CN110473971A - One kind is based on organic wide spectrum photodetector of ternary and preparation method thereof - Google Patents
One kind is based on organic wide spectrum photodetector of ternary and preparation method thereof Download PDFInfo
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Abstract
The invention discloses one kind to be based on the organic wide spectrum photodetector of ternary, and including the substrate set gradually from top to bottom, conductive cathode, electron transfer layer, photoactive layer, hole transmission layer and metal anode, the photoactive layer is by P3HT:IEICO-4F:PC71It is made after BM:HA mixing through spin coating proceeding, the P3HT:IEICO-4F:PC71The mass ratio of BM:HA is 1:0.9:0.1:(0.03~0.2), the invention discloses the preparation method of the photodetector, the present invention can reduce PC by adulterating HA solution71Aggregation of the BM in active layer hybrid films, make the film to be formed more evenly, while the contact of Donor acceptor can be increased, increases photoelectric current, electrons and holes can be made more effectively to transmit, the recombination fraction of carrier is reduced to reduce dark current, meanwhile, optimize the contact between transport layer and active layer, the molecular chain structure in active layer molecule can also be made more orderly, it mutually separates more effectively, reduces dark current, the final overall performance for promoting device.
Description
Technical field
The present invention relates to organic semiconductor thin-film photodetector technical fields, more particularly to a kind of ternary that is based on machine width
Spectrum photodetector and preparation method thereof.
Background technique
Organic photodetector is using with the sensor that can be realized photoelectric conversion made of photoelectric material.
Traditional optical detector is made of inorganic semiconductor material, and complex manufacturing technology is at high cost, and is unsuitable for making large area device
Part.It is light since organic material has efficient photaesthesia, it inexpensive, the features such as processing performance is excellent, is easier to prepare small size,
Low-power consumption, inexpensive sensitive detection parts can make up for it equipment valuableness generally existing in inorganic optical detector, complex process etc.
Defect.Miscellaneous organic semiconducting materials also provide very big may be selected for the development and innovation of organic photodetector part
Property, synthesize the new material with corresponding photoelectric characteristic as needed.Therefore organic photodetector will be empty with bigger research
Between and commercial value, such as in astronomy, environmental monitoring, light splitting and medicine detector device etc..
Existing organic photodetector spin coating active layer in transoid device, then solvent anneal are blended to form active layer
Film.Active layer is made of electron donor material and electron acceptor material, selects fullerene (PC in electron acceptor material71BM)
When, since the agglomeration of fullerene makes the interface of active layer more coarse, become the contact area between donor and receptor
It is small, it to prevent the exciton generated from efficiently separating, but also can make to have the defects that in active layer more, carrier is passing
It is easy to be captured in defeated process, increases the compound probability of carrier, seriously constrain the performance of device.Therefore, it studies such as
What optimization photoactive layer is one of emphasis and difficult point of current organic photodetector area research.
Summary of the invention
It is an object of the invention to: it provides a kind of based on organic wide spectrum photodetector of ternary and preparation method thereof, energy
Receptor PC in enough photolytic activities71BM reduce reunite, make annealing after formed film it is more fine and close smooth, optimization photoactive layer with
The contact of electron transfer layer, hole transmission layer promotes device performance and stability.
The technical solution adopted by the invention is as follows:
To achieve the above object, the present invention provides a kind of based on the organic wide spectrum photodetector of ternary, including photolytic activity
Layer, the photoactive layer are made after electron acceptor material and the mixing of humic acid material through spin coating proceeding, institute of electron donor material
State electron donor material, the mass ratio of electron acceptor material and humic acid material (HA) is 1:1:(0.03~0.2).
Preferably, the electron donor material is P3HT, and electron acceptor material is by IEICO-4F and PC71The mixed solution of BM
It is made, the electron donor material, the blend solution concentration of electron acceptor material and humic acid material is 30mg/mL.
Preferably, IEICO-4F and PC in the electron acceptor material71The mass ratio of BM is 9:1.
Preferably, the photoactive layer with a thickness of 50~300nm.
Preferably, the photodetector includes the substrate set gradually from top to bottom, conductive cathode, electron-transport
Layer, photoactive layer, hole transmission layer and metal anode.
