High-resistivity single crystal zinc oxide wafer based radiation detector and preparation method and use thereof

Abstract

The present invention discloses a high-resistivity single crystal zinc oxide (ZnO) wafer and a high-resistivity single crystal ZnO-based radiation detector, and preparation method and use thereof. The preparation method of the high-resistivity single crystal zinc oxide wafer is to place a single crystal ZnO wafer in a metal lithium electrochemical device for a constant-current discharge treatment, and then to place the single crystal ZnO wafer in a high-pressure oxygen atmosphere at 800 to 1000 C. and 10 to 30 atm for an annealing treatment for 20 to 28 hours. The preparation method of the radiation detector is to evaporate a metal electrode layer at both sides of the high-resistivity single crystal ZnO wafer, then to bond the wafer onto a circuit board, and to connect the wafer with the circuit board by a gold thread.

Claims

1. A preparation method of high-resistivity single crystal zinc oxide, wherein the preparation method comprises following steps: S1) placing a single crystal ZnO wafer in a metal lithium electrochemical device, for a constant-current discharge treatment; and S2) placing a ZnO single crystal treated in the step S1 in an oxygen atmosphere at 600 to 1000 C. and 5 to 30 atm for an annealing treatment for 10 to 28 hours to obtain a high-resistivity ZnO single crystal wafer.

2. The preparation method according to claim 1, wherein an electrolyte in the metal lithium electrochemical device mentioned in the step S1 is a 0.5 to 1.5M LiPF.sub.6 solution dispersed in a mixed solution of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate in a volume ratio of 2 to 5:2 to 4:2 to 4, and a polyethylene microporous membrane is used as an electronic diaphragm.

3. The preparation method according to claim 1, wherein the metal lithium electrochemical device mentioned in the step S1 is a lithium battery shell.

4. The preparation method according to claim 1, wherein a means of placing the single crystal ZnO wafer in the metal lithium electrochemical device mentioned in the step S1 is specifically assembling the single crystal ZnO wafer into a lithium battery shell in following order: an anode shell, the single crystal ZnO wafer, a polyethylene microporous membrane, a metal lithium sheet, an internal electrode, a spring electrode, a cathode shell.

5. The preparation method according to claim 1, wherein the constant-current discharge treatment mentioned in the step S1 is 1 to 4 A constant-current discharge treatment for 10 to 25 hours.

6. The preparation method according to claim 5, wherein the constant-current discharge treatment mentioned in the step S1 is 3 A constant-current discharge treatment for 15 hours.

7. The preparation method according to claim 1, wherein in the step S2, the ZnO single crystal treated in the step S1 is placed in an oxygen atmosphere furnace at 800 to 900 C. and 15 to 25 atm for the annealing treatment for 22 to 26 hours.

8. The preparation method according to claim 1, wherein in the step S2, the ZnO single crystal treated in the step S1 is placed in a high-pressure oxygen atmosphere at 800 C. and 20 atm for the annealing treatment for 24 hours.

9. A high-resistivity single crystal ZnO prepared by the preparation method according to claim 1.

10. Use of the high-resistivity single crystal ZnO according to claim 9 in preparing a radiation detector or a photoelectric detector.

11. A preparation method of a high-resistivity single crystal ZnO-based radiation detector, wherein the preparation method comprises following steps: S1) preparing a high-resistivity single crystal ZnO wafer; S2) evaporating a metal electrode layer at both sides of the high-resistivity single crystal ZnO wafer; and S3) bonding the wafer treated in the step S2 onto a circuit board, and connecting the wafer to the circuit board by a gold thread, wherein evaporating the metal electrode layer at the both sides of the high-resistivity single crystal ZnO wafer mentioned in the step S2 is specifically as follows: evaporating an inner metal layer and an outer metal layer at a side of the high-resistivity single crystal ZnO wafer, the inner metal layer being a nickel layer, a titanium layer or an aluminum layer, the outer metal layer being a gold layer or a silver layer; evaporating an indium layer at an other side of the high-resistivity single crystal ZnO wafer, or evaporating an inner metal layer and an outer metal layer at an other side of the high-resistivity single crystal ZnO wafer, the inner metal layer being a nickel layer, a titanium layer or an aluminum layer, the outer metal layer being a gold layer or a silver layer.

