CN116154017A - Ultra-wideband photoelectric detector and preparation method thereof - Google Patents

Ultra-wideband photoelectric detector and preparation method thereof Download PDF

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CN116154017A
CN116154017A CN202310261427.6A CN202310261427A CN116154017A CN 116154017 A CN116154017 A CN 116154017A CN 202310261427 A CN202310261427 A CN 202310261427A CN 116154017 A CN116154017 A CN 116154017A
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layer
photoelectric conversion
ultra
electrode layer
wideband
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梁广兴
李传昊
苏正华
陈烁
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Shenzhen University
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Shenzhen University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
    • H01L31/0327—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4 characterised by the doping material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
    • H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by at least one potential-jump barrier or surface barrier, e.g. phototransistors
    • H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
    • H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier or surface barrier
    • H01L31/109—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier or surface barrier the potential barrier being of the PN heterojunction type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses an ultra-wideband photoelectric detector and a preparation method thereof, the ultra-wideband photoelectric detector comprises a substrate, a first electrode layer, a photoelectric conversion layer, a buffer layer, a window layer and a second electrode layer which are sequentially laminated, wherein the photoelectric conversion layer comprises Cu 2 Zn 1‑x Cd x Sn(Se 1‑y Te y ) 4 Wherein x is more than or equal to 0.6 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.2. The introduction of Cd in the invention can reduce copper-zinc inversion defects, and the introduction of Se and Te widens the spectral response range, so that the spectral response range of the photoelectric detector reaches 300-1700nm. The photoelectric detector provided by the invention has the advantages of high response speed, high response degree, wide spectral response range and excellent reliability.

Description

Ultra-wideband photoelectric detector and preparation method thereof
Technical Field
The invention relates to the technical field of photoelectric detection, in particular to an ultra-wideband photoelectric detector and a preparation method thereof.
Background
The photoelectric detector can convert optical signals into electric signals, is a basic element of a modern information processing system, wherein the application of a short wave infrared region is important for the activities of human beings in military and civil fields, such as telecom, space, remote sensing, guidance of a laser radiation system, soil moisture content, mineral identification and the like. In order to realize wide-spectrum light detection from visible light to near infrared region and realize the application requirements of environmental friendliness, low cost, high efficiency and stability, the self-driven thin film photoelectric detector with the thin film characteristic gradually becomes a research hot spot.
The semiconductor Copper Zinc Tin Sulfide (CZTS) has the advantages of abundant raw material reserves, green low toxicity, easy preparation, ideal band gap matching, high light absorption coefficient, excellent photoelectric performance and the like, so that the CZTS is used as the material of the photoelectric conversion layer of the photoelectric detector in the research started by the inventor, but the inventor finds that the spectral response range of the photoelectric detector is only 300-1000nm, and has a great difference in spectral response range compared with the mature commercial high-performance photoelectric detectors such as InGaAs, si and the like.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide an ultra-wideband photodetector and a preparation method thereof, which aims to solve the problem that the spectral response range of the photodetector using CZTS as the photoelectric conversion layer is narrower.
The technical scheme of the invention is as follows:
the first aspect of the present invention provides an ultra wideband photodetector, comprising a substrate, a first electrode layer, a photoelectric conversion layer, a buffer layer, a window layer and a second electrode layer, which are sequentially stacked, wherein the photoelectric conversion layer comprises Cu 2 Zn 1- x Cd x Sn(Se 1-y Te y ) 4 Wherein x is more than or equal to 0.6 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.2.
Optionally, the photoelectric conversion layer forms a heterojunction with the buffer layer.
Optionally, the buffer layer includes one of a CdS buffer layer and a zinc tin oxide buffer layer.
Optionally, the material of the window layer includes one of indium tin oxide and aluminum doped zinc oxide.
Optionally, the material of the first electrode layer includes Mo; the material of the second electrode layer comprises one of silver and gold.
Optionally, the thickness of the first electrode layer is 500-1000nm; the thickness of the photoelectric conversion layer is 1-1.5 mu m; the thickness of the buffer layer is 50-100nm; the thickness of the window layer is 300-800nm.
