2 Fundamentals

Structure of Solids
Structure of Solids 1. Introduction 2. Types of Solids 3 Atomic 3. At i Bonding B di 4. Growth of Semiconductor Materials Reference D.A. Neamen, Semiconductor Physics and Devices (McGraw-Hill, Devices (McGraw-Hill 2003), 2003) Chapter 1 1.
Structure of Solids Introduction
1. Introduction
An IC comprises millions of interconnected transistors transistors, resistors resistors, capacitors capacitors, etc etc. Metals used for interconnects, contacts, and in the transistor structure structure. Examples: aluminium, copper, tungsten, polysilicon, metal silicides. Dielectrics Di l t i for f electrical l ti li insulation, l ti mechanical support and environmental protection; part of device structure (transistor, capacitor dielectric). dielectric) Examples: silicon dioxide, silicon nitride, various polymers. Semiconductors used to make the active device (transistors, LEDs, lasers). Examples: silicon, germanium, GaAs.
Intel Core i7 Processor 45nm process technology 731 million transistors
Structure of Solids - Introduction

Level 7 interconnect Metal vias connection between Interconnect levels. levels Dielectric provides insulation, support Level 1 interconnect Silicon surface devices reside here
Metal
Dielectric insulation
Semiconductor
Cross-section of IBM Microprocessor showing metallization & airgaps
Structure of Solids Introduction

1.2 Semiconductors So called because they have electrical conductivities between that of metals and insulators.
Resistivity at room temperature

1.3 Classes of semiconductors Elemental semiconductors Found in Group IV of periodic table table. E E.g. g silicon (Si) (Si), germanium (Ge) Used in ICs and discrete devices such as transistors, diodes. Compound semiconductors C Compounds d of fG Gp III & Gp G V (III-V (III V s/c / e.g. GaAs, G A GaN, G N AlGaAs) AlG A ) Compounds of Gp II & Gp VI (II-VI s/c e.g. ZnS, CdTe, HgSe) Used in light emitting devices such as LEDs and lasers. SiC used in high high-powered powered devices devices. Metal oxides Many metal oxides are also semiconductors (e.g. ZnO, SnO). Used for gas and chemical sensing. Organic semiconductors Long-chain Long chain polymers (e (e.g. g poly-paraphenylen-vinylene poly paraphenylen vinylene PPV) Small molecules (e.g. pentacene) Used in OLED displays and polymer electronics.
Atomic number Z Relative Atomic Mass
Common dopants for Si
* Group III (B, Ga, In) and Group V (P, As, Sb) elements used to dope Si.
Structure of Solids Types of Solids
2. Types of Solids
Classification according to the size of the ordered region: Amorphous Order in the range of a few atoms or on molecular dimensions Single-crystal One large crystal making up entire volume of material. Regularity of atomic arrangement present throughout entire solid. Polycrystalline y y High degree of order over many atomic / molecular dimensions. Ordered single-crystal regions are called grains. Grains vary in size and orientation. Grains are separated by grain boundaries.
Structure of Solids Types of Solids

Example: MOSFET
Symbol
Schematic
Polycrystalline silicon (Polysilicon)
Amorphous oxide
Single-crystal silicon
Electrical properties of single-crystal silicon are superior to those of polysilicon.
Structure of Solids Atomic Bonding
3. Atomic Bonding
3.1 Covalent Bonding in Silicon Silicon (atomic number = 14) has 14 electrons occupying 3 shells: shell n = 1: 2 electrons (complete shell) shell n = 2: 8 electrons (complete shell) shell n = 3: 4 electrons (partially filled shell) Th The outermost t t shell h ll (or ( the th valence l shell h ll) is i only l partially ti ll filled, fill d with ith 4 out of 8 possible states being occupied by electrons. Having g 4 electrons in the valence shell p places Silicon in Group p IV of the periodic table. Other Group IV elements include carbon (C) and germanium (Ge).

Covalent bonds are formed when 2 atoms share a pair of electrons to form closed / complete valence shells (of 8 electrons). Group IV elements such as C, Si, Ge, tend to form covalent bonds. Each atom has 4 valence electrons which form 4 covalent bonds with 4 adjacent atoms atoms. Results in a macromolecular solid.
Silicon atom forming 4 covalent bonds with 4 neighbouring atoms

The silicon atoms are arranged symmetrically in space the 4 atoms are arranged in a tetrahedron around the central atom. If we replicate arrangement of atoms, we end up with the diamond crystal structure. In a crystal, the atoms are positioned on a periodic array of points in space. Most Group IVA elements have the diamond structure C, Si, Ge, Sn.

Characteristics of covalently bonded solids (macromolecules): Hard & strong with high melting points, e.g. 3815oC for diamond, 1414oC for silicon (strong bonds). Brittle. Electrically insulating at low temperatures (valence electrons are involved in covalent bonding). Silicon and germanium are semiconductors at room temperature (explained later).

3.2 Metallic Bonding Simple metals have a valence shell with 1, 2, or 3 electrons (e g Na, (e.g. Na Ca Ca, Al) Al). In a solid metal, the valence electrons become free from the parent atom, and each metal atom contributes its valence electrons to a common pool of electrons. Can be visualized as positive metallic ion cores (atoms without their valence electrons) in a sea of electrons. Mobile free electrons give rise to good electrical & thermal conduction.
Structure of Solids Growth of Semiconductor Materials
4. Growth of Semiconductor Materials

Very Large Scale Integration (VLSI) ICs are fabricated on single-crystal silicon. The starting wafer is cut from a single-crystal of silicon. Typical wafer diameter in current p production is 300 mm. In the 1970s, , Si wafers were typically 75 mm in diameter. 450 mm wafer production is being planned.
Dicing Testing Packaging
300 mm wafer

4.1 Growth of silicon crystal using Czochralski (CZ) method Start with purified polysilicon chips in a crystal pulling furnace, & melted (m.p. = 1410oC). Desired impurities (dopants) added to melt to control the electrical characteristics of the grown crystal. Ti Tiny seed d crystal t l( (single-crystal i l t l of f desired crystal orientation, low defect density) is brought into contact with the surface of the melt. melt Seed crystal is withdrawn slowly as it is rotated. Liquid solidifies onto the seed crystal as it is pulled.

Ingot is sliced up into wafers ~1mm thick. Wafers are then lapped & polished.
Wafer Polishing
Ready for processing
Structure of Solids key knowledge

Rough orders of magnitude of carrier concentrations in metals & semiconductors. Group III elements (B, Al, Ga, In), Group IV elements (C, Si, Ge), and Group V elements (P, As, Sb). Classification of solids (amorphous (amorphous, polycrystalline polycrystalline, crystalline) crystalline). Nature and characteristics of bonding in Si (C, Ge). Nature of the metallic bond.
Band Theory
Band Theory 1. Energy Concepts 2. Formation of Energy Bands 3 Electrical 3. El t i l C Conduction d ti 4. Metals, Insulators, and Semiconductors Reference D.A. Neamen, Semiconductor Physics and Devices (McGraw-Hill, Devices (McGraw-Hill 2003), 2003) Chapter 3 3.
Band Theory Energy Concepts
1. Energy Concepts
1 1 Potential & Kinetic Energy of an Electron 1.1 Electron is a negatively-charged particle with a charge of ( e) or ( q) where e (or q) = 1.602 1 602 x 10-19 C is the fundamental unit of charge.
Consider a stationary electron (i.e., no kinetic energy, EKE = 0) in vacuum i b in between t 2 plates l t of f a bi biased d parallel plate capacitor (LH plate = 0V, RH plate = +5V). Between the plates, the voltage increases linearly from 0V to +5V.

