Ordering structure of scintillator and fabrication method

Abstract

An ordering structure scintillator of scintillator and fabrication method is disclosed. The ordering structure scintillator of scintillator comprises: a tubular template, which consists of a plurality of thin film oxidized metal tubes; a plurality of scintillators, filled in the thin film oxidized metal tubes; and a package layer, formed on the surface of the tubular template for protecting the tubular template. In addition, through the fabrication method, the ordering structure scintillator of scintillator can be made by anodic treatment and die casting technology with low cost and rapid production; moreover, the film oxidized metal tubes of the tubular template can be further manufactured to nano tubes by adjusting electrolyte composition, electrolysis voltage, and processing time of anodic treatment, and the aperture size, the thickness and the vessel density of the nano tube can be controlled and ranged from 10 nm to 500 nm, 0.1 m to 1000 m, and 10.sup.8 to 10.sup.12 tube/cm.sup.2, respectively.

Claims

1. A method for manufacturing a scintillator with sub-micron column structure, comprising the steps of: (1) fabricating a tubular template having a plurality of thin film oxidized metal tubes by processing an anodic treatment; (2) adjusting the tube diameter of the thin film oxidized metal tubes by a chemical etching process; (3) forming a thin film scintillator on the inner walls of the thin film oxidized metal tubes by a chemical impregnation process; (4) filling a liquid phase of scintillator material into the thin film oxidized metal tubes by a die casting process, so as to form a scintillator in each thin film oxidized metal tube; and (5) forming a package layer on the surface of the tubular template.

2. The method for manufacturing the scintillator with sub-micron column structure of claim 1, further comprising a step (2a) between the step (2) and the step (3), used for forming a reflective layer on the inner walls of the thin film oxidized metal tubes by a chemisorption process.

3. The method for manufacturing the scintillator with sub-micron column structure of claim 1, wherein the step (1) comprises the detailed steps of: (11) processing a surface treatment to a metal substrate by mechanical grinding, and then annealing the metal substrate; (12) disposing the metal substrate in a first electrolyte solution for processing an electrolytic polishing treatment under a first electrolyte voltage ranged from 5V to 50V and a first electrolyte temperature ranged from 2 C. to 40 C. for a first electrolyte time ranged from 1 minute to 10 minutes, wherein the first electrolyte solution comprises: HClO.sub.4, CH.sub.3(CH.sub.2).sub.3OCH.sub.2CH.sub.2OH and C.sub.2H.sub.6O; (13) disposing the metal substrate in a second electrolyte solution for processing a first-time anodic treatment under a second electrolyte voltage ranged from 50V to 200V and a second electrolyte temperature ranged from 5 C. to 15 C. for a second electrolyte time ranged from 1 minute to 24 hours; (14) disposing the product of the step (13) into a first remove solution, so as to remove the anodization film on the surface of the metal substrate under a first remove temperature ranged from 40 C. to 80 C. for a first remove time ranged from 10 minutes to 60 minutes, wherein the first remove solution comprises: CrO.sub.3 and H.sub.3PO.sub.4; (15) disposing the metal substrate in the second electrolyte solution again, so as to perform a second anodic treatment under the second electrolyte voltage and the second electrolyte temperature for the second electrolyte time; and (16) disposing the product of the step (15) into a second remove solution under a second remove temperature for a second remove time, so as to remove the metal substrate and obtain the tubular template having the thin film oxidized metal tubes, wherein the second remove temperature is room temperature and the second remove solution comprises: HCl and CuCl.sub.2.

4. The method for manufacturing the scintillator with sub-micron column structure of claim 3, wherein the composition of the second electrolyte solution is selected from the group comprising: H.sub.2SO.sub.4, H.sub.2CrO.sub.4, C.sub.2H.sub.2O.sub.4, HF, H.sub.3PO.sub.4, NH.sub.4F, and mixtures thereof.

5. The method for manufacturing the scintillator with sub-micron column structure of claim 1, wherein the material of the thin film oxidized metal tubes is selected from the group consisting of: ZrO.sub.2, TiO.sub.2, Al.sub.2O.sub.3, Ta.sub.3O.sub.5, ZrO.sub.2, and Nb.sub.2O.sub.3.

6. The method for manufacturing the scintillator with sub-micron column structure of claim 1, wherein the step (2) comprises the detailed steps of: (21) disposing the tubular template in a micro-structure modulation solution; and (22) adjusting the tube diameter of the thin film oxidized metal tubes under a micro-structure modulation temperature ranged from 20 C. to 80 C. for a micro-structure modulation time ranged from 0.5 hour to 5 hours.

