2D FETs with MoS2, WSe2, and black

phosphorous toward practical electronics

Seongil Im

E-mail: [email protected]
Lab. Website: Http://edlab.yonsei.ac.kr
 Introduction
The most widely studied 2-D material
Conical Dirac spectrum
Energy states without a bandgap
High mobility (< 100000cm2/Vs)
More conductive than copper
Attractive optical phenomena

More Flexible than rubber

Stretchable material
Stronger than diamond
Various formation (ribbon, tube, ball...)

K. S. Kim Nature 457, 706 (2009) K. S. Novoselov et al.Science 306, 666 (2004)

Limitation of Graphene
Gapless Band Structure → Unsuitable for switching devices
Transition Metal Dichalcogenides

Transition Metal Dichalcogenides (MX2)

Similar storyline of the graphene family
2D and layered (thin-film) structures
Covalently bonded X-M-X
held together by Van der Waals interactions
Broken symmetry in atomic basis

can make Band Gap of ~ 1 eV M. Chhowala et al. Nature Chem. 5, 263 (2013)

-S2 -Se2 -Te2

Nb Metal Metal Metal
Ta Metal Metal Metal
Semiconducting Semiconducting Semiconducting
Mo (1L : 1.8eV, Bulk : 1.2eV) (1L : 1.5eV, Bulk : 1.1eV) (1L : 1.1eV, Bulk : 1.0eV)
Semiconducting Semiconducting Semiconducting
W (1L : 1.9eV, Bulk : 1.4eV) (1L : 1.7eV, Bulk : 1.2eV) (1L : 1.1eV)
modified version of Q. H. Wang et al. Nature Nanotech. 7, 699 (2012)
Recent Progress on 2D Nanosheet
in World Researches
FET –countless many reports (e.g. A. Kis in Nat Nano. 2011)
1. Field-Effect Transistors Built from All Two-Dimensional Material Components, ACS Nano, 8, 6259 (2014)
2. Impact of Contact on the Operation and Performance of Back-Gated Monolayer MoS2 Field-Effect-Transistors, ACS Nano, 9, 7904 (2015)
3. Highly Stable, Dual-Gated MoS2 Transistors Encapsulated by Hexagonal Boron Nitride with Gate-Controllable Contact, Resistance,
and Threshold Voltage, ACS Nano, 9, 7019 (2015)
CMOS –several reports
1. High gain, low noise, fully complementary logic inverter based on bi-layer WSe2 field effect transistors,
Appl. Phys. Lett., 105, 083511 (2014)
2. High Gain Inverters Based on WSe2 Complementary Field-Effect Transistors, ACS Nano, 8, 4948 (2014)
3. High-Performance WSe2 Complementary Metal Oxide Semiconductor Technology and Integrated Circuits, Nano Letters, 15, 4928 (2015)
pn diode-several reports
1. Dual-Gated MoS2/WSe2 van der Waals Tunnel Diodes and Transistors, ACS Nano, 9, 2071 (2015)
2. Black Phosphorus–Monolayer MoS2 van der Waals Heterojunction p–n Diode, ACS Nano, 8, 8292 (2014)
3. Epitaxial growth of a monolayer WSe2-MoS2 lateral p-n junction with an atomically sharp interface, Science, 249, 524 (2015)
4. Vertical Heterostructure of Two-Dimensional MoS2 and WSe2 with Vertically Aligned Layers, Nano Letters, 15, 1031 (2015)
5. Lateral epitaxial growth of two-dimensional layered semiconductor heterojunctions, Nat. Nanotechnol., 9, 1024 (2014)

ACS Nano, 8, 8292 (2014)

