11 Structure and Properties and Diamo,nd Polytypes of Diamond

1 .O INTRODUCTION The first part of this book deals with graphite and carbon materials, their structure and properties, and theirvarious of carbon: diamond. Diamond has outstanding properties, summarized as follows: processes and applications. In this and the next three chapters, the focus is on the other major allotrope

It has the highest thermal conductivity of any solid at room temperature, five times that of copper. It is the ideal optical material capable of transmitting from the far infra-red to the ultraviolet. It has an unusually high index of refraction. light

Its semiconductor properties are remarkable, with fifteen times the average electric breakdown of common semiconductors, five times their average hole mobility and a dielectric constant that is half of that of silicon. It is extremely resistant to neutron radiation. material. in air, similar to that of

It is by far the hardest-known It has excellent TeflonTM. It has extremely

natural lubricity

high strength and rigidity. density of any material.

It has the highest atom-number

244

Structure

and Properties

of Diamond

245

However, researchers, and synthesize synthetic

diamond

is scarce

and costly

and this

has motivated nature of

in the last one hundred years or so, to try to duplicate it. These efforts are finally succeeding challenged by the large-scale

and the scarcity and production

high cost are now being diamond.

The properties of these synthetic diamonds are similar lower. Modern diamonds belong toone the only source of

(and in some cases superior) to those of natural diamond at a cost which may eventually be considerably The Four Categories of four distinct categories: 1. Natural diamond, still essentially in Ch. 12). gemstones and by far the leader in terms of monetary of Diamond.

value (reviewed

2. High-pressuresyntheticdiamond, takinganincreasing share of the industrial market, particularly in wear and abrasive applications 2. CVD (vapor-phase) in production (reviewed in Ch. 12). important but

diamond, potentially in Ch. 13).

still basicallyatthelaboratorystagewithfewapplications (reviewed

4. Diamond-like carbon (DLC), also recent butwith growing applications 14). in optics and other areas (reviewed in Ch.

2.0 2.1

STRUCTURE Analytical Diamond

OF DIAMOND

AND DIAMOND

POLYTYPES

Techniques is often found in combination to clearly identify with other carbon allotropes by determining its by the

and it is necessary structure, following techniques.

each material

atomic vibration,

and electron state. This is accomplished Diffraction techniques

Diffraction

Techniques.

can readily reveal the

crystalline structure of bulk diamond or graphite. constituents

However, in many cases, a

material may be a complex mixture of diamond, graphite, and amorphous on a size scale that makes them difficutt to resolve even with the have to be interpreted cautiously. electron microscopy and selected area diffraction (SAD). Consequently, results of these diffraction techniques

246

Carbon, Graphite,

Diamond,

and Fullerenes

In addition, electron diffraction similar to those of basal-plane analyzing the other. Unfortunately,

patterns of polycrystalline

diamond are

oriented polycrystalline

graphite and, when aggregates are

mixtures of the two, it may be difficult to separate one pattern from mixed graphite-carbon-diamond materials. an alternate solution to identifitechnique can This laser-optical theirvibrational Fortunately

common in natural and synthetic Raman Spectroscopy. determine with great’accuracy

cation is offered by Raman spectroscopy.

the bonding states of the carbon atoms (sp* properties.t’)

for graphite or sp3 for diamond) by displaying by lattice vibration As shown phonons.

The Raman spectra is the result of the inelastic scattering of optical photons in Fig. 11.1, the presence of diamond and/or graphite by

bonding is unambiguous

and clear. Single-crystal

diamond is identified

a single sharp Raman peak at 1332 cm (wave numbers), and several second-order features.

often referred to

as the D-band, and graphite by a broader peak near 1570 cm (the G-band)

I

I

I

I

I

I

I

8

-

500

1000

1500

2000

2500

3000

3500

Raman Shift (cm-l)
Figure 11.1. Raman spectra of diamond and graphite.

It is generally accepted that.10 of Ch. it for sp3 bonds for graphitic domains smaller than 10 nm.5). the technique must be recognized aggregation efficiency for sp2 bonds is more than fifty times minute amounts of graphite carbon). A single-phase or electron diffraction . one with a cubic symmetry with a hexagonal Sec. accounts for the tetrahedral state of four with four 2sp3 orbitals found in the diamond These orbitals are bonded to the orbitals of four other carbon with equal angles to each other of 109” 28’. However. Each diamond tetrahedron com- forms and polytypes. 11. 3. to be recognized as diamond. form strongly-bonded. unlike graphite. in contrast to the pronounced of graphite.Structure and Properties of Diamond 247 The Raman scattering the efficiency a result.2 Atomic Structure of Diamond of the carbon atom from the ground orbital state is described. the hybridization state to the hybrid sp3 (or tetragonal) that this hybridization valence structure. as atoms with a strong covalent bond (i. 2. 2. the atoms share a pair of electrons) to form a regular tetrahedron shown in Fig. for a material it must have the following characteristics: . it has several crystalline Diamond. 2. A crystalline morphology crystalline visible by electron microscopy structure detectable by x-ray . Cubic and Hexagonal bines with four other tetrahedrato and entirely covalent crystalline tures. three-dimensional Diamond has two such struc(see (the more common and stable) and one symmetry found in nature as the mineral lonsdaleite .2 (see also Fig. symmetry It is shown and the atomic In Ch. As is capable of detecting bonds (such as may present in some diamond-like that the techniques of the constituents.. 2). Sec. structures. cannot readily define the state of Diamond Characteristics. A clear diamond Raman spectrum with a sharp peak at 1332 cm 2. However.e. 2.3 Crystal Structures of Diamond Diamond is a relatively simple substance in the sense that its structure and properties anisotropy are essentially isotropic.

