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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
1.5 1.6 1.7 1.8
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 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. . . . . . .
11 12 17 18
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
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
First we will motivate the research and explain the physics of device operation. 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. In an eﬀort to increase the internal conversion eﬃciency of OLEDs. Then we will discuss device characterization and fabrication. eliminating the need for additional charge injection aiding layers thus creating a single layered device. and ﬁnally present the results achieved thus far. Here we investigate the fabrication and characterization of PHOLEDs doped with the iridium complex Ir(ppy)3 . have emerged as promising alternatives to solid state lighting applications and ﬂat panel displays. . phosphors are added to the active layer and Phosphorescent Organic Light Emitting Devices (PHOLEDs) are made.Abstract Phosphorescent Organic Light Emitting Devices by Glenn P. Gray Organic Light Emitting Devices (OLEDs).
Last but not least I’d like to thank my family for their love and support. Jeremy Olson. Chris France. and Guanmei Zhang. vii . Yvonne Rodriguez. I would also like to thank speciﬁc members of the lab who helped me in one way or another. Ben Balaban.Acknowledgments First I would like to thank Sue for allowing me to do this research.
speciﬁcally OLEDs doped with phosphors called PHOLEDs. 1 See Appendix for detailed step-by-step fabrication and characterization procedures. The experiment section outlines the procedure for making PHOLEDs1 . 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.Chapter 1 Introduction Here we present work done on fabricating and characterizing organic light emitting devices (OLEDs). The results section covers the progress made so far. followed by a review of basic OLED/PHOLED operation and device architectures. 1 . Next we will set the stage for the research conducted here by putting it into the context of work done so far. Then the physics of electroluminescence is explained. and the conclusion section summarizes the ﬁndings and suggests next steps for continuing the research done here.
ﬂexible. strong eﬃciencies. OLEDs are also scalable. or are polymer based (called PLEDs) and solution processable made using wet fabrication techniques such as spin casting. which require low power. and transparent. and long lifetimes. 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. and white OLEDs have already been made whose high eﬃciency and low power consumption make them ideal for general solid state lighting applications. One of the biggest advantages of OLED technology is the ability to deposit the materials onto virtually any substrate such as glass. meaning they can be made into large area devices such as large area billboards or large area white lights. OLEDs are thin ﬁlm devices made either from thermally evaporating small organic molecules (called SMOLEDs). or a PDA that can be rolled up and stored in a small space such as a pen. low operating voltages. In order for OLEDs to be competitive in these markets they must exhibit exceptional brightness. helping to reduce en- 2 . Also. or thin metal foils. plastic. Furthermore.1. doctor blading. the color of OLEDs can be tuned by introducing diﬀerent organic dopants.1 Motivation The next generation of ﬂat panel display (FPD) and general solid state lighting applications has arrived with the OLED. and ink-jet printing. resulting in devices that can be made paper thin. since OLED technology is thin and lightweight it is ideal for applications in portable displays such as cell phones.
which is a major issue in the United States where 20% of electrical energy consumption is used for lighting. multilayered devices. OLEDs are made from one or multiple organic layers sandwiched between a transparent anode and a metallic cathode. and dopants have been introduced to increase eﬃciency. reported by Tang and VanSlyke in 1987. 1. and over the last twenty years new materials. Second to improving eﬃciency in OLEDs has been understanding degradation mechanisms and increasing the lifetime of devices.ergy consumption. The trends in the literature show reports of high eﬃciency devices. The ﬁrst OLED was reported in 1965 by Helfrich and Schneider and was made from single crystal anthracene. however they were not very eﬃcient and required high operating voltages due to the thickness of the crystal. was a double layer device made from layers of aromatic diamine and 8-hydroxyquinoline aluminum (Alq3 ). Here we review some of the work done on OLEDs which have inﬂuenced current device structures and our current understanding. The ﬁrst SMOLED. sandwiched between a transparent indium tin oxide (ITO) anode and 3 .2 From OLEDs to PHOLEDs Obtaining high eﬃciencies has been the major driving force in OLED re- search and development. followed by methods of increasing device lifetime. which is required for competitiveness in the FPD and lighting industries and which will greatly contribute to understanding device physics.
