Patent Application
20240352312
Biomedical imaging is used in clinical diagnosis, therapy assessment, patient treatment, and surgical operations, allowing observation of pathological and physiological events with human diseases. Fluorescence imaging using near infrared (NIR) fluorophore, e.g., with fluorescence in the range of 700 nm to 900 nm, enables imaging of physiological, metabolic and molecular function in vivo. Imaging using NIR fluorophores is relevant for cancer detection and diagnosis and surgical resection, diagnosis of diseases such as neurological disorders, e.g., Alzheimer's disease, and in cardiovascular and plastic and reconstructive surgeries.
We describe here approaches to synthesis of cadmium-free near-infrared core-shell quantum dots based on I-III-VI ternary semiconductors. For instance, CuInS2, CuInSe2, AgInS2, or AgInSe2 quantum dot cores coated with ZnS or ZnSe shells can be produced. These quantum dots are biocompatible and fluoresce in the near infrared (NIR), e.g., with fluorescence emission wavelengths in the range of 650 to 840 nm. The synthesis processes described here provide mechanisms for precise control of the size, size distribution, and composition of the quantum dots (e.g., the quantum dot cores), all of which affect the fluorescence spectrum of the quantum dots.
The synthesis processes described here separate the nucleation and growth of the core of the quantum dots from further growth, annealing and shelling of the core quantum dots, enabling precise control of the size and composition of the resulting nanoparticles and hence control over the NIR emission spectrum of the nanoparticles. A microemulsion template assisted approach to nucleation and growth of the cores is used, followed by annealing and growth of the shell of the core quantum dots.
The resulting core-shell NIR quantum dots can be oil soluble or water soluble, depending on, e.g., the annealing approach and the identity of the surface ligands used to functionalize the core-shell quantum dots.
NIR quantum dots soluble in organic (e.g., hydrophobic) solvents (e.g., quantum dots coated with hydrophobic ligands) are useful in the context of, e.g., photovoltaic applications. Water soluble NIR quantum dots (e.g., quantum dots coated with hydrophilic ligands with functional groups which allow conjugation with various types of biomolecules) can be used in biological and medical applications such as biomedical diagnosis, drug delivery, and surgical assistance applications
In an aspect, a method for making ternary core-shell semiconductor nanoparticles includes providing an emulsion including droplets dispersed in a continuous phase of a non-polar solvent. The droplets include a solution of ions of a Group I element and ions of a Group III element in a polar solvent, and in which the droplets are encapsulated by an interfacially active material. The method includes exposing the emulsion to ions of a Group VI element to cause the ions of a Group VI element to react with the ions of the Group I element and ions of the Group III element in the droplets to form nanoparticles in the droplets; reacting the nanoparticles in the droplets with a first precursor to grow a shell on the nanoparticles, thereby forming core-shell nanoparticles; extracting the core-shell nanoparticles from the emulsion; thermally annealing the core-shell nanoparticles; and reacting the annealed core-shell nanoparticles with a second precursor to further grow the shell on the nanoparticles, thereby forming ternary core-shell semiconductor nanoparticles.
Embodiments can include one or any combination of two or more of the following features.
The method includes dissolving a first reactant and a second reactant in the polar solvent to form the solution of the ions of a Group I element and the ions of a Group III element. The first reactant includes a Group I element-containing compound and the second reactant includes a Group III element-containing compound. The first reactant includes a salt of the Group I element. The first reactant includes Copper (I) iodide (CuI), Copper (I) chloride (CuCl), Copper (I) bromide (CuBr), Cu(I) acetate (Cu(Ac)), Silver nitrate (Ag(NO3)), Silver acetate (Ag(Ac)), or Silver sulfate (Ag2(SO4)). The second reactant includes Indium (III) acetate (In(Ac)3), Indium (III) chloride (InCl3), Indium (III) sulfate (In2(SO4)3) or Indium (III) nitrate (In(NO3)3). The method includes adjusting the pH of the polar solvent to dissolve the first reactant and the second reactant in the polar solvent. Dissolving the first reactant and the second reactant in the polar solvent includes: dissolving the first reactant in a basic or acidic solution of the polar solvent; dissolving the second reactant in an acidic or basic solution of the polar solvent; and combining the basic solution with the dissolved first reactant and the acidic solution with the dissolved second reactant to form the solution of the ions of a Group I element and the ions of a Group III element.
The ions of the Group I element include ions of Cu or Ag.
The ions of the Group III element include ions of In or Ga.
The interfacially active material includes an amphiphilic block copolymer, a surfactant, a water-dispersible polymer, an amphiphilic molecule, a solid particle, or a solvent-swollen particle.
The nanoparticles have a composition ABXy, where A is the Group I element, B is the Group III element, and X is the Group VI element.
Exposing the emulsion to ions of the Group VI element includes contacting the emulsion with a gas, a solid, or an aqueous solution containing a Group VI element-containing compound. The gas, solid, or aqueous solution containing the Group VI element-containing compound includes a hydride of the Group VI element. The Group VI element-containing compound is soluble in a polar solvent.
The Group VI element includes S, Se, or Te.
Reacting the nanoparticles in the droplets with the first precursor includes exposing the emulsion to a precursor to the shell. The precursor to the shell includes a precursor to ZnS or ZnSe. The precursor to the shell includes a Zn+ precursor solution.
The method includes functionalizing the core-shell nanoparticles with hydrophilic surface ligands.
The method includes functionalizing the core-shell nanoparticles with hydrophobic surface ligands. The method includes exchanging the hydrophobic surface ligands for hydrophilic surface ligands following growth of the shell on the nanoparticles.
Thermally annealing the core-shell nanoparticles includes annealing the core-shell nanoparticles in a batch process.
Thermally annealing the core-shell nanoparticles includes exposing the nanoparticles to multiple cycles of heating and cooling. Thermally annealing the core-shell nanoparticles includes flowing an aqueous solution of the core-shell nanoparticles through a flow channel. The method includes applying heating fluid and cooling fluid to alternating portions of the flow channel to expose the nanoparticles to the multiple cycles of heating and cooling.
Reacting the annealed core-shell nanoparticles with the second precursor includes reacting the annealed core-shell nanoparticles with Zn2+ ions. Reacting the annealed core-shell nanoparticles with the second precursor includes dispersing droplets of a solution of the annealed core-shell nanoparticles and Zn2+ ions in a dispersant gas.
The method includes reacting the annealed core-shell nanoparticles with the second precursor in a tubular coiled reactor.
The ternary core-shell semiconductor nanoparticles have a fluorescence emission wavelength of between 650 nm and 840 nm.
The ternary core-shell semiconductor nanoparticles have a fluorescence emission spectrum with a full width at half maximum of less than or equal to 100 nm.
The ternary core-shell semiconductor nanoparticles have a quantum yield of at least 40% in an aqueous solvent.
In an aspect, a method for making ternary core-shell semiconductor nanoparticles includes providing an emulsion including droplets dispersed in a first solvent. The droplets include a solution of ions of a Group I element and ions of a Group III element in a second solvent, and in which the droplets are encapsulated by an interfacially active material, and in which the first solvent is immiscible with the second solvent. The method includes exposing the emulsion to ions of a Group VI element to cause the ions of the Group VI element to react with the ions of the Group I element and ions of the Group III element in the droplets to form nanoparticles in the droplets; reacting the nanoparticles in the droplets with a first precursor to grow a shell on the nanoparticles, thereby forming core-shell nanoparticles; and extracting the core-shell nanoparticles from the emulsion.
Embodiments can include one or any combination of two or more of the following features.
The core of the core-shell nanoparticles has a composition ABXy, where A is the Group I element, B is the Group III element, and X is the Group VI element. The core of the core-shell nanoparticles has a composition CuInS2, CuInSe2, AgInS2, or AgInSe2.
The first solvent includes a polar solvent and the second solvent includes a non-polar solvent.
The interfacially active material includes an amphiphilic block copolymer, a surfactant, a water-dispersible polymer, an amphiphilic molecule, a solid particle, or a solvent-swollen particle.
Exposing the emulsion to ions of the Group VI element includes contacting the emulsion with a gas, a solid, or an aqueous solution containing a Group VI element-containing compound. Contacting the emulsion with the gas containing the Group VI element-containing compound includes bubbling the gas into the emulsion.
Reacting the nanoparticles in the droplets with the precursor of higher band gap energy semiconductor includes exposing the emulsion to a precursor to the shell. The precursor to the shell includes a precursor to ZnS or ZnSe. The precursor to the shell includes a Zn2+ precursor solution.
Reacting the nanoparticles in the droplets with the first precursor causes the shell to grow to a thickness of 0.3 nm to 1 nm.
The method includes functionalizing the core-shell nanoparticles with hydrophilic surface ligands.
