CN108130512B - ZnO-Ga monocrystal nanorod array X-ray scintillation conversion screen and preparation method and application thereof - Google Patents
ZnO-Ga monocrystal nanorod array X-ray scintillation conversion screen and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a ZnO-Ga monocrystal nanorod array X-ray scintillation conversion screen, a preparation method and application thereof. Compared with the prior art, the ZnO-Ga monocrystal nanorod array has stable components, uniform thickness, no cracking, firm adhesion to a substrate and excellent scintillation luminescence performance, and the prepared ZnO-Ga monocrystal nanorod array X-ray scintillation conversion screen can be applied to high-spatial resolution and high-temporal resolution digital X-ray imaging.
Description
Technical Field
The invention belongs to the technical field of high-resolution digital X-ray imaging, and particularly relates to a ZnO-Ga single crystal nanorod array X-ray scintillation conversion screen, and a preparation method and application thereof.
Background
In the fields of nuclear fusion, plasma diagnosis, nondestructive detection, material microstructure, biomedicine and the like, the scintillation conversion screen is a core device for realizing X-ray detection and imaging. In recent years, digital recording of X-ray images has gradually replaced the conventional method of recording images on photosensitive films because of its advantages such as convenience, rapidness, easy storage, transfer, and image processing. A common X-ray digital imaging system comprises a scintillation conversion screen, an optical system and a visible light detection device. The basic principle is as follows: the X-ray image is converted into a visible light image by a flicker conversion screen, and the image is coupled to a common CCD through an optical system. Therefore, on the premise that visible light detection devices are becoming more and more perfect, the performance of the scintillation conversion screen is the key to influence the indexes of the X-ray imaging detection devices. Evaluating the performance of a scintillation conversion screen involves two key parameters, namely the luminescence decay time and the spatial resolution. It is a long-sought goal to obtain a flicker conversion screen which combines ultra-fast flicker luminescence with high spatial resolution.
Ga has exciton activation energy as high as 60meV and excellent light emitting performance at room temperature. Under the excitation of high-energy X-ray or particle, the material has high radiation hardness, exciton luminescence rising edge time of about 43ps, decay time of 82ps (20keV X-ray), and light yield of up to 15000photo/MeV (511keV gamma ray), and is an ultrafast scintillating material with great development potential. Furthermore, the one-dimensional ZnO-based single crystal nanorods have a good optical waveguide effect on exciton emission due to their high refractive index (n ═ 2.45). Therefore, if the ZnO-based single crystal nanorod array is applied to a scintillation conversion screen of high-energy rays or particles, the ZnO-based single crystal nanorod array not only has the characteristics of ultra-fast detection and imaging, but also avoids the lateral diffusion and propagation scattering of fluorescence due to the action of the optical waveguide, and greatly improves the spatial resolution of a scintillation detector.
According to the reports, there are generally two ways to achieve high spatial resolution detection and imaging: firstly, preparing a transparent scintillation film with excellent performance; in addition, a structured scintillation material is obtained. In the research of inorganic transparent scintillation films, great progress has been made in recent years internationally, and the highest imaging spatial resolution can reach submicron. The disadvantage of this approach is mainly due to the fact that the spatial resolution is limited by the thickness of the film. In order to achieve a spatial resolution in the micrometer range, the thickness of the thin film is generally controlled to be 1-3 μm, which will seriously affect the luminous intensity and thus the detection efficiency of the conversion screen. On the other hand, the development of structured scintillation conversion screens is a big trend to achieve high spatial resolution detection and imaging. At present, the scintillation material for realizing structured growth is mainly CsI: Tl. The material has high light output, is a practical scintillator with excellent comprehensive performance, and is widely applied to many fields of high-energy physics, nuclear medicine, security inspection and industrial CT. Tl X-ray detector micro-column diameter is generally in the range of 3-50 μm, micron-order spatial resolution imaging can be obtained, but microsecond-order attenuation time cannot meet application requirements in the aspects of high counting rate detection, ultra-fast imaging and the like.
