| 121 | 0 | 25 |
| 下载次数 | 被引频次 | 阅读次数 |
氮化铝(AlN)陶瓷因其具有优异的导热性、电绝缘性以及良好的机械性能，在电子封装、基板、散热等领域具有广阔的应用前景。然而，AlN固有的强共价键、低扩散性等使其难以致密化烧结，严重制约了其性能发挥与应用。添加烧结助剂是克服这一瓶颈、实现高性能AlN陶瓷制备的最有效途径之一。本文从烧结助剂的种类出发，主要梳理了近年来不同种类烧结助剂在优化AlN陶瓷性能方面的研究，分析其作用机理和对AlN陶瓷性能的影响，并对未来AlN陶瓷烧结助剂的研究进行了展望。
Abstract：Aluminum nitride(AlN) ceramics have excellent thermal conductivity,good electrical insulation properties,thermal expansion coefficient matching with silicon materials,and high mechanical strength.AlN ceramics show a wide application potential in high-tech fields such as electronic packaging,circuit substrates,and heat dissipation components.Especially with the rapid development of microelectronic technology to high power and high density integration,AlN ceramics have attracted great attention as an ideal heat dissipation and packaging material.However,AlN as a covalent bond compound,its inherent strong covalent bond,low diffusivity and high melting point make it difficult to achieve densification under conventional sintering conditions,thus restricting the optimization of its micro structure and the improvement of its performance,as well as its application in a wider range of fields.To overcome this bottleneck,the introduction of sintering aids becomes one of the most feasible and effective ways to achieve high density and high performance AlN ceramics.In recent years,researchers have extensively explored different types of sintering aid systems,including oxides,fluorides,composite additives,and other types of sintering aids.Their effects on the sintering behavior,microstructure and properties of AlN ceramics are investigated,obtaining the remarkable results.In this review,the sintering aids are divided into oxide sintering aids,fluoride sintering aids,composite sintering aids and other types of sintering aids according to the chemical composition.According to the different types of sintering aids,the performance optimization mechanism of AlN ceramics is analyzed.Rare-earth oxides(such as Y_2O3,CeO2,etc.) are the most widely used sintering aids.They can react with the inherent Al_2O3 oxide layer on the surface of AlN particles to form rare-earth aluminate liquid phase.The liquid phase has a low viscosity and a good wettability at high temperatures,which can promote the rearrangement of AlN particles.The oxygen impurities in the AlN lattice are effectively fixed at the grain boundary in the form of grain boundary phase.The degree of oxygen solid solution in the AlN lattice is significantly reduced,and the phonon scattering in the lattice is reduced.The unique advantage of fluoride sintering aids(such as CaF2,YF3,etc.) is that they can form eutectic liquid phase or react with Al_2O3 on the surface of AlN to form volatile fluorine-containing substances during sintering,thus promoting the rearrangement of AlN particles and filling the pores to achieve densification.There is no second phase residue at the grain boundary of AlN after sintering.The composite sintering additives can often reduce the lattice oxygen content through the synergistic effect of each component,i.e.,one of which focuses on removing oxygen impurities and the another focuses on forming an effective liquid phase at a lower temperature to promote densification.AlN ceramics can form a liquid phase,which is more conducive to sintering at a lower temperature,and achieve more fine regulation of grain microstructure.Other types of sintering aids are mainly represented by carbides or rare-earth hydrides,which also promote densification via forming a low melting point liquid phase,and remove oxygen impurities from the AlN lattice and fix them to the grain boundaries through chemical reactions.The mechanical and thermal properties of AlN ceramics are improved to achieve the purpose of obtaining AlN ceramics with a high strength and a high thermal conductivity.Summary and Prospects The comparison of the effect of different sintering aids on the properties of aluminum nitride ceramics indicates that the oxide sintering aid has the most significant effect on the improvement of thermal conductivity and the most mature application technology.However,the sintering temperature required is relatively high,and the second phase of grain boundary generates,affecting the high-temperature performance.It is more suitable for high performance electronic packaging substrate materials.Fluoride sintering aids can significantly reduce the sintering temperature and directly deoxygenate through gas phase volatilization.There is no residual second phase in the grain boundary,but the high temperature volatiles will corrode the sintering equipment,and the sintering process is difficult to control,which is not suitable for industrial production.The composite sintering aid can further reduce the sintering temperature or optimize the grain boundary phase through the synergistic effect,but the formula design is more complicated,and the mechanism of action still needs to be further explored,which is suitable for the pursuit of extreme performance or specific functions.The application cost of other sintering aids is low,but the research is less,the universality is low,and it is still in the experimental research stage.In the future,advanced characterization techniques can be used to reveal the mechanism of sintering additives,the migration path of oxygen impurities and the dynamic evolution process of grain boundary phase in the sintering process,which can provide a theoretical support for the design of sintering additive system.Nano-or submicron-sized sintering aids are obtained via optimizing the preparation process of sintering aids.Therefore,the utilization efficiency of sintering aids is improved,which is helpful to achieve densification at a lower addition amount.In addition,it can also be devoted to the development of new sintering additives,such as low rare-earth,no rare-earth or no residual sintering additive system,which can effectively reduce the residual impurities at the grain boundary and purify the grain boundary structure.A new type of nitrogen oxide grain boundary phase is constructed via accurately controlling the sintering atmosphere and the proportion of elements in the sintering aid.It can react with Al_2O3 to form a rare-earth aluminum nitrogen oxide with a higher thermal conductivity and a better electrical insulation or JEM phase and other crystalline phases to replace the low thermal conductivity aluminate glass phase.
