CN114899272A - Amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photoelectric detector and preparation method thereof - Google Patents
Amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photoelectric detector and preparation method thereof Download PDFInfo
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- 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
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- H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier or surface barrier
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Abstract
The invention discloses an amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector and a preparation method thereof.A layer of amorphous indium gallium zinc oxide film is deposited on a clean substrate by means of radio frequency magnetron sputtering, and the film is placed on a hot plate to finish annealing at a certain temperature and for a certain time; placing the annealed sample in a thermal evaporation coating machine to deposit a metal aluminum electrode, and depositing a lead sulfide quantum dot film of a 1, 2-Ethanedithiol (EDT) ligand with a certain thickness on the sample after the electrode deposition is finished by a solid ligand exchange method to obtain an amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector; the light responsivity is improved, a higher specific detectivity is obtained after a lower dark current and a higher photocurrent are obtained, and the response speed of the device is improved.
Description
Technical Field
The invention belongs to the technical field of semiconductors, and relates to an amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector and a preparation method thereof.
Background
Infrared photodetectors have a wide range of needs in the fields of industrial automation, unmanned driving, aerospace, remote sensing, imaging, optical communication, and the like. Currently, most of the commercialized infrared photodetectors employ an epitaxially grown semiconductor thin film as a light absorbing layer, such as InGaAs, HgCdTe, and the like. The semiconductor thin film needs expensive epitaxial growth equipment to deposit layer by layer, and the lattice matching and the thermal matching of the semiconductor thin film need to be strictly ensured in the deposition process, so that the equipment investment is high, the production cost is high and the process is complex in the device production process. With the rapid development of nano photoelectric materials such as quantum dots, perovskites and the like, researchers hope to replace the traditional epitaxial growth materials with the low-cost nano photoelectric materials to realize the design of a new generation of photoelectric detectors.
Taking the lead sulfide quantum dots prepared by the hot injection method as an example, the method has the following main advantages: (1) the band gap can be tuned by adjusting the size of the quantum dot, and the detection requirements of different wavelength ranges can be met; (2) the light absorption coefficient is high, the quantum dot film has excellent light absorption performance, the incident light can be fully absorbed within hundreds of nanometers, and meanwhile, the electrical performance of the lead sulfide quantum dot film can be remarkably improved after a proper ligand exchange process is adopted, so that the electrical performance of the film can meet the design requirement of a device; (3) the preparation process is simple, the investment on raw materials and equipment is low, the lead oxide and hexamethyldisilazane required by the preparation of the lead sulfide quantum dots are low-price chemicals, and the hot injection method adopted by the preparation does not need expensive equipment; (4) the method can be used for deposition by methods such as spin coating or blade coating, the deposition process is simple and low in cost, spin coating and blade coating equipment used for depositing the lead sulfide quantum dot film do not need high vacuum degree or inert gas atmosphere, the requirement on environment humidity is not strict, the preparation can be completed in an air environment, and the influence of the environment is small; (5) the requirements on lattice matching and thermal matching are low, the requirements on a substrate and annealing conditions are low, the device can be deposited on common clean white glass, and the lead sulfide quantum dot film does not need annealing; (6) the method has the potential of preparing flexible devices, and a certain amount of flexible lead sulfide quantum dot near-infrared detectors are reported at present. The application of the novel nano photoelectric material in the field of photoelectric detection is expected to remarkably reduce the device cost required by infrared photoelectric detection and meet the more extensive infrared detection requirement.
At this stage, lead sulfide quantum dots have been widely used in photodiodes, photoconductors, and photo field effect transistors. However, in the field of lead sulfide quantum dot based photoconductors, the problems of low optical responsivity, low specific detectivity and low response speed of devices still exist at present.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector and the preparation method thereof, which can obviously improve the photocurrent of the device, keep the dark current at a lower level and improve the response speed of the device.
In order to achieve the purpose, the application adopts the following technical scheme:
an amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector comprises a substrate, a radio frequency magnetron sputtering amorphous indium gallium zinc oxide film, an aluminum electrode and a 1, 2-ethanedithiol ligand lead sulfide quantum dot film deposited by a solid ligand exchange method from bottom to top in sequence.
A method for preparing amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photoelectric detector comprises the following steps:
step 1, placing a clean substrate and an indium gallium zinc oxide target material in a magnetron sputtering coating machine, vacuumizing, and introducing argon to finish radio frequency sputtering coating; taking out the sample, placing the sample on a high-temperature hot plate for annealing, and then placing the sample and high-purity aluminum wires in a thermal evaporation coating machine together to finish the deposition of an aluminum electrode;
step 2, adsorbing the sample obtained in the step 1 in a spin coater, covering a normal octane solution of lead sulfide quantum dots, performing spin coating, then covering an acetonitrile solution of 1, 2-ethanedithiol on the sample for a certain time, performing spin coating, then covering acetonitrile for multiple times, performing spin coating, covering acetonitrile again, and performing spin coating;
and repeating the step 2 for a plurality of times until a film with enough thickness is obtained, thus obtaining the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector.
Further, the substrate is a white glass substrate, a silicon substrate or a paper substrate.
