1 - 群馬大学
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1. 3 3 2 600 1200 1500 0 3 um ALO 0 1 um2. 18 ABER Vo Vp Henin E fir E HEI E Fig 2 8 2 5 2 Ar RAMANOR T64000 CCD Jobin Yvon detector 5145 BP filter Collective lens lt Analyzer Dispersion arrangement change Collective lens Incidence lens Smample Fig 2 9 Ar 5145 A
3. ON OFF WL Setup End 24 5 Measurement Go
4. 1 2 3 parameter 1 4 parameter 2 VI Windows XP Windows 7 Windows 7 EE 25 Current Grating f Set up i USA 1 urrent Description Dynamic Reserve
5. 2 17 1 5 13 Ga 3d
6. k Fig 4 14 Kesterite 1 0 eV 2 2 eV T 4 7 eV P Stannite 1 0 eV T 2 2 eV LLP 4 7 eV PT kK T I T I T I T T T T T T T T T T T T Cu ZnSnSe D 10 e Pol cr ssal 10 m SE Kesterite calc Stannite calc di di 5 5 0 1 1 1 1 1 0 L l 1 l 1 l 1 1 1 0 1 2 3 4 5 0 1 2 3 4 5 Photon energy eV Photon energy eV Fig 4 13 SE s
7. Vw p r LDA pr GGA GW GGA LDA LDA 2 GW 14 2 3 3 SCF Self Consistent Field HERE Fig 2 5 WE p p p
8. e Sn 1 20 30 e 10 Torr 31 3 2 2 1000 e e e
9. 0 1 Snell H SE A y N n ik e a N RU E Hi HI pd e v gt Fig 2 1 1 Fig 2 1
10. c E EI 2 15 BERRA KOGE n 12 E720 MTE v FF 5 E 2 E 2 E d E 2 2 2 Fig 2
11. Tm uu cf 53 4
12. EUROTHERM Fig 3 1 hil 30 da i c c EM NEN sol See br L Ze 40 e F 230L bel L bD 9 20 T F 10 i 400 600 800 1000 Temperature mg Fig 3 1 3 2 Cu ZnSnSe 3 2 1 e 5 5 mm 1 0 mm e 5 e e
13. 3 2 3 Se 220 20C Sn 232 08C Zn 419 68C 12 Cu OBL 900 15C h 1084 6 1150 36 lt 1 0 cm day 25 C cm Fig 3 2 CuZnSnSe4 Temperature 1150 C EEN 1 AN cette n OB pnm Se OO E S 12h 12h 12h 36h Fig 3 2 CuZnSnSe 32 3 3 3 3 1
14. Table 4 4 HE a c Cu ZnSnSe Stannite 5 68 11 33 42 Cu ZnSnSe Kesterite 5 68 11 36 4 5 5 77 11 55 I 42d Table 4 4 DU 432 Cu ZnSnSe Stannite Kesterite CunSe Fig 4 6 Fig 4 7 Fig 4 8 Cu ZnSnSe CulnSe CuZnSnSe lX CulnSe Stannite Kesterite CurZnSnSe Kesterite DOS Density of state Fig 4 9 Fig 4 7 Fig 4 9 Cu 3d Se 4p Sn 5s Se 5
15. Absorption coefficien reflectivity X 11 Fig 2 3 7
16. E 54
17. T puo E Poa SCF 15 B Y P new m lt 2 4 XRD X Ray Diffraction X X TL Ch 5 0C Fig 2 6
18. 20 300 K g2 0 1 mm 0 85 1 10 eV ATF hE 0 1 mm 2 14 Table4 1 R R SE 0 27 Fig 4 1 1 5 Cu ZnSnSe a 10cm UA Ge 0 9 1 0 1 1 Photon energy e V Fig 41 y h MILA F EEGEN be a E AE E 4 1 CuZnSnSe Fig 4 1 p Fig 4 2 Fig 4 2
19. XRD FHig 3 4 XRD Cu ZnSnSe Kesterite Stannite XRD T T T T I T p Cu ZnSnSe un 3 T T T T T I T 3 2 e e Pu M E E oi 8 e Cu ZnSnSe4 a S PDP a _ j 1 1 a jl a re 20 40 60 80 20 40 60 80 20 deg 20 deg Fig 3 3 Cu ZnSnSe XRD Fig 3 4 CuwZnSnSe X PDF 34 35 XRD Oi F