Internationally, a. taheri et al, 2013, proposed the concept of ZnO nanorods as scintillating materials. Based on ZnO-based materials, monocrystal nanorod arrays are relatively easy to prepare, and nanorods with submicron diameters can reach tens of microns in length, so that submicron spatial resolution imaging can be obtained on the premise of ensuring detection efficiency. In addition, in 2015, Masakazu Kobayashi et al in Japan initially tried to prepare an X-ray scintillation conversion screen by using ZnO nanowires, the thickness of the scintillation screen is only about 500nm, the scintillation luminescence is weak, and in order to obtain clear imaging, the required X-ray dose reaches 4 × 1011photons mm-2s-1Due to the excessive dosage of the X-ray, the practical imaging requirements of the X-ray scintillation conversion screen, especially the imaging requirements in the biological and medical fields, cannot be met. At present, no report of using ZnO-Ga monocrystal nanorod array as X-ray scintillation conversion screen exists in China. In general, there is no practical report of using ZnO-Ga monocrystal nanorod array to manufacture X-ray imaging detector with both high spatial resolution and high temporal resolution at home and abroad.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a ZnO-Ga single crystal nanorod array X-ray scintillation conversion screen, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a ZnO-Ga monocrystal nanorod array X-ray scintillation conversion screen is characterized in that a ZnO seed layer film is prepared on a substrate through radio frequency reaction magnetron sputtering, a ZnO-Ga monocrystal nanorod array is formed on the substrate through a low-temperature hydrothermal method, and then the ZnO-Ga monocrystal nanorod array X-ray scintillation conversion screen is prepared through hydrogen annealing treatment.
Preferably, the method comprises the steps of:
(1) plating a ZnO seed layer film on the substrate by adopting a radio frequency reaction magnetron sputtering method;
(2) annealing the substrate plated with the ZnO seed layer film in an air atmosphere;
(3) adding Zn (NO)3)·6H2O、Ga(NO3)3·6H2O and C6H12N14Respectively dissolving in deionized water, and uniformly mixing to form reactant solution;
(4) placing the substrate plated with the ZnO seed layer film in a reaction kettle, enabling the surface of the substrate plated with the ZnO seed layer film to face downwards, adding the reactant solution obtained in the step (3), carrying out low-temperature hydrothermal reaction, forming ZnO growing perpendicular to the substrate on the substrate, namely a Ga monocrystal nanorod array, and enabling the surface of the substrate plated with the ZnO seed layer film to face downwards to obtain a monocrystal nanorod array with relatively good quality;
(5) and (3) carrying out hydrogen annealing treatment on the substrate on which the ZnO and Ga single crystal nanorod array is formed to obtain the ZnO and Ga single crystal nanorod array X-ray scintillation conversion screen.
Preferably, the method for plating the ZnO seed layer film on the substrate by adopting the radio frequency reaction magnetron sputtering method comprises the following steps:
(a) sequentially carrying out ultrasonic treatment on the substrate in a mixed solution of acetone and ethanol, dilute nitric acid and deionized water, taking out, wiping, drying and storing for later use;
(b) fixing a substrate on a workpiece frame above a magnetron sputtering chamber, then placing a zinc target on a sputtering target, controlling the distance between the substrate and the zinc target to be 5-7 cm, and shielding the substrate and the zinc target by using a baffle before formal sputtering is started;
(c) vacuumizing to a vacuum degree of less than 1.0 × 10-3Pa, heating the substrate to 200-400 ℃, and uniformly rotating the workpiece frame at a rotating speed of 10-30 rpm before starting to evaporate the film;
(d) injecting argon and oxygen according to the volume ratio of 1:1 and the gas flow rate of 20-60 sccm, and controlling the gas pressure of the magnetron sputtering chamber to be 0.5-5 Pa;
(e) regulating the sputtering power to be 100-200W, and pre-sputtering for 10-60 min;
(f) and after the pre-sputtering is finished, opening the baffle, performing formal sputtering on the substrate for 10-30 min, and naturally cooling to room temperature in a vacuum environment after the sputtering is finished to finish the plating of the ZnO seed layer film on the substrate.
