HomeChemicalBondingMetalsandSemiconductors

Bondinginmetalsandsemiconductors
Chemicalbonding,part10of10
index|properties|models|covalent|polar|geometry|hybrid1|hybrid2
molecularorbitals|coordinationcomplexesmetalssemiconductors
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Propertiesofmetals
Molecularorbitalsinmetals
Originofmetallicproperties
Bandstructureofmetals
Semiconductors
Insulatorsandsemiconductors
Thermalproperties
ThePNjunction
SolarcellsandLEDs
Whatyoushouldbeabletodo
Conceptmap
Mostoftheknownchemicalelementsaremetals,andmanyofthese
combinewitheachothertoformalargenumberofintermetallic
compounds.Thespecialpropertiesofmetalstheirbright,lustrous
appearance,theirhighelectricalandthermalconductivities,andtheir
malleabilitysuggestthatthesesubstancesareboundtogetherina
veryspecialway.

1Propertiesofmetals
Thefactthatthemetallicelementsarefoundontheleftsideoftheperiodictableoffersanimportantcluetothe
natureofhowtheybondtogethertoformsolids.

TheseelementsallpossesslowelectronegativitiesandreadilyformpositiveionsMn+ .Becausetheyshow
notendencytoformnegativeions,thekindofbondingpresentinionicsolidscanimmediatelyberuled
out.
Themetallicelementshaveemptyornearlyemptyouterporbitals,sothereareneverenoughoutershell
electronstoplaceanoctetaroundanatom.
Thesepointsleadustothesimplestpictureofmetals,whichregardsthem
asalatticeofpositiveionsimmersedinaseaofelectronswhichcan
freelymigratethroughoutthesolid.Ineffecttheelectropositivenatureof
themetallicatomsallowstheirvalenceelectronstoexistasamobilefluid
whichcanbedisplacedbyanappliedelectricfield,hencegivingriseto
theirhighelectricalconductivities.Becauseeachionissurroundedbythe
electronfluidinalldirections,thebondinghasnodirectionalproperties
thisaccountsforthehighmalleabilityandductilityofmetals.
Thisviewisanoversimplificationthatfailstoexplainmetalsina
quantitativeway,norcanitaccountforthedifferencesinthepropertiesof
individualmetals.Amoredetailedtreatment,knownasthebondtheoryof
metals,appliestheideaofresonancehybridstometalliclattices.Inthecaseofanalkalimetal,forexample,this
wouldinvolvealargenumberofhybridstructuresinwhichagivenNaatomsharesitselectronwithitsvarious
neighbors.
2Molecularorbitalsinmetals
Themostusefultreatmentofmetallicsolidsisbasedonthemolecularorbitalapproach.
Itisbestunderstoodbyconsideringfirstasuccessionofmoleculesbasedonlithium(oranyotheralkalimetal
havingasingleselectroninitsvalenceshell).ThefigurebelowshowshowtheMOwavefunctionsforLi2,Li3
andLi4willlook.Theseareallconstructedbycombiningtheindividualatomicsfunctionsjustasisdonein
simpleMOtheory.Theonlythingnewhereisthatthenewmolecularorbitalsextendoveralltheatomsofthe
metal,andthattheorbitalsofintermediateenergypossessbothbondingandantibondingcharacterindifferent
regions.Everytimeweaddanotheratom,wegettwonewMOs,butsinceeachatomcontributesonlyasingle
valenceelectron,theMOsarenevermorethanhalffilled.IfweextrapolatethistoagiantmoleculeLiN
containingaverylargenumberofatoms,weget2NMOsthataresocloselyspacedinenergythattheyform
whatisknownasabandofallowedenergies.Inmetalliclithiumonlythelowerhalfofthisbandisoccupied.

3Originofmetallicproperties
Metallicsolidspossessspecial
propertiesthatsetthemapartfrom
otherclassesofsolidsandmake
themeasytoidentifyandfamiliarto
everyone.Alloftheseproperties
derivefromtheliberationofthe
valenceelectronsfromthecontrol
ofindividualatoms,allowingthem
tobehaveasahighlymobilefluid
thatfillstheentirecrystallattice.
Whatwerepreviouslyvalenceshell
orbitalsofindividualatomsbecome
splitintohugenumbersofclosely
spacedlevelsknownasbandsthat
extendthroughoutthecrystal.

