provided apparatus and method include partially fluorinated carbonates that can be used as heat transfer fluids.
• Partially fluorinated carbonates have one or more advantages of high specific heat capacity over a wide range of temperatures, high dielectric strength, low electrical conductivity, chemical inertness, and thermal stability with good environmental properties.
• Semiconductor processes can incorporate a device or a work-piece that has heat removed from it or has heat added to it.
• the heat transfer associated with either the heat removal or addition can take place over a wide temperature range.
• a heat transfer fluid is preferably used which has attributes such as low toxicity and low flammability.
• Heat transfer fluids that are presently used in semiconductor applications include perfluorocarbons (PFCs), perfluoropolyethers (PFPEs), perfluoroamines (PFAs), perfluoroethers (PFEs), water/glycol mixtures, deionized water, silicone oils and hydrocarbon oils.
• PFCs, PFPEs, PFAs and PFEs can exhibit atmospheric lifetime values of greater than 500 years, and up to 5,000 years. Additionally, these materials can exhibit high global warming potentials ("GWP").
• GWP is the integrated potential warming due to the release of one (1) kilogram of sample compound relative to the warming due to one (1) kilogram of CO2 over a specified integration time horizon.
• Water/glycol mixtures are temperature limited, that is, a typical low temperature limit of such mixtures is -4O 0 C. At low temperatures water/glycol mixtures also exhibit relatively high viscosity. The high viscosity at low temperature yields high pumping power. Deionized water has a low temperature limit of O 0 C. Silicone oils and hydrocarbon oils are typically flammable.
• the provided apparatus comprises a device and a mechanism for transferring heat to or from the device wherein the mechanism includes a heat transfer fluid.
• Examples of the provided apparatus include, but are not limited to, a test head used in automated test equipment for testing the performance of semiconductor dice, a wafer chuck used to hold silicon wafers in ashers, steppers, etchers, PECVD tools, a constant temperature bath, and a thermal shock test bath.
• the provided apparatus comprises a device.
• the device is a component, work- piece, assembly, etc. to be cooled, heated or maintained at a selected temperature.
• Such devices include electrical components, mechanical components and optical components.
• suitable devices of the provided apparatus include, but are not limited to a microprocessor, a wafer used to manufacture semiconductor devices, a power control semiconductor, an electrochemical cell (including a lithium-ion cell), an electrical distribution switch gear, power transformer, a circuit board, a multi-chip module, a packaged or unpackaged semiconductor device, a fuel cell, and a laser.
• the apparatus includes a heat transfer mechanism.
• the heat transfer mechanism when placed in thermal contact with the device, can remove heat from the device or provide heat to the device, or maintain the device at a selected temperature by removing or providing heat as necessary.
• thermal contact it is meant that device and the thermal-transfer fluid are in close enough proximity to enable heat to flow between them.
• the direction of heat flow is determined by the relative temperature difference between the device and the heat transfer mechanism.
• the heat transfer mechanism can include the whole system that is involved in heat transfer exclusive of the device.
• the system can include facilities for managing the heat transfer fluid.
• the facilities can include containers, pumps, conduits, thermostats, stirrers, heating means, cooling means, and all other peripheral devices excepting the heat transfer fluid that can be used to control the temperature of a device.
• the heating means and/or cooling means are well known by those of ordinary skill in the art and include, for example, heating coils or wires or cooling coils.
• the heat transfer mechanism includes the heat transfer fluid of the provided apparatus. In some embodiments, the heat transfer mechanism can maintain the device at a selected temperature by transferring heat to or from the device as needed to maintain the temperature of the device.
• the heat transfer mechanism can include facilities for managing the heat transfer fluid, including, e.g., pumps, valves, fluid containment systems, pressure control systems, condensers, heat exchangers, heat sources, heat sinks, refrigeration systems, active temperature control systems, and passive temperature control systems.
