CN1957645A - Light-emitting element and light-emitting device - Google Patents

Light-emitting element and light-emitting device Download PDF

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CN1957645A
CN1957645A CN 200580016049 CN200580016049A CN1957645A CN 1957645 A CN1957645 A CN 1957645A CN 200580016049 CN200580016049 CN 200580016049 CN 200580016049 A CN200580016049 A CN 200580016049A CN 1957645 A CN1957645 A CN 1957645A
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light
organometallic complex
emitting component
luminescent layer
family
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CN100482024C (en
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大泽信晴
安部宽子
井上英子
下垣智子
瀬尾哲史
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Semiconductor Energy Laboratory Co Ltd
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Semiconductor Energy Laboratory Co Ltd
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Abstract

It is an object of the present invention to obtain an organometallic complex that is capable of converting an excited triplet state into luminescence, a light-emitting element that can be driven for a long time, is high in luminous efficiency, and has a favorable long lifetime, and a light-emitting device using the light-emitting element. The present invention provides a light-emitting element that has a pair of electrodes (an anode and a cathode) and a light-emitting layer between a pair of electrodes, where the light-emitting layer includes an organometallic complex represented by the following general formula (5) and one of a compound that has a larger energy gap than the organometallic complex and a compound that has a larger ionization potential and a smaller electron affinity than the organometallic complex, and provides a light-emitting device using the light-emitting device.

Description

Light-emitting component and light-emitting device
Technical field
The present invention relates to a kind ofly can convert the organometallic complex of light, a kind of light-emitting device that uses the light-emitting component of this organometallic complex and use this light-emitting component to being excited triplet.
Background technology
Using the light-emitting component of organic compound is a kind of like this element, and the layer or the organic compound thin film that wherein contain organic compound are luminous when applying electric field.It is said that its luminescence mechanism is as follows: when on the electrode that accompanies organic compound thin film therebetween, applying voltage, the electronics that injects from negative electrode and combine in organic compound thin film from the hole that anode injects and to form a molecule exciton releases energy when this molecule exciton returns ground state and luminous.
In this type of light-emitting component, organic compound layer forms about 1 micron or a following film usually.In addition, because this type of light-emitting component is the luminous therein element of a kind of organic compound itself, so needn't use in conventional LCD, use backlight.Therefore, one of this type of light-emitting component big advantage is to make not only thin but also gently.In addition, for example, in organic compound thin film on 100 to the 200nm orders of magnitude time, consider the mobility of organic compound thin film charge carrier, be injected into the compound time from charge carrier and be about for tens nanoseconds, light just can send in several microseconds, even the process that being compound to of charge carrier is luminous is included.Therefore, response speed also is one of feature soon.Again, inject light-emitting component, can use direct voltage drive, be not easy to produce noise because this type of light-emitting component is a kind of charge carrier.As for driving voltage, when the organic compound film be film, the electrode material of uniform thick about 100nm select can reduce organic compound thin film charge carrier inject barrier and introduce heterostructure further when (referring to double-decker here), can realize 100cd/m at 5.5 volts 2Adequate brightness (for example, participate in non-patent literature 1).
(non-patent literature 1)
C.W.Tang etc., Applied Physics Letter, the 51st volume, the 12nd phase, 913-915 page or leaf (1987).
Except the element characteristic of thin, light, high-speed response, dc low-voltage driving and so on, the luminous color of the light-emitting component of use organic compound is full of variety and also can be described as a big advantage, and reason just is that organic compound itself is abundant.That is, can be neatly develop the material that is used for various glow colors and brought up the rich of color by MOLECULE DESIGN (for example introducing substituting group) or similar approach.So to say that, the largest application areas of utilizing the rich light-emitting component of this color is panchromatic flat-panel monitor, because the many organic compounds that can launch the three primary colors red, green, blue are arranged, thereby, can realize panchromatic image easily by the patterning (patterning) of organic compound.
The element characteristic that we can say that the above is thin, light, high-speed response, dc low-voltage drives and so on also is the appropriate characteristics of flat-panel monitor.Yet, attempting using phosphor material rather than fluorescent material to attempt further to improve luminous efficiency in recent years.For the light-emitting component that uses organic compound, light results from the molecule exciton and returns in the ground state, and this light can be to come from excited singlet state (S *) light (fluorescence) or come from excited triplet state (T *) light (phosphorescence).When using fluorescent material, that makes contributions only comes from S *Light (fluorescence).
Yet, generally believe S *With T *Between statistics generation ratio be S *: T *=1: 3 (for example, referring to non-patent literatures 2).Therefore, for the light-emitting component that uses fluorescent material, at S *: T *On=1: 3 the basis, the theoretical limit of internal quantum efficiency (photon of generation is to the ratio of the charge carrier that injected) is considered to 25%.In other words, for the light-emitting component that uses fluorescent material, the charge carrier that is injected has at least 75% to be wasted meaninglessly.
(non-patent literature 2)
Tetsuo TSUTSUI work, Textbook for the 3 RdWorkshop, Division of MolecularElectronics and Bioelectronics, Japan Society of Applied Physics, p31 (1993).
On the contrary, come from T when using *Light when being phosphorescence, it is believed that optical efficiency can improve.Yet, in the organic material that generally uses, come from T *Light (phosphorescence) when room temperature, do not observe, only observe usually and come from S *Light (fluorescence).This is because the ground state of organic compound singlet state ground state (S normally 0), thereby, T *→ S 0Transition is the transition of forbidding, and S *→ S 0Transition be the permission transition.In the reality, issued one and another light-emitting component in recent years, wherein from T *The energy of launching when returning ground state (calling the triplet excitation energy in the following text) can be converted into light (for example, participating in non-patent literature 3).
(non-patent literature 3)
Tetsuo TSUTSUI etc., Japanese Journal of Applied Physics, the 38th volume, ppL1502-L1504 (1999).
In non-patent literature 3, do luminescent material with iridium as the metal complex (calling " complex of iridium " in the following text) of central metal with a kind of, can regard one of feature as central metal the element of the 3rd transition system is introduced.This metal complex is a kind of material (calling " triplet luminescent material " in the following text) that excited triplet state at room temperature can be converted to light.As described in non-patent literature 3, use can convert triplet excitation to the light-emitting component of the organic compound of light and can realize than whenever all high in the past internal quantum efficiency.Again, when having realized higher internal quantum efficiency, luminous efficiency (1m/W) has also just been improved.
Yet according to the report of non-patent literature 3, the photocontrol of starting originally is at 500cd/m 2Weighing apparatus stream when driving, the luminous half-life is about 170 hours, so, use the light-emitting component of triplet luminescent material to exist the problem in useful life.On the other hand, for the light-emitting component that uses the singlet state luminescent material, the photocontrol of starting originally is at 500cd/m 2Weighing apparatus stream when driving, the luminous half-life reaches several thousand to 10,000 hours, so, we can say that this light-emitting component has practical value with regard to the life-span.
Therefore, in the light-emitting component that uses the triplet luminescent material, need a kind of element that can drive for a long time.This is because can obtain luminous efficiency height, long light-emitting component of life-span.
Summary of the invention
In view of the technical background of light-emitting component, the objective of the invention is to solve the problems of the prior art.The purpose of this invention is to provide a kind of material that can launch phosphorescence.Using and excited triplet state can being converted in the light-emitting component of luminous organometallic complex, the purpose of this invention is to provide a kind of can the driving for a long time, that is, and luminous efficiency height, long light-emitting component of life-span.Again, the objective of the invention is by use a kind of light-emitting component provide a kind of can be for a long time with the low-power consumption driven light emitting device.
The inventor has done a large amount of careful test and research in order to realize target, the final discovery: the organometallic complex with any one the represented structure in the general formula (1) to (4) can be launched phosphorescence, and the organometallic complex with any one the represented structure in the general formula (5) to (8) can be launched and can finish phosphorescence of the present invention.
The inventor has done a large amount of careful test and research in order to realize target, the final discovery: providing pair of electrodes (anode and a negative electrode) and at least one in this light-emitting component that layer that includes organic compounds between electrode is formed, when comprising specific compound in the one deck at least in the layer that is including organic compounds, can obtain and to drive for a long time, be luminous efficiency height, long light-emitting component of life-span, finish the present invention.
The inventor has done a large amount of careful test and research in order to realize target, and finally using described light-emitting component to finish can be with the long-time driven light emitting device of low-power consumption.
Below will narrate organometallic complex according to the present invention, light-emitting component and light-emitting device in regular turn.
According to a kind of organometallic complex in the organometallic complex of the present invention is the organometallic complex with the represented structure of following general formula (1).
Figure A20058001604900161
In general formula (1), R 1To R 5Each is selected from down any one that organize naturally: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group and heterocyclic radical, Ar are a kind of in aryl and the heterocyclic radical, and M is a kind of in the 9th family's element and the 10th family's element.Preferably, Ar has the aryl of electron withdraw group and has a kind of in the heterocyclic radical of electron withdraw group.When Ar is when having the aryl of electron withdraw group and having a kind of in the heterocyclic radical of electron withdraw group, can launch the phosphorescence of big emissive porwer.
Again, first light-emitting component according to the present invention is a kind of light-emitting component that comprises a luminescent layer between pair of electrodes, and wherein luminescent layer comprises the organometallic complex of (1) the represented structure that has general formula and has greater than the compound of the energy gap of this organometallic complex and have greater than the ionization potential of this organometallic complex and a kind of less than in the compound of the electron affinity of this organometallic complex.
According to a kind of organometallic complex in the organometallic complex of the present invention is the organometallic complex with the represented structure of following general formula (2).
In general formula (2), R 1To R 9Each is selected from down group any one naturally: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group and heterocyclic radical, R 6To R 9In at least a be electron withdraw group, M is a kind of in the 9th family's element and the 10th family's element.Work as R 6To R 9In at least a when being electron withdraw group, can launch the phosphorescence of big emissive porwer.
Again, second light-emitting component according to the present invention is a kind of light-emitting component that comprises a luminescent layer between pair of electrodes, and wherein luminescent layer comprises the organometallic complex of (2) the represented structure that has general formula and has greater than the compound of the energy gap of this organometallic complex and have greater than the ionization potential of this organometallic complex and a kind of less than in the compound of the electron affinity of this organometallic complex.
According to a kind of organometallic complex in the organometallic complex of the present invention is the organometallic complex with the represented structure of following general formula (3).
Figure A20058001604900172
In general formula (3), R 2To R 14Each is selected from down any one that organize naturally: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group, heterocyclic radical and electron withdraw group, M are a kind of in the 9th family's element and the 10th family's element.Preferably, R 6To R 9In at least a be electron withdraw group.This makes the phosphorescence of launching big emissive porwer become possibility.
Again, the 3rd light-emitting component according to the present invention is a kind of light-emitting component that comprises a luminescent layer between pair of electrodes, and wherein luminescent layer comprises the organometallic complex of (3) the represented structure that has general formula and has greater than the compound of the energy gap of this organometallic complex and have greater than the ionization potential of this organometallic complex and a kind of less than in the compound of the electron affinity of this organometallic complex.
According to a kind of organometallic complex in the organometallic complex of the present invention is the organometallic complex with the represented structure of following general formula (4).
Figure A20058001604900181
In general formula (4), R 15And R 16Each is selected from down any one that organize naturally: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group, heterocyclic radical and electron withdraw group, M are a kind of in the 9th family's element and the 10th family's element.Preferably, R 16It is electron withdraw group.This makes the phosphorescence of launching big emissive porwer become possibility.
Again, the 4th light-emitting component according to the present invention is a kind of light-emitting component that comprises a luminescent layer between pair of electrodes, and wherein luminescent layer comprises the organometallic complex of (4) the represented structure that has general formula and has greater than the compound of the energy gap of this organometallic complex and have greater than the ionization potential of this organometallic complex and a kind of less than in the compound of the electron affinity of this organometallic complex.
According to a kind of organometallic complex in the organometallic complex of the present invention is the organometallic complex with the represented structure of following general formula (5).
Figure A20058001604900182
In general formula (5), R 1To R 5Each is selected from down group any one naturally: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group and heterocyclic radical; Ar has the aryl of electron withdraw group and has a kind of in the heterocyclic radical of electron withdraw group; M is a kind of in the 9th family's element and the 10th family's element; n=2 when M is the element of the 9th family; and when M is the 10th group element n=1, L is a single anion ligand.When Ar is electron withdraw group, can launch the phosphorescence of big emissive porwer.
Again, the 5th light-emitting component according to the present invention is a kind of light-emitting component that comprises a luminescent layer between pair of electrodes, and wherein luminescent layer comprises the organometallic complex of (5) the represented structure that has general formula and has greater than the compound of the energy gap of this organometallic complex and have greater than the ionization potential of this organometallic complex and a kind of less than in the compound of the electron affinity of this organometallic complex.
According to a kind of organometallic complex in the organometallic complex of the present invention is the organometallic complex with the represented structure of following general formula (6).
Figure A20058001604900191
In general formula (6), R 1To R 5Each is selected from down group any one naturally: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group and heterocyclic radical, R 6To R 9Each is selected from down group any one naturally: hydrogen, acyl group, alkyl, alkoxyl, aryl, heterocyclic radical and electron withdraw group, preferred R 6To R 9In at least a be electron withdraw group, M is a kind of in the 9th family's element and the 10th family's element, n=2 when M is the element of the 9th family, and when M is the 10th group element n=1, L is any one in the single anion ligand with beta-diketon structure, the single anion bidentate ligand with carboxyl and the single anion bidentate ligand with phenolic hydroxyl group.Work as R 6To R 9In at least one be electron withdraw group, can launch the phosphorescence of big emissive porwer.
The invention provides organometallic complex, unless R by general formula (6) expression 1To R 9Each is hydrogen naturally, and anion ligand L is acetylacetone,2,4-pentanedione anion, perhaps R 6To R 9In at least one be not electron withdraw group.
Again, the 6th light-emitting component according to the present invention is a kind of light-emitting component that comprises a luminescent layer between pair of electrodes, and wherein luminescent layer comprises the organometallic complex of (6) the represented structure that has general formula and has greater than the compound of the energy gap of this organometallic complex and have greater than the ionization potential of this organometallic complex and a kind of less than in the compound of the electron affinity of this organometallic complex.
Should be pointed out that at open 2001-247859 (0086) Duan Zhongyong " (1-70) " of Japan special permission to have shown a kind of compound, and this compound corresponding to general formula (6) at R 1To R 9Each naturally hydrogen, M be that iridium, n are 2 and the organometallic complex of anion ligand L during corresponding to the acetylacetone,2,4-pentanedione anion, yet, in this compound, R 6To R 9Not electron withdraw group, but hydrogen.In addition, the synthetic method of compound, character or the like are not done at all to disclose in the open 2001-247859 of Japan's special permission.On the other hand, this compound is not included in according in the represented organometallic complex of general formula of the present invention (6), and R wherein 1To R 9Hydrogen, anion ligand L are anionic compound of acetylacetone,2,4-pentanedione or R wherein naturally for each 6To R 9All be hydrogen and not being not included in according in the organometallic complex by general formula (6) expression of the present invention with the compound of electron withdraw group.
(patent documentation 1)
The open 2001-247859 of Japan's special permission
According to a kind of organometallic complex in the organometallic complex of the present invention is the organometallic complex with the represented structure of following general formula (7).
Figure A20058001604900201
In general formula (7), R 2To R 14Each is selected from down group any one naturally: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group, heterocyclic radical and electron withdraw group; M is a kind of in the 9th family's element and the 10th family's element; n=2 when M is the element of the 9th family; and when M is the 10th group element n=1, L is an anion ligand.Preferably, R 6To R 9In at least one is an electron withdraw group.This makes the phosphorescence of launching big emissive porwer become possibility.
Again, the 7th light-emitting component according to the present invention is a kind of light-emitting component that comprises a luminescent layer between pair of electrodes, and wherein luminescent layer comprises the organometallic complex of (7) the represented structure that has general formula and has greater than the compound of the energy gap of this organometallic complex and have greater than the ionization potential of this organometallic complex and a kind of less than in the compound of the electron affinity of this organometallic complex.
According to a kind of organometallic complex in the organometallic complex of the present invention is the organometallic complex with the represented structure of following general formula (8).
Figure A20058001604900211
In general formula (8), R 15And R 16Each is selected from down group any one naturally: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group, heterocyclic radical and electron withdraw group; M is a kind of in the 9th family's element and the 10th family's element; n=2 when M is the element of the 9th family; and when M is the 10th group element n=1, L is an anion ligand.Preferably, R at least 16In one be electron withdraw group.This makes the phosphorescence of launching big emissive porwer become possibility.
Again, the 8th light-emitting component according to the present invention is a kind of light-emitting component that comprises a luminescent layer between pair of electrodes, and wherein luminescent layer comprises the organometallic complex of (8) the represented structure that has general formula and has greater than the compound of the energy gap of this organometallic complex and have greater than the ionization potential of this organometallic complex and a kind of less than in the compound of the electron affinity of this organometallic complex.
Here, have the organometallic complex of being represented by general formula (3) or (4) or having in the organometallic complex of being represented by general formula (7) or (8), electron withdraw group is preferably any one in halogen, haloalkyl, the cyano group.This has improved the colourity and the quantum efficiency of organometallic complex.In addition, fluorine-based is particularly preferred in the halogen group, and trifluoromethyl is particularly preferred in the haloalkyl.This has also improved electron trap efficient.
In the organometallic complex of general formula (7) or (8) expression, central metal M is heavy metal, particularly iridium or platinum preferably.This just can obtain heavy atoms effect.
The 9th light-emitting component according to the present invention is any one in first to the 8th light-emitting component, the compound that wherein has the energy gap bigger than organometallic complex is 4, a kind of in 4 '-two [N-(1-naphthyl)-N-phenyl amino] biphenyl and three (oxine closes) aluminium.
The tenth light-emitting component according to the present invention is any one in the 5th to the 8th light-emitting component, and wherein anion ligand L is a kind of in the single anion ligand with beta-diketon structure, the single anion bidentate ligand with carboxyl and the single anion bidentate ligand with phenolic hydroxyl group.
The 11 light-emitting component according to the present invention is any one in first to the 8th light-emitting component, and wherein luminescent layer comprises organometallic complex, big and electron mobility is equal to or greater than 10 than the energy gap of this organometallic complex -6Cm 2First compound of/Vs and/or than the energy gap of this organometallic complex big and hole mobility is equal to or greater than 10 -6Cm 2Second compound of/Vs.
The tenth two light emitting according to the present invention is any one in first to the 8th light-emitting component, and wherein luminescent layer comprises organometallic complex, electron affinity is equal to or greater than 10 less than this organometallic complex and electron mobility than the ionization potential of this organometallic complex is big -6Cm 2First compound of/Vs and/or than the ionization potential of this organometallic complex is big electron affinity is equal to or greater than 10 less than this organometallic complex and hole mobility -6Cm 2Second compound of/Vs.
The 13 light-emitting component according to the present invention is any one in the 11 or the tenth two light emitting, and wherein the hole transport compound is an aromatic amine compound, and the electric transmission compound is a metal complex.
The 14 light-emitting component according to the present invention is any one in the first to the 13 light-emitting component, and it further has at least a in hole injection layer, hole transmission layer, hole blocking layer, electron transfer layer and the electron injecting layer.
In addition, light-emitting device according to the present invention is the light-emitting device of any one manufacturing in a kind of use the first to the 14 light-emitting component.
According to the present invention, can obtain to launch the organometallic complex of phosphorescence.In addition, the light-emitting component with the luminescent layer that comprises this organometallic complex and the compound bigger than the energy gap of this organometallic complex can drive for a long time, luminous efficiency height, life-span be long.By using organometallic complex according to the present invention, can obtain a kind of colourity excellence, can produce the light-emitting component of ruddiness or little ruddiness as luminescent material.
In addition, by use according to of the present invention with organometallic complex as sensitizer, can obtain can efficiently luminous light-emitting component.Again, a kind of by using to the organometallic complex of wherein having introduced electron withdraw group, especially in organometallic complex scope according to the present invention, can obtain a kind of light-emitting component with splendid combined efficiency.
In addition, light-emitting device according to the present invention is because of using this light-emitting component excellent performance.
Description of drawings
In the accompanying drawing:
Fig. 1 is the figure that light emitting element structure of the present invention is shown;
Fig. 2 is the figure that light emitting element structure of the present invention is shown;
Fig. 3 is the figure that light-emitting device is shown;
Fig. 4 is the figure that the present invention's the 4th execution mode is shown;
Fig. 5 is the figure that the present invention's the 5th execution mode is shown;
Fig. 6 is the figure that the present invention's the 5th execution mode is shown;
Fig. 7 is the figure that the present invention's the 6th execution mode is shown;
Fig. 8 is the figure that the present invention's the 7th execution mode is shown;
Fig. 9 is the figure that the present invention's the 7th execution mode is shown;
Figure 10 is the figure that the present invention's the 7th execution mode is shown;
Figure 11 is the figure that the present invention's the 7th execution mode is shown;
Figure 12 A is the figure that shows the present invention's the 8th execution mode to 12C;
Figure 13 is the absorption spectrum and the emission spectrum figure of the organometallic complex that synthesis example 1 obtains in the execution mode 1;
Figure 14 is the absorption spectrum and the emission spectrum figure of the organometallic complex that synthesis example 2 obtains in the execution mode 1;
Figure 15 is the absorption spectrum and the emission spectrum figure of the organometallic complex that synthesis example 3 obtains in the execution mode 1;
Figure 16 is the absorption spectrum and the emission spectrum figure of the organometallic complex that synthesis example 4 obtains in the execution mode 1;
Figure 17 is the absorption spectrum and the emission spectrum figure of the organometallic complex that synthesis example 5 obtains in the execution mode 1;
Figure 18 A and 18B illustrate to show research organometallic complex [Ir (Fdpq) in the synthesis example 1 respectively 2(acac)] figure of the CV curve of oxidation characteristic and reduction characteristic;
Figure 19 illustrates the light emitting element structure in the execution mode 2 and the figure of manufacture method thereof;
Figure 20 A is the figure that is illustrated in the initial characteristic of the light-emitting component of making in the execution mode 2 to 20C;
Figure 21 is the figure that the result of the stable property testing of the light-emitting component of manufacturing in the execution mode 2 is shown;
Figure 22 illustrates the light emitting element structure of execution mode 3 and the figure of manufacture method thereof;
Figure 23 A is the figure that is illustrated in the initial characteristic of the light-emitting component of making in the execution mode 3 to 23C;
Figure 24 is the figure that the result of the stable property testing of the light-emitting component of manufacturing in the execution mode 3 is shown;
Figure 25 A is the figure that is illustrated in the initial characteristic of the light-emitting component of making in the execution mode 4 to 25C;
Figure 26 is the figure that the result of the stable property testing of the light-emitting component of manufacturing in the execution mode 4 is shown;
Figure 27 A is the figure that the operation characteristic of the light-emitting component of making in the execution mode 5 is shown to 27C;
Figure 28 is the figure that the result of the stable property testing of the light-emitting component of manufacturing in the execution mode 5 is shown;
Figure 29 A is the figure that the operation characteristic of the light-emitting component of making in the execution mode 6 is shown to 29C;
Figure 30 is the figure that the result of the stable property testing of the light-emitting component of manufacturing in the execution mode 6 is shown;
Figure 31 A is the figure that the operation characteristic of the light-emitting component of making in the execution mode 7 is shown to 31C;
Figure 32 is the figure that the result of the stable property testing of the light-emitting component of manufacturing in the execution mode 7 is shown;
Figure 33 A is the figure that the operation characteristic of the light-emitting component of making in the execution mode 8 is shown to 33C;
Figure 34 is the figure that the result of the stable property testing of the light-emitting component of manufacturing in the execution mode 8 is shown;
Figure 35 A and 35B are illustrated in the figure that pixel portion (pixel portion) has the light-emitting device (execution mode 9) according to light-emitting component of the present invention;
Figure 36 A is that the figure (execution mode 10) that has used according to the concrete example of the electronic equipment of light-emitting component of the present invention is shown to 36E;
Figure 37 is the figure that the topology example of a kind of white light emitting elements (execution mode 11) is shown;
Figure 38 is the figure that the structure of the white light emitting elements that uses phosphor material is shown, itself and structure different (execution modes 12) in the execution mode 11;
Figure 39 illustrates to use organometallic complex as the light-emitting component of luminescent material and the figure of manufacture method (execution mode 13) thereof;
Figure 40 is the figure that shows the emission spectrum of light-emitting component in the execution mode 13;
Figure 41 is presented in the execution mode 13 TPAQn's that uses 1The figure of H-NMR chart;
Figure 42 be illustrate use in synthesis example 3 synthetic organometallic complex as the light-emitting component of luminescent material and the figure of manufacture method (execution mode 14) thereof;
Figure 43 is the figure that shows the light-emitting component emission spectrum of making in the execution mode 14;
Figure 44 is the figure that shows the light-emitting component emission spectrum of making in the execution mode 15;
Figure 45 is the figure that shows the light-emitting component emission spectrum of making in the execution mode 16; And
Figure 46 is the figure that shows the light-emitting component emission spectrum of making in the execution mode 17.
