ZKE327: SOLID STATE LIGHTING 1

Assignment 1:
Use of Nanotechnology in White LEDs Fabrication
(Draft)

Prepared for:
Dr. Yam Fong Kwong
(Lecturer School of Physic)

Prepared by:

Nur Fitriah bt Rais 130310

Norfarhana bt Hamzah 130298

Norfatihah Bt Hasnawi 130299

ABSTRACT

In this paper, we report that there are a lot of uses of nanotechnology in white light emitting diode
fabrication this day. The true white emitting diode are difficult to build and actually not available.
This is because light emitting diode (LEDs) can only emit one wavelength. This can be shown
from the spectrum of colors, white can be obtained from a mixture of wavelength. Basically when
blue LED is combined with yellow phosphor then white LED (WLED) can be created. One of the
pivotal specification of white LED (WLEDs) called color temperature (Tc) used in variety of
lighting application. distributing various phosphors on top of the blue or ultra violet LED chip in
conventional phosphor conversion WLEDs (PC-WLED) color temperature can be controlled.
However phosphor is pricey and additional packaging process also required. Phosphor degradation
by internal damage also need to be solved to get best quality of PC-WLEDs [1] .The use of
nanotechnology can improve this matter. The use of nanotechnology also can hugely improve LED
color.

1.0 INTRODUCTION
Nanotechnology is the inspection of extremely small things and operated at nanoscale
level. The part of nanotechnology which associate with the operation and application of
nanostructures in called Nanofabrication. Nanotechnology finally has disclosed a lot of application
to improve quality of existing products. Such is LED lights. White light emitting diode (WLED)
are favorable devices used in many lighting application. Presently, LED use sophisticated
technology that can surpass the old and classical light sources as a result of greater efficiencies,
high continuance, fast switching, and compact size .
Up to the present, several paths have been encountered to generating white light including
use of nanotechnology in fabrication process. These had been looked into as nanotechnology is
believed can bring down the cost for production of white LED. Phosphor considered as costly and
limited earth source. Yet the classical WLED used phosphor. Several nanotechnology techniques
tried to decrease and replace this old approach. Lately quantum dots technique being used. The
toxicity of the element however is severe. Some used carbon. Carbon is said can emit visible light
when it is implied into nanoscale materials such carbon nanodots. Many had worked on phosphor-
free white LED (PF-WLEDs ) as it can give minimal color temperature variation from phosphor
degradation together with reducing production cost [1].
2.0 HISTORICAL DEVELOPMENT of WHITE LEDs
Generally, light emitting diode(LED) is a PN junction semiconductor diode which is able to emit
a monochromatic light when operated in a forward biased direction. Essentially it can produce
light from electroluminescence process caused by radiative recombination of injected minority
carrier in electron and holes [2].The very basic structure of LEDs is made up of light emitting
semiconductor material , a lead frame to hold the die and an encapsulation epoxy that will
surrounds and protect the die .The first commercially used LEDs developed and refined in 1960s
[3].After that several progress have been made over four decades resulted in further growth of
LEDs in 1990s. Blue LEDs is available that later lead to new development. Since blue is one of
the main color, blue LEDs have made the combination of red, green and blue (RGB) light
realizable to produce white light [4].
To get white light two or more wavelength are required to generate wider spectrum of light that is
a rough approximation of black body radiation curve. In order to produce additional color , material
that absorb light at one wavelength and emits at longer wavelength had been used. One of the
common material used is phosphor. Rare earth doped Yttrium aluminium garnet (YAG:R) and
cerium doped YAG that can absorb blue and ultraviolet light are example of phosphor used.
Basically there are three most known approaches as shown in Figure 1 [3].
Normally there will be pros and cons for these three approaches . The advantages of using a blue
LED and a yellow phosphor is its high theoretical efficacy, which is good for the creation of a
cheap, bright white-light source. However, this benefit comes at the expense of a lower value for
the colour-rendering index (CRI) which is typically so low that such devices are undesirable for
indoor use. Ultraviolet LEDs with phosphor mixtures provide a better CRI value and are suitable
for indoor applications but at the expense of poorer efficacy. To control white light dynamically,
the third approach, a combination of three (or more) LEDs of different wavelengths is attractive,
and may lead to higher efficacies than the ultravioletphosphor LEDs, but will generally be the
most expensive option until more advances are made further. Table 1 will show the summary of
these three approaches .

