PHYSICS o: SOLAR CELLS Jenny Nelson npr Cog >@e oePHYSICS o_O SOLAR CELLSPaty Pesce ostitur Pim (tar Seca Mo Ses Re AE (oie: 97S St ane ar, aon WC NE et rary Casing Pein Dae cpm ek ee mS Bey, Ai oe Tot. or ere. may mt pan ay frm ob ae. ste igi ga ran ona Fy horn mil ali pte pc ag ie wena sores FSeN (Seon gh Preface ‘Overseas tn years, photons ha mega to become an apliaton| of recoil potential and he atraced the interest of creasing pubes of students and researchers. Tie purpose af thls books provide an into. ‘dton 9, and overview ofthe physi of Une photvoiae cal Te coal ‘besuktabe for undergraduate physcte and engincers who ate lnterested in ‘thi application of eemizondactr pyc, abd not specas gradatar land others who require a backgrond inthe pbyseal prneples of solar cal ysl modes of photovlaie nvom and how thas elate tothe det ‘and faction of practical devies. should enable tho reeder to understand Tow solar ells work, to understand the concepts and model of solar ell ‘device physi, and to formulate nd sole eleva physical probes. A tough pratica materials nnd cevioe designs are taeda example, the book snot inended es 9 comprbersive review of photoveliaie mata sd doves, nor of te ats developments in photovolaisreerch (Chapter 1 lntroduces the sole cell as simple earrent generator and eins the performance caractortics which ge sd to dese 0 at pare solar cll- Chapter ?deseres In oneal terms bow ight energy is ‘converted ato electri, comparing the photovoteie converter with other ftom and evaluating the lta to efllency. Chapters 3 and 4 ove the ‘bse physi of the sericnduter, the seconductor transport equations sd the proses of light absorp apd earierreobiatio. Chaper 8 focues on the concept of the asymaetsic Junction, and datas the d= ferent typos of junction which are explated in phovovolnes. Chapter 6 apples the theory of eater ebapters to pn junsion, to easiea! model ofa colar ool Chapters 7 aud 8 ate concerned with the range of photo- Collie materials and device design, Chapter 7 dels with mouoeystline ‘rn jnnetion devices relating the model of Chaptar 6 to prctcal vies,“ ace ‘wing estan silcon and gli arsenide oll as examples. Chapter oul with tin th photoveltie materials, discussing physical procs tnd design ls relevant to tin films so focusing on the ways in which ‘he standard model mat be adapted fr thin fn devios, Chapter 9 dene ‘ith vriow techniques for manacing Light in onder to mastnke perfor: ‘mance, sa Chapter 10 cokers a range of approaches, sony thot, te increasing the efleleney of solar elle aoe the init for «singin band 0p plotoconverer Tam grateful tl of he people who have beled me poop thi book In pascu, to Keith Barer or passing the orginal proposal frm Ik eral Collage Pree in my directions to Leon Frere and David Ifeld for ‘ving me the opportniey to teach the pyc of wale cella to MSe st dente at Looghorough and so etal the baste ours from which this ‘bok developed to all the teuach student in photovliis at Imperial College fer rising many intersting questions, epedllyJeany Bars, James Cony and Benjunin Kufage: to Ralph Gotshal, Tom Marke ‘art and Peer Wore for hop with questions elated to material this Took; to Not BkineDankss and Jane Nelson for thes elf comments on the tox; to Clare Nelson forthe cove testi ad tall ther col Ingwer who hove bpd in ty seeurour to undead haw hes ings ror, in partir to Richard Corks, Joes Durrant, Michal Gree, Marti Green, Christiana Honsbeg,Stfan Ketan and Ellen Moons 1am grateful tothe Greenpeace Envitonnental Trust fo fang me to study solr calls before they were popu apd to the UK Rasiaeering and Physleal Sense Resaech Coun ad for an Adve Research Fellow ship whic allowed me o pend my Satay aRerboons writing chapters Instead of etree. Filly I am grateful to Joba Nava fr his encoutage seat to start on this projet and to Laurent Chaminade si bis staf et 16 ress and to Lakai Narayanan olleags at World Sees for their ep in sing it through This book is dediated to the memory of Stephan Rabizoon and MLV. Mecha, Jenny Nason London, Ape 2002 Contents Preface (Chapter 1 Introduction 11 Photous le, Electrons Out The Photovoltaic Etket 12, Biel History of the Selae 2a 13, Photovaltac Cells and Power Generation LL. Photovoltaic els mole and systems 182, Some unporaseceisions 1A, Characteritin of the Phoorltale Cal A Swmimary 11. Photocurent and quntum eficency 142 Dark current and open crit wolage 143. Bficieney TAA. Para eistaces TAS. Nowideal dode bbavioae 15, Sumay, References Chapter 2. Photons In, Electrons Outs Basic Principles of PV 2, Iaeoduction 22. The Solar Resnure 25. Types of Solar nerey Converter 24 Detaled Balance 21. In egulbsium 5 242 Under illminaticn 25, Work Available fom » Pstoveltaie Device 251, Photocurent . BEEEEN252. Daskcurent . 253. Limiting efseney 254. Biot of band gap 255. Elect of spectrum on iency 26, Requirements forthe Kal Phoaconveter 27. Summary References Chapter 3. Bleetrons and Holes in Sessiconductors 51 Tatoduetion 52. Basic Conepe 32: Bonde nnd bands incest 3.22. Flectzone, hols and conductivity 18, Election State in Soieonductre 331. Band smuctze 832 Conduction band 333. Valence band 38:4 Dizet and inet band ga 885 Density of states 886 Bletronditbution fusion 887. Bletron and hae currents 4 Seminndsctor in Eqllrium S41. Fermi Dirge waitice 4.2, Blectron and ole densities in equilib 443, Bolamann approximation 344. Blecteos and bole cureats to equlibc, 85, Impurities and Doping 51. Intrinsic semioonductone 852° neype doping 253. p type doping 354. Etec of heavy doping 355. Impefet and amerphonscystale 36. Semiconductor under Bie 361, uae thermal quite 362, Election and hoe dente under bist 363, Current densities under las 81. Dif snd Difforion ATA. Corent equations in terms of drift and dion 72. Validity ofthe dest ciusion eatations a8 3.73, Cument equation non eraline slide ‘Summary (Chapter 4 Generation and Recombination 41. Introduction: Semiconductor Taaspart Equations 42. Generation aad Reconblaaton 43, Quantum Mechanial Dexption of Tanition Rater 431, Ben Golden Rule 432. Optical pocemes ina two level ystems 44 Photopenertion 441 Photopeserstion rte 442. Thermaistion 443. Microscopie description of absorption 444, Dine: gap sconductors 445, Indivet gap semeonductors 445. Other txprof beainse 447. Beampler and data 45. Recombination 451. ‘Types of recombination 452, Rate resonbination 453, Simplified exresions for fadetive ecomblnation 454 Auger recombination 455. Shockley Read Hall recombination {£58 Sorfuce and grain boundary recombination 457, ‘Traps versus recombination centres 46, Formulation of the Transport Proble 4461. Commies on the transport problen 46.2. ‘Transport equations ina erystl 4, Bima, Reese Chapter 5 Junctions 51. Intoduction 52. Ongin of Photovtate Action 5.3. Work Funetion and Type of Jastion 5.4 Meta- Semiconductor Tunction S41, Betalishing fl 42, Bebviour in the light S49. Beluviour in the dark.S44 Obie contacts. 5:45. Limitations ofthe Sooty base ansion S55. Semiconductor Semiconductor Junctions 554. pen junction 552. pen juetion 553. pra hotornjunction : 56, Electtochemea! Junction 51. Justine in Orgale Materine 58. Suelo and ltetfce Slates 58:1. Susicw cates on fe srtuee 582. Bit ofterlee rates on junctions 59. Sammey Referee Chapter € Analysis of the p-n Junction G1 Introduction 62. The pn Junction 62: "Poomntion of p-n jnction 622. Outline of approach ©, Dapletion Approniation 31," Caleuaton of drpesion width 64. Calculation of Carer and Cucet Detities 6-41. Curate and enti denis in the nett regions 6.42. Cuments and earn donttie i the pace charge region 643, Total current dnaiy : 65. General Solution for J(V) 65, pen Junction in he Das 6.1. At equ 662. Under applied bis 67. pom Junetion under Muninatian Br. Shor crn 872. Photocurent and QE in special cases 873. _p-m junction as photovoltaic ell 88, Etets on pn Junetion Characteristics GSL. Bets of parasite rsstanese 682. Bet of erdiation G83. tect of temperate 4 re 1a 132 1 ro a 1 us 6 M6 12 14 156, 10 160 160 168 sr 160 1 m 1m 684 685, Other devin strstr ality ofthe apprximatios 69. Summary Referens Chapter 7 Monocrystalline Solar Cells TA. Intoducton: Pence of al Design 72, Matai and Design Isuet 72 yaa ra. Material dependet factor Desig factors General desig fetes op junction cals 7. Soon Material Properties 73 732 7a 73a ‘and strate and opt bsxpian Doping Recombination Carter anspor TA, Silicon Solt Cll Design TA. 742 748 Tat. 7a. 749. ‘asi sion soa all Cal tatiention Optimination of soon vole all dg Strategie to enance seoepion Strategies to ron surface ecobization Strategies to rede series eitance Evolution of lice cola ol design Future distons slic cl design Aerts to lon 7. II-V Semiconductor Matta Property 752 783 18 755 166. TIL semiconducor baad stuctre and optical sheorpsion Callum ansnide Doping Recouination (Cartier eaneport : Reflectivity 7, Gade Solar Call Design 751 162 763 764 asic Gas soit lls» Optmisition of GaAs Slee asign Stesogies to rodun ont ezine resrbination Steteges to redo series resistance 16 16. 1G 190 1 194 17 198 198 BSS2ER8 888785. Steatepes to seduce subtrte cust 71. Summary. A Referenies oo Chapter 8 Thin Film Solar Celts 8 Inteodaction| 82. Thin Film Photovoltaic Materials B21. Requirements fr eultale sterile 88. Amoephow Scan 83.1. Material propetie 83.2, Defects in amorphous material 888. Absorption 834. Doping 5 835. Transport 826 Stability. BST Related allye 84. Amogphows Silcon Solar Ct Design RAL Amorous eon p--n arctan 842, ptm anlr call device physice 843. Fubscation of ai solr ele S.G4. Strategies fo improve tell preformance 5. Defpets in Polycrystalline Tia Fn Materials BBL. Grain boundaries . 52. Bets of grain hounds on teaaspore 1853, Depletion approximation modal fr geuin boundary S54. Major cartier transport 855, Ede of Uumination 856, Minority erie transport 5.7. ete of grain houndary recombination op slar call perormance| ‘86. CulaSep Thin Film Solar Calle. 22 86.1, Materials properties 862, Beterojupetons in thin lia slr eal din 863. CulnGaSi sole eel den 87, CTe Thin Pil Solr Call STA. Materials propertice S72 Cae rolarcll design | 8S. Thin Film Silicon Solar Cains > 210 aun 58. Materials poperie 882. Microcrystalline slicon sla all devin 89. Summary. Referens Chapter 9. Managing Light 94 Ietodueton 92 Photon Pix: A Review and Overview of Light, ‘Management 921. Route to higher photon Bue 93, Minimicing Reotion 93.1. Optial propertin of umiconductrs 93.2. Amtireection coatings 9.4. Concentration BALL. Limits to concetetion 942, Practical concentrators 98, Bifects of Conssration on Device Physles D5: Low ijetion 852. High njetion 23. Limits to efciency under concentration DS. Temperature D5. Serie cesta 956. Concentrator ell eign 287. Concenteaor cll masa 96. Light Coufemext 96.1 Tighe paths and ray escing 962. Mirors 963. Rendomising clas 964 Toute cutis 965. Practical schemes 966, Light conning tuctures: restricted arceptance ste and external cavities 987. Beets af light raping on device pysice 97. Photon Reeling 8. Theory of too eeylng 9:72. Practical schemes 98, Summary References 2s 218 210 23 2st ast 8 200 28 268 20 267 m0 m0 m 5 28 280 21 282 236 288Paty Pesce ostitur Pim (tar Seca Mo Ses Re AE (oie: 97S St ane ar, aon WC NE et rary Casing Pein Dae cpm ek ee mS Bey, Ai oe Tot. or ere. may mt pan ay frm ob ae. ste igi ga ran ona Fy horn mil ali pte pc ag ie wena sores FSeN (Seon gh Preface ‘Overseas tn years, photons ha mega to become an apliaton| of recoil potential and he atraced the interest of creasing pubes of students and researchers. Tie purpose af thls books provide an into. ‘dton 9, and overview ofthe physi of Une photvoiae cal Te coal ‘besuktabe for undergraduate physcte and engincers who ate lnterested in ‘thi application of eemizondactr pyc, abd not specas gradatar land others who require a backgrond inthe pbyseal prneples of solar cal ysl modes of photovlaie nvom and how thas elate tothe det ‘and faction of practical devies. should enable tho reeder to understand Tow solar ells work, to understand the concepts and model of solar ell ‘device physi, and to formulate nd sole eleva physical probes. A tough pratica materials nnd cevioe designs are taeda example, the book snot inended es 9 comprbersive review of photoveliaie mata sd doves, nor of te ats developments in photovolaisreerch (Chapter 1 lntroduces the sole cell as simple earrent generator and eins the performance caractortics which ge sd to dese 0 at pare solar cll- Chapter ?deseres In oneal terms bow ight energy is ‘converted ato electri, comparing the photovoteie converter with other ftom and evaluating the lta to efllency. Chapters 3 and 4 ove the ‘bse physi of the sericnduter, the seconductor transport equations sd the proses of light absorp apd earierreobiatio. Chaper 8 focues on the concept of the asymaetsic Junction, and datas the d= ferent typos of junction which are explated in phovovolnes. Chapter 6 apples the theory of eater ebapters to pn junsion, to easiea! model ofa colar ool Chapters 7 aud 8 ate concerned with the range of photo- Collie materials and device design, Chapter 7 dels with mouoeystline ‘rn jnnetion devices relating the model of Chaptar 6 to prctcal vies,“ ace ‘wing estan silcon and gli arsenide oll as examples. Chapter oul with tin th photoveltie materials, discussing physical procs tnd design ls relevant to tin films so focusing on the ways in which ‘he standard model mat be adapted fr thin fn devios, Chapter 9 dene ‘ith vriow techniques for manacing Light in onder to mastnke perfor: ‘mance, sa Chapter 10 cokers a range of approaches, sony thot, te increasing the efleleney of solar elle aoe the init for «singin band 0p plotoconverer Tam grateful tl of he people who have beled me poop thi book In pascu, to Keith Barer or passing the orginal proposal frm Ik eral Collage Pree in my directions to Leon Frere and David Ifeld for ‘ving me the opportniey to teach the pyc of wale cella to MSe st dente at Looghorough and so etal the baste ours from which this ‘bok developed to all the teuach student in photovliis at Imperial College fer rising many intersting questions, epedllyJeany Bars, James Cony and Benjunin Kufage: to Ralph Gotshal, Tom Marke ‘art and Peer Wore for hop with questions elated to material this Took; to Not BkineDankss and Jane Nelson for thes elf comments on the tox; to Clare Nelson forthe cove testi ad tall ther col Ingwer who hove bpd in ty seeurour to undead haw hes ings ror, in partir to Richard Corks, Joes Durrant, Michal Gree, Marti Green, Christiana Honsbeg,Stfan Ketan and Ellen Moons 1am grateful tothe Greenpeace Envitonnental Trust fo fang me to study solr calls before they were popu apd to the UK Rasiaeering and Physleal Sense Resaech Coun ad for an Adve Research Fellow ship whic allowed me o pend my Satay aRerboons writing chapters Instead of etree. Filly I am grateful to Joba Nava fr his encoutage seat to start on this projet and to Laurent Chaminade si bis staf et 16 ress and to Lakai Narayanan olleags at World Sees for their ep in sing it through This book is dediated to the memory of Stephan Rabizoon and MLV. Mecha, Jenny Nason London, Ape 2002 Contents Preface (Chapter 1 Introduction 11 Photous le, Electrons Out The Photovoltaic Etket 12, Biel History of the Selae 2a 13, Photovaltac Cells and Power Generation LL. Photovoltaic els mole and systems 182, Some unporaseceisions 1A, Characteritin of the Phoorltale Cal A Swmimary 11. Photocurent and quntum eficency 142 Dark current and open crit wolage 143. Bficieney TAA. Para eistaces TAS. Nowideal dode bbavioae 15, Sumay, References Chapter 2. Photons In, Electrons Outs Basic Principles of PV 2, Iaeoduction 22. The Solar Resnure 25. Types of Solar nerey Converter 24 Detaled Balance 21. In egulbsium 5 242 Under illminaticn 25, Work Available fom » Pstoveltaie Device 251, Photocurent . BEEEEN252. Daskcurent . 253. Limiting efseney 254. Biot of band gap 255. Elect of spectrum on iency 26, Requirements forthe Kal Phoaconveter 27. Summary References Chapter 3. Bleetrons and Holes in Sessiconductors 51 Tatoduetion 52. Basic Conepe 32: Bonde nnd bands incest 3.22. Flectzone, hols and conductivity 18, Election State in Soieonductre 331. Band smuctze 832 Conduction band 333. Valence band 38:4 Dizet and inet band ga 885 Density of states 886 Bletronditbution fusion 887. Bletron and hae currents 4 Seminndsctor in Eqllrium S41. Fermi Dirge waitice 4.2, Blectron and ole densities in equilib 443, Bolamann approximation 344. Blecteos and bole cureats to equlibc, 85, Impurities and Doping 51. Intrinsic semioonductone 852° neype doping 253. p type doping 354. Etec of heavy doping 355. Impefet and amerphonscystale 36. Semiconductor under Bie 361, uae thermal quite 362, Election and hoe dente under bist 363, Current densities under las 81. Dif snd Difforion ATA. Corent equations in terms of drift and dion 72. Validity ofthe dest ciusion eatations a8 3.73, Cument equation non eraline slide ‘Summary (Chapter 4 Generation and Recombination 41. Introduction: Semiconductor Taaspart Equations 42. Generation aad Reconblaaton 43, Quantum Mechanial Dexption of Tanition Rater 431, Ben Golden Rule 432. Optical pocemes ina two level ystems 44 Photopenertion 441 Photopeserstion rte 442. Thermaistion 443. Microscopie description of absorption 444, Dine: gap sconductors 445, Indivet gap semeonductors 445. Other txprof beainse 447. Beampler and data 45. Recombination 451. ‘Types of recombination 452, Rate resonbination 453, Simplified exresions for fadetive ecomblnation 454 Auger recombination 455. Shockley Read Hall recombination {£58 Sorfuce and grain boundary recombination 457, ‘Traps versus recombination centres 46, Formulation of the Transport Proble 4461. Commies on the transport problen 46.2. ‘Transport equations ina erystl 4, Bima, Reese Chapter 5 Junctions 51. Intoduction 52. Ongin of Photovtate Action 5.3. Work Funetion and Type of Jastion 5.4 Meta- Semiconductor Tunction S41, Betalishing fl 42, Bebviour in the light S49. Beluviour in the dark.S44 Obie contacts. 