CN111883601A - Flexible photoelectric detector capable of adjusting detection wavelength and preparation method thereof - Google Patents

Flexible photoelectric detector capable of adjusting detection wavelength and preparation method thereof Download PDF

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CN111883601A
CN111883601A CN202010887386.8A CN202010887386A CN111883601A CN 111883601 A CN111883601 A CN 111883601A CN 202010887386 A CN202010887386 A CN 202010887386A CN 111883601 A CN111883601 A CN 111883601A
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layer
flexible
detection wavelength
substrate
photoelectric detector
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黄江
贾晓伟
李娜
刘洁尘
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University of Electronic Science and Technology of China
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Abstract

The invention discloses a flexible photoelectric detector capable of adjusting detection wavelength and a preparation method thereof, and relates to the field of photoelectric detection.

Description

Flexible photoelectric detector capable of adjusting detection wavelength and preparation method thereof
Technical Field
The invention relates to the field of photoelectric detection, in particular to a flexible photoelectric detector capable of adjusting detection wavelength and a preparation method thereof.
Background
The perovskite photoelectric detector has the characteristics of high carrier mobility, small dark current and the like, and has wide application in the aspects of numerous consumer electronic products, health care, resource detection, environmental protection and the like. In order to meet the requirements of practical applications, the perovskite photodetector should have a high detectivity and a narrow spectral response range to achieve more accurate detection. However, the excitons in the long wave band are difficult to separate, so that the external quantum efficiency of the device in the near infrared band is low, and the detection rate is low. And a single device only has one absorption peak and can only detect a single wavelength. Therefore, how to improve the detection capability and the dynamic detection capability of the near-infrared band while realizing more accurate detection, and how to realize that a single device can detect a plurality of wavelengths becomes the key point and the difficulty of research of the perovskite photoelectric detector.
For the device, the performance of the device is improved mainly by aiming at the structural design and the preparation process of the narrow-band detector with the near infrared band. In 2017, a Koen Vanderwal task group reports an optical microcavity structure-based donor-acceptor organic photodetector in advanced materials, so that the performance that the quantum efficiency can reach 40% outside a near-infrared band is finally realized, and a plurality of small devices with different functional thicknesses are integrated on a single large device to realize the detection of multiple wavelengths of the single device. With the discovery of rare earth element doped perovskite, an active layer perovskite which can be electromagnetically controlled to stretch enters the visual field of people. By electromagnetically controlling the thickness d of the active layer according to the formula
Figure BDA0002655980570000011
(wherein λ)mFor detecting wavelength, L is the thickness of the optical microcavity and n is the refraction of the active layerRate, m is a natural number greater than 0), the detection wavelength of the detector can be controlled.
Disclosure of Invention
The invention aims to: on the basis of solving the problems that the half-wave peak width of a perovskite photoelectric detector is large, the detection performance in a near infrared band is poor, and a single device cannot realize detection of multiple wavelengths, the flexible photoelectric detector capable of adjusting the detection wavelength and the preparation method thereof are provided.
The technical scheme adopted by the invention is as follows:
a flexible photoelectric detector capable of adjusting detection wavelength comprises a substrate, a flexible substrate, a semitransparent conductive electrode layer, an electron transmission layer, a rare earth perovskite active layer, a hole transmission layer and a metal electrode layer which are sequentially arranged from bottom to top.
Preferably, the flexible substrate includes, but is not limited to
a: plastic substrates are generally classified into 3 types: semi-crystalline thermoplastic polymers such as PET, PEN, PEEK, VHB, PDMS; ② amorphous polymers, such as PC and PES, are amorphous thermoplastics; ③ non-crystalline high glass transition temperature polymers, such as PAR, PCO, PNB and PI.
b: a stainless steel substrate.
c, ultra-thin glass substrate.
And d, paper substrate.
e, biological composite film substrate.
