CN112201711A - ZnO-based homojunction self-driven ultraviolet photoelectric detector and preparation method thereof - Google Patents
ZnO-based homojunction self-driven ultraviolet photoelectric detector and preparation method thereof Download PDFInfo
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Abstract
The invention provides a ZnO-based homojunction self-driven ultraviolet photoelectric detector and a preparation method thereof, wherein the ZnO-based homojunction self-driven ultraviolet photoelectric detector comprises the following components: a substrate; the first n-ZnO film layer is positioned on the surface of the substrate; the second n-ZnO film layer is positioned on one side of the first n-ZnO film layer, which is far away from the substrate, and the orthographic projection of the second n-ZnO film layer on the surface of the first n-ZnO film layer does not completely cover the first n-ZnO film layer; the nitrogen-doped p-type conductive BeZnOS thin film layer is positioned on one side of the second n-ZnO thin film layer, which is far away from the substrate; the first metal electrode layer is positioned on one side, far away from the substrate, of the nitrogen-doped p-type conductive BeZnOS thin film layer; and the second metal electrode layer is positioned on the partial surface of the first n-ZnO thin film layer except the second n-ZnO thin film layer. The photoelectric detector has low dark current and power consumption and high response speed, and can work under zero bias.
Description
Technical Field
The invention relates to an ultraviolet photoelectric detector, in particular to a ZnO-based homojunction self-driven ultraviolet photoelectric detector and a preparation method thereof.
Background
The ZnO material serving as a II-VI wide bandgap semiconductor has a wider bandgap (3.37eV) and a larger exciton confinement energy (60meV), has huge application potential in the field of ultraviolet photoelectricity, and is one of the best candidate materials for preparing an ultraviolet photoelectric detector. In recent years, various MSM (metal-semiconductor-metal) type ZnO-based photodetectors have received extensive attention and research, and have achieved many results. However, zinc oxide based MSM type photodetectors typically have a slow response speed. In addition, the MSM type detector needs an additional external bias voltage to drive the device to operate, resulting in high dark current and large power consumption of the device.
Aiming at the defects of low response speed, high dark current and high power consumption of the prior ZnO-based ultraviolet photodetector, the prior ZnO-based ultraviolet photodetector needs to be improved.
Disclosure of Invention
In view of this, the invention provides a ZnO-based homojunction self-driven ultraviolet photodetector and a preparation method thereof, so as to solve the technical problems of slow response speed, high dark current and large power consumption in the prior art.
In a first aspect, the present invention provides a ZnO-based homojunction self-driven ultraviolet photodetector, comprising:
a substrate;
the first n-ZnO film layer is positioned on the surface of the substrate;
the second n-ZnO thin film layer is positioned on the surface of one side, away from the substrate, of the first n-ZnO thin film layer, and the orthographic projection of the second n-ZnO thin film layer on the surface of the first n-ZnO thin film layer does not completely cover the first n-ZnO thin film layer;
the nitrogen-doped p-type conductive BeZnOS thin film layer is positioned on the surface of one side of the second n-ZnO thin film layer, which is far away from the substrate;
the first metal electrode layer is positioned on the surface of one side, far away from the substrate, of the nitrogen-doped p-type conductive BeZnOS thin film layer;
a second metal electrode layer arranged at the first n-ZnO thin film layer and outside the second n-ZnO thin film layer
A surface.
Optionally, the first metal electrode layer includes a gold electrode layer, and the second metal electrode layer includes an aluminum electrode layer.
In a second aspect, the present invention further provides a method for preparing a ZnO-based homojunction self-driven ultraviolet photodetector, including:
providing a ZnO ceramic target material and a BeZnOS ceramic target material;
providing a substrate, and preparing a first n-ZnO thin film layer on the surface of the substrate by using a ZnO ceramic target;
preparing a second n-ZnO thin film layer on the surface of one side, away from the substrate, of the first n-ZnO thin film layer, wherein the orthographic projection of the second n-ZnO thin film layer on the surface of the first n-ZnO thin film layer does not completely cover the first n-ZnO thin film layer;
preparing a nitrogen-doped p-type conductive BeZnOS thin film layer on the surface of the second n-ZnO thin film layer, which is far away from the substrate, by using a BeZnOS ceramic target;
preparing a first metal electrode layer on the surface of one side, away from the substrate, of the nitrogen-doped p-type conductive BeZnOS thin film layer;
and preparing a second metal electrode layer on the surface of the part of the first n-ZnO film layer, which is positioned outside the second n-ZnO film layer.
