Metal oxide based radiation sensor
10871580 ยท 2020-12-22
Assignee
Inventors
- Abdullah Nasser Alodhayb (Riyadh, SA)
- Hamad Abdulaziz Albrithen (Riyadh, SA)
- Khaled Zouher Shamma (Riyadh, SA)
Cpc classification
International classification
Abstract
A metal oxide based radiation sensor includes a titanium dioxide (TiO.sub.2) thin film layer on a microcantilever surface. The TiO.sub.2 thin film layer initially comprises anatase and rutile crystal structures. Exposure to radiation, such as gamma radiation, results in changes in structural features and mechanical behaviors of the metal oxide based radiation sensor. In particular, the resonant frequency changes with exposure to radiation dosages. The structural and mechanical behaviors of the metal oxide based radiation sensor change proportionally with dosage within a range of dosages.
Claims
1. A radiation sensor comprising: a substrate; a microcantilever having one end operatively coupled to the substrate; and a metal oxide layer arranged on a surface of the microcantiever, wherein the metal oxide layer comprises the metal oxide in at least one crystal form, the at least one crystal form being capable of transformation to a different form upon exposure to a radiation to be detected.
2. The radiation sensor of claim 1, wherein the metal oxide is titanium dioxide.
3. The radiation sensor of claim 2, wherein the at least one crystal form includes rutile.
4. The radiation sensor of claim 2, wherein the at least one crystal form includes rutile and anatase.
5. The radiation sensor of claim 2, wherein the microcantilever comprises a silicon based material.
6. The radiation sensor of claim 5, wherein the metal oxide layer has a first average thickness in a direction normal to the surface of the microcantilever on which the metal oxide layer is arranged and the microcantilever has a second average thickness in said direction, and the ratio of the first thickness to the second thickness is between 1:50 and 1:1.
7. The radiation sensor of claim 6 wherein the ratio of the first thickness to the second thickness is between 1:20 and 1:5.
8. The radiation sensor of claim 1, wherein the first thickness is uniform over the surface of the microcantilever on which the metal oxide layer is arranged.
9. The radiation sensor of claim 1, wherein the metal oxide layer comprises crystal grains having an initial grain size before exposure to the radiation to be detected and the crystal grains have a second grain size after exposure to the radiation to be detected, wherein the second grain size is smaller than the initial grain size.
10. A device comprising the radiation sensor of claim 1 and a structure for immobilizing the radiation sensor and enclosing the radiation sensor, the chamber being penetrable to the radiation to be detected.
11. The device of claim 10, wherein the chamber is configured to be worn on a person.
12. A method for detecting radiation exposure comprising steps of: measuring a detectable quantity of radiation in the radiation sensor of claim 1 to get a base value; exposing the radiation sensor to radiation; measuring the detectable quantity of radiation exposed to the radiation sensor to get an exposed value; and calculating a difference between the base value and the exposed value as a change in the detectable quantity of the radiation sensor.
13. The method of claim 12, wherein the detectable quantity is the resonant frequency of the microcantilever.
14. A method of fabricating a radiation sensor comprising: providing a microcantilever having one end coupled to a substrate; and coating a side of the microcantilever with a metal oxide layer, wherein the metal oxide layer comprises the metal oxide in at least one crystal form, the at least one crystal form being capable of transformation to a different form upon exposure to a radiation to be detected.
15. The method of claim 14, wherein the metal oxide layer is coated on the side of the microcantilever by means of atomic layer deposition.
