CN109860397A - Light-detecting device and optical detector - Google Patents
Light-detecting device and optical detector Download PDFInfo
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- CN109860397A CN109860397A CN201910236278.1A CN201910236278A CN109860397A CN 109860397 A CN109860397 A CN 109860397A CN 201910236278 A CN201910236278 A CN 201910236278A CN 109860397 A CN109860397 A CN 109860397A
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- indium tin
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Classifications
-
- 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
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The present invention provides a kind of light-detecting device and optical detectors.The light-detecting device includes indium tin oxide anode layer, photoactive layer, boundary layer and metal cathode layer；Wherein the photoactive layer is located at the upper layer of the indium tin oxide anode layer, and the photoactive layer is formed by the mixture comprising electron donor material and electron acceptor material；The boundary layer is located at the upper layer of the photoactive layer, and the metal cathode layer is located at the upper layer of the boundary layer.The present invention also provides a kind of optical detectors comprising the light-detecting device.Optical detector device and optical detector provided by the invention, can be improved the detectivity of high-molecular optical detector.
Description
Technical field
The present invention relates to organic semiconductor material field, it is related to a kind of light-detecting device and optical detector, has and be related to
Donor-receiver of the one kind based on the modification of 3,4- ethylenedioxy thiophene (3-4-ethylenedioxythiophene:EDOT) side chain
The photoactive layer that type macromolecule is formed, to realize a kind of simple Devices structure of highly sensitive high-molecular optical detector detection.
Background technique
Detected light can be converted into the semiconductor devices of electric signal as one kind, photodetector is in many fields
With important application, such as image sensing, data communication, long-range control, environmental monitoring.And conjugated polymer is as a kind of new
Type semiconductor material, due to its with it is at low cost, can be processed with solution, flexible and translucence advantage, cause academia
With the extensive concern of industry.And dark current present in high-molecular optical detector will affect the sensitivity of its detection, reduce
The multiple boundary layer modification taken in the strategy of dark current, and device architecture complexity is often inevitably led to, affect it
It uses.
Therefore, it finds and highly sensitive high-molecular optical detector can be achieved simultaneously with simple device architecture with important
Meaning.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is to propose a kind of light-detecting device and optical detector.
The present invention is that the following research institute based on inventor finds: in light-detecting device, formal dress device architecture (ITO/
Anode interface layer/photoactive layer/cathode interface layer/cathode) it is one of common device architecture of optical detector.In general, it is this just
Assembling structure can be using poly- 3,4- ethene dioxythiophene/poly styrene sulfonate (PEDOT:PSS) modification ito anode and photoactive layer
Between interface, to improve ITO substrate surface for roughness, adjust work function etc., and then quality of forming film can be improved and match light
The energy level of electron donor in active layer.The highly acid of PSS is in air however under atmosphere at room temperature environment, in PEDOT:PPS
ITO is easily corroded after water suction, accelerates ageing of electrode, reduces device lifetime.PEDOT:PSS is as boundary layer simultaneously, in macromolecule
It is difficult to effectively inhibit electron injection in optical detector, leads to high leakage current.As a result, it is desirable to which multiple boundary layer modification is to reduce device
Part dark current or noise.To solve the problems, such as that PEDOT:PSS exists, attempt to repair using the different anode of inverted structure and replacement
Layer or the method using multiple interface are adornd, device architecture complexity is all inevitably led to, is unfavorable for practical application.
In high-molecular optical detector, photoactive layer is mainly based upon bulk heteroj unction structure.This body heterojunction
Electron donor and electron acceptor material are contained, forms inierpeneirating network structure each other, is conducive to electric charge transfer, separation and biography
It is defeated.And the macromolecule of EDOT side chain modification greatly reduces the dark current of photoelectric detector, and improves photodetection rate.
For this purpose, the present invention provides a kind of device architectures of simple optical detector, for improving high-molecular optical detector
Detectivity.
Specifically, the present invention provides the following technical scheme that
According to the first aspect of the invention, the present invention provides a kind of light-detecting devices, comprising: indium tin oxide anode
Layer, photoactive layer, boundary layer and metal cathode layer；Wherein the photoactive layer is located at the upper of the indium tin oxide anode layer
Layer, the photoactive layer are formed by the mixture comprising electron donor material and electron acceptor material；The boundary layer is located at institute
The upper layer of photoactive layer is stated, the metal cathode layer is located at the upper layer of the boundary layer.Light-detecting device provided by the invention,
There is no PEDOT:PSS modification between photoactive layer and indium tin oxide anode layer, the dark electricity of light-detecting device can be substantially reduced
Stream, improves the detectivity of photodetector.The light-detecting device can be applied to various comprising 3,4- ethylenedioxy thiophene ring
In the donor-receiver type macromolecule of side chain modification, photoresponse is covered from UV to NIR.
According to an embodiment of the invention, light-detecting device described above may further include following technical characteristic:
In some embodiments of the invention, it between the indium tin oxide anode layer and the photoactive layer, does not deposit
In interface-modifying layer.
In some embodiments of the invention, it is not present between the indium tin oxide anode layer and the photoactive layer
The interface-modifying layer that PEDOT:PSS is formed.
In some embodiments of the invention, the photoactive layer be located at the indium tin oxide anode layer upper layer and with
The upper surface of indium tin oxide anode layer contacts, the boundary layer be located at the upper layer of the photoactive layer and with the photoactive layer
Upper surface contact, the metal cathode layer is located at the upper layer of the boundary layer and contacts with the upper layer of the boundary layer.
