Long Vacation Project Organic and Printed Electronics Demonstrators

Jirawit Ratanapreechachai, St Johns College CRSid: jr561 Project Partners: Sean Garnsey (California Polytechnic State University) Sunny Niu (Princeton University) Project Supervisors: Kai Sudau (InnovationLab GmbH) Dr. Gerardo Hernandez-Sosa (Karlsruhe Institute of Technology) Project Coordinator: Michaela Sauer (InnovationLab GmbH) This project was carried out at InnovationLab GmbH, Speyerer Strae 4, 69115 Heidelberg, Germany Project Duration: 10 June 2013 30 August 2013

Abstract
Three technology demonstrators for organic and printed electronics were built to show the unique features of the technology: built-in book lighting, lighting puzzle and hallway lighting controlled by distance infrared sensor. Organic light-emitting electrochemical cells (OLECs) were mainly employed as lighting components in the project. We began by finding the optimal solution for the active layer of OLECs. This was achieved by testing different solutions and varying their concentrations. The optimal solution consisted of small molecule green (SMG), poly(methyl methacrylate) 350 kg/mol (PMMA) and tetra-n-butylammonium fluoride (TBAF) in anisole with the ratio 1:0.375:0.075. Indium tin oxide (ITO) and silver were used as the cathode and the anode respectively. ITO was structured to a desired shape by etching an ITO-coated substrate with acid, while silver was evaporated on top of the active layer in a vacuum chamber. The devices with glass substrates worked very well, giving a maximum luminance of about 1500 cd/m2 for spin-coated devices and 500 cd/m2 for inkjet-printed devices. However, the attempts with polyethylene terephthalate (PET) substrates, which would demonstrate the flexibility of the devices, were unsuccessful. This was due to the nature of the surface of the PET substrate.

1 Introduction

Printed organic electronics is considered to be a high-potential technology and is a major research topic at InnovationLab GmbH. The advantages of organic electronic devices are that they can be made thin, energy-saving, lightweight, flexible and transparent. They are believed to be a promising replacement of today's silicon-based electronic devices (Figure 1). Organic light-emitting electrochemical cells (OLECs) are the main focus of this demonstrator project. OLEC devices can be prepared by using a wide range of different active layer solutions, but in this project, a solution of Small Molecule Green (SMG), Poly(methyl methacrylate) (PMMA) and Tetra-n-butylammonium fluoride (TBAF) in anisole was chosen, which resulted in green light-emitting OLEC devices. The final goal of the project is to design and build technology demonstrators, which reflect the unique features of printed organic electronic devices. To achieve this, we need to optimise the ratio of SMG to PMMA to TBAF of the active layer solution so that it gives devices, which are bright enough and can be inkjet-printed. The theoretical background behind the project is summarised in the next section. The concepts for the demonstrators are summarised in section 3. In section 4, the experimental methods, along with the precautions taken to get reliable results and working devices, are discussed in details. The results and discussions of the results are given in section 5. The conclusions are then given in section 6.

Figure 1: the flexibility of an OLEC device.

2 Theoretical Background
Organic Light-Emitting Electrochemical Cell It consists of three separate layers lying on top of a transparent substrate, which for example can be glass or polyethylene terephthalate (PET). Glass is more durable and rigid while PET is good for a flexible device. The three layers are the cathode, the active layer and the anode. In this project, indium tin oxide (ITO) and silver were chosen as the cathode and anode respectively. The ITO-coated substrate was structured to a desired shape by etching with acid and the active layer solution was then spin-coated or inkjet-printed onto the ITO layer. Finally, silver was evaporated in a vacuum chamber on top of the active layer. The structure of an OLEC is shown in Figure 2.

Figure 2: The schematic diagram of the layers of an OLEC. PET is the transparent substrate in this figure.

