CN106317129B - Amido ferrocene derivatives and Organic Light Emitting Diode - Google Patents
Amido ferrocene derivatives and Organic Light Emitting Diode Download PDFInfo
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Abstract
A kind of amido ferrocene derivatives, as shown in formula (I).In formula (I), Ar1、Ar2The C for being substituted or being unsubstituted is indicated identical or differently6~C10Aryl.Amido ferrocene derivatives of the invention can be as the p-type carrier generating layer in OLED, and the OLED (tandem OLED) after being concatenated can be made to have the characteristics such as high brightness, external quantum efficiency and current efficiency.
Description
Technical field
The invention relates to a kind of ferrocene (ferrocene) derivative and Organic Light Emitting Diode (organic
Light-emitting diode, OLED), particularly relate to a kind of amido ferrocene (aminoferrocene) derivative and comprising
The Organic Light Emitting Diode of the amido ferrocene derivatives.
Background technique
Organic Light Emitting Diode have can self-lighting, high contrast, high brightness, wide viewing angle and reaction speed it is fast etc. excellent
Point, for display popular in recent years.Compared to existing single layer OLED, while the series connection that several luminescence components are together in series
Formula Organic Light Emitting Diode (tandem OLED), because brightness identical with tradition OLED can be reached with lower current density,
Therefore it can possess longer service life, and the photochromic of each luminescence component can be adjusted separately, thus be suitable for application in white light
On OLED.
In OLED, the especially structure of tandem OLED, include the p-type carrier generating layer for generating electric hole
(charge generation layer, CGL), such as " J.Mater.Chem., 2011,21, p15332-15336 " is i.e. open
Using thiophene (thiophene) derivative as the p-type carrier generating layer in tandem OLED.However, previous literature is still less
For the material for the p-type carrier generating layer that can be used as OLED, and after how being improved using this layer material and being concatenated
Light emission luminance (luminance), external quantum efficiency (external quantum efficiency) and the current efficiency of OLED
Characteristics such as (current efficiency) carry out research in detail and discuss.
Therefore, a kind of compounds how are found, can be as the p-type carrier generating layer in OLED, and can make to be concatenated
OLED (tandem OLED) after several luminescence units, compared to conventional monolayers OLED component, can have simultaneously high brightness,
The characteristics such as external quantum efficiency and current efficiency become the target for endeavouring research at present.
Summary of the invention
The first object of the present invention be to provide it is a kind of can be as the p-type carrier generating layer in OLED, and can make to be concatenated
OLED (tandem OLED) after several luminescence units, compared to conventional monolayers OLED component, can have simultaneously high brightness,
The amido ferrocene derivatives of the characteristics such as external quantum efficiency and current efficiency.
Amido ferrocene derivatives of the present invention, as shown in following formula (I):
In formula (I), Ar1、Ar2The C for being substituted or being unsubstituted is indicated identical or differently6~C10Aryl.
The second object of the present invention is that providing a kind of includes amido ferrocene derivatives as the aforementioned, to carry as p-type
The Organic Light Emitting Diode of sub- generating layer.
The beneficial effects of the present invention are: due on ferrocene with supplied for electronic (electron-donating) ability-
NAr1Ar2Substituent group can improve the molecular weight of ferrocene and increase its thermal stability, make its more general organic semiconducting materials tool
Have higher HOMO can rank, thus enable amido ferrocene derivatives of the invention as the p-type carrier generating layer in OLED,
And can make to be concatenated the OLED (tandem OLED) after several luminescence units, compared to conventional monolayers OLED component, can have simultaneously
There are the characteristics such as high brightness, external quantum efficiency and current efficiency.
It will be described in detail below with regard to the content of present invention:
[amido ferrocene derivatives]
Amido ferrocene derivatives of the invention, as shown in following formula (I):
In formula (I), Ar1、Ar2The C for being substituted or being unsubstituted is indicated identical or differently6~C10Aryl.
Preferably, Ar1、Ar2The phenyl for being substituted or being unsubstituted is indicated identical or differently.
More preferably, Ar1、Ar2It is indicated identical or differently through at least one R1Substituted phenyl, R1Expression is substituted or not
The C being substituted1~C7Alkyl, the C for being substituted or being unsubstituted6~C18Aryl or ferrocene.Again more preferably, Ar1、Ar2It is identical or
It differently indicates through a R1Substituted phenyl, R1Indicate the C for being substituted or being unsubstituted1~C7Alkyl is substituted or without taking
The C in generation6~C18Aryl or ferrocene.Again more preferably, R1Indicate C1~C7Alkyl or the phenyl for being substituted or being unsubstituted.Again more
Goodly, R1Indicate methyl, the phenyl replaced through diphenyl amido or the phenyl being unsubstituted.
