Contents

Introduction ............................................................................................................................................ 4 RESEARCH TOPIC..................................................................................................................................... 4 DEFINITIONS............................................................................................................................................ 4 OPTOELECTRONICS ............................................................................................................................. 4 QUANTUM WELL................................................................................................................................. 4 QUANTUM WIRE ................................................................................................................................. 4 QUANTUM DOT .................................................................................................................................. 5 Background ......................................................................................................................................... 5 Literature Review ................................................................................................................................ 5 BAND THEORY ......................................................................................................................................... 7 MOLECULAR ORBITAL THEORY: .......................................................................................................... 7 VALENCE BAND AND CONDUCTION BAND ........................................................................................... 15 BASIC SEMICONDUCTOR PHYSICS ........................................................................................................ 16 ELEMENTAL SEMICONDUCTORS ........................................................................................................... 16 COMPOUND SEMICONDUCTORS .......................................................................................................... 17 INTRINSIC SEMICONDUCTORS .............................................................................................................. 17 EXTRINSIC SEMICONDUCTORS ............................................................................................................. 18 ACCEPTOR IMPURITIES: .................................................................................................................... 19 DOPING OF Ge CRYSTAL: .................................................................................................................. 19 THE FERMI LEVEL: ................................................................................................................................. 20 CHEMICAL POTENTIAL: ..................................................................................................................... 21 Fermi-level for an Intrinsic semiconductor ................................................................................... 23 Fermi level for an extrinsic semiconductor .................................................................................. 23 Fermi-level for n-type Semiconductor ........................................................................................ 23 Fermi-level for P-type semiconductor ........................................................................................ 24 EFFECTIVE MASS: .............................................................................................................................. 25 OPTICAL PROPERTIES OF BAND GAP: ................................................................................................... 28 ELECTRON ENERGY BAND GAPS: ...................................................................................................... 28 DIRECT AND INDIRECT BAND GAPS: ................................................................................................. 29 OPTICAL PROPERTIES OF DIRECT BAND GAP SEMICONDUCTOR: .................................................... 31 ADVANTAGE OF DIRECT BAND GAP SEMICONDUCTOR: .................................................................. 32 USES OF DIRECT BAND GAP SEMICONDUCTORS: ............................................................................. 32

BULK MATERIALS: ............................................................................................................................. 32 BULK SEMICONDUCTORS:.................................................................... Error! Bookmark not defined. Energy level ........................................................................................................................................... 33 Band gap ............................................................................................................................................... 33 Valence band ........................................................................................................................................ 34 Conduction band................................................................................................................................... 34 PHOTOLUMINESCENCE: ........................................................................................................................ 35 LUMINESCENCE:................................................................................................................................ 35 PHOTOLUMINESCENCE: ........................................................................................................................ 35 FORMS OF PHOTOLUMINESENCE: ........................................................................................................ 38 FLUORESCENCE: ................................................................................................................................ 38 PHOSPHORESCENCE: ........................................................................................................................ 38 QUANTUM WELL: ................................................................................................................................. 41 QUANTUM WELL: ........................................................................................................................... 41 HOW QUANTUM WELLS ARE MADE? ................................................................................................... 43 GaAs/AlGaAs Quantum wells:........................................................................................................... 44 Quantum Well Growth: .................................................................................................................... 45 MOLECULAR BEAM EPITAXY: ............................................................................................................ 46 OPTICAL PROPERTIE OF QUANTUM WELL:........................................................................................... 48 Quantum Well Electro absorption Physics ....................................................................................... 48 Quantum- Confined Stark Effect:...................................................................................................... 48 ENERGY AS A FUNCTION OF WELL WIDTH: ...................................................................... 48 APPLICATION/USES OF QUANTUM WELL: ............................................................................................ 50 QUANTUM WIRE AND QUANTUM DOT................................................................................................ 52 INTRODUCTION:................................................................................................................................ 52 QUANTUM WIRE:.................................................................................................................................. 53 QUANTUM WIRE GROWTH: ................................................................................................................. 54 T-shaped quantum wires: ................................................................................................................. 54 V-shaped quantum wires: ................................................................................................................. 56 OPTICAL PROPERTIES OF QUANTUM WIRE: ......................................................................................... 56 PHOTOLUMINESCENCE IN QUANTUM WIRE: ....................................................................................... 57 APPLICATIONS/USES OF QUANTUM WIRE: .......................................................................................... 58 QUANTUM DOT: ................................................................................................................................... 59 QUANTUM DOT GROWTH: ................................................................................................................... 60

OPTICAL PROPERTIES OF QUANTUM DOT:........................................................................................... 62 PHOTOLUMINESCENCE IN QUANTUM DOT: ........................................................................................ 63 APPLICATIONS / USES OF QUANTUM DOT: .......................................................................................... 66

Chapter 1. INTRODUCTION
Clearly it is of high importance to acquire this 'feel' in general terms before getting into some of the finer detail which, whilst very necessary, does not allow the enter relationship between the various aspects to remain sharply visible. The intention is that the similarity acquired by reading this research will facilitate and understanding of the other chapters in the research. Our keen interest for the modern views of optoelectronics has resulted from an utmost effort by many scientists, over many centuries, and a valuable appreciation of some of the delicates of the subjects can be obtained from the study of that effort. A brief summary of the historical development in the field of optoelectronics is our starting point.

1.1. RESEARCH TOPIC:

A brief description of Optical properties of quantum well, quantum wire and quantum dot.

1.2. DEFINITIONS:
1.2.1. OPTOELECTRONICS:
It is the study and application of electronic devices that source, detect and control light, usually considered a sub field of photonics. Optoelectronics is based on the quantum mechanical effects of light on electronic materials.

1.2.2. QUANTUM WELL:

Quantum well is a potential well with only discrete energy values. Quantum wells are formed in semiconductors by having a material like gallium arsenide sandwiched between two layers of a material with a wider band gap, like aluminium arsenide.

1.2.3. QUANTUM WIRE:

Quantum wire is an electrically conducting wire in which quantum effects are affecting transport properties.

1.2.4. QUANTUM DOT:

Quantum dot is a revolutionizing material where traditional semiconductors fall short. These dots are tiny nanoparticles with many applications. They can be turned to emit any colour of light from UV to what it is visible to the human eye.

1.3. BACKGROUND:
Since 1993, In GaN quantum wells (QW)-based light emitting diodes (LEDs) have been continuously improved and commercialized as light sources in the ultraviolet and visible spectral regions. Moreover white light LEDs, in which a blue LED is combined with a yellow phosphor, have been commercialized and offer a replacement for conventional incandescent and fluorescent light bulbs. However, these devices have not fulfilled their original promise as solid-state replacements for light bulbs as their light emission efficiencies have been limited. The most important requirement for a competitive LED for solid state lightening is the development of new methods to increase its quantum efficiency of light emission.

1.4. LITERATURE REVIEW:

Gallium was discovered by Lecoq de Boisbaudran when he was studying Zinc in 1875AD. Lecoq did not discover it by accident. He had been searching for it for years and since he knew about Dmitri Mendeleev's periodic trends, he had a hunch that it would be the next element by zinc and might be found in zinc ore. He was correct and found in Gallium. Albert the Great was an Alchemist in 1250 AD and was the first to form almost pure Arsenic. The many new ideas and scientists that were involved in developing Gallium Arsenide technology has been muddled and lost through history. Because of the complicated nature with the technologies that were developed with gallium arsenide, it is difficult to pinpoint specific dates or scientists that discovered its uses. Now, it had has been developed to serve many purposes. In 1907, the British discovered infrared emission from Gallium Arsenide. This was called electroluminescence http://galliumarsenide101.weebly.com/historical-background-of-gaas.html Gallium arsenide does not occur naturally. Gallium is present in the earths crust at 515 mg/kg and is recovered as a by-product of the extraction of aluminium and zinc from their ores (Beliles, 1994; Sabot & Lauvray, 1994).

Gallium arsenide has light-emitting properties, high electron mobility, electromagnetic properties and photovoltaic properties. As a semiconductor, it has several unique material properties which can be

utilized in high speed semi-conductor devices, high power microwave and millimetre-wave devices, and optoelectronic devices including fibre optic sources and detectors. Its advantages as a material for high speed devices are high electron mobility and saturation velocity, and relatively easy growth of semiinsulating substrates which render low parasitic and good device isolation. Other useful properties are controllable band gap by alloying, desirable ionization and optical absorption properties. Gallium arsenide has certain advantages over other semiconductor materials: (1) faster operation with lower power consumption, (2) better resistance to radiation and, most importantly, (3) it may be used to convert electrical into optical signals (Chakrabarti, 1992; Greber, 2003).

Many manufacturers have introduced new LEDs based on gallium arsenide technology which offer improvements over current LEDs. In many cases, the new LEDs are brighter, last longer and/or can be used in new applications (Kramer, 2002).

GaAs photodiodes are of particular interest for X-ray imaging detectors due to their improved photon detection efficiency compared to silicon photodiodes of comparable thickness. Detectors fabricated from GaAs have a linear attenuation coefficient for X-ray photons similar to that of germanium but are able to operate at, or close to, room temperature (Sellin 2001).

CHAPTER 2. BAND THEORY

2.1. INTRODUCTION:
In this chapter I started with molecular orbital theory. To fully understand the band structure, it is essential to start with molecular orbital theory. Further I discussed about semiconductors and their band gaps, which type of band gap semiconductor is useful for optical devices, their uses and optical properties are discussed below.

