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1

2 LCD EL SAW CVD dc rf Hall Hall van der Pauw van der Pauw i

3 m cm ii

4 iii

5 1 1.1 Liquid Crystal Display: LCD Plasma Display Panel: PDP ELElectro Luminescence LCD Thin Film Transistor: TFT PHS Personal Handy-phone System 5 ~ LCD PDP EL 4.1 ( 1.1) 1.1 : 2010, 2001, 1 1 : EL 2 : EL 7.1 ~ EL 3 : PDP FED 0.9 ~ EL p15 1

6 110-3 cm 380 ~ 780 nm 80% 3.2 ev 350 ~ 400 nm 1.2 Au, Ag, Pt, Cu, Rh, Pd, Al, Cr In O 2 3, SnO 2, ZnO, CdO, TiO2, Cd In O 2 4, Cd SnO 2, Zn SnO 2 2 4, In O ZnO 2 3 MgInO 4, CaGaO4 TiN, ZrN, HfN LaB : 166 p80 AuAgPtCuRhPdAlCr 3 ~ 15 nm ~ 10 cm cm ~ 10 cm n In 2 O 3 SnO 2 ZnOCdOCdIn 2 O 4 Cd 2 SnO 4 Zn 2 SnO 4 In 2 O 3 -ZnO In2O3 SnSnO2 SbFZnO InGaAl ~ 10 cm 10 3 ~ 10 4 cm 2

7 Al ZnO Zn Al Sn In O 2 3ITO: Indium Tin OxideITO nm 90% cm + ITO H In kg Zn 163 In 40,000 Flat Panel Display: FPD ITO ITO Zn 3

8 2 2.1 ZnO AlGa ZnOAZO, GZO ZnO P63mc 2.1 Zn O O 3/ nm Zn nm 4 O nm nm Zn-O 4 O Zn 4s-O 2p a = nmc = nm c c Zn (0001) O (0001) ZnO Zn 10% 4

9 2.1: ZnO v E v = µe (2.1) eτ µ = τ, m* m * 1 q ρ 1 qnµ = (2.2) n n ZnO n ZnO 1 ZnO [Zn ] + e + O2 2 i (2.3) 5

10 1 ZnO [Vo ] + e + O 2 (2.4) 2 i ] i ] [Zn ] 1 Zn [Vo 1 O e [Zn ] [Vo ZnO ev Zn O Zn n Zn O cm : ZnO 166 p137 6

11 rfradio frequency cm ZnO ZnO [Zn i '] [Vo'] Al [Al'] [Zn i '] [Vo'] Al cm 3 Al Zn m* k m* n ZnO m* = 0. 3me 5 BHD Brooks-Herring-Dingle theory I 4 µ Fermi-Dirac 24π ( ε ε ) h n r µ I = e m * ( x) Z n I ε 0 ε r Z n I (x) 4 1 ( x) = In x x 1+ 4 x 7

12 2 e m * x = πε ε h 3π n 0 r 1/3 N r N µ N 3 µ = m * e N 3 20ε ε h n µ µ ac eh ρu 2 π = E m * ( kt) ρ E k u1 1 n µ disl µ disl ε d 2π ( kt ) = N e f m disl λ d ε d f N λ disl εkt λ d = e n d 8

13 VolgerPetritz KazmerskiOrton PowellSeto Q t = Nl N l Qt 2 Q t < NL L n N E B E B 2 2 q Qt = εN 2 Lq EB µ g th = exp πm * kt kt l EB 2 µ g tun 2 Lq 2m * E = B 4πl m E 2 2 * B µ g tun exp h l n 2 h µ g tun µ µ = + + L µ µ 1 2 µ n ZnO n > cm -3 9

14 2.3.2 ZnO 3.3 ev 380 ~ 780 nm Burstein-Moss Burstein-Moss 2.3 : Burnstain-Moss 166 p cm 3 10

15 2.3.3 ZnO 2.1 H vap kj.mol C p (J/(degmol)) S p (J/deg) H t (kj/mol) (kj/mol) G t MJ/mol 3 kg/ m kg/1 kg H 2 O J/(smdeg) ZnO X -6 3 ~ 4 10 / ~ / : ZnO 2002 p ZnO ZnO ZnO 3.2 ~ 3.3 ev 11

16 ZnO LCD LCD: liquid crystal display (b) RGB TFT 5 LCD LCD /01/13 LCD ITO 2.5 LCD 30 nm 300/ 85 ~ 90% 12

17 2.4 : 166 p EL Electro Luminescence (EL) EL EL dc 1.5 lm/w 1000 cd/ EL 1987 EL 2.5 EL x, y EL 10µm 100 ~ 300 nm EL 0.1 ~ 0.2 µm 10 / 13