[1]RADHIKA E, THATIKONDA S K, CHILAKA R R, et al. Comparison of the effect of conventional and microwave sintering on structural and dielectric properties of Al N–CaZrO3 and Y2O3 composite ceramics[J].Ceram Int, 2025, 51(1):1002–1016.
[2]CAO Y, XU H X, ZHAN J, et al. Experimental and modeling studies on the microstructures and properties of oxidized aluminum nitride ceramic substrates[J]. J Mater Eng Perform, 2018, 27(7):3297–3303.
[3]KAYA P, SUYOLCU Y E, VAN AKEN P A, et al. Grain boundary blocking effects in Sm/Yb-doped Al N ceramics[J]. J Eur Ceram Soc,2021, 41(9):4870–4875.
[4]SHANG Q S, WANG Z J, LI J, et al. Gel-tape-casting of aluminum nitride ceramics[J]. J Adv Ceram, 2017, 6(1):67–72.
[5]LIANG D Y, LI X Q, YIN W L, et al. Synergistic enhancement of thermal conductivity, dielectric properties, and flexural strength in AlN ceramics via Y2O3–LiF sintering and annealing[J]. J Eur Ceram Soc,2026, 46(3):117895.
[6]张明华,蒋明学,肖国庆.关于Al N陶瓷导热性的讨论[J].陶瓷,1997(2):41–44.ZHANG Minghua, JIANG Mingxue, XIAO Guoqing. Ceramics,1997(2):41–44.
[7]JIANG H, HUO X Y, WANG X H, et al. Effect of YF3 on densification behavior and thermal conductivity of Al N ceramics with Y2O3–YF3additives under reducing atmosphere[J]. Ceram Int, 2023, 49(20):32929–32935.
[8]CHOI H S, IM H N, KIM Y M, et al. Structural, thermal and mechanical properties of aluminum nitride ceramics with CeO2 as a sintering aid[J]. Ceram Int, 2016, 42(10):11519–11524.
[9]PENG H, WEI L J, LIU Y, et al. Effect of Si3N4 doping and annealing on the thermal conductivity and mechanical properties of Al N ceramics[J]. J Aust Ceram Soc, 2025, 61(4):1487–1502.
[10]LEE S H, TANAKA H, AOYAGI T. Densification of AlN using boron and carbon additives[J]. J Eur Ceram Soc, 2009, 29(10):2021–2027.
[11]QIU J Y, HOTTA Y, WATARI K, et al. Low-temperature sintering behavior of the nano-sized AlN powder achieved by super-fine grinding mill with Y2O3 and CaO additives[J]. J Eur Ceram Soc, 2006, 26(4–5):385–390.
[12]LI M J, WANG C Y, WANG G Q, et al. Improvement of AlN thermal conductivity based on reductive compound additives[J]. J Wuhan Univ Technol Mater Sci Ed, 2023, 38(5):1025–1033.
[13]翁履谦,黄栋生,韩斌,等.添加Y2O3的AlN陶瓷材料的烧结过程[J].硅酸盐通报, 1996, 15(5):36–39.WENG Lüqian, HUANG Dongsheng, HAN Bin, et al. Bull Chin Ceram Soc, 1996, 15(5):36–39.
[14]FU L, QIAO L, ZHENG J W, et al. Phase, microstructure and sintering of aluminum nitride powder by the carbothermal reduction-nitridation process with Y2O3 addition[J]. J Eur Ceram Soc, 2018, 38(4):1170–1178.
[15]PEZZOTTI G, NAKAHIRA A, TAJIKA M. Effect of extended annealing cycles on the thermal conductivity of AlN/Y2O3 ceramics[J].J Eur Ceram Soc, 2000, 20(9):1319–1325.
