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Substrate selection for high-temperature superconducting thin films

Julia M. Phillips

Citation: Journal of Applied Physics 79, 1829 (1996); doi: 10.1063/1.362675


View online: https://doi.org/10.1063/1.362675
View Table of Contents: http://aip.scitation.org/toc/jap/79/4
Published by the American Institute of Physics

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APPLIED PHYSICS REVIEWS

Substrate selection for high-temperature superconducting thin films


Julia M. Phillipsa)
AT&T Bell Laboratories, Murray Hill, New Jersey 07974
~Received 1 August 1995; accepted for publication 30 October 1995!
Substrate selection presents particular challenges for the production of high-quality
high-temperature superconducting ~HTS! thin films suitable for applications. Because the substrate
is generally a passive component, it is often ignored and assumed to have a negligible effect on the
structure residing on top of it. There is also a technological motivation to use substrates that
conventional wisdom would argue are unlikely to support high-quality HTS films. These facts have
led to rediscovery of many of the fundamental issues governing the role of the substrate in
determining the properties of the thin film~s! it supports. For this reason, the study of issues in
substrate selection for HTS materials presents a microcosm for substrate selection more generally.
We consider the major issues governing the role of the substrate in HTS thin-film technology and
discuss many of the material classes and specific materials that have been studied for their suitability
as substrates for HTS films. © 1996 American Institute of Physics. @S0021-8979~96!06004-8#

TABLE OF CONTENTS HTS compounds present a particularly challenging set of


properties that make the realization of high-quality, repro-
I. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1829 ducible thin films potentially problematic. They are a chal-
II. Issues in substrate selection. . . . . . . . . . . . . . . . . . . 1830 lenge to grow under even the most ideal circumstances. A
A. Overview. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1830 major contributor to the difficulties that arise is the sheer
B. Global issues. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1830 complexity of the materials. All of the HTS compounds are
C. Issues for epitaxial films. . . . . . . . . . . . . . . . . . . 1832 composed of a minimum of four elements that must be de-
D. Issues for applications. . . . . . . . . . . . . . . . . . . . . 1834 posited within close tolerance of the correct ratio in order to
III. Substate materials. . . . . . . . . . . . . . . . . . . . . . . . . . . 1836 obtain optimized films. Most of the elements are highly re-
A. Overview. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1836 active, leading to the potential for unwanted chemical reac-
B. Perovskite-structure oxides. . . . . . . . . . . . . . . . . 1836 tions that lead to deviations from chemical purity in the
C. Non-perovskite-structure oxides. . . . . . . . . . . . . 1840 films. Each HTS material contains oxygen, an element that is
D. Semiconductors. . . . . . . . . . . . . . . . . . . . . . . . . . . 1844 incompatible with many aspects of traditional thin-film
E. Metals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1844 growth methods, especially the substrate heating necessary
F. Other materials. . . . . . . . . . . . . . . . . . . . . . . . . . . 1845 for producing films that are superconducting upon removal
IV. Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1846 from the growth chamber as well as hot filaments for evapo-
rators. The role of oxygen is also critical in determining the
properties of various film imperfections such as grain bound-
I. INTRODUCTION aries. The crystal structure of the materials is highly aniso-
tropic, as are the resultant electrical and superconducting
Soon after the discovery of high-temperature supercon- properties, meaning that crystallographic alignment in the
ductivity ~HTS! above liquid-nitrogen temperature,1–3 the films is critical.
first reports emerged of the growth of the new materials in All of these considerations make the structural quality of
thin-film form.4 Thin-film research has been motivated by a HTS film critical for obtaining the desired properties in a
two tantalizing possibilities. One is the potential of HTS thin reproducible manner. This has meant that many of the prob-
films to give insight into the fundamental mechanisms gov- lems that have plagued thin film growers in other materials
erning HTS.5 The other involves the various applications that systems have also been encountered in HTS, exacerbated by
high-quality thin films might enable, including low-loss mi- the special materials properties of the HTS materials that
crowave cavities and filters, bolometers, various supercon- present their own challenges.
ducting two- and three-terminal devices, flux transformers, One of the issues that presents particular challenges in
and dc and rf superconducting quantum interference devices the case of HTS materials is the substrate. Because the sub-
~SQUIDs!.6 There is also need for HTS interconnects to wire strate is generally a passive component of the entire struc-
together the various active devices.7 ture, there is a strong tendency to ignore it and to assume that
its role in the properties of the desired structure grown on top
a!
Present address: Sandia National Laboratories, Albuquerque, NM 87185- of it is nonexistent or at worst minimal. There is also a tech-
1411; Electronic mail: jmphill@sandia.gov nological motivation to use substrates that conventional wis-

J. Appl. Phys. 79 (4), 15 February 1996 0021-8979/96/79(4)/1829/20/$10.00 © 1996 American Institute of Physics 1829
TABLE I. Global issues in substrate selection.

ISSUE

Chemical Thermal exp. Surface Substrate Substrate Substrate Buffer


EFFECT compatibility match quality cleanliness homogeneity therm. stability layers

Max. processing 3 3 3 3
temperature
Reacted layer 3 3 3
at interface
Impurity in film 3 3 3
Impurity in 3 3
substrate
Film adhesion 3 3 3 3
Film buckling/ 3 3
cracking
Film 3 3 3 3 3
microstructure
Film 3 3
composition
Film 3 3 3 3 3
morphology
Film 3 3 3 3 3
uniformity
Superconducting 3 3 3 3 3 3 3
properties

dom would argue are unlikely to support high-quality HTS area of research that often accompanies the investigation and
films. These facts have led to rediscovery of many of the perfection of a film. Significant breakthroughs are required to
fundamental issues governing the role of the substrate in identify and produce materials that satisfy all of the require-
determining the properties of the thin film~s! it supports. In ments that HTS films and many of their applications pose.
some sense, the study of issues in substrate selection for HTS The quest for substrate materials that are capable of support-
materials presents a microcosm for substrate selection more ing excellent films of HTS materials has been in progress for
generally, with most of the important issues having been re- nearly as long as HTS thin films have been prepared. The list
discovered and/or elucidated in various papers over the last of desirable substrate properties contains a number of entries
10 years. that are common to good substrates for essentially all classes
As will become obvious, the ideal substrate for HTS of thin films. Some substrate requirements are independent
films does not exist. Specific applications require different of the details of the film they must support. These global
substrate materials which offer an acceptable compromise requirements are discussed in Sec. II B. In many cases it is
for the purpose at hand. Ideally, the substrate should provide desirable or even necessary for a film to be not only crystal-
only mechanical support but not interact with the film except line, often single crystalline, but also for the crystallographic
for sufficient adhesion, and in many cases the provision of a axes of the film to have well-defined orientations with re-
template for atomic ordering. In practice, however, the sub- spect to the substrate. This usually requires that the film be
strate exerts considerable influence on film characteristics. epitaxial on its substrate, a constraint that introduces addi-
The search for viable substrate materials is an active area of tional requirements that must be fulfilled by the substrate
research. It is fair to say that significant breakthroughs are material. These requirements are discussed in Sec. II C. Fi-
required to identify materials that satisfy all of the require- nally, the use of films for particular applications introduces
ments that HTS films pose. This review considers the major its own constraints; these are discussed in Sec. II D.
issues governing the role of the substrate in HTS thin-film
technology and discusses many of the material classes and
B. Global issues
specific materials that have been studied for their suitability
as substrates for HTS films. A number of issues are critical in substrate selection for
thin-film growth, regardless of the details of the film to be
II. ISSUES IN SUBSTRATE SELECTION produced. These are listed in Table I, together with the ma-
terials properties they affect. Each entry is discussed in more
A. Overview
detail in the rest of this section.
The importance of substrate selection in dictating all as- Chemical compatibility: One of the first issues that must
pects of film growth from ease or even feasibility of growth be dealt with in determining the suitability of a substrate for
to film quality cannot be overemphasized. In some materials a HTS film is the chemical compatibility of the two materi-
systems, including HTS, the best films that can currently be als. This is true whether or not the film is epitaxial. Ideally,
produced are grown on materials that have serious limita- there should not be any chemical reactions between the film
tions. The search for viable substrate materials is an active and substrate. The constraint is especially severe for HTS

