One kind contains organic compound and its application of the fluorenes of 9,9 '-spiral shell two
Technical field
The present invention relates to organic photoelectrical material technical field, contain 9 more particularly, to one kind, and 9 '-spiral shell two is fluorene structured to be
The compound-material of heart skeleton and its application in OLED fields.
Background technology
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology both can be used for make
New display product is made, can be used for making novel illumination product, be expected to substitute existing liquid crystal display and fluorescent lighting,
Application prospect is quite varied.
OLED luminescent devices just as the structure of sandwich, including electrode material film layer, and be clipped in Different electrodes film layer it
Between organic functional material, various difference in functionality materials are overlapped mutually according to purposes collectively constitutes OLED luminescent devices together.
As current device, when the two end electrodes to OLED luminescent devices apply voltage, and pass through electric field action organic layer functional material
Positive and negative charge in film layer, positive and negative charge is further compound in luminescent layer, that is, produces OLED electroluminescent.
Currently, OLED Display Techniques are applied in fields such as smart mobile phone, tablet personal computers, further will also be to electricity
Depending on etc. large scale application field extension, still, with reality products application requirement compare, the luminous efficiency of OLED, use
The performances such as life-span also need to further be lifted.
Proposing high performance research for OLED luminescent devices includes:The driving voltage of device is reduced, improves the luminous of device
Efficiency, improve service life of device etc..In order to realize the continuous lifting of the performance of OLED, not only need from OLED
The innovation of structure and manufacture craft, with greater need for the constantly research and innovation of oled light sulfate ferroelectric functional material, formulate out higher performance OLED
Functional material.
Oled light sulfate ferroelectric functional material applied to OLED can be divided into two major classes, i.e. electric charge injection transmission from purposes
Material and luminescent material, further, it can also inject charge into transmission material and be divided into electron injection transmission material, electronic blocking material
Luminescent material, can also be divided into main body luminescent material and dopant material by material, hole injection transmission material and hole barrier materials.
In order to make high performance OLED luminescent devices, it is desirable to various organic functional materials possess good photoelectric characteristic,
For example, as charge transport materials, it is desirable to there is good carrier mobility, high-vitrification conversion temperature etc., as luminous
The material of main part of layer requires that material has good bipolarity, appropriate HOMO/LUMO energy ranks etc..
The oled light sulfate ferroelectric functional material film layer for forming OLED comprises at least more than two layers structure, is applied in industry
OLED structure, then passed including hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electronics
A variety of film layers such as defeated layer, electron injecting layer, that is to say, that the photoelectric functional material applied to OLED is noted including at least hole
Enter material, hole mobile material, luminescent material, electron transport material etc., material type and collocation form have rich and more
The characteristics of sample.In addition, for the OLED collocation of different structure, used photoelectric functional material has stronger
Selectivity, performance of the identical material in different structure device, it is also possible to completely totally different.
Therefore, for the difference in functionality film layer of the industry application requirement of current OLED, and OLED, device
Photoelectric characteristic demand, it is necessary to which selection is more suitable for, and has high performance OLED functional materials or combination of materials, could realize device
The overall characteristic of high efficiency, long-life and low-voltage.For the actual demand that current OLED shows Lighting Industry, OLED at present
The development of material is also far from enough, lags behind the requirement of panel manufacturing enterprise, as the organic of material enterprise development higher performance
Functional material is particularly important.
The content of the invention
The technical problems to be solved by the invention are to provide one kind and contain 9, the organic compound of the fluorenes of 9 '-spiral shell two, have compared with
High glass transition temperature and molecule heat endurance, suitable HOMO and lumo energy, higher Eg, is optimized by device architecture, can
The effectively life-span of the photoelectric properties of lifting OLED and OLED.
The technical scheme that the present invention solves above-mentioned technical problem is as follows:One kind contains 9, the organic compound of the fluorenes of 9 '-spiral shell two,
Shown in the general structure of the compound such as formula (1):
Wherein, m, n, o or p=0 or 1, and be 0 when m, n, o or p difference;
R1、R2Independently be expressed as hydrogen atom, formula (2), formula (3), formula (4), formula (5), formula (6) institute
Show structure;R1With R2It is asynchronously hydrogen;
Work as R1Select for formula (2) or formula (3) structure when, R2Select as shown in formula (4), formula (5) or formula (6)
Structure;Work as R2Select for formula (2) or formula (3) structure when, R1Select to be tied shown in formula (4), formula (5) or formula (6)
Structure;
In formula (2), a is selected fromX1、X2、X3、X4Independently be expressed as oxygen
Atom, sulphur atom, C1-10The alkylidene of straight or branched alkyl substitution, the alkylidene of aryl substitution, alkyl or aryl substitute
One kind in tertiary amine groups;
Structure shown in formula (2), formula (3) is connected by simultaneously ring with carbazole in formula (1);
X is oxygen atom, sulphur atom, C in formula (4), formula (6)1-10Alkylidene, the aryl of straight or branched alkyl substitution
Substituted alkylidene, alkyl or aryl substitution tertiary amine groups in one kind;
R in formula (5)3、R4Independently be expressed as phenyl, naphthyl, dibiphenylyl, terphenyl, dibenzofurans,
Dibenzothiophenes or 9,9- dimethyl fluorenes or carbazole.
The beneficial effects of the invention are as follows:The compounds of this invention with the fluorenes of 9,9 '-spiral shell two for parent nucleus, connected symmetrical dendrimer or asymmetrical
Rigid radical, the crystallinity of saboteur, intermolecular aggtegation is avoided, there is high glass transition temperature, material is in OLED
When device is applied, high membranous layer stability can be kept, improves OLED service life.
On the basis of above-mentioned technical proposal, the present invention can also do following improvement.
