Source: https://patents.google.com/patent/US9534168B2/en
Timestamp: 2018-06-24 23:04:54
Document Index: 342940007

Matched Legal Cases: ['Application No. 60', 'Application No. 60', 'Application No. 60', 'Application No. 08', 'Application No. 08', 'Application No. 08', 'Application No. 2010', 'Application No. 2010', 'Application No. 10', 'Application No. 10']

US9534168B2 - Functionalized nanoparticles and method - Google Patents
US9534168B2
US9534168B2 US14500290 US201414500290A US9534168B2 US 9534168 B2 US9534168 B2 US 9534168B2 US 14500290 US14500290 US 14500290 US 201414500290 A US201414500290 A US 201414500290A US 9534168 B2 US9534168 B2 US 9534168B2
US14500290
US20150152324A1 (en )
A nanoparticle including an inorganic core comprising at least one metal and/or at least one semi-conductor compound comprising at least one metal includes a coating or shell disposed over at least a portion of a surface of the core. The coating can include one or more layers. Each layer of the coating can comprise a metal and/or at least one semiconductor compound. The nanoparticle further includes a ligand attached to a surface of the coating. The ligand is represented by the formula: X-Sp-Z, wherein X represents, e.g., a primary amine group, a secondary amine group, a urea, a thiourea, an imidizole group, an amide group, a phosphonic or arsonic acid group, a phosphinic or arsinic acid group, a phosphate or arsenate group, a phosphine or arsine oxide group; Sp represents a spacer group, such as a group capable of allowing a transfer of charge or an insulating group; and Z represents: (i) a reactive group capable of communicating specific chemical properties to the nanocrystal as well as provide specific chemical reactivity to the surface of the nanocrystal, and/or (ii) a group that is cyclic, halogenated, or polar a-protic. In certain embodiments, at least two chemically distinct ligands are attached to an surface of the coating, wherein the at least two ligands (I and II) are represented by the formula: X-Sp-Z. In ligand (I) X represents a phosphonic, phosphinic, or phosphategroup and in ligand (II) X represents a primary or secondary amine, or an imidizole, or an amide; In both ligands (I) and (II) Sp, which can be the same or different in the two compounds, represents a spacer group, such as a group capable of allowing a transfer of charge or an insulating group; Z, which can be the same or different in the two compounds, is a group chosen from among groups capable of communicating specific chemical properties to the nanoparticle as well as provide specific chemical reactivity to the surface of the nanoparticle. In preferred embodiments, the nanoparticle includes a core comprising a semiconductor material.
This application is a continuation of U.S. patent application Ser. No. 12/722,028 filed 11 Mar. 2010, which is a continuation of commonly owned International Application No. PCT/US2008/010651 filed 12 Sep. 2008, which was published in the English language as PCT Publication No. WO 2009/035657 on 19 Mar. 2009, which International application claims priority to U.S. Application Nos. 60/971,887, filed 12 Sep. 2007; 60/992,598, filed 5 Dec. 2007; and 61/083,998, filed 28 Jul. 2008; each of the foregoing hereby being incorporated herein by reference in its entirety.
International Application No. PCT/US2008/010651 further claims priority to U.S. Application Nos. 60/971,885, filed 12 Sep. 2007; 60/973,644, filed 19 Sep. 2007; and 61/016,227, filed 21 Dec. 2007. International Application No. PCT/US2008/010651 is also a continuation-in-part application of commonly owned International Application No. PCT/US2007/024750, filed 3 Dec. 2007. International Application No. PCT/US2008/010651 is also a continuation-in-part application of commonly owned International Application No. PCT/US2008/007902, filed 25 Jun. 2008. International Application No. PCT/US2008/010651 is also a continuation-in-part application of commonly owned International Application No. PCT/US2007/013152, filed 4 Jun. 2007, which was published in the English language as PCT Publication No. WO 2007/143197 on 13 Dec. 2007. PCT Application No. PCT/US2007/013152 claims priority from commonly owned U.S. patent application Nos. 60/810,767 filed 2 Jun. 2006, 60/810,914 filed 5 Jun. 2006, 60/804,921 filed 15 Jun. 2006, 60/825,373 filed 12 Sep. 2006, 60/825,374 filed 12 Sep. 2006, 60/825,370 filed 12 Sep. 2006, and 60/886,261 filed 23 Jan. 2007.
