Abstract:
High quantum yield InP nanocrystals are used in the bio-technology, bio-medical, and photovoltaic, specifically IV, III-V and III-VI nanocrystal technological applications. InP nanocrystals typically require post-generation HF treatment. Combining microwave methodologies with the presence of a fluorinated ionic liquid allows Fluorine ion etching without the hazards accompanying HF. Growing the InP nanocrystals in the presence of the ionic liquid allows in-situ etching to be achieved. The optimization of the PL QY is achieved by balancing growth and etching rates in the reaction.

Description:
CROSS REFERENCE TO RELATED APPLICATION 
     This application is a continuation of U.S. application Ser. No. 12/201,589, entitled “Ion Etching of Growing InP Nanocrystals using Microwave”, filed Aug. 29, 2008, which claims priority to U.S. Provisional Patent Application No. 61/079,478, entitled “Microwave Etching of Semiconductor Nanoparticles”, filed on Jul. 10, 2008, the contents of which are herein incorporated by reference. 
    
    
     STATEMENT OF GOVERNMENT INTEREST 
     This invention was made with Government support under Grant No. EB-R01-00832 awarded by the National Institutes of Health and Grant No. DMR-0701462 awarded by the National Science Foundation. The Government has certain rights in the invention. 
    
    
     FIELD OF INVENTION 
     This invention relates to nanocrystal generation. Specifically, the invention provides a novel method of generating nanocrystals with enhanced photoluminescent characteristics. 
     BACKGROUND OF THE INVENTION 
     Over the past decade, numerous advances have been made in the synthetic procedures for formation and isolation of high quality inorganic nanoparticles. The size dependent optical properties of colloidal semiconductor nanocrystals are ideal for applications in fields ranging from biological imaging, photovoltaics optoelectronic devices, biological tagging, optical switching, solid-state lighting, and solar cell applications. (Chan, W.; Nie, S.  Science.  1998, 281, 2016-2018; Bruchez, J.; Moronne, M.; Gin, P.; Weiss, S.; Alivisatos, A.  Science.  1998, 281, 2013-2016; Bharali, D. J.; Lucey, D. W.; Jayakumar, H.; Pudavar, H. E.; Prasad, P. N.  Journal of American Chemistry Society.  2005, 127, 11364-113671; Huynh, W.; Dittmer, J.; Alivisatos, A.  Science.  2002, 295, 2425-2427; Sun, B.; Marx, E.; Greenham, N.  Nano Letters.  2003, 3, 961-963; Gur, I.; Fromer, N.; Chen, C.; Kanaras, A.; Alivisatos, A.  Nano Letters.  2007, 7, 409-414). Due to the ease of synthesis, a significant fraction of the research to date has centered on the II-VI family of semiconductors utilizing the type I core-shell structures, namely CdSe/ZnS (Park, J.; Joo, J.; Kwon, S.; Jang, Y.; Hyeon, T.  Angew. Chem. Int. Ed.  2007, 46, 4630-4660; Embden, J.; Jasieniak, J.; Gómez, D.; Mulvaney, P.; Giersig, M.  Aust. J. Chem.  2007, 60, 457-471). Recent interest has focused on developing routes to the III-V family, namely InP (Xie, R.; Battaglia, D.; Peng, X.  Journal of American Chemistry Society.  2007, 129, 15432-15433; Gerbec, J.; Magana, D.; Washington, A.; Strouse, G.  Journal of American Chemistry Society.  2005, 127, 15791; Adam, S.; Talapin, D.; Borchert, H.; Lobo, A.; McGinley, C.; de Castro, A.; Hasse, M.; Weller, H.; Möller, T.  The Journal of Chemical Physics.  2005, 123, 084706; Borchert, H.; Haubold, S.; Haase, M.; Weller, H.; McGinley, C.; Riedler, M.; Moller, T.  Nano Letters.  2002, 2, 151-154), due to the perceived lower toxicity for InP based nanocrystals (Bharali, D. J.; et al., Journal of American Chemistry Society. 2005, 127, 11364-113671; Xie, R.; et al.,  Journal of American Chemistry Society.  2007, 129, 15432-15433; Oda, K.  Industrial Health.  1997, 35, 61-68; Zheng, W.; Winter, S. M.; Kattnig, M. J.; Carter, D. E.; Sipes, I. G.  J Toxicol Environ Health.  1994, 43, 483-494; Kabe, I.; Kazuyuki, O.; Hiroshi, N.; Nomiyama, T.; Uemura, T.; Hosoda, K.; Ishizuka, C.; Yamazaki, K.; Sakurai, H.  Journal of Occupational Health.  1996, 38, 6-12; Yamazk, I.; Tanaka, A.; Hirata, M.; Omura, M.; Makita, Y.; Inoue, N.; Sugio, K.; Sugimachi, K.,  Journal of Occupational Health.  2000, 42, 169-178). The downside to InP is the poor photoluminescence (PL) quantum yield (QY), which is typically &lt;4% once isolated from the reaction mixture, although core-shelling yields a value of ˜20% depending on size (Borchert, H.; et al.,  Nano Letters.  2002, 2, 151-154; Haubold, S.; Haase, M.; Kornowski, A.; Weller, H.  Chem Phys Chem.  2001, 2, 331-334). The poor PL QY performance for these materials can be traced to the presence of phosphorus vacancies (Adam, S.; et al.,  The Journal of Chemical Physics.  2005, 123, 084706) (V P ) in the material. 
