GRAPHENE SYNTHESIS USING CATALYTIC CHEMICAL VAPOUR DEPOSITION

PRESENTED BY, ARUNI S. MS, CNN M.G.UNIVERSITY

CONTENTS

CHEMICAL VAPOUR DEPOSITION

1. 2. 3. 4. 5. Introduction General outline and Mechanism Applications of CVD Advantages and disadvantages Classification

GRAPHENE CATALYTIC CHEMICAL VAPOUR DEPOSITION OF GRAPHENE

CHARACHTERISATION

APPLICATION CONCLUSION FUTURE REFERENCES

CHEMICAL VAPOUR DEPOSITION

Chemical Vapour Deposition (CVD) - is a chemical process used to produce high - purity, high performance solid materials - its often used in semiconductor industry to produce thin films and coatings - it is a technique for synthesizing materials in which chemical components in vapour phase reacts to form solid on a surface - the primary requirement is that the materials must start out in the vapour phase

GENERAL OUTLINE

Schematic Representation of a Chemical Vapour Depositor

GENERAL CVD PROCESS

Deposition of thin film includes the transport of one or more volatile precursors in vapour phase to the reaction chamber, where it decompose on a heated surface.

Steps involved in deposition

- Transport of the materials in gas phase to deposition zone - Diffusion or convection of gaseous precursors through the boundary layer - Adsorption of film precursors on to the growth surface - Surface diffusion precursors to growth sites - Surface chemical reactions leading to the deposition of a film - Desorption of by products - Transport of gaseous by products out of the reactor

MECHANISM OF DEPOSITION

Two main steps : - transport of gas phase materials to the reaction zone and reaction of materials - deposition of film on the substrate

Transport process involves gas supply, convection and diffusion of gaseous reactants Deposition process involves adsorption of reactant species on to the substrate surface, surface chemical reaction between the reactants, diffusion of the by products and film deposition Forced and Free convection Viscous friction Diffusion

SCHEMATICAL REPRESENTATION OF THE MECHANISM OF GROWTH

Important factors that influence the homogeneous reaction: - gas residence time near the surface and gas heating

Gas phase reactions are homogeneous and produce powdery material Surface reactions are heterogeneous and produce thin films In the end desorption and diffusion of by - products

APPLICATIONS OF CVD

Deposition of materials in micro and nano fabrication into various forms including monocrystalline, polycrystalline, amorphous. Silicon, Carbon fibre, Carbon nano fibres (CNF)/nano filaments/ nano rods, Silicon di oxide, Silicon Germanium, Tungsten, Silicon carbide nanostructure, Silicon nitride nanomaterials, Silicon oxynitride, Titanium nitride and various high k dielectrics can be deposited

Synthetic diamonds and nanodiamonds Largely hard coatings to improve the life and performance of cutting tools In microelectronics industry

In glass industry to coat large glass panels with SnO2, TiN or SiO2 Layers in solar cells, coatings for catalysts, membranes or optical layers in waveguides Synthetic gold coatings are deposited on large volumes of personal jewelry

ADVANTAGES & DISADVANTAGES

ADVANTAGES : Can deposit materials which are hard to evaporate Increased flexibility and Good reproducibility Low maintenance High yields High efficiency Can grow epitaxial films

DISADVANTAGES
High temperatures Complex processes Toxic and corrosive gasses

CLASSICATION OF CVD
Based on - means by which chemical reactions are initiated - process conditions

I. According to the operating pressure

Atmospheric Pressure CVD (APCVD) - occurs at atmospheric pressure

Low Pressure CVD (LPCVD) - occurs at sub atmospheric pressure

Ultrahigh Vacuum CVD (UHVCVD)

- the process takes place typically below 10-6 Pa

II. According to the physical characteristics of vapour used

Aerosol Assisted CVD (AACVD) : - precursors are transported to substrate through liquid/gas aerosol - suitable for involatile precursors

Direct Liquid Injection CVD (DLICVD)

- precursors are in liquid form

- suitable for solid and liquid precursors - high growth rates can be achieved

Metalorganic CVD (MOCVD)

- based on metalorganic precursors - deposition of a wide variety of materials - easy removal of by products - high purity

III. According to the source of energy supplied

Plasma enhanced CVD (PECVD) - plasma is created to enhance the chemical reaction rates of the precursors, by RF frequency or DC discharge - deposition at lower temperatures

- wide variety of nano materials can be deposited - high quality and good alignment

Rapid Thermal CVD (RTCVD) - heating only at substrate by heating lamps or other means - reduce unwanted gas phase reaction

Catalytic CVD (CCVD/Cat - CVD) - also known as Hot filament CVD (HFCVD) or Hot wire CVD (HWCVD) - hot filament is used to supply the required energy - nano diamond, CNT and graphene and a wide variety of nanomaterials can be produced

GRAPHENE

A flat monolayer carbon atoms highly packed into 2 D honey comb lattice and is a building block for graphite materials of all other dimensionalities Term coined by Hanns Peter Boehm

Allotrope of Carbon with one atom thick planar sheets of sp2 bonded carbon atoms C C bond length is 0.142 nm Nobel Prize in Physics for2010 for Andre Geim and Konstantin Novosolov

They extracted the material from a piece of graphite such as

that found in ordinary pencils using adhesive tape, repeating the tape - trick until they were left with miniscule flakes of graphene.

