Quantum dot photoresist composite based on poss connection and preparation method and application thereof

Abstract

The application discloses a quantum dot photoresist composite material based on POSS connection and a preparation method and application thereof. The quantum dot photoresist composite material comprises a plurality of POSS-quantum dot composites; the POSS-quantum dot composite comprises a bridging structure formed by connecting POSS structure monomers and quantum dots through covalent bonds or coordination bonds, and the quantum dots are uniformly embedded in the skeleton of the POSS structure monomers; or comprises a composite main network framework formed by combining the POSS structure monomers and resin monomers and the quantum dots uniformly embedded therein, and the three form a ternary hybrid network, or the quantum dots are directly mixed in a dispersed form between the composite main network frameworks. The quantum dot photoresist composite material can reduce migration, agglomeration and phase separation of the quantum dots, improve edge resolution and resolution of a pattern, and thus realize micron or even sub-micron three-color pixel-level patterning.

Description

Technical Field

[0001] This invention relates to a quantum dot photoresist composite material, specifically to a quantum dot photoresist composite material based on POSS interconnects and its preparation method, as well as its application in Micro-LED micro-displays, belonging to the field of optoelectronic display materials technology. Background Technology

[0002] Micro-LED, as a next-generation display technology, boasts advantages such as high brightness, high contrast, and high response speed, making it an ideal solution for AR / VR and high-end displays. However, one of the key aspects of achieving monolithic integrated full-color display with Micro-LED is the precise patterning of red, green, and blue quantum dots into micropixel areas to form high-resolution luminescent patterns.

[0003] Currently, commonly used quantum dot photoresists (QD-PR) typically employ the method of physically dispersing quantum dots within a photoresist resin. However, this method has the following problems:

[0004] 1. Lack of chemical fixation for quantum dots leads to poor thermal stability;

[0005] 2. The resolution of photolithography patterns is limited by factors such as quantum dot aggregation and refractive index mismatch.

[0006] Therefore, there is an urgent need to develop a novel composite material system that can simultaneously enhance the bonding ability between quantum dots and photoresist networks, improve stability and pattern conformability. Summary of the Invention

[0007] The main objective of this invention is to provide a quantum dot photoresist composite material connected by functionalized POSS structural units and its preparation method, so as to overcome the shortcomings of the prior art.

[0008] Another object of the present invention is to provide the application of the aforementioned POSS-based quantum dot photoresist composite material.

[0009] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0010] A first aspect of the present invention provides a quantum dot photoresist composite material based on POSS connections, which includes multiple POSS-quantum dot composites; the POSS-quantum dot composites include a bridging structure formed by connecting POSS structural monomers and quantum dots through covalent bonds or coordination bonds, the quantum dots are uniformly embedded in the framework of the POSS structural monomers to form a three-dimensional network structure, and a dense coating layer is formed on the surface of the quantum dots.

[0011] A second aspect of this invention also provides a method for preparing the aforementioned POSS-based quantum dot photoresist composite material, comprising:

[0012] Quantum dots are connected to POSS structure monomers through covalent or coordinate bonds to form POSS-quantum dot complexes;

[0013] The POSS-quantum dot composite is mixed, or the POSS-quantum dot composite is mixed with a photoresist system to obtain a quantum dot photoresist composite material based on POSS connections.

[0014] A third aspect of the present invention also provides another quantum dot photoresist composite material based on POSS connections, comprising: a composite host network framework formed by combining POSS structure monomers and resin monomers, and quantum dots, wherein the quantum dots are uniformly embedded inside the composite host network framework to form a ternary hybrid network, wherein the POSS structure monomers and quantum dots are connected by covalent bonds or coordination bonds, and a dense coating layer is formed on the surface of the quantum dots.

[0015] A fourth aspect of the present invention provides a method for preparing the POSS-connected quantum dot photoresist composite material, comprising: uniformly mixing POSS structure monomers, quantum dots, resin monomers, photoinitiators, and solvents to obtain the POSS-connected quantum dot photoresist composite material. A fifth aspect of the present invention provides another POSS-connected quantum dot photoresist composite material, comprising: a composite host network framework formed by combining POSS structure monomers and resin monomers, and quantum dots, wherein the quantum dots are directly mixed in a dispersed form between the composite host network framework.

[0016] The sixth aspect of the present invention also provides a method for preparing the quantum dot photoresist composite material based on POSS connections, which includes: firstly, combining POSS structure monomers with resin monomers to form a composite host network framework, and then directly mixing quantum dots in a dispersed form between the composite host network framework to obtain the quantum dot photoresist composite material based on POSS connections.

[0017] The seventh aspect of the present invention also provides the application of the aforementioned POSS-connected quantum dot photoresist composite material in Micro-LED full-color displays.

[0018] Accordingly, an eighth aspect of the present invention also provides a quantum dot patterning method, comprising:

[0019] The quantum dot photoresist composite material based on POSS connections is applied to the surface of a Micro-LED chip;

[0020] Graphical exposure can be performed using methods such as mask exposure, laser scanning, or TPP.

[0021] After development, a patterned quantum dot pattern of the corresponding color is obtained.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0023] 1) In the quantum dot photoresist composite material based on POSS connection provided by the present invention, quantum dots and functionalized POSS structural monomers form covalent or coordinated connections. The cage-like inorganic skeleton of POSS has high thermal stability and steric hindrance effect. After the adhesive is cured, it can form a stable three-dimensional microstructure in the polymer network, so that the quantum dots are uniformly fixed in the crosslinking matrix, which can reduce the migration, aggregation and phase separation of quantum dots, improve the edge resolution and resolution of the pattern, thereby realizing micron or even submicron level three-color pixel-level patterning, and improving the structural stability during the patterning process and under aging conditions.

[0024] 2) Because the quantum dot surface is coated with a surface coating layer, the coating layer can effectively suppress the ligand desorption of quantum dots under heating, light irradiation and chemical environment (solvent), reduce the generation of surface defects, thereby improving the luminescence efficiency of quantum dots and maintaining their long-term photostability, including anti-blue light bleaching ability and high heat resistance.

[0025] 3) In the quantum dot photoresist composite material based on POSS connection provided by the present invention, the functionalized POSS structure monomers serve as chemical bridges to fix the quantum dots on the one hand, and form a covalent network with the resin monomers on the other hand to enhance the overall mechanical stability. The dual anchoring effect enables the quantum dots to be evenly distributed in the composite host network framework, thereby improving the micron / submicron patterning accuracy.

[0026] 4) The quantum dot distribution in the quantum dot photoresist composite material based on POSS connection provided by this invention is more uniform, the patterned light emission is more stable, and the color saturation and uniformity are better than the prior art. It can be precisely patterned by photolithography. By adjusting different POSS-quantum dot composites, high-resolution full-color patterning of independent three-color channels can be achieved on a single Micro-LED chip, which is compatible with pixel-level full-color integration of Micro-LED and shows higher functionality and applicability in practical applications.

[0027] 5) The quantum dot photoresist composite material based on POSS connection provided by this invention is resistant to high temperature and aging, and is suitable for Micro-LED packaging and working environment. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 This is a photolithography result diagram of the photoresist material in Comparative Example 1;

[0030] Figure 2 This is a photolithography result of the quantum dot photoresist composite material based on POSS interconnection prepared in Example 1;

[0031] Figure 3 This is a photolithography result of the quantum dot photoresist composite material based on POSS connections prepared in Example 10;

[0032] Figure 4 This is a photolithography result of the quantum dot photoresist composite material based on POSS interconnects prepared in Example 21;

[0033] Figure 5 This is a lithographic result diagram of the QDs dissolution scheme in Example 26. Detailed Implementation

[0034] In view of the shortcomings of the existing technology, the inventors of this case, through long-term research and extensive practice, have proposed the technical solution of this invention, which mainly provides a composite material that connects quantum dots and photoresist resin through functionalized POSS structural units, suitable for monolithic integrated full-color patterning of Micro-LED micro-displays.

[0035] The following will further explain the technical solution, its implementation process, and its principles. However, it should be understood that within the scope of this invention, the above-mentioned technical features of this invention and the technical features specifically described below (in embodiments) can be combined with each other to form new or preferred technical solutions. Due to space limitations, they will not be described in detail here.

[0036] As one aspect of the technical solution of the present invention, a quantum dot photoresist composite material based on POSS connection includes multiple POSS-quantum dot composites; the POSS-quantum dot composite includes a bridging structure formed by connecting POSS structural monomers and quantum dots through covalent bonds or coordination bonds, the quantum dots are uniformly embedded in the skeleton of the POSS structural monomers to form a three-dimensional network structure, and a dense coating layer is formed on the surface of the quantum dots.

[0037] In some embodiments, the POSS-connected quantum dot photoresist composite material comprises a plurality of mutually cross-linked POSS-quantum dot composites.

[0038] In other embodiments, the POSS-connected quantum dot photoresist composite material further includes a photoresist matrix, in which a plurality of the POSS-quantum dot composites are uniformly dispersed.

[0039] In some embodiments, the POSS-quantum dot composite is formed by coordination bonding between a functionalized POSS structural monomer and a metal ion or group on the quantum dot surface via substitution. At least one end of the functionalized POSS structural monomer has a first functional group serving as a ligand group for bonding with the quantum dot surface. This first functional group may include, but is not limited to, one or more of the following: thiol, carboxyl, amino, phosphonic acid, phosphonoxy, selenol, acrylate, and epoxy groups. Introducing these functional groups onto the POSS structural monomer enables bonding with the quantum dot surface.

[0040] In some more specific implementation schemes, taking the scheme with carboxyl as the first functional group as an example, the functionalized POSS monomer is obtained by carboxylation (-COOH) modification. Specific modification methods can include: amidation / saltation reaction of aminopropyl-POSS (POSS–NH2) with tricarboxylic acids (such as 3-aminopropane-1,1,3-tricarboxylic acid), or acylation or esterification of the POSS end group by acryloyl chloride, succinic anhydride, etc. The mechanism of action of carboxylation-modified POSS monomers is as follows: First, the oxygen atom in the carboxyl group has a lone pair of electrons, which can interact with Cd on the quantum dot surface. 2+ Zn 2+ In 3+ First, it forms coordination bonds, with the carboxyl group specifically binding to the metal site on the quantum dot surface through bidentate or monodentate coordination. Second, the carboxyl group can replace the thiol / amine ligand, reducing defects and improving the fluorescence quantum yield. Third, the polarity of the carboxyl group increases the solvent dispersibility and resin compatibility of the POSS structure monomer. The advantages are that it not only has strong coordination force, but also repairs vacancy defects on the quantum dot surface, can form multi-point adsorption and coating layers, and enhances the chemical stability of the quantum dots.

