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United States Patent (19) 11, 3,909,270 Kishi Et Al

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United States Patent (19) 11, 3,909,270 Kishi Et Al United States Patent (19) 11, 3,909,270 Kishi et al. (45) Sept. 30, 1975 (54) DICHROIC REVERSIBLE 56 References Cited PHOTOSENSITIVE MATERALS UNITED STATES PATENTS 75) Inventors: Yasuo Kishi, Hirakata; Toshiaki 3,580,688 5/1971 Schneider...... ..., 356/256 Yokoo, Osaka; Terutoyo Imai, 3,720,926 3/1973 Schneider...... 340/173 CC Neyagawa; Keiichi Kanatani, 3,761,267 9/1973 Gilman et al......................... 96/ 108 Hirakata; Takehito Yazaki, Katano, 3,814,601 6/1974 Schneider............................... 96/88 all of Japan 73 Assignee: Director of Agency of Industrial Primary Evanniner-Won H. Louie, Jr. Science & Technology, Japan 57) ABSTRACT 22 Filed: Aug. 28, 1973 New materials are the dichroic reversible photosensi (21) Appl. No.: 392,302 tive materials which are the crystals of an alkali metal halide in which are contained an alkali metal ion hav 30) Foreign Application Priority Data ing smaller ion radius than that of the alkali metal in said alkali metal ion and one or more kinds of metal Aug. 30, 1972 Japan................................ 47-86608 ions other than alkali metal ion which possess an abil 52 U.S. C. ................... 96/88; 96/90 PC; 252/300 ity to act as an electron trap; which have M-center. (5) Int. Cl............................................ G03C 1/00 Said materials are useful as a reversible ultramicro 58 Field of Search.................... 96/88, 90 PC, 108; fish, an optical storage element for optical memory 340/73 CC: 356/256; 252/3OO system and the like. 10 Claims, No Drawings 3,909,270 1 2 DICHROIC REVERSIBLE PHOTOSENSTEVE rial which consists of the crystals of an alkali metal hal MATERIALS ide intermixed with one kind of a specific metallic cat This invention relates to dichroic reversible photo ion in which M-center is formed, and as a result of fur sensitive materials and a method for the preparation ther studies on using a new theory developed by them, thereof. More particularly, it concerns dichroic revers have succeeded to obtain new dichroic reversible pho ible photosensitive materials which consist of the crys tosensitive materials having a remarkably improved tals of an alkali metal halide which contain an alkali photosensitivity which consist of the crystals of an al metal ion having smaller ion radius than that of the al kali metal halide intermixed with one kind of alkali kali metal in said alkali metal halide and also one or metal ion having smaller ion radius than the alkali more kinds of other metal ions than alkali metal ion O metal in said alkali metal halide used as the base mate which possess an ability to act as an electron trap; rial and one or more kinds of metal ions other than the which have M-center, and a method for the preparation alkali metal ion which possess an ability to act as an therof. electron trap, which have M-center. The objects of this invention will become clear in the The alkali metal halide crystal to be used as the base following explanation. 15 material of this invention means the crystals of salts of It has been known that when crystals of an alkali an alkali metal such as lithium, sodium, potassium, ru metal halide such as sodium chloride, potassium chlo bidium or cesium, with a halogen such as chlorine, bro ride or the like are irradiated with an electron beam, mine, fluorine or iodine. The most preferred example proton, X-ray or y-ray, or treated in an atomosphere of of the alkali metal halide may be sodium fluoride. Pre alkali metal steam, negative ion vacancy is generally 20 ferred examples may be sodium chloride, sodium bro produced in the crystals. And the negative ion vacancy mide, potassium chloride, potassium fluoride, potas is one of color centers, because it can catch an electron sium bromide, lithium fluoride, rubidium fluoride, ru and absorb light at a definite wave length by which bidium bromide and the like. Besides, cesium fluoride, crystals are colored. An M-center is one of such color cesium bromide, sodium iodide and the like may be centers wherein two negative ion vacancies (F-center) 25 mentioned as other examples to be used in this inven stand adjacently to each other to the direction of (110) tion. or (110) and have two absorption bands and together The alkali metal ion in the compound producing an catch an electron. That is, the M-center oriented to the alkali metal ion having smaller ion radius than that of direction of (110), e.g., that of sodium fluoride shows the alkali metal in the alkali metal halide means, for in a maximum absorption band