CN109802037A - A kind of photodetector and preparation method thereof - Google Patents
A kind of photodetector and preparation method thereof Download PDFInfo
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Abstract
The application belongs to optical detector technology field, more particularly to a kind of photodetector and preparation method thereof.Existing photodetector mostly can only operate under single-mode, i.e., only has single spectral response mode, limit the use scope of photodetector.In addition, traditional photodetector can only operate under unidirectional bias, applying forward bias to it can make device breakdown damage.The application provides a kind of photodetector, substrate, electrode, electrode modification layer, active layer and semi-transparent metals electrode including stacking gradually arrangement；The active layer is mixed film, and the film includes electron donor material and electron acceptor material.So that integrated bi-directional bias/four kinds of bis- incident windows operating mode in individual devices, and different working modes have different spectral response ranges, four kinds of operating modes are integrated in individual devices with simple, inexpensive preparation method, realize narrowband and broadband optical detection.
Description
Technical field
The application belongs to optical detector technology field, more particularly to a kind of photodetector and preparation method thereof.
Background technique
Photodetector is a kind of device for converting optical signals to electric signal, it is seen that optical range photodetector at
The fields such as picture, spectral detection, accurate scientific research apparatus, biological monitoring, fluorescent marker, medical image etc. be civilian are widely used.Mesh
Before, the photodetector to have put it into commercial operation is all made of inorganic semiconductor material (such as silicon), these materials are all from rock
Middle exploitation is refined to obtain, this process causes greatly destruction, pollution to environment.Nature largely existing carbon (C), hydrogen
(H), oxygen (O) provides sufficient raw material to synthesize green novel organic semi-conductor material.Since organic semiconducting materials also have
Have the advantages that extinction coefficient it is high, it is at low cost, can be made into large area flexible device so that the research of organic photodetector is by pass
Note.
The working principle of existing organic photodetector is based primarily upon organic photovoltaic effect, i.e. organic semiconducting materials are captureed
It obtains photon and generates exciton, to acceptor interface, exciton is dissociated into exciton diffusion under the driving force effect to acceptor level difference
Free carrier, carrier are collected by electrode, and then generate photogenerated current, realize detection and response to optical signal.Respond model
Enclose be organic photodetector a key parameter.According to the spectral response range of detector, it can be classified as two major classes: one
It is to be capable of the photodetector of a certain wavelength channels of accurately detecting with narrow band light detectivity；Second is that having broadband light to visit
Survey ability from the broadband of ultraviolet, visible near-infrared, it can be achieved that detect.Due to by material extinction coefficient, exciton fission efficiency,
The external quantum efficiency of the influence of carrier transport and collection efficiency, this kind of photodetector is both less than 100%, for dim light or surpasses
The responsiveness of weak light detection, device is just restricted.
Existing photodetector mostly can only operate under single-mode, i.e., only has single spectral response mode, light
It is non-adjustable to compose response range, limits the use scope of photodetector.In addition, traditional photodetector can only operate in list
To under bias, applying forward bias to it can make device breakdown damage.
Summary of the invention
1. technical problems to be solved
It mostly can only operate under single-mode based on existing photodetector, i.e., only there is single spectral response mould
Formula, spectral response range is non-adjustable, limits the use scope of photodetector.In addition, traditional photodetector can only work
Make under unidirectional bias, applies the problem of forward bias can make device breakdown damage to it, this application provides a kind of photoelectricity
Detector and preparation method thereof.
2. technical solution
To achieve the above object, this application provides a kind of photodetector, including stack gradually arrangement substrate,
Electrode, electrode modification layer, active layer and semi-transparent metals electrode；
The active layer is mixed film, and the film includes electron donor material and electron acceptor material.
Optionally, the film thickness is 0.2~5.0 micron, the electron donor material and the electron acceptor material
Weight ratio be 5:1~200:1, the electron donor material be poly- 3- hexyl thiophene (P3HT) or quasi polymer (PBDT-
TS1), the electron acceptor material be fullerene derivate (PCBM, ICBA) or non-fullerene acceptor (DC-IDT2T,
ITIC)。
Optionally, the substrate is glass, and the electrode is tin indium oxide, and the electrode modification layer is [N, N '-bis- (third
Alkene dimethylamine) -3,4:9,10- imidodicarbonic diamide] (PDIN) or [9,9- dioctyl fluorene -9,9- bis- (N, N- DimethylAminopropyls)
Fluorenes] (PFN), the semi-transparent metals electrode is aluminium, silver or gold.
Optionally, for the electrode modification layer with a thickness of 20~40 nanometers, the semi-transparent metals thickness of electrode is 10~30
Nanometer.