2.2. MOLECULAR ORBITAL THEORY:

Molecular orbital (MO) theory uses a linear combination of atomic orbitals (LCAO) to represent molecular orbitals involving the whole molecule. These are often divided into bonding orbitals, antibonding orbitals, and non-bonding orbitals (Ceyer, 2008). Let us start with hydrogen atom. We take two hydrogen atoms having a symmetric wave function.

Now bring these two atoms at a distance of bonding or add these two wave functions or superimpose the wave functions of two hydrogen atoms. These two wave functions will overlap and it can be constructive or destructive interference. First we will do for constructive interference.

For constructive interference when these two wave functions overlap it becomes like,

This is the sum of constructive interference and called the molecular wave function. We name this molecular wave function a 1S. 1S shows the symmetry of wave functions or combination of two 1S orbital wave functions. And P shows the probability density.

= 1Sa + 1Sb P = [1S] 2 P = [1S] 2 = (1Sa + 1Sb) (1Sa + 1Sb) P = (1Sa) 2 + (1Sb) 2 + 2(1Sa) (1Sb)
If we take a particular case, means if we square the wave function of individual atom first and then we sum the two wave functions like this, 1S = (1Sa)2+(1Sb)2 , then in this case we havent allowed wave functions to interfere constructively and it will be non bonding. Here we have position and probability density graph (Ceyer, 2008).

The first curve shows the probability densities when we add the wave functions of two atoms and then square it. And second curve shows the probability density when we square the wave function of individual atom and then add them. For second curve the probability density is less (Ceyer, 2008). Now what will happens to the energy?

In fig: 2.5 (1Sa) and (1Sb) are the energy levels of two separated hydrogen atom. Once we allow two wave functions to interfere constructively, produce a new state 1S, that state is lower in energy from the individual hydrogen atom or we can say that this energy goes down and forms a new molecular state and the wave function in 1S is the molecular wave function. At low energy level there is bonding of two atoms (Ceyer, 2008). Now we will take the case of destructive interference. Again we will take same hydrogen atoms.

The wave function of 1Sb is going to cancel the wave function of 1Sa or we superimpose these two wave functions with different sign. And result is molecular wave function (Ceyer, 2008).

There is no overlapping in this case because we have destructive wave function and this is antibonding wave function. We labeled it same as we did for constructive interference but with star (*). We will represent destructive interference with *1S (Ceyer, 2008). Now the probability density is,

*1S = 1Sa - 1Sb P = [*1S] 2 P = [*1S] 2 = (1Sa - 1Sb) (1Sa - 1Sb) P = (1Sa) 2 + (1Sb) 2 - 2(1Sa) (1Sb)
The position and probability density graph is,

In this case fig: 2.8, probability density is very low. Non-bonding has more electron density then antibonding (Ceyer, 2008). Since anti-bonding = against bonding. Now the energy will be,

For destructive interference, its increase in energy. *1S and 1S two levels are at same distance from individual atom (Ceyer, 2008).

The first and second excited state of hydrogen molecule (H2) is,

But the ground state configuration of H2 is shown in fig: 2.11.

This was bonding and antibonding for ground state of H2 molecule. The electronic configuration for H2 molecule for ground state is,

H2 = (1S) 2 (*1S) 0
There are two electrons in bonding state (1S) and zero electrons in antibonding state ( Next is He2 molecule (Ceyer, 2008). There are two electrons in each He atom.
* 1S).

Two electrons will be at bonding state and two will be at antibonding state. Electronic configuration is,

He2 = (1S) 2 (*1S) 2

How strong the bond will be? It can be find through bond order. Bond order is defined as, 1/2 (no. of bonding electron no. of antibonding electron) So in case of He2. 1/2 (2 2) = 0, there is no bond. The bond order is equal to zero. He2 has no bond between them but He2 does have bond between them but its very small in value that we consider it as zero bond (Ceyer, 2008). In short, when there are n number of atoms there will be n number of energy levels or many energy levels starting at the highest antibonding, down to the lowest bonding. And the distance between the successive levels becomes small. They are so close together consider as band.

In the above basic theory, it was assumed that if atoms were brought together, they would form bonding, non-bonding and antibonding orbital of different energies. These molecular orbitals are described by wave functions. The most important point to come out of the theory is that for N atomic orbitals in a molecule, N molecular orbitals must be the outcome. For example, consider a molecule with two atomic orbitals. The result must be that two molecular orbitals will be formed from these atomic orbitals: one bonding and one antibonding, separated by certain energy.

If this is expanded to a molecule with three atoms, assuming 1 atomic orbital for each, then the result must be that 3 molecular orbitals will be formed: one bonding, one non-bonding and one anti-bonding.

Now, let's take it to 10 atoms. This will produce 10 molecular orbitals: 5 bonding and 5 antibonding. Now lets take a close look at the separation between each set of orbital. As the number of molecular orbital increases, the energy difference between the lowest bonding and the highest antibondig increases, while the space between each individual orbital decreases. As the number of molecular orbital increases with the number of atoms in a molecule, it will be observed that the spacing between the lowest bonding and highest antibonding orbital will reach a maximum.

Now consider a metal with an infinite number of atoms. This will form an infinite number of molecular orbital and forming a band. This whole process is shown in fig: 2.17.

In the above fig: 2.17, the origin for the band becomes quite clear because as the number of molecular orbital increases, they bonding and antibonding orbital get closer together filling in the middle. This results in the band seen on the right hand side. It becomes quite clear that the molecular orbitals become blurred and hence mix with each other.

 is valence band because these are bonding orbitals and * is antibonding orbitals called conduction
band. By describing the molecular orbitals it becomes much easier to understand the other materials like metals and semi-metals, insulators and semiconductors.

2.3. VALENCE BAND AND CONDUCTION BAND:

The band closest to the atomic nucleus called filled levels and the further band from the nucleus that has electrons in it called the valence band; all keep their electrons tightly in place. The next band out from that is called the conduction band and there electrons are free to move. Any solid has a large number of bands. Bands have different widths, based upon the properties of the atomic orbital from which they arise. In metals they have very high conductivity because there is no energy gap between valence band and conduction band thats why these are good conductors. In a conductor or metals the valence band is full of electrons, while the conduction band has some free electrons and many empty energy levels. The addition of a very small amount of energy will allow electrons to move within the conduction band, some rising to a higher level and others returning to lower levels. This movement of electrons is electrical conduction. In some conductors the valence band and the conduction band actually overlap.

In semiconductors or insulators, the lower most almost fully occupied band called the valence band. The upper most almost unoccupied band called conduction band because only when electrons are excited to the conduction band when current flow in these materials. The difference between insulators and semiconductors is only the forbidden band gap. In insulators the band gap between valence and conduction band is very large.

2.4. BASIC SEMICONDUCTOR PHYSICS:

The highest filled level at T = 0K is known as the valence band. Electrons in the valence band do not participate in the conduction process. The first unfilled level above the valence band is known as the conduction band. There is small energy gap between valence and conduction band therefore excitation of electrons easily take place. Insulators have an energy gap that is far greater than the thermal energy of the electron. While in semiconductor materials the energy gap is around 1eV.

2.4.1. ELEMENTAL SEMICONDUCTORS:

Semiconductors where each atom is of the same type such as Ge, Si. These atoms are bound together by covalent bonds, so that each atom shares an electron with its nearest neighbor, forming strong bonds.

2.4.2. COMPOUND SEMICONDUCTORS:

Compound semiconductors are made of two or more elements. Common examples are GaAs or InP. These compound semiconductors belong to the III-V semiconductors so called because first and second elements can be found in group III and group V of the periodic table respectively. Semiconductors are classified into two types. 1) Intrinsic semiconductors. 2) Extrinsic semiconductors.

2.5. INTRINSIC SEMICONDUCTORS:

A semiconductor in a very pure form is called an intrinsic semiconductor. Ge and Si are intrinsic semiconductors. Elemental and compound semiconductors can be intrinsic semiconductors. The crystalline structure of Ge and energy band is given in fig: 2.20.

At absolute zero all electrons of semiconductor are tightly held. The inner electrons are bound i.e. the valence electrons are engaged in covalent bonding. At this temperature the covalent bond is very strong and hence there are no free electrons. Therefore the semiconductor crystal behaves as a perfect insulator at absolute zero. At room temperature the valence electrons absorbs thermal energy and get excited. Due to absorption of energy the valence electrons jump from valence band to conduction band. Whenever valence electron drips from valence band to conduction band a vacancy is created in a valence band and vacancy is called a hole. Thus an electron hole pair is produced. Now if potential difference is applied across a semiconductor, current would flow through the

external circuit. This type of semiconductor where the conductivity is due to the movement of electrons and holes is called intrinsic semiconductors. If there are n free electrons there must also be n-holes in intrinsic semiconductors. The relationship can be expressed as n = p, where n is the number of electrons and p is the number of holes.

2.6. EXTRINSIC SEMICONDUCTORS:

Conductivity of intrinsic semiconductor is very less at room temperature. To increase the conductivity, a small amount of external impurity is added to a pure semiconductor. Such semiconductor then becomes an impure or extrinsic semiconductor. The process of deliberate addition of a very small amount of impurity into an intrinsic semiconductor to increase its conductivity is called doping and the impurities are called dopants. The impurities are classified as donor impurities and acceptor impurities.

2.6.1. DONAR IMPURITIES:

Donar impurities are those elements which donate excess of electrons for conduction. Pentavalent like antimony (Sb), phosphorus (P) and arsenic (As) are donor impurities.