Further preferably, the method for plating the ZnO seed layer film on the substrate by adopting the radio frequency reactive magnetron sputtering method comprises the following steps:
(a) sequentially carrying out ultrasonic treatment on the substrate in a mixed solution of acetone and ethanol, dilute nitric acid and deionized water, taking out, wiping, drying and storing for later use;
(b) fixing a substrate on a workpiece frame above a magnetron sputtering chamber, then placing a zinc target on a sputtering target, controlling the distance between the substrate and the zinc target to be 6cm, and shielding the substrate and the zinc target by using a baffle before formal sputtering is started;
(c) vacuum-pumping to 1.0 × 10-4Pa, heating the substrate to 250 ℃, and enabling the workpiece frame to rotate at a constant speed of 20rpm before starting to evaporate the film;
(d) injecting argon and oxygen according to the volume ratio of 1:1 and the gas flow rate of 30sccm, and controlling the gas pressure of the magnetron sputtering chamber to be 1 Pa;
(e) regulating the sputtering power to be 100W, and pre-sputtering for 30 min;
(f) and after the pre-sputtering is finished, opening the baffle, performing formal sputtering on the substrate, performing sputtering treatment for 10min, and naturally cooling to room temperature in a vacuum environment after the sputtering is finished to finish the plating of the ZnO seed layer film on the substrate.
Preferably, the temperature of the annealing treatment in the step (2) is 250-750 ℃, the time of the annealing treatment is 1-3 h, and after the annealing treatment is finished, the temperature is naturally reduced to the room temperature.
Further preferably, the temperature of the annealing treatment in the step (2) is 500 ℃, the time of the annealing treatment is 2 hours, and after the annealing treatment is finished, the temperature is naturally reduced to the room temperature.
And (3) adjusting the annealing treatment temperature in the step (2) to obtain the ZnO seed layer films with different grain sizes. The annealing temperature is selected so that the grain size increases as the annealing temperature increases, but when the temperature is too high, the grains sublimate and are vaporized.
Preferably, in the reactant solution of step (3), Zn (NO)3)·6H2O and C6H12N14In a concentration of 0.1 to 0.4mol/L, Zn (NO)3)·6H2O and C6H12N14In a molar ratio of 1:1, said Ga (NO)3)3·6H2And O is used for providing Ga doping elements to replace Zn elements in ZnO, and the doping concentration is 1-10%.
Preferably, the temperature of the low-temperature hydrothermal reaction in the step (4) is 80-150 ℃, and the reaction time is 7-12 h.
Further preferably, the temperature of the low-temperature hydrothermal reaction in the step (4) is 95 ℃ and the reaction time is 9 hours.
The low temperature hydrothermal reaction process of step (4) can be described by the following equation:
Zn(NO3)2·6H2O(s)→Zn2+(aq)+2NO3-(aq)+6H2O(1)(1)
Ga(NO3)3·xH2O(s)→Ga3+(aq)+3NO3-(aq)+xH2O(l)(2)
Zn2++xGa3++yOH-→ZnGax(OH)y→
ZnGaxO0.5y(s)+0.5yH2O，y＝3x+2 (5)
in the process of the low-temperature hydrothermal reaction, the surface of the substrate plated with the ZnO seed layer film faces downwards, because if the surface of the ZnO seed layer film faces upwards, ZnO particles generated by spontaneous nucleation in the solution fall onto the substrate, and the nano-rod cannot grow by means of the seed layer. The side of the seed layer faces downwards, the seed layer can grow downwards by means of gravity, the problem of coverage is avoided, and the quality of the single crystal nanorod array is good.
