CN113135945A - Organic boron semiconductor material and OLED device application - Google Patents
Organic boron semiconductor material and OLED device application Download PDFInfo
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Abstract
The invention discloses an organic boron semiconductor material and an organic light-emitting diode (OLED), which is characterized in that a light-emitting layer in an OLED device contains a light-emitting material with the following chemical structure general formula:
wherein R is1‑R5Containing at least one saturated or unsaturated aliphatic ring, or a chemical crosslinking group, or a group with X1‑X5The alkane spiro-ring is chemically bonded through an alkane chain, an alkane alkoxy chain and an alkane sulfur chain. The organic light-emitting device can be applied to an organic light-emitting device OLED formed by vapor deposition or solution film, the performance of a blue light-emitting device is improved, and the service life of the device is prolonged.
Description
Technical Field
The invention relates to an organic semiconductor compound and application thereof in an organic light-emitting device (OLED). In particular to the design and synthesis of novel organic blue luminescent layer material molecules, which improves the luminescent efficiency of luminescent materials, reduces the cost of the luminescent materials and improves the performance of OLED display devices.
Background
The organic semiconductor material belongs to a novel photoelectric material, and the large-scale research of the organic semiconductor material originates from the discovery of doped polyacetylene with the conductivity reaching the copper level by the white-skinned tree, A, Heeger and A, McDiamid in 1977. Subsequently, c.tang et al, Kodak corporation, 1987, invented small organic molecule light emitting diodes (OLEDs), and r.friend and a. Holmes, cambridge university, 1990, invented polymer light emitting diodes P-OLEDs, and s.forrest and m.thomson, 1998, invented higher efficiency phosphorescent organic light emitting diodes PHOLEDs. Since the organic semiconductor material has the advantages of easily adjustable structure, various types, adjustable energy band and low cost as the plastic film, and the organic semiconductor is applied to conductive films, electrostatic copying, photovoltaic solar cells, organic thin film transistor logic circuits, organic light-emitting OLED (organic light emitting diode) panel display, illumination and other applications, the Baichuan-Heeger-McDiamid three scientists obtain the Nobel prize in the year 2000.
As organic electroluminescent diodes for the next generation of flat panel display applications, organic photoelectric semiconductor materials require: 1. high luminous efficiency; 2. excellent electron and hole stability; 3. a suitable emission color; 4. excellent film forming processability; 5. lower cost compared to liquid crystal displays. In principle, most conjugated organic molecules (including star emitters), conjugated polymers, and organic heavy metal complexes containing conjugated chromophore ligands have electroluminescent properties and are used in a variety of light emitting diodes, such as organic small molecule light emitting diodes (OLEDs), polymer organic light emitting diodes (polleds), organic phosphorescent light emitting diodes (PHOLEDs), and organic thermally activated delayed fluorescence TADFOLEDs. Phosphorescence PHOLED combines the light-emitting mechanisms of singlet excited state (fluorescence) and triplet excited state (phosphorescence), obviously has much higher light-emitting efficiency than small molecule OLED and high molecule POLED, and has been applied to various modern mobile phone display screens, but the disadvantage is that precious metals such as iridium or platinum are required to be used, so that the cost of the OLED display screen mobile phone is high. The canon company pioneers the use of triplet state luminescent materials without precious metals in 2004 (US2006/0051616, US7749617, international priority 2004, 9/8), and obtains thermally Activated Delayed fluorescence tadf (thermal Activated Delayed fluorescence) by reverse exchange of risc (reverse interface system cross) between triplet and singlet systems, thereby enabling excitons in triplet state to efficiently fluoresce. Therefore, like the phosphorescent triplet-state luminescent material containing noble metal, the TADF material without noble metal has the luminescent efficiency 3-4 times that of the common fluorescent OLED material, and the internal quantum efficiency can reach 100%. Therefore, the TADF light-emitting material is expected to greatly reduce the cost of the high-efficiency organic light-emitting material and increase the competitiveness of the OLED display panel. As an organic electroluminescent blue light emitting material, a phosphorescent triplet organic metal light emitting material has 3 times higher efficiency than a fluorescent light emitting material, but due to a lifetime problem, a fluorescent blue light emitting material with lower efficiency but relatively longer lifetime has to be used in a commercial AMOLED at present. Therefore, the development of more stable and efficient electroluminescent blue-light emitting materials, especially TADF blue-light emitting materials with high efficiency, low cost and longer lifetime, has been a strategic issue in the industry.
In general organic semiconductor materials, the triplet state is lower in energy than the singlet state according to flood criteria, and the band difference (Δ Es1-t1) is usually 0.6eV or more, so that it is substantially impossible for an electron in the triplet state to return to the singlet state to emit a light wave. In the TADF material, by the molecular design, the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) in the molecular orbitals are rarely overlapped, and a fluorescent material having a reduced difference between the triplet level and the singlet level, even only 0.3eV or less, is prepared, so that it is possible to reverse-cross the electrons from the triplet state to the singlet state (or RISC) to obtain an electric-to-light emission efficiency as high as 100% as in phosphorescence. An example of a reported material is green-emitting 2, 6-dicyano-1, 3,4, 5-tricarbazolylbenzene.