16. The method of claim 14, wherein the metal oxide layer ranges from about 50 to about 200 nm thick.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)
(14) Similar reference characters denote corresponding features consistently throughout the attached drawings.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
(15) An embodiment of the present specification is directed to a radiation sensor, shown in
(16) In an embodiment, the metal oxide layer has a first average thickness in a direction normal to the surface of the microcantilever on which the metal oxide layer is arranged and the microcantilever has a second average thickness in said direction, and the ratio of the first thickness to the second thickness is between 1:50 and 1:1. In another embodiment, the ratio of the first thickness to the second thickness is between 1:20 and 1:5. The metal oxide layer may be arranged on a part or entirety of a surface of the microcantilever. The metal oxide layer has, in an embodiment, uniform thickness over the surface of the microcantilever on which the metal oxide layer is disposed. The absolute dimensions of the microcantilever and metal oxide layer can be such that the resonant frequency of the microcantilever with metal oxide layer is sensitive to changes due to loss of the metal oxide layer.
(17) The microcantilever is not particularly limited in shape. In one embodiment, the microcantilever is a rectangular prism with a width, length and second average thickness. In this case, the resonant frequency is approximated according to:
.sub.0=(k/m).sup.1/2, where k=Et.sup.3w/4].sup.3
(18) where resonant frequency (.sub.0) of the bare microcantilever is related to its spring constant (k) and mass (m). E=Young's modulus of Elasticity (a property of the microcantilever material), t=thickness, w=width, and l=length. The dimensions t, w and l of the microcantilever can be chosen such that k above is on the order of the mass of metal oxide arranged on the microcantilever. In particular embodiments, the length of the microcantilever is on the order of mm, i.e., 0.1-10 mm, 0.5-5 mm or 0.5-1 mm. The width of the microcantilever is 10-1000 microns, 50-500 microns or 50-100 microns; and the thickness of the microcantilever is 0.5-10 microns or 1-5 microns. The metal oxide layer may be 10-1000 microns thick, 50-500 microns thick, or 50-200 microns thick.
(19) In an embodiment, the metal oxide layer comprises crystal grains having an initial grain size before exposure to the radiation to be detected and the crystal grains have a second grain size after exposure to the radiation to be detected, wherein the second grain size is smaller than the initial grain size. The crystal grain size may be determined by any typical means of observing and calculating an average grain size, for example by XRD and calculating an average grain size using Scherrer's formula, as will be discussed below, or else direct imaging by SEM, TEM or AFM, for example, and calculating an average area of observed crystal grains.
(20) In another embodiment of the radiation sensor, exposing the radiation sensor to the radiation of a first dosage or a second dosage results in a first frequency shift or a second frequency shift, respectively, such that when the first dosage is greater than the second dosage, the first frequency shift is greater than the second frequency shift.
(21) The radiation to be detected is, in an embodiment, an ionizing radiation, such as radiation in the ultraviolet, x-ray or gamma ranges. In a particular embodiment, the radiation may be a gamma radiation.
(22) In an embodiment, the radiation sensor may be incorporated into a device that further includes a structure such as a chamber for immobilizing the radiation sensor and enclosing the radiation sensor, the chamber being penetrable to the radiation to be detected. In particular, the chamber may have dimensions suitable to be worn on a person. The device may further comprise a means of attaching to a person, such as a clip, a hook, a loop, etc. so that the device may be worn by the person, thereby being useful as a personal dosimeter.
(23) The present subject matter further includes a method for detecting radiation exposure comprising the steps of: measuring a detectable quantity of radiation using the radiation sensor to get a base value prior to exposing the radiation sensor to radiation; measuring the detectable quantity of the radiation sensor to get an exposed value; and calculating a difference between the base value and the exposed value as a change in the detectable quantity of the radiation sensor. The detectable quantity is, in an embodiment, the resonant frequency of the microcantilever.
(24) The present subject matter further includes a method of fabricating a radiation sensor that includes the steps of providing a microcantilever having one end coupled to a substrate, coating a side of the microcantilever with a metal oxide layer, such that the metal oxide layer comprises the metal oxide in at least one crystal form, the at least one crystal form being capable of transformation to a different form upon exposure to a radiation to be detected. In an embodiment, the metal oxide layer is coated on the side of the microcantilever by means of atomic layer deposition. In particular, the metal oxide layer may be between 50-200 nm thick.
