CN101215157A - 掺氟硅铝玻璃基低温共烧陶瓷材料及其制备方法 - Google Patents
掺氟硅铝玻璃基低温共烧陶瓷材料及其制备方法 Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 10
- -1 Fluorine silicon aluminum Chemical compound 0.000 title claims description 16
- 238000000034 method Methods 0.000 title abstract description 8
- 239000011521 glass Substances 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 230000003750 conditioning effect Effects 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 7
- 238000010791 quenching Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 230000000171 quenching effect Effects 0.000 claims abstract description 3
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 6
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 5
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract description 29
- 239000000919 ceramic Substances 0.000 abstract description 7
- 238000002844 melting Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 230000008018 melting Effects 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000004377 microelectronic Methods 0.000 abstract description 2
- 239000005022 packaging material Substances 0.000 abstract description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 239000005354 aluminosilicate glass Substances 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 9
- 239000004332 silver Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000011812 mixed powder Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 5
- 238000013001 point bending Methods 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 2
- 239000006112 glass ceramic composition Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 239000004020 conductor Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 238000000280 densification Methods 0.000 description 1
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- 239000003989 dielectric material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
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Abstract
本发明涉及一种掺氟硅铝玻璃基低温共烧陶瓷材料及其制备方法。本发明是将20～80wt％的SiO2、10～50wt％的AlF3和0～30wt％的调节剂按比例混合后，加入乙醇，研磨后烘干，在1300～1400℃下熔制成液态玻璃，淬火、粉碎后过筛得到玻璃粉，加入乙醇或水，球磨24～48小时，干燥后得到该低温共烧陶瓷材料。本发明低温共烧陶瓷材料具有以下优点：(1)烧结温度低(750－850℃)，烧结收缩率可控；(2)介电常数在5～8(1MHz)之间可调，介电损耗在0.002以下；(3)机械强度高，制备工艺简单；(4)可以应用于陶瓷基板，谐振器等电子器件以及其他微电子封装材料领域。