12. The preparation method according to claim 11, wherein a means of evaporating mentioned in the step S2 is a thermal evaporation method or an electron beam evaporation method.

13. The preparation method according to claim 11, wherein a metal of the metal electrode layer mentioned in the step S2 has a purity of 999 to 9999.

14. The preparation method according to claim 11, wherein the nickel layer has a thickness of 4 to 6 nm, the titanium layer has a thickness of 5 to 50 nm, and the gold layer has a thickness of 10 to 50 nm.

15. The preparation method according to claim 11, wherein the indium layer has a thickness of 1 m to 500 m.

16. The preparation method according to claim 11, wherein a specific means of bonding the wafer onto the circuit board mentioned in the step S3 is: melting the metal electrode layer at a side by heating, binding the wafer onto the circuit board by the molten metal electrode layer.

17. The preparation method according to claim 11, wherein a preparation method of the high-resistivity single crystal ZnO wafer mentioned in the step S1 is as follows: placing the single crystal ZnO wafer in a metal lithium electrochemical device, after a constant-current discharge treatment, placing the single crystal ZnO wafer in an oxygen atmosphere at 800 to 1000 C. and 10 to 30 atm for an annealing treatment for 20 to 28 hours to obtain a high-resistivity ZnO single crystal wafer.

18. A high-resistivity single crystal ZnO-based radiation detector prepared by the preparation method according to claim 11.

19. A preparation method of a high-resistivity single crystal ZnO-based radiation detector, wherein the preparation method comprises following steps: S1) preparing a high-resistivity single crystal ZnO wafer; S2) evaporating a metal electrode layer at both sides of the high-resistivity single crystal ZnO wafer; and S3) bonding the wafer treated in the step S2 onto a circuit board, and connecting the wafer to the circuit board by a gold thread, wherein a preparation method of the high-resistivity single crystal ZnO wafer mentioned in the step S1 is as follows: placing the single crystal ZnO wafer in a metal lithium electrochemical device, after a constant-current discharge treatment, placing the single crystal ZnO wafer in an oxygen atmosphere at 800 to 1000 C. and 10 to 30 atm for an annealing treatment for 20 to 28 hours to obtain a high-resistivity ZnO single crystal wafer.

20. A high-resistivity single crystal ZnO-based radiation detector prepared by the preparation method according to claim 19.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a configuration sequence diagram of an electrochemical cell in which a low-resistance zinc oxide crystal wafer is placed in a metal lithium battery shell when preparing a high-resistivity single crystal ZnO.

(2) FIG. 2 is an assembly structure diagram of the high-resistivity ZnO device of Embodiment 6.

(3) FIG. 3 is an alpha particle test response data of Embodiment 6.

(4) FIG. 4 is an assembly structure diagram of the high-resistivity ZnO device of Embodiment 7.

(5) FIG. 5 is an alpha particle test response data of Embodiment 7.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

(6) The present invention is further described below in combination with accompanying drawings and specific embodiments, but the embodiments do not intend to limit the present invention in any form. Unless otherwise stated, reagents, methods and apparatus adopted in the present invention are conventional reagents, methods and apparatus in the art.

(7) Unless otherwise stated, reagents and materials used in the present invention are commercially available.

Embodiment 1

(8) 1. Preparation of High-Resistivity ZnO Single Crystal

(9) (1) A high-quality low-resistance zinc oxide wafer of 10 centimeter squares was assembled into a commercial CR 2032 battery case in the order shown in FIG. 1 at room temperature in an argon-filled glove box, an electrolyte used was a 1 M LiPF6 solution dispersed in a mixed solution of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate in a volume ratio of 4:3:3, and a Celgard 2400 polyethylene microporous membrane was used as an electronic diaphragm.

