Article(id=1325123333762724646, tenantId=1146029695717560320, journalId=1255847867265597444, issueId=1325123175192855060, articleNumber=null, orderNo=null, doi=10.11858/gywlxb.20251248, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1762185600000, receivedDateStr=2025-11-04, revisedDate=1763654400000, revisedDateStr=2025-11-21, acceptedDate=null, acceptedDateStr=null, onlineDate=1793863622369, onlineDateStr=2026-11-05, pubDate=1788537600000, pubDateStr=2026-09-05, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1793863622369, onlineIssueDateStr=2026-11-05, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1793863622369, creator=13701087609, updateTime=1793863622369, updator=13701087609, issue=Issue{id=1325123175192855060, tenantId=1146029695717560320, journalId=1255847867265597444, year='2026', volume='40', issue='9', pageStart='090101-1', pageEnd='090114-12', issueExtLink='null', onlineDate='null', pubDate='1788537600000', pubDateStr='2026-09-05', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=0, createTime=1793863584564, creator='13701087609', updateTime=1793864402827, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1325126607446356730, tenantId=1146029695717560320, journalId=1255847867265597444, issueId=1325123175192855060, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1325126607450551035, tenantId=1146029695717560320, journalId=1255847867265597444, issueId=1325123175192855060, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=090103-1, endPage=090103-18, ext={EN=ArticleExt(id=1325123336199615271, articleId=1325123333762724646, tenantId=1146029695717560320, journalId=1255847867265597444, language=EN, title=Research Progress on Two-Dimensional Diamond, columnId=1325123176816050710, journalTitle=Chinese Journal of High Pressure Physics, columnName=Carbon under High Pressure, runingTitle=null, highlight=null, articleAbstract=

Two-dimensional (2D) diamond, an atomically thin carbon-based material, not only inherits the exceptional properties of bulk diamond but is also expected to exhibit unique physical characteristics arising from nanoscale effects. Currently, research on 2D diamond remains in its infancy, being primarily driven by theoretical investigations, while experimental efforts have mainly focused on its controllable synthesis and structural characterization. Owing to pronounced interfacial effects, the direct application of conventional high-pressure synthesis methods to nanoscale systems is considerably limited, making it challenging to achieve a stable transition from sp2 to sp3 hybridization, thereby posing numerous critical scientific challenges for the study of 2D diamond. This review systematically summarizes recent theoretical and experimental advances in the structural features, synthesis strategies, and physicochemical properties of 2D diamond, and provides perspectives on future research directions and scientific opportunities in the field of 2D diamond.

, authors=Jiaxin MING1, 2, Jiayin LI1, 2, Yabin CHEN1, 2, authorsList=Jiaxin MING, Jiayin LI, Yabin CHEN, authorCompany=null, correspAuthors=Yabin CHEN, authorNote=null, correspAuthorsNote=null, copyrightStatement=Copyright © 2026 Chinese Journal of High Pressure Physics. All rights reserved., copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1325123349654942524, articleId=1325123333762724646, tenantId=1146029695717560320, journalId=1255847867265597444, language=CN, title=二维金刚石的研究进展, columnId=1325123177629745688, journalTitle=高压物理学报, columnName=高压下的碳材料, runingTitle=null, highlight=null, articleAbstract=

二维金刚石作为一种新型的原子级超薄碳基材料,不仅继承了块体金刚石的优异性能,且有望展现出因量子尺度效应带来的独特物性。当前,二维金刚石研究仍处于以理论探索为主的起步阶段,实验研究则集中于可控制备与结构验证。受表界面效应及尺寸效应的多重影响,传统高压合成方法难以在纳米碳材料中直接实现由石墨烯中sp2向sp3杂化的高效稳定转化,这为二维金刚石研究带来了诸多亟待解决的关键科学问题。系统总结了近年来二维金刚石在结构特征、合成策略及物理化学性质等方面的理论与实验研究进展,并对二维金刚石未来的发展方向与潜在的应用场景进行了展望。

, authors=明嘉欣1, 2, 李嘉荫1, 2, 陈亚彬1, 2, authorsList=明嘉欣, 李嘉荫, 陈亚彬, authorCompany=null, correspAuthors=陈亚彬, authorNote=

明嘉欣(2000-),女,博士研究生,主要从事类金刚石材料研究. E-mail:

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陈亚彬(1984-),男,博士,教授,主要从事高压材料物理研究. E-mail:
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Nanotechnology, 2020, 31(33): 335711., articleTitle=null, refAbstract=null)], funds=null, companyList=[AuthorCompany(id=1325123351802426175, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, xref=1, ext=[AuthorCompanyExt(id=1325123352125387584, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, companyId=1325123351802426175, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China), AuthorCompanyExt(id=1325123352616121153, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, companyId=1325123351802426175, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1北京理工大学化学与化工学院, 北京 100081)]), AuthorCompany(id=1325123353434010434, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, xref=2, ext=[AuthorCompanyExt(id=1325123353496924995, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, companyId=1325123353434010434, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2School of Interdisciplinary Science, Beijing Institute of Technology, Beijing 100081, China), AuthorCompanyExt(id=1325123353819886404, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, companyId=1325123353434010434, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2北京理工大学前沿交叉科学院, 北京 100081)])], figs=[ArticleFig(id=1325123368554476389, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, language=EN, label=Fig. 1, caption=Atomic structures and schematic diagram of two-dimensional diamond (diamane): (a) graphane[26]; (b) diamane-I with AB stacking[26]; (c) diamane-Ⅱ with AA stacking[26]; atomic structures and electron localization functions of (d) non-Janus (C2X, X = H, F, Cl) and (e) Janus diamane (C4XY, X≠Y=H, F, Cl) [30], figureFileSmall=WprNsi7RdiLt5nurPrDy7A==, figureFileBig=4s/aQ+nijPT4+61gbZASFQ==, tableContent=null), ArticleFig(id=1325123368646751078, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, language=CN, label=图1, caption=二维金刚石的多样结构及其示意图:(a)石墨烷结构示意图[26],(b) AB堆垛方式的氢化二维金刚石(Diamane-Ⅰ)结构模型[26],(c) AA堆垛方式的氢化二维金刚石(Diamane-Ⅱ)结构模型[26],(d) 非Janus型二维金刚石(C2X, X=H, F, Cl)和 (e) Janus型二维金刚石(C4XY, X≠Y=H, F, Cl)的结构和电子态分布[30], figureFileSmall=WprNsi7RdiLt5nurPrDy7A==, figureFileBig=4s/aQ+nijPT4+61gbZASFQ==, tableContent=null), ArticleFig(id=1325123369326228327, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, language=EN, label=Fig. 2, caption=Theoretical calculations of the transition from FLG to 2D diamond: (a) atomic configurations of FLG and the corresponding diamond films with pristine and hydrogenated surfaces, along with the pressure-temperature phase diagram[17]; (b) Gibbs free energy evolution (ΔG) of hydrogenated (top) and fluorinated (bottom) as a function of the number of adsorbed atoms at ambient conditions[37]; (c) the dependences of formation energy and interlayer C―C spacing of BLG on Co (0001) on hydrogen coverage[38]; (d) formation energy of fully hydrogenated BLG on Co (0001) as a function of film thickness (Solid and open symbols correspond to the cubic and hexagonal diamond, respectively.)[38], figureFileSmall=L27JlxOHDVS8NmCuc5C5CQ==, figureFileBig=lVKAq0tjDH3zbDH3UWz5+w==, tableContent=null), ArticleFig(id=1325123369460446057, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, language=CN, label=图2, caption=FLG向二维金刚石转变的理论计算结果:(a)未修饰与表面修饰的多层石墨烯及其相应金刚石薄膜的结构示意图,以及随层数依赖的压力-温度相图[17];(b)常压下不同层数氢化(上)、氟化(下)石墨烯的相对吉布斯自由能ΔG随吸附原子数目的变化关系[37];(c) Co (0001)表面上氢化BLG的形成能(实心)及C―C层间距(空心)随吸附氢覆盖度的变化关系[38];(d) Co (0001)表面上完全氢化的BLG的形成能随厚度的变化关系(实心与空心符号分别对应立方和六方金刚石)[38], figureFileSmall=L27JlxOHDVS8NmCuc5C5CQ==, figureFileBig=lVKAq0tjDH3zbDH3UWz5+w==, tableContent=null), ArticleFig(id=1325123371490489195, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, language=EN, label=Fig. 3, caption=Experimental formation of hydrogenated 2D diamond: (a) typical infrared absorption spectrum of FLG after hydrogenation[47]; (b) ultraviolet (UV) Raman spectrum of hydrogenated FLG (The appearance of T band and the crystalline sp3-C peak indicate the formation of 2D diamond)[47]; (c) representative UV Raman spectrum of hydrogenated BLG, exhibiting a distinct sp3-C stretching feature[48]; (d) TEM image and corresponding SAED pattern of hydrogenated