CN114315340B - High-nonlinearity ZnO-based polycrystalline ceramic and preparation method and application thereof - Google Patents
High-nonlinearity ZnO-based polycrystalline ceramic and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a high non-linear ZnO-based polycrystalline ceramic and a preparation method and application thereof, a natural Schottky barrier structure can be formed at a ZnO polycrystalline ceramic crystal boundary formed by a sintering process, and a back-to-back Schottky barrier model device is formed in a series mode by utilizing a metal electrode and the prepared ZnO polycrystalline ceramic, so that the influence of the defects of the electrode and the material of the device on the performance of a nuclear radiation detector is reduced, and the X-ray detector with the ultra-large volume and the time resolution of 10ns order is realized at extremely low cost.
Description
Technical Field
The invention belongs to the field of semiconductor nuclear radiation X-ray detection devices, and particularly relates to a high-nonlinearity ZnO-based polycrystalline ceramic and a preparation method and application thereof.
Background
The semiconductor nuclear radiation detector has the characteristics of high sensitivity, high energy resolution, small volume, easy integration, high spatial resolution, high response speed, wide linear range and the like, and has application prospects in the aspects of nuclear monitoring, spatial navigation, detection of products of high-energy nuclear physical experiments and the like. Currently, commercial semiconductor nuclear radiation detector materials are still predominantly silicon (Si), germanium (Ge), cadmium telluride (CdTe), and other narrow bandgap semiconductors. In contrast, the wide bandgap semiconductor material has better radiation resistance due to larger binding energy, and the wide bandgap semiconductor material has lower intrinsic carrier concentration and can be normally used in normal temperature and even high temperature environments. Therefore, the wide-bandgap semiconductor-based nuclear radiation detector has wider application prospect. The zinc oxide (ZnO) is used as a wide bandgap semiconductor, has a bandgap width of 3.4eV, has good photoelectric properties and radiation resistance, and is a preparation material of a nuclear radiation detector with great potential.
The nuclear radiation typically penetrates deeper into the material than light, requiring a larger volume of semiconductor material. And the semiconductor nuclear radiation detector collects the electron-hole pairs generated by radiation under the action of an electric field, and the radiation-induced carriers are greatly influenced by material defects in the material transportation process. Therefore, the growth technology of the wide bandgap semiconductor material with large volume and high quality is not mature at present, and the application of the wide bandgap semiconductor material in the field of nuclear radiation detection is limited.
Disclosure of Invention
The invention aims to provide a high-nonlinearity ZnO-based polycrystalline ceramic and a preparation method and application thereof, so as to overcome the problems in the prior art, a natural Schottky barrier structure can be formed at a ZnO-based polycrystalline ceramic crystal boundary formed by a sintering process, a back-to-back Schottky barrier model device is formed in a series mode, the influence of device electrode and material defects on the performance of a nuclear radiation detector is reduced, and an X-ray detector with an ultra-large volume and 10 ns-order time resolution is realized at extremely low cost.
The invention is realized by the following technical scheme:
a preparation method of high-nonlinearity ZnO-based polycrystalline ceramic comprises the following steps:
1) Taking the following analytically pure raw materials according to the stoichiometric ratio: 93.42mol% of ZnO,1.2mol% of Bi 2 O 3 ，1.1mol％Co 2 O 3 ，0.5mol％MnCO 3 ，1.3mol％NiO，1.48mol％SiO 2 And 1mol% of Sb 2 O 3 Mixing after ball milling, drying, grinding and sieving the mixed slurry after ball milling to obtain precursor powder;
2) And granulating, ageing, tabletting and binder removal are carried out on the precursor powder, and then sintering is carried out in the air atmosphere, so as to obtain the high-nonlinearity ZnO-based polycrystalline ceramic.
Further, the rotation speed of the ball mill in the step 1) is 300 r.min -1 The ball milling time is 12h.
Further, the drying temperature in the step 1) is 80 ℃, and a 100-mesh screen is adopted during sieving.
Further, the granulation in the step 2) is specifically as follows: and adding a PVA aqueous solution into the precursor powder, wherein the mass ratio of the precursor powder to the PVA aqueous solution is 100.
Further, the ageing time in the step 2) is 24h; the pressure required by tabletting is 100Mpa; the rubber discharging temperature is 600 ℃, and the rubber discharging time is 3 hours.
Further, the sintering conditions in the step 2) are as follows: rising from room temperatureKeeping the temperature for 2h after the temperature is up to 1200 ℃, and then cooling to the room temperature, wherein the temperature rising speed is 200 ℃ h -1 The cooling speed is 150 ℃ h -1 。
A high non-linear ZnO-based polycrystalline ceramic is prepared by the preparation method.