In a second aspect of the present invention, there is provided a method for manufacturing the ultra-wideband photodetector according to the present invention, including the steps of:
providing a substrate;
sequentially forming a first electrode layer, a photoelectric conversion layer, a buffer layer, a window layer and a second electrode layer on the substrate to obtain the ultra-wideband photoelectric detector;
wherein the photoelectric conversion layer comprises Cu 2 Zn 1-x Cd x Sn(Se 1-y Te y ) 4 ，0.6≤x≤1，0≤y≤0.2。
Optionally, forming the photoelectric conversion layer on the first electrode layer specifically includes the steps of:
according to Cu 2 Zn 1-x Cd x SnS 4 Adding a copper source, a zinc source, a cadmium source, a tin source and a sulfur source into a solvent according to the stoichiometric ratio of each element, and mixing to obtain a precursor solution;
coating the precursor solution on the first electrode layer at a preset temperature to prepare Cu on the first electrode layer 2 Zn 1-x Cd x SnS 4 A film;
according to Cu 2 Zn 1-x Cd x Sn(Se 1-y Te y ) 4 Stoichiometric ratio of each element of the Cu 2 Zn 1-x Cd x SnS 4 Carrying out selenization and tellurization treatment on the film simultaneously to obtain the photoelectric conversion layer;
wherein x is more than or equal to 0.6 and less than or equal to 1.
Optionally, the preset temperature is 270-300 ℃. Alternatively, the selenization and tellurization treatments employ temperatures of 500-600 ℃.
The beneficial effects are that: the book is provided withThe invention introduces Cd into CZTS, and replaces S with Se and Te to form Cu 2 Zn 1- x Cd x Sn(Se 1-y Te y ) 4 And a photoelectric conversion layer. Wherein, the introduction of Cd can reduce the copper-zinc dislocation defect and reduce the band gap of CZTS, so that Cu 2 Zn 1-x Cd x Sn(Se 1-y Te y ) 4 The band gap is narrower, and the spectral response range of the photoelectric detector is widened; meanwhile, the spectral response range can be further widened by introducing Se and Te, so that the spectral response range of the photodetector reaches 300-1700nm. The invention uses Cu 2 Zn 1-x Cd x Sn(Se 1-y Te y ) 4 As a photoelectric conversion layer, the photoelectric conversion layer has the advantages of narrow band gap, low defect concentration, high response speed (response time reaches ns level), high response (reaching 738 mA/W), wide spectral response range (300-1700 nm), excellent reliability (can bear high temperature of 100 ℃ and low temperature of-50 ℃ and has stable optical response after being placed indoors for half a year).
Drawings
Fig. 1 is an XRD pattern of the photoelectric conversion layer in examples 1 and 2 of the present invention.
FIG. 2 is a response spectrum of the photodetector prepared in example 1 of the present invention.
FIG. 3 is a graph showing the results of photoelectric response test of the photodetector prepared in example 1 of the present invention.
Detailed Description
The invention provides a self-driven film type photoelectric detector, a preparation method thereof and a heart rate sensor, and the invention is further described in detail below for making the purposes, technical schemes and effects of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The semiconductor CZTS has the advantages of abundant raw material reserves, green low toxicity, easy preparation, ideal band gap matching, high light absorption coefficient, excellent photoelectric performance and the like, so that the CZTS is used as the material of the photoelectric conversion layer of the photoelectric detector in the research started by the inventor, and the inventor discovers that the spectral response range of the photoelectric detector is only 300-1300nm, and the response time is increased from tens of milliseconds to tens of microseconds. There is still a great gap in spectral range and response speed compared to the research of high performance photodetectors such as the mature commercial InGaAs and Ge. Based on the above, the embodiment of the invention provides an ultra-wideband photoelectric detector, which is characterized by comprising a substrate, a first electrode layer, a photoelectric conversion layer, a buffer layer, a window layer and a second electrode layer which are sequentially stacked, wherein the photoelectric conversion layer comprises Cu 2 Zn 1-x Cd x Sn(Se 1-y Te y ) 4 Wherein x is more than or equal to 0.6 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.2.
