CN106119807B - 一种掺硼金刚石粉末的制备方法 - Google Patents

一种掺硼金刚石粉末的制备方法 Download PDF

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CN106119807B
CN106119807B CN201610536965.1A CN201610536965A CN106119807B CN 106119807 B CN106119807 B CN 106119807B CN 201610536965 A CN201610536965 A CN 201610536965A CN 106119807 B CN106119807 B CN 106119807B
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张贵峰
索妮
王蕾
黄昊
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Dalian University of Technology
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment
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Abstract

本发明属于新材料合成领域，提供了一种掺硼金刚石粉末的制备方法。将硼源的乙醇溶液超声振荡形成分散液，滴到载体上，烘干即得衬底；采用HFCVD法制备金刚石薄膜，在100％氢气环境下，对衬底进行精细净化和活化处理，活化处理时间为20‑40min；活化处理与金刚石薄膜沉积过程中，温度维持2000‑2200℃，控制衬底温度为650‑950℃，反应室内总压强20‑70Torr；金刚石薄膜沉积时，甲烷浓度为0.5％‑2％，沉积时间1‑6h；将金刚石薄膜放入管式炉中，抽真空后通入保护气体，扩散退火处理。此方法具有简单、方便、安全、掺硼量可控等优点。特别适用于作燃料电池阴极催化剂的BDD电极制备。

