CN114242832A - Quantum dot mid-infrared photoelectric detector and preparation method thereof - Google Patents
Quantum dot mid-infrared photoelectric detector and preparation method thereof Download PDFInfo
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- CN114242832A CN114242832A CN202111365975.0A CN202111365975A CN114242832A CN 114242832 A CN114242832 A CN 114242832A CN 202111365975 A CN202111365975 A CN 202111365975A CN 114242832 A CN114242832 A CN 114242832A
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- 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
- H01L31/0352—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035209—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
- H01L31/035218—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures the quantum structure being quantum dots
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- H01L31/0264—Inorganic materials
- H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
- H01L31/02963—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe characterised by the doping material
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Abstract
The invention relates to a quantum dot mid-infrared photoelectric detector and a preparation method thereof. The preparation method comprises the following steps: growing an indium gallium zinc oxide conductive channel layer on a silicon/silicon dioxide substrate; preparing a source electrode and a drain electrode on the surface of the indium gallium zinc oxide conducting channel layer; patterning the indium gallium zinc oxide conducting channel layer; preparing single crystal tin telluride colloid quantum dots by a thermal injection method; spin-coating the single-crystal tin telluride colloid quantum dots on the surface of the patterned indium gallium zinc oxide conductive channel layer to obtain an initial device; and annealing the initial device to obtain the quantum dot mid-infrared photoelectric detector. The quantum dot mid-infrared photoelectric detector prepared by the method can solve the problem of non-toxicity of mid-infrared quantum dot materials and the problem of widening the response waveband of the quantum dot detector.
Description
Technical Field
The invention relates to the technical field of nano material photoelectric detection, in particular to a quantum dot mid-infrared photoelectric detector and a preparation method thereof.
Background
The quantum dot has the advantages of adjustable band gap, unique light sensitivity, quantum effect, solution processing and the like, and is one of the core competitive materials of a photoelectric detector, particularly a non-refrigeration infrared detector. Most of the response wave bands of the quantum dot devices are only in visible and near infrared, and the response wave bands are difficult to be widened to the intermediate infrared wave bands. Only the mercury telluride quantum dot detector has the middle infrared detection performance. However, the mercury telluride is high in toxicity and unstable, so that the application range and reliability of the mercury telluride quantum dot detector are limited due to the easiness in degradation. Therefore, the development of a nontoxic and stable medium wave quantum dot detector is a key problem to be solved urgently.
The existing preparation methods of some nontoxic and stable medium wave quantum dot detectors mainly aim at thin film devices prepared by CVD, MBE and PVD methods, and the preparation cost is high. Moreover, no research on single-crystal tin telluride colloidal quantum dots exists, and no device structure of a detector combined with IGZO exists.
Disclosure of Invention
The invention provides a quantum dot mid-infrared photoelectric detector and a preparation method thereof, aiming at solving the problems of non-toxicity of mid-infrared quantum dot materials and widening of the response wave band of the quantum dot detector.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a preparation method of an infrared photoelectric detector in quantum dots, which comprises the following steps:
on silicon/silicon dioxide (Si/SiO)2) Growing an Indium Gallium Zinc Oxide (IGZO) conductive channel layer on the substrate;
preparing a source electrode and a drain electrode on the surface of the indium gallium zinc oxide conducting channel layer;
patterning the indium gallium zinc oxide conducting channel layer;
preparing single crystal tin telluride (SnTe) colloid quantum dots by a thermal injection method;
spin-coating the single-crystal tin telluride colloid quantum dots on the surface of the patterned indium gallium zinc oxide conductive channel layer to obtain an initial device;
and annealing the initial device to obtain the quantum dot mid-infrared photoelectric detector.
According to one aspect of the invention, a magnetron sputtering coating process is utilized to prepare a grown indium gallium zinc oxide film to form the indium gallium zinc oxide conductive channel layer, and an annealing process is utilized to enable the carrier mobility of the indium gallium zinc oxide conductive channel layer to be 9.23m2V-1s-1On/off ratio of 5X 107The thickness is 10 to 100 nm. The indium gallium zinc oxide conductive channel layer has proper thickness and conductivity to play the best carrier transmission role, and the conductivity of the IGZO film is controllable through an annealing process.
