UNIVERSITY OF CALIFORNIA SANTA CRUZ PHOSPHORESCENT ORGANIC LIGHT EMITTING DEVICES A thesis submitted in partial satisfaction of the requirements

for the degree of MASTER OF SCIENCE in PHYSICS by Glenn P. Gray December 2010

The Thesis of Glenn P. Gray is approved:

Professor Sue A. Carter, Chair

Professor Joshua Deutsch

Professor David Belanger

Tyrus Miller Vice Provost and Dean of Graduate Studies

Copyright c by Glenn P. Gray 2010

Table of Contents

List of Figures Abstract Acknowledgments 1 Introduction 1.1 Motivation . . . . . . . . . . . . . . . . 1.2 From OLEDs to PHOLEDs . . . . . . . 1.3 Electroluminescence in Matter . . . . . 1.4 Basic OLED Operation and Structure . 1.4.1 Double and Multilayered OLEDs 1.4.2 Single Layer PHOLEDs . . . . . 1.5 OLED Efficiencies . . . . . . . . . . . . 1.5.1 Measurements . . . . . . . . . . 2 Experiment 3 Results 4 Conclusion and Next Steps A Preparing the Mix B Preparing the Substrate C Device Fabrication Procedure D Device Characterization Procedure Bibliography

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List of Figures

1.1 1.2

1.3 1.4

1.5 1.6 1.7 1.8

1.9 3.1

Energy level diagram showing the two types of luminescence; fluorescence and phosphorescence. . . . . . . . . . . . . . . . . . . . . . . . . Jablonski diagram illustrating the various absorption and emission processes in molecules. Internal conversion (IC) corresponds to nonradiative transitions between states of the same multiplicity, while intersystem crossing (ISC) corresponds to non-radiative transitions between states of differing multiplicity. Figure from reference[1] p.224. Simplified energy level diagram for single layer OLED showing chargeinjection EL process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . (a) Double layer OLED with the electron transport layer (ETL) as the emissive layer (EML). (b) Double layer device with the hole transport layer (HTL) as the EML. (c) Multilayer device where the EML is a separate layer, not a part of the ETL or HTL. . . . . . . . . . . . . . . Simplified energy level diagram for single layer PHOLED showing charge-injection EL process. . . . . . . . . . . . . . . . . . . . . . . . . Illustration of current J and recombination current Jr . . . . . . . . . . Radiometric quantities and their photometric analogs. . . . . . . . . . A graph of the photometric response of the eye superimposed with the visible spectrum. The peak is centered over green, meaning our eyes detect greens better than reds or blues, and we don’t see anything outside the visible spectrum. . . . . . . . . . . . . . . . . . . . . . . . Photometric responsivity of EG&G UV-100BQ photodiode. . . . . . .

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3.2 3.3

Comparison of photocurrent versus voltage for device made with PEDOT:PSS and LiF interfacial layers, and device made with PEDOT:PSS but no LiF interfacial layers. . . . . . . . . . . . . . . . . . 25 Current versus voltage and photocurrent versus voltage data for one device tested three times on three different days. . . . . . . . . . . . . 26 Current versus voltage and photocurrent versus voltage data for best device. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27

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3.4 3.5

Spectra from device made with PEDOT:PSS and LiF interfacial layers, and just PEDOT:PSS layer. . . . . . . . . . . . . . . . . . . . . . . . . 27 AFM image of morphology for device made which used 1,2 dichloroethane as the solvent. . . . . . . . . . . . . . . . . . . . . . . . 28

D.1 Experimental setup for taking spectra. . . . . . . . . . . . . . . . . . . 37 D.2 Experimental setup for taking current versus voltage and photocurrent versus voltage curves data. . . . . . . . . . . . . . . . . . . . . . . . . . 37

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In an effort to increase the internal conversion efficiency of OLEDs. First we will motivate the research and explain the physics of device operation. Then we will discuss device characterization and fabrication. and finally present the results achieved thus far. eliminating the need for additional charge injection aiding layers thus creating a single layered device.Abstract Phosphorescent Organic Light Emitting Devices by Glenn P. phosphors are added to the active layer and Phosphorescent Organic Light Emitting Devices (PHOLEDs) are made. Gray Organic Light Emitting Devices (OLEDs). a low molecular weight green emitter. have emerged as promising alternatives to solid state lighting applications and flat panel displays. Furthermore we will discuss the addition of the ionic salt Bu4 NBF4 and the use of thermo-electric annealing (TE annealing) to aid in charge injection. . Here we investigate the fabrication and characterization of PHOLEDs doped with the iridium complex Ir(ppy)3 .

