CN113064324A - Silicon quantum dot photoresist, color film layer, OLED display structure and display - Google Patents
Silicon quantum dot photoresist, color film layer, OLED display structure and display Download PDFInfo
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- CN113064324A CN113064324A CN202010001754.4A CN202010001754A CN113064324A CN 113064324 A CN113064324 A CN 113064324A CN 202010001754 A CN202010001754 A CN 202010001754A CN 113064324 A CN113064324 A CN 113064324A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/016—Diazonium salts or compounds
- G03F7/0166—Diazonium salts or compounds characterised by the non-macromolecular additives
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
- G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/016—Diazonium salts or compounds
- G03F7/0163—Non ionic diazonium compounds, e.g. diazosulphonates; Precursors thereof, e.g. triazenes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/856—Arrangements for extracting light from the devices comprising reflective means
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/30—Devices specially adapted for multicolour light emission
- H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]
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Abstract
The application discloses a silicon quantum dot photoresist, a color film layer, an OLED display structure and a display, wherein the OLED display structure comprises a photoinitiator, a phenolic resin derivative and a diazonaphthol derivative, and further comprises single-color silicon quantum dots; the single-color silicon quantum dots account for 2-7% of the total mass of the photoinitiator, the phenolic resin derivative and the diazonaphthol derivative. According to the technical scheme provided by the embodiment of the application, the silicon quantum dots which are free of heavy metal elements, good in optical property and good in chemical stability are used as quantum dot light emitting units and introduced into the photoresist, so that the use of the heavy metal quantum dots is avoided in the preparation process, and the photoresist is more environment-friendly. The organic light emitting diode can be applied to display devices such as Liquid Crystal Displays (LCDs), Organic Light Emitting Diodes (OLEDs) and the like, and can achieve the purpose of color display after being patterned through a photoetching process. The manufactured display device based on the silicon quantum dot color film has higher brightness, wider color gamut and better color purity.
Description
Technical Field
The present invention relates generally to the field of photoresists, and more particularly to silicon quantum dot photoresists, color film layers, OLED display structures, and displays.
Background
With the development of display technology, people have higher and higher requirements on the display quality of display devices. In a conventional method for realizing full color Display, a White LCD (Liquid Crystal Display) and a White OLED (White Organic Light-Emitting Diode) are used as backlight sources, and a Color Filter (CF) converts White Light into RGB three colors, so one of the key core parts determining the Display quality of the device is a color Filter layer. The conventional color filter layer is obtained by patterning color photoresist, the color photoresist mainly comprises pigment resin and photoresist, and the pigment resin has the defects of low transmittance and wide transmission spectrum, so that the manufactured device is difficult to realize the display requirements of high brightness and high color gamut. Therefore, the quantum dot photoresist prepared by using the quantum dots to replace common pigment resin has come into use, and the quantum dot photoresist is applied to a display device, so that the display device can meet the display requirements of high brightness, high color gamut and high color purity.
Quantum Dots (QDs) are generally spherical semiconductor nanocrystals composed of II-VI or I-III-VI elements, with particle diameters typically ranging from a few nanometers to tens of nanometers. Due to the fact that the particle size is close to the Bohr radius of the material, quantum confinement effect is generated, the energy level structure is changed from continuous to discrete, and QDs display a unique phenomenon of stimulated luminescence. Generally, the smaller the size of QDs, the larger the energy band gap, and the more energetic visible light is radiated after excitation, which is manifested as a "blue shift phenomenon" such as the size reduction of cadmium selenide (CdSe) from 6.6nm to 2.0nm, and the blue shift of the emission wavelength from 630nm to 460 nm. The QDs has high molar absorptivity, high light conversion efficiency and extremely narrow half-peak width which is generally less than 25nm, and is a perfect full-color display material capable of replacing pigment resin. However, to manufacture a quantum dot photoresist, quantum dots need to be dispersed in the photoresist, and because the photoresist contains various high molecular materials such as an initiator, a polymer monomer, a polymer, an additive and the like, the surface chemical environment of the quantum dots is complex, and the luminous efficiency of the quantum dots is greatly affected; in the process of synthesizing the traditional quantum dots, the introduction of heavy metal elements such as Cd, In, Pb and the like can cause cost increase, human harm and environmental pollution, and is not beneficial to mass production.
