CN113270510A - Photoelectric sensor chip, preparation method thereof and photoelectric sensor - Google Patents
Photoelectric sensor chip, preparation method thereof and photoelectric sensor Download PDFInfo
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- 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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- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
- H01L31/112—Devices sensitive to infrared, visible or ultraviolet radiation characterised by field-effect operation, e.g. junction field-effect phototransistor
- H01L31/113—Devices sensitive to infrared, visible or ultraviolet radiation characterised by field-effect operation, e.g. junction field-effect phototransistor being of the conductor-insulator-semiconductor type, e.g. metal-insulator-semiconductor field-effect transistor
- H01L31/1136—Devices sensitive to infrared, visible or ultraviolet radiation characterised by field-effect operation, e.g. junction field-effect phototransistor being of the conductor-insulator-semiconductor type, e.g. metal-insulator-semiconductor field-effect transistor the device being a metal-insulator-semiconductor field-effect transistor
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Abstract
The invention discloses a photoelectric sensor chip and a preparation method thereof and a photoelectric sensor, wherein the photoelectric sensor chip comprises a substrate, a source electrode, a drain electrode and a grid electrode which are arranged on the substrate at intervals, an active layer arranged on the substrate between the source electrode and the drain electrode and on the source electrode and the drain electrode, and a dielectric layer arranged on the active layer, wherein the active layer comprises an organic heterojunction material and a quantum dot material. The quantum dot material is introduced into the active layer and can be used as a defect center in the electron transportation process to effectively limit the movement of electrons, so that the dark current of the photoelectric sensor is reduced, and the sensitivity of the photoelectric sensor is improved. Meanwhile, an electronic defect state is introduced, so that the mobility of electrons is reduced, and the optical gain of the photoelectric sensor is improved. The preparation method provided by the invention is simple and easy to realize, and has higher practicability and economic value.
Description
Technical Field
The invention relates to the field of photoelectric sensors, in particular to a photoelectric sensor chip, a preparation method thereof and a photoelectric sensor.
Background
The nano-science refers to a science and technology for researching atomic and molecular dimensions. Typical nanomaterials are defined as: a material having at least one dimension between 1 and 100 nanometers. The physical, chemical and biological properties of the nano material are greatly different from those of the material with normal macroscopic scale, and the quantum mechanical effect of the nano material is also widely applied. The quantum dot, which is a kind of nanomaterial, generally refers to a semiconductor nanomaterial having a radius smaller than or close to an exciton bohr radius, or refers to a fine particle of a metal or semiconductor material having a size in the nanometer order. The quantum dot material is generally composed of II-VI group or III-V group elements, has stable property, can receive excitation to generate fluorescence, and has orderly atomic arrangement. In recent years, people have made a lot of researches on synthesis, performance analysis and characterization of quantum dot materials, and quantum dot materials are widely applied to the fields of LED display, detection technology, biological fluorescent labeling, laser and the like.
In the optical application range, the quantum dot material has the advantages of wide absorption wavelength range, stable absorption wavelength and the like, and the absorption wavelength can be adjusted by adjusting the size of the quantum dot material due to the unique physical characteristics of the quantum dot material. However, from another physical point of view, the performance of the quantum dot material itself with defect states in the photoelectric sensor hybrid material is still yet to be explored and developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention provides a photosensor chip, a method for manufacturing the same, and a photosensor, which are intended to improve the sensitivity and optical gain of the prior photosensor chip.
The technical scheme of the invention is as follows:
a photoelectric sensor chip comprises a substrate, a source electrode, a drain electrode and a grid electrode which are arranged on the substrate at intervals, an active layer arranged on the substrate between the source electrode and the drain electrode and on the source electrode and the drain electrode, and a dielectric layer arranged on the active layer, wherein the active layer comprises an organic heterojunction material and a quantum dot material.
Optionally, the mass ratio of the organic heterojunction material to the quantum dot material is 2: 1.
Optionally, the active layer is composed of an organic heterojunction layer formed by the organic heterojunction material and a quantum dot layer formed by the quantum dot material, the quantum dot layer is arranged below the organic heterojunction layer, and the quantum dot layer is attached to the substrate between the source electrode and the drain electrode;
or the active layer is composed of an organic heterojunction layer formed by the organic heterojunction material and a quantum dot layer formed by the quantum dot material, and the quantum dot layer is arranged above the organic heterojunction layer;
or the active layer is composed of an organic heterojunction layer formed by the organic heterojunction material and a quantum dot layer formed by the quantum dot material, and the quantum dot layers are simultaneously arranged above and below the organic heterojunction layer;
alternatively, the active layer is composed of the organic heterojunction material and the quantum dot material dispersed in the organic heterojunction material.
Optionally, when the quantum dot layer is arranged below the organic heterojunction layer, the thickness of the quantum dot layer is 45-55 nm;
or when the quantum dot layer is arranged above the organic heterojunction layer, the thickness of the quantum dot layer is 45-55 nm;
or when the quantum dot layers are arranged above and below the organic heterojunction layer at the same time, the total thickness of the quantum dot layers is 45-55 nm.
Optionally, the size of the quantum dot material is 3-6 nm.
Optionally, the quantum dot material is a red light quantum dot material.
Optionally, the red light quantum dot material is a core-shell structure red light quantum dot material.
