CN110783465B - Thermal electron photoelectric detector based on 8-hydroxyquinoline aluminum/metal heterojunction - Google Patents
Thermal electron photoelectric detector based on 8-hydroxyquinoline aluminum/metal heterojunction Download PDFInfo
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- CN110783465B CN110783465B CN201911073466.3A CN201911073466A CN110783465B CN 110783465 B CN110783465 B CN 110783465B CN 201911073466 A CN201911073466 A CN 201911073466A CN 110783465 B CN110783465 B CN 110783465B
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Abstract
The invention relates to the field of manufacturing of photoelectric detectors, in particular to a thermal electron photoelectric detector based on an 8-hydroxyquinoline aluminum/metal heterojunction. The invention also relates to a preparation method of the thermal electron photoelectric detector based on the 8-hydroxyquinoline aluminum/metal heterojunction.
Description
Technical Field
The invention relates to the field of manufacturing of photoelectric detectors, in particular to a thermal electron photoelectric detector based on an 8-hydroxyquinoline aluminum/metal heterojunction and a manufacturing method thereof.
Background
The development of image sensors and the communication industry has increasingly demanded flexible, low-cost, high-response speed photodetectors. Compared with inorganic semiconductors, organic semiconductors have the advantages of flexibility, rich varieties, adjustable band gap, low price and the like. However, the conventional organic semiconductor has a wide energy band, which is not favorable for photoelectric detection of the device in the near infrared/infrared band. In recent years, surface plasmons (SPPs) have attracted considerable attention for achieving manipulation of light-to-substance interactions, photon absorption, thermal emission, wavelength, and energy conversion. The thermal electrons generated by the attenuation of the localized surface plasmon resonance of the metal nanostructure can form a measurable photocurrent on a Schottky barrier formed by the semiconductor and the metal. Therefore, the absorption spectrum of the organic photoelectric detector is widened, and the requirements of people on a new generation of photoelectric detector in production and life are met.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: on the premise of ensuring the low cost advantage of the organic semiconductor device, the efficiency and the bandwidth of the device for absorbing incident light waves are enhanced.
The technical scheme adopted by the invention is as follows: a thermionic photoelectric detector based on an 8-hydroxyquinoline aluminum/metal heterojunction is composed of an anode layer, an organic semiconductor layer, a silver nanoparticle layer and a cathode layer, wherein the anode layer is Indium Tin Oxide (ITO), the silver nanoparticle layer and the cathode layer form a metal composite electrode layer, and the organic semiconductor layer and the metal composite electrode layer form a Schottky junction.
The organic semiconductor layer is 8-hydroxyquinoline aluminum Alq with the thickness of 50 nanometers +/-0.5 nanometers3The silver nano-particle layer is 5 +/-0.03 nano silver Ag nano-particles,
a method for manufacturing a thermionic photodetector based on an 8-hydroxyquinoline aluminum/metal heterojunction is carried out according to the following steps:
step one, ITO glass pretreatment, namely rubbing and washing the ITO glass by using a detergent and a cleaning powder, respectively ultrasonically cleaning the ITO glass for 15 minutes by using absolute ethyl alcohol, acetone and isopropanol, and standing by in the isopropanol.
Step two, thermal evaporation process, using ultraviolet light to irradiate the clean indium tin oxide conductive glass as an anode layer, and evaporating the organic semiconductor Alq with the thickness of 50 +/-0.5 nanometers at the speed of 0.2 nanometers/second3Layer, followed by 5 + -0.03 nm Ag nanoparticles at a low rate of 0.02 nm/sec, and finally 10 + -0.05 nm thick Al cathode at a rate of 0.4 nm/sec.
As a preferred mode: in the second step, Ag is facilitated to form nano particles at a low speed of 0.02 nm/s, and the Al electrode is subjected to shape-preserving evaporation at a high speed of 0.5 nm/s.
