Anil U. Mane
Nanocomposite Materials for
Microchannel Plate Detectors
CPAD Instrumentation Frontier Workshop 2018Brown University and Rhode Island Convention Center
Providence, Rhode Island(December 9-11, 2018)
• ALD group members
• ANL HEP Group
• CNM/ electron microscopy center
• UCB, UoC, UoHawaii, and Incom Inc.
• DOE for Funding, Contract No.“DE-AC02-06CH11357”
• DOE office of HEP and NA22
Acknowledgements
Outline
Introduction
Nanocomposites material developmento Atomic layer Deposition (ALD) method
o In-situ growth QCM studies
o Nanocomposites engineering
ALD nanocomposite application to MCPs
Summary
Microchannel Plates (MCPs)
HEP, NE, Astrophysics, and Materials Time-of-flight (ToF), mass spectrometry,
Photomultiplier tubes (PMTs)
Field emission displays, Night Vision Devices
Security Scanners, Neutron detector, SNM (U, Pu) detection
Medical imaging (PET scanners)
Airborne surveillance of moving objects, LIDAR, and 3-D topographic imaging
Microchannel Plates (MCPs)
Conventional Fabrication:– Draw lead glass fiber bundle
– Slice and polish
– Chemical etch,
– heat in hydrogen
Problems:– Expensive and need to import
– Resistance and secondary emission properties are linked
– Long conditioning process needed
– Contains lead (ES&H concerns)
– Small (1.5” diameter)
2D –Electron amplifiers
New Strategy – ALD Functionalization of Porous Glass
1) Resistive coating (ALD)
2) Emissive coating (ALD)
3) Contact electrode (PVD)
-Typically NiCr
A. Mane et. al., SPIE (2011)D. Beaulieu, et. al., Nucl. Instr. Meth. Phys. A, 633, S59, (2011)
6
Micro capillary array (MCA) Glass (Incom Inc) ALD Functionalization
Atomic Layer Deposition (ALD) method
• Precursor introduce separately in time and space
•Self-limiting material growth mechanism
Elam, Chem. Mater., Vol. 15, No. 4, 2003
e.g. 1)ALD of Al2O3 by TMA and H2O2) ALD of ZnO by DEZ and H2OExample: ALD Al2O3 using TMA-H2O
Uniform-Conformal Materials on 3D matters by ALD
AR=~10
Elam – APS/CNM Users Meeting – May 14, 2015
AlSiSE
SEM/EDXAspect ratio (AR) =
(length/width) ~ 3000
Variety of materials growth by ALD methods
Quartz Crystal Microbalance (QCM) for in-situ growth
f = -Cf mΔf - the observed frequency change, in Hz,Δm - the change in mass per unit area, in g/cm2
Cf - the sensitivity factor for the crystal used
In-situ QCM study for ALD process: E.g. ALD Al2O3
Rev. Sci. Instrum., Vol. 73, No. 8, August 2002
•Precursor introduce separately in time and space•Involved self-limiting film growth via alternate surface saturation reactions
Timings= TMA 1s—purge 5s—H2O 1s—Purge 5s
Precursor dose/purge time evaluation by QCM study
ALD Capabilities at Argonne
11
Substrate size (2”x18”), in situ QCM, QMS, FTIR, I-V
(ALD powder coater 1 kg ) 60” L x 6” dia. long tube ALD Portable ALD – in situ
synchrotron X-ray studies
12
Oxford FlexAL PEALD, 8” wafers, auto-load, in situ ellipsometry and emission spectrometry
Beneq TFS500 –3D chamber, large substrates, scale-up, batch coating (15x300mmwafers)
ALD Capabilities at Argonne
R006-20 Hz-1.07 torr
92 nmZnO
High-speed injector (20 Hz)
ALD: GaN, AlN etc.