Ben Balaban.Acknowledgments First I would like to thank Sue for allowing me to do this research. Yvonne Rodriguez. vii . I would also like to thank specific members of the lab who helped me in one way or another. Last but not least I’d like to thank my family for their love and support. and Guanmei Zhang. Jeremy Olson. Chris France.

specifically OLEDs doped with phosphors called PHOLEDs. Then the physics of electroluminescence is explained. The results section covers the progress made so far. 1 See Appendix for detailed step-by-step fabrication and characterization procedures. The introduction is concluded with an explanation of efficiencies and measurements used to characterize OLEDs. Next we will set the stage for the research conducted here by putting it into the context of work done so far. and the conclusion section summarizes the findings and suggests next steps for continuing the research done here.Chapter 1 Introduction Here we present work done on fabricating and characterizing organic light emitting devices (OLEDs). The experiment section outlines the procedure for making PHOLEDs1 . 1 . First we will motivate the research by highlighting some of the novel applications of PHOLEDs. followed by a review of basic OLED/PHOLED operation and device architectures.

the color of OLEDs can be tuned by introducing different organic dopants. and long lifetimes[2]. strong efficiencies. which require low power. resulting in devices that can be made paper thin. helping to reduce en- 2 . or a PDA that can be rolled up and stored in a small space such as a pen. OLEDs are thin film devices made either from thermally evaporating small organic molecules (called SMOLEDs). or are polymer based (called PLEDs) and solution processable made using wet fabrication techniques such as spin casting. and ink-jet printing[3].1 Motivation The next generation of flat panel display (FPD) and general solid state lighting applications has arrived with the OLED. since OLED technology is thin and lightweight it is ideal for applications in portable displays such as cell phones. flexible. doctor blading. low operating voltages. One of the biggest advantages of OLED technology is the ability to deposit the materials onto virtually any substrate such as glass. Imagine a TV in your living room that has the thickness of a wall poster and appears to be part of the wall until it is turned on. or thin metal foils. In order for OLEDs to be competitive in these markets they must exhibit exceptional brightness. Also. and transparent[4][5][6][7]. meaning they can be made into large area devices such as large area billboards or large area white lights. Furthermore. OLEDs are also scalable. plastic.1. and white OLEDs have already been made whose high efficiency and low power consumption make them ideal for general solid state lighting applications[8].

reported by Tang and VanSlyke in 1987. The first OLED was reported in 1965 by Helfrich and Schneider[10] and was made from single crystal anthracene. The trends in the literature show reports of high efficiency devices. and dopants have been introduced to increase efficiency.2 From OLEDs to PHOLEDs Obtaining high efficiencies has been the major driving force in OLED re- search and development. The first SMOLED. sandwiched between a transparent indium tin oxide (ITO) anode and 3 . Here we review some of the work done on OLEDs which have influenced current device structures and our current understanding. which is required for competitiveness in the FPD and lighting industries and which will greatly contribute to understanding device physics.ergy consumption. 1. OLEDs are made from one or multiple organic layers sandwiched between a transparent anode and a metallic cathode. and over the last twenty years new materials. however they were not very efficient and required high operating voltages due to the thickness of the crystal. which is a major issue in the United States where 20% of electrical energy consumption is used for lighting[9]. followed by methods of increasing device lifetime. Second to improving efficiency in OLEDs has been understanding degradation mechanisms and increasing the lifetime of devices. multilayered devices. was a double layer device made from layers of aromatic diamine and 8-hydroxyquinoline aluminum (Alq3 ).

The second generation PHOLEDs use iridium complexes such as Ir(ppy)3 as the phosphorescent dopant[17][18][19]. is limited to 25% based on spin statistics[15]. The first PLED made from the conjugated polymer poly(para-phenylene vinylene) (PPV) was reported by Friend et al.18-octaethyl-21H.7. and by Hoshino and Suzuki[14].8. with the introduction of a phosphorescent dopant and the birth of the phosphorescent OLED (PHOLED). of 1%[11]. However the internal quantum efficiency.a magnesium-silver alloy cathode. and had internal and external quantum efficiencies of 23% and 4% respectively[13]. which have internal quantum efficiencies of almost 2 2. These devices exhibited a ‘high’ external quantum efficiency. These two seminal reports marked the beginning of the OLED research and development boom. which increases device efficiency and hence lowers the current required to achieve a desired brightness[16].3. In phosphorescent devices the internal quantum efficiency can reach 100%. 23H-porphine platinum(II). The utilization of phosphorescent dopants in OLEDs was the logical next step in increasing the efficiency of OLEDs. defined as the ratio of photons generated within the material to injected electrons.[13].17. A major breakthrough in increasing efficiency was reached in 1998 by Baldo et al. in 1990[12]. In previous works OLEDs relied on the use of fluorescent materials to generate light. 4 . The first PHOLEDs used a platinum doped porphine complex PtOEP2 .12.13. which ultimately restricts the external quantum efficiency and hence device performance. defined as the fraction of photons emitted in the forward viewing direction to injected electrons.

