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Resistive switch Red-Ox behavior as mechanism behind the operation of polyaniline memristors and neural network elements
1.
Resistive switch Red-Ox behavior as mechanism behindthe operation of polyaniline memristors and neural
network elements and PANI-based thermolectrochemical
cells
O.Bogomolova1 , J.Boeva1, V.Sergeyev1, D.Godovsky2
1 Moscow State University, Chemistry Dept., Vorobievy Gory, 1 Moscow
2 INEOS RAS, Vavilova str, 28, Moscow
Also at LG TCM, LG Electronics, Moscow, Paveletskaya, 2/3
ICNAAM-2012
2.
LEON CHUA THEORY BEHIND THE OPERATION OFMEMRISTOR (1971)
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3.
PRINCIPLE OF OPERATION OF TiO2 MEMRISTOR(STAN WILLIAMS, HP LABS, 2012)
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4.
TYPES OF MEMRISTORSBESIDES MEMRISTORS THERE ARE NOW MEMCAPACITORS AND MEMINDUCTORS!
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5.
NEUROMORPHIC COMPUTERS – PROJECT SYNAPSE - DARPAvon Neumann
Machines
[log]
A trade between
universality and
efficiency
Machine
Complexity
e.g. Gates;
Memory;
Neurons;
Synapses
Power;
Size
• Human level performance
• Dawn of a new age
Dawn of a new
paradigm
Program Objective
“complex”
“simple”
Environmental Complexity
e.g. Input Combinatorics
Axonic electrode
Dendritic electrode
Crossbar synapse
Soma
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Neuromorphic
Machines
[log]
6.
NEUROMORPHIC COMPUTING ROADMAPICNAAM-2012
7.
PANi BASED MEMRISTOR – EROKHIN, FONTANA - 2008ICNAAM-2012
Ionic current
Electronic current
8.
FIRST ATTEMPTS TO INTERPRET PANi MEMRISTOROPERATION MECHANISM – EROKHIN, 2013
ICNAAM-2012
9.
SET OF 8 PANi BASED MEMRISTORS ON FLEXIBLE SUBSTRATESimple learning procedure
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Out 1 (nA)
Out 2 (nA)
Before training
120
32
After training
65
124
10.
RED-OX STATES OF PANi AND ELECTROCHEMICALTRANSITIONS BETWEEN THEM
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11.
MEASUREMENT SET UP AND EXPERIMENTAL PROCEDUREElectrochemical
potentiostat
Measured film
Solution
HCl/LiClO4
acetonytile,
water
ICNAAM-2012
ITO glasses
12.
PANi IN SOLUTION OF LiClO4/HCl CYCLOVOLTAMMETRYRed – Ox peaks are very broad, it is important
Cyclovoltammogramm in 0.1 M
HCl in water
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Cyclovoltammogramm in 0.1 M
LiClO4 in acetonytrile
13. ELECTROCHROMIC CYCLOVOLTAMMOGRAMM
ICNAAM-201214. SPECTROELECTROCHEMISTRY MEASUREMENTS
0.8 V0.7 V
0.6 V
0.5 V
0.4 V
0.3 V
0.2 V
0.1 V
0,8
0,8
0,6
0,4
I1
Absorbance
0,6
0.4 V back
0.5 V back
0.6 V back
0.7 V
0.5 V
0.3 V
0.1 V
1,0
0,4
0,2
0,2
0,0
0,0
400
500
600
700
800
900
Wavelength, nm
PANi film versus Ag/AgCl, 0.1 M HCl Water
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400
600
800
1000
Wavelenght, nm
Backwards, with memristive effect on
absorbance spectra
15.
MEMRISTIVE EFFECT IN_PLANE CONDUCTANCE (I-V CURVES)ICNAAM-2012
16. PANI FILM-THROUGH CONDUCTIVITY MEASUREMENT
-0.00152770996093750,012
Max I = 0.01 A
0,010
0,008
Current, Amp
0,006
0,004
0,002
0,000
-0,002
-0,004
-0,006
-0,2
0,0
0,2
0,4
0,6
Voltage, V
PANi film conductivity, 0.1M HCl water,
Ag/AgCl
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0,8
17.
