CN113622027B - 一种高阻氧化镓晶体及其制备方法与应用 - Google Patents
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Abstract
本发明涉及一种高阻氧化镓晶体及其制备方法与应用,所述高阻氧化镓晶体的分子式为β‑(Ga1‑xAlx)2O3,其中x的取值范围为0.07≤x≤0.3,采用包括光学浮区法、提拉法、导模法或下降法的熔体生长方法制备得到。与现有技术相比,本发明提供的掺铝高阻氧化镓晶体的电阻率≥109Ω·cm,晶体结晶质量高,基于该高阻氧化镓晶体制备的辐射探测器具有制作工艺简单、暗电流小、光暗电流比高、响应速度快、灵敏度高、信噪比高、能量分辨率好等优点。
Description
技术领域
本发明属于半导体晶体材料与核辐射探测器件领域,具体涉及一种高阻氧化镓晶体及其制备方法与应用。
背景技术
氧化镓(β-Ga2O3)晶体是一种新型超宽禁带半导体材料,具有禁带宽度大(~4.8eV)、理论击穿场强高(8MV/cm)、抗辐射能力强等优点,近年来受到广泛关注。非故意掺杂氧化镓晶体由于原料中残留的Si、Sn、Ge等杂质在晶体中形成浅施主,导致晶体具有一定浓度的自由电子,从而具有较低的电阻率。使用非故意掺杂氧化镓晶体制备的X射线辐射探测器件具有较高的暗电流,降低了器件的光暗电流比、灵敏度等核心参数,严重影响了探测器件的使用(如“Schottky x-ray detectors based on a bulkβ-Ga2O3 substrate”,Applied Physics Letters 112,103502,2018)。
在核辐射探测领域,为了使半导体探测器件具有高光暗电流比、高灵敏度、高信噪比、高能量分辨率等优良性能,需要使用高阻半导体材料以降低器件的暗电流,提高探测极限。对于氧化镓晶体而言,掺杂镁离子、铁离子、钙离子、锌离子可以起到受主补偿作用,降低晶体中的自由电子浓度,从而获得电阻率较高或半绝缘的氧化镓晶体(专利CN109537055A)。然而这些常用的受主补偿掺杂离子与镓不属于同族元素,电子结构相差较大,掺杂异族元素后会对氧化镓晶体的晶格造成较大畸变,影响高阻氧化镓晶体的结晶质量。
专利CN 113035999A公开了一种掺Al氧化镓X射线探测器及其制备方法,该专利通过在空气或氧气气氛1250-1600℃高温退火的方式来降低掺Al氧化镓单晶中的载流子浓度,并未通过调节Al离子掺杂浓度来获得高阻氧化镓晶体;该专利使用叉指电极制备的X射线探测器由于电场深度远远小于X射线的穿透深度,大部分光生电子空穴对无法被电极收集,造成载流子收集效率低,探测器的光电流不高,而且晶体的表面缺陷会产生大量的漏电流,导致探测器的暗电流提高,不利于器件应用于低剂量率探测。
发明内容
本发明的目的就是为了克服目前通过掺杂异族元素获得高阻氧化镓晶体容易造成较大的晶格畸变、晶体结晶质量较低,导致电子迁移率降低的不足的问题,提供一种高阻氧化镓晶体及其制备方法和应用。
本发明提供的掺铝高阻氧化镓晶体的电阻率≥109Ω·cm,晶体结晶质量高,基于该高阻氧化镓晶体制备的辐射探测器具有制作工艺简单、暗电流小、光暗电流比高、响应速度快、灵敏度高、信噪比高、能量分辨率好等优点。
本发明的目的通过以下技术方案实现:
一种高阻氧化镓晶体,所述高阻氧化镓晶体的分子式为β-(Ga1-xAlx)2O3,其中x的取值范围为0.07≤x≤0.3,x的取值范围对于获取具有优异性能的高阻氧化镓晶体具有重要影响,x值低于0.07时氧化镓晶体具有较高的载流子浓度,晶体的电阻率较低;x值高于0.3时,氧化镓晶体质量严重变差。
铝与镓属于同族元素,具有十分相似的电子结构,并且离子半径接近,掺杂铝离子不会导致氧化镓晶体较大的晶格畸变,因此可以在氧化镓晶体中掺杂较高浓度的铝离子。掺杂铝离子使氧化镓晶体电阻率升高的原理如下:氧化镓晶体的价带顶由O2p态决定,导带底由Ga4s态决定,掺杂铝离子后,价带谱测试得出β-(Ga1-xAlx)2O3晶体的价带顶位置与非故意掺杂β-Ga2O3晶体保持一致,β-(Ga1-xAlx)2O3晶体的价带顶仍由O2p态决定,因此掺杂铝离子不会对氧化镓晶体的价带顶位置造成明显的改变。然而β-(Ga1-xAlx)2O3晶体的导带受到Al3s态的影响,导带底向远离价带的方向移动,造成β-(Ga1-xAlx)2O3晶体的禁带宽度增大,导致β-(Ga1-xAlx)2O3晶体导带底距离施主能级的距离增大,即施主能级陷阱深度增大,施主能级向导带提供电子的能力被抑制,因此β-(Ga1-xAlx)2O3晶体的自由电子浓度大幅降低,氧化镓晶体的电阻率显著提高。本发明提供的高阻氧化镓晶体,室温下电阻率高达109-1012Ω·cm,禁带宽度为4.9eV-5.3eV。
上述高阻氧化镓晶体的制备方法可以采用光学浮区法、提拉法、导模法、下降法等熔体生长方法,优选的制备步骤如下:
(1)取Ga2O3粉末与Al2O3粉末,将上述原料粉末按照分子式准确称量并混合均匀,采用液压或等静压方式压制成型并高温固相烧结合成掺铝氧化镓多晶料;
(2)将多晶原料装入铱金坩埚或铂铑坩埚中,或固定在光学浮区炉的上转杆上。
(3)将定向籽晶固定在籽晶杆上。
(4)采用光学浮区法、提拉法、导模法、下降法进行掺铝氧化镓晶体生长。
步骤(1)所述的Ga2O3粉末纯度优选4N-6N,Al2O3粉末纯度优选4N-5N,高纯度的原料杂质含量更少,可以避免因杂质造成的晶体电阻率降低和晶体质量差等问题出现。
步骤(2)所述的当采用提拉法、导模法或下降法时,采用铱金或铂铑合金坩埚,二氧化碳或二氧化碳和氩气组成的混合气氛;当采用光学浮区法生长时,采用空气气氛或纯氧气气氛,气体流速优选1-5L/min。
本发明还提供了一种上述高阻氧化镓晶体在半导体辐射探测器件中的应用,基于此高阻氧化镓晶体制备的辐射探测器使用双面对称电极结构。
所述高阻氧化镓晶体经过切割、双面化学机械抛光,晶片厚度为0.4-4mm,晶片厚度低于0.4mm会导致不能完全吸收高能射线,使辐射探测器的光电流降低;晶片厚度大于4mm会导致载流子输运过程中的俘获几率增大,使探测器载流子收集效率降低、光电流降低。
所述探测器的双面对称电极为Ti/Au双层金属电极,Ti层厚度为5-50nm,Au层厚度为50-100nm,电极形状为圆形或矩形,电极面积为1-30mm2。
与现有技术相比,本发明具有以下优点:
(1)与掺杂铁、镁等异族元素相比,掺杂铝离子在提高氧化镓晶体电阻率的同时能够进一步增大禁带宽度,并且不会因掺铝而造成氧化镓晶体晶格严重畸变,获得的高阻氧化镓晶体结晶质量高。
