CN102282107A - 锗烷纯化 - Google Patents

锗烷纯化 Download PDF

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CN102282107A
CN102282107A CN2009801546674A CN200980154667A CN102282107A CN 102282107 A CN102282107 A CN 102282107A CN 2009801546674 A CN2009801546674 A CN 2009801546674A CN 200980154667 A CN200980154667 A CN 200980154667A CN 102282107 A CN102282107 A CN 102282107A
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加里·D·米勒
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Abstract

一种用于纯化含有磷化氢的锗烷，以提供纯化的锗烷产品的方法和系统。本发明的一方面是制备含有低于50ppb磷化氢的纯化的锗烷产品的方法，其包括提供磷化氢污染的锗烷气体和氢气的混合物；使锗烷气体氢气混合物通过选择性吸附磷化氢的吸附剂，以及产生纯化的锗烷气体和氢气的混合物；以及从氢气锗烷气体混合物中分离纯化的锗烷气体。

Description

锗烷纯化
发明背景
高纯度气流的提供在多种工业和研究应用中是非常重要的。气相处理技术，例如化学气相淀积在半导体工业中的快速发展与完全依赖于超高纯度处理气体传输的制造装备在半导体制备工厂中的部署和应用密切相关。
鉴于半导体制备中的气流中的杂质的存在，应当注意高质量薄膜电池和光电池的化学气相淀积生长或通过其他淀积技术的生长被多种低水平的加工杂质所抑制。这些杂质能造成缺陷，其通过增加不合格品从而降低产率，这可是非常昂贵的。这些杂质可以是微粒或化学污染物。
化学杂质可在原始气体产生过程中产生，或者在其随后的包装、运输、储存和处理中产生。虽然厂商通常要对传输到半导体制备工厂的原始气体材料进行分析，气体的纯度也可能由于交叉污染或不当配制的容器而发生变化，例如包装气体的贮气筒。杂质污染也可能由不当的贮气筒改变、渗漏到下游加工装备的污染或所述下游装备的意料不到的污染造成。
在多种工业和商业过程中，需要提供高纯度的锗烷。通常需要高纯度锗烷的一个领域是半导体装备的装配，例如晶体管、二极管、集成电路、检测器、太阳能电池等。在许多这些应用中，高纯度锗烷时常被用作淀积硅-锗合金或添加基质的气体。最近，由于将锗整合到活性硅结构中的新技术，四氢化锗在半导体和太阳能电池中的商业用途稳步增加。该新技术需要锗烷在更高的纯度水平下生产，其杂质浓度变化较小。
由于意料不到的原材料变化、意料不到的制备过程条件变化或意料不到的容器相关条件变化，锗烷可能含有磷化氢污染物。诸如锗烷和磷化氢的两种具有类似挥发性和相对类似的分子量的分子的分离使得杂质下降至低水平，低于50ppb，文献中未报道确切水平。
附图简述
图1是氢气中的锗烷样品的色谱图，其不含磷化氢。
图2是含有4300ppb磷化氢的氢气中的锗烷样品的色谱图，以及
图3是含有130ppb磷化氢的氢气中的锗烷样品的色谱图。
发明详述
开发了一种纯化被磷化氢污染的锗烷气体的方法。该方法基于下列发现：磷化氢，一种与锗烷具有类似挥发性和分子量的化合物可通过适当条件的分子筛从含有磷化氢的锗烷气体中选择性除去，所述分子筛具有约4埃或以上的有效孔径。磷化氢和锗烷的有效直径为3-4埃。磷化氢优选於锗烷之前被保留在分子筛中。优选地，所述分子筛具有约5埃或更大的有效孔径。更优选的，所述分子筛具有约5埃的有效孔径。
方法：
干燥吸附剂：
用于本发明的分子筛床通过加热至200℃-300℃干燥4-12小时，期间用干氦气净化。随后在干氦气净化条件下冷却至约23℃。加热和冷却净化也可使用诸如氮气和氢气的干燥气体。
条件：
