CN101222021A - Formulation and method for depositing a material on a substrate - Google Patents
Formulation and method for depositing a material on a substrate Download PDFInfo
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- CN101222021A CN101222021A CNA2008100087211A CN200810008721A CN101222021A CN 101222021 A CN101222021 A CN 101222021A CN A2008100087211 A CNA2008100087211 A CN A2008100087211A CN 200810008721 A CN200810008721 A CN 200810008721A CN 101222021 A CN101222021 A CN 101222021A
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- deposited
- deposition materials
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- 239000000463 material Substances 0.000 title claims abstract description 72
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims description 15
- 238000000151 deposition Methods 0.000 title abstract description 17
- 238000009472 formulation Methods 0.000 title abstract 3
- 239000000758 substrate Substances 0.000 title abstract 3
- 239000002904 solvent Substances 0.000 claims abstract description 50
- 238000009835 boiling Methods 0.000 claims abstract description 21
- 230000008021 deposition Effects 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 8
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 7
- 239000002800 charge carrier Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 34
- 239000000243 solution Substances 0.000 description 19
- 238000009826 distribution Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 4
- 239000011877 solvent mixture Substances 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- BFIMMTCNYPIMRN-UHFFFAOYSA-N 1,2,3,5-tetramethylbenzene Chemical compound CC1=CC(C)=C(C)C(C)=C1 BFIMMTCNYPIMRN-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000000935 solvent evaporation Methods 0.000 description 2
- -1 -isopropyl biphenyls Chemical class 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical class C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical group [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- SGDMQXAOPGGMAH-UHFFFAOYSA-N phenol;thiophene Chemical compound C=1C=CSC=1.OC1=CC=CC=C1 SGDMQXAOPGGMAH-UHFFFAOYSA-N 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
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- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
A formulation for depositing a material on a substrate, the formulation comprising the material to be deposited on the substrate dissolved in a solvent system comprising a first solvent component having a relatively high boiling point and which exhibits a relatively low solubility with respect to the material to be deposited, and a second solvent component having a relatively low boiling point and which exhibits a relatively high solubility with respect to the material to be deposited.
Description
The application is the dividing an application that be on February 27th, 2002, denomination of invention the applying date for the Chinese patent application 02805595.0 of " material prescription and the method for depositing on base material ".
The present invention relates to material is deposited on material prescription on the base material, relate to by inkjet deposited technology material is deposited on method on the base material, and relate to the method for making luminescent device by this deposition process.
As shown in Figure 1, luminescent device generally includes one deck and is clipped in electroluminescent polymer 3 between negative electrode 2 and the anode 1, so that charge carrier can move between two electrodes and electroluminescent polymer.This luminescent device is normally by being deposited on one deck electroluminescent polymer 3 on the glass baseplate 5 that scribbles anode layer 1 (as one deck indium-tin-oxide (ITO)), and cathode layer 2 (as the calcium layer) is deposited on the electroluminescent polymer 3 makes.This device also can comprise other layer, as is configured in hole transporting layer 4 between anode 1 and the electroluminescent polymer layer 3 (the polyethylene dioxy thiophene phenol that the one deck described in EP0686662 mixes) and is configured in electron supplying layer (displaying in the device shown in Figure 1) between negative electrode and the electroluminescent layer.
Can adopt ink-jet technology to deposit the electroluminescent polymer layer.This technology has had explanation in EP0880303A1, it is for reference that this document content has been listed this paper in.This technology consists essentially of and makes electroluminescent polymer reach the deposition of controlling filed photoluminescence polymer solution droplets by nozzle and solvent evaporation subsequently.This technology is specially adapted to the deposition of electroluminescent polymer patterned layer.For example, at the electroluminescent polymer layer that may require two layers to comprise orderly pixel array aspect some purposes, wherein each pixel is that single drop deposition by electroluminescent polymer solution is produced.Polymer is equally distributed in the little point that it is desirable in this case stay after solvent evaporation.
Usually, the solution of electroluminescent polymer in solvent (as isodurene) is used for this technology.Yet have been noted that this conventional solvent can produce following point: behind the droplet drying of deposit solution, it is annular that most of electroluminescent polymer is deposited on forming of little point on every side, and the core of little point has only very thin polymer film.This will cause device efficiency low.