Description

一种掺硼金刚石粉末的制备方法
技术领域
本发明属于新材料合成领域，涉及电化学催化或活化电极材料的合成，特别涉及纳米、亚微米或微米金刚石掺硼，获得具有导电特性的掺硼金刚石(Boron doped diamond，BDD)，以有效地应用于各电化学领域范围内。
背景技术
BDD是被广泛研究的电极催化材料，具有良好的物理与化学特性，如机械强度高、较高的硬度，电阻率和热导率、光透性好、生物相容性、化学惰性以及良好的导电性；在电化学上，具有电势窗口宽、较低的双层电容，吸附性及背景电流，在不同溶液中，具有极高的抗腐蚀性。作为催化剂材料，在电分析、电合成、污水处理、燃料电池、超级电容器以及生物化学传感器等领域都有广泛应用。
对燃料电池的阴极催化剂而言，主要以商用Pt/C为主。为了实现商业化应用，需要一定的Pt负载量，因Pt基催化剂价格昂贵，提高了催化剂的成本。此外，在直接甲醇燃料电池中，还易受甲醇渗透的影响，产生“混合电位”，大大降低燃料电池的效率和电池的输出功率，导致非Pt基催化剂成为了研究重点。在非Pt基催化剂中，BDD因可以改变碳材料的结构，进而影响其亲水性、导电性和催化活性等特性，电化学上，具有电势窗口宽、背景电流低、极高的化学稳定性、低吸附性及活性表面积大，能够有效提高电化学反应效率等优点，使BDD获得了广泛的关注与研究。
目前常用掺硼的方法是气相法，即在气相沉积金刚石薄膜的过程将硼烷通入反应室内，虽然掺硼量可精确控制，但由于硼烷毒性大，使用时需要十分小心谨慎。也有将B2O3溶于有机溶剂后，再用载气将含硼有机溶剂通入到反应室中，但此方法掺硼量不好控制。
本发明是将气相沉积与高温扩散结合起来，利用热丝化学气相沉积法(HFCVD)在硼粉或含硼纳米粉(如氮化硼、二硼化钛)上沉积金刚石，获得金刚石包覆的硼或含硼纳米颗粒，再通过高温真空扩散退火处理，致使硼原子以置换的形式替换金刚石晶格中的C原子从而获得BDD。粉末尺寸由硼或含硼纳米粉的颗粒尺寸确定，金刚石包覆厚度由气相沉积时间确定，掺硼量由扩散退火温度和时间确定。因此，本方法具有简单、方便、安全、掺硼量可控等优点。本发明特别适用于作燃料电池阴极催化剂的BDD电极制备。
发明内容
本发明的目的是提供了一种利用HFCVD在硼源(单质硼、氮化硼、二硼化钛)上沉积金刚石薄膜，通过控制退火温度与时间，制备BDD粉末的工艺方法。目的是通过掺硼的方式，使金刚石具有金属特性，并有效得应用于各电化学领域范围内。
本发明的技术方案：
一种掺硼金刚石粉末的制备方法，步骤如下：
(1)依次用丙酮、乙醇和去离子水超声清洗载体15min，烘干；
(2)将浓度为2.5-12.5mg/mL硼源的乙醇溶液超声振荡30min形成分散液，滴到载体上，烘干即得衬底；
(3)采用HFCVD法制备金刚石薄膜，在100％氢气环境下，对步骤(2)烘干后的衬底进行精细净化和活化处理，活化处理时间为20-40min；活化处理与金刚石薄膜沉积过程中，温度维持2000-2200℃，控制衬底温度为650-950℃，反应室内总压强20-70Torr；金刚石薄膜沉积时，甲烷浓度为0.5％-2％，沉积时间1-6h；
(4)将金刚石薄膜放入管式炉中，抽真空后通入保护气体，扩散退火处理，退火温度1100-1600℃，退火时间为3-6h。
所述的载体为硅片、不锈钢片、石墨片或钛片。
所述的硼源包括单质硼、氮化硼和二硼化钛。
在活化处理与金刚石薄膜沉积过程，灯丝材料选自钨、铼、钽和钼。
所述的保护气体选自氮气、氩气和氦气。
本发明的有益效果：将气相沉积与高温扩散结合起来，粉末尺寸由硼或含硼纳米粉的颗粒尺寸确定，金刚石包覆厚度由气相沉积时间确定，掺硼量由扩散退火温度和时间确定。此方法具有简单、方便、安全、掺硼量可控等优点。特别适用于作燃料电池阴极催化剂的BDD电极制备。
附图说明
图1是实施例1掺硼金刚石粉末的拉曼光谱图。
图2是实施例2掺硼金刚石粉末的拉曼光谱图。
具体实施方式
以下结合附图和技术方案，进一步说明本发明的具体实施方式。
实施例1：
(1)依次用丙酮、乙醇和去离子水超声清洗钛片载体15min，并吹干；
(2)将浓度为5mg/mL硼粉的乙醇溶液装入烧杯中，超声振荡30min形成分散液，滴在钛片上，烘干即得衬底；
(3)将烘干后的衬底放入反应室内的样品台上，本底真空抽至1×10-3Pa以上。通入氢气，并调节真空泵的抽速，使反应室内气压维持在30Torr；
(4)灯丝材料选为钽丝，加热至2000-2200℃，衬底温度为650-950℃，氢气刻蚀衬底表面40min；
(5)之后保持灯丝温度和衬底温度不变，通入甲烷，与氢气的百分比为1％，流量分别为1.5/100sccm，沉积时间4h；
(6)将金刚石包覆颗粒样品置于瓷舟中，放入管式炉石英管中的恒温区，缓慢抽真空后，通氩气将残余空气排出，并在石英管内存留部分氩气，作为保护气体；
(7)设定退火温度1400℃，退火时间3h，制备BDD粉末。
实施例2：
(1)依次用丙酮、酒精和去离子水超声清洗钛片载体15min，并吹干；
(2)将浓度为12mg/mL二硼化钛的乙醇溶液装入烧杯内，超声振荡30min形成分散液，滴在钛片上，烘干即得衬底；
(3)将烘干后的衬底放入反应室中的样品台上，本底真空抽至1×10-3Pa以上。通入氢气，并调节真空泵的抽速，使反应室内气压维持在50Torr；
(4)灯丝材料为钨丝，加热至2000-2200℃，衬底温度650-950℃，氢气刻蚀衬底表面30min；
(5)之后保持灯丝温度和衬底温度不变，通入甲烷，与氢气的百分比为1.5％，流量分别为1.5/100sccm，沉积时间2h；
(6)将金刚石包覆颗粒样品置于瓷舟中，放到管式炉石英管中的恒温区，缓慢抽真空后，通入氮气排出残余空气，并在石英管中存留部分氮气，作为保护气体；
(7)设定退火温度1100℃，退火时间4h，制备BDD粉末。

Claims (8)

