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TABLE I. Sample preparation conditions and crystal compositions derived from the ICP analysis for Bi2212 single crystals. The ICP
analysis on the third sample in the table was done on cleaved, single-phase samples from an ingot containing a small amount of SrCuO2
secondary phase.
Annealing condition
Nominal composition ICP results Bi:Sr ratio Growth atmosphere UD OP OD
Bi2⫹x Sr2⫺x CaCu2 O8⫹ ␦ crystals with varying values of x growth speed of 0.3–0.4 mm/h for Bi2201 and 0.15–0.2
were grown in order to evaluate the effect of Bi:Sr nonsto- mm/h for Bi2212. The growth atmospheres adopted for the
ichiometry. In addition, we also have grown Bi2212 growth are listed in Table I. Bi2201 single crystals
Bi2 Sr2 Ca1⫺y Yy Cu2 O8⫹ ␦ , and found that substitution of Y were grown in 1 atm of flowing O2 .
for Ca site helps to enforce Bi:Sr stoichiometry and to raise The growth condition for the x⫽0 Bi2212 sample was
T c to 96 K for y⫽0.08. more stringent than for the other samples. In order to obtain
Our results demonstrate that the cation disorder, in par- homogeneous polycrystalline feed rods, a mixture of starting
ticular that located at the Sr site, significantly affects the powders with the stoichiometric ratio Bi:Sr:Ca:Cu
maximum attainable T c (T c,max) in the Bi-based supercon- ⫽2:2:1:2 was calcinated in stages, at temperatures increas-
ductors. In order to explain our results we use a conceptual ing from 770 °C to 870 °C in 10 °C increments, with inter-
hierarchy that classifies and ranks the principal kinds of mediate grindings. The final calcination temperature
chemical disorder possible in these systems. We then extend (870 °C) was set to be just below the composition’s melting
our arguments to other cuprates to examine whether a gen- temperature (875 °C). The duration of each calcination was
eral trend exists in the hole-doped high-T c superconductors. about 20 h. To avoid possible compositional fluctuation in
This paper is organized as follows: Section II contains the feed rod, instead of premelting, the feed rod was sintered
detailed information about sample preparation and character- four times in the floating-zone furnace at a speed of 50
ization. The experimental results are presented in Sec. III and mm/h. This process allowed us to obtain dense feed rods,
discussed in Sec. IV, while the effects of disorder in other ⬇95% of the ideal density. The atmosphere required for
cuprates are addressed in Sec. V. stable crystal growth was (7⫾3)% O2 , a range much nar-
rower than for nonstoichiometric or Y-doped Bi2212. The
II. SAMPLE PREPARATION grown crystal rod contained small amounts of a single-
crystalline SrCuO2 secondary phase, indicating that the
Single crystals of Bi2201 and Bi2212 were grown using sample still suffers from Bi:Sr nonstoichiometry. Single-
the traveling-solvent floating-zone technique, which is now phase Bi2212 single crystals could be cleaved from the
the preferred method for synthesizing high-purity single grown rod. No traces of impurity phases were found in other
crystals of many transition-metal oxides. This technique al- compositions.
lows for greater control of the growth conditions than is pos- Inductively coupled plasma 共ICP兲 spectroscopy was car-
sible either by standard solid-state reactions or by the flux ried out to determine the chemical compositions of the crys-
method. tals. Additional electron-probe microanalysis was also car-
Powders of Bi2 O3 , SrCO3 , CaCO3 , Ln2 O3 (Ln⫽La, Pr, ried out on the Bi2201 crystals. The results confirm that the
Nd, Sm, Eu, Gd, Y兲, and CuO 共all of 99.99% or higher actual compositions follow the nominal compositions, as
purity兲 were well dried and mixed in the desired cation ratio listed in Table I for Bi2212. Hereafter, we basically denote
(Bi:Sr:Ln:Cu⫽2:2⫺x:x:1 for Bi2201 and Bi:Sr:Ca:Cu⫽2 the samples by nominal composition to avoid confusion. In
⫹x:2⫺x:1:2 for Bi2212兲, and then repeatedly calcinated at order to determine the maximum T c for each cation compo-
about 800 °C with intermediate grinding. Eventually, the sition 共i.e., to achieve optimal hole concentration兲, the
powder was finely ground and formed into a 100 mm long Bi2212 samples were annealed at various temperatures and
rod with a diameter of 5 mm. The crystal growth was per- oxygen partial pressures using a tube furnace equipped with
formed using a Crystal Systems Inc. infrared radiation fur- an oxygen monitor and a sample transfer arm, which allowed
nace equipped with four 150 W halogen lamps. Except for us to rapidly quench the annealed samples from high tem-
nearly stoichiometric (x⫽0) Bi2212, the rods were pre- peratures within a closed environment. This procedure en-
melted at 18 mm/h to form dense feed rods. The crystal sures that the variation of T c among the samples is primarily
growth was carried out without the use of a solvent and at a due to cation nonstoichiometry and not due to differing hole
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H. EISAKI et al. PHYSICAL REVIEW B 69, 064512 共2004兲
IV. DISCUSSION
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FIG. 3. 共Color兲 Classification of bulk high-T c cuprates in terms of the disorder site and the number of CuO2 layers. Materials belonging
to the same family are indicated by the same color. Halogen family denotes (Ca, Sr) 2 CuO2 A2 (A⫽Cl, F兲 based materials. Bi family denotes
Bi22 (n⫺1)n(n⫽1,2,3). Pb family denotes Pb2 Sr2 Can⫺1 Cun⫹1 Oz . 1L Tl family denotes one-Tl-layer cuprates, TlBa2 Can⫺1 Cun O3⫹2n⫹ ␦ .
