Lead selenide

Lead selenide (PbSe), or lead(II) selenide, a selenide of lead, is a semiconductor material. It forms cubic crystals of the NaCl structure; it has a direct bandgap of 0.27 eV at room temperature. (Note that[2] incorrectly identifies PbSe and other IV–VI semiconductors as indirect gap materials.) [3] It is a grey crystalline solid material.

Lead selenide
Names
Other names
Lead(II) selenide
Clausthalite
Identifiers
ECHA InfoCard 100.031.906
Properties
PbSe
Molar mass 286.16 g/mol
Melting point 1,078 °C (1,972 °F; 1,351 K)
Structure
Halite (cubic), cF8
Fm3m, No. 225
a = 6.12 Angstroms [1]
Octahedral (Pb2+)
Octahedral (Se2−)
Hazards
Repr. Cat. 1/3
Toxic (T)
Harmful (Xn)
Dangerous for the environment (N)
R-phrases (outdated) R61, R20/22, R23/25, R33, R62, R50/53
S-phrases (outdated) (S1/2), S20/21, S28, S53, S45, S60, S61
Related compounds
Other anions
 Lead(II) oxide
Lead(II) sulfide
Lead telluride
Other cations
 Carbon monoselenide
Silicon monoselenide
Germanium(II) selenide
Tin(II) selenide
Related compounds
 Thallium selenide
Bismuth selenide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YN ?)
Infobox references

It is used for manufacture of infrared detectors for thermal imaging,[4] operating at wavelengths between 1.5–5.2 μm. It does not require cooling, but performs better at lower temperatures. The peak sensitivity depends on temperature and varies between 3.7–4.7 μm.

Single crystal nanorods and polycrystalline nanotubes of lead selenide have been synthesized via controlled organism membranes. The diameter of the nanorods were approx. 45 nm and their length was up to 1100 nm, for nanotubes the diameter was 50 nm and the length up to 2000 nm.[5]

Lead selenide nanocrystals embedded into various materials can be used as quantum dots, for example in nanocrystal solar cells.

Lead selenide is a thermoelectric material. The material was identified as a potential high temperature thermoelectric with sodium or chlorine doping by Alekseva and co-workers at the A.F. Ioffe Institute in Russia. Subsequent theoretical work at Oak Ridge National Laboratory, USA predicted that its p-type performance could equal or exceed that of the sister compound, lead telluride.[6] Several groups have since reported thermoelectric figures of merit exceeding unity, which is the characteristic of a high performance thermoelectric.[7][8][9]

The mineral clausthalite is a naturally occurring lead selenide.

It may be formed by direct reaction between its constituent elements (lead and selenium).

Infrared detection

PbSe is one of the first materials sensitive to the infrared radiation used for military applications. Early research works on the material as infrared detector were carried out during the 1930s and the first useful devices were processed by Germans, Americans and British during and just after World War II. Since then, PbSe has been commonly used as an infrared photodetector in multiple applications, from spectrometers for gas and flame detection to infrared fuzes for artillery ammunition or Passive Infrared Cueing systems (PICs).[10]

As a sensitive material to the infrared radiation, PbSe has unique and outstanding characteristics: it can detect IR radiation of wavelengths from 1.5 to 5.2 μm (mid-wave infrared window, abbreviated MWIR – in some special conditions it is possible to extend its response beyond 6 μm), it has a high detectivity at room temperature (uncooled performance), and due to its quantum nature, it also presents a very fast response, which makes this material an excellent candidate as detector of low cost high speed infrared imagers.[11]

Theory of operation

PbSe is a photoconductor material. Its detection mechanism is based on a change of conductivity of a polycrystalline thin-film of the active material when photons are incident. These photons are absorbed inside the PbSe micro-crystals causing then the promotion of electrons from the valence band to the conduction band. Even though it has been extensively studied, today the mechanisms responsible of its high detectivity at room temperature are not well understood. What is widely accepted is that the material and the polycrystalline nature of the active thin film play a key role in both the reduction of the Auger mechanism and the reduction of the dark current associated with the presence of multiple intergrain depletion regions and potential barriers inside the polycrystalline thin films.

Methods to manufacture PbSe infrared detectors

Two methods are commonly used nowadays to manufacture infrared detectors based on PbSe.

Chemical bath deposition (CBD)

CBD is the classic manufacturing method (also known as the "standard" method).[12] It was developed in USA during the '60s and is based on the precipitation of the active material on a substrate rinsed in a controlled bath with selenourea, lead acetate, potassium iodine and other compounds. CBD method has been extensively used during last decades and is still used for processing PbSe infrared detectors. Because of technological limitations associated to this method of processing, nowadays the biggest CBD PbSe detector format commercialized is a linear array of 1x256 elements.

