CN112635676A - Visible blind near-infrared narrow-band organic photoelectric detector - Google Patents
Visible blind near-infrared narrow-band organic photoelectric detector Download PDFInfo
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
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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
- H10K30/80—Constructional details
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
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- Y02E10/549—Organic PV cells
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Abstract
The invention relates to a visible blind near-infrared narrow-band organic photoelectric detector, which sequentially comprises a substrate, an anode, a filter layer, a hole selection layer, a PN blending body heterojunction layer and a cathode. The hole selection layer is made of a material having a hole transport function and selectively passes only holes. The filter layer is formed by layering or blending P-type materials or P-type materials and N-type materials, and the PN blending body heterojunction layer is formed by blending P-type materials and N-type materials. In the filter layer, a band gap of at least one material is wider than a band gap of at least one material in the PN-blend bulk heterojunction layer. An anode interface layer is arranged between the anode and the filter layer, and a cathode interface layer is arranged between the PN blending body heterojunction layer and the cathode. The invention realizes the visible blind near infrared photoelectric detection function by a novel device structure without an external optical filter or other additional technical means, and can resist the ambient light interference.
Description
Technical Field
The invention relates to the field of organic photoelectron, in particular to a visible blind near-infrared narrow-band organic photoelectric detector.
Background
The photoelectric detector can convert optical signals into electric signals and is widely applied to the fields of imaging systems, environment monitoring, information communication, biological sensing and the like. Photodetectors can be classified into broad-spectrum-response and narrow-spectrum-response photodetectors according to their spectral response characteristics. The wide-spectrum-response photodetector generally has a photoelectric response to the entire ultraviolet-visible-infrared band, and thus is generally interfered by ambient light or background light in some application scenes of monochromatic light detection and imaging, so that signal distortion is caused. In contrast, the narrow-spectrum response photodetector is more suitable for monochromatic light detection and imaging systems, most typically, the visible blind near-infrared photodetector only responds to incident light with certain specific wavelengths in an infrared band, but has weak response to incident light with a visible band, and the property of environmental light interference resistance enables the photodetector to be widely applied to active biological pattern recognition and information communication fields, including face recognition, iris recognition, all-weather robots and automatic driving systems.
The visible blind near infrared photoelectric detector which is commercially used at present is realized by coupling an optical filter with a photodiode made of an inorganic material. However, this increases the structural complexity and fabrication cost of the photodetector. In addition, the use of the filtering system may generate an additional optical interface, reduce image definition, easily cause signal crosstalk, and cause obstacles for realizing an imaging system with higher pixel density.
The organic semiconductor material has the advantages of low price, flexibility, solution processing and the like, and meanwhile, the absorption spectrum of the organic semiconductor material can be adjusted through molecular structure design, so that the organic semiconductor material is more suitable for realizing spectrum modulation of a photoelectric detector. The implementation modes mainly include narrow spectrum detection by using a photosensitive material with narrow spectrum absorption, Charge Collection Narrowing (CCN) for controlling charge collection efficiency, Exciton Dissociation Narrowing (EDN) for controlling exciton dissociation efficiency and the like, but the detectors prepared by the strategies are difficult to give consideration to narrow detection peak half-peak width and high peak value responsivity, particularly in a near infrared band, the external quantum efficiency is generally lower than 30 percent, or the half-peak width is larger than 200 nanometers, and the requirements of environmental light interference resistance and high near infrared detection sensitivity cannot be well met.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the visible blind near-infrared narrow-band organic photoelectric detector is invented. The novel device structure realizes the visible blind near-infrared narrow-band photoelectric detection function without an optical filter or an additional technical means.
The purpose of the invention is realized by the following technical scheme:
a visible blind near-infrared narrow-band organic photoelectric detector is characterized in that a device structure of the visible blind near-infrared narrow-band organic photoelectric detector sequentially comprises a substrate, an anode, a filter layer, a hole selection layer, a PN blending body heterojunction layer and a cathode. The filter layer is formed by layering or blending P-type materials or P-type materials and N-type materials, and the PN blending body heterojunction layer is formed by blending P-type materials and N-type materials. In the filter layer, a band gap of at least one material is wider than a band gap of at least one material in the PN-blend bulk heterojunction layer.
