Research progress of pyroelectric characteristics of lead-free ferroelectric ceramics for infrared detection

Guo Shao-Bo; Yan Shi-Guang; Cao Fei; Yao Chun-Hua; Wang Gen-Shui; Dong Xian-Lin

doi:10.7498/aps.69.20200303

Abstract

Due to the excellent pyroelectric properties, ferroelectric ceramics containing lead element are widely used as sensitive materials in pyroelectric infrared detectors at present. The research and development of lead-free ferroelectric ceramics for this kind of detector has become a hot research spot in the areas of dielectric physics and materials in recent years. In this article, the recent research progress of the pyroelectric effect in series of important lead-free ferroelectric ceramic systems is reviewed, including barium titanate, sodium bismuth titanate, potassium sodium niobite, barium strontium niobite, etc. The methods of enhancing the pyroelectric effect are summarized, including doping modification, phase boundary design, process improvement, etc. Through comparative analysis of the relationship between pyroelectric properties and depolarization temperatures of different systems, it is concluded that bismuth sodium titanate based ceramics are the most potential lead-free materials in the future. The prospective research work of lead-free ferroelectric ceramics for infrared detection is also suggested.

Keywords:

Authors and contacts

1.
Key Laboratory of Inorganic Functional Materials and Devices, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2.
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
3.
State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Corresponding author: Wang Gen-Shui, genshuiwang@mail.sic.ac.cn ; Dong Xian-Lin, xldong@mail.sic.ac.cn

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References

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Cited By

图 1 铁电材料中的热释电效应起源示意图

Figure 1. Schematic illustration of the pyroelectric effect in ferroelectric materials.

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图 2 (a) BZT-BCT相图; (b) 0.5 Ba(Zr_0.2Ti_0.8)O₃-0.5(Ba_0.7Ca_0.3)TiO₃热释电系数温谱^[40,42]

Figure 2. (a) Phase diagram of the BZT-BCT system; (b) the pyroelectric coefficient of the 0.5Ba(Zr_0.2Ti_0.8)O₃-0.5(Ba_0.7Ca_0.3)TiO₃ ceramics^[40,42].

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图 3 钛酸铋钠BNT无铅铁电材料的相结构演变过程

Figure 3. Phase transitions of BNT lead-free material from low temperature to high temperature.

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图 4 BNT-BT固溶体组分温度相图^[50]

Figure 4. Phase diagram of BNT-BT solid solution^[50].

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图 5 0.98BNT-0.02BA-xNN陶瓷在20—80 ℃范围内的热释电性能　(a)电流响应优值F_i; (b)电压响应优值F_v; (c)探测率优值F_d; (d) 1 kHz下的介电温谱^[66]

Figure 5. Pyroelectric figure of merits (a) F_i, (b) F_v, (c) F_d and (d) dielectric constant as a function of temperature within 20—80 ℃ of 0.98BNT-0.02BA-xNN ceramics^[66].

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图 6 Sr/Ba比(30/70—50/50)对SBN铁电陶瓷电性能的影响规律　(a)介电温谱; (b)居里温度; (c)电滞回线; (d)热释电系数温谱^[71]

Figure 6. (a) Dielectric constant, (b) Curie temperature, (c) P-E hysteresis loops, and (d) pyroelectric constant as a function of temperature for SBN ceramics with different Sr/Ba ratio (30/70−50/50)^[71].

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图 7 (K_0.5Na_0.5)_2x(Sr_0.6Ba_0.4)_5–x Nb₁₀O₃₀ (KNSBN)陶瓷　(a)介电温谱; (b)热释电系数温谱^[76]

Figure 7. The dependence of (a) dielectric constant and (b) pyroelectric coefficient on temperature of (K_0.5Na_0.5)_2x(Sr_0.6Ba_0.4)_5–x Nb₁₀O₃₀ (KNSBN) ceramics^[76].

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图 8 CaNb₂O₆-SrNb₂O₆-BaNb₂O₆准三元系相图, 其中灰色区域为CSBN单相稳定存在的区域^[79]

Figure 8. Phase diagram of CaNb₂O₆-SrNb₂O₆-BaNb₂O₆ ternary system. The grayish area marks the stability field of CSBN^[79].