Nano Letters, 15, 4928 (2015)
Outline
l Introduction : Outline and Motivation

l Progress on 2D Nanosheets in World Researches

------------------------------------------------------------------------------------

l Progress on 2D Nanosheets in our Lab

§ Top-gate MoS2 FET, Nonvolatile Memory FETs and P-N diode

§ 2D-2D, 2D-1D, 2D-Organic Hybrid Complementary Inverter

§ Black Phosphorous Dual Gate FETs

§ NiOx-MoS2 van der Waals junction MESFET

§ Summary
Photo-Excited Charge Collection Spectroscopy
For n-channel FET (i. e. oxide semiconductor)
IGZO

Drain Current
e- EC Initial
e1 < e2 EFn
(dark state)

Dit: DOS of interfacial traps

e1 = hn1
Modification of Qeff
e2 = hn2 EV
EF
Result in Vth shift!!

Gate Voltage
Gate Dielectric n-channel

Making on-state All interfacial (electron) traps

(accumulation) are occupied…
C ox ¶Vth (ε)
Δ Vth (ε) ΔQeff = C ΔVth D it (CBM - ε) =
q ¶ε
 Recent Progress on 2D Nanosheet (IM)
1.Nanosheet Band-Gap & Thickness Modulation 2. Nanosheet-Dielectric Interface Trap
MoS2 Nanosheet Phototransistors with Thickness-modulated Trap density probing on top-gate MoS2 Nanosheet field-
Optical Energy Gap, Nano Lett. (2012) effect transistors by photo-excited charge collection
spectroscopy, Nanoscale (2015)

Number Trap density (X1012 cm-2) obtained from

of MoS2 Hystere- Hysteresis &
layer PECCS SS
sis PECCS
2 1.92 1.00 2.92 6.67
3 1.26 1.15 2.41 7.10
4 2.47 1.37 3.84 7.69
Recent Progress on 2D Nanosheet (IM)
3. Nonvolatile Memory FETs 4. 2D-2D van der Waals p-n diode
MoS2 Nanosheets for Top-Gate Nonvolatile Memory Enhanced device performance of WSe2-MoS2 van der
Transistor Channel, Small (2012) Waals junction p-n diode by fluoropolymer encapsulation,
JMC C (2015)

10-3
10-4
10-5
Drain Current (A)

write WR pulse
10-6 ER pulse
10-7 VD = 1 V

10-8
erase
10-9
10-10
10-11
10-12
-20 -15 -10 -5 0 5 10 15 20
Gate Voltage (V)
 2D-2D, 2D-1D, 2D-Organic
Hybrid Complementary Inverter

P. J. Jeon et al. ACS Appl. Mater. Interfaces, DOI: 10.1021/acsami.5b06027 (2015)

S. H. Hosseini Shokouh et al., Adv. Mater. 2015, 27, 150 (2015)
H.S. Lee et al. Small, 11, 2132 (2015)
Fabrication : Direct Imprinting Method

Step1 | Flake exfoliation Step2 | Alignment Step3 | Flake imprinting Transferred flakes
on patterned-gate

MoS2

WSe2

Source/Drain
patterning

MoS2
Au/Ti

Step4 | MoS2 transfer Step5 | WSe2 transfer Step6 | SD patterning Pt WSe2

10 μm
2D p-WSe2 and n-MoS2 FETs on Wafer
WSe2 FET Transfer Curve MoS2 FET Transfer Curve Output Curves
0.8 0.8
WSe2 FET MoS2 FET
VG=-10 V
0.6 0.6

-Drain Current (mA)

Drain Current (mA)

|∆VG|=2 V
VG=10 V
0.4 0.4

0.2 0.2

0.0 0.0
-1.0 -0.5 0.0 0.5 1.0
Drain Voltage (V)

10 μm
- 285 nm-thick SiO2/p+-Si substrate MoS2
- Large operation voltage in a range of VG=-20~10 V
(VTH=+5 V for p-WSe2, VTH=-15 V for n-MoS2)
WSe2
- Large gate-source leakage current of IGS~100 pA
- Large overlap area between un-patterned gate and source/drain electrodes
Complementary Inverter on Wafer
Complementary inverter VTC Dynamic switching
f=10 Hz
VDD=1~5 V 1 1 1 1
VDD=5 V 0
5

