CN112010258B - Preparation method of composite film with micro-nano structure array - Google Patents
Preparation method of composite film with micro-nano structure array Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 39
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- 239000000463 material Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 42
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- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 22
- 150000004760 silicates Chemical class 0.000 claims description 16
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- -1 polydimethylsiloxane Polymers 0.000 claims description 10
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 10
- 230000005855 radiation Effects 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 8
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 5
- 239000000084 colloidal system Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000004049 embossing Methods 0.000 claims description 4
- VIFIHLXNOOCGLJ-UHFFFAOYSA-N trichloro(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CC[Si](Cl)(Cl)Cl VIFIHLXNOOCGLJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 description 21
- 230000008020 evaporation Effects 0.000 description 18
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 18
- 239000010410 layer Substances 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000004806 packaging method and process Methods 0.000 description 12
- 238000005057 refrigeration Methods 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 238000000151 deposition Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
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- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
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- 101710162828 Flavin-dependent thymidylate synthase Proteins 0.000 description 3
- 101710135409 Probable flavin-dependent thymidylate synthase Proteins 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000003491 array Methods 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 238000012864 cross contamination Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
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- 239000007788 liquid Substances 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
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- 238000004020 luminiscence type Methods 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B7/00—Microstructural systems; Auxiliary parts of microstructural devices or systems
- B81B7/04—Networks or arrays of similar microstructural devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
- B81C1/00031—Regular or irregular arrays of nanoscale structures, e.g. etch mask layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00436—Shaping materials, i.e. techniques for structuring the substrate or the layers on the substrate
- B81C1/00444—Surface micromachining, i.e. structuring layers on the substrate
- B81C1/0046—Surface micromachining, i.e. structuring layers on the substrate using stamping, e.g. imprinting
-
- 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
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Computer Hardware Design (AREA)
- Nanotechnology (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a preparation method of a composite film with a micro-nano structure array, which prepares an organic-inorganic composite film material through an improved sol-gel technology, prepares the micro-nano structure array on a micro-lens through an ultraviolet soft imprinting technology and a secondary spin coating method.
Description
Technical Field
The invention relates to preparation of a micro-nano structure array on an organic-inorganic composite film, in particular to a preparation method of a composite film with the micro-nano structure array.
Background
The Organic Light Emitting Diode (OLED) has the characteristics of self luminescence, wide viewing angle, high reaction speed, high contrast, low energy consumption, green and environment-friendly property, long service life, flexible display and the like, is considered as a new generation of illumination and display technology following an LCD, however, most photons cannot escape to the air due to the influence of factors such as reflection and refraction of ITO, a glass substrate, an air surface layer and the like, the photon utilization rate is low, the development and the application of the OLED are hindered, in the past two decades, researchers propose a plurality of solutions, mainly comprising the utilization of photonic crystals, the utilization of micro-resonant cavity structures, the roughening of the substrate surface, the insertion of electrode control layers and the like, but the processes of the methods are complex, the cost is high, and the internal structure of the OLED needs to be changed. The method for improving the light extraction efficiency of the OLED by applying the micro-nano structure developed in recent years has the characteristics of simple manufacture, low cost, no influence on the radiation spectrum angle distribution and the like.
