CN110724901A - 一种硅锗热电材料的制备方法 - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 48
- 229910000577 Silicon-germanium Inorganic materials 0.000 title claims abstract description 20
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 45
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002159 nanocrystal Substances 0.000 claims abstract description 37
- 238000002493 microarray Methods 0.000 claims abstract description 33
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 32
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- 238000000034 method Methods 0.000 claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 23
- 238000000151 deposition Methods 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 19
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Abstract
本发明公开了一种硅锗热电材料的制备方法,包括:A.在清洁的锗基板进行表面氧化,形成超薄GeO2薄膜层;B.硅以离子束的形式冲击超薄GeO2薄膜层的上表面,产生化学反应:Si+GeO2→SiO↑+GeO↑;在超薄GeO2薄膜层上形成微型阵列孔;C.通过电沉积的方法,沉积7~11层硅原子在设置有微型阵列孔的超薄GeO2薄膜层,电沉积的硅足以填平微型阵列孔;D.硅继续通过电沉积的方法,沉积26~66层硅原子在设置有微型阵列孔的超薄GeO2薄膜层,继续沉积的硅原子被困在微型阵列孔的中,导致了球形纳米晶体的形成,继续沉积,球形纳米晶体长大,形成纳米硅球层;重复上述步骤形成多层超薄GeO2薄膜层和纳米硅球层的复合层,获得硅锗热电材料;上述工艺简单、结构稳定性好。
Description
技术领域
本发明涉及热电转化技术领域,具体涉及一种硅锗热电材料的制备方法。
背景技术
能源是人类经济社会发展的根本动力和重要的物质基础。
中国的能源呈现多煤少油缺气的结构现状,改善能源结构和提高能源利用率刻不容缓。而且目前能源的利用效率较低,提高的空间较大。
热电材料是一种可利用材料Seebeck效应和Peltier效应实现热能和电能直接相互转换的新型能源材料,在工业余热和汽车尾气废热回收利用及热电制冷等方面表现出广泛的应用前景。它具有装置结构简单、无机械传动部件、体积小、寿命长、可靠性高、工作无噪音及环境友好等诸多优点。
热电材料的性能主要由热电优值ZT决定,可以表示为ZT=σS2Т/κ,其中:S为Seebeck系数、σ为电导率、κ为热导率、Т为绝对温度。
当前的热电材料热导率较高的现状仍然突出,本发明涉及的热电材料可以大大降低材料的热导率,提高材料的热电性能。
发明内容
鉴于上述,本发明提供了一种硅锗热电材料的制备方法。
一种硅锗热电材料的制备方法,包括:
A.在温度为330℃~430℃、氧气分压力为(1.8~2.2)*10-4Pa的环境下,在清洁的锗基板进行表面氧化,氧化10~20min,形成超薄GeO2薄膜层;
B.升温至550℃~650℃,硅以离子束的形式冲击超薄GeO2薄膜层的上表面,产生如下的化学反应:
Si+GeO2→SiO↑+GeO↑;