Description
技术领域
本发明属于电子陶瓷材料领域，尤其涉及一种掺氟硅铝低温共烧玻璃陶瓷材料及其制备方法。
背景技术
近年来，在半导体技术飞速发展的带动下，电子元器件不断向小型化、集成化和高频化方向发展。选择适当的能与银等导电材料在不超过900℃的温度下低温共烧的陶瓷，从而制作多层元件或把无源器件埋入多层电路基板中，成为上述趋势的必然要求，作为无源集成元件主要介质材料的低温共烧陶瓷也因此成为一种重要的发展趋势。
目前，低温共烧陶瓷LTCC(Low Temperature Co-fired Ceramic)材料主要是将适量烧结助剂(低熔点氧化物或低熔点玻璃)引入介质陶瓷系统后，利用液相烧结机制促进材料的致密化。
例如，在BaO-TiO2-WO3体系中加入ZnO-B2O3-SiO2玻璃等可使烧结温度下降至1000℃(JP10294020-A)，在CaZrO3-SrTiO3体系中加入SiO2-B2O3体系玻璃可使烧结温度低1000℃，但烧结助剂降低烧结温度的能力是有限的，而且过量的烧结助剂还会影响器件的性能，如增大介电损耗等。为了获得烧结温度更低、介电性能更好控制的电子陶瓷材料，人们把注意力投向了易实现低温烧结的陶瓷材料体系上，如Bi-Zn-Nb-O体系 (FR2845685-A1)、Zr-Ti-Zn-O体系(US2003116891-A1，US6762142-B2)、ZnNb2O6和ZnTa2O6固溶体或MgNb2O6和MgTa2O6(US5756412-A，KR98001965-A；KR99008479-A；KR203515-B1)、Zn-Nb-O体系(JP7169330-A)、ZnTiO3(CN1773631，WO2005085154-A1)、(Ba1-xSrx)4LiNb3-yTayO12(CN1793004)、BaNd2+xTi5O14+1.5x(CN1634800)、Ba-Ti-Ge-Si(JP2000239061-A)、Li2+xNb3xTi1-4xO3(CN1821171和CN1915904)、Zn(1-x)Nb2O6-xTiO2(KR29499/98)、Bi(Nb1-xVx)O4(CN1793035)、Bi3XZn2(1-X)Nb2-XO7(CN1089247，CN1107128)、(Bi3xZn2-3x)(Znx-y/3Nb2-x-2y/3May)O7和(Bi3xZn2-3x)(ZnxNb2-x-yMby)O7，其中Ma＝Sn4+、Zr4+，Mb＝Sb5+、Ta5+、Mo5+(CN1431166)、(Bi3xM2-3x)(ZnxNb2-x)O7，其中，M为Zn2+，Ca2+，或Cd2+，或Sr2+(CN1792999)等等。这些材料体系本身烧结温度低，一般在950～1150℃，掺入少量玻璃或低熔点的氧化物(如Bi2O3、ZnO、CuO、V2O5等)可实现900℃左右低温烧结。
但是，低熔点添加剂的引入可能带来一系列问题，如烧结后材料的机械强度降低、介电损耗较高，以及工艺方面的复杂性等。因此，发展具有简单组分的低温共烧陶瓷材料是非常必要的。
发明内容
本发明的目的是提供一种烧结温度低，介电常数可控，介电损耗低，机械强度高的LTCC材料及其制备方法。
本发明所提供的一种掺氟硅铝玻璃基低温共烧陶瓷材料，各组分及其含量百分比为：
SiO2： 20～80wt％
AlF3： 10～50wt％
金属氟化物或氧化物调节剂：0～30wt％。
其中，所述的调节剂选自BaF2、CaF2、CaO、MgO、Al2O3、MgF2、LiF、或NaF中的一种或多种。
本发明所提供的掺氟硅铝玻璃基低温共烧陶瓷材料的制备方法，包括以下步骤：
1)将分析纯的AlF3·3H2O于NH4F的保护气氛下，在450～550℃煅烧1～2小时，得到无水AlF3；
2)将步骤1)制备的无水AlF3与SiO2和调节剂按配比混合后，加入混合物重量1.5～2.5倍的乙醇，研磨后烘干，再重新研磨成细粉后在1300～1400℃下熔制成液态玻璃，淬火、粉碎后过80目筛得到玻璃粉，加入玻璃粉重量1.5～2.5倍的乙醇或水，球磨24～48小时，干燥后得到掺氟硅铝玻璃基低温共烧陶瓷材料。
本发明所制备的低温共烧玻璃陶瓷材料使用方便，向其中添加适量粘结剂后经干压或冷等静压制成坯片，在750～850℃空气环境下烧成，保温2～4小时即可使用。
本发明通过改变体系的成分配比，来改善和控制材料的烧结收缩率、介电常数、强度以及热膨胀系数等性能。本发明可以较好的实现LTCC工艺，该体系材料可用于LTCC基板材料或其他封装材料。
与现有技术相比较，本发明具有以下优点：
1)烧结温度低，通过改变体系中个成分的配比，烧结温度在750～850℃之间，无需保护气氛；