1830 J. Appl. Phys., Vol. 79, No. 4, 15 February 1996 Appl. Phys. Rev.: Julia M. Phillips
films since these materials are reactive with many substrates to the thermal-expansion properties of the substrate and
that might otherwise be good candidates ~such as unbuffered therefore be under stress, whereas a thicker film may crack.
Si!.8,9 The relatively high temperatures required for growing Problems introduced by thermal-expansion mismatch are
even in situ films, or films that are superconducting upon more severe if the system must tolerate extreme tempera-
removal from the growth chamber ~>700 °C!10 make the tures, whether it be during film growth, processing, or the
compatibility requirement more critical than it would be if life of the finished product. Especially in the case of crystal-
high-quality films could be grown at lower temperature. The line films ~and most particularly for epitaxial ones!, a
higher the temperature, the more stringent the requirements thermal-expansion mismatch may cause the film properties
for chemical inertness. In the case of ex situ films, or films themselves to be altered from what they would be if the
that require an anneal external to the growth apparatus in mismatch were absent. For example, the lattice parameters of
order to become superconducting, the problem is even a film may be altered from their equilibrium values by be-
worse, since the maximum temperature that the film/ coming ‘‘locked in’’ to those of the substrate at an elevated
substrate couple must withstand is usually ;850 °C.11 The growth temperature. This deviation from the equilibrium
BaF2 process, which involves formation of YBa2Cu3O7 crystal structure may modify some film properties, for ex-
~YBCO! films by deposition of Y, BaF2 , and Cu at low tem- ample introducing anisotropy into a usually cubic material or
perature followed by a high-temperature ex situ anneal in wet otherwise modifying the electrical properties.
oxygen to hydrolyze the BaF2 is especially demanding, since Surface quality: The quality of the surface is one of the
the substrate must not be sensitive to water vapor at high most important properties of a substrate since it is here that
temperature, in addition to the other requirements already the film–substrate interaction occurs. A uniform surface is
discussed.11 necessary ~although not sufficient! to insure a uniform, ho-
Regardless of the specific film growth method used, the mogeneous film. If the surface is reactive with the film to be
substrate must be unreactive in the oxygen-rich ambient re- deposited, it must be passivated in a reproducible and uni-
quired for growth and processing. These considerations re- form manner. Various types of irregularities make up the
quire close examination of the composition of substrate ma- overall surface texture. The following categories of surface
terials and their possible chemical reactions. In general, one defects may be encountered:
is likely to encounter fewer problems with chemical compat-
~1! on the atomic scale: point defects, dislocation lines,
ibility if the film and substrate are composed of chemically
monatomic ledges on cleavage planes, twin boundaries;
similar species. For example, oxide substrates are more
~2! submicron features: polishing scratches, pores due to
likely to tolerate the growth of HTS materials than are non-
less than theoretical density of the substrate, impurity
oxide materials.
phases;
Thermal-expansion match: Most combinations of sub-
~3! micron scale: grinding scratches, crystalline boundaries
strates and films will be more or less mismatched in regard to
in polycrystalline materials, pores;
thermal expansion. This may result in loss of adhesion or
~4! macrodefects: surface warp, cracks.
film cracking during thermal cycling.
A good thermal-expansion match is necessary, whether Surface smoothness is important for a number of rea-
or not one is dealing with an epitaxial system. In the case of sons. If a complex heterostructure involving a series of thin
HTS materials, this requirement is particularly important be- films is to be fabricated, it is necessary that each layer be of
cause of the brittleness of the superconductor. Thus, YBCO uniform thickness so that the properties of the structure are
films on bulk Si substrates, even with a buffer layer of, say reproducible and predictable. Asperities on a surface may
yttria-stabilized zirconia ~YSZ!, develop cracks if they are have a significant impact on film nucleation, and the mor-
over 50 nm thick, due to the large difference between the phology and structure of the resulting film may be affected.
coefficients of thermal expansion of Si and YBCO.12 Films In some cases, scratches or crystallographic steps may influ-
on YSZ/Si layers on bulk sapphire do not have this problem ence the orientation of a crystalline film as well as its overall
as severely since sapphire has a thermal-expansion coeffi- microstructure.
cient that is much more similar to that of YBCO, and it is The impact of surface morphology has been especially
this value that dominates the system. Nevertheless, there is well illustrated in the case of YBCO film growth on YSZ
even a limit to the thickness of YBCO films that can be substrates.14 The in-plane orientation of the films on smooth
grown on sapphire due to the thermal-expansion mismatch.13 surfaces, as observed by atomic force microscopy ~AFM!,
This ‘‘critical thickness’’ is, however, about one order of was found to be sensitive to the deposition conditions, often
magnitude higher than in the case of a Si substrate. resulting in mixed orientations. At sufficiently high growth
The existence of a nonzero thermal-expansion mismatch, temperature, however, only a single orientation was ob-
which is the rule rather than the exception, can have many tained. Films on substrates with surface steps, resulting from
effects on the film. The severity of the problem depends on the deposition of a homoepitaxial buffer layer or from sub-
several properties of the layer. For example, if the film ma- strate annealing, had a different orientation at the same depo-
terial is very brittle, cracking is likely if the mismatch is sition temperature due to a graphoepitaxial mechanism. The
severe. This is especially true if the film is in tension, i.e., if density of substrate steps was also observed to affect the
the thermal expansion of the film exceeds that of the sub- c-axis lattice parameter, probably due to atomic scale disor-
strate. The effect of thermal mismatch on a film may depend der in the growing film resulting from a low density of ad-
on film thickness. For example, a thin film may ‘‘conform’’ sorption sites.

J. Appl. Phys., Vol. 79, No. 4, 15 February 1996 Appl. Phys. Rev.: Julia M. Phillips 1831
A related result has been documented in the case of of the substrate may also affect the quality of the surface,
YBCO film growth on MgO.15 The largest population of especially if the density is high. These are often nucleation
misoriented grains and poorest overall crystallinity was sites for defects in the film. Twin boundaries which propa-
found in films grown on the substrates that were the most gate throughout the substrate are likewise potential nucle-
featureless on an atomic scale. The best structural and super- ation sites for competing crystalline orientations in the film
conducting properties resulted from growth on substrates an- and may have other undesirable defects as well.
nealed to yield a high density of atomic steps. Substrate thermodynamic stability: The chemical stabil-
An ideal substrate would have a flat, dense surface and ity of the substrate was discussed above, but it is also highly
be free of twins and other structural inhomogeneities, al- desirable that the substrate be thermodynamically stable
though a number of materials in current use as HTS sub- within the temperature range required to grow and process
strates do have such problems.8 LaGaO3 in particular has the thin film. A phase transition within this region can have
been observed by optical microscopy to undergo surface dramatic effects on the surface quality of the substrate and on
roughening at its phase transition at 140 °C,16,17 which has the stresses the film must undergo, even if the chemistry is
serious implications for the integrity of HTS films deposited not a problem. If a phase transition is inevitable, it should be
on this material. It would be desirable, at the very least, to as minor as possible, i.e., second order with no discontinuous
grow films on a substrate that has no phase transitions within volume change and minimal structural change.
the temperature regime required for film processing. In the Buffer layers: Buffer layers have been used extensively
case of microwave applications, where the dielectric proper- in the study of HTS films. These are films that are grown
ties of the substrate have an important effect on device per- directly on the substrate in order to alleviate some of the
formance, the existence of a twinning transition in the pro- shortcomings that a substrate may have. The most common
cessing range is entirely unacceptable, since it precludes reason to use a buffer layer is to avoid unwanted reactions
device modeling.18 between film and substrate. Obviously, the buffer layer must
Substrate cleanliness: The cleanliness of the substrate be chemically compatible with both materials. Some reaction
surface exerts a decisive influence on film growth and adhe- between the buffer layer and substrate may be permissible if
sion. A thoroughly cleaned substrate is a prerequisite for the it is confined to a region near the interface.
preparation of films with reproducible properties. The choice Buffer layers may serve other purposes, as well. If the
of cleaning techniques depends on the nature of the sub- thermal-expansion mismatch between the HTS layer and
strate, the type of contaminants, and the degree of cleanliness substrate is large, a buffer layer with intermediate thermal
required. Residues from manufacturing and packaging, lint, properties may alleviate cracking of the film. Choosing a
fingerprints, oil, and airborne particulate matter are examples buffer material with a lattice constant intermediate between
of frequently encountered contaminants. Accordingly, it is the two materials may improve the epitaxial quality of the
necessary to address the questions of contaminant identifica- grown layer. In some cases, the buffer layer may even
tion and effective removal. Suitable answers can seldom be change the epitaxial orientation of the HTS film, so that grain
derived from general principles but usually require an em- boundaries can be engineered into the layer.19
pirical approach. Major progress has recently been reported in the use of
Rather little work has been done to study the effect of buffer layers for the growth of highly crystallographically
surface cleanliness on HTS film quality. There have been textured HTS films.20 The buffer layer texture is induced
studies of the effect of various chemical, mechanical, and using ion-beam-assisted deposition ~IBAD!, which estab-
thermal treatments of the substrate on film microstructure lishes orientation in the buffer layer ~typically YSZ! by in-
and morphology, but these have primarily addressed the ef- ducing alignment of the most open crystallographic axis
fect of surface morphology on the film structure and super- @~111! in the case of YSZ# with the incident ion beam ~typi-
conducting properties and not the cleanliness issue.15 The cally Ar with incident energy of tens to a few hundred eV!.
general protocol for substrate cleaning prior to HTS film This development has the potential to expand greatly the set
growth seems to be degreasing in organic solvents, possibly of substrate materials that can be considered for HTS film
followed by an anneal ~generally in oxygen if the substrate is growth.
an oxide!. This is an issue that clearly needs further attention
as HTS film growth studies progress.
C. Issues for epitaxial films
Substrate homogeneity: While issues in the surface qual-
ity of the substrate have already been dealt with, the quality The best HTS films grown to date, as determined by a
of the bulk of the substrate must also be reasonable. For multitude of metrics including critical current density, mor-
example, if a substrate is predominantly a single phase but phology, and stability over time, are epitaxial on their sub-
contains an appreciable amount of one or more additional strates. The crystal structures of YBCO, Bi2Sr2CaCu2O8
phases, the surface quality is likely to suffer, and the film ~BSCCO!, and Tl2Ba2Ca2Cu3O10 ~TBCCO! are shown in
may not grow equally well on all of the phases present. Fig. 1. Epitaxial growth requires the controlled crystallo-
Grain boundaries in the substrate that appear on the surface graphic orientation of the film with respect to the substrate.
may affect the microstructure and morphology of the film. In general, this necessitates matching the film and substrate
The substrate should have the theoretical density of its con- with respect to lattice parameters, atomic positions, crystal-
stituent, since voids will affect the quality of the growth lographic orientation, etc. The better the match of all of these
surface. Precipitates, dislocations, etc., throughout the bulk parameters, the more likely high-quality epitaxial growth is