Preferably, the substrate is made using transparent polymer material, and the transparent polymer material uses polyethylene, gathers
Methyl methacrylate, polycarbonate, polyurethanes, polyimides, vinyl chloride-vinyl acetate resin and polyacrylic acid it is one or more；
The material of the conductive cathode is ITO；The electron transport layer materials are ZnO sol gel solution, with a thickness of 30nm；The sky
It is MoO that layer material is transmitted in cave3, with a thickness of 15nm, the metal anode material is one of Ag, Al and Au or a variety of, thickness
For 100nm.
Preferably, the ZnO sol gel solution is made of zinc acetate and ethanol amine, and the weight of the zinc acetate accounts for 60%
~80%, surplus is ethanol amine.
The present invention also provides a kind of preparation methods based on the organic wide spectrum photodetector of ternary, including following preparation to walk
It is rapid:
(1) substrate being made of substrate and conductive cathode is cleaned, with being dried with nitrogen after cleaning；
(2) configured ZnO mixed solution is spin-coated to conductive cathode surface, and the substrate after spin coating is subjected to thermal annealing
Processing, obtains electron transfer layer；
(3) spin coating is total to by what electron donor material, electron acceptor material and humic acid material formed on the electron transport layer
Photoactive layer is made in miscible fluid；
It (4) is 3 × 10 in vacuum degree3Under the conditions of Pa, MoO is deposited on photoactive layer surface3, hole transmission layer is prepared；
(5) evaporation metal anode on the hole transport layer, is packaged to obtain photodetector later.
Preferably, the temperature of thermal annealing is 150 DEG C in the step (2), time 15min.
Preferably, the thermal annealing mode is using in Thermostatic platform heating, baking oven heating, Far-infrared Heating and Hot-blast Heating
It is one or more.
In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are:
1.HA is a kind of larger molecular organics matter, it have non-conductive, light specific gravity, it is pollution-free, be dissolved in usual vehicle, be easy to
The more excellent properties such as Compound Machining molding, the present invention in photoactive layer by adulterating HA, so that the PCBM in photoactive layer
Solution can reduce reunion under the influence of HA, can more evenly, entirely adhere on the electron transport layer, reduce due to
PC71Film inhomogeneities brought by BM reunion, and then keep the film formed after annealing more fine and close smooth, optimization active layer
Contact between electron transfer layer reduces the contact resistance between interface, improves short circuit current, improves device performance.
2. the present invention can allow active layer inner molecular structure more orderly, solve by adulterating HA in photoactive layer
Since acceptor material aggregation contacts untight problem, so that solution more rapidly, is more uniformly distributed, donor and receptor material can be allowed
Material forms effective mutually separation, promotes exciton fission, improves injection barrier, reduces dark current, is conducive to raising device performance.
3. the present invention so that the distribution between donor and receptor is more uniform, then is passed through by adulterating HA in photoactive layer
After making annealing treatment, the active layer film of formation is more smooth, to reduce the defect of active layer, reduces the compound of carrier
Probability, while increasing the dissociation of exciton, photoelectric current is improved, and the stability of device can be improved.
Detailed description of the invention
Examples of the present invention will be described by way of reference to the accompanying drawings, in which:
Fig. 1 is the structural schematic diagram of photodetector of the present invention；
Fig. 2 is HA chemical structural formula according to the present invention.
In the figure, it is marked as 1- substrate, 2- conductive cathode, 3- electron transfer layer, 4- photoactive layer, 5- hole transmission layer, 6-
Metal anode.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Reference examples
The substrate as composed by transparent substrates and transparent conductive cathode ITO to surface roughness less than 1nm cleans,
With being dried with nitrogen after cleaning；In transparent conductive cathode ITO surface spin coating ZnO precursor solution, and carry out thermal anneal process (150
DEG C, 15min) electron transfer layer is prepared, spin coating P3HT:IEICO-4F:PC on the electron transport layer71BM (1:0.9:0.1,30mg/
ML hole transmission layer MoO is deposited on photoactive layer surface in) photoactive layer (800rpm, 30s)3(15nm)；On the hole transport layer
Evaporation metal anode A g (100nm).