Optionally, the step of preparing the first n-ZnO thin film layer on the surface of the substrate by using the ZnO ceramic target specifically comprises: and placing the substrate in a vacuum cavity of a pulsed laser deposition system, heating the substrate to 600-700 ℃, introducing oxygen into the vacuum cavity, adjusting the pressure of a growth chamber to 1-5 Pa, and preparing a first n-ZnO film layer on the substrate by using a ZnO ceramic target material and adopting a pulsed laser ablation method.
Optionally, the step of preparing the nitrogen-doped p-type conductive BeZnOS thin film layer on the surface of the second n-ZnO thin film layer far away from the substrate by using the BeZnOS ceramic target specifically comprises the following steps:
placing the substrate in a vacuum cavity of a pulse laser deposition system, heating the substrate to 300-500 ℃, introducing nitric oxide gas into the vacuum cavity, adjusting the pressure of a growth chamber to 3-7 Pa, and preparing a nitrogen-doped BeZnOS film on the surface of a second n-ZnO film layer by using a BeZnOS ceramic target material and adopting a pulse laser ablation method;
and annealing the obtained nitrogen-doped BeZnOS thin film at 400-750 ℃ in the atmosphere of nitric oxide to obtain the nitrogen-doped p-type conductive BeZnOS thin film.
Optionally, the preparation method of the ZnO ceramic target includes:
adding water into ZnO powder, ball-milling, and drying;
pressing ZnO powder into a ZnO ceramic blank, and sintering the ZnO ceramic blank in a vacuum tube furnace at the temperature of 700-1300 ℃ to obtain the ZnO ceramic target.
Optionally, the preparation method of the BeZnOS ceramic target material includes:
mixing ZnS powder and BeO powder and then carrying out ball milling to obtain mixed powder;
pressing the mixed powder into a ceramic green sheet;
and sintering the ceramic green sheet in a vacuum tube furnace at the temperature of 700-1300 ℃ by taking ZnS as an oxygen scavenger and argon as a protective gas to obtain the BeZnOS ceramic target.
Optionally, the molar ratio of the ZnS powder to the BeO powder is 99: 1-70: 30.
Optionally, before placing the substrate in the vacuum chamber of the pulsed laser deposition system, the method further comprises cleaning the substrate with acetone, absolute ethyl alcohol, and deionized water in sequence.
Optionally, the substrate comprises a c-plane sapphire substrate.
Compared with the prior art, the preparation method of the ZnO-based homojunction self-driven ultraviolet photoelectric detector has the following beneficial effects:
(1) according to the ZnO-based homojunction self-driven ultraviolet photoelectric detector, a pn junction is formed between the nitrogen-doped p-type conductive BeZnOS thin film layer and the second n-ZnO thin film layer as well as the first n-ZnO thin film layer, and the nitrogen-doped p-type conductive BeZnOS thin film layer is used as a hole transport layer, so that the detector has high repeatability and stability, has low dark current and power consumption and high response speed compared with the traditional MSM detector, and can work under zero bias;
(2) the ZnO-based homojunction self-driven ultraviolet photoelectric detector is a photovoltaic semiconductor photoelectric detector and is characterized in that an external power supply is not needed, when light radiation generates unbalanced carriers, a built-in electric field of a pn junction separates holes and electrons and transmits the holes and the electrons to two ends of an electrode to generate photocurrent, so that dark current can be effectively reduced, and the photoresponse speed is improved;
(3) the preparation method of the ZnO-based homojunction self-driven ultraviolet photoelectric detector adopts the conventional pulse laser deposition technology for growth, and has simple equipment and operation process and easy control.
