CN114122187B - Ferroelectric-semiconductor heterojunction solar blind ultraviolet photoelectric detector and preparation method thereof - Google Patents
Ferroelectric-semiconductor heterojunction solar blind ultraviolet photoelectric detector and preparation method thereof Download PDFInfo
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Abstract
The invention provides a ferroelectric-semiconductor heterojunction solar blind ultraviolet photoelectric detector and a preparation method thereof, wherein the detector comprises: a substrate; ga2O3A thin film layer; hf (hafnium)xZr1‑xO2A thin film layer; a top electrode. Probe of the invention, HfxZr1‑xO2Is a ferroelectric material with very wide optical band gap and high dielectric constant, HfxZr1‑xO2And Ga2O3A heterojunction is formed between the two layers, and a photogenerated carrier is separated by a built-in electric field of a heterojunction interface; while HfxZr1‑xO2Spontaneous polarization of the ferroelectric layer causes a spontaneous polarization electric field to exist therein, the spontaneous polarization electric field and Ga2O3/HfxZr1‑xO2The coupling action of an electric field built in the heterojunction promotes the separation of photon-generated carriers together, thereby realizing the improvement of the performance of the device; furthermore, HfxZr1‑xO2The layer has good blocking effect on background carriers, and can greatly reduce dark current of the device.
Description
Technical Field
The invention relates to the technical field of semiconductor heterojunction solar blind ultraviolet photoelectric detectors, in particular to a ferroelectric-semiconductor heterojunction type solar blind ultraviolet photoelectric detector and a preparation method thereof.
Background
Due to the absorption of sunlight by the earth's ozone layer, the deep ultraviolet portion (200-280nm) of the solar spectrum cannot reach the earth's surface and is called solar blind light. Therefore, the solar blind ultraviolet photoelectric detector has the advantages of high sensitivity and strong anti-interference capability, and can be widely applied to the fields of bioaerosol detection, fire monitoring, missile early warning, deep space detection and the like. Compared with the traditional photoconductive semiconductor heterojunction solar-blind ultraviolet photoelectric detector, the self-driven semiconductor heterojunction solar-blind ultraviolet photoelectric detector generally has the advantages of small volume, easiness in integration, low power consumption and the like, and therefore has a wider application prospect.
To realize solar blind ultraviolet detection, the optical band gap of the functional layer of the device is required to be larger than 4.4 eV. Gallium oxide (Ga)2O3) The semiconductor material is a wide-bandgap semiconductor material, the bandgap width of the semiconductor material is about 4.8-4.9 eV, the semiconductor material is far larger than that of ZnO (3.4eV), 4H-SiC (3.3eV), GaN (3.4eV) and the like which are commonly used at present, and the semiconductor material has excellent chemical properties and thermal stability and is an ideal material for preparing a solar-blind ultraviolet detector.
The construction of the semiconductor heterojunction is a main approach for realizing a high-performance self-driven semiconductor heterojunction solar-blind ultraviolet photoelectric detector. As the band gap of the current commonly used semiconductor material is within the range of 3.0-4.0 eV, Ga 2O3The construction of heterojunctions with these semiconductor materials can cause the device to respond to non-solar blind light, thereby reducing the device's immunity to interference.
Based on the defects of the current day-blind ultraviolet light detector, improvement on the defect is needed.
Disclosure of Invention
In view of this, the present invention provides a ferroelectric-semiconductor heterojunction solar blind ultraviolet photodetector and a method for manufacturing the same, so as to solve the technical problems in the prior art.
In a first aspect, the present invention provides a ferroelectric-semiconductor heterojunction solar-blind ultraviolet photodetector, comprising:
a substrate;
Ga2O3the thin film layer is positioned on the surface of the substrate;
HfxZr1-xO2a thin film layer on the Ga2O3The surface of the thin film layer on the side away from the substrate;
a top electrode at said HfxZr1-xO2The surface of the thin film layer on the side away from the substrate;
wherein x is more than 0 and less than or equal to 1.
Preferably, the ferroelectric-semiconductor heterojunction type solar-blind ultraviolet photodetector is a HfxZr1-xO2The thickness of the thin film layer is 3-100 nm.
Preferably, the ferroelectric-semiconductor heterojunction solar-blind ultraviolet photodetector is a solar-blind ultraviolet photodetector, and the Ga is2O3The thickness of the thin film layer is 50-500 nm.
