novel precipitation method for producing dispersed
TRANSCRIPT
Novel Precipitation Method for Producing Novel Precipitation Method for Producing Dispersed Crystalline Copper PowdersDispersed Crystalline Copper Powders
for Electronic Applicationsfor Electronic Applications
I. Halaciuga, S. LaPlante, and D.V. GoiaClarkson University, Potsdam NY
CARTS USA 2009, The Passive Components Symposium and Exhibition
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FundingAdvisors:Prof. Dan V. Goia (Chemistry)Prof. Vladimir Privman (Physics)
Collaborators (students / postdocs):Dr. D.T. Robb (Berry College - GA)Dr. D. AndreescuDr. M. Jitianu (Rutgers University)Dr. R.K. Roy (Indian association for the cultivation of science)C. GoiaS. Chevalliot (University of Cincinnati)S. Reiche (Max Planck Institute - Berlin)D. Le (University of North Carolina at Chapel Hill)I. SevonkaevB. FarrellK. BalantrapuB. MorrowS. LaPlanteL. LuN. PorterW. Olson (General Electric)G. Burkey
www.clarkson.edu/programs/goia_group
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Instrumentation:
• SEM / FE-SEM• HRTEM / STEM• Particle sizing – Laser diffraction
– Dynamic light scattering• BET surface area and pore analyzer• Thermogravimetric analyzer (TGA)• Thermomechanical analyzer (TMA)• UV-Vis spectrophotometer• Powder X-ray diffraction analyzer• Zeta potential analyzer• Energy dispersive X – ray spectroscopy (EDX)• Inkjet printer• Profilometer• Viscometer• Attritor / mixers
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Why colloids?
– Colloid from “Kolla, Kolloid” – glue in ancient Greek.– Mixture where one component (e.g. particles) is dispersed evenly throughout another (e.g. solution).
e.g. milk, paint, ink, cosmetics, blood, smoke, styrofoam, mist, etc.
Why metal particles?
• Electronics• Catalysis• Metallurgy• Pigments• Medicine & Biology• Transparent conductive coatings• High density storage• Obscurant smokes
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Typical preparation approaches:
Phase break Phase break –– downdown- milling / grinding- atomization
Phase transformationPhase transformation- pirolysis / thermolysis- reduction
Phase build Phase build –– upup- condensation in gas phase- condensation in liquid phase
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CLUSTERS
METAL IONS / COMPLEXES
METAL ATOMS
Reduction
NANOSIZEPRIMARY PARTICLES
Diffusional growthNUCLEI (~8-10Å)
POLYCRYSTALLINEPARTICLES
CRYSTALLINEPARTICLES
Diffusional growth Aggregation
STABLENANOSYSTEMS
Me n+ + Red m- ⇔ Me0 + Ox m-n
ΔE0 = E01 - E0
2
ΔG0 = -nFΔE0
D. V. Goia: Preparation and formation mechanisms of uniform metallic particles in homogeneous solutionsJ. Mater. Chem. 14, 2004. pp. 451-458
Chemical precipitation:
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Properties of metal particles:
• Size and size distribution• Dispersion• Internal structure (crystalline, polycrystalline)• Internal composition • Morphology• Surface properties
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Wet film
Dry film
Sintered film
Drying
“Burn-out”
Sintering
“Clean” film
Industrial Applications:•MLCC
•Resistors
•Solar Cells / Panels
•Plastic Electronics
•Radio Frequency I.D. Tags
•Displays
Paste Deposition:•flexography•spin coating
•screen printing•ink-jet printing
Preparation of metallic layers via thick – film technology
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Fe(II) – citrate
complex
CuCl
dispersion
Simple, cheap, ‘clean’ method< 30$ / 1 Kg pure Copper
- Patented by E.I. DuPont de Nemours and Company
Synthesis of Cu particles
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0.01 0.1 1 10 100 1000 100000
2
4
6
8
10
12
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Vol
ume
(%)
Size (μm)
D (0.5) = 2.2 μm
Degree of dispersion (PSD)
Tap density > 3.5 g/cc
- Patented by E.I. DuPont de Nemours and Company
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Crystallinity (XRD)
30 40 50 60 70 80 90 100
1000
2000
3000
4000
5000
Inte
nsity
(a.u
.)
2 theta (degrees)
88 90 92
200
400
600
800
1000
Inte
nsity
(a.u
.)
2 theta (degrees)
24nm60
42nm20
Crystallite sizeTemperature ( oC)
- Patented by E.I. DuPont de Nemours and Company
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100 200 300 400 500 600 70098.0
98.5
99.0
99.5
100.0
100.5
101.0
101.5
102.0
Wei
ght (
%)
Temperature (oC)
Δ = ~ 0.49 %
0 200 400 600 800
100
105
110
115
120
125
Δ=24.36%
Wei
ght (
%)
Temperature (oC)
Purity and oxidation
in 5%H2 / 95%N2 in air
- Patented by E.I. DuPont de Nemours and Company
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Sintering of Cu particles
100 200 300 400 500 600 700 800 900-10
-8
-6
-4
-2
0
2
4
6
8
10
D
imen
sion
Cha
nge
(%)
Temperature (oC)
Commercial powder Precipitated powder
- Patented by E.I. DuPont de Nemours and Company
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Conclusions
Chemical precipitation is a versatile technique, offering many ways to control synthetic processes.
Understanding the mechanisms and parameters controlling the formation of metallic particles offers the capability to yield dispersed uniform Cu particles with controlled morphology.
The particle size is varied in a broad range (0.3 to 1.5 µm) without altering their uniformity and dispersity.
The simplicity of the process and the high concentration of metal make the described process an advantageous route to manufacture cost effectively in large scale dispersed copper particles for applications in electronic industry.
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FundingAdvisors:Prof. Dan V. Goia (Chemistry)Prof. Vladimir Privman (Physics)
Collaborators (students / postdocs):Dr. D.T. Robb (Berry College - GA)Dr. D. AndreescuDr. M. Jitianu (Rutgers University)Dr. R.K. Roy (Indian association for the cultivation of science)C. GoiaS. Chevalliot (University of Cincinnati)S. Reiche (Max Planck Institute - Berlin)D. Le (University of North Carolina at Chapel Hill)I. SevonkaevB. FarrellK. BalantrapuB. MorrowS. LaPlanteL. LuN. PorterW. Olson (General Electric)G. Burkey
www.clarkson.edu/programs/goia_group