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 ZnO-based homojunction self-driven ultraviolet photodetector of the present invention;
FIG. 2 is a process flow diagram of the fabrication method of the ZnO-based homojunction self-driven ultraviolet photodetector of the present invention;
fig. 3 is a current-voltage curve diagram of a ZnO-based homojunction self-driven ultraviolet photodetector prepared in example 1 of the present invention under a dark condition;
fig. 4 is a graph of response speed of a ZnO-based homojunction self-driven ultraviolet photodetector prepared in example 1 of the present invention under a bias voltage of 0V and under illumination of an ultraviolet light of 360 nm;
fig. 5 is a graph of response speed of the ZnO-based homojunction self-driven ultraviolet photodetector prepared in example 1 under the bias of 0V and under the illumination of closed 360nm ultraviolet light;
fig. 6 is a time-current curve diagram of a ZnO-based homojunction self-driven ultraviolet photodetector prepared in example 1 of the present invention under a bias voltage of 0V and under illumination of 360nm ultraviolet light;
fig. 7 is a graph showing the photoresponse curve of the ZnO-based homojunction self-driven ultraviolet photodetector prepared in example 1 of the present invention for different wavelengths under a bias of 0V.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described 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 any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
As shown in fig. 1, the present invention provides a ZnO-based homojunction self-driven ultraviolet photodetector, comprising:
a substrate 1;
the first n-ZnO film layer 2 is positioned on the surface of the substrate 1;
the second n-ZnO thin film layer 3 is positioned on the surface of one side of the first n-ZnO thin film layer 2, which is far away from the substrate 1, and the orthographic projection of the second n-ZnO thin film layer 3 on the surface of the first n-ZnO thin film layer 2 does not completely cover the first n-ZnO thin film layer 1;
the nitrogen-doped p-type conductive BeZnOS thin film layer 4 is positioned on the surface of one side of the second n-ZnO thin film layer 3, which is far away from the substrate 1;
the first metal electrode layer 5 is positioned on the surface of one side, away from the substrate 1, of the nitrogen-doped p-type conductive BeZnOS thin film layer 4;
and a second metal electrode layer 6 which is positioned on the partial surface of the first n-ZnO thin film layer 2 except the second n-ZnO thin film layer 3.
In the present embodiment, the substrate 1 includes a c-plane sapphire substrate or glass substrate, a silicon or quartz glass substrate, a GaN/sapphire (silicon) substrate, and the like, and the sapphire substrate contains alumina (Al) as a main component2O3) Specifically, the substrate in the present application is a c-plane sapphire substrate.
The n-ZnO thin film layers of the first n-ZnO thin film layer 2 and the second n-ZnO thin film layer 3 are n-type ZnO thin film layers.
In the embodiment of the application, the second n-ZnO thin film layer 3 is located on the surface of the first n-ZnO thin film layer 2 on the side away from the substrate 1, specifically, the surface of the first n-ZnO thin film layer 2 is divided into two equal parts, the right side and the left side, the orthographic projection of the second n-ZnO thin film layer 3 on the surface of the first n-ZnO thin film layer 2 is overlapped with the left side part of the surface of the first n-ZnO thin film layer 2, and the right side part of the surface of the first n-ZnO thin film layer 2 is completely exposed.
In the embodiment of the application, the first metal electrode layer 5 is a gold electrode layer, the second metal electrode layer 6 is an aluminum electrode layer, the nitrogen-doped p-type conductive BeZnOS thin film layer 4 is in ohmic contact with the first metal electrode layer 5, and the first n-ZnO thin film layer 2 is in ohmic contact with the second metal electrode layer.
According to the ZnO-based homojunction self-driven ultraviolet photoelectric detector, the nitrogen-doped p-type conductive BeZnOS thin film layer, the second n-ZnO thin film layer and the first n-ZnO thin film layer form a pn junction, the nitrogen-doped p-type conductive BeZnOS thin film layer serves as a hole transmission layer, the repeatability and the stability are high, compared with the traditional MSM type detector, the detector has the advantages of low dark current, low power consumption and high response speed, and can work under zero bias.
Based on the same inventive concept, the embodiment of the present application further provides a preparation method of the ZnO-based homojunction self-driven ultraviolet photodetector, as shown in fig. 2, including the following steps:
s1, providing a ZnO ceramic target and a BeZnOS ceramic target;
s2, providing a substrate, and preparing a first n-ZnO film layer on the surface of the substrate by using a ZnO ceramic target;
s3, preparing a second n-ZnO film layer on the surface of the first n-ZnO film layer, which is far away from the substrate side, wherein the orthographic projection of the second n-ZnO film layer on the surface of the first n-ZnO film layer does not completely cover the first n-ZnO film layer;
s4, preparing a nitrogen-doped p-type conductive BeZnOS thin film layer on the surface of the second n-ZnO thin film layer, which is far away from the substrate, by using a BeZnOS ceramic target;
s5, preparing a first metal electrode layer on the surface of the side, away from the substrate, of the nitrogen-doped p-type conductive BeZnOS thin film layer;
s6, preparing a second metal electrode layer on the surface of the first n-ZnO thin film layer, which is located outside the second n-ZnO thin film layer.
