CN106025070B - Photomultiplier transit type organic photodetector with spectral selection and preparation method thereof - Google Patents
Photomultiplier transit type organic photodetector with spectral selection and preparation method thereof Download PDFInfo
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Abstract
Photomultiplier transit type organic photodetector with spectral selection, including transparent substrates (1);The transparent electrode (2) being arranged on the transparent substrates (1);The transparent electrode decorative layer (3) being arranged on the transparent electrode (2);The active layer (4) being arranged on the transparent electrode decorative layer (3);And the metal electrode (5) being arranged on the active layer (4);Wherein, the active layer is the blend film of electron donor material and electron acceptor material, and the film thickness is 2.0-5.0 μm;The weight ratio of electron donor and electron acceptor material is 100 in the active layer:1;The electron donor material is poly- (3- hexyl thiophene) (P3HT) or quasi polymer (PBDT-TS1);The electron acceptor material is fullerene derivate (PCBM, ICBA) or non-fullerene acceptor (ITIC).
Description
Technical field
The present invention relates to optical detection fields.It is visited more particularly, to the organic light of photomultiplier transit type with spectral selection
Survey device and preparation method thereof.
Background technique
Organic semiconducting materials due to its extinction coefficient it is high, it is at low cost, green, can be made into large area flexible device and by
The concern of people.With the continuous development of organic semiconducting materials, there has also been big for the opto-electronic device performance based on organic material
Amplitude improves, and the research of organic photodetector is also by the concern of people.The current main base of organic photodetector reported in the literature
In organic photovoltaic effect.Organic material captures solar photon and generates exciton, exciton diffusion to the interface to acceptor material, solution
From at free carrier, carrier is collected by electrode, to generate photogenerated current, realizes detection and response to light.Due to by
Outer quantum to material extinction coefficient, the influence of exciton fission efficiency, carrier transport and collection efficiency, this kind of optical detector is imitated
Rate is both less than 100%, and for dim light or superweak optical detection, the responsiveness of device is just restricted.Therefore, in practical applications
Such detector needs plus preamplifier, is sampled, is amplified to faint electric signal, to realize the spy to faint light
It surveys, and the cost of detection system then will increase using preamplifier, while bringing new noise.
Organic photodetector based on photovoltaic effect, it is impossible to directly prepare organic optical detection with spectral selection
Device, it is 1 that active layer is to acceptor material by weight:0.8 to 1:4 ratio doping, to realize efficient exciton solution
From and carrier transport.Two kinds of organic semiconducting materials make the spectral response range of device wider, organic optical detection of preparation
Device does not have spectral selection, and spectral response range is typically greater than 100nm.Organic photodetector with spectral selection
It is all widely used in many fields, image, medicine sensing, security system etc., the common feature in these fields are to need
It detects the light of particular range of wavelengths and ignores background noise.It is common in order to improve the spectral selection of organic photodetector
Way is that the optical detector of wide spectrum response range and dichroic prism or band logical optical light filter are coupled.This nothing
The complexity that will increase organic photodetector manufacturing cost and application is doubted, the reduction of device performance is also resulted in.In addition, commercialization
Band logical optical filter do not cover it is all using required wave band so that the full width at half maximum (FWHM) of device is greater than
50nm。
Summary of the invention
It is an object of the present invention to provide a kind of photomultiplier transit type organic photodetector with spectral selection, with
Lower cost and simple device architecture realize photomultiplier transit and optical electivity function.
It is another object of the present invention to provide a kind of photomultiplier transit type organic photodetector with spectral selection
Preparation method photomultiplier transit and optical electivity function are realized with simple preparation method.
