Background
We are very familiar with the concept of miniature display through our smartphones, smartwatches, tablets, e-readers, etc. These displays have undergone a steady evolution through the years starting from Liquid Crystal Display(LCD) to LED Backlight to Active Matrix Organic LED(AMOLED) Display.
The next big development in this area is going to be – Flexible Display
Flexible Display is amenable to being folded/bent as opposed to traditional displays. This is possible due to the organic materials used in making these displays.
Despite being amenable by nature, organic materials have lower reliability and cannot be processed at higher temperatures[5][6][7].
This lacuna can only be overcome if we could
- Increase the reliability of organic materials (work in progress) or
- Use of inorganic materials to make Flexible Display
The possible use of inorganic materials warrants a hybrid heterostructure grown on two-dimensional (2D) layered materials like Graphene or hexagonal Boron Nitride(hBN)[2][18][19][20].
Accordingly, the article talks about the research carried out by two different groups using graphene as the template for GaN growth
In 2014, a research group at Seoul National University (SNU) grew Gallium nitride(GaN) on graphene using MOCVD paving the way for its adoption in Flexible Displays[1][8].
Similarly, in 2017, a Japanese research group grew crystalline GaN films using graphene buffer on an amorphous substrate(glass) with the use of Pulsed Sputtering Deposition (PSD)[2].
Material Characteristics
Graphene is a monolayer of carbon atoms arranged in a chicken wire or hexagonal pattern[1][9].

Graphite(3D) is formed by stacking graphene(2D) which are bonded by weak Van der Waal’s force. A monolayer of graphene was isolated from Graphite in 2004 at the University of Manchester by mechanical exfoliation.


III-Nitride Semiconductors like GaN and InN are used for making Light Emitting Diodes(LEDs) (along with quantum structures like quantum wells, quantum dots, etc.) for covering the entire Visible, Infrared(IR) and UltraViolet(UV) spectrum.
Research is also ongoing to make high-power, deep Ultra-Violet(DUV) LEDs using AlGaN or AlN which have applications in disinfection, curing, gas sensing, and sterilization[21][22][24].
Due to the unavailability of lattice-matched substrates, Nitrides are grown on non-native materials like Sapphire or Silicon Carbide(SiC)[12]. This leads to mismatch and generation of faults like stacking fault, threading dislocation(TDD) etc. at the boundary of GaN/substrate.
When devices are fabricated on these materials, the faults act as trap sites(for the charge carriers) thereby reducing the output and reliability of the LED[15].
Hence the best option is to grow GaN on materials that are lattice matched to it or have a low mismatch to it. This helps in adopting GaN for applications like flexible displays and devices beyond two terminals like HEMT etc.
III-Nitride for Flexible Display??
Organic materials used in fabricating OLEDs are a choice for making flexible displays. III-Nitride materials owing to their superior light output, ease of fabrication,n, and reliability can be adopted to make flexible displays if they meet the following criteria:
- Low-temperature growth
- Compatible with low-cost substrates like plastic, glass, etc.
Normally, III-Nitride semiconductors like GaN, AlGaN, InGaN, etc. are grown using Metal Organic Chemical Vapor Deposition(MOCVD) or Molecular Beam Epitaxy(MBE). Owing to this, the temperature required for a high-quality epitaxial film is more than 850oC [1][2][8].
Also, the substrate(sapphire/SiC) currently utilized for III-Nitride semiconductor growth is crystalline and hence resists any change in shape.
Hence, the substrate of choice should have low lattice mismatch, a similar structure, and be flexible(bendable) for III-Nitride semiconductor growth.
Considering this, one well-researched material meets the criteria – Graphene
Graphene for III-Nitride Growth
As discussed earlier, we are now going to delve into the research work by two groups on their efforts to grow GaN on graphene. The device outcome from the films is similar to GaN on Sapphire or GaN on Silicon Carbide(SiC).
A] Research at Seoul National University(SNU)[2014]
A research group at Seoul National University (SNU) grew Gallium nitride(GaN) on graphene using MOCVD[1][8]. Post-growth, they incorporated a transfer technique that assisted in measuring GaN LEDs on an organic(polyimide) substrate.
- Graphene Growth
Graphene films are grown on Cu foil using Chemical Vapor Deposition(CVD). The grown films are Multi-Layer Graphene(MLG) which is semi-transparent in nature[8].
- Transfer & Growth
This MLG graphene film is then transferred to a SiO2/Si substrate to act as a template for III-Nitride growth.
To grow the GaN micro-rods, MOCVD reactants were used along with nitrogen as the carrier gas. A 2-μm-thick GaN buffer layer was grown to improve the vertical alignment of the micro-rods.