     The general synthetic approach for preparation of colloidal semiconductor nanoparticles employs a bulky reaction flask under continuous Ar flow with a heating mantle operating in excess of 240° C. The reaction is initiated by rapid injection of the precursors, which are the source materials for the nanoparticles, at high temperatures and growth is controlled by the addition of a strongly coordinating ligand to control kinetics. And to a more limited extent, domestic microwave ovens have been used to synthesize nanoparticles. The high temperature method imposes a limiting factor for industrial scalabiity and rapid nanomaterial discovery for several reasons: random batch-to-batch irregularities such as temperature ramping rates and thermal instability; time and cost required for preparation for each individual reaction; and low product yield for device applications. 
     While recent advances in the field have developed better reactants, including inorganic single source precursors, metal salts, and oxides; better passivants, such as amines and non-coordinating solvents; and better reaction technologies, such as thermal flow reactors; the reactions are still limited by reproducibility. Coupled to this problem is the lack of control over reaction times, which require continuous monitoring. In the case of III-V compound semiconductors, the synthetic pathways have rates of growth on the order of days, while in the case of II-VI&#39;s, size control is very difficult and depends on the ability to rapidly cool the reaction. In these cases, the reaction depends on heating rate, heat uniformity over the reaction vessel, stirring and rapid and uniform cool-down. 
     Removal of the surface V P  sites by active ion etching with hydrofluoric acid (HF) improves the PL performance of these materials to ˜40% (Gerbec, J.; et al.,  Journal of American Chemistry Society.  2005, 127, 15791; Adam, S.; et al.,  The Journal of Chemical Physics.  2005, 123, 084706; Micic, O.; Sprague, J.; Lu, Z. Nozik, A.  Appl. Phys. Letters.  1996, 68, 3150-3152; Talapin, D.; Gaponik, N.; Borchert, H.; Rogach, A.; Haase, M.; Weller, H.  Journal of Physical Chemistry B.  2002, 106, 12659-12663). While the use of active ion etching with HF enhances the InP nanocrystal PL, it represents an inconvenient extra synthetic step that lowers solubility, broadens the excitonic absorption line width, and increases the difficulty for ZnS shelling. The development of an in-situ active ion etchant can simplify the preparation of this family of material, improve the PL QY, and maintain the optical properties of the nanocrystal. 
     The use of ionic liquids in synthesis have attracted attention due to the high thermal stability of the solvent, non-reactivity of the materials, and the added benefit of the solvent being recyclable (Antonietti, M.; Kuang, D.; Smarsly, B.; Zhou, Y.  Angew. Chem. Int. Ed.  2004, 43, 4988-4992). In an earlier report, our group demonstrated the advantages of using non-fluorinated ionic liquids in MW chemistry to accelerate growth of InP and CdSe nanocrystals (Gerbec, J.; et al.,  Journal of American Chemistry Society.  2005, 127, 15791). The isolated InP showed typical PL QYs for this family with values on the order of 4%. Following HF treatment the PL QY increases to 38% (Id.). The most notable effect of using an ionic liquid in MW chemistry is the efficient conversion of MW energy into thermal energy due to the high MW cross-section that ionic liquids possess. In MW chemistry, the molecule with the highest cross-section selectively absorbs the MW energy and through relaxation heats the solvent or the molecular precursors. The selective absorption leads to the “specific” microwave effects often quoted in the synthetic literature (Kappe, O.  Angew. Chem. Int. Ed.  2004, 43, 6250-6284). Ionic liquids typically are not directly involved in the reaction mechanism and can be considered a spectator solvent, allowing non-absorbing materials to be rapidly heated in the MW by convective loss; although ILs are believed to enhance reactions due to the highly ordered solvent framework (Antonietti, M.; et al.,  Angew. Chem. Int. Ed.  2004, 43, 4988-4992; Redel, E.; Thomann, R.; Janiak, C.  Chem. Commun.  2008, 1789-1791). 
     Nanocrystals, as well as the other systems, are rapidly finding applications in biological imaging, biomedical technologies, electronics and photovoltaics. However, current methods to remove materials defects, vacancy or add-ion removal requires annealing (long reaction time) or post reaction treatment with a highly dangerous (HF) solvent. The invention alleviated this shortcomings, allowing rapid isolation of materials and improved total yields. 
     SUMMARY OF THE INVENTION 
     The nanoparticles synthesized by the present invention may comprise semiconductor components. There is no limitation in their composition, but typical examples are single substances of Group IV elements, such as C, Si, Ge, or Sn, single substances of Group V elements, such as P (black phosphorus), single substances of Group VI elements, such as Se or Te, compounds of Group VI elements, such as SiC, and compound from multiple Groups, such as GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbS, PbSe, PbTe, AlN, AlP, AlAs, AlSb, GaN, GaP GaAs, GaSb, InN, InP, InAs, InSb, GaS, GaSe, GaTe, InS, InSe, InTe, TlS, TlSe, TlTe, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe and their ternary and quaternary alloys. Other compounds envisioned are As 2 S 3 , As 4 S 4 , As 2 Se 3 , As 2 Te 3 , Sb 2 Se 3 , Sb 2 Se 3 , Sb 2 Te 3 , Bi 2 S 3 , Bi 2 Se 3 , Bi 2 Te 3 , CuO, Cu 2 O, Ag 2 S and CuSe, CuCl, AgBr and AuCl, NiS 2 , PdS and PtSe, CoSe, RhS and IrSe, FeO, FeS, FeSe and RuS, MnO, MnS, MnSe and ReS, Cr 2 S 3 , Cr 2 Se 3  and MoS 2 , VS, VSe, and NbS, TiO 2 , TiS 2 , and ZrS 2 , BeO, MgS, and CaSe, and chalcogen spinnels, barium titanates (BaTiO 3 ). 
