Center for Precision Assembly of Superstratic and Superatomic Solids

(PAS3)

Superstratic Superatomic

The MRSEC Team

Herman

Oganesyan

Nuckolls

Marianetti

Steigerwald

Barmak Cacciuto

Kim

Reichman

Zhu

Tamargo

McDermott

BrusArchibald

Roy

Kymissis

Venkataraman

Millis

Crowther

Heinz

Pasupathy

Krusin-Elbaum

Dean

O’Brien

Hone

Ford

Lowes

Campos

MRSEC fellows: Rebeca Ribeiro, Lukas Zhao (IRG 1), Alexandra Velian, Haiming Zhu (IRG 2)

IRG 1: Heterostructures of van der Waals Materials

Create van der Waals heterostructures by lamination of 2D materials

Materials Properties Interactions and Emergent Behavior

IRG 1 Team

James Hone, Columbia Mechanical Engineering, Lia Krusin-Elbaum, CCNY Physics

Wayne ArchibaldUVI

Cory DeanColumbia

Tony HeinzColumbia/Stanford

Irving HermanColumbia

Philip KimHarvard

Chris MarianettiColumbia

Stephen O’BrienCCNY

Vadim OganesyanCUNY

Abhay PasupathyColumbia

Maria TamargoCCNY

Latha VenkataramanColumbia

Key collaborators: Sfeir, Stach, Sutter (BNL); Adam, Castro-Neto (NUS); Low (IBM); Taniguchi, Watanabe (NIMS)

TheanneSchiros

FIT

IRG 1: Heterostructures of van der Waals Materials

graphene h-BN

Dichalcogenides TopologicalInsulators

Oxides

Polymer-free transfer achieves atomically clean heterostructures

L. Wang et al, Science 2013, X. Cui et al Nature Nano

Examples

hBN-encapsulated MoS2

6L

4L

2L 3L

1L (CVD)

~ T-γ

10 T (K)

1 100

105

104

103

102

µ Hal

l (cm

2 /Vs)

a

WSe2

atomically thin p-n Junction

0.6

0.4

0.2

0.0

I ds (n

A)

‐30 0 30

Vg (V) ‐0.5 0.0 0.5 1.0

Vds (V)

ZnCd1-xSex

sapphire6 nm

10 nm

Bi2Se3

2 3 4

0.7

0.8

0.9

1.0

1.1

8 T 1.5 T 1 T 0.44 T 0.26 T 0.18 T 0.12 T 0.08 T 0.05T 0.025T 0 T

R /

Rn

T (K)

H || c

Interfacial superconductivit

Magnetic field tuned quantum metal in 2D NbSe2A. W. Tsen, B. Hunt, Y-D Kim, J. Hone, P. Kim, C. R. Dean, A. N. Pasupathy

Robust topological interfaces and charge transfer in epitaxial Bi2Se3/II-VI semiconductor superlattices (NanoLetters 2015)

(a)

10 nm

Bi2Se3ZnCdSe

S

-100 -50 0 50 100

0.0

0.5

1.0

S5 S6

Rxx

/ Rm

ax (a

.u)

Vg (V)

A

B

DC

Vg

-1.0 -0.5 0.0 0.5 1.0-15

-10

-5

0

B

l = 152.8 nm B = 7.05 mT

exp. fit

G (1

0-5S)

0H (T)

= 3.62

(d) (e)Zn terminated

Se terminated

d

Bi(1 Se(1) Zn(1)

40 45 50 55 60 65 70-0.10-0.050.000.050.10

Q(e

)

Z(Å)

(d)

Se(2)

25 30 35 40 45 50 55-0.05

0.00

0.05

Q(e

)

Z(Å)

Se(3)

(b)

(c)

Zhiyi Chen, Lukas Zhao, Kyungwha Park,Thor Axtmann Garcia, Maria C. Tamargo, and Lia Krusin-Elbaum

Creating Multifunctional Materials From Superatoms

Materials

Thermoelectrics

Novel Superconductors

Magnetic Memory

Photovoltaics

Ferroelectrics

……

Control

Band Structure

Spin/Magnetism

Dimensionality

Phonon Properties

Length Scale

…...

