CN111883666A - Organic photoelectric detector based on optical microcavity effect and preparation method thereof - Google Patents
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Abstract
The invention discloses an organic photoelectric detector based on an optical microcavity effect and a preparation method thereof, belonging to the field of photoelectric detectors. Photoelectric detector from the bottom up sets gradually into: the device comprises a glass substrate, a semitransparent conductive electrode layer, a double narrow-band modulation layer, an organic functional layer, a hole transport layer and a metal electrode layer. The optical microcavity structure formed by the semitransparent conductive electrode layer, the double narrow-band modulation layer, the organic functional layer, the hole transmission layer and the metal electrode layer can realize double narrow-band response to different wave bands, so that the dual-band narrow-band optical fiber has dual-band narrow-band detection capability. The invention effectively solves the problems that the half-wave peak width of the organic photoelectric detector is large, the detection performance in the near infrared band is not good, and the organic photoelectric detector only has single-band detection capability.
Description
Technical Field
The invention relates to the technical field of photoelectric detectors, in particular to an organic photoelectric detector based on an optical microcavity effect and a preparation method thereof.
Background
Compared with inorganic photovoltaic devices, organic photovoltaic devices have the characteristics of simple manufacturing process, low cost, large-area manufacturing on different substrates and the like, and the organic photovoltaic devices are rapidly developed and widely applied to the fields of organic solar cells, organic photodetectors and the like. The organic photoelectric detector has the characteristics of easy integration 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 organic photodetector should have a high detection rate and a narrow spectral response range to achieve more accurate detection.
The conventional organic photoelectric detector has low external quantum efficiency of the device in a near infrared band due to the difficulty in separating excitons in a long band, so that the detection rate is low. Therefore, how to realize more accurate detection and have dual-band narrow-band detection becomes a key point and a difficulty of organic photoelectric detector research.
Disclosure of Invention
The technical scheme adopted by the invention is as follows:
an organic photoelectric detector based on an optical microcavity effect comprises a glass substrate, a semitransparent conductive electrode layer, a double narrow-band modulation layer, an organic functional layer, a hole transport layer and a metal electrode layer which are sequentially arranged from bottom to top.
Preferably, the semitransparent conductive electrode layer is made of any one of Indium Tin Oxide (ITO), gold, silver, an aluminum electrode, a silver nanowire and a conductive polymer film, and the thickness of the semitransparent conductive electrode layer is 2-30 nm.
Preferably, the raw material composition of the double narrow-band modulation layers is PEIE, PC61BM、TiO2And ZnO and benzothiazolyl cyanine dye (3- (2- (((1l 2-diiodoalkyl) oxy) ethyl) -2- ((E) -2- ((E) -3- ((Z) -2- (3- (2-hydroxyethyl) benzo [ d [)]]Thiazol-2 (3H) -alkylene) ethylene) -2- (iodo-1-2-methyl) cyclohex-1-en-1-yl) ethylAlkenyl) benzo [ d]Thiazol-3-ium). The near-infrared absorbent has a selective absorption effect on light rays in a specific waveband, can realize effective utilization or protection on light rays with specific wavelength, and is not influenced by incident light angles.
Preferably, the organic functional layer is organic donor-acceptor material bulk heterojunction PBTTT: PCBM, TPDP: C60, P3HT: PCBM, C60: CuPc, the thickness of the organic functional layer is 100nm-200nm, and the energy band difference of the organic functional layer is 1.1-1.2 eV.
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 an organic photoelectric detector based on an optical microcavity effect comprises the following steps:
step 1: and cleaning and drying the glass substrate.
Step 1: in a high vacuum environment, a transparent conductive electrode layer is vapor-plated on a glass substrate;
step 2: spin-coating a mixture of an electron transport material and a near-infrared absorbent on a transparent conductive electrode layer at the rotation speed of 4000rpm for 20s, and then annealing at the annealing temperature of 150 ℃ for 15min to obtain a dual-narrow-band modulation layer;
and step 3: spin-coating an organic donor-acceptor solution on the double narrow-band modulation layer, and then carrying out annealing treatment at the annealing temperature of 110 ℃ for 60min to obtain an organic functional layer;
and 4, step 4: under a high vacuum environment, evaporating and plating a raw material of the hole transport layer on the organic functional layer to prepare the hole transport layer;
and 5: and evaporating a metal electrode on the hole transport layer in a high vacuum environment.
Step 6: and after the evaporation is finished, packaging the obtained device in an isolation environment to obtain the organic photoelectric detector.
Preferably, the high vacuum environment is a vacuum degree of less than 3.0 × 10-3Environment of Pa.
