198 Main Group Compounds and Ligands

3. J. G. Breitzer, J.-H. Chou, and T. B. Rauchfuss, Inorg. Chem. 37, 2080 (1998).
4. (a) P. Jeroschewski, Z. Chem. 21, 412 (1981); (b) P. Jeroschewski, P. Hansen, Sulfur Rep. 7, 1
(1986).
5. H. Lund, E. Hoyer, and R. G. Hazell, Acta Chem. Scand. B 36, 207 (1982).
6. (a) G. A. Holloway, K. K. Klausmeyer, and T. B. Rauchfuss, Organometallics 19, 5370 (2000); (b)
K. Kubo, A. Nakao, H. M. Yamamoto, and R. Kato, J. Am. Chem. Soc. 128, 12358 (2006).

37. MID-INFRARED EMITTING LEAD SELENIDE

NANOCRYSTAL QUANTUM DOTS

Submitted by JEFFREY M. PIETRYGA* and JENNIFER A.

HOLLINGSWORTH**
Checked by FUDONG WANGy and WILLIAM E. BUHROy

Pb…O2 CMe†2 ? 3H2 O ‡ SeˆP…C8 H17 †3 ® PbSe ‡ 2HO2 CMe ‡ 2H2 O ‡ OˆP…C8 H17 †3

Colloidal nanocrystal quantum dots (NQDs) couple size-tunable optical properties

with molecule-like chemical properties such as solubility, processability, and
chemical reactivity (the latter depending on the identity of the surface-bound
ligands).1 Photoluminescent NQDs are potentially useful as molecular probes in
biology and as materials for the construction of solid-state light-emitting devices.
Synthetic routes have previously been reported for NQDs that emit in the
ultraviolet (e.g., ZnSe),2 in the visible (e.g., CdSe),3 and in the near-IR (e.g.,
small-size PbSe <8 nm in diameter).4 Because bulk PbSe has a bandgap of 0.26 eV
(4.7 μm) at room temperature, PbSe NQDs have the potential to exhibit photo-
luminescence (PL) in the mid-IR energy range (2.5 μm).
The synthetic routes described here are useful for obtaining large-size PbSe
NQDs (8–17 nm) with demonstrated emission in the mid-IR (2.5–3.5 μm).5 The
key feature of the synthetic approach described in detail here is the use of a two-
step growth process. The first step involves nucleation and initial growth by rapid
injection of lead and selenium precursors into a hot surfactant/solvent mixture.
Under these conditions, growth is sufficiently fast that narrow size dispersions can
be obtained; the resulting PbSe NQDs are small and emit at wavelengths less than
2.5 μm. Additional particle growth to larger NQD sizes is accomplished in the
second step, which involves slow addition of precursors to the solution containing
the “seed” particles. In this way, large-size PbSe NQDs are obtained that possess
optimized optical properties and minimal size dispersions.
*
Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM 87545.
**
Materials Physics & Applications Division, Los Alamos National Laboratory, Los Alamos, NM 87545.
y
Department of Chemistry, Washington University, St. Louis, MO 63130.
 37. Mid-infrared Emitting Lead Selenide Nanocrystal Quantum Dots 199

General Procedures
Operations are conducted under nitrogen gas in a glove box (O2 <1 ppm) or by
using standard Schlenk manifold techniques. Trioctylphosphine (TOP, 90%,
Fluka) is heated to 200°C under an inert atmosphere for 2 h before use. Selenium
shot (99.999%, Alfa Aesar), diphenyl ether (99%, Acros), lead(II) acetate trihy-
drate (99.999%, Aldrich), and oleic acid (90%, Aldrich) are used without further
purification. Oleic acid is stored in the glove box freezer ( 30°C). The lead(II)
acetate trihydrate slowly dehydrates in the glove box and becomes less soluble;
therefore, use of fresh material is recommended. The 1 M TOPSe in TOP stock
solution is prepared by covering selenium shot (1.58 g, 20 mmol) with TOP
(20 mL) and stirring vigorously under inert atmosphere until the selenium dis-
solves (∼12 h). Temperature regulation is achieved using a temperature controller
(Barnant Standard Model) fitted with a heating mantle and thermocouple probe
(Type K). PL measurements are performed on dilute NQD solutions in hexane or
CDCl3; samples are excited at 808 nm, and emission is analyzed using a grating
monochromator and a chilled InSb detector.

