CN109709769A - Photoresist, pixilated photoluminescent color film containing photoresist and application of photoresist - Google Patents
Photoresist, pixilated photoluminescent color film containing photoresist and application of photoresist Download PDFInfo
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- CN109709769A CN109709769A CN201910137512.5A CN201910137512A CN109709769A CN 109709769 A CN109709769 A CN 109709769A CN 201910137512 A CN201910137512 A CN 201910137512A CN 109709769 A CN109709769 A CN 109709769A
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- photoresist
- quantum dot
- light
- pixel
- external sheath
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Links
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 113
- 239000000463 material Substances 0.000 claims abstract description 73
- 239000002096 quantum dot Substances 0.000 claims abstract description 56
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 16
- -1 quantum rods Substances 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 239000010408 film Substances 0.000 claims description 50
- 238000004020 luminiscence type Methods 0.000 claims description 30
- 239000005083 Zinc sulfide Substances 0.000 claims description 29
- 230000004048 modification Effects 0.000 claims description 29
- 238000012986 modification Methods 0.000 claims description 29
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical class [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 28
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 28
- 230000005540 biological transmission Effects 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 14
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 9
- 229940116367 cadmium sulfide Drugs 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical group OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 8
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 7
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 claims description 7
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000001259 photo etching Methods 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 150000001721 carbon Chemical group 0.000 claims description 4
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N n-Decanedioic acid Natural products OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 238000001228 spectrum Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N Heptanedioic acid Natural products OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N Nonanedioid acid Natural products OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N Suberic acid Natural products OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- FTWRSWRBSVXQPI-UHFFFAOYSA-N alumanylidynearsane;gallanylidynearsane Chemical compound [As]#[Al].[As]#[Ga] FTWRSWRBSVXQPI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910003460 diamond Inorganic materials 0.000 claims description 2
- 239000010432 diamond Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- GGYFMLJDMAMTAB-UHFFFAOYSA-N selanylidenelead Chemical compound [Pb]=[Se] GGYFMLJDMAMTAB-UHFFFAOYSA-N 0.000 claims description 2
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 claims description 2
- BTTOHACVRWMHOB-UHFFFAOYSA-N [Zn].[Se].[S] Chemical compound [Zn].[Se].[S] BTTOHACVRWMHOB-UHFFFAOYSA-N 0.000 claims 1
- 238000006862 quantum yield reaction Methods 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 11
- 238000013329 compounding Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 238000005424 photoluminescence Methods 0.000 abstract 4
- 239000002135 nanosheet Substances 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- 238000007711 solidification Methods 0.000 description 13
- 230000008023 solidification Effects 0.000 description 13
- 239000002105 nanoparticle Substances 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003086 colorant Substances 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012769 display material Substances 0.000 description 2
- 230000003760 hair shine Effects 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- XPMJOJJWEYSSFQ-UHFFFAOYSA-N [In].[S].[Se].[Zn] Chemical compound [In].[S].[Se].[Zn] XPMJOJJWEYSSFQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- KIGGRLQHVCRPDS-UHFFFAOYSA-N azanide oxygen(2-) titanium(4+) Chemical compound [O-2].N[Ti+3].[O-2].[O-2].N[Ti+3] KIGGRLQHVCRPDS-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention provides a photoresist, a pixelized photoluminescence color film containing the photoresist and application of the pixelized photoluminescence color film, wherein the photoresist comprises a photoresist body and a photoluminescence material which is dispersed in the photoresist body and is modified with carboxyl on the surface, and the photoluminescence material comprises any one or a mixture of at least two of quantum dots, quantum rods, nanosheets or perovskite crystals; the invention can improve the dispersibility of the photoluminescent material in the photoresist body by compounding the photoluminescent material with the surface modified carboxyl with the photoresist body, and reduce the defects of agglomeration, cavities and the like of the photoluminescent material in the photoresist curing process as much as possible on the premise of not influencing the quantum yield of the photoluminescent material.
Description
Technical field
The invention belongs to field of compound material more particularly to a kind of photoresists, contain its pixelation luminescence generated by light coloured silk film
And application thereof.
