CN1844300A - Method for making same dye molecule emit light with different colors by substrate induction - Google Patents
Method for making same dye molecule emit light with different colors by substrate induction Download PDFInfo
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- CN1844300A CN1844300A CN 200610016744 CN200610016744A CN1844300A CN 1844300 A CN1844300 A CN 1844300A CN 200610016744 CN200610016744 CN 200610016744 CN 200610016744 A CN200610016744 A CN 200610016744A CN 1844300 A CN1844300 A CN 1844300A
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Abstract
The invention belongs to fluorochrome molecular luminescence domain, concretely relates to a method for getting identical dye molecule of the identical base emit fluorescent lights with different colors by constructing different structural surfaces of backing materials and accordingly introducing coherent conditions of organic light-emitting molecule and oligomer light-emitting molecule. The said method includes the following steps: selecting inorganic background or polymeric background and performing treatment for substrate surface; constructing surfaces with microstructure by layered self-packaging, vapour deposition, LB film technology, nano autogram or stamping-cure selective elution technique for the treated background; depositing film of identical dye molecule on inorganic background or polymer background of micro-structural surface with vacuum degree of 1*10-4-5*10-4Pa and electric current of 5-10A; agitated by ultraviolet light, fluorescent lights with different colors can be observed on molecular surface of identical dye by fluorescence spectrometer or fluorescence microscope.
Description
Technical field
The invention belongs to the luminous field of luminescent dye molecule, be specifically related to by constructing the different micro-structure surfaces of substrate material, thereby induce the state of aggregation of luminescent organic molecule, oligopolymer light emitting molecule, and then make same suprabasil same dye molecule send out the method for different colours fluorescence.
Background technology
Report needs to introduce two or more different dyes molecule in order to realize fluorescigenic pattern structure in the document.Construct the pattern of sending out fluorescence different by selective adsorption as people such as T.Hammond, the method of at first using micro-contact printing and self-assembly is earlier with the gold surface patterning, make substrate surface have different functional groups, adopt the method for layer assembly (Layer-by-Layer) different dye molecules optionally to be adsorbed onto the surface of layer assembly then, thereby formed the regular pattern that different fluorescence are arranged (the Xue-ping Jiang that constitutes by dye molecule, Sarah L.Clark, and Paula T.Hammond, Adv.Mater.2001,13,1669).Tang in 1994 etc. have delivered the patent (U.S.Pat.No.5,871,709) by construct different fluorescence color patterns with mask plate (the shadow mask evaporation) method of hot evaporation first.Its method is to make light emitting molecule optionally deposit on the device substrate by mask plate by vacuum thermal evaporation, deposited after first kind of light emitting molecule, mobile mask plate, deposit second, third kind molecule, thereby obtain the pattern that constitutes by different light emitting molecules, obtained the pattern structure of different colours fluorescence.This method is updated (U.S.Pat.No.5,550,066; 5,688,551; 5,742,129; 5,871,709; 6,066,357; 6,184,049; 6,191,433; 6,337,102; 6,911,671).Construct the luminescence polymer method of patterning, generally include " spray ink Printing " (T.R.Hebner et al, Appl.Phys.Lett.1998,72,519), dry etching (C.C.Wu et al, Appl.Phys.Lett.1996,69,3117) or the like.The method of " spray ink Printing " is exactly that different luminescence polymers is printed to as " ink " in the substrate of device, forms the required different colours light pattern that sends.Dry etching may further comprise the steps: at first a kind of luminescence polymer is spun in the substrate that has electrode, the method for using the mask plate evaporation then is at corresponding position electrode evaporation, and the polymkeric substance of other parts is etched away.Before second kind of polymkeric substance of spin coating, adopt identical step to construct the structure of second kind of luminescence polymer and the structure of the third luminescence polymer then first part's structural defence.
Dye molecule is that different glow colors is arranged in different state of aggregation as a rule, monomeric glow color, and (if any), and the glow color of body is different to the glow color of aggregate for dimer, tripolymer or the like.But the different glow color of these aggregates particularly can't be regulated and control on the solid surface in the element manufacturing experimentation.Normally be wasted or be not utilized.Such as, quinacridone and derivative thereof (QA) (structure is shown in A) are in the construction process of device, just obtain the red fluorescence of aggregate film by organic vapor deposition, the green fluorescence that monomer material is strong is not utilized, pyrazoles anthracene (ANP) is at (structural formula is shown in B) that normally exist with trimerical form in the solid film for another example, three adjacent pyrazoles anthracene molecules with hydrogen bonded, send green fluorescence by two nitrogen on the pyrazoles; And the higher blue light of the brightness that monomeric pyrazoles anthracene sends also is unserviceable under state of aggregation.
A：
1：R
1＝R
2＝R
3＝H，R
4＝～CH
2CH
2CH
2CH
3 2：R
1＝R
2＝R
3＝H，R
4＝～C
6H
13
3：R
1＝R
2＝R
3＝H，R
4＝n～C
8H
17 4：R
1＝R
2＝R
3＝H，R
4＝n～C
12H
25
5：R
1＝R
2＝R
3＝H，R
4＝n～C
12H
25 6：R
1＝R
2＝R
3＝H，R
4＝n～C
12H
25
7：R
1＝R
2＝R
3＝H，R
4＝n～C
16H
33 8：R
1＝R
2＝R
3＝H，R
4＝n～C
12H
25
9：R
1＝R
3＝Me，R
2＝H，R
4＝n～C
4H
9 10：R
1＝R
3＝Me，R
2＝H，R
4＝n～C
4H
9
11：R
1＝R
3＝Me，R
2＝R
4＝H 12：R
1＝R
3＝H，R
2＝R
4＝t～Bu
13：R
1＝R
4＝H，R
2＝R
3＝OC
12H
25 14：R
1＝H，R
2＝R
3＝OC
12H
25，R
4＝CH
3
15：R
1＝R
3＝R
4＝H，R
2＝OC
12H
25 16：R
1＝R
3＝H，R
2＝OC
12H
25，R
4＝CH
3
17：R
1＝R
4＝H，R
2＝R
3＝OC
6H
13 18：R
1＝R
3＝R
4＝H，R
2＝OCH
2CH(C
11H
23)
2
19：R
1＝R
3＝H，R
2＝OCH
2CH(C
11H
23)
2，R
4＝CH
3
B：
If can be by realizing regulation and control someway to the accumulation shape of luminescent dye molecule, make luminescent dye molecule have different state of aggregation and send out the fluorescence of different colours, thereby realize realizing multiple colour light emitting with a kind of molecule (rather than with different luminescent dye molecules) in the different zone of same substrate.So not only develop and a kind of completely new concept, by selecting for use suitable molecule can finally realize realizing being used to showing the manufacturing of the red, green, blue device of three-primary colours with a kind of molecule, and can expect to have the advantage of simplifying device configuration, saving making step, reduce cost that reaches.This method can also be regulated and control by the pattern structure of the molecular layer on the electrode, because molecular layer can not stop the transport process of electric charge, can be applied in the future go in the development of electroluminescent device or indicating meter.
