CN104247073A - Organic electroluminescent element and method for manufacturing same - Google Patents

Organic electroluminescent element and method for manufacturing same Download PDF

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CN104247073A
CN104247073A CN201380019561.XA CN201380019561A CN104247073A CN 104247073 A CN104247073 A CN 104247073A CN 201380019561 A CN201380019561 A CN 201380019561A CN 104247073 A CN104247073 A CN 104247073A
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organic electroluminescent
electroluminescent device
compound
organic
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CN104247073B (en
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深川弘彦
清水贵央
森井克行
有元洋一
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Nippon Shokubai Co Ltd
Japan Broadcasting Corp
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Nippon Hoso Kyokai NHK
Nippon Shokubai Co Ltd
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Priority claimed from JP2012193519A external-priority patent/JP5993667B2/en
Priority claimed from JP2012228460A external-priority patent/JP6110099B2/en
Priority claimed from JP2013039901A external-priority patent/JP6226533B2/en
Application filed by Nippon Hoso Kyokai NHK, Nippon Shokubai Co Ltd filed Critical Nippon Hoso Kyokai NHK
Priority claimed from PCT/JP2013/060755 external-priority patent/WO2013157451A1/en
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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]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • 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
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

To provide: (1) an organic-inorganic hybrid-type organic electroluminescent element having excellent light-emission characteristics in which even when a low-molecular compound layer is used as the layer constituting the organic electroluminescent element, crystallization of the low-molecular compounds is suppressed; (2) an organic-inorganic hybrid-type organic electroluminescent element having even better light-emission characteristics than conventional organic-inorganic hybrid-type organic electroluminescent elements; and (3) an organic electroluminescent element that is easy to manufacture and that has excellent light-emission efficiency and lifespan. The present invention is an organic electroluminescent element having a structure in which a plurality of layers are stacked, the organic electroluminescent element being characterized in having a metal oxide layer between a first electrode and a second electrode and having, on the metal oxide layer, a buffer layer formed from an organic compound.

Description

Organic electroluminescent device and manufacture method thereof
Technical field
The present invention relates to organic electroluminescent device and manufacture method thereof.More specifically, the present invention relates to the organic electroluminescent device as display unit or the lighting device etc. such as display part of electronic equipment and manufacture method thereof.
Background technology
Organic electroluminescent device (organic EL element) is expected as the novel light-emitting element that can be applied to display device or illumination.
Organic electroluminescent device has thin, soft and flexible such feature, and when being used as display unit, compared with the liquid crystal indicator becoming now main flow or plasm display device, have and can realize high brightness, high-resolution display, have compared with liquid crystal indicator that visual angle is also broad waits excellent feature, thus expect organic electroluminescent device to expand from now on as the display etc. of television set or mobile phone purposes and be used as lighting device.
Organic EL element has the structure clipping the one kind or two or more layer comprising the luminescent layer formed containing photism organic compound between the anode and the cathode, utilize by anode injected holes with by negative electrode injected electrons again in conjunction with time energy excitation photism organic compound, thus obtain luminescence.Organic EL element is current drive-type element, in order to more efficiently apply flexibly circulated electric current, has carried out various improvement to component structure, and has also carried out various research for the material of the layer of composed component.
Organic electroluminescent device has be laminated with electron transfer layer, luminescent layer, hole transmission layer etc. 2 layers with the structure on upper strata between negative electrode and positive electrode, and the material for each layer of applicable formation is studied, develops.Such as, the luminescent material (see patent documentation 1) with the compound of ad hoc structure containing having boron atom is disclosed.Further, the hole blocking layer (see patent documentation 2) that the compound with ad hoc structure with boron atom is suitable as organic electroluminescent device is disclosed.
In addition, for utilize by anode injected holes with by negative electrode injected electrons again in conjunction with time energy excitation photism organic compound thus obtain luminescence organic electroluminescent device for, importantly, hole from anode is injected, electron injection from negative electrode is carried out all smoothly, therefore in order to make hole inject, electron injection is more successfully carried out, for hole injection layer, the material of electron injecting layer has also carried out various research, be recently reported a kind of organic electroluminescent device (see non-patent literature 1 ~ 3) of forward structure, it use polyethylene imine based or modify the material of polyethylene imine based compound as the electron injecting layer that can be coated with.
But for the organic electroluminescent device that the layer between negative electrode and positive electrode is all formed by organic compound, consequently, it is easily because of oxygen, water and deterioration occurs, and in order to prevent their intrusion, tight seal is integral.This becomes the reason making the manufacturing process of organic electroluminescent device become loaded down with trivial details.To this, organic-inorganic mixed type electroluminescent cell (HOILED element) (see patent documentation 3) that the part proposing the layer between negative electrode and positive electrode is formed by inorganic oxide.For this element, hole transmission layer, electron transfer layer are changed to inorganic oxide, FTO or ITO of electroconductive oxide electrode can be used as thus as negative electrode, use gold as anode.From the view point of element drives, this means to eliminate the restriction to electrode.Result makes without the need to using the metal that the work content such as alkali metal or alkali metal compound is little, can when carrying out luminescence without when tight seal.In addition, this HOILED element has following feature: it is standard that negative electrode is positioned at substrate next-door neighbour top, and anode moves to upper electrode and forms reverse geometry.Along with the development of oxide TFT, in research towards in the application of large-scale OLED display, organic EL of reverse geometry receives publicity due to the feature of the oxide TFT of N-shaped.This HOILED element is expected to develop to some extent as the alternative of reverse geometry organic EL element.
As the organic electroluminescent device of existing organic-inorganic mixed type, disclose organic film light-emitting component as described below, it has anode and negative electrode, be clipped in more than 1 layer or 2 layers organic compound layer between above-mentioned anode and above-mentioned negative electrode, and between above-mentioned anode and above-mentioned organic compound layer and between above-mentioned negative electrode and above-mentioned organic compound layer, have more than at least a kind metal-oxide film (see patent documentation 4).In addition, disclose organic thin film electroluminescent elements as described below, it has anode, negative electrode, is clipped in more than 1 layer or 2 layers organic compound layer between anode and negative electrode, and there is between anode and organic compound layer or between negative electrode and organic compound layer more than at least a kind metal-oxide film, there is more than 1 layer or 2 layers self-assembled monolayer between described each layer, this self-assembled monolayer is forming energy potential barrier for main charge carrier, not forming energy potential barrier (see patent documentation 5) for reverse carrier.In addition, disclose and have and will be added with iridic compound as the organic electroluminescent device (see non-patent literature 4) of the organic-inorganic mixed type of the structure of polyvinylcarbazole polymer lamination on metal oxide layer of dopant and poly-(9 of iridic compound will be added with, 9-dioctyl fluorenyl-2,7-bis-base) as the organic electroluminescent device (see non-patent literature 5) of the organic-inorganic mixed type of luminescent layer.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2011-184430 publication
Patent documentation 2: No. 2005/062676, International Publication
Patent documentation 3: Japanese Unexamined Patent Publication 2009-70954 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2007-53286 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2012-4492 publication
Non-patent literature
Non-patent literature 1:Tao Xiong and other 3 people " Applied Physics Letters " 93 volumes, 2008, pp123310-1
Non-patent literature 2:Yinhua Zhou and other 21 people " Science " No. 336,2012, pp327
Non-patent literature 3:Jianshan Chen and other 6 people " Journal of Materials Chemistry " 2012,22 volumes, pp5164
Non-patent literature 4:Henk J.Bolink and other 3 people " Advanced Materials ", 2010, the 22nd volume, p2198-2201
Non-patent literature 5:Henk J.Bolink and other 2 people " Chemistry of Materials ", 2009, the 21st volume, p439-441
Summary of the invention
Invent problem to be solved
As mentioned above, the organic electroluminescent device formed by organic substance for each layer being configured with electro-luminescence element and the organic electroluminescent device of organic-inorganic mixed type are studied, develop.
The organic electroluminescent device of organic-inorganic mixed type it is believed that intensity, durability that flexibility, mouldability and the inorganic constituents that can have organic principle concurrently and have have, and, compared with the organic electroluminescent device only forming each layer by organic compound, high to the patience of oxygen, water, the necessity therefore with each layer of tight seal element internal reduces, when manufacturing time of spending the also advantage such as few, it is practical is expected.On the other hand, compared with the organic electroluminescent device formed by organic substance with each layer being configured with electro-luminescence element, the organic electroluminescent device of organic-inorganic mixed type also has room for improvement in the various characteristics such as the characteristics of luminescence, therefore needs the organic electroluminescent device developing the organic-inorganic mixed type improving the characteristics such as the characteristics of luminescence further.
Usually, for the organic electroluminescent device that each layer being configured with electro-luminescence element is formed by organic substance, known to utilizing the method for two or more low molecular compound layer of method lamination such as vacuum evaporation or the element by making the guest molecule method etc. be doped in host molecule obtain having the high characteristics of luminescence.On the other hand, in the formation of the organic electroluminescent device of the organic-inorganic mixed type studied in the past, macromolecular compound coating film forming is become main flow as the formation of luminescent layer.To this, in order to improve the characteristics of luminescence of the organic electroluminescent device of organic-inorganic mixed type, the present inventor for use low molecular compound as formed luminescent layer, hole transmission layer etc. material and by the mode of two or more low molecular compound layers of method lamination such as vacuum evaporation with make the guest molecule mode be doped in host molecule carry out various research.The result done like this is, find to create new problem as described below: oxide skin(coating) negative electrode formed if be formed in contacts such formation with low molecular compound layer, then can cause the crystallization of the low molecular compound layer contacted with oxide skin(coating), leakage current increases and current efficiency reduction thus, can cannot obtain the luminous such unfavorable condition in uniform face in severe cases because crystallization produces.Although above-mentioned situation is not observed in the element with application type macromolecule organic layer, it is believed that also there is harmful effect, think that this problem of solution is very important for the long lifetime of the organic electroluminescent device of organic-inorganic mixed type.
In addition, for the organic electroluminescent device of organic-inorganic mixed type, there is following problem: compared with the injection in the hole from anode, the injection from the electronics of negative electrode is less, fails fully for luminescence from anode injected holes.In addition, the physical property electrical contact good for a long time of inorganic layer and organic layer is originally difficult to realize, and this causes the short life of device, and it is important topic.
For being expected to the organic electroluminescent device of the application expanded in the purposes such as display unit, lighting device, also be key factor owing to easily manufacturing, therefore highly expect the organic electroluminescent device without the need to the organic-inorganic mixed type of tight seal, and need the luminous efficiency of organic electroluminescent device and the method in life-span that improve organic-inorganic mixed type further.In addition, in display applications, the HOILED element with reverse geometry is useful in circuit, and its development is expected.
The present invention completes in view of the foregoing, its object is to the organic electroluminescent device that (1) provides a kind of organic-inorganic mixed type, even if when using low molecular compound layer as the crystallization that also can suppress low molecular compound when being configured with the layer of electro-luminescence element, excellent in luminous characteristics; (2) organic electroluminescent device of the organic-inorganic mixed type providing the characteristics of luminescence more excellent than the organic electroluminescent device of existing organic-inorganic mixed type; And (3) provide a kind of organic electroluminescent device, it easily manufactures, and luminous efficiency and life-span are all excellent.
For the means of dealing with problems
The present inventor finds, having in the organic electroluminescent device of organic-inorganic mixed type of metal oxide layer, by making metal oxide layer to have the resilient coating formed by organic compound, can solve above-mentioned problem between the 1st electrode and the 2nd electrode.So-called resilient coating refers to the layer of the problem of the organic electroluminescent device solving above-mentioned organic-inorganic mixed type herein, namely solves the crystallization of the organic layers such as luminescent layer, the physical property at low electron injection ability and interface and the layer of chemically long-time stability.Specifically, in order to prevent the crystallization caused by the concavo-convex grade that exists on oxide surface, the organic substance of preferred more HMW, in addition, in order to improve electron injection ability, preferably the energy level to luminescent layer is formed as stepped, in addition in order to make the pumping (pumping) of the energy existed as the distinctive problem of reverse geometry (put forward high-octane grade (to rise to, uphill)) successfully carry out, increase carrier number more particularly by methods such as doping.In order to improve electron injection ability, also have the method usually producing interface dipole by distributing a large amount of nitrogen unit from the teeth outwards, the method is also preferred.Further, in order to make them exist steadily in the long term, preferably prevent the existence of internal field or preparation from can tolerate the chemical bond of the existence of internal field.The former is that the charge carrier quantity increase realized by the method such as doping causes being formed the good electron energy level of significantly energy level variations and stair-stepping balance.The latter is the chemical bond of the metallic element of resilient coating organic substance and oxide surface etc.Hereinafter record concrete example.
The method of the characteristics of luminescence of the present inventor to the organic electroluminescent device improving organic-inorganic mixed type carries out various research, wherein find the new problem that the crystallization of low molecular compound layer is such, solution is studied, found that, the resilient coating of the regulation thickness formed by being coated with organic compounds is configured between the low molecular compound layers such as the oxide skin(coating) be formed on negative electrode and luminescent layer, the low molecular compound layer such as lamination luminescent layer on this resilient coating, if form above-mentioned formation, the crystallization of the low molecular compound then in low molecular compound layer is suppressed, thus, even if the organic electroluminescent device of organic-inorganic mixed type have the layer that formed by low molecular compound as also can be inhibited during luminescent layer etc. leakage current and uniform face luminous.In addition the present inventor finds, the boron-containing compound having ad hoc structure if use or boron polymer are as the organic compound forming resilient coating, then the resilient coating formed by this organic compound also can play excellent function as electron transfer layer.
In addition, the method of the characteristics of luminescence of the present inventor to the organic electroluminescent device improving organic-inorganic mixed type has carried out various research, found that, if be formed between the 1st electrode and the 2nd electrode and there is metal oxide layer, this metal oxide layer has the organic electroluminescent device that the resilient coating that formed by organic compound is formed like this, and make in the resilient coating of this organic electroluminescent device containing reducing agent, then the n-type dopant of reducing agent supply electronics plays a role, the organic electroluminescent device of the characteristics of luminescence than the organic electroluminescent device excellence of existing organic-inorganic mixed type can be formed.Find in addition, in the formation of the organic electroluminescent device formed, there is successively the 1st metal oxide layer, resilient coating, the low molecular compound layer comprising luminescent layer of lamination and the 2nd metal oxide layer on this resilient coating between the 1st electrode and the 2nd electrode, and when making to contain reducing agent in the resilient coating of this organic electroluminescent device, this organic electroluminescent device is preferred.
In addition, the present inventor has carried out various research to improving further without the need to the luminous efficiency of the organic electroluminescent device of the organic-inorganic mixed type of tight seal and the method in life-span, found that, if metal oxide layer had between the anode and the cathode is formed the nitrogenous film of specific thickness, then Electron Injection Characteristics improves, element long lifetime.Wherein also find, more preferably the nitrogenous film that there is the high nitrogenous film of nitrogen-atoms ratio in the atom forming nitrogenous film and/or formed by the method making nitrogen-containing compound decompose to form nitrogenous film, and then find, formed preferably by the decomposition of nitrogen-containing compound further and form the high nitrogenous film of nitrogen-atoms ratio in the atom of nitrogenous film.Use above-mentioned nitrogenous film as when forming the layer of organic electroluminescent device of organic inorganic mixed type, the present inventor find the organic electroluminescent device that formed not only luminous efficiency excellent and also drive stability high, drive the life-span long, and expect can ideally solving above-mentioned problem like this, thus complete the present invention.
Namely, the present invention is a kind of organic electroluminescent device, it is the organic electroluminescent device of the structure with the layer being laminated with more than 2 layers, it is characterized in that, above-mentioned organic electroluminescent device has metal oxide layer between the 1st electrode and the 2nd electrode, and above-mentioned metal oxide layer has the resilient coating formed by organic compound.
In addition, 1st optimal way of organic electroluminescent device of the present invention is organic electroluminescent device as described below, it is the organic electroluminescent device of the structure with the layer being laminated with more than 2 layers, it is characterized in that, above-mentioned organic electroluminescent device has the 1st metal oxide layer, resilient coating, the low molecular compound layer comprising luminescent layer of lamination and the 2nd metal oxide layer on above-mentioned resilient coating successively between the 1st electrode and the 2nd electrode, and above-mentioned resilient coating is the average thickness formed by the solution of coating containing organic compound is the layer of 5 ~ 50nm.
In addition, 2nd optimal way of organic electroluminescent device of the present invention is organic electroluminescent device as described below, it is the organic electroluminescent device of the structure with the layer being laminated with more than 2 layers, it is characterized in that, above-mentioned organic electroluminescent device has the 1st metal oxide layer, resilient coating, the low molecular compound layer comprising luminescent layer of lamination and the 2nd metal oxide layer on above-mentioned resilient coating successively between the 1st electrode and the 2nd electrode, and above-mentioned resilient coating contains reducing agent.
In addition, 3rd optimal way of organic electroluminescent device of the present invention is organic electroluminescent device as described below, it has the organic electroluminescent device being laminated with the structure of the layer of more than 2 layers between anode and the negative electrode being formed on substrate, it is characterized in that, above-mentioned organic electroluminescent device has metal oxide layer between the anode and the cathode, and it is the layer of 3 ~ 150nm that above-mentioned metal oxide layer has the average thickness be made up of nitrogenous film.
The present invention is described below in detail.
It should be noted that, be also optimal way of the present invention by the two or more mode of of the present invention various optimal way combination of the following stated.
Organic electroluminescent device of the present invention is the organic electroluminescent device of the structure with the layer being laminated with more than 2 layers, wherein, between the 1st electrode and the 2nd electrode, there is metal oxide layer, this metal oxide layer has the resilient coating formed by organic compound.
1st electrode is the negative electrode formed on substrate, the resilient coating having metal oxide layer successively and formed by organic compound between the anode as the 2nd electrode, and this is the optimal way of organic electroluminescent device of the present invention.
In addition, resilient coating is that the average thickness formed is the layer of more than 3nm by being coated with the solution containing organic compound, and this resilient coating is formed on metal oxide layer in a neighboring manner, and this is also the optimal way of organic electroluminescent device of the present invention.
Organic electroluminescent device of the present invention has three kinds of optimal ways that layer is formed and resilient coating is different of element.Hereinafter these three kinds of optimal ways are described successively.It should be noted that, the mode of more than two kinds met in these three kinds of optimal ways is also the optimal way of organic electroluminescent device of the present invention.
[organic electroluminescent device of the 1st optimal way of the present invention]
The organic electroluminescent device (being hereafter also designated as the 1st organic electroluminescent device of the present invention) of the 1st optimal way of the present invention has the 1st metal oxide layer, resilient coating, the low molecular compound layer comprising luminescent layer of lamination and the 2nd metal oxide layer on this resilient coating successively between the 1st electrode and the 2nd electrode, and the average thickness of resilient coating is 3nm.In addition, the average thickness of preferred resilient coating is 5 ~ 50nm.In addition, also preferred resilient coating has the electron energy level equaling the laminated order of these layers from the sequence of the electron energy level of each layer of the electrode formed at substrate to luminescent layer.
By having above-mentioned formation, even if thus when the layer making luminescent layer etc. be configured with electro-luminescence element is low molecular compound layer, 1st organic electroluminescent device of the present invention also can suppress the crystallization of low molecular compound layer, can suppress leakage current, obtain the luminescence of uniform face.
For the organic electroluminescent device of organic-inorganic mixed type, the reason of low molecular compound layer generation crystallization can be considered as follows.
In the organic electroluminescent device of organic-inorganic mixed type, have the 1st electrode on substrates such as being configured at glass and the 1st metal oxide layer, on it, film forming has the low molecular compound layer comprising luminescent layer.Herein, according to existing method, the 1st metal oxide layer is formed by method film forming such as spray heating decomposition, sol-gal process, sputtering methods, and air spots is sliding and have concavo-convex.When having by method film forming such as vacuum evaporations a low molecular compound layer comprising luminescent layer on the 1st metal oxide layer, the concavo-convex of surface of the 1st metal oxide layer becomes the nuclei of crystallization, facilitates the crystallization of the low molecular compound layer contacted with the 1st metal oxide layer.Therefore, even if complete organic electroluminescent device, also have larger leakage current flow, the uneven homogenize of light-emitting area, and the element of resistance to practicality cannot be obtained.
On the other hand, for not there is the organic electroluminescent device of the 1st metal oxide layer, i.e. so-called conventional structure on the 1st electrode, the element that the 1st electrode surface is polished fully level and smooth can be obtained, even if direct formation of film at surface goes out to comprise the low molecular compound layer of luminescent layer on the 1st electrode surface, also not easily cause the problem that crystallization is such.Therefore, this crystallization be organic-inorganic mixed type organic electroluminescent device specific to problem, 1st organic electroluminescent device of the present invention by having formation as above, problem specific to the organic electroluminescent device that can solve this organic-inorganic mixed type thus.
When 1st organic electroluminescent device of the present invention is above-mentioned preferred structure, if there is successively the 1st metal oxide layer between the 1st electrode and the 2nd electrode, resilient coating that the average thickness that formed by organic compound is 5 ~ 50nm, the low molecular compound layer comprising luminescent layer of lamination and the 2nd metal oxide layer on this resilient coating, then also can have other layer beyond them.
It should be noted that, in the present invention, low molecular compound refers to it is not the compound of macromolecular compound (polymer), might not refer to the compound that molecular weight is low.
The above-mentioned low molecular compound layer comprising luminescent layer refers to 1 layer of being formed by low molecular compound or more than 2 layers of being formed by low molecular compound long-pending layer by layer forms and wherein 1 layer be luminescent layer.That is, the low molecular compound layer comprising luminescent layer refers to the luminescent layer formed by low molecular compound or the luminescent layer formed by low molecular compound and any one in other the low molecular compound layer long-pending layer by layer formed by low molecular compound.Other layer formed by low molecular compound can be 1 layer also can be more than 2 layers.In addition, the laminated order of luminescent layer and other layer is not particularly limited.
Above-mentioned other layer formed by low molecular compound is preferably hole transmission layer or electron transfer layer.That is, when low molecular compound layer is made up of the layer of more than 2 layers, preferably there is hole transmission layer and/or electron transfer layer as other layer beyond luminescent layer.Thus, organic electroluminescent device has hole transmission layer and/or electron transfer layer is one of preferred implementation of the 1st organic electroluminescent device of the present invention as the independently layer different from luminescent layer.
When 1st organic electroluminescent device of the present invention has hole transmission layer as independently layer, preferably between luminescent layer and the 2nd metal oxide layer, there is hole transmission layer.When 1st organic electroluminescent device of the present invention has electron transfer layer as independently layer, preferably between the resilient coating formed by organic compound and luminescent layer, there is electron transfer layer.
When 1st organic electroluminescent device of the present invention does not have hole transmission layer, electron transfer layer as independently layer, any one formation in the layer had of necessity as the 1st organic electroluminescent device of the present invention has the function of above-mentioned layer concurrently.
One of optimal way of 1st organic electroluminescent device of the present invention is for as under type: organic electroluminescent device is only made up of the 1st electrode, the 1st metal oxide layer, the resilient coating formed by organic compound, luminescent layer, hole transmission layer, the 2nd metal oxide layer, the 2nd electrode, and any one in these layers has the function of electron transfer layer concurrently.
In addition, as one of optimal way that under type is also the 1st organic electroluminescent device of the present invention: organic electroluminescent device is only made up of the 1st electrode, the 1st metal oxide layer, the resilient coating formed by organic compound, luminescent layer, the 2nd metal oxide layer, the 2nd electrode, any one in these layers has the function of hole transmission layer and electron transfer layer concurrently.
In the 1st organic electroluminescent device of the present invention, the 1st electrode is negative electrode, and the 2nd electrode is anode.In organic electroluminescent device of the present invention, as anode and negative electrode, can suitably use known conductive material, but at least any one is transparent in order to light extracts preferably.As the example of known transparent conductive material, ITO (tin-doped indium oxide), ATO (Sb doped indium oxide), IZO (indium doping zinc oxide), AZO (aluminium-doped zinc oxide), FTO (Fluorin doped indium oxide), In can be enumerated 3o 3, SnO 2, containing the SnO of Sb 2, containing the oxide etc. such as ZnO of Al.As the example of opaque conductive material, calcium, magnesium, aluminium, tin, indium, copper, silver, gold, platinum or their alloy etc. can be enumerated.
As negative electrode, wherein, ITO, IZO, FTO is preferably.
As anode, Au, Pt, Ag, Cu, Al can be enumerated or comprise their alloy etc.Among these, be preferably Au, Ag, Al.
As mentioned above, owing to can the metal being generally used for anode be used in negative electrode and anode, therefore imagine and also can easily realize from the situation (top lighting structure) of upper electrode extraction light, above-mentioned various electrode can be selected in respective electrode.Such as, be Al as lower electrode, be ITO etc. for upper electrode.
The average thickness of above-mentioned 1st electrode is not particularly limited, is preferably 10 ~ 500nm.Be more preferably 100 ~ 200nm.The average thickness of the 1st electrode can utilize probe-type contourgraph, light splitting ellipsometer measures.
The average thickness of above-mentioned 2nd electrode is not particularly limited, is preferably 10 ~ 1000nm.Be more preferably 30 ~ 150nm.In addition, even if when using alternatively non-transparent material, such as, by making average thickness be about 10 ~ 30nm, the anode of top emission type and transparent type can be used as.
The average thickness of the 2nd electrode can utilize quartz vibrator film thickness gauge to measure when film forming.
Above-mentioned 1st metal oxide layer is the layer played a role as electron injecting layer or electrode (negative electrode), and the 2nd metal oxide layer is the layer played a role as hole injection layer.
As the 1st metal oxide layer, it is the layer that is made up of the metal oxide film of 1 layer of single or layer single metal oxide or two or more metal oxide being carried out lamination and/or the such semiconductor of the layer that mixes or insulator lamination film.As the metallic element forming metal oxide, be selected from the group be made up of magnesium, calcium, strontium, barium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, indium, gallium, iron, cobalt, nickel, copper, zinc, cadmium, aluminium, silicon, tin.Among these, the at least one be preferably in the metallic element forming lamination metal oxide layer or mixed-metal oxides layer is selected from the layer of magnesium, aluminium, calcium, zirconium, hafnium, silicon, titanium, zinc, tin, wherein if single metal oxide, then preferably comprise the metal oxide in the group being selected from and being made up of magnesium oxide, tungsten oxide, niobium oxide, iron oxide, aluminium oxide, zirconia, hafnium oxide, silica, titanium oxide, zinc oxide, tin oxide.
As the above-mentioned example of layer of single metal oxide or two or more metal oxide being carried out lamination and/or mixing, the layer that the combination of the metal oxides such as titanium oxide/zinc oxide, titanium oxide/magnesium oxide, titanium oxide/zirconia, titanium oxide/aluminium oxide, titanium oxide/hafnium oxide, titanium oxide/silica, zinc oxide/magnesium oxide, zinc oxide/zirconia, zinc oxide/hafnium oxide, Zinc oxide/silicon oxide, calcium oxide/aluminium oxide is carried out lamination and/or mixed can be enumerated; Or by the layer etc. that the combination of three kinds of metal oxides such as titanium oxide/zinc oxide/magnesium oxide, titanium oxide/zinc oxide/zirconia, titanium oxide/zinc oxide/alumina, titanium oxide/zinc oxide/hafnium oxide, titanium oxide/Zinc oxide/silicon oxide, indium oxide/gallium oxide/zinc oxide is carried out lamination and/or mixed.Among these, can also comprise as the IGZO of the oxide semiconductor demonstrating superperformance using the form of special composition, the 12CaO7Al as electron compound (electride) 2o 3.
It should be noted that, in the present invention, sheet resistance is classified as electric conductor lower than the material of 100 Ω/, sheet resistance is classified as semiconductor or insulator higher than the material of 100 Ω/.Therefore, the film such as ITO (tin-doped indium oxide), the ATO (Sb doped indium oxide) known as transparency electrode, IZO (indium doping zinc oxide), AZO (aluminium-doped zinc oxide), FTO (Fluorin doped indium oxide) is not comprised in the category of semiconductor or insulator because conductivity is high, therefore do not meet 1 layer that forms the 1st metal oxide layer of the present invention.
Be not particularly limited as above-mentioned 2nd metal oxide layer, vanadium oxide (V can be used 2o 5), molybdenum oxide (MoO 3), tungsten oxide (WO 3), ruthenium-oxide (RuO 2) etc. in one kind or two or more.Among these, preferably using vanadium oxide or molybdenum oxide as main component.If the 2nd metal oxide layer is formed as the material of main component by using vanadium oxide or molybdenum oxide, then the 2nd metal oxide layer is as from the 2nd electrode injection hole and to transfer to the function of luminescent layer or the such hole injection layer of hole transmission layer more excellent.In addition, vanadium oxide or molybdenum oxide high due to the hole transport ability of itself, therefore also have and suitably can prevent hole from the 2nd electrode to the advantage that the injection efficiency of luminescent layer or hole transmission layer reduces.More preferably be made up of vanadium oxide and/or molybdenum oxide.
The average thickness of above-mentioned 1st metal oxide layer can allow the degree from 1nm to several μm, is not particularly limited, and from forming the aspect can carrying out the organic electroluminescent device driven with low-voltage, is preferably 1 ~ 1000nm.Be more preferably 2 ~ 100nm.
The average thickness of above-mentioned 2nd metal oxide layer is not particularly limited, is preferably 1 ~ 1000nm.Be more preferably 5 ~ 50nm.
The average thickness of the 1st metal oxide layer can utilize probe-type contourgraph, light splitting ellipsometer measures.
The average thickness of the 2nd metal oxide layer can utilize quartz vibrator film thickness gauge to measure when film forming.
As the material of luminescent layer, also can use any one low molecular compound that usually can be used as the material of luminescent layer, can also be mixed them and use.
As low molecule system material, can enumerate and have 2 in ligand, three-fold coordination iridium complex, three (the 2-phenylpyridines) of 2 '-bipyridine-4,4 '-dicarboxylic acids close iridium (Ir (ppy) 3), oxine aluminium (Alq 3), three (4-methyl-oxine) aluminium (III) (Almq 3), oxine zinc (Znq 2), (1,10-phenanthroline) three [the fluoro-1-of 4,4,4-tri-(2-thienyl)-1,3-diacetyl] europium (III) (Eu (TTA) 3(phen)), 2,3,7,8,12,13,17,18-octaethyl-21H, the various metal complexs of 23H-porphines platinum (II) and so on; The benzene compounds of diphenylethyllene benzene (DSB), diaminourea bisstyryl benzene (DADSB) and so on; Naphthalene series compound; Luxuriant and rich with fragrance based compound; Bend based compound; Perylene based compound; Coronene based compound; Anthracene based compound; Pyrene based compound; Pyrans based compound; Acridine based compound; Stilbene based compound; Carbazole based compound; Thiophene based compound; Benzoxazole based compound; Benzimidazole based compound; Benzothiazole based compound; Butadiene-based compound; Naphthalimide based compound; Coumarin series compounds; Purple cyclic ketones based compound; Oxadiazole based compound; Aldazine based compound; Cyclopentadiene based compound; Quinacridone based compound; Pyridine based compound; 2,2 ', 7, the spiro-compound of 7 '-tetraphenyl-9,9 '-spiral shell two fluorenes and so on; Metal or nonmetallic phthalocyanine based compound; And Japanese Unexamined Patent Publication 2009-155325 publication, No. 2010-28273, Japanese Patent Application, No. 2010-230995, Japanese Patent Application and the boron compound material etc. described in No. 2011-6458, Japanese Patent Application, what can use in them is one kind or two or more.
Above-mentioned luminescent layer can contain dopant.As dopant, any compound that usually can be used as dopant also can be used.As the example that can be used as the compound of dopant, iridic compound can be enumerated; The low-molecular-weight organic compounds etc. such as 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi), what can use in them is one kind or two or more.
When above-mentioned luminescent layer contains dopant, relative to the material 100 quality % forming luminescent layer, the content of dopant is preferably 0.5 ~ 20 quality %.If above-mentioned content, then can form the element making the characteristics of luminescence better.Be more preferably 0.5 ~ 10 quality %, more preferably 1 ~ 6 quality %.