The method includes functionalizing the core-shell nanoparticles with hydrophobic surface ligands.
In an aspect, a method for making ternary core-shell semiconductor nanoparticles, the method includes extracting core-shell nanoparticles from an emulsion comprising droplets of a first solvent dispersed in a second solvent, in which the nanoparticles are contained in the droplets and in which the droplets are encapsulated by an interfacially active material, and in which the nanoparticles comprise a core coated with a shell, in which the core of the core-shell nanoparticles has a composition ABXy, where A is a Group I element, B is a Group III element, and X is a Group VI element; thermally annealing the core-shell nanoparticles, comprising exposing the nanoparticles to multiple cycles of heating and cooling; and reacting the annealed core-shell nanoparticles with a precursor to increase the thickness of the shell of the nanoparticles.
In an aspect, a method for making ternary core-shell semiconductor nanoparticles includes extracting core-shell nanoparticles from an emulsion including droplets of a first solvent dispersed in a second solvent. The nanoparticles are contained in the droplets and in which the droplets are encapsulated by an interfacially active material, and in which the nanoparticles include a core coated with a shell. The method includes thermally annealing the core-shell nanoparticles, including exposing the nanoparticles to multiple cycles of heating and cooling; and reacting the annealed core-shell nanoparticles with a precursor to increase the thickness of the shell of the nanoparticles.
Embodiments can include one or any combination of two or more of the following features.
The core of the core-shell nanoparticles has a composition ABXy, where A is a Group I element, B is a Group III element, and X is a Group VI element. The core of the core-shell nanoparticles has a composition CuInS2, CuInSe2, AgInS2, or AgInSe2.
The shell of the core-shell nanoparticles has a composition of ZnS or ZnSe.
The core-shell nanoparticles extracted from the emulsion are water soluble.
The core-shell nanoparticles extracted from the emulsion are soluble in an organic solvent.
Thermally annealing the core-shell nanoparticles includes flowing an aqueous solution of the core-shell nanoparticles through a flow channel. The method includes applying heating fluid and cooling fluid to alternating portions of the flow channel to expose the nanoparticles to the multiple cycles of heating and cooling.
Thermally annealing the core-shell nanoparticles includes alternately heating the core-shell nanoparticles to a temperature of between 200° C. and 250° C., and cooling the core-shell nanoparticles to a temperature of between 10° C. and 40° C.
Thermally annealing the core-shell nanoparticles includes exposing the nanoparticles to cycles of heating and cooling with a frequency of between 0.0001 Hz and 1 Hz.
Reacting the annealed core-shell nanoparticles with the second precursor includes reacting the annealed core-shell nanoparticles with Zn2+ ions. Reacting the annealed core-shell nanoparticles with the second precursor includes dispersing droplets of a solution of the annealed core-shell nanoparticles and Zn2+ ions in a feeding solution. The feeding solution acts as a source of sulfur for the shell of the nanoparticles.
The method includes reacting the annealed core-shell nanoparticles with the second precursor in a tubular coiled reactor.
In an aspect, a composition includes an emulsion containing droplets of a first solvent dispersed in a second solvent; an interfacially active material encapsulating each droplet of the emulsion; and a core-shell nanoparticle contained in each of at least some of the droplets. The core of each core-shell nanoparticles has a composition ABXy, where A is a Group I element, B is a Group III element, and X is a Group VI element.
Embodiments can include one or any combination of two or more of the following features.
The core of the core-shell nanoparticles has a composition CuInS2, CuInSe2, AgInS2, or AgInSe2.
The shell of the core-shell nanoparticles includes ZnS or ZnSe.
A thickness of the shell of the core-shell nanoparticles is between 0.3 nm and 1 nm.
A band gap of the shell of the core-shell nanoparticles is larger than a band gap of the core of the core-shell nanoparticles.
The first solvent is a polar solvent and the second solvent is a non-polar solvent.
The interfacially active material includes an amphiphilic block copolymer, a surfactant, a water-dispersible polymer, an amphiphilic molecule, a solid particle, or a solvent-swollen particle.
The core of the core-shell nanoparticles and the core-shell nanoparticles both have a fluorescence emission wavelength of between 650 nm and 840 nm.
A diameter of each droplet is between 30 nm and 40 nm.
In an aspect, a system for making ternary core-shell semiconductor nanoparticles includes a reaction vessel configured to receive an emulsion including droplets dispersed in a first solvent. The droplets include a solution of ions of a Group I element and ions of a Group III element in a second solvent, and in which the droplets are encapsulated by an interfacially active material. The system includes a source of inert gas fluidically connected to the reaction vessel. The system includes a source of a gaseous Group VI element-containing compound fluidically connected to the reaction vessel; and a flow controller configured to control the flow of the gaseous Group VI element-containing compound into the reaction vessel. When the gaseous Group VI element-containing compound is flowed into the reaction vessel, the ions of the Group I element and the ions of the Group III element react with ions of the Group VI element to form nanoparticles in the droplets.
In an aspect, a system for synthesizing ternary core-shell semiconductor nanoparticles includes a first reactor including a first fluid flow channel. An inlet of the fluid flow channel is configured to receive droplets of an aqueous solution dispersed in a carrier gas, the droplets of aqueous solution having nanoparticles contained therein. The first reactor includes a heating subsystem configured to heat first portions of the fluid flow channel; and a cooling subsystem configured to cool second portions of the fluid flow channel. The fluid flow channel includes multiple first portions and multiple second portions in an alternating arrangement. The system includes a second reactor including a second fluid flow channel having inlets configured to receive the aqueous solution of nanoparticles from the first reactor, a precursor solution, and a dispersant gas; and a coiled reactor configured to receive droplets of the aqueous solution of nanoparticles and the precursor solution dispersed in the dispersant gas.
Embodiments can include one or any combination of two or more of the following features.
The system includes a spectrometer disposed along the second fluid flow channel upstream of the coiled reactor.
The system includes a spectrometer disposed along the second fluid flow channel downstream of the coiled reactor.
The system includes a flow controller configured to control a flow rate of the aqueous solution of nanoparticles.
The system includes a flow controller configured to control a flow rate of the precursor solution.
The system includes a flow controller configured to control a flow rate of the dispersant gas.
The approaches described here can have one or more of the following advantages. The synthesis approaches described here can produce water soluble, biocompatible core-shell quantum dots with high fluorescence intensity, high quantum yield, and good photostability. For instance, core-shell quantum dots synthesized by the approaches described here can fluoresce in the near infrared and are free of heavy metals such as cadmium, thereby meeting criteria for diagnostic probes. The synthesis process produces large quantities of monodisperse quantum dots and enables precise control over the composition, size, and size distribution of the quantum dots. The synthesis process is scalable.
The details of one or more implementations are set forth in the accompanying drawings and the description below. Other features and advantages will be apparent from the description and drawings, and from the claims.
We describe here approaches to synthesis of cadmium-free near-infrared core-shell quantum dots (also sometimes referred to as nanoparticles) based on I-III-VI ternary semiconductors. For instance, CuInS2, CuInSe2, AgInS2, or AgInSe2 quantum dot cores coated with ZnS or ZnSe shells can be produced. These core-shell quantum dots are biocompatible and fluoresce in the near infrared (NIR), e.g., with fluorescence emission wavelengths in the range of 650 to 840 nm. The synthesis processes described here provide mechanisms for precise control of the size, size distribution, and composition of the quantum dots (e.g., the quantum dot cores), all of which affect the fluorescence spectrum of the core-shell quantum dots.
The synthesis processes described here separate the nucleation and growth of the core of the quantum dots from further growth, annealing, and shelling of the quantum dot cores, enabling precise control of the size and composition of the resulting core-shell quantum dots and hence control over their NIR emission spectrum. A microemulsion template assisted approach to nucleation and growth of the cores is used, followed by annealing and growth of the shell. The resulting core-shell NIR quantum dots can be soluble in water or in hydrophobic solvents and have a fluorescence emission spectrum in the NIR range.
I-III-VI semiconductor quantum dot cores are composed of three chemical elements belonging to groups I, III, and VI of the periodic table, e.g., two metals and a chalcogen. The quantum dot cores can have the general composition ABXy, where A is a Group I element such as Cu or Ag; B is a Group III element such as In or Ga; and X is a Group VI element such as S, Se, or Te. Specific example compositions for I-III-VI quantum dots that can be synthesized by the approaches described here include CuInS2, CuInSe2, AgInS2, or AgInSe2.
