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
1.5 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
Then we will discuss device characterization and fabrication.
. have emerged as promising alternatives to solid state lighting applications and ﬂat panel displays. a low molecular weight green emitter.Abstract
Phosphorescent Organic Light Emitting Devices by Glenn P. In an eﬀort to increase the internal conversion eﬃciency of OLEDs. phosphors are added to the active layer and Phosphorescent Organic Light Emitting Devices (PHOLEDs) are made. eliminating the need for additional charge injection aiding layers thus creating a single layered device. 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. Gray
Organic Light Emitting Devices (OLEDs). First we will motivate the research and explain the physics of device operation. 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 .
First I would like to thank Sue for allowing me to do this research. and Guanmei Zhang. Chris France. Last but not least I’d like to thank my family for their love and support.
. I would also like to thank speciﬁc members of the lab who helped me in one way or another. Jeremy Olson. Ben Balaban. Yvonne Rodriguez.
Chapter 1 Introduction
Here we present work done on fabricating and characterizing organic light emitting devices (OLEDs).
. Next we will set the stage for the research conducted here by putting it into the context of work done so far. speciﬁcally OLEDs doped with phosphors called PHOLEDs. The results section covers the progress made so far. and the conclusion section summarizes the ﬁndings and suggests next steps for continuing the research done here. First we will motivate the research by highlighting some of the novel applications of PHOLEDs.
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. followed by a review of basic OLED/PHOLED operation and device architectures. Then the physics of electroluminescence is explained. The experiment section outlines the procedure for making PHOLEDs1 .
helping to reduce en-
. low operating voltages. since OLED technology is thin and lightweight it is ideal for applications in portable displays such as cell phones. Furthermore. plastic. strong eﬃciencies. and ink-jet printing. or are polymer based (called PLEDs) and solution processable made using wet fabrication techniques such as spin casting. In order for OLEDs to be competitive in these markets they must exhibit exceptional brightness. One of the biggest advantages of OLED technology is the ability to deposit the materials onto virtually any substrate such as glass. and white OLEDs have already been made whose high eﬃciency and low power consumption make them ideal for general solid state lighting applications. or a PDA that can be rolled up and stored in a small space such as a pen. ﬂexible. meaning they can be made into large area devices such as large area billboards or large area white lights.1.1
The next generation of ﬂat panel display (FPD) and general solid state
lighting applications has arrived with the OLED. or thin metal foils. which require low power. and transparent. resulting in devices that can be made paper thin. 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. OLEDs are thin ﬁlm devices made either from thermally evaporating small organic molecules (called SMOLEDs). and long lifetimes. the color of OLEDs can be tuned by introducing diﬀerent organic dopants. Also. doctor blading. OLEDs are also scalable.
sandwiched between a transparent indium tin oxide (ITO) anode and
. The ﬁrst SMOLED. followed by methods of increasing device lifetime. which is a major issue in the United States where 20% of electrical energy consumption is used for lighting. OLEDs are made from one or multiple organic layers sandwiched between a transparent anode and a metallic cathode. The trends in the literature show reports of high eﬃciency devices. was a double layer device made from layers of aromatic diamine and 8-hydroxyquinoline aluminum (Alq3 ). multilayered devices. and dopants have been introduced to increase eﬃciency. however they were not very eﬃcient and required high operating voltages due to the thickness of the crystal.ergy consumption. Second to improving eﬃciency in OLEDs has been understanding degradation mechanisms and increasing the lifetime of devices. which is required for competitiveness in the FPD and lighting industries and which will greatly contribute to understanding device physics. Here we review some of the work done on OLEDs which have inﬂuenced current device structures and our current understanding. The ﬁrst OLED was reported in 1965 by Helfrich and Schneider and was made from single crystal anthracene. and over the last twenty years new materials.
