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{{NoteTA|G1=Physics}} |
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[[File:HPHTdiamonds2.JPG|thumb|right|高温高压条件下制成的各种颜色的[[合成钻石]]。尺寸在2毫米左右。]] |
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[[File:Diamond IR Spector.png|thumb|right|IaB型金刚石的红外吸收谱：（1）是氮杂质（这里主要是B中心）的吸收峰，（2）是片晶的吸收峰, （3）是金刚石晶格本身的吸收峰，（4）是位于{{val|3107|u=cm<sup>−1</sup>}}与{{val|3237|u=cm<sup>−1</sup>}}附近的氢吸收峰。]] |
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[[金刚石]]常会产生[[晶体缺陷]]。'''金刚石的晶体缺陷'''既有可能产生于不规则的晶格，也有可能产生自替位或填隙杂质，且在生长过程中和生长完成后都有可能形成。晶体缺陷会影响{{le|金刚石的材料性能|material properties of diamond}}并决定金刚石的分类。较为显著的影响包括通过改变电子[[能带结构]]而导致的金刚石颜色和[[电导率]]的变化。 |
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金刚石的晶体缺陷可以通过多种[[光谱学|谱学]]方法检测，其中包括[[电子自旋共振]]谱，[[光致发光]]或[[阴极射线发光]]光谱，及[[红外]]、[[可见光]]和[[紫外]]波段的吸收光谱等。[[吸收光谱]]不仅可以用来识别缺陷的种类，还可以用来估计缺陷的浓度，同时还可以用来鉴定一颗金刚石是天然形成的、还是[[合成钻石|人工合成]]的抑或是经过{{le|Diamond enhancement|钻石加工|加工}}的。<ref name=collins1>{{Cite journal | last1 = Collins | first1 = A. T. | title = The detection of colour-enhanced and synthetic gem diamonds by optical spectroscopy | doi = 10.1016/S0925-9635(03)00262-0 | journal = Diamond and Related Materials | volume = 12 | issue = 10–11 | pages = 1976–1983 | year = 2003 | bibcode = 2003DRM....12.1976C }}</ref> |
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==标记== |
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There is a tradition in diamond spectroscopy to label a defect-induced spectrum by a numbered acronym (e.g. GR1). This tradition has been followed in general with some notable deviations, such as A, B and C centers. Many acronyms are confusing though:<ref name=walker>{{Cite journal | last1 = Walker | first1 = J. | title = Optical absorption and luminescence in diamond|url=https://accreditedgemologists.org/lightingtaskforce/OpticalAbsorptionand.pdf | doi = 10.1088/0034-4885/42/10/001 | journal = Reports on Progress in Physics | volume = 42 | issue = 10 | pages = 1605–1659 | year = 1979 | bibcode = 1979RPPh...42.1605W | citeseerx = 10.1.1.467.443 }}</ref> |
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*Some symbols are too similar (e.g., 3H and H3). |
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*Accidentally, same labels were given to different centers detected by EPR and optical techniques (e.g., N3 EPR center and N3 optical center have no relation).<ref name=N3/> |
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*Whereas some acronyms are logical, such as N3 (N for natural, i.e. observed in natural diamond) or H3 (H for heated, i.e. observed after irradiation and heating), many are not. In particular, there is no clear distinction between the meaning of labels GR (general radiation), R (radiation) and TR (type-II radiation).<ref name=walker/> |
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==对称性== |
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The symmetry of defects in crystals is described by the [[point group]]s. They differ from the [[space group]]s describing the symmetry of crystals by absence of translations, and thus are much fewer in number. In diamond, only defects of the following symmetries have been observed thus far: [[tetrahedral]] (T<sub>d</sub>), [[tetragonal]] (D<sub>2d</sub>), [[trigonal]] (D<sub>3d</sub>,C<sub>3v</sub>), [[rhombus|rhombic]] (C<sub>2v</sub>), [[monoclinic]] (C<sub>2h</sub>, C<sub>1h</sub>, C<sub>2</sub>) and [[triclinic]] (C<sub>1</sub> or C<sub>S</sub>).<ref name=walker/><ref name=zaitsev>{{cite book| author = Zaitsev, A. M. | title = Optical Properties of Diamond : A Data Handbook| publisher = Springer | year = 2001| isbn = 978-3-540-66582-3}}</ref> |
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The defect symmetry allows predicting many optical properties. For example, one-phonon (infrared) absorption in pure diamond lattice is forbidden because the lattice has an [[Centrosymmetry|inversion center]]. However, introducing any defect (even "very symmetrical", such as N-N substitutional pair) breaks the crystal symmetry resulting in defect-induced infrared absorption, which is the most common tool to measure the defect concentrations in diamond.<ref name=walker/> |
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In synthetic diamond grown by the high-pressure high-temperature synthesis<ref name="align">{{Cite journal | last1 = Iakoubovskii | first1 = K. | last2 = Collins | first2 = A. T. | doi = 10.1088/0953-8984/16/39/022 | title = Alignment of Ni- and Co-related centres during the growth of high-pressure–high-temperature diamond |url=https://www.researchgate.net/publication/230954924| journal = Journal of Physics: Condensed Matter | volume = 16 | issue = 39 | pages = 6897 | year = 2004 | bibcode = 2004JPCM...16.6897I }}</ref> or [[chemical vapor deposition]],<ref>{{Cite journal | last1 = Edmonds | first1 = A. | last2 = d’Haenens-Johansson | first2 = U. | last3 = Cruddace | first3 = R. | last4 = Newton | first4 = M. | last5 = Fu | first5 = K. -M. | last6 = Santori | first6 = C. | last7 = Beausoleil | first7 = R. | last8 = Twitchen | first8 = D. | last9 = Markham | first9 = M. | title = Production of oriented nitrogen-vacancy color centers in synthetic diamond | doi = 10.1103/PhysRevB.86.035201 | journal = Physical Review B | volume = 86 | issue = 3 | pages = 035201 | year = 2012 | arxiv = 1112.5757 |bibcode = 2012PhRvB..86c5201E }}</ref><ref>{{Cite journal | last1 = d’Haenens-Johansson | first1 = U. | last2 = Edmonds | first2 = A. | last3 = Newton | first3 = M. | last4 = Goss | first4 = J. | last5 = Briddon | first5 = P. | last6 = Baker | first6 = J. | last7 = Martineau | first7 = P. | last8 = Khan | first8 = R. | last9 = Twitchen | first9 = D. | last10 = Williams | first10 = S. D. | title = EPR of a defect in CVD diamond involving both silicon and hydrogen that shows preferential alignment | doi = 10.1103/PhysRevB.82.155205 | journal = Physical Review B | volume = 82 | issue = 15 | pages = 155205 | year = 2010 | bibcode = 2010PhRvB..82o5205D }}</ref> defects with symmetry lower than tetrahedral align to the direction of the growth. Such alignment has also been observed in [[gallium arsenide]]<ref>{{Cite journal | last1 = Hogg | first1 = R. A. | last2 = Takahei | first2 = K. | last3 = Taguchi | first3 = A. | last4 = Horikoshi | first4 = Y. | title = Preferential alignment of Er–2O centers in GaAs:Er,O revealed by anisotropic host-excited photoluminescence | doi = 10.1063/1.116043 | journal = Applied Physics Letters | volume = 68 | issue = 23 | pages = 3317 | year = 1996 | bibcode = 1996ApPhL..68.3317H }}</ref> and thus is not unique to diamond. |
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==杂质缺陷== |
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Various elemental analyses of diamond reveal a wide range of impurities.<ref>{{cite journal|last1=Assali|first1=L. V. C.|last2=Machado|first2=W. V. M.|last3=Justo|first3=J. F.|title=3d transition metal impurities in diamond: electronic properties and chemical trends|journal=Phys. Rev. B|date=2011|volume=84|issue=15|page=155205|doi=10.1103/PhysRevB.84.155205|bibcode=2011PhRvB..84o5205A|arxiv=1307.3278}}</ref> They mostly originate, however, from inclusions of foreign materials in diamond, which could be nanometer-small and invisible in an [[optical microscope]]. Also, virtually any element can be hammered into diamond by [[ion implantation]]. More essential are elements which can be introduced into the diamond lattice as isolated atoms (or small atomic clusters) during the diamond growth. By 2008, those elements are [[nitrogen]], [[boron]], [[hydrogen]], [[silicon]], [[phosphorus]], [[nickel]], [[cobalt]] and perhaps [[sulfur]]. [[Manganese]]<ref>{{Cite journal | last1 = Iakoubovskii | first1 = K. | last2 = Stesmans | first2 = A. | doi = 10.1002/1521-396X(200108)186:2<199::AID-PSSA199>3.0.CO;2-R | title = Characterization of Defects in as-Grown CVD Diamond Films and HPHT Diamond Powders by Electron Paramagnetic Resonance|url=https://www.researchgate.net/publication/243596989 | journal = Physica Status Solidi A | volume = 186 | issue = 2 | pages = 199 | year = 2001 | bibcode = 2001PSSAR.186..199I }}</ref> and [[tungsten]]<ref>{{Cite journal | last1 = Lal | first1 = S. | last2 = Dallas | first2 = T. | last3 = Yi | first3 = S. | last4 = Gangopadhyay | first4 = S. | last5 = Holtz | first5 = M. | last6 = Anderson | first6 = F. | doi = 10.1103/PhysRevB.54.13428 | title = Defect photoluminescence in polycrystalline diamond films grown by arc-jet chemical-vapor deposition | journal = Physical Review B | volume = 54 | issue = 19 | pages = 13428 | year = 1996 | bibcode = 1996PhRvB..5413428L }}</ref> have been unambiguously detected in diamond, but they might originate from foreign inclusions. Detection of isolated [[iron]] in diamond<ref>{{Cite journal | last1 = Iakoubovskii | first1 = K. | last2 = Adriaenssens | first2 = G. J. | doi = 10.1088/0953-8984/14/4/104 | title = Evidence for a Fe-related defect centre in diamond|url=https://www.researchgate.net/publication/231021050 | journal = Journal of Physics: Condensed Matter | volume = 14 | issue = 4 | pages = L95 | year = 2002 | bibcode = 2002JPCM...14L..95I }}</ref> has later been re-interpreted in terms of micro-particles of [[ruby]] produced during the diamond synthesis.<ref>{{Cite journal | last1 = Iakoubovskii | first1 = K. | last2 = Adriaenssens | first2 = G. J. | doi = 10.1088/0953-8984/14/21/401 | title = Comment on 'Evidence for a Fe-related defect centre in diamond' |url=https://www.researchgate.net/publication/243411401| journal = Journal of Physics: Condensed Matter | volume = 14 | issue = 21 | pages = 5459 | year = 2002 | bibcode = 2002JPCM...14R.401I }}</ref> Oxygen is believed to be a major impurity in diamond,<ref name="kaiser"/> but it has not been spectroscopically identified in diamond yet.{{citation needed|date=January 2009}} Two [[electron paramagnetic resonance]] centers (OK1 and N3) have been assigned to nitrogen–oxygen complexes. However, the assignment is indirect and the corresponding concentrations are rather low (few parts per million).<ref>{{Cite journal | last1 = Newton | first1 = M. E. | last2 = Baker | first2 = J. M. | doi = 10.1088/0953-8984/1/51/024 | title = <sup>14</sup>N ENDOR of the OK1 centre in natural type Ib diamond | journal = Journal of Physics: Condensed Matter | volume = 1 | issue = 51 | pages = 10549 | year = 1989 | pmc = |bibcode = 1989JPCM....110549N }}</ref> |