5:45. Limitations ofthe Sooty base ansion S55. Semiconductor Semiconductor Junctions 554. pen junction 552. pen juetion 553. pra hotornjunction : 56, Electtochemea! Junction 51. Justine in Orgale Materine 58. Suelo and ltetfce Slates 58:1. Susicw cates on fe srtuee 582. Bit ofterlee rates on junctions 59. Sammey Referee Chapter € Analysis of the p-n Junction G1 Introduction 62. The pn Junction 62: "Poomntion of p-n jnction 622. Outline of approach ©, Dapletion Approniation 31," Caleuaton of drpesion width 64. Calculation of Carer and Cucet Detities 6-41. Curate and enti denis in the nett regions 6.42. Cuments and earn donttie i the pace charge region 643, Total current dnaiy : 65. General Solution for J(V) 65, pen Junction in he Das 6.1. At equ 662. Under applied bis 67. pom Junetion under Muninatian Br. Shor crn 872. Photocurent and QE in special cases 873. _p-m junction as photovoltaic ell 88, Etets on pn Junetion Characteristics GSL. Bets of parasite rsstanese 682. Bet of erdiation G83. tect of temperate 4 re 1a 132 1 ro a 1 us 6 M6 12 14 156, 10 160 160 168 sr 160 1 m 1m 684 685, Other devin strstr ality ofthe apprximatios 69. Summary Referens Chapter 7 Monocrystalline Solar Cells TA. Intoducton: Pence of al Design 72, Matai and Design Isuet 72 yaa ra. Material dependet factor Desig factors General desig fetes op junction cals 7. Soon Material Properties 73 732 7a 73a ‘and strate and opt bsxpian Doping Recombination Carter anspor TA, Silicon Solt Cll Design TA. 742 748 Tat. 7a. 749. ‘asi sion soa all Cal tatiention Optimination of soon vole all dg Strategie to enance seoepion Strategies to ron surface ecobization Strategies to rede series eitance Evolution of lice cola ol design Future distons slic cl design Aerts to lon 7. II-V Semiconductor Matta Property 752 783 18 755 166. TIL semiconducor baad stuctre and optical sheorpsion Callum ansnide Doping Recouination (Cartier eaneport : Reflectivity 7, Gade Solar Call Design 751 162 763 764 asic Gas soit lls» Optmisition of GaAs Slee asign Stesogies to rodun ont ezine resrbination Steteges to redo series resistance 16 16. 1G 190 1 194 17 198 198 BSS2ER8 888785. Steatepes to seduce subtrte cust 71. Summary. A Referenies oo Chapter 8 Thin Film Solar Celts 8 Inteodaction| 82. Thin Film Photovoltaic Materials B21. Requirements fr eultale sterile 88. Amoephow Scan 83.1. Material propetie 83.2, Defects in amorphous material 888. Absorption 834. Doping 5 835. Transport 826 Stability. BST Related allye 84. Amogphows Silcon Solar Ct Design RAL Amorous eon p--n arctan 842, ptm anlr call device physice 843. Fubscation of ai solr ele S.G4. Strategies fo improve tell preformance 5. Defpets in Polycrystalline Tia Fn Materials BBL. Grain boundaries . 52. Bets of grain hounds on teaaspore 1853, Depletion approximation modal fr geuin boundary S54. Major cartier transport 855, Ede of Uumination 856, Minority erie transport 5.7. ete of grain houndary recombination op slar call perormance| ‘86. CulaSep Thin Film Solar Calle. 22 86.1, Materials properties 862, Beterojupetons in thin lia slr eal din 863. CulnGaSi sole eel den 87, CTe Thin Pil Solr Call STA. Materials propertice S72 Cae rolarcll design | 8S. Thin Film Silicon Solar Cains > 210 aun 58. Materials poperie 882. Microcrystalline slicon sla all devin 89. Summary. Referens Chapter 9. Managing Light 94 Ietodueton 92 Photon Pix: A Review and Overview of Light, ‘Management 921. Route to higher photon Bue 93, Minimicing Reotion 93.1. Optial propertin of umiconductrs 93.2. Amtireection coatings 9.4. Concentration BALL. Limits to concetetion 942, Practical concentrators 98, Bifects of Conssration on Device Physles D5: Low ijetion 852. High njetion 23. Limits to efciency under concentration DS. Temperature D5. Serie cesta 956. Concentrator ell eign 287. Concenteaor cll masa 96. Light Coufemext 96.1 Tighe paths and ray escing 962. Mirors 963. Rendomising clas 964 Toute cutis 965. Practical schemes 966, Light conning tuctures: restricted arceptance ste and external cavities 987. Beets af light raping on device pysice 97. Photon Reeling 8. Theory of too eeylng 9:72. Practical schemes 98, Summary References 2s 218 210 23 2st ast 8 200 28 268 20 267 m0 m0 m 5 28 280 21 282 236 288{Chapter 10. Over the Limit 104, 102, toa, 04, 105. 106, ns, Introduction How Mach ie Out Thee? Tstodyoanic Limit to Efidney Detailed Balance Limit to Eteieney, Reviome ‘Multiple Band Gape ‘Tandem Calle 1003.1 Principe of tae cls 1082. Analyse 105.3. Praca andes syste Intermediate Band and Multiple Band Calle 100.1. Principles ofwtemneate snd mip band cell 1062. Conditions 1063. Practial rates Tnctosing the Work Per Photon sng "Hot' Carine 107.1. Principles of cooling aad hot carers 107.2. Analysis ofthe hot career ola cll 107.3. Practical trataies Import Iokation Solar Cll 10.81. Analy of impact sonsition sla ol Summary References Exercises Solutions to the Exercises Index undamental constants agrogere Planes courant Planes eonrtant/20 Alec privity of fe space Stefars contact speed of ight in enum olteannsconsant five eletron nse harge onthe electron Symbols used in the text opens sorption ceficient Spectil photon fx donty per unit coi angle slecteonanity ‘gust Fer evel parson or chemical potential of ight emissivity te. probably of photon emision ile pernitivity of semiconductor polaristionvecor of ght ‘work faeton estas eve Dower conversion cies Imaginary pot of refracive index of semiconductor ‘worelenth flight hernia pteaial ip ectron mobility; bole obly equency of iit critical angle st opin terface langle width ofthe oz ‘nrg density or esistiviy| conductivity Ime Trp seston itis hole iine angular requeacy flit solid ange ‘waveinetion 1; grad operator with repel to potion itd operator with reaps wavevetarlp probability of pasta absorption call ares, spectzal photon Bux density normal to surface Corfcet for bimolecular eaptare by tap of elections; bles oii of bimolecular radiative recombination Aaron cont ison cousin of ecteon difison coefficient of hole lectromogaetc ld strength Feel energy of Fat level lectron quasi Ferml energy lee; ble quas- Fer evel ‘band gap energy af trap state ‘norgy of vleas band edge ‘nergy of conduction bad edge Intinle enerey vel vacuum energy level lett eld force probability occupation faction fr electron tte at, Fermi Dire probability ooeupation fnction seomeria facortlating nota to angular photon fx ‘lensity for emission om: amblent; ell sun, concentrated light sours fi fer spectral photogeneration rata per unit volume sesertion rate per anit value fetron geoeration rate po ut Wome Dole generation rte per ni lune lent of eloetionic sates pat unt energy per walt eyatl vole Hamiltonian operator Incense cay crest density Short cele curse density “ark current declty ‘letton current deity hole cusest density Ini bp Bree ee zaas ™ so ppe pars goy ve zzz special electron current density; spectral hole eumtent deny fxyatl wavevector “fasion length or length of erstal sale {fio logth of leon ifsion Inet of hole Ade deay ator eduction band effective mase talence tad eflctive mas AUpole mats lament anit of eer pe wit volume quiibelum eeewor density latin ener denity telnctive inde of emote Aleit of acceptor impurity atom easy of dance inparity lame ‘flective conduction band density of sates ‘ffetive alence band deny of tates shared balground doping in iti layer lena of trp tates ent of terface sates per uni ane Aleweity of holes per unit vole power density ull hole density slags ‘quntum eicleney potion anton rate relectivity eles rsetance ‘hunt or paral rsstance etoe defining a point sla ‘deetron surface recobaation veoety hole surface recombination velcey tie tenpercure of an cowry density of raiasion pe unit woke ‘recombination rate per unit volume ‘deetzon recombination rate per unt volumeUy ole recombination rte pe uit voune hag Auger resombination rate Cat radiative recombination rate san Shoctdey Rent Hall eombinstion cate ye solute vrsocty Voltage o bas Vig ba ia Bie Vex open ciel voltage Ve donor ionisation enerey Vj acoptr loizationenerey ‘ty thelness of depletion eegion in yer; player X "concerti factor ‘Acronyas fem lacromotive fore se akernatingeuctent de dec current AM aiemase AML sir mas 1.5 spectrum — stand fo solr ell libration STC) Standard txt conditions (Ch condveton band YB lence bond FCR Ferns golden rule PV photovaltaion Si amorphowe acon 51 exytalline silicon peSi_—mleroerystaline slicon SEH hydtgensted amorous sion SIC amoepow alion-achon alloy ‘SiGe amorphous soon germanium allay DOS density of sates DOS joint desity of sates “region inttnse or undoped region of y-- junction SCR spac charge region QP unto icionsy SRI Sheeley: Res Hal Gade alm aenido Cate imium tele cas: AR PERL PESC ‘Teo QD qw copper indium gala ahelnide sotrefeeion passiveted emitter, rear bealy dif colar ell pasivta emit solr cll eanaparent conducting eile photon reyelng ‘act dot ‘gaara vel longitudinal optical of paonos)Chapter 1 Introduction 141, Photons Tn, Electrons Out: The Photovoltaic Eiect Solar otovltsic energy conversion a one sap conersion process which enero etrcl energy from ight nergy. The explanation relies on eas {fom quantum theory. Liht a made up af pactata a energy, alle photons, ‘whoweeneray depends only upoa the bequenes,o leu, ofthe Hpk. The ‘nergy of vile photos sleet o exc electrons, bound into sli upto higher eneegy levels wbete they aro more fee to move, An extreme ‘example of this he potoelet er, the esebrated experiment hie tres explained by Elstela in 190, wes blue o ltravoe eke provider ‘enough energy for electrons to erape completely fom the surtce of = tnetal, Normally, wen ight absorbed by tater, tons ae given vp %0 ‘rite elactros thighereaergystats within the water, but the exted tlotrons quickly relax bck tot round state. In potovaliie device, | couger_| | Fig 11, Compan fh potted th Sr os mt it a tc al a). Te2 he Phi of Str Cats ome thre ie some iin atyinmety which pulls the exited loctrons ‘ay bee they can relax ad feds thet an eternal cea The exe ‘nee ofthe ected elton generates a yotential difference, ot eto. motive force (om). This force devs th elatrons through ell a the ‘sternal eu oo abet work ‘The eferivenas of @photovaltsic device depends upon the cui of ligt absorbing materials end the way in which they ove connect to the ‘external el. The follwing eaptre wil del with the underlying pe. ical ideas, the device physics of slr els, the properties of photovehae ‘mali td solr ell design, Tn thie chapter we wll mmr the nai characteris of photovlaiecel witht die asig it pipe fneon, te doe 1.2. Brlef History of the Solar Coll ‘The pctv ct wae fit reported by Edmund Boge! 1699 hen be observed tha the ation of ight on i ted latino eae trode immersed in electrolyte rote an Clerc current. Forty Years Inter the fit sold stato phototlie device were construed by Work rs invetgatiog the rcentydlcovered phovoceatity of selenium. Ta 410 Witt Adams ad Richard Day fod ft 9 photocarent cold be produced in a smple of selenium when coutcted by tw het plat num contacts, The photovolse ston ofthe sleniun dire ow ts Bltacondactive ation in tat cure nas produced spontaneonly by ‘heaton oflight.Noexeral pone supply sata. Inti only phe tortie deve, rectifying jeion had been formed between te en fondictor and the mca cotat. Ix 1604, Chae ts prepared what was probably the fst ngs ate slr el by pening le seu betwen gold ad another meta Inthe flloitg ens photovelas eft wre observed in coppercoppe xe thin fm struct, n led spd se thallssmiphid. Thee ay cells te thin fin Schottky barter devices, where a sslesasparet layer of metal deposed on top of the seacondutor provided both the ssymmetsic elton uncon, bh a ‘2ecesty for poiovlae ation, and ace to the encio fr the ie eo gt. The poiovlaie efecto structure ke thi wa lated tothe existence of tata to current fw at oe of the semiconductor etal Interfase (., retin ction) by Golan ant Brody n 004 Laser, Aorne the 199s, the theory of meta-sesconducor barter layers was devcop by Waker Schoth, Nevile Mot ad oes. However, it was not ce photovoltaic propetine of materia ike sl ‘lum whieh excited researcer, fut the photocoudactivity Te fet that ‘the curent produced was proparcnal othe intensity ofthe ineider ight, and related othe wavelength in adefaive way mau that photacondactive ‘materials were ideal for photograph ght meters. The photovoltaic eect In barrie strucrores was an added banett, maaning thst he Hight eter oul operate without «power suply. It wae wot unl the 1950, with the evelopment of god quality sien was forappations ia the ne slid ‘tte electronic, that potently ful quis of power were produced by photowotale device in cryetaline seen. In the 10506, the development of sco estonia followed the dis cy ofa way to manufacture jonctons in alien, Nataly type scan wafers developed ap type akin wlan expoeed ta the gas boron ticle Part of the skin could be eched away to giv aces to the n type layer beneath. These p-n junction stentuesprodued mach beter setae ction than Schottky bases, and better photovolaie brio, Te Set ‘ion sole ell was reported by Chapin, Fuller and Peston in 1964 and converted sunlit with an eleey of 6, si ines bgher than the best previous attampt. That Aguze wat ri significa over the flowing Witt, theo ells were ot srouly onside for ome enrtion fo ey tral daades,Novrcels, the earsoon sla el i tod the pos “iby of power generation in emote cations where fi could not ety be delivered. ‘The obvious appleaon war to eatelltes where the re ‘ent of relality and low Week made the cot ofthe els ustsportat and during the 1950s and 6D, sion oar elle mete widely developed for sppletions in spe ‘Also in 1964, a cadmium sulplide pn junction was produced with an ficiency of 0%, aud in the Elloving yates of pn junction ph ‘ovolai dvics in glum arante, indium poeple ad aden tl luride wore snulcad by theoretical work indicating hat these materials ould offer e higher efeney. Haveve, soon reined abd remains the foremnst photovltle material, beaetng fom the advances of scan tck- ‘ology forth micocktronies icy Sore Mtoe of Ue solar alae ‘ven elsewhere [Shive 1859; Wolf 1972; Green, 19 Inthe 170s he exis in energy supply experianced by tho oil dependent ‘western world fo a suden grcwth of interest in alternative sources of nergy; and fending fr eexarch and development ia tour area. Photo voltae was «aubjet of intense terest during this period, aad a range of‘ ‘Te Pin of Slr Cale "trates for producing photovoltaic devioes and materials more cheaply nnd fo improving device efsioney were explored, Routes to lower cot fm ‘led photoeetrochersialjusctions, an alteaitve materials such as Polverytlionslcon, amorphous alco, other “hin fin’ material and orgie conductors. Stratis for higher eee inladed tacdem and foe mall band gap designs. Alsough none of Use le to widespread ‘smmeial development, our understanding ofthe srence of photorelties, Is mainly rote in this period. During the 198, interest in photovotaes expanded long with grow dng swacenest ofthe need to seazesouteu of wetrity alternative fons fuels. The trend coins with the widespread deregulation of the ‘letiiy markets and growing recognition ofthe viability of donated, over. Dating this period, the economits of photovoltaics hprowed pi Imari through economies of sale In the late 1980s the photovoleie pro 0) than under reves bine (VO), Tie rectilying behavoa 2 feature of photovlale devices sine a asym junction is needed to achiw charge separation. For wo ial de the dark exrrent deity Sa(V) vais lie Lanal¥) = Ie — 2) as) where Jy is @ constant, i Boltemaaa’s constant and Tis temperate fn depovs Kelvin ‘Thora current voltage reponse ofthe ell ts crret-eltagechar- acters ean be approximated the sum ofthe shot ctl photocurrent sod the daek current (Fig. 16) This step known atthe spersition ope proximation Although the reverse current which Hows in teponse to velage inn luninated ell ino orally equal to the current whieh fone a the lark, he apresimation i reuooable for many photovltal terials and» Phe Pigs of Star Cae Uplecwret Curent ens il be sed fr the present discussion, The sgn convertion fr eure and voltage in photovolass is such thet the photocerren is poli. This the oppoite to the usual convention for