FABRICATION AND CHARACTERIZATION OF ZnO FILM BY SPRAY PYROLYSIS AND ZnO POLYCRYSTALLINE SINTERED PELLETS DOPED WITH REAR

EARTH IONS

A Thesis Presented to

The Faculty of the Fritz J. and Dolores H. Russ College of Engineering and Technology Ohio University

In Partial Fulfillment of the Requirement for the Degree Master of Science

by

Ahmad Al-Ahrnadi November, 2003

OHIO UNlVERSlTY

LIBRARY

ACKNOWLEDGMENTS
In the name of Allah, the Most Beneficent, the Most Merciful. All praise and thanks to Allah. Lord of the universe and all that exists. Prayers and peace be upon His prophet Mohammed, the Last messenger for all humankind.

I thank Allah for his guidance and the completion of this work. I am deeply
thankful to my mother. 1will never forget her patience and dedication to my children, my wife and me. I thank my wife, Ameenah, for her support and patience during my work on this project. I also thank my brother and my sisters for inspiring me to reach higher. I would like to express my deepest appreciation to my advisor Prof. Henryk Lozykowski, for his continuous help and support through the completion of this work. I also appreciate my committee members, Dr. Savas Kaya , Dr. Jeffrey Dill and Dr. Nicolai Pavel, for their valuable advices and suggestion.

I am also indebted to Dr. Wojtek Jadwisienczak, who is so skillful with

experimental work and always helping me when I met with problems. Thank you to my friends Adel Al-Ahrnadi, Husain Al-Hazmi, Hamad Al-brathin, Abdulmajeed Al-Ghamdi Abdulqadir Alaqeeli, Saleh Alawairdy, Ahmad Alsolaim, Hamed Alsharari, Ibrahim Almazyad, Mahmoud Emara, Inad Aljarrah, Mazyad Almohailb, James Fonseca , Emil, Ania, Mohammed Alsharekh Thanking every one by name would take many pages. Therefore, for the people I did not mentioned, from my heart Thank you. Finally, I would like extend my thanks to Dr. Zahiah Bin Zaroor, My academic advisor at the Saddi Cultural Mission in Washington, DC.

TABLE OF CONTENTS
Chapter One ........................................................................................................................ 1 Introduction......................................................................................................................1 1.1 Review of Study on Zinc Oxide............................................................................2 1.2 Characteristics of Zinc Oxide .................................................................................. 4 1.3 Rare Earth ................................................................................................................ 6 1.4 4f-4f Luminescence of Rare Earth ......................................................................... 11 1.5 Characteristics of Europium ................................................................................13 1.6 Characteristics of Thulium.....................................................................................14 Chapter Two...................................................................................................................... 15 Sample Preparation ...........................................................................................................15 2.1 Deposition of Thin Film .........................................................................................15 2.1.1 Spray Pyrolysis ............................................................................................... 15 2.1.2 Film Preparation.............................................................................................. 16 2.2 Polycrystalline Sintered Pellets.............................................................................. 18 2.2.1 Pellet preparation ............................................................................................ 19 20 Chapter Three.................................................................................................................... 20 Experimental Setup ........................................................................................................... 3.1 X-Ray Diffraction (XRD) ......................................................................................20 22 3.1.1 Experimental Details....................................................................................... 3.2 Photoluminescence (PL) ......................................................................................25 3.2.1 Photoluminescence Experiment Setup............................................................26 3.3 Cathodoluminescence (CL) ................................................................................... 28 3.3.1 Cathodoluminescence Experiment Setup ...................................................... 29 Chapter Four ..................................................................................................................... 31 Results and Discussion ..................................................................................................... 31 31 4.1 ZnO: RE^+ Thin Films ........................................................................................... 4.1.1 Crystal Structure ............................................................................................. 31 33 4.1.2 Photoluminescent ............................................................................................ 4.1.2 Cathodoluminescent........................................................................................ 37

4.2 Polycrystalline Sintered Pellets ZnO: REC13.........................................................39 4.2.1 Crystal Structure of ZnO Doped with E U ~ +(ZnO: Eu. C13)............................ 39 4.2.2 Photoluminescence of Zinc Oxide Doped with Europium (ZnO: Eu.Cl) .......41 4.2.3 Cathodoluminescent of ZnO Doped with E U ~ + (ZnO: Eu. C13)...................... 44 4.2.4 Crystal Structure of Zinc Oxide Doped with Thulium (ZnO: Tm.Cl) ............45 4.2.5 Photo Luminescent of Zinc Oxide Doped with Thulium (ZnO: Tm,Cl)........ 47 4.2.6 Cathodoluminescent of Zinc Oxide Doped with Thulium (ZnO: Tm. C13).....49 50 Chapter Five ..................................................................................................................... 50 Excitation Mechanisms and Conclusion ........................................................................ 5.1 Excitation Mechanisms .......................................................................................... 50 5.2 Energy Transfer Mechanisms ................................................................................52 56 5.3 Conclusion ......................................................................................................... 5.4 Future Work ........................................................................................................... 57 References......................................................................................................................... 58

LIST OF TABLE
Table 1.1 Electronic Configurations of Trivalent Rare Earth ............................................. 8 Table 1.2 Number of Available Electron States in Some of the Electron Shells and Sub Shells............................................................................................................................... 10 Table 1.3 Characteristics of Europium .............................................................................13 Table 1.4 Charactenstics of Thulium................................................................................ 14 Table 2.1 Polycrystalline Sintered Pellets: ZnO: EuC13 and ZnO:TmC13....................... 18 Table 4.1 The Peak Assignment for the PL of ZnO: Eu.C1..............................................41 Table 4.2 The Peak Assignment for the PL of ZnO: Tm.Cl .........................................47
. .

LIST OF FIGURES
Figure 1.1 Periodic Table of the Elements [37] .................................................................7 Figure 1.2 Dieke diagram of the energy level of trivalent lanthanide ions [27] .............. 12 Figure 2.1 Setup of the spray pyrolysis system ............................................................... 17 Figure 3.1 Bragg X-ray diffraction condition (2d sin (0) = n 1)......................................21 Figure 3.2 Setup of the x-ray diffraction ........................................................................ 24 Figure 3.3 Photoluminescence experiment setup............................................................ 27 Figure 3.4 Schematic represent of bombardment (modifified after Potts; 1995) not that the emissions come from different depths; e.g., CL and X-ray are emitted from deeper section levels than secondary electrons............................................................................28 Figure 3.5 Cathodolurninescence experiment setup ........................................................30 Figure 4.1 XRD spectral of ZnO...................................................................................... 32 34 Figure 4.2 PL spectrum of ZnO: (Eu. C1) un-annealed ................................................... Figure 4.3 PL spectrum of ZnO: (Eu. C1) annealed at 550 "C .........................................35 Figure 4.4 PL spectrum of ZnO: (Eu. C1) annealed at 600 "C .........................................36 Figure 4.5 CL spectrum of ZnO: (Eu. C1) annealed at 600 and 700 "C (a).(b) measured at low temperature (15 K) and (c) at room temperature (300 K) ..........................................38 Figure 4.6 (a) ZnO powder 2 hr at 1000 O C in air. (b) Zn0:Eu powder 2 hr at 1000 O C in air. EuC13 with 0.07 in concentration . (c) ZnO: Eu powder 3 hr at 1000 O C in vacuum. EuCl3 with 0.07 in concentration...................................................................................... 40 Figure 4.7 PL emission spectra for ZnO : Eu sintered at 1000 "C in air..........................42 Figure 4.8 PL emission spectra for ZnO : Eu sintered at 1000 "C in vacuum .................43 Figure 4.9 CL emission spectra for ZnO : Eu sintered at 1000 O C in N2......................... 44 C in air. (b) ZnO: Tm Figure 4.10 (a) ZnO powder sintered in air for 2 hr at 1000 O powder sintered in vacuum for 3 hr at 1000 O C in vacuum. TmC13 with 0.07 inconcentration.................................................................................................................. 46

