CN100349908C - Organic metal complex, electroluminescent material using the complex and ectroluminescent element using the complex - Google Patents
Organic metal complex, electroluminescent material using the complex and ectroluminescent element using the complex Download PDFInfo
- Publication number
- CN100349908C CN100349908C CNB2004800042973A CN200480004297A CN100349908C CN 100349908 C CN100349908 C CN 100349908C CN B2004800042973 A CNB2004800042973 A CN B2004800042973A CN 200480004297 A CN200480004297 A CN 200480004297A CN 100349908 C CN100349908 C CN 100349908C
- Authority
- CN
- China
- Prior art keywords
- atom
- family
- organometallic complex
- chelating ligand
- anion type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
An object of the present invention is to provide novel organometal complexes which is obtainable with a good yield by using a ligand which can be easily synthesized. Particularly, it is intended to provide the organometal complexes which is excellent in heat resistance. Further, it is intended to provide an electroluminescence element having high light emission efficiency by manufacturing the electroluminescence element using the organometal complex. Therefore, the organometal complex represented by the general formula (1) is synthesized. Further, this is applied to the electroluminescence element.
Description
Technical field
The present invention relates to a kind of novel organometallic complex.Particularly relate to and triplet excited state can be changed into luminous organometallic complex.In addition, the present invention relates to use the electroluminescent material of above-mentioned organometallic complex.And then, the invention still further relates to the electroluminescent cell that uses above-mentioned organometallic complex, this luminous element has anode, negative electrode and contains a class can be by applying the layer (hereinafter referred to as " electroluminescent layer ") that electric field produces luminous organic compound.
Background technology
Organic compound (organic molecule) is in case absorb light will be transformed into the state (excited state) with energy.By via this excited state, might cause various reactions (photochemical reaction), cause luminous (luminescence), thereby can be used for various application.
As one of photochemical reaction example, can enumerate the reaction (oxygen addition) (for example with reference to non-patent literature 1) of singlet oxygen and unsaturated organic molecule.Because the ground state of oxygen molecule is triplet state, therefore, the oxygen (singlet oxygen) of a heavy attitude can not directly generate by optical excitation.Yet, other the triplet excited state molecule in the presence of just can generate singlet oxygen, and can cause the oxygen addition reaction.At this moment, the compound that can form above-mentioned triplet excited state molecule is called as photosensitizer.
3 people such as (non-patent literature 1) aboveground fine husband, Basic chemistry Courses, photochemistry I (ball is apt to Co., Ltd.), 106-110.Therefore, in order to generate singlet oxygen, must existence can form the photosensitizer of triplet excited state molecule by optical excitation.Yet, because the ground state of common organic compound is singlet, therefore, become forbidden transition jing towards the optical excitation of triplet excited state, be difficult to generate triplet excited state molecule (generating a heavy excited state molecule usually).Thereby as such photosensitizer, people's demand is a kind of to be caused easily from the compound of reporting to the leadship after accomplishing a task between the energy state of a heavy excited state and triplet excited state the compound of direct light activated forbidden transition jing towards triplet excited state (or break).In other words, such compound might be utilized as photosensitizer, can be described as useful compound.
In addition, such compound usually can be emitted phosphorescence.Phosphorescence be a kind of owing to the transition between the different-energy of multiplicity cause luminous, for common organic compound, be meant luminous (with respect to this, the luminous fluorescence that then is called when returning to a weight ground state) that when returning to a weight ground state by triplet excited state, produces by a heavy excited state.Can emit the compound of phosphorescence, just triplet excited state can be transformed into luminous compound (hereinafter referred to as " phosphorescent compounds "),, can enumerate and use the electroluminescent cell of organic compound as luminance compound as its Application Areas.
This electroluminescent cell since its have that thin form is in light weight, the characteristic of high-speed response, DC low-voltage driving etc., therefore be a kind of as a new generation flat panel displaying element and noticeable equipment.In addition, because of it is that emissive type and field-of-view angle are wide, sharpness is better, can think that therefore it can effectively use element as the display frame of handheld device.
When organic compound was used as twinkler, the luminous mechanism of electroluminescent cell was a carrier wave injection type.Promptly, electroluminescent layer in clamping between two electrodes, by to two electrode application voltage, make by the negative electrode injected electrons with combine again in electroluminescent layer by the anode injected holes, form excited molecule, when this excited molecule returns to ground state, just emit energy and simultaneously luminous.
As the kind of excited molecule, same with above-mentioned light activated situation, may be a heavy excited state (S
*) and triplet excited state (T
*).In addition, can think, in electroluminescent cell, S
*With T
*Statistics to produce ratio be S
*: T
*=1: 3 (for example with reference to non-patent literatures 2).
(non-patent literature 2) tube well wise man husband, Applied Physics association, the meeting of organic molecule biological electronics branch, the 3rd seminar textbook, 31-37 (1993)
Yet general organic compound does not observe luminous (phosphorescence) by triplet excited state at ambient temperature, can only observe luminous (fluorescence) by a heavy excited state usually.The ground state of organic compound is a heavy ground state (S normally
0), therefore, T
*→ S
0Transition (phosphorescence process) become strong forbidden transition jing, and S
*→ S
0Transition (fluorescence process) then becomes permitted transition.
Therefore, the theoretical boundary of the internal quantum in electroluminescent cell (photon of generation is to the ratio of injected carrier) is with S
*: T
*=1: 3 for according to the time be defined as 25%.
, if use above-mentioned phosphorescent compounds, then can allow T
*→ S
0Transition (phosphorescence process), therefore, it is possible in theory that inner quantum effect reaches 75～100%.That is to say that luminous efficiency might reach in the past 3～4 times.In fact, the report about the electroluminescent cell that uses phosphorescent compounds has been arranged in succession, the height of its luminous efficiency make one notice (for example with reference to non-patent literature 3, non-patent literature 4).
3 people such as (non-patent literature 3) D.F. オ Block ラ イ エ Application, " applied physics communication " (ア プ ラ イ De Off イ ジ Network ス レ one ズ), Vol.74, No.3,442-444 (1999)
8 people such as (non-patent literature 4) ラ Star オ ッ Star イ, " Japanese applicating physical magazine " (ジ ヤ パ ニ one ズ ジ ヤ one Na Le オ Block ア プ ラ イ De Off イ ジ Network ス), Vol.38, L1502-L1504 (1999)
Use a class with the metalloporphyrin complex of platinum as central metal in non-patent literature 3, and use a class with the organometallic complex of iridium as central metal in non-patent literature 4, any title complex wherein all is a phosphorescent compounds.
In addition, contain with iridium as the layer of the organometallic complex (hereinafter referred to as " complex of iridium ") of central metal and layer alternately lamination that contains as the DCM2 of known fluorescence compound by making, can so also help luminous (for example with reference to the non-patent literature 5) of DCM2 so that the triplet excitation energy that generates moves to DCM2 in complex of iridium.In this case, the amount (generally below 25%) of the heavy excited state of DCM2 is compared broadening to some extent with normal conditions, and the luminous efficiency of DCM2 is increased.This also can be described as because as the cause of the sensibilized of the iridium ligand of phosphorescent compounds.
2 people such as (non-patent literature 5) M.A. バ Le De, nature (London), Vol.403,750-753 (2000)
Shown in non-patent literature 3～non-patent literature 5, use the electroluminescent cell of phosphorescent compounds can reach than higher in the past luminous efficiency (that is, can be issued to high brightness) in less current.Therefore, can think, use the electroluminescent cell of phosphorescent compounds, as the method that is used to reach high brightness luminescent, high-luminous-efficiency, in exploitation from now on significant.
As mentioned above, phosphorescent compounds causes reporting to the leadship after accomplishing a task between energy state easily, and cause luminous (phosphorescence) by triplet excited state easily, therefore can be used as the photosensitizer utilization, perhaps can be used as phosphor material and be applicable to electroluminescent cell, be the compound that class people are expected, but this compounds is very few for number, this is present present situation.
In for the very few phosphorescent compounds of number, the complex of iridium that uses in non-patent literature 4 or the non-patent literature 5 is to be called a kind of in the organometallic complex of ortho position (ortho) metal complexes.Because the phosphorescent lifetime of this title complex is hundreds of nanoseconds, and the yield of phosphorescence quantum is also high, therefore, compare with above-mentioned metalloporphyrin complex, it is less that complex of iridium is accompanied by the rise reduction degree of the efficient caused of brightness, so be a kind of effective electroluminescent cell.On this meaning, such organometallic complex be a kind of cause easily that the direct sunshine towards triplet excited state excites or energy state between the compound of reporting to the leadship after accomplishing a task, we can say that also this is a pointer that is used for synthetic phosphorescent compounds.
The texture ratio of the ligand of the complex of iridium that uses in non-patent literature 4 or non-patent literature 5 is more simple, shows the good green emitting of purity of color, for illuminant colour being changed over other colors, just must change the structure of ligand.For example, in non-patent literature 6, synthesize various ligands and use this ligand to synthesize complex of iridium, and realized some kinds of glow colors.