The present invention also provides one kind and contains 9, and the preparation method of the organic compound of the fluorenes of 9 '-spiral shell two, reaction equation is such as
Under::
Specifically include following reactions steps:
1) with the fluorenes bromo-derivative of 9,9 '-spiral shell twoAnd amine compoundMix, adopt for raw material
Being dissolved with toluene, the toluene dosage is every gram 9, and the fluorenes bromo-derivative of 9 '-spiral shell two uses 30-50ml toluene, wherein, described 9,9 '-
The fluorenes bromo-derivative of spiral shell twoWith amine compoundMol ratio be 1:(1.2~5.0);
2) Pd is added into the reaction system of step 1)2(dba)3, tri-butyl phosphine and sodium tert-butoxide, wherein, the Pd2
(dba)3Mol ratio with the fluorenes bromo-derivative of 9,9 '-spiral shell two is (0.006~0.04):1, the tri-butyl phosphine and 9,9 '-spiral shell two
The mol ratio of fluorenes bromo-derivative is (0.006~0.04):1, the sodium tert-butoxide and 9, the mol ratio of the fluorenes bromo-derivative of 9 '-spiral shell two is
(2.0~8.0):1;
3) under nitrogen protection, by above-mentioned mixed solution in 95~110 DEG C, react 10~24 hours, naturally cool to room
Temperature, and filtering reacting solution, filtrate carry out vacuum rotary steam, cross neutral silica gel post, obtain target product.The condition of vacuum rotary steam
It is -0.09MPa, 85 DEG C.
The present invention also provides a kind of organic electroluminescence device, and at least one layer of functional layer contains any in claims 1 to 3
Contain the organic compound of the fluorenes of 9,9 '-spiral shell two described in.
The present invention also provides a kind of organic electroluminescence device, including electronic barrier layer, and the electronic blocking layer material is
The above-mentioned organic compound containing the fluorenes of 9,9 '-spiral shell two.
A kind of organic luminescent device as described above of the invention, further, in addition to transparent substrate layer, ito anode layer, hole
Implanted layer, hole transmission layer, luminescent layer, hole barrier/electron transfer layer, electron injecting layer and negative electrode reflection electrode layer, it is described
Transparent substrate layer, ito anode layer, hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole barrier/electronics pass
Defeated layer, electron injecting layer and negative electrode reflection electrode layer stack gradually arrangement from bottom to up.
Specifically, the hole injection layer is material HAT-CN, and thickness can be 10nm;Or/and hole transport/the electricity
Sub- barrier material is that its thickness can with the organic compound that the fluorenes of 9,9 '-spiral shell two is core described in any one of claims 1 to 3
80nm, or/and the luminescent layer are thought using CBP as material of main part, Ir (ppy)3As phosphorescence dopant material, the Hes of Ir (ppy) 3
CBP mass ratio is 1:9, thickness can be 30nm, or/and the hole barrier/electron transfer layer, its material are TPBI, thick
Spend for 40nm, and/or the electron injecting layer is LiF materials, its thickness can be 1nm, and/or the negative electrode reflection electrode layer
For materials A l, its thickness can be 100nm.
The present invention also provides a kind of organic electroluminescence device, including luminescent layer, the luminescent layer include it is above-mentioned containing 9,
The organic compound of the fluorenes of 9 '-spiral shell two.
The present invention also provides a kind of organic luminescent device, in addition to transparent substrate layer, ito anode layer, hole injection layer, sky
Cave transport layer, electronic barrier layer, hole barrier/electron transfer layer, electron injecting layer and negative electrode reflection electrode layer, the transparent base
Flaggy, ito anode layer, hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole barrier/electron transfer layer, electricity
Sub- implanted layer and negative electrode reflection electrode layer stacks gradually arrangement from bottom to up.
Specifically, the hole injection layer is material HAT-CN, thickness 10nm;Or/and the hole transport/electronics resistance
Barrier material is NPB, and thickness can be 80nm, or/and the luminescent layer is with the above-mentioned organic compound containing the fluorenes of 9,9 '-spiral shell two
As material of main part, Ir (ppy)3As phosphorescence dopant material, Ir (ppy)3With described using the fluorenes of 9,9 '-spiral shell two as the organic of core
The mass ratio of compound is 1:9, thickness can be 30nm, or/and the hole barrier/electron transfer layer, its material are TPBI,
Thickness can be 40nm, and/or the electron injecting layer is LiF materials, and its thickness can be 1nm, and/or negative electrode reflection
Electrode layer is materials A l, and its thickness can be 100nm.
The beneficial effects of the invention are as follows:The compounds of this invention structure make it that electronics and hole are more flat in the distribution of luminescent layer
Weighing apparatus, under appropriate HOMO energy levels, improves hole injection/transmission performance;Under suitable lumo energy, electronics is served again
The effect of stop, combined efficiency of the lifting exciton in luminescent layer;Light emitting functional layer materials'use as OLED luminescent devices
When, the 9 of aryl substitution, the side chain that the fluorenes of 9 '-spiral shell two is arranged in pairs or groups in the scope of the invention can effectively improve exciton utilization rate and high fluorescence spoke
Efficiency is penetrated, reduces the efficiency roll-off under high current density, reduces device voltage, improves current efficiency and the life-span of device.
Compound of the present invention has good application effect in OLED luminescent devices, before having good industrialization
Scape.
Brief description of the drawings
Fig. 1 is the materials application cited by the present invention in the structural representation of OLED;
Wherein, 1 is transparent substrate layer, and 2 be ito anode layer, and 3 be hole injection layer, and 4 be hole transmission layer, and 5 be that electronics hinders
Barrier, 6 be luminescent layer, and 7 be hole barrier/electron transfer layer, and 8 be electron injecting layer, and 9 be negative electrode reflection electrode layer.
Embodiment
The principle and feature of the present invention are described below in conjunction with accompanying drawing, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the present invention.
IntermediateSynthesis:
R11ForIn one kind
Ar1、Ar2Respectively phenyl, naphthyl or
R12For
X11、X12Respectively O, S,In one kind, R13For methyl or phenyl.
