CN116425552B - 一种氮化铝基板及其制备方法与应用 - Google Patents
一种氮化铝基板及其制备方法与应用 Download PDFInfo
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 title claims abstract description 131
- 239000000758 substrate Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 38
- 238000005245 sintering Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 26
- 150000004767 nitrides Chemical class 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 16
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 69
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- 238000000498 ball milling Methods 0.000 claims description 18
- 229910052582 BN Inorganic materials 0.000 claims description 11
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 235000015895 biscuits Nutrition 0.000 claims description 8
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- 238000002156 mixing Methods 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000919 ceramic Substances 0.000 abstract description 38
- 230000008569 process Effects 0.000 abstract description 20
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- 238000002485 combustion reaction Methods 0.000 description 8
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 238000004100 electronic packaging Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
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- 238000005054 agglomeration Methods 0.000 description 1
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- 125000003158 alcohol group Chemical group 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
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- 238000010924 continuous production Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
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- 238000010304 firing Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
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- 230000007704 transition Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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Abstract
本发明属于氮化物陶瓷制备技术领域,具体公开一种氮化铝基板及其制备方法与应用。本发明通过在氮化铝生坯表面涂覆或喷涂隔粘粉的方式,在基础隔粘的前提下,能够在氮化铝生坯片排胶或低温烧结过程中制造还原性环境,降低氮化铝基板中的氧杂质及第二相的含量,提高其导热率及强度。本发明的氮化铝基板的热导率在205W/(m·k)以上,强度在400MPa以上。
Description
技术领域
本发明涉及氮化物陶瓷制备技术领域,尤其是一种氮化铝基板及其制备方法与应用。
背景技术
氮化铝陶瓷具有高热导、高电阻、高击穿场强、低介电损耗、低膨胀、优异的耐热震性及良好的力学性能等特性,被认为是高集成度半导体基片和电子器件的理想封装材料。随着电子封装产品的应用领域越来越广泛,其应用环境越来越复杂,对氮化铝陶瓷的导热性和强度要求随之增高,因此,制备一种高综合性能的氮化铝陶瓷基板的需求显得十分迫切。
氮化铝陶瓷的热传导可以看作连续性的非谐振弹性波通过声子或热能与声子相互作用的量子来传播。因此,声子的散射是影响氮化铝陶瓷热导率的重要因素。固溶于氮化铝陶瓷中的氧元素形成的铝空位及氮化铝陶瓷中气孔均会降低声子平均自由程,进而降低其热导率。因此,氮化铝的理论热导率可达320W/(m·k),然而实际氮化铝陶瓷产品的热导率还不到200W/(m·k)。
现有方式主要是通过稀土金属氧化物、碱土金属氧化物等烧结助剂排除气孔,促进烧结,并通过与晶格中的氧反应生成第二相,净化晶格,提升热导率。而烧结助剂在烧结过程完成后可能挥发完全、残留于晶界或固溶于晶粒内部。当添加烧结助剂较少时,氮化铝陶瓷难以烧结;当烧结助剂过量时,产生的过量玻璃相会对致密化过程产生阻碍作用,且大量液相聚集在晶界之间形成浓密的“厚膜”,抑制晶界传质过程,并降低氮化铝陶瓷强度。在烧结后期,烧结助剂挥发不完全,部分玻璃相会固溶在氮化铝晶格内,甚至产生杂相破坏晶格完整性,降低热导率。因此,减少氮化铝中的氧杂质及第二相的含量对于开发高导热高强度氮化铝陶瓷基板是十分重要的。
发明内容
针对上述现有技术涉及的氮化铝中的氧杂质及第二相的含量降低氮化铝陶瓷的导热率的问题,本发明将提供一种氮化铝基板及其制备方法与应用。
为实现上述目的,具体包括以下技术方案:
一种氮化铝基板的制备方法,包括如下步骤:
(1)将氮化铝和烧结助剂经过混合、脱泡、陈腐、流延、冲压成型,得到氮化铝素坯片;
(2)将所述氮化铝素坯片表面涂覆或喷涂隔粘粉,然后进行叠片;所述隔粘粉为质量百分比为10-20%的无机碳粉和质量百分比为80-90%的氮化物的混合物,所述无机碳粉包括石墨粉、炭黑中的至少一种,所述氮化物为氮化铝或氮化硼中的至少一种,所述无机碳粉的平均粒径小于氮化物的平均粒径;
(3)将步骤(2)叠片后的氮化铝素坯片在空气气氛下进行排胶,得到生坯料;
(4)将所述生坯料置于氮气气氛下进行烧结,经除粉、表面研磨后得到氮化铝基板。
本发明通过在氮化铝生坯表面涂覆或喷涂隔粘粉方式,在基础隔粘的前提下,能够在氮化铝生坯片排胶或低温烧结过程中制造还原性环境,抑制空气中的氧分子进入到氮化铝中进而解决叠烧工艺中生坯中的氧原子进入AlN晶格产生Al空位,进而降低AlN陶瓷基板热导率及第二相含量偏高导致强度偏低的技术问题。
可能涉及的反应式如下:
(1)Al2O3+N2+3CO→2AlN+3CO2;
(2)CO2+C→2CO;
烧结助剂中存在Y2O3和YF2时还可涉及下述反应式:
(3)Al2Y4O9+N2+3CO=2AlN+2Y2O3+3CO2;
(4)Y2O3+N2+3CO→2YN+3CO2;
作为本发明优选的实施方式,步骤(1)中,所述烧结助剂包括质量百分比为2-7%的Y2O3和质量百分比为0-4%的YF2。
作为本发明优选的实施方式,步骤(1)中,所述氮化铝的平均粒径为0.75~1.4μm,比表面积为1.80~2.85m2/g,氧浓度为0.2~0.7wt%,杂质元素含量范围为300~500ppm。
作为本发明优选的实施方式,步骤(1)中,所述混合的方式为球磨,所述球磨的时间为1-2h,所述球磨的转速为200-300r/min,所述球磨气氛为惰性气体,所述球磨介质包括酒精、异丙醇中的至少一种,球磨内外衬材料为聚乙烯,磨球材质为氧化铝。
作为本发明优选的实施方式,步骤(1)中,所述冲压成型的压力为80-200MPa。
作为本发明优选的实施方式,步骤(2)中,所述无机碳粉的质量百分比为15-18%。
作为本发明优选的实施方式,所述无机碳粉的燃烧温度大于450℃,如石墨粉、炭黑中至少一种。
无机碳粉没有到达燃烧温度的时候,无机碳粉是稳定存在的,达到其燃烧温度后,无机碳粉被氧化,生成二氧化碳。当碳粉被氧化时会生成二氧化碳,重量会在相应的温度发生变化,所以燃烧温度可以通过TG/DSC测试进行确定。
