CN114497277A - 基于石墨烯/氧化镓异质结的二极管及其制备方法 - Google Patents
基于石墨烯/氧化镓异质结的二极管及其制备方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 64
- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 61
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000004544 sputter deposition Methods 0.000 claims description 15
- 238000000137 annealing Methods 0.000 claims description 9
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
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- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
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- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
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- 238000007738 vacuum evaporation Methods 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 abstract description 10
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- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
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- RNQKDQAVIXDKAG-UHFFFAOYSA-N aluminum gallium Chemical compound [Al].[Ga] RNQKDQAVIXDKAG-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明属于半导体技术领域，尤其涉及一种基于石墨烯/氧化镓异质结的二极管，从下至上依次为ITO衬底、氧化镓薄膜、石墨烯薄膜和铝电极层，其制备方法依次由衬底刻蚀、衬底准备、溅射氧化镓薄膜、退火处理、制备石墨烯、转移石墨烯以及蒸镀电极等步骤组成。该二极管具有制备方法简单，能够在常温下工作等特点，且器件表现出优异的整流行为和高透明性。
Description
技术领域
本发明属于半导体技术领域，尤其涉及一种基于石墨烯/氧化镓异质结的二极管及其制备方法。
背景技术
二极管是用半导体材料制成的一种电子器件，在各种电子电路中应用非常广泛。基于碳化硅和氮化镓的宽带隙半导体的高功率和高电压电子技术已经引起了人们的极大兴趣和开发努力，因为这些材料的品质因数比硅高几百倍。因此碳化硅和氮化镓晶体管和二极管已经商业化，在某些应用中的市场份额不断增加。
氧化镓是直接带隙的宽禁带氧化物半导体材料，其禁带宽度约为4.9eV,吸收波长在 250nm左右，对于紫外光的透过率可达80％以上，具有优异的深紫外吸收特性。由于氧化镓半导体材料所表现出的诸多优势，将加速基于氧化镓的二极管的发展，未来有望取代传统硅基大功率器件。氧化镓存在有五种同分异构体，其中β相氧化镓化学稳定性最好，拥有高临界电场强度，有助于打造超高功率的分立型半导体器件。然而氧化镓虽然有性能优势明显，但也有其明显的短板：氧化镓本征为N型半导体材料，对于氧化物而言解决P型掺杂问题相对比较困难，现有技术采用P型材料与氧化镓形成异质PN结接触结构来解决此问题，目前已知的异质结结构包括公开号为CN113675297涉及的氧化镓/氮化镓异质结、公开号为CN111599890涉及的氧化镓/二硫化钼异质结以及公开号为CN112086344涉及的氧化镓 /铝镓氧异质结，但是目前存在的异质结结构在P型材料匹配度不高或制备困难的问题。
发明内容
针对现有的异质结结构在P型材料匹配度不高或制备困难，导致最终得到的异质PN 结的性能不佳的问题，本发明提出一种基于石墨烯/氧化镓异质结的二极管。