is more compact than graphite interlayer spacing). as a stacking of energy of 711 kJ/mol (170 kcal/mol). 2.1/4. the diamond structure is isotropic and. l/2 x 6 at the faces and 4 of the structure are shown in Fig.26 g/cm3). one with origin at O.3. The covalent Cubic diamond is by far the more will be referred common structure and. . planes is ABCABC. and Fullerenes Figure 11.515 g/cm3 vs.154 nm) and a high bond l/8 x 8 at the corners. The diamond tetrahedron. except on the (111) plane. diamond is characterized atoms located as follows: 11. (sp3) bonds. structure and wide Consequently diamond has higher density than graph- ite (3.t*] inside the unit cube. Diamond. (a) and (b).2. With its fourfold coordinated (with its sp* anisotropic tetrahedral parallel axes. to as simply “diamond”. Graphite. in order to simplify the terminology.t21t31 The cubic structure of diamond can be visualized link between the carbon atoms of Each diamond unit cell has eight by asmall bond length (0.248 Carbon. Two representations puckered infinite layers (the{1 11) planes) or as atwoface-centered interpenwith etrating cubic lattices. The stacking sequence of the (111) of Diamond. Density so that every third layer is identical.1/4.and the other at l/4.O. 11. Structure of Cubic Diamond.3(c).O. as shown in Fig.

3. the molar density data of density of 0.5).[2][3] Diamond has the highest atom density of any material with a molar of all substances. diamond is the stiffest. As a result. in Table 11 .Structure and Properties of Diamond 249 Sequence Figure 11. The atomic and crystal structure diamond are summarized data for hexagonal diamond (see Sec.293 g-atom/cm 3. 2.I41Also included in the table are the .l .188 g-atom/cm 3. In comparison. hardest and least compressible of graphite is 0. Schematics of the structure of cubic diamond.

and cube-octahedral found.3/4 .l/2) (l/4 . and Fullerenes Table 11 .4 Diamond Crystal Forms Diamond occurs in several crystal forms (or habits) which include the octahedron.t6j In CVD diamond.15445 0. and others which are more complicated.314) (l/8 . nm bond a = 0. the (111) octahedral predominate faces surface.250 Carbon. . crystals are commonly Twinning occurs frequently Faceted crystals of cut diamonds are predominantly (100) surfaces.l/2 .i/2) (l/2 . Diamond.l/4 .5).213 .l/4 . the dodecahedron. the simple crystallographic crystal are shown in Fig.718) Property Space group Atoms per unit cell Atom position Cell constant at 298 K.5152 3.52 0.3/4) 0.154 2. the (110) dodecahedral octahedral (Fig.3567 Hexagonal Symmetry PGJmmc 4 (000) (00 .3/4 .110 and 111) in a cubic These simple planes correspond to the faces ofthe three major crystal forms of diamond: the (100) cubic.l/4) (3/4 .3/4) (3/4 . Both cubic and octahedral synthetic high-pressure and the (111) in surfaces predominate diamond where they are found alone or in combiand the (100) cubic surfaces combining both of these suron the (111) the (111) and nation to form blocky crystals.213 .l/4) (l/4 . g/cm3 Carbon-carbon distance. Graphite.0 .4.0) (0 .I. nm Theoretical density at 298 K.252 c = 0.142 3. As a reminder.l/2) (l/8 .t5j planes (100.l/2 . 11 . 11. Crystal Structure Data of Diamond Cubic Symmetry Fd3m 8 (000) (i/2 .

Indices of some simple planes in a cubic crystal. .4..Structure and Properties of Diamond 251 (100) Plane (110) Plane C b ‘_“..” . Major crystal forms of diamond. 0 @ (111) Plan: Figure 11.5.[q Cubic {loo} Dodecahedron (110) z t i Y v’. X Octahedron {ill} Figure 11.

ABC- Note ABAB Sequence Figure 11. Graphite. 11.0. Diamond. Schematic of the structure of hexagonal diamond (lonsdaleite).5 The Polytypes of Diamond Hexagonal Diamond. so that every second layer is identical as shown in Fig.6. Hexagonal diamond is an allotropic form of carbon which is close to cubic diamond in structure and properties. This two-layer hexagonal sequence (known as 2H diamond) is different in this respect from the three-layer sequence of cubic diamond (known as 3C diamond).m Hexagonal diamond has an ABAB stacking sequence. and Fullerenes Diamond Cleavage Planes.252 Carbon.~~ . cleavage Diamond breaks along well-defined of planes (the cleavage of a crystal being its characteristic breaking along given crystallographic planes where the yield strength is lower due to a high concentration of weaker bonds or a lower total number of bonds). 2. The cleavage energies of the various planes are reviewed in Sec.6. This cleavage characteristic is the key to the cutting of gemstones (see Ch. It is a polytype of diamond. The dominant cleavage plane is the (111) but many others have been observed. The crystallographic data of these two polytypes are listed in Table 11 .I . that is a special form of polymorph where the closepacked layers ((111) for cubic and (100) for hexagonal) are identical but have a different stacking sequence. 6. 12).

