Substrate for growing gallium arsenide epitaxial layers

FIELD: electronic engineering; materials for miscellaneous semiconductor devices using gallium arsenide epitaxial layers.

SUBSTANCE: intermetallic compounds chosen from group incorporating tin arsenide SnAs, palladium antimonide PdSb, manganese polyantimonide Mn2Sb, nickel stannate Ni3Sn2, nickel aluminate Ni2Al3, nickel germanate Ni2Ge, and cobalt germanate Co2Ge are used as materials of substrates for growing gallium arsenide epitaxial layers.

EFFECT: enhanced structural heterogeneity of gallium arsenide layers being grown.

1 cl

 

The invention relates to electronic devices, and in particular to materials intended for the manufacture of semiconductor devices of a wide class of applications using epitaxial layers of gallium arsenide.

It is known that gallium arsenide due to the peculiarities of the band structure of GaAs is widely used in opto - and microelectronics. Growing quality with the instrumental point of view of epitaxial layers of GaAs was noticeably easier than growing high-quality single crystals. This has stimulated work on growing high-quality epitaxial GaAs films. In further constraints to widespread use of epitaxial GaAs films, was the difficulty and high cost of growing GaAs single crystals of large cross-section for use as the material of the substrate for epitaxial layers of gallium arsenide.

To simplify and cheapen the production of epitaxial GaAs many attempts were made to replace the expensive and complicated to manufacture substrates of GaAs on other, cheaper, for example, of silicon as a direct application of silicon and through the application of intermediate layers between the silicon substrate and the epitaxial layer of GaAs [1]. Due to a number of physico-chemical characteristics of silicon as material these attempts were not very successful.

Friend the first approach to solving this problem was proposed in [2], which explains the growing layers on GaAs substrates made of single crystals of intermetallic-based alloys of transition metals 4 period 5 elements group of the periodic system of elements. This solution is the closest to the proposed invention.

Horizontal Bridgman method is the most common and cheapest method of growing single crystals of intermetallic compounds. Device for growing single crystals by this method is usually done in the form of a quartz tube (reactor) is placed inside a graphite or quartz crucible in a sealed ampoule or purged by a stream of pure hydrogen. The single crystal growth occurs in the process of pulling crucible with the melt formed from buried him in polycrystalline powder antimonide metal in thermal gradient field created dual-zone thermal oven or an induction heater. This method single crystals were grown NiSb, MnSb, CoSb and FeSb [2]. It was found, and then x-ray diffraction methods, it was confirmed that in the process of growing single crystals from a melt of intermetallic in the crucible partially evaporate a certain amount of antimony. Deposition of this vaporized antimony thin tantalum foil at the exit of the reactor and subsequent weighting of assessment was conducted kolichestvennoi from molten antimony by comparing the weight of the grown single crystal with the weight of the original polycrystalline sample in the crucible. It was found that the amount of vaporized antimony is determined by the difference between the composition corresponding to the composition of the grown single crystal of Nickel antimonide and composition, the corresponding Nickel border of Nickel antimonide in the state diagram Ni-Sb. It is known that this feature of the behavior of antimony is related to the fact that the main part of the above-mentioned intermetallic compounds, including Nickel antimonide, are compounds of variable composition. In the case of Nickel antimonide maximum fluctuations of the non-stoichiometric content of antimony in the NiSb is 10% (the boundaries of the homogeneity of Nickel antimonide).

Typically, the single crystals of these intermetallic compounds are grown in conditions close to equilibrium, so they grow with composition close to congruent. However, even the relatively moderate temperatures of crystallization ˜1150-1250°lead to constant evaporation from the surface of the non-stoichiometric volatile component is antimony from molten intermetallic, thereby stimulating the diffusion of antimony in the melt to the surface, leading to volumetric evaporation of volatile component and to the fact that the composition of the grown single crystal is slightly different from the original composition of the polycrystal loaded into the crucible. The measurement periods of the crystal lattices of the original polikristallicheskogo, the corresponding congruentes composition, (a(NiSb)=3,99Å) and grown from it monocrystal detects the relative difference of the periods of the lattices ˜±1,25%. Evaporation of antimony along the sagittal line of the ingot has been mixed, so the grown single crystal chemical composition along the crystal fickle and this complicates the use of single crystals of transition metal antimonides as a cheap and high-quality substrates for epitaxy of gallium arsenide.

The other major method of growing single crystals is the Czochralski method. In the process of growing single crystals described intermetallic compounds by this method is also the preferential evaporation of the more volatile component as the surface of the melt in the crucible and, especially, with the neck of the melt on the border of the melt with pulling the single crystal. The first leads to heterogeneous composition of intermetallic along the length of the crystal (the gradual evaporation of the antimony from the melt leads to depletion of the melt antimony in the tail of the single crystal intermetallic), the second to the axial inhomogeneity of the crystal (due to the depletion of antimony border of the melt with the environment).

The technical problem to be solved in the present invention is the increase in the uniformity of the structure of as-grown GaAs layers along the length of the single crystals is allow intermetallic compounds, used as substrates for epitaxial growth.

The specified technical task is solved in that the substrate for growing epitaxial layers of GaAs using the intermetallic compound selected from the group consisting of gallium tin SnAs, palladium antimonide PdSb, polyanionic manganese Mn2Sb, stannate Nickel Ni3Sn2, Nickel aluminate Ni2Al3, germanate Nickel Ni2Ge and germanate cobalt Co2Ge.

