Special Issue "Diamond Crystals"

A special issue of Crystals (ISSN 2073-4352). This special issue belongs to the section "Crystal Engineering".

Deadline for manuscript submissions: closed (30 June 2017)

Special Issue Editor

Guest Editor
Dr. Yuri N. Palyanov

1. VS Sobolev Institute of Geology and Mineralogy, Siberian Branch of Russian Academy of Sciences, Novosibirsk, Russia
2. Novosibirsk State University, Novosibirsk, Russia
Website | E-Mail
Interests: synthetic and natural diamond, diamond synthesis and growth, high pressure high temperature, experimental modelling of natural diamond formation, diamond mineralogy, diamond properties and applications.

Special Issue Information

Dear Colleagues,

Diamonds, which possess a remarkable range of extreme and outstanding properties superior to other materials, have been attracting huge interest as a versatile and technologically useful material. Advances in diamond synthesis and growth techniques have paved the way for this unique material to many existent and prospective applications, which now range from optics and electronics to biomedicine and quantum computing. Besides its importance as the strategic future of electronic material, diamond has been the classical model object of fundamental research in solid-state physics, chemistry and engineering. Diamond occupies a very special place in the Earth sciences, where it serves as an invaluable source of information about the Earth’s interior. And, of course, being the king of gems, diamond is the key stone for the gem industry and gemmological science.

We invite researchers to contribute to the Special Issue on “Diamond Crystals”, which is intended to serve as a unique multidisciplinary forum covering broad aspects of science, technology and the application of synthetic and natural diamonds.
 The potential topics include, but are not limited to:
-    Synthesis and growth of diamond crystals
-    Genesis of natural diamond
-    Diamond morphology
-    Real structure and properties of synthetic and natural diamond
-    Characterisation of diamond by spectroscopic, microscopic and other advanced techniques
-    Exploitation of the remarkable properties of diamond in various existent and emerging applications

Dr. Yuri N. Palyanov
Guest Editors

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Crystals is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1000 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

• Diamond crystals
• Diamond growth and synthesis
• High Pressure High Temperature (HPHT)
• Chemical Vapour Deposition (CVD)
• Natural diamond
• Diamond properties
• Characterization
• Diamond applications

Published Papers (12 papers)

