# Patent

## Title
Semiconductor nanoparticle capping agents

## Abstract

Embodiments of the invention involve semiconductor nanoparticle capping ligands, their production and use. Ligands may have the formula




with m ranging from approximately 8 to approximately 45. An embodiment provides a method of forming a compound of the formula





including the steps of providing a first starting material comprising poly(ethyleneglycol) and reacting the first starting material with a second starting material comprising a functional group for chelating to the surface of a nanoparticle to thereby form the compound.

## Background
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of and priority to co-pending U.S. Provisional Patent Application No. 61/031,218, filed Feb. 25, 2008, the entire contents of which are herein incorporated by reference.


FIELD OF THE INVENTION
This invention relates to semiconductor nanoparticle capping ligands, their production and their use in preparing functionalized semiconductor nanoparticles.
BACKGROUND
The size of a semiconductor nanoparticle helps determine the electronic properties of the material; the bandgap energy may be inversely proportional to the size of the semiconductor nanoparticle as a consequence of quantum confinement effects. In addition, the large surface area to volume ratio of the nanoparticle affects the physical and chemical properties of the nanoparticle.
Single-core nanoparticles that include a single semiconductor material typically have relatively low quantum efficiencies. These low quantum efficiencies arise from non-radiative electron-hole recombinations that occur at defects and dangling bonds at the surface of the nanoparticle.
Core-shell nanoparticles typically include a single semiconductor core material that has a shell of a second semiconductor material grown epitaxially on the surface of the core. The shell material usually has a wider bandgap and similar lattice dimensions to the core semiconductor material. The intention of adding the shell may be to eliminate defects and dangling bonds from the surface of the core, and thereby confine charge carriers within the core and away from surface states that may function as centers for non-radiative recombination.
Still, the surfaces of core, core-shell, and core-multishell nanoparticles may have highly reactive dangling bonds. These may be passivated by capping the surface atoms with organic ligand molecules that inhibit aggregation of particles, protect the particle from its surrounding chemical environment, and (at least in the case of core nanoparticles) provide electronic stabilization. The capping ligand compound may be the solvent that is employed in the core growth and/or shelling of the nanoparticles. Alternatively, the capping ligand may be dissolved in an inert solvent and then used in the core growth and/or shelling of the nanoparticles. Either way, the ligand compound caps the surface of the nanoparticle by donating lone-pair electrons to the surface metal atoms of the nanoparticle.
Nanoparticles may typically be synthesized in the presence of a lipophilic ligand compound, resulting in nanoparticles that may be soluble in non-polar media. To decrease or eliminate this solubility, the ligand compound may be exchanged for a different ligand compound of greater polarity; however, the quantum yield of the nanoparticles diminishes as a result.
The resulting semiconductor nanoparticles may be used in a range of different applications, in which the nanoparticles may be externally excited by photo-excitation, electro-excitation, or another form of excitation, leading to electron-hole recombination and subsequent emission of photons in the form of light of a predetermined wavelength, e.g., visible light. The use of surface functionalized nanoparticles in such applications has so far, however, been limited by the loss in quantum yield upon surface functionalization.
SUMMARY
Disclosed herein are methods that may obviate or mitigate one or more of the above problems with current methods for producing surface functionalized semiconductor nanoparticles.
Some embodiments provide for the fabrication of capping ligands for semiconductor nanoparticles as well as the precursors of the capping ligands. The capping ligands disclosed herein may be utilized in and during the synthesis of the nanoparticles, resulting in nanoparticles of high quantum yield and polarity. The resulting semiconductor nanoparticles may be used in a range of different applications, such as display applications whereby the semiconductor nanoparticles may be incorporated into a device or transparent material; or incorporation into polar solvents (e.g., water and water-based solvents). The resulting nanoparticles may also be incorporated into inks, polymers or glasses; or attached to cells, biomolecules, metals, molecules and the like. The compounds and methods disclosed herein thus overcome the problems with prior art methods for the surface functionalization of semiconductor nanoparticles which have previously hindered the use of surface functionalized nanoparticles in such applications.
In an aspect, an embodiment of the invention includes a ligand having the formula




with m ranging from 8 to 45.