BLG[48], figureFileSmall=aT0Rw4253tmff/P626eKVQ==, figureFileBig=QTXjwVqSHLw9KK1rPXxGqA==, tableContent=null), ArticleFig(id=1325123371876365164, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, language=CN, label=图3, caption=氢化二维金刚石的实验制备:(a) FLG氢化后的红外吸收光谱[47];(b) FLG氢化后的紫外拉曼光谱(T峰和结晶sp3-C峰的出现表明形成了氢化二维金刚石)[47];(c)氢化后BLG的典型紫外拉曼光谱,其具有明显的sp3-C伸缩振动特征峰[48];(d)氢化后双层石墨烯薄膜的TEM图像及相应的SAED图[48], figureFileSmall=aT0Rw4253tmff/P626eKVQ==, figureFileBig=QTXjwVqSHLw9KK1rPXxGqA==, tableContent=null), ArticleFig(id=1325123372371293037, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, language=EN, label=Fig. 4, caption=Experimental characterization of fluorinated 2D diamond: (a) XPS C1s spectrum of BLG after fluorination[22]; (b) cross-sectional HRTEM result of fluorinated BLG on the CuNi (111) and the corresponding DFT-simulated TEM images[22]; (c)−(d) in-situ Raman spectra of BLG during the fluorination on different substrates, showing double-sided fluorination on SiO2 and single-sided fluorination on hBN[54]; (e) TEM image of (C2F)n nanosheets obtained via liquid-phase exfoliation (The inset reveals the interlayer spacing is approximately 0.9 nm.)[55], figureFileSmall=7jdvYZsao7frnOtqHEvzpw==, figureFileBig=Vza6XahVP+3Wf2vU1/7qzQ==, tableContent=null), ArticleFig(id=1325123373122073454, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, language=CN, label=图4, caption=氟化二维金刚石的实验研究:(a) 氟化二维金刚石C1s的XPS光谱[22];(b) CuNi (111)基底上双层石墨烯氟化后的截面HRTEM图像及其DFT模拟结果[22];(c)~(d) 基底效应及不同基底表面双层石墨烯氟化过程的原位拉曼光谱,即 SiO2基底上的双面氟化和 hBN基底上的单面氟化[54];(e) 液相剥离得到的(C2F)n薄片TEM图像(插图为其边缘结构放大图,层间距约为0.9 nm)[55], figureFileSmall=7jdvYZsao7frnOtqHEvzpw==, figureFileBig=Vza6XahVP+3Wf2vU1/7qzQ==, tableContent=null), ArticleFig(id=1325123373218542447, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, language=EN, label=Fig. 5, caption=Localized pressure induced graphene to 2D diamond: (a) schematic illustration of the EFM experimental technique[21]; (b) EFM responses |Δω| of monolayer (square) and bilayer (circle) graphene on a SiOₓ substrate as a function of the applied force F[21]; (c) EFM responses of FLG at different temperatures (The inset shows the EFM response of FLG as a function of duration time.)[21]; (d) schematic of the AFM tip indenting the epitaxial BLG on SiC surface and the corresponding pressure-induced 2D diamond formation[40]; (e) AFM topographical images of residual indentation morphologies of 2L graphene and SiC[40]; (f) cross-sectional profiles of residual indentations in 2L, 5L graphene and SiC[40]; (g) average current as a function of normal load measured by C-AFM on 2L, 5L graphene films[40], figureFileSmall=0X5DEPtNiVnS8m3dcxnt+w==, figureFileBig=2ygmwZt9vLWXjGM7otfOwQ==, tableContent=null), ArticleFig(id=1325123373621195632, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, language=CN, label=图5, caption=局部压力诱导的石墨烯向二维金刚石转变:(a) EFM实验技术示意图[21],(b) SiOx基底上单层(方形)和双层(圆圈)石墨烯的EFM响应|Δω|随压力F的变化[21],(c) FLG在不同温度下的EFM响应(插图为EFM响应随加热时间的变化)[21],(d)双层石墨烯在SiC基底上的纳米压痕示意图及压力诱导的二维金刚石结构模型[40],(e) 纳米压痕后双层石墨烯和SiC基底的残余压痕形貌[40],(f) 双层、5层石墨烯和SiC基底中残余压痕的横截面轮廓[40],(g) C-AFM测得的双层与5层石墨烯的平均电流随法向载荷的依赖关系[40], figureFileSmall=0X5DEPtNiVnS8m3dcxnt+w==, figureFileBig=2ygmwZt9vLWXjGM7otfOwQ==, tableContent=null), ArticleFig(id=1325123374032237425, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, language=EN, label=Fig. 6, caption=Hydrostatic pressure induced transformation of graphene into 2D diamond in DAC; (a) schematic illustration of the in-situ high pressure Raman experimental technique in a DAC[23]; (b) pressure dependence of the G-band frequency difference (ΔωG=ωG(EL=2.54 eV)– ωG(EL=2.33 eV)) for BLG[23]; (c) schematic illustration of the formation of hydroxyl functionalized 2D diamond. (The blue, red, and gray spheres represent H, O, and C atoms, respectively)[23]; (d) schematic diagram of the four-terminal graphene nanodevice of graphene in the DAC[68]; (e) dependence of the transformation pressure from graphene to 2D diamond on layer number[69], figureFileSmall=rbOQEXCw1dKmJkKYSim/9w==, figureFileBig=k+Lvy8TcNfvh6a/hdyXrGQ==, tableContent=null), ArticleFig(id=1325123375684793202, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, language=CN, label=图6, caption=DAC极端高压诱导的石墨烯向二维金刚石转变:(a) DAC高压原位拉曼实验技术示意图[23];(b) 双层石墨烯的G峰频率差值ΔωG随压力的变化(ΔωG = ωG(EL=2.54 eV)– ωG(EL=2.33 