CN110872301A - Phosphorescent compound and organic light emitting diode device using the same - Google Patents

Phosphorescent compound and organic light emitting diode device using the same Download PDF

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CN110872301A
CN110872301A CN201910977539.5A CN201910977539A CN110872301A CN 110872301 A CN110872301 A CN 110872301A CN 201910977539 A CN201910977539 A CN 201910977539A CN 110872301 A CN110872301 A CN 110872301A
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phosphorescent compound
light emitting
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phosphorescent
independently selected
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郑贤哲
赵晓宇
华万鸣
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Zhejiang Hua Hui Photoelectric Technology Co Ltd
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Abstract

The present invention relates to a phosphorescent compound and an organic light emitting diode device using the same, and more particularly, to a soluble phosphorescent host compound having excellent color purity and high luminance and light emitting efficiency and an OLED device using the same. A phosphorescent compound characterized by: the structural formula is shown as formula 1 or formula 2,
Figure DDA0002234128930000011
the present invention uses the phosphorescent compounds represented by structural formulae 1 and 2 as the light emitting layer of the organic light emitting diode device, having excellent color purity and brightness and prolonged durability effect.

Description

Phosphorescent compound and organic light emitting diode device using the same
Technical Field
The present invention relates to a phosphorescent compound and an organic light emitting diode device using the same, and more particularly, to a soluble phosphorescent host compound having excellent color purity and high luminance and light emitting efficiency and an OLED device using the same.
Background
Recently, the demand for flat panel displays (e.g., liquid crystal displays and plasma display panels) is increasing. However, these flat panel displays have a lower response time and a narrower viewing angle than Cathode Ray Tubes (CRTs).
An Organic Light Emitting Diode (OLED) device is one of the next-generation flat panel displays that can solve the above problems and have a small footprint.
The elements of the OLED device may be formed on a flexible substrate, such as a plastic substrate. In addition, OLED devices have advantages in view angle, driving voltage, power consumption, and color purity. In addition, OLED devices are sufficient to produce full color images.
In general, a light emitting diode of an OLED device includes an anode, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Emitting Material Layer (EML), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and a cathode.
The OLED device emits light by: electrons and holes are injected into the light emitting compound layer from the cathode as an electron injection electrode and from the anode as a hole injection electrode, respectively, so that the electrons and the holes are recombined to generate excitons, and the excitons are made to transition from an excited state to a ground state.
The principle of luminescence can be divided into fluorescence and phosphorescence. In fluorescence emission, an organic molecule in a singlet excited state transits to a ground state, thereby emitting light. On the other hand, in phosphorescence, organic molecules in a triplet excited state transition to a ground state, thereby emitting light.
When the light emitting material layer emits light corresponding to the energy band gap, singlet excitons having 0 spin and triplet excitons having 1 spin are generated in a ratio of 1: 3. The ground state of the organic material is a singlet state, which allows singlet excitons to transition to the ground state with accompanying light emission. However, since the triplet excitons cannot undergo transition accompanied by light emission, the internal quantum efficiency of the OLED device using the fluorescent material is limited to within 25%.
On the other hand, if the spin orbit coupling momentum is high, the singlet state and the triplet state are mixed so that an intersystem crossing occurs between the singlet state and the triplet state, and the triplet exciton may also transition to the ground state with accompanying light emission. The phosphorescent material may use triplet excitons and singlet excitons, so that an OLED device using the phosphorescent material may have an internal quantum efficiency of 100%.
Recently, iridium complexes, such as bis (2-phenylquinoline) (acetylacetonate) iridium (iii) (Ir (2-phq)2(acac)), bis (2-benzo [ b ] thiophen-2-ylpyridine) (acetylacetonate) iridium (iii) (Ir (btp)2(acac)), and tris (2-phenylquinoline) iridium (iii) Ir (2-phq)3 dopants have been introduced.
