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 .

Organic semiconductors Long-chain Long chain polymers (e (e.g.g. diodes. G A GaN. ZnS. • • • . g silicon (Si) (Si). G N AlGaAs) AlG A ) Compounds of Gp II & Gp VI (II-VI s/c e.g. Metal oxides Many metal oxides are also semiconductors (e. germanium (Ge) Used in ICs and discrete devices such as transistors. pentacene) Used in OLED displays and polymer electronics.g. HgSe) Used in light emitting devices such as LEDs and lasers. GaAs. E E. CdTe. ZnO. Used for gas and chemical sensing.g. SiC used in high high-powered powered devices devices.Introduction 1.g. Compound semiconductors C Compounds d of fG Gp III & Gp G V (III-V (III V s/c / e. g poly-paraphenylen-vinylene poly paraphenylen vinylene PPV) Small molecules (e. SnO).Structure of Solids .3 Classes of semiconductors • Elemental semiconductors Found in Group IV of periodic table table.

As. In) and Group V (P.Introduction Atomic number Z Relative Atomic Mass Common dopants for Si * Group III (B.Structure of Solids . Ga. Sb) elements used to “dope” Si. .

• . Grains vary in size and orientation. Polycrystalline y y High degree of order over many atomic / molecular dimensions.Structure of Solids – Types of Solids 2. Grains are separated by grain boundaries. Ordered single-crystal regions are called grains. Regularity of atomic arrangement present throughout entire solid. 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.

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. .

fill d with ith 4 out of 8 possible states being occupied by electrons. Atomic Bonding 3. .Structure of Solids – Atomic Bonding 3. • Having g 4 electrons in the valence shell p places Silicon in Group p IV of the periodic table.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. • Other Group IV elements include carbon (C) and germanium (Ge).

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

the atoms are positioned on a periodic array of points in space. . In a crystal. • Most Group IVA elements have the diamond structure – C. Si. we end up with the diamond crystal structure. Sn.Structure of Solids – Atomic Bonding • 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. Ge.

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

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

Structure of Solids – Growth of Semiconductor Materials 4. • The starting “wafer” is cut from a single-crystal of silicon. 450 mm wafer production is being planned. In the 1970s. Dicing Testing Packaging 300 mm wafer . Typical wafer diameter in current p production is 300 mm. Si wafers were typically 75 mm in diameter. Growth of Semiconductor Materials • Very Large Scale Integration (VLSI) ICs are fabricated on single-crystal silicon. .

& melted (m.1 Growth of silicon crystal using Czochralski (CZ) method • Start with purified polysilicon chips in a crystal pulling furnace.Structure of Solids – Growth of Semiconductor Materials 4.p. = 1410oC). • Liquid solidifies onto the seed crystal as it is pulled. . • Ti Tiny seed d crystal t l( (single-crystal i l t l of f desired crystal orientation. melt • Seed crystal is withdrawn slowly as it is rotated. low defect density) is brought into contact with the surface of the melt. Desired impurities (dopants) added to melt to control the electrical characteristics of the grown crystal.

Structure of Solids – Growth of Semiconductor Materials • Ingot is sliced up into wafers ~1mm thick. • Wafers are then lapped & polished. Wafer Polishing Ready for processing .

• Nature of the metallic bond. As.Structure of Solids – key knowledge • Rough orders of magnitude of carrier concentrations in metals & semiconductors. • Classification of solids (amorphous (amorphous. • Group III elements (B. In). polycrystalline polycrystalline. • Nature and characteristics of bonding in Si (C. crystalline) crystalline). Group IV elements (C. . Si. Al. Ge). and Group V elements (P. Ga. Sb). Ge).

and Semiconductors Reference • D. Energy Concepts 2. El t i l C Conduction d ti 4. Neamen. Metals.A. 2003) Chapter 3 3. “Semiconductor Physics and Devices” (McGraw-Hill. Devices (McGraw-Hill 2003).Band Theory Band Theory 1. Insulators. Formation of Energy Bands 3 Electrical 3. .

• Between the plates. 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.Band Theory – Energy Concepts 1. the voltage increases linearly from 0V to +5V.602 1 602 x 10-19 C is the fundamental unit of charge. • Consider a stationary electron (i..e. no kinetic energy. Energy Concepts 1 1 Potential & Kinetic Energy of an Electron 1. RH plate = +5V).1 • Electron is a negatively-charged particle with a charge of (– e) or (– q) where e (or q) = 1. .

) of the electron (in vacuum) is given by the product of its charge. ) V(x) Example: if the electron is half-way between the plates where V = +2.5 V) = .4.5 V) = -2.V Q V(x) = ( (-e).602 x 10-19 C).Band Theory – Energy Concepts • The potential energy (P.602 x 10-19 J • Thus. where 1 eV ≡ 1. the “electron-Volt” (eV). EPE = Q.V) • Since we are dealing with electrons with an elementary charge of (– e). C Ca2+.5V. what h t would ld it its corresponding PE be at +2. and the potential / voltage that it is in.E.(+2. e) it is more convenient to adopt a unit of energy. then its potential energy is simply –(xxx) eV.005 x 10-19 J (or C.5 eV • This is of course very convenient – if an electron is at a voltage of xxx V.E. the P E of the electron is: P. we have EPE = Q.(+2. Q = – e.V(x) = (-e C).V = (-1. V(x): EPE = Q. Q: If you were dealing d li instead i t d with ith a positive iti i ion of f say. for the above example.5V? .

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

• The electron energy gains K. • If the electron is free to move. What if the electron is not stationary (i..Band Theory – Energy Concepts • So far. it has finite velocity & hence kinetic energy)? • Consider an electron initially at rest in vacuum next to the LH plate where V = 0V. we have considered only the potential energy.E. • The total energy of the electron remains the same as when it started: Etot = EPE + EKE .e. 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. at the expense of a drop in potential energy.