7. The method for manufacturing the scintillator with sub-micron column structure of claim 6, wherein the composition of the micro-structure modulation solution is selected from the group comprising: H.sub.2SO.sub.4, H.sub.2CrO.sub.4, C.sub.2H.sub.2O.sub.4, HF, H.sub.3PO.sub.4, NH.sub.4F, and mixtures thereof.

8. The method for manufacturing the scintillator with sub-micron column structure of claim 2, wherein the step (2a) comprises the detailed steps of: (2a1) disposing the tubular template in a sensitization solution for treating with a sensitization process under a sensitization temperature for a sensitization time, wherein the sensitization temperature is ranged from 10 C. to 40 C., and the sensitization time being ranged from 0.5 minute to 30 minutes; (2a2) disposing the product of the step (2a1) in an activation solution for treating with an activation process under an activation temperature for an activation time, wherein the activation temperature is ranged from 10 C. to 40 C., and the activation time being ranged from 0.5 minute to 30 minutes; and (2a3) disposing the product of the step (2a2) in an electro-less deposition solution for treating with an electro-less deposition process under an electro-less deposition temperature and an electro-less deposition pH value for an electro-less deposition time, so as to form the reflective layer on the inner walls of the thin film oxidized metal tubes, wherein the electro-less deposition temperature is ranged from 50 C. to 90 C., the electro-less deposition time being ranged from 1 minute to 60 minutes, and the electro-less deposition pH value is ranged from 4 to 5.5.

9. The method for manufacturing the scintillator with sub-micron column structure of claim 8, wherein the composition of the sensitization solution consists of SnCl.sub.2, HCl and H.sub.2O.

10. The method for manufacturing the scintillator with sub-micron column structure of claim 8, wherein the composition of the activation solution consists of PdCl.sub.2, HCl and H.sub.2O.

11. The method for manufacturing the scintillator with sub-micron column structure of claim 8, wherein the composition of the electro-less deposition solution comprises: NiSO.sub.4, NaH.sub.2PO.sub.2, Pb(NO.sub.3).sub.2, and Na.sub.3C.sub.6H.sub.5O.sub.7.

12. The method for manufacturing the scintillator with sub-micron column structure of claim 1, wherein the step (3) comprises the detailed steps of: (31) immersing the tubular template in an aqueous solution for an immersion time, wherein the aqueous solution includes a scintillator material having a specific weight percent opposite to the aqueous solution; and (32) treating the tubular template by a thermal process, so as to remove the water in the thin film oxidized metal tubes.

13. The method for manufacturing the scintillator with sub-micron column structure of claim 1, wherein the step (4) comprises the detailed steps of: (41) disposing the powder of the scintillator material on the surface of the tubular template; (42) treating the product of step (41) by a thermal process, so as to make the liquid phase of scintillator material cover the surface of the tubular template; (43) permeating the liquid phase of scintillator material into the thin film oxidized metal tubes by using a die-casting mold; and (44) waiting for the solidification of the liquid phase of scintillator material in the thin film oxidized metal tubes to form a scintillator column in each of the thin film oxidized metal tubes.

14. The method for manufacturing the scintillator with sub-micron column structure of claim 1, wherein the material of the package layer of the step (5) is the material selected from the group consisting of polymer, metal, ceramic, and combinations thereof, and is formed on the surface of the tubular template by a processing way selected from the group consisting of spin coating, vapor deposition, sputtering, and combinations thereof.

Description

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

(1) The invention as well as a preferred mode of use and advantages thereof will be best understood by referring to the following detailed description of an illustrative embodiment in conjunction with the accompanying drawings, wherein:

(2) FIG. 1 is a framework view of a scintillator with sub-micron column structure according to the present invention;

(3) FIG. 2 is a flowchart of a method for manufacturing scintillator with sub-micron column structure according to the present invention;

(4) FIG. 3 is a detailed flowchart of step (S1);

(5) FIG. 4 is a schematic manufacturing process diagram of the scintillator with sub-micron column structure;

(6) FIG. 5 is the schematic manufacturing process diagram of the scintillator with sub-micron column structure;

(7) FIG. 6 is a microstructure image of anodic aluminum oxide tubes with tube diameter of 500 nm;

(8) FIG. 7 is a microstructure image of anodic aluminum oxide tubes with tube diameter of 350 nm;

(9) FIG. 8 is a microstructure image of anodic aluminum oxide tubes with tube diameter of 250 nm;

(10) FIG. 9 is a microstructure image of anodic aluminum oxide tubes with tube diameter of 70 nm;

(11) FIG. 10 is a microstructure image of anodic aluminum oxide tubes with tube diameter of 40 nm;

(12) FIG. 11 is a microstructure image of anodic aluminum oxide tubes with tube diameter of 10 nm;

(13) FIG. 12 is a microstructure image of anodic titanium oxide tubes with tube diameter of 90 nm;

(14) FIG. 13 is a microstructure image of nickel tubes formed on the inner walls of the anodic titanium oxide tubes;

(15) FIG. 14 is an EDS analysis plot of the nickel tubes formed on the inner walls of the anodic titanium oxide tubes;

(16) FIG. 15 is a microstructure image of CsI film formed on the inner walls of the anodic titanium oxide tubes; and

(17) FIG. 16 is an EDS analysis plot of the CsI film formed on the inner walls of the anodic titanium oxide tubes.