Summary of the invention
The purpose of this invention is to provide a kind of method of sending multiple color fluorescence with a kind of light emitting molecule of inducing at same substrate surface.By substrate is handled, to induce with a kind of light emitting molecule on substrate, to exist, and then realize sending multiple color fluorescence with different state of aggregation, this method has widely in preparation transmitter, luminescent device or display device to be used.
We find after deliberation, quinacridone and derivative thereof, pyrazoles anthracene equiconjugate organic molecule have good luminescent characteristic, and this type of light emitting molecule presents different state of aggregation on the smooth substrates of differing materials, and causes sending out the fluorescence (as Fig. 1) of different colours thus.By telomerized polymer substrate material difference, can regulate the fluorescence peak position, our controlling polymers substrate material has been realized quinacridone and derivatives fluorescent peak position thereof (50nm) controlled in 530nm～580nm scope in the experiment; And the pyrazoles anthracene is equally by telomerized polymer substrate material difference, can realize fluorescence peak position (79nm) controlled in 418nm～497nm scope.Therefore, by substrate surface is constructed out regular pattern with different materials, can realize that a kind of light emitting molecule sends the fluorescence of different colours on same surface, thereby obtain the phosphor pattern of different colours.
Used quinacridone and derivative thereof, pyrazoles anthracene equiconjugate organic molecule are all by method synthetic (Kaiqi Ye, Jia Wang, the Hui Sun of bibliographical information among the present invention, Yu Liu, Zhongcheng Mu, Fei Li, ShimeiJiang, Jingying Zhang, Hongxing Zhang, Yue Wang, and Chi～Ming Che, J.Phys.Chem.B2005,109,8008～8116; Trofimenko, S.; Calabrese J.C.and Thopson, J.S.Inorg.Chem.1987,26,1507-1514; Trofimenko, S.; Calabrese J.C.; Kochi, J.K.; Wolowiec, S.; Hulsbergen, F.B.and Reedijk, J.Inorg.Chem.1987,26,1507-1514).Before the evaporation sample all through the vacuum-sublimation purification (Vacuum Sublimation and Crystallography of Quinacridones.F.H.Chung and R.W.Scott.J.Appl.Cryst. (1971) .4,506-511).
The same dye molecule of the described substrate induction of this patent is sent out the method for different colours fluorescence, comprises the steps:
A, choose inorganic substrates or polymeric substrates, and substrate surface is handled;
B, the substrate that will handle select elution technique to construct out the surface with microstructure by layered self-packaging, vapour deposition, LB film, nano impression or impression curing;
C, have on the inorganic or polymeric substrates of micro-structure surface, evaporation thickness is same a kind of dye molecule film of 1～500nm, and vacuum tightness is 1 * 10
-4～5 * 10
-4Pa, size of current are 5～10A;
D, use ultraviolet excitation, promptly can observe the fluorescence that different colours is sent out on same kind of dye molecule surface by spectrophotofluorometer or fluorescent microscope.
Inorganic or polymeric substrates described in the aforesaid method comprises polymkeric substance such as the silicon oxide of quartz, glass, ito glass, metal, silicon chip (silicon single crystal), sheet mica, modified monolayer or multilayered film material or metal, polydimethylsiloxane (PDMS), urethane (PU), polyvinyl chloride (PVC), polyethylene terephthalate (PET), polystyrene (PS), polyethylene (PE), polypropylene (PP), diazonium photoresist material, polymkeric substance is made into certain density solution or chooses suitable performed polymer, makes substrate through spin coating, heating or ultraviolet lighting polymerization again.
Inorganic substrates is at first used oxygen plasma system (Plasma System100, PVA-TEPLA, Germany) surface is handled: oxygen gas flow rate 80～120ml/min, power 100～300W, in 1～5 minute treatment time, used acetone, chloroform, dehydrated alcohol, high purity water ultrasonic cleaning then successively 2～15 minutes; Polymeric substrates is with dipping in after the absorbent cotton wiping of dehydrated alcohol the high purity water ultrasonic cleaning 2～15 minutes.
The layered self-packaging method: above-mentioned inorganic substrates such as the silicon single crystal of the clean dried that will handle immerses in the target solution of silane of finite concentration (0.1～10 μ g/ml), silicol (silanol etc.), alkyl silane (n-octyl dichlorosilane, octadecyl trichlorosilane etc.), aminosilane (aminopropyl triethoxysilane, hmds etc.) or the like, soak and take out after 20 seconds～24 hours with organic solvent (toluene, chloroform, ethanol or tetrahydrofuran (THF) etc.) ultrasonic cleaning three times, each 2～15 minutes, use the deionized water ultrasonic cleaning again two to three times, each 2～15 minutes, dry up with nitrogen then.This method can be modified into substrate the surface that has different functional groups, as make the surface have carboxyl, hydroxyl, alkyl, amino, halogeno-group, alkynyl, thiazolinyl, alkyl, fluorine substituted alkyl or the like, make it can the induced luminescence molecule produce different state of aggregations or the gathering nucleation rate granular size of dye molecule is exerted an influence, thus the fluorescent characteristic and the phosphor pattern of different modulating fluorescence molecule that can be by substrate modified monolayer film.
