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. . . . . . .


9 10

11 12 17 18

19 20

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


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


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

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. Yvonne Rodriguez. and Guanmei Zhang. vii .Acknowledgments First I would like to thank Sue for allowing me to do this research. Ben Balaban. Jeremy Olson. Chris France.

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). 1 . First we will motivate the research by highlighting some of the novel applications of PHOLEDs. The introduction is concluded with an explanation of efficiencies and measurements used to characterize OLEDs. followed by a review of basic OLED/PHOLED operation and device architectures. specifically OLEDs doped with phosphors called PHOLEDs. The experiment section outlines the procedure for making PHOLEDs1 . 1 See Appendix for detailed step-by-step fabrication and characterization procedures. The results section covers the progress made so far. Then the physics of electroluminescence is explained.

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

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

23H-porphine platinum(II). The first PLED made from the conjugated polymer poly(para-phenylene vinylene) (PPV) was reported by Friend et al. These devices exhibited a ‘high’ external quantum efficiency. which have internal quantum efficiencies of almost 2 2. The first PHOLEDs used a platinum doped porphine complex PtOEP2 . 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].18-octaethyl-21H. defined as the fraction of photons emitted in the forward viewing direction to injected electrons. with the introduction of a phosphorescent dopant and the birth of the phosphorescent OLED (PHOLED). which increases device efficiency and hence lowers the current required to achieve a desired brightness[16].12. of 1%[11]. A major breakthrough in increasing efficiency was reached in 1998 by Baldo et al.17. The utilization of phosphorescent dopants in OLEDs was the logical next step in increasing the efficiency of OLEDs.[13]. 4 . in 1990[12]. These two seminal reports marked the beginning of the OLED research and development boom.3. However the internal quantum efficiency. defined as the ratio of photons generated within the material to injected electrons. which ultimately restricts the external quantum efficiency and hence device performance.7.8. and had internal and external quantum efficiencies of 23% and 4% respectively[13].13. In previous works OLEDs relied on the use of fluorescent materials to generate light.a magnesium-silver alloy cathode. and by Hoshino and Suzuki[14]. In phosphorescent devices the internal quantum efficiency can reach 100%.

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

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

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

phosphorescence) are shown as straight lines. 1. or undergoes VR and does not emit a photon.(i) charge injection.fluorescence. P .1 because it includes vibrational energy levels. In the diagram absorption (A) and emission (F . and (v) light extraction.vibrational relaxation. falling down to the ground state. and the wavy lines correspond to non-radiative processes (IC .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. (iv) light emission. and must be fast for efficient phosphorescent materials. Electrons and holes are injected from the 8 . 1. The simple structure shown in Fig. Lifetimes of triplet states and triplet energy transfer have been studied in Alq3 based devices[25]. 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.3 illustrates the charge-injection EL process similar to almost all OLEDs.2 shows.can lead to luminescence in molecules. (iii) exciton formation.internal conversion. VR . ISC intersystem crossing). (ii) charge migration. 1. 1. The diagram is more detailed than 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. As Fig. which are located above each of the singlet and triplet levels.

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

and travel through the material in opposite directions.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. OLEDs are made up of one or more thin semicon- ducting organic layers sandwiched between a transparent anode (ITO) and a metal cathode. Not all excitons radiatively recombine. cathode and anode. Double layer devices are made up of an electron transport layer (ETL) 10 . If the electron and hole meet on a single molecule. singlet and triplet excitons are formed. and holes and electrons are assumed to recombine and emit light on a specific molecule [26][27][28]. Because the excitons have relatively high binding energies of ∼ 1eV they can travel throughout the material without dissociating.4.1 Double and Multilayered OLEDs As previously mentioned. for example in fluorescent OLEDs only 25% of excitons contribute to light generation. respectively. 1.Figure 1.

