Processing-composition-structure effects on the optical band gap of KNbO3-based ceramics

Transcription

1 Processing-composition-structure effects on the optical band gap of KNbO3-based ceramics PASCUAL-GONZALEZ, Cristina Available from Sheffield Hallam University Research Archive (SHURA) at: This document is the author deposited version. You are advised to consult the publisher's version if you wish to cite from it. Published version PASCUAL-GONZALEZ, Cristina (217). Processing-composition-structure effects on the optical band gap of KNbO3-based ceramics. Doctoral, Sheffield Hallam University. Copyright and re-use policy See Sheffield Hallam University Research Archive

2 APPENDICES Processing-composition-structure effects on the optical band gap of KNbO3-based ceramics Cristina Pascual-González A thesis submitted in partial fulfilment of the requirements of Sheffield Hallam University for the degree of Doctor of Philosophy October 217

3 APPENDIX A Contents Volume II APPENDIX A... 4 A.1. Rietveld Refinements plots... 4 A.2. EDX measurements... 9 A.3. FWHM values for XRD peaks from 55º to 57º APPENDIX B B.1. Rietveld Refinements plots B.2. EDX measurements B.3. P-E and S-E loops APPENDIX C... 3 C.1. Rietveld Refinements plots... 3 C.2. EDX measurements APPENDIX D D.1. Rietveld Refinements plots D.2. EDX measurements APPENDIX E E.1. Rietveld Refinements plots E.2. EDX measurements APPENDIX F F.1. Rietveld Refinements plots F.2. EDX measurements APPENDIX G G.1. Rietveld Refinements plots G.2. EDX measurements APPENDIX H

4 APPENDIX A H.1. Publications and Scientific Results H.1.1. Published papers H.1.2. Chapter book H.2. Attendance H.2.1. Placements H.2.2. Attended congresses H.2.3. Summer Schools H.3 Dissemination H.3.1 Oral contributions as presenting author H.3.2 Poster contributions as presenting author

5 APPENDIX A APPENDIX A Chapter 3: Processing and Characterisation of KNbO3 ceramics A.1. Rietveld Refinements plots A.1.1. KNbO3 Counts KN_178_2to8xrdml 9533-ICSD 1. % Position [ 2Theta] (Copper (Cu)) Figure A. 1.: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNbO 3. 4

6 APPENDIX A Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 2b Nb1 2a O1 2b O2 4d (5). Table A. 1 Occupancy, atomic fract. coordinates and Biso for KN A.1.2. K.95NbO2.975 Counts 4 K.95N_17-stripped 9533-ICSD 64.8 % 353-ICSD 35.2 % Position [ 2Theta] (Copper (Cu)) Figure A. 2: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for K.95NbO and K 4Nb 6O 17. 5

7 APPENDIX A Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 2b Nb1 2a O1 2b O2 4d Table A. 2: Occupancy, atomic fraction. coordinates and Biso for K.95NbO Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 Nb1 4a Nb2 4a Nb3 4a Nb4 4a Nb5 4a Nb6 4a K1 4a K2 4a K3 4a K4 4a O1 4a O2 4a O3 4a O4 4a O5 4a O6 4a O7 4a

8 APPENDIX A O8 4a O9 4a O1 4a O11 4a O12 4a O13 4a O14 4a O15 4a O16 4a O17 4a Table A. 3: Occupancy, atomic fraction. coordinates and Biso for K 4Nb 6O 17. Figure A. 3.: The pie chart represents the percent quantity of K.95NbO and K 4Nb 6O 17. 7

9 APPENDIX A A.1.3. KNb.95O3-δ Counts KN.95_16-stripped 9533-ICSD 1. % Position [ 2Theta] (Copper (Cu)) Figure A. 4.: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNb.95O Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 2b Nb1 2a O1 2b O2 4d (6). Table A. 4.: Occupancy, atomic fraction. coordinates and Biso for KNb.95O

10 APPENDIX A A.2. EDX measurements A.2.1. KNbO3 K (%) Nb (%) K/Nb Table A. 5: Theoretical K and Nb atomic percent for nominal KNbO 3 Measurements K (%) Nb (%) K/Nb Table A. 6.: K and Nb atomic percent for KNbO 3. 9

11 APPENDIX A A.2.2. K.95NbO2.975 K (%) Nb (%) K/Nb Table A. 7.: Atomic percent of K and Nb, for the nominal K.95NbO composition. Measurements K (%) Nb (%) K/Nb Table A. 8: Experimental atomic percent of K and Nb by EDX spectra for K.95NbO A.2.3. KNb.95O2.875 K (%) Nb (%) K/Nb 5 ~48 ~1.5 Table A. 9: Atomic percent of K and Nb, for the nominal KNb.95O composition. 1

12 APPENDIX A Measurements K (%) Nb (%) K/Nb Table A. 1: Experimental atomic percent of K and Nb by EDX spectra for KNb.95O A.3. FWHM values for XRD peaks from 55º to 57º Gaussian fitting permits to compare the FWHM values of the peaks from 55º to 57º (Figure A. 5) even if the entire quadruplet could not be fitted for the patterns. The FWHM values for K-excess compound (.13º,.129º and.191º) are much lower than pure (.28º and.189º) and K-deficiency (.339º and.241º) values. 11