Under standard test condition: AM 1.5,100mW/cm2, measure the dark current (Jd)=1.3 × 10 of device-6A/
cm2, photoelectric current (Jph)=2.7 × 10-3A/cm2, specific detecivity (D*)=2.47 × 1011Jones。
Embodiment 1
The substrate as composed by transparent substrates and transparent conductive cathode ITO to surface roughness less than 1nm cleans,
With being dried with nitrogen after cleaning；ZnO precursor solution is prepared in transparent conductive cathode ITO surface spin coating, then thermal anneal process
(150 DEG C, 15min) prepare electron transfer layer, prepare P3HT:IEICO-4F:PC on the electron transport layer71BM:HA (1:0.9:
0.1:0.03,30mg/ml) photoactive layer (800rpm, 30s), hole transmission layer MoO is deposited on photoactive layer surface3(15nm)；
Evaporation metal anode A g (100nm) on the hole transport layer.
Under standard test condition: AM 1.5,100mW/cm2, measure the dark current (Jd)=1.6 × 10 of device-6A/
cm2, photoelectric current (Jph)=3.3 × 10-3A/cm2, specific detecivity (D*)=4.2 × 1011Jones。
Embodiment 2
The substrate as composed by transparent substrates and transparent conductive cathode ITO to surface roughness less than 1nm cleans,
With being dried with nitrogen after cleaning；ZnO precursor solution is prepared in transparent conductive cathode ITO surface spin coating, and carries out thermal anneal process
(150 DEG C, 15min) prepare electron transfer layer, prepare P3HT:IEICO-4F:PC in electron transfer layer71BM:HA (1:0.9:0.1:
0.05,30mg/ml) hole transmission layer MoO is deposited on photoactive layer surface in photoactive layer (800rpm, 30s)3(15n m)；In
Evaporation metal anode A g (100nm) on hole transmission layer.
Under standard test condition: AM 1.5,100mW/cm2, measure the dark current (Jd)=1.43 × 10 of device-6A/
cm2, photoelectric current (Jph)=1.5 × 10-3A/cm2, specific detecivity (D*)=1.67 × 1011Jones。
Embodiment 3
The substrate as composed by transparent substrates and transparent conductive cathode ITO to surface roughness less than 1nm cleans,
With being dried with nitrogen after cleaning；ZnO precursor solution is prepared in transparent conductive cathode ITO surface spin coating, and carries out thermal anneal process
(150 DEG C, 15min) prepare electron transfer layer, prepare P3HT:IEICO-4F:PC on the electron transport layer71BM:HA (1:0.9:
0.1:0.08,30mg/ml) photoactive layer (800rpm, 30s), hole transmission layer MoO is deposited on photoactive layer surface3(15nm)；
Evaporation metal anode A g (100nm) on the hole transport layer.
Under standard test condition: AM 1.5,100mW/cm2, measure the dark current (Jd)=1.4 × 10 of device-6A/
cm2, photoelectric current (Jph)=6.1 × 10-3A/cm2, specific detecivity (D*)=3.4 × 1011Jones。
Embodiment 4
The substrate as composed by transparent substrates and transparent conductive cathode ITO to surface roughness less than 1nm cleans,
With being dried with nitrogen after cleaning；ZnO precursor solution is prepared in transparent conductive cathode ITO surface spin coating, and carries out thermal anneal process
(150 DEG C, 15min) prepare electron transfer layer, prepare P3HT:IEICO-4F:PC on the electron transport layer71BM:HA (1:0.9:
0.1:0.1,30mg/ml) photoactive layer (800rpm, 30s), hole transmission layer MoO is deposited on photoactive layer surface3(15n m)；
Evaporation metal anode A g (100nm) on the hole transport layer.
Under standard test condition: AM 1.5,100mW/cm2, measure the dark current (Jd)=1 × 10 of device-6A/cm2,
Photoelectric current (Jph)=8.3 × 10-3A/cm2, specific detecivity (D*)=7.86 × 1011Jones。
Embodiment 5
The substrate as composed by transparent substrates and transparent conductive cathode ITO to surface roughness less than 1nm cleans,
With being dried with nitrogen after cleaning；ZnO precursor solution is prepared in transparent conductive cathode ITO surface spin coating, and carries out thermal anneal process
(150 DEG C, 15min) prepare electron transfer layer, prepare P3HT:IEICO-4F:PC on the electron transport layer71BM:HA (1:0.9:
0.1:0.12,30mg/ml) photoactive layer (800rpm, 30s), hole transmission layer MoO is deposited on photoactive layer surface3(15nm)；
Evaporation metal anode A g (100nm) on the hole transport layer.
