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ADVANCEMENT OF PLED TECHNOLOGY: A review

Zachary Pipkin

Introduction

Semiconductors greatly interest society and impact our daily lives in countless ways. They

are the building blocks of the entire technological revolution. Every electrical technological

device relies on these powerhouses – small, lightweight, high speed, and low power

consumption. Semiconductors are often associated with silicon– the most common

semiconducting material in electronics. These types of metal semiconductors are known as

inorganic. However, other types of semiconductors exist, including organic ones. Organic

semiconductors can be either composed of small or large molecules (polymers), with each

type having advantages8. Organic materials, in general, and polymers, in particular, have

been extensively researched for decades, and the reasoning behind this research varies

across scientific disciplines. Some motivations include the ability to mimic biological

systems (DNA is a polymer) and implement polymeric properties into electronics 8. Organic

materials promise technological advantages; polymers are desirable for semiconductor

technology due to their low production cost and applications. Polymers can be easily

synthesized in labs, printed, and spun from solutions 9; unlike their inorganic counterparts,

polymer semiconductors do not require ultra-clean processing environments during any

production stage. Concerning light and color emittance, these materials can be easily

chemically tuned so their emission color can cover the entire visible spectrum 4. Therefore,
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polymeric semiconductors and organic semiconductors, in general, are a technology of the

future.

Organic semiconductor usage expands into many new emerging disciplines, such as

nanobiotechnology, and other disciplines not even fully realized, such as biocomputers.

Why are polymers useful in electronics? When you think of the word "polymer," think of

plastics. Plastics are polymers too and are a suitable example as to why polymers are

advantageous – plastic is: cheaply made, thin yet resilient, can be transparent or opaque,

can have a high or low melting point, can be brittle or tough, can be pliable or stiff; it can

exhibit a wide range of properties depending on its chemical subunits. This is the

advantage of using polymers in electrical production – cheap cost, biological applications,

and ways to physically apply them that aren't achievable with the rigidity of metal

semiconductors1. Because the topic of organic and polymer electronics is so broad, this

review emphasizes developing one type of polymer semiconductor. Light-emitting diodes

(LEDs) are semiconductors that emit light via photons when exposed to electrical current 7.

They are used in various technologies for illuminating electronics, food, cosmetics, and art

while emitting much less heat than other light sources. Organic light-emitting diodes

(OLEDs) and a type of OLEDs known as polymer organic light-emitting diodes (PLEDs)

have specific advantages in applications for emitting light.

The first OLEDs were demonstrated in 19876, and the first PLEDs in 19901. Since

then, both have been brought into the market, but plenty of research is still needed until a

complete understanding of the technology is realized. Polymer LEDs have the added benefit

of potential printable and flexible displays of electronic devices, which would impact all

industries10. The advancement of PLEDs showcased here also tracks the improvement of
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OLEDs and organic/polymer semiconductor technology. Also discussed are the benefits of

the emerging science of thin, printable, flexible electronics and possibilities for future

biological and medical applications. Electronic technology could be entirely revolutionized,

affecting all industries, sciences, health, and medicine. The way electronic technology is

actively involved in our world means a future revolution in light and electronic mediums

will change how current technology is used and create new technological devices for

bettering society. This will require engineers, chemists, physicists, and other people from

various disciplines to collaborate in understanding and developing this technology.

Emergence of PLEDs

By 1990 solid-state LEDs were integrated into society8. Inorganic LEDs were efficient and

found widespread application. Now molecular (organic) LEDs were being developed –

scientists were finding ways to exhibit a wide array of colors and make them more flexible.

Still, stability was an issue8 in the organic films. In 1989 the first polymer-based light

emitting diode (PLED) was discovered using PPV as the emissive layer 1. Burroughes et al.

explored the advancement of moving from molecular molecules in regular organic

semiconductors to macromolecular materials (polymers). Burroughes explained that

utilizing polymers for light emission is a good choice "since they should be able to produce

a high amount of photon emission, provide good transportation of electrons and provide

both good charge transport1." Research had explored conjugated polymers and their

properties as conducting materials but not as luminescence materials 1. Until then, polymer

research was focused on electrical flow only.

