高压物理学报

Sample	Mass fraction of Fe₃P/%	Morphology	Color	Inclusion
A	1	Octahedron	Yellow	No
B	2	Hexoctahedral	Yellow	Little
C	4	Hexoctahedral	Light yellow	Little
D	6	Hexoctahedral	Light yellow	Many
E	8	Skeletal crystal	Dark

Sample	Mass fraction of Fe₃P/%	Morphology	Color	Inclusion
A	1	Octahedron	Yellow	No
B	2	Hexoctahedral	Yellow	Little
C	4	Hexoctahedral	Light yellow	Little
D	6	Hexoctahedral	Light yellow	Many
E	8	Skeletal crystal	Dark

Sample	C_N/10⁻⁶
A	387
B	157
C	134
D	111

Sample	C_N/10⁻⁶
A	387
B	157
C	134
D	111

Sample	σ_h/GPa
A	0.052
B	0.107
C	0.149
D	0.194

Sample	σ_h/GPa
A	0.052
B	0.107
C	0.149
D	0.194

高温高压下FeNiCo-C体系中磷掺金刚石的合成与表征

张浩波 , 胡美华 , 李尚升 , 刘迪 , 和莎莎 , 李晓晓 , 王振阳

高压物理学报 | 高压下的碳材料 2026,40(9): 090113-1-090113-9

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高压物理学报 |高压下的碳材料 2026 , 40 (9) : 090113-1 -090113-9

高温高压下FeNiCo-C体系中磷掺金刚石的合成与表征

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张浩波（2001－），男，硕士研究生，主要从事金刚石晶体的高温高压合成与性能研究. E-mail：2213639769@qq.com

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张浩波, 胡美华, 李尚升, 刘迪, 和莎莎, 李晓晓, 王振阳

作者信息

河南理工大学材料科学与工程学院, 河南焦作　454003

通讯作者:

胡美华（1982－），男，博士，副教授，主要从事超硬材料的高压合成与性能研究. E-mail：humh@hpu.edu.cn

作者简介:

张浩波（2001－），男，硕士研究生，主要从事金刚石晶体的高温高压合成与性能研究. E-mail：2213639769@qq.com

Synthesis and Characterization of P-Doped Diamond Crystals in the FeNiCo-C System under High Temperature and High Pressure

Haobo ZHANG, Meihua HU, Shangsheng LI, Di LIU, Shasha HE, Xiaoxiao LI, Zhenyang WANG

Affiliations

School of Materials Science and Engineering, Henan Polytechnic University, Jiaozuo 454003, Henan, China

出版时间: 2026-09-05 doi: 10.11858/gywlxb.20251285

文章导航

摘要

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为探究磷掺杂对金刚石晶体生长的影响，在5.5 GPa、1 300 ℃的条件下，将Fe₃P掺入FeNiCo-C体系中，采用温度梯度法沿(111)晶面合成了磷掺杂金刚石单晶。对合成的金刚石样品进行傅里叶变换红外光谱、拉曼光谱、光致发光光谱以及X射线光电子能谱测试。随着Fe₃P添加量的上升，金刚石晶体颜色逐渐变浅，晶体结构由八面体向六-八面体转变。金刚石晶体中氮杂质含量随着Fe₃P添加量的上升呈下降趋势，原因是Fe₃P的掺入改变了触媒特性，使触媒的氮溶解度增加，从而减少了进入金刚石内部的氮原子数量。磷掺杂会使金刚石晶体内应力增大，产生晶格畸变，降低金刚石质量，这一结论可通过金刚石拉曼峰位偏移和半高宽变化得到证实。磷原子的掺入不利于金刚石晶体中NV⁻色心的形成。X射线光电子能谱测试结果证实，磷元素成功进入金刚石晶体内部。研究成果可为完善磷掺杂金刚石晶体合成机理以及推动磷掺杂金刚石晶体的潜在应用提供参考。