DETAILED DESCRIPTION OF THE INVENTION

(18) To more clearly describe a scintillator with sub-micron column structure and a manufacturing method thereof according to the present invention, embodiments of the present invention will be described in detail with reference to the attached drawings hereinafter.

(19) Please refer to FIG. 1, which illustrates a framework view of a scintillator with sub-micron column structure according to the present invention. As shown in FIG. 1, the scintillator with sub-micron column structure 1 mainly includes a tubular template 11, a plurality of scintillators 12 and a package layer 13, wherein the tubular template 11 consists of a plurality of thin film oxidized metal tubes 113, the scintillators 12 are respectively filled in the thin film oxidized metal tubes 113, and the package layer 13 is formed on the surface of the tubular template 11 for protecting the scintillators 12 from being damaged by water vapor and oxygen. In the present invention, the package layer 13 can be a polymer, a metal, a ceramic, or a combination thereof, and the package layer 13 is formed on the surface of the tubular template 11 by spin coating, vapor deposition, sputtering, or combination process thereof. In addition, the manufacturing material of the scintillator 12 can be cesium iodide (CsI), cesium iodide with doped sodium (CsI(Na)) or cesium iodide with doped thallium (CsI(Tl)).

(20) Moreover, for increasing the efficiency of the scintillators 12 to an external high-energy wave (for example, X-ray), it can further form a reflective film on the inner walls of the thin film oxidized metal tubes 113; therefore, the direct light or the refracted light with small refraction angle of the incident X-ray may efficiently get into a CCD device located under the scintillators 12. In the present invention, the material of the reflective layer can be nickel, zirconium, titanium, iron, cobalt, tungsten, copper, aluminum, and alloy made of these materials.

(21) Furthermore, for increasing the mechanical properties of the tubular template 11, a strengthening layer (not shown) can be formed on the bottom of the tubular template 11 when manufacturing this scintillator with sub-micron column structure 1; thus, it is able to avoid the thin film oxidized metal tubes 113 from being damaged when moving the tubular template 11 or filling the CsI into the thin film oxidized metal tubes 113. In the present invention, the material of the strengthening layer can be Nickel, zirconium, titanium, iron, cobalt, tungsten, and alloy made of these materials. Besides, it needs to further explain that, after completing the die casting process of the scintillators 12 under a vacuum or a non-vacuum environment, the strengthening layer can be next removed by chemical dissolution process.

(22) In the scintillator with sub-micron column structure 1 of the present invention, the tubular template 11 is manufactured by way of processing an anodic treatment to a metal substrate; moreover, the thin film oxidized metal tubes 113 of the tubular template 11 can be ZrO.sub.2, TiO.sub.2, Al.sub.2O.sub.3, Ta.sub.2O.sub.5, or Nb.sub.2O.sub.3 according to different metal substrates, wherein the thin film oxidized aluminum tubes (Al.sub.2O.sub.3) is also called as anodic aluminum oxide (AAO), anodic alumina nanoholds (AAN), anodic alumina membrane (AAM), or porous anodic alumina (PAA). In addition, by controlling the manufacturing parameters, the film oxidized metal tubes 113 of the tubular template 11 can be manufactured and include a specific tube diameter ranged from 10 nm to 500 nm, a specific thickness ranged from 5 m to 1000 m and a specific tube density ranged from 10.sup.8 tube/cm.sup.2 to 10.sup.12 tube/cm.sup.2.

(23) Thus, through above descriptions, the framework and element constitution of the scintillator with sub-micron column structure of the present invention have been completely and clearly introduced; next, a method for manufacturing scintillator with sub-micron column structure will be described in follows. Please refer to FIG. 2, there is shown a flowchart of the method for manufacturing scintillator with sub-micron column structure according to the present invention. As shown in FIG. 2, this manufacturing method includes 6 primary steps of:

(24) Step (S1), fabricating a tubular template 11 having a plurality of thin film oxidized metal tubes 113 by processing an anodic treatment;

(25) Step (S2), adjusting the tube diameter of the thin film oxidized metal tubes 113 by a chemical etching process;

(26) Step (S2a), forming a reflective layer on the inner walls of the thin film oxidized metal tubes 113 by a chemisorption process;

(27) Step (S3), forming a thin film scintillator on the inner walls of the thin film oxidized metal tubes 113 by a chemical impregnation process;

(28) Step (S4), filling a liquid phase of scintillator material into the thin film oxidized metal tubes 113 by a die casting process, so as to form a scintillator column 12 in each thin film oxidized metal tube 113; and

(29) Step (S5), forming a package layer 13 on the surface of the tubular template 11.