分子筛床必须调节至锗烷饱和的状态。锗烷被强烈地吸收到新干燥的分子筛上。该吸收放热，井显著於近乎从输入气流中完全清除了锗烷气体。输入調埋气通常包含约40％锗烷，优选约20-40％的在氢气中的锗烷通过分子筛床或与筛床保持接触。维持调节气流直到锗烷成分不再被筛床吸附。必需注意避免筛床过热以及可能的锗烷分解/爆燃。监测筛床温度避免过热，优选的筛床温度为约60℃或更低。筛床温度必需维持在锗烷分解/爆燃温度以下。
分子筛：
适用于本发明的分子筛实例通常包括4A、5A、10X和13X。这些分子筛可从众多供应商获得，这些分子筛有效孔径为约4埃或更大。分子筛是合成的沸石，其具有非常均一的孔和晶状腔。4A型号(4埃)分子筛是沸石的钠形式。4A型号能吸收临界直径低于4埃(0.4nm)的那些分子。5A型号(5埃)分子筛是沸石的钙形式，能吸收临界直径低于5埃(0.5nm)的那些分子。10X型号是钠沸石的修饰形式，具有约8埃的有效孔径。13X型号是钠沸石的修饰形式，具有约10埃(1nm)的有效孔径。
优选的分子筛是5A型号的，其具有组成0.80CaO:0.20Na2O:Al2O3:2.0±0.1SiO2:xH2O。用二价钙离子替换钠阳离子获得约5埃的孔径。
本发明将通过参考下列实施例进一步说明，但应当理解，本发明不受其限制。
纯化锗烷：
实施例1
一系列12个含有纯锗烷的贮气筒被最高约4500ppb的磷化氢污染。其中10个贮气筒中的锗烷气体根据本发明处理。测定每个贮气筒的磷化氢含量。10个经处理的贮气筒含有不超过50ppb的磷化氢。本例中磷化氢的检测限是50ppb。未处理以除去磷化氢的含锗烷贮气筒CS0998和CS0736分别含有4300ppb和4500ppb磷化氢。贮气筒样品通过气相色谱-电感耦合等离子质谱(GC-ICP-MS)分析。
Figure BDA0000076088010000031
方法：
上述样品通过GC-ICP-MS分析。使用10ppm磷化氢的标准贮存品校准，从10ppm系列稀释至130ppb。质谱调谐中使用碰撞反应池技术(CCT)以降低m/z 31-m/z 47的氧碰撞气体干扰。
色谱分析条件：
仪器：Thermo Scientific XSeries ICP-MS
柱：80mX0.32mm GasPro
载体：20psig的氢气
箱：45度等温
样品大小：250μl
Split：2.5ml/分
[0018]ICP-MS分析条件：
检测器：ICP-MS，m/z 47，500ms dwell
提取：-94v
Lens 1：-1130v
Lens 2：-80v
Lens 3：-189v
四极杆偏压：-3.8v
取样深度：109
Dl：-42.4v
聚焦：6.7v
CCT 2：0.06ml/分
D2：-121v
DA：-36v
六极杆偏压：-0.4v
Add.Das 1：187ml/分
实施例2
用锗烷调节分子筛：
使含有16.895kg锗烷的20％锗烷(摩尔分数)氢气通过含有54kg5A型号干分子筛的床体，其标称颗粒尺寸为4x7网孔(等价于1/8″小球)，具有约5埃的标称有效孔径。该分子筛装在串联的两根柱子中——每根柱子长8英尺，内径为6英寸。处理流速为3kg锗烷/小时，低温收集锗烷气体，由此从气体混合物中的氢气中分离锗烷。锗烷随后进行磷化氢分析。回收的锗烷为9.339kg。柱中的分子筛保留了7.556kg锗烷。
锗烷的分析通过实施例1中描述的步骤进行。
实施例3
锗烷回收：
将含有28.375kg锗烷的20％锗烷(摩尔分数)氢气通过含有54kg5A型号的与实施例2中相同的分子筛的床体，其具有约5埃的标称有效孔径。该过程耗时大约12小时。氢气中的锗烷被收集，以进行锗烷分析。回收的锗烷量为28.120kg，回收率99.10％。
图1是不含磷化氢的氢气中锗烷样品的色谱图。该样品使用250μlloop运转，色谱图中未检测到磷化氢。
图2是含磷化氢的氢气中锗烷样品的色谱图。该样品使用100μl loop运转，色谱图中检测到磷化氢，其保留时间为36000ms。
图3是含有130ppb磷化氢的氢气中的锗烷样品的色谱图。该样品使用250μl loop运转，色谱图中检测到磷化氢，其保留时间为36000ms。
含有4300ppb磷化氢的样品，图2，使用100μl loop运转以维持线性。