In order to achieve the above objectives, the present invention adopts the following technical solutions:
Photomultiplier transit type organic photodetector with spectral selection, including:
Transparent substrates (1);
The transparent electrode (2) being arranged on the transparent substrates (1);
The transparent electrode decorative layer (3) being arranged on the transparent electrode (2);
The active layer (4) being arranged on the transparent electrode decorative layer (3);And
The metal electrode (5) being arranged on the active layer (4),
Wherein, the active layer is the blend film of electron donor material and electron acceptor material, and the film thickness is
2.0-5.0μm;The weight ratio of electron donor and electron acceptor material is 100 in the active layer:1;Wherein, the electron donor
Material is poly- (3- hexyl thiophene) (P3HT) or quasi polymer (PBDT-TS1), and the electron acceptor material is derivative for fullerene
Object (PCBM, ICBA) or non-fullerene acceptor (ITIC).
Preferably, the transparent substrates are glass.
Preferably, the transparent electrode is indium tin oxide (ITO).
Preferably, the transparent electrode decorative layer is by poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid (PEDOT:
PSS), molybdenum oxide (MoO3) or [bis- (N, the N- DimethylAminopropyl) fluorenes of 9,9- dioctyl fluorene -9,9-] (PFN) composition.
Preferably, the metal electrode is aluminium or silver, with a thickness of 100nm.
Preferably, the blend film of the active layer is with a thickness of 2.0 μm.
The preparation method of photomultiplier transit type organic photodetector with spectral selection, includes the following steps:
Step 1:Using glass as transparent substrates;
Step 2:Transparent electrode is prepared in the transparent substrates;
Step 3:Transparent electrode decorative layer is prepared in the transparent electrode;
Step 4:Active layer is prepared on the transparent electrode decorative layer, including:By poly- (3- hexyl thiophene) (P3HT) or
Quasi polymer (PBDT-TS1) is used as electron donor material, by fullerene derivate (PCBM, ICBA) or non-fullerene acceptor
(ITIC) it is used as electron acceptor material;The electron donor material and the electron acceptor material are according to weight ratio 100:1 is dissolved in
In o-dichlorohenzene (o-DCB), be prepared into mixed solution, by the uniform drop coating of the mixed solution preparation transparent electrode decorative layer
On, reheating makes o-dichlorohenzene (o-DCB) quickly volatilize, and leaves with a thickness of 2.0-5.0 μm of electron donor material and electron acceptor
The blend film of material is as active layer, wherein the heating temperature is 80-120 DEG C;
Step 5:Metal electrode is prepared on the active layer.
Preferably, step 2 further comprises:Indium tin oxide (ITO) is plated in the transparent substrates, is then soaked respectively
It steeps in deionized water, dehydrated alcohol, then cleaned with ultrasonic washing instrument;With being dried with nitrogen after cleaning up, then use plasma
Cleaning device handles 1min.
Preferably, step 3 further comprises:Poly- (the 3,4- ethylene dioxy thiophene of spin coating in the transparent electrode prepared in step 2
Pheno)-polystyrolsulfon acid (PEDOT:PSS) or [bis- (N, the N- DimethylAminopropyl) fluorenes of 9,9- dioctyl fluorenes -9,9-] (PFN),
Wherein spin coating rate is 5000r/min, spin-coating time 40s, poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid (PEDOT:
PSS) dosage is 80 μ L;The 10min of annealing is placed on 150 DEG C of warm table after spin coating;Or the transparent electricity prepared in step 2
Molybdenum oxide (the MoO of one layer of 10nm thickness is deposited on extremely with the rate of 0.2nm/s3)。
Preferably, step 5 further comprises:Sample obtained in step 4 is put into the vacuum chamber for being placed with aluminium wire, institute
Vacuum degree in vacuum chamber is stated lower than 1 × 10-4Pa;Heating aluminium wire makes its evaporation, evaporation rate 0.2nm/s, evaporation with a thickness of
100nm。
Beneficial effects of the present invention are as follows:
1, the full width at half maximum (FWHM) of the organic photodetector method is less than 30nm, and then has spectral selection;
2, the organic photodetector has the external quantum efficiency for being greater than 100% and device architecture is simple;
3, the organic photodetector preparation method is economical and simple.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 shows organic photodetector structural schematic diagram of the present invention.