Embodiment
Below the present invention is described in more detail.At first will describe according to organometallic complex of the present invention.The invention provides novel organometallic complex, the light-emitting component that uses this organometallic complex and the light-emitting device that uses this light-emitting component.
Substituent R described above 1To R 16Object lesson as follows.Acyl group comprises acetyl group, propiono, isobutyryl and methacryl.Alkyl comprises methyl, ethyl, n-pro-pyl, isopropyl, the tert-butyl group and octyl group.Alkoxyl comprises methoxyl group, ethyoxyl and propoxyl group.Aryl comprises phenyl, 4-aminomethyl phenyl and 4-ethylphenyl.Heterocyclic radical comprises pyridine radicals, bipyridyl and picolyl.Electron withdraw group comprises fluorine-based, three fluoro group and cyano group.
In addition, the object lesson of the 9th family or the 10th family's element comprises iridium and platinum.Yet the 9th family or the 10th family's element should not be thought of as these elements that are confined to provide as an example.
So ligand L is any one in the single anion ligand with beta-diketon structure, the single anion bidentate ligand with carboxyl and the single anion bidentate ligand with phenolic hydroxyl group.Its object lesson comprises the anion by following general formula (9) to (15) expression.These parts are effectively, and this is because their coordination abilities are strong, low price.
The typical example of organometallic complex comprises the organometallic complex of the structure that (1)-(4) that have general formula are represented, promptly by following general formula (5)-(8) represented organometallic complex.Yet organometallic complex should not regarded as and is confined to these compounds.
Figure A20058001604900262
Figure A20058001604900281
Figure A20058001604900291
Figure A20058001604900311
Figure A20058001604900321
Figure A20058001604900331
Figure A20058001604900341
Figure A20058001604900351
Above-mentionedly can launch phosphorescence according to organometallic complex of the present invention.In addition, can be applied to light-emitting component as luminescent material according to organometallic complex of the present invention.In addition, can be applied to light-emitting component as photosensitizer according to organometallic complex of the present invention.
(according to the synthetic method of organometallic complex of the present invention)
Next, with the manufacture method of describing according to organometallic complex of the present invention, i.e. synthetic method.According to organometallic complex of the present invention, promptly have respectively organometallic complex, promptly can obtain with the positive metallization (orthometallation) of part by the organometallic complex of general formula (5)-(8) expression respectively by the structure of general formula (1)-(4) expression.For example, has organometallic complex by the represented part of following general formula (56), promptly have the organometallic complex of the represented structure of general formula (3) or, can obtain by just metallization by the represented part of following general formula (56) by the represented organometallic complex of general formula (7).Below will narrate the method for synthesizing the represented organometallic complex of general formula (7) of using by the represented part of following general formula (56).
Figure A20058001604900371
In general formula (56), R 2To R 14Each is selected from down group any one naturally: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group, heterocyclic radical and electron withdraw group.
The part that should be noted that general formula (56) can for example synthesize according to following synthetic schemes.In addition, can synthesize with similar method according to another part in the organometallic complex of the present invention.
Figure A20058001604900372
In formula (57), R 2To R 14Each is selected from down group any one naturally: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group, heterocyclic radical and electron withdraw group.
So the part of the general formula (56) that obtains is used to the synthesis of organometallic complex.Following synthetic method can be used as the reaction (just metallizing) of this case.
For example, when synthetic according to of the present invention when being the organometallic complex of central metal with iridium, at first use the hydration iridium chloride as the synthetic a kind of chlorine bridge binuclear complex of the raw material of central metal, method is that the part of hydration iridium chloride with general formula (56) mixed mutually, and makes hydration iridium chloride and part keep mixing under the backflow situation in blanket of nitrogen.
Synthetic schemes is represented with following formula (58).
Figure A20058001604900382
In formula (58), R 2To R 14Each is selected from down group any one naturally: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group, heterocyclic radical and electron withdraw group.
Next, mix mutually and make this binuclear complex keep mixing in reflux state under blanket of nitrogen with part in ligand L by the binuclear complex that will be obtained, the chlorine bridge is promptly cut off by ligand L, and acquisition is according to organometallic complex of the present invention.
Synthetic schemes is represented by following formula (59).
In formula (59), R 2To R 14Each is selected from down group any one naturally: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group, heterocyclic radical and electron withdraw group.
Should be noted that the synthetic method according to organometallic complex of the present invention should not be considered as being confined to synthetic method described above.
(according to the execution mode of light-emitting component of the present invention)
Next with reference to the accompanying drawings light-emitting component according to the present invention is described.
[Implementation Modes 1]
In the Implementation Modes 1, light-emitting component according to the present invention is done description with reference to Fig. 1.
As shown in Figure 1, the structure of light-emitting component of the present invention is: on substrate 100, be formed with first electrode 101, be formed with on first electrode 101 comprise luminescent material the layer 102, the second electrode 103 be formed at the layer 102 on.As the material of substrate 100, can use the employed material of conventional light-emitting component.For example, can use glass, quartz, transparent plastic, flexible base, board etc.In addition, electrode 101 in the Implementation Modes 1 and electrode 103 are respectively as anode and negative electrode.
That is, first electrode, 101 usefulness anode materials form.Operable anode material preferably uses metal, alloy, conductive compound or their mixture with big work content (work content is being equal to or greater than 4.0eV).Object lesson as anode material, except that ITO (tin indium oxide), ITSO (tin indium oxide silicon) with mix the IZO (indium zinc oxide) that the indium oxide of 2 to 20% zinc oxide (ZnO) forms, can use metal such as gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu) or palladium (Pd) and the metal nitride materials such as TiN.
On the other hand, as the cathode material that can be used for second electrode 103, preferred metal, alloy, conductive compound or their mixture that use with less work content (work content is equal to or less than 3.8eV).Remove the element belong to the periodic table of elements the 1st family or the 2nd family, i.e. alkali metal such as Li and Cs and alkaline-earth metal such as Mg, Ca and Sr and comprise alloy (Mg:Ag or Al:Li) and compound (LiF, CsF, the CaF of this element 2) outside, the object lesson of cathode material can form second electrode 103 with the transition metal that comprises rare earth metal.Second electrode 103 can also form with above-mentioned material with as the laminate layers of a kind of metal (comprising alloy) of Al, Ag or ITO and so on.
The film that is formed by above-mentioned anode material and be to form by the method such as vapour deposition method or sputtering method by the film that above-mentioned cathode material forms is used for forming respectively first electrode 101 and second electrode 103, and the thickness of film is preferably 10 to 500nm.Finally, form a protective layer (barrier layer) of forming by inorganic material such as SiN or organic material such as Teflon (registered trade mark) or polystyrene.The barrier layer can be transparent or opaque, and inorganic material layer or organic material layer are to form with the method for evaporation or sputter and so on.
In light-emitting component of the present invention, the light by the compound generation of charge carrier in luminescent layer outwards penetrates from one of them or both of first electrode 101 and second electrode 103.That is, when light when first electrode 101 penetrates, first electrode, 101 usefulness light transmissive materials form, and when light during from 103 ejaculations of second electrode, second electrode, 103 usefulness light transmissive materials form.The layer 102 that comprises luminescent material forms by piling up a plurality of layers in Implementation Modes 1, promptly piles up hole injection layer 111, hole transmission layer 112, luminescent layer 113, hole blocking layer 114 and electron transfer layer 115 in regular turn.
In comprising the layer 102 of luminescent material, hole injection layer 111 is arranged to contact first electrode 101.In addition, preferred use a kind of material that can receive to form hole injection layer 111 from the hole of first electrode 101, and with a kind of can to second electrode, 103 sides that are arranged at hole injection layer 111, contact with hole injection layer 111 layer in the material formation of injected hole.Particularly, preferably form hole injection layer 111 with phthalocyanine compound.Phthalocyanine compound comprises for example phthalocyanine (abbreviation: H 2-Pc) and CuPc (abbreviation: Cu-Pc).
In addition, aromatic amine compound is such as 4, (the abbreviation: DNTPD), 4 of 4 '-two [N-{4-(N, N-a two-tolyl amino) phenyl }-N-phenyl amino] biphenyl, 4 ', 4 " [N-(3-aminomethyl phenyl)-N-phenyl amino]-triphenylamine (abbreviation: MTDATA))-three.In addition, can use conduction inorganic compound (comprising semiconductor), such as molybdenum oxide (MoOx), vanadium oxide (VOx).Can use the mixture of the aromatic amine compound of conduction inorganic compound and the above or the following stated again.This mixture can form with the method that is total to evaporation and so on.
Preferred use can transporting holes material, particularly aromatic amine compound (that is the compound that, has phenyl ring-nitrogen key) form hole transmission layer 112.For example, remove 4, (the abbreviation: of 4 '-two [N-(3-aminomethyl phenyl)-N-phenyl amino] biphenyl TPD) with 4,4 '-two [N-(1-naphthyl)-N-phenyl amino] biphenyl is (outside abbreviation: the α-NPB), star burst (starburst) aromatic amine compound is such as above-mentioned MTDATA and 4,4 ', 4 "-three (N, N-diphenyl amino) triphenylamine (abbreviation: TDATA) preferably be used for forming hole transmission layer 112.In addition, can use such as molybdenum oxide (MoOx) and vanadium oxide conduction inorganic compounds (comprising semiconductor) such as (VOx) mixture with above-mentioned aromatic amine compound.This mixture can form with the method that is total to vapour deposition method and so on.
Preferably, the common evaporation of at least a organometallic complex of luminescent layer 113 usefulness and a kind of matrix (host) material forms.Organometallic complex is a kind of organometallic complex with structure shown in one of general formula (1)-(4), or a kind of organometallic complex by the expression of one of general formula (5)-(8).Host material preferably uses to have than the big material of organometallic complex energy gap (Eg), and described organometallic complex has structure shown in one of general formula (1)-(4) or represented by one of general formula (5)-(8).
In addition, especially, host material preferably uses than organometallic complex has the material that has big ionization potential (Ip) and less electron affinity (EA) than big energy gap, again, and described organometallic complex has structure shown in one of general formula (1)-(4) or represented by one of general formula (5)-(8).Its example comprises 4,4 '-two (N-carbazyl) biphenyl (abbreviation: CBP), 4,4 ', 4 "-three (N-carbazyl) triphenylamine (abbreviation: TCTA) and 1,3, (the abbreviation: TCPB) of 5-three [4-(N-carbazyl) phenyl] benzene.Again, more preferably, host material by a kind of can transporting holes and electronics in the material of any one or two kinds of charge carriers form, particularly a kind of carrier mobility is equal to or greater than 10 -6Cm 2The material of/Vs.So just can reduce driving voltage and improve component reliability.
The object lesson that can be used as the material of host material comprises the (abbreviation: Alq of α-NPD and three (oxine closes) aluminium 3).Should be noted that the hole mobility among α-NPD is about 10 -4Cm 2/ Vs, the and (abbreviation: Alq of three (oxine closes) aluminium 3) electron mobility 10 -5Cm 2/ Vs.As mentioned above, any one in hole and the electronics or two kinds of mobility of charge carrier rates preferably are equal to or greater than 10 -6Cm 2/ Vs.Yet host material should not be considered as being confined to α-NPD and Alq 3, above-mentioned arylamine blend such as TPD and metal complex are as (the abbreviation: Gaq of three (oxine closes) gallium 3) and (abbreviation: Almq of three (4-methyl-oxine closes) aluminium 3) also can be used as host material and use.These materials, Alq 3, Gaq 3And Almq 3, corresponding to the example of electric transmission metal complex.
When the luminescent layer 113 that forms has structure described above, the transmission in luminescent layer 113 easily of hole and electronics, and these holes and electronics capture collection effectively in organometallic complex, and by luminescent layer, to produce light.Therefore, hole or electronics are not easy by luminescent layer, and that the formation of exciton just becomes is more effective.Correspondingly, can construct luminous efficiency (that is deterioration in brightness) the less stable equipment that successively decreases.
Organometallic complex by general formula (16)-(55) expression receives the hole easily owing to organic moiety-metallic bond, again because the quinoxaline skeleton also receives electronics easily.Therefore, organometallic complex has the advantage that charge carrier can effectively be captureed collection.
Should be pointed out that the organometallic complex that preferred usefulness has fluorine-based or a trifluoromethyl group forms luminescent layer 113, especially in the organometallic complex shown in general formula (16)-(55) by the organometallic complex of general formula (16) and (18) expression.This has expanded the range of choice of host material.In addition, especially, increased compatibility to electronics just produced electronics can be by the advantage of prisoner's collection more effectively.
The preferred material with big ionization potential that uses forms hole blocking layer 114, such as (the abbreviation: BAlq) of two (2-methyl-oxine)-4-phenyl phenol-aluminium, 1,3-two [5-(to tert-butyl-phenyl)-1,3,4- diazole-2-yl] benzene (abbreviation: OXD-7), 3-(4-tert-butyl-phenyl)-4-phenyl-5-(4-xenyl)-1,2, (the abbreviation: TAZ) of 4-triazole, 3-(4-tert-butyl-phenyl)-4-(4-ethylphenyl)-5-(4-xenyl)-1,2, (the abbreviation: p-EtTAZ) of 4-triazole, bathophenanthroline (abbreviation: Bphen), or bathocuproine (abbreviation: BCP), more preferably use a kind of material formation hole blocking layer 114 than the big at least 0.3eV of ionization potential of luminescent layer 113.So just can prevent to inject second electrode 103 of the hole flow direction of the layer 102 that comprises luminescent material as negative electrode from first electrode, 101 sides.In addition, can prevent that luminous energy from shifting towards electron transfer layer 115.
Preferably in comprising the layer 102 of luminescent material, use and to form electron transfer layer 115 towards luminescent layer 113 transmission from material as second electrode, 103 injected electrons of negative electrode.In addition, the preferred bigger material of material ionization potential that has than forming luminescent layer 113 that uses forms electron transfer layer 115.Yet, in as the present invention, provide in the situation of a hole transmission layer 114, be not always must use than the big material of material ionization potential that forms luminescent layer 113.
The object lesson of this type of material comprises the metal complex with chinoline backbone or benzoquinoline skeleton, such as Alq 3, Gaq 3, Almq 3, and two (10-hydroxy benzo [h]-oxyquinoline closes) beryllium (abbreviation: BeBq 2) and aforesaid BAlq.In addition, has the metal complex of  azoles part or thiazole part, such as two [2-(2-hydroxyphenyl) benzoxazol] zinc (bis[2-(2-hydroxyphenyl) benzoxazolato] zinc) (abbreviation: Zn (BOX) 2) and two [2-(2-hydroxyphenyl) benzothiazole] zinc (bis[2-(2-hydroxyphenyl) benzothiazolato] zinc) (abbreviation: Zn (BTZ) 2) also can be used as the material that forms electron transfer layer 115.Again, remove above-mentioned 2-(4-xenyl)-5-(4-tert-butyl-phenyl)-1,3, (the abbreviation: PBD), outside OXD-7, TAZ, p-EtTAZ, BPhen, the BCP, also can use the inorganic material such as titanium oxide of 4- diazole.
The light-emitting component brightness of the present invention of above-mentioned foundation is less with the reduction of launch time, and the life-span is good.
[Implementation Modes 2]
With reference to Fig. 2 light-emitting component of the present invention is described.
Light-emitting component as shown in Figure 2 have on the substrate 200 as first electrode 201 of negative electrode, at the layer 202 that comprises luminescent material on first electrode and comprising second electrode 203 on the layer 202 of luminescent material as anode.As shown in Figure 2, the layer 202 that comprises luminescent material forms by piling up an electron transfer layer 211, a hole blocking layer 212, a luminescent layer 213, a hole transmission layer 214 and a hole injection layer 215 in regular turn, wherein electron transfer layer 211 and hole transmission layer 214 are separately positioned on first electrode, 201 sides and second electrode, 203 sides, and luminescent layer 213 is in central authorities.
Electron transfer layer 211, hole blocking layer 212, luminescent layer 213, hole transmission layer 214, and hole injection layer 215 can use respectively with Implementation Modes 1 in describe electron transfer layer 115, hole blocking layer 114, luminescent layer 113, hole transmission layer 112, and hole injection layer 111 identical materials form by evaporation or similar approach.As mentioned above, can use a kind of light-emitting component that wherein is arranged at substrate-side as the electrode of negative electrode.Should be pointed out that in light-emitting component of the present invention the light that generates because of charge carrier is compound in 202 at the layer that comprises luminescent material is one of from first electrode 201 and third electrode 203 or both ejaculations.
The light-emitting component brightness of the present invention of above-mentioned foundation is less with the reduction of launch time, and the life-span is good.
[Implementation Modes 3]
In Implementation Modes 3, on substrate 300, make a kind of light-emitting component that has used according to organometallic complex of the present invention, substrate 300 wherein is made up of glass, quartz, metal, (bulk) in bulk semiconductor, transparent plastic, flexible base, board etc.The light-emitting component that forms a plurality of uses organometallic complex of the present invention on substrate has just produced the passive matrix of light-emitting device.In addition, be different from the substrate that glass, quartz, transparent plastic, flexible base, board etc. are formed, for example, can make as illustrated in fig. 3 with the contacted light-emitting component of thin-film transistor (TFT) array, wherein light-emitting component 313 is made in the lump together with TFT311 and 312.
For light-emitting component 313, can make first electrode 314, comprise luminescent material the layer 315, second electrode 316.Again, making distribution 317 makes it to contact with first electrode 314.So, the driving that can produce light-emitting component is controlled by the active matrix light-emitting device of TFT.The structure that should be pointed out that TFT is not particularly limited.For example, can use the staggered TFT and the staggered TFT that falls.In addition, the degree of crystallinity of the semiconductor layer of formation TFT also is not particularly limited.Can use crystalline semiconductor layer and amorphous semiconductor layer.
[Implementation Modes 4]
With reference to Fig. 4 the example of use organometallic complex according to the present invention as the light-emitting component of luminescent material described.
What Fig. 4 showed is the light-emitting component that has luminescent layer 413 between first electrode 401 and second electrode 402.In luminescent layer 413, comprise and have by the organometallic complex of any one represented structure in general formula of the present invention (1)-(4) or by the organometallic complex of one of general formula of the present invention (5)-(8) expression.
In this light-emitting component,, bring organometallic complex of the present invention into excitation state from first electrode, 401 injected holes and compound luminescent layer 413 from second electrode, 402 injected electrons.So, emission bright dipping when the organometallic complex of the present invention that is in excitation state returns ground state.As mentioned above, organometallic complex of the present invention is as luminescent material.Should be pointed out that first electrode 401 and second electrode 402 are respectively as anode in the light-emitting component of this Implementation Modes and negative electrode.
Here, luminescent layer 413 is not particularly limited.Yet the layer that luminescent layer 413 is preferably such, organometallic complex promptly wherein according to the present invention are to be dispersed in the layer of a kind of energy gap material composition bigger than this organometallic complex.So just can prevent from light to be extinguished because of the concentrating (concentration) of organometallic complex of the present invention.Should be pointed out that energy gap is the energy difference distance that shows between lowest unoccupied molecular orbital (LUMO) lumo energy and highest occupied molecular orbital(HOMO) HOMO energy level.
Be used for disperseing the material of organometallic complex of the present invention to be not particularly limited.Yet, remove such as 2, (the abbreviation: of 3-two (4-diphenyl amino phenyl) quinoxaline TPAQn) with 4, (abbreviation: α-NPD) and so on has outside the mixture of arylamine skeleton 4 '-two [N-(1-naphthyl) N-phenyl amino]-biphenyl, and carbazole derivates preferably is such as 4, (the abbreviation: CBP), 4 of 4 '-two (N-carbazyl) biphenyl, 4 ', 4 "-three (N-carbazyl)-triphenylamine (abbreviation: TCTA) and such as two [2-(2 '-hydroxyphenyl)-pyridine] zinc (abridge: Znpp 2), two [2-(2 '-hydroxyphenyl)-benzoxazol] zinc (abbreviation: ZnBOX) and three (oxine closes) aluminium (abbreviation: Alq 3) and so on metal complex.
Should be pointed out that the organometallic complex with electron withdraw group such as halogen radical, haloalkyl or cyano group in preferably a kind of special use organometallic complex is as the light-emitting component of luminescent material.So just can obtain the light-emitting component of a kind of colourity and quantum efficiency excellence.