     The invention provides a method to remove defects, vacancies and surface add-ions during the growth of spherical, oblate or elliptical nanocrystals (1-10 nm) by generating in-situ an active ion etchant (halides (F, Cl, Br), oxygen). The in-situ generation of the active ion is achieved by the selective absorption of microwave energy into an ionic liquid which induces decomposition of the active ion containing counter ion (BF 4 , PF 6 , F, ClO 4 , PO 4 , chlorides, bromides, acetate, hydroxide, etc), improving the out-of batch optical performance of nanocrystals. 
     The in-situ active ion etching process is achieved using a microwave—(MW) based synthetic protocol with a decomposable ionic liquid (IL). In-situ generation of the active ion is achieved through direct MW absorption by the IL, thermal relaxation to the counter-ion, and subsequent production of active ion resulting in phosphorus vacancy (V p ) removal during the growth of the nanocrystal. Choosing an ionic liquid containing an active anion that thermally degrades circumvents the requitiste HF etching step by directly producing an in-situ ion source. The concentration of active anion is controlled by the microwave power, microwave cross section, thermal decomposition rate of counter ion, and concentration of the ionic liquid in the reaction mixture of the IL and subsequent thermal degradation of the anion source. 
     Using this methodology, the active ion is available at low concentrations during the reaction and actively removes defects, vacancies, and add-ions from the growing nanocrystal surface. Defect removal improves the materials crystallinity, optical properties, and electrical properties for a wide range of group IV (Si, Ge), II-VI, II-V, III-V, and III-VI semiconductor systems. Without limiting the invention, Group II family members include Cd, Zn, Hg; Group III members Al, Ga, and In; Group V family compound members N, P, As, and Sb; and Group VI family members O, S, Se, and Te. 
     The photoluminescence quantum yield (PL QY) for InP grown under in-situ etching conditions is 47% for the additive hmim BF 4  at a mole ratio of 1:10 (In 3+  to IL). Time dependent degradation studies of the InP grown with the IL indicates the PL properties are maintained in solution for an extended time frame with no detectable change in PL QY after 24 h. 
     The in-situ, microwave assisted active ion etching method represents the first technique to produce high PL QY InP nanocrystals out of batch without using post-generation HF treatment or core-shelling. Additionally, it allows in-situ vacancy or defect removal during the chemical preparation of nanocrystals. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       For a fuller understanding of the invention, reference should be made to the following detailed description, taken in connection with the accompanying drawings, in which: 
         FIG. 1  depicts a Balz-Schiemann type reaction equation, forming the free fluoride ion. 
         FIG. 2  depicts a diagramtic illustration of fluoride etching of a nanoparticle&#39;s surface. As seen in the illustration, the fluoride inhabits the etched regions. 
         FIG. 3  depicts a TEM image of grown InP with hmim BF 4 . 
         FIGS. 4(   a ) and ( b ) depict graphs of pXRD results for InP grown with a 1:10 mole ratio of A) bmpy BF 4  and B) InP grown with hmim BF 4 . 
         FIG. 5  depicts a  19 F MAS graph of InP grown with bmpy BF 4  (1:10 mole ratio), performed at room temperature on a Varian Unity/Inova 500 MHz spectrometer with a 2.5-mm broadband MAS probe tuned to  19 F (470.32 MHz). A spinning speed of 22 kHz, an acquisition time of 10 msec, recycling delay of 3 sec, and a contact time of 7 μsec was used. 
         FIG. 6  is a graph depicting the effect of the concentration of an ionic liquid on nanocrystal photoluminescence. Concentration ratios of the IL used are no ionic liquid (lower dark gray trace), 1:2 (black), 1:5 (light gray), and 1:10 (upper dark gray trace). 
         FIG. 7  depicts a graph comparing Abs and PL of InP grown with hmim BF 4 . Concentrations of the In 3+  precursor to the IL used are 1:0.1 (black), 1:1 (light gray), and 1:10 (dark gray). 
         FIG. 8  depicts a graph comparing the concentration dependence of PL for InP grown from bmpy BF 4  at a 1:0.1 (light gray), 1:1 (black), 1:10 (dark gray). 
         FIG. 9  PL QY for a series of In 3+ :IL mole ratios of InP grown with hmim BF 4  (solid) and InP grown with bmpy BF 4  (dash). 
         FIG. 10  Comparison of PL properties for InP grown with a 1:1 mole ratio of hmim PF 6  (dark gray), hmim BF 4  (light gray), and hmim Cl (black). 
     