The application also provides a kind of photodetector preparation method, and described method includes following steps:
Step 1: electrode is set in substrate；
Step 2: electrode modification layer is set on the electrodes；
Step 3: active layer is set on the electrode modification layer；
Step 4: semi-transparent metals electrode is set on the active layer.
Optionally, the step 3 includes by electron donor material and electron acceptor material according to weight ratio 5:1~200:1
It is dissolved in adjacent chlorodiphenyl, is prepared into mixed solution, by the uniform spin coating of the mixed solution or drop coating on the electrode modification layer,
Reheating makes adjacent chlorodiphenyl volatilize rapidly, prepares 0.2~5.0 micron of active layer 4.
Optionally, the heating temperature is 70~120 DEG C.
Optionally, the step 1 include by tin indium oxide plating on the substrate, be then soaked in respectively deionized water,
In dehydrated alcohol, then cleaned with ultrasonic washing instrument；With being dried with nitrogen after cleaning up, then handled with plasma cleaning instrument
1min。
Optionally, the step 2 includes [N, N '-bis- (propylene dimethylamine) -3,4:9, the 10- of spin coating on the electrodes
Imidodicarbonic diamide] (PDIN) or [bis- (N, the N- DimethylAminopropyl) fluorenes of 9,9- dioctyl fluorene -9,9-] (PFN).
Optionally, the step 4 includes being put into sample obtained in the step 3 to be equipped with aluminium ingot, silver ingot or ingot
Vacuum chamber in, heating aluminium ingot, silver ingot or ingot make its evaporation.
3. beneficial effect
Compared with prior art, a kind of beneficial effect of photodetector provided by the present application and preparation method thereof is:
Photodetector provided by the present application, by the substrate, the electrode, electrode modification layer, active layer that stack gradually arrangement
With semi-transparent metals electrode；Wherein active layer is mixed film made of electron donor material and electron acceptor material, so that
Integrated bi-directional bias/four kinds of bis- incident windows operating mode in individual devices, and different working modes have different spectral responses
Range has widened the application range of photodetector.Four kinds of works are integrated in individual devices with simple, inexpensive preparation method
Operation mode, realizes narrowband and broadband optical detection, and the full width at half maximum of the narrowband response is less than 50 nanometers, the broadband response
Full width at half maximum is greater than 260 nanometers, and has photomultiplier transit response, i.e. external quantum efficiency is greater than 100%.
Detailed description of the invention
Fig. 1 is a kind of photodetector structure schematic diagram of the application；
Fig. 2 is the photodetector of the application under Biaxial bending/bis- incident windows light current curve and Biaxial bending
Dark current curve；
Fig. 3 is the photodetector of 0.3 micron of active layer of the application in Biaxial bending/four kinds of bis- incident windows Working mould
External quantum efficiency spectra curve under formula；
Fig. 4 is the photodetector of the different-thickness active layer of the application in Biaxial bending/four kinds of bis- incident windows work
External quantum efficiency spectra curve under mode；
Fig. 5 is the photodetector of 3.6 microns of active layers of the application in Biaxial bending/four kinds of bis- incident windows Working mould
External quantum efficiency spectra curve under formula；
In figure: 1- substrate, 2- electrode, 3- electrode modification layer, 4- active layer, 5- semi-transparent metals electrode.
Specific embodiment
Hereinafter, specific embodiment of the reference attached drawing to the application is described in detail, it is detailed according to these
Description, one of ordinary skill in the art can implement the application it can be clearly understood that the application.Without prejudice to the application principle
In the case where, the feature in each different embodiment can be combined to obtain new embodiment, or be substituted certain
Certain features in embodiment, obtain other preferred embodiments.
Detector in practical applications based on organic photovoltaic effect must amplify system using complicated, expensive current operator
System extract useful information from noise.Photomultiplier transit response is introduced into organic photodetector then can be greatly
The responsiveness and signal-to-noise ratio of device are improved, realizes the sensitive detection to dim light.
Referring to Fig. 1~5, the application provides a kind of photodetector, it is characterised in that: the substrate including stacking gradually arrangement
1, electrode 2, electrode modification layer 3, active layer 4 and semi-transparent metals electrode 5；
The active layer 4 is mixed film, and the film includes electron donor material and electron acceptor material.
Here substrate 1 is transparent substrates, and electrode 2 is transparent electrode, which is arranged in the transparent substrates,
It is provided with electrode modification layer 3 in the transparent electrode, active layer 4 is set on the electrode modification layer 3, is arranged on the active layer 4
Semi-transparent metals electrode 5.