[0041] This invention introduces polycarboxyl active groups into a cage-like silsesquioxane (POSS) structure, enabling the resulting modified POSS monomer to form stable coordination bonds or chemical bonds with metal atoms on the surface of quantum dots, thus constructing a dense surface coating layer. This coating layer can effectively suppress ligand desorption of quantum dots under solvent, heating, and light conditions, reduce surface defects, thereby improving the luminescence efficiency of quantum dots and maintaining their long-term photostability.

[0042] Furthermore, the carboxyl groups in the modified POSS-structured monomers possess a certain degree of polarity, which can enhance the dispersion ability of quantum dots in organic phases, significantly reduce the risk of aggregation and sedimentation, and improve the uniformity and storage stability of the adhesive system. The coordination between the carboxyl groups and the quantum dot surface can reduce non-radiative recombination pathways, which is beneficial for maintaining high quantum yields.

[0043] Furthermore, the cage-like inorganic framework of the POSS structure monomer possesses high thermal stability and steric hindrance effect, enabling the formation of a stable three-dimensional microstructure within the polymer network after adhesive curing. This allows quantum dots to be uniformly fixed within the crosslinking matrix, suppressing migration, aggregation, and phase separation, and improving structural stability during patterning and aging. Thus, this invention achieves a comprehensive improvement in quantum dot dispersibility, heat resistance, and photolithographic patterning performance.

[0044] In some more specific implementation schemes, taking the scheme with thiol as the first functional group as an example, the functionalized POSS structure monomer is obtained by thiol (-SH) modification. Specific modification methods can include grafting a thiol silane (such as MPTMS) to the POSS terminal, or introducing a thiol group after ring-opening of the POSS crotonate. The mechanism of action of the thiol-modified POSS structure monomer lies in the interaction between -SH and metal oxide ions (such as Cd) on the quantum dot surface. 2+ Zn 2+ In 3+ (S–M covalent coordination occurs), with high bond energy (stronger than –COOH coordination), forming a POSS–S–Metal coordination structure, which can replace traditional small molecule thiol ligands, forming a more stable "multi-point anchoring" structure and a strong bonded shell, thus improving thermal stability.

[0045] In some more specific implementation schemes, taking the amino group as the first functional group as an example, the functionalized POSS monomer is obtained by amino (-NH2) modification. Specific modification methods can include: introducing a polyamine structure (such as ethylenediamine or triethylenetetramine) through ammonolysis, or directly using commercially available amino-POSS monomers. The mechanism of action of the amino-modified POSS monomer lies in the interaction between the amino group and Zn on the quantum dot surface. 2+ Cd 2+ The surface forms coordination and can further undergo ring-opening reactions with photoresist resins (such as with epoxy monomers), providing dual reactivity.

[0046] In some more specific implementation schemes, taking the scheme with the first functional group being a phosphonic acid group as an example, it is suitable for the shell of CdSe / ZnS and InP / ZnS. The coordination mechanism is the formation of bidentate coordination, which has a strong surface passivation effect and can suppress non-radiative recombination.

[0047] In other embodiments, the POSS-quantum dot complex is formed by coordinating functionalized POSS structural monomers with quantum dots having a first pre-modified ligand via coordinate bonds. The first pre-modified ligand may contain one or more combinations of phosphonic acid groups, mercapto groups, selenoyl groups, carboxyl groups, acrylate groups, epoxy groups, etc., but is not limited to these. These ligands can be matched with functionalized POSS structural monomers to achieve precise control of the bridging link length.

[0048] In some other preferred embodiments, in order to better adapt the quantum dots to the photoresist system, the surface of the quantum dots may also have a second pre-modified ligand as an active end group. For example, the second pre-modified ligand may include one or more combinations of acrylic ligands, methacrylic ligands (UV curable), epoxy ligands (reactive with epoxy resin), isocyanate ligands, mercapto ligands, amino ligands (for grafting), etc., but is not limited to these.

[0049] Furthermore, at least one end of the functionalized POSS monomer also has a second functional group that matches the second pre-modified ligand. The second functional group may include, but is not limited to, one or more combinations of acrylate groups, methacrylate groups, epoxy groups, amino groups, and mercapto groups. Among these, acrylate groups and methacrylate groups can participate in free radical polymerization with C=C ligands on the quantum dot surface to form a copolymer network, with the quantum dots uniformly locked within the framework. Epoxy groups can undergo ring-opening addition with carboxyl or hydroxyl ligands on the quantum dot surface. Amino and mercapto groups can undergo nucleophilic attack reactions with epoxy, isocyanate, and other groups on the quantum dot surface to form covalent bridges.

[0050] In some embodiments, at least one end of the functionalized POSS monomer further has a third functional group, which is a photopolymerization active group capable of participating in the photopolymerization reaction, thereby enhancing its binding ability with the resin and strengthening network crosslinking. Specifically, the third functional group is a functional group capable of absorbing light energy and generating active species or undergoing structural changes under light irradiation. It may include one or more combinations of α-carbonyl groups, acylphosphine oxide groups, photoacid-producing groups, aromatic sulfonium salts or iodonium salts, cinnamic acid ester groups, chalcone groups, azo groups, aromatic conjugated light-absorbing groups, and ultraviolet absorber groups. More specifically, the third functional group may include one or more combinations of acrylate groups, methacrylate groups, epoxy groups, vinyl groups, and alkoxysilyl groups, but is not limited to these. The mechanism of introducing acrylate / methacrylate groups is that, under the action of a photoinitiator, they can co-photopolymerize with the resin monomer to construct a highly crosslinked, rigidly enhanced network structure, thereby improving heat resistance, creep resistance, and anti-creep ability, and can also directly participate in photoresist curing. The mechanism of introducing epoxy groups is that epoxy groups can participate in ring-opening polymerization with amino and carboxyl groups in the resin system, strengthening the network and improving thermal stability. The mechanism of introducing alkoxy silanization (-SiOR) is that it can hydrolyze / condense during the curing process to form a siloxane covalent network with the resin, and can also enhance compatibility and the integrity of the network structure.

[0051] In some embodiments, at least one end of the functionalized POSS structural monomer further has a fourth functional group, which can be a hydrophilic group or a hydrophobic group. The hydrophilic group includes, but is not limited to, one or more combinations of carboxyl, hydroxyl, amino, sulfonic acid, phosphonic acid, and polyether segments. The hydrophobic group can be one or more combinations of alkyl, aromatic, fluorinated alkyl, and siloxane segments, thereby regulating resin compatibility and flexibility. In this case, the same functionalized POSS structural monomer simultaneously undertakes quantum dot fixation, resin crosslinking, and compatibility regulation, forming a covalent / coordinative ternary composite structure of POSS-quantum dot-resin, significantly enhancing patterning accuracy, aging resistance, and thermal stability.

[0052] Furthermore, in order to enhance crosslinking stability, the functionalized POSS structural monomer may introduce groups such as imidazole, triazine, maleimide, and silane coupling groups.

[0053] In some embodiments, the POSS structural monomer may include one or more combinations of closed cage-like silsesquioxanes, partially open cage-like silsesquioxanes, or ladder-like silsesquioxanes, preferably closed cage-like silsesquioxanes.

[0054] In some preferred embodiments, the POSS structural unit is a polyhedral or quasi-polyhedral structure with a Si–O–Si inorganic framework, and its basic structural unit can be represented as (RSiO) 1.5 ) n , where n is 6 to 20.

[0055] In some preferred embodiments, the POSS structural monomer may be a T8-type closed cage-like silsesquioxane, T... 10 Type polyhedral silsesquioxane, T 12 The product is a combination of one or more polyhedral silsesquioxanes, especially T8 type closed cage-like silsesquioxanes, which have uniform distribution of terminal functional groups, high structural stability, and are suitable for multifunctional modification and to form a stable bond with quantum dots and resin systems.

[0056] In some more preferred embodiments, the POSS structural monomer is selected from at least one of the following structures:

[0057] (1) T8 type closed cage-like silsesquioxane;

[0058] (2) T 10 Type polyhedral silsesquioxane or T 12 Polyhedral silsesquioxanes;

[0059] (3) Partially open-cage silsesquioxanes, whose cages contain at least one unclosed Si-OH or Si-OR site;

[0060] (4) Ladder-shaped silsesquioxanes, whose Si-O-Si main chain has a double-chain ladder structure.

[0061] All of the above-mentioned POSS structural monomers with different structural forms achieve chemical bonding or coordination with the quantum dot surface and resin matrix by introducing carboxyl, mercapto, amino, phosphonic acid, acrylate, epoxy or combinations thereof at the silicon atom end positions.

[0062] In some preferred embodiments, each of the T8-type closed cage-like silsesquioxanes contains 2 to 8 functional groups (coordination sites), which is much larger than that of traditional small molecule ligands. The functional groups are combinations of the first, second, third, and fourth functional groups.

[0063] In some more preferred embodiments, the ratio of the first functional group, the third functional group and the fourth functional group is 1:1:0 to 4:2:2.

[0064] The functional group ratio of the functionalized POSS structure monomer of the present invention can be precisely controlled by the number of corner points (8 or 12), which can control the quantum dot bonding density, prevent excessive ligand exchange from causing fluorescence quenching, and also control the resin participation, so as to achieve controllable network density after patterning.

[0065] In some more specific implementations, the functionalized POSS structural monomer has the structure shown in formula (Ⅰ):

[0066] Equation (I)

[0067] Wherein, R1 is the aforementioned first functional group, R2 is the aforementioned third functional group, and R includes R1 or R2, or other groups, for example, other angles can be selected for solubility adjustment or steric hindrance control.

[0068] This invention designs at least one corner-connected ligand group (thiol, carboxyl, phosphate ester, etc.) that can bond to the surface of quantum dots, allowing quantum dots to directly combine with functionalized POSS structure monomers through coordination or covalent bonds, forming a POSS-quantum dot (QDs) complex. When photoresist components are added to this POSS-quantum dot complex, the quantum dots are no longer independent particles, but are embedded in the framework of the functionalized POSS structure monomers, forming a holistic quantum dot-POSS-photoresist network structure. This not only provides domain confinement but also improves thermal, optical, and chemical stability, as well as resistance to blue light and photobleaching. The outer shell on the quantum dot surface also adds mechanical rigidity and a thermally stable layer, effectively reducing ligand detachment during exposure / baking.

[0069] Moreover, the quantum dots in this application are pre-fixed in colloid, which can reduce QD migration and aggregation, improve the resolution of image edges, and achieve high-resolution graphics.

[0070] Specifically, the functionalized POSS structural monomer can be designed with multiple groups to adapt to different monomer resin systems, thus possessing high compatibility.