In some embodiments of the invention, the indium tin oxide positive layer with a thickness of 120~140nm, preferably
130nm.Such as can use square resistance is 10 Ω/ indium tin oxide as indium tin oxide positive layer.
In some embodiments of the invention, the electron donor material is modified comprising 3,4-ethylene dioxythiophene ring side chain
Donor-receiver type macromolecule.
In some embodiments of the invention, the electron donor material is selected from the 3- (5- (4,8- modified through EDOT side chain
Bis- (7- (2- ethylhexyl) -2,3- dihydro thiophene simultaneously [3,4-B] [1,4] dioxine -5- base) benzo [1,2-B:4,5-
B'] Dithiophene -2- base) thiophene -2- base) and bis- (2- butyl octyl) -6- (thiophene -2- the base) -2,5- pyrrolin of -2,5- simultaneously [3,
4-c] pyrroles -1,4- diketone (PBD (EDOT)), ((4,8- is bis-, and (7- (2- ethylhexyl) -2,3- dihydro thiophene is simultaneously [3,4-B] by 5- by 1-
[1,4] dioxine -5- base) benzo [1,2-B:4,5-b'] Dithiophene -2- base) -6- octyl thiophene simultaneously [3,2-b] thiophene
Pheno -2- base) -5- (2- hexyl decyl) -3- (6- octyl thiophene [3,2-b] thiophene -2- base) -4H- thieno [3,4-c] pyrroles -
4,6 (5H)-diketone (PET-1), 4-5- (bis- (7- (2- ethylhexyl) -2,3- dihydro thiophene simultaneously [3,4-B] [1,4] dioxas of 4,8-
Cyclohexene -5- base) benzo [1,2-B:4,5-b'] Dithiophene -2- base) thiophene -2- base) two fluoro- 2- (2- hexyl decyl) of -5,6- -
At least one of 7- (thiophene -2- base) -2H- benzo [d] [1,2,3] triazole (J52-1).
In some embodiments of the invention, the electron acceptor material includes being selected from fullerene derivate, non-fowler
At least one of alkene small molecule and conjugated polymer.These have excellent electricity as representative electron acceptor material
Sub- ability to accept and transmittability.
In some embodiments of the invention, the weight ratio of the electron donor material and the electron acceptor material is 1:
0.5~1:2.Under the weight proportion, efficient charge can occur between electron donor material and electron acceptor material and turn
It moves and realizes effective transmission of hole and electronics, and then can be improved the detectivity of light-detecting device.
In some embodiments of the invention, the fullerene derivate is [6,6]-phenyl C61 methyl butyrate
(PC61BM).The substance has excellent electron acceptability and transmittability, the transmission for electric current.
In some embodiments of the invention, the non-fullerene small molecule be double 2,2'- [[6,6,12,12- tetra- (and 4- oneself
Base phenyl) -6,12- dihydro 1,4-Dithiapentalene simultaneously [2,3-d:2', 3'-d']-S- two indeno [1,2-b:5-, 6-b'] bithiophene -2,
8- diyl] bis- [(Z)-methine (fluoro--two subunits of 3- oxo -1H- indenes 2,1 (3H) of 5-)]] (IT-2F).The substance has excellent
Electron acceptability and transmittability, be conducive to the transmission of separation of charge and electronics.
In some embodiments of the invention, the conjugated polymer receptor is 4- ([2,2'- bithiophene] -5- base) -2,
Bis- (2- octyldodecyl) benzo [LMN] [3,8] phenanthroline -1,3,6,8- (2H, the 7H) tetrones (N2200) of 7-.Substance tool
There are excellent electron acceptability and transmittability, is conducive to the transmission of separation of charge and electronics.
In some embodiments of the invention, the boundary layer is selected from poly- [(9,9- bis- (3 '-(N, N- dimethylaminos) third
Base) -2,7- fluorenes)-alt-2,7- (9,9- dioctyl fluorene)] (PFN), poly- 3,3'- (tetra- anthrone of 1,3,8,10- simultaneously [2,1,9-DEF:
6,5,10-D'E'F'] -2,9 (1H, 3H, 8H, 10H)-diyl of two isoquinolin) bis- (N, N- dimethylpropane -1- amine oxides)
At least one of (PDINO).
In some embodiments of the invention, the metal cathode layer electrode is in Al electrode, Cu electrode, Ag electrode
It is at least one.
In some embodiments of the invention, the metal cathode layer with a thickness of 100nm~150nm, preferably 100~
120nm.Metal cathode layer thickness is excessively thin, is easy to cause contact bad；Metal cathode layer is blocked up, when needing longer electrode deposition
Between, while being also unfavorable for saving material.The thickness of metal cathode layer is set as between 100nm~150nm, production is on the one hand easy
Light-detecting device, while metal cathode layer can also be made to contact well with boundary layer.
In some embodiments of the invention, the photoactive layer with a thickness of 100nm~300nm.In the thickness condition
Under, device has low reversed dark current, and at the same time having sufficient charge transport ability.If photoactive layer thickness is excessively thin,
It is easy to produce high reversed dark current；Active layer is blocked up, can lead to low external quantum efficiency because of charge transport ability deficiency.
According to the second aspect of the invention, the present invention provides a kind of optical detector, the optical detector includes the present invention
Light-detecting device described in first aspect.Optical detector is properly termed as photodetector again, is capable of detecting when to be incident on its surface
Upper optical power, and corresponding electric current is converted by the variation of optical power.
According to an embodiment of the invention, the optical detector is semiconductor photodetector.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the light-detecting device provided according to the embodiment of the present invention experimental group.
Fig. 2 is the structural schematic diagram of the light-detecting device according to provided by the embodiment of the present invention control group.