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图 9 Ca_x(Sr_0.5Ba_0.5)_1–x Nb₂O₆ (x = 0, 0.10, 0.15, 0.20)无铅铁电陶瓷热释电性能　(a) 电流响应优值F_i; (b) 电压响应优值F_v; (c) 探测率优值F_d; (d) 热释电系数^[80]

Figure 9. Pyroelectric figures of merits (a) F_i, (b) F_v, (c) F_d, and (d) pyroelectric coefficient as a function of temperature for Ca_x(Sr_0.5Ba_0.5)_1–x Nb₂O₆ (x = 0, 0.10, 0.15, 0.20) ceramics^[80].

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图 10 Ca_x Sr_0.3–x Ba_0.7Nb₂O₆陶瓷热释电及退极化性能　(a) 热释电系数; (b)退极化性能(以样品高温退火后d_33T与完全极化d_33RT比值表示)^[82]

Figure 10. (a) Pyroelectric coefficient as a function of temperature of CSBN (x) ceramics; (b) the ratio of piezoelectric constant measured at different temperatures (d_33T) to room temperature piezoelectric constant (d_33RT) of ceramics and commercially PZT ceramics. The inset shows the depoling results for CSBN (x).

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图 11 (a) Sr_0.63Ba_0.37Nb₂O₆陶瓷普通烧结与热锻烧结的介电温谱与损耗温谱; (b) Sr_0.63Ba_0.37Nb₂O₆陶瓷热锻样品的室温电滞回线; (c) Sr_0.53Ba_0.47Nb₂O₆和Sr_0.63Ba_0.37Nb₂O₆陶瓷热锻样品热释电系数温谱; (d) Sr_0.53Ba_0.47Nb₂O₆和Sr_0.63Ba_0.37Nb₂O₆陶瓷热锻样品电流响应优值温谱^[84]

Figure 11. (a) Dielectric constant and loss as a function of temperature for the Sr_0.63Ba_0.37Nb₂O₆ ordinary sintering (O.S) and hot forging (H.F) ceramics (1. H.F∥; 2. O.S; 3. H.F⊥); (b) hysteresis loops for the Sr_0.63Ba_0.37Nb₂O₆ H.F ceramics at room temperature and 50 Hz; (c) pyroelectric coefficient as a function of temperature for SBN textured ceramics; (d) figure of merit F_i as a function of temperature for SBN textured ceramics^[84].

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图 12 不同体系铁电陶瓷的热释电系数与退极化温度关系图

Figure 12. Comparison of pyroelectric coefficient and depoling temperature between lead-free and lead-based ferroelectric ceramics.

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图 13 不同体系铁电陶瓷的电压响应优值与退极化温度的关系图

Figure 13. Comparison of pyroelectric figure of merit F_v and depoling temperature between lead-free and lead-based ferroelectric ceramics.

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表 1 BT基无铅铁电陶瓷的热释电性能列表

Table 1. Pyroelectric properties of BT-based lead-free ferroelectric ceramics.

材料组成	热释电系数/ 10^–4 C·m^–2·K^–1	介电常数	介电损耗	居里温度/℃	F_i/pm·V^–1	F_v/m²·C^–1	F_d/µPa^–1/2	文献
BaTiO₃	2.00	1200		120	80	0.0080	4.20	[28]
Ba_0.95Ca_0.05TiO₃	～2.00			113				[29]
Ba_0.90Sr_0.10TiO₃	4.70	1088	0.016	108		0.0173		[30]
Ba_0.80Sr_0.20TiO₃	4.20	1419	0.018	77		0.0118		[30]
BaSn_0.05Ti_0.95O₃	4.32	2520	0.029	77	228	0.0100	8.20	[35]
Porous BaSn_0.05Ti_0.95O₃	5.57	2180	0.035	/	355	0.01800	22.00	[35]
BaZr_0.025Ti_0.975O₃	7.50			105				[36]
BaCe_0.10Ti_0.90O₃	7.82			83	339	0.0110	10.39	[37]
0.5Ba(Zr_0.2Ti_0.8)O₃-0.5(Ba_0.7Ca_0.3)TiO₃	5.84			93				[32]
(Ba_0.85Ca_0.15)(Zr_0.1Ti_0.9)O₃-1 wt%Li	8.60	2590	0.033	79	407.6	0.0150	15.80	[43]
(Ba_0.85Sr_0.15)(Zr_0.1Ti_0.9)O₃	14.00	4691	0.041	46	600	0.0150	14.50	[45]
(Ba_0.84Ca_0.15Sr_0.01)(Zr_0.09Ti_0.9Sn_0.01)O₃	11.70	4200	0.020	83	479	0.0130	18.10	[44]
Modified PZT	3.80	290	0.003	230	152	0.0600	58.00	[15]
Modified PT	3.80	220	0.011	255	152	0.0800	33.00	[15]
PMN-PZT	3.56	218	0.007	226	142	0.0741	59.30	[12]

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表 2 BNT基无铅铁电陶瓷的热释电性能列表

Table 2. Pyroelectric properties of BNT-based lead-free ferroelectric ceramics.

