Physics and 30 nm

Materials Science
of Memristive
devices

Hewlett-Packard Laboratories, Palo Alto

CA

© 2005 Hewlett-Packard Development Company, L.P.

The information contained herein is subject to change without notice
People

• Jianhua Yang;
• Dmitry Strukov;
• Julien Borghetti;
• Matthew Picket;
• John Paul Stracham;
• Doug g Ohlberg;
g;
• Duncan Stewart;
• Phil Kuekes;
• Stan Williams;

2
Outline

• Memristor definition;
• Mixed conduction and memristive effect;
• Implementation;

3
History

• Memory effect in early MIM junctions (Au:SiO):

by Simmons and Verderber, Proc. Royal Society of London A, 301 (1967

1967) 77 4
 Currently….

• Stanford, U. Houston, Achen, Julich, Université Paris-

Sud Orsay,…
Sud, Orsay

• AMD, HP, IBM, Motorola, Samsung,

g Sharp…
p

5
3 fundamental circuit elements
Resistor – 1827
Georg Ohm

RESISTOR CAPACITOR
v=Ri q=Cv

Capacitor - 1745
Volta / von Kleist & van Musschenbroek
INDUCTOR
φ=Li Benjamin Franklin

Inductor – 1831
Faraday
Joseph Henry
page 6
3 fundamental circuit elements

1827 1745
v

dφ/dt = v

RESISTOR CAPACITOR
v=Ri q=Cv

i dq /dt = i q

INDUCTOR
φ=Li

φ
1831

page 7
Leon Chua 1971

1827 1745
v

dφ/dt = v

RESISTOR CAPACITOR
v=Ri q=Cv

i dq /dt = i q

INDUCTOR ?
φ=Li

φ
1831

page 8
Leon Chua 1971 – the memristor

1827 1745
v

dφ/dt = v

RESISTOR CAPACITOR
v=Ri q=Cv

i dq /dt = i q

INDUCTOR MEMRISTOR
φ=Li φ=Mq

φ
1831

L. O. Chua, “Memristor - the missing circuit element,” IEEE Trans. Circuit Theory 18, 507–519 (1971).
L. O. Chua and S. M. Kang, "Memristive devices and systems," Proc. IEEE, 64 (2), 209-23 (1976). page 9
Leon Chua 1971 – the memristor

1827 1745 Simple Memristor:

v

dφ/dt = v v = M ( w)i
dw
RESISTOR
v=Ri
CAPACITOR
q=Cv =i
dt
i dq /dt = i q

Generalized Memristor
(Memristive system):
INDUCTOR MEMRISTOR
φ=Li φ=Mq
v = M ( w, v)i
φ
1831 dw
MEMRISTIVE SYSTEMS = f ( w, i )
dt
L. O. Chua, “Memristor - the missing circuit element,” IEEE Trans. Circuit Theory 18, 507–519 (1971).
L. O. Chua and S. M. Kang, "Memristive devices and systems," Proc. IEEE, 64 (2), 209-23 (1976). page 10
Leon Chua 1971 – the memristor

1827 1745 Simple Memristor:

v

dφ/dt = v v = M ( w)i
dw
RESISTOR
v=Ri
CAPACITOR
q=Cv =i
dt
i dq /dt = i q

INDUCTOR MEMRISTOR
φ=Li φ=Mq

φ
1831
MEMRISTIVE SYSTEMS

L. O. Chua, “Memristor - the missing circuit element,” IEEE Trans. Circuit Theory 18, 507–519 (1971).
L. O. Chua and S. M. Kang, "Memristive devices and systems," Proc. IEEE, 64 (2), 209-23 (1976). page 11
Implementation

• Solid state ionic transport;

• Modulation off electronic transport;

• Dynamic electronics;

page 12
TiO2

rutile TiO2

3.0/3.2 eV semiconductor
dielectric ε ~ 80, bi-refringent
pigment, photocatalyst, O2 sensors
TiO2 : 1x Ti4+ + 2x O2-
anatase TiO2

13
TiO2-x

rutile TiO2

3.0/3.2 eV semiconductor

TiO2-x : x ~ 10-33 – 10-22

dopants all ionized Ei < 0.1 eV

oxygen vacancies VO2+ @ low T < 800C & high P(O2) and
Ti interstitials Tii4+ @ high T > 1000C & low P(O2):
creation ~ 3-5 eV
diffusion ~ 0.7 - 1.1 eV
mobility ~ 10-10 10 – 10-14
14 cm2/Vs