Figure 4.1 1 PL emission spectra for ZnO : Tm sintered at 1000 "C in vacuum ..............48 Figure 4.12 CL emission spectra for ZnO : Tm sintered at 1000 "C in N2 ..................... 49 Figure 5.1 A model of the excitation processes for ZnO doped with RE ions ................ 5 1 Figure 5.2 Schematic diagram of trapping electron on rare earth related state. The recombination of energy of trapped electron and the free hole excites the rear earth ions. .........................................................................................................................................52 Figure 5.3 Schematic diagram of trapping hole on rare earth related state. The recombination of energy of fiee electron and the trapped hole excites the rear earth ions. Figure 5.4 Schematic diagram of trapping electron and hole on impurity related state. The recombination of energy of trapped electron and hole excites the rear earth ions. ... 54 Figure 5.5 Schematic diagram of excitation electron and hole pair. The recombination of energy of free electron and hole excites the rear earth ions..............................................55

Chapter One Introduction

In modern optical technology, rare earth ions in solids play an important role as an active constituent of materials. This is because they show an affluence of sharp fluorescent transitions representing almost every region of the visible and near infrared portions of the electromagnetic spectrum. The sharpness of many lines is a result of the shielding effect of the outer electrons. Most of the sharp lines are duo to 4f electrons as long as the 4f shell is not completely filled with 14 electrons. A number of 4f levels are unoccupied and electrons already present in the 4f shell can be raised by light absorption into these empty level [I]. Semiconductors, such as ZnO, ZnSe, or ZnS, doped with rare earth ions [2, 31 may show evidence of electroluminescence; these materials are candidates for traditional semiconductor light emitting diodes and many enable new technologies for highly distinguishable emissive flat panel displays. It may also be used to improve many electro optical applications that rely on the direct generation of either narrow or broad spectra. In this study, we have prepared and investigated the effect of chlorine ions codoping on luminescence sensitization of ZnO samples doped with Eu and Tm ions by two methods. The first one is deposition of thin film ZnO: EuC13 grown by spray pyrolysis technique, and the second one is polycrystalline sintered pellets ZnO:REC13 phosphors. Characteristic 4 f luminescence of europium (EU~')and thulium ( ~ m ~ 'doped ) into ZnO was observed under photon excitation photoluminescence (PL) and electron excitation cathodoluminescence (CL). Furthermore, on the basis of luminescence results of the PL,

CL, and their kinetics, we will discuss the optical properties of ZnO: EuCl3, ZnO: TmCl3 related emissions under different excitation conditions. In addition, obtained results may indicate that codoping of Zn0:RE with chlorine leads to efficient sensitization of RE complexes in ZnO host. Finally, we presented some of this work at the Second International Workshop on Zinc Oxide held in Dayton, OH, 23-25 October, 2002.
1.1 Review of Study on Zinc Oxide

In the past century, much research has been conducted on luminescence of rare earth ions doped II-VI semiconductors compounds. Especially in the fifties and sixties rare earth ions doped II-VI semiconductors compounds have been studied widely by several research groups for possible applications in light emitting devices and for their unique optical properties. In the middle of seventies, a new impetus came from the activities aimed at multicolored electroluminescence displays. Lozykowski and Szczurek [4, 51 were the first to investigate the electroluminescence of ZnSe thin films activated with rare earth fluorides. Their study led to the conclusion that a wide variety of electroluminescence centers occur and that the direct impact excitation mechanism dominates. In the late seventies and early eighties, only a broad band from ZnO was observed [6,7, 81 in the photoluminescence spectra. In addition, the electroluminescence of these materials is somewhat similar from one doped sample to the other and consists of three different bands in the 390-640 nrn range [9]. Y. Hayashi and co-workers [lo] observed the red band luminescence from
EU~'

doped ZnO. The intensity and fine

structures of the E U ~ + luminescence and their temperature dependence are strongly influenced by the doping conditions. In particular, for the increase of the
EU~+

luminescence intensity, Li co-doping is not affective but stoichiometric control of Zn and

0 is essential. Moreover, the observed red band luminescence can be attributed to excess
oxygen. Y. Park and co-workers found from PL measurements that with increasing doping concentration, the broad-band emission centered around 530 nm gradually disappears while the sharp red emission peaks around 620 nm exhibit a pronounced increase [ l 11. J.C. Ronfard-Haret and co-workers conducted extensive investigation of the rare earth center in ZnO and they observed at room temperature the triboluminescence (emission of light caused by the application of mechanical energy to + , HO~', sm3' and ~m~~ ions. In the 400-850 nrn range, the solid) of ~ r ~ EU~+, triboluminescence spectra were compared with the electro and photo luminescence spectra of the pellets of the same composition and sintered under the same conditions. The triboluminescence and electroluminescence spectra showed only the sharp lines characteristic of transition between the 4f level of the

RE^+

ions, whereas the

photoluminescence spectra showed only the broad ZnO emission. It is concluded that the triboluminescence of the RE3+ ions is consecutive to a direct electrical excitation consequence of a breakdown in the rich inter granular material [12].