The average thickness of above-mentioned luminescent layer is not particularly limited, is preferably 10 ~ 150nm.Be more preferably 20 ~ 100nm.More preferably 40 ~ 100nm.
For the average thickness of luminescent layer, quartz vibrator film thickness gauge can be utilized measure when low molecular compound, contact contourgraph can be utilized measure when macromolecular compound.
As the material of above-mentioned hole transmission layer, also can use any low molecular compound of material that usually can be used as hole transmission layer, can also used in combination they.
As low molecular compound, arylcyloalkanes based compound can be enumerated, arylamine based compound, phenylenediamine based compound, carbazole based compound, Stilbene based compound, oxazole based compound, triphenylmenthane based compound, pyrazoline based compound, benzyne (benzyne) (cyclohexadiene) based compound, three azole compounds, imidazole compound, oxadiazole based compound, anthracene based compound, Fluorenone based compound, aniline based compound, silane based compound, azole series compound, fluorenes based compound, porphyrin based compound, quinacridone based compound, metal or nonmetallic phthalocyanine based compound, metal or nonmetallic naphthalene phthalocyanine based compound, benzidine based compound etc., what can use in them is one kind or two or more.
Among these, the arylamine based compound of preferably N, N '-two (1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4,4 '-diamines (α-NPD), TPTE and so on.
When 1st organic electroluminescent device of the present invention has the hole transmission layer as independently layer, the average thickness of hole transmission layer is not particularly limited, is preferably 10 ~ 150nm.Be more preferably 20 ~ 100nm, more preferably 40 ~ 100nm.
The average thickness of hole transmission layer can utilize quartz vibrator film thickness gauge to measure when film forming.
As the material of above-mentioned electron transfer layer, also can use any low molecular compound of material that usually can be used as electron transfer layer, can also used in combination they.
As the example that can be used as the low molecular compound of the material of electron transfer layer, except the boron-containing compound represented with formula described later (1), pyridine derivate, quinoline, pyrimidine derivatives, pyrazines derivatives, phenanthroline derivative, pyrrolotriazine derivatives, triazole derivative, oxazole derivative, oxadiazole derivative, imdazole derivatives, aromatic ring tetracarboxylic anhydride can also be enumerated; With (2-(4-methyl-2-hydroxy phenyl) benzothiazole) zinc (Zn (BTZ) 2), three (oxine) aluminium (Alq 3) etc. be the various metal complexs of representative; Cough up with thiophene the organic silane derivative etc. that derivative is representative, what can use in them is one kind or two or more.
Among these, preferred Alq 3and so on the pyridine derivate of metal complex, three-1,3,5-(3 '-(pyridine-3 "-Ji) phenyl) benzene (TmPyPhB) and so on.
When 1st organic electroluminescent device of the present invention has the electron transfer layer as independently layer, the average thickness of electron transfer layer is not particularly limited, is preferably 10 ~ 150nm.Be more preferably 20 ~ 100nm, more preferably 40 ~ 100nm.
The average thickness of electron transfer layer can utilize quartz vibrator film thickness gauge to measure when film forming.
For the 1st organic electroluminescent device of the present invention, formed the 1st, the 2nd metal oxide layer, the 2nd electrode, luminescent layer, hole transmission layer, electron transfer layer method be not particularly limited, the chemical vapor deposition methods (CVD) such as the plasma CVD of gas phase membrane formation process, hot CVD, laser CVD can be used as; The dry type plating methods such as vacuum evaporation, sputtering, ion plating; Hot spray process; And as electrolytic coating, the dipping wet type such as plating, the electroless plating plating method of liquid phase membrane formation process; Sol/gel method, MOD method, spray heating decomposition, use particle dispersion liquid scrape the printing technologies such as the skill in using a kitchen knife in cookery, spin-coating method, ink-jet method, silk screen print method; Ald (ALD) methods etc., can choice for use is suitable according to material method.
The resilient coating that 1st organic electroluminescent device of the present invention comprises is the layer that formed by the solution of coating containing organic compound.Formed the resilient coating of specific thickness by coating, effectively can suppress the crystallization of the low molecular compound of film forming on resilient coating thus.
The method above-mentioned coating being contained to the solution of organic compound is not particularly limited, and can use the various coating process such as spin-coating method, the tape casting, micro-gravure coating method, gravure coating method, stick coating method (bar coating), rolling method, line rod rubbing method (wire-bar coating), slot coated method, Dipcoat method, spraying process, silk screen print method, flexographic printing method, flexographic printing process, ink jet printing method.Wherein, preferred spin-coating method.
Go out resilient coating by coating film forming, make the concavo-convex smoothing existed on the 1st metal oxide layer surface thus, therefore inhibit the crystallization of the low molecular compound of film forming on resilient coating subsequently.
As in order to prepare the solvent that above-mentioned solution containing organic compound uses, as long as the solvent that can be dissolved with organic compounds is just not particularly limited, the inorganic solvents such as such as nitric acid, sulfuric acid, ammonia, hydrogen peroxide, water, carbon disulfide, carbon tetrachloride, ethylene carbonate can be enumerated; Ketone series solvent; Alcohol series solvent; Ether series solvent; Cellosolve series solvent; The Aliphatic hydrocarbon solvents such as hexane, pentane, heptane, cyclohexane; The aromatic hydrocarbon solvents such as toluene, dimethylbenzene, benzene; Aromatic heterocyclic compounds series solvent; Acid amides series solvent; Halogen contained compound series solvent; Ester series solvent; Sulfur-containing compound series solvent; Nitrile series solvent; The various organic solvents of organic acid series solvent and so on; Or contain their mixed solvent etc.Among these, be preferably THF, toluene, chloroform.
The above-mentioned concentration containing the organic compound in the solution preferred solvent of organic compound is 0.05 ~ 10 quality %.If above-mentioned concentration, then can suppress crawling when being coated with and concavo-convex generation.The concentration of the organic compound in solvent is more preferably 0.1 ~ 5 quality %, more preferably 0.1 ~ 3 quality %.
Above-mentioned resilient coating preferably has and equals the such electron energy level of the laminated order of these layers from the sequence of the electron energy level of each layer of the electrode formed at substrate to luminescent layer.Identical with laminated order from the sequence of the electron energy level of each layer of the electrode formed at substrate (negative electrode) to luminescent layer, the height of electron energy level is interim from electrode (negative electrode) to luminescent layer to be raised, and moves thus rising to process and can relatively successfully carry out from electrode (negative electrode) electronics to luminescent layer.
The preferred average thickness of above-mentioned resilient coating is 5 ~ 50nm.When average thickness is above-mentioned scope, the effect suppressing to comprise the crystallization of the low molecular compound layer of luminescent layer can be given full play to.If the average thickness of resilient coating is thinner than 5nm, then cannot make the concavo-convex abundant smoothing existed at the 1st metal oxide surface, likely cause leakage current increase and effect of the present invention can not be given full play to.In addition, if the average thickness of resilient coating is thicker than 50nm, then driving voltage rises, not preferred in practical.In addition, when using the compound of the preferred structure in the present invention described later as organic compound, resilient coating can also give full play to the function as electron transfer layer.The average thickness of above-mentioned resilient coating is more preferably 10 ~ 30nm.
The average thickness of resilient coating can utilize probe-type contourgraph, light splitting ellipsometer measures.
But, organic thin film electroluminescent elements as described below is disclosed in above-mentioned Japanese Unexamined Patent Publication 2012-4492 publication (patent documentation 5), it has anode, negative electrode, be clipped in more than 1 layer or 2 layers organic compound layer between anode and negative electrode, and there is more than at least a kind metal-oxide film between anode and organic compound layer or between negative electrode and organic compound layer, there is at above-mentioned each interlayer the self-assembled monolayer of more than 1 layer or 2 layers, this self-assembled monolayer becomes energy barrier for main charge carrier, not forming energy potential barrier for reverse carrier.Record following element about organic-inorganic mixed type electroluminescent cell in this patent documentation to form: will there is self-assembled monolayer (being coated on interior film build method by the comprising) film forming of particular level on oxide substrate, charge carrier reverse with main charge carrier thus due to tunnel effect by as carrier injection.In addition the carrier injection described caused by tunnel effect carries out well when this self-assembled monolayer is the film of below 2nm (according to the record of patent documentation 5, inferring that the average thickness of organic compound layer is below 2nm).On the other hand, as in embodiment described later, in order to obtain the abundant effect for problem to be solved by this invention, the average thickness of organic compound layer needs for more than 5nm.
Thus, the present invention is different from the means of invention problem to be solved disclosed in patent documentation 5, solution in itself, the two clear and definite Qu Do should be opened.
1st organic electroluminescent device of the present invention can be each layer that lamination is configured with electro-luminescence element on substrate.The each layer of lamination forms on substrate, preferably form each layer being formed on the 1st electrode on substrate.In this case, the 1st organic electroluminescent device of the present invention can be the top emission type element extracting light in the opposition side of the side having substrate, also can be the bottom emission type element extracting light in the side having substrate.
As the material of aforesaid substrate, the resin material of polyethylene terephthalate, Polyethylene Naphthalate, polypropylene, cyclic olefin polymer, polyamide, polyether sulfone, polymethyl methacrylate, Merlon, polyarylate and so on can be enumerated; Or the glass material etc. of quartz glass, soda-lime glass and so on, what can use in them is one kind or two or more.
In addition, when top emission type, opaque substrate can also be used, the substrate etc. such as can also use the substrate be made up of the ceramic material of aluminium oxide and so on, the substrate that the surface of the metal substrate of stainless steel and so on is formed with oxide-film (dielectric film), being made up of resin material.
The average thickness of aforesaid substrate is preferably 0.1 ~ 30mm.Be more preferably 0.1 ~ 10mm.
The average thickness of substrate can utilize digital display universal instrument, vernier caliper to measure.
1st organic electroluminescent device of the present invention has following formation: coating contains the solution of organic compound and forms resilient coating, low molecular compound layer such as lamination luminescent layer on it, problem specific to the organic electroluminescent device that can solve the such organic-inorganic mixed type of the crystallization of low molecular compound thus.The manufacture method of the organic electroluminescent device of the organic-inorganic mixed type of the 1st optimal way of the present invention so is also one of the present invention, that is: a kind of manufacture method with the organic electroluminescent device of the structure of the layer of lamination more than 2 layers, it is characterized in that, this manufacture method comprises and between the 1st electrode and the 2nd electrode, has the 1st metal oxide layer according to organic electroluminescent device successively, resilient coating, the low molecular compound layer comprising luminescent layer of lamination on this resilient coating, the operation of each layer of electro-luminescence element is configured with the mode lamination of the 2nd metal oxide layer, this lamination operation comprises coating and contains the solution of organic compound and form the operation that average thickness is the resilient coating of more than 3nm.
In the manufacture method of organic electroluminescent device of the present invention, the solution of coating containing organic compound and the operation that forms resilient coating are preferably and form average thickness is the operation of the resilient coating of 5 ~ 50nm.
Under the prerequisite comprising above-mentioned operation, the manufacture method of the organic electroluminescent device of the 1st optimal way of the invention described above also can comprise other operation, also can comprise formation the 1st, the 2nd metal oxide layer, resilient coating, comprise luminescent layer low molecular compound layer beyond the operation of layer.In addition, be formed the material of each layer of electro-luminescence element, formation method, organic compound, in order to the thickness preparing solvent and each layer used containing the solution of organic compound same with the 1st organic electroluminescent device of the present invention, preferred version is also same.
For the 1st organic electroluminescent device of the present invention, as long as the organic compound forming resilient coating just can be not particularly limited by being coated with the layer being formed with organic compounds, as the example of organic compound, the polyacetylene based compound of Trans-polyacetylene, cis-polyacetylene, poly-(dibenzenyl) (PDPA), poly-(alkyl phenyl acetylene) (PAPA) and so on can be enumerated; Poly (phenylenevinylene) based compound; Polythiophene based compound; Polyfluorene based compound; Polyparaphenylene based compound; Polycarbazole based compound; Polysilane based compound; Polyethylene imine based (PEI); With the boron-containing compound that following formula (1) represents; Monomer component containing the boron-containing compound represented with following formula (2) is carried out being polymerized and the boron-containing compound such as boron polymer obtained; Or 3TPYMB: three (2,4,6-trimethyl-3 (pyridin-3-yl) phenyl) the boracic electron transport material such as borine (Tris (2,4,6-triMethyl-3-(pyridin-3-yl) phenyl) borane).These can use a kind also can use two or more.
For the 1st organic electroluminescent device of the present invention, the organic compound forming resilient coating preferably has the organic compound of boron atom.The organic compound more preferably with boron atom is the compound of structure represented with following formula (1) or the boron polymer being carried out being polymerized by the monomer component containing the boron-containing compound represented with following formula (2) and obtain.
Namely, for the 1st organic electroluminescent device of the present invention, the compound that the organic compound with boron atom forming resilient coating is preferably the structure represented with following formula (1) or the boron polymer monomer component containing the boron-containing compound represented with following formula (2) being carried out being polymerized and obtains.
[changing 1]
(in above formula, dotted line arc representation forms ring structure together with the skeleton part represented with solid line.Dotted portion in the skeleton part represented with solid line represents that the 1 pair of atom connected with dotted line can connect with double bond.The arrow pointing to boron atom from nitrogen-atoms represents that nitrogen-atoms is coordinated in boron atom.Q 1and Q 2identical or different, they are the linking groups in the skeleton part represented with solid line, and at least local forms ring structure, their with or without substituting groups together with dotted line circular arc portion.X 1, X 2, X 3and X 4identical or different, represent hydrogen atom or as monovalent substituent substituent on ring structure, the ring structure of formation dotted line circular arc portion can be bonded with more than 2 X 1, X 2, X 3and X 4.N 1represent the integer of 2 ~ 10.Y 1for Direct Bonding or n 1the linking group of valency, represents and existing n 1individual except Y 1structure division is in addition bonded in the ring structure, the Q that form dotted line circular arc portion independently of one another 1, Q 2, X 1, X 2, X 3, X 4in arbitrary place);
[changing 2]
(in above formula, dotted line arc representation forms ring structure with connection boron atom together with a part for the skeleton part of nitrogen-atoms.Connect boron atom and represent that at least 1 pair of atom is connected with double bond with the dotted portion in the skeleton part of nitrogen-atoms, this double bond can form conjugation with ring structure.The arrow pointing to boron atom from nitrogen-atoms represents that nitrogen-atoms is coordinated in boron atom.X 5and X 6identical or different, represent hydrogen atom or as monovalent substituent substituent on ring structure, the ring structure of formation dotted line circular arc portion can be bonded with more than 2 X 5and X 6.R 1and R 2identical or different, represent hydrogen atom or monovalent substituent.X 5, X 6, R 1and R 2in at least 1 be the substituting group with reactive group).
For organic-inorganic mixed type electroluminescent cell, the known hole from anode is injected and is more efficiently occurred than the electron injection from negative electrode, and luminous position is present in cathode side oxide (being equivalent to the 1st metal oxide in the present invention) near interface.In order to avoid the luminescence from the resilient coating contacted with the 1st metal oxide layer, as the organic compound forming resilient coating, preferably select the compound with the HOMO energy level lower than the HOMO energy level of the luminance compound contained by luminescent layer.Further, energy in order to avoid the exciton generated by luminescent layer moves to the compound of resilient coating and luminous, as the organic compound forming resilient coating, more preferably select the compound with the HOMO-LUMO energy gap wider than the HOMO-LUMO energy gap of the luminance compound contained by luminescent layer.Above-mentioned represent with formula (1) boron-containing compound, the monomer component containing the boron-containing compound represented with formula (2) is carried out being polymerized and the boron polymer obtained has the HOMO-LUMO energy gap of low-down HOMO and non-constant width concurrently, and be the compound that can be coated with, therefore, it is possible to various luminescent layer is effectively played a role.
In addition, if the organic compound with boron atom is the compound with said structure, then the resilient coating formed by organic compound is also excellent as the function of electron transfer layer, without the need to arranging electron transfer layer separately beyond resilient coating.
Hereinafter, first, be described the boron-containing compound represented with above-mentioned formula (1), the boron polymer then obtained being polymerized by the monomer component containing the boron-containing compound represented with above-mentioned formula (2) is described.
The boron-containing compound represented with above-mentioned formula (1) has following various characteristic: (i) is thermal stability compound; (ii) energy level of HOMO, LUMO is low; (iii) good coated film etc. can be made, the material of the 1st organic electroluminescent device of the present invention can be suitable as.
In above-mentioned formula (1), dotted line arc representation is with the skeleton part represented with solid line, be namely connected boron atom and Q 1with the part of the skeleton part of nitrogen-atoms or be connected boron atom and Q 2the part of skeleton part form ring structure together.This represents: the compound represented with above-mentioned formula (1) at least has 4 ring structures in the structure, containing connecting boron atom, Q in above-mentioned formula (1) 1with the skeleton part of nitrogen-atoms and be connected boron atom and Q 2skeleton part as the part of this ring structure.It should be noted that, X 1in the ring structure of institute's bonding, its ring structure skeleton is made up of carbon atom and does not contain the atom beyond carbon atom.
In above-mentioned formula (1), the skeleton part represented with solid line, i.e. connection boron atom and Q 1with the skeleton part of nitrogen-atoms be connected boron atom and Q 2skeleton part in dotted portion represent in respective skeleton part with dotted line connect 1 pair of atom can connect with double bond.
In above-mentioned formula (1), the arrow pointing to boron atom from nitrogen-atoms represents that nitrogen-atoms is coordinated in boron atom.Herein, coordination refers to that nitrogen-atoms acts on boron atom and brings impact chemically as ligand, can form coordinate bond (covalent bond), also can not form coordinate bond.Be preferably formed coordinate bond.
In above-mentioned formula (1), Q 1and Q 2identical or different, they are the linking groups in the skeleton part represented with solid line, and at least local forms ring structure together with dotted line circular arc portion, and, their with or without substituting groups.This represents Q 1and Q 2include the part as described ring structure respectively in.
In above-mentioned formula (1), X 1, X 2, X 3and X 4identical or different, represent hydrogen atom or as monovalent substituent substituent on ring structure, the ring structure of formation dotted line circular arc portion can be bonded with more than 2 X 1, X 2, X 3and X 4.That is, X 1, X 2, X 3and X 4during for hydrogen atom, in the structure of the compound represented with above-mentioned formula (1), there is X 1, X 2, X 3and X 44 ring structures represent not there is substituting group; X 1, X 2, X 3and X 4in any or all when being monovalent substituent, any or all of these 4 ring structures has substituting group.In this case, the substituent quantity that 1 ring structure has can be 1 and also can be more than 2.
It should be noted that, the substituting group in this specification refers to the group of organic group and the carbon-free group such as halogen atom, hydroxyl comprised containing carbon.
In above-mentioned formula (1), n 1represent the integer of 2 ~ 10, Y 1for Direct Bonding or n 1the linking group of valency.That is, in the compound represented with above-mentioned formula (1), Y 1for Direct Bonding, itself and existing 2 are except Y 1structure division is in addition bonded in the ring structure, the Q that form dotted line circular arc portion independently of one another 1, Q 2, X 1, X 2, X 3, X 4in arbitrary place; Or Y 1for n 1the linking group of valency, in above-mentioned formula (1) except Y 1structure division in addition exists more than 2, and they are via the Y as linking group 1connect.
In above-mentioned formula (1), Y 1during for Direct Bonding, above-mentioned formula (1) represents: existing 2 except Y 1ring structure, the Q of the formation dotted line circular arc portion of one of structure division in addition 1, Q 2, X 1, X 2, X 3, X 4in arbitrary place and another is except Y 1ring structure, the Q of the formation dotted line circular arc portion of structure division in addition 1, Q 2, X 1, X 2, X 3, X 4in arbitrary place Direct Bonding.This bonding position is not particularly limited, preferably except Y 1the X of one of structure division in addition 1the ring of institute's bonding or X 2the ring of institute's bonding and another is except Y 1the X of structure division in addition 1the ring of institute's bonding or X 2the ring Direct Bonding of institute's bonding.More preferably except Y 1the X of one of structure division in addition 2the ring of institute's bonding and another is except Y 1the X of structure division in addition 2the ring Direct Bonding of institute's bonding.
In this case, existing 2 except Y 1the structure of structure division in addition can be the same or different.
In above-mentioned formula (1), work as Y 1for n 1in the linking group of valency, above-mentioned formula (1) except Y 1structure division in addition has more than 2 and they are via the Y as linking group 1during connection, such more than 2 that exist in above-mentioned formula (1) except Y 1structure division is in addition via the Y as linking group 1the structure connected with except Y 1the structure of structure division Direct Bonding is in addition compared, more resistance to oxidation, and masking also improves, and is therefore preferred.
It should be noted that, Y 1for n 1during the linking group of valency, itself and existing n 1individual except Y 1structure division is in addition bonded in the ring structure, the Q that form dotted line circular arc portion independently of one another 1, Q 2, X 1, X 2, X 3, X 4in arbitrary place, this refers to: except Y 1structure division is in addition forming ring structure, the Q of dotted line circular arc portion 1, Q 2, X 1, X 2, X 3, X 4in arbitrary place and Y 1bonding, for removing Y 1structure division in addition and Y 1bonding position, existing n 1individual except Y 1structure division is in addition independent separately, and can be all same area, can a part be also same area, can also be all different parts.This bonding position is not particularly limited, preferably existing n 1individual except Y 1structure division is in addition all at X 1the ring of institute's bonding or X 2the ring of institute's bonding and Y 1bonding.More preferably existing n 1individual except Y 1structure division is in addition all at X 2the ring of institute's bonding and Y 1bonding.
In addition, existing n 1individual except Y 1the structure of structure division in addition can be all identical, also can be a part of identical, can also be all different.
Y in above-mentioned formula (1) 1for n 1during the linking group of valency, as this linking group, the alkyl such as having or not there is substituent chain, branched or ring-type can be enumerated; There is or not have the substituent group containing assorted element; Have or not there is substituent aryl; Have or not there is substituent heterocyclic radical.Among these, preferably have or not there is substituent aryl, there is or do not have the group with aromatic rings of substituent heterocyclic radical and so on.That is, the Y in above-mentioned formula (1) 1for the group with aromatic rings is also one of the preferred embodiment of the present invention.
Further, Y 1it can also be the linking group of the structure with combination more than 2 above-mentioned linking groups.
As the alkyl of above-mentioned chain, branched or ring-type, preferably with any one group represented in following formula (3-1) ~ (3-8).Among these, be more preferably following formula (3-1), (3-7).
As the above-mentioned group containing assorted element, preferably with any one group represented in following formula (3-9) ~ (3-13).Among these, be more preferably following formula (3-12), (3-13).
As above-mentioned aryl, preferably with any one group represented in following formula (3-14) ~ (3-20).Among these, be more preferably following formula (3-14), (3-20).
As above-mentioned heterocyclic radical, preferably with any one group represented in following formula (3-21) ~ (3-27).Among these, be more preferably following formula (3-23), (3-24).
[changing 3]
As the alkyl of above-mentioned chain, branched or ring-type; Group containing assorted element; Aryl; The substituting group that heterocyclic radical has, can enumerate halogen atom; Haloalkyl; Carbon number is straight-chain or the branched-chain alkyl of 1 ~ 20; Carbon number is the cyclic alkyl of 5 ~ 7; Carbon number is straight-chain or the branched alkoxyl of 1 ~ 20; Nitro; Cyano group; There is the dialkyl amido that carbon number is the alkyl of 1 ~ 10; The ammonia diaryl base such as diphenyl amino, carbazyl; Acyl group; Carbon number is the alkenyl of 2 ~ 30; Carbon number is the alkynyl of 2 ~ 30; By substituted or unsubstituted aryl such as halogen atom, alkyl, alkoxyl, alkenyl, alkynyls; By halogen atom, alkyl, alkoxyl, alkenyl, alkynyl substituted or unsubstituted heterocyclic radical; N, N-dialkyl carbamyl; Dioxaborolanes base (Dioxaborolanyl), stannyl, silicyl, ester group, formoxyl, thioether group, epoxy radicals, NCO etc.It should be noted that, these groups can by replacements such as halogen atom, assorted element, alkyl, aromatic rings.
Among these, as Y 1in the alkyl of chain, branched or ring-type; Group containing assorted element; Aryl; The substituting group that heterocyclic radical has, be preferably halogen atom, carbon number be 1 ~ 20 straight-chain or branched-chain alkyl, carbon number be 1 ~ 20 straight-chain or branched alkoxyl, aryl, heterocyclic radical, ammonia diaryl base.Be more preferably alkyl, aryl, alkoxyl, ammonia diaryl base.
Above-mentioned Y 1in the alkyl of chain, branched or ring-type; Group containing assorted element; Aryl; When heterocyclic radical has substituting group, the position of substituting group institute bonding and quantity are not particularly limited.
N in above-mentioned formula (1) 1represent the integer of 2 ~ 10, be preferably 2 ~ 6.Be more preferably the integer of 2 ~ 5, more preferably the integer of 2 ~ 4, from deliquescent viewpoint in a solvent, be particularly preferably 2 or 3.Most preferably be 2.That is, the boron-containing compound represented with above-mentioned formula (1) most preferably is dimer.
As the Q in above-mentioned formula (1) 1and Q 2, the structure represented with following formula (4-1) ~ (4-8) can be enumerated.
[changing 4]
It should be noted that, above-mentioned formula (4-2) is the structure being bonded with 2 hydrogen atoms and being bonded with 3 atoms in addition on carbon atom, but is atom beyond hydrogen atom with 3 atoms of carbon atom bonding beyond this hydrogen atom.Any one among above-mentioned formula (4-1) ~ (4-8), preferably in (4-1), (4-7), (4-8).Be more preferably (4-1).That is, Q 1and Q 2identical or different and represent carbon number be 1 linking group be also one of the preferred embodiment of the present invention.
In above-mentioned formula (1), X 1the skeleton of the ring structure of institute's bonding is by under the prerequisite that carbon atom is formed, as long as the ring structure circulus formed by dotted line circular arc and the part of skeleton part that represents with solid line is just not particularly limited.
In above-mentioned formula (1), Y 1for Direct Bonding and n 1when being 2, as X 1the ring of institute's bonding, such as phenyl ring, naphthalene nucleus, anthracene nucleus, aphthacene ring, pentacene ring, benzo [9,10] phenanthrene ring, pyrene ring, fluorenes ring, indenes ring, thiphene ring, furan nucleus, pyrrole ring, benzothiophene ring, benzofuran ring, indole ring, dibenzothiophenes ring, dibenzofurans ring, carbazole ring, thiazole ring, benzothiazole Huan, oxazole ring, benzoxazole ring, imidazole ring, pyrazole ring, benzimidazole ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, quinoline ring, isoquinolin ring, quinoxaline ring, diazosulfide ring can be enumerated.
Among these, the ring that preferred ring structure skeleton is only made up of carbon atom, is preferably phenyl ring, naphthalene nucleus, anthracene nucleus, aphthacene ring, pentacene ring, benzo [9,10] phenanthrene ring, pyrene ring, fluorenes ring, indenes ring.Be more preferably phenyl ring, naphthalene nucleus, fluorenes ring, more preferably phenyl ring.
In above-mentioned formula (1), Y 1for Direct Bonding and n 1when being 2, as X 2the ring of institute's bonding, such as, can enumerate the ring represented with following formula (5-1) ~ (5-17).It should be noted that, the * mark in following formula (5-1) ~ (5-17) represents: form X 1the ring of institute's bonding and the connection boron atom formed in above-mentioned formula (1) and Q 1with carbon atom and any one bonding in the carbon atom marked with * of the skeleton part of nitrogen-atoms.In addition, can position beyond the carbon atom marked with * and other ring structure condense.Among these, be preferably pyridine ring, pyrimidine ring, quinoline ring, phenanthridines ring.Be more preferably pyridine ring, pyrimidine ring, quinoline ring.More preferably pyridine ring.
[changing 5]
In addition, in above-mentioned formula (1), Y 1for Direct Bonding and n 1when being 2, as X 3the ring of institute's bonding and X 4the ring of institute's bonding, can enumerate and above-mentioned Y 1for Direct Bonding and n 1x when being 2 1the ring that the ring of institute's bonding is same.Among these, be preferably phenyl ring, naphthalene nucleus, benzothiophene ring.Be more preferably phenyl ring.
In above-mentioned formula (1), X 1, X 2, X 3and X 4identical or different, represent hydrogen atom or as monovalent substituent substituent on ring structure.Be not particularly limited, as X as this monovalent substituent 1, X 2, X 3and X 4, such as hydrogen atom can be enumerated, have or not there is substituent aryl, heterocyclic radical, alkyl, alkenyl, alkynyl, alkoxyl, aryloxy group, aralkoxy, silicyl, hydroxyl, amino, halogen atom, carboxyl, sulfydryl, epoxy radicals, acyl group, there is or not have substituent oligomeric aryl (oligoaryl), the oligomeric heterocyclic radical of monovalence (オ リ ゴ Complex Su Ring yl), alkylthio group, arylthio, aralkyl, aralkoxy, aromatic alkylthio, azo group, stannyl, phosphino-, siloxy, have or not there is substituent aryloxy carbonyl, have or not there is substituent alkoxy carbonyl group, have or not there is substituent carbamyl, have or not there is substituent aryl carbonyl, have or not there is substituent alkyl-carbonyl, have or not there is substituent arylsulfonyl, have or not there is substituent alkyl sulphonyl, have or not there is substituent aryl sulfonyl kia, have or not there is substituent alkyl sulphinyl, formoxyl, cyano group, nitro, aryl-sulfonyl oxygen, alkylsulfonyloxy, the alkyl sulfonic acid ester groups such as Loprazolam ester group, ethane sulfonic acid ester group, trifluoromethayl sulfonic acid ester group, the aryl sulfonic acid ester groups such as benzene sulfonic acid ester group, p-methyl benzenesulfonic acid ester group, the sweet-smelling alkyl sulfonic acid ester groups such as benzylsulfonate base, monoborane base, sulfonium methyl, phosphorus methyl, phosphonate ester methyl, aryl sulfonic acid ester group, aldehyde radical, acetonitrile-base etc.
As above-mentioned X 1, X 2, X 3and X 4in substituting group, can halogen atom be enumerated; Haloalkyl; Carbon number is straight-chain or the branched-chain alkyl of 1 ~ 20; Carbon number is the cyclic alkyl of 5 ~ 7; Carbon number is straight-chain or the branched alkoxyl of 1 ~ 20; Hydroxyl; Sulfydryl; Nitro; Cyano group; Amino; Azo group; There is alkyl monosubstituted amino or dialkyl amido that carbon number is the alkyl of 1 ~ 40; The amino such as diphenyl amino, carbazyl; Acyl group; Carbon number is the alkenyl of 2 ~ 20; Carbon number is the alkynyl of 2 ~ 20; Alkenyloxy; Alkynyloxy group; The aryloxy group such as phenoxy group, naphthoxy, biphenylyloxy, pyrenyl oxygen base; The perfluoroalkyl of perfluoroalkyl and more long-chain; Monoborane base; Carbonyl; Carbonyl acyloxy; Alkoxy carbonyl group; Sulfinyl; Alkylsulfonyloxy; Aryl-sulfonyl oxygen; Phosphino-; Silicyl; Siloxy; Stannyl; By aryl such as the substituted or unsubstituted phenyl such as halogen atom, alkyl, alkoxyl, 2,6-xylyls, mesitylene base, duryl, xenyl, terphenyl, naphthyl, anthryl, pyrenyl, tolyl, methoxybenzyl, fluorophenyl, diphenylaminophenyl, dimethylamino phenyl, lignocaine phenyl, phenanthryl; The heterocyclic radicals such as thienyl, furyl, Silole Ji, oxazolyl, oxadiazolyl, thiazolyl, thiadiazolyl group, acridinyl, quinolyl, quinoxalinyl, phenanthroline base, benzothienyl, benzothiazolyl, indyl, carbazyl, pyridine radicals, pyrrole radicals, benzoxazolyl, pyrimidine radicals, imidazole radicals; Carboxyl; Carboxylate; Epoxy radicals; Isocyano group; Cyanate ester based; NCO; Thiocyanate groups; Isothiocyanate group; Carbamyl; N, N-dialkyl carbamyl; Formoxyl; Nitroso; Formyloxy; Etc..It should be noted that, these groups can by replacements such as halogen atom, alkyl, aryl, and in addition, these groups can form ring at any part bonding mutually.