13 Intensity (a.u.) Intensity (a.u.) APPENDIX A (a) KNbO 3 Fit Peak 1 Fit Peak 2 Cumulative Fit Peak Model Gauss Equation y=y + (A/(w*sqrt( PI/2)))*exp(-2*((xxc)/w)^2) Reduced Chi-Sqr E-6 Adj. R-Square.9914 Value Standard Error Peak1(B) y E E-5 Peak1(B) xc E-4 Peak1(B) w Peak1(B) A E-4 Peak1(B) sigma E-4 Peak1(B) FWHM Peak1(B) Height E-4 Peak2(B) y E E-5 Peak2(B) xc E-4 Peak2(B) w Peak2(B) A E-4 Peak2(B) sigma E-4 Peak2(B) FWHM Peak2(B) Height E (º) (b) K.95 NbO Fit Peak 1 Fit Peak 2 Cumulative Fit Peak Model Equation Gauss y=y + (A/(w*sqrt(PI/2)))*exp(-2*((x-xc)/w)^2) Reduced Chi-Sqr E-5 Adj. R-Square Value Standard Error Peak1(B) y E-4 Peak1(B) xc Peak1(B) w Peak1(B) A E-4 Peak1(B) sigma Peak1(B) FWHM Peak1(B) Height Peak2(B) y E-4 Peak2(B) xc Peak2(B) w Peak2(B) A E-4 Peak2(B) sigma Peak2(B) FWHM Peak2(B) Height (º) 12

14 Intensity (a.u.) APPENDIX A (c) KNb.95 O Fit Peak 1 Fit Peak 2 Fit Peak 3 Cumulative Fit Peak Model Equation Gauss y=y + (A/(w*sqrt(PI/2)))*exp(-2*((x-xc)/w)^2) Reduced Chi-Sqr E-5 Adj. R-Square Value Standard Error Peak1(B) y E-4 Peak1(B) xc Peak1(B) w Peak1(B) A E-4 Peak1(B) sigma Peak1(B) FWHM Peak1(B) Height Peak2(B) y E-4 Peak2(B) xc Peak2(B) w Peak2(B) A E-4 Peak2(B) sigma Peak2(B) FWHM Peak2(B) Height Peak3(B) y E-4 Peak3(B) xc Peak3(B) w Peak3(B) A E-4 Peak3(B) sigma Peak3(B) FWHM Peak3(B) Height (º) Figure A. 5: Gaussian fitting for estimation of the FWHM of peaks from 55º to 57º for (a) KNbO 3, (b) K.95NbO and (c) KNb.95O 2.875, suggesting a large degree of crystallisation in powders prepared with an excess of potassium. 13

15 APPENDIX B APPENDIX B Chapter 3: System (1 x) KNbO3-x(Ba.5Bi.5)(Zn.5Nb.5)O3 B.1. Rietveld Refinements plots B.1.1. (1-x) KNbO3-x BaBiNbZnO3 (KBNN) B x=.5 Counts 9 Kbbnz_.5_11_2to8long kbbnz x=.5 1. % Position [ 2Theta] (Cobalt (Co)) Figure B. 1.: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KBNNZ x=.5. 14

16 APPENDIX B Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K 2a Be 2a Bi 2a Nb 2b Zn 2b O 2a O 4e Table B. 1.: Occupancy, atomic fract. coordinates and Biso for orthorhombic KBBNZ x=.5 B x=.1 Counts Kbbnz_.1_11_2to8long KBBNZ1_cubic 28.2 % KBBNZ1_orto 71.8 % Position [ 2Theta] (Cobalt (Co)) Figure B. 2.: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KBNNZ x=.1. 15

17 APPENDIX B Figure B. 3.: The pie chart represents the percent quantity of the two polymorphs (orthorhombic and cubic) for KBBNZ x=.1. Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 1a Nb1 1b O1 3c Bi 1a Ba 1a Zn 1b Table B. 2.: Occupancy, atomic fract. coordinates and Biso for cubic KBBNZ x=.1 Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 2a

18 APPENDIX B Nb1 2b O1 2a O2 4e Bi 2a Ba 2a Zn 2b Table B. 3.: Occupancy, atomic fract. coordinates and Biso for orthorhombic KBBNZ x=.1 B x=.15 Counts 9 Kbbnz_.15_11_2to8long_ ICSD 71.5 % 9533-ICSD 28.5 % Position [ 2Theta] (Cobalt (Co)) Figure B. 4.: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KBNNZ x=.15 17

19 APPENDIX B Figure B. 5.: The pie chart represents the percent quantity of the two polymorphs (orthorhombic and cubic) for KBBNZ x=.15. Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 1b Nb1 1a O1 3d Ba 1b Bi 1b Zn 1a Table B. 4.: Occupancy, atomic fract. coordinates and Biso for cubic KBBNZ x=.15 Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 2b Nb1 2a