(10) A LAND BT2013A multi-channel battery testing system performed a constant-current discharge treatment at room temperature to realize an injection of lithium into the ZnO single crystal.

(11) A thickness of the high-quality low-resistance zinc oxide wafer used was 0.3 millimeters, a constant current discharge current was set to 3 A, and a discharge time was set to 15 hours.

(12) (2) The lithium-injected zinc oxide wafer treated in the above step (1) was placed in a high-temperature and high-pressure annealing furnace, and the lithium in the crystal lattice was removed to obtain a high-resistivity ZnO single crystal wafer.

(13) A lithium removal device used in this Embodiment can withstand a high-temperature high-pressure oxygen atmosphere. According to experimental requirements, an oxygen pressure was set to 20 standard atmosphere pressures, a temperature was set to 800 degrees Celsius, and an annealing time was set to 24 hours.

(14) The high-resistivity ZnO single crystal wafer prepared above had a resistivity of 10.sup.11 cm, which was 10.sup.11 higher than that before the treatment.

Embodiment 2

(15) 1. Preparation of high-resistivity single crystal ZnO

(16) The method differed from Embodiment 1 in that the thickness of the ZnO wafer in the step (1) was 0.2 millimeters, the constant current discharge current was set to 3 A, and the discharge time was set to 10 hours.

(17) Compared with Embodiment 1, this Embodiment shortened the discharge time due to a reduction of the thickness of the wafer, thereby obtaining a same processing result.

(18) 2. The high-resistivity ZnO single crystal wafer prepared by this Embodiment had a resistivity of 10.sup.11 cm, which was 10.sup.11 higher than that before treatment.

Embodiment 3

(19) 1. Preparation of high-resistivity single crystal ZnO

(20) The method differed from Embodiment 1 in that the thickness of the ZnO wafer in the step (1) was 0.5 millimeters, the constant current discharge current was set to 3 A, and the discharge time was set to 25 hours.

(21) Compared with Embodiment 1, this Embodiment prolonged the discharge time due to an increase in the thickness of the wafer, thereby obtaining the same processing result.

(22) 2. The high-resistivity ZnO single crystal wafer prepared by this Embodiment had a resistivity of 10.sup.11 cm, which was 10.sup.11 higher than that before treatment.

Embodiment 4

(23) 1. Preparation of high-resistivity single crystal ZnO

(24) (1) A high-quality low-resistance zinc oxide wafer with a thickness of 0.2 millimeters and 10 centimeter squares was assembled into the commercial CR 2032 battery case in the order shown in FIG. 1 at room temperature in the argon-filled glove box, the electrolyte used was the 1 M LiPF6 solution dispersed in a mixture solution of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate in a volume ratio of 1:1:1, and the Celgard 2400 polyethylene microporous membrane was used as the electronic diaphragm.

(25) The LAND BT2013A multi-channel battery testing system performed the constant-current discharge treatment at room temperature to realize the injection of lithium into the ZnO single crystal.

(26) The thickness of the high-quality low-resistance zinc oxide wafer used in this Embodiment was 0.2 millimeters, the constant current discharge current was set to 4 A, and the discharge time was set to 8 hours.

(27) (2) The lithium-injected zinc oxide wafer treated in the above step (1) was placed in the high-temperature and high-pressure annealing furnace, and the lithium in the crystal lattice was removed to obtain the high-resistivity ZnO single crystal wafer.

(28) The lithium removal device used in this Embodiment can withstand the high-temperature high-pressure oxygen atmosphere. According to the experimental requirements, the oxygen pressure was set to 25 standard atmosphere pressures, the temperature was set to 900 degrees Celsius, and the annealing time was set to 22 hours.

