‘Beeitiowocy exclusive Feature by Tuma and Knoll Lof 12 ‘CHEMICALS A comparison of fluorinated and Di/glycol heat transfer fluids Phil E. Tuma, 3M Electronics Markets Materials Division, St. Paul, Minnesota Scott Knoll, Lydall Industrial Thermal Solutions Many recirculating chiller applications in semiconductor manufacturing require electrically nonconductive or “dielectric” heat transfer fluids. A dielectric fluid may be required to maintain electrical isolation of components maintained at an electrical potential or may be desirable from a reliability viewpoint to prevent component damage in the event of a fluid leak. Although there are many dielectric fluids available, many are not suitable for use in semiconductor ‘manufacturing, For example, petroleum-based fluids, hydrocarbons, or silicone oils tend to be flammable or combustible. Others are elin nated for thermal stability reasons or because they leave behind residue and odor after a spill. Chlorinated fluids are discounted because they are ozone depleting or highly regulated for their toxicity [1] ‘The choices remaining are deionized (DI) fluids and fluorinated fluids, DI fluids — ineluding water and/or ethylene or propylene glycol — may also contain corrosion inhibitors, Referred to as “DU/glycol fluids,” they are still used quite often in etch, chemical vapor deposition (CVD), and even some automatic test (ATE) applications. However, they were most common prior to the early 1990s. At that time, evolving process temperatures necessitated use of fluorinated fluids, which include perfluorocarbon (PFC) fluids (2] and hydrofluoroether (HFE) fluids (3). Today, both Difglycol and fluorinated fluids are used. This paper discusses the inherent advantages and disadvantages of each category. As will be shown, fluorinated fluids, when used in « properly designed system, are more versatile, more economical, more reliable, and easier to use than Dl’glycol fluids. ‘Temperature range Fluorinated fluids are normally used at temperatures up to 10°C below their boiling point [4] ‘SIVISILYA SAY Wer Ary RTH 801LS-Z22-998‘Beeitiowocy exclusive Feature by Tuma and Knoll of 12 Using 30¢St as a eriterion for low temperature utility, fluorinated fluids typically have a useful Tiquid range (maxiumum use temperature minus minimum use temperature) between 130°C and 200°C (Fig. 1). The availability of fuids with boiling points ranging from 30°C to over 200°C greatly expands the breadth of fluorinated fluid applications. Fluorinated fluids have been used at temperatures as low as —120°C and well over 200°C. wie- Btn Bu nvacs 8 888 Micoany es NRE Babe os ‘Temperature (0) Figure 1. Viscosity vs. temperature plot for water, a $0% ethylene glycol solution, and fluorinated Nuids of ‘The maximum use temperature of a DIglycol system is practically limited to 60-80°C. This limitation is imposed by the temperature limit of deionizing beds used to maintain the electrical resistivity of the fluid. This limit may be further reduced by corrosion concems if high electrical resistivity is required. In the case of water, the minimum use temperature is fixed by the freezing point to about 10°C resulting in a 50-70°C operating range. In the case of glycol solutions, the low temperature limit is dictated by viscosity. Using the same 30¢St criterion, a 50% ethylene ¢glycol/water solution can reach -24°C and therefore has an operating range of 84-104°C [5]. A 50% propylene glycol/water solution has a narrower operating range, reaching 30eSt at —13°C. For this reason, propylene glycol is rarely used in semiconductor manufacturing applications. ‘SIVISILYA SAY & R . RK A iF 801LS-ZL2-998‘Beeitiowocy exclusive Feature by Tuma and Knoll 3of 12 Glycol solutions are hygroscopic under certain conditions and will absorb moisture from the ait. For example, pure ethylene glycol, if left to equilibrate with ambient air at 27°C (80°F) and 40% relative humidity (dewpoint 12°C or 53°F), will absorb water until the resultant solution contains about 85% ethylene glycol by weight [6] (see Fig. 2). If chilled to 15.6°C (60°F) but otherwise in equilibrium with the same ambient air, the solution will contain 59% ethylene glycol. All solutions, regardless of their concentration, will condense and absorb water from air if maintained below the dewpoint of that air. The rate of absorption depends strongly upon conditions. Absorption will be quite slow for a quiescent container