ALD of Nanocomposites:Case study M-Al2O3 (Where M = W or Mo)
ALD of M-Al2O3 Composites (Where M = W or Mo)
• Used thermal ALD method for synthesis
• Precursors used for ALD = Al(CH3)3, H2O, WF6, MoF6, Si2H6
• Precursors properties: High vapor pressure, availability, and low cost
• ALD growth:
Growth of pure layers : W, Mo and Al2O3
Growth composite layers : W-Al2O3, and Mo-Al2O3
• Low temperature deposition processes (100-400oC)
• Process scale up for commercialization
Mane et.al., (US20130280546) Elam et.al., ECS 2013Mane et.al., (US20140220244) W. Tong et.al., APL 102 (2013) 252901Mane et.al., SPIE 2013 Mane et.al., CVD (2013) 186 Mane et.al., ECS 2014 Mane et.al., SPIE 2016
M-Al2O3 Composite Films by ALD
Adjust properties with M/(M+Al2O3) cycle ratio
Combine 2 ALD processes:
‒ Oxide -- TMA/H2O → Al2O3 : insulator, ρ=1015 Ωcm
‒ Metal -- MF6/Si2H6 → M=W, Mo : conductor, ρ=10-5 Ωcm
In-situ QCM study: @ same growth T= 200oC
ALD W
•GR=5-5.5 A/cycle
•Nanocrystalline growth
150 155 160 165 170 175 18011000
11500
12000
12500
13000
13500
14000
14500
WF6
dose
WF6
dose
Si2H
6
dose
Time(s)
Ma
ss (
ng
/cm
2)
Si2H
6
dose
W on Al2O3//Si
ALD Al2O3
• GR=1.2-1.3 A/cycle
•Amorphous growth
0 10 20 30 40 500
40
80
120
Time(s)
Ma
ss (
ng
/cm
2)
TMA
dose
TMA
dose
H2O
dose
H2O
dose
ALD Mo
• GR=10-11A/cycle
•Nanocrystalline growth
570 580 590 600 610 6203000
3500
4000
4500
5000
Si2H6
Dose
Si2H6
DoseMoF6
Dose
MoF6
Dose
Time(s)
Ma
ss(n
g/c
m2)
MoF6
Dose
Al2O3//Si Mo on Al2O3//Si
400 600 800 1000
0
1000
2000
3000
4000
5000
6000
7000
Mass
TMA Dose
H2O Dose
MoF6 Dose
Si2H6 Dose
Time(s)
Ma
ss(n
g/c
m2)
400 600 800 1000 1200 1400
0
5000
10000
15000
20000
25000
TMA dose
H2O dose
WF6 dose
Si2H
6 dose
Time (s)
Ma
ss(n
g/c
m2)
Mass
•Nucleation delay, Mass uptake and compatibility of processes
Al2O3-Mo-Al2O3Al2O3-W-Al2O3
In-situ QCM study: Materials compatibility
20%W-80%Al2O3
ALD cycles
10%Mo-90%Al2O3
ALD cycles
In-situ QCM study: W-Al2O3 and Mo-Al2O3
Reproducible and linear growth with super cycles
Nanocomposites with tunable electrical parameters
for MCPs
Nanocomposites with tunable electrical parameters
Mane et.al., CVD (2013) 186 Mane et.al., ECS 2014
Tunable resistive coatings
Room Temperature MCPs
Microstructure of composite materials
21
1-2 nm nanoparticles embedded in amorphous matrix
E.g.30%W-70%Al2O3
ALD cycles
E.g.10%Mo-90%Al2O3
ALD cycles
Composition: XPS Depth Profiling
• Al bonded with O and F, AlOxFy and W or Mo mostly in metallic state
Nanocomposites Resistivity Adjustment by
• ALD cycle method
• Nucleation role
• Precursors sequencing
• Reducing precursors
102
103
104
105
106
107
108
109
102
103
104
105
106
107
108
109
1010
Rh
o(o
hm
-cm
)
E(V/m)
D-18 (9:1)
D-25 (18:2)
D-26 (27:3)
Longitudinal measurement(on comb structures)
(a)
Resistivity trend vs. ALD cycle method9xALO: 1xMo
18xALO: 2xMo
27xALO: 3xMo
104
105
106
107
108
109
102
103
104
105
106
107
108
109
1010
Rh
o(o
hm
-cm
)
E(V/m)
D-18 (9:1)
D-25 (18:2)
D-26 (27:3)
(b)
Transverse measurementGold bottom & Hg top electrodes
All other parameters are kept constant
E.g. 10Mo -90% Al2O3
Total Number of cycles kept constant
W nucleation role on composite layer properties
25% W:75%Al2O3//Si
1:3 2:6 3:9 4:12 5:15 7:2110
2
103
104
105
106
107
108
109
Re
sis
tivity (
-cm
)
W:Al2O
3 ALD cycle ratio
1:3 2:6 3:9 4:12 5:15 7:21
2
4
6
8
10
W a
tom
ic %
W:Al2O
3 ALD cycle ratio
1:3 2:6 3:9 4:12 5:15 7:211.0
1.1
1.2
1.3
1.4
1.5
Gro
wth
ra
te (
A/c
ycle
)
W:Al2O
3 ALD cycle ratio
ALOALOALOALO W W W W W W W W W0
200
400
600
800M
ass/A
LD
cycle
(n
g/c
m2)
ALD Cycle
QCM study
Pure Al2O3
Pure W
•Growth rate, Concentration, Electrical transport follows nucleation trend
25% W:75%Al2O3//Si
25% W: 75%Al2O3//Si
All other parametersare kept constant
In-situ QCM: “Precursors sequencing”
130 140 150 160 170 180 190 200 210130 140 150 160 170 180 190 200 210
400
500
600
700
800
H2O
H2O
TM
A
H2O
TM
A
WF
6
Ma
ss (
ng
/cm
2)
Time (s)
Si 2
H6
TM
A
H2O
H2O
TM
A
Si 2
H6
WF
6
240 250 260 270 280 290 300 310
600
700
800
900
1000
240 250 260 270 280 290 300 310