In the OLED device, charges are injected by injecting holes from the anode after a positive voltage is applied to the anode, injecting electrons after a negative voltage is applied to the cathode, passing through the electron transport layer and the hole transport layer, respectively, and simultaneously entering the host material or the host material of the emission layer, the electrons finally enter the Lowest Unoccupied Molecular Orbital (LUMO) of the light emitting dopant, and the holes enter the Highest Occupied Molecular Orbital (HOMO) of the light emitting dopant to form excited light emitting dopant molecules (exciton state). The exciton state reverts to the ground state with the emission of light energy at a wavelength corresponding to the energy gap (HOMO-LUMO energy level difference) of the light emitting molecular dopant. Among the organic semiconducting blue-emitting materials, document JP 2014-214148 discloses the use of indolocarbazoles in conjunction with a castor to obtain improved blue-doped material reports. Document (j. -a.seo, et al, ACS appl.mat.inter.,05.oct.2017) discloses indolocarbazoles as electron withdrawing groups, which in combination with fused arylamine groups form highly efficient deep blue TADF organic light emitting materials with maximum external quantum efficiency of 19.5%. But because the LUMO is high (LUMO ═ 2.4eV) and its electron injection electrochemical cycling CV test shows irreversible, the EQE efficiency is greatly reduced at higher current or high brightness. The recent document US20190058124 discloses that using boron containing organic semiconductors, highly efficient blue emitting materials are obtained, the OLED device emitting efficiency reaching and even exceeding the organometallic iridium blue emitting material FIrPic. The boron-containing organic luminescent material has the advantages that the difference between the triplet state energy level and the singlet state energy level is less than 0.3eV, the RISC thermal retardation fluorescence TADF luminescent characteristic is shown, the emission wavelength is blue, and the half-height peak width of the spectrum is as small as 30 nm.
Obviously, in order to meet the performance improvement requirement of continuous improvement of industrial production, the organic OLED display and lighting products with high efficiency, low cost and long service life are explored and obtained, and the development of better, more efficient and easily manufactured organic semiconductor materials is imperative.
Disclosure of Invention
The present invention is directed to the development trend of the prior art, and based on the scheme disclosed in document US20190058124, it is found that the use of cyclic alkane as the substitution has an unexpected effect of increasing the luminous efficiency or the lifetime of the light emitting device, compared to the light emitting material substituted by linear chain or other non-cyclic chain without alkyl substitution and the same carbon atom. The relaxation time of the TADF luminescent material exciton is generally in the order of microseconds and sub-microseconds, which is longer than that of the common fluorescent luminescent material (in the order of nanoseconds), or the intermolecular exciton transmission distance is longer, so that the TADF luminescent material is substituted by common methyl, ethyl, tert-butyl, etc., or it is difficult to effectively reduce the annihilation of the luminescent intermolecular exciton. We have unexpectedly found that organic luminescent boron compounds so substituted can reduce annihilation of excitons between luminescent molecules and increase luminous efficiency using cyclic alkyl substitution, even spirocycloalkane substitution. The formed organic molecular semiconductor has improved light-emitting efficiency of the TADF material OLED device, is particularly applied to an organic electroluminescent blue OLED, and obtains an OLED device with improved light-emitting efficiency or prolonged service life.
The organic semiconductor luminescent material can be applied to Organic Light Emitting Diodes (OLEDs). In OLED applications, an OLED light emitting device generally comprises: a base material such as glass, metal foil, or polymer film; an anode, such as transparent conductive indium tin oxide; a cathode, such as conductive aluminum or other metal; one or more layers of organic semiconductors, such as an electron injection layer between the light-emitting layer and the cathode, a hole injection layer between the light-emitting layer and the anode, wherein the light-emitting layer contains a light-emitting dopant mixed with a host material to form the light-emitting layer. The luminescent dopant material is typically doped into a host material at a concentration (weight percent) of 1-45%.
The invention discloses an organic light-emitting diode, which is characterized by comprising the following parts:
(a) a cathode having a cathode electrode and a cathode electrode,
(b) an electron transport layer adjacent to the cathode,
(c) an anode having a first electrode and a second electrode,
(d) a hole transport layer adjacent to the anode,
(e) an organic semiconductor light-emitting layer sandwiched between the electron-transporting layer and the hole-transporting layer, the light-emitting layer comprising an organic semiconductor compound having the general chemical structure:
wherein R is1、R2、R3、R4、R5Containing at least one saturated or unsaturated aliphatic ring;
the R is1、R2、R3、R4、R5The aliphatic ring comprises three-membered ring, four-membered ring, five-membered ring, six-membered ring, seven-membered ring, eight-membered ring, or C of each of the above rings1-C12Alkyl substitution of (C)1-C12Alkoxy-substituted radical of (A), C6-C12Aryl-substituted of (A), C5-C12Aryl-hetero-substituted of, C7-C12The fused aromatic heterocyclic group of (1) is substituted, F is substituted, Cl is substituted, Br is substituted, and isotope D is substituted;
within the scope of the present invention, the saturated or unsaturated aliphatic ring contained in the organic light emitting semiconductor compound includes, but is not limited to, the following structures:
x in the general formula (I)1、X2、X3、X4、X5Each independently selected from H, D, F, Cl, bromo, cyano, phenyl, substituted phenyl, furyl, substituted furyl, thienyl, substituted thienyl, pyridyl, substituted pyridyl, naphthyl, substituted naphthyl, anthracyl, substituted anthracyl, fused heteroaromatics, substituted fused heteroaromatics, -N (Y)1Y2)、-B(Y1Y2)、-OY1、 -SY1Wherein Y is1And Y2Is C1-C12Alkyl substitution, C6-C16Aryl substituted of, C5-C16Aryl-hetero-substituted radical of (A), C7-C16Fused heteroaryl substitution of (a);
wherein R is1、R2、R3、R4、R5Optionally with C on the same or different ring5-C16The chemical bonding is realized through an alkane chain, an alkoxy chain and an alkyl sulfide chain. Such linkages include, but are not limited to, inter alia the following spirocyclic alkanes:
according to the present disclosure, the organic semiconductor compound contained in the light-emitting layer of the organic light-emitting diode may have a variety of structures, typically having the following structure:
table 1: typical structure of organic semiconductor compound contained in light-emitting layer
R in the organic semiconductor compound of the light-emitting layer in the organic light-emitting diode described by the general formula (I)1、R2、R3、R4、 R5Optionally, a chemical crosslinking group. There are many options for chemical crosslinking groups, typically including those that are exposed to heat or ultraviolet light, such as vinyl, acrylate, or trifluoroethylene. Examples of the compound containing a vinyl group (A), a propenyl group (B) and a trifluorovinyl group (C) bonded to a benzene ring are as follows:
the above groups can be chemically bonded to the compound of the present invention in principle to achieve the corresponding effects.