The hydrothermal reaction conditions such as reactant concentration, reactant proportion and reaction time can regulate and control the thickness and length of the nanorods in the nanorod array. The greater the reactant concentration, the thicker the nanorods are long, but the shorter the length. The reactant ratio is generally good at 1:1, which would otherwise result in defects in the nanorods due to chemical mismatch.
Preferably, the temperature of the hydrogen annealing treatment in the step (5) is 350-650 ℃, and the annealing atmosphere Ar: H2The volume ratio of (A) is 80-95: 20-5, and the annealing time is 20-60 min.
Further preferably, the temperature of the hydrogen annealing treatment in the step (5) is 550 ℃, and the annealing atmosphere Ar: H2The volume ratio of (A) to (B) is 90:10, and the annealing time is 30 min.
If the amount of hydrogen is too small during the hydrogen annealing treatment, the X-ray luminescence property of the nanorod array cannot be significantly improved. However, if the hydrogen anneal is too late, it will result in the ZnO being reduced to metallic Zn. The purpose of this treatment step in the present invention is to dope only a small number of hydrogen atoms into the lattice of ZnO to optimize its luminescent properties.
Preferably, the substrate is a quartz substrate with double-side polishing.
The ZnO-Ga monocrystal nanorod array X-ray scintillation conversion screen is prepared by the method.
The nanorod array of the scintillation conversion screen prepared by the method is approximately vertical to the substrate for growth, the nanorod structure is excellent, the size is uniform, and the diameter and the length of the nanorod can be controlled.
The ZnO-Ga monocrystal nanorod array X-ray scintillation conversion screen is applied to X-ray imaging with high spatial resolution and high temporal resolution. Spatial resolution on the order of microns and temporal resolution on the order of sub-nanoseconds can be achieved.
Compared with the prior art, the method obtains the ZnO-Ga single crystal nanorod array which is nearly vertical to the substrate, has good crystallization performance, compact arrangement and submicron diameter and thickness of 20 mu m by adjusting the magnetron sputtering parameters and the hydrothermal growth conditions, thereby improving the spatial resolution of the X-ray imaging device and greatly improving the scintillation luminescence property of the ZnO-Ga single crystal nanorod array by hydrogen annealing treatment. The ZnO/Ga monocrystal nanorod array has stable components, uniform thickness, no cracking, very firm adhesion to a substrate, excellent scintillation luminescence performance and important application value in the aspects of ultrahigh space and time resolution X-ray imaging. The ZnO-Ga monocrystal nanorod array X-ray scintillation conversion screen with the array structure prepared by the method can be applied to high-spatial resolution and high-temporal resolution digital X-ray imaging. The invention has high popularization and application value and great potential for creating economic value.
Drawings
FIG. 1 is a schematic diagram of a ZnO-Ga single crystal nanorod array X-ray scintillation conversion panel, wherein FIG. 1(a) is a schematic diagram of a front side, and FIG. 1(b) is a schematic diagram of a back side;
FIG. 2 is a scanning electron micrograph of a scintillation conversion panel prepared in example 1, wherein FIG. 2(a) is a surface photograph and FIG. 2(b) is a side photograph;
FIG. 3 is an X-ray diffraction spectrum of a scintillation conversion screen prepared in example 1;
FIG. 4 is an X-ray excitation emission spectrum of a scintillation conversion screen prepared in example 1;
FIG. 5 is a luminescence decay time spectrum of the scintillation conversion panel prepared in example 1;
fig. 6 is an image obtained by imaging a resolution plate using the flicker conversion panel prepared in example 1, in which fig. 6(a) is a pattern of the entire resolution plate and fig. 6(b) is a pattern of an ultimate resolution of 1 μm.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
A preparation method of a ZnO-Ga monocrystal nanorod array X-ray scintillation conversion screen is characterized in that a ZnO seed layer film is prepared on a substrate through radio frequency reaction magnetron sputtering, a ZnO-Ga monocrystal nanorod array is formed on the substrate through a low-temperature hydrothermal method, and then the ZnO-Ga monocrystal nanorod array X-ray scintillation conversion screen is prepared through hydrogen annealing treatment.