The micro-rods were not grown selectively. The geometry of the GaN micro-rods depends on the growth time[8].
- Material Characterization
XRD
GaN micro-rods grown on graphene with/without a GaN buffer layer are examined using an XRD θ-2θ scan[8]. The range of scan was 20o-80o.
GaN with a buffer layer – Two Wurtzite Peaks
GaN with no buffer layer – Multiple Peaks

SEM
The FE-SEM image reveals the surface morphology of the GaN buffer layer and GaN micro-rods which is as expected[8].

TEM
TEM images of the sidewall Multi-Quantum Well(MQW)(shown below) of the GaN micro-rod LEDs indicate growth comparable to baseline substrates like Sapphire/SiC[8].

- Electrical Characterization
As the main objective of GaN growth on graphene is for flexible display applications, let us try to understand the electrical/optical output. Before doing the measurements, devices need to be fabricated on the grown films
Device Fabrication[8]
- Post GaN micro-rod LED growth, the cavity between LEDs is filled using an insulating layer – polyimide
- The top layer of GaN micro-rod LEDs is opened using oxygen plasma etching
- Ni/Au used to make ohmic contact with p-GaN
- SiO2/Si substrate removed using wet(BOE) etching
- A Ti/Au is deposited and Ag is added at the bottom of LEDs to provide a reliable end for the current injection
- Coaxial GaN micro-rod LEDs were then transferred onto a polyimide substrate

The emitted light from the fabricated LED despite the transfer process demonstrated reliable operation.

This operation continued even when the polyimide substrate was bent to change the radius of curvature. A radius of curvature of 6 mm for a 20-mm wide substrate under deformation(bent) does not cause the EL intensity & EL peak wavelength to change over 1000 cycles[8].

The methodology adopted by SNU researchers has the potential to integrate inorganic substrates with organic materials for future flexible displays. The requirement for a low thermal budget is accomplished by the introduction of a transfer technique.
B] Research at the University of Tokyo[2017]
A different approach was used by a research group at the University of Tokyo. Pulsed Sputtering Deposition(PSD) is used for III-Nitride film growth on glass using graphene as a buffer layer. In this technique, there is no transfer involved post-growth of GaN film[2].
- Graphene Growth
Graphene is grown on Ni sheets by Chemical Vapor Deposition(CVD) and subsequently transferred onto thermally oxidized SiO2 on Si substrates.
- GaN Growth
- Flexible substrates like glass, and plastic are amorphous in nature. For GaN growth on a glass substrate, a crystalline buffer layer should be introduced between GaN and glass
- PSD used for deposition enhances surface migration of the precursors thereby reducing the epitaxial growth temperature. The maximum temperature needed by PSD is 480oC in contrast to MOCVD for the growth of GaN[2]
- Material Characterization
SEM
The films grown by PSD were characterized using scanning electron microscopy (SEM)[2]. For comparative study, two sets of films were grown
GaN film grown on SiO2/Si – Rough Surface, small grains & size of several 100 nm
GaN film grown on Graphene Buffer/SiO2/Si – Smooth Surface

XRD
The GaN film using a graphene buffer layer was scanned using an XRD 2θ/ω plot. Diffraction peaks around 26.5o & 34.5o originate from graphene {0002} and GaN {0002}[2].
This shows that the crystal quality of the GaN film is improved by introducing the graphene buffer layer.

The GaN film grown using PSD consists of wurtzite and zincblende phases when grown on graphene at 750oC. Wurtzite Phase versus growth temperature is plotted for the GaN films[2].
Aluminum Nitride(AlN) interlayer/reaction blocking layer before GaN growth on graphene to ward off an interfacial reaction between GaN and graphene.