Among these, as X 1, X 2, X 3and X 4, be preferably hydrogen atom; Halogen atom, carboxyl, hydroxyl, sulfydryl, epoxy radicals, amino, azo group, acyl group, pi-allyl, nitro, alkoxy carbonyl group, formoxyl, cyano group, silicyl, stannyl, monoborane base, phosphino-, siloxy, aryl-sulfonyl oxygen, alkylsulfonyloxy isoreactivity group; Carbon number is straight-chain or the branched-chain alkyl of 1 ~ 20; By carbon number be 1 ~ 8 straight-chain or branched-chain alkyl, carbon number be 1 ~ 8 straight-chain branched alkoxyl, aryl, carbon number be 2 ~ 8 alkenyl, carbon number be 2 ~ 8 alkynyl or the carbon number that replaces of these reactive groups be 1 ~ 20 straight-chain or branched-chain alkyl; Carbon number is straight-chain or the branched alkoxyl of 1 ~ 20; By carbon number be 1 ~ 8 straight-chain or branched-chain alkyl, carbon number be 1 ~ 8 straight-chain branched alkoxyl, aryl, carbon number be 2 ~ 8 alkenyl, carbon number be 2 ~ 8 alkynyl or the carbon number that replaces of these reactive groups be 1 ~ 20 straight-chain or branched alkoxyl; Aryl; By carbon number be 1 ~ 8 straight-chain or branched-chain alkyl, carbon number be 1 ~ 8 straight-chain or branched alkoxyl, aryl, carbon number be 2 ~ 8 alkenyl, carbon number be 2 ~ 8 alkynyl or the aryl that replaces of these reactive groups; Oligomeric aryl; By carbon number be 1 ~ 8 straight-chain or branched-chain alkyl, carbon number be 1 ~ 8 straight-chain or branched alkoxyl, aryl, carbon number be 2 ~ 8 alkenyl, carbon number be 2 ~ 8 alkynyl or the oligomeric aryl that replaces of these reactive groups; Monovalence heterocyclic radical; By carbon number be 1 ~ 8 straight-chain or branched-chain alkyl, carbon number be 1 ~ 8 straight-chain or branched alkoxyl, aryl, carbon number be 2 ~ 8 alkenyl, carbon number be 2 ~ 8 alkynyl or the monovalence heterocyclic radical that replaces of these reactive groups; The oligomeric heterocyclic radical of monovalence; By carbon number be 1 ~ 8 straight-chain or branched-chain alkyl, carbon number be 1 ~ 8 straight-chain or branched alkoxyl, aryl, carbon number be 2 ~ 8 alkenyl, carbon number be 2 ~ 8 alkynyl or the oligomeric heterocyclic radical of monovalence that replaces of these reactive groups; Alkylthio group; Aryloxy group; Arylthio; Aralkyl; Aralkoxy; Aromatic alkylthio; Alkenyl; By carbon number be 1 ~ 8 straight-chain or branched-chain alkyl, carbon number be 1 ~ 8 straight-chain or branched alkoxyl, aryl, carbon number be 2 ~ 8 alkenyl, carbon number be 2 ~ 8 alkynyl or the alkenyl that replaces of these reactive groups; Alkynyl; By carbon number be 1 ~ 8 straight-chain or branched-chain alkyl, carbon number be 1 ~ 8 straight-chain or branched alkoxyl, aryl, carbon number be 2 ~ 8 alkenyl, carbon number be 2 ~ 8 alkynyl or the alkynyl that replaces of these reactive groups.
Be more preferably hydrogen atom, bromine atoms, atomic iodine, amino, monoborane base, alkynyl, alkenyl, formoxyl, silicyl, stannyl, phosphino-, by the aryl that these reactive groups replace, by the oligomeric aryl that these reactive groups replace, monovalence heterocyclic radical or the monovalence heterocyclic radical replaced by these reactive groups, by the oligomeric heterocyclic radical of monovalence that these reactive groups replace, alkenyl or the alkenyl replaced by these reactive groups, alkynyl or the alkynyl replaced by these reactive groups.Wherein, as X 1and X 2, the functional group of the more preferably resistance to reduction such as hydrogen atom, alkyl, aryl, nitrogen-containing hetero aryl, alkenyl, alkoxyl, aryloxy group, silicyl.Be particularly preferably hydrogen atom, aryl, nitrogen-containing hetero aryl.In addition, as X 3and X 4, the more preferably sludge proof functional group such as hydrogen atom, carbazyl, triphenylamino, thienyl, furyl, alkyl, aryl, indyl.Be particularly preferably hydrogen atom, carbazyl, triphenylamino, thienyl.Thus, there is the functional group of resistance to reduction as X if think 1and X 2, there is sludge proof functional group as X 3and X 4, then so formed as boron-containing compound entirety not only resistance to reduction but also sludge proof compound.
It should be noted that, in above-mentioned formula (1), X 1, X 2, X 3and X 4during for monovalent substituent, to X 1, X 2, X 3and X 4be not particularly limited with the bonding position of ring structure, the quantity of bonding.
In above-mentioned formula (1), Y 1for n 1the linking group of valency and n 1when being 2 ~ 10, as X 1the ring of institute's bonding, Y in itself and above-mentioned formula (1) 1for Direct Bonding and n 1x when being 2 1the ring of institute's bonding is same.Among these rings, be preferably phenyl ring, naphthalene nucleus, benzothiophene ring.Be more preferably phenyl ring.
In above-mentioned formula (1), Y 1for n 1the linking group of valency and n 1when being 2 ~ 10, as X 2ring, the X of institute's bonding 3the ring of institute's bonding and X 4the ring of institute's bonding, respectively with Y in above-mentioned formula (1) 1for Direct Bonding and n 1as X when being 2 2ring, the X of institute's bonding 3the ring of institute's bonding and X 4the ring cited by ring of institute's bonding is same, and preferred structure is also same.
That is, the Y in above-mentioned formula (1) 1for Direct Bonding and n 1when being 2 and Y 1for n 1the linking group of valency and n 1the boron-containing compound represented with above-mentioned formula (1) in any one situation in when being 2 ~ 10 is the boron-containing compound represented with following formula (6) is also one of the preferred embodiment of the present invention.
[changing 6]
(in formula, point to arrow, the X of boron atom from nitrogen-atoms 1, X 2, X 3, X 4, n 1and Y 1same with formula (1))
The boron-containing compound represented with above-mentioned formula (1) can synthesize by using the conventional various reactions such as Suzuki coupling reaction.In addition, can also Journal of the American Chemical Society be passed through, 2009, the 131st volume, No. 40, the method synthesis described in 14549-14559 page.
If enumerate an example of the synthetic schemes of the boron-containing compound represented with above-mentioned formula (1), as shown in following reaction equation.Following reaction equation (I) represents the Y represented with above-mentioned formula (1) 1for Direct Bonding and n 1be an example of the synthetic schemes of the boron-containing compound of 2, following reaction equation (II) represents the Y represented with above-mentioned formula (1) 1for n 1the linking group of valency and n 1it is an example of the synthetic schemes of the boron-containing compound of 2 ~ 10.Wherein, the manufacture method of the boron-containing compound represented with above-mentioned formula (1) is not limited thereto.
It should be noted that, in following proposal, (a) compound as raw material such as can pass through Journal of Organic Chemistry, 2010, the 75th volume, No. 24, the method synthesis described in 8709-8712 page.In addition, (b) compound as raw material can by carrying out (a) compound synthesizing with the boronation reaction that following reaction equation (III) represents.
[changing 7]
[changing 8]
[changing 9]
Then, the boron polymer obtained being polymerized by the monomer component containing the boron-containing compound represented with above-mentioned formula (2) is described.
In above-mentioned formula (2), dotted line arc representation forms ring structure with connection boron atom together with a part for the skeleton part of nitrogen-atoms.Namely represent, the boron-containing compound represented with above-mentioned formula (2) at least has 2 ring structures in the structure, containing the part of skeleton part as this ring structure connecting boron atom and nitrogen-atoms in above-mentioned formula (2).
In above-mentioned formula (2), connect boron atom and represent that at least 1 pair of atom is connected with double bond with the dotted portion in the skeleton part of nitrogen-atoms, represent that this double bond can form conjugation with ring structure.Among the compound represented with formula (1), form the example of conjugation as double bond and ring structure, such as, can enumerate the compound of the structure as following formula (7-1) ~ (7-4) and so on.
[changing 10]
In above-mentioned formula (2), the arrow pointing to boron atom from nitrogen-atoms represents that nitrogen-atoms is coordinated in boron atom.It is identical that the meaning and the nitrogen-atoms in above-mentioned formula (1) of coordination are coordinated in boron atom.
In above-mentioned formula (2), X 5and X 6identical or different, represent hydrogen atom or as monovalent substituent substituent on ring structure, the ring structure of formation dotted line circular arc portion can be bonded with more than 2 X 5and X 6.That is, X 5and X 6during for hydrogen atom, represent in the structure of the boron-containing compound represented with formula (2) that there is X 5and X 62 ring structures not there is substituting group; X 5and/or X 6during for monovalent substituent, these 2 ring structures one of them there is substituting group or both all have substituting group.In this case, the substituent quantity that 1 ring structure has can be 1 and also can be more than 2.
In above-mentioned formula (2), R 1and R 2identical or different, represent hydrogen atom or monovalent substituent.This R 1and R 2can be the same or different, preferably both are identical.As this R 1and R 2be not particularly limited, can enumerate such as hydrogen atom, there is or not have substituent aryl, heterocyclic radical, alkyl, alkoxyl, aralkoxy, silicyl, hydroxyl, monoborane oxygen base, amino, halogen atom, R 1with R 22 of bonding, 2 '-xenyl, has or does not have substituent oligomeric aryl, the oligomeric heterocyclic radical of monovalence, alkylthio group, arylthio, aralkyl, aralkoxy, aromatic alkylthio, azo group, stannyl, phosphino-, siloxy, aryl-sulfonyl oxygen, alkylsulfonyloxy; Alkyl sulfonic acid ester group; Aryl sulfonic acid ester group; Sweet-smelling alkyl sulfonic acid ester group; The monoborane bases such as the group represented with following formula (8-1) ~ (8-4); The sulfonium methyl such as the group represented with following formula (8-5) ~ (8-6); The phosphorus methyl such as the group represented with following formula (8-7); The phosphonate ester methyl such as the group represented with following formula (8-8); Aryl sulfonic acid ester group; Aldehyde radical; Acetonitrile-base; With the magnesium halide etc. that following formula (8-9) represents.
It should be noted that, in formula, Me represents methyl.Et represents ethyl.X represents halogen atom.R ' represents alkyl, aryl or aralkyl.
[changing 11]
As above-mentioned aryl, phenyl, xenyl, naphthyl, tetralyl, indenyl, indanyl etc. can be enumerated.Among these, be preferably phenyl, xenyl, naphthyl.
As above-mentioned heterocyclic radical, pyrrole radicals, pyridine radicals, quinolyl, piperidinyl, piperidyl, furyl, thienyl etc. can be enumerated.Among these, be preferably pyridine radicals, thienyl.
As above-mentioned halogen atom, fluorine atom, chlorine atom, bromine atoms, atomic iodine can be enumerated, among these, be preferably bromine atoms, atomic iodine.
As abovementioned alkyl, can enumerate carbon number be 1 ~ 30 straight-chain or branched alkyl, carbon number be 3 ~ 30 ester ring type alkyl.Namely, for the 1st organic electroluminescent device of the present invention, if under type is also one of the preferred embodiment of the present invention: the boron polymer that resilient coating obtains by being carried out being polymerized by the monomer component containing the boron-containing compound represented with above-mentioned formula (2) is formed, the R in the boron-containing compound represented with formula (2) 1and R 2identical or different, and represent carbon number be 1 ~ 30 straight-chain or branched alkyl or carbon number be 3 ~ 30 ester ring type alkyl.
As abovementioned alkyl, among above-mentioned, be preferably methyl, ethyl, isopropyl, isobutyl group, octyl group.Be more preferably methyl, ethyl, isobutyl group, octyl group.
As above-mentioned R 1and R 2in substituting group, the X with above-mentioned formula (1) can be enumerated 1~ X 4in the same substituting group of substituting group.
Among these, as above-mentioned R 1and R 2in the substituting group that has of monovalent substituent, be preferably halogen atom, carbon number be 1 ~ 4 straight-chain or branched-chain alkyl, carbon number be 1 ~ 8 straight-chain or branched alkoxyl, aryl, haloalkyl.Be more preferably ethyl, isopropyl, octyl group, fluorine atom, bromine atoms, vinyl, acetenyl, diphenyl amino, diphenylaminophenyl, trifluoromethyl.
As above-mentioned R 1and R 2among above-mentioned group, be more preferably hydrogen atom, bromine atoms, methyl, ethyl, isopropyl, isobutyl group, n-octyl, phenyl, 4-methoxyphenyl, 4-trifluoromethyl, pentafluorophenyl group, 4-bromo phenyl, 2,2 '-xenyl, styryl, diphenylaminophenyl.More preferably bromine atoms, methyl, ethyl, isopropyl, isobutyl group, n-octyl, phenyl, 4-methoxyphenyl, 4-trifluoromethyl, pentafluorophenyl group, 4-bromo phenyl, 2,2 '-xenyl, styryl, diphenylaminophenyl, be particularly preferably bromine atoms, isopropyl, isobutyl group, n-octyl, phenyl, 4-trifluoromethyl, pentafluorophenyl group, 4-bromo phenyl, 2,2 '-xenyl, styryl, diphenylaminophenyl.
In above-mentioned formula (2), X 5and X 6identical or different, represent hydrogen atom or as monovalent substituent substituent on ring structure.Be not particularly limited as this monovalent substituent, can enumerate and above-mentioned R 1and R 2same group.
Among these, as X 5and X 6, be preferably hydrogen atom; Halogen atom, carboxyl, hydroxyl, sulfydryl, epoxy radicals, NCO, amino, azo group, acyl group, pi-allyl, nitro, alkoxy carbonyl group, formoxyl, cyano group, silicyl, stannyl, boryl, phosphino-, siloxy, aryl-sulfonyl oxygen, alkylsulfonyloxy isoreactivity group; Carbon number be 1 ~ 4 straight-chain or branched-chain alkyl or by the carbon number that these reactive groups replace be 1 ~ 4 straight-chain or branched-chain alkyl; Carbon number be 1 ~ 8 straight-chain or branched alkoxyl or by the carbon number that these reactive groups replace be 1 ~ 8 straight-chain or branched alkoxyl; Aryl or the aryl replaced by these reactive groups; Oligomeric aryl or the oligomeric aryl replaced by these reactive groups; Monovalence heterocyclic radical or the monovalence heterocyclic radical replaced by these reactive groups; The oligomeric heterocyclic radical of monovalence or the oligomeric heterocyclic radical of monovalence replaced by these reactive groups; Alkylthio group; Aryloxy group; Arylthio; Aralkyl; Aralkoxy; Aromatic alkylthio; Alkenyl or the alkenyl replaced by these reactive groups; Alkynyl or the alkynyl replaced by these reactive groups.Be more preferably hydrogen atom, bromine atoms, atomic iodine, monoborane base, alkynyl, alkenyl, formoxyl, stannyl, phosphino-, the aryl that aryl or these this reactive groups replace, by the oligomeric aryl that these reactive groups replace, the amino such as diphenyl amino, the monovalence heterocyclic radicals such as the group represented with following formula (8-10) or the monovalence heterocyclic radical replaced by these reactive groups, by the oligomeric heterocyclic radical of monovalence that these reactive groups replace, alkenyl or the alkenyl replaced by these reactive groups, alkynyl or the alkynyl replaced by these reactive groups.
[changing 12]
X in above-mentioned formula (2) 5, X 6, R 1and R 2among one of at least substituting group for having reactive group.As the substituting group with reactive group, be preferably halogen atom, carboxyl, hydroxyl, sulfydryl, epoxy radicals, NCO, amino, azo group, acyl group, pi-allyl, nitro, alkoxy carbonyl group, formoxyl, cyano group, silicyl, stannyl, monoborane base, phosphino-, siloxy, aryl-sulfonyl oxygen, alkylsulfonyloxy isoreactivity group; By straight-chain or branched-chain alkyl that the carbon number that these reactive groups replace is 1 ~ 4; By straight-chain or branched alkoxyl that the carbon number that these reactive groups replace is 1 ~ 8; By the aryl that these reactive groups replace; By the oligomeric aryl that these reactive groups replace; By the monovalence heterocyclic radical that these reactive groups replace; By the oligomeric heterocyclic radical of monovalence that these reactive groups replace; Alkenyl or the alkenyl replaced by these reactive groups; Alkynyl or the alkynyl replaced by these reactive groups.The alkynyl being more preferably bromine atoms, atomic iodine, monoborane base, formoxyl, stannyl, phosphino-, the aryl replaced by these reactive groups, the oligomeric aryl replaced by these reactive groups, the monovalence heterocyclic radical replaced by these reactive groups, the oligomeric heterocyclic radical of monovalence, alkenyl or the alkenyl replaced by these reactive groups that are replaced by these reactive groups, alkynyl or being replaced by these reactive groups.More preferably bromine atoms, monoborane base, formoxyl, stannyl, phosphino-, the aryl replaced by these reactive groups, the oligomeric aryl replaced by these reactive groups, the monovalence heterocyclic radical replaced by these reactive groups, the oligomeric heterocyclic radical of monovalence, alkenyl or the alkenyl replaced by these reactive groups that are replaced by these reactive groups, alkynyl or the alkynyl that replaced by these reactive groups.
Above-mentioned X 5, X 6, R 1and R 2among both for having the substituting group of reactive group time, the reactive group that the substituting group of both is had is different, thus is formed the mode of a kind of boron-containing compound combination of the reactive group of polycondensation alone can be made to set; Or the boron-containing compound represented with formula (2) containing two or more thus there is the combination that these boron-containing compounds can be made to carry out the reactive group of copolymerization; Or there is the combination that the one kind or two or more boron-containing compound that represents with formula (2) and other compound at least with 1 reactive group can be made to carry out the reactive group of copolymerization, the raw material of polymer can be suitable as thus.
In above-mentioned formula (2), as X 5the ring of institute's bonding, can enumerate such as phenyl ring, thiphene ring, benzothiophene ring, thiazole ring, oxazole ring, naphthalene nucleus, anthracene nucleus, aphthacene ring, pentacene ring, imidazole ring, pyrazole ring, pyridine ring, pyridazine ring, pyrazine ring, pyrimidine ring, quinoline ring, isoquinolin ring, they represent with following formula (9-1) ~ (9-17) respectively.Among these, be preferably phenyl ring, naphthalene nucleus, benzothiophene ring.
[changing 13]
In addition, in above-mentioned formula (2), as X 6the ring of institute's bonding, can enumerate such as pyrrole ring, pyrazole ring, imidazole ring, pyridine ring, pyridazine ring, pyrazine ring, pyrimidine ring, indole ring, iso-indoles ring, quinoline ring, isoquinolin ring, phenanthridines ring, thiazole ring, oxazole ring.They represent with following formula (10-1) ~ (10-14) respectively.Among these, be preferably pyridine ring, pyrimidine ring, quinoline ring, phenanthridines ring.Be more preferably pyridine ring, pyrimidine ring, quinoline ring.
[changing 14]
In the boron-containing compound represented with above-mentioned formula (2), X 5and/or X 6during for monovalent substituent, to X 5and/or X 6be not particularly limited with the bonding position of ring structure and the quantity of bonding.
In addition, if under type is also one of the preferred embodiment of the present invention: as X 52 monovalent substituent are at least bonded with in ring structure, one in this monovalent substituent for having or not having substituent monoborane base, another in this monovalent substituent is for having or not having substituent pyridine radicals, and the nitrogen-atoms of this pyridine radicals is coordinated in the boron atom of this monoborane base.That is, if under type is also one of the preferred embodiment of the present invention: in the boron-containing compound represented with above-mentioned formula (2), the part that nitrogen-atoms is coordinated in boron atom has more than 2 in the structure.
In the present invention, if under type is also one of the preferred embodiment of the present invention: in above-mentioned formula (2), X 5and X 6in one of at least substituting group for having following structure: there are 2 atoms with doubly linked structure and by 1 atom in these 2 atoms and the ring structure bonding forming dotted line circular arc portion at terminal part.Namely, if under type is also one of the preferred embodiment of the present invention: the organic compound with boron atom being formed with the resilient coating of electro-luminescence element is boron polymer, and, as this boron polymer raw material monomer component contained by boron-containing compound be the boron-containing compound with boron atom and double bond, it is characterized in that, this boron-containing compound represents with following formula (2)
[changing 15]
(in above formula, dotted line arc representation forms ring structure with connection boron atom together with a part for the skeleton part of nitrogen-atoms.Connect boron atom and represent that at least 1 pair of atom is connected with double bond with the dotted portion in the skeleton part of nitrogen-atoms, this double bond can form conjugation with ring structure.The arrow pointing to boron atom from nitrogen-atoms represents that nitrogen-atoms is coordinated in boron atom.X 5and X 6identical or different, represent hydrogen atom or as monovalent substituent substituent on ring structure, the ring structure of formation dotted line circular arc portion can be bonded with more than 2 X 5and X 6.R 1and R 2identical or different, represent hydrogen atom or monovalent substituent), above-mentioned X 5and X 6in one of at least there is following structure: there are 2 atoms with doubly linked structure and by 1 atom in these 2 atoms and the ring structure bonding forming dotted line circular arc portion at terminal part.
Above-mentioned had 2 atoms with doubly linked structure at terminal part and to be referred to by the structure of 1 atom in these 2 atoms with the ring structure bonding forming dotted line circular arc portion, namely at formation X 5and/or X 6atomic group in, the terminal part of each self-structure at least exists 2, among this terminal part, with the terminal part of the ring structure bonding of the formation dotted line circular arc portion in above-mentioned formula (2), there is following structure: be connected with double bond with the atom of ring structure bonding and the adjacent atom of this atom that form dotted line circular arc portion.As this substituting group, the structure represented with following formula (11-1) ~ (11-2) can be enumerated.
It should be noted that, in formula (11-1) ~ (11-2), * represents the atom with the ring structure bonding of the formation dotted line circular arc portion in formula (2).R 1, r 2, r 3and r 4identical or different, expression can respectively at r 1with r 2between and r 3with r 4between form the atom of double bond.In formula (11-1), q 1represent hydrogen atom or monovalent organic group, and represent r 2on also can correspond to r 2valence and be bonded with the q of more than 2 1.In formula (11-2), dotted line arc representation with by r 3and r 4the double bond part formed forms ring structure together.Q 2represent hydrogen atom or as monovalent substituent substituent on ring structure, and the ring structure of formation dotted line circular arc portion in expression (11-2) also can be bonded with the q of more than 2 2.
[changing 16]
In above-mentioned formula (11-1) ~ (11-2), r 1, r 2, r 3and r 4identical or different, expression can respectively at r 1with r 2between and r 3with r 4between form the atom of double bond, be preferably carbon atom, nitrogen-atoms, phosphorus atoms, sulphur atom.Be more preferably carbon atom, nitrogen-atoms.
In above-mentioned formula (11-1), q 1represent hydrogen atom or monovalent organic group, and represent r 2on can correspond to r 2valence and be bonded with the q of more than 2 1, this represents: such as, r 2during for nitrogen-atoms, there is 1 q 1with r 2bonding; r 2during for carbon atom, there are 2 q 1with r 2bonding.There are more than 2 q 1with r 2during bonding, q 1can all identical also can be different separately.Be not particularly limited as above-mentioned monovalent organic group, can enumerate and the R in above-mentioned formula (2) 1and R 2same group.
Among these, as q 1, be preferably hydrogen atom; Halogen atom, carboxyl, hydroxyl, sulfydryl, epoxy radicals, NCO, amino, azo group, acyl group, pi-allyl, nitro, alkoxy carbonyl group, formoxyl, cyano group, silicyl, stannyl, monoborane base, phosphino-, siloxy, aryl-sulfonyl oxygen, alkylsulfonyloxy isoreactivity group; Carbon number be 1 ~ 4 straight-chain or branched-chain alkyl or by the carbon number that these reactive groups replace be 1 ~ 4 straight-chain or branched-chain alkyl; Carbon number be 1 ~ 8 straight-chain or branched alkoxyl or by the carbon number that these reactive groups replace be 1 ~ 8 straight-chain or branched alkoxyl; Aryl or the aryl replaced by these reactive groups; Oligomeric aryl or the oligomeric aryl replaced by these reactive groups; Monovalence heterocyclic radical or the monovalence heterocyclic radical replaced by these reactive groups; The oligomeric heterocyclic radical of monovalence or the oligomeric heterocyclic radical of monovalence replaced by these reactive groups; Alkylthio group; Aryloxy group; Arylthio; Aralkyl; Aralkoxy; Aromatic alkylthio; Alkenyl or the alkenyl replaced by these reactive groups; Alkynyl or the alkynyl replaced by these reactive groups.The oligomeric aryl be more preferably hydrogen atom, bromine atoms, atomic iodine, monoborane base, alkynyl, alkenyl, formoxyl, stannyl, phosphino-, aryl or the aryl replaced by these reactive groups, being replaced by these reactive groups, the monovalence heterocyclic radical replaced by these reactive groups, the oligomeric heterocyclic radical of monovalence, alkenyl or the alkenyl replaced by these reactive groups that are replaced by these reactive groups, alkynyl or the alkynyl replaced by these reactive groups.
In above-mentioned formula (11-2), q 2represent hydrogen atom or as monovalent substituent substituent on ring structure, the ring structure of the formation dotted line circular arc portion in expression (11-2) also can be bonded with more than 2 q 2.
That is, q 2during for hydrogen atom, represent, with in the structure that formula (11-2) represents, there is q 2ring structure not there is substituting group; q 2during for monovalent substituent, this ring structure has substituting group.In this case, the substituent quantity that this ring structure has can be 1 also can be more than 2.
As above-mentioned monovalent substituent, can enumerate and the X in above-mentioned formula (2) 5and X 6same group, among these, is particularly preferably the group, naphthyl, the phenyl that represent with above-mentioned formula (8-10).
In the present invention, in addition, if under type is also one of the preferred embodiment of the present invention: the X in above-mentioned formula (2) 5and X 6be to have and there are 2 atoms with doubly linked structure and by the substituting group of 1 atom in these 2 atoms with the structure of the ring structure bonding of formation dotted line circular arc portion at terminal part.Namely, if under type is also one of the preferred embodiment of the present invention: the organic compound with boron atom being formed with the resilient coating of electro-luminescence element is boron polymer, as this boron polymer raw material monomer component contained by boron-containing compound be the boron-containing compound with boron atom and double bond, it is characterized in that, this boron-containing compound represents with following formula (2)
[changing 17]
(in formula, dotted line arc representation forms ring structure with connection boron atom together with a part for the skeleton part of nitrogen-atoms.Connect boron atom and represent that at least 1 pair of atom is connected with double bond with the dotted portion in the skeleton part of nitrogen-atoms, this double bond can form conjugation with ring structure.The arrow pointing to boron atom from nitrogen-atoms represents that nitrogen-atoms is coordinated in boron atom.X 5and X 6identical or different, represent as monovalent substituent substituent on ring structure, the ring structure of formation dotted line circular arc portion can be bonded with more than 2 monovalent substituent.R 1and R 2identical or different, represent hydrogen atom or monovalent substituent), above-mentioned X 5and X 6all there is following structure: there are 2 atoms with doubly linked structure and by 1 atom in these 2 atoms and the ring structure bonding forming dotted line circular arc portion at terminal part.
As X in above-mentioned formula (2) 5and X 6all have and there are 2 atoms with doubly linked structure at terminal part and, by 1 atom in these 2 atoms and the boron-containing compound of structure of ring structure bonding forming dotted line circular arc portion, roughly can to list: the above-mentioned double bond part formed with the atom forming the ring structure bonding of dotted line circular arc portion in above-mentioned formula (2) does not form the mode of ring structure; And form the mode of a part for ring structure with the above-mentioned double bond part that the middle atom forming the ring structure bonding of dotted line circular arc portion of above-mentioned formula (2) is formed, specifically, the mode of following formula (2 '-1) ~ (2 '-4) can be enumerated.
It should be noted that, in formula (2 '-1) ~ (2 '-4), connect the dotted portion in the skeleton part of boron atom and nitrogen-atoms, point to arrow and the R of boron atom from nitrogen-atoms 1and R 2same with formula (1).In formula (2 '-1), dotted line circular arc is same with formula (2).In formula (2 '-2) ~ (2 '-4), with connect dotted line circular arc that boron atom and a part for the skeleton part of nitrogen-atoms connect and formula (2) and similarly represent and connect boron atom form ring structure together with a part for the skeleton part of nitrogen-atoms, in addition, with r 5and r 6the double bond part formed and/or r 7and r 8the dotted line arc representation that the double bond part formed connects forms ring structure together with corresponding double bond part.R 5~ r 8identical or different, with the r in above-mentioned formula (11-1) ~ (11-2) 1~ r 4equally.Q 3and q 4identical or different, with the q in above-mentioned formula (11-1) 1equally.Q 5and q 6identical or different, with the q in above-mentioned formula (11-2) 2equally.Wherein, when boron-containing compound is the compound of formula (2 '-4) mode, q 5, q 6in at least one is the substituting group with reactive group.
[changing 18]
Among these modes, preferably with above-mentioned formula (2) in form the ring structure bonding of dotted line circular arc portion the double bond part that forms of atom all do not form ring structure mode or all form ring structure a part mode in any one.That is, the mode of above-mentioned formula (2 '-1), (2 '-4) is preferably.
The organic compound with boron atom being formed with the resilient coating of electro-luminescence element is like this for being undertaken being polymerized by the monomer component stating the boron-containing compound that formula (2 '-4) represents containing boron-containing compound represented with above-mentioned formula (2 '-1) or more and the boron polymer obtained also is one of the preferred embodiment of the present invention.
In above-mentioned formula (2 '-1), dotted line circular arc and formula (1) similarly represent and form ring structure with connection boron atom together with a part for the skeleton part of nitrogen-atoms, in above-mentioned formula (2 '-1), as long as the ring structure circulus formed by dotted line circular arc and a part for the skeleton part being connected boron atom and nitrogen-atoms is just not particularly limited, as in formula (2 '-1), there is q 3the ring of group institute bonding, can enumerate and the X in formula (2) 5the ring that the ring of institute's bonding is same.In addition, as in formula (2 '-1), there is q 4the ring of group institute bonding, can enumerate and the X in formula (2) 6the ring that the ring of institute's bonding is same.
In above-mentioned formula (2 '-2) ~ (2 '-4), with connect dotted line circular arc that boron atom and a part for the skeleton part of nitrogen-atoms connect and formula (2) and similarly represent and connect boron atom form ring structure together with a part for the skeleton part of nitrogen-atoms, further, with r 5and r 6the double bond part formed and/or r 7and r 8the dotted line arc representation that the double bond part formed connects forms ring structure together with corresponding double bond part.Namely, the boron-containing compound that above-mentioned formula (2 '-2) ~ (2 '-3) represent represents: at least have 3 ring structures in the structure, containing connecting the skeleton part of boron atom and nitrogen-atoms and 1 the double bond part part as this ring structure.In addition, the boron-containing compound that above-mentioned formula (2 '-4) represents represents: at least have 4 ring structures in the structure, containing connecting the skeleton part of boron atom and nitrogen-atoms and 2 the double bond parts part as this ring structure.