eV))[23];(c)羟基化二维金刚石的形成过程示意图(蓝、红、灰球分别代表H、O和C原子)[23];(d) DAC中四端电学器件示意图[68];(e)石墨烯向二维金刚石的转变压力随层数的变化趋势[69], figureFileSmall=rbOQEXCw1dKmJkKYSim/9w==, figureFileBig=k+Lvy8TcNfvh6a/hdyXrGQ==, tableContent=null), ArticleFig(id=1325123376087446387, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, language=EN, label=Fig. 7, caption=Mechanical properties of diamane: (a) stress-strain curves of H-, F-, and Cl-diamane with different layer numbers[73]; (b) stress-strain curves of AB- and AA-stacked H-diamane at 10 K[75]; (c) temperature dependence of the Young’s modulus of hydrogenated 2D diamond[75]; (d) comparison of the in-plane Young’s modulus (E), shear modulus (G) and Poisson’s ratio (ν) among different 2D carbon nanomaterials[73, 77–80], figureFileSmall=nbBN0pioBCAgO61YI8ELJQ==, figureFileBig=xNeYv/qcYdvUUd9S3pqVEw==, tableContent=null), ArticleFig(id=1325123376477516660, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, language=CN, label=图7, caption=二维金刚石的力学性质:(a)不同层数的氢化、氟化和氯化二维金刚石的应力-应变曲线[73],(b) AB与AA堆垛氢化二维金刚石在10 K下的应力-应变曲线[75],(c)不同晶向氢化二维金刚石的杨氏模量随温度的变化关系[75],(d) 不同二维碳材料在面内杨氏模量(E)、剪切模量(G)和泊松比(ν)等力学性能方面的对比分析[73, 77–80], figureFileSmall=nbBN0pioBCAgO61YI8ELJQ==, figureFileBig=xNeYv/qcYdvUUd9S3pqVEw==, tableContent=null), ArticleFig(id=1325123376871781237, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, language=EN, label=Fig. 8, caption=Electronic and optical properties of diamane: (a) band structures of H-, F-, and Cl-diamane[30]; (b) bandgap of H-diamane as a function of layer number N obtained by DFT (The dashed line represents the bandgap of bulk diamond. The red and blue symbols represent cubic and hexagonal diamond, respectively.); (c) relationship between carrier mobility (μ) and bandgap (Eg) of diamane, compared with bulk Ⅲ-Ⅳ semiconductors (The solid line follows the empirical relation $ \mu=0.83\times10^4E_{\mathrm{g}}^{-3/2} $. Electron (μe) and hole mobilities (μh) correspond to the red and blue symbols, respectively.)[78]; optical absorption spectra of H-, F-diamane (d) and Cl-diamane (e) predicted using the HSE06 method[73], figureFileSmall=KmTHNjExCFapAl1uu/HXZA==, figureFileBig=4p9caudjrpzpytZC13XIBw==, tableContent=null), ArticleFig(id=1325123377035359094, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, language=CN, label=图8, caption=二维金刚石的电学与光学性质:(a) 氢化(左)、氟化(中)和氯化(右)二维金刚石的能带结构[30];(b) DFT计算的氢化二维金刚石带隙Eg随层数N的变化(虚线表示计算所得的体相金刚石带隙,红色与蓝色分别对应立方和六方金刚石相);(c) 氟化和氢化二维金刚石中载流子迁移率μ与带隙Eg的关系,与传统Ⅲ-Ⅳ族半导体进行对比(实线表示经验关系$ \mu=0.83\times10^4E_{\mathrm{g}}^{-3/2} $。电子与空穴迁移率(μe、μh)分别为红色与蓝色符号)[78];基于HSE06方法预测的氢化、氟化(d)和氯化(e)二维金刚石的光吸收特性[73], figureFileSmall=KmTHNjExCFapAl1uu/HXZA==, figureFileBig=4p9caudjrpzpytZC13XIBw==, tableContent=null), ArticleFig(id=1325123377471566711, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, language=EN, label=Fig. 9, caption=Thermal conductivity of diamane: temperature-dependent thermal conductivity of H-diamane with AB (a) and AA (b) stacking configurations (The blue dashed line indicates the thermal conductivity of graphane, while the triangles and hexagons represent the experimentally measured values of bulk diamond.)[90]; (c) thermal conductivities of H- and F-diamane obtained based on the RTA (dashed lines) and the CGP (solid lines) methods[91]; (d) thermal conductivities of non-Janus and Janus diamanes as a function of temperature using MTP method[30], figureFileSmall=hagxR3nA6V5UEU8wtHt9hQ==, figureFileBig=m2Fmi6XOnwbcg6k6bXy5KQ==, tableContent=null), ArticleFig(id=1325123377727419256, tenantId=1146029695717560320, journalId=1255847867265597444, articleId=1325123333762724646, language=CN, label=图9, caption=二维金刚石的热导率:理论计算得到的AB堆垛(a) 与AA堆垛(b) 氢化二维金刚石热导率随温度的变化曲线(蓝色虚线为石墨烷热导率,三角形与六边形为实验测得的体相金刚石热导率)[90];(c) 不同堆垛氟化与氢化二维金刚石的热导率与温度的关系,并与RTA(虚线)与CGP(实线)计算结果作对比[91];(d) 基于MTP方法计算的非Janus与Janus二维金刚石热导率随温度变化关系[30], figureFileSmall=hagxR3nA6V5UEU8wtHt9hQ==, figureFileBig=m2Fmi6XOnwbcg6k6bXy5KQ==, tableContent=null)], attaches=null, journal=Journal(id=1255846718311514113, delFlag=0, nameCn=高压物理学报, nameEn=Chinese Journal of High Pressure Physics, nameHistory1=null, nameHistory2=null, issn=1000-5773, eissn=null, cn=51-1147/O4, coden=null, periodic=0, language=CN, oaType=null, ccby=null, superviseOffice=null, ownerOffice=null, pubOffice=null, editorOffice=null, officeType=null, aims=null, clcCode=null, officeProv=null, officeCity=null, officeAddr=null, officeZip=null, officeEmail=null, officePhone=null, editDirector=null, officeDirector=null, officeDirectorPhone=null, officeStaffNum=null, officeEmpNum=null, coverPicUrl=KWePOcsfwWv2cMGG6VIsRw==, journalPrice=null, startedYear=null, abbrevIsoEn=Chinese Journal of High Pressure Physics, journalRemark=null, publicationField=null, createdTime=1777346790154, updatedTime=1788952099200, createdBy=18614031015, 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二维金刚石的研究进展