18 2.5 : EL 166 p TV TFT TFT 2004/01/1380 Plasma Display PannelPDP 2 20 ~ 30 mm 2.6- x, y ITO Cr-Cu-Cr MgO x, y Ne 14

19 2.6 : PDP 166 p pn n p n p 1991 Ru TiO 2 ZnO Ru Ru Si H ZnO + H 15

20 2.4.5 SAW ZnO surface acoustic wave: SAW CdS Cd ZnO ZnO c 2.5 CVD LiNbO3 LiTaO3 SAW ZnO ZnO resistorvariable - M ZnO ZnO 0.5 mol Bi O Cr O Sb O CoO MnO ns

21 ZnO 1975 CVD CVD Chemical vapor deposition: CVD ZnO Zn(C H H OH ZnO Zn(C 2 5 ) 2 2 H 5 ) 2 Zn(C 2 H 5 ) 2 C

22 2.7 : 2002 p Pa 1000 ~ 4000 K

23 : p ZnO Ga O

24 2.9 : 166 p212 1 ~ 10 Pa ev ev Ar ev ev 2 20

25 X Ar + Ar : p69 21

26 1 2.2 / 0.1 ~ ~ ~ ~ 0.1 ~ : 2002 p ~ dcrf dc 2.11 dc 22

27 1 Pa V Ar + dc rf 2.11 : dc 2002 p rf 2.12 rf 2.11 dc dc rf rf 23

28 dc dc dc 13.56MHz rf dc dc 2.12 : rf 2002 p

29 dc : 2002 p42 25

30 3 3.1 Hall Hall HL5500PC: ACCENTHall van der Pauw 3.2 Hall 1879 E. H. Hall Hall Hall effect Hall 3.3 Hall 3.1 : n Hall p238 I x n B v z x 26

31 qv B x z y G H G H y Hall E y Hall + y qe y Lorentz s force 0 qe ( qv B ) = 0 (3.1) y x I x b t p I = qnv bt (3.2) G H 3.2 R H V x x z V H 3.1 I xbz = E yb RH (3.3) t H = R H 1 = (3.4) ( q n) Hall coefficient R I [A] B [T]b [m]t [m]q [C]p [m-3] H V [V] R [m3/c] H H R H x z V H = 1 ( q p) (3.5) R H 2 p 2 n 1 pµ nµ = (3.6) q ( nµ + pµ ) 2 n p R H p 27

32 3.4~3.6 γ R H Si Ge γ = 3π 8 γ = 315π 512σ n σ n = qµ n n 3.4 γ R H σ n = µ qn ( qµ nn) = γµ n Hn = (3.7) µ Hall mobility H n µ H p ( qµ p p) = γµ p H p γ R Hσ p = µ qn = (3.8) 3.4 van der Pauw van der Pauw L. J. van der Pauw 1958 van der Pauw Hall n p van der Pauw Hall Hall van der Pauw Hall 3.2ab 28

33 1 cm 4 (b) 3.2 : van der Pauw A, B, C, D p223 Hall 3.5 van der Pauw 3.2 AB I CD V AB CD R AB, CD VCD R AB, CD = (3.9) I AB BC I DA V BC DA R BC, DA 29

34 AC I AC BD VDA R BC, DA = (3.10) I BC B V BD V BD R AC, BD = (3.11) I AC ρ n µ ( R + R ) πd AB, CD BC, DA RAB, CD ρ = f (3.12) In2 2 RBC, DA µ B n = e d (3.13) R AC, BD µ d R AC. BD = (3.14) B ρ e d f R AB, CD R BC, DA R R f exp = arccosh In2 ( In2/ ) AB, CD BC, DA f AB, CD+ RBC, DA 2 R (3.15) R AB CD RBC, DA, > f () R, CD / RBC, DA ( R) AB = R f van deru Pauw (3.3) 30

35 3.3 : van der Pauw f 2002 p O 2 RPDReactive Plasma Deposition (250 A) 31

36 4.1 : : 4.2 : 32

37 7 (1996) p

38 4.2.2 RPD ZnO Ga O 2 2 O : RPD ZnO

39 cm RPDMOCVDPLDrfMS PLD 1cm RPDMOCVDrfMS Corning # mm PLD RPD 200MOCVD rfMS 90MOCVD MOCVD rfms 35

40 4.1 : ZnO 1, 1m 2, 10 cm 15 ccm dcms : DC rfms : rf rfmrs : rf RPD : 166 p139 36

41 4.5 : 166 p : 166 p139 37

42 RPD 200 rfms rfms *, ** 4.2 : p RPD rfms 38

43 : 1m Hall Hall 1cm

44 Hall ± 300 mm RPD Ga 5.1 : 40

45 n 5.2 : 41

46 ± O : 42

47 5.3.3 RPD ρ ρ av : 100 ρ n nav : 100 n av av µ µ av : 100 µ av (5.1) (5.2) (5.3) 5.4 ~ 5.6 ± 6 ± 6 % ± 10 % 5.5 ± 8 % RPD ± 10 ~ ±15 % RPD 5.4 : 43