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Research

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Open AccessArticle Effect of Nitrogen Impurities on the Raman Line Width in Diamond, Revisited
Crystals 2017, 7(8), 239; doi:10.3390/cryst7080239
Received: 30 June 2017 / Revised: 25 July 2017 / Accepted: 28 July 2017 / Published: 31 July 2017
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Abstract
The results of a high-resolution Raman scattering study of a diamond crystal with a high content of single substitutional nitrogen impurities (550 ppm) in the temperature range from 50 to 673 K are presented and compared with the data for defect-free diamond. It
[...] Read more.
The results of a high-resolution Raman scattering study of a diamond crystal with a high content of single substitutional nitrogen impurities (550 ppm) in the temperature range from 50 to 673 K are presented and compared with the data for defect-free diamond. It is established that the increase of the nitrogen concentration in diamond leads to the temperature-independent increase of the Raman line width. Analysis of the experimental data allows us to conclude that this broadening should be attributed to the defect-induced shortening of the Raman phonon lifetime. We believe that this mechanism is responsible for the increase of the Raman line width caused by most point-like defects in diamond. No pronounced effects of the nitrogen defects on the Raman line position and phonon anharmonicity are observed. Full article
(This article belongs to the Special Issue Diamond Crystals)
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Open AccessArticle The Internal Structure of Yellow Cuboid Diamonds from Alluvial Placers of the Northeastern Siberian Platform
Crystals 2017, 7(8), 238; doi:10.3390/cryst7080238
Received: 30 June 2017 / Revised: 26 July 2017 / Accepted: 28 July 2017 / Published: 31 July 2017
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Abstract
Yellow cuboid diamonds are commonly found in diamondiferous alluvial placers of the Northeastern Siberian platform. The internal structure of these diamonds have been studied by optical microscopy, X-Ray topography (XRT) and electron backscatter diffraction (EBSD) techniques. Most of these crystals have typical resorption
[...] Read more.
Yellow cuboid diamonds are commonly found in diamondiferous alluvial placers of the Northeastern Siberian platform. The internal structure of these diamonds have been studied by optical microscopy, X-Ray topography (XRT) and electron backscatter diffraction (EBSD) techniques. Most of these crystals have typical resorption features and do not preserve primary growth morphology. The resorption leads to an evolution from an originally cubic shape to a rounded tetrahexahedroid. Specific fibrous or columnar internal structure of yellow cuboid diamonds has been revealed. Most of them are strongly deformed. Misorientations of the crystal lattice, found in the samples, may be caused by strains from their fibrous growth or/and post-growth plastic deformation. Full article
(This article belongs to the Special Issue Diamond Crystals)
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Open AccessArticle Non-Destructive In Situ Study of Plastic Deformations in Diamonds: X-ray Diffraction Topography and µFTIR Mapping of Two Super Deep Diamond Crystals from São Luiz (Juina, Brazil)
Crystals 2017, 7(8), 233; doi:10.3390/cryst7080233
Received: 29 June 2017 / Revised: 24 July 2017 / Accepted: 25 July 2017 / Published: 28 July 2017
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Abstract
Diamonds from Juina, Brazil, are well-known examples of superdeep diamond crystals formed under sublithospheric conditions and evidence would indicate their origins lie as deep as the Earth’s mantle transition zone and the Lower Mantle. Detailed characterization of these minerals and of inclusions trapped
[...] Read more.
Diamonds from Juina, Brazil, are well-known examples of superdeep diamond crystals formed under sublithospheric conditions and evidence would indicate their origins lie as deep as the Earth’s mantle transition zone and the Lower Mantle. Detailed characterization of these minerals and of inclusions trapped within them may thus provide precious minero-petrogenetic information on their growth history in these inaccessible environments. With the aim of studying non-destructively the structural defects in the entire crystalline volume, two diamond samples from this locality, labelled JUc4 and BZ270, respectively, were studied in transmission mode by means of X-ray Diffraction Topography (XRDT) and micro Fourier Transform InfraRed Spectroscopy (µFTIR). The combined use of these methods shows a good fit between the mapping of spatial distribution of extended defects observed on the topographic images and the µFTIR maps corresponding to the concentration of N and H point defects. The results obtained show that both samples are affected by plastic deformation. In particular, BZ270 shows a lower content of nitrogen and higher deformation, and actually consists of different, slightly misoriented grains that contain sub-grains with a rounded-elongated shape. These features are commonly associated with deformation processes by solid-state diffusion creep under high pressure and high temperature. Full article
(This article belongs to the Special Issue Diamond Crystals)
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Open AccessArticle Experimental and Theoretical Evidence for Surface-Induced Carbon and Nitrogen Fractionation during Diamond Crystallization at High Temperatures and High Pressures
Crystals 2017, 7(7), 190; doi:10.3390/cryst7070190
Received: 31 March 2017 / Revised: 21 June 2017 / Accepted: 22 June 2017 / Published: 26 June 2017
Cited by 1 | PDF Full-text (1925 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Isotopic and trace element variations within single diamond crystals are widely known from both natural stones and synthetic crystals. A number of processes can produce variations in carbon isotope composition and nitrogen abundance in the course of diamond crystallization. Here, we present evidence
[...] Read more.
Isotopic and trace element variations within single diamond crystals are widely known from both natural stones and synthetic crystals. A number of processes can produce variations in carbon isotope composition and nitrogen abundance in the course of diamond crystallization. Here, we present evidence of carbon and nitrogen fractionation related to the growing surfaces of a diamond. We document that difference in the carbon isotope composition between cubic and octahedral growth sectors is solvent-dependent and varies from 0.7‰ in a carbonate system to 0.4‰ in a metal-carbon system. Ab initio calculations suggest up to 4‰ instantaneous 13C depletion of cubic faces in comparison to octahedral faces when grown simultaneously. Cubic growth sectors always have lower nitrogen abundance in comparison to octahedral sectors within synthetic diamond crystals in both carbonate and metal-carbon systems. The stability of any particular growth faces of a diamond crystal depends upon the degree of carbon association in the solution. Octahedron is the dominant form in a high-associated solution while the cube is the dominant form in a low-associated solution. Fine-scale data from natural crystals potentially can provide information on the form of carbon, which was present in the growth media. Full article