ITO is a transparent metal; it is therefore suitable to be used as an electrode for a transparent OLEC. Silver was used because it is relatively easy to be evaporated. The active layer solution consists of SMG, PMMA and TBAF in anisole. SMG is the light-emitting agent; it is an organic semiconductor. PMMA and TBAF act like an electrolyte, providing mobile ions. In this project, the ratio of PMMA to TBAF was fixed at 5:1, while the ratio of SMG to PMMA was varied to find the optimal ratio. When a voltage is applied to the device, mobile ions within the active layer will move towards both sides creating a capacitor-like structure, which is equivalent to what happens in organic light-emitting diodes (OLEDs)1 in which there are hole injection and electron injection layers. The light-emitting agent is excited by the motion of electrons and holes and therefore emits phottons. PMMA exists in different chain lengths, as it is a polymer. It is expected that PMMA with longer chains should be more conductive than those with shorter chains and should give OLEC devices with better performance. However, it might have problems with clogging of the printers nozzle. The advantages of OLECs over OLEDs are that they do not depend on the difference in work functions2 of the two electrodes and that the thickness of the active layer can be much larger than that for OLEDs.

3 Demonstrator Concepts
Built-in Book Lighting This is a book cover that is designed to have a built-in lighting system to illuminate pages of the book. The light turns on or off automatically when the book is open or closed respectively. Flexibility is preferred so that we can adjust the angle such that it illuminates pages properly. Lighting Puzzle This is a six-piece puzzle that each puzzle piece has sections, which light up only when it is placed in its correct position. So each section will be one OLEC that completes its circuit with electrical contacts on the puzzle holder.

Hallway Lighting This consists of EL panels placed along a hallway. Each panel will light up depending on where a person is standing. An infrared distance sensor will be used to detect the position of the person standing in front of the panels.

4 Methods
Preparing the active layer solution The active layer solution is a mixture of SMG, PMMA and TBAF in anisole. PMMA was available in two different chain lengths: 15kg/mol and 350kg/mol. Firstly, the pure solutions were prepared separately: 25g/L of SMG and PMMA 15k and 20g/L of PMMA 350k. We arranged so that the TBAF solutions had the same concentrations as the corresponding PMMA solutions as we would like to keep the ratio of PMMA: TBAF to be fixed at 5:1. Hence, 25g/L of TBAF for PMMA 15k and 20g/L of the one for PMMA 350k were prepared. Solutions with different ratios of SMG: PMMA: TBAF in anisole were prepared as shown in Table 1 in order to find the optimal solution for OLEC devices.
Table 1: The ratios of SMG: PMMA: TBAF of the solutions that were prepared for the active layer of the OLEC devices for the project.

SMG: PMMA: TBAF PMMA 15k 1: 1.25: 0.25 1: 1: 0.2 1: 0.75: 0.15 1: 0.5: 0.1 1: 0.1: 0.02 PMMA 350k 1: 1: 0.2 1: 0.75: 0.15 1: 0.5: 0.1 1: 0.375: 0.075 -

All the containers used to prepare the solutions should be cleaned by rinsing them with isopropanol (IPA) and dried with nitrogen gun. As dust can cause dewetting of the active layer solution on the substrate and result in short devices in the end, so all the precautions should be taken to minimize the amount of dust introduced onto the devices. Fabricating the glass device ITO-structured glass substrates were already supplied by InnovationLab. They need to be cleaned by first rinsing with acetone, treating in an ultrasonic bath for 10 minutes, then rinsing with IPA, treating in an ultrasonic bath for another 10 minutes and drying with nitrogen gun accordingly. The active solution was then spin-coated onto the substrate as follows. The substrate was mounted onto a substrate holder in the spin coater (Figure 3) and the solution was then pipetted on top on the substrate. Spin coating was set for 60 seconds with a certain spin speed that needed to be determined.

Figure 3: The spin coater. The substrate holder is the metal platform inside the equipment.

The Veeco Dektak 150 profilometer (Figure 4) was used to measure the thickness of the active layer by making a scratch onto a spin-coated substrate. With different spin speeds, we can plot the layer thickness against the spin speed. Previous experiments suggested that the layer thickness of a working device should be approximately 100nm.

Figure 4: The Veeco Dektak 150 Profilometer.

Alternatively, the Dimatix materials printer (Figure 5) was also available to inkjetprint the active layer solution onto the substrate. The layer thickness of a printed device can be varied by changing the printing resolution. As before, the layer thickness was measured by Veeco Dektak 150 Profilometer.

Figure 5: The Dimatix materials printers.