Boronic acid compounds raw material I-1 and raw material II -1 are weighed, with toluene stirring and dissolving, under an inert atmosphere, adds carbonic acid
Potassium, four triphenyl phosphorus palladiums, the mixed solution of second alcohol and water, stirring are warming up to 110~120 DEG C, react 10~24 hours, reaction knot
Shu Hou, room temperature is cooled to, filtered, filtrate layered, take organic phase vacuum rotary steam to cross neutral silica gel post to without cut, obtain chemical combination
Thing intermediate S1;In above-mentioned reaction, the mol ratio of raw material I-1 and raw material II -1 is 1:1~2;Raw material I-1 and potassium carbonate mole
Than for 1:1~3;The mol ratio of raw material I-1 and four triphenyl phosphorus palladiums is 1:0.01~0.05;
Under an inert atmosphere, intermediate S1 prepared by previous step is dissolved in o-dichlorohenzene, triphenylphosphine is added, 170
Stirring reaction 12~16 hours at~190 DEG C, reaction are cooled to room temperature after terminating, and filter, and filtrate decompression is rotated to without cut, mistake
Neutral silica gel post, obtain target product intermediate S2;Intermediate S1 is 1 with triphenylphosphine mol ratio:1~2;
Weigh intermediate S2 to be dissolved in acetic acid, 0 DEG C is cooled to ice salt bath;Weigh bromine to be dissolved in glacial acetic acid, slowly drop
Add in the acetic acid solution containing intermediate S2, reaction is stirred at room temperature 6~12 hours, after reaction terminates, sodium hydroxide water is added dropwise
Solution neutralization reaction liquid, is extracted with dichloromethane, layering, takes organic phase to filter, filtrate decompression is rotated to without cut, excessively neutral silicon
Glue post, obtain intermediate S3;In above-mentioned reaction, the molar ratio of intermediate S2 and bromine is 1:1~3;
If being coupled at intermediate S3 bromos for C-N, experimental procedure is:Under nitrogen protection, weigh successively intermediate S3,
Raw material III -1, sodium tert-butoxide, Pd2(dba)3, tri-butyl phosphine, be stirred with toluene, be heated to 110~120 DEG C, backflow is anti-
Answer 12~24 hours, sample point plate, show that no intermediate S3 is remaining, reaction is complete;Room temperature is naturally cooled to, is filtered, filtrate is entered
Row vacuum rotary steam crosses neutral silica gel post, obtains intermediate compound I -1 to without cut.In above-mentioned reaction, intermediate S3 rubs with raw material III -1
You are than being 1:1~2;The mol ratio of intermediate S3 and sodium tert-butoxide is 1:1~3;Intermediate S3 and Pd2(dba)3And tri-tert
The mol ratio of phosphine is 1:0.01~0.05;
If being coupled at intermediate S3 bromos for C-C, experimental procedure is:Intermediate S3, raw material III -2 are weighed, it is molten with toluene
Solution, under an inert atmosphere, potassium carbonate, four triphenyl phosphorus palladiums, ethanol and the aqueous solution are added, stirring is warming up to 110~120 DEG C, instead
Answer 10~24 hours;After reaction terminates, room temperature is cooled to, is filtered, filtrate layered, takes organic phase vacuum rotary steam to without cut, mistake
Neutral silica gel post, obtain target product intermediate compound I -2.In above-mentioned reaction, the mol ratio of intermediate S3 and raw material III -2 is 1:1~
2;The mol ratio of intermediate S3 and potassium carbonate is 1:1~3;The mol ratio of intermediate S3 and four triphenyl phosphorus palladiums is 1:0.01~
0.05。
R14、R15RespectivelyIn one kind
X13Respectively O, S,In one kind, R13For methyl or phenyl.
Under nitrogen protection, raw material II -3, raw material III -3, sodium tert-butoxide, Pd are weighed successively2(dba)3, tri-butyl phosphine,
Add toluene to be stirred, be heated to 110~120 DEG C, back flow reaction 12~24 hours, sample point plate, show no raw material II -3
Residue, reaction are complete;Room temperature is naturally cooled to, is filtered, filtrate carries out vacuum rotary steam to without cut, crosses neutral silica gel post, obtains
Intermediate S4.In above-mentioned reaction, raw material II -3 is 1 with the mol ratio of raw material III -3:1~2;The mol ratio of raw material II -3 and potassium carbonate
For 1:1~3;Raw material II -3 and Pd2(dba)3Mol ratio with tri-butyl phosphine is 1:0.01~0.05;
Under nitrogen protection, intermediate S4, raw material I-3, sodium tert-butoxide, Pd are weighed successively2(dba)3, tri-butyl phosphine, use
Toluene is stirred, and is heated to 110~120 DEG C, back flow reaction 12~24 hours, sample point plate, is shown that no intermediate S4 is remaining,
Reaction is complete;Room temperature is naturally cooled to, is filtered, filtrate carries out vacuum rotary steam to without cut, crosses neutral silica gel post, obtains intermediate
Ⅱ-3;In above-mentioned reaction, intermediate S4 is 1 with raw material I-3 mol ratios:1~2;The mol ratio of intermediate S4 and potassium carbonate is 1:1
~3;Intermediate S4 and Pd2(dba)3Mol ratio with tri-butyl phosphine is 1:0.01~0.05.
R16、R17、R18RespectivelyIn one kind
X14For O, S,In one kind, R13For methyl or phenyl.
Under nitrogen protection, raw material I-4 (or raw material I-5), raw material II -4 (or raw material II -5), the tert-butyl alcohol are weighed successively
Sodium, Pd2(dba)3, tri-butyl phosphine, be stirred with toluene, be heated to 110~120 DEG C, back flow reaction 12~24 hours, take
Sampling point plate, show that no raw material I-4 (or raw material I-5) is remaining, reaction is complete;Room temperature is naturally cooled to, is filtered, filtrate is depressurized
Revolving crosses neutral silica gel post, obtains intermediate II -4 (or intermediate II -5) to without cut;
In above-mentioned reaction, if two side chains connected at raw material I-4 halos are identical, raw material I-4 rubs with raw material II -4
Your ratio is 1: 2~3;The mol ratio of raw material I-4 and sodium tert-butoxide is 1: 2~4;Raw material I-4 and Pd2(pda)3And tri-tert
The mol ratio of phosphine is 1: 0.05~0.1;If two side chain differences, raw material I-5 is 1: 1~1.5 with the mol ratio of raw material II -5,
Raw material I-5 is 1: 1~3 with sodium tert-butoxide mol ratio, raw material I-5 and Pd2(pda)3, tri-butyl phosphine mol ratio be 1:
0.01~0.05;Coupling is completed in two steps.
X15、X16For O, S,In one kind, R13For methyl or phenyl.