.Band Theory – Energy Concepts Example: mid-way collision event with 100% energy loss. Example: multiple collisions.

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

1 eV 4. • Some typical metal workfunctions: * At T = 0K Platinum ( (Pt) ) Gold (Au) Tungsten (W) Al i i Aluminium (Al) Cesium (Cs) 5. the valence electrons from the constituent atoms are delocalized from the parent atoms (ions) which allow them to be mobile and conduct electricity. 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.3 V 2.2 Workfunction of a Metal Surface • In a simple model of “free” electrons in a metal.65 eV 5.5 eV 4 3 eV 4. • While the conduction electrons can move around in the metal. • These electrons are not truly “free” in the sense than an electron in vacuum is free.Band Theory – Energy Concepts 1.1 eV .

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

* additional KE gained from the E-field. Most of the energy is dissipated as heat. but it does not gain much velocity before it undergoes a scattering event. • The resulting total energy (PE+KE) is thus nearly equal to to the PE. on top of the KE due to the random velocity of the electron . • If we assume that a conduction electron in the metal starts at rest from the LH end of the bar bar. Hence the average KE remains very small*.0eV (relative to the vacuum level).Band Theory – Energy Concepts • The potential energy an electron has in vacuum is represented by the vacuum level. • The electron is accelerated by y the electric field. The mean free path is typically of the order of nm. its initial total energy is 4.

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

Band Theory – Formation of Energy Bands
• 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

Band Theory – Formation of Energy Bands
• 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

Band Theory – Formation of Energy Bands
• 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

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

2 Formation of bands in Silicon (Z = 14) • Silicon atom has14 electrons in 3 shells. • Valence shell has 4 out of 8 states filled. electrons fill available states with the lowest energy levels. • In ground state. Silicon atom (schematic) and corresponding energy levels .Band Theory – Formation of Energy Bands 2.

each The 4N valence electrons completely occupy the lower band. 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. Formation of energy bands in silicon ** sp3 hybridization .Band Theory – Formation of Energy Bands • Unlike sodium.

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

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

• An electron that takes part in conduction will be in the conduction band. Insulators. and Semiconductors 4. Typical metal band diagram (at T = 0K) . • Electrons in the valence band correspond to the valence electrons of the constituent tit t atoms. Metals.Band Theory – Metals. and Semiconductors • Band theory allows us to explain the conduction behaviour in solids. t 4. Insulators.1 Metals • Good conductors of electricity because they have partially filled bands bands.

Typical insulator band diagram (at T = 0K) . • Bandgap between the valence band and the conduction band is ~several eV. Insulators. 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.2 Insulators • Most covalently bonded solids have valence bands that are completely filled. • At room temperature (300K) where the average thermal energy of a free electron is about 3/2kT (0. and Semiconductors 4. and the conduction band completely empty empty.04 eV). Material is therefore insulating.Band Theory – Metals.

insulator • However.insulating . e.. Insulators. and Semiconductors 4.Band Theory – Metals.g. while the conduction band is empty (no electrons). • At T = 0K.12eV at 300K.3 Semiconductors • Band diagram for semiconductors is basically the same as that of an insulator. Silicon band diagram at T = 0K (schematic) . the bandgap is 1. silicon is an insulator since the valence band is completely filled (no available empty states). for silicon. the bandgap is much smaller.

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. Insulators.04eV. and Semiconductors • At room temperature. • As the average thermal energy of the electrons is only ~0.semiconducting .1eV is very.Band Theory – Metals. 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. the fraction of electrons with thermal energy > 1. Silicon band diagram at T = 300K (schematic) .

and Semiconductors • An electron excited into the conduction band can now take part in electrical conduction (plenty of available. • 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. • The electron that used to occupy a state in the valence band has now left an empty state in the valence band. Silicon band diagram at T = 300K (schematic) .Band Theory – Metals. Insulators. 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 valence band is now no longer fully occupied.semiconducting . empty states in conduction band).

5eV) can become semiconducting at higher temperature as the average thermal energy of the electrons increases increases. • An insulator at room temperature (e. Insulators.Band Theory – Metals. diamond. bandgap 5.g. while semiconductors have smaller bandgaps. and Semiconductors • The difference between an insulator and a semiconductor is one of degree rather than kind – insulators have larger bandgaps. Silicon band diagram (schematic) & electron concentration in CB .

Insulators.42 0.4 Typical Bandgaps Semiconductor Silicon (Si) Germanium ( (Ge) ) Gallium Arsenide (GaAs) Indium Antimonide (InSb) Band gap in eV at 300 K * 1.12 0. and Semiconductors 4.66 1.17 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 – Metals.

•Typical / generic band structure of insulators. and semiconductors. and restriction on the number of states & electrons in a band. kf i •Concept of vacuum level. . understand what they represent. •Thermal generation of carriers in a semiconductor and how this leads to electrical conduction conduction. •PE of electron in a potential V. •Understand why conduction can only take place in partially-filled bands bands.Band Theory – Key knowledge Energy concepts •Unit of eV. Band theory •Appreciation of how energy bands are formed in a solid solid. •Concept C of f workfunction. Typical bandgaps of semiconductors semiconductors. •Energy of an electron in a biased metal conductor & what happens to the energy components t as the th electron l t moves. conductors. •Understand the filling of energy bands at ground state.

ANNEX – Periodic Table .

“Semiconductor Semiconductor Physics and Devices” (McGraw-Hill. Chapter 4. Doping of Semiconductors 3 Carrier 3. . Charge Carriers in Semiconductors 2.A.The Semiconductor in Equilibrium The Semiconductor in Equilibrium 1. C i C Concentration t ti Reference • D. Neamen. 2003).