3.0 DISCUSSION
The earlier days of LED technology only focus on increasing the optical power and also
reducing cost. This day, there are so many different specification that need to look for such as color
temperature (Tc). Color temperature controlled by using various types of phosphor. materials
which is distributed on blue or ultra violet LED chip during LED packaging process.
This material in fact is expensive and additional phosphor distribution needed in phosphor-
conversion white LED (PC-WLED) manufacturing when they are used [3]. Morever this phosphor
will gradually declined and degraded due to accumulated heat in PC-WLED during operation. This
will affect color temperature as it will unintentionally changed by deteriorating light conversion
efficiency of phosphors and blue shifted white emission will occurred.
 Practical in-situ nanostructure engineering strategy is suggested for fabricating Tc-
controlled phosphor-free white light-emitting diodes (PF-WLEDs) using metal-organic chemical
vapour deposition.

3.1- Nanotechnology
3.1.1 What is nanotechnology ?
Nanotechnology is the application of scientific knowledge for the purpose of
producing such materials and systems. Nanotechnology said to have key dimension
between 1100 nm scale as shown in Figure 2. In the present phase of investigating
elementary conditions of production, technological and basic scientific research are
merging. Wherever do not explicitly differentiate between nanotechnology and
nanoscience, the term nanotechnology includes nanoscience and nanoscale.[Error!
Reference source not found.1,12] Nanoscience is the study of phenomena and
manipulation of materials at atomic, molecular and macromolecular scales, in order to
understand and exploit properties that differ significantly from those on a larger scale. [03]
Materials at the nanoscale have far greater surface areas than corresponding bulk materials,
which also leads to new or at least amplified properties for coatings and surfaces [0].
Nanotechnologies are the design, characterization, production and application of
structures, devices and systems by controlling shape and size on a nanometer scale [03].
3.2.2 What makes nano special
The properties of matter nanotechnologies such as energy changed. This is a direct
consequence of the small size of nanomaterials, physically explained as quantum effects.
The consequence is that a material (e.g. a metal) when in a nano-sized form can assume
properties which are very different from those when the same material is in a bulk form.
Properties like electrical conductivity, colour, strength and weight change when the
nanoscale level is reached: the same metal can become a semiconductor or an insulator at
the nanoscale level. Nanomaterial also can fabricated atom by atom by a process called
bottom up. nanomaterials have an increased surface-to-volume ratio compared to bulk
materials. This has important consequences for all those processes that occur at the surface
of a material, such as catalysis and detection. The properties that make nanomaterials
special [04] .

3.2.3 Nano tools and fabrication techniques

The same may hold true for nanotechnology, at least in the coming decade before production
techniques are improved. According to market researchers Freedonia, the $245 million nanotech
tools industry will grow by 30 % annually over the next few years. Microscopes and related tools
dominate now, but measurement, fabrication/production and simulation/modelling tools will grow
the fastest. Electronics and life sciences markets will emerge first; industrial, construction, energy
generation and other applications will arise later.[0]
 Microscopy

Nanotechnology uses two main kinds of microscopy. The first involves a

stationary sample in line with a high-speed electron gun. Both the scanning electron
microscope (SEM) and transmission electron microscope (TEM) are based on this
technique. The second class of microscopy involves a stationary scanner and a
moving sample. The two microscopes in this class are the atomic force microscope
(AFM) and the scanning tunnelling microscope (STM). Microscopy plays a
paradoxical role in nanotechnology because, although it is the key to understanding
materials and processes, on a nanoscale samples can be damaged by the high-
energy electrons fired at them. This is not a problem with STM, but a further
drawback is that most microscopes require very stringent sample preparation. The
SEM, TEM, and STM need well prepared samples that are also electrically
conductive.[0]

Top-down and bottom-up synthesis techniques

Nonetheless lithography can be used for patterning substrates used to

produce nanomaterials, e.g. guiding the growth of quantum dots and nanowires.
The bottom-up approach starts with constituent materials (often gases or liquids)
and uses chemical, electrical, or physical forces to build a nanomaterial atom-by-
atom or molecule-by-molecule. The simplest bottom up synthesis route is
electroplating to create a material layer-by-layer, atom-by-atom. Most
nanostructured metals with high hardness values are created with this approach. [0]

Molecular self-assembly promises to be a revolutionary new way of

creating materials from the bottom up. This has proven very effective in creating
large grids of quantum dots. The bottom up approach promises an unheard-of level
of customisability in materials synthesis, but controlling the process is not easy and
can only produce simple structures, in time-consuming processes with extremely
low yields. It is not yet possible to produce integrated devices from the bottom up,
and any overall order aside from repeating grids cannot be done without some sort
of top-down influence like lithographic patterning. Nanotechnology synthesis is
thus mainly academic, with only a few companies in the world that can claim to be
nanotechnology manufacturers. And until understanding of synthesis is complete,
it will be impossible to reach a point of mass production [0]