(30) Please continuously refer to FIG. 3, which illustrates a detailed flowchart of the step (S1); moreover, please simultaneously refer to FIG. 4 and FIG. 5, there are shown schematic manufacturing process diagrams of the scintillator with sub-micron column structure. As shown in FIG. 3, the aforesaid step (S1) includes 6 detailed steps of:

(31) Firstly, in step (S11), it processes a surface treatment to a metal substrate by mechanical grinding, and then anneals the metal substrate. Herein, an aluminum substrate is exemplarily used as the metal substrate for further describing the step (S11): using a sandpaper machine to mechanically grind the aluminum substrate from 400# sandpaper to 2000# sandpaper, and then disposing the aluminum substrate in an atmosphere furnace for annealing under 550 C. for 1 hr.

(32) Next, in step (S12), it disposes the metal substrate in a first electrolyte solution for processing an electrolytic polishing treatment under a first electrolyte voltage and a first electrolyte temperature for a first electrolyte time. Similarly, the aluminum substrate is exemplarily used as the metal substrate for further describing the step (S12): disposing the aluminum substrate in the first electrolyte solution consisting of 520% HClO.sub.4, 520% CH.sub.3(CH.sub.2).sub.3OCH.sub.2CH.sub.2OH and 6090% C.sub.2H.sub.6O under the first electrolyte voltage of 5V50V and the first electrolyte temperature of 2 C.40 C. for the first electrolyte time of 1 min10 min. Moreover, it needs to further explain that the best conditions for the electrolytic polishing treatment in aforesaid step (S12) include: the electrolyte solution consisting of 15% HClO.sub.4, 15% CH.sub.3(CH.sub.2).sub.3OCH.sub.2CH.sub.2OH and 70% C.sub.2H.sub.6O, the first electrolyte voltage of 40V, the first electrolyte temperature of 25 C., and the first electrolyte time of 90 seconds.

(33) In step (S13), it disposes the metal substrate in a second electrolyte solution for processing a first-time anodic treatment under a second electrolyte voltage and a second electrolyte temperature for a second electrolyte time. Similarly, the aluminum substrate is exemplarily used as the metal substrate for further describing the step (S13): disposing the aluminum substrate in the second electrolyte solution consisting of 110 vol % H.sub.3PO.sub.4 for processing the first-time anodic treatment under the second electrolyte voltage of 50V200V and the second electrolyte temperature of 5 C.15 C. for the second electrolyte time of 1 min24 hr. Moreover, the best conditions for the first-time anodic treatment in aforesaid step (S13) include: the second electrolyte solution consisting of 1 vol % H.sub.3PO.sub.4, the second electrolyte voltage of 180V, the second electrolyte temperature of 0 C., and the second electrolyte time of 20 min.

(34) In step (S14), it disposes the product of the step (S13) into a first remove solution, so as to remove the anodization film on the surface of the metal substrate under a first remove temperature for a first remove time. Similarly, the aluminum substrate is exemplarily used as the metal substrate for further describing the step (S14): disposing the product of the step (S13) into the first remove solution consisting of 15 wt % CrO.sub.3 and 115 vol % H.sub.3PO.sub.4, so as to remove the thin film oxidized aluminum on the surface of the aluminum substrate under the first remove temperature of 40 C.80 C. for the first remove time of 10 min60 min. Moreover, the best conditions for the first-time anodic treatment in aforesaid step (S14) include: the first remove solution consisting of 1.8 wt % CrO.sub.3 and 6 vol % H.sub.3PO.sub.4, the first remove temperature of 60 C. and the first remove time of 30 min.

(35) In step (S15), it disposes the metal substrate in the second electrolyte solution again, so as to processing a second-time anodic treatment under the second electrolyte voltage and the second electrolyte temperature for the second electrolyte time. The process conditions of the second-time anodic treatment in step (S15) are the same to the first-time anodic treatment in step (S13); moreover, when processing the second-time anodic treatment, the thickness of thin film oxidized aluminum on the surface of the aluminum substrate increases with the processing electrolyte time, and the growth rate of thin film oxidized aluminum thickness is around 6 m/hr. As shown in FIG. 4(a) and FIG. 4(b), the stereo diagram and the side view of the metal substrate been processed twice anodic treatments is illustrated.