Charge Carriers in Semiconductors 1 1 Bond Model 1.2 Carrier Properties .The Semiconductor in Equilibrium – Charge Carriers in Semiconductors 1.1 1.

In the bond model of silicon. Silicon (Z = 14) ) has 4 valence electrons.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. At T = 0K. 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).) bil ) • • • . (Inner core electrons are tightly bound to the nucleus and are thus not mobile. all the valence electrons are involved in covalent bonds. No free electrons for electrical conduction.

The Semiconductor in Equilibrium – Charge Carriers in Semiconductors • In 2-dimensional representation: Silicon at T = 0K .

some of the electrons have sufficient thermal energy to break free from the covalent bond. Conduction Electron Silicon at T > 0K . d ti They are thus known as conduction electrons.The Semiconductor in Equilibrium – Charge Carriers in Semiconductors • • At temperatures above 0K. 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.

it leaves another behind it. etc.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. • Successive movement of electrons into spaces left behind . As another electron moves into the space.

The moving space may be treated as if it were a positively charged particle. 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. Holes are thus independent carriers. 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. called a hole.The Semiconductor in Equilibrium – Charge Carriers in Semiconductors • • • Instead of seeing a successive movement of electrons. .

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.

2.The Semiconductor in Equilibrium – Charge Carriers in Semiconductors 1.602 x 10-19 C 1.602 x 10-19 C Charge of hole = + e = + 1.2 Effective Mass • • Consider electrons first.1 Charge • • Charge of electron = – e = – 1. electron shells) Valence electron charge density .2 Carrier Properties 1.2. Electrons in CB are not entirely “free” as they are travelling in the background g p potential of the lattice atoms (nuclei.

The Semiconductor in Equilibrium – Charge Carriers in Semiconductors 1.g.108 x 10-31 kg) a = acceleration Internal and external forces acting on a conduction electron . m0 = free electron mass (9. g an electric field) is applied to the conduction electrons. When an external force Fext ( (e. the equation of motion for the electrons can be written as: Fext + Fint = m0 a • where.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.2.

we wish to hide the internal force term in the equation of motion. The effective mass now includes and takes care of the effects of the internal lattice forces on the electron. We can re-write the equation of motion as: * Fext = mn a • * where mn is the effective mass of an electron in the CB. • 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 • To treat the electrons as if they were truly free particles that respond to the external force (only). .

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. the car accelerates slowly. For the same external force. . as far as you are concerned. It has a larger effective mass.

For the same external force. It has a smaller effective mass.The Semiconductor in Equilibrium – Charge Carriers in Semiconductors An analogy – pushing a car (episode 3) • 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. as far as you are concerned. . the car accelerates more.

The Semiconductor in Equilibrium – Charge Carriers in Semiconductors An analogy – pushing a car (episode 3) • Motto M tt … choose h your friends f i d carefully! f ll ! .

28 0.26 0. • 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 0.12 0.49 0.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.067 Typical normalized effective masses in selected semiconductors at 300K . • The motion of a hole is thus also affected by the internal lattice forces.5 0.

their energy increases from the top of a band to the bottom of a band. • For electrons in the CB. which are positively charged. h l which hi h are at the top of the VB near EV.2. • H Holes l i in the h VB are f found di in the h lower-energy l states for f holes.3 Energy • By convention.The Semiconductor in Equilibrium – Charge Carriers in Semiconductors 1. with energy increasing from bottom to top top. . 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. energy band diagrams are energy diagrams for negatively charged electrons electrons.

2.The Semiconductor in Equilibrium – Charge Carriers in Semiconductors 1.3 Carrier motion in an electric field • Compare an electron in vacuum to an electron in the CB of silicon: .

• 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 • Under the influence of an external electric field. holes move in the opposite direction to electrons.

Energy increases downwards. valence band (VB).4 Summary Electrons Holes Occupy states at the bottom of the Occupy states at the top of the conduction band (CB).The Semiconductor in Equilibrium – Charge Carriers in Semiconductors 1. Energy increases upwards. 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. . + e (p (positive) ) Effective mass at the top of the VB * = mp Lowest energy states at the top of the VB.2.

“Semiconductor Semiconductor Physics and Devices” (McGraw-Hill. Charge Carriers in Semiconductors 2. C i C Concentration t ti Reference • D. Doping of Semiconductors 3 Carrier 3. 2003). .The Semiconductor in Equilibrium The Semiconductor in Equilibrium 1. Neamen. Chapter 4.A.

2 Doped Semiconductors 2.5 Semiconductor Doping Techniques 2.1 2. Doping of Semiconductors 2 1 Undoped Semiconductors 2.The Semiconductor in Equilibrium – Doping of Semiconductors 2.3 Majority and Minority Carriers 2.4 Charge Neutrality 2.S Equation Summary .

the electron and hole concentrations are equal. and such semiconductors said to be intrinsic semiconductors. In intrinsic semiconductors.1 Undoped Semiconductors • • • We have considered pure and ideal semiconductors with no impurities so far. since every electron that is thermally excited across the bandgap into the CB results in a hole in the VB VB.The Semiconductor in Equilibrium – Doping of Semiconductors 2. . The properties of the semiconductor are intrinsic to the material.

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

4 2 4 x 1013 cm-3 ni = 1..The Semiconductor in Equilibrium – Doping of Semiconductors • ni depends on: 1.43eV 1 43eV 3 ni = 2. Hence only around 1 out of 1013 valence electrons is excited across the bandgap! . .12eV Eg = 1.04 eV. at T = 300K: Ge: Si: GaAs: Eg = 0.g. so statistically very few electrons have sufficient energy to jump across the bandgap.5 x 1010 cm-3 ni = 1.g. bandgap. g . g p If the bandgap g p is small. Semiconductor p properties.67eV 0 67eV Eg = 1.8 1 8 x 106 cm-3 At 300K.. then more electrons can be excited across the bandgap at any given temperature compared to a large bandgap material. e. p . the average thermal energy of an electron is only about 3/2kT ~ 0 04 eV 0. Actually the fraction of electrons is very small – for silicon there are 2 x 1023 valence electrons / cm3 . e.