More preferably, Ar1、Ar2It is indicated identical or differently through aligning the phenyl for replacing or being unsubstituted.
In a specific embodiment of the present invention, which is compound Fc01 to Fc04, and Ph indicates benzene
Base:
[preparation methods of amido ferrocene derivatives]
Amido ferrocene derivatives of the invention are to make amido ferrocene and warp in the presence of catalyst, solvent and alkali
The aromatic rings that halogen replaces is reacted and is made.In a specific embodiment of the present invention, which is 4- bromine
Biphenyl (4-bromobiphenyl), 4- iodotoluene (4-iodotoluene) or 4'- bromo- N, N- diphenyl biphenyl -4- amine (4'-
bromo-N,N-diphenylbiphenyl-4-amine)。
Preferably, the catalyst is palladium catalyst.More preferably, which is by palladium compound and ligand (ligand)
It is formed.In a specific embodiment of the present invention, which is acid chloride [Pd (OAc)2] or it is bis- (dibenzalacetone)
Palladium [Pd (dba)2], which is bis- (diphenylphosphine) ferrocene (dppf) of 1,1'-, 2- cyclohexyl phosphine -2', 6'- diisopropyl oxygen
Base biphenyl (2-dicyclohexylphosphino-2', 6'-diisopropoxybiphenyl, RuPhos) or tributylphosphine
(tributylphosphine)。
In a specific embodiment of the present invention, which is toluene (toluene).
In a specific embodiment of the present invention, which is sodium tert-butoxide (NaOtBu)。
Detailed description of the invention
Fig. 1 is a schematic diagram, illustrates the tandem OLED structure of application examples 1；
Fig. 2 is a schematic diagram, illustrates the tandem OLED structure of application examples 5；
Fig. 3 is a schematic diagram, illustrates the OLED structure for comparing application examples 1；And
Fig. 4 is a schematic diagram, illustrates the OLED structure for comparing application examples 3.
Specific embodiment
The present invention will be described further with regard to following embodiment, however, it should be noted that the embodiment is only to illustrate
It is used, and is not necessarily to be construed as the limitation that the present invention is implemented.
<preparation example 1>
Prepare amido ferrocene
[reaction equation I]
Reaction equation I be amido ferrocene (preparation flow of compound c), detailed preparation step is as what follows:
Step (1): under nitrogen system, first by 10g (53.8mmol) ferrocene with 50mL anhydrous n-hexane (n-
Hexane it) dissolves, adds 18.1mL (84.5mmol) tetramethylethylenediamine (TMEDA) mixing, and be slowly added dropwise at 0 DEG C
After the hexane solution 48.0mL of 2.5M n-BuLi (n-BuLi), stirred at 25 DEG C.After agitated 12 hours, first remove molten
Agent, and will be formed by light crocus misfit object be added 200mL anhydrous ether (ethyl ether) be dispersed with stirring and be cooled to-
78 DEG C, diethyl ether solution (the 19.0g I of iodine is slowly added dropwise2/ 350mL ether) after, after slowly rising again to 25 DEG C and stirring 1 hour,
Reactant is poured into the iron chloride (FeCl of 100mL, 5wt%3) aqueous solution, the extraction of 200mL ether is recycled, gained organic layer is first
With 5wt% iron chloride (FeCl3) aqueous solution (100mL) washs 10 times, then after no longer being changed colour with water washing organic layer to water layer, with
Anhydrous magnesium sulfate (MgSO4) solvent is removed water and removes, it obtains color and is dark brown and is in liquid compound a and compound b
Mixture (the mole number ratio of compound a and b be 1:1；Compound a and b structure are shown in reaction equation I).
Step (2): first by the resulting mixture of 2.5g (6.67mol) step (1), 128mg (0.67mmol) cuprous iodide
(CuI), 107mg (0.67mmol) iron chloride (FeCl3), 540mg (13.3mmol) sodium hydroxide, (concentration is 30mL ammonium hydroxide
15M) and after 30mL ethyl alcohol (EtOH) merging 150mL reaction under high pressure pipe, after being reacted 12 hours at 90 DEG C and being down to 25 DEG C, note
Enter 200mL ether and washed 3 times with 150mL concentration for the sodium hydrate aqueous solution of 1.0M, then removes water and move with anhydrous magnesium sulfate
After solvent, tangerine brown crude product is obtained.Finally, purifying the tangerine brown crude product using column chromatography, [system that purges with is 1:2
(v/v) ethyl acetate and n-hexane], that is, obtain filemot amido ferrocene solid (yield 48%).
Gained amido ferrocene1H NMR(400MHz.CDCl3) test result: δ 4.08 (s, 5H), 3.97 (t, J=
1.6,2H), 3.82 (t, J=1.6,2H), 2.58 (br, 2H).