Vapour deposition process: drip 2～20 microlitre target silylating reagents in the vial in vacuum drier, silicol (silanol etc.), alkyl silane (n-octyl dichlorosilane, octadecyl trichlorosilane etc.), aminosilane (aminopropyl triethoxysilane, hmds etc.), halogeno-group silane (tert-butyl diphenyl chlorosilane, trichlorosilane etc.), thiazolinyl silane (vinyltriethoxysilane etc.), fluorine substituted alkyl silane (perfluoro normal hexane base trichlorosilane etc.) or the like, the above-mentioned inorganic substrates materials such as silicon single crystal that oxygen plasma treatment is crossed are fixed on the specimen holder in the vacuum drier, make the vacuum tightness in the vacuum drier remain on 0.01～0.015Mpa then, behind 15min～4 hour, take out sample, with deionized water ultrasonic cleaning 2～3 times, each 2～15 minutes, dry up with nitrogen then.
The LB membrane technique: with microsyringe with an amount of V
0(2～50 microlitre) finite concentration C
1(mixed solution (as the mixed solution of palmitinic acid, the tar acid that holds with both hands with both hands) of 0.1～10mg/ml) sample (amphiphilic straight-chain molecules such as two palmitinic acid phosphatidylcholines, palmitinic acid, the tar acid that holds with both hands with both hands) solution or certain proportion a (two kinds of above-mentioned amphiphilic straight-chain molecules with mol ratio 1～10: 1 mixes) spreads over high purity water and (handles through French MILLI～Q ultrapure water instrument, resistivity is 18.2M Ω cm) on the parfacies, treat solvent for some time t that volatilizees naturally
1(10min～24h), on LB film balance (the Britain 312D of Nima company film balance), use baffle plate with certain speed S
1(5～30cm
2/ min) compress, obtain the π～A curve of this sample, with the surface pressure of film in the Wihelmy film balance measurement compression process, (1～30mN/m), certain hour t keep-ups pressure to select suitable shift pressure P according to π～A curve then
2(10min～24h) on the sheet mica of newly peeling off of water flushing or the above-mentioned inorganic substrates such as monocrystalline silicon piece crossed of oxygen plasma system handles, lifts individual layer Langmuir film with vertical crystal pulling method, and putting forward film speed is S
2(1～50mm/min), whole process system temperature is controlled at room temperature (23 ℃ ± 3 ℃).
As the further improvement of LB technology, can also by the film surface evaporation metal that lifts (gold and silver, aluminium etc., evaporation thickness 0.5～10nm), thereby the surface differences of film is further enlarged.
The step that the nano impression legal system is equipped with polymkeric substance and the alternate micro-structure surface of substrate (as shown in Figure 2, wherein substrate 21, polymkeric substance barrier 22, rigid template 23): A. makes the rigid template 23 with target microstructure with the method for photoetching or electron beam lithography, and its surface modified one deck silylating reagent (such as (Heptadecafluoro-1 with vapour deposition process, 1.2,2-tetrahydradecyl) triethoxysilane, C
16H
19F
17O
3Si, ABCR GmbH﹠amp; Co.KG), be impressed into this rigid template on the treated above-mentioned inorganic or polymeric substrates 21 of the silicon single crystal etc. on spin on polymers blocking layer 22 reducing surface energy; B. keep certain pressure (10～70Bar), temperature (than high 50～100 degree of the glass transition temperature Tg of polymer barrier layer), time (2～30 minutes), molten polymer is flowed in template 23 grooves; C. reduce temperature to polymer Tg, template is peeled off; D. remove residual layer in polymer barrier layer 22 grooves with plasma etching again, expose substrate 21, promptly in substrate, obtain polymkeric substance micron, submicrometre structural surface with the rigid template complementary structure.
Related polymer barrier layer is polymethylmethacrylate (PMMA) in the aforesaid method, polystyrene (PS), urethane (PU), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), dibutene, polyvinyl alcohol (PVA), polystyrene butadienecopolymer (SBS), poly-to vinylbenzene polyoxyethylene alkene copolymer (PPVPE), ABS resin, the MEH-PPV of polyphenylene ethylene class (PPV), BEH-PPV and BuEH-PPV, poly-branch subchains such as PPP to the benzene class have flexibility, can spin-coating film, glass transition temperature tg is at the OK range polymer materials of (not being higher than 200 ℃).
Polyvinyl chloride (PVC), urethane polymkeric substance such as (PU) can directly be prepared certain density solution spin coating and prepare polymeric film (strength of solution 1～50 μ g/ml, the spin coating condition is: 800～5000 commentaries on classics/S, rotation 10～180S), carry out nano impression with this film as the blocking layer then, the preparation micro-structure surface, etch away polymer residue layer in the groove to expose base material with the oxygen plasma etch system then, promptly formed the alternate micro-structure surface of subject polymer and base material.