The purpose of this invention is to provide a kind of prescription, adopt this prescription, can on base material, be deposited as the film that desired thickness distributes by control drop deposition technique.
According to a first aspect of the invention, provide a kind of material has been deposited on material prescription on the base material, this prescription comprises and is dissolved in treating in a kind of dicyandiamide solution and is deposited on material on the base material, wherein dicyandiamide solution comprise a kind of boiling point higher, for treat that deposition materials has than first solvent composition of low solubility and a kind of boiling point is lower, for treating that deposition materials has second solvent composition of higher solubility.
About every kind of solvent composition the solubility of material is meant the solubility of this material in every kind of solvent composition.
Ink-jet technology requires about at the most 20 centipoises of viscosity of filling a prescription usually.Usually, supplying the viscosity of the prescription of ink-jet technology is about 10 centipoises.
First solvent composition can comprise one or more boiling points higher, for treating that deposition materials has the solvent than low solubility (with respect to second solvent composition), second solvent composition equally also can comprise one or more boiling points lower, for treating that deposition materials has the solvent of higher solubility (with respect to first solvent composition).
In one embodiment, the boiling spread of second solvent composition is 100-200 ℃, and the boiling spread of first solvent composition is 130-300 ℃.Boiling-point difference between first solvent composition and second solvent composition is preferably 30-250 ℃, more preferably 70-150 ℃.Treat that the solubility of deposition materials in first solvent composition preferably reaches 0.5 weight per volume %, more preferably scope is 0.03-0.3 weight per volume %, treat that the solubility of deposition materials in second solvent composition preferably is higher than 0.5 weight per volume %, more preferably is higher than 1.5 weight per volume %.
The selection of the ratio of first solvent composition is preferably: in case after removing second solvent composition, the concentration of the material that stays solution in first solvent composition can reach capacity or supersaturation basically.In one embodiment, the proportion of first solvent composition is 10-60 volume %, more preferably 20-50 volume %.
In one embodiment, the proportion of second solvent composition is 40-90 volume %, is preferably 50-80 volume %.
According to another aspect of the present invention, provide a kind of material that makes to be deposited on method on the base material, this method comprises according to ink-jet technology makes material solution by nozzle one or many material solutions are deposited on the base material, and make each droplets deposited drying, wherein material solution comprises aforesaid prescription.
The selection of dicyandiamide solution will make material in the solution begin precipitating in the stage early of droplet drying, promptly precipitating will take place when most of solvent still keeps not evaporating.
The selection of dicyandiamide solution will make on the base material varied in thickness of the dry little point of material less than 80% of maximum ga(u)ge, preferably less than 50%, and is more preferably less than 30%.Most preferred varied in thickness is less than 15%.
In one embodiment, it is 0.5 weight per volume % that the selection of dicyandiamide solution will make the content of material to be deposited in the prescription, dry micro polymer dot center thickness (promptly by thicker ring (if present) area surrounded) is the 60-140 nanometer, preferred about 70-100 nanometer, this is necessary for improving electroluminescent efficient and organic light-emitting device life-span.
As mentioned above, the material of depositing on base material can be the blend of organic material such as polymer or polymer for example.For a kind of purposes, this polymer comprises one or more semiconductive conjugated polymers such as charge transport polymer or light emitting polymer or both blends.
In accordance with a further aspect of the present invention, a kind of method of making luminescent device is provided, wherein luminescent device comprises that one deck is clipped in two interelectrode electroluminescent materials, so that charge carrier can move between two electrodes and electroluminescent material layer, wherein the electroluminescent material layer is made by said method.
According to a further aspect in the invention, provide above-mentioned prescription reducing or avoiding taking place purposes aspect the ring-type deposition.
Hereinafter will be to embodiment of the present invention (only as embodiment) and in conjunction with the accompanying drawings, wherein:
Fig. 1 is a kind of schematic diagram of luminescent device;
Fig. 2 and Fig. 3 are the prescriptions that adopts embodiment of the present invention, the little dot thickness distribution curve that obtains by ink-jet technology;
Fig. 4 adopts fully by 1, the little dot thickness distribution curve of the electroluminescent polymer that solvent deposited that the 2-dimethyl benzene is formed;
Fig. 5 is the prescription that adopts another embodiment of the invention, the little dot thickness distribution curve that obtains by ink-jet technology; And
What illustrate illustrated in Fig. 6 is some repetitive and polymer.
