Zinc oxide quantum dot nanoparticles absorb UV light but are optically transparent making them useful as the active ingredient of sunscreens. The absorption wavelength is a function of particle size when the particles are small. This synthesis involves particle growth at 65°C; samples removed at longer times give larger particles. The cut-off wavelength from the absorption spectra can be used to estimate the particle size.
- Wear eye protection
- Chemical gloves recommended
- Fumehood recommended
Step 1.Begin heating a large beaker of water to 65°C.
Step 2. Meanwhile, dissolve 0.10 g Zn(CH3CO2)2.H2O in 25 mL isopropanol with heating in a fume hood. (The actual elapsed time shown in the movie is about 15 minutes.)
Step 3. Meanwhile, prepare an ice bath by adding water to ice. Place 125 mL isopropanol in a flask and chill the flask in the ice bath.
Step 4. When the zinc acetate solid has all dissolved, add that solution to the 125 mL of chilled isopropanol. Also obtain 15 mL of 0.050 M NaOH in isopropanol and chill the solution. (A stock solution may already be chilled. See below.)
Step 5. Slowly transfer the chilled NaOH solution to the chilled and rapidly stirring zinc acetate solution using a pasteur pipet.
Step 6. Place the flask with the mixed solution in the 65°C water bath and start taking samples immediately. Record the UV spectra of each sample.
The x-intercept of the linear portion of the absorbance as a function of wavelength graph is a measure of Eg.
Eg = h c / λ
h = 6.626×10-34 J s
c = 2.998×108 m/s
e = 1.602×10-19 C
ε0 = 8.854×10-12 C2/N/m2
m0 = 9.110×10-31 kg
λbulk = 512 nm
ε = 5.7
me* = 0.19
mh* = 0.80
λbulk = 709 nm
ε = 10.6
me* = 0.13
mh* = 0.45
λbulk = 365 nm
ε = 8.66
me* = 0.24
mh* = 0.59
The effective mass model suggests
where r is the radius of the nanoparticle. The second term is the particle-in-a-box confinement energy for an electron-hole pair in a spherical quantum dot and the third term is the Coulomb attraction between an electron and hole modified by the screening of charges by the crystal.
After multiplying by r2, rearranging, and using the quadratic formula,
- What is the radius of the ZnO nanoparticles for each spectrum you recorded?
- Plot r3 versus the growth time.
- If the solution is heated for a long period of time, it eventually turns cloudy. Why?
- Zn(CH3CO2)2.H2O (0.10g per batch)
- (CH3)2CHOH (165mL per batch). Isopropanol vapors irritate the respiratory tract and eyes. Wear eye protection and use in a fume hood. Avoid skin contact.
Stock NaOH Solution for 6 batches:
Dissolve 0.20 g NaOH in 100 mL isopropanol with heating. (Quickly weigh out about 2 pellets of the hygroscopic NaOH and immediately transfer to the waiting solvent.) Chill the stock solution to prepare for use above.
- 1L beakers for hot water bath and ice bath
- thermometer to measure 65°C
- Stirbars and stirring hotplate
- 50 and 250 mL Erlenmeyer flasks
- 25 mL graduated cylinder
- 0.01 g balance
- UV spectrometer and cuvets