Optionally, the core-shell structure red light quantum dot material is selected from one or more of a core-shell structure InP/ZnS red light quantum dot material, a core-shell structure CdSe/ZnS red light quantum dot material, and a core-shell structure ZnSe/ZnS red light quantum dot material.
Optionally, the organic heterojunction material is composed of a P-type organic semiconductor and an N-type organic semiconductor.
The invention relates to a preparation method of a photoelectric sensor chip, which comprises the following steps:
providing a substrate;
preparing a source electrode, a drain electrode and a grid electrode on the substrate;
preparing an active layer on the substrate between the source electrode and the drain electrode and on the source electrode and the drain electrode, the active layer comprising an organic heterojunction material and a quantum dot material;
and preparing a dielectric layer on the active layer to obtain the photoelectric sensor chip.
A photoelectric sensor comprises the photoelectric sensor chip.
Has the advantages that: the invention provides a photoelectric sensor chip, a preparation method thereof and a photoelectric sensor. Meanwhile, an electronic defect state can be introduced, and the mobility of electrons is reduced, so that the optical gain of the photoelectric sensor is improved. The preparation method provided by the invention is simple and easy to realize, and has higher practicability and economic value.
Drawings
Fig. 1 is a schematic diagram of a first structure of a photosensor chip according to an embodiment of the present invention.
Fig. 2 is a second structural diagram of a photosensor chip according to an embodiment of the present invention.
Fig. 3 is a schematic diagram of a third structure of a photosensor chip according to an embodiment of the present invention.
Fig. 4 is a schematic diagram of a fourth structure of a photosensor chip according to an embodiment of the present invention.
FIG. 5 is a graph showing the results of the transfer curve test in dark and light for inventive example 1 and comparative example 1.
FIG. 6a is a graph showing the results of the on/off ratio test in the dark for example 1 of the present invention and comparative example 1.
FIG. 6b is a graph showing the results of the sensitivity test of example 1 of the present invention and comparative example 1.
Detailed Description
The invention provides a photoelectric sensor chip, a preparation method thereof and a photoelectric sensor, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear and definite. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a photoelectric sensor chip, which comprises a substrate, a source electrode, a drain electrode and a grid electrode which are arranged on the substrate at intervals, an active layer arranged on the substrate between the source electrode and the drain electrode and on the source electrode and the drain electrode, and a dielectric layer arranged on the active layer, wherein the active layer comprises an organic heterojunction material and a quantum dot material.
In this embodiment, a quantum dot material is introduced into the active layer, so that an electrical layer structure is formed at an interface between the quantum dot material and the organic heterojunction material. And because the quantum dots have the capability of absorbing light, the introduction of the quantum dot material in the active layer can widen the light detection range of the device. In addition, the quantum dot material can be used as a defect center in an electron transportation process, and effectively hinders the electron transportation, so that the dark current of the photoelectric sensor is reduced, and the sensitivity of the photoelectric sensor is improved. Meanwhile, the introduction of the quantum dots can introduce an electron defect state, reduce the electron mobility, enable the hole mobility of the device to be larger than the electron mobility, and finally improve the optical gain of the photoelectric sensor.
In this embodiment, the organic heterojunction material is used as a constituent material of the active layer, the organic heterojunction material can effectively absorb a spectrum in a wide wavelength range and generate photo-generated excitons, the excitons can be effectively separated into free electrons and holes by the energy band difference of the heterojunction, and the multiplication of photocurrent is realized due to the great difference in mobility of the electrons and the holes in the two semiconductor materials of the heterojunction, so that the photosensor with ultrahigh photoelectric sensitivity is obtained.
In one embodiment, the substrate has a thickness of 20 to 100 nm.
In one embodiment, the material of the substrate is selected from one of silicon wafer, silicon dioxide, polyimide, hydrogenated styrene-butadiene block copolymer, but is not limited thereto. The substrate material has good heat resistance.
In one embodiment, the source electrode, the drain electrode and the gate electrode are chromium-gold alloy electrodes.
In one embodiment, the chromium-gold alloy electrode is composed of a chromium adhesion layer and a gold conductive layer, wherein the thickness of the chromium adhesion layer is 40-50 nm, and the thickness of the gold conductive layer is 5-10 nm. The chromium adhesion layer is prepared on the substrate, and the gold conductive layer is prepared on the chromium adhesion layer.
In one embodiment, the connection between the source and drain is designed as an interdigitated structure or a serpentine structure.
When the connecting part between the source electrode and the drain electrode is designed to be an interdigital structure, the length of the formed conductive channel is less than or equal to 20 microns, the width of the formed conductive channel is more than 1cm, and the distance between the grid electrode and the conductive channel is less than or equal to 0.1 mm. The larger the aspect ratio of the conductive channel, the greater the density of the fingers, and the higher the sensitivity and response speed of the sensor.
In one embodiment, the mass ratio of the organic heterojunction material to the quantum dot material is 2: 1.
In one embodiment, the active layer is comprised of an organic heterojunction layer formed of the organic heterojunction material and a quantum dot layer formed of the quantum dot material, the quantum dot layer being disposed below the organic heterojunction layer, the quantum dot layer being disposed adjacent to the substrate side. Specifically, the structure of the photosensor chip having this structure is shown in fig. 1, and the photosensor chip includes a substrate 7, a source electrode 3, a drain electrode 6, and a gate electrode 1 which are disposed on the substrate 7 at intervals, an active layer disposed on the substrate 7 between the source electrode 3 and the drain electrode 6 and on the source electrode 3 and the drain electrode 6, and a dielectric layer 2 disposed on the active layer. Wherein the active layer is composed of an organic heterojunction layer 4 and a quantum dot layer 5, the quantum dot layer 5 is arranged below the organic heterojunction layer 4, and the quantum dot layer 5 is attached to a substrate 7 between the source electrode 3 and the drain electrode 6.