1832 J. Appl. Phys., Vol. 79, No. 4, 15 February 1996 Appl. Phys. Rev.: Julia M. Phillips
FIG. 1. Crystal structures of the most common HTS film materials: ~a!
YBa2Cu3O7 ; ~b! Bi2Sr2CaCu2O8 ; ~c! Tl2Ba2Ca2Cu3O10 .

to occur. These additional requirements on the material are epitaxial growth, frequently involving material on NaCl or
listed in Table II and are discussed in this subsection. some other substrate very different chemically and structur-
Lattice match: The first requirement that is generally ally from the film to be grown, indicated that a lattice mis-
considered in selecting a substrate for epitaxial growth is its match of less than 15% was required for there to be a pos-
lattice match with the film. Historically, the first studies of sibility of epitaxy.21 As the field of epitaxial growth

TABLE II. Issues in substrate selection for epitaxial films.

J. Appl. Phys., Vol. 79, No. 4, 15 February 1996 Appl. Phys. Rev.: Julia M. Phillips 1833
concentrated on semiconductor systems, in which the chem- Surface quality: The importance of surface properties in
istry of the film and substrate are very similar, it became determining the quality of a film grown on it was discussed
apparent that vanishingly small lattice mismatches were de- in Sec. II B. It needs to be emphasized that this parameter is
sirable to minimize the effects of dislocations and other de- even more critical for epitaxial growth. Misoriented grains
fects brought about by lattice dissimilarities.22–24 More re- frequently nucleate on irregularities on a surface, be they
cently, there have been attempts to combine materials with dirt, surface defects, or atomic steps due to substrate miscut
larger lattice mismatches ~several percent or higher!. In the or other treatment. In some cases, the presence of atomic
case of semiconductors, this has led to rediscovery of many steps can actually be useful in nucleating a particular epitax-
of the defects that had been minimized or avoided by small ial orientation preferentially over another orientation that oc-
mismatch. In the case of HTS materials, the issue is more curs on surfaces that do not have steps.14 The quality of a
open. In general, it seems desirable to minimize the lattice substrate surface can be affected by a number of treatments
mismatch as much as possible. This seems to improve the including cleaving, polishing of various sorts ~chemical
ability to obtain singly oriented films. Still, as is discussed at and/or mechanical!, and annealing in a variety of ambients.15
length later, several substrates with significant lattice Slight misorientations of the substrate can have a profound
matches have been used with considerable success, although effect on the epitaxial quality. For example, in the case of
the large lattice mismatch contributes to doubt regarding MgO, the mosaic spread of a YBCO film has been found to
their ability to support films of sufficient quality for some increase dramatically even at a vicinal angle as small as 1°.27
Structural quality: The structural quality of the substrate
applications.
is even more important when epitaxial films are required
Coincidence sites: In general, it is not enough simply to
than when they are not. It goes without saying that a single-
require that there be a close lattice match between the film
crystal film is possible essentially only when the substrate
and substrate. There must also be a reasonable number of
itself is single crystalline. Impurity phase inclusions in the
coincidence sites between the two lattices. These are atomic
substrate very likely will affect the surface quality and ulti-
positions ~preferably with the same or similar atomic sizes
mately the epitaxial quality as well. Twins in the substrate in
and valences! that coincide on either side of the interface.
many cases will affect the degree of orientation possible in
Frequently, although not always, this means that the film and the film. In general the crystalline quality of the film will be
substrate should have similar crystal structures ~e.g., perov- no greater than that of the substrate.
skite!. The higher the number of coincidence sites, the better
the chance of good epitaxy.
Similarity in structure is probably as important a crite- D. Issues for applications
rion in determining a suitable HTS epitaxial substrate as is
lattice match, although they are not independent.25 By ana- In developing a list of materials requirements for sub-
lyzing a variety of substrate structures, it has been shown in strates for HTS films, it is first useful to enumerate some of
Ref. 25 that it is the similarity in interatomic structure, in- the actual device applications of HTS layers that are contem-
cluding ionic distributions and distances, that is the primary plated. Each of these potential applications poses its own
requirements for the substrates as listed in Table III and dis-
consideration for substrate selection. The surface termination
cussed below.
of the substrate is also a crucial parameter in determining the
All-superconducting devices: The first application of su-
quality of oriented or epitaxial growth. It is argued that with
perconductors to electronics is for all superconducting de-
this understanding, the range of potential HTS substrates can
vices. Nearly all such devices that have been demonstrated to
be broadened substantially over what has been considered to
date involve some sort of Josephson junction, or region of
date. It must be remembered, however, that some of the other
restricted current flow.28,29 Possible means of accomplishing
issues already discussed, such as chemical compatibility, this include lithographic patterning of a single superconduct-
must be considered simultaneously. ing film, incorporation of a grain boundary into a single film,
When the substrate crystal is of higher symmetry than or use of a thin layer of metal or insulator between two
the crystal of the overgrown film, a finite number of differ- superconducting regions, through which superconducting
ently oriented island nuclei develop, which leads to a finite electrons can pass. The substrate must be able to support
number of discrete epitaxial orientations within the film.26 HTS films of adequate quality for reproducible junction fab-
This ‘‘degenerate epitaxy’’ is observed in the triple position- rication. Grain boundaries must exist only where desired, as
ing of tetragonal YBCO on lattice-matched cubic SrTiO3 in the grain-boundary junction. The grain-boundary junction
with 90° grain boundaries separating the different orienta- requires either processing of the substrate before HTS film
tions. The in situ growth of YBCO films on MgO~001! is a growth or the production of a bicrystal substrate.
good example of ‘‘coincidence epitaxy,’’ where the lattice A more recent all-superconducting device that has re-
misfit is large. Differently oriented island nuclei form to ceived attention from high-frequency circuit designers deal-
minimize interfacial energy by maximizing the lattice coin- ing with HTS is the superconducting flux-flow transistor
cidence and minimizing the misfit and strain energy across ~SFFT!.30 In this device a region of a single superconducting
the film–substrate interface. These examples serve to empha- film is thinned and perforated selectively, resulting in a re-
size the importance of matching as many parameters of the duced film cross section between the source and drain of the
film and substrate as possible, including lattice match, coin- device. The major requirement for the substrate, aside from
cidence sites, and crystallographic symmetry. the obvious necessity that it support a device-quality HTS

1834 J. Appl. Phys., Vol. 79, No. 4, 15 February 1996 Appl. Phys. Rev.: Julia M. Phillips
TABLE III. Issues in substrate selection for applications.

APPLICATION

Hybrid HTS– Integrated HTS


SUBSTRATE All HTS semiconductor and semiconductor Microwave Current-carrying
REQUIREMENT devices devices devices Interconnects applications applications

Support high- 3 3 3 3 3 3
quality films
Control grain 3 3 3
boundaries
Low dielectric varies 3 3 3
loss
Device-quality 3 3 3
semiconductor
layer
Low e 3 3
Large area 3 3 3 3
Isotropic 3
Low surface 3
resistance films
High-J c films 3 3

