CN114350184B - Repairing type photosensitive nano coating and preparation method and application thereof - Google Patents
Repairing type photosensitive nano coating and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of nano materials and optical etching, and particularly relates to a repair type photosensitive nano coating as well as a preparation method and application thereof.
Description
Technical Field
The invention belongs to the technical field of nano materials and optical etching, and particularly relates to a repair type photosensitive nano coating as well as a preparation method and application thereof.
Background
Currently, optical patterning methods for nanocrystals can be divided into two categories: (1) photoresist-based optical etching techniques. The photosensitive characteristic of the commercial finished photoresist is utilized to be combined with the traditional colloid nano crystal in a physical mixing mode. The specific process can be divided into two types, one is to construct a structural template by using a photoresist, fill a crystal into a template frame by a perfusion method, and finally strip the photoresist to realize patterning (fig. 1 a). Another type is to mix the nanocrystals with a photoresist and pattern them directly into the photoresist (fig. 1 b). After patterning, a portion of the photoresist remains, and the nanocrystals will be embedded in the photoresist template. (2) Photoresist-free lithography (fig. 1 c). Nanocrystal or sol-gel nanomaterials are converted into photosensitive nanocoatings by the introduction of photochemically active anionic or cationic ligand groups. Ligand groups decompose under specific illumination, resulting in a change in the stability of the nanocrystal, thereby causing a change in the solubility of the illuminated and non-illuminated portions in a particular solvent. The material of the non-illuminated portion was removed by rinsing with the corresponding solvent to obtain a nanocrystal pattern. The nano coating can be patterned by deep ultraviolet light (DUV, 254nm), and can be processed by photoetching by near ultraviolet light (i-line, 365nm), blue light (h-405nm) or even visible light (450 nm). The involved photosensitive groups can be divided into two classes, one is a Photoacid Generator System (PAGs), and the other is a bifunctional surface ligand.
The prior art has the following defects:
photoresist-based optical etching techniques inevitably require the use of a photoresist. Currently, commercial photoresists are generally composed of organic-polymer materials, and have no additional functions and are used only for masks, so that impurities are introduced while the process cost is increased, and the pattern resolution is too low due to solvent action and capillary effect. In addition, the high dependence of the method on the photoresist greatly influences the universality of the process. In addition, the nanocrystals patterned in this way have a large number of organic molecules attached to their surfaces, and these long-chain organic molecules severely hinder charge or heat transfer between the crystals, and also reduce the filling concentration of the nanocrystals in the device. Therefore, the organic-inorganic hybrid nano crystal is directly used for constructing a device, and has high energy consumption, poor thermal stability and low working efficiency.
For the photoresist-free lithography technology, a specific photosensitive ligand needs to be designed for each nanocrystal before use, so that the universality is poor, and the ligand selectivity is single. In addition, different photosensitive ligands have different surface functional groups, and hetero atoms are introduced into a crystal system in the process of replacing organic ligands to influence the original physicochemical properties of the crystal. Meanwhile, in the etching process, molecules generated after the photosensitive ligand is decomposed can cause irreversible damage to the nanocrystal. For example, in the case of bifunctional ligands, which are attached to the nanocrystal via a sulfhydryl (S-) group, the S-remains attached to the crystal surface and cannot be removed after photodecomposition, thus causing a change in the nanocrystal composition after photolithography. For the photo-acid generator system, acid or proton is generated in the process of illumination, and the stability of the crystal is changed through the interaction with the nano crystal or a surface ligand, so that patterning is realized. However, the acid generated in situ in this process can corrode the nanocrystals, seriously affecting the properties of the crystals themselves, such as causing fluorescence quenching of the nanocrystals, and preventing the patterned nanocrystals from being used in the field of electroluminescence or photoluminescence. Post-repair operations are required after patterning if the original properties of the nanocrystals are to be restored.