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明嘉欣 1, 2 , 李嘉荫 1, 2 , 陈亚彬 1, 2
高压物理学报 | 高压下的碳材料 2026,40(9): 090103-1-090103-18
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二维金刚石的研究进展
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明嘉欣(2000-),女,博士研究生,主要从事类金刚石材料研究. E-mail:

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明嘉欣1, 2 , 李嘉荫1, 2, 陈亚彬1, 2
作者信息
  • 1北京理工大学化学与化工学院, 北京 100081
  • 2北京理工大学前沿交叉科学院, 北京 100081
通讯作者:
陈亚彬(1984-),男,博士,教授,主要从事高压材料物理研究. E-mail:
作者简介:

明嘉欣(2000-),女,博士研究生,主要从事类金刚石材料研究. E-mail:

Research Progress on Two-Dimensional Diamond
Jiaxin MING1, 2 , Jiayin LI1, 2, Yabin CHEN1, 2
Affiliations
  • 1School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China
  • 2School of Interdisciplinary Science, Beijing Institute of Technology, Beijing 100081, China
出版时间: 2026-09-05 doi: 10.11858/gywlxb.20251248
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二维金刚石作为一种新型的原子级超薄碳基材料,不仅继承了块体金刚石的优异性能,且有望展现出因量子尺度效应带来的独特物性。当前,二维金刚石研究仍处于以理论探索为主的起步阶段,实验研究则集中于可控制备与结构验证。受表界面效应及尺寸效应的多重影响,传统高压合成方法难以在纳米碳材料中直接实现由石墨烯中sp2向sp3杂化的高效稳定转化,这为二维金刚石研究带来了诸多亟待解决的关键科学问题。系统总结了近年来二维金刚石在结构特征、合成策略及物理化学性质等方面的理论与实验研究进展,并对二维金刚石未来的发展方向与潜在的应用场景进行了展望。

二维金刚石  /  石墨烯  /  纳米碳材料  /  金刚石对顶砧  /  高压科学  /  结构相变

Two-dimensional (2D) diamond, an atomically thin carbon-based material, not only inherits the exceptional properties of bulk diamond but is also expected to exhibit unique physical characteristics arising from nanoscale effects. Currently, research on 2D diamond remains in its infancy, being primarily driven by theoretical investigations, while experimental efforts have mainly focused on its controllable synthesis and structural characterization. Owing to pronounced interfacial effects, the direct application of conventional high-pressure synthesis methods to nanoscale systems is considerably limited, making it challenging to achieve a stable transition from sp2 to sp3 hybridization, thereby posing numerous critical scientific challenges for the study of 2D diamond. This review systematically summarizes recent theoretical and experimental advances in the structural features, synthesis strategies, and physicochemical properties of 2D diamond, and provides perspectives on future research directions and scientific opportunities in the field of 2D diamond.

two-dimensional diamond  /  graphene  /  nanocarbon materials  /  diamond anvil cell  /  high pressure science  /  structural phase transition
明嘉欣, 李嘉荫, 陈亚彬. 二维金刚石的研究进展. 高压物理学报, 2026 , 40 (9) : 090103-1 -090103-18 . DOI: 10.11858/gywlxb.20251248
Jiaxin MING, Jiayin LI, Yabin CHEN. Research Progress on Two-Dimensional Diamond[J]. Chinese Journal of High Pressure Physics, 2026 , 40 (9) : 090103-1 -090103-18 . DOI: 10.11858/gywlxb.20251248
自2004年石墨烯通过机械剥离技术被成功制备以来[1],二维材料因其独特的物理化学性质引起了研究者的广泛关注[2–6]。当功能材料的厚度降低至纳米尺度时,其维度变化引发的小尺寸效应、量子尺寸效应及表界面效应等使其展现出与体相材料截然不同的新奇性能。例如,当三维石墨被减薄至单层时,石墨烯材料呈现出超高的载流子迁移率、半整数量子霍尔效应以及非常规超导等新颖现象[1, 7–11]。受此启发,研究者相继拓展出多种超薄纳米材料,构建了二维材料家族,并进一步推动了新型二维碳同素异形体的探索与合成。众所周知,金刚石与石墨是碳的两种典型同素异形体。金刚石兼具超宽光学带隙、超高弹性模量(约1 TPa)、超高热导率(室温下约2200 W/(m·K))、生物相容性以及化学惰性等优异特性,可在高温、高频、大功率及强辐射等复杂工况下稳定工作,在量子信息、高性能器件与传感等前沿领域具有广阔的应用前景[12–16]。因此,研究人员也开始尝试制备原子级厚度的金刚石薄膜;然而,不同于石墨层间较弱的范德华相互作用,金刚石中碳原子通过三维共价键紧密连接,阻碍了块体金刚石直接的自上而下剥离;同时,纳米尺度下的石墨化效应也会阻碍其形成并导致结构不稳定[17–20]。近年来,已有不少理论和实验研究表明,通过施加机械应力、引入原子自由基、官能团修饰或采用物理-化学协同驱动等方法,可有效诱导石墨烯中碳原子发生从sp2向sp3的杂化转变,从而形成原子级厚度的金刚石结构[21–26]。自2007年石墨烷(graphane)[27]的结构首次在理论上被提出以来,人们陆续预测并发现了多种具有不同官能团组成和结构特征的二维sp3杂化碳材料,如Diamane[26]、Diamene[28]、Diamondol[21]、Diamondene[23]、Diamanoid[29]等,这些原子级厚度的类金刚石薄膜在本研究中统称为二维金刚石。
相较于前期综述文章,本文将基于最新研究进展,系统综述二维金刚石的主要研究脉络,深入探讨其结构特征、可控制备策略(包括化学修饰与高压诱导法等)及其物理化学性质,重点总结二维金刚石及其衍生结构的形成机理与关键性能,旨在为后期深入研究提供一定的理论框架指导,并有效促进其在光电子学、量子器件及极端环境工程中的实际应用。
