CN1476047A - γ－LiAlO2/α－Al2O3复合衬底材料的制备方法 - Google Patents

γ－LiAlO2/α－Al2O3复合衬底材料的制备方法 Download PDF

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CN1476047A
CN1476047A CNA031296025A CN03129602A CN1476047A CN 1476047 A CN1476047 A CN 1476047A CN A031296025 A CNA031296025 A CN A031296025A CN 03129602 A CN03129602 A CN 03129602A CN 1476047 A CN1476047 A CN 1476047A
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军 徐
徐军
王海丽
周圣明
杨卫桥
彭观良
周国清
蒋成勇
宋词
杭寅
司继良
赵广军
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Shanghai Institute of Optics and Fine Mechanics of CAS
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Abstract

一种γ－LiAlO2/α－Al2O3复合衬底材料的制备方法，包括如下具体步骤：在铂金坩埚内，放置有带气孔的LiAlO2和Li2O混合料块；将双面抛光或单面抛光的蓝宝石α－Al2O3晶片置于或悬于铂金丝上，加上覆盖有LiAlO2和Li2O混合粉料和热电偶的坩埚盖，坩埚顶部加铂金盖密闭，置于电阻炉中；该电阻炉加热升温至1000～1400℃左右，恒温20～100小时，Li2O扩散到α－Al2O3晶片中，降温后可得到LiAlO2/α－Al2O3复合衬底材料。本发明克服了α－Al2O3衬底晶格失配度大和难以获得大尺寸高质量LiAlO2单晶衬底等问题，可用于生长高质量InN－GaN薄膜外延生长。