1. reported by Tang and VanSlyke in 1987.2
From OLEDs to PHOLEDs
Obtaining high eﬃciencies has been the major driving force in OLED re-
search and development.
which ultimately restricts the external quantum eﬃciency and hence device performance. which increases device eﬃciency and hence lowers the current required to achieve a desired brightness. In phosphorescent devices the internal quantum eﬃciency can reach 100%.. A major breakthrough in increasing eﬃciency was reached in 1998 by Baldo et al. The ﬁrst PHOLEDs used a platinum doped porphine complex PtOEP2 . These two seminal reports marked the beginning of the OLED research and development boom. of 1%. is limited to 25% based on spin statistics. The second generation PHOLEDs use iridium complexes such as Ir(ppy)3 as the phosphorescent dopant.12. which have internal quantum eﬃciencies of almost
2. and by Hoshino and Suzuki. However the internal quantum eﬃciency. deﬁned as the ratio of photons generated within the material to injected electrons.7. in 1990.17. deﬁned as the fraction of photons emitted in the forward viewing direction to injected electrons.13. 23H-porphine platinum(II).3. with the introduction of a phosphorescent dopant and the birth of the phosphorescent OLED (PHOLED). 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.
.a magnesium-silver alloy cathode.18-octaethyl-21H.8. In previous works OLEDs relied on the use of ﬂuorescent materials to generate light. The utilization of phosphorescent dopants in OLEDs was the logical next step in increasing the eﬃciency of OLEDs. and had internal and external quantum eﬃciencies of 23% and 4% respectively.
such as chemiluminescence. and mechanoluminescence. Photoluminescence (PL) is the simplest form in which an electron in a molecule absorbs a photon. which decay to the ground state and emit light. However there are many forms of luminescence. sonoluminescence. bioluminescence.100%.
. is excited to a higher energy and reemits another photon upon falling back to the ground state. Here we focus on charge-injection electroluminescence (EL). Devices based on Ir(ppy)3 with external quantum eﬃciencies of greater than 10% and lifetimes3 of greater than 10. 4 Luminescence is also known as ‘cold emission’ for this reason. 000h have been achieved for green and red PHOLEDs with initial brightness of 600cd/m2 and 300cd/m2 respectively. in which electrons and holes are injected into the luminescent material where they form singlet and triplet excitons. which depend on how the molecule was excited before luminescing. and is distinct from incandescence which is a high temperature process4 . 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. Device lifetimes in PHOLEDs have been shown to be inversely proportional to initial brightness which is a typical characteristic of ﬂuorescent OLEDs.
Electroluminescence in Matter
The process of radiative relaxation of molecules at low temperatures is
known as luminescence. Before explaining the charge-injection EL process it is useful to review the energy structure of electrons in molecules.
the spin is conserved from the initial to the ﬁnal state. The 6
. . The two types of emission are called ﬂuorescence for Sn → S0 transitions and phosphorescence for Tn → S0 transitions. S1 . T2 .1: Energy level diagram showing the two types of luminescence. Tn .
Figure 1. . from lowest energy to highest energy (starting from the ground state) they are S0 . and that ﬂuorescence transitions from excited singlet states to the ground state are spin-allowed. One way to o number these states is to consider their spin multiplicities.
It is important to note that normally the ground state is a singlet state. States with multiplicity of 3 are called triplet states Tn and have total spin angular momentum of 1.1. . ﬂuorescence and phosphorescence. .tionary states. Sn . Using these labels the energy structure of a molecule can be numbered. . . . which are represented by the eigenfunctions and eigenvalues of the molecule’s Hamiltonian found after solving the Schr¨dinger equation. and T1 . meaning the spin of the electron must ﬂip in order to go from a triplet state to a singlet state. Luminescence occurs when an electron in an excited singlet or triplet state relaxes to the singlet ground state. see Fig. States with multiplicity 1 are referred to as singlet states Sn and have total spin angular momentum of 0. This is not the case for phosphorescence. 1. where the transitions are spin-forbidden. .
