CN114907846A - Quantum dot material, preparation method and application - Google Patents
Quantum dot material, preparation method and application Download PDFInfo
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Abstract
The application discloses a quantum dot material, a preparation method and application. The quantum dot material is a colloidal quantum dot modified by a modified component; the modified component comprises a polyimide ligand and a lead halide ligand; the colloidal quantum dots comprise at least one of PbS and PbSe. The quantum dot material is a colloidal quantum dot cooperatively modified by organic polymer Polyimide (PI) and lead halide ligand, so that the surface defect of the quantum dot is greatly reduced, the mobility of a carrier is improved, the dark current noise of a detection device is reduced, and the detection performance is improved.
Description
Technical Field
The application relates to a quantum dot material, a preparation method and application thereof, and belongs to the technical field of photoelectric materials.
Background
At present, an organic phase synthesis method is generally adopted to prepare quantum dot materials, that is, quantum dots with uniform size distribution are synthesized by mixing and reacting metal organic compounds and nonmetal elements in an organic solvent environment with coordination property, wherein the organic solvent with coordination property comprises one or more of oleic acid, oleylamine, tri-n-octylphosphine oxide and trioctylphosphine. Excessive organic ligands are coated on the surfaces of the quantum dots to counteract van der waals acting force among the quantum dots, so that the stability of the quantum dot solution is maintained, and the storage and the transportation are facilitated. However, the existence of the organic ligand greatly hinders the transport process of carriers, and the mobility is extremely low, so that the prepared and synthesized quantum dots cannot be directly applied to photoelectric devices, especially photoelectric detectors.
The quantum dot material used in the existing preparation process of the quantum dot detector has inherent problems of low mobility, many surface defects and the like, which can cause the transmission effect of current carriers in the quantum dots to be poor and the defect leakage current to be increased, so that the quantum dot detector has the problems of large dark noise and low light responsiveness. In the existing preparation process, a large number of organic layers are added in a quantum dot layer at equal intervals to inhibit dark noise, but the scheme seriously increases the process difficulty and improves the cost, the photoelectric performance still cannot reach the minimum standard of industrial application, and the application space of the quantum dot detector is seriously influenced. How to realize the modification of quantum dot materials and improve the photoelectric performance of quantum dot detectors is the key of the current field.
Quantum dots passivated by mixed halogen ligands of traditional solid phase exchange (LBL) have the defects of multiple defects, poor mobility and the like, so that the dark current noise of the device is large, and the detection performance is directly influenced.
Disclosure of Invention
According to one aspect of the application, the quantum dot material is a colloidal quantum dot cooperatively modified by organic polymer Polyimide (PI) and a lead halide ligand, so that the surface defects of the quantum dot are greatly reduced, the mobility of carriers is improved, the dark current noise of a detection device is reduced, and the detection performance is improved.
A quantum dot material is a colloidal quantum dot modified by a modified component;
the modified component comprises polyimide and a lead halide ligand;
the colloidal quantum dots comprise at least one of PbS and PbSe.
Optionally, the polyimide ligand is selected from any one of a pyromellitic polyimide, a soluble polyimide, a polyamide-imide, and a polyether imide.
Optionally, the repeating unit in the polyimide ligand is selected from any one of groups with a structural formula shown in a formula I;
in formula I, R 2 Is selected from C 6 ～C 12 Arylene radical, C 6 ～C 15 Any of substituted arylenes.
The R is 2 Any one selected from the following groups;
optionally, the lead halide ligand is selected from PbI 2 、PbBr 2 At least one of (1).
Preferably, the lead halide ligand comprises PbI 2 And PbBr 2 。
PbI 2 And PbBr 2 The mass ratio of (A) to (B) is 4-8: 1.
According to another aspect of the present application, there is also provided a method for preparing the quantum dot material, the method comprising the steps of:
1) obtaining colloid quantum dots modified by lead halide;
2) and dissolving the lead halide modified colloidal quantum dots in an organic solution containing polyimide to obtain the quantum dot material.
Specifically, in the step 2), the colloidal quantum dots modified by the lead halide are dissolved in an organic solution containing polyimide, and the quantum dot material can be obtained by shaking and dissolving.