electronic devices With this gn ‘xavetion te net euret density in the ell ie JO) =e ~JinalY), ay heh becomes, fra del diode, Soda Lei 1), as "Thi reli dave in Chapter 6 ‘When the cntats re ole the potenti deren bas isa ‘le, the open er voliage VTi equlen othe cudton en the disk current and short ect photocusent exactly eaneel ot, Por the si y(t 4 (441) ro Elon sows at tay tty ‘eee cit prog nears Fave hn ht el a pi et cell generates power, when the voltage le between 0 and Voc. At ¥-< 0, the ‘ena nan see ors ees % Fle 12. gut ofa mol potocucent whic ie ght dgpentent but bias independent, At Y > Vow the device again conuren power. Tai i the regime whete ight eating ios opeae, We wil eater tin is some materials th dark curse accompany the eosin of i ‘leciicaly he cla eal equivalent to «current generator in parle sith an anymmetia on hover tstve element, tu diode (Fg 1.) ‘When lumina, the idea el fodvoas a photocurrent proportion to ‘height ines. That phorocura is dvided between the variale resis tance ofthe diode an te loin elo whic depends on the reste ofthe lad and the lea of lution. For higher rextances, more ofthe photocirens dows through the dee, resuking nm higer potential dier- ‘ice ben ll ils Lu male curren tough the loa Tae ‘ioe tas provides the photovoltge. Without the dinde, here e nothing te deve the photocurrent through the ad 148. ificieney ‘The operating regime ofthe sola cl x the ange of bis from Oto Vo, which the ell delivers power The cell power density i given by Pow an P reaches 9 maximum atthe cae operating point or maximum power ‘bois This occurs a some voltage Vth a coresponding crrent desley dos shown in Fig. 15, The optima laa ts basset rerisance ven ‘by Va The fl foto i dein the ratio oe af Jatea sa nd deveribes the oquazenes! of te J-V cure2 The Php f Str Cale Ccument density Bs votage,V ' S24, cata an nd png (pu) re fm Feed J a 9 hy hae of he ane tang Th ir real ‘oe hee saa " ‘The ficiency 9 of the calls the power density dlivered at operating on a8 tection ofthe Incident light poser density, Jala a= tafe a) ficcy i related oJ and Vo tlag FF Leva E na (10) ‘These four quantities: J, Vo, PP and 9 a the key perfomance ear acters of aor eal Allo thes sould he define for partial Juminstionconitions. The Standard Test Coton (STC) for sla el Js the Air Mass 1.5 spectrum, an incident power density of 1000 W mn? ‘sod temperature of 25°C, (Standard and oes sc spect re disco in Chapter 2) The performance characteris for the most common sot ell atria ae ited in Table 1. ‘Table 1.1 Shows that solar ell materials wit higher Jac tend to have lower Vax This i consequence of th material mde prdelaly of eee’) Va) In aA) FF iawn 00 Jeol mA em? Veet Fig 10, Plt oJ gins tol ie in Tal Mate with ih "Tobey hae tow the atop pec inthe crete! the band gap of he semiconductor. In Chapter 2 we will sce that sete ea ‘undamsental compromive between photorartent and voltage in photvatale coergy conversion. Figure L?ilrtrater the corrdation between Je ad Veo fr the eck im Table 11, together with the vlattonsip for 6 ell of smasimm eficiery Last, Parusitic resistances Tn reat ale powers dssipata through the resistance ofthe contacts and though lage eartonts and the sides of the devin. Tae eee areTre Php of Ser Coe Fle 140, runes ce ing wi an shat itn ® ® Pg 131, tf) ming le nd) ring pct vaitaoz ech ‘etc te mas po etna spate oe oa um ctl to wo pa esac in sce (Ry) ad in pa allel (Fu) with the cell (Fig. 1.10), ey 7 ‘Te sais resistance aries fom the restance ofthe ell mate to useot fom, particularly through the Hout alae to the contacts, ad ‘hom resistive contacts, Sais rasitance i particular problem at big, furent Gases, for instance under coneutated Fight. The paral ot shunt resitanoe aes from Klage of enrtent through the el, eo {he edges of the device and between contacts of dflrent poatity. Ii 8 role in poet recifng devi, Seros and parallel rsstanou edo th fl factor as showa ia Pig, Lt For aa ffcent cll we want Ry to beat sll ed Ray to bea lve a pombe, ‘When parnsitic eistances are included, the diode cguation bosons Jade eta) CATA any 145. Nonvidaat diode behaviour ‘The “ideal diode behaviour of Bq 1.5 be seldom son. It is common for the ack current to depend more weakly on Bias. Tho actual dependence on V ie quantified by an eality factor and the cztent-votage characteristic ‘Ben by tho wonideal die equation, Fade fev 1) au) 1m typically es bate 1 sad 2 The recone for nop-ideal bbevicu wll be dicunsed altar chapters 1.5. Summary Apltovlta ell costs of he absorbing materi] which s eannecrad tons external ciel nan aymmetsie manner. Charge carrer are gener ‘ted in the material by the absorption of photos of light, and are deve towards one or othor ofthe conta the bili pata aeymunatry. This light driven charge seperation eablshes a photovleage at open cca, tad gencraon a photerurent thet cet When led ent 20 "hs eternal cle the cell produces both eure ad wotage ad at do ected work, "The sae of the cuent generated by th cl in shor cies depend ‘pon the nent and the ener spectrum of the nsdent ight. Photocu reat i elated to ncdent spectrum hy the quant effnney ofthe cll, hich the probability of generating a eleirou per incident photon as = function of photon energy. When a loud preset, a potetal diferenoe i created between the ternal ofthe cl aad ths dive a cote, wally felled the dark current, a the o2postedection tothe photocurrent: As the lad rstance i inereoed, be potential diferance increases md the ne eurreat decreases until the phncocurrent and dar cate exactly canoe ‘out The potential diference a his plu scala the open cet wlage [At come pola belore Vo ie veacbed, the eurent-oltage product is max ‘imum, Tai sche masznum power polit and the cel should be operated ‘it Ind resistance which consponds to ths pol The dolar ell ean be modelo ara carent generar paral with an ea lode, ad the errent-voltge characters glen by the deal diode ‘uation, Ba. 1.5 In real elle, the behaviour le grade by the prenace of eries and parallel esstanoe,® he Pyles of Str Cale References D. Arden, Clan Bit fom Plt ed MD. Are nd. a, Ei aon: espera College Press, 2001). : 4. Goi Pls Cag Car BEB Pte tt pee Cy) low Ser Bris Bary of Potente Sytone (og, at Sr Bry A Mie: Malor ene faa Nc Wal rea elope wae Pe 8 Prue Sores ton 1072 In Dlr Caw CE Bash (ERE Ps 10) Chapter 2 Photons In, Electrons Out: Basic Principles of PV 24, Introduction I Chapter 1 the sla all was introduond and it performance character: {sts Ia vespnse to apple bias and light, wero defined. Tn this chapter we adres sone of the thermodsaamie axpets of photovoltnc solar en ‘erg convert, The chapter srg as follows it the radiant power ‘lll from he sun defied the photovoltaic el x dsingicbed from ther typ of aolar energy converter and the question of how mick eee trical werkcaa be extracted is addressed; the principle of detailed balance is troduced and used to esulte the performance characteristic of an eal photovolisiceerzyconverer, We shall sv tat efficiency depends on ‘he hand gap ofthe abmcbing mate al he incident sport. Final, he properties which are deealo for high efciny in Fal photovoltaic ‘material nd devon are dace, 2.2, ‘The Solar Resource "Teun ee ight with range of wavelengths, spanning the tase, slo andintnred sation ofthe ekctromagnetie spectrum. Figure 2.1 hows the amount of adit energy tesined from the sun per unit area per tai tne — the solar lerainnce — ar 8 fnetion of wavelength & point ont the Earth's atmephere. Sole iradianof greatest at visible ‘wavelengths, 00-800 nm, peaking ia the blue-green, "This extateeotvial spectrum reels the spite of black body 8 ST80 K_ A Black body emits quanta of radiation — photons — with a Astebtin of energie determined by ite characteristic temperature, Ty ‘Ata point onthe suse ofthe Hack ody the muuber of photons with eesng per nit imo, the seta photon fur 8(B, 2), gen by a = (ke Awnnamesiea 2, (8 —)anaue ax) where dS the ele of eutace 4s and do * ates around 6 and df he unit of solid ange around the dietion of exon of the ight (0,6). The Ds ove ero testes en y he component a need angle and resolved along dS, aa Scwrnasie = f 6.9.0.8) cosean ade Be (seme) osu ea) he Fem ior he fom inten oe he tlt angle rset a he sure fhe tee Se ie a ‘sa hemisphere and F, = 5, Away from the surface, a Sai estes, he nga tages Farsi hae as) hace Gan isthe bl angle subtended by the radiating boty to the poi ‘bare te Bux measure For the sun ae sen fom the eth = 0.206 {ot selon bye fetr of 4510" t2.16310-% Ihe temperature ‘all points os the surfco of the black body othe sume, then she ‘stzment scan be dropped fom by, and Ba. 22 ean be writen w= 2 (cee) on Tah rising ton of it eh int f he cher owl wb ad sot hes pn a ed poet reta Peto I Beton On Base Pine of PU » Box 2.1. The angular solved photon fae density, 8, lathe numberof ‘Photons of given ues) posing though nit are i unit tne, per vn Solid angle I dened nan entnt of surface are, sad te detion is dei! by the angle tothe stefce oem 8, ad an selmutbal ane, projected on the plan of the surface element In structures wit plana? ‘ynmatry i sflent to know the photon fax density resolved along the ‘ovr othe surface, be obtsined by iterating the components of ‘ocnal othe sufi over sod ale ‘Ta exit energy fx deity or radiance L(B), related tothe photon Bux density through = ey ce Inspating Ba. 2.4 oer gis the aa eed power des, oy whee Stan's cet, _ aed °° see 1 theese thi a power day of 62 MEW m2 Aa pint Js ute the Est atmonpire te sles eed (on acount of bureau geo hen) an tela poe dey seen torasa Wn! In Pig 21 the enteral slr ope pare sith te spectrum of 760K Back yee hy the tor 40 10% “The higher the higher the wecage energy the ented ration, ‘ack body a the temperate of he Bart, T, = 300K, ems not ‘ong inthe far infnedand reson eat be as. Fo he St, ‘eth = 510 K the lation strong a ve wavelength A ote Ton woul ee Hgt that appease eto wy wha oper shied 1 Shorter wavlengts on Fig 2 and weaker om wold apa ed (On psig shou he ape, igt abecbel and satred by ‘avo inpere ovata on th opecrum exching the arts» The Papo Str Cale E a : 5, Sesh eee Wavelength / nm $5 21, eres (Ae ao) sl pct (ik ea) cpa wiht SE Sana da ct ‘urface is bot ateonated and changed in shop, Ligh of wavelengths fess ‘han 300 mm efter out by atone and molecular cxygeo, oxen, aod nuttogen, Water ad COs absorb mainly i the ifhared and ate vesponate forthe dips inthe absorption spetrun a 90), 110, 1400 aud 1900 na (20) anda 1800 and 2600 nm (CO,). Attenuation by the wtnonere Gated by the Air Mas factor, nai defied follows optical Heese, 5) where the angle of elevation of the sun, es shown in Fg. 2.2.‘The Ait Mass maint spectrum is an extraterestil solar specu ate lo masa thivesses of an Earth atinasphete of standard ticks and ‘The standard spectrum fr tempartuce latitudes i Air Mose 4.5 ot AMIS, comesponding to the sun begat an ngle of elation of #2 ‘This atmospheric thickness shold attenuate the slr spot te & ean leatiace f around 900 W m-4. Howeew, fr commence, the stanford teres sla apectrum is defied the AML spectrum tortatved so {hat the iterated irradiance ie 1000 W mn-3, Acton itdlanee ely ‘ary on seeount of casual and diy vasiaione inthe potion of tho sug Peto I Beton Ou Base Pcie of PY Ps ‘Se atoms to arse he Fan war. Toi gh a he sie muna ome sod ein of te Bath nd enon of th Avenged al un ay ethan 10 Win ih doce 30 ‘vin epee (aly dace cones) a hoes P23 ara soe in we cel eee omyThe Phat of Sa Cale For eficient solar olltion, the solr collector shouldbe dtl facing the sun However, aviation inthe pasion ofthe sean tht ay Aa plate collector in fel position wil fos the sun only part of the ne ‘Teackng epsom canbe used to illo the sun but these tease the cos, Scattering of ight hy the auzcapere teass a fetion of the het ls sis, incident from all angle rather than det fom the sun Ths {action ie around 15% on average, bt larger at higher Intec, aad a feeions whee there isa sguifcant amount of cloud over Dies light resents diferent challenges fr photovoiae conversion. Sete light sore te aot pallet, they cannot be retraced or concentrated. Masel wit ough saces ae ratvly better sulted for difwe igh ny perfectly ‘Bt ucaces an are less sensitive to movements ofthe si, 2.3, Types of Sl 2a ert att Sogo nian marae Soe Sins eRe u ‘tmeray), or it can increase the potential energy of the electrons. Which of ie meresanaoriemme sta rere cere ela nto ours stm tceeie coer eer etait Seems oteeeceeem tee apie ioe sei esarnyamasamene as Seba oeaeae oie eae es oe Absorption of photon in matter causes the promotion of an electron tore movies mils teers Energy Convertor ‘Pleo I Bln Ont: Basic Pig of PY a be exacted, the exo stato choold be separated from the ground state lay an oneegy gop which lrg eeapared to hy, where by is Bolzmann's enstant Therefore the aera should eotaln two ot uote energy levels, for bands, which are separsted by more than byT. a Chapter $ wo will ee Unt i seeonductor i 8 wey good example of such a system. The Separation of the energy bands, or nd yp serves to maitaln the excited ‘etrons at the higher energy for long tine compared to be thermal ela tion time, s that they maybe cllete, Flectrons in ech ofthe diferent ‘handle o form lea herp equlibium, ello © qua thermal equ ‘rtm, witha dierent chemical potential or, quasi Porm levl Tn ato ‘bal aptem, the inereae in leroceral potential energy gen by the Gibbs fee energy, NA, whet N's the number of earns promoted and Sy the dfleenc inthe chenizlpoteatial baeween the exited popa- Inton and th ground stat populstin, The diference in which resus ‘fom the abeption of ight i sometimes called the chemical potential of radiation. In equibvium, dy = C, Extortion of electrochemical potential nery ffm ight ip ths woy mst efetive when the ground sate ill feially andthe acd sate py. Unlike the solar thermal converter, the photovoltaic converter extracts solar eneey nly frm thoee pons with eer aieient tn rie the tas gap. Since these muinly isrense the dectrochemical potetial en fey the increase in internal energy Is much ls. Tn practice, inensed tecperatre ean decrease tho efisiency of photoveltaic conversion and 60 photovokai eal are usually designed tobe in good thermal contact with the amen. ‘To complete the photovoltaic conversion proces, the excited eletrons mst he extracad aod collected "his eqs a mechan fr eharye ep- sation. Some intrinsic asymmetry i needed to drive the excited lctons ‘oma fom their point of eesti. (In general, cargo separation involves Daltve hola andor Sona as wel ax leer. We desribe the proves in ‘ema of eeeron for srpliity) This can be proved by let coracte such that caries with aed ood state) ae aleted a on contact fad the with low (ground tase tthe other. The difroce in chem cal potential beeweea tho contacts, A, then provide patentildiference ‘between the terminals ofthe eel Once sparatd, the charges should be sllowed to travel without los to a aterual cut aad do eetial work. Photovolaic conversion is slay to photochemical energy anwersion (9. photosynthesis), in that radiant energy produces an ioerese tn lecteoie potential ence, etn than eat Inthe eave of photoeso The Phy of Slr Cae {er yap ope act aay, ala {Reo promo ys weno cap pr Ti ing et ‘the ected sleton population drives cecal section, the conversion of (60s and water into carbolsdate, eater than driving a ltrs excrent But in itor eae thesola eneegy seule in ant fox of eletonie potential ‘nergy constituting work. The difrent modas of slat energy coaversion ‘rw cxplaived in deta by de os |e Vos, 192) Inthe following ections wo wl eaealate che amount of work sraable from « photovaltse devi 2. Detaled Balance (One ofthe fundamental physi imitations on the performance of phato- ‘oka el arises om the pine of deta alan, Ae wel absorbing, solar radiation the solr energy couvorer exchanger thermal adistion with its sucoundngs. Both the cll and th susounding environment radiate loog wavelength, thermal pbotons on secoust of ther finite emperstuse The rate of lon of photons by th call ast be matched by the fae of soto sbextion stan th tly ae henson ofeetone in the material rensie onetant, 24.1. In equilibria Fis me consider the olin the dat, ermal equim with the sbi et, Astuning that she ambien radiates ike x ack body a tempers Tay then, aecording to Eq. 2.1, it praducea spectral photon fx a pat ‘on the arace of the sla call of ean onesie = 25 (ay) anasus Photne my ros Ont Basis Prin of PY » Integrating over ditions we obtin the nsdent Sx of thermal photons ‘ormal to tho surface ofa fat plate sla cell eo, share the geometrical factor = 5, essuming that ambient radiation i Tocrived over a bemipbere The eulalent current density absorbed frm he ambient i Juw(E) = 9 RUBIACEAE) en were (Eb te probability of aborption ofa photon of exergy E and RUE) kthe probably of photon rellection.n(E) the eletzen cutest 0. Tn these eandtions spontaneous emisin is iereged ad dulE) Photon In Boone On: Base Pipe of PY the rate of eaieon depends upon This makes sense since whes more ‘estos tea aod eng, rlsaion events ave more equat.Actord- tng o gonealed form of Pld aaton Iw, ee spectral photon ux ‘nie rom a body oftamperatite Te and chemical potenti Ay ito 8 ‘medium of refacsive index rs iven by 6.0.0) = Be eo om er uit surface aren and solid ale (Werf, 1952; de Vos, 1902). Ite. [rating over the range of sald sage trough which photous ean sscape (0's 012 @) mechan the photen Bux etal normal she surface 2 3 3 a s.