This is why phosphorescent materials are used in glow-in-the-dark paints.2). When the spin-orbit coupling term in the Hamiltonian is strong.1 to 1 ns). The strength of the spin-orbit coupling also determines the lifetimes of the excited states. transitions between these triplets and singlets (phosphorescence) is possible.consequence of these spin-allowed and spin-forbidden transitions can be explained by the lifetime of the excited states. while electrons in triplet states can have much longer lifetimes (sometimes greater than 10s) since the transition is spin-forbidden. even in the dark. so electrons singlet states decay rapidly (0. The amount of mixing depends on the strength of the spin-orbit coupling term. making it possible for some materials with strong spin-orbit coupling to have phosphorescence transitions with the same lifetimes as ﬂuorescence. once the paint is ‘charged’ (electrons in the material are excited) it can emit light over a long period of time. The reason for this has to do with spin-orbit coupling. The phenomena of ﬂuorescence and phosphorescence is most readily illustrated using a Jablonski diagram (Fig. resulting in what are called “impure singlet” and “impure triplet” states. 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
. Strictly speaking transitions from triplet states to singlet states are spinforbidden and therefore have zero intensity. Electrons like to be in their lowest energy state. 1. more mixing corresponds to strong spin-orbit coupling. When the spin-orbit coupling term HSO is added to the molecule’s Hamiltonian and treated as a perturbation. nonetheless phosphorescent transitions occur.
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. As Fig.1 because it includes vibrational energy levels.3 illustrates the charge-injection EL process similar to almost all OLEDs. ISC intersystem crossing). 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. The diagram is more detailed than Fig. Electrons and holes are injected from the
. The rate of ISC is determined by how much mixing of singlet and triplet states occur due to spin-orbit coupling.phosphorescence) are shown as straight lines. In the diagram absorption (A) and emission (F . There are ﬁve processes involved in chargeinjection EL. P . and the wavy lines correspond to non-radiative processes (IC . falling down to the ground state.internal conversion.ﬂuorescence. (ii) charge migration. (iv) light emission. or undergoes VR and does not emit a photon. which are located above each of the singlet and triplet levels. and (v) light extraction.vibrational relaxation. and must be fast for eﬃcient phosphorescent materials. (iii) exciton formation. VR . 1. Lifetimes of triplet states and triplet energy transfer have been studied in Alq3 based devices.2 shows. 1. 1.
1.(i) charge injection.can lead to luminescence in molecules. The simple structure shown in Fig.
Internal conversion (IC) corresponds to non-radiative transitions between states of the same multiplicity.Figure 1.2: Jablonski diagram illustrating the various absorption and emission processes in molecules. Figure from reference p.
. while intersystem crossing (ISC) corresponds to non-radiative transitions between states of diﬀering multiplicity.224.
4. 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.Figure 1. If the electron and hole meet on a single molecule. Not all excitons radiatively recombine. 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.
1. Double layer devices are made up of an electron transport layer (ETL)
. and holes and electrons are assumed to recombine and emit light on a speciﬁc molecule . cathode and anode.3: Simpliﬁed energy level diagram for single layer OLED showing chargeinjection EL process. respectively.1
Double and Multilayered OLEDs
As previously mentioned. singlet and triplet excitons are formed. for example in ﬂuorescent OLEDs only 25% of excitons contribute to light generation.
4: (a) Double layer OLED with the electron transport layer (ETL) as the emissive layer (EML). not a part of the ETL or HTL. Figure 1. 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. The ETL or the HTL can be doped so that it becomes the emissive layer (EML). For example. in a double layer device. electrons and holes are injected into the ETL and HTL then meet at the EML to recombine and form excitons.
Figure 1.and a hole transport layer (HTL). and hence the charge balance factor.4 shows device architectures for double and multilayered devices. by conﬁning excitons to the EML. electron and/or hole blocking layers are introduced to aid in increasing the recombination current. followed by luminescence.