• suitable heat transfer mechanisms include, but are not limited to, a system for cooling wafer chucks in plasma-enhanced chemical vapor deposition (PECVD) tools, a system for controlling temperature in test heads for die performance testing, a system for controlling temperatures within semiconductor process equipment, a thermal management system for electrochemical cells such as lithium-ion cells, a system for thermal shock testing of an electronic device, and a system for maintaining constant temperature of an electronic device.
• PECVD plasma-enhanced chemical vapor deposition
• the apparatus includes a device, that can be an electronic device, requiring heat transfer and a mechanism for transferring heat to or from the device, the mechanism comprising a heat transfer fluid, wherein the heat transfer fluid includes a partially fluorinated dialkyl carbonate having the structure, RhOC(O)ORh'.
• the alkyl groups, Rh and Rh' can be identical or different and, independently, can contain from one to 12 carbon atoms.
• R h and R h ' can be linear, branched or cyclic and may, optionally, contain one or more catenated heteroatoms.
• At least one hydrogen atom is substituted with a fluorine atom.
• from about 35% to about 95% of the hydrogen atoms of the dialkyl carbonate can be substituted with fluorine atoms.
• from about 50% to about 95% of the hydrogen atoms of the dialkyl carbonate can be substituted with fluorine atoms.
• from about 60% to about 95% of the hydrogen atoms of the dialkyl carbonate can be substituted with fluorine atoms.
• the higher the degree of substitution of hydrogen by fluorine atoms the less flammable the material, which can be a safety advantage.
• one of Rh or Rh' can include a hydrocarbon alkyl group.
• the partially fluorinated dialkyl carbonate can have a structure, (Rf)R g OC(O)OR' g (Rf') n .
• Rf and R/ are independently perfluorinated or partially fluorinated linear, branched or cycloaliphatic groups having from 1 to 12 carbon atoms when n is zero or one.
• R g and R g ' can, independently, be a linear, branched, or cyclic alkylene moiety having from 1 to 6 carbon atoms.
• Rg and R g ' can contain one or more catenated heteroatoms.
• R g ' can be a linear, branched, or cyclic alkyl group having from 1 to 6 carbon atoms and can contain one or more catenated heteroatoms.
• the provided apparatus includes a heat transfer fluid that is represented by the following Structure (I).
• each of the groups Rl and R4 can, independently, be hydrogen or a linear, branched, or cyclic alkyl group having from 1 to 6 carbon atoms.
• Rl and R4 can, optionally, contain one or more catenated heteroatoms.
• "A" can be a single covalent bond or -CH 2 O-.
• R3 can be a perfluorinated or partially fluorinated linear or branched aliphatic group having from 1 to 10 carbon atoms and, optionally, can contain one or more catenated heteroatoms. In R3 at least 70% of the hydrogen atoms can be substituted with fluorine atoms.
• R2 can be either defined as Rl or R3.
• Y can be a single covalent bond or the group, C(R5)(R6), where each of R5 and R6 can, independently, be hydrogen, or an alkyl group having from 1 to 4 carbon atoms.
• Hydrofluorocarbonates that can be useful include those disclosed in the PCT application, PCT/US2007/087114, filed December 12, 2007 which claims priority to U.S. Provisional Patent Application No. 60/871,076, filed December 20, 2006. Additional hydrofluorocarbonates that can be useful are disclosed, for example, in M. C. Smart et al., Journal of Power Sources, 119-121, (2003) p. 359-367, U. S. Pat. No. 3,359,296 (Newallis et al.), and Euro. Pat. Publ. No. EP 599,534 (Yokoyama et al.).
• the partially fluorinated carbonates can be used alone or in admixture with each other or with other commonly-used solvents (for example, alcohols, ethers, alkanes, alkenes, perfluorocarbons, perfluorinated tertiary amines, perfluoroethers, cycloalkanes, esters, ketones, aromatics, siloxanes, chlorinated alkanes, chlorinated alkenes, carbonates, fluorinated ketones, fluorinated alkenes, hydrochlorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons, hydrofluoroethers, hydrofluoropolyethers, ionic liquids, and the like, and mixtures thereof).