Strategy

SA Composition

SA Size

Inter-SA coupling

SA Structure

SA Interface

……

IRG-2 Team & Management

Theory

David Reichman

Angelo Cacciuto

AndrewMillis

TimothyMueller

(DuPont)

Structure, Electronics, and Magnetism

JohnHill

(BNL)

KatayunBarmak

TheoSiegrist(FSU)

ErichStach(BNL)

Philip Kim

JohnKymissis

JimMisewich

(BNL)

GeorgeTulevski

(IBM)

Spectroscopy

AnnMcDermott

XiaoyangZhu

AndrewCrowther(Barnard)

LouisBrus

JonathanMalen(CMU)

IRGLeads

Synthesis

Xavier Roy

Colin Nuckolls

MichaelSteigerwald

LuisCampos

Design & Synthesis of Superatoms

• Tunable size, shape, & composition with Atomic precision (XRD, TEM, PXRD)

• Surface control for strong inter-SA interactions.

• Programmable properties: DOS, oxidation/reduction potential, electronic/magnetic, thermal, photochemical…

• First principles theory (e.g. DFT) <=> Spectroscopy

Design and Synthesis: Nuckolls, Roy, and Steigerwald

Co6Se8(PEt3)6 Cr6Te8(PEt3)6

Co6Te8(PEt3)6

Ni9Te6(PEt3)8 Ni20Te18(PEt3)12

Fe4Te4(PEt3)4 Si14(CH3)24

Co6Se8(PEt2phen)6

Fe8O4pz12Cl4 pz = pyrazolate phen= 9‐ethynylphenanthrene

Co6Te14(PEt3)6

M. L. Steigerwald et al., Inorg. Chem. 1994, 33, 3389; Inorg. Chem. 1993, 32, 5165; JACS 1989, 111, 9240.

Superatom assembly via charge transfer

Multi‐scale modeling Experiment• Parameterize inter‐SA interactions (ab initio & semi‐

empirical calculations)• Assembly dynamics as function of interactions (long‐

range electrostatics, CT,  short‐range anisotropy, van der Waals, polarization, etc…).

• Phase diagrams (Monte Carlo simulations…) Theory:

Cacciuto and Reichman

Synthesis and Assembly:Nuckolls, Roy, and Steigerwald

Structure:Barmak, Siegrist (FSU), Stach (BNL) and Stephens (BNL)

X. Roy et al. Science 2013, 341, 157.

Superatom AssemblyVibrational m

ode 

freq

uency

Cluster 1 Interface Cluster 2

Superlattice structure

Superatom and Interface atomic precision

Vibrational Landscape

Thermal Conductivity

Magnetic state of Superatoms

Inter‐Superatommagnetic coupling 

Magnetic Properties Example

Co6Se8diamagnetic

Co6Te8μeff = 8.2 μB

A

Si/SiO2 Au pad

Pt counter electrode

PEO/electrolyte e− from electrode

Li+ from electrolyte

+ −

e−

Superatom crystal

Electronic Properties

h2

h1

e

VB

CB

Intercalation

Van der Waals Solids from Self-Assembled Nanoscale Building Blocks B. Choi, D. W. Paley, J. Yu, C. H. Lee, P. Kim, M. L. Steigerwald, C. Nuckolls, X. Roy

Submitted

Self-Assembly

Director

Guest

Top View

Side View

10 Å

Layer CF [Co6Se8phen6][C60]2

Layer FL [C60]3

10 Å

Layer CF

Layer FL

2.63 nm

B C

D

A

Shared Materials Characterization Lab• New Space: 240 Havemeyer (renovated) and 540

Havemeyer• Manager: Dan Paley(1)SuperNova Single Crystal Diffractometer(2)Panalytical Powder X-ray Diffractometer(3)Bruker Fastscan AFM(4)Thermal Analysis DSC and TGA (5)XPS (refurbished)(6)SQUID Magnetometer

Other major new equipment to be purchased:1. He liquifier for 2 magnet cryostats2. Cryostat system at CCNY3. UV-vis spectrometer

Columbia Nanofabrication Laboratory

Current facility: 2000 ft2, class 10,000, >250 users from 12 departments in engineering and sciences, 2 technical staff.Renovation: add 1000 ft2, upgrade air handling and safety. Construction starts 2014, with phasing for continuous operation. Expansion to 4 technical staff funded by university.