Further, the active layer 4 is with a thickness of 0.2~5.0 micron, the electron donor material and the electron acceptor
The weight ratio of material is 5:1~200:1, and 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 (DC-
IDT2T,ITIC).The active layer 4, which absorbs a photon, can cause many carriers to flow through device, to obtain biggish
Photoelectric current, working mechanism are as follows: a small amount of electron acceptor forms discontinuous trap and trapped electron in active layer, near interface
Trapped electron forms coulomb electric field and induces interface band curvature, and then enhances tunneling injection of the hole from external circuit, from
And photomultiplier transit response is obtained, thus device has the external quantum efficiency greater than 100%.
Further, the substrate 1 is glass, and the electrode 2 is tin indium oxide (ITO), and the electrode modification layer 3 is
[N, N '-bis- (propylene dimethylamine) -3,4:9,10- imidodicarbonic diamide] (PDIN) or [bis- (N, N- bis- of 9,9- dioctyl fluorene -9,9-
Methyl amine propyl) fluorenes] (PFN), the semi-transparent metals electrode 5 is aluminium, silver or gold；It can be made using semi-transparent metals electrode 5
The photodetector has double incident windows.
Further, the electrode modification layer 3 is with a thickness of 20~40 nanometers, and the semi-transparent metals electrode 5 is with a thickness of 10
~30 nanometers.
Semi-transparent metals electrode 5 is preferably aluminium (Al), and thickness is preferably 16 nanometers；4 thickness of active layer is preferably 0.3 micron
With 3.6 microns.
Photodetector preparation method, described method includes following steps:
Step 1: electrode 2 is set on the base 1；
Step 2: electrode modification layer 3 is set on the electrode 2；
Step 3: active layer 4 is set on the electrode modification layer 3；
Step 4: semi-transparent metals electrode 5 is set on the active layer 4.
Further, the step 3 includes by electron donor material and electron acceptor material according to weight ratio 5:1~200:
1 is dissolved in adjacent chlorodiphenyl, is prepared into mixed solution, by the uniform spin coating of the mixed solution or drop coating in the electrode modification layer 3
On, reheating makes adjacent chlorodiphenyl volatilize rapidly, prepares 0.2~5.0 micron of active layer 4.Here preferred 100:1.
Further, the heating temperature is 70~120 DEG C.
Further, the step 1 includes being plated in tin indium oxide in the substrate 1, is then soaked in deionization respectively
In water, dehydrated alcohol, then cleaned with ultrasonic washing instrument；With being dried with nitrogen after cleaning up, then handled with plasma cleaning instrument
1min。
Further, the step 2 includes spin coating [N, N '-bis- (propylene dimethylamine) -3,4:9, the 10- on the electrode 2
Imidodicarbonic diamide] or [bis- (N, the N- DimethylAminopropyl) fluorenes of 9,9- dioctyl fluorene -9,9-].Wherein spin coating rate be 2000 turns/
Point, spin-coating time 35s, [N, N '-bis- (propylene dimethylamine) -3,4:9,10- imidodicarbonic diamide] (PDIN) or [9,9- dioctyls
Bis- (N, the N- DimethylAminopropyl) fluorenes of fluorenes -9,9-] (PFN) dosage be 60 microlitres.
Further, the step 4 includes being put into sample obtained in the step 3 to be equipped with aluminium ingot, silver ingot or gold
In the vacuum chamber of ingot, heating aluminium ingot, silver ingot or ingot make its evaporation.The pressure of vacuum chamber is lower than 1 × 10-4Pa；Evaporation rate is about
For 0.2 nm/sec, evaporation thickness is 10~30 nanometers.
Embodiment 1
A kind of photodetector, comprising: substrate 1, electrode 2, electrode modification layer 3, active layer 4 and semi-transparent metals electrode
5, as shown in Figure 1.
The substrate 1 is glass；The electrode 2 is ITO；The electrode modification layer 3 is PDIN or PFN；The active layer 4
The P3HT and PCBM mixed film for being 100:1 for mass ratio, with a thickness of 0.3 micron；The semi-transparent metals electrode 5 is aluminium (Al)
Electrode, with a thickness of 16 nanometers.
Above-mentioned organic photodetector preparation method the following steps are included:
Step 1: preparing transparent electrode ITO in substrate of glass, be then soaked in deionized water respectively, in dehydrated alcohol, use
Ultrasonic washing instrument cleaning；With being dried with nitrogen after cleaning up, dry substrate plasma cleaning instrument is handled into 1min, is improved
The cleannes of substrate surface and the work function on the surface ITO.