Figure 1. For example. followed by luminescence. So. which are chosen for their good electron and hole transport and charge injection from the cathode and anode respectively. electrons and holes are injected into the ETL and HTL then meet at the EML to recombine and form excitons. in a double layer device. (c) Multilayer device where the EML is a separate layer.and a hole transport layer (HTL). And devices made with double emission layers 11 . Multilayer devices incorporate more layers to control and improve device efficiency[29].4 shows device architectures for double and multilayered devices. The ETL or the HTL can be doped so that it becomes the emissive layer (EML). by confining excitons to the EML[30]. electron and/or hole blocking layers are introduced to aid in increasing the recombination current. (b) Double layer device with the hole transport layer (HTL) as the EML. Figure 1.4: (a) Double layer OLED with the electron transport layer (ETL) as the emissive layer (EML). not a part of the ETL or HTL. and hence the charge balance factor.

1. Furthermore. Figure 1.5: Simplified energy level diagram for single layer PHOLED showing chargeinjection EL process.2 Single Layer PHOLEDs Single layer PHOLEDs are made from a blend of a electron transport mate- rial (ETM).have been shown to be highly efficient[31]. a hole transport material (HTM).4. interfacial layers between the cathode and ETL and/or anode and HTL are commonly introduced to reduce the charge injection barrier. and a phosphorescent dye dispersed in a appropriate solvent(s). 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.5 shows a diagram of the energy structure of a single layer PHOLED. 12 . Figure 1. 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. aiding in charge injection.

either use interfacial layers between the cathode/organic layers and organic/anode layers. the phase separation of the different ingredients of the blend. As such. This is difficult to achieve with a one part solvent. and lithium fluoride (LiF) can be used as the interfacial layer between the anode (Al) and the organic layer[35]. i. so using a binary (two-part) solvent is recommended. When choosing a solvent two things must be kept in mind. yields the best devices with the most uniform light emission and highest efficiency.One of the biggest factors that determines the performance of a single layer PHOLED is the morphology.e. used a binary solvent of 1. Solvents with lower boiling points are not ideal for large scale wet deposition techniques such as ink-jet printing.2-dichloroethane and chloroform (3:1 mixing weight ratio) to achieve bright uniform EL[32][33][34]. A uniform morphology. To lower the charge injection barrier you can do two things.4-ethylenedioxythiophene) :poly(styrene sulfonate) 13 . The addition of the ionic salt tetrabutylammonium tetrafluoroborate 5 poly(3. the choice of the solvent(s) is very important in controlling the morphology of the single layer PHOLED film. Secondly. it is useful from an fabrication point of view to choose solvents that have a high boiling point. First and foremost the solvent must properly dissolve all of the materials. For example PEDOT:PSS5 can be used as the interfacial layer between the anode (ITO) and the organic layer. or add a small amount of salt additive and do a thermo-electric (TE) anneal as shown by Park et al. Park et al. which can be characterized by a smooth AFM image of the surface.[32][33][34].

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 salt is added in small amounts. The temperature of the anneal is chosen so that it is below the glass transition temperature of the materials used. 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. ηext . Here we define and explain the standard measurements quoted in the literature. First the external quantum efficiency.0025 wt. % to 0. anywhere from 0. After the devices are made the device is placed on a hot plate and heated to T ◦ C and biased with a voltage V. %. 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. It is important that the field points in the right direction or the ions will adsorb in the wrong direction. The difference arises from the fact that not all photons generated within the structure of the OLED make it out of the device.5 OLED Efficiencies It is important to standardize and define the different measurements used to characterize the luminescence of OLEDs[36]. This is different from the internal quantum efficiency ηint . 1.01 wt.(Bu4 NBF4 ) and using the TE anneal can also lower the charge injection barriers. some photons are re-absorbed by the material and some 14 . Once the device lights up the field is terminated and it is taken off the hot plate and cooled.

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

e. and φf is the fluorescence quantum yield.4) (1. The charge balance factor is a measure of the efficiency of charge recombination. J γ= (1. If we define the amount of current injected from the cathode and the anode as Je and Jh . and the amount of current that does not contribute to exciton formation (i.6). and they must be contained within the emissive region of the device7 . (1. J = Jh + Je = Je + Jh . if electrons and holes injected do not form excitons they merely travel through the material and out. 1. 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.where γ is the charge balance factor. J = Jr then γ = 1.3) where Jr is the electron-hole recombination current density. In terms of the injected current the charge balance factor is defined as Jr . and J is the measured current density. we can write down expressions for J and Jr (see Fig. and γ < 1 if Je or Jh is non-zero. In order to increase the efficiency of charge recombination (increase γ) a balance between injected holes and electrons must be obtained. the current that makes it through the device) as Je and Jh . 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. Jr = Jh − Jh = Je − Je .5) If all injected electrons and holes recombine within the emissive layer. β is the production efficiency of emissive excitations. 7 16 .