Optionally, the step 1) comprises:
1-a) obtaining a solution I containing colloidal quantum dots;
1-b) obtaining a solution II containing lead halides;
1-c) mixing the solution I and the solution II, layering to obtain a lower layer solution, and centrifuging to obtain the lead halide modified colloidal quantum dot.
Specifically, the colloidal quantum dots in the step 1-a) are organic ligand colloidal quantum dots, namely, colloidal quantum dots modified by organic ligands in the process of preparing quantum dots. The organic ligand is not critical herein, for example, the organic ligand may be selected from one or more of oleic acid, oleylamine, tri-n-octyloxyphosphine, trioctylphosphine.
The preparation method of the colloidal quantum dots in the present application is a method commonly used in the prior art, and the present application is not strictly limited.
Optionally, in the solution I, the content of the organic ligand colloidal quantum dots is 5-15 mg/mL.
In the step 1-a), the solvent in the solution I is a first organic solvent, and the first organic solvent comprises any one of n-octane, n-hexane and n-pentane;
in the step 1-b), the solvent in the solution II is a second organic solvent, and the second organic solvent comprises any one of N-N dimethyl diamide, dimethyl sulfoxide and methyl formamide.
Optionally, in the step 1-c), adding the solution I containing the organic ligand colloid quantum dots into the solution II containing the lead halide, and performing operation under a closed condition until delamination is achieved to obtain the quantum dots.
Specifically, in the step 1-c), the solution I and the solution II are mixed and operated to be separated under the closed conditionAnd (4) layering to obtain the quantum dot material. Operating under closed conditions, more O can be avoided 2 Contact avoids quantum dot oxidation and sufficient mixing can be achieved.
Optionally, step 1-c) comprises:
1. mixing the solution I and the solution II to obtain a mixed solution, and standing or slightly shaking the mixed solution in a sealed environment until the mixed solution is layered;
2. sucking out supernatant, adding n-octane into the rest solution, and standing or slightly shaking for layering;
3. repeating the step S300-2 for a plurality of times;
4. and centrifuging the obtained lower layer solution to obtain the quantum dot material.
In the step 1-c), adding n-octane into the solution II, adding the solution I, and mixing the solution I and the solution II; and then oscillating for layering, taking out and discarding the upper layer solution, then adding n-octane into the rest solution, oscillating for layering, taking out and discarding the upper layer solution, and thus obtaining the lower layer solution.
Centrifuging the lower layer solution for 4-6 min under the condition of 8000-10000 r/min, discarding the supernatant, and pumping the solvent under a vacuum state to obtain the lead halide modified colloidal quantum dots (powder).
Optionally, in step 4, centrifuging the obtained lower layer solution, discarding the supernatant, and placing the centrifuge tube into a glove box transition bin to drain the solvent (30min-1 h).
Optionally, the mass ratio of the organic ligand colloidal quantum dots to the lead halide is 0.1-1: 10 to 100.
Preferably, the mass ratio of the colloidal quantum dots to the lead halide is 1: 100 to 300.
Optionally, in the step 2), the solvent in the organic solution containing polyimide is at least one selected from N, N-dimethylformamide, N-butylamine, N-pentylamine, N-hexylamine, N-methylformamide, dimethyl sulfoxide, methanol, ethanol, propanol, benzene, toluene and ethylbenzene.
Optionally, the solvents in the organic solution containing polyimide are mixed organic solvents, namely an organic solvent a and an organic solvent b;
the organic solvent a is selected from any one of N, N-dimethylformamide, dimethyl sulfoxide, methanol, ethanol, propanol, benzene, toluene and ethylbenzene;
the organic solvent b is selected from any one of n-butylamine, n-pentylamine and n-hexylamine.
Optionally, in step 2), the organic solution containing polyimide is prepared by a method including at least the following steps:
i) dissolving polyimide in an organic solvent a, and stirring for 20-30 h at the temperature of 30-50 ℃ to obtain a solution i;
ii) adding an organic solvent b to the solution i to obtain the organic solution containing polyimide.
Specifically, the modified component Polyimide (PI) is added before film coating, and is preferably dissolved in N, N-dimethylformamide to prepare a dispersant with corresponding concentration with N-butylamine.
Optionally, in the solution i, the concentration of the polyimide is 10-100 mg/ml;
the volume ratio of the organic solvent b to the solution i is 1: 2-6.