Raw material I-6 and raw material II -6 are weighed, toluene stirring and dissolving is added, under an inert atmosphere, sequentially adds potassium carbonate, four
Triphenyl phosphorus palladium, ethanol and the aqueous solution, stirring are warming up to 110~120 DEG C, react 10~24 hours;After reaction terminates, it is cooled to
Room temperature, filtering.Filtrate layered, take organic phase vacuum rotary steam to cross neutral silica gel post to without cut, obtain target product intermediate compound I-
6.In above-mentioned reaction, the mol ratio of raw material I-6 and raw material II -6 is 1: 2~3;The mol ratio of raw material I-6 and potassium carbonate is 1:2~
6;The mol ratio of boronic acid compounds and four triphenyl phosphorus palladiums is 1:0.05~0.1.
Respectively by taking the synthesis of intermediate A 1, intermediate A 3, intermediate A 11 and intermediate A 14 as an example:
By taking intermediate A 1 as an example:
1) in 250ml there-necked flask, lead under nitrogen protection, addition 0.05mol dibenzo [b, d] furans -3- boric acid,
The bromo- 2- nitrobenzene of 0.06mol 1-, 100ml toluene are stirred, and add 0.025mol Pd (PPh3)4, 0.075mol carbonic acid
Potassium, 50ml water and ethanol 1:1 mixed solution, stirring are warming up to 120 DEG C, and back flow reaction 12 hours, sample point plate, display is without two
Benzo [b, d] furans -3- boric acid is remaining, and reaction is complete;Room temperature is naturally cooled to, filters, filtrate layered, takes organic phase to be subtracted
Pressure revolving crosses neutral silica gel post, obtains intermediate 1-1, HPLC purity 99.3%, yield 70.2% to without cut;
2) in 250ml there-necked flask, lead under nitrogen protection, add 0.04mol intermediate 1-1,0.04mol triphenyls
Phosphine, 100ml o-dichlorohenzenes are stirred, and are heated to 180 DEG C and are reacted 12 hours, sample point plate, show that no intermediate 1-1 is remaining,
Reaction is complete;Filtering, filtrate carry out vacuum rotary steam to without cut, cross neutral silica gel post, obtain intermediate 1-2, HPLC purity
99.2%, yield 71.5%;
3) in 250ml there-necked flask, 0.04mol intermediate 1-2,100ml acetic acid stirring and dissolvings is added, are dropped with ice salt bath
Temperature weighs 0.05mol Br to 0 DEG C250ml acetic acid is dissolved in, the acetic acid solution of bromine is slowly added dropwise into above-mentioned reaction system, is dripped
After adding end, it is warmed to room temperature, stirring reaction 12 hours;Sample point plate, show that no intermediate 1-2 is remaining, reaction is complete;Add NaOH
Aqueous solution neutralization reaction liquid, dichloromethane extraction being added, layering, takes organic phase to filter, filtrate carries out vacuum rotary steam to without cut,
Neutral silica gel post is crossed, obtains intermediate 1-3, HPLC purity 99.3%, yield 68.9%;
4) in 250ml there-necked flask, lead under nitrogen protection, add 0.03mol intermediate 1-3,0.036mol dibenzo
[b, d] furans -4- boric acid, 100ml toluene stirring and dissolvings, add 0.0015mol tetra-triphenylphosphine palladiums, 0.045mol carbonic acid
Potassium, 50ml water and ethanol 1:1 mixed solution, 120 DEG C are heated with stirring to, back flow reaction 12 hours, sample point plate, display is without in
Mesosome 1-3 is remaining, and reaction is complete;Room temperature is naturally cooled to, is filtered, filtrate layered, takes organic phase to carry out vacuum rotary steam to nothing and evaporates
Point, neutral silica gel post is crossed, obtains intermediate A 1, HPLC purity 99.3%, yield 65.9%;
Elementary analysis structure (molecular formula C30H17NO2):Theoretical value C, 85.09;H,4.05;N,3.31;O,7.56;Test
Value:C,82.42;H,5.08;N,5.85.
HPLC-MS(m/z):Theoretical value 423.13, measured value 423.15.
By taking intermediate A 3 as an example:
1) in 250ml there-necked flask, lead under nitrogen protection, add 0.05mol (9,9- dimethyl -9H- fluorenes) -3- boron
Acid, the bromo- 2- nitrobenzene of 0.06mol 1-, 100ml toluene are stirred, and add 0.025mol Pd (PPh3)4, 0.075mol carbon
Sour potassium, 50ml water and ethanol 1:1 mixed solution, stirring are warming up to 120 DEG C, back flow reaction 24 hours, sample point plate, show nothing
(9,9- dimethyl -9H- fluorenes) -3- boric acid is remaining, and reaction is complete;Room temperature is naturally cooled to, filters, filtrate layered, takes organic phase
Vacuum rotary steam is carried out to without cut, neutral silica gel post is crossed, obtains intermediate 2-1, HPLC purity 99.3%, yield 68.2%;
2) in 250ml there-necked flask, lead under nitrogen protection, add 0.04mol intermediate 2-1,0.04mol triphenyls
Phosphine, 100ml o-dichlorohenzenes are stirred, and are heated to 180 DEG C and are reacted 12 hours, sample point plate, show that no intermediate 2-1 is remaining,
Reaction is complete;Filtering, filtrate carry out vacuum rotary steam to without cut, cross neutral silica gel post, obtain intermediate 2-2, HPLC purity
99.2%, yield 70.5%;
3) in 250ml there-necked flask, 0.04mol intermediate 2-2,100ml acetic acid stirring and dissolvings is added, are dropped with ice salt bath
Temperature weighs 0.05mol Br to 0 DEG C250ml acetic acid is dissolved in, the acetic acid solution of bromine is slowly added dropwise into above-mentioned reaction system, is dripped
After adding end, it is warmed to room temperature, stirring reaction 12 hours;Sample point plate, show that no intermediate 2-2 is remaining, reaction is complete;Add NaOH
Aqueous solution neutralization reaction liquid, dichloromethane extraction being added, layering, takes organic phase to filter, filtrate carries out vacuum rotary steam to without cut,
Neutral silica gel post is crossed, obtains intermediate 2-3, HPLC purity 99.3%, yield 68.9%;
4) in 250ml there-necked flask, lead under nitrogen protection, add 0.03mol intermediates 2-3,0.036mol9,9- bis-
Methyl -9,10- acridan, 150ml toluene are stirred, and add 0.045mol sodium tert-butoxides, 0.0015molPd2
(dba)3, 0.0015mol tri-butyl phosphines, 115 DEG C are heated with stirring to, back flow reaction 24 hours, sample point plate, show no centre
Body 2-3 is remaining, and reaction is complete;Room temperature is naturally cooled to, is filtered, filtrate carries out vacuum rotary steam extremely without cut, crosses neutral silica gel post,
Obtain intermediate A 3, HPLC purity 99.3%, yield 65.9%;
Elementary analysis structure (molecular formula C33H24N2O):Theoretical value C, 85.32;H,5.21;N,6.03;O,3.44;Test
Value:C,85.32;H,5.21;N,6.04.
