CN113838983B - NPB/V-based 2 O 5 Organic photoelectric sensor of buffer layer and preparation method thereof - Google Patents
NPB/V-based 2 O 5 Organic photoelectric sensor of buffer layer and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of organic semiconductor photoelectrons, relates to an organic photoelectric sensor, and in particular relates to a photoelectric sensor based on NPB/V 2 O 5 An organic photoelectric sensor of a buffer layer and a preparation method thereof; is used for solving the problem of V-caused in the prior organic photoelectric sensor 2 O 5 A number of problems arise with energy level variations. The invention adopts V 2 O 5 The layer is used as a hole transport main layer, and an NPB layer is arranged between the hole transport main layer and the active layer and used as a hole transport modification layer; interface contact between the functional layers is effectively improved, and contact resistance of the interface can be effectively reduced, so that energy level matching is more reasonable; the energy level arrangement of the whole device is optimized, the collection efficiency of the photo-generated carriers after dissociation at the metal anode is improved, the reverse injection of the carriers during externally-applied bias voltage is inhibited, and the whole performance of the device is improved; at the same time NPB/V 2 O 5 The buffer layer can prevent the influence of water and oxygen in air on the active layer, so that the service life of the device is further prolonged.
Description
Technical Field
The invention belongs to the technical field of organic semiconductor photoelectrons, relates to an organic photoelectric sensor, and in particular relates to a photoelectric sensor based on NPB/V 2 O 5 An organic photoelectric sensor of buffer layer and its preparation method are provided.
Background
Photoelectric sensors have the ability to convert optical signals into electrical signals, and are important in photoelectric devices; they have a variety of applications such as optical communications, environmental monitoring, and biomedical imaging. The conventional photosensor exhibits excellent performance in terms of photosensitivity, responsivity and detectivity by means of an inorganic III-V semiconductor having high carrier mobility, good stability and small exciton binding energy; however, inorganic photosensors are limited in flexible applications and costs due to inherent disadvantages such as inflexibility and complicated manufacturing processes. Compared with an inorganic photoelectric sensor, the organic photoelectric sensor has the characteristics of low cost, simple manufacturing process, large-area preparation and mechanical flexibility, however, the lower carrier mobility and disordered molecular arrangement of the organic polymer lead to relatively slower response speed and less charge generation; in addition, therefore, many efforts have been made to improve the performance of organic photosensors.
The interface engineering plays an important role in improving the performance of the organic photoelectric sensor; firstly, by selecting a proper interface material, dark current reversely injected when a device is externally biased can be effectively reduced, meanwhile, light collection capacity and carrier transmission capacity can be improved, photocurrent is improved, and the on-off ratio of the device is increased; secondly, the proper interface material can isolate the active layer from water, oxygen and other unfavorable components in the external environment, so that the stability of the device is greatly improved; finally, appropriate interface materials may simplify processing techniques, thereby reducing manufacturing costs.
Inorganic metal oxides are currently the most commonThe anode buffer layer material of the (B) is widely used in OLED, solar cell and organic photoelectric sensor; wherein V is 2 O 5 Is one of the most widely used buffer layers. However, V prepared by different processes 2 O 5 The energy levels of (a) also differ so much that the device is not conducive to forming a good ohmic contact between the active layer and V 2 O 5 Forming an energy level barrier therebetween, which reduces the hole collection capability of the device; in addition, vacuum deposition V 2 O 5 May cause oxygen deficiency during the process of (2) to form oxygen vacancies, and V 2 O 5 The valence band energy level of (2) moves to deeper, forming an energy barrier that is unfavorable for hole transport; the existence of the defects is also easy to capture carriers, and the carriers are used as recombination centers of the carriers, so that the utilization rate of photo-generated carriers is reduced; in addition, V 2 O 5 The work function of the film is particularly sensitive to the external environment, such as air, humidity, temperature, etc., air exposure in a short time, oxygen adsorption and moisture absorption at the surface, resulting in V 2 O 5 The work function of the film is significantly reduced and the reduction of the surface work function reduces the effective hole injection or extraction.