Step 2: what is be disposed in step 1 is coated with spin coating PDIN or PFN in the glass substrate of ITO, and spin coating rate is
2000 revs/min, spin-coating time 35 seconds, PDIN or PFN dosage was 60 microlitres.
Step 3: P3HT and PCBM being dissolved in o-DCB according to weight ratio 100:1, is prepared into the mixing of 40 mg/mls
Solution takes 40 microlitres of mixed solution to be uniformly spin-coated on electrode modification layer PDIN or PFN, substrate is then transferred to 100 and is taken the photograph
So that the solvent in film is quickly volatilized on the heating platform of family name's degree, is prepared into 0.3 micron of thick mixed film.
Step 4: the sample in step 3 being put into vacuum chamber, vacuum chamber is vacuumized, pressure in vacuum chamber is made to be lower than 1
×10-4Pa.Aluminium ingot is heated, aluminium ingot is evaporated, evaporation rate is 0.2 nm/sec, is evaporated with a thickness of 16 nanometers, obtains having four
The multiplication type organic photodetector of kind operating mode.
According to the method for embodiment 1, it is semi-transparent for active layer, 16 nanometer thickness to be based on 0.3 micron of thickness P3HT:PCBM (100:1)
Dark current of the organic photodetector of bright aluminium electrode under Biaxial bending/bis- incident windows light current curve and Biaxial bending
Curve, as shown in Fig. 2, under 10 volts and -10 volt biass, dark current density is respectively 0.000379 milliamps per square centimeter,
0.000286 milliamps per square centimeter；Under 10 volts of biass, the light current density in the case of bottom incidence (side ITO) is 3.59 millis
Peace/square centimeter, the light current density headed into the case of penetrating (side Al) are 0.055 milliamps per square centimeter；In -10 volt biass
Under, the light current density in the case of incident (side ITO) is 0.39 milliamps per square centimeter, heads into and penetrates in the case of (side Al)
Light current density is 0.089 milliamps per square centimeter.
According to the method for embodiment 1, it is semi-transparent for active layer 4,16 nanometer thickness to be based on 0.3 micron of thickness P3HT:PCBM (100:1)
External quantum efficiency spectra of the organic photodetector of bright aluminium electrode under Biaxial bending/four kinds of bis- incident windows operating mode is bent
Line；A, bottom incidence/forward bias；B, bottom incidence/reverse biased；C, it heads into and penetrates/forward bias；D, it heads into and penetrates/reverse biased, institute
Stating bias size is 10 volts, as described in Figure 3, under the conditions of mode 1, i.e., under bottom incidence/forward bias, in 300~700 nanometers of models
Interior appearance band response is enclosed, the full width at half maximum of response is greater than 300 nanometers；Under the conditions of mode 2, i.e., under bottom incidence/reverse biased,
320~490 nanometers and 550~700 nanometers appearance peak, and a recess is formed between Liang Feng；Under the conditions of mode 3, i.e.,
Head into penetrate/forward bias under, the shape of response spectrum is similar with mode 2, and external quantum efficiency is lower than mode 2, but is still greater than
100%；Under the conditions of mode 4, that is, head into penetrate/reverse biased under, the shape of response spectrum is similar with mode 1, external quantum efficiency
It is lower than mode 2, but it is still greater than 100%.
Embodiment 2
4 thickness of active layer in embodiment 1 is respectively set to 1.8 microns, 2.4 microns, 3.0 microns and 3.6 microns,
External quantum efficiency spectra of the photodetector under Biaxial bending/four kinds of bis- incident windows operating mode with active layer thickness pass
System, the bias size is 20 volts, as shown in figure 4, in mode 1, i.e. bottom incidence/forward bias and mode 4, that is, head into penetrate/it is anti-
To under bias condition, external quantum efficiency reduces with the increase of active layer thickness, and the organic photoelectric detection in the case of two kinds
All there are two narrowband responses of U-typed in device；In mode 2, i.e. bottom incidence/reverse biased and mode 3, that is, heads into and penetrate/forward bias
Under the conditions of pressure, external quantum efficiency reduces with the increase of active layer thickness, and the response of organic photodetector is by double narrowbands
Response becomes single narrowband response.
3.6 microns are set by 4 thickness of active layer in embodiment 1, as shown in figure 5, having with the increase of institute's biasing
The external quantum efficiency of machine photodetector dramatically increases；Under 50 volts, mode 1 is in 310~400 nanometers and 600~700 nanometers
Occurs the narrowband response that full width at half maximum is 31 nanometers and 33 nanometers respectively, mode 4 is in 300~400 nanometers and 600~700 nanometers
There is the narrowband response that full width at half maximum is 37 nanometers and 45 nanometers respectively in place, and mode 2 half Gao Quan occurs in 610~700 nanometers
There is the narrowband response that full width at half maximum is 36 nanometers in 610~700 nanometers in the narrowband response that width is 30 nanometers, mode 3.
