CN109037454A - A kind of organic photoelectric multiplication detector based on surface plasmons - Google Patents

A kind of organic photoelectric multiplication detector based on surface plasmons Download PDF

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CN109037454A
CN109037454A CN201810831028.8A CN201810831028A CN109037454A CN 109037454 A CN109037454 A CN 109037454A CN 201810831028 A CN201810831028 A CN 201810831028A CN 109037454 A CN109037454 A CN 109037454A
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layer
active layer
organic
metal nano
optical gate
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CN109037454B (en
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张叶
梁强兵
崔艳霞
李国辉
王文艳
冀婷
郝玉英
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Taiyuan University of Technology
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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
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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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
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/87—Light-trapping means
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    • Y02E10/549—Organic PV cells

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Abstract

The present invention relates to organic photoelectric multiplication detector fields, a kind of organic photoelectric multiplication detector based on surface plasmons: using indium tin oxide ITO as anode layer, with poly- (3, 4- ethene dioxythiophene)-polystyrolsulfon acid PEDOT:PSS is as anode buffer layer, with 3- hexyl thiophene P3HT, poly- [[9- (1- octyl nonyl) -9H- carbazole -2, 7- diyl] -2, 5- thiophene diyl -2, 1, 3- diazosulfide -4, 7- diyl -2, 5- thiophene diyl PCDTBT, any one in PSBTBT:PC71BM is the donor material of organic active layer, using fullerene derivate PCBM as the acceptor material of organic active layer, donor material and acceptor material form organic active layer, with integrated metal nano light Grid matrix and metallic film are cathode layer, and nanometer grating matrix is embedded in organic active layer.