10 people such as (non-patent literature 6) M. ト Application プ ソ Application, the 10th time the world about inorganic and organic field luminescence is topic discussion (EL ' 00), 35-38.
Yet these ligands almost are only limited to those can form pentacyclic ligand with central metal, and present present situation is that people are exploring from the suitable illuminant colour that wherein sends.That is to say, still have the still less problem of kind of the ligand that is suitable for.
In addition, the majority in these ligands all is difficult to synthesize, and perhaps needed step is more in synthetic, so also causes the cost of material itself to rise.Consider that from the viewpoint of cost the yield of organometallic complex itself also is important.
In addition, organometallic complex generally all decomposes easily.Even be not easy to decompose, its decomposition temperature can be very not high yet.Therefore that is to say the shortage thermotolerance, often become problem in the time of in being applied to the electronics of electroluminescent cell etc.
In sum, people need a class to be easy to that the synthetic ligand is applicatory, its synthetic yield good and the also good organometallic complex of thermotolerance.By synthetic such organometallic complex, can obtain high photosensitizer of thermotolerance or phosphor material etc. at an easy rate.
Therefore, the purpose of this invention is to provide a class and use synthetic ligand and the good novel organometallic complex of yield of being easy to.In addition, purpose of the present invention particularly will provide a kind of new organometallic complex of excellent heat resistance.
And the objective of the invention is to provide a class luminous efficiency high electroluminescent cell by using above-mentioned organometallic complex to make electroluminescent cell.And then, the objective of the invention is and will make light-emitting device, to provide a class consumed power low light-emitting device by using above-mentioned electroluminescent cell.
Summary of the invention
Present inventors have carried out deep research, found that, carry out Cyclometalated reaction by making ligand and central metal raw material by following general formula (12) expression, can synthesize organometallic complex a kind of and central metal formation six-ring
Therefore, the invention provides a kind of organometallic complex that has by the part-structure of following general formula (1) expression.
(R1～R7 can represent hydrogen atom, halogen atom, low alkyl group, alkoxyl group, acyl group, nitro, cyano group, amino, dialkyl amido, ammonia diaryl base separately identical or differently, can have substituent vinyl, can have substituent aryl, can have any group in the substituent heterocycle residue; In addition, R1 and R2, R2 and R3, R4 and R5, R5 and R6 can mutually combine separately, form aromatic ring; In addition, X represents Sauerstoffatom or sulphur atom; Y represents to contain nitrogen-atoms as heteroatomic heterocycle residue; In addition, M represents the 9th family's atom or the 10th family's atom).
In addition, other schemes of the present invention provide the organometallic complex by following general formula (2) expression.
(R1～R7 can represent hydrogen atom, halogen atom, low alkyl group, alkoxyl group, acyl group, nitro, cyano group, amino, dialkyl amido, ammonia diaryl base separately identical or differently, can have substituent vinyl, can have substituent aryl, can have any group in the substituent heterocycle residue; In addition, R1 and R2, R2 and R3, R4 and R5, R5 and R6 can mutually combine separately, form aromatic ring; In addition, X represents Sauerstoffatom or sulphur atom; Y represents to contain nitrogen-atoms as heteroatomic heterocycle residue; In addition, M represents the 9th family's atom or the 10th family's atom, when above-mentioned M was the 9th family's atomic time, and n=2, when M was the 10th family's atomic time, n=1; In addition, L represent to have the single anion type of beta-diketon structure the double-core chelating ligand, have the single anion type of carboxyl the double-core chelating ligand, have any ligand in the double-core chelating ligand of single anion type of phenol hydroxyl).
Because the ligand by above-mentioned general formula (12) expression is easy to synthesize, therefore above-mentioned this type of organometallic complex has synthetic advantage at an easy rate.In addition, its yield is also good.
At this moment,, consider, preferably the heterocyclic radical that constitutes by five yuan or six-ring such as 2-pyridyl, 2- azoles base, 2-thiazolyl from the viewpoint of three-dimensional arrangement as the heterocycle residue Y in above-mentioned general formula (1) and the general formula (2).Particularly the 2-pyridyl is synthetic easily, and is therefore preferred.
In addition, more preferably scheme of the present invention provides a class to have the organometallic complex of the part-structure of being represented by following general formula (3).
(X represents Sauerstoffatom or sulphur atom.In addition, M represents the 9th family's atom or the 10th family's atom).
And then preferred other schemes of the present invention provide the organometallic complex by following general formula (4) expression.
(X Sauerstoffatom or sulphur atom.In addition, M represents the 9th family's atom or the 10th family's atom, when above-mentioned M was the 9th family's atomic time, and n=2, when M was the 10th family's atomic time, n=1; In addition, L represent to have the single anion type of beta-diketon structure the double-core chelating ligand, have the single anion type of carboxyl the double-core chelating ligand, have any ligand in the double-core chelating ligand of single anion type of phenol hydroxyl).
And then present inventors find that organometallic complex of the present invention can phosphoresce., in order can to phosphoresce more efficiently, consider from the viewpoint of heavy atom effect herein, preferably with heavy metal as central metal.Therefore, the invention is characterized in that central metal is iridium atom or pt atom.On the other hand, above-mentioned X oxygen more preferably.
In addition, in above-mentioned general formula (2) or above-mentioned general formula (4), any ligand in the double-core chelating ligand of the single anion type that ligand L can be double-core chelating ligand, the double-core chelating ligand with single anion type of carboxyl with single anion type of beta-diketon structure, have the phenol hydroxyl, but preferably by any ligand in the double-core chelating ligand of the single anion type of following structural formula (5)～(11) expression.The coordination ability height of the double-core chelating ligand of these single anion types, and can buy at an easy rate, be effective therefore.
, organometallic complex of the present invention can be transformed into triplet excited state luminous, therefore is applicable to electroluminescent cell, thereby can very effectively makes the element high efficiency.Therefore, the present invention also comprises the electroluminescent cell that uses organometallic complex of the present invention.
At this moment, organometallic complex of the present invention can be used as and is used to cause that the material of the sensibilized as described in the non-patent literature 5 uses, perhaps using as the material in the carrier wave transfer layer of hole transporting layer etc., still, is being effective aspect the luminous efficiency as the method for utilizing of twinkler.Therefore, feature of the present invention is a kind of electroluminescent cell that uses organometallic complex of the present invention as twinkler.
Should illustrate that so the electroluminescent cell of the present invention that obtains can be realized high luminous efficiency, therefore, uses this electroluminescent cell can realize the low consumption of electric energy as the light-emitting device of luminous element.Therefore, the present invention also comprises the light-emitting device that uses electroluminescent cell of the present invention.
Should illustrate that the light-emitting device in this specification sheets is meant that those use image display or the luminaire of electroluminescent cell as luminous element.Flexible print circuit (Flexible Printed Circuit)) or the module of TAB (band shape bonding automatically (TapeAutomated Bonding)) band or TCP (strip-like carrier packing (Tape CarrierPackage)), be provided with the module of printed-wiring board (PWB) or the mode by COG (Chip On Glass) also all is included in the module that IC (unicircuit) is directly installed on the electroluminescent cell in the light-emitting device before TAB band or TCP in addition, junctor, for example anisotropic conductive film (FPC: is installed in electroluminescent cell.
Description of drawings
Fig. 1 is the synoptic diagram of the component structure of the electroluminescent cell of expression embodiment 1.
Fig. 2 is the synoptic diagram of the component structure of the electroluminescent cell of expression embodiment 2.
Fig. 3 is the synoptic diagram of the component structure of the electroluminescent cell of expression embodiment 3.
Fig. 4 is the synoptic diagram of expression light-emitting device.
Fig. 5 is the synoptic diagram of expression electronics.
Fig. 6 is the synoptic diagram of the UV-Vis absorption spectrum of expression organometallic complex of the present invention.
Fig. 7 is the synoptic diagram of the emmission spectrum of expression organometallic complex of the present invention.
Fig. 8 is the UV-Vis absorption spectrum of expression organometallic complex of the present invention and the synoptic diagram of emmission spectrum.
Fig. 9 is the UV-Vis absorption spectrum of expression organometallic complex of the present invention and the synoptic diagram of emmission spectrum.
Figure 10 is the synoptic diagram of the characteristic of expression electroluminescent cell of the present invention.
Figure 11 is the synoptic diagram of the emmission spectrum of expression electroluminescent cell of the present invention.
Embodiment
Synthesize by the following synthetic route (a) that the ligand of following general formula (12) expression can be reacted by the iodide B that for example makes phenothiazine derivative A and heterogeneous ring compound.But synthetic method is not limited to this synthetic route.