1.0 μ m-thick P3HT are based on Fig. 2 shows of the present invention:PCBM(100:1) for active layer organic photodetector-
External quantum efficiency spectra curve under 20V bias.
Fig. 3, which is shown, of the present invention is based on 2.0 μm, 2.5 μm, 5.0 μm and 7.5 μ m-thick P3HT:PCBM(100:It 1) is active
External quantum efficiency spectra curve of the organic photodetector of layer under -20V bias.
Fig. 4 shows the method for the invention flow chart.
Fig. 5, which is shown, of the present invention is based on 2.0 μ m-thick P3HT:PCBM(100:1) for active layer organic photodetector-
External quantum efficiency spectra curve under 20V bias.
Fig. 6, which is shown, of the present invention is based on 2.0 μ m-thick P3HT:PCBM(100:1) for active layer organic photodetector-
Sensitivity curve under 20V bias.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further below with reference to preferred embodiments and drawings
It is bright.Similar component is indicated in attached drawing with identical appended drawing reference.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
As shown in Figure 1, the photomultiplier transit type organic photodetector with spectral selection, including transparent substrates 1;Setting exists
Transparent electrode 2 in the transparent substrates 1;Transparent electrode decorative layer 3 in the transparent electrode 2 is set;It is arranged in the transparent electricity
Active layer 4 on pole decorative layer 3;And the metal electrode 5 being arranged on the active layer (4).
The transparent substrates 1 are glass, and the transparent electrode 2 is indium tin oxide (ITO), the transparent electrode decorative layer
3 be poly- (3,4- ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), molybdenum oxide (MoO3) or [9,9- dioctyl fluorene-
Bis- (N, the N- DimethylAminopropyl) fluorenes of 9,9-] (PFN).
The active layer 4 is the blend film of electron donor material and electron acceptor material, in the present invention, blend film
Thickness is selected as 2.0-5.0 μm.Electron donor material be poly- (3- hexyl thiophene) (P3HT) or quasi polymer (PBDT-TS1),
Electron acceptor material is fullerene derivate (PCBM, ICBA) or non-fullerene acceptor (ITIC), and electron donor-acceptor (EDA) material is by weight
Amount is than being 100:1 proportion.
Wherein, the weight ratio of the electron donor-acceptor (EDA) material of active layer 4 is 100:1, by using a small amount of electron acceptor in device
Mass ratio in part obtains photomultiplier transit response, and device has the external quantum efficiency greater than 100%, while reducing device
Preparation cost;By regulating and controlling the thickness of active layer, make organic photodetector that there is spectral selection.
Many carriers can be caused to flow through device specifically, the active layer 4 absorbs a photon, thus obtain compared with
Big photoelectric current, working mechanism are:Electronic induction interface band curvature near interface in trap, to reduce hole injection
Potential barrier enhances tunneling injection of the hole from external circuit, obtains biggish photoelectric current.
It should be noted that if 4 blend film thickness of active layer less than 2.0 μm, as shown in Fig. 2, if device outer amount
As soon as sub- efficiency can also generate an external quantum efficiency peak value at short-wave band, there are two outer quantum to imitate in full spectral region for device
Rate peak value, this just affects the spectral selection of device;As shown in figure 3, the external quantum efficiency of device can be blended with active layer 4
The increase of film thickness and lower, if 4 blend film thickness of active layer between 5.0-7.5 μm, although segment thickness range
Interior external quantum efficiency is still greater than 100%, but in view of the error in practical application, has photoelectricity times to guarantee device still
Synergy is answered, so blend film should maintain between 2.0-5.0 μm.
Further, 2.0 μm and 5.0 μm are that organic photodetector described in practical application keeps narrowband detection (i.e. spectrum
Selectivity) and photomultiplier transit respond two critical values.
As shown in figure 4, the organic photodetector preparation process is as follows:
Step 1:Using glass as transparent substrates.