The application of the high-nonlinearity ZnO-based polycrystalline ceramic in a nuclear radiation detector for rapid X-ray detection is characterized in that metal electrodes are coated on two surfaces of the high-nonlinearity ZnO-based polycrystalline ceramic and are packaged to obtain the nuclear radiation detector for rapid X-ray detection.
Further, the metal electrode is an Au electrode.
Further, the dark field current density of the nuclear radiation detector for the rapid X-ray detection is less than 40nA cm -2 And the sensitivity to X-rays with the magnitude of 10keV is more than 100 nC.Gy -1 (ii) a The full pulse width is 50ns, and the time resolution is 10 ns.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the invention, a natural Schottky barrier structure can be formed at the grain boundary of the ZnO polycrystalline ceramic formed by a sintering process, so that the whole material has a natural Schottky barrier, and the problem of difficult preparation of large-area traditional metal-ZnO Schottky contact is avoided; in addition, the ceramic sintering process greatly reduces the material cost.
The back-to-back Schottky barrier model device is formed in a series mode by utilizing the metal electrode and the prepared ZnO polycrystalline ceramic. The radiation-induced electron-hole pairs move under the action of an electric field between depletion regions formed by Schottky barriers to form variable induced charges between crystal grains, the induced charges are sequentially transmitted through the crystal grains to form effective electric signals at two ends of the metal electrode, and finally the process of converting nuclear radiation energy into electric energy is realized. The process reduces the movement time of radiation-induced carriers, effectively reduces the influence of material defects on the carrier collection process, and reduces the requirement on high-quality materials.
Specifically, the metal-ZnO-metal structure device based on the ZnO ceramic is prepared by using the ZnO-based polycrystalline ceramic as a nuclear radiation energy collecting material, and the preparation method is simple and convenient to operate. In practical application, the ZnO ceramic has excellent uniformity, the size of the material is not limited, and a nuclear radiation detector with an ultra-large volume can be realized; according to the invention, the grain size and density of the ZnO polycrystalline ceramic can be adjusted by adjusting the process parameters such as raw material proportion, sintering time and the like, so that the regulation and control of the electrical characteristics such as breakdown voltage and electric leakage of a device and the response characteristics such as carrier collection time and efficiency are realized, the influence of material defects on the sensitivity and time resolution of the device is reduced, the harsh requirements of a semiconductor nuclear radiation detector on the quality of a semiconductor material are broken, and the obtained nuclear radiation detector for rapid X-ray detection has the best performance under the parameter condition of the invention.
Drawings
FIG. 1 is a nuclear radiation detector device structure;
FIG. 2 shows the device at a dose rate of 0.383Gy · s -1 Current-voltage characteristic curves in the X-ray radiation field and in the dark field;
fig. 3 is a graph of the pulsed X-ray response waveform of the device at 200V bias.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
A preparation method of high-nonlinearity ZnO-based polycrystalline ceramic comprises the following steps:
1) Selecting analytically pure raw materials: 93.42mol% of ZnO,1.2mol% of Bi 2 O 3 ,1.1mol％Co 2 O 3 ,0.5mol％MnCO 3 ,1.3mol％NiO,1.48mol％SiO 2 And 1mol% of Sb 2 O 3 Weighing according to stoichiometric ratio, ball-milling in a planetary ball mill, drying, grinding and sieving the mixed slurry after ball-milling, wherein the drying temperature is 80 ℃, the ball-milling time is 12h, and the ball-milling rotating speed is 300 r.min -1 The screen is a 100-mesh screen.
2) Preparation: after the step 1), granulating, ageing, tabletting and removing glue from the uniformly mixed precursor powder, and sintering in an air atmosphere; the sintering conditions are as follows: heating to room temperatureKeeping the temperature for 2h after 1200 ℃, then cooling to room temperature at the speed of 200 ℃ h -1 The cooling speed is 150 ℃ h -1 Obtaining high non-linear ZnO-based polycrystalline ceramic;
wherein, the PVA (polyvinyl alcohol) aqueous solution with the concentration of 3wt% is added according to the mass ratio of 100 (precursor powder) to 1 (PVA aqueous solution), the ageing time is 24 hours, the pressure required by tabletting is 100Mpa, the degumming temperature is 600 ℃, and the temperature is kept for 3 hours.
The effective area of the high-nonlinearity ZnO-based polycrystalline ceramic prepared by the invention can reach nearly 100cm 2 Resistivity greater than 10 11 Ω·cm。
A method for preparing a polycrystalline ceramic-based nuclear radiation detector for rapid X-ray detection comprises the following steps
1) For a metal electrode on the surface of a highly nonlinear ZnO-based polycrystalline ceramic, as shown in fig. 1, an Au electrode is used as the metal electrode in this embodiment.
2) And packaging the device.