Further, in the step 1, vacuum is pumped to 6X 10 -4 Introducing 45 milliliters of argon per minute in a standard state to finish radio frequency sputtering coating; in the sputtering process, the working air pressure of the magnetron sputtering coating machine is 0.36 Pa, the sputtering power is 60 watts, and the sputtering time is 5-20 minutes.
Further, annealing at 400 ℃ for 1 hour in the annealing in the step 1, cooling, putting the high-purity aluminum wire and the annealing in a thermal evaporation coating machine, and vacuumizing to 6 x 10 -4 Finishing the deposition of the aluminum electrode; the distance between the source electrode and the drain electrode of the electrode pattern is 100 microns, and the length-width ratio is 0.2.
Further, the concentration of the n-octane solution of the lead sulfide quantum dots covered in the step 2 is 20mg/mL, the speed of spin-coating the n-octane solution of the lead sulfide quantum dots is 3000 rpm, and the spin-coating time is 20 seconds.
Further, the concentration of the acetonitrile solution of the 1, 2-ethanedithiol covered in the step 2 is 0.02% by volume fraction, the covering time is 30 seconds, the speed of spin-coating the acetonitrile solution of the 1, 2-ethanedithiol is 3000 rpm, and the spin-coating time is 20 seconds; the speed of the spin coating of acetonitrile was 3000 rpm, and the spin coating time was 20 seconds.
Further, the preparation method of the lead sulfide quantum dots used in the n-octane solution of the lead sulfide quantum dots in the step 2 comprises the following steps:
step 1.1, filling 1.5mL of oleic acid, 35mL of octadecene, 0.4464 g of yellow lead oxide and a stirrer into a three-neck flask, vacuumizing, stirring and heating, wherein the reaction system is gradually clear and transparent; vacuumizing at the temperature and continuously stirring, then introducing nitrogen into the reaction system, vacuumizing, and repeating the process for many times to ensure that no water and no oxygen exist in the reaction system; heating the reaction system to 120 ℃, injecting 10mL of octadecylene solution of hexamethyldisilazane, closing a heat source to cool the reaction system to room temperature in a nitrogen environment after the hot injection is finished when the content of the hexamethyldisilazane in the solution is 2 mmol;
and step 1.2, adding methanol into the reaction product obtained in the step 1.1 until the solution is layered, discarding the supernatant through a separating funnel, adding sufficient acetone into the obtained black solution, centrifuging, discarding the supernatant, adding toluene to fully dissolve the precipitate, repeating the process for multiple times, and finally removing the toluene from the obtained precipitate, and performing vacuum drying to obtain the lead sulfide quantum dot with the first exciton absorption peak of 1100 nm.
Further, in the step 1.1, the oleic acid, the octadecene, the yellow lead oxide and the stirrer are placed in a three-necked flask, vacuumized, stirred for 20 minutes, heated to 95 ℃, the reaction system is gradually clear and transparent, and vacuumized at the temperature and continuously stirred for 2 hours.
Further, 20mL of methanol was added to the reaction product of step 1.1 in 1.2 until the solution was separated into layers, and the amount of toluene added was 1mL each time.
Compared with the prior art, the invention has the advantages that:
(1) the nano indium gallium zinc oxide layer prepared by introducing a layer of radio frequency magnetron sputtering promotes the separation of photon-generated carriers of the lead sulfide quantum dot layer through a p-n junction at the interface of the indium gallium zinc oxide layer and the lead sulfide quantum dot layer, and separated photon-generated electrons enter the indium gallium zinc oxide layer with high carrier mobility from the quantum electrical layer with low carrier mobility, so that the photocurrent of the device is obviously improved, namely the photoresponse is improved.
(2) The carrier concentration of the indium gallium zinc oxide layer deposited by the method is low, and the dark current of the indium gallium zinc oxide layer is similar to that of the lead sulfide quantum dot layer adopted by the method in a dark state, so that the dark current of the device can be kept at a lower level. After the low dark current and the high photocurrent are obtained simultaneously, the device obtains high specific detectivity.
(3) The amorphous indium gallium zinc oxide film adopted by the invention has high carrier mobility, and forms a p-n junction with the lead sulfide quantum dot film adopted by the invention, and under the action of an internal electric field, photo-generated electrons generated in the lead sulfide quantum dot layer are injected into the amorphous indium gallium zinc oxide layer to obtain larger photo-generated current, so that the device obtains high light responsivity and high specific detection rate, and the detection performance is improved.
(4) The sputtering power, the film thickness and the annealing process of the amorphous indium gallium zinc oxide film are designed according to the energy band structure and the electrical property characteristics of the lead sulfide quantum dots, and the adopted amorphous indium gallium zinc oxide film has the characteristics of low carrier concentration and high carrier mobility. Compared with the lead sulfide quantum dot single-layer photoconductor prepared by the same process, the response speed of the device is improved by introducing amorphous indium gallium zinc oxide.
(5) The selection of the aluminum electrode, the design of depositing the aluminum electrode on the amorphous indium gallium zinc oxide layer and then depositing the lead sulfide quantum dot layer and the design of the channel spacing ensure that the performance of the device is ensured, meanwhile, the cost of the device is maintained at a lower level, and the aluminum metal and the thermal evaporation coating method electrode deposition process do not need high material and equipment investment.