3 Electroluminescence in Matter The process of radiative relaxation of molecules at low temperatures is known as luminescence. in which electrons and holes are injected into the luminescent material where they form singlet and triplet excitons. Before explaining the charge-injection EL process it is useful to review the energy structure of electrons in molecules. sonoluminescence.100%[20][21]. and is distinct from incandescence which is a high temperature process4 . 000h have been achieved for green and red PHOLEDs with initial brightness of 600cd/m2 and 300cd/m2 respectively[23]. Here we focus on charge-injection electroluminescence (EL). which depend on how the molecule was excited before luminescing. Devices based on Ir(ppy)3 with external quantum efficiencies of greater than 10%[22] and lifetimes3 of greater than 10. is excited to a higher energy and reemits another photon upon falling back to the ground state. and mechanoluminescence. bioluminescence. 4 Luminescence is also known as ‘cold emission’ for this reason. which decay to the ground state and emit light. Photoluminescence (PL) is the simplest form in which an electron in a molecule absorbs a photon. The allowed energy levels of an electron in a molecule correspond to sta3 Device lifetime is defined as the amount of time a device takes to degrade from one half of its initial brightness. such as chemiluminescence. 5 . However there are many forms of luminescence. Device lifetimes in PHOLEDs have been shown to be inversely proportional to initial brightness which is a typical characteristic of fluorescent OLEDs[24]. 1.

T2 . States with multiplicity of 3 are called triplet states Tn and have total spin angular momentum of 1.tionary states. One way to o number these states is to consider their spin multiplicities. . . from lowest energy to highest energy (starting from the ground state) they are S0 . Tn . where the transitions are spin-forbidden. The 6 .1: Energy level diagram showing the two types of luminescence. . . the spin is conserved from the initial to the final state. and T1 . The two types of emission are called fluorescence for Sn → S0 transitions and phosphorescence for Tn → S0 transitions. . Figure 1. Sn . States with multiplicity 1 are referred to as singlet states Sn and have total spin angular momentum of 0. Luminescence occurs when an electron in an excited singlet or triplet state relaxes to the singlet ground state. see Fig. Using these labels the energy structure of a molecule can be numbered. 1. and that fluorescence transitions from excited singlet states to the ground state are spin-allowed. This is not the case for phosphorescence. . fluorescence and phosphorescence. .1. meaning the spin of the electron must flip in order to go from a triplet state to a singlet state. S1 . It is important to note that normally the ground state is a singlet state. . which are represented by the eigenfunctions and eigenvalues of the molecule’s Hamiltonian found after solving the Schr¨dinger equation.

resulting in what are called “impure singlet” and “impure triplet” states. The strength of the spin-orbit coupling also determines the lifetimes of the excited states. making it possible for some materials with strong spin-orbit coupling to have phosphorescence transitions with the same lifetimes as fluorescence. transitions between these triplets and singlets (phosphorescence) is possible.2). Strictly speaking transitions from triplet states to singlet states are spinforbidden and therefore have zero intensity. while electrons in triplet states can have much longer lifetimes (sometimes greater than 10s) since the transition is spin-forbidden. The reason for this has to do with spin-orbit coupling. When the spin-orbit coupling term HSO is added to the molecule’s Hamiltonian and treated as a perturbation. even in the dark. once the paint is ‘charged’ (electrons in the material are excited) it can emit light over a long period of time.1 to 1 ns). The amount of mixing depends on the strength of the spin-orbit coupling term. the new stationary states of the new hamiltonian are mixtures of singlet and triplet states from the old Hamiltonian. which shows the different processes that 7 . nonetheless phosphorescent transitions occur. more mixing corresponds to strong spin-orbit coupling. The phenomena of fluorescence and phosphorescence is most readily illustrated using a Jablonski diagram (Fig. This is why phosphorescent materials are used in glow-in-the-dark paints. 1. so electrons singlet states decay rapidly (0.consequence of these spin-allowed and spin-forbidden transitions can be explained by the lifetime of the excited states. When the spin-orbit coupling term in the Hamiltonian is strong. Electrons like to be in their lowest energy state.

The simple structure shown in Fig. 1.fluorescence. Electrons and holes are injected from the 8 . and must be fast for efficient phosphorescent materials. P . falling down to the ground state. 1. The diagram is more detailed than Fig.(i) charge injection. ISC intersystem crossing).4 Basic OLED Operation and Structure OLEDs are made up of one or multiple thin film organic semiconducting layers sandwiched between a metallic cathode and transparent anode. Lifetimes of triplet states and triplet energy transfer have been studied in Alq3 based devices[25].2 shows. There are five processes involved in chargeinjection EL. The rate of ISC is determined by how much mixing of singlet and triplet states occur due to spin-orbit coupling. and the wavy lines correspond to non-radiative processes (IC .3 illustrates the charge-injection EL process similar to almost all OLEDs.can lead to luminescence in molecules. (iii) exciton formation.internal conversion.vibrational relaxation. As Fig. phosphorescence occurs after an electron in an excited singlet state undergoes ISC to an excited triplet state (or one of the higher vibrational levels of that state) after which it phosphoresces. (ii) charge migration. VR .phosphorescence) are shown as straight lines. (iv) light emission. or undergoes VR and does not emit a photon. 1. 1. and (v) light extraction. In the diagram absorption (A) and emission (F . which are located above each of the singlet and triplet levels.1 because it includes vibrational energy levels.