20 APPENDIX B O1 2b O2 4d Ba 2b Bi 2b zn 2a Table B. 5.: Occupancy, atomic fract. coordinates and Biso for orthorhombic KBBNZ x=.15 B x=.2 Counts 9 Kbbnz_.2_11_2to8long 1992-ICSD 1. % Position [ 2Theta] (Cobalt (Co)) Figure B. 6: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KBNNZ x=.2 Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 1b

21 APPENDIX B Nb1 1a O1 3d Ba 1b bi 1b zn 1a Table B. 6.: Occupancy, atomic fract. coordinates and Biso for cubic KBBNZ x=.5 B x=.25 Counts Kbbnz_.25_11_2to8long kbbnz x= % Position [ 2Theta] (Cobalt (Co)) Figure B. 7 Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KBNNZ x=.25. Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K 1a Ba 1a

22 APPENDIX B Bi 1a Nb 1b Zn 1b O 1b O 2c Table B. 7.: Occupancy, atomic fract. coordinates and Biso for cubic KBBNZ x=.25 B.2. EDX measurements B.2.1. (1-x) KNbO3-x BaBiNbZnO3 (KNBBZ) B x=.5 K (%) Nb (%) Ba (%) Bi (%) Zn (%) K/Nb K/Ba K/Bi K/Zn Table B. 8.: Atomic percent of K, Nb, Ba, Bi, Zn and molar relations for the nominal KNBBZ x=.5composition. K (%) Nb (%) Ba (%) Bi (%) Zn (%) K/Nb K/Ba K/Bi K/Zn

23 APPENDIX B Table B. 9.: Experimental atomic percent of K, Nb, Ba, Bi, Zn and molar relations for KNBBZ x=.5 composition by EDX spectra. B x=.1 K (%) Nb (%) Ba (%) Bi (%) Zn (%) K/Nb K/Ba K/Bi K/Zn Table B. 1.: Atomic percent of K, Nb, Ba, Bi, Zn and molar relations for the nominal KNBBZ x=.1 composition. K (%) Nb (%) Ba (%) Bi (%) Zn (%) K/Nb K/Ba K/Bi K/Zn

24 APPENDIX B Table B. 11.: Experimental atomic percent of K, Nb, Ba, Bi, Zn and molar relations for the nominal KNBBZ x=.1 composition by EDX spectra. B x=.15 K (%) Nb (%) Ba (%) Bi (%) Zn (%) K/Nb K/Ba K/Bi K/Zn Table B. 12.: Atomic percent of K, Nb, Ba, Bi, Zn and molar relations for the nominal KNBBZ x=.15composition. K (%) Nb (%) Ba (%) Bi (%) Zn (%) K/Nb K/Ba K/Bi K/Zn

25 APPENDIX B Table B. 13.: Experimental atomic weight of K, Nb, Ba, Bi, Zn and molar relations for the nominal KNBBZ x=.15 composition by EDX spectra. B x=.2 K (%) Nb (%) Ba (%) Bi (%) Zn (%) K/Nb K/Ba K/Bi K/Zn Table B. 14.: Atomic percent of K, Nb, Ba, Bi, Zn and molar relations for the nominal KNBBZ x=.2 composition. K (%) Nb (%) Ba (%) Bi (%) Zn (%) K/Nb K/Ba K/Bi K/Zn

26 APPENDIX B Table B. 15.: Experimental atomic percent of K, Nb, Ba, Bi, Zn and molar relations for the nominal KNBBZ x=.2 composition by EDX spectra. B x=.25 K (%) Nb (%) Ba (%) Bi (%) Zn (%) K/Nb K/Ba K/Bi K/Zn Table B. 16.: Atomic percent of K, Nb, Ba, Bi, Zn and molar relations for the nominal KNBBZ x=.25 composition. K (%) Nb (%) Ba (%) Bi (%) Zn (%) K/Nb K/Ba K/Bi K/Zn

27 APPENDIX B Table B. 17.: Experimental atomic percent of K, Nb, Ba, Bi, Zn and molar relations for the nominal KNBBZ x=.25 composition by EDX spectra. B.3. P-E and S-E loops Figure B. 8: (a) P-E and (c) S-E loops up to 8 kv/cm at RT. (b) P-E and (d) S-E loops from RT up to 2º under electric field of 5 kv/cm for KN at 1 Hz. 26

28 Strain(%) Polarisation ( C/cm 2 ) APPENDIX B ºC 18ºC 16ºC 14ºC 12ºC 1ºC 8ºC 4ºC RT (a) (b) ºC 18ºC 16ºC 14ºC 12ºC 1ºC 8ºC 4ºC RT.1 (c) Electric Field (kv/cm) (d) Electric Field (kv/cm -1 ) Figure B. 9: (a) P-E and (c) S-E loops up to 8 kv/cm at RT. (b) P-E and (d) S-E loops from RT up to 2º under electric field of 5 kv/cm for KBBNZ x=.5 at 1 Hz. 27