A. LEAD SELENIDE NQDs EMITTING AT 2.5 μm (0.50 eV)

Procedure
A three-necked flask is fitted with a condenser (topped with a valved gas adapter), a
rubber septum, and a glass stopper. In a glove box, the flask is loaded with a stir
bar, lead(II) acetate trihydrate (0.87 g, 2.3 mmol), and oleic acid (2.3 mL,
7.2 mmol). The reactants are covered with diphenyl ether (2 mL) and TOP
(8 mL). The flask is sealed, removed from the glove box, and connected to a
Schlenk manifold through the valve at the top of the condenser. While keeping the
contents of the flask under an inert atmosphere, a thermocouple probe is passed
through the previously glass-stoppered neck using a PTFE 1/800 thermocouple
adapter (available from Chemglass or J-Kem Scientific). With stirring, the mixture
is heated to 65°C under dynamic vacuum for 1 h, forming a clear solution. In the
same manner, diphenyl ether (10 mL) is heated to 45°C under dynamic vacuum for
1 h in a four-necked flask fitted with a similarly valved condenser, septum,
thermocouple probe, and an addition funnel. Both flasks are then placed under
inert atmosphere. The three-necked flask is allowed to cool to room temperature,
while the four-necked flask is heated to 185°C. TOPSe stock solution (2.3 mL) is
then injected into the lead-containing flask, and an aliquot of this mixture (3.5 mL)
is removed and placed in the addition funnel on the four-necked flask. The
remaining reactant solution is then quickly injected into the rapidly stirring hot
diphenyl ether. The resulting mixture turns brown, indicating nucleation of PbSe
NQDs. After 4 min (as the solution returns to 185°C), the contents of the addition
200 Main Group Compounds and Ligands

funnel are added slowly over ∼5 min. Eleven minutes after the initial injection, the
flask is removed from the heat and the mixture is quenched by addition of cold
( 90°C) toluene (15 mL), and then allowed to cool to ∼50°C. Methanol (10–
20 mL) is added with stirring until the mixture is persistently cloudy, indicating
precipitation of the product NQDs. The solid is collected by centrifugation, and
redissolved in hexane (10 mL). The NQDs are reprecipitated by addition of
methanol (10 mL) and n-butanol (1 mL); this reprecipitation removes more of
the passivating ligands and allows removal of more unreacted precursors, but also
can result in loss of some passivating ligands, which can reduce the solubility and
PL intensity of the NQDs. Yield: 60 mg (9%, reckoned as PbSe).

Properties
PbSe NQDs prepared by this procedure are photoluminescent and emit between
2.5 and 2.7 μm. The emission is somewhat broad because a relatively wide range of
NQD particle sizes is produced by this procedure. As prepared, the NQDs are
hydrophobic and therefore soluble in common solvents such as hexane, toluene,
and chloroform. Both the powder form and solutions of the PbSe NQDs appear
brown in color. PbSe NQDs tend to oxidize over time, causing the emission bands
to broaden and shift to lower wavelengths (indicative of an increase in particle-size
dispersion). For best retention of optical properties, the particles should be stored
cold in the dark and under an inert atmosphere.

B. LEAD SELENIDE NQDs EMITTING AT 2.8 μm (0.44 eV)

Procedure
Two flasks are constructed and loaded with reactants and solvents exactly as
described in Section 37.A. The four-necked flask is loaded with diphenyl ether
(10 mL), while the three-necked flask is loaded with lead(II) acetate trihydrate
(0.98 g, 2.6 mmol), oleic acid (2.3 mL, 7.2 mmol), diphenyl ether (2 mL), and
TOP (10 mL). Both flasks are heated under vacuum for 1 h, exactly as above.
After being refilled with inert gas, the three-necked flask is cooled to room
temperature, and the four-necked flask is heated to 200°C. After TOPSe stock
solution (2.6 mL) is added to the lead-containing flask, an aliquot of this mixture
(6 mL) is removed and placed in the addition funnel on the four-necked flask.
The remaining reactant solution is quickly injected into the hot diphenyl ether.
After 4 min, the contents of the addition funnel are slowly added over ∼10 min.
Sixteen minutes after the initial injection, the flask is removed from heat, and the
reaction is quenched by addition of cold ( 90°C) toluene (15 mL). Precipitation
 37. Mid-infrared Emitting Lead Selenide Nanocrystal Quantum Dots 201

and collection of product is carried out by the same method as above. The second
precipitation can result in some loss of solubility and photoluminescent proper-
ties. Yield: 90 mg (12%).