Optionally, the mass-to-volume ratio of the lead halide modified colloidal quantum dots to the polyimide-containing organic solution is 80-100 mg: 200-400 μ L.
Specifically, in the solution i, the upper limit of the concentration of the polyimide is selected from 34mg/ml, 51mg/ml, 68mg/ml, 80 mg/ml; the lower limit of the concentration of the polyimide is selected from the group consisting of 20mg/ml, 34mg/ml, 51mg/ml, 68mg/ml and 80 mg/ml.
The upper limit of the volume ratio of the organic solvent b to the solution i is selected from 1:4 and 1: 6; the lower limit of the volume ratio of the organic solvent b to the solution i is selected from 1:2 and 1: 4.
Preferably, the mass volume ratio of the lead halide modified colloidal quantum dots to the polyimide-containing organic solution is 85-95: 230-270 mg/ml.
The following describes possible methods for preparing quantum dot materials:
the preparation method at least comprises the following steps:
s100, obtaining a solution I containing organic ligand colloidal quantum dots;
s200, obtaining a lead halide-containing solution II;
s300, mixing the solution I and the solution II, and layering to obtain the lead halide ligand modified colloidal quantum dots;
s400, obtaining an N, N-dimethylformamide solution III containing polyimide, mixing a certain amount of N, N-dimethylformamide solution III with N-butylamine, and dissolving the pumped and dried quantum dots modified by the lead halide ligand to obtain the quantum dot material.
In the application, ligand exchange is carried out on a halogen ligand and an organic ligand, and polyimide is introduced for auxiliary passivation before film coating, so that the surface performance of the quantum dot material can be improved.
According to a third aspect of the present application, there is also provided a quantum dot light absorption layer comprising a quantum dot material; the quantum dot material is selected from any one of the quantum dot material described in any one of the above and the quantum dot material obtained by the preparation method described in any one of the above.
The quantum dot light absorption layer provided by the application reduces surface defects to a certain extent through the passivation effect of organic matters on the surface after PI is introduced, so that the performance of a device is greatly improved.
Optionally, the thickness of the light absorption layer of the quantum dots is 100-700 nm.
According to a fourth aspect of the present application, there is also provided a method of preparing a quantum dot light absorbing layer, the method comprising:
and transferring the solution containing the quantum dot material to a substrate, and annealing to obtain the quantum dot light absorption layer.
Specifically, in one example, when the quantum dot light absorption layer is prepared in the device, a solution containing quantum dots may be coated in the substrate, and then annealed to obtain the quantum dot light absorption layer, and then other layered structures may be prepared on the quantum dot light absorption layer.
The "layered structure" in the present application may be a functional layer or a non-functional layer as long as it has a layered structure.
And centrifuging the solution containing the quantum dot material, transferring the solution onto a substrate, and annealing to obtain the quantum dot light absorption layer.
Optionally, the solvent in the solution containing the quantum dot material is selected from at least one of N, N-dimethylformamide, N-butylamine, N-pentylamine, N-hexylamine, N-methylformamide, and dimethyl sulfoxide.
Optionally, the solvent in the solution containing the quantum dot material is a mixed organic solvent, namely an organic solvent a and an organic solvent b. The organic solvent a is selected from any one of N, N-dimethylformamide, N-methylformamide and dimethyl sulfoxide; the organic solvent b is selected from any one of n-butylamine, n-pentylamine and n-hexylamine.
Preferably, the solvent is N-butylamine and N, N-dimethylformamide, and the volume ratio of the N-butylamine to the N, N-dimethylformamide is 1:2 to 6.
Optionally, in the solution containing the quantum dot material, the content of the quantum dot material is 200-600 mg/mL.
Optionally, the annealing conditions are: the annealing temperature is 60-120 ℃; the annealing time is 7-30 min.
Specifically, the upper limit of the annealing temperature is selected from 80 ℃, 90 ℃, 100 ℃, 110 ℃ and 120 ℃; the lower limit of the annealing temperature is selected from 60 deg.C, 80 deg.C, 90 deg.C, 100 deg.C, and 110 deg.C.
The upper limit of the annealing time is selected from 10min, 20min and 30 min; the lower limit of the annealing time is selected from 7min, 10min and 20 min.
According to a fifth aspect of the present application, there is also provided a device comprising the quantum dot light absorption layer as claimed in any one of the above claims, and the quantum dot light absorption layer obtained by the preparation method as claimed in any one of the above claims.