Description

A kind of organic photoelectric multiplication detector based on surface plasmons
Technical field
It is especially a kind of to do cathode using rectangular metal grating array the present invention relates to organic photoelectric multiplication detector field , excitating surface plasmon (Surface Plasmon Polaritions Mode) enhances the battery of active layer light absorption Structure.
Background technique
Organic photoelectric multiplication detector has many advantages, such as light weight, at low cost, materials are extensive, flexible, closely The extensive concern of researchers is received over year.It forms tunneling effect using electronics (hole) trap assist holes (electronics) and mentions External quantum efficiency (EQE) value of high detector.But the response speed of organic polymer photomultiplier detector is slow, it is right The collection performance of carrier is poor.For such issues that researchers inorganic nano or organic dye particles are mixed into bulk heterojunction Active layer in realize photomultiplier transit phenomenon.Such as: inorganic nanoparticles cadmium antimonide (CdTe) is mixed P3HT by Chen et al.: In the active layer of PCBM (mass ratio 1:1), a large amount of electron trap is brought by the introducing of CdTe, to realize that photomultiplier transit is imitated It answers, EQE maximum value can reach 8000%.Wang et al. discovery is changed by the atom self assembly time of adjusting electron donor P3HT Become P3HT molecules align mode, can also be improved hole mobility, so that external quantum efficiency reaches 115800%.Organic photoelectric times The structure for increasing detector and organic photovoltaic devices is substantially similar, and in organic photovoltaic devices, researchers utilize metal nano knot Structure excitating surface phasmon efficiently captures incident light in active layer, to improve the efficiency of light absorption of device, increases Its external quantum efficiency enhances the collection efficiency of carrier.External quantum efficiency is also the Key Performance Indicator of photomultiplier detector One of, the higher device of external quantum efficiency has higher response speed and response rate, and device is sensitiveer.Thus, it improves External quantum efficiency is to optimize an importance of photomultiplier detector performance.
Summary of the invention
The technical problems to be solved by the present invention are: how to utilize metal grating back electrode (cathode), organic photoelectric is improved The absorptivity of multiplication detector.
The technical scheme adopted by the invention is that: a kind of organic photoelectric multiplication detector based on surface plasmons: Using indium tin oxide ITO as anode layer, using poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid PEDOT:PSS as sun Pole buffer layer, with 3- hexyl thiophene P3HT, poly- [[9- (1- octyl nonyl) -9H- carbazole -2,7- diyl] -2,5- thiophene diyl - Any one in 2,1,3- diazosulfide -4,7- diyl -2,5- thiophene diyl PCDTBT, PSBTBT:PC71BM is organic The donor material of active layer, using fullerene derivate PCBM as the acceptor material of organic active layer, donor material and acceptor material Organic active layer is formed, using integrated metal nano optical gate matrix and metallic film as cathode layer, nanometer grating matrix is inlayed In organic active layer.
As a kind of preferred embodiment: anode layer with a thickness of 180nm, anode buffer layer with a thickness of 20nm, organic active Layer with a thickness of 100nm, in cathode layer, the unit nano metal column cross section of metal nano optical gate matrix is side length is 20nm's Square, in cathode layer metal nano optical gate matrix with a thickness of 32 nm, the duty ratio of metal nano optical gate matrix is 0.75, The integral thickness of cathode layer is 200nm.
As a kind of preferred embodiment: the quality of donor material is 100 times of acceptor material quality in organic active layer.
As a kind of preferred embodiment: the material of cathode layer is gold, silver, copper, any one in aluminium, nanometer grating matrix In.
As a kind of preferred embodiment: the manufacturing process of integrated metal nano optical gate matrix and metallic film is by true Sky vapor deposition obtains metallic film, is then etched by laser light and obtains metal nano optical gate matrix, ultimately forms integrated gold Belong to nanometer grating matrix and metallic film.
The beneficial effects of the present invention are: being carried by metal nano optical gate matrix excitating surface phasmon using its regulation Flow son transmission performance, auxiliary cathode interface electron capture with improve organic photoelectric multiplication detector response speed.It is quasi- to pass through The method of laser lithography is significantly mentioned in the relief pattern that the interface introduces rectangular array by excitating surface phasmon The response speed of high device.
Detailed description of the invention
Fig. 1 is layers of material schematic diagram of the invention；
Fig. 2 is three-dimensional structure schematic diagram of the invention；
Wherein, 1, anode layer, 2, anode buffer layer, 3, organic active layer, 4, integrated metal nano optical gate matrix and metal Film, 5, metal nano optical gate matrix, 6, metallic film.
Specific embodiment
The detector as shown in Figure 1, a kind of organic photoelectric based on surface plasmons doubles, structure are as follows: 180nm is thick Indium tin oxide (ITO) be used as anode, poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS) of 20nm As anode buffer layer, mass ratio is the organic matter P3HT:PC of 100:171BM is as active layer, integrated silver nanoparticle grating (Ag metal grating) matrix and silverskin (Ag film) do the back electrode (cathode) of battery jointly, wherein silver nanoparticle grating The square that the single silver-colored column cross-sectional width of matrix is 20 nm, single silver pillar height is 32 nm, and forming structure is ITO (180 nm)/PEDOT:PSS/(20 nm)/P3HT:PC71BM (40 nm)/Ag metal grating/Ag film (200 nm)).Its The silverskin can be obtained by vacuum evaporation；Silver nanoparticle optical gate matrix can be obtained by laser lithography；Other each organic function Ergosphere can be obtained on indium tin oxide by revolving Tu technique.
As shown in Fig. 2, the continued access metal nano optical gate matrix on metallic film substrate, exists by adjusting metal nano grating Duty in structure when metal nano grating height parameter, optimizes the light absorpting ability of active layer, greatly enhances active layer Efficiency of light absorption.Specific manufacturing process is: preparing anode buffer layer and active layer by revolving Tu technique on ito glass；Gold Belong to film to prepare using Vacuum Heat coating technique either magnetron sputtering technique；Metal nano optical gate matrix array is then directly to exist Back electrode is obtained using Laser lithography etching on metallic film.Metal nano optical gate matrix is completely embedded in active layer, Obtain a kind of organic photoelectric multiplication detector based on surface plasmons.
Metal nano optical gate matrix is rectangular array, closest metal nano light in used metal back electrode structure There is extra small spacing (5nm) between grid unit, compared with large ratio of height to width (32:15).Proposed by the present invention use has metal nano light The metal back electrode structure of grid significantly increases effect to active layer light absorpting ability, is different from from structure and in performance existing There is technology.
It is special can not only to show good light reflection for back electrode of the metal nano grating as device used in the present invention Property, increase incident light in the optical path of active layer, and can guarantee that surface plasmons can be excited successfully.Metal nano light Grid can not only make to penetrate light by local in the active layer around nanometer grating, enhance light absorption, and make metallic cathode attached More electronics are closely generated, narrow hole tunnel barrier, improves hole injection efficiency.
Used metal material is can be with one of the gold, silver, copper, aluminium of excitating surface plasmon.
In metallic cathode, metallic film is identical as the metal material of metal nano grating.Its arrangement mode is rectangle Two-dimensional array.Played the role of being that the surface plasmons excited by metal nano grating obtains efficient light absorption Performance.
The width and height of the metal nano grating are respectively 15nm and 32nm.
The duty ratio (width of metal nano grating compares its period) of the metal nano grating is 0.75.
The present invention is based on surface plasma body technique, the surface plasmons enhancing excited with metal nano grating is organic The light absorption of photomultiplier detector active layer obtains the organic photoelectric multiplication panel detector structure of efficient light absorption.