(25) It should be understood that the amounts of materials for the methods described herein are exemplary, and appropriate scaling of the amounts are encompassed by the present subject matter, as long as the relative ratios of materials are maintained. As used herein, the term about, when used to modify a numerical value, means within ten percent of that numerical value.
(26) In the following examples, TiO.sub.2 thin films were evaluated as a sensing layer on silicon-based cantilevers for detection of gamma-ray radiation and physically characterized. All samples were exposed to gamma rays produced by .sup.60Co at doses ranging between 0 kGy to 40 kGy. The optical properties of silicon wafers coated by a TiO.sub.2 thin film, wherein the TiO.sub.2 thin film was grown by atomic layer deposition (ALD) at 200 C. to a 100 nm thickness, were examined before and after irradiation using X-ray diffraction (XRD), scanning electron microscopy (SEM) and spectroscopic ellipsometry (SE). Atomic force microscopy (AFM) was performed on the TiO.sub.2 thin film coated silicon-based cantilevers to find a resonant frequency shift (f.sub.o) resulting from irradiation of the TiO.sub.2 thin films. Morphology and other physical properties of the TiO.sub.2 thin films on silicon wafers were examined as imaged by AFM.
(27) X-ray diffraction (XRD) results showed that the TiO.sub.2 thin films on silicon wafers initially exhibited a nanocrystalline structure of a mixture of rutile and anatase phases. After irradiation, the TiO.sub.2 thin films exhibited a nanocrystalline structure of only anatase. The TiO.sub.2 thin films on silicon microcantilevers as exemplary radiation detectors exhibited a resonant frequency shift (f.sub.o) measured in an atomic force microscopy (AFM) system that changed proportionally with radiation doses between 0 kGy and 20 kGy. AFM and SEM images of the TiO.sub.2 thin films before and after irradiation supported nanocrystalline structural change detected by XRD.
(28) Spectroscopic ellipsometry measurements showed a proportional relation between TiO.sub.2 thin film thickness, roughness and optical constants with irradiation dose when fit using the Cauchy model. Frequency shift (f.sub.o) is a convenient detectable parameter of the proposed dosimeter, in light of the reproducibility and sensitivity of measurements made according to the present methods, but one skilled in the art would understand that other detectable parameters, including crystal grain size, crystal type make-up, film thickness and roughness and optical constants may be used to detect radiation exposure and particularly radiation dosage in the range of a proportional response of the detectable parameter to the radiation dosage. The maximum detectable linear effect of the exemplary TiO.sub.2 thin films occurred at a dose of 20 kGy. Thus, the exemplary TiO.sub.2 thin films on a microcantilever or other substrate may be used as dosimeters for radiation exposure less than around 20 kGy, making them particularly useful in, for example, personal dosimeters.
(29) The following examples illustrate the present teachings.
EXAMPLES
Example 1
Synthesis of the TiO.SUB.2 .Thin Films on Silicon-Based Substrates
(30) Si (100) wafers (450 micron thickness) and Si microcantilever chips (Micromotive company, Octosensis micro cantilever Arrays Static-mode sensors, model: Octo-500, Cantilever length=450 m Cantilever width=90 m, Cantilever thickness=1 t 0.3 m, initial resonant frequency 4-8 KHz, 8 microcantilevers attached to substrate per chip) were cleaned prior to every experiment using a piranha-etch cleaning procedure [3:1 mixture of sulfuric acid (H.sub.2SO.sub.4) and 30% hydrogen peroxide (H.sub.2O.sub.2)]. The substrates were then dried and subject to ozone to remove organic contaminants (PSI) series digital UV benchtop ozone system operated at both 185 nm and 254 nm). TiO.sub.2 thin films were deposited on the cleaned Si wafers and eight microcantilevers (CA 1 to 8) of the by atomic layer deposition (ALD) (Beneq TFS 200). Film deposition was carried out at 200 C. and 17 mbar pressure. The TiO.sub.2 thin films were prepared from titanium tetrachloride (TiCl.sub.4) and deionized water as precursors. TiCl.sub.4 evaporation temperature was held at 25 C., while the deionized water evaporation temperature was held at 20 C. Flow rates of the carrier gas for TiCl.sub.4 and deionized water were 150 and 200 sccm, respectively, and pressures were 9 mbar and 8 mbar, respectively. High purity (99.9999%) nitrogen gas was used as a purging and carrying gas. 100 nm thick TiO.sub.2 films were formed by performing 2500 deposition cycles.