(36) As shown in FIG. 4, the thin film oxidized aluminum on the surface of the aluminum substrate presents a regular cell shape or a nano tube structure, and there is a barrier layer formed at the interface of the nano tube terminal and the aluminum substrate. This thin film oxidized aluminum is also called as anodic aluminum oxide (AAO), anodic alumina nanoholds (AAN), anodic alumina membrane (AAM), or porous anodic alumina (PAA). In the present invention, the anodic treatment is completed through the reaction formula of 2Al.sup.+3+3H.sub.2O.fwdarw.Al.sub.2O.sub.3+6H.sup.+, moreover, the pH value of the electrolyte solution must be controlled for being smaller than 4 (i.e., the electrolyte solution must be an acidic solution), and the applied voltage needs to be controlled for being greater than 1.8V (i.e., the applied voltage must be greater than standard hydrogen electrode potential (SHE)). Besides, H.sup.+ in above-mentioned reaction formula would become H.sub.2 gas by H.sup.++H.sup.+.fwdarw.H.sub.2, wherein the H.sub.2 gas may flow out of the thin film oxidized aluminum (Al.sub.2O.sub.3), so as to facilitate the formation of a porous thin film oxidized aluminum (i.e., the porous AAO). Therefore, it is able to know that, the thin film oxidized aluminum having a plurality of apertures with uniform pore size can be manufactured by controlling the flow out rate of H.sub.2 gas.

(37) To make more descriptions for thin film oxidized aluminum having apertures, the thin film oxidized aluminum (i.e., Al.sub.2O.sub.3 thin film) grows upwards by hexagonal pores type in the beginning; moreover, these hexagonal pores are then transformed to circular pores because the arrangement of the atoms around the hexagonal pores gets to disorder with the increase of the anodic treatment time. The change of the pore size can be calculated by formula of C=mV, where C presents the pore size, V presents the anodic treatment voltage and m is a constant (22.5). Generally, if the thin film oxidized aluminum on the surface of the aluminum substrate presents a regular cell structure with the pore size smaller than 100 nm, the thin film oxidized aluminum is then called nano oxidized aluminum tubes; Or, if the thin film oxidized aluminum on the surface of the aluminum substrate presents a regular cell structure with the pore size greater than 100 nm, the thin film oxidized aluminum is then called sub-micron oxidized aluminum tubes. In the present invention, the tube diameter of the thin film oxidized aluminum tubes can be controlled by using different manufacturing parameters; for example the thin film oxidized aluminum tubes with 8 nm tube diameter can be fabricated by using H.sub.2SO.sub.4 as anodic treatment solution, and the thin film oxidized aluminum tubes with 500 nm tube diameter can be made by using H.sub.3PO.sub.4 as anodic treatment solution.

(38) Finally, in step (S16), it disposes the product of the step (S15) into a second remove solution for a second remove temperature, so as to remove the metal substrate and obtain the tubular template having the thin film oxidized metal tubes. As shown in FIG. 5(a), the stereo diagram of the tubular template is illustrated, and FIG. 5(b) shows the tube diameter of this tubular template. Similarly, the aluminum substrate is exemplarily used as the metal substrate for further describing the step (S16): disposing the product of the step (S15) into a second remove solution consisting of HCl and CuCl.sub.2 under room temperature for a few minutes, and the microstructure image of the obtained tubular template having the thin film oxidized metal tubes (i.e., the thin film oxidized metal tubes 113) is shown in FIG. 6, wherein the tube diameter of the thin film oxidized metal tubes is 500 nm.

(39) Thus, the step (S1) of the manufacturing method is carried out and the tubular template 11 consists of the thin film oxidized metal tubes 113 is obtained by finishing above-mentioned step (S11)step (S16); next, the tube diameter of the thin film oxidized metal tubes 113 can be adjusted in step (S2) through the chemical etching process. In the present invention, the step (S2) includes the detailed steps of step (S21), disposing the tubular template 11 in a micro-structure modulation solution; and step (S22), adjusting the tube diameter of the thin film oxidized metal tubes 113 under a micro-structure modulation temperature for a micro-structure modulation time. Similarly, the aluminum substrate is exemplarily used as the metal substrate for further describing the steps (S21) and (S22): taking 5 vol % H.sub.3PO.sub.4 as the micro-structure modulation solution and using the micro-structure modulation temperature of 25 C. and the micro-structure modulation time of 2.5 hr as operation conditions, so as to adjust the tube diameter of the thin film oxidized aluminum tubes (AAO) shown in FIG. 6, and then obtain the thin film oxidized aluminum tubes with the tube diameter of 350 nm shown in FIG. 7. Or, taking 5 vol % H.sub.3PO.sub.4 as the micro-structure modulation solution and using the micro-structure modulation temperature of 25 C. and the micro-structure modulation time of 1 hr as operation conditions, so as to adjust the tube diameter of the thin film oxidized aluminum tubes (AAO) shown in FIG. 6, and then obtain the thin film oxidized aluminum tubes with the tube diameter of 250 nm shown in FIG. 8.