(6) The process for depositing the indium gallium zinc oxide film by the radio frequency magnetron sputtering method is stable, the utilization rate of raw materials is high, the cost is low, and the requirement of large-scale preparation is met.
(7) The preparation and deposition process of the lead sulfide quantum dots adopted by the invention has the advantages of low raw material cost, no need of high vacuum or inert gas atmosphere, stable process and long-term preservation of products. The invention fully considers the problem of cost control in the design link of the device.
Drawings
FIG. 1 is a schematic diagram of a device structure of the present invention;
fig. 2 is a typical dark current/photocurrent diagram of an amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector prepared in example 1;
fig. 3 is a photo current comparison graph of the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector prepared in example 1 and a device without an indium gallium zinc oxide layer irradiated by the same incident light and having the same other processes;
FIG. 4 is a graph of the specific detectivity of the amorphous InGaZn/Pb quantum dot double-layer heterojunction photoconductive photodetector prepared in example 1 as a function of incident light power;
fig. 5 is a graph showing the response speed of the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector prepared in example 1 as a function of incident light power.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below.
The invention discloses a preparation method of an amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photoelectric detector, which comprises the following steps:
firstly, the preparation of the lead sulfide quantum dots with the first exciton absorption peak of 1100 nm or 1400 nm is realized by adopting a thermal injection method, the quantum dots are cleaned, and the quantum dots are dissolved in n-octane at a certain concentration after being dried in vacuum. Depositing amorphous indium gallium zinc oxide film on a substrate by means of radio frequency magnetron sputtering under certain process conditions, taking out the film, placing the film on a high-temperature hot plate for annealing, cooling, and placing the film and a high-purity aluminum wire in a thermal evaporation coating machine to finish the evaporation of an aluminum electrode. Placing the sample on which the electrode is deposited in a spin coating machine, and spin-coating lead sulfide quantum dots; covering the acetonitrile solution of the 1, 2-ethanedithiol for a certain time, and spin-coating; covering with acetonitrile, and spin-coating; and again covered with acetonitrile and spin coated. This process, known as "solid-state ligand exchange", is repeated a number of times to obtain a sufficient thickness of the lead sulfide quantum dot film.
Specifically, the present invention may be based on the schematic device structure shown in fig. 1, and the detailed steps are as follows:
a preparation method of an amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photoelectric detector comprises the following steps:
1) a three-necked flask was charged with 1.5mL oleic acid (or 22mL), 35mL octadecene (or 44mL), and 0.4464 g (or 0.8928 g) yellow lead oxide with a stir bar. The three-necked flask was evacuated and then stirred. After 20 minutes, the temperature is raised to 95 ℃, at which time the reaction system is gradually clear and transparent, and the reaction system is stirred at the temperature for 2 hours under vacuum. And introducing nitrogen into the reaction system, vacuumizing, and repeating the process for three times to ensure that no water and no oxygen exist in the reaction system. The reaction was warmed to 120 ℃. 10mL of a solution of hexamethyldisilazane in octadecylene was injected into the reaction system, and the content of hexamethyldisilazane in the solution was 2mmol (or 4 mmol). After completion of the hot injection, the heat source was immediately turned off, and the reaction system was allowed to cool to room temperature in a nitrogen atmosphere.
2) To the reaction product in step 1), 20mL of methanol (or 40mL) was added until the solution was separated, and the supernatant was discarded through a separatory funnel. To the resulting black solution was added sufficient acetone, centrifuged, the supernatant discarded, and 1mL (or 2mL) of toluene was added to dissolve the precipitate sufficiently, and the process was repeated three times. Finally, the obtained precipitate is not added with toluene any more, and is dried overnight in vacuum, and the lead sulfide quantum dot with the first exciton absorption peak of 1100 nanometers (or 1400 nanometers) is obtained.
3) Putting clean white glass substrate or silicon substrate or paper substrate and indium gallium zinc oxide target material into a magnetron sputtering coating machine, vacuumizing to 6 x 10 -4 And introducing 45 mL of argon per minute in a standard state to finish the radio-frequency sputtering coating. In the sputtering process, the working air pressure of the magnetron sputtering coating machine is 0.36 Pa, the sputtering power is 60 watts, and the sputtering time is 5-20 minutes. Taking out the sample after the radio frequency sputtering coating, placing the sample on a high-temperature hot plate, annealing for 1 hour at 400 ℃, placing the sample and the high-purity aluminum wire in a thermal evaporation coating machine after cooling, and vacuumizing to 6 multiplied by 10 -4 And (5) finishing the deposition of the aluminum electrode. The distance between the source electrode and the drain electrode of the electrode pattern used in the process is 100 microns, and the length-width ratio is 0.2.
4) Adsorbing the sample obtained in the step 3) in a spin coater, covering with a normal octane solution of the lead sulfide quantum dots, and spin-coating. In the process, the concentration of the n-octane solution of the lead sulfide quantum dots is 20mg/mL, the spin-coating speed is 3000 rpm, and the spin-coating time is 20 seconds. The sample was then coated with a solution of 1, 2-ethanedithiol in acetonitrile for a certain period of time and spin-coated. In the process, the concentration of acetonitrile solution of the 1, 2-ethanedithiol is 0.02 percent by volume, the covering time is 30 seconds, the spin-coating speed is 3000 rpm, and the spin-coating time is 20 seconds. Subsequently, the substrate was covered with acetonitrile, spin-coated, and then covered with acetonitrile, at a spin speed of 3000 rpm for 20 seconds. The steps are repeated for three times to obtain a film with enough thickness, and the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photoelectric detector is obtained.