The membersofthis as 4H.1 .2 eV per carbon the growth mechanism is equivalent structure instead of cubic can readily occur. intermediate levels and consequently natural hexagonal (see Ch.0. These crystals are mostly cubic although have revealed the existence known as 6H diamond. The diamond in a cubic diamond structure fault at every two-atom layer and is generally of hexagonal is prevalent. 10H. has a mixed six-layer shown schematically The 6H structure AA’C’B’BC. Recent investigations diamond polytype This material is believed to belong to a hypothetical structures intermediate series are tentatively include hexagonal 1OH diamonds sequence between hexagonal identified and cubic. inclusion to having detrimental Because leading to the hexagonal of hexagonal a stacking between the two of only 0. Some meteoriies Diablo in Arizona. to optical and other properties. 8H and stacking of The diamond is in the form of polycrystalline form is also found.1 IMPURITIES Impurities IN DIAMOND AND CLASSIFICATION The properties of diamond are susceptible to impurities and the presence of even a minute amount of a foreign element such as nitrogen can cause drastic changes. during diamond of this small energy difference.t5) series of diamond typeswith The series would of 4H.p) It may exist in 3. 6H.tlO) The natural hexagonal contain diamond such as the one found in Canyon compacts crystals.0 3. hexagonal/cubic in Fig. Diamond Occurrence. the hexagonal another made up of submicron 6H Diamond. It is therefore important to know the composition of the . The formation Hexagonal diamond is usually favored where high carbon supersaturation high-pressure synthesi@lt9) a condition commonly found during CVD synthesis and occasionally lower supersaturation lonsdaleite. CVD diamond.Structure and Properties of Diamond 253 The cubic diamond nucleus is slightly more stable than the hexagonal with an energy difference atom. The existence has yet to be confirmed. 8H.1 1.7. Natural diamond grows at much diamond is known as the mineral is rarely found. 12). (2H) diamond on one end and cubic (3C) diamond on the other (the digit indicates the number of layers).

254 Carbon. B-B’ Cubic Stacking: Other adjacent Layers Figure 11. Diamond.f5] . Graphite. Schematic of the structure of 6H diamond.7. and Fullerenes A B C A’ B’ C’ A Hexagonal Stacking: A-A’.

magnesium. 1. Lattice These impurities are divided into two different types: impurities which consist of foreign elements a incorporated carbon atom.t12] Nitrogen impurity in diamond is detected and characterized and paramagnetic nitrogen resonance. in the lattice.8. Schematic diamond.[“] Isolated minor. free of impurities. by IR absorption 11. Other elemental impurities but probably Nitrogen. platelets are also may also be present but only in extremely small amounts and their effect on the properties of the material is still uncertain atoms within the diamond structure are arranged in pairs as shown atoms are rarer.8. They have small atomic radii and fit readily within the diamond structure. is never completely Types of Impurities. synthetic or natural.f”j found in diamond are nitrogen and The two major lattice impurities boron. the lattice. 2. Their exact form is still controversial. Inclusions. Nitrogen present and can be represented as a quasi-planar structure within the cube (100) plane of the diamond crystal. These two elements are the neighbors of carbon in the periodic table. or calcium such as olivine. The majority of nitrogen in Fig. the foreign atom replacing which are separate particles and not part of usually consist of silicates of aluminum.Lg] of a nitrogen pair impurity in the lattice structure of . Carbon atom 8% Nitrogen atom Figure 11.Structure and Properties of Diamond 255 material evaluation being tested as accurately of the measured as possible in order to obtain a true properties. Diamond.

1 % nitrogen in small aggregates Includes cl 0 % platelets Not paramagnetic lb Rare in nature (~0.2 Classification of Diamonds No two diamonds have exactly the same composition and properties.0 4.1 PHYSICAL PROPERTIES General Considerations Diamond is costly and available only in small crystals and. the determination of its properties is difficult and expensive. Table 11. one classification is universally accepted.2. and any number of classification schemes can be devised. Classification of Diamond Type la Origin 98% of all natural diamonds Impurities App.1%) Includes most highpressure synthetic diamonds Nitrogen 0.258 Carbon.2 (some diamonds may consist of more than one type). Graphite. Diamond. types. and Fullerenes 3. their origin.05 % in lattice Paramagnetic Ila Rare in nature Few ppm of nitrogen Usually clear Ilb Extremely rare in nature Produced by highpressure synthesis Less nitrogen than Ila Becomes semiconductor by boron doping 4. 0. and the amount . and their effect on optical and other properties are summarized in Table 11. However only It is based on the nature and amount of impurities contained within the structure and consists of four These types. as a result.

