300:
occupied dangling orbital at the surface. In that case, there is hardly any unpaired electron density, which results in a weak EPR signal for such materials. Clean cleaved surfaces of such materials form paired electron localized states on alternate sites resulting in a very weak to no EPR signal. Not well-cleaved surfaces and microcracks obtained from crushing, cleaving, abrading, neutron or high-energy ion irradiation or heating and rapid cooling in vacuum give a measurable EPR signal (a characteristic signal in Si at g = 2,0055). The presence of oxygen and hydrogen gas affects the EPR signal from microcracks by affecting the single electron spin centers. The gas molecules can get trapped and, when staying close to a spin center, affect the EPR signal. When a microcrack is sufficiently small, the wave functions of the dangling bond states extend beyond the surface and can overlap with wave functions from the opposite surface. This can create shear forces in the crystal surface, causing atom layers to realign while creating dangling bonds in the process.
226:.) The mechanism of this is thought to be as follows: The photon energy is transferred to the system which causes the weak Si-Si bonds to break, leading to the formation of two bound radicals. The free electrons being localized and being very close together is an unstable state, so hydrogen atoms “move” to the site of the breakage. This causes the electrons to be delocalized further apart which is a more stable state. For a hydrogen content of around 10%, the dangling bonds from only a very small fraction of displaced hydrogen atoms can lead to observable EPR signal increases. The diffusion of hydrogen plays a key role in the process and explains why long illumination is required. It has been found that illumination under increased temperatures increases the rate at which light-induced dangling bonds form. This can be explained by the increased hydrogen diffusion.
271:
183:
210:. For a material with dangling bonds, the absorption intensity depends on the polarization of the absorbed light. This is an effect of the symmetry in which the dangling bonds are distributed over the surface of the material. The dependence only occurs up to the energy at which an electron can be excited to the level of the gap but not to the valence band. This effect along with the polarization dependence disappearing after the dangling bonds have been annealed, shows that it is an effect of the dangling bonds and not just of the general symmetry of the material.
28:
312:
molecules to adsorb to. When no gas adsorption is possible (for example for clean surfaces in vacuum), the surface energy can be reduced by reorganizing bonding electrons, creating lattice strain in the process. In case of the (001) surface plane of silicon, a single dangling bond on each atom will be formed, while pairing the other electron with a neighboring atom. Removal of dangling bond surface states on the silicon (001) surface from the band gap can be achieved by treatment of the surface with a monolayer of
487:
in EPR analysis. Annealing Teflon under an argon atmosphere at 100 °C to 200 °C results also in ferromagnetic properties. However, annealing close to the melting temperature of Teflon makes the ferromagnetism disappear. Under longer air exposure, the magnetization is reduced due to adsorbed water molecules. It also appeared that no ferromagnetism would develop under annealing Teflon under water steam or cutting in a H
337:, display a high concentration of dangling bonds. Besides being of fundamental interest, these dangling bonds are important in modern semiconductor device operation. Hydrogen introduced to the silicon during the synthesis process is well known to saturate most dangling bonds, as are other elements such as oxygen, making the material suitable for applications (see
470:. Metal atoms were adsorbed by oxidizing metal from a foam and coordinating the metal ions to the dangling bonds on the oxygen of the graphene oxide. The resulting catalyst had a high density of catalytic centers and showed high activity, comparable to other non-noble metal catalysts in oxygen reduction reactions while maintaining stability in a wide range of
386:(PV) technology, passivation is the surface treatment of the wafer or thin film in order to reduce the surface and some of the bulk recombination of the minority carriers. There are two main ways to passivate the surface of the silicon wafer in order to saturate the dangling bonds: field-effect passivation of the surface with a dielectric layer of SiO
399:(RPHP). In the latter method, hydrogen, oxygen, and argon gases react inside the chamber, then, the hydrogen is dissociating to the atomic hydrogen under the plasma condition to diffuse into the silicon interface to saturate the dangling bonds. This saturation reduces the interface defect state, where the recombination takes place.
