Enhancement of hydrogen sulfide gas sensing of PbS colloidal quantum dots by remote doping through ligand exchange

Abstract Colloidal quantum dots (CQDs) are solution-synthesized semiconductor nanocrystals with size typically below 10 nm. Their large surface-to-volume ratio and abundant active surface sites, combined with the grain size effect and solution-processability make CQDs promising building blocks for low-cost and high-performance gas sensors. Here we employed the ligand exchange strategy to develop low-power and highly sensitive H 2 S gas sensors based on PbS CQDs. Following the layer-by-layer spin-coating of PbS CQDs capped with long-chain oleic acid ligands from synthesis, a surface treatment using different inorganic salts was conducted for ligand exchange in air ambient at room temperature. Upon exposure to 50 ppm of H 2 S at 135 °C, the resistance of all those sensors decreased shown as the response and the Pb(NO 3 ) 2 treatment yielded highest response (4218 at 135 °C) with shortest response/recovery time. We tentatively proposed a H 2 S-induced and temperature-promoted p-to-n transition of PbS CQDs as the sensing mechanism and the role of Pb(NO 3 ) 2 treatment was attributed to an n-type remote doping effect realized by the ligand exchange, which was further supported by the energy dispersive spectrometry (EDS) and ultraviolet photoelectron spectroscopy (UPS) analysis.

[1]  G. Zou,et al.  Resonant tunneling modulation in quasi-2D Cu2O/SnO2 p-n horizontal-multi-layer heterostructure for room temperature H2S sensor application , 2013, Scientific Reports.

[2]  Aram Amassian,et al.  Air-stable n-type colloidal quantum dot solids. , 2014, Nature materials.

[3]  William Mickelson,et al.  Low-power, fast, selective nanoparticle-based hydrogen sulfide gas sensor , 2012 .

[4]  Sunghoon Park,et al.  H2S gas sensing properties of CuO-functionalized WO3 nanowires , 2014 .

[5]  Jing‐Juan Xu,et al.  In situ activation of CdS electrochemiluminescence film and its application in H₂S detection. , 2014, Analytical chemistry.

[6]  Dongxiang Zhou,et al.  Properties and mechanism study of SnO2 nanocrystals for H2S thick-film sensors , 2009 .

[7]  Adisorn Tuantranont,et al.  H2S sensor based on SnO2 nanostructured film prepared by high current heating , 2014 .

[8]  M. Bangar,et al.  Polyaniline nanowires-gold nanoparticles hybrid network based chemiresistive hydrogen sulfide sensor , 2009 .

[9]  O. Voznyy,et al.  N‐Type Colloidal‐Quantum‐Dot Solids for Photovoltaics , 2012, Advanced materials.

[10]  R. Ruoff,et al.  All-organic vapor sensor using inkjet-printed reduced graphene oxide. , 2010, Angewandte Chemie.

[11]  Philippe Guyot-Sionnest,et al.  n-type colloidal semiconductor nanocrystals , 2000, Nature.

[12]  V. Bulović,et al.  Emergence of colloidal quantum-dot light-emitting technologies , 2012, Nature Photonics.

[13]  Yadong Yin,et al.  Colloidal nanocrystal synthesis and the organic–inorganic interface , 2005, Nature.

[14]  N. Bârsan,et al.  Conduction Model of Metal Oxide Gas Sensors , 2001 .

[15]  A Paul Alivisatos,et al.  Photovoltaic devices employing ternary PbSxSe1-x nanocrystals. , 2009, Nano letters.

[16]  G. Morell,et al.  Room temperature gas sensor based on tin dioxide-carbon nanotubes composite films , 2014 .

[17]  Jiang Tang,et al.  Resistive gas sensors based on colloidal quantum dot (CQD) solids for hydrogen sulfide detection , 2015 .

[18]  Il-Doo Kim,et al.  Selective detection of acetone and hydrogen sulfide for the diagnosis of diabetes and halitosis using SnO(2) nanofibers functionalized with reduced graphene oxide nanosheets. , 2014, ACS applied materials & interfaces.

[19]  D. K. Aswal,et al.  Kelvin probe studies of H2S exposed CuO:ZnO nanowires random networks , 2013 .

[20]  N. Hoa,et al.  Giant enhancement of H2S gas response by decorating n-type SnO2 nanowires with p-type NiO nanoparticles , 2012 .

[21]  M. Kovalenko,et al.  Prospects of colloidal nanocrystals for electronic and optoelectronic applications. , 2010, Chemical reviews.

[22]  Aram Amassian,et al.  Colloidal-quantum-dot photovoltaics using atomic-ligand passivation. , 2011, Nature materials.

[23]  Transduction in Semiconducting Metal Oxide Based Gas Sensors - Implications of the Conduction Mechanism , 2011 .

[24]  Lili Xing,et al.  Core–Shell In2O3/ZnO Nanoarray Nanogenerator as a Self-Powered Active Gas Sensor with High H2S Sensitivity and Selectivity at Room Temperature , 2014 .

[25]  Edward H. Sargent,et al.  Impact of dithiol treatment and air annealing on the conductivity, mobility, and hole density in PbS colloidal quantum dot solids , 2008 .

[26]  Nicolae Barsan,et al.  A p- to n-transition on α-Fe2O3-based thick film sensors studied by conductance and work function change measurements , 2004 .

[27]  Philippe Guyot-Sionnest,et al.  n-Type Conducting CdSe Nanocrystal Solids , 2003, Science.

[28]  Larissa Levina,et al.  Quantum junction solar cells. , 2012, Nano letters.

[29]  Dongxiang Zhou,et al.  Physically Flexible, Rapid‐Response Gas Sensor Based on Colloidal Quantum Dot Solids , 2014, Advanced materials.

[30]  Dongxiang Zhou,et al.  Tin oxide films for nitrogen dioxide gas detection at low temperatures , 2013 .