Description

γ-LiAlO2/α-Al2O3复合衬底材料的制备方法
技术领域
本发明涉及一种γ-LiAlO2/α-Al2O3复合衬底材料的制备方法。γ-LiAlO2/α-Al2O3复合衬底材料主要用作InN-GaN基蓝光半导体外延生长。
背景技术
III族氮化物半导体材料InN-GaN具有优异的特性，如稳定的物理和化学性质、高热导和高电子饱和速度、直接带隙材料的光跃迁几率比间接带隙的高一个数量级，因此，宽带隙InN-GaN基半导体在短波长发光二极管、激光器和紫外探测器以及高温电子器件方面显示出广阔的应用前景。由于InN-GaN熔点比较高，N2饱和蒸汽压较大，InN-GaN体单晶制备十分困难，因此InN-GaN一般是在异质衬底上用外延技术生长的。
白宝石晶体(α-Al2O3)，易于制备，价格便宜，且具有良好的高温稳定性等特点，α-Al2O3是目前最常用的InN-GaN外延衬底材料(参见Jpn.J.Appl.Phys.，第36卷，1997年，第1568页)。
铝酸锂(γ-LiAlO2)是近几年才受到重视的InN-GaN外延衬底材料，由于其与GaN外延膜的晶格失配度相当小，只有1.4％，这使它成为一种相当理想的GaN外延衬底材料(参见美国专利USP6218280，KrylioukOlga，Anderson Tim，Chai Bruce，“Method and apparatus for producinggroup-III nitrides”)。
在先衬底(α-Al2O3和γ-LiAlO2)存在的显著缺点是：(1)用α-Al2O3作衬底，α-Al2O3和GaN之间的晶格失配度高达14％，使制备的GaN薄膜具有较高的位错密度和大量的点缺陷；(2)由于LiAlO2熔体在高温下容易发生非化学计量比挥发，晶体生长困难，难以获得大尺寸、高质量的LiAlO2单晶体，而且，衬底的加工过程造成了大量的原材料的浪费。
发明内容
本发明要解决的技术问题在于克服上述现有技术的不足，提供一种用于生长高质量InN-GaN薄膜外延生长的γ-LiAlO2/α-Al2O3复合衬底材料的制备方法。
本发明的复合衬底材料(γ-LiAlO2/α-Al2O3)的制备方法是利用气相传输平衡(Vapor Transport Equilibration，简称VTE)技术，在高温、富锂的气氛中，通过锂离子的扩散，使Li2O和α-Al2O3发生固相反应，制备具有γ-LiAlO2覆盖层的α-Al2O3复合衬底材料(γ-LiAlO2/α-Al2O3)。
本发明的γ-LiAlO2/α-Al2O3复合衬底材料的制备方法，包括具体工艺流程如下：
<1>在铂金坩埚内，放置有带气孔的LiAlO2和Li2O混合料块；
<2>将双面抛光或单面抛光的蓝宝石α-Al2O3晶片置于或悬于铂金丝上，加上覆盖有LiAlO2和Li2O混合粉料和热电偶的坩埚盖，坩埚顶部加铂金盖密闭，置于电阻炉中；
<3>该电阻炉加热升温至1000～1400℃左右，恒温20～100小时，Li2O扩散到α-Al2O3晶片中，降温后可得到LiAlO2/α-Al2O3复合衬底材料。
所述的LiAlO2和Li2O混合料块的重量比的选取范围是[LiAlO2]/[Li2O]＝(0～95)∶(100～5)。
所述的电阻炉也可用硅碳棒炉或硅钼棒炉代替。
本发明与在先衬底(α-Al2O3和γ-LiAlO2)相比，其优点是：克服了在先α-Al2O3衬底晶格失配度大和难以获得大尺寸高质量LiAlO2单晶衬底等问题，可用于生长高质量InN-GaN薄膜外延生长。
附图说明
图1是气相传输平衡实验装置示意图。
具体实施方式
本发明所用的气相传输平衡(VTE)技术制备复合衬底材料γ-LiAlO2/α-Al2O3的实验装置示意图见图1，铂金坩埚1内，放置有带气孔2的一定配比的LiAlO2和Li2O混合料块3，料块3上部是铂金丝4，双面抛光或单面抛光的蓝宝石α-Al2O3晶片5置于铂金丝4上，料块3上部有铂金片6和LiAlO2和Li2O混合粉料7覆盖，热电偶8插入粉料7中，坩埚1顶部加铂金盖9密闭。
气相传输平衡(VTE)技术是一种质量传输过程，因此坩埚内应保证有足够的Li2O供应量，其次，气相的平衡是依靠Li2O源源不断地从LiAlO2和Li2O混合料块中挥发来维持的，为防止混合料块表面Li2O耗尽造成的平衡破坏，应使混合料块具有多孔结构。以尽量增加Li2O的挥发表面。
白宝石(α-Al2O3)晶片置于或悬于密闭的铂金坩埚内，然后将密闭的铂金坩埚放入电炉(硅碳棒炉或硅钼棒炉)内，加热到预定的平衡温度，保温一定的时间进行气相平衡扩散，为了加快扩散过程和结构调整过程，应选取尽可能高的平衡温度，一般选取1000～1400℃。
本发明的气相传输平衡(VTE)技术制备复合衬底材料γ-LiAlO2/α-Al2O3的具体工艺流程如下：
<1>在铂金坩埚1内，放置有带气孔2的LiAlO2和Li2O混合料块3，选取[LiAlO2]/[Li2O]＝(0～95)∶(100～5)重量比。
<2>将双面抛光或单面抛光的蓝宝石α-Al2O3晶片，置于或悬于铂金丝上，加上覆盖有LiAlO2和Li2O混合粉料7和热电偶8的坩埚盖，坩埚顶部加铂金盖9密闭，置于电阻炉中。
<3>加热升温至1000～1400℃左右，恒温20～100小时，Li2O扩散到α-Al2O3晶片中。从而得到了LiAlO2/α-Al2O3复合衬底材料。
下面是用上述的气相传输平衡实验装置和具体的工艺流程制备γ-LiAlO2/α-Al2O3复合衬底材料的具体实施例。
在φ100×80mm的鉑金坩埚内，放置有带气孔的LiAlO2和Li2O混合料块，选取[LiAlO2]/[Li2O]＝75∶25重量比。将双面抛光或单面抛光的蓝宝石α-Al2O3晶片，置于或悬于铂金丝上，加上覆盖有LiAlO2和Li2O混合粉料和热电偶的坩埚盖，坩埚顶部加铂金盖密闭，置于电阻炉中。加热电阻炉升温至1150℃，恒温100小时，Li2O扩散到α-Al2O3晶片中。从而得到了γ-LiAlO2/α-Al2O3复合衬底材料。该复合衬底可用于生长高质量InN-GaN薄膜外延生长。

Claims (3)

