38 Te(OH) 6 2NH 4 H 2 PO 4 (NH 4 ) 2 HPO 4

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Fig. A-1-1. Te(OH) NH H PO (NH ) HPO (TAAP). Projection of the crystal structure along the b direction [Ave]. 9 1. 7.5 ( a a )/ a [1 ] ( b b )/ b [1 ] 5..5 1.5 1 1.5 ( c c )/ c [1 ].5 1. 1.5. Angle β 1. 1.5 1..5 1 1.5 1 Fig. A-1-. Te(OH) NH H PO (NH ) HPO (TAAP). (a a )/a, (c c )/c, (b b )/b, β vs. T [9Prz]. a, b, c : extrapolated values of a, b, c, respectively, from the phase I.

5 κ 1 Dielectric constant κ 1 [1 ] 1 κ κ 5 1 15 5 1 Dielectric constant κ, κ [1 ] Fig. A-1-. Te(OH) NH H PO (NH ) HPO (TAAP). κ 1, κ, κ vs. T [91Cza]. κ 1 : dielectric constant for E parallel to the polar direction, κ 1 κ (11). κ = κ b. κ : dielectric constant for E along the direction perpendicular to both the polar axis and the b axis. Fig. A-1-. Te(OH) NH H PO (NH ) HPO (TAAP). κ a, κ b, κ c, κ 1 1 a, κ c vs. T [Gui].

. Inv. dielectric constant κ (11) [1 ] 1 1 f = 1 khz 1.5 1..5 Conductivity σ [1 Ω m ] 5 1 1 1 1 1 19 5 Fig. A-1-5. Te(OH) NH H PO (NH ) HPO (TAAP). κ, σ vs. T [9Cac]. κ (11) : dielectric constant perpendicular to (11). σ: ac conductivity. f = 1 khz.. 1 (11). 1 Dielectric constant κ (11) [1 ] 1. 1... 5 7 9 1 11 Temperature T [ C] Fig. A-1-. [Te(OH) NH H PO (NH ) HPO ] 1 x [Te(OD) ND D PO (ND ) DPO ] x. κ (11) vs. T [Sha]. 1: x =, : partially deuterated, : x 1. κ (11) : dielectric constant for E perpendicular to (11) face.

15 1 (11) [1 ] Inv. dielectric constant κ 1 9 1 5 7 9 1 11 Temperature T [ C] Fig. A-1-7. [Te(OH) NH H PO (NH ) HPO ] 1 x [Te(OD) ND D PO (ND ) DPO ] x. [Sha]. 1: x =, : partially deuterated, : x 1. κ 1 (11) vs. T f = 1 khz 1 (11) [1 ] Inv. dielectric constant κ 7 5 p = 5. 1 Pa 5.7..1..5.57 1.1 1 Pa Temperature T [ C] Fig. A-1-. Te(OH) NH H PO (NH ) HPO (TAAP). κ vs. T [9Fer]. Parameter: p. 1 (11)

Dielectric constant κ (11) [1 ] 1. 1. 1. 1..... T = C 1 1 1 (11) [1 ] Inv. dielectric constant κ 1 5 7 Pressure p [1 Pa] 1 Fig. A-1-9. Te(OH) NH H PO (NH ) HPO (TAAP). κ (11), κ vs. p [9Sha]. T = C. f = 1 khz. (11) T = 9 K f = 1 khz 1 (11) [1 ] Inv. dielectric constant κ 7 5..... Pressure p [1 Pa] Fig. A-1-1. Te(OH) NH H PO (NH ) HPO (TAAP). κ vs. p [9Fer]. T = 9 K. 1 (11)

Transition temperature Q f [ C] 1 5 Pressure p [1 Pa] Fig. A-1-11. Te(OH) NH H PO (NH ) HPO (TAAP). Θ f vs. p [9Sha]... R = min min 9 min 15 min Dielectric constant κ (11) [1 ] 1. 1... 5 7 9 1 5 7 9 51 5 Temperature T [ C] Fig. A-1-1. Te(OH) NH H PO (NH ) HPO (TAAP). κ (11) vs. T [91Sha]. Parameter: R. R: irradiation time of X-ray. X-ray from Cu target of kv, 5 ma was used.