Multilayer devices incorporate more layers to control and improve device eﬃciency. So. And devices made with double emission layers
. (b) Double layer device with the hole transport layer (HTL) as the EML.
Single Layer PHOLEDs
Single layer PHOLEDs are made from a blend of a electron transport mate-
rial (ETM).5: Simpliﬁed energy level diagram for single layer PHOLED showing chargeinjection EL process. a hole transport material (HTM). aiding in charge injection.have been shown to be highly eﬃcient. 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. 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).
Figure 1. Figure 1.5 shows a diagram of the energy structure of a single layer PHOLED. interfacial layers between the cathode and ETL and/or anode and HTL are commonly introduced to reduce the charge injection barrier. 12
2-dichloroethane and chloroform (3:1 mixing weight ratio) to achieve bright uniform EL. and lithium ﬂuoride (LiF) can be used as the interfacial layer between the anode (Al) and the organic layer.e. As such. either use interfacial layers between the cathode/organic layers and organic/anode layers. yields the best devices with the most uniform light emission and highest eﬃciency. used a binary solvent of 1. or add a small amount of salt additive and do a thermo-electric (TE) anneal as shown by Park et al.. i. Park et al. To lower the charge injection barrier you can do two things. the choice of the solvent(s) is very important in controlling the morphology of the single layer PHOLED ﬁlm.4-ethylenedioxythiophene) :poly(styrene sulfonate)
. it is useful from an fabrication point of view to choose solvents that have a high boiling point.One of the biggest factors that determines the performance of a single layer PHOLED is the morphology. the phase separation of the diﬀerent ingredients of the blend. which can be characterized by a smooth AFM image of the surface. When choosing a solvent two things must be kept in mind. First and foremost the solvent must properly dissolve all of the materials. This is diﬃcult to achieve with a one part solvent. Secondly. A uniform morphology. The addition of the ionic salt tetrabutylammonium tetraﬂuoroborate
poly(3. For example PEDOT:PSS5 can be used as the interfacial layer between the anode (ITO) and the organic layer. 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.
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. % to 0. Once the device lights up the ﬁeld is terminated and it is taken oﬀ the hot plate and cooled.01 wt.
1.(Bu4 NBF4 ) and using the TE anneal can also lower the charge injection barriers. This is diﬀerent from the internal quantum eﬃciency ηint . It is important that the ﬁeld points in the right direction or the ions will adsorb in the wrong direction. First the external quantum eﬃciency. The diﬀerence arises from the fact that not all photons generated within the structure of the OLED make it out of the device. ηext . some photons are re-absorbed by the material and some
. The salt is added in small amounts.0025 wt.5
It is important to standardize and deﬁne the diﬀerent measurements used
to characterize the luminescence of OLEDs. 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. %. anywhere from 0. 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. Here we deﬁne and explain the standard measurements quoted in the literature.
singlet and triplet excitons. The internal quantum eﬃciency ηint is deﬁned as ηint = γβφf .
(1. meaning the material is highly ﬂuorescent (as opposed to phosphorescent). are generated by charge recombination. Thirdly we assume that luminescence of the active material has a high ﬂuorescence quantum yield φf . i. so we only need to focus on charges injected from the electrodes. Second. ηext = ηc · ηint .are emitted in a direction other than the forward viewing direction. ηc to relate the external and internal quantum eﬃciencies. (1. 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. A more quantitative description of the internal and external quantum eﬃciencies can be obtained after making a few assumptions. 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. molecular excited states.
.e. most singlet excitons radiatively decay6 . and all electrons and holes recombine to create excitons which all radiatively decay and are coupled out of the device in the forward direction. Emission occurs when the singlet or triplet excitons radiatively decay to the ground state.2)
The eﬃciencies of PHOLEDs can be explained in a similar way to ﬂuorescent OLEDs. we assume that no charge is present in the active material without charge injection. We introduce the light output coupling factor. First of all.
Jr = Jh − Jh = Je − Je .6).
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. and φf is the ﬂuorescence quantum yield.