Vapour phase deposition (VPD)

This new processing method has been recently developed in Spain.[13] It is based on the deposition of the active material by thermal evaporation, followed by specific thermal treatments. This method has an intrinsic advantage compared with the CBD method, which is the compatibility with preprocessed substrates, like silicon CMOS-technology wafers, and the possibility of processing complex detectors, such as the focal plane arrays for imagers. In fact, this has been the most important milestone in the last decades concerning the manufacturing of PbSe detectors, as it has opened the technology to the market of uncooled MWIR high-resolution imaging cameras with high frame rates and reduced costs.[14]

Main Applications of the PbSe Detectors
  • Industrial
    • Gas analysis
    • Flame analysis
    • Infrared spectroscopy
    • Industrial process and quality control:
      • Glass
      • Plastic
      • Petrochemical
      • Automotive
      • Railway
      • Coal
      • Steel
    • Hot spot detection
    • High speed infrared imaging:
    • Fire detection
    • Environmental control
  • Defense
    • Passive Infrared Cueing Systems
    • Active protection systems
    • Low cost seekers
    • Proximity fuzes
    • Sniper detection
    • Sensor Fuzed Weapons
    • DIRCM

Main manufacturers of PbSe IR detectors
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See also

References
  1. Lead selenide (PbSe) crystal structure, lattice parameters, thermal expansion. Landolt-Börnstein – Group III Condensed Matter. 41C. 1998. pp. 1–4. doi:10.1007/10681727_903. ISBN 978-3-540-64583-2.
  2. Kittel, Charles (1986). Introduction to Solid State Physics (6th ed.). New York: Wiley & Sons. ISBN 978-0-471-87474-4.
  3. Ekuma, C. E.; Singh, D. J.; Moreno, J.; Jarrell, M. (2012). "Optical properties of PbTe and PbSe". Physical Review B. 85 (8): 085205. Bibcode:2012PhRvB..85h5205E. doi:10.1103/PhysRevB.85.085205.
  4. Lawson, W. D. (1951). "A Method of Growing Single Crystals of Lead Telluride and Lead Selenide". Journal of Applied Physics. 22 (12): 1444–1447. Bibcode:1951JAP....22.1444L. doi:10.1063/1.1699890.
  5. Li, L.; Wu, Q. S.; Ding, Y. P. (2004). "Living bio-membrane bi-template route for simultaneous synthesis of lead selenide nanorods and nanotubes". Nanotechnology. 15 (12): 1877–1881. Bibcode:2004Nanot..15.1877L. doi:10.1088/0957-4484/15/12/033.
  6. Parker, D.; Singh, D. J. (2010). "High-temperature thermoelectric performance of heavily doped PbSe" (PDF). Physical Review B. 82 (3): 035204. Bibcode:2010PhRvB..82c5204P. doi:10.1103/PhysRevB.82.035204.
  7. Wang, H.; Pei, Y.; Lalonde, A. D.; Snyder, G. J. (2011). "Heavily Doped p-Type PbSe with High Thermoelectric Performance: An Alternative for PbTe". Advanced Materials. 23 (11): 1366–1370. doi:10.1002/adma.201004200. PMID 21400597.
  8. Androulakis, J.; Todorov, I.; He, J.; Chung, D. Y.; Dravid, V.; Kanatzidis, M. (2011). "Thermoelectrics from Abundant Chemical Elements: High-Performance Nanostructured PbSe–PbS". Journal of the American Chemical Society. 133 (28): 10920–10927. doi:10.1021/ja203022c. PMID 21650209.
  9. Zhang, Q.; Cao, F.; Lukas, K.; Liu, W.; Esfarjani, K.; Opeil, C.; Broido, D.; Parker, D.; Singh, D. J.; Chen, G.; Ren, Z. (2012). "Study of the Thermoelectric Properties of Lead Selenide Doped with Boron, Gallium, Indium, or Thallium" (PDF). Journal of the American Chemical Society. 134 (42): 17731–17738. doi:10.1021/ja307910u. PMID 23025440.
  10. Lowell, D.J. (1968). Some Early Lead Salt Detectors Developments. University of Michigan.
  11. Vergara, G.; et al. (2007). Polycrystalline Lead Selenide. The Resurgence of an old IR Detector. Opto Electronics Review 15.
  12. Johnson, T.H. (1965). Solutions and methods for depositing lead selenide. U.S. Patent 3.178.312.
  13. Method of Treating Polycrystalline Lead Selenide Infrared Detectors. Spanish Ministry of Defence Patent EP1852920.
  14. Vergara, G.; et al. (2011). VPD PbSe Technology fills the existing gap in uncooled, low cost and fast IR imagers. 8012. Proc. SPIE. p. 146.
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