Nanomaterials: improving gas sensor performance

John Saffell Alphasense Ltd. Technical Director jrs@alphasense.com Paul Midgley Professor of Materials Science NANOMATERIALS 2010 University of Cambridge

We will consider:
Technologies and markets for gas sensing Nanometrology Nanomaterials as catalysts Nanomaterials in optical gas sensing

Technologies and markets in gas detection

A roadmap, which includes the matrix of technologies and markets is available on: www.gas-sensor-roadmap.com

Gas detection has many markets

Market segments Domestic safety Automotive Industrial safety Process control Military Emerging markets Niche Air quality Homeland security- Explosives/ terrorism Asthma, allergies Medical Hydrogen: fuel cells Extreme environments (space, volcanoes, oil) Breath analysis & capnography Existing markets Fire and home safety Leak detection Car emissions PM10, PM2.5 Industrial safety & LEL Confined space entry Stack emissions Process control and analysis Food processing, transport and storage Breathalyser / alcohol & drugs Ammonia Benzene, BTEX Outdoor air, Indoor air Odours (WWT, landfill)

Many technologies are employed

Components Lasers and optics UV, IR, microplasma sources Wavelength separation MEMS Low cost optics, detector arrays Fibre optics Micro GC Micro MS PID, IMS QMB, SAW, BAW Sensor arrays Microprocessors/ FPGAs/ PICs/ ASIC Wireless Technologies MEMS Nanomaterials (QDs, CNT, catalysts, nano MO) Polymers, liquid crystals Electrochemistry Separation science Physical chemistry (enthalpy, speed of sound) Products NIR spectrometers IR single line absorption IMS Micro GC/MS Nanoparticle fluorescence IR, Visible, THz gas cameras Ultrasound, thermal conductivity imaging Electrochem/ optical/polymer/ nano arrays LIDAR, DOAS

Nanometrology
Electron microscopy and AFM are regular tools for both R&D and quality control

Scanning Electrochemical Microscopy, improved Raman and near field microscopy are offering new opportunities

TEM: Daresbury analysis of our Pt/Ru catalyst, identifying oxides and allowing us to determine the growth pattern
(001)
55o

(100)

(010) (011) 3nm [001]

RuO2

Ru

(i)
- 4.28 %

(100)
+12.72%

(001)

(ii)
+ 4.65 %

(100)

+12.72%

(010)

(iii)
+ 4.65 %

(001)

- 4.28%

(110)

Growth mechanism

Ru nanocrystal s at oxide surface

Pt island deposited from solution Zn grain

RuO2 deposited columnar growth

time

We also use Energy Filtered TEM to identify the surface activity of our catalysts
Oxygen Map

SEM is routinely used to quantify catalyst primary particle size distribution

14 PtBO2 12 10 8 6 4 2 0 2 4 6 8 10 12 14 16 18 20
35 30 Dart 181A

Particle Counts

Particle Counts

25 20 15 10 5 0 2 4 6 8 10 12

Particle diameter (nm)

Particle Diameter (nm)

Nanoparticles agglomerate, so primary particle size does not tell the entire story

Small 2-6 nm particles can agglomerate to Ru black large particles

5nm 100nm

Nanomaterials as catalysts
We have been using nanomaterials as catalysts for decades- they have just been rebranded as nanoparticles. With better analytical tools, we now have better control of our catalysts.

Nanomaterials for gas detection: many choices

CNTs (MW) CNTs + polymer CNTS + metal oxides CNT + metal catalysts ZnO nanowires SnO2 nano powder Tungsten oxides III-V quantum dots

Many growth/ deposition methods

CVD PVD Nanopipette: QDs, MMOs, polymers electropolymerisation (polymers) in-situ CNT growth Flame ablation

NOAH: DTI funded project to make gas sensors from quantum dots and nanorods using single component CVD
(Universities of Manchester & Keele, Alphasense, Teer, Epichem)

Molecular structure of [Et2In(OS2CNMenBu)]2

SEM image of InS nanorods

-In2S3 films grown at 375 C

TEM shows straight In2S3 nanorods with average diameter of ca. 20 nm and ca. 400500 nm in length. High-resolution TEM confirms crystallinity by indicating well-resolved (103) lattice planes. The experimental lattice spacing, 0.66 nm is consistent with the 0.62 nm separation in bulk crystals. Good deposition, but poor gas response

TEM image of InS nanorods

Flame Spray Pyrolysis

SnO2 particles generated by flame spray pyrolysis

SnO2 by flame pyrolysis shows good response and strong temperature dependence

10 ppm C2H5OH (C). The sensors with Pd/Al2O3 filter (filled symbols) and without filter (open symbols) for both undoped SnO2 (black squares) and Pd-doped SnO2 (grey circles) are measured at 50% r.h. at 25C.

Carbons
Graphite CNT (single and multiwalled) boron doped diamond glassy carbon graphene?

5nm

2nm

2nm TEM can also be used to follow a process such as ball milling of graphite

5nm

5nm

Increased ball milling increases the amorphous layer thickness

PECVD Chamber for direct growth of CNT

Graphite heater used to heat substrates (Plasma) DC Voltage -630V Temperature of Growth: 550 900oC
Gas Exposure outlet for the samples
Graphite Stage heater connected

Top View Showing samples on a graphite stage

Gas Inlet for Ammonia, Acetylene and Nitrogen Rotary Pump Connected to the bell jar

Direct Growth of Carbon Nanotubes

Novel Technique to grow CNTs direct on chip Microheater heated to grow CNTs locally on the desired area in 5mins in vacuum at 0.2mbar. MWCNTs grown locally on the small heaters , radius 12um. SWCNTs can be grown at higher temperature and thinner catalyst deposition.
Small heater with CNTs

CNTs Grown on SOI Membranes

Resistive Electrodes with CNT on SOI Membrane
Deposition for 15mins using 2nm Fe catalyst

How the CNTs will work as sensors

Gases like NO2 are electrophillic so it can remove electrons from CNTs (For SWCNTs) For MWCNTs charge transfer mechanism. CNT conductance increases and therefore the resistance of the film decreases.

Reported CNT response to NO2

Room temperature Response Time (2ppm) = 30sec, Sensitivity = ~15% F.Udrea et al , IEDM 2007, December

ZnO nanowires
Growth on microhotplate: combining MEMS and nanomaterials

Nanowire grew properly in case of resistive sensor with Al metallization (Au plated) Resistance 10 k 300 k

Nanomaterials in optical gas sensing

Quantum dots re-emit light at much longer wavelengths than excitaion wavelength- this allows us to shift LED emissions to much longer wavelengths (Trackdale) Controlled nanoparticles on surfaces give repeatable Surface Enhanced Resonant Raman Spectroscopy (SERRS) Nanoparticles can replace metal surfaces as the conducting layer for surface plasmons (SPR)

Conclusion
Improved, lower cost analytical tools (electron microscopy and AFM) bring quality control to nanomaterials Catalyst are being improved with III-V and carbon based materials now added to our catalyst choices Optics are using the unusual emission and conduction properties of nanomaterials

Acknowledgements
Paul OBrien Manchester Chemistry Rod Jones Cambridge Chemistry Nicolae Barsan University of Tuebingen Physics Bill Milne, Sumita Santra and Florin Udrea Cambridge Engineering James Covington and Julian Gardner Warwick Engineering Paul Midgeley and Cate Ducatti Cambridge Materials Science and Metallurgy Cambridge CMOS Sensors Daresbury Laboratory Technology Strategy Board (ULoGS project funding)

Thank you for your attention