Further, the hole selection layer is made of a material having a hole transport function, and selectively passes only holes, and the material of the hole selection layer is any one or more of an organic P-type polymer material (e.g., poly (4-butyltriphenylamine) (poly-TPD), 3, 4-ethylenedioxythiophene mixed polystyrene sulfonate (PEDOT: PSS), etc.), an organic P-type small molecule material (e.g., 6, 13-bis (triisopropylsilaethynyl) pentacene, etc.), a metal oxide material (e.g., molybdenum oxide, nickel oxide, etc.), or a material having a similar function. Preferably, the hole selection layer is PEDOT PSS.
Further, the half-peak width of the response peak of the visible blind near-infrared narrow-band organic photodetector in an infrared region is less than 200 nanometers.
Further, the P-type material is a conjugated polymer or a conjugated small molecule material containing the following conjugated structure.
Wherein R is1-R6Can be a straight chain, branched chain or cyclic alkyl chain with 1-40 carbon atoms, wherein one or more carbon atoms can be replaced by oxygen atoms, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, amino groups, carbonyl groups, carboxyl groups, ester groups, cyano groups or nitro groups, and hydrogen atoms can be replaced by fluorine atoms, chlorine atoms, bromine atoms or iodine atoms; r1-R6And may be a substituent such as a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a thienyl group, a phenyl group. Preferably, the P-type material is polythiophene and derivatives thereof, such as P3HT, PDCBT, diketopyrrolopyrrole polymer material DT-PDPP2T-TT, and benzodithiophene-benzothiophene polymer material PTB 7-Th.
Further, the N-type material is a fullerene electron acceptor material or a non-fullerene electron acceptor material. Preferably, the N-type material is a fullerene electron acceptor material PC71BM and non-fullerene electron acceptor materials COi8DFIC and IEICO-4F.
Further, an anode interface layer is arranged between the anode and the light filter, the anode interface layer is made of any one or more of organic P-type polymer materials (such as poly (4-butyl triphenylamine) (poly-TPD), 3, 4-ethylenedioxythiophene mixed polystyrene sulfonate (PEDOT: PSS) and the like), organic P-type micromolecule materials (such as 6, 13-bis (triisopropyl silicon ethynyl) pentacene and the like), and metal oxide materials (such as molybdenum oxide, nickel oxide and the like), or materials with similar functions. Preferably, the anode interface layer material is molybdenum oxide and poly-TPD.
Further, a cathode interface layer is arranged between the PN blend bulk heterojunction layer and the cathode, and the cathode interface layer is made of a low work function metal material (such as calcium, barium, magnesium, etc.), a metal oxide material (such as zinc oxide, tin oxide, zinc magnesium oxide, zinc aluminum oxide, etc.), an ionic salt material (such as lithium fluoride, cesium fluoride, calcium fluoride, potassium fluoride, cesium carbonate, etc.), an organic N-type material (such as 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline (BCP), benzo [1,2-a:4,5-a '] diazolazine-3, 3' - (9, 9-dioctyl-9H-fluorene-2, 7-diyl) bis [6,7,14, 15-diyl ] chloride, etc.), a water-soluble alcohol material (such as [9, 9-dioctylfluorene-9, 9-bis (N, N-dimethylaminopropyl) fluorene ] (PFN), bromo- [9, 9-dioctylfluorene-9, 9-bis (N, N-dimethylaminopropyl) fluorene ] (PFN-Br), Polyethoxyethyleneimine (PEIE), etc.), or materials having similar functions. Preferably, the cathode interface layer material is lithium fluoride and PFN-Br.
Further, the anode material is Indium Tin Oxide (ITO), graphene, a metal nanowire, high-conductivity 3, 4-ethylenedioxythiophene mixed polystyrene sulfonate, nano silver paste, a metal grid or a carbon nanotube, or a material having a similar function. Preferably, the anode material is Indium Tin Oxide (ITO).