VIN (V)
Output Voltage (V)
-5
4 0 0 0 0
-10
3
2 1 1 1 1
2

VOUT (V)
VDD=1 V
1 0 0 0 0
0
0
-15 -10 -5 0 0.0 0.1 0.2 0.3 0.4
Input Voltage (V) Time (s)

10 104
- Negative transition voltage of VTR=-7.5 V
8 Gain
102

Gain (-dVOUT/dVIN)
(not suitable for practical applications

Power (nW)
6
100
- Voltage gain (–dVOUT/dVIN) : ~6 4
10-2
- Peak power consumption (P=VDDxIDD) : ~1 μW 2
10-4
Power
- Large switching delay of 10 ms 0
-20 -15 -10 -5 0 -20 -15 -10 -5 0
due to overlap capacitance-induced booster effects Input Voltage (V)
Input Voltage (V)
2D p-WSe2 and n-MoS2 FETs on Glass
WSe2 FET Transfer Curve MoS2 FET Transfer Curve Fluoropolymer CYTOP

CYTOP CF2 CF2

CF CF n

O CF2
CF2

- 50 nm-thin Al2O3 (ALD)/Patterned gate on glass substrate

: Low operation voltage of VG=-5 ~ +5 V
: Low gate-source leakage current of <100 fA
- Fluoropolymer CYTOP encapsulation (C-F bond-induced dipoles)
: Induced more hole carriers into thin p-WSe2 (positive VTH shift)
: Reduced electrons in thin n-MoS2 (reduced on-current).
 Complementary Inverter on Glass
VTC before CYTOP VTC after CYTOP Dynamic Switching
104 104 f=500 Hz
Pristine CYTOP 1
VDD=5 V VDD=5 V 0
5 5 encapsulation

VIN (V)
2 2
10 10
Output Voltage (V)

Output Voltage (V)

VDD=4 V VDD=4 V
4 4

Power (nW)

Power (nW)
-5
10 0
100 0
3 3
1
-2 -2 2
2 2

VOUT (V)
10 10
1 1
10-4 10-4 0 0
0 0 0 10 20 30
-2 -1 0 1 2 3 0 1 2 3 4 5 Time (ms)
Input Voltage (V) Input Voltage (V)

- Positive transition voltage shift after CYTOP encapsulation

(VTR; 0.1 V → 2.3 V)
- High voltage gain of 23 at VDD=5 V
- Subnanowatt power consumption : Ppeak~1 nW
- Ideal noise margin (NML=0.385xVDD, NMH=0.495xVDD at VDD=5 V)
- Switching delay : ~800 μs
Pass Transistor Logic Gates
NOT gate OR gate AND gate

3V A B

VIN
VOUT VOUT VOUT
0V B A
3 NOT; (VIN) OR; (A,B) AND; (A,B)
3 3
Output Voltage (V)

Output Voltage (V)

Output Voltage (V)

2 2 2

1 (0) (1) 1 (0,0) (0,1) (1,0) (1,1) 1 (0,0) (0,1) (1,0) (1,1)

0 0
0
0 5 10 15 20 0 10 20 30 40 0 10 20 30 40
Time (s) Time (s) Time (s)
A B VOUT=A+B A B VOUT=AxB
VIN VOUT
0 0 0 0 0 0
0 1
0 1 1 0 1 0
1 0
1 0 1 1 0 0
1 1 1 1 1 1
2D-1D Hybrid Complementary Inverter

Voltage gain of 60 and subnanowatt power consumption at static states

Highest gain and lowest power consumption for reported 2D material based inverter