The development and development of micro-nano structure arrays can be traced back to cat eye lens plate integrated photography proposed by lippman in the beginning of the 20 th century. Korean LG company researchers in 2007 reported that the use of high fill factor micro-nano structured arrays enhanced the light output efficiency of OLEDs. The micro-nano structure array with high filling factor is manufactured on the surface of the OLED device by using a micro-mechanical manufacturing process of channel forming and macromolecule pattern layer vapor deposition, so that the output efficiency of the OLED is improved by 48%; in 2012, francesco Galeotti et al, proposed a micro-nano structured array for enhancing light extraction in OLED, and a micro-nano structured array of cellular micropores was fabricated using Polydimethylsiloxane (PDMS) material, by which the light extraction capability of OLED can be enhanced, the light output coupling can be improved, and the external quantum efficiency can be enhanced by 34%, and in 2016 Hyun Soo Kim, seong Il Moon, proposed a novel preparation method of conical and hemispherical polymethyl methacrylate (PMMA) micro-nano structured array. Finally, new manufacturing methods for pyramid and hemispherical micro-nano structure arrays were successfully developed. The efficiency of the OLED device with the pyramid micro-nano structure array with the contact angle of 52.6 degrees, 35.7 degrees and 50.4 degrees is improved by 64 percent, 96 percent and 117 percent respectively compared with the brightness of the OLED without the micro-nano structure array. The Young Yun Kim of 2016 proposes a novel micro-nano structure array doped with Al 2O3 nano particles to improve the light emitting efficiency of OLED, and his study shows that the flexible polymer can effectively improve the external quantum efficiency of OLED, but these methods are difficult to ensure the integrity and uniformity of the structure morphology in the prepared micro-nano structure array.
Disclosure of Invention
The invention aims to: the invention aims to provide a preparation method of a composite film of a micro-nano structure array, which solves the problems of uneven imprinting and incomplete structure of the micro-nano structure array.
The technical scheme is as follows: the preparation method of the composite film with the micro-nano structure array comprises the following steps:
(1) Taking gamma-glycidoxypropyl trimethoxy silane and methacryloxypropyl trimethoxy silane as organic precursors, taking tetrabutyl titanate as inorganic precursors, stirring and mixing, and preparing organic-inorganic modified silicate material sol by a sol-gel method;
(2) Adding a bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide photoinitiator into the sol, and uniformly stirring at room temperature in a darkroom to obtain an organic-inorganic modified silicate composite film material;
(3) Mixing a precursor of polydimethylsiloxane with a curing agent, fully stirring, and standing until all bubbles disappear to obtain PDMS colloid;
(4) Pouring the PDMS colloid in the step (3) on the pretreated AAO template, putting the AAO template into a vacuum steam box, and removing the PDMS template from the template after complete solidification to obtain the PDMS template;
(5) Dispersing and dripping the organic-inorganic modified silicate composite film material prepared in the step (2) on a substrate by using polyethylene naphthalate as the substrate, and preparing the organic-inorganic modified silicate material into a film by adopting a spin coating method;
(6) Pressing the PDMS template prepared in the step (3) on the film prepared in the step (5), performing ultraviolet exposure after imprinting, and removing the PDMS template from the film after complete solidification to obtain the array film with the micro-nano structure;
(7) And (3) adsorbing the micro-nano structure array film on a spin coater, dripping the organic-inorganic modified silicate composite film material prepared in the step (2) at the center of the micro-nano structure array film, spin coating by adopting a spin coating method to form a layer of film which covers the micro-nano structure array, and drying after ultraviolet curing to obtain the double-layer micro-nano structure array film.
Wherein in the step (1), the molar ratio of tetra-n-butyl titanate, gamma-glycidoxypropyl trimethoxysilane and methacryloxypropyl trimethoxysilane is 1:1:1-3:2:2, and the stirring time is 24-27 hours.
The mass of the bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide added in the step (2) accounts for 4% of the total mass of the mixed solution, and the stirring time is 0.5-1 hour.
The ratio of the precursor of the Polydimethylsiloxane (PDMS) to the curing agent in the step (3) is 10:1-9:2, and the standing time is 15-30 minutes.
In order to facilitate the peeling of PDMS from the AAO template, the AAO template in the step (4) is pretreated by: firstly, soaking an AAO template in a mixture of 1H, 2H-perfluoro decyl trichlorosilane, absolute ethyl alcohol and acetic acid, then refrigerating in a refrigerator, and heating the whole in an oven after the refrigerating is finished.