关键词

高温高压 / 金刚石单晶 / 超硬材料 / 磷掺杂 / n型半导体

Abstract

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To investigate the effects of phosphorus doping on diamond crystal growth, diamond single crystals doped with phosphorus were synthesized along the (111) plane using the temperature gradient method. The experiments were conducted under conditions of 5.5 GPa and 1 300 ℃, with Fe₃P added into the FeNiCo-C system. The synthesized diamond samples were characterized by Fourier-transform infrared (FTIR) spectroscopy, Raman spectroscopy, photoluminescence (PL) spectroscopy, and X-ray photoelectron spectroscopy (XPS). With increasing Fe₃P addition, the diamond color gradually lightens, and the crystal morphology changes from octahedral to hexoctahedral. Moreover, the addition of Fe₃P alters the catalyst properties, leading to the increases of nitrogen solubility of the catalyst. Thus, fewer nitrogen atoms enter the diamond lattice, resulting in a decrease of nitrogen impurity content in the diamonds. Phosphorus doping increases internal stress and induces lattice distortion in the diamond crystal, resulting in degrading of the diamond quality. This conclusion is supported by the shift and broadening of the Raman peak. The incorporation of phosphorus atoms inhibits the formation of NV⁻ centers in diamond crystals. XPS results confirm the successful incorporation of phosphorus into the diamond lattice. This study provides useful insights for understanding the synthesis mechanism of phosphorus-doped diamond crystals, and supports potential applications of phosphorus-doped diamond crystals.

Key words

high-temperature and high-pressure / diamond single crystal / superhard materials / phosphorus doping / n-type semiconductor

引用本文

张浩波, 胡美华, 李尚升, 刘迪, 和莎莎, 李晓晓, 王振阳. 高温高压下FeNiCo-C体系中磷掺金刚石的合成与表征. 高压物理学报, 2026 , 40 (9) : 090113-1 -090113-9 . DOI: 10.11858/gywlxb.20251285

Haobo ZHANG, Meihua HU, Shangsheng LI, Di LIU, Shasha HE, Xiaoxiao LI, Zhenyang WANG. Synthesis and Characterization of P-Doped Diamond Crystals in the FeNiCo-C System under High Temperature and High Pressure[J]. Chinese Journal of High Pressure Physics, 2026 , 40 (9) : 090113-1 -090113-9 . DOI: 10.11858/gywlxb.20251285

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金刚石因具有高硬度、高导热性、宽透光波段、高载流子迁移率和耐腐蚀等突出优势，被广泛应用于航空航天、国防、机械加工等领域^[1–6]，在电子器件应用方面也拥有巨大的潜力。在金刚石大单晶的合成过程中，科研人员通过有目的地向金刚石晶格中掺入杂质来改变金刚石的性能^[7]。该技术可用于开发具有特殊性能的金刚石晶体，以满足实际生产需求。目前，针对掺杂硼（B）元素的p型金刚石的研究已较为成熟，但n型半导体金刚石的制备一直是一个具有挑战性的课题。这主要是由于，在施主元素掺杂过程中存在固溶度低和施主能级深等难题，从而限制了该领域的进展。磷（P）被认为是最佳的单元素施主杂质，其在金刚石晶体中可产生n型导电且施主能级较浅。目前，对于磷掺杂金刚石晶体的研究主要集中在化学气相沉积法合成的金刚石薄膜上^[8–10]。虽然高温高压（high pressure and high temperature, HPHT）合成金刚石技术凭借其易于产业化、生产成本低等技术优势，在人工金刚石晶体合成方面处于不可替代的地位，但高温高压条件下合成磷掺杂金刚石仍是一个尚未被深入探索的领域。在HPHT条件下合成磷掺杂金刚石晶体方面：Hu等^[11]将红磷加入FeNi-C体系中，发现磷的添加改变了金刚石的生长条件，导致晶体表面更粗糙且内部缺陷增加；Palyanov等^[12]采用磷单质为掺杂剂合成了磷掺杂金刚石晶体，得到了磷掺入金刚石的效率随着生长温度降低而提高的结论；Gong等^[13]合成了磷掺杂金刚石晶体，对样品进行了拉曼光谱测试，证明随着磷掺杂含量的上升，金刚石中的缺陷和杂质原子也会增加。Yu等^[14]使用Mn₃P₂作为磷源开展了合成金刚石晶体实验，相较于磷单质作为磷源所合成的金刚石，利用温度梯度法合成的磷掺杂金刚石晶体内的磷元素含量显著提升。Guo等^[15]采用高压热扩散方法制备了磷掺杂金刚石，通过高压缩小掺杂原子与碳原子之间的体积差，并利用热扩散将磷杂质掺入金刚石。Guo等^[16]以Fe₃P作为磷源加入FeNi-C体系中合成金刚石晶体，在成功合成磷掺杂金刚石的基础上，避免了额外杂质引入。

