CN111799380A - Organic-inorganic composite photoconductive detector and preparation method and application thereof - Google Patents

Organic-inorganic composite photoconductive detector and preparation method and application thereof Download PDF

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CN111799380A
CN111799380A CN202010704364.3A CN202010704364A CN111799380A CN 111799380 A CN111799380 A CN 111799380A CN 202010704364 A CN202010704364 A CN 202010704364A CN 111799380 A CN111799380 A CN 111799380A
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CN111799380B (en
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韩滔
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Xiangnan University
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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    • Y02E10/549—Organic PV cells

Abstract

The invention relates to the technical field of photoconductive detection devices, in particular to an organic-inorganic composite photoconductive detection device and a preparation method and application thereof. The work function of the inorganic semiconductor nano material in the inorganic semiconductor nano material layer in the organic-inorganic composite photoconductive detection device provided by the invention is larger than that of the donor: receptor: work function of the acceptor material in the PMMA blended layer; the donor: receptor: the PMMA blending layer is used for P-type charge transmission; the inorganic semiconductor nano material layer is in N-type charge transmission; the donor: receptor: and the interface between the PMMA blended layer and the inorganic semiconductor nano material layer forms a plane heterojunction structure. The photoconductive detection device can simultaneously realize the characteristics of low price, stability and quick response.

Description

Organic-inorganic composite photoconductive detector and preparation method and application thereof
Technical Field
The invention relates to the technical field of photoconductive detection devices, in particular to an organic-inorganic composite photoconductive detection device and a preparation method and application thereof.
Background
As is well known, the organic-inorganic composite photoconductive detector of the near-infrared bulk heterojunction polymer has the advantages of large-area processing of an organic semiconductor, high mechanical flexibility, high mobility and high crystallinity of an inorganic semiconductor, and is widely applied to emerging fields such as mobile devices (3D face recognition and mobile payment), unmanned aerial vehicle systems, Advanced Driving Assistance Systems (ADAS), augmented/virtual reality (AR/VR), and the like. The organic-inorganic composite photoconductive detector is easy to obtain high gain and wide electrode distance, so that the dark current of the detector is low, and the near infrared bulk heterojunction and the inorganic semiconductor nano material are combined, and the UV-Vis-NIR wide spectral response can be realized by a solution processing method. However, the main problems of the photoconductive detection device are that the problems of expensive near-infrared polymer raw material, low stability and slow response speed of the device cannot be effectively solved.
At present, aiming at the problem of unstable performance, methods such as packaging by a water-oxygen isolation layer, adopting an organic material which does not react with water and oxygen, selecting an organic single crystal material with high mobility and the like are mainly adopted, but the methods have no universality on near infrared polymers and can not effectively solve the problem that the near infrared materials are expensive. In addition, aiming at the problem of slow response speed of a photoconductive device, the prior art generally adopts passivated grain boundaries or selects low-defect 1D/2D materials; a heterojunction structure is constructed, energy level arrangement is optimized, and carrier transfer is enhanced to shorten free carrier transmission time; and (3) capturing photo-generated minority carriers by using a trap, transferring the photo-generated minority carriers out of the active layer to reduce the recombination life of the photo-generated minority carriers, and the like. However, these methods are either not suitable for near-infrared polymers or have a limited increase in response speed. In particular, these methods of increasing the response speed are not necessarily applicable when stability factors are considered together.
Disclosure of Invention
The invention aims to provide an organic-inorganic composite photoconductive detector, and a preparation method and application thereof, wherein the organic-inorganic composite photoconductive detector can simultaneously realize the characteristics of low price, stability and quick response.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an organic-inorganic composite photoconductive detector, which comprises a substrate layer, an inorganic semiconductor nano material layer and a donor which are sequentially stacked: receptor: a PMMA blending layer and a metal electrode layer;
or a base layer and a donor which are sequentially stacked: receptor: the PMMA blending layer, the inorganic semiconductor nano material layer and the metal electrode layer;
the work function of the inorganic semiconductor nano material in the inorganic semiconductor nano material layer is greater than that of the donor: receptor: work function of the acceptor material in the PMMA blended layer;
the donor: receptor: the PMMA blending layer is used for P-type charge transmission; the inorganic semiconductor nano material layer is in N-type charge transmission;
the donor: receptor: and the interface of the PMMA blended layer and the inorganic semiconductor nano material layer forms a plane heterojunction structure.