In one embodiment, when the quantum dot layer is disposed under the organic heterojunction layer, the quantum dot layer has a thickness of 45 to 55 nm.
In one embodiment, the active layer is composed of an organic heterojunction layer formed of the organic heterojunction material and a quantum dot layer formed of the quantum dot material, the quantum dot layer being disposed above the organic heterojunction layer, the organic heterojunction layer being disposed in contact with the substrate between the source and drain electrodes and being disposed on both the source and drain electrodes. Specifically, the structure of the photosensor chip having this structure is shown in fig. 2, and the photosensor chip includes a substrate 7, a source electrode 3, a drain electrode 6, and a gate electrode 1 which are disposed on the substrate 7 at intervals, an active layer disposed on the substrate 7 between the source electrode 3 and the drain electrode 6 and on the source electrode 3 and the drain electrode 6, and a dielectric layer 2 disposed on the active layer. Wherein the active layer is composed of an organic heterojunction layer 4 and a quantum dot layer 5, the quantum dot layer 5 is arranged above the organic heterojunction layer 4, and the organic heterojunction layer 4 is attached to a substrate 7 between the source electrode 3 and the drain electrode 6 and is simultaneously arranged on the source electrode 3 and the drain electrode 6.
In one embodiment, when the quantum dot layer is disposed above the organic heterojunction layer, the quantum dot layer has a thickness of 45 to 55 nm.
In one embodiment, the active layer is composed of an organic heterojunction layer formed of the organic heterojunction material and a quantum dot layer formed of the quantum dot material, the quantum dot layers are disposed above and below the organic heterojunction layer at the same time, and the quantum dot layer disposed below the organic heterojunction layer is attached to the substrate between the source and drain electrodes. Specifically, the structure of the photosensor chip having this structure is shown in fig. 3, and the photosensor chip includes a substrate 7, a source electrode 3, a drain electrode 6, and a gate electrode 1 which are disposed on the substrate 7 at intervals, an active layer disposed on the substrate 7 between the source electrode 3 and the drain electrode 6 and on the source electrode 3 and the drain electrode 6, and a dielectric layer 2 disposed on the active layer. Wherein, the active layer is composed of an organic heterojunction layer 4 and a quantum dot layer 5, the quantum dot layer 5 is simultaneously arranged above and below the organic heterojunction layer 4, and the quantum dot layer 5 arranged below the organic heterojunction layer 4 is attached to a substrate 7 between the source electrode 3 and the drain electrode 6.
In one embodiment, when the quantum dot layers are disposed both above and below the organic heterojunction layer, the quantum dot layers have a total thickness of 45 to 55 nm.
In one embodiment, the active layer is comprised of the organic heterojunction material and quantum dot material dispersed in the organic heterojunction material. Specifically, the structure of the photosensor chip having this structure is shown in fig. 4, and the photosensor chip includes a substrate 7, a source electrode 3, a drain electrode 6, and a gate electrode 1 which are disposed on the substrate 7 at intervals, an active layer disposed on the substrate 7 between the source electrode 3 and the drain electrode 6 and on the source electrode 3 and the drain electrode 6, and a dielectric layer 2 disposed on the active layer. Wherein the active layer consists of the organic heterojunction material 4 and the quantum dot material 5 dispersed in the organic heterojunction material 4.
In one embodiment, the size of the quantum dot material is 3-6 nm.
In one embodiment, the quantum dot material is a red light quantum dot material. The red light quantum dot material has the advantages of high luminous efficiency, good stability and the like.
In one embodiment, the red light quantum dot material is a core-shell structure red light quantum dot material.
In one embodiment, the core-shell structure red light quantum dot material is selected from one or more of core-shell structure InP/ZnS red light quantum dot materials, core-shell structure CdSe/ZnS red light quantum dot materials and core-shell structure ZnSe/ZnS red light quantum dot materials.
In one embodiment, the core-shell structure red light quantum dot material is a core-shell structure InP/ZnS red light quantum dot material. The core of the InP/ZnS red light quantum dot with the core-shell structure is InP, the shell is ZnS, and the density is 0.715g/cm3The size is 5nm, the photoluminescence peak wavelength is 621nm, and the photoluminescence half-peak width is 46 nm. The cadmium-free environment-friendly InP/ZnS red-light quantum dot with the core-shell structure effectively overcomes the defect of high toxicity of Cd-series quantum dots, and has the advantages of high extinction coefficient and obvious quantum confinement effectAnd the wide coverage range of spectral frequency is emitted.
In one embodiment, the thickness of the organic heterojunction layer is 100 to 200 nm.
In one embodiment, the organic heterojunction material is composed of a P-type organic semiconductor and an N-type organic semiconductor.
In one embodiment, the P-type organic semiconductor and the N-type organic semiconductor have a mass ratio of 1:1, which results in a device with relatively low dark current and higher sensitivity.