[0071] In some implementations, the quantum dot may include one or more combinations of group IV quantum dots, group II-VI quantum dots, group IV-VI quantum dots, group III-V quantum dots, etc., but is not limited thereto.

[0072] In some preferred embodiments, the quantum dot may include one or more combinations of CdSe / ZnS, CdS / ZnS, CdZnSe / ZnS, CdZnSeS / ZnS, CdSe / CdS, InP / ZnS, AgInGaS / ZnS, etc., but is not limited thereto.

[0073] In some embodiments, the content of quantum dots in the POSS-quantum dot composite is 5 to 50 wt%, preferably 5 to 40 wt%, and particularly preferably 5 to 30 wt%.

[0074] In some embodiments, when a photoresist matrix is ​​included, the content of the POSS-quantum dot composite material based on POSS connections is 1-40 wt%, preferably 1-30 wt%, particularly preferably 5-20 wt%, with the balance being the photoresist matrix. Furthermore, the quantum dot photoresist composite material of the present invention can contain various functionalized POSS structural monomers (long-chain, short-chain, flexible, rigid), and the density of the network structure can be controlled by their ratio, thereby improving the quantum dot luminescence retention rate, enhancing array uniformity, and ensuring that the pattern resolution is unaffected by quantum dot aggregation.

[0075] As another aspect of the technical solution of the present invention, the preparation method of the above-mentioned quantum dot photoresist composite material based on POSS connection includes:

[0076] Quantum dots are connected to POSS structure monomers through covalent or coordinate bonds to form POSS-quantum dot complexes;

[0077] The POSS-quantum dot composite material is prepared by mixing the POSS-quantum dot composite material or by mixing the POSS-quantum dot composite material with a photoresist system.

[0078] In some preferred embodiments, the mass ratio of the quantum dot to the POSS structure monomer is 1:1 to 1:9, preferably 1:2 to 1:4.

[0079] The photoresist system includes resin monomers, photoinitiators, and solvents.

[0080] In some embodiments, the resin monomer may include one or more of the following combinations: MMA (methyl methacrylate), MA (methyl acrylate), HEMA (2-hydroxyethyl methacrylate), BA (n-butyl acrylate), IBOA (isoborneol methacrylate, which can improve heat resistance and etching resistance), TMPTA (trimethylolpropane triacrylate), PETA (pentaerythritol tetraacrylate), N-acryloylmorpholine (ACMO) and its derivatives (which can improve high hardness and high heat resistance), but is not limited thereto.

[0081] In some preferred embodiments, the photoinitiator may include, but is not limited to, one or more combinations of TPO (2,4,6-tris(methylphenyl)phenylphosphine ketone (phenylphosphine photoinitiator)), Irgacure 819 (bis(2,4,6-trimethylphenyl)phosphonophenyl ketone), BAPO-type photoinitiator (bis(2,4,6-trimethylphenyl)phosphonophenyl ketone), cationic photoinitiators (such as triaryliodomonium salt), etc.

[0082] In some preferred embodiments, the solvent may include one or a combination of two of PGMEA (propylene glycol methyl ether acetate), GBL (gamma-butyrolactone), etc., but is not limited thereto.

[0083] As another aspect of the technical solution of the present invention, it relates to another POSS-connected quantum dot photoresist composite material, which includes: a composite host network framework formed by combining POSS structure monomers and resin monomers, and quantum dots, wherein the quantum dots are uniformly embedded in the composite host network framework to form a ternary hybrid network, wherein the POSS structure monomers and quantum dots are connected by covalent bonds or coordination bonds, and a dense coating layer is formed on the surface of the quantum dots.

[0084] In this quantum dot photoresist composite material, the POSS structure monomers and resin monomers combine to form a composite host network framework. The quantum dots are embedded inside the composite host network framework instead of being simply dispersed, which makes them more resistant to migration, swelling and exposure damage.

[0085] In this quantum dot photoresist composite material, quantum dots, POSS structure monomers and resin can form a ternary hybrid network, wherein quantum dots are bonded to POSS structure monomers, POSS structure monomers are bonded to resins, and resins are cross-linked with each other.

[0086] In some preferred embodiments, the types of functionalized POSS structural monomers, quantum dots, and resin monomers are as described above and will not be repeated here.

[0087] The mechanism by which the functionalized POSS structure monomers of the present invention combine with resin monomers includes chemical bonding mechanism, physical / non-covalent interaction mechanism and network structure effect.

[0088] Furthermore, the chemical bonding mechanism includes:

[0089] 1. Covalent crosslinking of carboxyl / amino groups with photopolymerizable monomers (i.e., resin monomers)

[0090] Functionalized POSS monomers introduce functional groups such as carboxyl (-COOH) and amino (-NH2) at their terminals. These functional groups can chemically react with the active groups in photopolymerizable monomers (such as acrylates, epoxides, or acrylamides). For example, carboxyl groups can form covalent bonds with the allyl groups of acrylate monomers through esterification; amino groups can form covalent bonds with epoxy groups through ring-opening reactions; the functionalized POSS monomer backbone can be directly cross-linked with photoresist monomer segments to form a chemically stable network structure.

[0091] 2. Coordination and quantum dot surface immobilization

[0092] The lone pair electrons in the carboxyl or amino groups at the end of the functionalized POSS monomer can interact with metal ions (such as Cd) on the quantum dot surface. 2+ Zn 2+ In 3+ Coordination bonds are formed to form a stable POSS-QD complex. When functionalized POSS structural monomers and resin monomers coexist, the functionalized POSS structural monomers act as chemical bridges to fix the quantum dots and also enhance the mechanical stability of the overall network through covalent bonds with the resin monomers.

[0093] Furthermore, physical / non-covalent interaction mechanisms include:

[0094] 1. Hydrogen bond network formation

[0095] The carboxyl or amino groups at the end of the functionalized POSS structure monomer can form hydrogen bonds with the hydroxyl, ether or ester groups in the resin monomer. These hydrogen bonds enhance the compatibility between the functionalized POSS structure monomer and the resin, enabling the functionalized POSS structure monomer to be uniformly dispersed in the photoresist and preventing agglomeration or precipitation.

[0096] 2. Van der Waals forces and steric hindrance

[0097] The cage-like rigid framework of functionalized POSS structural monomers provides steric hindrance at the molecular scale, preventing aggregation, while enabling resin segments to form a uniform network structure during curing. This three-dimensional spatial structure can increase crosslinking density and improve the mechanical properties and thermal stability of the resin.

[0098] Furthermore, network structure effects include:

[0099] 1. Double anchoring effect

[0100] Chemical bonding: Functionalized POSS monomers form a covalent network with resin monomers, enhancing the overall colloidal strength; Coordination / hydrogen bond fixation: Functionalized POSS monomers fix quantum dots, improving dispersibility and fluorescence stability; The dual effect ensures that quantum dots are uniformly distributed in the crosslinked network, improving the micron / submicron patterning precision;

[0101] 2. Adjustable crosslinking density

[0102] By controlling the ratio of carboxyl / amino groups at the end of functionalized POSS structure monomers to photopolymerizable monomers, the crosslinking density and rigidity of the network structure can be adjusted, thereby optimizing the viscosity, patternability, and high-temperature resistance of the photoresist.

[0103] 3. Interfacial chemical regulation

[0104] The organic end groups (i.e., the fourth functional group) of the functionalized POSS structure monomer backbone can regulate hydrophobicity / hydrophilicity, improve the compatibility between the functionalized POSS structure monomer and the resin, and prevent quantum dot migration or phase separation. At the same time, the carboxyl and amino groups can also form chemical anchors with the resin crosslinking network, further improving the heat resistance, light resistance and chemical aging resistance of the photoresist composite material.

[0105] In some preferred embodiments, the quantum dot content in the POSS-based quantum dot photoresist composite material is 0.1-50 wt%, and the content of functionalized POSS structural monomers is 1-30 wt%.

[0106] As another aspect of the technical solution of the present invention, the preparation method of the above-mentioned quantum dot photoresist composite material based on POSS connection includes: mixing POSS structure monomer, quantum dot, resin monomer, photoinitiator and solvent uniformly to obtain quantum dot photoresist composite material based on POSS connection.

[0107] In some embodiments, the preparation method includes: mixing functionalized POSS structure monomers, quantum dots, resin monomers, photoinitiators and solvents to form a mixture, and magnetically stirring for 30-180 min to obtain a quantum dot photoresist composite material based on POSS connections.

[0108] The mixture contains 1-20 wt% functionalized POSS monomers, 0.1-50 wt% quantum dots (preferably 0.5-10 wt%), 50-90 wt% resin monomers (preferably 50-85 wt%), and 0.1-5 wt% photoinitiator (preferably 1-5 wt%), with the remainder being solvent. The types of resin monomers, photoinitiators, and solvents are as previously described.

[0109] In some preferred embodiments, the mixture may also include additives, such as one or a combination of two of diluents, surfactants, etc., with the additives accounting for 0 to 5 wt% of the total mass.

[0110] As another aspect of the technical solution of the present invention, it relates to another POSS-connected quantum dot photoresist composite material, which includes: a composite host network framework formed by combining POSS structure monomers and resin monomers, and quantum dots, wherein the quantum dots are directly mixed in a dispersed form between the composite host network framework.

[0111] Furthermore, the types of functionalized POSS structure monomers and quantum dots are as previously described and will not be repeated here.

[0112] Accordingly, the preparation method of the POSS-connected quantum dot photoresist composite material includes: firstly, combining the POSS structure monomer with the resin monomer to form a composite main network framework, and then directly mixing the quantum dots in a dispersed form between the composite main network framework.

[0113] In some implementations, the POSS-based quantum dot photoresist composite material is suitable for two-photon polymerization (TPP) or ultraviolet lithography (UV) processes, and preferably can be precisely patterned by photolithography, with the characteristics of being pattern-friendly.

[0114] Furthermore, the POSS-based quantum dot photoresist composite material of the present invention can be used as a single-component quantum dot photoresist (QDPR) or a dispersed quantum dot photoresist (QDPR). The dispersed quantum dot photoresist can be added to a conventional resin system as a nano-concentrated slurry.

[0115] As another aspect of the technical solution of the present invention, it also relates to the application of the quantum dot photoresist composite material based on POSS connection in Micro-LED full-color display.

[0116] Accordingly, another aspect of the technical solution of the present invention also relates to a quantum dot patterning method, comprising the following steps:

[0117] The quantum dot photoresist composite material based on POSS connections is applied (e.g., spin-coated or drop-coated) to the surface of the Micro-LED chip;

[0118] Graphical exposure can be performed using methods such as mask exposure, laser scanning, or TPP.

[0119] After development, patterned quantum dot patterns of corresponding colors (red, green, and blue) are obtained.