The potential energy (P.E.) of the electron (in vacuum) is given by the product of its charge, Q = e, and the potential / voltage that it is in, V(x): EPE = Q.V Q V(x) = ( (-e). ) V(x) Example: if the electron is half-way between the plates where V = +2.5V, the P E of the electron is: P.E. EPE = Q.V = (-1.602 x 10-19 C).(+2.5 V) = - 4.005 x 10-19 J (or C.V) Since we are dealing with electrons with an elementary charge of ( e), e) it is more convenient to adopt a unit of energy, the electron-Volt (eV), where 1 eV 1.602 x 10-19 J Thus, for the above example, we have EPE = Q.V(x) = (-e C).(+2.5 V) = -2.5 eV This is of course very convenient if an electron is at a voltage of xxx V, then its potential energy is simply (xxx) eV. Q: If you were dealing d li instead i t d with ith a positive iti i ion of f say, C Ca2+, what h t would ld it its corresponding PE be at +2.5V?

If we plot the voltage and potential energy gy of the electron as a function of distance between the two plates, we see that the potential energy plot (units eV) for the electron is a mirror reflection of the voltage plot (units V).

So far, we have considered only the potential energy. What if the electron is not stationary (i.e., it has finite velocity & hence kinetic energy)? Consider an electron initially at rest in vacuum next to the LH plate where V = 0V. If the electron is free to move, it will be attracted tt t d towards t d the th +ve RH plate l t it is accelerated by the electric field between the plates. The electron energy gains K.E. at the expense of a drop in potential energy. The total energy of the electron remains the same as when it started: Etot = EPE + EKE

Example: mid-way collision event with 100% energy loss. Example: multiple collisions.

With frequent multiple collisions along the electron trajectory: 1. The KE remains small due to frequent collisions. 2. The total energy of the electron decreases almost continuously continuously. 3. The total energy (= PE + small KE) is close to the PE curve. In a conductor, electrons undergo frequent collisions (scattering) will discuss next next.
Analogy: ball rolling down a slope

1.2 Workfunction of a Metal Surface In a simple model of free electrons in a metal, the valence electrons from the constituent atoms are delocalized from the parent atoms (ions) which allow them to be mobile and conduct electricity. These electrons are not truly free in the sense than an electron in vacuum is free. While the conduction electrons can move around in the metal, they are still attracted by charges (positive metal ions and other (p electrons) in the metal. The energy required* to extract a conduction electron from a metal into vacuum is called the workfunction of the metal. Some typical metal workfunctions:
* At T = 0K
Platinum ( (Pt) ) Gold (Au) Tungsten (W) Al i i Aluminium (Al) Cesium (Cs)
5.65 eV 5.1 eV 4.5 eV 4 3 eV 4.3 V 2.1 eV

If we compare a (stationary) electron in vacuum, to a (stationary) electron in the metal at the same potential (voltage), the energy of the electron in the metal is lower by an amount equivalent to the workfunction. Returning to our illustration of the parallel plate capacitor, now let us place l ab bar of f metal t lb between t th the two electrodes so that the metal is biased. We can compare the potential energy of a conduction electron in the metal, metal and the energy of an electron in vacuum at the same position between the plates (assume workfunction = 4.0 4 0 eV)

The potential energy an electron has in vacuum is represented by the vacuum level. If we assume that a conduction electron in the metal starts at rest from the LH end of the bar bar, its initial total energy is 4.0eV (relative to the vacuum level). The electron is accelerated by y the electric field, but it does not gain much velocity before it undergoes a scattering event. The mean free path is typically of the order of nm. Hence the average KE remains very small*. The resulting total energy (PE+KE) is thus nearly equal to to the PE. Most of the energy is dissipated as heat.
* additional KE gained from the E-field, on top of the KE due to the random velocity of the electron
Band Theory Formation of Energy Bands
2. Formation of Energy Bands

2 1 Splitting of energy levels 2.1 Consider a simple metal atom, sodium (Na, Z = 11) In ground state, electrons fill available states with the lowest energy levels. Valence shell has 1 out of 8 states filled.
Sodium atom (schematic) and corresponding energy levels

Consider 2 sodium atoms brought together to form a bond. At bonding distance, the valence shells (3rd shells) of the 2 atoms overlap. When the shells overlap, the energy level of the shell splits into 2 (e.g. E3s now has a higher & a lower energy level). Number of states for the system of 2 atoms is preserved (Pauli Exclusion Principle) e Principle). e.g. g isolated atom has 2 states at E3s, 2 bonded atoms has 4 states at E3s split energy levels. Electrons occupy the lowest-energy states available in the system of 2 atoms.
Formation of bond between 2 sodium atoms

Each additional atom contributes an additional energy level. The total number of states are preserved. A sodium atom has 8 states in the valence (3rd) shell. If we have N sodium atoms bonded together, we end up with 8N states from this shell. Each atom has 11 electrons electrons. For a system of N atoms atoms, the 11 x N electrons fill up the available states starting with the lowest energy.
Formation of bond between 4 sodium atoms

In practice, we are dealing with a huge number of atoms, e.g., in 1cm3 of Na, there are ~2.5x1022 atoms. The atomic energy levels split into e e.g. g 2 2.5x10 5x1022 discrete energy levels that are very closely spaced, to form an energy band. The total number of states are still preserved, i.e., within the band there is a fixed number of states. The values of energy an electron can have within a band is almost continuous. BUT the energy levels are discrete, BUT, discrete and each has a fixed number of states states.
Formation of energy band in solid sodium

F For different diff materials, i l d depending di on the h way i in which hi h the h electron l shells h ll interact, some bands can overlap each other, forming a continuous band of energies without any breaks. If the energy bands are separated, then we end up with forbidden bands (no states) between allowed bands (states exist in the band). Electrons cannot exist in the forbidden band(s) since there are no states there there. They can only occupy states that are unoccupied in the allowed band(s).

2.2 Formation of bands in Silicon (Z = 14) Silicon atom has14 electrons in 3 shells. In ground state, electrons fill available states with the lowest energy levels. Valence shell has 4 out of 8 states filled.
Silicon atom (schematic) and corresponding energy levels

Unlike sodium, silicon with its 4 valence electrons (3rd shell) forms 4 covalent bonds with 4 neigbouring atoms. The result is that when N silicon atoms are bonded together, the 3s & 3p orbitals combine** and the energy levels split into 2 bands of 4N states each. each The 4N valence electrons completely occupy the lower band.
Formation of energy bands in silicon

** sp3 hybridization
Band Theory Electrical Conduction
3. Electrical Conduction
The energy band model of a solid has important implications: 1. An empty band cannot support electrical conduction there are no electrons in such a band to carry current. 2 A band that is fully occupied cannot support conduction either! A full 2. band has plenty of electrons, but it has no available states within the band for the electrons to move into. 3. For conduction to take place in a particular band, the band must have BOTH electrons AND empty states, i.e., the band is only partially occupied.
Band Theory Electrical Conduction

For electrical conduction to take place within a particular band, the electrons must be able to move & gain kinetic energy when an electric field is applied. If there are unoccupied p states above the occupied p p part of a p partially-filled y band, the electrons can move into these higher energy states. The increase in energy is the kinetic energy gained.
Band Theory Metals, Insulators, and Semiconductors
4. Metals, Insulators, and Semiconductors

Band theory allows us to explain the conduction behaviour in solids. An electron that takes part in conduction will be in the conduction band. Electrons in the valence band correspond to the valence electrons of the constituent tit t atoms. t 4.1 Metals Good conductors of electricity because they have partially filled bands bands.
Typical metal band diagram (at T = 0K)