The following are several specific examples.
Example 1:
1) a three-necked flask was charged with 1.5mL of oleic acid, 35mL of octadecene, and 0.4464 yellow lead oxide with a stir bar. The three-necked flask was evacuated and then stirred. After 20 minutes, the temperature is raised to 95 ℃, at which time the reaction system is gradually clear and transparent, and the reaction system is stirred at the temperature for 2 hours under vacuum. And introducing nitrogen into the reaction system, vacuumizing, and repeating the process for three times to ensure that no water and no oxygen exist in the reaction system. The reaction was warmed to 120 ℃. 10mL of an octadecylene solution of hexamethyldisilazane was injected into the reaction system, and the content of hexamethyldisilazane in the solution was 2 mmol. After completion of the hot injection, the heat source was immediately turned off, and the reaction system was allowed to cool to room temperature in a nitrogen atmosphere.
2) To the reaction product in step 1), 20mL of methanol was added until the solution was separated, and the supernatant was discarded through a separatory funnel. To the resulting black solution was added sufficient acetone, centrifuged, the supernatant discarded, and 1mL of toluene was added to dissolve the precipitate sufficiently, and the process was repeated three times. And finally, the obtained precipitate is not added with toluene any more, and is dried overnight in vacuum, so that the lead sulfide quantum dot with the first exciton absorption peak of 1100 nm is obtained.
3) Putting the clean white glass substrate and indium gallium zinc oxide target material in a magnetron sputtering coating machine, vacuumizing to 6 multiplied by 10 -4 And introducing 45 mL of argon per minute in a standard state to finish the radio-frequency sputtering coating. The working air pressure of the magnetron sputtering film plating machine in the sputtering process is 0.36 Pa, the sputtering power is 60 watts, and the sputtering time is 5 minutes. Taking out the sample after the radio frequency sputtering coating, placing the sample on a high-temperature hot plate, annealing for 1 hour at 400 ℃, placing the sample and the high-purity aluminum wire in a thermal evaporation coating machine after cooling, and vacuumizing to 6 multiplied by 10 -4 And (5) finishing the deposition of the aluminum electrode. The distance between the source electrode and the drain electrode of the electrode pattern used in the process is 100 microns, and the length-width ratio is 0.2.
4) Adsorbing the sample obtained in the step 3) in a spin coater, covering with a normal octane solution of the lead sulfide quantum dots, and spin-coating. In the process, the concentration of the n-octane solution of the lead sulfide quantum dots is 20mg/mL, the spin-coating speed is 3000 rpm, and the spin-coating time is 20 seconds. The sample was then coated with a solution of 1, 2-ethanedithiol in acetonitrile for a certain period of time and spin-coated. In the process, the concentration of acetonitrile solution of the 1, 2-ethanedithiol is 0.02 percent by volume, the covering time is 30 seconds, the spin-coating speed is 3000 rpm, and the spin-coating time is 20 seconds. Subsequently, the substrate was covered with acetonitrile, spin-coated, and then covered with acetonitrile, at a spin speed of 3000 rpm for 20 seconds. The steps are repeated for three times to obtain a film with enough thickness, and the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photoelectric detector is obtained.
Fig. 2 is a typical dark current/photocurrent diagram of the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector prepared in example 1, and it can be seen that the device exhibits a photocurrent in excess of 0.1 ma under irradiation of 1064 nm near-infrared light with a power of 11.3 microwatts, the dark current of the device is maintained in nanoampere level, and the signal-to-noise ratio of the device can reach 3.1 × 10 under a bias voltage of +40 v 5 。
Fig. 3 is a comparative graph of photocurrent of the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector prepared in example 1 under 1064 nm near-infrared light irradiation with power of 11.3 microwatts and photocurrent of a device without an indium gallium zinc oxide layer under the same incident light irradiation and with the same other processes. Therefore, the photocurrent of the device is improved by 3000 times by introducing the amorphous indium gallium zinc oxide layer.
Fig. 4 is a graph showing the change of specific detectivity of the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector prepared in example 1 with incident light power, which shows that the device has high specific detectivity and the specific detectivity of the device increases with the decrease of incident light power.
Fig. 5 is a graph showing the response speed of the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector prepared in example 1 as a function of incident light power, and it can be seen that the response speed of the device increases as the incident light power increases. The device of the invention exhibits a rise time of 1 millisecond and a fall time of 6 milliseconds under irradiation with 1064 nanometer near infrared light at a power of 11.3 microwatts; under the same incident light irradiation and other processes, the rise time and the fall time of the device without the indium gallium zinc oxide layer are respectively 4 milliseconds and 56 milliseconds, which proves that the response speed of the device is improved by introducing the indium gallium zinc oxide layer.