In addition to Polycrystalline sintered pellets, ZnO thin films can be prepared on several substrates by many techniques, such as vacuum evaporation 1131, photochemical deposition reactive evaporation [14], r.f sputtering [15], chemical vapor deposition CVD [16], sol-gel [17], pulsed laser deposition [18] and spray pyrolysis [19]. F. Paraguay and co-workers obtained uniform high quality ZnO thin films by spray pyrolysis [20]. The spray pyrolysis attracted several research groups because of its simplicity, efficient,

inexpensive technique, and it produced good quality films. In this process, the spray droplets strike the substrate directly where the pyrolytic reaction takes place leading to the formation of a thin film. M.O.Abou Helal and W.T.Seeber doped ZnO with rare earth element (Pr, Ce, Nd, Tb, Sm) by spray pyrolysis and they obtained films with optical transmission T > 85 % and structural uniformity in terms of average roughness < 10 nm [21]. Recent reports of prepared p-type ZnO [22, 231 open up a novel possibilities for optoelectronic light emitting devices. In the present time, successes in producing large area single crystals have opened up the possibility of producing blue and UV light emitters, high temperature, and high power transistors [24]. 1.2 Characteristics of Zinc Oxide Zinc oxide is a 11-VI semiconductor with properties similar to GaN(3.5 eV) and 6H-Sic (3 eV at 2K). It grows like GaN with a hexagonal crystal structure. The strangest point of ZnO is that it has a large exciton binding energy (60 meV), which is larger than other 11-VI compound semiconductors and much higher than that of GaN (21-25 meV). ZnO is a wide and direct band gap semiconductor, E,
= 3.2

eV at room temperature and

E, = 3.437 at 2K. Wide band gap semiconductor materials have come to the forefront in
the past decade because of an increasing need for short-wave length photonic devices, high power, and high frequency electronic devices. Also, ZnO, like indium oxide and tin oxide, is transparent in the visible region and electrically conductive with appropriate dopants. This property has been widely studied for its practical application, as transparent conducting (TCs) electrodes, which have a wide variety of uses. Their ability to reflect thermal infrared heat is exploited to make energy conserving windows. These low

ernissivity windows are the largest area of current use for TCs. Oven windows employ TCs to conserve energy and to maintain an outside temperature that makes them safe to touch. The electrical conductivity of TCs is exploited in front-surface electrodes for solar cells and flat-panel displays (FPDs). TCs can also be fonned into transparent electromagnetic shields, invisible security circuits on windows, and transparent radio antennas built into automobile windows. Indeed, polycrystalline ZnO has found numerous applications in such diverse areas as facial powders, piezoelectric transducers, varistors, phosphors, and transparent conducting films [36]. Zinc oxide is n-type semiconductor. It has molecular weight of 81.37 and enthalpy of formation (298.15K) of 350.5 KJ/mol. It crystallizes in a hexagonal wurtzite lattice, consisting of two interpenetrating hexagonal close packed lattices, one containing the cations (Zn ++), and the other the anions ( 0 - '). The lattice constants parameters a = 0.32495

* 0.00005 nrn and c = 0.52069

0.00005 nm at 298

* 5 K, which slightly

changes with stoichiometry of the composition. The melting point of ZnO is 2248 K. ZnO has a large exciton-binding energy of 60 meV that has attracted much recent attention. Zinc oxide thin films have valuable properties, such as chemical stability in hydrogen plasma, high optical transparency in the visible and near infrared region of the electromagnetic spectrum, and high refractive index [26].

1.3 Rare Earth

As mentioned earlier, rare-earth ions play an important role in much of modern optical technology as the active constituents of materials. The most well-known application is in rare-earth solid-state laser materials. Rare-earth ions also play a critical role in energy-efficient luminescent materials, such as phosphors for fluorescent lamps, cathode ray tubes (CRT's), and plasma displays. In the periodic table, various groups of elements can be distinguished, like the s and p-block elements, the 3d, 4d, and 5d transition elements, and the lanthanides and actinides Figure 1.1. The lanthanides form a special group of elements, usually shown at the bottom of the periodic table. They are characterized by an incompletely filled 4f shell.

--- - -

Figure 1.1 Periodic Table of the Elements [37]

The electronic configuration of trivalent rare earth ions in the ground states are shown in Table (1.1). Table 1.1 Electronic Configurations of Trivalent Rare Earth Electron Covalent Ground Electronegativity Configuration of Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Radius State Ion

Element

RE^' Ions

4f'5s25p6 4f5s25p6 4P5s25p6 4f45s25p6 4f55s25p6 4f65s25p6

4f75s25p6

4$5s25p6 4P5s25p6 4f'05s25p6 4f"5s25p6 4e25s25p6 4t35s25p6

As we see the lanthanides have one to fourteen 4f electrons added to their inner ~ +L U ~ + ) shell configuration, which is equivalent to Xe. Ions with no 4f electrons ( ~ a and have no electronic energy levels that can induce excitation and luminescence processes in or near the visible region. In contrast, the ions from ce3+to yb3+which have partially filled 4f orbital have energy levels characteristic of each ion and show a variety of luminescence properties around the visible region. For example, at cerium there is one 4f electron and it begins increasing through the element until it is filled at lutetium. The ground state is characterized by the Hund rules:
1. The maximum values of the total spin s allowed by the exclusion principle.

2. The maximum value of the orbital angular momentum L consistent with this value
of s.
3. The value of the total angular momentum J is equal to (L-S) when the shell is less

than half full and to (L+S) when the shell is more than half full. When the shell is half full, the application of the first rule gives L = 0, so that J = 0. The azimutal quantum number ( I ) of 4f orbital is 3 giving rise to 7 ( = 21 + 1 ) orbital, each of which can accommodate two electrons. In the ground state, electrons are distributed to provide the maximum combined spin angular momentum (s). The spin angular momentum s is further combined with the orbital angular momentum (L) to give the total angular momentum (J). An electronic state is indicated by notation 2 S + ' ~ Jwhere L represents S, P, D, F, G, H, I, K, L, M.. ., corresponding to L = 0 , 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 ....., respectively. Table 1.2 show the number of available electron states in some of the electron shells and sub shells.

Table 1.2 Number of Available Electron States in Some of the Electron Shells and Sub Shells Principal Quantum Number n Shell Designation Sub Shells Number of States Number of Electrons Per Sub Shell Number of Electrons Per Shell

1.4 4f-4f Luminescence of Rare Earth

The 4f electrons are shielded from external electric fields by the outer 5s2 and 5p6electrons so that the levels are not affected much by the environment, unlike 3d electrons located in an outer orbit which are heavily affected by the environmental or crystal electric field. Dieke and co-workers [27] have accurately investigated the characteristic energy level of 4f electrons of trivalent lanthanide ions and the results are shown in Figure (1.2), which is known as a Dieke diagram. In Figure (1.2), each level designated by the number J is split into a number of sublevels by the stark effect due to the crystal field. The number of split sublevels is (2J+1) or (J+1/2) for J integer or J of half integer, respectively. The number of levels is determined by the symmetry of the crystal field surrounding the rear earth ion. The width of each level indicates the range of splitting within each component. In the basis of the crystal field model [28], the Hamiltonian for the 4f electrons is written as H = Ho + Hee +Hso+Hcf (I .4.1)

(H, is Hartree-Fock part of the Hamiltonian, He, coulomb interaction between the electrons @art not contained in H,), H,, spin-orbit coupling, Hcf crystal-field potential). The free ion levels result from the splitting of the 4f configuration due to &,+H,,. In

addition, under the action of Hcfthe free ion are generally split into several components.