Fig. 3 is the macromolecule of the EDOT side chain modification provided according to the embodiment of the present invention in the solution or in solid
Abosrption spectrogram on film, wherein (a) is the abosrption spectrogram of the macromolecule of EDOT side chain modification in the solution, Fig. 3 in Fig. 3
In (b) be the modification of EDOT side chain abosrption spectrogram of the macromolecule on solid film.
Fig. 4 is (electric in the J-V of different photoactive layer thickness conditions for the light-detecting device provided according to the embodiment of the present invention
Stream-voltage) measurement result figure.What wherein (a) and (b) provided in Fig. 4 is derivative with EDOT macromolecule PBD (EDOT) and fullerene
The mixture of object is active layer, and the Al electrode of PFN modification is the measurement result of the device of cathode.
Fig. 5 is the J-V of the light-detecting device that is provided according to the embodiment of the present invention under different photoactive layer thickness conditions
(current-voltage) measurement result figure, wherein in Fig. 5 in (a) and (b) provide is with EDOT macromolecule PET-1 and non-fullerene
The mixture of small molecule receptor is active layer, and the Al electrode of PDINO modification is the measurement result of the device of cathode.
Fig. 6 is the J-V of the light-detecting device that is provided according to the embodiment of the present invention under different photoactive layer thickness conditions
Measurement result figure, what wherein (a) and (b) provided in Fig. 6 is with the mixture of EDOT macromolecule J52-1 and macromolecule receptor to live
Property layer, PDINO modification Al electrode be cathode device measurement result.
Fig. 7 is that the J-V (current-voltage) of the light-detecting device of the different systems provided according to the embodiment of the present invention is measured
As a result.Wherein in Fig. 7 (a) provide be using the mixture of EDOT macromolecule PBD (EDOT) and fullerene derivate as active layer,
The Al electrode of PFN modification is the measurement result of the device of cathode；What (b) was provided in Fig. 7 be with EDOT macromolecule PET-1 with it is non-lipid
The mixture for strangling alkene small molecule receptor is active layer, and the Al electrode of PDINO modification is the measurement result of the device of cathode；In Fig. 7
(c) what is provided is using the mixture of EDOT macromolecule J52-1 and macromolecule receptor as active layer, and the Al electrode of PDINO modification is
The measurement result of the device of cathode.
Fig. 8 gives EQE (the outer quantum effect of the light-detecting device of the different systems provided according to an embodiment of the present application
Rate) measurement result.What wherein (a) provided in Fig. 8 is to be with EDOT macromolecule PBD (EDOT) and the mixture of fullerene derivate
Active layer, the Al electrode of PFN modification are the EQE measurement result of the light-detecting device of cathode；What (b) was provided in Fig. 8 is with EDOT
The mixture of macromolecule PET-1 and non-fullerene small molecule receptor is active layer, and the Al electrode of PDINO modification is that the light of cathode is visited
Survey the EQE measurement result of device；What (c) was provided in Fig. 8 is with the mixture of EDOT macromolecule J52-1 and macromolecule receptor for work
Property layer, PDINO modification Al electrode be cathode light-detecting device EQE measurement result.
Fig. 9 gives the measurement of detectivity knot of the light-detecting device of the different systems provided according to an embodiment of the present application
Fruit.Wherein in Fig. 9 (a) provide be using the mixture of EDOT macromolecule PBD (EDOT) and fullerene derivate as active layer,
The Al electrode of PFN modification is the measurement of detectivity result of the light-detecting device of cathode；What (b) was provided in Fig. 9 is with EDOT high score
The mixture of sub- PET-1 and non-fullerene small molecule receptor is active layer, and the Al electrode of PDINO modification is the optical detector of cathode
The measurement of detectivity result of part；What (c) was provided in Fig. 9 is with the mixture of EDOT macromolecule J52-1 and macromolecule receptor for work
Property layer, PDINO modification Al electrode be cathode light-detecting device measurement of detectivity result.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to is used to explain the present invention, and is not considered as limiting the invention.
This application provides a kind of light-detecting device structures of achievable highly sensitive high-molecular optical detector.Simultaneously to pass
Unite positive assembling structure high-molecular optical detector as a comparison, provided light-detecting device have high sensitivity, Er Qiejie
Structure is simple, and preparation process is simple.
In certain embodiments of the present invention, to include: from anode to cathode successively include: provided light-detecting device
Indium tin oxide anode layer, photoactive layer, boundary layer and metal cathode layer；Wherein the photoactive layer is located at the indium tin oxygen
The upper surface of compound anode layer, the photoactive layer are formed by the mixture comprising electron donor material and electron acceptor material；
The boundary layer is located at the upper surface of the photoactive layer, and the metal cathode layer is located at the upper surface of the boundary layer.Herein
In, when statement " upper surface ", be using indium tin oxide anode layer as bottom for, other photoactive layers, boundary layer with
And metal cathode layer is respectively positioned on the upper layer of the indium tin oxide anode layer, therefore by taking photoactive layer as an example, " the upper table of photoactive layer
Face " refers to the side in two faces of photoactive layer far from indium tin oxide anode layer.
In at least some embodiments, the electron donor material includes the modification of 3,4-ethylene dioxythiophene ring side chain
Donor-receiver conjugated polymer, the electron acceptor material include that fullerene derivate, non-fullerene small molecule and conjugation are high
Molecule.