(1.where γ is the charge balance factor.5)
If all injected electrons and holes recombine within the emissive layer.e. we can write down expressions for J and Jr (see Fig.3)
where Jr is the electron-hole recombination current density. J = Jr then γ = 1. The charge balance factor is a measure of the eﬃciency of charge recombination. and they must be contained within the emissive region of the device7 . 1. In terms of the injected current the charge balance factor is deﬁned as Jr . the current that makes it through the device) as Je and Jh . 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. if electrons and holes injected do not form excitons they merely travel through the material and out.4)
(1. β is the production eﬃciency of emissive excitations. 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. and J is the measured current density.
. and γ < 1 if Je or Jh is non-zero.
J = Jh + Je = Je + Jh . J
Plugging in some numbers gives an estimate of the maximum external quantum eﬃciency of the OLED. the maximum ηext = 5.Figure 1. γ = 1.7. An estimate of the light output coupling factor χ can be derived from simple ray optics.0%. but is a useful measure to aid in the understanding of 17
. However it must be noted that this is not an exact ceiling value for eﬃciencies of OLEDs. A typical value for n in OLEDs is 1. giving the frequently used approximation for χ as 0. Taking χ = 0.2. and is taken to be π based on simple spin statistics.6: Illustration of current J and recombination current Jr .25.2. χ=1− 1− 1 . β = 0.
The eﬃciency of the production of emissive excitations β is deﬁned as the branching ratio for singlets and triplets.6)
where n is the index of refraction of the material. n2 (1. and φf = 1.
Figure 1. but zero photometric power eﬃciency. while photodetectors can (theoretically) detect the entire spectrum. and hence has units of watts (W). For example an OLED that emits in the UV (or anywhere outside the visible spectrum) will have a measurable radiometric power eﬃciency.OLED eﬃciency. except new units are introduced to account for the sensitivity of our eyes. radiometry and photometry. The ﬁeld of optical measurements is broken into two sub-ﬁelds. our eyes (see Fig. 1.7).
The need for photometric quantities arises from the fact that our eyes only see light from the visible spectrum. The lumen is deﬁned as the measure of the power of light perceived by
. 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.
Next we will deﬁne and explain the standard measurements used to char-
acterize OLED performance.8).5. These new units in the photometric quantities are the lumen (lm) and the candela (cd). Photometric quantities have analog radiometric quantities (see Fig. Radiometry deals with the measurement of energy per time.
meaning our eyes detect greens better than reds or blues.the human eye. the lumen can also be deﬁned in terms of the candela. The photocurrent is measured by a photodiode.8: A graph of the photometric response of the eye superimposed with the visible spectrum. The second setup involves measuring the current and photocurrent of the device as a function of bias voltage. The ﬁrst measurement setup is used to measure the spectra of the device. 1lm = 1cd·sr. which has its own photopic responsivity R(λ) that needs to be taken into account. The peak is centered over green. which amounts to biasing the device so that it is turned on and counting the number of photons emitted at each wavelength. Hence a light source that emits 1 candela uniformly in all directions emits a total of 4π lumens. and we don’t see anything outside the visible spectrum.
Figure 1. The external quantum eﬃciency ηext is deﬁned as q λIdet (λ)dλ hcf IOLED R(λ)dλ 19
When testing devices. two testing setups are needed due to the limitations of the equipment being used.7)
ηL = AL IOLED (1.
The luminous eﬃciency ηL is measured in candelas per amp.8)
where L is the luminance of the OLED (measured in [cd/m2 ]). and is very similar to ηext except that the luminous eﬃciency takes the photopic response of the eye into account. 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.where R(λ) is the photodiode responsivity (shown in Fig. 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. Idet (λ) is the photocurrent from the photodetector. q is the charge of the electron. 1. and c is the speed of light.