2.6.2. ACCEPTOR IMPURITIES:

Acceptor impurities are those elements which create positive carrier or holes that can accept electrons. Trivalent elements like boron (B), gallium (Ga) and indium (In) are acceptor impurities. Acceptor impurities are also known as P- type impurities.

Depending upon the type of impurities added the extrinsic semiconductor can be classified as, P- Type semiconductors. N- Type semiconductors.

2.7. DOPING OF Ge CRYSTAL:

If a pure Ge crystal, a small amount of pentavalent impurity like As is added then four of the five valence electrons forms a covalent bond with the four valence electrons of Ge and 5th one will be available for

conduction. These types of semiconductor where electrons are the current carriers are known as N- type semiconductor.

When trivalent impurities like B, Ga, In, is added to a pure Ge crystal, only 3 covalent bond are formed and there exists a vacancy in the 4th bond creating a hole. These types of semiconductors where positively charged holes are the current carriers are P- type semiconductors.

2.8. THE FERMI LEVEL:

The Fermi Level is defined as the highest occupied molecular orbital in the valence band at 0 K, so that there are many states available to accept electrons, if the case were a metal. It should be noted that this is not the case in insulators and semiconductors since the valence and conduction bands are separated. Therefore the Fermi-Level is located in the band gap.

It is important in determining the electrical and thermal properties of solids. The value of the Fermi level at absolute zero (273.15 C) is called the Fermi energy and is a constant for each solid. The Fermi level changes as the solid is warmed and as electrons are added to or withdrawn from the solid. Each of the much distinct energy with which an electron can be held within a solid is called an energy level. According to the laws of quantum mechanics, each energy level can accommodate only a limited number of electrons. The Fermi level is any energy level having the probability that it is exactly half filled with electrons. Levels of lower energy than the Fermi level tend to be entirely filled with electrons, whereas energy levels higher than the Fermi tend to be empty. When materials with different individual Fermi levels are placed in contact, some electrons flow from the material with the higher Fermi level into the other material. This transfer of electrons raises the lower Fermi level and lowers the higher Fermi level. When the transfer is complete, the Fermi levels of the two materials are equal. This behavior is important in electronic devices. The Fermi energy is a concept in quantum mechanics usually referring to the energy of the highest occupied quantum state in a system of fermions at absolute zero temperature. The Fermi level (also called chemical potential). The Fermi energy and chemical potential are the same at absolute zero, but differ at other temperatures. CHEMICAL POTENTIAL: Particles tend to move from higher chemical potential to lower chemical potential. In this way, chemical potential is a generalization of "potentials" in physics such as gravitational potential. When a ball rolls down a hill, it is moving from a higher gravitational potential (higher elevation) to a lower gravitational potential (lower elevation). In the same way, as molecules move, react, dissolve, melt, etc., they will always tend naturally to go from a higher chemical potential to a lower one. A molecule has a higher chemical potential in a higher-concentration area, and a lower chemical potential in a low concentration area. As always, the molecules move from higher chemical potential to lower chemical potential.

Another example is a glass of liquid water with ice cubes in it. Above 0C, an H2O molecule has a lower chemical potential as part of the liquid than as part of an ice cube. The ice melts as the H 2O molecules lower their chemical potential. Below 0C, the ice has a lower chemical potential, so the ice cubes grow. At exactly 0C, the chemical potential for water and ice are the same; the ice cubes will neither grow nor shrink, and the system is in equilibrium. Fermi level indicates the level of energy in the forbidden gap. The highest energy level in the crystal that can remain populated by electrons at a temperature of Absolute Zero. Electrons with greater energy than this may be available for conduction; electrons with less energy are bound to the crystal structure.

Diagram A in fig: 2.27 represents a good conductor, such as copper or silver. Here, at temperatures above Absolute Zero, electrons are always available to conduct electrical current, even with no applied energy. In metals, the valence and conduction bands actually overlap. Diagram B in fig: 2.27 showing a typical insulator, such as glass. All electrons are pretty much locked into the atomic structure, and are unavailable as current carriers. It will take a lot of energy to break any electrons loose for conduction. It's not impossible but it takes a lot of applied energy.

2.8.1. FERMI LEVEL FOR AN INTRINSIC SEMICONDUCTOR:

We know that the Intrinsic semiconductor acts as an insulator at absolute zero temperature because there are free electrons and holes available but as the temperature increases electron hole pairs are generated and hence number of electrons will be equal to number of holes. Therefore, the possibility of obtaining an electron in the conduction band will be equal to the probability of obtaining a hole in the valence band. If EC is the lowest energy level of Conduction band and EV is the highest energy level of the valence band then the Fermi level Ef is exactly at the center of these two levels as shown in diagram B in fig: 2.27.

2.8.2. FERMI LEVEL FOR AN EXTRINSIC SEMICONDUCTOR:

2.8.2.1. FERMI LEVEL FOR N-TYPE SEMICONDUCTOR:
Let a donor impurity is added to an intrinsic semiconductor then the donor energy level (ED) shown by the dotted line is very close to conduction band energy level (EC) shown in fig: 2.29. Therefore the unbounded valence electrons of the impurity atoms can very easily jump into the conduction band and become free electrons, thus at room temperature almost all the extra electrons of pentavalent impurity will jump to the conduction band. The donor energy level (ED) is just below conduction band level (EC) as shown in fig: 2.29. Due to a large number of free electrons, the probability of electrons occupying the energy level towards the conduction band will be more hence, Fermi level shifts towards the conduction band.

Diagram C fig: 2.27 represent the N-type semiconductor, the Fermi level gets pushed up close to the conduction band. If the doping level is heavy enough (large dosage of impurities), the Fermi level can actually enter the conduction band.

2.8.2.2. FERMI LEVEL FOR P-TYPE SEMICONDUCTOR:

Let an acceptor impurity is added to an intrinsic semiconductor then the acceptor energy level (EA) shown by dotted lines is very close to the valence band energy level (EV) shown in fig: 2.30.

The acceptor energy level (EA) is just above the valence band level as shown in fig: 2.30. Due to large number of holes the probability of holes occupying the energy level towards the valence band will be more and hence, the Fermi level gets shifted towards the valence band. Diagram D in fig: 2.27 represent a P-type semiconductor crystal. Here, the p-type impurities have left holes in the atomic structure, which tend to attract and hold free electrons. This pulls the Fermi level down until it gets close to the valence band. Similar to the highly-doped N-type crystal, a highly-doped P-type crystal will have its Fermi level within the valence band instead of just above it. There are important factors regarding the Fermi level in semiconductors that since the Fermi level is close to one of the working energy levels, it requires very little energy to push an electron over the edge and make it available for conduction. In an N-type crystal, only a very small applied voltage will kick the free electrons up into the conduction band to carry a current. In a P-type crystal, a small amount of energy will kick a bound electron just over the top of the valence band into the forbidden zone. This doesn't make the electron available for bulk conduction, but does allow the applied voltage to push the electron over into a hole, causing it to leave another hole behind it. In this way, a series of electrons can "hop" from bound state to bound state in a new location, allowing the hole to appear to move in the opposite direction. This is another way to think of hole conduction in semiconductor crystals.

2.9. EFFECTIVE MASS:

Suppose we have 100 electrons mutually interacting through a coulombic potential. The Schrdinger equation cannot be solved exactly because of the mutual coupling between all the electrons (electron 1 interacts with electron 2, 3, etc). To uncouple this many body system, we convert it into a system where we have "new electrons" interacting in a background potential. So, we look at the problem as if the new electrons are no longer interacting with each other but with some background potential. Since both systems need to be equivalent. We need to compare both systems: the original system as mutually interacting electrons, the new system has non interacting electrons in a certain potential well. To make sure that both systems are equivalent, we change the mass of the electrons in the second system, in such a way that both Schrdinger equations are describing the same reality. This new mass is the effective mass, which can be defined as the electron mass + some interactions (i.e. energy of those interactions) to uncouple the many body problem into many one body problems. That is the philosophy behind effective mass. Consider another example, a glass tube with water and glass tube with oil with some marbles. The flow of marbles in water would be faster than the oil, depends on viscosity and gravity. Now because of slow movement in oil it seems to think that marbles with less mass. The same concept, if we consider a

semiconductor crystal the free electrons attracted by the internal forces (free electrons interaction) and external forces (applied voltage) also, so the total force is equal to, Ftotal = Fexternal (applied voltage) + Finternal = ma m is the mass of rest electron. Now it is difficult to calculate the internal forces, so to compensate we are considering mass of electron as m*. m* is the effective mass, force = m* a. Effective mass would be different for Si, Ge When an electron is moving inside a solid material, the force between other atoms will affect its movement and it will not be described by Newton's law. So we introduce the concept of effective mass to describe the movement of electron in Newton's law. The effective mass can be negative or different due to circumstances. Generally, in the absence of an electric or magnetic field, the concept of effective mass does not apply. The expression for the effective mass is found from the dynamics of wave-packet, which represents a localized particle. The packet is made up of a small spread of frequencies; these are superimposed on each other. The wave-packet moves at the group velocity Vg.

Vg = Vg = dk = (1)

If an electric field Ef is applied, so that the wave-packet moves a distance dx in time dt. The change in energy of the wave-packet is,

dw = Fdx
We can write,

dE = Fdx dE = eEf dx

Putting values in equation (1).

dk =
We convert this to a time derivative.

dx

Since

= = =
The equation for the acceleration can be calculated from

.... (2)

= = = =
Putting values of from equation (2).