299:
has 5/4 dangling bond. Because of dehybridization of surface orbitals (caused by the decreased number of nearest neighbor atoms around the surface atom), a group 13 atom will have a largely unfilled dangling orbital since it has valence 3 and makes three bonds, while a group 15 atom will have a fully
194:
of a lattice. This allows for absorption and emission at longer wavelengths, because electrons can take smaller energy steps by moving to and from this extra level. The energy of the photons absorbed by or emitted from this level is not exactly equal to the energy difference between the bottom of the
74:
When speaking of a dangling bond, one is generally referring to the state described above, containing one electron and thus leading to a neutrally charged atom. There are also dangling bond defects containing two or no electrons. These are negatively and positively charged respectively. Dangling
486:
tape, a network of strongly coupling dangling bonds arises on surfaces where the polymer was broken (from cutting or in strain-induced cavities). In the case of weak structural deformation, where only very few dangling bonds are formed, the coupling is very weak and a paramagnetic signal is measured
320:
was proposed). Selenium can attach to the silicon (001) surface and can bind to surface dangling bonds, bridging between silicon atoms. This releases the strain in the silicon surface and terminates the dangling bonds, covering them from the outside environment. When exposed, dangling bonds can act
120:
localized on the silicon nucleus, with delocalized electron density around the three bonding orbitals, comparable to a p-orbital with more electron density localized on the silicon nucleus. The three remaining bonds tend to shift to a more planar configuration. It has also been found in experiments
173:
to that of another electron. Ferromagnetic properties in various carbon nanostructures can be described using dangling bonds and may be used to create metal-free organic spintronics and polymeric ferromagnetic materials (see
Applications). Creating dangling bonds with unpaired electrons can, for
311:
of gas molecules, the only remaining dangling bonds are located at oxygen vacancies. Dangling bonds form an sp-hybridized bond with the adsorbed molecule, which have a metallic character. They are often the only defect sites present on atomic semiconductors, which provide such "soft centers" for
274:
Schematic depiction of a semiconductor surface with the (001) plane exposed. The surface atoms will reorganize to pair dangling bonds, lowering the overall energy but creating some surface strain. In general, reorganization of surface atoms can shift several layers of atoms near the surface from
398:
Hydrogen passivation is one way to saturate these dangling bonds. This passivation process is carried out by one of the following mechanisms: deposition of a thin film from silicon nitride SiNx on the top of the polycrystalline silicon layer, or passivation by remote plasma hydrogen passivation
411:
on the top of crystalline silicon (c-Si) wafer, also called "tunnel passivation" is one of the passivation techniques used most widely in PV technology. This technique combines both chemical passivation and field-effect passivation. This strategy is based on the formation of a dielectric layer
453:) in the dielectric film, these fixed charges establish an electric field that repels one type of charge carrier and accumulates the other type at the interface. This repletion assures reducing one type of the charge carriers concentration at the interface wherein the recombination decreases.
374:, surface properties are still dependent on the dangling bonds, since they occur in a number density of around 10 per square centimeter, compared to dopant electrons or holes with a number density of 10 to 10 per cubic centimeter which are thus much less abundant on the material surface.
229:
It is thought that the formation mechanism of intrinsic dangling bonds (in hydrogenated silicon) is very similar to that of light induced dangling bonds, except that the energy source is heat rather than photons. This explains why the intrinsic dangling bond density is negligible at room
111:"; so, often, are molecules containing such atoms. When a free radical exists in an immobilized environment (for example, a solid), it is referred to as an "immobilized free radical" or a "dangling bond". A dangling bond in (bulk) crystalline silicon is often pictured as a single unbound
174:
example, be achieved by cutting or putting large mechanical strain on a polymer. In this process, covalent bonds between carbon atoms are broken. One electron can end up on each of the carbon atoms that originally contributed to the bond, leading to two unpaired dangling bonds.