Preferably, the semitransparent conductive electrode layer is made of any one of gold, silver, an aluminum electrode, a silver nanowire and a conductive polymer film, can play a role in charge transmission of the electrode and has strong reflectivity, and the thickness of the semitransparent conductive electrode layer is 2-30 nm.
Preferably, the raw material composition of the electron transport layer is PEIE, PC61BM、TiO2And ZnO.
Preferably, the thickness of the perovskite active layer is 100nm to 200nm, and the energy band difference is 1.1 to 1.2 eV.
Preferably, the rare earth perovskite active layer is LaMn03Class, LaNiO3Class (La)1-xRx)2/3Sr1/3MnO3，(R＝Sm，Tb)，La0.67Sr0.33Mn1-xFexO3,(La1-yTby)0.67Sr0.33MnO3，La0.8Sr0.2CoO3，La0.8Sr0.2MnO3And the thickness of the rare earth doped manganese perovskite compound is 100nm-200 nm.
Preferably, the hole transport layer has a material composition of MnO3PEDOT PSS, CuSCN, CuI and NiOm(m-2 or 4).
Preferably, the metal electrode layer is made of any one of gold, silver, an aluminum electrode, a silver nanowire and a conductive polymer film, and the thickness of the metal electrode layer is 50-150 nm.
A preparation method of a flexible photoelectric detector capable of adjusting detection wavelength comprises the following steps:
(1): sticking a layer of flexible substrate on the base plate;
(2): evaporating a semitransparent conductive electrode layer on a flexible substrate;
(3): spin-coating an electron transport layer on the semitransparent conductive electrode layer, and annealing for later use;
(4): spin-coating a rare earth perovskite functional layer solution on the electron transport layer to form a rare earth perovskite active layer, and annealing for later use;
(5): MnO is evaporated on the rare earth perovskite active layer3Forming a hole transport layer;
(6): and evaporating a silver electrode on the hole transport layer.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the invention can obtain the narrow-band detection performance of visible/near-infrared wave bands by utilizing the optical microcavity effect.
2. The invention can realize that the wearable body can be bent and folded to be suitable for various shapes by utilizing the stretchable flexible substrate.
3. The invention can change the thickness of the optical microcavity by externally adding an electromagnetic field and changing the thickness of the active layer by utilizing the magnetostrictive effect of the rare earth element doped perovskite active layer, and realizes the detection of different wave bands by adjusting the thickness of the optical microcavity, thereby realizing the dynamic detection capability of different wave bands.
4. The flexible photoelectric detector has a unique structure, has good detection capability by combining a simple and efficient spin coating process, and has guiding significance for large-scale industrial preparation of silicon-based photoelectric detectors and detectors in other fields.
Drawings
The invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is a schematic structural view of the present invention;
the drawings in fig. 1 illustrate: 1-substrate, 2-flexible substrate, 3-semitransparent conductive electrode layer, 4-electron transport layer, 5-rare earth perovskite active layer, 6-hole transport layer, 7-metal electrode layer and 8-incident light
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The utility model provides a photoelectric detector with detection wavelength is adjustable based on optics microcavity effect, includes base plate 1, paste flexible substrate 2 on the base plate 1, plated with semitransparent conductive electrode layer 3 on the flexible substrate 2, semitransparent conductive electrode layer 3 has scribbled electron transport layer 4, tombarthite perovskite active layer 5, hole transport layer 6 from bottom to top in proper order soon, metal electrode layer 7 has been plated on electron transport layer 6.
Wherein the flexible substrate 2 is PET.
The semitransparent conductive electrode layer 3 is an Au conductive electrode with a thickness of 30 nm.
The electron transport layer 4 used PEIE with a thickness of 10 nm.
The thickness of the rare earth perovskite active layer 5 is 150nm (La)0.7Sm0.3)2/3Sr1/3MnO3A bulk heterojunction.
The hole transport layer 6 adopts MnO with the thickness of 10nm3A film.
The metal electrode layer 7 is a silver electrode having a thickness of 100 nm.
A method for preparing a photoelectric detector with adjustable detection wavelength based on optical microcavity effect comprises the following preparation steps:
1. cleaning of the substrate 1: and sequentially putting the substrate 1 adhered with the flexible substrate layer 2 into a detergent, acetone, deionized water and isopropanol, ultrasonically cleaning for 15min each time, and then drying by inert gas.
