summary of the invention
The object of the invention is to the novel benzofluorene of proposition one class and carbazoles derivative, this compounds may be used for ORGANIC ELECTROLUMINESCENCE DISPLAYS field.Particularly, this compounds, in display of organic electroluminescence, as hole-injecting material or as hole mobile material, also can be used as light emitting host material or luminescent material in fluorescent device.
Especially, we find, in material of the present invention, if benzofluorene carbazole precursor structure only connects condensed-nuclei aromatics, instead of connect triaryl amine or fused heterocycle aromatic hydrocarbons, such as carbazole group, dibenzothiophene group, diphenylene-oxide group etc., such material is suitable as light emitting host material, device light emitting efficiency is improved a lot, and device lifetime is longer.And carbazole precursor structure being connected with triaryl amine or fused heterocycle aromatic hydrocarbons, such as carbazole group, dibenzothiophene group, diphenylene-oxide group etc. at benzofluorene, such material is suitable as hole mobile material.In a word, the use of material of the present invention, what reduce device opens bright voltage, improves the luminous efficiency of device, adds the work-ing life of device.
For this reason, the technical scheme that the present invention takes is:
A kind of 10,15-phenylbenzene benzofluorene carbazole derivative, have structure as shown in the formula (I):
Wherein: Ar
1-Ar
4independently be selected from the substituted or non-substituted aromatic hydrocarbon group of H, C6 ~ C30, the condensed-nuclei aromatics group of the substituted or non-substituted of C6 ~ C30, the substituted or non-substituted of C6 ~ C30 fused heterocycle group, five yuan, hexa-atomic heterocycle or substituted heterocycle, triarylamine group, aryl oxide group base group, C1 ~ C12 substituted or non-substituted aliphatic alkyl group in one;
Ar
5be selected from the one in the substituted or non-substituted aliphatic alkyl group of the substituted or non-substituted aromatic hydrocarbon group of C6 ~ C30, the substituted or non-substituted condensed-nuclei aromatics of C6 ~ C30 or fused heterocycle aromatic hydrocarbon group, C1 ~ C12.
Ar
6-Ar
7independently be selected from the substituted or non-substituted aromatic hydrocarbon group of H, C6 ~ C30, the condensed-nuclei aromatics group of the substituted or non-substituted of C6 ~ C30, the substituted or non-substituted of C1 ~ C12 aliphatic alkyl group in one.
Further, described Ar
1, Ar
2, Ar
6, Ar
7be H simultaneously.
Further, described Ar
5be selected from the alkyl of C1 ~ C6, phenyl, aminomethyl phenyl, ethylphenyl, p-methoxy-phenyl, xenyl, naphthyl, anthryl, phenanthryl, perylene base, pyrenyl.
Further, described Ar
3or Ar
4be selected from phenyl, phenyl, naphthyl, C
1-6alkyl, one or both groups replace in carbazyl phenyl, naphthyl, phenyl, naphthyl, C
1-6alkyl, one or both groups replace in carbazyl naphthyl, anthryl, phenyl, naphthyl, C
1-6alkyl, one or both groups replace in carbazyl anthryl, phenanthryl, phenyl, naphthyl, C
1-6alkyl, one or both groups replace in carbazyl phenanthryl , perylene base, phenyl, naphthyl, C
1-6alkyl, one or both groups replace perylene base, pyrenyl, phenyl, naphthyl, C in carbazyl
1-6alkyl, one or both groups replace in carbazyl pyrenyl, fluoranthene base, phenyl, naphthyl, C
1-6alkyl, one or both groups replace in carbazyl fluoranthene base,
base, phenyl, naphthyl, C
1-6alkyl, one or both groups replace in carbazyl
base, triphenylenyl, phenyl, naphthyl, C
1-6alkyl, one or both groups replace in carbazyl triphenylenyl, carbazyl, phenyl, naphthyl, C
1-6alkyl, one or both groups replace in carbazyl carbazyl, triarylamine, phenyl, naphthyl, C
1-6alkyl, one or both groups replace in carbazyl triarylamine, diaryl-amine base, N-phenyl carbazole base, N-phenylnaphthalene amido, dibenzothiophene base, dibenzofuran group, benzothienyl.