在超薄GeO2薄膜层上形成微型阵列孔,微型阵列孔的孔径为0.8nm~1.2nm,间距为3nm~5nm;
C.在550℃~650℃温度环境下,硅通过电沉积的方法,以(1~1.4)ML/min的沉积速率沉积7~11层硅原子在设置有微型阵列孔的超薄GeO2薄膜层,电沉积的硅足以填平微型阵列孔;
D.在550℃~650℃温度环境下,硅继续通过电沉积的方法,以(1~1.4)ML/min的沉积速率沉积26~66层硅原子在设置有微型阵列孔的超薄GeO2薄膜层,继续沉积的硅原子被困在微型阵列孔的中,导致了球形纳米晶体的形成,继续沉积,球形纳米晶体长大,相邻的球形纳米晶体在交界处达到接触状态,形成纳米硅球层。
优选的,D之后还包括:
E.将温度降至450℃~500℃环境温度,以(1.5~1.8)ML/min的沉积速率在步纳米硅球层上继续沉积13~123层的外延锗层。
优选的,相邻的球形纳米晶体在交界处设置有微孔洞;外延锗层的部分锗原子穿过微孔洞,填充相邻的球形纳米晶体之间的空隙。
优选的,穿过微孔洞的锗原子包裹、填充在球形纳米晶体的表面,保证球形纳米晶体的相对独立。
优选的,球形纳米晶体的晶粒尺寸为3nm~5nm,可以保证相互处于活跃的状态,能够最大限度的吸收热量,转化为有序的电子流,热电效率高。
优选的,E之后还包括:
F.在温度为330℃~430℃、氧气分压力为(1.8~2.2)*10-4Pa的环境下,对外延锗层进行表面氧化,氧化10~20min,形成超薄GeO2薄膜层;
G.重复B、C和D,获得第二层纳米硅球层。
优选的,A之前还包括:
A1.采用硫酸-过氧化氢混合溶液的稀释液和氢氟酸溶液对非掺杂的锗基板进行常规清洗;
A2.将进行常规清洗后的锗基板,在基本压力为(2.8~3.2)*x10-8Pa环境中,引入分子束外延室,升温至350℃~410℃脱气3小时~5小时后,在锗基板上生长出(80~120)nm的锗的缓冲层,进而形成清洁的锗表面。
优选的,A2之后,A之前还包括:
A3.利用高能电子衍射装置(RHEED)对锗表面进行观察,确定锗表面的清洁度。
优选的,超薄GeO2薄膜层有1~5层GeO2分子层。
优选的,超薄GeO2薄膜层有2~3层GeO2分子层。
本发明的目的在于:一种硅锗热电材料的制备方法,包括:A.在温度为330℃~430℃、氧气分压力为(1.8~2.2)*10-4Pa的环境下,在清洁的锗基板进行表面氧化,氧化10~20min,形成超薄GeO2薄膜层;B.升温至550℃~650℃,硅以离子束的形式冲击超薄GeO2薄膜层的上表面,产生化学反应:Si+GeO2→SiO↑+GeO↑;在超薄GeO2薄膜层上形成微型阵列孔,微型阵列孔的孔径为0.8nm~1.2nm,间距为3nm~5nm;C.在550℃~650℃温度环境下,硅通过电沉积的方法,以(1~1.4)ML/min的沉积速率沉积7~11层硅原子在设置有微型阵列孔的超薄GeO2薄膜层,电沉积的硅足以填平微型阵列孔;D.在550℃~650℃温度环境下,硅继续通过电沉积的方法,以(1~1.4)ML/min的沉积速率沉积26~66层硅原子在设置有微型阵列孔的超薄GeO2薄膜层,继续沉积的硅原子被困在微型阵列孔的中,导致了球形纳米晶体的形成,继续沉积,球形纳米晶体长大,相邻的球形纳米晶体在交界处达到接触状态,形成纳米硅球层。E.将温度降至450℃~500℃环境温度,以(1.5~1.8)ML/min的沉积速率在纳米硅球层上继续沉积13~123层的外延锗层。F.在温度为330℃~430℃、氧气分压力为(1.8~2.2)*10-4Pa的环境下,对外延锗层进行表面氧化,氧化10~20min,形成超薄GeO2薄膜层;G.重复B、C和D,获得第二层纳米硅球层。重复B、C、D、E和F获得第三层纳米硅球层、……、第N层纳米硅球层,N为自然数,N大于等于3。上述工艺简单,微型阵列孔的孔径为0.8nm~1.2nm,间距为3nm~5nm,保证了球形纳米晶体的晶粒尺寸为3~5nm,相互之间可以通过晶界交汇处进行结合和原子互换,也能够保证相互独立性,结构稳定性好。