[16]LI Q G, WANG Z, WU C, et al. Microstructure and mechanical properties of aluminum nitride Co-doped with cerium oxide via hot-pressing sintering[J]. J Alloys Compd, 2015, 640:275–279.
[17]QIAO L, ZHOU H P, LI C W. Microstructure and thermal conductivity of spark plasma sintering Al N ceramics[J]. Mater Sci Eng B, 2003,99(1–3):102–105.
[18]HUANG D, TIAN Z B, CUI W, et al. Effects of Y2O3 and yttrium aluminates as sintering additives on the thermal conductivity of Al N ceramic substrates[J]. Ceram Int, 2018, 44(16):20556–20559.
[19]CHEN Z Q, WANG L, DU P P, et al. Effects of different sintering additives Re2O3(Re=Y, Nd, Gd, Sm, and Yb)on the thermal conductivity, mechanical properties and dielectric properties of Al N ceramics[J]. J Alloys Compd, 2025, 1023:180180.
[20]MOLISANI A L, YOSHIMURA H N, GOLDENSTEIN H. Sintering mechanisms in aluminum nitride with Y or Ca-containing additive[J]. J Mater Sci Mater Electron, 2009, 20(1):1–8.
[21]MOLISANI A L, GOLDENSTEIN H, YOSHIMURA H N. The role of CaO additive on sintering of aluminum nitride ceramics[J]. Ceram Int,2017, 43(18):16972–16979.
[22]LUO Q, LI C H, ZHOU N Y, et al. Electrical properties, microstructure,and thermal conductivity of hot-pressed CaO-doped Al N ceramics[J].Ceram Int, 2024, 50(9):14200–14208.
[23]WANG M C, YANG C C, WU N C. Grain growth and electric properties of liquid phase sintered Al N ceramics with CaCN2additives[J]. Mater Sci Eng A, 2003, 343(1/2):97–106.
[24]QIAO L, ZHOU H P, FU R L. Thermal conductivity of AlN ceramics sintered with CaF2 and YF3[J]. Ceram Int, 2003, 29(8):893–896.
[25]XIONG Y, FU Z Y, WANG H, et al. Microstructure and IR transmittance of spark plasma sintering translucent Al N ceramics with CaF2 additive[J]. Mater Sci Eng B, 2005, 123(1):57–62.
[26]XIONG Y, WANG H, FU Z Y. Transient liquid-phase sintering of AlN ceramics with CaF2 additive[J]. J Eur Ceram Soc, 2013, 33(11):2199–2205.
[27]WANG T, XIE J J, CHEN C, et al. Fabrication translucent AlN ceramic under the strong magnetic field[J]. Opt Mater X, 2022, 14:100148.
[28]JARRIGE J, LECOMPTE J P, MULLOT J, et al. Effect of oxygen on the thermal conductivity of aluminium nitride ceramics[J]. J Eur Ceram Soc, 1997, 17(15/16):1891–1895.
[29]WANG D D, WANG C B, LI M J, et al. Effect of NH4F additive on purification of Al N ceramics[J]. J Mater Sci Mater Electron, 2017,28(9):6731–6736.
[30]SON H W, KIM B N, SUZUKI T S, et al. Fabrication of translucent Al N ceramics with Mg F2 additive by spark plasma sintering[J]. J Am Ceram Soc, 2018, 101(10):4430–4433.
[31]LIN K J, ZONG X, SHENG P F, et al. Effects of Sm F3 addition on aluminum nitride ceramics via pressureless sintering[J]. J Eur Ceram Soc, 2023, 43(15):6804–6814.
[32]KENFAUI D, GUILLEMET-FRITSCH S, VALDEZ-NAVA Z, et al.Tuning electrical conductivity in AlN-based ceramics by incorporating graphene[J]. J Eur Ceram Soc, 2023, 43(5):1887–1896.
[33]HE X L, YE F, ZHOU Z Q, et al. Thermal conductivity of spark plasma sintered AlN ceramics with multiple components sintering additive[J]. J Alloys Compd, 2010, 496(1–2):413–417.
[34]LEE H M, KIM D K. High-strength AlN ceramics by low-temperature sintering with CaZrO3–Y2O3 co-additives[J]. J Eur Ceram Soc, 2014,34(15):3627–3633.
[35]ZHAN J, WU Y, ZHANG H, et al. Secondary phases, microstructures and properties of Al N ceramics sintered by adding nitrate sintering additives[J]. Adv Appl Ceram, 2015, 114(2):77–81.
[36]QIAO L, ZHOU H P, XUE H, et al. Effect of Y2O3 on low temperature sintering and thermal conductivity of AlN ceramics[J]. J Eur Ceram Soc,2003, 23(1):61–67.