film, comes from the fact that this device is intended for again, substrates must be able to support not only the inter-
high-frequency operation. This requires that the substrate connects but also at least some of the semiconductor circuits.
have low dielectric losses. They must be low loss and compatible with both classes of
Hybrid superconductor–semiconductor applications: electronic material. Because of the high speeds involved, the
Hybrid superconductor–semiconductor devices and systems dielectric constant of the substrate must be as low as pos-
have been contemplated for many years. Typically, three lev- sible. In order to have an impact on the electronics industry,
els of hybridization are discussed: large-area substrates are required.
Microwave applications: Microwave-frequency devices
~1! combining superconductor and semiconductor in a single
such as filters and delay lines have been targeted by many as
device;
potential niches for HTS devices.33 In this regime, supercon-
~2! combining individual superconductor devices with semi-
ductors offer a number of potential advantages such as dy-
conductor devices in an integrated circuit; and
namic range and bandwidth. The large area occupied by
~3! combining superconducting circuits and semiconducting
many of these devices introduces the need for large-area sub-
circuits or chips into a complete system.31
strates. Operation at microwave frequencies imposes the
An example of a single device using both superconduct- need for low substrate loss. Since the dielectric properties of
ing and semiconducting materials is the semiconductor- the substrate have an important effect on device perfor-
coupled Josephson junction, in which the semiconductor acts mance, the existence of a twinning transition in the process-
as the weak link for tunneling between two superconducting ing range is entirely unacceptable, since it precludes device
regions.32 In this device, the substrate must either be a semi- modeling.18
conductor ~capable of supporting device-quality HTS mate- Microwave device applications impose a number of
rial at the interface! or be a material that can support both other property requirements on the HTS substrate material.
device-quality semiconducting and HTS layers. Microwave applications are not generally very sensitive to
The combination of superconducting devices with semi- the dielectric constant of the substrate ~as long as it is uni-
conducting ones in an integrated circuit requires, at least for form and, preferably, isotropic for modeling convenience!,
the present, the operation of the semiconducting devices at but they do depend on having a low value of the loss tangent.
77 K or below. If one is to fabricate integrated circuits using This precludes the use of materials that contain magnetic
active superconductor and semiconductor, one will require ions, such as most of the rare earths.
device-quality layers of both superconductors and semicon- Current-carrying applications: In some cases, supercon-
ductors to be combined on a single substrate that is compat- ducting films are desired strictly for their ability to carry
ible with both. large amounts of current with no loss. In such applications, a
At the system level, the greatest interest in combining metal substrate is generally preferred, since it serves as an
superconductors with semiconducting circuits has been on alternate-current path in the case of warming of the super-
superconducting interconnects, which can increase both conductor or other problem. In addition to being a metal,
bandwidth and wiring density.31 In the various analyses that substrates for these applications need to be able to support
have been performed, the level at which HTS interconnects superconducting films that have a high critical current den-
may become interesting is among gate-level circuits. Once sity and that probably are quite thick.

J. Appl. Phys., Vol. 79, No. 4, 15 February 1996 Appl. Phys. Rev.: Julia M. Phillips 1835
III. SUBSTRATE MATERIALS
A. Overview
Many materials have been tried as substrates for HTS
films, but most have met with limited success. In general, the
search for substrates that can support the growth of high-
quality HTS films has centered on materials having the per-
ovskite crystal structure, usually oxides.25 Most of the other
materials that have been studied extensively and/or met with
some success have fallen into one of the following catego-
ries:
~1! oxides with a crystal structure that is not based on the
perovskite cell;
~2! semiconductors;
~3! metals.
Only a few substrates do not fall into one of these categories.

B. Perovskite-structure oxides
The most studied and most successful substrates for HTS
materials to date are nearly all oxides with the perovskite
crystal structure. This arises quite naturally, since the crystal
structures of the HTS compounds are closely related to the
perovskite structure, giving a large number of coincidence
sites as shown in Fig. 2. The lattice constants also tend to be
quite similar. Finally, since these substrate materials are
themselves oxides, the chemical compatibility between them
and the HTS materials tends to be good. Some of the funda-
mental properties of these materials are discussed in Refs. 8
and 34 –37. The properties most relevant to the growth of
HTS films are listed in Table IV. The lattice mismatches
indicated are with YBCO.
SrTiO3 saw early success as a substrate material,4 which
is not surprising in view of its rather small lattice mismatch
with YBCO ~its lattice constant is a50.3905 nm! and its
ready availability. The prohibitively large dielectric constant
of this material ~e5277 at room temperature!, coupled with FIG. 2. ~a! The perovskite crystal structure, shown here for SrTiO3 . ~b! The
its unavailability in reasonable sizes, has spurred the search crystal structure of YBa2Cu3O7 . It is obvious that the two structures are
for alternatives. Still, SrTiO3 is able to support high-quality closely related, making epitaxial growth likely. The chemical compatibility
YBCO films with state-of-the-art properties, i.e., T c ;90 K between perovskite structure oxides and the HTS materials tends to be good.
Some of the fundamental properties of these materials are discussed in Refs.
and J c ~77 K!;53106 A/cm2 ~e.g., see Ref. 38!. Representa- 8 and 22–37. The properties most relevant to the growth of HTS films are
tive data for YBCO film resistivity as a function of tempera- listed in Table IV. The lattice mismatches indicated are with YBCO.
ture are shown in Fig. 3. Critical current density data are
plotted in Fig. 4.
The situation is not so clear for Biv Srw Cax Cuy Oz sputtering.41 The films consisted largely of the ~1201! phase
~BSCCO!. Liquid-phase-epitaxial ~LPE! films of the ~2212! with the c axis perpendicular to the plane of the film. T c 585
phase have T c 575 K ~see Fig. 5! and, as shown in Fig. 6, K; J c ~50 K!513103 A/cm2; J c ~5 K!513104 A/cm2. The
J c 533104 A/cm2 3° below the T c .39 Tlv Baw Cax Cuy Oz room-temperature resistivity of these films is a high 20–100
~TBCCO! ~2212! films on SrTiO3 have also been studied.40 mV cm.
The lattice mismatch in this case is 1.28%. In spite of the LaGaO3 was identified as a potential substrate material
rather small lattice mismatch, the film is not epitaxial; the c rather early.42 Its lattice matches and thermal-expansion
axis is predominantly perpendicular to the film surface, but match with HTS materials are quite good ~the lattice con-
the a axes are not aligned in the plane of the film. There is a stants are a50.5519 nm, b50.5494 nm, and c50.7770 nm!,
large amount of second-phase material in the film, as well as and its dielectric constant at room temperature is smaller
evidence for strong film–substrate reactions, with Sr and Ti than that of SrTiO3 by one order of magnitude ~e525!. The
present in the HTS film itself. The superconducting transition crystal structure is shown in Fig. 8. It is possible to grow
is at about 100 K ~see Fig. 7!, but there is an indication of LaGaO3 crystals by the Czochralski technique, so that large-
two transitions. The only report of Hgv Baw Cax Cuy Oz films area substrates are available, although demand for this mate-
involves their growth on SrTiO3 substrates by rf magnetron rial has been largely supplanted by that for more desirable

1836 J. Appl. Phys., Vol. 79, No. 4, 15 February 1996 Appl. Phys. Rev.: Julia M. Phillips
TABLE IV. Properties of perovskite substrates for HTS materials.

Da/a Db/b Dc/c CTE Phase mp


~%! ~%! ~%! ~ppm! e36 tan d36 transf. ~K! ~K!

SrTiO3 12.0 10.7 10.1 10.4 277a 631022 110b 2353


~100 K, 300 GHz!
LaGaO3 11.5 10.7 20.5 10.3 25 631023 420c 2023
~100 K, 500 GHz!
LaAlO3 20.9 22.2 23.0 11 23 331025 800b 2453
~77 K, 5 GHz!
NdGaO3 10.3 10.3 21.3 8.0 20 331024 .1300 1873
~77 K, 5 GHz!
NdAlO3 12.2 14.0 14.4 17 1820b 2363
YAlO3 24.5 25.4 24.0 5–10 16 131025 .1573 2148
~77 K, 10 GHz!
PrGaO3 20.9 20.2 10.8 7– 8 24 3.631024 .1300
~300 K, 1 kHz!
KTaO3 24.2 22.9 22.2 6.8 1630
YbFeO3 11.0 20.3 10.5 4 –5 yes
Sr2AlTaO6 11.7 20.1 0.0 9.0 23–30 431024
~100 K, 10 kHz!
GdBa2NbO6 210 28.8 28.0
a
Room-temperature values.
b
Second-order phase transformation.
c
First-order phase transformation.

substrates. There were early reports of the growth of high- due to chemical reactions at the high temperatures required
quality films on this substrate, with high T c ~;90 K for to grow the best films by this technique.
YBCO! and J c ~2.33106 A/cm2 at 77 K for YBCO!.38 BSCCO ~2212!,39 and TBCCO ~2212!,40 films have also
LaGaO3 has one serious drawback, however, namely its first- been grown on LaGaO3 , although the results have not been
order phase transition at 420 K,8 well within the processing quite as good as on some other materials. BSCCO films
region for HTS films grown by any technique. This transition grown by LPE show three peaks in the rocking curve, pre-
gives rise to steps on the surface of the substrate, which can sumably arising from the twinning transition in the
be particularly detrimental in the case of very thin or pat- substrate.39 The T c of these films is about 70 K, and J c ~4.2
terned films.17 YBCO films grown by the BaF2 process are K!533104 A/cm2 as shown in Fig. 6. The T c of TBCCO
not as good as those grown on other substrates,43 possibly ~2212! film is as high as 99 K in a two-step growth process.40
The films are predominantly c-axis oriented, but there is
some a-axis materials as well. Cracks in the films have been
attributed to the phase change in the substrate during film
processing. There is no evidence of chemical interaction with
the substrate.
LaAlO3 also offers small lattice and thermal mismatches
with HTS materials.44 The pseudocubic lattice constant is
0.5377 nm. The dielectric constant is 24, and tan d

FIG. 3. Resistivity as a function of temperature for a YBCO film grown on FIG. 4. log J c (t) vs log~12t! for YBCO films grown on SrTiO3 , LaAlO3 ,
SrTiO3 by PLD ~after Ref. 38!. and YSZ by PLD, where t is the reduced temperature ~after Ref. 38!.