With 1 of 60 volume %, 2-dimethyl benzene (boiling point: 144.4 ℃) and 40 volume % α-tetralones (boiling point: 255 ℃) are made solvent mixture.Adopt this solvent mixture prepare 0.5 weight per volume %, peak molecular weight is about 266000 9,9 one dioctyl fluorene unit and diazosulfide units alternately polymer (F8BT) solution.By ink-jet method the solution droplets that makes being deposited on modification becomes on the surface have than the polyimide base material of low-surface-energy.Make drop dry under room temperature and humidity (20 ℃ ± 1.0 ℃ reach 30-40% relative humidity) condition, and the micro polymer point of drying is carried out the Dektak mensuration of thickness distribution.Measurement result is shown among Fig. 2.
With 1 of 60 volume %, 2-dimethyl benzene and 40 volume % cyclohexyl benzenes are made solvent mixture.By ink-jet method the 0.5 weight per volume %F8BT polymer solution droplets identical with embodiment 1 is deposited on the polyimide base material of surface modification.The micro polymer point of drying is carried out the Dektak mensuration of thickness distribution.Measurement result is shown among Fig. 3.
Comparative examples
By ink-jet method will be identical with embodiment 1 and 2 the F8BT polymer 1,0.5 weight per volume % solution droplets in the 2-dimethyl benzene is deposited on the polyimide base material of surface modification.The micro polymer point of drying is carried out the Dektak mensuration of thickness distribution.Measurement result is shown among Fig. 4.
Compare as seen by Fig. 2,3 and 4, adopt the thickness evenness of the little point of dry polymer that prescription is made according to the present invention to increase significantly than comparative examples.Can think that the raising of thickness evenness is produced by following mechanism.In the droplet drying process, the rapidly evaporation and stayed the saturated solution of high boiling solvent of volatility low boiling point solvent so just can impel the quick precipitating of polymer and stops it that Radial Flow takes place in drop, therefore can form the uniform little point of distribution of polymer.
In addition, the center thickness of little point of same concentrations material had increased during the raising of thickness evenness made and fills a prescription.Can think that can control little dot center thickness be the key factor that improves the luminescent device efficient of being made by ink-jet technology.The present invention can improve center thickness under not increasing the concentration for the treatment of deposition materials in the prescription, therefore, manufacturing have require the size device pixel, that reach desired resolution aspect have clear superiority.
Employing is by 40 volume % dimethyl benzene isomer mixture (boiling point: 138 ℃) and 40 volume %1, and 2, the solvent mixture that 4-trimethylbenzene (boiling point: 168 ℃) and 20 volume %3-isopropyl biphenyls (boiling point: 295 ℃) are formed has also obtained good result.Shown in Figure 5 is the solution of blend polymer in three component solvent systems that adopts 5 weight per volume %, is deposited as the Dektak measurement result of the thickness distribution of the little point of dry polymer by ink-jet technology.The solubility of this blend polymer in preceding two kinds of low boiling point solvents is high in than the third high boiling solvent.
Claims (12)
1. one kind is deposited on material prescription on the base material by ink-jet technology with material, this prescription comprises and is dissolved in treating in a kind of dicyandiamide solution and is deposited on material on the base material, it is higher that wherein dicyandiamide solution comprises a kind of boiling point, lower for treating that deposition materials has than first solvent composition and a kind of boiling point of low solubility, for treating that deposition materials has second solvent composition of higher solubility, wherein the boiling-point difference between first solvent composition and second solvent composition is that 30-250 ℃ and the described deposition materials for the treatment of are higher 3 times than the dissolving in first solvent composition at least in the dissolving of second solvent composition.
2. according to the prescription of claim 1, wherein the boiling spread of second solvent composition is 100～200 ℃.
3. according to the prescription of claim 1 or 2, wherein the boiling spread of first solvent composition is 130-300 ℃.
4. according to the prescription of claim 1, wherein the boiling-point difference between first solvent composition and second solvent composition is 70-150 ℃.