According to an aspect of the present invention, the process of preparing the source electrode and the drain electrode includes: patterning the photoresist by using an ultraviolet lithography technology, and evaporating and plating a titanium/gold (Ti/Au) composite electrode film by using a thermal evaporation coating process to prepare and form the source electrode and the drain electrode.
According to one aspect of the invention, the patterning process of the indium gallium zinc oxide conductive channel layer comprises the following steps: realizing photoresist patterning by utilizing an ultraviolet exposure process, and patterning the indium gallium zinc oxide conductive channel layer by utilizing a wet etching process;
the graphical indium gallium zinc oxide conductive channel layer is independent units which are not connected with each other, and the length/width size of each independent unit is any one of 100/100 micrometers, 100/80 micrometers, 100/60 micrometers, 100/40 micrometers, 100/20 micrometers and 100/10 micrometers.
According to one aspect of the present invention, the process of preparing single crystal tin telluride colloidal quantum dots using the thermal injection method includes:
dissolving a tellurium source in tri-n-octylphosphine, heating, refluxing and stirring in an inert atmosphere to fully dissolve the tellurium source to form a transparent light green solution with the concentration of 90-96 mg/mL, and taking the transparent light green solution as a reaction tellurium source; preferably, the concentration of the tellurium source is 92-95 mg/mL.
Adding bis [ bis (trimethylsilyl) amino ] tin (II) into octadecene, heating and stirring at 40-120 ℃ in an inert atmosphere to fully dissolve the bis [ bis (trimethylsilyl) amino ] tin (II) to form a solution with the concentration of 20-28 mg/mL, wherein the solution is used as a tin source for reaction; preferably, the concentration of the tin source is 20-25 mg/mL.
Injecting the tin source into the oleylamine solution containing the tellurium source at 120-180 ℃ by using a hot injection method, reacting for 1-10 min, and synthesizing the tin telluride quantum dots; preferably, the reaction temperature is 150 ℃ and the reaction time is 8-10 min.
And cooling the synthesized tin telluride quantum dots to room temperature in an ice water bath, adding a surfactant to obtain a tin telluride quantum dot colloid, adding acetone/chloroform into the tin telluride quantum dot colloid for centrifugation, removing the supernatant, dispersing the supernatant in a quantum dot solvent, repeating the steps for 2-3 times, performing acetone/absolute ethyl alcohol/chloroform centrifugal purification, removing the supernatant, dispersing the supernatant in the quantum dot solvent, and repeating the steps for 2-3 times to obtain the single crystal tin telluride colloid quantum dots with the concentration of 20 mg/mL.
Optionally, the surfactant is oleic acid or n-dodecyl mercaptan. Preferably, the surfactant is n-dodecyl mercaptan.
According to one aspect of the invention, the quantum dot solvent is chloroform, n-hexane, n-octane or toluene; preferably, the quantum dot solvent is chloroform.
The grain size distribution of the single crystal tin telluride colloidal quantum dots is 50-100 nm, and the crystal orientation is mainly (111).
According to one aspect of the invention, the process of spin-coating the single-crystal tin telluride colloidal quantum dots on the surface of the patterned indium gallium zinc oxide conductive channel layer to obtain the initial device comprises the following steps:
ligand replacement is carried out by using a short-chain ligand 2-nitrothiophene, and the long-chain ligand is replaced to increase the conductivity of the quantum dot;
through repeated spin coating and ligand replacement, the thickness of the quantum dot thin film layer is 500-1000 nm.
Preferably, the thickness of the quantum dot thin film layer is 500-700 nm.
According to one aspect of the invention, annealing operation is carried out on the initial device in a mode of gradient temperature rise and then cooling to room temperature, so as to obtain the quantum dot mid-infrared photoelectric detector, wherein the annealing temperature is 100-350 ℃, the annealing time is 1-4 hours, and the atmosphere is inert gas.
The invention also provides a quantum dot mid-infrared photoelectric detector prepared by the preparation method, which comprises a silicon/silicon dioxide substrate, an indium gallium zinc oxide conductive channel layer and a tin telluride quantum dot photosensitive layer from bottom to top, wherein two ends of the indium gallium zinc oxide conductive channel layer are respectively connected with a source electrode and a drain electrode, and silicon is used as a bottom grid.