Background technique
At this stage, realize that the color filter film that colorization is shown is by red (R), green (G), blue (B) three mostly
The sub-pixel combinations of light transmission form, however, using dyestuff or fluorescent powder as the backlight in each sub-pixel in such method more
Wavelength conversion material, above-mentioned material can absorb a large amount of luminous energy, so that the capacity usage ratio of filter coating is very low, moreover, this to filter
Light film carry out colorization method, it can be achieved that gamut area it is smaller, colour purity is not high, and visual effect is poor.
The embedded photoluminescent materials such as quantum dot are a kind of nano particles being made of II-VI group or iii-v element, as one
The emerging semiconductor nano material of kind, the size in three dimensions are all not more than corresponding semiconductor material exciton Bohr half
Two times of diameter make its continuous band structure become have molecular characterization since electrons and holes therein are by quantum confinement
Discrete energy level structure, therefore fluorescence can be emitted after being excited, the feature of quantum dot maximum is that its band gap can be with the size of partial size
And change, partial size is bigger, and band gap is smaller, and the wavelength of stimulated luminescence is shorter, and partial size is smaller, and energy gap is got over
Greatly, stimulated luminescence wavelength is longer.
Since quanta point material has the characteristics that this different colours that can be realized by adjusting size shine, and produce
Raw light spectral is pure, and the quantum yield (QY) for emitting light is high, spectrum is accurate, half-peak width, is applied to display field
When, colour gamut has the advantages that high colour gamut and color adjustment are very flexible up to 100%.
It is existing to there is more ask using materials such as the optical filter of this embedded photoluminescent material of quantum dot or backlight panels
Topic, as disclosed a kind of quantum dot color filter, multiple pixels in structure in CN103278876A, if each pixel includes
The color sub-pixel of dry different colours, the colored filter further include the light generated after being excited formed by quanta point material
With the identical underlay substrate of color of the corresponding color sub-pixel and the color sub-pixel region formed by quanta point material,
For absorbing the filter layer for not exciting the light of quanta point material, the quanta point material used is zinc sulphide, zinc oxide, nitridation
Gallium, cadmium sulfide, gallium selenide, cadmium selenide, forming zinc, forms cadmium, GaAs, indium phosphide, at least one in lead telluride at zinc selenide
Kind.A kind of preparation method of quantum dot light photoresist is disclosed in CN105929635A, it is disclosed that by carrying out to quantum dot
Surface treatment, later mixes it with photoresist to prepare the sub-pixel in optical filter, the surface treatment of the quantum dot
Including quantum dot to be dissolved in dispersing agent, obtain quantum dot dispersion liquid, later, by tetraethyl orthosilicate, hexamethylene, just oneself
Alcohol, polyoxyethylene -8- octyl phenyl ether are mixed and stirred for uniformly, obtaining photodiffusion material stoste, by quantum dot dispersion liquid and light
The mixing of diffusion material stoste, adds ammonium hydroxide, by stirring or ultrasonic disperse said mixture is uniformly mixed.However, pressing
According to method disclosed in above-mentioned patent, when preparing pixelation luminescence generated by light coloured silk film with similar structure using photoetching process, due to
Quantum dot is inorganic matter and photoresist is organic polymer, and the intersolubility and dispersibility of the two are very poor, so that the picture after photocuring
Vegetarian refreshments will appear quantum dot agglomeration, and quantum dot covering can be generated in the pixel that micro- sem observation item can also be found not
The cavity arrived, moreover, quantum yield also will appear a degree of reduction, above-mentioned phenomenon is for obtained backlight or filter
The homogeneity of middle quantum dot dispersion and the utilization rate of backlight all can be very big influence.
Therefore, on the basis of existing technology, those skilled in the art needs by changing the luminescence generated by lights such as quantum dot
The suitability of material and photoresist ontology obtains a kind of novel photoresist, with to the existing backlight panel containing quantum dot or
Display device improves.
Summary of the invention
For the deficiencies in the prior art, the purpose of the present invention is to provide a kind of novel compound photoresists, lead to
The suitability for changing the embedded photoluminescent materials and photoresist ontology such as quantum dot in photoresist is crossed, to the existing back containing quantum dot
Optic panel or display device improve.