2)介电常数、烧结收缩率可控，介电损耗低，通过控制体系中成分的配比，控制烧结过程中结晶相的含量，从而控制烧结收缩率在10～20％之间变化，介电常数在5～8(1MHz)之间变化；并且改变体系的成分配比过程中，均可得到较低的介电损耗系数；
3)成本低，采用热处理后的AlF3·3H2O代替商业无水AlF3，极大的降低了生产成本，并且其它原料的成本也较低；
4)强度和热物理性能适当，三点弯曲强度在100～250MPa之间，并且热膨胀系数在5～9ppm/℃之间(20～200℃)，数值上较接近GaAs芯片的热膨胀系数；
5)制备工艺简单，采用传统的玻璃熔融方法和微晶玻璃制备方法，制得玻璃粉加入粘接剂后可直接烧结；
6)可以应用于LTCC基板材料，谐振器等电子器件以及其他微电子封装材料领域。
具体实施方式
实施例1
1)将AlF3·3H2O在NH4F保护气氛下在450℃煅烧1小时，去除结晶水，得到无水AlF3；
2)按下列成分配比称量各组分：
SiO2： 45g
AlF3： 36g
调节剂：MgF2 10g、CaF2 10g和LiF 5g
将上述混合粉料置于球磨罐中，加入约为混合物料总重量1.5倍的无水乙醇，球磨24小时后在烘箱(68℃)中烘干，将得到的混合粉体在1300℃下熔制成液态玻璃，淬火，干燥、粉碎后过80目筛；再将得到的玻璃粉置于球磨罐中，加入水(约为玻璃粉重量的2倍)，球磨24小时，干燥，得到掺氟硅铝玻璃基低温共烧陶瓷材料。
采用传统的陶瓷制备工艺，在步骤2)制备的低温共烧陶瓷材料中加入10％的聚乙烯醇PVA作为粘结剂，造粒后，按常规方法制成坯片，在800℃下烧结3小时，将烧结后的微晶玻璃片被银，烧银后进行性能测试，该组微晶玻璃的性能指标如下：
介电常数εr(1MHz)为7.0，介电损耗系数tanδ(1MHz)为0.0013，径向收缩率为15.2％，密度2.75g/cm3，热膨胀系数(20～200℃)为8.5ppm/℃，三点弯曲强度为212MPa。
实施例2
1)将AlF3·3H2O在NH4F保护气氛下在500℃煅烧1小时，去除结晶水，得到无水AlF3；
2)按下列成分配比称量各组分：
SiO2： 60g
AlF3： 15g
调节剂：BaF2 5g、CaF2 5g和MgO 10g
将上述混合粉料置于球磨罐中，加入无水乙醇(约为混合物料总重量的2倍)，球磨2 4小时后在烘箱中(68℃)烘干，将得到的混合粉体在1400℃下熔制成液态玻璃，淬火，干燥、粉碎后过80目筛；再将得到的玻璃粉于球磨罐中，加入水(约为玻璃粉重量的1.5倍)，球磨48小时，干燥，得到掺氟硅铝玻璃基低温共烧陶瓷材料。
采用传统的陶瓷制备工艺，在上述掺氟硅铝玻璃基低温共烧陶瓷材料中加入10％的PVA作为粘结剂，造粒后，按常规方法制成坯片，在850℃下烧结2小时，将烧结后的微晶玻璃片被银，烧银后进行性能测试，该组微晶玻璃的性能指标如下：
介电常数εr(1MHz)为6.5，介电损耗系数tanδ(1MHz)为0.0007，径向收缩率为14.0％，密度2.68g/cm3，热膨胀系数TCE为8.3ppm/℃(20～200℃)，三点弯曲强度为174MPa。
实施例3
1)将AlF3·3H2O在NH4F保护气氛下在550℃煅烧2小时，去除结晶水，得到无水AlF3；
2)按下列成分配比称量各组分：
SiO2： 50g
AlF3： 40g
调节剂 MgF2 10g、CaO 3g和NaF 2g
将上述混合粉料置于球磨罐中，加入无水乙醇(约为混合物料总重量的2.5倍)，球磨2 4小时后在烘箱中(68℃)烘干，将得到的混合粉体在1350℃下熔制成液态玻璃，淬火，干燥、粉碎后过80目筛；再将得到的玻璃粉于球磨罐中，加入水(约为玻璃粉重量的2.5倍)，球磨40小时，干燥，得到掺氟硅铝玻璃基低温共烧陶瓷材料。
采用传统的陶瓷制备工艺，在上述掺氟硅铝玻璃基低温共烧陶瓷材料中加入10％的PVA作为粘结剂，造粒后，按常规方法制成坯片，在825℃下烧结4小时，将烧结后的微晶玻璃片被银，烧银后进行性能测试，该组微晶玻璃的性能指标如下：
介电常数εr(1MHz)为5.8，介电损耗系数tanδ(1MHz)为0.0014，径向收缩率为17.0％，密度2.60g/cm3，热膨胀系数TCE为6.0ppm/℃(20～200℃)，三点弯曲强度为150MPa。
实施例4
1)先将AlF3·3H2O在NH4F保护气氛下在500℃煅烧1.5小时去除结晶水，得到无水AlF3；
2)按下列成分配比称量各组分：
SiO2： 40g
AlF3： 40g
调节剂：BaF2 20g和CaF2 5g
将上述混合粉料置于球磨罐中，加入无水乙醇(约为混合物料总重量的2倍)，球磨24小时后在烘箱中(68℃)烘干，将得到的混合粉体在1350℃下熔制成液态玻璃，淬火，干燥、粉碎后过80目筛；再将得到的玻璃粉于球磨罐中，加入水(约为玻璃粉重量的1.5倍)，球磨48小时，干燥，得到掺氟硅铝玻璃基低温共烧陶瓷材料。
采用传统的陶瓷制备工艺，在上述掺氟硅铝玻璃基低温共烧陶瓷材料中加入10％的PVA作为粘结剂，造粒后，按常规方法制成坯片，在750℃下烧结3小时，将烧结后的微晶玻璃片被银，烧银后进行性能测试，该组微晶玻璃的性能指标如下：