=0i-' (#) ‘by Sols aw, were ng the reactive index of be surromdng medium. ‘Avs uface with alt, no = 1 Be xaf = Fy = rand B ST Note tht thie seul isthe mane whether the integration ix taken over internal or external slid ange internal, my mst be reained but the angular range i inte to Be, while externally ng = 1 but the angular range ise henispbe ‘Now if i the probability poton emission, th equivalent curent ensty for photon emsion is Sn) = af REED HCEDME, A). ais) Tein cay ose that Bg 216 recur to Bs. 28 for the ell a equim, ‘where @= = and Ay = 0. Its wot immodiataly obvious how a(E) relates to e(B) forthe cll with A > 0, However, i has been shown elewere (Aso, 100d tom generated detalod Balsne argument Chat Bg. 2.9= The Phy of Sor Cals sll ols, provided that yo ie conta through the device. That result Wil be us below without prot ‘The net equilentearent density, fom Eas 2.10 and 2.45 in Jus) ~ al) mi (wr (t+ Bats) -r.on). aay ‘This may be divided into contributions fom net absorption (in exes to ‘hat a equiibiua, sot =a mini (4 Bie) ey shennan eres ety Jamon = a RUE AEN ACE, Au) — (8,09), (218) oting hat bE) = &(E,0). This radii recombination isan unaolde ble oss whith means tht abeobed solar radiant enegy can none be fly wise by ee solr ell. Radiative reeabintion le dscnsadfrts sn Chaat 4. Now we have enosgh infrmation to clelste the abgolute limiting efi cieney of a photovaltae converter. We will coer a two band spten for which the ground state (ler band) ie itily fall nad the ceed "ate (per band) empty. The bands are separated by tad gap Es fo that abt with E < Ey is not absorbed (ve Fie. 2.6) We wil cane at eectron in each band are in quasi thermal eqilrtm tthe saben temperate T andthe chanical potential for tht bad, 25.1, Photocurent Photocurent ls de to the net absorbed fsx du tothe sua, Bq, 2.17. Since the angust range ofthe sun i so sll compare tothe aba, ‘he coco teria Ea. 2.17 is usualy neghstt, Trench eeccron ban 0 probably, (8), of being collated, we obtain the photocurrent dvaty Phen In Blom On: atc Pine of PU ” te ih 2 By ven scons fn By ran tapsaain One eed the Sent tae sae say Berto sh sey epg ote ce tena[l aon-nomenone. — a ‘This ie Wewtlel to Ba. 1.1 wth the quant eicincy QE(E) given by the product ofthe collection atl absorption fine, wna [f onneae an cor se fenton haw ae 2 Pershore pon seeng mae a thal wi ‘ovate BoB, west s pane cv deen ste ‘oper We ter np: ee sg spn {Ron wich suv de abn nested te te tema ft dvr ote or se ce lB Ts git asin Prat tn od year et eee ee a eee” he Pai of Sor Cale sn absorbed photon ~ dows not happen, Then cewy-umaf) BR on “ Loe. ox Photocurrent i then © fenction ony of the band gap and the indent spectrum. Chel, the lower, the greier willbe Ja Tia le fom 1g 2.21 that itis necasary to define the spectrum for any statement of sffsoney, 25:2. Dark current Daskeurtent isthe current tha ows though the potovltic devi when ® bias sapped in che dark. We wl suppor eatin the ideal cell ate alo esate are lst through now-radtive recombination, for example ‘delete wien se mates Th ly le pres iret the ‘Soidable aitive ration of electrons through epoatansous eosin, esrb shove: The dark current dens due to ths proces i given by oes satan ne f0-RMENAE: a0) AABN, 2m ee ee SRR atpt ca noe al ms tom ler en ae ne ee Soaps aap oa a acer ese Scere eetek ey Woda we obain forthe ne lesen density, WW) 4 0-me ye) - 6460 -NiEANNE, =) ‘Pratn In Bttrone Ons Base Pris of PV a Tor the special cae ofthe stp ke absorption fnetion (Bq. 220), a) [is16-0e0n snore, aa 40 en hea a pa en 21 wet SV) = ta Sle =) here J ina (tmperataredepenent) constant forthe partlelar uteri ‘This exible the Heal code Es, 14 "The ne electron exerent ths doe to the diferance between the two photon fis dente: the aborted fis, which e disebuted vera wide range of poton energie above the thiesold Ey, and the ented fe, whichis eocentratd on photon enrgas near By. Av V faces, the ttl th inereaos andthe mt curtat dectaste. A the open cecal voltage Vor the otal emitted fh exaaly alanos the total aorbed Bux and the tet euerent ie ser. IF is ineresed tll futher, the etd ‘ux excseds the absorb andthe cll bogins to act ke ight exiting ove ging out ght a earn the applied etical pote eae [Nota that Vg ast aap hele than 2. The spectral Buses ean to thee regina are ilstratd n Pe. 27(), while Fig, 2.70) seats the resulting J(V) carves 25.8. Limiting efficiency ‘To ealtuate the power conversicneficeney we ned to calculate the i ‘idaut and extracted power fou the photon fuse. The incident power easly Ie obtained simply by intgrting the cen radiance (Ba 2.) tore photon ener, = fF eateae. 225) or the ourpu power we nod to know he lice potential energy of the extracted potoslectros. Fer the Meal photooaverter tf amed ‘that ao potential i st through stances aryl inthe cet There foro all collected electrons shoud ave Ay of ects potenti energy end aver Ay of work tothe extra cout, Sine Oy. me have for the2 Me Pye of Salar Cte es s ' z we se° Be ide HE ces TE: =| East] ° ‘Bias /V : © 27.) Ath (3) amted (91) atm bh spa tn feat et Sy ar Vat tangy as oy ee Sa (ese dois font ely td eer sda seco Pto I, Besons Ou Base Price of PY ® extract power density fom Ba. 1.8 P=vauy with J(V) given by Bg 224 cbovo."The power conversion iciency ie = (228) Masini efeeny is achieved when 4 fuww-o. em ‘The bins at which this occurs f the maximus power bis, Vitae in Chapter 1 ln Fig, 27(b) the ontput power density for 4 0.7 eV baad gap potoconverter ina black body curs plotted asa funean of bas. A the ‘maximum, Vg = 045 V, tho power conversion efceny is around 20%, 25k. Bifet of band gap Given al of tho assumptions mad above, the power eoavesion dency of the del two band photoconverter ea fuze only of ad the cident spectrum I the inden spectrum is xed, thon depends only on the band gap Inti ean sr that ery stall and very Ite Bao gene wll lad to poor photoconverters: inthe fst came bonnes the working tale of V too sal (Vp tke Voy 8 aay 6s chan Ey) and in the scone becanse the photocurrent is to smal. For any spectrum ther ‘ optimam band gap a which has » maxitm, Fite 2.8 shows the ‘aviation of with By ena in this way forthe standard AMIS clot — ‘and Gap evFn 5 ie be Pi 28, Poe waco ah tty a SHO Kan pom i ‘pect, I bas 8 maximum of about 33% at an Ey of aroind 1.4 eV, pimising the performance of tho ideal single bad gap photoconverte Ahereoce «mater of chosing the ight materi Jn Fig. 29 the evalable power spectrum for an opts band Exp fell at miximum powerpoint ie compared with the ncdent power fos & ‘ack boy sun. Cleat, n0 photons with carey Tee than Ey rete 'o the salible power. Photoneof E'> Ey are aberbei bu lve aly ‘Al an) of electrical energy tothe ld, so ouly Ap ofthis poe ' avilable, The figure sows how thie tnction falls aa incense, Eros st E = Fy only a racton /By of the incident powee ava, n< Ey 25.5. Rifect of spectrum on efficiency ‘To mode! the influences of spectrum on lmiag effcieney, it i convenient ‘to ues lack body spectrum at 7, tho iunioating sure The spt of 5700 K blak body wth the angular with ofthe sus goo mel of ‘heer terest (Ai Mass 0) spectrum au prec aitting een) of sround 256 at bandgap of 1.3 eV [Aca 184) sonnet wer tha the maxims eency in AML S. the spectrum sifted to the ee, by reducing the tmperatue of te see, the optimum bd gup and the imitng efceney ae both ec ‘Cea inthe mit whero Te ~The ol sin eqlitns wih he soe and there isn nt potoconvesion. Oa the other han ithe temperaine ofthe source Is neessed zlative to the cell ois the Photosonerion ‘Plaow ty Bstrone Ont: Base Pra of PY » ‘ficiency: In the Hmit where Ty +0, the radiative curent vanishes and bias bas no elect on the net photocurrent. The the optimum operating bina is V = Eg/a (anything Bho ie piyszallyunzeamonable) andi ll ‘arity are colsted with y= then the mass elcinsy i ven by Bf MEE Te BEE Thi a maximum of aod at» bad yp of 2:2 eV fora 100K ok boy wn, ieesng a ih vale ad higher bad pe bet sos, This limit nar rept by Shee end Queer (Shockey, 196] {the ukioate een of he whe al In pracize ee cooing af the tal below the ambit resto a inp of ey which rode het ‘Seine Aoter way of improving Us icency sous he speceun i 0 ster the angular wth of the at Rec fom E22 that the wl x cosas for Fy whic erent ald angle teed bythe 1h age inceael by cnsntrting the ih, then photon Wilicrene and the Gt te (ote in he ingrad nE 224 Siliereaecelteta tha seond (cated hn). One way flog as St cone that whe thea emi raation ill eto arb sung only fom anal wager rang. Teasing the ange nee inpoves the blanc, a dows reat i anglar euge freon. ‘Th willbe considered ia more dtl n Chapa . Opting he pomer ety then de ow {B) cre with a ihe sina ale Band gaps For ist which eect by factor of 1000, hing Aticlecy of shout SSE at By = L1 eV i pritd ary, 105, For 8 eoarzation factor of £4108 the msm) oer 4%. Howe, thee erties ignore the paca fit that adr bigh concentra ‘heal il be bead, nd emit ere ton 2.6. Requirements forthe Ideal Photoconverter Tithe above me made the following emunptons: ‘+ thot. our photvoltaie material ha an enray gap which separata tater ‘which are normally fill fom states which are normally empty: 1 tha all iniene light with B > Ey i bobo, 1 tha ead absorbed photon genatesexacdly one eaton-hle pai% Phe Pee of Str Cate + that excited charges do wot recombine except radiatively, a tequired by dead balance, that excited changes ace completely sepacted; Shs charge is taneperted tothe external cult without lass ‘Lets exaine what thes assumptions mia for el phe ystems, Energy gop Many soil tate and molecular materi sti the cudition othe ence ot baad gap, The nee for conductivity take semiconductors patil tullable, With band gop ia the range 0-8 semiondacor an bors Valle photons to excite elcetrone ates the band gop here ty ay be collected, The TI-V compound semkoadutere gallu arvenide (GaAs) ‘nd indium phosphide laP) have band sp chs tothe optima (LV and 1.35 eV, respectively at $00 K) abd are faved for high efclency coll The mest popular solar ell materi eon, has ales four ‘bandgap (Lt eV, manain efiieney of 2%) but behanp ant alm aot compared to thee II-V matetals Other compound semiconductors in portiulr cadmium telluride (CATs) and capper indium gal diss lene (CulnGasa) ate being developed for tin fm photowliaics, Recent velopment in semitonctingmoleeular materia adit that organic ‘miconductrs ar promising materia for photovltle energy eouvesan in the tae, ight absorption High absorption of tight with B > By le straightforward to echicwe in rineple. Increasing the tickses oft absorbing lage increases ia opti cal depth, and for most semicondictors alma perfect abworption ean bo ‘tev wth a layer fw teneof dreds of ancroos thick. Homer ‘ho reqlesests o high optial depth and perfec charg elton, ake ‘ey high demands of material quay, Charge separation For s current tobe delivered, the material should be contacted in such, ' way thatthe promoted eaetrone experience spatial asymmetry, whe ‘rive them away rom the plat of promotion. This ean be an cet fli, torn gredas is electron deny Phan my ocrone Ost: Bae Fic of PY 2 ‘This asymmetry canbe provide by preparing junction ato beneath ‘he sutface. The junction may be a interac btwevs to leteonially at ferent material or between layers of the same materi rented in ferent ‘weys ts normally lange in enea to maxis the amount of solar en. orgy intercepted. For effeientphotovelaeconverson the junction quality Js of centea importance sce eactron should lee as ltile as pose of ‘hei letreal potential energy whl being pled oy. In practice prep Ing his large area junetionsuscutly aad witout detent to ati ‘quality Is 8 challenge and nits the numberof slab teri, Lossless transport ‘To conduct the charge to the eateraal crit the mtesil should be 8 90d electrical conductor. Perfect conduction means that catiers mst pot combine with defects or impurities, and should not give up ery tothe ‘meu, Thete should be no resistive los (uo sree eit) or eurent leakage (pal! resistance. The matetial around the uneton shuld be ighly conducting nd make good Ohne contacts to the exe ecu Mechanisms for excitation, charge separation sad taneport ea be c= vied by the semiconductor pn fonction, whichis the clas modelo & ola ell Tn cis system charge eeparstion ie chived bya chargd junction bucween layers of semiconductor of diferent elatrnie properties: es te x/a, the energy pectrun repats ise. This a bene in period tate ith period 1; wavoveclors which dliler by maple of n/a cannot be distinguished* The Pre of Slr ae Fe 35, Sehontc band sat ira of et pp sect, For most eystaly, fork < Othe function E(k) is Wena to E(-K) since ‘ats with postve and negative Kare degenerate, Tete al the afr. ‘mation about E(k) is contained ia the range 0 < k < x/ay ad ony this section ness to be plotted. The point k= r/a is called the Brilen sone foundary. At thes points, the wave fanetion i a stauding wave and the sradient of B(k) vanishes. Whether the rnergy tects maximum ot © ‘minimum depends on the symmetry of he bat ‘Weare interested inthe minimum snd masz ersies ofthe exystal Inds ine these determine the bandgap, etd inthe fre of E(k) nese to ther stationary pots. 832. Conduction band For the conduction band the minimus of the eneey BtKk) may occur =O anther value of corespoding to an important direction i he cexystl Near to wlntnum of energy atk Ko it often convenient to expand the E(k) in powers of (J o.) ail apvonimate Bk) by _ aa whore Bg = Ba(ka) me Wa parameter with the dtatowe of mass and ‘cline rom the tao stctue by PEW) ae es) “Thins the port land apprvimation. The effete mas m2 isanalogons to the mas of ree elatrn my, ut difers fon rm Chrough the difeent forces experienced Uy an elton within weryetal ato, mg ean be roater for lens than my ange vlues ofr ply thatthe conduction eecrons fee strongly inBornced by te atmle peteatils. mz describes how the ‘momenta P conduction decteox responds to an app face, F Pam. oo “The vale of mie deters by the atone potenti, The festive maze sone gin which the () eater ito the eecteon aypanies in this ap pronation, In general n shouldbe a tersor —dependent onthe detion ft che eplind fore and the detioneof th eystal ase. Homever ose to the ba nium the bond structure fen lotopie and mca be spprosimated by constant "De to terns aE, 2.2 ceptesnt the potential and ine ener of ‘scondction band setron with waverecto Te he ured bo derive the ‘deeton voc, = hx) 0s) atk) sd momentum 60 3.8. Valence band Tn the valence band, we require an expression forthe eneray ofthe Bole ‘ea to the alos band meni. lnc «hol represents the abwence of fn election, and elcome prefer to have alte enorgy as posible, the Inost stable station fora oles where the electron energy i simu. "Thetfoe holes are moet ily to wt ear toa aleoe band esdnum, ‘snd hav Kineic energy which eros ue (kis tedced. Fora ale oat 1: VB masimu at k= ko, the energy can bo approximated by — ele? an hore Exp ~ (ks), reatag ina hole velocty of Nek) 3)Aik) ao) bere the VB efctive mas, mi defined though (2.10) fo thatthe mass is normally postive. In gene, tho efectve masses of slectons and bole in the sume selcendactor ate difeent, becouse the urvatute of the cordcton advice bands ze difecet. 