According to the sixth aspect of the application, a preparation method of the device is further provided, wherein the solution containing the quantum dots is transferred onto the substrate and annealed to obtain the quantum dot light absorption layer;
and coating other layered structures on the quantum dot light absorption layer to obtain the device.
According to a seventh aspect of the present application, there is also provided an infrared detector, which sequentially comprises, from bottom to top, ITO conductive glass, a ZnO electron transport layer, a quantum dot light-absorbing layer, a PbS-EDT hole transport layer, and an Au electrode;
the quantum dot light absorption layer is selected from any one of the quantum dot light absorption layer and the quantum dot light absorption layer obtained by the preparation method.
In this application, C 6 ～C 10 The number of carbon atoms contained in the group is 6-10;
the term "arylene" refers to a group formed by losing two hydrogen atoms on a benzene ring in an aromatic compound molecule, and may be two hydrogen atoms on the same benzene ring or two hydrogen atoms on different benzene rings.
"substituted arylene" refers to a group in which any hydrogen atom on the arylene group has been replaced with a substituent.
"PI" means polyimide.
"EDT" refers to 1, 2-ethanedithiol.
The beneficial effects that this application can produce include:
1) compared with the prior art, the ligand passivation modification of PbS/PbSe CQDs is mainly carried out by passivating short-chain organic matters or mixed halogen ligands, and compared with the modification mode, the invention introduces PI auxiliary passivation and performance adjustment in the mixed halogen ligands in the process of passivating PbS or PbSe colloid quantum dots, thereby obtaining more excellent passivation effect, and the performance of PC/PV devices prepared by quantum dots obtained by the method is obviously improved.
Drawings
FIG. 1 is a current-voltage plot (I-V) of a quantum dot detector of comparative example 1 of the present application without PI assisted passivation;
fig. 2 is a current-voltage graph (I-V) of a quantum dot detector using PI assisted passivation in an embodiment of the present application.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were purchased commercially, unless otherwise specified.
One, PbS-PbX 2 Ligand exchange
The process flow comprises the following steps:
1. weighing the mass of the quantum dots in the centrifuge tube, and taking n-octane by using a pipette to prepare a quantum dot solution with the concentration of 5-15mg/mL to ensure complete dissolution.
2. Weighing lead iodide (PbI) in a glove box 2 ) Lead bromide (PbBr) 2 ) Adding into a centrifuge tube (if ligand exchange is carried out in a glove box, adding into a glass bottle, sealing with a sealing glue and tin foil, and taking out), and adding 10-30mL DMF to prepare a ligand solution. Dissolution was accelerated by ultrasonic heating in an ultrasonic washer while shaking every few minutes.
3. The ligand solution was filtered into a clean glass vial using a syringe and filter head.
4. Filtering the quantum dot solution into a glass bottle filled with the ligand solution by using an injector and a filter head, screwing a bottle cap, manually oscillating, standing or slightly shaking to layer the solution; if no obvious layering exists after standing, the solution needs to be divided into two parts, diluted by n-octane and then the supernatant liquid is sucked out by a dropper.
5. Adding n-octane by using a pipette, manually oscillating, standing or slightly shaking to separate the solution, and sucking out supernatant and gray substances floating between the two layers by using a dropper. This was repeated twice.
6. Weigh the labeled centrifuge tube mass m 1. And (3) centrifuging the solution at the middle lower layer of the glass bottle in a centrifugal tube at 9000r for 5min, removing supernatant, wiping off residual liquid on the tube wall of the tube opening by using a cotton swab, and putting the centrifugal tube into a glove box transition bin to drain the solvent (30min-1 h).
7. Placing the centrifuge tube into a glove box, weighing mass m2 to obtain PbS-PbX with mass m2-m1 2 (i.e., quantum dot material) for use.
In step 6, a plurality of centrifuge tubes may be used, and those skilled in the art can select the centrifuge tubes according to actual needs.
Secondly, spin-coating PbS-PbX 2 Layer(s)
The process flow comprises the following steps:
1. polyimide (PI) is dissolved in DMF in a glove box to prepare a mixed solution with a certain concentration, the mixed solution is stirred at the low temperature of 40 ℃ for 24 hours, and when the mixed solution is used, the mixed solution is mixed with n-Butylamine (BTA), and the mixture is uniformly shaken to prepare an amine solution.