(40) Moreover, in the method for manufacturing scintillator with sub-micron column structure of the present invention, by modulating the manufacturing parameters and conditions of the first-time anodic treatment in step (S13), the second-time anodic treatment in step (S15), and the tube diameter adjusting process in step (S2), the tube diameter, the thickness and the tube density of thin film oxidized aluminum tubes (i.e., the thin film oxidized metal tubes 113 of the tubular template 11) can be controlled to 10500 nm, 0.11000 m and 10.sup.810.sup.12 tube/cm.sup.2, respectively.

(41) Please refer to FIG. 9, FIG. 10 and FIG. 11, there are shown microstructure images of anodic aluminum oxide tubes with tube diameter of 70 nm, 40 nm and 10 nm. The manufacturing parameters and conditions of the first-time anodic treatment in step (S13), the second-time anodic treatment in step (S15), and the tube diameter adjusting process in step (S2) for making the anodic aluminum oxide tubes shown in FIG. 9, FIG. 10 and FIG. 11 are listed in following table 2

(42) TABLE-US-00002 TABLE 2 anodic aluminum anodic aluminum anodic aluminum oxide tubes of FIG. oxide tubes of FIG. oxide tubes of FIG. 9 10 11 Step (S13) taking 3 wt % C.sub.2H.sub.2O.sub.4 taking 3 wt % C.sub.2H.sub.2O.sub.4 taking 10 vol % as the electrolyte as the electrolyte H.sub.2SO.sub.4 as the solution, and using solution, and using electrolyte solution, the electrolyte the electrolyte and using the voltage of 40 V, the voltage of 40 V, the electrolyte voltage of electrolyte electrolyte 18 V, the electrolyte temperature of 25 C., temperature of 25 C., temperature of 15 C., and the electrolyte and the electrolyte and the electrolyte time of 20 min as the time of 20 min as the time of 20 min as the anodic treatment anodic treatment anodic treatment conditions. conditions. conditions. Step (S15) the growth rate of the growth rate of the growth rate of thin film oxidized thin film oxidized thin film oxidized aluminum thickness aluminum thickness aluminum thickness is around 10 m/hr. is around 10 m/hr. is around 8 m/hr. Step (S2) taking 5 vol % H.sub.3PO.sub.4 as taking 5 vol % H.sub.3PO.sub.4 as taking 5 vol % H.sub.3PO.sub.4 as the micro-structure the micro-structure the micro-structure modulation solution and modulation solution and modulation solution and using the micro-structure using the micro-structure using the micro-structure modulation temperature modulation temperature modulation temperature of 25 C. and the of 25 C. and the of 25 C. and the micro-structure micro-structure micro-structure modulation time of modulation time of modulation time of 5 min 60 min as the operation 10 min as the operation as the operation conditions. conditions. conditions.

(43) Thus, FIG. 9 shows the microstructure image of anodic aluminum oxide (Al.sub.2O.sub.3) tubes with tube diameter of 70 nm, FIG. 10 shows the microstructure image of anodic aluminum oxide (Al.sub.2O.sub.3) tubes with tube diameter of 40 nm, and FIG. 11 shows the microstructure image of anodic aluminum oxide (Al.sub.2O.sub.3) tubes with tube diameter of 10 nm.

(44) In addition, it needs to further describe that, besides the aluminum substrate, titanium substrate can also be used as the metal substrate for making the tubular template 11 consisting of the thin film oxidized metal tubes 113 by the following manufacturing steps:

(45) Firstly, limiting the surface area of the titanium substrate under process by using a mould; next, processing an electrolytic polishing treatment to the limited surface area of the titanium substrate, wherein the electrolyte solution consists of 510% HClO.sub.4, 1050 vol % CH.sub.3(CH.sub.2).sub.3OCH.sub.2CH.sub.2OH and 4085% CH.sub.3OH, and the operation conditions include: the electrolyte voltage of 5V60V, the electrolyte temperature of 2 C.40 C., and the electrolyte time of 1 min10 min. Moreover, the best manufacturing parameters and conditions for the electrolytic polishing treatment include: the electrolyte solution consisting of 5 vol % HClO.sub.4, 42 vol % CH.sub.3(CH.sub.2).sub.3OCH.sub.2CH.sub.2OH and 53 vol % CH.sub.3OH, the electrolyte voltage of 52V, the electrolyte temperature of 25 C., and the electrolyte time of 3 min.