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===氮=== |
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金刚石中存在最为普遍的杂质是氮，质量占比可达1 %。<ref name="kaiser">{{Cite journal | last1 = Kaiser | first1 = W. | last2 = Bond | first2 = W. | doi = 10.1103/PhysRev.115.857 | title = Nitrogen, A Major Impurity in Common Type I Diamond | journal = Physical Review | volume = 115 | issue = 4 | pages = 857 | year = 1959 | bibcode = 1959PhRv..115..857K }}</ref> Previously, all lattice defects in diamond were thought to be the result of structural anomalies; later research revealed nitrogen to be present in most diamonds and in many different configurations. Most nitrogen enters the diamond lattice as a single atom (i.e. nitrogen-containing molecules dissociate before incorporation), however, molecular nitrogen incorporates into diamond as well.<ref>{{Cite journal | last1 = Iakoubovskii | first1 = K. | last2 = Adriaenssens | first2 = G. J. | last3 = Vohra | first3 = Y. K. | doi = 10.1088/0953-8984/12/30/106 | title = Nitrogen incorporation in diamond films homoepitaxially grown by chemical vapour deposition | journal = Journal of Physics: Condensed Matter | volume = 12 | issue = 30 | pages = L519 | year = 2000 | bibcode = 2000JPCM...12L.519I |url=https://www.researchgate.net/publication/231100286}}</ref> |
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Absorption of light and other material properties of diamond are highly dependent upon nitrogen content and aggregation state. Although all aggregate configurations cause absorption in the [[infrared]], diamonds containing aggregated nitrogen are usually colorless, i.e. have little absorption in the visible spectrum.<ref name=walker/> The four main nitrogen forms are as follows: |
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[[File:Ccenter.JPG|thumb|right|150px|Schematic of the C center]] |
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====C中心==== |
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The C center corresponds to electrically neutral single substitutional nitrogen [[atom]]s in the diamond lattice. These are easily seen in [[electron paramagnetic resonance]] spectra<ref>{{Cite journal | last1 = Smith | first1 = W. | last2 = Sorokin | first2 = P. | last3 = Gelles | first3 = I. | last4 = Lasher | first4 = G. | title = Electron-Spin Resonance of Nitrogen Donors in Diamond | doi = 10.1103/PhysRev.115.1546 | journal = Physical Review | volume = 115 | issue = 6 | pages = 1546 | year = 1959 | bibcode = 1959PhRv..115.1546S }}</ref> (in which they are confusingly called P1 centers). C centers impart a deep yellow to brown color; these diamonds are classed as ''type Ib'' and are commonly known as "canary diamonds", which are rare in [[gemstone|gem]] form. Most synthetic diamonds produced by high-pressure high-temperature (HPHT) technique contain a high level of nitrogen in the C form; nitrogen impurity originates from the atmosphere or from the graphite source. One nitrogen atom per 100,000 carbon atoms will produce yellow color.<ref>Nassau, Kurt (1980) "Gems made by man" [[Gemological Institute of America]], Santa Monica, California, {{ISBN|0-87311-016-1}}, p. 191</ref> Because the nitrogen atoms have five available [[electron]]s (one more than the [[carbon]] atoms they replace), they act as "deep [[Electron donor|donor]]s"; that is, each substituting nitrogen has an extra electron to donate and forms a donor [[energy level]] within the [[band gap]]. Light with energy above ~2.2 [[electron volt|eV]] can excite the donor electrons into the [[conduction band]], resulting in the yellow color.<ref name="p1">{{Cite journal | last1 = Iakoubovskii | first1 = K. | last2 = Adriaenssens | first2 = G. J. | doi = 10.1088/0953-8984/12/6/102 | title = Optical transitions at the substitutional nitrogen centre in diamond|url=https://www.researchgate.net/publication/258290449 | journal = Journal of Physics: Condensed Matter | volume = 12 | issue = 6 | pages = L77 | year = 2000 |bibcode = 2000JPCM...12L..77I }}</ref> |
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The C center produces a characteristic infrared absorption spectrum with a sharp peak at 1344 cm<sup>−1</sup> and a broader feature at 1130 cm<sup>−1</sup>. Absorption at those peaks is routinely used to measure the concentration of single nitrogen.<ref>I. Kiflawi et al. "Infrared-absorption by the single nitrogen and a defect centers in diamond" Philos. Mag. B 69 (1994) 1141</ref> Another proposed way, using the UV absorption at ~260 nm, has later been discarded as unreliable.<ref name="p1"/> |
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Acceptor defects in diamond ionize the fifth nitrogen electron in the C center converting it into C+ center. The latter has a characteristic IR absorption spectrum with a sharp peak at 1332 cm<sup>−1</sup> and broader and weaker peaks at 1115, 1046 and 950 cm<sup>−1</sup>.<ref>{{Cite journal | last1 = Lawson | first1 = S. C. | last2 = Fisher | first2 = D. | last3 = Hunt | first3 = D. C. | last4 = Newton | first4 = M. E. | title = On the existence of positively charged single-substitutional nitrogen in diamond | doi = 10.1088/0953-8984/10/27/016 | journal = Journal of Physics: Condensed Matter | volume = 10 | issue = 27 | pages = 6171 | year = 1998 | bibcode = 1998JPCM...10.6171L }}</ref> |
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[[File:Acenter.JPG|thumb|right|150px|Schematic of the A center]] |
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====A中心==== |
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The A center is probably the most common defect in natural diamonds. It consists of a neutral nearest-neighbor pair of nitrogen atoms substituting for the carbon atoms. The A center produces UV absorption threshold at ~4 eV (310 nm, i.e. invisible to eye) and thus causes no coloration. Diamond containing nitrogen predominantly in the A form as classed as ''type IaA''.<ref name=A>{{Cite journal | last1 = Davies | first1 = G. | title = The A nitrogen aggregate in diamond-its symmetry and possible structure | doi = 10.1088/0022-3719/9/19/005 | journal = Journal of Physics C: Solid State Physics | volume = 9 | issue = 19 | pages = L537–L542 | year = 1976 | bibcode = 1976JPhC....9L.537D }}</ref> |
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The A center is [[diamagnetic]], but if ionized by UV light or deep acceptors, it produces an [[electron paramagnetic resonance]] spectrum W24, whose analysis unambiguously proves the N=N structure.<ref>{{Cite journal | last1 = Tucker | first1 = O. | last2 = Newton | first2 = M. | last3 = Baker | first3 = J. | doi = 10.1103/PhysRevB.50.15586 | title = EPR and N14 electron-nuclear double-resonance measurements on the ionized nearest-neighbor dinitrogen center in diamond | journal = Physical Review B | volume = 50 | issue = 21 | pages = 15586 | year = 1994 | bibcode = 1994PhRvB..5015586T }}</ref> |
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The A center shows an IR absorption spectrum with no sharp features, which is distinctly different from that of the C or B centers. Its strongest peak at 1282 cm<sup>−1</sup> is routinely used to estimate the nitrogen concentration in the A form.<ref>{{Cite journal | last1 = Boyd | first1 = S. R. | last2 = Kiflawi | first2 = I. | last3 = Woods | first3 = G. S. | doi = 10.1080/01418639408240185 | title = The relationship between infrared absorption and the a defect concentration in diamond | journal = Philosophical Magazine B | volume = 69 | issue = 6 | pages = 1149 | year = 1994 | bibcode = 1994PMagB..69.1149B }}</ref> |
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[[File:Bcenter.JPG|thumb|right|150px|Schematic of the B center]] |
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====B中心==== |