基于石墨烯/氧化镓异质结的二极管，该二极管采用具有垂直结构的异质结器件，从下至上依次为ITO衬底、氧化镓薄膜、石墨烯薄膜和铝电极层。
基于石墨烯/氧化镓异质结的二极管的制备方法，包括以下步骤：
步骤1，衬底刻蚀：取用ITO衬底做基底，用胶带掩模遮盖ITO衬底，放入稀盐酸溶液中刻蚀；
步骤2，衬底准备：将步骤1制得的ITO衬底进行湿法清洗，然后用氮气喷枪吹干，再利用耐高温胶带掩模，掩模区域在ITO刻蚀台阶处；
步骤3，溅射氧化镓薄膜：采用射频磁控溅射法在步骤2制得的ITO衬底上制备氧化镓薄膜；
步骤4，退火处理：在步骤3制得的负载有氧化镓薄膜的基底进行退火处理；
步骤5，制备石墨烯：采用化学气相沉积法制备石墨烯薄膜；
步骤6，转移石墨烯：将制备的石墨烯薄膜转移到步骤4制得的基底上；
步骤7，蒸镀电极：将步骤6制得的器件粘在掩模板上，用真空蒸镀仪蒸镀铝电极。
具体的，步骤3所述射频磁控溅射法选用的设备真空度为8.0×10-4Pa以下，设定溅射压强为0.8-0.9Pa，溅射功率为180-190W，预溅射5min后计时溅射30-50min，厚度为 100-120nm。
具体的，步骤4所述退火处理的方法为将对制备的氧化镓薄膜在900℃环境中保温60min，升温速率为15℃/min。
具体的，步骤5制备石墨烯的方法为：
1)将铜箔预处理后压平放置于银托盘中，推入石英管中并密封石英管两端；
2)常温下在石英管中同时通入氩气和氢气30min，清洗石英管内余气；
3)以17℃/min的升温速率将石英管内温区温度升高至1000℃,还原铜箔表面的氧化层；
4)在1000℃下保温30min,使铜晶粒在高温下长大；
5)在石英管内通入甲烷进行石墨烯薄膜生长，反应时间为18min。
具体的，步骤6转移石墨烯的方法为：
1)裁剪生长有石墨烯薄膜的铜箔至所需大小,并置于FeCl3刻蚀液中，使铜箔刻蚀完全；
2)用清洗后的载玻片从刻蚀液中捞出石墨烯薄膜，并转移到去离子水中清洗三次，每次30 min；
3)用步骤4制得的基底缓慢地将石墨烯薄膜从去离子水中取出。
石墨烯因其独特的结构具有极高的载流子迁移率、局域的超强导电性、及其优异的光学特性在光电领域有着很大的发展潜力，能够将氧化镓更好的应用于光电子器件中。因此，基于氧化镓与石墨烯制备的二极管，具有化学稳定性好、大小可控、透明、整流特性好的优点，在集成电路微纳芯片合成等方面具有潜在的应用前景。这种构建石墨烯异质结的方式对石墨烯在半导体技术领域的应用提出了新的思路。
本发明先后采用射频磁控溅射法和化学气相沉积法在ITO衬底上制备出垂直结构的基于石墨烯/氧化镓异质结的二极管，在室温条件下溅射氧化镓薄膜，采用非原位退火的方式，制得的氧化镓薄膜结晶性较好。本发明制备的二极管制备方法简单，制备成本低廉，能够在常温下工作等特点，且器件表现出优异的整流行为和高透明性。
附图说明
图1为基于石墨烯/氧化镓异质结的二极管的结构示意图。
图2为制备得到的石墨烯薄膜的拉曼图谱。
图3为制备得到的氧化镓薄膜的X射线衍射图谱。
图4为基于石墨烯/氧化镓异质结的二极管的能带结构示意图。
图5为基于石墨烯/氧化镓异质结的二极管的I-V分析结果图。
其中，ITO衬底1，氧化镓薄膜2，石墨烯薄膜3，铝电极层4。
具体实施方式
实施例1：以下通过具体实施方式对本发明作进一步的详细说明，但不应将此理解为本发明的范围仅限于以下的实例。在不脱离本发明上述方法思想的情况下,根据本领域普通技术知识和惯用手段做出的各种替换或变更,均应包含在本发明的范围内。
如图1所示，基于石墨烯/氧化镓异质结的二极管，该二极管采用具有垂直结构的异质结器件，从下至上依次为ITO衬底、氧化镓薄膜、石墨烯薄膜和铝电极层。考虑到氧化镓电阻较大，故采用ITO衬底作底电极，二极管采用的石墨烯薄膜覆盖氧化镓薄膜，覆盖面积约为2cm×2cm作为结区。顶电极采用铝电极镀在石墨烯一端，最后点银浆，干燥后用于测试。
其制备方法包括以下的步骤：
步骤1，衬底刻蚀，取用尺寸为2.5cm×2.5cm的ITO衬底做基底，用胶带掩模遮盖约一半 ITO衬底，放入0.5mol/L的稀盐酸溶液中2h进行刻蚀；
步骤2，衬底准备，将刻蚀好的ITO衬底进行湿法清洗，然后用氮气喷枪吹干，再利用耐高温胶布掩模，露出面积为1cm×1cm，掩模区域要在ITO刻蚀台阶处；
步骤3，溅射氧化镓薄膜，采用射频磁控溅射法在ITO衬底上制备氧化镓薄膜；设备真空度为8.0×10-4Pa以下，设定溅射压强为0.9Pa，溅射功率为180W，预溅射5min后计时溅射 40min，厚度为113nm范围内；
步骤4：退火处理，对制备的负载有氧化镓薄膜的基底进行退火处理，900℃保温60min，升温速率为15℃/min。