Example 2
1) A three-necked flask was charged with 1.5mL of oleic acid, 35mL of octadecene, and 0.4464 g of yellow lead oxide with a stir bar. The three-necked flask was evacuated and then stirred. After 20 minutes, the temperature is raised to 95 ℃, at which time the reaction system is gradually clear and transparent, and the reaction system is stirred at the temperature for 2 hours under vacuum. And introducing nitrogen into the reaction system, vacuumizing, and repeating the process for three times to ensure that no water and no oxygen exist in the reaction system. The reaction was warmed to 120 ℃. 10mL of an octadecylene solution of hexamethyldisilazane was injected into the reaction system, and the content of hexamethyldisilazane in the solution was 2 mmol. After completion of the hot injection, the heat source was immediately turned off, and the reaction system was allowed to cool to room temperature in a nitrogen atmosphere.
2) To the reaction product in step 1), 20mL of methanol was added until the solution was separated, and the supernatant was discarded through a separatory funnel. To the resulting black solution was added sufficient acetone, centrifuged, the supernatant discarded, and 1mL of toluene was added to dissolve the precipitate sufficiently, and the process was repeated three times. And finally, the obtained precipitate is not added with toluene any more, and is dried overnight in vacuum, so that the lead sulfide quantum dot with the first exciton absorption peak of 1100 nm is obtained.
3) Putting clean white glass and indium gallium zinc oxide target material in a magnetron sputtering coating machine, vacuumizing to 6 x 10 -4 And introducing 45 mL of argon per minute in a standard state to finish the radio-frequency sputtering coating. The working air pressure of the magnetron sputtering film plating machine in the sputtering process is 0.36 Pa, the sputtering power is 60 watts, and the sputtering time is 10 minutes. Taking out the sample after the radio frequency sputtering coating, placing the sample on a high-temperature hot plate, annealing for 1 hour at 400 ℃, placing the sample and the high-purity aluminum wire in a thermal evaporation coating machine after cooling, and vacuumizing to 6 multiplied by 10 -4 And (5) finishing the deposition of the aluminum electrode. The distance between the source and drain electrodes of the electrode pattern used in the process is 100 micronsThe aspect ratio was 0.2.
4) Adsorbing the sample obtained in the step 3) in a spin coater, covering with a normal octane solution of the lead sulfide quantum dots, and spin-coating. In the process, the concentration of the n-octane solution of the lead sulfide quantum dots is 20mg/mL, the spin-coating speed is 3000 rpm, and the spin-coating time is 20 seconds. The sample was then coated with a solution of 1, 2-ethanedithiol in acetonitrile for a certain period of time and spin-coated. In the process, the concentration of acetonitrile solution of the 1, 2-ethanedithiol is 0.02 percent by volume, the covering time is 30 seconds, the spin-coating speed is 3000 rpm, and the spin-coating time is 20 seconds. Subsequently, the substrate was covered with acetonitrile, spin-coated, and then covered with acetonitrile, at a spin speed of 3000 rpm for 20 seconds. The steps are repeated for three times to obtain a film with enough thickness, and the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photoelectric detector is obtained.
Example 3
1) A three-necked flask was charged with 1.5mL of oleic acid, 35mL of octadecene, and 0.4464 g of yellow lead oxide with a stir bar. The three-necked flask was evacuated and then stirred. After 20 minutes, the temperature is raised to 95 ℃, at which time the reaction system is gradually clear and transparent, and the reaction system is stirred at the temperature for 2 hours under vacuum. And introducing nitrogen into the reaction system, vacuumizing, and repeating the process for three times to ensure that no water and no oxygen exist in the reaction system. The reaction was warmed to 120 ℃. 10mL of an octadecylene solution of hexamethyldisilazane was injected into the reaction system, and the content of hexamethyldisilazane in the solution was 2 mmol. After completion of the hot injection, the heat source was immediately turned off, and the reaction system was allowed to cool to room temperature in a nitrogen atmosphere.
2) To the reaction product in step 1), 20mL of methanol was added until the solution was separated, and the supernatant was discarded through a separatory funnel. To the resulting black solution was added sufficient acetone, centrifuged, the supernatant discarded, and 1mL of toluene was added to dissolve the precipitate sufficiently, and the process was repeated three times. And finally, the obtained precipitate is not added with toluene any more, and is dried overnight in vacuum, so that the lead sulfide quantum dot with the first exciton absorption peak of 1100 nm is obtained.
3) Putting the clean white glass substrate and indium gallium zinc oxide target material in a magnetron sputtering coating machine, vacuumizing to 6 multiplied by 10 -4 Perca, 45 mL of standard mL per minute was introducedAnd (4) finishing the radio-frequency sputtering coating. The working air pressure of the magnetron sputtering film plating machine in the sputtering process is 0.36 Pa, the sputtering power is 60 watts, and the sputtering time is 20 minutes. Taking out the sample after the radio frequency sputtering coating, placing the sample on a high-temperature hot plate, annealing for 1 hour at 400 ℃, placing the sample and the high-purity aluminum wire in a thermal evaporation coating machine after cooling, and vacuumizing to 6 multiplied by 10 -4 And (5) finishing the deposition of the aluminum electrode. The distance between the source electrode and the drain electrode of the electrode pattern used in the process is 100 microns, and the length-width ratio is 0.2.
