CN116705890A - Self-powered broad-spectrum weak light signal detection photoelectric detection device and preparation method thereof - Google Patents
Self-powered broad-spectrum weak light signal detection photoelectric detection device and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a self-powered broad-spectrum weak light signal detection photoelectric detection device and a preparation method thereof. The method comprises the following steps: si is selected as a substrate; depositing a ZnO film by using a direct current magnetron sputtering technology; depositing an ITO electrode layer on the surface of the ZnO film; spin-coating an In electrode on the back surface of the Si substrate; based on the coupling effect of the ZnO nano rod array structure and the pyroelectric semiconductor, the device has obvious self-driven ultrahigh light response to the wavelength range of 405nm-1550nm, and realizes the detection of weak light signals of visible light and near infrared light. The photoelectric detection device has the advantages of high responsivity, high detection rate, high response speed, good cycle stability and the like; the preparation process is simple, nontoxic and pollution-free, has higher product quality, is suitable for large-scale industrial production, and has great application prospect in the field of high-performance weak light photoelectric detection devices.
Description
Technical Field
The invention relates to a self-powered broad spectrum weak light signal detection photoelectric detection device and a preparation method thereof, in particular to a Si/ZnO heterojunction structure photoelectric detection device and a preparation method thereof, and belongs to the field of semiconductor photoelectronic devices.
Background
In recent years, a self-powered broad-spectrum weak light signal detection photoelectric detection device has attracted wide attention from people at home and abroad, and the weak light signal detection device is required to have higher sensitivity and detection rate, so that the detection device can work under a low-power density light source. The self-powered photoelectric detection device reduces the energy cost and the complexity of circuit design, realizes energy conservation and environmental protection, and reduces the pollution to the environment. In addition, the wide spectrum detection realizes the detection of a plurality of wave band optical signals, and improves the selectivity of the device for optical transmission and reception.
However, in the existing semiconductor photoelectric detector, the background carrier density is too high, the dark current is large, the detection rate is low, the detection of weak light signals is limited, and the response range is single and the response speed is slow due to the influence of the band gap width of the material, so that the photoelectric conversion efficiency is reduced, and the application range of the device is limited.
For example:
chinese patent application CN114671626a discloses a ZnO quantum dot/magnetron sputtering ZnO homojunction ultraviolet photodetector and a method for preparing the same.
Chinese patent application CN113299537B discloses an integrated narrow-frame photodetector and a method for manufacturing the same, which adopts CVD method to improve the detection efficiency and response rate of the device.
Chinese patent application CN115332385a discloses an infrared avalanche photodetector based on macroscopic assembly graphene/epitaxial silicon schottky junction and a preparation method thereof, which realizes sensitive detection of weak light signals.
However, most of the ZnO-based photoelectric detection devices disclosed above have a light response function to ultraviolet light, cannot realize photoelectric detection in the ultraviolet-visible-near infrared broadband range, and are weak in detection to weak light signals.
How to develop semiconductor materials with broadband light response, and further, on this basis, develop self-powered photodetectors for detecting weak light signals, has become a technical problem to be solved by those skilled in the field of semiconductor materials and devices.
Disclosure of Invention
The invention aims to provide a self-powered broadband Si/ZnO heterojunction photoelectric detection device for detecting weak light signals.
The invention aims to solve the technical problems that how to improve the internal structure of the material used by the light detector, break through the limit of the band gap of the semiconductor material and widen the response wave band from ultraviolet to near infrared; namely, an ITO-ZnO/Si-In device structure is formed by preparing a ZnO nano rod array, and the high light absorption of the device is realized by utilizing the nano rod array mechanism; the unique pyroelectric effect of ZnO materials is utilized to form the high-efficiency conversion of light-heat-electricity-multi-physical field coupling, the temperature difference change is generated in the device, the current in the device is correspondingly changed, and the device detects the light; dark current of the heterojunction is restrained by utilizing a barrier interface coupled with Si, and the device is used for detecting weak light signals.