MEMRISTIVITY: RESISTANCE AFTER SWITCH OFF VOLTAGECyclovoltammogramm
±2V
Supplied again
700mV
Switch off at 700 mV
Device is switched off here
I,
mA
Time,sec
Memristive effect as from voltage switch off/ switch on.
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18.
RESISTANCE IN PLANE, DRY FILM – AC CONDUCTIVITYResistance
Polarization potential
700
3000
500
2000
400
1500
300
1000
200
3000
2500
500
100
0
0
20
40
60
80
100
120
140
160
180
200
Approx. time / min
Bias voltage – 0, amplitude – 5 mV
Resistance / Ohm
Resistance/ Ohm
600
2500
Polarization potential / mV
800
3500
2000
1500
1000
500
0
0
200
400
600
Polarization potential / mV
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800
19. MEMRISTIVE EFFECT MOVIE
ICNAAM-201220.
BLOCK NATURE OF CONDUCTIVITY IN PANi– EXPLANATION OF MEMRISTANCE
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21.
PROPAGATION OF RED-OX FRONTS IN PANiAS A BASIS FOR NEURAL NETWORKS
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22.
USE OF PANi NEURAL NETWORK FOR IMAGE PROCESSINGImage processing operations
possible:
1.Image segmentation
2.Contrasting
3.Simple object recognition
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23.
PANi-NAFION INTERPOLYELECTROLYTE COMPLEXESFluoropolymer
base
H
N
H
N
N
H
*
*
Зеленая
эмеральдиновая
Green emeraldine
salt соль
+2e
*
N
H
H
N
N
H
Colourlessлейкоэмеральдин
leucoemeraldine
Бесцветный
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*
24.
PANi-NAFION IN SOLUTIONS OF LiClO4, Acetonytrile0,0020
500
0,0015
400
Absorbance, a.u.
Current,A
0,0010
0,0005
0,0000
-0,0005
-0,0010
300
200
100
0
-0,0015
-1,0
-0,5
0,0
0,5
1,0
1,5
2,0
Voltage, V against Ag/AgCl
Cyclovoltammogramm in 0.1MLiClO4,
acetonytrile, versus Ag/AgCl
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100
200
300
400
500
600
700
800
900
Wavelength, nm
Absorbance spectra of films during
cyclovoltammetry
25. CONCLUSIONS
• Polymer electrochemistry is a complicated matter• Polyaniline-based memristor operating mechanism is
determined by change of Red-Ox states of PANi
• Probably TiO2, VOx memristors operation is similar.
• It is not clear why PANi-Nafion films do not change Red-Ox
states
• It is possible to make simple neural networks based on PANi
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26.
Protonated PANiDeprotonated PANi
- H+
Ef
Built-in field
-- + +
- h h h+
+
+
- h h h+
Holes
Hot end
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holes
Thermo-emf
+
Protons
thermodifusion
+
+ + +
+ +
+ -
Protons
Cold end
27.
Power vs. temp difference0,6000
0,5291
0,5161
0,5000
Power output, W
0,4000
0,3691
0,3000
0,2831
Ряд1
0,2000
0,1450
0,1000
0,0442
0,0000
0,0000
0,0070
0
10
20
30
Temperature difference, C
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40
50
60
28.
Voltage vs temp difference, C2,5
2,13
2,1
2,085
2
Voltage, V
1,784
1,733
1,554
1,5
1,099
1
Ряд1
0,603
0,5
0,237
0
0,0039
0
10
20
30
Temp.difference, C
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40
50
60
29. Stability at 55oC
ICNAAM-201230. Discharge to short circuit
ICNAAM-201231. Discharge to 3 Ohm
ICNAAM-201232. I-V curve at 40 C
ICNAAM-201233. Impedance at 40 C
ICNAAM-201234. Results of approximation of equivalent circuit
ICNAAM-201235.
мАc
0,18
0,16
0,14
0,12
0,12
0,1
0,1
0,08
мА
0,06
0,06
0,04
c
0,04
0,02
0,02
0
-0,02 0
0,08
0,5
1
1,5
2
2,5
3
3,5
0
0
-0,02
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