Preferably, the ferroelectric-semiconductor heterojunction solar blind ultraviolet photodetector comprises an FTO conductive glass substrate, an ITO conductive glass substrate, Pt/Ti/SiO 2Any of the substrates of/Si.
Preferably, in the ferroelectric-semiconductor heterojunction type solar-blind ultraviolet photodetector, the top electrode includes any one of a Pt electrode, an Au electrode, an Al-doped ZnO electrode, and an ITO electrode.
In a second aspect, the invention further provides a preparation method of the ferroelectric-semiconductor heterojunction type solar-blind ultraviolet photodetector, which comprises the following steps:
providing a substrate;
preparing Ga on the surface of the substrate2O3A thin film layer;
in the Ga2O3Preparing Hf on the surface of the thin film layer far away from one side of the substratexZr1-xO2A thin film layer;
at the HfxZr1-xO2And preparing a top electrode on the surface of the thin film layer away from one side of the substrate.
Preferably, the ferroelectric-semiconductor heterojunction solar blind ultravioletMethod for preparing photoelectric detector, and Ga prepared on surface of substrate2O3The film layer is specifically as follows: with Ga2O3The Ga is prepared on the surface of the substrate by adopting a pulse laser deposition method, a magnetron sputtering method or a sol-gel method by taking ceramic as a target material2O3A thin film layer;
preparation of HfxZr1-xO2The film layer is specifically as follows: applying an atomic layer deposition method, a magnetron sputtering method, a pulsed laser deposition method or a sol-gel method to the Ga2O3Preparation of Hf on the surface of thin film layerxZr1-xO2A thin film layer;
the preparation of the top electrode specifically comprises the following steps: applying vacuum evaporation method, magnetron sputtering method or electron beam deposition method to the Hf xZr1- xO2Preparing a top electrode on the surface of the thin film layer.
Preferably, the preparation method of the ferroelectric-semiconductor heterojunction solar blind ultraviolet photoelectric detector adopts a pulse laser deposition method to prepare Ga2O3The film layer is specifically as follows:
with Ga2O3Ceramic is used as a target material, the temperature of a substrate is controlled to be 25-800 ℃, the Pulse laser energy is controlled to be 150-600 mJ/Pulse, the oxygen pressure is 0-8 Pa, the deposition time is 10-120 min, and Ga is formed by deposition on the surface of the substrate2O3A thin film layer.
Preferably, the preparation method of the ferroelectric-semiconductor heterojunction type solar blind ultraviolet photoelectric detector adopts an atomic layer deposition method to prepare HfxZr1-xO2The film layer is specifically as follows:
will be prepared with Ga2O3Placing the substrate of the thin film layer in a sample chamber of an atomic layer deposition system, and performing alternate deposition by using tetra (dimethylamino) hafnium and tetra (dimethylamino) zirconium as precursors to obtain HfxZr1-xO2A thin film layer.
Preferably, the preparation method of the ferroelectric-semiconductor heterojunction solar blind ultraviolet photodetector is that Ga2O3The preparation method of the ceramic target comprises the following steps:
to Ga2O3Adding water into the powder, carrying out ball milling, drying and pressing into ceramic green sheets;
firing the ceramic blank sheet at 1000-1400 ℃ for 1-4 h to obtain Ga2O3A ceramic target material.