one of the most refractory materials with a sublimation respect to graphite with a negative free-energy in all fairness. above it. is also a function of the environof carbide formers of cobalt.02 g) octahedral diamond-graphite For instance. pressure.Structure and Properties of Diamond 257 of testing uncertainty and published data are still limited. conversion practical years above. considerable is generally necessary. agreed that considerable particularly more testing and evaluation in the area of synthetic diamond. At that rises. shows the relationship between these two decreases The free-energy with temperature temperature. either natural or synthesized 4. Sec. for all of over a billion diagram. diamond natural diamonds in some alluvial deposits which wereformed ago and have not changed of carbon. the rate of the diamond-graphite small at ordinary temperatures and. It becomes especially rapid in the presence transformation can occur as low as 500°C.05 kJ/mol at approximately 1200°C. change of the diamond-graphite transition The carbon illustrated allotropes in Fig. 2. 12. in hydrogen diamond graphite-diamond. is stable up to 2000°C and in a high vacuum The opposite transformation. diamond However. room temperature Theoretically better qualified. is not “forever”. 2. graphite is the stable allotrope of carbon and is point above 4000 K Diamond has a different behavior and is unstable with change of 2. as evidenced since.88 kJ/moi at graphite would be and atmospheric at least. is stable. is reviewed in Ch. 3. However. it proceeds instance. graphite in less than three minutes at 21 00°C.3. The properties listed in this chapter are those of single-crystal at high pressure. carbon soluble metals. For the transition to graphite is observable with a rapidly increasing but still slow. to reach -10. . These problems and the it are dia- about the effect of impurities mentioned above contribute to the spread in the reported values often found in the literature.2 Thermal Sta biiity As mentioned at one atmosphere. converted to rate as the temperature crystal is completely a 0.t4] The transformation ment. by the presence phase is infinitesimally purposes.1 carat (0. mond. or the in the presence up to 1700°C.20 of Ch.

5 . Diamond.884 5.3 Effective Debye temperature.4 f 0. J/mol: at 300 K at 1800K at 3000 K 6..2 Thermal Conductivity One of the outstanding characteristics of impurity-free diamond its extremely-high thermal conductivity. J/mol. C.7 26.K 2. Table 11.428 1. Graphite.4000 la 17.2100 Ila 2000 .1100K 2220 + 20 K OK Thermal conductivity.1 at 193 K 0.3.8 at400-1200K Standard entropy: at 300 K. at 293 K Type Type at 80 K Type Type W/m-K: 600 . the highest by far of any solid at room .3. and Fullerenes 5.1000 la 2000 . 1c6/K: 0. Thermal Properties of Diamond Specific heat.8 + 0.1 at 293 K 1.000 Ila Linear thermal expansion.0 5.1 THERMAL Summary PROPERTIES OF DIAMOND of Thermal Properties The thermal properties of diamond are summarized in Table 11.4.195 24. J/mol. OD: 1860+ 10K 273.K Standard enthalpy of formation: at 300 K.256 Carbon.

Structure and Properties of Diamond 259 temperature and approximately of Thermal five times that of copper. in the diamond bonded to each other. is an excellent When few of these obstacles thermal conductor.tJ3) l occur mostly at high frequencies 40 x 1 01* Hz. 2. Table 3.n5t Nitrogen aggregates. Other phonons (via umklapp processes) . Plan&s This amount is equal to the frequency constant (6. are present to impede the passage of thermal in diamond is not completely free. which at ordinary tempera- structure. occurs in diamond when the carbon atoms are excited Quantum physics dictates in a given times the Latticevibration by a source of energy such as thermal energy. This conductivity Conductivity. for the mathematical of thermal conductivity). Such a mechanism unlike the thermal conductivity in metals which occurs transportt13)t14t (see Ch.3. and vacancy sites . by electron expression diamond occurs by latticevibration.nl) Consequently. that a discrete amount of energy is required to set off vibrations of the vibration Carbon atoms are small and have low mass and. Mechanism a flow of phonons. The thermal conductivity is characterized is in by similar to that of the graphite crystal in the ab direction (see Ch. system. the with a maxinecessary to make these atoms vibrate is large. 13. conductivity. Sec. are tightly and isotropically quantum energies means that their vibrations mum of approximately tures. 4. 3. 11 .6256 x 1O-27ergs). 2. waves and thermal conductivity the flow of phonons Several obstacles impede it by scattering the phonons and thus lowering the These obstacles include: diamond inclusions within the cubic structure Hexagonal and the resulting stacking faults they may create . Sec. Point defects due to 13C carbon isotopes. 3. lattice defects. diamond Conductivity. is unusually high. Crystallite boundaries. The relationship ductivity and nitrogen is shown in Fig. Effect of Impurities to conductivity especially substitutional on Thermal nitrogen. As a result. 3. normally 1 . few atomic vibrations However.6).g. Of all the obstacles between thermal confound listed above. Sec. a most important is the presence of impurities.1 and Ch. .6) l Point defects due to impurities are present.l % of all carbon atoms (See Ch.

260 Carbon. 1500 0 0 50 100 1500 Nitrogen Content.t131 . 2500 lb Diamond y Z 3 S . phonon scattering is minimized and these diamond types have the highest thermal conductivity. 1016 atoms/cm3). Diamond. The latter contain only a small amount of nitrogen (app. ppm Figure 11. and Fullerenes in Type la crystals.9.= -2 2 -E E g G e 500 1000 2000 . have a much stronger ability to scatter phonons than the lattice nitrogen found in Type Ha and lb crystals. Thermal conductivity of Type lb diamond as a function of nitrogen content. Graphite. Other impurities such as boron seemto have much less effect than nitrogen.