The charge transport of the P-type organic semiconductor is dominated by hole carriers, and the mobility of the hole carriers is high. The absorption of the P-type semiconductor is in the long wavelength range, typically 500nm to 900 nm. The charge transport of the N-type organic semiconductor is dominated by electron carriers, and the mobility of the electron carriers is low. The organic heterogeneous material can effectively absorb a spectrum in a wider wavelength range and generate photo-generated excitons, the excitons can be effectively separated into free electrons and holes by the energy band difference of the heterojunction, and the multiplication of photocurrent is realized due to the huge difference of the mobility of the electrons and the holes in two types of semiconductor materials of the heterojunction, so that the photoelectric sensor chip with ultrahigh photoelectric sensitivity is obtained.
In one embodiment, the P-type organic semiconductor is selected from one or more of polydithiophene-pyrrolopyrrole dione (PDPP-TT), polycarbazole-polythiophene-Polybenzthiadiazole (PCDTBT), poly [ [4, 8-bis [ (2-ethylhexyl) oxy ] -benzo [1,2-B:4,5-B' ] dithiophene-2, 6-diyl ] [ 3-fluoro-2- [ (2-ethylhexyl) carbonyl ] thieno [3,4-B ] thiophene ] (PTB7), poly (3-hexylthiophene-2, 5-diyl) (P3 HT).
In one embodiment, the N-type organic semiconductor is selected from one or more of (6,6) -phenyl-C61-methyl butyrate (PC61BM), (6,6) -phenyl-C71 methyl butyrate (PC71BM), and fullerenes.
In one embodiment, the thickness of the dielectric layer is 100 to 200 nm.
In one embodiment, the material of the dielectric layer is an ionic gel.
In one embodiment, the components used to prepare the ionic gel include polyethylene glycol diacrylate, 1-ethyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imide, 2-hydroxy-2-methyl-1-phenyl-1-propanone.
In one embodiment, the mass ratio of polyethylene glycol diacrylate, 1-ethyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imide, and 2-hydroxy-2-methyl-1-phenyl-1-propanone is 1:4: 7.
The embodiment of the invention also provides a preparation method of the photoelectric sensor chip, which comprises the following steps:
s1, providing a substrate;
s2, preparing a source electrode, a drain electrode and a grid electrode on the substrate;
s3, preparing an active layer on the substrate between the source electrode and the drain electrode and on the source electrode and the drain electrode, wherein the active layer comprises an organic heterojunction material and a quantum dot material;
and S4, preparing a dielectric layer on the active layer to obtain the photoelectric sensor chip.
In step S2, in one embodiment, a source electrode, a drain electrode, and a gate electrode are formed on the substrate by photolithography or vacuum thermal evaporation.
In one embodiment, the source electrode, the drain electrode, and the gate electrode are formed on the substrate by photolithography or vacuum thermal evaporation, the source electrode, the drain electrode, and the gate electrode each include an adhesion layer and a conductive layer, the adhesion layer is made of chromium metal, the conductive layer is made of gold metal, and the method specifically includes:
s21, carrying out photoetching or vacuum thermal evaporation on the substrate to form a chromium adhesion layer;
s22, photoetching or vacuum thermal evaporation plating a gold conducting layer on the chromium adhesion layer;
in one embodiment, after the step S2 and before the step S3, the method further includes a step of immersing the substrate including the source electrode, the drain electrode, and the gate electrode in an acetone solution for ultrasonic cleaning.
In step S3, in one embodiment, an active layer is prepared on the substrate between the source electrode and the drain electrode and on the source electrode and the drain electrode, the active layer includes an organic heterojunction material and a quantum dot material, the active layer is composed of an organic heterojunction layer formed by the organic heterojunction material and a quantum dot layer formed by the quantum dot material, the quantum dot layer is disposed below the organic heterojunction layer, and the quantum dot layer is attached to the substrate between the source electrode and the drain electrode, and the step of preparing the active layer in this embodiment specifically includes:
s311, providing a quantum dot solution and an organic heterojunction solution;
s312, the quantum dot solution is coated, thrown or ink-jet printed on the substrate between the source electrode and the drain electrode, and is annealed and then cooled to obtain a quantum dot layer;
s313, the organic heterojunction solution is coated and thrown on the source electrode, the drain electrode and the quantum dot layer, and the organic heterojunction layer is obtained.
In step S311, in one embodiment, the step of preparing the organic heterojunction solution specifically includes:
dissolving the P-type semiconductor in an organic solvent, heating, and filtering to obtain a P-type semiconductor solution;
dissolving the N-type semiconductor in an organic solvent, heating, and filtering to obtain an N-type semiconductor solution;
and mixing and heating the obtained P-type semiconductor solution and the N-type semiconductor solution to obtain the organic heterojunction material solution. Wherein the purpose of the filtration is to exclude large particles that are insoluble in the solution.
In step S312, the annealing is performed firstly to evaporate the solvent, and secondly to make the heterojunction film in step S313 more regular, thereby benefiting the charge transport.
In step S3, in one embodiment, an active layer is prepared on the substrate between the source electrode and the drain electrode and on the source electrode and the drain electrode, the active layer includes an organic heterojunction layer formed by the organic heterojunction material and a quantum dot material, the active layer is composed of an organic heterojunction layer formed by the organic heterojunction material and a quantum dot layer formed by the quantum dot material, the quantum dot layer is disposed above the organic heterojunction layer, and the organic heterojunction layer is attached to the substrate between the source electrode and the drain electrode and is disposed on the source electrode and the drain electrode at the same time, and the preparation step of the active layer of this embodiment specifically includes:
s321, providing a quantum dot solution and an organic heterojunction solution;
s322, coating or ink-jet printing the organic heterojunction solution on the substrate between the source electrode and the drain electrode and the source electrode and the drain electrode to obtain the organic heterojunction layer;
s323, coating the quantum dot solution on the organic heterojunction layer, and annealing to obtain the quantum dot layer.