In previous works OLEDs relied on the use of ﬂuorescent materials to generate light. deﬁned as the fraction of photons emitted in the forward viewing direction to injected electrons.a magnesium-silver alloy cathode. The utilization of phosphorescent dopants in OLEDs was the logical next step in increasing the eﬃciency of OLEDs.8. The ﬁrst PLED made from the conjugated polymer poly(para-phenylene vinylene) (PPV) was reported by Friend et al. is limited to 25% based on spin statistics.13. A major breakthrough in increasing eﬃciency was reached in 1998 by Baldo et al. However the internal quantum eﬃciency..18-octaethyl-21H. and had internal and external quantum eﬃciencies of 23% and 4% respectively. The second generation PHOLEDs use iridium complexes such as Ir(ppy)3 as the phosphorescent dopant. The ﬁrst PHOLEDs used a platinum doped porphine complex PtOEP2 . These devices exhibited a ‘high’ external quantum eﬃciency. which increases device eﬃciency and hence lowers the current required to achieve a desired brightness. which have internal quantum eﬃciencies of almost 2 2. with the introduction of a phosphorescent dopant and the birth of the phosphorescent OLED (PHOLED). 23H-porphine platinum(II).3. In phosphorescent devices the internal quantum eﬃciency can reach 100%.17. deﬁned as the ratio of photons generated within the material to injected electrons. which ultimately restricts the external quantum eﬃciency and hence device performance. of 1%. in 1990. and by Hoshino and Suzuki.7. 4 .12. These two seminal reports marked the beginning of the OLED research and development boom.
Device lifetimes in PHOLEDs have been shown to be inversely proportional to initial brightness which is a typical characteristic of ﬂuorescent OLEDs. such as chemiluminescence. sonoluminescence. 000h have been achieved for green and red PHOLEDs with initial brightness of 600cd/m2 and 300cd/m2 respectively. Here we focus on charge-injection electroluminescence (EL). and mechanoluminescence. 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. and is distinct from incandescence which is a high temperature process4 .100%. in which electrons and holes are injected into the luminescent material where they form singlet and triplet excitons. 5 . However there are many forms of luminescence. Photoluminescence (PL) is the simplest form in which an electron in a molecule absorbs a photon.3 Electroluminescence in Matter The process of radiative relaxation of molecules at low temperatures is known as luminescence. which decay to the ground state and emit light. is excited to a higher energy and reemits another photon upon falling back to the ground state. 1. Before explaining the charge-injection EL process it is useful to review the energy structure of electrons in molecules. which depend on how the molecule was excited before luminescing. Devices based on Ir(ppy)3 with external quantum eﬃciencies of greater than 10% and lifetimes3 of greater than 10. bioluminescence. 4 Luminescence is also known as ‘cold emission’ for this reason.
The two types of emission are called ﬂuorescence for Sn → S0 transitions and phosphorescence for Tn → S0 transitions. ﬂuorescence and phosphorescence. . States with multiplicity 1 are referred to as singlet states Sn and have total spin angular momentum of 0. . The 6 . Tn .1. Figure 1. . This is not the case for phosphorescence. S1 . It is important to note that normally the ground state is a singlet state. see Fig. T2 . the spin is conserved from the initial to the ﬁnal state. Sn . . States with multiplicity of 3 are called triplet states Tn and have total spin angular momentum of 1. . . meaning the spin of the electron must ﬂip in order to go from a triplet state to a singlet state.tionary states. Using these labels the energy structure of a molecule can be numbered. One way to o number these states is to consider their spin multiplicities. and that ﬂuorescence transitions from excited singlet states to the ground state are spin-allowed.1: Energy level diagram showing the two types of luminescence. which are represented by the eigenfunctions and eigenvalues of the molecule’s Hamiltonian found after solving the Schr¨dinger equation. . . Luminescence occurs when an electron in an excited singlet or triplet state relaxes to the singlet ground state. from lowest energy to highest energy (starting from the ground state) they are S0 . where the transitions are spin-forbidden. and T1 . 1.