K Figure 11. 11 -10 shows the effect of temperature on the thermal conductivity of several types of diamond.[13]-[151 The conductivity reaches a maximum at approximately 100 K and then gradually drops with increasing temperature.[“1[‘*1 of Types la and II diamonds and copper as .10.[14] I I I 10 100 300 1000 Temperature. several materials such as copper have higher conductivity. Fig. Below 40 K. Thermal conductivity function of temperature.Structure and Properties of Diamond 261 Effect of Temperature on Thermal Conductivity.

3. 3.0. the hav- propagation. The ultraviolet spectrum with wavelengths (CO.3 and Table 3.1 General Considerations It is now generally generation. copper is 17 ppm. and Fullerenes 5. IR radiations immediately above the visible (0.4.-1 mm).11.7 The near-infrared spectrum with wavelengths . room temperature.3.4 pm). Diamond.7 pm) and the far infrared (71_lm are a major source of heat.4 to 0. like that of all elements. It extends from 0.3 Thermal Expansion The reviewed mechanism of thermal expansion in a crystal material was At is in Ch. n accepted that the term “optics” encompasses and detection These of electromagnetic radiations comprise radiations and shorterthen microwaves.19 . (in comparison. immediately are . 4. Like graphite in the ab directions. Thevisiblespectrum Pm. increases 6.4 pm range. schematically spectra: . 5.4 Specific Heat The specific heat of diamond is generally comparable to that of with graphite and is higher than most metals (see Ch.8 ppm. 4.7 . slightly negative). the coefficient Unlike of thermal expansion diamond diamond is a strongly bonded solid and. ing wavelengths greaterthanx-rays in Fig. Sec.“C thermal as shown has an isotropic expansion which gradually increases with increasing temperature in Table 11. Sec.0 OPTICAL PROPERTIES OF DIAMOND 6. Graphite. (see Table 11. 11.262 Carbon. The specific temperature heat of diamond. below the visible Most UV applications found in the 0. . in the ab direction (CTE) is 0. as a result.5). it has a low thermal expansion.3).“C and graphite graphite. asshown the following which can be detected and identified as colors by the human eye.

The electromagnetic spectrum. 1 Blue I Green \ellow.11.nm I 600 i Vlslble Portion of the Spectrum Figure 11.Orang$ Red .A I 500 Wavelength.@ - -104 -10-a -10-2 -10-l -1 (lxu) (IA) nm Standard Broadcast 400 IViolet.Gamma Rays 102'10'9 - Photon Energy ov Wavelength.Structure and Properties of Diamond 263 Frequency. . Hertz Radiation . nm -107 -106 -10s .

The energy in the lower-frequency radiations such as infrared and visible is too low to excite the diamond electrons across the high bandgap and. diamond is capable of transmitting across a unusually broad spectral range from the x-ray region to the microwave and millimeter wavelengths and has the widest electromagnetic bandpass of any material. or the conduction of radiant energy through a medium. Graphite. as a result.14pm waveband) (Fig. To break these bonds (by exciting an electron across the bandgapl requires considerable energy since the bandgap is high (5. In the case of the visible light.13). giving diamond its unequalled brightness. increases gradually going from the infrared to the visible to the ultraviolet and x-rays. in the ideal crystal. there should be no absorption due to electronic excitation up to that level (Fig. as shown in Fig. The IR absorption is related to the creation of phonons and the intrinsic multiphonon absorption. At the short wavelength end of the optical spectrum. Transmission Mechanism.2 Transmission Transmission.48 eV at room temperature). 11. An infrared absorption which lies between 1400and 2350 wave number (cm-‘). Diamond. Transmittance over a wide range of optical wavelengths is one of the optical characteristics of diamond.264 Carbon. virtually none is absorbed and essentially all is transmitted or refracted. 11 . .l this frequency 1.12). The high transmittance is related to the nature and high strength of the diamond bond. is characterized by transmittance. This corresponds to an absorption edge of 230 nm and. This excitation can be accomplished by the action of a photon of an electromagnetic radiation. an ultraviolet absorption due to the electron transition across the bandgap. Absorption Bands. Pure diamond (which has never been found in would have only two intrinsic nature and has yet to be synthesized) absorption bands as follows:t16)[17) 1. which is the ratio of radiant power transmitted by a material to the incident radiant power. and Fullerenes 6. The energy of a photon is proportional to the frequency of the radiation and. 11. 2. Absorption is nil above 7pm (this includes all the major atmospheric windows in the 8 .