Disclosure of Invention
Aiming at the technical problems that long-chain organic molecules in the prior art are poor in thermal stability, so that charge transmission among crystals is easily hindered, and the filling concentration of the nanocrystals is reduced, the organic ligand is removed from the surface of the nanocrystals by using a ligand stripping technology, so that the interference of organic matters on the inorganic nanocrystals is reduced; aiming at the problems that the composition and the morphology of the crystal can be changed in the patterning process of the existing photosensitive ligand, the physicochemical properties of the crystal are further influenced, and the like, the invention designs a repair type photosensitive nano-coating by introducing PBGs (photobase generators) photosensitive ligand. The coating is utilized to repair the surface defects of the patterned colloid nano-crystals while realizing optical patterning, and improve and enhance the photoelectric properties of the nano-crystals, thereby establishing a nondestructive optical patterning method.
The technical scheme of the invention is as follows:
the invention provides a repair type photosensitive nano coating, which comprises a PBGs ligand and a nanocrystal, wherein the PBGs ligand is PBGs of which a decomposition product is amine after illumination.
Preferably, the PBGs ligands are ionic PBGs: the cation part is PBGs original structure, and the anion part is halide or sulfide inorganic ligand;
Or
The PBGs ligand is covalent PBGs: a cinnamic acid amide structure.
Preferably, the PBGs ligands are ionic PBGs and the cationic moiety is
R 1 Alkyl or aryl radicals, R 2 Alkyl or aryl;
the anionic moiety is: CdCl 3 - 、ZnBr 3 - 、SCN - 、Cl - 、Br - 、S 2- Any one or a combination of more of them. More preferably, R 1 Is n-butyl or methyl, R 1 Is n-butyl, methyl or benzyl.
Preferably, the covalent PBGs ligands are
Wherein R is alkyl. More preferably, R is n-butyl, n-pentyl, n-octyl or cyclohexyl.
Preferably, the nanocrystals are: semiconductor nanometer material, oxide nanometer material, metal nanometer material, magnetic nanometer material or nuclear shell structure nanometer material.
Preferably, the nanocrystals are: CdSe NCs, InP NCs, TiO 2 NCs、ZrO 2 NCs、Au NCs、Pt NCs、Fe 2 O 3 NCs, FeCo NCs, CdSe/ZnS NCs, ZnSe/ZnS NCs, InP/ZnS NCs. NCs stands for nanocrystals.
The preparation method of the repair type photosensitive nano coating comprises the following steps:
And 3, combining the PBGs ligand with the nanocrystal obtained in the step 2 through ligand exchange.
Preferably, the specific steps of step 2 are: respectively dissolving nanocrystals with carboxyl or amino on the surface and an exfoliation ligand in an organic solvent which can be mutually dissolved into one phase, wherein the concentration of each nanocrystal is 5-20mg/mL, mixing the nanocrystals and the exfoliation ligand according to a volume ratio of 10:1, centrifuging to obtain precipitates, and re-dispersing the precipitates in an aprotic polar solvent. More preferably, the exfoliating ligand is (NH) 4 ) 2 S、NOBF 4 、Et 3 OBF 4 Or Et 2 O·BF 3 。
Preferably, the ligand exchange method used in step 3 is any one of an in-phase method, a heterogeneous method and a two-step method;
the in-phase method comprises the following specific steps: dispersing the nano-crystal and the PBGs ligand in the same solvent, and separating the functionalized crystal in a precipitation form;
the heterogeneous method comprises the following specific steps: respectively dispersing the nano-crystal and the PBGs ligand in two immiscible solvents to form an upper phase and a lower phase, and after ligand exchange, transferring the crystal from the original solvent to the solvent containing the ligand and stably storing the crystal;
the two-step method comprises the following specific steps: and stripping the organic ligand carried on the surface of the nanocrystal by using a ligand stripping method, then directly introducing the ionic PBGs ligand, and combining the nanocrystal and the PBGs molecules to form the nano coating.
Preferably, in the step 3, when the PBGs ligand is combined with the nanocrystal in the step 2, the mass fraction of the PBGs ligand in the system is 0.2-0.4%.
The photochemical patterning process of the repair type photosensitive nano coating is characterized by comprising the following steps of:
step A, preparing a continuous, compact and thickness-controllable nanocrystal film on a substrate by using the repairing type photosensitive nano coating;
b, exposing the appointed part by using a light source and combining a mask plate;
step C, developing:
dissolving the nano crystal of the unexposed part by using a nonpolar solvent, and reserving the exposed part to realize normal phase etching;
or using a nonpolar solvent to dissolve the nano crystals of the exposed part and reserving the unexposed part to realize reverse etching.