Further, the cathode material is any one of lithium, magnesium, calcium, strontium, barium, aluminum, copper, gold, silver, indium or an alloy thereof, or a material with similar functions. Preferably, the cathode material is aluminum.
Further, the substrate is any one or more of glass, polymer, ceramic, metal, or a composite having similar functions. Preferably, the substrate is glass.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the visible blind near-infrared narrow-band organic photoelectric detector has self-filtering performance, can realize the visible blind near-infrared detection function without an additional optical filter or an additional technical means, and has a simple structure, avoids the introduction of an additional optical interface, reduces the probability of signal crosstalk between pixels, effectively reduces signal distortion and improves the signal-to-noise ratio compared with the prior art of realizing narrow-spectrum response by coupling the wide-spectrum response photoelectric detector with the optical filter.
(2) Compared with the existing structure based on PN layering, the photosensitive layer of the invention adopts a PN blending bulk heterojunction structure, is beneficial to the sufficient dissociation of charges at a PN interface, and improves the quantum efficiency and the responsivity.
(3) In the invention, the hole selection layer is arranged between the filter layer and the PN blending body heterojunction layer, and compared with the prior art, the introduction of the hole selection layer simplifies the preparation process and improves the device performance. Specifically, the filter layer and the PN blending body heterojunction layer have similar solubility, the prior art cannot realize two-phase layering of the filter layer and the PN blending body heterojunction layer through direct and continuous solution processing, and can only realize separation of two layers through cross-linking or a complex transfer printing process. On the other hand, the hole selection layer is beneficial to reducing the charge recombination loss at the interface of the filter layer and the PN blending bulk heterojunction layer and improving the charge transmission at the interface, so that the quantum efficiency and the responsivity of a detection peak can be further improved compared with the prior art.
(4) Compared with the prior art, the visible blind near-infrared narrow-band organic photoelectric detector has both a high responsivity peak value and a narrow response peak half-peak width.
Drawings
Fig. 1 shows a schematic structural view of an organic photodetector in embodiment 1 of the present invention.
Fig. 2 shows schematic structural diagrams of organic photodetectors in embodiments 2, 4, and 7 of the present invention.
Fig. 3 shows schematic structural diagrams of organic photodetectors in embodiments 3, 5, and 6 of the present invention.
Fig. 4 shows a responsivity spectrum curve of the organic photodetector in example 3 of the present invention.
Fig. 5 shows a responsivity spectrum curve of the organic photodetector in example 4 of the present invention.
Fig. 6 shows a responsivity spectrum curve of the organic photodetector in example 5 of the present invention.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
As shown in fig. 1, the device structure of the visible blind near-infrared narrow-band organic photodetector sequentially comprises a substrate 1, an anode 2, a filter layer 3, a hole selection layer 4, a PN blend bulk heterojunction layer 5 and a cathode 6.
The substrate 1 is glass; the anode 2 is Indium Tin Oxide (ITO); the filter layer 3 is made of a P-type material, the P-type material in the filter layer is DT-PDPP2T-TT, and the film thickness is 400 nanometers; the hole selection layer 4 is a poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT: PSS) film with the thickness of 30 nanometers; the PN blending body heterojunction layer 5 is formed by P type materials PTB7-Th and N type materials COi8DFIC and PC71The film thickness of the ternary blending system film formed by blending BM is 110 nanometers; the cathode 6 is aluminum and has a thickness of 100 nm. The band gap of the P-type material DT-PDPP2T-TT in the filter layer is wider than that of the N-type material COi8DFIC in the PN blending bulk heterojunction layer.
The preparation method of the organic photoelectric detector comprises the following steps:
step 1: and ultrasonically cleaning the glass substrate coated with the ITO layer by using acetone, a micron-sized semiconductor special detergent, deionized water and isopropanol in sequence, drying by drying with nitrogen, and placing in a culture dish for later use.
Step 2: chloroform (CF) and o-dichlorobenzene (o-DCB) are mixed according to the volume ratio of 100:7 to be used as a mixed solvent, a P type material DT-PDPP2T-TT is dissolved in the mixed solvent, and a filtering layer with the thickness of 400 nanometers is prepared on the anode ITO through spin coating.