3.2 - Metallic nanostructures for efficient LED lighting

Research efforts in nanophotonics have mainly focused on using nanostructures to

improve radioactice efficiency (rad) via modification of the local density of optical states
to which an emitter can decay. Metallic nanostructures may reduce the overall efficiency
of LED device. Metallic nanostructures benefit emission wavelength is in extracting
specific emission colors in defined directions, thereby controlling the angular and spectral
distributions of emitted light without diminishing significantly the device efficiency.[05]

The impact on metallic nanostructures on the performance of light-emitting

devices, metallic and dielectric nanostructures represent complementary approaches to
modifying the emission properties of light sources. In particular, wavelength-sized
dielectric structures have demonstrated improved light extraction, and accurate control of
radiation patterns and polarizations. Choosing between metals and dielectrics for
enhancement of light emission will depend on fabrication constraints and/or the limitations
associated with the particular goal. [05]

This three partial efficiencies are the general terms which can be use,

= (exc) (rad) (ext).

Where, (exc) is the excitation efficiency, (rad) is the radiative efficiency and (ext) is
the fraction of blue/green/red light that escape the device into the free space. [16] The
device (via total internal reflection) can trap the emitted light and eventually absorbed,
many light-emitting devices rely on the integration of light-extracting structures to increase
(ext). To determine the efficiency, other parameters defining the color of the emission
must be assessed when developing new LEDs.

3.2.1 Plasmonic- based light emission enhancement.

Inorganic blue LEDs based on InGaN/GaN multi-quantum-well heterostructures

are currently used in advanced architectures to obtain white-light emission. But, light
generated in the active region of the multi-quantum-well structure can be reflected at the
interfaces and trapped in the layered structure before it reaches the phosphor. To maximize
light extraction, metallic surfaces and nanostructures are used.

The metallic thin films used with SPPs have been applied directly to LEDs to
enhance the spontaneous emission rate of excitons in quantum wells. A metal layer is
grown at a distance smaller than the evanescent decay length of the SPPs, the electron
hole pairs recombine and giving their energy to the SPPs. Then, the metal provides
additional states for exciton recombination.[17] This phenomena will enhanced the density
of states for excitation and recombination can significantly increase the recombination rate.

3.3 - Phosphor layers are typically much thicker than quantum wells.

The potential of metallic nanoparticle arrays to modify the Lambertian emission

from such thick luminescent layers lasmon-enhanced emission from phosphor layers.
Figure 4 was used to enhance the emission of a 700-nm-thick phosphor layer consisting
of a high-QY and a photo-stable dye by more than a factor of 60 at certain wavelengths
and in defined directions. [18] This enhancement is illustrated for normal incidence, where
the extinction and photoluminescence enhancement (PLE) spectra are displayed,
respectively. The latter is given by the ratio of the emission from the dye layer with and
without the nanoantenna array. [19] The enhanced directional emission can be described
as follows. The photo-excited dye molecules relax, exciting collective resonances in the
particle array. The periodic structure of the array is responsible for the directional
outcoupling of the emission in defined directions.[20]

The narrow linewidths of the emission associated with the collective modes are a
direct consequence of the enhancement of the spatial coherence of the emission due to the
coherent scattering by the nanoantennas.[19] A visualization of this enhanced emission is
a photograph of the emission of a phosphor layer on top of a nanoantenna array. For direct
comparison, a reference sample consisting of the phosphor layer with the same thickness
but without the antenna array.The directionality of this emission enhancement can be
controlled depending on the application.[20]

Recent results demonstrating tailored enhanced directional emission in narrow

angular ranges for red light (=620nm) with hexagonal arrays of nanoantennas. [21]
Manipulating the separation distance between aluminum particles enables accurate control
over the directionality of the red emitted light in pcLEDs.