In order to be illustrated more clearly in content of the present invention, lower mask body describes 10, the 15-phenylbenzene benzofluorenes carbazole derivative preferred structure that the present invention relates to:
The invention provides and a kind ofly can be applicable to 10,15-phenylbenzene benzofluorenes in organic electroluminescence device and carbazole derivative.
Of the present invention 10,15-phenylbenzene benzofluorene carbazole derivative has higher hole migration ability, 10,15-described phenylbenzene benzofluorenes carbazole derivative can be used as hole-injecting material, hole mobile material or material of main part in organic electroluminescence device.
Present invention also offers a kind of organic electroluminescence device, comprise substrate, and form anode layer, organic luminescence function layer and cathode layer on the substrate successively;
Described organic luminescence function layer comprises hole transmission layer, organic luminous layer and electron transfer layer;
The hole mobile material of described hole transmission layer is 10,15-described phenylbenzene benzofluorenes and carbazole derivative.
Present invention also offers a kind of organic electroluminescence device, comprise substrate, and form anode layer, organic luminescence function layer and cathode layer on the substrate successively;
Described organic luminescence function layer comprises hole transmission layer, organic luminous layer and electron transfer layer;
The material of main part of described organic luminous layer contains 10,15-described phenylbenzene benzofluorenes and carbazole derivative.
Embodiment
Basic raw material used in the present invention, bromo-7,12-phenylbenzene benzo [k] fluoranthene of 3-, 2,4-bis-bromo nitrobenzene, 2,5-bis-bromo nitrobenzene, and bromo carbazole derivative, bromo diphenylene-oxide, bromo dibenzothiophene, bromo Chrysene, bromo triphenylene, bromo pyrene etc., can buy in each large industrial chemicals market at home.This laboratory oneself synthesis of 5-bromine benzophenanthrene system.
Embodiment
The synthesis of main intermediate 7,12-phenylbenzene benzo [k] fluoranthene-3-boric acid
Be dissolved in the THF of 120ml drying by bromo-for the 3-of 9.65g 7,12-phenylbenzene benzo [k] fluoranthene (molecular weight 482,0.02mol) ,-80 DEG C drip normal-butyl reason 9ml(2.5M, 0.0225mol), stir 15min, then drip triisopropyl boric acid ester 20ml.Hydrolysis, regulate pH to neutral, separate out boric acid derivatives 8.9g, productive rate is close to 100%.
Embodiment 1
The synthesis of compound 1
(1) the first step,
1000 milliliters of a bite bottles, join magnetic agitation, add 7,12-phenylbenzene benzo [k] fluoranthene-3-boric acid 18g(molecular weight 448,0.04mol), 2,4-bis-bromo nitrobenzene 11.4g(molecular weight 278,0.041mol), Pd (PPh3) 4 usage quantity 2.6g(molecular weight 1154,0.00253mol), sodium carbonate 200ml(2M), toluene 200ml, ethanol 200ml.After argon replaces, backflow, with TLC monitoring reaction, react completely after 3 hours, cooling, separated basic unit, evaporate to dryness, the ethyl acetate/petroleum ether with 1/10 carries out post separation, obtains 22.3g product, molecular weight 603, productive rate 92.6%.
(2) second step,
In a bite bottle, join magnetic agitation, add the final product 22.3g(molecular weight 603,0.037mol of the first step), triphenylphosphine 21.3g(molecular weight 262,0.0814mol), orthodichlorobenzene 300ml.Mixture is heated to 175 DEG C, stirs, by TCL board monitoring reaction process, reacts and complete for 15 hours.Cooling, solvent evaporation in vacuo, washing, dry, with pillar layer separation, ethyl acetate and petroleum ether mixtures drip washing, obtain target molecule 18.5g, molecular weight 571, productive rate 87.8%
(3) the 3rd steps,
500 milliliters of a bite bottles, join magnetic agitation, add second step final product 18.5g(molecular weight 571,0.032mol), iodobenzene 12.7g(molecular weight 204,0.05mol), cuprous iodide 1.0g(molecular weight 190,0.00526mol), salt of wormwood 13.8g(138,0.1mol), DMPU solvent 180ml.Mixture is heated to 175 DEG C, stirs, by TCL board monitoring reaction process, reacts and complete for 13 hours.Cooling, in impouring water, leaches, and dry, with pillar layer separation, ethyl acetate and petroleum ether mixtures drip washing, obtain target molecule 17.95g, molecular weight 647, productive rate 85.4%
(4) the 4th steps,
1000 milliliters of a bite bottles, join magnetic agitation, add above-mentioned 3rd step final product 17.95g(molecular weight 647,0.0277mol), triphenylamine-4-boric acid 9.0g(molecular weight 289,0.031mol), Pd (PPh
3)
4usage quantity 3.0g(molecular weight 1154,0.0026mol), sodium carbonate 220ml(2M), toluene 220ml, ethanol 220ml.After argon replaces, backflow, with TLC monitoring reaction, reacts completely after 4 hours, cooling, and product solid major part is separated out, and filters, and purifies (also can purify with post separation method if desired), obtain 17.1g product, productive rate 75.6% with recrystallization method.