In order to obtain high current luminous efficiency (Cd/a) using a phosphorescent material, excellent internal quantum efficiency, high color purity, and long lifetime are required. In particular, referring to fig. 1, the higher the color purity, i.e., the higher cie (x), the worse the color sensitivity. As a result, it is very difficult to obtain light emission efficiency at high internal quantum efficiency. Therefore, there is a need for novel red phosphorescent compounds having excellent color purity (CIE (X) ≧ 0.65) and high luminous efficiency.
On the other hand, in addition to the iridium complex described above, for example, 4,4-N, N-Carbazole Biphenyl (CBP) or other metal complexes are used as the red phosphorescent compound. However, these compounds do not have ideal solubility in a solvent, and thus cannot form a light emitting layer by a solution process. The light emitting layer should be formed through a deposition process, and thus, the manufacturing process is very complicated and the process efficiency is very low. In addition, the amount of waste material in the deposition process is very large, resulting in increased production costs.
Disclosure of Invention
The present invention is directed to provide a phosphorescent compound and an organic light emitting diode device using the same to solve the disadvantages of the related art.
The technical solution adopted by the present invention to solve the technical problems is to provide a phosphorescent compound of formula 1 or formula 2,
Figure BDA0002234128910000031
ar1 in the formulas 1 and 2 is independently selected from one of C6-C60 aryl, fluorenyl, C2-C60 heterocyclic radical containing at least one heteroatom of O, N, S, Si and P, C3-C60 alicyclic and C6-C60 aromatic ring condensed ring radical, C2-C20 alkenyl and C2-C20 alkynyl. L1 and L2 are independently selected from one of single bond, C6-C60 arylene group and fluorenylene group, C3-C60 alicyclic ring and C6-C60 aromatic ring condensed ring group, and C2-C60 heterocyclic group. X1-X2 are independently selected from N atoms or C atoms, wherein at least one of X1-X2 is N. Wherein Y is selected from O, S and Se. Further, Ar2 and Ar3 are selected from H, C6-C60 aryl, fluorenyl, C2-C60 heterocyclic group containing O, N, S, Si and P at least one heteroatom, C3-C60 alicyclic and C6-C60 aromatic ring condensed ring group, C2-C20 alkenyl, and C2-C20 alkynyl.
Further, formula 1 and formula 2 are independently selected from any one of the structures of formula 3 to formula 6:
Figure BDA0002234128910000032
further, the phosphorescent compound is independently selected from the following compounds:
Figure BDA0002234128910000041
Figure BDA0002234128910000051
Figure BDA0002234128910000061
Figure BDA0002234128910000071
Figure BDA0002234128910000081
Figure BDA0002234128910000091
Figure BDA0002234128910000101
Figure BDA0002234128910000111
Figure BDA0002234128910000121
Figure BDA0002234128910000131
Figure BDA0002234128910000141
Figure BDA0002234128910000151
Figure BDA0002234128910000161
Figure BDA0002234128910000171
Figure BDA0002234128910000181
Figure BDA0002234128910000191
Figure BDA0002234128910000201
Figure BDA0002234128910000211
further, the organic electroluminescent device comprises an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode which are deposited in sequence, and the phosphorescent compound is used as a main material of the light emitting layer.
The invention has the advantages that: the present invention uses the phosphorescent compound represented by formula 1 or formula 2 as the light emitting layer of the organic light emitting diode device, having excellent color purity and luminance and a prolonged durability effect.
Drawings
FIG. 1 is a graph of chromaticity and visibility of light emitted from an organic electroluminescent diode.
FIG. 2 is a structural formula of compounds copper (II) phthalocyanine (CuPc), NPB, (mxmq)2Ir (acac), Alq3 and CBP used in an embodiment of the present invention.
Detailed Description
In order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easy to understand, the invention is further described with reference to the figures and the specific embodiments.
As the red phosphorescent compounds with the structural formulas shown as the formula 1 and the formula 2 have excellent color purity, high brightness and excellent luminous efficiency, the technical scheme and the achieved technical effect provided by the invention are proved by taking preparation methods and test results of RH-001, RH-023, RH-036, RH-109, RH-131 and RH-144 as examples.