One or more of the following features may be included. The ligand may be proximate a core or a shell of a nanoparticle. The core of the nanoparticle may have at least one semiconductor material. The ligand may be disposed within a solvent having at least one nanoparticle precursor material.
In another aspect, an embodiment of the invention includes a method of forming a compound of the formula




where X is an atom or chemical group, Y is an atom or chemical group and m is an integer. A first starting material including poly(ethyleneglycol) is provided, and the first starting material is reacted with a second starting material having a functional group for chelating to the surface of a nanoparticle, thereby forming the compound.

One or more of the following features may be included. The first starting material has a terminal hydroxyl group, the second starting material has a leaving group, and reacting the first and second starting materials includes detaching the leaving group. At least one nanoparticle may be capped with the compound. Variable X may be selected from H, CH3, and —CH2CO2H. Variable Y may be selected from p-toluene sulphonate, carboxyl, —CH2CO2H, PhCO2H, SiPh2tBu, phenyl, —CH2Ph, thiol, amino, dithiocarbamato, phosphonic acid, phosphinic acid, vinyl, acetylene, aryl, and heteroaryl. Variable m may range from 8 to 45. At least one nanoparticle may include at least one semiconductor material.
In another aspect, an embodiment of the invention includes a method for producing capped nanoparticles including capping at least one nanoparticle with a compound of formula




where X is an atom or chemical group, Y is an atom or chemical group and m is an integer.

In yet another aspect, embodiments of the invention include nanoparticles capped with a compound of formula




where X is an atom or chemical group, Y is an atom or chemical group and m is an integer.

One or more of the following features may be included. Variable X may be H, CH3, and/or —CH2CO2H. Variable Y may be selected from p-toluene sulphonate, carboxyl, —CH2CO2H, -PhCO2H, —SiPh2tBu, phenyl, —CH2Ph, thiol, amino, dithiocarbamato, phosphonic acid, phosphinic acid, vinyl, acetylene, aryl, and/or heteroaryl. Variable m may range from 8 to 45. At least one nanoparticle may include at least one semiconductor material.
In another aspect, an embodiment of the invention includes a display device having a plurality of nanoparticles, each capped with a ligand having the formula




where m is an integer, disposed within a material substantially transparent to light.

One or more of the following features may be included. The display device may include means for exciting the plurality of nanoparticles such that the nanoparticles can emit visible light. Each of the plurality of nanoparticles may have a core including a first semiconductor material and a shell including a second semiconductor material different from the first semiconductor material.



BRIEF DESCRIPTION OF THE FIGURE
FIG. 1 schematically illustrates a quantum dot nanoparticle.



DETAILED DESCRIPTION
One embodiment provides for the preparation and use of a compound of the following formula in the production and capping of quantum dot nanoparticles:




where m may be between 0 and approximately 4500, such as between 0 and approximately 450, or even such as 0 and approximately 17. In some embodiments, m may be approximately 8, approximately 13, approximately 17, or approximately 45. These compounds may be suitable for use as a ligand compound (i.e., a capping agent) for core growth and/or shelling of quantum dot nanoparticles.

One embodiment provides a ligand having the formula




with m ranging from approximately 8 to approximately 45.

In one embodiment, the ligand is disposed proximate a core of a nanoparticle, where the core may include at least one semiconductor material. In a further embodiment, the ligand is disposed proximate a shell of a nanoparticle, the shell optionally including at least one semiconductor material. The ligand may be disposed within a solvent, in which case the solvent may further include at least one nanoparticle precursor material.
One embodiment of the invention relates to methods of synthesizing a compound of formula:




where m may be as defined above, X is selected from the group consisting of H, —CH3, and —CH2CO2H, and Y is selected from the group consisting of p-toluene sulphonate, carboxyl (e.g. —CH2CO2H or PhCO2H), SiPh2tBu, phenyl (e.g., —CH2Ph), thiol, amino, dithiocarbamato, phosphonic acid, phosphinic acid, vinyl, acetylene, aryl, heteroaryl, and the like.