The solution of the present invention is explained below in conjunction with embodiment.It will be understood to those of skill in the art that following
Embodiment is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Particular technique or item are not specified in embodiment
Part, it described technology or conditions or is carried out according to the literature in the art according to product description.Agents useful for same or instrument
Production firm person is not specified in device, and being can be with conventional products that are commercially available.It is described below EDOT (EH) as side chain
Some examples of D-A copolymer are accessed, however those skilled in the art should understand that other derivatives of EDOT are suitable for connecting
Donor monomer onto the main chain of copolymer.
Embodiment 1
(1) PBD (EDOT) is synthesized
Firstly, embodiment 1 synthesizes PBD (EDOT) with the following method.Include:
1. the Sn as donor monomer2The preparation of-BDT-EDOT (EH)
According to this group of document (Zhang L, Yang T, Shen L, et al.Advanced Materials.2015,27
(41): 6496-6503) method reported synthesizes Sn2-BDT-EDOT(EH)。
2. the Br as receptor unit2The preparation of-DPP (BO)
According to E.J.Zhou et al. (E.J.Zhou, S.P.Yamakawa, K.Tajima, C.H.Yang, K.Hashimoto,
Chem.Mater.2009,21,4055) method reported synthesizes 3,6- bis- (5- bromothiophene -2- bases)-two (2- butyl octyls)
Pyrrolo- [3,4-c] pyrroles -1,4 (2H, 5H)-diketone (Br2-DPP(BO))。
3. the preparation of donor-receiver copolymer
With Pd (PPh3)4Pass through double stannane BDT base donors using toluene/DMF mixture as reaction dissolvent for catalyst
Donor-receiver copolymer is prepared in Stille polycondensation reaction between unit and dibrominated receptor unit.
The preparation method of PBD (EDOT) is summarized as follows:
Sn is loaded onto 25 milliliters of predrying bottle2- BDT-EDOT (EH) (250 milligrams, 0.245 mM), Br2-
DPP (BO) (194.68 milligrams, 0.245 mM) and Pd (PPh3)4(11.3 milligrams, 0.010 mM).Bottle is first taken out very
Empty to be then charged into argon gas, this process is repeated 3 times.Then it is added toluene (9.8 milliliters) and DMF (0.98 milliliter).It will obtain
Mixture 120 DEG C keep the temperature 24 hours.Crude product is filtered through diatomite and acetone precipitation is collected.Then the solid that will be obtained
It is successively rinsed through MeOH, acetone, n-hexane and chloroform in Soxhlet extractor.By the product concentration in chloroform, then just
It is precipitated in hexane.After being dried under reduced pressure, PBD (EDOT) copolymer (301 milligrams), yield 92.55% are obtained.
(2) light-detecting device is prepared
Then using above-mentioned PBD (EDOT) copolymer being prepared, light-detecting device is prepared.And to the performance of device into
Row test.
Wherein, indium tin oxide (ITO) is bottom as anode, and conjugated polyelectrolytes PFN modified Al is cathode, EDOT
Macromolecule PBD (EDOT) and PC61The photoactive layer that BM is prepared is placed between two electrodes, is prepared for light-detecting device.
Wherein light-detecting device structure prepared by experimental group is ITO/ active layer/PFN/Al.Prepare light-detecting device
Method summary is as follows:
Successively washed dose of ITO substrate, deionized water, acetone, isopropanol ultrasonic cleaning.Then, by ITO substrate in baking oven
Middle drying, and handled 15 minutes in UV ozone room.Then, the substrate of ITO layer is transferred in the glove box filled with nitrogen.It will
The PBD (EDOT) and PC of above-mentioned preparation61BM (1:2, w/w) (PC61BM:[6,6]-phenyl C61 methyl butyrate) mixing, then will
Mixture is dissolved in chloroform/1,2- dichloro-benzenes (90:10, v/v).PC61The molecular structure of BM can be expressed as shown in formula (II),
PC61BM(II)
Obtained solution is spin-coated on ITO in glove box, to form active layer, with a thickness of about 190nm.It is depositing
Before Al electrode, poly- [(9,9- bis- (3 '-(N, N- dimethylamino) propyl) -2,7- fluorenes)-alt-2,7- is first covered on active layer
(9,9- dioctyl fluorene)] (PFN) layer.Finally, obtained structure is transferred to vacuum chamber, then 3 × 10-6The base pressure of mbar
Under power on PFN layer heat deposition about 100nm Al.The photoactive layer area of obtained device is 0.045cm2。
Measurement to the Current density-voltage (J-V) of obtained device is under AM1.5G solar simulator illumination
(100mW cm-2) measured and obtained in glove box by the 2400 source measuring unit of Keithley that computer controls.Device is secretly led
J-V characteristic curve is then in air by 2635 source measuring unit of the Keithley measurement of computer control.External quantum efficiency
It (EQE) is in glove box with Enlitech QE-R system testing.
Light-detecting device structure prepared by control group is ITO/PEDOT:PSS/ active layer/PFN/Al.The control group institute
Active layer material is identical as experimental group in the light-detecting device of preparation, but using the ITO of PEDOT:PSS modification as anode.
The preparation method is as follows:
By successively washed dose of ITO substrate, deionized water, acetone, isopropanol ultrasonic cleaning.Then, ITO substrate is being dried
It is dry in case, and handled 15 minutes in UV ozone room.PEDOT:PSS [poly- (3,4- ethene dioxythiophene): poly- (styrene sulphur
Acid)] aqueous solution through 0.22 μm of membrane filtration, then rotates into row spin coating 25s in ITO electrode with 3000, PEDOT:PSS made to exist
After the surface ITO forms the uniform film of one layer of about 40nm, 15min is placed on 150 DEG C of warm table to remove the water in film
Point.100 DEG C are cooled to after closing warm table, is placed into culture dish.It then, will be by ITO layer and the PEDOT:PSS layers of knot formed
Structure is transferred in the glove box filled with nitrogen, will be dissolved in the mixture even spread in chloroform/1,2- dichloro-benzenes (90:10, v/v)
On substrate, the active layer with experimental group same thickness is prepared.Then on PFN layer heat deposition about 100nm Al.It is obtained
The photoactive layer area of device is 0.045cm2。
J-V and EQE is carried out to device obtained in method identical with experimental group to test.
