Synthesis and Optical Properties

of ~uantum-sizeMetal sulfide Particles in Aqueous Solution

J. M. ~edelikovid?R. C. patel.' P. Kaufman.,C. Jovce-Pruden,
,~~
~ ~~
and N. O'Leary
~

Clarkson University, Potsdarn, New York 13699-5810

During the past decade, "small-particle" research has be- associates ( 3 , 4 )have used the elementary electron-hole in
come quite popular in various fields of chemistry and phys- a box model to account for the optical properties of small
ics ( I ) . The recognition of quantum-size effects in very colloidal particles and thin films. The confiied Wannier ex-
small colloidal particles has led to renewed interest in this citon Hamiltonian (eq 1)is used in the Schroedinger equa-
area (2)."Small particles" are clusters of atoms or mole- tion for the crystallite excited state.
cules ranging in size from 1nm to almost 10 nm or having
agglomeration numbers from 10 up to a few hundred. In
other words, small particles fall in size between single
atoms or molecules a i d bulk materials. The agglomeration
-
number specifies the number of individual atoms or mole-
cules in agiven cluster. For the inside R,
The research in this area is interdisciplinary, and i t links e2
colloidal science and molecular chemistry. The symbiosis of V(r)=-;+polarization terms
these two areas of research has revealed some intriguing
characteristics of small particles. Colloidal science teaches For the outside R, we get
us how to prepare very small semiconductor particles and
how to stabilize these aggregates with respect to coagula- V(r)= -
tion and formation of bulk material. The electronic proper- where R is the radius of the particle.
ties of the particles, on the other hand, are related to their
solid-state physics: An Approximate Solution
band structures and band gap The polarization terms are generally small (4)and can be
charge-carriermobilities and lifetimes neglected here. Since V depends on the relative position of
the electrochemical positioning of the band edge potential the electron and hole, this problem cannot be transformed
with respect to that of the solution to the center of mass coordinate. Thus, it cannot be solved
exactly. An approximate solution can be obtained by taking
Of particular importance are quantum effects that arise the solution for the first excited state of the particle in a
when the size of the semiconductor particles becomes box problem when assuming that the electron and hole are
smaller than the Bohr radius of the first exciton state. Nu- uncorrelated.
merous important properties of the semiconductor, such as We seek an approximate solution for the lowest S eigen-
its optical absorption and luminescence emission, undergo function of a particle in a spherical well of infinite depth.
drastic changes in this s u e domain.
Following Flugge (51,these functions are
Describing the States
The band gap of a semiconductor is by definition the en-
e r w necessarv to create an electron (e-) and hole (h') that
arFat rest with respect to the lattice and far enough apart
that their Coulombic attraction is neglib~ble. in spherical coordinates. This yields (see the appendix)

The Confined Wannier Exciton

If one carrier approaches the other, they may form a
bound state ONannier exciton) approximately described by
a hydrogenic Hamiltonian: where AE is the energy of the first excited state.
The fust term in eq 4 corresponds to the sum of the con-
finement cner& for the clcc;ron end the hole, while the
sccond expression is their Coulomb interaction energy. The
quantum confinement tcrm dominates as R decreases, and
where mh and me are the effective masses of the hole and the lowest excited state shift.; to an energy thxt is greater
electron; E is the semiconductor dielectric constant; and re than the band eao ofthe bulk scmiconductor This model
~-~----
~
is
---.
and rh are the positions of the hole and the electron. quite elementaryand ignores two important effects in real
crystallites: the coupling of electronic states to vibrations,
The Electronic Energy Levels and the structure of the crystallite surface.
Several attempts have been made to calculate the elec- Bulk Solids in Analogy with Polymers
tmnic energy levels in quantum-size particles. Brus and I t is easier to understand the transition from molecular
to bulk properties from the point of view of MO theory. For
'On leave from Boris Kidric Institute of Nuclear Sciences, Vinca, example, the relationship between bulk silicon and the sil-
11001 Belgrade, Yugoslavia. icon atom is similar to the relationship between organic
'~uthorto whom correspondence should be addressed.
polymers and their constituent monomers. A piece of bulk