Silicon has not been of interest as an indirect bandgap semiconductor for its light emitting properties. With the discovery of the mesoporous nano-silicon photoluminescence effect, people have dreamy for a long time to make the full-silicon photonic integrated device possible. With further research, researchers have found that the photoluminescence phenomenon of silicon is caused by quantum confinement effects. When the silicon particle size is reduced to near-bohr radius, the indirect bandgap gradually becomes like the direct bandgap, the probability of electron hole radiative recombination increases, and photoluminescence occurs, and these particles are collectively called silicon quantum dots (SiQDs). Through years of development, researchers can successfully prepare SiQDs spanning the whole visible spectrum, the half-peak width can be controlled within 20nm, and the internal quantum efficiency is close to 100%. More importantly, the surface modification of SiQDs is simple, polymerizable groups which can be copolymerized with the photoresist monomer can be modified on the surface of the SiQDs, in-situ film formation is carried out in the photoetching process, the film formation dispersibility and uniformity are improved, and the introduction of heavy metal quantum dots is avoided while the light efficiency is ensured.
Disclosure of Invention
In view of the above-mentioned defects or shortcomings in the prior art, it is desirable to provide a silicon quantum dot photoresist, a color film layer, an OLED display structure and a display.
The first aspect provides a silicon quantum dot photoresist which is characterized by comprising a photoinitiator, a phenolic resin derivative, a diazonaphthol derivative and a single-color silicon quantum dot;
the doping concentration of the single-color silicon quantum dots accounts for 2-7% of the total mass of the photoinitiator, the phenolic resin derivative and the diazonaphthol derivative.
In a second aspect, a color film layer is provided, which includes a red sub-pixel, a green sub-pixel, and a blue sub-pixel, and the red sub-pixel, the green sub-pixel, and the blue sub-pixel are all prepared by using the above silicon quantum dot photoresist.
In a third aspect, an OLED display structure is provided, which includes a blue backlight layer, a reflective layer is disposed on the blue backlight layer, the reflective layer is provided with the color film layer, and the color film layer is provided with a substrate.
In a fourth aspect, an OLED display is provided, which includes the OLED display structure.
According to the technical scheme provided by the embodiment of the application, the silicon quantum dots which are free of heavy metal elements, good in optical property and good in chemical stability are used as quantum dot light emitting units and introduced into the photoresist, so that the problem that the luminous efficiency is reduced due to the fact that fluorescence generated after the traditional II-IV group and I-III-VI group quantum dots are contacted with the photoresist in a complex chemical environment is quenched is solved, meanwhile, in the preparation process, the use of the heavy metal quantum dots is avoided, and the photoresist is more environment-friendly. The organic light emitting diode can be applied to display devices such as Liquid Crystal Displays (LCDs), Organic Light Emitting Diodes (OLEDs) and the like, and can achieve the purpose of color display after being patterned through a photoetching process. The manufactured display device based on the silicon quantum dot color film has higher brightness, wider color gamut and better color purity.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the following detailed description of non-limiting embodiments thereof, made with reference to the accompanying drawings in which:
fig. 1 is a schematic view of the OLED display structure in this embodiment.
Detailed Description
The present application will be described in further detail with reference to the following drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention. It should be noted that, for convenience of description, only the portions related to the present invention are shown in the drawings.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail below with reference to the embodiments with reference to the attached drawings.
The embodiment provides a silicon quantum dot photoresist, which comprises a photoinitiator, a phenolic resin derivative and a diazonaphthol derivative, and also comprises single-color silicon quantum dots;
the doping concentration of the single-color silicon quantum dots accounts for 2-7% of the total mass of the photoinitiator, the phenolic resin derivative and the diazonaphthol derivative.
In the embodiment, the silicon quantum dots are used as the quantum dot light emitting units, the silicon quantum dots are free of heavy metal elements, good in optical property and good in chemical stability, and the problem that the luminous efficiency is reduced due to the fact that traditional II-IV group and I-III-VI group quantum dots are subjected to fluorescence quenching after contacting with photoresist in a complex chemical environment is solved by introducing a photoinitiator, a phenolic resin derivative and a diazonaphthol derivative mixture.
Further, the photoinitiator comprises dibenzoyl peroxide and/or azodiiso-and/or peroxydicarbonate and/or lauroyl peroxide and/or azodiisobutyronitrile and/or dicyclohexyl peroxydicarbonate.
In the present embodiment, a photoinitiator is used as a raw material, which generates a radical under an illumination condition to further excite a polymerization reaction of a phenol resin derivative and a diazonaphthol derivative, which is a typical radical-induced polymerization reaction, according to the following formula.