3.4, Direct and indirect band gups ‘The minimum asnount of energy which wil promote an electro fom the ‘aloe bad ito the conduction hand eal the fundamental band gap Ifthe CB minimum aad VB maxiaiim occur tthe sane value of ke in a photon of enery By issuer to create a eletron le pat Th ‘ype of semiconductor i ell sie! land up tote, Now, ifthe CB nisin and VB maximum ocr a dierent vox ‘f; &photon with energy Epis not ot is own sat to cree an — i be © . i . we EN vo : +; = ou oa . = Fi 26, Damiy fest tenn 5) mind wih pol bands, Femi Be ut fanny (5) and emer eto, mB) a eens ad fe) at T= Oand fate eaperires he Phy of Slr Cay 3443. Boltzmann approsimation For aealedcior at ucate othe vane bad i sgl he leon an completly ed td hed td somal ny Ten tnt th eo rel sl mene in th bo up. Now. Ey lar noha Seth hand tee fo canbe ml ppovinatel te Matoa Sekeneen fe, te comin bad wn Ee IME BT) 8-807 29) sud inthe valence band whee By, a he 0 ryontos simply th seria he expe fn 1 abn En 27 and 399 In ch parse band meee ad Ea $18 and 3.17 for (8), aod pcan be eau oath We Sad ot n= Neexo((Be ~ B)/AyP) sn) hee the tnt lle the eve aed bao states and is given by ae eta non (sSt) om) Sty fe oe ey, Neen — Byun xy ‘hr he te ele band eyo ate — Nena( SS - qustons 331 and 9.8 sy, very simply, tat the electron and hole densities 7AY ‘anoowatally With he postion ofthe Fermi level nthe band san ‘Morsover, they tellus cat for any give tthe hat or any genta sen temperate p= Nae ar, (35) ‘Thierens ued to define constant propaty of the ance, the Indrnate corer dently nhenp=Nake ter (636) 18 equal ta the density of electors which ace thermally ected ita the (CB of pure camiconductr in tcrmal equim, and is pees also sul othe amber of les wh have Been le. bin Teis somtimes convenient to writen and pin terms of and an orn potential energy Bs, = men((Br ~ Bil?) ean) p= ox {(Eh— Eel/ta) 38) (29) 2, isan ener cle to the crs ofthe and gp, adie equal to the rn lev! of the pure semicondsctor in opis “Another physically importan quantity the electron ality of the semiconductor, x-x 6 the lst asian of energy required to remove an ‘letron frm te soli Its mesure from the conduction band edge to ho vacuum level Bye: By ‘be energy to which an eloctzon must be rane tobe fem of al ores fo the soi, Any spatial waitin a Be ‘re dost cletronatie Beds. Tle conduction and valence band ees and co meta x o Fan, meme a © seme cy ce and© he Ph of ar Cet he Fermi eel ean be related to Be tow: Fon Bux B= Bex (s40) Fe Bae —x~ heTl Ne = Bae ~~ By + hyn Ny Validity of Boltomann approvimation ‘The above approximations orm and p old wo lng as E ar >a, ab 1 ‘conditions which ace usually tru fora semicoaductor in equi. Hho porabois band approximation is aot spproprite, then the fora of Nand -X, wil be diferent, but te berg dependouce of and pw be the sane & shore, mand p divege from the simple exponetisl fon in eons ‘where th Fen! level approaches the lomest CB or highest VB lvl, This ‘ou happen i the semiconductor Is highly dopa (ace below) ori there i high deny of defect states inthe band gap, Ten the snlcondector 1s suid tobe dagenerte an the fll orm of the Fern Dirac dition, a, 324, must be usd 29 erate a >, 3.44, Blectro and hole currents én equilibrium mo Soe ee are cance pia comment oe Tiptieh Wetgy ate ge mu nana te eran Bos ond Hala Semiomdntrs a From the sbove argument we can an see tht fk) mutt be aay retin Ki the elateon and le cores ate no 9 eh 85. Impurities and Doping 6:1, Intrinse semiconductors ‘The sticonducor deveribd oo far it inirnsc — iti 9 perfect esata ‘containing no impute, The cal eneney Isls pcre eth loves of ld Ke wih aie rom the overlap of the atomic orbitals nt cs tal bands, ne deseribd shove The properties of thoee bande dete he Position ofthe Fer level oqsiiritn, and the density of eae, ‘ich have enough thermal energy to ces the bao gp and ont ene ‘rity. They alo determine ondetvty snc the intrinsic semiondetoe arm electone and holes sable for eoeceton ad condctvity is fray 2 im aoe where, ad ip re the mobilities ofthe slserons and ols reps, ad qs tho olctronic charg, In equibrina, and pare epced wth in By 3. [At rom temperate the conductivity ofan itinse semiondctor ie generally very small Por example for inteasc lion, ny = 1.0210" em* and ¢ = 8% 10" Obm™* ox, ab 300 K. Conductivity increase witb feerosing temperatare, and with deeming hod gap sace mario at eRe, For ezampl, germasinn with « baad gap of O74 oV has @ Conductivity of 210-7 Om" em whi alum atenie with band sap of 142 eV has a conductivity of 10-* Ohm-* en, many orders of ‘agate smal ‘Now suppose tha the crystal aleve by intoing an impurity aoe ora structural def. Th impurity or df: introduces bonds of dierent ‘Strength to those which makeup the perfect eeytal, and thorfore changes ‘he local estribution of electronic energy lvls. The altered energy levels seca (unless the density of fects is ery high), ual the extended estates which mako up the itis condudian ad Yalence bund states. tho impurity energy levels our wits the band gxp they can ft the elcome properties ofthe senicondacio.Iatrodulng occupied np tly levels abowe B; increases the Frm level, whieh increases the density of letons relative to hoes eqiibrinm (ass clear from Bap. 8.37 anda The Pin of Str Cae 3.38). Inthe same way, upoceapled owls below seduce the Fer level ‘snd increase the dens of holes relative to electrons, The deity ue he ‘ature ofthe carters inthe samlconductor an ths be cold by nding finite annus of impurities with energy levels lose to the eondtion oF valeace band ede, Thi alld doping 85.2. type doping [A semiconductor which os ben doped to ners the deity of ee ‘rons telative to oles sell m type. (The principal charge eatin ae _megtiv,) Occupied levels bueween Ey and Face introduced by replacing some ofthe atoms in the erystalatice wit imparty atoms whieh passa fone too many valence electrons forthe mbar of crystal bonds, Su ‘uses ae called dnar atoms becese they donate an ext eetton to the Ite, An eammple would be an atom ef phosphor, whch hat ve valence lctons, in the tetravaen leon lative. The ett leon ot tee inthe stony desetonal covalat bonds whith hold each atom to It four neighbour. Theefre i x mc Iss well bound than the oer talence elctzons and bested held rather ley ina Coulombic bound “inte with the porous atom: Tho donor ean be ani lately ey, leaving the extra election fee to move andthe faed donor atom pose) ‘hang. For typieal douns, he fniation energy, Vos some meV ot tens of meV: Assuming @ hydrogenie bound stat, the knsation ent is 9 procs by ow ere Se pee eee seee oa pore oe, Dee ee eee eee eee te 5 ol te oe Br ee ae | | | | e310, Scheme train of yp payne hd tt ad {frre can day dt ots a ‘oe ttn pty son fan ptt son nd hea samperature, then . an M ea) pons, 6) since np =n? at equlibm. The desea deosity sao rot incre vr ite oul value, wil te hole density io greatly reds, The tlectons are herecalled the majoryeariers andthe oles the minor ea ‘er: Relative othe intrinse ee, th fal ast of eres encom, to therelre eth eondatvity, Conduction a type secondary slay by eetzons. 85. p type doping ‘A sumiconctor whic la daped ta increase the dey of postive charge ‘ares relative to negative all p type Ts produced by eplising oe ofthe atoms inthe eystal with eneptor impurity stom, which eosteute too few valence ecteons forthe bonds they ted ta fore, Aa exaznple would ‘be the tian element bran in slicon. "The acceptor becomes oie’ by moving a vuenee electron fom anther ond to complete the bonding ‘etwean It ad ts four acighbour This releases hole ato the valence“ Tre Pes of Str Cale teat ora neta enna oe elm toe. tnd pct the hl wed tough ye the ‘nnd, ‘The energy of this oni sate is higher, by 6 small amount of soerzy Vp than the highest energy of «valence band elton, and the acceptor energy level appears in the ad gap cls tthe valence band ‘lge, The Perm level now ie between the aeceptr level end By ‘These p type senionductorscontnin an exces of poate caries, eles Fora doping dansty of Nm onsale seeps we fad pee (40) sod aye (oa) Amsin the total carter dinity and hence the conductivity le greatly ite eased, but now conduction is msaly by holes, which are the majority caries inthis case, Notice from Eqs. 2.57, 8.88 and $.42-245 how the changes tn and 1 se consistent with the changes in the Fett levl In an iti (ee, Dre) semiondtae Ep is roughly inthe mide of tho bad gep. The ‘ect of doping is ost the Fem! level say fom the eeatre of the band tmp, comards Ein type ate, and towards Bin p type material, ‘ote abo tht, unlike heating ad amination, doping tex way of ic creasing the conductive of the semiconductor at equities witout re ‘quiring constant input of enersy | | } | cy emma Ee niype Fg S12, Pain of Peel and spy hl nv to th ton ‘hee band lm Sted onde el by hon Pipe SSA Bffete of heavy doping eawy doping cases inpetietions la the cxytal tructare whieh appear ‘nates in the bandgap eos othe CB aad VB edges, Thee states ave the ofc of adding tll othe CB and VB density of stabs foneions, snd ao eflwtivelyreing the baud gp. The linc cei dent wl Inert, becane tora exiation actos the band gap easier and his Ins eonsequenes for solar cll performance. Heavy doping also Bly to incenso tho density of defect states Which et an centzes for carer recombination of trapping 3.5.5, Imperfect and amorphous erpatas As wll ar exticimprte, semiconductors may conta itis ects Which introduce lvl nt the band gap abd suo the elatoaie prop ‘ten Eten in a pereet onnerytline semiconductor, cofgurtinsl afc are rm broken bonds and stoetural rearaageient at fe Ina pelyerystaline semicondactor, made wp of guns of the sth ryt at ‘vious orientations, fete ook at grin bounds. Tse dicts tay ase a oerwise itis material to become aightly mo p pe alt oping. They an azo be responsible for charged boundary layers nets to surface or gran boundaies in deberataly doped material, which impede arse ranpor. ‘There is another important group of semicondostor matevials, sor ows semiconductors, Thas hve sir atactre to te ey on the ‘ort range, but have no long range order. Fe nan, in amorpkoaie ‘on, wile ech soon atom Bode to four neighbours wth speoxinate“ ‘he Pig of ar Cal ‘etd symmetry ust a in eystaline sco) he arrangement of a icon atoms four or ve hond lengths away appent alto rand, These ssall deviations in bond length and orientation give Hoe to» pro nergy level 20 thatthe density of tates neat the condoction band i ‘mur and valence Band masinn tends to dosy wit nergy int the bate 0p an Urbsch tal rather chen eating of abraplyy Armrphevs sn ‘orductos age aso very Hey to contain daft de to voids and broken bonds Incase defects and amorphovs secondaire wil be dcassd a Chapter ‘A vory high densiy of defect nthe baad gap is undescale, asthe ‘end to act setts for charge recombination we Chapt 4). Ila ives "eto an ff ald Feel level pining, where the density of ae band {8p tates sto high for oll the stats tobe lobed ut oom teperate, ‘dso the Ferme is xed among thea, This mast ileal to dope the semiconductor in the usual way ir level pinning can be 9 pela st interfices and i mentioned in Chapter 5. 3.6, Semiconductor under Blas So far we have considered the suicondctor at equilibrium. One fate ofthe material at equibrium I that no cure flows, ‘To understand she pectin of sola all, we ned to wndestatd wha happens tothe si ductor when i dspace tom equlion by expose to gt. Since Cortes Sows inthe opetating doar cel by delition the devie eaoot be ‘eli, 86.1, Quast thermal equilibrium Suppose the semiconductors dlturbed from equilibria by some inBunce ‘hleh changes the population of deetrone and ble. This col be expe to lok of energy E > By which increas the deity ofboth electrons at hoes above their equim vale, or ¢ cull be the lect eertion ‘of leerons and hols through an applied cee tas, In either ease, ad ‘ have ben disturbed 4 tht they are no longer deseibed by the Perm Dims equim dstibutionfantian and npn is no loge toe ‘Tho electron distribution is now goverond bythe gence datebaton function (hinted in Bq 8.20 above, Moseowes diferent deb ‘ion ftions, fle} and f(k,e), should apply for electron in conde Hon and valnce bands. f. and fy should te poston dependent, bese All pointe nthe semleonductor ae no lager ia eaiibriam,and abe Be Aependent becouse the applied bs may be drctional and may four occupation of sme estate ute thn ator of the sane. ‘Now — and bere comes on of ret seplications of semiconductor plyscs — ito disturbance ews: too great, oF not chaning too qu, he popilasioos of electrons ad les each rela to score ata of quot! ‘thermal equilibrium, What that reas e that the population of stone vithin the conduction band distribute therelves as hough they wece a Savi, with » common Feral lel and temperature, and the sles ‘tin the valeno band araoge tamseves a Hough they shard anther, {ieee Ferm level and poesbly + dierent temperature. in gas heal iii, Ak) 416, FT) and Sell) * fo, iy ‘The now apparent Fem lees dostone and Bois are called eet sud de gous Fert evel, Ey, nd py topes ‘The approxianion is poe braiee relation within etch band ‘> anichfstr than relation fence tbe bands, (Carrs relax thin the Bands mail by scattering fromthe Ince, with he eso ad b> ‘oxption of phonons This occurs ona tne sale of 10-10 ate tds, the carcers relax only by itoring with another carl, withthe ‘mision af a paton or with a deep trap Relaxation over these energie is ‘ch les ly Beene of he sony high nergy nots and pons ‘der normal conditions, and ime seas rw longer, ypclly10-*-10"° x) Tes pesibe fora dtorbanoe etch as optical generation — to be ton the tscale of elarationbatwoen Bide 20 Ct i continaoealy disturb ‘hesystem from eqibrium, bat sb on the smal of reason within an \Consering ony the conduction band forthe moment, f(y) exit ‘be empl describ by the qu therzaleqibriam ditibaion bom er noe, as me have soon above, fo emmetrc in, implying tht ‘0 current ‘ows ‘To del with thi a sal adtonal tem, fa, which is ‘ntisymmetri ink, sada to f "The eppronmston ie wisten, Elke) = $4EV Br Ta) + fat) 60){he Pig of Sor Cal shee TC am 4 can be found by setting wp std solving a Bookkeeping eqution for £ Called the Boltman Transport equation aoe Bex 2.4), Note tet beat ofthe wl dead pay af ya fa, only fy contibates to the expres for man p, while only fy contbute to Jy nad J 3.6.2. Blectron and hole densities under bias Assuming quasi thermal equim, the electron and bole densities in a ‘emicondictor under bias are given, using Ege. 3.87 and 3.8, by ne melre-EONa co and o pone! a) terms ofthe conduction and valent bao! energie wing Pg. 2.21, sud 3.34, by Neer oS pa Nee Pere, ay ‘hare, and Ty ate the econ nod hole fective temperature, In plc le Ta and T, may be dire from the ambien! temperature P Elton ‘with Z, > 7 ee cll "hot electrons ad ean zs In ituations whee the cavers gain exes kinetic energy fom stong ete lds meet, he ‘uitons giving re to ht caries do not usually apy in photoveltae deviees, and henceforth we wil aman that Ty = Tp = (We wil come ack toot eecttons in Chapter 10) Ti assed in Ep. 48-891 that Ex Bg hT and Fy Ey > ky? that Boltmann satis apply. Eguttons 2.48 and 3-49 are theme aa Bs 3.7 and 338 except ht Er, 4 Bip # Ee. Wesay thatthe Fermi lvls are split (ee Fi '813). "The difeeae in gsi Ferm ave, bum Fe, — Ep (352) = oe = {isthe diferece In chemi! potentials refered to la Chapter 2, and the sive of the epiting, Ay, depends upon the ltenaty ofthe disturbance "The dhetronhole producti ow given by p= nbetello? on In geaeal Ep, and Erp ae fantions of poston. At any pot witha the sieopdictor we wll supp eres a cl vas thea er and wo car dine local qua Fer levee 3.68. Current densities undor bins To find Ja and Jp we pod to find an aprenimatin forthe aay bart of JThiss done by eansdeing the difrentinBoeacs om f Bor 84 Balomonn Transport equation and the rlaration Ye oppo In this box we deive a for for fae on & conedertion ofthe processes by which careers are removed fom aay pact Kato, Sine fe function of, rand @, the ate of change off i given by Gone BaF vcs Bvt (as) ‘The terms inthis equation represent the various mays i I fe a ‘lange In the falling we will oe the denitons of welockty =f 55)~ The Phe of Slr Cie ad force a am (0.6) ‘To nd the devnntivs off with respec to dk we will approx J tf and fer the elet1on energy to ee conduction tan eg, Ba B+ Blt) (sn) (Gere we have ssumod, for cary, thatthe condition baad ison i thy = 0. The result the same for ky #0) Then een fh E a) ro) wt ate fore 69) where we have tse the definition of group velocity. (We haw lo ssued fh thers ma greiont a temperate a deste ewe In he oat eoeral case UT" 0 and the sealing expreion for caret contains term driven by temperature gradients} Suteetig back nto a. 4.54 me obtain 2 fe f Se =~ pte ke Be eR vy fe v Vat, + Se 00) where we have related VB tothe free onthe electron to cancel out the fe and hed eran ‘To sl tis fr f, wo need to make two aseutptons about the pro: ‘oso which change j.. One, telaation events within bd within bad reich more equent than exchangeof ears between band. Aa et ‘one above, relaxation ewets within a band are ually clisons wth the Inte and aro fst beeaute ofthe abundance of phonons, Therefore 3 Mh Z 2 letins | ‘Two, the dictation relaxes exponentially tarda the quasi equim fuetion with a characteristic ie constaut ao thst ea This isthe rlozation time eppresinaton, Than we can asl Ea. 60 in fhe sendy state to oben seo tolt- Zp-vote) 8 vines oa) Sutin fe nF 32 6am id 4 ey 1 10 (iS Lanna” (BE) scorer xt es Fiaaly, sepaclag the term in bracts by th whet gb the elatron ‘mobity, and n deine from fo as above, (Bq, 3.21) we have Fate) = wane Be (65) So, the cotton outa proportinal to the gradient in to electron quasi Fermi leva ‘ similac treatment for the vance band diribtion funstion fy pro tue the le cure dest ete) = map Wet 200) enefrth we wil we V0 mean Using the Holtamann ‘Traseport equation to snlve for the non ‘sqilbriua dstabuties function (ow Box 2.4), we sbtuin the fllowing felations fo the electron and hole crrat deli i x semiconductor une er bias oa an Be, (365) Sete) = se (P36)” The Psi of Slr Cate ‘hat the curent density at aay pot is proportional to the tele carter density and the gradient ofthe relevant quaat Ferm leve. We say ‘he current i divn by the gradient in th quae Fert level. na more sentra eas, Eg. $65 and 368 woud contain ter ia WT and VZp and the entets woud be dives alo by tmparstue gradients At any pict the et earrent i given bythe sun of the electron and bole canon at that pot Iie) = Ine) +50), on 8.47. Delft and Ditfosion S71. Current equations in terms of drift and diffusion nuations 3.65 and 3.68 are the most compact forms for Jy and Jp. Hom ver, the physical