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 
     InP nanocrystals are prepared using separate stock solutions of indium palmitate and tris-trimethylsilylphosphine [(TMS) 3 P] in a CEM Discover Microwave reactor vessel. Solutions of indium palmitate and tris-trimethylsilylphosphine (TMS) 3 P dissolved in decane were prepared at 50° C. under Argon. Predetermined concentrations of additive, listed in the Table, were added to the microwave reactor vessel. The indium palmitate and (TMS) 3 P solutions were injected into the microwave reactor vessel at a molar ratio of 2:1. The solutions were mixed prior to MW irradiation. MW growth is accomplished by ramping the reaction at 300 W (single mode, focused, 2.45 GHz), with a ramping time from 1-25 minutes depending on the choice of additive or MW system used. Once the desired temperature of 280° C. was reached, the reaction vessel was actively cooled using pressurized air, from about 3 psi to 30 psi, of the microwave cavity to remove latent heat. The reaction was allowed to progress for a reaction time of 15 minutes. Once the MW reaction was complete, the temperature is rapidly reduced to room temperature (˜2 min) using forced air cooling at approximately 70 psi. 
     [PF 6 ] −  and [BF 4 ] −  anions are prone to thermal decomposition producing controlled quantities of F −  ions. The thermal production of fluoride ions arises from a Balz-Schiemann type reaction, seen in  FIG. 1 . In fact, tetrafluoroborate-based ionic liquids thermally decompose at 240° C. at a rate of 0.017%/min. This results in the anionic fluoride radical etching the surface of the forming nanocrystal, seen in  FIG. 2 . In order to assess the affect on the PL QY of InP by the addition of fluorinated ILs during nanocrystal growth, a series of ILs were investigated, based on 1-hexyl-3-methyl-imidazolium (hmim), 1-butyl-4-methyl-pyridinium (bmpy), and tetrabutylammonium (TBA) with the counter-ions [BF 4 ] − , [PF 6 ] − , F − , and Cl − . 
     