In the step (4), the AAO template is a micro-nano structure array and is a symmetrical double-pass AAO template, the holes are all in a right circular shape, the arrangement mode is hexagonal close-packed, the holes are uniform in diameter, the internal pore channels are straight and parallel and do not intersect, the center-to-center distance of the holes is 450nm, the hole diameter is 170nm, and the hole diameter length is 40-60 mu m.
The spin coating time in the step (5) is 60-80 seconds, and the spin coating speed is 1200-1800 revolutions per minute.
The embossing pressure in the step (6) is 10000Pa, the embossing time is 15-30 minutes, the ultraviolet light exposure wavelength is 365nm, the radiation intensity at the 365nm wavelength is 900mW/cm 3, and the curing time is 20-40 minutes.
The spin coating time in the step (7) is 60-80 seconds, and the spin coating speed is 1000-3000 rpm.
The heating temperature of the drying in the step (7) is 80-90 ℃ and the heating time is 20-30 minutes. (
The beneficial effects are that: the micro-nano structure array is obtained by combining the organic-inorganic composite film and the micro-nano structure array structure and using the ultraviolet soft imprinting method, has clear overall outline, complete imprinting and clear structure, basically keeps the shape on the template, is regular in arrangement, does not change greatly, has good overall uniformity and smooth surface, does not have redundant impurities, has good appearance of a single micro-lens, has no obvious defect of range, and has obvious improvement on the current efficiency of the device after combining the micro-nano structure array with the OLED device.
Drawings
FIG. 1 is a surface topography of a micro-nano structure array on an organic-inorganic composite film obtained in example 1;
Fig. 2 is a current efficiency graph of the green OLED device obtained in example 1.
Detailed Description
The invention will be further described with reference to examples and figures.
Example 1
The invention discloses a preparation method of a composite film with a micro-nano structure array, which comprises the following steps:
(1) 1 mol of tetrabutyl titanate and 4 mol of acetylacetone, mixing and stirring for about 1 hour, 1 mol of gamma-glycidoxypropyl trimethoxysilane and 4 mol of absolute ethanol and 4 mol of deionized water, mixing and stirring for about 30 minutes, adding 0.01 mol of hydrochloric acid (concentration of 37 wt%) as a catalyst, and stirring the solution again for about 1 hour, 1 mol of methacryloxypropyl trimethoxysilane and 3 mol of isopropyl alcohol and 3 mol of deionized water, and adding 0.01 mol of hydrochloric acid (concentration of 37 wt%) as a catalyst, mixing and stirring for about 1 hour, three components according to TiO 2: GLYMO: mixing the MEMO with the molar ratio of 1:1:1, and continuing stirring for 24-27 hours;
(2) After the stirring is finished, adding 4% of bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide by weight of the total mass into the mixed solution as a photoinitiator, and continuously stirring at room temperature in a darkroom for about 0.5-1 hour, so that the carbon-carbon double bonds of MEMO in the mixed solution can be polymerized under the irradiation of UV light;
(3) Mixing a precursor of Polydimethylsiloxane (PDMS) and a curing agent thereof in a paper cup according to a ratio of 10:1, fully stirring, and standing for 15-30 minutes until all bubbles disappear;
(4) The AAO template is pretreated, the AAO template is soaked in a mixture of 1H, 2H-perfluoro decyl trichlorosilane (FDTS), absolute ethyl alcohol and acetic acid, the mixing ratio is 1:100:2, then the whole is stored in a refrigerator for refrigeration, the refrigeration temperature is 5 ℃, the refrigeration time is 24 hours, the whole is placed in an oven for heating after the refrigeration is finished, the temperature is 150 ℃ for 24 hours, the AAO template has lower surface free energy after the treatment, and PDMS can be easily removed from the AAO template;