Preferably, the thickness of the inorganic semiconductor nano material layer is 30-500 nm.
Preferably, the inorganic semiconductor nano material is a zinc oxide nano material or a gallium nitride nano material.
Preferably, the donor: receptor: the mass ratio of the donor to the acceptor to the PMMA in the PMMA blending layer is (1-7): (1-7): (1-7).
Preferably, the material of the receptor is (6,6) -phenyl-C61-butyric acid methyl ester or (6,6) -phenyl-C71-methyl butyrate.
Preferably, the material of the donor is one or more of polydithiophene pyrrolopyrrole dione-thiophene, polydithiophene pyrrolopyrrole dione, diketopyrrolopyrrole-thienothiophene and polythiophene-pyrrolopyrrole dione.
Preferably, the donor: receptor: the thickness of the PMMA blending layer is 80-300 nm.
The invention also provides a preparation method of the organic-inorganic composite photoconductive detector in the technical scheme, which comprises the following steps:
providing a suspension of inorganic semiconductor nano-materials;
providing a blend of donor, acceptor and PMMA;
coating the suspension of the inorganic semiconductor nano material and the mixed solution of the donor, the acceptor and PMMA on the upper surface of the substrate layer in sequence to obtain an inorganic semiconductor nano material layer and a donor: receptor: a PMMA blend layer;
in the donor: receptor: evaporating a metal electrode layer on the upper surface of the PMMA blending layer to obtain the organic-inorganic composite photoconductive detector;
or coating the mixed solution of the donor, the acceptor and PMMA and the suspension of the inorganic semiconductor nano material on the upper surface of the substrate layer in sequence to obtain a donor: receptor: a PMMA blending layer and an inorganic semiconductor nano material layer;
and evaporating a metal electrode layer on the upper surface of the inorganic semiconductor nano material layer to obtain the organic-inorganic composite photoconductive detector.
The invention also provides an application of the organic-inorganic composite photoconductive detector in the technical scheme or the organic-inorganic composite photoconductive detector prepared by the preparation method in the technical scheme in the fields of mobile equipment, unmanned aerial vehicle systems, advanced driving assistance systems or enhanced/virtual reality.
The invention provides an organic-inorganic composite photoconductive detector, which comprises a substrate layer, an inorganic semiconductor nano material layer and a donor which are sequentially stacked: receptor: a PMMA blending layer and a metal electrode layer; or a base layer and a donor which are sequentially stacked: receptor: the PMMA blending layer, the inorganic semiconductor nano material layer and the metal electrode layer; the work function of the inorganic semiconductor nano material in the inorganic semiconductor nano material layer is greater than that of the donor: receptor: work function of the acceptor material in the PMMA blended layer; the donor: receptor: the PMMA blending layer is used for P-type charge transmission; the inorganic semiconductor nano material layer is in N-type charge transmission; the donor: receptor: and the interface of the PMMA blended layer and the inorganic semiconductor nano material layer forms a plane heterojunction structure. The invention utilizes the blending of the donor, the acceptor and the PMMA as an organic blending layer, wherein the added PMMA can realize the purposes of low price and high stability; by constructing the bulk heterojunction type photoconductive detector with the plane-bulk heterojunction structure and the inorganic semiconductor nano material layer/organic blending layer (donor: acceptor: PMMA blending layer) integrated structure, the energy level gradient between the inorganic semiconductor nano material layer and the acceptor is utilized to promote the transfer of photominority carriers out of the active layer and capture the photominority carriers by the nano material layer, and simultaneously, the purposes of low price, stability and quick response are realized.
