CN111926389B - Bipolar organic single crystal grown by molecular blending, preparation method and application thereof - Google Patents
Bipolar organic single crystal grown by molecular blending, preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a bipolar organic single crystal grown by molecular blending, a preparation method and application thereof, belonging to the technical field of photoelectrons. The invention provides a method for growing a bipolar organic single crystal with balanced charge transmission by using controllable molecular blending aiming at the problem that the performance of an OLED device is limited by unbalanced unipolar charge transmission of the organic single crystal, solves the major difficult problem of poor performance of the OLED device and obviously improves the performance of the OLED device.
Description
Technical Field
The invention belongs to the technical field of photoelectrons, and particularly relates to a bipolar organic single crystal with balanced charge transmission prepared by controllable blending growth of p-type molecules and n-type molecules, which is applied to a light-emitting device comprising an organic field effect transistor OFET and an organic light-emitting diode OLED, so that the purpose of improving the performance of an organic single crystal photoelectric device is realized.
Background
Organic single crystal crystalline materials have higher charge transport characteristics and more excellent optical properties than amorphous thin films, which have attracted increasing attention in the field of optoelectronics and are applied to various types of optoelectronic devices, such as Organic Light Emitting Transistors (OLETs), Organic Field Effect Transistors (OFETs), optically pumped lasers and Organic Light Emitting Diodes (OLEDs). However, unipolar charge transport is a common problem in organic semiconductors, most of which have p-type characteristics, causing hole and electron mobilities that differ by up to 2-3 orders of magnitude. The highly unbalanced charge transport of unipolar organic semiconductors results in exciton recombination regions near the metal electrode and causes exciton quenching, or charge accumulation and higher electric fields at the metal and organic interface, which severely limits the high efficiency and stability of OLEDs.
The unbalanced charge transport of amorphous thin film OLEDs can be compensated by introducing pn or pin heterojunctions, thanks to their flexibility in device structure design and fabrication. However, the organic single crystal heterojunction of a multi-layered structure is difficult to prepare due to the limitation of the organic single crystal growth strategy. Therefore, new methods and techniques are urgently needed to solve the problem of unipolar charge transport of organic single crystal crystals.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for growing a bipolar organic single crystal with balanced charge transmission by using controllable molecular blending.
The invention is realized by the following technical scheme:
the method for growing the bipolar organic single crystal by using the molecular blending comprises the following specific steps:
firstly, mixing a p-type material and n-type material powder according to a certain mass ratio, placing the mixture in a mortar, adding an organic solvent, fully grinding the mixture for 10-30min, and placing the mixture in an oven to dry the mixture so as to remove the solvent, thereby obtaining uniformly mixed material powder; then, placing the uniformly mixed powder in a high-temperature sublimation area of a double-temperature-area tube furnace; and finally, introducing carrier gas with stable flow rate into the tube furnace, setting the respective temperature and growth time of the two temperature zones, starting heating, and growing the flaky bipolar single crystal suspended on the wall of the quartz tube by using a Physical Vapor Transport (PVT) method.
Further, the p-type material is 1, 4-bis (4-methylstyrene-based) benzene (BSB-Me), 2, 6-Diphenylanthracene (DPA),1, 4-bis (5-phenylthiophen-2-yl) benzene (AC5),2, 5-bis [4- (5 '-phenylthiophen-2' -yl) phenyl ]Thiophene (AC ' 7), trans-1, 4-distyrylbenzene (trans-DSB),2, 5-bis (4-biphenyl-4-yl) thiophene (BP1T),2, 5-bis (4' -methoxybiphenyl-4-yl) thiophene (BP1T-OMe), 5,5' -bis (4-biphenyl) -2, 2' -bithiophene (BP2T),5, 5'-bis ([1, 1' -biphenyl)]-4-yl) -2,2 '-bifuran (BP2F), tetraphenyl (TPPy), 4, 4' -diphenylethenylene anthracene (DPVA), 2, 5-diphenyl-1, 4-distyrylbenzene (trans-DPDSB), a, ω -bis (biphenyl) p-thiophene (BP3T),2, 7-dioctyl [1 ] o]Benzothieno [3,2-B]Benzothiophene (C8-BTBT), P6T, α -tetrathiophene (α -4T), α -dithiophene (α -6T), P-xylene (P-6P), anthracene, tetracene, pentacene, perylene or rubrene; the n-type material is 2,2' -bis [4- (trifluoromethyl) phenyl]-5,5' thiazole (BTPB), 1, 4-bis (5- [4- (trifluoromethyl) phenyl)]Thiophen-2-yl) benzenes (AC 5-CF)3) 2,5-bis (4' -cyanostilbene-4-yl) thiophene (BP1T-CN), fluorinated tetracyanoquinodimethane (F2-TCNQ), PDIF-CN2Or diimide (PTCDI), the mass ratio of p-type and n-type materials is 100: (0.1-50).