- Electrical Characterization
Material characterization for GaN film growth on graphene buffer will be followed by electrical characterization. Before doing the measurements, devices need to be fabricated on the grown films
Device Fabrication[2]
- AlN/graphene/amorphous SiO2 was the base structure
- n-type GaN layers were grown on the AlN interlayers
- Multiple quantum wells (MQWs) of InGaN/GaN and Mg-doped p-type GaN layers were grown on top
- Deposition of Pd/Au and In electrodes as ohmic contacts on the p- and n-type GaN surfaces

Electroluminescence (EL) measurements of the fabricated devices measured with various injection currents (2.1-10.8 mA)[2]. Blue/red LED’s grown by varying the Indium proportion were also characterized.

Conclusion
Considering the process flow, characterization, and reliability, III-Nitride semiconductors are a material of choice for displays, lighting, etc. Taking this point logically ahead, research groups and industry are trying to extend III-Nitride use in low thermal budget scenarios ie. III-Nitride on a low-cost substrate.
In this article, both the research groups have used graphene to grow GaN. LEDs made from GaN on graphene are comparable to those grown on Sapphire or SiC.
Innovative approaches can help to achieve the temperature requirement by permitting the usage of low-cost large-area substrates like glass. Pulsed Sputter Deposition(PSD) is an adapted sputter technique that is innovative and can be scaled up without any additional cost.
The next challenge will be to bring in polymeric substrates like plastic etc. These materials also support roll-to-roll processing & manufacturing like glass.
If you want to share your opinion kindly do so in the comments section or email me at u2d2tech@gmail.com.
References:
- https://publishing.aip.org/publishing/journal-highlights/bendy-leds
- J. Ohta et. al., “GaN-Based Light-Emitting Diodes with Graphene Buffers for Their Application to Large-Area Flexible Devices”, IEICE TRANS. ELECTRON., VOL.E100–C, NO.2 February 2017
- https://www.nature.com/articles/am2017118
- https://www.oled-info.com/flexible-oled
- M. Aleksandrova, “Specifics and Challenges to Flexible Organic Light-Emitting Devices”, Article ID 4081697, 8 pages, Advances in Materials Science and Engineering, Volume 2016
- L. Lin et. al., “Advances and challenges for flexible energy storage and conversion devices and systems “, Energy Environ. Sci., 7, 2101, 2014,
- S. Kim et. al., “Low-Power Flexible Organic Light-Emitting Diode Display Device“, Adv. Mater., 23, 3511–3516, 2011
- K. Chung et. al., “Growth and characterizations of GaN micro-rods on graphene films for flexible light emitting diodes”, APL Materials 2, 092512, 2014
- https://en.wikipedia.org/wiki/Graphene#Definition
- http://graphita.bo.imm.cnr.it/graphita2011/graphene.html
http://www.ledjournal.com/main/news/sapphire-substrate-continues-to-dominate-led-market/
- https://www.led-professional.com/resources-1/articles/high-quality-gan-substrates-for-modern-led-technology
- https://www.nature.com/articles/s41598-017-11757-1
- https://www.nature.com/articles/am2017118
K. Chung, C.-H. Lee, and G.-C. Yi, Science 330, 655,2010
- Y. Kobayashi, K. Kumakura, T. Akasaka, and T. Makimoto, Nature (London) 484, 223,2012
- C.-H. Lee, Y.-J. Kim, Y. J. Hong, S.-R. Jeon, S. Bae, B. H. Hong, and G.-C. Yi, Adv. Mater. 23, 4614, 2011
- http://www.appliedmaterials.com/en-in/node/3344641
P. Elmlinger et. al, “A Miniaturized UV-LED Based Optical Gas Sensor Utilizing Silica Waveguides for the Measurement of Nitrogen Dioxide and Sulphur Dioxide”, Proceedings 2017, 1(4), 55
S. Beck et.al, “Evaluating UV-C LED disinfection performance and investigating potential dual-wavelength synergy”, Volume 109, Pages 207-216, 2017
- http://www.ledsmagazine.com/articles/2016/02/nikkiso-delivers-50-mw-deep-uv-leds-with-10-000-hour-lifetime.html

Hi Shahaji,
Thanks for your feedback. Accordingly will cover that also.
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