with a slight leak, faster for an open container, and quite rapid for a well-agitated chiller with the reservoir left open. 100 90 80 ‘Am iont Conditions: & = 70 ° ° 23 | 227 C (80°F), 20% RH £3 60 ° ° so 27°C (80°F), 40% RH 5 5 50 83 y ar slant % Si 40 Einylone | Freezing Ze atone | Bait re) SE 30 & 7 7 e 20 20 7.8 a0] 23 10 a Dewpoints 80 46.8 0 0 5 10 18 20 25 30 35 40 Glycol Solution Temperature [°C] Figure 2. Concentration of ethylene glyc rium with ambient air at 80°F and 20% or 40% relative humidit This characteristic has important implications for chiller systems because the freezing temperature of a glycol solution increases with water content (Fig. 2). For example, to operate at ~15°C using a standard R404A/R507 chiller operating with a -26°C evaporation or “suction” temperature, one might prepare a solution that is 47 wt% ethylene glycol. This solution has a freezing point of -30°C assuming, of course, that the “pure” glycol one started with had not already absorbed water from ‘SIVISILYA SAY Wer Ary RTH 801LS-Z22-998‘Beeitiowocy exclusive Feature by Tuma and Knoll ambient air. If it is exposed to the ambient air described earlier (dew poi 4 of 12 12°C), this solution will quickly absorb moisture from the air. Ifthe concentration of ethylene glycol gets as low as 41 ‘wi% (representing a 15% weight increase), the freezing point will rise above ~24°C), where there is danger that the glycol will freeze and burst the evaporator. This characteristic requires that Di/glycol chiller reservoirs be very well sealed. Safety Perfluorocarbon (PFC) fluids are among the most inert materials known so they are generally rated as “practically nontoxic” with neither acute nor 8-hr exposure guidelines. The 8-hr exposure ‘guidelines for three HFEs vary, as shown in Table 1. Acute toxicity studies reveal toxicity levels are sufficiently low — acute exposure limits are not set. Industrial hygiene experiments have been conducted with HFEs using standard Fourier transform infrared (FTIR) monitoring techniques. Continuous sampling at various heights above 10 ft spills in spaces with 3 air changes/hr show that the 8-hr exposure guidelines are rarely reached even for short periods of time [7]. Exposures during normal filling and draining operations (i.., without spills) are exceedingly low so that use of these products is inherently safe. Though ethylene glycol has a relatively low 8-hr exposure guideline of SOppm, its low vapor pressure makes inhalation an unlikely exposure route. Table 1. Toxicological properties for commercially available HFES Novec HFE-7100 Novec HFE-7200 Novec HFE-7500 Boiling point PC (°F)] 61 (142) 76 (169) 128 (262) (cute lethal cone., 4-hr > > : G50 (gore) 100,000 92,000 NA Joral toxicity Practically nontoxic (>5ghkg) | Practically nontoxic >59%9) | i peosoomgikg E Negative Negative Negative ardiac sensitization > . faoahald top} 00,000 20,000 NA cular iritant No Mimimally iritating No mal irritant No No No Exposure guideline &-hr [FWA (ppm) 750 200 mM Exposure ceiling (ppmv) None None No “NA = Inhalation not a likely exposure route for this material due to low volaillity Environmental Neither HFE nor PFC fluids are ozone-depleting. PFC flui however, have high GWPs [8]. The semiconductor industry has been proactively reducing emissions of PFC gases for many years and ‘SIVISILYA SAY Wer Ary RTH 801LS-ZL2-998‘Beeitiowocy exclusive Feature by Tuma and Knoll Sof 12 has recently tured its attention to redueing usage and emissions of PFC liquids, HFE fluids are the preferred alternative. They share most of the desirable properties of PFC fluids, but have very short ‘atmospheric lifetimes and low GWPs [9] Heat transfer performance The thermal conductivity and specific heat of DI/glycol fluids are about 5-8 and 4 times, respectively, those of fluorinated fluids. Because DI/glycol fluids have much higher specific heat, they require lower flow rates to achieve a prescribed temperature change [10]. Under these conditions and assuming turbulent flow, water will produce higher heat transfer coefficients than fluorinated fluids. When compared with ethylene glycol at moderate temperatures, fluorinated fluids will produce similar heat transfer coefficients. At lower temperatures, the viscosity of glycol begins to increase (Fig. 1) and fluorinated fluids will produce higher heat transter coefficients. Figure 3 shows results of theoretical turbulent heat transfer calculations [111] for a 0.1 in. pipe with water flowing at 3 gallons/minute (gpm). Flow rates of the other fluids are adjusted to match the thermal capacity of the water, 2.06+05 -— eater 1.86+05 | = 50 vl Ethylene Giyeo! 