The organic semiconductor compound contained in the light-emitting layer in the organic light-emitting diode according to the present invention has, but does not exclusively include, the following structure:
table 2: chemically crosslinkable luminescent compounds
The luminescent compounds in table 2 are generally applied to the preparation of OLED light emitting devices by solution film formation. The luminescent compound in the luminescent layer forms a cross-linked network under heating or illumination, is insoluble and infusible, is favorable for fixing a thin film structure, and is particularly favorable for forming a multilayer OLED luminescent device after being subjected to solution film forming again.
In one case, for example, the vinyl-containing compound X-2, upon heating, undergoes the following chemical crosslinking reaction 1 and forms a crosslinked structure of an insoluble, infusible network:
crosslinking reaction 1
In another case, for example, an acrylate-containing X-3 compound undergoes the following crosslinking reaction 2 and forms an insoluble, infusible crosslinked network structure upon being subjected to heating:
crosslinking reaction 2
In another case, for example, the trifluoroethylene-containing X-6 compound, under heating, undergoes the following crosslinking reaction 3 and forms an insoluble and infusible crosslinked network structure:
crosslinking reaction 3
The organic semiconductor compound is mainly applied to an organic light-emitting diode as a light-emitting layer compound material. The light-emitting layer typically contains a light-emitting dopant compound mixed with a Host material (Host) or more than one Host material to form the light-emitting layer. The luminescent dopant compound is mixed in the host material in a certain proportion, which is beneficial to increasing the efficiency of luminescent molecules, reducing self-quenching between the luminescent dopant molecules and luminescent color change under different electric fields, and simultaneously reducing the dosage of expensive luminescent dopants. The mixed film can be formed by vacuum co-evaporation or by mixing and dissolving in solution for spin coating, spray coating or solution printing.
The light-emitting layer compound also comprises an application of the light-emitting layer compound in an organic light-emitting device (OLED organic light-emitting diode). When used as a light-emitting layer, in order to improve light-emitting efficiency, it is necessary to avoid aggregation of light-emitting molecules as much as possible, and a light-emitting (weight) material is usually doped into a host material at a concentration of less than 50%, preferably 1% to 40% of a dopant. Of course, the host material may be a mixture of more than one material, and in this case, the host material in a smaller amount is the auxiliary host material. Fig. 1 is a structural diagram of the OLED device, and the light-emitting layer is denoted by reference numeral 104.
According to the organic light emitting diode described in the present patent scope, one of the applications of the organic semiconductor compound of the present invention is as a light emitting material or a light emitting dopant of a light emitting layer, and as a TADF light emitting material. Different from charge transport materials which require that the carrier mobility is as large as possible, the organic semiconductor is used as a luminescent material to avoid intermolecular quenching as much as possible, and is beneficial to improving the luminous efficiency, so the organic semiconductor disclosed by the invention uses non-coplanarity of molecules as much as possible, and simultaneously uses proper cycloaliphatic alkyl, spiro cycloaliphatic alkyl and the like. Compared with the common methyl, ethyl, propyl, butyl, tert-butyl and other substitutions, the substitution of the cyclic fatty alkyl or the spiral cyclic fatty alkyl can more effectively avoid the annihilation or quenching of intermolecular excitons, thereby increasing the photoluminescence efficiency of the luminescent molecular material and finally improving the luminescence efficiency of the OLED device; compared with general branched alkyl substitution, the cyclic substitution with the same carbon atom number has short and large space effect, and the alkyl chain conformation is greatly reduced due to closed loop, so that the luminous efficiency of the luminescent material is improved; unlike the common branched alkyl group substituted "hyperextension" which brings the disadvantages of reduced luminous efficiency of the light-emitting molecule or increased driving voltage of the OLED device. Referring to table 3 below, it is shown that 1-ethyl-propyl substitution on the 3D molecular mimic molecule B has "hyperextension", which is liable to cause the disadvantage of lowering the luminous efficiency of the light-emitting molecule itself or raising the driving voltage of the OLED device.