J. Appl. Phys., Vol. 79, No. 4, 15 February 1996 Appl. Phys. Rev.: Julia M. Phillips 1837
FIG. 5. Resistivity vs temperature for a BSCCO film grown on SrTiO3 by
LPE ~after Ref. 39!.

5331025.45 It, too, has a phase transition within the film FIG. 7. ac inductance resonant frequency, indicating superconducting tran-
sitions, as a function of temperature for TBCCO films prepared on different
processing regime ~at 800 K!, but this transition is second substrates by a two-step process ~after Ref. 4!.
order.16 While this leads to substrate twinning, there is no
discontinuous volume change and surface steps are not a
problem. The twinning has not prevented the growth of high- TBCCO ~2212! and ~2223! films of high quality have
quality films on this substrate, but it does make the fabrica- also been grown, due in large part to the small ~1.63%! lat-
tion of complex microwave devices such as filters impos- tice mismatch with the substrate.40,47– 49 There is no evidence
sible, since the dielectric properties of the substrate vary of film–substrate reaction. T c as high as 106 K ~2212! and
from point to point in a manner that cannot be controlled or 123 K ~1223! have been measured. J c for the ~2212! phase
predicted. LaAlO3 has emerged as one of the most favored has been measured to be 23106 A/cm2 at 80 K and 13107
HTS substrates, which has stimulated considerable work on A/cm2 at 4.2 K.49 For the ~2223! phase, J c 55.53105 ~77
scaling up the diameter of crystals that can be grown by the K!.47 The J c of films deposited on LaAlO3 are reported to be
Czochralski technique. 100-cm-diam substrates are currently ;20 times higher than for those deposited on YSZ and MgO
available. There is no indication that larger diameters cannot and the magnetic-field dependence of the ac susceptibility of
be grown given sufficient demand. the films is lower.48 This has been attributed to less well-
As with all the other substrate materials, more work has defined boundaries between grains during film growth for
been done with YBCO films on LaAlO3 substrates than with films on LaAlO3 .48
other HTS films. State-of-the-art T c ~.90 K! and J c NdGaO3 ~e520! was introduced as a possible alternative
~.53106 A/cm2 at 77 K! have been reported for films grown to the La-containing perovskites.44 With an orthorhombic
by a wide variety of growth techniques. The films are typi- crystal structure and a50.5417 nm, b50.5499 nm, and
cally highly epitaxial with strong c-axis orientation. In fact, c50.7717 nm, it has smaller lattice mismatches than either
LaAlO3 seems to have become the substrate of choice for LaGaO3 or LaAlO3 . The coefficient of thermal expansion is
‘‘standard’’ YBCO films. The temperature dependence of the 5.831026/K,50 making this mismatch somewhat larger than
resistivity of a typical YBCO film on LaAlO3 is shown in
Fig. 9.
Epitaxial BSCCO ~2212! films have been grown on
LaAlO3 .46 The T c was measured to be 89 K ~see Fig. 10!,
and J c 523105 A/cm2 at 77 K and 13106 A/cm2 at 45 K.

FIG. 6. J c vs reduced temperature for LPE-grown BSCCO films on ~d! FIG. 8. The crystal structure of LaGaO3 . HTS films grow at epitaxially at a
SrTiO3 and ~s! LaGaO3 . The line represents the theoretical depairing cur- 45° angle to the a 0 and b 0 axes, so that a c is the relevant ‘‘lattice constant’’
rent density for BSCCO ~after Ref. 39!. to be used in calculating the lattice match.

1838 J. Appl. Phys., Vol. 79, No. 4, 15 February 1996 Appl. Phys. Rev.: Julia M. Phillips
NdAlO3 has been less studied than the perovskite mate-
rials already discussed. It has somewhat larger lattice mis-
matches with HTS compounds than the other materials, al-
though still smaller than some other heteroepitaxial systems
of current interest, e.g., GaAs on Si.37 Its main potential
advantage is the very high temperature of its second-order
phase transition, 1820 K. Only films grown by the BaF2 pro-
cess have been reported.43 These have T c 589.7 K, but the
J c ~77 K! is quite low, only 33104 A/cm2.
YAlO3 has been investigated to some extent as a poten-
tial HTS substrate material.6,53 Among its strengths is the
lack of twinning or phase transitions in the processing tem-
perature window required for HTS films. Its dielectric con-
FIG. 9. Resistivity vs temperature for a YBCO film grown on LaAlO3 by
the BaF2 process. stant of 16 is smaller than that of most of the perovskites. It
also has a promising loss tangent, with values at 10 GHz of
7.331025 at 300 K, 131025 at 77 K, and 231026 at 40 K. It
that of some of the other perovskite materials. It also has the does, however, have a large mismatch with YBCO, given its
advantage of having no phase transitions between its melting pseudocubic lattice parameters of a50.3662 nm, b50.3768
point and room temperature, so twin-free substrates are nm, and c50.3685 nm. Only small substrate sizes are avail-
available for YBCO growth. Na31 is a magnetic ion, how- able, probably because of the lack of motivation for scale-up.
ever, which precludes its use as a substrate for microwave The substrate supports YBCO films with T c .91 K and J c ~77
devices. There have been conflicting reports regarding the K!.7.23105 A/cm2.
quality of film that can be grown on this substrate. Using PrGaO3 has a distorted perovskite structure with
LPE,51 or pulsed laser deposition ~PLD!,52 high T c values a50.5462 nm, b50.5493 nm, and c50.7740 nm. YBCO
.89 K have been obtained. The PLD-grown films also have films have been grown on this material with T c 590 K.54 No
J c ~77 K!.23106 A/cm2. J c data have been reported.
NdGaO3 is quite an attractive substrate for the growth of There has been one report of a YBCO film on KTaO3 ,
a-axis-oriented YBCO films because of the low mismatch in which is cubic with a50.399 nm.55 The lattice mismatches
this orientation: 0.28% for the c axis and 0.10% for the b are somewhat larger than those of some of the other perov-
axis.50 Some of the better a-axis-oriented films that have
skite substrates, and the films are not as good. While T c is
been reported have been grown on this substrate.
quite high ~90 K!, J c is about 33105 A/cm2 at 77 K.
Results for TBCCO ~2212! films on NdGaO3 have also
YbFeO3 and other magnetic orthoferrite materials could
been somewhat mixed.40,45 In both reports T c ;100 K. J c ~77
be of interest as HTS substrates because of their magnetic
K! is 53105 A/cm2.45 The orientation of the films is excel-
lent, although there is a small amount of a-axis material in properties and structural compatibility with the films.56 This
the c-axis films.40 There is also evidence for a small amount material has lattice constants a50.536 nm, b50.550 nm, and
of chemical reaction between the film and substrate. c50.777 nm. The dielectric constant is much lower than that
Like LaGaO3 and LaAlO3 , NdGaO3 can be grown by the of most of the other HTS substrate candidates, having a
Czochralski technique, and the process has been scaled up to value of 4 –5. YBCO films grown on YbFeO3 have T c 588 K
about 50-cm-diam boules. Further scale-up should be pos- and J c ~77 K!,13105 A/cm2. There is a twinning transition
sible given sufficient demand, although there have been in this substrate in the HTS processing range which leads
some problems with crystal cracking during growth. both to twin formation in the substrate ~and hence unpredict-
able dielectric variations across the substrate! and to twin-
ning in the film beyond what might normally be expected.56
A number of complex perovskite materials has been pro-
posed as potential HTS substrates.57,58 Unfortunately, there
have been almost no reports of film growth on these materi-
als because of the unavailability of single-crystal substrates,
although there has been some success using Sr2AlTaO6 as
part of multilayer HTS structures.59,60 There is one report of
YBCO growth on GdBa2NbO6 substrates, although the sub-
strate itself was polycrystalline, which undoubtedly affected
the quality of the film.61 This material is cubic with a50.843
nm. The dielectric constant is ;26, and tan d;431024. A
YBCO film grown on this material by PLD had T c 590 K.
Other properties of the films were not reported. Work on
FIG. 10. Resistivity vs temperature for a BSCCO film grown on LaAlO3 by these materials is too premature to know what the prospects
metalorganic deposition ~after Ref. 46!. are with regard to obtaining large area substrates.

J. Appl. Phys., Vol. 79, No. 4, 15 February 1996 Appl. Phys. Rev.: Julia M. Phillips 1839
TABLE V. Properties of non-perovskite structure oxide substrates for HTS materials.

Da/a Db/b Dc/c CTE Phase mp


~%! ~%! ~%! ~ppm! e36 tan d36 transf. ~K! ~K!