HPLC-MS(m/z):Theoretical value 490.24, measured value 490.29.
By taking intermediate A 11 as an example:
1) in 250ml there-necked flask, lead under nitrogen protection, bromo- 9, the 9- dimethyl -9H- fluorenes of addition 0.03mol 2-,
0.036mol [1,1'- biphenyl] -2- amine, 150ml toluene are stirred, and add 0.045mol sodium tert-butoxides, 0.0015mol
Pd2(dba)3, 0.0015mol tri-butyl phosphines, 115 DEG C are heated with stirring to, back flow reaction 24 hours, sample point plate, show no 2-
Bromo- 9,9- dimethyl -9H- fluorenes is remaining, and reaction is complete;Room temperature is naturally cooled to, is filtered, filtrate carries out vacuum rotary steam to nothing and evaporated
Point, neutral silica gel post is crossed, obtains intermediate 3-1, HPLC purity 99.3%, yield 65.9%;
2) in 250ml there-necked flask, lead under nitrogen protection, it is bromo- to add 0.03mol intermediates 3-1,0.036mol 3-
9H- carbazoles, 150ml toluene are stirred, and add 0.045mol sodium tert-butoxides, 0.0015molPd2(dba)3, 0.0015mol
Tri-butyl phosphine, 115 DEG C are heated with stirring to, back flow reaction 24 hours, sample point plate, show that no intermediate 3-1 is remaining, reacted
Entirely;Room temperature is naturally cooled to, is filtered, filtrate carries out vacuum rotary steam extremely without cut, crosses neutral silica gel post, obtains intermediate A 11,
HPLC purity 99.3%, yield 65.9%;
Elementary analysis structure (molecular formula C39H30N2):Theoretical value C, 88.94;H,5.74;N,5.32;Test value:C,
88.87;H,5.76;N,5.38.
HPLC-MS(m/z):Theoretical value 526.24, measured value 526.27.
By taking intermediate A 14 as an example:
In 250ml there-necked flask, lead under nitrogen protection, add 0.05mol 3, the bromo- 9H- carbazoles of 6- bis-, 0.12mol bis-
Benzo [b, d] furans -4- boric acid, 100ml toluene stirring and dissolvings, add 0.005mol Pd (PPh3)4, 0.16mol potassium carbonate,
50ml second alcohol and water 1:1 mixed solution, 120 DEG C are heated with stirring to, back flow reaction 24 hours, sample point plate, display is without 3,6- bis-
Bromo- 9H- carbazoles are remaining, and reaction is complete;Room temperature is naturally cooled to, is filtered, filtrate layered, takes organic phase to carry out vacuum rotary steam to nothing
Cut, neutral silica gel post is crossed, obtains intermediate A 14, HPLC purity 99.3%, yield 69.2%;
Elementary analysis structure (molecular formula C36H21NO2):Theoretical value C, 86.55;H,4.24;N,2.80;O,6.41;Test
Value:C,86.48;H,4.29;N,2.75.
HPLC-MS(m/z):Theoretical value 499.16, measured value 499.18.
By raw material I, raw material II, raw material III and intermediate S synthesis material I, concrete structure are as shown in table 1;
Table 1
Embodiment 1
The synthesis of compound 2:
Synthetic route:
In 250ml there-necked flask, lead under nitrogen protection, add the bromo- fluorenes of 9,9'- spiral shells two of 0.01mol 3-, 0.012mol
Raw material A 1,150ml toluene are stirred, then addition 0.03mol sodium tert-butoxides, and 5 × 10-5molPd2(dba)3, 5 × 10-5mol
Tri-butyl phosphine, 105 DEG C are heated to, back flow reaction 24 hours, sample point plate, shows that no bromo-derivative is remaining, reaction is complete;It is natural
Room temperature is cooled to, is filtered, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product,
HPLC purity 99.1%, yield 65.4%;
Elementary analysis structure (molecular formula C55H31NO2):Theoretical value C, 89.53;H,4.23;N,1.90;O,4.34;Test
Value:C,89.49;H,4.24;N,1.92;O,4.35.
HPLC-MS:Material molecule amount is 737.24, surveys molecular weight 737.85.
Embodiment 2
The synthesis of compound 9:
Synthetic route:
In 250ml there-necked flask, lead under nitrogen protection, add the bromo- fluorenes of 9,9'- spiral shells two of 0.01mol 3-, 0.012mol
Raw material A 2,150ml toluene are stirred, then addition 0.03mol sodium tert-butoxides, and 5 × 10-5molPd2(dba)3, 5 × 10-5mol
Tri-butyl phosphine, 105 DEG C are heated to, back flow reaction 24 hours, sample point plate, shows that no bromo-derivative is remaining, reaction is complete;It is natural
Room temperature is cooled to, is filtered, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product,
HPLC purity 99.3%, yield 68.2%;
Elementary analysis structure (molecular formula C65H42N2):Theoretical value C, 91.73;H,4.97;N,3.29;Test value:C,
91.73;H,4.99;N,3.28.
HPLC-MS:Material molecule amount is 850.33, surveys molecular weight 850.78.