For this purpose, the photoresist includes photoresist sheet one of the objects of the present invention is to provide a kind of photoresist
Body and the surface modification being dispersed in photoresist ontology have the embedded photoluminescent material of carboxyl.
The embedded photoluminescent material include in quantum dot, quantum rod, nanoscale twins or perovskite crystal any one or
The mixture of at least two mixture, for example, quantum dot and quantum rod, the mixture of nanoscale twins and perovskite crystal or
Quantum dot, quantum rod and mixture of perovskite crystal etc..
The present invention is by that can improve it between photoresist ontology in traditional embedded photoluminescent material surface modification carboxyl
Compatibility, improve embedded photoluminescent material particle between repulsive force, the mixture of the two after hardening, will not be because of it
The dispersion homogeneity of middle embedded photoluminescent material is poor, it is made to occur phenomena such as reuniting, cavity after photocuring, will not be because of partial size
Or the variation of energy band leads to problems such as embedded photoluminescent material quantum yield decline occur.
Preferably, the surface modification has the embedded photoluminescent material of carboxyl by being immersed in embedded photoluminescent material containing extremely
It is obtained in the solution of the alkane compound of few two carboxyls.
Preferably, also need progress ultrasonic disperse and separating step that can just obtain the surface modification and have carboxyl after the submergence
Embedded photoluminescent material.
Preferably, in the alkane compound containing at least two carboxyls, 1~10 is contained in the main chain of alkane carbochain
(for example, 2,3,4,5,6,7,8 or 9) carbon atom, further preferably 5~10 carbon atoms, main chain
When the more alkane compound of middle carbon atom number is used for the surface modification of embedded photoluminescent material, luminescence generated by light can be further increased
Repulsion between material and the compatibility between photoresist ontology, to further increase embedded photoluminescent material in photoresist
The homogeneity dispersed in ontology.
Preferably, in the alkane compound containing at least two carboxyls, carbon containing odd number in the main chain of alkane carbochain
Atom, main chain are that the alkane compound containing at least two carboxyls of odd number carbon atom can be embedded photoluminescent material in photoetching
Bigger solubility is provided in glue ontology.
Preferably, the alkane compound containing at least two carboxyls be malonic acid, succinic acid, glutaric acid, the acid of second three,
It is 1,6- adipic acid, 1,7- pimelic acid, 1,8- suberic acid, any in three acid of 1,9- azelaic acid, 1,10- sebacic acid or 1,2,7- heptan
It is a kind of or at least two mixture, the considerations of for cost and dispersion effect, further preferably glutaric acid.
Preferably, the photoresist ontology is any one photoresist containing epoxy bond, photoresist and table containing epoxy bond
Face, which is modified between the embedded photoluminescent material of carboxyl, has bigger affinity, further preferably U.S. Microchem company
The SU8 type photoresist of production.
Preferably, the embedded photoluminescent material be quantum dot, quantum dot as embedded photoluminescent material with luminescent spectrum it is narrow,
The advantages that color purity is high, backlight absorption efficiency is high and display colour gamut is wide.
Preferably, the quantum dot is cadmiumsulfide quantum dot, indium sulphur quantum dot, carbon quantum dot, graphene quantum dot, calcium
Titanium ore quantum dot, alloy quantum dot, indium phosphide quantum dot, the CdSe quantum dots of external sheath zinc sulphide, external sheath vulcanization
The CdSe quantum dots of cadmium, the indium aluminium As quantum dots of external sheath aluminum gallium arsenide, external sheath zinc selenium sulfur indium phosphide quantum dot, outer
The layer cladding indium phosphide quantum dot of zinc sulphide, the lead selenide quantum dot of external sheath vulcanized lead, external sheath calcium sulfide and inside
Doped with the zinc sulphide gallium quantum dot of copper, the cadmium telluride quantum dot of external sheath cadmium sulfide, external sheath zinc sulphide tellurium
In cadmium quantum dot any one or at least two mixture, the further preferably cadmium selenide amount of external sheath zinc sulphide
The CdSe quantum dots of son point or external sheath cadmium sulfide.
