# Patent

## Title
Catalytic cathode composition for air-depolarized cell and method of

## Abstract

Certain Tm-containing iron garnet compositions provide layers having desirably low values of temperature coefficient of bubble collapse field and permit the fabrication of 1.2 .mu.m diameter magnetic bubble devices. The compositions, based on Tm-substitution on dodecahedral sites of [(La,Bi),(Sm,Eu),R].sub.3 (Fe,Al,Ga).sub.5 O.sub.12, are grown by liquid phase epitaxy onto suitable substrates. Bubble devices that incorporate the layers find applications in high density information storage.

## Background
1. Field of the Invention

This invention relates to magnetic bubble devices, and, more particularly, to Tm-containing garnet compositions for use in those devices.

2. Description of the Prior Art

A magnetic bubble memory consists of a thin film of magnetic garnet or other magnetic material in which microscopic cylindrical magnetic domains may be generated and moved. The axes of the domains are normal to the film surface; thus, when viewed end on (using polarized light) the domains have the appearance of small disks or "bubbles." In operation, the film is maintained in a bias field directed normal to the film. The magnitude of the bias field is kept within the range over which the bubbles are stable. At the lower limit of that range, the "strip-out field", the bubbles grow until they distort into elongated strips. At the upper limit, the bubbles collapse. Controlled perturbations of the magnitude and direction of the magnetic field near the bubbles are used to move the bubbles. To provide the greatest operating latitude, the bias field is set in the middle of the stable range, providing a characterisic bubble diameter. TThe smaller the bubble diameter, the greater the amount of information that can be stored in a particular area.

The diameter, d, of a magnetic bubble domain can be related to the characteristic length parameter, l

where A is the magnetic exchange constant, K.sub.u is the uniaxial magnetic anisotropy, and M.sub.s is the saturation magnetization. Nominal bubble diameter is d=8 l. Magnetization, as seen, plays an important role in determining the bubble size. Iron garnets such as (Y,Sm).sub.3 Fe.sub.5 O.sub.12 have a magnetization too high to support stable bubbles near 1.5 .mu.m diameter. Ge, Al, Ga, or another element is often substituted for Fe on the tetrahedral crystal site in these iron garnets to reduce the net magnetic moment of the iron sublattices and thereby the magnetization of the garnet bubble material.

One deleterious side-effect of such a substitution is that the Curie temperature, the temperature at which the magnetization drops precipitously to nearly zero, is decreased. For example, it has been noted (U.S. Pat. No. 3,886,533) that Ga-substitution for Fe results in a substantial lowering of the Curie temperature. The region of large change in magnetization with temperature, which is near the Curie temperature, is thus reduced to near the operating temperature range of a magnetic bubble memory device. A large temperature variation of the magnetization prevents the usual method of temperature stabilization of bubble memory devices; that is, adjustment of the temperature variation of the magnetic properties of the bubble material, principally the bubble collapse field, to about that of the temperature variation of the magnetization of the biasing magnet (U.S. Pat. No. 3,711,841).

Ga-substituted iron garnet compositions of the (La,Lu,Sm).sub.3 (Fe,Ga).sub.5 O.sub.12 system were studied for use as "small bubble materials" by S. L. Blank et al., J. Appl. Phys. 50, 2155 (1979). Within that system, they identified a composition that is suitable as a 1.3 .mu.m bubble material. However, that composition has limited usefulness, because the temperature coefficient of the bubble collapse field (.alpha..sub.bc) is too large.

In a series of patents issued to Blank (U.S. Pat. Nos. 4,002,803; 4,034,358; and 4,165,410), iron garnet systems using (Ca,Sr)- and (Ge,Si)-substitution for iron were disclosed, including various compositions that are suitable for layers capable of supporting stable magnetic bubbles. Among the compositions are ones that contain rare earth elements such as thulium (Tm) in octahedral sites in a relative molar concentration of from 0.01 to 0.1 per formula unit. Over a temperature range, the bubble collapse field for these compositions is claimed to vary with temperature at approximately the same average rate as the bias field variation with temperature over that range.

In accordance with the present invention, an iron garnet layer that is capable of supporting magnetic bubble domains is provided. The layer composition is nominally represented by the formula

(La,Bi).sub.a (Sm,Eu).sub.b Tm.sub.c R.sub.3-a-b-c (Fe,Al,Ga).sub.5 O.sub.12 where R is at least one element of the group consisting of yttrium and the elements having atomic number from 57 to 71, a is from about 0.10 to about 0.18, b is from about 0.50 to about 0.70, and c is from about 0.82 to about 2.22.