步骤5，制备石墨烯，采用化学气相沉积法制备石墨烯薄膜，具体方法为：
(1)将铜箔预处理后压平放置于银托盘中，将其缓缓推入石英管，后将密封石英管两端；
(2)常温下同时通入氩气和氢气30min，清洗石英管内的余气；
(3)以17℃/min的升温速率将温区温度升高至1000℃,调节氩气流量至90mL/min，进一步还原铜箔表面的氧化层；
(4)在1000℃下保温30min,使铜晶粒在高温下长大；
(5)通入甲烷进行石墨烯的生长，流量为50mL/min,反应时间为18min；
步骤6，转移石墨烯，将制备的石墨烯转移到负载有氧化镓薄膜的基底上，具体方法为：
(1)裁剪生长有石墨烯的铜箔至1cm×1cm,并置于FeCl3刻蚀液中反应2-3h,使铜箔刻蚀完全；
(2)用清洗后的载玻片从刻蚀液中小心捞出石墨烯薄膜，并转移到去离子水中清洗三次，每次30min；
(3)用负载有氧化镓薄膜的基底缓慢地将石墨烯从去离子水中取出，先用滤纸将基底表面的去离子水从侧面吸走，然后将器件竖直放置在培养皿中，直至完全干燥；
步骤7，蒸镀电极，将器件粘在掩模板上，用真空蒸镀仪蒸镀铝电极，电极尺寸为5mm×5 mm，厚度为50nm左右，ITO和Al分别作为底部和顶部电极。
如图2所示，实施例制得的石墨烯薄膜的标准峰D峰与G峰出现在1350cm-1和1590cm-1处，且D峰与G峰的比值ID/IG＝0.421，表明具有良好的单层石墨烯特性。
如图3所示，实施例制得的氧化镓薄膜主要沿着特征峰(400)、
(111)、
四个晶面的特征峰生长，900℃退火的氧化镓衍射峰较强，表明样品结晶性较好。
如图4所示，实施例制得的二极管的氧化镓与石墨烯带隙差距较大，故会发生能带的弯折，内部产生内建电场，在结区处产生耗尽区分离载流子。
如图5所示，该二极管表现出优异的整流特性，在负偏压区截止，在正偏压区导通，整流比—I黑暗条件(+10V)/I黑暗条件(-10V)高达3.3×102。并且器件在-10V至10V的较大偏压下仍能正常工作，表明了其能够承受较大的击穿电压，体现了氧化镓材料的性能优势。
Claims (6)
1.基于石墨烯/氧化镓异质结的二极管，其特征在于该二极管采用具有垂直结构的异质结器件，从下至上依次为ITO衬底、氧化镓薄膜、石墨烯薄膜和铝电极层。
2.基于石墨烯/氧化镓异质结的二极管的制备方法，其特征在于包括以下步骤：
步骤1，衬底刻蚀：取用ITO衬底做基底，用胶带掩模遮盖ITO衬底，放入稀盐酸溶液中刻蚀；
步骤2，衬底准备：将步骤1制得的ITO衬底进行湿法清洗，然后用氮气喷枪吹干，再利用耐高温胶带掩模，掩模区域在ITO刻蚀台阶处；
步骤3，溅射氧化镓薄膜：采用射频磁控溅射法在步骤2制得的ITO衬底上制备氧化镓薄膜；
步骤4，退火处理：在步骤3制得的负载有氧化镓薄膜的基底进行退火处理；
步骤5，制备石墨烯：采用化学气相沉积法制备石墨烯薄膜；
步骤6，转移石墨烯：将制备的石墨烯薄膜转移到步骤4制得的基底上；
步骤7，蒸镀电极：将步骤6制得的器件粘在掩模板上，用真空蒸镀仪蒸镀铝电极。
3.如权利要求2所述的基于石墨烯/氧化镓异质结的二极管的制备方法，其特征在于步骤3所述射频磁控溅射法选用的设备真空度为8.0×10-4 Pa以下，设定溅射压强为0.8-0.9Pa，溅射功率为180-190 W，预溅射5min后计时溅射30-50 min，厚度为100-120 nm。
4.如权利要求2所述的基于石墨烯/氧化镓异质结的二极管的制备方法，其特征在于步骤4所述退火处理的方法为将对制备的氧化镓薄膜在900 ℃环境中保温60 min，升温速率为15 ℃/min。
5.如权利要求2所述的基于石墨烯/氧化镓异质结的二极管的制备方法，其特征在于步骤5制备石墨烯的方法为：
将铜箔预处理后压平放置于银托盘中，推入石英管中并密封石英管两端；
常温下在石英管中同时通入氩气和氢气30 min，清洗石英管内余气；
以17 ℃/min的升温速率将石英管内温区温度升高至1000 ℃,还原铜箔表面的氧化层；
在1000 ℃下保温30 min,使铜晶粒在高温下长大；
在石英管内通入甲烷进行石墨烯薄膜生长，反应时间为18 min。
6.如权利要求2所述的基于石墨烯/氧化镓异质结的二极管的制备方法，其特征在于步骤6转移石墨烯的方法为：
裁剪生长有石墨烯薄膜的铜箔至所需大小,并置于FeCl3刻蚀液中，使铜箔刻蚀完全；
用清洗后的载玻片从刻蚀液中捞出石墨烯薄膜，并转移到去离子水中清洗三次，每次30 min；
用步骤4制得的基底缓慢地将石墨烯薄膜从去离子水中取出。
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