US006261694B1 (12) United States Patent (10) Patent N0.: US 6,261,694 B1 Iac0vangel0 (45) Date of Patent: Jul. 17,2001 (54) INFRARED REFLECTING COATINGS H. Bolt et al., Gradient Metal—a—C:H Coatings Deposited From Dense Plasma by a Combined PVD/CVD Process, 98 (75) Inventor: Charles Dominic Iacovangelo, Surface and Coatings Technology 1518—1523 (1998). Niskayuna, NY (US) DE. Brodie et al., Characterization of ZnO for the Fabri cation of Conductor—lnsulator—Semiconductor (CIS) Solar (73) Assignee: General Electric Company, Cells, Conf. Proc. for IEEE 14th Photovoltaic Spec. Conf. Schenectady, NY (US) 468—471 (Jan. 7—10, 1980). DA. Gerdeman and N.L. Hecht,Arc Plasma Technology in ( * ) Notice: Subject to any disclaimer, the term of this Materials Science 1—17 (1972). patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days. S. J ager et al., Comparison of Transparent Conductive Oxide Thin Films Prepared by AC. and DC. Reactive Magnetron Sputtering, 98 Surface and Coatings Technology 1304—1314 (21) Appl. No.: 09/271,658 (1998). (22) Filed: Mar. 17, 1999 Jianhua Hu and Roy G. Gordon, Deposition of Boron Doped Zinc Oxide Films and Their Electrical and Optical Proper (51) Int. Cl.7 .................................................... .. B32B 27/36 ties, 139 J. Electrochem. Soc. 2014—2022 (1992). Z.—C. Jin et al., Optical Properties of Sputter—Deposited (52) us. Cl. ........................ .. 428/412; 428/332; 428/458; ZnO:A1 Thin Films, 64 J. Appl. Phys. 5117—5131 (1988). 428/469 RA. MacGill et al., Cathodic Arc Deposition of Copper Oxide Thin Films, 78 Surface and Coatings Technology (58) Field of Search ................................... .. 428/412, 457, 168—72 (1996). 428/469, 332, 458 S. Major et al., Electrical and Optical Transport in Undoped and Indium—doped Zinc Oxide Films, 1 J. Mater. Res. (56) References Cited 300—310 (1986). U.S. PATENT DOCUMENTS S. Major et al., Highly Transparent and Conducting Indi um—Doped Zinc Oxide Films by Spray Pyrolysis, 108 Thin 3,161,615 12/1964 Goldberg . Solid Films 333—340 (1983). 3,220,973 11/1965 Goldberg . 3,312,659 4/1967 Kurkjy et a1. . (List continued on next page.) (List continued on next page.) Primary Examiner—D. S. Nakarani FOREIGN PATENT DOCUMENTS Assistant Examiner—Monique R. Jackson (74) Attorney, Agent, or Firm—Robert P. Santandrea; 0464789 7/1991 (EP). 0887433 12/1998 (EP). Noreen C. Johnson 2586245 8/1986 (FR). (57) ABSTRACT 11-070610 3/1999 (JP). 8901957 8/1988 (WO). An infrared radiation re?ecting and ultraviolet radiation 9011975 10/1990 (WO). absorbing coating is formed over a polymeric substrate. 9213517 2/1992 (WO). Preferably, the substrate is a transparent polycarbonate 9713802 10/1996 (WO). Window, and the coating comprises an IZO/Ag/IZO multi OTHER PUBLICATIONS layer ?lm. The layers are preferably deposited by are plasma deposition or by sputtering. S. Anders et al., Formation of Metal Oxides by Cathodic Arc Deposition, 76—77 Surface and Coatings Technology 167—73 (1995). 31 Claims, 13 Drawing Sheets (/ W3 (V2 1 US 6,261,694 B1 Page 2 US. PATENT DOCUMENTS Tadatsugu Minami et al., Group III Impurity Doped Zinc Oxide Thin Films Prepared by RF Magnetron Sputtering, 24 3,312,660 4/1967 Kurkjy et al. . Japanese J. of Appl. Phy. L781—L784, (1985). 3,313,777 4/1967 Elam et al. . 