2. To the bottom is provided with PbS-PbX 2 The amine solution is added into a solid centrifuge tube, the concentration is prepared to be 200-400mg/ml, and a small oscillator is used for slowly oscillating for 1-2min, so that the quantum dots are completely dissolved. (A total of about 300uL of solution was made up in this amount).
3. The solution was transferred to a small centrifuge tube and centrifuged at 3000r for 30s-1 min.
4. And (3) opening a power supply and an air pump of the spin coater, and setting the rotating speed to be 2500r/min, the time to be 40s and the acceleration to be 500. The device was attached to a tray and surface dust was blown off with an ear-washing bulb.
5. Spin coating of PbS-PbX 2 Amine solution.
6. Adjusting the temperature of the heating table to 60-100 ℃, annealing for 7-10min, and removing the amine solution.
The following describes a method for preparing organic ligand colloidal quantum dots (i.e., colloidal quantum dots):
preparing PbS quantum dots: refer to Diffusion-Controlled Synthesis of PbS and PbSe Quantum Dots with in Situ Hall Effect for Quantum Dot Solar cells ACS Nano 2014,8, 614-22.
Preparing PbSe quantum dots: refer to Diffusion-Controlled Synthesis of PbS and PbSe Quantum Dots with in Situ Hall Effect for Quantum Dot Solar cells ACS Nano 2014,8, 614-22.
The polyimide used in the examples was represented by the following formula, and was purchased from sigma with a polymerization degree n of 100 to 200.
Example 1 Quantum dot Material with PI-assisted passivation (PbS-PIPBX) 2 ) Is/are as followsPreparation of
a) Dissolving PbS quantum dots with an absorption peak value of 1300nm in n-octane to obtain a solution I containing organic ligand colloidal quantum dots with the concentration of 10 mg/mL;
b) weighing 1.8g of PbI 2 ，0.3g PbBr 2 20mL of N-N dimethylformamide is added into a 50mL centrifuge tube and dissolved in an ultrasonic machine in a water bath to obtain a mixed ligand, namely solution II.
c) 10mL of the mixed ligand (solution II) was placed in a clean 40mL glass vial, 10mL of n-octane was added to the vial, and 5mL of solution I was added.
d) Shaking the glass bottle until the solution is layered, wherein the lower layer solution is black, the upper layer solution is brown, taking out and discarding the upper layer solution, adding 10mL of n-octane into the glass bottle, shaking for 2min, taking out and discarding the upper layer solution.
e) The solution was centrifuged for 5min at 9000r/min in two 10mL centrifuge tubes. And centrifuging, removing supernatant, placing the centrifuge tube into a glove box transition bin, keeping the vacuumizing state for a certain period of 1 hour, and draining the solvent to obtain the quantum dot powder (namely the colloidal quantum dot modified by the lead halide) with the regulated surface state.
f) Polyimide powder was dissolved in DMF to prepare a 51mg/ml solution, stirred at 40 ℃ for 24h, then the stirring was stopped, filtered, and the filtered solution was mixed with n-butylamine (volume ratio of filtered solution to n-butylamine was 4:1) obtaining an organic solution containing polyimide;
dissolving the quantum dots (90mg) modified by the lead halide in organic solution (300 mu L) containing polyimide to form the quantum dot material PbS-PI/PbX 2 。
Comparative example 1 Quantum dot Material without PI-assisted passivation (PbS-PbX) 2 ) Preparation of (2)
a) Dissolving PbS quantum dots with an absorption peak value of 1300nm in n-octane to obtain a solution I containing organic ligand colloidal quantum dots with the concentration of 10 mg/mL;
b) weighing 1.8g of PbI 2 ，0.3g PbBr 2 20mL of the solution was added to a 50mL centrifuge tubeDissolving N-N dimethylformamide in water bath in an ultrasonic machine to obtain a mixed ligand, namely solution II.
c) 10mL of the mixed ligand (solution II) was placed in a clean 40mL glass vial, 10mL of n-octane was added to the vial, and 5mL of solution I was added.