(2)与现有技术专利CN 113035999A相比,本发明通过限定Al离子掺杂浓度降低氧化镓晶体的背底载流子浓度,实现氧化镓晶体高阻化;相比于低电阻率氧化镓晶体,采用本发明提供的高阻氧化镓晶体制备的半导体辐射探测器具有暗电流低、光暗电流比高、响应速度快(上升时间和下降时间均小于0.05s)等显著优势,探测灵敏度远远高于商业化的非晶硒X射线探测器,能量分辨率与碲锌镉伽马射线探测器相当。
(3)与现有技术专利CN 113035999A采用叉指电极的辐射探测器相比,本发明辐射探测器采用双面电极,具有器件制备工艺简单、可完全吸收高能射线、载流子收集效率高、受表面漏电流影响小等优点。
附图说明
图1为实施例1β-(Ga0.85Al0.15)2O3切割抛光后的晶体照片。
图2为β-(Ga1-xAlx)2O3,x=0.05、0.1、0.15晶体的透过光谱。
图3为β-(Ga1-xAlx)2O3,x=0.05、0.1、0.15晶体的禁带宽度图谱。
图4为β-(Ga1-xAlx)2O3晶体的能带示意图。
图5为β-(Ga1-xAlx)2O3晶体电阻率与x的关系图。
图6为基于β-(Ga1-xAlx)2O3晶体的辐射探测器件的结构图;
图6中1-Au,2-Ti,3-β-(Ga1-xAlx)2O3晶体,4-Ti,5-Au。
图7为基于β-(Ga0.85Al0.15)2O3晶体的辐射探测器的暗电流与光电流。
图8为基于β-(Ga0.85Al0.15)2O3晶体的辐射探测器在不同电压下对X射线的时间响应。
图9为β-(Ga0.95Al0.05)2O3晶体的I-V曲线。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。
实施例1:
光学浮区法生长β-(Ga0.85Al0.15)2O3晶体。
按照0.85:0.15摩尔比称取Ga2O3粉末和Al2O3粉末,研磨60分钟以使粉末混合均匀,将混合均匀的粉末使用漏斗装入长条状橡胶管制成原料棒,使用冷等静压机在50MPa压力下压制原料棒,将原料棒放入马弗炉中在空气中1450℃烧结20小时制成陶瓷状原料棒。使用光学浮区炉生长晶体,气氛为流动空气氛,将原料棒安装在上转杆,<010>方向的籽晶固定于下转杆,缓慢升高电压加热籽晶与原料棒,晶体生长速度为3mm/h,旋转速度为14rpm,空气流速为3L/min,生长结束后缓慢降至室温,取出晶体,该晶体无色透明,没有裂纹。将晶体切割、抛光,制成5×5×1mm3的晶片,如图1所示。(Ga0.85Al0.15)2O3晶体XRD图谱的衍射峰与β-Ga2O3标准卡片相一致。β-(Ga1-xAlx)2O3,x=0.05、0.1、0.15晶体的透过光谱如图2所示,自由电子会造成等离子体反射,从而降低红外波段的透过率,β-(Ga0.85Al0.15)2O3晶体在红外波段无明显吸收说明该晶体自由电子浓度极低。由图3可知,β-(Ga0.85Al0.15)2O3晶体的禁带宽度为5.11eV,掺铝之后氧化镓晶体的禁带宽度增大。β-(Ga0.85Al0.15)2O3晶体的价带谱测试得出其价带顶位置与β-Ga2O3晶体保持一致,表明掺铝并未改变β-Ga2O3晶体价带顶的位置。掺杂铝离子后,β-Ga2O3晶体的导带顶上移,远离原来的浅施主,施主能级在室温下向导带提供自由电子的能力被抑制。图4为β-(Ga1-xAlx)2O3晶体的能带示意图,其中Ec为导带能级,Ev为价带能级,ED为施主能级,EF为费米能级,β-(Ga0.85Al0.15)2O3晶体的导带底位置高于β-Ga2O3晶体,施主能级比β-Ga2O3晶体的更深。