Preferably, in the step A, the step B,
the substrate is glass, quartz, Si/SiO 2 And a polymer flexible film;
the substrate is treated by TAMI treatment (toluene-acetone-methanol-isopropanol) or piranha reagent treatment;
the preparation method of the nano-crystal film adopts a spin-coating method, a spraying method or a blade coating method.
The repair type photosensitive nano coating can be applied to a self-repair photoetching technology based on inorganic photoresist.
Compared with the prior art, the invention has the advantages that,
the existing photoresist-free photoetching technology is 1. adding new heteroatom ligands, which cannot be removed after photoetching to influence the composition of the original nano material; or 2, the surface of the nano material is changed through corrosion, so that the original photoelectric property of the material is influenced. If the stability and consistency of the patterned material performance are to be ensured, a post-processing process is added after the photolithography.
The invention utilizes a new photosensitive ligand to combine with the nano crystal to prepare the photosensitive coating with the self-repairing function. In the photoetching patterning process, the patterning is realized, simultaneously, the product decomposed by the photosensitive ligand is used for modifying the nanocrystal again, the original photoelectric property of the nanocrystal is kept or even improved, and the original two steps of development and post-treatment are combined into one step, so that the lossless optical patterning method is established.
Because the system is not mixed with the photoresist, the nano particles in the developing solution can be collected again by a precipitation method, and then are functionalized by the surface treatment method of the invention to be prepared into new photosensitive coating again, thereby realizing the recycling of the material.
Drawings
FIG. 1a is a photoresist-based optical etching technique 1; FIG. 1b is a photoresist-based optical etching technique 2; FIG. 1c is a photoresist-free lithography technique; FIG. 1d is a non-destructive optical patterning process of the present invention;
FIG. 2 is a flow chart of the preparation of a repair type photosensitive nano-coating;
FIG. 3 is a diagram of various repair-type photosensitive nanocoatings; the nanocrystals of the repairing type photosensitive nano coating are CdSe nanocrystal, CdSe/CdS core-shell nanocrystal, CdSe/CdSnSes core-shell nanocrystal, CdSnSes/ZnS core-shell nanocrystal and NaYF nanocrystal from left to right respectively 4 Up-conversion nanocrystals, PbS nanocrystals, Fe 2 O 3 Nanocrystals, PtFe alloy nanocrystals, silver nanocrystals, CdSe nanowires, CdSe nanosheets;
FIG. 4 is a decomposition equation of cinnamic acid type PBGs ligands under visible light;
FIG. 5 is a graph of the ultraviolet absorption spectrum of cinnamic acid type PBGs ligands decomposed under different light intensities;
FIG. 6 is a graph of the UV absorption spectra of a CdSe nanocrystal-based repair-type photosensitive nanocoating before and after illumination;
FIG. 7 is an absorption spectrum, a fluorescence spectrum and a fluorescence lifetime chart of CdZnSeS/ZnS core-shell structure quantum dots before and after being converted into photosensitive coating;
FIG. 8 is a TEM photograph of a repaired photosensitive nanocoating of CdZnSeS/ZnS core-shell nanocrystals and CdSe/CdS core-shell nanocrystals;
FIG. 9 is XRD spectra of CdSe quantum dots (top) under protection of organic ligands and CdSe quantum dots (bottom) in a healing type photosensitive nano-coating;
fig. 10 is a process of obtaining a nanocrystal pattern by a photochemical patterning process of a repair-type photosensitive nanocoating. From left to right are CdSe NCs, PbS NCs, and FePt NCs;
FIG. 11 is a core-shell CdZnSe/ZnS nanocrystal pattern obtained by a photochemical patterning process of a repair-type photosensitive nanocoating.