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There is a general consensus that B center (sometimes called B1) consists of a carbon vacancy surrounded by four nitrogen atoms substituting for carbon atoms.<ref name=collins1/><ref name=walker/><ref name=collins2/> This model is consistent with other experimental results, but there is no direct spectroscopic data corroborating it. Diamonds where most nitrogen forms B centers are rare and are classed as ''type IaB''; most gem diamonds contain a mixture of A and B centers, together with N3 centers. |
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Similar to the A centers, B centers do not induce color, and no UV or visible absorption can be attributed to the B centers. Early assignment of the N9 absorption system to the B center have been disproven later.<ref>{{Cite journal | last1 = Shiryaev | first1 = A. A. | last2 = Hutchison | first2 = M. T. | last3 = Dembo | first3 = K. A. | last4 = Dembo | first4 = A. T. | last5 = Iakoubovskii | first5 = K. | last6 = Klyuev | first6 = Y. A. | last7 = Naletov | first7 = A. M. | title = High-temperature high-pressure annealing of diamond |url=https://www.researchgate.net/publication/243227615| doi = 10.1016/S0921-4526(01)00750-5 | journal = Physica B: Condensed Matter | volume = 308-310 | pages = 598–603 | year = 2001 | bibcode = 2001PhyB..308..598S }}</ref> The B center has a characteristic IR absorption spectrum (see the infrared absorption picture above) with a sharp peak at 1332 cm<sup>−1</sup> and a broader feature at 1280 cm<sup>−1</sup>. The latter is routinely used to estimate the nitrogen concentration in the B form.<ref>{{Cite journal | last1 = Boyd | first1 = S. R. | last2 = Kiflawi | first2 = I. | last3 = Woods | first3 = G. S. | doi = 10.1080/13642819508239089 | title = Infrared absorption by the B nitrogen aggregate in diamond | journal = Philosophical Magazine B | volume = 72 | issue = 3 | pages = 351 | year = 1995 | bibcode = 1995PMagB..72..351B }}</ref> |
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Note that many optical peaks in diamond accidentally have similar spectral positions, which causes much confusion among gemologists. Spectroscopists use for defect identification the whole spectrum rather than one peak, and consider the history of the growth and processing of individual diamond.<ref name=collins1/><ref name=walker/><ref name=collins2/> |
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[[File:N3center.JPG|thumb|right|150px|Schematic of the N3 center]] |
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====N3中心==== |
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The N3 center consists of three nitrogen atoms surrounding a vacancy. Its concentration is always just a fraction of the A and B centers.<ref>Anderson, B.; Payne, J.; Mitchell, R.K. (ed.) (1998) "The spectroscope and gemology", p. 215, Robert Hale Limited, Clerkwood House, London. {{ISBN|0-7198-0261-X}}</ref> The N3 center is [[paramagnetism|paramagnetic]], so its structure is well justified from the analysis of the EPR spectrum P2.<ref name=N3>{{Cite journal | last1 = Wyk | first1 = J. A. V. | title = Carbon-12 hyperfine interaction of the unique carbon of the P2 (ESR) or N3 (optical) centre in diamond | doi = 10.1088/0022-3719/15/27/007 | journal = Journal of Physics C: Solid State Physics | volume = 15 | issue = 27 | pages = L981–L983 | year = 1982 | bibcode = 1982JPhC...15L.981V }}</ref> This defect produces a characteristic absorption and luminescence line at 415 nm and thus does not induce color on its own. However, the N3 center is always accompanied by the N2 center, having an absorption line at 478 nm (and no luminescence).<ref>{{Cite journal | last1 = Thomaz | first1 = M. F. | last2 = Davies | first2 = G. | doi = 10.1098/rspa.1978.0141 | title = The Decay Time of N3 Luminescence in Natural Diamond | journal = Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences | volume = 362 | issue = 1710 | pages = 405 | year = 1978 | bibcode = 1978RSPSA.362..405T }}</ref> As a result, diamonds rich in N3/N2 centers are yellow in color. |
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===硼=== |
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Diamonds containing boron as a substitutional impurity are termed ''type IIb''. Only one percent of natural diamonds are of this type, and most are blue to grey.<ref>O'Donoghue, M. (2002) "Synthetic, imitation & treated gemstones", Elsevier Butterworth-Heinemann, Great Britain. {{ISBN|0-7506-3173-2}}, p. 52</ref> Boron is an acceptor in diamond: boron atoms have one less available electron than the carbon atoms; therefore, each boron atom substituting for a carbon atom creates an [[electron hole]] in the band gap that can accept an electron from the [[valence band]]. This allows red light absorption, and due to the small energy (0.37 eV)<ref name="boron"/> needed for the electron to leave the valence band, holes can be thermally released from the boron atoms to the [[valence band]] even at room temperatures. These holes can move in an [[electric field]] and render the diamond [[Electrical conductivity|electrically conductive]] (i.e., a [[p-type semiconductor]]). Very few boron atoms are required for this to happen—a typical ratio is one boron atom per 1,000,000 carbon atoms. |
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Boron-doped diamonds transmit light down to ~250 nm and absorb some red and infrared light (hence the blue color); they may [[phosphorescence|phosphoresce]] blue after exposure to shortwave ultraviolet light.<ref name="boron">{{Cite journal | last1 = Collins | first1 = A. T. | title = The Optical and Electronic Properties of Semiconducting Diamond | doi = 10.1098/rsta.1993.0017 | journal = Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences | volume = 342 | issue = 1664 | pages = 233–244| year = 1993 | bibcode = 1993RSPTA.342..233C }}</ref> Apart from optical absorption, boron acceptors have been detected by electron paramagnetic resonance.<ref>{{Cite journal | last1 = Ammerlaan | first1 = C. A. J. | last2 = Kemp | first2 = R. V. | doi = 10.1088/0022-3719/18/13/009 | title = Magnetic resonance spectroscopy in semiconducting diamond | journal = Journal of Physics C: Solid State Physics | volume = 18 | issue = 13 | pages = 2623 | year = 1985 | bibcode = 1985JPhC...18.2623A }}</ref> |
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===磷=== |
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Phosphorus could be intentionally introduced into diamond grown by chemical vapor deposition (CVD) at concentrations up to ~0.01%.<ref name="Kociniewski">{{Cite journal | last1 = Kociniewski | first1 = T. | last2 = Barjon | first2 = J. | last3 = Pinault | first3 = M. -A. | last4 = Jomard | first4 = F. | last5 = Lusson | first5 = A. | last6 = Ballutaud | first6 = D. | last7 = Gorochov | first7 = O. | last8 = Laroche | first8 = J. M. | last9 = Rzepka | first9 = E. | last10 = Chevallier | doi = 10.1002/pssa.200671113 | first10 = J. | last11 = Saguy | first11 = C. | title = N-type CVD diamond doped with phosphorus using the MOCVD technology for dopant incorporation | journal = Physica Status Solidi A | volume = 203 | issue = 12 | pages = 3136 | year = 2006 | bibcode = 2006PSSAR.203.3136K }}</ref> Phosphorus substitutes carbon in the diamond lattice.<ref>{{Cite journal | last1 = Hasegawa | first1 = M. | last2 = Teraji | first2 = T. | last3 = Koizumi | first3 = S. | doi = 10.1063/1.1417514 | title = Lattice location of phosphorus in n-type homoepitaxial diamond films grown by chemical-vapor deposition | journal = Applied Physics Letters | volume = 79 | issue = 19 | pages = 3068 | year = 2001 | bibcode = 2001ApPhL..79.3068H }}</ref> Similar to nitrogen, phosphorus has one more electron than carbon and thus acts as a donor; however, the ionization energy of phosphorus (0.6 eV)<ref name="Kociniewski" /> is much smaller than that of nitrogen (1.7 eV)<ref>{{Cite journal | last1 = Farrer | first1 = R. G. | title = On the substitutional nitrogen donor in diamond | doi = 10.1016/0038-1098(69)90593-6 | journal = Solid State Communications | volume = 7 | issue = 9 | pages = 685–688 | year = 1969 | bibcode = 1969SSCom...7..685F }}</ref> and is small enough for room-temperature [[thermal ionization]]. This important property of phosphorus in diamond favors electronic applications, such as UV light emitting diodes ([[LED]]s, at 235 nm).<ref name="koizumi">{{Cite journal | last1 = Koizumi | first1 = S. | last2 = Watanabe | first2 = K. | last3 = Hasegawa | first3 = M. | last4 = Kanda | first4 = H. | title = Ultraviolet Emission from a Diamond pn Junction | doi = 10.1126/science.1060258 | journal = Science | volume = 292 | issue = 5523 | pages = 1899–1901 | year = 2001 | pmid = 11397942| pmc = |bibcode = 2001Sci...292.1899K }}</ref> |
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===氢=== |
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Hydrogen is one of the most technological important impurities in semiconductors, including diamond. Hydrogen-related defects are very different in natural diamond and in synthetic diamond films. Those films are produced by various [[chemical vapor deposition]] (CVD) techniques in an atmosphere rich in hydrogen (typical hydrogen/carbon ratio >100), under strong bombardment of growing diamond by the plasma ions. As a result, CVD diamond is always rich in hydrogen and lattice vacancies. In polycrystalline films, much of the hydrogen may be located at the boundaries between diamond 'grains', or in non-diamond carbon inclusions. Within the diamond lattice itself, hydrogen-vacancy<ref>{{Cite journal |