Compared with the prior art, the ferroelectric-semiconductor heterojunction solar blind ultraviolet photoelectric detector and the preparation method thereof have the following beneficial effects:
(1) The invention relates to a ferroelectric-semiconductor heterojunction solar blind ultraviolet photoelectric detector, which comprises HfxZr1-xO2Thin film layer, HfxZr1-xO2Is a ferroelectric material with very wide optical band gap (5.0-5.6 eV) and high dielectric constant, HfxZr1-xO2And Ga2O3A heterojunction is formed between the two layers, and on one hand, a photon-generated carrier is separated by a built-in electric field of a heterojunction interface; on the other hand, due to HfxZr1-xO2Spontaneous polarization of the ferroelectric layer causes a spontaneous polarization electric field to exist therein, the spontaneous polarization electric field and Ga2O3/HfxZr1-xO2The coupling action of an electric field built in the heterojunction promotes the separation of photon-generated carriers together, thereby realizing the improvement of the performance of the device; furthermore, HfxZr1-xO2The layer has good blocking effect on background carriers, and can greatly reduce dark current of the device.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a ferroelectric-semiconductor heterojunction solar-blind ultraviolet photodetector according to the present invention;
fig. 2 is a graph of a single-period I-t curve of the ferroelectric-semiconductor heterojunction type solar-blind ultraviolet photodetector prepared in example 1 of the present invention;
FIG. 3 is a view showing Ga obtained in comparative example 12O3A photocurrent response diagram of the self-driven solar blind ultraviolet photoelectric detector under the illumination of monochromatic light with the wavelength of 240 nm;
FIG. 4 shows Ga prepared in comparative example 12O3A single-period I-t curve chart of a self-driven solar blind ultraviolet photoelectric detector;
FIG. 5 is a dark current-voltage graph of the detectors prepared in example 1 and comparative example 1;
FIG. 6 shows ZnO/Ga prepared in comparative example 22O3An I-t curve chart of a self-driven solar blind ultraviolet photoelectric detector of the heterojunction under the irradiation of 240nm ultraviolet light;
FIG. 7 shows a ferroelectric-semiconductor heterojunction solar-blind UV photodetector prepared in example 1 of the present invention and Ga prepared in comparative example 12O3A spectral responsivity curve diagram of a self-driven solar blind ultraviolet photoelectric detector;
fig. 8 is a photocurrent response diagram of the ferroelectric-semiconductor heterojunction type solar-blind ultraviolet photodetector prepared in embodiment 2 of the present invention under the irradiation of monochromatic light with a wavelength of 240 nm.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments of the present invention, belong to the protection scope of the present invention.
As shown in fig. 1, the present invention provides a ferroelectric-semiconductor heterojunction solar-blind ultraviolet photodetector, comprising:
a substrate 1;
Ga2O3the thin film layer 2 is positioned on the surface of the substrate 1;
HfxZr1-xO2thin film layer 3 at Ga2O3The surface of the thin film layer 2 at the side far away from the substrate 1;
wherein x is more than 0 and less than or equal to 1.
It is noted that the ferroelectric-semiconductor heterojunction type solar blind ultraviolet photodetector of the present application comprises HfxZr1-xO2Thin film layer, HfxZr1-xO2Is a ferroelectric material with very wide optical band gap (5.0-5.6 eV) and high dielectric constant, HfxZr1-xO2And Ga2O3A heterojunction is formed between the two layers, and on one hand, a photon-generated carrier is separated by a built-in electric field of a heterojunction interface; on the other hand, due to Hf xZr1-xO2Spontaneous polarization of the ferroelectric layer causes a spontaneous polarization electric field to exist therein, the spontaneous polarization electric field and Ga2O3/HfxZr1-xO2The coupling action of an electric field built in the heterojunction promotes the separation of photon-generated carriers together, thereby realizing the improvement of the performance of the device; further, HfxZr1-xO2The layer has good blocking effect on background carriers, and can greatly reduce dark current of the device.
In some embodiments, HfxZr1-xO2The thickness of the thin film layer 3 is 3-100 nm. Preferably, HfxZr1-xO2The thickness of the thin film layer 3 was 5 nm.
In some embodiments, Ga2O3The thickness of the thin film layer 2 is 50-500 nm.
In some embodiments, substrate 1 comprises an FTO conductive glass substrate, an ITO conductive glass substrate, Pt/Ti/SiO2Any of the substrates of/Si.
Specifically, the FTO conductive glass refers to SnO doped with fluorine2The conductive glass is used for the substrate 1, and the thickness of the substrate is 1.0-2.5 mm. Pt/Ti/SiO2the/Si substrate means: sequential deposition of SiO on Si2、Ti、Pt。
In some embodiments, the top electrode 4 comprises any one of a Pt electrode, an Au electrode, an Al-doped ZnO electrode, an ITO electrode.
Based on the same inventive concept, the embodiment of the application also provides a preparation method of the ferroelectric-semiconductor heterojunction type solar blind ultraviolet photoelectric detector, which comprises the following steps:
S1, providing a substrate;
s2 preparation of Ga on the surface of the substrate2O3A thin film layer;
s3 at Ga2O3Preparing Hf on the surface of the thin film layer far away from one side of the substratexZr1-xO2A thin film layer;
s4 at HfxZr1-xO2And preparing a top electrode on the surface of the thin film layer away from one side of the substrate.