Specifically, a quartz substrate with two polished sides is selected, the quartz substrate is cleaned and then fixed on a workpiece rack of a magnetron sputtering chamber of a magnetron sputtering instrument, a zinc target is selected as a sputtering target material, the distance between the zinc target and the quartz is 6cm basically, and before formal sputtering is started, a baffle plate is used for blocking the space between the quartz substrate and the zinc target. Starting to vacuumize, firstly using a mechanical pump to vacuumize to 5Pa, and then using a molecular pump to vacuumize to 1.0 multiplied by 10-4Pa. The quartz substrate may be heated to a temperature of 350 c during the evacuation. When the vacuum degree of the magnetron sputtering chamber reaches 1.0 multiplied by 10-4And when Pa is needed, adjusting an air inlet valve, injecting high-purity argon and oxygen, wherein the volume ratio of the argon to the oxygen is 1:1, the flow rate of the gas is controlled at 30sccm, the air pressure of the magnetron sputtering chamber is controlled at 1Pa, and meanwhile, the workpiece frame uniformly rotates at the rotating speed of 20 rpm. And opening a magnetron sputtering power switch, setting the sputtering power to be 100W, opening a sputtering switch, performing pre-sputtering for 30min, stopping the space between the quartz and the zinc target by using a baffle plate, after the pre-sputtering is finished, opening the baffle plate under the control of a computer, starting formal sputtering on the quartz substrate, and setting the sputtering time to be 10min to prepare the ZnO seed layer film. And annealing the prepared ZnO seed layer film in a muffle furnace at 500 ℃ for 2 h. And taking out the cooled ZnO seed layer after annealing, and putting the ZnO seed layer into the bottom of a hydrothermal reaction kettle, wherein the side with the seed layer is downward and leans against the kettle wall of the reaction kettle. 7.0683624g of zinc nitrate hexahydrate is taken (chemical formula: zn (NO)3)2·6H2O]And 0.0613776g of gallium nitrate hexahydrate [ formula: ga (NO)3)3·6H2O]Put into 80ml deionized water and stirred for 30min at normal temperature. Then, 3.36456g of hexamethylenetetramine [ chemical formula: c6H12N4]Put into 80ml deionized water and stirred for 30min at normal temperature. Pouring the prepared two solutions into a hydrothermal reaction kettle in sequence, and pouringThe reaction kettle is sealed and put into a vacuum drying box, heated to 95 ℃ and kept warm for 9 hours. Taking out the quartz substrate in the reaction kettle after the temperature is reduced to room temperature to obtain the ZnO-Ga monocrystal nanorod array, and then carrying out hydrogen annealing treatment at the annealing temperature of 550 ℃ under the annealing atmosphere of Ar-H2The annealing time is 30min at 90: 10. And after the annealed array is cooled to room temperature, taking out the annealed array to obtain the ZnO-Ga monocrystal nanorod array X-ray scintillation conversion screen.
In this embodiment, the following method is used to clean the quartz substrate: sequentially carrying out ultrasonic treatment on the substrate in a mixed solution of acetone and ethanol, dilute nitric acid and deionized water, taking out, wiping, drying and storing for later use; the acetone and ethanol are prepared according to the ratio of 1:1, and the ultrasonic treatment time of each step is 30 min.
The real object diagram of the flicker conversion screen manufactured by the embodiment is shown in the attached figure 1. The size of the scintillation screen is 35mm in diameter and 1mm in thickness.
The scanning electron microscope image of the surface and the section of the scintillation conversion screen prepared in the embodiment is shown in the attached figure 2. As can be seen from the figure, the ZnO Ga nanorods have a diameter of about 500nm and a length of about 20 μm. The ZnO Ga nano-rod is highly compact and vertical to the quartz substrate, and the diameters of the nano-rods are substantially uniform, which is beneficial to X-ray imaging.