d) Shaking the glass bottle until the solution is layered, wherein the lower layer solution is black, the upper layer solution is brown, taking out and discarding the upper layer solution, adding 10mL of n-octane into the glass bottle, shaking for 2min, taking out and discarding the upper layer solution.
e) The solution was centrifuged for 5min at 9000r/min in two 10mL centrifuge tubes. And centrifuging, removing supernatant, putting the centrifuge tube into a glove box transition bin, keeping a vacuumizing state for a certain period of 1 hour, and vacuumizing to dry the solvent to obtain quantum dot powder (namely colloidal quantum dots modified by lead halide) with the regulated surface state.
f) DMF was mixed with n-butylamine in advance to form a mixed amine solution (volume ratio of DMF to n-butylamine was 4: 1).
Dissolving the quantum dots (90mg) modified by the lead halide in mixed amine solution (300 mu L) to form the quantum dot material PbS-PbX 2 。
Example 2PbS-PI/PbX 2 Preparation of quantum dot detector 1 #:
1) dissolving polyimide powder in DMF to prepare 34mg/ml solution, stirring at 40 ℃ for 24h, stopping stirring, filtering, mixing with n-butylamine to prepare a mixture with the volume ratio of 1:4 (ratio of n-butylamine to filtered solution) of weakly polar solution, PbS/PbX towards the bottom 2 Adding 300 mu L of weak polar solution into a centrifuge tube of quantum dot powder (90mg), and shaking for dissolving to obtain a surface state-regulated quantum dot solution (the concentration is 250 mg/mL).
2) And transferring the quantum dot solution with the regulated surface state into a small centrifuge tube, and centrifuging at 3000r for 1min to obtain a lower-layer solution.
3) Magnetron sputtering 300nm ZnO on clean ITO conductive glass to obtain an electron transport layer, spin-coating a quantum dot solution (i.e. a lower layer solution obtained by centrifugation) with surface state regulation and control at a rotation speed of 2500r/min on the electron transport layer, and then heating at 100 deg.CAnnealing for 15min to obtain PbS-PI/PbX 2 A quantum dot light absorption layer (thickness 200 nm);
4) and spin-coating PbS-EDT with the thickness of about 10nm on the quantum dot light absorption layer to obtain a hole transmission layer, and vapor-plating a 100nm Au electrode on the hole transmission layer to obtain the quantum dot detector for reducing the dark current, wherein the quantum dot detector is marked as a quantum dot detector 1 #.
Example 3PbS-PI/PbX 2 Preparation of quantum dot detector 2 #:
1) dissolving polyimide powder in DMF in advance to prepare a solution of 51mg/ml, stirring at 40 ℃ for 24 hours, stopping stirring, filtering, mixing with n-butylamine, and preparing a mixture with a volume ratio of 1:4 (ratio of n-butylamine to filtered solution) of weakly polar solution based on PbS/PbX 2 Adding 300 mu L of weak polar solution into a centrifuge tube of quantum dot powder (90mg), and shaking for dissolving to obtain a surface state-regulated quantum dot solution (the concentration is 250 mg/mL).
2) And transferring the quantum dot solution with the regulated surface state into a small centrifuge tube, and centrifuging at 3000r for 1min to obtain a lower-layer solution.
3) Carrying out magnetron sputtering on 300nm ZnO on clean ITO conductive glass to obtain an electron transmission layer, spin-coating a quantum dot solution (namely a lower layer solution obtained by centrifugation) with the surface state regulated after centrifugation on the electron transmission layer at the rotating speed of 2500r/min, and then annealing at 100 ℃ for 15min to obtain PbS-PI/PbX 2 A quantum dot light absorption layer (thickness of 200 nm);
4) and spin-coating PbS-EDT with the thickness of about 10nm on the quantum dot light absorption layer to obtain a hole transmission layer, and vapor-plating a 100nm Au electrode on the hole transmission layer to obtain the quantum dot detector for reducing the dark current, wherein the quantum dot detector is marked as a quantum dot detector 2 #.
Example 4PbS-PI/PbX 2 Preparation of quantum dot detector 3 #:
1) dissolving polyimide powder in DMF to prepare a 68mg/ml solution, stirring at 40 ℃ for 24 hours, stopping stirring, filtering, mixing with n-butylamine to prepare a mixture with a volume ratio of 1:4 (ratio of n-butylamine to filtered solution) of weakly polar solution, PbS/PbX towards the bottom 2 Adding 300 mu L of weak polar solution into a centrifugal tube of quantum dot powder (90mg), and oscillating for dissolving to obtain surface state-regulated quantum dot solution (the concentration is 250 mg)/mL)。
2) And transferring the quantum dot solution with the regulated surface state into a small centrifuge tube, and centrifuging at 3000r for 1min to obtain a lower-layer solution.