In some embodiments, Ga is prepared at the surface of a substrate2O3The film layer is specifically as follows: with Ga2O3The Ga is prepared on the surface of the substrate by adopting a pulse laser deposition method, a magnetron sputtering method or a sol-gel method by taking ceramic as a target material2O3A thin film layer;
preparation of HfxZr1-xO2The film layer is specifically as follows: applying an atomic layer deposition method, a magnetron sputtering method, a pulsed laser deposition method or a sol-gel method to the Ga2O3Preparation of Hf on the surface of thin film layerxZr1-xO2A thin film layer;
the preparation of the top electrode specifically comprises the following steps: applying vacuum evaporation method, magnetron sputtering method or electron beam deposition method to the HfxZr1- xO2And preparing a top electrode on the surface of the thin film layer.
In some embodiments, Ga is prepared at the surface of a substrate2O3The film layer also comprises: cleaning the substrate, blowing the substrate with high-purity nitrogen, and preparing Ga2O3A thin film layer; the specific cleaning method comprises the following steps: and cleaning the substrate by using acetone, absolute ethyl alcohol and deionized water in sequence, wherein the cleaning time of each cleaning process is 10-20 min, preferably 15 min.
In some embodiments, pulsed laser deposition is used to prepare Ga 2O3The film layer is specifically as follows:
with Ga2O3Ceramic is used as a target material, the temperature of a substrate is controlled to be 25-800 ℃, the Pulse laser energy is controlled to be 150-600 mJ/Pulse, the oxygen pressure is 0-8 Pa, the deposition time is 10-120 min, and Ga is formed by deposition on the surface of the substrate2O3A thin film layer.
In some embodiments, atomic layer deposition is used to prepare HfxZr1-xO2The film layer is specifically as follows:
will be prepared with Ga2O3Placing the substrate of the thin film layer in a sample chamber of an atomic layer deposition system, and performing alternate deposition by using tetra (dimethylamino) hafnium and tetra (dimethylamino) zirconium as precursors to obtain HfxZr1-xO2A thin film layer.
Specifically, alternating deposition is performed to obtain HfxZr1-xO2A thin film layer, further comprising p-HfxZr1-xO2Annealing the film at 450-550 ℃ for 25-45 s.
In some embodiments, Ga2O3The preparation method of the ceramic target comprises the following steps:
to Ga2O3Adding water into the powder, carrying out ball milling, drying and pressing into ceramic green sheets;
firing the ceramic blank sheet at 1000-1400 ℃ for 1-4 h to obtain Ga2O3A ceramic target material.
Specifically, the top electrode prepared by the vacuum evaporation method is specifically (taking an Au top electrode as an example): will be prepared with HfxZr1- xO2The substrate of the film layer is placed on a square mask plate and placed in an evaporation instrument, then a gold wire is placed in a tungsten boat, and the tungsten boat is vacuumized to 10 DEG-4And Pa, starting heating, closing the molecular pump after the Au wire is completely evaporated, closing the mechanical pump after the rotation speed of the molecular pump is 0, opening the air angle valve, introducing air, and taking out the sample when the pressure in the vacuum chamber is consistent with the outdoor pressure, namely finishing the preparation of the top electrode.
The following further describes a method for manufacturing the ferroelectric-semiconductor heterojunction type solar-blind ultraviolet photodetector according to the present application with specific examples.
Example 1
The embodiment of the application provides a ferroelectric-semiconductor heterojunction type solar blind ultraviolet photoelectric detector, which comprises an FTO conductive glass substrate and Ga2O3Thin film layer (thickness 150nm), Hf0.5Zr0.5O2A thin film layer (thickness of 5nm), and an Au top electrode (thickness of 50 nm).