Disclosure of Invention
The invention aims at solving a plurality of problems existing in the prior art and provides a method based on NPB/V 2 O 5 An organic photoelectric sensor with buffer layer and its preparing process are disclosed, which sequentially arrange a hole-transporting modifying layer NPB and a hole-transporting main layer V between active layer and conductive anode layer 2 O 5 Interface contact between the active layer and the metal anode is improved, and contact resistance of the interface is effectively reduced; the overall energy level arrangement of the device is optimized, so that the energy level matching is more reasonable, the collection efficiency of the photo-generated carriers after dissociation at the metal anode is improved, the reverse injection of the carriers during externally-applied bias voltage is inhibited, and the overall performance of the device is improved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
NPB/V-based 2 O 5 An organic photoelectric sensor of a buffer layer, comprising: transparent substrate layer and transparent conductive shade which are laminated in sequence from bottom to topThe anode comprises a pole layer, an electron transport layer, an active layer, a hole transport modification layer, a hole transport main body layer and a conductive anode layer, and is characterized in that the hole transport modification layer is also arranged between the hole transport main body layer and the active layer, and the hole transport main body layer adopts V 2 O 5 And the hole transport modification layer adopts an NPB film layer.
Further, the thickness of the hole transport modification layer is 5-50 nm, and the thickness of the hole transport host layer is 5-100 nm.
Further, the transparent basal layer is made of transparent quartz glass, the transparent conductive cathode layer is made of ITO, and the electron transport layer is made of ZnO or PEIE; the active layer is made of a donor material and a receptor material, wherein the donor material is P3HT or PBDB-T, and the receptor material is ITIC-Th or PCBM; the conductive anode layer is made of Ag or Au.
Based on NPB/V 2 O 5 The preparation method of the organic photoelectric sensor of the buffer layer comprises the following steps:
step 1: sequentially performing washing with a detergent, ultrasonic washing with deionized water, ultrasonic washing with acetone and ultrasonic washing with isopropanol on a transparent substrate of the prefabricated transparent conductive cathode layer, and treating with an ultraviolet ozone cleaner;
step 2: preparing an electron transport layer precursor solution, preparing an electron transport layer on the conductive cathode layer by using a spin coating method, and annealing the spin-coated film on a heating table at 150-250 ℃ for 20-40 minutes to obtain an electron transport layer with the thickness of 50-100 nm;
step 3: dissolving a donor material and a receptor material in chlorobenzene according to a mass ratio of 1:1, and stirring on a magnetic heating stirring table at 40-60 ℃ for 12-24 hours to prepare an active layer solution with a concentration of 10-30 mg/ml; preparing an active layer on the electron transport layer by using a spin coating method, and annealing the spin-coated film on a heating table at 100-200 ℃ for 5-15 minutes to obtain an active layer of 100-500 nm;
step 4: evaporating NPB layer on the active layer, and vacuumizing the vacuum chamber to a vacuum degree of less than 1×10 -4 Pa, regulating heating temperature to 150-200 ℃ and preheating for 5 minutes, and opening the evaporation boatThe temperature of the baffle is regulated until the growth rate reaches 0.01-0.03 nm/s, and the thickness of the baffle is 5-50 nm, so that an NPB layer is obtained;
step 5: vapor deposition of V on NPB layer 2 O 5 A layer for evacuating the vacuum chamber to a vacuum level of less than 1×10 -4 Pa, regulating heating temperature to 750-850 ℃ and preheating for 5 minutes, opening a baffle plate of an evaporation boat, regulating temperature to 0.01-0.03 nm/s of growth rate, evaporating until thickness is 5-100 nm, and obtaining V 2 O 5 A layer;
step 6: at V 2 O 5 Evaporating conductive anode layer on the layer, and vacuumizing the vacuum chamber to a vacuum degree lower than 3×10 -3 Pa, heating temperature is regulated to 850-950 ℃ for preheating for 5 minutes, a baffle plate of an evaporation boat is opened, the temperature is regulated to reach the growth rate of 0.01-0.03 nm/s, evaporation is carried out until the thickness is 100-200 nm, and a conductive anode layer is obtained.
Further, in the step 1, the deionized water ultrasonic cleaning is performed twice for 10 to 30 minutes each, the acetone ultrasonic cleaning is performed twice for 30 to 60 minutes each, the isopropanol ultrasonic cleaning is performed twice for 30 to 60 minutes each, and the treatment time of the ultraviolet ozone cleaning machine is 10 to 30 minutes.