The technical scheme adopted by the invention for realizing the purpose is that the self-powered wide-spectrum weak light signal detection photoelectric detection device is characterized by sequentially comprising an In bottom electrode layer, a Si single crystal substrate, a ZnO film layer and an ITO upper electrode layer from bottom to top; wherein:
the Si single crystal substrate is a base, and the thickness of the Si single crystal substrate is 0.2mm;
the ZnO film layer is deposited on the surface of the substrate by a direct current magnetron sputtering technology, has a nano rod structure and has a thickness of 400-450nm;
the ITO upper electrode layer is deposited on the surface of the ZnO film layer through a direct current magnetron sputtering technology, and the thickness of the ITO upper electrode layer is 50-100nm;
the In bottom electrode layer is spin-coated on the back surface of the Si substrate through hot melting, and the thickness of the In bottom electrode layer is 0.1-0.5mm;
the technical proposal directly brings the technical effects that the preparation material and the structure are started, namely, the photo-thermal-electric multi-physical field coupling conversion is realized by forming a unique pyroelectric effect different from the traditional semiconductor in the ZnO film, and the effect does not depend on the band gap range of the semiconductor material, so that the photoelectric detector can achieve breakthrough promotion in the ultraviolet to near infrared different wavelength ranges;
through detection, the ITO-ZnO/Si-In photoelectric detection device of the technical scheme has stronger light detection capability In the ultra-wide wavelength range of 405nm-1550nm, and lambda=405 nm and P=500 nW/cm 2 When the response is 550.6mA/W, the response speed is 0.13ms;
and, unlike conventional semiconductor photodetector devices, the photodetector process of the device does not require any external bias voltage to drive operation, and has a self-powered effect at zero bias. The energy cost is reduced to a great extent, the degeneracy of the circuit design is enhanced, and the integration level of the device is improved;
in addition, the photodetector device has a structure of 7.7X10 12 The higher detection rate of Jones realizes 1 mu W/cm for 405nm visible light and 980nm near infrared light 2 And (5) detecting a weak light signal.
For a better understanding of the above technical solution, a detailed description will be made in principle:
1. the technical effects achieved by using the ZnO semiconductor film layer are as follows: (1) The structural characteristics with specific surface area enhance the interaction between light and substances; (2) The photoelectric detector has a unique pyroelectric effect, and can enhance the photoelectric-thermal-electric conversion of the photoelectric detector; (3) The large number of grain boundaries between the nano rods inhibit thermal diffusion in a plane, increase transient temperature gradient and enhance the pyroelectric effect in the ZnO film; (4) The formation of the interface barrier effectively reduces dark current and improves the detection capability of the device for low laser power; (5) As an oxide semiconductor device, it can effectively operate in an air environment for a long period of time, and is durable and stable.
2. In the technical scheme, the main reason for adopting the ITO conductive glass with the thickness of 50-100nm as the upper electrode is as follows: (1) The ITO conductive glass has strong conductive heat conduction property and ultrahigh transmittance, can keep good electron collection capability in an air environment, and has strong light transmission and heat transmission capability; (2) Ohmic contact is formed between the ITO conductive glass and the film, so that transportation of photo-generated carriers is promoted.
Experiments prove that the self-powered wide-spectrum weak light signal detection photoelectric detection device has the advantages of self-driving, wide light response wave band, high response speed, high detection rate of the weak light signal, high stability and the like.
The second purpose of the invention is to provide a preparation method of the self-powered wide-spectrum weak light signal detection photoelectric detection device, which has the advantages of simple process, high yield, energy conservation and environmental protection, meets the requirements of wide-spectrum weak light signal detection, and is suitable for large-scale industrial production.
The technical scheme adopted by the invention for achieving the purpose is that the preparation method of the self-powered wide-spectrum weak light signal detection photoelectric detection device is characterized by comprising the following steps:
first, a pretreatment step of a Si single crystal substrate:
sequentially placing the Si single crystal substrate in alcohol, acetone and alcohol for ultrasonic cleaning for 3min; and taking out, and drying by using high-purity nitrogen.
Second, a ZnO film layer deposition step:
loading the pretreated Si single crystal substrate into a tray, placing the tray into a vacuum chamber, pumping the vacuum chamber into a first high vacuum, regulating the mixed pressure of argon and oxygen to be 0.1-1.0Pa, and regulating the argon-oxygen ratio to be 20: and 5, adjusting the Si single crystal substrate to a first temperature of 500-550 ℃, bombarding the ZnO target material by using ionized particles by adopting a radio frequency magnetron sputtering technology, and depositing a ZnO film layer on the surface of the Si single crystal substrate.