(46) Continuously, disposing the polished titanium substrate in the mould for processing anodic treatment by using constant voltage and current, so as to form the oxidized titanium (TiO.sub.2) on the titanium substrate; wherein the electrolyte solution for anodic treatment consists of 0.4 wt % NH.sub.4F, 2 vol % H.sub.2O and 98 vol % HOCH.sub.2CH.sub.2OH, and the operation conditions include: the constant voltage of 60V and the anodic treatment of 1 hr for first-time anodic treatment, and the constant current of 0.85 A and the anodic treatment of 3 hr for second-time anodic treatment.

(47) After completing the anodic treatment, the remaining electrolyte solution on the oxidized titanium (TiO.sub.2) is washed and removed by ethanol, and then baking the oxidized titanium (TiO.sub.2) for removing the residual liquid in the thin film oxidized titanium tubes of the TiO.sub.2. Thus, as the present of the microstructure image in FIG. 12, the anodic oxidized titanium (TiO.sub.2) having the thin film oxidized titanium tubes with tube diameter of 90 nm can be used as the tubular template 11 of the scintillator with sub-micron column structure 1.

(48) Therefore, after the tubular template 11 consisting of a plurality of thin film oxidized metal tubes 113 (i.e., the thin film oxidized aluminum tubes or the thin film oxidized titanium tubes) is fabricated; subsequently, for increasing the efficiency of the scintillators 12 to an external high-energy wave (for example, X-ray), the step (S2a) is adopted for forming a reflective layer on the inner walls of the thin film oxidized metal tubes 113 by the chemisorption process. The step (S2a) includes the detailed steps of:

(49) Firstly, in step (S2a1), it disposes the tubular template 11 in a sensitization solution for treating sensitization process under a sensitization temperature for a sensitization time. Herein, the thin film oxidized aluminum is exemplarily used as the tubular template 11 for further describing the step (S2a1): disposing the tubular template 11 in the sensitization solution consisting of 0.13 wt % SnCl.sub.2, 110 vol % HCl and H.sub.2O under a sensitization temperature of 10 C.40 C. for the sensitization time of 0.5 min30 min. Moreover, the best conditions for the sensitization process in aforesaid step (S2a1) include: the sensitization solution consisting of 0.3 wt % SnCl.sub.2, 2.5 vol % HCl and H.sub.2O, the sensitization temperature of 25 C., and the sensitization time of 3 min.

(50) In step (2a2), it disposes the product of the step (S2a1) in an activation solution for treating activation process under an activation temperature for an activation time. Similarly, the thin film oxidized aluminum is exemplarily used as the tubular template 11 for further describing the step (S2a2): disposing the product of the step (S2a1) in an activation solution consisting of 0.15 wt % PdCl.sub.2, 110 vol % HCl and H.sub.2O under the activation temperature of 10 C.40 C. for the activation time of 0.5 min30 min. Moreover, the best conditions for the activation process in aforesaid step (S2a2) include: the activation solution consisting of 0.1 wt % PdCl.sub.2, 1.0 vol % HCl and H.sub.2O, the activation temperature of 25 C., and the activation time of 3 min.

(51) In step (S2a3), it disposes the product of the step (2a2) in an electro-less deposition solution for treating electro-less deposition process under an electro-less deposition temperature and an electro-less deposition pH value for an electro-less deposition time, so as to form the reflective layer on the inner walls of the thin film oxidized metal tubes 113. Similarly, the thin film oxidized aluminum is exemplarily used as the tubular template 11 for further describing the step (S2a3): disposing the product of the step (S2a2) in the electro-less deposition solution consisting of 0.510 wt % NiSO.sub.4, 0.510 wt % NaH.sub.2PO.sub.2, 0.510 ppm Pb(NO.sub.3).sub.2, and 0.510 wt % Na.sub.3C.sub.6H.sub.5O.sub.7 under the electro-less deposition temperature of 50 C.90 C. and the electro-less deposition pH value of 45.5 for the electro-less deposition time of 1 min60 min. Moreover, the best conditions for the electro-less deposition process in aforesaid step (S2a3) include: the electro-less deposition solution consisting of 2 wt % NiSo.sub.4, 2 wt % NaH.sub.2PO.sub.2, 2 ppm Pb(NO.sub.3).sub.2, and 2 wt % Na.sub.3C.sub.6H.sub.5O.sub.7, the electro-less deposition temperature of 70 C., the electro-less deposition pH value of 5, and the electro-less deposition time of 330 min.

(52) Thus, by above-mentioned steps (S2a1)(S2a3), the nickel tubes are formed and attached on the inner walls of the thin film oxidized aluminum (Al.sub.2O.sub.3) tubes 113 of the tubular template 11, and the microstructure image and the EDS (energy dispersive spectrometer) analysis plot are respectively shown in FIG. 13 and FIG. 14.