<embodiment 1>
Prepare ferrocene derivatives (Fc01)
[reaction equation II]
Reaction equation II is the preparation flow of compound Fc01, and detailed preparation step is as what follows:
Step (1) [prepare compound BPAFc]: first by the resulting amido ferrocene of 300mg (1.49mmol) preparation example 1,
380mg (1.64mmol) 4- bromo biphenyl (4-bromobiphenyl), 17mg (0.075mmol) acid chloride [Pd (OAc)2]、67mg
Bis- (diphenylphosphine) ferrocene (dppf) of (0.12mmol) 1,1'- and 577mg (6mmol) sodium tert-butoxide (NaOtBu it) mixes, and
It using 5mL toluene as solvent, is reacted 72 hours at 90 DEG C, then pour into pure water, with 60mL ether extraction 5 times, gained organic layer
After removing water with anhydrous magnesium sulfate again and remove solvent, [n-hexane that system is 3:2 (v/v) is purged with using column chromatography purifying
With ethyl acetate], that is, obtain the compound BPAFc solid (yield 68%, structure is shown in reaction equation II) of orange.
Step (2) [prepare compound Fc01]: by the resulting compound BPAFc of 100mg (0.283mmol) step (1),
123mg (0.566mmol) 4- iodotoluene (4-iodotoluene), bis- (dibenzalacetone) palladium [Pd of 4mg (0.007mmol)
(dba)2], 7mg (0.015mmol) 2- cyclohexyl phosphine -2', 6'- diisopropoxy biphenyl (RuPhos) and 109mg
(1.13mmol) sodium tert-butoxide (NaOtBu it) mixes, and using 3mL toluene as solvent, after being reacted 72 hours at 130 DEG C, first with silicon
Diatomaceous earth and silica gel are filtered to remove palladium catalyst, and to remove solvent after ethyl acetate rinse, finally with column chromatography purifying [punching
Mention the n-hexane and ethyl acetate that system is 3:1 (v/v)], then after distilling twice, i.e. the compound Fc01 of acquisition Chinese red is solid
Body (yield 80%).
Compound BPAFc obtained by step (1)1H NMR(400MHz.CDCl3) test result: δ 7.54 (d, J=8.0Hz,
2H), 7.45 (d, J=8.8Hz, 2H), 7.38 (t, J=8.0Hz, 2H), 7.25 (t, J=7.6Hz, 1H), 6.95 (d, J=
8.8Hz,2H),4.99(br,1H),4.27(s,2H),4.20(s,5H),4.05(s,2H)；13C NMR(100MHz.CDCl3) survey
Test result: δ 141.0,131.8,128.9,128.7,127.7,126.9,126.4,126.3,114.9,68 .9,64.6 and
62.0；HRMS(EI+, m/z) and test result: C22H19NFe calculated value is 353.0867, discovery value 353.0869.
Compound Fc01 obtained by step (2)1H NMR(400MHz.CDCl3) test result: δ 7.55 (dd, J=8.0,
0.8Hz, 2H), 7.47 (dd, J=8.0,2.0Hz, 2H), 7.37 (t, J=8.0Hz, 2H), 7.30-7.23 (m, 3H), 7.21
(q, J=6.0Hz, 4H), 4.15 (s, 5H), 4.30 (t, J=1.6,2H), 4.10 (t, J=2.0,2H), 2.36 (s, 3H)；13C
NMR(100MHz.CDCl3) test result: δ 147.2,144.6,140.8,134.2,133.8,130.0,128.7,127.4,
And 21.0 126.7,126.6,121.8,106.9,68.9,63.9,60.1；HRMS(EI+, m/z) and test result: C29H25NFe meter
Calculation value is 443.1336, discovery value 443.1339.
<embodiment 2>
Prepare ferrocene derivatives (Fc02)
Reaction equation III is the preparation flow of compound DPABPAFc and compound Fc02, and detailed preparation step is for example following
It is described:
Step (1) [prepare compound DPABPAFc]: by the resulting amido ferrocene of 300mg (1.5mmol) preparation example 1,
1.8g (4.5mmol) 4'- bromo- N, N- diphenyl biphenyl -4- amine (4'-bromo-N, N-diphenylbiphenyl-4-
Amine), 17mg (0.075mmol) acid chloride [Pd (OAc)2], 0.1mL concentration be 10wt% tributylphosphine
(tributylphosphine) hexane solution and 1.13g (11.8mmol) sodium tert-butoxide (NaOtBu it) mixes, and with 6mL first
Benzene is solvent, after reacting 72 hours at 130 DEG C, is first filtered to remove palladium catalyst with diatomite and silica gel, and with ethyl acetate
Solvent is removed after flushing, finally [system that purges with is the n-hexane and acetic acid second of 4:1 to 3:2 (v/v) again with column chromatography purifying
Ester gradient purges with system], i.e. acquisition compound DPABPAFc (yield 50%, structure is shown in reaction equation III).
