Chapter 21 + Metal Organic Vapor Phase Epitaxy Chemical Kinetics 887 21.4 Reaction Kinetics of Organometallic Compounds The specific proposed reaction schemes for the wide variety of metal organic com- pounds form an extensive literature, The purpose herein is to outline features of many of the common metal organic systems. 21.4.1 Determination of the Gas Phase and Surface Kinetic Processes There have been experimental and computational approaches to the determination of the homogeneous and heterogeneous chemical kinetics associated with the commonly uused metal-organic compounds. These reaction pathways and rates are used in the development of reactor-scale models of the growth process and subsequently for reactor design, Experimentally, these reaction rates wete obtained by allowing the source molecule of interest to pass under conditions of controlled temperature, gas environ- ment, and pressure for a known period and the resulting gas phase or surface compo- sition monitored. In a typical and well-used experimental arrangement, the reactants of interest pass through a tube of constant temperature, typically referred to as a “flow tube” and the effluent monitored. Gas is sampled from within the heated region to prevent unwanted reactions that could be present if the reacted gas mixture was allowed to cool to room temperature. The composition of the gas is often determined by mass spectroscopy (66,67] or optical means, such as Fourier transform infrared spectroscopy [68], or deduced by deposition rates [69]. There are many common features to the decomposition or reaction networks. The most studied of the commonly used precursors are trimethyl and triethyl gallium, which exhibit many of the characteristics common to many of the group 15 alkyls, 21.4.2 Gallium Sources The most commonly used gallium source in MOVPE is trimethyl gallium. The initial studies of the pyrolysis of trimethyl gallium were conducted by Jacko and Price (70). In those studies, the (CHs)sGa was heated in a toluene carrier gas. The toluene is a scav- enger for methyl radicals through the formation of methane and Crli;, which would suppress the subsequent reaction of these radicals on the parent molecule [71]. This early study found that the homogeneous decomposition of (CHs)sGa occurred through the homolytic cleavage of methyl groups from the compound at elevated temperatures Ga(CH), +Ga(CHs), + CHs Ga(CHl,), +Ga(CH) + CI, n(GaCHs) -+(GaCHs) CH, + CH, Ge with an activation energy of 59.4 and 35.4 kcal mol”! for the first and second listed re- action, respectively. At a high enough concentration, the monomethyl Ga would poly- merize and non-scavenged methyl radicals would be able to form ethane. These reactions have also been subsequently studied in greater detail, Larson and coworkers a6)888 HANDBOOK OF CRYSTAL GROWTH 100 5 aol oh 2 of} $02 al 3 he B60) Nee Be rere / 2 0 2 2 ° ee 200 300 300 Goo Temperature (°C) FIGURE 21.11 Decomposition rate with temperature of (CHa in Hectoluene misture, Ne, He, Dp and Hy (66) ‘The dashed line, ealeulate for pure toluene carrer. From data of Ref (70). Partial Pressure (Torr) 200. 300. ~400~=«500.-~=«600 Temperature (°C) FIGURE 21.12 Decomposition products of (Hs)Ga in H 32) studied the decomposition of (CH;)3Ga in a variety of carrier gasses: He, Nz, Ho, and Dz in the presence and absence of toluene. The rate of decomposition and the distribution of measured reaction products are presented in Figures 21.11 and 21.12, respectively [66]. The change in decomposition rates with carrier gas indicates that there is an active role for hydrogen in scavenging methyl radicals resulting from decomposition. In addition to those reactions described by Eqn (21.16), in the case of a hydrogen carrierChapter 21 + Metal Organic Vapor Phase Epitaxy Chemical Kinetics 889 gas, there is an active reaction between the methyl radicals and hydrogen which accelerates the decomposition rate (66) Ga(CH,), +Ga(CH), + CH, CHy~Hh>CH, +H H+ Ga(Cl,), +GaCH, + CH, + CH, CH: = Cis *GHe ‘The heterogeneous reaction of (CH,)3Ga on a growth surface is equally complex and depends on the surface structure, surface orientation, and