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| doi = 10.1103/PhysRevLett.92.135502 |
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| last1 = Glover | first1 = C. |
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| last2 = Newton | first2 = M. E. |
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| last3 = Martineau | first3 = P. M. |
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| last4 = Quinn | first4 = S. |
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| last5 = Twitchen | first5 = D. J. |
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| title = Hydrogen incorporation in diamond: The vacancy-hydrogen complex |
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| journal = Physical Review Letters |
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| volume = 92 |
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| issue = 13 |
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| pages = 135502 |
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| year = 2004 |
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| pmid = 15089622 |
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|bibcode = 2004PhRvL..92m5502G }}</ref> and hydrogen-nitrogen-vacancy<ref>{{Cite journal | last1 = Glover | first1 = C. | last2 = Newton | first2 = M. | last3 = Martineau | first3 = P. | last4 = Twitchen | first4 = D. | last5 = Baker | first5 = J. | title = Hydrogen Incorporation in Diamond: The Nitrogen-Vacancy-Hydrogen Complex | doi = 10.1103/PhysRevLett.90.185507 | journal = Physical Review Letters | volume = 90 | issue = 18 | pages = 185507 | year = 2003 | pmid = 12786024| pmc = |bibcode = 2003PhRvL..90r5507G }}</ref> complexes have been identified in negative charge states by [[electron paramagnetic resonance]]. In addition, numerous hydrogen-related IR absorption peaks are documented.<ref>{{Cite journal | last1 = Fuchs | first1 = F. | last2 = Wild | first2 = C. | last3 = Schwarz | first3 = K. | last4 = MüLler-Sebert | first4 = W. | last5 = Koidl | first5 = P. | title = Hydrogen induced vibrational and electronic transitions in chemical vapor deposited diamond, identified by isotopic substitution | doi = 10.1063/1.113126 | journal = Applied Physics Letters | volume = 66 | issue = 2 | pages = 177 | year = 1995 | bibcode = 1995ApPhL..66..177F }}</ref> |
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It is experimentally demonstrated that hydrogen passivates electrically active boron<ref>{{Cite journal | last1 = Chevallier | first1 = J. | last2 = Theys | first2 = B. | last3 = Lusson | first3 = A. | last4 = Grattepain | first4 = C. | last5 = Deneuville | first5 = A. | last6 = Gheeraert | first6 = E. | doi = 10.1103/PhysRevB.58.7966 | title = Hydrogen-boron interactions in p-type diamond | journal = Physical Review B | volume = 58 | issue = 12 | pages = 7966 | year = 1998 | bibcode = 1998PhRvB..58.7966C }}</ref> and phosphorus<ref>{{Cite journal | last1 = Chevallier | first1 = J. | last2 = Jomard | first2 = F. | last3 = Teukam | first3 = Z. | last4 = Koizumi | first4 = S. | last5 = Kanda | first5 = H. | last6 = Sato | first6 = Y. | last7 = Deneuville | first7 = A. | last8 = Bernard | first8 = M. | doi = 10.1016/S0925-9635(02)00063-8 | title = Hydrogen in n-type diamond | journal = Diamond and Related Materials | volume = 11 | issue = 8 | pages = 1566 | year = 2002 | bibcode = 2002DRM....11.1566C }}</ref> impurities. As a result of such passivation, shallow donor centers are presumably produced.<ref>{{Cite journal | last1 = Teukam | first1 = Z. P. | last2 = Chevallier | first2 = J. | last3 = Saguy | first3 = C. C. | last4 = Kalish | first4 = R. | last5 = Ballutaud | first5 = D. | last6 = Barbé | first6 = M. | last7 = Jomard | first7 = F. O. | last8 = Tromson-Carli | first8 = A. | last9 = Cytermann | first9 = C. | last10 = Butler | doi = 10.1038/nmat929 | first10 = J. E. | last11 = Bernard | first11 = M. | last12 = Baron | first12 = C. L. | last13 = Deneuville | first13 = A. | title = Shallow donors with high n-type electrical conductivity in homoepitaxial deuterated boron-doped diamond layers |url=https://www.researchgate.net/publication/10647734| journal = Nature Materials | volume = 2 | issue = 7 | pages = 482–486 | year = 2003 | pmid = 12876564| pmc = |bibcode = 2003NatMa...2..482T }}</ref> |
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In natural diamonds, several hydrogen-related IR absorption peaks are commonly observed; the strongest ones are located at 1405, 3107 and 3237 cm<sup>−1</sup> (see IR absorption figure above). The microscopic structure of the corresponding defects is yet unknown and it is not even certain whether or not those defects originate in diamond or in foreign inclusions. Gray color in some diamonds from the [[Argyle diamond mine|Argyle mine]] in Australia is often associated with those hydrogen defects, but again, this assignment is yet unproven.<ref name="argyle">{{Cite journal | last1 = Iakoubovskii | first1 = K. | last2 = Adriaenssens | first2 = G. J. | doi = 10.1016/S0925-9635(01)00533-7 | title = Optical characterization of natural Argyle diamonds | journal = Diamond and Related Materials | volume = 11 | issue = 1 | pages = 125 | year = 2002 | bibcode = 2002DRM....11..125I|url=https://www.researchgate.net/publication/229242723 }}</ref> |
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===镍与钴=== |
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| footer= A micrograph (top) and UV-excited photoluminescence (bottom) from a synthetic diamond plate (width ~3 mm). Most of yellow color and green emission originate from nickel.}} |
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When diamonds are grown by the high-pressure high-temperature technique, nickel, cobalt or some other metals are usually added into the growth medium to facilitate catalytically the conversion of graphite into diamond. As a result, metallic inclusions are formed. Besides, isolated nickel and cobalt atoms incorporate into diamond lattice, as demonstrated through characteristic hyperfine structure in [[electron paramagnetic resonance]], optical absorption and photoluminescence spectra,<ref>{{Cite journal | last1 = Iakoubovskii | first1 = K. | last2 = Davies | first2 = G. | doi = 10.1103/PhysRevB.70.245206 | title = Vibronic effects in the 1.4-eV optical center in diamond|url=https://www.researchgate.net/publication/238970570 | journal = Physical Review B | volume = 70 | issue = 24 | pages = 245206 | year = 2004 | bibcode = 2004PhRvB..70x5206I }}</ref> and the concentration of isolated nickel can reach 0.01%.<ref name=Ni>{{Cite journal | last1 = Collins | first1 = A. T. | last2 = Kanda | first2 = H. | last3 = Isoya | first3 = J. | last4 = Ammerlaan | first4 = C. A. J. | last5 = Van Wyk | first5 = J. A. | title = Correlation between optical absorption and EPR in high-pressure diamond grown from a nickel solvent catalyst | doi = 10.1016/S0925-9635(97)00270-7 | journal = Diamond and Related Materials | volume = 7 | issue = 2–5 | pages = 333 | year = 1998 | bibcode = 1998DRM.....7..333C }}</ref> This fact is by all means unusual considering the large difference in size between carbon and transition metal atoms and the superior rigidity of the diamond lattice.<ref name=walker/><ref name=Ni/> |
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Numerous Ni-related defects have been detected by [[electron paramagnetic resonance]],<ref name="align"/><ref name="nadol"/> optical absorption and [[photoluminescence]],<ref name="align"/><ref name="nadol"/><ref>{{cite journal|last1=Larico|first1=R.|last2=Justo|first2=J. F.|last3=Machado|first3=W. V. M.|last4=Assali|first4=L. V. C.|title=Electronic properties and hyperfine fields of nickel-related complexes in diamond|journal=Phys. Rev. B|date=2009|volume=79|issue=11|page=115202|doi=10.1103/PhysRevB.79.115202|arxiv = 1208.3207 |bibcode = 2009PhRvB..79k5202L }}</ref> both in synthetic and natural diamonds.<ref name="argyle"/> Three major structures can be distinguished: substitutional Ni,<ref>{{Cite journal | last1 = Isoya | first1 = J. | last2 = Kanda | first2 = H. | last3 = Norris | first3 = J. | last4 = Tang | first4 = J. | last5 = Bowman | first5 = M. | title = Fourier-transform and continuous-wave EPR studies of nickel in synthetic diamond: Site and spin multiplicity | doi = 10.1103/PhysRevB.41.3905 | journal = Physical Review B | volume = 41 | issue = 7 | pages = 3905 | year = 1990 | bibcode = 1990PhRvB..41.3905I }}</ref> nickel-vacancy<ref name=NiV>{{Cite journal | last1 = Iakoubovskii | first1 = K. | doi = 10.1103/PhysRevB.70.205211 | title = Ni-vacancy defect in diamond detected by electron spin resonance |url=https://www.researchgate.net/publication/235600434| journal = Physical Review B | volume = 70 | issue = 20 | pages = 205211 | year = 2004 | bibcode = 2004PhRvB..70t5211I }}</ref> and nickel-vacancy complex decorated by one or more substitutional nitrogen atoms.<ref name="nadol">{{Cite journal | last1 = Nadolinny | first1 = V. A. | last2 = Yelisseyev | first2 = A. P. | last3 = Baker | first3 = J. M. | last4 = Newton | first4 = M. E. | last5 = Twitchen | first5 = D. J. | last6 = Lawson | first6 = S. C. | last7 = Yuryeva | first7 = O. P. | last8 = Feigelson | first8 = B. N. | doi = 10.1088/0953-8984/11/38/314 | title = A study of <sup>13</sup>C hyperfine structure in the EPR of nickel-nitrogen-containing centres in diamond and correlation with their optical properties | journal = Journal of Physics: Condensed Matter | volume = 11 | issue = 38 | pages = 7357 | year = 1999 | bibcode = 1999JPCM...11.7357N }}</ref> The "nickel-vacancy" structure, also called "semi-divacancy" is specific for most large impurities in diamond and silicon (e.g., tin in silicon<ref>{{Cite journal | last1 = Watkins | first1 = G. | title = Defects in irradiated silicon: EPR of the tin-vacancy pair | doi = 10.1103/PhysRevB.12.4383 | journal = Physical Review B | volume = 12 | issue = 10 | pages = 4383–4390 | year = 1975 | bibcode = 1975PhRvB..12.4383W }}</ref>). Its production mechanism is generally accepted as follows: large nickel atom incorporates substitutionally, then expels a nearby carbon (creating a neighboring vacancy), and shifts in-between the two sites. |