342 Journal of Chemical Education

 silicon is s i m ~ l va normal. albeit extremely
& " . large,
- . inor-
ganic molecule.
Consider a small silicon crvstallite mowing from Si
atoms. The Si atom has four sp hybrid o;bitalswhich, in
combination with neighboring orbitals, form doubly occu-
pied bonding and empty antibonding orbitals. Each new
atom adds one orbital to the bonding set and to the anti-
bonding set for each bond formed. spread of orbital ener-
-eies develops within each orbital set, and the HOMO-
LUMO separation in the molecule becomes the band gap of
the solid. The electronic properties of quantum-size semi-
conductor clusters have k d to remarkable discoveries: en-
hanced photoredox chemistry (6) and large nonlinear opti-
cal effects (7).
Quantum-size semiconductor particles have been pre-
pared from many materials. Particularly well-studied ex- 0.0
amples are sulfides (8-11) and selenides (6, 12). The prep- 3W 100 SW 6W 700
aration often involves chemical methods. Care must be Wavelength (nm)
taken to arrest the precipitation to prevent the formation
of large agglomerates. Thus, the synthesis is usually car- Figure I.Optical absorption spectrum of 2 x lo4 M PbS
ried out in the presence of a suitable protective agent. In
analogy wlth polymer~zat~on, the interactwn of protective H2S with a syringe through a rubber septum mounted on
agents w ~ t hclusters correspondi tu termlnatlon of the po- one neck of the flask. Immediately shake the flask vigor-
lymerization reaction. ously for 3 to 5 min.
Due to its use in solar energy conversion and enhanced A wine-red color should be seen when the flask is held
nonlinear optical properties, CdS is one of the most studied against a light source. Measure the absorption spectrum
semiconductor materials. Bulk CdS is a direct band-gap between the wavelengths of 250 and 700 nm (Fig. 1).This
semiconductor (E. = 2.53 eV). with a relative dielectric con- characteristic spectrum is associated with relaGvely mi-
stant of 5.7. B ~ C P is~ aS&all band-gap semiconductor form 4-nm PbS particles (14-16).
(E.= 0.41 eV). and conseauentlv the absomtion onset oc- Repeat the experiment in the absence of WA, and note
;;sin the ingared range;at adout 3,020 I&. the nearly black color due to the formation of bulk PbS. It
will also become immediately apparent that suspensions of
Experimental quantum-size particles are quite transparent. This is due
All the experiments described here can be readily com- to the low scattering of light. The turbidity is caused by the
pleted in a 3-h period, and they require commonly avail- very small particle size. The bulk PbS sample is very dif-
able chemicals. ferent in this respect.
Preparation of Colloidal Lead Sulfide Preparation of Colloidal Cadmium Sulfide
Caution:Hydrogen sulfie is toxic. The entire preparation Materials
must be carried out in a hood.
0.8 mL of 1x 1Cr2M cadmium perchlorate

.
Materials
a 3-neck 250-mL round-bottom flask
10 mL of 1%(w/w)of 10000-30000 molecular weight
3 mL of 1%(w/w) polybrene (Sigma)
1mL of freshly prepared 8 x lo3 M sodium sulfide
15.2 mL of distilled water
polyvinylalmhol (WA) N2 or Ar gas for purging
2 mL of 1x lo-' M lead acetate ice bath
88 mL of distilled water stirplate and stirbar
1mL of H2Sgas, Nz, or Ar gas for purging syringe
a 5-mL syllnge two beakers, 50-mL and 1-L
The HzS gas may be prepared by dissolving a small Procedure
amount (approximately 0.2 g) of sodium sulfide in 5 mL of
Combine 0.8 mL of 1 x lo-' M cadmium Derchlorate. 3
water contained in a 20-mL Erlenmeyer flask capped with r n of~ 1%(wIw)of polybrene, and 15.2mL of h i l l e d water
a rubber serum cap and a vent needle. This solution is in a 50-mL beaker placed in a n ice bath. Stir the solution
acidified by injecting 2 mL of 2 M hydrochloric acid.
on a stir plate whiie purging the solution with argon or
Enough H2S can be safely generated by this procedure to nitrogen gas for 20 min. Adjust the gas flow rate to avoid
serve over ten students or groups. excess foaming. When the purging is completed, very
We have found it satisfactory for the instructor to auicklv iniect 1mL of 8 x lo3 sodium sulfide solution.
demonstrate the sample preparation described below to
* hef final solution should be a clear and pale yellow. Mea-
the students, and then provide each student group with
sure the absomtion s~ectrumbetween the waveleneths of
enough material for a spectral scan. This procedure elimi-
nates the handling of H2Sby students. A detailed descrip- 250 and 550 n k ( ~ i g . ' ~ ) .
tion of gas transfer by this syringe technique can be found Calculating the Radius of Q-CdS
in the literature (13).
The blue shift in absorption due to confinement of charge
Procedure carriers can be observed for both semiconductors. The
Combine 10 mL of 1%(wlw) of PVA. 88 mL ofwater. and band-gap energy of quantum-size CdS particles can be de-
2 mL of 1 i 10." lead acetate in the 250-mI. round-bot- termined by substituting the experimentally determined
tom flask Bubble NAEIthrourrh the solut~onfor 30 min A absorption onset into the following equation. (See the in-
disposable pipet cozected to
tygon tubing can be used. tersection of the tangent with the wavelength axis in Fig-
Then close the system to the atmosphere. Inject 1 mL of ure 2.)