4.2 Insulators Most covalently bonded solids have valence bands that are completely filled, and the conduction band completely empty empty. Bandgap between the valence band and the conduction band is ~several eV. At room temperature (300K) where the average thermal energy of a free electron is about 3/2kT (0.04 eV), electrons at the top of the valence band do not have sufficient energy to hop across into the lowest available states at the bottom of the conduction band. Material is therefore insulating.
Typical insulator band diagram (at T = 0K)

4.3 Semiconductors Band diagram for semiconductors is basically the same as that of an insulator. insulator However, the bandgap is much smaller, e.g., for silicon, the bandgap is 1.12eV at 300K. At T = 0K, silicon is an insulator since the valence band is completely filled (no available empty states), while the conduction band is empty (no electrons).
Silicon band diagram at T = 0K (schematic) - insulating

At room temperature, some of the electrons nearer the top of the valence band have sufficient thermal energy that is greater than the bandgap to jump into states near the bottom of the conduction band. As the average thermal energy of the electrons is only ~0.04eV, the fraction of electrons with thermal energy > 1.1eV is very, very small. The probability of an electron at the top of the valence band jumping across the bandgap into a state at the bottom of the conduction band is only ~10-10 at 300K.
Silicon band diagram at T = 300K (schematic) - semiconducting

An electron excited into the conduction band can now take part in electrical conduction (plenty of available, empty states in conduction band). The electron that used to occupy a state in the valence band has now left an empty state in the valence band. The valence band is now no longer fully occupied. The empty state left in the valence band allows the now partially-empty partially empty valence band to take part in electrical conduction conduction. The motion of these empty states in the valence band give rise to the concept of positive charge carriers known as holes in the valence band.
Silicon band diagram at T = 300K (schematic) - semiconducting

The difference between an insulator and a semiconductor is one of degree rather than kind insulators have larger bandgaps, while semiconductors have smaller bandgaps. An insulator at room temperature (e.g. diamond, bandgap 5.5eV) can become semiconducting at higher temperature as the average thermal energy of the electrons increases increases.
Silicon band diagram (schematic) & electron concentration in CB

4.4 Typical Bandgaps
Semiconductor Silicon (Si) Germanium ( (Ge) ) Gallium Arsenide (GaAs) Indium Antimonide (InSb) Band gap in eV at 300 K * 1.12 0.66 1.42 0.17
Bandgaps of selected semiconductors at 300K (Note: Bandgap varies slightly with temperature)
Insulator Silicon Dioxide (SiO2) Silicon Nitride (Si3N4)
Band gap in eV at 300 K 9 5
Bandgaps of selected insulators
Band Theory Key knowledge

Energy concepts Unit of eV. PE of electron in a potential V. Concept C of f workfunction. kf i Concept of vacuum level. Energy of an electron in a biased metal conductor & what happens to the energy components t as the th electron l t moves. Band theory Appreciation of how energy bands are formed in a solid solid, understand what they represent, and restriction on the number of states & electrons in a band. Understand the filling of energy bands at ground state. Understand why conduction can only take place in partially-filled bands bands. Typical / generic band structure of insulators, conductors, and semiconductors. Thermal generation of carriers in a semiconductor and how this leads to electrical conduction conduction. Typical bandgaps of semiconductors semiconductors.
ANNEX Periodic Table
The Semiconductor in Equilibrium
The Semiconductor in Equilibrium 1. Charge Carriers in Semiconductors 2. Doping of Semiconductors 3 Carrier 3. C i C Concentration t ti Reference D.A. Neamen, Semiconductor Semiconductor Physics and Devices (McGraw-Hill, 2003), Chapter 4.
The Semiconductor in Equilibrium Charge Carriers in Semiconductors
1. Charge Carriers in Semiconductors 1 1 Bond Model 1.1 1.2 Carrier Properties
The Semiconductor in Equilibrium Charge Carriers in Semiconductors 1.1 Bond Model Purpose is to relate the energy band model d l with ith th the more elementary l t bond model which is less abstract. Silicon (Z = 14) ) has 4 valence electrons. In the bond model of silicon, silicon is bonded to 4 other silicon atoms by covalent bonds each covalent bond involves the sharing of a pair of electrons (one from each atom) atom). At T = 0K, all the valence electrons are involved in covalent bonds. No free electrons for electrical conduction. (Inner core electrons are tightly bound to the nucleus and are thus not mobile.) bil )
The Semiconductor in Equilibrium Charge Carriers in Semiconductors In 2-dimensional representation:
Silicon at T = 0K
The Semiconductor in Equilibrium Charge Carriers in Semiconductors At temperatures above 0K, some of the electrons have sufficient thermal energy to break free from the covalent bond. The free Th f electron l t are now mobile bil can t take k part t in i electrical l t i l conduction. d ti They are thus known as conduction electrons.
Conduction Electron
Silicon at T > 0K
The Semiconductor in Equilibrium Charge Carriers in Semiconductors The empty state left behind cannot in itself carry current, but it allows other electrons the opportunity of moving without any net input of energy into the system the energy to break a bond will be given given back back to the system when a new bond is formed. As another electron moves into the space, it leaves another behind it, etc.
Successive movement of electrons into spaces left behind
The Semiconductor in Equilibrium Charge Carriers in Semiconductors Instead of seeing a successive movement of electrons, we can instead consider the motion of the space that is left behind. Th net The t charge h surrounding di th the space i is +e. The moving space may be treated as if it were a positively charged particle, called a hole.
Successive movement of electrons seen as a movement of a hole
The motion of the hole is independent of the electron that once occupied that state. Holes are thus independent carriers.
The Semiconductor in Equilibrium Charge Carriers in Semiconductors Comparing the bond model with the band model At T = 0K
Energy required to break a covalent bond is equivalent to the bandgap Eg.
The Semiconductor in Equilibrium Charge Carriers in Semiconductors Comparing the bond model with the band model At T > 0K
Electron excited into CB is now mobile as there are unoccupied states available. il bl
The Semiconductor in Equilibrium Charge Carriers in Semiconductors Comparing the bond model with the band model At T > 0K
Available state in VB now allows successive electron movement in VB. S Seen as the th motion ti of fah hole l i in th the VB VB.
The Semiconductor in Equilibrium Charge Carriers in Semiconductors Definitions
The conduction band edge, EC, is the lowest energy level in the conduction band. Electrons in the CB normally reside at energy levels around EC as these are the lowest energy states in the CB. The valence band edge, EV, is the highest electron energy level in the valence band band. Holes in the VB normally reside at energy levels around EV as these are the lowest energy states for holes in the VB. The bandgap Eg = EC EV, is the minimum energy required to create an electron-hole pair (EHP). Note that thermal excitation across the bandgap always creates electrons and holes in pairs.
The Semiconductor in Equilibrium Charge Carriers in Semiconductors 1.2 Carrier Properties 1.2.1 Charge Charge of electron = e = 1.602 x 10-19 C Charge of hole = + e = + 1.602 x 10-19 C
1.2.2 Effective Mass Consider electrons first. Electrons in CB are not entirely free as they are travelling in the background g p potential of the lattice atoms (nuclei, electron shells)
Valence electron charge density
The Semiconductor in Equilibrium Charge Carriers in Semiconductors 1.2.2 Effective Mass Electrons experience internal forces Fint due d t to the th b background k d potential t ti l of f the lattice atoms. When an external force Fext ( (e.g. g an electric field) is applied to the conduction electrons, the equation of motion for the electrons can be written as:
Fext + Fint = m0 a
where, m0 = free electron mass (9.108 x 10-31 kg) a = acceleration

