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United States Patent (19) 11 Patent Number: 6,113,977 Soininen Et Al

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United States Patent (19) 11 Patent Number: 6,113,977 Soininen Et Al USOO6113977A United States Patent (19) 11 Patent Number: 6,113,977 Soininen et al. (45) Date of Patent: Sep. 5, 2000 54 METHOD OF GROWING AZNS:MN A. Yoshikawa et al., “MBE-Like” AMD “CVD-Like” PHOSPHORLAYER FOR USE IN THIN-FILM Atomic Layer Epitaxy of ZnSe in MOMBE System, Journal ELECTROLUMNESCENT COMPONENTS of Crystal Growth 101 (1990) pp. 86-90 (no mo.). 75 Inventors: Erkki Lauri Soininen; Gitte Y. Wu et al., “Atomic Layer Epitaxy of ZnS on GaAs Hárkönen; Marja Lahonen, all of Substrates by Metalorganic Molecular Beam Epitaxy”, Japa Espoo; Runar Törnqvist, Kauniainen; nese Journal of Applied Physics, vol. 29, No. 5, May, 1990, Juha Viljanen, Espoo, all of Finland pp. L727-L730. N. Shibata et al., “Monolayer Epitaxy of ZnSe on GaAs 73 Assignee: Planar International Oy Ltd., Espoo, Substrates by Alternating Adsorption of Diethylzinc and Finland Hydrogenselenide”, Journal of Crystal Growth 101 (1990) pp. 91-95 (no mo.) 21 Appl. No.: 08/927,523 I. Bhat, “Atomic Layer Epitaxial Growth Studies of ZnSe Using Dimethylzinc and Hydrogen Selenide”, Journal of 22 Filed: Sep. 11, 1997 Crystal Growth 138 (1994) pp. 127-130 (no mo.) 30 Foreign Application Priority Data M. Migita et al., “The Preparation of ZnS:Mn Electrolumi nescent Layers by MOCVD Using New Manganese Sep. 11, 1996 FI Finland .................................... 96.3587 Sources”,Journal of Crystal Growth 93 (1988) pp. 686–691 (51) Int. Cl." ........................................................ B05D 5/06 (no mo.). 52 U.S. Cl. .................. 427/64; 427/255.32; 427/255.33 58 Field of Search ........................ 117/88, 104; 427/64, Primary Examiner Janyce Bell 427/255.32, 66, 255.33 Attorney, Agent, or Firm McDermott, Will & Emery 56) References Cited 57 ABSTRACT U.S. PATENT DOCUMENTS The invention relates to a method of growing a ZnS:Mn 4,058,430 11/1977 Suntola et al. .......................... 156/611 phosphor layer Suitable for use in thin-film electrolumines 4.389.973 6/1983 Suntola et al. ... ... 118/725 cent components. According to the method, the ZnS:Mn 4,442,136 4/1984 Johnson .................................... 427/64 phosphor layer is grown on a Substrate by means of the ALE 5,624,705 4/1997 Stutzmann et al. ....................... 427/64 method using volatile Zinc, Sulfur and manganese com 5,695,809 12/1997 Chadha ..................................... 427/64 pounds as the precursors. According to the invention, an organozinc compound Such as diethylzinc or dimethylzinc is OTHER PUBLICATIONS used as precursor for Zinc, hydrogen Sulfide or an organo J. Hyvärinen et al., “Mass Spectrometry Study of ZnS Sulfur compound is used as precursor for Sulfur, and an Atomic Layer Epitaxy Process”, Journal of Crystal Growth organomanganese compound or organic manganese com 86 (1988) pp. 695-699 (no mo.). pleX compound is used as precursor for manganese. The M. Tammenmaa et al., “Growth of ZnS Thin Films Using invention provides a display component with drive-voltage Zinc Acetate as Zinc Source and Manganese and Lanthanoid Symmetrical light emission and Stable characteristics of B-Diketonates as Activator Sources”, First Symposium on luminance level and turn-on Voltage. Atomic Layer Epitaxy, pp. 18-21, VTT, Espoo, Finland, 1984 (no mo.). 20 Claims, 4 Drawing Sheets U.S. Patent Sep. 5, 2000 Sheet 1 of 4 6,113,977 TIME ms) F.G. 1 a ||--+ ©cootoC->oC> <!--©ooN,coLo<rçoçN<-c(> ar?III |||||||||||||||/||||||||||||||||||| |||||||||||||||||||||||||||||||||||||||| TTTTTTTTTT) TIME (ms) †|||||||||||||||||| |||||||||||||||||||||||||||||||||||||| 33 ---BA FG 1b. U.S. Sep. 5, 2000 Sheet 3 of 4 6,113,977 50 100 150 200 AGING TIME (h FG. 3a AGING TIME (h FIG. 3b U.S. Patent Sep. 5, 2000 Sheet 4 of 4 6,113,977 100 150 AGING TIME (h) FIG. 4a AGING TIME (h) FIG. 4b. 6,113,977 1 2 METHOD OF GROWING AZNS:MN reacts with the hydrogen sulfide forming zinc sulfide J. Hyv PHOSPHORLAYER FOR USE IN THIN-FILM arinen, M. Sonninen and R. Tornqvist: ELECTROLUMNESCENT COMPONENTS Journal of Cryst. Growth, Vol. 86 (1988), p. 695). BACKGROUND OF THE INVENTION Up to date, hundreds of thousands of thin-film electrolu minescent ZnS:Mn displays have been successfully made 1. Field of the Invention using the ALE method using chlorides as precursors for The present invention relates to the manufacture of thin depositing ZnS:Mn. However, this conventional technique film components. In particular, the present invention con involves a few evident disadvantages. An example of these cerns a method for growing a ZnS:Mn phosphor layer for is the asymmetric light emission of the electroluminescent use in inorganic thin-film electroluminescent components, ZnS:Mn structure. This phenomenon is elucidated in the wherein the ZnS:Mn phosphor layer is grown on a substrate appended FIG. 1a. AS is evident from the diagram, one by means of the Atomic Layer Epitaxy method. According polarity of the pixel drive Voltage produces higher light to the method, volatile (i.e., gaseous or vaporizable) Zinc, emission than the other polarity. In practice, this Sets limi Sulfur and manganese compounds are used as precursors for tations to the use of frequency modulation in the generation preparing the layer to be deposited. 