Volume 70 Number 4 April 1993 343

 6. Nedeukmif. J.M.; Nenadonc, M. T ; Mide, 0 . I.;Nozik,A J. J. Phys Chrm. lm,
90,12-13.
7. Shmitf-Rink, 8.; M i l l e ~D.A. B.; Chemla, D. S. Ph.w. Fm. B 1987,35,8113-8125.
8. Fojtik, A,; WeUer, N.;Roch, U.;Heng1ein.A. Ber Bunsews. Phys. Chem 1984 88,
"<" nnm
""z-z, ,.
9. Nazik,A. J.;Wfilims,F;Nenadovic,M.T.:R$lh,T.;Mide, 0.1. J. Phye Cham 1985,
89,397399.
10. L ~ ~ ~P: o ~sh,o m s sJ, K them ~ h y Len.
s 1896,125,2~02.
11. Herron, N.; Wan& Y.; EckPlt, H. J. Am. Cham. Soc 1990,112,1322-1326.
12. staigerwsla,M. C.;AIivisatos,A. P:(irbaon. J.M.:Hams,TD.: Kortan,R.;M"ller,
A. J.; Thayer, A. M.; Duncan, T M. Douglass, D. C.; E m . L. E. J. Am. C k m . Soc
19S8,110,30163050.
9 the Manipulation
13. M e N s l l ~J. P;Leong. K S.; Coopr,N. J J J C a c c u l u l T e ~ h h i q fff
of A&-Sensitive MeterialamIn E r p r i m n t o l O r g o m m f u l l l ChemlsIv:APmefi-
cum i n Synthesis and Chorocteriz=fion. ACS Symposium Senes No. 357:
A. L. Wayda: M. Y. Oarensbourg, Eds.; Amencan Chemiesl Smiety. Wsshingfon,
DC, 1987; p 6.
14. G a l l d o , S.: Gutlerree, M.; Henglein. A,: Janata, E. Ber Buns~ngeePhys. Chem
1989,93.108~1090.
15. Nenadovie, M. T.; Comor, M. I.;Vasie, V.;Mieic, 0. I. J. Phys. Cham. 1990,94,639&

16. Micie, 0. I.: Rajh,T; Comar,M. I.; Zee, S.:Nedeljkovif, J.M.:Patel,R. C. Maf.Rea.
Soe Symp Prm. 1891,206,127-132.
0.0
$00 350 m0 150 500
Wavelength (nm) Appendix
Derivation of the Equation for the First Excited State
Figure 2. Optical absorption spectrum of 4 x lo4 M CdS. The inter-
cept at 439 nm corresponds to the absorption onset. The Hamiltonian of the Wannier exciton can be written
as

It is easy to find the corresponding band-gap value (Eg= Assuming that the hole is in the center of the sphere,
2.83 eV) and the increase in band-gap energy due to quan-
tum-size effects (see eq 4).
AEg = EdR) - Ed-) = 0.3 eV

In the quantum-size region, band-gap energies are ex-

tremely sensitive to the particle size and thus can be used
for fairly accurate particle sizing. Effective masses of elec-
trons and holes are known (me= 0.19 m, mh = 0.8 m, where
m is the free-electron mass), so substitution into eq 4
yields: The Schrodinger equation in spherical coordinates is

The solution given by the wave function for S orbitals is

Rearranging, we get Cn nrrr

'?"=-sin-
[R]' + 1 . 5 x m [Rl - 8.1 x loA8m2 = 0 (6) r R
Solving eq 6, we get I t follows for the Schrodinger equation
R=2.2nm
Thus,
~ = 2 ~ = 4 4 . &

Summary
This experiment illustrates
simple colloidal techniques for the preparation of two differ-
ent types of quantum-size metal sulfide particles
the blue shift of the measured aotieal absomtion sectrawhen
in
the part& size is derreascd the quantum-sue rramr
use ofa simple quantum mtchand mudcl 10 rslculate the
r2e=~Ercos-
ar " R
nnr
R
sin-
nm
R
ane from ihe absorplinn onset measured for CdS

Literature Cited
1. Henglein,A. Top. Cum Chrm. 1988,143,113-180.

(;i
2. H.nglen.A.Cham.Re~. 1989.89.1861-1873.
3. B m , L E.J Chem Phys. 1983,79,55665571. nnr
4. R m , L E. J. Chem. Phys. 1984.80.4034409. = -C,r - sin -
5. Flugge. s Proctlol Quantum Mehonics; Sptinger: Berlin. 1971; Volume 1, p 155. R .

344 Journal of Chemical Education

For n = 1, and conversion to SI units,

Volume 70 Number 4 April 1993 345