上述研究大多在FeNi-C体系以及NiMnCo-C体系中掺入磷源合成磷掺杂金刚石晶体。众所周知，合金触媒中较高的镍含量会提高金刚石晶体的合成效率，但镍元素对氮有较强的亲和力，触媒中镍元素比例过高时易将氮带入金刚石晶格，导致合成的金刚石晶形欠佳^[17]。因此，在兼顾金刚石合成效率的基础上，本研究拟在减少铁基触媒中镍比例的同时引入少量的钴，在高温高压条件下，将Fe₃P作为磷源加入FeNiCo-C体系中合成磷掺杂金刚石晶体，并揭示磷杂质对金刚石晶体形貌、氮杂质含量、结晶质量以及内部NV⁻色心零声子线强度的影响，以期为掺磷金刚石的应用提供有价值的技术支持，并完善磷掺杂金刚石的生长机制。

1 实　验

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本实验采用温度梯度法，在国产六面顶压机（SPD-6×1200型）中进行。在1 300 ℃、5.5 GPa的高温高压条件下，以高纯石墨（纯度为99.9%，麦克林）为碳源，以FeNiCo合金（Fe、Ni、Co的质量比为54∶29∶17）为触媒进行磷掺杂金刚石晶体合成实验。为避免在金刚石合成过程中引入额外的杂质元素，以高纯Fe₃P粉（纯度为99.5%，麦克林）为添加剂，将尺寸为0.6～0.8 mm的合成金刚石作为籽晶，并以其(111)面作为初始生长晶面，生长时间均为12 h。合成组装如图1所示。实验中，通过铋（Bi）、钡（Ba）以及铊（Tl）在特定压力下发生的相变对合成压力进行标定；通过Pt-Rh30%/Pt-Rh6%热电偶的电动势与温度的对应关系标定合成温度^[18]。

实验结束之后，将取出的样品放入煮沸的稀硝酸中去除金属触媒，随后将金刚石晶体放入硝酸和硫酸混合溶液（硫酸与硝酸的体积比为3∶1）中去除晶体表面残留的石墨。使用光学显微镜确认晶体形貌。借助傅里叶变换红外（Fourier transform infrared, FTIR）光谱检测金刚石晶体内部N的含量以及N存在的状态；使用拉曼（Raman）光谱对晶体质量进行表征，采用液氮冷却的CCD相机记录信号，光谱分辨率设置为1 cm⁻¹，波长为532 nm；使用光致发光（photoluminescence, PL）光谱研究晶体内部NV⁻色心零声子线强度，其激光波长为532 nm；使用X射线光电子能谱（X-ray photoelectron spectroscopy, XPS）探究晶体内部磷原子的存在形式。

2 结果与讨论

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图2展示了1 300 ℃、5.5 GPa高温高压条件下，FeNiCo-C体系中添加不同质量分数（占碳源）的高纯Fe₃P粉末时，沿(111)面生长的Ⅰb型金刚石晶体。各个晶体的Fe₃P添加量和金刚石晶体生长结果如表1所示。