14
 O vacancy drift model for TiOx switch
A
⎡ ⎛ w(t ) ⎞⎤
w
dw(t ) R RON w(t )
V
doped = μV ON i (t ) w(t ) = μ V q (t ) v(t ) = ⎢ RON + ROFF ⎜1 − ⎟⎥i(t )
undoped dt L L ⎣ L ⎝ L ⎠⎦
3 v
L time (×10 )
0.0 0.1 0.2 0.3 0.4 0.5 0.6

dφ/dt = v
current (×10
1.0 10
0.5
voltage

RESISTOR CAPACITOR
5 v=Ri q=Cv
00
0.0 0

(
-0.5 -5 dq /dt = i
i q
-1.0 -10

-3
)
1.0
w/L

0.5 INDUCTOR MEMRISTOR

φ=Li φ=Mq

0.0
φ
0.0 0.1 0.2 0.3 0.4 0.5 0.6
3 MEMRISTIVE SYSTEMS
time (×10 )

10 0.6
0 6
charge
e

0.4
urrent (×10 )

0.2
-3

5
0.0
0 50
0 flux

-5
cu

-10

-1.0 -0.5 0.0 0.5 1.0

voltage page 15
 O vacancy drift model for TiOx switch
A
⎡ ⎛ w(t ) ⎞⎤
w
dw(t ) R RON w(t )
V
doped = μV ON i (t ) w(t ) = μ V q (t ) v(t ) = ⎢ RON + ROFF ⎜1 − ⎟⎥i(t )
undoped dt L L ⎣ L ⎝ L ⎠⎦
3 v
L time (×10 )
0.0 0.1 0.2 0.3 0.4 0.5 0.6

dφ/dt = v
current (×10
1.0 10
0.5
voltage

RESISTOR CAPACITOR
5 v=Ri q=Cv
00
0.0 0

(
-0.5 -5 dq /dt = i
i q
-1.0 -10

-3
)
1.0
w/L

0.5 INDUCTOR MEMRISTOR

φ=Li φ=Mq

0.0
φ
0.0 0.1 0.2 0.3 0.4 0.5 0.6
3 MEMRISTIVE SYSTEMS
time (×10 )

Generalized Memristor
10 0.6
0 6
charge
e

0.4 (Memristive system):

urrent (×10 )

0.2
-3

v = M ( w, v)i
5
0.0
0 50
0 flux

-5 dw
cu

-10 = f ( w, i )
-1.0 -0.5 0.0 0.5 1.0
dt
voltage page 16
O vacancy drift model for TiOx switch
w A
V
doped
undoped

3
time (×10 )
0.0 0.4 0.8 1.2 1.6
1 1.0
v o lta g e

w /L
0 0.5

-11 0.0
0.0 0.4 0.8 1.2 1.6
1.0 R /R = 50
OFF ON
0.5 v0 = 4 V
c u rre n t

0.0
-0.5
-1.0
10
-1.0 -0.5 0.0 0.5 1.0
voltage
page 17
O vacancy drift model for TiOx switch
w A
V
doped
undoped

3
time (×10 ) 4
0.0 0.4 0.8 1.2 1.6 7
1 1.0 4 Pt Expt Pt Expt 6
Ti Ti
v o lta g e

5
w /L

0 0.5 Pt 2
Pt 4
2 32
-1 0.0 1

C u rre n t (m A )
C u rre n t (m A )

0.0 0.4 0.8 1.2 1.6

0 0
1.0 R /R = 50
OFF ON
17
0.5 v0 = 4 V
c u rre n t

-2
-2 10
0.0
9
-0.5
05 -4 8
-1.0 -4
-1.0 -0.5 0.0 0.5 1.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5
Voltage (V)
voltage Voltage (V)

Dmitri Strukov, Greg Snider,

Duncan Stewart, R. Stanley Williams,
Nature 453, 80 - 83 (01 May 2008) page 18
Device operation

• Electroforming and bubbling

• Endurance;;

• Interface effects;

• Scalability;
page 19
O2 reduction at anode creates bubbles
in micron-sized
micron sized devices

20
O2 bubble movie

click for movie

21
Electroforming can induce O2 reduction
at anode

Anode ≡
Cathode (-) Anode (+) Where oxidation occurs

2e-
½ O2
TiO2+
Oxygen is oxidized from
2- to 0 charge
TiO2

E
22
Electroforming can induce O2 reduction
at anode

Cathode (-) Anode (+)

TiO2+ O2
TiO2+
2
2+ O
TiO O2 2
TiO2+ O2
TiO2+ O2
O2
TiO2 bubble

E
23
Nano-devices do NOT show bubbles

Micron-sized Nano-sized
30
15
m)
Z (nm

15

Z (nm)
10
0
0 4000 8000
X (nm)
5

0
TE 100 200
X (nm)

BE

BE

100
Z (nm)

50

0
4000 8000
X (nm)