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Although the physical and chemical properties of cobalt and nickel are rather similar, the concentrations of isolated cobalt in diamond are much smaller than those of nickel (parts per billion range). Several defects related to isolated cobalt have been detected by [[electron paramagnetic resonance]]<ref>{{Cite journal | last1 = Twitchen | first1 = D. | last2 = Baker | first2 = J. | last3 = Newton | first3 = M. | last4 = Johnston | first4 = K. | title = Identification of cobalt on a lattice site in diamond | doi = 10.1103/PhysRevB.61.9 | journal = Physical Review B | volume = 61 | issue = 1 | pages = 9 | year = 2000 | bibcode = 2000PhRvB..61....9T }}</ref> and [[photoluminescence]],<ref name="align"/><ref>{{Cite journal | last1 = Lawson | first1 = S. C. | last2 = Kanda | first2 = H. | last3 = Watanabe | first3 = K. | last4 = Kiflawi | first4 = I. | last5 = Sato | first5 = Y. | last6 = Collins | first6 = A. T. | doi = 10.1063/1.361744 | title = Spectroscopic study of cobalt-related optical centers in synthetic diamond | journal = Journal of Applied Physics | volume = 79 | issue = 8 | pages = 4348 | year = 1996 | bibcode = 1996JAP....79.4348L }}</ref> but their structure is yet unknown.<ref>{{cite journal|last1=Larico|first1=R.|last2=Assali|first2=L. V. C.|last3=Machado|first3=W. V. M.|last4=Justo|first4=J. F.|title=Cobalt-related impurity centers in diamond: electronic properties and hyperfine parameters|journal=J. Phys.: Condens. Matter|date=2008|volume=20|issue=41|page=415220|doi=10.1088/0953-8984/20/41/415220|arxiv = 1307.2866 |bibcode = 2008JPCM...20O5220L }}</ref> |
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===硅=== |
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[[File:semiv.JPG|thumb|right|150px|The semi-divacancy (impurity-vacancy) model for a large impurity in diamond (Ni, Co, Si, S, etc.), where a large pink impurity atom substitutes for two carbon atoms. Details on bonding with the diamond lattice are uncertain.]] |
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Silicon is a common impurity in diamond films grown by chemical vapor deposition and it originates either from silicon substrate or from silica windows or walls of the CVD reactor. It was also observed in natural diamonds in dispersed form.<ref>{{Cite journal | last1 = Iakoubovskii | first1 = K. | last2 = Adriaenssens | first2 = G. J. | last3 = Dogadkin | first3 = N. N. | last4 = Shiryaev | first4 = A. A. | title = Optical characterization of some irradiation-induced centers in diamond |url=https://www.researchgate.net/publication/229334290| doi = 10.1016/S0925-9635(00)00361-7 | journal = Diamond and Related Materials | volume = 10 | issue = 1 | pages = 18 | year = 2001 | bibcode = 2001DRM....10...18I }}</ref> Isolated silicon defects have been detected in diamond lattice through the sharp optical absorption peak at 738 nm<ref>{{Cite journal | last1 = Clark | first1 = C. | last2 = Kanda | first2 = H. | last3 = Kiflawi | first3 = I. | last4 = Sittas | first4 = G. | title = Silicon defects in diamond | doi = 10.1103/PhysRevB.51.16681 | journal = Physical Review B | volume = 51 | issue = 23 | pages = 16681 | year = 1995 | bibcode = 1995PhRvB..5116681C }}</ref> and [[electron paramagnetic resonance]].<ref name="edmonds">{{Cite journal | last1 = Edmonds | first1 = A. | last2 = Newton | first2 = M. | last3 = Martineau | first3 = P. | last4 = Twitchen | first4 = D. | last5 = Williams | first5 = S. | title = Electron paramagnetic resonance studies of silicon-related defects in diamond | doi = 10.1103/PhysRevB.77.245205 | journal = Physical Review B | volume = 77 | issue = 24 | pages = 245205 | year = 2008 | bibcode = 2008PhRvB..77x5205E }}</ref> Similar to other large impurities, the major form of silicon in diamond has been identified with a Si-vacancy complex (semi-divacancy site).<ref name="edmonds"/> This center is a deep donor having an ionization energy of 2 eV, and thus again is unsuitable for electronic applications.<ref>{{Cite journal | last1 = Iakoubovskii | first1 = K. | last2 = Adriaenssens | first2 = G. | doi = 10.1103/PhysRevB.61.10174 | title = Luminescence excitation spectra in diamond | journal = Physical Review B | volume = 61 | issue = 15 | pages = 10174 | year = 2000 | bibcode = 2000PhRvB..6110174I |url=https://www.researchgate.net/publication/235494828}}</ref> |
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[[Silicon-vacancy centre in diamond|Si-vacancies]] constitute minor fraction of total silicon. It is believed (though no proof exists) that much silicon substitutes for carbon thus becoming invisible to most spectroscopic techniques because silicon and carbon atoms have the same configuration of the outer electronic shells.<ref>{{Cite journal | last1 = d'Haenens-Johansson | first1 = U. | last2 = Edmonds | first2 = A. | last3 = Green | first3 = B. | last4 = Newton | first4 = M. | last5 = Davies | first5 = G. | last6 = Martineau | first6 = P. | last7 = Khan | first7 = R. | last8 = Twitchen | first8 = D. | doi = 10.1103/PhysRevB.84.245208 | title = Optical properties of the neutral silicon split-vacancy center in diamond | journal = Physical Review B | volume = 84 | issue = 24 | pages = 245208 | year = 2011 |bibcode = 2011PhRvB..84x5208D }}</ref> |
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===锗=== |
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Germanium is normally absent in diamond, but it can be introduced during the growth or by subsequent ion implantation. Germanium in diamond can be detected optically via the [[Germanium-vacancy centre in diamond|germanium-vacancy center]], which has similar properties to those of the [[Silicon-vacancy centre in diamond|Si-vacancy center]].<ref name=iwasaki2015>{{Cite journal | doi = 10.1038/srep12882| pmid = 26250337| pmc = 4528202| title = Germanium-Vacancy Single Color Centers in Diamond| journal = Scientific Reports| volume = 5| pages = 12882| year = 2015| last1 = Iwasaki | first1 = T. | last2 = Ishibashi | first2 = F. | last3 = Miyamoto | first3 = Y. | last4 = Doi | first4 = Y. | last5 = Kobayashi | first5 = S. | last6 = Miyazaki | first6 = T. | last7 = Tahara | first7 = K. | last8 = Jahnke | first8 = K. D. | last9 = Rogers | first9 = L. J. | last10 = Naydenov | first10 = B. | last11 = Jelezko | first11 = F. | last12 = Yamasaki | first12 = S. | last13 = Nagamachi | first13 = S. | last14 = Inubushi | first14 = T. | last15 = Mizuochi | first15 = N. | last16 = Hatano | first16 = M. | bibcode = 2015NatSR...512882I| arxiv = 1503.04938 }}</ref> |
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===硫=== |
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Around the year 2000, there was a wave of attempts to dope synthetic CVD diamond films by sulfur aiming at n-type conductivity with low activation energy. Successful reports have been published,<ref>{{Cite journal | last1 = Sakaguchi | first1 = I. | last2 = n.-Gamo | first2 = M. | last3 = Kikuchi | first3 = Y. | last4 = Yasu | first4 = E. | last5 = Haneda | first5 = H. | last6 = Suzuki | first6 = T. | last7 = Ando | first7 = T. | doi = 10.1103/PhysRevB.60.R2139 | title = Sulfur: A donor dopant for n-type diamond semiconductors | journal = Physical Review B | volume = 60 | issue = 4 | pages = R2139 | year = 1999 | bibcode = 1999PhRvB..60.2139S }}</ref> but then dismissed<ref>{{Cite journal | last1 = Kalish | first1 = R. | last2 = Reznik | first2 = A. | last3 = Uzan-Saguy | first3 = C. | last4 = Cytermann | first4 = C. | title = Is sulfur a donor in diamond? | doi = 10.1063/1.125885 | journal = Applied Physics Letters | volume = 76 | issue = 6 | pages = 757 | year = 2000 | bibcode = 2000ApPhL..76..757K }}</ref> as the conductivity was rendered p-type instead of n-type and associated not with sulfur, but with residual boron, which is a highly efficient p-type dopant in diamond. |
