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critical temperatures could be calculated through the interaction parameter and these critical values depend on the chosen model. The maximum mole fraction of indium incorporated into InxGa1-xN, which depends on the value of elastic strain of InxGa1-xN was studied. From this result, it can be suggested that the maximum mole fraction of indium incorporated into InxGa1-xN can be increased by decreasing the strain energy of InxGa1-xN.

2.3 Indium Nitride (InN) and Indium Gallium Nitride (InxGa1-xN) Growth

Challenges

There are several problems to be overcome for high crystalline InN and InxGa1-xN film growth. These problems are narrow region of growth temperature due to the low decomposition temperature, low cracking efficiency of NH3, no suitable nitrogen precursors to improve the decomposition efficiency of NH3, and carrier gas. These problems which occur during the growth of InN and InxGa1-xN are briefly discussed in this part.

2.3.1 Growth Temperature and V/III Ratio

The growth of InN is the most difficult among the III-nitrides because the equilibrium vapor pressure of nitrogen over the InN is several orders higher than AlN and GaN [Amb96]. Because of the low InN dissociation temperature and high equilibrium N2 vapor pressure over the InN film [McC70], the growth of InN requires a low growth temperature. Due to the low (~550 °C) growth temperature, the MOVPE growth of InN is thought to be restricted by a low decomposition rate of NH3. Although a higher growth temperature is expected to result in a higher decomposition rate of NH3, it can also result in thermal decomposition (thermal etching) of the grown InN. On the other hand, the growth at a low temperature (lower than 400 °C) is dominated by the formation of

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metallic indium droplets due to the shortage of reactive nitrogen. Epitaxial growth at low temperature becomes impossible due to reduced migration of the deposited materials. Therefore, the region suitable for the deposition of InN is very narrow.

Koukitu et al. carried out a thermodynamic study on the MOVPE growth of IIInitrides [Kou97b]. They pointed out that a high input V/III ratio, the use of an inert carrier gas, and a low mole fraction of the decomposed NH3 are required for the growth of InN. Experimental results also match well with the first two points (high input V/III ratio and the use of inert carrier gas) but are not clear on the last point (a low mole fraction of the decomposed NH3).

High input V/III provides sufficient amount of reactive nitrogen, since the NH3 decomposition rate is low at low growth temperature. NH3 is decomposed thermodynamically into H2 and N2 with low decomposition efficiency at temperature higher than 300 oC, which results in the increase of H2 partial pressure [this sentence does not make sense, there is low decomposition efficiency at T < 300oC, and at higher temperatures the H2 partial pressure increases]. Thus too high ratio of V/III significantly prevents the growth of InN and leads to the etching of InN due to the increase of H2 partial pressure (Eq. (2-10)). A suitable region of V/III ratio and growth temperature is required for the high quality InN growth without indium droplets formation during the growth.

The main problem in growing InxGa1-xN has been the phase separation at high indium incorporation (x (In) > 0.3) due to the very high equilibrium vapor pressure of nitrogen over InN. The compositional control has only been achieved for relatively low growth temperature, up to 650 oC. However, crystal quality is not good because the

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decomposition rate of NH3 is very low below 1000 oC. Yoshimoto et al. [Yos91] obtained the relatively high-quality InxGa1-xN using a high temperature (800 oC) and a high indium flow rate. In that case of the temperature growth (650-800 oC), the phase separation may occur because of the large mismatch (11 %) between InN and GaN. The lattice mismatch between InN and GaN (due to the very different tetrahedral radii) results in highly strained InxGa1-xN. Therefore at the growth temperature of 650-850 oC, phase separation is still a major concern.

2.3.2 Nitrogen Source

InN and InxGa1-xN are typically grown by MOVPE using conventional group III precursors such as tri-methyl indium and tri-ethyl indium with NH3 as the active nitrogen source. However, InN and InxGa1-xN are relatively difficult to produce with the high quality required for minority carrier devices due to high equilibrium N2 vapor pressure and the low decomposition efficiency of NH3 as discussed earlier.

NH3 is almost stable even at 1000 °C and decomposes only 15 % at 950 oC, even when catalyzed by GaN [Che91]. The combination of high growth temperatures and high nitrogen volatility leads to high concentrations of N vacancies in GaN and InN. This is often cited as the reason that the GaN and InN epitaxial layers are n-type.

Solution of this problem will probably require N precursor to give the high active nitrogen reduction at the low growth temperature. Hydrazine (N2H4) is an attractive N precursor because it contains no carbon atoms to be incorporated into the solid, and the hydrogen atoms are potentially beneficial for removal of the alkyl radicals (from the group III precursors) from the surface. It decomposes at temperatures as low as 400° C, considerably lower than temperatures required for NH3 because of the weaker N-N bond [Gas86], thus making it suitable for growth at temperatures well at the current growth

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temperature (~550 oC) and at low V/III ratio as low as 10 which prevents the waste of N precursor. It also has a favorable vapor pressure of approximately 10 Torr at 18°C, as indicated in Table 2-8. However, hydrazine is a toxic material, a rocket fuel, and explosive. When hydrazine is used in III-V nitride growth with the trimethyl-group III alkyls, the adduct formation between hydrazine and the group III precursors was observed. The layers were found to be contaminated with both oxygen and carbon. The hazard associated with the toxicity and explosiveness of hydrazine makes its use in a production environment unlikely.

Unsymmetrical dimethylhydrazine (H2N2 (CH3)2, 1,1 DMHy) is a considerably safer alternative to hydrazine. It has a vapor pressure of 157 Torr at 25 °C and pyrolyzes at temperatures considerable lower than for NH3. However, relatively high (>1019 cm-3) levels of oxygen and carbon were observed, both of which are associated with the use of DMHy.

A potentially less hazardous precursor, phenyl hydrazine, has also been explored [Jon95]. However, the vapor pressure of 0.03 Torr at room temperature is far too low to be acceptable.

Hydrogen azide, or hydrazoic acid (HN3) has also been successfully used for MOVPE growth in a low-pressure reactor [Cht97].This precursor is attractive because it has a high vapor pressure (the boiling temperature is 37 °C) and decomposes at approximately 300 °C to yield HN radicals with two dangling bonds, a potentially good source of atomic nitrogen, and N. However, it is highly toxic and potentially explosive.

The N precursor tertiary-butylamine ((C4H9)NH2 or TBAm) has a convenient vapor pressure of 340 Torr at 25 oC, a low toxicity, and is stable. However, the use of TBAm

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for the growth of GaN has proven unsuccessful [Rus96, Bea97]. They observed no GaN

deposition but rather deposition of a layer consisting mostly of carbon [Bea97].

In summary, several candidates for nitrogen sources were reviewed and all of them have some problems such as toxicity, explosion, low decomposition efficiency, and contamination. NH3 has been still widely used as a nitrogen source in spite of low decomposition efficiency. The design of the optimum nitrogen source for the growth of

III/V nitrides is still required even though it is tricky.

Table 2-8. Properties of nitrogen precursors for MOVPE.