Under standard test condition: AM 1.5,100mW/cm2, measure the dark current (Jd)=1.32 × 10 of device-6A/
cm2, photoelectric current (Jph)=9.2 × 10-3A/cm2, specific detecivity (D*)=9.54 × 1011Jones。
Embodiment 6
The substrate as composed by transparent substrates and transparent conductive cathode ITO to surface roughness less than 1nm cleans,
With being dried with nitrogen after cleaning；ZnO precursor solution is prepared in transparent conductive cathode ITO surface spin coating, and carries out thermal anneal process
(150 DEG C, 15min) prepare electron transfer layer, prepare P3HT:IEICO-4F:PC on the electron transport layer71BM:HA (1:0.9:
0.1:0.15,30mg/ml) photoactive layer (800rpm, 30s), layer hole transmission layer MoO is deposited on photoactive layer surface3
(15nm)；In hole transmission layer evaporation metal anode A g (100nm).
Under standard test condition: AM 1.5,100mW/cm2, measure the dark current (Jd)=1.26 × 10 of device-7A/
cm2, photoelectric current (Jph)=2.93 × 10-2A/cm2, specific detecivity (D*)=1.0 × 1012Jones。
Embodiment 7
The substrate as composed by transparent substrates and transparent conductive cathode ITO to surface roughness less than 1nm cleans,
With being dried with nitrogen after cleaning；ZnO precursor solution is prepared in transparent conductive cathode ITO surface spin coating, and carries out thermal anneal process
(150 DEG C, 15min) prepare electron transfer layer, prepare P3HT:IEICO-4F:PC on the electron transport layer71BM:HA (1:0.9:
0.1:0.18,30mg/ml) photoactive layer (800rpm, 30s), hole transmission layer MoO is deposited on photoactive layer surface3(15nm)；
Evaporation metal anode A g (100nm) on the hole transport layer.
Under standard test condition: AM 1.5,100mW/cm2, measure the dark current (Jd)=7.4 × 10 of device-5A/cm,
Photoelectric current (Jph)=2.14 × 10-3A/cm2, specific detecivity (D*)=3.35 × 1011Jones。
Embodiment 8
The substrate as composed by transparent substrates and transparent conductive cathode ITO to surface roughness less than 1nm cleans,
With being dried with nitrogen after cleaning；ZnO precursor solution is prepared in transparent conductive cathode ITO surface spin coating, and carries out thermal anneal process
(150 DEG C, 15min) prepare electron transfer layer, prepare P3HT:IEICO-4F:PC using spin coating on the electron transport layer71BM:HA
Hole transmission layer MoO is deposited on photoactive layer surface in (1:0.9:0.1:0.2,30mg/ml) photoactive layer (800rpm, 30s)3
(15nm)；Evaporation metal anode A g (100nm) on the hole transport layer.
Under standard test condition: AM 1.5,100mW/cm2, measure the dark current (Jd)=9.35 × 10 of device-5A/
cm2, photoelectric current (Jph)=3.93 × 10-4A/cm2, specific detecivity (D*)=1.17 × 108Jones。
The photoelectric detector performance parameter of the present invention of table 1
As can be seen from Table 1: by adulterating the organic photodetector of HA solution preparation in photoactive layer compared to not
HA solution is adulterated, density of photocurrent becomes larger, and dark current reduces, and the detectivity of device is greatly improved, and works as P3HT:
IEICO-4F:PC71When the mass ratio of BM:HA is 1:0.9:0.1:0.15, the best performance of device.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify to technical solution documented by previous embodiment, or some or all of the technical features are equal
Replacement；And these are modified or replaceed, the model for technical solution of the embodiment of the present invention that it does not separate the essence of the corresponding technical solution
It encloses, should all cover within the scope of the claims and the description of the invention.
Claims (10)
1. one kind is based on the organic wide spectrum photodetector of ternary, including photoactive layer (4), which is characterized in that the photolytic activity
Layer (4) is made after electron acceptor material and the mixing of humic acid material through spin coating proceeding, the electron donor of electron donor material
The mass ratio of material, electron acceptor material and humic acid material is 1:1:(0.03~0.2).