2: Jablonski diagram illustrating the various absorption and emission processes in molecules. Figure from reference[1] p.224. 9 . Internal conversion (IC) corresponds to non-radiative transitions between states of the same multiplicity. while intersystem crossing (ISC) corresponds to non-radiative transitions between states of differing multiplicity.Figure 1.

for example in fluorescent OLEDs only 25% of excitons contribute to light generation. respectively. singlet and triplet excitons are formed.4. OLEDs are made up of one or more thin semicon- ducting organic layers sandwiched between a transparent anode (ITO) and a metal cathode.1 Double and Multilayered OLEDs As previously mentioned. If the electron and hole meet on a single molecule.Figure 1. Double layer devices are made up of an electron transport layer (ETL) 10 . Because the excitons have relatively high binding energies of ∼ 1eV they can travel throughout the material without dissociating. cathode and anode. Not all excitons radiatively recombine. 1.3: Simplified energy level diagram for single layer OLED showing chargeinjection EL process. Charge transport through the organic material can be characterized by hopping between adjacent molecules. and travel through the material in opposite directions. and holes and electrons are assumed to recombine and emit light on a specific molecule [26][27][28].

For example. The ETL or the HTL can be doped so that it becomes the emissive layer (EML). electron and/or hole blocking layers are introduced to aid in increasing the recombination current. not a part of the ETL or HTL. Multilayer devices incorporate more layers to control and improve device efficiency[29]. followed by luminescence. So. which are chosen for their good electron and hole transport and charge injection from the cathode and anode respectively. (c) Multilayer device where the EML is a separate layer. Figure 1. And devices made with double emission layers 11 . (b) Double layer device with the hole transport layer (HTL) as the EML. in a double layer device. and hence the charge balance factor. Figure 1. by confining excitons to the EML[30].4 shows device architectures for double and multilayered devices.4: (a) Double layer OLED with the electron transport layer (ETL) as the emissive layer (EML). electrons and holes are injected into the ETL and HTL then meet at the EML to recombine and form excitons.and a hole transport layer (HTL).

and a phosphorescent dye dispersed in a appropriate solvent(s).4. interfacial layers between the cathode and ETL and/or anode and HTL are commonly introduced to reduce the charge injection barrier.have been shown to be highly efficient[31]. Furthermore. The ETM and HTM are doped polymers with good charge transport characteristics and make up the polymer matrix in which the phosphorescent dye is dispersed. a hole transport material (HTM).2 Single Layer PHOLEDs Single layer PHOLEDs are made from a blend of a electron transport mate- rial (ETM). Figure 1. 12 .5 shows a diagram of the energy structure of a single layer PHOLED.5: Simplified energy level diagram for single layer PHOLED showing chargeinjection EL process. Figure 1. 1. aiding in charge injection. The phosphorescent dye chosen has fast ISC rates (strong spin-orbit coupling) and has a low molecular weight to aid in the dispersion of the dye into the polymer matrix.

or add a small amount of salt additive and do a thermo-electric (TE) anneal as shown by Park et al. which can be characterized by a smooth AFM image of the surface.[32][33][34]. For example PEDOT:PSS5 can be used as the interfacial layer between the anode (ITO) and the organic layer. This is difficult to achieve with a one part solvent. First and foremost the solvent must properly dissolve all of the materials.e. The addition of the ionic salt tetrabutylammonium tetrafluoroborate 5 poly(3.2-dichloroethane and chloroform (3:1 mixing weight ratio) to achieve bright uniform EL[32][33][34]. When choosing a solvent two things must be kept in mind. Park et al. the choice of the solvent(s) is very important in controlling the morphology of the single layer PHOLED film. the phase separation of the different ingredients of the blend. As such. Secondly. i. To lower the charge injection barrier you can do two things. yields the best devices with the most uniform light emission and highest efficiency. so using a binary (two-part) solvent is recommended.4-ethylenedioxythiophene) :poly(styrene sulfonate) 13 .One of the biggest factors that determines the performance of a single layer PHOLED is the morphology. either use interfacial layers between the cathode/organic layers and organic/anode layers. it is useful from an fabrication point of view to choose solvents that have a high boiling point. used a binary solvent of 1. A uniform morphology. Solvents with lower boiling points are not ideal for large scale wet deposition techniques such as ink-jet printing. and lithium fluoride (LiF) can be used as the interfacial layer between the anode (Al) and the organic layer[35].

01 wt. is defined as the ratio of the number of photons emitted by the OLED in the forward viewing direction to the number of electrons injected. First the external quantum efficiency. This is different from the internal quantum efficiency ηint . The difference arises from the fact that not all photons generated within the structure of the OLED make it out of the device. It is important that the field points in the right direction or the ions will adsorb in the wrong direction. After the devices are made the device is placed on a hot plate and heated to T ◦ C and biased with a voltage V. %. anywhere from 0. Here we define and explain the standard measurements quoted in the literature.0025 wt. some photons are re-absorbed by the material and some 14 .(Bu4 NBF4 ) and using the TE anneal can also lower the charge injection barriers. The use of heat and electric field acts to split the salt into its cation and anion and allow for the adsorption of them toward the cathode and anode respectively. ηext . The salt is added in small amounts. % to 0. 1. which is defined as the ratio of the total number of photons generated within the structure of the OLED to the number of electrons injected. The temperature of the anneal is chosen so that it is below the glass transition temperature of the materials used.5 OLED Efficiencies It is important to standardize and define the different measurements used to characterize the luminescence of OLEDs[36]. Once the device lights up the field is terminated and it is taken off the hot plate and cooled.