Impression solidify to be selected elution technique: have in spin coating with traditional ultraviolet photolithographic technology (carving (exposure) method and device thereof referring to the CN90107038.6 large-area ultraviolet) and construct micro-structure surface on the above-mentioned inorganic or polymeric substrates of the silicon, glass, ito glass, quartz etc. on photoresist material blocking layer (photoetching is to carry out on the lithography machine of generally use, light source is the high voltage mercury lamp of power 800～1200W, and emission wavelength is at 370～410nm; Photoresist material spin coating condition is: 800～5000 commentaries on classics/S, and rotation 10～180S, the thickness of photoresist material is controlled at 200nm-5 μ m).As shown in Figure 3: the photoresist structure 32 (Fig. 3 steps A) of constructing micrometre or submicrometer structure on the treated above-mentioned inorganic or polymeric substrates 31 such as silicon single crystal that photoresist material is arranged in spin coating with above-mentioned ultraviolet photolithographic technology, be stamped in the polymkeric substance performed polymer 34 (Fig. 3 step B) that is spun on the smooth glass 33 as template again, 10～50bar keep-ups pressure, 2～15min, thereby polymkeric substance performed polymer coating 34 is clamp-oned in the groove of 32 of photoresist structures, form polymkeric substance performed polymer structure 35, then smooth glass 33 is peeled off, thereby in substrate 31, form the alternate structure of photoresist material 32 and polymkeric substance performed polymer 35, and smooth glass 33 can be abandoned (Fig. 3 step C) after peeling off as expendable material.After leaving standstill 2～6 hours, under the condition of heating, impel performed polymer structure 35 to be polymerized to polymer architecture 36 (Fig. 3 step D), dissolve away photoresist structure 32 according to what deliquescent difference was utilized solvent selectivity again, can in substrate 31, obtain polymkeric substance 36 body structure surfaces (Fig. 3 step e) of micron or submicron.
For the photoresist material blocking layer, it is characterized by uv-exposure region clustering body marriage chain disconnects, the become link of cross at random of easily dissolving (eurymeric photoresist material) or uv-exposure zone main chain is more tight, and increases from chain tenesmus thing, and polymeric solubleness reduces (negative photoresist).The photoresist material of using among the present invention is the BP212 type ultraviolet eurymeric photoresist material that Beijing Inst. of Chemical Reagent produces, viscosity (25 ℃): (37 ± 2) * 10
-3PaS.
Related polymkeric substance performed polymer coating is that virgin states such as polydimethylsiloxane (PDMS), vinylformic acid double cyclopentenyl ester, phthalic acid two rare third fat (DAP), Resins, epoxy are thick liquid in the aforesaid method, through heating or ultraviolet lighting handle can polymerizing curable material (polymkeric substance).
The organic molecular film evaporation carries out in automatic control multi-source organic vapor phase deposition system, and vacuum tightness is 1 * 10
-4～5 * 10
-4Pa, and by control current size (5～10A) control Heating temperatures, detect the thickness of evaporation rate and evaporation layer with the quiet sheet frequency change value of shaking, in this patent evaporation rate there is not strict demand, all feasible from 1nm/min～900nm/min, evaporation thickness is the dye molecule of 1～500nm on the above-mentioned inorganic or polymeric substrates of micro structured pattern thereby can have on the surface.
Discover, dye molecule luminous inorganic materials such as quartz that is different from polymeric substrates mainly is because there is the space in the interchain of polymkeric substance, fluorescent small molecule has been distributed between polymer chain in the space in the evaporate process, exist with monomeric form, i.e. the steric restriction effect of polymer chain structure has limited the state of aggregation of dye molecule.
Description of drawings
Fig. 1 (a): the fluorescence spectrum figure of the quinacridone correspondence of evaporation on quartzy and PDMS substrate;
Fig. 1 (b): the fluorescence spectrum figure of the pyrazoles anthracene correspondence of evaporation on quartzy and PDMS substrate;
Fig. 2: the nano impression legal system is equipped with the polymkeric substance micro-structure surface process synoptic diagram alternate with base material;
Fig. 3: impression solidifies the method synoptic diagram of selecting elution technique to construct two dimension micron, submicrometer structure;
Fig. 4: the fluorescence spectrum figure of the pyrazoles anthracene of evaporation on the monocrystalline substrate of alkyl (b) and fluorine (a) modification;
The fluorescent microscope photo (200 μ m * 200 μ m) of Fig. 5 (a): embodiment 3 preparation samples;
The fluorescence spectrum figure of Fig. 5 (b): embodiment 3 preparation samples (excitation wavelength 373nm, entrance slit is wide by 10, exit slit is wide by 5);
Fig. 6, (a): embodiment 4 preparation sample atoms force microscopes rap, (Tapping) pyrazoles anthracene state of aggregation image on sheet mica of pattern observation raps, (Tapping) the state of aggregation image gently please be skilful on sheet mica for the pyrazoles anthracene of pattern observation, (Tapping) the state of aggregation image gently please be skilful on sheet mica for the pyrazoles anthracene of pattern observation, (Tapping) pyrazoles anthracene state of aggregation image on sheet mica of pattern observation raps, (Tapping) pyrazoles anthracene state of aggregation image on sheet mica of pattern observation, (10 * 10 μ m);
Fig. 6 (b): embodiment 4 preparation sample atoms force microscopes rap the state of aggregation image (3 * 3 μ m) of pyrazoles anthracene on the sheet mica that the tar acid unitary film that holds with both hands with both hands is modified of (Tapping) pattern observation;
Fig. 7 (a): embodiment 5 sample atoms force microscopes rap the pyrazoles anthracene state of aggregation image (20 * 20 μ m) of (Tapping) pattern observation;
Fig. 7 (b): the fluorescent microscope photo of embodiment 5 samples (120 * 120 μ m);
Fig. 8 (a): embodiment 6 sample atoms force microscopes rap the pyrazoles anthracene state of aggregation image (20 * 20 μ m) of (Tapping) pattern observation;
Fig. 8 (b): the fluorescent microscope photo of embodiment 6 samples (200 * 200 μ m);
Fig. 9 (a): embodiment 7 sample atoms force microscopes rap the pyrazoles anthracene state of aggregation image (12.5 * 12.5 μ m) of (Tapping) pattern observation;
Fig. 9 (b): the fluorescent microscope photo of embodiment 7 samples (50 * 50 μ m);
Figure 10 (a): the fluorescent microscope photo behind the PDMS strip structure of constructing on embodiment 8 quartz substrate (cycles 50 μ m, PDMS band 20 μ m, groove 30 μ m, the degree of depth 2 μ m) the evaporation quinacridone;
Figure 10 (b): the fluorescent microscope photo behind the PDMS dots structure of constructing on embodiment 8 quartz substrate (PDMS spot diameter 20 μ m, some dot spacing 30 μ m, the degree of depth 2 μ m) the evaporation quinacridone; PDMS partly is green, and quartzy part is orange.