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So far (2009), there is only one reliable evidence (through hyperfine interaction structure in [[electron paramagnetic resonance]]) for isolated sulfur defects in diamond. The corresponding center called W31 has been observed in natural type-Ib diamonds in small concentrations (parts per million). It was assigned to a sulfur-vacancy complex – again, as in case of nickel and silicon, a semi-divacancy site.<ref>{{Cite journal | last1 = Baker | first1 = J. | last2 = Van Wyk | first2 = J. | last3 = Goss | first3 = J. | last4 = Briddon | first4 = P. | title = Electron paramagnetic resonance of sulfur at a split-vacancy site in diamond | doi = 10.1103/PhysRevB.78.235203 | journal = Physical Review B | volume = 78 | issue = 23 | pages = 235203 | year = 2008 |bibcode = 2008PhRvB..78w5203B }}</ref> |
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==本征缺陷== |
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The easiest way to produce intrinsic defects in diamond is by displacing carbon atoms through irradiation with high-energy particles, such as alpha (helium), beta (electrons) or gamma particles, protons, neutrons, ions, etc. The irradiation can occur in the laboratory or in the nature (see [[Artificially irradiated diamond|Diamond enhancement – Irradiation]]); it produces primary defects named [[frenkel defect]]s (carbon atoms knocked off their normal lattice sites to interstitial sites) and remaining lattice vacancies. An important difference between the vacancies and interstitials in diamond is that whereas interstitials are mobile during the irradiation, even at liquid nitrogen temperatures,<ref>{{Cite journal | last1 = Newton | first1 = M. E. | last2 = Campbell | first2 = B. A. | last3 = Twitchen | first3 = D. J. | last4 = Baker | first4 = J. M. | last5 = Anthony | first5 = T. R. | title = Recombination-enhanced diffusion of self-interstitial atoms and vacancy–interstitial recombination in diamond | doi = 10.1016/S0925-9635(01)00623-9 | journal = Diamond and Related Materials | volume = 11 | issue = 3–6 | pages = 618 | year = 2002 | bibcode = 2002DRM....11..618N }}</ref> however vacancies start migrating only at temperatures ~700 °C. |
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Vacancies and interstitials can also be produced in diamond by plastic deformation, though in much smaller concentrations. |
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===Isolated carbon interstitial=== |
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[[File:Model of the carbon split-interstitial in diamond.jpg|thumb|right|150px|Model of the carbon split-interstitial in diamond]] |
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Isolated [[Interstitial defect|interstitial]] has never been observed in diamond and is considered unstable. Its interaction with a regular carbon lattice atom produces a "split-interstitial", a defect where two carbon atoms share a lattice site and are covalently bonded with the carbon neighbors. This defect has been thoroughly characterized by [[electron paramagnetic resonance]] (R2 center)<ref>{{Cite journal | last1 = Hunt | first1 = D. | last2 = Twitchen | first2 = D. | last3 = Newton | first3 = M. | last4 = Baker | first4 = J. | last5 = Anthony | first5 = T. | last6 = Banholzer | first6 = W. | last7 = Vagarali | first7 = S. | doi = 10.1103/PhysRevB.61.3863 | title = Identification of the neutral carbon 〈100〉-split interstitial in diamond | journal = Physical Review B | volume = 61 | issue = 6 | pages = 3863 | year = 2000 | bibcode = 2000PhRvB..61.3863H }}</ref> and optical absorption,<ref>{{Cite journal | last1 = Smith | first1 = H. | last2 = Davies | first2 = G. | last3 = Newton | first3 = M. | last4 = Kanda | first4 = H. | title = Structure of the self-interstitial in diamond | doi = 10.1103/PhysRevB.69.045203 | journal = Physical Review B | volume = 69 | issue = 4 | pages = 045203 | year = 2004 | bibcode = 2004PhRvB..69d5203S }}</ref> and unlike most other defects in diamond, it does not produce [[photoluminescence]]. |
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===Interstitial complexes=== |
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[[File:2I.JPG|thumb|left|150px|One of the configurations of the carbon di-interstitials in diamond]] |
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The isolated split-interstitial moves through the diamond crystal during irradiation. When it meets other interstitials it aggregates into larger complexes of two and three split-interstitials, identified by [[electron paramagnetic resonance]] (R1 and O3 centers),<ref>{{Cite journal | last1 = Twitchen | first1 = D. | last2 = Newton | first2 = M. | last3 = Baker | first3 = J. | last4 = Tucker | first4 = O. | last5 = Anthony | first5 = T. | last6 = Banholzer | first6 = W. | doi = 10.1103/PhysRevB.54.6988 | title = Electron-paramagnetic-resonance measurements on the di-〈001〉-split interstitial center (R1) in diamond | journal = Physical Review B | volume = 54 | issue = 10 | pages = 6988 | year = 1996 | bibcode = 1996PhRvB..54.6988T }}</ref><ref>{{Cite journal | last1 = Hunt | first1 = D. | last2 = Twitchen | first2 = D. | last3 = Newton | first3 = M. | last4 = Baker | first4 = J. | last5 = Kirui | first5 = J. | last6 = Van Wyk | first6 = J. | last7 = Anthony | first7 = T. | last8 = Banholzer | first8 = W. | doi = 10.1103/PhysRevB.62.6587 | title = EPR data on the self-interstitial complex O3 in diamond | journal = Physical Review B | volume = 62 | issue = 10 | pages = 6587 | year = 2000 | bibcode = 2000PhRvB..62.6587H }}</ref> optical absorption and photoluminescence.<ref name="pb"/> |
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===Vacancy-interstitial complexes=== |
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Most high-energy particles, beside displacing carbon atom from the lattice site, also pass it enough surplus energy for a rapid migration through the lattice. However, when relatively gentle gamma irradiation is used, this extra energy is minimal. Thus the interstitials remain near the original vacancies and form vacancy-interstitials pairs identified through optical absorption.<ref name="pb">{{Cite journal | last1 = Iakoubovskii | first1 = K. | last2 = Dannefaer | first2 = S. | last3 = Stesmans | first3 = A. | title = Evidence for vacancy-interstitial pairs in Ib-type diamond |url=https://www.researchgate.net/publication/235548045| doi = 10.1103/PhysRevB.71.233201 | journal = Physical Review B | volume = 71 | issue = 23 | pages = 233201 | year = 2005 | bibcode = 2005PhRvB..71w3201I }}</ref><ref name=S1>{{Cite journal | last1 = Kiflawi | first1 = I. | last2 = Collins | first2 = A. T. | last3 = Iakoubovskii | first3 = K. | last4 = Fisher | first4 = D. | title = Electron irradiation and the formation of vacancy–interstitial pairs in diamond|url=https://www.researchgate.net/publication/231110579 | doi = 10.1088/0953-8984/19/4/046216 | journal = Journal of Physics: Condensed Matter | volume = 19 | issue = 4 | pages = 046216 | year = 2007 | bibcode = 2007JPCM...19d6216K }}</ref><ref>{{Cite journal | last1 = Iakoubovskii | first1 = K. | last2 = Kiflawi | first2 = I. | last3 = Johnston | first3 = K. | last4 = Collins | first4 = A. | last5 = Davies | first5 = G. | last6 = Stesmans | first6 = A. | doi = 10.1016/j.physb.2003.09.005 | title = Annealing of vacancies and interstitials in diamond | journal = Physica B: Condensed Matter | volume = 340–342 | pages = 67–75 | year = 2003 | bibcode = 2003PhyB..340...67I|url=https://www.researchgate.net/publication/236427847 }}</ref> |
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Vacancy-di-interstitial pairs have been also produced, though by electron irradiation and through a different mechanism:<ref>{{Cite journal | last1 = Iakoubovskii | first1 = K. | last2 = Baker | first2 = J. M. | last3 = Newton | first3 = M. E. | doi = 10.1002/pssa.200405163 | title = Electron spin resonance study of perturbed di-interstitials in diamond |url=https://www.researchgate.net/publication/239652459| journal = Physica Status Solidi A | volume = 201 | issue = 11 | pages = 2516 | year = 2004 | bibcode = 2004PSSAR.201.2516I }}</ref> Individual interstitials migrate during the irradiation and aggregate to form di-interstitials; this process occurs preferentially near the lattice vacancies. |
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===Isolated vacancy=== |
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[[File:irrdiamond.jpg|thumb|Pure diamonds, before and after irradiation and annealing. Clockwise from left bottom: 1) Initial (2×2 mm) 2–4) Irradiated by different doses of 2-MeV electrons 5–6) Irradiated by different doses and annealed at 800 °C.]] |
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Isolated [[Vacancy defect|vacancy]] is the most studied defect in diamond, both experimentally and theoretically. Its most important practical property is optical absorption, like in the [[color center]]s, which gives diamond green, or sometimes even green–blue color (in pure diamond). The characteristic feature of this absorption is a series of sharp lines called GR1-8, where GR1 line at 741 nm is the most prominent and important.<ref name=S1/> |
