CN113838983A - Based on NPB/V2O5Organic photoelectric sensor of buffer layer and preparation method thereof - Google Patents
Based on NPB/V2O5Organic 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 photoelectron, relates to an organic photoelectric sensor, and particularly relates to a photoelectric sensor based on NPB/V2O5An organic photoelectric sensor of a buffer layer and a preparation method thereof; used for solving the problem of V in the existing organic photoelectric sensor2O5The energy level variation causes many problems. The invention adopts V2O5The layer serves as a hole transport body layer and is in contact with the hole transport body layerAn NPB layer is arranged between the two layers and is used as a hole transport modification layer; interface contact among all functional layers is effectively improved, the contact resistance of the interface can be effectively reduced, and energy level matching is more reasonable; the energy level arrangement of the whole device is optimized, the collection efficiency of photo-generated carriers at the metal anode after dissociation is improved, the reverse injection of the carriers in the external bias is inhibited, and the integral performance of the device is improved; at the same time, NPB/V2O5The buffer layer can block the influence of water and oxygen in the air on the active layer, and the service life of the device is further prolonged.
Description
Technical Field
The invention belongs to the technical field of organic semiconductor photoelectron, relates to an organic photoelectric sensor, and particularly relates to a photoelectric sensor based on NPB/V2O5An organic photoelectric sensor of a buffer layer and a preparation method thereof.
Background
The photoelectric sensor has the capability of converting optical signals into electric signals and plays an important role in photoelectric devices; they have a variety of applications such as optical communications, environmental monitoring, biomedical imaging, and the like. The traditional photoelectric sensor shows excellent performances in the aspects of photosensitivity, responsivity and detectability by virtue of an inorganic III-V semiconductor with high carrier mobility, good stability and smaller exciton binding energy; however, inorganic photosensors are limited in flexible application and cost 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 relatively slow response speed and less charge generation are caused by the lower carrier mobility and disordered molecular arrangement of the organic polymer; in addition, therefore, many efforts have been made to improve the performance of the organic photosensor.
The interface engineering plays an important role in improving the performance of the organic photoelectric sensor; firstly, by selecting a proper interface material, the dark current reversely injected by the device under the action of an external bias voltage can be effectively reduced, and meanwhile, the light collection capability and the carrier transmission capability can be improved, the photocurrent can be improved, and the on-off ratio of the device can be increased; secondly, the active layer can be isolated from water, oxygen and other unfavorable components in the external environment by proper interface materials, so that the stability of the device is greatly improved; finally, suitable interface materials can simplify processing techniques, thereby reducing manufacturing costs.
Inorganic metal oxide is the most common anode buffer layer material at present, and is widely used in OLEDs, solar cells and organic photoelectric sensors; wherein, V2O5Is one of the most widely used buffer layers. However, V prepared by different processes2O5Are also very different, making the device unfavorable for forming good ohmic contact, in the active layer and V2O5An energy level barrier is formed between the two layers, so that the hole collecting capacity of the device is reduced; further, V is vacuum-deposited2O5May cause oxygen deficiency to form oxygen vacancies, and V2O5The valence band energy level of the electron transport layer moves to a deeper position to form an energy level barrier which is not beneficial to 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 photon-generated carriers is reduced; in addition, V2O5The film work function is particularly sensitive to the external environment, such as air, humidity, temperature, etc., air exposure in a short time, oxygen adsorption and moisture absorption of the surface, resulting in V2O5The film work function is significantly reduced, which reduces the effective hole injection or extraction.
Disclosure of Invention
The invention aims to provide a method based on NPB/V (neutral Point/Voltage)2O5The organic photoelectric sensor with buffer layer is prepared by sequentially arranging a hole transport modification layer NPB and a hole transport main body layer V between an active layer and a conductive anode layer2O5The interface contact between the active layer and the metal anode is improved, and the contact resistance of the interface is effectively reduced; optimize the deviceThe overall energy level arrangement ensures that the energy level matching is more reasonable, the collection efficiency of the photo-generated carriers at the metal anode after dissociation is improved, the reverse injection of the carriers in the process of external bias voltage is inhibited, and the overall performance of the device is improved.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
based on NPB/V2O5An organic photosensor of a buffer layer comprising: from up stacking gradually transparent stratum basale, transparent conductive cathode layer, electron transport layer, active layer, hole transport modification layer, hole transport bulk layer and the electrically conductive anode layer of setting down, its characterized in that, still be provided with hole transport modification layer between hole transport bulk layer and the active layer, hole transport bulk layer adopts V2O5And the hole transmission modification layer adopts an NPB thin film layer.