In addition, the trifluoromethyl in the fluorine-based and haloalkyl in the halogen radical is particularly preferred.Use has any one organometallic complex in these groups as luminescent material, just can obtain the high light-emitting component of combined efficiency.
Though first electrode 401 is not particularly limited, preferably first electrode 401 is being to form with the bigger material of work content in using as anode in this Implementation Modes.Particularly, except that tin indium oxide (ITO), comprise the tin indium oxide of silica and comprise the indium oxide of 2-20% zinc oxide, can use gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd) etc.First electrode 401 can for example form by sputtering method or vapour deposition method.
In addition, though second electrode 402 be not particularly limited, preferably when second electrode 402 in using as negative electrode in this Implementation Modes, be to form with the work content materials with smaller.Particularly, can use the materials such as aluminium that contain alkali metal or alkaline-earth metal such as lithium (Li) or magnesium (Mg).Second electrode 402 can for example form by sputtering method or vapour deposition method.
Again, for the light extraction that will launch comes to outside, preferably any one in first electrode 401 and second electrode 402 or both be a kind of by the electrode of forming such as the material of tin indium oxide or a kind of formed thickness in several to dozens of nanometers so that the electrode that visible light can see through.
In addition, between first electrode 401 and luminescent layer 413, a hole transmission layer 412 can be set, as shown in Figure 4.Here, hole transmission layer be one will be from first electrode, 401 injected holes transmission toward luminescent layer 413 layer.By hole transmission layer 412 is set first electrode 401 and luminescent layer 413 are separated like this, can prevent because the light that metal causes extinguishes.
Hole transmission layer 412 is not particularly limited, so can use for example layer of aromatic amine compound (referring to comprise the compound of phenyl ring-nitrogen bond) formation of a usefulness, such as 4,4 '-two [N-(1-naphthyl)-N-phenyl amino]-biphenyl (abbreviation: α-NPD), 4, (the abbreviation: TPD), 4 of 4 '-two [N-(3-aminomethyl phenyl)-N-phenyl amino] biphenyl, 4 '; 4 "-three (N, the N-diphenyl amino)-triphenylamine (abbreviation: TDATA) or 4,4 ', 4 "-three [N-(3-aminomethyl phenyl)-N-phenyl amino] triphenylamine (abbreviation: MTDATA).
In addition, hole transmission layer 412 can be a layer with sandwich construction, and sandwich construction wherein is to form by two or more layers of combination with each self-contained above-mentioned material.
Can an electron transfer layer 414 be set between second electrode 402 and luminescent layer 413, as shown in Figure 4 again.Here, electron transfer layer be one can be from second electrode, 402 injected electrons transmission toward luminescent layer 413 layer.By electron transfer layer 414 is set, second electrode 402 and luminescent layer 413 are separated like this, can prevent because the light that metal causes extinguishes.
Electron transfer layer 414 is not particularly limited, thus can use the layer that forms with the metal complex that for example has chinoline backbone or benzoquinoline skeleton, such as (the abbreviation: Alq of three (oxine closes) aluminium 3), three (4-methyl-oxine closes) aluminium (abbreviation: Almq 3), two (10-hydroxy benzo [h]-oxyquinoline closes) beryllium (abbreviation: BeBq 2) or (abbreviation: BAlq) of two (2-methyl-oxine)-4-phenyl phenol-aluminium.In addition, can use to comprise (the abbreviation: ZnBOX) or two [2-(2 '-hydroxyphenyl) benzothiazole] zinc (abbreviation: Zn (BTZ) of [2-(2 '-hydroxy phenyl)-benzoxazol] zinc such as two based on the part of  azoles or the layer that forms based on the metal complex of the part of thiazole 2).Again, can use with 2-(4-xenyl)-5-(4-tert-butyl-phenyl)-1,3, (the abbreviation: PBD), 1 of 4- diazole, 3-two [5-(to tert-butyl-phenyl)-1,3,4- diazole-2-yl] benzene (abbreviation: OXD-7), 3-(4-tert-butyl-phenyl)-4-phenyl-5-(4-xenyl)-1,2, (the abbreviation: TAZ), 3-(4-tert-butyl-phenyl)-4-(4-ethylphenyl)-5-(4-xenyl)-1 of 4-triazole, 2, (the abbreviation: p-EtTAZ), bathophenanthroline (abbreviation: BPhen), bathocuproine (abbreviation: BCP) wait the layer of formation of 4-triazole.
In addition, electron transfer layer 414 can be a layer with sandwich construction, and sandwich construction wherein is to form by a plurality of layers of combination of two work with each self-contained above-mentioned material.
Can a hole injection layer 411 be set between first electrode 401 and hole transmission layer 412, as shown in Figure 4 again.Here, hole injection layer is one and can assists from as the electrode injected hole of the anode layer to hole transmission layer 412.Should be pointed out that when especially hole transmission layer not being set, by between as the electrode of anode and luminescent layer, hole injection layer being set, can the injection of assist holes in luminescent layer.
Hole injection layer 411 is not particularly limited, thus can use the layer that forms with for example metal oxide, such as molybdenum oxide (MoOx), vanadium oxide (VOx), ruthenium-oxide (RuOx), tungsten oxide (WOx), manganese oxide (MnOx).In addition, can (abridge: H with phthalocyanine compound such as phthalocyanine 2Pc) or copper phthalocyanine (abbreviation: Cu-Pc), (abbreviation: PEDOT/PSS) wait formation hole injection layer 411 of a kind of poly-(ethylidene dioxy thiophene)/poly-(styrene sulfonate) aqueous solution.
Can an electron injecting layer 415 be set between second electrode 402 and electron transfer layer 414, as shown in Figure 4 again.Here, electron injecting layer is one and can assists from inject the layer of electronics to electron transfer layer 414 as the electrode of negative electrode.Should be pointed out that when especially electron transfer layer not being set, by between as the electrode of negative electrode and luminescent layer, electron injecting layer being set, can the injection of auxiliary electron in luminescent layer.
Electron injecting layer 415 is not particularly limited, thus can use the layer that forms with for example alkali metal or alkaline earth metal compounds, such as lithium fluoride (LiF), cesium fluoride (CsF) or calcirm-fluoride (CaF 2).In addition, as electron injecting layer 415, can also use electronic transmission performance is good therein material such as Alq 3Or 4,4-two (5-methyl benzoxazol-2-yl) Stilbene (abbreviation: BzOs) with alkali metal or alkaline-earth metal such as magnesium or lithium mix mutually layer.
In the light-emitting component of the invention described above, hole injection layer 411, hole transmission layer 412, luminescent layer 413, electron transfer layer 414, and electron injecting layer 415 in each can form by any means in for example vapour deposition method, gunite, the cladding process.In addition, first electrode 401 and second electrode 402 can form by any means in for example sputtering method or the vapour deposition method.
Because used organometallic complex of the present invention, above-mentioned light-emitting component according to the present invention can produce the ruddiness of colourity excellence.In addition, because can launch phosphorescence, according to light-emitting component luminous efficiency excellence of the present invention.Again, have an organometallic complex of the present invention therein be dispersed in by quinoxaline derivant constitute the layer in the layer light-emitting component luminous especially effectively.
[Implementation Modes 5]
A kind of light-emitting component according to the present invention has a plurality of luminescent layers.For example, by a plurality of luminescent layers being provided and will mixing mutually, just can obtain white light from the light of each luminescent layer.In this Implementation Modes, the example of the light-emitting component with a plurality of luminescent layers is described with reference to Fig. 5 and 6.
In Fig. 5, between first electrode 501 and second electrode 502, be provided with first luminescent layer 513 and second luminescent layer 515.Preferably between first luminescent layer 513 and second luminescent layer 515, separate layer 514 is set.
When the electromotive force that applies the voltage so that second electrode 502 is higher than the electromotive force of first electrode 501, electric current flows between first electrode 501 and second electrode 502, and hole and electronics are in first luminescent layer 513, in second luminescent layer 515 or compound in separate layer 514.The excitation energy that is generated is transferred to first luminescent layer 513 and second luminescent layer 515 by separate layer 514, and first luminescent material that is included in first luminescent layer 513 is excited with second luminescent material that is included in second luminescent layer 515.So the ground state time of returning separately when first and second luminescent materials that excite has just emitted.
It is the luminescent material of representative that first luminescent layer 513 comprises with fluorescent material or phosphor material, fluorescent material Bao Kuo perylene, 2 wherein, 5,8,11-four uncle Ding Ji perylenes (TBP), 4,4 '-two (2, the 2-diphenylacetylene) biphenyl (DPVBi), 4,4 '-two [2-(N-ethyl carbazole-3-yl) vinyl] biphenyl (BCzVBi), two (2-methyl-oxine)-4-phenylphenol aluminium (BAlq) or two (2-methyl-oxine closes)-chlorine gallium (Gamq 2Cl), phosphor material is such as pyridine carboxylic acid two [2-(3 ', 5 '-two (trifluoromethyl) phenyl) pyridine-N, C 2 '] iridium (III) (abbreviation: Ir (CF 3Ppy) 2(pic)), acetylacetone,2,4-pentanedione two [2-(4 ', 6 '-difluorophenyl) pyridine-N, C 2 '] iridium (III) (and the abbreviation: FIr (acac)) or pyridine carboxylic acid two [2-(4 ', 6 '-difluorophenyl) pyridine-N, C 2 '] iridium (III) (abbreviation: FIr (pic)), can obtain peak value the emission spectrum at 450 to 510nm light from these materials.
In addition, second luminescent layer 515 comprises organometallic complex of the present invention as luminescent material, can obtain peak value the emission spectrum at 580 to 680nm light from second luminescent layer 515.So, from the illuminant colour of the light of first luminescent layer 513 and from the illuminant colour of the light of second luminescent layer 515 by one of in first electrode 501 and second electrode 502 or both be transmitted into the outside.Be transmitted into each outside light and visually mix to look similarly to be white light mutually.
Preferably, first luminescent layer 513 is the layers that structure is following: a kind of luminescent material that can produce 450 to 510nm light is dispersed in the layer that is made of the energy gap material bigger than luminescent material (first matrix (first host)), or a layer that is made of the material that can produce 450 to 510nm light.As first matrix, except that above-mentioned α-NPD, CBP, TCTA, Znpp2 and ZnBOX, can use 9,10-two (2-naphthyl) anthracene (abbreviation: DNA), 9,10-two (2-naphthyl)-2-tert-butyl anthracene (abbreviation: t-BuDNA) etc.Again, preferably, second luminescent layer 515 is the layers that structure is following: a kind of organometallic complex according to the present invention is dispersed in the layer by the energy gap material bigger than organometallic complex of the present invention (second matrix (second host)) formation.As second matrix, can use TPAQn, α-NPD, CBP, TCTA, Znpp2, ZnBOX, Alq 3Deng material.Again, preferably, separate layer 514 forms the energy that generates be can be transferred in first luminescent layer 513 and second luminescent layer 515, and will form and have the function that prevents that energy one of only is transferred in first luminescent layer 513 and second luminescent layer 515.Particularly, separate layer 514 can use TPAQn, α-NPD, CBP, TCTA, Znpp 2, ZnBOX waits and forms.As mentioned above, by separate layer 514 is provided, just can prevent the problem that only obtains to obtain white light because of stronger emission one of from first luminescent layer 513 and second luminescent layer 515.
In this Implementation Modes, each luminescent material that is included in first luminescent layer 513 and second luminescent layer 515 is not particularly limited.Yet, as in this Implementation Modes, when organometallic complex of the present invention is used in comparison near as in the luminescent layer (second luminescent layer 515 in this Implementation Modes) of anode (second electrode 502 in this Implementation Modes) time, the luminous efficiency that is included in the luminescent material in each layer is higher.
In addition, in this Implementation Modes, description be the luminescent layer that is provided with two luminescent layers as shown in Figure 5.Yet the quantity of luminescent layer should not be regarded as being confined to 2, for example, can use 3 luminescent layers.Can combine from the light of each luminescent layer and look just as white light again.
In addition, as shown in Figure 5, between first luminescent layer 513 and first electrode 501, an electron transfer layer 512 can be set, except that electron transfer layer 512, between the electron transfer layer 512 and first electrode 501, an electron injecting layer 511 can be set also, between second luminescent layer 515 and second electrode 502, a hole transmission layer 516 can be set, as shown in Figure 5, and between the hole transmission layer 516 and second electrode 502, a hole injection layer 517 can be set.
Except that the light-emitting component of reference Fig. 5 narration, can use light-emitting component as shown in Figure 6.
Light-emitting component shown in Figure 6 has first luminescent layer 613 and second luminescent layer 618 between first electrode 601 and second electrode 602.Between first luminescent layer 613 and second luminescent layer 618, the ground floor 615 and the second layer 616 are set.
Ground floor 615 is layers that generate the hole, and the second layer 616 is layers that generate electronics.When applying voltage and make that the electromotive force of second electrode 602 is higher than the electromotive force of first electrode 601, from first electrode, 601 injected electrons and compound first luminescent layer 613, be included in the luminescent material emission light in first luminescent layer 613 from ground floor 615 injected holes.From second electrode, 602 injected holes and compound second luminescent layer 618, be included in the luminescent material emission light in second luminescent layer 618 from the second layer 616 injected electrons again.
In first luminescent layer 613, comprise a kind of organometallic complex according to the present invention as luminescent material, can from first luminescent layer 613, obtain peak value in the emission spectrum at 580 to 680nm light.In addition, comprising a kind of in second luminescent layer 618 is the luminescent material of representative with fluorescent material or phosphor material, wherein fluorescent material Bao Kuo perylene, TBP, DPVBi, BCzVBi, Balq or Gamq 2Cl, phosphor material is such as Ir (CF3ppy) 2(pic), Fir (acac) or FIr (pic), can obtain peak value the emission spectrum at 450 to 510nm light from these materials.From the light of first luminescent layer 613 and second luminescent layer 618 one of from first electrode 601 and second electrode 602 or both send.So, visually mix from the light of each luminescent layer and can regard white light as.
In first luminescent layer 613, organometallic complex preferably according to the present invention is dispersed in above-mentioned second matrix.Equally preferably, second luminescent layer 618 forms by the mode of above-mentioned first luminescent layer 513.
Preferably, ground floor 615 be a wherein good hole mobile material rather than electron transport material comprise a kind of to this good hole mobile material demonstrate electronics be subjected to main performance material the layer.As good hole mobile material, can use and form the material identical materials of hole transmission layer.In addition, as this good hole mobile material is demonstrated the material that electronics is accepted performance, can use molybdenum oxide, vanadium oxide, 7,7,8, (the abbreviation: TCNQ), 2,3,5 of 8-four cyano quino bismethane, 6-tetrafluoro-7,7,8, (the abbreviation: F4-TCQN) etc. of 8-four cyano quino bismethane.
Preferably, the second layer 616 is that a wherein good electron transport material rather than hole mobile material comprise a kind of layer that this good electron transport material is demonstrated the material of electronation performance.As good electron transport material, can use and form the material identical materials of electron transfer layer.In addition, the material as this good electron transport material being demonstrated the electronation performance can use alkali metal such as lithium and caesium, alkaline-earth metal such as magnesium and calcium, rare earth metal such as bait and ytterbium, or the like.
In addition, between first luminescent layer 613 and first electrode 601, an electron transfer layer 612 can be set, as shown in Figure 6, between the electron transfer layer 612 and first electrode 601, an electron injecting layer 611 can be set, between first luminescent layer 613 and ground floor 615, a hole transmission layer 614 can be set, between second luminescent layer 618 and second electrode 602, a hole transmission layer 619 can be set, between the hole transmission layer 619 and second electrode 602, a hole injection layer 620 can be set, between second luminescent layer 618 and the second layer 616, an electron transfer layer 617 can be set.
In addition, in this Implementation Modes, description be the luminescent layer that is provided with two luminescent layers as shown in Figure 6.Yet the quantity of luminescent layer should not be regarded as being confined to 2, for example, can use 3 luminescent layers.Can combine from the light of each luminescent layer and look just as white light again.
[Implementation Modes 6]
What Fig. 7 showed is the light-emitting component that has luminescent layer 713 between first electrode 701 and second electrode 702.In luminescent layer 713, comprise and have by the organometallic complex of any one represented structure in general formula of the present invention (1)-(4) or by the organometallic complex of one of general formula of the present invention (5)-(8) expression, and the fluorescent material that can produce the light longer than organometallic complex wavelength of the present invention.
In this light-emitting component,, bring fluorescent material into excitation state from first electrode, 701 injected holes and compound luminescent layer 713 from second electrode, 702 injected electrons.So, when the fluorescent material that is in excitation state returns ground state, the emission bright dipping.At this moment, organometallic complex increases the number of fluorescent material singlet excited as the sensitizer of fluorescent material.As mentioned above, the organometallic complex of the application of the invention can obtain the light-emitting component of luminous efficiency excellence as sensitizer.Should be pointed out that first electrode 701 and second electrode 702 are respectively as anode in the light-emitting component of this Implementation Modes and negative electrode.
Here, luminescent layer 713 is not particularly limited.Yet, the layer that luminescent layer 713 is preferably such, what promptly wherein comprised is to be dispersed in the layer that is made of the energy gap material bigger than this organometallic complex according to organometallic complex of the present invention and fluorescent material.So just can prevent from light to be extinguished because of the concentrating (concentration) of organometallic complex of the present invention.Should be pointed out that energy gap is the energy difference distance that shows between lowest unoccupied molecular orbital (LUMO) lumo energy and highest occupied molecular orbital(HOMO) HOMO energy level.
Here, though fluorescent material be not particularly limited,, show the compound of ruddiness to infrared light, be preferable such as magnesium phthalocyanine and phthalocyanine.
In addition, be used to disperse the material of organometallic complex of the present invention and fluorescent material to be not particularly limited, can use in Implementation Modes 3 being used to of describing to disperse the material etc. of organometallic complex of the present invention.
In addition, first electrode 701 or second electrode 702 are not particularly limited, so can use and first electrode 401 described in the Implementation Modes 4 and the material identical materials of second electrode 402.
In addition, a hole injection layer 711, a hole transmission layer 712 etc. can be set between first electrode 701 and luminescent layer 713, as shown in Figure 7, and an electron transfer layer 714, an electron injecting layer 715 etc. can be set also between second electrode 702 and luminescent layer 713.
For hole injection layer 711, hole transmission layer 712, electron transfer layer 714, and electron injecting layer 715, can use respectively and the hole injection layer of in Implementation Modes 4, describing 411, hole transmission layer 412, electron transfer layer 414, and the material identical materials of electron injecting layer 415.In addition, the functional layer that another function is different from hole injection layer 711, hole transmission layer 712, electron transfer layer 714, reaches electron injecting layer 715 can be set.
Use organometallic complex of the present invention can obtain above-mentioned light-emitting component as sensitizer.
[Implementation Modes 7]
Because the light-emitting component that comprises according to organometallic complex of the present invention demonstrates excellent luminous color, can obtain a kind of light-emitting device that has in the function that shows excellent image aspect the color by light-emitting component of the present invention being used as pixel.Because can be luminous effectively, can obtain a kind of with the low-power consumption driven light emitting device by light-emitting component of the present invention being used as pixel etc. according to light-emitting component of the present invention again.
In this Implementation Modes, a kind of circuit structure and driving method with light-emitting device of display function described with reference to Fig. 8 to 11.
Fig. 8 is a diagrammatic top view of having used light-emitting component of the present invention.In Fig. 8, substrate 800 is provided with pixel portion 811, source signal line drive circuit 812, writes signal line drive circuit 813, wipes grid signal-line driving circuit 814.Source signal line drive circuit 812, write signal line drive circuit 813 and wipe in the grid signal-line driving circuit 814 each be connected to flexible print circuit (FPC) 801, FPC801 be one by one group the wiring external input terminals.Again, source signal line drive circuit 812, write signal line drive circuit 813 and wipe in the grid signal-line driving circuit 814 each receive signal such as clock signal, commencing signal and reset signal from FPC801.In addition, printed substrate (PWB) 802 is connected in FPC801.Not should be pointed out that and always must be arranged at drive circuit portion on the substrate identical as described above with the substrate that pixel portion 811 is set.For example, by the TCP that uses to have the IC chip on the FPC that is formed with wiring pattern thereon, drive circuit portion can be arranged on the substrate outside.
In pixel portion 811, many source signal lines that extend along column direction are arranged in rows, and electric current supply line is arranged in rows, and the many signal lines that follow the direction extension are aligned to row.In pixel portion 811, be arranged with a plurality of circuit of each self-contained light-emitting component again.
Fig. 9 is the figure of the circuit of a pixel of display operation.Circuit shown in Figure 9 comprises the first transistor 901, transistor seconds 902 and light-emitting component 903.
In the first transistor 901 and the transistor seconds 902 each all is three terminal components with gate electrode, drain region and source region, and has a channel region between drain region and source region.Here because source region and drain region switch each other according to transistorized structure or operation conditions, therefore be difficult to determine which be the drain region which be the source region.Therefore, in this Implementation Modes, be known as first electrode and second electrode as the district in source region or drain region.
Signal line 911 is set and writes signal line drive circuit 913 so that be electrically connected or the electricity disconnection by switch 918, signal line 911 is set and wipes grid signal-line driving circuit 914, source signal line 912 is set so that be electrically connected in source signal line drive circuit 915 and the power supply 916 any one by switch 920 so that be electrically connected or electricity disconnects by switch 919.Again, the grid of the first transistor 901 is electrically connected to signal line 911, first electrode is electrically connected to source signal line 912 and second electrode is electrically connected to the grid of transistor seconds 902.First electrode of transistor seconds 902 is electrically connected to electric current supply line 917, and second electrode is electrically connected on the electrode in the light-emitting component 903.Should be pointed out that switch 918 can be included in writes in the signal line drive circuit 913, and switch 919 can be included in to be wiped in the grid signal-line driving circuit 914, and switch 920 can be included in the source signal line drive circuit 915.
In addition, the arrangement of transistor, light-emitting component etc. is not particularly limited.For example, can adopt the arrangement shown in the vertical view of Figure 10.In Figure 10, first electrode of the first transistor 1001 is connected in source signal line 1004, and second electrode is connected in the gate electrode of transistor seconds 1002.Again, first electrode of transistor seconds 1002 is connected in electric current supply line 1005, and second electrode is connected in the electrode 1006 of light-emitting component.A part of signal line 1003 is used as the gate electrode of the first transistor 1001.
Next driving method will be described.Figure 11 is the time service chart of each frame of explanation.In Figure 11, the sequence number of signal line is vertically represented in the laterally passage of express time.
When light-emitting device according to the present invention was used for show image, the rewrite operation and the image that repeat screen in a display cycle showed.Though the number of times that rewrites is not particularly limited, preferably, number of rewrites is about per second 60 times, so that do not make the spectators of image discover flicker.Here, the cycle at (frame) rewrite operation of a screen and display operation is known as a frame period.