The preparation method of the ferroelectric-semiconductor heterojunction solar blind ultraviolet photoelectric detector comprises the following steps:
s1, providing an FTO conductive glass substrate, sequentially placing the FTO conductive glass substrate in acetone, ethanol and deionized water for cleaning for 15min, blow-drying by using nitrogen gas, immediately placing in a vacuum chamber of a pulse laser deposition system, and then installing Ga2O3Ceramic target material, vacuum pumping to 10-4Pa；
S2, after the temperature of the substrate is raised to 650 ℃, introducing oxygen to maintain the air pressure at 4Pa in the whole film deposition process, setting the output energy of the laser to be 250mJ/pulse, setting the pulse frequency to be 5Hz, then starting the laser to deposit the film, closing the oxygen and heating after 30min of deposition, and finally naturally cooling the sample to room temperature and taking out;
s3, placing the sample prepared in the step S2 in a sample chamber of an atomic layer deposition system, and performing alternate deposition at the temperature of 300 ℃ by adopting an atomic layer deposition method and taking tetrakis (dimethylamino) hafnium and tetrakis (dimethylamino) zirconium as precursors to enable the Hf to be 0.5Zr0.5O2Film thickness of 5nm, Hf prepared after completion0.5Zr0.5O2Annealing the film at 500 ℃ for 30 s;
s4, placing the sample prepared in the step S3 on a square mask plate with the size of 0.5mm multiplied by 0.5mm and placing the square mask plate into an evaporation plating instrument, then placing 0.1g of gold wires into a tungsten boat, and vacuumizing to 10 DEG-4And Pa, starting heating, and preparing the Au top electrode after the Au wire is completely evaporated.
Example 2
The embodiment provides a ferroelectric-semiconductor heterojunction solar blind ultraviolet photoelectric detector which comprises an FTO conductive glass substrate and Ga2O3Thin film layer (thickness 150nm), Hf0.5Zr0.5O2A thin film layer (thickness of 30nm) and an Au top electrode (thickness of 50 nm).
The preparation method of the ferroelectric-semiconductor heterojunction solar blind ultraviolet photoelectric detector comprises the following steps:
s1, providing an FTO conductive glass substrate, sequentially placing the FTO conductive glass substrate in acetone, ethanol and deionized water for cleaning for 15min, blow-drying with nitrogen gas, immediately placing in a vacuum cavity of a pulse laser deposition system, and then installing Ga2O3Ceramic target material, vacuumizing to 10-4Pa；
S2, after the temperature of the substrate is raised to 650 ℃, introducing oxygen to maintain the air pressure at 4Pa in the whole film deposition process, setting the output energy of the laser to be 250mJ/pulse, setting the pulse frequency to be 5Hz, then starting the laser to deposit the film, closing the oxygen and heating after 30min of deposition, and finally naturally cooling the sample to room temperature and taking out;
S3, placing the sample prepared in the step S2 in a sample chamber of an atomic layer deposition system, adopting an atomic layer deposition method, taking tetrakis (dimethylamino) hafnium and tetrakis (dimethylamino) zirconium as precursors, and performing alternate deposition at the temperature of 300 ℃ to enable Hf to be obtained0.5Zr0.5O2Film thickness of 30nm, Hf prepared after completion0.5Zr0.5O2Annealing the film at 500 ℃ for 30 s;
s4, placing the sample prepared in the step S3 on a square mask plate with the size of 0.5mm multiplied by 0.5mm and placing the square mask plate into an evaporation instrument, then placing 0.1g of gold wires into a tungsten boat, and vacuumizing to 10 DEG-4And Pa, starting heating, and preparing the Au top electrode after the Au wire is completely evaporated.
Comparative example 1
This comparative example provides Ga2O3The self-driven solar blind ultraviolet photoelectric detector comprises an FTO conductive glass substrate and Ga from bottom to top2O3A thin film layer (150nm), and an Au top electrode (50 nm).
Ga as described above2O3The preparation method of the self-driven solar blind ultraviolet photoelectric detector comprises the following steps:
s1, providing an FTO conductive glass substrate, sequentially placing the FTO conductive glass substrate in acetone, ethanol and deionized water for cleaning for 15min, blow-drying by using nitrogen gas, immediately placing in a vacuum chamber of a pulse laser deposition system, and then installing Ga2O3Ceramic target material, vacuum pumping to 10 -4Pa；
S2, after the temperature of the substrate is raised to 650 ℃, introducing oxygen to maintain the air pressure at 4Pa in the whole film deposition process, setting the output energy of the laser to be 250mJ/pulse, setting the pulse frequency to be 5Hz, then starting the laser to deposit the film, closing the oxygen and heating after 30min of deposition, and finally naturally cooling the sample to room temperature and taking out;
s3, placing the sample prepared in the step S2 on a square mask plate with the size of 0.5mm multiplied by 0.5mm and placing the square mask plate into an evaporation plating instrument, then placing 0.1g of gold wires into a tungsten boat, and vacuumizing to 10 DEG-4And Pa, starting heating, and preparing the Au top electrode after the Au wire is completely evaporated.
