mª del prado lavín lópez - phantomsnet.net · dong, l.-x. and q. chen (2010). properties,...

CVD-GRAPHENE SYNTHESIS USING DIFFERENT TRANSITION

METALS AS CATALYST

Mª del Prado Lavín López

INTRODUCTION

Carbon allotrope

1 atom thick

sp2-hibridized atoms

2D hexagonal crystal

structure

Fullerene

0D

Graphite

3D Nanotube

1D

Geim, A.K. and K.S. Novoselov, The rise of graphene. Nature Materials, 2007. 6(3): p. 183-191.

High Mobility (105 cm2V-1s-1)

High Value of Young´s

ModuLus (~1 TPa)

High Specific Surface Area (2630 m2/g)

Optical Transparency

~97.7 %

High Thermal Conductivity

(~5000 Wm−1K−1) Minimum thickness (0.34 nm)

High fracture resistance

(~130 GPa)

High elasticity

(~0.25 TPa)

Zhu, Y., et al., Graphene and graphene oxide: Synthesis, properties, and applications. Advanced Materials, 2010. 22(35): p. 3906-3924. Dong, L.-X. and Q. Chen (2010). Properties, synthesis, and characterization of graphene. Frontiers of Materials Science in China 4(1): 45-51.

INTRODUCTION

http://www.google.es/url?sa=i&rct=j&q=&esrc=s&source=images&cd=&cad=rja&uact=8&ved=0CAcQjRxqFQoTCPqjyciy_scCFUlWFAodL8YKtg&url=http://3dprinting.com/news/worlds-first-commercial-conductive-graphene-filaments-for-3d-printing/&psig=AFQjCNESIXQ2WM-HDyNpmG4C2jLIfF7AtA&ust=1442590503716648

Flexibles displays

Frequencytransistors

Extremhardness

High speedInternet

Ultra

capacitors

Hydrogencontainers

Zhu, Y., et al., Graphene and graphene oxide: Synthesis, properties, and applications. Advanced Materials, 2010. 22(35): p. 3906-3924. Dong, L.-X. and Q. Chen (2010). Properties, synthesis, and characterization of graphene. Frontiers of Materials Science in China 4(1): 45-51.

INTRODUCTION

Avouris, P. and C. Dimitrakopoulos, Graphene: Synthesis and applications. Materials Today, 2012. 15(3): p. 86-97.

CARBON

GAS

SOURCE

GRAPHITE

GRAPHENE SHEET

GRAPHENE POWDER

Epitaxial Growth on SiC

Chemical Vapor Deposition (CVD)

Micromechanical

Exfoliation

Intercaled Graphite Compounds Exfoliation

Graphite Exfoliation in solvents

Unzipping CNTs

INTRODUCTION

Chemical Vapor Deposition (CVD) Chen, Z., et al., Bulk growth of mono- to few-layer graphene on nickel particles by chemical vapor deposition from methane. Carbon, 2010. 48(12): p. 3543-3550.

INTRODUCTION

Metallic

Catalyst

Metal support

(quart boat)

CH 4

C C

C C C

C

Graphene

CH 4

Tubular

Reactor

Thermocouple

Gas inlet

Gas Outlet

Furnace

Metal Sheet

EXPERIMENTAL

EXPERIMENTAL

Heating

Step

Reduction

Step

Reaction

Step

Cooling

Step

N2 N2 N2

H2 H2 H2

CH4

180 45 1-40 ˃180 t (min)

Tem

per

atu

re (

ºC)

900ºC 900-1050ºC

Room Tª

EXPERIMENTAL

RAMAN

SPECTROSCOPY

OPTICAL

MICROSCOPY

CHARACTERIZATION

TECHNIQUES

EXCEL-VBA

APPLICATION

1.Introducción

2. Objetivos

3. Metodología y

materiales

4. Resultados y

discusión

5. Conclusiones y

Recomendaciones

OPTICAL

MICROSCOPY

EXPERIMENTAL

EXCEL-VBA

APPLICATION

QUALITY: 1 – 1000

FWHM

(cm-1)

1.Introducción

2. Objetivos

3. Metodología y

materiales

4. Resultados y

discusión

5. Conclusiones y

Recomendaciones

RAMAN

SPECTROCOPY

I2D/IG ID/IG

EXPERIMENTAL

Lavin-Lopez, M.P., et al., Synthesis and characterization of graphene: Influence of synthesis variables. Physical Chemistry Chemical Physics, 2014. 16(7): p. 2962-2970.

Ferrari, A. C., J. C. Meyer, y col. (2006). Raman Spectrum of Graphene and Graphene Layers. Physical Review Letters 97(18): 187401.

RESULTS AND DISCUSSION

Reaction Temperature

• 900 - 1050ºC

Reaction Time

• 1 – 40 min

CH4/H2

Flow Rate Ratio

• 0.07 – 0.4 v/v

QT during reaction step

• 60 – 130 Nml/min

a)


Influence of the reaction Tª at different reaction times

Tª reaction=1050ºC, CH4/H2=0.3 v/v, timereaction=10 min, QT=130 Nml/min

% MULTILAYER

GRAPHENE

% FEW-LAYERS

GRAPHENE

% BILAYER

GRAPHENE QUALITY

81.34 17.00 1.66 4.2

COPPER


1000 1500 2000 2500 3000

Inte

nsi

ty (

a.u

.)