The notation (X,Y).sub.a as used in the specification and appended claims is understood to mean that elements X and Y are present in a combined quantity a in the formula unit, but the possibility that either X or Y is absent is not ruled out; e.g., X.sub.a is included.

In a preferred embodiment of the present invention, a magnetic bubble domain device comprises an iron garnet layer as described above; a magnet for maintaining in the layer a magnetic field that varies with temperature throughout a temperature range at an average variation rate; means adjacent to the layer for generating and moving the domain in the layer; and a substrate for supporting the device, whereby a bubble collapse field of the layer varies with temperature throughout the temperature range at about the average variation rate.

The garnet layers (or films) of the present invention may be grown by liquid phase epitaxy onto suitable substrates to provide a 1.2 .mu.m bubble diameter film having the low .vertline..alpha..sub.bc .vertline. that is needed for operation over a broad range of temperatures.

The present invention provides film compositions suitable for use in computer memory devices of 4 Mbit/cm.sup.2 storage density. The compositions are based on an (Al,Ga)-substituted iron garnet, where (La,Bi), (Sm,Eu),Tm, and, optionally, one or more other rare earth elements or Y are incorporated into the garnet lattice at dodecahedral sites. The compositions provide a lower .vertline..alpha..sub.bc .vertline. than did the compositions of the prior art, thus permitting the bubble memory devices that use the compositions to operate over a larger temperature range.

The prototypical iron garnet material is YIG, whose composition is routinely specified as Y.sub.3 Fe.sub.5 O.sub.12. That formula is based on the number of dodecahedral, octahedral, and tetrahedral sites in the lattice and assumes, for example, that Y occupies all the dodecahedral sites and no others. In fact, it is well known (see, e.g., D. M. Gualtieri et al., J. Appl. Phys. 52, 2335 (1981)) that Y substitutes to varying degrees for Fe on octahedral sites. Thus, the subscripts in the chemical formula for YIG, as well as for the other iron garnets described in this specification and in the claims, are nominal.

The identification of suitable magnetic bubble compositions based on YIG involves substituting for Y and Fe the appropriate cations, in the appropriate amounts, and at the appropriate lattice sites. In order to provide growth-induced uniaxial anisotropy (which permits fabrication of planar devices, without substrate bowing or other distortions that accompany strain-induced anisotropy), Sm or Eu or both substitute for Y. Additional growth-induced anisotropy results if a small ion, such as Lu, is also added. To compensate for the reduction in lattice constant that would otherwise result, (La,Bi) substitution may be made at a level necessary to achieve a match to the substrate lattice constant. In the limit, Y may be entirely replaced with Sm, La, and Lu. However, the magnetization of that composition is too high to support stable bubbles in the range of diameters d.apprxeq.1.5 .mu.m. Thus, Al and/or Ga may be substituted for Fe in order to reduce the magnetization, and a resulting compositions, (La,Sm,Lu).sub.3 (Fe,Ga).sub.5 O.sub.12, has been studied by S. L. Blank et al., op. cit. That composition and others of the general formula (La,Bi).sub.a (Sm,Eu).sub.b R.sub.3-a-b (Fe,Al,Ga).sub.5 O.sub.12 have a comparatively low Curie temperature, which in turn results in an undesirably large .vertline..alpha..sub.bc .vertline. in the normal operating temperature range (T.about.0.degree.-100.degree. C.). In order to overcome this effect, the present invention involves substitution of Tm at dodecahedral lattice sites.

The effect of Tm may be understood by first considering YIG. If the YIG lattice is thought of as a combination of individual sublattices, then the dodecahedral (or "c") sublattice, which is occupied by Y cations, has a larger temperature coefficient of magnetization than do the "a" and "d" sublattices, occupied by Fe. The net magnetization of the crystal, M, is given by M=M.sub.d -M.sub.a -M.sub.c, where, generally, M.sub.a .apprxeq.2M.sub.d /3. M, as well as its temperature variation, depend critically on the nature of the cations on the c-sublattice. The c-sublattice magnetization is large for some cations. Tm, for example, has such a large magnetic moment that Tm.sub.3 Fe.sub.5 O.sub.12 has a compensaion point in its variation of magnetization with temperature; that is, a temperature at which the c-sublattice magnetization just balances the net magnetization of the Fe-sublattices. Likewise, small substitutions of Tm for Y in Y.sub.3 Fe.sub.5 O.sub.12 cause a decrease in M.