Another embodiment provides for a method of forming a compound of the formula




where the method includes the steps of providing a first starting material including poly(ethyleneglycol), and reacting the first starting material with a second starting material that includes a functional group for chelating to the surface of a nanoparticle, thereby forming the compound.

The first starting material may include a terminal hydroxyl group, the second starting material may include a leaving group, and the step of reacting the first and second starting materials may include detaching the leaving group.
In another embodiment, the method further includes capping at least one nanoparticle with the compound. Accordingly, another embodiment relates to a method for producing capped nanoparticles including carrying out the method described above and then capping at least one nanoparticle with the resulting compound of formula




as defined above. Moreover, a further embodiment provides nanoparticles capped with a compound of formula





as defined above.

In another embodiment, the invention relates to a display device including a plurality of nanoparticles, each capped with a ligand having the formula




disposed within a material substantially transparent to light. The display device may include means for exciting the plurality of nanoparticles such that the nanoparticles emit visible light. Moreover, each of the plurality of nanoparticles may include a core including a first semiconductor material, and a shell including a second semiconductor material different from the first semiconductor material.

The above defined methods may include the steps of coupling, to an appropriately functionalized molecule of the formula X—W, the hydroxyl functionality of a poly(ethyleneglycol) starting material having the formula:




where m is as defined above, and Z is selected from the group consisting of H or —CH3. X is selected from the group consisting of a leaving group such as a halogen, p-toluene sulphonate, mesyl (CH3—S(O)2—O—) or a nucleophile such as OH, and W is a suitable functional group to chelate to the surface of a nanoparticle, such as a carboxyl or thio group.

Z may be pre-functionalized to include a head group to afford the desired solubility to nanoparticles capped with the ligand produced as a result of the reaction of X—W with




or Z may be subject to post-reaction modification so that it incorporates the desired head group, such as, but not limited to p-toluene sulphonate, carboxyl (e.g. —CH2CO2H or -PhCO2H), SiPh2tBu, phenyl (e.g. —CH2Ph), thiol, amino, dithiocarbamato, phosphonic acid, phosphinic acid, vinyl, acetylene, aryl, heteroaryl, and the like.

In one embodiment, the ligand has the formula:




where X is —CH3 and m is approximately 8 in both the poly(ethyleneglycol) methyl ether ( ̃350) starting material and ligand compound. Y is H in the poly(ethyleneglycol) methyl ether (having a molecular weight of approximately 350) starting material and Y is —CH2CO2H in the ligand compound.