• solvents for example, alcohols, ethers, alkanes, alkenes, perfluorocarbons, perfluorinated tertiary amines, perfluoroethers, cycloalkanes, esters, keto
• Such co-solvents can be chosen to modify or enhance the properties of a composition for a particular use and can be utilized in ratios (of co- solvent(s) to hydrofluorocarbonate(s)) such that the resulting composition preferably has no flash point.
• the hydro fluorocarbonates can be used in combination with other compounds that are very similar in properties relative to a particular use (e.g., other hydrofluorocarbonates) to form compositions that include the provided hydrofluorocarbonates.
• Useful compositions can comprise conventional additives such as, for example, surfactants, coloring agents, lubricants, stabilizers, anti-oxidants, flame retardants, and the like, and mixtures thereof.
• the provided apparatus and methods can include hydrofluorocarbonates that can be synthesized from their corresponding hydro fluoroalcohols by a number of well known methods used to synthesize organic carbonates.
• symmetrical organic carbonates can be made by reacting organic alcohols with phosgene (or triphosgene for ease of handling).
• Unsymmetrical organic carbonates can be synthesized from alkyl chloro formates.
• Other methods that can be used can include, for example, direct condensation of an alcohol and diethylcarbonate catalyzed by a reusable MgLa mixed oxide as described by Veldurthy et al., Chemical Communications, 734 (2004) or the reaction of alcohols with carbon dioxide as disclosed by Aresta et al., J. Org. Chem., 70, 6177 (2005).
• Some hydrofluoroalcohols are commercially available.
• Others can be prepared, for example, by free radical addition of a perfluoroolefm or perfluorovinyl ether and at least one hydrocarbon or addition-capable fluorocarbon alcohol as described in U. S. Pat. Publ. 2007/0051916 (Flynn et al.).
• a method for transferring heat that includes providing a device and providing a mechanism for transferring heat to or from the device, comprising a heat transfer fluid, wherein the heat transfer fluid comprises a partially fluorinated carbonate.
• the processes described in, for example, U. S. Re. Pat. No. 37,119 E (Sherwood) and U. S. Pat. No. 6,374,907 (Tousignant et al.) can be used for heat transfer.
• heat can be transferred between a heat source (for example, a silicon wafer or a component of a flat panel display) and a heat sink through the use of a heat transfer agent comprising at least one hydrofluoroether compound of the invention.
• the device can be a heat source or a heat sink depending upon the direction of heat flow (e.g., to or from the device).
• the hydro fluorocarbonates of the provided method are not mixtures of components of widely disparate molecular weights. Rather, the hydrofluorocarbonates are generally monodisperse (that is, of a narrow molecular weight range). This means that their physical properties remain relatively constant over time, thereby avoiding significant heat transfer performance deterioration.
• the hydrofluorocarbonates of the invention generally exhibit a wide liquid range, useful viscosity over that range, and relatively high thermal stability at end use temperatures, making them well-suited for use as heat transfer fluids.
• Hydrofluorocarbonates can have high heat capacities. Additionally, heat transfer fluids made with hydrofluorocarbonates can also have high heat capacities. Specific heat capacities (measured at 2O 0 C) of the provided heat transfer fluids can be greater than
• 2,2,3,3,4,4,4-heptafluorobutan-l-ol was made from the methyl ester of heptafluorobutyric acid (available from Alfa Aesar, Ward Hill, MA) by sodium borohydride reduction.
• the reaction mix was then quenched with 250 mL of saturated aqueous ammonium chloride.
• the methylene chloride product phase was then separated from the aqueous phase.
• One 200 mL portion of methylene chloride was used to extract product from the aqueous phase.
• the combined organic extracts were washed with 1x100 mL IN HCl, 1x100 mL saturated aqueous sodium bicarbonate, 1x100 mL deionized water and then dried over anhydrous magnesium sulfate.
• the structure was confirmed by GC/MS and NMR.
• the carbonate prepared in example 1 was evaluated for its stability towards strong acids.
• the sample which was refluxed with 98% sulfuric acid was then held for a total time of 24 hours at reflux after adding additional water to make an aqueous acid phase. At the end of this time period the fluorocarbonate phase was again analyzed by GC-FID and GC/MS for breakdown to alcohol. The analysis did not show an increase in alcohol concentration or a decrease in overall purity of the fluorocarbonate.