无机碳粉的燃烧温度高于450℃,其燃烧温度高于排胶温度点,如此可以避免涂覆或喷涂在生坯表面的无机碳源在空气氛围的排胶过程中发生燃烧,进而无机碳源可以有效地去除基板烧结过程中的氧杂质及二次相。燃烧温度与无机碳源的自身性质有关,所以我们选择燃烧温度大于450℃的石墨和/或炭黑作为隔粘粉中的无机碳源。
作为本发明优选的实施方式,步骤(2)中,所述无机碳粉的平均粒径为10~25μm。
作为本发明进一步优选的实施方式,步骤(2)中,所述无机碳粉的平均粒径为13~20μm。
作为本发明优选的实施方式,步骤(2)中,所述氮化物的质量百分比为82-85%。
作为本发明优选的实施方式,步骤(2)中,所述氮化物的平均粒径为30~80μm。
作为本发明进一步优选的实施方式,步骤(2)中,所述氮化物的平均粒径为40~65μm。
由于无机碳粉在高温条件下存在氧化反应,在高温烧结完成后,隔粘粉中防止叠烧片间相互粘连的主要是大颗粒的氮化物粉,若涂覆或喷涂前所制隔粘粉中无机碳粉较氮化物粉的粒径大或相等时,则烧结后的氮化铝基板麻坑严重,无法满足氮化铝陶瓷基板的使用要求,故采用小颗粒的无机碳粉与大颗粒的氮化物粉进行颗粒级配,能够使得小颗粒的无机碳粉均匀分布在大颗粒的氮化物粉间的间隙。
当无机碳粉的粒径过大时,要求氮化物粉的粒径会更大,因此小颗粒的无机碳粉在发生氧化反应后会使氮化物粉间的间隙过大,进而造成烧结后的氮化铝陶瓷基板表面粗糙度高,无法满足其使用要求;当无机碳粉粒径过小时,由于粒径越小越容易团聚,因此在涂覆或喷涂粉时会造成局部颗粒偏大,进而也容易导致氮化铝基板表面粗糙度高,且小粒径的无机碳粉会完全堵塞氮化物粉间的间隙,抑制叠烧工艺中氮化铝生坯片的排胶。因此,选择上述粒径的范围,能够减少大颗粒球形氮化物粉相互接触导致的氮化铝陶瓷表面凹凸,进而提升氮化铝陶瓷基板的表面粗糙度,氮化铝陶瓷基板性能更优。
当无机碳粉的添加量过多时,由于温度是由四周向中心传导,因此涂覆或喷涂在氮化铝素坯表面四周的无机碳粉会优先发生氧化反应,致使氮化铝生坯在烧结过程中四周与中心的温度存在差异,导致氮化铝生坯收缩差异明显,从而发生明显的边缘翘曲或形变,致使氮化铝陶瓷基板局部受力,强度偏低;当无机碳粉的添加量过少时,碳氧结合不够,导致氮化铝陶瓷基板中的氧杂质含量,使氮化铝陶瓷基板中存在YAG相,且YAG杂质相的含量高,导致氮化铝基板陶瓷导热低,强度低。因此,选择上述的含量范围,氮化铝陶瓷基板性能更优。
氮化铝粉烧结活性低,不同粒径的氮化铝粉比表面积存在差异,比表面积不同烧结活性不同,粒径越大,比表越小,烧结活性越低,因此,可以选用粒径较大的氮化铝粉成为氮化铝基板叠烧工艺的隔粘粉;氮化硼粉热稳定性好,在氮化铝陶瓷基板的烧结过程中不会发生反应,所以选择氮化铝或氮化硼粉都可以起到有效的作用。
作为本发明优选的实施方式,所述无机碳粉与所述烧结助剂的质量比为(1-2):(3-4)。
作为本发明进一步优选的实施方式,所述无机碳粉与所述烧结助剂的质量比为(1.3-1.7):(3.5-3.8)。
无机碳粉比例偏低,烧结后的氮化铝基板中的氧杂质及YAG相含量高,对氮化铝基板的导热和强度无明显改善作用;无机碳粉比例过高,由于温度是由四周向中心传导,因此涂覆或喷涂在氮化铝素坯表面四周的无机碳粉会优先发生氧化反应,致使氮化铝生坯在烧结过程中四周与中心的温度存在差异,导致氮化铝生坯收缩差异明显,从而发生明显的边缘翘曲或形变,致使氮化铝陶瓷基板局部受力,强度偏低。因此,选择上述的范围,氮化铝陶瓷基板性能更优。
作为本发明优选的实施方式,步骤(3)中,所述排胶的温度为400-550℃,所述排胶的时间为4-9h。
作为本发明优选的实施方式,步骤(4)中,所述烧结的温度为1700-1850℃,所述烧结的时间为5-12h。
本发明所述氮化铝基板可在制备半导体基片和电子器件封装材料中的应用,其具有高导热、高弯曲强度的特点。
相对于现有技术,本发明具有以下有益效果:
(1)氮化铝表面涂覆或喷涂无机碳粉与氮化物混合的隔粘粉,能够在氮化铝生坯片排胶或低温烧结过程中制造还原性环境,抑制空气中的氧分子进入到氮化铝中,且能够有效避免向氮化铝基板生产的原料中引入其他杂质元素,工艺简单,有利于工业连续化生产
(2)氮化铝表面涂覆或喷涂无机碳粉与氮化物混合的隔粘粉,通过C-O间的亲合力(Al2O3+3C+N2=2AlN+3CO),减少AlN中的氧杂质含量,通过减少铝空位的形成以提升氮化铝陶瓷基板的导热性;
(3)氮化铝表面涂覆或喷涂石墨粉与氮化物混合的隔粘粉,能够通过以下化学反应减少或消除晶界的第二相,有助于进一步提升氮化铝陶瓷基板的导热性和强度。