In step S321, the preparation step of the organic heterojunction solution is the same as that in step S311, and is not repeated here.
In step S322, in one embodiment, the thickness of the organic heterojunction layer is 100 to 200 nm.
In step S323, in one embodiment, the quantum dot layer has a thickness of 45-55 nm.
In step S3, in one embodiment, an active layer is formed on the substrate between the source electrode and the drain electrode and on the source electrode and the drain electrode, the active layer includes an organic heterojunction layer formed of the organic heterojunction material and a quantum dot material, the active layer is composed of an organic heterojunction layer formed of the organic heterojunction material and a quantum dot layer formed of the quantum dot material, the quantum dot layers are simultaneously disposed above and below the organic heterojunction layer, the quantum dot layer disposed below the organic heterojunction layer is attached to the substrate between the source electrode and the drain electrode, and the active layer of this embodiment is specifically formed by:
s331, providing a quantum dot solution and an organic heterojunction solution;
s332, coating and throwing or ink-jet printing the quantum dot solution on the substrate between the source electrode and the drain electrode, annealing and then cooling to obtain a quantum dot layer;
s333, coating and throwing the organic heterojunction solution on the source electrode, the drain electrode and the quantum dot layer to obtain the organic heterojunction layer;
and S334, coating and throwing or ink-jet printing the quantum dot solution on the organic heterojunction layer, annealing and then cooling to obtain the quantum dot layer.
In step S331, the preparation steps of the organic heterojunction solution are the same as those in step S311, and are not described herein again.
In step S332, the purpose of annealing is the same as that in step S312, and is not described herein again.
In one embodiment, the sum of the thicknesses of the quantum dot layers in the steps S332 and S334 is 45-55 nm.
In step S333, in one embodiment, the thickness of the organic heterojunction layer is 100 to 200 nm.
In step S3, in one embodiment, an active layer is prepared on the substrate between the source electrode and the drain electrode and on the source electrode and the drain electrode, the active layer includes an organic heterojunction material and a quantum dot material, the active layer is composed of the organic heterojunction material and the quantum dot material dispersed in the organic heterojunction material, and the preparation of the active layer of this embodiment specifically includes:
s341, providing a mixed solution containing a quantum dot material and an organic heterojunction material;
and S342, coating and throwing the mixed solution on the substrate between the source electrode and the drain electrode and the source electrode and the drain electrode to obtain the active layer.
In step S341, in one embodiment, the mixed solution of the quantum dot-containing material and the organic heterojunction material is prepared by dispersing the quantum dot material and the organic heterojunction material in a solvent (e.g., dichlorobenzene). The preparation steps of the organic heterojunction solution are as described above and will not be described herein.
In step S342, in one embodiment, the thickness of the active layer is 100 to 200 nm.
In step S4, in one embodiment, the step of preparing a dielectric layer on the active layer specifically includes:
s41, preparing ionic gel;
and S42, forming ionic gel on the active layer and the grid electrode to prepare the dielectric layer.
In step S42, in one embodiment, the dielectric layer has a thickness of 100 to 200 nm.
The invention is further illustrated by the following specific examples.
The methods for preparing the quantum dot solution, the organic heterojunction solution and the ionic gel in examples 1 to 4 were as follows.
1. Preparation of InP/ZnS red light quantum dot solution with water-soluble core-shell structure
0.58g of Zn (Ac)2·2H2O and 0.59g of thioglycolic acid were added to 20ml of deionized water, i.e., Zn2+Thioglycollic acid and Zn with the concentration of 0.13mol/L2+The amount ratio of the substances (a) to (b) is n (thioglycolic acid)/n (Zn)2+) 2.4. And then, adjusting the pH of the solution to 11 by using 1mol/L NaOH, and uniformly shaking to obtain a mercaptoacetic acid modified zinc ligand solution, namely precursor liquid M for short.
Dissolving 6mg of InP quantum dot solid powder in 10ml of mixed solution of hexane and butanol (the volume ratio of hexane to butanol is 2:1), ultrasonically dispersing for 2min, then adding 10ml of precursor liquid M into the mixed solution, stirring for 1h at the temperature of 40-60 ℃, transferring InP quantum dots to a water layer of the precursor liquid M, and then removing the hexane and butanol mixed organic layer to obtain the mercaptoacetic acid modified aqueous phase InP quantum dot solution.
Adding 6ml of precursor solution M into the aqueous phase InP quantum dot solution, stirring for 1h under the irradiation of ultraviolet light (lambda is 365nm) to obtain the water-soluble core-shell InP/ZnS red light quantum dot solution, wherein the core is InP, the shell is ZnS, and the density is 0.715g/cm3The size is 5nm, the photoluminescence peak wavelength is 621nm, and the photoluminescence half-peak width is 46 nm.
