Wafer Scale Integration - SEMICON · PDF file2015 2.2M € investment for ... FORMAT RAW...

Wafer Scale Integration

July, 2016

2 Private and confidential

Outline

•  What is Graphene?

•  Introduction to Graphenea

•  A market overview

•  Graphene wafer scale integration allows many applications

•  Wafer Scale Integration •  Graphenea Roadmap


Graphene has outstanding electronic, optical, thermal and mechanical properties


2004 2008 2009 2010 2011 2012 2013 2014

Geim & Novoselov publiish Science paper

Jesus de la Fuente writes first Business Case

First funding round closed $1,8 m

First Graphene produced in Graphenea

Moving to a larger

laboratory

Sigma-Aldrich selects

Graphenea as supplier

Graphenea is a high-quality graphene producer…

Repsol Energy

Ventures joins

Graphenea €1 m

Graphene Flasghip

approved €1 B 10 years

project

First commercial

order

Graphenea founded

€1 m sales milestone

US branch opened

Global Top 100 Ones to

Watch

2015

2.2M € investment for

scale up secured


Graphenea Sites Headquarters & Research (San Sebastian, Spain)

GO Production Lab @ Miramon Technology Park App Laboratory (Cambridge, MA)


…and key Scientific talent involved...

Dr. Jing Kong MIT Boston

Scientific Advisor 2011-2012

Prof. Manish Chhowalla Rutgers New Jersey

Scientific Advisor 2010-

Dr. Tomas Palacios MIT Boston


Dr. Luis Hueso CIC nanogune


Dr. Amaia Zurutuza Graphenea’s

Scientific Director

Dr. Andreas Berger CIC nanoGune

Scientific Advisor 2009-2010

Dr. Alexander Balandin University of California Riverside



CVD graphene!

SiC Sublimation

Mechanical Exfolliation

Chemical Exfoliation

(-) Large area (+)!

(-)

H

omog

enei

ty

(+

)!

Industrial scalability

Graphene synthesis technologies comparison

Mechanical exfoliation

Chemical exfoliation

SIC Sublimation

CVD

Graphenea is working with industrial-scalable technology CVD and GO


Graphenea is working with industrial-scalable technology CVD and GO

Mechanical exfoliation

FORMAT RAW MATERIAL

CVD (Chemical

Vapour Deposition)

GO (Graphene

Oxide)

PROPERTIES

CH4

Graphite

POTENTIAL

High electron mobility

Versatility Functionalization

High

Medium

MAIN APPLICATIONS

Electronics Optoelectronics

Sensors/Biosensors Membranes

Flexible Electrodes

Advanced Polymers Composites

Sensors Batteries

Supercaps


1.  Method for Transferring Graphene, EP15382430, filing date 24 Aug 2015

2.  Method for Obtaining Graphene Oxide, EP15382123, filing date 17 Mar 2015

3.  Quality Inspection of Thin Film Materials, PCT/EP2014/079171, filing date

23 Dec 2014

4.  Equipment and Method to Automatically Transfer a Graphene Monolayer

to a Substrate, EP14382148, filing date 24 Apr 2014

5.  Method of Manufacturing Graphene Monolayer on Insulating Substrates,

EP2679540, filing date 29 June 2012

Graphenea Intellectual Property


Graphenea site Official distributor site

Applications Laboratory

Headquarters

We are expanding our global presence


Graphenea has a growing customer base and distribution network…

INDUSTRIES RESEARCH CENTERS UNIVERSITIES

Note: Partial list – illustrative only


Market Overview


Each application requires a specific type and grade of graphene

RESEARCH APPLIED RESEARCH & DEVELOPMENT DEMONSTRATION COMMERCIAL

CVD

GO ADVANCED POLYMERS

DNA sequencing

Optoelectronics

Carbon Fiber

PHOTOSENSORS

LED lighting

MEMBRANES

Electron Microscopy

Solar Cells

CERAMIC COMPOSITES

Li-ion Batteries

Supercapacitors

BIOSENSORS

Flexible Transparent Conductors

Metal Alloys

Printed Electronics

Li-S Batteries

R&D Materials

TECHNOLOGY READINESS

LEVEL

1 BASIC

PRINCIPLES

2 TEHCN.

CONCEPT

3 PROOF OF CONCEPT

4 VALIDATION

LAB

5 VALIDATION

FIELD

6 PROTOTYPE

7 PROTOTYPE REAL ENV.

8 QUALIFIED & TESTED

9 OPERATION

Illustrative TRL application map


Graphene market is very small and driven by Research-related demand.