Whymetalshavehigh
strengthsandhighmelting
points
Thestrengthofa
metalderivesfromthe
electrostaticattraction
betweenthelatticeof
positiveionsandthe
fluidofvalence
electronsinwhichtheyare
immersed.Thelargerthenuclear
charge(atomicnumber)ofthe
atomickernelandthesmallerits
size,thegreaterthisattraction.As
withmanyotherperiodicproperties,
theseworkinoppositeways,asis
seenbycomparingthemelting
pointsofsomeoftheGroup13
metals(right).Otherfactors,particularlythelatticegeometryarealsoimportant,soexceptionssuchasisseenin
Mgarenotsurprising.
Ingeneral,thetransitionmetalswiththeirvalenceleveldelectronsarestrongerandhavehighermeltingpoints:
Fe,1539CRe3180,Os2727W3380C.
(Wistungsten,thehighestmeltingmetalofalldoyouknowwhatprincipalusederivesfromthisveryhigh
meltingpoint?)

Whymetalsaremalleableandductile
Thesetermsreferrespectivelytohowreadilyasolidcanbeshapedbypressure(forging,hammering,rolling
intoasheet)andbybeingdrawnoutintoawire.Metallicsolidsareknownandvaluedforthesequalities,which
derivefrom

derivefrom
thenon
directional
natureofthe
attractions
betweenthe
kernel
atomsandtheelectronfluid.
Thebondingwithinionicor
covalentsolidsmaybe
stronger,butitisalso
directional,makingthese
solidssubjecttofracture
(brittle)whenstruckwitha
hammer,forexample.A
metal,bycontrast,ismore
likelytobesimplydeformedordented.

Whymetalsaregoodelectricalconductors

Inorderforasubstancetoconductelectricity,itmustcontainchargedparticles(chargecarriers)thatare
sufficientlymobiletomoveinresponsetoanappliedelectricfield.Inthecaseofionicsolutionsandmelts,the
ionsthemselvesservethisfunction.(Ionicsolidscontainthesamechargecarriers,butbecausetheyarefixedin
place,thesesolidsareinsulators.)Inmetalsthechargecarriersaretheelectrons,andbecausetheymovefreely
throughthelattice,metalsarehighlyconductive.Theverylowmassandinertiaoftheelectronsallowsthemto
conducthighfrequencyalternatingcurrents,somethingthatelectrolyticsolutionsareincapableof.Intermsof
thebandstructure,applicationofanexternalfieldsimplyraisessomeoftheelectronstopreviouslyunoccupied
levelswhichpossessgreatermomentum.
Theconductivityofanelectrolyticsolutiondecreasesasthetemperaturefallsduetothedecreasein
viscositywhichinhibitsionicmobility.Themobilityoftheelectronfluidinmetalsispractically
unaffectedbytemperature,butmetalsdosufferaslightconductivitydecrease(oppositetoionic
solutions)asthetemperaturerisesthishappensbecausethemorevigorousthermalmotionsofthe
kernelionsdisruptstheuniformlatticestructurethatisrequiredforfreemotionoftheelectrons
withinthecrystal.Silveristhemostconductivemetal,followedbycopper,gold,andaluminum.
MetalsconductelectricityreadilybecauseoftheessentiallyinfinitesupplyofhigherenergyemptyMOsthat
electronscanpopulateastheyacquirehigherkineticenergies.Thisdiagramillustratestheoverlappingband
structure(explainedfartheron)inberyllium.TheMOlevelsaresocloselyspacedthateventhermalenergiescan
provideexcitationandcauseheattorapidlyspreadthroughthesolid.

Electricalconductivitiesofthemetallicelementsvaryoverawide
range.
Noticethatthoseofsilverandcopper(thehighestofanymetal)
areinclassesbythemselves.Goldandaluminumfollowclose
behind.

Whyaremetalsgoodheatconductors?
Everyoneknowsthattouchingametallicsurfaceatroom
temperatureproducesacoldersensationthantouchingapieceof
woodorplasticatthesametemperature.Theveryhighthermal
conductivityofmetalsallowsthemtodrawheatoutofourbodies
veryefficientlyiftheyarebelowbodytemperature.Inthesame
way,ametallicsurfacethatisabovebodytemperaturewillfeel
muchwarmerthanonemadeofsomeothermaterial.Thehigh
thermalconductivityofmetalsisattributedtovibrationalexcitations
ofthefluidlikeelectronsthisexcitationspreadsthroughthecrystal
farmorerapidlythanitdoesinnonmetallicsolidswhichdependon
vibrationalmotionsofatomswhicharemuchheavierandpossess
greaterinertia.