图1[26, 30]为二维金刚石的多样结构及其示意图。二维金刚石作为一种新兴的类金刚石碳材料,其起源可追溯至对二维石墨烷中sp3碳结构的理论研究。早在2007年,Sofo等[27]基于第一性原理计算提出了一种全新的二维碳氢化合物石墨烷。该结构由单层石墨烯衍生而来,表面被氢原子完全覆盖,化学式为CH。在石墨烷中,所有碳原子均为sp3杂化,构成六边形的椅式构象,而氢原子则以交替方式键合于碳平面的上下两侧,如图1(a)所示。理论计算表明,在碳氢原子比为1∶1的烃类化合物中,石墨烷是最稳定的结构,其结合能甚至高于苯和乙炔。随后,在2009年,Elias等[31]通过石墨烯与氢等离子体反应,在实验上实现了石墨烷的合成,从而使石墨烯从高导电性的半金属转变为绝缘体。值得注意的是,该过程具有可逆性,经退火处理后石墨烷可恢复为原始石墨烯。
受石墨烷启发,2009年Chernozatonskii等[26]提出了一种基于双层石墨烯(bilayer graphene,BLG)的新型层状结构C2H,并将其命名为二维金刚石(diamane-Ⅰ)。与石墨烷的结构类似,二维金刚石中每个碳原子均处于sp3杂化状态,由氢原子吸附在BLG的外侧形成C―H极性共价键,未氢化的碳原子则通过层间C―C共价键相连,从而构建出氢化的二维金刚石结构,如图1(b)所示。此外,他们还提出了由AA堆垛的BLG氢化得到的另一种构型,并将其命名为二维金刚石-Ⅱ,如图1(c)所示。由AB堆垛BLG得到的结构类似于立方金刚石(111)晶面的二维立方金刚石,即二维金刚石-Ⅰ;由AA堆垛BLG得到的结构具有六方金刚石(0001)晶面结构的二维六方金刚石,即二维金刚石-Ⅱ。其中,二维金刚石-Ⅰ的形成能更低,碳层间的距离更短,在热力学上表现更稳定。值得注意的是,理论计算表明,二维金刚石的形成能低于石墨烷,说明其结构稳定性更高。此外,进一步的理论研究指出,存在多种晶面取向的二维金刚石,如(111)、(100)和(110)二维金刚石等[32–34]。
二维金刚石的化学结构具有很强的可拓展性。除H外,二维金刚石表面的悬挂键还可以通过多种功能团进行饱和,如卤化、羟基化或氨基化等[35–36]。按照二维金刚石两侧的官能团是否一致,可分为Janus型和非Janus型。Raeisi等[30]基于第一性原理计算,系统研究了非Janus型C2H、C2F、C2Cl及其对应的Janus型C4HF、C4HCl、C4FCl二维金刚石的化学结构与稳定性,图1(d)~图1(e)展示了几何优化后的化学结构和电子态分布。电子局域函数分析结果表明,这些二维金刚石中均存在较强的共价相互作用;同时,声子色散谱结果进一步表明,无论是氢、氟、氯功能化的非Janus型还是Janus型二维金刚石都表现出良好的稳定性,与功能团类别没有依赖性。与非Janus型结构相比,Janus型二维金刚石因两侧表面修饰不对称,展现出新颖的结构特性和潜在的物性调控能力,这为二维金刚石材料的设计提供了新的方向。
少层石墨烯(few-layer graphene,FLG)向二维金刚石转变的理论计算研究如图2[17, 37–38]所示。除层数与官能化外,基底效应在二维金刚石的成键势垒与最终构型等方面同样发挥了关键作用[38–40]。一方面,金属基底可以通过与石墨烯表面的悬挂键相互作用进而实现有效钝化;另一方面,石墨烯的顶面可暴露于活性气氛环境,从而协同推动其向金刚石结构的转变。Odkhuu等[38]基于第一性原理计算发现,过渡金属的引入不仅显著降低了氢化BLG向二维金刚石转变的反应势垒,还通过碳原子sp3杂化轨道与金属表面$ {d}_{{\textit{z}^{2}}} $轨道之间的波函数叠加,显著增强了所得二维金刚石的结构稳定性。进一步研究表明,Co (0001)基底上BLG的形成能及层间距随顶层氢覆盖度x的变化表现出较强的关联性,如图2(c)所示。其中,垂直虚线表示临界覆盖度(x=1/3),左下和右上插图分别展示了临界覆盖度以下(x=0.25)和以上(x=0.50)对应的产物结构。随着x的增加,形成能的绝对值逐渐增大,当x>1/3时,层间C―C键的形成导致层间距急剧收缩;而在低浓度区间,两层碳之间仍保持着范德华间距。此外,厚度对金属基底上氢化二维金刚石的稳定性亦具有重要影响。如图2(d)所示,当薄膜厚度不超过7层时,Co (0001)基底上sp3键合的二维金刚石薄膜在热力学与结构上均表现出良好的稳定性。图2(d)插图为Co基底上不同构型类金刚石薄膜的侧视图。
大量理论研究表明,在特定条件下,二维金刚石有望在常温常压下稳定存在;同时,石墨烯层数、表面原子键合程度及基底效应等因素对其转变势垒与临界压力具有显著影响[17, 35, 37–38, 41]。相关理论计算结果为理解二维金刚石的结构稳定性及其实验合成路径提供了重要的指导。然而,由于二维金刚石的制备涉及碳从sp2到sp3的杂化转变,这通常需要苛刻的外界激励,因此,从实验角度实现二维金刚石的可控制备仍面临着巨大挑战。近年来,随着高压技术和化学修饰方法的不断发展和进步,研究者逐步探索并实现了多种可行的二维金刚石合成路径,并通过多种表征手段部分验证了其几何结构与物理性能。
化学修饰法通过在碳骨架上引入杂原子或官能团,以诱导晶格重构和化学键的重新杂化。石墨烯表面可被诱导与自由基发生化学反应,这种反应能在无需施加极端压力或加热的条件下发生;通过降低碳原子向sp3杂化构型的转变能垒,从而在更温和的外部条件下实现碳原子的重构[42]。以下将通过氢化和氟化两类反应阐述二维金刚石的化学修饰合成方法。
氢原子官能团化是最早被理论预测能诱导sp2向sp3转化的化学修饰策略[43–45]。众所周知,C―H共价σ键及其对应的碳氢结构具有高度的热力学稳定性。基于C―H键的特殊性,理论工作者提出了石墨烷的概念,进一步推演出氢化二维金刚石的结构。鉴于理论计算成果,实验方面对氢化诱导成键及相变过程已进行了一定研究。
Luo等[46]系统研究了SiO2基底上不同层数石墨烯的氢化过程。拉曼光谱测试显示,氢化后2L~4L样品的D、D'峰增强,并出现D+G合频峰,表明形成了sp3杂化的C―H键。X射线光电子能谱(X-ray photoelectron spectroscopy,XPS)结果进一步证实,3层和5层样品中的sp3含量高于单层,说明单层石墨烯的氢化反应活性低于双层和多层样品。此外,该反应过程具有良好的可逆性,通过退火可实现结构恢复。为进一步探究氢化石墨烯向金刚石结构的转变机制,研究者们引入对相变高度敏感的紫外拉曼光谱技术,对氢化二维金刚石的形成过程进行了深入表征。2019年,Piazza等[47]报道了在FLG中从sp2到sp3转变的直接实验证据。如图3(b)所示,紫外拉曼光谱显示氢化后出现的2个新峰,归因于sp3 C―C键的伸缩振动,其中1063 cm−1峰对应于非晶碳膜中的T峰;1323 cm−1与氢化二维金刚石的理论预测值(1320 cm−1)较为吻合。红外光谱中在约2846 cm−1处的特征峰对应C―H伸缩振动,进一步验证了C―H键的存在(图3(a)),插图为C―H伸缩振动积分强度的显微图。对于层数大于3层的FLG,受堆垛方式限制,sp2-C到sp3-C的转化主要发生在表层,形成所谓的类金刚石结构(diamanoid)[29]。
2020年,Piazza等[48]进一步实现了BLG向二维金刚石的完全转化,并且首次给出了直观的拉曼光谱证据。氢化前,BLG的拉曼光谱在1582 cm−1处的尖峰源自于G峰,氢化后G峰消失;在1344~1367 cm−1范围内出现尖锐的拉曼散射峰(图3(c)),表明BLG已完全转化为真正的金刚石。但实验峰位略高于理论值,可能与堆垛方式差异以及残余应力等有关。同时,氢化的薄膜产物表面出现了裂纹(图3(d)),选区电子衍射图像(selected-area electron diffraction,SAED)亦显示样品内存在微小的扭转角(图3(d)),这些现象均可归因于应力的影响;更重要的是,SAED结果直接验证了二维金刚石的晶体结构。
与氢化相比,氟官能团化后的石墨烯具有多重优势。首先,C、H和F的电负性分别为2.5、2.2和4.0,因此C―F键的极性远强于C―H键。原子序数更大的F在成键后,可通过常规的表征手段直接检测,如XPS、能量色散X射线光谱和电子能量损失谱(electron energy-loss spectroscopy,EELS)等[47, 49]。此外,在气相反应中实现石墨烯的官能团化往往需要自由基参与,这些高活性的自由基需要通过加热、高压或等离子体等方法产生。与石墨烯的氢化过程相比,氟化反应在实验上更易实现,可在近室温与常/低压的温和条件下进行,例如,采用XeF2蒸气作为常见的氟源[22, 50–52]。理论研究表明,氟化体系的形成能显著低于氢化体系,说明氟化二维金刚石在热力学上更稳定,为化学合成sp3杂化石墨烯和二维金刚石提供了更可行的转化路径[32, 53]。目前,从实验策略而言,主要通过“自上而下”和“自下而上”两种方法制备氟化二维金刚石。