All these compounds are used as substrates, have good negotiation periods lattices with periods of the crystal lattice of gallium arsenide appropriate orientation.

Connection SnAs, PdSb and Mn2Sb due to the low melting point have a low vapor pressure component that allows you to grow crystals for substrates with high chemical homogeneity along the sagittal line. Connection SnAs, PdSb have the stoichiometric composition, which also contributes to the growth of homogeneous along the length of the single crystal.

The difference in the vapor pressure of the component compounds: stannate Nickel - Ni3Sn2(the melting point - 1138° (C), the Nickel aluminate - Ni2Al3(the melting point - 1264° (C), cobalt germanate Co2Ge (melting point - 1200°C)Ni2Ge (t-RA melting - 1200° (C) in point is their melting differ less than an order of magnitude, while the absolute vapour pressure of the components of these compounds has a small amount (<105mm Hg), which avoids the evaporation of one component in the process of growing single crystals and to obtain their high uniformity of composition in the longitudinal and transverse sections.

It is also known that the growth of the epitaxial structures at low temperatures favors the creation of sharp boundaries of the film - substrate interface due to the suppression of mutual diffusion component between the film and the substrate, which occurs at high temperatures cultivation of these structures. Modern technology for the growth of epitaxial films of gallium arsenide (such as molecular beam epitaxy and MOS technology) allow to grow epitaxial films already at 300°C. for these cases are the most suitable low-temperature substrate.

Below is an example of a specific implementation.

The single crystals of gallium-tin were grown as follows.

For carrying out the synthesis of polycrystalline source material is gallium tin SnAs - weighed 77,382 g (polycrystal) arsenic, 122,618 g of tin (in pieces), both materials were loaded in a quartz ampoule, and then the ampoule was pumped through the process in a vacuum unit, and after reaching a vacuum of 10-5mm Hg in the mule was otbivalas.

Sealed ampoule was placed in a two-zone furnace. Oven temperature for 0.5 hours was increased to 250°C. When the tin is melted and was saturated with arsenic. In the process of further increasing the temperature to the temperature of formation of gallium tin (605° (C) the crucible rocked to improve saturation tin arsenic. The vial was maintained at the melting temperature for three hours and then slowly cooled under the program up to 50°C. Thus was synthesized 200 g SnAs. The ampoule was broken, the resulting polycrystal was razmalyvanija, grinded, then the resulting powder was filled in a crucible. The crucible was placed in a quartz ampoule, which was pumped, otbivalas, then placed into a two-zone furnace, and the sample in the crucible is melted. The single crystal was grown by pulling the melt through a temperature gradient of 10°With a speed of 4 mm/hour.

This same technology was grown single crystals of palladium antimonide PdSb, polyanionic manganese Mn2Sb, stannate Nickel Ni3Sn2, Nickel aluminate Ni2Al3, germanate Nickel Ni2Ge and germanate cobalt Co2Ge. The difference in the conditions of growing single crystals was only in their melting temperatures: single crystals of stannate Nickel Ni3Sn2, Nickel aluminate Ni2Al3, germanate Nickel Ni2Ge and Germany the ATA cobalt Co 2Ge was grown in a furnace with induction heating of the crucible. The grown single crystals of intermetallic compounds were subjected to the standard procedure orientation and cutting on the substrate and subsequent chemical-mechanical polishing. Before being placed in the loading chamber with the substrate was removed protective coating after chemical-mechanical polishing.

Epitaxial layers of gallium arsenide grown on these substrates by molecular-beam epitaxy installation APPEARS. The temperature of deposition of epitaxial layers ranged from 250°750°depending on the substrate material. Electron diffraction study of the orientation of the grown epitaxial films of gallium arsenide showed that when grown on substrates selected orientation (right side column) on these intermetallics following orientation relationship:

Using x-ray microanalyzer "Camebax" was measured chemical composition of the primary (head) and tail parts of the crystals. It turned out that for all of the grown crystals in length ˜150-200 mm heterogeneity of the chemical composition along the length does not exceed 0.1%. The results were confirmed by the results of x-ray diffraction measurements of the periods of the crystal lattices. It is established that considers the aspects of the change periods for the three sections of ingots of single crystals: the beginning, the middle and end of the crystal, not greater than 0.05%. The results suggest that within the accuracy of the measurement of a sufficiently high uniformity of the grown single crystals listed intermetallics.

The study of quality of epitaxial GaAs films grown by molecular-beam epitaxy on substrates made of single crystals of these intermetallic compounds, shows that the density of dislocations in epitaxial films are almost identical on substrates selected from different sections along the length of the single crystals and changes in the range of 102-104/cm2depending on the substrate material. It is important to specify that the grown films are uncompensated, significant interaction epitaxial films with the material of the substrate is not marked.

Literature

1. .Kadowia et al. "Study of initial buffer in GaAs-on-Si growth" Journal of Crystal Growth 115 (1991), 128-132.

2. RF patent №2209260, IPC SW 19/12 "Substrate for growing epitaxial layers of gallium arsenide."

The substrate for growing epitaxial layers of gallium arsenide, is made of single crystal intermetallic compounds, characterized in that the intermetallic compound selected from the group consisting of gallium tin SnAs, palladium antimonide PdSb, polyanionic manganese Mn2Sb, stannate Nickel Ni3Sn2, the Nickel aluminate Ni2Al3, germanate Nickel Ni2Ge and germanate cobalt Co3Ge.



 

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