Drawings
FIG. 1 is a schematic structural diagram of an organic-inorganic composite photoconductive detector device according to the present invention;
fig. 2 is a schematic view of the structures of a photoconductive device described in comparative example 1 and an organic-inorganic composite photoconductive detection device described in example 1;
FIG. 3 is a schematic diagram of a photoconductive detector device testing system in accordance with the present invention;
FIG. 4 is a graph of response times for a photoconductive device as described in comparative example 1 and an organic-inorganic composite photoconductive detector device as described in example 1;
fig. 5 is a graph showing the device stability of the photoconductive device described in comparative example 1 and the organic-inorganic composite photoconductive detection device described in example 1.
Detailed Description
The invention provides an organic-inorganic composite photoconductive detector, which comprises a substrate layer, an inorganic semiconductor nano material layer and a donor which are sequentially stacked: receptor: a PMMA blended layer and a metal electrode layer (as shown in (a) of fig. 1);
or a base layer and a donor which are sequentially stacked: receptor: a PMMA blended layer, an inorganic semiconductor nano material layer and a metal electrode layer (as shown in a (b) diagram in figure 1);
the work function of the inorganic semiconductor nano material in the inorganic semiconductor nano material layer is greater than that of the donor: receptor: work function of the acceptor material in the PMMA blended layer;
the donor: receptor: the PMMA blending layer is used for P-type charge transmission; the inorganic semiconductor nano material layer is of an N type;
the donor: receptor: and the interface of the PMMA blended layer and the inorganic semiconductor nano material layer forms a plane heterojunction structure.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
The organic-inorganic composite photoconductive detection device provided by the invention comprises a substrate layer, wherein the substrate layer is preferably a quartz plate or a silicon plate. The thickness of the substrate layer is not particularly limited in the present invention, and may be any thickness known to those skilled in the art.
The organic-inorganic composite photoconductive detection device provided by the invention comprises an inorganic semiconductor nano material layer. In the invention, the thickness of the inorganic semiconductor nano material layer is preferably 30-500 nm. The inorganic semiconductor nano material in the inorganic semiconductor nano material layer is preferably a zinc oxide nano material or a gallium nitride nano material; the zinc oxide nano material is preferably zinc oxide nano particles or zinc oxide nano rods; the gallium nitride nanomaterial is preferably a gallium nitride nanowire. In the invention, when the inorganic semiconductor nano material comprises zinc oxide nano particles, the particle size of the zinc oxide nano particles is preferably 5-60 nm, and more preferably 10-50 nm; when the inorganic semiconductor nano material comprises a zinc oxide nano rod, the diameter of the zinc oxide nano rod is preferably 10-50 nm, more preferably 20-40 nm, and the length of the zinc oxide nano rod is preferably 200-2000 nm, more preferably 300-1200 nm; when the inorganic semiconductor nano material comprises a gallium nitride nanowire, the diameter of the gallium nitride nanowire is preferably 10-100 nm, more preferably 20-80 nm, and the length of the gallium nitride nanowire is preferably 1-5 μm, more preferably 2-4 μm. In the invention, when the material of the inorganic semiconductor nano material layer is a zinc oxide nano material, the thickness of the inorganic semiconductor nano material layer is more preferably 30-300 nm; when the material of the inorganic semiconductor nano material layer is a gallium nitride nano material, the thickness of the inorganic semiconductor nano material layer is more preferably 100-500 nm.
In the invention, the inorganic semiconductor nano material layer is an active layer which can generate photon-generated carriers after absorbing ultraviolet light; the donor: receptor: the PMMA blended layer is also an active layer that can generate photogenerated carriers upon absorption of visible and near infrared light.