1.75 1.5 f =5MHz 9 MHz Dielectric constant κ'[11] [1 ] 1.5 1..75.5 GHz MHz GHz.5. GHz 15 GHz 77 GHz 1. 1.5 15. 17.5..5 5. 7.5..5 5. Fig. A-1-1. Te(OH) NH H PO (NH ) HPO (TAAP). κ [11 ] vs. T [9Sob]. Parameter: f. κ [11 ] dielectric constant for E [11]. : real part of

7 f = GHz MHz Dielectric constant κ''[11] 5 9 MHz GHz GHz. GHz 15 GHz 1 5 MHz 77 GHz 1. 1.5 15. 17.5..5 5. 7.5..5 5. Fig. A-1-1. Te(OH) NH H PO (NH ) HPO (TAAP). κ [11 ] vs. T [9Sob]. Parameter: f. κ [11 ] : imaginary part of dielectric constant for E [11].

1. T f =. K Dielectric constant κ'[11] [1 ] 1... K 1.5 K 7 1 1 1 9 1 1 1 11 Frequency f [Hz] Fig. A-1-15. Te(OH) NH H PO (NH ) HPO (TAAP). κ [11] vs. f [9Sob]. Parameter: T Θ f. T f =. K Dielectric constant κ''[11] K 1.5 K 1 7 1 1 9 1 1 1 11 Frequency f [Hz] Fig. A-1-1. Te(OH) NH H PO (NH ) HPO (TAAP). κ [11] vs. f [9Sob]. Parameter: T Θ f.

1 Dielectric constant κ''[11] f =. GHz GHz 1. K. K GHz 1. K. K 5GHz 1 1 1 1 1 Dielectric constant κ' [11] T f =.5 K MHz 1 MHz 5 MHz Fig. A-1-17. Te(OH) NH H PO (NH ) HPO (TAAP). κ [11] vs. κ [11] (Cole-Cole diagram) [9Sob]. Parameter: T Θ f, f. Cross: center of circular arc. 15 [1 s ] 1 9 1 ( πτ ) 1 5 1 15 5 5 Fig. A-1-1. Te(OH) NH H PO (NH ) HPO (TAAP). (πτ) 1 vs. T [9Sob]. τ: dielectric relaxation time.

Dielectric constant κ (11) [1 ] 5 1 f = 1 khz 5.5 E bias = 9. 1 E bias = 1. 1 V m 1 1. 1 V m 1 17 1 19 Fig. A-1-19. Te(OH) NH H PO (NH ) HPO (TAAP). κ (11) vs. T [9Cac]. Parameter: E bias. κ (11) : dielectric constant for E perpendicular to (11) face. Fig. A-1-. Te(OH) NH H PO (NH ) HPO (TAAP). P s, P s vs. T [Gui]. P s : spontaneous polarization measured on (11) plate.

. 1.5 Polarization P s [1 C m ] 1..5 5 1 15 Fig. A-1-1. Te(OH) NH H PO (NH ) HPO (TAAP). P s vs. T [9Cac]. 1. 1. ( P / P ) [1 ] s s.. 5 Temperature T [ C] Fig. A-1-. Te(OH) NH H PO (NH ) HPO (TAAP). (P s / P s ) vs. T [9Fer]. P s : saturated spontaneous polarization: P s =.1 1 C m.