29 Strain (%) Polarisation ( C/cm 2 ) Strain (%) Polarisation ( C/cm 2 ) APPENDIX B RT 4ºC 8ºC 1ºC 14ºC 18ºC (b) RT 4ºC 8ºC 1ºC 14ºC 18ºC.1.5 (c) Electric Field (kv/cm) Electric Field (kv/cm) Figure B. 1: (a) P-E and (c) S-E loops up to 8 kv/cm at RT. (b) P-E and (d) S-E loops from RT up to 2º under electric field of 5 kv/cm for KBBNZ x=.5 at 1 Hz RT 4ºC 8ºC 1ºC 14ºC 18ºC (a) (c) RT 4ºC 8ºC 1ºC 14ºC 18ºC (c) Electric Field (kv/cm) Electric Field (kv/cm) Figure B. 11.:(a) P-E and (c) S-E loops up to 8 kv/cm at RT. (b) P-E and (d) S-E loops from RT up to 18ºC under electric field of 5 kv/cm for KBBNZ x=.15 at 1 Hz. (d) 28

30 Strain (%) Polarisation ( C/cm 2 ) Strain(%) Polarisation ( C/cm 2 ) APPENDIX B RT 4ºC 8ºC 1ºC 14ºC 18ºC (a) (b) RT 4ºC.35 8ºC.3 1ºC 14ºC.25 18ºC (c) Electric Field (kv/cm) Electric Field (kv/cm) (d) Figure B.12.: (a) P-E and (c) S-E loops up to 8 kv/cm at RT. (b) P-E and (d) S-E loops from RT up to 18ºC under electric field of 5 kv/cm for KBBNZ x=.2 at 1 Hz RT 4ºC 8ºC 1ºC 14ºC 18ºC -1-2 (a) RT 4ºC 8ºC 1ºC 14ºC 18ºC (b) Electric Field (kv/cm) (c) Figure B. 13: (a) P-E and (b) S-E loops up to 8 kv/cm at RT. (c) P-E and (d) S-E loops from RT up to 18ºC under electric field of 5 kv/cm for KBBNZ x=.25 at 1 Hz. -.1 Electric Field (kv/cm) (d) 29

31 APPENDIX C APPENDIX C Chapter 5: System (1-x) KNbO3- x BiFeO3 C.1. Rietveld Refinements plots C.1.1. (1-x) KNbO3- x BiFeO3 C x=.5 Counts knbf_.5_2to8_long knbf x=.5 1. % Position [ 2Theta] (Cobalt (Co)) Figure C. 1.: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNBF x=.5. 3

32 APPENDIX C Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K 2a Bi 2a Nb 2b (9).5 Fe 2b O 2a O 4e Table C. 1.: Occupancy, atomic fract. coordinates and Biso for orthorhombic KNBF x=.5 C x=.1 Counts knbf_.1_2to8_long knbf x=.1 1. % Position [ 2Theta] (Cobalt (Co)) Figure C. 2.: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNBF x=.1. 31

33 APPENDIX C Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K 2a Bi 2a Nb 2b Fe 2b O 2a o 4e Table C. 2.: Occupancy, atomic fract. coordinates and Biso for orthorhombic KNBF x=.1 C X=.15 Counts knbf_.15_2to8_long knbf x= % Position [ 2Theta] (Cobalt (Co)) Figure C. 3.: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNBF x=.15. Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 32

34 APPENDIX C K 2a Bi 2a Nb 2b Fe 2b a o 4e Table C. 3.: Occupancy, atomic fract. coordinates and Biso for orthorhombic KNBF x=.15. C X=.2 Counts knbf_.2_2to8_long knbf x=.2 1. % Position [ 2Theta] (Cobalt (Co)) Figure C. 4.: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNBF x=.2. Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 33

35 APPENDIX C K 2a Bi 2a Nb 2b Fe 2b O 2a o 4e Table C. 4.: Occupancy, atomic fract. coordinates and Biso for orthorhombic KNBF x=.2 C X=.25 Counts 9 knbf_.25_2to8_long knbf x= % Position [ 2Theta] (Cobalt (Co)) Figure C. 5.: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNBF x=.25. Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 34

36 APPENDIX C k 2a Bi 2a Nb 2b Fe 2b O 2a O 4e Table C. 5.: Occupancy, atomic fract. coordinates and Biso for orthorhombic KNBF x=.25. C.2. EDX measurements C.2.1. (1-x) KNbO3- x BiFeO3 C x=.5 K(%) Nb(%) Bi(%) Fe(%) K/Nb K/Bi K/Fe Table C. 6.: Atomic weight of K, Nb, Bi, Fe and molar relations for the nominal KNBF x=.5composition. K(%) Nb(%) Bi(%) Fe(%) K/Nb K/Bi K/Fe

37 APPENDIX C Table C. 7.: Experimental atomic weight of K, Nb, Bi, Fe and molar relations for KNBF x=.5 composition by EDX spectra. C x=.1 K(%) Nb(%) Bi(%) Fe(%) K/Nb K/Bi K/Fe Table C. 8.: Atomic weight of K, Nb, Bi, Fe and molar relations for the nominal KNBF x=.1 composition K(%) Nb(%) Bi(%) Fe(%) K/Nb K/Bi K/Fe