Further, the ground organic solvent is acetone or ethanol, the dosage is 1-5mL, the drying temperature is 100-120 ℃, and the drying time is 1-2 h; the mass of the mixed powder used for growing the single crystal is 2-5mg, the carrier gas is argon, the flow rate is 20-45mL/min, the temperature of the high-temperature region of the double-temperature-region tubular furnace is 270 DEG, the temperature of the low-temperature region is 230 DEG and 245 DEG, and the growth time is 120 DEG and 300 min.
The invention also provides application of the organic single crystal prepared by the method for growing the bipolar organic single crystal by molecular blending in the aspect of a luminescent device, which comprises the following steps:
firstly, the method for preparing the OFET device by using the bipolar organic single crystal comprises the following specific steps:
(1) preparing a substrate:
firstly, ultrasonically cleaning a substrate in acetone, ethanol and deionized water for 10-30min, drying the substrate by using nitrogen, placing the substrate in a culture dish, and placing the culture dish in an oven at 95 ℃ for 5-10 min; then, putting the substrate into a vacuum chamber of a plasma cleaning machine, and introducing oxygen to carry out hydrophilic modification on the surface of the plasma;
(2) and preparing an OFET device:
spin-coating a uniform organic polymer layer on the substrate by spin coater to form an insulating layer, and mixing with dense SiO2The films are used as a double-layer insulating layer together; then, toThermally annealing the substrate coated with the insulating layer in a spinning mode, and transferring the bipolar single crystal to the insulating layer of the substrate by using anti-static tweezers after thermal annealing; subsequently, gold wires were used as OFET source and drain masks on the surface of the organic crystal; finally, placing the device behind the gold wire mask in an organic vacuum evaporation chamber, and growing a source drain electrode to finish the preparation of the whole device; wherein the gate is highly doped conductive Si.
Further, the substrate is a highly doped silicon substrate of single-sided silicon dioxide, i.e. Si/SiO2A substrate having dimensions of 2cm x 1.8 cm; the surface hydrophilic modification treatment method is to introduce oxygen gas flow into a plasma vacuum cavity at the flow rate of 20-50mL/min for 3-10 min.
Further, the organic polymer insulating layer is polymethyl methacrylate (PMMA), the concentration is 30-60mg/mL, the solvent is toluene or anisole, the dosage is 50-300 mu L, the spin-coating rotating speed is 2000-4000 r/min, the spin-coating time is 5-20s, and the thickness is 50-200 nm; the thermal annealing process is firstly carried out in a nitrogen glove box (<0.1ppm O2；<0.1ppm H2O) is pre-annealed for 1 to 3 hours at the temperature of between 90 and 120 ℃, and then secondary annealing is carried out for 10 to 30min at the temperature of between 60 and 90 ℃; the diameter of the gold wire is 10-30 μm; the source and drain electrodes are composite electrodes of Ca/Ag or Au, the thicknesses of the composite electrodes are 8-15nm/80-120nm and 80-120nm respectively, the growth speeds of the composite electrodes are respectively
Secondly, the OLED device is prepared by using the bipolar organic single crystal, and the specific steps are as follows:
the preparation sequence of each layer in the device structure is as follows: hole transport layer/anode growth → template lift-off transfer → electron transport layer/cathode growth;
(1) preparing a substrate:
firstly, ultrasonically cleaning a substrate in acetone, ethanol and deionized water for 10-30min, drying the substrate by using nitrogen, placing the substrate in a culture dish, and placing the culture dish in an oven at 95 ℃ for 5-10 min; secondly, dripping the hydrophobic modifier on the blank of the bottom of the culture dish containing the substrate by using a pipette and covering and sealing the blank, and further placing the whole culture dish in a vacuum oven to volatilize the hydrophobic modifier and perform super-hydrophobic modification on the surface of the substrate; finally, the substrate which is finished with modification is sequentially placed in acetone, ethanol and deionized water for ultrasonic cleaning for 10-30min, and is dried by nitrogen;
(2) And preparing an OLED device:
transferring the bipolar organic single crystal to a substrate which is subjected to hydrophobic treatment and is cleaned; covering an anode mask plate under the condition of not damaging the crystal, putting the anode mask plate into an organic vacuum evaporation chamber, and depositing a hole transport layer and an anode on the organic crystal through thermal evaporation; then, a drop of photoresist was placed on the device and pressed against a glass substrate, which spread the photoresist over the edge of the entire glass; subsequently, exposure to UV light, the photoresist cured and the device was peeled from the substrate with a blade, i.e. the device was transferred to a glass substrate; and finally, placing the device in an organic vacuum evaporation chamber again, covering a cathode mask plate, and sequentially growing an electron transport layer and a cathode to finish the preparation of the whole device.