图5为电阻率测试得出的β-(Ga1- xAlx)2O3晶体电阻率与x的关系图,β-(Ga0.85Al0.15)2O3晶体的电阻率为1.5×1012Ω·cm。制备了基于β-(Ga0.85Al0.15)2O3晶体的辐射探测器,在晶体的上、下表面分别沉积正方形的Ti/Au电极,其厚度为20nm/50nm,边长为3mm,探测器结构如图6所示。使用管电压为50kV的X射线源测试该辐射探测器对X射线的探测性能。图7表明当X射线剂量率为0.15Gy/s、器件电压为200V时,探测器的光暗电流比高达700。图8为当X射线剂量率为9.8μGy/s时,探测器在不同电压下的响应,结果表明探测器的响应速度极快,上升时间和下降时间均小于0.05s;当电压为350V时,探测器对X射线的探测灵敏度为851μC Gy-1cm-2,为商业化的非晶硒X射线探测器灵敏度的42倍;各个电压下探测器的信噪比均高于20,符合实用要求。使用铯-137、钴-60等伽马射线源测试探测器对伽玛射线的响应,其能量分辨率与碲锌镉伽马射线探测器相当。以上结果表明基于β-(Ga0.85Al0.15)2O3晶体的辐射探测器对X射线和伽马射线均表现出优异的探测性能。
对比例1:
光学浮区法生长β-(Ga0.95Al0.05)2O3晶体。
按照0.95:0.05摩尔比称取Ga2O3粉末和Al2O3粉末,研磨60分钟以使粉末混合均匀,将混合均匀的粉末使用漏斗装入长条状橡胶管制成原料棒,使用冷等静压机在50MPa压力下压制原料棒,将原料棒放入马弗炉中在空气中1450℃烧结20小时制成陶瓷状原料棒。使用光学浮区炉生长晶体,气氛为流动空气氛,将原料棒安装在上转杆,<010>方向的籽晶固定于下转杆,缓慢升高电压加热籽晶与原料棒,晶体生长速度为3mm/h,旋转速度为14rpm,空气流速为3L/min,生长结束后缓慢降至室温,取出晶体。将晶体切割、抛光,制成5×5×1mm3的晶片。如图2所示,β-(Ga0.95Al0.05)2O3晶体存在明显的红外吸收,说明该晶体具有较高的自由电子浓度。图9为β-(Ga0.95Al0.05)2O3晶体的I-V曲线图,低电压下就能达到较大的电流,因此该晶体电阻率较低。基于β-(Ga0.95Al0.05)2O3晶体制备的辐射探测器具有较大的暗电流。
实施例2:
光学浮区法生长β-(Ga0.9Al0.1)2O3晶体。
按照0.9:0.1摩尔比称取Ga2O3粉末和Al2O3粉末,研磨60分钟以使粉末混合均匀,将混合均匀的粉末使用漏斗装入长条状橡胶管制成原料棒,使用冷等静压机在50MPa压力下压制原料棒,将原料棒放入马弗炉中在空气中1450℃烧结20小时制成陶瓷状原料棒。使用光学浮区炉生长晶体,气氛为流动氧气氛,将原料棒安装在上转杆,<010>方向的籽晶固定于下转杆,缓慢升高电压加热籽晶与原料棒,晶体生长速度为4mm/h,旋转速度为14rpm,氧气流速为1L/min,生长结束后缓慢降至室温,取出晶体。将晶体切割、抛光,制成5×5×1mm3的晶片。如图2所示,β-(Ga0.9Al0.1)2O3晶体无明显红外吸收,其禁带宽度为4.96eV。如图5所示,电阻率测试得出β-(Ga0.9Al0.1)2O3晶体的电阻率为3.8×1011Ω·cm。制备了基于β-(Ga0.9Al0.1)2O3晶体的辐射探测器,电压200V时其对X射线的探测灵敏度为283μCGy-1cm-2。
实施例3:
光学浮区法生长β-(Ga0.7Al0.3)2O3晶体。
按照0.7:0.3摩尔比称取Ga2O3粉末和Al2O3粉末,研磨60分钟以使粉末混合均匀,将混合均匀的粉末使用漏斗装入长条状橡胶管制成原料棒,使用冷等静压机在50MPa压力下压制原料棒,将原料棒放入马弗炉中在空气中1450℃烧结20小时制成陶瓷状原料棒。使用光学浮区炉生长晶体,气氛为流动空气氛,将原料棒安装在上转杆,<010>方向的籽晶固定于下转杆,缓慢升高电压加热籽晶与原料棒,晶体生长速度为2mm/h,旋转速度为14rpm,空气流速为5L/min,生长结束后缓慢降至室温,取出晶体。将晶体切割、抛光,制成5×5×1mm3的晶片。β-(Ga0.7Al0.3)2O3晶体无色透明,无裂纹。如图5所示,电阻率测试得出β-(Ga0.7Al0.3)2O3晶体的电阻率为2.5×1012Ω·cm。制备了基于β-(Ga0.7Al0.3)2O3晶体的辐射探测器,电压350V时其对X射线的探测灵敏度为721μC Gy-1cm-2。
对比例2:
光学浮区法生长β-(Ga0.68Al0.32)2O3晶体。
按照0.68:0.32摩尔比称取Ga2O3粉末和Al2O3粉末,研磨60分钟以使粉末混合均匀,将混合均匀的粉末使用漏斗装入长条状橡胶管制成原料棒,使用冷等静压机在50MPa压力下压制原料棒,将原料棒放入马弗炉中在空气中1450℃烧结20小时制成陶瓷状原料棒。使用光学浮区炉生长晶体,气氛为流动空气氛,将原料棒安装在上转杆,<010>方向的籽晶固定于下转杆,缓慢升高电压加热籽晶与原料棒,晶体生长速度为2mm/h,旋转速度为14rpm,空气流速为5L/min,生长结束后缓慢降至室温,取出晶体,该晶体浑浊不透明且有裂纹,晶体质量较差。
实施例4:
下降法生长β-(Ga0.88Al0.12)2O3晶体。
按照0.88:0.12摩尔比称取Ga2O3粉末和Al2O3粉末,研磨60分钟以使粉末混合均匀,使用液压机将混合均匀的粉末压制成型,将原料放入马弗炉中在空气中1450℃烧结20h制成多晶料。将原料放入铂铑坩埚中,使用<010>方向的籽晶,抽真空至5Pa,充入CO2气体至1.03MPa,加热至原料完全熔化,恒温2小时,使坩埚以0.5mm/h的速率缓慢下降,生长结束后缓慢降至室温,取出晶体。将晶体切割、抛光,制成5×5×1mm3的晶片。如图5所示,电阻率测试得出β-(Ga0.88Al0.12)2O3晶体的电阻率为9.1×1011Ω·cm。制备了基于β-(Ga0.88Al0.12)2O3晶体的辐射探测器,电压200V时其对X射线的探测灵敏度为379μC Gy-1cm-2。
实施例5:
提拉法生长β-(Ga0.93Al0.07)2O3晶体。
按照0.93:0.07摩尔比称取Ga2O3粉末和Al2O3粉末,研磨60分钟以使粉末混合均匀,使用液压机将混合均匀的粉末压制成饼状,将原料放入马弗炉中在空气中1450℃烧结20h制成多晶料。将原料放入铱金坩埚中,将<010>方向的籽晶固定于籽晶杆夹具中。抽真空至5Pa,按照Ar:CO2=2:8的比例充入混合气体至1.04MPa,加热升温至原料完全熔化,下降籽晶与熔体接触,20分钟后提拉籽晶,提拉速度为3mm/h,经过缩颈、放肩、等径生长阶段,生长结束后缓慢降至室温,取出晶体。将晶体切割、抛光,制成5×5×1mm3的晶片。如图5所示,电阻率测试得出β-(Ga0.93Al0.07)2O3晶体的电阻率为8.5×109Ω·cm。制备了基于β-(Ga0.93Al0.07)2O3晶体的辐射探测器,电压200V时其对X射线的探测灵敏度为174μC Gy-1cm-2。