(29) 2. The high-resistivity ZnO single crystal wafer prepared by the above had a resistivity of 10.sup.11 cm, which was 10.sup.11 higher than that before treatment.

Embodiment 5

(30) 1. Preparation of high-resistivity single crystal ZnO

(31) (1) A high-quality low-resistance zinc oxide wafer with a thickness of 0.2 millimeters and 10 centimeter squares was assembled into the commercial CR 2032 battery case in the order shown in FIG. 1 at room temperature in the argon-filled glove box, the electrolyte used was the 1 M LiPF6 solution dispersed in a mixture solution of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate in a volume ratio of 5:4:4, and the Celgard 2400 polyethylene microporous membrane was used as the electronic diaphragm.

(32) The LAND BT2013A multi-channel battery testing system performed the constant-current discharge treatment at room temperature to realize the injection of lithium into the ZnO single crystal.

(33) The thickness of the high-quality low-resistance zinc oxide wafer used in this Embodiment was 0.5 millimeters, the constant current discharge current was set to 3 A, and the discharge time was set to 25 hours.

(34) (2) The lithium-injected zinc oxide wafer treated in the above step (1) was placed in the high-temperature and high-pressure annealing furnace, and the lithium in the crystal lattice was removed to obtain the high-resistivity ZnO single crystal wafer.

(35) The lithium removal device used in this Embodiment can withstand the high-temperature high-pressure oxygen atmosphere. According to the experimental requirements, the oxygen pressure was set to 15 standard atmosphere pressures, the temperature was set to 900 degrees Celsius, and the annealing time was set to 26 hours.

(36) 2. The high-resistivity ZnO single crystal wafer prepared by the above had a resistivity of 10.sup.11 cm, which was 10.sup.11 higher than that before treatment.

Embodiment 6

(37) 1. Preparation of High-Resistivity Single Crystal ZnO-Based Radiation Detector

(38) Using a thermal/electron beam evaporation method, a surface of one side of the high-resistivity ZnO wafer was evaporated with a two-layer metal electrode of 5 nm of nickel and 20 nm of gold in the order shown in FIG. 2, wherein the metal used had a purity of 999 to 9999.

(39) A thicker (1 m to 500 m) metal indium electrode was then plated on the other side of the ZnO wafer.

(40) Both sides of the electrode formed a good electrical contact.

(41) The wafer was bonded to a circuit board by molten indium through a heating device and the wafer was connected to the circuit board by a gold thread.

(42) 2. Testing

(43) The obtained high-resistivity single crystal ZnO-based radiation detector was placed in a vacuum to reduce an energy loss of alpha particles during flight. A response test of the detector utilized a 5.486 MeV alpha-ray irradiation detector from a .sup.241Am radiation source. counted by a front amplifier, and then a signal was transmitted to a main amplifier and transmitted to a multi-channel analyzer, and finally the signal was collected by a microcomputer, as shown in FIG. 3.

(44) The above results show that the high-resistivity single crystal ZnO-based detector has obvious practical capability in the field of radiation detection, and especially its effective response to weak alpha source reflects the sensitivity of the device.

Embodiment 7

(45) 1. A high-resistivity ZnO single crystal was prepared with the method same as Embodiment 1.

(46) 2. Preparation of High-Resistivity Single Crystal ZnO-Based Radiation Detector

(47) Using the thermal/electron beam evaporation method, the surface of one side of the high-resistivity ZnO wafer was evaporated with a two-layer metal electrode of 35 nm of titanium and 20 nm of gold in the order shown in FIG. 4.

(48) The thicker metal indium electrode was then plated on the other side of the ZnO wafer.

(49) Both sides of the electrode formed a good electrical contact.

(50) The wafer was bonded to the circuit board by molten indium through the heating device and the wafer was connected to the circuit board by the gold thread.

