Continuous flow reactor for the synthesis of nanoparticles

Abstract

A continuous flow reactor for the efficient synthesis of nanoparticles with a high degree of crystallinity, uniform particle size, and homogenous stoichiometry throughout the crystal is described. Disclosed embodiments include a flow reactor with an energy source for rapid nucleation of the procurors following precursors to form nucleates followed by a separate heating source for growing the nucleates. Segmented flow may be provided to facilitate mixing and uniform energy absorption of the precursors, and post production quality testing in communication with a control system allow automatic real-time adjustment of the production parameters. The nucleation energy source can be monomodal, multimodal, or multivariable frequency microwave energy and tuned to allow different precursors to nucleate at substantially the same time thereby resulting in a substantially homogenous nanoparticle. A shell application system may also be provided to allow one or more shell layers to be formed onto each nanoparticle.

We claim: 
     
       1. A method for producing uniformly sized quantum dot nanoparticles comprising:
 blending at least a first precursor and at least a second precursor together to form a liquid precursor mixture; 
 conducting the liquid precursor mixture along a continuous flow path comprising one or more tubes through which the liquid precursor mixture flows, wherein at least one of the one or more tubes comprises an inner diameter of ¼ inch to ½ inch; 
 introducing gas into the continuous flow path fluidically so as to form partitions of the gas in the continuous flow path; 
 after introducing the gas into the continuous flow path, activating the liquid precursor mixture with one or more of multimodal and multivariable frequency microwave energy from a microwave energy source along the continuous flow path for a first duration at a first energy level thereby allowing uniform nucleation of quantum dot nucleates in the mixture of precursors; 
 heating the liquid precursor mixture with a heating source along the continuous flow path for a second duration at a controlled temperature, thereby promoting uniform thermodynamic growth around previously formed the quantum dot nucleates previously formed to form desired core sized nanoparticles core quantum dot nanoparticles, wherein the core quantum dot nanoparticles fluoresce with a full width half max (FWHM) of less than 50 nm at wavelengths from 400 nm-700 nm; and 
 quenching the growth of the quantum dot nanoparticles after heating. 
 
     
     
       2. The method of  claim 1 , wherein the microwave energy is multimodal. 
     
     
       3. The method of  claim 1 , wherein the microwave energy is multivariable in frequency. 
     
     
       4. The method of  claim 1 , further comprising introducing gas into the continuous flow path fluidically upstream of the microwave energy source, so as to form partitions of wherein the gas in the is introduced into multiple lines, which separate adjacent segments of the liquid precursor mixture of the continuous flow path. 
     
     
       5. The method of  claim 4 , wherein the gas includes one or more of nitrogen and argon. 
     
     
       6. The method of  claim 1 , wherein the first duration is less than or equal to 60 seconds. 
     
     
       7. The method of  claim 1 , wherein the first duration is less than or equal to 10 seconds. 
     
     
       8. The method of  claim 1 , wherein the first duration is less than or equal to 3 seconds. 
     
     
       9. The method of  claim 1 , wherein the first duration is less than or equal to 2 seconds. 
     
     
       10. The method of  claim 1 , further comprising monitoring a quality of the quantum dot nanoparticles via one or more sensors; and adjusting the first duration, first energy level, second duration, and temperature, via one or more actuators, in response to the detected quality of the quantum dot nanoparticles. 
     