• Example 2 Preparation of bis(2,2,3,3-tetrafluoropropyl) carbonate 2,2,3, 3-tetrafluoropropan-l-ol (100 g, 0.76 mol), pyridine (120 g, 1.5 mol) and methylene chloride (150 rnL) were combined in a IL 3 -neck round bottom flask.
• the flask was equipped with an overhead stirring mechanism, thermocouple, addition funnel, cold water condenser, CCVethylene glycol bath and a nitrogen line.
• Triphosgene 40 g, 0.13 mol was dissolved in 150 mL of methylene chloride and added via an addition funnel at a rate such that the temperature did not exceed O 0 C.
• the mix was allowed to warm to room temperature on its own.
• the reaction mix was then quenched with 200 mL of saturated aqueous ammonium chloride.
• the methylene chloride product phase was then separated from the aqueous phase.
• One 200 mL portion of methylene chloride was used to extract product from the aqueous phase.
• the combined organic extracts were washed with 5x100 mL IN HCl, 1x100 mL saturated aqueous sodium bicarbonate, 1x100 mL deionized water and then dried over anhydrous magnesium sulfate.
• the structure of the product was confirmed by
• 2,2,3,4,4,4-hexafluorobutan-l-ol 140 g, 0.76 mol
• pyridine 120 g, 1.5 mol
• methylene chloride 150 mL
• Triphosgene 40 g, 0.13 mol
• the reaction mix was then quenched with 250 mL of saturated aqueous ammonium chloride.
• the methylene chloride product phase was then separated from the aqueous phase.
• One 200 mL portion of methylene chloride was used to extract product from the aqueous phase.
• the combined organic extracts were washed with 1x100 mL IN HCl, 1x100 mL saturated aqueous sodium bicarbonate, 1x100 mL deionized water and then dried over anhydrous magnesium sulfate.
• the structure was confirmed by GC/MS and NMR.
• 2,2,3,3,4,4,4-heptafluorobutan-l-ol 152 g, 0.76 mol
• pyridine 120 g, 1.5 mol
• methylene chloride 150 mL
• Triphosgene 40 g, 0.13 mol
• the reaction mix was then quenched with 200 mL of saturated aqueous ammonium chloride.
• the methylene chloride product phase was then separated from the aqueous phase.
• One 200 mL portion of methylene chloride was used to extract product from the aqueous phase.
• the combined organic extracts were washed with 5x100 mL IN HCl, 1x100 mL saturated aqueous sodium bicarbonate, 1x100 mL deionized water and then dried over anhydrous magnesium sulfate.
• the structure was confirmed by GC/MS and NMR.
• Example 5 Preparation of bis(2,2,2-trifluoroethyl) carbonate 2,2,2-trifluoroethanol (76 g, 0.76 mol), pyridine (120 g, 1.5 mol) and methylene chloride (150 mL) were combined in a IL 3 -neck round bottom flask.
• the flask was equipped with an overhead stirring mechanism, thermocouple, addition funnel, cold water condenser, C ⁇ 2 /ethylene glycol bath and a nitrogen line.
• Triphosgene 40 g, 0.13 mol was dissolved in 150 mL of methylene chloride and added via an addition funnel at a rate such that the temperature did not exceed O 0 C. Once the addition was complete the mix was allowed to warm to room temperature on its own.
• the reaction mix was then quenched with 200 mL of saturated aqueous ammonium chloride.
• the methylene chloride product phase was then separated from the aqueous phase.
• One 200 mL portion of methylene chloride was used to extract product from the aqueous phase.
• the combined organic extracts were washed with 5x100 mL IN HCl, 1x100 mL saturated aqueous sodium bicarbonate, 1x100 mL deionized water and then dried over anhydrous magnesium sulfate.
• the structure was confirmed by GC/MS and NMR.