Preferably, in percentage by weight, surface modification has the embedded photoluminescent material of carboxyl to contain in the photoresist
Amount be 5~25wt%, for example, 6wt%, 8wt%, 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, 20wt%,
22wt% or 24wt% etc..
Preferably, light diffusing particles are also contained in the photoresist, after the introducing of light diffusing particles has raising solidification
The soft degree and the advantages that backlight utilization ratio of shining of photoresist.
Preferably, in percentage by weight, the content of light diffusing particles is 5~25wt% in the photoresist, such as
For 6wt%, 8wt%, 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, 20wt%, 22wt% or 24wt% etc..
Preferably, partial size >=100nm of the light diffusing particles, the scattering effect of light diffusing particles of the partial size greater than 100nm
Fruit is more excellent, for example, 150nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm or 1000nm etc.,
Further preferably 100~500nm.
Preferably, the light diffusing particles are TiO 2 particles and/or silicon dioxide granule.
The second object of the present invention is to provide a kind of pixelation luminescence generated by light coloured silk film, the pixelation luminescence generated by light coloured silk film
Including black substrate film, and the light transmission sub-pixel for penetrating and being dispersed in the black substrate film.
The light transmission sub-pixel is obtained by foregoing photoetching adhesive curing.
Preferably, the light transmission sub-pixel is any one in red sub-pixel, green sub-pixels or blue subpixels
Or at least two mixture, the color in light transmission sub-pixel has the photic hair of carboxyl by surface modification in the photoresist after solidifying
The stimulated emission spectrum of luminescent material determines, and is mutually not attached between the different light transmission sub-pixel of any two color, when backlight
When exciting light is blue light, the blue subpixels can be not provided with or to be set as colourless transparent material, when backlight exciting light
When for ultraviolet light, the sub-pixel of above-mentioned three kinds of colors is both needed to be arranged.
Preferably, also contain yellow sub-pixel in the light transmission sub-pixel.
Preferably, the light transmission sub-pixel includes rectangle, square, circle in the shape on the thin film planar of fast black base bottom
Any one in shape, ellipse, triangle or diamond shape or at least two figures.
Preferably, the light transmission sub-pixel is 20~100 μm in the maximum gauge on the thin film planar of fast black base bottom, such as
It is 25 μm, 35 μm, 45 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm or 95 μm etc..
The third object of the present invention be to provide a kind of foregoing pixelation luminescence generated by light coloured silk film in backlight panel or
Application in display device.
Numberical range of the present invention not only includes enumerated point value, further includes the above-mentioned numerical value not included
Arbitrary point value between range, as space is limited and for concise consideration, range described in the present invention no longer exclusive list includes
Specific point value.
Compared with prior art, the invention has the benefit that
The present invention by the surface modification carboxyl of traditional embedded photoluminescent material, and by it with conventional lithography glue ontology by compounding
It uses, can be improved dispersibility of traditional embedded photoluminescent material in photoresist ontology, do not influencing embedded photoluminescent material quantum
Reunion, cavity that embedded photoluminescent material occurs in photoresist ontology solidification process etc. is reduced under the premise of yield as far as possible to lack
It falls into, can be used as the backlights such as pixelation luminescence generated by light coloured silk film after the compounding photoetching adhesive curing or display material uses, compare other
Existing product has higher backlight trap, the soft degree that shines, color purity and display colour gamut, can obtain higher quality
Display effect.
Detailed description of the invention
Fig. 1 is that the obtained photoresist 1 of embodiment 1 is after film and solidification in the specific embodiment of the invention, amount therein
Optical photograph when son point is stimulated.
Fig. 2 is that the obtained photoresist 2 of embodiment 2 is after film and solidification in the specific embodiment of the invention, amount therein
Optical photograph when son point is stimulated.
Fig. 3 is that the obtained photoresist 11 of reference examples 3 is after film and solidification in the specific embodiment of the invention, amount therein
Optical photograph when son point is stimulated.
Fig. 4 is that the obtained photoresist 12 of reference examples 4 is after film and solidification in the specific embodiment of the invention, amount therein
Optical photograph when son point is stimulated.