38 APPENDIX C Table C. 9.: Experimental atomic weight of K, Nb, Bi, Fe and molar relations for KNBF x=.1 composition by EDX spectra. C x=.15 K(%) Nb(%) Bi(%) Fe(%) K/Nb K/Bi K/Fe Table C. 1.: Atomic weight of K, Nb, Bi, Fe and molar relations for the nominal KNBF x=.15 composition. K(%) Nb(%) Bi(%) Fe(%) K/Nb K/Bi K/Fe

39 APPENDIX C Table C. 11.: Experimental atomic weight of K, Nb, Bi, Fe and molar relations for KNBF x=.15 composition by EDX spectra. C x=.2 K(%) Nb(%) Bi(%) Fe(%) K/Nb K/Bi K/Fe Table C. 12.: Atomic weight of K, Nb, Bi, Fe and molar relations for the nominal KNBF x=.2 composition. K(%) Nb(%) Bi(%) Fe(%) K/Nb K/Bi K/Fe

40 APPENDIX C Table C. 13.: Experimental atomic weight of K, Nb, Bi, Fe and molar relations for KNBF x=.2 composition by EDX spectra. C x=.25 K(%) Nb(%) Bi(%) Fe(%) K/Nb K/Bi K/Fe Table C. 14.: Atomic weight of K, Nb, Bi, Fe and molar relations for the nominal KNBF x=.25 composition K(%) Nb(%) Bi(%) Fe(%) K/Nb K/Bi K/Fe

41 APPENDIX C Table C. 15.: Experimental atomic weight of K, Nb, Bi, Fe and molar relations for KNBF x=.25 composition by EDX spectra. 4

42 APPENDIX D APPENDIX D Chapter 6: System (1-x) KNbO3- x BiMnO3 D.1. Rietveld Refinements plots D.1.1. (1-x) KNbO3- x BiMnO3 D x=.5 Counts KNBMn_.5_ ICSD 22.8 % 1992-ICSD 77.2 % Position [ 2Theta] (Cobalt (Co)) Figure D. 1.: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNBM x=.5. 41

43 APPENDIX D Figure D. 2.: The pie chart represents the percent quantity of the two polymorphs (orthorhombic and cubic) for KNBM x=.5. Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 2b Nb1 2a O1 2b O2 4d Bi 2b Mn 2a Table D. 1.: Occupancy, atomic fraction coordinates and Biso for orthorhombic KNBF x=.5. 42

44 APPENDIX D Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 1b Nb1 1a O1 3d Bi 1b Mn 1a Table D. 2.: Occupancy, atomic fraction coordinates and Biso for cubic KNBF x=.5. D x=. 1 Counts KNBMn_.1_ ICSD 85.9 % 9533-ICSD 14.1 % Position [ 2Theta] (Cobalt (Co)) Figure D. 3.: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNBM x=.1. 43

45 APPENDIX D Figure D. 4.: The pie chart represents the percent quantity of the two polymorphs (orthorhombic and cubic) for KNBM x=.1. Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 1b Nb1 1a O1 3d bi 1b Mn 1a Table D. 3.: Occupancy, atomic fraction coordinates and Biso for cubic. KNBF x=.1. Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 2b Nb1 2a O1 2b

46 APPENDIX D O2 4d Bi 2b Mn 2a Table D. 4.: Occupancy, atomic fraction coordinates and Biso for orthorhombic KNBF x=.1. D x=.15 Counts KNBMn_.15_ ICSD 94.6 % 9533-ICSD 5.4 % Position [ 2Theta] (Cobalt (Co)) Figure D. 5.: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNBM x=

47 APPENDIX D Figure D. 6.: The pie chart represents the percent quantity of the two polymorphs (orthorhombic and cubic) for KNBM x=.15. Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 1b Nb1 1a O1 3d Bi 1b Mn 1a Table D. 5.: Occupancy, atomic fraction coordinates and Biso for cubic KNBF x=

48 APPENDIX D Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 2b Nb1 2a O1 2b O2 4d Bi 2b Mn 2a Table D. 6.: Occupancy, atomic fraction coordinates and Biso for orthorhombic KNBF x=.15. D x=.2 Counts 36 KNBMn_.2_ ICSD 1. % Position [ 2Theta] (Cobalt (Co)) Figure D. 7.: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNBM x=.2. 47

49 APPENDIX D Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 1b Nb1 1a O1 3d Bi 1b Mn 1a Table D. 7.: Occupancy, atomic fraction coordinates and Biso for cubic KNBF x=.2. D x=.25 Counts KNBMn_.25_ ICSD 1. % Position [ 2Theta] (Cobalt (Co)) Figure D. 8.: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNBM x=

50 APPENDIX D Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 1b Nb1 1a O1 3d Bi 1b Mn 1a Table D. 8.: Occupancy, atomic fraction coordinates and Biso for cubic KNBF x=.25. D.2. EDX measurements D.2.1. (1-x) KNbO3- x BiMnO3 D x=.5 K (%) Nb (%) Bi (%) Mn (%) K/Nb K/Bi K/Mn Table D. 9: Atomic weight of K, Nb, Bi, Mn and molar relations for the nominal KNBM x=.5composition. K (%) Nb (%) Bi (%) Mn (%) K/Nb K/Bi K/Mn