The organic-inorganic composite photoconductive detector provided by the invention further comprises a donor: receptor: a PMMA blend layer. In the present invention, the donor: receptor: the material of the PMMA blended layer preferably includes donor, acceptor and PMMA. In the present inventionThe material of the donor is preferably one or more of polydithiophene pyrrolopyrrole-dione-thiophene (PDPPBTT), polydithiophene pyrrolopyrrole-pyrrole-dione (DPP-DTT), diketopyrrolopyrrole-thienothiophene (PDPP2T-TT-OD) and polythiophene-pyrrolopyrrole-dione (PDPP 3T); when the material of the donor is more than two of the above specific choices, the invention does not have any special limitation on the proportion of the above specific materials, and the materials can be mixed according to any proportion. In the present invention, the material of the receptor is preferably (6,6) -phenyl-C61-butyric acid methyl ester (PC)61BM) or (6,6) -phenyl-C71-butyric acid methyl ester (PC)71BM). In the invention, the mass ratio of the donor to the acceptor to the PMMA is preferably (1-7): (1-7): (1 to 7), more preferably 1:1: (1-7). In the present invention, the donor: receptor: the thickness of the PMMA blending layer is preferably 80-300 nm, and more preferably 100-200 nm.
In the present invention, the donor: receptor: the PMMA blending layer presents a P-type charge transfer characteristic, the proportion of the donor, the acceptor and PMMA is controlled within the range, and a planar P-N heterojunction structure can be formed on the inorganic semiconductor nano material layer; meanwhile, since PMMA has the function of resisting water and oxygen, after PMMA is mixed with a donor and an acceptor, the contact chance of donor and acceptor materials which are easy to react with water and oxygen with air is reduced, and the function of improving the stability of the device is achieved; on the other hand, because PMMA is low in price, the donor and acceptor materials are expensive, and when the PMMA, the donor and acceptor materials are blended, the concentrations of the donor and the acceptor are diluted, and the effect of reducing the cost is achieved.
In the present invention, the donor: receptor: the PMMA blending layer is used for P-type charge transmission; the inorganic semiconductor nano material layer is in N-type charge transmission; the donor: receptor: and the interface between the PMMA blended layer and the inorganic semiconductor nano material layer forms a plane heterojunction structure. The structure can enable the inorganic semiconductor nano material and the receptor material to form an energy level gradient, promote the capture of photon-generated minority carriers and greatly improve the response speed of the photoconductive detection device.
The organic-inorganic composite photoconductive detection device also comprises a metal electrode layer; the metal electrode layer comprises a positive electrode and a negative electrode; the material of the metal electrode layer is preferably silver, gold or aluminum. The thickness of the metal electrode layer is preferably 50-200 nm, and more preferably 100-150 nm. The electrode length of the positive electrode and the negative electrode is preferably 1000 μm, and the width is preferably 40 μm.
The invention also provides a preparation method of the organic-inorganic composite photoconductive detector in the technical scheme, which comprises the following steps:
providing a suspension of inorganic semiconductor nano-materials;
providing a blend of donor, acceptor and PMMA;
coating the suspension of the inorganic semiconductor nano material and the mixed solution of the donor, the acceptor and PMMA on the upper surface of the substrate layer in sequence to obtain an inorganic semiconductor nano material layer and a donor: receptor: a PMMA blend layer;
in the donor: receptor: evaporating a metal electrode layer on the upper surface of the PMMA blending layer to obtain the organic-inorganic composite photoconductive detector;
or coating the mixed solution of the donor, the acceptor and PMMA and the suspension of the inorganic semiconductor nano material on the upper surface of the substrate layer in sequence to obtain a donor: receptor: a PMMA blending layer and an inorganic semiconductor nano material layer;
and evaporating a metal electrode layer on the upper surface of the inorganic semiconductor nano material layer to obtain the organic-inorganic composite photoconductive detector.
The preparation method comprises the step of providing a suspension of the inorganic semiconductor nano material. In the present invention, when the inorganic semiconductor nanomaterial is a zinc oxide nanomaterial, the method for preparing the suspension of the inorganic semiconductor nanomaterial is preferably to mix the zinc oxide nanomaterial with chlorobenzene to obtain the suspension of the zinc oxide nanomaterial. The present invention does not limit the mixing in any particular way, and the mixing may be carried out by a process known to those skilled in the art. The mass concentration of the suspension of the zinc oxide nanomaterial is preferably 1 wt%. In the present invention, when the inorganic semiconductor nanomaterial is a gallium nitride nanomaterial, the method for preparing the suspension of the inorganic semiconductor nanomaterial is preferably to mix the gallium nitride nanomaterial with ethanol to obtain the suspension of the gallium nitride nanomaterial. The present invention does not limit the mixing in any particular way, and the mixing may be carried out by a process known to those skilled in the art. The mass concentration of the suspension of the gallium nitride nanomaterial is preferably 1 wt%.