The polycrystalline ceramic-based nuclear radiation detector for rapid X-ray detection adopts a vertical structure, polycrystalline ceramic with double grain boundary potential barriers at the grain boundaries prepared by the method is used as a detection medium, metal electrode layers are arranged on the upper surface and the lower surface of the polycrystalline ceramic material, and due to the particularity of the ZnO polycrystalline ceramic material prepared by the method, the influence of the electrode material type on the electrical property of a device can be ignored, and the influence of the electrode area of the device and the thickness of the ZnO ceramic material on the dark current density can be ignored.
FIG. 2 shows a nuclear radiation detector at a dose rate of 0.383Gy · s -1 Current-voltage characteristic curves in the X-ray radiation field and in the dark field. The device is in an X-ray radiation field environment, and X-rays absorbed inside the device generate electron-hole pairs, so that the conductive property of the device is influenced; the measurement of the dose rate characteristic of the X-ray radiation field is realized by comparing the electrical characteristics of the device in the environment with/without the X-ray radiation field. From FIG. 2, it can be calculated that the sensitivity of the device is greater than 100 nC-Gy at a bias voltage of 200V -1 。
Fig. 3 is a graph of a pulsed X-ray response waveform of a nuclear radiation detector at 200V bias. The device-to-pulse X-ray temporal resolution is on the order of 10 ns.
In conclusion, the invention adopts the ceramic medium with ultra-low cost and large volume to prepare the electrode with the area reaching nearly 100cm 2 Dark field current density of the device is 40nA cm -2 Sensitivity to X-rays of the order of 10keV of 100 nC.Gy -1 Compared with a high-resistance single crystal device with the same structure, the semiconductor nuclear radiation detector has the advantages that the size of an electrode can be improved in a numerical order, the consistency of the device is excellent, the mass production and the preparation are low in cost, and the secondary processing is easy; meanwhile, the device has fast X-ray response, realizes the detection of the pulse X-ray with the full pulse width of 50ns and the time resolution of 10ns magnitude. The material of the invention has simple preparation process and extremely low cost, and the semiconductor nuclear radiation detector based on the ceramic material has the characteristic of time resolution capability of 10ns magnitude.
Claims (9)
1. A preparation method of a high-nonlinearity ZnO-based polycrystalline ceramic is characterized by comprising the following steps:
1) Taking the following analytically pure raw materials according to the stoichiometric ratio: 93.42mol% of ZnO,1.2mol% of Bi 2 O 3 ，1.1mol％Co 2 O 3 ，0.5mol％MnCO 3 ，1.3mol％NiO，1.48mol％SiO 2 And 1mol% of Sb 2 O 3 Mixing after ball milling, drying, grinding and sieving the mixed slurry after ball milling to obtain precursor powder;
wherein, a 100-mesh screen is adopted during sieving;
2) Granulating, ageing, tabletting and binder removal of precursor powder, and sintering in air atmosphere to obtain high-nonlinearity ZnO-based polycrystalline ceramic;
wherein the pressure required by tabletting is 100MPa; the binder removal temperature is 600 ℃, the binder removal time is 3h, and the sintering conditions are as follows: raising the temperature from room temperature to 1200 ℃, then preserving the heat for 2h, and then reducing the temperature to the room temperature, wherein the speed of raising the temperature is 200 ℃ h -1 The cooling speed is 150 ℃ h -1 。
2. The method for preparing a highly nonlinear ZnO-based polycrystalline ceramic as claimed in claim 1, wherein the ball milling speed in step 1) is 300 r-min -1 Ball millingThe time is 12h.
3. The method for preparing a highly nonlinear ZnO-based polycrystalline ceramic as claimed in claim 1, wherein the baking temperature in step 1) is 80 ℃.
4. The method for preparing the high nonlinearity ZnO-based polycrystalline ceramic according to claim 1, wherein the granulation in step 2) is specifically: adding PVA aqueous solution into the precursor powder, wherein the mass ratio of the precursor powder to the PVA aqueous solution is 100.
5. The method for preparing a highly nonlinear ZnO-based polycrystalline ceramic as claimed in claim 1, wherein the aging time in step 2) is 24h.
6. A highly nonlinear ZnO-based polycrystalline ceramic, characterized by being produced by the production method described in any one of claims 1 to 5.
7. The application of the high-nonlinearity ZnO-based polycrystalline ceramic of claim 6 to a nuclear radiation detector for rapid X-ray detection, wherein metal electrodes are coated on two surfaces of the high-nonlinearity ZnO-based polycrystalline ceramic, and the high-nonlinearity ZnO-based polycrystalline ceramic is packaged to obtain the nuclear radiation detector for rapid X-ray detection.
8. Use according to claim 7, wherein the metal electrode is an Au electrode.
9. Use according to claim 7, characterized in that the dark field current density of the nuclear radiation detector for fast X-ray detection is less than 40 nA-cm -2 Sensitivity of more than 100 nC.Gy to X-ray of 10keV magnitude -1 (ii) a The full pulse width is 50ns, and the time resolution is 10 ns.
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