材料组成	热释电系数/10^–4 C·m^–2·K^–1	介电常数	介电损耗	居里温度/℃	退极化温度/℃	F_i/pm·V^–1	F_v/m²·C^–1	F_d/µPa^–1/2	文献
(Bi_0.5Na_0.5)TiO₃	2.50			320	200				[49]
0.94BNT-0.06BT	3.15	396	0.0436		115	112	0.0210	9.080	[50]
0.94(Bi_0.52Na_0.52)TiO₃-0.06BT	6.99				55	250	0.0470	16.630	[50]
0.94BNT-0.06BT-0.005La+0.002Ta	12.92	671	0.0472		40	461	0.0780	2.760	[54]
0.94BNT-0.06BT-0.005La	7.42				69	265	0.0480	1.400	[52]
0.94BNT-0.06Ba_1.02TiO₃	3.54				85	124	0.0095	8.300	[51]
0.80BNT-0.20BT	2.42				209		0.0268	15.300	[55]
0.93BNT-0.07Ba(Zr_0.055Ti_0.945)O₃	5.70				87	203	0.0220	10.500	[56]
0.93BNT-0.07Ba(Zr_0.055Ti_0.945)O₃-0.00125Mn	6.10			～300	72	217	0.0230	12.600	[58]
0.94BNT-0.06Ba(Zr_0.25Ti_0.75)O₃	27.20	1462	0.0460	300	38		0.0750		[57]
0.95(0.95BNT-0.05BKT)-0.05BT	3.25	853	0.0278			1945	0.0260	13.430	[52]
0.95(0.94BNT-0.016BLT-0.05BKT)-0.05BT	3.60	858	0.0294			221	0.0290	14.750	[52]
0.82BNT-0.18BKT-0.008Mn	17.00	605	0.0160	～350	～150			65.600	[53]
0.88BNT-0.084BKT-0.036BT	3.66	933	0.0235	301	165	215	0.0260	15.408	[61]
0.98BNT-0.02BA	3.87	330	0.0110	～300	190	138	0.0471	23.300	[66]
0.98(0.98BNT-0.02BA)-0.02NN	7.48	372	0.0110	～300	155	266	0.0807	42.200	[66]
0.97(0.99BNT-0.01BA)-0.03KNN	3.70	512	0.0290	282	118	132	0.0289	11.500	[67]
0.98(0.98BNT-0.02BA)-0.02KNN	8.42	880	0.0400	～280		303	0.0390	17.200	[68]
0.715BNT-0.22ST-0.065BT-0.4 wt%glass	6.80	734	0.1430	157	/		0.0370	8.850	[65]
0.98BNT-0.02BN	4.42	465	0.0080		195	171	0.0382	27.400	[64]
0.97BNT-0.03BNN	5.60	549	0.0090		143	217	0.041	30.100	[64]

DownLoad: CSV

表 4 KNN基铁电陶瓷的热释电性能列表

Table 4. Pyroelectric properties of KNN-based lead-free ferroelectric ceramics.

材料组成	热释电系数/ 10^–4 C·m^–2·K^–1	介电常数	介电损耗	居里温度/℃	退极化温度/℃	F_i/pm·V^–1	F_v/m²·C^–1	F_d/µPa^–1/2	文献
KNN	1.40	472		410					[92]
0.97KNN-0.03BKT+0.8 wt%MnO	2.21	1277	0.031	～350		90.07	0.0080	4.81	[93]
0.97KNN-0.03BKT+2 wt%MnO	2.18	980	0.035	～350		99.4	0.0114	5.71	[93]
0.96(K_0.5N_0.5)(Nb_0.8Ta_0.2)O₃-0.04Li(Nb_0.8Ta_0.2)O₃	1.65	1230	0.018			123.5	0.0110	8.82	[62]
0.96(K_0.5N_0.5)(Nb_0.84Ta_0.1Sb_0.06)O₃-0.04Li(Nb_0.84Ta_0.1Sb_0.06)O₃	1.90	1520	0.018			93.1	0.0070	5.98	[62]
0.95(K_0.45Na_0.55) NbO₃-0.05LiSbO₃	15.00	891			35				[94]
NaNbO₃-0.01MnO-0.005Bi₂O₃	1.85				270	67	0.0333	53.20	[96]
0.85NaNbO₃-0.15Ba_0.6(Bi_0.5Na_0.5)_0.4TiO₃	3.11	1151	0.016		110	104	0.0102	8.10	[95]
0.95AgNbO₃-0.05LiTaO₃	3.68	252	0.022		130	138	0.0602	19.70	[97]

DownLoad: CSV

表 3 SBN基无铅铁电陶瓷的热释电性能列表

Table 3. Pyroelectric properties of SBN-based lead-free ferroelectric ceramics.