Table 3: comparison of cyclic and branched alkane substituted 3D configurations
The luminescent layer of the luminescent device contains the luminescent dopant and forms the luminescent layer with a host material by a co-evaporation or solution co-coating method; the thickness of the luminescent layer is 15-60 nm, and the triplet state energy level of the host material is 2.2-2.9eV, which depends on the wavelength of the emitted light. If it is blue emitting, the triplet level of the host material should be greater than 2.75 eV; if it is green, the triplet level of the host material should be greater than 2.40 eV; in the case of red emission, the triplet level of the host material should be greater than 2.15 eV. One application of the luminescent material of the invention is blue light with the luminescent wavelength of 430-480 nm, and the luminescent material is applied to an OLED luminescent layer as a TADF luminescent dopant.
The molecules of the organic light-emitting layer compounds listed in tables 1 and 2 of the invention contain electronegative boron-bonded aromatic heterocyclic rings and electron-donating nitrogen-bonded aromatic amine rings, and the compounds have both electron-accepting and electron-donating bipolar nature and are mainly used for emitting blue light with the wavelength of 430-480 nm. Without departing from the scope of the present invention, for example, the longer conjugated system is adopted, the luminescent material of the present invention can also be green light with the luminescent wavelength of 510-550nm, or yellow light with the luminescent wavelength of 551-580nm, or even red light with the luminescent wavelength of 581-630 nm.
When a green, yellow, or red light emitting material with lower energy is doped in a blue light emitting material, the low energy material preferentially emits light due to the energy transfer principle, while the higher energy blue light emitting material only functions as a host material or is sensitized to emit light. Therefore, the organic semiconductor of the present invention can be obviously used as a host material of a green, yellow and red light emitting OLED light emitting layer, that is, the light emitting layer contains the organic light emitting material of the present invention as a host material and then is doped with other light emitting materials of green, yellow and red light with longer wavelength and smaller energy. When charges are injected into the thus-constituted light-emitting layer in both directions, the generated excitons emit wavelengths in the light-emitting material with the lowest energy.
In another case, a conventional host material and a conventional red, green, or blue light emitting dopant may be used for the light emitting layer, and the organic semiconductor compound according to the present invention may be incorporated into the light emitting layer as an energy transfer sensitizing material. The semiconductor energy level of the sensitization functional material is between the main material and the luminous dopant, and injected electrons and holes are sequentially transferred from the main material in the luminous layer to the sensitization material and then to the luminous dopant according to the energy transfer principle. This stepped energy transfer often increases device lifetime and increases device efficiency.
To obtain efficient green and red OLEDs, usually either a TADF emissive material using triplet phosphorescent OLED materials or using triplet emission mechanisms is used. The emissive layer containing a phosphorescent light-emitting material, e.g. Ir (ppy)3Is green light, or Ir (Piq)3As a red dopant, a light-emitting (weight) material is doped into a host material at a concentration of 2 to 20%. Numerous other triplet red, green and even yellow light-emitting materials have been developed in the literature or commercially and are likewise suitable for use in the context of the present invention.
To obtain highly efficient blue OLEDs, usually a TADF light emitting material using triplet phosphorescent OLED materials or using triplet emission regime is used. The emissive layer contains phosphorescent emissive materials, such as modified mFirPic, which have higher luminous efficiency, but lack lifetime and color coding. While the efficiency EQE is about 10% with the fluorescent light emitting material, such as B6, the lifetime and color scale can substantially meet the current commercial AMOLED requirements. Numerous other blue-emitting phosphors have been developed in the literature or commercially and are equally suitable for use within the scope of the present invention.
In a conventional organic light emitting diode chip, a hole injection layer HIL is usually vapor-deposited on a transparent conductive glass or ITO plated indium-tin oxide, and then a hole transport layer HTL, a light emitting layer EML, an electron transport layer ETL, an electron injection layer EIL are sequentially deposited, and finally a metal layer, such as an aluminum metal layer, is added to serve as an anode conductive and sealing layer. (FIG. 1) when ITO is positively charged and aluminum is negatively charged to a certain electric field, holes are injected from ITO through HIL and HTL to EML, and electrons are injected from EIL connected with aluminum and then are transported through ETL to EML. The electrons and holes meet in the EML, recombine into excitons (excitons), and then part of the excitons release energy in the form of light radiation back to the ground state. The wavelength of the optical radiation is determined by the energy gap of the light emitting dopant in the EML layer. Numerous other simple or more complex OLED light emitting device structures have been developed in the literature or commercially and are equally applicable to the scope of the present invention.
The main material is commonly used as a material containing carbazole or arylamine structure. One commonly used known host material is 4,4 '-N, N' -dicarbazole-biphenyl (CBP):
for TADF blue OLEDs, electron injection and higher triplet energy levels are required, often using DPEPO or mCBP materials as host materials as follows:
to achieve good light emitting device performance, a hole injection layer, such as phthalocyanine blue (CuPc) or other aromatic amine-containing compounds (appl. phys. lett.,69,2160(1996), such as m-TDATA, may optionally be provided on the anode.
Similarly, between the hole injection layer and the emissive layer EML, a hole transport layer may be selected, for example, using 4, 4' -bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl (α -NPD)
To balance the injection of electrons and holes and improve luminous efficiency, an Electron Transport Hole Blocking (ETHB) material can be optionally selected, and an example is 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene TPBi, the structure of which is as follows:
between the ETL and the cathode, an electron injection layer is also typically used. The electron injection layer is typically metal hah with a lower work function, lithium fluoride or compounds thereof such as 8-hydroxyquinoline hah (Liq):
numerous other hole injection materials, hole transport materials, host materials, electron transport materials, electron injection materials, exciton blocking materials, which have been developed in the literature or commercially, may likewise be suitable for use within the scope of the present invention.