The average thermal energy increases with temperature which allows more electrons to make it across the bandgap. Element Six Limited and NT&T use chemical vapour deposition to place a coating of diamond on a polycrystalline diamond substrate Intrinsic carrier concentrations for Si. i d t An example is diamond which is used as a semiconductor for devices operating p g at several hundred oC. Ge.net. Temperature.The Semiconductor in Equilibrium – Doping of Semiconductors 2. 7 January 2008. 09:35 A BRITISH based firm has worked with Nippon Telegraph & Telephone (NT&T) to create a transistor that will clock 120GHz. and GaAs . “Diamond transistor” clocks 120GHz Give us De Beers. some materials that are insulators at room temperature become semiconductors. At high temperatures.T p By INQUIRER staff Monday. At T = 0K. all “semiconductors” are insulators since there are no carriers carriers. oh NT&amp. According to nikkei.

2 Doped Semiconductors • Elements in Groups III & V are incorporated as impurities in Group IV semiconductors such as Ge and Si Si.The Semiconductor in Equilibrium – Doping of Semiconductors 2. B = Boron P = Phosphorus Ga = Gallium As = Arsenic In = Indium Sb = Antimony .

g. • If an As atom replaces a Si atom (i. Sb) Group V elements have 5 valence electrons electrons.1 Donors • Donors for silicon (Group IV) come from Group V of the periodic table (e. it forms a substitutional impurity) it will form 4 covalent bonds with the 4 surrounding Si atoms.e. As Sb). As.The Semiconductor in Equilibrium – Doping of Semiconductors 2. This leaves an unbonded 5th electron. .. P.2.

P.1 Donors • Donors for silicon (Group IV) come from Group V of the periodic table (e. and at T = 0K remains bound to the parent (like an electron orbiting the nucleus) nucleus). .g..The Semiconductor in Equilibrium – Doping of Semiconductors 2. • If an As atom replaces a Si atom (i. • The 5th electron is loosely coupled to the parent As atom.e. Sb) Group V elements have 5 valence electrons electrons.2. it forms a substitutional impurity) it will form 4 covalent bonds with the 4 surrounding Si atoms. As. This leaves an unbonded 5th electron. As Sb).

• The freed electron can now conduct electricity.The Semiconductor in Equilibrium – Doping of Semiconductors • The amount of energy required to free the loosely-bound electron is of the order of 10s of meV in Silicon. but this ion is covalently bonded to the Si lattice lattice. • As the temperature increases. At T > ~150K. practically all the As atoms in Si are ionized. charge . but a fixed charge. • The As atom is now ionized and becomes an As+ ion. more and more of the As atoms become ionized. It is not a charge carrier carrier.

. it travels at the bottom of the conduction band.049eV below EC. at the conduction band edge EC. • Since the freed electron is now a conduction electron.The Semiconductor in Equilibrium – Doping of Semiconductors • 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.049eV (for As in Si). • If the energy required to free the electron (the ionization energy) is 0. then the donor level must be 0.

• An otherwise pure semiconductor that has impurities introduced (donors or acceptors) is said to be doped. The impurities are called dopants.049 0.039 Properties of donor dopants . • Other Group V elements also act as donors in Group IV Si and Ge.044 0.0127 0.0120 0. Ionization energy (eV) Element Phosphorus (P) Arsenic (As) Antimony y( (Sb) ) Z 15 33 51 Type Donor Donor Donor Ge 0 0120 0.The Semiconductor in Equilibrium – Doping of Semiconductors • The As atom is known as a donor in the Si lattice since it donates a (conduction) electron when it is ionized ionized.0096 Si 0 044 0. • The ionization energy EC – ED required to ionize the donor depends on the dopant as well as the host semiconductor.

so the material remains electrically neutral. 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. By the way. cm-3 C) • ..The Semiconductor in Equilibrium – Doping of Semiconductors • If there are ND (cm-3) donors in the lattice.. • Doping concentrations (1013 – 1019 cm-3) are LOW compared to the number of silicon atoms (5 x 1022 cm-3 for Si). • Note that an equal number of positively charged donor ions are left behind. ~ 1013 3 at 150°C). they will contribute ND electrons to the conduction band when they are fully ionized.

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

In) Group III elements have 3 valence electrons electrons.2. Ga Ga.g. B. This leaves an incomplete 4th bond.e. .The Semiconductor in Equilibrium – Doping of Semiconductors 2. • They accept electrons from the silicon lattice to create holes. form 3 covalent bonds with the 3 surrounding Si atoms. (i e it forms a substitutional impurity) it will • If a B atom replaces a Si atom (i.. In).2 Acceptors • Acceptors for silicon (Group IV) come from Group III of the periodic table (e g B (e.

. you need Eg ~1. you only get back (Eg .05eV). To break a SiSi bond.1eV. the empty state resulting from the incomplete 4th bond is not free to move – it is bound to the parent B atom atom.0. and hence it is not a hole hole. • The reason is that a Si-Si bond is stronger than a B-Si bond. • You need an ionization energy of ~ 0.05 eV in order to create a (mobile) hole.The Semiconductor in Equilibrium – Doping of Semiconductors • At T = 0K. When a B-Si bond is formed.