Fluorescence spectrum behind the PDMS strip structure evaporation quinacridone of constructing on Figure 11: embodiment 8 quartz substrate, excitation wavelength 495nm, incident exit slit value is 3.
Spectrophotofluorometer spectrogram behind the PVC strip structure evaporation quinacridone of constructing on Figure 12: embodiment 9 quartz substrate, excitation wavelength 495nm, incident exit slit value is 3.
Spectrophotofluorometer spectrogram behind the PU strip structure evaporation quinacridone of constructing on Figure 13: embodiment 10 quartz substrate, excitation wavelength 495nm, incident exit slit value is 5.
Figure 14 (a): the fluorescent microscope photo behind the PDMS strip structure of constructing on embodiment 11 quartz substrate (cycles 50 μ m, PDMS band 20 μ m, groove 30 μ m, the degree of depth 2 μ m) the evaporation ANP;
Figure 14 (b): the fluorescent microscope photo behind the PDMS dots structure of constructing on embodiment 11 quartz substrate (PDMS spot diameter 20 μ m, some dot spacing 30 μ m, the degree of depth 2 μ m) the evaporation ANP; Dark color is the PDMS blue portion, and light color is quartzy green portion.
Spectrophotofluorometer spectrogram behind the PDMS strip structure evaporation pyrazoles anthracene of constructing on Figure 15: embodiment 11 quartz substrate, excitation wavelength 373nm, the entrance slit value is 5, the exit slit value is 3.
Figure 16: embodiment 12 fluorescent microscope photos (500 * 500 μ m), the a-quadrant is a quartz substrate, the substrate of B zone for having PDMS and the alternate microstructure of quartz substrate.
Embodiment
Further illustrate the inventive method and application below by embodiment, rather than will limit the present invention with these embodiment.The present invention has adopted quinacridone and derivative and pyrazoles anthracene two class light emitting molecules thereof to carry out the modulation of different colours fluorescence and the making of phosphor pattern, equally also can be widely used in other light emitting molecule material.
Embodiment 1:
Get PDMS (Silicone elastomer KIT 184, Daw corning, KIT 184 type silicon rubber, Dow Corning Corporation) performed polymer 10ml, add the polymerization starter of 500mg, fully stir evenly, leave standstill the removal bubble, pour into plastic culture dish again and left standstill 2 hours, put into baking oven then 70 ℃ of following heated polymerizables 6 hours.The thin slice of clip 1cm * 2cm (thickness 1.5mm).
Get the quartz plate of this PDMS sheet and 1cm * 2cm thickness 1.5mm respectively, the quinacridone that evaporation 5nm～500nm is thick.Excite down gained fluorogram such as Fig. 1 (a) at the 495nm incident light.Quartzy upward peak is 580nm, and corresponding fluorescence color is orange; The PDMS upward peak is 537nm, and corresponding fluorescence color is green.Promptly because the difference of base material makes same dye molecule send out the fluorescence of different colours under the same conditions.
Have similar phenomena for pyrazoles anthracene molecule equally, as Fig. 1 (b), quartzy upward peak is 500nm, and corresponding fluorescence color is green; The PDMS upward peak is 410nm, and corresponding fluorescence color is blue.
Embodiment 2:
With the method for liquid phase assembling with alkyl silane reagent (Octadecyltrimethoxysilane, tech., 90%, Sigma～aldrich.inc) is assembled into monocrystalline silicon surface (alkyl silane reagent 5 μ g/ml toluene solutions soak 2h).With the method for gas phase assembling with silicon fluoride reagent ((Heptadecafluoro-1,1.2,2-tetrahydradecyl) triethoxysilane, C
16H
19F
17O
3Si, ABCR GmbH﹠amp; Co.KG) be assembled into monocrystalline silicon surface (Dropwise 5 μ l silicon fluoride reagent is kept pressure 0.012 ± 0.002Mpa, deposition 30min).
The learn from else's experience silicon single crystal of above-mentioned processing, the ANP that evaporation 5nm is thick.Spectrophotofluorometer test shows, look (418nm) fluorescence that on the silicon single crystal that fluorine is modified, turns blue, and on the silicon single crystal that alkyl is modified green-emitting (478nm) fluorescence (as Fig. 4).
Implementation column 3:
Control liquid phase built-up time can make alkyl silane reagent (OTS) part be assembled into monocrystalline silicon surface, and rest part still is exposed monocrystalline silicon surface (K.Ekelund, M.Grunze, A.A Baski, L.F.Chi, W.Schrepp, and H.Fuchs Langmuir 1995,11,2143～2150).
Method with the liquid phase assembling makes OTS partly cover monocrystalline silicon surface (alkyl silane reagent 5 μ g/ml toluene solutions soak 15min); Method with the gas phase assembling installs to the exposed monocrystalline silicon surface of residue (Dropwise 5 μ l silicon fluoride reagent is kept pressure 0.012 ± 0.002Mpa, deposition 30min) with the silicon fluoride reagent set then.
The learn from else's experience silicon single crystal of above-mentioned processing, the ANP that evaporation 5nm is thick.With fluorescent microscope (OlympusReflected Fluorescence System BX51, Japan) observe, (Fig. 5 a) can see that the fluorochemical cover part is bright blue bright spot (light color), and the part that OTS covers is more weak green fluorescence (dark color) on the fluorescent microscope photo.Spectrophotofluorometer test shows (Fig. 5 b), and this sample sends the fluorescence of two kinds of different colours, and green glow is because fluorescence is on the weak side, and only the form with acromion occurs in the position of 470nm.
Embodiment 4:
On sheet mica, lift the tar acid that holds with both hands with both hands (purity＞99%, C at the sheet mica of just having peeled off with the LB technology respectively
23H
47COOH purchases the Chemicals in Lardan Fine, Malmo, the pyrazoles anthracene of evaporation 5nm on unitary film Sweden).