Embodiment 3
The synthesis of compound 10:
Synthetic route:
In 250ml there-necked flask, lead under nitrogen protection, add the bromo- fluorenes of 9,9'- spiral shells two of 0.01mol 2-, 0.012mol
Raw material A 3,150ml toluene are stirred, then addition 0.03mol sodium tert-butoxides, and 5 × 10-5molPd2(dba)3, 5 × 10-5mol
Tri-butyl phosphine, 105 DEG C are heated to, back flow reaction 24 hours, sample point plate, shows that no bromo-derivative is remaining, reaction is complete;It is natural
Room temperature is cooled to, is filtered, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product,
HPLC purity 99.5%, yield 72.3%;
Elementary analysis structure (molecular formula C61H44N2):Theoretical value C, 91.01;H,5.51;N,3.48;Test value:C,
91.01;H,5.52;N,3.47.
HPLC-MS:Material molecule amount is 804.35, surveys molecular weight 804.96.
Embodiment 4
The synthesis of compound 12:
Synthetic route:
In 250ml there-necked flask, lead under nitrogen protection, add the bromo- fluorenes of 9,9'- spiral shells two of 0.01mol 3-, 0.012mol
Raw material A 4,150ml toluene are stirred, then addition 0.03mol sodium tert-butoxides, and 5 × 10-5molPd2(dba)3, 5 × 10-5mol
Tri-butyl phosphine, 105 DEG C are heated to, back flow reaction 24 hours, sample point plate, shows that no bromo-derivative is remaining, reaction is complete;It is natural
Room temperature is cooled to, is filtered, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product,
HPLC purity 99.2%, yield 68.7%;
Elementary analysis structure (molecular formula C61H44N2):Theoretical value C, 91.01;H,5.51;N,3.48;Test value:C,
91.01;H,5.52;N,3.47.
HPLC-MS:Material molecule amount is 804.35, surveys molecular weight 804.92.
Embodiment 5
The synthesis of compound 16:
Synthetic route:
In 250ml there-necked flask, lead under nitrogen protection, add the bromo- fluorenes of 9,9'- spiral shells two of 0.01mol 3-, 0.012mol
Raw material A 5,150ml toluene are stirred, then addition 0.03mol sodium tert-butoxides, and 5 × 10-5molPd2(dba)3, 5 × 10-5mol
Tri-butyl phosphine, 105 DEG C are heated to, back flow reaction 24 hours, sample point plate, shows that no bromo-derivative is remaining, reaction is complete;It is natural
Room temperature is cooled to, is filtered, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product,
HPLC purity 99.4%, yield 75.7%;
Elementary analysis structure (molecular formula C58H40N2):Theoretical value C, 91.07;H,5.27;N,3.66;Test value:C,
91.09;H,5.26;N,3.65.
HPLC-MS:Material molecule amount is 764.32, surveys molecular weight 764.83.
Embodiment 6
The synthesis of compound 21:
Synthetic route:
Prepared by the synthetic method of compound 2 in embodiment 1, difference is to replace raw material A 1 with raw material A 6;
Elementary analysis structure (molecular formula C58H40N2O):Theoretical value C, 89.20;H,5.16;N,3.59;O,2.05;Test
Value:C,89.21;H,5.15;N,3.58;O,2.06.
HPLC-MS:Material molecule amount is 780.31, surveys molecular weight 780.89.
Embodiment 7
The synthesis of compound 22:
Synthetic route:
Prepared by the synthetic method of compound 2 in embodiment 1, difference is to replace raw material A 1 with raw material A 7;
Elementary analysis structure (molecular formula C58H37NOS):Theoretical value C, 87.52;H,4.69;N,1.76;O,2.01;S,
4.03;Test value:C,87.54;H,4.68;N,1.75;O,2.02;S,4.01.
HPLC-MS:Material molecule amount is 795.26, surveys molecular weight 795.89.
Embodiment 8
The synthesis of compound 25:
Synthetic route:
Prepared by the synthetic method of compound 2 in embodiment 1, difference is to replace raw material A 1 with raw material A 8;
Elementary analysis structure (molecular formula C61H44N2O):Theoretical value C, 89.24;H,5.40;N,3.41;O,1.95;Test
Value:C,89.25;H,5.41;N,3.40;O,1.94.
HPLC-MS:Material molecule amount is 820.35, surveys molecular weight 820.89.
Embodiment 9
The synthesis of compound 27:
Synthetic route:
Prepared by the synthetic method of compound 10 in embodiment 3, difference is to replace raw material A 3 with raw material A 9;
Elementary analysis structure (molecular formula C70H48N2O):Theoretical value C, 90.10;H,5.18;N,3.00;O,1.71;Test
Value:C,90.09;H,5.19;N,3.02;O,1.70.
HPLC-MS:Material molecule amount is 932.38, surveys molecular weight 932.95.
Embodiment 10
The synthesis of compound 31:
Synthetic route:
Prepared by the synthetic method of compound 2 in embodiment 1, difference is to replace raw material A 1 with raw material A 10;
Elementary analysis structure (molecular formula C49H32N2):Theoretical value C, 90.71;H,4.97;N,4.32;Test value:C,
90.72;H,4.95;N,4.33.
HPLC-MS:Material molecule amount is 648.26, surveys molecular weight 648.71.
Embodiment 11
The synthesis of compound 33:
Synthetic route:
In 250ml there-necked flask, lead to nitrogen protection under, add 0.01mol 3,6- bis- bromo- 9, the fluorenes of 9 '-spiral shell two,
0.024mol raw material As 10,150ml toluene are stirred, then addition 0.04mol sodium tert-butoxides, and 1 × 10-4molPd2(dba)3,
1×10-4Mol tri-butyl phosphines, 105 DEG C are heated to, back flow reaction 24 hours, sample point plate, shows that no bromo-derivative is remaining, reaction
Completely;Room temperature is naturally cooled to, is filtered, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains mesh
Mark product, HPLC purity 98.9%, yield 65.5%;
Elementary analysis structure (molecular formula C73H48N4):Theoretical value C, 89.36;H,4.93;N,5.71;Test value:C,
89.34;H,4.94;N,5.72.
HPLC-MS:Material molecule amount is 980.39, surveys molecular weight 980.93.