15 of different gray levels on an electroluminescent display, 2. Description of Related Art because visible flicker of the emitted light will occur at low Flat electroluminescent displays are used in applications drive frequencies due to the asymmetric light emission. requiring a wide viewing angle, a wide temperature range Chiefly due to the low vapor preSSure of manganese and a rugged device Structure. The most important electrolu chloride, the chloride process presupposes a Substrate tem minescent phosphor material is manganese-doped Zinc Sul perature of at least 500 C. This temperature is already very fide (ZnS:Mn) which is conventionally used in all mono close to the Softening point of Soda lime glass. Because a chrome electroluminescent displayS emitting yellow light. Soda lime glass Substrate is favored on economical grounds, Also polychrome electroluminescent displayS emitting red the process temperature must be kept close to 500° C. (in the and green are based on the same phosphor material, whereby 25 range 500-520° C.), although layers of improved perfor the red and green colors are obtained by filtration from the mance could be obtained at a higher temperature. Because emission spectrum of ZnS:Mn. Soda lime glass is Subject to Softening already in the tem Thin-film electroluminescent (TFEL) layers of ZnS:Mn perature range conventionally used, this phenomenon gives have been made in the art by means of different methods: rise to extra costs in the manufacturing process of EL evaporation, Sputtering, metalorganic chemical vapor depo displayS. sition (MOCVD) and atomic layer epitaxy (ALE). Of these For the handling of both Zinc and manganese chloride, the methods, evaporation and ALE are used in the commercial ALE deposition equipment must be provided with Sublima manufacture of TFEL displays. In an industrial process, both tion sources which are both clumsy to handle and difficult to the economic efficiency of the method and the performance control. Furthermore, as Zinc chloride forming the matrix of of the electroluminescent ZnS:Mn thin film thus obtained 35 the thin-film compound is consumed at a higher rate of the are crucial. two precursors, Zinc chloride is obviously the one causing Of gas-phase deposition methods, the most widely used more problems. are MOCVD and ALE. In the MOCVD method, the pre cursors are introduced simultaneously into the reactor. The SUMMARY OF INVENTION film growth mechanism is principally based on the pyrolysis 40 It is an object of the present invention to overcome the of the precursors on the Substrate Surface, whereby the mass drawbacks of the above-described technique and to provide flow rates of the precursors can be adjusted to essentially an entirely novel approach to the growth of manganese control the film growth rate. In the ALE method, the doped Zinc Sulfide phosphor layers for use in electrolumi precursors are Sequentially pulsed into the reactor. Herein, neScent display components. It is a particular object of the the growth mechanism is not based on pyrolysis, but instead, 45 on eXchange reactions on the Substrate Surface. Thus, a invention to improve the performance of electroluminescent Self-limiting growth rate is obtained, that is, the growth rate ZnS: Mn thin films produced by ALE and to simplify the is independent from the mass flow rates of the precursors. manufacturing process of Such thin films. Therefore, it is more difficult in the MOCVD method to These and other objects, together with the advantages achieve good uniformity of the deposited film, which 50 thereof over known methods and processes, which shall explains why this method has not been used in the large become apparent from the Specification which follows, are scale production of electroluminescent ZnS:Mn thin-film accomplished by the invention as hereinafter described and components. In contrast, the ALE method uses a clearly claimed. different approach, whereby thin films made by means of The present invention is based on using a organozinc this process exhibit Sufficiently uniform thicknesses and 55 compounds as Volatile Zinc compounds and organomanga compositions for the commercial manufacture of electrolu nese compounds or organic manganese complex compounds minescent displayS. as manganese compounds in the ALE process. Conventionally, the best electroluminescent ZnS:Mn thin Deposition of ZnS:Mn thin films from an organic man films made using the ALE method have been prepared using ganese complex compound used as precursor by ALE is Zinc chloride, manganese chloride and hydrogen Sulfide as 60 known in the art. For instance, under laboratory conditions, precursors, whereby the Substrate Surface temperature has ZnS:Mn thin films have been grown using Zinc oxyacetate, been in the range from 500 to 520° C.
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