(51) 3. Testing

(52) The obtained high-resistivity ZnO-based radiation detector was placed in a vacuum to reduce an energy loss of alpha particles during flight. A response test of the detector utilized a .sup.243Am-.sup.244Cm dual-energy radiation alpha source illumination detector. front amplifier, and then the signal was transmitted to the main amplifier and transmitted to the multi-channel analyzer, and finally the signal was collected by the microcomputer, as shown in FIG. 5.

(53) The above results show that the high-resistivity single crystal ZnO-based detector has obvious practical capability in the field of radiation detection, and especially its effective response to the dual alpha source and distinction reflect that the device has excellent capability of energy resolution.

Embodiment 8

(54) 1. A high-resistivity ZnO single crystal was prepared with the method same as Embodiment 1.

(55) 2. Preparation of high-resistivity single crystal ZnO-based radiation detector

(56) Using the thermal/electron beam evaporation method, the surface of one side of the high-resistivity ZnO wafer was evaporated with a two-layer metal electrode of 4 nm of nickel and 10 nm of gold in the order shown in FIG. 2, wherein the metal used had a purity of 999 to 9999.

(57) A thicker (1 m to 500 m) metal indium electrode was then plated on the other side of the ZnO wafer.

(58) Both sides of the electrode formed a good electrical contact.

(59) The wafer was bonded to the circuit board by molten indium through the heating device and the wafer was connected to the circuit board by the gold thread.

(60) 3. Testing

(61) The obtained high-resistivity ZnO-based detector was placed in a vacuum to reduce an energy loss of alpha particles during flight. A response test of the detector utilized the .sup.243Am-.sup.244Cm dual-energy radiation alpha source illumination detector. It was counted by the front amplifier, and then the signal was transmitted to the main amplifier and transmitted to the multi-channel analyzer, and finally the signal was collected by the microcomputer.

(62) The results show that the high-resistivity single crystal ZnO-based detector has obvious practical capability in the field of radiation detection, and especially its effective response to the dual alpha source and distinction effect that the device has excellent capability of energy resolution.

Embodiment 9

(63) 1. A high-resistivity ZnO single crystal was prepared with the method same as Embodiment 1.

(64) 2. Preparation of high-resistivity single crystal ZnO-based radiation detector

(65) Using the thermal/electron beam evaporation method, the surface of one side of the high-resistivity ZnO wafer was evaporated with a two-layer metal electrode of 5 nm of titanium and 10 nm of gold in the order shown in FIG. 4.

(66) A thicker (1 m to 500 m) metal indium electrode was then plated on the other side of the ZnO wafer.

(67) Both sides of the electrode formed a good electrical contact.

(68) The wafer was bonded to the circuit board by molten indium through the heating device and the wafer was connected to the circuit board by the gold thread.

(69) 3. Testing

(70) The obtained high-resistivity ZnO-based detector was placed in a vacuum to reduce an energy loss of alpha particles during flight. A response test of the detector utilized the .sup.243Am-.sup.244Cm dual-energy radiation alpha source illumination detector. It was counted by the front amplifier, and then the signal was transmitted to the main amplifier and transmitted to the multi-channel analyzer, and finally the signal was collected by the microcomputer.

(71) The results show that the high-resistivity single crystal ZnO-based detector has obvious practical capability in the field of radiation detection, and especially its effective response to the dual alpha source and distinction reflect that the device has excellent capability of energy resolution.

Embodiment 10

(72) 1. A high-resistivity ZnO single crystal was prepared with the method same as Embodiment 1.

(73) 2. Preparation of high-resistivity single crystal ZnO-based radiation detector

(74) Using the thermal/electron beam evaporation method, the surface of one side of the high-resistivity ZnO wafer was evaporated with a two-layer metal electrode of 6 nm of nickel and 50 nm of gold in the order shown in FIG. 2, wherein the metal used had a purity of 999 to 9999.

(75) A thicker (1 m to 500 m) metal indium electrode was then plated on the other side of the ZnO wafer.