Product MS(m/e): 812, ultimate analysis (C
62h
40n
2): theoretical value C:91.60%, H:4.96%, N:3.45%; Measured value C:91.63%, H:4.93%, N:3.44%.
Embodiment 2
The synthesis of compound 2
Synthesis step is same as the four-step reaction in embodiment 1, just in the 4th step, triphenylamine-4-boric acid is changed into 4-(N-phenyl-N-(1-naphthyl) amino)) phenylo boric acid, obtain compound 2.
Product MS(m/e): 862, ultimate analysis (C
66h
42n
2): theoretical value C:91.85%, H:4.91%, N:3.25%; Measured value C:91.80%, H:4.92%, N:3.28%.
Embodiment 3
The synthesis of compound 3
Synthesis step is same as the four-step reaction in embodiment 1, just in the 4th step, triphenylamine-4-boric acid is changed into 4-(carbazole-9-base)) phenylo boric acid, obtain compound 3.
Product MS(m/e): 810, ultimate analysis (C
62h
38n
2): theoretical value C:91.82%, H:4.72%, N:3.45%; Measured value C:91.81%, H:4.76%, N:3.43%.
Embodiment 4
The synthesis of compound 4
Synthesis step is same as the four-step reaction in embodiment 1, just in the 4th step, triphenylamine-4-boric acid is changed into N-phenyl carbazole-3-boric acid, obtains compound 4.
Product MS(m/e): 810, ultimate analysis (C
62h
38n
2): theoretical value C:91.82%, H:4.72%, N:3.45%; Measured value C:91.84%, H:4.76%, N:3.40%.
Embodiment 5
The synthesis of compound 5
Synthesis step is same as the four-step reaction in embodiment 1, just in the 4th step, triphenylamine-4-boric acid is changed into dibenzothiophene-2-boric acid, obtains compound 5.
Product MS(m/e): 751, ultimate analysis (C
56h
33nS): theoretical value C:89.45%, H:4.42%, N:1.86%, S:4.26%; Measured value C:89.42%, H:4.44%, N:1.85%, S:4.29%.
Embodiment 6
The synthesis of compound 6
Synthesis step is same as the four-step reaction in embodiment 1, just in the 4th step, triphenylamine-4-boric acid is changed into dibenzothiophene-4-boric acid, obtains compound 6.
Product MS(m/e): 751, ultimate analysis (C
56h
33nS): theoretical value C:89.45%, H:4.42%, N:1.86%, S:4.26%; Measured value C:89.43%, H:4.46%, N:1.83%, S:4.28%.
Embodiment 7
The synthesis of compound 7
Synthesis step is same as the four-step reaction in embodiment 1, just in the 4th step, triphenylamine-4-boric acid is changed into diphenylene-oxide-2-boric acid, obtains compound 7.
Product MS(m/e): 735, ultimate analysis (C
56h
33nO): theoretical value C:91.40%, H:4.52%, N:1.90%, O:2.17%; Measured value C:91.44%, H:4.51%, N:1.93%, O:2.12%.
Embodiment 8
The synthesis of compound 8
Synthesis step is same as the four-step reaction in embodiment 1, just in the 4th step, triphenylamine-4-boric acid is changed into diphenylene-oxide-4-boric acid, obtains compound 8.
Product MS(m/e): 735, ultimate analysis (C
56h
33nO): theoretical value C:91.40%, H:4.52%, N:1.90%, O:2.17%; Measured value C:91.42%, H:4.50%, N:1.92%, O:2.16%.
Embodiment 9
The synthesis of compound 9
Synthesis step is totally four steps, and first three walks the front three-step reaction be same as in embodiment 1, obtains intermediate bromo-derivative.