And step 3: mixing PEDOT, PSS solution, surfactant TERGITOL NP-10 and isopropanol, stirring overnight at room temperature, spin-coating on the filter layer DT-PDPP2T-TT to form a 30-nanometer-thick hole selection layer, and then placing on a 120 ℃ heating table for annealing treatment for 10 minutes.
And 4, step 4: mixing P type material PTB7-Th with N type material COi8DFIC and PC71BM is as follows: 1.1: 0.4, dissolving in chlorobenzene solvent, adding 1, 8-Diiodooctane (DIO) which is 1 percent of the volume fraction of the solution, spin-coating on the hole selection layer to obtain a PN blending bulk heterojunction layer with the thickness of 110 nanometers, and then removing the DIO in a low-pressure device.
And 5: and (3) performing vacuum thermal evaporation on the PN blending body heterojunction layer to form aluminum with the thickness of 100 nanometers as a cathode.
Example 2
Example 1 is repeated with the addition of a cathode interface layer 8 between the PN-blended bulk heterojunction layer 5 and the cathode 6. Specifically, as shown in fig. 2, the device structure of the visible blind near-infrared narrow-band organic photodetector sequentially comprises a substrate 1, an anode 2, a filter layer 3, a hole selection layer 4, a PN blend bulk heterojunction layer 5, a cathode interface layer 8 and a cathode 6.
The substrate 1 is glass; the anode 2 is Indium Tin Oxide (ITO); the filter layer 3 is made of a P-type material, the P-type material in the filter layer is DT-PDPP2T-TT, and the film thickness is 400 nanometers; the hole selection layer 4 is a poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT: PSS) film with the thickness of 30 nanometers; the PN blending body heterojunction layer 5 is formed by P type materials PTB7-Th and N type materials COi8DFIC and PC71The film thickness of the ternary blending system film formed by blending BM is 110 nanometers; the cathode 6 is aluminum and has a thickness of 100 nanometers; the cathode interface layer 8 is made of lithium fluoride and has a thickness of 0.6 nm.
The preparation method of the organic photoelectric detector comprises the following steps:
step 1: and ultrasonically cleaning the glass substrate coated with the ITO layer by using acetone, a micron-sized semiconductor special detergent, deionized water and isopropanol in sequence, drying by drying with nitrogen, and placing in a culture dish for later use.
Step 2: chloroform (CF) and o-dichlorobenzene (o-DCB) are mixed according to the volume ratio of 100:7 to be used as a mixed solvent, a P type material DT-PDPP2T-TT is dissolved in the mixed solvent, and a filtering layer with the thickness of 400 nanometers is prepared on the anode ITO through spin coating.
And step 3: mixing PEDOT, PSS solution, surfactant TERGITOL NP-10 and isopropanol, stirring overnight at room temperature, spin-coating on the filter layer DT-PDPP2T-TT to form a 30-nanometer-thick hole selection layer, and then placing on a 120 ℃ heating table for annealing treatment for 10 minutes.
And 4, step 4: mixing P type material PTB7-Th with N type material COi8DFIC and PC71BM is as follows: 1.1: 0.4, dissolving in chlorobenzene solvent, adding 1, 8-Diiodooctane (DIO) which is 1 percent of the volume fraction of the solution, spin-coating on the hole selection layer to obtain a PN blending bulk heterojunction layer with the thickness of 110 nanometers, and then removing the DIO in a low-pressure device.
And 5: and (3) performing vacuum thermal evaporation on the PN blending body heterojunction layer to form a lithium fluoride cathode interface layer with the thickness of 0.6 nanometer.
Step 6: and (3) performing vacuum thermal evaporation on the cathode interface layer to form aluminum with the thickness of 100 nanometers as a cathode.
Example 3
Example 2 was repeated with the addition of an anode interface layer 7 between the anode 2 and the filter layer 3. The method comprises the following specific steps: as shown in fig. 3, the device structure of the visible blind near-infrared narrow-band organic photodetector sequentially comprises a substrate 1, an anode 2, an anode interface layer 7, a filter layer 3, a hole selection layer 4, a PN blend bulk heterojunction layer 5, a cathode interface layer 8 and a cathode 6.