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As discovered by Burroughes, conjugated polymers with more significant

semiconductor gaps can show high photoluminescence yields. This study used poly (p-

phenylene vinylene) or PPV to make high-quality luminescent films 8. The advantage of

polymeric organic semiconductors is the processability of polymers. This work set a

foundation for all advancement in polymer LEDs and future lighting technology. Polymers

do exhibit luminescence depending on what type of polymers you use and how you

chemically alter parts of their chains11. Thus solid-state electroluminescence can be

developed from polymers, which allow for large-scale, cost-beneficial production and fine-

tuning of the electrical and light emittance properties. This research advanced light

emittance technology in OLEDs and started the new field of PLEDs. Polymers are

advantageous since they are composed of chemical subunits and thus can be altered quite

easily in labs. The physical aspects of polymers are unique as a macroscopic materials. Still,

the chemical properties at a small scale describe how chains interact through their

chemical bonds and can output changes in color, strength, stiffness, solubility, and more.

Due to its stability, processability, and electrical and optical properties, PPV has been

considered for various applications, including electron donating in solar-powered cells 9.

PLEDs Cover the Visible Spectra

As PLEDs emerged as commercial products, research began to look for different ways to

fine-tune their optical and electrical properties by varying their polymer structure.

Research led by Ego, Friend et al. in 2003 focused solely on developing full-color flat-panel

displays and tuning the colors that PLEDs emit. Friend was also an active research

participant in Burroughes' study. The objective of Friend's study deals with keeping the
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PLEDs easy to process while ensuring they exhibit high luminescence with low turn-on and

operating voltages and "good chemical and electrical stability as well as photostability 4." At

the time, color tuning was only known to be achieved by substituting chemical groups in

the polymers, controlling effective conjugation length, or blending it with another emissive

material (chromophores)4. Chromophores are "the group of atoms and electrons forming

part of an organic molecule that causes it to be colored 11." By blending red-emitting

tetraphenylporphyrin into a blue-emitting polyfluorene, for example, a red-emitting LED is

produced. However, these dyes tend to show phase separation over time and lead to device

instability. The research's solution is to attach the dye covalently to the polymer instead of

blending it. Ego et al. could tune emission colors over the visible region by linking perylene

dyes to polyfluorene chains as either comonomers in the main chain, end-capping groups at

chain termini, or pendant side groups. Since polymers can be synthesized in labs, the length

of chains, type of subunits, and atoms present in the large chain molecules can be chosen,

giving the technology customized properties. This research further exploits this idea by

showcasing the different color emittance potential of PLEDs.

Ultrathin, Highly Flexible, and Stretchable PLEDs for a New Tomorrow

A research study in Nature Photonics in June 2013 produced the first PLEDs that can be

stretched and crumpled while lit. Thinner PLEDs can be more flexible. Though today's

PLEDs are very thin (just a few hundred nanometers thick), they must be surrounded by

bulky layers of electrode metals12. Also, today's commercial PLED materials are sensitive to

air and water and need a protective layer that encapsulates them. White et al. produced

their PLEDs on a 1.4µm thick foil substrate (extremely thin). It's hard to spin-coat PLED
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materials onto such thin films. Still, they achieved it by sticking the films onto rigid silicone-

coated glass, which holds them in place using van der Waals forces alone, allowing easy

post-fabrication removal, basically peeling the foil off 12. However, the devices' electrode

materials weren't air-stable and only worked for a few hours. Being so thin gave their

devices uniquely small bending radii, which allowed them to be crumpled. Attaching the

films to an extended elastomeric tape made stretchable PLEDs 11. When the tape contracts,

the PLEDs fold and pull flat again when stretched. This advancement of light-emitting foils