In summary, compared with the prior art, the invention has the following beneficial effects:
1) The invention adopts the vacuum evaporation method to prepare NPB/V 2 O 5 The buffer layer can avoid the damage of the solvent to the lower active layer in the preparation process of the solution method, effectively protects the active layer, has flexible parameter regulation and control capability, is easy to prepare buffer layers with different parameter configurations, and meets different design requirements;
2) The invention can protect the active layer and avoid the active layer from evaporating the V with higher melting point because the NPB buffer layer with lower melting point is evaporated firstly 2 O 5 When the active layer is damaged, the integrity of the active layer is ensured;
3) The invention is provided with NPB/V 2 O 5 The buffer layer can block the influence of water and oxygen in the air on the active layer, prolong the service life of the device and ensure that the photocurrent is improved;
4) According to the invention, as the NPB buffer layer is arranged, the interface contact between the functional layers is improved, the contact resistance of the interface can be effectively reduced, and the energy level matching is more reasonable; the overall energy level arrangement of the device is optimized, the collection efficiency of photo-generated carriers after dissociation at the metal anode is improved, the reverse injection of the carriers during externally applied bias is inhibited, the overall performance of the device is improved, and the device plays a positive role in further development of the organic photoelectric sensor.
Drawings
FIG. 1 shows the NPB/V based method of the present invention 2 O 5 The organic photoelectric sensor of the buffer layer is structurally schematic, wherein 1 is a transparent substrate layer, 2 is a transparent conductive cathode layer, 3 is an electron transport layer, 4 is an active layer, 5 is a hole transport modification layer, 6 is a hole transport main body layer, and 7 is a conductive anode layer.
FIG. 2 shows the NPB/V based method of the present invention 2 O 5 The energy level structure of the organic photoelectric sensor of the buffer layer is schematically shown.
FIG. 3 is a graph of spectral scanning photocurrent densities of organic photosensors of various NPB thicknesses under bias in an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following examples and the accompanying drawings.
Example 1
The embodiment provides a NPB/V-based system 2 O 5 The structure of the organic photoelectric sensor of the buffer layer is shown in fig. 1, and specifically includes: a transparent base layer 1, a transparent conductive cathode layer 2, an electron transport layer 3, an active layer 4, an NPB layer 5, and a V layer sequentially laminated on the transparent base layer 1 2 O 5 Layer 6 and conductive anode layer 7; in this embodiment, the transparent substrate layer 1 is made of transparent glass, the conductive cathode layer 2 is made of ITO, the electron transport layer 3 is made of ZnO, the active layer 4 is made of a mixed film of P3HT and ITIC-Th, and the conductive anode layer 7 is made of Ag.
Based on NPB/V 2 O 5 The preparation method of the organic photoelectric sensor of the buffer layer comprises the following steps:
step 1, pre-cleaning;
the transparent substrate layer 1 of the preset conductive cathode layer 2 is adopted, and firstly, dust, fingerprints, greasy dirt and other impurities attached to the surface of the substrate are rubbed off by using dust-free cloth and detergent; then sequentially using deionized water for ultrasonic cleaning twice for 30 minutes respectively, acetone for ultrasonic cleaning twice for 1 hour respectively, and isopropanol for ultrasonic cleaning twice for 30 minutes respectively; finally, drying by using nitrogen and treating for 20 minutes by using an ultraviolet ozone cleaning machine;
step 2, preparing an electron transport layer 3 on the conductive cathode layer 2;
uniformly dripping 35ul of ZnO precursor solution on the conductive cathode layer 2, spin-coating at the speed of 4000rpm for 40s, and annealing at 200 ℃ for 30 minutes in an air atmosphere to form an electron transport layer with the thickness of 60nm on the conductive cathode layer;
preferably, the configuration of the ZnO precursor solution: 500mg zinc acetate dihydrate +500mg ethanolamine +506ul 2-methoxyethanol, and stirring for more than 2 hours at room temperature to obtain a ZnO precursor solution;
step 3, preparing an active layer 4 on the electron transport layer 3;
uniformly dripping 30ul of active layer solution on the electron transport layer 3, spin-coating at a speed of 2000rpm for 40s, and annealing at 110 ℃ for 10 minutes in a nitrogen atmosphere to form an active layer with a thickness of 150nm on the electron transport layer;
preferably, the donor material in the active layer solution is P3HT, the acceptor material is ITIC-Th, the mass ratio is 1:1, 0.5% DIO is added as an additive, chlorobenzene is used as a solvent, stirring is carried out in a glove box for more than 12 hours, the active layer solution is obtained, and the concentration of the prepared solution is 20mg/ml;
step 4, preparing a hole transport modification layer 5 on the active layer 4;