The embodiment of the invention carries out continuous research in the prior research, introduces Cd in CZTS, and completely replaces S in the CZTS with Se and Te to form Cu 2 Zn 1-x Cd x Sn(Se 1-y Te y ) 4 And a photoelectric conversion layer. Wherein, the introduction of Cd can reduce the copper-zinc dislocation defect and reduce the band gap of CZTS, so that Cu 2 Zn 1-x Cd x Sn(Se 1-y Te y ) 4 The band gap is narrower, and the spectral response range of the photoelectric detector is widened; meanwhile, the spectral response range can be further widened by introducing Se and Te, so that the spectral response range of the photodetector reaches 300-1700nm. The invention uses Cu 2 Zn 1-x Cd x Sn(Se 1-y Te y ) 4 As a photoelectric conversion layer, the photoelectric conversion layer has the advantages of narrow band gap, low defect concentration, high response speed (response time reaches ns level), high response (reaching 738 mA/W), wide spectral response range (300-1700 nm), excellent reliability (can bear high temperature of 100 ℃ and low temperature of-50 ℃ and has stable optical response after being placed indoors for half a year).
In one embodiment, the thickness of the photoelectric conversion layer is 1 to 1.5 μm. For example, 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, or 1.5 μm may be used. The copper zinc tin sulfur-based film with the thickness has higher responsivity.
In one embodiment, the substrate includes, but is not limited to, one of a glass substrate, a stainless steel substrate.
In a specific embodiment, the glass substrate is a soda lime glass substrate, sodium diffuses into the photoelectric conversion layer, and the performance of the photoelectric detector can be improved.
In one embodiment, the thickness of the buffer layer is 50-100nm, for example, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, or the like. The buffer layer of this thickness facilitates the transmission of incident light and the collection of electrons.
In one embodiment, the photoelectric conversion layer forms a heterojunction with the buffer layer. In one embodiment, the buffer layer includes one of a CdS buffer layer, a zinc tin oxide buffer layer (i.e., a ZTO buffer layer, in which the zinc tin molar ratio is 1:1 to 4:1), but is not limited thereto. Currently, most photodetectors require an external bias voltage as a driving force to prevent recombination of photo-generated electron-hole pairs, which generates a large dark current, and thus challenges the application space and the lifetime. In the present embodiment, the CdS or ZTO buffer layer and Cu 2 Zn 1-x Cd x Sn(Se 1-y Te y. ) 4 The photoelectric conversion layer forms a PN junction, electrons and holes generated under illumination can be spontaneously separated, so that the photoelectric detector can generate a photoelectric conversion process without externally applying bias voltage, and the ultra-wideband photoelectric detector is a self-driven ultra-wideband photoelectric detector.
In one embodiment, the window layer has a thickness of 300-800nm, which may be 300nm, 400nm, 500nm, 600nm, 700nm, or 800nm, for example. The window layer of this thickness facilitates light transmission and has a small resistance value.
In one embodiment, the material of the window layer includes one of indium tin oxide and aluminum doped zinc oxide, but is not limited thereto.
In one embodiment, the first electrodeThe material of the layer includes, but is not limited to Mo. Mo vs Cu 2 Zn 1-x Cd x Sn(Se 1-y Te y ) 4 The photoelectric conversion layer has good adhesion, that is, cu 2 Zn 1-x Cd x Sn(Se 1-y Te y ) 4 Can be well adhered to Mo material to form photoelectric conversion layer, first electrode layer (Mo layer) and Cu 2 Zn 1-x Cd x Sn(Se 1-y Te y ) 4 The photoelectric conversion layer is tightly attached, so that the performance of the photoelectric detector is improved.
In one embodiment, the first electrode layer has a thickness of 500-1000nm.
In one embodiment, the material of the second electrode layer includes one of silver and gold, but is not limited thereto. The thickness of the second electrode layer is not limited, and may be set according to actual needs.