4th step is undertaken by following formula reaction and step:
1000 milliliters of a bite bottles; join electric stirring, nitrogen protection, add the 3rd step intermediate bromo-derivative 15.8g(molecular weight 647; 0.0244mol); N-phenyl-2-naphthylamine 11g(molecular weight 219,0.05mol), cuprous iodide 3.0g(molecular weight 190; 0.0158mol); salt of wormwood 40g(138,0.1mol), DMPU solvent 400ml.Mixture is heated to 175 DEG C, high degree of agitation, by TCL board monitoring reaction process, reacts and completes for 15 hours.Cooling, in impouring water, leaches, dry, and with pillar layer separation, ethyl acetate and petroleum ether mixtures drip washing, obtain compound 9 15.1g altogether, productive rate 78.5%.
Product MS(m/e): 786, ultimate analysis (C
60h
38n
2): theoretical value C:91.57%, H:4.87%, N:3.56%; Measured value C:91.55%, H:4.86%, N:3.59%.
Embodiment 10
The synthesis of compound 10
Synthesis step is same as the four-step reaction in embodiment 1, just in the 4th step, triphenylamine-4-boric acid is changed into fluoranthene-3-boric acid, obtains compound 10.
Product MS(m/e): 769, ultimate analysis (C
60h
35n): theoretical value C:93.60%, H:4.58%, N:1.82%; Measured value C:93.63%, H:4.60%, N:1.77%.
Embodiment 11
The synthesis of compound 11
Synthesis step is same as the four-step reaction in embodiment 1, just in the 4th step, triphenylamine-4-boric acid is changed into fluoranthene-3-boric acid, obtains compound 11.
Product MS(m/e): 769, ultimate analysis (C
60h
35n): theoretical value C:93.60%, H:4.58%, N:1.82%; Measured value C:93.62%, H:4.59%, N:1.79%.
Embodiment 12
The synthesis of compound 12
Synthesis step is same as the four-step reaction in embodiment 1, just in the 4th step, triphenylamine-4-boric acid is changed into triphenylene-2-boric acid, obtains compound 12.
Product MS(m/e): 795, ultimate analysis (C
62h
37n): theoretical value C:93.55%, H:4.69%, N:1.76%; Measured value C:93.57%, H:4.66%, N:1.77%.
Embodiment 13
The synthesis of compound 13
Synthesis step is same as the four-step reaction in embodiment 1, just in the first step, 2,4-bis-bromo nitrobenzene is changed into 2,5-bis-bromo nitrobenzene, obtains compound 13.
Product MS(m/e): 812, ultimate analysis (C
62h
40n
2): theoretical value C:91.60%, H:4.96%, N:3.45%; Measured value C:91.62%, H:4.97%, N:3.41%.
Embodiment 14
The synthesis of compound 14
Synthesis step is same as the four-step reaction in embodiment 1, just in the first step, 2,4-bis-bromo nitrobenzene is changed into 2,5-bis-bromo nitrobenzene; In the 4th step, triphenylamine-4-boric acid is changed into 4-(N-phenyl-N-(1-naphthyl) amino) phenylo boric acid, obtain compound 14.
Product MS(m/e): 862, ultimate analysis (C
66h
42n
2): theoretical value C:91.85%, H:4.91%, N:3.25%; Measured value C:91.83%, H:4.90%, N:3.27%.
Embodiment 15
The synthesis of compound 15
Synthesis step is same as the four-step reaction in embodiment 1, just in the first step, 2,4-bis-bromo nitrobenzene is changed into 2,5-bis-bromo nitrobenzene; In the 4th step, triphenylamine-4-boric acid is changed into N-phenyl carbazole-3-boric acid, obtain compound 15.
Product MS(m/e): 810, ultimate analysis (C
62h
38n
2): theoretical value C:91.82%, H:4.72%, N:3.45%; Measured value C:91.80%, H:4.74%, N:3.46%.
Embodiment 16
The synthesis of compound 16
Synthesis step is same as the four-step reaction in embodiment 1, just in the first step, 2,4-bis-bromo nitrobenzene is changed into 2,5-bis-bromo nitrobenzene; In the 4th step, triphenylamine-4-boric acid is changed into dibenzothiophene-2-boric acid, obtains compound 16.