51 APPENDIX D Table D. 1 Experimental atomic weight of K, Nb, Bi, n and molar relations for KNBM x=.5 composition by EDX spectra. D x=.1 K (%) Nb (%) Bi (%) Mn (%) K/Nb K/Bi K/Mn Table D. 11: Atomic weight of K, Nb, Bi, Mn and molar relations for the nominal KNBM x=.1 composition. K (%) Nb (%) Bi (%) Mn (%) K/Nb K/Bi K/Mn

52 APPENDIX D Table D. 12: Experimental atomic weight of K, Nb, Bi, Mn and molar relations for KNBM x=.1 composition by EDX spectra. D x=.15 K (%) Nb (%) Bi (%) Mn (%) K/Nb K/Bi K/Mn Table D. 13: Atomic weight of K, Nb, Bi, Mn and molar relations for the nominal KNBM x=.15 composition. K (%) Nb (%) Bi (%) Mn (%) K/Nb K/Bi K/Mn Table D. 14: Experimental atomic weight of K, Nb, Bi, Mn and molar relations for KNBM x=.15 composition by EDX spectra. 51

53 APPENDIX D D x=.2 K (%) Nb (%) Bi (%) Mn (%) K/Nb K/Bi K/Mn Table D. 15.: Atomic weight of K, Nb, Bi, Mn and molar relations for the nominal KNBM x=.2 composition. K (%) Nb (%) Bi (%) Mn (%) K/Nb K/Bi K/Mn Table D. 16.: Experimental atomic weight of K, Nb, Bi, Mn and molar relations for KNBM x=.2 composition by EDX spectra. 52

54 APPENDIX D D x=.25 K (%) Nb (%) Bi (%) Mn (%) K/Nb K/Bi K/Mn Table D. 17.: Atomic weight of K, Nb, Bi, Mn and molar relations for the nominal KNBM x=.25 composition. K (%) Nb (%) Bi (%) Mn (%) K/Nb K/Bi K/Mn Table D. 18.: Experimental atomic weight of K, Nb, Bi, Mn and molar relations for KNBM x=.25 composition by EDX spectra. 53

55 APPENDIX E APPENDIX E Chapter 7: System (1 x) KNbO3-x BiCoO3 E.1. Rietveld Refinements plots E.1.1. (1-x) KNbO3-x BiCoO3 (KNBC) E x=.5 Counts KNCoBi_.5_188_bigpellet 1992-ICSD 91.9 % 9533-ICSD 8.1 % Position [ 2Theta] (Cobalt (Co)) Figure E. 1: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNBC x=.5. 54

56 APPENDIX E Figure E. 2: Coexistence of two phases, (a) cubic and (b) orthorhombic, refined by Rietveld method for KNBC x=.5 Figure E. 3.: The pie chart represents the percent quantity of the two polymorphs (orthorhombic and cubic) for KNBC x=.5. Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 2b Nb1 2a O1 2b O2 4d Bi 2b

57 APPENDIX E Co 2a Table E. 1: Occupancy, atomic fract. coordinates and Biso for orthorhombic KNBC x=.5 Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 1b Nb1 1a O1 3d Bi 1b Co 1a Table E. 2: Occupancy, atomic fract. coordinates and Biso for cubic KNBC x=.5 E x=.1 Counts KNCoBi_.1_ ICSD 1. % Position [ 2Theta] (Cobalt (Co)) Figure E. 4: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNBC x=.1. 56

58 APPENDIX E Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 1b Nb1 1a O1 3d Bi 1b Co 1a Table E. 3: Occupancy, atomic fract. coordinates and Biso for cubic KNBC x=.1 E x=.15 Counts KNCoBi_.15_ ICSD 1. % Position [ 2Theta] (Cobalt (Co)) Figure E. 5: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNBC x=

59 APPENDIX E Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 1b Nb1 1a O1 3d Bi 1b Co 1a Table E. 4: Occupancy, atomic fract. coordinates and Biso for cubic KNBC x=.15 E x=.2 Counts 16 KNCoBi_.2_ ICSD 1. % Position [ 2Theta] (Cobalt (Co)) Figure E. 6: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNBC x=.2 58

60 APPENDIX E Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 1b Nb1 1a O1 3d Bi 1b Co 1a Table E. 5: Occupancy, atomic fract. coordinates and Biso for cubic KNBC x=.2 E x=.25 Counts KNCoBi_.25_ ICSD 1. % Position [ 2Theta] (Cobalt (Co)) Figure E. 7: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNBC x=

61 APPENDIX E Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 1b Nb1 1a O1 3d Bi 1b Co 1a Table E. 6: Occupancy, atomic fract. coordinates and Biso for cubic KBBNZ x=.25 E.2. EDX measurements E.2.1. (1-x) KNbO3- x BiCoO3 E x=.5 K (%) Nb (%) Bi (%) Co (%) K/Nb K/Bi K/Co Table E. 7: Atomic percent of K, Nb, Bi, Co and molar relations for the nominal KNBC x=.5composition. K (%) Nb (%) Bi (%) Co (%) K/Nb K/Bi K/Fe