interpeetaton of « quar Fermi lve gradient my be ‘omewbat cero f we use the eels, ad within the Boltniaan spp imation hat ver =B-MvIn+ Biv, a) os vey kaT Be, ~ By 3 by) ‘Tis was mule in obtaining the det diforion forms fam the quasi Fr level gradients, In degenerate semiconductor (where the Bltnann ‘pprenimation fs) the defintone i terme of Ferm level gradients are St veld and should bo use, + Compositional invariance "This was made in replacing the bad edge gradient with F, For «com posionally varying teri contributions tothe eset will ls aise from any variation Inthe electron aint band gep, and efctve mass ‘and canbe included by wing Eqs, 3:73 ad 3.74 3.7.8. Current equations for non-erystalline solide ‘The drift dlfosion pictur is clearly nt valid in the cae of dalstive ee talie or amorphous materia, when the deity of tate athe band gap SS high, Then the flloing eects may apy 1 the number density of letcons and hole my be diferent sensitive to tempat, elect eld and lominsion, + the motity may be temperature, fod and cartier density dependent; * there oay e's contsibuton to the eatreat whit comes from conduction between locale states inthe band gap. ‘There area numberof diferent way of describing he currents in defective materials, A thorough description is beyond the scope ofthis caper is often aonumod thatthe currents due to ecto and hoes moving in localised states in the eoueton and vlene bad cat be deserbed by ‘the Boltzmann tanspert theory, ce, drift diftsion quate apply. There ray be an aditional earrent due to electron (or ol) tnction between rose Hal n Sods 7" looaeed sates i the band 9, Jatt dps (2s) ‘This Incline state current can be descbd with th ad of a energy apendent mobility, (E}, in ankogy to the definition of eurent a acyl ‘howe ya where (Fiche dent foaled sate sn (5) the (aly Fem Dire) dtebution onetin. The form of w(F) depends onthe mechani of tensor betmeen lilac states, For cramp, for thermally wsisted topping abould he thermally acted locale contin or valence band tas can be dstingiced frmn loci nea bandgap tats ty a mabey ee. In practi, ti i he coery a which the roby becomes tmperature sented. Thee wil be ‘iseumed in mare detain Chapter & Does B ace) (sy) 88, Summary Semiconductors are stble materials fr photovltae o account of the Tad gap between cerupled and unocenpied bands which can be bridged ly’ vine photoo, and the ene of charge tnarport through the etal tends, In crystal semiconductors, elecron promoted te conduction Ud ean be rete he ney fe pasteles witha wel/defied wavewetar ‘id a efloctive tse which recta theft of the Inte stone. Absent ‘deco inthe valeoe baud ae low as hols and can be teed a8 Deetively charged particles with an eectve mass detenmied by the o- lence bad structure, Electrons and le can be eee approinisaly ac independent particles, The bad stscture the reatonhip between the energy of the electron ad le waveweton. The tot important point are ‘he tlence baud waimum and eondueton baad minimum, The form of th Band stracture ls determined by the erystalstevetre but I eppecs- imately parabolic nae to the eal pots Teqilielum, tate re fled by lotr according tothe Fen Disc Aisaibution function. Ins pure samieondyzor the Fer level es within he band gap and the elcton and hole dente depend exponentally spon Ep. Doping with impurities of diferent valence increases the denity™ Phe Pain of Str Cale of electrons or holes in the semiconductor at equilibrium and moves By towards the bands Heavy doping fs the density ofthe dominant caer. ‘A quilt, ltr and oles cute ae always eo. ‘The semiconductor can be dstrbe foun equilibrium by the action of light or an applied slectle bis. Away fom equilibrium the dstrbation function is changed but can be approximated by a Ferm Dire funtion with sparse patally varying Fer lees ell quasi Fer levels, for ‘he eletron and hoe In general, diferent electro shoe temperatures aay apply but in practical conions th ambeatwanperatare is usully vai Amliaton of bias produc lat anol escent, In conditions wee seaterng events within Baad being fate th ritions between bands (the relation time approximation), the cures ae proportional ‘tw the gratiente inthe respective quis Ferm lel ad tothe respective ‘mobilities. ‘The quasi Fermi lvel gradient may he consdred as dt ing fore for conduction. By reaving the ast Fer level gaint ino ‘eerste potential and ear denety gradient, te cree eas bee presse atx sum of eld deven ‘ri escent and sttitialy den ‘aision’ enrent In nowerysaline materi the samo concepts of as Freeland mobility ean be applied, vt he fective moby may be svat dependent Chapter 4 Generation and Recombination 4.1, Introduction: Semiconductor ‘Transport Equations "The eset function of solar ll sth generation of phetocurent. The contpit i determined hy «balonebrtween lg sbsorpion, current ga eration and charge recombination Cortents due to eletons and hols in ‘enicondactors were csezod in Chapter 3, and Chapter § wil del with {he mockaniame of charge tparsion which dive the photococent. Thi chapter is concerned ith the presses of charge carter generation and ‘eeombinstion We intron thn iorete! Formalin fr entree tr ‘tions in semiconductors ad use tito drive the rates of photogeeration tnd the principal recombination aochanisms, We wil derive some of tho ommonly used formule fr recombination rata, and attempt show how ‘he ates are dependent upon the loonie tacture, materials propertis snd operating conditions. The dealled derivation wil ot be relevant to sll odors, but we nla to suggct ow the famalions ean be adapted 'o dal with ater, novel photovolic waters and structures. ‘The basic equations of devies physics the wemiconductor transport ‘egutone, are band on two simple principles: thatthe numer of eat ‘ev of each type mst ho conserved; aad tat the electrostatic potential ‘due to tho carts charges obays Poston's equation. Fors semleonductor ‘ontaining elactons aud hols, onseration of electon namber reiee at om m Bebe Gy— Uy (aay {or electrons and 173,40)-U, aa a0 Pee Papin of Slr Cale — — te) went) barvand ig 42. ukraine tay autos. On ating ugh 3 sal ol, ‘ae hes changa Wy (Je as) l) eda Tamara ape the ltrs ‘stooge tn tan (Oe se for hoes, where Gy 6 the volame rte of generation of ltons (hale, ‘nd Us the vllimo rate of recombination, Poisson's equation in the Areata form is (a shee is the elertrotaic pont, the diltie perntivity ofthe remsiconductor and pga the local density of Ged cee, ‘The continuity Ege 4.1 and 42 ean be understood by conserng 2 small volune 6 Tn unt time, 57 x G, elactzons are generate within the volume end 59x Uy setons ae rmoved. Electrons may albo be iakodod ot te moved by eurrentsHowing isto and out of he vue, Coser ony the = ‘omponeat ofthe curen. ln uit time 1J(t-+2) 6A leone lave te ‘volume tough the right hand boundary while Ly) 64 eater tom the eft, eunsing a net change of £28 x yin the mimber of electrons. Adding te ie nein whe fr he ae of ag of cco dnt per unit wolume, fn _ 10% a1 GU ‘Inthe dimensions this generac quite eit the fra given in (4.1), hove. Bguatons (4.2) and (42) ace completely gonora. Once we Know how the J,G and U depend on n,p and g, and other material or envionment parameter, we hav a st a sct of couple diferontal equations which fan be solved for tho three unknowns. Tho patcula frm of J, @ ne 7 ‘ipendson th material and enviroment. In Chapter 3 we loked tt how ‘Tad ware define fora crystalinesenionducor. I tis chapter we wl Jock a the mechani which determine U and C. 42. Generation and Recombination Generation i a elictrone exation event which inereses the number office caves valable to carry charge. Recombination js an electronic Felmation event wich reluoes the numberof fe carriers, Generation == (puroran input of nergy while recombination releases energy. The energy input ean be povided by the vibrational energy ofthe lati (phonons), Tight (photon) or te Kinetic energy of another eave. The sensed en say talun up by these same mechanime. For every generation process "here is an equivalent recombination proces. This is de to microscopic reverblity, ad van important prieple in understanding the funtion of photovoltaic dees. ‘Generation may be the promotion of an electron fom valence ta oom Acton band which ete a elcton-ole alot fom vlene bad nto ‘lonlied state in the band gap, which geese only bole, or om @ locale state io the conduction band, which gonertas oly an electron. Forte solar el the moet important form of generation opin, the absorption of photon. Recotbinition Is the los ofan lotro or hole Urough the decay of| ‘electron to lower energy state. Agnin thi may be fom band to band, Getroying an elactoarole pai, of it may be fom conduction band to ‘wap slate or fom tap stats to vale band removing only an electron ‘or hoe, seepectvely: The ene releaso can be given up a8 photon (radiative ecominston), as het through phonon emsion (non raiative recvmbintoo) or aa Kine energy to another roe eee (Auge Cone ‘nation. ‘Thermal generation ond recombination [At absote zero in the absence of any external bis cectrons occupy al of the euerny levee lb wp tothe Fermi level, and pe recombination ot merston processes oar As the temperate ere, he ltl gains ‘bratona Knetc energy and some ofthis maybe given upto an eletzon{te Pig of Sor Cate Lo romeo get uy le The omen a ction on theta gp ical Serge Soa tea twa! ea ston nae og eee ‘we ita tel goth te Te es se Ch wy tema ents thay ie ea ‘oso ptt a pantech ‘rts nd ond seo tad Seana ne ‘Neeprocmer exactly rate wie aa eee trmprae nh! alin, ect cy et room ahd ey bythe nie ft apn ad Eien eas Te the oa eon gS en Tet moet 7. Sine we ate intareted inthe dstrdane ofthe populations frm ald ‘um, We send consider only the wxcem orobination and generation ata Pa (ty ae O,= 0p —up (a) tod oo ‘Thus thermal generation i ot inched explicitly a8 eontibution to For band-to-band generation and rcoibiatin pocesee, he tates re aul for deetone ad ole end " u =u as aed G=6,<6. 1 this chapter we wil ist conser how satiation rates may bo ‘weated microscopically using Perl's Golden Rin Soe 4 I Sesh ‘will aro the proce of hotogceaton a show how the eeorp- tion oofieat of «semiconductor is derived. In Sc. 48 we conser the \ifecent types of recombination: rede, Auge, nonradiative va tape | cd surface recombination, aad stow how the renmbinaton rate ze 26 Inte tothe steal properties Section 4.6 arene the teniconductor ‘snaport equations aga and Indeats same simplied cases, 4. Quantum Mechanical Description of Transition Rates 484, Fermi’s Golden Rule Ta easay cases elton transitions can be described by Ferns Golden ale This ean apprinatio, sad on fest order perturbation theory, ft fll quantum mecha tension rate. According to Feri Golden ule, the transition probity per uit tise fom ap ntl ed sta | of enorgy Eto fl emp state) of energy Ey which dies a eer) ty B under the sein of ome pucurbing Hamionian Wis given by 2E ny PaCEs ~ B+). 4s) “The em in racks [0 8a element couphg al an ad ‘se Te deer hei of ti ier betwen thet tte er the given pettrbdon ay reprnn he tof ight Belo fc conserves of energy. A argv sgn appli for extn re tach as aboepton wb i > Bands unt af ergy Bi omored trom theprtrbing fl nds pote ig for ela eves ho ‘sombinton, whee By End qs Bete ‘Bos LL, Devtation of Fermi Golden Pale "To obiain the tnaition rae we ueed to mliply by the probable ‘hat he initial stat ls oseupieg, f= (E(k) and that che final state sre, Lf, = (1 F(E {hh bore f(B) ithe electron eeapatien feson Then the rat of transitions Fi given by aaa MBuPKe— BHI ‘hese Hy ie ehorthd forthe mates eleeat, (In Bq. 4.7 an clectton Dromoton event (By > Ei le seamed, The analss apples equally to the ‘ase Ej o ny fot a — = © ig. 42. () Aberin of » pots ope an alaton (0) Rltion oan ‘tee sept sap sin) Spin poo 4th probity th a ton inate E, gente aw) 1 the pobiity Has see poo, Hay he pt sai ‘element, me Spctenon emia proce a te HP feof) (410) ‘The come matrix element controls absorption and spontansous emi wea of mleroscope reverb: althoogh the initia and ial sates in Ferals Galen Rule hav heen ecchangd, the vale of H3,remalzs the hte steady tate, the aes ofall tro proces must balance. Siting (an) we find that 8) ce Wwe have ned the definition of Sy. ay be, a9) eis ea rom Bq 419 that sr intent ight ld lense greater ‘separation in quai Fermi level For this reason, somtimes refered tora the ‘heel ote of bation” [Woe 198] ifthe quas-equilriam oceapaton function for photons. Thos the umber dena of photons of energy Ba qual thea quibriam given br yal) ~ HE)aa(E) (420) shee ay ( ithe dent of photon states. Ava on equim n(B) Tl be detersined by the eng ofthe eleteomeaneti Bld equation 417 alo gee the useful ul that: BAL = Bim Fe =f) en 44, Photogeneration hotoganertion is by far the mot important gnertion proces Ln pho toyota deviow. By photogenention ove mean the generation of mobile sletrons and bole trough the eiorption of gt inthe senicondaror (Other generation proces of rlace to photovliaics ar rap asta snd Anger groration, which wil be mentions in Chapters @ and 10, respective "Though mort relevant for photovoltaics, thi ie at the only opel ‘roces which occu in semiconductors. Photons may akeraativly be hoor to incteam the Iinetic energy’ of motile ears fre earser% The Popes of Sar Cale sheoption) or to generate phonons, o t promote eleteons betmeen Io fal stats, or they may be scared. "The fst two ofthese ace ust aly imporast only at photon eoersee mach smaller than the bal eu {(< 100 meV) ad theft only thigh carne dense. Net tothe baad ‘9p, bad to band and loa ette ko ban teantions are dominate Srateing, paticulrly by interfaces andy inhomogeneities in non ‘unormmiia renoves ight fom the incident beara without generating farrier, and $9 ie undesirable fr photovolaes. Howeves, it may be ex lot in sole ell stretares which are design to tap th light and ao Amplify the poten Geld, This wl be dicased in Chapter 9. 4.1. Photogenenstion rate ‘The macroscopic absorption eoeicint a decbes how th Hight intensity Us attenuated on passing through tho material, aE) many be conde! {he sum of the absorption eros seetons per uit value of material fr {he various optical prooesc. Suppoee a ben of photons of nergy and Intensity Joi worl incident nla of sbaoring material Acton ((6) de ofthe photons of eacray eataing sla of thickness dil ‘be alworbed and the ight lntemity J) will be altemoatd hy factor etn Hea (42) Inceprating Eq 422 fora atari of no uniorm the ely a depth fle) ingen by Mea) = Hoje 5 oH any where 10) the intensity juss ase the sure (i aftr sesoting fr reflection). For uniform ay this reduces to the spe Baer-Lammbet law, Te) = 1)e-* (Fig, 43) Te ean be show that I ated to the ing ‘ary pat ofthorefactivelindex (a) through = SURE where A tho vavelength flight. «define this way may alo cola contebutions from scattering; however, thse ar not consderd in the mierosopic deviation ek [i we can assume tht all photons are absorbed to generate fe carriers ‘hen the ate of ari generation, per uni vole, a a dept x below the surface Is ven by 916.2) = BE.2)a(B,2) an) i Atnennnnne Rd T= (T-R)T,expax) —_ —_ RT, Ta Fg 42. Atamatn of gh tnt no fabri a ene A fin aie ita at te oe a ‘Sunt tia thn Daa in Phe Sent strate oe ap. sree b the photon rat 2. Notie that tthe number and mot the aeey ofthe photons which determine the photogeneration rate, To eate {tothe indent x we eet allow for section of photon tt urface Ad attenuation within the material, Thos (8,2) = (L~ R{E))a(Bp(B)e™ 1 9! as) wha (ithe icons Sx aad RCE) be the eeectvity of hw surace to noraally ince gt of energy E. Thi the sects photogrnertion ‘te To ind te stl geneaton eat atx we oun over photon energies cue fata as ‘Th integral shouldbe extent onl over energies where photon absorption ry seus in fee ersorgontation. 44.2. Thermalization Photogeneration does ot depend upon the eneray of the absorbed pn- ton, except in that the energy exceed the band gap. Won hight energy photous are bvorbed, chy generete carers with higher kinetic nergy, tos chat energy gully lst and only By of potential encrgy remains to be calcd, as chown in Fig. 4. Th important quantity is the mem- ber of excitation events and not che amount of energy abeotbed. This i coon of the most porta concept a understanding phatovlai deviceThe Popes of Str Cate PA. Photogostiog oa crn pt alo of exes dt al be ‘haem bert oe rep als, 1 nao the mental difrencebeewien photovoltaic and sola Cherm ‘The photogenerated caries lane any extra Knaic energy by thermal ‘ation, of eotng. Microscopically, this reas that they undergo repent hy, Ey cabo ‘elected in the mumoraor ad thc absorption coofiient ha ie qadate form By aay ‘Tae bsorption cocficent of an indvct sue as very diferent be ‘viou to a direct gap material and dows not reflect the JDOS 38 pho ‘on energies close to the band ede. af) i generally smaller and thes ‘wore amoothly from the band edge than in det gp materials, Si Jas bobaviour ie obuerved in high doped emaconduetos where elton ‘eatterng rather than phonon embson aad sbsrpion, asst the optical ‘AX higher photon ene, diet opti reasons are allowed in the Indiet gap material. The cotsittion of thee det transitions should ‘elec the JDOS without any phono contributions and 0 rte plywe ‘The Php of Str Cae with energy than the indirect contributions. The diet contin wa ally appre os «change in eurvatue na). 