at 505 mpu to the light po 30 stance, lithium ion to sodium ion, or sodium or lithium larized to the direction of (110) and an absorption ion to potassium ion or the like. The compound pro band at 340 Mpu to the light polarized to the direction ducing an alkali metal ion having smaller ion radius of (110). The band at long wave length side between than that of the alkali metal in the alkali metal halide two absorption bands is called as the first absorption is one producing an alkali metal ion as mentioned band and one at short wave length side as the second 35 above, preferably a halide compound of the same kind absorption band. M-center possesses a property of of halogen as that of the alkali metal halide used. being not reoriented by the light of first absorption The metal ion in the compound producing metal ion band but reoriented by the light of second absorption other than the alkali metal ion which possesses an abil band to the direction of polarization, e.g., the M-center ity to act as an electron trap, means the ion derived oriented to the direction of (110) is reoriented to the 40 from metals as mentioned below. direction of (110) by irradiation of the light at second i. an alkali earth metal such as beryllium, magnesium, absorption band polarized to the direction of (110). calcium, strontium or barium. Accordingly, it will be possible to write and read an in ii. a metal belonging to the group I B of the periodic formation in using such property of M-center. When an table such as copper or silver. information O is applied for the M-center oriented to 45 iii. a metal belonging to the group II B of the periodic the direction of (1 1 O) and an information 1 for the M table such as zinc, cadmium or mercury. center oriented to the direction of (110), writing of the iv. a metal belonging to the group III B of the periodic information O in crystals by the light of second absorp table such as gallium, indium or thallium. tion band polarized to the direction of (110) will be v. a metal belonging to the group IV B of the periodic possible. And it will be also possible to erase an infor SO table such as lead or tin. mation 0 in M-center by the light polarized to the direc vi. a transition metal such as iron, cobalt, nickel, tita tion of (l 10) and stimutaneously to write a new infor nium, Vanadium, chronium or magnesium. mation 1. vii. a rare earth metal such as samarium or europium. Also, as numbers of M-center to be reoriented are The compound producing metal ion other than alkali proportional to exposing energy of writing light, the 55 metal ion which possesses an ability to act as an elec crystals having M-center will possess a capacity of an tron trap means the compound producing the metal analogue record for voluntary pattern such as charac ions as mentioned above. Preferable one is a halide ters, figures and the like as well as of a digital record compound of the same kind of halogen as that of the as mentioned above. They will, therefore, be usable for alkali metal halide to be used. a photosensitive material as equivalent to photographic 60 Speaking of the method for preparing the object ma films. Furthermore, a great advantage to use M-center terials in this invention, an appropriate amount of alkali as above is that crystals having M-center become a re metal halide crystal is firstly melted, e.g., in a melting versible photosensitive material which is capable of re pot or bath, to which are added one kind of compound cording and erasing an information repeatedly. There producing alkali metal ion and one or more kinds of fore the crystals are promising as a memory element. 65 compounds producing metal ions and melted. Crystals In utilization of M-center, the inventors of this inven are grown and isolated in accordance with a conven tion have discovered a reversible photosensitive mate tional method, e.g., Kyropoulos method. See, e.g., 3,909,270 3 4. Color Centers In Solids, J. H. Schulman and W. D. plicatively increased, as compared with that of the crys Compton, Pergamon Press, New York (1963), pages tals of alkali metal halide intermixed with either alkali 32-34. metal ion or other metal ion. The crystals of this inven The addition amount of each of the compound pro tion may be cleaved to make a thin plate which can be ducing alkali metal ion and the compounds producing used as a reversible ultramicrofiche, to which a graphic metal ion may be about 0.00001 - 1 O.O molar percent description is copied through a polarizer. Besides, they age to the crystals of alkali metal halide as the base ma may be used as an optical storage element for optical terial, preferably about 0.1 ~ 2.0 molar percentage.
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