(4)本发明制得是一种高导热和高强度的氮化铝基板,其热导率在205W/(m·k)以上,弯曲强度在400MPa以上。
具体实施方式
为更好地说明本发明的目的、技术方案和优点,下面将通过具体实施例对本发明作进一步说明。
下述实施例和对比例所涉及的原料皆可从市场购买得到或通过自制得到。
实施例1-19和对比例1-13
(1)将平均粒径为1μm、比表面积为2m2/g、氧浓度为1.8wt%和杂质元素含量为600ppm的93wt%AlN粉体、5wt%的Y2O3、2wt%的YF2,进行称量混合后,经过球磨、脱泡、陈腐、流延、冲压成型后制备得到一定尺寸的氮化铝素坯片;所述球磨的时间为1h,球磨的转速为200r/min,球磨气氛为氮气,球磨介质为酒精,球磨内外衬材料为聚乙烯,磨球材质为氧化铝,冲压成型压力为100MPa;
(2)将步骤(1)中得到的氮化铝生坯片的表面喷涂按表1中的配方混合得到的隔粘粉,然后以10片/叠进行正反叠片,且对应的无机碳粉与步骤(1)中混合助烧剂的含量比例详见表1。
(3)将步骤(2)制备的氮化铝生坯片在空气气氛下经400℃排胶5h,排胶完成后在氮气气氛的常压条件下1800℃进行烧结,保温10h。
(4)将烧结后的氮化铝陶瓷基片进行除粉,表面研磨,得到氮化铝基板。
表1实施例和对比例的原料配方
注:无机碳粉质量百分比+氮化物的质量百分比=100wt%,所以表1中只列出无机碳粉质量百分含量,其中实施例2、6、10、14、17的氮化物选择氮化铝,其余均为氮化硼。
基板的测试方法
1、粗糙度:
测试仪器:粗糙度仪,测量范围-200μm~160μm,测量误差≤3%;
测试方法:将每组试验烧结后的氮化铝基板各取5片,测量时单片放置在平面上,每片各取边缘4点及中间1点直接用仪器进行测量,以每组的平均值作为该试验组的粗糙度值。
2、热导率:
测试仪器:Hot Disk热常数分析仪TPS2500S型;
测试方法:瞬变平面热源法,瞬变平面热源法测定材料热物性的原理是基于无限大介质中跃迁加热的圆盘形热源产生的瞬态温度相应。利用电阻性材料做成一个平面的探头,同时作为热源和温度传感器。镍的热阻系数—温度和电阻的关系呈线性关系,即通过了解电阻的变化可以知道热量的损失,从而反映物体的导热性能。
3、弯曲强度测试方法:
测试仪器:万能材料试验机INSTRON;
测试方法:弯曲强度:三点抗弯测试,跨距30mm,加载速率0.05mm/min,测试样品尺寸:40*24mm。
表2实施例和对比例制得的氮化铝陶瓷基板的性能数据
由上述的实施例和对比例,可以得到如下内容:
(1)由实施例1、7-9和对比例4可知,当无机碳粉的平均粒径大于25μm时,要求氮化铝或氮化硼粉的粒径会更大,因此小颗粒的无机碳粉在发生氧化反应后会使氮化铝或氮化硼粉间的间隙过大,进而造成烧结后的氮化铝陶瓷基板表面粗糙度达到0.635μm,粗糙度极值达到了14.331μm,无法满足氮化铝基板表面平整度使用要求(Ra<0.4μm);
(2)由实施例1、7-9和对比例3可知,当无机碳粉粒径小于10μm时,无机碳存在团聚颗粒,导致氮化铝基板表面粗糙度达到了0.551μm,粗糙度极值,达到了11.095μm,且小粒径的无机碳粉会完全堵塞氮化铝或氮化硼粉间的间隙,抑制叠烧工艺中氮化铝生坯片的排胶,对氮化铝基板的导热性及强度无改善作用;
(3)由实施例1、2-5和对比例2可知,当无机碳粉的添加量过多时,由于温度是由四周向中心传导,因此涂覆或喷涂在氮化铝素坯表面四周的无机碳粉会优先发生氧化反应,致使氮化铝生坯在烧结过程中四周与中心的温度存在差异,导致氮化铝生坯收缩差异明显,基板存在明显的边缘翘曲或形变现象,致使氮化铝陶瓷基板局部受力,强度偏低,低于强度要求值400MPa;
(4)由实施例1、2-5和对比例1可知,当无机碳粉的添加量过少时,碳氧结合不够,导致氮化铝陶瓷基板中的氧杂质含量,使氮化铝陶瓷基板中存在YAG相,且YAG杂质相的含量高,导致氮化铝基板陶瓷导热低,热导率在170W/(m·k)左右,强度低于要求值400MPa;
(5)由实施例1和对比例7可知,选用燃烧温度点低(300~400℃)的活性炭,致使涂覆或喷涂在氮化铝基板表面的活性炭在生坯排胶过程发生燃烧排除,对氮化铝基板烧结过程的氧杂质排除及二次相的析出无明显效果,热导率低于170W/(m·k),抗折强度低于400MPa;
(6)实施例1、10-13和对比例5可知,当与无机碳源混合的氮化铝或氮化硼粉粒径小于30μm时,氮化铝或氮化硼粉间的间隙变小,在相同的排胶工艺下,素坯内部的残胶量高,烧结后的氮化铝基板存在YAG相,且氮化铝基板存在翘曲变形,致使热导率低于170W/(m·k),强度低于要求值400MPa;
(7)实施例1、10-13和对比例6可知,当与无机碳源混合的氮化铝或氮化硼粉粒径大于80μm时,氮化铝表面的粗糙度为0.738μm,无法满足氮化铝基板表面平整度的使用要求;