It is not a charge carrier. more and more of the B atoms become ionized. • The hole created can now conduct electricity. practically all the B atoms in Si are ionized. • The B atom is now ionized and becomes an B ion. At T > ~150K.The Semiconductor in Equilibrium – Doping of Semiconductors • The amount of energy required to create a hole is of the order of 10s of meV in Silicon Silicon. but this ion is covalently bonded to the Si S lattice. but a fixed f –ve charge. • As the temperature increases. - .

before ionization) or the acceptor level. at the valence band edge EV. then the acceptor level must be 0. • If the energy required to create the hole (the ionization energy) is 0.The Semiconductor in Equilibrium – Doping of Semiconductors • We can locate the position of the acceptor state in the energy band diagram (the energy of the empty state state.045eV above EV. • The created hole travels at the top of the valence band. .045eV (for B in Si).

so the material remains electrically neutral. compared with 0 cm-3 3 at T = 300K. . at low temperatures. not all the acceptors are fully ionized in the freeze-out range.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. .The Semiconductor in Equilibrium – Doping of Semiconductors • If there are NA (cm-3) acceptors in the lattice. ni ~ 1010 300K • The electron & hole concentrations of the Si are then no longer controlled by properties p of Si. • e. n = 1015 cm-3 for Si doped with 1015 cm-3 donors.. Note that an equal number of negatively charged acceptor ions are left behind. but by y the dopants.g. they will contribute NA holes to the valence band when they are fully ionized.2. p the intrinsic p • The semiconductor is then said to be an extrinsic semiconductor. 2. • As with donors.

semiconductor Group III elements Holes Negative. semiconductor Group V elements Electrons Positive. fixed charge Slightly g y below the CB Acceptors Fewer valence electrons than host semiconductor.2. fixed charge Slightly g y above the VB .The Semiconductor in Equilibrium – Doping of Semiconductors 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.

• Consider donor doping.3 Majority and Minority Carriers • In an undoped semiconductor. • Usually the doping levels are such that ND >> ni. then each donor will contribute 1 electron to the conduction band band. • Hence if ND = 1015 cm-3. and if the temperature is sufficiently high for complete ionization. • At thermal equilibrium. then n = 1015 cm-3 >> ni.5 x 1010 cm-3 for Si at 300K. where ni ~ 1. • Q: What happens to the hole concentration? . electrons and holes are created in pairs.The Semiconductor in Equilibrium – Doping of Semiconductors 2. When you dope a semiconductor with donors. so the electron concentration is n ≅ ND. p = n = ni.

. n ~ ND) in the CB.The Semiconductor in Equilibrium – Doping of Semiconductors • 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.

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

From the law of mass action. Example: As (gp V. then t e (to be s shown o later): ate ) n0 ≈ N D = 10 016 c cm −3 + where N D = conc. • 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. 5 10 p0 n0 = ni2 ⇒ p0 = 1016 Only ~22.The Semiconductor in Equilibrium – Doping of Semiconductors 2.). donor) doped Si + If we e dope S Si with t ND = 10 016 c cm-3.1 Law of mass action • Under typical doping. versa. of minority carriers.25 ×104 cm−3 × 1 .3. conc. of ionized donors (assumed fully ionized at room temp. 10 2 ( ) = 2. of majority carriers >> conc. or ~12 orders of magnitude fewer holes compared to electrons! .000 holes per cm3. If you increase the electron concentration then the hole concentration will decrease and vice versa concentration.

this let us consider an electrically neutral region in the semiconductor where both (ionized) donors and acceptors may co-exist.The Semiconductor in Equilibrium – Doping of Semiconductors 2. 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 . • 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. their effects cancel – only the excess of one above the other has an effect on the carrier density.4 Charge Neutrality • If both donors and acceptors are added to the same crystal. • To see this.

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

The Semiconductor in Equilibrium – Doping of Semiconductors Case 2: p-type semiconductor with only acceptors present (ND = 0) − + n0 + N A = p0 + N D . − If N A >> ni (true for most practical cases of doping) then we can neglect the 4ni2 term in the square root. 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 2 We only take the +ve solution as negative values for hole concentration make no physical sense. and write: − p0 ≈ N A and n0 = ni2 p0 .

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 .)… ) . To see why only net concentration of ionized dopants matters (thought expt expt.The Semiconductor in Equilibrium – Doping of Semiconductors 2. 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.

holes in undoped semiconductor. carrier. • Electrons from VB excited into remaining state at EA • Holes become maj. • NA electrons from ED occupy low-energy states (holes) in VB. • Electrons from CB occupy low-energy states at EA.The Semiconductor in Equilibrium – Doping of Semiconductors Undoped silicon @ TE Doping with acceptors Resulting carrier concentration • Few electrons. p0~NA. n0 << ni. • Remaining (ND-NA) electrons excited into CB to form majority electrons. • Electrons become min min. Doping with donors Final carrier concentration • Now add ND (>NA) dopants. . carrier.

. i. for example. • This “trick” can be repeated several times.4.e. • An important consequence of this compensation is that it is possible to change. the material is said to be partially compensated. • However. . so that the n-type semiconductor can be changed back into a p-type semiconductor by adding even more acceptors. N D = N A then their effects cancel out and: n0 = ni & p0 = ni • The semiconductor is then said to be compensated. 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. the total concentration of dopants increases each time the material is changed from f p-type to n-type and vice versa.1 Compensated semiconductor + − • If the concentration of ionized donors and acceptors are equal. This can adversely affect other properties of the semiconductor. • If the concentrations of the ionized dopants are not equal.The Semiconductor in Equilibrium – Doping of Semiconductors 2.

The Semiconductor in Equilibrium – Doping of Semiconductors 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. with a hole concentration of 2x1015 cm-3. y dope p a volume with ND = 5x1015 cm-3 donors. The silicon is thus p-type. • 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.