     
       11. The method of  claim 1 , wherein a mixture of two or more precursors from Groups B or C herein, having different microwave absorption cross sections, nucleate with a precursor from Group A herein, at substantially equal rates upon flowing through the microwave energy source,
 wherein Group A includes H 2 X where X=O, S, Se, Te; R 3 PX where R=H, (CH 2 ) n CH 3 , C 6 H 5 , C 6 H 4 R′, n=3-18, R′=(CH 2 ) m CH 3 , CH(CH 3 ) 2 , C(CH 3 ) 3 , m=0-17, X=Se, Te; R 3 NX where R=H, (CH 2 ) n CH 3 , Si(CH 3 ) 3 , n=0-4, X=S, Se, Te; ((CH 3 ) 3 Si) 2 X where X=S, Se, Te; HX(CH 2 ) n CH 3  where X=O, S, Se, Te, n=1-18; HO(CH 2 )(CH(OH)) n (CH 3 ) where n=1-50; HO(CH 2 )(CH(OH)) n (CH 2 OH) where n=1-50; H 2 NNH 2 ; NaBH 4 , NaCNBH 3 ; and mixtures thereof including anionic precursors and/or reducing agents, 
 wherein Group B includes ML y  where M=Tl, Ag, Cu when y=1, M=Zn, Cd, Hg, Cu, Pb, Ni when y=2, M=Al, Ga, B, In, Bi, Fe when y=3, L=O 2  C(CH 2 ) n CH 3 , O 2 C(CH 2 ) m CHCH(CH 2 )OCH 3 ) O 2 C(CH 2 ) m CH═CH(CH 2 ) o CH 3 , S(CH 2 ) n CH 3 , PR 3 , OPR 3 , n=2-24, m and o=1-15, R=(CH 2 ) p CH 3 , C 6 H 5 , C 6 H 4 R′, p=0-18, R′=(CH 2 ) p CH 3 , CH(CH 3 ) 2 , C(CH 3 ) 3 ; and mixtures thereof, and 
 wherein Group C includes: ML y  where M=Na, K, Rb, Cs, Ag, Cu when y=1, M=Mg, Ca, Sr, Ba, Pd, Pt, Cu, Ni when y=2, M=La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Au when y=3, M=Ti, Zr, Hf, Pt, Pd when y=4, L=O 2 CCH 3 , Cl, F, NO 3 ; and mixtures thereof. 
 
     
     
       12. The method of  claim 1 , wherein nucleation of the first and second precursors over the first duration results in a substantially homogeneous quantum dot nanoparticle. 
     
     
       13. The method of  claim 1 , further comprising:
 using a continuous-flow process to expose the quantum dot nanoparticles to a mixture of at least a third precursor from Group A herein and a fourth precursor from Group B or Group C herein; and 
 heating the exposed quantum dot nanoparticles in a heat source to form a first shell around the quantum dot nanoparticle, 
 wherein Group A includes: H 2 X where X=O, S, Se, Te; R 3 PX where R=H, (CH 2 ) n CH 3 , C 6 H 5 , C 6 H 4 R′, n=3-18, R′=(CH 2 ) m CH 3 , CH(CH 3 ) 2 , C(CH 3 ) 3 , m=0-17, X=Se, Te; R 3 NX where R=H, (CH 2 ) n CH 3 , Si(CH 3 ) 3 , n=0-4, X=S, Se, Te; ((CH 3 ) 3 Si) 2 X where X=S, Se, Te; HX(CH 2 ) n CH 3  where X=O, S, Se, Te, n=1-18; HO(CH 2 )(CH(OH)) n (CH 3 ) where n=1-50; HO(CH 2 )(CH(OH)) n (CH 2 OH) where n=1-50; H 2 NNH 2 ; NaBH 4 , NaCNBH 3 ; and mixtures thereof including anionic precursors and/or reducing agents, 
 wherein Group B includes: ML y  where M=Tl, Ag, Cu when y=1, M=Zn, Cd, Hg, Cu, Pb, Ni when y=2, M=Al, Ga, B, In, Bi, Fe when y=3, L=O 2 C(CH) n CH 3 , O 2 C(CH 2 ) m CHCH(CH 2 )OCH 3 ) O 2 C(CH 2 ) m CH═CH(CH 2 ) o CH 3 , S(CH 2 ) n CH 3 , PR 3 , OPR 3 , n=2-24, m and o=1-15, R=(CH 2 ) n CH 3 , C 6 H 5 , C 6 H 4 R′, p=0-18, R′=(CH 2 ) p CH 3 , CH(CH 3 ) 2 , C(CH 3 ) 3 ; and mixtures thereof, and 
 wherein Group C includes: ML y  where M=Na, K, Rb, Cs, Ag, Cu when y=1, M=Mg, Ca, Sr, Ba, Pd, Pt, Cu, Ni when y=2, M=La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Au when y=3, M=Ti, Zr, Hf, Pt, Pd when y=4, L=O 2 CCH 3 , Cl, F, NO 3 ; and mixtures thereof. 
 
     
     
       14. The method of  claim 13 , further comprising:
 using a continuous-flow process to expose the quantum dot nanoparticles to a mixture of a fifth precursor and a sixth precursor; and 
 heating the exposed quantum dot nanoparticle to form a second shell around the first shell. 
 