filling 100mg of NPB into evaporation boat, placing the evaporation boat into evaporation tank, closing evaporation boat baffle, and vacuumizing to below 1×10 -4 Pa, opening the base station to rotate, regulating the temperature of the evaporation boat to 150 ℃, preheating for 5 minutes, opening the evaporation boat baffle, regulating the temperature to reach and keep the growth rate at 0.01nm/s, and evaporating until the thickness is reachedThe temperature is regulated again until the growth rate reaches and is kept at 0.03nm/s, and the vapor deposition is carried out until the thickness is 20nm;
step 5, preparing a hole transport main body layer 6 on the hole transport modification layer 5;
2g of V 2 O 5 Filling the evaporation boat into the evaporation tank, closing the evaporation boat baffle, and vacuumizing to a level below 1×10 -4 Pa, opening a base table for rotation, regulating the temperature of an evaporation boat to 750 ℃, preheating for five minutes, opening an evaporation boat baffle, regulating the temperature to reach and keep the growth rate at 0.01nm/s, evaporating to reach the thickness of 5nm, regulating the temperature again to reach and keep the growth rate at 0.03nm/s, evaporating to reach the thickness of 10nm;
step 6, preparing a conductive anode layer 7 on the hole transport modification layer 6:
filling 2g of Ag into the evaporation boat, placing the evaporation boat into the evaporation tank, closing the evaporation boat baffle, and vacuumizing to below 3×10 -3 Pa, opening a base table for rotation, regulating the temperature of an evaporation boat to 850 ℃ for preheating for five minutes, opening an evaporation boat baffle, regulating the temperature to reach and keep the growth rate at 0.02nm/s, evaporating to reach the thickness of 5nm, regulating the temperature again to reach and keep the growth rate at 0.05nm/s, evaporating to reach the thickness of 100nm;
namely, the NPB/V-based catalyst is prepared 2 O 5 Organic photoelectric sensor of buffer layer.
In terms of working principle:
the invention adopts V 2 O 5 A layer is used as a hole transport main layer, an NPB layer is arranged between the hole transport main layer and the active layer as a hole transport modification layer, and finally the layer is based on NPB/V 2 O 5 The energy level structure of the organic photoelectric sensor of the buffer layer is schematically shown in fig. 2, and it can be seen that, compared with the conventional structure (without NPB layer), there are a plurality of problems: due to V in the evaporation process 2 O 5 Is easy to generate oxygen vacancy, generates oxygen deficiency, V 2 O 5 Fluctuations in HOMO energy levels of (B) result in ITIC-Th and V 2 O 5 The energy level difference is unstable, which is unfavorable for forming good ohmic contact and shadowEfficiency of collecting sound and holes; after the NPB layer is added, the energy level can be kept unchanged after vacuum evaporation due to the characteristics of small organic molecules, a good energy level matching structure and ohmic contact are formed, and V is solved 2 O 5 The energy level change causes problems, and the utilization efficiency of the photo-generated carriers is also improved due to the reduction of defects.
In addition, if V is to be used in the conventional structure 2 O 5 Although the thickness of the device is increased, the influence of water and oxygen in the air on the device can be delayed, the effective working time of the device is prolonged, the dark current of the device under the reverse bias working condition is reduced, the hole recombination can occur due to the increase of the migration length, the collection efficiency of the device hole is influenced, and the photocurrent of the device is reduced; in the present invention, by introducing a layer of NPB, it can be seen in FIG. 3 that the photocurrent is not reduced but increased with increasing film thickness, thereby compensating for a single V 2 O 5 Because of the problems associated with the increased thickness, the effective operating time of the device is extended.
Example 2
The embodiment provides a NPB/V-based system 2 O 5 The only difference between the organic photoelectric sensor of the buffer layer and the embodiment 1 is that: the thickness of the NPB buffer layer is 10nm, and the corresponding preparation method of the NPB buffer layer comprises the following steps:
filling 100mg of NPB into evaporation boat, placing the evaporation boat into evaporation tank, closing evaporation boat baffle, and vacuumizing to below 1×10 -4 Pa, opening a base table for rotation, regulating the temperature of an evaporation boat to 150 ℃, preheating for 5 minutes, opening an evaporation boat baffle, regulating the temperature to reach and keep the growth rate at 0.01nm/s, evaporating to reach the thickness of 5nm, regulating the temperature again to reach and keep the growth rate at 0.03nm/s, evaporating to reach the thickness of 10nm;
NPB/V based provided for example 1 and example 2 2 O 5 The organic photoelectric sensor of the buffer layer performs spectrum scanning test, the spectrum scanning photocurrent density diagram under bias is shown in figure 3, and the diagram can be seen at fixed V 2 O 5 With a thickness of 10nm, as the NPB is thickThe degree gradually increases from 0nm to 10nm and then to 20nm, and the photocurrent of the device also gradually increases, mainly due to NPB/V 2 O 5 Good energy level structure and ohmic contact are formed between the composite buffer layer and the active layer, the capture of defects on photon-generated carriers is reduced, and the collection efficiency of the device on holes is improved.