As scheme institute 11 and show that a frame is divided into four subframes: 1101,1102,1103 and 1104, have 1101a write cycle, 1102a, 1103a and 1104a respectively and retain cycle 1101b, 1102b, 1103b and 1104b.In the cycle of retaining, the light-emitting component that has been given luminous signal enters luminance.The ratio that retains Cycle Length of each subframe is 1103: the four subframe 1104=2 of first subframe, 1102: the three subframes of 1101: the second subframes 3: 2 2: 2 1: 2 0=8: 4: 2: 1.This makes the classification of 4-bit become possibility.Yet bit number or branch progression are not limited to person described here.For example, can provide 8 subframes, so that carry out the classification of 8-bit.
To the operation of a frame be described.At first, in subframe 1101, press each the row execution write operation of delegation to the end of ordered pair first row.Therefore, according to the row difference, write cycle 1101a the time started difference.When write cycle, 1101a finished, row moved into according to the order of sequence and retains cycle 1101b.In retaining cycle 1101b, the light-emitting component that has been given luminous signal enters luminance.Again, when retaining cycle 1101b end, row moves into next subframe 1102 according to the order of sequence, and as in subframe 1101, presses each the row execution write operation of delegation to the end of ordered pair first row.Repeat aforesaid operations to finish the cycle that the retains 1104b of subframe 1104.When the operation of subframe 1104 was finished, row moved into next frame.So, the total time of sending light in each subframe is the launch time of each light-emitting component in each frame.By each light-emitting component is changed this launch time so that in a pixel combination miscellaneous is arranged, can obtain the display color of various brightness and colourity.
As in subframe 1104, carry out the forced termination cycle that retains when needing writing of delegation in the end to carry out before finishing when one being write the row of having finished to move into RT, an erase cycle 1104c preferably is set after retaining cycle 1104b, row is controlled so that force to enter non-emission state.Force to enter the row of non-emission state at non-emission state maintenance some cycles (this cycle is known as non-emission cycle 1104d) again.So, after in the end 1104a write cycle of delegation finishes, at once these row are moved into next write cycle (or next frame) according to the order of sequence, since first row.So just can prevent subframe 1104 write cycle 1104a and the write cycle of next subframe overlapping.
A horizontal cycle is issued two cycles: a selection cycle and the selection cycle to another row input signal of video signal to row input erase signal, the signal that input to source signal line 912 switches according to each selection cycle.According to this method of operation, by non-emission cycle 1104d is set, the cycle 1104b of retaining can become and be shorter than required time when writing all row.
Though the subframe 1101 to 1104 in this Implementation Modes be by RT from the longest to the shortest tactic, always necessary as the arrangement in this Implementation Modes.For example, subframe 1101 to 1104 can perhaps be arranged with random sequence by RT from being short to most the longest sequence arrangement.In addition, these subframes can further be divided into a plurality of frames.That is, the scanning of signal line can be carried out once above and provide identical signal of video signal.
Below, key diagram 9 operations of described circuit in write cycle and erase cycle.
Operation when at first, describing write cycle time.In write cycle time, n root (n is a natural number) signal line 911 is electrically connected to by switch 918 and writes signal line drive circuit 913, but not with wipe grid signal-line driving circuit 914 and be connected.In addition, source signal line 912 is electrically connected to source signal line drive circuit 915 by switch 920.This situation, the grid of signal input the first transistor 901 is to start the first transistor 901, and this transistor is connected to n root (n is a natural number) signal line 911.At this moment, picture signal is input to first simultaneously to last source signal line 912.It should be noted that from the picture signal input of each source signal line 912 independently of one another.Picture signal input from each source signal line 912 is input to transistor seconds transistor 902 by the first transistor 901 that links to each other with source signal line 912.At this moment, the signal according to input transistor seconds 902 comes control switch transistor seconds 902.Therefore, according to the signal of the gate electrode of importing transistor seconds 902, determine whether light-emitting component 903 has launched light.For example, when transistor seconds 902 is the p-channel transistor, make light-emitting component 903 emission light by gate electrode input low level signal at transistor seconds 902.On the other hand, when transistor seconds 902 is the n-channel transistor, make light-emitting component 903 emission light by import high-level signal at the gate electrode of transistor seconds 902.
Next, be described in the operation of erase cycle.In erase cycle, n root (n is a natural number) signal line 911 is electrically connected to by switch 919 wipes grid signal-line driving circuit 914, but not with write signal line drive circuit 913 and be connected.In addition, source signal line 912 is electrically connected to power supply 916 by switch 920.In this case, signal is transfused to the grid of the first transistor 901 to start the first transistor 901, and transistor 901 is connected to n root (n is a natural number) signal line 911.At this moment, erase signal is input to first simultaneously to last source signal line 912.Be transfused to the gate electrode of transistor seconds 902 by the first transistor 901 that links to each other with source signal line 912 from the erase signal input of each source signal line 912.At this moment, the electric current supply from electric current supply line 917 supply light-emitting components 903 is blocked (block) according to the signal input of importing transistor seconds 902.Then, light-emitting component 903 is forced to be in and does not launch attitude.For example, when transistor seconds 902 is the p-channel transistor, make light-emitting component 903 not launch light by gate electrode with high-level signal input transistor seconds 902.On the other hand, when transistor seconds 902 is the n-channel transistor, make light-emitting component 903 not launch light by the gate electrode of low level signal being imported transistor seconds 902.
It should be noted that as for n capable (n is a natural number), operate erase cycle is described, the signal input that will be used to wipe according to top.But as mentioned above, n is capable when erase cycle, and other row (being called m capable (m is a natural number)) can be in write cycle.This situation, with same root holding wire, it is capable to m to import the signal that is used to wipe signal capable to n and that input is used to write.Therefore, preferred operation described below.
After making n light-emitting component 903 not launch light by operation in above-mentioned erase cycle, at once make signal line 911 and wipe grid signal-line driving circuit 914 and do not link to each other each other, and switch 920 is transformed into source signal line 912 is linked to each other with source signal line drive circuit 915.Then, except source signal line 912 is connected to the source signal line drive circuit 915, signal line 911 is connected to writes signal line drive circuit 913.Then, signal is imported m root signal line 911 from writing signal line drive circuit 913 selectivity, with startup the first transistor 901, and the signal that is used to write is input to first to last source signal line 912 from source signal line drive circuit 915.This signal makes m light-emitting component 903 be in emission or does not launch attitude.
Finish as mentioned above m after capable write cycle, get started erase cycle (n+1) row.For this purpose, make signal line 911 and write signal line drive circuit 913 and do not link to each other each other, and switch 920 is transformed into connects source signal line 912 and power supply 916.In addition, make and be not connected to the signal line 911 that writes signal line drive circuit 913 and be connected to and wipe grid signal-line driving circuit 914.Then, signal is imported (n+1) root signal line 911 from wiping grid signal-line driving circuit 914 selectivity, with startup the first transistor 901, and from power supply 916 input erase signals.After finishing erase cycle, get started write cycle to (m+1) row to (n+1) row.Then, repeat erase cycle and write cycle according to same way as, up to the erase cycle of finishing last row.
Though by this Implementation Modes described the erase cycle capable to n and to (n+1) row erase cycle between the example of capable write cycle to m is provided, the invention is not restricted to this Implementation Modes.To m capable write cycle can be to the erase cycle of (n-1) row and between to the capable erase cycle of n.
In addition, in this Implementation Modes, when providing in the subframe (sub-frame) 1104 when not launching cycle 1104d, repeat to make and wipe grid signal-line driving circuit 914 and be not connected each other with a signal line 911 and make and write the operation that signal line drive circuit 913 links to each other with all the other signal lines 911.Such operation can be carried out not providing especially in the subframe of not launching the cycle.
[Implementation Modes 8]
Referring to Figure 12 A to 12C, the cross section of an example of light-emitting device that comprises light-emitting component of the present invention is described.
In each figure of Figure 12 A to 12C, the part of dotted line provides the transistor 1211 that drives light-emitting component 1212 of the present invention.Light-emitting component 1212 is light-emitting components of the present invention, has layer 1215, and wherein, piling up between first electrode 1213 and second electrode 1214 has the layer that produces cavitation layer, electrogenesis sublayer and comprise luminescent substance.First electrode 1213 is electrically connected by distribution 1217 mutually with the drain electrode of transistor 1211, and this distribution 1217 passes first intermediate insulating film 1216 (1216a to 1216c).In addition, light-emitting component 1212 is separated by separator 1218 and adjacent another light-emitting component.Light-emitting device with this structure of the present invention is provided on substrate 1210.
It should be noted that the transistor 1211 shown in each figure of Figure 12 A to 12C is a top grid (top-gate) TFT, wherein, gate electrode is on the face relative with substrate as the semiconductor layer of central core.But the structure of transistor 1211 specifically is not limited to this structure.For example can adopt bottom-gate TFT.In bottom-gate TFT situation, can use the TFT (passage-protection TFT) that diaphragm is arranged on the semiconductor layer that forms passage, or the part of formation passage is the TFT (passage-etching TFT) of concave surface in the use semiconductor layer.
In addition, the semiconductor layer that forms transistor 1211 can be a crystal or unbodied, perhaps can be partly unbodied.
Half amorphous semiconductor is described below.Half amorphous semiconductor is the intermediate structure that has between amorphous and crystal (as monocrystalline or polycrystalline) structure, and has the semiconductor of the stable elicit illness state of free energy, and this based semiconductor comprises the crystal region with shortrange order and distortion of lattice.In addition, the crystal grain that at least one zone of half amorphous semiconductor film, comprises 0.5-20nm.The Raman spectrum of half amorphous semiconductor has to less than 520cm -1The drift of wave number.In X-ray diffraction, observe (111) and (220) diffraction maximum of Si crystal lattices.Comprising the hydrogen or halogen that is equal to or greater than 1 atom % in this half amorphous semiconductor, is terminal with the dangling bonds.Therefore, half amorphous semiconductor is also referred to as crystallite semiconductor.Silicide gas is decomposed by glow discharge (plasma CVD), forms half amorphous semiconductor.Except SiH 4Can use as Si outward, 2H 6, SiH 2Cl 2, SiHCl 3, SiCl 4Or SiF 4And so on gas as silicide gas.This silicide gas can be used H 2Dilution or use H 2Dilute with one or more rare gas that are selected from He, Ar, Kr or Ne, dilution ratio is 2: 1 to 1000: 1.Pressure during glow discharge is about 0.1-133Pa, and supply frequency is in the 1-120MHz scope, preferred 13-60MHz.The substrate heating-up temperature is for being less than or equal to 300 ℃, preferred 100-250 ℃.The impurity that atmosphere is formed in requirement such as the concentration of oxygen, nitrogen or carbon are controlled at that impurity element is 1 * 10 in the film 20/ cm 3Or lower, particularly oxygen concentration is controlled at and is less than or equal to 5 * 10 19/ cm 3, preferably be less than or equal to 1 * 10 19/ cm 3In addition, use the mobility of the TFT (thin-film transistor) of this half amorphous semiconductor to be about 1-10m 2/ V sec.
In addition, the object lesson of the crystalline semiconductor of semiconductor layer is comprised monocrystalline silicon or polysilicon and silicon-germanium, they can form by laser crystallization, perhaps by using the solid state growth crystallization such as the element of nickel to form.
Using for example situation of amorphous silicon formation semiconductor layer of amorphous materials, transistor 1211 and other transistor in the circuit of preferred light-emitting device (forming the transistor of the circuit of driven light-emitting element) all are the n-channel transistors.Other situation, the circuit of light-emitting device one of can comprise in n-channel transistor and the p-channel transistor or comprise simultaneously n-channel transistor and p-channel transistor.
In addition, the dielectric film 1216 in first intermediate layer can be the multilayer shown in Figure 12 A and 12C, or individual layer.The first insulating film of intermediate layer 1216a comprises the inorganic substances as silica or silicon nitride, and the first insulating film of intermediate layer 1216b comprises the material from flatness of having that can be used for plating deposition, as acrylic compounds, siloxanes or silica.It should be noted that siloxanes has the frame structure that the key between silicon (Si) and the oxygen (O) forms, wherein, with comprising that the organic group (for example, alkyl or aromatic hydrocarbon group) of hydrogen is as substituting group at least.Available fluoro-containing group or the organic group that comprises hydrogen and fluorin radical at least are as substituting group.In addition, the first insulating film of intermediate layer 1216c has the silicon nitride film that comprises argon (Ar).The material that comprises in each layer is had no particular limits, therefore, can use other material except the material of addressing at this.And, can make up the layer that comprises the material outside these materials.Like this, can use inorganic material and organic material, perhaps a kind of formation first insulating film of intermediate layer 1216 in inorganic material and the organic material.
For separator 1218, preferred marginal portion is a radius of curvature continually varying shape.In addition, use material to form separator 1218 as acrylic compounds, siloxanes, photoresist (resist) or silica.Form separator 1218 with a kind of in inorganic material and the organic material or both.
Among Figure 12 A and Figure 12 C, between transistor 1211 and light-emitting component 1212, only provide first insulating film of intermediate layer.Yet, shown in Figure 12 B, except that first insulating film of intermediate layer 1216 (1216a and 1216b), also provide second insulating film of intermediate layer 1219 (1219a and 1219b).In the light-emitting device shown in Figure 12 B, first electrode 1213 is connected to distribution 1217 by second insulating film of intermediate layer 1219.
Second insulating film of intermediate layer 1219 and first insulating film of intermediate layer 1216 are multilayer or individual layer in the same way.The second insulating film of intermediate layer 1219a comprises the material from flatness of having that can be used for plating deposition, as acrylic compounds, siloxanes or silica.It should be noted that siloxanes has the frame structure that the key between silicon (Si) and the oxygen (O) forms, wherein, with comprising the organic group (for example, alkyl or aromatic hydrocarbon group) of hydrogen as substituting group at least.Available fluoro-containing group or the organic group that comprises hydrogen and fluorin radical at least are as substituting group.In addition, the second insulating film of intermediate layer 1219b has the silicon nitride film that comprises argon (Ar).The material that comprises in each layer is had no particular limits, therefore, can use other material except the material of addressing at this.And, can make up the layer that comprises the material outside these materials.Like this, can use inorganic material and organic material, perhaps a kind of formation second insulating film of intermediate layer 1219 in inorganic material and the organic material.
The situation that first electrode 1213 in the light-emitting component 1212 and second electrode 1214 all form with light transmissive material, the light of emission extracts from first electrode, 1213 sides and second electrode, 1214 sides, shown in the arrow among Figure 12 A.In the situation of having only second electrode, 1214 usefulness light transmissive materials to form, the light of emission only extracts from second electrode, 1214 sides, shown in the arrow among Figure 12 B.In this case, preferred first electrode 1213 comprises high reflecting material, the film (reflectance coating) that perhaps provides high reflecting material to constitute below first electrode 1213.In the situation of having only first electrode, 1213 usefulness light transmissive materials to form, the light of emission only extracts from first electrode, 1213 sides, shown in the arrow among Figure 12 C.In this case, preferred second electrode 1214 comprises high reflecting material, perhaps cremasteric reflex film on second electrode 1214.
In addition, layer 1215 can pile up in a certain way, light-emitting component 1212 runnings when applying voltage, make the electromotive force of second electrode 1214 be higher than the electromotive force of first electrode 1213, perhaps layer 1215 can pile up in a certain way, light-emitting component 1212 running when applying voltage makes the electromotive force of second electrode 1214 be lower than the electromotive force of first electrode 1213.In last situation, transistor 1211 is n-channel transistors, and in back one situation, transistor 1211 is p-channel transistors.
As mentioned above, the active illuminating device that is driven by the transistor controls light-emitting component is described in this Implementation Modes.Yet in addition, the present invention can be applicable to not provide the passive light-emitting device of driving element such as transistorized light-emitting component.The situation of passive light-emitting device when passive light-emitting device comprises light-emitting component of the present invention, can drive with low energy consumption, and described light-emitting component can be operated under low driving voltage.
[execution mode]
Below, describe the present invention in detail according to execution mode.But, the invention is not restricted to these execution modes naturally.At first, the synthetic example of the organometallic complex that is used for light-emitting component of the present invention and the character of these organometallic complexs are described, then, the structure and the manufacture method thereof of light-emitting component of the present invention are described, the example of light-emitting device is described.
[execution mode 1: the synthetic example of organometallic complex and the character of this complex]
(synthesis example 1)
This synthesis example is (acetylacetonato) iridium (III) (abbreviation: Ir (Fdpq) of formula (16) representative { 2,3-two (4-fluorophenyl) quinoxaline oxygen (quinoxalinato) } (acetylacetone,2,4-pentanedione) 2(acac)) synthesis example.
＜step 1: synthetic ligands (HFdpq) 〉
At first, with 3.71 grams 4,4 '-difluoro benzil and 1.71 gram o-phenylenediamines added thermal agitation 6 hours in solvent (200mL chloroform).Reaction solution is cooled to room temperature,, uses dried over mgso with HCl (1N) and saturated aqueous sodium chloride washing.Remove and desolvate, obtain part HFdpq (2,3-two (4-fluorophenyl) quinoxaline) (pale yellow powder, productive rate: 99%).
The synthetic schemes of part HFdpq and structural formula are by with shown in the following formula (60).
＜step 2: synthetic binuclear complex [Ir (Fdpq) 2Cl] 2
As solvent, restrain iridium chloride (IrCl with the mixture of 30mL cellosolvo and 10mL water with 3.61 gram part HFdpq (2,3-two (4-fluorophenyl) quinoxaline) and 1.35 3HClH 2O) mix, in blanket of nitrogen, keep refluxing 17 hours, obtain binuclear complex [Ir (Fdpq) 2Cl] 2(brown ceramic powder, productive rate: 99%).
Binuclear complex [Ir (FdPq) 2Cl] 2Synthetic schemes and structural formula by illustrating with following formula (61).
Figure A20058001604900612
＜step 3: the synthetic organometallic complex Ir (Fdpq) that is used for light-emitting component of the present invention 2(acac) 〉
The 30mL cellosolvo is as solvent, with 2.00 gram binuclear complex [Ir (Fdpq) of above-mentioned steps 2 acquisitions 2Cl] 2, 0.44mL acetylacetone,2,4-pentanedione (Hacac) and 1.23 gram sodium carbonate mix, and keep refluxing 20 hours in blanket of nitrogen, obtain the organometallic complex Ir (Fdpq) by formula of the present invention (16) expression 2(acac) (red powder, productive rate: 44%).
This synthetic schemes is by illustrating with following formula (62).
Figure A20058001604900621
Organometallic complex Ir (Fdpq) 2Nulcear magnetic resonance (NMR) (acac) ( 1H-NMR) analysis result is as follows.
1H-NMR.δ(CDCl 3)：8.20(d，2H)，8.11(d，2H)，8.01(brs，4H)，7.68(t，2H)，7.52(t，2H)，7.32(brm，4H)，7.08(m，2H)，6.39(td，2H)，6.05(dd，2H)，4.71(s，1H)，1.62(s，6H)
In addition, (, TG/DTA-320) measure the Ir that obtains (Fdpq) with thermogravimetric/differential thermal analysis synchronized measurement system from Seiko Instruments Inc. 2(acac) pyrolysis temperature Td finds Td=365 ℃, therefore, determines this organometallic complex Ir (Fdpq) 2(acac) show favourable thermal endurance (heatresistance).
In addition, Figure 13 illustrates the Ir that obtains (Fdpq) 2(acac) absorption spectrum in carrene and emission spectrum (Photo Luminescence).It should be noted that when with wavelength being the light of 469nm during as excitation source, obtain emission spectrum, wavelength 469nm only extracts by using slit that the light from Halogen lamp LED is separated.Among Figure 13, transverse axis is represented wavelength (nm), and the longitudinal axis on the left side is represented absorbance (no unit), and the right side longitudinal axis is represented emissive porwer (a.u.: supplementary unit).As shown in figure 13, organometallic complex Ir of the present invention (Fdpq) 2(acac) absworption peak at 232nm, 284nm, 371nm and 472nm is arranged.In addition, emission spectrum shows the luminous of 644nm emission peak, and that sees is this luminous for red light.
The Ir (Fdpq) that is obtaining 2(acac) situation is observed several absworption peaks.This is the absorption that organometallic complex just has, and as the situation at virgin metalization (orthometalated) complex etc., believes it is corresponding to single MLCT transition, triple π-π *Transition, triple MLCT (metal shifts to the part electric charge) transition etc.Particularly, at visual range one broad peak is arranged, can think that this peak is the absorption spectrum that has only triple MLCT transition just to have at the absworption peak of long wavelength side.That is, determine Ir (Fdpq) 2(acac) be can direct sunshine to be excited to the triplet that excites and the compound of intersystem crossing.
In addition, the oxygen-containing gas injection is contained the Ir (Fdpq) that is obtained 2(acac) in the dichloromethane solution, test makes Ir (Fdpq) 2When (acac) producing luminous (luminescence) with the oxygen that dissolves, Ir (Fdpq) 2(acac) emissive porwer.In addition, the gas that will contain argon injects and to contain the Ir (Fdpq) that is obtained 2(acac) in the dichloromethane solution, test makes Ir (Fdpq) 2(acac) argon with dissolving produces when luminous Ir (Fdpq) 2(acac) emissive porwer.Can determine by these results, from Ir (Fdpq) 2(acac) the luminous trend that luminous demonstration is identical with phosphorus, this trend is, the luminous intensity of the luminous intensity during the dissolving argon during greater than dissolved oxygen.Therefore, believe from Ir (Fdpq) 2(acac) luminous is phosphorescence.
(synthesis example 2)
This synthesis example is by two (2,3-diphenyl quinoxaline oxygen) (acetylacetone,2,4-pentanedione) iridium (III) of formula (17) expression (abbreviation: Ir (dpq) 2(acac)) synthesis example.
＜step 1: synthetic binuclear complex [Ir (dpq) 2Cl] 2
At first, will be as the 30mL cellosolvo of solvent and mixture and the 2.36 gram part Hdpq (2,3-diphenyl quinoxaline) and the 1.00 gram iridium chloride (IrCl of 10mL water 3HClH 2O) mix, in blanket of nitrogen, keep refluxing 15 hours, obtain binuclear complex [Ir (dpq) 2Cl] 2(dark-brown powder, productive rate: 91%).
Binuclear complex [Ir (dpq) 2Cl] 2Synthetic schemes and structural formula by with shown in the following formula (63).
＜step 2: synthetic organometallic complex Ir of the present invention (dpq) 2(acac) 〉
As solvent, restrain binuclear complex [Ir (dpq) with the 30mL cellosolvo with 1.00 of top step 1 acquisition 2Cl] 2, 0.20mL acetylacetone,2,4-pentanedione (Hacac) and 0.67 gram sodium carbonate mixes, in blanket of nitrogen, keep refluxing 15 hours.Filter this reaction solution, provide column chromatography, carry out purifying with dichloromethane solvent to the solution that obtains.Use carrene/alcohol solvent to carry out recrystallization, obtain organometallic complex Ir of the present invention (dpq) 2(acac) (little rufous powder, productive rate: 40%).