3) Carrying out magnetron sputtering on 300nm ZnO on clean ITO conductive glass to obtain an electron transmission layer, spin-coating a quantum dot solution (namely a lower layer solution obtained by centrifugation) with a surface state regulated and controlled on the electron transmission layer at a rotating speed of 2500r/min, and then annealing at 100 ℃ for 15min to obtain PbS-PI/PbX 2 A quantum dot light absorption layer (thickness 200 nm);
4) and spin-coating PbS-EDT with the thickness of about 10nm on the quantum dot light absorption layer to obtain a hole transmission layer, and vapor-plating a 100nm Au electrode on the hole transmission layer to obtain the quantum dot detector for reducing the dark current, wherein the quantum dot detector is marked as a quantum dot detector 3 #.
Comparative example 1 preparation of a Quantum dot Detector without PI-assisted passivation
The preparation of a quantum dot detector without PI-assisted passivation was similar to the preparation of detector 1# in example 1, except that: the PI-DMF from example 1 was replaced by pure DMF.
Example 5 Performance testing of a Quantum dot Detector (with and without PI-assisted passivation)
The quantum dot detector 1# adopting PI auxiliary passivation and the quantum dot detector not adopting PI auxiliary passivation in the comparative example 1 are respectively tested, and the test results are shown in figures 1 and 2;
fig. 1 is a graph of current-voltage curves (I-V) for a device made in comparative example 1 without PI-assisted passivation. In fig. 1, P1, P2, P3 and P4 respectively represent different operating points selected on the same device according to the principle of uniform collection, where "dark" represents a current value obtained by testing a dark current of the device under the dark and no-light conditions, and "bright" represents a current value obtained by testing a photocurrent generated when the device is irradiated by 1300nm light.
Table 1 shows dark currents (J) at 0.01V and 0.5V at four different operating points, 1,2, 3 and 4, selected on the same device according to the principle of uniform collection, of a photodetector device which is not passivated with the aid of PI and is numbered in comparative example 1 dark ) With photoelectric External Quantum Efficiency (EQE)Numerical size wherein the external quantum efficiency of the data of Table one is according to the formula
And (6) calculating.
TABLE 1
As can be seen from fig. 1 and table 1: the dark current (-0.5V) of the device is about 30000nA, the EQE (-0.5V) is about 30 percent, and the starting voltage is about 0.26V (which indicates that the device has more defects and larger series resistance)
Fig. 2 is a graph of the current-voltage curves (I-V) for a device fabricated using PI assisted passivation in example 1. In fig. 2, P1, P2, P3 and P6 respectively represent different operating points selected on the same device according to the principle of uniform collection, where "dark" represents a current value obtained by testing a dark current of the device under the dark and non-illumination conditions, and "bright" represents a current value obtained by testing a photocurrent generated when the device is irradiated by 1300nm light.
Table 2 shows dark currents (J) at 0.01V and 0.5V at four different operating points P1, P2, P3 and P6 selected on the same device according to the principle of uniform collection for the photodetector device using PI-assisted passivation in example 1 (J) dark ) And the magnitude of the External Quantum Efficiency (EQE), wherein the external quantum efficiency of the data in table one is according to the formula
And (6) calculating.
TABLE 2
As can be seen from fig. 2 and table 2: the dark current (-0.5V) of the device is about 500-600nA (the reduction is about two orders of magnitude), the EQE (-0.5V) is about 50%, and the detection performance of the device is greatly improved, wherein the turn-on voltage of the device is-0.28V (the defect of the device is less, and the series resistance is small).
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. The quantum dot material is characterized in that the quantum dot material is a colloidal quantum dot modified by a modified component;
the modified component comprises polyimide and a lead halide ligand;
the colloidal quantum dots comprise at least one of PbS and PbSe.
2. The quantum dot material of claim 1, wherein the polyimide is selected from any one of a pyromellitic polyimide, a soluble polyimide, a polyamide-imide, and a polyether imide.
