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 behind
the 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 OF
MEMRISTOR (1971)
ICNAAM-2012

3.

PRINCIPLE OF OPERATION OF TiO2 MEMRISTOR
(STAN WILLIAMS, HP LABS, 2012)
ICNAAM-2012

4.

TYPES OF MEMRISTORS
BESIDES MEMRISTORS THERE ARE NOW MEMCAPACITORS AND MEMINDUCTORS!
ICNAAM-2012

5.

NEUROMORPHIC COMPUTERS – PROJECT SYNAPSE - DARPA
von 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
ICNAAM-2012
Neuromorphic
Machines
[log]

6.

NEUROMORPHIC COMPUTING ROADMAP
ICNAAM-2012

7.

PANi BASED MEMRISTOR – EROKHIN, FONTANA - 2008
ICNAAM-2012
Ionic current
Electronic current

8.

FIRST ATTEMPTS TO INTERPRET PANi MEMRISTOR
OPERATION MECHANISM – EROKHIN, 2013
ICNAAM-2012

9.

SET OF 8 PANi BASED MEMRISTORS ON FLEXIBLE SUBSTRATE
Simple learning procedure
ICNAAM-2012
Out 1 (nA)
Out 2 (nA)
Before training
120
32
After training
65
124

10.

RED-OX STATES OF PANi AND ELECTROCHEMICAL
TRANSITIONS BETWEEN THEM
ICNAAM-2012

11.

MEASUREMENT SET UP AND EXPERIMENTAL PROCEDURE
Electrochemical
potentiostat
Measured film
Solution
HCl/LiClO4
acetonytile,
water
ICNAAM-2012
ITO glasses

12.

PANi IN SOLUTION OF LiClO4/HCl CYCLOVOLTAMMETRY
Red – Ox peaks are very broad, it is important
Cyclovoltammogramm in 0.1 M
HCl in water
ICNAAM-2012
Cyclovoltammogramm in 0.1 M
LiClO4 in acetonytrile

13. ELECTROCHROMIC CYCLOVOLTAMMOGRAMM

ICNAAM-2012

14. SPECTROELECTROCHEMISTRY MEASUREMENTS

0.8 V
0.7 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
ICNAAM-2012
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

-0.0015277099609375
0,012
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
ICNAAM-2012
0,8

17.

MEMRISTIVITY: RESISTANCE AFTER SWITCH OFF VOLTAGE
Cyclovoltammogramm
±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.
ICNAAM-2012

18.

RESISTANCE IN PLANE, DRY FILM – AC CONDUCTIVITY
Resistance
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
ICNAAM-2012
800

19. MEMRISTIVE EFFECT MOVIE

ICNAAM-2012

20.

BLOCK NATURE OF CONDUCTIVITY IN PANi
– EXPLANATION OF MEMRISTANCE
ICNAAM-2012

21.

PROPAGATION OF RED-OX FRONTS IN PANi
AS A BASIS FOR NEURAL NETWORKS
ICNAAM-2012

22.

USE OF PANi NEURAL NETWORK FOR IMAGE PROCESSING
Image processing operations
possible:
1.Image segmentation
2.Contrasting
3.Simple object recognition
ICNAAM-2012

23.

PANi-NAFION INTERPOLYELECTROLYTE COMPLEXES
Fluoropolymer
base
H
N
H
N
N
H
*
*
Зеленая
эмеральдиновая
Green emeraldine
salt соль
+2e
*
N
H
H
N
N
H
Colourlessлейкоэмеральдин
leucoemeraldine
Бесцветный
ICNAAM-2012
*

24.

PANi-NAFION IN SOLUTIONS OF LiClO4, Acetonytrile
0,0020
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
ICNAAM-2012
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
ICNAAM-2012

26.

Protonated PANi
Deprotonated PANi
- H+
Ef
Built-in field
-- + +
- h h h+
+
+
- h h h+
Holes
Hot end
ICNAAM-2012
holes
Thermo-emf
+
Protons
thermodifusion
+
+ + +
+ +
+ -
Protons
Cold end

27.

Power vs. temp difference
0,6000
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
ICNAAM-2012
40
50
60

28.

Voltage vs temp difference, C
2,5
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
ICNAAM-2012
40
50
60

29. Stability at 55oC

ICNAAM-2012

30. Discharge to short circuit

ICNAAM-2012

31. Discharge to 3 Ohm

ICNAAM-2012

32. I-V curve at 40 C

ICNAAM-2012

33. Impedance at 40 C

ICNAAM-2012

34. Results of approximation of equivalent circuit

ICNAAM-2012

35.

мА
c
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
ICNAAM-2012
1
2
3
4