Third, a deposition step of an ITO upper electrode:
after the sample is taken out from the vacuum chamber, a mask sheet with a round hole structure is covered on the surface, and the diameter of the round hole is 50 mu m-0.5mm. Then placing the sample in a tray, placing the sample in a vacuum chamber, and pumping the vacuum chamber into a second high vacuum; and (3) regulating the temperature of the sample covered with the mask plate to a second temperature of 200-250 ℃, regulating the argon pressure to a second pressure of 0.1-1.0Pa, bombarding the ITO target material with ionized ions under the condition of constant sputtering power of 20W by adopting a direct current magnetron sputtering technology, and depositing an ITO electrode layer on the surface of the ZnO film layer.
Fourth, spin coating the In bottom electrode:
heating to 150-200deg.C by using electric iron, melting metal indium wire, and spin-coating on the back of the Si monocrystal substrate.
3. The method for manufacturing a self-powered broad spectrum weak light signal detection photoelectric detection device according to claim 2, wherein the purity of the argon is more than 99.999%;
the film growth substrate is a Si single crystal substrate with (100) crystal face orientation;
the purity of the ZnO target material is 99.9%;
the purity of the ITO target is 99.99%;
the target base distance of the ZnO target and the ITO target is 35mm.
4. The method for manufacturing a self-powered broad spectrum weak light signal detection photoelectric detection device according to claim 2, wherein the first temperature is 500-550 ℃, and the first high vacuum is 1×10 -4 -5×10 -4 Pa, the first pressure is 0.1-1.0Pa.
5. The method for manufacturing a self-powered broad spectrum weak light signal detection photoelectric detector according to claim 2, wherein the second temperature is 200-250 ℃, and the second high vacuum is 1 x 10 -4 -5×10 -4 Pa, the second pressure is 0.1-1.0Pa.
Preferably, the purity of the argon gas is more than 99.999%;
the film growth substrate is a Si single crystal substrate with (100) crystal face orientation;
the purity of the ZnO target material is 99.9%;
the purity of the ITO target is 99.99%;
the target base distances of the ZnO target and the ITO target are 35mm;
the technical proposal directly brings the technical effects that the distance can not only meet the requirement that the ions collide with the working gas fully in the movement process to reduce the kinetic energy, but also ensure that the ions have enough adhesive force in the film forming process;
further preferably, the first temperature is 550 c,the first high vacuum is 5×10 -4 Pa, the first pressure is 0.6Pa.
The technical proposal directly brings the technical effects that the crystal quality and purity of the ZnO film can be improved, and the requirement that ions have enough adhesive force in the film forming process and a high-quality nano rod structure is grown can be met;
further preferably, the second temperature is 200deg.C and the second high vacuum is 5×10 -4 Pa, the second pressure being 1.0Pa;
the technical scheme directly brings the technical effects of further improving the film forming quality of the ITO electrode, improving the crystallinity of the film and ensuring that the ITO has enough adhesive force in the film forming process.
The technical proposal directly brings the technical effects of simple process, high yield, suitability for large-scale industrial production, no use of toxic and harmful raw materials, no generation of toxic and harmful waste or exhaust emission, and environment-friendly and pollution-free whole process flow.
In summary, compared with the prior art, the invention has the following beneficial effects:
1. the photoelectric detection device with the ITO-ZnO/Si-In structure has the advantages of self-driving, wide light response wave band, high response speed, high detection rate of low-light-level signals, high stability and the like, and can be used for detecting wide-spectrum low-light-level signals.
The ITO-ZnO/Si-In photoelectric detection device has obvious light response characteristics In the wavelength range of 405nm-1550nm under the condition of zero bias application: wherein, at λ=405 nm, p=500 nW/cm 2 When the responsivity is 550.6mA/W, the detection rate is as high as 7.7X10 12 Jones, response speed was 0.13ms.
2. The preparation method of the light detector has the characteristics of simple process, simple and convenient parameter control, high yield, suitability for large-scale industrial production, low manufacturing cost, energy conservation, environmental protection, stable product quality and the like.