Specifically, in the embodiment of the present application, the preparation method of the ZnO ceramic target includes:
weighing 10g of high-purity ZnO powder in a ball milling tank, adding deionized water accounting for 60% of the total mass of the ZnO powder, carrying out ball milling for 8 hours, then placing the ball-milled ZnO powder in a vacuum drying oven, drying at 120 ℃ for 8 hours, then adding absolute ethyl alcohol accounting for 3% of the total mass of the powder into the dried ZnO powder, grinding and stirring uniformly to obtain ceramic blanks which are mixed and bonded together, and pressing the ceramic blanks into ZnO ceramic blanks in a tablet press under the pressure of 4 MPa; and sintering the obtained ZnO ceramic green sheet in a vacuum tube furnace at 1200 ℃ in an oxygen atmosphere to obtain the ZnO ceramic target.
In the embodiment of the application, the preparation method of the BeZnOS ceramic target comprises the following steps: weighing ZnS and BeO powder with a molar ratio of 94:6 in a ball milling tank to obtain mixed powder, and then adding deionized water accounting for 60 percent of the total mass of the powder into the mixed powder to perform ball milling for 8 hours; putting the mixed powder after ball milling into a vacuum drying oven, and drying for 8 hours at the temperature of 120 ℃; then, adding absolute ethyl alcohol accounting for 3% of the total mass of the powder into the dried powder, grinding and uniformly stirring to obtain ceramic blanks which are mixed and bonded together, and pressing the ceramic blanks into BeZnOS ceramic blanks with the thickness of 3mm in a tablet press at the pressure of 4 MPa; and sintering the sintered product in a vacuum tube furnace at the temperature of 1200 ℃ by taking ZnS as an oxygen scavenger and argon as a protective gas to obtain the BeZnOS ceramic target material.
In the embodiment of the application, c-plane sapphire is a substrate for thin film growth, the substrate is sequentially washed by acetone, absolute ethyl alcohol and deionized water for 15 minutes, then dried by high-purity nitrogen, the clean substrate is obtained and put into a vacuum cavity of a pulse laser deposition system, and the vacuum cavity is vacuumized to 1 × 10-4Pa, heating the substrate to 700 ℃, and introducing high-purity O2In the vacuum cavity, adjusting the air pressure of a growth chamber to 3Pa, and growing an n-ZnO film on a substrate by using a ZnO ceramic target material by adopting a pulse laser ablation method to obtain a first n-ZnO film layer; covering the surface part of the first n-ZnO thin film layer by using a mask, specifically, covering the part on the right side of the first n-ZnO thin film layer by using the mask, and preparing a second n-ZnO thin film layer on the left side of the first n-ZnO thin film layer by using the same method; then heating the substrate with the second n-ZnO film layer to 400 ℃, introducing nitric oxide gas into the vacuum cavity, adjusting the pressure of the growth chamber to 7Pa, and growing the nitrogen-doped BeZnOS film on the surface of the second n-ZnO film layer by using a pulse laser ablation method by using a BeZnOS ceramic target material to obtain the nitrogen-doped BeZnOS film; and then annealing the nitrogen-doped BeZnOS film at the temperature of 550 ℃ in the atmosphere of nitrogen oxide to obtain the nitrogen-doped p-type conductive BeZnOS film.
In the embodiment of the application, the first metal electrode layer and the second metal layer can be prepared by chemical vapor deposition, physical vapor deposition, evaporation and other methods.
The ZnO-based homojunction self-driven ultraviolet photoelectric detector prepared by the embodiment of the application is a photovoltaic semiconductor photoelectric detector, and is characterized in that an external power supply is not needed, when light radiation generates unbalanced carriers, a built-in electric field of a pn junction separates holes and electrons and transmits the holes and the electrons to two ends of an electrode to generate photocurrent, so that dark current can be effectively reduced, and the photoresponse speed can be improved.