Global Graphene market forecast ($M)

BCC has reduced it market expectation in 2017 from 270 MM$ to 122.9 MM$, fully aligned with IDTechEx forecasted market of 100 MM$ in 2018, Lux Research estimates $126 in 2020

0

100

200

300

400

500

600

700

800

900

1.000

2010 2011 2012 2013 2014 2015 2016 2017 2018 2019 2020 2021 2022

BCC IDTechEx Lux Research

Early-stage applications demand Research-related demand

Source: BCC, IDTechEx, Lux Research, Graphenea elaboration


Quantum dots…How things can change dramatically


Graphene wafer scale integration allows many applications


Nanowires on graphene enables UV LEDs

By growing AlGaN (aluminium gallium nitride) nanowires on graphene, graphene

will be used both as a substrate and as a UV transparent electrode in order to achieve

a high external efficiency

Food Processing Air Purification Water Disinfection

UV LED Dies


Flexible WiFi receivers

•  2.4 GHz receiver circuits on plastic •  Ideal for IoT and flexible electronics

Source: McKinsey


Flexible Hall sensor

•  High sensitivity, linearity and

flexibility •  The key factor determining

sensitivity of Hall effect sensors is high electron mobility

Source: Honeywell


Ultra-sensitive and low-cost Graphene Quantum-Dot Photodetector

Non-invasive health monitoring applications


CMOS-Fab Integration

CVD growth on Cu foil

Automated transfer of graphene on CMOS

wafer

Transfer on a carrier substrate

Patterning of Graphene structures and contact metals

Functional material deposition and encapsulation

Pick and Place assembly

Final testing and calibration

ü Graphenea allows integration for graphene


 Graphene on a carrier substrate

 Important factors to consider •  Transfer method selection •  Substrate type •  Semiconductor industry requirements: metal impurities,

contamination, wafer uniformity •  Large scale quality control method



•  Quality of the transfer •  Substrate supporting the graphene •  Quality of the interface between

graphene & substrate

Graphene on catalyst Graphene on

the desired substrate

Large impact on graphene properties & device

performance



 Graphene on a carrier substrate to facilitate integration

Graphenea End user



•  WetTransfer

•  DryTransfer

•  Semi-dryTransfer

There is non standard process for all the substrates and applications



Conven&onalwettransferprocess

G

Cu

G

Cu Polymer

G

Polymer

Sisubstrate

G

Protec&vepolymercoa&ng

G

PolymerSisubstrate

TransferontothefinalsubstrateRemovalofthesacrificialpolymer

Cleaningsteps(H2O)

MetaletchingProtec&vePolymer



Drytransferprocess



 Alternative to Cu etching – electrochemical delamination

ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms1702

NATURE COMMUNICATIONS | 3:699 | DOI: 10.1038/ncomms1702 | www.nature.com/naturecommunications

© 2012 Macmillan Publishers Limited. All rights reserved.

with different orientations, similar to the graphene grains grown on Cu foils by LP-CVD21. Note that the size of the single-crystal grains in this graphene is at least 150 m, larger than those grown on Cu foils by AP-CVD (usually about 20 m)21,22, but little smaller than the dendritic graphene grown on Cu by LP-CVD19.

It is first important to note that the predominant hexagonal graph-ene grains grown on Pt substrates have no reflex angle at the edges and no visible lines in their planes even in high-resolution scanning

electron microscope images. Second, the size of the graphene grains is inversely proportional to the nucleation density of graphene. The nucleation density of graphene grains on Pt at a low CH4 concentra-tion is very low, with a spacing of more than 1 mm, which provides space for the growth of large graphene grains. Third, with increas-ing growth time, no new nuclei are observed and only the continu-ous growth of graphene grains is observed. The lateral size of the graphene grains is roughly proportional to the growth time, with a mean growth rate of ~4 m min − 1 under the present growth condi-tions, which is about four times faster than that (~1 m min − 1) of the growth of hexagonal graphene grains on Cu. All the above facts indicate that the hexagonal grains with obtuse angles grown on Pt substrates should be single-crystal graphene grains, which are simi-lar to the hexagonal single-crystal graphene grains grown on Cu foils by AP-CVD22, but have a much larger size up to more than a millimetre. It is worth noting that, by further increasing the growth time, large graphene grains join together and eventually form a con-tinuous graphene film with grain boundaries, shown in Fig. 2.