OLED light emitting devices are complex multilayer structures and fig. 1 is a typical, but not the only, architecture of application. Wherein the organic semiconductor layer has an overall thickness of 50 to 250 nm, preferably an overall thickness of 80 to 180 nm. The compounds of the invention can in principle be used in complex multilayer light-emitting devices of OLEDs, for example using exciton blocking layers, including electron-transporting hole blocking, hole-transporting electron blocking layers, between the light-emitting layer and the charge transport layer, provided that the singlet and triplet states of the material are greater than those of the light-emitting material.
The invention also discloses an organic semiconductor compound, which has the chemical structural general formula as follows:
wherein R is1、R2、R3、R4、R5Containing at least one saturated or unsaturated aliphatic ring;
the R is1、R2、R3、R4、R5The aliphatic ring comprises three-membered ring, four-membered ring, five-membered ring, six-membered ring, seven-membered ring, eight-membered ring, or C of each of the above rings1-C12Alkyl substitution of (C)1-C12Alkoxy-substituted radical of (A), C6-C12Aryl-substituted of (A), C5-C12Aryl-hetero-substituted of, C7-C12The fused aromatic heterocyclic group of (1) is substituted, F is substituted, Cl is substituted, Br is substituted, and isotope D is substituted;
wherein X is1、X2、X3、X4、X5Each independently selected from H, D, F, Cl, phenyl, substituted phenyl, furyl, substituted furyl, thienyl, substituted thienyl, pyridyl, substituted pyridyl, naphthyl, substituted naphthyl, anthracenyl, substituted anthracenyl, fused heteroaryl, substituted fused heteroaryl, -N (Y)1Y2)、-B(Y1Y2)、-OY1、-SY1Wherein Y is1And Y2Is C1-C12Alkyl substitution, C6-C16Aryl substituted of, C5-C16Aryl-hetero-substituted radical of (A), C7-C16A fused heteroaryl substituent of (a), or a chemical crosslinking group;
wherein R is1、R2、R3、R4、R5Optionally with X on the same or different ring1、X2、X3、X4、X5Chemically bonded through an alkyl chain, alkoxy chain, alkylthio chain, or optionally containing a chemical crosslinking group.
According to the organic semiconductor compound, the organic semiconductor compound includes but is not limited to the following structure:
and the following crosslinkable structures:
although the above crosslinkable structures differ in structure, they proceed in principle according to a similar principle to the crosslinking reactions 1, 2,3, resulting in corresponding insoluble, infusible crosslinked network structures.
The organic semiconductor luminescent material of the invention generally belongs to electronegative boron-containing atoms and organic bonding of power supply aromatic amine, wherein the boron-containing aromatic heterocycle responsible for electron injection dominates LUMO, and the aromatic heterocycle responsible for hole injection dominates HOMO, and Gaussian functional molecular calculation shows that the overlapping performance of HOMO and LUMO is little, which is beneficial to generating reverse channeling system exchange (RISC) to generate TADF luminescent mechanism, and the high efficiency of single-state and three-state luminescence is obtained. Reverse cross-over (RISC) generally occurs between S1 and T1, and recent research has shown that S1 and Tn (n is 2,3,4, etc.) may also occur. The energy level difference Delta E (S1-T1) between the singlet state and the triplet state of the organic luminescent layer compound disclosed by the invention is less than 0.4eV, the fluorescence relaxation time is at the level of microseconds and sub-microseconds, and the fluorescence relaxation time is different from the fluorescence with the nanosecond (nano-second) level, so that the internal quantum efficiency is more than 25% when the organic luminescent layer compound is applied to an organic light-emitting diode, and the TADF light-emitting diode is obtained. The organic semiconductor luminescent material has low cost, high charge transmission and good processing performance, and is applied to preparing organic light emitting diodes to obtain improved high efficiency, low voltage and long service life. Especially for TADF blue materials, the improvement and increase of lifetime is an important advance in the industry.
The organic light emitting diode can be used as a light emitting lattice to be applied to a full-color OLED display screen. The organic semiconductor material provided by the invention can be applied to an organic light-emitting diode to obtain white light after regulation of RGB (red, green and blue) three colors, and is applied to OLED (organic light-emitting diode) illumination. The OLED panel screen is used for displaying, and can be applied to mobile phone screens, i-Pack screens, television screens, computer screens and the like, or used as lighting walls, light-emitting plates, light-emitting lamps and the like.
Drawings
Fig. 1 is a schematic diagram of an organic light emitting diode structure.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, specific embodiments accompanied with examples are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention can be implemented in many ways other than those described herein and similar generalizations can be made by those skilled in the art without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.
General methods for the synthetic preparation of compounds:
the organic semiconducting compounds of the present invention may be prepared using a variety of synthetic routes, of which the following reaction schemes are typically followed:
reaction synthetic route
Example 1: synthesis preparation of Compound C-3 Material
1) Compound C-3 was prepared according to the following chemical synthetic route,
a250 ml three-necked flask was charged with Compound 1(14.4g, 44mmol), dry THF (120ml), palladium acetate (0.52g, 2.24mmol), phosphorus ligand (2.0g, 4.6mmol), zinc cyclopentylalkyl bromide (272ml, 132mmol), purged with nitrogen and warmed to 60 ℃ for 16 hours. The reaction was terminated with aqueous sodium carbonate (1M). The reaction solution was filtered through celite, rinsed with EtOAC, and the organic phase was washed 3 times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was spun off in vacuo to obtain oil 3(10.48g, 78%% yield) after passing through a silica gel column (PE: EtOAC ═ 9: 1).