Should illustrate, in above-mentioned general formula (12), R1～R7 can represent hydrogen atom, halogen atom, low alkyl group, alkoxyl group, acyl group, nitro, cyano group, amino, dialkyl amido, ammonia diaryl base separately identical or differently, can have substituent vinyl, can have substituent aryl, can have any group in the substituent heterocycle residue; In addition, R1 and R2, R2 and R3, R4 and R5, R5 and R6 can mutually combine separately, form aromatic ring.
At this moment, as low alkyl group, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, hexyl etc., preferably carbonatoms is the alkyl of 1-6.In addition, also can be the cycloalkyl of the haloalkyl of trifluoromethyl etc. or cyclohexyl etc.As alkoxyl group, can enumerate methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert.-butoxy, hexyloxy etc., preferably carbonatoms is 1～6 alkoxyl group.As acyl group, can be ethanoyl etc.As dialkyl amido, can enumerate dimethylamino, diethylin etc., preferably the carbonatoms of alkyl chain is 1～4 dialkyl amido.As ammonia diaryl base, can enumerate diphenyl amino, two (Alpha-Naphthyl) amino etc., also can be the substituted aryl amino as two (tolyl) is amino.As vinyl, can be as diphenylacetylene, to have substituent vinyl.As aryl, can be that phenyl, naphthyl etc. do not have the aryl that replaces, in addition, can be that phenyl, naphthyl etc. do not have the aryl that replaces, in addition, also can be the substituted aryl of o-tolyl, a tolyl, p-methylphenyl, xylyl, methoxyphenyl, phenelyl, fluorophenyl etc.As heterocycle residue, can enumerate pyridyl, furyl, thienyl etc.
In addition, in above-mentioned general formula (12), X represents Sauerstoffatom or sulphur atom.In addition, as heterocycle residue Y, can be the condensed ring formula group that resembles 2-benzoxazol Kina sample, still, and if considering not hinder to metal-complexing and coordination is easy to three-dimensional arrangement, the heterocycle residue of five-ring or six-ring preferably then.Can be 2-pyridyl, 4-pyrimidyl, 2- azoles base, 2-thiazolyl etc. particularly.
Example more specifically as the ligand of representing by above-mentioned general formula (12), can enumerate 10-(2-pyridyl) thiodiphenylamine, 10-(2-pyridyl)-3,7-dimethyl thiodiphenylamine, 10-(2-pyridyl)-4,6-dimethyl thiodiphenylamine, 10-(2-pyridyl)-3,7-dimethoxy thiodiphenylamine, 10-(2-pyridyl)-3, two (diphenyl amino) thiodiphenylamine of 7-, 10-(2-pyridyl)-3, two (diphenylacetylene) thiodiphenylamine of 7-, 10-(2-pyridyl)-dibenzo [c] [h]-thiodiphenylamine, 10-(2- azoles base) thiodiphenylamine, 10-(2-thiazolyl) thiodiphenylamine, 10-(2-pyridyl) fen piperazine, 10-(2-pyridyl)-3,7-dimethyl fen piperazine, 10-(2-pyridyl)-4,6-dimethyl fen piperazine, 10-(2-pyridyl)-3,7-dimethoxy fen piperazine, 10-(2-pyridyl)-3, two (dimethylamino) fen piperazines of 7-, 10-(2-pyridyl)-3, two (diphenyl amino) fen piperazines of 7-, 10-(2-pyridyl)-3, two (diphenylacetylene) fen piperazines of 7-, 10-(2-pyridyl)-dibenzo [c] [h]-fen piperazine, 10-(2- azoles base) fen piperazine, 10-(2-thiazolyl) fen piperazine etc., but the present invention is not limited to these concrete examples.
Use ligand as described above (12) to form the organometallic complex of the present invention that has by the part-structure of following general formula (1) expression below.Should give explanation, R1～R7, the X in following general formula (1), Y and R1～R7, X, Y in above-mentioned ligand general formula (12) are same group.In addition, M represents the 9th family's atom or the 10th family's atom, pt atom or iridium atom etc. specifically.
Give an example below the method for using double-core chelating ligand L to form the organometallic complex of being represented by following general formula (2) of the present invention is described.Should give explanation, R1～R7, the X in following general formula (2), Y and R1～R7, X, Y in above-mentioned ligand general formula (12) are same group.In addition, M represents the 9th family's atom or the 10th family's atom, pt atom or iridium atom etc. specifically.Should give explanation, when above-mentioned M was the 9th family's atomic time, n=2, when M was the 10th family's atomic time, n=1.
As Cyclometalated reaction at this moment, can use known synthesis method.For example, synthetic when being the organometallic complex of the present invention of central metal with iridium, hydrate by using iridium chloride is as the central metal raw material, its ligand with above-mentioned general formula (12) is mixed, reflux under nitrogen atmosphere at first synthesizes the crosslinked polynuclear coordination compound title complex of chlorine (following synthetic route (b)).Then, mix with binuclear chelate ligand L, under nitrogen atmosphere, reflux, make chlorine crosslinked, thereby obtain organometallic complex of the present invention (following synthetic route (c)) by double-core chelating ligand L cut-out by the above-mentioned polynuclear coordination compound title complex that will be obtained.
Should illustrate, L represent to have the single anion type of beta-diketon structure the double-core chelating ligand, have the single anion type of carboxyl the double-core chelating ligand, have any ligand in the double-core chelating ligand of single anion type of phenol hydroxyl, can enumerate particularly: methyl ethyl diketone, dimethyl malonate, pyridine carboxylic acid, proline(Pro), salicylidene amine, salicylic aldehyde, oxine etc.
As the concrete example of the organometallic complex of the present invention of acquisition like this, can enumerate for example organometallic complex of following structural formula (13)～(20) etc.Wherein, though disclosed in structural formula (16) and (20) be transconfiguration, cis-structure also is fine.
Though more than show an example of the formation of using double-core chelating ligand L, organometallic complex of the present invention is not limited to these title complexs.
For example, as what represent, also can be to use ortho-metalated ligand (in structural formula (21)～(24), being the 2-phenylpyridine) to replace the formation of above-mentioned double-core chelating ligand L by following structural formula (21)～(24).These organometallic complexs can synthesize via the resultant of above-mentioned reaction formula (C).For example, the organometallic complex of structural formula (21) can obtain by above-mentioned structural formula (13) and 2-phenylpyridine are reacted.Should also illustrate, in the majority with the occasion that forms the cis-structure formula under the situation of the cyclic metal complex of platinum, therefore the structure of cis is disclosed in structural formula (22) and (24), still trans structure also is fine.
Perhaps, also can be as following structural formula (25)～(28) expressions, as the formation of use with a kind of ligand.About these organometallic complexs, also can synthesize via the resultant of above-mentioned reaction formula (c).For example, the organometallic complex of structural formula (25) can react and obtain by making said structure formula (13) and 10-(2-pyridyl) thiodiphenylamine.Should give explanation, in the majority with the occasion that forms the cis-structure body under the situation of the cyclic metal complex of platinum, therefore the structure of cis is disclosed in structural formula (26) and (28), still trans structure also is fine.
Aforesaid organometallic complex of the present invention can be used as photosensitizer or phosphor material uses, and then describes the scheme that it is applicable to electroluminescent cell below.
Electroluminescent cell of the present invention is that a kind of element that the electroluminescent layer (contain luminescent layer at least, and be made of any layer or the multiple layer that are selected from hole injection layer, hole transporting layer, luminescent layer, hole blocking layer, electron supplying layer, the electron injecting layer) of the organometallic complex that contains the invention described above in clamping between pair of electrodes (anode and negative electrode) constitutes basically.
In addition, the material as beyond the organometallic complex of the present invention that uses in electroluminescent layer can use material known, also can use in low branch subclass material and the high score subclass material any.Should give explanation,, be not limited to only constitute, wherein also can contain the mineral compound of some by organic compound material as the material that is used to form electroluminescent layer.
Explain the embodiment of electroluminescent cell of the present invention below.
[embodiment 1]
In the present embodiment 1, utilize the element of Fig. 1 light field electroluminescent element to constitute, hole injection layer, hole transporting layer, hole blocking layer and electron supplying layer that this electroluminescent cell has the luminescent layer that contains organometallic complex of the present invention, is made of low branch subclass material.
Structure shown in Figure 1 is to form the 1st electrode 101 on the substrate 100, form electroluminescent layer 102 on the 1st electrode 101, forming the 2nd electrode 103 more in the above.
Should illustrate,,,, for example can use the material that constitutes by glass, quartz, transparent plastics etc. in traditional electroluminescent cell herein so long as the material that uses gets final product as the material that is used for substrate 100.
In addition, the 1st electrode 101 in the present embodiment 1 works as anode, and the 2nd electrode 103 then works as negative electrode.
That is to say that the 1st electrode 101 is formed by anode material, herein, as operational anode material, preferably metal, alloy, conductive compound and their mixture etc. of work function big (work function is more than 4.0eV).As the concrete example of anode material, can use ITO (tin indium oxide), in Indium sesquioxide, be mixed into the IZO (indium zinc oxide) of 2～20% zinc oxide (ZnO) and the nitride (TiN) of gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd) or metallic substance etc.
