High density fast phosphor for electron microscopy

Abstract

A fast-decaying, dense phosphor having relatively high light emission is described. Through a combination of material selection, growth and deposition technique, phosphor thin films are made that preserve the necessary light output when used in thin-films, unlike common fast phosphors, such as P-46, P-47, and also have an afterglow that decays much faster than common bright phosphors, such as P-43. Use of the phosphor is described in applications where acquiring many frames/images very quickly is required.

Claims

1. A thin film sensor for emitting light when excited by an electron beam, comprising: a cerium-doped or praseodymium-doped, non-transparent, garnet crystalline phosphor powder comprised of particles having a grain size substantially between 1 and 5 microns, wherein the thin film sensor has a thickness of 100 m or less, said phosphor having a light output primary decay time to less than a factor of 1/e (0.37) of peak light emission at 1 microsecond or less after excitation by the electron beam has ceased, and said phosphor having an emission efficiency equal to or greater than 25% of phosphor P-43.

2. The thin film sensor of claim 1, wherein said phosphor exhibits an afterglow of less than 1% of peak light emission intensity at 100 microseconds or less after excitation by the electron beam has ceased.

3. The thin film sensor of claim 1 wherein said phosphor powder has a density of about 6.0 gm/cm.sup.3.

4. The thin film sensor of claim 1 wherein said phosphor powder comprises particles heat-treated at greater than 1400 degrees Celsius and said heat-treated particles exhibit crystallinity in garnet phase as determined by x-ray diffraction.

5. The thin film sensor of claim 1, wherein said heat-treated particles are milled to reduce average particle size to less than about 5 m.

6. The thin film sensor of claim 5, wherein said milling comprises attrition milling, ball milling, cryo-milling or jet-milling.

7. The thin film sensor of claim 5, comprising particle agglomerates substantially greater than about 1 micron and less than about 10 micron after said milling.

8. The thin film sensor of claim 5, wherein said particles vary in size by no more than a factor of 5.

9. The thin film sensor of claim 1, wherein said phosphor has the chemical formula of: (Gd.sub.1-w-x-yY.sub.xLu.sub.yCe.sub.w).sub.3(Ga.sub.1-zAl.sub.z).sub.5O.sub.12, where x<1, y=0 to 1, w=0.00067 to 0.05, and z=0 to 1.

10. The thin film sensor of claim 9, wherein w is substantially 0.0067, and z is substantially 0.5.

11. The thin film sensor of claim 9, further comprising: a fiber-optic faceplate or thin substrate, wherein said phosphor is structurally bound to the fiber-optic faceplate or thin substrate.

12. The thin film sensor of claim 11 wherein said phosphor is structurally bound to said fiber-optic faceplate or thin substrate with sodium silicate, ethyl cellulose, ammonium polymethacrylate, or cellulose nitrate.

13. An electron beam sensor comprising the thin film sensor of claim 11, the electron beam sensor further comprising: an optical detector array image sensor configured to receive light from the thin film sensor.

14. An electron beam sensor of claim 13, wherein the optical detector array image sensor is configured to be read out at 1000 frames per second or greater.

15. A thin film sensor for emitting light when excited by an electron beam, comprising: a cerium-doped or praseodymium-doped, non-transparent, garnet crystalline energy conversion phosphor powder, comprised of particles having a grain size substantially between 1 and 5 microns, said phosphor having a light output primary decay time to less than a factor 1/e (0.37) of peak light emission at 1 microsecond or less after excitation by an electron beam has ceased and having an emission efficiency in a thin film sensor equal to or greater than 25% of phosphor P-43.

16. The thin film sensor of claim 15, wherein said phosphor exhibits an afterglow of less than 1% of peak light emission intensity at 100 microseconds or less after excitation by the electron beam has ceased.

17. The thin film sensor of claim 15 having a density of about 6.0 gm/cm.sup.3.

18. The thin film sensor of claim 15 wherein said particles are heat treated at greater than 1400 degrees Celsius and said heat-treated particles exhibit crystallinity in garnet phase as determined by x-ray diffraction.

19. The thin film sensor of claim 15, wherein said particles are milled to reduce average particle size to less than about 5 m.