4) Adsorbing the sample obtained in the step 3) in a spin coater, covering with a normal octane solution of the lead sulfide quantum dots, and spin-coating. In the process, the concentration of the n-octane solution of the lead sulfide quantum dots is 20mg/mL, the spin-coating speed is 3000 rpm, and the spin-coating time is 20 seconds. The sample was then coated with a solution of 1, 2-ethanedithiol in acetonitrile for a certain period of time and spin-coated. In the process, the concentration of acetonitrile solution of the 1, 2-ethanedithiol is 0.02 percent by volume, the covering time is 30 seconds, the spin-coating speed is 3000 rpm, and the spin-coating time is 20 seconds. Subsequently, the substrate was covered with acetonitrile, spin-coated, and then covered with acetonitrile, at a spin speed of 3000 rpm for 20 seconds. The steps are repeated for three times to obtain a film with enough thickness, and the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photoelectric detector is obtained.
Example 4
1) A three-necked flask was charged with 1.5mL of oleic acid, 35mL of octadecene, and 0.4464 g of yellow lead oxide with a stir bar. The three-necked flask was evacuated and then stirred. After 20 minutes, the temperature is raised to 95 ℃, at which time the reaction system is gradually clear and transparent, and the reaction system is stirred at the temperature for 2 hours under vacuum. And introducing nitrogen into the reaction system, vacuumizing, and repeating the process for three times to ensure that no water and no oxygen exist in the reaction system. The reaction was warmed to 120 ℃. 10mL of an octadecylene solution of hexamethyldisilazane was injected into the reaction system, and the content of hexamethyldisilazane in the solution was 2 mmol. After completion of the hot injection, the heat source was immediately turned off, and the reaction system was allowed to cool to room temperature in a nitrogen atmosphere.
2) To the reaction product in step 1), 20mL of methanol was added until the solution was separated, and the supernatant was discarded through a separatory funnel. To the resulting black solution was added sufficient acetone, centrifuged, the supernatant discarded, and 1mL of toluene was added to dissolve the precipitate sufficiently, and the process was repeated three times. And finally, the obtained precipitate is not added with toluene any more, and is dried overnight in vacuum, so that the lead sulfide quantum dot with the first exciton absorption peak of 1100 nm is obtained.
3) Putting the clean silicon substrate and indium gallium zinc oxide target material in a magnetron sputtering coating machine, vacuumizing to 6 multiplied by 10 -4 And introducing 45 mL of argon per minute in a standard state to finish the radio-frequency sputtering coating. The working air pressure of the magnetron sputtering film plating machine in the sputtering process is 0.36 Pa, the sputtering power is 60 watts, and the sputtering time is 5 minutes. Taking out the sample after the radio frequency sputtering coating, placing the sample on a high-temperature hot plate, annealing for 1 hour at 400 ℃, placing the sample and the high-purity aluminum wire in a thermal evaporation coating machine after cooling, and vacuumizing to 6 multiplied by 10 -4 And completing the deposition of the aluminum electrode. The distance between the source electrode and the drain electrode of the electrode pattern used in the process is 100 microns, and the length-width ratio is 0.2.
4) Adsorbing the sample obtained in the step 3) in a spin coater, covering the sample with the n-octane solution of the lead sulfide quantum dots, and spin-coating. In the process, the concentration of the n-octane solution of the lead sulfide quantum dots is 20mg/mL, the spin-coating speed is 3000 rpm, and the spin-coating time is 20 seconds. The sample was then coated with a solution of 1, 2-ethanedithiol in acetonitrile for a certain period of time and spin-coated. In the process, the concentration of acetonitrile solution of the 1, 2-ethanedithiol is 0.02 percent by volume, the covering time is 30 seconds, the spin-coating speed is 3000 rpm, and the spin-coating time is 20 seconds. Subsequently, the substrate was covered with acetonitrile, spin-coated, and then covered with acetonitrile, at a spin speed of 3000 rpm for 20 seconds. The steps are repeated for three times to obtain a film with enough thickness, and the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photoelectric detector is obtained.
Example 5
1) A three-necked flask was charged with 1.5mL of oleic acid, 35mL of octadecene, and 0.4464 g of yellow lead oxide with a stir bar. The three-necked flask was evacuated and then stirred. After 20 minutes, the temperature is raised to 95 ℃, at which time the reaction system is gradually clear and transparent, and the reaction system is stirred at the temperature for 2 hours under vacuum. And introducing nitrogen into the reaction system, vacuumizing, and repeating the process for three times to ensure that no water and no oxygen exist in the reaction system. The reaction was warmed to 120 ℃. 10mL of an octadecylene solution of hexamethyldisilazane was injected into the reaction system, and the content of hexamethyldisilazane in the solution was 2 mmol. After completion of the hot injection, the heat source was immediately turned off, and the reaction system was allowed to cool to room temperature in a nitrogen atmosphere.
2) To the reaction product in step 1), 20mL of methanol was added until the solution was separated, and the supernatant was discarded through a separatory funnel. To the resulting black solution was added sufficient acetone, centrifuged, the supernatant discarded, and 1mL of toluene was added to dissolve the precipitate sufficiently, and the process was repeated three times. And finally, the obtained precipitate is not added with toluene any more, and is dried overnight in vacuum, so that the lead sulfide quantum dot with the first exciton absorption peak of 1100 nm is obtained.