In the following embodiments, NPB is 4,4 ' -bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl, CBP is 4,4 ' -N, N ' -dicarbakisbiphenyl, CuPc is copper phthalocyanine, LiF lithium fluoride, ITO is indium tin oxide, and Alq3 is tris (8-hydroxyquinoline) aluminum.
LC-MS, liquid chromatography-mass spectrometer, M/Z: ratio of number of protons/number of charges.
Examples of formation
1. Synthesis of intermediate Sub-1:
Figure BDA0002234128910000231
a2000 mL reaction flask was charged with 2-bromonitrobenzene (150.0g,742.5mmol), 2-aminophenylboronic acid pinacol ester (179.0g,816.8mmol), and tetrakis(triphenylphosphine) palladium (5 mol%), sodium bicarbonate (187.1g,2227.6mmol), ethylene glycol dimethyl ether (1200mL) and water (200 mL). The reaction system is heated to 90 ℃ and reacts for 12 hours under the protection of nitrogen. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and recrystallized to give a crude product, which was passed through a silica gel column to obtain an intermediate, Sub-1(133.6g, yield 84%), LC-MS: M/Z215.2 (M + H)+。
2. Synthesis of intermediate Sub-2:
Figure BDA0002234128910000232
a2000 mL reaction flask was charged with a mixture of intermediate Sub-1(130.0g,606.9mmol), water (800mL) and concentrated hydrochloric acid (200mL) and heated to 60 ℃ to give a clear solution. The mixture was diazotized at 5 ℃ by addition of an aqueous solution (150mL) of sodium nitrite (46.1g,667.5 mmol). After stirring for 30 minutes, an aqueous solution (300mL) of potassium iodide (120.9g,728.2mmol) was added rapidly to the mixture, which was then heated slowly to boiling point and refluxed for 6 hours. After the reaction was completed, it was cooled to room temperature. The mixture was quenched by addition of saturated sodium sulfate solution and the pH was adjusted to 8-10 with saturated aqueous sodium hydroxide solution. The combined organic solvents were extracted with ethyl acetate, dried over sodium sulfate and concentrated under reduced pressure. Chromatography (ethyl acetate/petroleum ether-1/30) gave intermediate Sub-2(153.9g, 78% yield). LC-MS M/Z326.1(M + H)+。
3. Synthesis of intermediate Sub-3:
Figure BDA0002234128910000241
after intermediate Sub-2(150.0g,461.4mmol) in dry dichloromethane (1500mL), m-chloroperoxybenzoic acid (119.4g,692.1mmol) and trifluoromethanesulfonic acid (122.5mL,1384.2mmol) were added with stirring. The above mixture was stirred at room temperature for 2 hours. The dichloromethane was removed by rotary evaporation, then diethyl ether was added and the mixture stirred for 30 minutes and filtered. The collected solid was washed three times with ether and dried in vacuo to give intermediate Sub-3(172.4g, yield 79%). LC-MS: M/Z 474.2(M+H)+。
4. Synthesis of intermediate Sub-4:
Figure BDA0002234128910000242
a2000 mL three-necked flask was charged with intermediate Sub-3(170.0g,359.3mmol), naphthalene-1, 8-diboronic acid (78.2g,395.2mmol), palladium acetate (10 mol%), potassium carbonate (124.1g,898.3mmol), ethylene glycol dimethyl ether (1000mL) and water (450 mL). The reaction system is heated to 120 ℃ and reacts for 14 hours under the protection of nitrogen. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with ethyl acetate and water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and recrystallized to give crude product, which was then passed through a silica gel column to give intermediate Sub-4(41.8g, yield 36%). LC-MS: M/Z324.3 (M + H)+。
5. Synthesis of intermediate Sub-5:
Figure BDA0002234128910000251
a500 mL reaction flask was charged with intermediate Sub-4(40.0g,123.7mmol) and triethyl phosphite (200 mL). The reaction system is heated to 80 ℃ and reacts for 18 hours under the protection of nitrogen. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with o-dichlorobenzene and water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and recrystallized to give a crude product which was passed through a silica gel column to give an intermediate, Sub-5(20.9g, yield 58%), LC-MS: M/Z292.4 (M + H)+。
Synthesis of RH-001:
Figure BDA0002234128910000252