S. H. Hosseini Shokouh et al., Adv. Mater. 2015, 27, 150 (2015)

2D-Organic Hybrid Complementary Inverter

Forecast some possibility to use 2D FET combined

with Org. Elec. ? H.S. Lee et al. Small, 11, 2132 (2015)
 Dual gate black phosphorous field effect
transistors on glass for NOR logic and organic
light emitting diode switching

J. S. Kim et al. Nanoletters, 15, 5778, (2015)

Images and Raman spectra

Thickness
~ 12 nm
I-V Characteristics of Dual gate FET
Voltage shifts & Logic gate

NOT logic NOR logic

ambipolar transition voltage shifts from -0.5 to 1.5 V by applied top gate bias
Dynamic OLED Switching

Well switching operated as Green, blue OLED pixel

Dynamic OLED Switching

Well switching operated as Green, blue OLED pixel

 NiOx-MoS2 metal-semiconductor
field-effect transistor
for high mobility and photoswitching speed

H.S. Lee et al. ACS Nano, 9, 8312, (2015)

Structure of MoS2 MESFET

“Thermally evaporated NiOx is known to have quite a deep work function of more
than 5.1~5.2 eV as a Ni-rich semi-transparent conducting oxide (x~0.9).”
NiOx van der Waals Schottky Interface
Schottky diode IV curves Energy band diagram

- The better rectifying behavior

for the thinner MoS2
MESFET : Channel Thickness Effects

MESFET Transfer Curve MESFET switching Thickness dependency

MESFET
Mobility , where
4-Probe Hall Measurement
MoS2 Hall Coeff-H(T) Curve MoS2 Nd conc. (T) plot
4x106 1017 0.2

RH(H) - RH(0) (MW)

6 200 K 220 K 300 K
3x10 0.1
240 K 260 K
RH(H) - RH(0) (W)

2x106 280 K 300 K 0.0

Nd (cm-3)
1x106 -0.1
-0.2
0 1016 -10 -5 0 5 10
H (T)
-1x106
-2x106
-3x106
-4x106 1015
-10 -5 0 5 10 200 220 240 260 280 300
H (T) Temperature (K)

- ns=4.03 x 1010 cm-2 (2.52 x 1016 cm-3)

for 16 nm-thick MoS2 at 300 K
- Hall mobility of 16 nm-thick MoS2 : ~200 cm2/V s
MESFET vs. MISFET

Saturation behavior in MESFET

: easier channel-depletion (pinch-off) in drain side
MESFET vs. MISFET
“The carrier transport in MESFET may hardly be interfered
by insulator-semiconductor interface traps or an on-state gate field.”

Parameters MESFET MISFET

Subthreshold swing 83 mV/dec 200 mV/dec
Mobility 950 cm2/V s 13 cm2/V s
Hysteresis 0.06 V 8.56 V
Threshold voltage -1 V -25 V
Photo-detecting properties & Dynamic

MESFET MISFET

Photo-to-dark
2.85x103 1.4x102
current ratio

Responsivity
5000 A/W
(ON state)

Responsivity
1.1 A/W
(OFF state)

Delay 2 ms 250 ms
Summary

§ 2D-FETs
analysis MoS2 band gap, nonvolatile memory, p-n diode

§ Hybrid complimentary Inverter: nW power, high gain

2D-2D, 2D-1D, 2D-Organic

§ Black Phosphorous Dual Gate FETs: High current, NOR gate

TG BG bipolar transition voltage shifts, OLED switching

§ NiOx-MoS2 van der Waals junction MESFET:

Intrinsic high mobility and photo-switching speed
 IM’s group activity on 2D Devices
FET
1. MoS2 nanosheet phototransistors with thickness-modulated optical energy gap, Nano Letters, 12, 3695 (2012)
2. MoS2 nanosheets for top-gate nonvolatile memory transistor channel, Small, 20, 3111 (2012)
3. Nanosheet thickness-modulated MoS2 dielectric property evidenced by field-effect transistor performance, Nanoscale, 5, 548 (2013)
4. Direct imprint of MoS2 flakes on the patterned gate for nanosheet transistors, Journal of Materials Chemistry C, 1, 7803, (2013)
5. Graphene versus ohmic metal as source-drain electrode for MoS2 nanosheet transistor channel, Small, 10, 2356, (2014)
6. Trap density probing on top-gate MoS2 nanosheet field-effect transistors by photo-excited charge collection spectroscopy
Nanoscale, 7, 5617 (2015)
7. Metal Semiconductor Field-Effect Transistor with MoS2/Conducting NiOx van der Waals Schottky Interface for Intrinsic
High Mobility and Photoswitching Speed, ACS Nano, 9, 8312, (2015)
8. Dual Gate Black Phosphorus Field Effect Transistors on Glass for NOR Logic and Organic Light Emitting Diode Switching,
Nano letters, 15, 5778, (2015)
9. High Performance Air Stable Top-gate p-channel WSe₂Field Effect Transistor with Fluoropolymer Buffer Layer,
Adv. Funct. Mater., DOI: 10.1002/adfm.201502008, (2015)
 Im’s group activity toward 2D semi.
Hybrid (Complimentary) Inverter
10. Molybdenum disulfide nanoflake-zinc oxide nanowire hybrid photoinverter, ACS Nano, 8, 5174 (2014)
11. Top and back gate molybdenum disulfide transistors coupled for logic and photo-inverter operation,
Journal of Materials Chemistry C, 2, 6023, (2014)
12. High-gain subnanowatt power consumption hybrid complementary logic inverter with WSe2 nanosheet and ZnO nanowire transistors on glass
Advanced Materials, 27, 150 (2015)
13. Few layer MoS2-organic thin film hybrid complementary inverter pixel fabricated on glass substrate
Small, 11, 2132 (2015)
14. Low Power Consumption Complementary Inverters with n-MoS2 and p-WSe2 Dichalcogenide Nanosheets on Glass for Logic
and Light-Emitting Diode Circuits, ACS Appl. Mater. Interfaces, DOI: 10.1021/acsami.5b06027, (2015)

P-N and Schottky Diode

15. Multifunctional Schottky-diode circuit comprising palladium/molybdenum disulfide nanosheet, Small, 10, 23, (2014)
16. Enhanced device performances of WSe2–MoS2 van der Waals junction p–n diode by fluoropolymer encapsulation
Journal of Materials Chemistry C, 3, 2751, (2015)

Memory FET
17. MoS2 nanosheet channel and guanine DNA-base charge injection layer for high performance memory transistors
Journal of Materials Chemistry C, 2, 5411, (2014)
18. Nonvolatile Ferroelectric Memory Circuit Using Black Phosphorous Nanosheet-based Field Effect Transistors with P (VDF-TrFE) Polymer,
ACS Nano, DOI: 10.1021/acsnano.5b04592, (2015)
Collaboration Groups & Acknowledgment

Acknowledgement
• National Research Foundation of Korea
National Research Laboratory: 2014R1A2A1A01004815,
Nano-Materials Technology Development: 2012M3A7B4034985)
• Yonsei University
Future-leading Research Initiative of 2014: 2014-22-0168
• Brain Korea 21 plus

Collaboration Groups
• LG Display & Samsung Display
• Dr. Won-Kook Choi ( KIST - Optoelectronic Materials and Devices Post-Silicon Semiconductor)
• Prof. Takhee Lee (Seoul National Univ. - Dept. of Physics and Astronomy)
• Prof. Myung Mo Sung (Hanyang Univ. - Dept. of Chemistry)
• Prof. Jae Hoon Kim, Hyoung Joon Choi, Yeonjin Yi (Yonsei Univ. - Dept. of Physics)
• Prof. Hyungjun Kim, Jong-Hyun Ahn (Yonsei Univ. - Dept. EE)
Thank you for listening

E-mail: [email protected]
Lab. Website: Http://edlab.yonsei.ac.kr