The embodiment of the invention also provides a preparation method of the self-driven film type photoelectric detector, which comprises the following steps:
s1, providing a substrate;
s2, sequentially forming a first electrode layer, a photoelectric conversion layer, a buffer layer, a window layer and a second electrode layer on the substrate to obtain the ultra-wideband photoelectric detector;
wherein the photoelectric conversion layer comprises Cu 2 Zn 1-x Cd x Sn(Se 1-y Te y ) 4 ，0.6≤x≤1，0≤y≤0.2。
The preparation method provided by the embodiment of the invention is simple and efficient, the prepared photoelectric detector has high response speed (the response time reaches ns level), high response (as high as 738 mA/W), wide spectral response range (300-1700 nm), excellent reliability (can bear high temperature of 100 ℃ and low temperature of 50 ℃ below zero), and stable optical response after being placed indoors for half a year).
In step S1, the specific type of the substrate may be referred to above, and will not be described herein.
In step S2, in one embodiment, a first electrode layer is formed on the substrate using a magnetron sputtering method. The substrate containing the first electrode layer is also commercially available. The material of the first electrode layer is described above, and will not be described here again.
In one embodiment, forming the photoelectric conversion layer on the first electrode layer specifically includes the steps of:
s211 according to Cu 2 Zn 1-x Cd x SnS 4 Adding a copper source, a zinc source, a cadmium source, a tin source and a sulfur source into a solvent according to the stoichiometric ratio of each element, and mixing to obtain a precursor solution;
s212, coating the precursor solution on the first electrode layer at a preset temperature to prepare Cu on the first electrode layer 2 Zn 1-x Cd x SnS 4 A film;
s213 according to Cu 2 Zn 1-x Cd x Sn(Se 1-y Te y ) 4 Stoichiometric ratio of each element of the Cu 2 Zn 1- x Cd x SnS 4 Carrying out selenization and tellurization treatment on the film simultaneously to obtain the photoelectric conversion layer;
wherein x is more than or equal to 0.6 and less than or equal to 1.
In the embodiment, the Cu-Zn-Cd-Sn-S film is improved on the basis of the Cu-Zn-Cd-Sn-S film so as to reduce the band gap width and widen the spectral response range. Wherein, the introduction of Cd can reduce the copper-zinc dislocation defect and reduce the band gap of CZTS, so that Cu 2 Zn 1-x Cd x Sn(Se 1-y Te y ) 4 The band gap is narrower, and the spectral response range of the photoelectric detector is widened; meanwhile, the spectral response range can be further widened by introducing Se and Te, so that the spectral response range of the photodetector reaches 300-1700nm. In the present embodiment, when y=0, cu 2 Zn 1-x Cd x SnSe 4 The spectral response of (C) can reach 300-1600nm, when 0<When y is less than or equal to 0.2, that is to say Cu 2 Zn 1-x Cd x SnSe 4 Te is introduced into to form Cu 2 Zn 1-x Cd x Sn(Se 1-y Te y ) 4 The spectral response range can be further widened to 3001700nm. The photoelectric conversion layer prepared by the solution coating method has the advantages of simplicity and low cost.
In step S211, in one embodiment, the copper source is at least one selected from cuprous chloride and cupric acetate, but is not limited thereto.
In one embodiment, the zinc source is selected from at least one of zinc acetate and zinc chloride, but is not limited thereto.
In one embodiment, the cadmium source is selected from at least one of cadmium chloride, cadmium sulfate, but is not limited thereto.
In one embodiment, the tin source is selected from at least one of tin tetrachloride and stannous chloride, but is not limited thereto.
In one embodiment, the sulfur source includes, but is not limited to, thiourea.
In one embodiment, the solvent includes, but is not limited to, ethylene glycol methyl ether.
In step S212, the preset temperature is 270-300 ℃. For example, 270 ℃, 280 ℃, 290 ℃, 300 ℃, or the like can be used.
In step S213, the selenization and tellurization processes are performed at a temperature of 500-600 ℃.