48 5.5 : 5.6 : 44

49 5.3.4 Atomic Force Microscope: AFM JSPM-4210JEOL 5.7 ~ 5.11 AFM d ~ g (nm) (nm) d 40 ~ ~ 70 e 20 ~ ~ 40 g 30 ~ ~ 50 k 20 ~ ~ 30 s 40 ~ ~ : AFM e 45

50 ~ Ga 46

51 5.7 : 5.8 : e 47

52 5.9 : g 5.10 : k 48

53 5.11 : s m sccm 10 sccm 10 sccm 10 sccm 10 sccm 5.3 : Hall 49

54 5.12 : 5.13 : 50

55 cm 10 cm RPD Hall ( : 10 cm m 5.14 : 51

56 sccm 5 sccm 5 sccm 10 sccm 10 sccm 20 sccm 5.15 : 5.4 Hall 52

57 6 6.1 Hall Hall Hall van der Pauw 1 m RPD rfmsrf 1 m 53

58 6.2 Ga 54

59 ZnO PIXE 20 PIXE [] EL /2/ (1996) Pauw 32, 11 (1963) (1973) L.J. van der PauwPhilips Tech. Rev. 20 (1958/59) (2000) Vol.50, No.9, (1999) T. Yamamoto and H. Katayama-Yoshida" Solution Using a Codoping Method to Unipolarity for the Fabrication of p-type ZnO", Jpn. J. Appl. Phys. 38 (1999) L166-L T. Yamamoto and H. Katayama-Yoshida, "Unipolarity of ZnO with a wide-band gap and its solution using codoping method", Journal of Crystal Growth 214/215 (2000) T. Yamamoto and Hiroshi Katayama-Yoshida, "Control of Valence States in ZnO by Co-doping Method", Mater. Res. Soc. Proc. 623 (2000) T. Yamamoto and H. Katayama-Yoshida, "Physics and Control of Valence States in ZnO by Codoping Method", Physica B, 302/303 (2001)

60 20. T. Yamamoto and H. Katayama-Yoshida,"Materials design for the fabrication of p-type ZnO by codoping method":proc. 25th Int. Conf. on the Physics of Semiconductors (ICPS25), Osaka, 2000(Springer, Berlin, 2001)p T. Yamamoto, "Control of Valence States for ZnO and ZnS With a Wide-Band Gap by a Co-Doping Method", Mat. Res. Soc. Symp. Proc. 719 (2002) (Symposium F:Defect and Impurity Engineered Semiconductors and Devices III. Editors: S. Ashok, J. Chevallier, N.M. Johnson, B.L. Sopori,H. Okushi). 22. T. Yamamoto, "Codoping for the fabrication of p-type ZnO", Thin Solid Films, (2002) T. Yamamoto, "Codoping Method for Solutions to Doping Problems in Wide-Band-Gap Semiconductors", physica status solidi (a) 193, No.3 (2002) S. Shirakata, T. Sakemi, K. Awai and T. Yamamoto, "Optical and electrical properties of ZnO films prepared by URT-IP Method", Thin Solid Films, 445 (2003) T. Yamamoto,"Control of N-Impurity States in N-Doped ZnO, ZnS and ZnTe", Jpn. J. Appl. Phys. Vol. 42 (2003) pp. L514-L K. Iwata, T. Sakemi, A. Yamada, P. Fons, K. Awai, T. Yamamoto, M. Matsubara, H. Tampo and S. Niki,"Growth and electrical properties of ZnO thin films deposited by novel ion plating method", Thin Solid Films, 445 (2003) T. Sakemi, S. Shirakata, K. Iwata, K. Matsubara, H. Tampo, P. Fons, S. Niki, K. Awai, T. Yamamoto, High-Quality Transparent Conducting Oxide Films Deposited by a Novel Ion Plating Technique, MRS Proceedings Volume 763, B7.4, Editors: Rommel Noufi, William N. Shafarman, David Cahen, Lars Stolt. 28. S. Shirakata, T. Sakemi, K. Awai and T. Yamamoto, "Optical and electrical properties of URT-IP ZnO thin films for photovoltaic devices", to be published in Thin Solid Films. 29. T. Yamamoto, T. Sakemi, K. Awai and S. Shirakata, "Dependence of carrier concentrations on oxygen pressure for Ga-doped ZnO prepared by ion plating method", to be published in Thin Solid Films. 56

61 AFM 13 57

36 th IChO : - 3 ( ) , G O O D L U C K final 1

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