A predominant method for the synthesis of colloidal quantum dots involves reactions done in high boiling solvents, such as trioctylphosphine oxide (TOPO), trioctylphosphine (TOP), aliphatic phosphonic or carboxylic acids, and aliphatic amine species. The ligand capping groups on the surface of the quantum dots are, therefore, believed to be a statistical distribution of TOPO, TOP, acid, and amine. Throughout the quantum dot literature, in order to affect surface chemistry changes on a particular quantum dot sample (e.g. making water-soluble quantum dots), typical procedures involve cap exchange reactions, whereby already synthesized quantum dots (core or core-shell) are placed in a solution of another ligand and heated for an extended period of time in order to drive off the existing ligands and replace them with the alternate species. These procedures can be detrimental to maintaining the optical properties of the quantum dots and often result in drastically reduced emission efficiencies and stability.
Preferred ligands include benzylphosphonic acid, benzylphosphonic acid including at least one substituent group on the ring of the benzyl group, a conjugate base of such acids, and mixtures including one or more of the foregoing. In certain embodiments, a ligand comprises 4-hydroxybenzylphosphonic acid, a conjugate base of the acid, and a mixture of the foregoing. In certain embodiments, a ligand comprises 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, a conjugate base of the acid, or a mixture of the foregoing.
Preferred ligands include benzylphosphonic acid, benzylphosphonic acid including at least one substituent group on the ring of the benzyl group, a conjugate base of such acids, and mixtures including one or more of the foregoing. In certain embodiments, a ligand comprises 4-hydroxybenzylphosphonic acid, a conjugate base of the acid, and mixtures including one or more of the foregoing. In certain embodiments, a ligand comprises 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, a conjugate base of the acid, or a mixture of the foregoing.
In certain embodiments, a cyclic group can comprise a saturated or unsaturated cyclic (including, but not limited to, a single ring, a bicyclic structure, a multi-cyclic structure, etc.) compound or aromatic compound. In certain embodiments, the cyclic group can include at least one hetero-atom.
In certain embodiments, the cyclic group can include at least one substituent group (including, for example, but not limited to, a reactive chemical group, an organic group (alky, aryl, etc.), etc.). Other examples of cyclic groups are provided herein.
In certain embodiments, the predetermined composition of the coating material comprises a semiconductor material, preferably a nanocrystalline semiconductor material.
For a better understanding to the present, invention, together with other advantages and capabilities thereof, reference is made to the following disclosure and appended claims in connection with the above-described drawings.
Examples of reactive groups include, without limitation, functional, bifunctional, and polyfunctional reagents (e.g., homobifunctional or heterobifunctional), and reactive chemical groups (e.g., thiol, or carboxyl, hydroxyl, amino, amine, sulfo, and the like). Examples of additional reactive groups include carbodithioate, carbodithioic acid, thiourea, amide, phosphine oxide, phosphonic or phosphinic acid, thiophosphonic or thiophosphinic acid, which can be substituted with alkyl and/or aryl units that are perhalogenated or partially halogenated. Examples of cyclic groups include, but are not limited to, saturated or unsaturated cyclic or bicyclic compounds (e.g. cyclohexyl, isobornyl, etc.), or aromatic compounds (e.g. phenyl, benyl, naphthyl, biphenyl, fluorenyl, triarylamine, etc.). In certain embodiments, a cyclic group can include one or more substituent groups (including, for example, but not limited to, a reactive chemical group, an organic group (alky, aryl, etc.), etc.). Halogenated groups include, but are not limited to, fluorinated groups, perfluorinated groups, (e.g. perfluoroalkyl, perfluorophenyl, perfluoroamines, etc.), chlorinated groups, perchlorinated groups. Examples of polar a-protic groups include, but are not limited to, ketones, aldehydes, amides, ureas, urethanes, imines, etc.
In certain embodiments in which the method is carried out in a liquid medium, the mole ratio of total moles of the liquid medium to total moles of ligand represented by the formula X-Sp-Z is in the range from about 500:1 to about 2:1. In certain embodiments, the mole ratio of total moles of the liquid medium to total moles of ligand represented by the formula X-Sp-Z is in the range from about 100:1 to about 5:1. In certain embodiments, the mole ratio of total moles of the liquid medium to total moles of ligand represented by the formula X-Sp-Z is in the range from about 50:1 to about 5:1.