This synthetic schemes is by illustrating with following formula (64).
Organometallic complex Ir (dpq) 2Nulcear magnetic resonance (NMR) (acac) ( 1H-NMR) analysis result is as follows.
1H-NMR.δ(CDCl 3)：8.15(t，4H)，7.89(brs，4H)，7.79(t，2H)，7.69(m，8H)，6.94(d，2H)，6.57(t，2H)，6.48(t，2H)，6.33(d，2H)，4.81(s，1H)，1.64(s，6H)
In addition, (, TG/DTA-320) measure the Ir that obtains (dpq) with thermogravimetric/differential thermal analysis synchronized measurement system from Seiko Instruments Inc. 2(acac) pyrolysis temperature Td finds Td=340 ℃, therefore, determines this organometallic complex Ir (dpq) 2(acac) show favourable thermal endurance.
In addition, Figure 14 illustrates the Ir that obtains (dpq) 2(acac) absorption spectrum in carrene and emission spectrum thereof (PL).It should be noted that when with wavelength being the light of 469nm during as excitation source, obtain emission spectrum, its medium wavelength 469nm only extracts by using slit that the light from Halogen lamp LED is separated.Among Figure 14, transverse axis is represented wavelength (nm), and the longitudinal axis on the left side is represented absorbance (no unit), and the right side longitudinal axis is represented emissive porwer (a.u.: supplementary unit).As shown in figure 14, the organometallic complex Ir (dpq) of gained 2(acac) absworption peak at 248nm, 283nm, 387nm and 479nm is arranged.In addition, emission spectrum shows the luminous of 687nm emission peak, and that sees is luminous for red light.
The Ir (dpq) that is obtaining 2(acac) situation is observed several absworption peaks.This is the absorption that organometallic complex just has, and as the situation at virgin metal complex etc., believes it is corresponding to single MLCT transition, triple π-π *Transition, triple MLCT transition etc.Particularly, one broad peak is arranged in the visual field, can think that this peak is the absorption spectrum that has only triple MLCT transition just to have at the absworption peak of long wavelength side.That is, determine Ir (dpq) 2(acac) be can direct sunshine to be excited to the triplet that excites and the compound of intersystem crossing.
In addition, the oxygen-containing gas injection is contained the Ir (dpq) that is obtained 2(acac) in the dichloromethane solution, test makes Ir (dpq) 2(acac) oxygen with dissolving produces when luminous Ir (dpq) 2(acac) emissive porwer.In addition, the gas that will contain argon injects and to contain the Ir (dpq) that is obtained 2(acac) in the dichloromethane solution, test makes Ir (dpq) 2(acac) argon with dissolving produces when luminous Ir (dpq) 2(acac) emissive porwer.Can determine by these results, from Ir (dpq) 2(acac) the luminous trend that luminous demonstration is identical with phosphorus, this trend is, the luminous intensity of the luminous intensity during the dissolving argon during greater than dissolved oxygen.Therefore, believe from Ir (dpq) 2(acac) luminous is phosphorescence.
(synthesis example 3)
This synthesis example is by (the abbreviation: Ir (Fdpq) of following formula (65) expression { 2,3-two (4-fluorophenyl) quinoxaline oxygen } (the pyridine carboxylic acid root closes (picolinato)) iridium (III) 2(pic)) synthesis example.
Ir (Fdpq) 2(pic) structural formula is by with shown in the following formula (65).
Figure A20058001604900661
At first, the binuclear complex [Ir (FdPq) that obtains with step 1 in the synthesis example 1 2Cl] 2As raw material.With the 30mL carrene as solvent, with 2.87 the gram [Ir (Fdpq) 2Cl] 2Mix with 1.67 gram pyridine carboxylic acids (Hpic), in blanket of nitrogen, keep refluxing 16 hours.Filter this reaction solution, obtain organometallic complex Ir (Fdpq) 2(pic) (red powder, productive rate: 56%).
This synthetic schemes is by illustrating with following formula (66).
Figure A20058001604900671
Organometallic complex Ir (Fdpq) 2Nulcear magnetic resonance (NMR) (pic) ( 1H-NMR) analysis result is as follows.
1H-NMR.δ(CDCl 3)：8.66(d，IH)，8.45(d，IH)，8.04(m，4H)，7.95(d，1H)，7.81(m，3H)，7.69(m，2H)，7.59(t，1H)，7.53(t，1H)，7.33(m，5H)，7.18(t，1H)，7.07(t，2H)，6.51(td，1H)，6.38(m，2H)，5.78(dd，1H)
In addition, (, TG/DTA-320) measure the Ir that obtains (Fdpq) with thermogravimetric/differential thermal analysis synchronized measurement system from Seiko Instruments Inc. 2(acac) pyrolysis temperature T d, find T d=347 ℃, therefore, determine this organometallic complex Ir (Fdpq) 2(pic) show favourable thermal endurance.
In addition, Figure 15 illustrates the Ir that obtains (Fdpq) 2(pic) absorption spectrum in carrene and emission spectrum (PL).It should be noted that when with wavelength being the light of 468nm during as exciting light, obtain emission spectrum, its medium wavelength 468nm only extracts by using slit that the light from Halogen lamp LED is separated.Among Figure 15, transverse axis is represented wavelength (nm), and the longitudinal axis on the left side is represented absorbance (no unit), and the right side longitudinal axis is represented emissive porwer (a.u.).As shown in figure 15, the organometallic complex Ir (Fdpq) of gained 2(pic) a plurality of absworption peaks are arranged.In addition, emission spectrum shows the luminous of 625nm emission peak, and that sees is luminous for red light.
Absworption peak at long wavelength side has a broad peak in the visual field, can think that this peak is the absorption spectrum that triple MLCT transition just have.That is, determine Ir (Fdpq) 2(pic) be can direct sunshine to be excited to the triplet that excites and the compound of intersystem crossing.
(synthesis example 4)
In this synthesis example, describe synthetic by { 2,3-two (3, the 5-difluorophenyl) quinoxaline oxygen } (acetylacetone,2,4-pentanedione) iridium (III) with following formula (67) expression.
Ir (3,5-Fdpq) 2(acac) structural formula is by illustrating with following formula (67).
Figure A20058001604900681
＜step 1: synthesize 3,3 ', 5,5 '-ptfe benzyl 〉
3,3 ', 5,5 '-ptfe benzyl is the following synthetic material that is used for part.At first, with 3.16 gram magnesium be suspended in 3mL oxolane (tetrahydrofran) (abbreviation: THF), add a small amount of 1, the 2-methylene bromide.In this mixture, drip 25.00 gram 1-bromo-3, the solution of 5-two fluorobenzene in 130mL THF stirred 1.5 hours when heating keeps refluxing.Next, in being cooled to this solution of room temperature, add 9.24 grams 1,4-lupetazin-2, the 3-diketone stirred 13 hours when heating keeps refluxing.
In addition, the hydrochloric acid adding with 200mL 10% is cooled in this solution of room temperature the organic layer chloroform extraction.After dried over sodium sulfate, concentrated solvent.At last, carry out purifying, obtain 3,3 ', 5,5 '-ptfe benzyl (yellow powder, productive rate: 46%) by column chromatography (hexanes/ch system).
Synthetic schemes is illustrated by following formula (68).
＜step 2: synthetic ligands H (3,5-Fdpq) 〉
With chloroform (300mL) join 8.32 synthetic grams 3,3 of step 1 ', 5,5 '-ptfe benzyl and 3.19 grams 1, in the 2-phenylenediamine, when heating keeps refluxing, stirred 10 hours.The solution that is cooled to room temperature is washed with hydrochloric acid (1N), with the saturated aqueous sodium chloride washing, use dried over mgso then.Then, solvent concentrates, and obtains 2,3-two (3, the 5-difluorophenyl) quinoxaline (part H (3,5-Fdpq)) (white powder, productive rate: 98%).
(3, synthetic schemes 5-Fdpq) and structural formula are by illustrating with following formula (69) for part H.
Figure A20058001604900691
＜step 3: synthetic binuclear complex [Ir (3,5-Fdpq) 2Cl] 2
At first, with the mixture of 30mL cellosolvo and 10mL water as solvent, with part H synthetic in the 2.46 gram steps 2 (3,5-Fdpq) and 0.83 gram iridium chloride (IrCl 3HClH 2O) mix, in blanket of nitrogen, keep refluxing 17 hours, and the acquisition binuclear complex [Ir (3,5-Fdpq) 2Cl] 2(little rufous powder, productive rate: 78%).
Binuclear complex [Ir (3,5-Fdpq) 2Cl] 2Synthetic schemes and structural formula by illustrating with following formula (70).
＜step 3: synthesis of organometallic complex Ir (3,5-Fdpq) 2(acac) 〉
With the 30mL cellosolvo is solvent, with the 2.34 gram binuclear complexs that in above-mentioned steps 3, obtain [Ir (and 3,5-Fdpq) 2Cl] 2, 0.39mL acetylacetone,2,4-pentanedione (Hacac) and 1.32 gram sodium carbonate mix, and keep refluxing 20 hours in blanket of nitrogen, obtains the organometallic complex Ir that represents by following formula (67) of the present invention (3,5-Fdpq) 2(acac) (peony powder, productive rate: 22%).
This synthetic schemes is shown in following formula (71).
Figure A20058001604900711
Organometallic complex Ir (3,5-Fdpq) 2Nulcear magnetic resonance (NMR) (acac) ( 1H-NMR) analysis result is as follows.
1H-NMR.δ(CDCl 3)：8.10(t，4H)，7.75(t，2H)，7.61(m，4H)，7.30(m，2H)，7.09(tt，2H)，6.77(dd，2H)，6.20(td，2H)，4.67(s，1H)，1.61(s，6H)
In addition, with thermogravimetric/differential thermal analysis synchronized measurement system (from Seiko Instruments Inc., TG/DTA-320) measure the Ir that obtains (3,5-Fdpq) 2(acac) pyrolysis temperature T d, find T d=342 ℃, therefore, determine this organometallic complex Ir (Fdpq) 2(pic) show favourable thermal endurance.
In addition, Figure 16 illustrate the Ir that obtains (3,5-Fdpq) 2(acac) absorption spectrum in carrene and emission spectrum (PL).It should be noted that when with wavelength being the light of 468nm during as exciting light, obtain emission spectrum, its medium wavelength 468nm only extracts by using slit that the light from Halogen lamp LED is separated.Among Figure 16, transverse axis is represented wavelength (nm), and the longitudinal axis on the left side is represented absorbance (no unit), and the right side longitudinal axis is represented emissive porwer (a.u.).As shown in figure 16, and the organometallic complex Ir of gained (3,5-Fdpq) 2(acac) a plurality of absworption peaks are arranged.In addition, emission spectrum shows the luminous of 666nm emission peak, and that sees is luminous for dark red coloured light.
Absworption peak at long wavelength side has a broad peak in the visual field, can think that this peak is the absorption spectrum that has only triple MLCT transition just to have.That is, determine Ir (3,5-Fdpq) 2(acac) be can direct sunshine to be excited to the triplet that excites and the compound of intersystem crossing.
(synthesis example 5)
In this synthesis example, synthetic by { 2,3-two (3, the 5-difluorophenyl) quinoxaline oxygen } (the pyridine carboxylic acid root closes) iridium (III) of following formula (72) expression described.
Ir (3,5-Fdpq) 2(pic) structural formula is by illustrating with following formula (72).
Figure A20058001604900721
With the 30mL carrene is solvent, with 2.54 grams in the step 3 of synthesis example 4 synthetic binuclear complex [Ir (and 3,5-Fdpq) 2Cl] 2Mix with 1.34 gram pyridine carboxylic acids (Hpic), in blanket of nitrogen, keep refluxing 16 hours.Filter this solution, obtain organometallic complex Ir of the present invention (3,5-Fdpq) 2(pic) (red powder, productive rate: 14%).
Synthetic schemes is shown in following formula (73).
Figure A20058001604900731
Organometallic complex Ir (3,5-Fdpq) 2Nulcear magnetic resonance (NMR) (pic) ( 1H-NMR) analysis result is as follows.
1H-NMR.δ(CDCl 3)：8.65(d，1H)，8.54(d，1H)，8.06(m，2H)，7.87-7.54(m，8H)，7.32(m，3H)，7.12(m，3H)，6.85(d，1H)，6.74(d，1H)，6.37(t，1H)，6.17(t，1H)
In addition, with thermogravimetric/differential thermal analysis synchronized measurement system (from Seiko Instruments Inc., TG/DTA-320) measure the Ir that obtains (3,5-Fdpq) 2(pic) pyrolysis temperature T d, find T d=347 ℃, therefore, determine this organometallic complex Ir (Fdpq) 2(pic) show favourable thermal endurance.
In addition, Figure 17 illustrate the Ir that obtains (3,5-Fdpq) 2(pic) absorption spectrum in carrene and emission spectrum (PL).It should be noted that when with wavelength being the light of 468nm during as exciting light, obtain emission spectrum, its medium wavelength 468nm only extracts by using slit that the light from Halogen lamp LED is separated.Among Figure 17, transverse axis is represented wavelength (nm), and the longitudinal axis on the left side is represented absorbance (no unit), and the right side longitudinal axis is represented emissive porwer (a.u.).As shown in figure 17, and the organometallic complex Ir of gained (3,5-Fdpq) 2(pic) a plurality of absworption peaks are arranged.In addition, emission spectrum shows the luminous of 645nm emission peak, and that sees is luminous for red light.
Absworption peak at long wavelength side has a broad peak in the visual field, can think that this peak is the absorption spectrum that has only triple MLCT transition just to have.That is, determine Ir (3,5-Fdpq) 2(pic) be can direct sunshine to be excited to the triplet that excites and the compound of intersystem crossing.
Can be used as luminescent substance or sensitising agent according to the organometallic complex described in the synthesis example 1 to 5 of the present invention.
Next, by the absorption spectrum of the organometallic complex of the present invention that obtains in synthesis example 1 to 5, i.e. Figure 13 to Figure 17 can find the energy gap of each organometallic complex.By being energy along the wavelength Conversion of (absorption edge), calculate energy gap with the ABSORPTION EDGE of absorption spectrum.Table 1 is listed these results.
(table 1)
The abbreviation of organometallic complex of the present invention Energy gap [eV]
Synthesis example 1 Ir(Fdpq) 2(acac) 2.0
Synthesis example 2 Ir(dpq) 2(acac) 1.9
Synthesis example 3 Ir(Fdpq) 2(pic) 2.0
Synthesis example 4 Ir(3，5-Fdpq) 2(acac) 1.9
Synthesis example 5 Ir(3，5-Fdpq) 2(pic) 2.0
It should be noted that preferably each organometallic complex with the invention described above suitably is dispersed in the host material when using the organometallic complex conduct to be used for the luminescent material of light-emitting component.Table 2 has been listed the energy gap of the typical host material of measuring according to mode same as described above.
(table 2)
The abbreviation of typical case's host material Energy gap [eV]
TPAQn 2.8
CBP 3.5
α-NPD 3.1
Alq 3 2.8
By last table 1 and table 2 as can be known, therefore the energy gap of above-mentioned every kind of host material can be used as the host material of organometallic complex of the present invention all greater than organometallic complex of the present invention.
In addition, except energy gap, employing cyclic voltammetry (CV) is determined at the oxidation and the reduction characteristic of the organometallic complex of the present invention that obtains in the synthesis example, to estimate ionization potential and electron affinity.At first, use the organometallic complex Ir (Fdpq) of synthesis example 1 2(acac), the step that CV measures is described below as an example.
With electrochemical analyser (ALS Model 600A is from BAS) as measuring system.Be the solution that preparation is used in CV measures, will be as the tetra n butyl ammonium perchlorate (n-Bu of supporting electrolyte 4NClO 4) be dissolved in dimethyl formamide (DMF) solvent of dehydration, reach the concentration of 100mmol, will be as the Ir (Fdpq) of determination object 2(acac) further be dissolved to the concentration that reaches 1mmol.In addition, with platinum electrode (the PTE platinum electrode is from BAS), platinum electrode (the Pt counterelectrode that is used for VC-3 is from BAS) and Ag/Ag +Electrode (reference electrode of RE5 nonaqueous solvents is from BAS) is respectively as work electrode, auxiliary electrode and reference electrode.
By changing electromotive force, measure oxidation characteristic, at first from-0.4V to 1.2V, subsequently from 1.2V to-0.4V with respect to the work electrode of reference electrode.By changing electromotive force, measure reduction characteristic, at first from-0.4V to-2.4V, subsequently from-2.4V to-0.4V with respect to the work electrode of reference electrode.It should be noted that the sweep speed when CV measured is controlled at 0.1V/s.
Respectively expression Ir (Fdpq) shown in Figure 18 A and the 18B 2The CV curve of oxidation characteristic (acac) and expression Ir (Fdpq) 2The CV curve of reduction characteristic (acac).In Figure 18 A and 18B, the transverse axis and the longitudinal axis represent that respectively work electrode is with respect to the electromotive force (V) of reference electrode and the current value (1 * 10 between work electrode and the auxiliary electrode -5A).By Figure 18 A, can determine oxidation peak electromotive force (E Ox) be that 0.88V is (with respect to Ag/Ag +Electrode).In addition, by Figure 18 B, can determine reduction peak electromotive force (E Re) be-1.58V is (with respect to Ag/Ag +Electrode).
According to same assay method, also measured the oxidation peak electromotive force (E of each organometallic complex of the present invention that in synthesis example 2 and 3, obtains Ox) and reduction peak electromotive force (E Re).CV measures the results are shown in table 3.It should be noted that in these organometallic complex situations of the present invention, even the peak position of each CV curve of oxidation and reduction situation and peak intensity repeat all almost not change after 100 CV measure.Therefore, can also determine that described organometallic complex is all very stable to oxidation and reduction reaction.
(table 3)
The abbreviation of organometallic complex of the present invention E ox[eV] E re[eV]
Synthesis example 1 Ir(Fdpq) 2(acac) 0.88 -1.58
Synthesis example 2 Ir(dpq) 2(acac) 0.7-0.8 * -1.82
Synthesis example 3 Ir(Fdpq) 2(pic) 1.0-1.1 * -1.51
*The peak is unintelligible
In addition, when being used for the luminescent substance of light-emitting component, preferably organometallic complex suitably is dispersed in the host material with above-mentioned organometallic complex conduct of the present invention.As a result, according to same assay method, measure the oxidation peak electromotive force and the reduction peak electromotive force of typical host material.The results are shown in following table 4.
(table 4)
The abbreviation of typical case's host material E ox[eV] E re[eV]
TPAQ n 0.69 -2.05
CBP *1 1.25 -2.3 to-2.4 *2
α-NPD 0.45 -2.8 to-2.9 *2
Alq 3 0.7 to 0.8 *2 -2.20
*1 usefulness carrene is as solvent.
*2 peaks are unintelligible.
When comparison sheet 4 and table 3, determine that at first the reduction potential of each organometallic complex of the present invention is greater than host material (absolute value of reduction potential is less).Be that this electron affinity that shows organometallic complex of the present invention is greater than host material (easier being reduced), therefore propose the character that organometallic complex of the present invention has acceptant electronics, and can effectively catch charge carrier by organometallic complex being dispersed in the above-mentioned host material.
In addition, according to particular combinations, the oxidation potential of organometallic complex of the present invention is less than host material (for example, Ir (Fdpq) 2(acac) and Alq 3Combination, and with the situation of CBP as host material).In this combination, the ionization potential of organometallic complex of the present invention is less than host material (easier to be oxidized).Therefore, this applied in any combination when the light-emitting component, can not only effectively be caught electronics, can also effective dose catch the hole.
Preferred use can make organometallic complex of the present invention effectively catch the material in electronics and hole as host material.Yet host material needn't not only be caught electronics but also catch the hole, can catch any.In addition, when the energy gap of host material during, needn't always be to use to make organometallic complex of the present invention effectively catch the material in electronics and hole greater than the energy gap of organometallic complex.
[execution mode 2]
In this execution mode, the structure and the manufacture method thereof of light-emitting component of the present invention described referring to Figure 19.
At first, on substrate 1300, by the deposition tin indium oxide, forming film thickness is first electrode 1301 of 110nm.It should be noted that and adopt sputtering method to deposit.
Next, by deposited copper phthalocyanine on first electrode 1301, forming film thickness is the hole injection layer 1311 of 20nm.Carry out evaporation by being heated by resistive, deposit in the following manner, the substrate that is formed with first electrode 1301 on it is fixed on the substrate holder of commercially available vacuum deposition system, make form first electrode 1301 thereon the surface down, and copper phthalocyanine is placed in the vapor deposition source in this vacuum deposition system.
Next, by α-NPD deposition, form hole transmission layer 1312 on hole injection layer 1311, making film thickness is 40 nanometers.Deposit by evaporation according to the mode identical with forming hole injection layer 1311.
Next, α-NPD forms luminescent layer 1313 by deposition, make { 2,3-two (4-fluorophenyl) quinoxaline oxygen } (acetylacetone,2,4-pentanedione) iridium (III) that formula (16) represents (below be called Ir (Fdpq) 2(acac)) content is 8 weight % in α-NPD.By α-NPD and Ir (Fdpq) as vapor deposition source 2(acac) evaporation deposits altogether, to reach 30 nanometer film thickness.At this, the function of α-NPD is as host material.
Next, on luminescent layer 1313, pass through depositing Al q 3, form electron transfer layer 1314, making film thickness is 30 nanometers.Deposit by evaporation according to the mode identical with forming hole injection layer 1311.Then, on this electron transfer layer 1314, by depositing fluorinated calcium (CaF 2) form electron injecting layer 1315, making film thickness is 1 nanometer.Deposit by evaporation according to the mode identical with forming hole injection layer 1311.
Like this, the layer that comprises luminescent substance 1302 can pass through stacked hole injection layer 1311, hole transmission layer 1312, luminescent layer 1313, electron transfer layer 1314 and electron injecting layer 1315 formation.
Next, form second electrode 1303 by deposition of aluminum on electron injecting layer 1315, making film thickness is 150 nanometers.Deposit by evaporation according to the mode identical with forming hole injection layer 1311.
In addition, the glove box with in the light-emitting component immigration blanket of nitrogen of making seals with the encapsulant in the glove box.Behind the sealed light emitting element, light-emitting component is taken out room temperature (about 25 ℃) test current density-luminosity characteristic, voltage-luminosity characteristic and luminosity-current efficiency characteristic under initial condition in glove box.In addition, carry out the operational stability test with constant current driven, with the life-span of testing element.