while electrons in triplet states can have much longer lifetimes (sometimes greater than 10s) since the transition is spin-forbidden.2). more mixing corresponds to strong spin-orbit coupling. The amount of mixing depends on the strength of the spin-orbit coupling term. Strictly speaking transitions from triplet states to singlet states are spinforbidden and therefore have zero intensity. When the spin-orbit coupling term in the Hamiltonian is strong.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 HSO is added to the molecule’s Hamiltonian and treated as a perturbation. once the paint is ‘charged’ (electrons in the material are excited) it can emit light over a long period of time. nonetheless phosphorescent transitions occur. transitions between these triplets and singlets (phosphorescence) is possible. resulting in what are called “impure singlet” and “impure triplet” states. making it possible for some materials with strong spin-orbit coupling to have phosphorescence transitions with the same lifetimes as ﬂuorescence. so electrons singlet states decay rapidly (0. The phenomena of ﬂuorescence and phosphorescence is most readily illustrated using a Jablonski diagram (Fig. even in the dark. the new stationary states of the new hamiltonian are mixtures of singlet and triplet states from the old Hamiltonian. 1.1 to 1 ns). The reason for this has to do with spin-orbit coupling. The strength of the spin-orbit coupling also determines the lifetimes of the excited states. Electrons like to be in their lowest energy state. which shows the diﬀerent processes that 7 . This is why phosphorescent materials are used in glow-in-the-dark paints.
or undergoes VR and does not emit a photon.(i) charge injection. There are ﬁve processes involved in chargeinjection EL.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. 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. P . 1. Electrons and holes are injected from the 8 . The simple structure shown in Fig. Lifetimes of triplet states and triplet energy transfer have been studied in Alq3 based devices. 1.vibrational relaxation. and must be fast for eﬃcient phosphorescent materials. 1. In the diagram absorption (A) and emission (F . As Fig.phosphorescence) are shown as straight lines. which are located above each of the singlet and triplet levels.ﬂuorescence.internal conversion. The rate of ISC is determined by how much mixing of singlet and triplet states occur due to spin-orbit coupling. falling down to the ground state. VR . ISC intersystem crossing).can lead to luminescence in molecules. (iv) light emission. and (v) light extraction. The diagram is more detailed than Fig. (iii) exciton formation.1 because it includes vibrational energy levels. and the wavy lines correspond to non-radiative processes (IC .2 shows.3 illustrates the charge-injection EL process similar to almost all OLEDs. 1. (ii) charge migration.
224.2: Jablonski diagram illustrating the various absorption and emission processes in molecules. Internal conversion (IC) corresponds to non-radiative transitions between states of the same multiplicity. 9 . Figure from reference p.Figure 1. while intersystem crossing (ISC) corresponds to non-radiative transitions between states of diﬀering multiplicity.
Charge transport through the organic material can be characterized by hopping between adjacent molecules.3: Simpliﬁed energy level diagram for single layer OLED showing chargeinjection EL process. Not all excitons radiatively recombine. cathode and anode. If the electron and hole meet on a single molecule. Because the excitons have relatively high binding energies of ∼ 1eV they can travel throughout the material without dissociating. and travel through the material in opposite directions. singlet and triplet excitons are formed. 1. OLEDs are made up of one or more thin semicon- ducting organic layers sandwiched between a transparent anode (ITO) and a metal cathode. Double layer devices are made up of an electron transport layer (ETL) 10 .1 Double and Multilayered OLEDs As previously mentioned. for example in ﬂuorescent OLEDs only 25% of excitons contribute to light generation.4. and holes and electrons are assumed to recombine and emit light on a speciﬁc molecule . respectively.Figure 1.
followed by luminescence. electrons and holes are injected into the ETL and HTL then meet at the EML to recombine and form excitons. (b) Double layer device with the hole transport layer (HTL) as the EML. And devices made with double emission layers 11 .and a hole transport layer (HTL). Multilayer devices incorporate more layers to control and improve device eﬃciency.4 shows device architectures for double and multilayered devices. (c) Multilayer device where the EML is a separate layer. in a double layer device. not a part of the ETL or HTL. So. which are chosen for their good electron and hole transport and charge injection from the cathode and anode respectively. 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. and hence the charge balance factor. For example. Figure 1.4: (a) Double layer OLED with the electron transport layer (ETL) as the emissive layer (EML). by conﬁning excitons to the EML. 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. a hole transport material (HTM). interfacial layers between the cathode and ETL and/or anode and HTL are commonly introduced to reduce the charge injection barrier.5 shows a diagram of the energy structure of a single layer PHOLED. 1. aiding in charge injection. Figure 1.5: Simpliﬁed energy level diagram for single layer PHOLED showing chargeinjection EL process. Furthermore.2 Single Layer PHOLEDs Single layer PHOLEDs are made from a blend of a electron transport mate- rial (ETM).4. 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. and a phosphorescent dye dispersed in a appropriate solvent(s).have been shown to be highly eﬃcient. Figure 1. 12 .