2. Evaporating the semitransparent conductive electrode layer 3: then transferring the substrate 1 to a vacuum evaporation device under a vacuum degree of less than 3.0 × 10-3And evaporating an Au electrode layer in the Pa environment. And then placing the semitransparent conductive electrode layer 3 into an ozone machine for UV treatment for 10 min.
3. Spin coating the electron transport layer 4: and spin-coating a PEIE electron transport layer 4 on the semitransparent conductive electrode layer 3 after ozone treatment, controlling the rotating speed to be 4000rpm and the time to be 20s, and then carrying out annealing treatment, wherein the annealing temperature is controlled to be 150 ℃ and the time to be 15 min.
4. Spin coating of the rare earth perovskite active layer 5: preheating the substrate 1 with the electron transport layer 4 and the rare earth perovskite solution at 100 ℃, absorbing the rare earth perovskite solution by a spin coater, spin-coating the rare earth perovskite solution on the surface of the electron transport layer 4, then placing the electron transport layer on a hot bench for annealing, and carrying out heat preservation annealing at 110 ℃ for 1 h.
5. Evaporation of hole transport layer 6: transferring the substrate to vacuum evaporation equipment under vacuum degree of less than 3 × 10-3Evaporating a layer of MnO in Pa environment3And then cooled for 30min under a vacuum environment.
8. And (3) evaporating a metal electrode 7: then the vacuum degree is less than 3.0 multiplied by 10-3And evaporating a layer of Ag electrode in a Pa environment.
Before testing, willThe PET flexible substrate 2 and the film thereon are taken down from the base plate 1, and the bendable flexible detector is obtained. Under standard test conditions, a light beam is extracted from the light source, so that the incident light 8 perpendicularly enters the bendable flexible detector. Under the condition of no external magnetic field, the thickness of the rare earth perovskite active layer is about 130nm, the test result shows that the bendable flexible detector has near-infrared narrow-band detection capability at 780nm, and the detection rate is-1012Jones, peak width at half wave is 29 nm. When an external electromagnetic field is applied to the detector to cause the thickness of the microcavity to contract by 5nm and extend by 5nm, the detection wavelength becomes 760nm and 805 nm. The device has the function that a single device can be adjusted by an external electromagnetic field to detect the wavelength. And the flexible detector can be bent, and has good wearing performance.
Example 2
This example is different from example 1 in that (La) is used as the rare earth perovskite active layer 5, based on example 10.45Tb0.55)2/3Sr1/3MnO3A bulk heterojunction.
Before testing, the PET flexible substrate 2 and the film thereon are taken off from the base plate 1, and the bendable flexible detector is obtained. Under the standard test condition, a light beam is led out from a light source, so that incident light 8 is vertically incident to the bendable flexible detector, the test result is that when the flexible substrate 2 is properly bent, the curvature radius is 14cm, the thickness of the rare earth perovskite active layer 5 is about 130nm, the test result is that the photoelectric detector has near infrared narrow-band detection capability at 760nm, and the detection rate is 10 to 1012Jones, peak width at half wave is 25 nm. When an external electromagnetic field is applied to the detector to cause the thickness of the microcavity to contract by 5nm and extend by 5nm, the detection wavelength is changed to 735nm and 782 nm. The device has the function that a single device can be adjusted by an external electromagnetic field to detect the wavelength.
Example 3
On the basis of embodiment 1, the present embodiment is different from embodiment 1 in that the bendable PET flexible substrate 2 is exchanged for a stretchable VHB flexible substrate 2.
Before testing, the VHB flexible substrate 2 and the film on the VHB flexible substrate are taken off from the base plate 1, and the stretchable flexible detector is obtained. In thatUnder the standard test condition, light beams are led out from a light source, so that incident light 8 is perpendicularly incident to the bendable flexible detector, the test result is that when the flexible substrate is properly stretched, the rare earth perovskite active layer is about 135nm, the test result is that the bendable flexible detector has near-infrared narrow-band detection capability at 621nm, and the detection rate is 10 to 1012Jones, a half-wave peak width of 30 nm. When an external electromagnetic field is applied to the detector under the bending state of the device, so that the thickness of the microcavity is contracted by 5nm and is expanded by 5nm, the detection wavelength is changed to 600nm and 650 nm. The device has the function that a single device can be adjusted by an external electromagnetic field to detect the wavelength.