MgO 29.0 26.7 27.4 10.5 9.65 531024 ••• 3100


~100 K, 300 GHz!
Al2O3 29.4 27.0 211.2 8.4 9.34 331025 ••• 2300
~77 K, 5 GHz!
YSZ 13.6 16.3 15.8 8.8 25 831023 ••• 3000
~100 K, 300 GHz!
CeO2 0.0 11.3 11.9 17 ••• 2900
CaNdAlO4 13.6 14.9 13.8 19 131024 ••• 2093
~77 K, 5 GHz!
CaYAlO4 14.7 15.9 21.5 20 431025 •••
~77 K, 5 GHz!
SrLaAlO4 21.9 13.2 13.8 7.4 17 531024 ••• 1923
~100 K, 8 GHz!
SrLaGaO4 10.4 20.9 27.7 10–19 22–26 531025 ••• 1793
~77 K, 5 GHz!
Sr2RuO4 21.1 10.2 28.8
Mg2TiO4 210 28.8 28.1 12 10–15 1.531023 ••• 2029
MgAl2O4 25.6 24.2 23.5 12 531024 ••• 2408
~300 K, 1 MHz!
Y3Al5O12 24.6 23.2 22.6 10 931024 2243 2383
~300 K, 1 MHz!
Gd3Ga5O12 27.9 26.5 25.8 15 1.131023
~300 K, 1 MHz!
LiNbO3 14.8 16.2 16.7 23– 44 231023 1526
~300 K, 1 GHz!
MgLaAl11O19 23.2 21.8 16.3 11 731024
~300 K, 9.4 GHz!

C. Non-perovskite-structure oxides tensive investigations of substrate materials that have other


crystal structures. Many of these materials are oxides and, as
As discussed in the previous subsection, a number of
problems have emerged with HTS substrate materials with such, their chemical compatibility with HTS films may still
be good. In general, however, the structural matching be-
perovskite-related crystal structures. These include high sub-
strate cost, dielectric constant values that are higher than tween film and substrate is poorer for non-perovskite sub-
strates, making the growth of films with multiple orientations
desired for many applications, twinning transitions within
the HTS processing range in a number of the materials, ques- and many grain boundaries more likely. On the other hand, a
tions of the scalability of substrate size to arbitrary diameter, number of these substrates are already available in large
sizes at reasonable cost. They may also have more favorable
and large dielectric losses in many of the substrates due to
the presence of magnetic ions. These issues have led to ex- dielectric properties and be known to be compatible with
other technologically important materials such as semicon-
ductors. Some of the properties of the most studied of these

FIG. 12. Resistivity vs temperature for YBCO films grown on: ~a! chemi-
cally polished MgO~100!; ~b! mechanically polished MgO; ~c! thermally
FIG. 11. The crystal structure of MgO ~after Ref. 142!. annealed MgO ~after Ref. 15!.

1840 J. Appl. Phys., Vol. 79, No. 4, 15 February 1996 Appl. Phys. Rev.: Julia M. Phillips
FIG. 14. The cubic fluorite crystal structure. YSZ, CeO2 , CaF2 , SrF2 , and
FIG. 13. The crystal structure of sapphire ~after Ref. 142!. BaF2 have this structure.

oxides with non-perovskite crystal structures are listed in MgO has also been investigated as a substrate for
Table V. The lattice mismatches indicated are with YBCO. TBCCO ~2212! films, where the lattice mismatch is
MgO, with the NaCl crystal structure shown in Fig. 11, 8.45%.40,68 This gives rise to weak in-plane orientation, al-
has received a good deal of interest in light of its ready though the c axis of the film is perpendicular to the substrate
availability and its modest dielectric constant ~e59.65!.15 It surface. There is little evidence of chemical reaction between
has a 9% lattice mismatch with YBCO, but with proper sub- MgO and the film.40 T c ;105 K has been reported,68 with
strate preparation high-quality epitaxial films can be grown. J c ~77 K!51.23105 A/cm2 and J c ~4.2 K!51.13106 A/cm2.
Substrate preparation has been shown to have a major effect Sapphire ~Al2O3! is of considerable interest as a sub-
on the properties of YBCO films on MgO. Thermal anneal- strate in view of its modest dielectric constant ~e59.34! and
ing of the substrates produces films with good structural and its commercial availability in large-diameter wafers as well
superconducting properties at reasonable growth tempera- as its demonstrated compatibility with silicon in the silicon-
tures, whereas alternative chemical and mechanical treat- on-sapphire technology. Its crystal structure is shown in Fig.
ments lead to the formation of large-angle tilt boundaries and 13. Sapphire reacts with HTS materials, making growth on
degraded superconducting properties, such as the supercon- unbuffered substrates challenging. The best results for
ducting transition shown in Fig. 12.15 Such annealing treat- YBCO films on unbuffered sapphire give T c 585– 88 K,69
ment has been shown to be responsible for improving the and J c ~67 K!513106 A/cm2.70 A buffer layer ~such as
properties of YBCO films as thin as 5 nm.62 The miscut of SrTiO3 , MgO, or LaAlO3! must be used in order to obtain
the substrate is also very important in determining the mo- high-quality films. Using a SrTiO3 buffer layer, T c 587 K
saic spread in the film.27 In the case of films grown by metal- and J c ~74 K!523106 A/cm2.70 Because the crystal structure
organic chemical-vapor deposition ~MOCVD!, epitaxial is not cubic, the dielectric properties of sapphire are aniso-
grains predominate in the films only when there is a high tropic, which makes the modeling of microwave device per-
density of steps on the MgO surface. Even the best films, formance difficult. ZrO2 has served as a buffer layer for
however, tend to have some high-angle grain boundaries, YBCO growth on ~11̄02! sapphire substrates.71 This yields
which is probably responsible for the fact that such films T c 589.5 K and J c ~77 K!51.53106 A/cm2. In this structure
have poorer high-frequency characteristics than do the best there is evidence of Al in the ZrO2 layer but not in the
films grown on other substrates. MgO also reacts with water YBCO. CeO2 has also been used as a buffer layer between
vapor, which precludes its use as a substrate for films grown sapphire and YBCO.6,72 Only a 20 nm layer is necessary to
by methods that require the presence of water. passivate the Al2O3 . These buffer layers still do not alleviate
MgO is one of the substrates that has been used to sup- the mismatch in the thermal-expansion coefficient of the sap-
port a-axis-oriented YBCO layers,63,64 but the level of suc- phire and HTS materials, which causes films thicker than
cess reported has been mixed,38 possibly due to the sensitiv- ;400 nm to crack. Even thinner films can develop microc-
ity of film quality to substrate surface preparation for this racks with thermal cycling.6
material. The best a-axis films 100–200 nm thick have TBCCO films have been grown on sapphire ~0001! using
T c 590 K and J c 53–53106 A/cm2. Even 10-nm-thick films a two-step postdeposition anneal.40 These films were not
of this orientation have T c 589 K.63 aligned with the substrate and showed a large population of
There has been a number of studies of BSCCO film secondary phases along with strong film–substrate reactions.
growth on MgO, using a variety of film growth techniques The interface was seen to be Tl deficient, and there was
including sputtering,65 PLD,66 and LPE.67 It seems to be rela- evidence of BaAl2O4 . The T c onset from ac susceptibility
tively straightforward to produce ~2212! films with T c .80 measurements was 99.5 K, but the transition was not com-
K. The J c values tend to be rather modest, the best report to plete at 77 K. The film consisted mostly of the 2212 phase,
date being a value of 13104 A/cm2 at 65 K.66 but a small amount of the 2223 phase was also observed.