Furthermore, the thickness of the hole transmission modification layer is 5-50 nm, and the thickness of the hole transmission main body layer is 5-100 nm.
Further, the transparent substrate layer is made of transparent quartz glass, the transparent conductive cathode layer is made of ITO, and the electron transmission layer is made of ZnO or PEIE; the active layer is made of a donor material and an acceptor material, 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.
The above-mentioned NPB/V-based2O5The preparation method of the organic photoelectric sensor of the buffer layer comprises the following steps:
step 1: sequentially carrying out detergent rubbing, deionized water ultrasonic cleaning, acetone ultrasonic cleaning and isopropanol ultrasonic cleaning on the transparent substrate of the prefabricated transparent conductive cathode layer, and treating by using an ultraviolet ozone cleaning machine;
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;
and step 3: dissolving a donor material and an acceptor material in chlorobenzene according to a mass ratio of 1:1, and stirring for 12-24 hours on a magnetic heating stirring table at 40-60 ℃ 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 with the thickness of 100-500 nm;
and 4, step 4: depositing NPB layer on the active layer, and pumping vacuum chamber to vacuum degree lower than 1 × 10-4Pa, adjusting the heating temperature to 150-200 ℃, preheating for 5 minutes, opening a baffle of an evaporation boat, adjusting the temperature until the growth rate reaches 0.01-0.03 nm/s, and evaporating until the thickness is 5-50 nm to obtain an NPB layer;
and 5: vapor plating of V on the NPB layer2O5Layer, pumping the vacuum chamber to a degree of vacuum of less than 1 × 10-4Pa, regulating the heating temperature to 750-850 ℃, preheating for 5 minutes, opening a baffle of an evaporation boat, regulating the temperature until the growth rate reaches 0.01-0.03 nm/s, and evaporating until the thickness is 5-100 nm to obtain V2O5A layer;
step 6: at V2O5Evaporating and plating a conductive anode layer on the layer, and pumping the vacuum degree of the vacuum cavity to be lower than 3 multiplied by 10-3Pa, regulating the heating temperature to 850-950 ℃ for preheating for 5 minutes, opening a baffle of an evaporation boat, regulating the temperature until the growth rate reaches 0.01-0.03 nm/s, and evaporating to the thickness of 100-200 nm to obtain the conductive anode layer.
Further, in the step 1, the deionized water ultrasonic cleaning is performed twice for 10-30 minutes each, the acetone ultrasonic cleaning is performed twice for 30-60 minutes each, the isopropanol ultrasonic cleaning is performed twice for 30-60 minutes each, and the treatment time of the ultraviolet ozone cleaning machine is 10-30 minutes.
In summary, compared with the prior art, the invention has the beneficial effects that:
1) the invention adopts the vacuum evaporation method to prepare NPB/V2O5The buffer layer can avoid the damage of a 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) according to the invention, the NPB buffer layer with a lower melting point is evaporated, so that the active layer can be protected, and V of the active layer with a higher melting point in evaporation is avoided2O5The integrity of the active layer is ensured by damage;
3) the invention is provided with NPB/V2O5The 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) because the NPB buffer layer is arranged, the interface contact among all 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 at the metal anode after dissociation is improved, the reverse injection of the carriers in the external 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 that the present invention is based on NPB/V2O5The structure schematic diagram of the organic photoelectric sensor of the buffer layer is shown in the specification, wherein 1 is a transparent basal layer, 2 is a transparent conductive cathode layer, 3 is an electron transmission layer, 4 is an active layer, 5 is a hole transmission modification layer, 6 is a hole transmission main body layer, and 7 is a conductive anode layer.
FIG. 2 shows that the present invention is based on NPB/V2O5Schematic diagram of energy level structure of organic photoelectric sensor of buffer layer.
FIG. 3 is a graph of the spectral scanning photocurrent density of each NPB thickness organic photosensor 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 further described in detail with reference to the following embodiments and the accompanying drawings.
Example 1
The embodiment provides a method based on NPB/V2O5The structure of the organic photoelectric sensor with the buffer layer is shown in fig. 1, and specifically comprises: a transparent substrate layer 1 on the transparent substrate layer 1A transparent conductive cathode layer 2, an electron transport layer 3, an active layer 4, an NPB layer 5, and a V layer2O5Layer 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.