In specific implementation, the Cu can be prepared by 2 Zn 1-x Cd x SnS 4 The film is placed in a graphite box, a quartz boat containing selenium particles and tellurium particles (or selenium powder and tellurium powder) is placed in the graphite box, and then the graphite box is placed in a tubular furnace, argon is introduced at the temperature of 500-600 ℃, and selenization and tellurization are carried out simultaneously.
In step S2, in one embodiment, the method for preparing the buffer layer includes the steps of:
s221, mixing cadmium sulfate, thiourea, ammonia water and water to obtain a mixed solution;
s222, placing the substrate containing the first electrode layer and the photoelectric conversion layer into the mixed solution, and performing chemical water bath deposition at a preset temperature to obtain the CdS buffer layer.
In step S221, in one embodiment, the concentration of the cadmium sulfate in the mixed solution is 0.01-0.02mol/L, the concentration of the thiourea is 0.5-1mol/L, NH in the ammonia water 3 28-30% of ammonia water and water in a mass ratio of 1:7.
cadmium sulfide is insoluble in water and soluble in ammonia water, and as the heating reaction proceeds, the ammonia water volatilizes, so that the cadmium sulfide slowly separates out and is deposited on the photoelectric conversion layer.
In step S222, in one embodiment, the preset temperature is 75-85 ℃. For example, the temperature may be 75 ℃, 80 ℃, 85 ℃, or the like.
In step S2, the window layer may be prepared by using a magnetron sputtering method. The magnetron sputtering method is a method commonly used in the prior art, and will not be described here again. The material of the window layer is described above and will not be described in detail here.
The second electrode layer may be prepared by a thermal evaporation method, and in particular, an Ag electrode may be prepared by a thermal evaporation method. The thermal evaporation method is a method commonly used in the prior art, and is not described here again.
The following is a detailed description of specific examples.
Example 1
The embodiment provides an ultra-wideband photoelectric detector, which comprises a soda lime glass substrate, a Mo layer and Cu which are sequentially laminated 2 Zn 0.4 Cd 0.6 Sn(Se 0.9 Te 0.1 ) 4 The photoelectric conversion layer, the CdS buffer layer, the ITO window layer and the Ag electrode layer. Wherein the soda lime glass substrate has a thickness of 2mm, the Mo layer has a thickness of 800nm, cu 2 Zn 0.4 Cd 0.6 Sn(Se 0.9 Te 0.1 ) 4 The thickness of the photoelectric conversion layer was 1.3 μm, the thickness of the CdS buffer layer was 60nm, the thickness of the ITO window layer was 600nm, and the thickness of the Ag electrode layer was 800nm.
The preparation method of the ultra-wideband photoelectric detector comprises the following steps:
providing a soda lime glass substrate;
forming an Mo layer with the thickness of 800nm on a soda-lime glass substrate by adopting a magnetron sputtering method;
according to Cu 2 Zn 0.4 Cd 0.6 SnS 4 Stoichiometric ratio of each elementNamely adding 20mmol of cuprous chloride, 4mmol of zinc acetate, 6mmol of cadmium chloride, 10mmol of stannic chloride and 40mmol of thiourea into 20mL of ethylene glycol methyl ether according to the molar ratio of Cu to Zn to Cd to S=2:0.4:0.6:1:4, and uniformly mixing to obtain a precursor solution;
placing the glass substrate containing Mo layer on a 280 deg.C heating table, spin-coating the precursor solution on the Mo layer to form Cu with thickness of 1.3 μm 2 Zn 0.4 Cd 0.6 SnS 4 A precursor film;
will contain Cu 2 Zn 0.4 Cd 0.6 SnS 4 The precursor film and the soda lime glass substrate of the Mo layer are placed in an ink box according to Cu 2 Zn 0.4 Cd 0.6 Sn(Se 0.9 Te 0.1 ) 4 The stoichiometric ratio of each element is that a quartz boat with selenium particles and tellurium particles is put into a graphite box, then the graphite box is put into a tube furnace for heating at 555 ℃ and argon is introduced into the graphite box, and Cu is treated 2 Zn 0.4 Cd 0.6 SnS 4 Selenizing and tellurizing the precursor film to obtain Cu 2 Zn 0.4 Cd 0.6 Sn(Se 0.9 Te 0.1 ) 4 A photoelectric conversion layer;
adding cadmium sulfate, thiourea and ammonia water into water to form a mixed solution (wherein the concentration of the cadmium sulfate is 0.015mol/L, the concentration of the thiourea is 0.75mol/L and NH in the ammonia water) 3 28% by mass of ammonia water to water in a mass ratio of 1:7), in Cu 2 Zn 0.4 Cd 0.6 Sn(Se 0.9 Te 0.1 ) 4 Depositing on the photoelectric conversion layer in a chemical water bath at 80 ℃ for 9 minutes to obtain a CdS buffer layer with the thickness of 60 nm;
under the conditions of pressure and power of 0.4Pa and 120W respectively, an ITO window layer with the thickness of 600nm is deposited on the CdS buffer layer by magnetron sputtering;
an Ag electrode having a thickness of 800nm was thermally evaporated on the ITO window layer.