According to another aspect of the invention, the silicon dioxide (SiO) in the silicon/silicon dioxide substrate2) The thickness of (A) is 50 to 200nm, and the thickness of silicon (Si) is 300 to 500 μm.
Preferably, the thickness of the silicon dioxide is 50-80 nm.
Has the advantages that:
according to the scheme of the invention, the quantum dots in the infrared detector in the SnTe quantum dots have single crystal characteristics, are mainly in the (111) crystal direction, have non-toxic and stable properties, and have photoelectric response in the waveband of 3-5 μm of mid-infrared. The colloid quantum dot has cheap raw materials and simple process, has good photoelectric characteristics such as high light absorption coefficient, adjustable forbidden bandwidth and the like, and provides a basis for the rapid application and development of colloid quantum dot materials in the photoelectric field.
The quantum dot mid-infrared photoelectric detector prepared by the preparation method of the quantum dot mid-infrared photoelectric detector comprises a tin telluride (SnTe) quantum dot photosensitive layer, an Indium Gallium Zinc Oxide (IGZO) conductive channel layer, and a Si/SiO2The photoelectric transistor device comprises a substrate, a source electrode, a drain electrode and a bottom grid. The SnTe quantum dots are excited by light to generate photon-generated carriers, and photocurrent is formed by source-drain voltages at two ends of the conductive channel layer, so that infrared photoelectric detection is realized. Then the IGZO current carrier is regulated and controlled by the bottom gateAnd the concentration improves the whole photoelectric responsivity and detectivity of the device.
Drawings
Fig. 1 schematically shows a flow chart of a method of manufacturing an infrared photodetector in quantum dots according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a structure of an infrared photodetector in quantum dots prepared according to an embodiment of the present invention;
FIG. 3 schematically shows an XRD spectrum of a tin telluride quantum dot prepared according to an embodiment of the present invention;
FIG. 4 is a Fourier infrared spectrum of a tin telluride quantum dot film prepared according to one embodiment of the present invention;
FIG. 5 schematically represents the optoelectronic data under 637nm laser irradiation according to the invention;
FIG. 6 is a schematic representation of the optoelectronic data of the present invention under 1310nm laser radiation;
FIG. 7 is a schematic representation of the optoelectronic data under irradiation by a 2000nm laser according to the present invention;
FIG. 8 schematically shows the optoelectronic data under 4000nm laser irradiation according to the invention.
Detailed Description
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 embodiments will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
The present invention is described in detail below with reference to the drawings and the specific embodiments, which are not repeated herein, but the embodiments of the present invention are not limited to the following embodiments.
Fig. 1 schematically shows a flowchart of a method for manufacturing an infrared photodetector in quantum dots according to various embodiments of the present invention. The following examples were carried out according to the preparation process scheme shown in FIG. 1.
Example 1
(1) In Si/SiO2On the substrate by magnetron sputtering on Ar/O2Growing an IGZO thin film with the thickness of about 10-100 nm in the mixed atmosphere. The IGZO thin film serves as a conductive channel layer. The background vacuum degree reaches 10-4～10-5Pa; the pressure in the chamber during growth is 0.7 Pa. Annealing the plated IGZO film at 200-500 ℃ to enable the carrier mobility to reach 9.23m2V-1s-1On/off ratio of 5X 107。
(2) And preparing a source electrode and a drain electrode on the surface of the IGZO thin film. Specifically, patterning of photoresist is realized through an ultraviolet exposure process or an ultraviolet lithography technology, and a Ti/Au composite electrode film is evaporated through a thermal evaporation coating process to be used as a source electrode and a drain electrode. Wherein the Ti film has a thickness of 5-10 nm, and the Au film has a thickness of 50-200 nm.
(3) And patterning the IGZO conductive channel layer. And patterning the photoresist by an ultraviolet exposure process, and patterning the IGZO conductive channel layer by using hydrochloric acid as an etching agent, wherein the patterned IGZO is an independent unit which is not connected with each other. The channel size (length/width) of the IGZO channel is any one of 100/100 μm, 100/80 μm, 100/60 μm, 100/40 μm, 100/20 μm and 100/10 μm.