Embodiment 2
(1) PET-1 is synthesized
Synthesize PET-1 with the following method first, comprising:
1. the Sn as donor monomer2The preparation of-BDT-EDOT (EH)
To have obtained donor monomer Sn with identical method in example 12-BDT-EDOT(EH)。
2. the Br as receptor unit2The preparation of-TPD
According to Y.P.Zou et al. (Y.P.Zou, A.Najari, P.Berrouard, S.Beaupre, B.R.Aich,
Y.Tao, M.Leclerc, J.Am.Chem.Soc.2010,132,5330) report the step of to synthesize receptor unit 1,3- bis- bromo-
5- octyl -4H- thieno [3,4-c] pyrroles -4,6 (5H)-diketone (Br2-TPD)。
3. the preparation of donor-receiver copolymer
The synthesis of PET-1 is carried out according to following steps:
Sn2-BDT-EDOT (EH) (178.6 milligrams, 0.175 mM) are packed into 10 milliliters of drying round-bottomed flask,
Br2-C8TPD (HD) (181.3 milligrams, 0.175 mM) and Pd (PPh3) 4 (5.05 milligrams, 0.0044 mM).Bottle
It vacuumizes, is filled with argon gas, repeat the operation three times, be then added toluene (4.2 milliliters) and DMF (0.42 milliliter).By mixture
It flows back 24 hours at 120 DEG C.To after the reaction was completed, be down to room temperature, solid is collected, through methanol, acetone, just in Soxhlet extractor
It rinses in hexane, is finally dissolved out with chloroform.It by the product concentration in chloroform, then precipitates in methyl alcohol, collects solid, it is dry
It obtains copolymer (259.3 milligrams), yield 94.3%.
(2) light-detecting device is prepared
Then a kind of light-detecting device is prepared using the PET-1 of prepared acquisition.Experimental group and control group respectively.
Experimental group
Wherein the light-detecting device result of experimental group preparation is ITO/ active layer/PDINO/Al, and indium tin oxide (ITO) is
Bottom is as anode, and conjugated polyelectrolytes PDINO modified Al is cathode, what EDOT macromolecule PET-1 and IT-2F were prepared
Photoactive layer is placed between two electrodes, is prepared for light-detecting device.
The method summary for preparing light-detecting device is as follows.ITO substrate successive washed dose, deionized water, acetone, isopropanol
Ultrasonic cleaning.Then, ITO substrate is dried in an oven, and is handled 15 minutes in UV ozone room.The ITO handled well is served as a contrast
Bottom is put into nitrogen glove box.The PET-1 prepared in example 2 and IT-2F (1:1, w/w) are mixed, mixture is then dissolved in first
In benzene/diphenyl ether (99:1, v/v).The molecular structure of IT-2F can be expressed as shown in formula (III),
IT-2F(III)
Obtained solution is spin-coated on ITO in glove box, to form active layer, with a thickness of about 200nm.It is depositing
Before Al electrode, (1,3,8,10- tetra- anthrone simultaneously [2,1,9-DEF:6,5,10-D'E'F'] two poly- 3,3'- are first covered on active layer
Isoquinolin -2,9 (1H, 3H, 8H, 10H)-diyl) bis- (N, N- dimethylpropane -1- amine oxide) (PDINO) layers.Finally, will
To structure be transferred to vacuum chamber, then 3 × 10-6Under the reference pressure of mbar on PDINO layer heat deposition about 100nm
Al.The photoactive layer area of obtained device is 0.045cm2。
J-V and EQE is carried out to device obtained in the same manner as in the example 1 to test.
Control group
Light-detecting device structure prepared by control group is ITO/PEDOT:PSS/ active layer/PDINO/Al.In the control
In group, used active layer material is identical as experimental group, compared to control group, uses the ITO of PEDOT:PSS modification as sun
Pole.
Preparation method is as follows, and successively washed dose of ITO substrate, deionized water, acetone, isopropanol are cleaned by ultrasonic.Then,
ITO substrate is dried in an oven, and is handled 15 minutes in UV ozone room.PEDOT:PSS [poly- (3,4- ethylene dioxy thiophene
Pheno): poly- (styrene sulfonic acid)] aqueous solution through 0.22 μm of membrane filtration, then rotates into row spin coating 25s in ITO electrode with 3000,
Make PEDOT:PSS after the uniform film that the surface ITO forms one layer of about 40nm, is placed on 150 DEG C of warm table 15min to go
Except the moisture in film.100 DEG C are cooled to after closing warm table, is placed into culture dish.It then, will be by ITO layer and PEDOT:
The structure of PSS layer composition is transferred in the glove box filled with nitrogen, will be dissolved in the PET-1 of toluene/diphenyl ether (99:1, v/v)
On substrate with IT-2F (1:1, w/w) mixture even spread, the active layer with same thickness in example 5 is prepared.Then exist
The Al of heat deposition about 100nm on PDINO layer.The photoactive layer area of obtained device is 0.045cm2。
J-V and EQE is carried out to device obtained in the same manner as in Example 1 to test.