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The vacancy behaves as a deep electron donor/acceptor, whose electronic properties depend on the charge state. The energy level for the +/0 states is at 0.6 eV and for the 0/- states is at 2.5 eV above the [[valence band]].<ref name="v+">{{Cite journal | last1 = Dannefaer | first1 = S. | last2 = Iakoubovskii | first2 = K. | doi = 10.1088/0953-8984/20/23/235225 | pmid = 21694316 | title = Defects in electron irradiated boron-doped diamonds investigated by positron annihilation and optical absorption |url=https://www.researchgate.net/publication/51239495| journal = Journal of Physics: Condensed Matter | volume = 20 | issue = 23 | pages = 235225 | year = 2008 | bibcode = 2008JPCM...20w5225D }}</ref> |
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===Multivacancy complexes=== |
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<!-- Deleted image removed: [[File:Fancy colors.jpg|thumb|right|311px|Color in irradiated diamonds, with (two left stones) and without annealing (right){{puic|1=Fancy colors.jpg|log=2009 August 30}}]] --> |
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Upon annealing of pure diamond at ~700 °C, vacancies migrate and form divacancies, characterized by optical absorption and [[electron paramagnetic resonance]].<ref>{{Cite journal | last1 = Twitchen | first1 = D. | last2 = Newton | first2 = M. | last3 = Baker | first3 = J. | last4 = Anthony | first4 = T. | last5 = Banholzer | first5 = W. | title = Electron-paramagnetic-resonance measurements on the divacancy defect center R4/W6 in diamond | doi = 10.1103/PhysRevB.59.12900 | journal = Physical Review B | volume = 59 | issue = 20 | pages = 12900 | year = 1999 | bibcode = 1999PhRvB..5912900T }}</ref> |
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Similar to single interstitials, divacancies do not produce photoluminescence. Divacancies, in turn, anneal out at ~900 °C creating multivacancy chains detected by EPR<ref name=chains>{{Cite journal | last1 = Iakoubovskii | first1 = K. | last2 = Stesmans | first2 = A. | doi = 10.1103/PhysRevB.66.045406 | title = Dominant paramagnetic centers in <sup>17</sup>O-implanted diamond |url=https://www.researchgate.net/publication/243435184| journal = Physical Review B | volume = 66 | issue = 4 | pages = 045406 | year = 2002 | bibcode = 2002PhRvB..66d5406I }}</ref> and presumably hexavacancy rings. The latter should be invisible to most spectroscopies, and indeed, they have not been detected thus far.<ref name=chains/> Annealing of vacancies changes diamond color from green to yellow-brown. Similar mechanism (vacancy aggregation) is also believed to cause brown color of plastically deformed natural diamonds.<ref>{{Cite journal | last1 = Hounsome | first1 = L. | last2 = Jones | first2 = R. | last3 = Martineau | first3 = P. | last4 = Fisher | first4 = D. | last5 = Shaw | first5 = M. | last6 = Briddon | first6 = P. | last7 = Öberg | first7 = S. | title = Origin of brown coloration in diamond | doi = 10.1103/PhysRevB.73.125203 | journal = Physical Review B | volume = 73 | issue = 12 | pages = 125203 | year = 2006 | bibcode = 2006PhRvB..73l5203H }}</ref> |
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===Dislocations=== |
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[[Dislocation]]s are the most common structural defect in natural diamond. The two major types of dislocations are the ''glide set'', in which [[chemical bond|bonds]] break between layers of atoms with different indices (those not lying directly above each other) and the ''shuffle set'', in which the breaks occur between atoms of the same index. The dislocations produce dangling bonds which introduce energy levels into the band gap, enabling the absorption of light.<ref>Kolodzie, A.T. and Bleloch, A.L. [http://www.icem15.com/Documents/Diamonds.pdf Investigation of band gap energy states at dislocations in natural diamond] {{webarchive|url=https://web.archive.org/web/20050528202931/http://www.icem15.com/Documents/Diamonds.pdf |date=May 28, 2005 }}. Cavendish Laboratory, University of Cambridge; Cambridge, England.</ref> Broadband blue [[photoluminescence]] has been reliably identified with dislocations by direct observation in an [[electron microscope]], however, it was noted that not all dislocations are luminescent, and there is no correlation between the dislocation type and the parameters of the emission.<ref>{{Cite journal | last1 = Hanley | first1 = P. L. | last2 = Kiflawi | first2 = I. | last3 = Lang | first3 = A. R. | doi = 10.1098/rsta.1977.0012 | title = On Topographically Identifiable Sources of Cathodoluminescence in Natural Diamonds | journal = Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences | volume = 284 | issue = 1324 | pages = 329 | year = 1977 | bibcode = 1977RSPTA.284..329H }}</ref> |
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===Platelets=== |
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[[File:Platelets.JPG|thumb|right|Electron micrograph of platelets in diamond viewed normal to the cubic axis.<ref name="plat"/> Image width 1.5 µm]] |
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Most natural diamonds contain extended planar defects in the <100> lattice planes, which are called platelets. Their size ranges from nanometers to many micrometers, and large ones are easily observed in an [[optical microscope]] via their luminescence.<ref>{{Cite journal | doi = 10.1038/267036a0| title = Polarised infrared cathodoluminescence from platelet defects in natural diamonds| journal = Nature| volume = 267| issue = 5606| pages = 36| year = 1977| last1 = Kiflawi | first1 = I.| last2 = Lang | first2 = A. R.|bibcode = 1977Natur.267...36K }}</ref> For a long time, platelets were tentatively associated with large nitrogen complexes — nitrogen sinks produced as a result of nitrogen aggregation at high temperatures of the diamond synthesis. However, direct measurement of nitrogen in the platelets by [[EELS]] (an analytical technique of electron microscopy) revealed very little nitrogen.<ref name="plat"/> The currently accepted model of platelets is a large regular array of carbon interstitials.<ref>{{Cite journal | last1 = Goss | first1 = J. | last2 = Coomer | first2 = B. | last3 = Jones | first3 = R. | last4 = Fall | first4 = C. | last5 = Briddon | first5 = P. | last6 = Öberg | first6 = S. | doi = 10.1103/PhysRevB.67.165208 | title = Extended defects in diamond: The interstitial platelet | journal = Physical Review B | volume = 67 | issue = 16 | pages = 165208 | year = 2003 | bibcode = 2003PhRvB..67p5208G }}</ref> |
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Platelets produce sharp absorption peaks at 1359–1375 and 330 cm<sup>−1</sup> in IR absorption spectra; remarkably, the position of the first peak depends on the platelet size.<ref name="plat">{{Cite journal | last1 = Kiflawi | first1 = I. | last2 = Bruley | first2 = J. | last3 = Luyten | first3 = W. | last4 = Van Tendeloo | first4 = G. | title = 'Natural' and 'man-made' platelets in type-Ia diamonds |url=http://ematweb.cmi.ua.ac.be/emat/pdf/0956.pdf| doi = 10.1080/014186398258104 | journal = Philosophical Magazine B | volume = 78 | issue = 3 | pages = 299 | year = 1998 | pmid = | pmc = | bibcode = 1998PMagB..78..299K }}</ref> <ref name="platnew">{{Cite journal | last1 = Speich | first1 = L. | last2 = Kohn | first2 = S.C. | last3 = Wirth | first3 = R. | last4 = Bulanova | first4 = G.P. | last5 = Smith | first5 = C.B. | title = The relationship between platelet size and the B′ infrared peak of natural diamonds revisited | doi = 10.1016/j.lithos.2017.02.010 | journal = Lithos | volume = 278-281 | pages = 419–426 | year = 2017 | pmid = | pmc = | bibcode = 2017Litho.278..419S | url = https://research-information.bristol.ac.uk/en/publications/the-relationship-between-platelet-size-and-the-b-infrared-peak-of-natural-diamonds-revisited(34ba5767-e947-43d2-a4da-41dd88455f70).html }}</ref> As with dislocations, a broad photoluminescence centered at ~1000 nm was associated with platelets by direct observation in an electron microscope. By studying this luminescence, it was deduced that platelets have a "bandgap" of ~1.7 eV.<ref>{{Cite journal | last1 = Iakoubovskii | first1 = K. | last2 = Adriaenssens | first2 = G. J. | doi = 10.1080/095008300403594 | title = Characterization of platelet-related infrared luminescence in diamond | journal = Philosophical Magazine Letters | volume = 80 | issue = 6 | pages = 441 | year = 2000 | bibcode = 2000PMagL..80..441A|url=https://www.researchgate.net/publication/253678224 }}</ref> |
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===Voidites=== |
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[[File:Voidites.jpg|thumb|left|upright|Electron micrograph showing several octahedral voidites]] |