(4) Preparing the single crystal SnTe colloid quantum dots. The single crystal SnTe colloidal quantum dots are prepared by a thermal injection method, the particle size distribution is 50-100 nm, and the crystal orientation is mainly (111), as shown in figure 3. The preparation method comprises the following specific steps:
a) preparation of tellurium source
And dissolving tellurium powder in tri-n-octylphosphine, heating, refluxing and stirring under an inert atmosphere to fully dissolve the tellurium powder, wherein the tellurium powder is transparent and light green after being dissolved and is used as a tellurium source for reaction, and the concentration is 90-96 mg/mL, preferably 92-95 mg/mL.
b) Preparation of tin source
Adding bis [ bis (trimethylsilyl) amino ] tin (II) into octadecene, heating and stirring under an inert atmosphere, and fully dissolving to obtain a tin source as a reaction tin source, wherein the concentration of the tin source is 20-28 mg/mL, the preferable dissolving temperature is 40-120 ℃, and the concentration of the tin source is 20-25 mg/mL.
c) Synthesis of tin telluride quantum dots
And injecting the tin source into the oleylamine solution containing the tellurium source at the temperature of 120-180 ℃ by using a hot injection method, and reacting for 1-10 min to obtain the tin telluride quantum dot. The preferable reaction temperature is 150 ℃, and the reaction time is 8-10 min. After the synthesis of the quantum dots is finished, the quantum dots are cooled to room temperature through an ice water bath, and a surfactant is added. The surfactant can be oleic acid, and can also be n-dodecanethiol, preferably n-dodecanethiol.
d) Centrifugal purification of tin telluride quantum dots
Adding acetone/chloroform into the prepared tin telluride quantum dot colloidal body for centrifugation, removing supernatant, dispersing in chloroform (quantum dot solvent), and repeating for 2-3 times; and then carrying out centrifugal purification by using acetone/absolute ethyl alcohol/chloroform, removing supernate, dispersing in chloroform (quantum dot solvent), and repeating for 2-3 times. The quantum dot solvent can be selected from chloroform, n-hexane, n-octane or toluene, preferably chloroform. And controlling the concentration of the tin telluride quantum dots to be about 20mg/mL for preparing the film.
(5) And (3) spin-coating the SnTe colloidal quantum dots obtained in the step (4) on the patterned IGZO surface in the step (3), and replacing ligands by using a short-chain ligand 2-nitrothiophene and replacing a long-chain ligand so as to increase the conductivity of the quantum dots. Multiple spin-coating and ligand replacement are required as necessary to achieve the desired thickness of the quantum dot film. The thickness of the quantum dot thin film layer is 500-1000 nm, and the preferred thickness is 500-700 nm.
(6) And (5) annealing the initial device obtained in the step (5) in the atmosphere of inert gas, heating in a gradient manner, then cooling to room temperature, and keeping the temperature constant to obtain the final intermediate infrared detection device. Wherein the annealing temperature is 100-350 ℃, and the annealing time is 1-4 h.
FIG. 4 is an infrared absorption spectrum of the thin film device, and it can be seen that the infrared absorption peak of the quantum dot thin film is just located at 3-5 μm of the mid-infrared, which also lays a foundation for the mid-infrared photoelectric response of the later device.
Example 2
(1) In Si/SiO2On the substrate by magnetron sputtering on Ar/O2Growing an IGZO thin film with the thickness of 40nm in the mixed atmosphere. IGZO thin film asIs a conductive channel layer. The background vacuum degree reaches 5 multiplied by 10-4Pa; the pressure in the chamber during growth is 0.7 Pa. The target material is prepared from the following components In, Ga, Zn and 2:2:1 In an atomic ratio of In, Ga, Zn and 99.99% In purity. And annealing the plated IGZO thin film at 350 ℃.
(2) And preparing a source electrode and a drain electrode on the surface of the IGZO. The patterning of the photoresist is realized through an ultraviolet exposure process or an ultraviolet lithography technology, and a Ti/Au composite electrode film is evaporated and plated through a thermal evaporation coating process to be used as a source electrode and a drain electrode. Wherein the Ti film has a thickness of 5-10 nm, and the Au film has a thickness of 50-200 nm.