446. Other types of behaviour Tn prc, the (EB)! behaviour prods by Eq 444 ie selon se, ‘A ences above By the DOS fantions diverge fom the pars spre ‘imation, while at energies jst below E ezeitonsinfuenc the ania, The pacabic band sppranimatin only good claw to the baad ex ema ypclly within 100 me At wes ff fon the band ete ‘he E(k) curse bens to atten nt, ad booomen stationary at ote hgh symmetry values of. This leads to local maxi aad other features io In the DOS, which ean ften be identified frm peaks inthe absorption ‘As tir apprasimation to (6) than (E —)!,paamsti ara nay be derived for groupe of semiconductors sting a ail crystal src tse. These wll depend typically upon the energie ofthe portant sy netey points, band gaps and dipole matrix elements, Vaious odds have bea developed forthe TV and I-VI file of semiconductors [Adachi 190, ‘Multiple step photogeneration [Arlt dret band to band photogentatio, fe charge aris any be suratd inet, where the photon is aborbed to create an exit tale Thich sobsoqenty dsociats to tlase one or ste tee eve Exar ples ae absorption by excitons and by senses. Eaton are Coulombic bound stats of electron pals, abd were introdued in Chapter 8. An ‘excton can be created by a photon of energy analler than By. The 3 ference baton the exciton cy and the bandgap, eal the exciton binding energy, is usually es than fp and so mow excitons docile ‘as 1oom temperature However the Bndig energy wil be atoog in xe ‘whate the photogenerated clean said hole wavefunctions are lealied, {in the cso of low dinensioel semiondector structures and molec Ir semiconductors. In those eases the excitons are important features of the room temperature absorption. The magnitude ofthe excitonic absorp- ti, is ealltor strength, is geacraly Igor for more etongly bound cect. Note that only stationary (ke = 0) excitons ean be generate ‘pte ‘Te imporeanc point fr application to photoolais i that excitonic absorption docs not automatieally generate mobile earrets, The exit seeds to dissociate at, and ay emmnbtebie that happens. Tete. fore in modeling devi behavinus we sbould we for the nel generation rate of foe cztes om exciton generations distention, and not sin ply ee opel exstation rate Sensisers ate analogous to exitons and ate ust dliberetely ne ‘woduced ae optical sborbers. The smite tnty be a aslecular species such as ade molecule, ors mal solid rate particle in contact with @ semiconductor surface. Sach eysems aro widely sed i photography. The ‘photon erences an excited slate, which may thin daocat atom charged lt flloving the sequence Ste 9 St pee shoe S, S* and S* represent the ground tate exit sat, and lois State ofthe sensitizer. The nal stage involves inetion of the fv eater Inv the semlconduror. Sastzer at heterojunction may inject charges of pponite ign iat the two diferent mein ferming the junction (Has, 29 nthe cas of ebaoepion by excitons or seastvr the apical generation rate tld be repced y 152) = (L~ RE nn EAB Bj fo here nin) tho quantum eiane fo diweiaton, i, the probability ‘hat ope abaoebed photon of energy E wll generate «fee cate Amorphous materiale Tn amorphous oon-ertallne) materia the ack of langeaage odes mee ‘hat crystal momeatum ned nt be conserved is an epic] tanto. Tae land gap i alvays dizet™ Absorption eventa are therfore more Hiely ‘han in the oquialnt crystalline material for example, the absorption ‘ofc is Ire in amorphous than in eryetaline son. The form of ‘9(E) is dominated by the JDOS without k consermtion rosretins, This vl be diseussd fe the ese of amorphous soo in Chapt 8he Ps of Ser Cals {Absorption em Photon Energy /eV ig $6, Atrios paca ws comnon peti mist Not how Seti eft ieee Gt oats ‘InP sharpton aif ty cient. ew 44:7. Beomplee and data igus 4.6 sows tho absorption spect of « munber of semlconduetrs which are important for photovoltaics Notice how the abeorptien edge fo the diet band gap semiconductors GaAs a InP, is shsper than fr he indie band exp materia, slcon and germanivm Notice how the shope ‘ofthe cures for Gas, InP and Al Gaye arent de to tit Siler crystal struc, ‘The absorption length of a photovoltale material is 6 useful quant ‘Tiss defied as the dtance gh of patent wavelength ust tre ‘before he intensity fatennatd by actor e andi given by At vee ‘waelsngt the dtet band yap materials GaAs and InP have abeorption lengths of las than oue meron. This tans that only afew microns of ‘unter are needed to absorb vitally allo the light. In conta, the indiet gap material Shae an absorption Int of tens of mer, 20 ‘hat wafers ene or hundreds of an th re nerd for good slmopton. Refesvty has not boon tented expitly inthis seta, For typical semiconductors R(E) is = 30-10% at vale wavelngt, and cof an important factor. The net refuetty of «semiconductor eufac can be redo sing ant efletion coating rere txtrng thee ae tested Capea 45, Recombination 454. Types of recombination By recombination we re othe bs of bile electrons or bole by au of| numberof removal mechsisns. Ul generation, where one mechani ie dominans, several diferent recenbioation machaniss ae inporeant fr the photovoltaic devs ‘We should ditinguish two eaegris: naoidelereombinetion pro cms which are due tothe event phil proces i the inti a tell and aoidble proceaee whch ar larga vet perf msttial. ‘Amongst the unsvoidable rexmbination processes ate the proses ‘whieh rel ftm optical generation, spontancous and aknulated emison {re Se. 43) For photoes, ke imnetimporaat ofthe spontaneous ‘lesion, whieh aio kaown erative recombination, ‘The other important unnecdabe proves the lteralan of a ele ‘oon of hole with second sar exrie, resulting in the devay of one carter aro the Band gap and the inte inthe kinetic eae ofthe tote cari by stout equa to the band gap. This is calle Auger recombination, eis tho reere of rare generation proves whe ater vith kinetic anergy gents than de Ll gay ble gre pon of it antic nary co exalts an eletzon across the gap (aeussed a Chap ter 10) Anger recombination i uaportnt in low bad gap materia with high carte densities, where cae carrier interactions ate stonse. ‘Avoidable recombination procenes ually involv relation by way of ‘locas trap state, Those trp ate are duet imprest the cyt or defects in the crystal structure Thee are on know ae not-adlative _scombintin poets (although Auger ir alo non-tatve) ad re us aly the dominant mechanisms. Recombination in somiondctors ts well cowced by Landsberg [Landsbers, 1090) and many smlcondactor text= ‘oak such at She (Shu, 1900) or 'Tyag Tyagi, 1951, 452. Radiative recombination ‘Bos 4.2. Derivation ofthe radiate recombination rte ee we are gol to deve ax expression for the rate of radiative re- ‘eumbuation sing out rau for absorption coeticeat. From Se. 43 above we know thatthe rate of spontansous relation ‘vets fom an nal tte |) = ke) of energy to aia ae) =10 ‘he Phys of lor Cle _ 4 L a eo aot eee aso Tena a sooner leapt ~ Fe At Nav tnd, ara ont ge reeainton Ik) eer Be en br ry folk t) (419) ite too ene of ebaorption ie ame = PHRF (fe — 1) (24.410 where ft the probsbiiy that chet x photon of enc B (E.~ &;). Ae qua thermalequiliriam the two cules match and we obtain Bg. 418 for f. We wl ell this f(B). Away from equa 4) ‘Now, under ancient eld the probity that there i photon of enetsy E is elated to the (non-equity) auunber density of photons gu by _te im as) here gp the density of photon states in he energy range BtoB + dB. In an optically tropic mam of eftactve nex ne (asa) ast) Gneeon on Rsinatin wa [Nom we ct relate the spostanous esi rte tothe alzapton coll: den, wing Ba. 4.35 to relate rae to, ran e FE sander = Lal Bhopt El) as) Seng rg a fw have mt i ae (4s) Tie the volume rato tv recombi, ta ela ct enison. Tor apoio dvi ete motes itera the mination le ang «pra ee nat cs he some ear gn yatta ya te cna ae ‘Seiad tr ton toy = aa OE (450) ‘This ate can be expressed in terms ofthe photon fhe fn (base) Hack body, 1) AE, Bp) (ass) here ond BB On) = grea showin Eq 2.14, whore F = frelon normal to the cel surlce aad = ‘We obtain the total radiative recombination rte by integrating 456 ore photon energies: uel “f (ENE, Auld As explain in See. 4.1, to obtln the net reoubinaion rate we must ‘uberec the at at thermal equim, which i the rte when Ay =O Vous “f (EME, anae~ [~ oe nie.oee (450) Sil vriatlons tn the recombination rate enter though spatial vasiatons 4 yu) (oe alo Wiefl [Woe 198] sad Stern (Sten, 1963)45.3. Simplified ezpressions for radiative recombination Tn odor 0 woe the recombination rata into th tranpont equations i would ‘be ual tobe able to expres Ung im tema ofthe easier denies. Tn noo-degterate weniondutor, B~ Aye hy forall enereas Bat which the rte, Bg, 455, lo uan-glgbe. Then, 8 good approximation, snag sing the rolation for @ semiconductor under bin, Ea 3.52, we can weite Bg. 4.56 ae Una = Batre = 2?) sn ier = BS. i da(k}e ROT Eup, (458) ‘The radiative recombination coef Brag cso density independ fond ba proparty ofthe mater. ‘The expresionslaplifes farther for doped inate If the denity of photogenerated elecvons and hoes is each etal t0 nthe Ia p ype satel wit a doping density, 98) = (00+ 8) p0 + Bn) — nape = Bn, whore ny and ar the clecton and hole densities a equlbu, gives ‘by n/N and Ny, epectvely. Tis moans that Usa i prepotinal the excess minovty ease dest, Ung = = (459) where tot Ba be 5s the minority crrer rite Wietime. A sini anayss shows tat a ‘type material of doping deny Na, oom Una (aon enti nary Re 4S. neat ean pcm ff Cake wt eal ‘yo dace Leb th an le nent ed ii sp Reson vit (402) ‘The raiative time ean be mesa fom the tne reese spontanaous ‘nision following instantaneous cptcal excitation of the semiconductor (called photoluninesence or fuorsonc). Ba canbe determined exper laaly fom the variation of ru with dopo Equation 58 shows hat Ba ager fo incall with «high absorp tion coefieat and therefore reve recombination nore importa ia let band gap materiale The eon era men tat, relative to hsrption,coatebations from enay loves closer tothe Bad edges are ‘much wore important. Te alo rst at radlive recombination from her Band to impurity stats inside te band gap ean be very important, ud can dome ovet bandto-atd evens, Ti cass where the chomlal potatialwiform, thy redatve come ‘sation rate ean be diet telatd tobi f(a) ~ g¥theoughon the ater then, sing Bq. 4.57, Vina = Uiaeleov*T 1 (463) Whore Ung «material dependent conrtantmw The Php of Star Cate Radiative recombination is unlportant for practical ells at operating ols but inthe limit of perfct material isthe sbachanism whieh its ‘iene, Tor 48, Binalecalar reomination - The detailed trestnent of radltive recombination shove show how the tte of recombination is proportinal to the denies ofboth pe of atre- Infact, il usual or Bando nd eosonbinatlon peosemes wih lo ot depend on the presence of a thied qvasity tow He v were Bis mteril snd process dependent constant. We show here that ‘hiss consistent with Femi's Golden Rae Fur tramsitlons from valence 19 conduction band, we may replace (fee) with (1~ f). fe ln Bg 427. Siow under orl conditions the ‘condection hand is manly empty while the valuuee aud is mainly fill, ‘he Ferm Dirar fonctions very exponential with enrgy ove the celevant ange of By and Be The factors fad fae terlore Mkly toe the most rapidly varying factors If the nar lena i nly weak depen lent om itil and al tate energies, it an be cken outside the integral In the expression for the transtion rate ina the integrations cre he eon ‘ietion and valence bands separate In the ese whee the band stuctore te tear, w= Bie [0 riennboes (O eeontmat. 469 “Tho two lavgrale in Ba. 4.64 aren fact the density of oles in the valence tn and lettons in the condeton band. Ths, the transition rte i yt potioual to the product of the fw eater deste, U ac np. (Remeber ‘that th themal ecombinaton rate mist be subtracted to bia the net recombination ral) Por trations fom conduction band to lacaied site o from loeaied sit to valence band, we replace the conduction (or valente) baad DOS, funton withthe DOS forth locals state andl n (orp) withthe density felons (or hols) inthe oes state. For conduction band aoe fate tanons we have Um Bom f) ass) bere Ns the density of locas states and f the probability thatthe located sae soci, ‘Relationship betwen rats and cree densities ate moe completed hen the intial to fnal stato transient a mal step proces and when ‘the trnion depends on th elit of «tid entity. Sholay Read Hall recombination via'm tap sate inthe band sup ison example of 9 molt atep proces and Ange recombination, considered nex, i iver 45.4. Auger recombination. In Auger recombination, «eosin betwee two sila crits reeks in the excitation of oo eater to higher Kinet energy, ad the recombine sion ofthe other actos the band gxp with x eariee of opposite pola ‘The eoeray which released trough recombination is given up as kine saray tothe other earn URinntly that ext energy wl be lost a heat {2 the exited ease relates tothe band eg For band-to-band Anger reombination, at slketron and two ole or & Ile and tm electrons ae involved. By a sinlar argument to that tad owe, the rte ie proportional othe deities of al thee eacres 2 Ut {he net rat ares ke Tang Aelsp~ nu) ‘or twoactroncltisons and aug = Aaa? ~ 98) (400) for two-hole collsons. Auger process are most importa whete ater, fensiteo ae high, fr tmtance im low band expand doped mata, high temperature, The dependence on doping density tong. In pype doped material the cectronhstne for band to-bane Age esablasion iepiven ty vane RE oy Ss th hol tii pe mea i “oe” aRca a Pen af Sr Coe iy. 42. Boer nine epretatinn Ae rombntion ace (a) 8 at (a) bund ap mach tone heme ‘of tion tar ot se om hen bet ‘nt tye aa a en yen Ut item ment se py aa he ‘Auger resombination can ako opear vs trap state An electron coding ith an occupiod tap state claw to the contin band ean stimnla the ‘combination ofthe electron i the tap sate with a valenow band hay ist gaining inet energy. Silay hl alliting with an embry th ‘lose to the vance bun ean stile Auger reombintion. In theo as {he inary cate tans vary Bike ye adhe Auger evens conserve momentum as Well ae ergy An elaeton with ‘energy E and momentum Kean recmbine with «bale of energy EE ‘and momentum Ki, provided tha there isan elatton state available 6: (E+E), kW (ee Fig 49) Tai means that Auger scombination can occur in indirect band gap materials unlike adativeeeaesination which 1s suppresed. Anger reombuntin i therefore ach tore important ia Inet than dice: bund gop material and ithe dint lose mechs In vary pare alicon and geri, 45.5. Shockley Read Hall recombination By far the most important recombination proces in real semiconductors ‘are thowe which involve detector trap states a the bandgap. Sine ta) ‘at is spatially localised wht the fs eeczon oc hole locale, we «a think ofthe rs eurier a being captured by the tap. The sie ex subesqunily be reload by thermal atnsion, Alternatively if the tap cape a crierf the opposite platy before the Bist ease i lease, then th trap bas been emptied agua and the tno aries have in ct recone. Thi ie Hratd ini. 11. Locale states wich servo Tana to captore and else onb one type of earor ar usally ealed toape. Thos which capture both Spex of earie ar alle recombination entres, Unually recombination cose ie doper into the bead gap thas oe ‘Box LL, Deaton of the Shockley Rd Hall (SRH) recombination mae Consider semiconductor conning a dansity Ny tzep tates at an sey B; in the band gap. Empey tops ean capture deetons from the ‘eduction band, aud filed taps can capture bole fom the valence band ‘The rate t which clecttos are cpgedin ths binocular proces sven yg 468 Uae = Bandit f) ‘shore fe th probably that therap i accuie The coeficest at be exposed us By= 04 (26) Were ty the mean cher vl of the electron, and gy the capture ‘ose section of the tap for elecaous, It wil alo be usfl to define a stine for detran capture bythe tap 1 smn By (400) ‘The rate st which elctone are lee from the tap depen on the cupation of the taps and ean be written on = Mh (a0) thre the rele time rae determine by the condition that Uae = Gye In quia. Then follows hat Gag = Bare an hr the value ofthe lectcadenity when the lcton Fermi level equal to ee tap lve, nee ye BIT, ancy The Phy of Ser ate In asic may, ales ave captured ata rate pe = Boose fan) where By ine an od Yoana = (25) nd rns atx rato Gye = BeeaMilt~ 4) (475) Where ps the value ofthe hole deatlty when Ex, =F, prenetminat am In genera, the rates of eaptare and rele for letons and hols wil be iret, depending onthe adit ofthe trap fr eeccons or holes and its positon ia the band yap. Howovr inthe say state the net eat of slecroneaptare by the taps Us ~ Gye mst a eal tothe et rate of ol capture Ups ~ Gye tac csgee cant be allowed to bil upon te ‘raps, Thi onion fea te value off Ban B Tigenys BFR) ‘can then be liinated tom the expeaions for U — G. Finally we Bod