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Voidites are [[Octahedron|octahedral]] nanometer-sized clusters present in many natural diamonds, as revealed by [[electron microscopy]].<ref>{{Cite journal | last1 = Chen | first1 = J. H. | last2 = Bernaerts | first2 = D. | last3 = Seo | first3 = J. W. | last4 = Van Tendeloo | first4 = G. | last5 = Kagi | first5 = H. | title = Voidites in polycrystalline natural diamond |url=https://www.researchgate.net/publication/263263432| doi = 10.1080/095008398178561 | journal = Philosophical Magazine Letters | volume = 77 | issue = 3 | pages = 135 | year = 1998 | bibcode = 1998PMagL..77..135H }}</ref> Laboratory experiments demonstrated that annealing of type-IaB diamond at high temperatures and pressures (>2600 °C) results in break-up of the platelets and formation of dislocation loops and voidites, i.e. that voidites are a result of thermal degradation of platelets. Contrary to platelets, voidites do contain much nitrogen, in the molecular form.<ref>{{Cite journal | last1 = Kiflawi | first1 = I. | last2 = Bruley | first2 = J. | doi = 10.1016/S0925-9635(99)00265-4 | title = The nitrogen aggregation sequence and the formation of voidites in diamond | journal = Diamond and Related Materials | volume = 9 | issue = 1 | pages = 87 | year = 2000 | bibcode = 2000DRM.....9...87K }}</ref> |
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==复合缺陷== |
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Extrinsic and intrinsic defects can interact producing new defect complexes. Such interaction usually occurs if a diamond containing extrinsic defects (impurities) is either plastically deformed or is irradiated and annealed. |
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[[File:H3center.JPG|thumb|right|150px|Schematic of the H3 and H2 centers]] |
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Most important is the interaction of vacancies and interstitials with nitrogen. Carbon interstitials react with substitutional nitrogen producing a bond-centered nitrogen interstitial showing strong IR absorption at 1450 cm<sup>−1</sup>.<ref>{{Cite journal | last1 = Kiflawi | first1 = I. | last2 = Mainwood | first2 = A. | last3 = Kanda | first3 = H. | last4 = Fisher | first4 = D. | title = Nitrogen interstitials in diamond | doi = 10.1103/PhysRevB.54.16719 | journal = Physical Review B | volume = 54 | issue = 23 | pages = 16719 | year = 1996 | bibcode = 1996PhRvB..5416719K }}</ref> Vacancies are efficiently trapped by the A, B and C nitrogen centers. The trapping rate is the highest for the C centers, 8 times lower for the A centers and 30 times lower for the B centers.<ref>{{cite journal | last1 = Iakoubovskii | first1 = Konstantin | last2 = Adriaenssens | first2 = Guy J | year = 2001 | title = Trapping of vacancies by defects in diamond |url=https://www.researchgate.net/publication/230912003| journal = Journal of Physics: Condensed Matter | volume = 13 | issue = 26 | pages = 6015 | doi = 10.1088/0953-8984/13/26/316 |bibcode = 2001JPCM...13.6015I }}</ref> The C center (single nitrogen) by trapping a vacancy forms the famous [[nitrogen-vacancy center]], which can be neutral or negatively charged;<ref>{{Cite journal | last1 = Iakoubovskii | first1 = K. | last2 = Adriaenssens | first2 = G. J. | last3 = Nesladek | first3 = M. | doi = 10.1088/0953-8984/12/2/308 | title = Photochromism of vacancy-related centres in diamond |url=https://www.researchgate.net/publication/231101413| journal = Journal of Physics: Condensed Matter | volume = 12 | issue = 2 | pages = 189 | year = 2000 | bibcode = 2000JPCM...12..189I }}</ref><ref>{{Cite journal | last1 = Mita | first1 = Y. | title = Change of absorption spectra in type-Ib diamond with heavy neutron irradiation | doi = 10.1103/PhysRevB.53.11360 | journal = Physical Review B | volume = 53 | issue = 17 | pages = 11360–11364 | year = 1996 | bibcode = 1996PhRvB..5311360M }}</ref> the negatively charged state has potential applications in [[quantum computing]]. A and B centers upon trapping a vacancy create corresponding 2N-V (H3<ref>{{Cite journal | last1 = Davies | first1 = G. | last2 = Nazare | first2 = M. H. | last3 = Hamer | first3 = M. F. | doi = 10.1098/rspa.1976.0140 | title = The H3 (2.463 eV) Vibronic Band in Diamond: Uniaxial Stress Effects and the Breakdown of Mirror Symmetry | journal = Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences | volume = 351 | issue = 1665 | pages = 245 | year = 1976 | bibcode = 1976RSPSA.351..245D }}</ref> and H2<ref>{{Cite journal | last1 = Lawson | first1 = S. C. | last2 = Davies | first2 = G. | last3 = Collins | first3 = A. T. | last4 = Mainwood | first4 = A. | title = The 'H2' optical transition in diamond: The effects of uniaxial stress perturbations, temperature and isotopic substitution | doi = 10.1088/0953-8984/4/13/008 | journal = Journal of Physics: Condensed Matter | volume = 4 | issue = 13 | pages = 3439 | year = 1992 | bibcode = 1992JPCM....4.3439L }}</ref> centers, where H2 is simply a negatively charged H3 center<ref>{{Cite journal | last1 = Mita | first1 = Y. | last2 = Nisida | first2 = Y. | last3 = Suito | first3 = K. | last4 = Onodera | first4 = A. | last5 = Yazu | first5 = S. | title = Photochromism of H2 and H3 centres in synthetic type Ib diamonds | doi = 10.1088/0953-8984/2/43/002 | journal = Journal of Physics: Condensed Matter | volume = 2 | issue = 43 | pages = 8567 | year = 1990 | bibcode = 1990JPCM....2.8567M }}</ref>) and the neutral 4N-2V (H4 center<ref>{{Cite journal | last1 = Sa | first1 = E. S. D. | last2 = Davies | first2 = G. | doi = 10.1098/rspa.1977.0165 | title = Uniaxial Stress Studies of the 2.498 eV (H4), 2.417 eV and 2.536 eV Vibronic Bands in Diamond | journal = Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences | volume = 357 | issue = 1689 | pages = 231 | year = 1977 | pmid = | pmc = | bibcode = 1977RSPSA.357..231S }}</ref>). The H2, H3 and H4 centers are important because they are present in many natural diamonds and their optical absorption can be strong enough to alter the diamond color (H3 or H4 – yellow, H2 – green). |
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Boron interacts with carbon interstitials forming a neutral boron–interstitial complex with a sharp optical absorption at 0.552 eV (2250 nm).<ref name="v+"/> No evidence is known so far (2009) for complexes of boron and vacancy.<ref name=collins2>{{Cite journal | last1 = Collins | first1 = A. T. | title = Things we still don't know about optical centres in diamond | doi = 10.1016/S0925-9635(99)00013-8 | journal = Diamond and Related Materials | volume = 8 | issue = 8–9 | pages = 1455–1462 | year = 1999 | bibcode = 1999DRM.....8.1455C }}</ref> |
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In contrast, silicon does react with vacancies, creating the described above optical absorption at 738 nm.<ref>{{Cite journal | last1 = Collins | first1 = A. T. | last2 = Allers | first2 = L. | last3 = Wort | first3 = C. J. H. | last4 = Scarsbrook | first4 = G. A. | title = The annealing of radiation damage in De Beers colourless CVD diamond | doi = 10.1016/0925-9635(94)90302-6 | journal = Diamond and Related Materials | volume = 3 | issue = 4–6 | pages = 932 | year = 1994 | bibcode = 1994DRM.....3..932C }}</ref> The assumed mechanism is trapping of migrating vacancy by substitutional silicon resulting in the Si-V (semi-divacancy) configuration.<ref>{{Cite journal | last1 = Goss | first1 = J. | last2 = Jones | first2 = R. | last3 = Breuer | first3 = S. | last4 = Briddon | first4 = P. | last5 = Öberg | first5 = S. | title = The Twelve-Line 1.682 eV Luminescence Center in Diamond and the Vacancy-Silicon Complex | doi = 10.1103/PhysRevLett.77.3041 | journal = Physical Review Letters | volume = 77 | issue = 14 | pages = 3041–3044 | year = 1996 | pmid = 10062116| pmc = |bibcode = 1996PhRvL..77.3041G }}</ref> |
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A similar mechanism is expected for nickel, for which both substitutional and semi-divacancy configurations are reliably identified (see subsection "nickel and cobalt" above). In an unpublished study, diamonds rich in substitutional nickel were electron irradiated and annealed, with following careful optical measurements performed after each annealing step, but no evidence for creation or enhancement of Ni-vacancy centers was obtained.<ref name=NiV/> |
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==See also== |
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{{div col|colwidth=30em}} |
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*[[Chemical vapor deposition of diamond]] |
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*[[Crystallographic defect]] |
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*[[Diamond color]] |
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*[[Diamond enhancement]] |
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*[[Gemstone irradiation]] |
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*[[Material properties of diamond]] |
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*[[Nitrogen-vacancy center]] |
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*[[Synthetic diamond]] |
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{{div col end}} |
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==References== |
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{{reflist|35em}} |
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{{DEFAULTSORT:Crystallographic Defects In Diamond}} |
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[[Category:钻石]] |
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[[Category:晶体缺陷]] |
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