2. Preparation of organic heterojunction solution
Dissolving a certain amount of P-type semiconductor PDPP2T in a certain amount of dichlorobenzene, stirring for 6 hours at 95 ℃ by magnetic beads until the mixture is uniform, then filtering by a filter membrane to remove insoluble large particles in the solution, and obtaining the dichlorobenzene solution of PDPP2T with the concentration of PDPP2T of 7 mg/ml.
Mixing a certain amount of N-type semiconductor PC61BM is dissolved in a certain amount of dichlorobenzene, stirred for 6 hours at 95 ℃ by magnetic beads until uniform, then filtered by a filter membrane to remove large particles which can not be dissolved in the solution to obtain PC61PC with BM concentration of 7mg/ml61Dichlorobenzene solution of BM.
Mixing a dichlorobenzene solution of PDPP2T and PC61The dichlorobenzene solutions of BM were mixed and heated at ×, yielding an organic heterojunction solution.
3. Preparation of Ionic gels
Providing a cleaned ionic gel mold;
mixing polyethylene glycol diacrylate and 2-hydroxy-2-methyl-1-phenyl-1-acetone in a mass ratio of 1:7, adding small magnetic beads, placing the mixture on a magnetic stirring table, stirring the mixture for 1 hour, adding methylimidazoline bis (trifluoromethylsulfonyl) imide ionic liquid (wherein the mass ratio of the polyethylene glycol diacrylate to the 1-ethyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imide to the 2-hydroxy-2-methyl-1-phenyl-1-acetone is 1:4:7), and continuously stirring the mixture on the magnetic stirring table for 20 minutes to prepare an ionic gel solution;
and pouring the ionic gel solution into a mould, putting the mould into a vacuum drying oven when bubbles completely disappear, baking the mould at 70 ℃ for 24 hours, and taking the mould out to obtain the cuboid ionic gel.
Example 1
Drawing of a chip die was performed using a CAD drawing tool, in which the connection between the source and drain electrodes was an interdigital structure, and the formed conductive channel had a length of 15 μm and a width of 1.5 cm.
And thermally evaporating a chromium adhesion layer with the thickness of 8nm on a SEBS substrate with the thickness of 50nm in vacuum, and thermally evaporating a gold conductive layer with the thickness of 80nm on the chromium adhesion layer in vacuum to prepare three chromium-gold alloy electrodes which are arranged at intervals and respectively used as a source electrode, a drain electrode and a grid electrode. The distance between the grid and the conducting channel is less than or equal to 0.1 mm.
And soaking the substrate containing the source electrode, the drain electrode and the grid electrode in an acetone solution, and carrying out surface ultrasonic cleaning by an ultrasonic cleaning machine.
Diluting the water-soluble InP/ZnS red light quantum dot solution with water to 2.5mg/ml, and coating the water-soluble InP/ZnS red light quantum dot solution with 2.5mg/ml on a substrate between a source electrode and a drain electrode by using a spin coater. The front rotation speed of the spin coater is set to be 500r/min, the time is 5s, the rotation speed is set to be 2000r/min, and the time is 60s after the water-soluble InP/ZnS red light quantum dot solution is uniformly spread on the substrate. Annealing at 120 deg.C for 5min, and cooling for 2min to obtain 50nm quantum dot layer.
The organic heterojunction solution is prepared according to the proportion of PDPP2T: PC by a spin coater61BM (InP/ZnS) is coated and thrown on the quantum dot layer and the source electrode and the drain electrode in a mass ratio of 1:1:1, the forward rotation speed of a spin coater is set to be 500r/min for 5s, and after the organic heterojunction solution is uniformly spread, the rotation speed is set to be 2000r/min for 60 s. Annealing at 120 ℃ for 20 minutes resulted in an organic heterojunction layer with a thickness of 140 nm.
And covering the active layer with 150 nm-thick ionic gel to obtain the photoelectric sensor.
Example 2
Drawing of a chip die was performed using a CAD drawing tool, in which the connection between the source and drain electrodes was an interdigital structure, and the formed conductive channel had a length of 15 μm and a width of 1.5 cm.
And thermally evaporating a chromium adhesion layer with the thickness of 8nm on a SEBS substrate with the thickness of 50nm in vacuum, and thermally evaporating a gold conductive layer with the thickness of 80nm on the chromium adhesion layer in vacuum to prepare three chromium-gold alloy electrodes which are arranged at intervals and respectively used as a source electrode, a drain electrode and a grid electrode. The distance between the grid and the conducting channel is less than or equal to 0.1 mm.
And soaking the substrate containing the source electrode, the drain electrode and the grid electrode in an acetone solution, and carrying out surface ultrasonic cleaning by an ultrasonic cleaning machine.
The organic heterojunction solution is prepared according to the proportion of PDPP2T: PC by a spin coater61BM (InP/ZnS) is in a mass ratio of 1:1:1Firstly, coating and throwing the organic heterojunction solution on a substrate between a source electrode and a drain electrode and the source electrode and the drain electrode, setting the forward rotation speed of a spin coater to be 500r/min and the time to be 5s, and setting the rotation speed to be 2000r/min and the time to be 60s after the organic heterojunction solution is uniformly spread. Annealing at 120 ℃ for 20 minutes resulted in an organic heterojunction layer with a thickness of 140 nm.