-1

*--city
* ( I

.A$

' a ,

Ce

Pr

Nd

Pm

Sm

Err

Figure 1.2 Dieke diagram of the energy level of trivalent lanthanide ions [27]

1.5 Characteristics of Europium

Europium was discovered by E. Demarcay, a French chemist, in 1896. He was able to produce reasonably pure europium in 1901. Today, europium is primarily obtained through an ion exchange process from monazite sand, a material rich in rare earth elements. Europium is the most reactive of the rare earth elements; it quickly oxidizes in air. There are no commercial applications for Europium metal. Due to its ability to absorb neutrons, it is also being studied for use in nuclear reactors. Europium Oxide (Eu203)is widely used as a red phosphor in television (CRT) . Table 1.3 shows the characteristics of Europium [33]. Table 1.3 Cha~ Symbol Atomic Number Atomic Mass Melting Point Boiling Point Number of Protons/Electrons Number of Neutrons Crystal Structure Density @ 293 K Color silver Cubic 151.964 amu C (1095.15 OK, 1511.6 OF) 822.0 O ,istics of Europium Eu

1.6 Characteristics of Thulium

Thulium was discovered in 1879 by Cleve. Thulium occurs in small quantities along with other rare earths in a number of minerals. It is obtained commercially from monazite, which contains about 0.007% of the element. Thulium is the least abundant of the rare earth elements, yet with new sources recently discovered, it is now considered to be as rare as silver, gold, or cadmium. Ion-exchange and solvent extraction techniques have recently permitted much easier separations of the rare earths with much lower costs. Table 1.4 shows the characteristics of Thulium [33]. Symbol Table 1.4 Characteristics of Thulium Tm

Atomic Mass Melting Point Boiling Point Number of Protons/Electrons

168.9342 amu 1545.0 O C (1818.15 OK, 2813.0 OF) C (2000.15 OK, 3140.6 OF) 1727.0 O

1 Number of Neutrons
Crystal Structure Density @ 293 K Color

I1

69 100

Hexagonal 9.321 &m3 silverfish

Chapter Two Sample Preparation

In this study, we have prepared and investigated the effect of chlorine ions codoping on luminescence sensitization of ZnO samples doped with Eu and Tm ions by two methods. The first one is deposition of thin film ZnO: EuC13 grown by spray pyrolysis technique and the second one is polycrystalline sintered pellets ZnO:REC13phosphors.

2.1 Deposition of Thin Film

As mention earlier there are several different techniques used for depositing ZnO thin film. For example, films have been deposited by vacuum evaporation, photochemical deposition reactive evaporation, r.f sputtering, chemical vapor deposition CVD, sol-gel, pulsed laser deposition, and spray pyrolysis. We will discuss spray pyrolysis deposition techniques, which we used in this work. 2.1.1 Spray Pyrolysis The spray pyrolysis technique is a method that has been widely used for more than two decades, due to its simple, inexpensive technique and possibility to produce large area films. Spray pyrolysis offers several advantages over conventional routes for particle synthesis. Particles produced by this route are often more uniform in size and composition than powders produced by other methods. This technique dissolves elements of the compound material in solution and the solution is sprayed onto a heated substrate in the form of small droplets generated by an ultrasonic spray generator or aerosol generator. The spray nozzle can be driven by gravity or forced by gas pressure. Gas pressure can be controlled by the flow and used as part of the compounds, such as oxygen

or dry air, to deposit oxides and nitrogen or inert gas to avoid chemical reactions between the compound materials. Another important technique is preheating the solution. This technique is especially useful to accelerate the reaction to get good quality films. On the other hand, it is also important to heat the substrate enough to make sure that the compound solvents are completely evaporated. The film's thickness depends on the concentration of the solution and deposition time.

2.1.2 Film Preparation

Thin films of un-doped and rare earth doped ZnO were deposited on a glass substrate cleaned by using de-ionized water and acetone to achieve successful deposition. For undoped thin films, the spraying solution was prepared by dissolved zinc acetate dehydrate (ZnC4H604.2H20) with a molar concentration of (0.2M) in a mixture of de-ionized water and methanol (3:l). Using zinc acetate as a precursor makes it possible to obtain layers without chlorine contamination. The additional advantage of zinc acetate is its high vapor pressure. For the rear earth doped ZnO films, a stock solution of (0.2M) zinc acetate was mixed in appropriate ratios with EuC13 to provide spray solution containing certain (0.5, 2,4) percentage of rare earth dopants comparative to zinc. The solution reaches the substrate which is inside the furnace at a temperature of (500-550 "C) in the form of small droplets where they are decomposed. The elements react endothermic ally and they are deposited as a thin film, whereas the other unstable species are evaporated. The spraying time is 5-35 minutes. After deposition, the samples were annealed in furnace at temperature (550-700 "C) for 1-3 hour in air or N2 at atmospheric pressure. Figure 2.1 show the setup of the spray pyrolysis system.

Ventilation

I
Sample Furnace
I

-TT0

Quartz Tube
0 0
O

oOoo .P$Oo;;oo 40 0

4 -

4-

4-

Carrier Gas N2

Temperature Control

Nebulizer

Figure 2.1 Setup of the spray pyrolysis system

2.2 Polycrystalline Sintered Pellets

Powders of ZnO and rear earth compounds were carefully weighed and mixed, as shown in the table below (2.1).

Table 2.1 Polycrystalline Sintered Pellets: ZnO: EuC13and ZnO:TmC13 RE Compound RE ions Concentration Firing Conditions [atomic (at).%] EuC13 0.01 - 0.07 C in air 2 hr at 1000 O C in N2 +HC1 2 hr at 1000 O
3 hr at 1050 O C in vacuum

2 hr at 1000 O C in air 2 hr at 1000 "C in N2 + HC1

3 hr at 1050 O C in vacuum

2.2.1 Pellet preparation

In our investigation, all samples were polycrystalline sintered materials with wurtzite structure. The powder of ZnO and rare earth compound are mixed by hand in ethanol solution. The thoroughly mixed solution is then dried on a hot plate for 5 minuets. After that, the semi-dry mixture is pressed under a mechanical press (20000 Ibs) to form tablets of IOmm in diameter and 1-2 mm thick. The tablets are annealed in electric furnace under three conditions: 1. The pellet was sintered for two hours at 1000 O C in air. C in N2 + HCl. 2. The pellet was sintered for two hours at 1000 O
3. The pellet was encapsulated by a quartz tube and sealed at about 2 ~ 1 0 Torr -~

vacuum and sintered at 1050 O C for 3 hours.

Chapter Three Experimental Setup

Luminescence is the emission of light from a solid when it is supplied with some form of energy. We may distinguish between the various type of luminescence by the method of excitation. For example in photoluminescence (PL) the excitation arises from the absorption of photons, in cathodoluminescence the excitation is by bombardment with a beam of electrons, and in electroluminescence the excitation results from the application of an electric field (which may be either a.c or d.c). Whatever the form of energy input to the luminescing material, the final stage in the process is an electronic transition between two energy levels which either emit or absorb a photon. In this chapter, we discuss X-ray diffraction, photoluminescence and cathodoluminescence.