The preparation method of the invention also comprises the step of providing a blend of the donor, the acceptor and the PMMA. In the invention, the donor, the acceptor, PMMA and an organic solvent are mixed to obtain a blended solution of the donor, the acceptor and PMMA; in the present invention, the organic solvent is preferably chlorobenzene or o-dichlorobenzene. In the invention, the concentration of the donor in the blending liquid of the donor, the acceptor and PMMA is preferably 2-3 mg/mL, and more preferably 2.5 mg/mL. In the present invention, the mixing is preferably performed under stirring conditions, and the stirring speed in the present invention is not particularly limited, and may be performed at a speed known to those skilled in the art. In the invention, the stirring time is preferably 10-15 h, and more preferably 12 h.
The preparation method of the invention also comprises the following steps of sequentially coating the suspension of the inorganic semiconductor nano material and the blending liquid of the donor, the acceptor and PMMA on the upper surface of the substrate layer to obtain an inorganic semiconductor nano material layer and the donor: receptor: a PMMA blend layer. In the present invention, the base layer is preferably subjected to a pretreatment. The pretreatment preferably comprises washing and drying; the cleaning is preferably performed by sequentially adopting deionized water, acetone and isopropanol; the drying is preferably oven drying. In the invention, when the inorganic semiconductor nano-material suspension is coated, when the inorganic semiconductor nano-material suspension is zinc oxide nano-material suspension, the coating mode is preferably spin coating, and the rotation speed of the spin coating is preferably 1000-4000 r.p.m, more preferably 1500-3500 r.p.m, and most preferably 2000-3000 r.p.m; when the suspension of the inorganic semiconductor nanomaterial is a suspension of a gallium nitride nanomaterial, the coating is preferably performed by drop coating. In the dripping process, the substrate layer is preferably arranged on a heating table, and the temperature of the heating table is preferably 65-75 ℃, and more preferably 70 ℃. The coating times are not limited in any way, and the thickness of the gallium nitride nanometer material layer can reach 100-500 nm by adopting the times known by the technicians in the field. In the invention, the mode of coating the blending liquid of the donor, the acceptor and PMMA is preferably spin coating, and the rotating speed of the spin coating is preferably 1000-3000 r.p.m.
The preparation method of the invention also comprises the following steps of: receptor: and evaporating a metal electrode layer on the upper surface of the PMMA blending layer to obtain the organic-inorganic composite photoconductive detector. In the present invention, the rate of the evaporation is preferably set to be lower than the rate of the evaporation
Figure BDA0002594119810000071
Or, the preparation method of the invention comprises the following steps of sequentially coating the donor, the receptor and PMMA blended solution and the inorganic semiconductor nano material suspension on the upper surface of the substrate layer to obtain the donor: receptor: a PMMA blending layer and an inorganic semiconductor nano material layer;
and evaporating a metal electrode layer on the upper surface of the inorganic semiconductor nano material layer to obtain the organic-inorganic composite photoconductive detector.
Preparation of the donor: receptor: the procedure for PMMA blending layer, inorganic semiconductor nanomaterial layer and metal electrode layer is preferably described with reference to the above donor: receptor: the preparation processes of the PMMA blending layer, the inorganic semiconductor nano material layer and the metal electrode layer are not described in detail herein.
In the present invention, the fabrication process of the organic-inorganic composite photoconductive detector is preferably performed in a glove box.