(76) Both sides of the electrode formed a good electrical contact.

(77) The wafer was bonded to the circuit board by molten indium through the heating device and the wafer was connected to the circuit board by the gold thread.

(78) 3. Testing

(79) The obtained high-resistivity ZnO-based detector was placed in a vacuum to reduce an energy loss of alpha particles during flight. A response test of the detector utilized the .sup.243Am-.sup.244Cm dual-energy radiation alpha source illumination detector. It was counted by the front amplifier, and then the signal was transmitted to the main amplifier and transmitted to the multi-channel analyzer, and finally the signal was collected by the microcomputer.

(80) The results show that the high-resistivity single crystal ZnO-based detector has obvious practical capability in the field of radiation detection, and especially its effective response to the dual alpha source and distinction reflect that the device has excellent capability of energy resolution.

Embodiment 11

(81) 1. A high-resistivity ZnO single crystal was prepared with the method same as Embodiment 1.

(82) 2. Preparation of high-resistivity single crystal ZnO-based radiation detector

(83) Using the thermal/electron beam evaporation method, the surface of one side of the high-resistivity ZnO wafer was evaporated with a two-layer metal electrode of 50 nm of titanium and 50 nm of gold in the order shown in FIG. 4.

(84) A thicker (1 m to 500 m) metal indium electrode was then plated on the other side of the ZnO wafer.

(85) Both sides of the electrode formed a good electrical contact.

(86) The wafer was bonded to the circuit board by molten indium through the heating device and the wafer was connected to the circuit board by the gold thread.

(87) 3. Testing

(88) The obtained high-resistivity ZnO-based detector was placed in a vacuum to reduce an energy loss of alpha particles during flight. A response test of the detector utilized the .sup.243Am-.sup.244Cm dual-energy radiation alpha source illumination detector. It was counted by the front amplifier, and then the signal was transmitted to the main amplifier and transmitted to the multi-channel analyzer, and finally the signal was collected by the microcomputer.

(89) The results show that the high-resistivity single crystal ZnO-based detector has obvious practical capability in the field of radiation detection, and especially its effective response to the dual alpha source and distinction reflect that the device has excellent capability of energy resolution.

Embodiment 12

(90) 1. A high-resistivity ZnO single crystal was prepared with the method same as Embodiment 1.

(91) 2. Preparation of high-resistivity single crystal ZnO-based radiation detector

(92) Using the thermal/electron beam evaporation method, surfaces of both sides of the high-resistivity ZnO wafer were evaporated with a metal layer.

(93) It differed from Embodiment 7 in that: the metal layer evaporated on the both sides is symmetrical, that is, the both sides are evaporated with an inner metal layer of 35 nm of titanium and an outer metal layer of 20 nm of gold.

(94) A thicker metal indium electrode was then plated on the other side of the ZnO wafer.

(95) Both sides of the electrode formed a good electrical contact.

(96) The wafer was bonded to the circuit board by molten indium through the heating device and the wafer was connected to the circuit board by the gold thread.

(97) 3. Testing

(98) The obtained high-resistivity ZnO-based detector was placed in a vacuum to reduce an energy loss of alpha particles during flight. A response test of the detector utilized the .sup.243Am-.sup.244Cm dual-energy radiation alpha source illumination detector. front amplifier, and then the signal was transmitted to the main amplifier and transmitted to the multi-channel analyzer, and finally the signal was collected by the microcomputer, as shown in FIG. 5.

(99) The results show that the high-resistivity single crystal ZnO-based detector has obvious practical capability in the field of radiation detection, and especially its effective response to the dual alpha source and distinction reflect that the device has excellent capability of energy resolution.

(100) The above-described embodiments are preferred implementations of the present invention, but the implementations of the present invention are not limited by the embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principles of the present invention shall be equivalent substitutions, and are all included in the scope of protection of the present invention.