On the other hand, as the cathode material that can be used for forming the 2nd electrode 103, preferably use metal, alloy, conductive compound and their mixture of work function little (work function is below 3.8eV).Should illustrate, concrete example as cathode material, can use those element that belongs to the periodic table of elements the 1st family or the 2nd family, the just alkaline-earth metal of the basic metal of Li or Cs etc. and Mg, Ca, Sr etc. and alloy (Mg:Ag, Al:Li) or compound (LiF, CsF, CaF that contains these metals
2) and comprise that the transition metal of rare earth metal forms, also can form by metal (comprising alloy) lamination with Al, Ag, ITO etc.
In addition, can pass through vapour deposition method, sputtering method etc. above-mentioned anode material and cathode material are formed film, thereby form the 1st electrode 101 and the 2nd electrode 103 respectively.Thickness is preferably 10～500nm.
In addition, the structure in electroluminescent cell of the present invention is that the light that is produced by the combination again of the carrier wave in the electroluminescent layer is transmitted into the outside from a side or two sides of the 1st electrode 101 or the 2nd electrode 103.That is to say that launching the light time by the 1st electrode 101, the material of the 1st electrode 101 usefulness light transmissions forms, and is launching the light time by the 2nd electrode 103 sides, the material of the 2nd electrode 103 usefulness light transmissions forms.
In addition, electroluminescent layer 102 can be by form many laminated layer together, and in the present embodiment 1, by hole injection layer 111, hole transporting layer 112, luminescent layer 113, hole blocking layer 114 and electron supplying layer 115 laminations are formed together.
As the hole-injecting material that is used to form hole injection layer 111, phthalocyanine-like compound is effective.For example, can use phthalocyanine (to be called for short: H
2Pc), copper phthalocyanine (is called for short: CuPc) etc.
As the hole transporting material that is used to form hole transporting layer 112, the compound of aromatic amine (that is, having phenyl ring-nitrogen key) preferably.As extensive operational material, for example can enumerate: 4,4 '-two [N-(3-aminomethyl phenyl)-N-phenyl amino] biphenyl (is called for short: TPD) and as 4 of its derivative, 4 '-two [N-(1-naphthyl)-N-phenyl amino] biphenyl (is called for short: α-NPD) or 4,4 ', 4 " three (N; N-diphenyl amino) triphenylamine (be called for short: TDATA), 4; 4 ', 4 " three [N-(3-aminomethyl phenyl)-N-phenyl amino] triphenylamine (is called for short: the MTDATA) asterism of Denging (ス one バ one ス ト) type aromatic amine compounds.
As the hole barrier layer material that is used to form hole blocking layer 114, can use two (2-methyl-8-quinolinolate)-4-phenyl aluminium phenolates (to be called for short: BAlq), 1, two [the 5-(to tert-butyl-phenyl)-1 of 3-, 3,4- diazole-2-yl] benzene (abbreviation: OXD-7), 3-(4-tert-butyl-phenyl)-4-phenyl-5-(4-xenyl)-1,2, the 4-triazole (is called for short: TAZ), 3-(4-tert-butyl-phenyl)-4-(4-ethylphenyl)-5-(4-xenyl)-1,2, the 4-triazole (is called for short: P-EtTAZ), 4,7-phenylbenzene-1, the 10-phenanthroline (is called for short: BPhen), molten copper spirit (is called for short: BCP) etc.
As the electron transport materials when forming electron supplying layer 115, preferably three (8-quinolinolate) aluminium (is called for short: Alq
3), three (5-methyl-8-quinolinolate) aluminium (is called for short: Almq
3), two (10-hydroxy benzo [h]-quinolinic acid) beryllium (is called for short: BeBq
2), BAlq As mentioned above etc. has the metal complexes of chinoline backbone or benzoquinoline skeleton.Can also enumerate two [2-(2-hydroxyphenyl)-benzoxazol acid] zinc in addition (is called for short: Zn (BOX)
2), two [2-(2-hydroxyphenyl)-benzothiazoleacetic acid] zinc (is called for short: Zn (BTZ)
2) wait have the azole, the metal complexes of thiazoles ligand.And then, except metal complexes, 2-(4-xenyl)-5-(4-tert-butyl-phenyl)-1,3,4- diazole (is called for short: PBD) or at the OXD-7 that above addresses, TAZ, p-EtTAZ, Bphen, BCP etc. also can be used as the electron transport materials use.
According to above-mentioned method, can form a kind of electroluminescent cell of hole injection layer 111, hole transporting layer 112, hole blocking layer 114 and the electron supplying layer 115 that has the luminescent layer 113 that contains organometallic complex of the present invention, constitutes by low molecule based material.
Should illustrate that the present embodiment 1 is a kind of with the light that sent by the organometallic complex of the present invention electroluminescent cell as glow color.
[embodiment 2]
In the present embodiment 2, utilize Fig. 2 to illustrate and a kind ofly have the luminescent layer that contains organometallic complex of the present invention, and the hole injection layer that constitutes by the macromolecular material, and its element of handling the electroluminescent cell that forms is constituted by the wet processed method.
Should give explanation,, can use with embodiment 1 identical materials also to form after the same method, therefore omit its explanation for substrate the 200, the 1st electrode the 201, the 2nd electrode 203.
In addition, in the present embodiment 2, by hole injection layer 211, luminescent layer 212 laminations are formed electroluminescent layer 202.
As the hole-injecting material that is used to form hole injection layer 211, can use to be doped with polystyrolsulfon acid (be called for short: polyethylene dihydroxyl thiophene PSS) (is called for short: PEDOT) or be doped with four cyano quino-bismethane and (be called for short: TCNQ) wait the polyaniline of acceptor (to be called for short: PAni) or Polyvinyl carbazole (abbreviation: PVK) etc.
According to above-mentioned method, can obtain a kind of hole injection layer 211 that has the luminescent layer 212 that contains organometallic complex of the present invention, constitutes by high score subclass material, and it be handled the electroluminescent cell that forms by the wet processed method.
Should illustrate that the present embodiment 2 is a kind of light that sends with organometallic complex of the present invention electroluminescent cells as glow color.
[embodiment 3]
In the present embodiment 3, utilize that Fig. 3 illustrates a kind of luminescent layer with two kinds of guest materialss that contain organometallic complex of the present invention and fluorescence compound, the element of the electroluminescent cell of the hole injection layer, hole transporting layer, hole blocking layer and the electron supplying layer that are made of low branch subclass material constitutes.
Should illustrate, for substrate the 300, the 1st electrode the 301, the 2nd electrode 303, hole injection layer 311, hole transporting layer 312, hole blocking layer 314, electron supplying layer 315, can use with embodiment 1 identical materials also to form after the same method, therefore omit its explanation.
In addition, in the present embodiment 3, by hole injection layer 311, hole transporting layer 312, luminescent layer 313, hole blocking layer 314, electron supplying layer 315 laminations are formed electroluminescent layer 302.
The luminescent layer 313 of the present embodiment is by material of main part, as the organometallic complex of the present invention of first guest materials, constitute as the fluorescence compound of second guest materials.As material of main part, can use the material of in embodiment 1, addressing.
In addition,, can use known fluorescence compound, can use DCM1, DCM2, DCJTB, quinoline a word used for translation ketone, N particularly, N-dimethyl quinoline a word used for translation ketone, rubrene, perylene, DPT, Co-6, PMDFB, BTX, ABTX etc. as second guest materials.
In the present embodiment 3.Same with non-patent literature 6, in luminescent layer 313, organometallic complex of the present invention as first guest materials works as a kind of material of sensibilized that causes, it impels the amount as a heavy excited state of the fluorescence compound of second guest materials to increase.Therefore, the electroluminescent cell of the present embodiment 3 is a kind of with the light that sent by the fluorescence compound luminous element as glow color, and its luminous efficiency increases than the electroluminescent cell that uses traditional fluorescence compound.
[embodiment]
Embodiment of the present invention are described with reference to the accompanying drawings.But the present invention can implement by many different schemes, can carry out various changes to its scheme and detailed step under the condition that does not break away from main thought of the present invention and scope thereof, so long as those skilled in the art can understand easily.Therefore, the present invention can not be interpreted as only being defined in the content that the present embodiment is put down in writing.
(synthesis example 1)
The organometallic complex of the present invention that example illustrates by said structure formula (13) expression in this synthesis example (is called for short: Ir (ppt)
2(acac)) synthetic method.