(3) And patterning the IGZO conductive channel layer. And patterning the photoresist by an ultraviolet exposure process, and patterning the IGZO conductive channel layer by using hydrochloric acid as an etching agent, wherein the patterned IGZO is an independent unit which is not connected with each other. The IGZO channel has a rectangular structure with dimensions of 100 μm × 100 μm in length × width.
(4) Preparing the single crystal SnTe colloid quantum dots. The single crystal SnTe colloidal quantum dots are prepared by a thermal injection method, the particle size distribution is 50-100 nm, and the crystal orientation is mainly (111), as shown in figure 3. The preparation method comprises the following specific steps:
a) preparation of tellurium source
285mg of tellurium powder (Te) was weighed using an analytical balance, and then added to a three-necked flask, and 3.1mL of tri-n-octylphosphine (TOP) was added using a syringe while the mouth of the flask was plugged with a rubber stopper, ultrasonically dispersed for 30min, and then heated to be dissolved with an oil bath pan. During the dissolving process, magnetically stirring under the protection of inert gas, heating to 200 ℃ for reaction for 4h, and forming a tellurium source (Te/TOP) with the mass concentration of tellurium element of 92mg/mL after the tellurium powder is dissolved and turns into light green.
b) Preparation of tin source
10mL of octadecene was added to a round bottom flask and degassed by heating with magnetic stirring under inert gas. Then, 200uL of bis [ bis (trimethylsilyl) amino ] tin (II) was added at a concentration of 1.136g/mL using an injection syringe to dissolve the organotin sufficiently in octadecene. The degassing process described above, and also the addition of organotin, ensures that the tin source is not oxidized and is carried out in an inert gas atmosphere.
c) Synthesis of tin telluride quantum dots
After the tellurium source and the tin source are prepared according to the method in the steps a and b, in the quantum dot preparation process, the oleylamine is degassed in the same way, and the constant temperature is kept at 150 ℃. And after degassing, injecting a tin source into the oleylamine solution of Te/TOP by using an injector to react to generate the tin telluride quantum dot. And (3) the injection temperature of the tin source is 40 ℃, the reaction time is 8-10 min, after the reaction is finished, the temperature is rapidly cooled to room temperature by using an ice water bath, and then 2mL of n-dodecanethiol is added.
d) Centrifugal purification of tin telluride quantum dots
And adding chloroform and acetone into the tin telluride quantum dots, and carrying out centrifugal purification for 4-6 times. Firstly, centrifuging at the rotating speed of 4000-6000 r/min for 8-15 min, removing supernatant, adding chloroform, and then performing ultrasonic dispersion treatment; secondly, adding acetone, performing centrifugal operation at the rotating speed of 4000-6000 r/min for 5-10 min, removing supernate, adding chloroform, and performing ultrasonic dispersion treatment; thirdly, adding acetone and absolute ethyl alcohol, performing centrifugal operation at the rotating speed of 6000-9000 r/min for 8-15 min, removing supernate, adding chloroform, and performing ultrasonic dispersion treatment; the subsequent centrifugation processes of the fourth, fifth and sixth and third times are identical. And finally, adding the centrifuged tin telluride quantum dots into chloroform for dispersion and purification to obtain the tin telluride quantum dot colloidal solution with the concentration of about 20 mg/mL.
(5) And (3) depositing the tin telluride quantum dot colloid solution with the concentration of about 20mg/mL obtained in the step (4) on the IGZO surface patterned in the step (3) by using a spin coater at the rotation speed of 1500r/min for 30s, performing spin coating for three times for 3min, wherein the concentration of the ligand 2-nitrothiophene is 0.05mol/L, the solvent is absolute ethyl alcohol, and repeating the spin coating replacement process for 3 times to finally obtain the quantum dot thin film layer with the thickness of 500 nm.
(6) And (5) annealing the initial device obtained in the step (5), heating in a gradient manner, then cooling to room temperature, and keeping the temperature constant to obtain the final intermediate infrared detection device. Wherein the annealing temperature is 200 ℃, and the annealing time is 2 h.