材料组成	热释电系数 /10^–4C·m^–2·K^–1	介电常数	介电损耗	居里温度/℃	F_i/pm·V^–1	F_v/m²·C^–1	F_d/µPa^–1/2	文献
Sr_0.5Ba_0.5Nb₂O₆	2.00			84				[71]
Gd_0.01Sr_0.515Ba_0.47Nb₂O₆	2.85	2480		149			4.5	[74]
(K_0.5Na_0.5)_2.3(Sr_0.6Ba_0.4)_3.85Nb₁₀O₃₀	2.11	～1600		227			14.1	[76]
Ca_0.15(Sr_0.5Ba_0.5)_0.85Nb₂O₆	3.61	933	0.0270	～90	172	0.0210	11.5	[80]
Sr_0.525Ca_0.125Ba_0.35Nb₂O₆	2.37			～50				[81]
Ca_0.2Sr_0.1Ba_0.7Nb₂O₆	1.24			217	60	0.0203	6.1	[82]
Sr_0.53Ba_0.47Nb₂O₆ H.F(⊥)	5.10	980	0.0180	～105	230	0.0281	18.7	[84]
Sr_0.53Ba_0.47Nb₂O₆ H.F(//)	4.00	468	0.0050	～115	189	0.0456	40.6	[84]
Sr_0.53Ba_0.47Nb₂O₆ TGG(⊥)	2.90	770	0.0360	148				[86]
Sr_0.3Ba_0.7Nb₂O₆ O.F	0.71	491	0.0469	163	34	0.0078	2.4	[90]
Sr_0.3Ba_0.7Nb₂O₆ H.P(200 MPa⊥)	2.38	676	0.0534	163	113	0.0189	6.3	[90]

DownLoad: CSV

表 5 BLSF铁电陶瓷的热释电性能列表

Table 5. Pyroelectric properties of KNN-based lead-free ferroelectric ceramics.

材料组成	热释电系数 /10^–4 C·m^–2·K^–1	介电常数	介电损耗	居里温度/℃	F_i/pm·V^–1	F_v/m²·C^–1	F_d/µPa^–1/2	文献
(NaBi)Bi₄Ti₄O₁₅+1 wt%MnCO₃(O.F)	0.560	140	0.0029	658	18.70	0.015	9.88	[102]
(NaBi)Bi₄Ti₄O₁₅+1 wt%MnCO₃(H.F)	1.300	149	0.0032	660	43.50	0.033	21.1	[102]
(NaBi)_0.95Ca_0.05Bi₄Ti₄O₁₅+1 wt%MnCO₃(O.F)	0.820	148	0.0016	680	29.10	0.027	63.5	[102]
(NaBi)_0.95Ca_0.05Bi₄Ti₄O₁₅+1 wt%MnCO₃(H.F)	1.000	134	0.0017	665	35.20	0.032	78.4	[102]
Sr_1.1Bi_3.9Ti_3.9Ta_0.1O₁₅+0.5 wt%MnCO₃	1.300	190	0.0010	～520		0.030	40.0	[100]
CaBi₄Ti₄O₁₅	0.359	145	0.0080	790	14.74	0.012	4.6	[99]
CaBi₄Ti_3.95Nb_0.05O₁₅	0.440	136	0.0060	790	18.07	0.015	6.7	[99]
CaBi₄Ti₄O₁₅+0.2 wt%MnO₂	0.582	130	0.0050	790	23.90	0.021	10.0	[99]
CaBi₄Ti_3.95Nb_0.05O₁₅+0.2 wt%MnO₂	0.844	99	0.0020	790	34.65	0.040	24.4	[99]
Bi₄Ti_2.9W_0.1O₁₂-0.04%Mn	0.571	147	0.0030	655				[101]

DownLoad: CSV

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Vol. 69, Issue 12 - 2020-06-20

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