Embodiment 3
(1) J52-1 is synthesized
Synthesize J52-1 with the following method first, comprising:
1. the Sn as donor monomer2The preparation of-BDT-EDOT (EH)
To have obtained donor monomer Sn with identical method in example 12-BDT-EDOT(EH)。
2. the Br as receptor unit2The preparation of-FTAZ (HD)
According to Y.F.Li et al. (Bin H, Zhang Z G, Gao L, et al.Journal of the American
Chemical Society, 2016,138 (13): 4657-4664) report the step of synthesize receptor unit fluorine benzotriazole
(Br2-FTAZ(HD))。
3. the preparation of donor-receiver copolymer
The synthesis of J52-1 is carried out according to following steps:
Sn is packed into 25 milliliters of drying round-bottomed flask2- BDT-EDOT (EH) (255.2 milligrams, 0.250 mM),
Br2- FTAZ (HD) (175.4 milligrams, 0.250 mM) and Pd (PPh3)4(10 milligrams, 0.0086 mM).Bottle is taken out true
Sky is filled with argon gas, repeats the operation three times, is then added toluene (10 milliliters) and DMF (1 milliliter).Mixture is returned at 120 DEG C
Stream 12 hours.To after the reaction was completed, be down to room temperature, solid is collected, through floating in methanol, acetone, n-hexane in Soxhlet extractor
It washes, is finally dissolved out with chloroform.It by the product concentration in chloroform, then precipitates in methyl alcohol, collects solid, dry copolymer
(297.5 milligrams), yield 96.2%.
(2) light-detecting device is prepared
Then J52-1 is prepared using above-mentioned, prepares light-detecting device.Including experimental group and control group.
Experimental group
The light-detecting device structure that experimental group provides is ITO/ active layer/PDINO/Al, and wherein indium tin oxide (ITO) is
For bottom as anode, conjugated polyelectrolytes PFN modified Al is cathode, the light that EDOT macromolecule J52-1 and N2200 are prepared
Activity is placed between two electrodes, is prepared for light-detecting device.
The method summary for preparing light-detecting device is as follows.ITO substrate successive washed dose, deionized water, acetone, isopropanol
Ultrasonic cleaning.Then, ITO substrate is dried in an oven, and is handled 15 minutes in UV ozone room.Then, by the lining of ITO layer
Bottom is transferred in the glove box filled with nitrogen.The J52-1 prepared in example 3 and N2200 (6.5:3, w/w) are mixed, then will
Mixture is dissolved in chloroform/1,8- diiodo-octane (99.5:0.5, v/v).The molecular structure of N2200 can be expressed as formula (IV) institute
Show,
N2200(IV)
Obtained solution is spin-coated on ITO in glove box, to form active layer, with a thickness of about 180nm.It is depositing
Before Al electrode, (PDINO) layer is first covered on active layer.Finally, obtained structure is transferred to vacuum chamber, then 3 × 10- 6Under the reference pressure of mbar on PDINO layer heat deposition about 100nm Al.The photoactive layer area of obtained device is
0.045cm2。
J-V and EQE is carried out to device obtained in the same manner as in the example 1 to test.
Control group
Light-detecting device structure prepared by control group is ITO/PEDOT:PSS/ active layer/PDINO/Al.Wherein, the light
Sensitive detection parts structure used active layer material it is identical as above-mentioned experimental group, compared to experimental group, repaired using PEDOT:PSS
The ITO of decorations is as anode.
Preparation method is as follows, and successively washed dose of ITO substrate, deionized water, acetone, isopropanol are cleaned by ultrasonic.Then,
ITO substrate is dried in an oven, and is handled 15 minutes in UV ozone room.PEDOT:PSS [poly- (3,4- ethylene dioxy thiophene
Pheno): poly- (styrene sulfonic acid)] aqueous solution through 0.22 μm of membrane filtration, then rotates into row spin coating 25s in ITO electrode with 3000,
Make PEDOT:PSS after the uniform film that the surface ITO forms one layer of about 40nm, is placed on 150 DEG C of warm table 15min to go
Except the moisture in film.100 DEG C are cooled to after closing warm table, is placed into culture dish.It then, will be by ITO layer and PEDOT:
The structure of PSS layer composition is transferred in the glove box filled with nitrogen, will be dissolved in chloroform/1,8- diiodo-octane (99.5:0.5, v/v)
In mixture even spread on substrate, preparation with experimental group in same thickness active layer.Then heat sink on PDINO layer
The Al of product about 100nm.The photoactive layer area of obtained device is 0.045cm2。
J-V and EQE is carried out to device obtained in the same manner as in the example 1 to test.
As a result
Fig. 1 gives the structural schematic diagram of the light-detecting device of 1 experimental group of the embodiment of the present application offer, and Fig. 2 gives reality
The structural schematic diagram of the light-detecting device of 1 control group of example offer is provided.The light-detecting device that wherein Fig. 1 is provided does not have PEDOT:PSS
Modification；The light-detecting device that Fig. 2 is provided has PEDOT:PSS interface-modifying layer between photoactive layer and ito anode layer, as biography
System formal dress device, is contrasted.
Fig. 3 gives absorption spectrum of the macromolecule of EDOT side chain modification in the solution or on solid film, wherein
(a) is the abosrption spectrogram of the macromolecule of EDOT side chain modification in the solution in Fig. 3, and (b) is the height of EDOT side chain modification in Fig. 3
Abosrption spectrogram of the molecule in solid film.From figure 3, it can be seen that the macromolecule modified through EDOT side chain, spectral response can
To extend near infrared region from ultraviolet region.