Internal and external forces acting on a conduction electron
The Semiconductor in Equilibrium Charge Carriers in Semiconductors To treat the electrons as if they were truly free particles that respond to the external force (only), we wish to hide the internal force term in the equation of motion. We can re-write the equation of motion as:
* Fext = mn a
* where mn is the effective mass of an electron in the CB.
The effective mass now includes and takes care of the effects of the internal lattice forces on the electron. Electrons residing near the bottom of the CB behave like free electrons electrons, but * with an effective mass given by mn .
The Semiconductor in Equilibrium Charge Carriers in Semiconductors An analogy pushing a car
M Motion ti of f car is i governed db by th the f force you exert t (th (the external t lf force), ) and d th the true mass of the car.
The Semiconductor in Equilibrium Charge Carriers in Semiconductors An analogy pushing a car (episode 2)
Th The internal i t lf forces (the (th applied li d b brakes) k ) opposes your exerted t df force and d makes the car feel heavier to you. It has a larger effective mass, as far as you are concerned. For the same external force, the car accelerates slowly.
Th The internal i t lf forces (the (th engine) i ) assists i t your exerted t df force and d makes k th the car feel lighter to you. It has a smaller effective mass, as far as you are concerned. For the same external force, the car accelerates more.
Motto M tt choose h your friends f i d carefully! f ll !
The Semiconductor in Equilibrium Charge Carriers in Semiconductors Effective mass for holes Motion of holes at the top of the VB results from the collective effects produced by electrons moving in a nearly full band band. The motion of a hole is thus also affected by the internal lattice forces. The equation of motion for a hole is
Fext = m* pa
where h is th the effective ff ti mass of f a hole. h l m* p i

* mn m0
Material Si Ge GaAs
m* p m0
0.49 0.28 0.5
0.26 0.12 0.067
Typical normalized effective masses in selected semiconductors at 300K
The Semiconductor in Equilibrium Charge Carriers in Semiconductors 1.2.3 Energy By convention, energy band diagrams are energy diagrams for negatively charged electrons electrons, with energy increasing from bottom to top top. For electrons in the CB, the lowest energy states are at the bottom of the CB, and hence electrons tend to stay in these low energy states near EC. For holes, which are positively charged, their energy increases from the top of a band to the bottom of a band. H Holes l i in the h VB are f found di in the h lower-energy l states for f holes, h l which hi h are at the top of the VB near EV.
The Semiconductor in Equilibrium Charge Carriers in Semiconductors 1.2.3 Carrier motion in an electric field Compare an electron in vacuum to an electron in the CB of silicon:
The Semiconductor in Equilibrium Charge Carriers in Semiconductors Under the influence of an external electric field, holes move in the opposite direction to electrons. Currents are in the same direction (due to opposite charge direction of current is direction of flow of +ve charge). Note that the energy for holes increase from the top of the VB to the t e bottom botto o of t the e VB.
The Semiconductor in Equilibrium Charge Carriers in Semiconductors 1.2.4 Summary
Electrons
Holes
Occupy states at the bottom of the Occupy states at the top of the conduction band (CB). valence band (VB). Charge g Effective mass Energy e( (negative) g ) Effective mass at the bottom of * the CB = mn Lowest energy states at the bottom of the CB. Energy increases upwards. + e (p (positive) ) Effective mass at the top of the VB * = mp Lowest energy states at the top of the VB. Energy increases downwards.
The Semiconductor in Equilibrium 1. Charge Carriers in Semiconductors 2. Doping of Semiconductors 3 Carrier 3. C i C Concentration t ti Reference D.A. Neamen, Semiconductor Semiconductor Physics and Devices (McGraw-Hill, 2003), Chapter 4.
The Semiconductor in Equilibrium Doping of Semiconductors
2. Doping of Semiconductors 2 1 Undoped Semiconductors 2.1 2.2 Doped Semiconductors 2.3 Majority and Minority Carriers 2.4 Charge Neutrality 2.5 Semiconductor Doping Techniques 2.S Equation Summary

2.1 Undoped Semiconductors We have considered pure and ideal semiconductors with no impurities so far. The properties of the semiconductor are intrinsic to the material, and such semiconductors said to be intrinsic semiconductors. In intrinsic semiconductors, the electron and hole concentrations are equal, since every electron that is thermally excited across the bandgap into the CB results in a hole in the VB VB.

At thermal equilibrium, the electron concentration, n0 (cm 3 ) , and the hole 3 concentration, p0 (cm ) , can be written as:
n0 = p0 = ni
where ni is known as the intrinsic carrier concentration. The subscript 0 is used to denote thermal equilibrium conditions.
Thermal Equilibrium At thermal equilibrium, the energy in a system is everywhere equalized and evenly distributed, and is at equilibrium with its ambient temperature. There is no energy input (or output) from heat, voltage, or optical excitation. In this course, we specifically mean that there is no optical excitation (light shining on the semiconductor), and no net motion of charge (no net current t flow). fl )

ni depends on:
1. Semiconductor p properties, p , e.g., g , bandgap. g p If the bandgap g p is small, , then more electrons can be excited across the bandgap at any given temperature compared to a large bandgap material, e.g., at T = 300K: Ge: Si: GaAs: Eg = 0.67eV 0 67eV Eg = 1.12eV Eg = 1.43eV 1 43eV
3 ni = 2.4 2 4 x 1013 cm-3
ni = 1.5 x 1010 cm-3 ni = 1.8 1 8 x 106 cm-3
At 300K, the average thermal energy of an electron is only about 3/2kT ~ 0 04 eV 0.04 eV, so statistically very few electrons have sufficient energy to jump across the bandgap. Actually the fraction of electrons is very small for silicon there are 2 x 1023 valence electrons / cm3 . Hence only around 1 out of 1013 valence electrons is excited across the bandgap!

2. Temperature. The average thermal energy increases with temperature which allows more electrons to make it across the bandgap. At T = 0K, all semiconductors are insulators since there are no carriers carriers. At high temperatures, some materials that are insulators at room temperature become semiconductors. i d t An example is diamond which is used as a semiconductor for devices operating p g at several hundred oC.
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Intrinsic carrier concentrations for Si, Ge, and GaAs

2.2 Doped Semiconductors Elements in Groups III & V are incorporated as impurities in Group IV semiconductors such as Ge and Si Si.
B = Boron
P = Phosphorus
Ga = Gallium
As = Arsenic
In = Indium
Sb = Antimony

2.2.1 Donors Donors for silicon (Group IV) come from Group V of the periodic table (e.g. P, As Sb). As, Sb) Group V elements have 5 valence electrons electrons. If an As atom replaces a Si atom (i.e., it forms a substitutional impurity) it will form 4 covalent bonds with the 4 surrounding Si atoms. This leaves an unbonded 5th electron.

2.2.1 Donors Donors for silicon (Group IV) come from Group V of the periodic table (e.g. P, As Sb). As, Sb) Group V elements have 5 valence electrons electrons. If an As atom replaces a Si atom (i.e., it forms a substitutional impurity) it will form 4 covalent bonds with the 4 surrounding Si atoms. This leaves an unbonded 5th electron. The 5th electron is loosely coupled to the parent As atom, and at T = 0K remains bound to the parent (like an electron orbiting the nucleus) nucleus).

