GaAs single crystal substrate and epitaxial wafer using the same

Abstract: A GaAs single crystal substrate and an epitaxial wafer using the same which suppress generation of slips when the epitaxial layer is grown and enable improvement of withstanding characteristic of devices can be obtained. A GaAs single crystal substrate has mean dislocation density in plane of at most 2 × 10 4 cm -2 , carbon concentration of 2.5 to 20.0 × 10 15 cm -3 , boron concentration of 2.0 to 20.0 × 10 16 cm -3 , impurity concentration other than carbon and boron of at most 1 × 10 17 cm -3 , EL2 concentration of 5.0 to 10.0 × 10 15 cm -3 , resistivity of 1.0 to 5.0 × 10 8 Ω· cm and mean residual strain measured by photoelastic analysis of at most 1.0 × 10 -5 .

Description: BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a GaAs single crystal substrate and an epitaxial wafer using the same. More specifically, the present invention relates to a GaAs (gallium arsenide) single crystal substrate used for an integrated circuit and a microwave element, and to an epitaxial wafer using the same. Description of the Background Art Semi-insulating GaAs crystal has been conventionally fabricated through a manufacturing method such as Liquid Encapsulated Czochralski method (LEC method) and Vertical Bridgeman method (VB method). It has been possible to control dislocation density of the GaAs single crystal substrate within the range of 1000 to 100000 cm -2 , by adjusting temperature gradient and cooling rate at the time of growth. Carbon concentration and EL2 concentration of the GaAs single crystal substrate have been controlled by adjusting impurity concentration of a solution, ratio of Ga with respect to As and thermal hysterisis after solidification. Generally, two concentrations, that is, the carbon concentration and the EL2 concentration are considered as factors controlling resistivity. With the carbon concentration being in the range of 0.9 to 10.0 × 10 15 cm -3 and EL2 concentration being 12.0 to 16.0 × 10 15 cm -3 , a substrate having the resistivity of about 0.1 to about 2.0 × 10 8 Ω ·cm has been manufactured. Reference 1 (T. Kawase et al. Proc. Of the 9th Conf. on Semiconducting and Insulating Materials, Toulouse, France (1996) 275-278) discloses an example of a GaAs single crystal substrate having low dislocation density fabricated through the VB method. The GaAs single crystal substrate has carbon density of 7 to 8 × 10 15 cm -3 , EL2 concentration after heat treatment of 1.3 × 10 16 cm -3 , resistivity of 3.5 to 6.5 × 10 7 Ω·cm, mean dislocation density in plane of 1000 to 2000 cm -2 , and mean residual strain measured by photoelastic analysis of 0.2 to 0.3 × 10 -5 . The conventional GaAs single crystal substrate has been expected as a substrate material of electronic devices requiring high speed operation and low power consumption. Among substrates used for electronic devices, a substrate having an epitaxial thin film layer grown thereon to provide a device operation layer is referred to as an "epitaxial wafer." In manufacturing the epitaxial wafer, when the epitaxial thin film layer is grown, it is necessary to heat the substrate to a temperature called growth temperature, and to bring the surface of the substrate to be in contact with Ga, As and a small amount of impurity called dopant, in liquid or gas phase. The epitaxial wafer having a plurality of epitaxial layers stacked on the substrate is subjected to surface etching, deposition of metal for electrodes, and processed into chips, whereby electronic devices are formed. Fundamental characteristic of thus formed electronic device is amplification of a voltage input signal. Particularly, an electronic device used for satellite communication or the like is required of high output and operability at high voltage. Therefore, there has been greater need for the GaAs single crystal substrate having superior withstanding characteristic. The conventional single crystal substrate, however, generally has low carbon concentration and therefore it cannot withstand thermal stress-strain when the temperature is increased to form the actual epitaxial layer, so that steps, which are referred to as slips, result on the substrate surface. When devices are fabricated on the steps, desired device characteristics cannot be attained, and hence production yield is significantly degraded. Further, the substrate has low resistivity and a number of deep levels such as EL2 within an energy band, and therefore only the devices having low withstanding characteristic can be provided. SUMMARY OF THE INVENTION An object of the present invention is to solve the above-described problems and to provide a GaAs single crystal substrate and an epitaxial wafer using the same, which suppress generation of slips at the time of growth of