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 utilizes benzothiazolyl cyanine dye (3- (2- (((1l 2-diiodoalkyl) oxy) ethyl) -2- ((E) -2- ((E) -3- ((Z) -2- (3- (2-hydroxyethyl) benzo [ d ] ] thiazole-2 (3H) -alkylidene) ethylidene) -2- (iodo-1-2-methyl) cyclohex-1-en-1-yl) ethenyl) benzo [ d ] thiazol-3-onium) which can be doped in an electron transport material and has a strong absorption peak at 800-820 nm, the response waveband of a PBTTT: PCBM organic detector based on optical microcavity effect is 760-860 nm, and the response waveband after passing through a double narrow-band modulation layer containing the benzothiazolyl cyanine dye is 760-800 nm, 820-860 nm, and has dual-band narrow-band detection capability.
3. The organic 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 the organic photoelectric detector and detectors in other fields.
Drawings
FIG. 1 is a schematic structural diagram of an organic photodetector based on the optical microcavity effect according to the present invention;
FIG. 2 is a schematic diagram of the optical microcavity structure of FIG. 2.
Description of the figures:
the light-emitting diode comprises a glass substrate 1, a semitransparent conductive electrode layer 2, a double narrow-band modulation layer 3, an organic functional layer 4, a hole transport layer 5, a metal electrode layer 6 and incident light 7.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "disposed" or "connected" to another element, it can be directly disposed or connected to the other element or intervening elements may also be present.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
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.
All other embodiments obtained are within the scope of protection of the present invention.
An organic photoelectric detector based on an optical microcavity effect comprises a glass substrate 1, a semitransparent conductive electrode layer 2, a double narrow-band modulation layer 3, an organic functional layer 4, a hole transport layer 5 and a metal electrode layer 6 which are sequentially arranged from bottom to top. The semitransparent conductive electrode layer 2 is made of any one of Indium Tin Oxide (ITO), gold, silver, an aluminum electrode, a silver nanowire and a conductive polymer film, and the thickness of the semitransparent conductive electrode layer is 2-30 nm. The raw material composition of the double narrow-band modulation layer 3 is PEIE, PC61BM、TiO2And ZnO and benzothiazolyl cyanine dye (3- (2- (((1l 2-diiodoalkyl) oxy) ethyl) -2- ((E) -2- ((E) -3- ((Z) -2- (3- (2-hydroxyethyl) benzo [ d [)]]Thiazol-2 (3H) -alkylene) ethylene) -2- (iodo-1-2-methyl) cyclohex-1-en-1-yl) ethenyl) benzo [ d]Thiazol-3-ium). The organic functional layer 4 is organic donor-acceptor material bulk heterojunction PBTTT PCBM, TPDP C60, P3HT PCBM, C60 CuPc with the thickness of 100nm-200nm and the energy band difference of 1.1-1.2 eV. The hole transport layer 5 has a material composition of MnO3、PEDOT:PSS、CuSCN、CuI and NiOm(m-2 or 4). The metal electrode layer 6 is made of any one of gold, silver and aluminum electrodes, silver nanowires and conductive polymer films, and the thickness of the metal electrode layer is 50-150 nm.
Example 1
Cleaning the glass substrate 1: and sequentially putting the glass substrate 1 into a detergent, acetone, deionized water and isopropanol, ultrasonically cleaning for 15min each time, and then blowing and drying by inert gas. Then transferring the glass substrate 1 to a vacuum evaporation device with a vacuum degree of less than 3.0 × 10-3And evaporating an Au electrode layer in the Pa environment. And then placing the transparent conductive electrode layer 2 into an ozone machine for UV treatment for 10 min. And (3) spin-coating a mixture of PEIE and benzothiazole cyanine dye on the transparent conductive electrode layer 2 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 is 15 min. . The glass substrate 1 with the double narrow-band modulation layer 3 spin-coated and the organic donor-acceptor solution are preheated at 100 ℃, the acceptor solution is spin-coated on the surface of the double narrow-band modulation layer 3 by a suction machine of a spin coater, then the double narrow-band modulation layer is placed on a hot bench for annealing, and the annealing is carried out for 1h at 110 ℃. Transferring the glass substrate 1 to a vacuum evaporation device under a vacuum degree of less than 3 × 10-3Evaporating a layer of MnO in Pa environment3Cooling in vacuum environment for 30min, and vacuum degree of less than 3.0 × 10-3And evaporating a layer of Ag electrode in a Pa environment. And packaging the obtained device in an isolation environment to obtain the organic photoelectric detector. The semitransparent conductive electrode layer 2 is an Au conductive electrode layer with the thickness of 30 nm. The double narrow-band modulation layer 3 is a mixture of PEIE and benzothiazolium cyanine dyes with a thickness of 10 nm. The organic functional layer 4 adopts PBTTT (Poly-p-phenylene benzobisoxazole) PCBM with the thickness of 150 nm. The hole transport layer 5 adopts a MnO3 thin film with the thickness of 10 nm. The metal electrode layer 6 is a silver electrode with the thickness of 100 nm.