Step 2:Indium tin oxide (ITO) is plated in the transparent substrates, is then soaked in deionized water, anhydrous respectively
In ethyl alcohol, then cleaned with ultrasonic washing instrument;With being dried with nitrogen after cleaning up, then with plasma cleaning instrument handle 1min.
Step 3:Poly- (3,4- the ethene dioxythiophene)-polystyrene sulphur of spin coating on indium tin oxide (ITO) layer in step 2
Acid (PEDOT:PSS) or [bis- (N, the N- DimethylAminopropyl) fluorenes of 9,9- dioctyl fluorenes -9,9-] (PFN), spin coating rate are
5000r/min, spin-coating time 40s, poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS) dosage is 80 μ L;
The 10min of annealing is placed on 150 DEG C of warm table after spin coating;Or in step 2 on indium tin oxide (ITO) layer with 0.2nm/
Molybdenum oxide (the MoO of one layer of 10nm thickness is deposited in the rate of s3)。
Step 4:It regard poly- (3- hexyl thiophene) (P3HT) or quasi polymer (PBDT-TS1) as electron donor material, it will
Fullerene derivate (PCBM, ICBA) or non-fullerene acceptor (ITIC) are used as electron acceptor material;The electron donor material
With the electron acceptor material according to weight ratio 100:1 is dissolved in o-dichlorohenzene (o-DCB), is prepared into mixed solution, will be described
The uniform drop coating of mixed solution (3,4- ethene dioxythiophene)-polystyrolsulfon acid (PEDOT poly- in step 3:PSS) on layer, then
Heating makes o-dichlorohenzene (o-DCB) quickly volatilize, and leaves the blend film of electron donor material and electron acceptor material, wherein
The heating temperature is 80-120 DEG C, and blend film is with a thickness of 2.0-5.0 μm.
Step 5:Sample obtained in step 4 is put into the vacuum chamber for being placed with aluminium wire, the vacuum degree in vacuum chamber is low
In 1 × 10-4Pa;Heating aluminium wire makes its evaporation, and evaporation rate 0.2nm/s is evaporated with a thickness of 100nm, obtained with spectrum choosing
The photomultiplier transit type organic photodetector of selecting property.
Embodiment one
Photomultiplier transit type organic photodetector with spectral selection includes:Transparent substrates 1, transparent electrode 2, transparent electricity
Pole decorative layer 3, active layer 4 and metal electrode 5.
The transparent electrode 2 is transparent ITO electrode;The transparent electrode decorative layer 3 is poly- (3,4- ethylene dioxy thiophene
Pheno)-polystyrolsulfon acid (PEDOT:PSS);The active layer 4 is poly- (3- hexyl thiophene) P3HT and fullerene derivate PCBM
Blend film, wherein the mass ratio of poly- (3- hexyl thiophene) P3HT and fullerene derivate PCBM be 100:1, active layer 4 is thick
Degree is 2.0 μm;The metal electrode 5 is aluminium.
Above-mentioned organic photodetector preparation method includes the following steps:
Step 1:It is 4cm by area2Glass is as transparent substrates.
Step 2:Indium tin oxide (ITO) is plated in the transparent substrates, is then soaked in deionized water, anhydrous respectively
In ethyl alcohol, cleaned with ultrasonic washing instrument;With being dried with nitrogen after cleaning up, by dry substrate surface plasma cleaning instrument
1min is handled, the cleannes of substrate surface and the work function on the surface ITO are improved.
Step 3:What is be disposed in step 2 is coated with spin coating PEDOT in the glass substrate of ITO:PSS, spin coating rate
For 5000r/min, capacity 80 μ L, spin-coating time 40s, it is then placed on 150 DEG C of warm table the 10min that anneals, removes PEDOT:
Moisture content in PSS film.