本发明,提供工艺简单的热电材料的制备方法,以推动热电材料科学的发展,以锗为基底且含有外延硅纳米点的热电材料及其制备方案,利用锗为衬底生长外延硅纳米点的复合纳米结构的热电材料,可以分别有效的控制材料的热导率和电导率,提高材料的热电优值。
有益的效果:材料中的热导率是由声子控制的,电导率是由电子控制的,本发明中的热电材料和现有结构的热电材料相比,该热电材料可以分别控制热导率和电导率;声子在通过外延生长的球形纳米晶体(纳米点)的时候会发生散射,从而增大了声子输运的阻力,进而降低了材料的热导率;而这种结构对电子输运的阻力影响比较小,所以根据热电优值的公式可知,降低材料的热导率、提高电导率可以提高热电优值,进而提高材料的热电性能。硅、锗都是良好的半导体材料,但是他们的单质都具有较高的热导率,在锗中掺杂硅之后可明显降低其热导率。
附图说明
下面结合附图对本发明一种硅锗热电材料的制备方法。
图1是本发明一种硅锗热电材料的制备方法的流程示意图。
图2是本发明一种硅锗热电材料的制备方法的制备的硅锗热电材料的结构示意图。
图3是本发明一种硅锗热电材料的制备方法的制备的硅锗热电材料的结构示意图的图2的A处的局部放大图。
图中:
1-锗基板;2-超薄GeO2薄膜层;3-球形纳米晶体;30-纳米硅球层;4-外延锗层。
具体实施方式
下面结合附图1~3对本发明一种硅锗热电材料的制备方法进一步说明。
一种硅锗热电材料的制备方法,包括:
A.在温度为330℃~430℃、氧气分压力为(1.8~2.2)*10-4Pa的环境下,在清洁的锗基板1进行表面氧化,氧化10~20min,形成超薄GeO2薄膜层2;
B.升温至550℃~650℃,硅以离子束的形式冲击超薄GeO2薄膜层2的上表面,产生如下的化学反应:
Si+GeO2→SiO↑+GeO↑;
在超薄GeO2薄膜层上形成微型阵列孔,微型阵列孔的孔径为0.8nm~1.2nm,间距为3nm~5nm;
C.在550℃~650℃温度环境下,硅通过电沉积的方法,以(1~1.4)ML/min的沉积速率沉积7~11层硅原子在设置有微型阵列孔的超薄GeO2薄膜层2,电沉积的硅足以填平微型阵列孔;
D.在550℃~650℃温度环境下,硅继续通过电沉积的方法,以(1~1.4)ML/min的沉积速率沉积26~66层硅原子在设置有微型阵列孔的超薄GeO2薄膜层2,继续沉积的硅原子被困在微型阵列孔的中,导致了球形纳米晶体3的形成,继续沉积,球形纳米晶体3长大,相邻的球形纳米晶体3在交界处达到接触状态,形成纳米硅球层30。
本实施例中,D之后还包括:
E.将温度降至450℃~500℃环境温度,以(1.5~1.8)ML/min的沉积速率在纳米硅球层30上继续沉积13~123层的外延锗层4。
本实施例中,相邻的球形纳米晶体3在交界处设置有微孔洞;外延锗层4的部分锗原子穿过微孔洞,填充相邻的球形纳米晶体3之间的空隙。
本实施例中,穿过微孔洞的锗原子包裹、填充在球形纳米晶体3的表面,保证球形纳米晶体3的相对独立。
本实施例中,球形纳米晶体3的晶粒尺寸为3nm~5nm,可以保证相互处于活跃的状态,能够最大限度的吸收热量,转化为有序的电子流,热电效率高。
本实施例中,E之后还包括:
F.在温度为330℃~430℃、氧气分压力为(1.8~2.2)*10-4Pa的环境下,对外延锗层4进行表面氧化,氧化10~20min,形成超薄GeO2薄膜层2;
G.重复B、C和D,获得第二层纳米硅球层30。
本实施例中,A之前还包括:
A1.采用硫酸-过氧化氢混合溶液的稀释液和氢氟酸溶液对非掺杂的锗基板1进行常规清洗;
A2.将进行常规清洗后的锗基板1,在基本压力为(2.8~3.2)*x10-8Pa环境中,引入分子束外延室,升温至350℃~410℃脱气3小时~5小时后,在锗基板1上生长出(80~120)nm的锗的缓冲层,进而形成清洁的锗表面。
本实施例中,A2之后,A之前还包括:
A3.利用高能电子衍射装置(RHEED)对锗表面进行观察,确定锗表面的清洁度。
本实施例中,超薄GeO2薄膜层2有1~5层GeO2分子层。
本实施例中,超薄GeO2薄膜层2有2~3层GeO2分子层。