This review presents and discusses new methods for enhancing the efficiency of
LEDs using metals structured on the nanometer scale. We have provided a general
overview of state-of-the-art LED lighting, discussing the main requirements of both
quantum wells and phosphors for efficient generation of white light.
REFERENCE
[1] Min, D. et al. Crafted phosphor-free white light emitters via in-situ nanostructure
engineering. Scientific Reports,7(2017),1-9.
[2] Russel D. Dupuis, Michael R. Kranes. History ,Development and Applications of High
Brightness Visible Light Emitting Diodes, Journal of Lightwave
Technology,26(2008),Page1.
[3] Siddha Pimputkar, James Speck, Steven Denbaars, Prospects for LED Lighting, Nature
Photonics 3,4(2009),1-3.
[4] Committee on Assessment on Solid -State Lighting. Solid-State Lighting Applications,
Assessment of Advanced Solid State Lighting,2(2013), 72-84.
[5] Ashton Acton. Nanoelectronics, Advances inNanotechnology Research and Application,
2012 Ed. (2012), page 3265.
[6] H.Panda. Assembly of Nanocrystals,Nanotechnology Handbook,(2009),44-45.
[7] DOE/Oak Ridge National Laboratory. "Nanotechnology Being Used In Next-generation
LED Lights." ScienceDaily. ScienceDaily, 23 March 2007.
[8] Gorazd Planinsic. Light Emitting Diodes: Solving Complex Problems, The Physics Teacher
. 53(2015), 291-297.
[9] Timothy T.Y.Tan. Yellow Emitting Phosphors, Rare Earth Nanotechnology, 2012 Ed.
(2012),217-218
[10] Colin J. Humphreys. Solid State Lighting, Use and Efficiency Lighting,33(2008),1-13
[11] Gregor Schiemann, Nanotechnology and Nature, International Journal for Philosophy of
Chemistry, Vol. 11 (2005), No. 1, 81
[12] Jeff Perkel, whats nano: a nanotechnology primer, Nanotechnology: The Promises and
Pitfalls of Science at the Nanoscale, Vol. 2 (2000), 6.
[13] Dr. Christoph Lauterwasser, Nano tools and fabrication techniques, Opportunities and
risks of Nanotechnologies, Vol. 2 (1999), 11.
[14] Luisa Filipponi and Duncan Sutherland, Nano tools and fabrication techniques,
Nanotechnologies: Principles, Applications,Implications and Hands-on Activities Vol. 1
(2013), 22.
[15] Gabriel Lozano, Said RK Rodriguez, Marc A Verschuuren, Jaime Gmez Rivas, Metallic
nanostructures for efficient LED lighting, Nanotechnologies Light: Science & Applications
(2016), 5.
[16] Maria Davoren. Insight: Nanotechnology, Small particle, Big risks?. Pacific
Envionment,(2017),1.
[17] Lozano G, Grzela G, Verschuuren MA, Ramezani M, Rivas JG. Tailor-made directional
emission in nanoimprinted plasmonic-based light-emitting devices. Nanoscale 2014.
[18] Lumdee C, Toroghi S, Kik PG. Post-fabrication voltage controlled resonance tuning of
nanoscale plasmonic antennas. ACS Nano 2012.
[19] Mller J, Snnichsen C, von Poschinger H, von Plessen G, Klar TA et al. Electrically
controlled light scattering with single metal nanoparticles. Appl Phys Lett 2002.
[20] Jin P, Tazawa M, Xu G. Reversible tuning of surface plasmon resonance of silver
nanoparticles using a thermochromic matrix. J Appl Phys 2006.
APPENDIX

Figure 1. The three most popular approaches are shown above. These are a blue LED with
yellow phosphors; an ultraviolet LED with blue and yellow phosphors (or red, green and blue
phosphors); and a device that combines red, green and blue LEDs. (After Ref. [3]. Reprinted from
Siddha Pimputkar, James Speck, Steven Denbaars, Prospects for LED Lighting, Nature Photonics
3,4(2009),1-3)

FIGURE 2. Key dimension of nano scales. (After Ref. [16]. Reprinted from Maria Davoren.
Insight: Nanotechnology,Small particle,Big risks?.Pacific Envionment,(2017),1)
Figure 3. Metallic nanostructures for efficient LED lighting. Reprinted from Gabriel Lozano, Said
RK Rodriguez, Marc A Verschuuren and Jaime Gomes Rivas.

Figure 4.
(a) Scanning electron micrograph of a square array of aluminum nanoparticles. The inset is a sketch
of a metal nanoparticle array pcLED, where the phosphor layer is represented by the transparent
red layer. (b) Extinction and (c) PLE of an aluminum nanoparticle array covered by a thin phosphor
layer. Reprinted with permission from Macmillan Publishers Ltd33, copyright 2013. (d)
Photograph of the emission of a standard pcLED (left) and a pcLED that exhibits
enhanced emission due to the integration of a hexagonal array of metal nanoparticles (right). (e)
Fourier image of the unpolarized red emission (610620nm) of an unstructured pcLED. (fh)
Fourier images of the unpolarized red emission of a similar pcLED that features a hexagonal array
of Al nanoparticles with lattice constants (f) 475nm, (g) 425nm and (h) 375nm. Reproduced from
Ref. 42 with permission from The Royal Society of Chemistry.

Blue LED with Ultraviolet LED with Device that combines

yellow phosphors blue and yellow red, green and blue
phosphors LEDs

Pros High theoretical Value of color High efficacy

efficacy rendering index (CRI)
high

Cons Value of color Low efficacy Most expensive

rendering index (CRI)
lower

Table1. Summary of pros and cons of using a blue LED with yellow phosphors; an ultraviolet
LED with blue and yellow phosphors and a device that combines red, green and blue LEDs.