Embodiment 12
The synthesis of compound 36:
Synthetic route:
In 250ml there-necked flask, lead under nitrogen protection, addition 0.01mol3, the bromo- fluorenes of 9,9'- spiral shells two of 3', 6- tri-,
0.035mol raw material As 10,200ml toluene are stirred, then addition 0.05mol sodium tert-butoxides, and 2 × 10-4molPd2(dba)3,
2×10-4Mol tri-butyl phosphines, 105 DEG C are heated to, back flow reaction 24 hours, sample point plate, shows that no bromo-derivative is remaining, reaction
Completely;Room temperature is naturally cooled to, is filtered, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains mesh
Mark product, HPLC purity 98.5%, yield 54.7%;
Elementary analysis structure (molecular formula C97H64N6):Theoretical value C, 88.69;H,4.91;N,6.40;Test value:C,
88.68;H,4.90;N,6.42.
HPLC-MS:Material molecule amount is 1312.52, surveys molecular weight 1312.97.
Embodiment 13
The synthesis of compound 38:
Synthetic route:
Prepared by the synthetic method of compound 2 in embodiment 1, difference is to replace raw material A 1 with raw material A 11;
Elementary analysis structure (molecular formula C64H44N2):Theoretical value C, 91.40;H,5.27;N,3.33;Test value:C,
91.43;H,5.26;N,3.31.
HPLC-MS:Material molecule amount is 840.35, surveys molecular weight 840.79.
Embodiment 14
The synthesis of compound 43:
Synthetic route:
Prepared by the synthetic method of compound 2 in embodiment 1, difference is to replace raw material A 1 with raw material A 12;
Elementary analysis structure (molecular formula C64H43N3O):Theoretical value C, 88.35;H,4.98;N,4.83;O,1.84;Test
Value:C,88.35;H,4.99;N,4.81;O,1.85.
HPLC-MS:Material molecule amount is 869.34, surveys molecular weight 869.85.
Embodiment 15
The synthesis of compound 46:
Synthetic route:
In 250ml there-necked flask, lead under nitrogen protection, addition 0.01mol 3, the bromo- fluorenes of 9,9'- spiral shells two of 3'- bis-,
0.024mol raw material As 13,150ml toluene are stirred, then addition 0.04mol sodium tert-butoxides, and 1 × 10-4molPd2(dba)3,
1×10-4Mol tri-butyl phosphines, 105 DEG C are heated to, back flow reaction 24 hours, sample point plate, shows that no bromo-derivative is remaining, reaction
Completely;Room temperature is naturally cooled to, is filtered, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains mesh
Mark product, HPLC purity 99.1%, yield 63.7%;
Elementary analysis structure (molecular formula C79H56N4):Theoretical value C, 89.40;H,5.32;N,5.28;Test value:C,
89.43;H,5.31;N,5.26.
HPLC-MS:Material molecule amount is 1060.45, surveys molecular weight 1060.84.
Embodiment 16
The synthesis of compound 48:
Synthetic route:
Prepared by the synthetic method of compound 2 in embodiment 1, difference is to replace raw material A 1 with raw material A 14;
Elementary analysis structure (molecular formula C61H35NO2):Theoretical value C, 90.01;H,4.33;N,1.72;O,3.93;Test
Value:C,90.01;H,4.35;N,1.73;O,3.91.
HPLC-MS:Material molecule amount is 813.27, surveys molecular weight 813.68
Embodiment 17
The synthesis of compound 52:
Synthetic route:
Prepared by the synthetic method of compound 2 in embodiment 1, difference is to replace raw material A 1 with raw material A 15;
Elementary analysis structure (molecular formula C67H49N3):Theoretical value C, 89.80;H,5.51;N,4.69;Test value:C,
89.81;H,5.52;N,4.67.
HPLC-MS:Material molecule amount is 895.39, surveys molecular weight 895.94.
Embodiment 18
The synthesis of compound 67:
Synthetic route:
Prepared by the synthetic method of compound 10 in embodiment 3, difference is to replace raw material A 3 with raw material A 16;
Elementary analysis structure (molecular formula C64H43N3):Theoretical value C, 90.01;H,5.07;N,4.92;Test value:C,
90.00;H,5.05;N,4.95.
HPLC-MS:Material molecule amount is 853.35, surveys molecular weight 853.92.
Embodiment 19
The synthesis of compound 68:
Synthetic route:
Prepared by the synthetic method of compound 2 in embodiment 1, difference is to replace raw material A 1 with raw material A 17;
Elementary analysis structure (molecular formula C64H43N3):Theoretical value C, 90.01;H,5.07;N,4.92;Test value:C,
90.00;H,5.06;N,4.94.
HPLC-MS:Material molecule amount is 853.35, surveys molecular weight 853.87.
Embodiment 20
The synthesis of compound 70:
Synthetic route:
Prepared by the synthetic method of compound 2 in embodiment 1, difference is to replace raw material A 1 with raw material A 18;
Elementary analysis structure (molecular formula C61H39N3):Theoretical value C, 90.01;H,4.83;N,5.16;Test value:C,
90.01;H,4.84;N,5.15.
HPLC-MS:Material molecule amount is 813.31, surveys molecular weight 813.89.
The compounds of this invention uses in luminescent device, can be used as electronic blocking layer material, can also be used as luminescent layer
Subjective and Objective materials'use.The compounds of this invention 12,16,22,25,31,38,43,48,52,68 is carried out respectively hot property and
The test of HOMO energy levels, testing result are as shown in table 2.
Table 2
Note:Glass transition temperature Tg is by differential scanning calorimetry (DSC, German Nai Chi companies DSC204F1 differential scanning calorimetries
Instrument) measure, 10 DEG C/min of heating rate;Thermal weight loss temperature Td is the temperature of the weightlessness 1% in nitrogen atmosphere, public in Japanese Shimadzu
It is measured on the TGA-50H thermogravimetric analyzers of department, nitrogen flow 20mL/min;Highest occupied molecular orbital HOMO energy levels are
Tested, tested as atmospheric environment by photoelectron emissions spectrometer (AC-2 type PESA).
From upper table data, the compounds of this invention has suitable HOMO energy levels, can be applied to different functional layers, this
Invention 9, the fluorene compound of 9 '-spiral shell two has higher heat endurance so that the made OLED devices containing the compounds of this invention
Part life-span upgrading.
The OLED material of the invention synthesized is described in detail below by way of device embodiments 1~10 and comparative example 1 in the devices
Application effect.Device embodiments 2~10 of the present invention, the making work of the device compared with device embodiments 1 of comparative example 1
Skill is identical, and employed identical baseplate material and electrode material, the thickness of electrode material are also consistent, and institute is not
Same is that the material of main part or electronic blocking layer material of the luminescent layer 6 in device are changed.Each embodiment obtained device
The performance test results are as shown in table 3.
