One problem in developing more efficient organic LED light bulbs and displays for TVs and phones is that much of the light is polarized in one direction and thus trapped within the light-emitting diode, or LED. University of Utah physicists believe they have solved the problem by creating a new organic molecule that is shaped like rotelle – wagon-wheel pasta – rather than spaghetti.

The rotelle-shaped molecule – known as a “pi-conjugated spoked-wheel macrocycle” – acts the opposite of polarizing sunglasses, which screen out glare reflected off water and other surfaces and allow only direct sunlight to enter the eyes.

The new study showed wagon-wheel molecules emit light randomly in all directions – a necessary feature for a more efficient OLED, or organic LED. Existing OLEDs now in some smart phones and TVs use spaghetti-shaped polymers – chains of repeating molecular units – that emit only polarized light.

“This work shows it is possible to scramble the polarization of light from OLEDs and thereby build displays where light doesn’t get trapped inside the OLED,” says University of Utah physicist John Lupton, lead author of a study of the spoked-wheel-shaped molecules published online Sunday, Sept. 29 in the journal Nature Chemistry.

“We made a molecule that is perfectly symmetrical, and that makes the light it generates perfectly random,” he adds. “It can generate light more efficiently because it is scrambling the polarization. That holds promise for future OLEDs that would use less electricity and thus increase battery life for phones, and for OLED light bulbs that are more efficient and cheaper to operate.”

Lupton emphasizes the study is basic science, and new OLEDs based on the rotelle-shaped molecules are “quite a way down the road.”

He says OLEDs now are used in smart phones, particularly the Samsung Galaxy series; in pricey new super-thin TVs being introduced by Sony, Samsung, LG and others; and in lighting.

“OLEDs in smart phones have caught on because they are somewhat more efficient than conventional liquid-crystal displays like those used in the iPhone,” he says. “That means longer battery life. Samsung has already demonstrated flexible, full-color OLED displays for future roll-up smart phones.” Lupton says smart phones could produce light more efficiently using molecules that don’t trap as much light.

The large rotelle-shaped molecules also can “catch” other molecules and thus would make effective biological sensors; they also have potential use in solar cells and switches, he adds.

The study was funded by the Volkswagen Foundation, the German Chemical Industry Fund, the David and Lucille Packard Foundation and the European Research Council.

Lupton is a research professor of physics and astronomy at the University of Utah and also on the faculty of the University of Regensburg, Germany. He conducted the study with Utah physics graduate student Alexander Thiessen; Sigurd Höger, Vikas Aggarwal, Alissa Idelson, Daniel Kalle and Stefan-S. Jester of the University of Bonn; and Dominik Würsch, Thomas Stangl, Florian Steiner and Jan Vogelsang of the University of Regensburg.

Freeing Trapped Light

While conventional LEDs use silicon semiconductors, OLEDs in some of the latest cell phones and TVs are made with “pi-conjugated polymers,” which are plastic-like, organic semiconductors made of a chain of repeating molecular units.

“Conjugated polymers are a terrible mess,” Lupton says. “They now make only mediocre OLEDs, although people like to claim the opposite.”

For one thing, three-quarters of the light energy is in a state that normally is inaccessible – a problem addressed by another recent University of Utah study of OLEDs. Lupton says his study deals with another problem, which exists even if the other problem is overcome: the polarization of light in pi-conjugated polymers that leads to the “trapping” or loss of up to 80 percent of the light generated.

“Light is an oscillating field like a wave, and a wave moves in a certain direction,” Lupton says. “We call this direction of oscillation a polarization.”

Because polymers are long molecules like spaghetti, when an electrical current is applied to a polymer, “the electrons can only flow in one direction and that generates the light waves,” Lupton says. “Because those light waves only oscillate in one direction, the light can get trapped inside the OLED, which is a little bit like an optical fiber.”

That, he adds, is why even with the latest OLED smart phones, “your battery is dead in two days because the display uses a lot of the electricity.”

“The rotelle – technically called oligomers – are basically wrapped-up polymers,” Lupton says. “They all have the same shape, but they do not emit polarized light because they are round. They generate waves that vibrate in all directions. The light doesn’t have a fixed polarization; it doesn’t vibrate in a fixed direction. It always can get out.”

Lupton compares the ability of the wagon-wheel molecules to emit unpolarized light in all directions to what happens when a pencil is balanced perfectly on its tip and falls in a different, random direction each time.

Cooking up a Wagon Wheel-Shaped Molecule

The international team of physicists and chemists set out to make molecules that generate light waves in all directions rather than in a fixed direction. In the new study, they report how the created the spoked-wheel molecules, made images of them and did single-molecule experiments, including looking at photons, or light particles, emitted one at a time from a single molecule. In those experiments, they shined an ultraviolet light on the rotelle-shaped molecules to generate visible light photons.

“We showed that every photon that comes out has a scrambled polarization, the polarization changes randomly from photon to photon,” Lupton says.

The emitted light is blue-green, Lupton says, but images accompanying the paper – taken with a scanning tunneling electron microscope – show the rotelle- and spaghetti-shaped molecules with a false yellow-brown color to provide good contrast.

Each wagon-wheel molecule measures only six nanometers wide, which is large for a molecule but tiny compared with the 100,000 nanometer width of a human hair.

Using rotelle-shaped oligomers instead of spaghetti-shaped polymers, “in principle, we should be able to double the efficiency of getting the light out” – although that remains to be proved, Lupton says.

“Even if we scramble the polarization, we’re always going to have a bit of light trapped in the OLED,” he says. “Those losses are now 80 percent, and we probably could get down to 50 or 60 percent.”