20. The thin film sensor of claim 19, wherein said milling comprises attrition-milling, ball-milling, cryo-milling or jet-milling.

21. The thin film sensor of claim 19 wherein said particle agglomerates are greater than about 1 micron but less than about 10 micron after said milling.

22. The thin film sensor of claim 21 wherein said particles vary in size by no more than a factor of 5.

23. The thin film sensor of claim 15 wherein said phosphor has the chemical formula of: (Gd.sub.1-w-x-yY.sub.xLu.sub.yCe.sub.w).sub.3(Ga.sub.1-zAl.sub.z).sub.5O.sub.12, where x<1, y=0 to 1, w=0.00067 to 0.05, and z=0 to 1.

24. The thin film sensor of claim 23 wherein w is substantially 0.0067, and z is substantially 0.5.

25. A method of preparing the thin film sensor of claim 15 comprising: producing nanoparticles of the phosphor powder by flame-spray pyrolysis; heat-treating said nanoparticles in air to grow them in size and turn the particles into a crystallized form; confirming crystallinity of said heat-treated nanoparticles by x-ray diffraction; milling said heat-treated nanoparticles to a size between 1 and 10 microns; forming a thin film by mixing the phosphor material in a liquid dispersant with a binding agent; and depositing said thin film on an optical element, a thin substrate or directly to an image sensor.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a cross section of an electron detector;

(2) FIG. 2A is a simulated path of electrons at 60 keV;

(3) FIG. 2B is a simulated path of electrons at 100 keV;

(4) FIG. 2C is a simulated path of electrons at 160 keV;

(5) FIG. 2D is a simulated path of electrons at 200 keV;

(6) FIG. 2E is a simulated path of electrons at 300 keV;

(7) FIG. 3 is a graph of predicted deposited energy level versus thin-film phosphor thickness for an exemplary phosphor according to the invention;

(8) FIG. 4 shows light output vs. time for phosphors P46 and P47

(9) FIG. 5 is a comparison of phosphor light output for phosphors heat treated at various temperatures;

(10) FIG. 6A shows exemplary heat-treated Cerium doped garnet particles ball milled for 5 minutes;

(11) FIG. 6B shows the exemplary heat-treated Cerium doped garnet particles of FIG. 5A ball milled for an additional 60 minutes;

(12) FIG. 7 is a graph of test data comparing emission spectra of an exemplary cerium-doped phosphor: GYGAG:Ce with two phosphors YAG:Ce and YGAG:Ce;

(13) FIG. 8 shows light output from four phosphors, including two exemplary embodiments according to aspects of the invention;

(14) FIG. 9 is a graph of representative decay data showing the decay time to 1% for both P-43 and an exemplary phosphor according to aspects of the invention;

(15) FIG. 10 is an exemplary STEM with EELS including an exemplary sensor having a thin film phosphor scintillator as described herein; and

(16) FIG. 11 is a diagram of an exemplary system for optically imaging a thin-film phosphor mounted on a thin substrate.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

(17) Those skilled in the art will recognize other detailed designs and methods that can be developed employing the teachings of the present invention. The examples provided here are illustrative and do not limit the scope of the invention, which is defined by the attached claims. The following detailed description refers to the accompanying drawings. The same reference numbers in different drawings may identify the same or similar elements.

(18) In an aspect of the invention, a detector for electron microscopy is made of cerium-doped or praseodymium-doped, non-transparent, garnet crystalline phosphor powder comprised of particles of about 1-5 micron grain size. In a further aspect, the powder is a cerium-doped garnet of with the chemical formula of (Gd.sub.1-w-x-yY.sub.xLu.sub.yCe.sub.w).sub.3(Ga.sub.1-zAlz).sub.5O.sub.12, where x<1, y=0 to 1, w=0.00067 to 0.05, and z=0 to 1. In a more particular embodiment, the cerium-doped garnet of the preceding formula is such that w is substantially 0.0067, x<1.0, y=0-1.0, and z is substantially 0.5. In an exemplary embodiment, the phosphor has a primary decay time of less than 200 nanoseconds, and less than 1% afterglow at 100 microseconds. The emission efficiency, i.e., the generated photon flux in lumens per incident beam electron, based on an equivalent thin layer geometry (i.e. about 100 m or less), of the phosphor is greater than 25% of that of P-43.