166+05 | ee HFE-7200 14e+05 | SOMHFE-7500 Heat Transfer Coefficient, h (Wim?-K] Figure 3. Theoretical turbulent heat transfer coefficients for a 0.1 in. pi with water flowing at 3 gpm. Flow rates of the other fluids were adjusted to match the thermal capacity of water. 11 is important to note, however, that as long as the fluid viscosity is not prohibitive, both classes of fluids will perform well. This is because the limiting thermal resistance within a semiconductor ‘SIVISILYA SAY Wer Ary RTH 801-722-998‘Beeitiowocy exclusive Feature by Tuma and Knoll Gof 12 ‘manufacturing system is rarely the fluid itself: For example, in CVD applications, the wafer typically sits atop a chuck made of a stainless steel or aluminum alloy. Fluid is pumped through the chuck to maintain its temperature but rarely is the thermal resistance between the fluid and the inner surfaces of the chuck limiting. Most often, the conduction within the chuck or interface resistances between the chuck and wafer dominate, The same can be said of test applications in which cooled heat sinks are held in physical contact with integrated circuit packages. Other considerations In transient applications, the lower specific heat of'a fluorinated fluid, which is often believed to be a shortcoming, can be an advantage. Because the volumetric thermal mass of a fluorinated fluid is typically 50% that of water or an ethylene glycol solution, the amount of heating or cooling power required to achieve a certain rate of temperature change is reduced accordingly. Many ATE thermal stress, CVD, and etch applications require frequent process temperature changes and decreased ‘temperature ramp time increases throughput. In a typical wide spanning chiller application, a standard, six horsepower, low temperature scroll compressor system operating with HFE-7500 is, able to ramp a thermal chip handling machine from ~40°C to 100°C in 20 minutes and from 100°C to 45°C in under 15 minutes, With the same unit and a 50% ethylene glycol solution ramping from -20° to 80°C or 80°C to ~20°C would exceed 40 min [12] Electrical properties ‘The resistivity of PFC and HFE fluids are typically 10'S and 10° ohm-cm, respectively. The solubility of ionic contaminants in fluorinated fluids is exceedingly low (<10 ppb), so the electrical resistivity of a fluorinated fluid will not change considerably under use or spill conditions. The dielectric strength of a fluorinated fluid is typically in the 10-60kV range for a 1/L0th inch gap. This value is sensitive to the water content and may be as low as 10-20kV when dewpoints reach ambient temperature (saturation). The dielectric strength is relatively insensitive to other dissolved contaminants, such as organic oils, but can be affected by particulate. The dielectric constant of PFC fluids is typically 1.7-2.0. HFE fluids have dielectric constants between 5.0 and 8.0. PFC and HEE fluids are transparent to visible light and also much of the ultraviolet (UV) and microwave spectrum. HFE fluids will absorb energy at microwave wavelengths, The best attainable resistivities for DI water and DI/glycol are about 10’ and 10% ohm-em, respectively. The resistivity of D/glycol fluids can degrade quickly if the deionizing bed is not ‘SIVISILYA SAY Wer Ary RTH 801LS-ZL2-998‘Beeitiowocy exclusive Feature by Tuma and Knoll Tot 12 properly maintained or if the fluid is spilled. The dielectric constants of ethylene glycol and water ate 38 and 78, respectively [13], at 25°C. ‘Material compatibility Fluorinated fluids are very chemically inert and function very well with most hard polymers including: acrylic, polyethylene, polypropylene, polyoxymethylene, polyvinylehloride (PVC), polycarbonate, polyamide, polytetrafluoroethylene (PTFE), polysulfone, polyphenylene sulfide, phenolic, polyetheretherketone (PEEK), polyimide, and many others. Fluorinated fluids perform best with elastomeric polymers that contain little extractable oil or plasticizer. There are a variety of inexpensive and readily available butyl, ethylene propylene (EP), and polyurethane materials that perform well. Silicone and fluorocarbon elastomers are prone to swelling and permeation but often perform quite well in