Fig. 5 is that the obtained photoresist 1 of embodiment 1 is after film and solidification in the specific embodiment of the invention, amount therein
Microscope photo when son point is stimulated.
Fig. 6 is that the obtained photoresist 9 of reference examples 1 is after film and solidification in the specific embodiment of the invention, amount therein
Microscope photo when son point is stimulated.
Fig. 7 is that the obtained photoresist 10 of reference examples 2 is after film and solidification in the specific embodiment of the invention, amount therein
Microscope photo when son point is stimulated.
Fig. 8 is the pixelation luminescence generated by light coloured silk film that the photoresist 1~3 obtained using the embodiment of the present invention 1~3 is prepared
Structural schematic diagram, wherein 100 be black substrate film；201 be red sub-pixel；202 be green sub-pixels；203 be blue
Sub-pixel.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
The Quantaurus-QY that quantum yield numerical value in each embodiment and reference examples is produced by Bin Song company
Plus type UV-NIR absolute quantum yield tester measures.
Embodiment 1
It is by CdSe quantum dots (CdSe/ZnS), 15g partial size that 10g surface modification has the external sheath zinc sulphide of carboxyl
The titanium dioxide nano-particle of 100nm is uniformly mixed with the SU8 type photoresist that Microchem company, the U.S. 75g produces, and obtains light
Photoresist 1.
Wherein, the surface modification has the CdSe quantum dots of the external sheath zinc sulphide of carboxyl to make by the following method
It is standby:
The CdSe quantum dots of 100mg external sheath zinc sulphide are dispersed in the hexamethylene for the glutaric acid that concentration is 6.25g/L
In alkane solution, simultaneously mixture 2h is stirred at room temperature in ultrasonic disperse, is centrifugally separating to obtain later and is stated surface modification and have the outer of carboxyl
The CdSe quantum dots of layer cladding zinc sulphide.
After obtained 1 film of photoresist, solidifies in the case where wavelength is the ultraviolet light of 360nm, obtain with a thickness of 4.5 μm
Photoresist film, test obtains it and glows under the irradiation of exciting light, and quantum yield 71.5% passes through microscope photo
The dispersion of observation wherein embedded photoluminescent material it is found that dispersion is good in the photoresist of quanta point material after hardening,
Do not occur reuniting and cavitation, stimulated luminescence are soft uniformly.
Embodiment 2
Difference with embodiment 1 is only that, the CdSe quantum dots of external sheath zinc sulphide are replaced with external sheath sulphur
The CdSe quantum dots of cadmium, and identical surface modification step is carried out to it makes its surface with carboxyl.
Embodiment 2 obtains photoresist 2, after its film, solidifies in the case where wavelength is the ultraviolet light of 360nm, obtains thickness
The photoresist film that degree is 4.5 μm, test obtain it in the irradiation emitted green light of exciting light, and quantum yield 62.5% passes through
Microscope photo observes the dispersion of wherein embedded photoluminescent material it is found that dispersing in the photoresist of quanta point material after hardening
It is all right, do not occur reuniting and cavitation, stimulated luminescence are soft uniformly.
Embodiment 3
Difference with embodiment 1 is only that, the CdSe quantum dots of external sheath zinc sulphide are replaced with indium phosphide quantum
Point, and identical surface modification step is carried out to it makes its surface with carboxyl.
Embodiment 3 obtains photoresist 3, after its film, solidifies in the case where wavelength is the ultraviolet light of 360nm, obtains thickness
The photoresist film that degree is 4.5 μm, test obtain its blue light-emitting under the irradiation of exciting light, and quantum yield 54.8% passes through
Microscope photo observes the dispersion of wherein embedded photoluminescent material it is found that dispersing in the photoresist of quanta point material after hardening
It is all right, do not occur reuniting and cavitation, stimulated luminescence are soft uniformly.
Embodiment 4
The additional amount that surface modification has the CdSe quantum dots of the external sheath zinc sulphide of carboxyl is 5g, nano titania
The additional amount of particle is 5g and partial size is the wavelength (360nm) of backlight exciting light, and the additional amount of SU8 type photoresist is 90g.
Embodiment 4 obtains photoresist 4.