The ZnO-based homojunction self-driven ultraviolet photoelectric detector prepared by the embodiment of the application is tested for the performance of the ultraviolet photoelectric detector, and I-V tests show that the zinc oxide-based homojunction has a good rectification effect and the starting voltage is 2.2V. The detector has the advantages that the rising response time of the detector under 0V bias and 360nm illumination is 6ms, the attenuation time is 10ms, 7 periodic tests are repeated, the detector has excellent repeatability, no response to visible light, and high responsivity to ultraviolet light (the highest response is at 370nm, 5.4mA/W), and the detector has ultra-fast response speed, excellent stability and repeatability and excellent light selectivity.
Example 2
In the same embodiment 1, the method for preparing the ZnO-based homojunction self-driven ultraviolet photodetector in the embodiment of the present application includes the following steps:
s1, providing a ZnO ceramic target and a BeZnOS ceramic target;
s2, providing a substrate, and preparing a first n-ZnO film layer on the surface of the substrate by using a ZnO ceramic target;
s3, preparing a second n-ZnO film layer on the surface of the first n-ZnO film layer far away from the substrate side
In the method, the orthographic projection of the second n-ZnO thin film layer on the surface of the first n-ZnO thin film layer does not completely cover the first n-ZnO thin film layer;
s4, preparing a nitrogen-doped p-type conductive BeZnOS thin film layer on the surface of the second n-ZnO thin film layer, which is far away from the substrate, by using a BeZnOS ceramic target;
s5, preparing a first metal electrode layer on the surface of the side, away from the substrate, of the nitrogen-doped p-type conductive BeZnOS thin film layer;
s6, preparing a second metal electrode layer on the surface of the first n-ZnO thin film layer, which is located outside the second n-ZnO thin film layer.
Specifically, in the embodiment of the present application, the method for preparing the ZnO ceramic target includes:
weighing 10g of high-purity ZnO powder in a ball milling tank, adding deionized water accounting for 50% of the total mass of the ZnO powder, carrying out ball milling for 10 hours, then placing the ball-milled ZnO powder in a vacuum drying oven, drying at the temperature of 110 ℃ for 8 hours, then adding absolute ethyl alcohol accounting for 5% of the total mass of the powder into the dried ZnO powder, grinding and stirring uniformly to obtain ceramic blanks which are mixed and bonded together, and pressing in a tablet press at the pressure of 4MPa to prepare ZnO ceramic blanks; and sintering the obtained ZnO ceramic green sheet in a vacuum tube furnace at 1200 ℃ in an oxygen atmosphere to obtain the ZnO ceramic target.
In the embodiment of the application, the preparation method of the BeZnOS ceramic target comprises the following steps: weighing ZnS and BeO powder with a molar ratio of 94:6 in a ball milling tank to obtain mixed powder, and then adding deionized water accounting for 50% of the total mass of the powder into the mixed powder to perform ball milling for 10 hours; putting the mixed powder after ball milling into a vacuum drying oven, and drying for 8 hours at the temperature of 120 ℃; then, adding absolute ethyl alcohol accounting for 5 percent of the total mass of the powder into the dried powder, grinding and uniformly stirring to obtain ceramic blanks which are mixed and bonded together, and pressing the ceramic blanks into BeZnOS ceramic blanks with the thickness of 3mm in a tablet press at the pressure of 4 MPa; and sintering the sintered product in a vacuum tube furnace at the temperature of 1200 ℃ by taking ZnS as an oxygen scavenger and argon as a protective gas to obtain the BeZnOS ceramic target material.
In the embodiment of the application, c-plane sapphire is a substrate for thin film growth, the substrate is sequentially washed by acetone, absolute ethyl alcohol and deionized water for 15 minutes, then dried by high-purity nitrogen, the clean substrate is obtained and put into a vacuum cavity of a pulse laser deposition system, and the vacuum cavity is vacuumized to 1 × 10-4Pa, heating the substrate to 700 ℃, and introducing high-purity O2In a vacuum chamber, adjustingThe air pressure of the growth chamber is 3Pa, and the growth of an n-ZnO film is carried out on the substrate by using a ZnO ceramic target material and adopting a pulse laser ablation method, so that a first n-ZnO film layer is prepared; covering the surface part of the first n-ZnO thin film layer by using a mask, specifically, covering the part on the right side of the first n-ZnO thin film layer by using the mask, and preparing a second n-ZnO thin film layer on the left side of the first n-ZnO thin film layer by using the same method; then heating the substrate with the second n-ZnO film layer to 400 ℃, introducing nitric oxide gas into the vacuum cavity, adjusting the pressure of the growth chamber to 7Pa, and growing the nitrogen-doped BeZnOS film on the surface of the second n-ZnO film layer by using a pulse laser ablation method by using a BeZnOS ceramic target material to obtain the nitrogen-doped BeZnOS film; and then annealing the nitrogen-doped BeZnOS film at the temperature of 600 ℃ in the atmosphere of nitrogen oxide to obtain the nitrogen-doped p-type conductive BeZnOS film layer.