[14] 100II s I I 80 s 0 . nm Figure 11.E 60 g .12.6 I- 54 8 g 48 % ._ 5 32 2 It 15 Type la Diamond (with nitrogen impurities) Sample Thickness: 1mm 0 200 250 300 350 400 450 500 550 600 650 700 Wave Length.!j 40 c + 20 L Type Ila Diamond Sample Thickness: 1mm 0 4000 3550 3100 2650 2200 1750 1300 850 400 Wave Numbers (cm-l) Figure 11. Transmission of Type Ila diamond in the infrared spectrum. Transmission of Types la and Ila natural diamonds in the UV and visible spectra.[141 .Structureand PropertiesofDiamond 265 Photon Energy 80 m .13.

and Fuiierenes Effect diamond conditions of impurities and Structural Defects. absorbed. Diamond. defects and other obstacles transmittance. Continuous absorption below 5. and had a perfect structure. As seen above.tll] of light (the one with less photon energy) are per 1 Or’ atoms is necessary A minimum of one vacancy Table 11.266 Carbon. two mentioned of photons in the IR region as shown in Table 11. to the free movement are never completely achieved.4. diamond Lattice vacancies (missing atoms) may considerably bonds and cause electrons to be exited by a much smaller amount of energy (such as produced by a photon of red light) that would normally be required in a perfect lattice. particularly nitrogen.5-25 microns UV: absorption at 237 nm . Optical Absorption of Diamond by Type Type la Optical absorption IR: 6-13 microns UV: ~225 nm bands lb IR: 6-l 3 microns UV: <225 nm Ila Closer to ideal crystal. A diamond containing such lattice vacancies appears for the blue since the red components blue color to be noticeable. Graphite.4eV Ilb I R: no significant absorption from 2. particularly remains the best optical material. and impuritiesand These obstacles add a number of absorption above.4. alter the valence in spite of this. No absorption in the range cl 332 cm-‘. would be the ideal transparent material if it were totally free of Howeverthese crystal-lattice affect its bands to the impurities.

rutile: 2.5.O: 2.4 Index of Refraction The index of refraction of diamond is high as shown in Table 11.t12)t181t191 6.43554 2.7151 1.456 1.4237 2.4 and 2.4099 2.539 1.589 Quartz Crown glass Air * Near cut-off in the ultraviolet .28 (C-line) 589.5 and only a few materials have higher indices (Si: 3.7. particularly is a well-known optical property of single crystal This luminescence and of characteristic and is caused by impurities (CL) is another diamond is described in the blue and green regions. Index of Refraction of Diamond and Selected Materials Wavelength Material Diamond Index 2.7).000 (nm) 546. Table 11.361 2 0.41726 2.9.1 (Hg green) 656.13 (F-line) 226.5 * 0.497 1. Cu.Structure and Properties of Diamond 267 6.5. All ionic crystals have lower indices.29 (D-line) 486.656 0.3 Luminescence Visible luminescence diamond originates diamond. in the states at mid-bandgap Cathodoluminescence The CL of single crystal lattice defects. AIC.8 eV (from green to purple-blue).574 1.185 0. luminescence as a band-A and the peak of the spectra is found between 2.: 2.

. Graphite.1 4. X-ray transmission of a 0.268 Carbon.1 1. and oxygen. Diamond. in thin sections. carbon.[“] 8.t20] 100 80 20 0 B C N 0 F Ne Na Mg Al Si P S Cl Ar K Ca Generating Element hka diamond window of the Figure 11. unlike thermal conductivity and optical absorption which are associated with high-frequency vibrations.0 ACOUSTICAL PROPERTIES OF DIAMOND Sound waves are carried by vibrations in the low-frequency range (a few hundred Hertz). The x-ray transmission of a 0.5 mm-thick characteristic radiation of a series of elements. and Fullerenes 7.14.0 X-RAY TRANSMISSION OF DIAMOND X-ray transmission of diamond is excellent by virtue of its low atomic number and. it even allows the transmission of characteristic x-rays generated by low-energy elements such as boron.5 mm-thick diamond of the characteristic radiation of a series of elements is shown in Fig. it compares favorably with the standard x-ray window material: beryllium. In this respect.

05 106 2.2). 6. Electron Hole 2200 1600 9. Q-m Type I and most Type Ila Type Ilb Dielectric Dielectric Saturated Constant Strength. at 300 K V/cm 1 O7 cm/s 10’8 103.7 electron velocity. of up to 20 km/s are reported.tlll 9.89 km/s and in silicon slightly less than 10 km/s.trg] The high strength of the insulators . the speed of sound in beryllium is 12. cm*/Vs Carrier mobility.70 + 0.105 5. Electrical and Semiconductor Properties of Diamond Resistivity.6.6 .2 Resistivity and Dielectric Constant Pure single-crystal best solid electrical diamond. is one of the (see Sec.1 Summary of Electrical and Semiconductor properties Properties of diamond are summa- The electrical and semiconductor rized in Table 11 .Structure and Properties of Diamond 269 The structure material of diamond favors low-frequency Measurements transmission and the has high sound velocity.[*‘I Table 11.48 eV. with a bandgap of 5. By comparison.0 ELECTRICAL DIAMOND AND SEMICONDUCTOR PROPERTIES OF 9.