the epitaxial layer and which enable improvement in withstanding characteristic of the devices. Through various experiments made to attain the above described objects, the inventors have found that in order to prevent generation of slips and to improve withstanding characteristic of the devices, it is important to control boron concentration, which finding has lead to the present invention. As will be described in the following, the present invention is characterized in that in the GaAs single crystal substrate, an appropriate boron concentration is defined. According to an aspect of the present invention, a GaAs single crystal substrate is provided, which has mean dislocation density in plane of at most 2 × 10 cm -2 , carbon concentration of 2.5 to 20.0 × 10 15 cm -3 , boron concentration of 2.0 to 20.0 × 10 16 cm -3 , impurity concentration other than carbon and boron of at most 1 × 10 17 cm -3 , EL2 concentration of 5.0 to 10.0 × 10 15 cm -3 , resistivity of 1.0 to 5.0 × 10 3 Ω · cm, and mean residual strain measured by photoelastic analysis of at most 1.0 × 10 -5 . Carbon concentration, boron concentration and impurity concentration other than carbon and boron can be adjusted to 2.5 to 20.0 × 10 15 cm -3 , 2.0 to 20.0 × 10 16 cm -3 and at most 1 × 10 17 cm -3 , respectively, by adjusting carbon concentration and boron concentration in the row material melt when the crystal is grown. The mean dislocation density in plane, EL2 concentration and resistivity can be adjusted to at most 2 × 10 4 cm -2 , 5.0 to 10.0 × 10 15 cm -3 and 1.0 to 5.0 × 10 8 Ω ·cm, respectively, by adjusting ratio of Ga with respect to As and thermal hysterisis after crystal solidification. Further, the mean residual strain (|Sr - St|) measured by photoelastic analysis can also be suppressed to at most 1.0 × 10 c m -5 , by controlling thermal hysterisis after solidification. When the GaAs single crystal substrate in accordance with the present invention is used as a substrate for an epitaxial wafer, generation of slips when the temperature is increased can be suppressed, because of the influence of carbon and boron impurity concentrations and because of the characteristics of lower residual strain and dislocation density attained by thermal hysterisis control. As a result, production yield of the devices can be improved significantly. Further, as the EL2 concentration is kept low while boron concentration is increased, high resistance is realized. As a result, withstanding characteristic can be improved when the devices are fabricated. Preferably, the GaAs single crystal substrate in accordance with the present invention may further be characterized in that a deep level (activation energy of 0.31 ± 0.05eV) detected by thermally stimulated current method is at least 1 × 10 15 cm -3 . The deep level (activation energy of 0.31 ± 0.05eV) detected by the thermally stimulated current method can be adjusted to a value of at least 1 × 10 15 cm -3 , by adjusting the ratio of Ga and As and by controlling thermal hysterisis after crystal solidification. In this manner, by controlling concentrations of impurities in the raw material melt and controlling thermal hysterisis after solidification, the GaAs single crystal substrate which meets the characteristics of the present invention can be fabricated. Further, when the GaAs single crystal substrate in accordance with the present invention is used as a substrate for an epitaxial wafer, higher resistance can be attained, as the deep level (activation energy of 0.31 ± 05eV) detected by the thermally stimulated current method is high. As a result, withstanding characteristic at the time of fabricating devices can further be improved. According to another aspect of the present invention, an epitaxial wafer is provided, which has a thin film of at least 0.1 µm in thickness epitaxially grown on the GaAs single crystal substrate in accordance with the present invention described above. The foregoing and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph representing thermally stimulated current spectrum after heat treatment. Fig. 2 is a cross sectional view showing a structure of the FET fabricated as an example of the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS Example Samples of GaAs single crystal having the diameter of 100 mm and the length of straight body of 100 mm were grown through the VB method. Other than raw material GaAs, carbon and boron were added with the amounts to be added changed variously in the order of ppm, melt together with the raw material GaAs, and crystal was grown in thermal environment having temperature gradient of 2 to 10°C/cm. After the crystal was grown, the samples were cooled at a rate of 10 to 100°C/hour. Thereafter, the crystal samples were subjected to heat treatment at the temperature