Further, the substrate is a silicon substrate with double-sided silicon dioxide, and the size of the substrate is 1.6cm multiplied by 1.4 cm; the hydrophobic modifier is Octadecyltrichlorosilane (OTS), the dosage is 10-30 mu L, the modification temperature is 40-60 ℃, and the modification time is 4-12 h; the vacuum degree of the vacuum drying oven is 0.1 MPa.
Further, the hole transport layer/anode is MoO3Ag, thickness of 4-12nm and 80-200nm, growth rate of 
And
the photoresist used was NOA63 in an amount of 100-300 μ L, the photoresist stabilization time was 3-8min, and the exposure curing time under UV lamp was 15-17 min; the electron transport layer/cathode is TPBi/Ca/Ag, wherein TPBi is the electron transport layer, Ca/Ag is the composite cathode, the thicknesses are respectively 40-80nm, 8-15nm and 15-25nm, the growth speeds are respectively
And
compared with the prior art, the invention has the following advantages:
(1) the bipolar organic single crystal prepared by blending and growing the p-type molecules and the n-type molecules balances charge transmission to the maximum extent, improves exciton recombination efficiency and finally obviously improves the luminous performance of the organic single crystal OLED device.
(2) The invention uses a single light-emitting layer to replace a multi-layer structure of a pn or pin heterojunction, and simplifies the structure and the processing technology of the device.
Drawings
FIG. 1 is a graph showing the variation trend of electron and hole mobility of bipolar organic single crystals with different BTPB mixing ratios according to the present invention;
FIG. 2 is a luminance graph of bipolar organic single-crystal OLED devices with different BTPB mixing ratios according to the present invention;
FIG. 3 is a current efficiency diagram of bipolar organic single-crystal OLED devices with different BTPB mixing ratios according to the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
Example 1
The method for growing the bipolar organic single crystal by using the molecular blending comprises the following specific steps:
firstly, mixing a p-type material and n-type material powder according to a certain mass ratio, placing the mixture in a mortar, adding an organic solvent, fully grinding the mixture for 10-30min, and placing the mixture in an oven to dry the mixture so as to remove the solvent, thereby obtaining uniformly mixed material powder; then, placing the uniformly mixed powder in a high-temperature sublimation area of a double-temperature-area tube furnace; and finally, introducing carrier gas with stable flow rate into the tube furnace, setting the respective temperature and growth time of the two temperature zones, starting heating, and growing the flaky bipolar single crystal suspended on the wall of the quartz tube by using a Physical Vapor Transport (PVT) method.
The p-type material is 1, 4-bis (4-methyl styryl) benzene (BSB-Me), the n-type material is 2,2 '-bis [4- (trifluoromethyl) phenyl ] -5,5' thiazole (BTPB), and the mass ratio of the p-type material to the n-type material is 100: (1-15); the used ground organic solvent is acetone or ethanol, the dosage is 1-5mL, the drying temperature is 100-; the mass of the mixed powder used for growing the single crystal is 2-5mg, the carrier gas is argon, the flow rate is 20-45mL/min, the temperature of the high-temperature region of the double-temperature-region tubular furnace is 270 DEG, the temperature of the low-temperature region is 230 DEG and 245 DEG, and the growth time is 120 DEG and 300 min.