In accordance with certain embodiments, there is provided a method for functionalizing a nanoparticle. The method comprises reacting precursors for forming a nanoparticle having a predetermined composition in the presence of two or more chemically distinct ligands, at least one of said ligands being represented by the formula:
wherein R12 is an alkyl or alkylene group or an aryl or arylene group; R5 represents hydrogen, an alkyl group including one or more functional groups, an alkylene group, an aryl or arylene group, —OR13, —NHR13, —NR13R13, —SR13, wherein R13 represents hydrogen, an alkyl group, or an aryl group; R6 represents hydrogen; R7 represents hydrogen, an alkyl or alkylene group, an aryl or arylene group, —OR14, —NHR14, —NR14R14, —SR14, wherein R14 represents hydrogen, an alkyl group, or an aryl group; Re and R9, which can be the same or different, represent a bond, an alkylene group, an aryl or arylene group, a fluorocarbon group,
Functionalizing Surface of the Semiconductor Nanocrystal with Terminal Hydroxyl Groups.
Examples of Coupling Species to Hydroxy-Terminated Semiconductor Nanocrystals
wherein R1 represents a hydroxyl group; R2 represents hydrogen, an alkyl or alkylene group, an aryl or arylene group, —OR11, —NHR11, —NR11R11, —SR11, wherein R11 represents hydrogen, an alkyl group, or an aryl group; R3 and R4, which can be the same or different, represent a bond, an alkyl or alkylene group, an aryl or arylene group, a fluorocarbon group,
wherein R12 is an alkyl or alkylene group or an aryl or arylene group; R5 represents hydrogen, an alkyl group including one or more functional groups, an alkylene group, an aryl or arylene group, —OR13, —NHR13, —NR13R13, —SR13, wherein R13 represents hydrogen, an alkyl group, or an aryl group; R6 represents hydrogen; R7 represents hydrogen, an alkyl or alkylene group, an aryl or arylene group, —OR14, —NHR14, —NR14R14, —SR14, wherein R14 represents hydrogen, an alkyl group, or an aryl group; R8 and R9, which can be the same or different, represent a bond, an alkyl or alkylene group, an aryl or arylene group, a fluorocarbon group,
1 mmol cadmium acetate was dissolved in 8.96 mmol of tri-n-octylphosphine at 100° C. in a 20 mL vial and then dried and degassed for one hour. 15.5 mmol of trioctylphosphine oxide and 2 mmol of octadecylphosphonic acid were added to a 3-neck flask and dried and degassed at 140° C. for one hour. After degassing, the Cd solution was added to the oxide/acid flask and the mixture was heated to 270° C. under nitrogen. Once the temperature reached 270° C., 8 mmol of tri-n-butylphosphine was injected into the flask. The temperature was brought back to 270° C. where 1.1 mL of 1.5 M TBP-Se was then rapidly injected. The reaction mixture was heated at 270° C. for 15-30 minutes while aliquots of the solution were removed periodically in order to monitor the growth of the nanocrystals. Once the first absorption peak of the nanocrystals reached 565-575 nm, the reaction was stopped by cooling the mixture to room temperature. The CdSe cores were precipitated out of the growth solution inside a nitrogen atmosphere glovebox by adding a 3:1 mixture of methanol and isopropanol. The isolated cores were then dissolved in hexane and used to make core-shell materials.
25.86 mmol of trioctylphosphine oxide and 2.4 mmol of benzylphosphonic acid were loaded into a four-neck flask. The mixture was then dried and degassed in the reaction vessel by heating to 120° C. for about an hour. The flask was then cooled to 75° C. and the hexane solution containing isolated CdSe cores (0.1 mmol Cd content) was added to the reaction mixture. The hexane was removed under reduced pressure and then 2.4 mmol of phenylethylamine was added to the reaction mixture. Dimethyl cadmium, diethyl zinc, and hexamethyldisilathiane were used as the Cd, Zn, and S precursors, respectively. The Cd and Zn were mixed in equimolar ratios while the S was in two-fold excess relative to the Cd and Zn. The Cd/Zn and S samples were each dissolved in 4 mL of trioctylphosphine inside a nitrogen atmosphere glove box. Once the precursor solutions were prepared, the reaction flask was heated to 155° C. under nitrogen. The precursor solutions were added dropwise over the course of 2 hours at 155° C. using a syringe pump. After the shell growth, the nanocrystals were transferred to a nitrogen atmosphere glovebox and precipitated out of the growth solution by adding a 3:1 mixture of methanol and isopropanol. The isolated core-shell nanocrystals were then dissolved in toluene. The semiconductor nanocrystals had an emission maximum of 616 nm with a FWHM of 34 nm and a solution quantum yield of 50%.