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Additived used in InP Synthesis 
               
             
          
           
               
                   
                   
                   
                   
                 PL  
                 Ramp  
               
               
                 Anion 
                 Additive 
                 Abbreviation 
                 Ratio 
                 QY  
                 Time (sec) 
               
               
                   
               
             
          
           
               
                 [BF 4 ] −   
                 1-hexyl-3-methyl- 
                 hmim BF 4   
                 1:20 
                 35.3 
                 55 
               
               
                   
                 imidazolium BF 4   
                 hmim BF 4   
                 1:10 
                 47.1 
                 70 
               
               
                   
                   
                 hmim BF 4   
                 1:5 
                 41.6 
                 725 
               
               
                   
                   
                 hmim BF 4   
                 1:3 
                 34.6 
                 410 
               
               
                   
                   
                 hmim BF 4   
                 1:2 
                 8.8 
                 340 
               
               
                   
                   
                 hmim BF 4   
                 1:1 
                 1.7 
                 760 
               
               
                   
                   
                 hmim BF 4   
                 1:0.1 
                 1.2 
                 810 
               
               
                   
                 1-butyl-4-methyl- 
                 bmpy BF 4   
                 1:20 
                 29.5 
                 180 
               
               
                   
                 pyridinium BF 4   
                 bmpy BF 4   
                 1:10 
                 43.2 
                 220 
               
               
                   
                   
                 bmpy BF 4   
                 1:5 
                 9.9 
                 250 
               
               
                   
                   
                 bmpy BE 4   
                 1:3 
                 2.7 
                 325 
               
               
                   
                   
                 bmpy BE 4   
                 1:2 
                 3.8 
                 435 
               
               
                   
                   
                 bmpy BF 4   
                 1:1 
                 1.6 
                 590 
               
               
                   
                   
                 bmpy BF 4   
                 1:0.1 
                 1.3 
                 1320 
               
               
                   
                 tetrabutylammonium  
                 TBA BF 4   
                 1:10 
                 11.2 
                 170 
               
               
                   
                 BF 4   
                 TBA BF 4   
                 1:1 
                 4.2 
                 370 
               
               
                   
                   
                 TBA BF 4   
                 1:0.1 
                 1 
                 1735 
               
               
                 [PF 6 ] −   
                 1-hexyl-3-methyl- 
                 hmim PF 6   
                 1:10 
                 24.5 
                 150 
               
               
                   
                 imidazolium PF 6   
                 hmim PF 6   
                 1:1 
                 5.7 
                 310 
               
               
                   
                   
                 hmim PF 6   
                 1:0.1 
                 1.8 
                 485 
               
               
                   