氟化二维金刚石的实验研究如图4所示[22, 54–55]。在“自下而上”方法中,Bakharev等[22]首次在常压条件下,将化学气相沉积(chemical vapor deposition,CVD)生长在CuNi (111)基底上的AB堆垛BLG暴露于XeF2蒸气中,实现了大面积、可控的氟化反应,成功合成了稳定的氟化二维金刚石(F-diamane)。基于密度泛函理论(density functional theory,DFT)计算,研究者优化了2种C2F构型,分别对应无层间成键和具有层间C―C共价键结构。计算结果表明,含层间成键构型的能量最低且最为稳定,从而排除了无层间键的C2F模型。进一步地,通过系列显微和光谱技术验证了该结构的存在。XPS分析显示,C1s能谱中C―F和C―CF(sp3)峰相较于C―C(sp2)峰的结合能出现显著的蓝移,如图4(a)所示。角分辨XPS(AR-XPS)结果表明,C―F键在石墨烯上下两层中分布均匀,证实了体系已转变为氟化金刚石。高分辨透射电子显微镜(high-resolution transmission electron microscope,HRTEM)图像清晰地显示出层间C―C键的存在,与模拟结果十分吻合,如图4(b)所示。光吸收测试表明,氟化后的样品出现了约3.3 eV的光学带隙,与理论计算值2.87 eV接近,表明所得二维金刚石材料为宽带隙半导体。值得注意的是,该研究首次在TEM中直接观察到二维金刚石的微观结构。在此基础上,Son等[54]进一步探索了基底对氟化反应的调控作用,通过调控石墨烯与基底之间的相互作用,实现了BLG的选择性氟化。在粗糙的SiO2基底上,氟原子能够渗透至石墨烯与基底之间,从而实现双面的氟化反应(图4(c));而在原子级平整的六方氮化硼(hBN)基底上,仅石墨烯顶层被氟化(图4(d))。氟化方式的差异显著影响产物材料的电子特性:双面氟化的BLG呈现绝缘性,而单面官能团化导致两层碳原子的电子态有效解耦[56],形成了“单面绝缘、单面导电”的Janus型结构,该研究为Janus型二维材料的设计提供了新思路。
与基于CVD、工艺条件苛刻、成本较高的“自下而上”方法不同,液相剥离作为“自上而下”策略具有操作简便、成本低廉及可规模化制备等优势[57–59]。Chen等[55]基于超声辅助溶剂剥离方法,开发了一种用于(C2F)n的新型液相制备方法,成功获得了具有类氟化二维金刚石结构的少层纳米片。如图4(e)所示,纳米片边缘的HRTEM图像显示其厚度约为2L~3L,层间距约为0.9 nm,该结果与理论预测模型高度一致。相应的SAED图样与已报道的氟化二维金刚石结果相符,进一步证实了所获得的薄片产物为氟化二维金刚石。
化学修饰法已被证明可以促成层间成键,但非碳杂原子的引入会极大降低材料的化学纯度,从而难以获得高洁净度的二维金刚石并掩盖其固有性质。为获得本征二维金刚石结构,有必要进一步探索无掺杂条件下由外场驱动的相变途径。受三维石墨向块体金刚石相变研究的启发[60–62],极端压力和应变在调控石墨烯向二维金刚石相变的热力学平衡中起到关键作用。外场加载能够有效改变两相的吉布斯自由能差,在特定的极端压力与应变条件下能够诱导碳原子从sp2构型重排为sp3构型[63]。极端高压法可分为局部针尖加载法和金刚石对顶砧(diamond anvil cell,DAC)高压法。
局部针尖加载法主要基于原子力显微镜(atomic force microscope,AFM),借助小尺寸的针尖对石墨烯前驱物施加局域的单轴力载荷。2011年,Barboza等[21]首次在室温条件下实现了FLG的压缩诱导金刚石化转变,综合第一性原理计算与实验结果发现,当FLG(尤其是2L~3L)表面在含水环境中发生羟基化修饰时,外加压力可驱动层间碳原子形成C―C共价键,从而自发形成表面羟基修饰的二维金刚石结构(Diamondol)。在该结构中,FLG只有最上面的两层发生金刚石化,而其他层仍保持类石墨烯结构,是一种铁磁绝缘体,带隙约为0.6 eV。在实验方面,Barboza等[21]进一步利用静电力显微镜(electrostatic force microscope,EFM)在不同载荷条件下对单层、双层及FLG进行了电荷注入与监测实验(图5(a))。测试结果显示,随着载荷的增加,双层及FLG的静电力响应显著降低,表明体系的能隙随载荷增加而增大,电子逐渐被局域化。这一现象可归因于外压诱导的sp2-sp3杂化转变以及相变后其带隙的打开;而单层石墨烯的电荷注入行为则未表现出明显的压力依赖性(图5(b))。此外,在不同温度(25与120 ℃)下进行的电荷注入实验结果(图5(c))显示,高温下EFM响应衰减幅度减小,表明环境中水分的减少会明显抑制羟基化反应,从而阻碍压力诱导的相变过程。综合来看,该相变的发生至少依赖于两层石墨烯之间的层间耦合以及表面羟基基团的协同作用。
2018年,Gao等[40]通过改进的AFM针尖施加局部压力,首次报道了在常温条件下BLG向超硬的二维金刚石亚稳态(Diamene)的可逆相变。该研究首次在实验上验证了二维金刚石具有与块体金刚石可比的力学性能,为二维金刚石的形成提供了直接证据。该研究采用具有亚埃级分辨率的调制纳米压痕AFM技术(图5(d)),对外延生长在碳化硅(SiC)(0001)晶面上的外延石墨烯薄膜进行原位力学测试。结果表明,当石墨烯层数超过5层时,其弹性模量接近于块体石墨;单层石墨烯缓冲层的弹性模量与本征SiC基底相似,而力载荷下双层外延石墨烯的弹性模量显著高于SiC基底(大于400 GPa),表明双层外延石墨烯在局部压应力下发生了结构重构,形成了具有高强度的亚稳态sp3相。压痕后的AFM形貌图像进一步表明,金刚石压头几乎无法在BLG表面产生塑性形变(图5(e))。这些结果表明,SiC基底上外延生长的BLG可在局部应力作用下转变为具有与块体金刚石相当刚度和硬度的二维金刚石。载荷依赖的导电AFM(C-AFM)实验(图5(g))进一步显示,在双层样品中,当载荷超过约260 nN时,电流信号突然下降,表明体系在此阈值下发生了向sp3含量更高、导电性更低的结构相变。在力载荷卸载后,电流恢复至初始值,说明该相变在室温下具有良好的可逆性。理论计算结果表明,在SiC基底上的双层外延石墨烯中,缓冲层中的部分碳原子与基底形成共价键,促进了sp2-sp3相变(图5(d)),这种特殊结构有助于饱和金刚石的悬挂键,并为相变创造条件[40, 64]。理论与实验结果共同表明,二维金刚石的形成仅限于含有缓冲层的双层外延石墨烯体系,而在更厚的多层结构中,会抑制sp2-sp3相变的发生。此外,对比研究发现,在仅机械加压条件下,机械剥离至SiO2基底上的任意厚度石墨烯均未观察到二维金刚石的形成,这可能是因为SiO2基底无法键合二维金刚石表面的单电子。
相比于利用原子力显微镜针尖进行局部施压的方法,金刚石对顶砧高压技术能够在更大尺度上对样品施加极端静水压载荷,从而实现整个样品区域的同步相变。此外,DAC还可与原位拉曼光谱、光致发光(photoluminescence,PL)光谱以及同步辐射X射线衍射(X-ray diffraction,XRD)等多种表征方法联用[65–67],使得在极端高压环境下对结构演化、键合重构及电子性质变化的实时原位监测与在线精确分析成为了可能。
DAC极端高压诱导的石墨烯向二维金刚石转变如图6[23, 68–69]所示。2017年,Martins等[23]以水为传压介质,将CVD法制备的BLG转移至惰性的Teflon基底上(以避免碳原子与基底成键),开展了细致的高压原位拉曼光谱测试(图6(a)),并提供了二维金刚石产物的光谱学证据。随着压力升高,G峰发生明显蓝移,并伴随半峰宽增大(图6(b))。当压力升至约7.5 GPa时,G峰频率对激发激光能量(2.33 和2.54 eV)表现出色散性,即出现能量分裂现象(图6(b)),表明体系中同时存在sp2和sp3杂化态的碳原子[70]。值得注意的是,该拉曼峰变化在卸压后具有可逆性,而在单层石墨烯或以矿物油为传压介质的BLG实验中均未观察到该现象,证实了水分子提供的羟基或氢官能团及BLG的层间耦合在二维金刚石形成过程中起到关键作用。如图6(c)所示,理论计算结果进一步表明,在氢或羟基基团存在下,当压力超过约4.7 GPa时,BLG的层间距收缩至2.7 Å 以下,形成了稳定的层间C―C共价键,实现了由sp2向sp3的转变,从而生成了表面羟基化的二维金刚石(Diamondene)。上述结果说明氢或羟基的存在显著降低了石墨烯转变为二维金刚石的临界压力。之后,该研究团队以水作为传压介质,对SiO2基底上机械剥离制备的BLG进行加压,也观测到类似的拉曼光谱行为与临界压力(约6.3 GPa),且卸压后结构完全恢复为石墨烯相,进一步验证了该相变的可逆性[71]。
随后,多个研究组在高压条件下观测到类似的可逆相变过程。Ke等[68–69]以Daphne 7373或氩气为传压介质,将不同层数的石墨烯转移至金刚石表面进行原位电学(图6(d))与吸收光谱测试。结果表明,室温下对机械剥离制备的3层及以上石墨烯施加高压可诱导其发生由sp2向sp3的结构转变,表现为电阻显著升高及光学带隙打开。进一步分析发现,石墨烯向二维金刚石转变的临界压力随层数增加而降低(图6(e)),且在减压过程中该高压相可稳定保持至约1 GPa。理论研究结果也证实,未经化学官能化的3层石墨烯在高压下可转变为超薄的六方二维金刚石结构,其带隙约为2.7 eV,从理论上验证了DAC高压诱导sp2向sp3相变的可行性。
2021年,Tao等[72]进一步研究了本征石墨烯在高压下的结构相变行为。他们将石墨烯转移至金网表面形成自支撑的悬空样品,以彻底消除基底的影响,并利用DAC进行高压原位拉曼测试。结果显示,当压力升至约37 GPa时,BLG的G峰完全消失,表明层间发生sp2向sp3的转变。相比之下,采用硅油作为传压介质时BLG的拉曼光谱变化不显著[69, 72],而单层石墨烯在水中压缩时也未观察到类似现象,说明水在促进层间C―C键形成中起关键作用。理论模拟结果进一步揭示,BLG表面的氢或羟基官能团有助于稳定层间的sp3键。
在前述对二维金刚石结构特征与形成机理探讨的基础上,进一步理解其物理化学特性对于揭示其本征性质及潜在的应用具有重要意义。作为厚度极限仅为单原子层的类金刚石相,二维金刚石被认为是迄今最薄的金刚石薄膜,不仅在理论上延续了块体金刚石的强共价键特征与高力学模量,还可能因尺寸效应与表界面效应而展现出独特的物理性质。当前,对二维金刚石物性的研究仍主要依赖于理论计算,实验层面的验证相对有限,其理论预测与实验结果之间仍需进一步验证与统一。为进一步揭示二维金刚石从结构到性能的内在联系,以下将从力学、电学、光学及热学特征等方面展开讨论。