Under the standard test condition, a light beam is led out from a light source, so that an incident light ray 7 vertically enters the organic photoelectric detector, the test result shows that the organic photoelectric detector has near-infrared narrow-band detection capability at 780nm and 840nm, the half-wave peak widths are 6nm and 8nm respectively, and the detection rates are up to ℃ -1011Jones and 1012Jones。
Example 2:
cleaning the glass substrate 1: and sequentially putting the glass substrate 1 into a detergent, acetone, deionized water and isopropanol, ultrasonically cleaning for 15min each time, and then blowing and drying by inert gas. Then transferring the glass substrate 1 to a vacuum evaporation device with a vacuum degree of less than 3.0 × 10-3And evaporating an Au electrode layer in the Pa environment. And then placing the transparent conductive electrode layer 2 into an ozone machine for UV treatment for 10 min. And (3) spin-coating a mixture of PEIE and benzothiazole cyanine dye on the transparent conductive electrode layer 2 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 is 15 min. . The glass substrate 1 with the double narrow-band modulation layer 3 spin-coated and the organic donor-acceptor solution are preheated at 100 ℃, the acceptor solution is spin-coated on the surface of the double narrow-band modulation layer 3 by a suction machine of a spin coater, then the double narrow-band modulation layer is placed on a hot bench for annealing, and the annealing is carried out for 1h at 110 ℃. Transferring the glass substrate 1 to a vacuum evaporation device under a vacuum degree of less than 3 × 10-3Evaporating a layer of MnO in Pa environment3Cooling in vacuum environment for 30min, and vacuum degree of less than 3.0 × 10-3And evaporating a layer of Ag electrode in a Pa environment. And packaging the obtained device in an isolation environment to obtain the organic photoelectric detector. The semitransparent conductive electrode layer 2 is an Au conductive electrode layer with the thickness of 30 nm. The double narrow-band modulation layer 3 is a mixture of PEIE and benzothiazolium cyanine dyes with a thickness of 10 nm. The organic functional layer 4 adopts TPDP C60 with the thickness of 100 nm. The hole transport layer 5 adopts a MnO3 thin film with the thickness of 10 nm. The metal electrode layer 6 is a silver electrode with the thickness of 100 nm.
Under the standard test condition, light beams are led out from a light source, so that incident light rays 7 vertically enter the organic photoelectric detector, the test result shows that the organic photoelectric detector has near-infrared narrow-band detection capability at 760nm and 850nm, the half-wave peak widths are respectively 5nm and 7nm, and the detection rates are respectively 10 to 1011Jones and 1012Jones。
As can be seen from the examples 1 and 2, the organic photodetector adopting the organic functional layer with the thickness of 100nm and TPDP of C60 has near-infrared narrow-band detection capability at 760nm and 850nm, and the half-wave peak widths are 5nm and 7nm respectively; the organic photoelectric detector adopting the PBTTT with the organic functional layer thickness of 150nm has near-infrared narrow-band detection capability at 780nm and 840nm, and the half-wave peak width is 6nm and 8nm respectively. The dual-band narrowband detection is realized.
Claims (8)
1. An organic photoelectric detector based on an optical microcavity effect is characterized by comprising a glass substrate (1), a semitransparent conductive electrode layer (2), a double narrow-band modulation layer (3), an organic functional layer (4), a hole transport layer (5) and a metal electrode layer (6) which are sequentially arranged from bottom to top;
the organic functional layer (4) is any one of organic donor-acceptor material bulk heterojunction PBTTT (poly-P-butylene-terephthalate) PCBM (poly-P-phenylene-terephthalate), P3HT PCBM (poly-P-phenylene-terephthalate), TPDP (poly-P-phenylene-terephthalate) C60, C60 and CuPc, the thickness is 100nm-200nm, and the energy band difference is 1.1-1.2 eV.
2. The organic photoelectric detector based on the optical microcavity effect as claimed in claim 1, wherein the semitransparent conductive electrode layer (2) is made of any one of indium tin oxide, gold, silver, aluminum electrode, silver nanowire and conductive polymer film, and has a thickness of 2-30 nm.
3. An organic photodetector based on optical microcavity effect according to claim 1, characterized in that the material composition of the dual narrow-band modulation layer (3) is PEIE, PC61BM、TiO2And ZnO and a near infrared absorber.