Example 2
1. The method for preparing the OFET device by utilizing the bipolar organic single crystal grown by molecular blending comprises the following specific steps:
(1) preparing a substrate;
first, Si/SiO2Substrate (Single-sided SiO)2) Sequentially carrying out ultrasonic cleaning in acetone, ethanol and deionized water for 30min, blow-drying with nitrogen, placing in a culture dish, placing in an oven at 95 deg.C, and standing for 8 min; then, putting the substrate into a vacuum chamber of a plasma cleaning machine, introducing stable oxygen gas flow with the flow rate of 30ml/min, and treating for 10min to obtain the substrate with hydrophilic modification;
(2) blending and growing bipolar organic single crystals;
firstly, p-type BSB-Me and n-type BTPB material powder are mixed according to a certain mass ratio and then placed in a mortar, and the mixing mass ratio of the p-type BSB-Me to the n-type BTPB material powder is 100:2, 100:5 and 100:10 respectively. Putting the mixed material into a mortar, adding 2mL of acetone, fully grinding the mixture for 30min, and drying the mixture in an oven at 100 ℃ for 40min to remove the solvent to obtain uniformly mixed monocrystalline material powder; then, 5mg of the uniformly mixed powder was placed in the high temperature sublimation zone of a two-temperature zone tube furnace. Finally, stable argon gas flow with the flow rate of 35mL/min is introduced, the respective temperature and growth time of the two temperature zones are set, the temperature of the high temperature zone is 275 ℃, the temperature of the low temperature zone is 225 ℃, the growth time is 180min, and a flaky bipolar organic single crystal suspended on the wall of the quartz tube is grown by utilizing a physical vapor transport method (PVT);
(3) Preparing a bipolar organic single crystal OFET device;
firstly, uniformly spin-coating 240 μ L of PMMA solution with concentration of 60mg/mL dissolved in toluene as an insulating layer on the substrate in the step (1), rotating at 3500 rpm/min for 18s, and then putting the substrate on which the PMMA insulating layer is spin-coated into a nitrogen glove box (1)<0.1ppm O2；<0.1ppm H2O) at 103 ℃ for 2h, then carrying out secondary annealing at 80 ℃ for 25min, and transferring the bipolar organic single crystal grown in the step (2) onto the substrate insulating layer by using anti-static tweezers after thermal annealing. Subsequently, gold wires with a diameter of 20 μm were used as OFET source and drain masks on the surface of the organic crystal. Finally, the device after the gold wire mask is placed in a high vacuum organic evaporation chamber, the source and the leakage level are grown, the thickness of the composite electrode Ca/Ag is 11nm/100nm, the growth speed is respectively
Au electrodes with a thickness of 90nm and a growth rate of
And finishing the preparation of the whole device. Wherein the gate is highly doped conductive Si. The insulating layer is dense SiO2The film and the spin-coated PMMA film jointly form a double-layer insulating layer.
As can be seen from FIG. 1, the hole mobility of BSB-Me bipolar organic single crystal mixed by pure BSB-Me and 2%, 5%, 10% BTPB is 0.14 + -0.07 cm in sequence 2/(Vs)，9.28±0.1×10-2cm2/(Vs),7.1±0.17×10-2cm2/(Vs),4.5±0.12×10-2cm2/(Vs), the electron mobility was 8.19. + -. 0.5X 10 in this order-4cm2/(Vs)，4.1±0.11×10-3cm2/(Vs),9.7±0.45×10-3cm2/(Vs)，4.0±0.14×10-2cm2/(Vs). It can be seen that the electron mobility of the pure p-type BSB-Me organic single crystal is three orders of magnitude lower than the hole mobility, and serious unbalanced charge transmission exists. The difference value of electron and hole mobility of the bipolar organic single crystal which is blended with the n-type BTPB molecule and grows is reduced to the minimum, and finally the two are almost completely equal, so that good charge transmission balance in the organic single crystal is realized.
Example 3
And preparing the OLED device by using the bipolar organic single crystal grown by molecular blending.