重复B、C、D、E和F获得第三层纳米硅球层、……、第N层纳米硅球层,N为自然数,N大于等于3。
上述工艺简单,微型阵列孔的孔径为0.8nm~1.2nm,间距为3nm~5nm,保证了球形纳米晶体的晶粒尺寸为3~5nm,相互之间可以通过晶界交汇处进行结合和原子互换,也能够保证相互独立性,结构稳定性好。
以上仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下还可以作出若干改进,这些改进也应视为本发明的保护范围。
Claims (10)
1.一种硅锗热电材料的制备方法,其特征在于,包括:
A.在温度为330℃~430℃、氧气分压力为(1.8~2.2)*10-4Pa的环境下,在清洁的锗基板(1)进行表面氧化,氧化10~20min,形成超薄GeO2薄膜层(2);
B.升温至550℃~650℃,硅以离子束的形式冲击所述超薄GeO2薄膜层(2)的上表面,产生如下的化学反应:
Si+GeO2→SiO↑+GeO↑;
在所述超薄GeO2薄膜层(2)上形成微型阵列孔,所述微型阵列孔的孔径为0.8nm~1.2nm,间距为3nm~5nm;
C.在550℃~650℃温度环境下,硅通过电沉积的方法,以(1~1.4)ML/min的沉积速率沉积7~11层硅原子在所述设置有微型阵列孔的超薄GeO2薄膜层(2),电沉积的硅足以填平所述微型阵列孔;
D.在550℃~650℃温度环境下,硅继续通过电沉积的方法,以(1~1.4)ML/min的沉积速率沉积26~66层硅原子在所述设置有微型阵列孔的超薄GeO2薄膜层(2),继续沉积的硅原子被困在所述微型阵列孔的中,导致了球形纳米晶体(3)的形成,继续沉积,球形纳米晶体(3)长大,相邻的球形纳米晶体(3)在交界处达到接触状态,形成纳米硅球层(30)。
2.如权利要求1所述硅锗热电材料的制备方法,其特征在于,所述D之后还包括:
E.将温度降至450℃~500℃环境温度,以(1.5~1.8)ML/min的沉积速率在纳米硅球层(30)上继续沉积13~123层的外延锗层(4)。
3.如权利要求2所述硅锗热电材料的制备方法,其特征在于,相邻的球形纳米晶体(3)在交界处设置有微孔洞;所述外延锗层(4)的部分锗原子穿过所述微孔洞,填充相邻的球形纳米晶体(3)之间的空隙。
4.如权利要求3所述硅锗热电材料的制备方法,其特征在于,穿过所述微孔洞的锗原子包裹、填充在球形纳米晶体(3)的表面,保证球形纳米晶体(3)的相对独立。
5.如权利要求3所述硅锗热电材料的制备方法,其特征在于,所述球形纳米晶体(3)的晶粒尺寸为3nm~5nm,可以保证相互处于活跃的状态,能够最大限度的吸收热量,转化为有序的电子流,热电效率高。
6.如权利要求2所述硅锗热电材料的制备方法,其特征在于,所述E之后还包括:
F.在温度为330℃~430℃、氧气分压力为(1.8~2.2)*10-4Pa的环境下,对所述外延锗层(4)进行表面氧化,氧化10~20min,形成超薄GeO2薄膜层(2);
G.重复B、C和D,获得第二层纳米硅球层(30)。
7.如权利要求1所述硅锗热电材料的制备方法,其特征在于,所述A之前还包括:
A1.采用硫酸-过氧化氢混合溶液的稀释液和氢氟酸溶液对非掺杂的锗基板(1)进行常规清洗;
A2.将所述进行常规清洗后的锗基板(1),在基本压力为(2.8~3.2)*x10-8Pa环境中,引入分子束外延室,升温至350℃~410℃脱气3小时~5小时后,在所述锗基板(1)上生长出(80~120)nm的锗的缓冲层,进而形成清洁的锗表面。
8.如权利要求7所述硅锗热电材料的制备方法,其特征在于,所述A2之后,A之前还包括:
A3.利用高能电子衍射装置(RHEED)对锗表面进行观察,确定锗表面的清洁度。
9.如权利要求1所述硅锗热电材料的制备方法,其特征在于,所述超薄GeO2薄膜层(2)有1~5层GeO2分子层。
10.如权利要求9所述硅锗热电材料的制备方法,其特征在于,所述超薄GeO2薄膜层(2)有2~3层GeO2分子层。
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