The preparation parameter of LB film: V
0=20 μ l, C
1=1mg/ml, CHCl
3Solution, t
1=30min,
S
1＝15cm
2/min，P＝22mN/m，t
2＝30min，S
2＝2mm/min
With atomic force microscope Tapping pattern observation pyrazoles anthracene state of aggregation respectively as shown in Figure 6, figure a is random gathering for the state of aggregation of the pyrazoles anthracene on the mica of just having peeled off, and the part of light color is the pyrazoles anthracene; Figure b is the state of aggregation of the pyrazoles anthracene on the unitary film that lifts the tar acid that holds with both hands with both hands on the sheet mica with the LB technology, is point-like and assembles, and the part of light color is the pyrazoles anthracene.This embodiment has proved that single-layer membrane structure can induce the dye molecule of several nanometers to tens nanometer thickness that different state of aggregation is arranged, make to hang and carry that membrane means is constructed rule or irregular pattern induces dye molecule to assemble with different shape in different zones, thereby this research contents of light of sending out different colours becomes possibility by different base.This routine fluorescence spectrum shows that fluorescence peak is positioned at 500nm, is green emitting.
Embodiment 5:
Palmitinic acid (C
15H
31COOH, purity＞99% is purchased the Chemicals in Lardan Fine, Malmo, Sweden) and the tar acid (C that holds with both hands with both hands
23H
47COOH) 1: 1 usefulness LB of mixture control mol ratio technology lifts into the individual layer hybrid films, tar acid and the palmitinic acid meeting on liquid gas two-phase interface that holds with both hands with both hands be separated, form micron submicron order sea-island two dimensional structure, the unitary film of this sea-island structure can be transferred to (K.Ekelund on the solid substrate in the process of lifting, E.sparr, J.Engblom, H.Wennerstrom and S.Engstrom.Langmuir 1999,15,6946～6949).
We do substrate with the sheet mica of newly peeling off and lift palmitinic acid and the mixture of the tar acid that holds with both hands with both hands, the pyrazoles anthracene of vacuum evaporation 3nm in the sheet mica substrate of this unitary film modified then with the LB technology.
The preparation parameter of LB film: V
0=20 μ l, C
1=1.376mg/ml, CHCl
3Solution, a mol ratio=1: 1,
t
1＝15h，S
1＝15cm
2/min，P＝22mN/m，t
2＝30min，S
2＝2mm/min
Observe pyrazoles anthracene state of aggregation and phosphor pattern respectively as shown in Figure 7 with atomic force microscope Tapping pattern and fluorescent microscope respectively.Figure a is an atomic force microscope Tapping pattern observation pyrazoles anthracene state of aggregation image, can find that pyrazoles anthracene (bright spot) is big and measure more at palmitinic acid surface aggregation grain diameter, and it is little and measure less at the grain diameter of the tar acid surface aggregation that holds with both hands with both hands, explanation is under same experimental conditions, and the mixed monolayer film of the palmitinic acid and the tar acid that holds with both hands with both hands can induce the state of aggregation of pyrazoles anthracene different with aggregate amount; Figure b is corresponding fluorescent microscope photo, and the pyrazoles anthracene that covers on the palmitinic acid sends green fluorescence (light-colored part) under ultraviolet excitation, the part that covers the tar acid that holds with both hands with both hands then since pyrazoles anthracene amount few luminous faint be dark color.
Embodiment 6:
The argent of evaporation 3～4nm on the mixed monolayer film of embodiment 5, silver can preferential deposition at palmitinic acid (C
15H
31COOH) on.(M.Gleiche，L.F.Chi，Fuchs.Thin?solid?Films327-329(1998)268-272)
(vacuum tightness is 5 * 10 with the argent of the automatic control metal multi-source organic vapor phase deposition evaporation 3nm of system of development and design voluntarily earlier on the palmitinic acid of micron submicron order sea-island two dimensional structure and the tar acid hybrid films that holds with both hands with both hands for we
-4Pa, evaporation current 40A), evaporation 10nm pyrazoles anthracene organic molecular film and then in this silver plated substrate.
Observe pyrazoles anthracene state of aggregation and phosphor pattern respectively as shown in Figure 8 with atomic force microscope Tapping pattern and fluorescent microscope respectively.Figure a is an atomic force microscope Tapping pattern observation pyrazoles anthracene state of aggregation image, the tar acid of can finding to hold with both hands with both hands is all covered by pyrazoles anthracene (bright spot), and almost do not had the pyrazoles anthracene on the palmitinic acid of silver covering, explanation is under same experimental conditions, and the pyrazoles anthracene can preferentially accumulate in surface coverage to be had in the substrate of the tar acid that holds with both hands with both hands; Figure b is corresponding fluorescent microscope photo, and the pyrazoles anthracene that covers equally on the tar acid that holds with both hands with both hands sends green fluorescence (light-colored part) under ultraviolet excitation, the palmitinic acid that is covered by silver then because of not luminous be dark color.
Embodiment 7:
2000, amphipathic organic molecules such as discoveries such as Gleiche M two palmitinic acid phosphatidylcholine DPPC lift fast in low pressure (3.0mN/m) with the L-B technology under the condition of (1000 μ m/s) can performance period controlled groove array structure (GLEICHE M, CHI L F, FUCHS H.Nanoscopic channellattices with controlled anisotropic wetting, Nature, 2000,403:173-175).
We carry membrane technique with L-B and lift two palmitinic acid phosphatidylcholines (DPPC 〉=99% is purchased the Aldrich in Sigma), the pyrazoles anthracene that evaporation 10nm is thick thereon on mica substrate.