In the embodiment of the application, the first metal electrode layer and the second metal electrode layer can be prepared by methods such as chemical vapor deposition, physical vapor deposition and evaporation.
The ZnO-based homojunction self-driven ultraviolet photoelectric detector prepared by the embodiment of the application is tested for the performance of the ultraviolet photoelectric detector, and I-V tests show that the ZnO-based homojunction has a good rectification effect and the starting voltage is 0.59V. The detector has the advantages that the rising response time of the detector under 0V bias and 360nm illumination is 22ms, the decay time is 25ms, a plurality of periodic tests are repeated, and the detector has excellent repeatability, so that the detector has ultra-fast response speed, and excellent stability and repeatability are shown.
Example 3
In the same embodiment 1, the method for preparing the ZnO-based homojunction self-driven ultraviolet photodetector in the embodiment of the present application includes the following steps:
s1, providing a ZnO ceramic target and a BeZnOS ceramic target;
s2, providing a substrate, and preparing a first n-ZnO film layer on the surface of the substrate by using a ZnO ceramic target;
s3, preparing a second n-ZnO film layer on the surface of the first n-ZnO film layer far away from the substrate side
In the method, the orthographic projection of the second n-ZnO thin film layer on the surface of the first n-ZnO thin film layer does not completely cover the first n-ZnO thin film layer;
s4, preparing a nitrogen-doped p-type conductive BeZnOS thin film layer on the surface of the second n-ZnO thin film layer, which is far away from the substrate, by using a BeZnOS ceramic target;
s5, preparing a first metal electrode layer on the surface of the side, away from the substrate, of the nitrogen-doped p-type conductive BeZnOS thin film layer;
s6, preparing a second metal electrode layer on the surface of the first n-ZnO thin film layer, which is located outside the second n-ZnO thin film layer.
Specifically, in the embodiment of the present application, the method for preparing the ZnO ceramic target includes:
weighing 10g of high-purity ZnO powder in a ball milling tank, adding deionized water accounting for 30% of the total mass of the ZnO powder, performing ball milling for 12 hours, then placing the ball-milled ZnO powder in a vacuum drying oven, drying at 115 ℃ for 10 hours, then adding absolute ethyl alcohol accounting for 6% of the total mass of the powder into the dried ZnO powder, uniformly grinding and stirring to obtain ceramic blanks which are mixed and bonded together, and pressing the ceramic blanks into ZnO ceramic blanks in a tablet press under the pressure of 4 MPa; and sintering the obtained ZnO ceramic green sheet at 1250 ℃ in a vacuum tube furnace in an oxygen atmosphere to obtain the ZnO ceramic target.
In the embodiment of the application, the preparation method of the BeZnOS ceramic target comprises the following steps: weighing ZnS and BeO powder with a molar ratio of 94:6 in a ball milling tank to obtain mixed powder, and then adding deionized water accounting for 55% of the total mass of the powder into the mixed powder to perform ball milling for 12 hours; putting the mixed powder after ball milling into a vacuum drying oven, and drying for 10 hours at the temperature of 115 ℃; then, absolute ethyl alcohol with the total mass of 6% of the powder is added into the dried powder, the mixture is ground and stirred uniformly to obtain ceramic blanks which are mixed and bonded together, and the ceramic blanks are pressed into BeZnOS ceramic blanks with the thickness of 3mm in a tablet press at the pressure of 4 MPa; and sintering the sintered product in a vacuum tube furnace at 1250 ℃ by taking ZnS as an oxygen scavenger and argon as protective gas to obtain the BeZnOS ceramic target material.