2) Intermediate compound 5 was prepared according to the following reaction:
a100 ml three-necked flask was charged with compound 4(3.7g, 16.37mmol), compound 3(5.0g, 16.37mmol), dried toluene (60ml) dissolved, palladium acetate (0.037g, 0.164mmol), tert-butyl sodium (3.15g, 32.7mmol), tri-tert-butylphosphine ligand TTBP (0.13g, 0.64mmol), purged with nitrogen, and heated to 110 ℃ for 8 hours. After cooling to room temperature, the reaction solution was filtered through celite, rinsed with EtOAC, and the organic phase was washed 3 times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was dried under vacuum and the column was passed over silica gel (PE: EtOAC ═ 8: 2) to give oil 5(5.9g, 80%% yield).
3) Intermediate compound 6 was prepared according to the following reaction:
A100-mL three-necked flask was charged with compound 5(5.9g, 13.0mmol), compound 3(4.58g, 15.0mmol), dried toluene (60mL) dissolved, palladium acetate (0.037g, 0.164mmol), tert-butyl sodium (3.15g, 32.7mmol), tri-tert-butylphosphine ligand (0.13g, 0.64mmol), and nitrogen sparged to remove air, and the mixture was heated to 110 ℃ for reaction at 8 hours. After cooling to room temperature, the reaction solution was filtered through celite, rinsed with EtOAC, and the organic phase was washed 3 times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was dried under vacuum and the silica gel was passed through a column (PE: DCM ═ 8: 2) to give 6(6.55g, 70% yield) as a white solid.
4) Intermediate compound C-3 was prepared according to the following reaction:
a100 ml three-neck flask was charged with compound 6(6.55g, 9.1mmol), dried tert-butylbenzene (60ml), bubbled with nitrogen to remove air, then frozen and cooled to-30 deg.C, and a solution of tert-butyl hacherries (9.6mmol, 5.65ml x1.7M) in n-hexane was added dropwise, after which the temperature was raised to 60 deg.C and stirred for 2 hours. The low boiling solvent n-hexane was distilled off under reduced pressure. The reaction was cooled to-30 ℃ and boron tribromide (2.74g, 10.92mmol) was added, and the temperature was allowed to rise to room temperature and stirred for 0.5 h. The reaction mixture was cooled to 0 ℃ again, diisopropylethylamine (2.35g, 18.22mmol) was added thereto, and the mixture was stirred at room temperature for 1 hour, then heated to 120 ℃ and stirred for 3 hours. And after the reaction is finished, cooling to room temperature, dropwise adding a sodium acetate aqueous solution in an ice water bath to quench the reaction, and adding n-hexane for further phase separation. The organic phase was passed through a short column of silica gel and rinsed with n-hexane. The organic phase was evaporated to dryness under reduced pressure and dissolved in a minimum amount of toluene, and n-hexane was added for precipitation. The product was obtained as C-3(2.52g, 40% yield) as a pale yellow solid. C50H53BN2Molecular formula calculated molecular weight is 692.78, mass spectrum detection M/z is 692.43, photoluminescence wavelength is blue light PL 457nm, and half-height peak width FWMH is 30nm。
Example 2: synthesis preparation of deuterated ring-substituted compound C-4 material
Compound 3(5.0g, 16.37mmol), DMSO-d6(34.3ml, 491.1mmol), sodium t-butoxide (0.786g, 8.18mmol) were added to a 100ml flask, the reaction was heated to 60 ℃ for 16 hours and then cooled to room temperature, 120ml of deionized water was added and 3X100ml was extracted with ethyl acetate. The organic phase was washed 2 × 100ml with brine, the organic phase was evaporated to dryness under reduced pressure and the product 3D was obtained on column (4.5g, 90% yield).
Product C-4(2.54g, 40% yield) was obtained following the procedure 2), 3), 4) of example 1. C50H49D4BN2The molecular formula calculated molecular weight is 696.80, mass spectrum detection M/z is 696.46, photoluminescence wavelength is that blue light PL is 458nm, and half-height peak width FWMH is 30 nm.
Example 3: synthetic preparation of other compound materials
Similarly, according to the above synthetic chemistry principle, the following organic semiconductor luminescent material compounds were synthesized, and the specific listed compounds were verified by mass spectrometry for molecular weight and fragments of molecules, and specifically shown in table 4 below, without departing from the scope of the present invention:
table 4: compound synthesis and characterization
Example 4: quantum mechanical calculation of organic semiconductor compound:
the highest occupied molecular orbital energy level (HOMO) and the lowest unoccupied molecular orbital energy Level (LUMO), as well as the singlet energy level and the triplet energy level of the following compounds were calculated using the Gaussian 04 version of the quantum mechanical DFT functional. Examples of the following molecular calculations are:
the above shows that the above molecule emits blue light (S1 ═ 462nm), and the difference between the triplet T1, T2 level and the singlet S1 level is less than 0.4eV, which is advantageous for achieving the TADF light emission mechanism by RISC, and the efficiency of light emission is improved by reverse channeling by fully utilizing the triplet occupying 75% of the excitons. Other molecules were calculated similarly and are listed in tables 4, 5.