And diluting the water-soluble InP/ZnS red light quantum dot solution with the core-shell structure to 2.5mg/ml with water, and coating the water-soluble InP/ZnS red light quantum dot solution with the concentration of 2.5mg/ml on the organic heterojunction layer by using a spin coater. The front rotation speed of the spin coater is set to be 500r/min, the time is 5s, the rotation speed is set to be 2000r/min, and the time is 60s after the water-soluble InP/ZnS red light quantum dot solution is uniformly spread on the substrate. Annealing at 120 deg.C for 5min, and cooling for 2min to obtain 50nm quantum dot layer.
And covering the active layer with 100 nm-thick ionic gel to obtain the photoelectric sensor chip.
Example 3
Drawing of a chip die was performed using a CAD drawing tool, in which the connection between the source and drain electrodes was an interdigital structure, and the formed conductive channel had a length of 15 μm and a width of 1.5 cm.
And thermally evaporating a chromium adhesion layer with the thickness of 8nm on a SEBS substrate with the thickness of 50nm in vacuum, and thermally evaporating a gold conductive layer with the thickness of 80nm on the chromium adhesion layer in vacuum to prepare three chromium-gold alloy electrodes which are arranged at intervals and respectively used as a source electrode, a drain electrode and a grid electrode. The distance between the grid and the conducting channel is less than or equal to 0.1 mm.
And soaking the substrate containing the source electrode, the drain electrode and the grid electrode in an acetone solution, and carrying out surface ultrasonic cleaning by an ultrasonic cleaning machine.
Diluting the water-soluble InP/ZnS red light quantum dot solution with water to 2.5mg/ml, and coating the water-soluble InP/ZnS red light quantum dot solution with 2.5mg/ml on a substrate between a source electrode and a drain electrode by using a spin coater. The front rotation speed of the spin coater is set to be 500r/min, the time is 5s, the rotation speed is set to be 2000r/min, and the time is 60s after the water-soluble InP/ZnS red light quantum dot solution is uniformly spread on the substrate. Annealing at 180 deg.C for 5min, and cooling for 2min to obtain 25nm quantum dot layer.
The organic heterojunction solution is prepared according to the proportion of PDPP2T: PC by a spin coater61BM (InP/ZnS) is coated and thrown on the quantum dot layer and the source electrode and the drain electrode in a mass ratio of 1:1:0.5, the forward rotation speed of a spin coater is set to be 500r/min for 5s, and after the organic heterojunction solution is uniformly spread, the rotation speed is set to be 2000r/min for 60 s. Annealing at 120 ℃ for 20 minutes resulted in an organic heterojunction layer with a thickness of 140 nm.
And 2.5mg/ml of water-soluble InP/ZnS red light quantum dot solution is coated and spun on the organic heterojunction layer by using a spin coater. The front rotation speed of the spin coater is set to be 500r/min, the time is 5s, the rotation speed is set to be 2000r/min, and the time is 60s after the water-soluble InP/ZnS red light quantum dot solution is uniformly spread on the substrate. Annealing at 180 deg.C for 5min, and cooling to obtain 25nm quantum dot layer.
Covering the active layer with 200nm ionic gel to obtain the photoelectric sensor chip.
Example 4
Drawing of a chip die was performed using a CAD drawing tool, in which the connection between the source and drain electrodes was an interdigital structure, and the formed conductive channel had a length of 15 μm and a width of 1.5 cm.
And thermally evaporating a chromium adhesion layer with the thickness of 8nm on a SEBS substrate with the thickness of 50nm in vacuum, and thermally evaporating a gold conductive layer with the thickness of 80nm on the chromium adhesion layer in vacuum to prepare three chromium-gold alloy electrodes which are arranged at intervals and respectively used as a source electrode, a drain electrode and a grid electrode. The distance between the grid and the conducting channel is less than or equal to 0.1 mm.
And soaking the substrate containing the source electrode, the drain electrode and the grid electrode in an acetone solution, and carrying out surface ultrasonic cleaning by an ultrasonic cleaning machine.
Diluting the water-soluble InP/ZnS red light quantum dot solution with core-shell structure to 2.5mg/ml with water, and mixing with the organic heterojunction solution according to PDPP2T: PC61And mixing the materials in a mass ratio of 1:1:1 to obtain a mixed solution of the quantum dots and the organic heterojunction, and coating the mixed solution on the substrate between the source electrode and the drain electrode and the source electrode and the drain electrode by using a spin coater. Glue homogenizingThe front rotation speed of the machine is set to be 500r/min, the time is 5s, after the water-soluble InP/ZnS red light quantum dot solution is uniformly spread on the substrate, the rotation speed is set to be 2000r/min, and the time is 60 s. Annealing at 120 deg.C for 20min to obtain 160nm thick organic heterojunction layer with quantum dots dispersed therein.
Covering the organic heterojunction layer with the ionic gel with the thickness of 180nm to obtain the photoelectric sensor chip.
Comparative example 1
Drawing of a chip die was performed using a CAD drawing tool, in which the connection between the source and drain electrodes was an interdigital structure, and the formed conductive channel had a length of 15 μm and a width of 1.5 cm.
And thermally evaporating a chromium adhesion layer with the thickness of 8nm on a SEBS substrate with the thickness of 50nm in vacuum, and thermally evaporating a gold conductive layer with the thickness of 80nm on the chromium adhesion layer in vacuum to prepare three chromium-gold alloy electrodes which are arranged at intervals and respectively used as a source electrode, a drain electrode and a grid electrode. The distance between the grid and the conducting channel is less than or equal to 0.1 mm.