The substrate 1 is glass; the anode 2 is Indium Tin Oxide (ITO); the filter layer 3 is made of a P-type material, the P-type material in the filter layer is DT-PDPP2T-TT, and the film thickness is 400 nanometers; the hole selection layer 4 is a poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT: PSS) film with the thickness of 30 nanometers; the PN blending body heterojunction layer 5 is formed by P type materials PTB7-Th and N type materials COi8DFIC and PC71BMThe thickness of the ternary blending system film formed by blending is 110 nanometers; the cathode 6 is aluminum and has a thickness of 100 nanometers; the anode interface layer 7 is molybdenum oxide and has the thickness of 10 nanometers; the cathode interface layer 8 is made of lithium fluoride and has a thickness of 0.6 nm.
The preparation method of the organic photoelectric detector comprises the following steps:
step 1: and ultrasonically cleaning the glass substrate coated with the ITO layer by using acetone, a micron-sized semiconductor special detergent, deionized water and isopropanol in sequence, drying by drying with nitrogen, and placing in a culture dish for later use.
Step 2: and performing vacuum thermal evaporation on the ITO to form a molybdenum oxide film with the thickness of 10 nanometers as an anode interface layer.
And step 3: chloroform (CF) and o-dichlorobenzene (o-DCB) are mixed according to the volume ratio of 100:7 to be used as a mixed solvent, a P type material DT-PDPP2T-TT is dissolved in the mixed solvent, and a filter layer with the thickness of 400 nanometers is prepared on an anode interface layer through spin coating.
And 4, step 4: mixing PEDOT, PSS solution, surfactant TERGITOL NP-10 and isopropanol, stirring overnight at room temperature, spin-coating on the filter layer DT-PDPP2T-TT to form a 30-nanometer-thick hole selection layer, and then placing on a 120 ℃ heating table for annealing treatment for 10 minutes.
And 5: mixing P type material PTB7-Th with N type material COi8DFIC and PC71BM is as follows: 1.1: 0.4, dissolving in chlorobenzene solvent, adding 1, 8-Diiodooctane (DIO) which is 1 percent of the volume fraction of the solution, spin-coating on the hole selection layer to obtain a PN blending bulk heterojunction layer with the thickness of 110 nanometers, and then removing the DIO in a low-pressure device.
Step 6: and (3) performing vacuum thermal evaporation on the PN blending body heterojunction layer to form a lithium fluoride cathode interface layer with the thickness of 0.6 nanometer.
And 7: and (3) performing vacuum thermal evaporation on the cathode interface layer to form aluminum with the thickness of 100 nanometers as a cathode.
The organic photodetector prepared in example 3 is subjected to a correlation performance test, and a responsivity spectral curve obtained by the test without an external bias is shown in fig. 4, and it can be seen that the organic photodetector has an obvious response peak in a near infrared band, the peak value is close to 940 nm, and meanwhile, the organic photodetector is accompanied by a weak response in a 400-700 nm band.
Example 4
Example 2 was repeated with the addition of a P-type layer, so that the filter layer was composed of multiple P-type materials in layers. The method comprises the following specific steps: as shown in fig. 2, the device structure of the visible blind near-infrared narrow-band organic photodetector sequentially comprises a substrate 1, an anode 2, a filter layer 3, a hole selection layer 4, a PN blend bulk heterojunction layer 5, a cathode interface layer 8 and a cathode 6.
The substrate 1 is glass; the anode 2 is Indium Tin Oxide (ITO); the filter layer 3 is formed by layering two P-type materials, the first P-type layer is a poly (3-hexylthiophene) (P3HT) film with the thickness of 350nm, and the second P-type layer is a DT-PDPP2T-TT film with the thickness of 400 nm; the hole selection layer 4 is a poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT: PSS) film with the thickness of 30 nanometers; the PN blending body heterojunction layer 5 is formed by P type materials PTB7-Th and N type materials COi8DFIC and PC71The film thickness of the ternary blending system film formed by blending BM is 110 nanometers; the cathode 6 is aluminum and has a thickness of 100 nanometers; the cathode interface layer 8 is made of lithium fluoride and has a thickness of 0.6 nm. The band gaps of the P type material P3HT and DT-PDPP2T-TT in the filter layer are both wider than the band gap of the N type material COi8DFIC in the PN blending bulk heterojunction layer.