3) Putting the clean paper-based substrate and the indium gallium zinc oxide target material into a magnetron sputtering coating machine, and vacuumizing to 6 multiplied by 10 -4 And introducing 45 mL of argon per minute in a standard state to finish the radio-frequency sputtering coating. The working air pressure of the magnetron sputtering film plating machine in the sputtering process is 0.36 Pa, the sputtering power is 60 watts, and the sputtering time is 5 minutes. Taking out the sample after the radio frequency sputtering coating, placing the sample on a high-temperature hot plate, annealing for 1 hour at 100 ℃, placing the sample and the high-purity aluminum wire in a thermal evaporation coating machine after cooling, and vacuumizing to 6 multiplied by 10 -4 And (5) finishing the deposition of the aluminum electrode. The distance between the source electrode and the drain electrode of the electrode pattern used in the process is 100 microns, and the length-width ratio is 0.2.
4) Adsorbing the sample obtained in the step 3) in a spin coater, covering with a normal octane solution of the lead sulfide quantum dots, and spin-coating. In the process, the concentration of the n-octane solution of the lead sulfide quantum dots is 20mg/mL, the spin-coating speed is 3000 rpm, and the spin-coating time is 20 seconds. The sample was then coated with a solution of 1, 2-ethanedithiol in acetonitrile for a certain period of time and spin-coated. In the process, the concentration of acetonitrile solution of the 1, 2-ethanedithiol is 0.02 percent by volume, the covering time is 30 seconds, the spin-coating speed is 3000 rpm, and the spin-coating time is 20 seconds. Subsequently, the substrate was covered with acetonitrile, spin-coated, and then covered with acetonitrile, at a spin speed of 3000 rpm for 20 seconds. The steps are repeated for three times to obtain a film with enough thickness, and the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photoelectric detector is obtained.
Example 6
1) A three-necked flask was charged with 22mL of oleic acid, 44mL of octadecene, and 0.8928 g of yellow lead oxide, and a stir bar. The three-necked flask was evacuated and then stirred. After 20 minutes, the temperature is raised to 95 ℃, at which time the reaction system is gradually clear and transparent, and the reaction system is stirred at the temperature for 2 hours under vacuum. And introducing nitrogen into the reaction system, vacuumizing, and repeating the process for three times to ensure that no water and no oxygen exist in the reaction system. The reaction was warmed to 120 ℃. 10mL of an octadecylene solution of hexamethyldisilazane was injected into the reaction system, and the content of hexamethyldisilazane in the solution was 4 mmol. After completion of the hot injection, the heat source was immediately turned off, and the reaction system was allowed to cool to room temperature in a nitrogen atmosphere.
2) 40mL of methanol was added to the reaction product in step 1) until the solution was separated, and the supernatant was discarded through a separatory funnel. To the resulting black solution was added sufficient acetone, centrifuged, the supernatant discarded, and 2mL of toluene was added to dissolve the precipitate sufficiently, and the process was repeated three times. And finally, the obtained precipitate is not added with toluene any more, and is dried overnight in vacuum, so that the lead sulfide quantum dot with the first exciton absorption peak of 1400 nm is obtained.
3) Putting the clean white glass substrate and indium gallium zinc oxide target material in a magnetron sputtering coating machine, vacuumizing to 6 multiplied by 10 -4 And introducing 45 mL of argon per minute in a standard state to finish the radio-frequency sputtering coating. The working air pressure of the magnetron sputtering film plating machine in the sputtering process is 0.36 Pa, the sputtering power is 60 watts, and the sputtering time is 5 minutes. Taking out the sample after the radio frequency sputtering coating, placing the sample on a high-temperature hot plate, annealing for 1 hour at 400 ℃, placing the sample and the high-purity aluminum wire in a thermal evaporation coating machine after cooling, and vacuumizing to 6 multiplied by 10 -4 And (5) finishing the deposition of the aluminum electrode. The distance between the source electrode and the drain electrode of the electrode pattern used in the process is 100 microns, and the length-width ratio is 0.2.
4) Adsorbing the sample obtained in the step 3) in a spin coater, covering with a normal octane solution of the lead sulfide quantum dots, and spin-coating. In the process, the concentration of the n-octane solution of the lead sulfide quantum dots is 20mg/mL, the spin-coating speed is 3000 rpm, and the spin-coating time is 20 seconds. The sample was then coated with a solution of 1, 2-ethanedithiol in acetonitrile for a certain period of time and spin-coated. In the process, the concentration of acetonitrile solution of the 1, 2-ethanedithiol is 0.02 percent by volume, the covering time is 30 seconds, the spin-coating speed is 3000 rpm, and the spin-coating time is 20 seconds. Subsequently, the substrate was covered with acetonitrile, spin-coated, and then covered with acetonitrile, at a spin speed of 3000 rpm for 20 seconds. The steps are repeated for three times to obtain a film with enough thickness, and the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photoelectric detector is obtained.
Claims (10)
1. An amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector is characterized in that: the method comprises the steps of sequentially depositing a 1, 2-ethanedithiol ligand lead sulfide quantum dot film on a substrate, a radio frequency magnetron sputtering amorphous indium gallium zinc oxide film, an aluminum electrode and a solid ligand exchange method from bottom to top.