Product MS(m/e): 751, ultimate analysis (C
56h
33nS): theoretical value C:89.45%, H:4.42%, N:1.86%, S:4.26%; Measured value C:89.46%, H:4.44%, N:1.83%, S:4.27%.
Embodiment 17
The synthesis of compound 17
Synthesis step is same as the four-step reaction in embodiment 1, just in the first step, 2,4-bis-bromo nitrobenzene is changed into 2,5-bis-bromo nitrobenzene; In the 4th step, triphenylamine-4-boric acid is changed into dibenzothiophene-4-boric acid, obtains compound 17.
Product MS(m/e): 751, ultimate analysis (C
56h
33nS): theoretical value C:89.45%, H:4.42%, N:1.86%, S:4.26%; Measured value C:89.42%, H:4.43%, N:1.87%, S:4.28%.
Embodiment 18
The synthesis of compound 18
Synthesis step is same as the four-step reaction in embodiment 1, just in the first step, 2,4-bis-bromo nitrobenzene is changed into 2,5-bis-bromo nitrobenzene; In the 4th step, triphenylamine-4-boric acid is changed into diphenylene-oxide-4-boric acid, obtains compound 18.
Product MS(m/e): 735, ultimate analysis (C
56h
33nO): theoretical value C:91.40%, H:4.52%, N:1.90%, O:2.17%; Measured value C:91.43%, H:4.51%, N:1.92%, O:2.14%.
Embodiment 19
The synthesis of compound 19
Synthesis step is same as the four-step reaction in embodiment 1, just in the first step, 2,4-bis-bromo nitrobenzene is changed into 2,5-bis-bromo nitrobenzene; In the 4th step, triphenylamine-4-boric acid is changed into diphenylene-oxide-2-boric acid, obtains compound 19.
Product MS(m/e): 735, ultimate analysis (C
56h
33nO): theoretical value C:91.40%, H:4.52%, N:1.90%, O:2.17%; Measured value C:91.41%, H:4.54%, N:1.92%, O:2.13%.
Here is the Application Example of each compound of the present invention:
The structure of organic electroluminescence device used in the present embodiment is: substrate/anode/hole injection layer (HIL)/hole transmission layer (HTL)/organic luminous layer (EL)/electron transfer layer (ETL)/negative electrode.
Substrate can be glass substrate, plastics or stainless steel, and the present embodiment uses glass substrate.
Anode layer can be the metal of work function comparatively large (being greater than 4.0eV), alloy, electroconductive oxide or its mixture, as ITO (tin indium oxide), and IZO(indium zinc oxide) or ZnO.The present embodiment uses ITO, and thickness is 180nm.
Hole injection layer, the hole-injecting material used in the present embodiment is the compound in the present invention.In order to realize better device performance, these materials also can adulterate with some oxygenants, and provide hole to inject effect, as doped F 4-TCNQ, the two part by weight is 100:4, and total thickness is 150nm.In comparative example, hole injection layer 3 can be starlike polyamines, polyaniline etc., as m-MTDATA, 2-TNATA, 1-TNATA.This time comparative example uses 1-TNATA doping 2,3,5,6-tetrafluoro Kui bismethane (F4-TCNQ), and the two part by weight is 100:4, and total thickness is 150nm.
Hole transmission layer, can be aromatic amine chemicals, '-two-(1-naphthyl)-N, N '-phenylbenzene-1,1 '-xenyl-4,4 '-diamines (NPB) as N, N.Use NPB in the present embodiment, thickness is 20nm.
Luminescent layer, the mode of body-dopant luminescent dye can be adopted, luminescent dye can for launching the dyestuff of any one colors such as red, green, blue, yellow, orange or white, AND doping DSA-ph is used in the present embodiment, ADN(title: 9,10-bis-(2-naphthyl) anthracene) be material of main part, DSA-ph(title, 4-bis--(4-N, N-phenylbenzene) Amino-styrene base benzene) be sky blue light luminescent dye, doping ratio is 5%(weight ratio), namely the ratio of ADN and DSA-ph is 100:5, and light emitting layer thickness is 30nm.
Electron injecting layer and negative electrode can be the metal of work function lower (being less than 4eV), alloy, electroconductive oxide or its mixture, if Mg and Ag doping is as cathode layer, or LiF/Al, or Li
2o/Al, or LiQ/Al.Electron injecting layer in the present embodiment and cathode layer are LiF and Al, and thickness is respectively 0.5nm and 150nm, and Al layer plating is on described LiF layer.