TE

TE
BE

24
Endurance: 200-400 traces on 50
nanometer
a o ete Pt/TiOx/Pt
t/ O / t devices
de ces

200
Pt a c +V push
OV vacancies
i
Switching I-V
TiOx
100
TiO2

C urrent ( uA )
-V attract
50 nm hp OV vacancies
Pt 0
b 4
-3
3
Pt
C urrent ( nA )

10
TiO2
+
2 V -6
TiOx - -100 10
Pt
-9
0 10
Vi i II-V
Virgin V -1
1 0 1

-2 -1 0 1 2 -200-2 -1 0 1 2
Voltage ( V ) Voltage ( V )

25
Role of interface: Devices on
Single
g crystal
y TiO2 Preparation
p
Create Vo2+ by annealing
Single crystal TiO2 rutile
was annealed at 700 oC
in N2/H2 for 2hrs;
TiO2 bulk crystal, Rutile

Create more Vo2+

2 locally by Ti

Pt
1 2 Ti
3 4
Ti+TiO2=>TiO2-x creating Vo2+

TiO2 bulk crystal

Many two-terminal permutations (devices)

I3-4

2 3 +
1 Pt Pt 4 V
-
Pt Ti Ti Pt
TiO2

TiO2-X

J. Joshua Yang 26
Role of interface
I2-3

V Pt
2 3 -
1
1
Pt Pt 4 TiO2
Pt Ti Ti Pt
3 Ti
TiO2
Pt
TiO2-X

w
w
Φb TiO2-X
Φb

Pt TiO2
Ti TiO2

J. Joshua Yang 27
Role of interface: I-V curves
I2-3
+
10 2-3

Current (mA)
2 3 V
-
1 Pt Pt 4
0
Pt Ti Ti Pt Pt 2
TiO2 Ti
TiO2-x
TiO2-X Ti
-10
10 Pt 3
• identical contacts Æ Symmetric I-V;
• 5nmTi/TiO2ÆOhmic contacts (Pads 2,3);
-0.4 0.0 0.4
• The single crystal TiO2 is very conductive;
Voltage (V)
I1-4
+
2 3 V
- 500 1- 4

Currentt (nA)
1 Pt Pt 4
Pt Ti Ti Pt
TiO2 0
TiO2-X Pt 1
- 500 TiO2-x
Pt 4
• identical contacts Æ Symmetric I-V;
• Pt/TiO2ÆSchottky contact (pads 1,4);
• Interfaces dominates the I-V (bulk TiO2 contact). - 0.4 0. 0 0.4
V oltag e ( V)
J. Joshua Yang 28
Role of interface: I-V curves
I2-4
0
2 3 + 2 4 G nd
2-

urrent (μA)
1 Pt Pt 4 V
-
Pt Ti Ti Pt
TiO2
- 200 2 Pt
Ti
TiO2-x
TiO2-X

Cu
4 Pt

- 400
I2-3 - 0.4 0 0. 4
+ V oltag e ( V)
V
2 3 - 400 1-3 G n d
μA)
1 Pt Pt 4
Current (μ 1 Pt
Pt Ti Ti Pt
TiO2 200 TiO2-x
Ti
3 Pt
TiO2-X

0
- 0.4 0. 0 0. 4
J. Joshua Yang V oltag e ( V) 29
Scalability: from micron- to nano-
p
crosspoint jjunctions
5x5 micronmeter2 50x50 nanometer2

Pt
10~100nm
A
V TiO2-x
50 nm
500μm
Pt half-pitch
HP Labs

20
OFF 200
-3 OFF
10 -5
5
10
-5
10
10
• Large on/off
-7
10
-7 100
10
ratio (~103)
Current (mA)

-9
10

Currentt ( uA )
-3 -2 -1 0 1 -2.0 -1.0 0.0 1.0

0 • Low power,
power 0

(~10 pJ/b)
ON
-10
• Fast (<50ns) -100
ON
• Bi-polar
Bi polar
-3 -2 -1 0 1 2 -200
Voltage (V) • Non-volatile -2 -1 0
Voltage ( V )
1 2

J. Joshua Yang 30
Conclusions

• Dynamic electronics opens up a new

class of devices, that can be configured
in real time;

• New
applications can be found in
memory, signal conditioning, etc.

page 31
• The end

page 32
Switching features: localized or
uniform
Question: Is pad 4 uniformly or locally changed?!

I2-4
V 4
2 3
2-4
1

Current (mA)
Pt Pt 41 42
Pt Ti Ti 2 2-41
TiO2

TiO2-X

0
2-42

-2
-1 0 1
Voltage (V)

3. Localized channels

J. Joshua Yang 33