Practice of the present applicationIn the example, c-plane sapphire is a substrate for thin film growth, the substrate is sequentially washed by acetone, absolute ethyl alcohol and deionized water for 15 minutes, then is dried by high-purity nitrogen gas to obtain a clean substrate, the clean substrate is placed into a vacuum cavity of a pulse laser deposition system, and the vacuum cavity is vacuumized to 2 multiplied by 10-4Pa, heating the substrate to 700 ℃, and introducing high-purity O2In the vacuum cavity, adjusting the air pressure of a growth chamber to 3Pa, and growing an n-ZnO film on a substrate by using a ZnO ceramic target material by adopting a pulse laser ablation method to obtain a first n-ZnO film layer; covering the surface part of the first n-ZnO thin film layer by using a mask, specifically, covering the part on the right side of the first n-ZnO thin film layer by using the mask, and preparing a second n-ZnO thin film layer on the left side of the first n-ZnO thin film layer by using the same method; then heating the substrate with the second n-n-ZnO film layer to 400 ℃, introducing nitric oxide gas into the vacuum cavity, adjusting the pressure of the growth chamber to 7Pa, and growing the nitrogen-doped BeZnOS film on the surface of the second n-ZnO film layer by using a pulse laser ablation method by using a BeZnOS ceramic target material to obtain the nitrogen-doped BeZnOS film; and then annealing the nitrogen-doped BeZnOS film at 575 ℃ in the atmosphere of nitrogen oxide to obtain the nitrogen-doped p-type conductive BeZnOS film layer.
In the embodiment of the application, the first metal electrode layer and the second metal electrode layer can be prepared by methods such as chemical vapor deposition, physical vapor deposition and evaporation.
The current-voltage curve of the ZnO-based homojunction self-driven ultraviolet photodetector prepared in embodiment 1 of the present application under a dark condition is tested, and the result is shown in fig. 3, it can be seen from fig. 3 that the ZnO-based homojunction self-driven ultraviolet photodetector has a good rectification effect, and the turn-on voltage is 2.2V.
The response speed of the ZnO-based homojunction self-driven ultraviolet photodetector prepared in embodiment 1 of the present application is tested when the 360nm ultraviolet light is turned on for illumination under the bias voltage of 0V, and the result is shown in fig. 4, and it can be known from fig. 4 that the rise response time of the ZnO-based homojunction self-driven ultraviolet photodetector under the bias voltage of 0V and the illumination of 360nm is 6ms, and the decay time is 10 ms.
The response speed of the ZnO-based homojunction self-driven ultraviolet photodetector prepared in example 1 of the present application when the illumination of 360nm ultraviolet light is turned off under the bias voltage of 0V is tested, and the result is shown in fig. 5.
The time current curve (7 cycles) of the ZnO-based homojunction self-driven ultraviolet photodetector prepared in embodiment 1 of the present application under the irradiation of ultraviolet light of 360nm under the bias voltage of 0V is tested, and the result is shown in fig. 6, and as can be seen from fig. 6, the ZnO-based homojunction self-driven ultraviolet photodetector has excellent repeatability after 7 cycle tests are repeated.
The ZnO-based homojunction self-driven ultraviolet photoelectric detector prepared in the embodiment 1 of the application is tested to the light responsivity curves of different wavelengths under the bias of 0V, and the result is shown in fig. 7, and as can be seen from fig. 7, the ZnO-based homojunction self-driven ultraviolet photoelectric detector has no response to visible light and has high responsivity to ultraviolet light (the highest responsivity is 5.4mA/W at 370 nm), which indicates that the detector has an ultra-fast response speed, excellent stability and repeatability and excellent light selectivity.
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 (10)
- ZnO-based homojunction self-driven ultraviolet photoelectric detector, comprising:a substrate;the first n-ZnO film layer is positioned on the surface of the substrate;the second n-ZnO thin film layer is positioned on the surface of one side, away from the substrate, of the first n-ZnO thin film layer, and the orthographic projection of the second n-ZnO thin film layer on the surface of the first n-ZnO thin film layer does not completely cover the first n-ZnO thin film layer;the nitrogen-doped p-type conductive BeZnOS thin film layer is positioned on the surface of one side of the second n-ZnO thin film layer, which is far away from the substrate;the first metal electrode layer is positioned on the surface of one side, far away from the substrate, of the nitrogen-doped p-type conductive BeZnOS thin film layer;and the second metal electrode layer is positioned on the partial surface of the first n-ZnO thin film layer except the second n-ZnO thin film layer.