The current-voltage characteristic of the light-detecting device under different photoactive layer thickness is had studied simultaneously.Wherein embodiment 1~
The current-voltage characteristic that embodiment 3 prepares the light-detecting device of different photoactive layer thickness is as shown in Figure 4, Figure 5 and Figure 6.Such as Fig. 4
In shown in (a) and (b), the thickness of photoactive layer is respectively 80nm, 140nm, 200nm and 300nm, for PBD (EDOT):
PC61BM system, with the increase of photoactive layer thickness, the dark current under light-detecting device reverse biased can be reduced.Compared to having
PEDOT:PSS, no PEDOT:PSS device show lower dark current density under reverse bias.Thickness reach 200nm with
Afterwards, the reversed dark current of device reaches than preferably numerical value, is optimal value in 250nm or so.Further increase thickness extremely
300nm, the dark current under reverse biased do not continue to reduce.In Fig. 5 shown in (a) and (b), the thickness of photoactive layer is respectively
In 130nm, 190nm, 260nm and 340nm and Fig. 6 shown in (a) and (b), the thickness of photoactive layer be respectively 90nm,
130nm, 180nm and 230nm are dark under light-detecting device reverse biased for PET-1:IT-2F and J52-1:N2200 system
Electric current is reduced with the increase of photoactive layer thickness, and the device without PEDOT:PSS compares the device table for having PEDOT:PSS
Reveal lower reversed dark current density, these and PBD (EDOT): PC61BM system rule is similar.Wherein difference,
The optimal thickness of PET-1:IT-2F system is in 200nm or so, and the optimal thickness of J52-1:N2200 system is in 180nm or so.
The current-voltage characteristic of optimal light-detecting device prepared by 1~embodiment of embodiment 3 is as shown in fig. 7, be free of
The short-circuit current density of the short-circuit current density of the light-detecting device of PEDOT:PSS interface-modifying layer and traditional formal dress device is can
It matches in excellence or beauty, shows that carrier can be generated effectively in both device architecture systems.Wherein, in Fig. 7 (a) provide be with
The mixture of EDOT macromolecule PBD (EDOT) and fullerene derivate is active layer, and the Al electrode of PFN modification is the device of cathode
Measurement result.Under backward voltage, dark current ratio that the device modified from no PEDOT:PSS is observed is from traditional formal dress device
The low about 1 most magnitude of the dark current observed, reaches 1.6 × 10 in the commutating ratio that ± 2V is generated7.And (b) is provided in Fig. 7
It is using the mixture of EDOT macromolecule PET-1 and non-fullerene small molecule receptor as active layer, the Al electrode of PDINO modification is yin
The measurement result of the device of pole.Under backward voltage, dark current ratio that the simple Devices modified from no PEDOT:PSS are observed from
Low about 1 order of magnitude of the dark current that traditional formal dress device is observed reaches 6.3 × 10 in the commutating ratio that ± 2V is generated6.In Fig. 7
(c) what is provided is using the mixture of EDOT macromolecule J52-1 and macromolecule receptor as active layer, and the Al electrode of PDINO modification is
The measurement result of the device of cathode.Under backward voltage, never observed in the light-detecting device of PEDOT:PSS modification dark
Electric current about 1 order of magnitude lower than the dark current observed from traditional formal dress device, reach 3.7 in the commutating ratio that ± 2V is generated ×
106。
The good diode characteristic that the device modified from no PEDOT:PSS is observed shows compared to more traditional formal dress device
The device of part, no PEDOT:PSS modification is not only prepared simply, but also more conducively deposition of the macromolecule donor in substrate, Ke Yixian
Land the intrinsic leakage current for inhibiting diode under the conditions of secretly leading.This phenomenon is in the height based on EDOT as conjugation side chain modification
Molecule, respectively and including fullerene derivate PC61BM, non-fullerene small molecule IT-2F and tri- kinds of macromolecule N2200 it is different
Receptor is blended, and is observed in the photodiode of preparation.Also, in 1~embodiment of embodiment 3, no PEDOT:PSS is repaired
The simple Devices of decorations compare the device modified through PEDOT:PSS, the photoelectric current under AM1.5G 100mW/cm2 light-intensity conditions
Curve is not substantially reduced, and illustrates that the extraction of photo-generated carrier in the device of no PEDOT:PSS modification is efficient.
Fig. 8 gives the response rate of the high-molecular optical electric explorer prepared in 1~embodiment of embodiment 3, and parameter indicates
Its photon-charge transfer capability.As can be seen that in fullerene or small molecule systems, regardless of whether there is PEDOT:PSS modification
Device can effectively capture corresponding light and effectively generate photoelectric current.And in overall height molecular system, no PEDOT:PSS
The device photoelectric transfer capability of modification slightly reduces, but influences on its detectivity unobvious.In field of photodetectors, it to be used for table
The performance of sign photodetector has several important parameters.One of parameter is noise equivalent power (NEP), it can be with table
It states are as follows:
NEP=(A Δ f)1/2/D*
Wherein A is the effective area of detector, and unit is cm2, Δ f is electric bandwidth, and unit is that Hz and D* is detectivity,
Unit is cm Hz-1/2W-1(or Jones).If not considering thermal noise and frequency noise, only consider dark current to shot noise
Contribution, detectivity can be stated are as follows:
D*=R/ (2qJd)1/2
D* value is calculated, wherein R is response rate, and q is the absolute quantity of electric charge 1.60 × 10-19C, JdIt is the dark current of device, it is single
Position is A cm-2.Fig. 9 gives the detectivity of high-molecular optical electric explorer.In EDOT macromolecule and fullerene acceptor system, nothing
Dark current of the simple Devices of PEDOT:PSS modification at -0.2V is 2.02 × 10-11A/cm2, reach 8.64 in wavelength 780nm
×1013Jones.However, highest only has 1.36 × 10 within the scope of its response spectrum in traditional formal dress device13Jones
Detectivity.For non-fullerene small molecule systems, the device of no PEDOT:PSS modification has highest detectable rate in 750nm
7.69×1013Jones, an order of magnitude higher than the detectivity of traditional formal dress device architecture.Similarly, in overall height molecular system
In, the device of no PEDOT:PSS modification also has similar feature, and the detectivity than traditional formal dress device architecture is more than one
The order of magnitude.The result shows that these are based on the macromolecule that EDOT side chain is modified, without including the modification of PEDOT:PSS arbitrary interface layer
High sensitivity may be implemented in device, while ensure that the device architecture of simple optical detector.This method is for being used for
Simplify preparation process, raising high-molecular optical detector detectivity is of great significance.