3.1 X-Ray Diffraction (XRD)

The most basic properties to be characterized are the crystal structure. W.L. Bragg derived a simple equation treating diffraction as reflection from planes in the lattice. Figure 3.1 show the Bragg X-ray diffraction condition 2d sin(0)
=

nh

(3.1)

Incident

Diffracted beam

d = plane distance

c
Figure 3.1 Bragg X-ray diffraction condition (2d sin (8) = n h) X-ray Diffraction (XRD) is one of the most useful and powerful non-destructive technique methods for characterizing crystalline materials. It provides information on structures, phases, preferred crystal orientations (texture), and other structural parameters, such as average grain size, crystallinity, strain, and crystal defects. X-ray diffraction peaks are produced by constructive interference of monochromatic beam scattered from each set of lattice planes at specific angles. X-ray diffraction from crystalline solids occurs as a result of the interaction of X-rays with the electron charge distribution in the crystal lattice. The ordered nature of the electron charge distribution, which is distributed around atomic nuclei and is regularly arranged with translational periodicity, means that superposition of the scattered X-ray amplitudes will give rise to regions of constructive and destructive interference producing a diffraction pattern. The X-ray has a wavelength range from approximately 0.1 to 100 8, They occur in that portion of the electromagnetic

spectrum between gamma-rays and the ultraviolet. Like so many other absorption phenomena, the coefficient absorption of X-ray by a solid follows the equation:
1= 10 exp (ppx)

(3.2)

where p is the mass absorption coefficient p is the density and x is the thickness of the specimen.

3.1.1 Experimental Details

X-rays produced by bombarding a metal target with 40 keV electrons produce a continuous spectrum as well as sharp, very intense spectral features characteristic of the atoms of the target. For the Rigaku Geigerflex DMAX-B the target in the source tube is Cu and the characteristic X-rays have wavelengths K,,= 1.5405 and K , 2
=

1.5443 (taken

together as the K, = 1.542 A). There are also nearby less intense lines designated Kp at 1.392 A. In this instrument we have a monochromating crystal "C" which is a specially bent piece of pyrolitic graphite. The angle between the incoming beam and the crystal is equal to the angle between the detector and the crystal. They are fixed to select the Cu
K, by Bragg scattering from the grapheme planes. Notice that the monochromating

crystal is used after the X-ray has been scattered from the sample and before the detector. In the theta-theta goniometer on this machine, the sample sits still and the source and detector arms each turn in the opposite direction by an angle 0, with respect to the plane of the sample surface. There are sets of slits that help to define the solid angle of the beam reaching the detector. The first slit, which is nearest the source, is the divergence slit (DS) which limits the area of the sample exposed to the beam. The scatter slit (SS), which limits the scattered X-rays incident on the analyzer and which is a mating slit to

the DS comes next. The receiving slit (RS), which is at the image position of the source reflected in the sample and which also limits the scattered X-rays incident on the analyzer, is important in determining the angular resolution of the measurement. The resolution is also affected by the narrowness of the beam itself, which is determined by the takeoff angle. In this instrument, the takeoff angle is fixed. The monochromator receiving slit (RSM) is at the image position of the RS reflected in the mirror of the bent graphite crystal and which limits the X-rays entering the counter. These slits come in various sizes that may be selected depending on the needs of the experiment. In many diffraction measurements above 20 = 20, the slits are chosen to be: DS lo, SS lo, RS 0.3

mm and RMS 0.45 mm. This selection gives an adequate combination of intensity and
resolution for most purposes [34]. The computer is used to determine the crystal structures by x-ray diffraction by collecting the data and controlling the processing of the experiment. In our experiment we used theta-theta Gonoimeter model CN 2182 D61 CN 2182D7. A typical X-ray setup is illustrated in Figure 3.2.The divergence beam X-ray is controlled by two sets of slits placed between focus and the samples and the samples and scatter slit, respectively. To convert the diffracted X-ray photons into voltage pulses, a photon detector is placed behind the receiving slit. The diffracted beams travel back toward the x-ray tube and strike the flat film. Each diffracted beam leaves a spot on the exposed film. The position of the spots can be converted to angular readings of the orientation of the atomic plane causing the spot, using a special chart called a Greninger chart. These angular readings are plotted on a stereographic projection, from which the

angles between planes can be read. With experience, luck, and a bit of trial and error, the crystallographic indices of the planes can be deduced, and then the orientation of the crystal is specified.

Detector
\

Slit

I Sample

Source tube Cu

Figure 3.2 Setup of the x-ray diffraction

3.2 Photoluminescence (PL)

In photoluminescence, we measure physical and chemical properties of materials by using photons to induce excited electronic states in the material system and analyzing the optical emission as these states relax. Typically, light is directed onto the sample for excitation, and the emitted luminescence is collected by a lens and passed through an optical spectrometer onto a photo-detector. The spectral distribution and time dependence of the emission are related to electronic transition probabilities within the sample and can be used to provide qualitative and sometimes quantitative information about chemical composition, structure, impurities, kinetic processes and energy transfer. In a typical PL experiment, the sample is cooled to 10 K in a cryostat and the excitation source is a laser. In general, the laser light will create a non-thermal distribution of electrons and holes. Efficient non-radiative processes will however, rapidly bring the carriers into a quasiequilibrium described by the quasi-Fermi levels. Finally, the electron-hole pairs emit photons as they recombine. The recombination takes place on a time scale determined by the transition probability. The PL spectrum is obtained by analyzing the spectral content of the emitted light.

3.2.1 Photoluminescence Experiment Setup A typical PL setup is illustrated in Figure 3.3. The sample is excited by He-Cd
(Helium Cadmium) laser which emits 325nm (UV) light. The beam is directed through mirrors and focused by a quartz lens onto the sample surface mounted on a cold finger in the optical cryostat. The luminescence emitted from the sample is collected by a quartz lens, and it passes through a filter (d) which cuts off all luminescence below 345 nrn and the laser line. The cryostat is pumped to below (Pfeiffer Vacuum TCP 015). Once it reaches Torr using the vacuum system Torr, the valve is closed and the

cryostat is cooled down to temperatures 9 K. The cooling system is a closed circuit liquid Helium system by CTI Cryogenics (model 22C) and the cooling temperature is controlled by the Palm Beach model 4057 thermo controller. Low temperature measurements are necessary to obtain the hllest spectroscopic information by minimizing thermally activated non-radiative recombination processes and thermal line broadening. The monochromator separates the polychromatic light it receives into monochromatic light of individual wavelength. The wavelengths, which are scanned across the exit slit opening, are detected by using a Hamamatsu R 928 photomultiplier tube (PMT) and measured for intensity at individual wavelengths. Individual wavelengths are focused at different horizontal positions along the exit port of the spectrograph and detected simultaneously by the CCD system. The signal from CCD is sent to a computer through a controller as ASCII data.

