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Carbon Nanotubes and Graphene for Electronics Applications: Technologies, Players & Opportunities 2009-7-16 11:23

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July 2009

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Carbon Nanotubes Graphene Electronics

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Summary

Carbon Nanotubes (CNTs) and graphene exhibit extraordinary electrical properties for organic materials, and have a huge potential in electrical and electronic applications such as sensors, semiconductor devices, displays, conductors and energy conversion devices (e.g., fuel cells, harvesters and batteries). This report brings all of this together, covering the latest work from 78 organizations around the World to details of the latest progress applying the technologies. Challenges and opportunities with material production and application are given.

Applications of Carbon Nanotubes and Graphene for electronics applications
Depending on their chemical structure, carbon nanotubes (CNTs) can be used as an alternative to organic or inorganic semiconductors as well as conductors, but the cost is currently the greatest restraint. However, that has the ability to rapidly fall as new, cheaper mass production processes are established, which we cover in this report. In electronics, other than electromagnetic shielding, one of the first large applications for CNTs will be conductors. In addition to their high conductance, they can be transparent, flexible and even stretchable. Here, applications are for displays, replacing ITO; touch screens, photovoltaics and display bus bars and beyond.

In addition, interest is high as CNTs have demonstrated mobilities which are magnitudes higher than silicon, meaning that fast switching transistors can be fabricated. In addition, CNTs can be solution processed, i.e. printed. In other words, CNTs will be able to provide high performing devices which can ultimately be made in low cost manufacturing processes such as printing, over large areas. They have application to supercapacitors, which bridge the gap between batteries and capacitors, leveraging the energy density of batteries with the power density of capacitors and transistors. Challenges are material purity, device fabrication, and the need for other device materials such as suitable dielectrics. However, the opportunity is large, given the high performance, flexibility, transparency and printability. Companies that we surveyed report growth rates as high as 300% over the next five years.

Graphene, a cheap organic material, is being enhanced by companies that are increasing its conductivity, to be used in some applications as a significantly cheaper printed conductor compared to silver ink. All this work is covered in this new report.

Activity from 78 organizations profiled
We have researched 78 companies and academic institutions working on carbon nanotubes and graphene, all profiled in the report. While manufacturers in North America focus more on single wall CNTs (SWCNTs); Asia and Europe, with Japan on top and China second, are leading the production of multi wall CNTS (MWCNTs) with Showa Denko, Mitsui and Hodogaya Chemical being among the largest suppliers. The split of number of organizations working on the topic by territory is shown below.

Opportunities for Carbon Nanotube material supply
A number of companies are already selling CNTs with metallic and semiconducting properties grown by several techniques in a commercial scale but mostly as raw material and in limited quantities. However, the selective and uniform production of CNTs with specific diameter, length and electrical properties is yet to be achieved in commercial scale. A significant limitation for the use of CNTs in electronic applications is the coexistence of semiconducting and metallic CNTs after synthesis in the same batch. Several separation methods have been discovered over the last few years which are covered in the report, as is the need for purification.

Opportunities for Carbon Nanotube device manufacture
There are still some hurdles to overcome when using printing for the fabrication of thin carbon nanotube films. There is relatively poor quality of the nanotube starting material, which mostly shows a low crystallinity, low purity and high bundling. Subsequently, purifying the raw material without significantly degrading the quality is difficult. Furthermore there is also the issue to achieve good dispersions in solution and to remove the deployed surfactants from the deposited films. The latest work by company is featured in the report.

Key benefits of purchasing this report
This concise and unique report gives an in-depth review to the applications, technologies, emerging solutions and players. It addresses specific topics such as:

Activities of 78 global organizations which are active in the development of materials or devices using carbon nanotubes or graphene.
Application to conductors, displays, transistors, super capacitors, photovoltaics and much more
Types of carbon nanotubes and graphene and their properties and impact on electronics
Current challenges in production and use and opportunities
Forecasts for the entire printed electronics market which carbon nanotubes and printed electronics could impact

For those involved in making or using carbon nanotubes, or those developing displays, photovoltaics, transistors, energy storage devices and conductors and want to learn about how they can benefit from this technology, this is a must-read report.