Existing Space

New Space

CUNY ASRC NanoFabricationFacility

inductively coupled plasma (ICP) etcher

Other major tools: ▪ SEM, ▪ PECVD, ▪ RIE ▪ ALD ▪ sputtering and evaporation tools, ▪ an advanced metrology suite, and ▪ a true 3D laser lithography, ▪ LPCVD, TOES, and Oxidation furnaces.

e-beam lithography

The new NanoFab: 5,000 ft2 of ISO 6 (Class 1,000) and ISO 5 (Class 100) cleanroom space; additional lab space for back-end processing and support areas; 6-inch wafer handling capability; CUNY funded technical staff.

e-beam / thermal evaporatorphotolithography

Electron Microscopy at CU and CCNY

820 sq. ft. space under renovation

FEI TalosF200A

Katayun Barmak

Helios NanoLab 660 (FIB/SEM

Titan Themis 200 (S)TEMTecnai G2 Spirit BioTwin: Advanced 120 kV TEM

Nova NanoSEM 450

Columbia CUNY

Additional capabilities at BNL (+Rutgers/BNL)

Instrument Development: Inert Atmosphere Assembly System

Transfer stage Compact Auto-Finder

• User facility for MRSEC• Combines auto-finder and transfer

stage• AFM/Raman for characterization• Metal evaporation / Parylene

deposition for large-scale encapsulation

Combined AFM/Raman

Instrument Development: Time-Resolved ARPES with VUV laser source for complete mapping of valence and

conduction bands

Extreme UV laser source: 47-13 nm (26-95 e

Profs. Henry Kapteyn & Margaret Murnane

h2

h1

e

VB

CB

Nature 471, 490 (2011) 

* Two femtosecond laser ARPES setups in XYZ lab (hv ≤ 6 eV).

* Extending to VUV complete mapping of VB & CB structure with fs time resolution.

e.g., electronic phase transition in 1T-TiSe2

MRSEC Institutions and Partners

Harvard

Stanford

UVI

CSSMSEHSMSESchool @ ColumbiaColumbia Journalism

LaGuardia Community College

CUNY College of Staten Island

DuPont

IBM TJ Watson

Brookhaven National Lab

ColumbiaCCNYBarnard

ColumbiaNWC Building

CCNYASRC Buildin

Management and StaffDirector James HoneAssociate Director Colin Nuckolls

Executive CommitteeJames Hone

Colin NuckollsLia Krusin

Xiaoyang ZhuJeffrey Kash (convener)James Misewich (BNL)

Postdoc Fellow

IRG 1James HoneLia Krusin

IRG 2Colin NuckollsXiaoyang Zhu External Partners and Collaborators

G. Michael Purdy, Columbia EVPRDean Mary Boyce, Columbia SEASDean David Madigan, Columbia A&S

Education, Human Resources, and Diversity Committee

External Advisory Board

Student Leadership Council

Catherine Tissot – MRSEC administration Dario Vasquez – outreach, seminars, website

Xiomara Perez-Betances: CNI DOEmily Ford – SEAS outreach director

Integrated Education / Outreach Program

Level Activities

Primary Integrated Project Week at TSC

Secondary RET programScience Honors Program – Nano courseHS research program:  CSSMSE partnership

Undergraduate LaGuardia Community College partnershipCurriculum developmentREU programUndergraduate research

PhD/Postdoc CurriculumWorkshops and SeminarsShort CoursesStudent Leadership council

Public Science celebration, Materials open houseJournalism school pilot

REU Symposium Day 

ENG trip to Brookhaven National Laboratory

Research Experiences for Teachers (RET)

Research Experiences for Undergraduates (REU)

LaGuardia Community College Columbia Secondary School (K‐12 school)

Engineering the Next Generation (ENG)

Summer MRSEC outreach and education programs at Columbia University / CCNY

The Columbia / CCNY MRSEC inaugurated its summer research education program in 2015 by hosting 44 summer researchers, including teachers, undergraduates, community college students, and high school students