Step (2) [prepare compound Fc02]: the reaction step of step (2) is identical as condition and abovementioned steps (1), poor
It is not, the equivalents of 4'- bromo- N, N- diphenyl biphenyl -4- amine is promoted to 7.90 grams (19.7mmol), and through col-umn chromatography
Method after purification, need to be distilled twice again, can be obtained red compound Fc02 solid (yield 40%).
Compound DPABPAFc obtained by step (1)1H NMR(400MHz.CDCl3) test result: δ 7.42 (t, J=
8.0Hz, 4H), 7.24 (t, J=8.0Hz, 4H), 7.11 (d, J=8.0Hz, 4H), 7.00 (t, J=7.2Hz, 2H), 6.92 (d,
J=7.6Hz, 2H), 4.89 (br, 1H), 4.29 (s, 2H), 4.21 (s, 5H), 4.08 (s, 2H)；13C NMR
(100MHz.CDCl3) test result: δ 147.8,146.2,141.9,135.3,131.2,129.2,127.2,127.0,
And 61.8 124.4,124.1,122.6,115.1,69.0,64.7；HRMS(EI+, m/z) and test result: C34H28N2Fe calculated value
For 520.1602, discovery value 520.1599.
Compound Fc02 obtained by step (2)1H NMR(400MHz.CDCl3) test result: δ 7.52 (d, J=8.4Hz,
4H), 7.46 (d, J=8.8Hz, 4H), 7.33 (d, J=8.4Hz, 4H), 7.27-7.23 (m, 8H), 7.11 (d, J=8.4Hz,
8H), 7.02 (d, J=8.0Hz, 4H), 4.17 (s, 5H), 4.11 (s, 2H), 4.04 (s, 2H)；13C NMR(100MHz.CDCl3)
Test result: δ 147.7,147.7,146.5,141.9,135.0,129.2,127.5,127.4,127.2,12 4.5,124.3,
And 60.4 124.2,124.0,122.8,122.7,118.0,69.0,64.0；HRMS(FAB+, m/z) and test result: C58H46N3Fe
Calculated value is 840.3041, discovery value 840.3044.
<embodiment 3>
Prepare ferrocene derivatives (Fc03)
[reaction equation IV]
Reaction equation IV is the preparation flow of compound Fc03, and detailed preparation step is identical as (2) the step of embodiment 1,
The difference is that the present embodiment is to carry out substituted compound using the resulting compound DPABPAFc of 132mg (0.283mmol) embodiment 2
Object BPAFc, and purged with for the n-hexane using 3:1 to 1:1 (v/v) with ethyl acetate gradient in col-umn chromatography purification process and be
System, and the compound Fc03 solid that finally can be obtained Chinese red through sublimation step twice is also needed in column chromatography after purification
(yield 55%).
Compound Fc03's1H NMR(400MHz.CDCl3) test result: δ 7.43 (t, J=8.0Hz, 4H), 7.26-
7.16 (m, 8H), 7.11-7.02 (m, 5H), 7.00 (t, J=7.6Hz, 2H), 4.15 (s, 5H), 4.01 (s, 2H), 4.00 (s,
2H),2.35(s,3H)；13C NMR(100MHz.CDCl3) test result: δ 147.7,146.8,146.5,134.9,134.0,
133.6,129.9,129.4,129.2,127.2,126.9,126.8,126.4,124.2,124.1,122.7,122.3,68.8,
63.8,60.0 and 21.0.
<embodiment 4>
Prepare ferrocene derivatives (Fc04)
[reaction equation V]
Reaction equation V is the preparation flow of compound Fc04, and detailed preparation step is identical as (1) the step of embodiment 1, poor
It is not, the amount of the added 4- bromo biphenyl (4-bromobiphenyl) of the present embodiment is 840mg (3.61mmol), and in tubing string
The n-hexane and ethyl acetate that system is 3:1 (v/v) are purged with used in during purification by chromatography, and pure in column chromatography
It also needs finally to can be obtained red compound Fc04 solid (yield 42%) through sublimation step twice after change.
Compound Fc04's1H NMR(400MHz.CDCl3) test result: δ 7.60-7.55 (m, 8H), 7.42 (t, J=
8.0Hz, 4H), 7.34 (d, J=8.4Hz, 4H), 7.31 (t, J=7.6Hz, 2H), 4.18 (s, 5H), 4.10 (s, 2H), 4.05
(s,2H)；13C NMR(100MHz.CDCl3) test result: δ 146.8,140.6,135.7,128.8,127.7,126.9,
And 60.5 126.8,124.5,69.0,64.0.