γ = 1.2.2. Plugging in some numbers gives an estimate of the maximum external quantum efficiency of the OLED. and φf = 1. n2 (1.25. An estimate of the light output coupling factor χ can be derived from simple ray optics. χ=1− 1− 1 . Taking χ = 0. A typical value for n in OLEDs is 1.7. β = 0.6) where n is the index of refraction of the material. giving the frequently used approximation for χ as 0.Figure 1.0%. but is a useful measure to aid in the understanding of 17 . The efficiency of the production of emissive excitations β is defined as the branching ratio for singlets and triplets. the maximum ηext = 5.6: Illustration of current J and recombination current Jr . However it must be noted that this is not an exact ceiling value for efficiencies of OLEDs. and is taken to be π based on simple spin statistics.

radiometry and photometry. while photodetectors can (theoretically) detect the entire spectrum. 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. The field of optical measurements is broken into two sub-fields. 1. 1. For example an OLED that emits in the UV (or anywhere outside the visible spectrum) will have a measurable radiometric power efficiency.8). The lumen is defined as the measure of the power of light perceived by 18 . The need for photometric quantities arises from the fact that our eyes only see light from the visible spectrum.5.1 Measurements Next we will define and explain the standard measurements used to char- acterize OLED performance. Figure 1. and hence has units of watts (W). Photometric quantities have analog radiometric quantities (see Fig.7). except new units are introduced to account for the sensitivity of our eyes. 1. but zero photometric power efficiency.OLED efficiency. our eyes (see Fig. These new units in the photometric quantities are the lumen (lm) and the candela (cd).7: Radiometric quantities and their photometric analogs. Radiometry deals with the measurement of energy per time.

7) . Hence a light source that emits 1 candela uniformly in all directions emits a total of 4π lumens. 1lm = 1cd·sr. which amounts to biasing the device so that it is turned on and counting the number of photons emitted at each wavelength. and we don’t see anything outside the visible spectrum.the human eye. The photocurrent is measured by a photodiode. two testing setups are needed due to the limitations of the equipment being used. meaning our eyes detect greens better than reds or blues. The first measurement setup is used to measure the spectra of the device. Figure 1.8: A graph of the photometric response of the eye superimposed with the visible spectrum. the lumen can also be defined in terms of the candela. The peak is centered over green. The second setup involves measuring the current and photocurrent of the device as a function of bias voltage. which has its own photopic responsivity R(λ) that needs to be taken into account. When testing devices. The external quantum efficiency ηext is defined as q λIdet (λ)dλ hcf IOLED R(λ)dλ 19 ηext = (1.

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

9) Alternatively we can define ηP explicitly in terms of the photopic response of the eye.LP to the power used by the OLED at a particular voltage.10) where φ0 = 683lm/W is the peak photopic response at λ = 555nm. 21 . ηP = φ0 g(λ)Idet (λ)/R(λ)dλ f IOLED V (1. ηP = LP IOLED V (1.

1’biphenyl-4.06 0. and the hole transporting host material PVK4 in 1. the green emitter Ir(ppy)3 3 . % % % % where the weight percentages are with respect to the solvent. wt.2 dichloroethane. The small amount of Ir(ppy)3 was chosen to prevent concentration quenching.32 0. wt. Specifically the blend consisted of TPD Bu-PBD Ir(ppy)3 PVK 0. the electron transporting material Bu-PBD2 .4’-diamine 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1.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. wt. The active material consisted of a blend of the hole transporting material TPD1 . and evaporating an aluminum top electrode.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-oxadiazole 3 tris(2-phenylpyridinato) iridium 4 Poly(9-vinylcarbazole) 22 .34 wt.3.