Device embodiments 1
A kind of electroluminescent device, its preparation process include:
A) the ito anode layer 2 cleaned on transparent substrate layer 1, cleans each 15 with deionized water, acetone, EtOH Sonicate respectively
Minute, then handled 2 minutes in plasma cleaner;
B) on ito anode layer 2, hole injection layer material HAT-CN, thickness 10nm are deposited by vacuum evaporation mode,
This layer is as hole injection layer 3;
C) on hole injection layer 3, hole mobile material NPB, thickness 60nm, the layer are deposited by vacuum evaporation mode
For hole transmission layer 4;
D) on hole transmission layer 4, electronic blocking layer material NPB, thickness 20nm are deposited by vacuum evaporation mode, should
Layer is electronic barrier layer 5;
E) luminescent layer 6 is deposited on electronic barrier layer 5, using the compounds of this invention 12 as being used as material of main part, Ir
(ppy)3As dopant material, Ir (ppy)3Mass ratio with compound 12 is 1:9, thickness 30nm;
E) on luminescent layer 6, electron transport material TPBI, thickness 40nm, this layer are deposited by vacuum evaporation mode
Organic material uses as hole barrier/electron transfer layer 7;
F) on hole barrier/electron transfer layer 7, vacuum evaporation electron injecting layer LiF, thickness 1nm, the layer is electricity
Sub- implanted layer 8;
G) on electron injecting layer 8, vacuum evaporation negative electrode Al (100nm), the layer is negative electrode reflection electrode layer 9;
After the making that electroluminescent device is completed according to above-mentioned steps, the current efficiency of measurement device and life-span, its result
It is shown in Table 3.
The molecular machinery formula of associated materials is as follows:
Device embodiments 2
The difference of the present embodiment and device embodiments 1 is:The luminescent layer material of main part of electroluminescent device is changed into
The compounds of this invention 22, dopant material are Ir (ppy)3, Ir (ppy)3Mass ratio with compound 22 is 1:9, gained electroluminescent
The detection data of device are shown in Table 3.
Device embodiments 3
The difference of the present embodiment and device embodiments 1 is:The luminescent layer material of main part of electroluminescent device is changed into
The compounds of this invention 48, dopant material are Ir (ppy)3, Ir (ppy)3Mass ratio with compound 48 is 1:9, gained electroluminescent
The detection data of device are shown in Table 3.
Device embodiments 4
The difference of the present embodiment and device embodiments 1 is:The material of the electronic barrier layer 5 of electroluminescent device becomes
For the compounds of this invention 16, the material of main part of luminescent layer 6 is known compound CBP, and dopant material is Ir (ppy)3, Ir (ppy)3
Mass ratio with CBP is 1:9, the detection data of gained electroluminescent device are shown in Table 3.
Device embodiments 5
The difference of the present embodiment and device embodiments 1 is:The material of the electronic barrier layer 5 of electroluminescent device becomes
For the compounds of this invention 31, the material of main part of luminescent layer 5 is known compound CBP, and dopant material is Ir (ppy)3, Ir (ppy)3
Mass ratio with CBP is 1:9, the detection data of gained electroluminescent device are shown in Table 3.
Device embodiments 6
The difference of the present embodiment and device embodiments 1 is:The material of electroluminescent device electronic barrier layer 5 is changed into
The compounds of this invention 38, the material of main part of luminescent layer 5 is known compound CBP, and dopant material is Ir (ppy)3, Ir (ppy)3With
CBP mass ratio is 1:9, the detection data of gained electroluminescent device are shown in Table 3.
Device embodiments 7
The difference of the present embodiment and device embodiments 1 is:The material of the electronic barrier layer 5 of electroluminescent device becomes
For the compounds of this invention 43, the material of main part of luminescent layer 5 is known compound CBP, and dopant material is Ir (ppy)3, Ir (ppy)3
Mass ratio with CBP is 1:9, the detection data of gained electroluminescent device are shown in Table 3.
Device embodiments 8
The difference of the present embodiment and device embodiments 1 is:The luminescent layer material of main part of electroluminescent device is changed into
The compounds of this invention 25 and compound GHN, dopant material are Ir (ppy)3, compound 25, GHN and Ir (ppy)3Three's mass ratio
For for 60:30:10, the detection data of gained electroluminescent device are shown in Table 3.
Device embodiments 9
The difference of the present embodiment and device embodiments 1 is:The luminescent layer material of main part of electroluminescent device is changed into
The compounds of this invention 52 and compound GHN, dopant material are Ir (ppy)3, compound 52, GHN and Ir (ppy)3Three's mass ratio
For for 60:30:10, the detection data of gained electroluminescent device are shown in Table 3.
Device embodiments 10
The difference of the present embodiment and device embodiments 1 is:The luminescent layer material of main part of electroluminescent device is changed into
The compounds of this invention 68 and compound GHN, dopant material are Ir (ppy)3, compound 68, GHN and Ir (ppy)3Three's mass ratio
For for 60:30:10, the detection data of gained electroluminescent device are shown in Table 3.
Device comparative example 1
The difference of the present embodiment and device embodiments 1 is:The luminescent layer material of main part of electroluminescent device is changed into
Known compound CBP, the detection data of gained electroluminescent device are shown in Table 3.
Table 3
Note:For device detection performance using device comparative example 1 as reference, the device property indices of comparative example 1 are set to 1.0.
The current efficiency of comparative example 1 is 28cd/A (@10mA/cm2);CIE chromaticity coordinates is (0.33,0.63);The LT95 longevity under 5000 brightness
Life decays to 2.5Hr.Life time decay test of the present invention can select model M6000OLED life-span test systems, can also adopt
With M7000OLED photoelectricity and life-span integrated test system.
It can be seen that the machine compound fluorene structured containing 9,9 '-spiral shell two of the present invention can be applied to by the result of table 3
OLED luminescent devices make, and compared with comparative example 1, either efficiency or life-span obtain larger than known OLED material
Take on a new look, particularly the life time decay of device obtains larger lifting.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.