The invention has the beneficial effects that: the invention utilizes the surface plasmon effect of the metal Ag nano particles to enhance the absorption efficiency and bandwidth of the device to incident light waves on the premise of ensuring the low cost advantage of the organic semiconductor device. And then obtain the photoelectric detector of high performance, relative to not adding the device of Ag nanoparticle, can obviously increase the bright current under the forward bias to improve the device performance.
The photoelectric detector designed in the invention keeps the dark current at the level of dozens of pico amperes under the condition of forward bias voltage, and the bright current is in an on state.
Drawings
FIG. 1: the invention ultraviolet-visible absorption spectrum;
FIG. 2 is a schematic diagram: the current-voltage curve of the invention under the illumination of 850 nm;
FIG. 3: the current-voltage curve of the invention under 375 nm illumination.
Detailed Description
The materials used in the present invention are: high purity aluminum wire (Al), high purity silver grain (Ag), 8-hydroxyquinoline aluminum (Alq)3) The carvings-carving brand detergent (the components are softened water, surfactant, vitamin E ester and lemon essence) and the deionized water (H)2O), acetone (CH)3COCH3) Isopropyl alcohol (C)3H8OH). The combined dosage is as follows:
al: 2000 mg of
Ag: 1000 mg of
Alq3: 200 mg of
Acetone: 250 ml of
Deionized water: 2000 ml
Isopropyl alcohol: 300 ml
Liquid detergent: 2 plus or minus 0.5 ml
Conductive glass (indium tin oxide ITO): 25 mmol/l × 1 mmol/l
The organic photoelectric detector has four-layer structure including anode layer of ITO, organic semiconductor layer, nanometer silver particle layer and cathode layerA transparent electrode prepared on the glass substrate as a base layer, an organic semiconductor Alq arranged above the anode layer3A layer; ag nano particles are arranged above the organic semiconductor layer; an Al cathode layer is arranged on the cathode layer.
The preparation method comprises the following steps:
(1) selecting chemicals
The chemical material required by preparation is selected, and the quality, purity, concentration, fineness and precision are controlled as follows: (milligrams)
Al: solid filamentous shape with filamentous diameter of 2 mm and purity of 99.99%
Ag: solid particles, phi 2 x 5 mm purity 99.99%
Alq3: solid powder with particle size not more than 28 microns and purity of 98 percent
Acetone: liquid with purity of 99.5%
Deionized water: liquid with purity of 99.99 percent
Isopropyl alcohol: liquid with purity of 99.5%
Conductive glass (indium tin oxide ITO): indium Tin Oxide (ITO), solid, 86% transmittance, sheet resistance of 10 omega/□, surface roughness Ra of 0.16-0.32 nm
(2) Pretreatment of conductive glass
1) Placing indium tin oxide conductive glass in a mixed solution of SDS (sodium dodecyl sulfate) powder and detergent, and carrying out ultrasonic treatment for 1 hour;
2) repeatedly rubbing the front and back sides of the indium tin oxide conductive glass with disposable gloves until the front and back sides are washed by deionized water to form water films;
3) placing the conductive glass in an ultrasonic cleaner, adding deionized water, and ultrasonically cleaning for 15 minutes;
4) placing the conductive glass in an ultrasonic cleaner, adding acetone, and ultrasonically cleaning for 15 minutes;
5) placing the conductive glass in an ultrasonic cleaner, adding isopropanol, and ultrasonically cleaning for 15 minutes;
(3) vacuum evaporation, form conversion, vapor deposition, film growth and preparation of organic photoelectric detector
1) The preparation is carried out in a vacuum evaporation furnace;
2) placing conductive glass
Opening the vacuum evaporation furnace, fixing the conductive glass on a turntable at the top of the furnace chamber, wherein the indium tin oxide surface of the conductive glass faces downwards;
3) winding 2000 mg of aluminum wire on tungsten wire, placing 1000 mg of high-purity silver particles in a tantalum boat, and placing 200 mg of quinoline aluminum in a quartz crucible;