                 1-butyl-4-methyl- 
                 bmpy PF 6   
                 1:10 
                 N/A 
                 220 
               
               
                   
                 pyridinium PF 6   
                 bmpy PF 6   
                 1:1 
                 1.8 
                 302 
               
               
                   
                   
                 bmpy PF 6   
                 1:0.1 
                 1 
                 485 
               
               
                   
                 tetrabutylammonium  
                 TBA PF 6   
                 1:10 
                 N/A 
                 305 
               
               
                   
                 PF 6   
                 TBA PF 6   
                 1:1 
                 1 
                 432 
               
               
                   
                   
                 TBA PF 6   
                 1:0.1 
                 1 
                 1065 
               
               
                 F −   
                 tetrabutylammonium  
                 TBA F 
                 1:10 
                 N/A 
                 190 
               
               
                   
                 fluoride 
                 TBA F 
                 1:1 
                 N/A 
                 295 
               
               
                   
                   
                 TBA F 
                 1:0.1 
                 1 
                 720 
               
               
                 Cl −   
                 1-hexyl-3-methyl- 
                 hmim Cl 
                 1:10 
                 N/A 
                 135 
               
               
                   
                 imidazolium Cl 
                 hmim Cl 
                 1:1 
                 N/A 
                 430 
               
               
                   
                   
                 hmim Cl 
                 1:0.1 
                 2.3 
                 670 
               
               
                   
                 1-butyl-4-methyl- 
                 bmpy Cl 
                 1:10 
                 N/A 
                 140 
               
               
                   
                 pyridinium Cl 
                 bmpy Cl 
                 1:1 
                 N/A 
                 494 
               
               
                   
                   
                 bmpy Cl 
                 1:0.1 
                 1.5 
                 1332 
               
               
                   
               
             
          
         
       
     
