Quantum chemical study of parasitic reaction in III–V nitride semiconductor crystal growth

Nakamura, Kōichi; Makino, Osamu; Tachibana, Akitomo; Matsumoto, Koh

doi:10.1016/s0022-328x(00)00403-4

Cited by 77 publications

(101 citation statements)

References 30 publications

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“…From the viewpoint of the substituent effect, the Mulliken charges of the alkyl groups R clearly show the well-known order of the ability for electron donation, -t-C 4 H 9 > -C 2 H 5 > -CH 3 . The ability for electron donation contributes to suppression of the intramolecular polarization that prevents the coordination interaction [9][10][11]. However, the M-N bond orders and the quantities of the Mulliken charge transfer from NH 3 to MR 3 inform us that 2 has the same degree of M-N coordination interaction as (C 2 H 5 ) 3 M⋅NH 3 for each M though it has a stronger one than (CH 3 ) 3 M⋅NH 3 , because three bulky t-butyl groups prevent the metal atom from configuring the distinct tetrahedral coordination observed in (CH 3 ) 3 M⋅NH 3 and (C 2 H 5 ) 3 M⋅NH 3 [9,10]: the tetrahedral coordination of M is quite easy to receive the lone pair of NH 3 .…”

Section: Resultsmentioning

confidence: 99%

“…On the other hand, the growth of AlGaN layers at atmospheric-pressure MOVPE is inhibited by gas-phase reactions among precursors leading to adduct formation, called "parasitic reactions" [3 -5]. We have studied the mechanism of gas-phase reactions in MR 3 /H 2 /NH 3 (M = Al, Ga, In; R = CH 3 , C 2 H 5 ) systems by a quantum chemical approach [9 -17], and have clarified that the Al source gases and their deviates enhance reactivity to the parasitic reactions [9][10][11][12][13][14]. In order to suppress the parasitic reactions, we have to consider another Al source gas for the growth of AlGaN.…”

Section: Introductionmentioning

confidence: 99%

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Quantum chemical study on substituent effect of gas‐phase reactions in III–V nitride semiconductor crystal growth

Okada

Doi

Nakamura

et al. 2004

Physica Status Solidi (b)

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We have carried out ab initio quantum chemical calculations to discuss the substituent effect of the metal source on the coordination interaction and the reactivity in the gas-phase parasitic reactions in M(t-C 4 H 9 ) 3 /H 2 /NH 3 (M = Al, Ga) systems following the elimination of isobutane. We found that t-butyl groups play two important roles: high ability for electron donation leading to large M -N interaction and high bulkiness leading to large steric repulsion. It is expected that the extension of chain adducts obstructing the growth of AlGaN would be suppressed by the steric hindrance due to bulky substituents lifting up the activation energies in the parasitic reactions.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Quantum chemical study on substituent effect of gas‐phase reactions in III–V nitride semiconductor crystal growth

Okada

Doi

Nakamura

et al. 2004

Physica Status Solidi (b)

Self Cite

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“…28 No matter which one is dominant, the Lewis acid-base adducts (CH 3 ) 3 M:NH 3 are agreed to be the first product formed upon the precursor mixing at the entrance inlet. 29 When these adducts undergo irreversible decomposition into amide (CH 3 ) 2 MNH 2 or imide (CH 3 )MNH intermediates, further association (oligomerization) could bring them to initiate nanoparticle formations. Such a reaction channel is referred to as "adduct parasitic pathway".…”

Section: 27mentioning

confidence: 99%

Incorporation Behaviors of In and Ga in the Two-Heater MOVPE Growth of InGaN Films

Cheng

Lee

et al. 2016

ECS J. Solid State Sci. Technol.

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Incorporation behaviors of In and Ga of InGaN films grown by the two-heater metal-organic vapor-phase epitaxial horizontal reactor is investigated by varying growth parameters, such as the substrate temperature, ceiling temperature and reactor pressure. Two In loss mechanisms are observed by the analysis of the concentration and temperature profiles in the deposition zone. The gas-phase parasitic-loss mechanism (activation energy ∼ 34.2 ± 0.1 kcal/mol) is significant in the ceiling temperature T ceil ≥ 800 • C and at substrate temperature (T sub ) of 600 • C. The decomposition-loss mechanism, which arises from In desorption on the growing surface, is significant in T sub > 625 • C region. The desorption activation energy obtained is 28.0 ± 0.1 kcal/mol, which is close to that of . This suggests the In decomposition-loss mechanism in InGaN growth does not differ substantially from that in binary InN growth. On the other hand, the gas-phase parasitic-loss mechanism of Ga is negligible in the growth condition that we have explored. Exception is found for reactor pressure at T ceil = 950 • C, where both factors advantageous and disadvantageous to Ga incorporation are unambiguously observed. We have proposed explanation for the above observation. The promising electronic and optical properties of InGaN alloy, such as high two-dimensional electron gas (2DEG) electron mobility, wide tunability of photon emission energy from 0.7 to 3.4 eV, have given rise to numbers of applications in the past decade. These include high power and high electron mobility transistor (HEMT), visible light emitting devices, tandem solar cell, and solid state lighting.1-7 To realize, a method that capable of growing device-quality III-V nitrides is essential. Among all growth methods, metal-organic vapor-phase epitaxy (MOVPE) has proved itself to be the most reliable and major tool to produce these devices with mass-production feasibility. However, difficulties arise for this method in preparing high In content In x Ga 1−x N film (x > 30%) with acceptable optical and electrical properties. This stems mainly from the intrinsic properties of material itself, such as thermal instability of InN, wide miscibility gap, and large thermal-and lattice-mismatch between InGaN layer and underlying GaN base layer, and poor cracking efficiency of NH 3 . These lead to generations of considerable amounts of nitrogen vacancies, pits, In-rich clusters and/or structure defects in the film to deteriorate its material properties. [8][9][10][11][12][13][14][15][16][17] In our previous work, we have employed a so-called the two-heater MOVPE horizontal reactor, consisting of a pair of paralleled ceiling and substrate heaters, 18 to grow InGaN films. We demonstrated its ability in preparing high In-content thick InGaN films with emission wavelength extended into infrared color region, and more importantly exhibiting good optical-quality and high spectral uniformity. For instance, a sample with x = 0.40 In x Ga 1−x N film has a mean emission wavelength of 808 ± 6 nm a...

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“…The parasitic reaction is expected to be responsible for the phenomena. It has been reported that NH 3 can reduce the potential energy barrier of trimers and higher n-mers formation (Nakamura et al, 2000). Therefore, with the increase of the flux of NH 3 , the quantities of trimers and higher nmers which do not contribute to the growth will increase, and the growth rate of AlN will decrease.…”

Section: Parasitic Reaction Between Tmal and Nh 3 In Mocvdmentioning

confidence: 99%

GaN Based Ultraviolet Photodetectors

Zhao¹,

Jiang²

2011

Photodiodes - World Activities in 2011

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Quantum chemical study of parasitic reaction in III–V nitride semiconductor crystal growth

Cited by 77 publications

References 30 publications

Quantum chemical study on substituent effect of gas‐phase reactions in III–V nitride semiconductor crystal growth

Quantum chemical study on substituent effect of gas‐phase reactions in III–V nitride semiconductor crystal growth

Incorporation Behaviors of In and Ga in the Two-Heater MOVPE Growth of InGaN Films

GaN Based Ultraviolet Photodetectors

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