. To lower the charge injection barrier you can do two things. As such. yields the best devices with the most uniform light emission and highest eﬃciency. The addition of the ionic salt tetrabutylammonium tetraﬂuoroborate 5 poly(3. so using a binary (two-part) solvent is recommended. Solvents with lower boiling points are not ideal for large scale wet deposition techniques such as ink-jet printing.4-ethylenedioxythiophene) :poly(styrene sulfonate) 13 . Secondly. When choosing a solvent two things must be kept in mind. Park et al. This is diﬃcult to achieve with a one part solvent. the phase separation of the diﬀerent ingredients of the blend. A uniform morphology. which can be characterized by a smooth AFM image of the surface. First and foremost the solvent must properly dissolve all of the materials.2-dichloroethane and chloroform (3:1 mixing weight ratio) to achieve bright uniform EL. the choice of the solvent(s) is very important in controlling the morphology of the single layer PHOLED ﬁlm. it is useful from an fabrication point of view to choose solvents that have a high boiling point. either use interfacial layers between the cathode/organic layers and organic/anode layers. For example PEDOT:PSS5 can be used as the interfacial layer between the anode (ITO) and the organic layer.One of the biggest factors that determines the performance of a single layer PHOLED is the morphology. i. and lithium ﬂuoride (LiF) can be used as the interfacial layer between the anode (Al) 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.e. used a binary solvent of 1.
5 OLED Eﬃciencies It is important to standardize and deﬁne the diﬀerent measurements used to characterize the luminescence of OLEDs. The temperature of the anneal is chosen so that it is below the glass transition temperature of the materials used. 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. 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. %. % to 0.01 wt. 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. 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. This is diﬀerent from the internal quantum eﬃciency ηint . anywhere from 0. ηext . The salt is added in small amounts.0025 wt. 1.(Bu4 NBF4 ) and using the TE anneal can also lower the charge injection barriers. After the devices are made the device is placed on a hot plate and heated to T ◦ C and biased with a voltage V. 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. First the external quantum eﬃciency. Here we deﬁne and explain the standard measurements quoted in the literature.
most singlet excitons radiatively decay6 . meaning the material is highly ﬂuorescent (as opposed to phosphorescent). The internal quantum eﬃciency ηint is deﬁned as ηint = γβφf . (1.e. molecular excited states. Emission occurs when the singlet or triplet excitons radiatively decay to the ground state. singlet and triplet excitons. A more quantitative description of the internal and external quantum eﬃciencies can be obtained after making a few assumptions. i.are emitted in a direction other than the forward viewing direction. Thirdly we assume that luminescence of the active material has a high ﬂuorescence quantum yield φf .2) The eﬃciencies of PHOLEDs can be explained in a similar way to ﬂuorescent OLEDs. 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. so we only need to focus on charges injected from the electrodes. We introduce the light output coupling factor. ηc to relate the external and internal quantum eﬃciencies. First of all. and all electrons and holes recombine to create excitons which all radiatively decay and are coupled out of the device in the forward direction. 15 . however the rate of intersystem crossing must be taken into account as well as the phosphorescence quantum yield φp .1) Note that in a perfect system the same number of electrons and holes are injected. are generated by charge recombination. Second. 6 (1. we assume that no charge is present in the active material without charge injection. ηext = ηc · ηint .