The quantum dot cores 102 in the microemulsion templates 104 are coated with a thin shell 106 of a high band gap material, such as ZnS or ZnSe, to produce thin-shelled quantum dots 108 (sometimes also referred to as core-shell nanoparticles). By high band gap material, we mean that the band gap of the shell 106 is larger than the band gap of the core 102. In some examples, the thin-shelled quantum dots 108, still in the microemulsion templates 104, are capped with hydrophilic surface ligands, rendering the thin-shelled quantum dots 108 water soluble and facilitating their extraction from the microemulsion. In some examples, the thin-shelled quantum dots 108 in the microemulsion templates 104 are capped with hydrophobic surface ligands, rendering the thin-shelled quantum dots 108 soluble in hydrophobic solvents, e.g., organic solvents such as hexane and facilitating their extraction from the microemulsion.
Once extracted from the microemulsion, the thin-shelled quantum dots 108 are thermally annealed at high temperature and the shell is grown to a larger thickness to produce core-shell quantum dots 122. The thicker shell is the same material as the thin shell of the thin-shelled quantum dots 108, e.g., a high band gap material such as ZnS or ZnSe. The annealing and growth of a thick shell stabilizes the core-shell quantum dots and removes crystal defects, thereby enhancing their quantum yield. In the example of
Referring to
In a microemulsion template approach to quantum dot core synthesis, the microemulsion templates are formed by self-assembly of ternary systems including a polar solvent, a non-polar solvent, and an interfacially active material, such as surfactants, amphiphilic block copolymers, water-dispersible polymers, amphiphilic molecules, solid particles, or solvent-swollen particles. The templates are formed by self-assembly of the interfacially active material in the presence of the polar solvent and the non-polar solvent in a specified ratio. The shape of the nanostructure material synthesized according to the microemulsion template approach is controlled by the composition of the ternary self-assembled templates. The size of the quantum dot cores and their composition are controlled by the concentration of precursor reactants and the molar ratio of precursor reactants supplied to the templates.
Referring specifically to
Suitable polar solvents include, e.g., water or formamide. Suitable non-polar solvents are immiscible with the polar solvent and include, e.g., organic solvents such as alkenes, e.g., p-xylene; alkanes, e.g., n-hexane, n-heptane, or n-octane. The interfacially active material can include surfactants, amphiphilic block copolymers, water-dispersible polymers, amphiphilic molecules, solid particles, or solvent-swollen particles. Suitable amphiphilic block copolymers include, e.g., block copolymers composed of poly (ethylene oxide) (PEO) and poly (propylene oxide) (PPO), such as PEO-PPO-PEO; block copolymers made by joining PEO or poly (acrylic acid) blocks with polystyrene, polybutylene, or polymethylsiloxane; or other amphiphilic block copolymers. Suitable surfactants include, e.g., natural surfactants (e.g., lipids), synthetic surfactants (e.g., alkylbenzyl sulfonates), ionic surfactants (e.g., sodium dodecyl sulfate), cationic surfactants (e.g., alkyl-trimethylammonium chloride), nonionic surfactants (e.g., alkyl ethoxylates), or zwitterionic surfactants (e.g. betaine). The surfactants can be a single species (e.g., one type of molecule present) or mixtures of species (e.g., mixture of anionic and cationic surfactants, mixture of an ionic surfactant and an aliphatic alcohol). The surfactants can be monodisperse or polydisperse. Suitable water-dispersible polymers can include dextran, guar gum, and gelatine. Suitable solid particles can include silica, aluminum oxide, and titanium oxide. Suitable solvent-swollen particles can include latexes.
In the specific example of
In some examples, a reagent is added to the polar solvent to increase or decrease the pH of the aqueous solution, thereby promote dissolution of the precursor reactants and increasing the solubility of the metal ions. The reagent can be an acid, such as hydrochloric acid (HCl), or a base, such as ammonia hydroxide (NH4—OH), that will not interfere with the stability of the microemulsion template droplets (discussed infra). In some examples, each of the precursor reactants is dissolved in its own solution and the two solutions are then mixed. For instance, the Group I precursor reactant can be dissolved in an acidic solution and the Group III precursor reactant can be dissolved in a basic solution. The Group I precursor reactant can also be dissolved in a basic solution and the Group III precursor reactant can be dissolved in an acid solution. One of the Group I precursor reactant and Group III precursor reactant or both of them can be dissolved in a neutral solution, such as DI water.
The mixture is stirred or ultrasonically agitated, yielding an emulsion 210 of the polar solvent dispersed in a continuous phase of the non-polar solvent. The emulsion 210 contains stable droplets 212 of the polar solvent dispersed in the non-polar solvent and encapsulated by the interfacially active material. Each droplet 212 contains a solution (e.g., an aqueous solution) of ions of the Groups I and III metals (e.g., Cu1+ and In3+ ions, in the example of
The emulsion 210 is exposed to a Group VI element-containing compound, such as a compound containing S, Se, or Te, e.g., by bubbling a gaseous Group VI element-containing compound into the emulsion 210. The gaseous Group VI element-containing compound can be a Group VI element-containing hydride (e.g., H2S gas or H2Se gas) or a gaseous Te-containing compound (e.g., vapors of dimethyl-Te, diethyl-Te, or diisopropyl-Te). The gaseous Group VI element-containing compound can be diluted in a carrier gas with a concentration in a range of, e.g., about 1% to about 10%, e.g., about 1%, about 2%, about 4%, about 6%, about 8%, or about 10%. The carrier gas is a gas that does not react with the ions of the Groups I and III metals, the Group VI element-containing compound, the stable microemulsion, or a product of the quantum dot synthesis approach described here. Example carrier gases include hydrogen, nitrogen, helium, and argon. For instance, H2S gas can be diluted in H2 to a concentration of 1% H2S and 99% H2. In some examples, the group VI element-containing compound can be an aqueous solution, such as a water solution of sodium sulfide (Na2S). In some examples, the group VI element-containing compound can be a solid powder, such as pure anhydrous sodium sulfide (Na2S) or iron sulfide (FeS)
The synthesis process can be performed at a temperature of, e.g., between about 5° C. and about 50° C., e.g., about 5° C., about 10° C., about 15° C., about 20° C., about 25° C., about 30° C., about 35° C., about 40° C., about 45° C., or about 50° C. The process can be performed at a pressure of, e.g., between about 1 and 5 atmospheres (atm) of pressure, e.g., about 1 atm, about 2 atm, about 3 atm, about 4 atm, or 5 atm. The flow rate of pure inert gas flow rate can range from about 5 milliliter per minute (mL/min) to about 120 mL/min, e.g., about 5 mL/min, about 10 mL/min, about 20 mL/min, about 30 mL/min, about 40 mL/min, about 50 mL/min, about 60 mL/min, about 70 mL/min, about 80 mL/min, about 90 mL/min, about 100 mL/min, about 110 mL/min, or about 120 mL/min. The flow rate of the diluted gas containing Group VI element compound can depend on the reactor size. For instance, for reactors with size between about 20 mL and about 500 mL, the flow rate can be between about 5 mL/min and about 40 mL/min, e.g., about 5 mL/min, about 10 mL/min, about 15 mL/min, about 20 mL/min, about 25 mL/min, about 30 mL/min, about 35 mL/min, or about 40 mL/min. For reactors with size bigger than about 500 mL, the flow rate can be between about 20 mL/min and about 100 m/min, e.g., about 20 mL/min, about 30 mL/min, about 40 mL/min, about 50 m/min, about 60 mL/min, about 70 mL/min, about 80 mL/min, about 90 mL/min, or about 100 mL/min. Other values for temperature, pressure, and flow rate can also be used to maintain the microemulsion template in a stable condition.
When the Group VI element-containing compound is bubbled into the emulsion (216), ions of the group VI element (e.g., S2− ions, in the example of
The size of the cores 222 depends on the initial concentration of the Groups I and III metal precursor reactants in the polar (e.g., aqueous solution), but does not depend on reaction time. The composition of the cores 222 depends on the ratio of the Group I metal precursor reactant to the Group III metal precursor reactant in the polar solution. Both the concentration and the ratio can be controlled precisely, enabling precise control over the size and size distribution of the cores 222 that are synthesized in this microemulsion template approach. The size distribution of the cores 222 depends on the size distribution of the droplets 212, which is a thermodynamically controlled process that can be controlled to deliver high size uniformity (e.g., narrow size distribution).
Further description of microemulsion template approaches to nanoparticle synthesis can be found in U.S. Patent Application Publication No. 2005/0006800 and U.S. Pat. No. 7,608,237, the contents of both of which are incorporated here by reference in their entirety.