20. Fig 3 5 P Cu ZnSnSe 173 cm 196 cm 1 231 em iz Z7 Cu ZnSnSe 173 196 231 Intensity a u xd 200 30 400 aman intensity a u R 50 100 150 200 250 300 Raman Shift cm Fig 3 5 CuZnSnSe O 35 1 2 3 4 5 2002 1990 H Matsushita T Maeda A Katsui and T Takizawa Jounal of Grystal Growth 208 416 2000 S Schorr Solar Energy Materials and Solar Cell 95 1482 1488 2011 M Altosaar J Raudoja K Timmo M Danilson M Grossberg J Krustok and E Mellikov Phys Stat sol a 205 167 170 2008 36 4 Cu ZnSnSe RE PEST 41 Table 4 1 WNW
21. CwZnSnSe CuZnSnSe Fig 1 2 3 4 5 6 E UN 11 OT Z wT4 5212 IO IV Si In TI Zn IV Sn 4 NN CTS HI V GaAs CuuZnSnSe CIS SN Fig 1 2 2 SEN i Case Fig 1 2 b Fig I IH VI CulnSe 12 THA EX Ax bi WS xz IL I H IV VI Cuj nSnSe Cu ZnSnSe 1 4 eV Fig 1 1 1 4 eV 1 5 eV a b c Fig 1 2 CuInSe Cu ZnSnSe
22. Schrodinger Hy E 2 16 HAIL hT wil FII Ch 4 ol p p 93 77 Z N 1 e erter 2 17 1 2 3 4 5 Schrodinger
23. 3 ESIS HIE TY y HI Bridgman Stockbarger Brigman Stockberger vertical Bridgman
24. 1989 1995 1993 7 2004 P Hohenberg and W Kohn Phys Rev 136 B864 1964 W Kohn and L J Sham Phys Rev 140 A1133 1965 J P Perdew Phys Rev Lett 55 1665 1985 M S Hybertsen and S G Louie Phys Rev B 34 5390 1986 ARAR WAER X 1979 R A Alberty P W Atkins ORK SEDE SAR m HW 29 3 3 1 3 1 1
25. 7 eV Zn 3g Zn 3d Cu 3d Se 4p Zn 41 Energy eV T r N Wave vector Fig 4 6 Cu ZnSnSe Stannite Energy e V Wave vector Fig 4 8 CuInSe 42 DOS States eV Energy eV Fig 4 7 Cu ZnSnSe Kesterite Wave Vector T T T Cuj ZnSnSe Kesterite 20 Cu 10 1 o 4 n I I 4 20 Cuj ZnSnSe Kesterite cen L Zn 4 Io i OL T T CuoZnSnSe Kesterite 20 n 10 1 l AL 1 0 T T T Cuj ZnSnSe Kesterite 20 Se 10 0 1 I 15 10 Energy e V Fig 4 9 CuoZnSnSe DOS 433
26. H c 333 2500 33 35 300 600 C REA m 3h SE 1 Table T ERR
27. VGF vertical gradient freezing GaAs InP 312 Bol i auc uc
28. rv Vo Vp Vo t Vs Fig 2 7 17 P aE 2 22 e amp Py Axx Q yy P Og Qy X Ey 2 23 P 2 Oy r r COS 2Z 7 2 24 eg r
29. x I x 1 R I 2 11 2 7 em 7 I 1 R Iy exp 2ad 2 12 1 RY I exp ad 2 13 7 L 1 R exp ad 1 1 A exp 2g9 A 7 1 amp T 2 14 1 R I exp ad RI Fig 2 3 11
30. Ellipsometry HEIL p s mc A w Spectroscopic Ellipsometry HI HI a Ank EK x H 2 1 2
31. fa Kesterite E A E lc 0 1 2 3 4 5 6 Photon energy eV Photon energy eV Fig 4 10 S 2n 1 a 0 0 T 2 0 0 0 N 2n 1 a 1 a 0 2n 1 a l a 1 2c L 2n 1 a 0 1 2c T 2n 0 0 1 Fig 4 11 Cu ZnSnSe 43 0 1 2 3 4 5 6 0 1 2 3 4 5 Photon energy eV Photon energy eV Kesterite E c b Stannite E c Kesterite 0 1 2 3 4 5 6 0 1 2 3 4 5 Photon energy eV Photon energy eV c Kesterite E Lc d Stannite E Lc Fig 4 12 26 k RORE 44 Poly 2gg gg Je 3 4 3 SE s Fig 4 13 Cu ZnSnSe Kesterite Stannite Kesterite
32. 50 Table 3 1 RE 3 1 300 600 450C 300 550 600 5S00 550 500 3 4 XRD mm 500 XRD PDF Fig 3 3 CuZnSnSe PDF CuZnSnSe PDF