Figure 1.9). A is the device area. and IOLED is the current through the OLED. Experimentally. h is Plank’s constant. ηP measured in lumens per watt is deﬁned as the ratio of the luminous power emitted in the forward direction 20
. or luminosity.
LP to the power used by the OLED at a particular voltage.
. ηP = φ0 g(λ)Idet (λ)/R(λ)dλ f IOLED V (1.10)
where φ0 = 683lm/W is the peak photopic response at λ = 555nm. ηP = LP IOLED V (1.9)
Alternatively we can deﬁne ηP explicitly in terms of the photopic response of the eye.
and the hole transporting host material PVK4 in 1.Chapter 2 Experiment
Green PHOLEDs were fabricated by spincasting a solution of active material onto a glass slide printed with indium tin oxide (ITO).32 0. wt. wt. and to aid in solubility as Ir(ppy)3 has been shown to have poor solubility in commonly used solvents (such
N. wt.08 0. the green emitter Ir(ppy)3 3 .4-oxadiazole 3 tris(2-phenylpyridinato) iridium 4 Poly(9-vinylcarbazole)
.4’-diamine 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1.34 wt.2 dichloroethane. the electron transporting material Bu-PBD2 . The active material consisted of a blend of the hole transporting material TPD1 . The small amount of Ir(ppy)3 was chosen to prevent concentration quenching.N’-bis(3-methylphenyl)-1. and evaporating an aluminum top electrode.06 0.N’-diphenyl-N.1’biphenyl-4. Speciﬁcally the blend consisted of TPD Bu-PBD Ir(ppy)3 PVK 0. % % % %
where the weight percentages are with respect to the solvent.3.
1 and Fig. and photocurrent versus voltage measurements were taken in the glovebox. Spectra. The active layer was formed by spincasting 60µL of the blend and vacuum annealing for 30min at 100-110 ◦ C. and 1. see Fig. current versus voltage.as toluene. tetrahydrofuran. and testing devices can be found in the Appendices. 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.
The amount and spin speed chosen yielded full coverage of the glass substrate. Typically5 150µL of ﬁltered PEDOT:PSS was spun at 1500rpm and annealed at 100-110 ◦ C for 2030min. Procedures for preparing the active blend. Devices incorporated PEDOT:PSS and/or LiF interfacial layers to aid in charge injection into the active layer.2-dichloroethane).005wt.0.001 . The interfacial layer PEDOT:PSS and active material were spun in a fumehood. preparing the substrates. chlorobenzene. A Single layer devices incorporated 0.% Bu4 NBF4 in the active solution and were TE annealed.
. and annealed in a vacuum oven. depositing the materials.2. The TE anneal was performed in the glovebox on a hot plate at 85-95 ◦ C while being sourced by 7V. D. D.
34 wt.1).2 dichloroethane. % % % %
. 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.08 0. and the spectra for each device was almost identical (see Fig. wt.4). As expected. indicating that such ﬂuctuations should not 24 0.Chapter 3 Results
The performance of devices made with PEDOT:PSS and LiF interfacial layers were compared. wt. during testing of the best device O2 levels in the glovebox ﬂuctuated between 6ppm and 100ppm. 3. wt. 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 1.06 0. On another note.32 0. 3.
2. as was previously thought. 3. 3. 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.
. see Fig. Pixels with bright spots degraded quickly after multiple JV/PJV testing runs. all devices that were made worked in one way or another.3. Furthermore.1: 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. and currents were too high indicating poor eﬃciency. This means that all of the devices emitted light in one of two ways.Figure 3. The JV and PJV data for the best device is shown in Fig. 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. signiﬁcantly eﬀect device performance.
2: Current versus voltage and photocurrent versus voltage data for one device tested three times on three diﬀerent days.
and just PEDOT:PSS layer.
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.
which has aggregates on the order of a few hundred nanometers. 3. Hence binary solvents with diﬀerent mixing weight ratios were used to improve morphology.