In some examples, a thin shell of a high band gap material (e.g., ZnS or ZnSe) is grown on the surface of the cores 222 while the cores are still contained in the interior of the droplets 212. For instance, one or more precursor compounds can be provided into the emulsion under conditions suitable for the precursor compounds or ions thereof to diffuse into the interior of the droplets 212. The precursors are a material that can form a semiconductor with a higher band gap than the band gap energy of the cores 222. In some examples, S or Se is provided by bubbling a hydride gas (e.g., H2S or H2Se) into the emulsion. In some examples, a liquid solution, e.g., a solution of Na2S, Thiourea, or Selenourea is mixed into the emulsion. An aqueous solution containing zinc salt (e.g., Zinc acetate, Zinc sulfate, Zinc chloride, Zinc nitrate) can be used as Zn2+ precursor to react with S or Se precursor to form the shell. The concentration and volume of the precursor compounds can affect the stability and thickness of the shell. Due to the limitation of volume of polar solvent to form stable spherical emulsion droplets, a high concentration of Zn2+ and S2− or Se2− precursor can be used, e.g., a concentration of 1M or 2M or a concentration that approaches or reaches a maximum solubility limit. In some examples, a solid, such as a solid powder, e.g., pure anhydrous of Na2S, Thiourea, or Selenourea solid chemical, is mixed directly with the emulsion. The solid chemical slowly dissolves in the polar phase of the microemulsion and decomposes and hydrolyses to form precursor ions. A solid chemical containing zinc salt (e.g., Zinc acetate, Zinc sulfate, Zinc chloride, Zinc nitrate) can also be used as Zn2+ precursor to be dissolved into microemulsion droplets to react with S2− or Se2− precursor to form the shell. Using solid powder of salts as a precursor takes a longer time to grow the shell. If both shell precursors are provided as solid powder, the second precursor is not added until all of the first precursor solid is completely dissolved into the microemulsion droplets. Coating core dots with a thin shell inside microemulsion template can be performed at a temperature that does not affect the stability of the microemulsion template, e.g., a temperature between about 5° C. and about 50° C., e.g., about 5° C., about 10° C., about 15° C., about 20° C., about 25° C., about 30° C., about 35° C., about 40° C., about 45° C., or about 50° C. In some examples, a specific volume of Na2S aqueous solution is mixed with specific volume of microemulsion which contains specific size of core dots and is allowed to react at room temperature with magnetic stirring for, e.g., 4-24 hours, following by adding an equal molar amount of Zn2+ precursor aqueous solution to react with the S2− precursor. The whole mixture is continuously stirred for, e.g., 24 hours or sonicate for, e.g., 30-60 minutes to complete the reaction. In some examples, especially for the synthesis of core nanoparticles with excess amount of the Group VI element, adding only the Zn2+ precursor can be sufficient to grow a thin ZnS shell. The Zn2+ precursor can be provided as an aqueous solution or as a solid powder. A specific volume of Zn2+ precursor aqueous solution or precursor salt powder is mixed with a microemulsion which contains a specific size of core quantum dots and is allowed to react at room temperature with magnetic stirring for, e.g., at least 24 hours to complete the shell growing reaction. The amount of ZnS or ZnSe precursor to be added can be estimated by knowing the thickness of shell expected and the size of core dots. The thickness of the thin shell formed on the core dots in the microemulsion template approach can be between, e.g., about 0.3 nm and about 1 nm. The resulting structure, formed of an I-II-VI semiconductor core capped with a thin shell of a high band gap material, is referred to as a thin-shell quantum dot.
The thin-shell quantum dots are functionalized with ligands, such as hydrophobic or hydrophilic ligands. Functionalization with hydrophilic ligands can occur while the thin-shell quantum dots are still contained in the interior of the droplets 212. Functionalization with hydrophobic ligands can occurs when the droplets 212 are broken. This functionalization helps with extraction of the thin-shell quantum dots from the emulsion. The thin-shell quantum dots typically have surface defects and weak emission. Upon extraction, the thin-shell quantum dots are annealed and a thicker shell is grown thereon, thereby improving the quantum yield and stability of the quantum dots and producing core-shell quantum dots soluble in water or organic solvents. In some examples, core-shell quantum dots soluble in organic solvents (e.g., functionalized with hydrophobic ligands) are surface modified by ligand exchange to form water soluble core-shell quantum dots, e.g., quantum dots with functional groups capable of bio-conjugation.
Examples of hydrophilic surface ligands for functionalization of the thin-shell quantum dots in the microemulsion can be thiol-carboxylic acid or thiol-hydroxyls (e.g., mercaptosuccinic acid, 3-mercaptopropionic acid, thiol-(PEG)n-carboxylic acid, thiol-(PEG)n-hydroxyl, mercaptoundecanoic acid, mercapohexadecanoic acid, mercaptopropanol, mercaptohexanol, or other suitable ligands). In a specific example, the surface functionalization and extraction process can be performed as follows for functionalization with hydrophilic ligands: a specific amount of pure thiol-carboxylic acid is added into a specific volume of microemulsion which contains thin-shell quantum dots and mixed with magnetic stirring for, e.g., a minimum of 24 hours at room temperature. An at least equal volume of a solvent, such as methanol or ethanol, is mixed with this microemulsion mixture to break down the microemulsion, followed by adding a basic chemical solution (e.g., 1M sodium hydroxide water solution, 1M tetramethylammonium hydroxide water solution, 1M potassium tert-butoxide methanol solution, or another suitable basic solution) to deprotonate the carboxylic acid group. The amount of thiol-carboxylic acid and basic chemical added depends on the volume of microemulsion treated. As an example, to treat 5 mL of microemulsion which contains thin-shell quantum dots, 5-30 mg of mercaptopropionic acid is added to functionalize the surface of the quantum dots, and 50-400 μl of 1M NaOH solution is added to deprotonate the carboxylic acid. A strong non-polar solvent (e.g., diethyl ether) is added into the methanol-microemulsion mixture which contains the hydrophilic thin-shell quantum dots to help precipitate the hydrophilic dots. The volume of non-polar solvent added in is, e.g., at least 20% more than that the volume of the methanol-microemulsion mixture (e.g., for 10 mL of methanol-microemulsion mixture, at least 12 ml of diethyl ether is added). Centrifugation can be performed to accelerate the precipitation process. The liquid phase chemicals are discarded after centrifugation, and the solid hydrophilic quantum dots are dispersed in a polar solvent, e.g., water, for further annealing and shell growth process.
Examples of hydrophobic surface ligands include, e.g., fatty acids, such as lauric acid, oleic acid, or other suitable fatty acids; alkanamines, such as hexadecylamine, oleic amine, dodecylamine, or other suitable alkanamines; phosphines, such as trioctylphosphine, tributyl phosphine, trioctylphosphine oxide, or other suitable phosphines; or alkanethiols, such as 1-dodecanethiol or other suitable alkanethiols; or other suitable hydrophobic ligands, or mixtures thereof. In a specific example, the surface functionalization and extraction process can be performed as follows for functionalization with hydrophobic ligands: a specific amount of hexadecylamine is dissolved in methanol. The methanol-hexadecylamine solution is added into a specific volume of microemulsion which contains thin-shell quantum dots and mixed with magnetic stirring for, e.g., a minimum of 2 hours at room temperature to break down the microemulsion and passivate the thin-shell quantum dots with hydrophobic surface ligands. The amount of hydrophobic ligand and the volume of methanol is estimated based on the volume of microemulsion processed. As an example, to treat 5 mL of microemulsion which contains thin-shell quantum dots, 0.1-0.5 g of hexadecylamine is added to passivate the quantum dots surface, and 5-10 mL of methanol is added to break down the microemulsion. The hydrophobic ligand passivated thin shell quantum dots will precipitate out of the methanol-P-xylene-P105 mixture. Centrifugation can be performed to accelerate the precipitation process. The liquid phase chemicals are discarded after centrifuge, and solid hydrophobic quantum dots are dispersed in an organic solvent, such as hexane, heptane or methanol for further annealing and shell process performed. For instance, hydrophobic thin-shell quantum dots can be annealed and shelled in a batch reactor at high reaction temperature.
In the example of
In the example of
The gaseous Group VI element-containing compound diluted in a carrier gas (e.g., H2S diluted in H2) is provided from a gas source 308 and bubbled into the reactor 302. The flow rate of the gas from the gas source 308 is controlled by a flow controller 310 including one or more valves and flow meter. The gaseous Group VI element-containing compound diffuses into the microemulsion droplets, reacting with the precursor reactants to form I-III-VI semiconductor quantum dot cores (e.g., nanocrystals of CuInS2) in the microemulsion template droplets. Excess of the gaseous Group VI element-containing compound that did not diffuse into the microemulsion droplets or was not absorbed by microemulsion template is burned off at a cracking furnace 312.