= a=
We know that,

F = m*a m* =
Since F = eE

Putting all the values and we get.

m* =
This is the effective mass of electron.

2.10. OPTICAL PROPERTIES OF BAND GAP:

2.10.1. ELECTRON ENERGY BAND GAPS:
The gap in energy between the atom-bound "valence band" electrons and the wandering "conduction band" electrons is known as the electron energy band gap: it is a "forbidden" zone. The energy separation, the width of the band gap, differs in different materials and physical conditions; it greatly influences optical and other properties. The theory explains certain color phenomena; it also explains the lack of color in many pure gem materials. Materials having a band gap can be grouped into one of three types, depending upon their chemistry and crystal structure.

Those with a band gap larger than the whole energy range of visible light, for example colorless type diamonds. In these materials even violet light, the highest energy visible light, is insufficient to raise the energy level of any valence band electron so that it can jump the band gap and become a conduction

band electron. Because of this, no visible light interacts with any electron; therefore, no light is absorbed and the material appears transparent and colorless, so long as it is pure. An example of this type is diamonds which are colorless when pure.

Those with a band gap smaller than the lowest energy of visible light i.e. even lower than the energy of red light then all the visible light that enters the material interacts with electrons and is absorbed. This means that the material is opaque in the visible region.

Those with band gap energy range which overlaps that of visible light, for example yellow type and blue type diamonds. When either nitrogen or boron is present as isolated atoms in the diamond structure, energy levels are produced in the forbidden gap between the valence band and the conduction band. Electrons jumping to or from these levels causes absorption of light from part of the visible light spectrum and consequently a residual color is seen.

2.11. DIRECT AND INDIRECT BAND GAP SEMICONDUCTOR:

In semiconductor physics, the band gap of a semiconductor is always one of two types, a direct band gap and indirect band gap. Let's say that we have an unknown material and we wanted to determine whether it has an indirect or a direct band gap.

Suppose we bombard the surface of the semiconductor with a specific wavelength of light and look for emissions of another wavelength. If the emitted wavelengths have a different frequency than the impinging wavelengths, then there the band gap must be indirect because some of the added energy would have to be converted to phonon energy in order for an emission to take place. In a direct band gap semiconductor, the top of the valence band and the bottom of the conduction band occur at the same value of momentum.

In an indirect band gap semiconductor, the maximum energy of the valence band occurs at a different value of momentum to the minimum in the conduction band energy.

The difference between the two is most important in optical devices. A photon can provide the energy to produce an electron-hole pair. Each photon of energy E has momentum P = E/c, where c is the velocity of light. An optical photon has energy of the order of 1019 J and, since c = 3 108 ms1, a typical photon has a very small amount of momentum. A photon of energy Eg, where Eg is the band gap energy, can produce an electron-hole pair in a direct band gap semiconductor quite easily, because the electron does not need to be given very much momentum. However, an electron must also undergo a significant change in its momentum for a photon of energy Eg produce an electron-hole pair in an indirect band gap semiconductor. This is possible, but it requires such an electron to interact not only with the photon to gain energy, but also with a lattice vibration called a phonon.

2.12. OPTICAL PROPERTIES OF DIRECT BAND GAP SEMICONDUCTOR:

Another advantage of direct band gap semiconductor is that it has optical properties. The minimum photon energy that is needed to excite an electron into the conduction band is associated with the band gap of material. When electron-hole pairs undergo recombination, photons are generated with energies that correspond to the magnitude of the band gap. A phonon is required in the process of absorption or emission in the case of an indirect band gap. There must be a direct band gap in applications of optical devices.

2.13. ADVANTAGE OF DIRECT BAND GAP SEMICONDUCTOR:

Direct band gap has conductance band minima and valence band maxima at the same wave vector. An indirect band gap does not. This becomes important for optical reasons. In a direct band gap semiconductor, like GaAs, it has absorption and emission of photons without requiring phonons for momentum conservation. If we give the semiconductor some energy and if it makes light, its direct. But indirect band gap will produce no light. Sometimes direct band gap semiconductors called optically active.

2.14. USE OF DIRECT BAND GAP SEMICONDUCTORS:

Band gap value is important for light generation in LEDs and semiconductors lasers and it determines the energy of emitted photons. Direct band gap semiconductors are use for making LEDs and lasers because light generation occurs with greater probability. GaAs is one of the best direct band semiconductor and use to make optical devices such as LEDs and semiconductor lasers, whereas silicon which is an indirect band gap semiconductor is not.

2.15. BULK SEMICONDUCTOR:

Material in which electron in any band can move in all directions. It is 3 dimensional systems. Bulk semiconductors are materials that are sold in bulk that can be used to make semiconductors. There are two common materials that are used: silicon and gallium arsenide. Silicon is one of the most abundant elements on the planet. Gallium arsenide is a compound that is produced exclusively for the semiconductor industry. These materials must be purified and synthesized before they are used in electronics. Within a bulk semiconductor crystal, electrons may occupy states in one of two continuous energy bands - the valence band, which is heavily populated with low energy electrons and the conduction band, which is sparsely populated with high energy electrons. The two energy bands are separated by an energy band gap in which there are no permitted states available for electrons to occupy.

2.15.1. ENERGY LEVEL:

By the solution of Schrdingers equations, the electrons in a semiconductor can have only certain allowable energies, which are associated with energy levels. No electrons can exist in between these levels, or in other words can have energies in between the allowed energies. In addition, from Paulis Exclusion Principle, only 2 electrons with opposite spin can exist at any one energy level. Thus, the electrons start filling from the lowest energy levels. Greater the number of atoms in a crystal, the difference in allowable energies become very small, thus the distance between energy levels decreases. However, this distance can never be zero. For a bulk semiconductor, due to the large number of atoms, the distance between energy levels is very small and for all practical purpose the energy levels can be described as continuous fig: 2.35.

2.15.2. BAND GAP:

From the solution of Schrdingers equations, there are a set of energies which is not allowable, and thus no energy levels can exist in this region. This region is called the band gap and is a quantum mechanical phenomenon (Figure 3). In a bulk semiconductor the band gap is fixed; whereas in a quantum dot nanoparticle the band gap varies with the size of the nanoparticle.

2.15.3. VALENCE BAND:

In bulk semiconductors, since the energy levels can be considered as continuous, they are also termed as energy bands. Valence band contains electrons from the lowest energy level to the energy level at the lower edge of the band gap (Figure 3). Since filling of energy is from the lowest energy level, this band is usually almost full.

2.15.4. CONDUCTION BAND:

The conduction band consists of energy levels from the upper edge of the band gap and higher (Figure 3). To reach the conduction band, the electrons in the valence band should have enough energy to cross the band gap. Once the electrons are excited, they subsequently relax back to the valence band (either radiatively or non-radiatively) followed by a subsequent emission of radiation.

CHAPTER 3. PHOTOLUMINESCENCE

3.1. LUMINESCENCE:
Luminescence is "cold light" that can be emitted at normal and lower temperatures. In luminescence, some energy source kicks an electron of an atom out of its lowest energy "ground" state into a higher energy "excited" state; then the electron returns the energy in the form of light so it can fall back to its "ground" state. With few exceptions, the excitation energy is always greater than the energy (wavelength, color) of the emitted light. If we lift a rock, our muscles are supplying energy to raise the rock to a higher-energy position. If we then drop the rock, the energy we supplied is released, some of it in the form of sound, as it drops back to its original low-energy position. It is somewhat the same with luminescence, with electrical attraction replacing gravity, the atomic nucleus replacing the earth, an electron replacing the rock, and light replacing the sound. There are several varieties of luminescence, each named according to the source of energy. Many materials are capable of emitting visible luminescence when subjected to some form of excitation such as UV light (photoluminescence), nuclear radiation such as rays and and particles

(scintillation), mechanical shock (triboluminescence), heat (thermo luminescence), chemical reactions (chemiluminescence), and electric fields (electroluminescence). There are two pre-requisites for luminescence: (1) the luminescent material must have a semiconductor structure with a nonzero band gap Eg (e.g. metals do not luminescent since they have no band gap); (2) energy must be imparted to this material before luminescence can take place.

3.2 PHOTOLUMINESCENCE:
Photoluminescence (abbreviated as PL) is a process in which a substance absorbs photons (electromagnetic radiation) and then re-radiates photons. Quantum mechanically, this can be described as an excitation to a higher energy state and then a return to a lower energy state by the emission of a photon. The mechanism of photoluminescence in semiconductors is schematically illustrated in Figure 3.1, which plots the E-k diagrams for a direct band gap material (left) and an indirect gap material (right), where E and k are respectively the kinetic energy and wave vector (or "momentum vector") of the electron or hole (E = k2
2

/ 2m* where

= h / 2 is the Planck constant and m* is the electron or hole

effective mass). The direct and indirect gap materials are distinguished by their relative positions of the conduction band minimum and the valence band maximum. In a direct gap material, both the conduction

band minimum and the valence band maximum occur at the zone center where k = 0. In an indirect gap material, however, the conduction band minimum does not occur at k = 0, but rather at some other values of k.