Obviously the larger the properties of diamond material. the smaller the possibility of electron transfer and large-bandgap This is the case for of 500°C or temperature can be used at higher temperature. is higherthan high-intensity silicon.15. unlike other semiconductors. Sec. as a semiconductor It is an indirect bandgap and has the widest bandgap of any semiconductor material no longer functions semiconductors higher. 13. band becomes greater due temperature. the upper limit of silicon is 150°C and that of GaAS Diamond can be changed from an intrinsic to an extrinsic semiconductor at room temperature by doping with other elements such as boron and during the synthesis of by CVD (see Ch. When a semiconductor transfer from thevalence to the thermal excitation material is heated.270 Carbon. resistivity measured. that is. fields as shown in Fig. or silicon carbide its high rate in and. as with the optical properties. the probability limiting of electron the band to the conduction and. above a certain as a semiconductor. Graphite. the velocity this velocity high electric fields. Diamond. and Fullerenes electron bond makes it unlikely that an electron would be exited out of the valence band.t4] are excellent and it has (see Sec. applications. gallium arsenide. However. 11 .3 Semiconductor Diamond The semiconductor good potential semiconductor 6.7) is low compared to that of 4). Diamond has an excellent germanium saturated carrier velocity. .4). the presence of impurities can drastically electronic alter its electronic state and the inclusion of s$ (graphite) bonds decrease the resistivity and render the material useless for constant of diamond (5. bandgap. In pure diamond. electron-carrier Doped natural diamond is also found (Type Ilb) but is rare.2).t4)t2*) This doping can be accomplished diamond either by high pressure or especially 4. mobility exceeded at which electrons maintains only by The move in phosphorus. is 250°C. in the p-type and by gallium arsenide in the n-type. diamond which has an upper limit semiconductor In comparison. such as silicon or germanium but not as low as most will considerably greater than 10’s S&m has been The dielectric other semiconductors organic polymers (in the 2 to 4 range) or glasses (approximately 9.

1 Summary PROPERTIES OF DIAMOND of Mechanical Properties that the strength properties available show are difficult and a material of It should be emphasized expensive and configuration. of diamond are summarized in Table either were measured of a high-strength on single-crystal diamond natural or produced by high pressure.t23] The properties includes the properties to measure due to the lack of diamond of the required test size The data presently properties strength and rigidity. namely alumina. materials.0 MECHANICAL 10.7 . . For comparison purposes.15. considerable The mechanical 11 . the table ceramic.Structure and Properties of Diamond 271 Steady-State Velocity-Field Characteristics I I I 104 105 105 Electric Field (V/cm) Figure 11. Electron-carrier mobility of diamond and other semiconductor 10.

53 3.2100 0.7.9600 0.10400 6900 .16. The hardness of diamond is compared with that of other hard materials in Fig.0.68 .400 2.16 2000 .400 kg/mm*.1 near 1 10. Diamond.05 .10400 7500 . Mechanical Properties of Diamond and Alumina at 23°C Property Diamond Alumina Density. g/cm3 Young’s modulus.700 to over 10.272 Carbon.0.10 . relation between hardness can also be determined .22 0.52 910.1250 8. GPa 3. is the hardest known material makes it difficult to measure its hardness since only another diamond can be used This may explain the wide variations in reported values which range from 5.98 380 .16.1 1.2 Hardness The very fact that diamond as an indenter. kg/mm* overall 111 plane 100 plane Poisson’s ratio Coefficient of friction in air in vacuum 5700 .7.75 Compression Knoop hardness. a function coefficients coefficients. GPa strength. The test method is the Knoop hardness test which is considered the most accurateforcrystalline of the crystal orientation of diamond is a linear as there The hardness materials. The hardness is also form the elastic and these as shown in Table 11. and Fullerenes Table 11. Graphite.

Structure and Properties of Diamond 273 Diamond 10000 “E g 2 f 6 t x 8000 Reported Range f 6000 CBN PSiC I 8 g 4000 Y 2000 0 lLd!AI.3 Cleavage Planes Diamond cleavage behaves as a brittle solid and fractures readily along its between of planes.t23] Cleavage planes is considerable meters per second. w.[171 Figure 11.c and other hard materials.O. and has been measured at several thousands .8. Cleavage occurs mostly along the (11 I} planes but can velocity in all these also occur along the other planes since the energy differences planes is small as shown in Table 11 . Hardness of diamond 10.16.

structure. (g) . Graphite. The reaction is as follows: C(diamond) + 0. In the latter case. This low friction however is a surface property which is on the presence of oxygen and other adsorbed apparently dependent impurities. diamond has one of the lowest coefficients of friction of any solid.8. the chemisorbed species are removed and the coefficient of friction increases considerably and approaches one.4 Friction Measured in air. the onset of oxidation has been shown to start at temperature as low as 250°C for finely divided powders and to become rapid above 600°C. In pure oxygen.f24) 11. it is expected that grain boundary.6 11. --+ CO. and Fullerenes Table 11. Theoretical Cleavage Energies of Diamond Angie between plane and (111) plane 0” and 70” 32’ lo”0 15” 48’ 22” 0 35” 16’ and 90” 54” 44 Cleavage energy (Jam-*) 10.274 Carbon.0 18. Diamond.7 12. Diamond burns brightly in an oxygen jet at 720°C. to polycrystalline films. In high vacuum.l Oxidation Diamond is generally inert to most chemical environments with the notable exception of oxidation. and the concentration of impurities at the boundaries play a role in controlling the chemical properties.6 13.0 CHEMICAL PROPERTIES OF DIAMOND Much of the information on the chemical properties of diamond refers to the single-crystal material. either natural or high-pressure synthesized and.2 12. 11 .4 Plane 111 332 221 331 110 100 10. in some cases.