After that, silver was evaporated on top of the active layer in the vacuum chamber (Figure 6) as follows. The substrates were put into a substrate holder in the chamber and covered by the InnovationLab-patterned evaporation mask (Figure 7). The holder was then spun during evaporation for homogeneity of the silver layer. The heating power was gradually increased until the thickness of the silver layer was about 100nm.

Figure 6: The vacuum chamber evaporation machine. On the right are the power control screen and the plot showing the silver deposition rate. The sample is kept under vacuum inside the chamber.

Figure 7: The silver evaporation mask (Left) and the finished OLEC devices after evaporation (Right).

The fact that the active layer glows under ultraviolet light therefore provided us with a means to look at the homogeneity of the layer, i.e. to see if there are dewetting issues or dust particles. Also, a multimeter was used to do a quick check whether final devices were short so that these short devices could be skipped when a detailed check was done. The whole process was carried out in a clean room to ensure as less dust as possible on the final devices . Optimising the device The above fabrication process was repeated with all the active layer solutions specified above. The finished devices were then tested by applying a voltage and measuring the current passing through each of them and the luminance that each device gave out. This had to be done in a dark room to reduce the background noise. The current needed to be monitored to prevent a very high current from a short circuit burning the device and the measuring instrument (Figure 8).

Figure 8: The instrument for measuring the luminance of the OLEC device. Two pixels on the left worked very well, while the other two were short.

Moving on to the PET-based device ITO-coated PET substrates were provided by InnovationLab. These needed to be structured by inkjet-printing the PMMA 15k solution on top of the substrate and then etching in an acid bath. In this context, PMMA acts as an acid resist to protect certain parts of ITO from being etched off the substrate. Acid etching enables us to have a more complicated structure of ITO, which is required for the demonstrators. A multimeter can be used to check whether ITO has been etched off the substrate completely. Built-in Book Lighting The book cover mock up was made from a piece of cardboard. The folding mechanism was developed from the folding chair contraption. The OLEC devices were attached to the folding parts. Round magnets were used to hold the structure and define the ON/OFF positions.

Figure 9: The built-in book light in the ON position (Left) and in the OFF position (Right).

Lighting Puzzle All the layer design was done in Adobe Illustrator. The puzzle holder was also designed in Adobe Illustrator and cut from a piece of plexiglass by using a laser cutter. The evaporation mask was made for silver evaporation. The three layers of the device are illustrated in Figure 10.

Figure 10: The ITO layer design (yellow), the active layer design (green) and the metal mask for silver evaporation (bottom).

Hallway Lighting This project made use of electroluminescence3 (EL) panels instead of OLECs. One important requirement when using EL panels is that it needs a very high alternating voltage (about 100V). Therefore, direct touching with the circuit should be avoided. It was decided to use a 5V DC voltage source as it is more convenient and portable than connecting to a wall socket; therefore a DC/AC converter was required to convert the 5V DC voltage into a much higher AC voltage. The Arduino Uno is at the heart of this project (Figure 11). It is a microcontroller board that can be programmed with the Arduino software. It can communicate with other electronic components via its 14 digital input/output pins and 6 analog input pins.

Figure 11: The Arduino Uno microcontroller board.

The Sharp distance infrared sensor (GP2Y0A710K0F) (Figure 12) was connected to an analog input pin. Four EL panels were connected to a relay board, which was connected to four of the digital pins, and to the DC/AC converter the other end.

Figure 12: The Sharp distance infrared sensor (GP2Y0A710K0F).

The code contains some important parts as follows. 1. Assign each panel to a range of sensor readings. 2. In each range or sensor readings, turn on the corresponding relay switch so that the correct EL panel lights up. 3. If the reading is out of all the ranges, turn off all the relay switches so no EL panel lights up

Figure 13: The circuit diagram of the hallway lighting project, showing the infrared distance sensor, the Arduino microcontroller, the relay board and the electroluminescence panels .

5 Results & Discussions

Luminance4 For PMMA 15k, the devices with the ratio 1:0.5:0.1 gave the highest luminance of about 450 cd/m2 at a voltage of 18 V (Figure 14). For PMMA 350k, the brightest devices were those with the ratio 1:0.375:0.075, which gave a luminance of about 1500 cd/m2 at a voltage of 17 V (Figure 14). The brightest devices with PMMA 350k were significantly brighter than the brightest ones with PMMA 15k. Both turned on at about the same voltage. Therefore, our OLEC demonstrators would be made from the PMMA 350k-based active layer solution with the ratio SMG: PMMA: TBAF of 1:0.375:0.075.