Figure 3. should improve device characteristics. hence improving the morphology.5: AFM image of morphology for device made which used 1.2 dichloroethane as the solvent.5 shows an AFM image of the morphology of the best device. Fig.
. however an ideal morphology was not achieved.One explanation for the high power and non-uniform light emission is poor morphology of the ﬁlms. Decreasing the size of these aggregates. As previously stated it is hard to dissolve multiple materials into one solvent.
however they lacked the desired eﬃciency exhibited by devices made in other groups. PHOLEDs made from the iridium complex Ir(ppy)3 were fabricated. Improving morphology will yield a signiﬁcant improvement in eﬃciency by lowering the currents and voltages required for bright light emission. 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. Furthermore. Future research should focus on improving the morphology of the ﬁlms. 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.Chapter 4 Conclusion and Next Steps
. optimizing the dispersion of the materials in the blend by choosing and appropriate solvent(s).
the weight percentages are the same as what is in the Single Layer PHOLED section.2-dichloroethane.01mg 16. weighing each component out.04mg
First weigh out the diﬀerent materials and add them to the vial.Appendix A Preparing the Mix
Preparing the mix of ingredients for the active layer consists of choosing a solvent. The amount of solvent is chosen so that the material with the smallest wt.00mg 17. and leaving the mix on a stir-plate for 24 hours before making devices. So the mix uses 5. the mix used 4ml of 1. then pipet the 30
. The scale can measure accurately down to about 1mg. % required can be weighed out on the scale. Here is an example. putting everything in a vial with a stir-bar. which has a density of 1.03mg 3.253 g/ml. calculating how much of each material to use from the weight of the solvent. so the amount of solvent must be chosen accordingly.012g of solvent and TPD Bu-PBD Ir(ppy)3 PVK 4.
this method uses less material but requires more bookkeeping. To make a stock solution.005 wt. and put it on the stir-plate over night1 To add a small amount of salt. Now the stock solution has a density of 1mg/ml.put it in a vial with a stir bar and add 1ml of solvent.solvent into the vial.which translates into 0.25mg of salt. add a stir-bar. say 0.
. % of Bu4 NBF4 .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 The mix can also be made by making stock solutions for each of the diﬀerent materials.say 1mg . To add 0. one way to check is to hold the vial up to the light and see if there are any materials still ﬂoating around. weigh out a small amount of material . make a stock solution because the scale is not accurate enough to weigh such a small amount of material.
Sonicate in Alconox for 60min4 3. Rinse oﬀ slides with de-ionized water. but up to ten can be cleaned at once if they are doubled up in the staining jar1 . Cleaning ﬁve slides at once is common. make sure the ITO sides are not touching. and dispose of waste in the hazardous liquids container in the fumehood.Appendix B Preparing the Substrate
The ﬁrst thing that needs to be done is clean the ITO coated glass slides. 4 I usually set the temperature of the sonicator to 40◦ C during the cleaning process. 2.
. Using a razor blade. for instance the amount of time in each step is variable. Sonicate in DI H2 O for 30min
If you do clean ten at once. DI H2 O. scrape oﬀ old material3 in a petri dish ﬁlled with Alconox. three times over the sink 4. 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. 2 Again this cleaning procedure is not hard and fast. and second I can be doing other work while the slides are cleaning 3 If the slides are new this step is unnecessary. place the slides in the staining jar so they are glass-to-glass.
5. Dry slides with ﬁltered nitrogen Now that the slides are clean devices can be made.
. Using a cotton tipped swab. 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. Sonicate in ethanol for 30min 7.
The important thing here is getting a nice uniform ﬁlm. Anneal in the vacuum oven at 100◦ C to 110◦ C for 30min. there are four basic steps: (1) deposit PEDOT:PSS interfacial layer. (3) evaporate LiF interfacial layer. The device fabrication procedure is as follows: 1. but also use more material if you’re not getting good coverage. Filter PEDOT:PSS using 45µm syringe tip ﬁlter. Spin down 150µl PEDOT:PSS at 1500rpm1 3.