(5) The symmetrical bi-pass AAO is used as a template, the center-to-center distance of the holes is 450nm, the aperture is 170nm, and the aperture length is 40-60 mu m. Pouring PDMS on a template, placing the template into a vacuum steam box, heating at 90 ℃ for 30 minutes after pouring the whole silicon wafer, and taking off the template from the photoresist template gently in order to remove bubbles generated by pouring and solidify PDMS liquid;
(6) Using polyethylene naphthalate (PEN) with the size of 2cm multiplied by 2cm as a flexible substrate, adsorbing the flexible substrate on a sucker of a spin coater, dripping a small amount of the organic-inorganic modified silicate material prepared in (2) on the substrate by using a needle tube, and performing spin coating at the spin coating rate of 1200 revolutions per minute for 60 seconds to prepare an organic-inorganic composite film on the flexible substrate;
(7) Pressing the PDMS template prepared in the step (4) on the film prepared in the step (5), applying pressure with the pressure of 10000Pa, then placing the whole under an ultraviolet xenon lamp for ultraviolet exposure with the ultraviolet exposure wavelength of 365nm, the radiation intensity at 365nm being 900mW/cm 3 and the curing time being 30 minutes, and removing the PDMS template from the film after complete curing;
(8) Adsorbing the torn micro-nano structure array on a spin coater again, taking a small amount of the organic-inorganic modified silicate material prepared in the step (2) at the center of the structure by using a needle tube, performing rapid spin coating by using a spin coating method, wherein the spin coating speed is 1000 revolutions per minute, the spin coating time is 60 seconds, forming a layer of thinner film to cover the array, forming a double-layer irregular film structure, performing ultraviolet curing again, wherein the ultraviolet exposure wavelength is 365nm, the radiation intensity at 365nm is 900mW/cm 3, and the curing time is 15-30 minutes;
(9) Placing the micro-nano structure array prepared in the step (8) into an oven, heating to remove water of a solvent, wherein the heating temperature is 80-90 ℃, the heating time is 20-30 minutes, and after heating is finished, manufacturing the micro-nano structure array on the flexible substrate;
(10) The OLED device structure is MoO3 (3 mm)/Ag (15 mm)/MoO 3 (10 mm)/NPB (60 mm)/Alq 3 (60 mm)/Liq (2 mm)/Al (100 mm), wherein MoO3/Ag/MoO3 is used as an anode, NPB is used as a hole transport layer, alq3 is used as a light emitting layer, and Liq/Al is used as a cathode. The evaporation process can be divided into three steps: depositing an organic-inorganic composite film, depositing an electrode and packaging in a glove box. When depositing organic-inorganic composite film, firstly placing the treated sample into a vacuum evaporation cabin of an evaporator, closing the cabin door, vacuumizing, evaporating when the vacuum degree of the cabin body reaches 4 x 10 -4 Pa, and keeping the evaporation rate of the small molecular material at the same time In order to prevent cross contamination of materials in the cabin during evaporation, a baffle plate is required to be used for shielding when the evaporation materials are replaced. Then metal electrode evaporation is carried out, and the metal electrode density is higher, so that a higher evaporation rate is needed, and the metal electrode density is generally kept at/>After the electrodes are steamed, the device is moved from the rear cabin door into a glove box for packaging, and a glass sheet coated with a mixture of packaging glue and calcium oxide is adopted during packaging.