Embodiment 5
It is 25g that surface modification, which has the additional amount of the CdSe quantum dots of the external sheath zinc sulphide of carboxyl, and titanium dioxide is received
The additional amount of rice corpuscles is 25g and partial size is 500nm, and the additional amount of SU8 type photoresist is 50g.
Embodiment 5 obtains photoresist 5.
Embodiment 6
Difference with embodiment 1 is only that, the CdSe quantum dots of external sheath zinc sulphide are replaced with perovskite crystal,
And identical surface modification step is carried out to it makes its surface with carboxyl, and titanium dioxide nano-particle is replaced with same particle size
Nano particles of silicon dioxide.
Embodiment 6 obtains photoresist 6.
Embodiment 7
Difference with embodiment 1 is only that, the cyclohexane solution of glutaric acid is replaced with to 1, the 10- sebacic acid of same concentrations
Cyclohexane solution, embodiment 7 obtains photoresist 7.
After obtained 7 film of photoresist, solidifies in the case where wavelength is the ultraviolet light of 360nm, obtain with a thickness of 4.5 μm
Photoresist film, test obtains it and glows under the irradiation of exciting light, and quantum yield 66.5% passes through microscope photo
The dispersion of observation wherein embedded photoluminescent material it is found that dispersion is good in the photoresist of quanta point material after hardening,
Do not occur reuniting and cavitation, stimulated luminescence are soft uniformly.
Embodiment 8
Difference with embodiment 1 is only that, the cyclohexane solution of glutaric acid is replaced with to the ring of the succinic acid of same concentrations
Hexane solution, embodiment 8 obtain photoresist 8.
After obtained 8 film of photoresist, solidifies in the case where wavelength is the ultraviolet light of 360nm, obtain with a thickness of 4.5 μm
Photoresist film, test obtains it and glows under the irradiation of exciting light, and quantum yield 61.5% passes through microscope photo
The dispersion of observation wherein embedded photoluminescent material it is found that dispersion is preferable in the photoresist of quanta point material after hardening,
There is a little reunion and a little cavity, stimulated luminescence is milder uniformly.
Reference examples 1
It is the two of 100nm that 10g surface modification, which is had CdSe quantum dots, the 15g partial size of the external sheath zinc sulphide of sulfydryl,
Titanium oxide nanoparticles are uniformly mixed with the SU8 type photoresist that Microchem company, the U.S. 75g produces, and obtain photoresist 9.
Wherein, the surface modification has the CdSe quantum dots of the external sheath zinc sulphide of sulfydryl to make by the following method
It is standby:
The CdSe quantum dots of 100mg external sheath zinc sulphide are dispersed in the 3- mercaptopropionic acid that concentration is 6.25g/L
In cyclohexane solution, simultaneously mixture 2h is stirred at room temperature in ultrasonic disperse, is centrifugally separating to obtain later and is stated surface modification and have sulfydryl
External sheath zinc sulphide CdSe quantum dots.
After obtained 9 film of photoresist, solidifies in the case where wavelength is the ultraviolet light of 360nm, obtain with a thickness of 4.5 μm
Photoresist film, test obtains it and glows under the irradiation of exciting light, and quantum yield 57.1% passes through microscope photo
The dispersion of observation wherein embedded photoluminescent material it is found that dispersion is general in the photoresist of quanta point material after hardening,
There is more reunion and cavity, stimulated luminescence is uneven, it is evident that the stain of small volume in photo.
Reference examples 2
It is the two of 100nm that 10g surface modification, which is had CdSe quantum dots, the 15g partial size of the external sheath zinc sulphide of amino,
Titanium oxide nanoparticles are uniformly mixed with the SU8 type photoresist that Microchem company, the U.S. 75g produces, and obtain photoresist 10.
Wherein, the surface modification has the CdSe quantum dots of the external sheath zinc sulphide of amino to make by the following method
It is standby:
The CdSe quantum dots of 100mg external sheath zinc sulphide are dispersed in the p-aminobenzoic acid that concentration is 6.25g/L
Cyclohexane solution in, simultaneously mixture 2h is stirred at room temperature in ultrasonic disperse, is centrifugally separating to obtain later and states surface modification and have ammonia
The CdSe quantum dots of the external sheath zinc sulphide of base.