观察金刚石晶体的光学照片可以看出，随着Fe₃P掺杂质量分数的增加（1%～8%），金刚石晶体的晶型由八面体转化为六-八面体直至变为骸晶。同时可以看出，样品A～样品D的晶型主要以(111)面为主，这是因为，在金刚石生长过程中，各晶面趋向于能量最低的状态，而金刚石中的(111)面是碳原子密堆积面，因此，(111)晶面的能量最低^[19]，从而出现了随着Fe₃P掺杂质量分数的增加，金刚石晶体的生长更加趋向于(111)面的情况。当Fe₃P掺杂质量分数增加到8%时，金刚石晶体转变成骸晶，这是由于磷的原子半径大于碳原子，掺杂后在晶体结构中诱导产生过饱和空位。这些过饱和空位在高温高压条件下会聚集塌陷形成位错线，导致晶体内部出现位错界面，为骸晶的形成提供了条件^[20]。在金刚石晶体的生长过程中，作为杂质的磷原子会导致碳原子层堆叠结构遭到破坏，引起晶体内部应力集中并产生晶格畸变，最终导致金刚石晶体转变为骸晶。

先前的研究已经证实，金刚石合成压力不变但温度升高时，沿(111)面生长的金刚石晶体会从六面体转变为六-八面体直至八面体^[21]。在本研究中，合成压力和温度不变的条件下，随着Fe₃P掺杂质量分数的增加，晶体从八面体转变为六-八面体直至骸晶，这种现象产生的原因是：Fe₃P的加入使金刚石晶体生长的“V型区”上移^[22]。当使用Fe、Ni、Co、Mn及其合金在内的过渡金属元素作为金刚石晶体合成过程的触媒时，会降低石墨向金刚石转化所需的温度和压力。相比之下，磷作为非金属元素进入合金催化剂中时，会使晶体生长所需的合成温度和压力升高^[23]。由此可以得到，Fe₃P改变金刚石晶体生长“V型区”的机理是：Fe₃P的掺入改变了触媒活性及其对石墨的溶解度，从而使金刚石生长的“V型区”上移。

同时，可以观察到，随着Fe₃P质量分数的增加，金刚石晶体颜色逐渐变浅，内部包裹体数量增多。众所周知，Ⅰb型金刚石晶体的颜色在一定程度上受晶格中离散态孤氮原子（C心）的影响。因此，可以推测，随着Fe₃P质量分数的增加，磷掺杂金刚石晶体中的C心含量降低，这一假设通过FTIR表征结果得到了证实。

在不破坏金刚石晶体的前提下，FTIR测试能够有效地识别金刚石内部的杂质元素及其存在形式，因此，采用FTIR对金刚石晶体的氮杂质进行测试和分析。图3展示了掺磷金刚石晶体的红外光谱测试结果。金刚石的特征峰分别位于1 970、2 030和2 160 cm^–1，它们均由C―C键的振动引起^[24–25]。位于1 130和1 344 cm^–1的峰为C心相关特征峰，且图3中并未出现聚集态氮原子A心相关峰（1 282 cm^–1）和B心相关峰（1 175 cm^–1），未识别出的原因可能是由于金刚石晶体样品中A心和B心的浓度低于检测线，因此，将C心含量作为晶体中总的氮含量。

根据红外光谱测试得到的数据，计算该批金刚石晶体的氮含量，计算公式^[26–27]为

(1)

$ {C}_{\text{N}}= 5.5\times 25\times10^{-6}\times\mu ({\text{1 130 cm}}^{-1})/\mu ({\text{2 120 cm}}^{-1}) $

(2)

$ \mu ({\text{1 130 cm}}^{-1})=[A({\text{1 290 cm}}^{-1})-A({\text{1 370 cm}}^{-1})]/0.31 $