2. A method for preparing the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector as claimed in claim 1, characterized by comprising the following steps:
step 1, placing a clean substrate and an indium gallium zinc oxide target material in a magnetron sputtering coating machine, vacuumizing, and introducing argon to finish radio frequency sputtering coating; taking out the sample, placing the sample on a high-temperature hot plate for annealing, and then placing the sample and high-purity aluminum wires in a thermal evaporation coating machine together to finish the deposition of an aluminum electrode;
step 2, adsorbing the sample obtained in the step 1 in a spin coater, covering a normal octane solution of lead sulfide quantum dots, performing spin coating, then covering an acetonitrile solution of 1, 2-ethanedithiol on the sample for a certain time, performing spin coating, then covering acetonitrile for multiple times, performing spin coating, covering acetonitrile again, and performing spin coating;
and repeating the step 2 for a plurality of times until a film with enough thickness is obtained, thus obtaining the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector.
3. The method for preparing the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector as claimed in claim 2, wherein the method comprises the following steps: the substrate is a white glass substrate, a silicon substrate or a paper substrate.
4. The method for preparing the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector as claimed in claim 2, wherein the method comprises the following steps: in the step 1, vacuum is pumped to 6 x 10 -4 Introducing 45 milliliters of argon per minute in a standard state to finish radio frequency sputtering coating; in the sputtering process, the working air pressure of the magnetron sputtering coating machine is 0.36 Pa, the sputtering power is 60 watts, and the sputtering time is 5-20 minutes.
5. The method for preparing the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector as claimed in claim 2, wherein the method comprises the following steps: annealing at 400 ℃ for 1 hour in the annealing in the step 1, cooling, putting the aluminum wire and the high-purity aluminum wire into a thermal evaporation coating machine, and vacuumizing to 6 x 10 -4 Finishing the deposition of the aluminum electrode; the distance between the source electrode and the drain electrode of the electrode pattern is 100 microns, and the length-width ratio is 0.2.
6. The method for preparing the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector as claimed in claim 2, wherein the method comprises the following steps: the concentration of the n-octane solution of the lead sulfide quantum dots covered in the step 2 is 20mg/mL, the speed of spin-coating the n-octane solution of the lead sulfide quantum dots is 3000 rpm, and the spin-coating time is 20 seconds.
7. The method for preparing the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector as claimed in claim 2, wherein the method comprises the following steps: the concentration of the acetonitrile solution of the 1, 2-ethanedithiol covered in the step 2 is 0.02 percent by volume, the covering time is 30 seconds, the speed of spin-coating the acetonitrile solution of the 1, 2-ethanedithiol is 3000 rpm, and the spin-coating time is 20 seconds; the speed of the spin coating of acetonitrile was 3000 rpm, and the spin coating time was 20 seconds.
8. The method for preparing an amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector as claimed in claim 2, wherein the method for preparing the lead sulfide quantum dots used in the n-octane solution of the lead sulfide quantum dots in the step 2 comprises the following steps:
step 1.1, filling 1.5mL of oleic acid, 35mL of octadecene, 0.4464 g of yellow lead oxide and a stirrer into a three-neck flask, vacuumizing, stirring and heating, wherein the reaction system is gradually clear and transparent; vacuumizing at the temperature and continuously stirring, then introducing nitrogen into the reaction system, vacuumizing, and repeating the process for many times to ensure that no water and no oxygen exist in the reaction system; heating the reaction system to 120 ℃, injecting 10mL of octadecylene solution of hexamethyldisilazane, closing a heat source to cool the reaction system to room temperature in a nitrogen environment after the hot injection is finished when the content of the hexamethyldisilazane in the solution is 2 mmol;
and step 1.2, adding methanol into the reaction product obtained in the step 1.1 until the solution is layered, discarding the supernatant through a separating funnel, adding sufficient acetone into the obtained black solution, centrifuging, discarding the supernatant, adding toluene to fully dissolve the precipitate, repeating the process for multiple times, and finally removing the toluene from the obtained precipitate, and performing vacuum drying to obtain the lead sulfide quantum dot with the first exciton absorption peak of 1100 nm.
9. The method for preparing the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector as claimed in claim 8, wherein the method comprises the following steps: in the step 1.1, oleic acid, octadecene, yellow lead oxide and a stirrer are put into a three-necked flask, vacuumized, stirred for 20 minutes, heated to 95 ℃, the reaction system is gradually clear and transparent, and vacuumized at the temperature and continuously stirred for 2 hours.
10. The method for preparing the amorphous indium gallium zinc oxide/lead sulfide quantum dot double-layer heterojunction photoconductive photodetector as claimed in claim 8, wherein the method comprises the following steps: in the 1.2, 20mL of methanol is added to the reaction product of the step 1.1 until the solution is layered, and the amount of added toluene is 1mL each time.
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| EP3734671A1 (en) * | 2019-04-30 | 2020-11-04 | Fundació Institut de Ciències Fotòniques | A method for obtaining an n-type doped metal chalcogenide quantum dot solid-state film, and an optoelectronic device comprising the obtained film |
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