The amount of energy required to free the loosely-bound electron is of the order of 10s of meV in Silicon. As the temperature increases, more and more of the As atoms become ionized. At T > ~150K, practically all the As atoms in Si are ionized. The freed electron can now conduct electricity. The As atom is now ionized and becomes an As+ ion, but this ion is covalently bonded to the Si lattice lattice. It is not a charge carrier carrier, but a fixed charge. charge
We can locate the position of the donor state in the energy band diagram (the energy of the loosely-bound loosely bound electron electron, before ionization) or the donor level. Since the freed electron is now a conduction electron, it travels at the bottom of the conduction band, at the conduction band edge EC. If the energy required to free the electron (the ionization energy) is 0.049eV (for As in Si), then the donor level must be 0.049eV below EC.
The As atom is known as a donor in the Si lattice since it donates a (conduction) electron when it is ionized ionized. Other Group V elements also act as donors in Group IV Si and Ge. An otherwise pure semiconductor that has impurities introduced (donors or acceptors) is said to be doped. The impurities are called dopants. The ionization energy EC ED required to ionize the donor depends on the dopant as well as the host semiconductor. Ionization energy (eV) Element Phosphorus (P) Arsenic (As) Antimony y( (Sb) ) Z 15 33 51 Type Donor Donor Donor Ge 0 0120 0.0120 0.0127 0.0096 Si 0 044 0.044 0.049 0.039
Properties of donor dopants

If there are ND (cm-3) donors in the lattice, they will contribute ND electrons to the conduction band when they are fully ionized. Note that an equal number of positively charged donor ions are left behind, so the material remains electrically neutral.
By the way... Doping concentrations (1013 1019 cm-3) are LOW compared to the number of silicon atoms (5 x 1022 cm-3 for Si). The doping concentrations are typically HIGH compared to the intrinsic carrier concentration at typical device operating temperatures (for Si: ~ 1010 cm-3 at room temperature, ~ 1013 3 at 150C). cm-3 C)

For silicon with the usual dopants, the dopants are practically fully-ionized at temperatures above ~150K. We normally assume that the dopants are fully-ionized at room temperature (and above). At low temperatures temperatures, not all the donors are fully ionized in the freeze-out range, e.g., for ND = 1015 cm-3:

2.2.2 Acceptors Acceptors for silicon (Group IV) come from Group III of the periodic table (e g B (e.g. B, Ga Ga, In). In) Group III elements have 3 valence electrons electrons. They accept electrons from the silicon lattice to create holes. (i e it forms a substitutional impurity) it will If a B atom replaces a Si atom (i.e., form 3 covalent bonds with the 3 surrounding Si atoms. This leaves an incomplete 4th bond.
At T = 0K, the empty state resulting from the incomplete 4th bond is not free to move it is bound to the parent B atom atom, and hence it is not a hole hole. You need an ionization energy of ~ 0.05 eV in order to create a (mobile) hole. The reason is that a Si-Si bond is stronger than a B-Si bond. To break a SiSi bond, you need Eg ~1.1eV. When a B-Si bond is formed, you only get back (Eg - 0.05eV).
The amount of energy required to create a hole is of the order of 10s of meV in Silicon Silicon. As the temperature increases, more and more of the B atoms become ionized. At T > ~150K, practically all the B atoms in Si are ionized. The hole created can now conduct electricity. The B atom is now ionized and becomes an B ion, but this ion is covalently bonded to the Si S lattice. It is not a charge carrier, but a fixed f ve charge.
-
We can locate the position of the acceptor state in the energy band diagram (the energy of the empty state state, before ionization) or the acceptor level. The created hole travels at the top of the valence band, at the valence band edge EV. If the energy required to create the hole (the ionization energy) is 0.045eV (for B in Si), then the acceptor level must be 0.045eV above EV.
If there are NA (cm-3) acceptors in the lattice, they will contribute NA holes to the valence band when they are fully ionized. Note that an equal number of negatively charged acceptor ions are left behind, so the material remains electrically neutral. As with donors, at low temperatures, not all the acceptors are fully ionized in the freeze-out range.
2.2.3 Extrinsic semiconductors Carrier concentrations ( (electrons or holes) ) introduced by y dopants p are usually y much higher than the intrinsic carrier concentration of the semiconductor. e.g., n = 1015 cm-3 for Si doped with 1015 cm-3 donors, compared with 0 cm-3 3 at T = 300K. ni ~ 1010 300K The electron & hole concentrations of the Si are then no longer controlled by properties p of Si, , but by y the dopants. p the intrinsic p The semiconductor is then said to be an extrinsic semiconductor.

2.2.4 Summary of properties of donors & acceptors
Donors Valence electrons For Group IV host Carrier created Ionized dopant Energy level of d donor/acceptor / t state t t More valence electrons than host semiconductor. semiconductor Group V elements Electrons Positive, fixed charge Slightly g y below the CB
Acceptors Fewer valence electrons than host semiconductor. semiconductor Group III elements Holes Negative, fixed charge Slightly g y above the VB

2.3 Majority and Minority Carriers In an undoped semiconductor, electrons and holes are created in pairs. At thermal equilibrium, p = n = ni, where ni ~ 1.5 x 1010 cm-3 for Si at 300K.
Consider donor doping. When you dope a semiconductor with donors, and if the temperature is sufficiently high for complete ionization, then each donor will contribute 1 electron to the conduction band band. Usually the doping levels are such that ND >> ni, so the electron concentration is n ND. Hence if ND = 1015 cm-3, then n = 1015 cm-3 >> ni. Q: What happens to the hole concentration?

Thought experiment:
Undoped semiconductor at room temperature
Adding in ND donors (>> ni)
Final carrier population in CB and VB
n0 = ni p0 = ni
ni ~ 1010 cm 3
Electrons from ED fill up the low energy states (holes) in VB. Remaining electrons from ED thermally excited to CB
Most of the holes in the VB annihilated. Large concentration of electrons (mainly from the donors, n ~ ND) in the CB.

Introduction of donors results in: A large concentration of electrons, which become the majority carriers. Reduction in the hole concentration, which become the minority carriers. Material is said to be n-type (n for negative, charge of majority electrons). Introduction of acceptors results in: A large concentration of holes, which become the majority carriers. Reduction in the electron concentration, which become the minority carriers. Material is said to be p-type (p for positive, charge of majority holes). Summary Semiconductor doped with: Semiconductor type Majority carriers Minority carriers Donors n-type electrons holes Acceptors p-type holes electrons

2.3.1 Law of mass action Under typical doping, conc. of majority carriers >> conc. of minority carriers. The law of mass action at thermal equilibrium states that:
p0 n0 = ni2
Obvious for an intrinsic semiconductor where p0 = n0 = ni Also holds for extrinsic semiconductors. If you increase the electron concentration then the hole concentration will decrease and vice versa concentration, versa. Example: As (gp V, donor) doped Si
+ If we e dope S Si with t ND = 10 016 c cm-3, then t e (to be s shown o later): ate ) n0 N D = 10 016 c cm 3 + where N D = conc. of ionized donors (assumed fully ionized at room temp.).
From the law of mass action,

10 2 ( ) = 2.25 104 cm3 1 . 5 10 p0 n0 = ni2 p0 =
1016
Only ~22,000 holes per cm3, or ~12 orders of magnitude fewer holes compared to electrons!