Emission occurs when the singlet or triplet excitons radiatively decay to the ground state. First of all. 15 . most singlet excitons radiatively decay6 .are emitted in a direction other than the forward viewing direction. meaning the material is highly fluorescent (as opposed to phosphorescent). singlet and triplet excitons. molecular excited states.e. i. however the rate of intersystem crossing must be taken into account as well as the phosphorescence quantum yield φp . and all electrons and holes recombine to create excitons which all radiatively decay and are coupled out of the device in the forward direction. ηext = ηc · ηint . Second. 6 (1. This means that excitons are generated when a hole from the anode combines with an electron from the cathode to create singlet and triplet excitons.1) Note that in a perfect system the same number of electrons and holes are injected. Thirdly we assume that luminescence of the active material has a high fluorescence quantum yield φf . We introduce the light output coupling factor. A more quantitative description of the internal and external quantum efficiencies can be obtained after making a few assumptions. The internal quantum efficiency ηint is defined as ηint = γβφf . we assume that no charge is present in the active material without charge injection. so we only need to focus on charges injected from the electrodes.2) The efficiencies of PHOLEDs can be explained in a similar way to fluorescent OLEDs. (1. are generated by charge recombination. ηc to relate the external and internal quantum efficiencies.

and the amount of current that does not contribute to exciton formation (i. In single layer devices this amounts to adjusting the charge injection barrier at the electrode/organic interface and/or balancing the mobilities of the electrons and holes. we can write down expressions for J and Jr (see Fig.3) where Jr is the electron-hole recombination current density.4) (1. β is the production efficiency of emissive excitations. and they must be contained within the emissive region of the device7 .e. if electrons and holes injected do not form excitons they merely travel through the material and out. Jr = Jh − Jh = Je − Je .5) If all injected electrons and holes recombine within the emissive layer. and J is the measured current density. 7 16 .where γ is the charge balance factor. The charge balance factor is a measure of the efficiency of charge recombination. the current that makes it through the device) as Je and Jh . J = Jr then γ = 1. J = Jh + Je = Je + Jh . J γ= (1.6). In order to increase the efficiency of charge recombination (increase γ) a balance between injected holes and electrons must be obtained. In multilayer devices electron blocking and hole blocking layers can be introduced to increase the efficiency of charge recombination by aiding in the confinement of injected electrons and holes. and φf is the fluorescence quantum yield. and γ < 1 if Je or Jh is non-zero. In terms of the injected current the charge balance factor is defined as Jr . (1. 1. If we define the amount of current injected from the cathode and the anode as Je and Jh .

n2 (1.Figure 1. χ=1− 1− 1 . the maximum ηext = 5. The efficiency of the production of emissive excitations β is defined as the branching ratio for singlets and triplets.0%.7. However it must be noted that this is not an exact ceiling value for efficiencies of OLEDs. β = 0. and φf = 1. γ = 1. giving the frequently used approximation for χ as 0. An estimate of the light output coupling factor χ can be derived from simple ray optics.6: Illustration of current J and recombination current Jr .25. A typical value for n in OLEDs is 1.2. and is taken to be π based on simple spin statistics. Plugging in some numbers gives an estimate of the maximum external quantum efficiency of the OLED. but is a useful measure to aid in the understanding of 17 . Taking χ = 0.2.6) where n is the index of refraction of the material.

The lumen is defined as the measure of the power of light perceived by 18 .7: Radiometric quantities and their photometric analogs. except new units are introduced to account for the sensitivity of our eyes. The field of optical measurements is broken into two sub-fields. radiometry and photometry. The need for photometric quantities arises from the fact that our eyes only see light from the visible spectrum. These new units in the photometric quantities are the lumen (lm) and the candela (cd). Radiometry deals with the measurement of energy per time. but zero photometric power efficiency. while photodetectors can (theoretically) detect the entire spectrum.7).1 Measurements Next we will define and explain the standard measurements used to char- acterize OLED performance.OLED efficiency. For example an OLED that emits in the UV (or anywhere outside the visible spectrum) will have a measurable radiometric power efficiency.8). 1.5. 1. our eyes (see Fig. 1. and hence has units of watts (W). Photometric quantities have analog radiometric quantities (see Fig. Figure 1. However radiometric quantities are ill-suited for describing the performance of light emitting displays since they do not account for the sensitivity of our personal light detectors.

which amounts to biasing the device so that it is turned on and counting the number of photons emitted at each wavelength. meaning our eyes detect greens better than reds or blues. Hence a light source that emits 1 candela uniformly in all directions emits a total of 4π lumens. two testing setups are needed due to the limitations of the equipment being used. 1lm = 1cd·sr. the lumen can also be defined in terms of the candela. Figure 1. The peak is centered over green. The external quantum efficiency ηext is defined as q λIdet (λ)dλ hcf IOLED R(λ)dλ 19 ηext = (1. which has its own photopic responsivity R(λ) that needs to be taken into account. When testing devices.7) .the human eye. and we don’t see anything outside the visible spectrum. The second setup involves measuring the current and photocurrent of the device as a function of bias voltage.8: A graph of the photometric response of the eye superimposed with the visible spectrum. The first measurement setup is used to measure the spectra of the device. The photocurrent is measured by a photodiode.