Example 2
The invention discloses a preparation method of a composite film with a micro-nano structure array, which comprises the following steps:
(1) 1 mol of tetrabutyl titanate and 4 mol of acetylacetone, mixing and stirring for about 1 hour, 1 mol of gamma-glycidoxypropyl trimethoxysilane and 4 mol of absolute ethanol and 4 mol of deionized water, mixing and stirring for about 30 minutes, adding 0.01 mol of hydrochloric acid (concentration of 37 wt%) as a catalyst, and stirring the solution again for about 1 hour, 1 mol of methacryloxypropyl trimethoxysilane and 3 mol of isopropyl alcohol and 3 mol of deionized water, and adding 0.01 mol of hydrochloric acid (concentration of 37 wt%) as a catalyst, mixing and stirring for about 1 hour, three components according to TiO 2: GLYMO: mixing the MEMO with the molar ratio of 5:4:4, and continuing stirring for 24 hours;
(2) After the stirring is finished, adding 4% of bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide by weight of the total mass into the mixed solution as a photoinitiator, and continuously stirring at room temperature in a darkroom for about 0.5-1 hour, so that the carbon-carbon double bonds of MEMO in the mixed solution can be polymerized under the irradiation of UV light;
(3) Mixing a precursor of Polydimethylsiloxane (PDMS) and a curing agent thereof in a paper cup according to a ratio of 10:2, fully stirring, and standing for 15 minutes until all bubbles disappear;
(4) The AAO template is pretreated, the AAO template is soaked in a mixture of 1H, 2H-perfluoro decyl trichlorosilane (FDTS), absolute ethyl alcohol and acetic acid, the mixing ratio is 1:100:2, then the whole is stored in a refrigerator for refrigeration, the refrigeration temperature is 5 ℃, the refrigeration time is 24 hours, the whole is placed in an oven for heating after the refrigeration is finished, the temperature is 150 ℃ for 24 hours, the AAO template has lower surface free energy after the treatment, and PDMS can be easily removed from the AAO template;
(5) The symmetrical bi-pass AAO is used as a template, the center-to-center distance of the holes is 450nm, the aperture is 170nm, and the aperture length is 40-60 mu m. Pouring PDMS on a template, placing the template into a vacuum steam box, heating at 90 ℃ for 30 minutes after pouring the whole silicon wafer, and taking off the template from the photoresist template gently in order to remove bubbles generated by pouring and solidify PDMS liquid;
(6) Using polyethylene naphthalate (PEN) with the size of 2cm multiplied by 2cm as a flexible substrate, adsorbing the flexible substrate on a sucker of a spin coater, dripping a small amount of the organic-inorganic modified silicate material prepared in (2) on the substrate by using a needle tube, and performing spin coating at the spin coating rate of 1500 rpm for 70 seconds to prepare an organic-inorganic composite film on the flexible substrate;
(7) Pressing the PDMS template prepared in the step (4) on the film prepared in the step (5), applying pressure with the pressure of 10000Pa and the imprinting time of 15-30 minutes, then placing the whole under an ultraviolet xenon lamp for ultraviolet exposure with the ultraviolet exposure wavelength of 365nm, and taking off the PDMS template from the film after complete curing, wherein the radiation intensity at the wavelength of 365nm is 900mW/cm 3 and the curing time is 20-40 minutes;
(8) Adsorbing the torn micro-nano structure array on a spin coater again, taking a small amount of the organic-inorganic modified silicate material prepared in the step (2) at the center of the structure by using a needle tube, performing rapid spin coating by using a spin coating method, wherein the spin coating speed is 2000 rpm, the spin coating time is 70 seconds, forming a layer of thinner film to cover the array, forming a double-layer irregular film structure, performing ultraviolet curing again, wherein the ultraviolet exposure wavelength is 365nm, the radiation intensity at 365nm is 900mW/cm 3, and the curing time is 15-30 minutes;
(9) Placing the micro-nano structure array prepared in the step (8) into an oven, heating to remove water of a solvent, wherein the heating temperature is 80-90 ℃, the heating time is 20-30 minutes, and after heating is finished, manufacturing the micro-nano structure array on the flexible substrate;
(10) The OLED device structure is MoO3 (3 mm)/Ag (15 mm)/MoO 3 (10 mm)/NPB (60 mm)/Alq 3 (60 mm)/Liq (2 mm)/Al (100 mm), wherein MoO3/Ag/MoO3 is used as an anode, NPB is used as a hole transport layer, alq3 is used as a light emitting layer, and Liq/Al is used as a cathode. The evaporation process can be divided into three steps: depositing an organic-inorganic composite film, depositing an electrode and packaging in a glove box. When depositing organic-inorganic composite film, firstly placing the treated sample into a vacuum evaporation cabin of an evaporator, closing the cabin door, vacuumizing, evaporating when the vacuum degree of the cabin body reaches 4 x 10 -4 Pa, and keeping the evaporation rate of the small molecular material at the same time In order to prevent cross contamination of materials in the cabin during evaporation, a baffle plate is required to be used for shielding when the evaporation materials are replaced. Then metal electrode evaporation is carried out, and the metal electrode density is higher, so that a higher evaporation rate is needed, and the metal electrode density is generally kept at/>After the electrodes are steamed, the device is moved from the rear cabin door into a glove box for packaging, and a glass sheet coated with a mixture of packaging glue and calcium oxide is adopted during packaging.