2.4 Charge Neutrality If both donors and acceptors are added to the same crystal, their effects cancel only the excess of one above the other has an effect on the carrier density. To see this, this let us consider an electrically neutral region in the semiconductor where both (ionized) donors and acceptors may co-exist. Charge neutrality simply states that the net charge must be zero, or that the negative ti charges h must tb balance l out t th the positive iti charges. h Since there are 4 types of charges in a semiconductor:
+ n0 + N A = p0 + N D
mobile electrons fixed ionized acceptors t
mobile holes
fixed ionized d donors

Case 1: n-type semiconductor with only donors present (NA = 0)
+ n0 + N A = p0 + N D
p0 n0 = ni2
ni2 + n0 = + ND n0
2 + n0 ND n0 ni2 = 0
S l i th Solving the quadratic, d ti we get t
n0 =
+ ND
+2 ND
+ 4ni2
We only take the +ve solution as negative values for electron concentration make no physical sense.
+ If N D >> ni (true for most practical cases of doping) then we can neglect the 4ni2 term in the square root, and write: + n0 N D
and
p0 = ni2 n0

Case 2: p-type semiconductor with only acceptors present (ND = 0)
+ n0 + N A = p0 + N D
p0 n0 = ni2
ni2 + NA = p0 p0
2 p0 NA p0 ni2 = 0
S l i th Solving the quadratic, d ti we get t
p0 =
NA
2 NA
+ 4ni2
We only take the +ve solution as negative values for hole concentration make no physical sense.
If N A >> ni (true for most practical cases of doping) then we can neglect the 4ni2 term in the square root, and write: p0 N A
and n0 = ni2 p0

2.4 Charge Neutrality Case 3: Semiconductor with both donors & acceptors present
+ If N A ND >> ni then there are simple solutions: + (a) if N A > N D , the material is p-type and + p0 = N A ND
and n0 = ni2 p0
+ > NA (b) if N D , th the material t i li is n-type t and d + n0 = N D NA
and
p0 = ni2 n0
+ ND > If N A /> / ni then the exact values for the carrier concentrations need to
obtained by solving the quadratic in full.
To see why only net concentration of ionized dopants matters (thought expt expt.) )
Undoped silicon @ TE
Doping with acceptors
Resulting carrier concentration
Few electrons, holes in undoped semiconductor.
Electrons from CB occupy low-energy states at EA. Electrons from VB excited into remaining state at EA
Holes become maj. carrier, p0~NA. Electrons become min min. carrier, n0 << ni.
Doping with donors
Final carrier concentration
Now add ND (>NA) dopants. NA electrons from ED occupy low-energy states (holes) in VB.
Remaining (ND-NA) electrons excited into CB to form majority electrons.

2.4.1 Compensated semiconductor
+ If the concentration of ionized donors and acceptors are equal, i.e., N D = N A then their effects cancel out and: n0 = ni & p0 = ni
The semiconductor is then said to be compensated. If the concentrations of the ionized dopants are not equal, the material is said to be partially compensated. An important consequence of this compensation is that it is possible to change, for example, a p-type semiconductor into an n-type semiconductor by y doping p g the original g p p-type yp semiconductor with more donors than there were original acceptors. This trick can be repeated several times, so that the n-type semiconductor can be changed back into a p-type semiconductor by adding even more acceptors. However, the total concentration of dopants increases each time the material is changed from f p-type to n-type and vice versa. This can adversely affect other properties of the semiconductor.

Example
3 C Consider id a silicon ili substrate b t t with ith an i initial iti l d doping i of f NA1 = 2x10 2 1015 cm-3 acceptors. The silicon is thus p-type, with a hole concentration of 2x1015 cm-3.
y dope p a volume with ND = 5x1015 cm-3 donors. We now selectively As there are more donors than acceptors, the selected volume is now ntype with an electron concentration of n = ND NA1 = 3x1015 cm-3.

Example W We now selectively l ti l dope d a smaller ll selected l t d volume l with ith an additional dditi l doping of NA2 = 7x1015 cm-3 acceptors. As there are more acceptors p than donors in this volume, , it is now p-type p yp with a hole concentration of p = NA1 ND + NA2 = 4x1015 cm-3.

Example A silicon sample is doped with 2x1016 cm-3 acceptors and 5x1016 cm-3 donors. What are electron and hole concentrations at thermal equilibrium at T=300K? 300K? Step 1: Determine if the Si is n- or p- type If NA > ND -> p p-type, yp majority j y carriers are holes, minority y electrons. If ND > NA -> n-type, majority carriers are electrons, minority holes. If ND = NA -> Si is fully compensated, intrinsic carrier concentrations. In this case, ND > NA, so Si is n-type, & majority carriers are electrons. p 2: Calculate majority j y carrier concentration ( (if applicable) pp ) Step Majority carrier concentration = NET ionized dopant concentration, assuming |NA ND| >> ni. (within a factor of 5 or so), ) then have to If |NA ND| is comparable to ni ( solve the quadratic (see Section 2.4 earlier). If the material is fully compensated, then p0=n0=ni (nothing else to be done). In this case, the temperature is 300K and hence we can assume full-ionization of dopants, and ND NA = (5x1016 2x1016) = 3x1016 cm-3 = n0 (>> ni = 1.5x1010cm-3)

Step 3: Finally, calculate the minority carrier concentration The minority carrier concentration at thermal equilibrium is given by p0n0=ni2. For n-type, p0 = ni2/n0 For p-type, n0 = ni2/p0 In this case, since n0 = 3x1016 cm-3, and using ni = 1.5x1010 cm-3 (at T = 300K), we have,
p0 =
ni2 n0
(1.5 10 )
3 1016
10 2
= 7.5 103 cm 3

2.5 Semiconductor Doping Techniques Apart from dopants which are added into the silicon melt during the growth of the silicon ingot from which the wafers are cut cut, dopants can be introduced selectively into the surface of a semiconductor by ion implantation. An ion implanter produces a high-energy beam (1keV up to 2MeV) of the d i di desired ions ( (e.g. B+, As A +, P+) which hi h i is th then scanned d over th the silicon ili wafer f t to be implanted. Selective implantation is achieved by opening windows in a masking layer (say, an oxide layer).
Ribbon ion beam scanning a wafer (Varian Associates)
Depending on the ion energy, the ions will come to a stop after a certain range of travel in the material material, be it the mask or the silicon silicon.
Simulated dopant distribution after implantation through oxide mask and metallization

2.5.1 Implantation Damage Implantation of ions into the substrate causes a lot of damage where the silicon crystal lattice is disrupted as silicon atoms are displaced displaced. The damage appears in the form of point defects, induced dislocations, and amorphous regions.
(a) TEM image showing the crosssection of a silicon wafer implanted with silicon. (b) amorphous regions visible and ( (c) ) mainly y amorphous p region at a greater depth
Moreover, the implanted atoms are not electrically active unless they are in substitutional sites in the silicon lattice lattice. Hence an annealing process is needed after ion implantation to allow atomic diffusion to take place to repair the damage and activate the dopants.
Anneal
20/07/2010
J Thong
107
MD simulation of 5keV As ion implant into silicon (movie)
MD simulation of recrystallization of Si (movie)
Source: www.ele.uva.es/~simulacion/MD.htm
Tube furnace annealing
Laser annealing system
Rapid Thermal Annealing (using halogen lamps)

2.S Equation Summary (a) Law of mass action only applicable under thermal equilibrium conditions:
p0 n0 = ni2
where
p0 & n0 are the hole and electron concentrations at thermal equilibrium.
(b) Neutrality only applicable in an electrically neutral region:

+ n + NA = p + ND
+ NA and N D are the ionized acceptor and donor concentrations.
(c) Majority carrier concentration (i) For n-type material, where N D > N A
+ n0 N D NA
+ NA >> ni provided N D
(ii) For p-type material, where N A > N D

+ + p0 N A ND ND >> ni provided N A
The Semiconductor in Equilibrium 1. Charge Carriers in Semiconductors 2. Doping of Semiconductors 3 Carrier 3. C i C Concentration t ti Reference D.A. Neamen, Semiconductor Semiconductor Physics and Devices (McGraw-Hill, 2003), Sect. 3.5, Chapter 4.
The Semiconductor in Equilibrium Carrier Concentration
3. Carrier Concentration 3.1 Density y of States 3.2 Fermi-Dirac Distribution 3 3 Carrier Concentration in a Band 3.3 3.4 Electron and Hole Concentrations 3 5 Law of Mass Action for Semiconductors 3.5 3.6 Position of Fermi Level 37C 3.7 Carrier i C Concentrations t ti at t Hi High hT Temperature t 3.8 Fermi Level Considerations 3.S S Equation Summary S

3.1 Density of States We have shown that a crystalline solid has a number of energy bands, each comprising i i ah huge number b of f states t t th that t closely-spaced l l di in t terms of f energy. However, so far, we have not described how these states are distributed within each band. In general, the states are not uniformly distributed.
Schematic illustration of states in a hypothetical band

We use the concept of density of states g(E) to describe the distribution of the states in a band.
g(E).dE is the number of states (per unit volume) of the material at energy level E in an energy interval of dE.
The total number of states in the band (per unit volume) is g ( E ).dE integrated from the bottom to the top of the band.