(31) All samples prepared as above were exposed to gamma source Cobalt-60 (Nordionmodel GC-220) with a 5.2714 years half-life and 927.299 Gy/h dose rate. The samples were exposed to different doses of 10, 20, 30 and 40 kGy. The dosage was controlled by controlling the exposure time of the samples inside the radiation gamma cell.
Example 2
Characterization of TiO.SUB.2 .Thin Films Exposed to Radiation
(32) Structural properties of as-deposited and gamma-irradiated TiO.sub.2 thin films on Si wafer were evaluated by Scanning Electron Microscope (SEM; JEOL JSM-7600F) and X-Ray Diffractometry (XRD; Rigakumodel Ultima IV) with a CuK radiation source (=1.5406 ) at 40 kV/40 mA. Spectroscopic ellipsometry (WVASE-J. A. Woolam) was used to determine the index of refraction for thickness in the range of 600-2500 nm. Ellipsometry measurements were fit using the Cauchy model. Resonant frequency shift (f.sub.o) for TiO.sub.2 thin film coated microcantilevers were investgated by Atomic Force Microscope (AFM; Veeco-Bruker SPMs). AFM was also used to investigate the surface topography and roughness of the as-deposited and irradiated Tio.sub.2 thin films on silicon wafers. Scanning Probe Image Processor (SPIP) software was used to process and analyze the AFM images.
(33) Results of Characterization of TiO.sub.2 Thin Films Exposed to Radiation
(34) Xrd Analysis:
(35) XRD analysis was performed on all samples. The scanning angle was changed between 20=35-60.
D=0.94/ cos (1)
where D is the average grain size, is the X-ray wavelength (=1.5406 A, Cu-K), is the diffraction angle and is the line broadening at half the maximum (FWHM) of the observed diffraction peak. The average grain size of the TiO.sub.2 thin films at the strongest peak (004) decreased from 100.9 to 44.1 nm as the gamma dose increased from 0 kGy to 40 kGy.
(36) Resonant Frequency Shift Analysis:
(37) AFM was used to find the resonant frequency shift (f.sub.o) caused by changing the gamma dose from 0 to 40 kGy. The radiation was applied on the top of the microcantilevers coated with TiO.sub.2, as shown in
(38) Structural Properties of the Exemplary TiO.sub.2 Thin Films on Si Wafers:
(39) AFM and SEM images obtained of Si wafers with TiO.sub.2 thin films of the same thickness, deposition method and gamma irradiation doses applied on the Si microcantilever coated by TiO.sub.2.
(40) AFM Analysis of Structural Properties:
(41) Scanning Probe Image Processor (SPIP) software was used to process AFM images taken over 10 m10 m area to find surface roughness and changes in detected particle specification parameters such as length, breadth, diameter, volume, height and area for the as-deposited and irradiated TiO.sub.2 thin films on Si wafers.
(42) Table 1 represents the roughness of the TiO.sub.2 thin films measured by AFM. The roughness increased linearly from 17 nm for non-irradiated samples to 19 nm for radiation doses of 20 kGy. Then, the surface improved partially with roughness 18 nm at 30 kGy, for higher doses the surface becomes roughly about 15.4 nm.