Photodetector provided by the present application, by the substrate, the electrode, electrode modification layer, active layer that stack gradually arrangement
With semi-transparent metals electrode；Wherein active layer is mixed film made of electron donor material and electron acceptor material, so that
Integrated bi-directional bias/four kinds of bis- incident windows operating mode in individual devices realizes narrowband and broadband optical detection, with simple, low
The preparation method of cost integrates four kinds of operating modes in individual devices, realizes narrowband and broadband optical detection.And the narrowband is rung
For the full width at half maximum answered less than 50 nanometers, the full width at half maximum of the broadband response is greater than 260 nanometers, and there is photomultiplier transit to ring
It answers, i.e., external quantum efficiency is greater than 100%.
Although the application is described above by referring to specific embodiment, one of ordinary skill in the art are answered
Work as understanding, in principle disclosed in the present application and range, many modifications can be made for configuration disclosed in the present application and details.
The protection scope of the application is determined by the attached claims, and claim is intended to technical characteristic in claim
Equivalent literal meaning or range whole modifications for being included.
Claims (10)
1. a kind of photodetector, it is characterised in that: substrate, electrode, electrode modification layer, active layer including stacking gradually arrangement
With semi-transparent metals electrode；
The active layer is mixed film, and the film includes electron donor material and electron acceptor material.
2. photodetector as described in claim 1, it is characterised in that: the active layer is with a thickness of 0.2~5.0 micron, institute
The weight ratio for stating electron donor material and the electron acceptor material is 5:1~200:1, the electron donor material be poly- 3- oneself
Perhaps the quasi polymer electron acceptor material is fullerene derivate or non-fullerene acceptor to base thiophene.
3. photodetector as described in claim 1, it is characterised in that: the substrate is glass, and the electrode is indium oxide
Tin, the electrode modification layer are [N, N '-bis- (propylene dimethylamine) -3,4:9,10- imidodicarbonic diamide] or [9,9- dioctyl fluorenes -
9,9- bis- (N, N- DimethylAminopropyl) fluorenes], the semi-transparent metals electrode is aluminium, silver or gold.
4. photodetector according to any one of claims 1 to 3, it is characterised in that: the electrode modification layer with a thickness of
20~40 nanometers, the semi-transparent metals thickness of electrode is 10~30 nanometers.
5. a kind of photodetector preparation method, it is characterised in that: described method includes following steps:
Step 1: electrode is set in substrate；
Step 2: electrode modification layer is set on the electrodes；
Step 3: active layer is set on the electrode modification layer；
Step 4: semi-transparent metals electrode is set on the active layer.
6. photodetector preparation method as claimed in claim 5, it is characterised in that: the step 3 includes by electron donor
Material and electron acceptor material are dissolved in adjacent chlorodiphenyl according to weight ratio 5:1~200:1, are prepared into mixed solution, will be described mixed
The uniform spin coating of solution or drop coating are closed on the electrode modification layer, reheating makes adjacent chlorodiphenyl volatilize rapidly, prepare 0.2~
5.0 microns of active layer.
7. photodetector preparation method as claimed in claim 6, it is characterised in that: the heating temperature is 70~120 DEG C.
8. photodetector preparation method as claimed in claim 5, it is characterised in that: the step 1 includes by tin indium oxide
Plating on the substrate, is then soaked in deionized water, in dehydrated alcohol, then cleaned with ultrasonic washing instrument respectively；Cleaning is dry
With being dried with nitrogen after net, then with plasma cleaning instrument processing 1min.
9. photodetector preparation method as claimed in claim 5, it is characterised in that: the step 2 is included in the electrode
Upper spin coating [N, N '-bis- (propylene dimethylamine) -3,4:9,10- imidodicarbonic diamide] or [bis- (N, the N- bis- of 9,9- dioctyl fluorene -9,9-
Methyl amine propyl) fluorenes].
10. photodetector preparation method as claimed in claim 5, it is characterised in that: the step 4 includes by the step
Sample obtained in 3 is put into the vacuum chamber for being equipped with aluminium ingot, silver ingot or ingot, and heating aluminium ingot, silver ingot or ingot make its evaporation.
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| CN112271259A (en) * | 2020-10-29 | 2021-01-26 | 电子科技大学 | Flexible 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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Application publication date: 20190524 |