62 APPENDIX E Table E. 8: Experimental atomic percent of K, Nb, Bi, Co and molar relations for KNBC x=.5 composition by EDX spectra. 61

63 APPENDIX E E x=.1 K (%) Nb (%) Bi (%) Co (%) K/Nb K/Bi K/Co Table E. 9: Atomic percent of K, Nb, Bi, Co and molar relations for the nominal KNBC x=.1 composition K (%) Nb (%) Bi (%) Co (%) K/Nb K/Bi K/Co Table E. 1: Experimental atomic percent of K, Nb, Bi, Co and molar relations for KNBC x=.1 composition by EDX spectra. 62

64 APPENDIX E E x=.15 K (%) Nb (%) Bi (%) Co (%) K/Nb K/Bi K/Co Table E. 11: Atomic percent of K, Nb, Bi, Fe and molar relations for the nominal KNBC x=.15 composition K (%) Nb (%) Bi (%) Co (%) K/Nb K/Bi K/Co Table E. 12: Experimental atomic percent of K, Nb, Bi, Co and molar relations for KNBC x=.15 composition by EDX spectra. 63

65 APPENDIX E E x=.2 K (%) Nb (%) Bi (%) Co (%) K/Nb K/Bi K/Co Table E. 13: Atomic percent of K, Nb, Bi, Co and molar relations for the nominal KNBC x=.2 composition. K (%) Nb (%) Bi (%) Co (%) K/Nb K/Bi K/Co Table E. 14: Experimental atomic percent of K, Nb, Bi, Co and molar relations for KNBC x=.2 composition by EDX spectra. 64

66 APPENDIX E E x=.25 K (%) Nb (%) Bi (%) Co (%) K/Nb K/Bi K/Co Table E. 15: Atomic percent of K, Nb, Bi, Co and molar relations for the nominal KNBC x=.25 composition K (%) Nb (%) Bi (%) Co (%) K/Nb K/Bi K/Fe Table E. 16: Experimental atomic percent of K, Nb, Bi, Co and molar relations for KNBC x=.25 composition by EDX spectra. 65

67 APPENDIX F APPENDIX F Chapter 8: System (1-x) KNbO3- x BiNiO3 F.1. Rietveld Refinements plots F.1.1. (1-x) KNbO3- x BiNiO3 F x=.5 Counts KN-BN_.5_ ICSD 72.1 % 9533-ICSD 27.9 % Position [ 2Theta] (Copper (Cu)) Figure F. 1: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNBN x=.5. 66

68 APPENDIX F Figure F. 2: The pie chart represents the percent quantity of the two polymorphs (orthorhombic and cubic) for KNBN x=.5. Figure F. 3: Coexistence of two phases, (a) cubic and (b) orthorhombic, refined by Rietveld method for KNBC x=.5 Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 2b Nb1 2a O1 2b O2 4d Bi 2b Ni 2a Table F. 1: Occupancy, atomic fract. coordinates and Biso for orthorhombic KNBN x=.5 67

69 APPENDIX F Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 1b Nb1 1a O1 3d Bi 1b Ni 1a Table F. 2: Occupancy, atomic fract. coordinates and Biso for cubic KNBN x=.5 F x=.1 Counts KN-BN_.1_ ICSD 1. % Position [ 2Theta] (Copper (Cu)) Figure F. 4: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNBN x=.1. 68

70 APPENDIX F Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 1b Nb1 1a O1 3d Bi 1b Ni 1a Table F. 3: Occupancy, atomic fract. coordinates and Biso for orthorhombic KNBN x=.1 F Alternative Rietveld refinement for x=.1 into orthorhombic symmetry. Counts KN-BN_.1_ ICSD 1. % Position [ 2Theta] (Copper (Cu)) Figure F. 5: Alternative refinement. Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNBN x=.1 into orthorhombic phase. 69

71 APPENDIX F Space Group Amm2 Density (Experimental) (g/cm 3 ) 4.2(2) Density (calculated) (g/cm 3 ) 4.971(3) Relative Density (%) 84(1) a (Å) 4.148(1) b (Å) 5.677(2) c (Å) (7) V/1 6 (pm 3 ) (2) Rexp.812 Rp Rwp GOF Table F. 4: Experimental and theoretical density, lattice parameters and agreement indices calculated by Rietveld Refinement for KNBN (x=.1) F X=.15 Counts KN-BN_.15_ ICSD 1. % Position [ 2Theta] (Copper (Cu)) Figure F. 6: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNBN x=.15. 7

72 APPENDIX F Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 1b Nb1 1a O1 3d Bi 1b Ni 1a Table F. 5: Occupancy, atomic fract. coordinates and Biso for orthorhombic KNBN x=.15. F X=.2 Counts KN-BN_.2_ ICSD 1. % Position [ 2Theta] (Copper (Cu)) Figure F. 7: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNBN x=.2. 71