Detailed Description
Nanomaterial synthesis
Cadmium selenide nanocrystals (CdSe NCs). Cadmium oleate (Cd (OA) is prepared by mixing CdO (643mg, 5mmol) with 10mL Oleic Acid (OA) 2 ) Stock solutions. After degassing at 150 ℃, the flask was heated to 250 ℃ under dry nitrogen. The suspension then turned into a colorless solution, indicating the formation of Cd (OA) 2 . It was then degassed again at 150 ℃ to remove water produced and stored as a waxy solid. To synthesize wurtzite CdSe NCs, we shall call Cd (OA) 2 Stock solution (2.25mL), TOPO (1.2g) and ODE (12mL) were mixed and degassed under vacuum at 100 ℃. The temperature was then raised to 300 ℃ under nitrogen. At this time, a mixture containing 4mL of TOPSe (1.0M) and 3mL of oleylamine was quickly injected into the flask. The reaction was held for 7 minutes and then cooled to room temperature. Ethanol was added to precipitate the resulting nanocrystals, which were then re-dissolved in toluene. The washing process was repeated 3 times, and finally the purified NCs were dissolved in 5mL of toluene.
Titanium dioxide nanocrystals (TiO) 2 NCs). Ammonium fluoride (14.8mg), stearyl alcohol (2.70g), octadecene (8mL), oleylamine (0.5 m)L) and oleic acid (0.5mL) were combined in a three-necked flask. After heating at 120 ℃ in vacuo, the flask was refilled with nitrogen and 1mmol of Ti (OBu) was injected 4 . The temperature was then raised to 280 ℃. After heating for 60 minutes, the flask was allowed to cool to 60 ℃. The resulting nanocrystals were washed with acetone and redissolved in 5mL of toluene.
CdZnSeS/ZnS core-shell nanocrystal. A zinc oleate stock solution is prepared by mixing 405mg (5mmol) of zinc oxide with 10mL of oleic acid. After heating to 120 ℃ under vacuum, the flask was charged with nitrogen and the temperature was raised to 240 ℃. The suspension then turned into a pale yellow solution, indicating the formation of zinc oleate. The heater was removed and the flask was allowed to cool to 100 ℃ before 15mL octadecene and 25mL oleylamine were added. The resulting solution was degassed at 120 ℃ and stored in a glove box. To form the core-shell NCs, 0.24mmol of TOPSe +4mmol of TOPS mixture was first injected into 0.24mmol of cadmium oleate and 4mmol of zinc oleate to form CdZnSeS nanocrystals. Then, 2.5mL of zinc oleate (0.08M) and 1-octanethiol (0.09M) were injected simultaneously at a rate of 2.5mL/h by a two-channel syringe pump. The obtained CdZnSeS/ZnS core-shell nanocrystal is washed by toluene/ethanol and finally re-dissolved in toluene.
CdZnS/ZnS core-shell nanocrystal. Cadmium oxide (1mmol), zinc acetate (5mmol), OA (3.5mL) and octadecene (7.5mL) were mixed in a three-necked flask. After degassing at 100 ℃ it was heated to 300 ℃ under nitrogen. 1mmol of sulfur powder was completely dissolved in octadecene (1.5mL) at about 100 deg.C, and the solution was quickly poured into the flask when the temperature reached 300 deg.C. The reaction was held at 310 ℃ for 8 minutes. Then, 1.5mL of tetrabutylphosphine containing 4mmol of sulfur was injected for shell growth. The shell growth step lasts 40 minutes. The resulting CdZnS/ZnS nanocrystals were washed with hexane/acetone and finally re-dissolved in hexane.
Surface treatment process
In the surface treatment process, the nanocrystalline and the inorganic ligand are respectively dissolved in toluene and Dimethylformamide (DMF) (the dimethylformamide can also be replaced by the methylformamide), the concentration is 5-20mg/mL, the nanocrystalline and the inorganic ligand are mixed according to the volume ratio of 10:1, the two solvents are mutually dissolved into one phase, the nanocrystalline and the inorganic ligand are subjected to surface reaction in the phase, and the generated nanocrystalline with a naked surface cannot be continuously dissolved in the toluene and is separated out in a precipitation form so as to be separated from the free ligand. After centrifugation, the nanocrystal can be redispersed in aprotic polar solvents such as DMF, methylformamide (NMF) and the like, and has good solubility, so that a stable colloidal solution is obtained.