Table of Contents

EXECUTIVE SUMMARY AND CONCLUSIONS
1. INTRODUCTION
1.1. What are Carbon Nanotubes
1.1.2. History of CNTs
1.2. What is Graphene
1.2.1. Manufacturing graphene
1.3. Properties for electronic and electrical applications
1.4. Manufacture of CNTs
1.4.2. Arc Method
1.4.3. Laser Ablation Method
1.4.4. Chemical Vapor Deposition (CVD)
1.5. Printing Carbon Nanotubes
1.6. Latest progress with printing carbon nanotubes
1.6.1. Application of printed carbon nanotubes to flexible displays
1.6.2. Application of printed carbon nanotubes to transistors
1.6.3. Application of printed carbon nanotubes to energy storage devices-supercapacitors
2. CNT/GRAPHENE TRANSISTOR
2.1. Comparison to other semiconductors
2.2. Latest progress with CNT/Graphene Transistors
2.2.1. Separating metallic and semiconductor carbon nanotubes
2.2.2. Graphene field effect transistors
2.3. Challenges
3. CARBON NANOTUBES AS CONDUCTORS
3.2. Comparison to other conductors
3.3. Conductor deposition technologies and main applications
3.4. Latest progress with Carbon Nanotube conductors
3.5. Challenges
4. OTHER APPLICATIONS OF CNTS
4.1. NRAM data storage device
4.2. Organic photovoltaic devices and hybrid organic-inorganic photovoltaics
4.3. Supercapacitors and/or batteries
4.4. CNTs for smart textiles
4.5. Thin film loudspeakers
5. COMPANIES PROFILES
5.1. Angstron Materials LLC., USA
5.2. Apex Nanomaterials, USA
5.3. Applied Nanotech, USA
5.4. Arry International Group, Hong Kong
5.5. BASF, Germany
5.6. Bayer MaterialScience, Germany
5.7. Canatu Ltd., Finland
5.8. Carben Semicon Ltd, Russia
5.9. Carbon Solutions, Inc., USA
5.10. CarboLex, Inc., USA
5.11. Cap-XX Australia
5.12. CheapTubes, USA
5.13. Chengdu Organic Chemicals Co. Ltd. (Timesnano), China
5.14. Cornell University, USA
5.15. CSIRO, Australia
5.16. Dainippon Screen Mfg. Co., Ltd., Japan
5.17. DuPont, USA
5.18. Eikos, USA
5.19. Frontier Carbon Corporation (FCC), Japan
5.20. Fujitsu Laboratories, Japan
5.21. Georgia Tech Research Institute (GTRI), USA
5.22. Graphene Energy Inc., USA
5.23. Graphene Industries Ltd., UK
5.24. HeJi, Inc., China
5.25. Helix Material Solutions Inc., USA
5.26. Hodogaya Chemical Co., Ltd., Japan
5.27. Honjo Chemical Corporation, Japan
5.28. HRL Laboratories, USA
5.29. Hyperion Catalysis International, Inc.
5.30. IBM, USA
5.31. ILJIN Nanotech Co. Ltd., Korea
5.32. Intelligent Materials PVT. Ltd. (Nanoshel), India
5.33. MER Corporation, USA
5.34. MIT, USA
5.35. Mitsui Co., Ltd, Japan
5.36. Mknano, Canada
5.37. Nano-c, USA
5.38. NanoCarbLab (NCL), Russia
5.39. Nano Carbon Technologies Co., Ltd. (NCT)
5.40. Nanocs, USA
5.41. Nanocyl s.a., Belgium
5.42. NanoIntegris, USA
5.43. NanoLab, Inc., USA
5.44. NanoMas Technologies, USA
5.45. Nano-Proprietary, Inc., USA
5.46. Nanoshel, Korea
5.47. Nanostructured & Amorphous Materials, Inc., USA
5.48. Nanothinx S.A. , Greece
5.49. Nantero, USA
5.50. NEC Corporation, Japan
5.51. Noritake Co., Japan
5.52. Optomec, USA
5.53. Rutgers University, USA
5.54. Samsung Electronics, Korea
5.55. SES Research, USA
5.56. Shenzhen Nanotechnologies Co. Ltd. (NTP)
5.57. Showa Denko Carbon, Inc. (SDK), USA
5.58. ST Microelectronics, Switzerland
5.59. SouthWest NanoTechnologies (SWeNT), USA
5.60. Sungkyunkwan University Advanced Institute of Nano Technology (SAINT), Korea
5.61. Sun Nanotech Co, Ltd., China
5.62. Surrey NanoSystems, UK
5.63. Toray Industries, Japan
5.64. Tsinghua University, China
5.65. Unidym, Inc., USA
5.66. University of California Los Angeles (UCLA), USA
5.67. University of Cincinnati (UC), USA
5.68. University of Oklahoma, USA
5.69. University of Southern California (USC), USA
5.70. University of Stanford, USA
5.71. University of Stuttgart, Germany
5.72. University of Surrey, UK
5.73. University of Texas at Austin, USA
5.74. University of Tokyo, Japan
5.75. Vorbeck Materials Corp, USA
5.76. XG Sciences, USA
5.77. Xintek Nanotechnology Innovations, USA
5.78. Zyvex, Inc., USA
6. FORECASTS AND COSTS
6.1. Market Opportunity and roadmap for Carbon Nanotubes and Graphene
6.2. Costs of SWCNTs
6.3. New Focus for Printed Electronics-the importance of flexible electronics
6.4. Focus on invisible electronics
6.5. Shakeout in organics
6.6. Market pull