Cleaned glass substrates were washed in a plasma preen and coated with PEDOT:PSS (70 nm). Substrates were taken into a nitrogen environment and baked at 120 C for 20 minutes. 50 nm E105 (N,N′-Bis(3-methylphenyl)-N,N′-bis-(phenyl)-9,9-spiro-bifluorene, LumTec) was evaporated in a vacuum chamber below 2e-6 Torr via thermal evaporation. Application of aromatic quantum dots was accomplished via contact printing. A dispersion of semiconductor nanocrystals with an optical density (OD) of 0.3 at the 1st absorption feature was spin-coated at 3000 rpm on a parylene coated stamp for 60 seconds, which was then stamped onto the E105 substrates depositing a mono-layer of aromatic quantum dots. Substrates were then taken back into the thermal evaporation chamber, and 5 nm and 15 nm, respectively, of CBP (4,4′-Bis(carbazol-9-yl)biphenyl, LumTec) were evaporated below 2e-6 Torr. FIGS. 2-5 depict images of the samples described in this Sample Fabrication example.
Example 1-B Preparation of Semiconductor Nanocrystals Capable of Emitting Green Light
Synthesis of ZnSe Cores:
0.69 mmol diethyl zinc was dissolved in 5 mL of tri-n-octylphosphine and mixed with 1 mL of 1 M TBP-Se. 28.9 mmol of Oleylamine was loaded into a 3-neck flask, dried and degassed at 90° C. for one hour. After degassing, the flask was heated to 310° C. under nitrogen. Once the temperature reached 310° C., the Zn solution was injected and the reaction mixture was heated at 270° C. for 15-30 minutes while aliquots of the solution were removed periodically in order to monitor the growth of the nanocrystals. Once the first absorption peak of the nanocrystals reached 350 nm, the reaction was stopped by dropping the flask temperature to 160° C. and used without further purification for preparation of CdZnSe cores.
Synthesis of CdZnSe Cores:
1.12 mmol dimethylcadmium was dissolved in 5 mL of tri-n-octylphosphine and mixed with 1 mL of 1 M TBP-Se. In a 4-neck flask, 41.38 mmol of trioctylphosphine oxide and 4 mmol of hexylphosphonic acid were loaded, dried and degassed at 120° C. for one hour. After degassing, the oxide/acid was heated to 160° C. under nitrogen and 8 ml of the ZnSe core growth solution was transferred at 160° C. into the flask, immediately followed by the addition of Cd/Se solution over the course of 20 minutes via syringe pump. The reaction mixture was then heated at 150° C. for 16-20 hours while aliquots of the solution were removed periodically in order to monitor the growth of the nanocrystals. Once the emission peak of the nanocrystals reached 500 nm, the reaction was stopped by cooling the mixture to room temperature. The CdZnSe cores were precipitated out of the growth solution inside a nitrogen atmosphere glovebox by adding a 2:1 mixture of methanol and n-butanol. The isolated cores were then dissolved in hexane and used to make core-shell materials.
Synthesis of CdZnSe/CdZnS Core-Shell Nanocrystals:
25.86 mmol of trioctylphosphine oxide and 2.4 mmol of benzylphosphonic acid were loaded into a four-neck flask. The mixture was then dried and degassed in the reaction vessel by heating to 120° C. for about an hour. The flask was then cooled to 75° C. and the hexane solution containing isolated CdZnSe cores (0.1 mmol Cd content) was added to the reaction mixture. The hexane was removed under reduced pressure. Dimethyl cadmium, diethyl zinc, and hexamethyldisilathiane were used as the Cd, Zn, and S precursors, respectively. The Cd and Zn were mixed in equimolar ratios while the S was in two-fold excess relative to the Cd and Zn. The Cd/Zn and S samples were each dissolved in 4 mL of trioctylphosphine inside a nitrogen atmosphere glove box. Once the precursor solutions were prepared, the reaction flask was heated to 150° C. under nitrogen. The precursor solutions were added dropwise over the course of 1 hour at 150° C. using a syringe pump. After the shell growth, the nanocrystals were transferred to a nitrogen atmosphere glovebox and precipitated out of the growth solution by adding a 3:1 mixture of methanol and isopropanol. The isolated core-shell nanocrystals were then dissolved in hexane and used to make semiconductor nanocrystal composite materials.