The invention also provides an application of the organic-inorganic composite photoconductive detector in the technical scheme or the organic-inorganic composite photoconductive detector prepared by the preparation method in the technical scheme in the fields of mobile equipment, unmanned aerial vehicle systems, advanced driving assistance systems or enhanced/virtual reality.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Cleaning the quartz plate by sequentially adopting deionized water, acetone and isopropanol, and drying to obtain a clean quartz plate;
mixing zinc oxide nano particles with the particle size of 5nm with chlorobenzene to obtain zinc oxide suspension with the mass concentration of 1 wt%;
under stirring, according to PDPPBTT and PC61The mass ratio of BM to PMMA is 1:1: 4, mixing PDPPBTT and PC61Mixing BM, PMMA and chlorobenzene for 12h to obtain a blended solution of a donor, an acceptor and PMMA, wherein the concentration of PDPPBTT in the blended solution of the donor, the acceptor and the PMMA is 2.5 mg/mL;
putting the clean quartz plate into a glove box, and spin-coating the zinc oxide suspension on the upper surface of the clean quartz plate at the rotation speed of 2500r.p.m to obtain an inorganic semiconductor nano material layer (the thickness is 150 nm);
and spin-coating the blend of the donor, the acceptor and PMMA on the upper surface of the inorganic semiconductor nano material layer at the spin-coating speed of 2500r.p.m, so as to obtain a donor: receptor: a PMMA blend layer (thickness 120 nm);
by means of a mask, at the donor: receptor: and evaporating a silver electrode layer (the thickness is 100nm, the length of the electrode is 1000 μm, and the width of the electrode is 40 μm) on the upper surface of the PMMA blended layer to obtain the organic-inorganic composite photoconductive detector (the structure is shown in the right diagram of FIG. 2).
Example 2
Cleaning the quartz plate by sequentially adopting deionized water, acetone and isopropanol, and drying to obtain a clean quartz plate;
mixing gallium nitride nanowires with the diameter of 80nm and the length of 3 mu m with ethanol to obtain a gallium nitride suspension with the mass concentration of 1 wt%;
under stirring, the mixture is mixed according to PDPP3T and PC71The mass ratio of BM to PMMA is 1:3:6, and PDPP3T and PC are added71Mixing BM, PMMA and chlorobenzene for 12h to obtain a blending liquid of a donor, an acceptor and PMMA, wherein the concentration of PDPP3T in the blending liquid of the donor, the acceptor and the PMMA is 2.0 mg/mL;
putting the clean quartz plate into a glove box, and dripping the gallium nitride suspension liquid on the upper surface of the clean quartz plate to obtain an inorganic semiconductor nano material layer (the thickness is 300 nm);
and spin-coating the blend of the donor, the acceptor and PMMA on the upper surface of the inorganic semiconductor nano material layer at the spin-coating speed of 2500r.p.m, so as to obtain a donor: receptor: a PMMA blend layer (thickness 150 nm);
by means of a mask, at the donor: receptor: and evaporating a silver electrode layer (the thickness is 100nm, the length of the electrode is 1000 mu m, and the width of the electrode is 40 mu m) on the upper surface of the PMMA blended layer to obtain the organic-inorganic composite photoconductive detector.
Example 3
Cleaning the quartz plate by sequentially adopting deionized water, acetone and isopropanol, and drying to obtain a clean quartz plate;
mixing a zinc oxide nanorod with the diameter of 20nm and the length of 300nm with ethanol to obtain a zinc oxide suspension with the mass concentration of 1 wt%;
under stirring, according to DPP-DTT and PC61The mass ratio of BM to PMMA is 1: 2: 4, DPP-DTT and PC61Mixing BM, PMMA and o-dichlorobenzene for 12 hours to obtain a blending solution of a donor, an acceptor and PMMA, wherein the concentration of DPP-DTT in the blending solution of the donor, the acceptor and the PMMA is 2.0 mg/mL;
putting the clean quartz plate into a glove box, and spin-coating the zinc oxide suspension on the upper surface of the clean quartz plate at a rotation speed of 1500r.p.m to obtain an inorganic semiconductor nano material layer (with the thickness of 200 nm);
and spin-coating the blend of the donor, the acceptor and PMMA on the upper surface of the inorganic semiconductor nano material layer at the spin-coating speed of 2500r.p.m, so as to obtain a donor: receptor: a PMMA blend layer (thickness 150 nm);
by means of a mask, at the donor: receptor: and evaporating a silver electrode layer (the thickness is 100nm, the length of the electrode is 1000 mu m, and the width of the electrode is 40 mu m) on the upper surface of the PMMA blended layer to obtain the organic-inorganic composite photoconductive detector.