[0120] Furthermore, the thickness of the quantum dot photoresist composite material based on POSS connections applied to the surface of the Micro-LED chip is generally 1~10 µm.

[0121] This invention coats the aforementioned quantum dot photoresist composite material based on POSS connections onto a Micro-LED chip array, enabling: selective patterning of red and green wavelength QD-POSS materials; formation of corresponding color fluorescent patterns between Micro-LED pixels after development; and submicron-level high-resolution patterns, meeting the requirements of full-color single-chip Micro-LEDs.

[0122] Furthermore, by adjusting the different ligand groups of the POSS-quantum dot complex, the present invention can achieve independent patterning of RGB channels, adapting to the pixel-level full-color integration of Micro-LEDs.

[0123] The quantum dot photoresist composite material of this invention exhibits a more uniform distribution of quantum dots (high dispersion), more stable patterned light emission, and superior color saturation and uniformity compared to existing technologies. Furthermore, this invention enables high-resolution full-color patterning with independent three-color channels on a single Micro-LED wafer, demonstrating greater functionality and applicability in practical applications.

[0124] The specific embodiments of the present invention will be described in more detail below with reference to examples, but these embodiments do not constitute a limitation of the present invention. All modifications that are conceived or derived from the content disclosed in this invention are considered to be within the scope of protection of this invention.

[0125] All raw materials used in the embodiments of this invention were purchased from the market.

[0126] The instruments and equipment used in the following examples are all conventional equipment in the relevant fields, and the performance tests are all conducted in accordance with the requirements of conventional standards.

[0127] The thiol exchange method used in the following examples can be achieved using anhydrous organic solvents such as chloroform (CHCl3), toluene, or dichloromethane (DCM). The quantum dot solution and functionalized POSS monomer are mixed at a molar ratio of 1:3 to 1:10 (POSS in excess to ensure complete exchange). The mixture is stirred magnetically for 2 to 12 hours at room temperature or with slight heating (25–50 °C) to prevent quantum dot degradation; the mixture can be adjusted according to the concentrations of quantum dots and POSS. After exchange, the free POSS and residual pro-ligands are removed by precipitation with ethanol or acetone, centrifugation, and redispersed in the target solvent (such as toluene or photoresist resin solvent).

[0128] Example 1: Preparation of CdSe / ZnS quantum dot photoresist composite material based on POSS linkage

[0129] 1. Provide a functionalized POSS structural unit (POSS-(-CH2=CHCOO-)6-(SH)2), the structure of which is shown in formula (Ⅱ):

[0130] Formula (II)

[0131] Wherein, R1 is -SH and R2 is an acrylate group.

[0132] 2. Quantum dot modification

[0133] CdSe / ZnS quantum dots coated with tri-n-octylphosphine (TOP) / trioctylphosphine oxide (TOPO) were used to replace some of the surface ligands with thiol sites in POSS-(-CH2=CHCOO-)6-(SH)2 via thiol exchange, forming a POSS-QDs complex. The thiol exchange was carried out in an organic solvent at room temperature to 50 °C for 2–12 h. The POSS monomer was added in excess of the quantum dot surface ligands to achieve partial or complete ligand replacement.

[0134] 3. Preparation of photoresist composite materials

[0135] The POSS-QDs complex prepared in step 2 was dispersed in the following mixture: 50 wt% of trifunctional acrylic acid monomer (TMPTA), 2 wt% of photoinitiator (TPO), 30 wt% of PGMEA solvent, and 18 wt% of POSS-QDs complex, of which the content of QDs was 15 wt%.

[0136] After magnetic stirring for 30 minutes and ultrasonic degassing for 1-20 minutes, a transparent and stable quantum dot photoresist composite material was obtained by filtration.

[0137] 4. Graphical processing

[0138] The quantum dot photoresist composite material prepared in step 3 was spin-coated onto a Micro LED substrate, exposed with an ultraviolet mask, cured for 60 seconds, and developed to form a red pattern with a resolution of 10 μm.

[0139] In this embodiment, the quantum dots in the quantum dot photoresist composite material are directly connected, uniformly distributed, highly stable, and have good pattern conformation.

[0140] Example 2

[0141] Preparation of CdSe / CdS quantum dot photoresist composite material based on carboxyl-functionalized POSS linkage

[0142] 1. Provide functional POS structure units

[0143] A carboxyl-functionalized POSS structure monomer is provided, whose structure is represented as: POSS-(COOH)2-(CH2=CHCOO-)6, wherein the carboxyl group serves as the quantum dot coordinating group and the acrylate group serves as the photopolymerization active group.

[0144] 2. Quantum dot modification

[0145] Using CdSe / CdS core-shell quantum dots coated with oleic acid / oleylamine ligands, carboxyl groups were replaced by carboxyl groups from POSS monomers via carboxyl coordination exchange, forming a POSS-QDs complex. This coordination exchange was carried out in an organic solvent at room temperature to 60 °C for 4–12 h, with the POSS monomer added in excess of the ligands on the quantum dot surface.

[0146] 3. Preparation of photoresist composite materials

[0147] The POSS-QDs complex obtained in step 2 was dispersed in the following mixture: 50 wt% of trifunctional acrylic acid monomer (TMPTA), 2 wt% of photoinitiator (TPO), 30 wt% of PGMEA solvent, and 18 wt% of POSS-QDs complex, wherein the quantum dot content was 15 wt%.

[0148] After magnetic stirring for 30-60 minutes, ultrasonic degassing for 1-20 minutes, and filtration, a transparent and stable quantum dot photoresist composite material is obtained.

[0149] 4. Graphical processing

[0150] The above-mentioned quantum dot photoresist composite material was spin-coated onto the surface of a Micro-LED substrate, cured by exposure to a UV mask for 60 seconds, and developed to form a red luminescent pattern with a resolution of approximately 2 μm.

[0151] Example 3

[0152] Preparation of InP / ZnS quantum dot photoresist composite material based on amino-functionalized POSS linkage

[0153] 1. Provide functional POS structure units

[0154] An amino-functionalized POSS monomer is provided, the structure of which is represented as: POSS-(NH2)2-(CH2=CHCOO-)6, wherein the amino group serves as a surface coordination and reactive group of the quantum dot.

[0155] 2. Quantum dot modification

[0156] Using InP / ZnS core-shell quantum dots with a surface coated with aliphatic amine ligands, the interaction between the amino group and the Zn group on the quantum dot surface is achieved. 2+ The coordination effect of POSS anchors the POSS structure monomers onto the quantum dot surface, forming a POSS-QDs complex. The reaction is carried out under an inert atmosphere at 30–70 °C for 2–8 h.

[0157] 3. Preparation of photoresist composite materials

[0158] The obtained POSS-QDs composite was added to the following photoresist system: 48 wt% IBOA / ACMO mixed monomer, 10 wt% TMPTA, 2 wt% photoinitiator (TPO or Irgacure 819), 22 wt% PGMEA, and 18 wt% POSS-QDs composite, wherein the quantum dot content was 10 wt%.

[0159] After thorough mixing and degassing and filtration, a quantum dot photoresist composite material suitable for photolithography is obtained.

[0160] 4. Graphical processing

[0161] By using ultraviolet exposure for patterning, highly uniform green luminescent micro-patterns can be obtained.

[0162] Example 4

[0163] Preparation of AgInGaS / ZnS quantum dot photoresist composite material based on phosphonate-functionalized POSS linkage

[0164] 1. Provide functional POS structure units

[0165] A phosphonic acid-functionalized POSS structure monomer is provided, whose structure is represented as: POSS-(PO3H2)2-(CH2=CHCOO-)6, where the phosphonic acid group is used to form a strong coordination bond with the surface of the quantum dot shell.

[0166] 2. Quantum dot modification

[0167] AgInGaS / ZnS quantum dots coated with thiol or amine ligands are used to fix POSS structure monomers on the surface of quantum dots through polydentate coordination between phosphonic acid groups and the ZnS shell surface, forming a stable POSS-QDs complex. The reaction is carried out at 40~80 °C for 4~10 h.

[0168] 3. Preparation of photoresist composite materials

[0169] The POSS-QDs composite was mixed with the following components: 45 wt% TMPTA, 10 wt% PETA, 2 wt% photoinitiator (BAPO), 25 wt% GBL / PGMEA mixed solvent, and 18 wt% POSS-QDs composite, wherein the quantum dot content was 30 wt%.

[0170] Quantum dot photoresist composite material was prepared by thorough mixing and degassing.

[0171] 4. Graphical processing

[0172] By using a mask exposure method for curing and development, a stable green luminescent pattern can be formed.

[0173] Example 5

[0174] Quantum dot photoresist composites based on phosphoxy or selenol functionalized POSS linkages

[0175] The steps in this embodiment are basically the same as those in embodiments 2-4, except that: phosphoxy groups (P=O) or selenoyl groups (–SeH) are introduced at the end of the functionalized POSS structure monomer. The phosphoxy groups bind to the metal ions on the quantum dot surface through strong polar coordination; the selenoyl groups form M–Se bonds with the metal on the quantum dot surface, which have higher thermal stability than M–S bonds.

[0176] The resulting quantum dot photoresist composite material maintains high luminescence intensity and pattern integrity even under high-temperature exposure and long-term aging conditions.

[0177] Example 6

[0178] Preparation of CdSe / ZnS quantum dot photoresist composite material based on ligand-exchanged quantum dots combined with unmodified POSS

[0179] 1. Quantum dot ligand exchange

[0180] We provide CdSe / ZnS core-shell quantum dots with a surface coated with tri-n-octylphosphine (TOP) / trioctylphosphine oxide (TOPO).

[0181] The CdSe / ZnS core-shell quantum dots were mixed with low-molecular-weight ligands containing thiol groups (such as mercaptoacetic acid, mercaptoacrylic acid, or dithiol compounds) in an organic solvent. Through thiol exchange, some ligands on the quantum dot surface were replaced by thiol ligands, resulting in quantum dots with thiol-containing active sites on their surface. The ligand exchange reaction was carried out at 25–60 °C for 2–10 h, with the thiol ligands added in excess relative to the ligands on the quantum dot surface.

[0182] 2. Combination of quantum dots and POSS

[0183] The surface-modified quantum dots obtained in step 1 are mixed with unfunctionalized POSS molecules (such as octaisobutyl POSS or octaphenyl POSS). Under stirring conditions, the thiol groups on the surface of the quantum dots are stably bonded to the Si–O backbone of POSS or its surface organic groups through coordination, hydrogen bonding or van der Waals interactions to obtain the POSS-QDs complex.

[0184] 3. Preparation of photoresist composite materials

[0185] The above-mentioned POSS-QDs composite was added to the following photoresist system: 50 wt% trifunctional acrylic acid monomer (TMPTA), 2 wt% photoinitiator (TPO), 30 wt% PGMEA solvent, and 18 wt% POSS-QDs composite, wherein the quantum dot content was 20 wt%.