Incorporation of Tm into a magnetic bubble composition, taking care to assure correct lattice parameter match between the magnetic film and a non-magnetic substrate, would allow less Ga-substitution for Fe for the same bubble diameter. The temperature dependence of the magnetization in the operating region of the bubble device is decreased, and this allows stable operation of the bubble device over a larger temperature range.

Thus, the present invention concerns the dodecahedral (c-sublattice) incorporation of Tm ions as a means of reducing the net magnetization of the material to allow reduced cationic substitution for Fe for a given magnetization. In order to permit Tm-substitution while maintaining the same lattice constant, the rare earth elements being replaced by Tm in (La,Bi).sub.a (Sm,Eu).sub.b R.sub.3-a-b (Fe,Ga,Al).sub.5 O.sub.12 preferably include at least one whose cationic size is less than that of Tm. Thus, in Tm.sub.c (La,Sm,Lu).sub.3-c (Fe,Ga).sub.5 O.sub.12, a preferred composition, Lu is smaller than Tm, and while Tm-substitution for Lu desirably reduces net magnetization and .vertline..alpha..sub.bc .vertline., it also causes lattice mismatch with a substrate.

Since the sole purpose of La in the composition is to increase the lattice constant of the magnetic film to match it to the substrate, the amount of La can be adjusted to allow for the replacement of Lu with Tm. Likewise, Ga can be replaced by Fe (i.e., less Ga substituted for Fe) and La removed to maintain the lattice parameter match between film and substrate. The actual amount of Tm incorporated depends on the value of the temperature dependence of the magnetization required to suit device properties.

Characteristics of an ideal iron garnet bubble memory composition for use with bubble diameters of about 1.2 .mu.m can be identified. As was discussed above, a low value of .vertline..alpha..sub.bc .vertline. in the temperature range between about 0.degree. and 100.degree. C. requires a relatively high Curie temperature, which translates into a minimum value for the exchange constant, A. The bias field, H.sub.o, should be as low as possible, consistent with an anisotropy field, H.sub.k, that is high enough to provide stable bubbles. A quality factor, Q, for bubble stability is defined by Q=H.sub.k /4.pi.M.sub.s.

Barium ferrite is a preferred material for providing the bias field, and its temperature coefficient of magnetization should be matched by bc of the film. Gadolinium gallium garnet (GGG) is a preferred substrate material. To avoid undesirable blowing that otherwise results, film lattice constant, corrected for strain induced when the film is deposited on the substrate, should closely match substrate lattice constant. Optimum values of parameters for a 1.2 .mu.m bubble film appear in Table 1. ______________________________________ Exchange constant (erg/cm) A > 2.45 .times. 10.sup.-7 Thickness (.mu.m)    0.90 .ltoreq. h .ltoreq. 1.30 Stripe width (.mu.m) 1.00 .ltoreq. w .ltoreq. 1.40 Collapse field (Oe)  300 .ltoreq. H.sub.o .ltoreq. 350 Anisotropy field (Oe) 1800 .ltoreq. H.sub.k .ltoreq. 2200 Quality factor       Q .gtoreq. 2.8 Temperature coefficient of 0.21 .ltoreq. .vertline..alpha..sub.bc .vertline. .ltoreq. 0.23 the bubble collapse field (%/.degree.C. at 50.degree. C.) Film/substrate lattice .vertline..DELTA.a.vertline. < 0.3 pm constant mismatch (corrected for strain) ______________________________________

Film thickness should be about 0.8 times the stripe width of the finished film, dictated by considerations of maximum bubble stability consistent with sufficient fringing field for easy bubble detection. Since it is sometimes desirable to implant certain ions subsequent to film growth, "as grown" thickness, in those cases, may be more nearly equal to or even greater than stripe width. Bias field is chosen to provide bubble diameter approximately equal to stripe width.

The quantities in Table 1 are not independent. Consequently, there are only certain regions of the (h,w) space that are accessible to the specifications at a given Q value. A guide to determining the accessible regions is provided in D. M. Gualtieri, IEEE Trans. on Mag., Vol. MAG-16(6), 1440 (1980).

The garnet films of the present invention are grown by the liquid phase epitaxy method, which has been described by S. L. Blank et al., J. Cryst. Growth 17, 302 (1972). A substrate, preferably GGG, is held at the end of a rod and, while rotating about a vertical axis in the plane of the substrate, the substrate is dipped into a supersaturated solution of the proper composition and temperature.

The following examples are presented in order to provide a more complete understanding of the invention. The specific techniques, conditions, materials, and reported data set forth to illustrate the principles and practice of the invention are exemplary and should not be construed as limiting the scope of the invention.