(43) TABLE-US-00001 TABLE 1 Summary of the roughness measured by AFM, roughness measured by SE and best-fit parameters of the ellipsometric model of TiO.sub.2 thin films after gamma radiation doses of 0-40 kGy Roughness Roughness Dose (AFM) (SE) Cauchy model parameters (kGy) (nm) (nm) A.sub.n B.sub.n C.sub.n 0 17.196 26.433 2.3093 0.0895 0.00925 10 17.84 26.456 2.3019 0.11054 0.01932 20 18.741 24.162 2.2832 0.13658 0.02671 30 18.067 26.643 2.3055 0.10044 0.01503 40 15.481 22.676 2.2739 0.16458 0.04121
(44) SEM Analysis of Structural Properties:
(45) SEM micrographs of as-deposited and irradiated TiO.sub.2 thin films are shown in
(46) Spectroscopic Ellipsometry Analysis:
(47) Spectroscopic ellipsometry was performed using polarized light with an angle of incidence of 650 and 75 on the TiO.sub.2 thin film samples prepared on silicon wafers. The Cauchy dispersion model was used to obtain best fit parameters , and refractive index n. Specifically, these SE data were fit using the equation:
(48)
where is the incident light wavelength and A.sub.n, B.sub.n and C.sub.n are Cauchy parameters. Spectroscopic ellipsometric measurements were performed on bare and TiO.sub.2 thin film coated silicon wafers subjected to 0-40 kGy radiation doses.
(49) SE Measurements of Si Wafers without TiO.sub.2 Thin Film:
(50) The optical constants of Si wafers without TiO.sub.2 thin film at gamma radiation doses 0 kGy, 1 kGy, 10 kGy and 20 kGy were calculated. Each sample was assumed to consist of a Si substrate with a native SiO.sub.2 layer. Measurements were performed using light over wavelengths from 124-2500 nm. Radiation of any tested dosage did not affect the optical properties of the control uncoated Si wafer, as can be observed in
(51) The thickness change indicates a mass change, which is inversely related to frequency change. Therefore, the results shown in
(52) SE Measurements of Si Wafers with TiO.sub.2 Thin Film:
(53) Exemplary TiO.sub.2 thin films were subjected to SE, as-deposited and irradiated at 10, 20, 30, and 40 kGy. The physical model assumptions used in fitting are shown in the inset of
(54)
(55) The thickness and roughness, determined by SE, of the exemplary TiO.sub.2 thin films subject to different radiation doses are shown in
(56)
(57) Exemplary TiO.sub.2 thin films were prepared by atomic layer deposition performed at 200 C. to a 100 nm thickness on silicon wafers and silicon cantilevers. The exemplary TiO.sub.2 thin films and TiO.sub.2 thin film coated microcantilevers, in particular, were reliable radiation detectors for a range of gamma ray dosages and were very reproducible, accurate and sensitive dosimeters for detection of gamma radiation between (0-20) kGy. XRD demonstrated that the exemplary TiO.sub.2 thin films comprised a mixture of rutile and anatase phases before irradiation and changed to anatase phase after irradiation. This change was correlated with a linear resonant frequency shift with a radiation dose for dosages between (0-20) kGy. This linear change is consistent with structural changes in the exemplary TiO.sub.2 thin films measured by spectroscopic ellipsometry, such as model film layer thicknesses and roughnesses. The above experiments control for the possiblitity of any contribution from the Si substrates, showing that the linear dose sensistive changes arise from the exemplary TiO.sub.2 thin films. The exemplary MEMS dosimeter (TiO.sub.2 thin film coated microcantilever) is particularly useful as, for example, personal dosimetric purposes.
(58) It is to be understood that the metal oxide based radiation sensor and related methods are not limited to the specific embodiments described above, but encompasses any and all embodiments within the scope of the generic language of the following claims enabled by the embodiments described herein, or otherwise shown in the drawings or described above in terms sufficient to enable one of ordinary skill in the art to make and use the claimed subject matter.