Stepper Motor

- - - - - - - - - _ _ _ _ _ CCD -Camera -

Controller

- I

Monochromator
I

Controller of Stepper Motor

I ,'
I

'\ \

Filter

,'

&, Lens
,
\ \

Computer PC

:
I

,
\
\ \

Ionization Gauge Control

Temperature Controller

Modulator Cooling System

Figure 3.3 Photoluminescence experiment setup

3.3 Cathodoluminescence (CL) Cathodoluminescence (CL) is the emission of photons due to the bombardment of an energetic electron beam on luminescent materials. The CL technique has been recognized as a powerful and sensitive tool for micro characterization of luminescent materials, especially in the field of optoelectronic semiconductor materials. The interaction of the beam with the sample gives rise to a number of effects: the emission of secondary electrons (SE), back scattering of electrons (BSE), electron absorption, X-ray and CL emission Figure 3.4. Most energy of the beam is converted into heat. The penetration depth of electrons and accordingly, the excitation depth depend on the energy of the electrons.

I ' Cathodoluminescence I I
Secondary Electrons Thin Section inelastically Scattered Electron Elastically Scattered Electron

Incident Electron Beam

Unscattered Electrons

Figure 3.4 Schematic represent of bombardment (modifified after Potts; 1995) not that the emissions come from different depths; e.g., CL and X-ray are emitted from deeper section levels than secondary electrons.

The mechanisms leading to the emission of light in a solid are similar for different forms of the excitation energy. An advantage of CL, in addition to the high spatial resolution is its ability to obtain more detailed depth resolved information by varying the electron beam energy. Luminescence can be divided into intrinsic CL, which is characteristic of the host lattice, and extrinsic CL, which results from impurities. Recombination of electron hole pairs may occur via nonradiatively which can decrease the emission. This decrease is referred to as concentration quenching. It can be explained by the transfer of a part of the excitation energy to other activator ions, which is more effective than luminescence emission. Quenching due to lattice defects may occur if the crystal structure is damaged by mechanical processes, radiation, growth defects, or impurities. These lattice defects create new energy levels between the conduction and the valence bands resulting in absorption of the excitation energy, non-luminescent energy transfer, or low frequency emission. Another process which may be responsible for lowering the luminescence intensity is thermal quenching [32].

3.3.1 Cathodoluminescence Experiment Setup

A typical CL setup is illustrated in Figure 3.5. The sample was mounted on a sample holder situated inside the optical cryostat and excited by an electron beam (up to 5 keV and maximum current emission -75pA),which was incident upon the sample at a 45" angle from an electron gun (Electronscan EG5 VSW). The optical cryostat is pumped to Torr and cooled by a closed cycle helium gas to 9 K. The emitted light

was collected by a quartz lens on the entrance slit of the spectrograph monochromator. The monochromator separates polychromatic light it receives into monochromatic light

of individual wavelengths. Individual wavelengths are focused at different horizontal positions along the exit port of the spectrograph and detected simultaneously by the CCD system. The signal from CCD is sent to a computer through a controller as ASCII data.

I/------./ -------------.

Stepper Motor Controller of Stepper Motor

:------<I Monochromator
I I I

2 Z a

Controller
3

'1
Electron Gun EG5 Vacuum System Compressor

rn
L Computer PC

L J
Cryostat

Sample

Gauge

Ionization Gauge Control

-

Temperature Controller

Modulator Cooling System

Figure 3.5 Cathodoluminescence experiment setup

Chapter Four Results and Discussion

4.1 ZnO:

RE^+ Thin Films

Undoped and rare earth doped thin ZnO films used inthis study were prepared by spray pyrolysis on glass substrates; as have been described in Chapter 2. The crystal structure and phase were identified using a Rigaku Geigerflex X-ray diffraction. A He-Cd laser was used as the excitation source for PL measurement. The cathode electron gun was used as the excitation source for CL measurement.

4.1.1 Crystal Structure

Figure 4.1 shows the XRD spectra of ZnO films deposited on glass substrates heated to 480 "C. The film was found to be polycrystalline with a (002) preferred orientation and this indicated that the grains were strongly oriented along with the c axis of the ZnO wurtzite structure, perpendicular to the substrate surface. The (002) peaks are located at 34.76O for pure ZnO. In addition, there are peaks at 32.14O, 36.61, and 47.84", which correspond to the ZnO (loo), (101), and (102) planes. When the Eu3+ ion is situated at the ZnO grain boundary, the ZnO crystal lattice does not affect by Eu3+ions and diffractive peaks related to the Eu can be detected by the XRD measurement. But in our experiments, only the ZnO wurtzite structure is obtained and the lattice deformation is observed, which indicates that the Eu3+ions are inside the ZnO grains and substituted for the zn2+ion position in the host matrice successfully. Because all the ions mix well in the sol, the Eu3+ ion could be doped in the ZnO crystal lattice easily during the crystallization process [3].

annealed at 600 O C

md
1 (002)

(101) (102)

unannealed

(102)
t
I
I

Figure 4.1 XRD spectral of ZnO

4.1.2 Photoluminescent
In a semiconductor crystal that contains no defects there would be mostly the luminescence line due to radiative recombination of the free exciton (FE) on the luminescence spectra. But if there are defects such as donor and acceptor impurities in the crystal, than most of the excitons will be bound to defects and form the so called bound excitons (BE'S). The BE has a lower energy by the binding energy between the defect and exciton compared to the FE. The BE'S can be categorized into three main types: a neutral donor bound exciton (DOX),a neutral accepter bound exciton (AOX),and an ionized donor bound exciton (D'x). We have studied the PL spectra of ZnO films at room temperature (300 k) and 15 k with an excitation wavelength 325nm (UV) light from He-Cd laser. Figure 4.2 shows

PL spectra of unannealed ZnO: (Eu,C13) with 0.5 % of Eu concentration which has two
distinct peaks. The first one around 380 is from the bound exciton (BE) and the second one at 520nrn is duo to the host (ZnO). The peak of the green band spectra exists at 500 nrn and it does not shift between 15 K and 300 K. We found that there is no emission due C , we found that there are peaks to rear earth. But when we annealed the sample at 550 O from emissions of
E U ~ +overlapping

with the broad band luminescence of ZnO around

620nm. We found that at low temperature, around (15 K), the luminescence from the rare earth ions is stronger than the luminescence at room temperature. This is also shown in C , there is no big difference Figure 4.3. In addition, when we annealed the sample at 600 O between the emissions from the sample. Only the band edge emission decreased as shown in Figure 4.4.