2. according to claim 1 a kind of based on the organic wide spectrum photodetector of ternary, which is characterized in that the electronics
Donor material is P3HT, and electron acceptor material is by IEICO-4F and PC71The mixed solution of BM is made, the electron donor material,
The blend solution concentration of electron acceptor material and humic acid material is 30mg/mL.
3. according to claim 2 a kind of based on the organic wide spectrum photodetector of ternary, which is characterized in that the electronics
The mass ratio of IEICO-4F and PC71BM is 9:1 in acceptor material.
4. according to claim 1 a kind of based on the organic wide spectrum photodetector of ternary, which is characterized in that the light is living
Property layer (4) with a thickness of 50~300nm.
5. according to any one of claims 1 to 4 a kind of based on the organic wide spectrum photodetector of ternary, feature exists
In the photodetector includes the substrate (1) set gradually from top to bottom, conductive cathode (2), electron transfer layer (3), light
Active layer (4), hole transmission layer (5) and metal anode (6).
6. according to claim 5 a kind of based on the organic wide spectrum photodetector of ternary, which is characterized in that the substrate
(1) it is made using transparent polymer material, the transparent polymer material uses polyethylene, polymethyl methacrylate, poly- carbon
Acid esters, polyurethanes, polyimides, vinyl chloride-vinyl acetate resin and polyacrylic acid it is one or more；The material of the conductive cathode (2)
Material is ITO；Electron transfer layer (3) material is ZnO sol gel solution, with a thickness of 30nm；Hole transmission layer (5) material
Material is MoO3, with a thickness of 15nm；Metal anode (6) material is one of Ag, Al and Au or a variety of, with a thickness of 100nm.
7. according to claim 6 a kind of based on the organic wide spectrum photodetector of ternary, which is characterized in that the ZnO
Sol gel solution is made of zinc acetate and ethanol amine, and the weight of the zinc acetate accounts for 60%~80%, and surplus is ethanol amine.
8. described in any item a kind of preparation methods based on the organic wide spectrum photodetector of ternary according to claim 1~7,
It is characterised in that it includes following preparation step:
(1) substrate being made of substrate and conductive cathode is cleaned, with being dried with nitrogen after cleaning；
(2) configured ZnO mixed solution is spin-coated to conductive cathode surface, and the substrate after spin coating is carried out at thermal annealing
Reason, obtains electron transfer layer；
(3) by electron donor material, the blending of electron acceptor material and humic acid material composition is molten for spin coating on the electron transport layer
Photoactive layer is made in liquid；
It (4) is 3 × 10 in vacuum degree3Under the conditions of Pa, MoO is deposited on photoactive layer surface3, hole transmission layer is prepared；
(5) evaporation metal anode on the hole transport layer, is packaged to obtain photodetector later.
9. a kind of preparation method based on the organic wide spectrum photodetector of ternary according to claim 8, feature exist
In the temperature of thermal annealing is 150 DEG C in the step (2), time 15min.
10. a kind of preparation method based on the organic wide spectrum photodetector of ternary according to claim 8, feature exist
In the thermal annealing mode uses one of Thermostatic platform heating, baking oven heating, Far-infrared Heating and Hot-blast Heating or more
Kind.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112490265A (en) * | 2020-11-27 | 2021-03-12 | 电子科技大学 | Up-conversion low-turn-on voltage infrared detection-light emitting device and preparation method thereof |
| CN112928213A (en) * | 2021-02-05 | 2021-06-08 | 电子科技大学 | Ultra-high-sensitivity near-infrared transistor photoelectric detector and preparation method thereof |
| CN113540356A (en) * | 2021-06-08 | 2021-10-22 | 中国科学院大学 | Self-driven organic photoelectric detector with high detection rate for near infrared light |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112490265A (en) * | 2020-11-27 | 2021-03-12 | 电子科技大学 | Up-conversion low-turn-on voltage infrared detection-light emitting device and preparation method thereof |
| CN112928213A (en) * | 2021-02-05 | 2021-06-08 | 电子科技大学 | Ultra-high-sensitivity near-infrared transistor photoelectric detector and preparation method thereof |
| CN113540356A (en) * | 2021-06-08 | 2021-10-22 | 中国科学院大学 | Self-driven organic photoelectric detector with high detection rate for near infrared light |
| CN113540356B (en) * | 2021-06-08 | 2024-04-05 | 中国科学院大学 | Self-driven organic photoelectric detector with high detection rate for near infrared light |
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