The preparation method of the organic photoelectric detector comprises the following steps:
step 1: and ultrasonically cleaning the glass substrate coated with the ITO layer by using acetone, a micron-sized semiconductor special detergent, deionized water and isopropanol in sequence, drying by drying with nitrogen, and placing in a culture dish for later use.
Step 2: taking P type material poly (3-hexylthiophene) (P3HT) as a main material, taking fluorinated phenyl azide (S-FPA) as a cross-linking agent, mixing the main material and the cross-linking agent according to a mass ratio of 10:1, dissolving in Chlorobenzene (CB) to prepare a mixed solution, spin-coating the mixed solution on ITO, irradiating for 6min by an ultraviolet lamp, and then washing by a solvent to obtain a dry film with the thickness of 350nm as a first P type layer; and then mixing Chloroform (CF) and o-dichlorobenzene (o-DCB) according to the volume ratio of 100:7 to obtain a mixed solvent, dissolving a P-type material DT-PDPP2T-TT in the mixed solvent, and performing spin coating on the first P-type layer P3HT to obtain a second P-type layer with the thickness of 400 nanometers. The first P type layer and the second P type layer jointly form a filter layer.
And step 3: and mixing the PEDOT, namely PSS solution, a surfactant TERGITOL NP-10 and isopropanol, stirring at room temperature overnight, spin-coating on the filter layer to form a 30-nanometer-thick hole selection layer, and then placing the hole selection layer on a heating table at 120 ℃ for annealing treatment for 10 minutes.
And 4, step 4: mixing P type material PTB7-Th with N type material COi8DFIC and PC71BM is as follows: 1.1: 0.4, dissolving in chlorobenzene solvent, adding 1, 8-Diiodooctane (DIO) which is 1 percent of the volume fraction of the solution, spin-coating on the hole selection layer to obtain a PN blending bulk heterojunction layer with the thickness of 110 nanometers, and then removing the DIO in a low-pressure device.
And 5: and (3) performing vacuum thermal evaporation on the PN blending body heterojunction layer to form a lithium fluoride cathode interface layer with the thickness of 0.6 nanometer.
Step 6: and (3) performing vacuum thermal evaporation on the cathode interface layer to form aluminum with the thickness of 100 nanometers as a cathode.
The organic photodetector prepared in example 4 was tested for its correlation performance, and the responsivity spectrum curve obtained by the test without external bias is shown in fig. 5, and comparing fig. 4, it can be seen that the response of the 400-700 nm band is further suppressed by adopting the absorption complementary dual P-type layer structure, while the response peak of the infrared part is not significantly changed, the peak responsivity is close to 0.45 a/w, and the half-peak width is less than 200 nm.
Example 5
Example 3 was repeated with the addition of another N-type material PC to the filter layer71BM, the filter layer is formed by blending a P-type material and an N-type material. The band gap of the P-type material DT-PDPP2T-TT in the filter layer is wider than that of the N-type material COi8DFIC in the PN blending bulk heterojunction layer. The method comprises the following specific steps: as shown in fig. 3, the device structure of the visible blind near-infrared narrow-band organic photodetector sequentially comprises a substrate 1, an anode 2, an anode interface layer 7, a filter layer 3, a hole selection layer 4, a PN blend bulk heterojunction layer 5, a cathode interface layer 8 and a cathode 6.