Example 3
The invention discloses a preparation method of a composite film with a micro-nano structure array, which comprises the following steps:
(1) 1 mol of tetrabutyl titanate and 4 mol of acetylacetone, mixing and stirring for about 1 hour, 1 mol of gamma-glycidoxypropyl trimethoxysilane and 4 mol of absolute ethanol and 4 mol of deionized water, mixing and stirring for about 30 minutes, adding 0.01 mol of hydrochloric acid (concentration of 37 wt%) as a catalyst, and stirring the solution again for about 1 hour, 1 mol of methacryloxypropyl trimethoxysilane and 3 mol of isopropyl alcohol and 3 mol of deionized water, and adding 0.01 mol of hydrochloric acid (concentration of 37 wt%) as a catalyst, mixing and stirring for about 1 hour, three components according to TiO 2: GLYMO: mixing the MEMO with the molar ratio of 3:2:2, and continuously stirring for 24 hours;
(2) After the stirring is finished, adding 4% of bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide by weight of the total mass into the mixed solution as a photoinitiator, and continuously stirring at room temperature in a darkroom for about 0.5-1 hour, so that the carbon-carbon double bonds of MEMO in the mixed solution can be polymerized under the irradiation of UV light;
(3) Mixing a precursor of Polydimethylsiloxane (PDMS) and a curing agent thereof in a paper cup according to the proportion of 9:2, fully stirring, and standing for 15-30 minutes until all bubbles disappear;
(4) The AAO template is pretreated, the AAO template is soaked in a mixture of 1H, 2H-perfluoro decyl trichlorosilane (FDTS), absolute ethyl alcohol and acetic acid, the mixing ratio is 1:100:2, then the whole is stored in a refrigerator for refrigeration, the refrigeration temperature is 5 ℃, the refrigeration time is 24 hours, the whole is placed in an oven for heating after the refrigeration is finished, the temperature is 150 ℃ for 24 hours, the AAO template has lower surface free energy after the treatment, and PDMS can be easily removed from the AAO template;
(5) The symmetrical bi-pass AAO is used as a template, the center-to-center distance of the holes is 450nm, the aperture is 170nm, and the aperture length is 40-60 mu m. Pouring PDMS on a template, placing the template into a vacuum steam box, heating at 90 ℃ for 30 minutes after pouring the whole silicon wafer, and taking off the template from the photoresist template gently in order to remove bubbles generated by pouring and solidify PDMS liquid;
(6) Using polyethylene naphthalate (PEN) with the size of 2cm multiplied by 2cm as a flexible substrate, adsorbing the flexible substrate on a sucker of a spin coater, dripping a small amount of the organic-inorganic modified silicate material prepared in (2) on the substrate by using a needle tube, and performing spin coating at the spin coating rate of 1800 revolutions per minute for 80 seconds to prepare an organic-inorganic composite film on the flexible substrate;
(7) Pressing the PDMS template prepared in the step (4) on the film prepared in the step (5), applying pressure with the pressure of 10000Pa, then placing the whole under an ultraviolet xenon lamp for ultraviolet exposure with the ultraviolet exposure wavelength of 365nm, the radiation intensity at 365nm being 900mW/cm 3 and the curing time being 30 minutes, and removing the PDMS template from the film after complete curing;