448:
by thermal oxidation, the process acts as chemical passivation since, on the one hand, the formation of the oxide layer reacts with the dangling bonds on the surface wherein it reduces the defects states at the interface. On the other hand, since there are fixed charges
107:, two atoms each contribute one unpaired electron, and the resulting pair of electrons is shared between them. Atoms that possess too few bonding partners to satisfy their valences and that possess unpaired electrons are termed "
115:
on the silicon atom, with the other three sp orbitals facing away from the unbound orbital. In reality, the dangling bond unbound orbital is better described by having more than half of the dangling bond
165:
in materials that are normally magnetically inactive, such as polymers and hydrogenated graphitic materials. A dangling bond contains/consists of an electron and can thus contribute its own net (para)
245:. These IVAP defects consist of a dangling bond containing two electrons (D) and a dangling bond containing no electrons (D). When one of these pairs is illuminated, it can capture an electron or an
1284:
Qu Y, Wang L, Li Z, Li P, Zhang Q, Lin Y, et al. (November 2019). "Ambient
Synthesis of Single-Atom Catalysts from Bulk Metal via Trapping of Atoms by Surface Dangling Bonds".
291:
elements show EPR signals from a surface after crushing. Crystals of elements from groups 13 to 15 prefer to have the (110) plane exposed as a surface. On this surface, an atom of
141:
Both free and immobilized radicals display very different chemical characteristics from atoms and molecules containing only complete bonds. Generally, they are extremely
344:
The dangling bond states have wave functions that extend beyond the surface and can occupy states above the valence band. The resulting difference in surface and bulk
186:
A configuration-coordinate diagram of the valence band, conduction band and dangling bond energy band in silicon. The arrows indicate the relaxation energies.
507:
in structure creation, in which an atom is inadvertently drawn with too few bonding partners, or a bond is mistakenly drawn with an atom at only one end.
482:
An example of an organic ferromagnetic polymer is presented in an article by Yuwei Ma et al.: by cutting with ceramic scissors or stretching a piece of
408:
145:. Immobilized free radicals, like their mobile counterparts, are highly unstable, but they gain some kinetic stability because of limited mobility and
530:"Method for Direct Determination of the Effective Correlation Energy of Defects in Semiconductors: Optical Modulation Spectroscopy of Dangling Bonds"
1194:
Tutsch, Leonard; Feldmann, Frank; Polzin, Jana; Luderer, Christoph; Bivour, Martin; Moldovan, Anamaria; Rentsch, Jochen; Hermle, Martin (2019).
466:
In experiments by
Yunteng Qu et al., dangling bonds on graphene oxide were used to bind single metal atoms (Fe, Co, Ni, Cu) for applications in
1180:
1083:
195:
conduction band and the dangling bond or the top of the valence band and the dangling bond. This is due to lattice relaxation which causes a
382:
By definition, passivation is a treatment process of the surface of the layers to reduce the effects of the surrounding environment. In
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Light can also induce dangling bond formation in materials with intimately related valence alternation pairs (IVAP), such as
390:, also known as \Atalla passivation", and hydrogen passivation, which is one of the chemical methods used for passivation.
133:
to the silicon from hydrogen on a dangling bond. It also appeared that the Si-Si and Si-H bonds are about equally strong.
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In hydrogenated silicon, dangling bonds can be induced by (long) exposure to light. This causes a decrease in the
122:
1503:
17:
1196:"Implementing transparent conducting oxides by DC sputtering on ultrathin SiOx / poly-Si passivating contacts"
949:
Haneman D (1974-01-01). "Review of
Electron Paramagnetic Resonance Investigations of Semiconductor Surfaces".
855:
Pankove JI, Wu CP, Magee CW, McGinn JT (September 1980). "Laser annealing of hydrogenated amorphous silicon".
812:
Dersch H, Stuke J, Beichler J (1981-03-15). "Light-induced dangling bonds in hydrogenated amorphous silicon".
191:
80:
76:
367:. Consequently, the dangling bond density at the surface is much lower and no Fermi level pinning occurs.
270:
223:
196:
906:
Smith ZE, Wagner S (October 1985). "Intrinsic dangling-bond density in hydrogenated amorphous silicon".
206:
Another way in which the presence of dangling bonds affects the optical properties of a material is via
471:
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Solar energy : the physics and engineering of photovoltaic conversion, technologies and systems
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149:. While free radicals are usually short-lived, immobilized free radicals often exhibit a longer
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182:
142:
1147:
Smets, Arno H. M.; Jäger, Klaus; Isabella, Olindo; Swaaij, René ACMM van; Zeman, Miro (2016).