Example 5: synthesis preparation of crosslinkable compound material
Following the general synthetic route and following the specific procedures of example 1, the following crosslinkable compound materials were synthesized, and analyzed by MALDI-TOF mass spectrometry to determine molecular weights and fragment characteristics, as shown in Table 5:
table 5: synthesis and characterization of crosslinkable Compounds
Example 6 evaporation OLED device application example-the compounds of the invention as light emitting dopant materials:
and (3) evaporating an OLED device manufacturing process: at a background vacuum of 10-5In multi-source evaporation OLED preparation equipment of Pa, the following device structure is adopted: anode ITO/HIL
/HTL
EBL (50A)/Host 1-40% of luminescent dopant
/HBL(50A)/ET
/EI
the/Al cathode evaluates the performance of each material applied to the OLED device. The specific OLED device structure is ITO/HTACN
/NPB
/mCBP(50A)/DPEPO:dopant 5％
/Liq
/TPBi
/LiF
Al, varying the use of different luminescent doping materials of the invention versus the comparison Ref 1, Ref2, Ref3 luminescent materials (US patent application US 20190058124).
Table 6: adopted contrast material structure
Table 7: performance of the obtained OLED device (room temperature @300 nits):
for reference, the driving voltage of the comparative device a was 5.2V, the external quantum efficiency EQE was 12.5%, the EL emission spectrum CIE (x, y) was (0.13,0.11), and the lifetime was LT 80% at 1000 nits, i.e., 90 hours at 300 nits.
As can be seen from the comparison of the above table 7 with A, B blue OLED devices, the material of the invention, as a luminescent material, has the effects of reducing the working voltage, increasing the luminous efficiency of the device by 5-15% and increasing the service life of the device by 10-19% when applied to the blue OLED devices.
Comparing the device C with the device 9, namely the light blue OLED device, the utilization of the biphenyl compound containing cyclopentane substituent has the effects of improving the efficiency by 14% and prolonging the service life of the device by 8%.
Comparing the device 1 with the device 2, it can be seen that the deuterated cyclopentane compound C-4 has similar luminous efficiency and voltage compared with the C-3 with similar structure, but the device 2 has 5% effect of prolonging the service life compared with the device 1.
In conclusion, it is demonstrated that the organoboron luminescent material adopting cyclic substitution or spirocycloalkyl substitution has the effects of obviously increasing the luminous efficiency (EQE) of the device and prolonging the service life LT 80%.
Example 7: evaporation OLED device application example-application of the compounds of the invention as host material and dopant material of the light emitting layer:
table 8: the compound of the invention is used as a host material and a dopant material of a luminescent layer
The results in Table 8 show that the organic semiconductor material of the present invention, such as C-32, has both electron and hole ambipolar properties, and can also be used as a green host material of OLED. Device 2 shows that the blue material C-32 of the invention is doped with a small amount of red light doped luminescent material Ir (Piq)3(such as 0.6 percent) can simultaneously realize the composite light of red light and blue light emission, namely the application of a white light device.
Example 8: evaporation OLED device application example-application of the compounds of the invention as luminescent layer sensitizing dopants:
the specific OLED device structure is ITO/HTACN
/NPB
mCBP (50A)/DPEPO (96%): sensitizer (1%)
/Liq
/TPBi
/LiF
/Al
The above table shows that the material of the present invention, such as C-5, can be used as "sensitizing" dopant, and the DPEPO material is used as host, and is doped with phosphorescent material mFirPic or fluorescent dye B6 with high luminous efficiency, and the singlet excitons in the TADF material disclosed herein transfer energy to the luminous doped material through efficient Forster transfer, and emit light from the latter, so that high-performance OLED can be obtained. Comparing the device 1 with A, C-5 as sensitizing material, the efficiency can be improved from 10.6% to 14.2% by doping 1% into the host material, and the service life can be improved by 91%. Comparing device 2 with B, C-5 as a sensitizing material, the efficiency was improved from EQE 7.0% to 11.3% by incorporating 1% into the host material.
Example 9: the application of the cross-linkable luminescent material in the solution coating OLED device comprises the following steps:
after a conductive glass ITO surface is cleaned by a solvent and plasma, a PEDOT conductive polymer is spin-coated in solution to serve as a hole injection layer HIL, a poly (triphenylamine-9.9-diheptane fluorene) solution spin-coating film is used as a hole transmission layer HTL, and then a light-emitting layer is spin-coated in 10% of the crosslinkable light-emitting material and a main body material solution (95% of the main body material: 5% of light-emitting dopant). Heating to 160 ℃ under nitrogen for 30 minutes to crosslink the film into an infusible and insoluble luminescent layer EML; finally reaching a background vacuum of 10-5In the multisource evaporation OLED production equipment of pa, an OLED device was produced similarly to example 4 by evaporation of the BL layer, the electron transport layer ETL and the electron injection layer EIL. The comparative experiment was that the solution spin coating of the light emitting layer was not followed by a treatment of heating to 160 ℃ under nitrogen for 30 minutes, and the other steps were identical. The OLED device results show that the two starting OLEDs perform similarly, and the lifetime of the thermally crosslinked OLED device increases by 20%.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Those skilled in the art can make numerous possible variations and modifications to the disclosed embodiments, or modify equivalent embodiments, without departing from the scope of the invention, using the teachings disclosed above. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the protection scope of the technical solution of the present invention, unless the content of the technical solution of the present invention is departed from.
