Fabrication of luminescent quantum dot thiol-yne nanocomposites with tailorable optical, thermal and mechanical properties
Inventors
Boyd, Darryl A. • Stewart, Michael H. • Susumu, Kimihiro • Oh, Eunkeu • Wissman, James P.
Assignees
Publication Number
US-12247152-B2
Publication Date
2025-03-11
Expiration Date
2038-10-05
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Abstract
This disclosure concerns a method of making a ligand for Quantum Dot functionalization, a method of making a functionalized Quantum Dot (QD) with a ligand, and a method of making a transparent luminescent quantum dot thiol-yne nanocomposite with tailorable optical, thermal, and mechanical properties. The prepolymer solution and functionalized Quantum Dot can be used in additive manufacturing.
Core Innovation
This invention relates to the development of polymeric materials made using thiol-yne chemistry, with incorporated quantum dot (QD) nanoparticles, resulting in transparent, luminescent materials whose optical, mechanical, and thermal properties can be tailored. The method involves synthesizing novel ligands to functionalize QDs, incorporating these functionalized QDs into a thiol-yne prepolymer matrix, and subsequently polymerizing the mixture by photopolymerization or thermal curing to form luminescent QD thiol-yne nanocomposites.
The problem addressed by this invention arises from the need for display materials that simultaneously provide flexibility, stretchability, durability, scratch resistance, transparency, and shatterproof qualities while also enhancing color characteristics to produce brighter and more realistic visual outputs in modern devices like mobile phones, flat screen televisions, and touch screen car panels. Existing materials do not combine these properties effectively. Moreover, polymers made with thiol-yne chemistry, which offer improved mechanical and thermal properties with high-quality optical features, have not been previously combined with luminescent QDs for device display applications.
The disclosed process emphasizes the advantage of using thiol-yne chemistry because it provides unique characteristics such as high strength, flexibility, and high refractive index, which are difficult to achieve with other polymer chemistries. Thiol-yne chemistry also avoids oxygen inhibition common in other polymerizations and allows incorporation of nanoparticles like QDs without significant loss of material properties. The invention also discloses flexible alternatives including the use of related thiol chemistries, other types of nanoparticles besides QDs, alternate monomers for prepolymer preparation, and various polymerization methods, thus presenting a versatile approach to fabricating luminescent nanocomposite materials.
Claims Coverage
The patent includes one independent claim detailing a method for making a transparent luminescent quantum dot thiol-yne nanocomposite with specific steps, supported by dependent claims that provide additional process refinements and optional features. There are seven main inventive features addressed in the claims.
Method of making functionalized Quantum Dots with synthesized ligands
Mixing quantum dots (QDs) with a chloroform solution containing synthesized ligands to produce functionalized QDs, and suspending these functionalized QDs in a 1.5 μM chloroform solution.
Preparation of a thiol-yne prepolymer
Combining 1 mole equivalent of selected monovinyl, monoalkynyl, polyvinyl, polyalkynyl monomers or combinations thereof with 1 mole equivalent of selected monothiol, polythiol monomers or combinations to form the prepolymer, specifically combining tetrathiol pentaerythritol tetrakis (3-mercaptopropionate) (PETMP) with dialkyne 1,7-octadiyne (ODY).
Mixing and agitating thiol-yne prepolymer with functionalized Quantum Dots solution
Combining the prepared thiol-yne prepolymer with the functionalized QD solution and agitating to form a single phase.
Polymerization of the nanocomposite by thermal curing
Polymerizing the mixed thiol-yne prepolymer and functionalized QD solution by thermal curing, specifically at about 80° C. for approximately 30 minutes.
Polymerization of the nanocomposite by ultraviolet irradiation
Polymerizing by ultraviolet irradiation at about 365 nm for about 10 seconds, with prior addition of less than 1 mol % 2,2-dimethoxy-2-phenylacetophenone (DMPA) photoinitiator to the mixture.
Modifying prepolymer viscosity with silica gel
Mixing silica gel with the thiol-yne prepolymer to adjust the viscosity of the prepolymer solution.
Use of the luminescent quantum dot thiol-yne nanocomposite in additive manufacturing
Adding the quantum dot thiol-yne nanocomposite to materials used in additive manufacturing techniques to form solid materials.
The claims cover a methodical approach to producing transparent, luminescent quantum dot thiol-yne nanocomposites through ligand-functionalized QDs combined with tailored thiol-yne prepolymers, polymerized either thermally or photochemically, with provisions for viscosity modification and application in additive manufacturing, thereby defining the inventive scope across material synthesis, processing, and utility.
Stated Advantages
Creation of novel ligands for functionalizing nanoparticles.
Capability to fabricate materials by both thermal polymerization and photopolymerization.
Materials with tailorable optical properties depending on monomers and incorporated quantum dots.
Materials with tailorable mechanical properties influenced by monomer formulations and quantum dot content.
Materials exhibiting tailorable thermal properties adjustable through monomer and quantum dot selection.
Documented Applications
Use as screens in device displays providing improved flexibility, durability, transparency, and enhanced color characteristics.
Use as materials in additive manufacturing.
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