forthe net recombination rate fh any npn Venn = Saami Fr) eps am hero we have weed he definitions of and pet Tiss the Shockley [Resd Fal expresion for recombintia tough 9 age ap state For doped sesiconductors, Una simpli Inp type terial provided that ral 3 ym aed Na > py Uae Becomes propordanal to he exces cnr density, @ ra} Van as In type materi Vena as) However, when mat 7, oF when 7 nt and rps fr by ondes of ‘magni, the Uniting forms may not apply: Thea the fll expression ret be wed SR recombination stronger when and pave fs magne By examining a 79 can ae that fora mid gap tap with ual eaare tis, U haste maxima when 1 = p. (See Pg. 410.) Ths mas tata undoped egies, where mand p may besa, SRH recombination ote imporent relative to radiative oombination, (Equation 4.57 shows that radiative recombination depends only onthe np product, whieh constant fer tailor Ay.) This dependence on the n/p rato tafwnces the Bie Sependeace of the SRH resrbination rate, Wo wil ia Cpa 6 that SU recnnbination vase Uke e897 i doped materia ut like 282° in the depleted’ Iyer betwen te dillereatly doped materials, Tn eal semiconductors, tere may be several rp Inve in the bd exp sud arse may recombine by more than one step. Howeve, the largest ‘oatribution roms tp which are lated lose to the eats of the band {, for n'= p. Soy for bulk rater witha niform densty of taps, the ‘ppeoimaticn te oully made that combination throwgh one pareale teap lel is dominant Malte recombination dss by Landsbone [Randsbere, 1900, SAH recombination este np e430. Stetson testi hon Leip st mi.0 The Physi of Star Cte 4.5.6. Surface and grain boundary recombination According to Ea, 79, spatial vstatlons im sna cn be use by varia ‘ons in wand po by spiel vation nthe nature or mutber density ‘ofthe dainant tap. A higher density of ra states shortens the lcton ‘and hole piace tes. In real materia, deft are much more lly to ‘ocur at surfaces and at tho interfaren betwesn diferent crystal tela ‘ mubiryetaline or hetretrctared material. Locals state suaces ‘nn interfcce include both eystal defect de to broken bonds, and ex. ‘wise impute which are deposited from the extemal envio or hich are concntteted et interfues duniag growth, In such eur te ap ates responsible for reobination ate coceatated in «to-dnenionl ‘aber tha thee dimensional rps aad es nich more ming toe ees the recombination in terms ofthe trap deaity per nit ea of he surface or interface, than pet unit volune The relevant quansity wl be & ecumbination fx — the nmber of caries secoining eth lntetlace ‘er unit aren pet unl ne, rather hau 4 vale rennbination rate a surface contains density N cape pr uni ate, then within «vey thin layer 6, around the surface, the surface rsonbiation ax wll bo (em per unit area, whee ny, ae the elctron ad le densities atthe surface 5 the surfce enmbiation pln fo electrons, died by, 5.2 (ass) nd 5p Ue surface rosomblnaton velocity for holes, Sp BN (aso) 1 this definition, both, and, te deste towards the eulce fon he le Th p type moter, Ba, 482 reduces to Us = Syl — a} ‘Ts leslage of minority cartes to the sufce results in a surface reco ination cement The mugnitute ofthe cutest ean be obtained frm the ‘leiron umtimty equation, Inthe dank, at steady state, Eq. requires {hat V-Ja-= ay ntgrating this aeons the interface loee we ad hat Cs ase (ect ht) =a (0-H) a0 f ten aBuno | =====seseseSe — ie) 9804-9 ts Say, the change in le curt density at an interface in type mae tevin by syana[ oa i Matin so 45.7. Thups vermas recombination centres ‘When caries is captured by tp, tay then be elesed ort may be sonilated by the eaptze ofthe epee type af eerie. Whon the tine {brlecizon reas by theta seaton 1 tana EL ~ piyyeBBa! le rmich shorter than the tne foreapeure of «ae ae he sate canbe considered an elaton rap rather than recombination ‘eat, The may bappen ifthe tate i one energy to the condotion “and eg, ot the tos aston fr eeton capture ie much Lege than ‘erhole capt, a, or instance, ra peitively polaroed defect. Similarly, Joced sates which are let the Yalesoe un oe which ba a higher ‘ross scion fr ole eapaze set a9 Hoe traps raps weve to show dow Uh transport of rine bo Ube do wot remove then.aa ‘The Pye of Slr ite a ® © Fe, 404) Recuon tagig adage) see nb {(€) hole trapping and detrapping 7 a 4.6. Formulation ofthe Transport Problem, Fal ec poe ose the ne set ois fo mp aa wt ot in the introduction to this chapter. In one dimension, a 2m _ 12h be a (487) & 18h, BE toe (489) wad 2 £8 obras eno. as or Gy aad Gp we provi the photogenetton te that po. Fo Sandon entation G = Gy = Gy gn by Ee 428 and 28, Photogematin the ony stertion poe normaly ens ee ‘fro cls thrma eertin ofa taken tose cath th eprnions fr recombination, To enlete Gl) we eal how te abnptin coc Bs) te ct By, aad ee siden oon fe day) For ot Uy we stole poi the wu ofl te so isin jronace rating, Aug and tp ented ase hey of mm ¢ at 2. Fa rate setbiation te od en Sonica Ba (Fa. 457 a 58) Fr dager ema ae oe ‘Auger cots (Bg 46. or St ronson the balk ce eed {te dey and pton of ted tp wea and th oe fea es (Ee ho he a ination velocitiee (Eqs. 4.83 and 4.84), " | neato nd Rembinton na For the fod charge density in Pobon's equation we need the doping role Pesl2) = (Nae) + al) (490) nase Ny and Ng sprees the dein of inired acoeplars ad anor ‘ao Jy are dered for exytaline material Chapter 8. According to qe 165 and 3.86, the currents canbe expresed in ters of the eletron ‘dole qua! Fel evl,n pe dinension, ee, Jn wn Be ar, Je oye For a crptaline mate, these can be exposed in tems of = and ‘wing the deiitions of Ep, Ez, (Eas. 321 and 8.34) For nonecystaline ‘aerials we must substitute lteenativeeppropriat expression for Jy and Jp such 8g 381 ‘Whe Je and Jp arautesiited ato Bx 487 and 4.88, we hav act ofthe equations which ean be ole to deliver np and ga function of {and asuming tha all materia parameter ace known. Boundary cond ‘lon ae provided by the external eetrieal conditions and by the sue ecombination endtions, and by te tine dependence ofthe electrical and pica contions forthe rensient problem, 46.1. Comments on the tronsport problem Steady state soins Sine sla ol operte in he steady state we ae wally inteestein the cone where om _ op am sad solve the transport equations for steady sate lfuminstion snd lac Atle conditions [nthe steady state, the ection and ole deste in each ‘td and in locale ates mst be constant, Tis meson thatthe gem. ration and capture term for the exchange of eae betwen band and trap sates (ax oppoond to reconbioton cnt) snit canes xt, nd 20 ‘tapping can bells out ofthe continuty equations, The consequence i_ Tre Pref Slr Cae ha the generation and recombintion process are al lectively bunds torband: G, = Gy and Uy = Uy The trapped eburge density wl oBence "he soln tote te ed eharge tern in Poisson's equation nthe transiat ease where traps are being lla ov emptied, hen the term for capture and release fous tape tat he iced sant ener ‘ion rate fr holo aad electrons ae maser, Photon entity Until now, we have assumed tha the deity of photons at pit is de ‘ecmined solely by th absorption within the materia. That, we have scsued thatthe density of photons resting frm radiative tecumbin ‘os i ngligble compared to the acon xdeaiy, In meses wth ‘high radiative eicincy, or under Bi ination conditions, thee to ‘jee photons may be sgaieant. Then «furber continuity eamtion ‘egird, for photons, and a further uaknowa eads to be oun, ptan lux density (2) The eas of photon weeling ie teated in Chapter 8. 4.02. Thunsport equations in @ crystal "Tum unt eter context tor convestiontl photovoliaey is a aoe dimensionally varying crystalne materi in the sendy sate, The quay of ners is the net eument at ier ofthe ternal, Jy Jp wd ts do pence on applied bias and ination To hs weit need to st wp the transport equations and salve for n, pad 6, as decibed above ‘We proceed by combining the curreat equations fr compositionally luvatiant ryt (Eqs. 8.75 and 3.76) wth the steady state continlty ep ‘lon to obtain pai of wcond ard efeetial equations govern tnd ln oe dimension ean) sad (aon) Wile @ i wily function of postion only, U generally depends 5 U genealy depends upon loth este densities. Ths eouplo th traneport equations for elects ‘and oles. In certain situations, however, depends om mr onl and he ‘uations canbe solved independent, In particulate, hen 10) ove cain type greatly ences te ott and the recombination rate mplifsfo the tonomolcue form Ur (0 ~ not (Eq 480), nd {ay the electric eld Fle aero of constant che tansport equations for niority ears smiplfy to the analytically soluble for: @u , oF do {nm , Gls) = foe ae ao for eectrons nthe p eon, and fo, oF do (o-m) , OG) 9 ase Etre yt Dy nd fo bole inthe eon. ee me bave sed he Einstein elation w = $8 (Bq 8.7) fr yond have ator the difusion lenph or electrons be (495) _ by = ved (4.96) ‘etn ag maf ae dn ay | = ———S—N Se oo) pfs «sn _ sn | _~=sSseseNN Sia Ses ms a Dread wi fn —~h—™hmré<“—™~s—™—S—S—S—S—S—Sé;C tbh geno seo onl ope | = _es sort enantio ntinset anor ae Rip we hid sys Ep 1582 bo 47. Summary Photocurrent generation by «soar call slink to charge easier gener ‘tion and resombintin hy enseriation ofthe umber of electrons anda6 The Phy of Sor Cty ‘oles, Photogeneration isthe primary carer generation proc in poto- lac cell, For dvet gap eemicanductor, the absorption oust tan ‘be descr mathematrlly by o's Golden Ral, st nar to the band dg it depenis oa photon energy epprxinstaly us {© — "Ford ‘ect ap material, ght absorption require phonon almortion oes, ‘he absorption coefiient i genealy muller and ea more grado he (E~ By), nea the band edge. Phtogeraton foalyneqles te di ‘sintion of an eacted state and ot Lentcal to light aorption in one ‘compound or organic materials wher this isolation ie ncenplete ‘The min recombination mechanisms te radiative, Age, ad rapa sited recombination inthe blk ors he eurface, Rate recambinaton ie te eelaxation of an eleciron sero the baa gap together withthe emia, sion ofa photon. Is unaredable ina ight abmrbing materia ad st Important when absorption is stong, in diet gop smiondctare: The radiative recombination eat is described by a goneralied Planck feral and vavies approximately as np. Auger recombination i the elation of hare uve to excite a soon ari to higher euegy state wit the bund. The rte depons on cartier dente to third eed and i sronget ‘when the charge cares deaitis are high. Trap aatisedtecombinaton i ' mahiple step relaxation procs, usually involving inteiedlate state fhe band gap. Th eneay lost by relmation i given ups hea. Ton rate ‘epends upon the density and poston of then internat sas ado the relative densities of eeetrons and ble. Iti strongest foe de trays ‘when mand pare simi. In doped materia eben inca and can be tharctrised bya single recombition tine, hop aaisted rocubination le peticulely important at acuta on secon of tla sates, Series ‘combination becomes Inna ls doped tater ad ean be satScteied ‘by asurace rombination volt whith depends on the demi of eusfece defies tn real materials tap assed recombination is dominaet- Ta he limit of pefoct material redative recombination i dominant and Auger ‘becom important fo law baad gp and ndnet gap material Formulae forthe generation and recombination rates can be wel to Set up transport equations fr each of the charge eatties Togsber with Poisson's equation, these fm ast of coupled difeentil equations Which ‘canbe ole forthe charge carve densities, outrents and the electrostatic Potential. In general he problem is mpl: bat ean be greatly stoplifed rough senning linac recombination rte and ueleting elec fel, ‘condos which are veld ia many devie strate References 5. Adah Phyl Proprio II-V Somiconuctor Compounds (Chis: “Wi Ba and Pati Paran lnc Sater ond Opti! Drains "Sak (Oso Pee, 17) = 6. taars aoe Meche Apel to Sonicndctor Heer (Ea Actelte Badnetle orotic of Sar Pay Conese (Oxted 3. Fue Sar Ca Denes Phe (ew Yok London: Awe 18), MA. Gea Sion Str Cas And Pcp on Pos ey Can {ert Photons Bagong, 1) is A. Haglt snd Crt, Mole photos, er Chem, Lam: Rembton a Sein (Nor Yak Candis Us 4. Patan, pt Psaes in Semionduor (Baplewod Clit: Preatice M.S Psa of Senior Das (Eahwod Cie; Prt Hs, P. Suan, “Bemean tect of the otal propria, Sold State Ms. Tyan nett Senior Mural and Dies (Chih Wat“ me ptf maa, 7. Phy © ‘mi 38, sos Se Stei t | Chapter 5 Junctions SA. Introduction ‘Photovltale enegr conversion ela fom charge generation, charg xp aration and charge taneport. In haptars 3 an 4, the process of pho- togiteaton and charge anspor in & semiconductor wete disused. The tomaning tage, charge separate, requires some kind of diving fore. ‘This driving force ie aeoltly ay for photovlae energy conversion and tans be bu in to our device. Le the language of Chapter 3, ebe desing fev cn mgt bo Ngtinduced gradient in the ust Fee Lvs for ckettons ead ble, Ia an arate leek pietare, the Tks a> torhing mntval i conected tothe extaral erat by paths of diferent ‘esstance: one which hae me Ler resstancn for negative than postive ‘hays, andthe other which hat much loner rtance fr positive than egative (Fig. 6). Taplacile, the te many wae of providing a charge separating mech sia tenon proved by seta variation a the deceone env ronment, In v erytaline semicoulucter device, «Junction between oe yet => 4.51, Sctemaiol tare separtin metal a two devi. On "Spo lw et uk hr cu at sta ow, se th tes Perle ay ach hor bt tr cu Sch amy be od yw itr clewone ron tha {he Pg of ler iy lectronicallydiferont intel provides an electrostatic foes. In phox 'symthess — where charge partion i aio a rele —cnted eleteons sre driven acros the photoryathetic membrane by diferenom inthe five ‘acer of mole acoeptors. In both aan the foro aes omn a compe. sonal gradient. ths chapter me will discuss, without mathematical deal, various ‘types of junetion ws In photovolae deview, Caer 6 complete the esrpton of photovlae action with detailed apis ofthe mos Portant example, the pm jason, 5.2. Origin of Photovoltac Action Jn phoovhaideve et oe spration of ere Ta has satin ten ves et pisces sea) pots velage open cout). The photo acon ars a ng ‘ec spaaing ear. Hee wy wl nse ts erm te ct Sein tthe toca, (ean omy el beamed tes courts othe potraage Fane, LS) Now, roms Chapter 3 Es 3.5-3657) wa fr the urea te pot ht Jp = mune, + tyBVEry. cn By defintin, fr sericonductor in equinus, By, nd Fy, ae weal ‘and constant end J =0 everywhere. Soo alewephotorlal ction, we ‘st hve tno ws Kh os grade a ‘quasi Feral levels, : a Hom could that happen? Using dhe dit dftson forms for Jy at J from Chapter 8 (Eqs :753.7) me have thot . 1DaVla~ na) + l= mg) —Vy-KEVInN). (62) sod e WD eVU9— mi) + tal —w)QP Vx VE + KEVIN) (63) where no, fo represent dhe carer dense Ja sqiibrum and we have rade we ofthe fact that Jy = Jp = Oi equim. Insite egetion, the at arm represents dean aad the eosnd repreaents dy ser te et electric ld, which ede to ompontional gradient, a Wal go any cleccosttl Bld (as sown in Fig 5.2). When the esuntions are wien ‘i this form, both terms are ecially zero in equim, Ve lumination,n > ng ap > po Than, ifthe etal ld n00 sero net di curontwl ele Alanna that so elcid, but there ae gradients in the enter densities, then a net difsioncucent rin rorl "A lc led whic exis incur clea“ fit and is due to compositions fate. Ve sal se Below how a bila lecto- ‘aie ld ie establiced atthe iaerface bawoen tuo material of diferent ‘rove fusction. As shown in Cheer 3, a0 eft teed may leo ‘esl om gradients in tho elton aft, band gap, and fective band Aeaityof eats. An lactic fli is fective for charge eparction since it says dives p and n caries in oppsite diretions (Carrie density gradients rot roa gradiets i th geecation ot r= sora ae, In an others rotopic environment gradient inthe get- triton rate ofeletombole pcan re nm net eazet ony ifthe ‘ifson constants for slate aod holes azeifrent If they ae the ‘une, thin the electron and hele dilfarion curents cancel out exactly "The potential diference created by symmetry in difason constant, the ember potential is nt ural large enough fr elective photovoltaic scion in erystaline materi, although i may be large Us molecular Taree difmive currents can be achicted, however, ip an symetrc ceoironment where thre spice aliitional mechani which seletvly ‘emove eertrons or hols. This cal be &eottact which hat low rsstance {or deetrons au hgh fr holes, Such a coutct or dargd region prea tially removes eletrons fom dhe light absorbing region and eeates & (dient inthe eecron density. Kr may be considered ae an electron ink ‘That denaiy gran dives on eheton duion current Ta hie tution there is na hele cure to ented the eeetron cazrents sce holes wete ot eollesed. There maybe a sc eatact which peferetaly removes Jol, apd this crests bole difiion current which adds tothe electron Tn the following, we consider the contsibtione to the change separating fa ‘Bax 5.1 Conriatons to the hye separating fd Figur 5.2 shows « band prot representation ofthe various pose ‘oatubutions tothe electric fed experienced by electron the conduction Tad. (Not tat each of thee coaguratons ren ian eleteoneurent