早在2009年,Chernozatonskii等[26]通过模拟压痕研究指出,氢化二维金刚石的刚度显著高于石墨烷和石墨烯,但同时也表现出更高的脆性。后续研究表明,层数、堆垛方式及表面官能团对其力学性能具有显著影响。Mortazavi等[73]基于第一性原理计算评估了H、F、Cl等官能团及厚度效应,如图7(a)所示,发现随着层数增加,二维金刚石的弹性模量与拉伸强度均提高,且从H到Cl官能团,厚度依赖性更为明显。随着厚度增加,导致官能团作用减弱,其力学性能逐渐趋近于块体金刚石[32, 73]。进一步研究发现,层间堆垛对二维金刚石的力学性能影响较小[74],但其晶体取向依赖性显著[75],如图7(b)所示。沿扶手椅与锯齿形方向的弹性模量接近,表现出弹性各向同性;但锯齿形方向的断裂强度和延展性更加优异,AB堆垛氢化二维金刚石在扶手椅方向和锯齿方向的断裂强度分别为64和77 GPa,对应的断裂应变约为17%和26%,展现出显著的力学各向异性。通过原子构型分析表明,无论拉伸应变方向如何,断裂过程均由沿锯齿形方向的裂纹扩展所主导[75–76]。此外,二维金刚石的力学性能具有明显的温度依赖性,图7(c)显示随着温度升高,杨氏模量显著下降,当温度超过1000 K时结构趋于失稳或分解。
实验方面,Gao等[40]首次在室温下通过压痕实验证实生长于SiC基底表面的双层外延石墨烯可发生由石墨向类金刚石结构的可逆转变,其刚度与硬度接近金刚石,首次从实验上证明了二维金刚石的超高刚度。进一步地,亚埃级压痕实验表明,其刚度高达(1079±69) GPa,超过常见的蓝宝石及CVD金刚石等超硬材料[28]。随后,Rejhon等[81]深入研究了其塑性行为,结果表明,形成亚稳态类金刚石结构后,SiC表面硬度提升近一倍。此外,我们对二维金刚石与其他典型二维碳材料的力学性质进行了系统的比较,如图7(d)所示。由于二维材料仅具有原子级厚度,其厚度通常为一个不确定的量,传统的三维力学参数已不再适用,因此通常采用约化的二维面内杨氏模量与二维剪切模量等力学参数来表征其力学特征。值得注意的是,二维金刚石还具有极高的弯曲刚度,其值约为41.0 $ \text{eV∙} $Å2[75],远高于石墨烯的3.4 $ \text{eV∙} $Å2[82]。这种兼具卓越的力学强度、弯曲刚度及原子级厚度的优异性能,使其在新型柔性电子器件与纳米机电系统中展现出极大的应用潜力。
二维金刚石兼具金刚石的宽带隙特征及二维材料的可调电子结构,被一致认为是新型低维宽带隙半导体的重要候选材料。理论与实验研究均表明,其电子性质对表面官能团类型、层数以及外部调控等因素高度敏感,可在较宽能隙范围内实现电子结构的精准调控。如图8(a)所示,对氢化、氟化和氯化二维金刚石的电子能带结构分析表明,这些体系均在Г点处显现出直接带隙[26, 30, 73, 78, 83]。其中,氢化结构的带隙约为3.86 eV;当H被F取代后,带隙显著增大至约5.68 eV,即典型的宽带隙半导体,而H被Cl取代后的带隙则减小至约2.42 eV。进一步的理论研究发现,非Janus型与Janus型结构的带隙可覆盖0.86~5.68 eV的宽能隙范围[30],表明通过调控表面官能团种类及其分布情况,可在宽范围内实现带隙的连续调节。
受量子限域效应影响,二维金刚石的带隙可随层数不同而变化[73, 84–85]。图8(b)显示了DFT计算的氢化二维金刚石的带隙大小随层数的依赖关系,发现随着层数由1层增至5层,其带隙逐渐减小[84]。在实验方面,Ke等[69]通过光吸收光谱结合理论计算,证实了无表面修饰的六方二维金刚石的带隙与层数的依赖关系,与Kvashnin等[86]的理论预测高度一致。除层数效应外,外场调控同样能够显著影响其电子结构特征。例如,外加电场[87]、机械应力及应变[73]等因素均可有效调节二维金刚石的能带结构。值得注意的是,二维金刚石不仅具备可调带隙特性,还展现出优异的电输运性能。一般而言,常规半导体的载流子迁移率通常随带隙增大而降低[88],但得益于二维金刚石的高弹性模量与较小载流子有效质量,氢化与氟化体系的电子与空穴迁移率仍维持在较高水平[78](图8(c)),其中氢化二维金刚石的空穴迁移率约为1565 cm2/(V·s),氟化二维金刚石电子迁移率高达2732 cm2/(V·s),显示出其作为高性能宽带隙半导体材料的应用潜力。
此外,二维金刚石还展现出由宽带隙特性主导的独特光学行为[73, 89]。已有研究表明,氢化与氟化结构在可见光区几乎无明显的光吸收率,仅在紫外区出现强吸收峰;而氯化结构则在可见光及更宽能量范围内表现出显著的吸收[73](图8(d)~图8(e))。同时,二维金刚石在可见至紫外区域(高至37 eV)具有明显的反射响应[89]。这些结果表明,表面官能化不仅决定二维金刚石的电子能带结构,还能有效调控材料的光学性能,为二维金刚石在高性能光电子器件、深紫外探测及量子光学等领域的实际应用提供了广阔的设计空间。
二维金刚石因其优异的力学强度与光电可调特性,被视为在极端环境下实现高性能电子器件应用的理想候选材料。然而,在此类器件的实际应用中,散热问题始终是限制其稳定运行与长期可靠性的关键因素。因此,系统理解二维金刚石的热输运特性具有重要的现实意义。二维金刚石的热导率如图9[30, 90–91]所示。理论研究表明,二维金刚石的导热行为受表面官能团、堆垛方式及晶体对称性等多种因素的协同调控[30, 92]。Zhu等[90]系统研究了氢化二维金刚石的热导率κ,结果显示,氢化二维金刚石展现出与块体金刚石相当的高热导率,其热输运行为主要由面外声学声子(z-axis acoustic,ZA)振动模式主导。值得注意的是,热导率对堆垛方式高度敏感,其中AA堆垛结构的热导率显著高于AB堆垛,并接近体相金刚石(图9(a)~图9(b))。这可归因于AA堆垛中存在的水平反射对称性有效限制了声子散射相空间,从而延长了声子寿命并导致热导率的提升[90]。为进一步探究官能团效应,Zhu等[91]比较了氢化与氟化二维金刚石的热输运性质(图9(c))。研究发现,氟化后的热导率显著降低,且主导热传输的声子模式由氢化体系中的ZA模式转变为氟化中的光学支;其原因在于较重的卤素原子使得声子色散软化,导致声子的群速度降低,致使非弹性散射增强,从而抑制了整体的热输运能力。此外,Janus型结构的热导率通常介于其非Janus对应物之间[30],如图9(d)所示。这些结果表明,通过调节表面官能团的种类,可实现对二维金刚石热输运特性的调控。总体趋势显示,随着官能团原子量的增加,体系中光学模式的贡献比例显著上升,而声学模式的主导作用逐渐减弱,体现出官能团中原子质量对热输运机制的关键调控作用。同时,应变亦对二维金刚石的热输运行为具有显著的影响[93]。研究表明,当拉伸应变达到10%时,其室温热导率约降至本征值的11%,但在低应变范围内仍保持较高的热导率,超过1000 W/(m·K)。由此可见,二维金刚石兼具优异的力学性能、可调电子结构以及高热导率等特性,在高温、高压及高频等极端环境下展现出广阔的发展前景与应用潜力。
本文系统综述了二维金刚石的最新研究进展,包括其发展过程、结构特征、实验合成方法及物理化学性质。尽管近年来对二维金刚石的研究已取得了部分重要进展,但是相关的可控合成与调控策略亟待进一步完善与优化。首先,需要深入阐明从sp2到sp3转变的驱动力及其微观相变机制,并明确相变过程中的动力学行为与演化路径。其次,应通过优化压力温度条件、外场作用、化学修饰及基底界面相互作用等手段,实现对结构形成与演化的精确调控,从而获得多样化的二维金刚石结构。最后,有必要系统研究提升二维金刚石稳定性的有效策略,以确保其在常温常压下长期稳定存在。
二维金刚石兼具高硬度、可调带隙、高载流子迁移率、高热导率以及优异光学透明性等特征,在高功率电子器件、量子计算、光电器件及纳米传感等前沿领域展现出广阔的应用潜力。然而,实现高质量样品的规模化制备及对其本征性质的精准测量与调控仍是当前研究的主要挑战。未来,通过物理和化学手段的协同调控,结合先进的表征手段,有望实现二维金刚石及其衍生结构可控制备与性能优化,进一步推动其从基础研究迈向实际应用。

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2026年第40卷第9期
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doi: 10.11858/gywlxb.20251248
  • 接收时间:2025-11-04
  • 首发时间:2026-11-05
  • 出版时间:2026-09-05
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  • 收稿日期:2025-11-04
  • 修回日期:2025-11-21
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    1北京理工大学化学与化工学院, 北京 100081
    2北京理工大学前沿交叉科学院, 北京 100081

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陈亚彬(1984-),男,博士,教授,主要从事高压材料物理研究. E-mail:
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2种不同金属材料的力学参数
科
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属数
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genus
种数
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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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