is formed from 244 to 370°C by the interaction characteristic of diamond. hydrogen is chemisorbed not until a temperature considered the result of the formation of surface on the surface of diamond but is probably is generally However in Diamond of 400°C is reached. Co. provides the mechanism resistant material. is below -78°C.Structure and Properties of Diamond 275 The by-product provides no surface exposed and oxidation Under normal of the reaction is carbon dioxide which. which is used to good advantage elimination films and the selective of the co- 11. the presence of residual oxygen results in the formation 11. However strong oxidizers as NaOH. inert to molecular hydrogen (as opposed to graphite). attack by atomic hydrogen occurs above 1000°C. and by molten hydroxides It is resistant to alkalis and solvents. of a dense film of graphite.2 Reaction with Hydrogen Like oxygen. such as sodium and potassium acids at room including by such it can be etched by several compounds nitrates above 500°C At approximately of high-pressure fluxes of sodium and potassium chlorates. CO.144°C oxygen of 0. Al. a characteristic the deposition deposited of diamond graphite (see Ch.3 General Chemical Reactions Diamond is resistant to all liquid organic and inorganic temperature. This characteristic (see Ch. no adsorption occurs if the temperature is chemisorbed. 4. in air is less rapid with the onset of the reaction at approximately conditions. However. 12. passivation.5). being a gas. diamond can be considered . Yet diamond is far less reactive than graphite. Ni. A fresh diamond surface is always Oxidation 500°C. This chemisorption hydrides. Generally one of the most-chemically 1000°C synthesis as metals such as Fe. Ta. it reacts readily with carbide-forming B. 10. and speaking. From 0 . As mentioned with the diamond surface. Sec. of proceeds parabolically oxygen with temperature. for the hydrophillic the formation frictional properties. of surface oxides is also an important factor in the control of At 600°C and low pressure. 13).[24] Adsorbed oxygen and carbon oxides account in Sec. is adsorbed on the surface diamond after exposure to air (or oxygen) for a period of time.4.

539-554.. a. Wiley & Sons. (1966) Optics.. C. Nemanich. 969:i 65-l 84. J. The Properties of Diamond.. E. Bristol.. F. Mater. et al. 69:144-152. Academic Press. PropertiesofDiamond. 969:117-123. 19. S. J. and White. B. J. E. E. E. J. Field. Sot. Bundy. 703-710. Adam Hilger Ltd. P. 16. C. Yazu S. G. 72(2):171-191 (1969) John Eggers. Sci. Press. Jr. 7. Addison-Wesley Publishing. A. Vat. (J. MA (1956) Spear. F. ed. Elements of Physical Metallurgy. H. Sato. G. N. Academic Press. W. 10. (NOV.. G. Diamond Optics.. ChemicalPhysics.. and Fullerenes REFERENCES 1. Holly. Holly.. (Y.). eds. Am. SPIE. 3-23.. and Halsey. Physical Chemistry. London (1979) (J. eds. Addison-Wesley Publishing. MA (1959) Cullity. UK (1964) Sellschrop. la. 1966) and S.. 46(9) (1967) Angus. ed... Diamond Optics.. J. SPIE (1966) Lettington. P. (1966) K. Ceramic Bulletin. K. D. 3. Elements of X-Ray Diffraction. Singer. Feldman (Apr.. IO& 163. 1990) Res. S. J.). B. Ceram.. 6. Applications of Diamond Films and Related Materials.). Jr.. R. Field. Elsevier Science Publishers (1991) Kawarada. E. J.). J. Technol.. A6(3):1763-1766 i 988) (May/June 2. Diamond Optics. (1966) Davies.. J.276 Carbon. Tzeng. Diamond. Reading. Reading. Diamond Optics.). 5. ofApp. 5(1 i):2271-65 Dawson. and Kasper. London (1979) (J. 67(6):1006-1009 Spear. A. Diamond SPIE (1988) Seal M. 9. The PropertiesofDiamond. W. R. J. B. (A... Guy. D. 15. Feldman and S. 969:166-l 77. 12. G. 11. W. Field. and Fujimori. F. S. Jpn.. ed.).. D.. A. H .. Graphite. 4.. Davies. SPIE (I 988) ... New York (1964) Gardinier. London (1979) 13. 17. SPIE. Physics. Berman. Diamond. 27(4):663-6 (A. eds. Academic 14. 969:2-13. and van Enckevort. Phelps.

Field. London (1979) 22. 2(2):10-l 5 (1988) Field. Cork on Thin Films. Academic Press. J. P.. 79-106. Fujimori. (J. and Lightowlers. ed. A. ed. N. E. New 24. 21. Gorham. Collins. Properties of Diamond. York (1966) .Structure and Properties of Diamond 277 20.... H. CVD Diamond-Beyond High-Performance the Laboratory.). L. New Diamond. T. in Proc. GAMI. Boehm. E. Press. Conner. E. The Properties Academic of Diamond.). AdvancesinCatalysis. 23. Field. (J.. ME (1988) E. Academic Press. C. London (1979) 179-272. 282-324.

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