Characterization techniques
Transmission Electron Microscopy (TEM). TEM images were obtained using a JEOL JEM-2800 electron microscope. The acceleration voltage is 200 kv.
Ultraviolet and visible absorption spectrum. The ultraviolet-visible absorption spectrum of the material was obtained using an Agilent Cary 5000 spectrophotometer.
Fluorescence spectrum and fluorescence lifetime test. And obtaining a material fluorescence spectrum and a fluorescence attenuation curve by using a HORIBA FL-3 fluorescence spectrometer.
Wide angle X-ray diffraction (XRD). XRD of the powdered material was collected using Bruker D8 XRD, operating at 40 kv and 40 ma.
Zeta potential. The zeta potential of the material in solution was measured using a Malvern Nano-Z instrument at a test temperature of 298K.
Example 1:
this example illustrates a method for preparing a repair-type photosensitive nanocoating based on cadmium selenide nanocrystals and a patterning process flow.
Firstly, cadmium selenide nanocrystals (CdSe NCs) with surface ligands of oleylamine and oleic acid are synthesized in an anhydrous and oxygen-free environment by a thermal injection method. The nano crystal is stabilized in toluene to form a colloidal solution, and the concentration of the colloidal solution is prepared to be 10 mg/mL. Then, 0.1mL of inorganic ligand (NH) was added to 1mL of the above solution 4 ) 2 And (3) exchanging organic ligands with a methyl formamide solution (10mg/mL) of S to convert the nanocrystal from oleophilic type to hydrophilic type, negatively charging the surface, re-dispersing after centrifugation, and stabilizing in methyl formamide. Cationic PBGs (the mass fraction is 0.2-0.4%) are added into the solution and combined with surface anionic ligands to obtain the photosensitive nanocrystalline coating with the concentration of 20-30 mg/mL. The specific steps of patterning are divided into film making, exposure and development (as shown in fig. 1 d). The photosensitive nano coating forms a continuous, compact and thickness-controllable nano crystal film on the silicon substrate treated by the piranha reagent by a spin coating method, and the spin coating parameters are 3500rpm and 60 s. By depth Ultraviolet light source (wavelength 254nm) combined with mask plate with specific pattern exposes the specified part of the nanocrystalline film with exposure dose of 50-75mJ/cm 2 . The coating on the illuminated part of the film generates photochemical reaction, primary amine in the product exchanges the inorganic ligand on the surface of the nanocrystal while repairing the surface defect of the CdSe NCs, and the hydrophilic type is converted into oleophilic type; and the part which is not illuminated by light still keeps the original property, and can be dissolved by methyl formamide in the subsequent development step, thereby realizing the normal phase etching of the nano crystal.
Cationic PBGs used in this example:
the cation part is
Wherein R is 1 N-butyl, R 2 N-butyl;
the anionic moiety is: s 2- 。
The repairing type photosensitive nano coating prepared by the embodiment is a clear and transparent colloidal solution as shown in fig. 3.
In this example, the cationic moiety
In (1),
R 1 n-butyl, R 2 Methyl group;
or R 1 Methyl, R 2 A phenyl group;
or R 1 Methyl, R 2 When being benzyl:
the photosensitive coating with the self-repairing function can be prepared, and the nano-crystal is modified again by using the product after the decomposition of the photosensitive ligand while realizing patterning in the photoetching patterning process, so that the original photoelectric property of the nano-crystal is maintained or even improved.
In this example, CdCl was partially selected as the anion 3 - 、ZnBr 3 - 、SCN - 、Cl - 、Br - 、S 2- Any one or combination of more of the above can be used for preparing the photosensitive coating with the self-repairing function, and the nano-crystal is modified again by using the product after decomposition of the photosensitive ligand while realizing patterning in the photoetching patterning process, so that the original photoelectric property of the nano-crystal is maintained or even improved.