At first, Figure 20 A to Figure 20 C illustrates the initial characteristic of the light-emitting component of making.Figure 20 A illustrates current density-luminosity characteristic, and Figure 20 B illustrates voltage-luminosity characteristic, and Figure 20 C illustrates luminosity-current efficiency characteristic.By voltage-luminosity characteristic, can determine when applying 9.0V voltage, with 440cd/m 2Luminosity emission bright dipping, luminous efficiency in this case is 1.0cd/A.In addition, emission spectrum has at the peak of 647 nano wave lengths, and the cie color coordinate that this element has is for (x y)=(0.67,0.32), can be determined by Ir (Fdpq) by this coordinate 2The redness of the very high color purity that (acac) provides or erythroid luminous.
Next, carry out the operational stability test, apply the electric current of the constant current value of certain hour in this test with constant current driven.Test method is, will be with 440cd/m under initial condition 2Required current density (the 44.3mA/cm of luminosity emission light 2) electric current keep the specific time, with test luminosity over time.As a result, remain on 68% of luminosity under the initial condition, do not reduce half through the luminosity after 3800 hours.The result can determine that the luminosity decline in time of light-emitting component of the present invention is less thus, has the favourable life-span.
In addition, proceed this operational stability test.Figure 21 illustrates result of the test, transverse axis express time among the figure (hour), the longitudinal axis is represented the ratio (that is relative luminosity (%)) of the luminosity under luminosity and the initial condition.According to result shown in Figure 21, adopt extrapolation to estimate that the half-life of this luminosity is about 8000 hours.
[execution mode 3]
In the embodiments of the present invention, describe the present invention referring to Figure 22 and use Alq 3Structure and manufacture method thereof as the light-emitting component of host material.
At first, on substrate 1400, by the deposition tin indium oxide, forming film thickness is first electrode 1401 of 110nm.
Next, by deposit DNTPD on first electrode 1401, form hole injection layer 1411, making film thickness is 20nm.Carry out evaporation by being heated by resistive device, deposit in the following manner, the substrate that is formed with first electrode 1401 on it is fixed on the substrate holder of commercially available vacuum deposition system, make form first electrode 1401 thereon the surface down, and DNTPD is placed in the vapor deposition source in this vacuum deposition system.
Next, by α-NPD deposition, form hole transmission layer 1412 on hole injection layer 1411, making film thickness is 10 nanometers.Deposit by evaporation according to the mode identical with forming hole injection layer 1411.
Next, by depositing Al q 3Form luminescent layer 1413, make formula (16) expression { 2,3-two (4-fluorophenyl) quinoxaline oxygen } (acetylacetone,2,4-pentanedione) iridium (III) (below be called Ir (Fdpq) 2(acac)) at Alq 3Middle content is 8 weight %.By Alq as vapor deposition source 3With Ir (Fdpq) 2(acac) evaporation deposits altogether, to reach 30 nanometer film thickness.At this, Alq 3Function be as host material.
Next, on luminescent layer 1413, pass through depositing Al q 3, form electron transfer layer 1414, making film thickness is 30 nanometers.Deposit by evaporation according to the mode identical with forming hole injection layer 1411.
Then, on this electron transfer layer 1414, by depositing fluorinated calcium (CaF 2) form electron injecting layer 1415, making film thickness is 1 nanometer.Deposit by evaporation according to the mode identical with forming hole injection layer 1411.
Like this, the layer that comprises luminescent substance 1402 can pass through stacked hole injection layer 1411, hole transmission layer 1412, luminescent layer 1413, electron transfer layer 1414 and electron injecting layer 1415 formation.
Next, form second electrode 1403 by deposition of aluminum on electron injecting layer 1415, making film thickness is 150 nanometers.Deposit by evaporation according to the mode identical with forming hole injection layer 1411.
In addition, the glove box with in the light-emitting component immigration blanket of nitrogen of making seals with the encapsulant in the glove box.Behind the sealed light emitting element, light-emitting component is taken out room temperature (about 25 ℃) test current density-luminosity characteristic, voltage-luminosity characteristic and luminosity-current efficiency characteristic under initial condition in glove box.In addition, carry out the operational stability test with constant current driven, with the life-span of testing element.
At first, Figure 23 A to Figure 23 C illustrates the initial characteristic of the light-emitting component of making.Figure 23 A illustrates current density-luminosity characteristic, and Figure 23 B illustrates voltage-luminosity characteristic, and Figure 23 C illustrates luminosity-current efficiency characteristic.By voltage-luminosity characteristic, can determine when applying 10.6V voltage, with 470cd/m 2Luminosity emission light, luminous efficiency in this case is 1.1cd/A.In addition, emission spectrum has at the peak of 659 nano wave lengths, and the cie color coordinate that this element has is for (x y)=(0.70,0.30), can be determined by Ir (Fdpq) by this coordinate 2The redness of the very high color purity that (acac) provides or erythroid luminous.
Next, carry out the operational stability test with constant current driven.Test method is, will be with 470cd/m under initial condition 2Required current density (the 41.7mA/cm of luminosity emission light 2) electric current keep the specific time, with test luminosity over time.As a result, after 1400 hours, luminosity remains on 89% of luminosity under the initial condition, does not reduce half.The result can determine that the luminosity decline in time of light-emitting component of the present invention is less thus, has the favourable life-span.
In addition, proceed this operational stability test.Figure 24 illustrates result of the test, transverse axis express time among the figure (hour), the longitudinal axis is represented the ratio (that is relative luminosity (%)) of the luminosity under luminosity and the initial condition.According to result shown in Figure 24, adopt extrapolation to estimate that the half-life of this luminosity is about 34000 hours.
[execution mode 4]
In this execution mode, describe and use two kinds of material α-NPD and Alq 3Example as the light-emitting component of host material.Element in this execution mode is made according to the mode identical with execution mode 3, and difference is to adopt the structure of luminescent layer 1413 described below.
Luminescent layer 1413 forms by three source evaporations, wherein, is 0.4nm/s with the evaporation rate setting of α-NPD, Alq 3The evaporation rate setting when being 0.1nm/s to the Ir (Fdpq) of formula (16) expression 2(acac) carry out evaporation.In this case, with Ir (Fdpq) 2(acac) it is 8 weight % that addition is controlled at respect to α-NPD.In addition, making the film thickness of luminescent layer 1413 is 30 nanometers.At this, α-NPD and Alq 3Function be as host material.
In addition, the glove box with in the light-emitting component immigration blanket of nitrogen of making seals with the encapsulant in the glove box.Behind the sealed light emitting element, light-emitting component is taken out room temperature (about 25 ℃) test current density-luminosity characteristic, voltage-luminosity characteristic and luminosity-current efficiency characteristic under initial condition in glove box.In addition, carry out the operational stability test with constant current driven, with the life-span of testing element.
At first, Figure 25 A to Figure 25 C illustrates the initial characteristic of the light-emitting component of making.Figure 25 A illustrates current density-luminosity characteristic, and Figure 25 B illustrates voltage-luminosity characteristic, and Figure 25 C illustrates luminosity-current efficiency characteristic.By these results, can determine when applying 7.6V voltage, with 510cd/m 2Luminosity emission light, luminous efficiency is 1.3cd/A.In addition, emission spectrum has at the peak of 640 nano wave lengths, and the cie color coordinate that this element has is for (x y)=(0.70,0.30), can be determined by Ir (Fdpq) by this coordinate 2Red or the erythroid light of the very high color purity that (acac) provides.
Next, carry out the operational stability test with constant current driven.Test method is, will be with 510cd/m under initial condition 2Required current density (the 37.8mA/cm of luminosity emission light 2) electric current keep the specific time, with test luminosity over time.As a result, after 1200 hours, luminosity remains on 90% of luminosity under the initial condition, does not reduce half.The result can determine that the luminosity decline in time of light-emitting component of the present invention is less thus, has the favourable life-span.
In addition, proceed this operational stability test.Figure 26 illustrates result of the test, transverse axis express time among the figure (hour), the longitudinal axis is represented the ratio (that is relative luminosity (%)) of the luminosity under luminosity and the initial condition.According to result shown in Figure 26, adopt extrapolation to estimate that the half-life of this luminosity is about 40000 hours.
[execution mode 5]
In this execution mode, structure and the manufacture method thereof of use organometallic complex of the present invention as the light-emitting component of luminescent substance described referring to Figure 19.This execution mode is that wherein luminescent layer has the structure identical with execution mode 2, and to the thickness of other layer and material preferably with an example of further raising luminous efficiency.
At substrate 1300, the tin indium oxide by sputter formation silicon oxide-containing forms first electrode 1301.Its film thickness is 110 nanometers.
Next, the substrate 1300 that is formed with first electrode 1301 on it is fixed on the substrate holder in the vacuum deposition system, make be formed with first electrode 1301 the surface downwards.
Next,, carry out evaporation by being heated by resistive device at first electrode 1301, deposition 4,4 '-two [N-{4-(N, N-two--toluidino) phenyl }-the N-phenyl amino] (abbreviation: DNTPD), film thickness is 50 nanometers to biphenyl, forms hole injection layer 1311.
Next, on hole injection layer 1311, carry out evaporation by being heated by resistive device, deposition α-NPD, film thickness is 10 nanometers, forms hole transmission layer 1312.
Next, on hole transmission layer 1312, by being total to vapor deposition Ir (Fdpq) 2(acac) and α-NPD, film thickness is 30 nanometers, forms luminescent layer 1313.At this, make Ir (Fdpq) 2(acac) the quality ratio with α-NPD is 1: 0.08 (=α-NPD: Ir (Fdpq) 2(acac)).This ratio can make Ir (Fdpq) 2(acac) be dispersed in the layer of forming by α-NPD.It should be noted that common evaporation is a kind of like this evaporation coating method, promptly carries out evaporation by a plurality of vapor deposition source simultaneously in an operating room.
Next, on luminescent layer 1313, carry out evaporation, depositing Al q by being heated by resistive device 3, film thickness is 70 nanometers, forms electron transfer layer 1314.
Next, on electron transfer layer 1314, carry out evaporation by being heated by resistive device, depositing fluorinated calcium, film thickness are 1 nanometer, form electron injecting layer 1315.
Next, on electron injecting layer 1315, carry out evaporation by being heated by resistive device, deposition of aluminum, film thickness is 200 nanometers, forms second electrode 1303.
In blanket of nitrogen, the light-emitting component of making is like this sealed.Afterwards,, apply voltage, make the electromotive force of first electrode 1301 be higher than the electromotive force of second electrode 1303 for the test operation characteristic.It should be noted that under maintenance room temperature (25 ℃) and measure.Figure 27 A to 27C illustrates the result of this mensuration.Figure 27 A illustrates the test result of current density-luminosity characteristic, and Figure 27 B illustrates the test result of voltage-luminosity characteristic, and Figure 27 C illustrates the test result of luminosity-current efficiency characteristic.In Figure 27 A, the transverse axis and the longitudinal axis are represented current density (mA/cm respectively 2) and luminosity (cd/m 2).At Figure 27 B, the transverse axis and the longitudinal axis are represented voltage (V) and luminosity (cd/m respectively 2).Among Figure 27 C, the transverse axis and the longitudinal axis are represented luminosity (cd/m respectively 2) and current efficiency (cd/A).
By these results, can determine when applying 7.2V voltage, with 520cd/m 2Luminosity emission light.Luminous efficiency in this case is 3.8cd/A.In addition, emission spectrum has at the peak of 644 nano wave lengths, and the cie color coordinate that this element has is for (x y)=(0.66,0.33), can be determined by Ir (Fdpq) by this coordinate 2The redness of the very high color purity that (acac) provides or erythroid luminous.
Next, by the operational stability test, test luminosity over time.The operational stability test is carried out in the following manner, will be with 520cd/m under initial condition 2(light-emitting component for present embodiment is 13.9mA/cm to the required current density of luminosity emission light 2) electric current keep the specific time, test is in the luminosity of the time period in each past.It should be noted that this test remains on room temperature (25 ℃) and carries out.
Figure 28 illustrates the result of operational stability test.Transverse axis express time in Figure 28 (hour), the longitudinal axis is represented the ratio (that is relative luminosity (%)) of the luminosity under luminosity and the initial condition.By Figure 28, can determine that the relative luminosity after 1400 hours is 95%, promptly initial luminosity descends 5%, does not reach half of initial luminosity.That is, can determine that light-emitting component of the present invention is the element with favourable life-span.In addition, according to the result of Figure 28, adopt extrapolation to estimate that the half-life of this luminosity is about 19000 hours.
[execution mode 6]
In this execution mode, structure and the manufacture method thereof of use organometallic complex of the present invention as the luminescent layer of luminescent substance described referring to Figure 22.Execution mode 6 is that wherein light-emitting component has the structure identical with execution mode 3, and to the thickness of other layer and material preferably with an example of further raising luminous efficiency.
On substrate 1400, the tin indium oxide by sputter formation silicon oxide-containing forms first electrode 1401.Its film thickness is 110 nanometers.
Next, the substrate 1400 that is formed with first electrode 1401 on it is fixed on the substrate holder in the vacuum deposition system, make be formed with first electrode 1401 the surface downwards.
Next, on first electrode 1401, carry out evaporation by being heated by resistive device, deposition DNTPD, film thickness is 50 nanometers, forms hole injection layer 1411.
Next, on hole injection layer 1411, carry out evaporation by being heated by resistive device, deposition α-NPD, film thickness is 10 nanometers, forms hole transmission layer 1412.
Next, on hole transmission layer 1412, by being total to evaporation, deposition Ir (Fdpq) 2(acac) and Alq 3, film thickness is 30 nanometers, forms luminescent layer 1413.At this, make Ir (Fdpq) 2(acac) and Alq 3Quality ratio be 1: 0.08 (=Alq 3: Ir (Fdpq) 2(acac)).This ratio can make Ir (Fdpq) 2(acac) be dispersed in by Alq 3In the layer of forming.It should be noted that common evaporation is a kind of like this evaporation coating method, promptly carries out evaporation by a plurality of vapor deposition source simultaneously in an operating room.
Next, on luminescent layer 1413, carry out evaporation, depositing Al q by being heated by resistive device 3, film thickness is 70 nanometers, forms electron transfer layer 1414.
Next, on electron transfer layer 1414, carry out evaporation by being heated by resistive device, depositing fluorinated calcium, film thickness are 1 nanometer, form electron injecting layer 1415.
Next, on electron injecting layer 1415, carry out evaporation by being heated by resistive device, deposition of aluminum, film thickness is 200 nanometers, forms second electrode 1403.
In blanket of nitrogen, the light-emitting component of making is like this sealed.Afterwards,, apply voltage, make the electromotive force of first electrode 1401 be higher than the electromotive force of second electrode 1403 for the test operation characteristic.It should be noted that under maintenance room temperature (25 ℃) and measure.Figure 29 A to 29C illustrates the result of this mensuration.Figure 29 A illustrates the test result of current density-luminosity characteristic, and Figure 29 B illustrates the test result of voltage-luminosity characteristic, and Figure 29 C illustrates the test result of luminosity-current efficiency characteristic.In Figure 29 A, the transverse axis and the longitudinal axis are represented current density (mA/cm respectively 2) and luminosity (cd/m 2).At Figure 29 B, the transverse axis and the longitudinal axis are represented voltage (V) and luminosity (cd/m respectively 2).Among Figure 29 C, the transverse axis and the longitudinal axis are represented luminosity (cd/m respectively 2) and current efficiency (cd/A).
By these results, can determine when applying 8.6V voltage, with 490cd/m 2Luminosity emission light.Luminous efficiency in this case is 3.7cd/A.In addition, emission spectrum has at the peak of 656 nano wave lengths, and the cie color coordinate that this element has is for (x y)=(0.64,0.34), is determined by Ir (Fdpq) by this coordinate cocoa 2The redness of the very high color purity that (acac) provides or erythroid luminous.
Next, by the operational stability test, test luminosity over time.The operational stability test is carried out in the following manner, will be with 490cd/m under initial condition 2(light-emitting component for present embodiment is 13.3mA/cm to the required current density of luminosity emission light 2) electric current keep the specific time, test is in the luminosity of the time period in each past.It should be noted that this test remains under the room temperature (25 ℃) carries out.
Figure 30 illustrates the result of operational stability test.Transverse axis express time in Figure 30 (hour), the longitudinal axis is represented the ratio (that is relative luminosity (%)) of the luminosity under luminosity and the initial condition.By Figure 30, can determine that the relative luminosity after 1800 hours is 84%, promptly initial luminosity descends 16%, does not reach half of initial luminosity.That is, can determine that light-emitting component of the present invention is the element with favourable life-span.In addition, according to the result of Figure 30, adopt extrapolation to estimate that the half-life of this luminosity is about 33000 hours.
[execution mode 7]
This execution mode is an example of the light-emitting component made referring to the mode according to identical with execution mode 6 that Figure 22 describes, and difference is the structure that has changed electron transfer layer 1414 and electron injecting layer 1415 as described below.
In this execution mode, making electron transfer layer 1414 film thicknesses is 30 nanometers.In addition, by being total to evaporating Al q 3Form electron injecting layer 1415 with Li, its film thickness is 40 nanometers.At this, make Li and Alq 3Quality ratio be 1: 0.01 (=Alq 3: Li).
In blanket of nitrogen, the light-emitting component of making is like this sealed.Afterwards,, apply voltage, make the electromotive force of first electrode 1401 be higher than the electromotive force of second electrode 1403 for the test operation characteristic.It should be noted that under maintenance room temperature (25 ℃) and measure.Figure 31 A to 31C illustrates the result of this mensuration.Figure 31 A illustrates the test result of current density-luminosity characteristic, and Figure 31 B illustrates the test result of voltage-luminosity characteristic, and Figure 31 C illustrates the test result of luminosity-current efficiency characteristic.In Figure 31 A, the transverse axis and the longitudinal axis are represented current density (mA/cm respectively 2) and luminosity (cd/m 2).At Figure 31 B, the transverse axis and the longitudinal axis are represented voltage (V) and luminosity (cd/m respectively 2).Among Figure 31 C, the transverse axis and the longitudinal axis are represented luminosity (cd/m respectively 2) and current efficiency (cd/A).
By these results, can determine when applying 7.6V voltage, with 480cd/m 2Luminosity emission light.Current efficiency in this case is 3.5cd/A.In addition, emission spectrum has at the peak of 656 nano wave lengths, and the cie color coordinate that this element has is for (x y)=(0.66,0.33), is determined by Ir (Fdpq) by this coordinate cocoa 2The redness of the very high color purity that (acac) provides or erythroid luminous.
Next, by the operational stability test, test luminosity over time.The operational stability test is carried out in the following manner, will be with 480cd/m under initial condition 2(the light-emitting component situation of present embodiment is 13.7mA/cm to the required current density of luminosity emission light 2) electric current keep the specific time, test is in the luminosity of the time period in each past.It should be noted that this test carries out under the room temperature (25 ℃) keeping.Figure 32 illustrates the structure of operational stability test.Among Figure 32, the transverse axis express time (hour), the longitudinal axis is represented the ratio (that is relative luminosity (%)) of luminosity under luminosity and the initial condition.By Figure 32, can determine that the relative luminosity after 740 hours is 86%, promptly initial luminosity descends 14%, does not reach half of initial luminosity.That is, can determine that light-emitting component of the present invention is the element with favourable life-span.In addition, according to the result of Figure 32, adopt extrapolation to estimate that the half-life of this luminosity is about 36000 hours.
[execution mode 8]
Execution mode 8 is to have and execution mode 4 same structures, and to the thickness of other layer and material preferably with example of luminescent layer of further raising luminous efficiency, and according to an example of the light-emitting component made from execution mode 6 same way as, difference is the structure that has changed electron transfer layer 1414 and electron injecting layer 1415 as described below.Describe referring to Figure 22.
In this execution mode, luminescent layer 1413 is by carrying out α-NPD, Alq simultaneously 3And Ir (Fdpq) 2(acac) three source evaporations of evaporation form.In this case, setting deposition ratio is Alq 3: α-NPD: Ir (Fdpq) 2(acac) quality ratio=1: 1: 0.08.In addition, the film thickness of luminescent layer 1413 is 30 nanometers.At this, α-NPD and Alq 3Function be as host material.In addition, the film thickness of electron transfer layer 1414 is 60 nanometers.
In blanket of nitrogen, the light-emitting component of making is like this sealed.Afterwards,, apply voltage, make the electromotive force of first electrode 1401 be higher than the electromotive force of second electrode 1403 for the test operation characteristic.It should be noted that under maintenance room temperature (25 ℃) and measure.Figure 33 A to 33C illustrates the result of this mensuration.Figure 33 A illustrates the test result of current density-luminosity characteristic, and Figure 33 B illustrates the test result of voltage-luminosity characteristic, and Figure 33 C illustrates the test result of luminosity-current efficiency characteristic.In Figure 33 A, the transverse axis and the longitudinal axis are represented current density (mA/cm respectively 2) and luminosity (cd/m 2).At Figure 33 B, the transverse axis and the longitudinal axis are represented voltage (V) and luminosity (cd/m respectively 2).Among Figure 33 C, the transverse axis and the longitudinal axis are represented luminosity (cd/m respectively 2) and current efficiency (cd/A).
By these results, can determine when applying 7.8V voltage, with 560cd/m 2Luminosity emission light.Luminous efficiency in this case is 3.6cd/A.In addition, emission spectrum has at the peak of 651 nano wave lengths, and the cie color coordinate that this element has is for (x y)=(0.68,0.31), is determined by Ir (Fdpq) by this coordinate cocoa 2The redness of the very high color purity that (acac) provides or erythroid luminous.
Next, by the operational stability test, test luminosity over time.The operational stability test is carried out in the following manner, will be with 560cd/m under initial condition 2(the light-emitting component situation in present embodiment is 15.6mA/cm to the required current density of luminosity emission light 2) electric current keep the specific time, test is in the luminosity of the time period in each past.It should be noted that this test carries out under the room temperature (25 ℃) keeping.
Figure 34 illustrates the structure of operational stability test.Among Figure 34, the transverse axis express time (hour), the longitudinal axis is represented the ratio (that is relative luminosity (%)) of the luminosity under luminosity and the initial condition.By Figure 34, can determine that the relative luminosity after 640 hours is 84%, promptly initial luminosity descends 16%, does not reach half of initial luminosity.That is, can determine that light-emitting component of the present invention is the element with favourable life-span.In addition, according to the result of Figure 34, adopt extrapolation to estimate that the half-life of this luminosity is about 68000 hours.