• 2,2,3, 4,4,4-hexafluorobutan-l-ol (184 g, 1.012 moles, available from Lancaster Synthesis Ltd., Ward Hill, MA), triethylamine (102 g, 1.008 moles) and methyl-t-butyl ether (350 mL) in a 1-L round bottom flask that was maintained at a temperature between 5°C and 15°C with a CCVwater bath.
• ethylchloroformate 100 g, 0.92 moles was added from a jacketed addition funnel that was maintained between 5°C and 15°C.
• the ethylchloroformate was added over a period of 4 h. Once addition was complete, the reaction mixture was stirred for an additional 16 h and was allowed to warm to room temperature. Then 100 mL of distilled water was added to the reaction mixture. The organic phase was collected. The water phase was extracted twice with 100 mL portions of methyl t-butyl ether and all of the organic phases were combined. The organic phase was washed with a 100 mL portion of distilled water and a 100 mL portion of IN HCl. The ether was removed by rotary evaporation. The remaining sample was purified by fractional distillation, using a concentric tube column. The product was analyzed by GC/MS.
• the reaction mixture was stirred for about 18 h at ambient temperature.
• the reaction mixture was combined, with stirring, with a premixed solution of 200 mL of 1.023 N HCl and 300 mL of deionized water.
• the resulting mixture separated into two phases.
• the organic phase was washed sequentially with 400 mL of water, 400 mL of 5% Na 2 CO 3 , and two 400 mL portions of water.
• the organic phase was treated for 3 days with activated 3A molecular sieves.
• the product was collected by fractional distillation, under nitrogen, at atmospheric pressure and a head temperature of 151.2-153.0 0 C.
• the product was analyzed by GC/MS and the purity was measured as
• 2,2,3,3-tetrafluoropropan-l-ol (121 g 0.92 mol), pyridine (76 g 0.96 mol) and 350 mL of methyl-t-butyl ether were combined in a 1 L 3 -neck round bottom flask.
• the flask was equipped with an overhead stirring mechanism, thermocouple, addition funnel, cold water condenser, and a dry nitrogen bubbler.
• the reaction flask was kept cool using solid CO 2 in a water bath.
• Ethylchloroformate (100 g, 0.92 mol) was added via an addition funnel dropwise at a rate such that the temperature of the reaction mix did not exceed O 0 C. Once the addition was complete the mix was allowed to warm to room temperature on its own.
• the reaction mix was then quenched with 10OmL of water.
• the water portion was extracted with 2 xlOOmL portions of methyl t-butyl ether.
• the combined organic extracts were washed with 100 mL of IN HCl and 100 mL of water.
• the solvent was removed by rotary evaporation and the carbonate was purified by fractional distillation using a concentric tube column.
• the structure of the product was confirmed by GC/MS and the purity by GC-FID was 99.05% of the desired compound.
• 2,2,2-trifluoroethanol 105 g 1.05 mol
• pyridine 87 g 1.1 mol
• 300 mL of methylene chloride 300 mL
• the flask was equipped with an overhead stirring mechanism, thermocouple, addition funnel, cold water condenser, and a dry nitrogen bubbler.
• the reaction flask was kept cool using a dry ice/acetone bath to keep the temperature in the range of -20 0 C to -15 0 C.
• Methylchloro formate 100 g 1.05 mol
• Cp Specific Heat Capacity
• Perkin Elmer thermal analysis software was used to calculate the heat capacity and was calibrated against the known heat capacity of a sapphire reference.
• Heat Capacity data were taken starting with -20 0 C in 20 0 C increments, reporting one heat capacity value in the middle of each 20 0 C heating range in order to avoid transient data at the beginning and end of each heating range. Data was reported (see
• Comparative Example 1 is a commercial hydrofluoroether compound, CF 3 CF 2 CF 2 CF(OCH 2 CH 3 )CF(CFS) 2 , available as NOVEC 7500 Engineered Fluid, from 3M Company, St. Paul, MN.
• CF 3 CF 2 CF 2 CF(OCH 2 CH 3 )CF(CFS) 2 available as NOVEC 7500 Engineered Fluid, from 3M Company, St. Paul, MN.

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