Figure 3.1. Schematic band diagrams for the photoluminescence processes in a direct gap material and an indirect gap material. The shaded states at the bottom of the conduction band and the empty states at the top of the valence band respectively represent the electrons and holes created by the absorption of photons with energy > Eg. In a direct gap material, the conduction band minimum and the valence band maximum occur at the same k values. Both the photon absorption and emission (i.e. the electron-hole recombination) processes can conserve momentum without the assistance of phonons, since the momentum of the absorbed or emitted photon is negligible compared to the momentum of the electron. Therefore photon absorption and emission processes are represent by vertical arrows on E-k diagrams. In an indirect gap material, the conduction band minimum and the valence band maximum occur at different k values. As a result, to conserve momentum, the photon absorption process must involve either absorption (indicated by a "+" sign) or emission (indicated by a "-" sign) of a phonon, while the PL process requires the emission of a photon. Since the energy of a phonon (~ 0.01 eV) is much smaller than the energy of the PL photon, for an indirect gap material, the peak energy of the PL also roughly reflects

its band gap. Upon absorption of an UV or visible photon with an energy exceeding the band gap Eg (the gap in energy between the valence band and the conduction band) of the material, an electron-hole pair is created and the electron is excited to states high up in the conduction band. For an indirect band gap material of which the conduction band minimum and the valence band maximum have different k values. Conservation of momentum implies that the photon absorption process must be assisted by either absorbing or emitting a phonon (a quantum of lattice vibration), because the electron wave vector must change significantly in jumping from the valence band in state to a state in the conduction band, and the absorption of a photon alone cannot provide the required momentum change. The excited electron and hole will not remain in their initial excited states for very long; instead, they will relax very rapidly (~ 10-13 s) to the lowest energy states within their respective bands by emitting phonons. When the electron finally arrives at the top of the valence band, the electron-hole pair can recombine radiatively with the emission of a photon (luminescence), or nonradiatively by transferring the electron's energy. Just like the photon absorption process discussed above, the electron-hole recombination in a direct band gap material does not involve any phonons since there is no need for momentum change for the electron. In contrast, in an indirect gap material, the excited electron located in the conduction band needs to undergo a change in momentum state before it can recombine with a hole in the valence band; conservation of momentum demands that the electron-hole recombination must be accompanied by the emission of a phonon, since it is not possible to make this recombination by the emission of a photon alone. Compared to the photon absorption process in an indirect gap material for which conservation of momentum can be fulfilled by either absorption or emission of a phonon, in the electron-hole recombination process phonon absorption becomes negligible, whereas phonon emission becomes the dominant momentum conservation mediator because (1) the number of phonons available for absorption is small and is rapidly decreasing at lower temperatures, whereas the emission of phonons by electrons which are already at a high-energy state is very probable; and (2) an optical transition assisted by phonon emission occurs at a lower photon energy Eg - h phonon absorption results in a higher photon energy of at least Eg + h
phon

than the gap energy, whereas which can be more readily

phon)

phon,

re-absorbed by the semiconductor nanoparticle. But note that the energy of a phonon (h

is just in

the order of ~ 0.01 eV, much smaller than the energy of the electron-hole recombination luminescence photon. The energy separation between the electrons and the holes approximately equals to the energy of the band gap. Therefore, the luminescence emitted by both types of semiconductors occurs at

energy close to the band gap Eg. The PL efficiency is determined by the competition between radiative and nonradiative recombination. For an indirect gap material, the PL process, which requires a change in both energy and momentum for the excited electron and hence involves both a photon and a phonon, is a second-order process with a long radiative lifetime (~ 10-5 -10-3 s), and therefore a relatively small efficiency because of the competition with non radiative combination. In contrast, in a direct gap material, the emission of a PL photon does not need the assistance of a phonon to conserve momentum. Therefore, the PL process in a direct gap material is a first-order process with a much shorter radiative lifetime (~ 10-9 -10-8 s) and a much higher PL efficiency in comparison with an indirect gap material.

3.3. FORMS OF PHOTOLUMINESENCE:

3.3.1. FLUORESCENCE:
When a source of energy such as thermal energy is applied to a fluorescent material, high energy particles or photons collide with the electrons in the material causing them to become excited and jump to a higher energy level. The electrons in the excited state have the same spin as they did in the ground state. The electrons in the excited state are not stable and become de-excited and move back down to lower energy level releasing energy in the form of light. When the source of energy is removed the light emission ceases. A fluorescent state can exist for only 10- 5 to 10- 8 seconds. One example of this phenomenon is a black light poster. Black light poster is painted with fluorescent ink. When ink is exposed to black light, it absorbs the black light which excites the electron in the ink. As the electron moves back to their ground state they emit light in the green and yellow wavelength.

3.3.2. PHOSPHORESCENCE:
Phosphorescence is similar to fluorescence except the light emission continues even after the source of energy is removed. A phosphorescence material emits light after it absorbs energy. The absorbed energy excites electron in a phosphorescence material. While excited, the electron experiences the change in spin. This change in spin placed the electron in a metastable position from which they cannot move back into the ground state. As they do so they emit light because of the slow glow decay due to the electrons change in spin the light continues after the exciting source is removed. In another words we can say that when electron gets excited and its spin does flip it takes much longer for it to release the energy and come back down to the ground electronic state, this is phosphorescence. Phosphorescence is temperature dependent and it can exist 10- 4 seconds to several hours.

Phosphorescent materials are used in glow in the dark toys that emit light for many hours after a light source is removed. Example of phosphorescence is glow in a dark pumpkin. Luminous zinc sulfide use as a glow powder. Glow powder works by absorbing surrounding light energy and then releasing that energy when the light goes out. When the electrons in the atom of zinc sulfide become excited, they move further away from the nucleus into higher orbit. The electron will remains in the excited state as long as they receive light to energize them. But when the light used as an exciter is removed, the electron will slowly return to their original lower orbit. They give up the energy that excited them in the form of light.

The major difference in the two processes is the decay time of the emitted light. Fluorescence is fast, of the order of milliseconds. Phosphorescence is slow, of the order of seconds to minutes or even hours. The reason for the difference is the electronic processes involved.

CHAPTER 4. QUANTUM WELL

4.1. QUANTUM WELL:

We think of a normal well as a hole in the ground. A quantum well is analogous and represents the same concept: Energy. For example, if the hole in the ground was 10 meters down, then we need energy of our mass times the height of the well. Now lets apply this concept to the world of quantum mechanics. Lets use an electron as the item trapped in a well. Lets look at the simplest case of electron motion: 1 dimension, or a straight line. Lets say there are atomic forces on either side of the electron pushing against it, preventing it from going past them. Now from the famous Schrdinger equation that defines electron motion, knowing that the energy with which the atoms on either side 'push' on the electron, produces a startling result: the amount of energy that electron has is quantized. For example the electron can have 1 joule or 2 joule, but nothing in between. The energy levels of the electron can only exist in these discrete values until it has enough energy to overcome the barrier and 'escape'. Another interesting result of the quantum well, is that the electron motion is stationary! Electrons do not 'bounce' back and forth in a well like we imagine a rubber ball hitting a wall. The Schrdingers equation describes a wave like nature of an electron and therefore there will be certain 'vibrations' of this wave that don't look like they are moving at all. We can verify this by vibrating a string faster and faster until we don't

see the string moving. Increasing it faster and faster makes it move again until it comes to the next vibration that looks standing still (this is called a standing wave and only occurs at certain frequencies or 'vibrations'). In order to calculate these energies we need to solve the Schrdinger equation.

The Schrodinger wave equation is,

H = E
Where

H=

+V + V = E

But for free particle moving in one dimension i.e. along x-axis,

Where

= E

= h/2, h is planks constant, m is the mass of the particle, is the wave function, V is the

magnitude of the potential and E is the particles total energy. The wave function and quantized energy levels are,

= sin ( E=

) )
n = 1, 2, 3.

Where L is the size of the box. The energy levels increase with n2, meanings that high energy levels are separated from each other by a greater amount than low energy levels are. The lowest possible energy for the particle (its zero-point energy) is found in state 1.

E1 =

Note that the lowest possible energy, namely E1, is not zero although the potential is zero within the well. Only discrete energy values are obtained. The energy difference between adjacent energy levels increases as the energy increases. An electron occupying one of the energy levels can have a positive or negative spin

(s = or s = -).

4.2. HOW QUANTUM WELLS ARE MADE?

Quantum well uses the properties of electron behavior and band gaps to work. Band gaps are area in an electrons orbital between the ground state where the electrons rest normally and the conduction band, the higher energy orbital electron move to when they are excited. The gaps are barrier between the ground state band and conduction band which prevent the electrons from reaching the conduction band without gaining more energy than they have in their ground states. The larger the band gap, the more energy is necessary for the electron to jump this gap, and reaches the conduction band. Once the electron reaches the conduction band, it releases its excess energy and fall back into its ground state. By placing microscopically thin semiconductor between metal with band gaps too wide for electrons not to jump easily, scientists can force the electrons to remains in the two dimensional area of the thin semiconductor. Trapping electrons in this manner allows for specific energy manipulation. Since the electrons can only move in two directions. Quantum well is named wells not only because of their behavior of trapping electrons like a well would trap water but also because of their appearance when graphed. When quantum wells are pictured on energy versus position graph, they look like deep valleys, or well in a rectangular shape, figure 4.3.

Now if a semiconductor material with a small energy gap is sandwiched between energy barriers made of a semiconductor material with a large energy gap, a quantum well is formed between the barriers. Once an electron is captured into this well, the probability to escape from the well is limited. Moreover the restriction on the movement of electron into this plane a two dimensional world, affects also the energy as compared to a free electron in the three dimensional case. Energy and position is dependent on the height and width of the barrier.