1.一种掺硼金刚石粉末的制备方法，其特征在于，步骤如下：
(1)依次用丙酮、乙醇和去离子水超声清洗载体15min，烘干；
(2)将浓度为2.5-12.5mg/mL硼源的乙醇溶液超声振荡30min形成分散液，滴到载体上，烘干即得衬底；
(3)采用HFCVD法制备金刚石薄膜，在100％氢气环境下，对步骤(2)烘干后的衬底进行精细净化和活化处理，活化处理时间为20-40min；活化处理与金刚石薄膜沉积过程中，温度维持2000-2200℃，控制衬底温度为650-950℃，反应室内总压强20-70Torr；金刚石薄膜沉积时，甲烷浓度为0.5％-2％，沉积时间1-6h；
(4)将金刚石薄膜放入管式炉中，抽真空后通入保护气体，扩散退火处理，退火温度1100-1600℃，退火时间为3-6h。
2.根据权利要求1所述的制备方法，其特征在于，所述的载体为硅片、不锈钢片、石墨片或钛片。
3.根据权利要求1或2所述的制备方法，其特征在于，所述的硼源包括单质硼、氮化硼和二硼化钛。
4.根据权利要求1或2所述的制备方法，其特征在于，在活化处理与金刚石薄膜沉积过程，灯丝材料选自钨、铼、钽和钼。
5.根据权利要求3所述的制备方法，其特征在于，在活化处理与金刚石薄膜沉积过程，灯丝材料选自钨、铼、钽和钼。
6.根据权利要求1、2或5所述的制备方法，其特征在于，所述的保护气体选自氮气、氩气和氦气。
7.根据权利要求3所述的制备方法，其特征在于，所述的保护气体选自氮气、氩气和氦气。
8.根据权利要求4所述的制备方法，其特征在于，所述的保护气体选自氮气、氩气和氦气。
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Families Citing this family (7)

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Publication number Priority date Publication date Assignee Title
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CN106835133A (zh) * 2016-12-21 2017-06-13 中国科学院深圳先进技术研究院 一种具有二硼化钛‑金刚石复合涂层的工件及其制备方法
CN111115625A (zh) * 2018-11-01 2020-05-08 深圳先进技术研究院 掺杂型金刚石粉的制备方法
WO2020087429A1 (zh) * 2018-11-01 2020-05-07 深圳先进技术研究院 掺杂型金刚石粉的制备方法
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CN114751408B (zh) * 2022-03-25 2023-09-05 浙江工业大学 一种低压下基于石墨制备金刚石的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101956178A (zh) * 2010-09-28 2011-01-26 浙江工业大学 一种硼掺杂纳米金刚石薄膜及制备方法
CN102102220A (zh) * 2009-12-22 2011-06-22 中国科学院物理研究所 金刚石（111）面上的石墨烯制备方法
CN104164702A (zh) * 2014-08-08 2014-11-26 上海交通大学 一种硼掺杂超/精细金刚石单晶微粉的制备方法
CN105624642A (zh) * 2016-03-16 2016-06-01 大连理工大学 一种石墨衬底上直接沉积金刚石薄膜的方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5290656B2 (ja) * 2008-07-22 2013-09-18 東海旅客鉄道株式会社 ホウ素ドープダイヤモンドの製造方法
KR101427710B1 (ko) * 2012-11-30 2014-08-13 한국과학기술연구원 기체로부터의 입자 합성을 이용한 다이아몬드 파우더의 제조 방법 및 이에 의하여 제조된 다이아몬드 파우더

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102102220A (zh) * 2009-12-22 2011-06-22 中国科学院物理研究所 金刚石（111）面上的石墨烯制备方法
CN101956178A (zh) * 2010-09-28 2011-01-26 浙江工业大学 一种硼掺杂纳米金刚石薄膜及制备方法
CN104164702A (zh) * 2014-08-08 2014-11-26 上海交通大学 一种硼掺杂超/精细金刚石单晶微粉的制备方法
CN105624642A (zh) * 2016-03-16 2016-06-01 大连理工大学 一种石墨衬底上直接沉积金刚石薄膜的方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Deposition of boron doped diamond and carbon nanomaterials on graphite foam electrodes;Marian Marton, et al.,;《Applied Surface Science》;20140901;第312卷;第139-144页 *
Effect of B/C ratio on the physical properties of highly boron-doped diamond films;Fuchao Jia, et al.,;《Vacuum》;20100304;第84卷(第7期);第930-934页 *

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