3) where Jr is the electron-hole recombination current density. and γ < 1 if Je or Jh is non-zero. J = Jh + Je = Je + Jh . (1. The charge balance factor is a measure of the eﬃciency of charge recombination.5) If all injected electrons and holes recombine within the emissive layer.4) (1. if electrons and holes injected do not form excitons they merely travel through the material and out. and the amount of current that does not contribute to exciton formation (i. 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.6). J γ= (1.e.where γ is the charge balance factor. the current that makes it through the device) as Je and Jh . β is the production eﬃciency of emissive excitations. 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. In order to increase the eﬃciency of charge recombination (increase γ) a balance between injected holes and electrons must be obtained. and φf is the ﬂuorescence quantum yield. In terms of the injected current the charge balance factor is deﬁned as Jr . If we deﬁne the amount of current injected from the cathode and the anode as Je and Jh . 7 16 . and they must be contained within the emissive region of the device7 . and J is the measured current density. Jr = Jh − Jh = Je − Je . J = Jr then γ = 1. we can write down expressions for J and Jr (see Fig.
25.2. The eﬃciency of the production of emissive excitations β is deﬁned as the branching ratio for singlets and triplets.Figure 1. n2 (1.6) where n is the index of refraction of the material. A typical value for n in OLEDs is 1.2. and φf = 1. γ = 1. the maximum ηext = 5. Taking χ = 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 .7. Plugging in some numbers gives an estimate of the maximum external quantum eﬃciency of the OLED.0%. β = 0. However it must be noted that this is not an exact ceiling value for eﬃciencies of OLEDs. but is a useful measure to aid in the understanding of 17 . and is taken to be π based on simple spin statistics. giving the frequently used approximation for χ as 0. χ=1− 1− 1 .
Photometric quantities have analog radiometric quantities (see Fig. The need for photometric quantities arises from the fact that our eyes only see light from the visible spectrum. and hence has units of watts (W).OLED eﬃciency. Radiometry deals with the measurement of energy per time. The ﬁeld of optical measurements is broken into two sub-ﬁelds. while photodetectors can (theoretically) detect the entire spectrum. The lumen is deﬁned as the measure of the power of light perceived by 18 .8). For example an OLED that emits in the UV (or anywhere outside the visible spectrum) will have a measurable radiometric power eﬃciency. 1.5. These new units in the photometric quantities are the lumen (lm) and the candela (cd). 1.7). radiometry and photometry. Figure 1.7: Radiometric quantities and their photometric analogs. 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. our eyes (see Fig. 1. but zero photometric power eﬃciency.1 Measurements Next we will deﬁne and explain the standard measurements used to char- acterize OLED performance. except new units are introduced to account for the sensitivity of our eyes.
Hence a light source that emits 1 candela uniformly in all directions emits a total of 4π lumens. Figure 1. which has its own photopic responsivity R(λ) that needs to be taken into account. The photocurrent is measured by a photodiode. two testing setups are needed due to the limitations of the equipment being used. The second setup involves measuring the current and photocurrent of the device as a function of bias voltage. 1lm = 1cd·sr.the human eye.7) . The external quantum eﬃciency ηext is deﬁned as q λIdet (λ)dλ hcf IOLED R(λ)dλ 19 ηext = (1. The ﬁrst measurement setup is used to measure the spectra of the device. The peak is centered over green. meaning our eyes detect greens better than reds or blues. which amounts to biasing the device so that it is turned on and counting the number of photons emitted at each wavelength.8: A graph of the photometric response of the eye superimposed with the visible spectrum. When testing devices. the lumen can also be deﬁned in terms of the candela. and we don’t see anything outside the visible spectrum.
9). and IOLED is the current through the OLED. Figure 1. f is the fraction of light emitted from the device to the light coupled into the detector.8) where L is the luminance of the OLED (measured in [cd/m2 ]).where R(λ) is the photodiode responsivity (shown in Fig. A is the device area. ηL = AL IOLED (1.9: Photometric responsivity of EG&G UV-100BQ photodiode. The luminous power eﬃciency. and c is the speed of light. q is the charge of the electron. or luminosity. h is Plank’s constant. and is very similar to ηext except that the luminous eﬃciency takes the photopic response of the eye into account. Idet (λ) is the photocurrent from the photodetector. Experimentally. 1. The luminous eﬃciency ηL is measured in candelas per amp. it is best for the photodetector to be larger in area and as close as possible to the device in order to maximize f . ηP measured in lumens per watt is deﬁned as the ratio of the luminous power emitted in the forward direction 20 .