Claims (10)
1. An organic light emitting diode comprising:
(a) a cathode having a cathode electrode and a cathode electrode,
(b) an electron transport layer adjacent to the cathode,
(c) an anode having a first electrode and a second electrode,
(d) a hole transport layer adjacent to the anode,
(e) a light-emitting layer sandwiched between the electron-transporting layer and the hole-transporting layer, the light-emitting layer comprising an organic semiconductor compound having a general chemical structure:
wherein R is1、R2、R3、R4、R5Containing at least one saturated or unsaturated aliphatic ring;
the R is1、R2、R3、R4、R5The aliphatic ring comprises three-membered ring, four-membered ring, five-membered ring, six-membered ring, seven-membered ring, eight-membered ring, or C of each of the above rings1-C12Alkyl substitution of (C)1-C12Alkoxy-substituted radical of (A), C6-C12Aryl-substituted of (A), C5-C12Aryl-hetero-substituted of, C7-C12The fused aromatic heterocyclic group of (1) is substituted, F is substituted, Cl is substituted, Br is substituted, and isotope D is substituted;
wherein X is1、X2、X3、X4、X5Each independently selected from H, D, F, Cl, phenyl, substituted phenyl, furylSubstituted furyl, thienyl, substituted thienyl, pyridyl, substituted pyridyl, naphthyl, substituted naphthyl, anthracenyl, substituted anthracenyl, fused heteroaryl, substituted fused heteroaryl, -N (Y)1Y2)、-B(Y1Y2)、-OY1、-SY1Wherein Y is1And Y2Is C1-C12Alkyl substitution, C6-C16Aryl substituted of, C5-C16Aryl-hetero-substituted radical of (A), C7-C16A fused heteroaryl substituent of (a), or a chemical crosslinking group;
wherein R is1、R2、R3、R4、R5Optionally with X on the same or different ring1、X2、X3、X4、X5Chemically bonded through an alkyl chain, alkoxy chain, alkylthio chain, or optionally containing a chemical crosslinking group.
2. The organic light emitting diode of claim 1, wherein the organic semiconductor compound in the light emitting layer of the light emitting diode comprises a saturated or unsaturated aliphatic ring selected from the group consisting of:
3. the organic light emitting diode as claimed in claim 1, wherein R is an organic semiconductor compound in an emitting layer of the light emitting diode1、R2、R3、R4、R5Optionally with X on the same or different ring1、X2、X3、X4、X5Chemically bonded through an alkane chain, an alkoxide chain and an alkane-sulfide chain, and is selected from the following bonding structures:
4. the organic light emitting diode as claimed in claim 1, wherein R is an organic semiconductor compound in an emitting layer of the light emitting diode1、R2、R3、R4、R5The chemical crosslinking group in (1) is selected from vinyl, acrylate or trifluorovinyl.
5. The organic light emitting diode according to claims 1, 2,3 and 4, wherein the organic semiconductor compound of the light emitting layer in the light emitting diode has the following structure:
and the following crosslinkable and crosslinked structures:
6. an organic semiconductor compound having a chemical structural formula:
wherein R is1、R2、R3、R4、R5Containing at least one saturated or unsaturated aliphatic ring;
the R is1、R2、R3、R4、R5The aliphatic ring comprises three-membered ring, four-membered ring, five-membered ring, six-membered ring, seven-membered ring, eight-membered ring, or C of each of the above rings1-C12Alkyl substitution of (C)1-C12Alkoxy-substituted radical of (A), C6-C12Aryl-substituted of (A), C5-C12Aryl-hetero-substituted of, C7-C12The fused aromatic heterocyclic group of (1) is substituted, F is substituted, Cl is substituted, Br is substituted, and isotope D is substituted;
wherein X is1、X2、X3、X4、X5Each independently selected from H, D, F, Cl, phenyl, substituted phenyl, furyl, substituted furyl, thienyl, substituted thienyl, pyridyl, substituted pyridyl, naphthyl, substituted naphthyl,Anthracenyl, substituted anthracenyl, fused heteroaryl, substituted fused heteroaryl, -N (Y)1Y2)、-B(Y1Y2)、-OY1、-SY1Wherein Y is1And Y2Is C1-C12Alkyl substitution, C6-C16Aryl substituted of, C5-C16Aryl-hetero-substituted radical of (A), C7-C16A fused heteroaryl substituent of (a), or a chemical crosslinking group;
wherein R is1、R2、R3、R4、R5Optionally with X on the same or different ring1、X2、X3、X4、X5Chemically bonded through an alkyl chain, alkoxy chain, alkylthio chain, or optionally containing a chemical crosslinking group.
7. The organic semiconducting compound of claim 6, having the structure:
and the following crosslinkable and crosslinked structures:
8. the organic light emitting diode according to claim 1 to 5, wherein the organic semiconductor compound in the light emitting diode is a light emitting dopant in a light emitting layer.
9. The organic light-emitting diode according to claim 1 to 6, wherein the organic semiconductor compound in the organic light-emitting diode is a host material in a light-emitting layer.
10. The organic light-emitting diode according to claim 1 to 6, wherein the organic semiconductor compound in the organic light-emitting diode is a sensitizing material for energy transfer in a light-emitting layer.
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| WO2022078431A1 (en) * | 2020-10-14 | 2022-04-21 | 浙江光昊光电科技有限公司 | Organic compound and use thereof in photoelectric field |
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