[37]JIANG H, LU Y Y, DING L W, et al. Effects of Y2O3–LaF3 on the low temperature sintering and thermal conductivity of Al N ceramics[J].Microelectron Int, 2019, 36(1):22–25.
[38]LIU C, GUO W M, SUN S K, et al. Texture, microstructures, and mechanical properties of Al N-based ceramics with Si3N4–Y2O3additives[J]. J Am Ceram Soc, 2017, 100(8):3380–3384.
[39]LIN K J, NIE G L, SHENG P F, et al. Effects of doping Al-metal powder on thermal, mechanical and dielectric properties of Al N ceramics[J]. Ceram Int, 2022, 48(24):36210–36217.
[40]JIANG H, DING N, ZOU Z Y, et al. Investigation of thermal conductivity and dielectric properties of AlN-based ceramics with ZnO addition by impedance spectroscopy analysis[J]. J Asian Ceram Soc,2022, 10(2):489–497.
[41]QIAO L, ZHOU H P, CHEN K X, et al. Effects of Li2O on the low temperature sintering and thermal conductivity of AlN ceramics[J]. J Eur Ceram Soc, 2003, 23(9):1517–1524.
[42]KOBAYASHI R, NAKAJIMA Y, MOCHIZUKI K, et al. Densification of Al N ceramics by spark plasma sintering under 1550℃[J]. Adv Powder Technol, 2016, 27(3):860–863.
[43]MOLISANI A L, GOLDENSTEIN H, YOSHIMURA H N. Secondphase evolution and densification behavior of Al N with CaO–Y2O3–C multicomponent additive system[J]. Ceram Int, 2022, 48(5):6615–6626.
[44]ZHAN J, CAO Y, ZHANG H, et al. Low-temperature sintering of AlN ceramics by Sm2O3–Y2O3–CaO sintering additives formed via decomposition of nitrate solutions[J]. J Mater Eng Perform, 2017, 26(1):453–459.
[45]KIM J I, KIM J, LEE S M, et al. Low-temperature hot-press sintering of Al N ceramics with Mg O–CaO–Al2O3–SiO2 glass additives for ceramic heater applications[J]. Ceram Int, 2022, 48(18):26022–26027.
[46]BAEK S H, JEONG H, RYU S S. Al N with high strength and high thermal conductivity based on an MCAS–Y2O3–YSZ multi-additive system[J]. J Eur Ceram Soc, 2022, 42(3):898–904.
[47]JIANG H, CAI Q F, WANG X H, et al. Synergistic improvement of thermal conductivity and flexural strength of Al N ceramics with Si3N4–C additives[J]. Ceram Int, 2025, 51(24):42178–42185.
[48]WANG M C, HONG C K, TSAI M S, et al. Effect of CaCN2 addition on the densification behavior and electric properties of AlN ceramics[J].Jpn J Appl Phys, 2000, 39(10R):5953.
[49]WANG M C, YANG C C, WU N C. Densification and structural development in the sintering of AlN ceramics with CaCN2 additives[J].J Eur Ceram Soc, 2001, 21(12):2185–2192.
[50]KUROKAWA Y, UTSUMI K, TAKAMIZAWA H. Development and microstructural characterization of high-thermal-conductivity aluminum nitride ceramics[J]. J Am Ceram Soc, 1988, 71(7):588–594.
[51]LI X L, WANG L Y. The microstructure and thermal conductivity of aluminum nitride ceramics sintered at high pressure with CaC2[J]. Chin Phys Lett, 2012, 29(5):050703.
[52]WANG L, GUO W M, SHENG P F, et al. Effects of YH2 addition on pressureless sintered Al N ceramics[J]. J Eur Ceram Soc, 2023, 43(3):862–870.
[53]齐于杰,林坤吉,赵哲,等. Sm2O3-Sm F3烧结助剂对无压烧结Al N陶瓷性能的影响[J].热加工工艺, 2025, 54(13):93–98.QI Yujie, LIN Kunji, ZHAO Zhe, et al. Hot Work Technol, 2025, 54(13):93–98.
基本信息:
DOI：10.14062/j.issn.0454-5648.20250817
中图分类号:TQ174.1
引用信息:
[1]李圆梦,田晓,王群,等.烧结助剂对氮化铝陶瓷性能影响的研究进展[J].硅酸盐学报,2026,54(09):3254-3263.DOI:10.14062/j.issn.0454-5648.20250817.
基金信息:
内蒙古自治区自然科学基金（2024MS05017）
2025-11-07
2025
2026-08-05
2026-05-07
2026
1
2026-08-18
2026-08-18
2026-08-18