Further, the monochromatic silicon quantum dots comprise red silicon quantum dots, and the doping concentration of the red silicon quantum dots is 4% -6%.
In this embodiment, silicon quantum dots with different colors are added to the mixture to prepare photoresists with different colors, and further, the photoresists with different colors can be used for preparing sub-pixels with different colors on a color film, wherein the prepared photoresists are negative resists, and monochromatic silicon quantum dot color films with different patterns are prepared by an exposure and development method. The doping concentration of the red silicon quantum dots is controlled to be 4% -6%, a fluorescence quenching phenomenon can occur after the doping concentration exceeds 6%, and the preferred doping concentration of the red silicon quantum dots is 5%.
Further, the monochromatic silicon quantum dots comprise green silicon quantum dots, and the doping concentration of the green silicon quantum dots is 2% -3%. The green silicon quantum dot photoresist is prepared by doping the green silicon quantum dots, the doping concentration is controlled to be between 2% and 3%, a fluorescence quenching phenomenon can occur after the doping concentration exceeds 3%, a phenomenon of red shift of a PL (Photoluminescence) spectrum can occur, and the preferred doping concentration of the green silicon quantum dots is 3%.
Further, the monochromatic silicon quantum dots comprise blue silicon quantum dots, and the doping concentration of the blue silicon quantum dots is 5% -7%. The blue silicon quantum dot photoresist is prepared by doping the blue silicon quantum dots, the doping concentration is controlled to be between 5% and 7%, a fluorescence quenching phenomenon can occur after the doping concentration exceeds 7%, a phenomenon of red shift of a PL (Photoluminescence) spectrum can occur, and the preferred doping concentration of the blue silicon quantum dots is 7%.
The embodiment also provides a preparation method of the silicon quantum dots, wherein the silicon quantum dots with different emission wavelengths are prepared according to the etching regulation time, and the preparation method comprises the following steps:
the method comprises the following steps of (1) taking silsesquioxane as a raw material, feeding the silsesquioxane into a high-temperature furnace (1100 ℃), introducing a mixed gas of 5% of hydrogen and 95% of argon, and reacting for 12 hours to prepare silicon oxide-coated monocrystalline silicon;
preparing 60mL of etching solution with ethanol content of 70% and HF content of 30%;
respectively putting monocrystalline silicon (5g) wrapped by silicon oxide into 20mL of HF etching solution, putting the monocrystalline silicon into an ultrasonic reactor, and setting the power to be 1.5W/cm and the frequency to be 30 kH;
carrying out ultrasonic reaction for 2H to generate silicon quantum dots with the particle size of 6-8 nm, wherein the light emitting peak value is 620nm (red), and the surface functional group is a Si-H bond;
carrying out ultrasonic reaction for 4H to generate silicon quantum dots with the particle size of 4-5 nm, wherein the light emitting peak value is 550nm (green), and the surface functional group is a Si-H bond;
and carrying out ultrasonic reaction for 8H to generate silicon quantum dots with the particle size of 2-3 nm, wherein the light emitting peak value is 450nm (blue), and the surface functional group is a Si-H bond.
The prepared silicon quantum dots have the excellent characteristics of long service life, narrow half-peak width, weaker aggregation induction and chemical induction fluorescence quenching phenomena than traditional II-IV group and I-III-VI group quantum dots and the like, and are used for preparing subsequent silicon quantum dot colored films.
The embodiment also provides a color film layer, which comprises a red sub-pixel, a green sub-pixel and a blue sub-pixel, wherein the red sub-pixel, the green sub-pixel and the blue sub-pixel are all prepared by adopting the silicon quantum dot photoresist.
In the implementation, the silicon quantum dot photoresists with different colors are used for preparing the color film layer, and the prepared color film layer can be applied to, but not limited to, Liquid Crystal Displays (LCDs), Organic Light Emitting Diodes (OLEDs) and other display devices to realize high-brightness and high-color-gamut display.
As shown in fig. 1, the present embodiment further provides an OLED display device, which includes a blue backlight layer 2, a reflective layer 3 is disposed on the blue backlight layer 2, the color film layer 1 is disposed on the reflective layer 3, and a substrate 4 is disposed on the color film layer 1.