Claims (21)

1.一种制备纯化的锗烷产品的方法，包括：提供含有磷化氢的锗烷气体；使该含有磷化氢的锗烷气体通过吸附剂，其选择性吸附含有的磷化氢，以产生纯化的锗烷气体。
2.权利要求1的方法，其中所述纯化的锗烷气体含有低于50ppb的磷化氢。
3.权利要求1的方法，其中所述含有磷化氢的锗烷气体最多占氢气的约40％。
4.权利要求1的方法，其中所述含有磷化氢的锗烷气体占氢气的约20-40％。
5.权利要求3的方法，还包括从氢气中分离纯化的锗烷产品。
6.权利要求1的方法，其中所述吸附剂是沸石。
7.权利要求1的方法，其中所述吸附剂是分子筛，其选自4A、5A、10X、13X及其组合。
8.权利要求7的方法，其中所述分子筛是5A。
9.权利要求1的方法，其中所述吸附剂具有约4埃或更大的有效孔径。
10.权利要求1的方法，其中所述吸附剂具有约4埃的有效孔径。
11.权利要求1的方法，其中所述吸附剂被干燥。
12.权利要求1的方法，其中所述吸附剂通过使锗烷通过干燥的吸附剂进行调节。
13.权利要求1的方法，其中所述吸附剂在干燥气体净化下干燥约4-12小时。
14.权利要求1的方法，其中所述吸附剂在200℃-300℃下干燥。
15.权利要求1的方法，其中所述吸附剂通过使锗烷气流通过吸附剂进行调节，直到锗烷不再显著地保留在吸附剂中。
16.调节吸附剂的方法，包括：干燥吸附剂和通过使锗烷通过干燥的吸附剂从而调节吸附剂。
17.权利要求16的方法，其中所述吸附剂在200℃-300℃下干燥。
18.权利要求16的方法，其中所述吸附剂在干燥气体净化下干燥约4-12小时。
19.权利要求16的方法，其中所述吸附剂通过使锗烷气流通过吸附剂进行调节，直到锗烷不再显著地保留在吸附剂中。
20.权利要求16的方法，其中所述吸附剂是静态床。
21.权利要求16的方法，其中所述吸附剂是流通床。
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CN111777040A (zh) * 2020-07-31 2020-10-16 江西华特电子化学品有限公司 一种高纯锗烷的纯化生产工艺及其生产系统

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CN117216577B (zh) * 2023-11-07 2024-02-27 博纯材料股份有限公司 基于锗烷提纯系统的温度监测方法及系统

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DE112009004270B4 (de) 2014-09-11
CN102282107B (zh) 2014-07-23
RU2518602C2 (ru) 2014-06-10
US20100122628A1 (en) 2010-05-20
WO2010057073A1 (en) 2010-05-20
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DE112009004270T5 (de) 2013-01-10
JP5701217B2 (ja) 2015-04-15

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