(8)由实施例1、15-19和对比例8、10、12可知,当无机碳源与助溶剂的比例偏低时,碳的添加量过低,致使烧结后的氮化铝基板中存在YAG玻璃相,热导率在170W/(m·k)左右,强度低于要求值400MPa;
(9)由实施例1、15-19和对比例9、11、13可知,当无机碳源与助溶剂的比例偏高时,碳的添加量相对较高,有助于析出氮化铝基板内部的氧杂质和第二相,使氮化铝基板的热导率高于200W/(m·k),但烧结后的产品存在翘曲变形,致使氮化铝基板的强度低于400MPa。
最后所应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (8)
1.一种氮化铝基板的制备方法,其特征在于,包括如下步骤:
(1)将氮化铝和烧结助剂经过混合、脱泡、陈腐、流延、冲压成型,得到氮化铝素坯片;
(2)将所述氮化铝素坯片表面涂覆或喷涂隔粘粉,然后进行叠片;所述隔粘粉为质量百分比为10-20%的无机碳粉和质量百分比为80-90%的氮化物的混合物,所述无机碳粉包括石墨粉、炭黑中的至少一种,所述氮化物为氮化铝、氮化硼中的至少一种,所述无机碳粉的平均粒径小于氮化物的平均粒径;所述无机碳粉的平均粒径为10~25μm;所述氮化物的平均粒径为30~80μm;所述无机碳粉与所述烧结助剂的质量比为(1-2):(3-4);
(3)将步骤(2)叠片后的氮化铝素坯片在空气气氛下进行排胶,得到生坯料;
(4)将所述生坯料置于氮气气氛下进行烧结,经除粉、表面研磨后得到氮化铝基板。
2.如权利要求1所述的氮化铝基板的制备方法,其特征在于,步骤(2)中,所述无机碳粉的平均粒径为13~20μm;步骤(2)中,所述氮化物的平均粒径为40~65μm。
3.如权利要求1所述的氮化铝基板的制备方法,其特征在于,所述无机碳粉与所述烧结助剂的质量比为(1.3-1.7):(3.5-3.8)。
4.如权利要求1所述的氮化铝基板的制备方法,其特征在于,步骤(3)中,所述排胶的温度为400-550℃,所述排胶的时间为4-9h;步骤(4)中,所述烧结的温度为1700-1850℃,所述烧结的时间为5-12h。
5.如权利要求1所述的氮化铝基板的制备方法,其特征在于,步骤(1)中,所述氮化铝的质量百分比为89-98%,所述烧结助剂包括质量百分比为2-7%的Y2O3和质量百分比为0-4%的YF2;步骤(2)中,所述无机碳粉的质量百分比为15-18%;步骤(2)中,所述氮化物的质量百分比为82-85%。
6.如权利要求1所述的氮化铝基板的制备方法,其特征在于,步骤(1)中,所述氮化铝的平均粒径为0.75~1.4μm,比表面积为1.80~2.85m2/g,氧浓度为0.2~0.7wt%,杂质元素含量范围为300~500ppm;步骤(1)中,所述混合的方式为球磨,所述球磨的时间为1-2h,所述球磨的转速为200-300r/min,所述球磨气氛为惰性气体,所述球磨介质包括酒精、异丙醇中的至少一种;步骤(1)中,所述冲压成型的压力为80-200MPa。
7.一种权利要求1~6任一项所述的氮化铝基板的制备方法制得的氮化铝基板。
8.一种权利要求7所述的氮化铝基板在制备半导体基片和电子器件封装材料中的应用。
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Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4478785A (en) * | 1983-08-01 | 1984-10-23 | General Electric Company | Process of pressureless sintering to produce dense, high thermal conductivity aluminum nitride ceramic body |
US4578364A (en) * | 1984-12-07 | 1986-03-25 | General Electric Company | High thermal conductivity ceramic body of aluminum nitride |
JPH03146472A (ja) * | 1989-10-31 | 1991-06-21 | Asahi Glass Co Ltd | 窒化アルミニウム基板組成物 |
CN1242349A (zh) * | 1998-07-22 | 2000-01-26 | 住友电气工业株式会社 | 氮化铝烧结体及其制备方法 |