After obtained 10 film of photoresist, solidifies in the case where wavelength is the ultraviolet light of 360nm, obtain with a thickness of 4.5 μ
The photoresist film of m, test obtain it and glow under the irradiation of exciting light, and quantum yield 47.2% is shone by microscope
The dispersion of piece observation wherein embedded photoluminescent material is it is found that dispersion one in the photoresist of quanta point material after hardening
As, there is obvious reunion and cavity, stimulated luminescence is uneven, it is evident that the biggish stain of volume in photo.
Reference examples 3
By the CdSe quantum dots of 10g external sheath zinc sulphide, 15g partial size be 100nm titanium dioxide nano-particle with
The SU8 type photoresist of Microchem company, the U.S. 75g production is uniformly mixed, and obtains photoresist 11.
Reference examples 4
By the CdSe quantum dots of 10g external sheath cadmium sulfide, 15g partial size be 100nm titanium dioxide nano-particle with
The SU8 type photoresist of Microchem company, the U.S. 75g production is uniformly mixed, and obtains photoresist 12.
FIG. 1 to FIG. 4 be respectively embodiment 1, embodiment 2, reference examples 3 and reference examples 4 obtain photoresist 1, photoresist 2,
Photoresist 11 and photoresist 12 are after film and solidification, optical photograph when quantum dot therein is stimulated, wherein can be obvious
Find out, after the surface modification carboxyl to quanta point material, the dispersion performance in photoresist ontology is obviously improved,
In stimulated luminescence, occur without obvious reunion and cavity, it is suitable for using as luminescence generated by light coloured silk film that shine homogeneous soft.
Fig. 5~Fig. 7 is respectively photoresist 1, photoresist 9 and the photoresist 10 that embodiment 1, reference examples 1 and reference examples 2 obtain
After film and solidification, microscope photo when quantum dot therein is stimulated, therefrom, it is apparent that compared to other bases
Group such as amino and sulfydryl can be such that it has more with common Other substrate materials in embedded photoluminescent material surface modification carboxyl
Matched compatibility influences the quantum efficiency of embedded photoluminescent material itself also smaller.
The photoresist 1~3 obtained using Examples 1 to 3 can also be used to prepare a kind of pixelation luminescence generated by light coloured silk film, institute
The structural schematic diagram of pixelation luminescence generated by light coloured silk film is stated as shown in figure 8, by black substrate film 100 and penetrating and being dispersed in this
Light transmission sub-pixel group in black substrate film 100 is at the light transmission sub-pixel includes the red sub-pixel 201 of rectangle, six sides
The green sub-pixels 202 of shape and the blue subpixels 203 of round rectangle are obtained by the solidification of photoresist 1~3, all light transmissions respectively
Sub-pixel is 20~100 μm in the maximum gauge on the thin film planar of fast black base bottom, and obtained pixelation luminescence generated by light coloured silk film can
To be used as backlight panel or display device.
In conclusion the present invention is by by the surface modification carboxyl of traditional embedded photoluminescent material, and by itself and conventional lithography
Glue ontology is used in compounding, and can be improved dispersibility of traditional embedded photoluminescent material in photoresist ontology, is not influencing photic hair
The group that embedded photoluminescent material occurs in photoresist ontology solidification process is reduced under the premise of luminescent material quantum yield as far as possible
The defects of poly-, empty, can be used as the backlights such as pixelation luminescence generated by light coloured silk film or display material after the compounding photoetching adhesive curing makes
With comparing other existing products has higher backlight trap, the soft degree that shines, color purity and display colour gamut, can obtain
Obtain the display effect of higher quality.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of photoresist, which is characterized in that the photoresist includes photoresist ontology and is dispersed in photoresist ontology
Surface modification has the embedded photoluminescent material of carboxyl；
The embedded photoluminescent material include in quantum dot, quantum rod, nanoscale twins or perovskite crystal any one or at least
Two kinds of mixture.