Ma
ss (
ng
/cm
2)
TM
A
H2O
WF
6
Time (s)
Si 2
H6
H2O
TM
A
H2O
TM
A
Si 2
H6
WF
6
H2O
TM
A
280 290 300 310 320 330 340 350 360
600
700
800
900
1000
1100
280 290 300 310 320 330 340 350 360
TM
A
H2O
TM
A
Si 2
H6
Si 2
H6
WF
6
TM
A
TM
A
TM
A
H2O
H2O
H2O
Ma
ss (
ng
/cm
2)
Time (s)
WF
6
360 370 380 390 400 410 420 430 440
1400
1500
1600
1700
1800
1900
360 380 400 420 440
TM
A
Si 2
H6
WF
6
H2O
Ma
ss(n
g/c
m2)
TM
A
TM
A
H2O
TM
A
H2O
TM
A
H2O
WF
6
Si 2
H6
Time (s)
Layer Precursors sequence Notation Average Mass uptake (ng/cm2 /ALD cycle)
Al2O3 1x(TMA-H2O) Steady state 37
W 1x(Si2H6-WF6) Steady state 930
25:75% ALD
cycles
3xAl2O3 1xW Super cycle Total
W:Al2O3 3x(TMA-H2O)-1x(Si2H6-WF6) THSW 63 129 192
W:Al2O3 3x(TMA-H2O)-1x(WF6-Si2H6) THWS 52 136 188
W:Al2O3 3x(H2O-TMA)-1x(Si2H6-WF6) HTSW 62 87 146
W:Al2O3 3x(H2O-TMA)-1x(WF6-Si2H6) HTWS 53 89 142
26
E.g. W:Al2O3 with 25:75% ALD cycles Growth temperature = 200oC
105
106
107
108
104
105
106
107
108
109
Re
sis
tivity (
-cm
)
E(V/M)
THSW
THWS
HTWS
HTSW
Temperature coefficient of resistance (TCR) of ALD
nanocomposites
Can we control TCR through material design and engineering?
Important parameter for tunable R coatings which defines thermal runaway for devices E.g. (MEMS/NEMS, detectors, Sensors, etc.) Mane et. al, ALD 2017
Adjusting Resistivity of MCPs for various operations
• Process -1 for Around Room Temperature MCP operation• Process -2 for Low Temperature MCP operation (Liquid Ar)• Process -3 for High Temperature MCP operation
MCPs Fabrication
MCP Fabrication and Performance
• A. Mane et. al., Chem. Vap. Deposition, 19, 186–193, (2013)• A. Mane et. al., Physics Procedia, 37, 722-732 (2012)• O. Siegmund et. al. , Physics Procedia, 37, 803-810 (2012)Small form easy to functionalized by ALD
Capillary Glass Array Substrates for MCPs
• Very challenging substrate to coat for any thin film deposition method
20cm
20cm • Surface area = 8.7 m2
• Pore size = 20m• Thickness of plate=1.2mm• Aspect Ratio = 60• No. of Pores = ~80Millions• Porosity = 65%• Bias Angle = 8o
• Sensitive Surface to OH• Complex Geometry
Large Area ALD MCPs
• High Gain (>105)/mcp• Very Low Background• 10x psec time resolution• 100m spatial resolution• Excellent Stability• Short (2-3days) scrubbing time
Bare MCA ALD MCP
ALD MCPs in Photodetector
8”x8” MCP-photodetector tile
8”x8” MCPGain Map
World’s Largest MCP
Large Area ALD MCPs
• High Gain (>105)/mcp• Very Low Background• 10x psec time resolution• 100m spatial resolution• Excellent Stability• Short (2-3days) scrubbing time
Bare MCA ALD MCP
ALD MCPs in Photodetector
8”x8” MCP-photodetector tile
8”x8” MCPGain Map
World’s Largest MCP
Made in USA
Photographs of various types of ALD MCPsCurtesy : ANL, Incom Inc. UCB and LAPPD
60mmx60mm
140mm
Tested many prototype photodetectors based on ALD MCPs
33mm
6cmx6cm
10cmx10cm
20cmx20cm
2 x 3 Super-Module Mockup• Great cost saving!!! • Varity of applications
Argonne Sensor Science LLCUCB
Incom Inc
UoC
http://www.hamamatsu.com/
20cm
Used 13000 PMTs
Super-Kamioka Neutrino Detection Experiment Japan
Jiangmen Underground Neutrino Observatory (JUNO), China
(dynode type PMTs)
Using 15000 PMTs
Geometry factor, better time and special resolution Suffers image reconstruction capabilities and cost
Next generationneutrino expt.(?)
LAPPDTM
20cmx20cm
ALD-MCP technology is commercialized and products are available @ Incom Inc. MA
Publications ~200 (https://psec.uchicago.edu/)
ALD nanocomposites for Functional Components and
built-up charge quashing applications
& many more in 3D printing space…….
Next Plan :
In-situ ALD on MCP and performance testing system
• ALD Process optimization • Quick screening of high / low SEE materials• MCP performance optimization• (Gain, stability , TCR, and environmental study)
Summary
Demonstrated
• Various aspects of ALD for nanostructure materials
development and engineering
• Applications of ALD nanocomposite materials
• Process Scale up and Technology commercialization
Thank you !!
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