1一种γ-LiAlO2/α-Al2O3复合衬底材料的制备方法，其特征在于包括如下具体步骤：
①在铂金坩埚内，放置有带气孔的LiAlO2和Li2O混合料块；
②将双面抛光或单面抛光的蓝宝石α-Al2O3晶片置于或悬于铂金丝上，加上覆盖有LiAlO2和Li2O混合粉料和热电偶的坩埚盖，坩埚顶部加铂金盖密闭，置于电阻炉中；
③该电阻炉加热升温至1000～1400℃，恒温20～100小时，Li2O扩散到α-Al2O3晶片中，降温后可得到LiAlO2/α-Al2O3复合衬底材料。
2、根据潜力要求1所述的γ-LiAlO2/α-Al2O3复合衬底材料的制备方法，其特征在于所述的LiAlO2和Li2O混合料块(3)的重量比的选取范围是[LiAlO2]/[Li2O]＝(0～95)∶(100～5)。
3、根据权利要求1或2所述的γ-LiAlO2/α-Al2O3复合衬底材料的制备方法，其特征在于所述的电阻炉也可用硅碳棒炉或硅钼棒炉代替。
CN 03129602 2003-06-27 2003-06-27 γ－LiAlO2/α－Al2O3复合衬底材料的制备方法 Expired - Fee Related CN1204598C (zh)

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PCT/CN2004/000303 WO2005001907A1 (en) 2003-06-27 2004-04-02 THE METHOD OF PREPARING COMPOSITE SUBSTRATE MATERIALS OF Ϝ-LiAlO2 /α-Al2O3

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7045223B2 (en) 2003-09-23 2006-05-16 Saint-Gobain Ceramics & Plastics, Inc. Spinel articles and methods for forming same
CN1308499C (zh) * 2005-02-23 2007-04-04 中国科学院上海光学精密机械研究所 掺钛铝酸锂晶片的制备方法
CN1322175C (zh) * 2004-09-28 2007-06-20 中国科学院上海光学精密机械研究所 脉冲激光沉积制备γ－LiAlO2单晶薄膜覆盖层衬底的方法
CN1322176C (zh) * 2004-09-28 2007-06-20 中国科学院上海光学精密机械研究所 具有γ－LiAlO2单晶薄膜覆盖层衬底的制备方法
US7326477B2 (en) 2003-09-23 2008-02-05 Saint-Gobain Ceramics & Plastics, Inc. Spinel boules, wafers, and methods for fabricating same
CN100457630C (zh) * 2006-12-18 2009-02-04 天津理工大学 一种铝酸锂衬底材料制备法
US7919815B1 (en) 2005-02-24 2011-04-05 Saint-Gobain Ceramics & Plastics, Inc. Spinel wafers and methods of preparation

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US5625202A (en) * 1995-06-08 1997-04-29 University Of Central Florida Modified wurtzite structure oxide compounds as substrates for III-V nitride compound semiconductor epitaxial thin film growth
CN1062317C (zh) * 1997-01-30 2001-02-21 中国科学院上海光学精密机械研究所 垂直温梯法生长铝酸锂和镓酸锂晶体
CN1185690C (zh) * 2002-05-31 2005-01-19 南京大学 制备ZnAl2O4/α－Al2O3复合衬底并在ZnAl2O4上生长GaN薄膜的方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7045223B2 (en) 2003-09-23 2006-05-16 Saint-Gobain Ceramics & Plastics, Inc. Spinel articles and methods for forming same
US7326477B2 (en) 2003-09-23 2008-02-05 Saint-Gobain Ceramics & Plastics, Inc. Spinel boules, wafers, and methods for fabricating same
CN1322175C (zh) * 2004-09-28 2007-06-20 中国科学院上海光学精密机械研究所 脉冲激光沉积制备γ－LiAlO2单晶薄膜覆盖层衬底的方法
CN1322176C (zh) * 2004-09-28 2007-06-20 中国科学院上海光学精密机械研究所 具有γ－LiAlO2单晶薄膜覆盖层衬底的制备方法
CN1308499C (zh) * 2005-02-23 2007-04-04 中国科学院上海光学精密机械研究所 掺钛铝酸锂晶片的制备方法
US7919815B1 (en) 2005-02-24 2011-04-05 Saint-Gobain Ceramics & Plastics, Inc. Spinel wafers and methods of preparation
CN100457630C (zh) * 2006-12-18 2009-02-04 天津理工大学 一种铝酸锂衬底材料制备法

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