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US5198189.Pdf |||||||||||| USOO598 89A United States Patent (19) 11 Patent Number: 5,198,189 Booth et al. r (45) Date of Patent: Mar. 30, 1993 54) LIQUID METAL MATRIXTHERMAL PASTE FOREIGN PATENT DOCUMENTS (75) Inventors: Richard B. Booth, Wappingers Falls; 0009605 4/1980 European Pat. Off. Gary W. Grube, Washingtonville; 332981 4/1972 U.S.S.R. ............................. 420/.555 Peter A. Gruber, Mohegan Lake; Igor Y. Khandros, Peekskill; Arthur OTHER PUBLICATIONS R. Zingher, White Plains, all of N.Y. Patent Abstracts of Japan, vol. 12, No. 342 (E-658), 73 Assignee: International Business Machines Sep. 14th, 1988; JP-A-63 102 345 (Fujitsu Ltd) May 7, 1988. Corporation, Armonk, N.Y. Patent Abstracts of Japan, vol. 8, No. 236 (C-249), Oct. 21 Appl. No.: 870,152 30th, 1984; and JP-A-59 16 357 (Hitachi Seisakusho K.K.) Jul. 5, 1984. (22 Filed: Apr. 13, 1992 Patent Abstracts of Japan, vol. 7, No. 218 (E-200), Sep. 28th, 1983; and JP-A-58 111 354 (Hitachi Seisakusho Related U.S. Application Data K.K.) Jul. 2, 1983. a Patent Abstracts of Japan, vol. 11, No. 3 (C-395), Jan. 63 Continuation of Ser. No. 389,131, Aug. 3, 1989. 7th, 1987; and JP-A-61 179 844 (Tokuriki Honten Co., 51) Int. C. .............................................. C22C 28/00 Ltd) Aug. 12, 1986. 52 U.S. Cl. ..................................... 420/555; 252/387 Primary Examiner-Peter D. Rosenberg 58 Field of Search ..................... 420/555; 228/1802; Attorney, Agent, or Firm-Philip J. Feig 252/38 7 57 ABSTRACT (56) References Cited A liquid metal matrix thermal paste comprises a disper U.S. PATENT DOCUMENTS sion of non-reacting thermally conductive particles in a 3,150,901 9/1964 Esten et all 308/241 low melting temperature liquid metal matrix. The parti 3,169,859 2/1965 Treaftis et al........ 75/134 cles preferably are silicon, molybdenum, tungsten or 3,175,893 3/1965 Meretsky et al. ... .25/19, other materials which do not react with gallium at ten 3,209,450 10/1965 Klein et al. .......... 29/492 peratures below approximately 100° C. The preferred 3,839,780 10/1974 Freedman et al. ... 29/50 liquid metals are gallium and indium eutectic, gallium 4,092,697 5/1976 Spaight ... - - - - - - 361/386 and tin eutectic and gallium, indium and tin ternary 4,233,103 11/1980 Shaheen ... a > 0 a 56/33 eutectic. The particles may be coated with a noble metal 4,239,534 12/1980 Taketoshi ................. 75/13T to minimize surface oxidation and enhance wettability 4,323,914 4/1982 Berndlmaier et al. ... a 357/82 of the particles. The liquid metal matrix thermal paste is 4,398,975 8/1983 Ohsawa et al. .......... 4,659,384 4/1987 Daigo et al. ......... 1. used aS a high thermally conducting paste in cooling 5,012,858 5/1991 Natori et al. ..... .420/$55 high power dissipation components in conjunction with 5,024,264 6/1991 Natori et al. ..... .420/555 a conventional fluid cooling system. 5,053,195 10/1991 MacKay ....... ... 420/.555 5,056,706 10/1991 Dolbear et al. - - - - - - - - - 228/80.2 20 Claims, 3 Drawing Sheets U.S. Patent Mar. 30, 1993 Sheet 1 of 3 5,198,189 F G. 2A FIG. 2B U.S. Patent Mar. 30, 1993 Sheet 2 of 3 5,198,189 F. G. 3 ATOMIC PERCENT TN O 40 20 30 40 50 6O 70 80 90 00 300 250 200 50 400 50 LOUD + T IN 20.50C O (a Sn) 00 GO Sn 65 wt % Sn U.S. Patent Mar. 30, 1993 Sheet 3 of 3 5,198,189 5, 198,189 1. 2 scopic filling of liquid metal. Also, U.S. Pat. No. LIQUID METAL MATRIXTHERMAL PASTE 4,323,914 teaches the coating of the entire chip with a parylene film coating and then adding a macroscopic This application is a continuation of application Ser. metal joint to the cooling cap. Both of these patents No. 07/389,131 filed Aug. 3, 1989. 5 degrade the thermal conductivity of the joint by includ BACKGROUND OF THE INVENTION ing a poor thermal conductivity plastic film. The present invention relates to thermal paste and SUMMARY OF THE INVENTION particularly relates to a liquid metal matrix thermal The present invention provides a liquid metal matrix paste containing fine thermally conducting particles O thermal paste containing fine thermally conductive dispersed in a low melting temperature liquid metal particles dispersed in a low melting temperature liquid matrix and having high overall thermal conductivity. metal matrix. Preferably, the particles are metal or con The thermal paste is used to form a thermal joint be ductive non-metals selected to be non-reactive with the tween an electronic component, such as a chip, and a liquid metal matrix at low temperature in order to pro cooling system. 