Commercial p-type organic single crystal material BSB-Me with low defect density and high fluorescence quantum efficiency and n-type organic single crystal material BTPB with high electron mobility and high stability are selected and controllably blended to grow and prepare the bipolar organic single crystal with balanced charge transmission. Furthermore, the bipolar organic single crystal is used as an OLED device light emitting layer, and excitons are effectively limited in the light emitting layer through balanced charge transmission in the bipolar organic single crystal, so that the composite light emitting efficiency is improved, and finally the light emitting efficiency of the organic single crystal OLED is effectively improved.
The preparation method of the OLED device by utilizing the bipolar organic single crystal grown by molecular blending comprises the following specific steps:
(1) Preparing a substrate;
firstly, ultrasonically cleaning a substrate in acetone, ethanol and deionized water for 30min, blow-drying the substrate by using nitrogen, placing the substrate in a culture dish, and placing the culture dish in an oven at 95 ℃ for 5-10 min; then, dripping 10 mu L of OTS on the blank position of the bottom of the culture dish containing the substrate by using a pipette gun, covering and sealing, and further placing the whole culture dish in a vacuum oven, wherein the OTS treatment temperature is 60 ℃, and the treatment time is 4h, so that the OTS is volatilized and the surface of the substrate is subjected to super-hydrophobic modification; finally, the substrate which is finished with modification is sequentially placed in acetone, ethanol and deionized water for ultrasonic cleaning for 30min, and is dried by nitrogen;
(2) blending and growing bipolar organic single crystals;
firstly, p-type BSB-Me and n-type BTPB material powder are mixed according to a certain mass ratio and then placed in a mortar, and the mixing mass ratio of the p-type BSB-Me to the n-type BTPB material powder is 100:2, 100:5 and 100:10 respectively. Putting the mixed material into a mortar, adding 2mL of acetone, fully grinding the mixture for 30min, and drying the mixture in an oven at 100 ℃ for 40min to remove the solvent to obtain uniformly mixed monocrystalline material powder; then, 5mg of the uniformly mixed powder was placed in the high-temperature sublimation zone of a two-temperature zone tube furnace. Finally, stable argon gas flow with the flow rate of 35mL/min is introduced, the respective temperature and growth time of the two temperature zones are set, the temperature of the high temperature zone is 275 ℃, the temperature of the low temperature zone is 225 ℃, the growth time is 180min, and a flaky bipolar organic single crystal suspended on the wall of the quartz tube is grown by utilizing a physical vapor transport method (PVT);
(3) Preparing a bipolar organic single-crystal OLED device;
the preparation sequence of each layer in the device structure is as follows: hole transport layer/anode growth → template lift-off transfer → electron transport layer/cathode growth; the hole transport layer/anode material is MoO3The electron transport layer/cathode material is TPBi/composite cathode Ca/Ag; firstly, the bipolar organic single crystal grown in the step (2) is transferred to the step (1) of OTS treatment and clean Si/SiO2On a substrate. Covering an anode mask plate under the condition of not damaging crystals, putting the anode mask plate into an organic vacuum evaporation chamber, and sequentially evaporating a hole transport layer MoO by thermal evaporation3And an anode Ag, the growth rate is controlled to
And
growth thicknesses were 8nm and 100nm, respectively, then a drop of 300 μ L NOA63 photoresist was placed on the uppermost layer of the device and pressed against a glass substrate, which spread NOA63 to the edge of the entire glass; subsequently, exposure to UV light for 20min, the photoresist cured and the device was peeled from the substrate with a blade, i.e. the device was transferred to a glass substrate. Finally, the device is placed in an organic vacuum evaporation chamber again, a cathode mask plate is covered, an electron transport layer TPBi and a composite cathode Ca/Ag are sequentially grown, and the growth speeds are controlled to be respectively 
The growth thicknesses are respectively 50nm,5nm and 15nm, and the preparation of the whole device is completed.
As can be seen from FIG. 2, the luminance of the BSB-Me bipolar organic single-crystal OLED device grown by blending BTPB is obviously improved along with the increase of the mixing proportion of BTPB, and the optimal luminance of the BSB-Me bipolar single-crystal OLED device with three different mixing proportions of 2%, 5% and 10% of pure BSB-Me is 132cd cm-2,454cd cm-2，645cd cm-2，1116cd cm-2It can be seen that, as the mixing ratio of BTPB increases, the bipolar transmission characteristics of the blended crystal tend to be well balanced, and finally, the brightness of the bipolar single-crystal OLED device is improved to 8 times that of the unipolar single-crystal OLED device.