Example 1-C Preparation of Semiconductor Nanocrystals Capable of Emitting Red Light
25.86 mmol of trioctylphosphine oxide and 2.4 mmol of benzylphosphonic acid were loaded into a four-neck flask. The mixture was then dried and degassed in the reaction vessel by heating to 120° C. for about an hour. The flask was then cooled to 75° C. and the hexane solution containing isolated CdSe cores (0.1 mmol Cd content) was added to the reaction mixture. The hexane was removed under reduced pressure. Dimethyl cadmium, diethyl zinc, and hexamethyldisilathiane were used as the Cd, Zn, and S precursors, respectively. The Cd and Zn were mixed in equimolar ratios while the S was in two-fold excess relative to the Cd and Zn. The Cd/Zn and S samples were each dissolved in 4 mL of trioctylphosphine inside a nitrogen atmosphere glove box. Once the precursor solutions were prepared, the reaction flask was heated to 155° C. under nitrogen. The precursor solutions were added dropwise over the course of 2 hours at 155° C. using a syringe pump. After the shell growth, the nanocrystals were transferred to a nitrogen atmosphere glovebox and precipitated out of the growth solution by adding a 3:1 mixture of methanol and isopropanol. The isolated core-shell nanocrystals were then dissolved in toluene and used to make quantum dot composite materials.
Example 4 Preparation of Semiconductor Nanocrystals Capable of Emitting Red Light
25.86 mmol of trioctylphosphine oxide and 2.4 mmol of octadecylphosphonic acid were loaded into a four-neck flask. The mixture was then dried and degassed in the reaction vessel by heating to 120° C. for about an hour. The flask was then cooled to 75° C. and the hexane solution containing isolated CdSe cores (0.1 mmol Cd content) was added to the reaction mixture. The hexane was removed under reduced pressure and then 2.4 mmol of 6-amino-1-hexanol was added to the reaction mixture. Dimethyl cadmium, diethyl zinc, and hexamethyldisilathiane were used as the Cd, Zn, and S precursors, respectively. The Cd and Zn were mixed in equimolar ratios while the S was in two-fold excess relative to the Cd and Zn. The Cd/Zn and S samples were each dissolved in 4 mL of trioctylphosphine inside a nitrogen atmosphere glove box. Once the precursor solutions were prepared, the reaction flask was heated to 155° C. under nitrogen. The precursor solutions were added dropwise over the course of 2 hours at 155° C. using a syringe pump. After the shell growth, the nanocrystals were transferred to a nitrogen atmosphere glovebox and precipitated out of the growth solution by adding a 3:1 mixture of methanol and isopropanol. The isolated core-shell nanocrystals were then dissolved in hexane.
Color/Batch # Emis- tion
(Nanocrystal Sol- sion QY
Prep. Example #) vent Ligand(s) (nm) FWHM (%)
(Ex. 4) amino-1-hexanol
1H-NMR (CDCl3): δ 7.066 (d, Ar—H, 2H, JP-H=2.8 Hz), 5.145 (s, 1H, —OH), 4.06-3.92 (m, —CH2CH3, 4H, H—H and long-range P—H couplings), 3.057 (d, Ar—CH 2, 2H, JP-H=21.0 Hz), 1.412 (s, —C(CH 3)3, 18H), 1.222 (t, —CH2CH 3, 6H).
13C-NMR (CDCl3): δ 153.98 (aromatic), 136.22 (aromatic), 126.61 (aromatic), 122.07 (aromatic), 62.14 (—OCH2CH3, JP-C=24.4 Hz), 33.63 (Ar—CH2, JP-C=552.4 Hz), 34.53 [—C(CH3)3], 30.54 [—C(CH3)3], 16.66 (—CH2 CH3, JP-C=24.4 Hz).
37 ml of RD-12, a low viscosity reactive diluent commercially available from Radcure Corp, 9 Audrey Pl, Fairfield, N.J. 07004-3401, United States, is added to 4.68 gram of semiconductor nanocrystals under vacuum. The vessel is then backfilled with nitrogen and the mixture is mixed using a vortex mixer. After the semiconductor nanocrystals are pre-solubilized in the reactive diluent, 156 ml of DR-150, an UV-curable acrylic formulation commercially available Radcure, is added slowly under vacuum. The vessel is then backfilled with nitrogen and the mixture is mixed using a vortex mixer.