9) Alternatively we can deﬁne ηP explicitly in terms of the photopic response of the eye.10) where φ0 = 683lm/W is the peak photopic response at λ = 555nm. 21 .LP to the power used by the OLED at a particular voltage. ηP = φ0 g(λ)Idet (λ)/R(λ)dλ f IOLED V (1. ηP = LP IOLED V (1.
The small amount of Ir(ppy)3 was chosen to prevent concentration quenching.N’-bis(3-methylphenyl)-1.3. Speciﬁcally the blend consisted of TPD Bu-PBD Ir(ppy)3 PVK 0. the green emitter Ir(ppy)3 3 . wt.34 wt.4’-diamine 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1.4-oxadiazole 3 tris(2-phenylpyridinato) iridium 4 Poly(9-vinylcarbazole) 22 .2 dichloroethane.1’biphenyl-4.32 0. wt. and evaporating an aluminum top electrode. % % % % where the weight percentages are with respect to the solvent. wt. and the hole transporting host material PVK4 in 1.08 0.N’-diphenyl-N.Chapter 2 Experiment Green PHOLEDs were fabricated by spincasting a solution of active material onto a glass slide printed with indium tin oxide (ITO). The active material consisted of a blend of the hole transporting material TPD1 .06 0. the electron transporting material Bu-PBD2 . and to aid in solubility as Ir(ppy)3 has been shown to have poor solubility in commonly used solvents (such 1 2 N.
and 1. A Single layer devices incorporated 0.0. preparing the substrates. 5 The amount and spin speed chosen yielded full coverage of the glass substrate.2-dichloroethane). depositing the materials. current versus voltage. and photocurrent versus voltage measurements were taken in the glovebox. 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. and annealed in a vacuum oven. The interfacial layer PEDOT:PSS and active material were spun in a fumehood. tetrahydrofuran.005wt. Procedures for preparing the active blend. The active layer was formed by spincasting 60µL of the blend and vacuum annealing for 30min at 100-110 ◦ C. chlorobenzene. Typically5 150µL of ﬁltered PEDOT:PSS was spun at 1500rpm and annealed at 100-110 ◦ C for 2030min.% Bu4 NBF4 in the active solution and were TE annealed. The TE anneal was performed in the glovebox on a hot plate at 85-95 ◦ C while being sourced by 7V.1 and Fig. D.2. 23 . Devices incorporated PEDOT:PSS and/or LiF interfacial layers to aid in charge injection into the active layer.as toluene. and testing devices can be found in the Appendices. see Fig. Spectra.001 . D.
06 0. % % % % . during testing of the best device O2 levels in the glovebox ﬂuctuated between 6ppm and 100ppm. wt. 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. 3. As expected. and the spectra for each device was almost identical (see Fig.32 0.Chapter 3 Results The performance of devices made with PEDOT:PSS and LiF interfacial layers were compared.08 0. indicating that such ﬂuctuations should not 24 0. wt.2 dichloroethane. 3. wt.4). 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 1.34 wt.1). On another note.
Figure 3. 25 .2. 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. and device made with PEDOT:PSS but no LiF interfacial layers. all devices that were made worked in one way or another. Finally the turn on voltages for the devices made here were too high. 3. Pixels with bright spots degraded quickly after multiple JV/PJV testing runs.3. and the bright spots turned into dark spots after multiple JV/PJV tests. see Fig. Furthermore. as was previously thought. This means that all of the devices emitted light in one of two ways. 3. signiﬁcantly eﬀect device performance. and currents were too high indicating poor eﬃciency.1: Comparison of photocurrent versus voltage for device made with PEDOT:PSS and LiF interfacial layers. The JV and PJV data for the best device is shown in Fig.
Figure 3. 26 .2: Current versus voltage and photocurrent versus voltage data for one device tested three times on three diﬀerent days.
Figure 3.Figure 3. 27 .4: Spectra from device made with PEDOT:PSS and LiF interfacial layers.3: Current versus voltage and photocurrent versus voltage data for best device. and just PEDOT:PSS layer.