Appearance:whyaremetalsshiny?

Weusuallyrecognizeametalbyitsmetalliclustre,whichreferstoitsabilityofreflectlight.Whenlightfalls
onametal,itsrapidlychangingelectromagneticfieldinducessimilarmotionsinthemorelooselybound
electronsnearthesurface(thiscouldnothappeniftheelectronswereconfinedtotheatomicvalenceshells.)A
vibratingchargeisitselfanemitterofelectromagneticradiation,sotheeffectistocausethemetaltoreemit,or
reflect,theincidentlight,producingtheshinyappearance.Whatcolorisametal?Withthetwoexceptionsof
copperandgold,thecloselyspacedlevelsinthebandsallowmetalstoabsorballwavelengthsequallywell,so
mostmetalsarebasicallyblack,butthisisordinarilyevidentonlywhenthemetallicparticlesaresosmallthat
thebandstructureisnotestablished.

ThedistinctivecolorofgoldisaconsequenceofEinstein'stheoryofspecialrelativityactingonthe
extremelyhighmomentumoftheinnershellelectrons,increasingtheirmassandcausingthe
orbitalstocontract.Theouter(5d)electronsarelessaffected,andthisgivesrisetoincreasedblue
lightabsorption,resultinginenhancedreflectionofyellowandredlight.

Thethermioniceffect:escapeoftheelectrongas
Theelectronswithintheelectronfluidhaveadistributionofvelocitiesverymuchlikethatofmoleculesinagas.
Whenametalisheatedsufficiently,afractionoftheseelectronswillacquiresufficientkineticenergytoescape
themetalaltogethersomeoftheelectronsareessentiallyboiledoutofthemetal.Thisthermioniceffect,
whichwasfirstobservedbyThomasEdison,wasutilizedinvacuumtubeswhichservedasthebasisof
electronicsfromitsbeginningaround1910untilsemiconductorsbecamedominantinthe1960s.

IllustrationfromaU.ofSt.AndrewsarticleonThermionicemission

4Bandmodelofmetals
Mostmetalsaremadeofatomsthathaveanouterconfigurationofs2,whichwewouldexpecttocompletelyfill
thebandofMOswehavedescribed.Withthebandcompletelyfilledandnoemptylevelsabove,wewouldnot
expectelementssuchasberylliumtobemetallic.Whathappensisthattheemptyporbitalsalsosplitintoa
band.Althoughtheenergyofthe2porbitalofanisolatedBeatomisabout160kJgreaterthanthatofthe2s
orbital,thebottompartofthe2pbandoverlapstheupperpartofthe2sband,yieldingacontinuousconduction
bandthathasplentyofunoccupiedorbitals.Itisonlywhenthesebandsbecomefilledwith2pelectronsthatthe
elementslosetheirmetalliccharacter.
Thisdiagramillustratesthebandstructureina3rd
rowmetalsuchasNaorMg,andhowitarisesfrom
MOsplittinginverysmallunitsM2M6.The
conductionbandsforthe"infinite"moleculeMN
areshaded.
Inmostmetalstherewillbebandsderivedfromthe
outermosts,p,anddatomiclevels,leadingtoa
systemofbands,someofwhichwilloverlapas
describedabove.Whereoverlapdoesnotoccur,the
almostcontinuousenergylevelsofthebandsare
separatedbyaforbiddenzone,orbandgap.Only
theoutermostatomicorbitalsformbandstheinner
orbitalsremainlocalizedontheindividualatoms
andarenotinvolvedinbonding.

Initsmathematical
development,theband
modelreliesstronglyon
thewaythatthefree
electronswithinthemetal
interactwiththeordered
regularityofthecrystal
lattice.Thealternative
viewshownhere
emphasizesthisaspectby
showingtheinnerorbitals
aslocalizedtotheatomic
cores,whilethevalence
electronsaredelocalized
andbelongtothemetalas
awhole,whichinasense
constitutesahuge
moleculeinitsownright.

5Chemicalbondinginsemiconductors
Thebandtheoryofsolidsprovidesaclearsetofcriteriafordistinguishingbetweenconductors(metals),
insulatorsandsemiconductors.Aswehaveseen,aconductormustpossesanupperrangeofallowedlevelsthat
areonlypartiallyfilledwithvalenceelectrons.Theselevelscanbewithinasingleband,ortheycanbethe
combinationoftwooverlappingbands.Abandstructureofthistypeisknownasaconductionband.