The Semiconductor in Equilibrium – Doping of Semiconductors 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. . . it is now p-type p yp with a hole concentration of p = NA1 – ND + NA2 = 4x1015 cm-3. • As there are more acceptors p than donors in this volume.

p 2: Calculate majority j y carrier concentration ( (if applicable) pp ) Step • Majority carrier concentration = NET ionized dopant concentration.The Semiconductor in Equilibrium – Doping of Semiconductors Example A silicon sample is doped with 2x1016 cm-3 acceptors and 5x1016 cm-3 donors. then p0=n0=ni (nothing else to be done).type • If NA > ND -> p p-type. • If the material is fully compensated. & majority carriers are electrons. yp majority j y carriers are holes. assuming |NA – ND| >> ni. In this case. • If ND > NA -> n-type. so Si is n-type. ) then have to • If |NA – ND| is comparable to ni ( solve the quadratic (see Section 2. What are electron and hole concentrations at thermal equilibrium at T=300K? 300K? Step 1: Determine if the Si is n. and ND – NA = (5x1016 – 2x1016) = 3x1016 cm-3 = n0 (>> ni = 1.4 earlier). minority holes.5x1010cm-3) . In this case. minority y electrons. (within a factor of 5 or so). majority carriers are electrons. the temperature is 300K and hence we can assume full-ionization of dopants.or p. intrinsic carrier concentrations. ND > NA. • If ND = NA -> Si is fully compensated.

5 ×103 cm −3 . we have.The Semiconductor in Equilibrium – Doping of Semiconductors Step 3: Finally. since n0 = 3x1016 cm-3. p0 = ni2/n0 • For p-type. • For n-type. calculate the minority carrier concentration • The minority carrier concentration at thermal equilibrium is given by p0n0=ni2. n0 = ni2/p0 In this case.5x1010 cm-3 (at T = 300K).5 ×10 ) 3 ×1016 10 2 = 7. and using ni = 1. p0 = ni2 n0 = (1.

an oxide layer). As A +.The Semiconductor in Equilibrium – Doping of Semiconductors 2.g. Ribbon ion beam scanning a wafer (Varian Associates) . B+. Selective implantation is achieved by opening windows in a masking layer (say.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. • An ion implanter produces a high-energy beam (1keV up to 2MeV) of the d i di desired ions ( (e. P+) which hi h i is th then scanned d over th the silicon ili wafer f t to be implanted. dopants can be introduced selectively into the surface of a semiconductor by ion implantation.

The Semiconductor in Equilibrium – Doping of Semiconductors

• 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

The Semiconductor in Equilibrium – Doping of Semiconductors
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

The Semiconductor in Equilibrium – Doping of Semiconductors

• 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

ele.uva.20/07/2010 © J Thong The Semiconductor in Equilibrium – Doping of Semiconductors 107 MD simulation of 5keV As ion implant into silicon (movie) MD simulation of recrystallization of Si (movie) Source: www.es/~simulacion/MD.htm .

The Semiconductor in Equilibrium – Doping of Semiconductors Tube furnace annealing Laser annealing system Rapid Thermal Annealing (using halogen lamps) .

(b) Neutrality – only applicable in an electrically neutral region: − + n + NA = p + ND − + NA and N D are the ionized acceptor and donor concentrations. where N A > N D − + − + p0 ≈ N A − ND − ND >> ni provided N A .The Semiconductor in Equilibrium – Doping of Semiconductors 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. where N D > N A + − n0 ≈ N D − NA + − − NA >> ni provided N D (ii) For p-type material. (c) Majority carrier concentration (i) For n-type material.

5. 2003). Sect. C i C Concentration t ti Reference • D. Neamen.A. “Semiconductor Semiconductor Physics and Devices” (McGraw-Hill. 3. . Doping of Semiconductors 3 Carrier 3. Chapter 4.The Semiconductor in Equilibrium The Semiconductor in Equilibrium 1. Charge Carriers in Semiconductors 2.

6 Position of Fermi Level 37C 3.S S Equation Summary S .8 Fermi Level Considerations 3.2 Fermi-Dirac Distribution 3 3 Carrier Concentration in a Band 3.7 Carrier i C Concentrations t ti at t Hi High hT Temperature t 3.The Semiconductor in Equilibrium – Carrier Concentration 3. Carrier Concentration 3.4 Electron and Hole Concentrations 3 5 Law of Mass Action for Semiconductors 3.5 3.3 3.1 Density y of States 3.

1 Density of States • • • We have shown that a crystalline solid has a number of energy bands. However. In general. 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. we have not described how these states are distributed within each band. the states are not uniformly distributed.The Semiconductor in Equilibrium – Carrier Concentration 3. Schematic illustration of states in a hypothetical band . so far.

dE integrated from the bottom to the top of the band. • The total number of states in the band (per unit volume) is ∫ g ( E ).The Semiconductor in Equilibrium – Carrier Concentration • 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. .

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. g(E) = 0.. i.The Semiconductor in Equilibrium – Carrier Concentration 3.e. .1 Density of States • • In a semiconductor. there are NO states. we are interested in the CB and VB.

• 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. k is the Boltzmann constant (1 381x10-23 J/K). 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. but we have not determined whether these states are actually filled (occupied by electrons).5.381x10 J/K) and T is the absolute temperature temperature.The Semiconductor in Equilibrium – Carrier Concentration 3. The energy distribution of electrons in a solid is described by Fermi-Dirac statistics. . (1.2 Fermi-Dirac Distribution Function • • So far we have described how the states are distributed.

The Semiconductor in Equilibrium – Carrier Concentration 3.2 Fermi-Dirac Distribution Function fF (E) = Th FD function: The f ti 1 ⎛ E − EF ⎞ 1 + exp⎜ ⎟ ⎝ kT ⎠ .