.. Polarization P s [1 C m ] 1. 1... 5.1.5.1 1 Pa 1.... p =1. 1 Pa Temperature T [ C] Fig. A-1-. Te(OH) NH H PO (NH ) HPO (TAAP). P s vs. T [9Sha]. Parameter: p.. p =. Polarization P s [1 C m ] 1. 1... p = 1. 1 Pa..5.1 1 Pa 1 1 Reduced temperature T [K] Fig. A-1-. Te(OH) NH H PO (NH ) HPO (TAAP). P s vs. T Θ f [9Sha]. Parameter: p. f

1. T =.5 K 1. ( P / P ) [1 ] s s...5..5..5 Pressure p [1 Pa] Fig. A-1-5. Te(OH) NH H PO (NH ) HPO (TAAP). (P s /P s ) vs. p at.5 K [9Fer]. P s : saturated spontaneous polarization; P s =.1 1 C m. 5 1 Pyroelectric coefficient p 1 [1 C m K ] 1 5 1 15 Fig. A-1-. Te(OH) NH H PO (NH ) HPO (TAAP). p 1 vs. T [91Cza]. p 1 : pyroelectric coefficient measured perpendicular to (11) face.

1 1 Specific heat c p [1 J K kg ] 1 1 1 1 1 1 1 1 Fig. A-1-7. Te(OH) NH H PO (NH ) HPO (TAAP). c p vs. T [Gui]. c p : specific heat capacity at constant pressure. Circle: adiabatic calorimeter method; plus sign: pyroelectric method. ( υ υ o )/ υ o [1 ] 1 f =1MHz MHz 5 MHz 1 1 5 5 5 55 5 7 Temperature T [ C] Fig. A-1-. Te(OH) NH H PO (NH ) HPO (TAAP). (υ υ )/υ vs. T [91Ban]. Parameter: f. υ: longitudinal ultrasonic wave velocity perpendicular to (11). υ : υ at 1 C.

5 f =1MHz MHz 5 MHz 5 15 Attenuation α [1 db m ] 1 5. 5......75.5.5. 5 5 5 55 5 Temperature T [ C] Fig. A-1-9. Te(OH) NH H PO (NH ) HPO (TAAP). α vs. T [91Ban]. Parameter: f. α: attenuation coefficient of longitudinal ultrasonic wave perpendicular to (11) face. c n P s 5 b n β 1 =5 n 1 a Fig. A-1-. Te(OH) NH H PO (NH ) HPO (TAAP). Orientation of principal axes of optical indicatrix [9Prz, Gui]. Rotation of the optical indicatrix with temperature: see Fig. A-1-1.

.7..5 Rotation angle θ [ ]....1 5 Temperature T [ C] Fig. A-1-1. Te(OH) NH H PO (NH ) HPO (TAAP). θ vs. T [Gui]. θ: rotation angle of optical indicatrix. See Fig. A-1-... ( n 1 ) [1 ].... δ ( n 1 ) [1 ].... 5 1.9 5 1 Fig. A-1-. Te(OH) NH H PO (NH ) HPO (TAAP). ( n 1 ), δ( n 1 ) vs. T [9Prz]. λ =. nm. ( n 1 ) = n 1 (T) n 1 (9 K), n 1 = n n. δ( n 1 ): deflection of n 1 from that of the extrapolated values of phase I. n 1, n, n : principal refractive indices. See Fig. A-1-. Full line: extrapolated value from the phase I.

1 1 δ ( n ) [1 ] 5 δ ( n ) [1 ] 7.5 1. 1.5 15. 17.5. 5 1 15 Fig. A-1-. Te(OH) NH H PO (NH ) HPO (TAAP). δ( n ), δ( n ) vs. T [9Prz]. λ =. nm. δ( n i ): deflection of n i from that of the extrapolated values of the phase I. n = n n 1, n = n 1 n. n 1, n, n : principal refractive indices; see Fig. A-1-. Fig. A-1-. Te(OH) NH H PO (NH ) HPO (TAAP). ν vs. T [Gai]. ν : 1 P chemical shift. ν L = 1 MHz.

1 1 Inv. time t m [1 s ] 1. 1. 1. 1..... T = 7.7 C..5. 9. 5. 15.. C 1 5 5 1 Electric field E [1 Vm ] Fig. A-1-5. Te(OH) NH H PO (NH ) HPO (TAAP). t vs. E [91Sha]. Parameter: T. t m : time corresponding to the maximum switching current. 1 m