[step 1: ligand (ppt) synthetic]
At first, use orthodichlorobenzene 20ml as solvent, to wherein being mixed into thiodiphenylamine (Tokyo changes into industrial society system) 2.35g (11.8mmol), 2-iodine pyridine (Tokyo changes into industrial society system) 3.63g (17.7mmol), salt of wormwood 6.55g, copper powder 1.5g, 18-hat-6-ether 0.31g, in nitrogen atmosphere, refluxed 16 hours.Then, remove copper and inorganic salt, in toluene solvant, carry out column purification, obtain ligand ppt (10-(2-pyridyl) thiodiphenylamine) (off-white powder, yield 70%) thus.The summary of synthetic route is shown in following (a-1).
Should give explanation, when measuring the IR absorption spectrum of the off-white powder that obtains, find, from the N-H stretching vibration (3340cm of thiodiphenylamine
-1) disappear, this shows and reacts.
[step 2: polynuclear coordination compound title complex ([Ir (ppt)
2Cl]
2) synthetic]
Then, with the mixed solution of cellosolvo 30ml and water 10ml as solvent, with ppt 1.19g (4.3mmol), the iridium chloride (IrCl of itself and above-mentioned acquisition
3HClH
2O) (KISHIDA chemistry society system) 0.50g (1.7mmol) mixes, and refluxes 18 hours in nitrogen atmosphere, has obtained polynuclear coordination compound title complex [Ir (ppt)
2Cl]
2(yellow powder, yield 70%).The summary of synthetic route is shown in following (b-1).
[step 3: organometallic complex of the present invention (Ir (ppt)
2Synthesizing (acac))]
And then, with cellosolvo 30ml as solvent, with [the Ir (ppt) of itself and above-mentioned acquisition
2Cl]
20.78g (0.50mmol), methyl ethyl diketone 0.15ml (1.5mmol), yellow soda ash 0.53g mix, in nitrogen atmosphere, refluxed 18 hours.The yellow powder that is obtained is carried out column purification with methylene dichloride as solvent, obtained organometallic complex Ir of the present invention (ppt)
2(acac) (yellow powder, yield 60%).The summary of synthetic route is shown in following (c-1).
Should give explanation, when the yellow powder that is obtained is carried out mass spectroscopy (ESI-MS), find, as Ir (ppt)
2(acac) (chemical formula C
39H
29IrN
4O
2S
2, molecular weight: m/z 840,841,842,843,844 places before and after the molecular weight 842) observe isotopic ion.In addition, as Ir (ppt)
2(acac) sodium affixture observes same isotopic ion at m/z 863,864,865,866,867 places.Coming to the same thing of the figure of the ionic strength of these isotopic peaks and Theoretical Calculation.Therefore, can think and obtained organometallic complex Ir of the present invention (ppt) by said structure formula (13) expression
2(acac).
In addition, the measurement result of IH-NMR (DMSO-d6) is as follows.
δ/ppm＝8.29(d，2H)、7.69(t，2H)、7.46(t，2H)、7.16(d，2H)、7.08(t，2H)、7.00(t，2H)、6.90(t，2H)、6.71(d，4H)、6.62(d，2H)、6.46(d，2H)、5.74(s，1H)、1.93(s，6H)。
In addition, utilizing TG-DTA to measure the organometallic complex Ir of the present invention (ppt) that is obtained
2Find that Td=337 ℃, this shows that it has good thermotolerance during (acac) decomposition temperature Td.In addition, also have above-mentioned good yield, also very good aspect cost.
Secondly, Ir (ppt)
2(acac) absorption peak in ethylene dichloride is shown among Fig. 6.Should give explanation, in Fig. 6, also put down in writing the absorption peak of ligand ppt simultaneously.Ligand ppt has absorption peak near 280nm and 300nm.On the other hand, organometallic complex Ir of the present invention (ppt)
2(acac) near 4 positions (1) 300nm, (2) 350nm, (3) 380nm, (4) 425nm have absorption peak.
Absorption peak (1) is consistent basically with the absorption of ligand ppt, and it is the singlet π-π that is caused by ligand
*Migration.In addition, the absorption peak of (2), (3), (4) is the common distinctive absorption of organometallic complex in ortho metal complex etc., can analogize it and singlet MLCT migration, triplet state π-π
*Migration, triplet state MLCT migration etc. are corresponding.Particularly the absorption peak of (4) extends roomy bottom at visible waveband, can think, this is that triplet state MLCT moves distinctive absorption peak.That is to say, can think, Ir (ppt)
2(acac) to the direct sunshine of triplet excited state excite or energy state between to report to the leadship after accomplishing a task be a kind of possible compound.
In addition, Ir (ppt)
2(acac) emmission spectrum of powder (photoluminescence) is shown among Fig. 7.With 365nm as exciting light.As shown in Figure 7, show the green light that has glow peak for the 520nm place at normal temperatures.When considering the absorption peak of Fig. 6, can think that it is the phosphorescence that sends.
[comparative example 1]
The traditional complex of iridium that synthesizes by following structural formula (29) expression (is called for short: Ir (tpy)
2(acac)), utilize TG-DTA to measure its decomposition temperature T
d, the result is T
d=298 ℃.
On the other hand, the organometallic complex Ir of the present invention (ppt) that in synthesis example 1, addresses
2(acac) T
dBe 337 ℃, and traditional complex of iridium Ir (tpy)
2(acac) T
dLower nearly 40 ℃ than this value.Therefore show that the thermotolerance of organometallic complex of the present invention is also good.
(synthesis example 2)
The organometallic complex of the present invention that example illustrates by said structure formula (17) expression in this synthesis example (is called for short: Ir (ppx)
2(acac)) synthetic method.
[step 1: ligand (ppx) synthetic]
At first, as solvent, it is mixed with fen piperazine 1.73g, 2-iodine pyridine 2.90g, salt of wormwood 5.24g, copper powder 1.2g, 18-hat-6-ether 0.25g, in nitrogen atmosphere, refluxed 8 hours with orthodichlorobenzene 20ml.Then, remove copper and inorganic salt, in methylene dichloride flux, carry out column purification, obtained ligand ppx (1-(2-pyridyl) fen piperazine) (white powder, yield 91%).The summary of synthetic route is shown in following (a-2).
[step 2: polynuclear coordination compound ([Ir (ppx)
2Cl]
2) synthetic]
Then, with the mixed solution of cellosolvo 30ml and water 10ml as solvent, with ppx 2.18g, the iridium chloride (IrCl of itself and above-mentioned acquisition
3HClH
2O) 1.00g mixes, and refluxes 14 hours in nitrogen atmosphere, has obtained polynuclear coordination compound [Ir (ppx)
2Cl]
2(yellow powder, yield 96%).The summary of synthetic route is shown in following (b-2).
[step 3: organometallic complex of the present invention ([Ir (ppx)
2Synthesizing (acac)])]
And then, with cellosolvo 30ml as solvent, with [the Ir (ppx) of itself and above-mentioned acquisition
2Cl]
21.00g, methyl ethyl diketone (Hacac) 0.21ml, yellow soda ash 0.71g mix, in nitrogen atmosphere, refluxed 14 hours.The solid that is obtained is washed in water, ethanol, ether solvent, obtained organometallic complex Ir of the present invention (ppx)
2(acac) (yellow powder, yield 87%).The summary of synthetic route is shown in following (c-2).
In addition, when utilizing TG-DTA to measure the organometallic complex Ir of the present invention (ppx) that is obtained
2(acac) decomposition temperature T
dThe time, the result is T
d=345 ℃, with the Ir (tpy) of comparative example 1
2(acac) (T
d=298 ℃) compare, can think to show good thermotolerance.In addition, also have above-mentioned good yield like that, the cost aspect is also good.
In addition, the measurement result of 1H-NMR (DMSO-d6) is as follows.
δ/ppm＝7.78(d，2H)、7.69(t，2H)、7.31(d，2H)、7.20(m，6H)、7.01(d，2H)、6.79(t，2H)、6.50(d，2H)、6.39(t，2H)、5.61(d，2H)、4.97(s，1H)、1.62(s，6H)。
Secondly, with Ir (ppx)
2(acac) absorption spectrum in methylene dichloride and emmission spectrum (photoluminescence) are shown among Fig. 8.Organometallic complex Ir of the present invention (ppx)
2(acac) have absorption peak at 256nm, 314nm, 348nm and 410nm place, same with synthesis example 1, present a kind of common in ortho metal complex etc., be the peculiar absorption peak of organometallic complex.In addition, emmission spectrum has the peak at the 524nm place, is green light.
(synthesis example 3)
The organometallic complex of the present invention that example illustrates by said structure formula (18) expression in this synthesis example (is called for short: Ir (ppx)
2(pic)) synthetic method.As raw material, use polynuclear coordination compound [Ir (ppx) by step 2 acquisition of above-mentioned synthesis example 2
2Cl]
2
At first, with cellosolvo 30ml as solvent, with its with [Ir (ppx)
2Cl]
21.00g, pyridine carboxylic acid (pic) 0.25g, yellow soda ash 0.71g mix, in nitrogen atmosphere, refluxed 14 hours.Then, solid water, ethanol, ether solvent washing with being obtained have obtained organometallic complex Ir of the present invention (ppx)
2(pic) (yellow powder, yield 72%).The summary of synthetic route is shown in following (c-3).