Figure 14: The graphs of the luminance against the voltage for various spin-coated OLEC devices. These were used to find the optimal active layer solution.

Improvements Due to limited time, it was constrained to prepare only 2 devices per each ratio. The results would be much more reliable if more measurements had been done. Other ratios than these should be tested as well to see if there are better ratios to use for the active layer. High luminance and low turn-on voltage were two factors that were relevant to this project.

Printability Although the optimal active layer solution was PMMA 350k-based, it was expected that PMMA 350k would clog the nozzle of the inkjet printer because of its long chain. So OLECs made from solutions containing PMMA 350k would not be able to be inkjet-printed. Surprisingly, no clogging had been found. So it was decided to fabricate PMMA 350k-based devices by inkjet printing and compare these two different fabrication methods.

Figure 15: The plot of the luminance against the voltage for the inkjet-printed OLECs using the optimal active layer solution.

The devices, which were fabricated by inkjet printing, gave more reliable performance compared to those spin-coated. This is reasonable because inkjet printing is less manual than spin coating. Also, the luminance now just reached 500 cd/m2 (Figure 15), while it reached 1500 cd/m2 when it was fabricated by spin coating. This was addressed to dewetting issues because dewetting normally became more noticeable with inkjet printing than spin coating, so the active layer would be less homogenous than when it was spin-coated. Despite spending all the time working on OLECs, we did not manage to get any PETbased OLEC to work during the internship period whether the active solution was spin-coated or inkjet-printed on to the PET substrate. Therefore, we decided to concentrate all the effort on the book lighting and hallway lighting projects and move on to the puzzle project if time allowed. Book Lighting The folding mechanism was finished but experiments with PET devices were unsuccessful. Therefore, the prototype was built only to demonstrate the concept and folding mechanism. The PET devices will be put in place once they are finished and the battery will be hidden along the book spine. According to previous experiments on glass devices that were successful, they would need about 18 V to operate properly.

Lighting Puzzle This project had the same problem of not having any PET working device. Moreover, the puzzle requires a more complicated shape of the ITO layer. So it would be more difficult to get it working. The puzzle holder was finished. It consists of two parts. The lower part is the battery compartment and the upper part is the platform for the puzzle pieces to rest on. Hallway Lighting This was the only project that was completely finished. Initially, the sensor gave imprecise readings when it detected things far from itself. This caused undesired flickering of the EL panels. This was solved by averaging a number of readings first and then comparing one average to successive averages to see whether it was anomalous. The sensor responds differently depending on the brightness of the environment (background noise). Therefore, it should be kept in mind what the brightness of the environment was when the program was calibrated. The major problem is that the sensor responds precisely up until about 3.5m from the sensor. So in order to increase the working distance, more than 1 sensor must be used or a better sensor should be used instead of the current one. This has not been done within the internship period.

6 Conclusions
1. The structure of an OLEC consists of three layers on top of a substrate: cathode (ITO), active layer (SMG, PMMA and TBAF in anisole) and anode (silver) 2. The luminance of an OLEC depends on the solution used, the concentrations of each component and the fabrication techniques used. 3. The optimal solution is PMMA 350k-based and has the ratio SMG: PMMA: TBAF of 1:0.375:0.075 4. Glass substrates work very well, while PET substrates still need some more work in order to get them work properly

7 References
1. Ullrich Mitschke, Peter Bauerle, 2000. In The Electroluminescence of Organic Materials, pp1-2. The Royal Society of Chemistry. 2. Stephen Gasiorowicz, 1996. In Quantum Physics (2nd edition), pp9-10. John Wiley & Sons. 3. H.M. Sauer, C. Ranfeld, E. Drsam, 2010. In An investigation of the screen printing process for electroluminescent panels and the influence of printing and operation parameters on the performance of the panels, p1. LOPE-C. 4. M.V. Klein, T.E. Furtak, 1986. In Optics (2nd edition), pp210-212. John Wiley & Sons.