Claims (7)

1. The utility model provides an adjustable detection wavelength's flexible photoelectric detector, includes base plate (1) that the below set up, its characterized in that, flexible substrate (2) have been pasted on base plate (1), flexible substrate (2) evaporation plating has translucent conductive electrode layer (3), scribbles electron transport layer (4), tombarthite perovskite active layer (5), hole transport layer (6), metal electrode layer (7) from bottom to top in proper order soon again.
2. A flexible photodetector with adjustable detection wavelength according to claim 1, characterized in that the flexible substrate (2) comprises
a: a plastic substrate comprising a semi-crystalline thermoplastic polymer, a non-crystalline high glass transition temperature polymer;
b: a stainless steel substrate;
c, an ultrathin glass substrate;
d, paper substrate;
e, biological composite film substrate
Any one of them.
3. The flexible photoelectric detector capable of adjusting detection wavelength according to claim 1,
the raw material of the semitransparent conductive electrode layer (3) is any one of gold, silver, aluminum electrode, silver nanowire and conductive polymer film,
the thickness of the semitransparent conductive electrode layer (3) is 2-30 nm.
4. The flexible photoelectric detector capable of adjusting detection wavelength according to claim 1,
the raw material composition of the electron transport layer (4) is PEIE, PC61BM、TiO2Any one of spiro-OMeTAD and ZnO.
5. The flexible photoelectric detector capable of adjusting detection wavelength according to claim 1,
the rare earth perovskite active layer (5) is a rare earth doped manganese perovskite compound,
the thickness of the rare earth perovskite active layer (5) is 100nm-200nm, and the energy band difference is 1.1-1.2 eV.
6. The flexible photoelectric detector capable of adjusting detection wavelength according to claim 1,
the hole transport layer (6) has a material composition of MnO3、PEDOT:PSS、CuSCN、CuI、PC61BM and NiOm(m-2 or 4).
7. A preparation method of a flexible photoelectric detector capable of adjusting detection wavelength is characterized by comprising the following steps:
a) a layer of flexible substrate (2) is pasted on the base plate (1);
b) a layer of semitransparent conductive electrode layer (3) is evaporated on the flexible substrate (2);
c) spin-coating an electron transmission layer (4) on the semitransparent conductive electrode layer (3), and annealing for later use;
d) spin-coating the rare earth perovskite functional layer solution on the electron transport layer (4) to form a rare earth perovskite active layer (5), and annealing for later use;
e) MnO is evaporated on the rare earth perovskite active layer (5)3Forming a hole transport layer (6);
f) and evaporating a silver electrode on the hole transport layer (6).
CN202010887386.8A 2020-08-28 2020-08-28 Flexible photoelectric detector capable of adjusting detection wavelength and preparation method thereof Pending CN111883601A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114335347A (en) * 2021-12-14 2022-04-12 电子科技大学 Flexible stretchable photoelectric detector with adjustable spectral range and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105957966A (en) * 2016-05-31 2016-09-21 华东师范大学 REO (rare earth oxide) down-conversion material perovskite solar cell and preparation method
CN108389976A (en) * 2018-04-20 2018-08-10 北京大学 A kind of organic inorganic hybridization perovskite solar cell and preparation method thereof of a small amount of rare earth ion doping
CN109841739A (en) * 2019-03-13 2019-06-04 电子科技大学 A kind of perovskite photodetector and preparation method thereof with optical microcavity structure
CN111180585A (en) * 2019-12-30 2020-05-19 电子科技大学 Flexible perovskite detector based on optical microcavity and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105957966A (en) * 2016-05-31 2016-09-21 华东师范大学 REO (rare earth oxide) down-conversion material perovskite solar cell and preparation method
CN108389976A (en) * 2018-04-20 2018-08-10 北京大学 A kind of organic inorganic hybridization perovskite solar cell and preparation method thereof of a small amount of rare earth ion doping
CN109841739A (en) * 2019-03-13 2019-06-04 电子科技大学 A kind of perovskite photodetector and preparation method thereof with optical microcavity structure
CN111180585A (en) * 2019-12-30 2020-05-19 电子科技大学 Flexible perovskite detector based on optical microcavity and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114335347A (en) * 2021-12-14 2022-04-12 电子科技大学 Flexible stretchable photoelectric detector with adjustable spectral range and preparation method thereof

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