5. according to the prescription of aforementioned each claim, treat that wherein the solubility of deposition materials in first solvent composition reaches 0.5 weight per volume %.
6. according to the prescription of claim 5, treat that wherein the solubility of deposition materials in first solvent composition is 0.03-0.3 weight per volume %.
7. according to the prescription of aforementioned each claim, treat that wherein the solubility of deposition materials in second solvent composition is higher than 0.5 weight per volume %.
8. according to the prescription of claim 7, treat that wherein the solubility of deposition materials in second solvent composition is higher than 1.5 weight per volume %.
9. according to the prescription of aforementioned each claim, in case wherein in the prescription selection of the consumption of material and the first solvent composition ratio to make remove second solvent composition after, the solution concentration of the material that stays in first solvent composition should be in saturated or supersaturation.
10. one kind is deposited on method on the base material with material, this method comprises according to ink-jet technology makes material solution by nozzle one or many material solutions are deposited on the base material, and make droplet drying, wherein material solution comprises the formula components according to aforementioned each claim.
11. according to the method for claim 10, wherein the varied in thickness of dry little point is less than 30% of maximum ga(u)ge.
12. method of making luminescent device, wherein luminescent device comprises that one deck is clipped in two interelectrode electroluminescent materials, so that charge carrier can move between two electrodes and electroluminescent material layer, wherein the electroluminescent material layer is by making according to claim 10 or 11 methods.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB0104875.0A GB0104875D0 (en) | 2001-02-28 | 2001-02-28 | A formulation for depositing a conjugated polymer layer |
| GB0104875.0 | 2001-02-28 | ||
| GBGB0107740.3A GB0107740D0 (en) | 2001-03-28 | 2001-03-28 | Formulation and method for depositing a material on a substrate |
| GB0107740.3 | 2001-03-28 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028055950A Division CN100377380C (en) | 2001-02-28 | 2002-02-27 | Formulation and method for depositing a material on a substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101222021A true CN101222021A (en) | 2008-07-16 |
| CN101222021B CN101222021B (en) | 2012-05-30 |
Family
ID=9909640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100087211A Expired - Lifetime CN101222021B (en) | 2001-02-28 | 2002-02-27 | Formulation and method for depositing a material on a substrate |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN101222021B (en) |
| GB (1) | GB0104875D0 (en) |
| TW (1) | TW527432B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9556323B2 (en) | 2013-11-11 | 2017-01-31 | Lg Display Co., Ltd. | Ink for display device manufacturing and method for manufacturing of the same, method for manufacturing using the same |
| WO2018095381A1 (en) * | 2016-11-23 | 2018-05-31 | 广州华睿光电材料有限公司 | Printing ink composition, preparation method therefor, and uses thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5091004A (en) * | 1987-09-22 | 1992-02-25 | Dainippon Ink And Chemicals, Inc. | Ink composition |
| TW508975B (en) * | 1999-03-29 | 2002-11-01 | Seiko Epson Corp | Composition, film manufacturing method, as well as functional device and manufacturing method therefor |
-
2001
- 2001-02-27 TW TW090104585A patent/TW527432B/en not_active IP Right Cessation
- 2001-02-28 GB GBGB0104875.0A patent/GB0104875D0/en not_active Ceased
-
2002
- 2002-02-27 CN CN2008100087211A patent/CN101222021B/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9556323B2 (en) | 2013-11-11 | 2017-01-31 | Lg Display Co., Ltd. | Ink for display device manufacturing and method for manufacturing of the same, method for manufacturing using the same |
| CN104638198B (en) * | 2013-11-11 | 2018-05-18 | 乐金显示有限公司 | The ink of display device manufacture, its manufacturing method and the method for manufacturing display device |
| WO2018095381A1 (en) * | 2016-11-23 | 2018-05-31 | 广州华睿光电材料有限公司 | Printing ink composition, preparation method therefor, and uses thereof |
| US11248138B2 (en) | 2016-11-23 | 2022-02-15 | Guangzhou Chinaray Optoelectronic Materials Ltd. | Printing ink formulations, preparation methods and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0104875D0 (en) | 2001-04-18 |
| CN101222021B (en) | 2012-05-30 |
| TW527432B (en) | 2003-04-11 |
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Granted publication date: 20120530 |