The synthesis process can be performed at a temperature of, e.g., between about 5° C. and about 50° C., e.g., about 5° C., about 10° C., about 15° C., about 20° C., about 25° C., about 30° C., about 35° C., about 40° C., about 45° C., or about 50° C. The process can be performed at a pressure of, e.g., between about 1 and 5 atmospheres (atm) of pressure, e.g., about 1 atm, about 2 atm, about 3 atm, about 4 atm, or 5 atm. The flow rate of pure inert gas flow rate can range from about 5 milliliter per minute (mL/min) to about 120 mL/min, e.g., about 5 mL/min, about 10 mL/min, about 20 mL/min, about 30 mL/min, about 40 mL/min, about 50 mL/min, about 60 mL/min, about 70 mL/min, about 80 mL/min, about 90 mL/min, about 100 mL/min, about 110 mL/min, or about 120 mL/min. The flow rate of the diluted gas containing Group VI element compound can depend on the reactor size. For instance, for reactors with size between about 20 mL and about 500 mL, the flow rate can be between about 5 mL/min and about 40 mL/min, e.g., about 5 mL/min, about 10 mL/min, about 15 mL/min, about 20 mL/min, about 25 mL/min, about 30 mL/min, about 35 mL/min, or about 40 mL/min. For reactors with size bigger than about 500 mL, e.g., between 500 mL and 10 L, the flow rate can be between about 20 mL/min and about 100 mL/min, e.g., about 20 mL/min, about 30 mL/min, about 40 mL/min, about 50 mL/min, about 60 mL/min, about 70 mL/min, about 80 mL/min, about 90 mL/min, or about 100 mL/min. Other values for temperature, pressure, and flow rate can also be used to maintain the microemulsion template in a stable condition.
The reaction time depends on the flow rate of diluted gas containing Group VI element compound, the precursor concentration and the size of reactor. In general, the flow rate is selected such that the reaction time is not too short to be controlled. As an example, for a 100 mL reactor which contains microemulsion using 0.3 M precursor concentration, and 20 mL/min flow rate, the reaction is completed in about 10-12 minutes.
The size and crystal structure of the quantum dots is affected by factors including concentration of the precursor reactants in the polar solvent, the ratio of Group I metal precursor reactant to the group III precursor reactant, the flow rate and flow time of the gaseous Group VI element-containing compound, and the relative concentrations of the polar solvent, the non-polar solvent, and the interfacially active material.
Following synthesis of the quantum dot cores, a thin shell of a high band gap material (e.g., ZnS or ZnSe) is grown on the surface of the cores while the cores are still contained in the interior of the droplets. The thin-shell quantum dots are functionalized with hydrophilic surface ligands or hydrophobic ligands to assist with extraction of the quantum dots from the emulsion. The extracted, ligand-functionalized thin-shell quantum dots can be dispersed in an appropriate solvent. For instance, thin-shell quantum dots passivated with hydrophilic surface ligands are dissolved in water. Thin-shell quantum dots passivated with hydrophobic ligands are dissolved in an organic solvent such as hexane, heptane, methanol, chloroform, or another appropriate organic solvent.
The synthesis of thin-shell quantum dots and functionalization of the quantum dots with hydrophilic or hydrophobic surface ligands occurs in a single reactor. The extracted, functionalized thin-shell quantum dots are water soluble or soluble in organic solvents, depending on the nature of the ligands, and can be provided directed to an annealing process (described infra) without purification, further functionalization, or solvent switching. The annealing process can be a continuous flow anneal process or a batch anneal process.
In some examples, the extracted thin-shell quantum dots synthesized using the microemulsion template approach described supra are annealed in a continuous flow, dynamic annealing process. The dynamic annealing process stabilizes the quantum dots and facilitates the removal of defects from the crystalline structure of the quantum dots, thereby increasing their quantum yield. In a dynamic annealing process, the quantum dots are subjected to repeated heating-cooling cycles. In each heating-cooling cycle, the quantum dots are heated to a target heating temperature and then cooled to a target cooling temperature. The heating portion of the heating-cooling cycle promotes surface restructuring of the quantum dots. The cooling portion of the heating-cooling cycle promotes surface relaxation of the quantum dots. This dynamic annealing process helps to prevent secondary degradation of the organic ligands of the quantum dots, which can result in a broadening of the size distribution of the quantum dots. The cycling of the dynamic annealing process to temperatures below the boiling point of most solvents enhances safety and enables the use of a range of solvents, including water, during the annealing process.
The frequency of the heating-cooling cycles of the dynamic annealing process is between about 0.0001 Hz and about 1 Hz, e.g., about 0.0001 Hz, about 0.001 Hz, about 0.01 Hz, about 0.1 Hz, about 0.5 Hz, or about 1 Hz. The dynamic annealing process includes at least 10 heating-cooling cycles, e.g., between 10 and 1000 heating-cooling cycles, e.g., 10, 50, 100, 500, or 1000 heating-cooling cycles. During the heating portion of the heating-cooling cycle, the NIR QDs are heated to a temperature of between about 200° C. and about 250° C., e.g., about 200° C., about 225° C., or about 250° C. During the cooling portion of the heating-cooling cycle, the NIR QDs are cooled to a temperature of between about 10° C. and about 40° C., e.g., about 10° C., about 15° C., about 20° C., about 25° C., about 30° C., about 35° C., or about 40° C. The temperatures in the heating and cooling portions are selected such that the heating temperature does not evaporate the ligands, and the low temperature keeps the solution of quantum dots as a flowable liquid.
In some examples, the emission spectra of the NIR QDs are testing inline along the tube 406 to determine quantum yield. For instance, the dynamic annealing processing following microemulsion template synthesis of NIR QDs results in a quantum yield of greater than about 40% in an aqueous medium. Other characterization of the NIR QDs, e.g., characterization of particle size, surface morphology, or other appropriate characterizations, can be performed ex situ following completion of the dynamic annealing process.
The droplets 510 pass through a tubular coiled reactor 516 at sufficient velocity to achieve desired residence times in the reactor 516. The residence times can be between about 1 minute and about 300 minutes, e.g., about 1 minute, about 5 minutes, about 10 minutes, about 15 minutes, about 30 minutes, about 60 minutes, about 90 minutes, about 120 minutes, about 150 minutes, about 180 minutes, about 210 minutes, about 240 minutes, about 270 minutes, or about 300 minutes. The output of the reactor 516 is water soluble quantum dots having a thick shell of a high band gap material, e.g., ZnS or ZnSe, and exhibiting fluorescence emission in a target wavelength range, with narrow FWHM and high brightness. A second characterization station 518 implementing, e.g., UV-vis or fluorescence spectroscopy, characterizes the quantum dots output from the reactor 516. For instance, the size, optical properties, stability, or other characteristics of the quantum dots can be characterized.
The flow rate of the thin-shell quantum dots 502 and the precursor 504 are controlled by flow controllers, e.g., syringe pumps, valves, or other appropriate flow controllers. The temperature of elements of the system is controlled by temperature controllers, e.g., thermal reservoirs such as oil baths. The flow of the dispersant gas 508 is blended and maintained using gas flow controllers, e.g., thermal mass flow controllers.
The thin-shell quantum dots 502 and the precursor 504 can be flowed at flow rates of between about 0.01-5 mL/min, e.g., about 0.01 mL/min, about 0.05 mL/min, about 0.1 mL/min, about 0.5 mL/min, about 1 mL/min, about 2 mL/min, about 3 mL/min, about 4 mL/min, or about 5 mL/min. The dispersant gas 508 can be flowed at a flow rate of between about 0 and about 200 sccm, e.g., about 0 sccm, about 1 sccm, about 5 sccm, about 10 sccm, about 25 sccm, about 50 sccm, about 100 sccm, about 150 sccm, or about 200 sccm. Elements of the system can be maintained at a temperature of between about 20° C. and about 200° C., e.g., about 20° C., about 50° C., about 75° C., about 100° C., about 125° C., about 150° C., about 175° C., or about 200° C.