3. The quantum dot material of claim 1, wherein the repeating unit in the polyimide is selected from any one of groups having a structural formula shown in formula I;
in the formula I, R 2 Is selected from C 6 ～C 12 Arylene radical, C 6 ～C 15 Any of substituted arylenes;
preferably, said R is 2 Selected from any one of the following groups,
4. the quantum dot material of claim 1, wherein the lead halide ligands are selected from PbI 2 、PbBr 2 At least one of (a).
5. A method of preparing a quantum dot material according to any of claims 1 to 4, characterized in that the method comprises the steps of:
1) obtaining colloid quantum dots modified by lead halide;
2) and dissolving the colloidal quantum dot modified by the lead halide in an organic solution containing polyimide to obtain the quantum dot material.
6. The method of claim 5, wherein the step 1) comprises:
1-a) obtaining a solution I containing colloidal quantum dots;
1-b) obtaining a solution II containing lead halides;
1-c) mixing the solution I and the solution II, layering to obtain a lower layer solution, and centrifuging to obtain lead halide modified colloidal quantum dots;
preferably, in the step 2), the solvent in the organic solution containing polyimide is at least one selected from the group consisting of N, N-dimethylformamide, N-butylamine, N-pentylamine, N-hexylamine, N-methylformamide, dimethyl sulfoxide, methanol, ethanol, propanol, benzene, toluene, and ethylbenzene;
preferably, the solvent in the organic solution containing polyimide is a mixed organic solvent, namely an organic solvent a and an organic solvent b;
the organic solvent a is selected from any one of N, N-dimethylformamide, N-methylformamide, dimethyl sulfoxide, methanol, ethanol, propanol, benzene, toluene and ethylbenzene;
the organic solvent b is selected from any one of n-butylamine, n-pentylamine and n-hexylamine;
preferably, in the step 2), the organic solution containing polyimide is prepared by a method at least comprising the following steps:
i) dissolving polyimide in an organic solvent a, and stirring for 20-30 h at the temperature of 30-50 ℃ to obtain a solution i;
ii) adding an organic solvent b to the solution i to obtain the organic solution containing polyimide;
preferably, in the solution i, the concentration of the polyimide is 10-100 mg/ml;
the volume ratio of the organic solvent b to the solution i is 1: 2-6;
preferably, the mass-to-volume ratio of the lead halide modified colloidal quantum dots to the polyimide-containing organic solution is 80-100 mg: 200-400 μ L.
7. A quantum dot light absorption layer is characterized by comprising a quantum dot material;
the quantum dot material is selected from any one of the quantum dot material of any one of claims 1 to 4, or the quantum dot material obtained by the preparation method of any one of claims 5 or 6;
preferably, the thickness of the quantum dot light absorption layer is 100-700 nm.
8. The method for preparing a light absorbing layer of quantum dots as claimed in claim 7, wherein the method comprises:
transferring the solution containing the quantum dot material to a substrate, and annealing to obtain the quantum dot light absorption layer;
preferably, the solvent in the solution containing the quantum dot material is selected from at least one of N, N-dimethylformamide, N-butylamine, N-pentylamine, N-hexylamine, N-methylformamide, and dimethyl sulfoxide;
preferably, the solvent in the solution containing the quantum dot material is a mixed organic solvent, namely an organic solvent a and an organic solvent b;
preferably, in the solution containing the quantum dot material, the content of the quantum dot material is 200-600 mg/mL;
preferably, the annealing conditions are: the annealing temperature is 60-120 ℃; the annealing time is 7-30 min.
9. A device comprising the quantum dot light absorbing layer of claim 7, the quantum dot light absorbing layer obtained by the preparation method of claim 8;
preferably, the solution containing the quantum dots is transferred to a substrate and annealed to obtain a quantum dot light absorption layer;
and coating other layered structures on the quantum dot light absorption layer to obtain the device.
10. An infrared detector is characterized by comprising ITO conductive glass, a ZnO electron transmission layer, a quantum dot light absorption layer, a PbS-EDT hole transmission layer and an Au electrode from bottom to top in sequence; wherein, the quantum dot light absorption layer is selected from any one of the quantum dot light absorption layer in claim 7 and the quantum dot light absorption layer obtained by the preparation method in claim 8.
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