(3)

$ \mu {(2\;120\;{\mathrm{ cm}}^{-1})=[40}A{(2 \;030\; {\mathrm{cm}}^{-1})+87} A{(2\;160 \;{\mathrm{cm}}^{-1})]/127-}A{(2\;120 \;{\mathrm{cm}}^{-1})} $

式中：C_N为C心浓度（因测试晶体样品中未检测出A心和B心，所以C心浓度即为晶体中总的氮浓度），μ为对特征峰的吸收系数，A为相应特征峰的吸收强度。

表2展示了各个金刚石晶体中N含量的计算结果。从表2可以看出，金刚石晶体样品中的氮含量随着Fe₃P掺入质量分数的增加呈下降趋势，说明磷元素的掺入抑制了氮元素进入金刚石晶格。引起金刚石晶体N含量改变主要有引入额外的N源和改变合金触媒溶剂对N原子的溶解度^[28]2个原因。当触媒对氮杂质的溶解度升高时，会使进入金刚石晶体中的氮原子减少，反之亦然。因此，本研究中观察到的金刚石晶体中氮含量变化的原因是：磷元素进入合成体系中时会影响合金触媒的溶氮能力以及熔融态触媒的流动性，从而使金属触媒对氮的溶解度上升^[29]，造成进入金刚石晶体中的氮杂质数量减少，这一效应在磷掺杂金刚石晶体上的宏观表现为随着Fe₃P掺杂量的上升，晶体颜色逐渐变浅。

本研究通过对金刚石晶体进行拉曼光谱分析探究磷含量变化对金刚石晶体内部结构的影响。图4展示了Fe₃P质量分数对金刚石晶体的拉曼峰位及半高宽（full width at half maximum, FWHM）的影响。由图4(a)和图4(b)可知，磷掺杂金刚石单晶的拉曼光谱呈现出高信噪比，谱图中仅在1 332.0 cm^–1附近存在一个强且尖锐的峰，该峰明确归属于金刚石的典型拉曼特征峰，由C―C键的sp³杂化引起。随着Fe₃P质量分数的持续上升，金刚石晶体的特征峰强度会逐渐减弱，与Yan等^[30]的研究成果相吻合。当Fe₃P的质量分数为1%、2%、4%和6%时，对应的金刚石晶体的拉曼特征峰分别位于1 331.85、1 331.69、1 331.57和1 331.44 cm^–1，金刚石晶体特征峰的半高宽分别为7.09、7.14、7.18和7.22 cm^–1，随着Fe₃P添加质量分数的上升，金刚石晶体特征峰持续向左偏移，且金刚石晶体特征峰的半高宽逐渐变大。金刚石的拉曼峰位及其半高宽与晶体质量有关，当晶体中晶格缺陷变多、晶体内部应力增加、晶格畸变程度增加时，晶体品质变差，体现在拉曼光谱中是峰位偏移和半高宽增大^[31–32]。

不同Fe₃P质量分数的金刚石晶体内部应力可以表示为

(4)

$ {\sigma }_{\text{h}}=({\gamma }_{0}-\gamma )/2.88 $

式中：σ_h为晶体中的残余应力，γ₀为未掺杂的高质量金刚石的拉曼峰位（1 332.0 cm⁻¹），γ为测得的拉曼峰位。计算所得的正负代表应力方向，其中，正号代表压应力，负号代表拉应力，计算结果如表3所示。

由表3可知，随着触媒中Fe₃P质量分数的提高，金刚石晶体中的内应力不断增大。结合以上结果可以看出，触媒中Fe₃P添加量的上升同样会引起金刚石晶体的拉曼峰位左移及其FWHM变大。我们认为造成该现象的内在机理是：在合成金刚石晶体过程中引入磷元素时，因磷的原子半径大于碳原子，且C―P键的键长大于C―C键的键长，这直接影响金刚石晶体中sp³键碳原子之间的距离，使金刚石晶体内部产生应力从而导致晶格畸变。尽管这些晶体的特征峰发生了偏移，半高宽有所增大，但掺杂后的晶体仍然具有明显的金刚石特征峰，说明磷掺杂金刚石仍具有典型的sp³结构。

