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United States Patent Office Patented Mar 3,373,279 United States Patent Office Patented Mar. 2, 1968 1. 2 3,373,279 are as follows: the body should be optically integral, EUROPUM ACTIVATED STRONTIUM have good efficiency of energy conversion, have the ODOE SCNTLLATORS desirable geometry of the mass for energy absorption, Robert Hofstadter, Stanford, Calif., assignor, by mesne and have favorable geometry of the mass for light assignments, to Kewanee Oil Company, Bryn Mawr, Pa., emission reflector surface quality, and Window surface a corporation of Delaware quality. There usually should be a reflector surrounding No Drawing. Filed Jan. 29, 1965, Ser. No. 429,141 the crystal and it should have a high efficiency of reflec 5 Claims. (C. 250-71.5) tion and be uniformly and intimately fitted against the surface of the crystal. The window or light-pipe, which 0 may be nothing more than a portion of the crystal surface ABSTRACT OF THE DISCLOSURE not covered by the reflector, should have a good uniform This invention comprises a scintilation crystal com optical coupling with the mass of the crystal and have a posed of strontium iodide activated by europium. The good light transmitting efficiency from the crystal to the invention also comprises a radiation detector having a light detector. detecting element and a chamber optically coupled to Europium when used in amounts as low as about 10 this detecting element, having within the chamber a parts per million causes an emission peak at about scintillator consisting of strontium iodide activated with 4300-50 angstroms. about 10-16,000 parts per million of europium. The strontium iodide crystals of the present invention containing from about 10 p.p.m. (part per million) to 20 about 16,000 p.p.m. of europium can be used as scintil This invention relates to strontium iodide scintillation lation crystals. crystals. More particularly it relates to substantially The discovery that europium activated strontium iodide optically integral single crystals and polycrystalline can be used effectively as a scintillator provides a mate masses of strontium iodide doped with europium and rial which, having a higher stopping power than sodium which may be grown according to the conventional grow 25 iodide, may be used in smaller sections to obtain the same ing techniques such as the Stockbarger-Bridgman proce stopping power. Being able to use smaller sections is of dure (U.S. Patent 2,149,076) or the Czochralski proce advantage. dure Z. Phys. Chem. 92,219 (1918). The europium activated strontium iodide scintillators The europium activated strontium iodide crystals of of the present invention are hygroscopic and deteriorate the present invention may be used as scintillators 30 rapidly in humid atmosphere. In order to take advantage similarly to crystalline-thallium-activated sodium iodide. of the crystal's Scintillation properties, the crystals must See Hofstadter, U.S. Patent 2,585,551. The strontium be kept in a substantially anhydrous environment. Con iodide crystals convert a large proportion of the energy veniently, the crystal is “canned' in a hermetically sealed from ionizing radiation to light flashes in the region of container having an optical window providing for com high spectral sensitivity of photomultiplier tubes and munication of light. The crystal may be coupled optically other light detectors. Moreover the duration and rise of to the window with an optical fluid, or cement or the the light pulse (decay time constant) is such that each crystal may be supported within the container at a suitable pulse can be converted by the photomultiplier tube into vantage point so the scintillation of the crystal may be electrical pulses which may be amplified, and counted or observed and detected through the window. The container integrated effectively. 40 or a part thereof is composed of a radiation permeable The decay time constant of any luminescent material material. determines its suitability for use as a scintillator. Many As previously mentioned, the scintillation crystals of phosphors can never be used as scintillators because of a the present invention are hygroscopic and must be kept slow decay time constant. That a crystal is "optically at all times in a Substantially anhydrous atmosphere. integral' presupposes a high degree of transparency of the When fabricating, packing, canning or using the instant crystal for its own emitted light. If the crystal or crystal crystals, it is of advantage to perform all of the operations line body is sufficiently transparent then it must addi in an atmosphere having a dew point of -60° C. or tionally be in an "optically integral' form or mass of less. Moreover, if the crystal is to be used outside of a such character that the light pulses generated anywhere hernetically sealed container, it is considered within the therein from ionizing radiations may be transmitted 50 Scope