CN1403409A (zh) * | 2001-09-07 | 2003-03-19 | 北京航空材料研究院 | 一种制备氮化铝陶瓷基片的方法 |
CN101037333A (zh) * | 2007-02-13 | 2007-09-19 | 武汉理工大学 | 一种制备氮化铝/石墨叠层复合陶瓷材料的方法 |
CN104725050A (zh) * | 2015-04-20 | 2015-06-24 | 福建华清电子材料科技有限公司 | 一种采用自蔓延粉体制备高导热氮化铝陶瓷的方法 |
CN109987944A (zh) * | 2019-03-06 | 2019-07-09 | 清华大学 | 一种高导热氮化硅陶瓷基板及其制备方法 |
KR20200021023A (ko) * | 2018-08-17 | 2020-02-27 | (주) 존인피니티 | 180 W/mk 내지 230 W/mk의 열전도성을 갖는 질화알루미늄 기판의 제조방법 |
CN112811909A (zh) * | 2021-01-06 | 2021-05-18 | 北京科技大学 | 一种热压烧结制备高强度高热导率氮化铝的方法 |
WO2022135571A1 (zh) * | 2020-12-25 | 2022-06-30 | 中材高新氮化物陶瓷有限公司 | 一种高导热氮化硅陶瓷绝缘板及其制备方法 |
CN115304383A (zh) * | 2022-08-19 | 2022-11-08 | 广东省先进陶瓷材料科技有限公司 | 一种氮化铝基板及其制备方法与应用 |
-
2023
- 2023-04-24 CN CN202310447182.6A patent/CN116425552B/zh active Active
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4478785A (en) * | 1983-08-01 | 1984-10-23 | General Electric Company | Process of pressureless sintering to produce dense, high thermal conductivity aluminum nitride ceramic body |
US4578364A (en) * | 1984-12-07 | 1986-03-25 | General Electric Company | High thermal conductivity ceramic body of aluminum nitride |
JPH03146472A (ja) * | 1989-10-31 | 1991-06-21 | Asahi Glass Co Ltd | 窒化アルミニウム基板組成物 |
CN1242349A (zh) * | 1998-07-22 | 2000-01-26 | 住友电气工业株式会社 | 氮化铝烧结体及其制备方法 |
CN1403409A (zh) * | 2001-09-07 | 2003-03-19 | 北京航空材料研究院 | 一种制备氮化铝陶瓷基片的方法 |
CN101037333A (zh) * | 2007-02-13 | 2007-09-19 | 武汉理工大学 | 一种制备氮化铝/石墨叠层复合陶瓷材料的方法 |
CN104725050A (zh) * | 2015-04-20 | 2015-06-24 | 福建华清电子材料科技有限公司 | 一种采用自蔓延粉体制备高导热氮化铝陶瓷的方法 |
KR20200021023A (ko) * | 2018-08-17 | 2020-02-27 | (주) 존인피니티 | 180 W/mk 내지 230 W/mk의 열전도성을 갖는 질화알루미늄 기판의 제조방법 |
CN109987944A (zh) * | 2019-03-06 | 2019-07-09 | 清华大学 | 一种高导热氮化硅陶瓷基板及其制备方法 |
WO2022135571A1 (zh) * | 2020-12-25 | 2022-06-30 | 中材高新氮化物陶瓷有限公司 | 一种高导热氮化硅陶瓷绝缘板及其制备方法 |
CN112811909A (zh) * | 2021-01-06 | 2021-05-18 | 北京科技大学 | 一种热压烧结制备高强度高热导率氮化铝的方法 |
CN115304383A (zh) * | 2022-08-19 | 2022-11-08 | 广东省先进陶瓷材料科技有限公司 | 一种氮化铝基板及其制备方法与应用 |
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