One explanation for the high power and non-uniform light emission is poor morphology of the ﬁlms.2 dichloroethane as the solvent.5: AFM image of morphology for device made which used 1. hence improving the morphology. Hence binary solvents with diﬀerent mixing weight ratios were used to improve morphology.5 shows an AFM image of the morphology of the best device. should improve device characteristics. however an ideal morphology was not achieved. Decreasing the size of these aggregates. As previously stated it is hard to dissolve multiple materials into one solvent. which has aggregates on the order of a few hundred nanometers. 28 . Fig. 3. Figure 3.
however they lacked the desired eﬃciency exhibited by devices made in other groups.Chapter 4 Conclusion and Next Steps In conclusion. Improving morphology will yield a signiﬁcant improvement in eﬃciency by lowering the currents and voltages required for bright light emission. Future research should focus on improving the morphology of the ﬁlms. Furthermore. PHOLEDs made from the iridium complex Ir(ppy)3 were fabricated. 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. optimizing the dispersion of the materials in the blend by choosing and appropriate solvent(s). 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. 29 .
calculating how much of each material to use from the weight of the solvent. weighing each component out. The scale can measure accurately down to about 1mg. So the mix uses 5. which has a density of 1.2-dichloroethane.012g of solvent and TPD Bu-PBD Ir(ppy)3 PVK 4.00mg 17.253 g/ml.04mg First weigh out the diﬀerent materials and add them to the vial. % required can be weighed out on the scale. The amount of solvent is chosen so that the material with the smallest wt. so the amount of solvent must be chosen accordingly. then pipet the 30 . the mix used 4ml of 1. the weight percentages are the same as what is in the Single Layer PHOLED section.01mg 16. putting everything in a vial with a stir-bar.03mg 3.Appendix A Preparing the Mix Preparing the mix of ingredients for the active layer consists of choosing a solvent. Here is an example. and leaving the mix on a stir-plate for 24 hours before making devices.
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.which translates into 0.say 1mg . weigh out a small amount of material . 1 31 . To make a stock solution.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. % of Bu4 NBF4 .solvent into the vial. Now the stock solution has a density of 1mg/ml. make a stock solution because the scale is not accurate enough to weigh such a small amount of material.005 wt. this method uses less material but requires more bookkeeping. add a stir-bar. say 0.25mg of salt. To add 0. 2 The mix can also be made by making stock solutions for each of the diﬀerent materials. and put it on the stir-plate over night1 To add a small amount of salt.
for instance the amount of time in each step is variable. three times over the sink 4. 1 32 . make sure the ITO sides are not touching.Appendix B Preparing the Substrate The ﬁrst thing that needs to be done is clean the ITO coated glass slides. Sonicate in DI H2 O for 30min If you do clean ten at once. scrape oﬀ old material3 in a petri dish ﬁlled with Alconox. place the slides in the staining jar so they are glass-to-glass. A commonly used slide cleaning procedure is as follows2 : 1. Letting the slides sonicate for a long time is advantageous for two reasons: ﬁrst I’m conﬁdent they are clean. 4 I usually set the temperature of the sonicator to 40◦ C during the cleaning process. 2. Using a razor blade. but up to ten can be cleaned at once if they are doubled up in the staining jar1 . 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. and dispose of waste in the hazardous liquids container in the fumehood. Rinse oﬀ slides with de-ionized water. Cleaning ﬁve slides at once is common. Sonicate in Alconox for 60min4 3. 2 Again this cleaning procedure is not hard and fast.
Dry slides with ﬁltered nitrogen Now that the slides are clean devices can be made. 33 . 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. swab both sides of each slide in a petri dish ﬁlled with ethanol 6. Using a cotton tipped swab.5. Sonicate in ethanol for 30min 7.
Appendix C Device Fabrication Procedure The procedure here will include the deposition of PEDOT:PSS and LiF layers. Using clean slides will help. The device fabrication procedure is as follows: 1. but also use more material if you’re not getting good coverage. 1 34 . Here is the general order of operations. (3) evaporate LiF interfacial layer. Steps (1) and (2) are done at the spinning station in the fumehood. Spin down 150µl PEDOT:PSS at 1500rpm1 3. The important thing here is getting a nice uniform ﬁlm. and steps (3) and (4) are done in the evaporation chamber in the glovebox. Also the spin speed can be increased or decreased to change the thickness of the diﬀerent layers. there are four basic steps: (1) deposit PEDOT:PSS interfacial layer. Anneal in the vacuum oven at 100◦ C to 110◦ C for 30min. 2. Filter PEDOT:PSS using 45µm syringe tip ﬁlter. and (4) evaporate Al top electrode. (2) deposit active layer.