and 1. Spectra. D.1 and Fig. The interfacial layer PEDOT:PSS and active material were spun in a fumehood. depositing the materials. current versus voltage. and photocurrent versus voltage measurements were taken in the glovebox. chlorobenzene. A Single layer devices incorporated 0.005wt. and testing devices can be found in the toluene. Procedures for preparing the active blend. D.2. Devices incorporated PEDOT:PSS and/or LiF interfacial layers to aid in charge injection into the active layer. and annealed in a vacuum oven.0. The TE anneal was performed in the glovebox on a hot plate at 85-95 ◦ C while being sourced by 7V. The active layer was formed by spincasting 60µL of the blend and vacuum annealing for 30min at 100-110 ◦ C. 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. preparing the substrates. see Fig. Typically5 150µL of filtered PEDOT:PSS was spun at 1500rpm and annealed at 100-110 ◦ C for 2030min. tetrahydrofuran.% Bu4 NBF4 in the active solution and were TE annealed. 5 The amount and spin speed chosen yielded full coverage of the glass substrate.2-dichloroethane). 23 .001 .

2 dichloroethane. indicating that such fluctuations should not 24 0. wt. 3.1). 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. wt.4).06 0. and the spectra for each device was almost identical (see Fig. wt.Chapter 3 Results The performance of devices made with PEDOT:PSS and LiF interfacial layers were compared.08 0.34 wt. 3. As expected. % % % % . 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. during testing of the best device O2 levels in the glovebox fluctuated between 6ppm and 100ppm.32 0. On another note.

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

26 .Figure 3.2: Current versus voltage and photocurrent versus voltage data for one device tested three times on three different days.

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

however an ideal morphology was not achieved. 3. As previously stated it is hard to dissolve multiple materials into one solvent. which has aggregates on the order of a few hundred nanometers. Decreasing the size of these aggregates.One explanation for the high power and non-uniform light emission is poor morphology of the films.5: AFM image of morphology for device made which used 1. Hence binary solvents with different mixing weight ratios were used to improve morphology. Fig. 28 . should improve device characteristics. Figure 3.5 shows an AFM image of the morphology of the best device.2 dichloroethane as the solvent. hence improving the morphology.

Chapter 4 Conclusion and Next Steps In conclusion. Future research should focus on improving the morphology of the films. Furthermore. Improving morphology will yield a significant improvement in efficiency by lowering the currents and voltages required for bright light emission. 29 . 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. PHOLEDs made from the iridium complex Ir(ppy)3 were fabricated. however they lacked the desired efficiency exhibited by devices made in other groups. 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.

00mg 17. Here is an example. The scale can measure accurately down to about 1mg.012g of solvent and TPD Bu-PBD Ir(ppy)3 PVK 4.04mg First weigh out the different materials and add them to the vial. the mix used 4ml of 1. so the amount of solvent must be chosen accordingly. putting everything in a vial with a stir-bar. which has a density of 1.253 g/ml.Appendix A Preparing the Mix Preparing the mix of ingredients for the active layer consists of choosing a solvent.2-dichloroethane. % required can be weighed out on the scale.01mg 16. and leaving the mix on a stir-plate for 24 hours before making devices. weighing each component out. So the mix uses 5. then pipet the 30 . the weight percentages are the same as what is in the Single Layer PHOLED section. calculating how much of each material to use from the weight of the solvent. The amount of solvent is chosen so that the material with the smallest wt.03mg 3.

this method uses less material but requires more bookkeeping. make a stock solution because the scale is not accurate enough to weigh such a small amount of material. % of Bu4 NBF4 . Now the stock solution has a density of 1mg/ml.say 1mg .solvent into the vial.005 wt. 1 31 . To make a stock solution.which translates into 0. weigh out a small amount of material . To add 0. add a stir-bar.put it in a vial with a stir bar and add 1ml of solvent. one way to check is to hold the vial up to the light and see if there are any materials still floating around. say 0.25mg of salt. and put it on the stir-plate over night1 To add a small amount 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.

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

33 . Dry slides with filtered nitrogen Now that the slides are clean devices can be made.5. swab both sides of each slide in a petri dish filled with ethanol 6. 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. Using a cotton tipped swab. Sonicate in ethanol for 30min 7.

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

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

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

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

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

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

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