[execution mode 9]
In this execution mode, the light-emitting device that has light-emitting component of the present invention in the pixel portion is described referring to Figure 35 A and 35B.Figure 35 A is the vertical view that this light-emitting device is shown, and Figure 35 B is the sectional view of getting along A-A ' line among Figure 35 A.The label 1501 of with dashed lines mark refers to driving circuit section (source drive circuit), and label 1502 refers to pixel portion, and label 1503 refers to driving circuit section (gate electrode side (gate side) drive circuit).In addition, label 1504 and 1505 refers to hermetic sealing substrate and encapsulant respectively.The inside 1506 that is surrounded by encapsulant 1505 is spaces.
In addition, label 1507 refer to will input signal be transferred to source drive circuit 1501 and gate side drive circuit 1503 and accept as the distribution of the signal of vision signal, clock signal, enabling signal and reset signal from FPC (flexible print circuit) 1508,1508 are used as outside input terminal.Though it should be noted that FPC only is shown in the accompanying drawings, printed circuit board (PCB) (PWB) can be connected with this FPC.Light-emitting device of the present invention not only comprises the light-emitting device main body, also comprises the state that FPC or PWB are connected with light-emitting device.
Next, the structure of section is described referring to Figure 35 B.Though on substrate 1509, formed drive circuit and pixel portion, this illustrate as the source drive circuit 1501 and the pixel portion 1502 of driving circuit section.
In the source drive circuit 1501,, n-passage TFT1517 forms cmos circuit by being combined with p-passage TFT1518.The TFT that forms drive circuit can adopt known cmos circuit, PMOS circuit or nmos circuit to form.Though present embodiment shows a kind of integrated-type and drive that wherein form drive circuit on substrate, this is not essential, drive circuit can be on substrate, but is formed at the substrate outside.
Pixel portion 1502 has a plurality of pixels, and they comprise conversion TFT1510, circuit control TFT1511 separately and are electrically connected to first electrode 1512 of the drain electrode of control TFT1511.In addition, form insulator 1513, to cover the side of first electrode 1512.At this, with the acrylic resin film formation insulator 1513 of positive sensitization.
In addition, for reaching useful covering, the insulator 1513 of formation has the top section or the base section of the curved surface of certain curvature.For example, with the situation of positive sensitization acrylic compounds, preferably have only the base section of insulator 1513 to have the curved surface of certain curvature radius (0.2-3 micron) as the material of insulator 1513.In addition, negative photosensitive material becomes when being subjected to illumination and is insoluble to etchant, and positive photosensitive material becomes when being subjected to illumination and is dissolved in etchant, can described any negative photosensitive material and just photosensitive material be used for insulator 1513.In addition, not only can use organic substance also can use the material of inorganic substances, for example, can use silica and silicon oxynitride as insulator 1513.
On first electrode 1512, can form the layer 1514 that comprises the luminescent substance and second electrode 1515.At this, preferred use has the material of the material conduct of big work content as first electrode 1512 of anode.For example, except as comprise the monofilm of the film of tin indium oxide, the film that includes the tin indium oxide of silica, the film that comprises indium zinc oxide, titanium nitride film, chromium film, tungsten film, Zn film and Pt film, can use stepped construction, as titanium nitride film and contain the sandwich that aluminium is the film of key component, and titanium nitride film, contain the three-decker that aluminium is the film and the titanium nitride film of key component.When adopting stepped construction, may as distribution the time, have low resistance, have favourable ohmic contact, and can be used as anode.
In addition, by using deposition mask or, forming the layer 1514 that comprises luminescent substance by ink-jet.The layer 1514 that comprises luminescent substance comprises organometallic complex of the present invention.Can use low molecular weight substance, middle molecular substances (comprising oligomer and branch polymers (dendrimer)) or polymeric material as the material that combines with organometallic complex.In addition, the material as the layer that is used to comprise luminescent substance often uses organic material to be used for individual layer or sandwich.Yet, the present invention includes the structure of a part that inorganic compound is used to include the film of organic compounds.
In addition,, can use the material of less work content as the material that is used for forming second electrode (negative electrode) 1515 on the layer 1514 of luminescent substance containing, for example Al, Ag, Li or Ca, and alloy, as Mg:Ag, Mg:In, Al:Li, or metallic compound, as CaF 2Or CaN.The optical transmission that produces in comprising the layer 1514 of luminescent substance is by under the situation of second electrode 1515, preferred less metallic film and nesa coating (for example, the alloy (In of the alloy of indium oxide and tin oxide (ITO), indium oxide and zinc oxide of film thickness that use 2O 3-ZnO) or zinc oxide (ZnO)) sandwich as second electrode (negative electrode) 1515.
In addition, hermetic sealing substrate 1504 bonds with substrate 1509 usefulness encapsulants 1505, in the structure of formation, provides light-emitting component 1516 in the space that is surrounded by substrate 1509, hermetic sealing substrate 1504 and encapsulant 1505.Except the situation of filling with inert gas (for example nitrogen or argon gas), this space 1506 also comprises the structure of filling with encapsulant 1505.
It should be noted that the preferred epoxy resin of using is as encapsulant 1505.In addition, require to use the material that is difficult to make moisture or oxygen infiltration.In addition, to material, except glass substrate and quartz base plate, can use by FRP (plastics that fibrous glass strengthens) PVF (polyvinyl fluoride), Mylar, polyester, the plastic base that acrylic compounds etc. constitute as hermetic sealing substrate 1504.
As mentioned above, can obtain to have the light-emitting device of light-emitting component of the present invention.In the light-emitting device of the invention described above, emitting component height of the present invention, and can drive for a long time.Therefore, this light-emitting device has low energy consumption and long-life.
[execution mode 10]
In this execution mode, the various electrical equipment made from the light-emitting device with light-emitting component of the present invention are described.Because light-emitting device of the present invention has low energy consumption and long-life, uses the electronic device of this light-emitting device also can use for a long time by the power that for example reduces display part and illumination section.
Adopt the electrical equipment of the light-emitting device manufacturing of manufacturing of the present invention to comprise: television set, camera, digital camera, goggle-type display (being installed in the display of head), navigation system, audio reproducing apparatus (as automobile-used sound system or sound part), laptop PC, game machine, personal digital assistant (as, movable computer, portable phone, portable game machine or e-book etc.), the image reproducing apparatus that recording medium arranged (particularly, the equipment of energy regenerative recording media such as digital universal disc (DVD), it comprises the display device that can show its image) and lighting apparatus.Some object lesson of electrical equipment is described referring to Figure 36 A to 36E.These object lessons that use the electrical equipment of light-emitting device of the present invention to be not limited to list.
Be a display shown in Figure 36 A, it comprises: casing 1600, support 1601, display part 1602, loudspeaker part 1603 and video input terminal 1604.Available light-emitting device of the present invention is made the display part 1602 of display.Display comprises all devices that are used for display message, for example, is used for PC, is used to receive TV broadcasting, is used for display ads etc.
Be a laptop computer shown in Figure 36 B, it comprises main body 1700, casing 1701, display part 1702, keyboard 1703, external connection port 1704, indication mouse 1705.The display part 1702 that the available light-emitting device that light-emitting component of the present invention arranged is made laptop computer.
Be a camera shown in Figure 36 C, it comprises main body 1800, display part 1801, casing 1802, external connection port 1803, Long-distance Control receiving unit 1804, image receiving unit 1805, battery 1806, audio frequency importation 1807, operation keys 1808 and ocular lens 1809.Light-emitting device with light-emitting component of the present invention can be used to make the display part 1801 of camera.
Figure 36 D is desk-top lighting apparatus, and it comprises illumination section 1900, lampshade 1901, variable arm 1902, support 1903, base 1904 and power supply 1905.The light-emitting device that is formed by light-emitting component of the present invention can be used to make the illumination section 1900 of desk-top lighting apparatus.It should be noted that this lighting apparatus comprises the lighting apparatus and the wall-hanging lighting apparatus that can be fixed to ceiling.
Be a kind of portable phone shown in Figure 36 E, it comprises, and main body 2000, casing 2001, display part 2002, audio frequency importation 2003, audio output part divide 2004, operation keys 2005, external connection port 2006 and antenna 2007.Light-emitting device with light-emitting component of the present invention can be used to make the display part 2002 of portable phone.
As mentioned above, can use light-emitting component of the present invention to make electrical equipment.In addition, in the above-mentioned various electrical equipment of the present invention, emitting component height of the present invention can drive for a long time.Therefore, described electrical equipment can drive for a long time in low energy consumption, is economical therefore.
[execution mode 11]
In this execution mode, the situation of using luminescent substance of the present invention and another kind of luminescent substance to form the element of emission white light is described.
For form the element of emission white light with luminescent substance of the present invention, must between first electrode and second electrode, provide a plurality of luminous zones, and control the color of sending light from each luminous zone, to obtain whole white light.Yet, when formation comprises the luminous zone that luminescent substance of the present invention is redness or blush phosphorus, when making it to contact with another luminous zone that comprises another kind of luminescent substance, energy takes place between luminescent substance to be shifted, there is the possibility that following phenomenon takes place, promptly only to the luminous stronger light of color emission of arbitrary luminescent substance wherein, and to the more weak light of the luminous color emission of all the other luminescent substances.For improving this unbalanced glow color, between the luminous zone, provide independently layer.Require this independent stratum to have the biography light property, and can adopt electron transport material or both hole and electron transferring material to form.Particularly, can use at electron transport material described in the Implementation Modes and hole mobile material.
Next, the example of the component structure of the emission white light that provides two luminous zones shown in Figure 37.Among Figure 37, first luminous zone 2102 and second luminous zone 2104 are arranged between first electrode 2101 and second electrode 2105, and between first luminous zone 2102 and second luminous zone 2104, have one independently the layer 2103.Label 2100 refers to substrate.When phosphor material of the present invention is used for first luminous zone 2102, when the blue-green luminescent substance is used for second luminous zone 2104, can obtain white light on the whole.
The blue-green luminescent substance that forms second luminous zone 2104 comprises following fluorescent material such as perylene, 2,5,8, (the abbreviation: TBP) of 11-four-uncle Ding Ji perylene, 4,4 '-two (2-diphenylacetylene) biphenyl (DPVBi), 4,4 '-two [2-(N-ethyl carbazole-3-yl) vinyl] biphenyl (abbreviation: BCzVBi), (abbreviation: of two (2-methyl-oxine)-4-phenylphenol (phenolato)-aluminium BAlq) with (abbreviation: Gamq of two (2-methyl-oxine closes)-chlorine galliums 2Cl), and phosphorus, as pyridine carboxylic acid (picolinate) two [2-(3,5-two (trifluoromethyl) phenyl) pyridine acid oxygen (pyridinato)-N, C 2 '] iridium (III) (Ir (CF3ppy) 2(pic)), acetylacetone,2,4-pentanedione two [2-(4 ', 6 '-difluorophenyl) pyridine acid oxygen-N, C 2 '] iridium (III) (FIr (acac)) and pyridine carboxylic acid two [2-(4 ', 6 '-difluorophenyl) pyridine acid oxygen-N, C 2 '] iridium (III) (FIr (pic)).
Specifically describe structure shown in Figure 37 below.On substrate 2100, deposition is as the ITO of first electrode 2101, and film thickness is 110 nanometers.
Next, form first luminous zone 2102.Particularly, DNTPD is the hole injected material, and α-NPD is the hole transport material, deposits the DNTPD of 50 nanometers and the α-NPD of 30 nanometers respectively.Afterwards, by being total to evaporation, deposit redness of the present invention or blush phosphorus and α-NPD, film thickness is 30 nanometers, makes Ir (Fdpq) 2(acac) content is 8 weight %.
Next, thickness of deposited film is the CBP of 5 nanometers, as independent stratum 2103.Afterwards, form second luminous zone 2104.Particularly, deposition blue-green phosphorus Ir (CF 3Ppy) 2(pic) and CBP, film thickness is 25 nanometers, makes Ir (CF 3Ppy) 2(pic) content is 8 weight %.Then, deposit the BCP of 10 nanometers, BCP is hole blocking material (and electron transport material), deposits the Alq of 20 nanometers again 3As electron transfer layer.After this, deposit the calcirm-fluoride (abbreviation: CaF of 1 nano thickness 2) as electron injecting layer.
After this, deposit the Al of 150 nanometers as second electrode 2105.
According to the method, can obtain to launch the element of white light with phosphorus of the present invention and blue-green phosphorus.In structure shown in Figure 37, bipolar material is used for independent stratum 2103.Yet, can use hole transport material, electron transport material, hole blocking material etc., and be not limited to bipolar material.In addition, though, can provide more luminous zone, to obtain whole white light at the example of two light-emitting components shown in this execution mode.
Perhaps, under the situation of the element that forms the emission white light with the blue-green fluorescent material, the ITO that deposits 110 nanometers is as first electrode 2101, deposit respectively 50 nanometers as the DNTPD of hole injected material and the α-NPD as the hole transport material of 30 nanometers, and to first luminous zone 2102, common evaporation is provided, and depositing of the present invention is the Ir (Fdpq) of redness or blush phosphorus 2(acac) and α-NPD, film thickness is 30 nanometers, makes Ir (Fdpq) 2(acac) content is 8 weight %.After this, the CBP that deposits 5 nanometers for second luminous zone 2104, deposits blue-green Ying light Wu Zhi perylene and Balq as independent stratum 2103, and film thickness is that the content of 25 nanometer ， Shi perylenes is 1 weight %.Then, deposit the Alq of 30 nanometers 3As electron transfer layer.After this, deposit the CaF of 1 nanometer 2As electron injecting layer, last, the Al that deposits 150 nanometers is as second electrode 2105.According to the method, can obtain to launch the element of white light with redness or blush phosphorus and blue-green fluorescent material.
[execution mode 12]
In this execution mode, referring to Figure 38 the situation of using phosphorus of the present invention to form the element of emission white light is described, its structure is different from the structure of execution mode 11.
Among Figure 38, first luminous zone 2202, second luminous zone 2204 and the 3rd luminous zone 2206 are arranged between first electrode 2201 and second electrode 2207.In addition, between first luminous zone 2202 and second luminous zone 2204, exist charge carrier to generate layer 2203, and the charge carrier between second luminous zone 2204 and the 3rd luminous zone 2206 generate layer 2205.Respectively phosphorus of the present invention, green or little green emitting material and blue or little blue-light-emitting material are used for first luminous zone 2202, second luminous zone 2204 and the 3rd luminous zone 2206.
Blue or little blue-light-emitting material comprises fluorescent material, as the ， perylene, 2,5,8,11-four-uncle Ding Ji perylene (abbreviation: TBP), 1,1,4, (the abbreviation: TPB) of 4-tetraphenyl-1,3-butadiene, 9,9 '-dianthranide (abbreviation: BiAnt), 9, (the abbreviation: DPA) of 10-diphenylanthrancene, 9,10-two (2-naphthyl) anthracene (abbreviation: DNA), 9,10-two (2-naphthyl)-2-tert-butyl anthracene (abbreviation: t-BuDNA), phosphorus, as four (1-pyrazolyl) boric acid two [2-(4 ', 6 '-difluorophenyl) pyridine acid oxygen-N, C 2 '] iridium (III) (abbreviation: FIr6).
Green or be the green emitting material and comprise: fluorescent material, as, coumarin 6, cumarin 545T, N, and N '-dimethyl quinoline a word used for translation diketone (abbreviation: DMQd), 5, (the abbreviation: of 12-diphenyl aphthacene DPT) with three (oxine closes) aluminium, phosphorus, as, three (2-phenylpyridine acid oxygen-N, C 2 ') iridium (abbreviation: Ir (ppy) 3), acetylacetone,2,4-pentanedione two (2-phenylpyridine acid oxygen-N, C 2 ') iridium (III) (abbreviation: Ir (ppy) 2And acetylacetone,2,4-pentanedione two [2-(4-aminomethyl phenyl) pyridine acid oxygen-N, C (acac)) 2 '] iridium (III) (abbreviation: Ir (tpy) 2(acac)).
In addition, generate layer with nesa coating as charge carrier.Specifically have: tin indium oxide (abbreviation: ITO), siliceous tin indium oxide, comprise the indium oxide of 2-20% zinc oxide.
Specifically describe the structure shown in Figure 38 below.On substrate 2200, deposition is as the ITO of first electrode 2201, and film thickness is 110 nanometers.Particularly, by evaporation altogether, deposit the molybdenum oxide of 50 nanometer film thickness and α-NPD as hole injection layer, the quality ratio that makes molybdenum oxide and α-NPD is 1: 0.25 (=α-NPD: molybdenum oxide), deposit the hole transport material α-NPD of 10 nanometers.Next, form first luminous zone 2202.Particularly, by being total to evaporation, deposit redness of the present invention or blush phosphorus Ir (Fdpq) 2(acac) and Alq 3, film thickness is 37.5 nanometers, makes Ir (Fdpq) 2(acac) content is 8 weight %.Deposit the Alq of 27.5 nanometers 3As electron transfer layer, and by being total to evaporation, deposition BCP and Li are as electron injecting layer, and film thickness is 10 nanometers, and the quality ratio that makes Li and BCP is 1: 0.005 (=BCP: Li).Then, deposit the ITO of 20 nanometer film thickness as charge carrier generation layer (nesa coating) 2203.
On nesa coating 2203, form second luminous zone 2204.Particularly, by evaporation altogether, deposition α-NPD and molybdenum oxide be as hole injection layer, film thickness 50 nanometers, and the quality ratio that makes molybdenum oxide and α-NPD is that (=α-NPD: molybdenum oxide), and the α-NPD that deposits 10 nanometers was as the hole transport material in 1: 0.25.Then, by being total to evaporation coumarin 6 and Alq 3, as the green or little green emitting material that is used for second luminous zone 2204, film thickness is 37.5 nanometers.Then, deposit the Alq of 27.5 nanometers 3As electron transfer layer, by being total to evaporation, deposition BCP and Li are as electron injecting layer, and film thickness is 10 nanometers, and the quality ratio that makes Li and BCP is 1: 0.005 (=BCP: Li).Then, thickness of deposited film is that the ITO of 20 nanometers generates layer (nesa coating) 2205 as charge carrier.
On nesa coating 2205, form the 3rd luminous zone 2206 in a similar way.Particularly, by being total to evaporation, deposition α-NPD and molybdenum oxide are as hole injection layer, and film thickness is 50 nanometers, and the quality ratio that makes molybdenum oxide and α-NPD is 1: 0.25 (=α-NPD: molybdenum oxide), deposit the hole transport material α-NPD of 10 nanometers.Then, thickness of deposited film is that the t-BuDNA of 37.5 nanometers is as the blue or little blue-light-emitting material that is used for the 3rd luminous zone 2206.Then, deposit the Alq of 27.5 nanometers 3As electron transfer layer, by being total to evaporation, deposition BCP and Li are as electron injecting layer, and film thickness is 10 nanometers, and the quality ratio that makes Li and BCP is 1: 0.005 (=BCP: Li).Then, thickness of deposited film is that the aluminium of 200 nanometers is as second electrode 2207.Like this, can obtain to have introduced the element of the emission white light of redness of the present invention or blush phosphorus.
Though at this execution mode the example of three luminous zones is shown,, can provides two luminous zones or four or more a plurality of luminous zone for obtaining whole white light.
[execution mode 13]
This execution mode is described with light-emitting component and the manufacture method thereof of organometallic complex of the present invention as luminescent substance referring to Figure 39.
On substrate 2300,, form first electrode 2301 by sputtering and depositing tin indium oxide.Its film thickness is 110 nanometers.
Next, the substrate that will be formed with first electrode 2301 is fixed on the substrate holder of commercially available vacuum deposition system, make be formed with first electrode 2301 on it the surface down.
Next, carry out evaporation by being heated by resistive device, deposited copper phthalocyanine on first electrode 2301, film thickness are 20nm, form hole injection layer 2302.
Next, on hole injection layer 2302, carry out evaporation by being heated by resistive device, deposition α-NPD, thickness is 40 nanometers, forms hole transmission layer 2303.
Next, on hole transmission layer 2303, by being total to evaporation, deposition Ir (Fdpq) 2(acac) and TPAQn, film thickness is 30 nanometers, forms luminescent layer 2304.At this, deposition Ir (Fdpq) 2(acac) and TPAQn, make Ir (Fdpq) 2(acac) ratio with 8 weight % is included in the layer of being made up of TPAQn.This ratio makes Ir (Fdpq) 2(acac) be dispersed in the layer of forming by TPAQn.It should be noted that common evaporation is the method for being carried out evaporation in an operating room by a plurality of vapor deposition source simultaneously.
Next, on luminescent layer 2304, carry out evaporation, depositing Al q by being heated by resistive device 3, film thickness is 30 nanometers, forms electron transfer layer 2305.
Next, on electron transfer layer 2305, carry out evaporation by being heated by resistive device, depositing fluorinated calcium, film thickness are 2 nanometers, form electron injecting layer 2306.
Next, on electron injecting layer 2306, carry out evaporation by being heated by resistive device, thickness of deposited film is the aluminium of 150 nanometers, forms second electrode 2307.
On the light-emitting component of making, apply voltage, make the electromotive force of first electrode 2301 be higher than the electromotive force of second electrode 2307.Then, when applying 7.6V voltage, with 466cd/m 2Luminosity emission light.This moment, current efficiency was 1.56cd/A.In addition, emission spectrum has a peak at 652nm.Figure 40 illustrates emission spectrum.In addition, the cie color coordinate that this element has for (x, y)=(0.65,0.33).
As mentioned above, use organometallic complex of the present invention, can obtain to provide useful redness or the luminous light-emitting component of blush with useful colourity.In addition, in this execution mode, organometallic complex of the present invention is combined the formation luminescent layer with quinoxaline derivant, during as light-emitting component, can make organometallic complex more effectively luminous.
It should be noted that the material that is used to make the light-emitting component that has used organometallic complex of the present invention is not limited to above-mentioned substance, except the described material of this execution mode, can use at material described in the Implementation Modes and other known substance.In addition, the layer structure of light-emitting component is not limited in the described structure of this execution mode, or can appropriate change.In addition, the method for making light-emitting component is had no particular limits.Electrode as anode can at first be made according to this execution mode, or at first makes as the electrode of negative electrode.
The synthesis example of＜TPAQn 〉
Used TPAQn is the novel materials by following structural formula (74) expression in execution mode 13.The method of the quinoxaline derivant of synthetic following formula (74) expression is described below.
＜Synthetic 2,3-two (4-bromophenyl) quinoxaline 〉
At first, in 500mL recovery flask, drop into 10g (27.4mmol) 4-bromine benzil and 3.5g (33.5mmol) o-phenylenediamine, in chloroform, keep refluxing 8 hours.Then, be cooled to room temperature after, remove residual o-phenylenediamine by column chromatography, obtain 2,3-two (4-bromophenyl) quinoxaline.