<HOMO and LUMO the energy rank of measurement compound Fc01~Fc04>
It is utilized respectively cyclic voltammetric (cyclic voltammetry, CV) instrument (manufacturer CH Instruments), photoelectron
Spectrum (photoelectron spectroscopy) instrument AC-2 and ultraviolet light photoelectron spectroscopy (ultraviolet
Photoelectron spectroscopy, UPS) instrument (NSRRC beamline 24A1) measurement compound Fc01~Fc04 is (in fact
Apply example 1~4) HOMO and LUMO can rank, acquired results are as shown in table 1.
Table 1
<application examples 1>
Series type organic LED (using compound Fc03 as p-type carrier generating layer)
[structure I]
ITO (150)/NPB (50)/TCTA:4wt%Ir (piq)3(30)/BPhen (20)/BPhen:6wt%LiF (5)/
Al(1)/C60(4)/Fc03(1)/MoO3(1)/NPB (50)/TCTA:4wt%Ir (ppy)3(30)/BPhen(20)/LiF(1)/
Al(100)
Signal of the tandem OLED structure such as aforementioned structure I [numerical value indicates thickness (nm) in bracket] of application examples 1 with Fig. 1
Shown in figure, component representated by each component numerals of Fig. 1 see the table below 2 using material and each thickness degree respectively.
Table 2
In table 2, compound represented by each material abbreviation is as follows:
ITO: tin indium oxide (indium tin oxide)；
NPB:N, N'- bis- phenyl-N, N'- bis- (1- naphthalene) -1,1'- biphenyl -4,4'- diamines [N, N'-bisphenyl-N,
N'-bis(1-naphthalenyl)-1,1'-biphenyl-4,4'-diamine]；
TCTA: ginseng (4- carbazole -9- base-phenyl) amine [tris (4-carbazoyl-9-yl-phenyl) amine]
Ir(piq)3: ginseng (1- phenyl-isoquinolin) iridium (III) [tris (1-phenyl-isoquinoline) iridium
(III)]；
BPhen:4,7- diphenyl -1,10- phenanthroline (4,7-diphenyl-1,10-phenanthroline)；
MoO3: molybdenum trioxide (molybdenum trioxide)；
Ir(ppy)3: three (2- phenyl-pyridin) iridium (III) [tris (2-phenyl-pyridine) iridium (III)].
<application examples 2>
Series type organic LED (using compound Fc03 as p-type carrier generating layer)
[structure I I]
ITO (150)/NPB (50)/TCTA:4wt%Ir (ppy)3(30)/BPhen (20)/BPhen:6wt%LiF (5)/
Al(1)/C60(4)/Fc03(1)/MoO3(1)/NPB (50)/TCTA:4wt%Ir (piq)3(30)/BPhen(20)/LiF(1)/
Al(100)
Refering to fig. 1 with above structure II [in bracket numerical value indicate thickness (nm)], the tandem OLED of application examples 2 and application
Example 1 is similar, the difference is that, 3 material of luminescent layer of application examples 2 is that TCTA adulterates 4wt%Ir (ppy) with application examples 13, shine
11 material of layer are that TCTA adulterates 4wt%Ir (piq)3。
<application examples 3>
Series type organic LED (using compound Fc04 as p-type carrier generating layer)
[structure III]
ITO (150)/NPB (50)/TCTA:4wt%Ir (ppy)3(30)/BPhen (20)/BPhen:6wt%LiF (5)/
Al(1)/C60(4)/Fc04(1)/MoO3(1)/NPB (50)/TCTA:4wt%Ir (ppy)3(30)/BPhen(20)/LiF(1)/
Al(100)
Refering to fig. 1 with above structure III [in bracket numerical value indicate thickness (nm)], the tandem OLED of application examples 3 with answer
Use-case 1 is similar, the difference is that, 3 material of luminescent layer of application examples 3 is that TCTA adulterates 4wt%Ir (ppy) with application examples 13, p-
8 material of type carrier generating layer is compound Fc04 (embodiment 4).
<application examples 4>
Series type organic LED (using compound Fc04 as p-type carrier generating layer)
[structure I V]
ITO (150)/NPB (50)/TCTA:4wt%Ir (piq)3(30)/BPhen (20)/BPhen:6wt%LiF (5)/
Al(1)/C60(4)/Fc04(1)/MoO3(1)/NPB (50)/TCTA:4wt%Ir (ppy)3(30)/BPhen(20)/LiF(1)/
Al(100)
Refering to fig. 1 with above structure IV [in bracket numerical value indicate thickness (nm)], the tandem OLED of application examples 4 and application
Example 1 is similar, the difference is that, 8 material of p-type carrier generating layer of application examples 4 is compound Fc04 (embodiment with application examples 1
4)。
<application examples 5>
Series type organic LED (using compound Fc04 as p-type carrier generating layer)
[structure V]
ITO (150)/NPB (30)/TCTA (20)/TCTA:TPBi:8wt%Ir (ppy)3(30)/TPBi(60)/TPBi:
6wt%LiF (5)/Al (1)/C60(4)/Fc04(1)/MoO3(1)/NPB (30)/TCTA (20)/TCTA:TPBi:8wt%Ir
(ppy)3/TPBi(60)/LiF(1)/Al(100)
Signal of the tandem OLED structure such as aforementioned structure V [numerical value indicates thickness (nm) in bracket] of application examples 5 with Fig. 2
Shown in figure, component representated by each component numerals of Fig. 2 see the table below 3 using material and each thickness degree respectively.