In some examples, to improve the quantum yield and remove surface defects of thin-shell quantum dots, such as hydrophobic thin-shell quantum dots, the annealing and shelling processes are performed in a high temperature batch reactor system. Hydrophobic thin-shell quantum dots dispersed in an organic solvent such as hexane, heptane, methanol, or other appropriate organic solvent are transferred into a batch reactor which contains hydrophobic surface ligands as high temperature coordinating solvents. The coordinating solvents can be, e.g., fatty acids, such as lauric acid, oleic acid, or other suitable fatty acids; alkanamines, such as hexadecylamine, oleic amine, dodecylamine, or other suitable alkanamine; phosphines, such as trioctylphosphine, tributyl phosphine, trioctylphosphine oxide, or other suitable phosphines; or alkanethiols, such as 1-dodecanethiol or other suitable alkanethiols; or other suitable hydrophobic ligands, or mixtures thereof. The coordinating solvent can be only one type of hydrophobic surface ligands or a mixture of several different types of surface ligands with specific ratio. The hydrophobic thin-shell quantum dots with coordinating solvents are heated in a batch reactor under an inert atmosphere (e.g., N2 or Argon) to a high temperature, e.g., between about 200° C. and about 300° C. and kept for, e.g., between about 1 hour and about 3 hours. The temperature is then reduced to a lower temperature, e.g., between about 60° C. and about 100° C., and the reaction mixture is maintained at this lower temperature for another, e.g., 2-4 hours to complete the annealing process. To coat hydrophobic thin-shell quantum dots with a thicker shell, a mixture of precursors of the shell composition are injected into the batch reactor, e.g., as droplets, resulting in the formation of core-shell structures. The precursors can be, e.g., a mixture of precursors to ZnS in trioctylphosphine or tributylphosphine. The sulfur precursor can be, e.g., hexamethyl(disilathiane)(TMS2S) and the zinc precursor can be, e.g., diethylzinc or dimethylzinc, zinc acetate, zinc stearate, or zinc acetylacetonate, or other suitable zinc precursor. If an alkanethiol is used as the coordinating solvent, the coordinating solvent can also function as sulfur precursor. The shelling temperature or the shell precursor injection temperature can be between, e.g., about 130° C. and about 220° C. The precursor injection temperature is determined based on the size of the core dots, with a higher injection temperature used for larger size cores and relatively lower injection temperature used for smaller core sizes. After completion of shell precursor solution injection, the reaction mixture is kept at precursor injection temperature for, e.g., 0.5-2 hours to form a semiconductor shell with a crystalline structure. The reactor temperature is subsequently reduced to, e.g., between about 60° C. and about 100° C. and kept for several hours to complete the annealing and shelling process, resulting in NIR core shell quantum dots with high quantum yield.
In some examples, following the annealing and shelling process, hydrophobic NIR core-shell quantum dots are converted into water soluble NIR core-shell quantum dots by ligand exchanging with hydrophilic surface ligands, such as thiol-carboxylic acid and thiol-hydroxyl, i.e. mercaptopropionic acid, mercaptoundecanoic acid, mercaptohexadecanoic acid, thiol-(PEG)n-carboxylic acid, thiol-(PEG)n-hydroxyl, mercaptopropanol and mercaptohexanol, The hydrophilic surface ligands used for ligand exchange can all have the same functional group, or a combination of different functional groups can be used, e.g., to produce quantum dots functionalized with both —COOH and —OH functional groups.
A first reactant and a second reactant are dissolved in polar solvent to form a solution of ions of a Group I element (e.g., ions of Cu or Ag) and ions of a Group III element (e.g., ions of In or Ga) (600). The first reactant includes a Group I element-containing compound, such as a salt of the Group I element, e.g., CuI, CuCl, or AgNO3. The second reactant includes a Group III element-containing compound, such as Indium (III) acetate or Indium (III) sulfate. The polar solvent is water or formamide.
In some examples, dissolving the first and second reactants in the polar solvent includes adjusting the pH of the polar solvent, e.g., by adding an acid or a base to the polar solvent, to promote dissolution of the first and second reactants. In some examples, the first reactant is dissolved in a basic solution of the polar solvent and the second reactant is dissolved in an acidic solution of the polar solvent, and the two solutions are combined to form the solution of the ions of a Group I element and the ions of a Group III element.
The solution of the ions of the Group I element and ions of the Group III element in the polar solvent is mixed with a non-polar solvent and an interfacially active material to form an emulsion (602). The emulsion includes droplets of the solution of the ions of the Group I element and ions of the Group III element in the polar solvent dispersed in a continuous phase of the non-polar solvent. The droplets are encapsulated by an interfacially active material. The non-polar solvent includes an alkane or an alkene. The interfacially active material includes an amphiphilic block copolymer, a surfactant, a water-dispersible polymer, an amphiphilic molecule, a solid particle, or a solvent-swollen particle.
The emulsion is exposed to ions of a Group VI element, such as S, Se, or Te, under conditions sufficient to permit the ions of a Group VI element to react with the ions of the Group I element and ions of the Group III element in the droplets to form nanoparticles in the droplets (604). The emulsion can be exposed to the ions of the Group VI element by contacting the emulsion with a gas containing a Group VI element-containing compound, such as a hydride of the Group VI element, e.g., by bubbling the gas into the emulsion.
The nanoparticles have a composition ABXy, where A is the Group I element, B is the Group III element, and X is the Group VI element. For instance, the nanoparticles can be CuInS2, CuInSe2, AgInS2, or AgInSe2 nanoparticles.
By introducing zinc and sulfur or selenium precursors into the microemulsion droplets, the two precursors can react and grow a thin shell around the core of nanoparticles, thereby forming thin-shell core-shell nanoparticles (606) in the microemulsion droplets. The thin shell can be ZnS or ZnSe; the zinc precursor can be, e.g., zinc acetate, zinc sulfate, zinc chloride, or another appropriate zinc precursor; the sulfur precursor can be, e.g., sodium sulfide, thiourea, hydrogen sulfide gas, or another suitable sulfur precursor; and the selenium precursor can be, e.g., selenourea, hydrogen selenide, or another appropriate selenium precursor.
The thin-shell core-shell nanoparticles are passivated with hydrophilic or hydrophobic surface ligands (608), depending on the desired solubility for the nanoparticles, and extracted from the emulsion (610).
The extracted thin-shell core-shell nanoparticles are thermally annealed (612). In some examples, the annealing is a continuous flow anneal process in which the nanoparticles are exposed to multiple cycles of heating and cooling. Thermally annealing the nanoparticles can include flowing a solution of the nanoparticles (e.g., an aqueous solution of hydrophilic nanoparticles) through a flow channel and applying heating fluid and cooling fluid to alternating portions of the flow channel to expose the nanoparticles to the multiple cycles of heating and cooling. The multiple cycles of heating and cooling can be an alternation between heating the nanoparticles to a temperature of between 200° C. and 250° C. and cooling the nanoparticles to a temperature of between 10° C. and 40° C., e.g., with a frequency of between 0.0001 Hz and 1 Hz. In some examples, the annealing is a batch anneal process in which the thin-shell core-shell nanoparticles (e.g., a solution of hydrophobic nanoparticles in an organic solvent) are heated to a high temperature in a batch reactor.
The annealed nanoparticles are reacted with a second precursor to thicken the shell on the nanoparticles, thereby forming ternary core-shell nanoparticles (614). The shell can have the same composition as the thin shell, e.g., ZnS or ZnSe, and the second precursor can be a precursor to the ZnS or ZnSe composition. The shell growth process can be a continuous flow process or a batch process.
The resulting ternary core-shell nanoparticles have a fluorescence emission wavelength of between 650 nm and 840 nm, a fluorescence emission spectrum with a full width at half maximum of less than 100 nm, and a quantum yield of at least 40% in aqueous solution.
CuInS2 quantum dot cores were synthesized according to the microemulsion template approach described supra. To synthesize this composition, sufficient Cu1+ and In3+ ions were dissolved in water starting from precursors including CuI or CuCl and Indium (III) acetate or Indium (III) sulfate, respectively. To enhance the solubility of these precursors, both the Cu1− and the In3+ precursors were dissolved in a diluted ammonium hydroxide solution (2N) or hydrochloric acid (HCl) solution (3N) to reach the desired precursors concentration. These acid solution or base solution or neutral inorganic salts water solution were used as the polar phase to prepare the microemulsion templates. CuInS2 quantum dot cores then were synthesized by introducing sulfur precursor into the microemulsion droplets. The sulfur precursor sources can be sodium sulfide (Na2S) water solution, solid Na2S powder or hydrogen sulfide (H2S) gas.
A second synthesis experiment was performed by dissolving a Cu1+ precursor (CuI) in a 3N NH4 basic solution and an In3+ precursor (In(Ac)3) in a 1N HCl acid solution. The two solutions were mixed together and quantum dots were synthesized according to the microemulsion template approach.
The effect of different Cu1+ precursors was also studied. Quantum dot cores were synthesized using the microemulsion template approach described here, by dissolving both CuI and Indium (III) acetate in a 2 N HCl solution (spectrum 804) to a concentration of 0.1 M, both CuI and Indium (III) acetate in a 2 N NH4 solution spectrum (806) to a concentration of 0.1 M, and both CuCl and Indium (III) acetate in a 2 N HCl solution (spectrum 808) to a concentration of 0.1 M. As can be seen from the various spectra, the solubility of the precursor in aqueous solution affects the optical properties of the resulting quantum dot cores.
In addition to different Cu1+ precursor sources, CuInS2 nanoparticle synthesis experiments were also performed using different In3+ precursor sources, including In2(SO4)3, and different S2− precursor sources, such as H2S gas, and following the microemulsion template approach described here. An example group of CuInS2 nanoparticles with different molar precursor concentrations from 0.15M to 0.5M were synthesized according to the following processes using various precursors different from those addressed in the foregoing examples.