(This article belongs to the Special Issue Diamond Crystals)
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Open AccessArticle Evolution in Time of Radiation Defects Induced by Negative Pions and Muons in Crystals with a Diamond Structure
Crystals 2017, 7(6), 174; doi:10.3390/cryst7060174
Received: 27 March 2017 / Revised: 29 May 2017 / Accepted: 9 June 2017 / Published: 14 June 2017
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Abstract
Evolution in time of radiation defects induced by negatively-charged pions and muons in crystals with diamond structures is considered. Negative pions and muons are captured by the nucleus and ionize an appropriate host atom, forming a positively-charged radiation defect in a lattice. As
[...] Read more.
Evolution in time of radiation defects induced by negatively-charged pions and muons in crystals with diamond structures is considered. Negative pions and muons are captured by the nucleus and ionize an appropriate host atom, forming a positively-charged radiation defect in a lattice. As a result of an evolution in time, this radiation defect transforms into the acceptor center. An analysis of the full evolution process is considered for the first time. Formation of this acceptor center can be divided into three stages. At the first stage, the radiation defect interacts with a radiation trace and captures electrons. The radiation defect is neutralized completely in Si and Ge for a short time t 10 11 s, but in diamond, the complete neutralization time is very large t 10 6 s. At the second stage, broken chemical bonds of the radiation defect are restored. In Si and Ge, this process takes place for the neutral radiation defect, but in diamond, it goes for a positively-charged state. The characteristic time of this stage is t < 10 8 s for Si and Ge and t < 10 11 s for diamond. After the chemical bonds’ restoration, the positively-charged, but chemically-bound radiation defect in diamond is quickly neutralized because of the electron density redistribution. The neutralization process is characterized by the lattice relaxation time. At the third stage, a neutral chemically-bound radiation defect captures an additional electron to saturate all chemical bonds and forms an ionized acceptor center. The existence of a sufficiently big electric dipolar moment leads to the electron capture. Qualitative estimates for the time of this process were obtained for diamond, silicon and germanium crystals. It was sown that this time is the shortest for diamond (≤ 10 8 s) and the longest for silicon (≤ 10 7 s) Full article
(This article belongs to the Special Issue Diamond Crystals)
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Open AccessArticle Morphology of Diamond Layers Grown on Different Facets of Single Crystal Diamond Substrates by a Microwave Plasma CVD in CH4-H2-N2 Gas Mixtures
Crystals 2017, 7(6), 166; doi:10.3390/cryst7060166
Received: 30 April 2017 / Revised: 29 May 2017 / Accepted: 31 May 2017 / Published: 6 June 2017
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Abstract
Epitaxial growth of diamond films on different facets of synthetic IIa-type single crystal (SC) high-pressure high temperature (HPHT) diamond substrate by a microwave plasma CVD in CH4-H2-N2 gas mixture with the high concentration (4%) of nitrogen is studied.
[...] Read more.
Epitaxial growth of diamond films on different facets of synthetic IIa-type single crystal (SC) high-pressure high temperature (HPHT) diamond substrate by a microwave plasma CVD in CH4-H2-N2 gas mixture with the high concentration (4%) of nitrogen is studied. A beveled SC diamond embraced with low-index {100}, {110}, {111}, {211}, and {311} faces was used as the substrate. Only the {100} face is found to sustain homoepitaxial growth at the present experimental parameters, while nanocrystalline diamond (NCD) films are produced on other planes. This observation is important for the choice of appropriate growth parameters, in particular, for the production of bi-layer or multilayer NCD-on-microcrystalline diamond (MCD) superhard coatings on tools when the deposition of continuous conformal NCD film on all facet is required. The development of the film morphology with growth time is examined with SEM. The structure of hillocks, with or without polycrystalline aggregates, that appear on {100} face is analyzed, and the stress field (up to 0.4 GPa) within the hillocks is evaluated based on high-resolution mapping of photoluminescence spectra of nitrogen-vacancy NV optical centers in the film. Full article
(This article belongs to the Special Issue Diamond Crystals)
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Open AccessArticle Specific Internal Structure of Diamonds from Zarnitsa Kimberlite Pipe
Crystals 2017, 7(5), 133; doi:10.3390/cryst7050133
Received: 30 March 2017 / Revised: 4 May 2017 / Accepted: 7 May 2017 / Published: 11 May 2017
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Abstract
The Zarnitsa kimberlite pipe is one of the largest pipes of the Yakutian diamondiferous province. Currently, some limited published data exists on the diamonds from this deposit. Among the diamond population of this pipe there is a specific series of dark gray to
[...] Read more.
The Zarnitsa kimberlite pipe is one of the largest pipes of the Yakutian diamondiferous province. Currently, some limited published data exists on the diamonds from this deposit. Among the diamond population of this pipe there is a specific series of dark gray to black diamonds with transition morphologies between octahedron and rounded rhombic dodecahedron. These diamonds have specific zonal and sectorial mosaic-block internal structures. The inner parts of these crystals have polycrystalline structure with significant misorientations between sub-individuals. The high consistency of the mechanical admixtures (inclusions) in the diamonds cores can cause a high grid stress of the crystal structure and promote the block (polycrystalline) structure of the core components. These diamond crystals have subsequently been formed due to crystallization of bigger sub-individuals on the polycrystalline cores according to the geometric selection law. Full article
(This article belongs to the Special Issue Diamond Crystals)
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Open AccessArticle Nanoscale Sensing Using Point Defects in Single-Crystal Diamond: Recent Progress on Nitrogen Vacancy Center-Based Sensors
Crystals 2017, 7(5), 124; doi:10.3390/cryst7050124
Received: 8 April 2017 / Revised: 21 April 2017 / Accepted: 24 April 2017 / Published: 28 April 2017