In above-mentioned formula (2 '-2) ~ (2 '-4), as long as the ring structure circulus formed by a part for the dotted line circular arc connected with a part for the skeleton part being connected boron atom and nitrogen-atoms and the skeleton part that connects boron atom and nitrogen-atoms is just not particularly limited, as containing r 5and r 6the ring of the group institute bonding of the double bond part formed, can enumerate and the X in formula (2) 5the ring that the ring of institute's bonding is same.In addition, as containing r 7and r 8the ring of the group institute bonding of the double bond part formed, can enumerate and the X in formula (2) 6the ring that the ring of institute's bonding is same.
In addition, in above-mentioned formula (2 '-2) ~ (2 '-4), as by with r 5and r 6the double bond part formed and/or r 7and r 8the dotted line circular arc that the double bond part formed connects and the ring structure that corresponding double bond part is formed, such as, can enumerate and the X in formula (2) 5x in the ring of institute's bonding and formula (2) 6the ring that the ring of institute's bonding is same.It should be noted that, in above-mentioned formula (2 '-4), by with r 5and r 6the double bond part formed and r 7and r 8the dotted line circular arc that the double bond part formed connects and the ring structure that this double bond part is formed at least exist 2, and they can be the same or different.
The manufacture method of the boron-containing compound represented with above-mentioned formula (2) is not particularly limited, such as can by the method manufacture described in Japanese Unexamined Patent Publication 2011-184430 publication.
Carried out being polymerized by monomer component containing the boron-containing compound represented with above-mentioned formula (2) and the boron polymer obtained has following repetitive, this repetitive is the X in formula (2) 5, X 6, R 1and R 2in at least 2 groups carry out polycondensation or at least 1 group carries out being polymerized and the repetitive formed.That is, for having the boron polymer of the structure of the repetitive represented with following formula (12),
[changing 19]
(in formula, dotted line circular arc, the dotted portion connected in the skeleton part of boron atom and nitrogen-atoms, the arrow pointing to boron atom from nitrogen-atoms are same with formula (2).X 5', X 6', R 1' and R 2' be the X with formula (2) respectively 5, X 6, R 1and R 2same group, represents divalent group, trivalent radical or Direct Bonding).Above-mentioned formula (12) refers to, X 5', X 6', R 1' and R 2' at least more than one part as the main chain of polymer and form key.X in above-mentioned formula (2) 5, X 6, R 1and R 2in at least 2 group polycondensations and when forming boron polymer, the X in above-mentioned formula (12) 5', X 6', R 1' and R 2' at least two be divalent group or Direct Bonding.X in above-mentioned formula (2) 5, X 6, R 1and R 2in at least 1 group when being polymerized separately and forming boron polymer, the X in above-mentioned formula (12) 5', X 6', R 1' and R 2' at least one be trivalent radical or Direct Bonding.
The boron polymer with the repetitive represented with above-mentioned formula (12) can be made up of the one in the structure represented with above-mentioned formula (12), also can containing the structure of more than two kinds represented with above-mentioned formula (12).During containing the structure of more than two kinds represented with above-mentioned formula (12), this structure of more than two kinds can be atactic polymer, also can be block polymer, can also be graft polymers etc.In addition, also can be situation or the dendrimer, dendritic polymer that in high polymer main chain, there is branch thus have more than 3 terminal parts.
Among the boron polymer with the structure of the repetitive represented with above-mentioned formula (12), the R in above-mentioned formula (12) 1' and R 2' be preferably respectively with the R in formula (2) 1and R 2same group.Further, the R in above-mentioned formula (12) 1' and R 2' be more preferably carbon number be 1 ~ 30 straight-chain or branched alkyl, carbon number be 3 ~ 30 ester ring type alkyl.
Namely, if under type is also one of the preferred embodiment of the present invention: the organic compound with boron atom being formed with the resilient coating of electro-luminescence element is the boron polymer being carried out being polymerized by the monomer component containing the boron-containing compound represented with formula (2) and obtain, wherein, the R in formula (2) 1and R 2identical or different, represent carbon number be 1 ~ 30 straight-chain or branched alkyl or carbon number be 3 ~ 30 ester ring type alkyl.
The structure obtained by polycondensation among concrete example as the structure of the repetitive represented with above-mentioned formula (12), such as, just like the structure of following formula (13-1) ~ (13-6) and so on.Among these, be preferably the structure of (13-1), (13-6).Be more preferably the structure of (13-1).That is, by there is the structure that represents with formula (2) and X in formula (2) 5and X 6the boron polymer obtained for the substituent boron-containing compound with reactive group is also one of the present invention.
[changing 20-1]
[changing 20-2]
[changing 20-3]
As above-mentioned can the combination of reactive group of polycondensation, just be not particularly limited as long as can be polymerized, such as carboxyl and hydroxyl can be enumerated, carboxyl and sulfydryl, carboxyl and amino, carboxylate and amino, carboxyl and epoxy radicals, hydroxyl and epoxy radicals, sulfydryl and epoxy radicals, amino and epoxy radicals, NCO and hydroxyl, NCO and sulfydryl, NCO and amino, hydroxyl and halogen atom, sulfydryl and halogen atom, monoborane base and halogen atom, stannyl and halogen atom, aldehyde radical and phosphorus methyl, vinyl and halogen atom, aldehyde radical and phosphonate ester methyl, haloalkyl and haloalkyl, sulfonium methyl and sulfonium methyl, aldehyde radical and acetonitrile-base, aldehyde radical and aldehyde radical, halogen atom and monoborane base, halogen atom and magnesium halide, halogen atom and halogen atom etc.
Among these, be preferably the combination of the combination of halogen atom and monoborane base, halogen atom and halogen atom.
X in above-mentioned formula (2) 5, X 6, R 1and R 2in at least 2 group polycondensations and when forming boron polymer, the X in above-mentioned formula (12) 5', X 6', R 1' and R 2' among at least two represent divalent groups or Direct Bonding, this divalent group represent not because of there is reactive group substituting group between polycondensation reaction and the residue that departs from.Formed above-mentioned can the combination of reactive group of polycondensation such substituting group with reactive group when having carried out polycondensation reaction, have situation and residual situation that residue remains in the polymer, the former when, X 5', X 6', R 1' and R 2' among at least one represent not because of there is reactive group substituting group between polycondensation reaction and the residue that departs from, when the latter, X 5', X 6', R 1' and R 2' among at least one represent Direct Bonding.
In addition, when continuous more than 2 of the repetitive that above-mentioned formula (12) represents, between 2 repetitives, such as-X is formed with 5'-X 6the X of '-such 5', X 6', R 1' and R 2' among two connected keys, in this case, any one among these two is Direct Bonding.
Forming the above-mentioned substituting group of the such reactive group of the combination of reactive group of polycondensation can carrying out polycondensation reaction and remain the concrete example of the situation of residue in the polymer as having, the substituting group with carboxyl and the substituent combination with hydroxyl can be enumerated.Such as ,-CH 2cOOH base and-CH 2cH 2when OH base has carried out polycondensation reaction, residue residual is in the polymer-CH 2(CO)-O-CH 2cH 2-Ji.In addition, such as, the reaction as-COOH base and-OH base is such, and when the substituting group with reactive group is only made up of reactive group, the residue remained in the polymer is-(CO)-O-base.
In addition, as above-mentioned can the combination of reactive group of polycondensation carry out polycondensation reaction after remain without residue in the polymer time concrete example, the combination of monoborane base and halogen atom, halogen atom and halogen atom can be enumerated.
Among the concrete example of the structure of the repetitive represented with above-mentioned formula (12), as the X in above-mentioned formula (2) 5, X 6, R 1and R 2at least 1 group be polymerized separately and the structure obtained, such as X 6polymerization and the structure that obtains are the structure as following formula (14).So, the X in formula (2) 6during for having the substituting group of the reactive group that can be polymerized separately in structure, form X 6' be the repetitive of the structure of trivalent radical or Direct Bonding.Similarly, the X in formula (2) 5, X 6, R 1or R 2in any one when being the substituting group in structure with the reactive group that can be polymerized separately, form X respectively 5', X 6', R 1', R 2' be the repetitive of the structure of trivalent radical or Direct Bonding.
[changing 21]
As the above-mentioned reactive group that can be polymerized separately, 3,5-dibromo phenyl, alkenyl, alkynyl, epoxy radicals, halogen atom etc. can be enumerated.The boron-containing compound of above-mentioned formula (2) has any one at least 1 these group, and the boron-containing compound of above-mentioned formula (2) can be polymerized separately thus.Among these, be preferably alkenyl, epoxy radicals, 3,5-dibromo phenyls.
X in above-mentioned formula (2) 5, X 6, R 1and R 2among, the group carrying out polycondensation be have in the structure above-mentioned can the substituting group of reactive group of polycondensation.Similarly, the group carrying out homopolymerization is the substituting group in the structure with the above-mentioned reactive group that can be polymerized separately.As such substituting group, can enumerate carbon number be 1 ~ 4 straight-chain or branched-chain alkyl, carbon number be 3 ~ 7 cyclic alkyl, carbon number be the straight-chain of 1 ~ 8 or the hydrogen atom of any one group such as branched alkoxyl, aryl or heterocyclic radical by above-mentioned can the group that replaces of the reactive group of polycondensation, the reactive group that can be polymerized separately.Among these, be preferably styryl, 3,5-dibromo phenyls.
As long as the material that boron polymer of the present invention is obtained by the monomer component containing the boron-containing compound represented with above-mentioned formula (2), just other monomer can be contained in monomer component.
That is, the boron-containing compound represented with formula (2) is carried out being polymerized with other monomer represented with following formula (15) and the boron polymer formed is also included within the boron polymer in the present invention.
[changing 22]
X 7-A-X 8 (15)
(in formula, A represents divalent group.X 7and X 8identical or different, represent hydrogen atom or monovalent substituent, X 7and X 8in at least 1 group be the substituting group with reactive group)
Above-mentioned formula (15) if in A be just not particularly limited for divalent group, meet the compound title of its structure if enumerate, then can enumerate such as benzene, naphthalene, anthracene, luxuriant and rich with fragrance, 1,2-benzophenanthrene, rubrene, pyrene, perylene, indenes, azulenes, adamantane, fluorenes, Fluorenone, dibenzofurans, carbazole, dibenzothiophenes, furans, pyrroles, pyrrolin, pyrrolidines, thiophene, dioxolanes, pyrazoles, pyrazoline, pyrazolidine, imidazoles, oxazole, thiazole, oxadiazole, triazole, thiadiazoles, pyrans, pyridine, piperidines, dioxane, morpholine, pyridazine, pyrimidine, pyrazine, piperazine, triazine, trithiane, norborene, benzofuran, indoles, benzothiophene, benzimidazole, benzoxazole, benzothiazole, diazosulfide, Ben Bing oxadiazole, purine, quinoline, isoquinolin, cumarin, cinnolines, quinoxaline, acridine, phenanthroline, phenthazine, flavones, triphenylamine, acetylacetone,2,4-pentanedione, dibenzoyl methane, pyridine carboxylic acid, thiophene is coughed up, porphyrin, the metal complex of iridium etc., or, they have substituent derivative, the polymer of the structure containing these derivatives or oligomer etc.
It should be noted that, as above-mentioned substituting group, can use and above-mentioned R 1and R 2in the same group of substituting group.
As above-mentioned A, except above-mentioned group, the structure of such as following formula (16-1) ~ (16-4) can also be enumerated.
[changing 23]
-Ar1- (16-1)
-Ar1-Z1-(Ar2-Z2)a-Ar3- (16-2)
-Ar1-Z2- (16-3)
-Z2- (16-4)
(in formula, Ar1, Ar2, Ar3 are identical or different, represent arlydene, divalent heterocycle or have the divalent group of structure of metal complex.Z1 represent-C ≡ C-,-N (Q3)-,-(SiQ4Q5) b-or Direct Bonding.Z2 represent-CQ1=CQ2-,-C ≡ C-,-N (Q3)-,-(SiQ4Q5) b-or Direct Bonding.Q1 and Q2 is identical or different, represents hydrogen atom, alkyl, aryl, monovalence heterocyclic radical, carboxyl, alkoxy carbonyl group, aryloxy carbonyl, aryl alkyl carbonyl oxygen, Heteroaryloxycarbonyl or cyano group.Q3, Q4 and Q5 are identical or different, represent hydrogen atom, alkyl, aryl, monovalence heterocyclic radical or aralkyl.A represents the integer of 0 ~ 1.B represents the integer of 1 ~ 12)
Above-mentioned arlydene refers to from aromatic hydrocarbon and removes the atomic group after 2 hydrogen atoms, and the carbon number forming ring is generally the degree of 6 ~ 60, is preferably 6 ~ 20.As this aromatic hydrocarbon, also comprise the aromatic hydrocarbon with condensed ring, more than 2 independently phenyl ring or condensed ring Direct Bonding or the aromatic hydrocarbons that are formed by connecting via bases such as ethenylidenes.
As above-mentioned arlydene, can enumerate such as with the group etc. that following formula (17-1) ~ (17-23) represents.Phenylene, biphenylene, fluorenylidene, sub-Stilbene base is preferably among these.
It should be noted that, in formula (17-1) ~ (17-23), R is identical or different, represent hydrogen atom, halogen atom, alkyl, alkoxyl, alkylthio group, aryl, aryloxy group, arylthio, aralkyl, aralkoxy, aromatic alkylthio, acyl group, acyloxy, amide groups, imide, imines residue, amino, substituted-amino, replace silicyl, replace siloxy, replace silylthio, replace silylamino, monovalence heterocyclic radical, heteroaryloxy, heteroarylthio, aromatic yl alkenyl, aryl ethane base, carboxyl, alkoxy carbonyl group, aryloxy carbonyl, aryl alkyl carbonyl oxygen, Heteroaryloxycarbonyl or cyano group.The such line marked with intersecting with ring structure of the line represented with x-y in formula (17-1) is ring structure and the atom Direct Bonding be bonded in part.That is, refer in formula (17-1) and any one Direct Bonding formed in the carbon atom of the ring being marked with the line represented with x-y, the bonding position in this ring structure is not limited.The such line being marked on the summit of ring structure of the line represented with z-in formula (17-10) is that ring structure is in this position and the atom Direct Bonding be bonded in part.In addition, refer to the line that the R of ring structure intersection marks marks, on this ring structure can bonding 1 R also can bonding more than 2 R, its bonding position is not also limited.
In addition, in formula (17-1) ~ (17-10) and (17-15) ~ (17-20), carbon atom can be replaced by nitrogen-atoms, oxygen atom or sulphur atom, and hydrogen atom can be replaced by fluorine atom.
[changing 24-1]
[changing 24-2]
Atomic group residual after above-mentioned divalent heterocycle refers to and removes 2 hydrogen atoms from heterocyclic compound, the carbon number forming ring is generally the degree of 3 ~ 60.As this heterocyclic compound, be also included in the element forming ring in the organic compound with ring structures and be not only carbon atom, in ring, also contain the heteroatomic organic compounds with ring structures such as aerobic, sulphur, nitrogen, phosphorus, boron, arsenic.
As above-mentioned divalent heterocycle, can enumerate such as with the heterocyclic radical etc. that following formula (18-1) ~ (18-38) represents.
It should be noted that, in formula (18-1) ~ (18-38), R is same with the R that above-mentioned arlydene has.Y represents O, S, SO, SO 2, Se or Te.For the line marked with intersecting with ring structure, be marked on ring structure summit line, with the line that marks on the R of ring structure intersection marks for, same with formula (17-1) ~ (17-23).
In addition, in formula (18-1) ~ (18-38), carbon atom can be replaced by nitrogen-atoms, oxygen atom or sulphur atom, and hydrogen atom can be replaced by fluorine atom.
[changing 25-1]
[changing 25-2]
Divalent group residual after the above-mentioned divalent group with structure of metal complex refers to and removes 2 hydrogen atoms from the organic ligand of the metal complex with organic ligand.The carbon number of this organic ligand is generally the degree of 4 ~ 60, can enumerate such as oxine and derivative thereof, benzo oxyquinoline and derivative, 2-phenyl-pyridin and derivative thereof, 2-phenyl-benzothiazol and derivative, 2-phenyl-benzoxazole and derivative, Porphyrin and its derivative etc.
As the central metal of above-mentioned metal complex, such as aluminium, zinc, beryllium, iridium, platinum, gold, europium, terbium etc. can be enumerated, as the above-mentioned metal complex with organic ligand, can enumerate as low molecular fluorescent material, phosphor material and known metal complex, triplet emissive complexes etc.
As the above-mentioned divalent group with structure of metal complex, specifically, can enumerate such as with the group that following formula (19-1) ~ (19-7) represents.
It should be noted that, in formula (19-1) ~ (19-7), R is same with the R that above-mentioned arlydene has.For be marked on ring structure summit line for, refer to Direct Bonding with formula (17-1) ~ (17-23) is same.
In addition, in formula (19-1) ~ (19-7), carbon atom can be replaced by nitrogen-atoms, oxygen atom or sulphur atom, and hydrogen atom can be replaced by fluorine atom.
[changing 26-1]
[changing 26-2]
In addition, as the structure of A, the structure of following formula (16-5) and so on can also be enumerated.
[changing 27]
(in formula, Ar4, Ar5, Ar6 and Ar7 are identical or different, represent arlydene or divalent heterocycle.Ar8, Ar9 and Ar10 are identical or different, represent aryl or monovalence heterocyclic radical.O and p is identical or different, represents 0 or 1, and 0≤o+p≤1)
As the concrete example of the structure represented with above-mentioned formula (16-5), the structure represented with following formula (20-1) ~ (20-8) can be enumerated.
[changing 28-1]
[changing 28-2]
It should be noted that, in formula (20-1) ~ (20-8), R is same with the R that above-mentioned arlydene has.For be marked on ring structure summit line for, refer to Direct Bonding with formula (17-1) ~ (17-23) is same.In above-mentioned formula (20-1) ~ (20-8), have more than 2 R in 1 structural formula, these R can identically also can be different groups.In order to improve dissolubility in a solvent, preferably there is more than 1 atom except hydrogen atom, and the symmetrical shape preferably containing substituent structure is low.Further, in above-mentioned formula (20-1) ~ (20-8), R contains aryl, heterocyclic radical in its part, these groups can also have more than 1 substituting group.In addition, R is in the substituent situation containing alkyl chain, alkyl chain can be the combination of any one or they in straight chain, side chain or ring-type, as the situation not being straight chain, such as isopentyl, 2-ethylhexyl, 3,7-dimethyl octyl groups, cyclohexyl, 4-C1 ~ C12 alkyl-cyclohexyl etc. can be enumerated.In order to improve boracic copolymer of the present invention dissolubility in a solvent, containing ring-type or branched alkyl chain in the R preferably more than 1.
In addition, more than 2 R can connect and form ring.In addition, when R is the group containing alkyl chain, this alkyl chain can by containing heteroatomic group interrupt.As this hetero-atom, oxygen atom, sulphur atom, nitrogen-atoms etc. can be enumerated.
As the structure of above-mentioned A, in said structure, be preferably formula (16-5), formula (17-9), formula (18-16), formula (18-28).
Above-mentioned boron polymer has the X in formula (2) 5, X 6, R 1and R 2in at least 1 group and X in formula (15) 7and X 8in at least 1 radical polymerisation and the repetitive formed.That is, the boron polymer with the structure of the repetitive represented with following formula (21) is also included within boron polymer of the present invention.
[changing 29]
(in formula, dotted line circular arc, the dotted portion connected in the skeleton part of boron atom and nitrogen-atoms, the arrow pointing to boron atom from nitrogen-atoms are same with formula (2).X 5', X 6', R 1' and R 2' same with formula (12).A is identical or different, represents divalent group.X 7' and X 8' represent the X with formula (15) respectively 7and X 8same group, divalent group, trivalent radical or Direct Bonding).
Above-mentioned formula (21) refers to, X 5', X 6', R 1' and R 2' in any more than 1 part as the main chain of polymer and form key and X 7' and X 8' in any more than 1 part as the main chain of polymer and form key.
In the boron polymer with the repetitive represented with above-mentioned formula (21), deriving from the repetitive of above-mentioned formula (2), derive from the repetitive of above-mentioned formula (15) can be atactic polymer, also can be block polymer, can also be graft polymers.In addition, can also be high polymer main chain Zhong You branch and have situation or the dendrimer, dendritic polymer of more than 3 terminal parts.In addition, also can be the polymer formed with above-mentioned formula (2) boron-containing compound represented and the compound polycondensation represented with above-mentioned formula (15).
In addition, the boron polymer with the repetitive represented with above-mentioned formula (21) containing deriving from the repetitive of above-mentioned formula (2), deriving from each a kind of the repetitive of above-mentioned formula (15), also can contain two or more.During containing two or more repetitive, this structure of more than two kinds can be atactic polymer, also can be block polymer, can also be graft polymers.In addition, can also be high polymer main chain Zhong You branch and have situation or the dendrimer, dendritic polymer of more than 3 terminal parts.
As the boron polymer represented with above-mentioned formula (21), there is following situation: the X in (i) above-mentioned formula (2) 5, X 6, R 1and R 2in any two with the X in above-mentioned formula (15) 7and X 8form the situation of key and a part as the main chain of polymer; (ii) X in above-mentioned formula (2) 5, X 6, R 1and R 2in X in any one and above-mentioned formula (15) 7and X 8in any 1 group form the situation of key and a part as the main chain of polymer.As the concrete example of the structure of the repetitive of above-mentioned situation, such as, there is the structure of following formula (22), (23) and so on.
[changing 30]
X in (i) above-mentioned formula (2) 5, X 6, R 1and R 2in any two with the X in above-mentioned formula (15) 7and X 8formed key and a part as the main chain of polymer when, can be the repetitive deriving from above-mentioned formula (2), the repetitive that derives from above-mentioned formula (15) carries out random addition polymerization and form, also can be that block addition polymerization forms, can also be the X in above-mentioned formula (2) 5, X 6, R 1and R 2in any one group and X in above-mentioned formula (15) 7and/or X 8polycondensation, among these, as the X in above-mentioned formula (2) 5, X 6, R 1and R 2in any 2 groups and X in above-mentioned formula (15) 7and/or X 8an example of the polymer of polycondensation, the X in above-mentioned formula (2) 5, X 6with the X in above-mentioned formula (15) 7and X 8the material of polycondensation is the structure that will represent using following formula (24) polymer as repetitive.
[changing 31]
When above-mentioned (i) structure, among the repetitive represented with above-mentioned formula (21), as the concrete example of structure division deriving from above-mentioned formula (2), have the structure of above-mentioned formula (13-1) ~ (13-6) and so on.Among these, be preferably the structure of (13-1), (13-6).Be more preferably the structure of (13-1).
As the X in above-mentioned formula (2) 5, X 6, R 1and R 2in any one group and X in above-mentioned formula (15) 7and X 8in any one group polycondensation time the combination of reactive group, the combination same with the combination of above-mentioned reactive group can be enumerated.That is, the X in above-mentioned formula (2) 5, X 6, R 1and R 2in any one group and X in above-mentioned formula (15) 7and X 8in any one group polycondensation time, the X in above-mentioned formula (15) 7and X 8among, carry out the group of polycondensation as this, preferably have in the structure above-mentioned can polycondensation reactive group substituting group in any one.
In addition, the X in above-mentioned formula (15) 7and X 8in any one when being the substituting group in the structure with the reactive group that can be polymerized separately, this substituting group is preferably any one having in the structure in the substituting group of the reactive group that can be polymerized separately above-mentioned.
The group of the two end bondings with boron polymer of the present invention is not particularly limited, also can be the same or different.As the above-mentioned group with two end bondings, such as hydrogen atom, halogen atom can be enumerated, there is or do not have substituent aryl, oligomeric aryl, monovalence heterocyclic radical, the oligomeric heterocyclic radical of monovalence, alkyl, alkoxyl, alkylthio group, aryloxy group, arylthio, aralkyl, aralkoxy, aromatic alkylthio, alkenyl, alkynyl, pi-allyl, amino, azo group, carboxyl, acyl group, alkoxy carbonyl group, formoxyl, nitro, cyano group, silicyl, stannyl, monoborane base, phosphino-, siloxy, aryl-sulfonyl oxygen, alkylsulfonyloxy etc.
The weight average molecular weight of the boron polymer in the present invention is preferably 10 3~ 10 8.If weight average molecular weight is above-mentioned scope, then can filming well.Be more preferably 10 3~ 10 7, more preferably 10 4~ 10 6.
Above-mentioned weight average molecular weight can utilize the gel permeation chromatography (GPC device, developing solvent: chloroform) based on polystyrene conversion to be measured by following apparatus and condition determination.
Efficient GPC device: HLC-8220GPC (manufacture of Dong Cao company)
Developing solvent chloroform
Post TSK-gel GMHXL × 2 piece
Eluent flow 1ml/ minute
Column temperature 40 DEG C
Boron polymer in the present invention is by being undertaken being polymerized by the monomer component containing the boron-containing compound represented with above-mentioned formula (2) and manufacturing.This monomer component is under the prerequisite containing the boron-containing compound represented with above-mentioned formula (2), also other monomer can be contained, preferably relative to whole monomer component 100 quality %, the boron-containing compound represented with above-mentioned formula (2) containing 0.1 ~ 99.9 quality %.Be more preferably 10 ~ 90 quality %.
In addition, during polymerization reaction, the solid component concentration of monomer component suitably can set in the scope of 0.01 quality % ~ soluble Cmax, if excessive rarefied, reaction efficiency is poor, if overrich, be likely difficult to control reaction, be therefore preferably 0.1 ~ 20 quality %.
As other monomer above-mentioned, preferably there is the monomer of the structure represented with above-mentioned formula (15).It should be noted that, in above-mentioned monomer component, containing a kind, also can contain two or more together with the boron-containing compound represented with above-mentioned formula (2), the compound that represents with formula (15) interior.
As other monomer above-mentioned, containing when there is the compound of the structure represented with above-mentioned formula (15), preferably relative to the boron-containing compound 1 mole represented with above-mentioned formula (2) contained in monomer component, contain the compound with the structure represented with above-mentioned formula (15) with the ratio of 0.3 ~ 3 mole.More preferably be the ratio of 0.2 ~ 2 mole relative to the boron-containing compound represented with above-mentioned formula (2) 1 mole.
In the compound represented with above-mentioned formula (15), X 7and X 8can use and above-mentioned X 5and X 6in the same group of the substituting group with reactive group.
When boron polymer in the present invention is formed by polycondensation reaction, the manufacture method of boron polymer is not particularly limited, such as, can be manufactured by the manufacture method described in Japanese Unexamined Patent Publication 2011-184430 publication.
The boron-containing compound represented with above-mentioned formula (1), the monomer component containing the boron-containing compound represented with above-mentioned formula (2) is carried out being polymerized and the boron polymer obtained all can utilize coating to carry out uniform film forming, there is low HOMO, lumo energy, therefore, it is possible to be suitable as the material of the 1st organic electroluminescent device of the present invention.
[organic electroluminescent device of the 2nd optimal way of the present invention]
In the organic electroluminescent device (being hereinafter also designated as the 2nd organic electroluminescent device of the present invention) of the 2nd optimal way of the present invention, resilient coating contains reducing agent.
In organic electroluminescent device of the present invention, as described later, the 1st electrode is negative electrode, and the 2nd electrode is anode, and resilient coating is the layer that can play the function as electron transfer layer by selecting the material of formation resilient coating.
In organic electroluminescent device, from anode supply hole, from negative electrode supply electronics, they to combine and luminous at luminescent layer again, from the part in the hole of anode supply by the 2nd metal oxide layer, luminescent layer, resilient coating, the 1st metal oxide layer and arrive negative electrode, think that this is the reason causing the efficiency of organic electroluminescent device to reduce.By arranging the resilient coating of specific thickness, hole can be suppressed to arrive negative electrode, therefore, it is possible to improve the efficiency of element.But on the other hand, if thicken the thickness of resilient coating, electronics then can be hindered from negative electrode to the movement of luminescent layer, and the ratio that between the part beyond the relatively little edge part of the impact of the thickness of resilient coating and edge part, electronics arrives luminescent layer produces difference, causes the phenomenon of only edge part luminescence.If in contrast, containing the reducing agent with supply electric function in resilient coating, then effectively can carry out being combined again of electronics and hole to the sufficient electronics of luminescent layer supply, the driving voltage required for luminescence also reduces.Thereby, it is possible to form the significantly excellent organic electroluminescent device of luminous efficiency.
2nd organic electroluminescent device of the present invention is preferred: between the 1st electrode and the 2nd electrode, have the 1st metal oxide layer, resilient coating, the low molecular compound layer comprising luminescent layer of lamination and the 2nd metal oxide layer on this resilient coating successively, this resilient coating contains reducing agent.
As long as the 2nd organic electroluminescent device of the present invention has the 1st metal oxide layer, resilient coating, the low molecular compound layer comprising luminescent layer of lamination and the 2nd metal oxide layer on this resilient coating successively between the 1st electrode and the 2nd electrode, then also can have other layer other than the above.The meaning of the low molecular compound in the present invention is described above.
In the 2nd organic electroluminescent device of the present invention, preferred resilient coating is that the average thickness formed is the layer of 5 ~ 100nm by being coated with the solution containing organic compound.
In the 2nd organic electroluminescent device of the present invention, be formed in when being laminated with the formation of the low molecular compound layer comprising luminescent layer on the 1st metal oxide layer, the low molecular compound layer generation crystallization contacted with metal oxide layer causes that leakage current increases thus and current efficiency reduces, and likely can produce because of crystallization and cannot obtain the luminous such unfavorable condition in uniform face in significant situation.In the organic electroluminescent device of organic-inorganic mixed type, the reason of low molecular compound layer generation crystallization is described above.
Such crystallization be organic-inorganic mixed type organic electroluminescent device specific to problem, it uses low molecular compound as the problem of the stylish generation of main body of luminescent layer.
For above-mentioned problem, the solution containing organic compound is coated with and the average thickness formed is the resilient coating of 5 ~ 100nm if be provided with between the 1st metal oxide layer and the low molecular compound layer comprising luminescent layer, the crystallization of the low molecular compound then in low molecular compound layer is suppressed, thus, even the organic electroluminescent device of organic-inorganic mixed type has the layer formed by low molecular compound also can suppress leakage current as during luminescent layer etc., further, the uneven face caused by leakage current can be suppressed luminous.
As mentioned above, if thicken the thickness of resilient coating, then compared with other parts, only strong luminescence phenomenon is observed in the marginal portion of luminescent layer, and on the other hand, by containing reducing agent in resilient coating, then can suppress the luminescence of this only edge part, uniform face can be obtained luminous.Therefore, if use the present invention, even if then the average thickness of resilient coating is that 5 ~ 100nm also can obtain good element characteristic.
So, 2nd organic electroluminescent device of the present invention is formed with the resilient coating that can play a role as electron transfer layer by coating, containing the reducing agent as n-type dopant in this resilient coating, by forming above-mentioned formation, low molecular compound then also can be utilized to form luminescent layer, and luminous efficiency is also excellent.
For the formation method, material, preferred thickness etc. of resilient coating, be described below.
As long as the compound of the reducing agent electron donating property contained by above-mentioned resilient coating is just not particularly limited, the hydride reducer of hydride reduction preferably can be carried out.
As hydride reducer, 2,3-dihydrobenzo [d] imidazolium compounds can be used; 2,3-dihydrobenzo [d] thiazolium compounds; 2,3-dihydrobenzo [d] oxazole compounds; Triphenylmethane compound; One kind or two or more in dihydropyridine compound etc.
So, if under type is also one of the preferred embodiment of the present invention: hydride reducer is for being selected from by 2,3-dihydrobenzo [d] imidazolium compounds, 2,3-dihydrobenzo [d] thiazolium compounds, 2,3-dihydrobenzos [at least one compound in the group of d] oxazole compounds, triphenylmethane compound and dihydropyridine compound composition.