Honey comb structure of graphene

Can be wrapped up to 0D fullerenes 1D nanotubes 3D graphite

PROPERTIES

Atomic properties Electronic properties Mechanical properties Thermal properties Biological properties

CATALYTIC CHEMICAL VAPOUR DEPOSITION OF FEW LAYERED GRAPHENE

MgO Co catalyst is used Catalyst prepared by dissolving 5 g MgO in 0.36 g Cobalt nitrate hexahydrate in 100ml ethanol Ultra sonication for 1hr and drying for 1300C for 12hr and ground to fine powder

Catalyst loaded in ceramic boat in CCVD is reacted with methane at a rate of 375ml/min at 10000C for 30 min. Purification: - Product is acidized by con. HCl to remove MgO and Co particles - Washing with demineralised water to attain neutral pH and dried at 700C

RESULT

After purification 50g graphene was obtained from 500g of loaded catalyst. Therefore the yield of reaction is 10%.

CHARACHTERISATION

Scanning Electron Microscopy (SEM) High Resolution Transfer Electron Microscopy (HRTEM) Atomic Force Microscopy (AFM) XPS Raman Spectroscopy X-ray Diffraction Spectroscopy (XRD)

SEM

Fig. a a) Field-emission SEM image of few-layered graphene grown by CVD. b) High-magnification SEM image of few-layered graphene.

Fig. b

HRTEM

Fig. a
a) b) c)

Fig. b

Fig. c

HRTEM image of few-layered graphene, showing individual graphene sheets with the edges of the graphitized layers. HRTEM image of sutured and crumpled graphene paper; solid triangles indicate ripples in the few-layered graphene. HRTEM image of as-grown graphene without purified treatment process.

AFM, XPS & RAMAN SPECTRUM

AFM image of the few layered graphene materials

a. Wide survey of XPS spectrum of sample b. Typical Raman spectrum for few layered graphene

XRD

APPLICATIONS

Semi conductor interconnects & IC chips Chemical and gas sensors Quantum computers Paper battery and Battery electrodes EMI & RFI shielding applications Electrostatic paints especially for automobile parts Conducting ink

Printed Electronics Fuel cells and ultra capacitors Aerospace Thin film industry Composite application Defense application Solar panels and cells Bio devices mainly for DNA sequencing

DEVELOPED PRODUCTS

Transparent graphene electrode

Ultra strong paper from graphene Proof of principle transistors, loop device and circuitry

Graphene microchip

Flexible touch screen made of graphene Transparent conductive films on PI and glass substrates

Graphene armour

Graphene ink Solar panel coating

CONCLUSION
The successful synthesis of few layered graphene through catalytic chemical vapour deposition can bescaled upto large scale. This approach not only opens a new, low cost, method to produce graphene industrially, but it also provides a realistic possibility of graphene applications in molecular electronics and polymer composites.

PROMISING FUTURE

REFERENCES

Chemical Vapour Deposition by Xianbao Wang, Haijun You, Fangming Liu, Mingjian Li, Li Wan, Qin Li, Yang Xu, Rong Tian, Ziyong Yu, Dong Xiang and Jing Cheng Substrate free synthesis of large area, continuous multi - layer graphene film by Fang Liu, Yong Zhang

Graphene Synthesis by CVD on Copper Substrate by Mark Borysiak. Formation of Bilayer Bernal Graphene: Layer by Layer Epitaxy via Chemical Vapour Deposition by Kai Yan, Hailin Peng, Yu Zhou, Hui Li and Zhongfan Liu Large Area, Few Layer Graphene Films on Arbitrary Substrates by Chemical Vapour Deposition by Alfonso Reina, Xiaoting Jia, John Ho, Daniel Nezich, Hyungbin Son, Vladimir Bulovic, Mildred S., Dresselhaus and Jing Jong

Direct Chemical Vapour Deposition of Graphene on Dielectric Surfaces by Ariel Ismach, Clara Druzgalski, Samuel Penwell, Adam Schwartzberg, Maxwell Zheng, Ali Javey, Jeffrey Bokor and Yuegang Zhang Introduction to Nanoscience and Nanotechnology by Chattopadhyay Chemical Vapour Deposition Mechanism by Conggin Miao, Churan Zheng, Owen Liang and Ya Hong Xie.

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