Next evaporate 100nm of Al at about 1˚/s.4. now devices are ready for top electrode evaporation. 3 2 35 . the slower the deposition rate the more uniform the layer will be). Using a cotton tipped swab dipped in ethanol. 7. Using a cotton tipped swab dipped in ethanol. for thicker devices reduce the spin speed. carefully clean oﬀ the outer edges of the device to expose the ITO pads. Now that the top electrode is ready to be evaporated. but they survived in the glovebox for up to seven days with the O2 concentration between 5ppm and 45ppm. 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. These devices do not like oxygen. Then ˚ evaporate 1nm to 10nm of LiF (at about . Spin down 60µl of active material at 1000rpm2 for 45sec. Then raise the bell jar. Now A the devices are made and ready to be tested3 .5A/s. Again. This means that devices can be made at night and then tested the next morning. load the devices. clean oﬀ the outer area of the device exposing the ITO pads. ﬁrst transfer the slides to the glovebox and load the slides into the evaporation mask. put LiF and Al in their boats. 6. and close the bell jar. 5. If devices are shorting try a thicker layer.
one for taking the spectra of the pixel. then using the Keithely 2400 source with current and measure the voltage. and ramp up the source current while watching for the device to light up1 . and ramp up in steps of 1mA 1 36 . The basic idea consists of sourcing the device with Devices reported here had high turn on voltages and high currents. There are two measurement setups. hence start at a low current of 1mA. and the other for taking current versus voltage and photocurrent versus voltage curves. Remember that these devices only work in forward bias.Appendix D Device Characterization Procedure The ﬁrst thing to do before you test the devices is see if they work.vi program are used. Figures D. so make sure that you pin out to the pixel correctly. To take spectra of the device the Ocean Optics mini spectrometer and spectrum. Set the device holder near the window of the glovebox so that you can see it.1 and D.2 show the setups for the two measurements. If the pixel lights up the device is ready to be tested. Load the slide into the device holder and pin out to one pixel.
Figure D.1: Experimental setup for taking spectra. 37 .2: Experimental setup for taking current versus voltage and photocurrent versus voltage curves data. Figure D.
and the number of counts can be adjusted by using the ’averaging’ and integration time to increase the signal. Use the 600µm ﬁber and the UV-Vis grating. 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. Set the 2 Remember. Then place the Ocean Optics ﬁber into the hole on the ﬁber holder and take the spectrum. and also ramp up the source voltage to make the device brighter.enough voltage so that it is very bright and the spectrum. there is no need to take spectra data for each pixel. Once the ﬁber holder is attached.vi program gives a plot of the spectrum. To take JV and PJV curves use the multisweep program (an Igor program) on the left hand side computer2 . and no sphere.vi program and load the device into the device holder. visually check to see if the pixel lights up before taking JV/PJV data 38 . First turn on the spectrum. it allows you to choose what combination of ﬁber size. spectrum.vi (the icon on the desktop says “run spectrum”) is setup to take diﬀerent types of spectra. grating. Good spectra data counts are in the 3000 range. 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. Now. using a small allen-head screwdriver and the marking tape. align and ﬁx the ﬁber holder to the device holder. and integrating sphere. When ready to take spectra. click start and the spectra will appear on the screen. Fix the photodiode to the device tester and pin out to the pixel to be tested. Next.
39 .ammeter so that it is on auto-range mode. and ending voltage at the top separated by commas. with the step size. Finally click start and multisweep will take the data. and tell multisweep where the ﬁle is. To set the voltage range create a text ﬁle (for example V in. and a name for the data about to be taken. Then click “acquire photocurrent” to measure photocurrent and current versus voltage at the same time. Make sure the GPIB cables from both of the Keithley’s are connected to the left hand side computer. Then specify the ﬁle path where data is to be saved. starting voltage.txt).
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