(53) After the step (S2) is finished, the step (S3) is continuously used for forming a thin film scintillator on the inner walls of the thin film oxidized metal tubes 113 by a chemical impregnation process. The step (S3) includes the detailed steps of (S31) and (S32). In step (S31), it immerses the tubular template 11 in an aqueous solution for an immersion time, wherein the aqueous solution includes a scintillator material having a specific weight percent opposite to the aqueous solution. Then, in step (S32), it treats the tubular template 11 by thermal process, so as to remove the water in the thin film oxidized metal tubes 113.

(54) Herein, the thin film oxidized aluminum is exemplarily used as the tubular template 11 for further describing the steps (S31) and (S32): immersing the thin film oxidized aluminum in the aqueous solution having 120 wt % CsI for 5 min60 min, and then treating the thin film oxidized aluminum by thermal process under 100 C.600 C. for 5 min120 min, so as to remove the water in the thin film oxidized aluminum tubes. Moreover, the best conditions for the immersing treatment in aforesaid step (S31) include: the aqueous solution having 1 wt % CsI and the immersing time of 10 min; besides, the best conditions for the thermal process in aforesaid step (S32) include: the thermal temperature off 400 C. and the thermal time of 10 min. Thus, by above-mentioned steps (S31)(S32), the thin film CsI are formed and attached on the inner walls of the thin film oxidized aluminum (Al.sub.2O.sub.3) tubes 113 of the tubular template 11, and the microstructure image and the EDS (energy dispersive spectrometer) analysis plot are respectively shown in FIG. 15 and FIG. 16.

(55) After the step (S3) is finished, the step (S4) is continuously used for filling a liquid phase of scintillator material into the thin film oxidized metal tubes 113 by a die casting process, so as to form a scintillator column 12 in each thin film oxidized metal tube 113. The step (S4) includes the 4 detailed steps of:

(56) Firstly, in step (S41), it disposes the powder of the scintillator material on the surface of the tubular template 11; next, in step (S42), it treats the product of step (S41) by thermal process, so as to make the melted scintillator material cover the surface of the tubular template 11. Subsequently, in step (S43), it permeates the melted scintillator material in to the thin film oxidized metal tubes 113 by using a die-casting mold; and eventually, in step (S44), it waits for the solidification of the melted scintillator material in the thin film oxidized metal tubes 113, and then a scintillator column 12 is formed in each thin film oxidized metal tube 113.

(57) Similarly, the thin film oxidized aluminum is exemplarily used as the tubular template 11 for further describing the steps (S41)(S44), disposing the CsI (or CsI doped with Tl) power on the surface of the thin film oxidized aluminum, and then heating the thin film oxidized aluminum until the thermal temperature reaches 650 C. (650 C. is greater than the melting point (621 C.) of the CsI) for making the melted CsI cover the thin film oxidized aluminum; and next to permeate the melted CsI in to the thin film oxidized aluminum tubes of the oxidized aluminum by using the die-casting mold; eventually, after the solidification of the melted CsI is completed, the CsI column is formed in each thin film oxidized aluminum tube.

(58) Finally, for protecting the scintillators 12 from being damaged by water vapor and oxygen, a package layer is formed on the surface of the tubular template 11 via the step (S5). In the present invention, the material of the package layer 13 can be polymer, metal, ceramic, and combination thereof, and which is formed on the surface of the tubular template by spin coating, vapor deposition, sputtering, and combination process thereof.

(59) Therefore, the above descriptions have been clearly and completely introduced the scintillator with sub-micron column structure and the manufacturing method thereof of the present invention; in summary, the present invention has the following advantages:

(60) 1. In the present invention, it utilizes anodic treatment and die casting technology with low cost and rapid production to manufacture a high-value scintillator with sub-micron column structure, and this scintillator with sub-micron column structure can also be manufactured by mass production.
2. By using the manufacturing method proposed by the present invention, the scintillator with sub-micron column structure or nano column structure can be made for being applied in medical equipments, nuclear medicine, and security detection technologies.
3. Inheriting to above point 2, the thin film oxidized metal tubes of the tubular template can be further manufactured to nano tubes by adjusting electrolyte composition, electrolysis voltage, and processing time of anodic treatment, and the aperture size, the thickness and the vessel density of the nano tube can be controlled and ranged from 10 nm to 500 nm, 0.1 m to 1000 m, and 10.sup.8 to 10.sup.12 tube/cm.sup.2, respectively.

(61) The above description is made on embodiments of the present invention. However, the embodiments are not intended to limit scope of the present invention, and all equivalent implementations or alterations within the spirit of the present invention still fall within the scope of the present invention.