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C. M. Expt. 6 Determination of Number of ZnS Shells on CdSe/ZnS Quantum Dots Developed by Karen S.

Quaal, Department of Chemistry and Biochemistry, Siena College, Loudonville, NY. Jennifer Z. Gillies, Evident Technologies, Troy, NY. quaal@siena.edu The Crash and Suspend procedure was used to remove the organic ligands from the surface of the quantum dot (QD). Crash and Suspend Procedure: A known volume of approximately 1 micromole* of a CdSe/ZnS in toluene sample was added to a glass centrifuge tube. The centrifuge tube was filled ~5/6 full with methanol. The tube was shaken and put in ice for twenty minutes. After icing, the tube was placed in a centrifuge for twenty minutes. When removed from the centrifuge, the supernatant was clear and CdSe/ZnS crystals were in the bottom of the tube. If the supernatant is not clear, repeat the icing and centrifuge procedure. The supernatant was removed and a minimum amount of toluene was added in order to resuspend the crystals. A sonicator was used to aid in resuspension. Methanol was added and the procedure was repeated two additional times. Note: The quantum dots become progressively more difficult to resuspend as they are stripped of their ligands. *Moles based on concentration determined by using Beer’s Law, UV/VIS spectrum and molar absorptivity of CdSe, which is available in Yu1 et al or at the following website: www.evidenttech.com. A sample calculation of molar mass for CdSe quantum dot: From Yu1 et al article or Evident Technologies’ website: λ max= 528 nm Cd-Se bond length 0.36 nm Calculation of Formula units of CdSe across diameter of QD: Diameter/CdSe bond length: 2.4 nm/0.36 nm= 6.66 units Calculation of # of CdSe units in a sphere of d=2.4 nm diameter: (4/3)π(d/2)3=(4/3)(3.14)(6.66/2) 3 =154.6 units of CdSe in the Q.D. Calculation of Molar Mass of Q.D: (154.6 units of CdSe)(molar mass Cd+ molar mass Se)=29,580 g/Mol, the molar ε=57,000 cm-1M-1 Diameter= 2.4 nm

and weighed in order to determine the constant mass of the dried crystals. The centrifuge tube was then placed under vacuum. B. After the solution was removed from the centrifuge tube. Analysis of Atomic Absorption Spectroscopic Data: A. the tube was cleaned. A piece of filter paper was secured over the centrifuge tube. This solution was allowed to sit overnight.mass of CdSe Q.D. High purity concentrated Hydrochloric Acid (5-6 drops) was added to the centrifuge tube. and a small hole was punched in the filter paper to allow airflow.4 nm. dried. the supernatant was removed a final time. . then weighed. To determine the concentration of CdSe in mg/mL in the original sample. The mass of Zn was divided by the molar mass of Zn (65. The mass of Cd was then added to the mass of Se to give the total mass of CdSe in the constant weight sample. at 70 °C. This process was repeated until a constant weight for the dried CdSe sample was obtained and recorded. the mass of Zn in the constant weight sample was determined. The tube was then placed in a hot water bath and left until the solution was clear and contained no solids (2-3 hours). C. The moles of Cd were then multiplied by the molar mass of Se (78. To determine the mass of ZnS: Using the concentration of Zn as determined by AA and the volume of the dilution. that has a diameter of 2. The moles of Zn were then multiplied by the molar mass of S (32.96 g/mol) to give the mass of Se in the constant weight sample. Digestion Procedure: High Purity concentrated Nitric Acid (2 mL) was added to the centrifuge tube containing the dry nanocrystals. D. The tube was cooled in a desiccator. The mass of Cd was divided by the molar mass of Cd (112. Mass of CdSe: Using the concentration of Cd as determined by AA and the volume of the dilution. the mass of Cd in the constant weight sample was determined. The mass of Zn was then added to the mass of S to give the total mass of ZnS (as determined by AA spectroscopy) in the constant weight sample.066 g/mol) to give the mass of S in the constant weight sample. Constant Mass: The constant mass of the dry crystals was divided by the original sample volume used for the Crash and Suspend procedure to give the constant mass of crystals per mL (g/mL).411 g/mol) to give the number of moles of Cd in constant weight sample. Constant Weight Procedure: After the Crash and Suspend procedure was repeated three times. The solution was then diluted for AA spectroscopic analysis to determine the cadmium and zinc concentrations.39 g/mol) to give the number of moles of Zn in constant weight sample. divide the total mass of CdSe (as determined by AA spectroscopy) in the constant weight sample by the original sample volume. for 1 hour. The filter paper was replaced and the tube was dried in a vacuum at 70°C for an additional hour.

dTOTAL was determined. and using the AA data for the left side of the equation. 4) (mg Cd divided by mg Zn) = (mg CdSe/dot divided by mg ZnS/dot) The milligrams of CdSe/dot were determined by multiplying the number of units of CdSe/dot by the molar mass of CdSe (191 g/mol) and then dividing by Avogadro’s number to get grams of CdSe/dot. Using Equation 2 VTOTAL was determined.1x10 -21 g/nm3) to obtain the volume of the shell in nm3. VSHELL was determined by dividing the mg ZnS/dot by the density of ZnS (4. was obtained by adding the mass of CdSe to the mass of ZnS. as determined by AA spectroscopy. Using equation 1. Number of ZnS Shells on CdSe/ZnS QD procedure: Information needed: Diameter of CdSe (nm) based on spectral data1 # units of CdSe across diameter # units of CdSe/dot Density of ZnS (4. Using equation 4.1x10-21 g/nm3) Single ZnS shell thickness (0. To verify that the digestion process was valid. .31 nm) Equations: 1) VTOTAL = (4/3)π (dTOTAL/2)3 2) VTOTAL = VCORE + VSHELL 3) dTOTAL = d1 +d2 + dCORE Where d1 = d2 and represent the thickness of the ZnS shells encapsulating the core along a diameter through the center of the sphere. the mg of ZnS/dot was determined utilizing both the mg CdSe/dot calculated in step 1. which is then converted to milligrams to give mg CdSe/dot.E. The total mass of CdSe/ZnS quantum dots in the original sample. VCORE was determined using equation 1 and substituting the diameter of the core (CdSe) for dTOTAL. the total mass (as determined by AA spectroscopy) and the constant weight were compared.

Mater. Guo W. Yu..31 nm).. 2003.. References: 1. Experimental Determination of Extinction Coefficient of CdTe. 15 (14) 28542860 . CdSe. Dividing by 2 gives the thickness of the shell. d1 + d2 was determined.. Chem. W.Using Equation 3. Qu L. the thickness of the shell was divided by the Single ZnS shell thickness (0. and CdS Nanocrystals. To determine the number of shells. and Peng X.