In this embodiment, the nanocrystals of the repair-type photosensitive nano-coating are selected from CdSe/CdS core-shell nanocrystals, CdSe/CdZnSeS core-shell nanocrystals, CdZnSeS/ZnS core-shell nanocrystals, NaYF 4 Up-conversion nanocrystals, PbS nanocrystals, Fe 2 O 3 The experimental results for the nanocrystals, the PtFe alloy nanocrystals, the silver nanocrystals, the CdSe nanowires, and the CdSe nanosheets are shown in FIG. 3. The absorption spectrogram, the fluorescence spectrogram and the fluorescence lifetime chart of the CdZnSeS/ZnS core-shell structure quantum dot before and after being converted into the photosensitive coating are shown in FIG. 7, which shows that the optical property of the nanocrystal body is not influenced. A TEM photograph of the repair type photosensitive nano-coating of the CdZnSeS/ZnS core-shell nanocrystal and the CdSe/CdS core-shell nanocrystal is shown in FIG. 8. The material in the electron microscope image has good appearance and uniform size.
The ultraviolet absorption spectrogram of the CdSe nanocrystal-based repair-type photosensitive nano-coating before and after illumination is shown in FIG. 6, and the XRD spectrogram is shown in FIG. 9. Comparison of the absorption spectra before and after exposure can indicate decomposition of the photoactive ligand.
The patterns of nanocrystals obtained by the photochemical patterning process of the repair-type photosensitive nanocoates (nanocrystals, CdSe NCs, PbS NCs, and FePt NCs, respectively) prepared in this example are shown in fig. 10. The pattern boundary is clear, the background is clean, the resolution reaches the micron level, and the requirements of practical application of electronic devices and the like can be met.
The core-shell CdZnSe/ZnS nanocrystal pattern obtained by the photochemical patterning process of the repair-type photosensitive nanocoating prepared in this example is shown in fig. 11. The nano-crystal in the pattern has good photoluminescence performance, and is equivalent to the level of the nano-crystal without surface treatment.
Example 2:
this example illustrates a method for preparing a repair-type photosensitive nanocoating based on oxide nanocrystals and a patterning process flow.
Firstly, synthesizing titanium dioxide nanocrystalline (TiO) with surface ligand of oleylamine and oleic acid in anhydrous and oxygen-free environment by a colloid chemical method 2 NCs). The nano crystal is stabilized in toluene to form a colloidal solution, and the concentration of the colloidal solution is prepared to be 10 mg/mL. Then, 0.1mL of a stripping ligand (NOBF) was added to 1mL of the above solution 4 、Et 3 OBF 4 Or Et 2 O·BF 3 ) The methyl formamide solution (10mg/mL) completely removes the organic ligand, changes the nano crystal from oleophilic type to hydrophilic type, has positive electricity on the surface, disperses again after centrifugation, and is stabilized in DMF solvent. To this solution, cinnamic acid type PBGs (mass fraction 0.3%) was added, and the molecular structure is shown in fig. 4, where R ═ n-butyl in this example, to obtain a photosensitive nanocrystal coating with a concentration of 20-30mg/mL (see scheme 2). The specific steps of patterning are divided into film making, exposure and development (as shown in fig. 1 d). The photosensitive nano coating forms a continuous, compact and thickness-controllable nano crystal film on the silicon substrate treated by the piranha reagent by a spin coating method, and the spin coating parameters are 2000rpm and 60 s. Exposing the appointed part of the nanocrystalline film by using a deep ultraviolet light source (wavelength 254nm) and combining a mask plate with a specific pattern, wherein the exposure dose is 200- 2 . The coating on the illuminated part of the film has photochemical reaction (the reaction formula is shown in figure 4, the ultraviolet absorption spectrum chart of the cinnamic acid type PBGs ligand decomposed under different light intensities is shown in figure 5, and the change of the spectrum shows that 300mJ/cm 2 The exposure dose of (b) can almost completely decompose the photosensitive ligand), the primary amine in the product is used for repairing TiO 2 When NCs have surface defects, the coating is changed from hydrophilic type to oleophilic type; and the part which is not illuminated by light still keeps the original property, and can be dissolved by methyl formamide in the subsequent development step, thereby realizing the normal phase etching of the nano crystal.