[0186] After magnetic stirring for 30 minutes, degassing, and filtration, a transparent and stable quantum dot photoresist composite material was obtained.

[0187] 4. Graphical processing

[0188] Quantum dot photoresist composite material is spin-coated onto the substrate surface, cured and developed by ultraviolet exposure to form a high-resolution luminescent pattern.

[0189] Example 7

[0190] Preparation of InP / ZnS quantum dot photoresist composite material based on the combination of carboxyl ligand-modified quantum dots and unmodified POSS

[0191] 1. Quantum dot ligand exchange

[0192] A core-shell InP / ZnS quantum dot with a surface coated with aliphatic amine ligands is provided. The quantum dots are ligand exchanged using carboxyl ligands (such as acrylic acid, methacrylic acid or polycarboxyl molecules) to enable the quantum dot surface to carry carboxyl functional groups.

[0193] 2. Combination of quantum dots and POSS

[0194] Quantum dots with carboxyl groups on their surface are mixed with unmodified POSS molecules. The carboxyl groups and the silicon-oxygen framework of POSS or its organic substituents form a composite structure through multi-point weak coordination and intermolecular interactions, resulting in the POSS-QDs composite.

[0195] 3. Preparation of photoresist composite materials

[0196] The POSS-QDs complex was dispersed in the following system: 45 wt% IBOA / ACMO mixed monomers, 10 wt% TMPTA, 2 wt% photoinitiator (Irgacure 819), 25 wt% PGMEA, and 18 wt% POSS-QDs complex, of which the quantum dot content was 25 wt%.

[0197] Quantum dot photoresist composite material was prepared by thorough mixing.

[0198] 4. Graphical processing

[0199] A uniform and stable green luminescent pattern was obtained by using ultraviolet mask exposure for patterning.

[0200] Example 8

[0201] Preparation of AgInGaS / ZnS quantum dot photoresist composite material based on the combination of phosphonic acid ligand-modified quantum dots and unmodified POSS

[0202] 1. Quantum dot ligand exchange

[0203] We provide AgInGaS / ZnS core-shell quantum dots and use phosphonic acid-containing ligands (such as alkylphosphonic acid or polyphosphonic acid ligands) to perform surface ligand exchange, so that the surface of the quantum dots carries phosphonic acid groups.

[0204] 2. Combination of quantum dots and POSS

[0205] When phosphonic acid-modified quantum dots are mixed with unfunctionalized POSS molecules, the phosphonic acid groups form strong coordination with the metal ions on the quantum dot shell, while POSS coats the quantum dots through multi-point adsorption, forming a POSS-QDs complex.

[0206] 3. Preparation of photoresist composite materials

[0207] The POSS-QDs complex was mixed with the following components: 45 wt% TMPTA, 10 wt% PETA, 2 wt% photoinitiator (BAPO), 25 wt% GBL / PGMEA mixed solvent, and 18 wt% POSS-QDs complex, wherein the quantum dot content was 40 wt%.

[0208] Quantum dot photoresist composite material was prepared by thorough mixing.

[0209] 4. Graphical processing

[0210] Highly stable red-orange luminescent micropatterns can be obtained through exposure and development processes.

[0211] Example 9

[0212] Based on Examples 6-8, the quantum dot ligands were replaced with one or more of amino, phosphoxy, and selenool groups.

[0213] POSS structural monomers are cage-like siloxane molecules without the introduction of photopolymerizable active groups.

[0214] Quantum dots form composite structures through multi-point interactions between surface functional ligands and POSS, and are then mixed with photoresist resin systems to prepare quantum dot photoresist composite materials.

[0215] Example 10

[0216] Preparation of CdSe / ZnS quantum dot photoresist composites based on functionalized POSS linked by the introduction of methacrylate photopolymerization active groups

[0217] 1. Provision of functional POS structure units

[0218] A functionalized POSS-structured monomer with photopolymerization active groups of methacrylate is provided, and its structure is represented as: POSS-(–O–CO–C(CH3)=CH2)6–(SH)2, wherein POSS is a cage-like silsesquioxane structure, with methacrylate groups introduced at some terminal positions as photopolymerization active sites and thiol groups introduced at some terminal positions as quantum dot binding sites.

[0219] 2. Quantum dot modification and bonding

[0220] We provide CdSe / ZnS core-shell quantum dots with a surface coated with tri-n-octylphosphine (TOP) / trioctylphosphine oxide (TOPO).

[0221] The quantum dots are mixed with the functionalized POSS monomer from step 1 in an anhydrous organic solvent. Through the coordination of thiol groups with metal ions on the surface of the quantum dots, the ligands on the surface of the quantum dots are partially replaced, forming a POSS-QDs complex.

[0222] 3. Preparation of photoresist composite materials

[0223] The above-mentioned POSS-QDs complex was added to the following system: 45 wt% trimethylolpropane methacrylate (TMPTMA), 20 wt% functionalized POSS-QDs complex (including 45 wt% quantum dots), 2 wt% photoinitiator (TPO), and 33 wt% PGMEA solvent;

[0224] After magnetic stirring for 30 minutes, degassing, and filtration, a uniform and transparent quantum dot photoresist composite material was obtained.

[0225] 4. Graphical processing

[0226] Quantum dot photoresist is spin-coated onto the substrate surface, cured and developed after 60 seconds of UV exposure, which can form a red luminescent pattern with a resolution better than 2 μm.

[0227] Example 11

[0228] Preparation of InP / ZnS quantum dot photoresist composite material based on methacrylate-functionalized POSS

[0229] 1. Provision of Functional POS Systems

[0230] A class of POSS monomers with methacrylate groups at the terminal positions are provided, wherein the number of methacrylate groups introduced in the structure is 2 to 8, for participation in photoinitiated free radical polymerization reactions.

[0231] 2. Quantum dot bonding

[0232] InP / ZnS quantum dots with surface modified by carboxyl or amino ligands are mixed with the functionalized POSS to form a stable POSS-QDs complex through coordination and intermolecular forces.

[0233] 3. Construction of photoresist system

[0234] The POSS-QDs complex was added to the following mixture: IBOA 30 wt%, ACMO 15 wt%, TMPTMA 10 wt%, photoinitiator (Irgacure 819) 2 wt%, solvent (PGMEA): 43 wt%; wherein, the quantum dot content in the POSS-QDs complex was 26 wt%.

[0235] 4. Graphical applications

[0236] After ultraviolet exposure and development, a uniform and stable green luminescent pattern is obtained.

[0237] Example 12

[0238] In the above embodiments 10 and 11, the photopolymerization active group is a methacrylate group, which can directly participate in the UV-initiated free radical polymerization reaction, so that the functionalized POSS is embedded in the photoresist resin network as a crosslinking node; the quantum dots are fixed in the crosslinking network through the multi-point anchoring effect of POSS, thereby significantly improving the dispersion stability, heat resistance and pattern conformation ability of quantum dots in photoresist.

[0239] Example 13

[0240] Preparation of CdSe / CdS quantum dot photoresist composites based on functionalized POSS with introduced epoxy photopolymerization active groups

[0241] 1. Provision of functional POS structure units

[0242] A functionalized POSS monomer with terminal epoxy groups is provided, the structure of which is represented as: POSS-(–CH2–CHO–CH2)6–(SH)2, wherein POSS is a cage-like silsesquioxane structure, with some terminal epoxy groups introduced as photopolymerization active sites and some terminal thiol groups introduced for coordination bonding of quantum dots.

[0243] 2. Quantum dot bonding

[0244] We provide CdSe / CdS quantum dots with TOP / TOPO coating.

[0245] Quantum dots are mixed with the functionalized POSS structure monomers from step 1 in an anhydrous solvent. Through the coordination of thiol groups with metal ions on the surface of quantum dots, partial replacement of surface ligands is achieved, forming a stable POSS-QDs complex.

[0246] 3. Preparation of photoresist composite materials

[0247] The above-mentioned POSS-QDs composite was added to the following system: 40 wt% epoxy resin monomer (such as bisphenol A type epoxy resin), 15 wt% reactive diluent (such as 1,4-butanediol diglycidyl ether), 20 wt% POSS-QDs composite, of which the quantum dot content was 20 wt%, 2 wt% cationic photoinitiator (such as triaryliodonium salt), and 23 wt% PGMEA solvent;

[0248] After stirring and degassing, a uniform and stable quantum dot photoresist composite material was obtained.

[0249] 4. Graphical processing

[0250] Photoresist is spin-coated onto the substrate surface, and after exposure to ultraviolet light for 60 seconds, a cationic ring-opening polymerization reaction of epoxy groups occurs. After development, a red luminescent pattern is obtained.

[0251] Example 14

[0252] Preparation of functionalized POSS-linked AgInGaS / ZnS quantum dot photoresist composites based on the introduction of vinyl photopolymerization active groups

[0253] 1. Provision of functional POS structure units

[0254] A functionalized POSS monomer with vinyl groups introduced at the end is provided, and its structure is represented as: POSS-(–CH=CH2)6–(COOH)2, wherein the vinyl group is used to participate in the free radical polymerization reaction, and the carboxyl group is used to form a coordination bond with the metal ions on the surface of the quantum dot.

[0255] 2. Quantum dot modification and bonding

[0256] AgInGaS / ZnS quantum dots with surface pre-modified by carboxyl ligands are provided, and they are mixed with the functionalized POSS structure monomer to form a POSS-QDs complex through multi-point coordination.

[0257] 3. Construction of photoresist system

[0258] The POSS-QDs complex was added to the following mixture: 35 wt% acrylate monomer (IBOA), 15 wt% vinyl monomer (styrene or vinyl ether), 18 wt% POSS-QDs complex (with a quantum dot content of 5.6 wt%), 2 wt% photoinitiator (BAPO), and 30 wt% solvent (GBL).

[0259] A quantum dot photoresist composite material was prepared after thorough mixing.

[0260] 4. Graphical processing

[0261] Ultraviolet exposure is used to induce free radical polymerization of vinyl groups, and a stable luminescent pattern is formed after development.

[0262] Example 15

[0263] Preparation of POSS-quantum dot photoresist composite material with high quantum dot anchoring density

[0264] 1. Provision of functional POS structure units

[0265] A functionalized POSS-structured monomer is provided, the structure of which is represented as: POSS-(SH)4-(MA)2-(R)2, wherein -SH is a quantum dot bonding group; MA is a methacrylate group; and -R is an inert short-chain alkyl group (such as methyl or ethyl), wherein the ratio of -SH, MA to inert short-chain alkyl is 4:2:2.