34

D'X

ZnO:Eu,Cl unannealed EU* Concentration : 0.05 at.% hexc = 325 nm

I I

400

600

800

1000

Wavevlength [nm]

Figure 4.2 PL spectrum of ZnO: (Eu, C1) un-annealed

ZnO:Eu,Cl annealed at 550 "C EU~' Concentration : 0.05 at.%

400

500

600

700

800

900

1000

Wavevlength [nm]
Figure 4.3 PL spectrum of ZnO: (Eu, C1) annealed at 550 "C

ZnO:Eu,Cl annealed at 600 "C EU" Concentration : 0.05 at.% h = 325 nm

400

500

600

700

800

900

1000

Wavevlength [nm]
Figure 4.4 PL spectrum of ZnO: (Eu, C1) annealed at 600 O C

4.1.2 Cathodoluminescent

Figure 4.5 presents the CL spectrum of ZnO: Eu,Cl3 thin films measured at room temperature (300 K) and at low temperature (15 K) using an excitation voltage of 5kV. The peak of the green band spectra exists at 500 nm and it does slightly shift between 15 K and 300K; also the emission intensity increases with decreasing sample temperature. The sharp red-emission peak at 615nm is characteristic of the transition between electronic energy level of E U ~ +ions ' D O- 7~~ (J = 1 to 6). The annealing process causes an increase in the CL intensity. The CL intensity was found generally to increase with increasing annealing temperature, while emission peak position did not change. This increase may be due to two effects. First the crystallite size increases with higher annealing temperature, and second there is increase in the density of Oxygen Vacancies.

615 nm ZnO:Eu,Cl on glass substrates

Concentration : 2at.%

Wavelength [nm]
Figure 4.5 CL spectrum of ZnO: (Eu, Cl) annealed at 600 and 700 "C (a),(b) measured at low temperature (15 K) and (c) at room temperature (300 K)

4.2 Polycrystalline Sintered Pellets ZnO: RECl3

In this study, we have investigated the effect of chlorine ions co-doping on luminescence sensitization of europium (Eu) and thulium (Tm) ions doped ZnO samples.

4.2.1 Crystal Structure of ZnO Doped with E U ~ + (ZnO: Eu, CIS).

Figure 4.6a shows the XRD spectral of undoped ZnO sintered in air for 2 hours at temperatures of 1000 "C. The diffraction peaks corresponding to the ZnO (100) , (002) , (101) and (102) planes of the wurtzite structure can be seen. For comparison, the XRD spectral of ZnO: EuC13 with a percentage concentration of 0.07 and sintered in air for 2 hours at temperatures of 1000 "C is shown in Figure 4.6b. In addition to the wurzite peaks of ZnO host, new diffraction peaks are clearly seen. These peaks are identified as (1 11) and (401) corresponding to the cubic phase of Eu203. For sample sintered in vacuum atmosphere new peaks have appeared corresponding to tetragonal phase of EuOCl compound as shown in Figure 4 . 6 ~ .These results suggest that for the case of sintering in air atmosphere, most chlorine ions escape from the pellet resulting in formation of Eu203. For the case of sintering in vacuum atmosphere, however, it seems that
EU~'

ion substitutes into zn2+site and couples with oxygen in ZnO lattice together

with the interstitial C1- as a charge compensator leading to the formation of EuOCl complex. These results are in agreement with reported work by Ref [2].

Figure 4.6 (a) ZnO powder 2 hr at 1000 O C in air. (b) Zn0:Eu powder 2 hr at 1000 "C in C in vacuum, air, EuC13 with 0.07 in concentration . (c) ZnO: Eu powder 3 hr at 1000 O EuCI3with 0.07 in concentration.

4.2.2 Photoluminescence of Zinc Oxide Doped with Europium (ZnO: Eu,CI).

Photoluminescence was observed from 9 K to 300 K in direct and indirect excitation processes. In Figure 4.7, we can see the PL emission spectra for ZnO with two different EuC13 concentrations sintered in air. On the top of the broad emission from the ZnO host, sharp emission lines can be seen in the 6 10-620 nrn range and at 700nm. The structures of these sharp emission lines indicate that they are due to E U ~ +ions. Shown in Figure 4.8 are the PL spectra for Zn0:Eu phosphors with varying EuC13 concentration sintered in vacuum at 1000 "C. It is not clear at this point what mechanism is responsible for the quenching of unwanted broad emissions from the ZnO host. It is clear, however, that this effect is closely related to earlier finding from XRD measurement, where we observe that Eu couples with the ZnO host lattice by forming an EuOCl complex in samples sintered in vacuum. The peak assignment of the transitions is shown in Table 4.1

Peak Position

Table 4.1 The Peak Assignment for the PL of ZnO: Eu,Cl. Transition of Tm

Figure 4.7 PL emission spectra for ZnO : Eu sintered at 1000 "C in air

Z n 0 : E u phosphor sintered in vacuum

EU~+ Concentration:

626 nm
h exc
n

a: 0.07 at% b: 0.025 at% = 325 nm, 300 K

3 d

or(

$ 2

'D 0

-F
7

(J=1..6)

Q) . y

n
I 4

I'
(a)

P1

520 nm

I
'4
I I
L

.
I
I

(b)
I
I

400

500

600

700

800

900

Wavelength [nm]

Figure 4.8 PL emission spectra for ZnO : Eu sintered at 1000 "C in vacuum

4.2.3 Cathodoluminescent of ZnO Doped with E U ~ +(ZnO: Eu, Cl).

In Figure 4.9, we can see the CL emission spectra for ZnO: Eu with a percentage concentration of 0.025 and sintered in N2 for 2 hours at temperatures of 1000 "C. The broad CL spectra for ZnO: Eu sintered in N2 is known to result for the suppression of broad band emission centered at 520 nm due to recombination between self-activated defect levels, which are Zn interstitial and 0 vacancies. Emission line at 620 nrn is due to Zn vacancies and oxygen interstitial. Luminescence was observed from 9 K to 300 K in direct and indirect excitation processes.

ZnO:Eu,Cl annealed 2h at 1000 O C in N,

D,,-'F~

(5=1..6)

J
Wavelength [nm]

Figure 4.9 CL emission spectra for ZnO : Eu sintered at 1000 O C in N2

4.2.4 Crystal Structure of Zinc Oxide Doped with Thulium (ZnO: Tm,Cl). Figure 4.10a shows the XRD spectral of undoped ZnO sintered in air for 2 hours at temperatures of 1000 "C. The diffraction peaks corresponding to the ZnO (loo), (002), (101), and (102) planes of the wurtzite structure can be seen. For comparison, the XRD spectral of ZnO: TmC13 with a percentage concentration of 0.07 and sintered in vacuum for 3 hours at temperatures 1000 "C are shown in Figure 4.10b. In addition to the wurzite peaks of ZnO host, new diffraction peaks are clearly seen. However, it seems that ~ m ~ + ion substitutes into zn2+site and couples with oxygen in ZnO lattice together with the interstitial Cl- as a charge compensator leading to the formation of TmOCl complex [2,

351.

Figure 4.10 (a) ZnO powder sintered in air for 2 hr at 1000 O C in air. (b) ZnO: Tm powder sintered in vacuum for 3 hr at 1000 O C in vacuum, TmC13 with 0.07 inconcentration.