As shown in fig. 2, by the quantum dots in the above two embodimentsThe infrared photoelectric detector in quantum dots prepared by the preparation method of the infrared photoelectric detector comprises a tin telluride (SnTe) quantum dot photosensitive layer, an Indium Gallium Zinc Oxide (IGZO) conductive channel layer, and a Si/SiO2The photoelectric transistor device comprises a substrate, a source electrode, a drain electrode and a bottom grid. The SnTe quantum dots are excited by light to generate photon-generated carriers, and photocurrent is formed by source-drain voltages at two ends of the conductive channel layer, so that infrared photoelectric detection is realized. And the IGZO carrier concentration is regulated and controlled through the bottom gate, so that the overall photoelectric responsivity and the detection rate of the device are improved.
The photoelectric response test is performed on the device, and fig. 5 to 8 are photoelectric switch diagrams of the device at 637nm,1310nm,2 μm and 4 μm wavelengths when the source-drain voltage is 10V and the gate voltage (Vg) is not applied. When the on-off state of the light source is switched, the device shows obvious on-off ratio from visible light to mid-infrared light and has obvious mid-infrared response characteristics.
Infrared photoelectric detector in quantum dot includes from bottom to top: silicon/silicon dioxide (Si/SiO)2) The substrate, Indium Gallium Zinc Oxide (IGZO) conducting channel layer and tin telluride (SnTe) quantum dot photosensitive layer, wherein two ends of the Indium Gallium Zinc Oxide (IGZO) conducting channel layer are respectively connected with the source electrode and the drain electrode, and silicon is used as a bottom grid electrode. Silicon dioxide (SiO) in silicon/silicon dioxide substrates2) The thickness of (A) is 50 to 200nm, and the thickness of silicon (Si) is 300 to 500 μm. Preferably, the thickness of the silicon dioxide is 50-80 nm.
The embodiment of the invention utilizes a chemical method to prepare the tin telluride colloidal quantum dot material, the tin telluride exists in a colloidal form, a large-area uniform conductive film can be formed on the surface of any substrate through a spin coating process, lattice matching is not needed, and the material preparation cost and the device preparation process cost are far lower than those of thin film devices prepared by CVD, MBE and PVD methods. The tin telluride quantum dot material prepared by the above embodiment of the invention takes (111) crystal orientation as a main part (as shown in fig. 3), and the interplanar spacing is 0.185 nm. The tin telluride colloid quantum dot material has the characteristic of mid-infrared absorption, and an IGZO is adopted as a transmission layer on the device structure, and quantum dots are used as an upper light absorption layer.
The size of the quantum dot can be regulated and controlled through a preparation process, so that the optical band gap of the quantum dot can be regulated and controlled, and the wavelength selectivity of the quantum dot photoelectric device is realized. This is incomparable with tin telluride thin film devices prepared by physical methods. Meanwhile, the intermediate infrared detection device based on the tin telluride quantum dots is expected to replace mercury telluride, becomes a next generation intermediate infrared quantum dot detector working at room temperature, and is a device for realizing intermediate infrared photoelectric response of the quantum dots for the first time in China.
The above description is only one embodiment of the present invention, and is not intended to limit the present invention, and it is apparent to those skilled in the art that various modifications and variations can be made in the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of an infrared photoelectric detector in quantum dots comprises the following steps:
growing an indium gallium zinc oxide conductive channel layer on a silicon/silicon dioxide substrate;
preparing a source electrode and a drain electrode on the surface of the indium gallium zinc oxide conducting channel layer;
patterning the indium gallium zinc oxide conducting channel layer;
preparing single crystal tin telluride colloid quantum dots by a thermal injection method;
spin-coating the single-crystal tin telluride colloid quantum dots on the surface of the patterned indium gallium zinc oxide conductive channel layer to obtain an initial device;
and annealing the initial device to obtain the quantum dot mid-infrared photoelectric detector.
2. The method as claimed in claim 1, wherein a magnetron sputtering coating process is used to prepare a grown InGaZn thin film to form the InGaZn conductive channel layer, and an annealing process is used to make the carrier mobility of the InGaZn conductive channel layer 9.23m2V-1s-1On/off ratio of 5X 107The thickness is 10 to 100 nm.