range of 100 to 1000°C in a heat treatment furnace. Characteristics of the crystal samples obtained in this manner are as shown in Tables 1 to 3. Carbon concentration and EL2 concentration were calculated based on absorption of light at a prescribed wavelength. Impurity concentration other than carbon was evaluated by glow discharge mass spectrometry (GDMS), the resistivity was evaluated by Hall and resistivity measurement (the van der Pauw method), the residual strain was evaluated by photoelastic analysis using infrared light, and the deep level was evaluated by the thermally stimulated current method. In the thermally stimulated current method, samples cooled to 80K in the dark were irradiated with single color light having the wavelength of 830 nm until photocurrent attained to a stable state, and thereafter, the samples were again heated in the dark and electric signals were captured. Carrier concentration and temperature dependency of life time were normalized based on temperature dependency of photoconductive gain coefficient, and level concentration of activation energy of 0.31eV was found. Fig. 1 is a graph representing thermally stimulated current spectrum after heat treatment, in which the abscissa represents temperature (K) and the ordinate represents thermally stimulated current (A). Referring to Fig. 1, in this example, the concentration of the level of 0.31eV is 3.8 × 10 14 cm -3 . As to the number of slips, samples were heated to 600°C at the rate of 100°C/hour using an MBE furnace, whereby GaAs layer having the thickness of 1 µm was epitaxially grown. After growth, the samples were cooled at the same rate, steps on the surfaces of the taken out substrates were measured, and number of slips per one substrate was counted. As to the breakdown voltage (Vbd), FETs each having the structure shown in Fig. 2 were fabricated by device processing after crystal growth by MBE method, and the voltage at which current started to flow in the reverse bias state between the gate and the drain was measured. Referring to Tables 1 to 3, samples 1 to 12 are GaAs single crystal substrates satisfying the characteristics of the present invention according to claim 1, and particularly, samples 1 to 9 are GaAs single crystal substrates which also satisfy the requirements of the present invention according to claim 2. As compared with samples 10 to 12, these samples have higher value of Vbd in general, and it can be seen that withstanding characteristic at the time of fabricating devices is further improved. Samples 13 to 21 are GaAs single crystal substrates of comparative examples. More specifically, sample 13 has carbon concentration, boron concentration and resistivity value out of the ranges defined by the present invention. Samples 14 has EL2 concentration and the 0.31eV level concentration out of the ranges defined by the present invention. Sample 15 has boron concentration out of the range defined by the present invention. Sample 16 has dislocation density, carbon concentration, boron concentration, EL2 concentration, resistivity, mean residual strain and 0.31eV level concentration out of the ranges defined by the present invention. Sample 17 has boron concentration and resistivity out of the ranges defined by the present invention. Samples 18 to 21 have the boron concentration out of the range defined by the present invention. It can be seen that the GaAs single crystal substrates of the comparative examples generally have larger number of slips and smaller Vbd values.

Claims: A GaAs single crystal substrate, having mean dislocation density in plane of at most 2 × 10 4 cm -2 , carbon concentration of 2.5 to 20.0 × 10 15 cm -3 , boron concentration of 2.0 to 20.0 × 10 16 cm -3 , impurity concentration other than carbon and boron of at most 1 × 10 17 cm -3 , EL2 concentration of 5.0 to 10.0 × 10 15 cm -3 , resistivity of 1.0 to 5.0 × 10 8 Ω·cm, and mean residual strain measured by photoelastic analysis of at most 1.0×10 -5 . The GaAs single crystal substrate according to claim 1, characterized in that deep level (activation energy of 0.31±0.05eV) detected by thermally stimulated current method is at least 1 × 10 15 cm -3 . An epitaxial wafer having a thin film of at least 0.1 µm in thickness epiataxially grown on the GaAs single crystal substrate according to claim 1. An epitaxial wafer having a thin film of at least 0.1 µm in thickness epitaxially grown on the GaAs single crystal substrate according to claim 2.

Inventors: HAGI YOSHIAKI, NAKAI RYUSUKE, HAGI, YOSHIAKI, NAKAI, RYUSUKE, Hagi, Yoshiaki, c/o Itami Works of Sumitomo E.Ind., Nakai, Ryusuke, c/o Itami Works of Sumitomo E.Ind.
Applicants: SUMITOMO ELECTRIC INDUSTRIES, SUMITOMO ELECTRIC INDUSTRIES, LTD.
Application year: 1999
Main classification: C30B11
IPC codes: C30B11, C30B29, H01L21