Example 2
The present embodiment provides an ultra-wideband photodetector, which differs from embodiment 1 only in that: the photoelectric conversion layer is Cu 2 CdSn(Se 0.9 Te 0.1 ) 4 。
The preparation method of the ultra-wideband photoelectric detector is different from embodiment 1 only in that:
according to Cu 2 CdSnS 4 The stoichiometric ratio of each element in (namely, according to the molar ratio of Cu: cd: sn: S=2:1:1:4), 20mmol of cuprous chloride, 10mmol of cadmium chloride, 10mmol of stannic chloride and 40mmol of thiourea are added into 20mL of ethylene glycol monomethyl ether to be uniformly mixed, so as to obtain a precursor solution;
according to Cu 2 CdSn(Se 0.9 Te 0.1 ) 4 The quartz boat with selenium particles and tellurium particles is placed into an ink box according to the stoichiometric ratio of each element.
And (3) testing:
(1) For Cu in examples 1 and 2 2 Zn 0.4 Cd 0.6 Sn(Se 0.9 Te 0.1 ) 4 、Cu 2 CdSn(Se 0.9 Te 0.1 ) 4 XRD test is carried out on the photoelectric conversion layer, and the result is shown in figure 1, so that both crystal forms are good, and no impurity peak appears.
(2) The responsivity test was performed on the photodetector in example 1, and the grating-controlled light source sequentially provided 300-1700nm monochromatic light (10 nm increase from 300nm, i.e., 300, 310, 320··1690, 1700 nm) and the source meter collected the current values generated by the detector under monochromatic light of different wavelengths, and the process was computer-controlled and data was collected. As a result, as shown in FIG. 2, it can be seen that the spectral response range of the photodetector in example 1 is wider than that of a commercial detector using Si as the photoelectric conversion material, and the wavelength range can be 300-1700nm. Wherein, the response degree reaches 738mA/W, and the response time is less than 100ns.
(3) The photodetector of example 1 was subjected to a light response test at 1550nm laser under the following conditions: 0V bias voltage and light intensity of 77mW/cm 2 The laser wavelength was 1550nm, and the result is shown in fig. 3, and it can be seen that the photodetector has a good stable optical response at 1550 nm.
(4) The photodetector in example 1 was left at 100℃and-50℃for 1 hour without a significant decrease in responsivity, and the photodetector in example 1 was still stable in optical response (slightly decreased in responsivity) after being left at room temperature for half a year, and it was found that the photodetector had excellent reliability and was able to withstand high temperatures of 100℃and low temperatures of-50 ℃.