J. Appl. Phys., Vol. 79, No. 4, 15 February 1996 Appl. Phys. Rev.: Julia M. Phillips 1841
Yttria-stabilized ZrO2 ~YSZ! has been investigated ex-
tensively both as a substrate in its own right and as a buffer
layer between other substrates and HTS films.38 It has the
cubic fluorite crystal structure shown in Fig. 14. The interest
stems from its availability, fair lattice match with both
YBCO and Si, and the ability to grow it in thin-film form.
State-of-the-art T c ~92 K! and J c ~77 K! ~53106 A/cm2! have
been reported for YBCO films grown on YSZ,73 but the sub-
strate is not without its challenges. There have been numer-
ous reports of misoriented subgrains in generally epitaxial
layers, with well-defined misorientation angles.73 There are
also many reports of BaZrO3 at the film–substrate interface,
indicating chemical reactions, although they seem to be con-
fined to the near-interface region.73 A recent report demon-
strates that the in-plane orientation of YBCO films on YSZ
substrates depends strongly on the deposition conditions.14
On smooth substrates ~i.e., no intentional miscut!, the epitax-
ial orientation is @110#YBCOi@110#YSZ. Surface steps can
be produced on such YSZ substrates by homoepitaxial
growth or by suitable annealing. Such surfaces give a differ-
ent epitaxial orientation: @110#YBCOi@100#YSZ. These films
have better superconducting properties than do those on
smooth surfaces.
The growth of highly oriented YBCO films on both rigid
and flexible randomly oriented polycrystalline YSZ sub-
strates has also been reported.74 c-axis perpendicular films
with mosaic spread of ;1° can be obtained. T c 589 K on
well-polished substrates. J c ~77 K!51.43103 A/cm2 on rigid
substrates. The T c of films deposited on flexible substrates
does not change on repeated bending, but the resistivity of FIG. 15. The K2NiF4 crystal structure, shown here as CaNdAlO4 .
the films increases, presumably due to the development of
microcracks. These findings are rather encouraging for appli-
cations requiring flexible substrates and/or current-carrying A number of oxides with the tetragonal K2NiF4 structure
ability in the HTS film. shown in Fig. 15 have been investigated as potential HTS
The quality of TBCCO films on YSZ substrates has gen- substrate materials. In general, they have dielectric properties
erally not been as high as that of films produced on other that are rather similar to those of the perovskite-based oxides
materials. The best results for the ~2212! phase yield T c 5106 and reasonable lattice matches with the HTS materials. One
K and J c ~77 K!51.73104 A/cm2.75 Interestingly, TBCCO advantage that they pose compared with some of the near-
films grown on flexible polycrystalline substrates yielded the perovskite materials is the lack of twinning. One of these
same properties.76 YSZ has successfully supported the materials is CaNdAlO4 .45,79– 82 It has a dielectric constant
growth of the ~2223! phase of TBCCO, with a T c of 121 K.77 e519 and tan d5131024. Its lattice constants of a50.369
No J c data were reported. nm and c51.215 nm give a reasonable lattice match to the
CeO2 , with the same crystal structure ~inverse fluorite— HTS materials. The YBCO films were grown by pulsed laser
see Fig. 14! as that of YSZ has also received attention as a deposition, while the TBCCO films were grown by a two-
buffer layer, although not as a bulk substrate. The properties step process. Films on YBCO have been grown with T c as
of films are similar to those on YSZ. For example, use of a high as 88 K and J c ~77 K!51.03106 A/cm2.45 BSCCO films
double YSZ/CeO2 buffer layer on silicon on sapphire allows grown by sputtering have T c ;75 K.79 Films of TBCCO have
the growth of YBCO films with T c .90 K and J c ~77 T c 5100 K and J c ~77 K!53.53105 A/cm2.45 The chemical
K!.23106 A/cm2.78 The discovery of high-angle grain- reactivity of the substrate with HTS materials is the subject
boundary junctions with reproducible characteristics moti- of some debate. One report indicates that the interface of
vated the search for convenient ways to grow such bound- BSCCO films with CaNdAlO4 is sharper by Auger electron
aries reliably. The finding that different classes of substrate spectroscopy than that between BSCCO and LaGaO3 ,79,80
support different orientations of YBCO under the same while another indicates that the chemical instability of the
growth conditions19 offered such an opportunity. By starting material at high process temperatures will probably limit the
with a substrate of, say, MgO, it is possible to grow a buffer attractiveness of this material as an HTS substrate.45 Another
layer of another material such as SrTiO3 or CeO2 on part of problem with CaNdAlO4 is the sharp increase in microwave
the substrate. The different orientations of the YBCO on the loss at temperatures below 100 K.83 This is explained by
buffered and unbuffered regions give a reproducible grain magnetic ordering of the Nd ions and limits the appeal of the
boundary at the edge of the buffered film. substrate for many HTS film applications.

1842 J. Appl. Phys., Vol. 79, No. 4, 15 February 1996 Appl. Phys. Rev.: Julia M. Phillips
K. The measurement of J c is difficult due to the conductivity
of the substrate.
Mg2TiO4 has been grown on MgO by solid-state reaction
and then investigated as a substrate for YBCO.90–93 It is a
cubic material with a50.844 nm. The coefficient of thermal
expansion is 1231026/K, matching quite well with the HTS
materials. The dielectric constant is 12; tan d has been mea-
sured to be 1531024.90 The highest T c reported to date is
86.5 K. No J c values are in the literature.
MgAl2O4 ~spinel! is a cubic material with lattice param-
eter a50.8083 nm. The dielectric constant at 9.1 GHz is 12.
YBCO films with T c 577 K have been grown on this sub-
strate by PLD.94 BaF2 process films grown by the same
group were considerably worse.
Y3Al5O12 @yttrium aluminum garnet ~YAG!# is also cu-
bic with a lattice parameter a51.2009 nm. The dielectric
constant at 9.1 GHz is 10. PLD-deposited films have T c 587
K.94 Gd3Ga5O12 @gallium gadolinium garnet, ~GGG!# has
FIG. 16. The crystal structure of LiNbO3 ~after Ref. 142!. also been shown to support YBCO films with T c 591 K.
These films have primarily the a-axis orientation.95
LiNbO3 , with the crystal structure shown in Fig. 16, has
CaYAlO4 is another potential substrate material with the been tested as a substrate for YBCO, but the results have
K2NiF4 structure.84 It has lattice parameters a5b50.3648 been rather inconsistent.96 –98 This is a hexagonal crystal,
nm and c51.189 nm. The dielectric constant is 20; with a50.5148 nm and c51.3868 nm. In two cases, films of
tan d5431025 at 77 K and 5 GHz. YBCO and TBCCO fair quality with the c axis perpendicular to the growth di-
~2212! films on this substrate have worse properties than rection were grown on unbuffered substrates with T c 588 K
those on CaNdAlO4 . In the case of YBCO T c ;86 K and and J c ~77 K!;23105 A/cm2.96,97 In this case, T c 590 K for
J c ~77 K!523105 A/cm2. For TBCCO films T c ;90 K and films more than 100 nm thick. The T c was degraded for
J c ~77 K!523105 A/cm2. As in the case of CaNdAlO4 , reac- thinner films, with T c 576 K for 50 nm layers. For the thick-
tions between the film and substrate were cited as being a est films studied ~600 nm!, J c ~77 K!523105 A/cm2 and
significant problem. J c ~4.2 K!583105 A/cm2. The room-temperature resistivity
LaSrAlO4 has a 3% lattice mismatch with YBCO, with of the films is quite high, 1 mV cm. The dependence of the
a5b50.3754 nm and c51.1263 nm.81,85,86 Its dielectric film properties on thickness is indicative of serious film–
properties are quoted as being ‘‘similar’’ to those of LaAlO3 , substrate interactions, which was substantiated by the work
while the coefficient of thermal expansion is less than that of
of another group.98 This report stated that the T c of the films
the perovskites. Films have been grown on the ~001! and
is seriously degraded if there is no buffer, being in the range
~111̄8̄! orientations. On ~001!, YBCO films have a high de-
50–70 K. YSZ is a good buffer in this case, raising T c to 89
gree of a-axis orientation and T c 580 K. On ~111̄8̄!, T c .90
K. No J c values were reported.
K, and J c ~77 K!52–33105 A/cm2.
MgLaAl11O19 is another hexagonal material with
LaSrGaO4 also has the K2NiF4 structure, with lattice pa-
a50.5583 nm and c52.1953 nm, giving a lattice mismatch
rameters a50.384 nm and c51.2676 nm. The coefficient of
thermal expansion is 1031026/K. The dielectric constant is with YBCO of less than 2%.99,100 The dielectric constant of
22; tan d has been measured to be 531025.87 Only YBCO 11 is lower than that of many candidate substrate materials.
films have been reported on this substrate. In the first report tan d seems to be rather high, measured as 731024 at 9.4
on this substrate, it was stated that a-axis YBCO films re- GHz. Films grown on the ~110! surface of this material by
sulted from PLD growth under the same conditions that give PLD have the c axis perpendicular to the growth direction
rise to c-axis-oriented films on other substrates.88 The sub- and T c 589.5 K.
strate supports high-quality films, with T c 591 K and J c ~77 Substrate materials with the gehlenite structure, such as
K!53.53106 A/cm2.87 BaLaGa3O7 and SrLaGa3O7 have received a limited amount
Sr2RuO4 is of interest because it exhibits metallic con- of attention.80,101 Both have tetragonal crystal structures,
ductivity in two dimensions, with rab 51024 V at 300 K.89 It with a50.815 nm and c50.5399 nm for BaLaGa3O7 and
is semiconducting in the third dimension. The other oxide a50.806 nm and c50.534 nm for SrLaGa3O7 . The dielectric
substrate materials discussed in this subsection are all insu- constants for both materials are rather promising, lying in the
lators or semiconductors. The metallic nature of the conduc- range of 9–13. Attempts to grow YBCO and BSCCO films
tivity, coupled with the potential chemical and structural on these substrates have been unsuccessful due to diffusion
compatibility of the material with HTS compounds, is a very of Ba and Ga into the film.
attractive combination of properties for some applications. Y2BaCuO5 has been investigated as a polycrystalline
Sr2RuO4 has a tetragonal crystal structure with a50.387 nm substrate for relatively thick films ~10 mm! deposited by rf
and c51.274 nm. YBCO films on this substrate have T c 586 sputtering and silk-screen printing.102,103 Needless to say, the

J. Appl. Phys., Vol. 79, No. 4, 15 February 1996 Appl. Phys. Rev.: Julia M. Phillips 1843
FIG. 17. Resistivity vs temperature for a 50 nm PLD-grown YBCO film on FIG. 18. Resistance vs temperature of a YBCO film on MgO/GaAs ~after
YSZ/Si ~after Ref. 12!. Ref. 113!.