Further embodiments provide semiconductor quantum dot nanoparticles incorporating the capping ligands defined above and methods for producing the same employing standard synthetic methods for binding such ligands to the nanoparticle surface.
The semiconductor material included in the nanoparticles capped with the above-defined capping ligands may incorporate ions from any one or more of groups 2 to 16 of the periodic table, including binary, ternary and quaternary materials, that is, materials incorporating two, three or four different ions respectively. By way of example, the nanoparticles may incorporate a core semiconductor material, such as, but not limited to, CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, InP, InAs, InSb, AlP, Al2S3, AlAs, AlSb, GaN, GaP, GaAs, GaSb, PbS, PbSe, Si, Ge and combinations thereof. Nanoparticles may possess cores with mean diameters of less than around 20 nm, such as less than around 15 nm and further such as in the range of around 2 nm to around 5 nm.
As mentioned above, in order to at least partially address issues related to non-radiative electron-hole recombinations that occur at defects and dangling bonds at the nanoparticle surface resulting in undesirably low quantum efficiencies, nanoparticle cores may be at least partially coated with one or more layers (also referred to herein as “shells”) of a different material to the core, for example, a semiconductor material. Thus, the nanoparticles capped using ligands disclosed herein may incorporate one or more shell layers. The material included in the or each shell may incorporate ions from any one or more of groups 2 to 16 of the periodic table. Where a nanoparticle includes two or more shells, each shell may be formed of a different material. In an exemplary core/shell material, the core may be formed from one of the materials specified above and the shell may include a semiconductor material of larger band-gap energy and similar lattice dimensions to the core material. Example shell materials include, but are not limited to, ZnS, MgS, MgSe, MgTe and GaN. The confinement of charge carriers within the core and away from surface states provides quantum dots of greater stability and higher quantum yield. It will be appreciated that where two materials may be provided in adjacent layers of a semiconductor nanoparticle whose lattice structures do not correspond closely, it may be appropriate to ease any lattice strain that exists at the interface of the two materials by introducing a graded layer in between the two layers of material. The graded layer will typically include most, if not all, of the ions in each of the two adjacent layers but the proportions of the ions will vary from the core to the shell. The region of the graded layer adjacent to the core will include a majority of at least one of the ions in the core material, and the region of the graded layer adjacent to the shell will include a majority of the at least one of the ions in the shell material.
The mean diameter of quantum dot nanoparticles, which may be capped using the ligands disclosed herein, may be varied to modify the emission wavelength. The energy levels and hence the frequency of the quantum-dot fluorescence emission may be controlled by the material from which the quantum dot is made and the size of the quantum dot. Generally, quantum dots made of the same material have a more pronounced red emission the larger the quantum dot. In some embodiments, the quantum dots have diameters of around 1 nm to around 15 nm, such as around 1 nm to around 10 nm. The quantum dots preferably emit light having a wavelength of around 400 nm to around 900 nm, such as around 400 nm to around 700 nm.
Typically, as a result of the core and/or shelling procedures employed to produce the core, core/shell or core/multishell nanoparticles, the nanoparticles are at least partially coated with a surface binding ligand, such as myristic acid, hexadecylamine and/or trioctylphosphineoxide. Such ligands may typically be derived from the solvent in which the core and/or shelling procedures were carried out. While ligands of this type may increase the stability of the nanoparticles in non-polar media, provide electronic stabilization and/or negate undesirable nanoparticle agglomeration, as mentioned previously, such ligands usually prevent the nanoparticles from stably dispersing or dissolving in more polar media, such as aqueous solvents.
In some embodiments, quantum dots may be included that are aqueous-compatible, stable, small and of high quantum yield (see FIG. 1). Where lipophilic surface binding ligand(s) are coordinated to the surface of the quantum dots as a result of the core and/or shelling procedures (examples include hexadecylamine, trioctylphosphineoxide, myristic acid), such ligands may be exchanged entirely or partially with ligands disclosed herein using standard methods known to the skilled person, or the ligands disclosed herein may interchelate with the existing lipophilic surface binding ligands, again using standard methods.
Embodiments of the invention will now be illustrated by the following examples, which are given for the purpose of illustration only and without any intention of limiting the scope of the present invention.
EXAMPLES
Glassware was dried (120° C.) in an oven overnight. Dichloromethane (“DCM”) and triethylamine (“TEA”) were distilled from calcium hydride after heating at reflux for at least 1 hour. Tetrahydrofuran was distilled from Na/benzophenone after heating at reflux for at least 1 hour. Poly(ethylene glycols) were heated at 120° C. under high vacuum for 1 hour. All other reagents were used as received from a commercial supplier. All reaction mixtures were stirred magnetically and conducted under an atmosphere of dinitrogen gas.
Example 1
Synthesis of monomethyl ether poly(oxyethylene qlycol)350 phthalimide
A. Synthesis of poly(oxyethylene glycol)350 monomethyl ether p-toluene sulfonate