Raman Shift (cm-1

)

MULTILAYER GRAPHENE

FEW-LAYER GRAPHENE

BILAYER GRAPHENE

ID/IG=0.16

ID/IG=0.04

ID/IG=0.04

I2D/IG=0.74FWMH=65 cm-1

RAMAN SHIFT=2691 cm-1





1

2

3

b)

OPTIMUM

CONDITIONS

Tª=1050ºC

Time=10 min

a)

COPPER


Influence of the CH4/H2 Flow Rate Ratio



% MULTILAYER

GRAPHENE

% FEW-LAYERS

GRAPHENE

% BILAYER

GRAPHENE QUALITY

19.67 50.92 29.41 34.7

1000 1500 2000 2500 3000

BILAYER GRAPHENE

FEW-LAYER GRAPHENE

Inte

nsit

y (

a.u

.)

Raman Shift (cm-1)

MULTILAYER GRAPHENE

3

2

1

ID/IG=0.16 I2D/IG=0.56FWMH=65 cm-1






b)

OPTIMUM

CONDITIONS CH4/H2=0,07 v/v

a)

COPPER


Influence of the QT during the reaction step



% MULTILAYER

GRAPHENE

% FEW-LAYERS

GRAPHENE

% BILAYER

GRAPHENE

QUALITY

10.87 33.27 55.86 59.3

1000 1500 2000 2500 3000

Inte

nsi

ty (

a.u

.)

Raman Shift (cm-1)

BILAYER GRAPHENE

FEW-LAYER GRAPHENE

MULTILAYER GRAPHENE







ID/IG=0.08

ID/IG=0.05

ID/IG=0.09

b)

OPTIMUM

CONDITIONS QT=60 Nml/min


Lavin-Lopez, M.P., et al., Thickness control of graphene deposited over polycrystalline nickel. New Journal of Chemistry, 2015.

NICKEL

Influence of the reaction temperature


% MULTILAYER

GRAPHENE

% FEW-LAYERS

GRAPHENE

% BILAYER

GRAPHENE

% MONOLAYER

GRAPHENE QUALITY

0.87 40.20 21.80 37.13 397

MONOLAYER GRAPHENE

1000 1500 2000 2500 3000

Inte

nsi

dad

(u.a

.)

Señal Raman (cm-1)

ID/IG=0.184

ID/IG=0.006

ID/IG=0.001

ID/IG=0.027

I2D/IG=2.494 FWHM=37 cm-1








BILAYER GRAPHENE

FEW-LAYERS GRAPHENE

MULTILAYER GRAPHENE

Inte

nsi

ty (

a.u

.)

Raman Shift (cm-1)

OPTIMUM

CONDITIONS Tª=980ºC



NICKEL


% MULTILAYER

GRAPHENE

% FEW-LAYERS

GRAPHENE

% BILAYER

GRAPHENE

% MONOLAYER

GRAPHENE QUALITY

0.45 27.15 20.39 51.99 536

Influence of the CH4/H2 Flow Rate Ratio

1000 1500 2000 2500 3000

Inte

nsi

dad

(u.a

.)

Señal Raman (cm-1)



ID/IG=0.142

ID/IG=0.027

ID/IG=0.006

ID/IG=0.062







MONOLAYER GRAPHENE

BILAYER GRAPHENE

FEW-LAYERS GRAPHENE

MULTILAYER GRAPHENE

Inte

nsi

ty (

a.u

.)

Raman Shift (cm-1)

OPTIMUM

CONDITIONS CH4/H2=0,07 v/v



NICKEL

Influence of the QT during the reaction step

at different times


% MULTILAYER

GRAPHENE

% FEW-LAYERS

GRAPHENE

% BILAYER

GRAPHENE

% MONOLAYER

GRAPHENE QUALITY

0.33 11.15 8.41 80.12 810

1000 1500 2000 2500 3000

Inte

nsi

dad (

u.a

.)

Señal Raman (cm-1)

ID/IG=0.075

ID/IG=0.019

ID/IG=0.005

ID/IG=0.006



I2D/IG=1.003

FWHM=58 cm-1 RAMAN SHIFT=2714 cm-1



I2D/IG=0.460

FWHM=79 cm-1 RAMAN SHIFT=2711 cm-1

MONOLAYER GRAPHENE

BILAYER GRAPHENE

FEW-LAYERS GRAPHENE

MULTILAYER GRAPHENE

Inte

nsi

ty (

a.u

.)

Raman Shift (cm-1)

OPTIMUM

CONDITIONS

QT=80Nml/min

Time=1 min

CONCLUSIONS

VARIABLE COPPER NICKEL

REACTION Tª 1050 ºC 980 ºC

CH4/H2 FLOW RATE RATIO

0.07 v/v 0.07 v/v

QT DURING REACTION STEP

60 Nml/min 80 Nml/min

REACTION TIME 10 min 1 min

GRAPHENE

QUALITY 59 810

CVD-GRAPHENE SYNTHESIS USING DIFFERENT TRANSITION

METALS AS CATALYST

Mª del Prado Lavín López

mª del prado lavín lópez - phantomsnet.net · dong, l.-x. and q. chen (2010). properties,...

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