The X-ray diffraction pattern of the scintillation conversion screen prepared in this example is shown in FIG. 3. As can be seen from the figure, the nanorods have an intense (002) diffraction peak, indicating that the nanorods all grow along the [0001] plane, which is favorable for light to propagate along the nanorods.
The X-ray excitation emission spectrum of the scintillation conversion screen prepared in the embodiment is shown in the attached figure 4. As can be seen from the figure, the nanorod array has an intense UV emission at 390nm by hydrogen annealing.
The luminescence decay time spectrum of the scintillation conversion screen prepared by the embodiment is shown in figure 5. It can be seen from the figure that the decay time of the scintillation conversion screen almost completely coincides with the instrument response (the limit decay time of the instrument is 0.1ns), indicating that the decay time of the scintillation conversion screen reaches the sub-nanosecond level.
Ga ZnO is utilized on Shanghai light source BL13W1 line stationThe single crystal nanorod array was used to image JIMART RC-02B resolution plate produced by Japan society of Detector manufacturers at an X-ray dose of about 1.0X 106photons mm-2s-1The resulting image is shown in figure 6. The resolution can be used for resolving resolution lines of 1 μm at the limit. The spatial resolution of the ZnO-Ga nanorod array scintillation conversion screen reaches the micrometer level.
Example 2
This example is substantially the same as example 1 except that in this example, the zinc target is located at a distance of 5cm from the quartz substrate, and the space between the quartz substrate and the zinc target is blocked by a shutter before the start of main sputtering. Starting to vacuumize, firstly using a mechanical pump to vacuumize to 5Pa, and then using a molecular pump to vacuumize to a vacuum degree of less than 1.0 multiplied by 10-3Pa is needed. The quartz substrate may be heated to a temperature of 200 c during evacuation. The vacuum degree of the magnetron sputtering chamber is less than 1.0 multiplied by 10-3And when Pa is needed, adjusting an air inlet valve, injecting high-purity argon and oxygen, controlling the volume ratio of the argon to the oxygen to be 1:1, controlling the flow rate of the gas to be 60sccm, controlling the air pressure of the magnetron sputtering chamber to be 0.5Pa, and uniformly rotating the workpiece holder at the rotating speed of 30 rpm. And opening a magnetron sputtering power switch, setting the sputtering power to be 150W, opening a sputtering switch, performing pre-sputtering for 10min, stopping the space between the quartz and the zinc target by using a baffle plate, opening the baffle plate under the control of a computer after the pre-sputtering is finished, starting formal sputtering on the quartz substrate, and setting the sputtering time to be 20min to prepare the ZnO seed layer film. And annealing the prepared ZnO seed layer film in a muffle furnace at 250 ℃ for 3 h. And taking out the cooled ZnO seed layer after annealing, and putting the ZnO seed layer into the bottom of a hydrothermal reaction kettle, wherein the side with the seed layer is downward and leans against the kettle wall of the reaction kettle. Taking zinc nitrate hexahydrate (chemical formula: zn (NO)3)2·6H2O]And gallium nitrate hexahydrate [ chemical formula: ga (NO)3)3·6H2O]Put into 80ml deionized water and stirred for 30min at normal temperature. Then, taking hexamethylenetetramine [ chemical formula: c6H12N4]Put into 80ml deionized water and stirred for 30min at normal temperature. The prepared two areThe seed solution is poured into a hydrothermal reaction kettle in sequence to serve as a reactant solution, Zn (NO) is added into the reactant solution3)·6H2O and C6H12N14Has a concentration of 0.1mol/L, Zn (NO)3)·6H2O and C6H12N14In a molar ratio of 1:1, Ga (NO)3)3·6H2O is used to provide Ga doping element with a doping concentration of 1%. Sealing the reaction kettle, putting the reaction kettle into a vacuum drying box, heating the reaction kettle to 80 ℃, and preserving the heat for 12 hours. Taking out the quartz substrate in the reaction kettle after the temperature is reduced to room temperature to obtain the ZnO-Ga monocrystal nanorod array, and then carrying out hydrogen annealing treatment at the annealing temperature of 350 ℃ under the annealing atmosphere of Ar-H2Annealing time 60min at 95: 5. And after the annealed array is cooled to room temperature, taking out the annealed array to obtain the ZnO-Ga monocrystal nanorod array X-ray scintillation conversion screen.