As hydride reducer, among above-mentioned, be preferably 2,3-dihydrobenzo [d] imidazolium compounds, dihydropyridine compound.Be more preferably (4-(1,3-dimethyl-2,3-dihydro-1H-benzimidazolyl-2 radicals-Ji) phenyl) dimethylamine (N-DMBI) or 2,6-dimethyl-1,4-dihydropyridine-3,5-diethyl dicarboxylate (this ester of the Chinese (Hantzsch ester)).
Relative to the organic compound 100 quality % forming resilient coating, the amount of the reducing agent contained by above-mentioned resilient coating is preferably 0.1 ~ 15 quality %.If contain reducing agent with aforementioned proportion, then the luminous efficiency of organic electroluminescent device can be made fully high.Relative to the organic compound 100 quality % forming resilient coating, the amount of the reducing agent contained by above-mentioned resilient coating is more preferably 0.5 ~ 10 quality %, more preferably 1 ~ 5 quality %.
2nd organic electroluminescent device of the present invention is included in the low molecular compound layer comprising luminescent layer of lamination on resilient coating, and the low molecular compound layer comprising luminescent layer refers to the individual layer that formed by low molecular compound or more than 2 layers of being formed by low molecular compound long-pending layer by layer forms and wherein one deck is the layer of luminescent layer.That is, the low molecular compound layer comprising luminescent layer refers to the luminescent layer formed by low molecular compound or the luminescent layer formed by low molecular compound and any one in other layer long-pending layer by layer formed by low molecular compound.Other layer formed by low molecular compound can be 1 layer also can be more than 2 layers.In addition, the laminated order of luminescent layer and other layer is not particularly limited.
Above-mentioned other layer formed by low molecular compound is preferably hole transmission layer or electron transfer layer.That is, when low molecular compound layer is made up of the layer of more than 2 layers, preferably there is hole transmission layer and/or electron transfer layer as other layer beyond luminescent layer.So, organic electroluminescent device has hole transmission layer and/or electron transfer layer is one of preferred implementation of the 2nd organic electroluminescent device of the present invention as the independently layer different from luminescent layer.
When 2nd organic electroluminescent device of the present invention has hole transmission layer in the mode of independently layer, preferably between luminescent layer and the 2nd metal oxide layer, there is hole transmission layer.When 2nd organic electroluminescent device of the present invention has electron transfer layer in the mode of independently layer, preferably between resilient coating and luminescent layer, there is electron transfer layer.
When 2nd organic electroluminescent device of the present invention does not have as the hole transmission layer of independently layer and/or electron transfer layer, form as necessity of the 2nd organic electroluminescent device of the present invention and some layer in the layer that has has the function of these layers concurrently.
One of optimal way of 2nd organic electroluminescent device of the present invention is as under type: organic electroluminescent device is only made up of the 1st electrode, the 1st metal oxide layer, resilient coating, luminescent layer, hole transmission layer, the 2nd metal oxide layer, the 2nd electrode, and some layer in these layers has the function of electron transfer layer concurrently.
In addition, as one of optimal way that under type is also the 2nd organic electroluminescent device of the present invention: organic electroluminescent device is only made up of the 1st electrode, the 1st metal oxide layer, resilient coating, luminescent layer, the 2nd metal oxide layer, the 2nd electrode, and some layer in these layers has the function of hole transmission layer and electron transfer layer concurrently.
In 2nd organic electroluminescent device of the present invention, the 1st electrode is negative electrode, and the 2nd electrode is anode.The compound of the 1st electrode, the 2nd electrode can be used as and wherein preferred compound is same with the 1st organic electroluminescent device of the invention described above.
In addition, of the present invention 1st organic electroluminescent device of the preferred value of the average thickness of the 1st electrode, the 2nd electrode also with above-mentioned is same.
Above-mentioned 1st metal oxide layer is the layer played a role as electron injecting layer, and the 2nd metal oxide layer is the layer played a role as hole injection layer.
Formed the 1st metal oxide layer, the 2nd metal oxide layer compound concrete example and wherein preferred example is same with the 1st organic electroluminescent device of the invention described above.
The average thickness of above-mentioned 1st metal oxide layer is not particularly limited, is preferably 1 ~ 1000nm.Be more preferably 2 ~ 100nm.
The average thickness of above-mentioned 2nd metal oxide layer is not particularly limited, is preferably 1 ~ 1000nm.Be more preferably 5 ~ 50nm.
The average thickness of the 1st metal oxide layer can utilize probe-type contourgraph, light splitting ellipsometer measures.
The average thickness of the 2nd metal oxide layer can utilize quartz vibrator film thickness gauge to measure when film forming.
As the material of luminescent layer, any one low molecular compound of material that usually can be used as luminescent layer can be used, can also used in combination they.
As low molecule based compound, the compound same with the low molecule based compound in the 1st organic electroluminescent device of the invention described above can be used.
Above-mentioned luminescent layer can contain dopant.As dopant, can use the material same with the dopant in the 1st organic electroluminescent device of the invention described above, the preferable range of the content of dopant when luminescent layer contains dopant is also same with the situation of the 1st organic electroluminescent device of the invention described above.
In above-mentioned luminescent layer, the luminescent layer of the 2nd organic electroluminescent device of the present invention is preferably the luminescent layer containing phosphorescent light-emitting materials.By making luminescent layer contain phosphorescent light-emitting materials, the luminous efficiency of organic electroluminescent device is more excellent thus.
When luminescent layer contains phosphorescent light-emitting materials, preferably form luminescent layer by containing the material of phosphorescent light-emitting materials as guest materials (dopant) in material of main part.When luminescent layer is formed by above-mentioned material, dopant phosphorescent light-emitting materials preferably contains dopant relative to the content of material forming luminescent layer during with above-mentioned luminescent layer is same relative to the content of the material forming luminescent layer.
As above-mentioned phosphorescent light-emitting materials, phosphorescent light-emitting materials suitably can use the compound represented with arbitrary formula in following formula (25), (26).
[changing 32]
(in formula (25), dotted line arc representation forms ring structure together with a part for the skeleton part be made up of with 3 carbon atoms oxygen atom, comprises nitrogen-atoms and the ring structure formed is heterocycle structure.X ', X " identical or different, represent hydrogen atom or as monovalent substituent substituent on ring structure, the ring structure of formation dotted line circular arc portion can be bonded with more than 2 X ', X ".X ', X " can bonding and with together with a part for 2 of dotted line arc representation ring structures, form new ring structure.In addition, n 2when being more than 2, the X ' of more than 2 each other or X " each other can bonding and form 1 substituting group.Dotted line in the skeleton part be made up of with 3 carbon atoms nitrogen-atoms represents that 2 atoms be connected with dotted line are with singly-bound or double bond bonding.M ' represents metallic atom.The arrow pointing to M ' from nitrogen-atoms represents that nitrogen-atoms is coordinated in M ' atom.N 2represent the valence mumber of metallic atom M ')
[changing 33]
(in formula (26), dotted line arc representation forms ring structure together with a part for the skeleton part be made up of with 3 carbon atoms oxygen atom, comprises nitrogen-atoms and the ring structure formed is heterocycle structure.X ', X " identical or different, represent hydrogen atom or as monovalent substituent substituent on ring structure, the ring structure of formation dotted line circular arc portion can be bonded with more than 2 X ', X ".X ', X " can bonding and with together with a part for 2 of dotted line arc representation ring structures, form new ring structure.Dotted line in the skeleton part be made up of with 3 carbon atoms nitrogen-atoms represents that 2 atoms be connected with dotted line are with singly-bound or double bond bonding.M ' represents metallic atom.The arrow pointing to M ' from nitrogen-atoms represents that nitrogen-atoms is coordinated in M ' atom.N 2represent the valence mumber of metallic atom M '.Connect X awith X bsolid line arc representation X aand X bconnect via at least 1 other atom, can with X aand X bform ring structure together.X a, X bidentical or different, represent any one in oxygen atom, nitrogen-atoms, carbon atom.From X bthe arrow pointing to M ' represents X bbe coordinated in M ' atom.M ' is the number of 1 ~ 3)
As in above-mentioned formula (25) and formula (26) with the ring structure of dotted line arc representation, aromatic rings or heterocycle that carbon number is 2 ~ 20 can be enumerated, the aromatic hydrocarbon rings such as phenyl ring, naphthalene nucleus, anthracene nucleus can be enumerated; The heterocycles such as pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, benzothiazole ring, benzo mercaptan ring, benzoxazole ring, piperonyl cyclonene, benzimidazole ring, quinoline ring, isoquinolin ring, quinoxaline ring and phenanthridines ring, thiphene ring, furan nucleus, benzothiophene ring, benzofuran ring.
In above-mentioned formula (25) and formula (26), as with X ', X " substituting group that the ring structure that represents has, can halogen atom be enumerated, carbon number is the alkyl of 1 ~ 20 (preferred carbon number is 1 ~ 10), carbon number is the aralkyl of 1 ~ 20 (preferred carbon number is 1 ~ 10), carbon number is the alkenyl of 1 ~ 20 (preferred carbon number is 1 ~ 10), carbon number is the aryl of 1 ~ 20 (preferred carbon number is 1 ~ 10), arylamino, cyano group, amino, acyl group, carbon number is the alkoxy carbonyl group of 1 ~ 20 (preferred carbon number is 1 ~ 10), carboxyl, carbon number is the alkoxyl of 1 ~ 20 (preferred carbon number is 1 ~ 10), carbon number is the alkyl amino of 1 ~ 20 (preferred carbon number is 1 ~ 10), carbon number is the dialkyl amido of 1 ~ 20 (preferred carbon number is 1 ~ 10), carbon number is the aryl alkyl amino of 1 ~ 20 (preferred carbon number is 1 ~ 10), carbon number is the haloalkyl of 1 ~ 20 (preferred carbon number is 1 ~ 10), hydroxyl, aryloxy group, carbazyl etc.
It should be noted that, with X ', X " substituting group that has of the ring structure that represents is when being aryl, arylamino; the aromatic rings comprised in aryl, arylamino can also have substituting group; as substituting group in this case, can enumerate with above-mentioned with X ', X " group that the substituent concrete example that represents is identical.
In above-mentioned formula (25) and formula (26), with X ', X " substituting group that represents bonds together and with when forming new ring structure with a part for 2 of dotted line arc representation ring structures; as combination with the ring structure of 2 of dotted line arc representation ring structures and new ring structure, such as, can enumerate the structure of following (27-1), (27-2) and so on.
[changing 34]
In above-mentioned formula (25) and formula (26), as the metallic atom represented with M ', ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum and gold can be enumerated.
As the structure represented with above-mentioned formula (26), the structure etc. of following formula (28-1), (28-2) can be enumerated.
[changing 35]
(in formula (28-1), (28-2), R 3~ R 5identical or different, represent hydrogen atom or monovalent substituent.In formula (28-2), R 3~ R 5during for monovalent substituent, ring structure can have more than 2 monovalent substituent.Point to the arrow of M ' from nitrogen-atoms and represent that nitrogen-atoms, oxygen atom ligand are in M ' atom from the arrow of oxygen atom sensing M '.Dotted line, X ', X in the skeleton part be made up of dotted line circular arc, nitrogen-atoms and 3 carbon atoms ", M ', n 2, m ' is same with formula (26))
As R 3~ R 5monovalent substituent, can enumerate with in above-mentioned formula (25), (26) with X ', X " the same group of the substituting group that has of the ring structure that represents.
As the concrete example of the compound represented with above-mentioned formula (25), formula (26), the compound etc. represented with following formula (29-1) ~ (29-30) can be enumerated.
[changing 36-1]
[changing 36-2]
[changing 36-3]
[changing 36-4]
As the phosphorescent light-emitting materials in the present invention, what can use in above-mentioned material is one kind or two or more, among these, is preferably three (the 2-phenylpyridines) represented with above-mentioned formula (29-1) and closes iridium (Ir (ppy) 3), three (the 1-phenyl isoquinolin quinolines) that represent with above-mentioned formula (29-19) close iridium (Ir (piq) 3), (acetylacetone,2,4-pentanedione) two (2-methyldiphenyl is quinoxaline also-[f, h]) of representing with above-mentioned formula (29-27) close iridium (Ir (MDQ) 2(acac) three [the 3-methyl-2-phenylpyridines]), represented with above-mentioned formula (29-28) close iridium (Ir (mpy) 3) etc.
As aforementioned body material, can enumerate the metal complex represented with following formula (30), the metal complex represented with following formula (31), the metal complex that represents with following formula (32), what can use in them is one kind or two or more.
[changing 37]
(in formula (30), dotted line arc representation forms ring structure with connection oxygen atom together with a part for the skeleton part of nitrogen-atoms, comprises Z 1the ring structure formed with nitrogen-atoms is heterocycle structure.X ', X " identical or different, represent hydrogen atom or as monovalent substituent substituent on ring structure, the ring structure of formation dotted line circular arc portion can be bonded with more than 2 X ', X ".X ', X " can bonding and with together with a part for 2 of dotted line arc representation ring structures, form new ring structure.Connect oxygen atom and the dotted line in the skeleton part of nitrogen-atoms and represent that 2 atoms be connected with dotted line are with singly-bound or double bond bonding.M represents metallic atom.Z 1represent carbon atom or nitrogen-atoms.The arrow pointing to M from nitrogen-atoms represents that nitrogen-atoms is coordinated in M atom.R 0represent monovalent substituent or divalent linker.M represents R 0quantity, it is the number of 0 or 1.N 3represent the valence mumber of metallic atom M.R is the number of 1 or 2);
[changing 38]
(in formula, X ', X " identical or different, represent hydrogen atom or as monovalent substituent substituent on quinoline ring structure, quinoline ring structure can be bonded with more than 2 X ', X ".M represents metallic atom.The arrow pointing to M from nitrogen-atoms represents that nitrogen-atoms is coordinated in M atom.R 0represent monovalent substituent or divalent linker.M represents R 0quantity, it is the number of 0 or 1.N 3represent the valence mumber of metallic atom M.R is the number of 1 or 2);
[changing 39]
(in formula, dotted line arc representation forms ring structure with connection oxygen atom together with a part for the skeleton part of nitrogen-atoms, comprises Z 1the ring structure formed with nitrogen-atoms is heterocycle structure.X ', X " identical or different, represent hydrogen atom or as monovalent substituent substituent on ring structure, the ring structure of formation dotted line circular arc portion can be bonded with more than 2 X ', X ".X ', X " can bonding and with together with a part for 2 of dotted line arc representation ring structures, form new ring structure.Connect oxygen atom and the dotted line in the skeleton part of nitrogen-atoms and represent that 2 atoms be connected with dotted line are with singly-bound or double bond bonding.M represents metallic atom.Z 1represent carbon atom or nitrogen-atoms.The arrow pointing to M from nitrogen-atoms represents that nitrogen-atoms is coordinated in M atom.N 3represent the valence mumber of metallic atom M.Connect X aand X bsolid line arc representation X aand X bconnect via at least 1 other atom, can with X aand X bform ring structure together.And at the X across at least 1 other atom awith X bkey in can contain coordinate bond.X a, X bidentical or different, represent any one in oxygen atom, nitrogen-atoms, carbon atom.From X bthe arrow pointing to M represents X bbe coordinated in atom.M ' is the number of 1 ~ 3)
In above-mentioned formula (30), when r is 1, form the metal complex represented with following formula (33-1) in the structure with 1 M atom; When r is 2, form the metal complex represented with following formula (33-2) in the structure with 2 M atoms.
[changing 40]
In above-mentioned formula (30), formula (32), as with the ring structure of dotted line arc representation, can be the ring structure be made up of 1 ring, also can be the ring structure be made up of the ring of more than 2.As such ring structure, aromatic rings or heterocycle that carbon number is 2 ~ 20 can be enumerated, the aromatic rings such as phenyl ring, naphthalene nucleus, anthracene nucleus can be enumerated; The heterocycles such as diazole ring, thiazole ring, isothiazole Huan, oxazole ring, isoxazole ring, Thiadiazole, oxadiazole rings, triazole ring, imidazole ring, imidazoline ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, diazine ring, triazine ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, BTA ring.
Among these, be preferably phenyl ring, thiazole ring, isothiazole Huan, oxazole ring, isoxazole ring, Thiadiazole, oxadiazole rings, triazole ring, imidazole ring, imidazoline ring, pyridine ring, pyridazine ring, pyrimidine ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, BTA ring.
In above-mentioned formula (30) ~ (32), as with X ', X " substituting group that has of the ring structure that represents, can enumerate with in above-mentioned formula (25), formula (26) with X ', X " the same group of the substituting group that has of the ring structure that represents.
In above-mentioned formula (30), formula (32), with X ', X " substituting group that has of the ring structure that represents bonds together and with form new ring structure together with a part for 2 of dotted line arc representation ring structures time; as combination with the ring structure of 2 of dotted line arc representation ring structures and new ring structure, such as, can enumerate the structure of above-mentioned (27-1), (27-2) and so on.
In above-mentioned formula (30) ~ (32), as the metallic atom represented with M, be preferably the metallic atom of 1st ~ 3 races of periodic table, 9 races, 10 races, 12 races or 13 races, be preferably any one in zinc, aluminium, gallium, platinum, rhodium, iridium, beryllium, magnesium.
In above-mentioned formula (30), formula (31), R 0during for monovalent substituent, monovalent substituent is preferably any one in following formula (34-1) ~ (34-3).
[changing 41]
(in formula, Ar 1~ Ar 5represent the structure or do not have with substituent aromatic rings, heterocycle or more than 2 aromatic rings or heterocycle Direct Bonding, Ar 3~ Ar 5can be that same structure also can for different structure.Q 0represent silicon atom or germanium atom)
As Ar 1~ Ar 5aromatic rings or the concrete example of heterocycle, can enumerate with in above-mentioned formula (30) with the example that the concrete example of the aromatic rings of the ring structure of dotted line arc representation or heterocycle is same, as the structure of more than 2 aromatic rings or heterocycle Direct Bonding, these are as aromatic rings or the concrete example of heterocycle and the structure of the ring structure Direct Bonding enumerated can to enumerate more than 2.It should be noted that, in this case, the aromatic rings of more than 2 of Direct Bonding or heterocycle can be that identical ring structure also can for different ring structures.
As the substituent concrete example of aromatic rings or heterocycle, can enumerate with in above-mentioned formula (30) with the group that the substituent concrete example of the aromatic rings of the ring structure of dotted line arc representation or heterocycle is same.
In above-mentioned formula (30), formula (31), R 0during for divalent linker, R 0be preferably any one in-O-,-CO-.
In above-mentioned formula (32), by X a, X bbe connected X aand X bthe structure that formed of solid line circular arc can comprise more than 1 or 2 ring structure.Ring structure can comprise X a, X band formed, as ring structure in this case, can enumerate with in above-mentioned formula (30), formula (32) with the same ring structure of the ring structure of dotted line arc representation or pyrazole ring.Preferably comprise X a, X band form the structure of pyrazole ring.
In above-mentioned formula (32), connect X aand X bsolid line circular arc can only be made up of carbon atom, also can contain other atom.As other atom, boron atom, nitrogen-atoms, sulphur atom etc. can be enumerated.
And connect X aand X bsolid line circular arc can comprise X containing more than 1 or 2 a, X band the ring structure beyond the ring structure formed, as ring structure in this case, can enumerate with in above-mentioned formula (30), formula (32) with the same ring structure of the ring structure of dotted line arc representation or pyrazole ring.
As the structure represented with above-mentioned formula (32), the structure etc. of following formula (35) can be enumerated.
[changing 42]
(in formula (35), R 3~ R 5identical or different, represent hydrogen atom or monovalent substituent.Point to the arrow of M from nitrogen-atoms and represent that nitrogen-atoms, oxygen atom ligand are in M atom from the arrow of oxygen atom sensing M.Dotted line circular arc, dotted line, X ', the X connected in the skeleton part of oxygen atom and nitrogen-atoms ", M, Z 1, n 3, m ' is same with formula (32))
As the R of formula (35) 3~ R 5monovalent substituent, can enumerate with in above-mentioned formula (25), (26) with X ', X " the same group of the substituting group that has of the ring structure that represents.
As the concrete example of the compound represented with above-mentioned formula (30), the compound etc. of the structure represented with following formula (36-1) ~ (36-40) can be enumerated.
[changing 43-1]
[changing 43-2]
[changing 43-3]
[changing 43-4]
As the concrete example of the compound represented with above-mentioned formula (31), the compound etc. of the structure represented with following formula (37-1) ~ (37-3) can be enumerated.
[changing 44]
As the concrete example of the compound represented with above-mentioned formula (32), the compound etc. of the structure represented with following formula (38-1) ~ (38-8) can be enumerated.
[changing 45]
As the material of main part in the present invention, what can use in above-mentioned material is one kind or two or more, among these, be preferably two [2-(2-[4-morpholinodithio base) phenol] zinc represented with above-mentioned formula (36-11), two (10-hydroxy benzo [h] quinoline) beryllium (Bebq represented with above-mentioned formula (36-34) 2), two (2-(2-hydroxy phenyl) pyridine) beryllium (Bepp of representing with above-mentioned formula (36-35) 2).
The average thickness of above-mentioned luminescent layer is not particularly limited, is preferably 10 ~ 150nm.Be more preferably 20 ~ 100nm.
The average thickness of luminescent layer can utilize quartz vibrator film thickness gauge to measure when film forming.
As the material of above-mentioned hole transmission layer, the material same with the material of the hole transmission layer in the 1st organic electroluminescent device of the invention described above can be used.
In addition, the preferred value of the average thickness of hole transmission layer is also same with the situation of the 1st organic electroluminescent device of the invention described above.
As the material of above-mentioned electron transfer layer, the material same with the material of the electron transfer layer in the 1st organic electroluminescent device of the invention described above can be used.
In addition, the preferred value of the average thickness of electron transfer layer is also same with the situation of the 1st organic electroluminescent device of the invention described above.
For organic electroluminescent device of the present invention, the method for formation the 1st, the 2nd metal oxide layer, the 2nd electrode, luminescent layer, hole transmission layer, electron transfer layer is also same with the formation method of these layers in the 1st organic electroluminescent device of the invention described above.
As mentioned above, the layer that the resilient coating that organic electroluminescent device of the present invention comprises is formed preferably by the solution be coated with containing organic compound.The crystallization of the low molecular compound of film forming on resilient coating effectively can be suppressed thus by the resilient coating of coating formation specific thickness.
Above-mentioned coating contain the solution of organic compound method, in order to method, solvent and the concentration concentration preparing the organic compound in the solvent and solvent that use containing the solution of organic compound also contains the solution of organic compound and forms resilient coating during with the coating in the 1st organic electroluminescent device of the invention described above same.
Go out resilient coating by coating film forming, what exist on the 1st metal oxide layer surface is concavo-convex by smoothing, therefore inhibits the crystallization of the low molecular compound of film forming on resilient coating subsequently.
The difference of such resilient coating and Japanese Unexamined Patent Publication 2012-4492 publication (patent documentation 5) invention disclosed is described above.
The average thickness of above-mentioned resilient coating is preferably 5 ~ 100nm.Be above-mentioned scope by average thickness, the effect suppressing to comprise the crystallization of the low molecular compound layer of luminescent layer can be played fully.If the average thickness of resilient coating is thinner than 5nm, then likely can not make the concavo-convex smoothing existed at the 1st metal oxide surface fully, leakage current increases and can not play the effect forming resilient coating fully.In addition, if the average thickness of resilient coating is thicker than 100nm, then driving voltage rise and not preferred in practicality.In addition, as organic compound, when using the compound of the preferred structure in the present invention described later, resilient coating can also give full play to the function as electron transfer layer.The average thickness of above-mentioned resilient coating is more preferably 10 ~ 60nm.
The average thickness of resilient coating can utilize probe-type contourgraph, light splitting ellipsometer measures.
2nd organic electroluminescent device of the present invention can be each layer that lamination is configured with electro-luminescence element on substrate.It, for when each layer of lamination forms on substrate, preferably forms each layer being formed on the 1st electrode on substrate.In this case, organic electroluminescent device of the present invention can be the top emission type element extracting light in the opposition side with the side having substrate, also can be the bottom emission type element extracting light in the side having substrate.
The material of the material of aforesaid substrate, the average thickness of substrate and the substrate in the 1st organic electroluminescent device of the invention described above, the average thickness of substrate are same.
For the 2nd organic electroluminescent device of the present invention, as the example of the organic compound of formation resilient coating, the organic compound same with the organic compound of the formation resilient coating in the 1st organic electroluminescent device of the invention described above can be enumerated.
In addition, for the 2nd organic electroluminescent device of the present invention, the organic compound forming resilient coating preferably has the organic compound of boron atom, is more preferably the boron-containing compound represented with above-mentioned formula (1).The reason of the boron-containing compound of preferred this structure is as noted before.
And the preferred structure in the boron-containing compound represented with formula (1) is also same with the situation of the 1st organic electroluminescent device of the present invention.
The boron-containing compound represented with above-mentioned formula (1) can carry out uniform film forming by coating, has low HOMO, lumo energy, therefore, it is possible to be suitable as the material of the 2nd organic electroluminescent device of the present invention.
2nd organic electroluminescent device of the present invention is organic electroluminescent device of the present invention, and resilient coating contains reducing agent, thus, can make the excellent in luminous characteristics of organic electroluminescent device.Among the 2nd organic electroluminescent device of the present invention like this, preferably there is successively the 1st metal oxide layer, resilient coating, the low molecular compound layer comprising luminescent layer of lamination and the 2nd metal oxide layer on this resilient coating between the 1st electrode and the 2nd electrode, and this resilient coating contains reducing agent.
The manufacture method of the organic electroluminescent device of the organic-inorganic mixed type of the 2nd optimal way of the present invention like this, i.e. a kind of manufacture method with the organic electroluminescent device of the structure of the layer being laminated with more than 2 layers, it is characterized in that, this manufacture method comprises following operation: between the 1st electrode and the 2nd electrode, have the 1st metal oxide layer according to organic electroluminescent device successively, resilient coating containing reducing agent, the low molecular compound layer comprising luminescent layer of lamination on this resilient coating, each layer of electro-luminescence element is configured with the mode lamination of the 2nd metal oxide layer, the manufacture method of the organic electroluminescent device of the 2nd optimal way of the present invention so is also one of the present invention.
The manufacture method of the organic electroluminescent device of the 2nd optimal way of the present invention preferably comprises coating and contains the solution of organic compound and form the operation that average thickness is the resilient coating of 5 ~ 100nm.
The manufacture method of the organic electroluminescent device of the 2nd optimal way of the invention described above also can comprise other operation under the prerequisite comprising above-mentioned operation, also can comprise formation the 1st, the 2nd metal oxide layer, resilient coating, comprise luminescent layer low molecular compound layer beyond the operation of layer.In addition, be formed the material of each layer of electro-luminescence element, formation method, organic compound, in order to the thickness preparing solvent and each layer used containing the solution of organic compound same with the 2nd organic electroluminescent device of the present invention, preferred scheme is also same.
[organic electroluminescent device of the 3rd optimal way of the present invention]
The organic illuminating element (being hereinafter also designated as the 3rd organic electroluminescent device of the present invention) of the 3rd optimal way of the present invention is: the organic illuminating element of to be the average thickness be made up of nitrogenous film the be layer of 3 ~ 150nm of the resilient coating in organic illuminating element of the present invention.
In other words, 3rd organic electroluminescent device of the present invention is the organic electroluminescent device between anode and the negative electrode being formed on substrate with the structure of the layer being laminated with more than 2 layers, wherein, above-mentioned organic electroluminescent device has metal oxide layer between the anode and the cathode, and it is the layer of 3 ~ 150nm that above-mentioned metal oxide layer has the average thickness be made up of nitrogenous film.
Nitrogenous film does not preferably have the nitrogenous film of electron-transporting.It should be noted that, the electron-transporting that do not have of indication refers to that electron mobility is extremely low herein.Specifically refer to that meeting electron mobility is less than 10 -6cm 2degree or the conductivity of/Vs are less than 10 -6any one in the degree of S/m.
3rd organic electroluminescent device of the present invention is the organic electroluminescent device between anode and the negative electrode being formed on substrate with the reverse geometry of the structure of the layer being laminated with more than 2 layers, between the anode and the cathode there is metal oxide layer, it is the layer of 3 ~ 150nm that this metal oxide layer has the average thickness be made up of nitrogenous film, as long as so, then be not particularly limited the quantity of other layer, the order of material and lamination that forms other layer, preferable alloy oxide skin(coating) and nitrogen containing compound layer are between negative electrode and luminescent layer.The Electron Injection Characteristics of nitrogen-containing compound is excellent, and the organic electroluminescent device with this layer formation has high Electron Injection Characteristics, is formed as the element of luminous efficiency excellence.
The nitrogenous film total used in the 3rd organic electroluminescent device of the present invention has following 4 kinds: the nitrogenous film that (1) is formed by nitrogen-containing compound on metal oxide layer; (2) the nitrogenous film of the height formed by nitrogen-containing compound on metal oxide layer; (3) the nitrogenous film formed by making nitrogen-containing compound decompose on metal oxide layer; (4) the nitrogenous film of height formed by making nitrogen-containing compound decompose on metal oxide layer.
Making for by forming such film the reason that the performance of organic electroluminescent device improves, being inferred as described below.
First, during containing nitrogen-atoms, its isolated electron forms key to tending to the metallic atom in base material.Polarized meter between this metal-nitrogen key reveals strong Electron Injection Characteristics.The whole nitrogenous film of above-mentioned (1) ~ (4) all meets above-mentioned situation.It is further preferred that above-mentioned (2) that have the right nitrogen-atoms ratio of isolated electron high are more suitable for.
For above-mentioned (3), (4), be present in film on base material, fruiting period rich and varied metal-nitrogen key to appear to high-density owing to forming nitrogen-atoms to the phenomenon and expecting that film generates relevant decomposition.And think wherein also there is than ever firmly metal-nitrogen key.Further, according to the situation of decomposing, other one-tenth branch such as unwanted carbon disappears sometimes, and make nitrogen-atoms mark relatively increase thus, result achieves the environment (4) be more suitable for.In these nitrogenous films, main nitrogen source is metal-nitrogen key, therefore can expect to gather nitrogen-atoms with the density higher than the physical absorption of common molecule.Thinking due to these reasons, by having this nitrogenous film, making the luminous efficiency excellence of organic electroluminescent device, element drives stability and component life excellent.In fact, the phenomenon caused by decomposition of above-mentioned nitrogen-containing compound can be confirmed by the X-ray photoelectron spectroscopy as one of surface analysis method.Concrete result illustrates in an embodiment, to use containing nitrogen and carbon as the compound of constitution element as nitrogen-containing compound, carry out the process making this compound decomposition, observe carbon thus: nitrogen ratio (CN ratio), for from 2:1 to 1:1, defines high nitrogen ratio.And observe, by above-mentioned process, the half-peak breadth of the spectrum of nitrogen increases, and this result shows chemical environment expansion, has also implied the more firmly appearance of metal-nitrogen key simultaneously.
Therefore, think that the substrate of the layer be made up of nitrogenous film also contributes to showing the effect that the 3rd organic electroluminescent device of the present invention as above plays widely for the film containing metallic element.
The nitrogenous film of above-mentioned (1), (2) is the film be made up of nitrogen-containing compound formed on metal oxide layer, defines film namely there is not the condition of decomposing at nitrogen-containing compound under.The compound that the nitrogenous film of above-mentioned (2) uses nitrogen-atoms number high relative to the ratio of the whole atomicities forming nitrogen-containing compound is formed as nitrogen-containing compound.
The formation method of the nitrogenous film of above-mentioned (1), (2) is not particularly limited, but is applicable to the method that uses making solvent evaporates after the solution coat of nitrogen-containing compound is on metal oxide layer.
The nitrogenous film of above-mentioned (3), (4) is the film formed by making nitrogen-containing compound decompose on metal oxide layer, but also can remain a part of undecomposed nitrogen-containing compound.Preferred nitrogen-containing compound all decomposes.
The formation method of the nitrogenous film of above-mentioned (3), (4) is not particularly limited, but applicable use makes nitrogen-containing compound decompose and the method for formation after the solution coat of nitrogen-containing compound is on metal oxide layer.