Comparative example 2
This comparative example provides a ZnO/Ga2O3A self-driven solar blind ultraviolet photoelectric detector of heterojunction comprises an FTO conductive glass substrate and Ga from bottom to top2O3A film layer (150nm), a ZnO film layer (100nm), and an Au top electrode (50 nm).
The above ZnO/Ga2O3The preparation method of the self-driven solar blind ultraviolet photoelectric detector of the heterojunction comprises the following steps:
s1, providing an FTO conductive glass substrate, sequentially placing the FTO conductive glass substrate in acetone, ethanol and deionized water for cleaning for 15min, blow-drying by using nitrogen gas, immediately placing in a vacuum chamber of a pulse laser deposition system, and then installing Ga 2O3Vacuum pumping the target material and ZnO target material to 10-4Pa；
S2, after the temperature of the substrate is raised to 650 ℃, introducing oxygen to ensure thatThe gas pressure is maintained at 4Pa during the whole film deposition process, and Ga is deposited firstly2O3The method comprises the following steps of (1) film forming, setting the output energy of a laser to be 250mJ/pulse, setting the pulse frequency to be 5Hz, then starting the laser to deposit the film, and closing oxygen and heating after 30min of deposition; then, the substrate temperature is made to be 350 ℃, a ZnO film is deposited, the output energy of a laser is set to be 250mJ/pulse, the pulse frequency is 5Hz, then, the laser is started to deposit the film, and oxygen and heating are turned off after 30min of deposition; and finally, naturally cooling the sample to room temperature and taking out.
S4, placing the sample prepared in the step S2 on a square mask plate with the size of 0.5mm multiplied by 0.5mm and placing the square mask plate into an evaporation instrument, then placing 0.1g of gold wires into a tungsten boat, and vacuumizing to 10 DEG-4And Pa, starting heating, and preparing the Au top electrode after the Au wire is completely evaporated.
Performance testing
The ferroelectric-semiconductor heterojunction type solar-blind ultraviolet photodetector prepared in test example 1 has an I-t curve of a single period under irradiation of ultraviolet light at 240nm, and the result is shown in fig. 2.
As can be seen from fig. 2, the rise/fall response time of the device is 0.093s/0.63 s.
Ga prepared in comparative example 1 was tested2O3The result of the photocurrent response spectrum of the self-driven solar blind ultraviolet photoelectric detector under the irradiation of monochromatic light with the wavelength of 240nm is shown in figure 3. It can be seen from fig. 3 that the device exhibits a strong photocurrent response to monochromatic light at 240 nm.
Ga prepared in comparative example 1 was tested2O3The result is shown in fig. 4 based on the one-cycle I-t curve of the self-driven solar blind ultraviolet photodetector.
It can be seen from fig. 4 that the rise response time and the fall response time of the device are 0.149s and 3.40s, respectively.
The ferroelectric-semiconductor heterojunction type solar-blind ultraviolet photodetector prepared in example 1 and the Ga prepared in comparative example 1 were tested2O3The result is shown in fig. 5 based on the dark-state current-voltage curve of the self-driven solar-blind ultraviolet photodetector.
As can be seen from fig. 5, the ferroelectric-semiconductor heterojunction type solar-blind ultraviolet photoelectric detector prepared in example 1 has a significantly smaller dark current than the detector in comparative example 1.
Testing of ZnO/Ga prepared in comparative example 22O3The I-t curve of the heterojunction self-driven solar-blind ultraviolet photodetector under the irradiation of 240nm ultraviolet light is shown in figure 6.
As can be seen from FIG. 6, the prepared detector has a relatively obvious photocurrent response to ultraviolet light of 240nm, and the maximum current of the detector can reach 29.5 pA; however, its photocurrent response was higher than that of Ga prepared in comparative example 1 2O3The self-driven solar blind ultraviolet photoelectric detector is weak, and the solar blind ultraviolet photoelectric detector is ZnO/Ga2O3The band gap narrowing of the ZnO layer in the heterojunction absorbs deep ultraviolet light, resulting in Ga2O3The layer is not functional.
The ferroelectric-semiconductor heterojunction-type solar-blind ultraviolet photodetector prepared in example 1 and the Ga prepared in comparative example 1 were tested2O3Based on the spectral responsivity curve graph of the self-driven solar blind ultraviolet photoelectric detector, the result is shown in fig. 7. Au/Ga in FIG. 72O3FTO denotes the detector prepared in comparative example 1, Au/HfZrO2/Ga2O3the/FTO denotes the probe prepared in example 1.