介电常数εr(1MHz)为7.3，介电损耗系数tanδ(1MHz)为0.0008，径向收缩率为15.0％，密度2.80g/cm3，热膨胀系数TCE为7.55ppm/℃(20～100℃)，三点弯曲强度为226MPa。
Claims (3)
1.一种掺氟硅铝玻璃基低温共烧陶瓷材料，其特征在于，各组分及其质量百分比为：
SiO2： 20～80wt％
AlF3： 10～50wt％
金属氟化物或氧化物调节剂：0～30wt％。
2.根据权利要求1所述的低温共烧陶瓷材料，其特征在于，所述的调节剂选自BaF2、CaF2、CaO、MgO、Al2O3、MgF2、LiF或NaF中的一种或多种。
3.根据权利要求1或2所述的掺氟硅铝玻璃基低温共烧陶瓷材料的制备方法，其特征在于，包括以下步骤：
1)将分析纯的AlF3·3H2O于NH4F的保护气氛下，在450～550℃煅烧1～2小时，得到无水AlF3；
2)将步骤1)制备的无水AlF3与SiO2和调节剂按配比混合后，加入混合物重量1.5～2.5倍量的乙醇，研磨后烘干，再重新研磨成细粉后在1300～1400℃下熔制成液态玻璃，淬火、粉碎后过80目筛得到玻璃粉，加入玻璃粉重量1.5～2.5倍量的乙醇或水，球磨24～48小时，干燥后得到掺氟硅铝玻璃基低温共烧陶瓷材料。
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| CN2008801222420A CN101952221A (zh) | 2008-01-11 | 2008-11-04 | 低温共烧陶瓷粉及其专用原料与应用 |
| JP2010541676A JP5073064B2 (ja) | 2008-01-11 | 2008-11-04 | 低温同時焼成セラミック粉末及び特別な原料、並びにその使用 |
| US12/679,007 US8298971B2 (en) | 2008-01-11 | 2008-11-04 | Low temperature co-fired ceramic powder and special raw material and use thereof |
| PCT/CN2008/001842 WO2009086724A1 (zh) | 2008-01-11 | 2008-11-04 | 低温共烧陶瓷粉及其专用原料与应用 |
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- 2008-11-04 WO PCT/CN2008/001842 patent/WO2009086724A1/zh active Application Filing
- 2008-11-04 US US12/679,007 patent/US8298971B2/en not_active Expired - Fee Related
- 2008-11-04 CN CN2008801222420A patent/CN101952221A/zh active Pending
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| CN114163242B (zh) * | 2021-12-30 | 2022-11-18 | 杭州电子科技大学 | 一种低介电常数高品质因数的微波介质陶瓷及其制备方法 |
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| CN115124331A (zh) * | 2022-06-21 | 2022-09-30 | 电子科技大学 | 一种高导热高膨胀低温共烧陶瓷材料及其制备方法 |
| CN115124329A (zh) * | 2022-06-27 | 2022-09-30 | 清华大学深圳国际研究生院 | 一种ltcc基板及其制备方法 |
| CN115124329B (zh) * | 2022-06-27 | 2023-08-08 | 清华大学深圳国际研究生院 | 一种ltcc基板及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011509232A (ja) | 2011-03-24 |
| JP5073064B2 (ja) | 2012-11-14 |
| US8298971B2 (en) | 2012-10-30 |
| CN101215157B (zh) | 2011-08-17 |
| WO2009086724A1 (zh) | 2009-07-16 |
| CN101952221A (zh) | 2011-01-19 |
| US20100210446A1 (en) | 2010-08-19 |
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