(19) The above definition of emission efficiency is relevant for phosphor use in electron microscopy. However, existing published data on phosphor performance often uses other energy efficiency metrics such as lumens per Watt, which refers to light output as a function of incident radiation power, or lumens per micro-Amp, which may refer to direct excitation by electron beams or to the current used in method where an X-ray source provides incident radiation to excite the phosphor. Furthermore, the results are often obtained using bulk phosphors or thick films, as opposed to a relevant thin film geometry. A suitable method of one type of energy efficiency measurement is described in Standard Reference Phosphors for Quantum Efficiency Measurement, Yuji International, 1250 Oakmead Parkway Suite 210 Sunnyvale, Calif. 94085. A table of efficiencies corresponding to various scintillator materials is provided below in Table 1, including the results obtained for an embodiment of the phosphor described herein. Table 1 below shows that published x-ray efficiency data shows other fast phosphors that would have greater than 25% of the light yield of P-43. However, when those phosphors are put into a thin-film geometry, their low density becomes an important effect, and the measured emission efficiency achieved is much lower than the efficiency when in a standard x-ray excitation measurement. Therefore, while published efficiencies of a phosphor may suggest sufficient performance will be obtained in the desired application, the efficiency in the desired geometry, in practice, is not sufficient.

(20) TABLE-US-00001 TABLE 1 Published Measured thin film Efficiency Published Emission Efficiency (electron beam, Efficiency; (electron beam, 15 kV) (lm/A) Percentage Density 200 kV) TYPE Composition [4] of P-43 (g/cm.sup.3) (Relative to P-43) P-43 Gd.sub.2O.sub.2S:Tb 0.71 100% 7.3 100% P-46 Y.sub.3Al.sub.5O.sub.12:Ce 0.25 35% 4.55 14% P-47 Y.sub.2SiO.sub.5:Ce,Tb 0.18 25% 4.45 12% Presently Ce-doped No prior No prior 6.4 25-50% Disclosed garnet/Pr- published data published Phosphor doped data garnet

(21) Consistent with embodiments described herein, the starting material for the garnet crystalline powder of the novel material is made by flame-spray pyrolysis producing nanoparticles with typical sizes of 10 to 80 nm. Nanoparticles can be fabricated by other means, particularly by solution and other means of combustion. The invention is not limited to the listed means for producing the starting material. The starting material nanoparticles are not highly crystalline, nanometers in size and not useful as a scintillator directly. The particles are heated in air to grow them in size and also to turn the particles into a crystallized form, which greatly enhances the light yield.

(22) FIG. 5 shows relative light output for an exemplary Cerium-doped garnet powder in which each sample is treated to the indicated heating temperature in degrees Celsius. It can be seen from FIG. 5 that light output peaks once the material is heated to 1400 C. and that heating above that temperature in the conditioning process does not produce material additional light output. The heating step creates a material with particles sizes in the 1 to 30 micron range and forms crystals of the material. The crystallinity may be confirmed by x-ray diffraction. The heating step also can result in some agglomeration of the material. To be used as a thin film scintillator, the particle grain size should be in approximately the 1 to 10 and preferably 1 to 5 micron range and the individual particles unbound to each other. In an exemplary embodiment, the particles have a particle size distribution such that they vary in size by less than about a factor of 5.

(23) This reduction in size may be achieved by milling the material formed in the heating step described above. FIGS. 6A, 6B show exemplary Cerium doped garnet particles as modified by above heating step and then ball milled for 5 minutes (6A) and for 60 additional minutes (6B). Although ball milling is described above, various other methods for milling can be used consistent with embodiments described herein including ball milling, jet milling, rod milling, disc milling, cryo-milling and, pestle and mortar for example.