     
     
       15. The method of  claim 13 , further comprising: using a continuous-flow process to expose the quantum dot nanoparticles to a mixture of a fifth precursor to from Group A herein and a sixth precursor from Group B or Group C herein; and
 heating the exposed quantum dot nanoparticle to form a second shell around the first shell, 
 wherein Group A includes: H 2 X where X=O, S, Se, Te; R 3 PX where R=H, (CH 2 ) n CH 3 , C 6 H 5 , C 6 H 4 R′, n=3-18, R′=(CH 2 ) m CH 3 , CH(CH 3 ) 2 , C(CH 3 ) 3 , m=0-17, X=Se, Te; R 3 NX where R=H, (CH 2 ) n CH 3 , Si(CH 3 ) 3 , n=0-4, X=S, Se, Te; ((CH 3 ) 3 Si) 2 X where X=S, Se, Te; HX(CH 2 ) n CH 3  where X=O, S, Se, Te, n=1-18; HO(CH 2 )(CH(OH)) n (CH 3 ) where n=1-50; HO(CH 2 )(CH(OH)) n (CH 2 OH) where n=1-50; H 2 NNH 2 ; NaBH 4 , NaCNBH 3 ; and mixtures thereof including anionic precursors and/or reducing agents, 
 wherein Group B includes: ML y  where M=Tl, Ag, Cu when y=1, M=Zn, Cd, Hg, Cu, Pb, Ni when y=2, M=Al, Ga, B, In, Bi, Fe when y=3, L=O 2 C(CH 2 ) n CH 3 , O 2 C(CH 2 ) m CHCH(CH 2 )OCH 3 ) O 2 C(CH 2 ) m CH═CH(CH 2 ) o CH 3 , S(CH 2 )CH 3 , PR 3 , OPR 3 , n=2-24, m and o=1-15, R=(CH 2 ) p CH 3 , C 6 H 5 , C 6 H 4 R′, p=0-18, R′=(CH 2 ) p CH 3 , CH(CH 3 ) 2 , C(CH 3 ) 3 ; and mixtures thereof, and 
 wherein Group C includes: ML y  where M=Na, K, Rb, Cs, Ag, Cu when y=1, M=Mg, Ca, Sr, Ba, Pd, Pt, Cu, Ni when y=2, M=La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Au when y=3, M=Ti, Zr, Hf, Pt, Pd when y=4, L=O 2 CCH 3 , Cl, F, NO 3 ; and mixtures thereof. 
 
     
     
       16. The method of  claim 15 , further comprising:
 using a continuous-flow process to expose the quantum dot nanoparticles to a mixture of a seventh precursor from Group A herein and a an eighth precursor from Group B or Group C herein; and 
 heating the exposed quantum dot nanoparticle to form a third shell around the second shell. 
 
     
     
       17. The method of  claim 4 , further including the step of separating the gas from the quantum dot nanoparticles following the step of quenching the growth of the quantum dot nanoparticle. 
     
     
       18. The method of  claim 1 , wherein the continuous flow path comprises multiple lines, and wherein one or more of the multiple lines comprises an inner diameter between 1/16 of an inch and 1 inch. 
     
     
       19. The method of  claim 18 , wherein one or more of the multiple lines has an inner diameter between ¼ and ½ inch. 
     
     
       20. The nanoparticle method of  claim 1 , wherein the microwave energy operates at frequencies that cause the first and second precursors to nucleate at substantially the same time thereby producing substantially homogenous quantum dot nanoparticles. 
     
     
       21. A method for producing uniformly sized quantum dot nanoparticles comprising:
 blending together a first and second precursor to form a liquid precursor mixture; 
 conducting the liquid precursor mixture along multiple lines of a continuous flow path comprising one or more tubes through which the liquid precursor mixture flows, wherein at least one tube of the one or more tubes comprises an inner diameter of ¼ inch to ½ inch; 
 introducing gas into the continuous flow path fluidically upstream of the microwave energy source, so as to form partitions of the gas in the multiple lines, which separate adjacent segments of the liquid precursor mixture; 
 activating the liquid precursor mixture with multimodal and/or multivariable frequency microwave energy from a microwave energy source in the continuous flow path, the microwave energy source configured to uniformly irradiate the multiple lines and thereby uniformly nucleate the liquid precursor mixture, for a first duration at a first energy level, to form quantum dot nucleates; 
 heating the activated liquid precursor mixture with a heating source in the continuous flow path for a second duration at a controlled temperature, thereby promoting uniform thermodynamic growth around previously formed the quantum dot nucleates previously formed to form desired core sized nanoparticles core quantum dot nanoparticles, wherein the core quantum dot nanoparticles fluoresce with a full width half max (FWHM) of less than 50 nm at wavelengths from 400 nm-700 nm; and 
 quenching the growth of the quantum dot nanoparticles after heating. 
 