4) adjusting the quartz thickness measuring probe and the quartz monitoring probe on the furnace wall to make the quartz thickness measuring probe align with the conductive glass on the turntable and make the quartz monitoring probe align with Al, Ag and Alq respectively3；
5) Closing the door of the vacuum evaporation furnace and sealing;
6) starting a mechanical vacuum pump and a molecular vacuum pump, and extracting air in the furnace cavity to ensure that the vacuum degree in the furnace is less than or equal to 0.0005 Pa and the vacuum degree is kept constant;
7) starting the turntable, rotating the conductive glass along with the turntable, and rotating the turntable at a speed of 8 r/min;
8) opening a quartz thickness measuring probe;
9) evaporating a quinoline aluminum organic semiconductor layer:
opening to fill Alq3 After the temperature of the quartz crucible is raised to 150 ℃, the quartz crucible is heated to 5 ℃ for one time and slowly raised to about 190 ℃, and at the moment, Alq3 The powder is sublimated from solid state to gas state, the gas state molecules are deposited and grown on the thin silver layer to form a plane film layer, the quartz crucible heating power supply control key is adjusted, the temperature is increased, the film growth rate is maintained at 0.01 nanometer/second, and the film layer thickness is 50 +/-0.5 nanometer;
10) evaporating silver nanoparticles:
firstly, rotating a mask conversion turntable at the top of the furnace chamber to adjust the mask conversion turntable into an electrode mask; starting a power supply of the tantalum boat containing the silver to sublimate the silver from a solid state to a gas state, wherein the gas state molecules are in Alq3 Depositing and growing on the layer, forming Ag into nano particles at a low rate, adjusting a tantalum boat power supply control knob, increasing the current, and maintaining the particle growth rate at 0.02 nm/s and the thickness of 5 +/-0.03 nm;
11) aluminum-plated transparent electrode:
starting a tungsten filament power supply wound with Al to sublimate the Al from a solid state to a gas state, depositing and growing gas molecules on the Ag nano particles to form a covering film layer, adjusting a tantalum boat power supply control knob, increasing current, and maintaining the film growth rate at 0.4 nm/s, wherein the film layer thickness is 10 +/-0.05 nm;
in the 9-11 preparation process, a quartz thickness measuring probe measures the evaporation thickness, and the thickness value is displayed by a display screen;
in the 9-11 preparation process, a middle observation window is used for observing the evaporation process and the evaporation condition;
in the preparation process of 9-11, the evaporation material is heated to sublimate, the form is converted, vapor deposition is carried out on the indium tin oxide surface of the conductive glass, and Alq3 Forming a planar film layer with Al, and forming nano particles with Ag;
14) standing and cooling along with the furnace in vacuum state
After the film layer is evaporated, the organic photoelectric detector is placed in a vacuum furnace to be cooled for 30 minutes;
15) collecting a product: hot electron photoelectric detector based on organic/metal Schottky junction
Closing the molecular vacuum pump and the mechanical vacuum pump;
opening an air inlet valve;
opening a door of the evaporation cabin;
the conductive glass from which the OPD device was prepared was taken out, namely: thermionic photodetectors based on an 8-hydroxyquinoline aluminum/metal heterojunction.
(4) Detection, analysis, characterization
Detecting, analyzing and representing the performance of the prepared organic photoelectric detector;
the transflective integrating sphere is used for representing the light absorption performance of the device in a 300-1100 nanometer wave band; thorlabs M375L4, M850L4 LED light source and semiconductor parameter analyzer B1500A were used to test the dark state and constant illumination current-voltage curves of the devices.