33. 0 Pir 0 1 SR 2 p AHE mu H LL H E En H Y s GE n Sin d n sin Snell s Law 2 1 Ep n COS no COS 3s F Y 2a E ncos N cos E N COS Q N COS 08 0 1 d 2 2b E njcos n cos E 2n cos fs 2 2c n COS n COS E 2n COS 15 l 9 d 2 2d E 7 njcos n cos 1 m ntik Fresnel Fresnel p s TA ra e d p s poryr A A A
34. 50 Stannite CP exper cal eV El Elc energy eV transition energy eV transition Eoa 1 03 I 123 124 1 125 126 1 03 123 124 gt 1 125 126 Eos 1 08 I 121 122 1 125 126 1 08 121 122 gt 125 126 Eoc 1 27 T 119 120 gt T 125 126 1 27 119 120 gt 125 126 E 25 2 3 123 124 gt 125 126 2 5 N 123 124 N 125 126 2 8 P 119 120 P 125 126 L 123 124 L 125 126 T 121 122 125 126 E 39 3 6 113 114 gt 125 126 E 49 4 8 119 120 gt 129 130 4 9 105 106 gt 125 126 L 119 120 L 131 132 N 119 120 N 129 130 5 119 120 gt 5 129 130 L 119 120 L 131 132 N 119 120 N 129 130 123 124 gt 1 131 132 105 106 gt 125 126 Table 4 6 Stannite WEDS Lon 123 124 125 126 51 1 2 3 4 5 6 7 8 9 S Ozaki M Sasaki and S Adachi Phys Status Solidi A 203 2648 2006 S Ozaki and S Adachi J Appl Phys 100 113526 2006 C Bellabarba and C Rincon Jpn J Appl Phys Suppl 32 599 1993 J J M Binsma L J Giling and J Bloem J Lumin 27 55 1982 N Yamamoto H Horinaka and T Miyauchi Jpn J Appl Phys Part 1 18 255 1979 P W Yu W J Anderson and Y S Park Solid State Commun 13 1883 1973 A Bauknecht S Siebentritt J Albert Y
35. 9 Setun End Setup End e gt fSetup End Faart RTRuE m LC SEELEN Le ER deene GE Ee E i SES B ls Sound Output Clear vi UUHUHUHUUHHUHUHUUHUHUHHUUUHUHUHUUUHUHUHUUUHUHUUHUHUHUHUHUHUHUHUHUHUHUURHUHHUHUHUHHHUHUHUHHUHHUUHUUU UUHUHHUHUUHUHUHHUHUUHUHHUUUHHUHUUUHUHUHUHUUU Fig 2 13 28 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 FUR 2003 57 1868 1988 62 1197 1993 DVA 36VW A S Adachi Optical properties of crystalline and amorphous semiconductors materials and Fundamental principles Kluwer Academic Publishers Boston 1999 Harland G Tompkins A User s Guide to ellipsometory Academic Press Boston 1993
36. 5610B HORIBA 1 MicroHR SCIENTIFIC INSTRUMENTS SU M9700 GPIB GPIB US Table 2 2 20 2 6 2 LabVIEW LabVIEW C BASIC LabWindows CVI 23 LabVIEW LabVIEW GPITB VI
37. 2 1200 500 nm 300 600 Grating Setup End 3 Lock In Setup o Data Code 1 Data Code 2 Output Data J b Lock m Setnp End 4 Wavelength and Temperature Setup
38. Es 5o R exp A 2 3a r exp A 2 3b p RJ eas tany ei 2 4 p EX 5 X nx gt w A 2 D e er i W M 2g 2 2b 2 3 12 i sing tan Ng 7 2 5 1 1 2 4 n n tan Z E ie 1 2 6 1 p e n Ei n sin tan hl cos 2y 2y sin A 2 7a 1 sin2y cos 2n sin tan sin 2y cos 2y sin 2 7b 1 sin 2y cos A 213
39. E E cos2zvot 2 25 r 1 1 P E GE cos2zv t a E cos 2zv 5 P cos2zt V 7 SE Cos2z v Ve t 2 26 P v r r v v Y ELOV
40. 4 3 1 WIEN2k WIEN2k L APW lo 1728 12x12x12 64 4x4x4