surface composition. For example, (CHs),Ga resulting from the gas phase decomposition will react rapidly at an arsenic site on the GaAs (001) surface. It will also react, albeit at a much slower rate, on the Ga-terminated GaAs (001) (72]. As noted above, the relative populations of As and Ga on the growth front will depend on the gas phase ambient and temperature. (CH3),Ga will decompose more rapidly in the presence of Astly. Iligh (V/IID ratios of AsiI to (CHis}sGa do lead to reduced carbon incorporation (73). This is attributed to the reaction of surface-adsorbed methyl radicals with hydrogen arising from surface AsH, species or AsHs in the gas phase. AsH will, therefore, accelerate the decomposition of (CHs)sGa [32,74] through enhancing its decomposition. Triethyl gallium, (ColIs);Ga, exhibits a different reaction behavior from (Cl1s);Ga. ‘There ate two primary reactions accessible for the decomposition of (CoHs),Ga in the gas phase, which have been noted: the homolytic cleavage of the ethyl radical and the B- elimination reaction, an (CoH), Ga—+ (CyHe),Ga-+ GoHs (GH,),Ga—+(H,),HGa +H, 18) ‘The f-elimination reaction has been experimentally shown to occur much more rapidly within the CVD gas phase environment (67,751. This is shown in Figure 21.13, where the decomposition rate is relatively independent of the carrier gas unlike that seen for (CHs)sGa [67]. The f-elimination reaction leads to a reduced carbon incorporation because the C2H, leaving group does not interact with the growth surface under typical MOVPE growth conditions (76). The lower decomposition temperature also allows this gallium source to be used in applications where low growth temperatures are required, such as in the formation of low melting point materials and metastable alloys. ‘The heterogeneous reactions of (CHs);Ga have been studied in some detail because of its use in a high vacuum-based technology called chemical beam epitaxy (77) and in studies of atomic layer epitaxy [78]. The surface chemistry of all these organometallic compounds is complex. As with (CHs);Ga, the adsorption and reaction of (CrHs)sGa depends on a wide variety of factors and there is an extensive literature associated with it, (CHs)sGa rapidly adsorbs onto an arsenic site and appears to undergo dissociation to (Calls).Ga, (CzH1s) Ga, Ga adatoms, and ethyl radicals on the surface [79]. These surface ethyl radicals further desorb or decompose to ethylene or desorb. Other gallium sources have been investigated, such as isopropyl gallium [90,81] and gallane (GazHig) based adduct compounds (82-84), The adduct compounds stabilize the890 HANDBOOK OF CRYSTAL GROWTH TeGa int, 8 coy ES ine cobs x5 Sie ss G8" C075) rere 500 600 700 800 Temp ik) FIGURE 21.13 Decomposition products of (GH4)Ga in Hy and He (67 gallane from rapid decomposition at room temperature. These sources have not gained widespread use because of their difficulty in synthesis, purification, and storage. 21.4.3 Aluminum Sources Trimethyl aluminum, (CHi}sAl, has been a primary growth source used in MOVPE, particularly in the growth of AlGa,»As, Al(In,Ga),,P, and AlGa-N. Unlike (CHs)sGa, (CHs)sAl is dimer in the liquid phase and in the gas phase at near-room temperature conditions. Unlike the analogous gallium source, the thermal pyrolysis of (CHs)sAl leads to the formation of Al;C; and not Al metal (85-87). Overall, (CHs)sAl appears to initially decompose through similar mechanism as (CI13)3Ga, with homolytic cleavage of the methyl radicals. Triethyl aluminum, (CzHs)sAl, and triisoburyl aluminum, ((CHs),CHCH,}sAl, decompose through a f-elimination reaction [88] and can lead to the deposition of metallic Al (89). Alane or AIH; has also been extensively used in the growth of aluminum-bearing alloys. In these studies, the alane forms an adduct with a primary amine, such as trimethyl amine, (Clig)5N [90,91]. The adduct bond is relatively weak and is thought to dissociate at low temperatures within the reactor. The absence of a direct aluminum-carbon bond in alane has led to a strong decrease in the background carbon incorporated into a growing film relative to the other sources described.Chapter 