     
     
       22. The method of  claim 21 , wherein first duration is less than or equal to 10 seconds. 
     
     
       23. The method of  claim 21 , wherein the first duration is less than or equal to 3 seconds. 
     
     
       24. The method of  claim 21 , wherein the first duration is less than or equal to 2 seconds. 
     
     
       25. The method of  claim 21 , wherein the microwave energy is multimodal. 
     
     
       26. The method of  claim 21 , the microwave energy is of multivariable frequency. 
     
     
       27. The method of  claim 21 , wherein the gas includes one or more of nitrogen and argon. 
     
     
       28. The method of  claim 21 , further comprising monitoring a quality of the quantum dot nanoparticles via one or more sensors; and adjusting the first duration, first energy level, second duration, and temperature, via one or more actuators, in response to the detected quality of the quantum dot nanoparticles. 
     
     
       29. The method of  claim 21 , wherein a mixture of two or more precursors from Groups B or C herein, having different microwave absorption cross sections, nucleate with a precursor from Group A herein, at substantially equal rates upon flowing through the first energy source,
 wherein Group A includes: H 2 X where X=O, S, Se, Te; R 3 PX where R=H, (CH 2 ) n CH 3 , C 6 H 5 , C 6 H 4 R′, n=3-18, R′=(CH 2 ) m CH 3 , CH(CH 3 ) 2 , C(CH 3 ) 3 , m=0-17, X=Se, Te; R 3 NX where R=H, (CH 2 ) n CH 3 , Si(CH 3 ) 3 , n=0-4, X=S, Se, Te; ((CH 3 ) 3 Si) 2 X where X=S, Se, Te; HX(CH 2 ) n CH 3  where X=O, S, Se, Te, n=1-18; HO(CH 2 )(CH(OH)) n (CH 3 ) where n=1-50; HO(CH 2 )(CH(OH)) n (CH 2 OH) where n=1-50; H 2 NNH 2 ; NaBH 4 , NaCNBH 3 ; and mixtures thereof including anionic precursors and/or reducing agents, 
 wherein Group B includes: ML y  where M=Tl, Ag, Cu when y=1, M=Zn, Cd, Hg, Cu, Pb, Ni when y=2, M=Al, Ga, B, In, Bi, Fe when y=3, L=O 2 C(CH 2 ) n CH 3 , O 2 C(CH 2 ) m CHCH(CH 2 )OCH 3 )OCH 3 ) O 2 C(CH 2 ) m CH═CH(CH 2 ) o CH 3 , S(CH 2 ) n CH 3 , PR 3 , OPR 3 , n=2-24, m and o=1-15, R=(CH 2 ) p CH 3 , C 6 H 5 , C 6 H 4 R′, p=0-18, R′=(CH 2 ) p CH 3 , CH(CH 3 ) 2 , C(CH 3 ) 3 ; and mixtures thereof, and 
 wherein Group C includes: ML y  where M=Na, K, Rb, Cs, Ag, Cu when y=1, M=Mg, Ca, Sr, Ba, Pd, Pt, Cu, Ni when y=2, M=La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Au when y=3, M=Ti, Zr, Hf, Pt, Pd when y=4, L=O 2 CCH 3 , Cl, F, NO 3 ; and mixtures thereof. 
 
     
     
       30. The method of  claim 29 , wherein the nucleation of the first and second precursors over the first duration results in substantially homogeneous quantum dot nanoparticles. 
     
     
       31. The method of  claim 1  wherein the first and second precursors are blended prior to conduction along the continuous flow path. 
     
     
       32. The method of  claim 1  wherein the first and second precursors are blended during conduction along the continuous flow path. 
     
     
       33. The method of  claim 4 , wherein the continuous flow path comprises at least one line having an inner diameter between 1/16 of an inch and 1 inch two or more lines of the multiple lines have an inner diameter of ¼ inch to ½ inch. 
     
     
       34. The method of  claim 33 , wherein the at least one line has an inner diameter between ¼ and ½ inch. 
     
     
       35. The method of claim 1, wherein the continuous flow path comprises multiple flow cell tubes that pass through a same microwave reactor cavity. 
     
     
       36. The method of claim 1, wherein the multivariable frequency microwave energy is tuned to a first frequency for the first precursor and is tuned to a second frequency for the second precursor.