APPENDIX 1: GLOSSARY
APPENDIX 2: PUBLICATIONS AND CONSULTANCY

TABLES
2.1. Comparison of the main options for semiconductors
3.2. Typical Sheet Resistivity figures for conductors
3.3. Main applications of conductive inks and some major suppliers today
5.1. Baytubes product specifications
5.2. Results of pulse-heat CVD
5.3. Characteristics of the CNT-FED compared with LEDs
6.1. Market forecast by component type for 2009 to 2029 in US $ billions, for printed and potentially printed electronics including organic, inorganic and composites
6.2. Costs of SWeNTs
6.3. SES Research
6.4. Nanothinx S.A. (price per gram in Euros)
6.5. Nanocs
6.6. Arry International Group
6.7. Carbon Solutions
6.8. Carbolex
6.9. Cheaptubes
6.10. Helix Material Solutions
6.11. MER Corporation

FIGURES
1.1. Structure of single-walled carbon nanotubes
1.2. The chiral vector is represented by a pair of indices (n, m). T denotes the tube axis, and a1 and a2 are the unit vectors of graphene in real space.
1.3. Traditional CNT film processes are complex
1.4. CNT networks for flexible displays
1.5. CNT Transistors through Specialized Printing Processes from NEC Corporation
2.1. Atomic Force Microscope image of carbon nanotubes before and after processing.
2.2. Carbon nanotube Field Effect transistors
2.3. Epitaxial graphene FETs on a two-inch wafer scale
2.4. Graphene field effect transistor from IBM
2.5. An enlarged photo of a several-millimeter square chip with graphene transistors. The graphene transistors can be seen in the enlarged photo of the tips of the two electrodes.
2.6. An LSI mounted on a flexible substrate by using CNT bumps
2.7. Printed CNT-TFT on a DuPont® Kapton® FPC polyimide film: (a) schematic structure cross-section view, [(b) and (c)] picture of the CNT-TFT, (b) circuit, and (c) optical microphotography of the CNT-TFT (top view). The CNT-TFT is in a top-gated configuratio
3.1. Potential applications are flexible solar cells, displays and touch screens.
3.2. Targeted applications for carbon nanotubes by Eikos
3.3. Conductance in ohms per square for the different printable conductive materials compared with bulk metal
3.4. New printable elastic conductors made of carbon nanotubes are used to connect OLEDs in a stretchable display that can be spread over a curved surface.
3.5. Stretchable mesh of transistors connected by elastic conductors
3.6. Hybrid graphene-carbon nanotube G-CNT conductors
4.1. A three-terminal memory cell based on suspended carbon nanotubes: (a) nonconducting state '0', (b) conducting state '1', and (c) Nantero's NRAM™.
4.2. Georgia Tech Research Institute (GTRI) scientists have demonstrated an ability to precisely grow "towers" composed of carbon nanotubes atop silicon wafers. The work could be the basis for more efficient solar power for soldiers in the field.
4.3. The carbon nanotube supercapacitor versus batteries and traditional capacitors
4.4. Anatomy of a supercapacitor: two films combining Indium Oxide (In2O3) separated by a layer of Nafion film
4.5. Transparent film holds embedded nanotube/nanowire capacitor with high energy density and storage capacity
4.6. Battery from Rensselaer Polytechnic Institute, USA