21 + Metal Organic Vapor Phase Epitaxy Chemical Kinetics 891 FIGURE 21.14 Decomposition products of (CAs in De (22. Partial Pressure (tor) tov” zuv suD uy buy oe Temperature (°C) 21.4.4 Indium Sources The two most commonly used In sources are trimethyl indium, (CHs)sIn, and triethyl indium, (C)Hs)sIn, which are solid and liquid, respectively. As with the Ga and Al compounds, these sources have been studied through various pyrolysis experiments. ‘The thermal pyrolysis of the In alkyls is thought to be similar to the Ga-based com- pounds. The weaker In-C bond leads to lower decomposition temperatures (92,93), well lower than the range of 450-500 °C which is characteristic of the Ga and Al compounds. A feature of (CH,)sIn decomposition is the subsequent formation of ethane as @ reaction product in the absence of a group 15 source, as shown in Figure 21.14 (66). This has been rationalized by the reaction (66) CH, + (CHy),In>(CH,),In + CoH, ) CH, + (CH,),ln-+(CH,), CHIn + CH, oui Initial studies of the growth of In-base’ semiconductors were plagued by surface and gas phase decomposition within the growth environment within the cold regions of the reactor. This was eventually attributed impurities remaining within the metal alkyl source and eliminated through the further purification of the trimethyl indium source material 21.5 Reaction Kinetics of Group 15 Compounds 21.5.1 Arsenic and Phosphorus Sources. The group 15 elements also form compounds of the type XRs, where R =H, CHs, CH, CgHlg, and so on. The most used sources of As and P have been the hydrides (R = 1) AsHz and phosphine (PH,). There are severe toxicity concems with these P, As, and Sb compounds [65]. In addition, as gases stored in high-pressure gas cylinders, these sources present a high safety hazard which must be addressed through strict adherence to local safety standards for their use, storage and handling [94). AsHy and PHs have been892 HANDBOOK OF CRYSTAL GROWTH used extensively in the MOVPE based growth of most arsenide and phosphide materials. The gas phase pyrolysis of these materials is slow at the low temperatures characteristic of the bulk of the reactor gas phase environment, Two reaction pathways have been proposed for the homogeneous gas phase reaction, both AsH, and PH (@)AsHh Ast =H (D)ASH, ASH +H, 21.20) Previous calculations have indicated that the second reaction, Eqn (21.20b), has a much higher rate over a broad range of temperature and pressure should be favored for ho- mogeneous gas phase decomposition (26). There have been some experimental de- terminations of the homogeneous gas phase decomposition of these hydrides [95]. In one study, ASH; decomposition performed in a D2 carrier gas did not lead to any for- mation of HD as would be expected if the reaction Eqn (21.20b) was present. In subsequent studies, the lack of the formation of HD led to the conclusion that the decomposition is dominated by the heterogeneous surface reaction wherein the hydride is adsorbed at the surface and decomposes by the loss of an H atom to the surface. Surface-absorbed H atoms then recombined to form H (96]. In all cases, the gas phase decomposition rates are slow at typical gas phase temperatures within the reactor, except close to the growth front, and AsH; decomposition has been shown to be dominated by surface reactions. The dominance of the heterogeneous reaction in the MOVPE environment is further substantiated because the decomposition rate of AsHls [96-99] is greatly accelerated by the presence of a GaAs substrate, adsorbing and reacting on a Ga surface site. Phosphine may react in a similar manner to AsHIs, with the characteristic temperatures for decomposition being somewhat higher. The group 15 alkyls have also been used in MOVPE growth systems. The most commonly used organo-As and organo-P sources are t-butyl arsine and phosphine, (CallghAstlp and (Cylls)PH2. One study has indicated that the gas phase decomposition of these compounds can be rationalized by the existence of two major decomposition routes: (1) a low activation energy pathway producing isobutane and AsH, and (2) a higher activation energy, f-elimination pathway producing isobutene and AsHs (100,101). These compounds are used as an alternative to gas sources, arsine and phosphine, and as liquid sources they present a reduced safety hazard. They decompose at substantially lower temperatures than the hydrides and are used in the low temper- ature growth of several compound semiconductors. 