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Abstract
Individual, luminescent point defects in solids, so-called color centers, are atomic-sized quantum systems enabling sensing and imaging with nanoscale spatial resolution. In this overview, we introduce nanoscale sensing based on individual nitrogen vacancy (NV) centers in diamond. We discuss two central challenges of
[...] Read more.
Individual, luminescent point defects in solids, so-called color centers, are atomic-sized quantum systems enabling sensing and imaging with nanoscale spatial resolution. In this overview, we introduce nanoscale sensing based on individual nitrogen vacancy (NV) centers in diamond. We discuss two central challenges of the field: first, the creation of highly-coherent, shallow NV centers less than 10 nm below the surface of a single-crystal diamond; second, the fabrication of tip-like photonic nanostructures that enable efficient fluorescence collection and can be used for scanning probe imaging based on color centers with nanoscale resolution. Full article
(This article belongs to the Special Issue Diamond Crystals)
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Open AccessArticle HPHT Diamond Crystallization in the Mg-Si-C System: Effect of Mg/Si Composition
Crystals 2017, 7(5), 119; doi:10.3390/cryst7050119
Received: 31 March 2017 / Revised: 21 April 2017 / Accepted: 23 April 2017 / Published: 25 April 2017
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Abstract
Crystallization of diamond in the Mg-Si-C system has been studied at 7.5 GPa and 1800 °C with the Mg-Si compositions spanning the range from Mg-C to Si-C end-systems. It is found that as Si content of the system increases from 0 to 2
[...] Read more.
Crystallization of diamond in the Mg-Si-C system has been studied at 7.5 GPa and 1800 °C with the Mg-Si compositions spanning the range from Mg-C to Si-C end-systems. It is found that as Si content of the system increases from 0 to 2 wt %, the degree of the graphite-to-diamond conversion increases from about 50 to 100% and remains at about this level up to 20 wt % Si. A further increase in Si content of the system leads to a decrease in the graphite-to-diamond conversion degree down to complete termination of diamond synthesis at Si content >50 wt %. Depending on the Si content crystallization of diamond, joint crystallization of diamond and silicon carbide and crystallization of silicon carbide only are found to take place. The cubic growth of diamond, typical of the Mg-C system, transforms to the cube-octahedron upon adding 1 wt % Si and then to the octahedron at a Si content of 2 wt % and higher. The crystallized diamonds are studied by a suite of optical spectroscopy techniques and the major characteristics of their defect-and-impurity structure are revealed. The correlations between the Si content of the Mg-Si-C system and the properties of the produced diamond crystals are established. Full article
(This article belongs to the Special Issue Diamond Crystals)
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Open AccessArticle Thermochemical Wear of Single Crystal Diamond Catalyzed by Ferrous Materials at Elevated Temperature
Crystals 2017, 7(4), 116; doi:10.3390/cryst7040116
Received: 25 March 2017 / Revised: 15 April 2017 / Accepted: 17 April 2017 / Published: 19 April 2017
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Abstract
Single crystal diamond has been recognized as the optimal tool material in ultra-precision machining. However, the excessive tool wear prevents it from cutting ferrous materials. This paper conducts a series of thermal analysis tests under the conditions of different gas atmospheres, heating temperatures,
[...] Read more.
Single crystal diamond has been recognized as the optimal tool material in ultra-precision machining. However, the excessive tool wear prevents it from cutting ferrous materials. This paper conducts a series of thermal analysis tests under the conditions of different gas atmospheres, heating temperatures, crystallographic planes and workpiece materials, in order to clarify the details of thermochemical wear of diamond catalyzed by iron at elevated temperature. Raman scattering analysis was performed to identify the transformation of diamond crystal structure. Energy dispersive X-ray analysis was used to detect the change in chemical composition of the work material. X-ray photoelectron spectroscopy was adopted to confirm the resultants of interfacial thermochemical reactions. The experimental results revealed that the diamond wear included the graphitization, diffusion and oxidation. Temperature was considered as the key factor affecting these wear mechanisms. The initial graphitization temperatures of diamond catalyzed by iron under different conditions were obtained, and the graphitized degree relied heavily on the crystallographic plane while being insensitive to the workpiece material. The diffusion wear rule was preliminarily achieved by the established prediction model of the carbon atoms diffusing into the iron lattice, and the types and resultants of interfacial chemical reactions were deduced. Full article
(This article belongs to the Special Issue Diamond Crystals)
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Open AccessArticle Fabrication of Low Dislocation Density, Single-Crystalline Diamond via Two-Step Epitaxial Lateral Overgrowth
Crystals 2017, 7(4), 114; doi:10.3390/cryst7040114
Received: 15 March 2017 / Revised: 13 April 2017 / Accepted: 17 April 2017 / Published: 18 April 2017
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Abstract
Continuous diamond films with low dislocation density were obtained by two-step epitaxial lateral overgrowth (ELO). Grooves were fabricated by inductively coupled plasma etching. Mo/Pd stripes sputtered in the grooves were used to inhibit the propagation of dislocations originating from the diamond substrate. Coalescent
[...] Read more.
Continuous diamond films with low dislocation density were obtained by two-step epitaxial lateral overgrowth (ELO). Grooves were fabricated by inductively coupled plasma etching. Mo/Pd stripes sputtered in the grooves were used to inhibit the propagation of dislocations originating from the diamond substrate. Coalescent diamond films were achieved by ELO via microwave plasma-enhanced chemical vapor deposition. Etch-pits were formed intentionally to characterize the quality of the epitaxial films and distinguish different growth areas, as dislocations served as preferential sites for etching. In the window regions, a high density of dislocations, displayed as dense etch-pits, was generated. By contrast, the etch-pit density was clearly lower in the overgrowth regions. After the second ELO step, the dislocation density was further decreased. Raman spectroscopy analysis suggested that the lateral overgrowth of diamond is a promising method for achieving low dislocation density films. Full article
(This article belongs to the Special Issue Diamond Crystals)
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Review