is vital for PLEDs integrating with materials like biotextiles and artificial skin. Stretchable

electronics open up new possibilities –we could apply them to various surfaces, including

our bodies. Materials used in electronics, even conducting and semiconducting polymers,

do not currently share this property. It is also compatible with spin coating, screen-

printing, ink-jet printing, and a multitude of other processing techniques, according to the

researchers. The ultrathin PLEDs presented in this work are the thinnest and most flexible

electroluminescent devices to date. This work represents a significant step towards the

realization of newer medical technology. Combining flexible, stretchable surface molding

electronics could allow us to incorporate electronics into medical fabrics.

Integrating OLEDs into Wearable Products with Medical Applications

S.K. Attili et al. focused on ambulatory photodynamic therapy (PDT) in their 2009 article.

PDT is a popular treatment for nonmelanoma skin cancer with clearance rates between

70% and 100%. Although reported to have a superior cosmetic outcome, the inconvenience

of hospital visits and discomfort experienced during therapy are PDT's shortcomings. The

pain associated with PDT for skin cancer isn't well understood, but the degree of pain
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depends on the light source used and the intensity of light delivery2. S.K. Attili et al. attempt

to study an ambulatory PDT device. Twelve patients invited to participate in the study had

lesions prepared via gentle superficial curettage without local anesthesia, and a self-

adhesive gel layer was applied (to prevent slippage). A small device made from a power

supply and patch containing the OLED was administered while patients sat in a waiting

room for the entire treatment period; lesions were assessed for the efficacy of treatment at

three, six, nine, and twelve months following the surgical treatment. Patients were asked to

score maximal pain and discomfort levels as well. Overall, the efficiency of the device

wasn't statistically shown. A possibility is that the lesions treated with the device were

>one-five centimeters in diameter, while the patch the patients applied had only a two-

centimeter diameter. Perhaps a larger patch would've worked, and the research suggests

that improved outcomes would have been obtained with larger devices. This study has

other beneficial information - it still indicates that OLED-PDT is less painful than

conventional PDT with the added advantage of being lightweight and therefore has the

potential for more convenient 'home PDT.' It can be incorporated into potentially

disposable and lightweight OLEDs so patients can remain mobile 2. Again, polymers' wide

range of properties allows them to be integrated into future devices such as these. This

means that light applications can be applied to a stretchable material, and the material

itself is responsible for the elastic properties as well as the light emission.

Deep Blue PLED Emission and Phototherapy Potential

Research has since been able to manufacture PLEDs that emit many different wavelengths

due to the knowledge of how to bond chromophores to molecules covalently. In a study by

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U. Giovanella et al. in 2013, the knowledge of fluorinated phenylene as an alternating

copolymer is used to develop blue polymeric emitters. Deep blue light is produced in the

study, and the possibility of biomedical applications is explored. It is challenging to create

deep blue and UV-efficient emitters with PLEDs6. Polyfluorene derivatives have attracted

interest due to their high photoluminescent efficiency but have been limited due to their

poor color stability during the operation lifetime of the PLEDs 10. By introducing fluorinated

functional groups, the research team reduced oxidation and provided an intelligent

strategy to improve the color purity and durability of the materials in the devices 6. They

used a method known as Suzuki coupling to achieve this.

Since the electroluminescence of their new polymer poly[(9,9-di-n-octylfluorene-

2,7-diyl)-alt-tetrafluoro-p-phenylene] (PFO–TFP) falls in the border region of the visible

spectrum, the PLED performance fulfills the requirements for devices to maintain tissue

sterility2. A photostability test was performed under ultraviolet irradiation or sterilization

of the surface to be placed in contact with the wounded skin. A 100 mW UV lamp directly

heated the polymer at 365 nm for five minutes. The photodegradation of PFO–TFP is

reduced. This means that deep blues can now be more easily understood and applied in

full-color high-definition displays6. Before, balancing the large band gap between the

materials and the charge balance was hard to equalize for the optimum properties you

need for deep blue light. Besides creating new displays, blue light therapy could be

incorporated into biomedical applications.