In summary, the invention provides an ultra wideband photoelectric detector and a preparation method thereof, which introduces Cd in CZTS and completely replaces S therein with Se and Te to form Cu 2 Zn 1-x Cd x Sn(Se 1-y Te y ) 4 And a photoelectric conversion layer. Wherein the introduction of Cd can reduce the copper-zinc dislocation defect, reduce the band gap of CZTS or CZTSSe, and lead Cu to be 2 Zn 1-x Cd x Sn(Se 1-y Te y ) 4 The band gap is narrower, and the spectral response range of the photoelectric detector is widened; meanwhile, the spectral response range can be further widened by introducing Se and Te, so that the spectral response range of the photodetector reaches 300-1700nm. The invention uses Cu 2 Zn 1-x Cd x Sn(Se 1- y Te y ) 4 As a photoelectric conversion layer, the band gap is narrow, the defect concentration is low, and a heterojunction is formed through the cooperative regulation and control of the functional layer, so that self-driving work without external bias voltage is realized. The photoelectric detector provided by the invention has the advantages of high response speed (response time reaches ns level), high response (reaching 738 mA/W), wide spectral response range (300-1700 nm), excellent reliability (can bear high temperature of 100 ℃ and low temperature of minus 50 ℃, has stable optical response after being placed indoors for half a year), and can realize self-driven operation under no external bias.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.

Claims (10)

1. The ultra-wideband photoelectric detector is characterized by comprising a substrate, a first electrode layer, a photoelectric conversion layer, a buffer layer, a window layer and a second electrode layer which are sequentially laminated, wherein the photoelectric conversion layer comprises Cu 2 Zn 1-x Cd x Sn(Se 1-y Te y ) 4 Wherein 0.6≤x≤1，0≤y≤0.2。
2. The ultra-wideband photodetector of claim 1, wherein said photoelectric conversion layer forms a heterojunction with said buffer layer.
3. The ultra-wideband photodetector of claim 2, wherein said buffer layer comprises one of a CdS buffer layer, a zinc tin oxide buffer layer.
4. The ultra-wideband photodetector of claim 1, wherein the material of the window layer comprises one of indium tin oxide, aluminum doped zinc oxide.
5. The ultra-wideband photodetector of claim 1, wherein the material of said first electrode layer comprises Mo; the material of the second electrode layer comprises one of silver and gold.
6. The ultra-wideband photodetector of claim 1, wherein,
the thickness of the first electrode layer is 500-1000nm;
the thickness of the photoelectric conversion layer is 1-1.5 mu m;
the thickness of the buffer layer is 50-100nm;
the thickness of the window layer is 300-800nm.
7. A method of manufacturing an ultra-wideband photodetector as claimed in any one of claims 1 to 6, comprising the steps of:
providing a substrate;
sequentially forming a first electrode layer, a photoelectric conversion layer, a buffer layer, a window layer and a second electrode layer on the substrate to obtain the ultra-wideband photoelectric detector;
wherein the photoelectric conversion layer comprises Cu 2 Zn 1-x Cd x Sn(Se 1-y Te y ) 4 ，0.6≤x≤1，0≤y≤0.2。
8. The method of manufacturing according to claim 7, wherein forming the photoelectric conversion layer on the first electrode layer specifically includes the steps of:
according to Cu 2 Zn 1-x Cd x SnS 4 Adding a copper source, a zinc source, a cadmium source, a tin source and a sulfur source into a solvent according to the stoichiometric ratio of each element, and mixing to obtain a precursor solution;
coating the precursor solution on the first electrode layer at a preset temperature to prepare Cu on the first electrode layer 2 Zn 1-x Cd x SnS 4 A film;
according to Cu 2 Zn 1-x Cd x Sn(Se 1-y Te y ) 4 Stoichiometric ratio of each element of the Cu 2 Zn 1-x Cd x SnS 4 Carrying out selenization and tellurization treatment on the film simultaneously to obtain the photoelectric conversion layer;
wherein x is more than or equal to 0.6 and less than or equal to 1.
9. The method according to claim 8, wherein the preset temperature is 270 to 300 ℃.
10. The method of claim 8, wherein the selenization and tellurization treatments are performed at a temperature of 500-600 ℃.
CN202310261427.6A 2023-03-09 2023-03-09 Ultra-wideband photoelectric detector and preparation method thereof Pending CN116154017A (en)

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