The preparation parameter of LB film: V
0=20 μ l, C
1=1mg/ml, CHCl
3Solution, t
1=15min,
S
1＝15cm
2/min，P＝2.5mN/m，t
2＝5min，S
2＝10mm/min
Observe pyrazoles anthracene state of aggregation and phosphor pattern respectively as shown in Figure 9 with atomic force microscope Tapping pattern and fluorescent microscope respectively.Figure a is that atomic force microscope is rapped (Tapping) pattern observation pyrazoles anthracene state of aggregation image, can find that the pyrazoles anthracene can preferentially accumulate in surface coverage and have in the substrate of the solid-state DPPC of class; Figure b be corresponding fluorescent microscope photo, the pyrazoles anthracene that covers equally on the solid-state DPPC of class sends green fluorescence (light-colored part) under ultraviolet excitation, fluid-like state DPPC then because of not luminous be the dark color.
Embodiment 8:
Adopt the impression polymerization to select elution method on quartz substrate, to construct out regular pattern (ribbon structure: cycles 50 μ m, PDMS band 20 μ m, groove 30 μ m, the degree of depth 2 μ m with PDMS; Point shape structure: PDMS spot diameter 20 μ m, point dot spacing 30 μ m, the degree of depth 2 μ m), then, with the quartz substrate of 20nm quinacridone evaporation, promptly can be observed the regular pattern (Figure 10) that constitutes by green (light colour) and orange (dark colour) with vacuum evaporation under the fluorescent microscope to patterning.
From fluorescence spectrum (Shimadzu RF～5301PC spectrophotometer), can see that two emission peaks are arranged.Lay respectively at 541nm and 581nm, respectively corresponding green and fluorescent orange are seen Figure 11.
Embodiment 9:
On quartz substrate, construct out regular pattern (cycles 50 μ m with the nano impression method with PVC, PVC band 20 μ m, groove 30 μ m, the degree of depth 2 μ m), then,, can obtain the quartz substrate of 30nm quinacridone evaporation with the method for vacuum evaporation by green and the orange regular pattern that constitutes (similar embodiment 9) to patterning.
From fluorescence spectrum, can see that two emission peaks are arranged.Lay respectively at 548nm and 579nm, corresponding respectively green and orange, see Figure 12.
Embodiment 10:
On quartz substrate, construct out regular pattern (cycles 50 μ m with the nano impression method with PU, PU band 20 μ m, groove 30 μ m, the degree of depth 2 μ m), then,, promptly can be observed under the fluorescent microscope the quartz substrate of 25nm quinacridone evaporation with the method for vacuum evaporation by green and the orange regular pattern that constitutes (similar embodiment 9) to patterning.
From fluorescence spectrum, can see that two emission peaks are arranged.Lay respectively at 547nm and 580nm, corresponding respectively green and orange (seeing Figure 13).
Embodiment 11:
Adopt the impression polymerization to select elution method on quartz substrate, to construct out regular pattern with PDMS, then,, promptly can be observed under the fluorescent microscope the quartz substrate of 10nm ANP evaporation with vacuum evaporation by the blue and green regular pattern (seeing Figure 14) that constitutes to patterning.
From fluorescence spectrum, can see that two emission peaks are arranged.Lay respectively at 419nm and 500nm, corresponding respectively blue and green, see Figure 15.
Embodiment 12:
In the experimentation of embodiment 11, because elution time is long in constructing the last elution step of microstructure, cause part PDMS band to be washed away shown in Figure 16 a-quadrant, the B zone is the PDMS microstructure alternate with quartz substrate, bright part is that PDMS band (blueness) width is 20 μ m, and dark part is that quartz substrate (green) width also is 20 μ m; The a-quadrant is quartz substrate, but because some part of quartz substrate was once covered by PDMS before evaporation ANP, only owing to this fine difference, we just can find that in Figure 16 a-quadrant ANP can preferentially accumulate in the zone that was once covered by PDMS.
This assembles the method for arranging for we provide a kind of dye molecule that makes fully on one-dimensional plane by regular pattern, and huge potential application is arranged in the manufacturing of transmitter and display device.
Embodiment 13:
Adopt the impression polymerization to select elution method on glass, monocrystal silicon substrate, to construct out regular pattern respectively with PDMS, then,, promptly can be observed under the fluorescent microscope the substrate of 25nm quinacridone evaporation with the method for vacuum evaporation by green and the orange regular pattern that constitutes (similar embodiment 9) to patterning.Can see that two emission peak PDMS are arranged from fluorescence spectrum, the green glow zone (540nm) that is positioned on glass is positioned at orange light zone (580nm) on the silicon single crystal.
Embodiment 14:
Adopt the impression polymerization to select elution method on quartz substrate, to construct out regular pattern with PDMS, then, with the method for vacuum evaporation with the quartz substrate of 25nm quinacridone derivative (1,2,9,11 among the structural formula figure A) evaporation to patterning, promptly can be observed under the fluorescent microscope by green and the orange regular pattern that constitutes (as
Embodiment 8).
1. n, n～dibutyl quinacridone, 2. n, n～dihexyl quinacridone, 9. 1,3,8,10～tetramethyl-n, n～dibutyl quinacridone, 11. 1,3,8,10～tetramethyl-quinacridone (the derivative detailed structure is referring to formula 1) all can see having two emission peak: PDMS to be positioned at green glow zone (540nm) from fluorescence spectrum, quartz is positioned at orange light zone (580nm).
Claims (10)
1, the same dye molecule of substrate induction is sent out the method for different colours fluorescence, comprises the steps:
A, choose inorganic substrates or polymeric substrates, and primary surface is handled;
B, the substrate that will handle select elution technique to construct out the surface with microstructure by layered self-packaging, vapour deposition, LB film, nano impression or impression curing;
C, on the inorganic or polymeric substrates of micro-structure surface, evaporation thickness is same a kind of dye molecule film of 1～500nm, vacuum tightness is 1 * 10
-4～5 * 10
-4Pa, size of current are 5～10A;
D, use ultraviolet excitation, promptly can observe the fluorescence that different colours is sent out on same kind of dye molecule surface by spectrophotofluorometer or fluorescent microscope.