Cu1+ precursor bulk solution was prepared by dissolving an appropriate amount of CuI salt in 2N NH4-OH water solution to reach 1M concentration. In3+ precursor bulk solution was prepared by dissolving an appropriate amount of In2(SO4)3 in DI water to reach 1M concentration. Then 0.15M, 0.2M, 0.25M, 0.3M, 0.35M, 0.4M, 0.45M, and 0.5M Cu1+ and In3+ solutions with a Cu1+/In1+ molar ratio 1:1 were prepared by mixing an appropriate volume of each precursor bulk solution and diluting with DI water. The precursor water solution was subsequently mixed with P-xylene and Pluronic® P105 and stirred overnight to form stable microemulsion templates. Hydrogen sulfide gas was introduced into a glass bottle reactor which contained the stable microemulsion template in order to be absorbed by the microemulsion and then react with Cu1+ and In3+ ions to form CuInS2 nanoclusters inside each microemulsion droplet. The hydrogen sulfide gas was produced by a house-made gas reactor. The glass bottle containing microemulsion templates with Cu1− and In3+ ions was put into a secondary container which can be sealed without leaking. A small vial which contained an appropriate amount of iron sulfide (FeS) solid powder was also put into the same container. The secondary container was sealed and 5M hydrogen sulfate acid water solution was injected drop-wise, slowly and continuously, into the small vial which contained FeS to allow FeS react with H2SO4 to produce H2S gas. The generated H2S gas was absorbed by the microemulsion templates and the gas molecules subsequently diffused into the microemulsion droplets to react with Cu1+ and In3+ ions. The color of the microemulsion changed from a light yellow-green color into a dark brown color, which indicated the formation of CuInS2 nanoparticles.
The reaction can be performed for up to 24 hours, but the longer the reaction lasts, more excess of H2S is absorbed by the microemulsion. A minimum of 4 hours of reaction time is suitable for 40 mL of microemulsion template. For a larger volume of microemulsion, longer H2S exposure time is appropriate. Nanoparticle synthesis with these combinations of precursors were carried out in S2− ion-rich conditions. The photoluminescence properties of as-prepared CuInS2 nanoparticles in microemulsion were measured and are illustrated in
Unlike the emission spectra for nanoparticles synthesized under S2− ion deficiency conditions, the peak emission wavelength of CuInS2 nanoparticles synthesized with H2S gas saturation condition in microemulsion templates show a negative correlation with precursor concentration at lower precursor concentration range. As shown in
Without being bound by theory, one possible reason for these unexpected phenomena is the saturation or over excess of hydrogen gas contained in the microemulsion template. In order to verify this hypothesis, zinc acetate water solution was added to each sample to react with the excess of hydrogen sulfide to form ZnS shell around the CuInS2 nanoparticles. The amount of Zn2+ added into each sample was equal to the molar amount of Cu+1/In3+ precursor contained in the microemulsion. The fluorescence emission of ZnS coated CuInS2 nanoparticles synthesized under sulfur rich conditions were measured and results are shown in
Adding zinc acetate water solution into a microemulsion which contains CuInS2 core nanoparticles and an excess of free S2− ions can grow ZnS shell above core nanoparticles inside microemulsion directly. Results indicated that coating CuInS2 core nanoparticles with ZnS significantly increased the florescence emission intensity, especially for core nanoparticles synthesized with high precursor concentration (
AgInS2 has a band gap energy similar to that of CuInS2. Therefore, by adjusting the size and composition of AgInS2 nanoparticles, AgInS2 nanoparticles can act as NIR emission materials. AgInS2 quantum dot cores were synthesized according to the microemulsion template approach described supra.
Silver Nitrate (AgNO3) was used as an Ag1+ precursor, Indium acetate and Indium sulfate were tested to determine which one is able to react with Ag1+ and S2− more efficiently. An Ag1+ precursor bulk solution was prepared by dissolving an appropriate amount of AgNO3 salt in DI water to reach 1.5M concentration. When indium acetate was used as an In3+ precursor, an In3+ precursor bulk solution was prepared by dissolving an appropriate amount of In(Ac)3 in 2N HCL water solution to reach LOM concentration. When indium sulfate was used as an In3+ precursor, an In3+ precursor bulk solution was prepared by dissolving an appropriate amount of In2(SO4)3 in DI water to reach 1M concentration. Then a 0.2M Ag1+ and In3+ solution with an Ag1+/In3+ molar ratio 1:1 was prepared by mixing an appropriate volume of each precursor bulk solution and diluting with DI water. The precursor water solution was subsequently mixed with P-xylene and Pluronic® P105 and stirred overnight to form stable microemulsion templates. Solid sodium sulfide powder was used as a S2− precursor. The amount of S2− added was controlled to make the stoichiometric ratio of S2−/Ag1+ equal to 2. After adding an appropriate amount of Na2S powder to the microemulsion which contained Ag1+ and In3, the microemulsion was stirred to allow Na2S hydrolysis to generate H2S gas. The H2S gas diffused into the microemulsion droplets and reacted with Ag+1-In3+ precursors to form AgInS2 nanoparticles. The color of the microemulsion changed from a light grey color to a light yellow-brown or dark red-color, which indicated the formation of AgInS2 nanoparticles.
For AgInS2 nanoparticles synthesized with the same Ag1+ and In3+ precursor concentration (0.2M), the sample which used In(Ac)3 as the In3+ precursor showed an emission peak around 500 nm, while the sample which used In2(SO4)3 as the In3+ precursor showed two emission peaks, one around 600 nm and the other around 850 nm. For nanoparticles synthesized using In(Ac)3 as the In3+ precursor, apparently due to presence of hydrogen chloride acid inside the microemulsion droplets for dissolving In(Ac)3, the as-prepared AgInS2 nanoparticles decomposed very fast as losing of S2− ions. It was difficult to form an Ag—S donor-acceptor recombination conductive band gap, which is the major contributor to near infrared emission. For samples synthesized using In2(SO4)3 as the In3+ precursor, the Ag—S conductive band gap was partially formed, which was indicated with the NIR emission around 850 nm.
Experiments were subsequently performed by using In2(SO4)3 as the In3+ precursor but with increasing precursor concentration. The Ag1+ ion precursor, S2− ion precursor, and experimental condition were kept the same. The optical spectra for the as-prepared core AgInS2 nanoparticles are shown in
To improve the NIR emission intensity, attempts were made to grow a ZnS shell directly above “naked” AgInS2 core nanoparticles inside the microemulsion. 10 mL of as-prepared core AgInS2 nanoparticles synthesized with various precursor concentrations and passivated by microemulsion micelles was used as the base for grown of ZnS shells. Sodium sulfide water solution (with concentration of 2M) was added to the microemulsion and the samples were stirred for at least 2 hours to allow a sufficient amount of S2− ions be generated inside the microemulsion droplets. The amount of sodium sulfide added was equal to the molar amount of Ag and In precursors contained in the as-prepared core nanoparticles-microemulsion. As the microemulsion color became darker, indicating generation of H2S gas inside the microemulsion droplets, an equal molar amount of zinc acetate (1.5M zinc acetate water solution) was added and the mixture was continuously stirred overnight to complete the shell growth. The fluorescence emission of core/shell AgInS2/ZnS core-shell nanoparticles synthesized using with various precursor concentrations in microemulsion were measured and the results are illustrated in
Referring to
Without being bound by theory, one possible reason for these observed phenomena is a deficiency of S2− ions. Synthesized core AgInS2 nanocrystals with excess of S2− ions may avoid the domination of formation of In—S recombination emission but make Ag—S recombination NIR become dominant for fixed Ag/In ratio. Experiments synthesizing AgInS2 nanoparticles with a saturation of S2− ions were performed to verify the hypothesis.
For this group of experiments, AgNO3 was used as the Ag1+ precursor source, In2(SO4)3 was used as the In3+ precursor source, and H2S gas was used as the S2− precursor source. AgInS2 core nanoparticles were synthesized with different molar precursor concentrations from 0.15M to 0.6M by following the microemulsion template approach described here.