a250 mL three-necked flask was charged with intermediate I-1(3.0g,9.1mmol), intermediate Sub-5(2.9g,10.0mmol), tris (dibenzylideneacetone) dipalladium (4 mol%), tri-tert-butylphosphine (8 mol%), potassium tert-butoxide (3.1g,27.2mmol) and o-xylene (80 mL). The reaction system is heated to 120 ℃ and reacts for 14 hours under the protection of nitrogen. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with o-dichlorobenzene and water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and concentratedThe crude product thus obtained was passed through a silica gel column to obtain RH-001(3.7g, yield 70%). LC-MS: M/Z586.7 (M + H)+。
Synthesis of RH-023:
Figure BDA0002234128910000261
a250 mL three-necked flask was charged with intermediate I-2(3.0g,7.4mmol), intermediate Sub-5(2.4g,8.1mmol), tris (dibenzylideneacetone) dipalladium (4 mol%), tri-tert-butylphosphine (8 mol%), potassium tert-butoxide (2.5g,22.1mmol) and o-xylene (80 mL). The reaction system is heated to 120 ℃ and reacts for 14 hours under the protection of nitrogen. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with o-dichlorobenzene and water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and recrystallized to give a crude product, which was then passed through a silica gel column to obtain RH-023(3.3g, yield 68%). LC-MS: M/Z662.8 (M + H)+。
Synthesis of RH-036:
Figure BDA0002234128910000262
a250 mL three-necked flask was charged with intermediate I-3(3.0g,6.0mmol), intermediate Sub-5(1.9g,6.7mmol), tris (dibenzylideneacetone) dipalladium (4 mol%), tri-tert-butylphosphine (8 mol%), potassium tert-butoxide (2.1g,18.6mmol) and o-xylene (80 mL). The reaction system is heated to 120 ℃ and reacts for 14 hours under the protection of nitrogen. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with o-dichlorobenzene and water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and recrystallized to give crude RH-036(2.8g, yield 62%) through silica gel column. LC-MS: M/Z751.8 (M + H)+。
Synthesis of RH-109:
Figure BDA0002234128910000271
a250 mL three-necked flask was charged with intermediate I-4(3.0g,9.1mmol), intermediate Sub-5(2.9g,10.0mmol), tris (dibenzylideneacetone) dipalladium (4 mol%), tri-tert-butylphosphine (8 mol%), potassium tert-butoxide (3.1g,27.2mmol) and o-xylene (80 mL). Reaction System literThe temperature is raised to 120 ℃, and the reaction is carried out for 14 hours under the protection of nitrogen. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with o-dichlorobenzene and water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and recrystallized to give crude RH-109(3.6g, yield 67%). LC-MS: M/Z586.7 (M + H)+。
Synthesis of RH-131:
Figure BDA0002234128910000272
a250 mL three-necked flask was charged with intermediate I-5(3.0g,7.4mmol), intermediate Sub-5(2.4g,8.1mmol), tris (dibenzylideneacetone) dipalladium (4 mol%), tri-tert-butylphosphine (8 mol%), potassium tert-butoxide (2.5g,22.1mmol) and o-xylene (80 mL). The reaction system is heated to 120 ℃ and reacts for 14 hours under the protection of nitrogen. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with o-dichlorobenzene and water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and recrystallized to give a crude product, which was then passed through a silica gel column to obtain RH-131(3.2g, yield 68%). LC-MS: M/Z662.8 (M + H)+。
Synthesis of RH-144:
Figure BDA0002234128910000281
a250 mL three-necked flask was charged with intermediate I-6(3.0g,6.0mmol), intermediate Sub-5(1.9g,6.7mmol), tris (dibenzylideneacetone) dipalladium (4 mol%), tri-tert-butylphosphine (8 mol%), potassium tert-butoxide (2.1g,18.6mmol) and o-xylene (80 mL). The reaction system is heated to 120 ℃ and reacts for 14 hours under the protection of nitrogen. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with o-dichlorobenzene and water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and recrystallized to give crude RH-144(2.8g, yield 61%). LC-MS: M/Z751.8 (M + H)+。
Detailed description of the preferred embodiments
1. First embodiment
The ITO glass substrate was patterned to have a light-emitting area of 3mm × 3 mm. Then, the patterned ITO glass substrate was washed.