73 APPENDIX F Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 1b Nb1 1a O1 3d Bi 1b Ni 1a Table F. 6: Occupancy, atomic fract. coordinates and Biso for orthorhombic KNBN x=.2 F X=.25 Counts 16 KN-BN_.25_ ICSD 1. % Position [ 2Theta] (Copper (Cu)) Figure F. 8: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNBN x=

74 APPENDIX F Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 1b Nb1 1a O1 3d Bi 1b Ni 1a Table F. 7.: Occupancy, atomic fract. coordinates and Biso for orthorhombic KNBF x=.25. F.2. EDX measurements F.2.1. (1-x) KNbO3- x BiNiO3 F x=.5 K (%) Nb (%) Bi (%) Ni (%) K/Nb K/Bi K/Ni Table F. 8: Atomic percent of K, Nb, Bi, Ni and molar relations for the nominal KNBN x=.5composition. K (%) Nb (%) Bi (%) Ni (%) K/Nb K/Bi K/Ni Table F. 9: Experimental atomic percent of K, Nb, Bi, Ni and molar relations for KNBN x=.5 composition by EDX spectra. 73

75 APPENDIX F F x=.1 K (%) Nb (%) Bi (%) Ni (%) K/Nb K/Bi K/Ni Table F. 1: Atomic percent of K, Nb, Bi, Ni and molar relations for the nominal KNBN x=.1 composition K (%) Nb (%) Bi (%) Ni (%) K/Nb K/Bi K/Ni Table F. 11: Experimental atomic percent of K, Nb, Bi, Ni and molar relations for KNBN x=.1 composition by EDX spectra. 74

76 APPENDIX F F x=.15 K (%) Nb (%) Bi (%) Ni (%) K/Nb K/Bi K/Ni Table F. 12: Atomic percent of K, Nb, Bi, Ni and molar relations for the nominal KNBN x=.15 composition. K (%) Nb (%) Bi (%) Ni (%) K/Nb K/Bi K/Ni Table F. 13: Experimental atomic percent of K, Nb, Bi, Ni and molar relations for KNBN x=.15 composition by EDX spectra. 75

77 APPENDIX F F x=.2 K (%) Nb (%) Bi (%) Ni (%) K/Nb K/Bi K/Ni Table F. 14: Atomic percent of K, Nb, Bi, Ni and molar relations for the nominal KNBN x=.2 composition. K (%) Nb (%) Bi (%) Ni (%) K/Nb K/Bi K/Ni Table F. 15: Experimental atomic percent of K, Nb, Bi, Ni and molar relations for KNBN x=.2 composition by EDX spectra. F x=.25 K (%) Nb (%) Bi (%) Ni (%) K/Nb K/Bi K/Ni Table F. 76: Atomic percent of K, Nb, Bi, Ni and molar relations for the nominal KNBN x=.25 composition K (%) Nb (%) Bi (%) Ni (%) K/Nb K/Bi K/Ni

78 APPENDIX F Table F. 17: Experimental atomic percent of K, Nb, Bi, Ni and molar relations for KNBN x=.25 composition by EDX spectra. 77

79 APPENDIX G APPENDIX G Chapter 9: Ferroelectric and optical properties for: KNbO3 vs K.9Ba.1Nb.95Ni.5O3 K.5Na.5NbO3 vs K.49Na.49Ba.2Nb.99Ni.1O3 G.1. Rietveld Refinements plots G.1.1. KNbO3. Counts KN_178_2to8xrdml 9533-ICSD 1. % Position [ 2Theta] (Copper (Cu)) Figure G. 1.: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNbO 3 ceramic. 78

80 APPENDIX G Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 2b Nb1 2a O1 2b O2 4d (5). Table G. 1.: Occupancy, atomic fract. coordinates and Biso for orthorhombic KN. G KNbO3-.1 BaNb.5Ni.5O3 (KN-BNN) Counts KBaNbNi_.1_ ICSD 1. % Position [ 2Theta] (Copper (Cu)) Figure G. 2: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KN-BNN ceramic. 79

81 APPENDIX G Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 2b Nb1 2a O1 2b O2 4d Ba 2b Ni 2a Table G. 2: Occupancy, atomic fract. coordinates and Biso for orthorhombic KN-BNN. G.1.3. K.5Na.5NbO3 Counts KNN_ _1hour scan 9533-ICSD 1. % Position [ 2Theta] (Cobalt (Co)) Figure G. 3.: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for KNN ceramic. 8

82 APPENDIX G Atom Wyck. s.o.f. x y z Biso/ 1^4 pm^2 K1 2b Nb1 2a O1 2b O2 4d Na 2b Table G. 3.: Occupancy, atomic fract. coordinates and Biso for orthorhombic KNN. G K.5Na.5NbO3-.2 BaNb.5Ni.5O3 (KNN-BNN) Counts 4 KNNBNN_ ICSD 1. % Position [ 2Theta] (Cobalt (Co)) Figure G. 4.: Experimental X-ray diffraction data (red), calculated fitting profile (blue) and difference plot for.98 K.5Na.5NbO 3-.2 BaNb.5Ni.5O 3 ceramic. 81