Thickness = 72 μm FWHM = 36 nm
Lambda em = 633.1 nm % A450 nm = 82.6%
% EQE = 50.0%
Red/Sample #2 Chloroform BHT 633 36 50.0
Also refer to The Chemistry of Organophosphorus Compounds. Volume 4: Ter- and Quinque-Valent Phosphorus Acids and Their Derivatives, Frank R. Hartley (Editor), April 1996 for more general synthetic procedures for generating phosphonic acid derivatives.
25.86 mmol of trioctylphosphine oxide and 2.4 mmol of octadecylphosphonic acid were loaded into a four-neck flask. The mixture was then dried and degassed in the reaction vessel by heating to 120° C. for about an hour. The flask was then cooled to 75° C. and the hexane solution containing isolated CdSe cores (0.1 mmol Cd content) was added to the reaction mixture. The hexane was removed under reduced pressure and then 2.4 mmol of 6-amino-1-hexanol was added to the reaction mixture. Dimethyl cadmium, diethyl zinc, and hexamethyldisilathiane were used as the Cd, Zn, and S precursors, respectively. The Cd and Zn were mixed in equimolar ratios while the S was in two-fold excess relative to the Cd and Zn. The Cd/Zn and S samples were each dissolved in 4 mL of trioctylphosphine inside a nitrogen atmosphere glove box. Once the precursor solutions were prepared, the reaction flask was heated to 155° C. under nitrogen. The precursor solutions were added dropwise over the course of 2 hours at 155° C. using a syringe pump. After the shell growth, the nanocrystals were transferred to a nitrogen atmosphere glovebox and precipitated out of the growth solution by adding a 3:1 mixture of methanol and isopropanol. The isolated core-shell nanocrystals were then dissolved in hexane and their solution-state quantum yield assessed. (QY˜80%)
25.86 mmol of trioctylphosphine oxide and 2.4 mmol of octadecylphosphonic acid were loaded into a four-neck flask. The mixture was then dried and degassed in the reaction vessel by heating to 120° C. for about an hour. The flask was then cooled to 75° C. and the hexane solution containing isolated CdSe cores (0.1 mmol Cd content) was added to the reaction mixture. The hexane was removed under reduced pressure and then 2.4 mmol of decylamine was added to the reaction mixture. Dimethyl cadmium, diethyl zinc, and hexamethyldisilathiane were used as the Cd, Zn, and S precursors, respectively. The Cd and Zn were mixed in equimolar ratios while the S was in two-fold excess relative to the Cd and Zn. The Cd/Zn and S samples were each dissolved in 4 mL of trioctylphosphine inside a nitrogen atmosphere glove box. Once the precursor solutions were prepared, the reaction flask was heated to 155° C. under nitrogen. The precursor solutions were added dropwise over the course of 2 hours at 155° C. using a syringe pump. After the shell growth, the nanocrystals were transferred to a nitrogen atmosphere glovebox and precipitated out of the growth solution by adding a 3:1 mixture of methanol and isopropanol. The isolated core-shell nanocrystals were then dissolved in hexane and used for cap exchange reactions. (QY˜80%)
Cap-Exchange Reaction (1) on CdSe/CdZnS Core-Shell Nanocrystals:
10 mL of toluene and 42.6 mmol of 6-amino-1-hexanol were loaded into a four-neck flask. The flask was evacuated and refilled with nitrogen three times. The flask was then heated to 40° C. and the hexane solution containing isolated CdSe/CdZnS core/shell (1 prep) was added to the reaction mixture. The mixture was heated at 40° C. overnight. Finally, the cap-exchanged semiconductor nanocrystals were precipitated out of the growth solution by adding hexane. The isolated core-shell nanocrystals were then dissolved in a 3:1 methanol and isopropanol mixture and their solution-state quantum yield assessed. (QY˜15%)
Cap-Exchange Reaction (2) on CdSe/CdZnS Core-Shell Nanocrystals:
25.86 mmol of trioctylphosphine oxide, 2.4 mmol of octadecylphosphonic acid, and 2.4 mmol of 6-amino-1-hexanol were loaded into a four-neck flask. The mixture was then dried and degassed in the reaction vessel by heating to 120° C. for about an hour. The flask was then cooled to 40° C. and the hexane solution containing isolated CdSe/CdZnS core/shell (1 prep) was added to the reaction mixture. The mixture was heated at 40° C. overnight. Finally, the cap-exchanged semiconductor nanocrystals were precipitated out of the growth solution by adding a 3:1 mixture of methanol and isopropanol. The isolated core-shell nanocrystals were then dissolved in hexane and their solution-state quantum yield assessed. (QY˜19%)
In certain embodiments, nanoparticles comprise chemically synthesized colloidal nanoparticles (nanoparticles), such as semiconductor nanocrystals or quantum dots. In certain preferred embodiments, the nanoparticles (e.g., semiconductor nanocrystals) have a diameter in a range from about 1 to about 10 nm. In certain embodiments, at least a portion of the nanoparticles, and preferably all of the nanoparticles, include one or more ligands attached to a surface of a nanoparticle. See, C. B. Murray et al., Annu. Rev. Mat. Sci., 30, 545-610 (2000), which is incorporated in its entirety. These zero-dimensional structures show strong quantum confinement effects that can be harnessed in designing bottom-up chemical approaches to create complex heterostructures with electronic and optical properties that are tunable with the size of the nanocrystals.