of the invention to house the entire detector or efficiently to a suitable detector such as a photomultiplier analyzer apparatus in a dry chamber along with the tube or other light sensitive indicator. For the purposes of crystal. the present invention, the expression "optically integral' Combinations of the crystals of the present invention means that there is an optical continuity or optical with photo-multiplier tubes having their own anhydrous coupling between parts of the whole body. In bodies with 55 chambers or enclosures for the europium activated stron simple geometry, over half of the light originating at any tium iodide provide an article of manufacture capable point therein travels a complex path with numerous of delivering an electrical signal analogous to that of an reflections from the surface of the body or outside reflec equivalent unii containing a crystal of thallium-activated tor. To be most useful as a radiation detector, the Sodium iodide. efficiencies of the light paths from all points in the body 60 The optically integral europium activated strontium to a window should be nearly equal. The efficiency of iodide crystals of the present invention advantageously the paths ultimately affects the pulse height or signal may be used with conventional systems designed for count strength, and the equality of efficiency of the various ing radiation pulses or in systems designed for measuring paths affects the resolution. integrated radiation intensities. The crystal is optically cou That a mass is optically integral is generally apparent 65 pled to a means for converting the fluorescence of the to the eye of one experienced in preparing and testing crystal to electrical energy such as a photomultiplier tube devices with the material in question. It is immediately or the like. The pulses of light emitted by the scintillator evident in the pulse height spectrum in that the photo are converted to electrical signals corresponding to the peak from a body which is not optically integral will be energy of the radiation. In order to measure the pulse broadened or split into several components. 70 height, the integrated electrical signals are selected ac Desirable properties of a scintillator detector device cording to intensity, stored in magnetic or other accumu 3,378,279 3. 4. lators and read out by any convenient means such as an When the characteristic red color of the mother liquor oscilloscope or an electric typewriter. had faded substantially each ampoule was heated to about An important feature of the present inention is the 60° C. and held at this temperature until any remaining formation of the scintilation crystals or bodies under color had disappeared completely. The ampoules were then controlled growth conditions. The rate at which these 5 in stepwise succession, heated for a second 24-hour period bodies are grown depends on the temperatures of at 90° C., a third 24-hour period at 150° C. and a fourth two Zones and the flow of heat through the growth 24-hour period at 300° C., pumping being continued interface. The rate of growth and crucible size must be throughout the entire dehydration. The strontium iodide considered in determining the proper conditions neces charge in each ampoule was then substantially free from sary for obtaining a body having the desired physical 0 water of hydration. characteristics. These factors are, of course, well known The following examples set forth the melting and grow to those skilled in the art and need no further discussion. ing of scintillation crystals according to the present in Where optical bodies are to be produced, the growth vention. rate is especially important; discontinuities, which accom Example I pany casting or fast solidification affect the light trans mission characteristics. For best results, the growth rate One of the ampoules containing a charge of strontium should be several orders of magnitude slower than the iodide and 26 parts per million of europium chloride de flow of heat would permit. In other words, the amount hydrated according to Example B, is sealed off while under of heat being conducted through the solidifying mass is a vacuum having a pressure of about 0.01 mm. Hg ab many times (103-105) the amount of heat given off by the solute or less. The filled amopule was then placed in a Solid being formed due to its latent heat of fusion. In growing furnace of the Stockbarger type as described in bodies being formed under condition of controlled growth, U.S. Patent 2,149,076 wherein the strontium iodide charge discontinuities in the materials comprising the solid move was fused and grown into a crystal at a rate of about 1 toward the heat source at a rate dependent upon vapor to 6 mm. per hour. After the charge had been solidified pressure of the material and the thermal gradient main 25 completely forming a crystalline ingot, the furnace and tained in the solid.
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