Now taking a material like gallium arsenide a semiconductor which is sandwiched between two layers of a material with a wider band gap like aluminum gallium arsenide.

4.3. GaAs/AlGaAs QUANTUM WELL:

A quantum well is usually made of material like gallium arsenide surrounded by aluminium gallium arsenide. The band gap of AlGaAs is larger than that of GaAs and the band lies up so that the lowest

conduction band and valence band states of the GaAs lie within the gap of the AlGaAs. This means that the electrons in the GaAs layer are trapped by potential barriers at each side due to the discontinuity in the conduction band. Similarly holes are trapped by the discontinuity in the valence band. These barriers quantize the states in the z-direction but the motion in the x-y plane is still free.

GaAs is a semiconductor having a direct band gap of 1.42eV while AlAs has an indirect band gap of 2.17eV. The energy band gap of AlxGa1-xAs alloys depends on the aluminum content x. The ternary Alx Ga1-x As for < 0.45 is a direct gap semiconductor, having a band gap of 1.42+1.25(x) eV. Where x is the aluminium fraction Alx Ga1-x As alloy. If one GaAs is sandwiched between two pieces of Alx Ga1-x As creates the quantum well system.

4.4. QUANTUM WELL GROWTH:

There are at least two techniques by which quantum well structures can be grown, molecular beam epitaxy (MBE) and metal-organic chemical vapor deposition (MOCVD). Both can achieve a layer thickness control close to about one atomic layer. MBE is essentially a very high vacuum technique in

which beams of the constituent atoms or molecules (e.g., Ga, Al, or As) emerge from ovens, land on the surface of a heated substrate, and there grow layers of material. Which material is grown can be controlled by opening and closing shutters in front of the ovens. For example, with a shutter closed in front of the Al oven, but open shutters in front of the Ga and As ovens, GaAs layers will be grown.

Opening the Al shutter will then grow the alloy AlGaAs, with the relative proportion of Ga and Al controlled by the temperatures of the ovens. With additional ovens and shutters for the doping materials, structures of any sequence of GaAs, AlAs, and AlGaAs can be grown with essentially arbitrary doping.

4.4.1. MOLECULAR BEAM EPITAXY:

Epitaxy = Epi+taxis, epi means upon and taxis means arranged. The arrangement of atoms on an ordered substrate. Two principle commercial processes exist for depositing epitaxial layers of GaAs and AlGaAs. These are metal organic chemical vapor deposition (MOCVD) and molecular beam epitaxy (MBE). Although both of these processes are capable of depositing the required layers, only MBE affords the precise control necessary to grow high quality quantum well structures. In these epitaxial growth techniques, one begins with a substrate on which the layers are grown. A substrate, also called a wafer, is usually a 2 or 3 single crystal of GaAs about 500m thick. Molecular beam epitaxy takes place in high vacuum or ultra-high vacuum (108 Pa). The most important aspect of MBE is the slow deposition rate (typically less than 1000 nm per hour), which allows the films

to grow epitaxially. The slow deposition rates require proportionally better vacuum to achieve the same impurity levels as other deposition techniques. In solid-source MBE, ultra-pure elements such as gallium and arsenic are heated in separate quasiKnudsen effusion cells until they begin to slowly sublimate. The gaseous elements then condense on the wafer, where they may react with each other. In the example of gallium and arsenic, single crystal gallium arsenide is formed. The term "beam" means that evaporated atoms do not interact with each other or vacuum chamber gases until they reach the wafer, due to the long mean free paths of the atoms.

During operation, reflection high energy electron diffraction (RHEED) is often used for monitoring the growth of the crystal layers. A computer controls shutters in front of each furnace, allowing precise control of the thickness of each layer, down to a single layer of atoms. Intricate structures of layers of different materials may be fabricated this way. Such control has allowed the development of structures where the electrons can be confined in space, giving quantum wells or even quantum dots. Such layers are now a critical part of many modern semiconductor devices, including semiconductor lasers and light emitting diodes. In systems where the substrate needs to be cooled, the ultra-high vacuum environment within the growth chamber is maintained by a system of cryopumps, and cryopanels, chilled using liquid nitrogen or cold nitrogen gas to a temperature close to 77 Kelvin. Cryogenic temperatures act as a sink for impurities in

the vacuum, so vacuum levels need to be several orders of magnitude better to deposit films under these conditions. In other systems, the wafers on which the crystals are grown may be mounted on a rotating platter which can be heated to several hundred degrees Celsius during operation. In addition to growing GaAs and AlGaAs, an additional silicon source allows one to grow N-type GaAs/AlGaAs and a beryllium source allows one to grow P-type GaAs/AlGaAs. Many other materials have been successfully grown by MBE. These include; InAs, InGaAs, InGaAsP, GaSb, silicon and germanium.

4.5. OPTICAL PROPERTIE OF QUANTUM WELL:

4.5.1. QUANTUM WELL ELECTRO ABSORPTION PHYSICS:
When electric fields are applied to quantum wells, their optical absorption spectrum near to the band gap energy can be changed, and effect we can call electro absorption. Such effects have been extensively investigated for optical modulators and switches. There are two very distinct directions in which we can apply electric fields to quantum wells, either with the electric fields parallel to the layers or with the electric field perpendicular to the layers. The case of fields perpendicular to the layers is the one most peculiar to quantum wells, and it is called the Quantum-Confined Stark Effect (QCSE).

4.5.1.1. QUANTUM-CONFINED STARK EFFECT:

The quantum-confined Stark effect (QCSE) describes the effect of an external electric field upon the light absorption spectrum or emission spectrum of a quantum well (QW). In the absence of an external electric field, electrons and holes within the quantum well may only occupy states within a discrete set of energy sub bands. Consequently, only a discrete set of frequencies of light may be absorbed or emitted by the system. When an external electric field is applied, the electron states shift to lower energies, while the hole states shift to higher energies. This reduces the permitted light absorption or emission frequencies. Additionally, the external electric field shifts electrons and holes to opposite sides of the well, which in turn reduces the recombination efficiency (i.e. fluorescence quantum yield) of the system. The spatial separation between the electrons and holes is limited by the presence of the potential barriers around the quantum well, meaning that excitons are able to exist in the system even under the influence of an electric field. The quantum-confined Stark effect is used in QCSE optical modulators, which allow optical communications signals to be switched on and off rapidly.

4.5.1.2. ENERGY AS A FUNCTION OF WELL WIDTH:

We are now much familiar with quantum well. We take length of the well from zero to L, this is called well width which play important role in quantum well physics.

We know that the wave function of a particle in a well is,

n = sin ( H = eEx
First order perturbation theory is,
( )

= < nHn> = =

( )

( )

Now second order perturbation theory is,

( )

( )

( )

We can write,
( )

|
( )

|
( )

Where,

We will get,
( )

For L= 25nm,

( )

= = =

For L= 50nm,

( )

For L= 100nm,

( )

The following figure shows the exciton binding energy in an infinitely deep quantum well as a function of well width.

4.6. APPLICATION/USES OF QUANTUM WELL:

The rapid development of two dimensional semiconductor structures, so called quantum wells, is potential for various electronics applications. Such devices based on quantum wells are widely used already today, but are predicted to considerably gain in importance in the future, in particular within the areas of opto-electronics and high-speed devices. We encounter examples on such applications in daily life, e.g. laser and detector structures in CD players or cash registers, high-frequency modulators in cellular phones and other Tele-communication applications. This rapid development has been possible by

the introduction of growth techniques to manufacture high quality semiconductor structures. These advanced techniques allow growth of a semiconductor structure with a precision down to a single atomic layer. Semiconductor quantum wells are often used in the active regions of laser diodes, where they are sandwiched between two wider layers with higher band gap energy. If a large amount of optical gain or absorption is required, multiple quantum wells (MQWs) can be used, with a spacing typically chosen large enough to avoid overlap of the corresponding wave functions. GaAs and AlGaAs have recently gained much attention in the electronics industry. GaAs infrared light emitting diodes and detectors are being used in remote control equipment. High speed GaAs transistors are now used in satellite communication systems, and the first GaAs computer logic is being developed. The best controlled III-V quantum system is the GaAs/AlGaAs structure with emission in the red range.

CHAPTER 5. QUANTUM WIRE AND QUANTUM DOT

5.1. INTRODUCTION:
During the 1980s, the improved growth techniques have enabled experimentalists to fabricate systems of lower dimensionality, namely quantum wires and quantum dots. In contrast to quantum wells (QWs), where carriers are confined in the direction perpendicular to the layers but move freely in the layer plane, in quantum wires (QWRs) carriers are confined in two directions and move freely along the wire axis. In quantum dots (QDs) they are confined in all three directions resulting in a totally discrete energy spectrum. Semiconductor QWRs has been studied intensively worldwide for a wide spectrum of materials. Such one-dimensional (1D) nanostructure is not only interesting for fundamental research due to their unique structural and physical properties relative to their bulk counterparts, but also offers fascinating potential for future technological applications. QWRs are promising candidates for optoelectronic and microelectronic devices, following the next generation of classical heterostructures and QWs which are now widely used in many applications. In particular, a QWR structure has been proposed as a 1D active region for a semiconductor laser where the electron and hole carriers are allowed to move only in one direction. In contrast, more familiar semiconductor lasers are 3D double heterostructure lasers and 2D QW lasers. Because the 1D density of states (DOS) becomes more enhanced at the bottom of its band edge than the 2D or 3D DOS, a QWR laser is expected to show improvement in lasing performance. Why QWRs are attractive for lasing and also consider the device applications based on 1D quantum structures. The decreased dimensionality of the free carrier motion results in a modification of the DOS of the carriers. The physical meaning of DOS is a measure of the maximum number of carriers that can occupy an energy range. The DOS, due to carrier motion in the x-, y- and z-directions of the active region in a bulk structure, shown in fig: 5.1(a). It can be seen that for a given conduction band or valence band, the DOS is small near the edge of the band and increases with increasing energy. The corresponding DOS, due to confined carrier motion in the z-direction has a step-like shape offering an improvement over the bulk system, shown in fig: 5.1(b). In the QW the number of electrons and holes populating the CB and VB is largest near the edge; therefore such 2D confined quantum structure is more attractive for a laser device. Further limit the motion of the carriers in the y-direction, as in a QWR fig: 5.1(c) where carriers are confined in two directions, or also in x-direction considering a QD fig: 5.1(d) where carriers are confined in all three directions and thus move in zero dimension. The shape of the DOS in QWR and

QD is further improved compared to QW. It has an infinite value near the edges of the bands for the QWR whereas in the QD, carriers occupy discrete levels.