. Here is the general order of operations. Also the spin speed can be increased or decreased to change the thickness of the diﬀerent layers. Steps (1) and (2) are done at the spinning station in the fumehood.Appendix C Device Fabrication Procedure
The procedure here will include the deposition of PEDOT:PSS and LiF layers. 2. and (4) evaporate Al top electrode. (2) deposit active layer. and steps (3) and (4) are done in the evaporation chamber in the glovebox. Using clean slides will help.
Anneal in the vacuum oven for 30min at 100◦ C to 110◦ C. for thicker devices reduce the spin speed. carefully clean oﬀ the outer edges of the device to expose the ITO pads. 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. put LiF and Al in their boats.
Again. Now that the top electrode is ready to be evaporated. Then ˚ evaporate 1nm to 10nm of LiF (at about .5A/s. 7. Spin down 60µl of active material at 1000rpm2 for 45sec. the slower the deposition rate the more uniform the layer will be). clean oﬀ the outer area of the device exposing the ITO pads. load the devices. Next evaporate 100nm of Al at about 1˚/s. Now A the devices are made and ready to be tested3 . 6. and close the bell jar. Using a cotton tipped swab dipped in ethanol. This means that devices can be made at night and then tested the next morning.
.4. Then raise the bell jar. ﬁrst transfer the slides to the glovebox and load the slides into the evaporation mask. 5. These devices do not like oxygen. If devices are shorting try a thicker layer. now devices are ready for top electrode evaporation. Using a cotton tipped swab dipped in ethanol.
There are two measurement setups. Load the slide into the device holder and pin out to one pixel. Figures D. If the pixel lights up the device is ready to be tested. so make sure that you pin out to the pixel correctly.vi program are used. Remember that these devices only work in forward bias. one for taking the spectra of the pixel.1 and D. The basic idea consists of sourcing the device with
Devices reported here had high turn on voltages and high currents. hence start at a low current of 1mA. and ramp up in steps of 1mA
. and the other for taking current versus voltage and photocurrent versus voltage curves. 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.Appendix D Device Characterization Procedure
The ﬁrst thing to do before you test the devices is see if they work. then using the Keithely 2400 source with current and measure the voltage.2 show the setups for the two measurements. Set the device holder near the window of the glovebox so that you can see it.
Figure D.Figure D.2: Experimental setup for taking current versus voltage and photocurrent versus voltage curves data.
.1: Experimental setup for taking spectra.
Then place the Ocean Optics ﬁber into the hole on the ﬁber holder and take the spectrum. Set the
Remember. visually check to see if the pixel lights up before taking JV/PJV data
.vi program and load the device into the device holder. First turn on the spectrum. 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. When ready to take spectra.enough voltage so that it is very bright and the spectrum. Now. spectrum. and also ramp up the source voltage to make the device brighter. The pins are connected to the Keithley 2400 source meter and the photodiode is connected to the Keithley 485 picoammeter. grating. using a small allen-head screwdriver and the marking tape. and no sphere.vi (the icon on the desktop says “run spectrum”) is setup to take diﬀerent types of spectra. 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. 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 . Next. and integrating sphere. align and ﬁx the ﬁber holder to the device holder. click start and the spectra will appear on the screen. there is no need to take spectra data for each pixel. Use the 600µm ﬁber and the UV-Vis grating. and the number of counts can be adjusted by using the ’averaging’ and integration time to increase the signal.vi program gives a plot of the spectrum. Good spectra data counts are in the 3000 range. Once the ﬁber holder is attached.
Then click “acquire photocurrent” to measure photocurrent and current versus voltage at the same time.
. Then specify the ﬁle path where data is to be saved. starting voltage. with the step size. 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. and tell multisweep where the ﬁle is. Finally click start and multisweep will take the data. and ending voltage at the top separated by commas. To set the voltage range create a text ﬁle (for example V in.txt).ammeter so that it is on auto-range mode.
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