2, the same dye molecule of substrate induction as claimed in claim 1 is sent out the method for different colours fluorescence, it is characterized in that: inorganic or polymeric substrates comprises silicon oxide or metal, polydimethylsiloxane, urethane, polyvinyl chloride, polyethylene terephthalate, polystyrene, polyethylene, polypropylene or the diazonium photoresist material polymeric substrates of quartz, glass, ito glass, metal, monocrystalline silicon piece, sheet mica, modified monolayer or multilayered film material.
3, the same dye molecule of substrate induction as claimed in claim 1 is sent out the method for different colours fluorescence, it is characterized in that: inorganic substrates is at first handled with oxygen plasma system his-and-hers watches face, oxygen gas flow rate 80～120ml/min, power 100～300W, in 1～5 minute treatment time, used acetone, chloroform, dehydrated alcohol, high purity water ultrasonic cleaning then successively 2～15 minutes; Polymeric substrates is with dipping in after the absorbent cotton wiping of dehydrated alcohol the high purity water ultrasonic cleaning 2～15 minutes.
4, the same dye molecule of substrate induction as claimed in claim 1 is sent out the method for different colours fluorescence, it is characterized in that: the layered self-packaging method is that to immerse concentration be in the target solution of silane of 0.1～10 μ g/ml to the above-mentioned inorganic substrates of the clean dried that will handle, soak after 20 seconds～24 hours and to take out with toluene, chloroform, ethanol or the ultrasonic cleaning of tetrahydrofuran (THF) organic solvent three times, each 2～15 minutes, use the deionized water ultrasonic cleaning again 2～3 times, each 2～15 minutes, dry up with nitrogen then, thereby in substrate, obtain being modified with the picture on surface of single thin film.
5, the same dye molecule of substrate induction as claimed in claim 1 is sent out the method for different colours fluorescence, it is characterized in that: vapour deposition process is to drip 2～20 microlitre target silylating reagents in vacuum drier in the vial, the above-mentioned inorganic substrates of the clean dried handled is fixed on the specimen holder in the vacuum drier, make the vacuum tightness in the vacuum drier remain on 0.01～0.015Mpa then, behind 15min～4 hour, take out sample, with deionized water ultrasonic cleaning 2～3 times, each 2～15 minutes, dry up with nitrogen then.
6, the same dye molecule of substrate induction as claimed in claim 1 is sent out the method for different colours fluorescence, it is characterized in that: the LB technology is to be that the amphiphilic straight-chain molecule solution of two palmitinic acid phosphatidylcholines, palmitinic acid or the tar acid that holds with both hands with both hands of 0.1～10mg/ml or mol ratio are that the mixed solution of two kinds of above-mentioned amphiphilics of 1～10: 1 spreads on the high purity water parfacies with microsyringe with 2～50 microlitres, concentration, treat that solvent volatilizees behind 10min～24h naturally, on the LB film balance, use baffle plate with 5～30cm
2The speed of/min is compressed, obtain the ～A curve of this sample, measure the surface pressure of film in the compression process, select suitable shift pressure according to ～A curve then, pressure 10min～the 24h that keeps 1～30mN/m on the sheet mica of newly peeling off of water flushing or on the above-mentioned inorganic substrates of clean dried, lifts unitary film with vertical crystal pulling method, putting forward film speed is 1～50mm/min, and whole process system temperature is controlled at room temperature.
7, the same dye molecule of substrate induction as claimed in claim 6 is sent out the method for different colours fluorescence, it is characterized in that: pass through evaporation gold and silver or aluminum metal at the film surface that lifts, evaporation thickness 0.5～10nm, thus the surface differences of film is further enlarged.
8, the same dye molecule of substrate induction as claimed in claim 1 is sent out the method for different colours fluorescence, it is characterized in that: the step that nano impression prepares polymkeric substance and the alternate micro-structure surface of substrate is,
A. the method with photoetching or electron beam lithography makes the rigid template with target microstructure, and its surface modified one deck silylating reagent reducing surface energy with vapour deposition process, this rigid template is impressed on the inorganic or polymeric substrates of the above-mentioned clean dried on spin on polymers blocking layer;
B. under the conditions of high 50～100 degree than polymer barrier layer glass transition temperature Tg, the 10～70Bar that keep-ups pressure, 2～30 minutes flows in the template groove molten polymer;
C. reduce temperature to polymer barrier layer glass transition temperature Tg, template is peeled off;
D. remove residual layer in the polymer barrier layer groove with plasma etching again, promptly obtain polymkeric substance micron, submicrometre structural surface with the rigid template complementary structure.
9, the same dye molecule of substrate induction as claimed in claim 1 is sent out the method for different colours fluorescence, it is characterized in that: it is the photoresist structure 32 that constructing micrometre on the above-mentioned inorganic or polymeric substrates 31 of clean dried of photoresist material or submicrometer structure are arranged in spin coating with traditional ultraviolet photolithographic technology that impression solidify to be selected elution technique; Be stamped in the polymkeric substance performed polymer 34 that is spun on the smooth glass 33 as template again, 10～50bar, 2～15min keep-up pressure, thereby polymkeric substance performed polymer coating 34 is clamp-oned in the groove of 32 of photoresist structures, form polymkeric substance performed polymer structure 35, then smooth glass 33 is peeled off, thereby in substrate 31, form the alternate structure of photoresist material 32 and polymkeric substance performed polymer 35, and smooth glass 33 can be abandoned after peeling off as expendable material; After leaving standstill 2～6 hours, under the condition of heating, impel performed polymer structure 35 to be polymerized to polymer architecture 36, dissolve away photoresist structure 32 according to what deliquescent difference was utilized solvent selectivity again, can in substrate 31, obtain polymkeric substance 36 body structure surfaces of micron or submicron.
10, the application of any one method of claim 1-9 in preparation transmitter, luminescent device or display device.
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| CN102649625A (en) * | 2012-05-03 | 2012-08-29 | 北京鼎臣超导科技有限公司 | Method for cleaning glass substrate for coating |
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