实施例6:
导模法生长β-(Ga0.92Al0.08)2O3晶体。
按照0.92:0.08摩尔比称取Ga2O3粉末和Al2O3粉末,研磨60分钟以使粉末混合均匀,使用液压机将混合均匀的粉末压制成饼状,将原料放入马弗炉中在空气中1450℃烧结20h制成多晶料。将多晶料放入铱金坩埚中,盖好坩埚盖,将<010>方向的籽晶固定于籽晶杆夹具中。抽真空至7Pa,充入CO2气体至1.05MPa,加热至原料完全熔化,下降籽晶与模具顶熔体接触,引晶缩颈后,提拉速度为3mm/h,待晶体放满至模具宽度后提拉速度为5mm/h进行等径生长,生长结束后缓慢降至室温,取出晶体。将晶体切割、抛光,制成5×5×1mm3的晶片。如图5所示,电阻率测试得出β-(Ga0.92Al0.08)2O3晶体的电阻率为3.2×1010Ω·cm。制备了基于β-(Ga0.92Al0.08)2O3晶体的辐射探测器,电压200V时其对X射线的探测灵敏度为215μC Gy- 1cm-2。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (9)
1.一种高阻氧化镓晶体,其特征在于,所述高阻氧化镓晶体的分子式为β-(Ga1-xAlx)2O3,其中x为0.07、0.08、0.12、0.15或0.3。
2.如权利要求1所述的一种高阻氧化镓晶体的制备方法,其特征在于,采用包括光学浮区法、提拉法、导模法或下降法的熔体生长方法制备得到。
3.根据权利要求2所述的一种高阻氧化镓晶体的制备方法,其特征在于,包括如下步骤:
(1)取Ga2O3粉末与Al2O3粉末,将原料粉末按照分子式准确称量并混合均匀,采用液压或等静压方式压制成型并高温固相烧结合成掺铝氧化镓多晶料;
(2)将多晶原料装入铱金坩埚或铂铑坩埚中,或固定在光学浮区炉的上转杆上;
(3)将定向籽晶固定在籽晶杆上;
(4)采用光学浮区法、提拉法、导模法、下降法进行掺铝氧化镓晶体生长。
4.根据权利要求3所述的一种高阻氧化镓晶体的制备方法,其特征在于,步骤(1)所述的Ga2O3粉末纯度为4N-6N,Al2O3粉末纯度为4N-5N。
5.根据权利要求3所述的一种高阻氧化镓晶体的制备方法,其特征在于,步骤(2),当采用提拉法、导模法或下降法时,采用铱金或铂铑合金坩埚,二氧化碳或二氧化碳和氩气组成的混合气氛;当采用光学浮区法生长时,采用空气气氛或纯氧气气氛,气体流速为1-5L/min。
6.如权利要求1所述的一种高阻氧化镓晶体的应用,其特征在于,所述高阻氧化镓晶体用于制作半导体辐射探测器。
7.根据权利要求6所述的一种高阻氧化镓晶体的应用,其特征在于,所述的辐射探测器使用双面对称电极结构,双面对称电极为Ti/Au双层金属电极。
8.根据权利要求7所述的一种高阻氧化镓晶体的应用,其特征在于,Ti层厚度为5-50nm,Au层厚度为50-100nm,电极形状为圆形或矩形,电极面积为1-30mm2。
9.根据权利要求8所述的一种高阻氧化镓晶体的应用,其特征在于,所述高阻氧化镓晶体经过切割、双面化学机械抛光,晶片厚度为0.4-4mm。
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