Subsequently placing the substrate onA vacuum chamber. The standard pressure was set to 1X 10-6And (4) supporting. Thereafter, on the ITO substrate
Figure BDA0002234128910000283
Figure BDA0002234128910000284
And
Figure BDA0002234128910000285
the sequence of (a) and (b) forming layers of organic material.
At 0.9mA, the brightness is equal to 1758d/m2(5.2V). In this case, CIEx is 0.657 and CIEy is 0.340.
2. Second embodiment
The ITO glass substrate was patterned to have a light-emitting area of 3mm × 3 mm. Then, the patterned ITO glass substrate was washed.
The substrate is then placed in a vacuum chamber. The standard pressure was set to 1X 10-6And (4) supporting. Thereafter, on the ITO substrate
Figure BDA0002234128910000282
Figure BDA0002234128910000291
And
Figure BDA0002234128910000292
the sequence of (a) and (b) forming layers of organic material.
At 0.9mA, the luminance is equal to 1732cd/m2(5.3V). At this time, CIEx ═ 0.658CIEy ═ 0.340.
3. Third embodiment
The ITO glass substrate was patterned to have a light-emitting area of 3mm × 3 mm. Then, the patterned ITO glass substrate was washed.
The substrate is then placed in a vacuum chamber. The standard pressure was set to 1X 10-6And (4) supporting. Thereafter, on the ITO substrate
Figure BDA00022341289100002913
Figure BDA0002234128910000295
And
Figure BDA0002234128910000296
the sequence of (a) and (b) forming layers of organic material.
At 0.9mA, the luminance is equal to 1712cd/m2(5.4V). At this time, CIEx is 0.658 and CIEy is 0.339.
4. Fourth embodiment
The ITO glass substrate was patterned to have a light-emitting area of 3mm × 3 mm. Then, the patterned ITO glass substrate was washed.
The substrate is then placed in a vacuum chamber. The standard pressure was set to 1X 10-6And (4) supporting. Thereafter, on the ITO substrate
Figure BDA0002234128910000297
Figure BDA0002234128910000298
And
Figure BDA0002234128910000299
the sequence of (a) and (b) forming layers of organic material.
At 0.9mA, the luminance was equal to 1741cd/m2(5.2V). In this case, CIEx is 0.657 and CIEy is 0.341.
5. Fifth embodiment
The ITO glass substrate was patterned to have a light-emitting area of 3mm × 3 mm. Then, the patterned ITO glass substrate was washed.
The substrate is then placed in a vacuum chamber. The standard pressure was set to 1X 10-6And (4) supporting. Thereafter, on the ITO substrate
Figure BDA00022341289100002910
Figure BDA00022341289100002911
And
Figure BDA00022341289100002912
is sequentially formed withA layer of a substance.
At 0.9mA, the luminance is equal to 1719cd/m2(5.2V). In this case, CIEx is 0.657 and CIEy is 0.340.
6. Sixth embodiment
The ITO glass substrate was patterned to have a light-emitting area of 3mm × 3 mm. Then, the patterned ITO glass substrate was washed.