5 vide a semi-liquid fully compliant structure for an indef Modern very high performance electronic systems inite period of time. The particles are preferably tung often require a high density of chips having many high sten, molybdenum, silicon or other metals or high ther power gates. These electronic systems require cooling a mal conductivity materials which have a very low inter high power density through a limited temperature drop action rate with gallium, tin and indium at low tempera from a device junction to a cooling system. In order to 20 achieve the cooling requirement, the thermal joint from ture, i.e. at temperatures below approximately 100° C. the chip to the cooling system must possess a high ther The particles can also be non-metals having high ther mal conductivity. The thermal paste described hereinaf mal conductivity, such as diamonds. The particles can ter provides the highest available thermal conductivity be coated to enhance wettability. The preferred liquid thermal joint between a chip or component and the 25 metal matrix are gallium and indium eutectic alloys, cooling system obtained to date. gallium and tin eutectic alloys, and gallium, indium and In practical applications, the joint, in addition to pro tinternary eutectic alloys. viding high thermal conductivity, must compensate for The liquid metal matrix thermal paste is formulated as certain manufacturing tolerances inherent in any elec described below as a gallium-metal paste which perma tronic assembly. For instance, when assembling chips 30 nently and indefinitely retains its semi-liquid state under using the so-called controlled collapse circuit connector normal operating conditions and environment to serve technique (hereinafter referred to as C4), as a result of as a compliant thermal interface. The resultant paste variations in the size and shape of the solder ball arrays acts as a high thermal conductive medium which is used to connect the chip to a printed circuit board, there formed into a desired shape to enhance thermal transfer. are significant variations in chip height and tilt relative 35 By retaining its semi-liquid state under normal operat to the printed circuit board. The electrical connections, ing conditions without solidifying, the enhanced ther the C4 solder balls, are very fragile and the thermal mal transfer via the paste is sustained during many on joint must permit a certain amount of differential mo off power cycles when the components of the cooling tion of the individual chips forming an electrical system system expand and contract. The differential expansion assembly. Also, manufacturing tolerances cause varia of the various components results in significant thermal tions of the gap between the chip and the cooling sys stresses, which are particularly damaging at the compo tem. The combination of geometric variations and toler nent interfaces. A paste which solidifies over time, and ances conflict with the goal of achieving good thermal therefore, does not provide a compliant interface, will conduction by causing a very thin paste layer to be eventually crack after repeated expansion and contrac manifest between certain of the chips and the cooling 45 tion and cease to function as a good thermal transfer system. Despite the difficulty encountered, good ther medium. mal conduction is still achievable by using a paste hav A principal object of the present invention is, there ing high bulk thermal conductivity properties. fore, the provision of liquid metal matrix thermal paste Using known conventional thermal paste has pro having a high thermal conductivity while remaining in vided moderately good heat transfer plus moderate SO a semi-liquid state for an indefinite period of time. compliance. A commonly used paste contains a mixture Another object of the invention is the provision of a of zinc oxide in mineral oil. Such pastes have an upper liquid metal matrix thermal paste having high thermal limit of thermal conductivity. Also, the liquid and parti conductivity and adjustable viscosity. cles tend to phase separate after many power on-off A further object of the invention is the provision of a cycles. The conventional pastes rely upon the percula 55 liquid metal matrix thermal paste having high thermal tion of oxide particles in a low conductivity oil matrix conductivity for use as a thermal joint between an elec for thermal conductivity. The use of a low conductivity trical component, such as a chip, and a cooling system, oil matrix is the primary limiting factor in achieving or between successive parts of a cooling system. high thermal conductivity. The present invention pro A still further object of the invention is the provision vides for a high thermal conductivity of both the liquid of a liquid metal matrix thermal paste containing fine matrix and the dispersed particles. thermally conducting particles dispersed in a low tem There have been many proposals to use liquid metal perature liquid metal matrix which is stable for an indef thermal joints, particularly mercury, which may be inite period of time.
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