Semiconductor nanocrystals can have high emission quantum efficiencies such as greater than 10%, 20%, 30%, 40%, 50%, 60%, 70%, or 80%. The semiconductor forming the nanocrystals can include Group IV elements, Group II-VI compounds, Group II-V compounds, Group III-VI compounds, Group III-V compounds, Group IV-VI compounds, Group I-III-VI compounds, Group II-IV-VI compounds, or Group II-IV-V compounds, for example, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, GaSe, InN, InP, InAs, InSb, TlN, TIP, TIAs, TISb, PbS, PbSe, PbTe, or mixtures thereof.
The M donor can be an inorganic compound, an organometallic compound, or elemental metal. For example, M can be cadmium, zinc, magnesium, mercury, aluminum, gallium, indium or thallium. The X donor is a compound capable of reacting with the M donor to form a material with the general formula MX. Typically, the X donor is a chalcogenide donor or a pnictide donor, such as a phosphine chalcogenide, a bis(silyl) chalcogenide, dioxygen, an ammonium salt, or a tris(silyl) pnictide. Suitable X donors include dioxygen, bis(trimethylsilyl) selenide ((TMS)2Se), trialkyl phosphine selenides such as (tri-n-octylphosphine) selenide (TOPSe) or (tri-n-butylphosphine) selenide (TBPSe), trialkyl phosphine tellurides such as (tri-n-octylphosphine) telluride (TOPTe) or hexapropylphosphorustriamide telluride (HPPTTe), bis(trimethylsilyl)telluride ((TMS)2Te), bis(trimethylsilyl)sulfide ((TMS)2S), a trialkyl phosphine sulfide such as (tri-n-octylphosphine) sulfide (TOPS), an ammonium salt such as an ammonium halide (e.g., NH4Cl), tris(trimethylsilyl)phosphide ((TMS)3P), tris(trimethylsilyl) arsenide ((TMS)3As), or tris(trimethylsilyl) antimonide ((TMS)3Sb). In certain embodiments, the M donor and the X donor can be moieties within the same molecule.
A coordinating solvent can help control the growth of nanocrystals. The coordinating solvent is a compound having a donor lone pair that, for example, has a lone electron pair available to coordinate to a surface of the growing nanocrystal. Solvent coordination can stabilize the growing nanocrystal. Typical coordinating solvents include alkyl phosphines, alkyl phosphine oxides, alkyl phosphonic acids, or alkyl phosphinic acids, however, other coordinating solvents, such as pyridines, furans, and amines may also be suitable for the nanocrystal production. Examples of suitable coordinating solvents include pyridine, tri-n-octyl phosphine (TOP), tri-n-octyl phosphine oxide (TOPO) and tris-hydroxylpropylphosphine (tHPP). Technical grade TOPO can be used.
Semiconductor nanocrystals include, for example, inorganic crystallites between about 1 nm and about 1000 nm in diameter, preferably between about 2 nm and about 50 um, more preferably about 1 nm to about 20 nm (such as about 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 nm).