With knowledge from the following and forthcoming articles, phototherapy could

one day be implemented into medical textiles. Ready-to-use bandages that emit this blue

light could be envisioned. Mass production of this PLED phototherapy would allow for
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transportable therapy. Instead of sitting around for light therapy treatment, people could

wear materials with the electrical phototherapy, walk around and enjoy their day. This

technology has the potential to revolutionize the way we use phototherapy. Flesh wound

treatment on-the-go in materials such as medical gauze can be envisioned, and lower rates

of infection are disease spread are possible. This technology can also be envisaged to

revolutionize other avenues of phototherapy, such as treating psoriasis with phototherapy-

embedded textiles or being able to treat jaundiced babies while they remain mobile,

embedding the phototherapy technology into blankets, bandages, or clothes. PLEDs offer

not only targeted medical treatment but indirect treatment as well. Light regulates a

human's biological clock and can significantly influence people, affecting their psycho-

physiological processes such as mood, seasonal depression, and anxiety levels. By

harnessing PLED light and using it effectively in healthcare facilities, one can enhance the

healing environment and play a key role in promoting the well-being of patients and staff 13.

Conclusions

This article has generalized the study of PLEDs since their discovery, the benefits of organic

luminescence, and its potential benefits: unprecedented physical applications, the

possibility of medical applications, and cheaper production of electronic systems overall.

Since the technology is relatively new, a more underlying understanding of this technology

should be developed, and possibilities of advancement in PLED technology will come to

fruition alongside the knowledge of the complex and variable properties of PLEDs. PLED

science has advanced dramatically, yet there is still much research to be done in perfecting

the chemistry and physics to achieve the properties we desire and ease of production.
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Growing alongside PLED technology, polymer semiconductors as a whole will advance.

Still, for now, processes associated with plastic electronics must be run to remain

significantly less expensive than those associated with the established and more efficient

silicon electronics industry. Eventually, it will be more accessible and cheaper for large-

scale applications. Concerning medical applications, any technology from simple adhesive

bandages to complex medical devices could benefit.

The advantages of PLEDs are numerous, with a significant benefit in biomedical

textiles and the emerging flexible electronics industry. Polymers can have seemingly

limitless options for physical characteristics and colors. Applying this to LED technology

will open the door to an electronic and textile revolution, pushing medicine forward. As

polymer science, organic semiconductor science, and their engineering techniques develop,

further advances will be made in polymer semiconductors to fulfill other uses that

inorganics and small organic molecules cannot. Once fully understanding the technology, it

can be integrated into carriers, such as biomedical textiles and biological systems. For

healthcare devices that come into contact with our skin, there are also specific challenges

related to avoiding allergic responses, ensuring biocompatibility, and sterilization. The

invention of devices such as sensor-filled adhesive bandages will change how we combat

disease and infection. Phototherapy can be more efficiently employed and accessible.

The ability to produce transparent and flexible displays will emerge as the ability to

blend electronics with fibers and textiles becomes a reality. Electronic medical textiles

could display patient information such as heart rate and oxygen levels on clothing and

gowns; electronic papers could automatically change information, and biocomputers could

be created inside living cells to interact directly with cellular processes. Medical device
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improvement and electrical integration with our clothing and bodies can advance in ways

we've only imagined. Research in the near future will most likely deal with understanding

how to make organic semiconductors do precisely what we need by altering their chemical

subunits and molecular geometry and how to move toward the wide-scale use of printable

electronic technology eventually. As of now, organic thin-film transistors have been

developed3. If we can easily do this in the future, we will have cheaper material and

solution processing and lower production cost. Some applications discussed may come to

fruition in the next several years, and some in the next several decades. Regardless, we are

on the cusp of a better technology with polymeric organic semiconductors.

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