Experimentally. and c is the speed of light. and IOLED is the current through the OLED. ηL = AL IOLED (1. ηP measured in lumens per watt is defined as the ratio of the luminous power emitted in the forward direction 20 .9: Photometric responsivity of EG&G UV-100BQ photodiode.9). it is best for the photodetector to be larger in area and as close as possible to the device in order to maximize f . The luminous power efficiency.where R(λ) is the photodiode responsivity (shown in Fig. 1. q is the charge of the electron. The luminous efficiency ηL is measured in candelas per amp. Figure 1. and is very similar to ηext except that the luminous efficiency takes the photopic response of the eye into account.8) where L is the luminance of the OLED (measured in [cd/m2 ]). A is the device area. or luminosity. f is the fraction of light emitted from the device to the light coupled into the detector. h is Plank’s constant. Idet (λ) is the photocurrent from the photodetector.

LP to the power used by the OLED at a particular voltage.9) Alternatively we can define ηP explicitly in terms of the photopic response of the eye. 21 . ηP = φ0 g(λ)Idet (λ)/R(λ)dλ f IOLED V (1.10) where φ0 = 683lm/W is the peak photopic response at λ = 555nm. ηP = LP IOLED V (1.

Specifically the blend consisted of TPD Bu-PBD Ir(ppy)3 PVK 0.3.1’biphenyl-4. wt.2 dichloroethane. The small amount of Ir(ppy)3 was chosen to prevent concentration quenching. The active material consisted of a blend of the hole transporting material TPD1 . the green emitter Ir(ppy)3 3 .34 wt. the electron transporting material Bu-PBD2 . % % % % where the weight percentages are with respect to the solvent.4-oxadiazole 3 tris(2-phenylpyridinato) iridium 4 Poly(9-vinylcarbazole) 22 . and evaporating an aluminum top electrode. wt.Chapter 2 Experiment Green PHOLEDs were fabricated by spincasting a solution of active material onto a glass slide printed with indium tin oxide (ITO).4’-diamine 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1. wt. and the hole transporting host material PVK4 in 1.06 0.N’-diphenyl-N.N’-bis(3-methylphenyl)-1.08 0. and to aid in solubility as Ir(ppy)3 has been shown to have poor solubility in commonly used solvents[37] (such 1 2 N.32 0.

D. depositing the materials. chlorobenzene. The interfacial layer PEDOT:PSS and active material were spun in a fumehood.% Bu4 NBF4 in the active solution and were TE annealed. Spectra. The active layer was formed by spincasting 60µL of the blend and vacuum annealing for 30min at 100-110 ◦ C. tetrahydrofuran. see Fig. Procedures for preparing the active blend.as toluene. D. 5 The amount and spin speed chosen yielded full coverage of the glass substrate.005wt.001 . and testing devices can be found in the Appendices.1 and Fig. and photocurrent versus voltage measurements were taken in the glovebox.2. Devices incorporated PEDOT:PSS and/or LiF interfacial layers to aid in charge injection into the active layer. and 1. preparing the substrates.2-dichloroethane). current versus voltage. and annealed in a vacuum oven. The TE anneal was performed in the glovebox on a hot plate at 85-95 ◦ C while being sourced by 7V.0. Typically5 150µL of filtered PEDOT:PSS was spun at 1500rpm and annealed at 100-110 ◦ C for 2030min. A Single layer devices incorporated 0. The LiF interfacial layer and aluminum top electrode were evaporated in a vacuum chamber below 2×10−6 T orr at approximately 1˚/sec to achieve thicknesses of 1nm and 50-100nm respectively. 23 .

3. the turn on voltage for the devices made with both PEDOT and LiF interfacial layers was lower than devices made with only PEDOT (see Fig. Two device structures were used to investigate the role of the interfacial layers: ITO/PEDOT:PSS/active material without salt/LiF/Al ITO/PEDOT:PSS/active material without salt/Al The active layer was a mix of TPD Bu-PBD Ir(ppy)3 PVK in 1.1).06 0. and the spectra for each device was almost identical (see Fig. % % % % .34 wt.2 dichloroethane. during testing of the best device O2 levels in the glovebox fluctuated between 6ppm and 100ppm.4). 3.Chapter 3 Results The performance of devices made with PEDOT:PSS and LiF interfacial layers were compared.08 0. As expected. indicating that such fluctuations should not 24 0.32 0. wt. wt. On another note. wt.

either the pixel had a uniform glow or there was a very bright spot on the pixel and the rest of the pixel was dim.3.2. Furthermore. and device made with PEDOT:PSS but no LiF interfacial layers. and currents were too high indicating poor efficiency. 3. The JV and PJV data for the best device is shown in Fig. 25 .1: Comparison of photocurrent versus voltage for device made with PEDOT:PSS and LiF interfacial layers. Finally the turn on voltages for the devices made here were too high. 3. all devices that were made worked in one way or another. significantly effect device performance.Figure 3. as was previously thought. and the bright spots turned into dark spots after multiple JV/PJV tests. see Fig. This means that all of the devices emitted light in one of two ways. Pixels with bright spots degraded quickly after multiple JV/PJV testing runs.