41. kt 33 EE 33 EE EE 33 ee EE 34 34 XRD kk 34 3 5 tees ei etat tura t a ri Md 35 SEA 36 4 CujZnSnSe EE je O JC KE 37 RE 37 AL M ON EE 39 WR ael EE a I PO CPE as 41 4o eb oed mediae a ada 41 432 pake E su mu uma umu mamaku a ta LI LU Ca GE LO AL ALS AS 41 EE 43 46 52 5 E EE 53 EE 54 1 1 4 Si 1 1 eV CutnSe CIS 1 19 5 51
42. W n ik 1 2 1 2 le el DI 2 2 24 2 ya ix 2 9 2 R 2 2 n 1 k 2 1 4 SB RI Fig 2 2 Sample 222227 2 Lamp Polarizer Detector Monochromator Fig 2 2 SE DVA 36VW A 200 1100 nm Xe 3i Table 2 1 SE 10 22 2 2 1
43. CuzZnSnSe 4 Cu ZnSnSe 1 02 eV E SE 2 2 eV 4 7 eV 3 6eV Cu ZnSnSe Kesterite Stannite Kesterite Stannite SE SE
44. 0 1nm Xe SGi 70 30 1 2 5 5 eV Table 4 3 SE GEN EE E EE EE 8 Cu ZnSnSe 0 3 um 6 0 1 um 0 05 um 4L 2 L L so j 42 1 a SI 2 3 4 5 Photon energy eV Fig 4 3 a 0 3 um b 0 1 um Fig 4 4 39 0 05 Fig 4 5 SE g e Ri lis lt C SE lt 2 2 eV 3 6 eV 4 7 eV e N Cu ZnSnSe 3 Photon energy eV 2 Fig 4 5 SE 40 4 3
45. Fig 4 10 Kesterite Stannite O c ey ss FHig 4 11 k Fig 4 12 s Kesteraite 2 8 eV 3 9 eV C T 4 7 eV c lt 3 eV G T P RDS OBA ELc TL Stanite c 2 8 eV TPR 4 8 eV TT LOO Lc 2 5 eV CN A 3 6eV CP 4 9 eV TP N 1 0 eV T Fig 4 12
46. 37 20 K 300 K lt 0 02 eV 1 01 eV FEC Cu ZnSnSe 1 4 eV 1 0 eV FE D 1 06 1 04 gt 2 M 1 02 experiment P ssler 1 00 0 100 200 300 Temperature K Fig 4 2 p Passler E r E 0 77 i el 4 2 e 7 Passler
47. X 2 b 2 Fig 2 8 X 6 27sin Bragg 2dsin0 n 2 18 Bragg X X
48. Fig 4 2 Table 4 2 E eV 10 eV K K p 1 034 0 23 450 4 0 Table 4 2 Passler 38 4 2 SE Table 4 3 SE 0 3 0 1 0 05 um 3 Fig 4 3 Br M 10 x3 Fig 4 4 a b c Fig 4 4 0 1 um Fig 4 3 O lum
49. PM 2 6 3 GPIB USB USB Fig 2 11 PC VI Fig 2 11
50. 28 FE CusZnSnSe SOS PHBE a 4 PC NSR 4 ze TO as Rus sss Tun nus Sun mas 5 12 Ge 6 LE SEE ILE m 7 Eeer 7 DEM E EN E 7 EE 7 21 3 CHLOE eA OO BUR m 9 E WEE 10 TEE 11 2 2 1 EE Eed 12 EE 13 p x WI E A a EE EE 13 232 Density Functional Theory i 14 23 3 SCE Self Consistent Field bk 15 2 4 XRD X Ray Diffraction YNS 16 E m unas ba au dene 17 EE 17 de co nrc T 19 2 6 LabVIEW 20 DG DEE 20 26 2 EE 21 21 2 6 4 GUI Graphic User Interface i 22 e DIEM 29 EE EE 30 EHE T e 30 S jep s to EE 30 3 1 2 30 39 60DZPS0S6 31 Bol 2s B Q mua EE 31 E Ee 32 32 e 33 3 3 1
51. E Jobin Yvon T64000 Ye Ye 19 2 6 LabVIEW 261 NATIONAL INSTRUMENTS LabVIEW 2011 VD VI VI Fig 2 10
52. X 20 Fig 2 6 Bragg 16 25 2 5 1 1928 Raman UU
53. r Einstein E hv 2 19 Eo E hv hv 2 20 E E v hv hcv 2 21 100 4000 cm r 1 v tv vy
54. Analysis Frequency Setup End Range He r1 Reference Ga E nuumnuuuuuuuuugumnuugumnuuuuguuuuuunuuuugumnuuuuuuuuusuuuuuun Output Data 1000000 ToT 10000 MEL LTS MIN eV Kaes SEH 26 E Pi min amm ESD p H x ae 1 Parameter 2 Build XY Graph WA XY 2 T d Ir CK 27
55. In 4d 2 3 2 DFT Density Functional Theory 1964 P Hohenberg W Kohn 5 2 1965 W Kohn L J Sham ry E 4