2 Fermi-Dirac Distribution Function As the temperature increases. the function stretches out: .The Semiconductor in Equilibrium – Carrier Concentration 3.

The Semiconductor in Equilibrium – Carrier Concentration 3. fF(E) = 0. all the lowest available energy states are filled up.. At absolute zero. we first consider a metal since this has a simple energy band diagram. • • • .e.1 Fermi Level in a Metal • To understand how the FD function relates to the occupancy of states in a band. The Fermi level is at (or just above) the highest filled energy level level. i. since the state above this is unoccupied. The characteristic of a metal band diagram is a partially occupied band which allows electrical conduction to take place place.2.

would be 1). 1) while those above are empty (fF(E) = 0). Note that there are NO states in the forbidden band. if it had existed. so there are no electrons there (although the probability of occupancy of a state here.The Semiconductor in Equilibrium – Carrier Concentration 3. . .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).2.

1 Fermi Level in a Metal • Now consider what happens at finite temperatures.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.The Semiconductor in Equilibrium – Carrier Concentration 3. Java applet • . e. 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.2. while leaving behind now unoccupied states below the Fermi level.

Th DOS g(E). N (E ) = g (E ) ⋅ f F (E ) • • Hence in the energy interval between E and (E+dE). The product of g(E) and fF(E) then gives us the number of electrons per unit energy (per unit volume) at energy E.The Semiconductor in Equilibrium – Carrier Concentration 3. 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. there are N(E).3 Carrier Concentration in a Band • We now have 2 functions: • • • The DOS. The FD function. 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.dE electrons (per unit volume). which tells us the probability p y that a state at energy E is occupied by an electron. ET = botto bottom & top o of the band. . and. fF(E). respectively. .

. while states above are completely empty.1 Carrier distribution within the band • Consider the band diagram of a metal – at T = 0K. states below EF are fully occupied.3.The Semiconductor in Equilibrium – Carrier Concentration 3.

states at energy levels above EF.3. • . fF(E) is no longer zero above the Fermi level. Some of the electrons are excited to.1 Carrier distribution within the band • At finite temperatures. some of the states below EF that would have been occupied at 0K are now empty empty. At the same time. and therefore occupy.The Semiconductor in Equilibrium – Carrier Concentration 3.

1eV 0 1 V above/below b /b l th the Fermi F i level.The Semiconductor in Equilibrium – Carrier Concentration Example • 4 states are located 0.05eV above/below the Fermi level.1eV relative to EF. 580K d determine: t i (a) the probability of occupancy of the states at ±0. Likewise. and (b) the corresponding number of electrons at these energy levels. .05eV and ±0. 16 states t t are located l t d 0. l l At 580K.

The Semiconductor in Equilibrium – Carrier Concentration .

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 ) ).The Semiconductor in Equilibrium – Carrier Concentration 3. we find that the Fermi level is near the middle of the bandgap. So the distribution of holes in the VB is N p ( E ) = (1 − f F ( E ) ) ⋅ g p ( E ) . since a hole is an unoccupied electron state in the VB VB.4 Electron and Hole Concentrations • • • For an intrinsic semiconductor. Although there are no states for an electron to occupy in the bandgap. 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 ). fF(E) still gives the probability of occupancy of a state. if it exists.

The Semiconductor in Equilibrium – Carrier Concentration 3.4 Electron and Hole Concentrations • We can sketch the DOS. . 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. FD distribution.

4.The Semiconductor in Equilibrium – Carrier Concentration 3. Note that NC has a temperature dependence of NC ∝ T 3 / 2 . NC is about 2.1 Electron concentration in the conduction band • We can evaluate the total number of electrons (cm–3) 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).8 x 1019 cm–3 for silicon.

we can evaluate the total number of holes (cm–3) 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.04 x 1019 cm–3 for silicon. Note that NV also has a temperature dependence: NV ∝ T 3 / 2 .2 Hole concentration in the valence band • Similarly. NV is about 1.4. • • At room temperature (300K).The Semiconductor in Equilibrium – Carrier Concentration 3.

k. 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). the expressions for electron and hole concentrations look more compact: ⎛ E − EF ⎞ n0 = N C exp ⎜ − C ⎟ kT ⎝ ⎠ ⎛ E − EV ⎞ p0 = NV exp⎜ − F ⎟ kT ⎝ ⎠ • 2 points to note: • • The equations are only for carrier concentrations at thermal equilibrium. unless we are dealing with very heavy doping (> ~1018 /cm3). .3 Equations for carrier concentrations • By using the effective DOS.The Semiconductor in Equilibrium – Carrier Concentration 3. Usually o.4.

At the same time.The Semiconductor in Equilibrium – Carrier Concentration 3.e...4 Effect of carrier concentrations on the Fermi level position • From the equation.e. the Fermi level is close to the conduction band edge). the Fermi level is close to the valence band edge). At the same time.4. • C Conversely l f from ⎛ E − EV ⎞ p0 = NV exp⎜ − F ⎟ kT ⎠ ⎝ the hole concentration p0 is large when ( EF − EV ) is small (i. the electron concentration diminishes. the hole concentration diminishes. . ⎛ E − EF ⎞ n0 = N C exp ⎜ − C ⎟ kT ⎝ ⎠ we see that the electron concentration n0 is large g when ( EC − EF ) is small (i.

d Java applet . 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.The Semiconductor in Equilibrium – Carrier Concentration • 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.

the carrier concentrations both become very small. stretches . at low temperatures. where the FD function approaches a steplike function. ( ) Low (a) L temperature t t (b) High Hi h temperature t t Java applet .4. NV & the denominator in the exponential function as the FD function “stretches”.The Semiconductor in Equilibrium – Carrier Concentration 3. Likewise.5 Effect of temperature on carrier concentrations • • Both n0 & p0 become larger at higher temperatures through both NC.

effective ff i DOS NC & NV). At a given temperature this becomes the Law of Mass Action.The Semiconductor in Equilibrium – Carrier Concentration 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. ) • It does not depend on doping / Fermi level position. and hence applies to both extrinsic and intrinsic semiconductors. and o the h ki kind d of f semiconductor i d (b (bandgap d Eg. p0 n0 = ni2 = constant • .