Table 3
In table 3, TPBi 1,3,5- tri- (N- Phenyl-benzoimidazol -2- base) benzene [1,3,5-tris (N-
Phenylbenzimidizol-2-yl) benzene] abbreviation, compound structure is as follows:
<application examples 6>
Series type organic LED (using compound Fc01 as p-type carrier generating layer)
[structure VI]
ITO (150)/NPB (30)/TCTA (20)/TCTA:TPBi:8wt%Ir (ppy)3(30)/TPBi(60)/TPBi:
6wt%LiF (5)/Al (1)/C60(4)/Fc01 (1)/MoO3 (1)/NPB (30)/TCTA (20)/TCTA:TPBi:8wt%Ir
(ppy)3/TPBi(60)/LiF(1)/Al(100)
Refering to Fig. 2 and above structure VI [numerical value indicates thickness (nm) in bracket], the tandem OLED of application examples 6 and application
Example 5 is similar, the difference is that, 23 material of p-type carrier generating layer of application examples 6 is compound Fc01 (embodiment with application examples 5
1)。
<application examples 7>
Series type organic LED (using compound Fc03 as p-type carrier generating layer)
[structure VII]
ITO (150)/NPB (30)/TCTA (20)/TCTA:TPBi:8wt%Ir (ppy)3(30)/TPBi(60)/TPBi:
6wt%LiF (5)/Al (1)/C60(4)/Fc03(1)/MoO3(1)/NPB (30)/TCTA (20)/TCTA:TPBi:8wt%Ir
(ppy)3/TPBi(60)/LiF(1)/Al(100)
Refering to Fig. 2 and above structure VII [numerical value indicates thickness (nm) in bracket], the tandem OLED of application examples 7 with answer
Use-case 5 is similar, the difference is that, 23 material of p-type carrier generating layer of application examples 7 is that compound Fc03 (is implemented with application examples 5
Example 3).
<comparing application examples 1>
Organic Light Emitting Diode (is not concatenated)
[structure VIII]
ITO (150)/NPB (50)/TCTA:4wt%Ir (piq)3(30)/BPhen(20)/LiF(1)/Al(100)
Compare the OLED structure schematic diagram such as aforementioned structure VIII [in bracket numerical value indicate thickness (nm)] and figure of application examples 1
Shown in 3, component representated by each component numerals of Fig. 3 see the table below 4 using material and each thickness degree respectively.
Table 4
<comparing application examples 2>
Organic Light Emitting Diode (is not concatenated)
[structure I X]
ITO (150)/NPB (50)/TCTA:4wt%Ir (ppy)3(30)/BPhen(20)/LiF(1)/Al(100)
Refering to Fig. 3 and above structure IX [numerical value indicates thickness (nm) in bracket], the OLED for comparing application examples 2 is answered compared with
Use-case 1 is similar, the application examples 1 compared with the difference is that, compare application examples 2 luminescent layer 33 be TCTA adulterate 4wt%Ir
(ppy)3。
<comparing application examples 3>
Organic Light Emitting Diode (is not concatenated)
[structure X]
ITO (150)/NPB (30)/TCTA (20)/TCTA:TPBi:8wt%Ir (ppy)3(30)/TPBi(60)/TPBi:
6wt%LiF (5)/Al (100)
Compare OLED structure schematic diagram such as aforementioned structure X [numerical value indicates thickness (nm) in bracket] and Fig. 4 institute of application examples 3
Show, component representated by each component numerals of Fig. 4 see the table below 5 using material and each thickness degree respectively.
Table 5
<comparing application examples 4>
Organic Light Emitting Diode (is not concatenated)
[structure XI]
ITO (150)/NPB (30)/TCTA (20)/TCTA:TPBi:8wt%Ir (ppy)3(30)/TPBi(60)/LiF
(1)/Al(100)
Refering to Fig. 4 and above structure XI [numerical value indicates thickness (nm) in bracket], the OLED for comparing application examples 4 is answered compared with
Use-case 3 is similar, the application examples 3 compared with the difference is that, compare application examples 4 electron injecting layer 42 be thickness 1nm LiF.