3.1 Density of States In a semiconductor, we are interested in the CB and VB. If we sketch the DOS for the CB and the VB near the band edges EC and EV: Note that in the bandgap (forbidden band) between the CB and VB, there are NO states, i.e., g(E) = 0.

3.2 Fermi-Dirac Distribution Function So far we have described how the states are distributed, but we have not determined whether these states are actually filled (occupied by electrons). The energy distribution of electrons in a solid is described by Fermi-Dirac statistics. The Fermi-Dirac (FD) distribution function is given by:
fF (E) =
1 E EF 1 + exp kT
where f F ( E ) is the probability of a state at energy E being occupied by an electron at thermal equilibrium. k is the Boltzmann constant (1 381x10-23 J/K), (1.381x10 J/K) and T is the absolute temperature temperature.
EF is the Fermi level and is defined as the energy level where the probability of a state being g occupied p by y an electron is 0.5.

3.2 Fermi-Dirac Distribution Function
fF (E) = Th FD function: The f ti
1 E EF 1 + exp kT

3.2 Fermi-Dirac Distribution Function As the temperature increases, the function stretches out:

3.2.1 Fermi Level in a Metal To understand how the FD function relates to the occupancy of states in a band, we first consider a metal since this has a simple energy band diagram. The characteristic of a metal band diagram is a partially occupied band which allows electrical conduction to take place place. At absolute zero, all the lowest available energy states are filled up. The Fermi level is at (or just above) the highest filled energy level level, since the state above this is unoccupied, i.e., fF(E) = 0.

3.2.1 Fermi Level in a Metal If we now display the FD function at T = 0K alongside
We see that W th t all ll th the states t t below b l the th Fermi F i Level L l are occupied i d (fF(E) = 1), 1) while those above are empty (fF(E) = 0). Note that there are NO states in the forbidden band, , so there are no electrons there (although the probability of occupancy of a state here, if it had existed, would be 1).

3.2.1 Fermi Level in a Metal Now consider what happens at finite temperatures, e.g. T = 300K:
Some electrons S l t near th the F Fermi il level lh have sufficient ffi i t th thermal l energy t to occupy states higher than the Fermi level, while leaving behind now unoccupied states below the Fermi level. Hence there is now a gradual transition of fF(E) from full occupancy (1) to zero occupancy (0) as the energy goes from below to above EF. Java applet

3.3 Carrier Concentration in a Band We now have 2 functions: The DOS, Th DOS g(E), which hi h t tells ll us h how many states t t th there are per unit it energy (per unit volume) within the band at energy E, and, The FD function, , fF(E), which tells us the probability p y that a state at energy E is occupied by an electron.
The product of g(E) and fF(E) then gives us the number of electrons per unit energy (per unit volume) at energy E,
N (E ) = g (E ) f F (E )
Hence in the energy interval between E and (E+dE), there are N(E).dE electrons (per unit volume). The total number of electrons per unit volume (or electron concentration) is thus:
n = N ( E )dE = g (E ) f F (E )dE
EB EB ET ET
where e e EB, ET = botto bottom & top o of the band, respectively.

3.3.1 Carrier distribution within the band Consider the band diagram of a metal at T = 0K, states below EF are fully occupied, while states above are completely empty.

3.3.1 Carrier distribution within the band At finite temperatures, fF(E) is no longer zero above the Fermi level. Some of the electrons are excited to, and therefore occupy, states at energy levels above EF. At the same time, some of the states below EF that would have been occupied at 0K are now empty empty.

Example 4 states are located 0.05eV above/below the Fermi level. Likewise, 16 states t t are located l t d 0.1eV 0 1 V above/below b /b l th the Fermi F i level. l l At 580K, 580K d determine: t i
(a) the probability of occupancy of the states at 0.05eV and 0.1eV relative to EF, and (b) the corresponding number of electrons at these energy levels.

3.4 Electron and Hole Concentrations For an intrinsic semiconductor, we find that the Fermi level is near the middle of the bandgap. Although there are no states for an electron to occupy in the bandgap, fF(E) still gives the probability of occupancy of a state, if it exists. The distribution of electrons (concentration of electrons per unit energy) in the CB at energy E is then given by the product of fF(E) and the density of ), states for electrons gn(E)
Nn (E ) = f F (E ) gn (E )
What about holes? The probability of a hole occupying a state in the valence band at energy E is simply (1 f F ( E ) ), since a hole is an unoccupied electron state in the VB VB. So the distribution of holes in the VB is
N p ( E ) = (1 f F ( E ) ) g p ( E )

3.4 Electron and Hole Concentrations We can sketch the DOS, FD distribution, and carrier distribution as follows:
We see that most of the electrons and holes occupy states at energy levels close to their respective band edges.

3.4.1 Electron concentration in the conduction band We can evaluate the total number of electrons (cm3) in the conduction band (at thermal equilibrium) by integrating Nn(E) from the bottom to the top of the conduction band to obtain:
E EF n0 = N C exp p C kT
where NC is known as the effective density of states for electrons in the conduction band. At room temperature (300K), NC is about 2.8 x 1019 cm3 for silicon. Note that NC has a temperature dependence of
NC T 3 / 2

3.4.2 Hole concentration in the valence band Similarly, we can evaluate the total number of holes (cm3) in the valence band (at thermal equilibrium) by integrating Np(E) from the top to the bottom of the valence band to obtain:
E EV p0 = NV exp F kT
where NV is known as the effective density of states for holes in the valence band. At room temperature (300K), NV is about 1.04 x 1019 cm3 for silicon. Note that NV also has a temperature dependence:
NV T 3 / 2

3.4.3 Equations for carrier concentrations By using the effective DOS, the expressions for electron and hole concentrations look more compact:
E EF n0 = N C exp C kT
2 points to note: The equations are only for carrier concentrations at thermal equilibrium. These derived equations are only accurate provided the Fermi level should not be too close to the conduction band (for n0 expression) and valence band (for p0 expression). Usually o.k. unless we are dealing with very heavy doping (> ~1018 /cm3).