Step 4:By poly- (3- hexyl thiophene) P3HT and fullerene derivate PCBM according to weight ratio 100:1 is dissolved in adjacent dichloro
In benzene (o-DCB), it is prepared into 40mg/ml mixed solution, takes the uniform drop coating of mixed solution of 50 μ L in PEDOT:PSS/ITO substrate
On, being then transferred to substrate on 80 DEG C of heating platform makes the solvent in film quickly volatilize, and it is thin to be prepared into 2.0 μm of mixing
Film.
Step 5:Sample is put into vacuum chamber, vacuum chamber is vacuumized, vacuum degree is made to reach 4 × 10-5Pa.Heat aluminium
Silk, evaporates aluminium wire, evaporation rate 0.2nm/s, evaporates with a thickness of 100nm, obtains the photomultiplier transit with spectral selection
Type organic photodetector.
As shown in Figure 5 and Figure 6, manufactured 2.0 μm active mixed film organic photodetectors are under -20V bias,
Maximum external quantum efficiency reaches 610% at 645nm, and detectivity is 1.71 × 1014Jones.
The electron donor material of active layer 4 poly- (3- hexyl thiophene) (P3HT) and electron acceptor material fullerene derivate
(PCBM) 100 are pressed:The blend film that 1 weight ratio is mixed with obtains photoelectricity by reducing the mass ratio of electron acceptor in the devices
Multiplication effect, the i.e. organic photodetector have the external quantum efficiency greater than 100%, while reducing the preparation cost of device;
By regulating and controlling the blend film i.e. thickness of active layer, make the organic photodetector that there is spectral selection;Specifically, setting
Active layer blend film makes the organic photodetector full width at half maximum (FWHM) be less than 30nm with a thickness of 2.0 μm, thus has light
Spectral selectivity.
Embodiment two
4 blend film thickness of active layer in embodiment one is respectively set to 2.5 μm and 5.0 μm, as shown in figure 3, two
Organic photodetector external quantum efficiency in the case of kind is all larger than 100%, and full width at half maximum (FWHM) is respectively less than 30nm, and then has
There is spectral selection.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, such as the preparation of active layer can be there are many selection, and electron donor material can
Think any one in poly- (3- hexyl thiophene) (P3HT) and quasi polymer (PBDT-TS1), electron acceptor material can be richness
Any one in ene derivative (PCBM, ICBA) or non-fullerene acceptor (ITIC) is strangled, it here can not be to all embodiments
It is exhaustive, it is all to belong to obvious changes or variations that technical solution of the present invention is extended out still in of the invention
The column of protection scope.
Claims (10)
1. the photomultiplier transit type organic photodetector with spectral selection, including:
Transparent substrates (1);
The transparent electrode (2) being arranged on the transparent substrates (1);
The transparent electrode decorative layer (3) being arranged on the transparent electrode (2);
The active layer (4) being arranged on the transparent electrode decorative layer (3);And
The metal electrode (5) being arranged on the active layer (4);
It is characterized in that, the active layer is the blend film of electron donor material and electron acceptor material, the film thickness
It is 2.0-5.0 μm;The weight ratio of electron donor and electron acceptor material is 100 in the active layer:1;Wherein, the electronics is given
Body material is poly- (3- hexyl thiophene) (P3HT) or quasi polymer PBDT-TS1, and the electron acceptor material is derivative for fullerene
Object PCBM or ICBA or non-fullerene acceptor ITIC.
2. organic photodetector according to claim 1, which is characterized in that the transparent substrates are glass.
3. organic photodetector according to claim 1, which is characterized in that the transparent electrode is indium tin oxide
(ITO)。
4. organic photodetector according to claim 1, which is characterized in that the transparent electrode decorative layer is by poly- (3,4-
Ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), molybdenum oxide (MoO3) or [9,9- dioctyl fluorene -9,9- bis- (N, N-
DimethylAminopropyl) fluorenes] (PFN) composition.