215.2 Nitrogen, Group 12, and Antimony Sources Organometallic sources exist for the other common anions used in compound semi- conductor alloy growth. There are many alkyl sources for antimony, selenium, and tellurium that were developed in response to the formation of GaAs ,Sby and for I-VI materials, such as ZnSe or Hg,Cd)_.Te, Commercially available sources are of the form, SbRs where R=CHs, CH, CsHy,... or similar sources of Zn and Cd (e.g, (CH3)sZn) These sources generally decompose and similar manner to that described for (CHs),GaChapter 21 + Metal Organic Vapor Phase Epitaxy Chemical Kinetics 893, with homolytic fissure of the alkyl group (102). The use of organometallic compounds as both the anion and cation sources in the growth of GaAs;_Sb, has led to the complex interaction of these species when combined with the complex strain-related phase di- agrams associated with this alloy system [63,64,103,104]. The growth exhibits a complex dependence of the composition on the gas phase composition, which is dependent on the specific chemical sources, growth temperature, and strain state of the epitaxial film. In the case of selenium and sulfur, commercially available compressed gas hydrides do exist and are used along with organo-S and Se compounds. Ammonia, NH, is the most common source used in the growth of nitride-based semiconductors such as GaN or In,Ga;_,N. The homogeneous gas phase reaction pathways of ammonia are well known [26,105]. Given the high temperature decomposition temperatures associated with ammonia, 1,1-dimethylhydrazine, (CHs)2NNH», has also been used (106), particularly in the growth of In,Gay_,N. In,Ga;_,N requires lower growth temperatures than used for AIN or GaN because of the evaporative loss of indium from the surface. A common feature of the decomposition of these sources is the generation of ‘NIL, and ‘NH radicals, which are considered to be a precursor to subsequent nitrogen incorporation {107,108} ‘The interaction of these radicals with the H carrier gas and the other gas phase species could alter the nature and concentration of these initially radical species at the growth front, There have been other nittogen sources that are based on the analogy to the decomposition kinetics of other group 3 and 5 sources, such as tertiary-butyl hydrazine, (-C,HgNHNH; [109], and tertiary-butyl amine, -C,HsNHz, but they have not been as extensively studied (110 21.5.3 Reactions between Precursors ‘The previous section presented the reaction pathways associated with individual pre- cursors used in the MOVPE technology. The growth of the film is not generally the su- perposition of the individual reactions. There are many reactions between these reactive compounds in the gas phase and at the surface. In the case of group 13 sources, the exchange of ligands within the gas phase has been previously noted (111-113). For example, mixtures of (CHs)3In and (CoHls)sGa lead to the formation of mixed ligand alkyls within the reactor [111] (e.g., (CHs)x(Colls)s_sIn}. There are more substantial re- actions between the group 13 and group 15 sources in the gas phase and at the growth surface. The group 13 alkyls are Lewis acids, whereas the group 15 sources are Lewis bases. ‘These compounds can form adducts or Lewis acid-base compounds. The bond energies associated with the native bonds are typically weaker than the covalent bonds within the source molecule [114]. As an example, the adduct between (CHs);Ga and ammonia, (CHis)sGa:NH, is important in the growth of GaN given the high concentration of ammonia within the reactor for the growth of nitride materials. This adduct can rapidly form, particularly at low gas phase temperatures. This adduct bond has a measured bond strength of ~18 kcal mol”? [115]. The initial Ga~CHy bond strength for comparison is