3.4.4 Effect of carrier concentrations on the Fermi level position From the equation,
E EF n0 = N C exp C kT
we see that the electron concentration n0 is large g when ( EC EF ) is small (i.e., the Fermi level is close to the conduction band edge). At the same time, the hole concentration diminishes. C Conversely l f from
the hole concentration p0 is large when ( EF EV ) is small (i.e., the Fermi level is close to the valence band edge). At the same time, the electron concentration diminishes.
The electron and hole concentrations are comparable when the Fermi level is in the middle of the bandgap (the difference being due to the slightly different values for NC and NV.
ermi i level l l in i the th middle iddl of f the th bandgap b d (b) Fermi F i level l l closer l to t CB edge. d Java applet

3.4.5 Effect of temperature on carrier concentrations Both n0 & p0 become larger at higher temperatures through both NC, NV & the denominator in the exponential function as the FD function stretches. stretches . Likewise, at low temperatures, where the FD function approaches a steplike function, the carrier concentrations both become very small.
( ) Low (a) L temperature t t (b) High Hi h temperature t t Java applet

3.5 Law of Mass Action for Semiconductors If we multiply the expressions for n0 and p0 we get:
E EV p0 n0 = N C NV exp C kT Eg = N N exp C V kT
The right-hand-side is dependent only on: o the temperature, and o the h ki kind d of f semiconductor i d (b (bandgap d Eg, effective ff i DOS NC & NV). )
It does not depend on doping / Fermi level position, and hence applies to both extrinsic and intrinsic semiconductors. At a given temperature this becomes the Law of Mass Action,
p0 n0 = ni2 = constant

3.6 Position of Fermi Level A second important result comes from dividing p0 by n0:
p0 NV E + EV 2 EF = exp C n0 NC kT NC kT n0 E + EV kT EF = C l ln + l ln 2 2 N 2 p V 0
Middle of bandgap
Small offset for Si about -0.013eV at 300K
Depends on the ratio of the carrier concentrations

3.6.1 Intrinsic semiconductor If the semiconductor were intrinsic, then p0 = n0 and we have
E + EV kT N C kT n0 ln + ln E Fi = C 2 2 NV 2 p0
where EFi is the intrinsic Fermi level. The term involving the effective DOS is quite small about -0.013eV in Si at 300K so the intrinsic Fermi level is almost in the middle of the bandgap (just below).

3.6.2 Extrinsic Semiconductor The position of the Fermi level for an extrinsic semiconductor shifts towards the majority carrier band band.
kT n0 E + EV kT N C kT n0 + = + ln ln ln EF = C E Fi 2 2 p0 2 NV 2 p0
For n-type semiconductor n0 >> p0, & EF goes above EFi towards the CB. For p-type p type semiconductor p0 >> n0, & EF goes below EFi towards the VB VB. If the material is doped more heavily, EF goes up / down further.

3.6.3 Alternative expressions for n0, p0 Equation for n0:
E EF n0 = NC exp C kT
For an intrinsic semiconductor we have
E EFi ni = NC exp C kT
Dividing the two equations, we get
E EF NC exp C n0 kT = exp EF EFi n = n exp EF EFi = i 0 ni kT kT EC EFi NC exp kT
Similarly, from expression for p0, we obtain:

E EF p0 = ni exp Fi kT

3.6.4 Degenerate doping At very high doping concentrations (~ 1019-20 cm-3 in silicon), the Fermi level moves into the CB (for n-type) or VB (for p-type). When this happens, the semiconductor is said to be degenerate. Degenerately-doped semiconductors are denoted n++ or p++, while heavily doped semiconductors are denoted n+ or p+.
In n++ material, I t i l th the conduction d ti b band di is partially ti ll occupied, i d while hil i in p++ material, t i l th the top of the VB is empty, also giving you a partially occupied band. Hence degenerately-doped semiconductors behave like metals in electrical conduction.

3.6.5 Calculation Example Position of Fermi level relative to band edge: Si doped with ND donors only Assume that all donors are ionized (check that T > 150K)
+ = ND Hence N D
If the net dopant concentration (in this case ND) is >> ni,
+ then n0 N D = N D
Inserting this into the equation for n0, we get
E EF n0 = NC exp C kT NC EC EF = kT ln n 0 NC EC EF = kT ln N D
Q: Calculate the Fermi level position for ND = 5x1016 cm-3 for Si at 300K. (NC = 2.8x1019cm-3)

3.7 Carrier Concentrations at High Temperature From the Law of Mass Action,
Eg EC EV = ni2 p0 n0 = N C NV exp = N C NV exp kT kT Eg ni = N C NV exp 2kT
We note that the effective DOS DOS, NC and NV, have a T3/2 dependence. dependence So the intrinsic carrier concentration is related to temperature via
ni T
3/ 2
Eg exp 2kT
The bandgap Eg is weakly dependent on temperature as the material expands d or contracts, t t but b t this thi i is small ll relative l ti t to th the T in i the th denominator. d i t

3.7.1 Carrier concentration as function of temperature The intrinsic carrier concentration increases rapidly with temperature temperature.
Eg ni T 3 / 2 exp 2kT
Room Temp.
At high temperature, ni can exceed the dopant concentration of a doped semiconductors, and the approximation of N A N D >> ni may no longer hold.

Consider a Si sample doped with 1015cm-3 donors: At around 500K 500K, the intrinsic carrier concentration exceeds the donor concentration. At higher hi h t temperature, t ni dominates. The number of electrons and holes are equal since i th the EHP EHPs generated t d across the bandgap greatly exceeds the number of electrons contributed by the donors. donors Hence temperatures beyond 500K form the intrinsic range where the silicon behaves intrinsically.

3.8 Fermi Level Considerations 3.8.1 Fermi Level and Thermal Equilibrium 3.8.2 Fermi Level and Workfunction 3.8.3 Fermi Level and Biasing g

3.8.1 Fermi Level and Thermal Equilibrium For a system in thermal equilibrium, the Fermi level is uniform throughout the system. y Consider 2 blocks of metal A and B where EFA < EFB initially y( (a). ) If we bring A and B together (b), the probability of an electron occupying a state at energy level E1 in B is higher than in A, i.e., there are more electrons at this energy level in B than in A A. Electrons from B will diffuse to A, charging A ve, while B charges +ve. The corresponding p gp potential energy gy of A increases, while that of B decreases, until the Fermi levels line up at thermal equilibrium (no further net charge transfer) (c).

3.8.2 Fermi Level and Workfunction We had earlier defined [Band Theory, Sect 1 Sect. 1.2] 2] the workfunction (for a metal) as the energy required to remove a conduction electron at T = 0K to the vacuum level. More specifically, the electron is located at the Fermi level. Hence, the workfunction of a metal:
em = Evac EF

In a semiconductor, there are usually no states at the Fermi level, but the workfunction is still defined as:
es = Evac EF
Clearly, the workfunction will depend on the position of the Fermi level If the semiconductor is n level. ntype, then its workfunction will be smaller than if it were p-type

What is fixed for a particular semiconductor (element) is the electron affinity, defined as:
e s = Evac EC
The workfunction can thus be determine if the position of the Fermi level relative to the conduction band edge is known:
es = e s + (EC EF )
Element Silicon, Si Germanium, Ge Gallium Arsenide, GaAs Electron affinity (eV) 4.01 4.13 4.07

3.8.3 Fermi Level and Biasing An external voltage bias applied to a system appears as a corresponding difference between the Fermi levels. Consider a parallel-plate capacitor with aluminium plates (Al, workfunction 4.3eV) ) shown. A +3V applied voltage applied to the RH plate lowers its potential energy by 3eV. This appears as a lowering of the vacuum level of the RH plate by 3eV relative to the LH plate. l Hence the Fermi level of the RH plate l t i is l lower b by 3 3eV V relative l ti t to th the LH plate.

3.S Equation Summary (a) Fermi-Dirac distribution function gives the probability of occupancy of a state by an electron:
fF (E) =
1 E EF 1 + exp kT
(b) Electron and hole concentrations (at thermal equilibrium) as function of Fermi level position:
E EF E EFi n0 = NC exp C or n0 = ni exp F kT kT E EV p0 = NV exp F or kT E EF p0 = ni exp Fi kT
(c) Intrinsic carrier concentration (derived)

Eg ni = N C NV exp 2kT

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Structure of Solids

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