Figure 3. 26 .2: Current versus voltage and photocurrent versus voltage data for one device tested three times on three different days.

Figure 3. and just PEDOT:PSS layer. 27 .4: Spectra from device made with PEDOT:PSS and LiF interfacial layers. Figure 3.3: Current versus voltage and photocurrent versus voltage data for best device.

As previously stated it is hard to dissolve multiple materials into one solvent. Fig. Figure 3. hence improving the morphology.5 shows an AFM image of the morphology of the best device.5: AFM image of morphology for device made which used 1. 3. 28 .2 dichloroethane as the solvent. however an ideal morphology was not achieved. Decreasing the size of these aggregates. Hence binary solvents with different mixing weight ratios were used to improve morphology. should improve device characteristics. which has aggregates on the order of a few hundred nanometers.One explanation for the high power and non-uniform light emission is poor morphology of the films.

29 .Chapter 4 Conclusion and Next Steps In conclusion. Future research should focus on improving the morphology of the films. optimizing the dispersion of the materials in the blend by choosing and appropriate solvent(s). with the goal of achieving turn on voltages and operating currents comparable to devices made without salt and with PEDOT:PSS and LiF interfacial layers. PHOLEDs made from the iridium complex Ir(ppy)3 were fabricated. once the proper solvent(s) and desired morphology have been found more work can be done on devices made with the salt additive and the TE anneal. Improving morphology will yield a significant improvement in efficiency by lowering the currents and voltages required for bright light emission. Furthermore. however they lacked the desired efficiency exhibited by devices made in other groups.

01mg 16. which has a density of 1.03mg 3.00mg 17. Here is an example. % required can be weighed out on the scale.253 g/ml.012g of solvent and TPD Bu-PBD Ir(ppy)3 PVK 4. The amount of solvent is chosen so that the material with the smallest wt.2-dichloroethane. so the amount of solvent must be chosen accordingly. and leaving the mix on a stir-plate for 24 hours before making devices.Appendix A Preparing the Mix Preparing the mix of ingredients for the active layer consists of choosing a solvent. The scale can measure accurately down to about 1mg.04mg First weigh out the different materials and add them to the vial. calculating how much of each material to use from the weight of the solvent. weighing each component out. the weight percentages are the same as what is in the Single Layer PHOLED section. then pipet the 30 . the mix used 4ml of 1. putting everything in a vial with a stir-bar. So the mix uses 5.

and put it on the stir-plate over night1 To add a small amount of salt.25mg of salt. 2 The mix can also be made by making stock solutions for each of the different materials.25mg of salt pipet 250µl of the stock solution into the mix2 Leave the mix on the stir-plate long enough so that all the materials can be dissolved. Now the stock solution has a density of 1mg/ml.005 wt. say 0. weigh out a small amount of material . add a stir-bar. make a stock solution because the scale is not accurate enough to weigh such a small amount of material.solvent into the vial. this method uses less material but requires more bookkeeping. % of Bu4 NBF4 .which translates into 0. 1 31 .put it in a vial with a stir bar and add 1ml of solvent. To add 0.say 1mg . To make a stock solution. one way to check is to hold the vial up to the light and see if there are any materials still floating around.

Cleaning five slides at once is common. 4 I usually set the temperature of the sonicator to 40◦ C during the cleaning process. Sonicate in DI H2 O for 30min If you do clean ten at once. place the slides in the staining jar so they are glass-to-glass.Appendix B Preparing the Substrate The first thing that needs to be done is clean the ITO coated glass slides. and second I can be doing other work while the slides are cleaning 3 If the slides are new this step is unnecessary. Sonicate in Alconox for 60min4 3. make sure the ITO sides are not touching. scrape off old material3 in a petri dish filled with Alconox. Using a razor blade. three times over the sink 4. 2 Again this cleaning procedure is not hard and fast. DI H2 O. A commonly used slide cleaning procedure is as follows2 : 1. 1 32 . Letting the slides sonicate for a long time is advantageous for two reasons: first I’m confident they are clean. but up to ten can be cleaned at once if they are doubled up in the staining jar1 . 2. and dispose of waste in the hazardous liquids container in the fumehood. Rinse off slides with de-ionized water. for instance the amount of time in each step is variable.

Sonicate in ethanol for 30min 7.5. It is a good idea to turn on the vacuum oven at least 30min before making devices as it takes that long to get to the correct temperature. 33 . swab both sides of each slide in a petri dish filled with ethanol 6. Using a cotton tipped swab. Dry slides with filtered nitrogen Now that the slides are clean devices can be made.