The above-mentioned NPB/V-based2O5The preparation method of the organic photoelectric sensor of the buffer layer comprises the following steps:
step 1, pre-cleaning;
adopting a transparent substrate layer 1 with a preset conductive cathode layer 2, firstly, scrubbing with dust-free cloth and detergent to remove impurities such as dust, fingerprints and oil stains attached to the surface of the substrate; then, ultrasonic cleaning is carried out for two times and 30 minutes respectively by using deionized water, ultrasonic cleaning is carried out for two times and 1 hour respectively by using acetone, and ultrasonic cleaning is carried out for two times and 30 minutes respectively by using isopropanol; finally, nitrogen gas is used for blowing dry and an ultraviolet ozone cleaning machine is used for processing for 20 minutes;
uniformly dripping 35ul of ZnO precursor solution on the conductive cathode layer 2, spin-coating at 4000rpm for 40s, annealing at 200 ℃ for 30 minutes in air atmosphere, and forming an electron transport layer with the thickness of 60nm on the conductive cathode layer;
preferably, the preparation of the ZnO precursor solution: stirring 500mg of zinc acetate dihydrate, 500mg of ethanolamine and 506ul of 2-methoxyethanol at room temperature for more than 2 hours to obtain a ZnO precursor solution;
uniformly dripping 30ul of the active layer solution on the electron transport layer 3, spin-coating at 2000rpm for 40s, annealing at 110 ℃ for 10 minutes in a nitrogen atmosphere, and forming an active layer with the 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% of DIO is added as an additive, chlorobenzene is used as a solvent, the mixture is stirred in a glove box for more than 12 hours to obtain an active layer solution, and the concentration of the prepared solution is 20 mg/ml;
filling 100mg of NPB into an evaporation boat, putting the evaporation boat into an evaporation tank, closing an evaporation boat baffle, and pumping the pre-vacuum degree to be lower than 1 × 10-4Pa, opening the base station to rotate, adjusting the temperature of the evaporation boat to 150 ℃, preheating for 5 minutes, opening a baffle of the evaporation boat, adjusting the temperature until the growth rate reaches and keeps at 0.01nm/s, evaporating until the thickness is 5nm, adjusting the temperature again until the growth rate reaches and keeps at 0.03nm/s, and evaporating until the thickness is 20 nm;
take 2g of V2O5Filling into evaporation boat, placing the evaporation boat into evaporation tank, closing the baffle of evaporation boat, and pumping the pre-vacuum degree to below 1 × 10-4Pa, opening the base station to rotate, adjusting the temperature of the evaporation boat to 750 ℃, preheating for five minutes, opening a baffle of the evaporation boat, adjusting the temperature until the growth rate reaches and keeps at 0.01nm/s, evaporating to 5nm in thickness, adjusting the temperature again until the growth rate reaches and keeps at 0.03nm/s, and evaporating to 10nm in thickness;
filling 2g of Ag into an evaporation boat, putting the evaporation boat into an evaporation tank, closing an evaporation boat baffle, and pumping the pre-vacuum degree to be lower than 3 x 10-3Pa, opening the base station to rotate, adjusting the temperature of the evaporation boat to 850 ℃ to preheat for five minutes, opening a baffle of the evaporation boat, adjusting the temperature until the growth rate reaches and keeps at 0.02nm/s, evaporating until the thickness is 5nm, adjusting the temperature again until the growth rate reaches and keeps at 0.05nm/s, and evaporating until the thickness is 100 nm;
namely the preparation of the above-mentioned NPB/V-based2O5And an organic photoelectric sensor of the buffer layer.
In terms of working principle:
the invention adopts V2O5The layer serves as a hole transport host layer and is between the hole transport host layer and the active layerSetting NPB layer as hole transmission modification layer, and finally based on NPB/V2O5The energy level structure of the organic photoelectric sensor with the buffer layer is schematically shown in fig. 2, and it can be seen from the figure that compared with the conventional structure (without the NPB layer), the structure has many problems: because V is in the process of vapor deposition2O5Oxygen vacancy, oxygen deficiency, V, easily occurs2O5The HOMO energy level of (A) fluctuates, resulting in ITIC-Th and V2O5The energy level difference is unstable, which is not beneficial to forming good ohmic contact and influencing the hole collection efficiency; after the NPB layer is added, the energy level can be kept unchanged after vacuum evaporation due to the characteristics of organic micromolecules, a good energy level matching structure and ohmic contact are formed, and V is solved2O5The problem of energy level variation and the efficiency of photon-generated carrier utilization due to the reduction of defects are also improved.
In addition, in the conventional structure, if V is set2O5The thickness of the device is increased, so that the influence of water and oxygen in the air on the device can be delayed, the effective working time of the device is prolonged, and the dark current of the device under the reverse bias working condition is reduced, but 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 from fig. 3 that as the film thickness increases, the photocurrent does not decrease but increases, thereby making up for a single V2O5Due to the problems associated with the increased thickness, the effective operating time of the device is prolonged.