     For the optical studies, the InP nanocrystals were isolated from the reaction mixture by initial addition of toluene and precipitation by addition of acetone, followed by treatment with toluene/MeOH (2×). The quantum yields were determined by comparing the emission of InP with that from rhodamine 6G in ethanol (QY=95%). (Gerbec, J.; et al.,  Journal of American Chemistry Society.  2005, 127, 15791). 
     Using transmission electron microscopy (TEM), the MW-grown InP are 2.7±0.3 nm spherical, cubic morphology nanocrystals, seen in  FIG. 3 . The large disparity represents an upper limit due to imaging limitations for these materials at this size regime. Powder X-ray diffraction (pXRD) analysis of the sample indicates a Zn-blende structure (F-43m) is formed, as seen in  FIG. 4 . Scherrer analysis of the pXRD confirms the TEM size measurement. Solid state nuclear magnetic resonance spectroscopy shows that fluorine is still present after material isolation on the InP samples grown by these methods, seen in  FIG. 5 , indicating that InP has been HF etched. 
     The magnitude of enhancement resulting from adding hmim BF 4  to the MW reactor is clearly evidenced in the dramatic PL improvement observed for the InP nanocrystal grown in the presence and absence of the IL, seen in  FIG. 6  and data not shown. The changes in the absorption and PL spectra for InP grown with the additive added in a 1:0.1, 1:1, and 1:10 mole ratio of In 3+  to hmim BF 4  are shown in  FIG. 7 . The PL QYs for each additive condition are compiled in the Table. The [BF 4 ] −  salts showed the highest overall PL QY improvement, followed by the [PF 6 ] −  based ILs lower QYs, while the F −  and Cl −  salts did not produce highly emissive materials or led to loss of the nanocrystal. The highest PL QY arises for the ionic liquid hmim BF 4  at a concentration of 1:10. At this concentration it was possible to reproducibly grow InP with a PL QY of 47%. No spectral shift for the PL profile is observed for the various concentrations of hmim BF 4 , seen in  FIG. 7 , or bmpy BF 4 , as seen in  FIG. 8 ; however as the concentration of IL is increased the InP PL QY asymptotes for the hmim BF 4  at a concentration above 1:5, while bmpy BF 4  asymptotes at 1:10, seen in  FIG. 9 . The difference in hmim and bmpy can be explained due to the higher polarity of hmim, and therefore higher MW absorption and subsequent thermal transfer from the IL to the counterion. (Aki, S., et al.,  Chem. Commum.  2001, 413-414) The higher thermal transfer leads to higher fluoride ion release in the reaction. 
     The observed InP PL QY depends on the type of IL and the concentration of IL. For samples grown with a 1:10 mole ratio of the IL the trend observed is BF 4   − &gt;PF 6   − &gt;&gt;&gt;Cl − , while at a 1:1 ratio the PL QY follows the trend PF 6   − &gt;BF 4   − &gt;&gt;&gt;Cl − , seen in  FIG. 10 . The observed anion dependence on IL mole ratio reflects the magnitude of F −  production, with [PF 6 ] −  having the highest fluoride ion production in time compared to [BF 4 ] − . The level of fluoride ion production mirrors the bond energies for the B—F bond (174 kcal/mol) compared to the P—F bond (96 kcal/mol) (Lide, D., CRC Handbook of Chemistry and Physics. 88th Ed. 2007-2008). The weaker bond strength in P—F will result in more facile thermal degradation and therefore higher fluoride ion concentrations. At high IL mole ratios the increased fluoride ion concentration leads to aggressive etching and subsequent loss of the materials. 
     To assess whether the PL improvement requires an IL with a high MW cross section or just an anion capable of producing fluoride ion, TBA salts of [BF 4 ] − , [PF 6 ] − , and F −  were tested at reaction temperatures of 280° C., which is high enough to initiate anion degradation. The Table illustrates the combination of IL and counter-ion necessary to achieve high PL QY in these materials. Although PL QY improvement is observed for TBA BF 4 , the PL QY for TBA BF 4  was far lower (11%) than observed for either hmim BF 4  (47%) or bmpy BF 4  (43%). For the TBA salts, the magnitude of PL QY followed the trend [BF 4 ] − &gt;&gt;&gt;[PF 6 ] − ˜F − . At high concentrations of the [PF 6 ] −  or F −  salts the InP nanocrystals are not formed. As noted earlier, it is believed that for the [PF 6 ] −  and F −  salts, more rapid fluoride generation exists in the reaction and the resultant F −  ions inhibit InP growth due to formation of InF 3  and reaction with the P source with subsequent formation of PF 3 . The difference in PL QY between TBA and hmim can be explained due to the lower microwave absorption by TBA during the reaction resulting in lower F −  production for the ILs during the InP growth. The lower MW cross section for TBA is clearly evidenced by the longer MW ramp times observed for the TBA salts, seen in the Table. 
     The experimental results suggest that a slow, controlled production of fluoride ions during nanocrystal growth is crucial to produce the highest PL QY in InP. The slow production of fluoride ions apparently allows controlled removal of defects to compete with nanocrystal growth. At high fluoride ion concentrations ([PF 6 ] −  vs. [BF 4 ] − ), the rate of etching is faster than the rate of growth resulting in poor material performance. At low fluoride ion content (hmim BF 4  vs. bmpy BF 4 ) the reaction results in faster growth than etching, which yields poor PL QYs. The balance of etching and growth imply that during synthesis of InP nanocrystals an ionic liquid with a fluoride counter ion serves to super-heat the reaction through the high absorption cross section for microwave energy of the IL converting that energy to convective energy, and produce a transient in-situ source for fluoride ions by thermal degradation of the counter-ion. MW chemistry allows the careful control of etching relative to growth by balancing the MW cross section of the reactants with the thermal degradation rate for the fluoride containing IL. The careful control provided by the MW leads to a rapid, convenient synthetic methodology allowing isolation of InP nanocrystals with nearly 50% PL QYs that are adaptable to a flow through technology. Such a technology allows the use of these materials in bio-imaging applications where toxicity issues are a concern for bio-nanotechnology. 
     It is also to be understood that the following claims are intended to cover all of the generic and specific features of the invention herein described, and all statements of the scope of the invention which, as a matter of language, might be said to fall therebetween.