[0266] 2. Quantum dot bonding

[0267] CdSe / ZnS quantum dots with TOP / TOPO ligands on their surface are mixed with the above-mentioned functionalized POSS structure monomers, and high-density surface anchoring is achieved through multi-site thiol coordination to form a POSS-QDs complex.

[0268] 3. Photoresist preparation and patterning

[0269] The photoresist was prepared using the same acrylate system as in Example 1 and then exposed and developed.

[0270] Test results show that the quantum dots in the quantum dot photoresist composite material of this embodiment are strongly anchored, making it suitable for high-brightness and long-life applications.

[0271] Example 16

[0272] POSS-quantum dot photoresist composite material that balances quantum dot stability and patterning precision

[0273] 1. Functional POS Structure Monolith

[0274] A functionalized POSS structural monomer is provided, the structure of which is represented as: POSS-(COOH)2-(MA)4-(C8H 17 )2, in which -COOH, MA and -C8H 17 The ratio of their quantities is 2:4:2.

[0275] 2. Quantum dot bonding

[0276] Stable POSS-QDs complexes are formed by coordinating InP / ZnS quantum dots with the above-mentioned functionalized POSS structure monomers via carboxyl groups.

[0277] 3. Photoresist preparation

[0278] The above-mentioned POSS-QDs complex was added to the following system: TMPTA 50 wt%, IBOA 20 wt%, POSS-QDs complex 10 wt%, BAPO-type photoinitiator 2 wt%, and PGMEA solvent 18 wt%.

[0279] After stirring and degassing, a uniform and stable quantum dot photoresist composite material was obtained.

[0280] After UV exposure and development, it can be concluded that this embodiment achieves a good balance between dispersibility, crosslinking density, and pattern boundary clarity, making it suitable for fine patterning of Micro-LEDs.

[0281] Example 17

[0282] Highly cross-linked, highly resistant to humidity and heat POSS-quantum dot photoresist composite material

[0283] 1. Functional POS Structure Monolith

[0284] A functionalized POSS structural monomer is provided, whose structure is represented as: POSS-(PO3H2)1-(Epoxy)5-(C 12 H 25 )2, where -PO3H2, Epoxy and -C 12 H 25 The ratio of their quantities is 1:5:2.

[0285] 2. Quantum dot bonding

[0286] AgInGaS / ZnS quantum dots are used to form stable POSS-QDs complexes by connecting them to the functionalized POSS structure monomers through single-point coordination of phosphonic acid groups.

[0287] 3. Photoresist preparation and curing

[0288] The photoresist was prepared and exposed and developed using the same epoxy cationic photoinitiator system as in Example 12. It can be concluded that in this example, the functionalized POSS structure monomers deeply participate in network crosslinking, quantum dot migration is suppressed by the network structure, and the material exhibits excellent resistance to damp heat and aging.

[0289] Example 18

[0290] POSS-quantum dot photoresist composite material based on methacrylate resin monomers

[0291] 1. Resin monomers include: methyl methacrylate (MMA) and borneol methacrylate (IBOMA);

[0292] 2. The composite system comprises: MMA / IBOMA 45 wt%, functionalized POSS-QDs composite (same as in Example 2) 20 wt%, photoinitiator (TPO) 2 wt%, and PGMEA 33 wt%.

[0293] After stirring and degassing, a uniform and stable quantum dot photoresist composite material was obtained.

[0294] 3. After UV exposure and development, it can be concluded that the system has small exposure shrinkage and stable pattern edges, making it suitable for high-resolution Micro-LED patterning.

[0295] Example 19

[0296] POSS-quantum dot photoresist composite material based on multifunctional acrylate crosslinked resin

[0297] 1. Resin monomers include: trimethylolpropane triacrylate (TMPTA) and pentaerythritol tetraacrylate (PETA);

[0298] 2. The composite system comprises: 50 wt% TMPTA / PETA, 18 wt% functionalized POSS-QDs composite (same as in Example 2), 2 wt% photoinitiator (BAPO), and 30 wt% solvent (GBL).

[0299] After stirring and degassing, a uniform and stable quantum dot photoresist composite material was obtained.

[0300] 3. After UV exposure and development, it can be concluded that the system has a high cross-linking density, POSS structural monomers participate in network construction, and the heat resistance and aging resistance are significantly improved.

[0301] Example 20

[0302] POSS-quantum dot photoresist composite material based on epoxy resin monomers

[0303] 1. Resin monomers include: bisphenol A type epoxy resin and 1,4-butanediol diglycidyl ether (reactive diluent).

[0304] 2. The composite system comprises: 40 wt% epoxy resin system, 20 wt% functionalized POSS-QDs composite (same as in Example 12), 2 wt% cationic photoinitiator (iodonium salt), and 38 wt% PGMEA;

[0305] After stirring and degassing, a uniform and stable quantum dot photoresist composite material was obtained.

[0306] 3. Through ultraviolet exposure and development, it can be concluded that the system is not affected by oxygen inhibition during the exposure process and is suitable for thick films and high-depth patterns.

[0307] Example 21

[0308] POSS-quantum dot photoresist composite material based on vinyl / styrene resin monomers

[0309] 1. Resin monomers, including: styrene and vinyl ether monomers;

[0310] 2. The composite system comprises: 35 wt% vinyl resin system, 22 wt% POSS-QDs composite (same as in Example 13), 2 wt% photoinitiator (BAPO), and 41 wt% solvent (GBL);

[0311] After stirring and degassing, a uniform and stable quantum dot photoresist composite material was obtained.

[0312] 3. After UV exposure and development, it can be concluded that the hydrophobic network and the POSS cage structure work together to significantly suppress fluorescence decay caused by water vapor intrusion.

[0313] Example 22

[0314] POSS-quantum dot photoresist composite material based on hydroxyl-containing functional monomers

[0315] 1. Resin monomers, including: 2-hydroxyethyl methacrylate (HEMA), ACMO or its derivatives;

[0316] 2. The composite system comprises: HEMA / ACMO 40 wt%, the same POSS-QDs composite as in Example 7 20 wt%, photoinitiator (Irgacure 819) 2 wt%, and PGMEA 38 wt%.

[0317] After stirring and degassing, a uniform and stable quantum dot photoresist composite material was obtained.

[0318] 3. After UV exposure and development, it can be seen that hydroxyl groups form hydrogen bonds with the surface of POSS / QDs, which improves dispersion stability and pattern uniformity.

[0319] Example 23

[0320] Based on photopolymerization-functionalized POSS-quantum dot photoresist composite material

[0321] 1. Functional POS Structure Monolith

[0322] A functionalized POSS-structured monomer containing photopolymerizable active groups is provided, the structure of which is represented as: POSS-(methacrylate)6-(thiol)2, wherein the thiol group is used for coordination with the quantum dot surface, and the methacrylate group is used for photopolymer crosslinking.

[0323] 2. Quantum dot modification

[0324] CdSe / ZnS quantum dots with TOP / TOPO coatings on their surface are mixed with the above-mentioned functionalized POSS structure monomers under an inert atmosphere, and ligand exchange is carried out through thiol-metal coordination to form a POSS-QDs complex.

[0325] 3. Preparation of resin-free photoresist

[0326] The above-mentioned POSS-QDs complex was directly added to the following system: 98 wt% POSS-QDs complex, 2 wt% photoinitiator (TPO);

[0327] After thorough mixing, a quantum dot photoresist composite material without resin monomers is obtained.

[0328] 4. Graphical processing

[0329] The obtained material was spin-coated onto the surface of a Micro-LED substrate. After UV exposure, the methacrylate groups at the POSS terminals underwent cross-linking and curing. After development, a stable red quantum dot pattern was formed.

[0330] Example 24

[0331] Based on epoxy-functionalized POSS-quantum dot photoresist composite material

[0332] 1. Functional POS Structure Monolith

[0333] An epoxy-functionalized POSS structure monomer is provided, the structure of which is represented as: POSS-(epoxy)6-(phosphonic acid)2;

[0334] 2. Quantum dot modification

[0335] InP / ZnS quantum dots with phosphonic acid ligands pre-modified on their surface are mixed with the functionalized POSS structure monomer to form a POSS-QDs complex through phosphonic acid-metal coordination.

[0336] 3. Preparation of resin-free composite materials

[0337] The obtained POSS-QDs complex was added to the following system: 97 wt% POSS-QDs complex, 3 wt% cationic photoinitiator (iodonium salt);

[0338] After thorough mixing, a quantum dot photoresist composite material without resin monomers is obtained.

[0339] 4. Graphical processing

[0340] Under ultraviolet light exposure, the terminal epoxy groups of POSS undergo ring-opening polymerization, self-constructing a three-dimensional cross-linked network to achieve pattern curing.

[0341] Example 25

[0342] Based on sol-gel POSS-quantum dot photoresist composite material

[0343] 1. Functional POS Structure Monolith

[0344] A POSS-structured monomer containing a hydrolyzable silane group is provided, the structure of which is represented as: POSS-(Si-OR)6-(mercapto)2;

[0345] 2. Quantum dot modification

[0346] The CdSe / CdS quantum dots are subjected to thiol exchange with the functionalized POSS structure monomer to form a POSS-QDs complex.

[0347] 3. Preparation of resin-free film-forming system

[0348] The POSS-QDs complex was dissolved in an alcohol solvent, and a trace amount of water and an acidic catalyst were added to initiate the hydrolysis and condensation reaction of Si-OR to form a silicon-oxygen network.

[0349] 4. Graphical processing

[0350] Patterned film formation can be achieved by controlling the gelation area through mask exposure or local heating.

[0351] Example 26

[0352] Quantum dot photoresist composite material based on POSS-resin network and quantum dot physical embedding.

[0353] 1. Construction of the POSS-resin composite matrix network

[0354] A functionalized POSS structural monomer, POSS-(methacrylate)8, is provided and mixed with an acrylic resin monomer (TMPTA) at a mass ratio of 1:4. Under the action of a photoinitiator (TPO), the mixture is exposed to ultraviolet light to form a three-dimensional cross-linked POSS-resin composite main network framework. The POSS structural monomer participates in free radical polymerization through its terminal methacrylate groups, embedding itself in the resin network as a multifunctional cross-linking node, thereby improving the network's rigidity and thermal stability.

[0355] 2. Physical embedding of quantum dots

[0356] CdSe / ZnS quantum dots with TOP / TOPO coating were directly added to the above-mentioned POSS-resin prepolymer solution and magnetically stirred for 30 min to ensure that the quantum dots were uniformly dispersed in the system.

[0357] The quantum dots are not covalently or coordinately bonded to the POSS structural monomers or resin monomers, and exist only in a physically dispersed form in the mixed system before the formation of the POSS-resin crosslinking network.