Above-mentioned nitrogenous film is formed preferably by the method being included in operation metal oxide layer being coated with the solution containing nitrogen-containing compound.Form nitrogenous film by the method comprising above-mentioned operation, the organic electroluminescent device thus with metal oxide layer can suppress leakage current, can obtain uniform face luminous.
Its reason with in the 1st organic illuminating element of the invention described above by there is the solution and the resilient coating that formed that are coated with containing organic compound thus can leakage current being suppressed and to obtain the reason of uniform face luminescence identical.
Above-mentioned nitrogenous film contains nitrogen element and carbon as the element forming film, and the ratio that exists of the nitrogen-atoms and carbon atom that form this film preferably meets following relation:
Nitrogen-atoms number/(nitrogen-atoms number+carbon number) >1/8.
So, if the ratio of the nitrogen-atoms number in nitrogenous film is high, then the sum of metal-nitrogen key increases, and result makes Electron Injection Characteristics higher due to stronger polarization.Nitrogen-atoms number in nitrogenous film/(nitrogen-atoms number+carbon number) is more preferably greater than 1/5.
There is ratio and can be measured by electron spectroscopy for chemical analysis (XPS) of nitrogen element in nitrogenous film, carbon.
Above-mentioned (3), (4) as long as nitrogenous film by make on metal oxide layer nitrogen-containing compound decompose and formed, the method then making nitrogen-containing compound decompose just is not particularly limited, and is formed preferably by heating makes nitrogen-containing compound decompose.
If make nitrogen-containing compound decompose by heating, then the metallic atom in metal oxide layer and the bonding of nitrogen-atoms strengthen, and thus, organic electroluminescent device can play high driving stability in longer-term ground.
Therefore, the method that above-mentioned nitrogenous film is formed containing making nitrogen-containing compound decompose by heating after the solution of nitrogen-containing compound most preferably by coating on metal oxide layer is formed, formed by this method, can be inhibited leakage current and obtain the effect of uniform face luminescence and play the high effect driving stability with making organic electroluminescent device longer-term thus.
The manufacture method of such HOILED element, i.e. a kind of manufacture method between anode and the negative electrode being formed on substrate with the organic electroluminescent device of the structure of the layer being laminated with more than 2 layers, it is characterized in that, above-mentioned manufacture method comprises: the operation of the solution of coating containing nitrogen-containing compound on metal oxide layer; Manufacture the operation of the layer be made up of nitrogenous film of the present invention with carrying out heat treated at the temperature occurring to decompose at this nitrogen-containing compound, the manufacture method of above-mentioned organic electroluminescent device is also one of the present invention.
The above-mentioned heat treated for making nitrogen-containing compound decompose preferably is carried out under air.By carrying out under air, fully can promote the decomposition of nitrogen-containing compound thus, organic electroluminescent device can be made to play higher driving stability chronically.
The temperature of the above-mentioned heat treated for making nitrogen-containing compound decompose is preferably 80 ~ 200 DEG C, and the time is preferably 1 ~ 30 minute.
The temperature and time of heat treated suitably can set according to the kind of nitrogen-containing compound among above-mentioned scope.Such as, when using the following polymer in main chain backbone with polyalkyleneimine structure as nitrogen-containing compound, the larger then decomposition temperature of molecular weight of polymer is higher, therefore can consider the molecular weight of polymer, suitably set the temperature and time of heat treated with reference to the heat treated condition in embodiment described later.
Whether nitrogen-containing compound decomposition occurs can be confirmed by X-ray photoelectron spectroscopy (XPS) mensuration.
For above-mentioned nitrogenous film, after having carried out the operation making nitrogen-containing compound decompose on metal oxide layer, the operation utilizing the surface of the organic solvent such as ethanol, methyl cellosolve to film to clean can also be carried out, form above-mentioned nitrogenous film thus.
As above-mentioned nitrogen-containing compound, such as, can enumerate the pyridines of the phenyl amines or polyvinylpyridine and so on of the pyroles or polyaniline and so on of the pyrrolidinone compounds of polyvinylpyrrolidone and so on, polypyrrole and so on, similarly can enumerate pyrrolidines, imidazoles, piperidines, miazines, triazines etc. there is nitrogenous heterocyclic compound, amines.Wherein, be preferably the compound that nitrogen content is many, be preferably polynary amine or the compound containing triazine ring.
Polynary amine due to nitrogen-atoms number high relative to the ratio of whole atomicities forming compound, therefore from the viewpoint of making organic electroluminescent device have high electron injection and drive the more applicable of stability.
As polynary amine, preferably can by coating cambial polynary amine, can be low molecular compound also can be macromolecular compound.As low molecular compound, preferably use the polyalkylene polyamine of diethylenetriamines and so on, for macromolecular compound, preferably use the polymer with polyalkyleneimine structure.Be particularly preferably polyethylene imine based.
It should be noted that, low molecular compound herein refers to not to be the compound of macromolecular compound (polymer), might not refer to the compound that molecular weight is low.
Among above-mentioned polynary amine, one of polymer the preferred embodiment of the present invention being used in main chain backbone the straight chain structure with polyalkyleneimine structure.
Among polynary amine, by using the polymer of this structure, make element drives stability and component life more excellent.This infers it is because, this polymer in main chain backbone with polyalkyleneimine structure is due to for straight chain structure but solid, stably exists in the devices thus.
The nitrogenous film formed on metal oxide layer by this polymer in main chain backbone with the straight chain structure of polyalkyleneimine structure becomes the nitrogenous film of above-mentioned (1).
It should be noted that, as long as the polymer in main chain backbone with the straight chain structure of polyalkyleneimine structure is formed, the major part of polyalkyleneimine structure of main chain backbone is formed by connecting with straight-chain, locally can have branched structure.Be preferably formed the polyalkyleneimine structure of main chain backbone more than 80% is formed by connecting with straight-chain, more preferably more than 90% be formed by connecting with straight-chain, preferably more than 95% be formed by connecting with straight-chain further, most preferably form the polyalkyleneimine structure of main chain backbone 100% is formed by connecting with straight-chain.
The above-mentioned polyalkyleneimine structure with the polymer of polyalkyleneimine structure is preferably the structure that the alkylene imine being 2 ~ 4 by carbon number is formed.The structure that the alkylene imine that to be more preferably by carbon number be 2 or 3 is formed.
The polymer as long as above-mentioned with polyalkyleneimine structure has polyalkyleneimine structure in main chain backbone, also can be the copolymer of the structure had beyond polyalkyleneimine structure.
When the above-mentioned polymer with polyalkyleneimine structure has the structure beyond polyalkyleneimine structure, as the monomer of the raw material of the structure become beyond polyalkyleneimine structure, can enumerate such as ethene, propylene, butylene, acetylene, acrylic acid, styrene or vinylcarbazole etc., what can use in them is one kind or two or more.In addition, the monomer of the structure replaced by other organic group with the hydrogen atom of the carbon atom bonding of these monomers can also be used suitably.Alternatively other organic group of hydrogen atom, such as can enumerate the carbon number containing at least one atom in the group selecting free oxygen atom, nitrogen-atoms, sulphur atom to form to be the alkyl etc. of 1 ~ 10.
The monomer that the above-mentioned polymer with polyalkyleneimine structure preferably forms polyalkyleneimine structure among the monomer component 100 quality % of main chain backbone forming polymer is more than 50 quality %.Be more preferably more than 66 quality %, more preferably more than 80 quality %.The monomer most preferably being formation polyalkyleneimine structure is 100 quality %, the polymer namely with polyalkyleneimine structure is the homopolymers of polyalkyleneimine.
The above-mentioned weight average molecular weight with the polymer of polyalkyleneimine structure is preferably less than 100000.Use the polymer with polyalkyleneimine structure of such weight average molecular weight, carry out heat treated there is the temperature of decomposing at polymer under and form layer, the driving stability of organic electroluminescent device can be made thus more excellent.Be more preferably less than 10000, more preferably 100 ~ 1000.
In addition, when the polymer with polyalkyleneimine structure is the polymer of above-mentioned straight chain structure, the weight average molecular weight of polymer is more preferably less than 250000, and more preferably 10000 ~ 50000.
Weight average molecular weight can be obtained by GPC (gel permeation chromatography) mensuration according to following condition.
Sensing equipment: Waters Alliance (2695) (trade name, Waters company manufactures)
Molecular weight post: TSKguard column α, TSKgel α-3000, TSKgel α-4000, TSKgel α-5000 (being Dong Cao company to manufacture) are connected in series use
Eluent: the solution mixing 50mM sodium hydrate aqueous solution 96g and acetonitrile 3600g in 100mM boric acid aqueous solution 14304g
Calibration curve standard substance: polyethylene glycol (manufacture of Dong Cao company)
Assay method: measuring object is dissolved in eluent by the mode being about 0.2 quality % according to solid constituent, using utilize the material after metre filter as working sample determining molecular weight.
As the above-mentioned compound containing triazine ring, melamine or guanidine amine are owing to being nitrogenous cyclic compound, and nitrogen-atoms number is high relative to the ratio of the whole atomicities forming compound and be rigidity, are therefore applicable.When metal oxide layer is formed with the film be made up of melamine or guanidine amine, form the nitrogenous film of height of above-mentioned (2).
As the above-mentioned compound containing triazine ring, except the guanidine amines such as melamine or benzoguanamine/methyl guanamines, methylolated melamine or guanidine amine, melmac/guanamine resin etc. can also be used to have the one kind or two or more of the compound of melamine/guanamines skeleton, among these, nitrogen-atoms relative to form compound whole atoms in ratio high in consider be preferably melamine.
And as above-mentioned, there is nitrogenous heterocyclic compound or amines, compatibly can also use polymer or the triethylamine of formula (48), the ethylenediamine of formula (49) of the repetitive with the structure represented with following formula (39) ~ (47).
[changing 46-1]
[changing 46-2]
In addition, if make these nitrogen-containing compounds decompose on metal oxide layer, then form the nitrogenous film of above-mentioned (3) or the nitrogenous film of height of (4).Think by using polynary amine or the analyte of nitrogen-containing compound then can being made containing the compound that the nitrogenous ratio of the compound etc. and so on of triazine ring is high to be deposited in more densely on metal oxide layer as nitrogen-containing compound.On this metal oxide is also one of invention containing nitrogen film.For containing nitrogen film, hereinafter can be further detailed.
The average thickness of the nitrogenous film in the present invention is 3 ~ 150nm.If nitrogenous film is above-mentioned average thickness, then can play the above-mentioned effect with nitrogenous film well.The average thickness of nitrogenous film is preferably 5 ~ 100nm.Be more preferably 5 ~ 50nm.Particularly when the nitrogenous film that nitrogen-containing compound decomposes, be preferably 5 ~ 100nm, be more preferably 5 ~ 50nm.
The average thickness of nitrogenous film can utilize contact contourgraph to measure when film forming.Contact contourgraph, when measuring very thin films, depends on mensuration environment widely, causes the deviation of measured value larger.Therefore, when measuring the average thickness in this patent, the mean value measured by more than 2 times is determined.
The organic compound layer of more than 1 layer or 2 layers that 3rd organic electroluminescent device of the present invention preferably has anode and negative electrode and is clipped between above-mentioned anode and above-mentioned negative electrode, between above-mentioned negative electrode and above-mentioned organic compound layer, there is metal oxide layer, and there is the layer be made up of nitrogenous film of the present invention between above-mentioned metal oxide layer and above-mentioned organic compound layer.Organic compound layer is herein the layer comprising luminescent layer and comprise electron transfer layer, hole transmission layer in addition as required.
Wherein, 3rd organic electroluminescent device of the present invention is preferably: it is the organic electroluminescent device forming negative electrode in a neighboring manner and have the organic-inorganic mixed type of metal oxide layer between the anode and the cathode on substrate, wherein, there is luminescent layer and anode, there is electron injecting layer and optional electron transfer layer as required between negative electrode and luminescent layer, there is hole transmission layer and/or hole injection layer between anode and luminescent layer.3rd organic electroluminescent device of the present invention can have other layer between above-mentioned each layer, but the element be preferably only made up of above-mentioned each layer.Namely the element of negative electrode, electron injecting layer, as required optional electron transfer layer, luminescent layer, hole transmission layer and/or hole injection layer, each layer of anode adjacent lamination is successively preferably.It should be noted that, above-mentioned each layer can be formed by 1 layer, also can form by more than 2 layers.
As mentioned above, nitrogenous film, due to Electron Injection Characteristics excellence, is therefore preferably used in electron injection side, i.e. cathode side.And as described later, metal oxide layer preferably carries out lamination as a part for negative electrode or 1 layer of electron injecting layer and/or carries out lamination as a part for anode or 1 layer of hole injection layer.
For the organic electric-field element of above-mentioned formation, when element does not have electron transfer layer, electron injecting layer is adjacent with luminescent layer.In addition, when element only has any one layer in hole transmission layer, hole injection layer, this kind of layer is with the mode lamination adjacent with anode with luminescent layer, when element has hole transmission layer and hole injection layer, these layers are according to the order lamination in a neighboring manner of luminescent layer, hole transmission layer, hole injection layer, anode.
In 3rd organic electroluminescent device of the present invention, as the material forming luminescent layer, also can use any one compound that usually can be used as in the material of luminescent layer, can be low molecular compound also can be macromolecular compound, can also used in combination they.
It should be noted that, the low molecule material in the present invention refers to it is not the material of macromolecular material (polymer), might not refer to the organic compound that molecular weight is low.
As the macromolecular material of above-mentioned formation luminescent layer, such as can enumerate in the 1st organic illuminating element of the invention described above as formed resilient coating organic compound example described in compound among compound except polyethylene imine based (PEI) and No. 2010-230995, Japanese Patent Application, boron compound system macromolecular material etc. described in No. 2011-6457, Japanese Patent Application.
As the low molecule material of above-mentioned formation luminescent layer, such as, can use same with the low molecular compound that can be used as the material of luminescent layer in the 1st organic illuminating element of the invention described above material.
The average thickness of above-mentioned luminescent layer is not particularly limited, preferably same with the average thickness of the luminescent layer of the 1st organic illuminating element of the invention described above.
When 3rd organic electroluminescent device of the present invention has electron transfer layer, as its material, also can use any one compound of material that usually can be used as electron transfer layer, can also used in combination they.
As the example that can be used as the compound of the material of electron transfer layer, can enumerate the compound same with the low molecular compound that can be used as the material of electron transfer layer in the 1st organic illuminating element of the invention described above, preferred compound is also same.
When 3rd organic electroluminescent device of the present invention has hole transmission layer, the hole transport ability organic material as hole transmission layer can be used alone or combinationally use various p-type macromolecular material or various p-type low molecule material.
As p-type macromolecular material (organic polymer), such as polyarylamine, fluorenes-arylamine copolymer, fluorenes-bis-thiophene copolymers, poly-(N-vinylcarbazole), polyvinyl pyrene, polyvinyl anthracene, polythiophene, poly-alkylthrophene, poly-hexyl thiophene, poly-(to phenylene vinylidene), poly-sub-thienyl ethenylidene, pyrene formaldehyde resin, ethyl carbazole formaldehyde resin or derivatives thereof etc. can be enumerated.
And these compounds can also use with the form of the mixture with other compound.As an example, as the mixture containing polythiophene, can enumerate poly-(3,4-Ethylenedioxy Thiophene)-gather (styrene sulfonic acid) (PEDOT/PSS) etc.
As above-mentioned p-type low molecule material, the compound that the low molecular compound that can be used as the material of hole transmission layer is same can be enumerated in the 1st organic illuminating element with the invention described above.
When 3rd organic electroluminescent device of the present invention has electron transfer layer, hole transmission layer, the average thickness of these layers is not particularly limited, preferably same with the average thickness of the electron transfer layer in the 1st organic illuminating element of the invention described above, hole transmission layer.
For the average thickness of electron transfer layer, hole transmission layer, quartz vibrator film thickness gauge can be utilized measure when low molecular compound; Contact contourgraph can be utilized measure when macromolecular compound.
3rd organic electroluminescent device of the present invention from negative electrode to luminescent layer, from anode to luminescent layer in arbitrary or two there is metal oxide layer, preferably from negative electrode to luminescent layer and between luminescent layer to anode, this two all has metal oxide layer.Metal oxide layer between negative electrode to luminescent layer is set as the 1st metal oxide layer, metal oxide layer between anode to luminescent layer is set as the 2nd metal oxide layer, if illustrate an example of the formation of the preferred element of the 3rd organic electroluminescent device of the present invention, then following formation is shown: negative electrode, the 1st metal oxide layer, the layer be made up of nitrogenous film, luminescent layer, hole transmission layer, the 2nd metal oxide layer, anode lamination in a neighboring manner successively.It should be noted that can have electron transfer layer as required between the layer be made up of nitrogenous film and luminescent layer.With regard to the importance of metal oxide layer, the importance of the 1st metal oxide layer is higher, and the 2nd metal oxide layer can use such as HATCN, F 4the organic material that the such lowest unoccupied molecular orbital of TCNQ is extremely low is replaced.
The material of above-mentioned 1st metal oxide layer, the 2nd metal oxide layer and the formation of layer and the average thickness of layer same with the record in the 1st organic illuminating element of the invention described above.
In 3rd organic illuminating element of the present invention, the material of anode and negative electrode and average thickness same with the record in the 1st organic illuminating element of the invention described above.
3rd organic electroluminescent device of the present invention is a kind of organic electroluminescent device of the present invention, and wherein, resilient coating is the average thickness be made up of nitrogenous film is the layer of 3 ~ 150nm, thereby, it is possible to make luminous efficiency and the life-span excellence of organic electroluminescent device.
The manufacture method of the organic electroluminescent device of the organic-inorganic mixed type of the 3rd optimal way of the present invention like this, i.e. a kind of manufacture method with the organic electroluminescent device of the structure of the layer being laminated with more than 2 layers, it is characterized in that, this manufacture method comprises and between the 1st electrode and the 2nd electrode, has metal oxide layer according to organic electroluminescent device successively, the mode lamination of the layer that nitrogenous film be made up of of lamination on this metal oxide layer is configured with the operation of each layer of electro-luminescence element, this lamination operation comprises the operation that formation average thickness is the nitrogenous film of 3 ~ 150nm, the manufacture method of the organic electroluminescent device of the 3rd optimal way of the invention described above is also one of the present invention.
The manufacture method of the organic electroluminescent device of the 3rd optimal way of the invention described above also can comprise other operation under the prerequisite comprising above-mentioned operation, also can comprise the operation of the layer formed beyond metal oxide layer, the layer that is made up of nitrogenous film.In addition, be formed the material of each layer of electro-luminescence element, formation method, organic compound, in order to the thickness preparing solvent and each layer used containing the solution of organic compound same with the 3rd organic electroluminescent device of the present invention, preferred scheme is also the same.
For organic electroluminescent device of the present invention, the film build method of the layer formed by organic compound is not particularly limited, various method can be suitably used according to properties of materials, when solution can be made to be coated with, various rubbing methods when forming resilient coating can be used in the 1st organic illuminating element of the invention described above to carry out film forming.Wherein, from the viewpoint of preferably spin-coating method, the slot coated method that more easily control thickness.As example when being applicable to not being coated with or when solvent solubility is low, vacuum vapour deposition or ESDUS (super subtle solution evaporation injection sedimentation, Evaporative Spray Deposition from Ultra-dilute Solution) method etc. can be enumerated.
When being coated with solution of organic compound and forming the above-mentioned layer formed by organic compound, as the solvent for being dissolved with organic compounds, can use in the 1st organic illuminating element with the invention described above to prepare the same solvent of the solvent that uses containing the solution of organic compound, among them, as solvent, non-polar solven is more applicable, can enumerate the aromatic hydrocarbon solvents such as such as dimethylbenzene, toluene, cyclohexyl benzene, Dihydrobenzofuranes, trimethylbenzene, durol; The aromatic heterocyclic compounds series solvent such as pyridine, pyrazine, furans, pyrroles, thiophene, methyl pyrrolidone; The Aliphatic hydrocarbon solvents etc. such as hexane, pentane, heptane, cyclohexane, can be used alone or as a mixture them.
When using polynary amine as above-mentioned nitrogen-containing compound, water or lower alcohol can be used as the solvent of the solution containing nitrogen-containing compound.As lower alcohol, preferably use carbon number to be the alcohol of 1 ~ 4, methyl alcohol, ethanol, propyl alcohol, ethoxy ethanol, methyl cellosolve etc. can be used alone or as a mixture.
Above-mentioned negative electrode, anode and oxide skin(coating) can be formed by the identical method of the method for formation the 1st, the 2nd metal oxide layer in above-mentioned 1st organic electroluminescent device, the 2nd electrode, luminescent layer, hole transmission layer, electron transfer layer.For formation anode, negative electrode, the joint of metal forming can also be used.These methods are preferably selected according to the characteristic of layers of material, and the manufacture method of each layer can be different.Among said method, the 2nd metal oxide layer more preferably uses gas phase masking method to be formed.By gas phase masking method, can clean under the condition on surface not destroying organic compound layer and with anode good contact form the 2nd metal oxide layer, its result makes the above-mentioned effect brought because having the 2nd metal oxide layer more remarkable.
Improve the reasons such as the characteristic of the 3rd organic electroluminescent device of the present invention from further, such as hole blocking layer, layer of electronic components etc. can be had as required.As the material for the formation of these layers, use by the material for the formation of these layers, and layer can be formed by the method being generally used for being formed these layers.
With whole layers of composed component compared with the organic electroluminescent device that organic compound is formed, the 3rd organic electroluminescent device of the present invention without the need to tight seal, but also can implement sealing when necessity.As sealing process, suitably conventional method can be used.Such as can enumerate the method engaging airtight container in inert gas or the direct method etc. forming diaphragm seal on organic EL element.The method of enclosing absorbent material can also be share on the basis of these methods.
3rd organic electroluminescent device of the present invention is the organic electroluminescent device of the reverse geometry being formed with negative electrode on substrate in a neighboring manner.3rd organic electroluminescent device of the present invention can be the top emission type element extracting light in the opposition side of the side having substrate, also can be the bottom emission type element extracting light in the side having substrate.
The material of aforesaid substrate and average thickness same with above-mentioned 1st organic electroluminescent device.
As mentioned above, organic electroluminescent device of the present invention has the layer be made up of nitrogenous film on metal oxide layer, and Electron Injection Characteristics improves and makes luminous efficiency excellent thus, make simultaneously the driving stability of element and component life also excellent.
The effect of such raising Electron Injection Characteristics is not limited only to organic electroluminescent device, is also contribute to putting forward high performance advantageous effects for other opto-electronic device such as solar cell or organic semiconductor.The nitrogenous film contributing to raising opto-electronic device performance like this, i.e. a kind of film containing nitrogen, it is characterized in that, this film is being formed containing on the base material of metal, is formed by the nitrogen-containing compound of solid; Or containing nitrogen element and carbon as the element forming film, the ratio that exists of the nitrogen-atoms and carbon atom that form this film meets following relation:
Nitrogen-atoms number/(nitrogen-atoms number+carbon number) >1/8,
Nitrogenous film so is also one of the present invention.
The optimal way of nitrogenous film of the present invention and manufacture method same with the layer be made up of nitrogenous film in the organic electroluminescent device of the invention described above.
Electroluminescent cell of the present invention can make it luminous by applying voltage (being generally less than 15 volts) between antianode and negative electrode.Usual applying direct voltage, but also can comprise alternating current component.
Organic electroluminescent device of the present invention is the element of organic-inorganic mixed type, but the crystallization of low molecular compound is suppressed specific to the element of organic-inorganic mixed type, can realize suppressing leakage current and the luminescence of uniform face, and the material of display unit or lighting device can be suitable as.Organic electroluminescent device of the present invention can change glow color by suitably selecting the material of organic compound layer, can also share colour filter etc. and obtain desired glow color.Therefore, it is possible to be suitable as luminous site or the lighting device of display unit.Particularly due to the characteristic that reverse geometry is such, be therefore well suited for for the display unit combined with oxide TFT.
This use the organic electroluminescent device of the present invention and display unit formed also is one of the present invention.Further use the organic electroluminescent device of the present invention and lighting device formed also is one of the present invention.
Invention effect
1st organic electroluminescent device of the present invention by above-mentioned form form, can realize suppressing leakage current and uniform face luminous.
And the 2nd organic electroluminescent device of the present invention is owing to having resilient coating, and luminescent lifetime is long compared with the organic electroluminescent device of existing organic-inorganic mixed type thus, and make luminous efficiency excellent because resilient coating contains reducing agent.The organic electroluminescent device of organic-inorganic mixed type has each layer advantage that all necessity etc. of each layer of tight seal manufactures by the organic electroluminescent device that organic substance is formed reduced as being configured with electro-luminescence element, and it has such advantage and the excellent characteristics of luminescence such as luminescent lifetime, luminous efficiency.
Further, 3rd organic electroluminescent device of the present invention is by the above-mentioned organic electroluminescent device with the reverse geometry of organic-inorganic mixed type without the need to tight seal formed, its luminous efficiency is excellent, the height simultaneously with luminous repetition stability and luminous excellent in uniformity drives stability, and the life-span of element is also long.
Organic electroluminescent device of the present invention has the characteristic of above-mentioned excellence, and it can be suitable as the material etc. of display unit or lighting device.
Accompanying drawing explanation
Fig. 1 is the SEM photo of solution coat in time being with the transparent glass substrate of ITO that will boron-containing compound 1 made to be dissolved in THF.
Fig. 2 is the curve chart of the voltage-to-current efficiency characteristic representing the organic electroluminescent device made in embodiment 1 and comparative example 1.
Fig. 3 is the curve chart of the voltage-to-current efficiency characteristic representing the organic electroluminescent device made in embodiment 2 ~ 4 and comparative example 2.
Fig. 4 is the curve chart of the voltage-to-current efficiency characteristic representing the organic electroluminescent device made in embodiment 5 and comparative example 2.
Fig. 5 is the curve chart of the voltage-to-current efficiency characteristic representing the organic electroluminescent device made in embodiment 6 and comparative example 3.
Fig. 6 is the curve chart of the voltage-luminance characteristics representing the organic electroluminescent device made in embodiment 7 and comparative example 4.
Fig. 7 is the curve chart of the current density-current efficiency characteristics representing the organic electroluminescent device made in embodiment 7 and comparative example 4.
Fig. 8 is the curve chart of the voltage-luminance characteristics representing the organic electroluminescent device made in embodiment 8 and comparative example 5.
Fig. 9 is the curve chart of the current density-current efficiency characteristics representing the organic electroluminescent device made in embodiment 8 and comparative example 5.
Figure 10 is the curve chart of the voltage-luminance characteristics representing the organic electroluminescent device made in embodiment 9,10 and comparative example 6.
Figure 11 is the curve chart of the current density-current efficiency characteristics representing the organic electroluminescent device made in embodiment 9,10 and comparative example 6.
Figure 12 is the curve chart of the voltage-luminance characteristics representing the organic electroluminescent device made in embodiment 11 and comparative example 7.
Figure 13 is the curve chart of the current density-current efficiency characteristics representing the organic electroluminescent device made in embodiment 11 and comparative example 7.
Figure 14 is the curve chart of the voltage-luminance characteristics representing the organic electroluminescent device made in embodiment 12 and comparative example 8.
Figure 15 is the curve chart of the current density-current efficiency characteristics representing the organic electroluminescent device made in embodiment 12,13 and comparative example 8.
Figure 16 is the schematic diagram of an example of the laminated structure representing the 3rd organic electroluminescent device shown in the present invention.
Figure 17-1 represents (a) voltage-current density/light characteristic of organic electroluminescent device of making in embodiment 14, the figure of the measurement result of (b) current density-current efficiency characteristics.
Figure 17-2 represents the organic electroluminescent device of making in embodiment 14 under (c-1) constant current density (corresponding to 100cd/m 2) Continuous Drive characteristic and under (c-2) constant current density (corresponding to 1000cd/m 2) the figure of measurement result of Continuous Drive characteristic.
Figure 18 is the figure representing (a) voltage-current density/light characteristic of organic electroluminescent device and the measurement result of (b) current density-current efficiency characteristics made in comparative example 9.
Figure 19-1 represents (a) voltage-current density/light characteristic of organic electroluminescent device of making in embodiment 15, the figure of the measurement result of (b) current density-current efficiency characteristics.
Figure 19-2 represents the organic electroluminescent device of making in embodiment 15 under (c-2) constant current density (corresponding to 1000cd/m 2) the figure of measurement result of Continuous Drive characteristic.
Figure 20-1 represents (a) voltage-current density/light characteristic of organic electroluminescent device of making in embodiment 16, the figure of the measurement result of (b) current density-current efficiency characteristics.
Figure 20-2 represents the organic electroluminescent device of making in embodiment 16 under (c-2) constant current density (corresponding to 1000cd/m 2) the figure of measurement result of Continuous Drive characteristic.
Figure 21 be represent in embodiment 17 make organic electroluminescent device (a) voltage-current density/light characteristic and under (c-1) constant current density (corresponding to 100cd/m 2) the figure of measurement result of Continuous Drive characteristic.
Figure 22-1 represents (a) voltage-current density/light characteristic of organic electroluminescent device of making in embodiment 18, the figure of the measurement result of (b) current density-current efficiency characteristics.
Figure 22-2 represents the organic electroluminescent device of making in embodiment 18 under (c-1) constant current density (corresponding to 100cd/m 2) the figure of measurement result of Continuous Drive characteristic.
Figure 23-1 represents (a) voltage-current density/light characteristic of organic electroluminescent device of making in embodiment 19, the figure of the measurement result of (b) current density-current efficiency characteristics.
Figure 23-2 be represent in embodiment 19 make organic electroluminescent device under (c-1) constant current density (corresponding to 100cd/m 2) the figure of measurement result of Continuous Drive characteristic.
Figure 24-1 represents (a) voltage-current density/light characteristic of organic electroluminescent device of making in embodiment 20, the figure of the measurement result of (b) current density-current efficiency characteristics.
Figure 24-2 represents the organic electroluminescent device of making in embodiment 20 under (c-2) constant current density (corresponding to 1000cd/m 2) the figure of measurement result of Continuous Drive characteristic.
Figure 25-1 represents (a) voltage-current density/light characteristic of organic electroluminescent device of making in embodiment 21, the figure of the measurement result of (b) current density-current efficiency characteristics.
Figure 25-2 represents the organic electroluminescent device of making in embodiment 21 under (c-2) constant current density (corresponding to 1000cd/m 2) the figure of measurement result of Continuous Drive characteristic.
Figure 26-1 represents (a) voltage-current density/light characteristic of organic electroluminescent device of making in embodiment 22, the figure of the measurement result of (b) current density-current efficiency characteristics.
Figure 26-2 be represent in embodiment 22 make organic electroluminescent device under (c-1) constant current density (corresponding to 100cd/m 2) the figure of measurement result of Continuous Drive characteristic.
Figure 27-1 represents (a) voltage-current density/light characteristic of organic electroluminescent device of making in embodiment 23, the figure of the measurement result of (b) current density-current efficiency characteristics.
Figure 27-2 represents the organic electroluminescent device of making in embodiment 23 under (c-2) constant current density (corresponding to 1000cd/m 2) the figure of measurement result of Continuous Drive characteristic.
Figure 28 represents the figure nitrogenous film made in Production Example 1 being carried out to the result of photoelectron spectroscopy mensuration.
Figure 29 represents the figure nitrogenous film made in Production Example 2 being carried out to the result of photoelectron spectroscopy mensuration.
Figure 30 represents the figure nitrogenous film made in Production Example 3 being carried out to the result of photoelectron spectroscopy mensuration.
Figure 31 represents the figure nitrogenous film made in Production Example 4 being carried out to the result of photoelectron spectroscopy mensuration.
Figure 32 is the figure representing (a) voltage-current density/light characteristic of the organic electroluminescent device made in embodiment 24-1 and the measurement result of (b) current density-current efficiency characteristics.
Figure 33 is the figure representing (a) voltage-current density/light characteristic of the organic electroluminescent device made in embodiment 24-2 and the measurement result of (b) current density-current efficiency characteristics.