5.2. QUANTUM WIRE:

A quantum wire is a cable or a wire, often similar in function to copper wire, but made with nanotubes of a specific element, usually carbon. Quantum wires are usually conductors, but may also be made as insulators or semiconductors. These wires are ideal for electrical wiring functions and for use on spacecrafts because they are smaller and lighter than their metal counterparts. They are, however, expensive to produce. Nanotubes are man-made microscopic tubes with a diameter of 1 nanometer, which measures 1 billionth of a meter. In comparison, the diameter of a single human hair is measured in micrometers, which are 1,000 times larger than a nanometer. Nanotubes are not only used to create quantum wire, but are used in a variety of scientific fields, including medical research. Nanotubes must be linked or twisted together in chains to form quantum wires, which have a higher conductivity than copper wires, the best metallic conductor of electricity. In theory, a quantum wire has one-sixth of the weight of a copper wire and can conduct electricity up to ten times more efficiently.

Metallic quantum wires may be made out of nickel (Ni) or gold (Au). These wires are largely still experimental, but have uses in electronics and optics.

A quantum wire is an electrically conducting wire, in which quantum effects are affecting transport properties. Due to the confinement of conduction electrons in the transverse direction of the wire, their transverse energy is quantized into a series of discrete values E0 ("ground state" energy, with lower value), E1. One consequence of this quantization is that the resistance of a quantum wire cannot be deduced from the classical formula ( resistivity, l length, S cross section of the wire). Instead an exact calculation of the transverse energies of the confined electrons has to be performed to calculate the wire resistance. Following from the quantization of electron energy, the resistance is also found to be quantized. The importance of the quantization is inversely proportional to the diameter of the nanowire for a given material. From material to material, it is dependent on the electronic properties, especially on the effective mass of the electrons. In simple words, it means that it will depend on how conduction electrons interact with the atoms within a given material.

5.3. QUANTUM WIRE GROWTH:

In the fabrication technology of semiconductor nanometer sized structures, a large number of growth techniques have been developed to fabricate QWRs. A first step toward the realization of a 1D QWR was reported by Petroff in 1982 where GaAs/AlGaAs quantum well-wires with dimensions as small as 200200 A were fabricated using MBE combined with electron-beam lithography and wet/dry chemical etching. However, large wire size fluctuations resulting from lithography and chemical etching processes was observed, and the wire dimensions were rather large, i.e. of order 1000 oA. In 1987 Kapon fabricated GaAs/AlGaAs V-shaped QWR (V-QWR). The V-QWRs were grown by metal-organic vapor phase epitaxy (MOVPE) growth method. A year later, a GaAs/AlGaAs T-shaped QWR (T-QWR) was obtained by Pfeiffer using a MBE machine and cleaved-edge-overgrowth (CEO) technique.

5.3.1. T-SHAPED QUANTUM WIRE:

The concept of the T-shaped QWR structure was originally proposed by Chang, Chang and Esaki in 1985. In 1990, the CEO method combined with MBE was developed by Pfeiffer, which enabled them to combine two thin-film growth processes in two different directions to define QWRs. In fact, they not only fabricated the T-QWR structure by the CEO method, but also showed PL results in 1992. The fabrication process consists of three steps, as illustrated in Fig: 5.3. In the first step, a GaAs/AlGaAs single or multiple QW is grown on a [001] GaAs substrate Fig: 5.3(a). Then, the sample is cleaved in ultrahigh vacuum chamber of a MBE machine to expose the [110] surface Fig: 5.3(b). In the third step, a second MBE growth is immediately performed after the cleavage on the exposed [110] surface. With such method two different structures can be grown: a modulation-doped AlGaAs layer Fig: 5.3(c) or a GaAs well layer followed by an AlGaAs barrier layer Fig. 5.3(d).

In the first structure, electrons are electrostatically confined at the intersection of the first grown QW and the overgrown modulation-doped AlGaAs layers. In the second structure, 1D electronic and hole states are formed at the T intersection of two parent QWs, namely the first QW forming the 'stem' part of the

letter 'T' and the second QW forming the 'arm' part of it, as schematically shown in Fig: 5.3(d). The TQWR is a convenient structure for electron transport since the 1D electron is smoothly connected to the arm QW. This makes the formation of electrical contacts to QWRs easier. The properties of 1D excitons have been intensively studied in such T-QWR structures.

5.3.2. V-SHAPED QUANTUM WIRE:

The typical fabrication process of V-QWR is illustrated in Fig: 5.4. First, using photolithography or electron-beam lithography a photoresist pattern is formed on a GaAs substrate Fig. 5.4(a). Then, Vshaped grooves composed of two intersecting (111) a sidewall facets were realized by wet chemical etching Fig: 5.4(b). In the final step, GaAs QWRs were fabricated at the V-groove bottom by growing GaAs/AlGaAs multilayer on this substrate because the growth rate of GaAs at the V-groove bottom is usually higher than that on the sidewall facets under the growth conditions Fig. 5.4(c). Such vertically stacked GaAs/AlGaAs V-QWRs were obtained. The V-QWR structure has proved itself as one of the most studied structure for 1D exciton properties. A large number of publications have been devoted to the investigation of such V-QWR structures.

5.4. OPTICAL PROPERTIES OF QUANTUM WIRE:

Structural and geometric factors play an important role in determining the various attributes of nanowires, such as their electrical, optical and magnetic properties. Electrical transport properties of nanowires are important for nanowire characterization, electronic device applications, and the investigation of unusual transport phenomena arising from one-dimensional quantum effects. Important factors that determine the transport properties of nanowires include the wire diameter, which is important

for both classical and quantum size effects, material composition, surface conditions, crystal quality, or the carrier mobility. Optical methods provide an easy tool for measuring the electronic structure of nanowires. A variety of optical techniques have shown that the properties of nanowires are different from those of their bulk counterparts. Although optical properties have been shown to provide an extremely important tool for the characterization of nanowire. The wavelength of light used to probe the sample is usually smaller than the wire length, but larger than the wire diameter. Hence, the probe light used in an optical measurement cannot be focused solely onto the wire, and the wire and the substrate on which the wire rests are simultaneously probed. For measurements, such as photoluminescence (PL), if the substrate does not luminescence or absorb in the frequency range of the measurements, PL directly measures the luminescence of the nanowires and the substrate can be ignored. The common method to study nanowires is by photoluminescence. Emission techniques probe the nanowires directly and the effect of the host material does not have to be considered.

5.4.1. PHOTOLUMINESCENCE IN QUANTUM WIRE:

In a photoluminescence (PL) experiment electrons and holes are created by optical excitation. The optically generated electrons and holes rapidly thermalize and relax to the band edge. The charge carriers can also diffuse in the semiconductor material and transfer across heterostructure interfaces, such as from the large band gap shell to the low band gap core in a core-shell nanowire. The electrons and holes can then either recombine radiatively across the band gap, and via energy states in the band gap such as dopants, giving rise to luminescence, or recombine non-radiatively, via lower lying (midgap) energy levels in the band gap, for example surface states. For a nanowire, where the surface to volume ratio is very large and the carriers are close to the surface, the surface states are important non-radiative recombination centers. Since non-radiative recombination processes compete with the radiative recombination for the charge carriers, the number of non-radiative recombination possibilities should be reduced for an efficient light emission. The quantum wire luminescence could not be excited with a laser wavelength of 700 nm. Decreasing the excitation wavelength to 620 nm and below, results in an increase of the wire luminescence. As the band gap increases when the diameter of quantum wire decreased and the energy bands gradually convert into discrete molecular electronic levels. Photoluminescence depends upon the diameter of the wire. The diameter of the wire increases the photoluminescence energy decreases. If the nanowire diameter is small enough, then quantum confinement effect causes the luminescence peak to shift to the high energy side. Indeed,

photoluminescence measurements revealed a clear blue shift of the excitonic emission from single nanowires with decreasing diameter. And increase in diameter, photoluminescence energy decreases and emits red light fig: 5.5.