In this embodiment, when the cinnamic acid type PBGs, or R ═ n-pentyl, or R ═ n-octyl, or R ═ cyclohexyl, all the photosensitive coatings with self-repairing function can be prepared, and in the photolithographic patterning process, the product decomposed by the photosensitive ligand is used to modify the nanocrystal again while realizing patterning, so as to maintain or even improve the original photoelectric properties of the nanocrystal.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and all equivalent substitutions or substitutions made on the above-mentioned embodiments are included in the scope of the present invention.
Claims (7)
1. A kind of repairing type photosensitive nanometer paint, characterized by, including PBGs ligand and nanocrystal, the said PBGs ligand is PBGs that the decomposition product is amine after the illumination;
the PBGs ligand is ionic PBGs, and the cationic part is ionic PBGs
R 1 Alkyl or aryl radicals, R 2 Alkyl or aryl;
the anionic moiety is: CdCl 3 - 、ZnBr 3 - 、SCN - 、Cl - 、Br - 、S 2- Any one or a combination of more of them;
or
The PBGs ligand is
Wherein R is alkyl;
the nanocrystals are: CdSe NCs, InP NCs, TiO 2 NCs、ZrO 2 NCs、Au NCs、Pt NCs、Fe 2 O 3 NCs, FeCo NCs, CdSe/CdS NCs, CdSe/ZnS NCs, ZnSe/ZnS NCs, or InP/ZnS NCs.
2. The preparation method of the repair type photosensitive nano paint according to claim 1, which comprises the following steps:
step 1, stabilizing nanocrystals with carboxylic acid ligands or amine ligands on the surface in a non-polar solvent in a colloidal form;
step 2, completely removing the organic ligand by using the stripping ligand, converting the nano crystal in the step 1 from oleophilic type to hydrophilic type, and stabilizing the nano crystal in a polar solvent;
and 3, combining the PBGs ligand with the nanocrystal obtained in the step 2 through ligand exchange.
3. The method for preparing a repairing photosensitive nano paint according to claim 2, wherein the ligand exchange method used in the step 3 is any one of an in-phase method, a heterogeneous method and a two-step method;
The in-phase method comprises the following specific steps: dispersing the nano-crystal and the PBGs ligand in the same solvent, and separating the functionalized crystal in a precipitation form;
the heterogeneous method comprises the following specific steps: respectively dispersing the nano-crystal and the PBGs ligand in two immiscible solvents to form an upper phase and a lower phase, and after ligand exchange, transferring the crystal from the original solvent to the solvent containing the ligand and stably storing the crystal;
the two-step method comprises the following specific steps: and stripping the organic ligand carried on the surface of the nanocrystal by using a ligand stripping method, then directly introducing the ionic PBGs ligand, and combining the nanocrystal and the PBGs molecules to form the nano coating.
4. The preparation method of the repair type photosensitive nano paint according to claim 2, wherein the specific steps of the step 2 are as follows: respectively dissolving nanocrystals with carboxyl or amino on the surface and an exfoliation ligand in an organic solvent which can be mutually dissolved into one phase, wherein the concentration of each nanocrystal is 5-20mg/mL, mixing the nanocrystals and the exfoliation ligand according to a volume ratio of 10:1, centrifuging to obtain precipitates, and re-dispersing the precipitates in an aprotic polar solvent.
5. The method for preparing a repairing photosensitive nano paint according to claim 2, wherein in the step 3, when the PBGs ligand is combined with the nano crystal in the step 2, the mass fraction of the PBGs ligand in the system is 0.2-0.4%.
6. A photochemical patterning process based on the restorative-type photosensitive nanocoating of claim 1, comprising the steps of:
step A, preparing a nanocrystal film on a substrate by using the repairing type photosensitive nano coating;
b, exposing the appointed part by using a light source and combining a mask plate;
step C, developing:
dissolving the nano crystal of the unexposed part by using a nonpolar solvent, and reserving the exposed part to realize normal phase etching;
or using a nonpolar solvent to dissolve the nano crystals of the exposed part and reserving the unexposed part to realize reverse etching.
7. The application of the repair type photosensitive nano-coating of claim 1 in a self-repairing optical etching technology based on inorganic photoresist.
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| CN114350184A (en) | 2022-04-15 |
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