Nondestructive transfer of graphene from Pt substrates. The cur-rently used etching-based transfer methods are not suitable for the transfer of graphene grown on Pt, as Pt is chemically inert and more expensive compared with Cu and Ni. Recently, an electrochemical delamination method was reported to transfer graphene grown on Cu25, but it was found that a thin layer of Cu, about 40 nm thick, was etched away during one transfer process. For graphene grown on Pt substrates, we have developed a bubbling transfer process, similar to the recently reported method25, to transfer the material based on a water electrolysis process32 (Fig. 3). After CVD growth, a Pt substrate with the graphene grown on it was first spin-coated with polymethyl methacrylate (PMMA) followed by curing. Then the PMMA/graphene/Pt was dipped into an NaOH aqueous solu-tion and used as the cathode of an electrolysis cell with a constant current supply. It is worth noting that the graphene would be easily oxidized if the PMMA/graphene/Pt was used as the anode. At the negatively charged cathode, a water reduction reaction took place to produce H2. The reaction can be represented as follows:

2 2 22 2H O l H g OH aq( ) ( ) ( )e

We observed that the PMMA/graphene layer was detached from the Pt substrate after tens of seconds as a result of the forma-tion of a large number of H2 bubbles at the interface between the graphene and Pt substrate. This is much faster than the detach-ment of graphene by substrate etching, which usually takes tens of minutes to etch away substrates such as Cu and Ni. After clean-ing with pure water, the floating PMMA/graphene layer was

50

40

30

20

10

0

c d

a b

e f

Figure 2 | Coalescence of graphene grains. Scanning electron microscope (SEM) image of the coalescence of different graphene grains: (a) two; (b) three; (c) many; (d) continuous graphene film formed from grains. The graphene film completely covers the Pt substrates without any gaps. (e) Optical image of two coalesced graphene grains. (f) Raman mapping of the intensity of D band (1,300–1,400 cm − 1) at the joint area of the two coalesced grains indicated by a red box in (e). The strong intensities along the line in the mapping indicate a grain boundary. The scale bars in (a–d) are 400 m, in (e) 50 m, and in (f) 20 m.

1 M NaOH

+ –

–

PMMA/GraphenePMMA

Cathode SeparateBubbling

H2 bubble

Figure 3 | Illustration of the bubbling transfer process of graphene from a Pt substrate. (a) A Pt foil with grown graphene covered by a PMMA layer. (b) The PMMA/graphene/Pt in (a) was used as a cathode, and a Pt foil was used as an anode. (c) The PMMA/graphene was gradually separated from the Pt substrate driven by the H2 bubbles produced at the cathode after applying a constant current. (d) The completely separated PMMA/graphene layer and Pt foil after bubbling for tens of seconds. The PMMA/graphene layer is indicated by a red arrow in (c) and (d).

Gao et.al. Nat. Commun. 3, 699 (2012)

Semi-Drytransferprocess



Imaging spectroscopic ellipsometry

•  Thickness •  Impurities •  Defects

1x1cm2,7minat10xobjecAve

•  Micromapping of Delta and Psi at 480nm related with the thickness of the material and refractive index

Graphene Wafer In-line quality control


Roadmap

Graphenea CVD production capacity roadmap

PHASE 0 1 cm x 1 cm/2 hour

PHASE 2 8” wafer/ 30 min

PHASE 3 12” wafer/30 min

2010-2012 2013-2014

PHASE 1 4” wafer/ 2 hour

2015-2016 2018-…

AUTO TRANSFER

RESEARCH DEVELOPMENT COMMERCIAL

310 €/cm2 5 €/cm2 0.80 €/cm2

0.25 €/cm2

www.graphenea.com

[email protected]

Wafer Scale Integration - SEMICON · PDF file2015 2.2M € investment for ... FORMAT RAW...

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