The substrate 1 is glass; the anode 2 is Indium Tin Oxide (ITO); the filter layer 3 is formed by blending a P-type material and an N-type material, the film thickness is 400 nanometers, the P-type material in the filter layer is DT-PDPP2T-TT, and the N-type material in the filter layer is PC71BM; the hole selection layer 4 is a poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid (PEDOT: PSS) film with the thickness of 30 nanometers; the PN blending body heterojunction layer 5 is formed by P type materials PTB7-Th and N type materials COi8DFIC and PC71The film thickness of the ternary blending system film formed by blending BM is 110 nanometers; the cathode 6 is aluminum and has a thickness of 100 nanometers; the anode interface layer 7 is poly (4-butyl triphenylamine) (poly-TPD) with the thickness of 30 nanometers; the cathode interface layer 8 is bromo- [9, 9-dioctyl fluorene-9, 9-bis (N, N-dimethyl aminopropyl) fluorene](PFN-Br) 8 nm thick.
The preparation method of the organic photoelectric detector comprises the following steps:
step 1: and ultrasonically cleaning the glass substrate coated with the ITO layer by using acetone, a micron-sized semiconductor special detergent, deionized water and isopropanol in sequence, drying by drying with nitrogen, and placing in a culture dish for later use.
Step 2: dissolving poly-TPD in Chlorobenzene (CB), spin-coating on ITO to obtain a film with the thickness of 30 nanometers, and then carrying out thermal annealing at 120 ℃ for 30 minutes and ultraviolet lamp irradiation for 30 minutes to crosslink the film.
And step 3: mixing Chloroform (CF) and o-dichlorobenzene (o-DCB) according to a volume ratio of 100:7 to obtain a mixed solvent, and mixing a P type material DT-PDPP2T-TT and an N type material PC71BM is as follows: 3, dissolving in the mixed solvent, and spin-coating on the anode interface layer to obtain a filter layer with a thickness of 500 nm.
And 4, step 4: PSS solution PEDOT (from Clevios, model Clevios)TMHTL Solar) was spin-coated on the filter layer to form a 30 nm thick hole selection layer, which was then annealed in a 120 ℃ hot plate for 10 minutes.
And 5: mixing P type material PTB7-Th with N type material COi8DFIC and PC71BM is as follows: 1.1: 0.4, dissolving in chlorobenzene solvent, and adding 1, 8-diiodooctane as additive accounting for 1% of the volume fraction of the solution(DIO) spin coating on the hole selection layer to produce a PN-blended bulk heterojunction layer with a thickness of 110 nm, and then pumping out the additive DIO in a low-pressure apparatus.
Step 6: and spin-coating a PFN-Br film with the thickness of 8 nanometers on the PN blending body heterojunction layer to be used as a cathode interface layer.
And 7: and (3) performing vacuum thermal evaporation on the cathode interface layer to form aluminum with the thickness of 100 nanometers as a cathode.
The organic photodetector prepared in example 5 was subjected to a correlation performance test, and the responsivity spectrum curve obtained by the test without an external bias voltage was shown in fig. 6.
Example 6
Example 3 was repeated with the addition of another P-type material PDCBT in the filter layer, so that the filter layer was made of a blend of P-type materials. The band gaps of the P-type materials PDCBT and DT-PDPP2T-TT in the filter layer are both wider than the band gap of the N-type material COi8DFIC in the PN blending bulk heterojunction layer.
Example 7
Example 4 was repeated to change the N-type material in the PN bulk heterojunction layer 5, so that the PN bulk heterojunction layer 5 was a binary blend system thin film formed by blending the P-type material PTB7-Th and the N-type material IEICO-4F, and the film thickness was 200 nm.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A visible blind near-infrared narrow-band organic photoelectric detector is characterized in that a device structure of the visible blind near-infrared narrow-band organic photoelectric detector sequentially comprises a substrate (1), an anode (2), a filter layer (3), a hole selection layer (4), a PN blending body heterojunction layer (5) and a cathode (6); the filter layer is formed by layering or blending P-type materials or can be formed by blending P-type materials and N-type materials; the PN blending body heterojunction layer is formed by blending a P-type material and an N-type material; in the filter layer, a band gap of at least one material is wider than a band gap of at least one material in the PN-blend bulk heterojunction layer.