(8) Adsorbing the torn micro-nano structure array on a spin coater again, taking a small amount of the organic-inorganic modified silicate material prepared in the step (2) at the center of the structure by using a needle tube, performing rapid spin coating by using a spin coating method, wherein the spin coating speed is 3000 rpm, the spin coating time is 80 seconds, forming a layer of thinner film to cover the array, forming a double-layer irregular film structure, performing ultraviolet curing again, wherein the ultraviolet exposure wavelength is 365nm, the radiation intensity at 365nm is 900mW/cm 3, and the curing time is 15-30 minutes;
(9) Placing the micro-nano structure array prepared in the step (8) into an oven, heating to remove water of a solvent, wherein the heating temperature is 80 ℃, the heating time is 20-30 minutes, and after heating is finished, manufacturing the micro-nano structure array on the flexible substrate;
(10) The OLED device structure is MoO3 (3 mm)/Ag (15 mm)/MoO 3 (10 mm)/NPB (60 mm)/Alq 3 (60 mm)/Liq (2 mm)/Al (100 mm), wherein MoO3/Ag/MoO3 is used as an anode, NPB is used as a hole transport layer, alq3 is used as a light emitting layer, and Liq/Al is used as a cathode. The evaporation process can be divided into three steps: depositing an organic-inorganic composite film, depositing an electrode and packaging in a glove box. When depositing organic-inorganic composite film, firstly placing the treated sample into a vacuum evaporation cabin of an evaporator, closing the cabin door, vacuumizing, evaporating when the vacuum degree of the cabin body reaches 4 x 10 -4 Pa, and keeping the evaporation rate of the small molecular material at the same time In order to prevent cross contamination of materials in the cabin during evaporation, a baffle plate is required to be used for shielding when the evaporation materials are replaced. Then metal electrode evaporation is carried out, and the metal electrode density is higher, so that a higher evaporation rate is needed, and the metal electrode density is generally kept at/>After the electrodes are steamed, the device is moved from the rear cabin door into a glove box for packaging, and a glass sheet coated with a mixture of packaging glue and calcium oxide is adopted during packaging.
The micro-nano structure array on the organic-inorganic composite film obtained in the embodiment 1 is subjected to scanning electron microscope test, and the result is shown in fig. 1, and the micro-nano structure array on the composite film obtained by imprinting is clear in outline, the micro-nano structure array basically keeps the shape on a template, has no large change, good overall uniformity, smooth surface, no redundant impurities, good appearance of a single hole and no defects with obvious scope, so that the imprinting process is basically successful.
Fig. 2 is a graph of current efficiency of the OLED device obtained in example 1, a curve represented by square points is a current efficiency curve of a standard sample, the standard sample is an OLED device without adding an organic-inorganic composite film to prepare a micro-nano structure array, a curve represented by round points is an OLED device with a symmetrical double-pass AAO structure array added on an OLED device substrate, and it can be seen from the graph that after the micro-nano structure array prepared by adding the organic-inorganic composite film to the OLED device, the current efficiency of the OLED device is significantly improved by about 30%.