Bandarrangementsinconductors.Metallicconductionrequiresthepresenceofemptylevelsintowhich
electronscanmoveastheyacquiremomentum.Thiscanbeachievedwhenabandisonlypartiallyoccupiedor
overlapsanemptyband(right),orwhenthegapbetweenafilledbandandanupperemptyoneissufficiently
small(left)toallowordinarythermalenergytosupplythepromotionenergy.
Insulatorsandsemiconductors
Aninsulatorischaracterizedbyalargebandgapbetweenthehighestfilledbandandanevenhigherempty
band.Thebandgapissufficientlygreattopreventanysignificantpopulationoftheupperbandbythermal
excitationofelectronsfromthelowerone.Thepresenceofaveryintenseelectricfieldmaybeabletosupply
therequiredenergy,inwhichcasetheinsulatorundergoesdielectricbreakdown.Mostmolecularcrystalsare
insulators,asarecovalentcrystalssuchasdiamond.

Ifthebandgapissufficientlysmalltoallowelectronsinthefilledbandbelowittojumpintotheupperempty
bandbythermalexcitation,thesolidisknownasasemiconductor.Incontrasttometals,whoseelectrical
conductivitydecreaseswithtemperature(themoreintenselatticevibrationsinterferewiththetransferof
momentumbytheelectronfluid),theconductivityofsemiconductorsincreaseswithtemperature.Inmanycases
theexcitationenergycanbeprovidedbyabsorptionoflight,somostsemiconductorsarealsophotoconductors.
ExamplesofsemiconductingelementsareSe,Te,Bi,Ge,Si,andgraphite.

Semiconductormaterialshavetraditionallybeentotallyinorganic,composedmostlyofthelighter
Pblockelements.Morerecently,organicsemiconductorshavebecomeanimportantfieldofstudy
anddevelopment.
Thepresenceofanimpurityinasemiconductorcanintroduceanewbandintothesystem.Ifthisnewbandis
situatedwithintheforbiddenregion,itcreatesanewandsmallerbandgapthatwillincreasetheconductivity.
Thehugesemiconductorindustryisbasedontheabilitytotailorthebandgaptofitthedesiredapplicationby
introducinganappropriateimpurityatom(dopant)intothesemiconductorlattice.Thedopantelementsare
normallyatomswhosevalanceshellscontainoneelectronmoreorlessthantheatomsofthehostcrystal.
Thermalpropertiesofsemiconductors
Atabsolutezero,allofthechargecarriersresideinlowerofthebandsbelow
thesmallbandgapinasemiconductor(thatis,inthevalencebandofthe
illustrationontheleftabove,orintheimpuritybandoftheoneontheright.)
Athighertemperatures,thermalexcitationoftheelectronsallowsan
increasingfractionjumpacrossthisbandgapandpopulateeithertheempty
impuritybandortheconductionbandasshownattheright.Theeffectisthe
sameineithercasethesemiconductorbecomesmoreconductiveasthe
temperatureisraised.Notethatthisisjusttheoppositetotheway
temperatureaffectstheconductivityofmetals.
HowNandPtypematerialsconductelectricity
Forexample,aphosphorusatomintroducedasan
impurityintoasiliconlatticepossessesonemore
valenceelectronthanSi.Thiselectronis
delocalizedwithintheimpuritybandandserves
asthechargecarrierinwhatisknownasanN
typesemiconductor.InasemiconductoroftheP
type,thedopantmightbearsenic,whichhasonly
threevalenceelectrons.Thiscreateswhat
amountstoanelectrondeficiencyorholeinthe
electronfabricofthecrystal,althoughthesolid
remainselectricallyneutraloverall.Asthis
vacancyisfilledbytheelectronsfromsiliconatomsthevacancyhopstoanotherlocation,sothechargecarrier
iseffectivelyapositivelychargedhole,hencethePtypedesignation.

StructureofAs(magenta)dopedintocrystalline
Si(yellow.)[source]
Substitutionofjustonedopantatominto107atoms
ofSicanincreasetheconductivitybyafactorof
100,000.