<HOMO and LUMO energy the rank analysis of application examples 1~7>
Utilize HOMO and LUMO the energy rank of layers of material in UPS instrument measurement application examples 1~7,1~4 acquired results of application examples
As shown in table 6 below, 5~7 acquired results of application examples are as shown in table 7 below.
Table 6
Table 7
HOMO and LUMO the energy order evidence of table 6, compound Fc03 (embodiment 3) and compound Fc04 (embodiment 4) are observed,
Its HOMO energy rank is respectively 5.1eV and 5.3eV and neighbouring MoO3The HOMO of (electric hole implanted layer) can rank (5.3ev) it is close or
It is identical, in addition, the LUMO of compound Fc03 and compound Fc04 can rank be respectively 2.8eV and 3.0eV, equally also and MoO3LUMO
Energy rank (2.3eV) is close；In addition, HOMO and LUMO the energy order evidence of observation table 7, compound Fc04 (embodiment 4), compound
Fc01 (embodiment 1) and compound Fc03 (embodiment 3), HOMO can rank be respectively 5.3eV, 5.4eV and 5.1eV and neighbouring
MoO3The HOMO energy rank (5.3ev) of (electric hole implanted layer) is close or identical, in addition, compound Fc04, compound Fc01 and chemical combination
The LUMO energy rank of object Fc03 is respectively 3.0eV, 3.0eV and 2.8eV, is equally also approached with the LUMO of MoO3 energy rank (2.3eV), by
Preceding description is it is found that compound Fc01, compound Fc03 and compound Fc04 are all suitable for the load of the p-type in tandem OLED
Sub- generating layer.Therefore, amido ferrocene derivatives of the present invention can be as the p-type carrier generating layer in OLED.
<the various luminous efficacies of the application examples 1~2 compared with of application examples 1~4 are tested>
Respectively by the OLED of tandem OLED application examples 1~2 compared with of application examples 1~4, various luminous efficacy surveys are carried out
Examination, gained start voltage (Vd), maximum luminousing brightness (L), maximum external quantum efficiency (ηext), maximum current efficiency (ηc), most
Big energy efficiency (power efficiency, ηp), maximum gives out light wavelength (λem) and the arrangement of CIE coordinate result is as shown in table 8 below.
It should be noted that the V in luminous efficacy test of the present inventiond、L、ηext、ηcAnd ηpIt is using being installed with Newport 818-ST silicon light
2400 Source of Keithley of electric diode (silicon photodiode)Power supply measurement unit instrument and
Newport 1835-C light intensity meter (optical meter) is measured；λemIt is using Hitachi F-4500 fluorescence spectrum
Instrument (fluorescence spectrophotometer) is measured.
Table 8
As shown in Table 8, application examples 1 or 2 compared with using compound Fc03 to connect with Fc04 as p-type carrier generating layer
Application examples 1~4 (tandem OLED), maximum luminousing brightness, maximum external quantum efficiency and maximum current efficiency be all higher than than
Compared with application examples 1~2 (without concatenated OLED), and by CIE coordinate it can be found that application examples 1~4 is compared to comparing application examples 1
~2, closer to white light, illustrate that amido ferrocene derivatives of the invention can be as the p-type carrier generating layer of OLED, and can make
OLED (tandem OLED) after being concatenated several luminescence units while there is high brightness, external quantum efficiency and electric current effect
The characteristics such as rate, and be suitable for application on white light OLED.
In addition, the OLED of tandem OLED application examples 1~2 compared with of application examples 1~4, in same current density
Under (current density, J), measured voltage (V), light emission luminance (L), external quantum efficiency (ηext), current efficiency
(ηc) and energy efficiency (ηp) as shown in table 9 below.
Table 9
As shown in Table 9, (10 mA/cm under same current density2), use compound Fc03 and Fc04 to carry as p-type
The application examples 1~4 (tandem OLED) of application examples 1 or 2 is compared in the series connection of sub- generating layer, light emission luminance, external quantum efficiency and
Current efficiency is equally all higher than and compares application examples 1~2 (without concatenated OLED), illustrates that amido ferrocene of the invention spreads out again
P-type carrier generating layer of the biological energy source as OLED, and it is same to make to be concatenated the OLED (tandem OLED) after several luminescence units
When there are the characteristics such as high brightness, external quantum efficiency and current efficiency.
<the various luminous efficacies of the application examples 3~4 compared with of application examples 5~7 are tested>
Respectively by the OLED of tandem OLED application examples 3~4 compared with of application examples 5~7, various luminous efficacy surveys are carried out
Examination, gained start voltage (Vd), maximum luminousing brightness (L), maximum external quantum efficiency (ηext), maximum current efficiency (ηc), most
Big energy efficiency (ηp), maximum gives out light wavelength (λem) and the arrangement of CIE coordinate result is as shown in the following table 10.