Properties
NQDs prepared by this route are characterized by an emission wavelength of
2.8 μm. Otherwise, properties are similar to those described for 2.5 μm emitting
PbSe NQDs.

C. LEAD SELENIDE NQDs EMITTING AT 3.3 μm (0.38 eV)

Procedure
Two flasks are constructed as described in Section 37.A. The three-necked flask is
charged with lead acetate trihydrate (0.98 g, 2.6 mmol), oleic acid (2.5 mL,
7.9 mmol), diphenyl ether (2 mL), and TOP (9 mL). The four-necked flask is loaded
with diphenyl ether (10 mL). Both flasks are heated under vacuum, and then refilled
with inert gas as above. The three-necked flask is cooled to room temperature, while
the four-necked flask is heated to 220°C. TOPSe stock solution (2.6 mL) is added to
the lead-containing flask, and an aliquot of this mixture (5.5 mL) is placed in the
addition funnel on the four-necked flask. The remaining reactant solution is quickly
injected into the hot diphenyl ether. After 3.5 min, the contents of the addition funnel
are slowly added over ∼8.5 min. Fifteen minutes after the initial injection, the flask is
removed from heat, and the reaction is quenched by addition of cold ( 90°C) toluene
(20 mL). Precipitation and collection of product is carried out by the same method as
above, with the same loss of photoluminescent properties and solubility after the
second precipitation. Yield: 155 mg (21%).

Properties
NQDs prepared by this route are characterized by an emission wavelength of
3.3 μm. Otherwise, properties are similar to those described for 2.5 μm emitting
PbSe NQDs.

D. LEAD SELENIDE NQDs EMITTING AT 3.5 μm (0.35 eV)

Procedure
Two flasks are constructed as described in Section 37.A. The three-necked flask is
charged with lead acetate trihydrate (1.56 g, 4.1 mmol), oleic acid (5 mL,
202 Main Group Compounds and Ligands

11 mmol), diphenyl ether (3.5 mL), and TOP (11 mL). The four-necked flask is
loaded with diphenyl ether (10 mL). Both flasks are heated under vacuum, and then
refilled with inert gas as above. The three-necked flask is cooled to room
temperature, while the four-necked flask is heated to 205°C. TOPSe stock solution
(4.5 mL) is added to the lead-containing flask, and an aliquot of this mixture
(13 mL) is placed in the addition funnel on the four-necked flask. The remaining
reactant solution is quickly injected into the hot diphenyl ether. After 4 min, the
contents of the addition funnel are slowly added over ∼15 min. Twenty-three
minutes after the initial injection, the flask is removed from heat, and the reaction
quenched by addition of cold toluene (20 mL). Precipitation and collection of
product is carried out by the same method, but care must be exercised to avoid
adding too much methanol, as the product very quickly loses solubility if over-
rinsed. Photoluminescent properties and solubility both suffer even more with each
subsequent precipitation step. Yield: 270 mg (23%).

Properties
NQDs prepared by this route are characterized by an emission wavelength of
3.5 μm. Otherwise, properties are similar to those described for 2.5 μm emitting
PbSe NQDs.

References
1. J. A. Hollingsworth and V. I. Klimov, in Semiconductor and Metal Nanocrystals: Synthesis,
Electronic and Optical Properties, V. I. Klimov, ed., Marcel Dekker, New York, 2003, Chapter 1.
2. M. Hines and P. Guyot-Sionnest, J. Phys. Chem. B 102, 3655 (1998).
3. (a) C. B. Murray, D. J. Norris, and M. G. Bawendi, J. Am. Chem. Soc. 115, 8706 (1993); (b) L. H. Qu
and X. G. Peng, J. Am. Chem. Soc. 124, 2049 (2002).
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47 (2001); (b) H. Du, C. Chen, R. Krishnan, T. D. Krauss, J. M. Harbold, F. W. Wise, M. G. Thomas,
and J. Silcox, Nano Lett. 2, 1321 (2002); (c) B. L. Wehrenberg, C. Wang, and P. Guyot-Sionnest,
J. Phys. Chem. B 106, 10634 (2002).
5. J. M. Pietryga, R. D. Schaller, D. Werder, M. H. Stewart, V. I. Klimov, and J. A. Hollingsworth,
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