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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

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

    图 2  (a) BZT-BCT相图; (b) 0.5 Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)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(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 ceramics[40,42].

    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.

    图 4  BNT-BT固溶体组分温度相图[50]

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

    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Fi; (b)电压响应优值Fv; (c)探测率优值Fd; (d) 1 kHz下的介电温谱[66]

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

    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].

    图 7  (K0.5Na0.5)2x(Sr0.6Ba0.4)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 (K0.5Na0.5)2x(Sr0.6Ba0.4)5–x Nb10O30 (KNSBN) ceramics[76].

    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].

    图 9  Cax(Sr0.5Ba0.5)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Fi; (b) 电压响应优值Fv; (c) 探测率优值Fd; (d) 热释电系数[80]

    Figure 9.  Pyroelectric figures of merits (a) Fi, (b) Fv, (c) Fd, and (d) pyroelectric coefficient as a function of temperature for Cax(Sr0.5Ba0.5)1–x Nb2O6 (x = 0, 0.10, 0.15, 0.20) ceramics[80].

    图 10  Cax Sr0.3–x Ba0.7Nb2O6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d33T与完全极化d33RT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 (d33T) to room temperature piezoelectric constant (d33RT) of ceramics and commercially PZT ceramics. The inset shows the depoling results for CSBN (x).

    图 11  (a) Sr0.63Ba0.37Nb2O6陶瓷普通烧结与热锻烧结的介电温谱与损耗温谱; (b) Sr0.63Ba0.37Nb2O6陶瓷热锻样品的室温电滞回线; (c) Sr0.53Ba0.47Nb2O6和Sr0.63Ba0.37Nb2O6陶瓷热锻样品热释电系数温谱; (d) Sr0.53Ba0.47Nb2O6和Sr0.63Ba0.37Nb2O6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 Sr0.63Ba0.37Nb2O6 ordinary sintering (O.S) and hot forging (H.F) ceramics (1. H.F∥; 2. O.S; 3. H.F⊥); (b) hysteresis loops for the Sr0.63Ba0.37Nb2O6 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 Fi as a function of temperature for SBN textured ceramics[84].

    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.

    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 Fv and depoling temperature between lead-free and lead-based ferroelectric ceramics.

    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/℃
    Fi/pm·V–1Fv/m2·C–1Fd/µPa–1/2文献
    BaTiO32.001200120800.00804.20[28]
    Ba0.95Ca0.05TiO3~2.00113[29]
    Ba0.90Sr0.10TiO34.7010880.0161080.0173[30]
    Ba0.80Sr0.20TiO34.2014190.018770.0118[30]
    BaSn0.05Ti0.95O34.3225200.029772280.01008.20[35]
    Porous BaSn0.05Ti0.95O35.5721800.035/3550.0180022.00[35]
    BaZr0.025Ti0.975O37.50105[36]
    BaCe0.10Ti0.90O37.82833390.011010.39[37]
    0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO35.8493[32]
    (Ba0.85Ca0.15)(Zr0.1Ti0.9)O3-1 wt%Li8.6025900.03379407.60.015015.80[43]
    (Ba0.85Sr0.15)(Zr0.1Ti0.9)O314.0046910.041466000.015014.50[45]
    (Ba0.84Ca0.15Sr0.01)(Zr0.09Ti0.9Sn0.01)O311.7042000.020834790.013018.10[44]
    Modified PZT3.802900.0032301520.060058.00[15]
    Modified PT3.802200.0112551520.080033.00[15]
    PMN-PZT3.562180.0072261420.074159.30[12]
    DownLoad: CSV