In addition, when utilizing TG-DTA to measure the organometallic complex Ir of the present invention (ppx) that is obtained
2(pic) decomposition temperature T
dThe time, the result is T
d=396 ℃, with the Ir (tpy) of comparative example 1
2(acac) (T
d=298 ℃) compare, it demonstrates good thermotolerance as can be seen.In addition, also have above-mentioned good yield like that, the cost aspect is also good.
In addition, the measurement result of 1H-NMR (DMSO-d6) is as follows.
δ/ppm＝8.57(d，1H)、8.00(t，1H)、7.89(d，2H)、7.75(d，1H)、7.63(d，2H)、7.33(m，2H)、7.24(m，5H)、7.11(m，2H)、7.00(t，1H)、6.81(t，1H)、6.64(m，4H)、6.45(t，1H)、6.22(d，1H)、5.86(d，1H)、5.49(d，1H)。
Secondly, Ir (ppx)
2(pic) absorption spectrum in methylene dichloride and emmission spectrum (photoluminescence) are shown among Fig. 9.Organometallic complex Ir of the present invention (ppx)
2(pic) have absorption peak at 226nm, 314nm, 338nm and 396nm place, same with synthesis example 1, present a kind of common in ortho metal complex etc., be the peculiar absorption peak of organometallic complex.In addition, emmission spectrum has the peak at the 551nm place, is yellowish green light.
[embodiment 1]
A kind of organometallic complex of the present invention (Ir (ppx) that in synthesis example 2, obtains that uses of illustration particularly in the present embodiment by said structure formula (17) expression
2(acac)) as the electroluminescent cell of twinkler.Use structure shown in Figure 1 as component structure and use vacuum vapour deposition as becoming embrane method.Should give explanation, in the present embodiment, with the 1st electrode 101 as anode, with the 2nd electrode 103 as negative electrode.
At first, use the substrate 100 of tin indium oxide (ITO) film that has formed 110nm as the 1st electrode 101.The size of the 1st electrode 101 is that 2mm is square.The CuPc film that forms 20nm on the 1st electrode 101 is as hole injection layer 111, and the α-NPD film that then forms 30nm is as vacuum transfer layer 112.
And then, adopt CBP and Ir (ppx)
2(acac) method of evaporation forms the film of 30nm as luminescent layer 113 on hole transporting layer 112 altogether.At this moment, adjust evaporation rate, so that make Ir (ppx)
2(acac) in luminescent layer 113, contain 8wt% approximately.
Then, the BCP film that in turn forms 10nm is as hole blocking layer 114, and then the Alq of formation 20nm
3Film is as electron supplying layer 115.More than be equivalent to electroluminescent layer 102.At last, form the Calcium Fluoride (Fluorspan) film of 2nm and the aluminium film of 100nm, with it as the 2nd electrode 103.
The element characteristic of present embodiment has been shown among Figure 10.Figure 10 (a) is brightness-voltage characteristic, and Figure 10 (b) is brightness-current density characteristic, and Figure 10 (c) is current efficiency-light characteristic.By apply the voltage of 7.0v to this element, this element will be with 0.694mA/cm
2Current density by electric current, thereby with 118cd/m
2Brightness luminous.In addition, current efficiency at this moment is 17.0cd/A, and external quantum efficiency is about 5.5%.Therefore, can obtain to substantially exceed the high-level efficiency of those utilizations by the electroluminescent cell of a heavy excited state luminous (fluorescence).Can think that this is because electroluminescent cell of the present invention shows the cause by triplet excited state luminous (phosphorescence).
Figure 11 illustrates the emmission spectrum of the electroluminescent cell of present embodiment.As shown in figure 11, this is a kind ofly to have the green light of peak value at about 520nm place.Ir (ppx) in this and the solution shown in Figure 8
2(acac) emmission spectrum is consistent basically, and this fact shows, is by Ir (ppx) in the present embodiment
2(acac) luminous.Should give explanation, the cie color coordinate be (x, y)=(0.27,0.60).
[embodiment 2]
Utilize Fig. 4 to come a kind of light-emitting device that has an electroluminescent cell of the present invention in pixel portions is described in the present embodiment.Should give explanation, Fig. 4 (A) is the vertical view of expression light-emitting device, and Fig. 4 (B) is the sectional view of Fig. 4 (A) being cut open along A-A ' line.What be represented by dotted lines 401 is mains side driving circuits, the 402nd, and pixel portions, the 403rd, gate side driver circuit.In addition, the 404th, hermetic sealing substrate, the 405th, sealing agent, sealed dose 405 inboard that surrounds becomes space 407.
In addition, guiding distribution 408 is the distributions that are used for to mains side driving circuit 401 and gate side driver circuit 403 transmission input signals, and it is also accepted from the vision signal of the FPC that becomes external input terminals (flexible print circuit) 409, clocksignal, start signal, reset signal etc.Should give explanation,, printed circuit substrate (PWB) can be installed herein on this FPC though FPC is not shown in the drawings.In the described light-emitting device of this specification sheets, be not only limited to light-emitting device itself, and be also contained in the state that FPC or PWB wherein are installed.
Secondly, utilize Fig. 4 (B) that cross section structure is described.On substrate 410, formed driving circuit portion and pixel portions, but what illustrate herein is mains side driving circuit 401 and pixel portions 402 as driving circuit portion.
In addition, mains side driving loop 401 can form by the cmos circuit that is combined by n channel-style TFT 423 and p channel-style TFT 424.In addition, the TFT of formation driving circuit also can be formed by known cmos circuit, PMOS circuit or nmos circuit.In addition, it is one-piece type that the driving mechanism that forms driving circuit has been shown in the present embodiment on substrate, but this is optional, also can be not on substrate but externally form driving circuit.
In addition, pixel portions 402 forms with TFT 412 and its many pixels that are connected to the 1st electrode 413 on the drain electrode with TFT 411, current control by comprising switch.In addition, formed the insulant 414 of the end that is covered with the 1st electrode 413.Herein, form by the photosensitivity acrylic resin film that uses eurymeric.
In addition, reach good order and condition, form curved surface with curvature in the upper end or the bottom of insulant 414 in order to make the visual field.For example, at the photosensitivity acrylic resin that uses eurymeric during, preferably only form curved surface with radius-of-curvature (0.2 μ m～3 μ m) in the upper end of insulant 414 as the material of insulant 414.In addition,, can use those minus that when being subjected to photosensitive light action, becomes insoluble in etching reagent, perhaps be subjected to any in the deliquescent eurymeric of becoming as the time spent in etching reagent of light as insulant 414.
On the 1st electrode 413, form electroluminescent layer 416 and the 2nd electrode 417 respectively.Herein, the material as using in the 1st electrode 413 that plays anodize preferably uses the big material of work function.For example, can use the unitary film of ITO (tin indium oxide) film, indium zinc oxide (IZO) film, titanium nitride film, chromium film, tungsten film, Zn film, Pt film etc., with by titanium nitride film with the film formed lamination structure of aluminium as principal constituent, and by titanium nitride film and with aluminium as the film of principal constituent and the film formed 3-tier architecture of titanium nitride etc.In addition, when forming lamination structure,, can also play as the anodic function if adopt the low good resistive conductor of resistance as distribution.
In addition, electroluminescent layer 416 can form by vapour deposition method or the ink jet method of using deposition mask.In electroluminescent layer 416, can use an organometallic complex conduct of the present invention part wherein, itself and other combination of materials is used, as the material that can Gong be used in combination, can be low branch subclass material, also can be high score subclass material.In addition, as the material that can be used for electroluminescent layer, usually majority is that organic compound is pressed the situation that individual layer or lamination use, but in the present invention, also comprises the constituting an of part that mineral compound is used for the film that is made of organic compound.
And then the material as using in the 2nd electrode (negative electrode) 417 that forms on electroluminescent layer 416 preferably uses the little material of work function (Al, Ag, Li, Ca or their alloy MgAg, MgIn, AlLi, CaF
2Or CaN).In addition, when the occasion of light transmission the 2nd electrode 417 that produces by electroluminescent layer 416, as the 2nd electrode (negative electrode) 417, the preferred use by thickness thin metallic film and nesa coating (ITO (Indium sesquioxide stannic oxide alloy), Indium sesquioxide zinc oxide alloy (In
2O
3-ZnO), zinc oxide (ZnO) etc.) laminated film that forms.
And then, by hermetic sealing substrate 404 and device substrate 410 being fitted, form a kind of structure that in the space 407 that is surrounded by substrate 410, hermetic sealing substrate 404 and sealing agent 405, possesses electroluminescent cell 418 with sealing agent 405.Should give explanation, in space 407, except available rare gas element (nitrogen or argon etc.) is filled, also comprise the structure of using sealing agent 405 to fill.