Figure 34 is the figure representing (a) voltage-current density/light characteristic of organic electroluminescent device and the measurement result of (b) current density-current efficiency characteristics made in embodiment 25.
Figure 35 is the figure representing (a) voltage-current density/light characteristic of organic electroluminescent device and the measurement result of (b) current density-current efficiency characteristics made in comparative example 10.
Embodiment
Enumerate embodiment below to illustrate in greater detail the present invention, but the present invention is not limited in these embodiments.It should be noted that, as long as no special declaration, " part " just refers to " weight portion ", and " % " just refers to " quality % ".
In the following embodiments, various physical property measures according to as described below.
< 1H-NMR>
Obtained boron-containing compound is made the solution of deuterochloroform, use high resolution nuclear magnetic resonance device (ProductName " Gemini 2000 "; 300MHz, Varian, Inc. company manufactures) measure.Chemical shift is to be positioned at 1/1000000th (ppm of the downfield side of tetramethylsilane; δ value) form record, with the proton of tetramethylsilane (δ 0.00) for reference.
< 13C-NMR>
Obtained boron-containing compound is made the solution of deuterochloroform, use high resolution nuclear magnetic resonance device (ProductName " Gemini 2000 "; 75MHz, Varian, Inc. company manufactures) measure.Chemical shift is to be positioned at 1/1000000th (ppm of the downfield side of tetramethylsilane; δ value) form record, with the carbon core (CDCl in NMR solvent 3: δ=77.0, CD 2cl 2: δ=53.1, CD 3cN: δ=1.32, DMSO-d 6: δ=39.52) be reference.
< 11B-NMR>
Obtained boron-containing compound is made the solution of deuterochloroform, use high resolution nuclear magnetic resonance device (ProductName " Mercury-400 "; 128MHz, Varian, Inc. company manufactures) measure.Chemical shift is according to 1/1000000th (ppm being benchmark with the boron core (δ=0.00) of boron trifluoride-diethyl ether complex compound; δ value) form record.
< high resolution mass spec >
Use high resolution mass spectrometer (ProductName " JMS-SX101A ", " JMS-MS700 ", " JMS-BU250 ", NEC company manufactures), measured by electron ionization method (EI) or high-velocity electrons blast technique (FAB).
< weight average molecular weight >
Weight average molecular weight utilizes gel permeation chromatography (GPC device, developing solvent based on polystyrene conversion; Chloroform) measured by following apparatus and condition determination.
Efficient GPC device: HLC-8220GPC (manufacture of Dong Cao company)
Condition determination:
Developing solvent chloroform
Post TSK-gel GMHXL × 2 piece
Eluent flow 1ml/ minute
Column temperature 40 DEG C
< the 1st organic electroluminescent device > of the present invention
(synthesis example 1)
(synthesis of two (3-dibenzo boron heterocyclic pentylene base-4-pyridinylphenyl)-9,9 '-spiral shell two fluorenes of 2,7-)
2-(dibenzo boron heterocyclic pentylene base phenyl)-5-bromopyridine (2.6g, 6.5mmol), 2 is added in 100mL bis-neck eggplant type flask, 7-two (4,4,5,5-tetramethyl-1,3,2-dioxaborolyl)-9,9 '-spiral shell two fluorenes (1.5g, 2.7mmol), Pd (PtBu 3) 2(170mg, 0.32mmol), makes to be under nitrogen atmosphere in flask, adds THF (65mL), stir.
Add the 2M tripotassium phosphate aqueous solution (11mL, 22mmol) wherein, make it reflux at 70 DEG C and carry out adding thermal agitation.After 12 hours, be cooled to room temperature, add water after reaction solution being moved to separatory funnel, utilize ethyl acetate to extract.After being utilized by organic layer 3N hydrochloric acid, water, saturated aqueous common salt to clean, magnesium sulfate is utilized to carry out drying.Filtrate after filtering is concentrated, utilize the solid that washed with methanol obtains, two (3-dibenzo boron heterocyclic pentylene base-4-pyridinylphenyl)-9,9 '-spiral shell two fluorenes (boron-containing compound 1) (1.2g, 1.3mmol) of 2,7-is obtained thus with the yield of 47%.
Its physics value is as follows.
1H-NMR(CDCl 3)：δ6.67(d,J＝7.6Hz,2H),6.75(d,J＝1.2Hz,2H),6.82(d,J＝7.2Hz,4H),6.97(dt,J＝7.2,1.2Hz,4H),7.09(dt,J＝7.2,0.8Hz,2H),7.24-7.40(m,14H),7.74-7.77(m,6H),7.84-7.95(m,10H)
In addition, the reaction of synthesis example 1 represents according to following reaction equation.
[changing 47]
For the boron-containing compound 1 of synthesis in synthesis example 1, element physical property as follows is evaluated.
< is coated with masking >
If by making boron-containing compound 1 be dissolved in the solution coat of THF in the transparent glass substrate of band ITO, then level and smooth film can be obtained.By shown in Figure 1 for its SEM (scanning electron microscopy) photo (multiplying power: 10000 times).According to this result, demonstrate boron-containing compound 1 and be low molecular compound and coating masking can be carried out by solution.
(synthesis example 2)
Under an argon, add ethyl diisopropylamine (39mg, 0.30mmol) in the dichloromethane solution (0.3ml) containing the bromo-2-of 5-(4-bromophenyl) pyridine (94mg, 0.30mmol) after, Boron tribromide (1.0M, 0.9ml, 0.9mmol) is added, stirring at room temperature 9 hours at 0 DEG C.After reaction solution being cooled to 0 DEG C, add unsaturated carbonate aqueous solutions of potassium, utilize chloroform to extract.Utilize saline solution to clean organic layer, and utilize magnesium sulfate to make its dry filter.After utilizing rotary evaporator to make filtrate concentrated, filter out the white solid of generation, utilize hexane to clean, obtain with the yield of 28% boron-containing compound 2 (40mg, 0.082mmol) represented with following formula (50) thus.
[changing 48]
Its physics value is as follows.
1H-NMR(CDCl 3)：7.57-7.59(m,2H),7.80(dd,J＝8.4,0.6Hz,1H),7.99(s,1H),8.27(dd,J＝8.4,2.1Hz,1H),9.01(d,J＝1.5Hz,1H)；
(synthesis example 3)
In a nitrogen atmosphere, the diethyl ether solution (1M, 61.2ml, 70.4mmol) of pentafluorophenyl group magnesium bromide is cooled to 0 DEG C, stirs the diethyl ether solution (1M, 17ml, 17mmol) dripping zinc chloride wherein.After dropping terminates, stirring at room temperature 1 hour.Add the toluene solution (80ml) containing the bromo-2-of 5-(the 4-bromo-2-dibromo monoborane base phenyl) pyridine (3.8g, 8mmol) represented with above-mentioned formula (26) wherein, add thermal agitation 15 hours at 80 DEG C.Be cooled to room temperature, reaction solution be added in frozen water, utilize chloroform to extract.Utilize saturated aqueous common salt to clean organic layer, utilize sodium sulphate to make it dry, then filter.After utilizing rotary evaporator that filtrate is concentrated, carry out purifying by silica gel chromatography (hexane: carrene=1:1), obtain with the yield of 58% boron-containing compound 3 (2.2g, 4.61mmol) represented with following formula (51) thus.
[changing 49]
Its physics value is as follows.
1H-NMR(CDCl 3)：δ7.16-7.26(m,10H),7.45-7.48(m,1H),7.69-7.71(m,1H),7.81(d,J＝2.0Hz,1H),7.90(d,J＝8.0Hz,1H),8.15-8.18(m,1H),8.56(d,J＝2.0Hz,1H)
(synthesis example 4)
The BC6F5 dibromide (boron-containing compound 3) (337mg, 0.51mmol) making to represent with above-mentioned formula (51), the F8 boric acid diester (292mg, 0.52mmol) represented with following formula (52) are dissolved in toluene (3ml) and THF (3ml), under an argon, stirring at room temperature 10 minutes.Add Aliquat336 (21mg), 25 quality %Et wherein 4the mixed aqueous solution of the NOH aqueous solution (0.86ml) and distilled water (0.75ml), under an argon, stirs further in room temperature and completes degassed in 20 minutes.After adding tetrakis triphenylphosphine palladium (8.9mg, 0.007mmol) wherein, make it reflux at 115 DEG C and add thermal agitation 48 hours.In order to make endcapped, adding bromobenzene (105mg, 0.67mmol) and stirring 5 hours, add phenylboric acid (294mg, 2.41mmol) further and stir 5 hours.Naturally cool to room temperature, by utilize with the reaction solution after dilution with toluene hydrochloric acid carry out 1 time, utilize pure water to carry out twice separatory cleaning, organic layer is concentrated into about several milliliters.Concentrate to be dropped in the methyl alcohol of 300ml and to stir 10 minutes with this state, filtering out obtained precipitation.Repeatedly carry out the purge process that total 3 times is same, make solid drying under reduced pressure, resulting in the boron polymer F8BC6F5 represented with following formula (53).The weight average molecular weight of boron polymer F8BC6F5 is 126000.
[changing 50]
[changing 51]
(making of organic electroluminescent device)
In the following embodiments, the average thickness of resilient coating uses probe-type contourgraph (ProductName " Alpha-Step IQ ", KLA TENCOR company manufactures) to measure.
(embodiment 1)
[1] transparent glass substrate that commercially available average thickness is the band ITO electrode layer of 0.7mm is prepared.Now, the ITO electrode (the 1st electrode) of substrate uses and has carried out the ITO electrode of patterning with 2mm width.By this substrate respectively in acetone, carry out 10 minutes Ultrasonic Cleanings in isopropyl alcohol after, in isopropyl alcohol, boil 5 minutes.This substrate is taken out from isopropyl alcohol, utilizes nitrogen stream to make it dry, carry out 20 minutes UV ozone clean.
[2] this substrate is fixed on the frame substrate of the subtend target formula sputter equipment (Mirrortron Sputtering System) with zinc metallic target.Be decompressed to about 1 × 10 -4after Pa, sputter under the state after importing argon and oxygen, made the zinc oxide film that thickness is about 2nm.Now in order to take out electrode, share metal mask and making a part for ITO electrode film forming can not have zinc oxide.
[3] water-ethanol (taking volume basis as the 1:3) mixed solution of 1% magnesium acetate is made.The substrate made in operation [2] is again cleaned in the same manner as operation [1].The substrate of the band zinc-oxide film after cleaning is placed in spin coater.On this substrate, drip magnesium acetate solution, make it rotate 60 seconds with 1300 turns per minute.Utilize the heating plate being set to 400 DEG C that it is fired 2 hours in an atmosphere, thus form zinc oxide/magnesium oxide layer (the 1st metal oxide layer).
[4] tetrahydrofuran solution of 0.2% boron-containing compound 1 is made.The substrate of the band zinc oxide/magnesia film made in operation [3] is placed in spin coater.On this substrate, drip boron-containing compound 1 solution, make it rotate 30 seconds with 2000 turns per minute, thus form the resilient coating be made up of boracic organic compound.The average thickness of resilient coating is 5nm.
[5] substrate till after the layer forming boracic organic compound is fixed on the frame substrate of vacuum deposition apparatus.Respectively 4,4 '-bis-[9-bis-carbazyl]-2,2 '-biphenyl (CBP), three (1-phenyl isoquinolin quinolines) are closed iridium (Ir (piq) 3), N, N '-two (1-naphthyl)-N, N '-be placed in vapor deposition source after diphenyl-1,1 '-biphenyl-4,4 '-diamines (α-NPD) is added to alumina crucible.About 1 × 10 will be decompressed in vacuum deposition apparatus -5pa, based on CBP, Ir (piq) 3for dopant evaporation 35nm altogether, thus film forming goes out luminescent layer.Now, doping content is set as Ir (piq) 3be 6 % by weight relative to luminescent layer entirety.Then, the α-NPD of evaporation 60nm, thus film forming goes out hole transmission layer.Then, after carrying out a nitrogen purging, molybdenum trioxide, gold are placed in vapor deposition source after adding alumina crucible.About 1 × 10 will be decompressed in vacuum deposition apparatus -5pa, according to the mode evaporation molybdenum trioxide (the 2nd metal oxide layer) forming 10nm thickness.Then, according to the mode gold evaporation (the 2nd electrode) forming 50nm thickness, thus organic electroluminescent device 1-1 has been made.During evaporation the 2nd electrode, the mode using the deposition mask of stainless steel to be formed as the band shape of 2mm width according to evaporation face is carried out.The light-emitting area of namely made organic electroluminescent device is 4mm 2.
(comparative example 1)
Except omitting operation [4], carry out similarly to Example 1, made organic electroluminescent device 1-2.
(embodiment 2)
[1] transparent glass substrate that commercially available average thickness is the band ITO electrode layer of 0.7mm is prepared.Now, the ITO electrode (the 1st electrode) of substrate uses and has carried out the ITO electrode after patterning with 2mm width.By this substrate respectively in acetone, carry out 10 minutes Ultrasonic Cleanings in isopropyl alcohol after, in isopropyl alcohol, boil 5 minutes.This substrate is taken out from isopropyl alcohol, utilizes nitrogen stream to make it dry, carry out 20 minutes UV ozone clean.
[2] this substrate is fixed on the frame substrate of the subtend target formula sputter equipment with zinc metallic target.Be decompressed to about 1 × 10 -4after Pa, sputter under the state after importing argon and oxygen, made the zinc oxide film (the 1st metal oxide layer) that thickness is about 2nm.Now in order to take out electrode, share metal mask and making a part for ITO electrode film forming can not have zinc oxide.
[3] tetrahydrofuran solution of 0.2% boron polymer F8BC6F5 is made.The substrate of the band zinc-oxide film made in operation [2] is placed in spin coater.On this substrate, drip boron polymer F8BC6F5 solution, make it rotate 30 seconds with 2000 turns per minute, define the resilient coating be made up of boracic organic compound.The average thickness of resilient coating is 10nm.
[4] substrate till after the layer forming boracic organic compound is fixed on the frame substrate of vacuum deposition apparatus.Respectively by three (oxine) aluminium (Alq 3), N, N '-two (1-naphthyl)-N, N '-be placed in vapor deposition source after diphenyl-1,1 '-biphenyl-4,4 '-diamines (α-NPD) is added to alumina crucible.About 1 × 10 will be decompressed in vacuum deposition apparatus -4pa, the altogether Alq of evaporation 65nm 3, thus film forming goes out luminescent layer.Then, the α-NPD of evaporation 60nm, thus film forming goes out hole transmission layer.Then, after carrying out a nitrogen purging, molybdenum trioxide, gold are placed in vapor deposition source after being added to alumina crucible.About 1 × 10 will be decompressed in vacuum deposition apparatus -4pa, according to the mode evaporation molybdenum trioxide (the 2nd metal oxide layer) forming 10nm thickness.Then, according to the mode gold evaporation (the 2nd electrode) forming 30nm thickness, thus organic electroluminescent device 1-3 has been made.During evaporation the 2nd electrode, the deposition mask of stainless steel is used to carry out according to the mode that evaporation face is the band shape of 2mm width.The light-emitting area of namely made organic electroluminescent device is 4mm 2.
(embodiment 3)
The tetrahydrofuran solution of the 0.2% boron polymer F8BC6F5 used in the operation [3] in embodiment 2 is changed to the 0.2% commercially available xylene solution gathering (dioctyl fluorene-alternately-diazosulfide) (F8BT), similarly carry out in addition, made organic electroluminescent device 1-4.The average thickness of resilient coating is 10nm.
(embodiment 4)
The tetrahydrofuran solution of the 0.2% boron polymer F8BC6F5 used in the operation [3] in embodiment 2 is changed to the 0.2% commercially available xylene solution gathering (dioctyl fluorene) (PFO), similarly carry out in addition, made organic electroluminescent device 1-5.The average thickness of resilient coating is 10nm.
(comparative example 2)
Except omitting operation [3], carry out similarly to Example 2, made organic electroluminescent device 1-6.
(embodiment 5)
The tetrahydrofuran solution of the 0.2% boron polymer F8BC6F5 used in the operation [3] in embodiment 2 is changed to the ethanolic solution of the polyethylene imine based SP-200 that 1% Japanese catalyst company manufactures, similarly carry out in addition, made organic electroluminescent device 1-7.The average thickness of resilient coating is 10nm.
(embodiment 6)
[1] transparent glass substrate that commercially available average thickness is the band ITO electrode layer of 0.7mm is prepared.Now, the ITO electrode (the 1st electrode) of substrate uses and has carried out the ITO electrode after patterning with 2mm width.By this substrate respectively in acetone, carry out 10 minutes Ultrasonic Cleanings in isopropyl alcohol after, in isopropyl alcohol, boil 5 minutes.This substrate is taken out from isopropyl alcohol, utilizes nitrogen stream to make it dry, carry out 20 minutes UV ozone clean.
[2] this substrate is fixed on the frame substrate of the subtend target formula sputter equipment with titanium metal target.Be decompressed to about 1 × 10 -4after Pa, sputter under the state after importing argon and oxygen, made the titanium oxide layer (the 1st metal oxide layer) that thickness is about 2nm.Now in order to take out electrode, share metal mask and making a part for ITO electrode film forming can not have titanium oxide.
[3] tetrahydrofuran solution of 0.2% boron polymer F8BC6F5 is made.The substrate of the band thin film of titanium oxide made in operation [2] is placed in spin coater.On this substrate, drip boron polymer F8BC6F5 solution, make it rotate 30 seconds with 2000 turns per minute, define the resilient coating be made up of boracic organic compound.The average thickness of resilient coating is 10nm.
[4] substrate till after the layer forming boracic organic compound is fixed on the frame substrate of vacuum deposition apparatus.Respectively by three (oxine) aluminium (Alq 3), N, N '-two (1-naphthyl)-N, N '-be placed in vapor deposition source after diphenyl-1,1 '-biphenyl-4,4 '-diamines (α-NPD) is added to alumina crucible.About 1 × 10 will be decompressed in vacuum deposition apparatus -4pa, the altogether Alq of evaporation 65nm 3, film forming goes out luminescent layer.Then, the α-NPD of evaporation 60nm, thus film forming goes out hole transmission layer.Then, after carrying out a nitrogen purging, molybdenum trioxide, gold are placed in vapor deposition source after being added to alumina crucible.About 1 × 10 will be decompressed in vacuum deposition apparatus -4pa, according to the mode evaporation molybdenum trioxide (the 2nd metal oxide layer) forming 10nm thickness.Then, according to the mode gold evaporation (the 2nd electrode) forming 30nm thickness, thus organic electroluminescent device 1-8 has been made.During evaporation the 2nd electrode, the deposition mask of stainless steel is used to carry out according to the mode that evaporation face is the band shape of 2mm width.The light-emitting area of namely made organic electroluminescent device is 4mm 2.
(comparative example 3)
Replace, except operation [3], carrying out similarly to Example 6, having made organic electroluminescent device 1-9 except carrying out operation [3b].
[3b] made with ethanol by described in [0064] ~ [0066] section of Japanese Unexamined Patent Publication 2012-4492 publication (patent documentation 5) self-assembled monolayer material F8TES dilution be 1% solution.The substrate of the band thin film of titanium oxide made in operation [2] is placed in spin coater.On this substrate, drip self-assembled monolayer material F8TES solution, make it rotate 30 seconds with 2000 turns per minute.Then utilize ethanol to carry out rinsing immediately, utilize ethanol to carry out 10 minutes Ultrasonic Cleanings further.After rinsing, utilize heating plate to carry out immobilization in 10 minutes at 90 DEG C, thus define self-assembled monolayer layer.The average thickness of resilient coating is 2nm.F8TES is the compound of following formula (54).
[changing 52]
(characteristics of luminescence of organic electroluminescent device measures)
" the 2400 type Source Meter " that utilize Keithley company to manufacture has carried out applying voltage to element and measuring electric current." LS-100 " that utilize Konica Minolta company to manufacture determines luminosity.In addition, the uniformity of light-emitting area is confirmed by range estimation.
By shown in Figure 2 for the voltage-to-current efficiency characteristic when organic electroluminescent device made in embodiment 1 and comparative example 1 being applied under an argon to the direct voltage of 4V ~ 10V.The current efficiency of the element made in known comparative example 1 is low, leakage current is large.On the other hand, the current efficiency of the element made in known embodiment 1 is high, leakage current is suppressed.In addition, by visual observations, the element made in embodiment 1 can confirm very uniform luminous.
By shown in Figure 3 for the voltage-to-current efficiency characteristic when organic electroluminescent device made in embodiment 2 ~ 4 and comparative example 2 being applied under an argon to the direct voltage of 4V ~ 15V.In addition, by shown in Figure 4 for the voltage-to-current efficiency characteristic when organic electroluminescent device made in embodiment 5 and comparative example 2 being applied under an argon to the direct voltage of 4V ~ 15V.The leakage current of the element made in comparative example 2 does not very have luminescence greatly and completely.On the other hand, the current efficiency of the element made in known embodiment 2 ~ 5 is high, leakage current is suppressed.In addition, by visual observations, the element made in embodiment 2 ~ 5 can confirm very uniform luminous.
By shown in Figure 5 for the voltage-to-current efficiency characteristic when organic electroluminescent device made in embodiment 6 and comparative example 3 being applied under an argon to the direct voltage of 4V ~ 15V.The leakage current of the element made in comparative example 3 is very large, completely not luminous immediately after moment luminescence.On the other hand, the current efficiency of the element made in known embodiment 6 is high, leakage current is suppressed.In addition, by visual observations, the element made in embodiment 6 can confirm very uniform luminous.
Confirm according to above-mentioned: for the organic electroluminescent device of organic-inorganic mixed type, the layer being gone out organic compound by coating film forming can realize suppressing leakage current and the luminescence of uniform face.
< the 2nd organic electroluminescent device > of the present invention
In following embodiment, the average thickness being configured with each layer of electro-luminescence element uses probe-type contourgraph (ProductName " Alpha-Step IQ ", KLA TENCOR company manufactures) to measure.
(making of organic electroluminescent device)
(embodiment 7)
[1] transparent glass substrate that commercially available average thickness is the band ITO electrode layer of 0.7mm is prepared.Now, the ITO electrode (the 1st electrode) of substrate uses and has carried out the ITO electrode after patterning with 2mm width.By this substrate respectively in acetone, carry out 10 minutes Ultrasonic Cleanings in isopropyl alcohol after, in isopropyl alcohol, boil 5 minutes.This substrate is taken out from isopropyl alcohol, utilizes nitrogen stream to make it dry, carry out 20 minutes UV ozone clean.
[2] this substrate is fixed on the frame substrate of the subtend target formula sputter equipment with zinc metallic target.Be decompressed to about 1 × 10 -4after Pa, sputter under the state after importing argon and oxygen, made the zinc oxide film that thickness is about 2nm.Now in order to take out electrode, share metal mask and making a part for ITO electrode film forming can not have zinc oxide.Utilize the heating plate being set to 400 DEG C that it is fired 1 hour in an atmosphere, thus form zinc oxide film (the 1st metal oxide layer).
[3] boron-containing compound 1 making in above-mentioned synthesis example 1 synthesis is 0.2%, (4-(1,3-dimethyl-2,3-dihydro-1H-benzimidazolyl-2 radicals-Ji) phenyl) dimethylamine (N-DMBI) be 0.002% 1,2-dichloroethanes mixed solution.The substrate of the band zinc-oxide film made in operation [2] is placed in spin coater.On this substrate, drip boron-containing compound 1, N-DMBI mixed solution, make it rotate 30 seconds with 2000 turns per minute, thus define the resilient coating containing boracic organic compound.Further, the heating plate being set to 100 DEG C is utilized to implement 1 hour annealing in process to it in a nitrogen atmosphere.The average thickness of resilient coating is 10nm.
[4] substrate till after the layer forming boracic organic compound is fixed on the frame substrate of vacuum deposition apparatus.Respectively will two (10-hydroxy benzo [h] quinoline) beryllium (Bebq 2), three (1-phenyl isoquinolin quinolines) close iridium (Ir (piq) 3), N, N'-bis-(1-naphthyl)-N, N'-diphenyl-1,1'-biphenyl-4,4'-diamines (α-NPD) is placed in vapor deposition source after being added to alumina crucible.About 1 × 10 will be decompressed in vacuum deposition apparatus -5pa, with Bebq 2for main body, Ir (piq) 3for dopant evaporation 35nm altogether, film forming goes out luminescent layer.Now, doping content is according to Ir (piq) 3the mode being 6 % by weight relative to luminescent layer entirety sets.Then, the α-NPD of evaporation 60nm, thus film forming goes out hole transmission layer.
[5] then, after carrying out a nitrogen purging, molybdenum trioxide, gold are placed in vapor deposition source after being added to alumina crucible.About 1 × 10 will be decompressed in vacuum deposition apparatus -5pa, according to the mode evaporation molybdenum trioxide (the 2nd metal oxide layer) forming 10nm thickness.Then, according to the mode gold evaporation (the 2nd electrode) forming 50nm thickness, thus organic electroluminescent device 2-1 has been made.During evaporation the 2nd electrode, the deposition mask of stainless steel is used to carry out according to the mode that evaporation face is the band shape of 2mm width.The light-emitting area of namely made organic electroluminescent device is set as 4mm 2.
(comparative example 4)
In operation [3], 1,2-dichloroethane solution of 0.2% boron-containing compound 1 is used to replace 1, the 2-dichloroethanes mixed solution that boron-containing compound 1 is 0.2%, N-DMBI is 0.002%, carry out similarly to Example 7 in addition, made organic electroluminescent device 2-2.
(embodiment 8)
In operation [3], use boron-containing compound 1 is 1%, N-DMBI is 0.01% 1,2-dichloroethanes mixed solution replacement boron-containing compound 1 is 0.2%, N-DMBI is 0.002% 1,2-dichloroethanes mixed solution, carry out similarly to Example 7 in addition, made organic electroluminescent device 2-3.The average thickness of resilient coating is 60nm.
(comparative example 5)
In operation [3], 1,2-dichloroethane solution of 1% boron-containing compound 1 is used to replace 1, the 2-dichloroethanes mixed solution that boron-containing compound 1 is 1%, N-DMBI is 0.01%, carry out similarly to Example 8 in addition, made organic electroluminescent device 2-4.
(embodiment 9)
Carry out operation [4b] and replace operation [4], carry out similarly to Example 8 in addition, made organic electroluminescent device 2-5.
Substrate till after the layer forming boracic organic compound is fixed on the frame substrate of vacuum deposition apparatus by [4b].Respectively by three (oxine) aluminium (Alq 3), N, N'-bis-(1-naphthyl)-N, N'-diphenyl-1,1'-biphenyl-4,4'-diamines (α-NPD) is placed in vapor deposition source after adding alumina crucible.About 1 × 10 will be decompressed in vacuum deposition apparatus -4pa, the Alq of evaporation 35nm 3, thus film forming goes out luminescent layer.Then, the α-NPD of evaporation 60nm, thus film forming goes out hole transmission layer.
(embodiment 10)
In operation [3], use boron-containing compound 1 is 1%, N-DMBI is 0.05% 1,2-dichloroethanes mixed solution replacement boron-containing compound 1 is 1%, N-DMBI is 0.01% 1,2-dichloroethanes mixed solution, carry out similarly to Example 7 in addition, made organic electroluminescent device 2-6.The average thickness of resilient coating is 60nm.
(comparative example 6)
Carry out operation [4b] and replace operation [4], carry out in the same manner as comparative example 5 in addition, made organic electroluminescent device 2-7.
(embodiment 11)
In operation [3], boron-containing compound 1 is 1%, N-DMBI is 0.01% 1 to use commercially available poly-(dioctyl fluorene-alternately-diazosulfide) oxolane mixed solution that (F8BT) is 1%, N-DMBI is 0.01% to replace, 2-dichloroethanes mixed solution, carry out similarly to Example 9 in addition, obtain organic electroluminescent device 2-8.
(comparative example 7)
In operation [3], use the tetrahydrofuran solution of 1%F8BT to replace the oxolane mixed solution that F8BT is 1%, N-DMBI is 0.01%, carry out similarly to Example 10 in addition, made organic electroluminescent device 2-9.
(embodiment 12)
Carry out operation [3b] and replace operation [3], carry out similarly to Example 9 in addition, made organic electroluminescent device 2-10.
[3b] makes 1, the 2-dichloroethanes mixed solution that boron-containing compound 1 is 1%, leuco crystal violet is 0.01%.The substrate of the band zinc-oxide film made in operation [2] is placed in spin coater.On this substrate, drip boron-containing compound 1, leuco crystal violet mixed solution, make it rotate 30 seconds with 2000 turns per minute, thus define the resilient coating containing boracic organic compound.Further, the heating plate being set to 200 DEG C is utilized to implement 1 hour annealing in process to it in a nitrogen atmosphere.The average thickness of resilient coating is 60nm.
(comparative example 8)
In operation [3b], 1,2-dichloroethane solution of 1% boron-containing compound 1 is used to replace 1, the 2-dichloroethanes mixed solution that boron-containing compound 1 is 1%, leuco crystal violet is 0.01%, carry out similarly to Example 11 in addition, made organic electroluminescent device 2-11.
(embodiment 13)
In operation [3b], use this ester of the Chinese (=2,6-dimethyl-Isosorbide-5-Nitrae-dihydropyridine-3,5-diethyl dicarboxylate) to replace leuco crystal violet, carry out similarly to Example 12 in addition, made organic electroluminescent device 2-12.
By being shown in Table 1 gathering of organic electroluminescent device of making in embodiment 7 ~ 13, comparative example 4 ~ 8.The ratio that % by weight of reducing agent is the amount relative to the organic compound used in resilient coating.
[table 1]
(characteristics of luminescence of organic electroluminescent device measures)
" the 2400 type Source Meter " that utilize Keithley company to manufacture has carried out applying voltage to element and measuring electric current." LS-100 " that utilize Konica Minolta company to manufacture determines luminosity.
Voltage-luminance characteristics when applying direct voltage under an argon to the organic electroluminescent device made in embodiment 7 ~ 13 and comparative example 4 ~ 8, current density-current efficiency characteristics are shown in Fig. 6 ~ 15.Known: in any one situation, compared with the unadulterated element made in comparative example, brightness, the current efficiency of the element after the doping made in embodiment are all higher, and characteristic is all excellent.
< the 3rd organic electroluminescent device > of the present invention
(making of organic electroluminescent device)
(embodiment 14)
[1] transparent glass substrate 1 of the band ITO electrode layer of commercially available average thickness 0.7mm is prepared.Now, the ITO electrode 2 of substrate uses and has carried out the ITO electrode after patterning with the width of 2mm.By this substrate respectively in acetone, carry out 10 minutes Ultrasonic Cleanings in isopropyl alcohol after, in isopropyl alcohol, boil 5 minutes.This substrate is taken out from isopropyl alcohol, utilizes nitrogen stream to make it dry, carry out 20 minutes UV ozone clean.
[2] this substrate is fixed on again the frame substrate of the subtend target formula sputter equipment with zinc metallic target.Be decompressed to about 1 × 10 -4after Pa, sputter under the state after importing argon and oxygen, made thickness and be about the zinc oxide film of 2nm as the 1st metal oxide layer 3.Now in order to take out electrode, share metal mask and making a part for ITO electrode film forming can not have zinc oxide.
[3] this substrate is carried out again the matting of [1] (after respectively in acetone, carrying out 10 minutes Ultrasonic Cleanings in isopropyl alcohol, 5 minutes are boiled in isopropyl alcohol, then nitrogen stream is utilized to make it dry, carry out 20 minutes UV ozone clean) after, the heating plate of 400 DEG C carries out annealing in 1 hour.
[4] then in order to form the layer 4 of nitrogenous film, polyethylene imine based (registered trade mark: EPOMIN) that Japanese catalyst company manufactures being utilized ethanol to be diluted to after 0.5 % by weight and carrying out spin coating under 2000rpm, the condition of 30 seconds.