The embodiment also provides an embodiment of an OLED display device, wherein the display device adopts the color film layer 1 prepared by the silicon quantum dot photoresist, the OLED display device includes a blue backlight layer 2, the blue backlight layer 2 can improve the light-emitting conversion efficiency of the color film layer of the silicon quantum dots to the greatest extent, the blue light can excite the red silicon quantum dots and the green silicon quantum dots to emit light, and meanwhile, the blue silicon quantum dot color film can correct the blue light-emitting of the OLED, so as to optimize the half-peak width.
Further, the wavelength of the blue light in the blue backlight layer is 360nm-430 nm. The blue light with the wavelength in the blue backlight layer provided in the embodiment can effectively excite red and green light, so that high-brightness and high-color-gamut display is realized.
Further, the reflective layer is a bragg reflective layer. In this embodiment, a bragg reflection layer is further disposed between the color film layer and the backlight layer, and the bragg reflection layer is made of two or more slave materials with relatively large transparent refractive indexes, and can resonantly enhance blue light, emit red and green light, increase red and green light, and realize high-brightness and high-color-gamut display.
When the blue backlight penetrates through the Bragg reflection layer to reach the blue quantum dot colored glue, the light with the short wavelength is not influenced by the refractive index deviation, and the light is emitted normally; when the blue backlight penetrates through the Bragg reflecting layer to the green quantum dot colored glue, the quantum dots absorb blue light energy to emit green light, and the green light polarized downwards is emitted in the Bragg reflecting layer due to refractive index deviation, so that the light emitting efficiency of the green light is enhanced; when the blue backlight penetrates through the Bragg reflecting layer to the red quantum dot color adhesive, the quantum dots absorb the energy of the blue light to emit red light, and the red light polarized downwards reflects to enhance the light emission of the red light; finally, the effect of high-brightness and high-color gamut display is realized.
The embodiment also provides an OLED display, which includes the OLED display structure.
According to the application, the silicon quantum dots with different colors are used as the light emitting units and added into the photoresist to prepare the silicon quantum dot photoresist with different colors, so that the problem that the fluorescence generated by the traditional II-IV group and I-III-VI group quantum dots after contacting the photoresist with a complex chemical environment is quenched and the luminous efficiency is reduced is solved, and meanwhile, in the preparation process, the use of heavy metal quantum dots is avoided, so that the preparation method is more environment-friendly. The prepared silicon quantum dot photoresists with different colors can be used for preparing color films, and are applied to display devices such as LCDs (liquid crystal displays), OLEDs (organic light emitting diodes) and the like to realize the effects of high brightness and high color gamut display.
The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Claims (10)
1. The silicon quantum dot photoresist is characterized by comprising a photoinitiator, a phenolic resin derivative and a diazonaphthol derivative, and also comprising single-color silicon quantum dots;
the doping concentration of the single-color silicon quantum dots accounts for 2-7% of the total mass of the photoinitiator, the phenolic resin derivative and the diazonaphthol derivative.
2. The silicon quantum dot photoresist of claim 1, wherein the photoinitiator comprises dibenzoyl peroxide and/or azodiiso-and/or peroxydicarbonate and/or lauroyl peroxide and/or azobisisobutyronitrile and/or dicyclohexyl peroxydicarbonate.
3. The silicon quantum dot photoresist of claim 1 or 2, wherein the single-color silicon quantum dots comprise red silicon quantum dots, and the doping concentration of the red silicon quantum dots is 4% -6%.
4. The silicon quantum dot photoresist of claim 1 or 2, wherein the monochromatic silicon quantum dots comprise green silicon quantum dots, and the doping concentration of the green silicon quantum dots is 2% -3%.
5. The silicon quantum dot photoresist of claim 1 or 2, wherein the monochromatic silicon quantum dots comprise blue silicon quantum dots, and the doping concentration of the blue silicon quantum dots is 5% -7%.
6. A color film layer comprising a red sub-pixel, a green sub-pixel and a blue sub-pixel, wherein the red sub-pixel, the green sub-pixel and the blue sub-pixel are all prepared by using the silicon quantum dot photoresist of any one of claims 1 to 5.
7. An OLED display structure, comprising a blue backlight layer, wherein a reflective layer is disposed on the blue backlight layer, a color film layer according to claim 6 is disposed on the reflective layer, and a substrate is disposed on the color film layer.
8. The OLED display structure of claim 7 wherein the blue light in the blue backlight layer has a wavelength of 360nm to 430 nm.
9. The OLED display structure of claim 7, wherein said reflective layer is a bragg reflective layer.
10. An OLED display comprising the OLED display structure of any one of claims 7-9.
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