Example 3
This example is substantially the same as example 1 except that in this example, the zinc target is located at a substantial distance of 7cm from the quartz, and the quartz substrate and the zinc target are blocked by a shutter before the start of main sputtering. Starting to vacuumize, firstly using a mechanical pump to vacuumize to 5Pa, and then using a molecular pump to vacuumize to a vacuum degree of less than 1.0 multiplied by 10-3Pa is needed. The quartz substrate may be heated to a temperature of 400 c during evacuation. The vacuum degree of the magnetron sputtering chamber is less than 1.0 multiplied by 10-3And when Pa is needed, adjusting an air inlet valve, injecting high-purity argon and oxygen, wherein the volume ratio of the argon to the oxygen is 1:1, the flow rate of the gas is controlled at 20sccm, the air pressure of the magnetron sputtering chamber is controlled at 5Pa, and meanwhile, the workpiece frame uniformly rotates at the rotating speed of 10 rpm. And opening a magnetron sputtering power switch, setting the sputtering power to be 200W, opening a sputtering switch, performing pre-sputtering for 60min, stopping the space between the quartz and the zinc target by using a baffle plate, after the pre-sputtering is finished, opening the baffle plate under the control of a computer, starting formal sputtering on the quartz substrate, and setting the sputtering time to be 30min to prepare the ZnO seed layer film. And annealing the prepared ZnO seed layer film in a muffle furnace at 750 ℃ for 1 h. Taking out the cooled ZnO seed layer after annealing and placing the ZnO seed layer at the bottom of a hydrothermal reaction kettle, whereinThe side plated with the seed layer faces downwards and leans against the kettle wall of the reaction kettle. Taking zinc nitrate hexahydrate (chemical formula: zn (NO)3)2·6H2O]And gallium nitrate hexahydrate [ chemical formula: ga (NO)3)3·6H2O]Put into 80ml deionized water and stirred for 30min at normal temperature. Then, taking hexamethylenetetramine [ chemical formula: c6H12N4]Put into 80ml deionized water and stirred for 30min at normal temperature. Pouring the prepared two solutions into a hydrothermal reaction kettle in sequence to serve as reactant solution, wherein Zn (NO) is added into the reactant solution3)·6H2O and C6H12N14Has a concentration of 0.4mol/L, Zn (NO)3)·6H2O and C6H12N14In a molar ratio of 1:1, Ga (NO)3)3·6H2O is used to provide the Ga doping element with a doping concentration of 10%. The reaction kettle is sealed and put into a vacuum drying box, heated to 150 ℃ and kept warm for 7 hours. Taking out the quartz substrate in the reaction kettle after the temperature is reduced to room temperature to obtain the ZnO-Ga monocrystal nanorod array, and then carrying out hydrogen annealing treatment at the annealing temperature of 650 ℃ under the annealing atmosphere of Ar-H2The annealing time is 20min at 80: 20. And after the annealed array is cooled to room temperature, taking out the annealed array to obtain the ZnO-Ga monocrystal nanorod array X-ray scintillation conversion screen.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. A preparation method of a ZnO/Ga single crystal nanorod array X-ray scintillation conversion screen is characterized in that a ZnO seed layer film is prepared on a substrate by utilizing radio frequency reaction magnetron sputtering, then a ZnO/Ga single crystal nanorod array is formed on the substrate by utilizing a low-temperature hydrothermal method, and then the ZnO/Ga single crystal nanorod array X-ray scintillation conversion screen is prepared by hydrogen annealing treatment;
the method comprises the following steps:
(1) plating a ZnO seed layer film on the substrate by adopting a radio frequency reaction magnetron sputtering method;
(2) annealing the substrate plated with the ZnO seed layer film in an air atmosphere;
(3) adding Zn (NO)3)·6H2O、Ga(NO3)3·6H2O and C6H12N14Respectively dissolving in deionized water, and uniformly mixing to form reactant solution;