Example 4
Cleaning the quartz plate by sequentially adopting deionized water, acetone and isopropanol, and drying to obtain a clean quartz plate;
mixing zinc oxide nano particles with the diameter of 30nm with chlorobenzene to obtain zinc oxide suspension with the mass concentration of 1 wt%;
under stirring, according to PDPP2T-TT-OD, PC71The mass ratio of BM to PMMA is 1:1:5, and PDPP2T-TT-OD and PC are added71Mixing BM, PMMA and o-dichlorobenzene for 12 hours to obtain a blending liquid of a donor, an acceptor and PMMA, wherein the concentration of PDPP2T-TT-OD in the blending liquid of the donor, the acceptor and the PMMA is 2.5 mg/mL;
putting the clean quartz plate into a glove box, and spin-coating the zinc oxide suspension on the upper surface of the clean quartz plate at the rotation speed of 2000r.p.m to obtain an inorganic semiconductor nano material layer (the thickness is 160 nm);
and spin-coating the blend of the donor, the acceptor and PMMA on the upper surface of the inorganic semiconductor nano material layer at the spin-coating speed of 2500r.p.m, so as to obtain a donor: receptor: a PMMA blend layer (thickness 180 nm);
by means of a mask, at the donor: receptor: and evaporating a silver electrode layer (the thickness is 100nm, the length of the electrode is 1000 mu m, and the width of the electrode is 40 mu m) on the upper surface of the PMMA blended layer to obtain the organic-inorganic composite photoconductive detector.
Comparative example 1
Cleaning the quartz plate by sequentially adopting deionized water, acetone and isopropanol, and drying to obtain a clean quartz plate;
under stirring, according to PDPPBTT and PC61The mass ratio of BM is 1:1, mixing PDPPBTT and PC61BM and chlorobenzene are mixed for 12 hours to obtain a blending solution, and the concentration of PDPPBTT in the blending solution is 2.5 mg/mL;
placing the clean quartz plate in a glove box, and spin-coating the blend on the upper surface of the clean quartz plate, wherein the spin-coating speed is 2000r.p.m, so as to obtain a donor: receptor layer (thickness 120 nm);
by means of a mask, at the donor: and evaporating a silver electrode layer (with the thickness of 100nm, the length of the electrode of 1000 μm and the width of 40 μm) on the upper surface of the receptor layer to obtain the photoconductive detection device (the structure is shown in the left diagram in FIG. 2).
Test example
The response time of the device is tested by utilizing a photoconductive detection device testing system consisting of a semiconductor analyzer, a probe station, a microscope and lasers with different wavelengths (355nm single-wavelength laser, 405nm single-wavelength laser and 410-2400nm continuous laser). As shown in fig. 3, the laser is applied through an optical fiber and a microscope to the middle of the positive and negative electrodes of the device. When the device is subjected to dark state to illumination change, the time required for the current value to rise from 10% to 90% is the rising time; when the device is subjected to light illumination to dark state change, the time required for the current value to drop from 90% to 10% is the drop time. The device is tested in a dark room, and when illumination is needed, a laser is used as a light source to apply illumination to the device. The test result of the photoconductive detection device is shown in fig. 4, wherein the left graph in fig. 4 is a response time graph of the photoconductive detection device described in comparative example 1, the right graph in fig. 4 is a response time graph of the organic-inorganic composite photoconductive detection device described in example 1, and as can be seen from fig. 4, the rise time of the photoconductive detection device described in comparative example 1 is 93ms, and the fall time is 114 ms; the rise time and the fall time of the organic-inorganic composite photoconductive detection device described in example 1 are 7ms and 4.5ms, which shows that the response speed of the organic-inorganic composite photoconductive detection device described in example 1 is obviously improved.