[0358] 3. Preparation of photoresist composite materials

[0359] The above-mentioned mixed system was spin-coated onto the surface of a substrate. After exposure to ultraviolet light, POSS and resin monomers cross-linked and cured to form a continuous three-dimensional network structure. Quantum dots were confined between the mesh pores of this network structure, resulting in a quantum dot photoresist composite material based on a POSS-resin network.

[0360] 4. Graphical processing

[0361] The obtained quantum dot photoresist composite material was applied to the surface of a Micro-LED chip, and patterned quantum dot light-emitting areas were obtained through ultraviolet mask exposure and development processes.

[0362] Example 27

[0363] Quantum dot confined photoresist composite material based on high cross-linking density POSS-resin network

[0364] 1. Construction of composite subject network

[0365] Functionalized POSS-structured monomer POSS-(methacrylate)6-(hydrophobic alkyl)2 is mixed with multifunctional acrylate monomers TMPTA and PETA in a certain proportion to form a high crosslinking density prepolymer system.

[0366] 2. Methods of adding quantum dots

[0367] AgInS2 / ZnS quantum dots are directly dispersed in the above prepolymer system. The quantum dots do not carry reactive ligands and do not chemically bond with POSS or resin. They exist only in a physically dispersed state.

[0368] 3. Curing and Confinement

[0369] After exposure to ultraviolet light, POSS rapidly crosslinks with the resin monomers to form a dense network, and the quantum dots are confined in the nanoscale pores of the crosslinked network.

[0370] Example 28

[0371] Preparation of quantum dot photoresist composite materials based on POSS-resin-quantum dot ternary hybrid network

[0372] 1. Premixing of functionalized POSS structural monomers and resin monomers

[0373] A functionalized POSS structure monomer is provided, wherein the functionalized POSS structure monomer is a T8-type closed cage-like silsesquioxane, and two types of functional groups are introduced on the outside of the cage: one type is a thiol functional group that can coordinate or covalently connect with the surface of quantum dots; the other type is an acrylate functional group that can participate in photopolymerization reaction.

[0374] The functionalized POSS structural monomer is mixed with the resin monomer, wherein the resin monomer is trimethylolpropane triacrylate (TMPTA), and the mass ratio of the functionalized POSS structural monomer to the resin monomer is 10:90. The photoinitiator diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) is added at an amount of 2 wt% of the total mass of the system, and propylene glycol methyl ether acetate (PGMEA) is added as a solvent at an amount of 30 wt% of the total mass of the system. The mixture is magnetically stirred to form a homogeneous and transparent precursor mixture.

[0375] 2. Introduction of quantum dots and construction of ternary hybrid networks

[0376] CdSe / ZnS core-shell structured quantum dots with surface-coated tri-n-octylphosphine (TOP) / trioctylphosphine oxide (TOPO) are provided and added to the precursor mixture obtained in step 1.

[0377] Under stirring conditions, metal ions on the surface of quantum dots coordinate with thiol functional groups on functionalized POSS monomers. Simultaneously, acrylate functional groups on functionalized POSS monomers participate in subsequent photopolymerization reactions together with resin monomers.

[0378] In the above manner, quantum dots are anchored in a three-dimensional network framework jointly constructed by POSS structural monomers and resin monomers during the reaction process. The quantum dots are uniformly embedded inside the composite main network framework to form a POSS-resin-quantum dot ternary hybrid network structure, in which the quantum dots act as nodes or cross-linking points in the network.

[0379] 3. Preparation of quantum dot photoresist composite materials

[0380] The above mixture was further magnetically stirred for 30 min to ensure that the quantum dots, functionalized POSS structure monomers, and resin monomers reacted fully and were evenly distributed. Then, it was subjected to ultrasonic degassing for 5 min and filtered through a 0.45 μm filter membrane to obtain a stable and transparent quantum dot photoresist composite material based on a ternary hybrid network structure. The quantum dots contained in the composite material were 35 wt%.

[0381] 4. Graphical processing

[0382] The quantum dot photoresist composite material obtained in step 3 was spin-coated onto the surface of a Micro-LED chip. After pre-baking, it was patterned and cured by exposure to a UV mask for 60 seconds. After development, a patterned red quantum dot luminescent pattern was obtained with a minimum resolution of 10 μm.

[0383] In this embodiment, quantum dots form coordination connections with functionalized POSS structure monomers and further participate in the photopolymerization network construction of POSS-resin, enabling the quantum dots to be uniformly embedded within the composite host network framework, forming a stable ternary hybrid network structure. This structure effectively restricts the migration and aggregation of quantum dots in the photoresist system, improves the stability of quantum dots under light, heat, and humid environments, and ensures good pattern resolution and pattern conformal properties.

[0384] Full-color graphical representation of test cases

[0385] Red (CdSe) and green (InP) POSS-QDs photoresist composites were prepared according to the method in Example 1.

[0386] By using three mask alignment exposure steps, three color regions are patterned on the Micro LED chip to achieve single-chip full-color display function.

[0387] Each pattern measures 3 μm × 3 μm with a 2 μm spacing. Tests show no color crosstalk and superior heat resistance compared to conventional QD-doped photoresists.

[0388] Comparative Example 1

[0389] Compared with Example 1, this comparative example uses the same photoresist system and quantum dots, but the difference is that the POSS structure monomer does not contain ligand groups (only terminal acrylates).

[0390] The quantum dot photoresist composite material prepared in this comparative example was spin-coated onto a Micro LED substrate, exposed with an ultraviolet mask, cured for 60 seconds, developed, and the distribution of quantum dots and pattern formation were observed.

[0391] The observation results are as follows:

[0392] 1) Quantum dots do not form covalent / coordinate connections with POSS structure monomers and can only be maintained by network confinement or dispersants;

[0393] 2) Quantum dots are freely dispersed, and after solidification, they undergo severe self-absorption, reducing resolution;

[0394] 3) The thermal, light, and humidity stability is lower than that of Example 1.

[0395] Table 1 shows the test data for blue light aging and damp heat aging of the materials in Examples 1-28 and Comparative Example 1.

[0396] Table 1. Test data of materials in Examples 1-28 and Comparative Example 1.

[0397] Example Material type Blue light aging retention rate / 1000h (%) Retention rate after damp heat aging at 85℃ / 85%RH for 1000h (%) Example 1 POSS-CdSe / ZnS thiol bonding 91 90 Example 2 POSS-CdSe / ZnS carboxyl bonds 90 90 Example 3 POSS-InP / ZnS amino bonds 92 91 Example 4 POSS-AgInGaS / ZnS phosphonate bonding 93 92 Example 5 POSS-CdSe / ZnS phosphine oxide bond 90 89 Example 6 POSS-CdSe / ZnS thiol bonding 95 94 Example 7 POSS-InP / ZnS carboxyl bonds 88 87 Example 8 POSS-AgInGaS / ZnS phosphonate bonding 89 88 Example 9 POSS-InP / ZnS phosphooxy bonds 90 89 Example 10 Functionalization of photopolymerizable active groups of methacrylates with POSS-CdSe / ZnS-thiol bonding 88 87 Example 11 Methacrylate-functionalized POSS-InP / ZnS 90 89 Example 12 The photopolymerization active group is a POSS-CdSe / ZnS carboxyl bond of methacrylate. 70 70 Example 13 The photopolymerization active group is a POSS-CdSe / CdS thiol bond of epoxy. 71 70 Example 14 The photopolymerization active group is a POSS-AgInGaS / ZnS carboxyl bond of vinyl groups. 70 70 Example 15 POSS-CdSe / ZnS thiol bonding 69 70 Example 16 POSS-InP / ZnS carboxyl bonds 70 70 Example 17 POSS-AgInGaS / ZnS phosphonate bonding 92 91 Example 18 Based on methacrylate resin monomers 90 89 Example 19 Based on multifunctional acrylate crosslinking resin 91 90 Example 20 Based on epoxy resin monomers 90 89 Example 21 Based on vinyl / styrene resin monomers 93 92 Example 22 Based on hydroxyl-containing functional monomers 91 90 Example 23 No resin monomer -POSS-CdSe / ZnS mercapto bonding added 68 67 Example 24 No resin monomer -POSS-CdSe / ZnS phosphonic acid bonding added 71 70 Example 25 No resin monomer -POSS-CdSe / ZnS mercapto bonding added 72 71 Example 26 QDs are physically dispersed in a POSS-resin network 65 64 Example 27 High crosslinking density POSS-resin network + QDs physical dispersion 66 65 Example 28 POSS-resin-quantum dot ternary hybrid network structure 92 95 Comparative Example 1 QDs are only physically dispersed and have no POSS modification. 45 42

[0398] Figure 1 This is a photolithography result diagram of the photoresist material in Comparative Example 1; Figure 2 This is a photolithography result of the quantum dot photoresist composite material based on POSS interconnection prepared in Example 1; Figure 3 This is a photolithography result of the quantum dot photoresist composite material based on POSS connections prepared in Example 10; Figure 4 This is a photolithography result of the quantum dot photoresist composite material based on POSS interconnects prepared in Example 21; Figure 5 This is a lithographic result diagram of the QDs dissolution scheme in Example 26.

[0399] Comparing the results of the above embodiments with those of Comparative Example 1, it can be concluded that: In the POSS-connected quantum dot photoresist composite material of the present invention, the quantum dots are uniformly dispersed in the photoresist, and can maintain their in-situ distribution after curing. The pattern edges are clear, and cross-contamination between pixels is significantly reduced, achieving high-resolution micron-level or even submicron-level three-color pixel patterning. The quantum dots are stably distributed in the cured network, exhibiting excellent durability and resistance to blue light bleaching under thermal, light, and humidity conditions. In contrast, the quantum dots in Comparative Example 1 rely only on physical dispersion or network confinement, and are prone to aggregation, migration, or edge blurring after curing. The three-color patterning effect is unstable, and the thermal and light stability is significantly lower than that of the above embodiments.

[0400] Therefore, the quantum dot photoresist composite material based on POSS interconnection of the present invention has achieved unexpected technical effects in terms of quantum dot distribution uniformity, pattern conformity, stability, and pixel-level full-color integration.

[0401] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.

[0402] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0403] Although this application has been described with reference to illustrative embodiments, those skilled in the art will understand that various other changes, omissions, and / or additions can be made without departing from the spirit and scope of this application, and that elements of the described embodiments can be substituted with substantially equivalents. Furthermore, many modifications can be made without departing from the scope of this application to adapt particular situations or materials to the teachings of this application. Therefore, this application is not intended to be limited to the specific embodiments disclosed for carrying out this application, but rather is intended to include all embodiments falling within the scope of the appended claims.