＜synthetic TPAQn 〉
In addition, drop into the 4.40g (10.0mmol) 2 that obtains in a there-necked flask, 3-two (4-bromophenyl) quinoxaline is dissolved in nitrogen current in the 75mL toluene.Then, add 0.22g (0.2mmol) Pd (dba) 2, 2.88g (30mmol) NaO-t-Bu and 3.46g (20.4mmol) diphenylamines, add the 10 weight % hexane solutions of 1.8mL three (tert-butyl group phosphine) again, added thermal agitation 8 hours at 80 ℃.
Then, be cooled to room temperature after, add entry, finish this reaction, extract with chloroform.After the saturated aqueous sodium chloride washing, use MgSO 4Carry out drying.After this,, obtain 2, (the abbreviation: TPAQn) (yellow green crystal, productive rate: 2.7g (44%)) of 3-two (4-diphenyl amino phenyl) quinoxaline from the chloroform recrystallization.
Above-mentioned synthetic synthetic schemes (75) is as follows.
Figure 41 illustrates by the above-mentioned synthetic TPAQn's that is obtained 1The H-NMR collection of illustrative plates.
The pyrolysis temperature of the TPAQn that is obtained is 411 ℃.Measuring system synchronously by thermogravimetric/differential thermal analysis (from Seiko Instruments Inc., TG/DTA-320) measures.
[execution mode 14]
This execution mode is described with light-emitting component and the manufacture method thereof of organometallic complex synthetic in the synthetic execution mode 3 of the present invention as luminescent substance referring to Figure 42.
At first, on substrate 2400, comprise the tin indium oxide of silica, form first electrode 2401 by sputtering sedimentation.Its film thickness is 110 nanometers.
Next, the substrate that is formed with first electrode 2401 on it is fixed on the substrate holder of commercially available vacuum deposition system, make form first electrode 2401 on it the surface down.
Then, carry out evaporation by being heated by resistive device, on first electrode 2401, deposit 4,4 '-two [N-{4-(N, N-a two-tolyl amino) phenyl }-the N-phenyl amino] (abbreviation: DNTPD), film thickness is 50nm to biphenyl, forms hole injection layer 2402.
Next, on hole injection layer 2402, carry out evaporation by being heated by resistive device, deposition α-NPD, thickness is 10 nanometers, forms hole transmission layer 2403.
Next, on hole transmission layer 2403, by being total to evaporation, deposition Ir (Fdpq) 2(acac) and TPAQn, film thickness is 30 nanometers, forms luminescent layer 2404.At this, deposition Ir (Fdpq) 2(acac) and TPAQn, make Ir (Fdpq) 2(acac) quality ratio is 1: 0.05 (=TPAQn: Ir (Fdpq) 2(pic)).This ratio makes Ir (Fdpq) 2(acac) be dispersed in the layer of forming by TPAQn.It should be noted that common evaporation is the method for being carried out evaporation in an operating room by a plurality of vapor deposition source simultaneously.
Next, on luminescent layer 2404, carry out evaporation, deposition BAlq by being heated by resistive device 3, film thickness is 10 nanometers, forms electron transfer layer 2405.
Next, on hole blocking layer 2405, carry out evaporation, depositing Al q by being heated by resistive device 3, film thickness is 50 nanometers, forms electron transfer layer 2406.
Next, on electron transfer layer 2406, carry out evaporation by being heated by resistive device, depositing fluorinated calcium, film thickness are 1 nanometer, form electron injecting layer 2407.
Next, on electron injecting layer 2407, carry out evaporation by being heated by resistive device, thickness of deposited film is the aluminium of 200 nanometers, forms second electrode 2408.
On the light-emitting component of making, apply voltage, make the electromotive force of first electrode 2401 be higher than the electromotive force of second electrode 2408, determined when applying 11.0V voltage, with 460cd/m 2Luminosity emission light.This moment, current efficiency was 3.2cd/A.In addition, emission spectrum has a peak at 622nm.Figure 43 illustrates emission spectrum.In addition, the cie color coordinate that this element has for (x, y)=(0.68,0.32).
As mentioned above, use organometallic complex of the present invention, can obtain to provide useful redness or the luminous light-emitting component of blush with useful colourity.
It should be noted that the light-emitting component at this execution mode has hole blocking layer 2405 between luminescent layer 2404 and electron transfer layer 2406.Hole blocking layer 2405 has useful electric transmission character, can prevent Ir (Fdpq) 2(pic) excitation energy that is excited in luminescent layer 2404 is transferred to electron transfer layer 2406, and has the blocking-up hole is transferred to electron transfer layer 2406 from luminescent layer 2404 function.Therefore, by providing hole blocking layer to improve luminous efficiency.Hole blocking layer can be with having big energy gap in the material that forms electron transfer layer and than the material of heavy ion electrochemical potential, forming as Balq.As mentioned above, except electron transfer layer or hole transmission layer, between luminescent layer and electrode various functional layers are provided.
[execution mode 15]
This execution mode is an example making light-emitting component according to the mode identical with execution mode 14, and difference is to change TPAQn in the luminescent layer 2404 of execution mode 14 into CBP.
On this light-emitting component, apply voltage, when making the electromotive force of first electrode 2401 be higher than the electromotive force of second electrode 2408, determine when applying 12.4V voltage, with 480cd/m 2Luminosity emission light.This moment, current efficiency was 3.0cd/A.In addition, emission spectrum has a peak at 622nm.Figure 44 illustrates emission spectrum.It should be noted that the transverse axis and the longitudinal axis among this figure represent wavelength (nanometer) and emissive porwer (a.u.) respectively.In addition, the cie color coordinate that this element has for (x, y)=(0.66,0.33).
As mentioned above, use organometallic complex of the present invention, can obtain to provide useful redness or the luminous light-emitting component of blush with useful colourity.
[execution mode 16]
This execution mode is described light emitting element structure and the manufacture method thereof of using organometallic complex synthetic in the synthetic execution mode 4 referring to Figure 42.
At first, on substrate 2400,, form first electrode 2401 by the sputtering sedimentation silica.Its film thickness is 110 nanometers.
Next, the substrate that will be formed with first electrode 2401 is fixed on the substrate holder of commercially available vacuum deposition system, make be formed with first electrode 2401 on it the surface downwards.
Then, carry out evaporation by being heated by resistive device, on first electrode 2401, deposit 4,4 '-two [N-{4-(N, N-a two-tolyl amino) phenyl }-the N-phenyl amino] (abbreviation: DNTPD), film thickness is 50 nanometers to biphenyl, forms hole injection layer 2402.
Next, on hole injection layer 2402, carry out evaporation by being heated by resistive device, deposition α-NPD, thickness is 10 nanometers, forms hole transmission layer 2403.
Next, on hole transmission layer 2403, by common evaporation, deposition Ir (3,5-Fdpq) 2(acac) and CBP, film thickness is 30 nanometers, forms luminescent layer 2404.At this, and Ir (3,5-Fdpq) 2(acac) with the quality ratio of CBP be 1: 0.025 (=CBP: Ir (and 3,5-Fdpq) 2(acac)).This ratio make Ir (3,5-Fdpq) 2(acac) be dispersed in the layer of forming by CBP.It should be noted that common evaporation is the method for being carried out evaporation in an operating room by a plurality of vapor deposition source simultaneously.
Next, on luminescent layer 2404, carry out evaporation by being heated by resistive device, deposition BCP, film thickness is 10 nanometers, forms hole blocking layer 2405.
Next, on hole blocking layer 2405, carry out evaporation, depositing Al q by being heated by resistive device 3, film thickness is 20 nanometers, forms electron transfer layer 2406.
Next, on electron transfer layer 2406, carry out evaporation by being heated by resistive device, depositing fluorinated calcium, film thickness are 1 nanometer, form electron injecting layer 2407.
Next, on electron injecting layer 2407, carry out evaporation by being heated by resistive device, thickness of deposited film is the aluminium of 200 nanometers, forms second electrode 2408.
On the light-emitting component of making, apply voltage, make the electromotive force of first electrode 2401 be higher than the electromotive force of second electrode 2408.Then, when applying 10.2V voltage, with 520cd/m 2Luminosity emission light.This moment, current efficiency was 0.98cd/A.In addition, emission spectrum has a peak at 664nm.Figure 45 illustrates emission spectrum.In addition, the cie color coordinate that this element has for (x, y)=(0.71,0.28).
As mentioned above, use organometallic complex of the present invention, can obtain to provide useful redness or the luminous light-emitting component of blush with useful colourity.
[execution mode 17]
In this execution mode, make light-emitting component according to the mode identical with execution mode 16, difference is to change the BCP in CBP and the hole blocking layer 2405 in the luminescent layer 2404 of execution mode 16 into Alq respectively 3And Balq.
On this light-emitting component, apply voltage, make the electromotive force of first electrode 2401 be higher than the electromotive force of second electrode 2408.Then, when applying 10.0V voltage, with 460cd/m 2Luminosity emission light.This moment, current efficiency was 1.2cd/A.In addition, emission spectrum has a peak at 665nm.Figure 46 illustrates emission spectrum.It should be noted that the transverse axis and the longitudinal axis among this figure represent wavelength (nanometer) and emissive porwer (a.u.) respectively.In addition, the cie color coordinate that this element has for (x, y)=(0.69,0.30).
As mentioned above, use organometallic complex of the present invention, can obtain to provide useful redness or the luminous light-emitting component of blush with useful colourity.
Though fully described the present invention with way of example referring to accompanying drawing, should be understood that various changes and modification will be apparent to those skilled in the art.Therefore, unless these changes and modification have departed from the scope of the present invention of definition, they are contemplated as falling with within the scope of the invention.
The application submits to the Japanese patent application sequence number 2004-151035 of Japan Patent office based on 2+0 day in May, 2004, submitted to the Japanese patent application sequence number 2004-226382 of Japan Patent office on August 3rd, 2004, Japanese patent application sequence number 2004-231742 with submitting to Japan Patent office on August 6th, 2004 includes its full content in this paper as a reference.

Claims (33)

1. light-emitting component that between pair of electrodes, comprises a luminescent layer,
Wherein, described luminescent layer comprises the organometallic complex of (1) the represented structure that has general formula and the energy gap compound greater than described organometallic complex,
Figure A2005800160490002C1
In the formula, R 1To R 5Each is selected from down group naturally: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group and heterocyclic radical, Ar are a kind of in aryl with electron withdraw group and the heterocyclic radical with electron withdraw group, and M is a kind of in the 9th family's element and the 10th family's element.
2. light-emitting component that between pair of electrodes, comprises a luminescent layer,
Wherein, described luminescent layer comprises the organometallic complex of (2) the represented structure that has general formula and the energy gap compound greater than described organometallic complex,
In the formula, R 1To R 9Be selected from down group separately: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group and heterocyclic radical, R 6To R 9In at least a be electron withdraw group, M is a kind of in the 9th family's element and the 10th family's element.
3. light-emitting component that between pair of electrodes, comprises a luminescent layer,
Wherein, described luminescent layer comprises the organometallic complex of (3) the represented structure that has general formula and the energy gap compound greater than described organometallic complex,
Figure A2005800160490003C1
In the formula, R 2To R 14Be selected from down group separately: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group and heterocyclic radical, M are a kind of in the 9th family's element and the 10th family's element.
4. light-emitting component that between pair of electrodes, comprises a luminescent layer,
Wherein, described luminescent layer comprises the organometallic complex of (4) the represented structure that has general formula and the energy gap compound greater than described organometallic complex,
Figure A2005800160490003C2
In the formula, R 15And R 16Be selected from down group separately: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group and heterocyclic radical, M are a kind of in the 9th family's element and the 10th family's element.
5. light-emitting component that between pair of electrodes, comprises a luminescent layer,
Wherein, described luminescent layer comprises the represented organometallic complex of general formula (5) and the energy gap compound greater than described organometallic complex,
Figure A2005800160490003C3
In the formula, R 1To R 5Be selected from down group separately: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group and heterocyclic radical; Ar has the aryl of electron withdraw group and has a kind of in the heterocyclic radical of electron withdraw group; M is a kind of in the 9th family's element and the 10th family's element; n=2 when M is the element of the 9th family; and when M is the 10th group element n=1, L is an anion ligand.
6. light-emitting component that between pair of electrodes, comprises a luminescent layer,
Wherein, described luminescent layer comprises the represented organometallic complex of general formula (6) and the energy gap compound greater than described organometallic complex,
Figure A2005800160490004C1
In the formula, R 1To R 9Be selected from down group separately: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group and heterocyclic radical, R 6To R 9In at least one is an electron withdraw group, M is a kind of in the 9th family's element and the 10th family's element, n=2 when M is the element of the 9th family, and when M is the 10th group element n=1, L is an anion ligand.
7. light-emitting component that between pair of electrodes, comprises a luminescent layer,
Wherein, described luminescent layer comprises the represented organometallic complex of general formula (7) and the energy gap compound greater than described organometallic complex,
Figure A2005800160490004C2
In the formula, R 2To R 14Be selected from down group separately: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group and heterocyclic radical; M is a kind of in the 9th family's element and the 10th family's element; n=2 when M is the element of the 9th family, and when M is the 10th group element n=1, L is an anion ligand.
8. light-emitting component that between pair of electrodes, comprises a luminescent layer,
Wherein, described luminescent layer comprises the represented organometallic complex of general formula (8) and the energy gap compound greater than described organometallic complex,
Figure A2005800160490005C1
In the formula, R 15And R 16Be selected from down group separately: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group and heterocyclic radical; M is a kind of in the 9th family's element and the 10th family's element; n=2 when M is the element of the 9th family, and when M is the 10th group element n=1, L is an anion ligand.
9. as each described light-emitting component in the claim 1 to 8, it is characterized in that described energy gap is 4 greater than the compound of described organometallic complex, a kind of in 4 '-two [N-(1-naphthyl)-N-phenyl amino] biphenyl and three (oxine closes) aluminium.
10. as each described light-emitting component in the claim 5 to 8, it is characterized in that described anion ligand L is a kind of in the anion ligand with beta-diketon structure, the anion bidentate ligand with carboxyl and the anion bidentate ligand with phenolic hydroxyl group.
11., it is characterized in that described anion ligand L is any one the represented part in following general formula (9)-(15) as each described light-emitting component in the claim 5 to 8:
12., it is characterized in that described luminescent layer comprises described organometallic complex and big and electron mobility is equal to or greater than 10 than the energy gap of described organometallic complex as each described light-emitting component in the claim 1 to 8 -6Cm 2First compound of/Vs and than the energy gap of described organometallic complex big and hole mobility is equal to or greater than 10 -6Cm 2A kind of in second compound of/Vs.
13., it is characterized in that described luminescent layer comprises described organometallic complex and big and electron mobility is equal to or greater than 10 than the energy gap of described organometallic complex as each described light-emitting component in the claim 1 to 8 -6Cm 2First compound of/Vs and than the energy gap of described organometallic complex big and hole mobility is equal to or greater than 10 -6Cm 2Second compound of/Vs.
14. light-emitting component as claimed in claim 12 is characterized in that, described first compound is a metal complex, and second compound is an aromatic amine compound.
15. light-emitting component as claimed in claim 13 is characterized in that, described first compound is a metal complex, and second compound is an aromatic amine compound.
16. a light-emitting component that between pair of electrodes, comprises a luminescent layer,
Wherein, described luminescent layer comprise the organometallic complex of (1) the represented structure that has general formula and ionization potential greater than described organometallic complex electron affinity less than the compound of described organometallic complex,
Figure A2005800160490007C1
In the formula, R 1To R 5Each is selected from down group naturally: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group and heterocyclic radical, Ar are a kind of in aryl with electron withdraw group and the heterocyclic radical with electron withdraw group, and M is a kind of in the 9th family's element and the 10th family's element.
17. a light-emitting component that between pair of electrodes, comprises a luminescent layer,
Wherein, described luminescent layer comprise the organometallic complex of (2) the represented structure that has general formula and ionization potential greater than described organometallic complex electron affinity less than the compound of described organometallic complex,
In the formula, R 1To R 9Be selected from down group separately: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group and heterocyclic radical, M are a kind of in the 9th family's element and the 10th family's element.
18. a light-emitting component that between pair of electrodes, comprises a luminescent layer,
Wherein, described luminescent layer comprise the organometallic complex of (3) the represented structure that has general formula and ionization potential greater than described organometallic complex electron affinity less than the compound of described organometallic complex,
In the formula, R 2To R 14Be selected from down group separately: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group and heterocyclic radical, M are a kind of in the 9th family's element and the 10th family's element.
19. a light-emitting component that between pair of electrodes, comprises a luminescent layer,
Wherein, described luminescent layer comprise the organometallic complex of (4) the represented structure that has general formula and ionization potential greater than described organometallic complex electron affinity less than the compound of described organometallic complex,
Figure A2005800160490008C2
In the formula, R 15And R 16Be selected from down group separately: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group and heterocyclic radical, M are a kind of in the 9th family's element and the 10th family's element.
20. a light-emitting component that between pair of electrodes, comprises a luminescent layer,
Wherein, described luminescent layer comprise the represented organometallic complex of general formula (5) and ionization potential greater than described organometallic complex electron affinity less than the compound of described organometallic complex, and
Figure A2005800160490008C3
In the formula, R 1To R 5Be selected from down group separately: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group and heterocyclic radical; Ar has the aryl of electron withdraw group and has a kind of in the heterocyclic radical of electron withdraw group; M is a kind of in the 9th family's element and the 10th family's element; n=2 when M is the element of the 9th family; and when M is the 10th group element n=1, L is an anion ligand.
21. a light-emitting component that between pair of electrodes, comprises a luminescent layer,
Wherein, described luminescent layer comprise the represented organometallic complex of general formula (6) and ionization potential greater than described organometallic complex electron affinity less than the compound of described organometallic complex,
In the formula, R 1To R 9Be selected from down any one that organize naturally: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group and heterocyclic radical, R 6To R 9In at least one is an electron withdraw group, M is a kind of in the 9th family's element and the 10th family's element, n=2 when M is the element of the 9th family, and when M is the 10th group element n=1, L is an anion ligand.
22. a light-emitting component that between pair of electrodes, comprises a luminescent layer,
Wherein, described luminescent layer comprise the represented organometallic complex of general formula (7) and ionization potential greater than described organometallic complex electron affinity less than the compound of described organometallic complex,
In the formula, R 2To R 14Be selected from down group separately: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group and heterocyclic radical; M is a kind of in the 9th family's element and the 10th family's element; n=2 when M is the element of the 9th family, and when M is the 10th group element n=1, L is an anion ligand.
23. a light-emitting component that between pair of electrodes, comprises a luminescent layer,
Wherein, described luminescent layer comprise the represented organometallic complex of general formula (8) and ionization potential greater than described organometallic complex electron affinity less than the compound of described organometallic complex,
In the formula, R 15And R 16Be selected from down group separately: hydrogen, halogen, acyl group, alkyl, alkoxyl, aryl, cyano group and heterocyclic radical; M is a kind of in the 9th family's element and the 10th family's element; n=2 when M is the element of the 9th family, and when M is the 10th group element n=1, L is an anion ligand.
24. as each described light-emitting component in the claim 20 to 23, it is characterized in that described anion ligand L is a kind of in the anion ligand with beta-diketon structure, the anion bidentate ligand with carboxyl and the single anion bidentate ligand with phenolic hydroxyl group.
25., it is characterized in that described anion ligand L is any one the represented part in following formula (9)-(15) as each described light-emitting component in the claim 20 to 23:
26. as each described light-emitting component in the claim 16 to 23, it is characterized in that, described luminescent layer comprises described organometallic complex, and bigger than the ionization potential of described organometallic complex, little and electron mobility is equal to or greater than 10 than the electron affinity of described organometallic complex -6Cm 2First compound of/Vs and bigger than the ionization potential of described organometallic complex, little and hole mobility is equal to or greater than 10 than the electron affinity of described organometallic complex -6Cm 2A kind of in second compound of/Vs.
27. as each described light-emitting component in the claim 16 to 23, it is characterized in that, described luminescent layer comprises described organometallic complex, and bigger than the ionization potential of described organometallic complex, little and electron mobility is equal to or greater than 10 than the electron affinity of described organometallic complex -6Cm 2First compound of/Vs and bigger than the ionization potential of described organometallic complex, little and hole mobility is equal to or greater than 10 than the electron affinity of described organometallic complex -6Cm 2Second compound of/Vs.
28. light-emitting component as claimed in claim 26 is characterized in that, described first compound is a metal complex, and second compound is an aromatic amine compound.
29. light-emitting component as claimed in claim 27 is characterized in that, described first compound is a metal complex, and second compound is an aromatic amine compound.
30., also comprise the one deck at least in hole injection layer, hole transmission layer, hole blocking layer, electron transfer layer and the electron injecting layer as each described light-emitting component in the claim 1 to 8.
31., also comprise the one deck at least in hole injection layer, hole transmission layer, hole blocking layer, electron transfer layer and the electron injecting layer as each described light-emitting component in the claim 16 to 23.
32. the luminaire of each described light-emitting component in use such as the claim 1 to 8.
33. the luminaire of each described light-emitting component in use such as the claim 16 to 23.
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CN104672152A (en) * 2013-11-28 2015-06-03 株式会社半导体能源研究所 Organic compound and use thereof in synthesis of organometallic complex
CN104795507A (en) * 2015-04-16 2015-07-22 京东方科技集团股份有限公司 Organic light-emitting device, method for manufacturing same and electronic equipment
US9978960B2 (en) 2013-06-14 2018-05-22 Semiconductor Energy Laboratory Co., Ltd. Organometallic iridium complex, light-emitting element, light-emitting device, and lighting device

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US6821645B2 (en) * 1999-12-27 2004-11-23 Fuji Photo Film Co., Ltd. Light-emitting material comprising orthometalated iridium complex, light-emitting device, high efficiency red light-emitting device, and novel iridium complex
JP4154139B2 (en) * 2000-09-26 2008-09-24 キヤノン株式会社 Light emitting element
US6835469B2 (en) * 2001-10-17 2004-12-28 The University Of Southern California Phosphorescent compounds and devices comprising the same

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US9978960B2 (en) 2013-06-14 2018-05-22 Semiconductor Energy Laboratory Co., Ltd. Organometallic iridium complex, light-emitting element, light-emitting device, and lighting device
US10431752B2 (en) 2013-06-14 2019-10-01 Semiconductor Energy Laboratory Co., Ltd. Organometallic iridium complex, light-emitting element, light-emitting device, and lighting device
CN104672152A (en) * 2013-11-28 2015-06-03 株式会社半导体能源研究所 Organic compound and use thereof in synthesis of organometallic complex
CN104795507A (en) * 2015-04-16 2015-07-22 京东方科技集团股份有限公司 Organic light-emitting device, method for manufacturing same and electronic equipment
US10115909B2 (en) 2015-04-16 2018-10-30 Boe Technology Group Co., Ltd. Organic electroluminescent device, manufacturing method thereof and electronic equipment

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