Drawings
FIG. 1 is a schematic diagram of the structure of the ITO-ZnO/Si-In photoelectric detection device;
FIG. 2 is an X-ray diffraction pattern of the ZnO thin film prepared in the example;
FIG. 3 is an I-V curve of the ITO-ZnO/Si-In photodetector device prepared In the example under 405nm visible light irradiation and under dark conditions;
FIG. 4 shows that the ITO-ZnO/Si-In photodetector device prepared In the example has a 405nm laser of 1.0 μm/cm under no bias voltage 2 Dynamic response curve under weak light signal irradiation;
FIG. 5 shows 980nm laser 1.0 μm/cm under no bias voltage of the ITO-ZnO/Si-In photodetector device fabricated In the example 2 Dynamic response curve under weak light signal irradiation;
FIG. 6 is a graph showing the dynamic response of the ITO-ZnO/Si-In photodetector device prepared In the example under the irradiation of laser light of 355nm and 1550nm without bias voltage.
Detailed Description
The present invention will be described in detail with reference to the following examples and the accompanying drawings.
The preparation method comprises the following steps:
(1) Pretreatment of Si substrate:
sequentially placing the Si single crystal substrate in alcohol, acetone and alcohol for ultrasonic cleaning for 3min; and taking out, and drying by using high-purity nitrogen.
(2) The preparation method of the ZnO film layer comprises the following steps:
placing the Si single crystal substrate cleaned and dried by high-purity nitrogen into a tray, placing the tray into a vacuum chamber, and pumping the vacuum chamber to 5 multiplied by 10 -4 Pa, the mixed pressure of argon and oxygen is adjusted to be 0.6Pa, and the argon-oxygen ratio is 20: and 5, adjusting the temperature of the Si single crystal substrate to 550 ℃, bombarding the ZnO target material by using ionized particles by adopting a radio frequency magnetron sputtering technology, and depositing a ZnO film layer on the surface of the Si single crystal substrate.
(3) A step of depositing an electrode on ITO:
after the sample is taken out from the vacuum chamber, a mask sheet with a round hole structure is covered on the surface, and the diameter of the round hole is 50 mu m-0.5mm. The sample is then placed in a tray and placed in a vacuum chamber, which is evacuated to 5X 10 -4 Pa; and (3) regulating the temperature of the sample covered with the mask plate to 200 ℃, regulating the pressure of argon gas to 1.0Pa, adopting a direct current magnetron sputtering technology, bombarding an ITO target material with ionized ions under the condition of constant sputtering power of 20W, and depositing an ITO electrode layer on the surface of the ZnO film layer.
(4) Spin coating of In bottom electrode:
heating to 150-200deg.C by using electric iron, melting metal indium wire, and uniformly coating on the back of the sample Si monocrystal substrate as lower electrode.
Through detection, the prepared ITO-ZnO/Si-In photoelectric detection device has obvious light response characteristics In the wavelength range of 405nm-1550nm under the condition of zero bias application: wherein, at λ=405 nm, p=500 nW/cm 2 When the responsivity is 550.6mA/W, the detection rate is as high as 7.7X10 12 Jones, response speed was 0.13ms.
The following describes the detection results in detail with reference to the accompanying drawings:
FIG. 1 is a schematic diagram of the structure of the ITO-ZnO/Si-In photoelectric detection device;
as shown in the figure, si is used as a substrate, a ZnO film layer is arranged on the surface of the substrate, and ITO is used as an upper electrode and is arranged on the surface of the ZnO film layer. In is placed as a bottom electrode on the lower surface of the Si substrate.
FIG. 2 is an X-ray diffraction pattern of the ZnO thin film prepared in the example;
as shown in the figure, only one ZnO (002) crystal face with a diffraction peak of 34.32 degrees is shown in the figure. Thus, znO we prepared has a single crystal structure with preferential orientation of the C-axis.
FIG. 3 is an I-V curve of the ITO-ZnO/Si-In photodetector device prepared In the example under 405nm visible light irradiation and under dark conditions;
as shown in the figure, the surface of the device has obvious rectifying property and self-powered property.
FIG. 4 shows that the ITO-ZnO/Si-In photodetector device prepared In the example has a 405nm laser of 1.0 μm/cm under no bias voltage 2 Dynamic response curve under weak light signal irradiation;
as shown, the photoresponse has the unique four-stage pyroelectric characteristics of ZnO without an applied voltage; the response period is stable, and the self-driven rapid optical response is realized; there is still a significant response characteristic for weak light signals in the visible range.