As can be seen from FIG. 3, the current efficiency of the BSB-Me bipolar organic single-crystal OLED device grown by blending BTPB is remarkably improved along with the increase of the BTPB mixing ratio, and the optimal current efficiency of the bipolar single-crystal OLED device with pure BSB-Me, 2%, 5% and 10% of three different BTPB mixing ratios is 0.16cd A-1，0.34cd A-1,0.46cd A-1，0.64cd A-1. It can be seen that with the increase of the BTPB mixing ratio, the current efficiency of the bipolar organic single-crystal OLED device is improved to 4 times of the brightness of the unipolar single-crystal OLED.
Controllable molecular blending provides a feasible growth strategy for preparing the bipolar organic single crystal with balanced charge transmission. In addition, due to well-balanced bipolar transmission characteristics, exciton recombination efficiency in the organic single crystal is greatly improved, and finally, the light emitting performance of the organic single crystal OLED device is remarkably improved.
Claims (8)
1. The method for growing the bipolar organic single crystal by using the molecular blending is characterized by comprising the following specific steps of:
firstly, mixing a p-type material and n-type material powder according to a certain mass ratio, placing the mixture in a mortar, adding an organic solvent, fully grinding the mixture for 10-30min, and placing the mixture in an oven to dry the mixture so as to remove the solvent, thereby obtaining uniformly mixed material powder; then, placing the uniformly mixed powder in a high-temperature sublimation area of a double-temperature-area tube furnace; finally, introducing carrier gas with stable flow rate into the tube furnace, setting the respective temperature and growth time of the two temperature zones, starting heating, and growing the flaky bipolar single crystal suspended on the wall of the quartz tube by using a Physical Vapor Transport (PVT) method; the p-type material is 1, 4-bis (4-methyl styryl) benzene (BSB-Me), the n-type material is 2,2 '-bis [4- (trifluoromethyl) phenyl ] -5,5' thiazole (BTPB), and the mass ratio of the p-type material to the n-type material is 100: (0.1-50).
2. The method for growing bipolar organic single crystal by molecular blending according to claim 1, wherein the organic solvent used for grinding is acetone or ethanol, the amount is 1-5mL, the drying temperature is 100-120 ℃, and the drying time is 1-2 h; the mass of the mixed powder used for growing the single crystal is 2-5mg, the carrier gas is argon, the flow rate is 20-45mL/min, the temperature of the high-temperature region of the double-temperature-region tubular furnace is 270 DEG, the temperature of the low-temperature region is 230 DEG and 245 DEG, and the growth time is 120 DEG and 300 min.
3. A bipolar organic single crystal produced by the method according to any one of claims 1 to 2.
4. Use of the organic single crystal prepared by the method for growing a bipolar organic single crystal using molecular blending according to claim 1 in a light-emitting device.
5. Use of the organic single crystal produced by the method for growing a bipolar organic single crystal using molecular blending according to claim 4 for a light-emitting device,
the method for preparing the OFET device by using the bipolar organic single crystal comprises the following specific steps:
(1) preparing a substrate:
firstly, ultrasonically cleaning a substrate in acetone, ethanol and deionized water for 10-30min, drying the substrate by using nitrogen, placing the substrate in a culture dish, and placing the culture dish in an oven at 95 ℃ for 5-10 min; then, putting the substrate into a vacuum chamber of a plasma cleaning machine, and introducing oxygen to carry out hydrophilic modification on the surface of the plasma;
(2) and preparing an OFET device:
spin-coating a uniform organic polymer layer on the substrate by spin coater to form an insulating layer, and mixing with dense SiO2The films are used as a double-layer insulating layer together; then, carrying out thermal annealing treatment on the substrate coated with the insulating layer in a rotating manner, and transferring the bipolar single crystal to the insulating layer of the substrate by using anti-static tweezers after the thermal annealing treatment; subsequently, gold wires were used as OFET source and drain masks on the surface of the organic crystal; finally, placing the device behind the gold wire mask in an organic vacuum evaporation chamber, and growing a source drain electrode to finish the preparation of the whole device; wherein the gate is highly doped conductive Si.