(4) placing the substrate plated with the ZnO seed layer film in a reaction kettle, enabling the surface of the substrate plated with the ZnO seed layer film to face downwards, adding the reactant solution obtained in the step (3), and carrying out low-temperature hydrothermal reaction to form a ZnO-Ga single crystal nanorod array which grows perpendicular to the substrate on the substrate;
(5) carrying out hydrogen annealing treatment on the substrate on which the ZnO and Ga single crystal nanorod array is formed to obtain a ZnO and Ga single crystal nanorod array X-ray scintillation conversion screen;
the temperature of the annealing treatment in the step (2) is 250-750 ℃, the time of the annealing treatment is 1-3 h, and after the annealing treatment is finished, the temperature is naturally reduced to the room temperature;
the temperature of hydrogen annealing treatment in the step (5) is 350-650 ℃, and the annealing atmosphere Ar: H2The volume ratio of (A) is 80-95: 20-5, and the annealing time is 20-60 min.
2. The preparation method of the ZnO-Ga single crystal nanorod array X-ray scintillation conversion screen as claimed in claim 1, wherein the method for plating the ZnO seed layer film on the substrate by using the radio frequency reaction magnetron sputtering method comprises the following steps:
(a) sequentially carrying out ultrasonic treatment on the substrate in a mixed solution of acetone and ethanol, dilute nitric acid and deionized water, taking out, wiping, drying and storing for later use;
(b) fixing a substrate on a workpiece frame above a magnetron sputtering chamber, then placing a zinc target on a sputtering target, controlling the distance between the substrate and the zinc target to be 5-7 cm, and shielding the substrate and the zinc target by using a baffle before formal sputtering is started;
(c) vacuumizing to a vacuum degree of less than 1.0 × 10-3Pa, heating the substrate to 200-400 ℃, and uniformly rotating the workpiece frame at a rotating speed of 10-30 rpm before starting to evaporate the film;
(d) injecting argon and oxygen according to the volume ratio of 1:1 and the gas flow rate of 20-60 sccm, and controlling the gas pressure of the magnetron sputtering chamber to be 0.5-5 Pa;
(e) regulating the sputtering power to be 100-200W, and pre-sputtering for 10-60 min;
(f) and after the pre-sputtering is finished, opening the baffle, performing formal sputtering on the substrate for 10-30 min, and naturally cooling to room temperature in a vacuum environment after the sputtering is finished to finish the plating of the ZnO seed layer film on the substrate.
3. The method for preparing the ZnO Ga single crystal nanorod array X-ray scintillation conversion screen according to claim 1, wherein Zn (NO) is contained in the reactant solution in the step (3)3)·6H2O and C6H12N14In a concentration of 0.1 to 0.4mol/L, Zn (NO)3)·6H2O and C6H12N14In a molar ratio of 1:1, said Ga (NO)3)3·6H2And O is used for providing Ga doping elements, and the doping concentration is 1-10%.
4. The preparation method of the ZnO-Ga single crystal nanorod array X-ray scintillation conversion screen according to claim 1, wherein the temperature of the low-temperature hydrothermal reaction in the step (4) is 80-150 ℃, and the reaction time is 7-12 h.
5. The method for preparing the ZnO-Ga single crystal nanorod array X-ray scintillation conversion screen according to claim 1, wherein the substrate is a quartz substrate.
6. A ZnO-Ga monocrystal nanorod array X-ray scintillation conversion screen is characterized by being prepared by the method of any one of claims 1-5.
7. Application of the ZnO Ga single crystal nanorod array X-ray scintillation conversion screen as claimed in claim 6, characterized in that the screen is applied to high spatial resolution and high temporal resolution X-ray imaging.
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