3. The method of claim 1, wherein the source and drain electrodes are prepared by a process comprising: patterning the photoresist by using an ultraviolet lithography technology, and evaporating and plating a titanium/gold composite electrode film by using a thermal evaporation coating process to prepare and form the source electrode and the drain electrode.
4. The method of claim 1, wherein the patterning of the indium gallium zinc oxide conductive channel layer comprises: realizing photoresist patterning by utilizing an ultraviolet exposure process, and patterning the indium gallium zinc oxide conductive channel layer by utilizing a wet etching process;
the graphical indium gallium zinc oxide conductive channel layer is independent units which are not connected with each other, and the length/width size of each independent unit is any one of 100/100 micrometers, 100/80 micrometers, 100/60 micrometers, 100/40 micrometers, 100/20 micrometers and 100/10 micrometers.
5. The method of claim 1, wherein the step of preparing the single crystal tin telluride colloidal quantum dots by the thermal injection method comprises:
dissolving a tellurium source in tri-n-octylphosphine, heating, refluxing and stirring in an inert atmosphere to fully dissolve the tellurium source to form a transparent light green solution with the concentration of 90-96 mg/mL, and taking the transparent light green solution as a reaction tellurium source;
adding bis [ bis (trimethylsilyl) amino ] tin (II) into octadecene, heating and stirring at 40-120 ℃ in an inert atmosphere to fully dissolve the bis [ bis (trimethylsilyl) amino ] tin (II) to form a solution with the concentration of 20-28 mg/mL, wherein the solution is used as a tin source for reaction;
injecting the tin source into the oleylamine solution containing the tellurium source at 120-180 ℃ by using a hot injection method, reacting for 1-10 min, and synthesizing the tin telluride quantum dots;
and cooling the synthesized tin telluride quantum dots to room temperature in an ice water bath, adding a surfactant to obtain a tin telluride quantum dot colloid, adding acetone/chloroform into the tin telluride quantum dot colloid for centrifugation, removing the supernatant, dispersing the supernatant in a quantum dot solvent, repeating the steps for 2-3 times, performing acetone/absolute ethyl alcohol/chloroform centrifugal purification, removing the supernatant, dispersing the supernatant in the quantum dot solvent, and repeating the steps for 2-3 times to obtain the single crystal tin telluride colloid quantum dots with the concentration of 20 mg/mL.
6. The method of claim 5, wherein the quantum dot solvent is chloroform, n-hexane, n-octane, or toluene;
the grain size distribution of the single crystal tin telluride colloidal quantum dots is 50-100 nm, and the crystal orientation is mainly (111).
7. The method of claim 1, wherein the step of spin-coating the single-crystal tin telluride colloidal quantum dots on the surface of the patterned indium gallium zinc oxide conductive channel layer to obtain the initial device comprises:
ligand replacement is carried out by using a short-chain ligand 2-nitrothiophene, and the long-chain ligand is replaced to increase the conductivity of the quantum dot;
through repeated spin coating and ligand replacement, the thickness of the quantum dot thin film layer is 500-1000 nm.
8. The method according to claim 1, wherein annealing operation is performed on the initial device in a mode of gradient temperature rise and then cooling to room temperature to obtain the quantum dot mid-infrared photoelectric detector, wherein the annealing temperature is 100-350 ℃, the annealing time is 1-4 hours, and the atmosphere is inert gas.
9. The quantum dot mid-infrared photoelectric detector prepared by the preparation method of claims 1 to 8 is characterized by comprising a silicon/silicon dioxide substrate, an indium gallium zinc oxide conductive channel layer and a tin telluride quantum dot photosensitive layer from bottom to top, wherein two ends of the indium gallium zinc oxide conductive channel layer are respectively connected with a source electrode and a drain electrode, and silicon is used as a bottom grid.
10. The quantum dot mid-infrared photodetector as claimed in claim 9, wherein the thickness of the silicon dioxide in the silicon/silicon dioxide substrate is 50-200 nm, and the thickness of the silicon is 300-500 μm.
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