films are not epitaxial. T c 588 K and J c ~77 K!513103 growth of c-axis-oriented YBCO films. The best T c that has
A/cm2. been obtained with this structure is 84 K. Use of CaF2 as a
Sr2Ca2Cu4Oy substrates have been investigated for buffer layer has not been very successful: T c 569 K.108
BSCCO films produced by a rather novel process.104 The There are no reports of TBCCO films on either buffered
polycrystalline ceramic substrates had a layer of Bi evapo- or unbuffered Si, but there have been several attempts to
rated on them, followed by an anneal, so that the HTS layer grow BSCCO layers.105,109 As with YBCO, the only success
was formed by reaction of the Bi with the substrate itself. has involved buffer layers. In the case of TiN/Ti/Ag buffers,
The ~2212! phase predominated. A T c of 78 K and J c ~70 K! a T c of 78 K was reported.105 For MgO buffer layers, T c 580
of 13103 A/cm2 were measured for 1-mm-thick films. K and J c ~77 K!513104 A/cm2.
Growth of HTS films on GaAs has proven to be even
more difficult than similar depositions on Si because of the
D. Semiconductors
lower temperatures tolerated by the compound semiconduc-
In spite of serious problems with chemical reactivity, Si tor. A number of buffer layers has been tried, mostly with
has received considerable attention as a substrate material limited success. Examples include CaF2 , AlGaO3 , indium tin
due to the tantalizing possibilities of integrating semiconduc- oxide, Al2O3 , YSZ, and a YSZ/Si3N4 double-buffer
tors with superconductors. Some of the potential applications layer.110–112 Of these, the Al2O3 buffer gave the best results,
of HTS films outlined in Sec. II D require intimate contact with T c 580 K and J c ~5 K!513106 A/cm2. Recent progress
between semiconducting and superconducting layers. One has included the growth of reasonable quality YBCO films
natural way of accomplishing this is to have the semiconduc- ~T c 587 K; J c ~77 K!51.53105 A/cm2! on GaAs using a
tor serve as the substrate. Si is by far the most common MgO buffer layer ~see Fig. 18!, possibly coupled with a
semiconductor in use today. It also offers a reasonable lattice BaTiO3 layer on top of that.113 It has been found that the
match with the HTS compounds. Unfortunately, the good MgO buffer layer may be nonuniform and rough unless the
points of Si as a substrate for HTS films stop there. The GaAs surface is passivated by Sb prior to the MgO
reactivity between Si and HTS materials is extremely severe. growth.114
In addition, the coefficients of thermal expansion are very
badly matched, being 3– 4 times less in Si than in the HTS
E. Metals
compounds. For these reasons, the results on YBCO films
grown on Si have been extremely disappointing. The T c of Attempts to grow high-quality HTS films on metallic
YBCO grown on bare Si is typically in the range of 50 K.105 substrates have been proceeding almost as long as HTS films
The best results on bare Si, reported to be T c 581.5 K and have been grown on any substrate. This interest has been
J c ~4.2 K!;104 A/cm2, have been achieved at growth tem- spurred by the desirability of metallic substrates as an alter-
peratures much lower than those required to obtain state-of- native current-carrying path, which is desirable for a number
the-art films, due to the reactivity of the substrate.106 Under of applications. The flexibility of thin metal substrates is also
these conditions, the films are granular and/or porous and attractive for many purposes. These applications usually re-
contain several atomic percent Si. quire thick films so that the techniques used for film deposi-
The best results that have been achieved to date for tion tend to be different from those used on nonmetallic sub-
YBCO films on Si have involved the use of YSZ as a buffer strates. Whereas physical vapor deposition techniques of
layer.12 In this case, as shown in Fig. 17, T c 586 – 88 K, and various sorts tend to be favored for growth on nonmetallic
J c ~77 K!52.23106 A/cm2. The best films are less than 50 substrates of HTS films that are perhaps a few hundred nm
nm thick, unrelaxed and under tensile strain, exhibiting a thick, various chemical and spray deposition techniques have
distorted unit cell. The thermal mismatch of Si and YBCO is been studied most extensively for films on metal substrates.
a serious problem that limits the ultimate YBCO thickness This by itself tends to result in a difference in the film quality
that can be grown without film cracking to about 50 nm. that has been reported, since physical deposition techniques
CeO2 has also been used as a buffer layer.107 It promotes the have been more highly developed to give optimized super-

1844 J. Appl. Phys., Vol. 79, No. 4, 15 February 1996 Appl. Phys. Rev.: Julia M. Phillips
FIG. 19. J c ~77 K! dependence on in-plane texturing for YBCO films on
~d! YSZ/Pt/Hastelloy and ~s! YSZ/Hastelloy ~after Ref. 123!. FIG. 20. The crystal structure of MgF2 ~after Ref. 142!.

conducting properties. Whether this will remain an obstacle K!;1–23104 A/cm2. Until recently, the best results, perhaps
to high-quality HTS films on metals remains to be seen. Un- for any metal substrate, involved the growth of a biaxially
fortunately, metallic substrates pose many other challenges textured YSZ layer obtained by a bias sputtering technique
as HTS substrates. First, the crystal structures of metals is on Hastelloy.123 YBCO films grown on this substrate had
very different from that of the HTS compounds, so that epi- T c 590 K and J c ~77 K!533105 A/cm2, as shown in Fig. 19.
taxy is not likely or even possible on most metal substrates. The rough morphology resulting from this protocol could be
Second, many metals react strongly with the HTS materials, largely eliminated by interposing a thin Pt layer between the
degrading the superconducting properties substantially. Fi- Hastelloy and YSZ. The superconducting properties of this
nally, the coefficient of thermal expansion of metals tends to more complex structure were not reported. Elemental nickel
be quite different from that of HTS films, giving problems has also been investigated as a HTS substrate.130–132 The
with film cracking, etc. Nevertheless, the growth of HTS results are quite similar to those for Hastelloy. Recently, a
films on metal substrates continues to be an active area of substantial improvement in the properties of YBCO films on
research that has met with some success. YSZ-buffered Hastelloy has been reported.133,134 The crystal-
Silver is one of the metals that has received the most lographic alignment of the YSZ buffer layer grown by ion-
attention as a HTS substrate115–119 because it does not react beam-assisted deposition in this work is dramatically im-
with HTS compounds in a detrimental way and, in fact, is proved over previous results, which is likely a significant
used to improve the transport properties of bulk HTS mate- contributor to the improved superconducting properties.
rial. MOCVD-deposited YBCO films on Ag substrates have YBCO films as thick as 1 mm have been grown with J c ~77
T c .85 K,117 and J c ~77 K!;1.53104 A/cm2. BSCCO films K! of 13106 A/cm2. The films, which were grown on 130-
with mixed phases have been deposited on both YSZ buff- mm-thick Hastelloy, can undergo considerable and repeated
ered and unbuffered Ag.118 The T c of the films is 80 K in bending without loss of superconducting quality.
both cases. The J c of films on the unbuffered substrate is
3.93105 A/cm2 at 5.5 K.120
Gold has not been used as successfully as a HTS sub-
F. Other materials
strate because it has a more detrimental effect on the super-
conducting properties of the film. There is, however, a report Of the substrate materials that have been considered for
of its use as a substrate for TBCCO ~2212! films grown by HTS films that do not fall into one of the categories already
MOCVD.121 The film is highly textured with the crystallite c discussed, the alkaline earth fluorides, MgF2 , CaF2 , SrF2 ,
axes oriented perpendicular to the substrate surface. The and BaF2 , have probably received the most attention.135–138
magnetically derived T c is about 80 K. No J c data were MgF2 has the crystal structure shown in Fig. 20. CaF2 , SrF2 ,
reported. and BaF2 have the cubic fluorite structure shown in Fig. 14.
Copper also tends to react with HTS materials unless a They are attractive because of their reasonable dielectric
buffer layer is used.122 In this report, the Cu substrate was properties @e in the range of 6 –7 ~Ref. 139!# and coefficients
first coated with a layer of Ti, followed with a layer of MgO. of thermal expansion that rather closely match those of the
The highest T c of YBCO films deposited by sputtering on HTS materials ~between 931026/K for MgF2 and
such substrates was 85.9 K, with a J c ~77 K! of 1.53104 1831026/K for CaF2!.135,139 The investigations have been
A/cm2. confined to YBCO. The quality of films grown directly on
Hastelloy ~Ni–Cr–Mo alloy! has been studied exten- fluoride substrates depends strongly on which fluoride is be-
sively as a potential HTS substrate.120,123–129 A buffer layer is ing considered. CaF2 is reported as being the worst substrate
essential to prevent harmful film–substrate reactions. The in this family, reacting strongly with the films and yielding
buffer layers that have been studied include YSZ,120,123,125,128 insulating layers under all conditions studied. The reports on
Pt,123 SrTiO3 ,124 TiN,127 and BaTiO3 .126,129 SrTiO3 was re- MgF2 as a substrate vary substantially, ranging from reports
ported to give poor results. Most of the other buffer layers of extensive reaction at elevated temperature, weak film ori-
gave T c for YBCO between 80 and 85 K and J c ~77 entation, and no T c ,136,137 to giving the best result of all

J. Appl. Phys., Vol. 79, No. 4, 15 February 1996 Appl. Phys. Rev.: Julia M. Phillips 1845
field, and it is likely that much better substrate materials will
be available in the relatively near future than can be obtained
today.

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