5. organic photodetector according to claim 1, which is characterized in that the metal electrode be aluminium or silver, with a thickness of
100nm。
6. organic photodetector according to claim 1, which is characterized in that the blend film of the active layer with a thickness of
2.0μm。
7. the preparation method of the photomultiplier transit type organic photodetector with spectral selection, which is characterized in that the method packet
Include following steps:
Step 1:Using glass as transparent substrates;
Step 2:Transparent electrode is prepared in the transparent substrates;
Step 3:Transparent electrode decorative layer is prepared in the transparent electrode;
Step 4:Active layer is prepared on the transparent electrode decorative layer, including:By poly- (3- hexyl thiophene) (P3HT) or class
Polymer P BDT-TS1 as electron donor material, using fullerene derivate PCBM or ICBA or non-fullerene acceptor ITIC as
Electron acceptor material;The electron donor material and the electron acceptor material are according to weight ratio 100:1 is dissolved in o-dichlorohenzene (o-
DCB in), it is prepared into mixed solution, by the uniform drop coating of the mixed solution on the transparent electrode decorative layer of preparation, reheating makes
O-dichlorohenzene (o-DCB) quickly volatilizees, and leaves thin with a thickness of 2.0-5.0 μm of electron donor material and being blended for electron acceptor material
Film is as active layer, wherein the heating temperature is 80-120 DEG C;
Step 5:Metal electrode is prepared on the active layer.
8. the method according to the description of claim 7 is characterized in that step 2 further comprises:Indium tin oxide (ITO) is plated
In the transparent substrates, it is then soaked in deionized water respectively, in dehydrated alcohol, then cleaned with ultrasonic washing instrument;Cleaning
With being dried with nitrogen after clean, then with plasma cleaning instrument processing 1min.
9. the method according to the description of claim 7 is characterized in that step 3 further comprises:What is prepared in step 2 is transparent
Poly- (the 3,4- ethene dioxythiophene)-polystyrolsulfon acid (PEDOT of spin coating on electrode:PSS) or [9,9- dioctyl fluorene -9,9- is double
(N, N- DimethylAminopropyl) fluorenes] (PFN), wherein spin coating rate is 5000r/min, spin-coating time 40s, poly- (3,4- ethylene two
Oxygen thiophene)-polystyrolsulfon acid (PEDOT:PSS) dosage is 80 μ L;It is placed on 150 DEG C of warm table and anneals after spin coating
10min;Or molybdenum oxide (the MoO of one layer of 10nm thickness is deposited in the transparent electrode prepared in step 2 with the rate of 0.2nm/s3)。
10. the method according to the description of claim 7 is characterized in that step 5 further comprises:By sample obtained in step 4
It is put into the vacuum chamber for being placed with aluminium wire, the vacuum degree in vacuum chamber is lower than 1 × 10-4Pa;Heating aluminium wire makes its evaporation, evaporation speed
Rate is 0.2nm/s, is evaporated with a thickness of 100nm.
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CN109802037A (en) * | 2018-12-27 | 2019-05-24 | 北京交通大学 | A kind of photodetector and preparation method thereof |
CN110364626B (en) * | 2019-06-28 | 2020-12-01 | 北京交通大学 | Narrow-band photoelectric detector and preparation method thereof |
CN111682110B (en) * | 2020-05-13 | 2022-04-22 | 华南理工大学 | Near infrared spectrum response polymer light detection device containing non-fullerene receptor |
CN112366276B (en) * | 2020-10-20 | 2022-12-06 | 泰山学院 | Ultrahigh multiplication type organic photoelectric detector and preparation method thereof |
CN112201753B (en) * | 2020-12-01 | 2021-03-23 | 江汉大学 | Organic electric storage device and preparation method thereof |
TW202315186A (en) * | 2021-09-15 | 2023-04-01 | 天光材料科技股份有限公司 | Structure of the photodiode |
CN114284435B (en) * | 2021-12-14 | 2023-05-12 | 电子科技大学 | Low dark current organic multiplication type photoelectric detector and preparation method thereof |
CN116528638A (en) * | 2023-03-29 | 2023-08-01 | 北京大学深圳研究生院 | Preparation method of active layer, narrow-band near-infrared photodiode and preparation method thereof |
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