certain applications. The effect of DI/glycol fluids on polymers is similar to that of fluorinated fluids. While hard polymers may be relatively unaffected, elastomeric polymers may shrink or become brittle as low molecular weight material is leached by the fluid. EPDM, nitrile, and fluorocarbon elastomers are typically recommended for use with ethylene glycol, Corrosion Fluorinated fluids are nonpolar, chemically inert, and inherently noncorrosive. When observed in a fluorinated fluid system, corrosion can usually be linked to water added inadvertently by an ‘operator or water condensed from ambient air through a reservoir vent on a system operating at cold temperatures. The latter is avoided by drying the fluid with common reagents (silica gel, molecular sieve, or calcium sulfate) or by sealing the reservoir Because they are very polar, DI/glycol fluids have a strong tendency to solvate metal ions and can, therefore, be corrosive toward metals. For this reason, copper, zine, and brass are generally not used in Di/glycol based chillers when resistivity levels must exceed 2-3 Mohm-cm regardless of the temperature range. Over time, all Di/glycol fluid chillers requiring operation above 60°C — even when built with 100% welded or brazed stainless steel — show signs of corrosion Glycols can cause corrosion by another mechanism, They produce organic acids as they oxidize. If left in solution, these acids will lower the fluid’s pH leading to metallic corrosion rates greater than ‘SIVISILYA SAY Wer Ary RTH 801LS-ZL2-998‘Beeitiowocy exclusive Feature by Tuma and Knoll Bof 12 plain water. Inhibitors are typically added to passivate metalic surfaces and buffer the pH of the glycol solution. Consumption of these inhibitors and oxidation of the glycol are accelerated by high temperatures, the presence of copper or aluminum, and exposure to a renewable oxygen source like air [14]. That is another reason that reservoirs in such systems must be well sealed and one reason many DI beds also have a deoxygenation (DO) function. Costs Initial costs. Fluorinated fluids range in cost from $200-S00/gallon. Fluorinated fluid chillers can be plumbed with inexpensive brazed copper or brass components, but generally require a more expensive magnetically coupled or canned pump. DI/glycol systems require DI or DI/DO beds and special sensors and control, and may require stainless steel construction. In general, a fluorinated ‘luid chiller will be 0-35% more expensive — depending upon temperature range — than a sub-1 Mohm-cm Di/glycol chiller plumbed copper, but 25-50% less expensive than a high resistivity Dl/glycol chiller made of stainless steel. For applications with <8—S0 gallons/system (by far the majority), these savings usually compensate for the additional cost of a fluorinated fluid. Maintenance s. Fluorinated fluids have essentially an infinite usage life and, if properly used, should never need replacement. Maintenance costs associated with fluorinated fluid heat transfer systems are limited to the cost of fluid used to “top off” the system to compensate for losses. In the early 1990s, fluorinated fluid heat transfer systems were rightly perceived to be quite “leaky.” Often fluorinated fluids were put into systems designed for use with aqueous fluids. Because ‘fluorinated fluids are highly wetting, low surface tension liquids, they would leak from the pumps, valves and seals designed for aqueous fluids. Other times, fluorinated fluids were put into chillers that allowed the fluid to evaporate [15]. Although designers unaccustomed to fluorinated fluids do still occasionally struggle with sealing problems, today the industry as a whole has a greater appreciation of the design requirements of fluorinated fluids. Leakage from moder systems is exceedingly low. Some require topping off less than once every two years ‘The corrosiveness of high purity Dl/glycol (compounded at high temperatures), coupled with the electrical conductivity of low purity DI/glycol means that a system often must operate in a narrow resistivity range. Resistivity monitoring can be done manually or automatically by the chiller, which may also keep the resistivity below a maximum setting or indicate when the DI or DI/DO bed must be changed to maintain a minimum resistivity. Though D/DO resin beds cost only ‘SIVISILYA SAY Wer Ary RTH 801LS-ZL2-998‘Beeitiowocy exclusive Feature by Tuma and Knoll 9 of 12 ~$120, they