This invention relates to ferromagnetic materials.

Ferromagnetic materials display a marked increase in magnetisation in an independently established magnetic field. Ferromagnetic materials may be used in a wide variety of uses including motors or galvanometers. The temperature at which ferromagnetism changes to paramagnetism is defined as the Curie

Temperature, T _c *

Ferromagnetic materials based on rare earth elements may have Curie Temperatures up to 700-800 C, but they oxidise [Goldsch iαt Report Reviews Information A/75 no.35 ana 2/79 no. 8]. The inclusion of iron within an alloy is a well established possible method of producing a f errromagnetic material. Nd ₉ Fe.,B has one of the highest reported Curie Temperatures (315 C) of rare earth-iron based alloys. Iron may in turn be used to dope GaAs in order to produce a material with ferromagnetic properties. One of the most recent reports of such material is that of I.E.. Harris et al. in the Journal of Crystal Growth ____ pp450- 458 1987. This publication reported the growth of Fe-GaAs as a ferromagnetic material (Curie Temperature=about 100 C) and discussed this alloy with reference to previous work carried out on iron doped GaAs.

The present invention provides an improved stable ferromagnetic GaAs based material with an increased Curie Temperature.

According to this invention a ferromagnetic material comprises _t he alloy M ₃ Ga ₂ _ _χ As _χ where 0.15.___0.99, and where k may represent Fe or a component of the alloy where iron is partially substituted by either manganese or cobalt.

Where M represents Fe„ and x is a value within the continuous range 0.15-x^0.99, then x would have the preferred range of 0.15 x.0.85. The most preferential range for x in this alloy may be expressed as 0.15<x 0.75.

where M„ represents Fe_ and the range of x is 0.21.x.0.99, as cast material consists of single phase Fe_GaAs with a eutectic mixture at the grain boundaries. In the range 0.15.x _* 0.21 for the same alloy the as cast material exhibits phases in addition to a eutectic mixture at grain boundaries.

In as cast material where „ represents Fe_ and the range of x is 0.854x.0.99, the predominant phase is hexagonal B8 -type

Fe_Ga_ As with a minimal amount of the phase GaAs. Within the 3 2-x x

B8 -type (Ni„In-type) the In-type sub-lattice is filled by a combination of Ga and As atoms and three quarters of the two nickel type sites are taken up by the iron atoms.

Lattice structural transition (ordering) occurs within the composition range of 0.75-1x^0.85. The structure is still hexagonal, but there is a change of the a and c spacings such that a =2a.. and c ₉ =c ₁ , where a and c ₁ are the a and c spacings of the B8 -type structure and a. and c. are the a and c spacings of the new structure. In the composition range 0.15<- ^' x.0.75 the ordering process is complete.

The ferromagnetic material Fe,Ga„ As may subsequently be variously heat treated in order to achieve higher Curie Temperatures. Suitable annealing temperatures would be between approximately b00°C and 900°C.

Where M represents partial substitution of iron with manganese, then this substitution is used to maintain high Curie Temperatures .

This invention will now be described by way of example only with reference to the accompanying diagrams of which:-

Figure _1_ is a schematic representation of Liquid Encapsulation Czochralski (LEC) growing equipment.

Figure 2_ is a graph of the saturation magnetisation of M, __ Ga„._~X As X against the atomic percentage of Gallium for as cast material where M represents Fe„.

Figure _3_ is a graph of the variation in Curie Temperature with increasing Gallium content for as cast material where M_ represents Fe .

Figure ^ is a graph of the a-spacing versus the atomic percentage of Gallium in the alloy for as cast material where M,, represents Fe .

The ferromagnetic material M„Ga__ As may be produced using

«j _< ^— X X typical methods such as casting or single crystal growth. Both methods require encapsulation of mel t cons tituents to prevent loss of arsenic from the melt whilst in a furnace environment. Boric oxide is an example of a commonly used encapsulation material.

The Liquid Encapsulation Czochralski technique for growth of single crystal material may be used for the growth of the alloy

^ J _d Ga„ 2-x AS x ,' and has been described in U.K. Patent Number

1 113 069. As shown in Figure 1 , the melt constituents 1 (Fe,Ga and GaAs) of applicable ratios are placed in a silica crucible 2 and covered with boric oxide 3. The crucible 2 and contents 1 are then heated by electric heaters 4 fed through a power supply 5. An orientated seed 6 is lowered into the pressurised chamber 7 by a motor 8. When the seed 6 has been partially immersed in the molten alloy 1, controlled growth takes place by rotating and retracting the seed 6 away from the mel t 1 , through the encapsulant 3 and into . the pressurised chamber environment 7. This results in a single crystal, or near single crystal, boule 9. All growth procedures are controlled by a control panel 10.

Specific compositions will now be given by way of example only where all examples are as cast material except Example 6:-

Example _1_

I_3≤*ι. ₈₅ ^0.15

This composition has a saturation magnetisation of 84 emu g at

298K (Figure 2) and a Curie Temperature of 431°C (Figure 3).

Example 2_

This composition has a saturation magnetisation of 97 emu g at 298K (Figure 2) , a Curie Temperature of 370°C (Figure 3) and an a-spacing of 4.07A (Figure 4).

Example _3_

This composition has a saturation magnetisation of 88 emu g at 298K (Figure 2) , a Curie Temperature of 240°C (Figure 3) and an a-spacing of 4.055A (Figure 4).

Example 4_

Fe ₃ Ga _1<35 As _Q .75

This composition has a saturation magnetisation of 72 emu g at 298K (Figure 2), a Curie Temperature of 232°C (Figure 3) and an a-spacing of 4.048A (Figure 4).

Example 5_

This composition has a saturation magnetisation of 79 emu g at 298K (Figure 2), a Curie Temperature of 215° (Figure 3) and an a- spacing of 4.033A.

Example 6_

Fe.Ga. As_ , —"1♦4- ^: - ^Q .6

Alloys may be variously heat treated to homogenise the microstructure. The heat treatment may occur within a vacuum or without a vacuum. The heat treatment may require an air, inert gas or arsenic ambient at air or other pressures, or a flowing medium of any of these. The annealing temperatures employed is dependent upon the annealing environment used and the material properties required.

This composition in the as cast state has a Curie Temperature of

244 C. After annealing the example at about 600 C in a vacuum of

10 Torr for three days the Curie Temperature increases to 282°C.

Example 7_

This composition has a saturation magnetisation of 94 emu g at

298K and a Curie Temperature of 416°C.

Example 8_

— ^^. 0.3^1.85^0.15

This composition has a saturation magnetisation of 71 emu g at

298K and a Curie Temperature of 346°C.