Example 2
The embodiment provides a method based on NPB/V2O5The only difference between the buffer layer of the organic photoelectric sensor and the embodiment 1 is that: the thickness of the NPB buffer layer is 10nm, and the preparation method of the corresponding NPB buffer layer comprises the following steps:
filling 100mg of NPB into an evaporation boat, putting the evaporation boat into an evaporation tank, closing an evaporation boat baffle, and pumping the pre-vacuum degree to be lower than 1 × 10-4Pa, opening the base station to rotate, adjusting the temperature of the evaporation boat to 150 ℃ to preheat for 5 minutes, opening the evaporation boat to blockAdjusting the temperature until the growth rate reaches and keeps 0.01nm/s, evaporating to 5nm in thickness, adjusting the temperature again until the growth rate reaches and keeps 0.03nm/s, and evaporating to 10nm in thickness;
NPB/V-based data provided in examples 1 and 22O5The organic photoelectric sensor of the buffer layer is subjected to spectrum scanning test, and a spectrum scanning photocurrent density graph under bias voltage is shown in figure 3, as can be seen from the graph, at a fixed V2O5In the case of a thickness of 10nm, the photocurrent of the device gradually increases as the NPB thickness gradually increases from 0nm to 10nm and then to 20nm, mainly due to NPB/V2O5Good energy level structure and ohmic contact are formed between the composite buffer layer and the active layer, the capture of defects to photon-generated carriers is reduced, and the collection efficiency of the device to holes is improved.
While the invention has been described with reference to specific embodiments, any feature disclosed in this specification may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise; all of the disclosed features, or all of the method or process steps, may be combined in any combination, except mutually exclusive features and/or steps.
Claims (4)
1. Based on NPB/V2O5An organic photosensor of a buffer layer comprising: from up stacking gradually transparent stratum basale, transparent conductive cathode layer, electron transport layer, active layer, hole transport modification layer, hole transport bulk layer and the electrically conductive anode layer of setting down, its characterized in that, still be provided with hole transport modification layer between hole transport bulk layer and the active layer, hole transport bulk layer adopts V2O5And the hole transmission modification layer adopts an NPB thin film layer.
2. Based on NPB/V as claimed in claim 12O5The organic photoelectric sensor of the buffer layer is characterized in that the thickness of the hole transmission modification layer is 5-50 nm, and the thickness of the hole transmission main body layer is 5-100 nm.
3. Based on NPB/V as claimed in claim 12O5The organic photoelectric sensor of the buffer layer is characterized in that the transparent substrate layer is made of transparent quartz glass, the transparent conductive cathode layer is made of ITO, and the electron transmission layer is made of ZnO or PEIE; the active layer is made of a donor material and an acceptor material, 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. Based on NPB/V as claimed in claim 12O5The preparation method of the organic photoelectric sensor of the buffer layer is characterized by comprising the following steps:
step 1: sequentially carrying out detergent rubbing, deionized water ultrasonic cleaning, acetone ultrasonic cleaning and isopropanol ultrasonic cleaning on the transparent substrate of the prefabricated transparent conductive cathode layer, and treating by using an ultraviolet ozone cleaning machine;
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;
and step 3: dissolving a donor material and an acceptor material in chlorobenzene according to a mass ratio of 1:1, and stirring for 12-24 hours on a magnetic heating stirring table at 40-60 ℃ 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 with the thickness of 100-500 nm;
and 4, step 4: depositing NPB layer on the active layer, and pumping vacuum chamber to vacuum degree lower than 1 × 10-4Pa, adjusting the heating temperature to 150-200 ℃, preheating for 5 minutes, opening a baffle of an evaporation boat, adjusting the temperature until the growth rate reaches 0.01-0.03 nm/s, and evaporating until the thickness is 5-50 nm to obtain an NPB layer;
and 5: vapor plating of V on the NPB layer2O5Layer, pumping the vacuum chamber to a degree of vacuum of less than 1 × 10-4Pa, regulating the heating temperature to 750-850 ℃, preheating for 5 minutes, opening a baffle of an evaporation boat, regulating the temperature until the growth rate reaches 0.01-0.03 nm/s, and evaporating until the thickness is 5-100 nm to obtain V2O5A layer;
step 6: at V2O5Evaporating and plating a conductive anode layer on the layer, and pumping the vacuum degree of the vacuum cavity to be lower than 3 multiplied by 10-3Pa, regulating the heating temperature to 850-950 ℃ for preheating for 5 minutes, opening a baffle of an evaporation boat, regulating the temperature until the growth rate reaches 0.01-0.03 nm/s, and evaporating to the thickness of 100-200 nm to obtain the conductive anode layer.
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