And soaking the substrate containing the source electrode, the drain electrode and the grid electrode in an acetone solution, and carrying out surface ultrasonic cleaning by an ultrasonic cleaning machine.
And (3) coating the organic heterojunction solution on the substrate between the source electrode and the drain electrode and the source electrode and the drain electrode by using a spin coater (wherein the use amount of the organic heterojunction solution is the same as that in the embodiment 1,2 or 3), setting the forward rotation speed of the spin coater to be 500r/min and the time to be 5s, and setting the rotation speed to be 2000r/min and the time to be 60s after the organic heterojunction solution is uniformly spread. Annealing at 120 ℃ for 20 minutes resulted in an organic heterojunction layer with a thickness of 140 nm.
And covering the ionic gel with the thickness of 150nm on the active layer to obtain the photoelectric sensor chip.
The photosensor chips of example 1 and comparative example 1 were subjected to the FET test, and the test results are shown in fig. 5 and fig. 6a to 6b, and it can be seen that the photosensor of comparative example 1 (i.e., a photosensor having no quantum dot in the active layer) had a minimum dark current of 10-8A, and the photo-sensor chip in embodiment 1 (i.e., photo-sensing with quantum dots in the active layer)Device chip) with a minimum dark current of 10-10A. The sensitivity of the photosensor chip in comparative example 1 (i.e., the photosensor chip without quantum dots in the active layer) was 250, while the sensitivity of the photosensor chip in example 1 (i.e., the photosensor chip with quantum dots in the active layer) was 104. The photosensor chip in comparative example 1 (i.e., the photosensor chip without the quantum dot in the active layer) had a switching ratio of 10 in the dark5Whereas the photosensor chip in example 1 (i.e., the photosensor chip having quantum dots in the active layer) had a switching ratio of 4 × 10 in the dark6. The above tests can show that the photosensor chip with quantum dots in the active layer has lower dark current and higher sensitivity.
In summary, the invention provides a photoelectric sensor chip, a preparation method thereof and a photoelectric sensor, wherein quantum dots are introduced into an active layer to modify the active layer, and the quantum dots can be used as defect centers in an electron transportation process to effectively limit the movement of electrons, thereby reducing the dark current of the photoelectric sensor and improving the sensitivity of the photoelectric sensor. Meanwhile, an electronic defect state is introduced, so that the mobility of electrons is reduced, and the optical gain of the photoelectric sensor is improved. The dark current of the photoelectric sensor provided by the invention can reach 10-10A, sensitivity can reach 104. The preparation method provided by the invention is simple and easy to realize, and has higher practicability and economic value.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A photoelectric sensor chip is characterized by comprising a substrate, a source electrode, a drain electrode and a grid electrode which are arranged on the substrate at intervals, an active layer arranged on the substrate between the source electrode and the drain electrode and on the source electrode and the drain electrode, and a dielectric layer arranged on the active layer, wherein the active layer comprises an organic heterojunction material and a quantum dot material.
2. The photosensor chip of claim 1, wherein the mass ratio of the organic heterojunction material to the quantum dot material is 2: 1.
3. The photosensor chip according to claim 1, wherein the active layer is composed of an organic heterojunction layer formed of the organic heterojunction material and a quantum dot layer formed of the quantum dot material, the quantum dot layer being disposed below the organic heterojunction layer, the quantum dot layer being attached to the substrate between the source electrode and the drain electrode;
or the active layer is composed of an organic heterojunction layer formed by the organic heterojunction material and a quantum dot layer formed by the quantum dot material, and the quantum dot layer is arranged above the organic heterojunction layer;
or the active layer is composed of an organic heterojunction layer formed by the organic heterojunction material and a quantum dot layer formed by the quantum dot material, and the quantum dot layers are simultaneously arranged above and below the organic heterojunction layer;
alternatively, the active layer is composed of the organic heterojunction material and the quantum dot material dispersed in the organic heterojunction material.
4. The photosensor chip of claim 3, wherein when the quantum dot layer is disposed below the organic heterojunction layer, the quantum dot layer has a thickness of 45-55 nm;
or when the quantum dot layer is arranged above the organic heterojunction layer, the thickness of the quantum dot layer is 45-55 nm;
or when the quantum dot layers are simultaneously arranged above and below the organic heterojunction layer, the total thickness of the quantum dot layers is 45-55 nm.
5. The photosensor chip of claim 1, wherein the quantum dot material is 3-6nm in size.
6. The photosensor chip of claim 5, wherein the quantum dot material is a red light quantum dot material.
7. The photosensor chip of claim 6, wherein the red light quantum dot material is a core-shell red light quantum dot material.
8. The photoelectric sensor chip of claim 7, wherein the core-shell red light quantum dot material is selected from one or more of core-shell InP/ZnS red light quantum dot material, core-shell CdSe/ZnS red light quantum dot material, and core-shell ZnSe/ZnS red light quantum dot material.
9. A method for preparing a photosensor chip according to any one of claims 1 to 8, comprising the steps of:
providing a substrate;
preparing a source electrode, a drain electrode and a grid electrode on the substrate;
preparing an active layer on the substrate between the source electrode and the drain electrode and on the source electrode and the drain electrode, the active layer comprising an organic heterojunction material and a quantum dot material;
and preparing a dielectric layer on the active layer to obtain the photoelectric sensor chip.
10. A photosensor comprising the photosensor chip according to any one of claims 1 to 8.
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