本研究采用PL光谱探究金刚石晶体中氮相关空位色心。图5展示了磷掺杂金刚石的PL光谱测试结果。由图5可知，磷掺杂金刚石在572 nm处均出现了强烈的金刚石一阶拉曼位移峰，并在612 nm处出现了金刚石的二阶拉曼位移峰。此外，在637和660 nm处也存在2条零声子线，637 nm峰对应NV⁻色心，660 nm峰则对应带负电的取代镍（W8色心）^[33–34]。从图5还可以看出，随着Fe₃P添加量的不断增加，对应NV⁻色心的637 nm处峰强度不断减弱，直至NV⁻色心数量低于检测限，637 nm处峰信号消失。这些结果表明，晶体合成过程中，较高的磷掺杂量不利于金刚石中NV⁻色心的形成。结合FTIR光谱测试中对氮杂质含量的计算来分析，NV⁻色心数量减少的原因是：随着磷掺杂量的不断提高，金刚石晶体中的氮杂质数量不断减少，从而引起氮相关空位色心数量不断下降。

X射线光电子能谱（X-ray photoelectron spectroscopy, XPS）可准确反映金刚石晶体中元素的结合能及相应的化学价态。本研究通过XPS分析C1s、N1s和P2p的高分辨率能谱，以确定晶体中是否存在磷元素。图6展示了Fe₃P质量分数为2%的金刚石晶体的XPS测试结果。

图6(a)、图6(b)和图6(c)分别展示了Fe₃P质量分数为2%的金刚石晶体的C1s、N1s和P2p的XPS。拟合后的C1s的谱图中出现了284.8、285.5、286.5和288.2 eV 4个信号峰，分别对应C―C、C―N、C―O和C＝O键。拟合后的N1s的谱图中出现了399.7和401.2 eV 2个信号峰，分别对应N―C和N―N键。拟合后的P2p的谱图中出现了133.1和134.1 eV 2个信号峰，分别对应P―C 2p_3/2键和P―C 2p_1/2键^[15]。这表明磷元素进入金刚石晶体内部，证实本实验成功合成了磷掺杂金刚石。

值得注意的是，磷在金刚石晶体中作为替代式杂质时会提供一个深施主能级，表明室温下只有少数的磷原子能够电离并向导带提供自由电子，导致电阻率较大。下一步尝试使用协同掺杂的方法对金刚石电学性能进行优化。

3 结　论

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采用温度梯度法，在1 300 ℃、5.5 GPa的高温高压条件下，将Fe₃P掺入FeNiCo-C体系中，以(111)面为生长面合成了磷掺杂金刚石晶体，探究了磷杂质对金刚石生长的影响，得到以下主要结论：

(1) 随着磷添加量的增加，晶体颜色会逐渐变浅，且晶型由八面体转化为六-八面体直至变为骸晶；

(2) FTIR光谱分析表明，磷元素的添加降低了金刚石晶体中的氮浓度；

(3) 拉曼光谱分析表明，合成体系中磷原子的引入会使金刚石晶体内部应力增加，晶体质量下降。

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文献

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2026年第40卷第9期

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doi: 10.11858/gywlxb.20251285

接收时间：2025-12-26
首发时间：2026-11-05
出版时间：2026-09-05

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收稿日期：2025-12-26
修回日期：2026-02-08
录用日期：2026-07-14

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河南理工大学材料科学与工程学院, 河南焦作　454003

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胡美华（1982－），男，博士，副教授，主要从事超硬材料的高压合成与性能研究. E-mail：humh@hpu.edu.cn

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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