56. RSR SE fot ee pa ee Sr Cu ZnSnSe Kesterite A Cu ZnSnSe Stannite S Poly crystal 4 10 al 10 0 1 2 3 4 5 6 0 1 2 3 4 5 6 Photon energy eV Photon energy eV Fig 4 14 45 4 3 4 FHig 4 15 Fig 4 16 Kesterite Fig 4 18 Fig 4 19 Stannite TARY FHE Z Fig 4 17 Fig 4 20 Table 4 5 Table 4 6 1 2 3 4 5 6 0 1 2 3 4 5 Photon energy eV Photon energy eV Fig 4 15 Kesterite L Cu ZnSnSe Kesterite Poly crystal Photon energy eV Fig 4 16 SE Kesterite 46 A9 AS1ouq Wave vector Fig 4 17 Kesterite O73 47 Kesterite CP exper cal eV
57. 21 2 6 4 GUI Graphic User Interface Fig 2 13 Pt Z k l GUI Fig 2 12 a b t Fig 2 12 a GUI 22 Measurement 5 K im fev 8 i Parameter 1 Parameter 2 Current WL i Fen 10 0 897999 nm 10 GN irl MB GUI o gt 12 b H Fig 2 23 1 Setup Table 2 3 Force Initialization Connect Initialzed Micro HR Automated GPIBO 2 INSTR GPIBO 15 INSTR Table 2 3 2 Grating Control
58. 4 Ge Monochromator Ge E JE Lockin Chopper Lenses Halogen Lamp ites 16 Sample Pinhole Ref Fig 2 4 12 2 3 2 3 1 M Car Parrinello Schrodinger Dirac
59. Cu ZnSnSe b ILIV VL Cuj ZnSnSe 72 1 S Chen and X Gong Phys Rev 79 165211 2009 2 X Y Shi F Q Huang M L Liu and L D Chen Appl Phys Lett 94 122103 2009 12 5 1 2 3 4 Cu ZnSnSe 5 c z4 gt 2 21 2 1 1
60. Tomm and M C Lux steiner Jpn J Appl Phys Suppl 39 322 2000 S Ahn S Jung J Gwak A Cho K Sin K Yoon D Park H Cheong and J H Yun Appl Phys Part 1 97 021905 2010 P Blaha K Schwarz K H Madsen D Kvasnicka and J Luitz WIEN2k An Augmented Plane Wave Local Orbitals Program for Calculating Crystal Properties Karlheinz Schwartz Techn Universtat Wien Austria 2001 ISBN 3 9501031 1 2 52 5 L IL IV VL CusZnSnSe XRD SE 2 LabVIEW 3 Cu ZnSnSe S00C XRD
61. Elle energy eV transition energy eV transition Eoa 1 03 I 123 124 1 125 126 1 03 123 124 gt 1 125 126 Eos 1 07 I 121 122 1 125 126 1 07 121 122 gt 125 126 Eoc 1 15 I 119 120 1 125 126 1 15 119 120 gt 125 126 Ei 2 2 N 123 124 N 125 126 2 2 N 123 124 N 125 126 123 124 gt 125 126 123 124 gt 125 126 E 2 5 2 8 123 124 125 126 2 8 123 124 125 126 L 123 124 L 125 126 123 124 1 125 126 E 39 3 9 123 124 127 128 3 9 123 124 gt 127 128 4 3 121 124 gt 129 130 4 7 123 124 gt 1 131 132 123 124 gt 1 131 132 121 122 gt 131 132 121 122 gt 1 131 132 119 120 gt 131 132 119 120 gt 131 132 4 9 5 3 119 120 gt 133 134 5 2 119 120 gt 133 134 105 106 gt 125 126 L 119 120 L 129 130 Table4 5 123 124 125 126 48 1 Stannite Elc 1 E E 1 1 4 1 1 2 3 4 5 1 2 3 4 5 6 Photon energy eV Photon energy eV Fig 4 18 Stannite Cu ZnSnSe Stannite Pol Photon energy eV Fig 4 19 SE Stannte 49 Stannite IN Q un E N N 5 Wave vector Fig 4 20 Stannite
62. Si 10 2 Si lt 3 7 4 CIS 2 PV2030 CIS 2030 25 40 AAW 7 CTIS m 1 In
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