4.7. (a) SEM image of CMG particle surface, (b) TEM image showing individual graphene sheets extending from CMG particle surface, (c) low and high (inset) magnification SEM images of CMG particle electrode surface, and (d) schematic of test cell assembly.
4.8. Proposed battery design from UCLA
4.9. Four scanning electron microscope images of the spinning of carbon nanotube fibres
4.10. Photographs of CNT-cotton yarn. (a) Comparison of the original and surface modified yarn. (b) 1 meter long piece as made. (c) Demonstration of LED emission with the current passing through the yarn.
4.11. The CNT thin film was put on a flag to make a flexible flag loudspeaker
4.12. Carbon nanotube thin film loudspeakers
5.1. Directly produced prepatterned films
5.2. Cap-XX supercapacitor technology with carbon coating.
5.3. Layout of CNT-FE BLU fabricated through pulse
5.4. Schematic illustration of experimental setup
5.5. Illustrations of micro-patterned cathodes
5.6. SEM images of CNTs on Samples C, D and E
5.7. Field emission properties of CNT-emitters patterned on a glass substrate by pulse-heat CVD. Luminescence images from the backsides of the cathode at various applied voltages are indicated in inset.
5.8. SEM images of CNTs on the micro-patterned electrodes with interline spacing (a) 20, (b) 50, (c) 100 and (d)200 !m (top view).
5.9. CNT Ink Production Process
5.10. Target application areas of Eikos
5.11. The graphene microchip mostly based on relatively standard chip processing technology
5.12. Color pixel; 3mm, display area; 48mm x480mm
5.13. Color pixel; 1.8mm, display area; 57.6mm x 460.8mm.
5.14. A prototype display of digital signage.
5.15. Application images of public displays.
5.16. Schematic structure of CNT-FED using line rib spacer.
5.17. Phosphor-dot pattern and conductive black-matrix pattern.
5.18. An application on the information desk. The color pixel pitch were 3mm(left) and 1.8mm (right).
5.19. A photograph of a displayed color character pattern in two lines. The color pixel pitch was 1.8mm.
5.20. SEM images of CNT deposited metal electrode.(a) A photograph of the CNT deposited metal frame. (b) SEM image; boundary of barrier area. (c) SEM image; surface of the CNT layer. (d) SEM image; a surface morphology of CNT.
5.21. One of prototype displays on the vending machine. The display was under field-testing in out-door. The CNT-FED and display module were under testing continuously during ca.15months in Osaka-city up to date, and they were still continued.
5.22. A photograph of driving system. A solar cell and the charging controller, yellow small battery and CNT-FED module.
5.23. A photograph of a displayed color character which was driven by solar cell and small battery. The color pixel pitch was 1.8mm.
5.24. CNT films from Rutgers University
5.25. Optical microscope image of Xintek's CNT films
5.26. A field emission image of an array of CNT dots of 2mm in diameter (1.55V/μm)
6.1. Supercapacitors
6.2. Market forecast by component type for 2009-2019 in US $ billions, for printed and potentially printed electronics including organic, inorganic and composites
6.3. Chengdu Organic Chemicals Co. Ltd. (Timesnano)
6.4. HeJi Inc
6.5. The percentage of printed and partly printed electronics that is flexible 2009-2019
6.6. Evolution of printed electronics structures