4. An organic photodetector based on the optical microcavity effect according to claim 3, wherein the near-infrared absorber comprises:
A. inorganic substances
(a) The metal oxide comprises tungsten oxide, titanium oxide and zinc oxide, wherein the tungsten oxide particles have better absorption effect on near infrared light with wave bands of 1400-1600 nm and 1900-2200 nm.
(b) The metal sulfide and the sulfide after nanocrystallization have very good near infrared light absorption characteristics due to the energy band transition, wherein the copper sulfide nano particles (Cu)xS, x is more than or equal to 1 and less than or equal to 2) has better absorption effect at 1400-2500 nm.
(c) The nano metal has better absorption effect in a near infrared light area of 750nm to 2500 nm.
B. Organic class
(a) Cyanine dyes
[ the lambda max range of cyanine dyes, polymethine cyanine dyes is centered at 340-1400 nm, and the lambda max of carotenoids is centered at 580-700 nm, wherein the benzothiazolyl cyanine dye 3- (2- (((1l 2-diiodoalkyl) oxy) ethyl) -2- ((E) -2- ((E) -3- ((Z) -2- (3- (2-hydroxyethyl) benzo [ d ] thiazol-2 (3H) -alkylene) ethylene) -2- (iodo-1-2-methyl) cyclohex-1-en-1-yl) vinyl) benzo [ d ] thiazol-3-ium has an absorption peak at 810 nm.
Phthalocyanine and naphthalocyanine dyes, wherein the structure of the phthalocyanine compound can be divided into two parts, one part is an external functional group, and hydrogen atoms, alkyl groups, benzo groups and heterocycles can be used as the external functional group; the other part is a central atom, often a nitrogen atom. The phthalocyanine dye absorbs light with a wavelength of about 650-750 nm.
(b) Nocyanine dyes
③ the range of the lambda max of the azo dye and the monoazo type near infrared dye is concentrated between 700 and 778nm, and the range of the polyazo near infrared absorption dye lambda max is concentrated between 700 and 800 nm.
Fourthly, the quinone dyes are divided into three types: naphthoquinone, anthraquinone, naphthoquinone imine methine dyes. Quinone dyes can change their maximum absorption wavelength by changing the electron donating ability of the electron donating group or changing the molecular structure of the dye. The method of introducing the electroattractive group to the benzene ring at the other end of the anthraquinone skeleton can lead the maximum absorption wavelength of the anthraquinone dye to generate red shift, and the stronger the electroattractive property of the electroattractive group is, the larger the generated red shift is.
A metal complex dye with good absorption effect in the range of 780-2520 nm.
Sixthly, the free radical type dye is a 'colored' dye containing a conjugated structure.
The aromatic methane dye can generate red shift of lambda max by increasing the number of conjugated olefinic bonds and can extend to a near infrared region.
The dye of the kind of the eight (r) takes place the condensation reaction with 3,4,9, 10-tetracarboxylic dianhydride and amine to produce, light stability, thermostability, photochemical inertia and water-resisting property are all good.
5. An organic photodetector based on the optical microcavity effect as claimed in claim 1, characterized in that the hole transport layer (5) has a composition of MnO as the raw material3PEDOT PSS, CuSCN, CuI and NiOm(m-2 or 4).
6. The organic photodetector based on the optical microcavity effect as claimed in claim 1, wherein the metal electrode layer (6) is made of one or more of silver, aluminum and copper, and has a thickness of 50-150 nm.
7. A preparation method of an organic photoelectric detector based on an optical microcavity effect is characterized by comprising the following steps:
step 1: cleaning and drying the glass substrate;
step 1: in a high vacuum environment, a transparent conductive electrode layer is vapor-plated on a glass substrate;
step 2: spin-coating a mixture of an electron transport material and a near-infrared absorbent on a transparent conductive electrode layer at the rotation speed of 4000rpm for 20s, and then annealing at the annealing temperature of 150 ℃ for 15min to obtain a dual-narrow-band modulation layer;
and step 3: spin-coating an organic donor-acceptor solution on the double narrow-band modulation layer, and then carrying out annealing treatment at the annealing temperature of 110 ℃ for 60min to obtain an organic functional layer;
and 4, step 4: under a high vacuum environment, evaporating and plating a raw material of the hole transport layer on the organic functional layer to prepare the hole transport layer;
and 5: evaporating a metal electrode on the hole transport layer in a high vacuum environment;
step 6: and after the evaporation is finished, packaging the obtained device in an isolation environment to obtain the organic photoelectric detector.
8. The method of claim 7, wherein the high vacuum environment is a vacuum degree of less than 3.0 x 10-3Environment of Pa.
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