3,576,656 4/1971 Webb et al. . Tadatsugu Minami et al., Highly Conductive and Transpar 3,666,614 5/1972 Snedeker et al. . ent Silicon Doped Zinc Oxide Thin Films Prepared by RF 3,989,672 11/1976 Vestergaard . Magnetron Sputtering, 25 Japanese J. of Appl. Phys. 4,194,038 3/1980 Baker et al. . 4,200,681 4/1980 Hall et al. . L776—L779, (1986). 4,210,699 7/1980 Schroeter et al. . M. MiyaZaki and E. Ando, Durability Improvement of 4,224,378 9/1980 Schroeter et al. . Ag—Based LoW—Emissivity Coatings, 178 J. Non—Crystal 4,242,381 12/1980 Goossens et al. . 4,454,275 6/1984 Rosenquist . line Solids 245—249 (1994). 4,799,745 * 1/1989 Meyer et al. ...................... .. 359/360 4,842,941 6/1989 Devins et al. . C.X. Qiu and I. Shih, Tin—and Indium—Doped Zinc Oxide 4,871,580 10/1989 Schram et al. . Films Prepared by RF Magnetron Sputtering, 13 Solar 4,927,704 5/1990 Reed et al. . Energy Materials 75—84 (1986). 4,943,484 7/1990 Goodman ........................... .. 428/441 4,948,485 8/1990 Wallsten et al. . D. Raviendra and J .K. Sharma, Electroless Deposition of 5,008,148 4/1991 Thurm et al. . Cadmium Stannate, Zinc Oxide, and Aluminum—Doped 5,019,458 * 5/1991 Elgat et al. ........................ .. 428/630 Zinc Oxide Films, 58 J. Appl. Phys. 838—844 (1985). 5,051,308 9/1991 Reed et al. . 5,156,882 10/1992 RZad 6t 61. . R.E.I. Schropp et al., Transparent and Conductive Thin 5,271,994 12/1993 Termath ............................. .. 428/216 Films of ZnO for Photovoltaic Applications Prepared by RF 5,298,587 3/1994 Hu 6181.. Magnetron Sputtering, 1 Conf. Rec. of 20th IEEE Photo 5,320,875 6/1994 Hu 6181.. voltaic Spec. Conf. 273—276 (Sep. 26, 1988). 5,342,676 * 8/1994 Zagdoun ............................ .. 428/216 5,433,786 7/1995 Hu 6181.. BE. Sernelius et al., Band—Gap Tailoring of ZnO by Means 5,463,013 10/1995 Tokuda et al. . of Heavy A1 Doping, 37 Physical RevieW B of Am. Phys. 5,480,722 1/1996 Tomonaga et al. . 5,494,712 2/1996 Hu et 61.. Soc., 10244—10248 (1998). 5,510,448 4/1996 Fontane et al. . I. Shih and C.X. Qiu, Indium—Doped Zinc Oxide Thin Films 5,614,248 3/1997 Schiller et al. . Prepared by RF Magnetron Sputtering, 58 J. Appl. Phys 5,635,087 6/1997 Schiller et al. . 5,718,967 2/1998 Hu 6181.. 2400—2401 (1985). OTHER PUBLICATIONS S. Sreedhara Reddy et al., Optical Properties of Spray Deposited ZnO Films, 77 Solid State Communications S. Maniv et al., Transparent Conducting Zinc Oxide and Indium—Tin Oxide Films Prepared by Modi?ed Reactive 899—901 (1991). Planar Magnetron Sputtering, A1 J. Vac. Sci. Tech. 1370—1375 (1983). * cited by examiner U.S. Patent Jul. 17, 2001 Sheet 1 0f 13 US 6,261,694 B1 R>>o.E_._m_ > ______ mC.FOQ5EIn‘c 26N<mM2N222ON£7*W2NN2222w222222222: wm#N0NA#M2N32W2..E..2222222..22Z2222 WN.W.225263:26 ww2z5M<5¢65o5 53 w._m_w_> ____________(u?o ___ _____________\ ____ U.S. Patent Jul. 17, 2001 Sheet 2 0f 13 US 6,261,694 B1 x F FIG. 2A FIG. 2B U.S. Patent Jul. 17, 2001 Sheet 3 0f 13 US 6,261,694 B1 FIG. 3A FIG. 38 5143 2 FIG. 3C FIG. 30 41532 6 FIG. 3E FIG. 3F U.S. Patent Jul. 17, 2001 Sheet 4 0f 13 US 6,261,694 B1 l\\\\\\\\\\| 11 21 ‘X N\l g //////// f F4IG. l\ \\\\\\\\l 25Z PK‘ F2 24 6122 \ \\\\\ | I\\\\\\\\ 1O ZR“ 13 U.S. Patent Jul. 17, 2001 Sheet 6 6f 13 US 6,261,694 B1 U.S. Patent Jul. 17, 2001 Sheet 8 0f 13 US 6,261,694 B1 NN/ ow U.QmE 2 NF