125:(EPR) spectra of amorphous hydrogenated silicon (a-Si:H) do not differ significantly from the
359:, stronger electron pairing is observed at the surface, making for almost filled orbitals in
112:
36:
1102:"Removal of dangling bonds and surface states on silicon (001) with a monolayer of selenium"
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Tao, Meng; Udeshi, Darshak; Basit, Nasir; Maldonado, Eduardo; Kirk, Wiley P. (2003-03-10).
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658:"Hydrogen dangling bonds induce ferromagnetism in two-dimensional metal-free graphitic-C
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Buriak JM (May 2002). "Organometallic
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Biegelsen DK, Stutzmann M (December 1985). "29Si hyperfine measurements in a-Si:H".
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calculation of these energy differences and the experimentally measured energies.
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Yates JT (1991). "Surface chemistry of silicon-the behaviour of dangling bonds".
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580:"Calculation of the optical properties of the isolated dangling bond in silicon"
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Bonilla, Ruy S.; Hoex, Bram; Hamer, Phillip; Wilshaw, Peter R. (2017-06-12).
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Ma YW, Lu YH, Yi JB, Feng YP, Herng TS, Liu X, et al. (March 2012).
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of the material and those with none have an energy that is closer to the
767:"Optical properties of dangling-bond states at cleaved silicon surfaces"
718:"Room temperature ferromagnetism in Teflon due to carbon dangling bonds"
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of the material. (This is the most named explanation for the so-called
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169:. This only happens when the dangling bond electron does not pair its
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Xu K, Li X, Chen P, Zhou D, Wu C, Guo Y, et al. (January 2015).
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1237:"Dielectric surface passivation for silicon solar cells: A review"
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in the energy. This shift accounts for the difference between a
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317:
1000:
Lemke B, Haneman D (1978-02-15). "Dangling bonds on silicon".
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67:, a reference to its structural and chemical similarity to a
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Luminous chemical vapor deposition and interface engineering
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56:
436:) on the top of the c-Si substrate be the mean of thermal
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and the abundancy of surface states pins the Fermi level.
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counterpart, a-Si:D, suggesting that there is hardly any
59:. An atom with a dangling bond is also referred to as an
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1234:
1099:
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Principles of adsorption and reaction on solid surfaces
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A dangling bond adds an extra energy level between the
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Advanced Free
Radical Reactions for Organic Synthesis
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bonds with two electrons have an energy close to the
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103:with other atoms. In the simplest case, that of a
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577:
91:In order to gain enough electrons to fill their
1406:Carlos WE, Taylor PC (1982). "H1 NMR in a-Si".
578:Petit, J.; Lannoo, M.; Allan, G. (1986-12-01).
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35:. The dangling bonds are depicted as blue-red
31:A schematic illustration of dangling bonds in
303:Due to the reactivity of dangling bonds, the
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321:as surface states in electronic processes.
161:The presence of dangling bonds can lead to
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1179:: CS1 maint: location missing publisher (
1082:: CS1 maint: location missing publisher (
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503:, a dangling bond generally represents an
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444:(ALD). In the case of the formation of SiO
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153:because of this reduction in reactivity.
287:are active in EPR measurements. Mainly
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440:or other deposition techniques such as
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262:Here, D is an uncharged dangling bond.
14:
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1343:. Amsterdam: Elsevier. pp. 1–35.
1200:Solar Energy Materials and Solar Cells
295:has 3/4 dangling bond, and an atom of
249:resulting in the following reactions:
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765:Assmann, J.; Mönch, W. (1980-09-01).
1445:Journal of Physics: Condensed Matter
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528:Vardeny, Z.; Tauc, J. (1985-04-22).
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951:Japanese Journal of Applied Physics
378:Passivation (silicon photovoltaics)
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627:Journal of Non-Crystalline Solids
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474:, comparable to Pt/C electrodes.
279:Surfaces of silicon, germanium,
192:valence band and conduction band
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857:Journal of Electronic Materials
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355:For the compound semiconductor
123:Electron Paramagnetic Resonance
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363:and almost empty orbitals for
307:native oxide will form due to
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1213:10.1016/j.solmat.2019.109960
791:10.1016/0039-6028(80)90574-9
643:10.1016/0022-3093(85)90755-0
604:10.1016/0038-1098(86)90823-9
461:
403:Dielectric layer passivation
289:group 14 (formerly group IV)
7:
1362:. New York: Marcel Dekker.