2. A visible blind near-infrared narrow-band organic photodetector according to claim 1, characterized in that a hole selection layer (4) is provided between the filter layer (3) and the PN-blended bulk heterojunction layer (5); the hole selection layer material is any one or more of an organic P-type polymer material, an organic P-type micromolecule material and a metal oxide material; the organic P-type polymer material comprises poly (4-butyl triphenylamine) (poly-TPD) or 3, 4-ethylenedioxythiophene mixed polystyrene sulfonate (PEDOT: PSS); the organic P-type micromolecule material comprises 6, 13-bis (triisopropylsilylethynyl) pentacene; the metal oxide based material includes molybdenum oxide or nickel oxide.
3. The visible blind near-infrared narrow-band organic photodetector as claimed in claim 1, wherein the half-width of the response peak of the visible blind near-infrared narrow-band organic photodetector in the infrared region is less than 200 nm.
4. The visible blind near-infrared narrow-band organic photodetector as claimed in claim 1, wherein the P-type material is a conjugated polymer or conjugated small molecule material containing the following conjugated structure;
5. the visible-blind near-infrared narrow-band organic photodetector as claimed in claim 4, wherein R is1-R6Is a straight chain having 1 to 40 carbon atoms, a branched chain having 1 to 40 carbon atoms or a cyclic alkyl chain having 1 to 40 carbon atoms.
6. The visible blind near-infrared narrow-band organic photodetector as claimed in claim 5, wherein one or more carbon atoms in the straight chain of 1 to 40 carbon atoms, the branched chain of 1 to 40 carbon atoms or the cyclic alkyl chain of 1 to 40 carbon atoms are substituted by oxygen atom, alkenyl group, alkynyl group, aryl group, hydroxyl group, amino group, carbonyl group, carboxyl group, ester group, cyano group or nitro group, and the hydrogen atom is substituted by fluorine atom, chlorine atom, bromine atom or iodine atom.
7. The visible-blind near-infrared narrow-band organic photodetector as claimed in claim 4, wherein R is1-R6Is a substituent group, and the substituent group is hydrogen, fluorine, chlorine, cyano-group, nitryl, thienyl or phenyl.
8. The visible blind near-infrared narrow-band organic photodetector as claimed in claim 1, wherein the N-type material is a fullerene electron acceptor material or a non-fullerene electron acceptor material.
9. The visible blind near-infrared narrow-band organic photodetector as claimed in claim 1, characterized in that an anode interface layer (7) is disposed between the anode (2) and the filter layer (3), and the anode interface layer is made of any one or more of organic P-type polymer materials, organic P-type small molecule materials, and metal oxide materials; the organic P-type polymer material comprises poly (4-butyl triphenylamine) (poly-TPD) and 3, 4-ethylenedioxythiophene mixed polystyrene sulfonate (PEDOT: PSS); the organic P-type micromolecule material comprises 6, 13-bis (triisopropylsilylethynyl) pentacene; the metal oxide based material includes molybdenum oxide or nickel oxide.
10. The visible blind near-infrared narrow-band organic photodetector as claimed in claim 1, wherein a cathode interface layer (8) is disposed between the PN blend bulk heterojunction layer (5) and the cathode (6), and the cathode interface layer is made of any one or more of low work function metal materials, metal oxide materials, ionic salt materials, organic N-type materials, and water-soluble materials; the low work function metal material comprises calcium, barium or magnesium; the metal oxide material comprises zinc oxide, tin oxide, zinc magnesium oxide or zinc aluminum oxide; the ionic salt material comprises lithium fluoride, cesium fluoride, calcium fluoride, potassium fluoride or cesium carbonate; the organic N-type material comprises 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline (BCP), benzo [1,2-a:4,5-a '] diazolazine-3, 3' - (9, 9-dioctyl-9H-fluorene-2, 7-diyl) bis [6,7,14, 15-diyl ] chloride salt; the water alcohol soluble material comprises [9, 9-dioctyl fluorene-9, 9-bis (N, N-dimethyl amine propyl) fluorene ] (PFN), bromo- [9, 9-dioctyl fluorene-9, 9-bis (N, N-dimethyl amine propyl) fluorene ] (PFN-Br) or Polyethoxy Ethylene Imine (PEIE).
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