HowPNjunctionswork
WhenPandNtypematerialsarebroughtintocontact,creatinga
PNjunction.HolesinthePmaterialandelectronsintheNmaterial
drifttowardandneutralizeeachother,creatingadepletionregion
thatisdevoidofchargecarriers.Butthedestructionofthesecarriers
leavesimmobilepositiveionsintheNmaterialandnegativeionsin
thePmaterial,givingrisetoaninterfacialpotentialdifference
("spacecharge")asdipictedhere.Asthischargebuildsup,itactsto
resistthefurtherdiffusionofelectronsandholes,leavingacarrier
freedepletionregionwhichactsasabarrieratthejunctioninterface.
AnewclassoforganicPNjunctionsmakesuseofmobilepositiveandnegativeionsaschargecarriers.
HowsolarcellsandLEDswork
ManyofthepracticalapplicationsofsemiconductorsdependonthemanipulationofthisPNjunctionpotential.
Amongthesearecertaintypesofphotovoltaicsolarcells.

Theeffectofthedepletionregionistocreateapotential
energybarriertothediffusionofelectronsfromtheNinto
thePmaterial.Thisisexpressedby"bending"the
conductionandvalencebandsasisshownhere.(Notethat
thesediagramsareconstructedforelectronsthepositive
chargeoftheholescausesthisbarriertoappearinvertedon
suchadiagram.)

(1)

Ifanexternalpotentialdifferenceisappliedtothejunction
soastocounteractthespacecharge,thenegativechargeon
theNsideraisestheenergyoftheelectronsinthe
conductionbandandoftheholesinthevalenceband,
reducingthebarrierheightsforboth(andreducingthewidth
ofthedepletionzone.)Electronsandholescannowtunnel
acrossthiszone.AforwardbiasedjunctionallowsthePN
junctionasawholetobehaveverymuchlikeaconductor.
(2)

Anotherwayofboostingtheenergyofthechargecarriersto
overcomethedepletionzonebarrieristouseamaterials
thatarecapableofabsorbinglightofanappropriate
wavelengthandwhichcanefficientlycoupletheenergyof
theabsorbedphotonstothechargecarriers.Thisisthebasis
oftheveryimportantphotovoltaicorsolarcell.
Therearemanyotherkindsofphotovoltaiccells.Seethis
Wikipediaarticleformoreinformation.
(3)

IfanexternalpotentialisappliedtoaPNjunctionsoasto
reinforcethespacechargeswithinthetworegions,the
barrierheightanddepletionzonewidthareincreased,
greatlyinhibitingtheflowofeitherkindofcarrierintothe
oppositeregion.
APNjunctionthusactsasanelectricaldiode,allowing
currenttopassthroughinonlyonedirection.Ifan
alternatingvoltageisappliedtothediode,itactsasa
rectifier,converingacintointerrupteddc.

(4)

Byselectingtherightkindsof
semiconductormaterials,theelectrons
enteringthePsideofaforwardbiased
junctioncanbemadetofallintotheholes
alreadypresentinthevalenceband
(comparethisdiagramwith(1)above.)
Theenergylostbytheelectrons(vertical
redarrows)isemittedaslight,creatinga
lightemittingdiodeorLED.
(5)

SeethisWikipediaarticleformuchmoreonlightemitting
diodes.

Whatyoushouldbeabletodo
Makesureyouthoroughlyunderstandthefollowingessentialideaswhichhavebeenpresentedabove.
Explainthefundamentaldifferencebetweenthebondinginmetallicsolidscomparedtothatinothertypes
ofsolidsandwithinmolecules.Namesomephysicalpropertiesofmetalsthatreflectthisdifference.
SketchoutadiagramillustratinghowasimplemolecularorbitalapproachtobondinginmetalsofGroups
1and2alwaysleavessomeupperMO'sempty.
Describe,atthesimplestlevel,theoriginofelectron"bands"inmetals.
Describehowtheelectricalandthermalconductivityofmetalscanbeexplainedaccordingtobandtheory.
Explainwhytheelectricalconductivityofametaldecreaseswithtemperature,whereasthatofa
semiconductorincreases.
Withtheaidofsimplediagrams,showhowdifferentbandenergyrangesinsolidscanproduce
conductors,insulators,andsemiconductors.
DescribethenatureandbehaviorofasimplePNjunction.
ConceptMap

index|properties|models|covalent|polar|geometry|hybrid1|hybrid2
molecularorbitals|coordinationcomplexesmetalssemiconductors
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semiconductors,thePNjunction,solarcellsandLEDs.Itcanbeaccesseddirectlyat
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