    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/℃
    Fi/pm·V–1Fv/m2·C–1Fd/µPa–1/2文献
    (Bi0.5Na0.5)TiO32.50320200[49]
    0.94BNT-0.06BT3.153960.04361151120.02109.080[50]
    0.94(Bi0.52Na0.52)TiO3-0.06BT6.99552500.047016.630[50]
    0.94BNT-0.06BT-0.005La+0.002Ta12.926710.0472404610.07802.760[54]
    0.94BNT-0.06BT-0.005La7.42692650.04801.400[52]
    0.94BNT-0.06Ba1.02TiO33.54851240.00958.300[51]
    0.80BNT-0.20BT2.422090.026815.300[55]
    0.93BNT-0.07Ba(Zr0.055Ti0.945)O35.70872030.022010.500[56]
    0.93BNT-0.07Ba(Zr0.055Ti0.945)O3-0.00125Mn6.10~300722170.023012.600[58]
    0.94BNT-0.06Ba(Zr0.25Ti0.75)O327.2014620.0460300380.0750[57]
    0.95(0.95BNT-0.05BKT)-0.05BT3.258530.027819450.026013.430[52]
    0.95(0.94BNT-0.016BLT-0.05BKT)-0.05BT3.608580.02942210.029014.750[52]
    0.82BNT-0.18BKT-0.008Mn17.006050.0160~350~15065.600[53]
    0.88BNT-0.084BKT-0.036BT3.669330.02353011652150.026015.408[61]
    0.98BNT-0.02BA3.873300.0110~3001901380.047123.300[66]
    0.98(0.98BNT-0.02BA)-0.02NN7.483720.0110~3001552660.080742.200[66]
    0.97(0.99BNT-0.01BA)-0.03KNN3.705120.02902821181320.028911.500[67]
    0.98(0.98BNT-0.02BA)-0.02KNN8.428800.0400~2803030.039017.200[68]
    0.715BNT-0.22ST-0.065BT-0.4 wt%glass6.807340.1430157/0.03708.850[65]
    0.98BNT-0.02BN4.424650.00801951710.038227.400[64]
    0.97BNT-0.03BNN5.605490.00901432170.04130.100[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/℃
    Fi/pm·V–1Fv/m2·C–1Fd/µPa–1/2文献
    KNN1.40472410[92]
    0.97KNN-0.03BKT+0.8 wt%MnO2.2112770.031~35090.070.00804.81[93]
    0.97KNN-0.03BKT+2 wt%MnO2.189800.035~35099.40.01145.71[93]
    0.96(K0.5N0.5)(Nb0.8Ta0.2)O3-0.04Li(Nb0.8Ta0.2)O31.6512300.018123.50.01108.82[62]
    0.96(K0.5N0.5)(Nb0.84Ta0.1Sb0.06)O3-0.04Li(Nb0.84Ta0.1Sb0.06)O31.9015200.01893.10.00705.98[62]
    0.95(K0.45Na0.55) NbO3-0.05LiSbO315.0089135[94]
    NaNbO3-0.01MnO-0.005Bi2O31.85270670.033353.20[96]
    0.85NaNbO3-0.15Ba0.6(Bi0.5Na0.5)0.4TiO33.1111510.0161101040.01028.10[95]
    0.95AgNbO3-0.05LiTaO33.682520.0221301380.060219.70[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/℃
    Fi/pm·V–1Fv/m2·C–1Fd/µPa–1/2文献
    Sr0.5Ba0.5Nb2O62.0084[71]
    Gd0.01Sr0.515Ba0.47Nb2O62.8524801494.5[74]
    (K0.5Na0.5)2.3(Sr0.6Ba0.4)3.85Nb10O302.11~160022714.1[76]
    Ca0.15(Sr0.5Ba0.5)0.85Nb2O63.619330.0270~901720.021011.5[80]
    Sr0.525Ca0.125Ba0.35Nb2O62.37~50[81]
    Ca0.2Sr0.1Ba0.7Nb2O61.24217600.02036.1[82]
    Sr0.53Ba0.47Nb2O6 H.F(⊥)5.109800.0180~1052300.028118.7[84]
    Sr0.53Ba0.47Nb2O6 H.F(//)4.004680.0050~1151890.045640.6[84]
    Sr0.53Ba0.47Nb2O6 TGG(⊥)2.907700.0360148[86]
    Sr0.3Ba0.7Nb2O6 O.F0.714910.0469163340.00782.4[90]
    Sr0.3Ba0.7Nb2O6 H.P(200 MPa⊥)2.386760.05341631130.01896.3[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/℃
    Fi/pm·V–1Fv/m2·C–1Fd/µPa–1/2文献
    (NaBi)Bi4Ti4O15+1 wt%MnCO3(O.F)0.5601400.002965818.700.0159.88[102]
    (NaBi)Bi4Ti4O15+1 wt%MnCO3(H.F)1.3001490.003266043.500.03321.1[102]
    (NaBi)0.95Ca0.05Bi4Ti4O15+1 wt%MnCO3(O.F)0.8201480.001668029.100.02763.5[102]
    (NaBi)0.95Ca0.05Bi4Ti4O15+1 wt%MnCO3(H.F)1.0001340.001766535.200.03278.4[102]
    Sr1.1Bi3.9Ti3.9Ta0.1O15+0.5 wt%MnCO31.3001900.0010~5200.03040.0[100]
    CaBi4Ti4O150.3591450.008079014.740.0124.6[99]
    CaBi4Ti3.95Nb0.05O150.4401360.006079018.070.0156.7[99]
    CaBi4Ti4O15+0.2 wt%MnO20.5821300.005079023.900.02110.0[99]
    CaBi4Ti3.95Nb0.05O15+0.2 wt%MnO20.844990.002079034.650.04024.4[99]
    Bi4Ti2.9W0.1O12-0.04%Mn0.5711470.0030655[101]
    DownLoad: CSV
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Metrics
  • Abstract views:  15868
  • PDF Downloads:  433
  • Cited By: 0
Publishing process
  • Received Date:  27 February 2020
  • Accepted Date:  14 April 2020
  • Published Online:  20 June 2020

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