Embodiment 20
What the present embodiment was enumerated is the example of the compound in the present invention as hole injection layer.The device architecture of the present embodiment is: ITO/HIL:F4TCNQ (150nm, 4wt%)/NPB (20nm)/AND:DSA-ph(30nm, 5wt%)/Alq
3(20nm)/LiF (0.5nm)/Al (150nm).
The method preparing the organic electroluminescence device in the present embodiment is as follows:
1. by the ultrasonic detergent boiled and deionized water ultrasonic method, glass substrate is cleaned, and dry under being placed on infrared lamp.
2. on glass, sputter one deck ITO as anode, thickness is 180nm;
3. the above-mentioned glass substrate with anode ITO is placed in vacuum chamber, is evacuated to 1 × 10
-5pa-1 × 10
-3pa, on above-mentioned anode tunic, evaporation 1-TDATA and F4-TCNQ doped layer are as hole injection layer, and speed is 0.1nm/s, and evaporation thickness is 150nm, as a comparison case; Compound 1,2,9,13,14 difference doped F 4-TCNQ in evaporation the present invention is as the hole injection layer in embodiment.
4. continue evaporation one deck NPB film as hole transmission layer, speed is 0.1nm/s, and evaporation thickness is 20nm;
5. the method adopting double source to steam altogether again carries out the evaporation doping of luminescent layer, and the material of main part of luminescent layer is ADN, and luminescent dye is DSA-ph, and doping content is 5wt ﹪, and evaporation thickness is 30nm;
6., on luminescent layer, evaporation one deck electron transfer layer Alq is continued
3, its evaporation rate is 0.1nm/s, and evaporation total film thickness is 20nm;
7. last, on above-mentioned luminescent layer, evaporation LiF layer and Al layer are as the electron injecting layer of device and cathode layer successively, and wherein the evaporation rate of LiF layer is 0.01 ~ 0.02nm/s, and thickness is the evaporation rate of 0.5nm, Al layer is 1nm/s, and thickness is 150nm.
Organic electroluminescence device performance in table 1 embodiment 20
As can be seen from the above embodiments, the compound 1,2,9,13,14 in employing the present invention, as the hole injection layer of device, can realize the efficiency higher than comparative example and lower voltage.It should be noted that, when the compound in the present invention is as hole injection layer, also can undope F4TCNQ, only can reach better effect after doped F 4TCNQ.
Embodiment 21
What the present embodiment was enumerated is the example of the compound in the present invention as hole transmission layer.The device architecture of the present embodiment is: ITO/1-TNATA:F4TCNQ (150nm, compound (20nm)/AND:DSA-ph(30nm, 5wt% in 4wt%)/the present invention)/Alq3 (20nm)/LiF (0.5nm)/Al (150nm).Its preparation method is with reference to embodiment 20, and difference is that the hole injection layer in device architecture adopts 1-TNATA doped F 4-TCNQ, and hole transmission layer adopts the compound 3,4,5,6,7,8,15,16,17,18,19 in the present invention, and all the other are all identical.
Organic electroluminescence device performance in table 2 embodiment 21
As can be seen from the above embodiments, the compound 3,4,5,6,7,8,15,16,17,18,19 in employing the present invention, as the hole transmission layer of device, can realize the efficiency higher than comparative example and lower voltage.
Embodiment 22
What the present embodiment was enumerated is the example of the compound in the present invention as main body.The device architecture of the present embodiment is be that the hole transmission layer in device architecture adopts NPB with the difference of preparation method and embodiment 21, and the compound 10,11,12 in the present invention of luminescent layer material of main part, all the other are all identical.
Organic electroluminescence device performance in table 3 embodiment 22
As can be seen from the above embodiments, the compound 10,11,12 in employing the present invention, as the material of main part of device, can realize the efficiency higher than comparative example and lower voltage.
Above result shows, new organic materials of the present invention is used for organic electroluminescence device, can effectively reduce landing voltage, and improving current efficiency, is hole-injecting material of good performance and light emitting host material.
Although describe the present invention in conjunction with the embodiments, the present invention is not limited to above-described embodiment, should be appreciated that, under the guiding of the present invention's design, those skilled in the art can carry out various amendment and improvement, and claims summarise scope of the present invention.