And (4) conclusion: as can be seen from the absorption spectra of the devices with and without Ag nanoparticles (FIG. 1), the addition of Ag nanoparticlesAfter Ag nano particles are formed, the absorption of the device in a 300-1100 nano wave band is obviously improved. From Alq3The absorption spectrum of the film shows that it absorbs little light at a wavelength of 450 nm, which indicates that the thermionic photodetector based on an 8-hydroxyquinoline aluminum/metal heterojunction prepared by us absorbs light substantially by metal at a wavelength of 450 nm, and generates photocurrent. From the contrast graphs (fig. 2 and 3) of the current-voltage in the bright state and the dark state, after the positive bias is applied, the device has good response no matter the 375 nm organic layer with 9.14 mw/cm absorbs the light with the wave band or the 850 nm organic layer with 64 mw/cm does not absorb the light with the wave band, and the photocurrent is caused by the thermal electron emission effect generated by the surface plasmon resonance of the metal nanoparticles. Since the work function of metallic Al is 4.3 electron volts, Alq3The energy levels of HOMO and LUMO are respectively 3.0 electron volt and 5.7 electron volt, the different Fermi energy levels of metal and semiconductor can form Schottky junction after contact, Ag nano particles are added into the prepared device, the local surface plasmon resonance effect of the Ag nano particles can be excited after incident light irradiation, and generated hot electrons can tunnel through the Schottky junction and reach photocurrent formed by two end electrodes. By combining the analysis, the light absorption efficiency of the photoelectric detector is improved by adding the Ag nano particles, so that the bright current of the device is improved, and the thermal electron photoelectric detector based on the 8-hydroxyquinoline aluminum/metal heterojunction is finally obtained.
Compared with the background art, the invention has obvious advancement. An organic semiconductor Alq is prepared on an ITO glass substrate by using a vacuum thermal evaporation technology3The layer, the Ag nano-particle layer and the Al electrode layer finally obtain the thermal electron photoelectric detector based on the 8-hydroxyquinoline aluminum/metal heterojunction. By comparing devices containing and not containing Ag nanoparticles, it was found that the absorption of the photodetector is increased and a bright current is generated in a band that is not absorbed by the organic layer after the Ag nanoparticles are added. Compared with an inorganic semiconductor, the Schottky formed by the organic semiconductor and the metal has the advantages of lower cost and flexibility, and the photoelectric detector with excellent performance can be obtained, so that the potential application value is realized.
Claims (3)
1. A thermal electron photoelectric detector based on 8-hydroxyquinoline aluminum/metal heterojunction is composed of an anode layer, an organic semiconductor layer, a silver nanoparticle layer and a cathode layer, and is characterized in that: the anode layer is Indium Tin Oxide (ITO), the silver nanoparticle layer and the cathode layer form a metal composite electrode layer, the organic semiconductor layer and the metal composite electrode layer form a Schottky junction, and the organic semiconductor layer is 8-hydroxyquinoline aluminum (Alq) with the thickness of 50 nanometers +/-0.5 nanometers3The silver nano-particle layer is 5 +/-0.03 nano silver Ag nano-particles.
2. The method for manufacturing the thermionic photoelectric detector based on the 8-hydroxyquinoline aluminum/metal heterojunction is characterized by comprising the following steps:
rubbing and washing indium tin oxide conductive glass, respectively cleaning the indium tin oxide conductive glass by using deionized water, absolute ethyl alcohol, acetone and isopropanol under an ultrasonic condition, then putting the indium tin oxide conductive glass into an evaporation furnace, and starting evaporation when the pressure is reduced to be below 0.0005 Pa;
secondly, evaporating 50 +/-0.5 nm thick organic semiconductor Alq at the rate of 0.2 nm/sec on the indium tin oxide conductive glass under the rotation condition3Layer, followed by 5 + -0.03 nm silver nanoparticles at a low rate of 0.02 nm/sec, and finally 10 + -0.05 nm thick Al cathode at a rate of 0.4 nm/sec.
3. A method of fabricating a thermionic photodetector based on an 8-hydroxyquinoline aluminum/metal heterojunction as claimed in claim 2 wherein: in the second step, Ag is evaporated at a low rate to form nanoparticles, and then an Al electrode needs to be evaporated in a shape-preserving manner.
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