Claims (5)

  1. The detector 1. a kind of organic photoelectric based on surface plasmons doubles, it is characterised in that: with indium tin oxide ITO work For anode layer, using poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid PEDOT:PSS as anode buffer layer, with 3- hexyl Thiophene P3HT, poly- [[9- (1- octyl nonyl) -9H- carbazole -2,7- diyl] -2,5- thiophene diyl -2,1,3- diazosulfide - Any one in 4,7- diyl -2,5- thiophene diyls PCDTBT, PSBTBT:PC71BM is the donor material of organic active layer, Using fullerene derivate PCBM as the acceptor material of organic active layer, donor material and acceptor material form organic active layer, with Integrated metal nano optical gate matrix and metallic film are cathode layer, and nanometer grating matrix is embedded in organic active layer.
  2. The detector 2. a kind of organic photoelectric based on surface plasmons according to claim 1 doubles, feature exist In: anode layer with a thickness of 180nm, anode buffer layer with a thickness of 20nm, organic active layer with a thickness of 40-100nm, cathode The unit nano metal column cross section of metal nano optical gate matrix is the square that side length is 20nm in layer, and metal is received in cathode layer Rice optical gate matrix with a thickness of 32 nm, the duty ratio of metal nano optical gate matrix is 0.75, and the integral thickness of cathode layer is 200nm。
  3. The detector 3. a kind of organic photoelectric based on surface plasmons according to claim 1 doubles, feature exist In: the quality of donor material is 100 times of acceptor material quality in organic active layer.
  4. The detector 4. a kind of organic photoelectric based on surface plasmons according to claim 1 doubles, feature exist In: the material of cathode layer be gold, silver, copper, any one in aluminium, in nanometer grating matrix.
  5. The detector 5. a kind of organic photoelectric based on surface plasmons according to claim 1 doubles, feature exist In: the manufacturing process of integrated metal nano optical gate matrix and metallic film is to obtain metallic film by vacuum evaporation, so It is etched afterwards by laser light and obtains metal nano optical gate matrix, ultimately form integrated metal nano optical gate matrix and metal foil Film.
CN201810831028.8A 2018-07-26 2018-07-26 Organic photomultiplier detector based on surface plasmon polariton Active CN109037454B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110783465A (en) * 2019-11-06 2020-02-11 太原理工大学 Thermal electron photoelectric detector based on 8-hydroxyquinoline aluminum/metal heterojunction
CN111883664A (en) * 2020-06-30 2020-11-03 西安理工大学 Double-injection multiplication type organic photoelectric detector and preparation method thereof
CN113130761A (en) * 2021-03-19 2021-07-16 太原理工大学 Organic photomultiplier with bidirectional bias response and preparation method thereof
CN115004386A (en) * 2020-01-14 2022-09-02 金勋 Surface plasma photonics electric field enhanced photoelectric detector and image sensor

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102184975A (en) * 2011-04-11 2011-09-14 复旦大学 Thin film solar cell with improved photoelectric conversion efficiency and manufacturing method thereof
CN204333040U (en) * 2015-01-23 2015-05-13 刘红兵 A kind of thin film organic solar battery
US20160155994A1 (en) * 2013-08-09 2016-06-02 Electronics And Telecommunications Research Institute Organic light-emitting diode and method of fabricating the same
CN106129255A (en) * 2016-08-25 2016-11-16 太原理工大学 Organic solar batteries based on extra small cycle silver nanometer column array and preparation method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102184975A (en) * 2011-04-11 2011-09-14 复旦大学 Thin film solar cell with improved photoelectric conversion efficiency and manufacturing method thereof
US20160155994A1 (en) * 2013-08-09 2016-06-02 Electronics And Telecommunications Research Institute Organic light-emitting diode and method of fabricating the same
CN204333040U (en) * 2015-01-23 2015-05-13 刘红兵 A kind of thin film organic solar battery
CN106129255A (en) * 2016-08-25 2016-11-16 太原理工大学 Organic solar batteries based on extra small cycle silver nanometer column array and preparation method

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110783465A (en) * 2019-11-06 2020-02-11 太原理工大学 Thermal electron photoelectric detector based on 8-hydroxyquinoline aluminum/metal heterojunction
CN115004386A (en) * 2020-01-14 2022-09-02 金勋 Surface plasma photonics electric field enhanced photoelectric detector and image sensor
CN111883664A (en) * 2020-06-30 2020-11-03 西安理工大学 Double-injection multiplication type organic photoelectric detector and preparation method thereof
CN111883664B (en) * 2020-06-30 2022-09-23 西安理工大学 Double-injection multiplication type organic photoelectric detector and preparation method thereof
CN113130761A (en) * 2021-03-19 2021-07-16 太原理工大学 Organic photomultiplier with bidirectional bias response and preparation method thereof
CN113130761B (en) * 2021-03-19 2022-04-19 太原理工大学 Organic photomultiplier with bidirectional bias response and preparation method thereof

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