By inserting platinum atoms into an organic semiconductor, University of Utah physicists were able to “tune” the plastic-like polymer to emit light of different colors – a step toward more efficient, less expensive and truly white organic LEDs for light bulbs of the future.

University of Utah physicist Z. Valy Vardeny works in a glove box where light-emitting polymers are studied under clean conditions.

“These new, platinum-rich polymers hold promise for white organic light-emitting diodes and new kinds of more efficient solar cells,” says University of Utah physicist Z. Valy Vardeny, who led a study of the polymers published online Friday, Sept. 13 in the journal Scientific Reports.

Certain existing white light bulbs use LEDs, or light-emitting diodes, and some phone displays use organic LEDs, or OLEDs. Neither are truly white LEDs, but instead use LEDs made of different materials that each emit a different color, then combine or convert those colors to create white light, Vardeny says.

In the new study, Vardeny and colleagues report how they inserted platinum metal atoms at different intervals along a chain-like organic polymer, and thus were able to adjust or tune the colors emitted. That is a step toward a truly white OLED generated by multiple colors from a single polymer.

Existing white OLED displays – like those in recent cell phones – use different organic polymers that emit different colors, which are arranged in pixels of red, green and blue and then combined to make white light, says Vardeny, a distinguished professor of physics. “This new polymer has all those colors simultaneously, so no need for small pixels and complicated engineering to create them.”

“This polymer emits light in the blue and red spectral range, and can be tuned to cover the whole visible spectrum,” he adds. “As such, it can serve as the active [or working] layer in white OLEDs that are predicted to replace regular light bulbs.”

Vardeny says the new polymer also could be used in a new type of solar power cell in which the platinum would help the polymer convert sunlight to electricity more efficiently. And because the platinum-rich polymer would allow physicists to “read” the information stored in electrons’ “spins” or intrinsic angular momentum, the new polymers also have potential uses for computer memory.

Not quite yet an OLED

In the new study, the researchers made the new platinum-rich polymers and then used various optical methods to characterize their properties and show how they light up when stimulated by light.

The polymers in the new study aren’t quite OLEDs because they emit light when stimulated by other light. An OLED is a polymer that emits light when stimulated by electrical current.

“We haven’t yet fabricated an OLED with it,” Vardeny says. “The paper shows we get multiple colors simultaneously from one polymer,” making it possible to develop an OLED in which single pixels emit white light.

Vardeny predicts about one year until design of a “platinum-rich pi-conjugated polymer” that is tuned to emit white light when stimulated by light, and about two years until development of true white organic LEDs.

A sample of the yellowish-colored, platinum-rich polymer known as Pt-1, emits light as a laser beam hits it at a University of Utah physics laboratory.

“The whole project is supported by the U.S. Department of Energy for replacing white light from regular [incandescent] bulbs,” he says.

The University of Utah conducted the research with the department’s Los Alamos National Laboratory. Additional funding came from the National Science Foundation’s Materials Research Science and Engineering Center program at the University of Utah, the National Natural Science Foundation of China, and China’s Fundamental Research Funds for the Central Universities.

Using platinum to tune polymer color emissions

Inorganic semiconductors were used to generate colors in the original LEDs, introduced in the 1960s. Organic LEDs, or OLEDs, generate light with organic polymers which are “plastic” semiconductors and are used in many of the latest cell phones, digital camera displays and big-screen televisions.

Existing white LEDs are not truly white. White results from combining colors of the entire spectrum, but light from blue, green and red LEDs can be combined to create white light, as is the case with many cell phone displays. Other “white” LEDs use blue LEDs, “down-convert” some of the blue to yellow, and then mix the blue and yellow to produce light that appears white.

The new platinum-doped polymers hold promise for making white OLEDs, but can convert more energy to light than other OLEDs now under development, Vardeny says. That is because the addition of platinum to the polymer makes accessible more energy stored within the polymer molecules.

Polymers have two kinds of electronic states:

A “singlet” state that can be stimulated by light or electricity to emit higher energy, fluorescent blue light. Until now, OLEDs derived their light only from this state, allowing them to convert only 25 percent of energy into light – better than incandescent bulbs but far from perfect.

A normally inaccessible “triplet” state that theoretically could emit lower energy phosphorescent red light, but normally does not, leaving 75 percent of electrical energy that goes into the polymer inaccessible for conversion to light.

Vardeny says he and his colleagues decided to add platinum atoms to a polymer because it already was known that “if you put a heavy atom in molecules in general, it can make the triplet state more accessible to being stimulated by light and emitting light.”

Ideally, a new generation of white OLEDs would not only produce true white light, but also be much more energy efficient because they would use both fluorescence and phosphorescence, he adds.

For the study, the researchers used two versions of the same polymer. One version, Pt-1, had a platinum atom in every unit or link in the chain-like semiconducting polymer. Pt-1 emitted violet and yellow light. The other version, Pt-3, had a platinum atom every third unit, and emitted blue and orange light.

By varying the amount of platinum in the polymer, the physicists could create and adjust emissions of fluorescent and phosphorescent light, and adjust the relative intensity of one color over another.

“What is new here is that we can tune the colors the polymer emits and the relative intensities of those colors by changing the abundance of this heavy atom in the polymer,” Vardeny says. “The idea, ultimately, is to mix this polymer with different platinum units so we can cover the whole spectrum easily and produce white light.”

Vardeny conducted the new study with former University of Utah postdoctoral researcher Chuanxiang Sheng, now at Nanjing University of Science and Technology in China; Sergei Tretiak of Los Alamos National Laboratory; and with University of Utah graduate students Sanjeev Singh, Alessio Gambetta, Tomer Drori and Minghong Tong. The physicists hired chemist Leonard Wojcik to synthesize the platinum-rich polymers.