The core can have an overcoating on a surface of the core. The overcoating can be a semiconductor material having a composition different from the composition of the core. The overcoat of a semiconductor material on a surface of the nanocrystal can include a Group II-VI compound, Group II-V compound, Group III-VI compound, Group III-V compound, Group IV-VI compound, Group I-III-VI compound, Group II-IV-VI compound, and Group II-IV-V compound, for example, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, GaSe, InN, InP, InAs, InSb, TlN, TIP, TIAs, TISb, PbS, PbSe, PbTe, or mixtures thereof. In certain embodiments, a nanocrystal can comprise a Group IV element.
Narrow FWHM of nanocrystals can result in saturated color emission. This can lead to efficient nanocrystal-light emitting devices even in the red and blue parts of the spectrum, since in nanocrystal emitting devices no photons are lost to infrared and UV emission. The broadly tunable, saturated color emission over the entire visible spectrum of a single material system is unmatched by any class of organic chromophores. Furthermore, environmental stability of covalently bonded inorganic nanocrystals suggests that device lifetimes of hybrid organic/inorganic light emitting devices should match or exceed that of all-organic light emitting devices, when nanocrystals are used as luminescent centers. The degeneracy of the band edge energy levels of nanocrystals facilitates capture and radiative recombination of all possible excitons, whether generated by direct charge injection or energy transfer. The maximum theoretical nanocrystal-light emitting device efficiencies are therefore comparable to the unity efficiency of phosphorescent organic light emitting devices. The nanocrystal's excited state lifetime (τ) is much shorter (τ˜10 ns) than a typical phosphor (τ>0.5 μs), enabling nanocrystal-light emitting devices to operate efficiently even at high current density.
Semiconductor nanocrystals in accordance with the present inventions can be included in photoluminescent applications including, but not limited to, those described in U.S. Application No. 60/971,885, of Coe-Sullivan, et al., entitled “Optical Component, System Including An Optical Component, Devices, And Composition”, filed 12 Sep. 2007, and U.S. Application No. 60/973,644, entitled “Optical Component, System Including An Optical Component, Devices, And Composition”, of Coe-Sullivan, et al., filed 19 Sep. 2007, each of which is hereby incorporated herein by reference in its entirety.
Other materials, techniques, methods, applications, and information that may be useful with the present invention are described in International Patent Application No. PCT/US2007/24750, entitled “Improved Composites And Devices Including Nanoparticles”, of Coe-Sullivan, et al, filed 3 Dec. 2007, and U.S. Application No. 60/971,887, entitled “Functionalized Semiconductor Nanocrystals And Method”, of Breen, et al., filed 12 Sep. 2007; and International Application No. PCT/US2007/014711, entitled “Methods For Depositing Nanomaterial, Methods For Fabricating A Device, And Methods For Fabricating An Array Of Devices”, of QD Vision, Inc. et al., filed 25 Jun. 2007; each of the foregoing being hereby incorporated herein by reference in its entirety.
wherein X represents a secondary amine group; Sp represents a spacer group, such as a group capable of allowing a transfer of charge or an insulating group; and Z represents: (i) a reactive group capable of communicating specific chemical properties to the nanoparticle as well as provide specific chemical reactivity to the surface of the nanoparticle, and/or (ii) a group that is cyclic, halogenated, and/or polar a-protic, wherein Z in all cases is not reactive upon exposure to light, and wherein a native ligand is a ligand that attaches or coordinates to the nanoparticle surface during the growth thereof or overcoating thereof with an overcoating material comprising a semiconductor material.
15. A nanoparticle in accordance with claim 1 wherein the ligand represented by the formula X-Sp-Z comprises an organic amine including a terminal hydroxyl group or a fluorinated organic amine.
16. A nanoparticle in accordance with claim 1 wherein the nanoparticle includes two or more chemically distinct native ligands attached to a surface thereof, at least one of said ligands being represented by the formula:
17. A nanoparticle in accordance with claim 1 wherein the nanoparticle has higher quantum yield than if the same ligand was attached to the nanoparticle by a ligand exchange process.
18. A nanoparticle in accordance with claim 9 wherein the nanoparticle includes two or more chemically distinct native ligands attached to a surface thereof, at least one of said ligands being represented by the formula:
19. A nanoparticle in accordance with claim 9 wherein the ligand represented by the formula X-Sp-Z comprises an organic amine including a terminal hydroxyl group or a fluorinated organic amine.
20. A nanoparticle in accordance with claim 1 wherein Sp comprises a straight or branched C1-C18 hydrocarbon chain.
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