Claims

1. A quantum dot photoresist composite material based on POSS interconnects, characterized in that, The invention includes multiple POSS-quantum dot complexes. Each POSS-quantum dot complex comprises a bridging structure formed by functionalized POSS structural monomers and quantum dots having a first pre-modified ligand, connected by coordination bonds or group substitution. The quantum dots are uniformly embedded in the framework of the POSS structural monomers to form a three-dimensional network structure, and a dense coating layer is formed on the surface of the quantum dots. At least one end of each functionalized POSS structural monomer has a first functional group, serving as a ligand group, for connection with the surface of the quantum dots. The first functional group is selected from one or more combinations of thiol, carboxyl, amino, phosphonic acid, phosphonoxy, selenol, acrylate, and epoxy groups. The first pre-modified ligand contains one or more combinations of phosphonic acid, thiol, selenol, carboxyl, acrylate, and epoxy groups.

2. The quantum dot photoresist composite material based on POSS interconnection according to claim 1, characterized in that: The quantum dot surface also has a second pre-modified ligand as an active end group, the second pre-modified ligand being selected from one or more combinations of acrylic ligands, methacrylic ligands, epoxy ligands, isocyanate ligands, thiol ligands, and amino ligands; at least one end of the functionalized POSS structural monomer also has a second functional group that matches the second pre-modified ligand, the second functional group being selected from one or more combinations of acrylate groups, methacrylate groups, epoxy groups, amino groups, and thiol groups.

3. The quantum dot photoresist composite material based on POSS interconnection according to claim 1, characterized in that: At least one end of the functionalized POSS structural monomer also has a third functional group that can participate in the photopolymerization reaction and serve as a photopolymerization active group; the third functional group is a functional group that can absorb light energy and generate active species or undergo structural changes under light irradiation conditions, and is selected from one or more combinations of α-carbonyl groups, acylphosphine oxide groups, photoacid-producing groups, aromatic sulfonium salts or iodonium salts, cinnamic acid ester groups, chalcone groups, azo groups, aromatic conjugated light-absorbing groups, and ultraviolet absorber groups.

4. The quantum dot photoresist composite material based on POSS interconnection according to claim 1, characterized in that: At least one end of the functionalized POSS structural monomer also has a fourth functional group, which is a hydrophilic group or a hydrophobic group. The hydrophilic group is selected from one or more combinations of carboxyl, hydroxyl, amino, sulfonic acid, phosphonic acid, and polyether segments. The hydrophobic group is selected from one or more combinations of alkyl, aromatic, fluorinated alkyl, and siloxane segments.

5. The quantum dot photoresist composite material based on POSS interconnection according to claim 1, characterized in that: The POSS structure monomer is selected from one or more combinations of closed cage-like silsesquioxanes, partially open cage-like silsesquioxanes, or ladder-like silsesquioxanes.

6. The quantum dot photoresist composite material based on POSS interconnection according to claim 5, characterized in that: The POSS structural unit is a polyhedral or quasi-polyhedral structure with a Si–O–Si inorganic framework.

7. The quantum dot photoresist composite material based on POSS interconnection according to claim 6, characterized in that: The POSS structural monomer includes T8-type closed cage-like silsesquioxane, T... 10 Type polyhedral silsesquioxane, T 12 One or more of the polyhedral silsesquioxanes.

8. The quantum dot photoresist composite material based on POSS interconnection according to claim 7, characterized in that: The POSS structure monomer is a T8-type closed cage-like silsesquioxane, which contains 2 to 8 functional groups. The functional groups are a combination of a first functional group, a second functional group, a third functional group, and a fourth functional group, and the ratio of the first functional group, the third functional group to the fourth functional group is 1:1:0 to 4:2:

2.

9. The quantum dot photoresist composite material based on POSS interconnection according to claim 1, characterized in that: Multiple POSS-quantum dot complexes are cross-linked with each other; Alternatively, the POSS-connected quantum dot photoresist composite material further includes a photoresist matrix, wherein the POSS-quantum dot composite is uniformly dispersed in the photoresist matrix, and the content of the POSS-quantum dot composite in the POSS-connected quantum dot photoresist composite material is 1~40wt%, with the remainder being the photoresist matrix.

10. The quantum dot photoresist composite material based on POSS interconnection according to claim 1, characterized in that: The quantum dots are selected from one or more combinations of group IV quantum dots, group II-VI quantum dots, group IV-VI quantum dots, and group III-V quantum dots.

11. The quantum dot photoresist composite material based on POSS interconnection according to claim 1, characterized in that: The content of quantum dots in the POSS-quantum dot composite is 5~50 wt%.

12. The method for preparing the quantum dot photoresist composite material based on POSS interconnection as described in any one of claims 1 to 11, characterized in that, include: Quantum dots are connected to POSS structure monomers through covalent or coordinate bonds to form POSS-quantum dot complexes; The POSS-quantum dot composite is mixed, or the POSS-quantum dot composite is mixed with a photoresist system to obtain a quantum dot photoresist composite material based on POSS connections.

13. A quantum dot photoresist composite material based on POSS interconnects, characterized in that, include: A composite host network framework formed by combining POSS structure monomers and resin monomers, and quantum dots, wherein the quantum dots are uniformly embedded inside the composite host network framework to form a ternary hybrid network, the POSS structure monomers and quantum dots are connected by covalent bonds or coordination bonds, and a dense coating layer is formed on the surface of the quantum dots. The POSS structural monomer is a functionalized POSS structural monomer. At least one end of the functionalized POSS structural monomer has a first functional group as a ligand group for connection with the quantum dot surface having a first pre-modified ligand via coordination bond or group substitution. The first functional group is selected from one or more combinations of thiol, carboxyl, amino, phosphonic acid, phosphonoxy, selenol, acrylate, and epoxy groups. The first pre-modified ligand contains one or more combinations of phosphonic acid, thiol, selenol, carboxyl, acrylate, and epoxy groups.

14. The quantum dot photoresist composite material based on POSS interconnection according to claim 13, characterized in that: The resin monomer is selected from one or more combinations of methyl methacrylate, methyl acrylate, 2-hydroxyethyl methacrylate, n-butyl acrylate, isoborneol methacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, N-acryloylmorpholine, and N-acryloylmorpholine derivatives.

15. The quantum dot photoresist composite material based on POSS interconnection according to claim 13, characterized in that: The quantum dot surface also has a second pre-modified ligand as an active end group, the second pre-modified ligand being selected from one or more combinations of acrylic ligands, methacrylic ligands, epoxy ligands, isocyanate ligands, thiol ligands, and amino ligands; at least one end of the functionalized POSS structural monomer also has a second functional group that matches the second pre-modified ligand, the second functional group being selected from one or more combinations of acrylate groups, methacrylate groups, epoxy groups, amino groups, and thiol groups.

16. The quantum dot photoresist composite material based on POSS interconnection according to claim 13, characterized in that: At least one end of the functionalized POSS structural monomer also has a third functional group that can participate in the photopolymerization reaction and serve as a photopolymerization active group; the third functional group is a functional group that can absorb light energy and generate active species or undergo structural changes under light irradiation conditions, and is selected from one or more combinations of α-carbonyl groups, acylphosphine oxide groups, photoacid-producing groups, aromatic sulfonium salts or iodonium salts, cinnamic acid ester groups, chalcone groups, azo groups, aromatic conjugated light-absorbing groups, and ultraviolet absorber groups.

17. The quantum dot photoresist composite material based on POSS interconnection according to claim 13, characterized in that: At least one end of the functionalized POSS structural monomer also has a fourth functional group, which is a hydrophilic group or a hydrophobic group. The hydrophilic group is selected from one or more combinations of carboxyl, hydroxyl, amino, sulfonic acid, phosphonic acid, and polyether segments. The hydrophobic group is selected from one or more combinations of alkyl, aromatic, fluorinated alkyl, and siloxane segments.

18. The quantum dot photoresist composite material based on POSS interconnection according to claim 13, characterized in that: The POSS structure monomer is selected from one or more combinations of closed cage-like silsesquioxanes, partially open cage-like silsesquioxanes, or ladder-like silsesquioxanes.

19. The quantum dot photoresist composite material based on POSS interconnection according to claim 18, characterized in that: The POSS structural unit is a polyhedral or quasi-polyhedral structure with a Si–O–Si inorganic framework.

20. The quantum dot photoresist composite material based on POSS interconnection according to claim 19, characterized in that: The POSS structural monomer is selected from T8 type closed cage-like silsesquioxane, T... 10 Type polyhedral silsesquioxane, T 12 One or more of the polyhedral silsesquioxanes.

21. The quantum dot photoresist composite material based on POSS interconnection according to claim 20, characterized in that: The POSS structure monomer is a T8-type closed cage-like silsesquioxane, which contains 2 to 8 functional groups. The functional groups are a combination of a first functional group, a second functional group, a third functional group, and a fourth functional group, and the ratio of the first functional group, the third functional group to the fourth functional group is 1:1:0 to 4:2:

2.

22. The quantum dot photoresist composite material based on POSS interconnection according to claim 13, characterized in that: The quantum dots are selected from one or more combinations of group IV quantum dots, group II-VI quantum dots, group IV-VI quantum dots, and group III-V quantum dots.

23. The quantum dot photoresist composite material based on POSS interconnection according to claim 13, characterized in that: The quantum dot photoresist composite material based on POSS connections contains 0.1-50 wt% quantum dots and 1-30 wt% functionalized POSS structural monomers.

24. The method for preparing a quantum dot photoresist composite material based on POSS interconnection as described in any one of claims 13 to 23, characterized in that, include: The POSS structure monomer, quantum dots, resin monomer, photoinitiator and solvent are mixed uniformly to prepare a quantum dot photoresist composite material based on POSS connection.

25. The preparation method according to claim 24, characterized in that: The photoinitiator is selected from one or more combinations of TPO, Irgacure 819, and BAPO; and / or, the solvent is selected from one or two combinations of PGMEA and GBL.

26. The preparation method according to claim 24, characterized in that, include: Functionalized POSS structure monomers, quantum dots, resin monomers, photoinitiators and solvents are mixed to form a mixture, which is then magnetically stirred for 30~180 min to obtain a quantum dot photoresist composite material based on POSS connections. The mixture contains 1-20 wt% functionalized POSS monomers, 0.1-50 wt% quantum dots, 50-90 wt% resin monomers, 0.1-5 wt% photoinitiator, and the remainder is solvent. And / or, the mixture further includes an additive selected from one or a combination of two of diluents and surface agents.

27. A method for patterning quantum dots, characterized in that, include: The quantum dot photoresist composite material based on POSS connection as described in any one of claims 1-11 and 13-23 is applied to the surface of a Micro-LED chip; Graphical exposure can be performed using methods such as mask exposure, laser scanning, or TPP. After development, a patterned quantum dot pattern of the corresponding color is obtained.

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