In addition, as sealing agent 405, preferably using epoxy is resin.In addition, as these materials, the preferred material that does not see through moisture and oxygen as far as possible that uses.In addition, as the material that is used for hermetic sealing substrate 404, except using glass substrate or quartz base plate, can also use the plastic base that constitutes by FRP (fiberglass-reinforced plastic), PVF (fluorinated ethylene propylene), polyester film, polyester or acrylic acid or the like etc.
According to above method, can obtain to have the light-emitting device of electroluminescent cell of the present invention.
[embodiment 3]
In the present embodiment, use being had the various electrical equipments that the light-emitting device of electroluminescent cell of the present invention finishes describes.
Has the electrical equipment that the light-emitting device of electroluminescent cell of the present invention is made as use, can enumerate: pick up camera, digital camera, goggle-type indicating meter (being fixed in the indicating meter of head), navigationsystem, audio player (vehicle audio, audio gain device etc.), subnotebook PC, game machine, portable data assistance (mobile computer, mobile telephone, portable game machine or e-book etc.), has image playing device (can make multifunction digital CD (DVD) etc. can play recording medium specifically, and can show the display unit of its image) of recording medium etc.The particular instantiation of these electrical equipments is in Fig. 5.
Fig. 5 (A) is a display unit, wherein contains framework 5101, supports platform 5102, display part 5103, speaker portion 5104, image input terminal 5105 etc.Be used for above-mentioned display part 5103 by the light-emitting device that will have electroluminescent cell of the present invention, can make above-mentioned display unit.Should give explanation, said display unit comprises that Personal Computer is used, TV sends all information demonstration devices such as reception is used, the advertisement demonstration is used.
Fig. 5 (B) is a subnotebook PC, comprises main body 5201, framework 5202, display part 5203, keyboard 5204, external interface 5205, mouse 5206 etc.Be used for above-mentioned display part 5203 by the light-emitting device that will have electroluminescent cell of the present invention, can make above-mentioned notebook personal computer.
Fig. 5 (C) is a mobile computer, comprises main body 5301, display part 5302, switch 5303, operated key 5304, infrared rays inlet 5305 etc.Be used for above-mentioned display part 5302 by the light-emitting device that will have electroluminescent cell of the present invention, can make above-mentioned mobile computer.
Fig. 5 (D) is the portable image playing device (DVD playing device specifically) with recording medium, comprises main body 5401, framework 5402, display part A5403, display part B5404, recording medium (DVD etc.) reading part 5405, operated key 5406, speaker portion 5407 etc.The main displays image information of display part A5403, the main display text information of display part B5404 is used for above-mentioned display part A5403 and display part B5404 by the light-emitting device that will have electroluminescent cell of the present invention, can make above-mentioned image playing device.Should give explanation, in having the image playing device of recording medium, also comprise home-use game machine interior.
Fig. 5 (E) is goggle-type indicating meter (being fixed in the indicating meter of head), wherein comprises main body 5501, display part 5502, arm 5503.Be used for above-mentioned display part 5502 by the light-emitting device that will have electroluminescent cell of the present invention, can make above-mentioned goggle-type indicating meter.
Fig. 5 (F) is a pick up camera, wherein comprises main body 5601, display part 5602, framework 5603, external interface 5604, remote control acceptance division 5605, image pickup part 5606, battery 5607, sound input part 5608, operated key 5609, connects eye 5610 etc.Be used for above-mentioned display part 5602 by the light-emitting device that will have electroluminescent cell of the present invention, can make above-mentioned video recorder.
Fig. 5 (G) is a mobile telephone, wherein comprises main body 5701, framework 5702, display part 5703, sound input part 5704, audio output unit 5705, operated key 5706, outside Link Port 5707, antenna 5708 etc.Be used for above-mentioned display part 5703 by the light-emitting device that will have electroluminescent cell of the present invention, can make above-mentioned mobile telephone.Should give explanation, display part 5703 if under the background of black the literal of display white, then can reduce the current consumption of portable phone.
As mentioned above, the scope of application of light-emitting device with electroluminescent cell of the present invention is extremely wide, and this light-emitting device might be applicable to the electrical equipment in all various fields.
Industrial applicibility
According to the present invention, can provide ligand that a kind of use is easy to synthesize and can be with well The novel organometallic complex that yield obtains. Particularly can provide a kind of excellent heat resistance Novel organometallic complex.
In addition, by making electroluminescent cell with above-mentioned organometallic complex, can To provide luminous efficiency high electroluminescent cell. And then, by using above-mentioned electroluminescent Element is made light-emitting device, can provide electric energy consumption low light-emitting device.
Claims (25)
1. one kind contains the luminescent material that has by the organometallic complex of the structure of following general formula (1) expression,
R1～R7 represents any in hydrogen atom, halogen atom, low alkyl group, alkoxyl group, acyl group, nitro, cyano group, amino, dialkyl amido, ammonia diaryl base, vinyl, aryl, the heterocycle residue separately; X represents Sauerstoffatom or sulphur atom; Y represents 2-pyridyl, 2- azoles base or 2-thiazolyl; M represents the 9th family's atom or the 10th family's atom.
2. one kind contains the luminescent material that has by the organometallic complex of the structure of following general formula (2) expression,
R1～R7 represents any in hydrogen atom, halogen atom, low alkyl group, alkoxyl group, acyl group, nitro, cyano group, amino, dialkyl amido, ammonia diaryl base, vinyl, aryl, the heterocycle residue separately; X represents Sauerstoffatom or sulphur atom; Y represents 2-pyridyl, 2- azoles base or 2-thiazolyl etc.; M represents the 9th family's atom or the 10th family's atom, when described M was the 9th family's atomic time, and n=2, when M was the 10th family's atomic time, n=1; In addition, L represent to have the single anion type of beta-diketon structure the bidentate chelating ligand, have the single anion type of carboxyl the bidentate chelating ligand, have in the bidentate chelating ligand of single anion type of phenol hydroxyl any.
3. luminescent material as claimed in claim 1 or 2, wherein said Y are the 2-pyridyl.
4. one kind contains the luminescent material that has by the organometallic complex of the structure of following general formula (3) expression,
X represents Sauerstoffatom or sulphur atom, and in addition, M represents the 9th family's atom or the 10th family's atom.
5. one kind contains the luminescent material that has by the organometallic complex of the structure of following general formula (4) expression,
X represents Sauerstoffatom or sulphur atom; M represents the 9th family's atom or the 10th family's atom, when described M was the 9th family's atomic time, and n=2, when M was the 10th family's atomic time, n=1; In addition, L represent to have the single anion type of beta-diketon structure the bidentate chelating ligand, have the single anion type of carboxyl the bidentate chelating ligand, have in the bidentate chelating ligand of single anion type of phenol hydroxyl any.
6. luminescent material as claimed in claim 1, wherein said M are iridium or platinum.
7. luminescent material as claimed in claim 2, wherein said M are iridium or platinum.
8. luminescent material as claimed in claim 4, wherein said M are iridium or platinum.
9. luminescent material as claimed in claim 5, wherein said M are iridium or platinum.
10. luminous organic material as claimed in claim 2, wherein said L are any in the bidentate chelating ligand of the single anion type shown in the following structural formula (5) to (11),
11. luminous organic material as claimed in claim 5, wherein said L are in the bidentate chelating ligand of the single anion type shown in the following structural formula (5) to (11) any,
12. an electronics, its have use claim 1,2,4,5 each described in the electroluminescent cell of luminescent material.
13. a luminescent material, it contains the organometallic complex that has by the structure of following general formula (1) expression,
R
2With R
3, R
4With R
5Interosculate separately, form aromatic ring; X represents Sauerstoffatom or sulphur atom; Y represents 2-pyridyl, 2- azoles base or 2-thiazolyl; M represents the 9th family's atom or the 10th family's atom.
14. a luminescent material, it contains the organometallic complex that has by the structure of following general formula (2) expression,
R
2With R
3, R
4With R
5Interosculate separately, form aromatic ring; X represents Sauerstoffatom or sulphur atom; Y represents 2-pyridyl, 2- azoles base or 2-thiazolyl; M represents the 9th family's atom or the 10th family's atom, when described M was the 9th family's atomic time, and n=2, when M was the 10th family's atomic time, n=1; In addition, L represent to have the single anion type of beta-diketon structure the bidentate chelating ligand, have the single anion type of carboxyl the bidentate chelating ligand, have any ligand in the bidentate chelating ligand of single anion type of phenol hydroxyl.
15. as claim 13 or 14 described luminescent materials, wherein said Y is the 2-pyridyl.
16. luminescent material as claimed in claim 13, wherein said M are iridium atom or pt atom.
17. luminescent material as claimed in claim 14, wherein said M are iridium atom or pt atom.
18. luminous organic material as claimed in claim 14, wherein said L are in the bidentate chelating ligand of the single anion type shown in the following structural formula (5) to (11) any,
19. an electronics, it has the electroluminescent cell that uses claim 13 or 14 described luminescent materials.