4.2.5 Photo Luminescent of Zinc Oxide Doped with Thulium (ZnO: Tm,Cl).
We have studied the PL spectra of ZnO films at room temperatures (300 K) and 10 K with an excitation wavelength 325nm (UV) light from He-Cd (Helium Cadmium) Laser. In Figure 4.1 1 we can see the PL emission spectra for ZnO: Tm sintered in vacuum with (0.01) at % concentrations and annealed for 2.5 hours at 1000 "C. The first peak is from the bound exciton (BE). In addition to the ZnO luminescence, it shows a sharp peak at 476 nm, depending upon the relative positions of the
' ~

and 4 3

~ levels 6

of

~ (blue + emission due to thulium). Also, it shows a sharp peak at 800 nm the ~ m ion which depend upon the relative positions '
~

and 4 3

~ transition. 5

The peak assignment of

the transitions is shown in Table 4.2. For more information on Tm in various hosts references [2,3, and 281 are good sources.

Peak Position

Table 4.2 The Peak Assignment for the PL of ZnO: Tm,Cl. Transition of Tm

Figure 4.11 PL emission spectra for ZnO : Tm sintered at 1000 "C in vacuum

4.2.6 Cathodoluminescent of Zinc Oxide Doped with Thulium (ZnO: Tm,CI).

In Figure 4.12 we can see the CL emission spectra for ZnO: Tm sintered in N2 with (0.025) M/M concentrations. The first peak is from the bound exciton (BE). The peak of the green band spectra exists at 500 nrn and there is no emission due to Tm rear earth ions.

300

400

500

600

700

800

900

1000

Wavelength [nm]

Figure 4.12 CL emission spectra for ZnO : Tm sintered at 1000 O C in N2

Chapter Five Excitation Mechanisms and Conclusion

5.1 Excitation Mechanisms

An electron and a hole may be bound together by their attractive coulomb

interaction. The bound electron hole pair is called an exciton. It can move through the crystal and transport energy; it does not transport charge because it is electrically neutral. When Zn0:RE material is excited by an electron beam, a number of physical processes occur. Primary electrons penetrate the ZnO host and produce electron hole pairs, which then diffuse through the ZnO host and either transfer their energy to rare earth ions that subsequently emit light, or recombine at killer centers nonradiatively [29]. Luminescence excitation of a material below the fundamental absorption edge, or forbidden energy gap (E,) is called direct excitation mechanism. Excitation by photon with an energy greater than the band gap results in the creation of a hot electron hole pairs which transfer energy to the 4f electron system. We call this process Indirect excitation mechanism. The excitation mechanism in CL and EL involves direct impact excitation of RE3+ ions by hot electrons, as well as an energy transfer from the generated electron-hole pairs, or by impact excitation (or ionization) involving impurity states outside the 43shel1, with subsequent energy transfer to this shell

[301.
Figure 5.1 shows a model of the excitation processes for ZnO doped with RE ions. It is assumed that the indirect excitation of RE ions in ZnO proceeds through the nonradiative transfer of energy from the exciton bound to the RE complex trap, which

contains RE ions and native defects or impurities required for charge compensation in the ZnO host. The energy overlap between the broad-band emission and RE energy level does not guarantee energy transfer because the local environment around the RE ion plays a significant part in the transfer process so that any one RE configuration may only couple to a selected band. Also, if the collapsing energy of an exciton bound to such a complex center is not sufficient to excite the 4f shell of the

RE^' ion ,the characteristic 4f

emission of the RE ion will not be present. For some ions, the lowest 4f energy levels are excited and only infrared emission is observed. In the case of CL, excitation occurs through both direct impact excitations of RE ions by hot electrons or indirectly by generation electron hole pairs and transfers energy to the 4f shell via the mechanism discussed previously [3 I].

Figure 5.1 A model of the excitation processes for ZnO doped with RE ions

5.2 Energy Transfer Mechanisms

In the indirect excitation, there are four possible mechanisms for the energy transfer in ZnO doped rare earth [31]. The first mechanisms is shown in Figure 5.2, the excitation electron excites the electron hole pair and the generated electron could be trapped by some impurity state which is related to the rare earth ions and inside the forbidden gap.

Figure 5.2 Schematic diagram of trapping electron on rare earth related state. The recombination of energy of trapped electron and the free hole excites the rear earth ions.

In the second mechanisms shown in Figure 5.3, the hole in the valance band is trapped by the impurity state that is related to the rare earth ions. Then by Auger energy transfer process, the recombination energy of the bound electron and free hole (or the recombination energy of the free electron and the bound hole) is transferred to the rear earth luminescence center.

Figure 5.3 Schematic diagram of trapping hole on rare earth related state. The recombination of energy of free electron and the trapped hole excites the rear earth ions.

The third mechanism is shown in Figure 5.4, where both the electron and the hole are trapped by the impurity state inside the forbidden gap.

D-A Pair energy transfer mechanism

Figure 5.4 Schematic diagram of trapping electron and hole on impurity related state. The recombination of energy of trapped electron and hole excites the rear earth ions.

For the fourth mechanism, shown in Figure 5.5, it is possible for the recombination energy of the free exciton is transferred to the localized rare earth ions 4f state, where the electron is in the conduction band and the hole is in the valance band [2,29].

Figure 5.5 Schematic diagram of excitation electron and hole pair. The recombination of energy of free electron and hole excites the rear earth ions.

5.3 Conclusion

In this study we have prepared and investigated the effect of chlorine ions codoping on luminescence sensitization of Eu and Tm ions doped ZnO samples. We have successfully obtained polycrystalline thin films of un-doped and E U ~ +doped ZnO by spray pyrolysis technique. We have investigated and studied the optical characterization of the sample by X-ray diffraction, photoluminescence and cathodoluminescence. The peak of ZnO green band spectra exists at 500 nm and it does not shift between 15 K and 300 K. We found that there is no emission due to rear earth in as grown ZnO. But when we annealed the sample at 550 "C we found that there are peaks from emissions of E U ~ + overlapping with the broad band luminescence of ZnO around 620nm. We found that at low temperatures around (15 K), the luminescence from the rare earth ions is stronger than the luminescence at room temperature. We also studied the sintered polycrystalline ZnO: RE pellets co-doped with C1-. The analysis of XRD measurements indicate that for ZnO:Eu,C13 and ZnO:Tm,C13 sintered in vacuum Eu and Tm exist in the host lattice as EuOCl and TmOC1. The presence of the complexes effectively removes the ZnO broad band host emission here was not observed quenching of RE emission due to concentration effect in the investigated doping range. Both Zn0:Eu and Zn0:Tm show Re 4f4f emissions overlapped with broad host emission band. Luminescence was observed from 15 K to 300 K in direct and indirect excitation processes.

5.4 Future Work

As mentioned earlier ZnO is usually n-type. The carrier concentrations (electrons) in the as-grown films are usually high, which makes p-type doping of ZnO very difficult due to a self compensation effect. Zhenguo Ji and his coworker reported that they obtained P-type ZnO by spray pyrolysis [23]. More experimental investigation of p-type doped with rear earth ions can be undertaken. Present of both n-type and p-type doping would enable us more complicated device structures such as p-i-n diodes and detectors.

References
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