EPOMIN as used herein to be molecular weight be 300 sp003.
[5] film (substrate) made in [4] is carried out annealing in 150 DEG C, 5 minutes on hot plate under air.The average thickness of the layer of the nitrogenous film measured after annealing is 5nm.
[6] then, being directed into vacuum plant by having carried out the substrate that [5] process, being decompressed to 1 × 10 -4below Pa.As organic compound layer 5, distinguish the lamination Alq as luminescent layer of 32.5nm successively by vacuum vapour deposition 3, 60nm the α-NPD as hole transmission layer.
[7] then, on organic compound layer 5, the 2nd metal oxide layer 6 is defined.At this, by defining the molybdenum oxide of 10nm as the vacuum vapour deposition of gas phase masking method.
[8] then, as final operation, the 2nd metal oxide layer 6 defines anode 7.At this, made the aluminium film of 150nm by vacuum vapour deposition.
[9] by following the characteristics of luminescence of the organic electroluminescent device (measure) and (the life characteristic mensuration of organic electroluminescent device) determine organic electroluminescent device characteristic (voltage-current density/light characteristic, current density-current efficiency characteristics, under constant current density (corresponding to 100cd/m 2, corresponding to 1000cd/m 2) Continuous Drive characteristic).Measurement result is shown in Figure 17-1,17-2 (a), (b), (c-1) and (c-2) in.
(characteristics of luminescence of organic electroluminescent device measures)
" the 2400 type Source Meter " that utilize Keithley company to manufacture has carried out applying voltage to element and measuring electric current." BM-7 " that utilize Topcon company to manufacture determines luminosity.Mensuration is carried out under an argon.
(life characteristic of organic electroluminescent device measures)
" the organic EL biometrics device " that utilize System Engineers company to manufacture has carried out applying voltage to element and measuring relative brightness.In this device, the mode of constant current is had automatically to adjust voltage, while utilize photodiode to carry out relative brightness mensuration according to making flowing in element.100cd/m is reached according to the brightness measured when starting 2and 1000cd/m 2mode for each components set current value.These results in each embodiment and comparative example are shown in (c-1), (c-2).
It should be noted that, figure (c-1), (c-2) marge be such as " t 1/2=200h@1000cd/m 2" etc. record represent the half-life, refer in above-mentioned situation, when continuing to be provided in initial with constant current correspond to 1000cd/m 2current density time the brightness half-life be 200 hours.
(comparative example 9)
Omit operation [4] [5] of embodiment 14, similarly carry out in addition, make organic electroluminescent device, determine voltage-current density/light characteristic and the current density-current efficiency characteristics of organic electroluminescent device similarly to Example 14.Their result is shown in Figure 18 (a), (b).
(embodiment 15)
The operation of the operation [4] of embodiment 14 is become following [4-2], similarly carry out in addition, made organic electroluminescent device, determine similarly to Example 14 the voltage-current density/light characteristic of organic electroluminescent device, current density-current efficiency characteristics and under constant current density (corresponding to 1000cd/m 2) Continuous Drive characteristic.Their result is shown in Figure 19-1,19-2 (a), (b) and (c-2) in.It should be noted that, the average film thickness of the layer of nitrogenous film is 6nm.
Polyethylene imine based (registered trade mark: EPOMIN) that Japanese catalyst company manufactures then, in order to form the layer 4 of nitrogenous film, utilizing ethanol to be diluted to after 0.5 % by weight and carrying out spin coating under 2000rpm, the condition of 30 seconds by [4-2].EPOMIN as used herein to be molecular weight be 70000 P1000.
(embodiment 16)
The operation of operation [4] [5] of embodiment 14 is become following [4-3] [5-3], similarly carry out in addition, made organic electroluminescent device, determine similarly to Example 14 the voltage-current density/light characteristic of organic electroluminescent device, current density-current efficiency characteristics and under constant current density (corresponding to 1000cd/m 2) under Continuous Drive characteristic.Their result is shown in Figure 20-1,20-2 (a), (b) and (c-2) in.It should be noted that, the average film thickness of the layer of nitrogenous film is 5nm.
Diethylenetriamines then, in order to form the layer 4 of nitrogenous film, utilizing ethanol to be diluted to after 1.0 % by weight and carrying out spin coating under 2000rpm, the condition of 30 seconds by [4-3].
The film (substrate) made in [4-3] has been carried out annealing in 100 DEG C, 2 minutes on hot plate by [5-3] under air.
(embodiment 17)
Omit the operation [5] of embodiment 14, similarly carry out in addition, make organic electroluminescent device, determined similarly to Example 14 under the voltage-current density/light characteristic of organic electroluminescent device and constant current density (corresponding to 100cd/m 2) under Continuous Drive characteristic.Their result is shown in Figure 21 (a) and (c-1).It should be noted that, for the thickness of the layer of nitrogenous film, owing to annealing, therefore this film is uncured and cannot measure, but can reduce due to the annealing under air according to the thickness of the layer of the nitrogenous film after the annealing in embodiment 14 and known thickness, be speculated as about 10nm thus.
(embodiment 18)
The operation of the operation [4] of embodiment 14 is become above-mentioned [4-2], the operation of [5] is become following [5-5], similarly carry out in addition, made organic electroluminescent device, determine similarly to Example 14 the voltage-current density/light characteristic of organic electroluminescent device, current density-current efficiency characteristics and under constant current density (corresponding to 100cd/m 2) under Continuous Drive characteristic.Their result is shown in Figure 22-1,22-2 (a), (b) and (c-1) in.It should be noted that, the average film thickness of the layer of nitrogenous film is 8nm.
The film (substrate) made in [4-2] is carried out annealing in 100 DEG C, 10 minutes on hot plate by [5-5] under air.
(embodiment 19)
The operation of the operation [4] of embodiment 14 is become above-mentioned [4-2], the operation of [5] is become following [5-6], similarly carry out in addition, made organic electroluminescent device, determine similarly to Example 14 the voltage-current density/light characteristic of organic electroluminescent device, current density-current efficiency characteristics and under constant current density (corresponding to 100cd/m 2) under Continuous Drive characteristic.Their result is shown in Figure 23-1,23-2 (a), (b) and (c-1) in.It should be noted that, the average film thickness of the layer of nitrogenous film is 7nm.
The film (substrate) made in [4-2] is carried out annealing in 150 DEG C, 10 minutes on hot plate by [5-6] under air.
(embodiment 20)
The operation of the operation [4] of embodiment 14 is become above-mentioned [4-2], the operation of [5] is become following [5-7], similarly carry out in addition, made organic electroluminescent device, measure similarly to Example 14 the voltage-current density/light characteristic of organic electroluminescent device, current density-current efficiency characteristics and under constant current density (corresponding to 1000cd/m 2) under Continuous Drive characteristic.Their result is shown in Figure 24-1,24-2 (a), (b) and (c-2) in.It should be noted that, the average film thickness of the layer of nitrogenous film is 5nm.
The film (substrate) made in [4-2] is carried out annealing in 150 DEG C, 30 minutes on hot plate by [5-7] under air.
(embodiment 21)
The operation of the operation [5] of embodiment 14 is become following [5-8], similarly carry out in addition, made organic electroluminescent device, determine similarly to Example 14 the voltage-current density/light characteristic of organic electroluminescent device, current density-current efficiency characteristics and under constant current density (corresponding to 1000cd/m 2) under Continuous Drive characteristic.Their result is shown in Figure 25-1,25-2 (a), (b) and (c-2) in.It should be noted that, the average film thickness of the layer of nitrogenous film is 5nm.
The film (substrate) made in [4] is carried out annealing in 100 DEG C, 30 minutes on hot plate by [5-8] under air.
(embodiment 22)
The operation of the operation [4] of embodiment 14 is become above-mentioned [4-2], the operation of [5] is become following [5-9], similarly carry out in addition, made organic electroluminescent device, determine similarly to Example 14 the voltage-current density/light characteristic of organic electroluminescent device, current density-current efficiency characteristics and under constant current density (corresponding to 100cd/m 2) under Continuous Drive characteristic.Their result is shown in Figure 26-1,26-2 (a), (b) and (c-1) in.It should be noted that, the average film thickness of the layer of nitrogenous film is 8nm.
The film (substrate) made in [4-2] is carried out annealing in 150 DEG C, 10 minutes on hot plate by [5-9] under nitrogen.
(embodiment 23)
The operation of the operation [5] of embodiment 14 is become following [5-11], similarly carry out in addition, made organic electroluminescent device, determine similarly to Example 14 the voltage-current density/light characteristic of organic electroluminescent device, current density-current efficiency characteristics and under constant current density (corresponding to 1000cd/m 2) under Continuous Drive characteristic.Their result is shown in Figure 27-1,27-2 (a), (b) and (c-2) in.It should be noted that, the average film thickness of the layer of nitrogenous film is 5nm.
The film (substrate) made in [4] is carried out annealing in 150 DEG C, 5 minutes on hot plate by [5-11] under air.Then, ethanol is utilized to carry out rinsing.
(Production Example 1)
The nitrogenous film obtained for the operation till [1] ~ [5] by embodiment 14, has carried out following photoelectron spectroscopy and has measured.
By carrying out the mensuration of carbon 1S track and nitrogen 1S track simultaneously, by this has been quantitative analysis.
They are shown in Figure 28 (d), (e).
(mensuration of X-ray photoelectron spectroscopy)
The photoelectron spectroscopy determinator of (JPS-9000MX) that use NEC company to manufacture, measures under the following conditions.
X-ray source: MgK α
Beam power output (accelerating voltage-magnitude of current): 10kV-10mA
Logical energy (Pass Energy): 10eV
Step-length (Step): 0.1eV
(Production Example 2)
The nitrogenous film obtained for the operation till [1] ~ [4] by embodiment 14, has carried out above-mentioned photoelectron spectroscopy and has measured.
By carrying out the mensuration of carbon 1S track and nitrogen 1S track simultaneously, by this has been quantitative analysis.
They are shown in Figure 29 (d), (e).
(Production Example 3)
For the nitrogenous film made by the operation of [1] ~ [3] of embodiment 14 and the operation of following [4-12] and [5-12], carry out above-mentioned photoelectron spectroscopy mensuration.It should be noted that, the average film thickness of the layer of nitrogenous film is 10nm.
[4-12] then, in order to form the layer 4 of nitrogenous film, the polyethylene imine based ethoxylate (molecular weight: 70000) utilize ethoxy ethanol to be diluted to after 0.4 % by weight and carry out spin coating under 5000rpm, the condition of 60 seconds that Aldrich is manufactured.
The film (substrate) made in [4-12] is carried out annealing in 100 DEG C, 10 minutes on hot plate by [5-12] under air.
By carrying out the mensuration of carbon 1S track and nitrogen 1S track simultaneously, by this has been quantitative analysis.
They are shown in Figure 30 (d), (e).
(Production Example 4)
Till carrying out the operation of [1] ~ [3] of embodiment 14, [4-13] and [5] as follows successively, for obtained nitrogenous film, carry out above-mentioned photoelectron spectroscopy and measured.It should be noted that, even if the thickness of the layer of nitrogenous film is the thickness by repeatedly measuring this degree that also cannot estimate average film thickness.Thus, supposition is less than 3nm.
Japanese catalyst company then, in order to form the layer 4 of nitrogenous film, being manufactured polyethylene imine based (registered trade mark: EPOMIN) and utilizing ethanol to be diluted to after 0.125 % by weight to carry out spin coating under 2000rpm, the condition of 30 seconds by [4-13].EPOMIN as used herein to be molecular weight be 70000 P1000.
By carrying out the mensuration of carbon 1S track and nitrogen 1S track simultaneously, by this has been quantitative analysis.
They are shown in Figure 31 (d), (e).
(embodiment 24-1)
The operation [4] of embodiment 14 and the operation of [5] are become following [4-18] [5-18], similarly carry out in addition, make organic electroluminescent device, determine the voltage-current density/light characteristic of organic electroluminescent device, current density-current efficiency characteristics similarly to Example 14.Their result is shown in Figure 32 (a) and (b).It should be noted that, the average film thickness of the layer of nitrogenous film is 10nm.
[4-18] then, in order to form the layer 4 of nitrogenous film, (buys polyethylene imine based for straight chain from Polysciences company, molecular weight: 25000) utilize ethanol to be diluted to after 0.1 % by weight and carry out spin coating under 2000rpm, the condition of 30 seconds.
The film (substrate) made in [4-18] is carried out annealing in 150 DEG C, 5 minutes on hot plate by [5-18] under air.
(embodiment 24-2)
Eliminate the operation [5-18] of embodiment 24-1, similarly carry out in addition, make organic electroluminescent device, determine the voltage-current density/light characteristic of organic electroluminescent device, current density-current efficiency characteristics similarly to Example 14.Their result is shown in Figure 33 (a) and (b).It should be noted that, the average film thickness of the layer of nitrogenous film is 12nm.
(embodiment 25)
The operation [4] of embodiment 14 and the operation of [5] are become following [4-20] [5-20], similarly carry out in addition, make organic electroluminescent device, determine the voltage-current density/light characteristic of organic electroluminescent device, current density-current efficiency characteristics similarly to Example 14.Their result is shown in Figure 34 (a) and (b).It should be noted that, the average film thickness of the layer of nitrogenous film is 10nm.
[4-20] then, in order to apply the nitrogen-containing compound of melmac as the layer 4 for the formation of nitrogenous film, melamine and formaldehyde are mixed with 1:3, mixed solution is dissolved in methyl alcohol with 0.1 % by weight: after in the mixed solvent of water=1:1, under 2000rpm, the condition of 30 seconds, carry out spin coating.
The film (substrate) made in [4-20] is carried out annealing in 80 DEG C, 60 minutes on hot plate by [5-20] under air.
(comparative example 10)
The operation [4] of embodiment 14 and the operation of [5] are become following [4-21] [5-21], similarly carry out in addition, make organic electroluminescent device, determine the voltage-current density/light characteristic of organic electroluminescent device, current density-current efficiency characteristics similarly to Example 14.Their result is shown in Figure 35 (a) and (b).
[4-21] then, uses toluene to go out polystyrene film (10nm) as the layer 4 not containing the organic film of nitrogen and replace nitrogenous film by spin coating masking.
The film (substrate) made in [4-21] is carried out annealing in 150 DEG C, 5 minutes on hot plate by [5-21] under air.
Following content is represented respectively about Figure 17 ~ Figure 27 and Figure 32 ~ Figure 35, (a) ~ (c).
A () is voltage-current density (black circles)/brightness (white circle) characteristic.The first, person is better for brightness height.The second, person is better can to show high brightness with more low-voltage.
B () is current density-current efficiency (black diamonds) characteristic.The first, current efficiency (being hereafter expressed as " efficiency ") height is advisable.The second, it keeps constant and is also advisable.Especially in areas of high current density (high-brightness region) for high and to be constantly advisable.
C at this, () expression (refers to that original intensity reaches 1000cd/m at constant current 2current value) under voltage over time with relative brightness over time.The first, relative brightness changes little (can maintain original intensity for a long time) (being hereafter expressed as " life-span is long ") in time and is advisable.The second, the voltage rise of period is little is advisable, but this is and above-mentioned first relevant content.
Brightness, efficiency, life-span 3 key elements are all important, but in practicality, wherein the life-span should be first matter of priority.
Premised on above-mentioned, to Figure 17 ~ 27,32 ~ 34 result be described.
Figure 17: luminous from low-voltage (about 2V), arrives 3000cd/m at 6V 2such high brightness.Efficiency is also higher in general, is more than 4cd/A.In addition, about change in long term, to brightness reduces by half, need 200 hours, can high reliability be realized.Be 100cd/m at original intensity 2another drive condition under, estimate the half-life with several thousand hours, therefore known reproducibility is also high.
Figure 18: Figure 18 is the measurement result for the element between metal oxide layer and luminescent layer without layer.Known brightness, efficiency are less than 1/10 of Figure 17.In the measurement result of below Figure 19, because it must be more excellent than the value of this Figure 18, show that the layer with nitrogenous film is effective thus.
Figure 19: although efficiency is better than Figure 17 (element of embodiment 14), initially in several hours, brightness sharply declines, and in the life-span, the result of Figure 17 is more excellent.Go out according to this results presumption, be in the stability under redox in membrane form, the element of embodiment 14 is more excellent.
Figure 20: brightness, efficiency all can be equal to Figure 17 (element of embodiment 14).In the life-span, the passing to initial 10 hours is also equal with Figure 17.But, obtain the result that sharply deterioration occurs afterwards.
According to Figure 19,20 result, obtain following result: even if use different polyethylene imine based of molecular weight, initial characteristic also can not produce significantly difference, all more excellent compared with not having the element of nitrogenous film.But, in long-time stability, obtain the result defining difference.
In Figure 21 ~ Figure 27 (embodiment 17 ~ 23), confirm be coated with nitrogen-containing compound be filmed after technique (annealing conditions (temperature, time, atmosphere) and the rinsing) impact (process dependency) on element characteristic.In addition, the molecular weight dependence for them is shown.
Figure 21: the measurement result being element characteristic when using liquid side chain polyethylene imine based (low-molecular-weight) under the condition without annealing.Substantially do not find luminescence, do not reach the level that can be called characteristic.
Figure 22 and Figure 23: be to using liquid side chain polyethylene imine based (HMW) and the result that measures of the characteristic of the element changing annealing temperature and obtain.The element that annealing temperature is high obtains all good result of brightness, efficiency.Annealing temperature is slightly remarkable on the impact in life-span, and it is more than 2 times good like this results that the element of annealing under high temperature obtains the half-life.Can find out that its difference is because the element brightness in the early stage of high annealing declines little.Comprise Figure 21, which imply annealing is effective to long lifetime, i.e. redox long-time stability.Although do not record at this, when annealing for 200 DEG C, because variable color is dark brownly therefore do not carry out element mensuration.Being inferred by above-mentioned, there is optimal value in the temperature about annealing.
Figure 24: embodiment 20 is under the optimum value of the annealing temperature obtained according to the result of embodiment 17 ~ 19 (Figure 21 ~ 23), the i.e. condition of 150 DEG C, changes the result that annealing time carries out the making of nitrogenous film.Brightness, efficiency all slightly reduce compared with Figure 23 (embodiment 19).In addition, about life curve, also the deterioration at known initial stage starts to display slightly by force.Being inferred by above-mentioned, also there is optimal value in annealing time.
Figure 26: be last under above-mentioned optimum condition to the result that the atmosphere of annealing is studied.When utilizing the condition of Figure 23 (embodiment 19) to carry out the making of nitrogenous film under a nitrogen, do not find there is larger difference between initial characteristic (brightness, efficiency) and Figure 23.Inferred by above-mentioned, the effect with nitrogenous film is here the sucting electronic effect that the polarization (polarization between the metal-nitrogen not in chemisorbed situation) between the metal-nitrogen in physical absorption situation and the polarization between the carbon-nitrogen in molecule produce.It should be noted, the life-span becomes extremely short in fig. 26.Accordingly, think and cause the annealing process in the present invention of long lifetime and be not only the change of desolventizing, pattern, be probably attended by and chemically change.(about being which kind of chemical change, describing hereinafter)
Figure 25: although be no doubt depend on material according to the results presumption annealing conditions of above-mentioned investigation, also depend on material molecule amount, thus to the result that it is studied.
Side chain for liquid state polyethylene imine based (low-molecular-weight), long term annealing has been carried out at lower than the temperature of optimum temperature, result brightness in initial characteristic, efficiency all obtain the result close with Figure 17, but under the voltage before luminescence and under reverse bias, observe that current density value is higher.This means to have the flowing (being hereafter expressed as " leakage current ") being helpless to luminous useless electric current, in most cases have problems in long-time stability.This time as the same, brightness is sharply fallen from initially, and the life-span is shorter, thinks that reason is due to above-mentioned leakage current.
According to the above results, although show that the optimum value of annealing conditions no doubt depends on material, also depend on material molecule amount.In addition, even if carry out long annealing like this also superperformance cannot be obtained below optimum temperature, imply also there is the temperature threshold depending on material and molecular weight thus.
Figure 27: if confirm the wash effect under above-mentioned optimum condition (condition of embodiment 14), then initial characteristic (brightness, efficiency) and Figure 17 (embodiment 14) are roughly equal, but leakage current is bigger.Think that rinsing causes the reason that life characteristic is deteriorated compared with Figure 17 (embodiment 14).But although do not display in the figure, the characteristic inequality between made element reduces, and increases in reproducibility.Think that this is important technique from practical viewpoint.Think and also make moderate progress in the life-span by finding better rinsing condition.
Figure 32 and Figure 33: be use the polyethylene imine based result as nitrogen-containing compound of straight chain.Have nothing to do with or without annealing in process, all show good initial characteristic (brightness, efficiency).Think that its reason is that straight chain is polyethylene imine based is solid because straight chain is polyethylene imine based polyethylene imine based different from side chain.That is, the effect of annealing is speculated as following 3 points.I () makes it solidify.(ii) by rich and variedization of metal-nitrogen key, firmly of bonding is provided.(iii) change carbon: the ratio of nitrogen element, relatively improve nitrogen element and there is ratio.
About the effect of above-mentioned annealing, further describe hereinafter.
Figure 34: be the result that melmac that correspondence is used as the high material of nitrogen ratio carries out studying.Compared with Figure 18, obtain good result, it is effective for can confirming.Because luminescence also exists inequality, therefore think if find meticulous optimal conditions, then can obtain better result.
Figure 35: the result being the organic film applied not containing nitrogen.In initial characteristic, known brightness, efficiency are all poor than Figure 19.Think thus, this organic film only plays a role as insulating barrier.Further, the life-span of this element is extremely short, is a few minutes, and the anticipation of the mechanism of electron injection is caused by the band curvature owing to causing luminescent layer at the charge accumulation of luminescent layer.Think for polystyrene, by also can initial characteristic be improved to studying in great detail of condition, but due to drive mechanism as implied above, therefore think and cannot expect that performance is as element of the present invention reliably and with long-term.
Then, Figure 28 ~ 31 (Production Example 1 ~ 4) is described.
In Production Example 1 ~ 4, before the annealing of nitrogenous film, all can not measure under the whole circumstances that liquid side chain is polyethylene imine based.On the other hand, become can measure by annealing.Imply thus, annealed by certain effect (only can not be derived as from this result and decompose such conclusion) and make it solidify (above-mentioned effect (i)).
The result (e) that the result (d) of the x-ray photoelectron power spectrum mensuration of the carbon 1s track of Figure 28 ~ 31 and the x-ray photoelectron power spectrum of nitrogen 1s track measure is all the measurement result after annealing.Before annealing, except Figure 30, all confirm as C:N ≈ 2:1.In Figure 30, be C:N ≈ 4:1 before annealing.These ratios are values consistent with the stoichiometric proportion estimated by chemical constitution.It is estimated by the ratio of the peak area of respective track that this element exists ratio.Figure 28 and Figure 29 relatively in, confirm because there is the example and the unconverted example of ratio that ratio changes with or without annealing.Due to annealing, the peak area of carbon and nitrogen all reduces, but the minimizing at carbon peak is larger, causes nitrogen element ratio relatively to improve.In Figure 30, also do not change, it can thus be appreciated that there is no obvious chemical change compared with (stoichiometric proportion) before annealing after annealing.Which imply, record in above-mentioned non-patent literature 1 ~ 3 by polyethylene imine based, to modify passing through of carrying out in effect that film that polyethylene imine based compound formed brings and the present invention effect that film that the side chain polyethylene imine based (low-molecular-weight) of liquid state is changed brings of annealing not equal.Figure 31 is by by more than polyethylene imine based for the side chain of liquid state (HMW) filming to polyethylene imine based equal of low-molecular-weight side chain, by the result that this has been same annealing in process.In this result, the polyethylene imine based element of HMW exists ratio also not to be changed.Implied thus, carbon: nitrogen element there is ratio if not under certain conditions, (above-mentioned effect (iii)) would not be changed under such as low-molecular-weight.
(f) of Figure 28 ~ 30 be represent the result that the x-ray photoelectron power spectrum of nitrogen 1s track is measured carried out peak segmentation after the figure of result.In this system, the kind of the key of nitrogen-atoms is assumed to be carbon-nitrogen bond and metal-two kinds, nitrogen key.According to existing document, the peak of minimum energy side belongs to as metal-nitrogen key.Further, then about another peak, if belong to carbon-nitrogen bond, then whole two peak-to-peak energy differences are 0.6eV ~ 0.7eV, roughly unanimously, have implied that the segmentation of these peaks and ownership are correct.
It should be noted that, although not shown at this, before annealing, in all embodiments of Figure 28 ~ Figure 30, half-peak breadth is all 1.2eV.Think thus, when Figure 28 and Figure 30, half-peak breadth increases, and this causes long lifetime (above-mentioned effect (ii)).
Think according to above-mentioned, in the example of Figure 28, show above-mentioned (i) ~ whole effects of (iii), initial characteristic (brightness, efficiency) and long-term reliability (life-span) can be realized.In Figure 30, infer because (i) and (ii) can realize initial characteristic and life-span to a certain degree, similarly, Tu29Zhong, infers because (i) effect can realize initial characteristic and life-span to a certain degree.Although embody in the result that above-mentioned supposition content does not measure in x-ray photoelectron power spectrum, although the straight chain of the solid used in Figure 32 and Figure 33 is polyethylene imine based it is believed that the life-span not have effect of annealing also can realize to a certain degree owing to achieving (i).Also be same in Figure 34.
According to the above results, indicate following content.
Confirm with comparing of other figure according to Figure 18, when being configured on the oxide be positioned on lower cathodic containing nitrogen film, cause the characteristic of the organic electroluminescent device such as brightness, efficiency to improve.About annealing in process, confirmed by Figure 33, sometimes do not need annealing because material is different, annealing is not necessarily necessary.But confirm, by annealing, the life characteristic in most cases corresponding to long-term reliability is improved.In addition, for use material, confirm the nitrogen-containing compound that polyethylene imine based (the different or shape Different L EssT.LTssT.LT straight chain of molecular weight and side chain >), diethylenetriamines, melmac and so on can be used various.In addition, also confirm their need according to material and according to molecular weight, shape to select technique.Particularly straight chain is polyethylene imine based polyethylene imine based different from other, thinks because it is solid, even if also can show effect without annealing.In addition, it is also effective for carrying out rinsing after also confirming masking.
Symbol description
1: substrate
2: negative electrode
3: the 1 metal oxide layers
4: the layer of nitrogenous film
5: organic compound layer
6: the 2 metal oxide layers
7: anode

Claims (17)

1. an organic electroluminescent device, it is the organic electroluminescent device of the structure with the layer being laminated with more than 2 layers, it is characterized in that, this organic electroluminescent device has metal oxide layer between the 1st electrode and the 2nd electrode, and this metal oxide layer has the resilient coating formed by organic compound.
2. organic electroluminescent device as claimed in claim 1, it is characterized in that, described 1st electrode is the negative electrode formed on substrate, the resilient coating having metal oxide layer successively and formed by organic compound between the anode as described 2nd electrode.
3. organic electroluminescent device as claimed in claim 1 or 2, it is characterized in that, described resilient coating is that the average thickness formed is the layer of more than 3nm by being coated with the solution containing organic compound, and this resilient coating is formed on metal oxide layer in a neighboring manner.
4. the organic electroluminescent device according to any one of claims 1 to 3, is characterized in that, the layer of described resilient coating to be average thickness be 5nm ~ 50nm.
5. the organic electroluminescent device according to any one of Claims 1 to 4, is characterized in that, described organic compound is the organic compound with boron atom.
6. organic electroluminescent device as claimed in claim 5, it is characterized in that, described have the organic compound of boron atom for the boron-containing compound represented with following formula (1) or the boron polymer being carried out being polymerized by the monomer component containing the boron-containing compound represented with following formula (2) and obtain
[changing 1]
In formula (1), dotted line arc representation forms ring structure together with the skeleton part represented with solid line; Dotted portion in the skeleton part represented with solid line represent with dotted line connect 1 pair of atom with double bond connect or do not connect with double bond; The arrow pointing to boron atom from nitrogen-atoms represents that nitrogen-atoms is coordinated in boron atom; Q 1and Q 2identical or different, they are the linking groups in the skeleton part represented with solid line, and at least local forms ring structure, their with or without substituting groups together with dotted line circular arc portion; X 1, X 2, X 3and X 4identical or different, represent hydrogen atom or as monovalent substituent substituent on ring structure, the ring structure of formation dotted line circular arc portion can be bonded with more than 2 X 1, X 2, X 3and X 4; n 1represent the integer of 2 ~ 10; Y 1for Direct Bonding or n 1the linking group of valency, represents and existing n 1individual except Y 1structure division is in addition bonded in the ring structure, the Q that form dotted line circular arc portion independently of one another 1, Q 2, X 1, X 2, X 3, X 4in arbitrary place,
[changing 2]
In formula (2), dotted line arc representation forms ring structure with connection boron atom together with a part for the skeleton part of nitrogen-atoms; Connect boron atom and represent that at least 1 pair of atom is connected with double bond with the dotted portion in the skeleton part of nitrogen-atoms, this double bond and ring structure conjugation or non-conjugation; The arrow pointing to boron atom from nitrogen-atoms represents that nitrogen-atoms is coordinated in boron atom; X 5and X 6identical or different, represent hydrogen atom or as monovalent substituent substituent on ring structure, can bonding more than 2 X on the ring structure forming dotted line circular arc portion 5and X 6; R 1and R 2identical or different, represent hydrogen atom or monovalent substituent; X 5, X 6, R 1and R 2in at least one be the substituting group with reactive group.
7. the organic electroluminescent device according to any one of claims 1 to 3, is characterized in that, described resilient coating contains reducing agent.
8. organic electroluminescent device as claimed in claim 7, is characterized in that, described resilient coating is that the average thickness formed is the layer of 5nm ~ 100nm by being coated with the solution containing organic compound.
9. organic electroluminescent device as claimed in claim 7 or 8, it is characterized in that, described reducing agent is hydride reducer.
10. organic electroluminescent device as claimed in claim 9, it is characterized in that, described hydride reducer is for being selected from by 2,3-dihydrobenzo [d] imidazolium compounds, 2,3-dihydrobenzo [d] thiazolium compounds, 2,3-dihydrobenzos [at least one compound in the group of d] oxazole compounds, triphenylmethane compound and dihydropyridine compound composition.
11. organic electroluminescent devices according to any one of claims 1 to 3, it is characterized in that, described resilient coating is the average thickness be made up of nitrogenous film is the layer of 3nm ~ 150nm.
12. organic electroluminescent devices as claimed in claim 11, it is characterized in that, described nitrogenous film is formed by nitrogen-containing compound; Or containing nitrogen element and carbon as the element forming film, the ratio that exists of the nitrogen-atoms and carbon atom that form this film meets following relation:
Nitrogen-atoms number/(nitrogen-atoms number+carbon number) >1/8.
13. organic electroluminescent devices as described in claim 11 or 12, is characterized in that, by heating, nitrogen-containing compound are decomposed, form described nitrogenous film thus.
14. organic electroluminescent devices according to any one of claim 11 ~ 13, is characterized in that, described nitrogen-containing compound is polynary amine or the compound containing triazine ring.
15. 1 kinds of display unit, is characterized in that, it uses the organic electroluminescent device according to any one of claim 1 ~ 14 and is formed.
16. 1 kinds of lighting devices, is characterized in that, it uses the organic electroluminescent device according to any one of claim 1 ~ 14 and is formed.
The manufacture method of 17. 1 kinds of organic electroluminescent devices, it is the manufacture method of the organic electroluminescent device of the structure of the layer with lamination more than 2 layers, it is characterized in that, this manufacture method comprises and between the 1st electrode and the 2nd electrode, has the 1st metal oxide layer according to organic electroluminescent device successively, resilient coating, the low molecular compound layer comprising luminescent layer of lamination on this resilient coating, the operation of each layer of electro-luminescence element is configured with the mode lamination of the 2nd metal oxide layer, this lamination operation comprises coating and contains the solution of organic compound and form the operation that average thickness is the resilient coating of more than 3nm.
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