20. the organometallic complex of following general formula (1) expression,
R1～R7 represents any in hydrogen atom, halogen atom, low alkyl group, alkoxyl group, acyl group, nitro, cyano group, amino, dialkyl amido, ammonia diaryl base, vinyl, aryl, the heterocycle residue separately; X represents Sauerstoffatom or sulphur atom; Y represents 2-pyridyl, 2- azoles base or 2-thiazolyl; M represents the 9th family's atom or the 10th family's atom.
21. the organometallic complex of following general formula (2) expression,
R1～R7 represents any in hydrogen atom, halogen atom, low alkyl group, alkoxyl group, acyl group, nitro, cyano group, amino, dialkyl amido, ammonia diaryl base, vinyl, aryl, the heterocycle residue separately; X represents Sauerstoffatom or sulphur atom; Y represents 2-pyridyl, 2- azoles base or 2-thiazolyl etc.; M represents the 9th family's atom or the 10th family's atom, when described M was the 9th family's atomic time, and n=2, when M was the 10th family's atomic time, n=1; In addition, L represent to have the single anion type of beta-diketon structure the bidentate chelating ligand, have the single anion type of carboxyl the bidentate chelating ligand, have in the bidentate chelating ligand of single anion type of phenol hydroxyl any.
22. the organometallic complex of following general formula (3) expression,
X represents Sauerstoffatom or sulphur atom, and M represents the 9th family's atom or the 10th family's atom.
23. the organometallic complex of following general formula (4) expression,
X represents Sauerstoffatom or sulphur atom; M represents the 9th family's atom or the 10th family's atom, when described M was the 9th family's atomic time, and n=2, when M was the 10th family's atomic time, n=1; In addition, L represent to have the single anion type of beta-diketon structure the bidentate chelating ligand, have the single anion type of carboxyl the bidentate chelating ligand, have in the bidentate chelating ligand of single anion type of phenol hydroxyl any.
24. the organometallic complex of following general formula (1) expression,
R
2With R
3, R
4With R
5Interosculate separately, form aromatic ring; X represents Sauerstoffatom or sulphur atom; Y represents 2-pyridyl, 2- azoles base or 2-thiazolyl; M represents the 9th family's atom or the 10th family's atom.
25. the organometallic complex of following general formula (2) expression,
R
2With R
3, R
4With R
5Interosculate separately, form aromatic ring; X represents Sauerstoffatom or sulphur atom; Y represents 2-pyridyl, 2- azoles base or 2-thiazolyl; M represents the 9th family's atom or the 10th family's atom, when described M was the 9th family's atomic time, and n=2, when M was the 10th family's atomic time, n=1; In addition, L represent to have the single anion type of beta-diketon structure the bidentate chelating ligand, have the single anion type of carboxyl the bidentate chelating ligand, have any ligand in the bidentate chelating ligand of single anion type of phenol hydroxyl.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP035969/2003 | 2003-02-14 | ||
| JP2003035969 | 2003-02-14 | ||
| JP188960/2003 | 2003-06-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1751055A CN1751055A (en) | 2006-03-22 |
| CN100349908C true CN100349908C (en) | 2007-11-21 |
Family
ID=36605995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800042973A Expired - Fee Related CN100349908C (en) | 2003-02-14 | 2004-02-05 | Organic metal complex, electroluminescent material using the complex and ectroluminescent element using the complex |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100349908C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102134951B1 (en) | 2011-02-16 | 2020-07-16 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Light-emitting element |
| TWI641603B (en) * | 2013-08-09 | 2018-11-21 | Kyushu University, National University Corporation | Organic metal complex, light-emitting material, delayed fluorescence emitter and organic electroluminescence device |
| CN103819423B (en) * | 2014-02-13 | 2015-04-15 | 江苏傲伦达科技实业股份有限公司 | Method for synthesizing N-aryl-phenoxazine compounds |
| CN107001336A (en) * | 2014-12-11 | 2017-08-01 | 广州华睿光电材料有限公司 | A kind of organometallic complex, the polymer comprising it, mixture, composition, organic electronic device and application |
| US9724651B2 (en) * | 2015-07-14 | 2017-08-08 | Lg Nanoh2O, Inc. | Chemical additives for water flux enhancement |
| WO2017092545A1 (en) * | 2015-12-04 | 2017-06-08 | 广州华睿光电材料有限公司 | Organometallic complex and application thereof in electronic device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996010617A1 (en) * | 1994-09-30 | 1996-04-11 | Hoechst Aktiengesellschaft | Poly(paraphenylene vinylene) derivatives and their use as electroluminescent materials |
| WO1996017035A1 (en) * | 1994-11-25 | 1996-06-06 | Hoechst Aktiengesellschaft | Heterospiro-compounds and their use as electroluminescent materials |
| WO2000026323A1 (en) * | 1998-11-02 | 2000-05-11 | South Bank University Enterprises Ltd. | Electrolumiscent materials |
| WO2001018144A1 (en) * | 1999-09-06 | 2001-03-15 | Sekisui Chemical Co., Ltd. | Photocurable pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| US20020034656A1 (en) * | 1998-09-14 | 2002-03-21 | Thompson Mark E. | Organometallic complexes as phosphorescent emitters in organic LEDs |
| EP1191613A2 (en) * | 2000-09-26 | 2002-03-27 | Canon Kabushiki Kaisha | Luminescence device, display apparatus and metal coordination compound |
-
2004
- 2004-02-05 CN CNB2004800042973A patent/CN100349908C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996010617A1 (en) * | 1994-09-30 | 1996-04-11 | Hoechst Aktiengesellschaft | Poly(paraphenylene vinylene) derivatives and their use as electroluminescent materials |
| WO1996017035A1 (en) * | 1994-11-25 | 1996-06-06 | Hoechst Aktiengesellschaft | Heterospiro-compounds and their use as electroluminescent materials |
| US20020034656A1 (en) * | 1998-09-14 | 2002-03-21 | Thompson Mark E. | Organometallic complexes as phosphorescent emitters in organic LEDs |
| WO2000026323A1 (en) * | 1998-11-02 | 2000-05-11 | South Bank University Enterprises Ltd. | Electrolumiscent materials |
| WO2001018144A1 (en) * | 1999-09-06 | 2001-03-15 | Sekisui Chemical Co., Ltd. | Photocurable pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| EP1191613A2 (en) * | 2000-09-26 | 2002-03-27 | Canon Kabushiki Kaisha | Luminescence device, display apparatus and metal coordination compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1751055A (en) | 2006-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101435503B1 (en) | Light-emitting device | |
| JP4913122B2 (en) | Red phosphorescent compound and organic electroluminescent device using the same | |
| JP5171910B2 (en) | Binuclear complex, organometallic complex, and method for producing organometallic complex | |
| CN1890255A (en) | Organic metal complex and light-emitting device using same | |
| JP4913121B2 (en) | Red phosphorescent compound and organic electroluminescent device using the same | |
| CN106229417B (en) | Light-emitting device, electronic equipment and the lighting device to be shone using phosphorescence | |
| KR101540037B1 (en) | Quinoxaline derivative, and light emitting element, light emitting device, and electronic appliance using the same | |
| CN101074245A (en) | Phosphorescent heteronuclear copper(I)-iridium(III) complex and organic electroluminescence device using the same | |
| CN1781912A (en) | Organic metal complex and photoelectronic device, light-emitting element and light-emitting device using thereof | |
| CN1866576A (en) | Light emitting device and electronic appliance using the same | |
| CN1628491A (en) | Organic light emitting devices having carrier transporting layers comprising metal complexes | |
| CN1777592A (en) | Quinoxaline derivatives, and organic semiconductor devices, electroluminescent devices and electronic appliances, made by using the derivatives | |
| CN1911943A (en) | Organometallic complex, and light emitting element and electronic appliance using the same | |
| CN1609101A (en) | Organometallic complex and light-emitting element containing the same | |
| CN1487778A (en) | 1,3,6,8-tetra substituted pyrene compound, organic electroluminescent elements using the same compound, and organis electroluminescent display device | |
| CN1681828A (en) | Organic light emitting materials with anionic ligand | |
| CN1397148A (en) | Luminescent element material and luminescent element comprising the same | |
| CN1413426A (en) | Complexes of form L2MX as phosphorescent dopants for organic LEDS | |
| CN1788012A (en) | Phenyl-pyrazole complexes of Ir | |
| CN1681904A (en) | Organic light emitting materials and devices | |
| CN1610465A (en) | Light emitting element and light emitting device | |
| CN1881649A (en) | Organic electroluminescence device and manufacturing method thereof | |
| CN1829702A (en) | Quinoxaline derivative and luminescent element comprising the same | |
| CN1513045A (en) | Organic light-emitting device and light-emitting apparatus comprising the device | |
| CN1934909A (en) | Material for organic electroluminescent element and organic electroluminescent element using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071121 Termination date: 20210205 |