In the description of the present invention, it is to be understood that, term " center ", " longitudinal direction ", " transverse direction ", " length ", " width ",
" thickness ", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom" "inner", "outside", etc. instruction
Orientation or positional relationship be based on the orientation or positional relationship shown in the drawings, be merely for convenience of description the present invention and simplification retouch
It states, rather than the device or element of indication or suggestion meaning must have a particular orientation, be constructed and operated in a specific orientation,
Therefore it is not considered as limiting the invention.
In addition, term " first ", " second " are used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance
Or implicitly indicate the quantity of indicated technical characteristic.Define " first " as a result, the feature of " second " can be expressed or
Implicitly include at least one this feature.In the description of the present invention, the meaning of " plurality " is at least two, such as two, three
It is a etc., unless otherwise specifically defined.
In the present invention unless specifically defined or limited otherwise, term " installation ", " connected ", " connection ", " fixation " etc.
Term shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or integral；It can be electrical connection
Or it can communicate each other；It can be directly connected, the company inside two elements can also be can be indirectly connected through an intermediary
Logical or two elements interaction relationship, unless otherwise restricted clearly.For the ordinary skill in the art, may be used
To understand the concrete meaning of above-mentioned term in the present invention as the case may be.
In the present invention unless specifically defined or limited otherwise, fisrt feature in the second feature " on " or " down " can be with
It is that the first and second features directly contact or the first and second features pass through intermediary mediate contact.Moreover, fisrt feature exists
Second feature " on ", " top " and " above " but fisrt feature be directly above or diagonally above the second feature, or be merely representative of
First feature horizontal height is higher than second feature.Fisrt feature can be under the second feature " below ", " below " and " below "
One feature is directly under or diagonally below the second feature, or is merely representative of first feature horizontal height less than second feature.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be any
It can be combined in any suitable manner in a or multiple embodiment or examples.In addition, without conflicting with each other, the technology of this field
The feature of different embodiments or examples described in this specification and different embodiments or examples can be combined by personnel
And combination.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of light-detecting device characterized by comprising
Indium tin oxide anode layer, photoactive layer, boundary layer and metal cathode layer；
Wherein the photoactive layer is located at the upper layer of the indium tin oxide anode layer, and the photoactive layer is by including electron donor
The mixture of material and electron acceptor material is formed；
The boundary layer is located at the upper layer of the photoactive layer, and the metal cathode layer is located at the upper layer of the boundary layer.
2. light-detecting device according to claim 1, which is characterized in that in the indium tin oxide anode layer and the light
Between active layer, interface-modifying layer is not present；
Optionally, there is no the interfaces that PEDOT:PSS is formed between the indium tin oxide anode layer and the photoactive layer
Decorative layer；
Optionally, the photoactive layer is located at the upper layer of the indium tin oxide anode layer and upper with indium tin oxide anode layer
Surface contact, the boundary layer are located at the upper layer of the photoactive layer and contact with the upper surface of the photoactive layer, the gold
Belong to cathode layer to be located at the upper layer of the boundary layer and contact with the upper layer of the boundary layer.
3. light-detecting device according to claim 1, which is characterized in that the indium tin oxide positive layer with a thickness of
120nm~140nm, preferably 130nm.
4. light-detecting device according to claim 1, which is characterized in that the electron donor material includes 3,4- ethylene two
The donor-receiver type macromolecule of oxygen thiphene ring side chain modification；
Optionally, the electron donor material is selected from least one of PBD (EDOT), PET-1, J52-1.
5. light-detecting device according to claim 1, which is characterized in that the electron acceptor material includes being selected from fowler
At least one of ene derivative, non-fullerene small molecule and conjugated polymer；
Optionally, the weight ratio of the electron donor material and the electron acceptor material is 1:0.5~1:2.
6. light-detecting device according to claim 5, wherein the fullerene derivate is PC61BM；
Optionally, the non-fullerene small molecule is IT-2F；
Optionally, the conjugated polymer receptor is N2200.
7. light-detecting device according to claim 1, which is characterized in that the boundary layer in PFN, PDINO extremely
Few one kind.
8. light-detecting device according to claim 1, which is characterized in that the metal cathode layer electrode be selected from Al electrode,
At least one of Cu electrode, Ag electrode；
Optionally, the metal cathode layer with a thickness of 100nm~150nm, preferably 100nm~120nm.
9. light-detecting device according to claim 1, which is characterized in that the photoactive layer with a thickness of 100nm~
300nm, preferably 150nm~250nm.
10. a kind of optical detector, which is characterized in that including light-detecting device according to any one of claims 1 to 9；
Optionally, the optical detector is semiconductor photodetector.
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