- 2. The ZnO-based homojunction self-driven uv photodetector of claim 1, wherein the first metal electrode layer comprises a gold electrode layer and the second metal electrode layer comprises an aluminum electrode layer.
- 3. A preparation method of a ZnO-based homojunction self-driven ultraviolet photoelectric detector is characterized by comprising the following steps:providing a ZnO ceramic target material and a BeZnOS ceramic target material;providing a substrate, and preparing a first n-ZnO thin film layer on the surface of the substrate by using a ZnO ceramic target;preparing a second n-ZnO thin film layer on the surface of one side, away from the substrate, of the first n-ZnO thin film layer, wherein the orthographic projection of the second n-ZnO thin film layer on the surface of the first n-ZnO thin film layer does not completely cover the first n-ZnO thin film layer;preparing a nitrogen-doped p-type conductive BeZnOS thin film layer on the surface of the second n-ZnO thin film layer, which is far away from the substrate, by using a BeZnOS ceramic target;preparing a first metal electrode layer on the surface of one side, away from the substrate, of the nitrogen-doped p-type conductive BeZnOS thin film layer;and preparing a second metal electrode layer on the surface of the part of the first n-ZnO film layer, which is positioned outside the second n-ZnO film layer.
- 4. The method of claim 3, wherein the step of preparing the first n-ZnO thin film layer on the surface of the substrate by using the ZnO ceramic target specifically comprises: and placing the substrate in a vacuum cavity of a pulsed laser deposition system, heating the substrate to 600-700 ℃, introducing oxygen into the vacuum cavity, adjusting the pressure of a growth chamber to 1-5 Pa, and preparing a first n-ZnO film layer on the substrate by using a ZnO ceramic target material and adopting a pulsed laser ablation method.
- 5. The method for preparing the ZnO-based homojunction self-driven ultraviolet photodetector as claimed in claim 3, wherein the step of preparing the nitrogen-doped p-type conductive BeZnOS thin film layer on the surface of the second n-ZnO thin film layer away from the substrate by using the BeZnOS ceramic target material specifically comprises the steps of:placing the substrate in a vacuum cavity of a pulse laser deposition system, heating the substrate to 300-500 ℃, introducing nitric oxide gas into the vacuum cavity, adjusting the pressure of a growth chamber to 3-7 Pa, and preparing a nitrogen-doped BeZnOS film on the surface of a second n-ZnO film layer by using a BeZnOS ceramic target material and adopting a pulse laser ablation method;and annealing the obtained nitrogen-doped BeZnOS thin film at 400-750 ℃ in the atmosphere of nitric oxide to obtain the nitrogen-doped p-type conductive BeZnOS thin film.
- 6. The method for preparing the ZnO-based homojunction self-driven ultraviolet photodetector as claimed in claim 3, wherein the method for preparing the ZnO ceramic target comprises:adding water into ZnO powder, ball-milling, and drying;pressing ZnO powder into a ZnO ceramic blank, and sintering the ZnO ceramic blank in a vacuum tube furnace at the temperature of 700-1300 ℃ to obtain the ZnO ceramic target.
- 7. The method for preparing the ZnO-based homojunction self-driven ultraviolet photodetector as claimed in claim 3, wherein the method for preparing the BeZnOS ceramic target material comprises the following steps:mixing ZnS powder and BeO powder and then carrying out ball milling to obtain mixed powder;pressing the mixed powder into a ceramic green sheet;and sintering the ceramic green sheet in a vacuum tube furnace at the temperature of 700-1300 ℃ by taking ZnS as an oxygen scavenger and argon as a protective gas to obtain the BeZnOS ceramic target.
- 8. The method for preparing the ZnO-based homojunction self-driven ultraviolet photodetector as claimed in claim 7, wherein the molar ratio of the ZnS powder to the BeO powder is 99:1 to 70: 30.
- 9. The method of claim 3, wherein the step of placing the substrate in a vacuum chamber of a pulsed laser deposition system further comprises the step of sequentially cleaning the substrate with acetone, absolute ethyl alcohol, and deionized water.
- 10. The method of fabricating a ZnO-based homojunction self-driven ultraviolet photodetector of claim 3, wherein the substrate comprises a c-plane sapphire substrate.
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