5.5. APPLICATIONS/USES OF QUANTUM WIRE:

Nanowires still belong to the experimental world of laboratories. However, they may complement or replace carbon nanotubes in some applications. Some early experiments have shown how they can be used to build the next generation of computing devices. The most obvious use for nanowires is in electronics. Some nanowires are very good conductors or semiconductors, and their miniscule size means that manufacturers could fit millions more transistors on a single microprocessor. As a result, computer speed would increase dramatically. Nanowires may play an important role in the field of quantum computers. A team of researchers in the Netherlands created nanowires out of indium arsenide and attached them to aluminium electrodes. At temperatures near absolute zero, aluminum becomes a superconductor, meaning it can conduct electricity without any resistance. The nanowires also became superconductors due to the proximity effect. The researchers could control the superconductivity of the nanowires by running various voltages through the substrate under the wires. Nanowires may also play an important role in nano-size devices like nanorobots. Doctors could use the nanorobots to treat diseases like cancer. Many groups have been able to use nanowires successfully to create such things as memory devices and transistors. For example, groups at the University of Southern California and the NASA Ames Research

Center have created a memory device that will be able to store 40 gigabites per square centimeter, an amazing amount within such a small area.

5.6. QUANTUM DOT:

It is hard to think about a life without semiconductor technology: The entire global information and communications infrastructure is based on semiconductors, and in every one of these applications, size matters. To create computer chips that operate at ever-increasing speeds, engineers must search for ways to decrease device size. One promising way of doing this is to replace electronic semiconductor devices with photonic ones, such as quantum dots. Quantum dots are small devices that contain a tiny droplet of free electrons. They are fabricated in semiconductor materials and have typical dimensions ranging from nanometres to a few microns. The size and shape of these structures and therefore the number of electrons they contain can be precisely controlled; a quantum dot can have anything from a single electron to a collection of several thousands. Quantum dots are semiconductor nanocrystals that are so small thats why consider as dimensionless. Range of quantum dots are from 2-10 nanometers (10-15 atoms) in a diameter.

A quantum dot is a particle having an approximate size of one nanometer which has the display properties of a semiconductor. A semiconductor is a solid material that possesses some amount of electrical conductivity. Silicon is one of the most popular materials used in creating a quantum dot. The size of the quantum dot, one-billionth of a meter, can cause it to exhibit unusual properties that are not present in larger samples of a semiconductor material. These properties could have some benefits to humans including, but not limited to, energy and light production. Unlike some forms of nanotechnology, the quantum dot is not theoretical. It has been created in a real-world setting. The key to the quantum dot is in the electrons. Electrons occupy one of two bands in a materials crystal. By providing the proper stimuli, an electron, or perhaps more than one, can be encouraged to move from

one band to the other. As it moves from one band to the other, it creates a hole, which is positively charged. Together, the hole and the electron are referred to as an exciton. The electron and the hole in the exciton normally keep their distance from each other. This is called the Exciton Bohr Radius. However, if the crystal is reduced in size, it crowds this gap. Once that happens, it changes the crystals ability to absorb and emit energy. At this point, the quantum dot is created. Different colors can be obtained by reducing or increasing the size of the quantum dot. Just as in an atom, the energy levels are quantized due to the confinement of electrons. In some quantum dots even if one electron leaves the structure there is a significant change in the properties. However in the quantum wells density of state is continuous, while in the quantum dot density of state is discrete.

5.7. QUANTUM DOT GROWTH:

Quantum dots are man-made structures, which are constructed by combining different types of semiconductors. For this reason, they are part of a larger group called heterostructures. The most important thing to know about semiconductors is that they have what is called a `band gap', a range of forbidden electron energies. For example, in GaAs, it is not possible for an electron to have any energy between 0 eV and 1.424 eV. However, an electron can have any energy above or below this point. The idea of a band gap is all that is really needed for a qualitative understanding of a quantum dot. There are a number of different ways of constructing quantum dots, and here I discussed gives dots of extremely high quality. Using Molecular Beam Epitaxy (MBE), researchers are able to deposit a semiconductor on a substrate one monolayer at a time. A MBE device consists of a substrate and any number of molecular beams housed in a chamber under strong vacuum. The vacuum ensures that the semiconductors grown in the chamber will be extremely pure. By turning on a combination of molecular beams focused on the substrate, a thin layer of semiconductor can be grown on that substrate.

A MBE setup with three molecular beams, one containing gallium (Ga), one containing arsenide (As), and one containing indium (In). By turning on the Ga and As beams, we can grow a layer of semiconductor GaAs. Next, turn on all three of the beams and grow a very thin layer of InGaAs. Because the lattice constants of the GaAs and the InGaAs are not exactly matched, this layer will be strained. This causes the InGaAs to island, forming small clusters on the nanometer scale. At the initial stage of growth, these islands are dislocation free. The In beam is then turned off and the islands are capped with a second layer of GaAs. These islands of InGaAs embedded within the GaAs matrix are the quantum dots.

The interesting thing about such a creation results from the differences between the band gaps of the two materials. GaAs has a band gap of 1.424 eV and InGaAs has a band gap of 0.75 eV. Therefore, taking a slice through one of the dots, and considering the band gap as a function of the growth axis z shown in Figure. We have what amounts to a `potential well'. This potential well is depicted in Figure. All energies above the solid line in Figure are accessible, but electrons with energies between 0.75 eV and 1.424 eV are `trapped' in the InGaAs dot. If the structure is made small enough, electron motion is essentially impossible. This means that the electrons trapped in the InGaAs have 0 degrees of freedom. Because of this the electrons are in some sense `point-like', and these structures are referred to as quantum dots. the smaller the quantum dot, the more noticeable will be the quantization of the electron's energy levels in the dot. Why should we be interested in such structures? The answer is quantum confinement. An electron's energy becomes quantized in such a structure, like the particle in a square well or like an electron in an atom. Indeed, quantum dots are sometimes called `artificial atoms'.

5.8. OPTICAL PROPERTIES OF QUANTUM DOT:

Quantum dots are tiny particles, or nanoparticles, of a semiconductor material, which range from 2 to 10 nanometers in diameter (about the width of 50 atoms). Because of their small size, quantum dots

display unique optical properties that are different in character to those of the corresponding bulk material. The most immediately apparent of these is the emission of photons under excitation, which are visible to the human eye as light. Moreover, the wavelength of these photon emissions depends not on the material from which the quantum dot is made, but its size. The ability to precisely control the size of a quantum dot enables the manufacturer to determine the wavelength of the emission, which in turn determines the colour of light the human eye perceives. Quantum dots can therefore be tuned during production to emit any colour of light desired. The ability to control, or tune the emission from the quantum dot by changing its core size is called the size quantization effect. The height and energy difference, between energy level increases as the size of the quantum dot decreases. The smaller the dot, the closer it is to the blue end of the spectrum, and the larger the dot, the closer to the red end. Dots can even be tuned beyond visible light, into the infra-red or into the ultraviolet.

5.8.1. PHOTOLUMINESCENCE IN QUANTUM DOT:

As we know that quantum dot band gap is smaller than the surrounding material, so electrons will tend to fall into the dot to reach a lower energy configuration. We can use a laser to excite electrons into the conduction band. Recombination will often produce a photon. The energy of this photon tells us what state the electron and hole were in.

In fig 5.11 shows a simple model for the energy levels in a quantum dot. The grey regions in the diagram represent the conduction and valence band in GaAs. In this experiment, light or laser light shines on the quantum dot and causes electrons to be ejected from the GaAs valence band and pumped up to the GaAs conduction band. These electrons then decay down into the ground conduction state of the quantum dot where they recombine with the hole states in the quantum dot and as a result emits light.

In the strong quantum-confinement regime, the quantum dot size is smaller than the electron hole interaction length, resulting in widely spaced energy states. The quantum dot sizes can be so small that the energy spacing between the allowed states in the conduction and valence bands is large enough, this is called phonon bottleneck. The phonon bottleneck arises when we consider the relaxation of electrons from the conduction band in GaAs into the ground conduction state of the quantum dot. When electrons make a transition between states in the quantum dot, the energy they lose is carried away in the form of phonons. In most semiconductors, excited electrons can relax down to the bottom of the conduction band by losing energy. However, a phonon bottleneck occurs when the spacing between energy states is much larger as is the case in strong quantum confinement. In this case, the probability for a carrier in a higher energetic state to lose its energy to a lower energetic state through these interactions becomes very low. As a

result, electrons cannot relax to the bottom of the conduction band, and so quantum dots with strong quantum confinement should not be expected to emit light from the normal transition across the band gap. Electrons in a quantum dot for which the confinement is suitably small are not able to relax to the ground state where they can radiatively recombine with holes. This should result in a much lower radiative efficiency for quantum dots. However, this phonon bottleneck has not been observed experimentally.

5.9. APPLICATIONS / USES OF QUANTUM DOT:

The ability to tune the size of quantum dots is advantageous for many applications. For instance, larger quantum dots have a greater spectrum-shift towards red compared to smaller dots, and exhibit less pronounced quantum properties. Being zero dimensional, quantum dots have a sharper density of states than higher-dimensional structures. As a result, they have superior transport and optical properties, and are being researched for use in diode lasers, amplifiers, and biological sensors. By adding quantum wires to a quantum dot, these could be used in circuits in place of traditional wires. The benefit of using quantum dots is that there are so many different colors available that more then 1 or 2 different things can be tagged at a time. Another benefit is that quantum dots typically have a much longer life time for florescence then organic dyes. They are used in biology,solar cells, photovoltaics devices, photodetectors devices, and light emitting devices. Using quantum dots as light-emitting diodes to make displays and other light sources, such as "QD-LED" displays, and "QD-WLED" (White LED). White LEDs can make by replacing incandescent light bulbs with red, green, and blue QDs to get white light. It is a developing technology and so there are many applications that have yet to be fully discovered.