Bubble films were grown by liquid phase epitaxy onto GGG substrates by the process described by S. L. Blank et al., op. cit. The unidirectional substrate rotation rate in each case was 200 rev/min, with a supercooling of about 9.5.degree. C. The melt composition is set out below. The "R" parameters are those described by S. L. Blank et al., IEEE Trans. on Mag., Vol. MAG-13(5), 1095 (1977), and (RE).sub.2 O.sub.3 symbolizes the total amount of rare earth oxides. An advantage of this melt composition is that flux-spotting is minimized.

Table 2 lists the growth parameters and resulting film properties. The calculated properties were derived by using the approach discussed in D. M. Gualtieri, op. cit. The .vertline..alpha..sub.bc .vertline. values are the slope at 50.degree. C. of the second-order polynominal fit of collapse field data taken at 5.degree. intervals from 25.degree.-100.degree. C. X-ray fluorescence spectroscopy of the films yielded a nominal composition of O.sub.12.18

The process of Examples 1-4 was used with the melt composition below. The unidirectional substrate rotation rate in each case was 200 rev/min., with a supercooling of about 6.5.degree. C.

Table 3 lists the growth parameters and resulting film properties. Calculated properties were determined as described for Examples 1-4 above. ______________________________________ Example     1        2        3      4 ______________________________________ Growth temp. (.degree.C.) 967.0    967.5    966.3  965.6 Growth rate 0.85     0.65     0.84   0.90 (.mu.m/min) Thickness (.mu.m) 1.36     0.93     1.22   1.12 Stripe width (.mu.m) 1.26     1.11     1.20   1.17 Curie temp. (K.) 470.2    468.7    470.8  470.7 Collapse field (Oe) 369.4    315.2    358.9  349.0 Exchange const. 2.72     2.69     2.73   2.72 (10.sup.-7 erg/cm) Magnetization 675      681      681    688 (4.pi.M.sub.s, G) Characteristic 0.132    0.134    0.131  0.132 length (.mu.m) Anisotropy const. 5.30     5.68     5.33   5.70 (10.sup.4 erg/cm.sup.3) Quality     2.92     3.08     2.89   3.03 Anisotropy field 1970     2100     1970   2080 (Oe) Lattice const. (nm) --       --       --     1.23861 (corrected for strain) Lattice const. --       --       --     +0.28 mismatch (film-substrate, pm) Temp. coef. of -0.227   --       --     -0.214 collapse field (%/.degree.C. at 50.degree. C.) ______________________________________ ______________________________________ Example     5         6        7      8 ______________________________________ Growth temp. (.degree.C.) 960.8     960.0    960.2  960.1 Growth rate 0.64      0.90     0.95   0.82 (.mu.m/min) Thickness (.mu.m) 1.76      1.48     1.09   2.03 Stripe width (.mu.m) 1.46      1.33     1.18   1.53 Curie temp. (K.) 467.4     468.7    469.6  469.1 Collapse field (Oe) 378.0     362.3    326.0  397.0 Exchange const. 2.67      2.69     2.71   2.70 (10.sup.-7 erg/cm) Magnetization 649       650      650    646 (4.pi.M.sub.s, G) Characteristic 0.142     0.137    0.136  0.138 length (.mu.m) Anisotropy const. 5.31      4.92     5.07   4.89 (10.sup.4 erg/cm.sup.3) Quality     3.17      2.92     2.94   2.94 Anisotropy field 2060      1900     1940   1900 (Oe) Lattice const. (nm) 1.23815   --       --     -- (corrected for strain) Lattice const. -0.29     --       --     -- mismatch (film-substrate, pm) Temp. coef. of --        -0.241   -0.222 -0.252 collapse field (%/.degree.C. at 50.degree. C.) ______________________________________

## Claims

1. A magnetic bubble domain device comprising an iron garnet layer that is capable of supporting magnetic bubble domains and that has a composition nominally represented by the formula: O.sub.12 where R is at least one element of the group consisting of Y and the elements having atomic number from 57 to 71, a is from about 0.10 to about 0.18, b is from about 0.50 to about 0.70 and c is from about 0.8 to about 2.22; temperature throughout a temperature range at an average variation rate; layer; and bubble collapse field of the layer varies with temperature throughout the temperature range at about the average variation rate.

2. The device of claim 1 in which R includes at least one element whose cationic size is smaller than that of Tm.

3. The device of claim 1 in which the composition is nominally represented by the formula

4. The device of claim 3 in which the composition is nominally represented by the formula O.sub.12.28.

5. The device of claim 1 in which the magnet is barium ferrite.