(24) FIG. 7 shows test data for the emission spectrum of an exemplary Ce-doped garnet phosphor [(Gd,Y).sub.3(Ga,Al).sub.5O.sub.12] according to an aspect of the invention, compared to phosphors: YGAG:Ce [Y.sub.3(Ga,Al).sub.5O.sub.12] and GYGAG:Ce [(Gd,Y).sub.3(Ga,Al).sub.5O.sub.12]. The intensity units on the Y axis are arbitrary. The excitation is provided by ultraviolet light of wavelength 320 nm. This graph shows that the phosphors emit at different frequencies.

(25) In further embodiments, the garnets containing Lu and Tb in addition to Gd and Y as noted exhibit similar emission spectra.

(26) Once the phosphor material has been processed to a useful size, a thin film containing the phosphor is made. The thin film may be made by mixing the phosphor material in a liquid dispersant with a binding agent including but not limited to: sodium silicate, ethyl cellulose, ammonium polymethacrylate or cellulose nitrate. The phosphor/binder mixture is applied on top of an image processing device, which may be, for example, a fiber-optic plate as shown in FIG. 1. The film can be deposited in many ways, for example, by silk-screening or gravitational settling. In an exemplary embodiment, the final scintillator film should have a density of at least 6.0 gm/cm.sup.3.

(27) FIG. 8 shows a light-yield comparison between P-47 and P-43 phosphor films (bottom two squares) and two exemplary embodiments of the cerium-doped garnet described herein (top two squares). The bottom left is a film of P-47. The bottom right is a film of P-43. The top left square is about 50% the brightness of the P-43 (bottom right) square. The top right square is about 25% of the brightness of the P-43 square. The P-47 square is about 14% the brightness of the P-43 square.

(28) FIG. 9 shows a graph of representative decay data showing the decay time to 1% for both P-43 (large dashed) and an embodiment of an exemplary phosphor as described herein for a 1 ms duration 200 kV electron beam exposure. It can be seen that the P-43 light emission reaches the 1% level after about 2 ms, while an exemplary phosphor as described hererein reaches 1% in less than 0.112 ms.

(29) FIG. 10 is a block diagram for an exemplary Scanning Transmission Electron Microscope (STEM) equipped for Electron Energy Loss Spectroscopy and having an imaging device incorporating exemplary phosphors as described herein. An exemplary STEM includes a microscope/probe deflector 111 positioned above a specimen 112. A spectrometer 120 placed after the specimen includes one or more beam blankers 121, an energy-dispersing prism 122, one or more energy shifters 123, one or more spectrum deflectors 124, and an image-receiving sensor 125 comprising a scintillator made according to the processes described herein and using the phosphors described herein. One or more microcontrollers or computers 126 are connected to and control the deflectors 111, beam blankers 121, energy shifters 123 and spectrum deflectors 124 and are connected as well as to the image sensor 125 to receive the image produced by it. In a system such as this, the image sensor may be readout at speeds of 1000 frames per second or greater.

(30) In a further embodiment, one or more of the phosphors described herein may be supported on a thin substrate and light generated by the phosphors is imaged via optical elements. FIG. 11 is a simplified diagram of an exemplary system comprising a thin substrate 1120 to which is applied a phosphor layer 1110. The combined substrate/phosphor is inserted in the path of an electron beam 1140. Light 1150 produced by the phosphor layer 1110 is focused by one or more optical lenses 1130. The substrate may be a film or a screen. Preferred materials for the substrate have a low atomic number to reduce scattering of the incident electron beam and are as transparent as possible to electrons. Exemplary materials include a beryllium metal film or a polymer film, each of which have elements with low atomic numbers.

(31) Although the invention has been described in detail above, it is expressly understood that it will be apparent to persons skilled in the relevant art that the invention may be modified without departing from the spirit of the invention. Various changes of form, design, or arrangement may be made to the invention without departing from the spirit and scope of the invention. Therefore, the above-mentioned description is to be considered exemplary, rather than limiting, and the true scope of the invention is that defined in the following claims.

(32) No element, act, or instruction used in the description of the present application should be construed as critical or essential to the invention unless explicitly described as such. Also, as used herein, the article a is intended to include one or more items. Further, the phrase based on is intended to mean based, at least in part, on unless explicitly stated otherwise.