must be replaced quite frequently when used in high temperatureiresistivity applications (Table 2). ‘Table 2. Typical replacement schedule” Low resistivity | High resistivity (<3 Mohm-cm) | (>4 Mohm-cm) High temperature) | 2-3 months 4 month (plumbed with SS beg oh (e50°C) sr eepeer') (SSor PTFE only) Mid-low 1-9 month 2-3 months, temperature 5 mons «| (orimariy with SS ( Mantexance = ‘Weekly monitoring of eistvty & Periodic changing of Dior DIDO bed _ | Varies ftom none to ocesionalop-off = Periodic cleasng i replacement | (typically “10% year) s Monitoring of heal concentation = Rela Ba Tay wa rome to esis beakdowa oF zg yea prone io freeze None & Risk of electra shoring in tho event ofa leak Disposal ‘aris by Tale Typialy spot ethylene glycol must be disposed of nan | Fluid may be re-used indefinitely appropriate waste stream. When compared with DI/glycol, fluorinated fluids offer superior temperature range, electrical properties and service life. Both fluorinated and DI/glycol fluids perform well above about -20°C where fluid thermal resistance is not limiting. Fluorinated fluids can be used well below this, temperature where glycol viscosity and freezing point are prohibitive and also above 80°C where DI beds do not operate. The additional cost of a high resistivity D/glycol chiller usually offsets the & & : A iF cost of a fluorinated fluid. Even for low resistivity applications, the cost of operating a modern fluorinated fluid system is typically lower when one considers costs associated with maintenance of a Di/glycol system. Lastly, fluorinated fluid systems are free of many of the reliability concerns associated with D/glycol systems. . 801LS-ZL2-998‘Beeitiowocy exclusive Feature by Tuma and Knoll i of 12 References 1. The inherent limitations of these and other fluids are discussed in: P. Tuma, “Segregated Hydrofluoroethers: Long Term Alternative Heat Transfer Liquids,” Proceedings of the 2000 Earth Technologies Forum, Washington DC, pp. 266-275, Oct. 30-Nov. 1, 2002. 2. These are sold under the 3M trade name Fluorinert and the Solvay trade name Galden 3. These are sold under the 3M trade name Novee. 4. Itis possible to run fluorinated fluid systems above the flu’ boiling point by pressurizing the fluid or by allowing it to boil from a heated component while the circulator is turned off. This must be conducted within thermal stability limits, which vary from fTuid to fluid. 5. Data taken from the ASHRAE Handbook of Fundamentals, The American Society of Heating Reftigerating & Air Conditioning Engineers, 1997. 6. Based on relative humectant data obtained from Dow literature “Physical Properties of Glycols.” 7. 3M Industrial Hygiene Reports. 8. The atmospheric lifetime of a PFC used in heat transfer applications is generally over 2000 years with a GWP in excess of 6000 based on a 10-year integrated time horizon (ITH), 9. P. Tuma and L. Tousignant, “Reducing Emissions of PFC Heat Transfer Fluids,” Sent Technical Symposium, Innovations in Semiconductor Manufacturing, SEMICON West 2001, pp. 99-115. 10. This is equivalent to matching the thermal capacity of the fluids. This is the product of the fluid’s mass flow rate and specific heat. This has SI units of W/°C. 11, Calculation method described in: P.E, Tuma, L. Tousignant, “New ‘Green’ Heat Transfer Liquids,” Solid State Technology, pp.175-182, June 2000, 12. Tests were conducted with a steady state SOOW load applied during all tests. Results vary based on an application’s metallic mass. 13. CRC Handbook of Chemistry and Physics, CRC Press Inc., 1979. 14, K. Wheeler, “Technical Insights into Uninhibited Fthylene Glycol,” Process Cooling, pp. 19 23, July/August 2002. 15. The mechanism of vapor loss is discussed in: PE. ‘Tuma, L. Tous'gnant, “Modeling Vapor Leak Rate and System Pressures for Heat Transfer Systems that Utilize FC Heat Transfer Liquids,” 3M Technical Service Brief. Authors Phil E. Tuma is an application development specialist in the Heat Transfer Library of the 3M_ Electronics Markets Materials Division, St. Paul, MN 55144: ph 651/737-9895; fax 651/737-4335, ‘SIVISILYA SAY aE RRR Wer Hy, 801LS-ZL2-998‘Beeitiowocy exclusive Feature by Tuma and Knoll 12 of 12 petuma@mmm.com, Scott Knoll is US business development manager and Asia regional manager at Lydall’s Affinity Chiller Division, Ossipee, NH. Scott can be reached at sknoll@lydall.com. —END— ‘SIVISILYA SAY Wer Ary RTH 801LS-ZL2-998