2. photoresist according to claim 1, which is characterized in that the surface modification has the embedded photoluminescent material of carboxyl logical
It crosses in the solution that embedded photoluminescent material is immersed in the alkane compound containing at least two carboxyls and obtains；
Preferably, in the alkane compound containing at least two carboxyls, 1~10 carbon original is contained in the main chain of alkane carbochain
Son, further preferably 5~10 carbon atoms；
Preferably, in the alkane compound containing at least two carboxyls, carbon atom containing odd number in the main chain of alkane carbochain；
Preferably, the alkane compound containing at least two carboxyls is malonic acid, succinic acid, glutaric acid, three acid of second, 1,6-
Adipic acid, 1,7- pimelic acid, 1,8- suberic acid, any one in three acid of 1,9- azelaic acid, 1,10- sebacic acid or 1,2,7- heptan
Or at least two mixture, further preferably glutaric acid.
3. photoresist according to claim 1 or 2, which is characterized in that the photoresist ontology is that any one contains epoxy
The photoresist of key, further preferably SU8 type photoresist.
4. photoresist described according to claim 1~one of 3, which is characterized in that the embedded photoluminescent material is quantum dot；
Preferably, the quantum dot is cadmiumsulfide quantum dot, indium sulphur quantum dot, carbon quantum dot, graphene quantum dot, perovskite
Quantum dot, alloy quantum dot, indium phosphide quantum dot, the CdSe quantum dots of external sheath zinc sulphide, external sheath cadmium sulfide
CdSe quantum dots, the indium aluminium As quantum dots of external sheath aluminum gallium arsenide, the indium phosphide quantum dot of external sheath zinc selenium sulfur, outer layer packet
Cover the indium phosphide quantum dot of zinc sulphide, the lead selenide quantum dot of external sheath vulcanized lead, external sheath calcium sulfide and internal doping
There is the cadmium telluride of the zinc sulphide gallium quantum dot of copper, the cadmium telluride quantum dot of external sheath cadmium sulfide, external sheath zinc sulphide
In quantum dot any one or at least two mixture, further preferably CdSe quantum dots of external sheath zinc sulphide
Or the CdSe quantum dots of external sheath cadmium sulfide.
5. photoresist described according to claim 1~one of 4, which is characterized in that in percentage by weight, the photoresist
The content that middle surface modification has the embedded photoluminescent material of carboxyl is 5~25wt%.
6. photoresist described according to claim 1~one of 5, which is characterized in that also scatter grain containing light in the photoresist
Son；
Preferably, in percentage by weight, the content of light diffusing particles is 5~25wt% in the photoresist；
Preferably, partial size >=100nm of the light diffusing particles, further preferably 100~500nm；
Preferably, the light diffusing particles are TiO 2 particles and/or silicon dioxide granule.
7. a kind of pixelation luminescence generated by light coloured silk film, which is characterized in that the pixelation luminescence generated by light coloured silk film includes that fast black base bottom is thin
Film (100), and the light transmission sub-pixel (200) for penetrating and being dispersed in the black substrate film (100)；
The light transmission sub-pixel (200) is obtained as the photoetching adhesive curing as described in one of claim 1~6.
8. pixelation luminescence generated by light coloured silk film according to claim 7, which is characterized in that the light transmission sub-pixel (200) is
In red sub-pixel (201), green sub-pixels (202) or blue subpixels (203) any one or at least two mixing
Object, color in light transmission sub-pixel (200) by surface modification in the photoresist after solidifying have carboxyl embedded photoluminescent material by
Stimulated emission light spectrum determines, and is mutually not attached between the different light transmission sub-pixel (200) of any two color；
Preferably, also contain yellow sub-pixel in the light transmission sub-pixel (200).
9. pixelation luminescence generated by light coloured silk film according to claim 7 or 8, which is characterized in that the light transmission sub-pixel (200)
It include in rectangle, square, circle, ellipse, triangle or diamond shape in the shape on fast black base bottom thin film planar (100)
Any one or at least two figures；
Preferably, the light transmission sub-pixel (200) is 20~100 μ in the maximum gauge in black substrate film (100) plane
m。
10. a kind of pixelation luminescence generated by light coloured silk film as described in one of claim 7~9 is in backlight panel or display device
Using.
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