2. Steps (1) and (2) are done at the spinning station in the fumehood. there are four basic steps: (1) deposit PEDOT:PSS interfacial layer. (3) evaporate LiF interfacial layer. and steps (3) and (4) are done in the evaporation chamber in the glovebox.Appendix C Device Fabrication Procedure The procedure here will include the deposition of PEDOT:PSS and LiF layers. (2) deposit active layer. The important thing here is getting a nice uniform film. 1 34 . Anneal in the vacuum oven at 100◦ C to 110◦ C for 30min. but also use more material if you’re not getting good coverage. Also the spin speed can be increased or decreased to change the thickness of the different layers. Filter PEDOT:PSS using 45µm syringe tip filter. Using clean slides will help. The device fabrication procedure is as follows: 1. and (4) evaporate Al top electrode. Here is the general order of operations. Spin down 150µl PEDOT:PSS at 1500rpm1 3.

but they survived in the glovebox for up to seven days with the O2 concentration between 5ppm and 45ppm. clean off the outer area of the device exposing the ITO pads. 6. If devices are shorting try a thicker layer. which is advantageous for efficiently using alloted time on lab equipment during business hours during the week. Next evaporate 100nm of Al at about 1˚/s. 5. Again. These devices do not like oxygen. Spin down 60µl of active material at 1000rpm2 for 45sec. for thicker devices reduce the spin speed.4. now devices are ready for top electrode evaporation. first transfer the slides to the glovebox and load the slides into the evaporation mask. Then ˚ evaporate 1nm to 10nm of LiF (at about . and close the bell jar. Using a cotton tipped swab dipped in ethanol. 3 2 35 . carefully clean off the outer edges of the device to expose the ITO pads. 7. Then raise the bell jar. put LiF and Al in their boats.5A/s. load the devices. This means that devices can be made at night and then tested the next morning. Now that the top electrode is ready to be evaporated. the slower the deposition rate the more uniform the layer will be). Anneal in the vacuum oven for 30min at 100◦ C to 110◦ C. Now A the devices are made and ready to be tested3 . Using a cotton tipped swab dipped in ethanol.

If the pixel lights up the device is ready to be tested. then using the Keithely 2400 source with current and measure the voltage. There are two measurement setups.2 show the setups for the two measurements. The basic idea consists of sourcing the device with Devices reported here had high turn on voltages and high currents. Figures D. Set the device holder near the window of the glovebox so that you can see it.vi program are used. so make sure that you pin out to the pixel correctly. and ramp up the source current while watching for the device to light up1 . To take spectra of the device the Ocean Optics mini spectrometer and spectrum. hence start at a low current of 1mA. and ramp up in steps of 1mA 1 36 .1 and D. Remember that these devices only work in forward bias. one for taking the spectra of the pixel. Load the slide into the device holder and pin out to one pixel. and the other for taking current versus voltage and photocurrent versus voltage curves.Appendix D Device Characterization Procedure The first thing to do before you test the devices is see if they work.

Figure D.2: Experimental setup for taking current versus voltage and photocurrent versus voltage curves data.1: Experimental setup for taking spectra. Figure D. 37 .

Use the 600µm fiber and the UV-Vis grating. click start and the spectra will appear on the screen. and also ramp up the source voltage to make the device brighter.vi program gives a plot of the spectrum. Then place the Ocean Optics fiber into the hole on the fiber holder and take the spectrum. Set the 2 Remember. Now. using a small allen-head screwdriver and the marking tape. Good spectra data counts are in the 3000 range. and the number of counts can be adjusted by using the ’averaging’ and integration time to increase the signal. When ready to take spectra. it allows you to choose what combination of fiber size.vi (the icon on the desktop says “run spectrum”) is setup to take different types of spectra. there is no need to take spectra data for each pixel. and no sphere. grating. Fix the photodiode to the device tester and pin out to the pixel to be tested. First turn on the spectrum. source the pixel of the device that will be used for spectrum data and move the hole in the fiber holder over the desired pixel. Once the fiber holder is attached. visually check to see if the pixel lights up before taking JV/PJV data 38 . spectrum. align and fix the fiber holder to the device holder. and integrating sphere. Next. Once the spectra of the pixel is taken the JV and PJV curves can be taken for the rest of the device. The pins are connected to the Keithley 2400 source meter and the photodiode is connected to the Keithley 485 picoammeter. To take JV and PJV curves use the multisweep program (an Igor program) on the left hand side computer2 .vi program and load the device into the device holder.enough voltage so that it is very bright and the spectrum.

and a name for the data about to be taken. Make sure the GPIB cables from both of the Keithley’s are connected to the left hand side computer. with the step size.ammeter so that it is on auto-range mode. and tell multisweep where the file is. Then click “acquire photocurrent” to measure photocurrent and current versus voltage at the same time. 39 . Then specify the file path where data is to be saved. and ending voltage at the top separated by commas. To set the voltage range create a text file (for example V in. Finally click start and multisweep will take the data.txt). starting voltage.

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