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Open AccessReview Incorporation of Large Impurity Atoms into the Diamond Crystal Lattice: EPR of Split-Vacancy Defects in Diamond
Crystals 2017, 7(8), 237; doi:10.3390/cryst7080237
Received: 27 June 2017 / Revised: 27 July 2017 / Accepted: 28 July 2017 / Published: 31 July 2017
PDF Full-text (1127 KB) | HTML Full-text | XML Full-text
Abstract
Diamond is a unique mineral widely used in diverse fields due to its remarkable properties. The development of synthesis technology made it possible to create diamond-based semiconductor devices. In addition, doped diamond can be used as single photon emitters in various luminescence applications.
[...] Read more.
Diamond is a unique mineral widely used in diverse fields due to its remarkable properties. The development of synthesis technology made it possible to create diamond-based semiconductor devices. In addition, doped diamond can be used as single photon emitters in various luminescence applications. Different properties are the result of the presence of impurities or intrinsic defects in diamond. Thus, the investigation of the defect formation process is of particular interest. Although hydrogen, nitrogen, and boron have been known to form different point defects, the possibility for large impurity atoms to incorporate into the diamond crystal structure has been questioned for a long time. In the current paper, the paramagnetic nickel split-vacancy defect in diamond is described, and the further investigation of nickel-, cobalt-, titanium-, phosphorus-, silicon-, and germanium-related defects is discussed. Full article
(This article belongs to the Special Issue Diamond Crystals)
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