An Ag+ precursor bulk solution was prepared by dissolving an appropriate amount of AgNO3 salt in DI water to reach 1.5M concentration. An In3+ precursor bulk solution was prepared by dissolving an appropriate amount of In2(SO4)3 in DI water to reach 1M concentration. Then 0.15M, 0.25M, 0.3M, 0.35M, 0.45M, 0.5M, 0.55M and 0.6M Ag1+ and In3+ solutions with Ag1+/In3+ molar ratio 1:1 were prepared by mixing an appropriate volume of each precursor bulk solution and diluting with DI water. The precursor water solution was subsequently mixed with P-xylene and Pluronic® P105 and stirred overnight to form stable microemulsion templates. Hydrogen sulfide gas was introduced into a glass bottle reactor which contained the stable microemulsion template in order to be absorbed by the microemulsion and then react with Ag1+ and In3+ ions to form AgInS2 nanoclusters inside each microemulsion droplet. The hydrogen sulfide gas was produced by a house-made gas reactor. The glass bottle containing microemulsion templates with Ag1+ and In1+ ions was put into a secondary container which can be sealed without leaking. A small vial which contained an appropriate amount of iron sulfide (FeS) solid powder was also put into the same container. The secondary container was sealed and 5M hydrogen sulfate acid water solution was injected drop-wise, slowly and continuously, into the small vial which contained FeS to allow FeS react with H2SO4 to produce H2S gas. The generated H2S gas was absorbed by the microemulsion templates and the gas molecules subsequently diffused into the microemulsion droplets to react with Ag1+ and In3+ ions. The color of the microemulsion changed from a light grey color into a dark red or dark brown color, depending on the precursor concentration, which indicated the formation of CuInS2 nanoparticles. For each sample, the reaction was performed for 5 hours to complete the synthesis. The photoluminescence properties of as-prepared AgInS2 core nanoparticles in microemulsion were measured and the results are illustrated in
These results confirmed that AgInS2 core nanoparticle synthesis in microemulsion templates prefers rich sulfur experimental condition. The Ag—S donor-acceptor recombination NIR emission is dominant for AgInS2 nanoparticles synthesis with an excess of H2S existing in the microemulsion template. The peak emission wavelength of the as-prepared core nanoparticles showed a red shift with increasing the precursor concentration, with both excitation and emission scanning confirming the trend. By changing the precursor concentration from 0.15M to 0.6M, the peak emission wavelength of the core AgInS2 nanoparticles shifts from ˜730 nm up to 820 nm. Core AgInS2 nanoparticles synthesized with lower precursor concentration also exhibited very strong emission compared with those synthesized with high precursor concentration.
The as-prepared core AgInS2 nanoparticles synthesized under rich S2− conditions were coated with a thin ZnS shell directly within the microemulsion droplets to verify whether the coating would passivate the surface of the core nanoparticles and thereby increase the brightness of the core nanoparticles.
Due to the large excess of H2S in the as-prepared core nanoparticle microemulsion, ZnS shell growth was performed by adding Zn2+ precursors only instead of both Zn2+ and S2− precursors. 10 mL of as-prepared core AgInS2 nanoparticles synthesized with various precursor concentrations in rich H2S and passivated by microemulsion micelles was used as a base for growth of ZnS shells. A 1.5M Zn(Ac)2 water solution was used as the Zn2+ precursor source. The amount of zinc acetate added was equal to the molar amount of Ag and In precursor contained in the as-prepared core nanoparticle microemulsion. The solution of the core nanoparticle microemulsion with the added Zn(Ac)2 water solution was stirred overnight to complete the shell growth.
The fluorescence emission of core/shell AgInS2/ZnS nanoparticles synthesized in microemulsion with an excess of S2− and with various precursor concentrations was measured and the results are illustrated in
Referring to
To investigate the effect of ZnS shell coating on “naked” AgInS2 nanoparticles synthesized in microemulsion with an excess of S2−, 80 mL of AgInS2 core nanoparticles in microemulsion with 0.4M precursor concentration were synthesized according to the microemulsion template assisted method described here. Silver Nitrate (AgNO3) and Indium Sulfate (In2(SO4)3) salts were used as Ag1+ and In3+ precursor sources, respectively, and hydrogen sulfide gas was used as the S2− precursor source. 1.5M silver nitrate and 1M Indium sulfate concentrated bulk solutions were prepared by dissolving an appropriate amount of the inorganic salt in DI water. A 0.4M Ag1+ and In3+ solution with an Ag1+/In3+ molar ratio of 1:1 was prepared by mixing an appropriate volume of each precursor bulk solution and diluting with DI water. The precursor water solution was subsequently mixed with P-xylene and Pluronic® P105 and stirred overnight to form stable microemulsion templates. Hydrogen sulfide gas was introduced into a glass bottle reactor which contained the stable microemulsion template in order to be absorbed by the microemulsion and then react with Ag1+ and In3+ ions to form AgInS2 nanoclusters inside each microemulsion droplet. The color of the microemulsion changed from a light grey color to a dark brown color, indicating the formation of AgInS2 nanocrystals. The as-prepared AgInS2 nanoparticles in microemulsion were stored in dark condition for one week before performing the shell coating study in order to stabilize the core nanoparticles.
Five samples of nanoparticles in microemulsion were prepared for the shelling condition investigation. Each sample contained 10 mL as-prepared, one week matured AgInS2 nanoparticles in microemulsion. Five shell coatings were performed as follows. For each sample, the as-prepared core dots in microemulsion was used except for Shell #5. For Shell #5, the clear microemulsion layer, which did not contain a large amount of excess sulfur, was collected for use in the shell coating process.
Shell #1: a molar amount of sodium sulfide (2M water solution) equal to the molar amount of Ag and In precursors contained in the as-prepared AgInS2 nanoparticles in microemulsion was added to the emulsion. The mixture was stirred at room temperature for 2 hours, then an equal molar amount of zinc acetate (1.5M zinc acetate water solution) was added and the mixture was continuously stirred overnight.
Shell #2: an equal molar amount of zinc acetate only (1.5M water solution) was added to the nanoparticles in microemulsion and the sample was stirred overnight.
Shell #3: an equal molar amount of zinc acetate only (dry solid chemical) was added to the nanoparticles in microemulsion and the sample was stirred overnight.
Shell #4: a double molar amount of zinc acetate only (dry solid chemical) was added to the nanoparticles in microemulsion and the sample was stirred overnight.
Shell #5: a double molar amount of zinc acetate only (dry solid chemical) was added to the nanoparticles in microemulsion and the sample was stirred overnight.
The fluorescence properties of all shell samples were tested, and the un-coated core nanoparticles in microemulsion were used for comparison.
Referring to
Notably, as illustrated in
Since the major mechanism for NIR emission of I-III-VI type ternary nanoparticles comes from donor-acceptor recombination, the binding capability of different donor ions with acceptor ions is important. Therefore, changing the precursor ratio in the synthesis of I-III-VI nanoparticles may have a significant effect on the optical properties of the ternary nanoparticles. A group of experiments were performed in which AgInS2 nanoparticles were synthesized according to the microemulsion template method described supra and using various Ag/In precursor ratios.
20 mL of AgInS2 core nanoparticles in microemulsion with 0.4M precursor concentration and different ion ratios were prepared using AgNO3 as the Ag1+ precursors source, In2(SO4)3 as the In3+ precursor source, and sodium sulfide powder as the S2− precursor source. 1.5M silver nitrate and 1M Indium sulfate concentrated bulk solutions were prepared by dissolving an appropriate amount of inorganic salt in DI water. Solutions containing 0.4M In3+ precursor and various Ag1+ concentration with Ag1+/In3+ molar ratio (specifically, 0.9:1, 0.5:1, 0.3:1, and 0.25:1) were prepared by mixing an appropriate volume of each precursor bulk solution and diluting with DI water. The precursor water solution was subsequently mixed with P-xylene and Pluronic® P105 and stirred overnight to form stable microemulsion templates. An appropriate amount of Na2S powder was added to each sample and continuously stirred for 8 hours. The amount of Na2S was added to each sample was controlled to maintain a stoichiometric ratio of In/S=1.2. The color of the microemulsion emulsion changed from a light grey color to a dark yellow color for samples with low Ag+/In3+ ratio and to a dark brown color for samples with higher Ag1+/In3+ ratio.
The fluorescence emission spectra for AgInS2 core nanoparticles synthesized with various Ag1+/In3+ ratios are shown in
These experiments reveal that precursor concentration, precursor ratios, and shell growth affect the emission spectrum of the quantum dot cores significantly. With the experimental conditions described above, the emission wavelengths of the quantum dot cores reached a maximum peak emission wavelength of 840 nm. These experiments also demonstrated that larger size CuInS2 and AgInS2 quantum dot cores have weaker emission intensity than smaller quantum dots. Annealing and further shell coating of the core quantum dots can be performed to enhance the quantum yield.
Surface modification of core or core/shell nanoparticles with suitable surface ligands can be performed, e.g., based on desired functionality for the nanoparticles.
Particular embodiments of the subject matter have been described. Other embodiments are within the scope of the following claims.
This application claims the benefit of priority to U.S. Provisional Application No. 63/215,186, filed on Jun. 25, 2021, the contents of which are incorporated here by reference in their entirety.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2022/034875 | 6/24/2022 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 63215186 | Jun 2021 | US |