The Semiconductor in Equilibrium – Carrier Concentration 3.013eV at 300K Depends on the ratio of the carrier concentrations .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.

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.1 Intrinsic semiconductor • If the semiconductor were intrinsic.6. .013eV in Si at 300K – so the intrinsic Fermi level is almost in the middle of the bandgap (just below). The term involving the effective DOS is quite small – about -0.The Semiconductor in Equilibrium – Carrier Concentration 3.

For p-type p type semiconductor p0 >> n0. & EF goes below EFi towards the VB VB. 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 up / down further.6.The Semiconductor in Equilibrium – Carrier Concentration 3. If the material is doped more heavily. .2 Extrinsic Semiconductor • The position of the Fermi level for an extrinsic semiconductor shifts towards the majority carrier band band. & EF goes above EFi towards the CB.

from expression for p0. 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 obtain: ⎛ E − EF ⎞ p0 = ni exp⎜ Fi ⎟ kT ⎝ ⎠ .3 Alternative expressions for n0. 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.6.The Semiconductor in Equilibrium – Carrier Concentration 3.

the Fermi level moves into the CB (for n-type) or VB (for p-type).The Semiconductor in Equilibrium – Carrier Concentration 3. t i l th the top of the VB is empty. • • In n++ material. i d while hil i in p++ material. Degenerately-doped semiconductors are denoted n++ or p++. When this happens. also giving you a partially occupied band. I t i l th the conduction d ti b band di is partially ti ll occupied. while heavily doped semiconductors are denoted n+ or p+. .6. Hence degenerately-doped semiconductors behave like metals in electrical conduction.4 Degenerate doping • At very high doping concentrations (~ 1019-20 cm-3 in silicon). the semiconductor is said to be degenerate.

6. (NC = 2.The Semiconductor in Equilibrium – Carrier Concentration 3. 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.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 ¾ Hence N D • If the net dopant concentration (in this case ND) is >> ni. + ¾ then n0 ≈ N D = N D • Inserting this into the equation for n0.8x1019cm-3) .

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.7 Carrier Concentrations at High Temperature • From the Law of Mass Action. have a T3/2 dependence. d i t . t t but b t this thi i is small ll relative l ti t to th the T in i the th denominator.The Semiconductor in Equilibrium – Carrier Concentration 3. NC and NV. ⎛ 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.

. ni can exceed the dopant concentration of a doped semiconductors.7. ⎛ Eg ⎞ ni ∝ T 3 / 2 exp⎜ ⎟ ⎜ − 2kT ⎟ ⎝ ⎠ Room Temp. and the approximation of N A − N D >> ni may no longer hold. • At high temperature.The Semiconductor in Equilibrium – Carrier Concentration 3.1 Carrier concentration as function of temperature • The intrinsic carrier concentration increases rapidly with temperature temperature.

• • . donors Hence temperatures beyond 500K form the intrinsic range where the silicon behaves intrinsically.The Semiconductor in Equilibrium – Carrier Concentration • Consider a Si sample doped with 1015cm-3 donors: • At around 500K 500K. t ni dominates. the intrinsic carrier concentration exceeds the donor concentration. 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. At higher hi h t temperature.

2 Fermi Level and Workfunction 3.8.The Semiconductor in Equilibrium – Carrier Concentration 3.8.3 Fermi Level and Biasing g .8 Fermi Level Considerations 3.8.1 Fermi Level and Thermal Equilibrium 3.

while that of B decreases.The Semiconductor in Equilibrium – Carrier Concentration 3. the probability of an electron occupying a state at energy level E1 in B is higher than in A.8. the Fermi level is uniform throughout the system.1 Fermi Level and Thermal Equilibrium • • For a system in thermal equilibrium. until the Fermi levels line up at thermal equilibrium (no further net charge transfer) (c).e. ) If we bring A and B together (b).. Electrons from B will diffuse to A. i. charging A –ve. The corresponding p gp potential energy gy of A increases. y Consider 2 blocks of metal A and B where EFA < EFB initially y( (a). there are more electrons at this energy level in B than in A A. • . while B charges +ve.

The Semiconductor in Equilibrium – Carrier Concentration
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:

eφm = Evac − EF

The Semiconductor in Equilibrium – Carrier Concentration
• In a semiconductor, there are usually no states at the Fermi level, but the workfunction is still defined as:

eφs = 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

The Semiconductor in Equilibrium – Carrier Concentration
• What is fixed for a particular semiconductor (element) is the electron affinity, defined as:

eχ s = Evac − EC
• The workfunction can thus be determine if the position of the Fermi level relative to the conduction band edge is known:

eφs = eχ s + (EC − EF )
Element Silicon, Si Germanium, Ge Gallium Arsenide, GaAs Electron affinity (eV) 4.01 4.13 4.07

workfunction 4. This appears as a lowering of the vacuum level of the RH plate by 3eV relative to the LH plate.8. Consider a parallel-plate capacitor with aluminium plates (Al. • • • .3eV) ) shown.3 Fermi Level and Biasing • An external voltage bias applied to a system appears as a corresponding difference between the Fermi levels.The Semiconductor in Equilibrium – Carrier Concentration 3. A +3V applied voltage applied to the RH plate lowers its potential energy by 3eV. 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.

The Semiconductor in Equilibrium – Carrier Concentration 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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