FIG. 5 shows 980nm laser 1.0 μm/cm under no bias voltage of the ITO-ZnO/Si-In photodetector device fabricated In the example 2 Dynamic response curve under weak light signal irradiation;
as shown, in the absence of an applied voltage, there is still a distinct response characteristic for weak light signals in the near infrared range.
FIG. 6 is a graph showing the dynamic response of the ITO-ZnO/Si-In photodetector device prepared In the example under the irradiation of laser light of 355nm and 1550nm without bias voltage.
As shown, the device has obvious four-stage fast stable light response characteristics for incident light of ultraviolet 355nm and near infrared 1500 nm.
Claims (5)
1. A self-powered broad spectrum weak light signal detection photoelectric detection device and a preparation method thereof are characterized In that the device comprises a longitudinal layered superposition structure, an In bottom electrode layer, a Si single crystal substrate, a ZnO film layer and an ITO upper electrode layer from bottom to top In sequence; wherein:
the Si single crystal substrate is a coating substrate;
the ZnO film layer is deposited on the surface of the substrate through a direct current magnetron sputtering technology and is of a nano rod structure, and the thickness of the ZnO film layer is 400-450nm;
the ITO upper electrode layer is deposited on the surface of the ZnO film layer through a direct current magnetron sputtering technology;
and the In bottom electrode layer is spin-coated on the back surface of the Si substrate through an electric soldering iron.
2. A method of fabricating a self-powered broad spectrum weak light signal detection photodetecting device according to claim 1, comprising the steps of:
first, a pretreatment step of a Si single crystal substrate:
sequentially placing the Si single crystal substrate in alcohol, acetone and alcohol for ultrasonic cleaning for 3min; taking out, and drying with high-purity nitrogen;
second, a ZnO film layer deposition step:
the Si single crystal substrate which is cleaned and dried by high-purity nitrogen is put into a tray, and is put into a vacuum chamber, the vacuum chamber is pumped to a first high vacuum, the mixed pressure of argon and oxygen is regulated to be 0.1 Pa to 1.0Pa, and the ratio of argon to oxygen is 20:5, adjusting the Si single crystal substrate to a first temperature of 500-550 ℃, bombarding the ZnO target material by using ionized particles by adopting a radio frequency magnetron sputtering technology, and depositing a ZnO film layer on the surface of the Si single crystal substrate;
third, a deposition step of an ITO upper electrode:
after the sample is taken out from the vacuum chamber, a mask sheet with a round hole structure is covered on the surface, and the diameter of the round hole is 50 mu m-0.5mm. Then placing the sample in a tray, placing the sample in a vacuum chamber, and pumping the vacuum chamber into a second high vacuum; and (3) regulating the temperature of the sample covered with the mask plate to a second temperature of 200-250 ℃, regulating the argon pressure to a second pressure of 0.1-1.0Pa, bombarding the ITO target material with ionized ions under the condition of constant sputtering power of 20W by adopting a direct current magnetron sputtering technology, and depositing an ITO electrode layer on the surface of the ZnO film layer.
Fourth, spin coating the In bottom electrode:
and heating to 150-200 ℃ by using an electric iron, melting the metal indium wires, and uniformly coating the metal indium wires on the back surface of the Si single crystal substrate of the sample.
3. The method for manufacturing a self-powered broad spectrum weak light signal detection photoelectric detection device according to claim 2, wherein the purity of the argon is more than 99.999%;
the film growth substrate is a Si single crystal substrate with (100) crystal face orientation;
the purity of the ZnO target material is 99.9%;
the purity of the ITO target is 99.99%;
the target base distance of the ZnO target and the ITO target is 35mm.
4. The method for manufacturing a self-powered broad spectrum weak light signal detection photoelectric detection device according to claim 2, wherein the first temperature is 500-550 ℃, and the first high vacuum is 1×10 -4 -5×10 -4 Pa, the first pressure is 0.1-1.0Pa.
5. The method for manufacturing a self-powered broad spectrum weak light signal detection photoelectric detector according to claim 2, wherein the second temperature is 200-250 ℃, and the second high vacuum is 1 x 10 -4 -5×10 -4 Pa, the second pressure is 0.1-1.0Pa.
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