A semiconductor analyzer, a probe station, a microscope and a photoconductive detection device testing system composed of lasers with different wavelengths (355nm single-wavelength lasers, 405nm single-wavelength lasers and 410-2400nm continuous lasers) are used for testing the stability of the device. As shown in fig. 3, the laser is applied through an optical fiber and a microscope to the middle of the positive and negative electrodes of the device. When testing the stability, the device is continuously illuminated, the whole testing process is carried out in a darkroom, and the light source is provided by a laser. As shown in fig. 5, it can be seen from fig. 5 that the photocurrent of the organic-inorganic composite photoconductive detection device described in example 1 was substantially stable with time, while the photocurrent of the photoconductive device described in comparative example 1 was rapidly attenuated with time.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. An organic-inorganic composite photoconductive detector comprises a substrate layer, an inorganic semiconductor nano material layer and a donor which are sequentially stacked: receptor: a PMMA blending layer and a metal electrode layer;
or a base layer and a donor which are sequentially stacked: receptor: the PMMA blending layer, the inorganic semiconductor nano material layer and the metal electrode layer;
the work function of the inorganic semiconductor nano material in the inorganic semiconductor nano material layer is greater than that of the donor: receptor: work function of the acceptor material in the PMMA blended layer;
the donor: receptor: the PMMA blending layer is used for P-type charge transmission; the inorganic semiconductor nano material layer is in N-type charge transmission;
the donor: receptor: and the interface of the PMMA blended layer and the inorganic semiconductor nano material layer forms a plane heterojunction structure.
2. The organic-inorganic composite photoconductive detector device of claim 1, wherein the thickness of the inorganic semiconductor nanomaterial layer is 30 to 500 nm.
3. The organic-inorganic composite photoconductive detector device of claim 1 or 2, wherein the inorganic semiconductor nanomaterial is a zinc oxide nanomaterial or a gallium nitride nanomaterial.
4. The organic-inorganic composite photoconductive detector device of claim 1, wherein the donor: receptor: the mass ratio of the donor to the acceptor to the PMMA in the PMMA blending layer is (1-7): (1-7): (1-7).
5. The organic-inorganic composite photoconductive detector device of claim 4, wherein the material of the acceptor is (6,6) -phenyl-C61-butyric acid methyl ester or (6,6) -phenyl-C71-methyl butyrate.
6. The organic-inorganic composite photoconductive detector of claim 4, wherein the donor material is one or more of polydithiophene pyrrolopyrrole dione-thiophene, polydithiophene-pyrrolopyrrole dione, diketopyrrolopyrrole-thienothiophene and polythiophene-pyrrolopyrrole dione.
7. The organic-inorganic composite photoconductive detector device according to any one of claims 1 and 4 to 6, wherein the donor: receptor: the thickness of the PMMA blending layer is 80-300 nm.
8. The method for preparing an organic-inorganic composite photoconductive detector device as claimed in any one of claims 1 to 7, characterized by comprising the steps of:
providing a suspension of inorganic semiconductor nano-materials;
providing a blend of donor, acceptor and PMMA;
coating the suspension of the inorganic semiconductor nano material and the mixed solution of the donor, the acceptor and PMMA on the upper surface of the substrate layer in sequence to obtain an inorganic semiconductor nano material layer and a donor: receptor: a PMMA blend layer;
in the donor: receptor: evaporating a metal electrode layer on the upper surface of the PMMA blending layer to obtain the organic-inorganic composite photoconductive detector;
or coating the mixed solution of the donor, the acceptor and PMMA and the suspension of the inorganic semiconductor nano material on the upper surface of the substrate layer in sequence to obtain a donor: receptor: a PMMA blending layer and an inorganic semiconductor nano material layer;
and evaporating a metal electrode layer on the upper surface of the inorganic semiconductor nano material layer to obtain the organic-inorganic composite photoconductive detector.
9. Use of the organic-inorganic composite photoconductive detector device according to any one of claims 1 to 7 or the organic-inorganic composite photoconductive detector device prepared by the preparation method according to claim 8 in mobile devices, unmanned aerial vehicle systems, advanced driving assistance systems or enhanced/virtual reality fields.
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