A solution of TsCl (27.792 g, 143.00 mmol) in DCM (80 mL) was added drop-wise over 2 hours to an ice-cooled solution of poly(oxyethylene glycol)350 monomethyl ether (50.000 g, 143.00 mmol), triethylamine (40.30 mL, 290.0 mmol), and DMAP (0.177 g, 1.4 mmol) in DCM (75 mL), and the resultant mixture was left to stir overnight while warming to room temperature. The reaction mixture was washed with distilled water (2×200 mL), saturated sodium bicarbonate solution (2×100 mL), saturated citric acid solution (2×100 mL), dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to give a yellow-colored oil. This oil was dissolved in hexane (3×200 mL) and the unreacted TsCl was separated from the reaction mixture by filtration. The filtrate was concentrated under reduced pressure to provide poly(oxyethylene glycol)350 monomethyl ether p-toluene sulfonate as a pale yellow-colored oil.
B. Synthesis of monomethyl ether poly(oxyethylene glycol)350 phthalimide




Potassium phthalimide (2.679 g, 14.48 mmol) was added to a solution of poly(oxyethylene glycol)350 monomethyl ether p-toluene sulfonate (5.000 g, 9.65 mmol) in DMF (45 mL)/water (6 mL) and then stirred overnight (80° C.).
The reaction mixture was allowed to cool to room temperature, dissolved in DCM (100 mL) and washed sequentially with distilled water (6×500 mL), saturated brine (6×500 mL) (to remove DMF), distilled water (500 mL), then dried over anhydrous magnesium sulphate, filtered and concentrated under reduced pressure. The resultant oil was dissolved in the minimum volume of DCM, filtered, and then concentrated under reduced pressure to give monomethyl ether poly(oxyethylene glycol)350 phthalimide.
The phthalimide group of the monomethyl ether poly(oxyethylene glycol)350 phthalimide compound is an example of a terminal functional group that may be conveniently converted into another group (such as an amino group, e.g. —NH2, when treated with a base) to confer to the resulting ligand the ability to bind to the surface of nanoparticles and/or the ability to modify the solubility of nanoparticles to which the ligand is bound.
Example 2
Synthesis of poly(oxyethylene glycol)350 monomethyl ether acetic acid
A solution of bromoacetic acid (162.83 g, 1.1719 moles) in tetrahydrofuran (500 mL) was added dropwise to a suspension of sodium hydride (93.744 g, 2.3436 moles) in tetrahydrofuran (500 mL) that was stirred and cooled (0° C.). Poly(oxyethylene glycol)350 monomethyl ether that had previously been dried (120° C., high vacuum, 1 hour) was dissolved in tetrahydrofuran (150 mL) and added dropwise to the reaction mixture. The reaction mixture was stirred while warming to room temperature overnight.
The reaction mixture was poured over ice, acidified (pH=1) and then concentrated under reduced pressure to give a white solid suspended in a yellow-colored oil. The oil was dissolved in CH2Cl2 (2.5 L) and the white solid was separated by filtration. The filtrate was washed with saturated NaHCO3 (5×50 mL) and then concentrated under reduced pressure to give a yellow-colored oil. The oil was dissolved in water (2 L) and washed with diethyl ether (5×50 mL). The aqueous phase (pH of approximately 3) was acidified with 1M HCl(aq) to pH of approximately 1 and washed with diethyl ether (50 mL). The aqueous phase was concentrated under reduced pressure to give a colorless oil (298.78 g).
Example 3
Capping of Quantum Dots
Representative quantum-dot materials compatible with embodiments disclosed herein include CdSe, GaAs, InAs, InP, CuInS2, CuInSe2, and CuIn1-xGaxSe2. Nanoparticle synthesis may be carried out using techniques described, for example, in U.S. Pat. No. 6,379,635 and co-pending U.S. patent application Ser. Nos. 11/579,050 and 11/588,880. The nanoparticles may be characterized by any conventional technique (e.g., XRD, UV/Vis/Near-IR spectrometry, SEM, TEM, EDAX, photoluminescence spectrometry, elemental analysis).
QDs may be capped with the ligands described above (e.g. poly(oxyethylene glycol)350 monomethyl ether acetic acid) using any one of a number of suitable methods known to the skilled person, which may optionally include ligand exchange and/or ligand interchelation methodologies.
The invention may be embodied in other specific forms without departing form the spirit or essential characteristics thereof. The foregoing embodiments are therefore to be considered in all respects illustrative rather than limiting on the invention described herein. Scope of the invention is thus indicated by the appended claims rather than by the foregoing description, and all changes that come within the meaning and range of equivalency of the claims are intended to be embraced therein.