While the invention has been described in terms of specific embodiments, any feature disclosed in this specification may be replaced by alternative features serving the equivalent or similar purpose, unless expressly stated otherwise; all of the features disclosed, or all of the steps in a method or process, except for mutually exclusive features and/or steps, may be combined in any manner.
Claims (4)
1. NPB/V-based 2 O 5 An organic photoelectric sensor of a buffer layer, comprising: the transparent substrate layer, the transparent conductive cathode layer, the electron transport layer, the active layer, the hole transport modification layer, the hole transport main body layer and the conductive anode layer are sequentially stacked from bottom to top, and the transparent substrate layer is characterized in that the hole transport modification layer is further arranged between the hole transport main body layer and the active layer, and the hole transport main body layer adopts V 2 O 5 The hole transport modification layer adopts an NPB film layer; the active layer is made of a donor material and an acceptor material, the NPB film layer and the acceptor material form an energy level matching structure, and the thickness of the hole transport modification layer is 10-20 nm.
2. NPB/V based 2 O 5 The organic photoelectric sensor of the buffer layer is characterized in that the thickness of the hole transport main body layer is 5-100 nm.
3. NPB/V based 2 O 5 The organic photoelectric sensor of the buffer layer is characterized in that the transparent basal layer is made of transparent quartz glass, the transparent conductive cathode layer is made of ITO, and the electron transport layer is made of ZnO or PEIE; the active layer adopts a donor material and a receptor materialThe material is prepared, the donor material is P3HT or PBDB-T, and the acceptor material is ITIC-Th or PCBM; the conductive anode layer is made of Ag or Au.
4. NPB/V based 2 O 5 The preparation method of the organic photoelectric sensor of the buffer layer is characterized by comprising the following steps of:
step 1: sequentially performing washing with a detergent, ultrasonic washing with deionized water, ultrasonic washing with acetone and ultrasonic washing with isopropanol on a transparent substrate of the prefabricated transparent conductive cathode layer, and treating with an ultraviolet ozone cleaner;
step 2: preparing an electron transport layer precursor solution, preparing an electron transport layer on the conductive cathode layer by using a spin coating method, and annealing the spin-coated film on a heating table at 150-250 ℃ for 20-40 minutes to obtain an electron transport layer with the thickness of 50-100 nm;
step 3: dissolving a donor material and a receptor material in chlorobenzene according to a mass ratio of 1:1, and stirring on a magnetic heating stirring table at 40-60 ℃ for 12-24 hours to prepare an active layer solution with a concentration of 10-30 mg/ml; preparing an active layer on the electron transport layer by using a spin coating method, and annealing the spin-coated film on a heating table at 100-200 ℃ for 5-15 minutes to obtain an active layer of 100-500 nm;
step 4: evaporating NPB layer on the active layer, and vacuumizing the vacuum chamber to a vacuum degree of less than 1×10 -4 Pa, regulating the heating temperature to 150-200 ℃ for preheating for 5 minutes, opening a baffle plate of an evaporation boat, regulating the temperature to reach the growth rate of 0.01-0.03 nm/s, evaporating until the thickness is 5-50 nm, and obtaining an NPB layer;
step 5: vapor deposition of V on NPB layer 2 O 5 A layer for evacuating the vacuum chamber to a vacuum level of less than 1×10 -4 Pa, regulating heating temperature to 750-850 ℃ and preheating for 5 minutes, opening a baffle plate of an evaporation boat, regulating temperature to 0.01-0.03 nm/s of growth rate, evaporating until thickness is 5-100 nm, and obtaining V 2 O 5 A layer;
step 6: at V 2 O 5 Evaporating conductive anode layer on the layer, and vacuumizing the vacuum chamber to a vacuum degree lower than 3×10 -3 Pa, adjusting the heating temperature toPreheating for 5 minutes at 850-950 ℃, opening a baffle plate of an evaporation boat, adjusting the temperature to reach the growth rate of 0.01-0.03 nm/s, evaporating until the thickness is 100-200 nm, and obtaining the conductive anode layer.
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