Claims (10)
1. The preparation method of the composite film with the micro-nano structure array is characterized by comprising the following steps of:
(1) Taking gamma-glycidoxypropyl trimethoxy silane and methacryloxypropyl trimethoxy silane as organic precursors, taking tetrabutyl titanate as inorganic precursors, stirring and mixing, and preparing organic-inorganic modified silicate material sol by a sol-gel method;
(2) Adding a bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide photoinitiator into the sol, and uniformly stirring at room temperature in a darkroom to obtain an organic-inorganic modified silicate composite film material;
(3) Mixing a precursor of polydimethylsiloxane with a curing agent, fully stirring, and standing until all bubbles disappear to obtain PDMS colloid;
(4) Pouring the PDMS colloid in the step (3) on the pretreated AAO template, putting the AAO template into a vacuum steam box, and removing the PDMS template from the template after complete solidification to obtain the PDMS template;
(5) Dispersing and dripping the organic-inorganic modified silicate composite film material prepared in the step (2) on a substrate by using polyethylene naphthalate as the substrate, and preparing the organic-inorganic modified silicate material into a film by adopting a spin coating method;
(6) Pressing the PDMS template prepared in the step (3) on the film prepared in the step (5), performing ultraviolet exposure after imprinting, and removing the PDMS template from the film after complete curing to obtain the array film with the micro-nano structure;
(7) And (3) adsorbing the micro-nano structure array film on a spin coater, dripping the organic-inorganic modified silicate composite film material prepared in the step (2) at the center of the micro-nano structure array film, spin coating by adopting a spin coating method to form a layer of film which covers the micro-nano structure array, and drying after ultraviolet curing to obtain the double-layer micro-nano structure array film.
2. The method for preparing a composite film with a micro-nano structure array according to claim 1, wherein in the step (1), the molar ratio of tetra-n-butyl titanate, gamma-glycidoxypropyl trimethoxysilane and methacryloxypropyl trimethoxysilane is 1:1:1-3:2:2, and the stirring time is 24-27 hours.
3. The method for preparing a composite film with a micro-nano structure array according to claim 1, wherein the mass of the bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide added in the step (2) accounts for 4% of the total mass of the mixed solution, and the stirring time is 0.5-1 hour.
4. The method of claim 1, wherein the ratio of the precursor of Polydimethylsiloxane (PDMS) to the curing agent in the step (3) is 10:1-9:2, standing for 15-30 minutes.
5. The method for preparing a composite film with micro-nano structure array according to claim 1, wherein the pretreatment process of the AAO template in the step (4) is as follows: firstly, soaking an AAO template in a mixture of 1H, 1H, 2H, 2H-perfluoro decyl trichlorosilane, absolute ethyl alcohol and acetic acid, then refrigerating in a refrigerator, and heating the whole body in an oven after the refrigerating is finished.
6. The method for preparing a composite film with a micro-nano structure array according to claim 1, wherein in the step (4), the AAO template is a symmetrical double-pass AAO template, the holes are all in a right circular shape, the arrangement mode is hexagonal close-packed, the holes are uniform in diameter, the internal holes are straight and parallel and do not intersect, the center-to-center distance of the holes is 450nm, the hole diameter is 170nm, and the hole diameter length is 40-60 μm.
7. The method of claim 1, wherein the spin-coating time in the step (5) is 60-80 seconds, and the spin-coating rate is 1200-1800 rpm.
8. The method of claim 1, wherein the embossing pressure in the step (6) is 10000Pa, the embossing time is 15-30 minutes, the uv exposure wavelength is 365nm, the radiation intensity at 365nm is 900mW/cm 3, and the curing time is 20-40 minutes.
9. The method for preparing a composite film with a micro-nano structure array according to claim 1, wherein the spin coating time in the step (7) is 60-80 seconds, and the spin coating rate is 1000-3000 rpm.
10. The method for preparing a composite film with a micro-nano structure array according to claim 1, wherein the heating temperature of the drying in the step (7) is 80-90 ℃ and the heating time is 20-30 minutes.
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| CN109251338A (en) * | 2018-10-30 | 2019-01-22 | 南京邮电大学 | A kind of titanium dioxide/3-(isobutene acyl-oxygen) propyl trimethoxy silicane organic, inorganic composite film preparation method and application |
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| CN108681206A (en) * | 2018-05-11 | 2018-10-19 | 南京邮电大学 | Has the function of the composite film material and preparation method thereof of up-conversion luminescence and ultraviolet light sensitive characteristic simultaneously |
| CN109251338A (en) * | 2018-10-30 | 2019-01-22 | 南京邮电大学 | A kind of titanium dioxide/3-(isobutene acyl-oxygen) propyl trimethoxy silicane organic, inorganic composite film preparation method and application |
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