## Claims

1. A method for producing capped nanoparticles comprising capping at least one nanoparticle with a compound of formula XO—(CH2CH2O)m—Y, wherein X is selected from the group consisting of H, CH3, and —CH2CO2H, Y is selected from the group consisting of p-toluene sulphonate, carboxyl, —CH2CO2H, -PhCO2H, —SiPh2tBu, phenyl, —CH2Ph and phthalamide, and m is an integer, and wherein the capping comprises exchanging at least some existing ligands coating the nanoparticle for the compound of formula XO—(CH2CH2)m—Y.

2. The method of claim 1, wherein m ranges from 8 to 45.

3. The method of claim 1, wherein the at least one nanoparticle comprises at least one semiconductor material.

4. The method of claim 3, wherein the semiconductor material is selected from one or more of the group of semiconductor materials consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, InP, InAs, InSb, AlP, Al2S3, AlAs, AISb, GaN, GaP, GaAs, GaSb, PbS, PbSe, Si, and Ge.

5. The method of claim 1, wherein the existing ligands are lipophilic surface binding ligands.

6. The method of claim 1, wherein the existing ligands are selected from the group consisting of myristic acid, hexadecylamine and trioctylphosphineoxide.

7. The method of claim 1, wherein the capping increases the stability of the nanoparticle in aqueous media.

8. A method for producing capped nanoparticles comprising capping at least one nanoparticle with a compound of formula XO—(CH2CH2O)m—Y wherein X is selected from the group consisting of H, CH3, and —CH2CO2H, Y is selected from the group consisting of p-toluene sulphonate, carboxyl, —CH2CO2H, -PhCO2H, —SiPh2tBu, phenyl, —CH2Ph and phthalamide, and m is an integer, wherein capping comprises interchelating the compound of formula XO—(CH2CH2O)m—Y into existing ligands coating the nanoparticle.

9. The method of claim 8, wherein the existing ligands are lipophilic surface binding ligands.

10. The method of claim 8, wherein the existing ligands are selected from the group consisting of myristic acid, hexadecylamine and trioctylphosphineoxide.

11. A method of producing capped nanoparticles, the method comprising: forming a compound of the formula


XO—(CH2CH2O)m—Y

wherein X is selected from the group consisting of H, CH3, and —CH2CO2H, Y is selected from the group consisting of p-toluene sulphonate, carboxyl, —CH2CO2H, -PhCO2H, —SiPh2tBu, phenyl, —CH2Ph and phthalamide and m is an integer, by:
providing a first starting material comprising poly(ethyleneglycol) and a terminal hydroxyl group;
reacting the first starting material with a second starting material comprising a leaving group and a functional group for chelating to the surface of a nanoparticle thereby detaching the leaving group and forming the compound; and
capping at least one nanoparticle with a compound of formula XO—(CH2CH2O)m—Y.

12. The method of claim 11, wherein the leaving group is p-toluene sulfonate.

13. Nanoparticles capped with a compound of formula


XO—(CH2CH2O)m—Y

wherein X is selected from the group consisting of H, CH3, and —CH2CO2H, Y is selected from the group consisting of p-toluene sulphonate, carboxyl, —CH2CO2H, -PhCO2H, —SiPh2tBu, phenyl, —CH2Ph and phthalamide and m is an integer, and wherein at least one of the nanoparticles comprises a semiconductor material selected from one or more of the group of semiconductor materials consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, InP, InAs, InSb, AlP, Al2S3, AlAs, AlSb, GaN, GaP, GaAs, GaSb, PbS, PbSe, Si, and Ge.