The substrate is then placed in a vacuum chamber. The standard pressure was set to 1X 10-6And (4) supporting. Thereafter, on the ITO substrate
Figure BDA0002234128910000301
Figure BDA0002234128910000302
And
Figure BDA0002234128910000303
the sequence of (a) and (b) forming layers of organic material.
At 0.9mA, the luminance is equal to 1702cd/m2(5.3V). At this time, CIEx is 0.658 and CIEy is 0.339.
7. Comparative example
The ITO glass substrate was patterned to have a light-emitting area of 3mm × 3 mm. Then, the patterned ITO glass substrate was washed.
The substrate is then placed in a vacuum chamber. The standard pressure was set to 1X 10-6And (4) supporting. On an ITO substrate
Figure BDA0002234128910000304
Figure BDA0002234128910000305
And
Figure BDA0002234128910000306
the sequence of (a) and (b) forming layers of organic material.
At 0.9mA, the luminance was equal to 1409cd/m2(5.7V). In this case, CIEx is 0.657 and CIEy is 0.341.
It is shown in fig. 1 that the color purity of the organic electroluminescent device increases (i.e., the X value becomes larger as the chromaticity coordinate becomes larger) and the visibility decreases.
The characteristics of efficiency, chromaticity coordinates, and luminance according to the above-described embodiments and comparative examples are shown in table 1 below.
TABLE 1
Figure BDA0002234128910000307
Figure BDA0002234128910000311
As shown in table 1, the device operates at high efficiency at low voltage even when the color purity is high. Also, the current efficiency of the second embodiment is increased by 20% or more compared to the comparative example.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (4)

1. A phosphorescent compound characterized by: the structural formula is shown as formula 1 or formula 2,
Figure FDA0002234128900000011
ar1 in the formulas 1 and 2 is independently selected from one of C6-C60 aryl, fluorenyl, C2-C60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P, C3-C60 alicyclic and C6-C60 aromatic ring condensed ring group, C2-C20 alkenyl and C2-C20 alkynyl; l1 and L2 are respectively and independently selected from one of a single bond, C6-C60 arylene and fluorenylene, C3-C60 alicyclic and C6-C60 aromatic ring condensed ring group, and C2-C60 heterocyclic group; X1-X2 are independently selected from N atoms or C atoms, wherein at least one of X1-X2 is N; wherein Y is selected from O, S and Se; wherein Ar2 and Ar3 are selected from H, C6-C60 aryl, fluorenyl, C2-C60 heterocyclic group containing O, N, S, Si and P at least one heteroatom, C3-C60 alicyclic and C6-C60 aromatic ring condensed ring group, C2-C20 alkenyl, C2-C20 alkynyl.
2. The phosphorescent compound according to any one of claim 1, wherein the formulae 1 and 2 are independently selected from any one of the structures of formulae 3 to 6:
Figure FDA0002234128900000012
3. the phosphorescent compound according to any one of claims 1 to 2, wherein: the phosphorescent compounds are independently selected from the following compounds:
Figure FDA0002234128900000021
Figure FDA0002234128900000031
Figure FDA0002234128900000041
Figure FDA0002234128900000051
Figure FDA0002234128900000061
Figure FDA0002234128900000071
Figure FDA0002234128900000081
Figure FDA0002234128900000091
Figure FDA0002234128900000101
Figure FDA0002234128900000111
Figure FDA0002234128900000121
Figure FDA0002234128900000131
Figure FDA0002234128900000141
Figure FDA0002234128900000151
Figure FDA0002234128900000161
Figure FDA0002234128900000171
Figure FDA0002234128900000181
Figure 3
4. an organic electroluminescent diode device using the phosphorescent compound according to any one of claims 1 to 3, characterized in that: the organic electroluminescent device sequentially comprises a deposited anode, a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer and a cathode, and the phosphorescent compound is used as a main material of the luminescent layer.
CN201910977539.5A 2019-10-15 2019-10-15 Phosphorescent compound and organic light emitting diode device using the same Pending CN110872301A (en)

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