554:10.1103/PhysRevLett.54.1844
412:(mostly silicon dioxide SiO
156:
10:
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1048:Masel, Richard I. (1996).
584:Solid State Communications
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1465:10.1088/0953-8984/3/S/024
1054:. New York. p. 198.
472:electrochemical potential
1499:Condensed matter physics
1428:10.1103/PhysRevB.26.3605
1022:10.1103/PhysRevB.17.1893
928:10.1103/PhysRevB.32.5510
275:their original position.
99:), many atoms will form
61:immobilized free radical
1241:Physica Status Solidi A
1206:. Elsevier BV: 109960.
1106:Applied Physics Letters
814:Applied Physics Letters
534:Physical Review Letters
501:computational chemistry
495:Computational chemistry
442:atomic layer deposition
224:Staebler-Wronski effect
1306:10.1002/adma.201904496
1262:10.1002/pssa.201700293
1151:. Cambridge, England.
478:Ferromagnetic polymers
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1504:Solid-state chemistry
1247:(7). Wiley: 1700293.
971:10.7567/JJAPS.2S2.371
722:Nature Communications
339:semiconductor devices
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185:
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394:Hydrogen passivation
372:doped semiconductors
333:of silicon, such as
1457:1991JPCM....3S.143Y
1420:1982PhRvB..26.3605C
1298:2019AdM....3104496Q
1253:2017PSSAR.21400293B
1118:2003ApPhL..82.1559T
1014:1978PhRvB..17.1893L
963:1974JJAPS..13..371H
920:1985PhRvB..32.5510S
869:1980JEMat...9..905P
826:1981ApPhL..38..456D
783:1980SurSc..99...34A
734:2012NatCo...3..727M
635:1985JNCS...77..703B
596:1986SSCom..60..861P
546:1985PhRvL..54.1844V
230:temperature.
197:Franck-Condon shift
65:immobilized radical
1286:Advanced Materials
877:10.1007/BF02822725
743:10.1038/ncomms1689
682:10.1039/C4SC02576H
629:. 77–78: 703–706.
285:germanium-silicide
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55:on an immobilized
51:is an unsatisfied
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37:hybrid sp orbitals
1408:Physical Review B
1391:10.1021/cr000064s
1369:978-0-8247-5788-5
1358:Yasuda H (2005).
1350:978-0-08-044374-4
1158:978-1-906860-32-5
1126:10.1063/1.1559418
1112:(10): 1559–1561.
1002:Physical Review B
908:Physical Review B
540:(16): 1844–1847.
407:Passivation by a
335:amorphous silicon
325:In semiconductors
220:photoconductivity
113:hybrid sp orbital
33:amorphous silicon
16:(Redirected from
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73:
69:free radical
64:
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666:nanosheets"
346:Fermi level
131:backbonding
105:single bond
1493:Categories
728:(1): 727.
511:References
331:allotropes
309:adsorption
137:Reactivity
127:deuterated
97:octet rule
95:(see also
87:Properties
1481:250870056
1473:0953-8984
1436:0163-1829
1322:202562115
1271:1862-6300
1222:0927-0248
1175:cite book
1167:944318061
1134:0003-6951
1078:cite book
1030:0163-1829
979:0021-4922
885:0361-5235
842:0003-6951
799:0039-6028
612:0038-1098
468:catalysis
462:Catalysis
438:oxidation
45:chemistry
1399:11996538
1314:31512296
1070:32429536
987:98799174
893:93272408
752:22395618
700:28580096
562:10031155
314:selenium
297:group 15
293:group 13
281:graphite
157:Magnetic
151:lifetime
143:reactive
1453:Bibcode
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1294:Bibcode
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936:9937788
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779:Bibcode
730:Bibcode
691:5435869
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365:gallium
361:arsenic
266:Surface
214:Induced
178:Optical
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505:error
428:, or
329:Some
121:that
1469:ISSN
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1395:PMID
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1267:ISSN
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1181:link
1163:OCLC
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