6. Use of the organic single crystal produced by the method for growing a bipolar organic single crystal using molecular blending according to claim 5 for a light-emitting device,
the substrate is a highly doped silicon substrate of single-sided silicon dioxide, i.e. Si/SiO2A substrate having dimensions of 2cm x 1.8 cm; introducing oxygen gas flow into a plasma vacuum cavity, wherein the flow rate is 20-50 mL/min, and the time is 3-10 min;
the organic polymer insulating layer is polymethyl methacrylate (PMMA) with the concentration of 30-60mg/mL, the solvent is toluene or anisole with the dosage of 50-300 mu L, the spin-coating rotating speed is 2000-4000 r/min, the spin-coating time is 5-20 s, and the thickness is 50-200 nm; the thermal annealing process is firstly carried out in a nitrogen glove box (<0.1ppm O2; <0.1 ppm H2O) is pre-annealed for 1 to 3 hours at the temperature of between 90 and 120 ℃, and then secondary annealing is carried out for 10 to 30min at the temperature of between 60 and 90 ℃; the diameter of the gold wire is 10-30 μm; the source-drain electrode is composite electrode Ca/Ag or Au, the thickness is respectively 8-15 nm/80-120 nm, the growth speed is respectively 0.08-0.28A/s/0.7-1.3A/s, and the growth speed is respectively 0.2-0.6As。
7. Use of the organic single crystal produced by the method for growing a bipolar organic single crystal using molecular blending according to claim 4 for a light-emitting device,
The method for preparing the OLED device by using the bipolar organic single crystal comprises the following specific steps:
the preparation sequence of each layer in the device structure is as follows: hole transport layer/anode growth → template lift-off transfer → electron transport layer/cathode growth;
(1) preparing a substrate:
firstly, ultrasonically cleaning a substrate in acetone, ethanol and deionized water for 10-30min, drying the substrate by using nitrogen, placing the substrate in a culture dish, and placing the culture dish in an oven at 95 ℃ for 5-10 min; secondly, dripping the hydrophobic modifier on the blank of the bottom of the culture dish containing the substrate by using a pipette and covering and sealing the blank, and further placing the whole culture dish in a vacuum oven to volatilize the hydrophobic modifier and perform super-hydrophobic modification on the surface of the substrate; finally, the substrate which is finished with modification is sequentially placed in acetone, ethanol and deionized water for ultrasonic cleaning for 10-30min, and is dried by nitrogen;
(2) and preparing an OLED device:
transferring the bipolar organic single crystal to a substrate which is subjected to hydrophobic treatment and is cleaned; covering an anode mask plate under the condition of not damaging the crystal, putting the anode mask plate into an organic vacuum evaporation chamber, and depositing a hole transport layer and an anode on the organic crystal through thermal evaporation; then, a drop of photoresist was placed on the device and pressed against a glass substrate, which spread the photoresist over the edge of the entire glass; subsequently, exposure to UV light, the photoresist cured and the device was peeled from the substrate with a blade, i.e. the device was transferred to a glass substrate; and finally, placing the device in an organic vacuum evaporation chamber again, covering a cathode mask plate, and sequentially growing an electron transport layer and a cathode to finish the preparation of the whole device.
8. Use of the organic single crystal produced by the method for growing a bipolar organic single crystal using molecular blending according to claim 6 for a light-emitting device,
the substrate is a silicon substrate with double-sided silicon dioxide, and the size of the substrate is 1.6cm multiplied by 1.4 cm; the hydrophobic modifier is Octadecyltrichlorosilane (OTS), the dosage is 10-30 mu L, the modification temperature is 40-60 ℃, and the modification time is 4-12 h; the vacuum degree of the vacuum drying oven is 0.1 Mpa;
the hole transport layer/anode is MoO3Ag with thicknesses of 4-12nm and 80-200nm respectively and growth speeds of 0.1-0.4A/s and 0.7-1.3A/s respectively; the used photoresist is NOA63, the dosage is 100-300 mu L, the photoresist stabilization time is 3-8min, and the exposure curing time under a UV lamp is 15-17 min; the electron transport layer/cathode is TPBi/Ca/Ag, wherein TPBi is an electron transport layer, Ca/Ag is a composite cathode, the thicknesses are 40-80nm, 8-15nm and 15-25nm, respectively, and the growth rates are 0.7-1.1 a/s, 0.08-0.5 a/s and 0.7-1.3 a/s, respectively.
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