Table 10
As shown in Table 10, application examples 3 compared with using compound Fc04, Fc01 to connect with Fc03 as p-type carrier generating layer
Or 4 application examples 5~7 (tandem OLED), maximum external quantum efficiency and maximum current efficiency, which are all higher than, compares application examples 3
~4 (without concatenated OLED), illustrate amido ferrocene derivatives of the invention can as the p-type carrier generating layer of OLED, and
OLED (tandem OLED) after several luminescence units can be made to be concatenated while there is high external quantum efficiency and current efficiency etc.
Characteristic.
And the OLED of tandem OLED application examples 3~4 compared with of application examples 5~7, under same current density (J), institute
Voltage (V), the light emission luminance (L), external quantum efficiency (η measuredext), current efficiency (ηc) and energy efficiency (ηp) such as the following table 11
It is shown.
Table 11
As shown in Table 11, (the 10mA/cm under same current density2), use compound Fc04, Fc01 and Fc03 as p-
Type carrier generating layer, which is connected, compares the application examples 5~7 (tandem OLED) of application examples 3 or 4, light emission luminance, internal quantum effect
Rate and current efficiency, which are all higher than, compares application examples 3~4 (without concatenated OLED), illustrates that amido ferrocene of the invention spreads out again
P-type carrier generating layer of the biological energy source as OLED, and it is same to make to be concatenated the OLED (tandem OLED) after several luminescence units
When there are the characteristics such as high brightness, external quantum efficiency and current efficiency.
In addition, the OLED of tandem OLED application examples 3~4 compared with of application examples 5~7, Yu Xiangtong light emission luminance (L)
Under, measured voltage (V), current density (J), external quantum efficiency (ηext), current efficiency (ηc) and energy efficiency (ηp) such as
Shown in the following table 12.
Table 12
As shown in Table 12, (100cd/m under Yu Xiangtong light emission luminance2), use compound Fc04, Fc01 and Fc03 as p-
Type carrier generating layer, which is connected, compares the application examples 5~7 (tandem OLED) of application examples 1 or 2, external quantum efficiency and electric current effect
Rate, which is all higher than, compares application examples 3~4 (without concatenated OLED), illustrates that amido ferrocene derivatives of the invention really can conduct
The p-type carrier generating layer of OLED, and can make to be concatenated the OLED (tandem OLED) after several luminescence units while have outside height
The characteristics such as portion's quantum efficiency and current efficiency.In addition it is noted that current density needed for application examples 5~7 is also obvious low
In comparing application examples 3~4, illustrate that the tandem OLED of application examples 5~7 can be reached and be compared application examples with lower current density
The identical brightness of 3~4 (i.e. single layer OLED).
In conclusion amido ferrocene derivatives of the invention can be as the p-type carrier generating layer in OLED, and can make
OLED (tandem OLED) after being concatenated several luminescence units can have high luminance compared to single layer OLED component simultaneously
The characteristics such as degree, external quantum efficiency and current efficiency, so the purpose of the present invention can be reached really.
Only as described above, only the embodiment of the present invention is all when cannot be limited the scope of implementation of the present invention with this
It is all still to belong to the present invention according to simple equivalent changes and modifications made by scope of the present invention patent and patent specification content
In the range of patent covers.
Claims (4)
1. a kind of amido ferrocene derivatives, it is characterised in that: shown in the amido ferrocene derivatives such as following formula (I):
In formula (I), Ar1、Ar2It is indicated identical or differently through at least one R1Substituted phenyl, R1Indicate the benzene being unsubstituted
Base, the phenyl or ferrocene replaced through diphenyl amido.
2. amido ferrocene derivatives according to claim 1, it is characterised in that: R1What expression replaced through diphenyl amido
Phenyl or the phenyl being unsubstituted.
3. amido ferrocene derivatives according to claim 1, it is characterised in that: Ar1、Ar2Indicate contraposition through R1Replace
Phenyl.
4. a kind of Organic Light Emitting Diode, it is characterised in that: the Organic Light Emitting Diode includes the amine as shown in following formula (I)
Base ferrocene derivatives, using as p-type carrier generating layer:
In formula (I), Ar1、Ar2It is indicated identical or differently through at least one R1Substituted phenyl, R1Indicate the benzene being unsubstituted
Base, the phenyl or ferrocene replaced through diphenyl amido.
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Non-Patent Citations (2)
| Title |
|---|
| Synthesis and Properties of a (Diarylamino)ferrocene and Its Radical Cation;Arjun Mendiratta et al.;《Organometallics》;19990114;第18卷(第3期);scheme1 * |
| The Anomalous Electrochemistry of the Ferrocenylamines;Wayne E. Britton et al.;《Organometallics》;19860531;第5卷(第5期);表II * |
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