As can be seen from FIG. 7, the responsivity of both detectors reached a maximum at 240nm, wherein the responsivity (14.64mA/W) of the ferroelectric-semiconductor heterojunction type solar-blind ultraviolet photodetector prepared in example 1 was significantly higher than that (8.98mA/W) of the detector prepared in comparative example 1, due to the detector Hf in example 10.5Zr0.5O2/Ga2O3The heterojunction built-in electric field and the ferroelectric spontaneous polarization electric field are caused by the synergistic separation effect of the photogenerated carriers; further, as can be seen from fig. 2 and 4, the rise/fall response times of the ferroelectric-semiconductor heterojunction type solar-blind ultraviolet photodetector prepared in example 1 are both shorter than those of the Ga prepared in comparative example 1 2O3Based onThe solar blind ultraviolet photodetector is driven, and the response speed of the detector prepared in the embodiment 1 is higher.
The photocurrent response spectrum of the ferroelectric-semiconductor heterojunction type solar-blind ultraviolet photodetector prepared in example 2 under the irradiation of monochromatic light with a wavelength of 240nm was tested, and the result is shown in fig. 8.
As can be seen from FIG. 8, the detector in example 2 has a significant photocurrent response to monochromatic light at 240nm, but is weaker than that of the detector in comparative example 1 due to Hf of the detector in example 20.5Zr0.5O2The film thickness is too thick, resulting in a weak photocurrent response of the detector.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (2)
1. A preparation method of a ferroelectric-semiconductor heterojunction type solar-blind ultraviolet photoelectric detector is characterized in that the ferroelectric-semiconductor heterojunction type solar-blind ultraviolet photoelectric detector comprises the following steps:
a substrate;
Ga2O3the thin film layer is positioned on the surface of the substrate;
Hf0.5Zr0.5O2a thin film layer on the Ga2O3The surface of the thin film layer on the side away from the substrate;
A top electrode at said Hf0.5Zr0.5O2The surface of the thin film layer on the side away from the substrate;
the substrate is FTO conductive glass substrate, Ga2O3The thickness of the thin film layer is 150nm, Hf0.5Zr0.5O2The thickness of the thin film layer is 5nm, the top electrode is an Au top electrode, and the thickness of the top electrode is 50 nm;
the preparation method of the ferroelectric-semiconductor heterojunction solar blind ultraviolet photoelectric detector comprises the following steps:
s1, providing an FTO conductive glass substrate, sequentially placing the FTO conductive glass substrate in acetone, ethanol and deionized water for cleaning for 15 min, blow-drying by using nitrogen gas, immediately placing in a vacuum chamber of a pulse laser deposition system, and then installing Ga2O3Ceramic target material, vacuumizing to 10-4 Pa；
S2, after the temperature of the substrate is raised to 650 ℃, introducing oxygen to maintain the air pressure at 4 Pa in the whole film deposition process, setting the output energy of the laser to be 250 mJ/pulse, setting the pulse frequency to be 5 Hz, then starting the laser to deposit the film, closing the oxygen and heating after depositing for 30 min, and finally naturally cooling the sample to room temperature and taking out;
s3, placing the sample prepared in the step S2 in a sample chamber of an atomic layer deposition system, and performing alternate deposition at the temperature of 300 ℃ by adopting an atomic layer deposition method and taking tetrakis (dimethylamino) hafnium and tetrakis (dimethylamino) zirconium as precursors to enable the Hf to be 0.5Zr0.5O2Film thickness of 5 nm, Hf prepared after completion0.5Zr0.5O2Annealing the film at 500 ℃ for 30 s;
s4, placing the sample prepared in the step S3 on a square mask plate with the size of 0.5 mm multiplied by 0.5 mm and placing the square mask plate into an evaporation instrument, then placing 0.1g of gold wires into a tungsten boat, and vacuumizing to 10 DEG-4And Pa, starting heating, and preparing the Au top electrode after the Au wire is completely evaporated.
2. The method of claim 1, wherein the Ga is used to fabricate the ferroelectric-semiconductor heterojunction solar-blind uv photodetector2O3The preparation method of the ceramic comprises the following steps:
to Ga2O3Adding water into the powder, carrying out ball milling, drying and pressing into ceramic green sheets;
firing the ceramic blank sheet at 1000-1400 ℃ for 1-4 h to obtain Ga2O3A ceramic.
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