2L Tl family denotes two-Tl-layer cuprates, Tl2 Ba2 Can⫺1 Cun O4⫹2n⫹ ␦ . La family denotes La2 Can⫺1 Cun O2⫹2n . YBCO family denotes
LnBa2 Cu3 O6⫹ ␦ . Hg family denotes HgBa2 Can⫺1 Cun O2⫹2n⫹ ␦ . The transition temperatures are compiled from works listed in Ref. 21.
length scale observed in the STM/STS studies. V. DISORDER EFFECTS IN THE CUPRATES
Recent 89Y NMR experiments on yttrium barium copper
The two main lessons to be learned from our Bi2201 and
oxide 共YBCO兲 indicate that the spatial inhomogeniety in this Bi2212 case studies are that 共1兲 chemical inhomogeneity af-
system is much less severe than in LSCO or Bi2212.5 This is fects T c,max and that 共2兲 the effect of disorder differs depend-
reasonable since the latter two systems exhibit a much higher ing on its location. In the following, we attempt to classify
degree of disorder located at the A site 关La site 共LSCO兲 and the various sites at which chemical disorder is possible and
Sr site 共Bi2212兲兴, whereas YBCO 共Ba site兲 is thought to be categorize other superconducting families on the basis of
free from such cation disorder. Indeed, recent penetration which kind of disorder is prevalent in each system.
depth measurements on the YBCO variant In Fig. 3, we classify 25 cuprate superconductors based
Nd1⫹x Ba2⫺x Cu3 O7⫺ ␦ , with cationic disorder at the Ba site, on the pattern of the chemical disorder and the number of
demonstrate that the superconducting properties of this sys- CuO2 planes in the unit cell.21 In the first row, we illustrate
tem change quite sensitively with the degree of Nd/Ba three possible locations of chemical disorder relative to the
nonstoichiometry.20 CuO5 pyramids in multilayer materials, or to the CuO6 octa-
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H. EISAKI et al. PHYSICAL REVIEW B 69, 064512 共2004兲
hedra in single-layer materials. Pattern 共a兲 corresponds to the This trend is closely obeyed when one concentrates on the
Bi:Sr nonstoichiometry in Bi2201 and Bi2212, or Sr2⫹ ions variation within a single family of materials, each denoted by
doped into the La site in LSCO, referred to as A-site disorder a different color in the chart. For example, across the first
so far. The disorder is located next to the apical oxygen. row, oxygen-intercalated La2 CuO4⫹ ␦ located in 共c-1兲 has
Pattern 共b兲 corresponds to Y3⫹ substitution for Ca2⫹ in higher T c,max than Sr-substituted La2 CuO4 共a-1兲. Down the
Bi2212 and represents disorder located next to the CuO2 column, T c,max of the bilayer La-based system
plane, but at a position where there are no apical oxygen La2⫺x Srx CaCu2 O6 共a-2兲 is higher than that of its single-layer
atoms with which to bond. There is no corresponding 共b兲 site cousin. The classification suggests a negative correlation be-
in single-layer materials. Pattern 共c兲 disorder is further away tween the effective magnitude of chemical disorder and
from the CuO2 plane. We include excess oxygen ␦ in Bi- and T c,max . Additional remarks are made in Refs. 22–24.
Tl-based cuprates, oxygen defects in CuO chains in We note that one may also have to consider other factors
YBa2 Cu3 O7⫺ ␦ , and Hg deficiency y as well as excess oxy- which characterize the global material properties and are
gen ␦ in Hg1⫺y Ba2 Can⫺1 Cun O2n⫹2⫹ ␦ in this category. We likely to play a significant role as well in determining T c,max ,
note that the materials are cataloged based on the primary such as Madelung potential,26 bond valence sum,25 band
form of disorder that they are believed to exhibit. structure,27 block layer,28 multilayer,29 etc. Although the
As demonstrated in the present case study, the effect of present scheme is somewhat oversimplified and does not
the chemical disorder is expected to be stronger for pattern take account of these parameters, we believe it serves as a
共a兲 than for pattern 共b兲, which is reasonable considering the useful framework within which to consider the chemical dis-
role of the apical oxygen atom in passing on the effect of order effects prevalent in these materials, at least some of
disorder to nearby Cu atoms. First, the random Coulomb which, if ignored, have the potential to lead to the misinter-
potential caused by type 共a兲 disorder changes the energy lev- pretation of experimental data. Finally, similar to previous
els of the apical oxygen orbitals, which can be transmitted to work on Tl1223 共Ref. 15兲 and to the present work on
CuO2 planes through the hybridization between the apical Bi2212, it might be possible to raise T c,max of certain other
O(2p z ) orbital and the Cu(3d r 2 ⫺3z 2 ) orbital. Second, the cuprates by minimizing the effects of chemical disorder.
displacement of the apical oxygen caused by type 共a兲 disor-
der brings about a local lattice distortion to the CuO2 planes. VI. SUMMARY
The effect of pattern 共c兲 disorder is expected to be weakest
since the disorder is located relatively far away from the In summary, we present case studies of the effects of
CuO2 plane. chemical disorder on the superconducting transition tempera-
The number of CuO2 planes per unit cell may be regarded ture of the single-layer and double-layer Bi-based cuprate
as another parameter that, in effect, determines the magni- superconductors. We find that the superconducting transition
tude of the chemical disorder. As demonstrated in Bi2212, temperature of Bi2212 can be increased up to 96 K by low-
multilayer materials can accommodate heterovalent ions by ering the impact of Sr site disorder, the primary type of dis-
making use of type 共b兲 substitution whose effect on T c was order inherent to the bismuth family of materials, at the ex-
seen to be weaker than type 共a兲 substitution. Furthermore, the pense of Ca site disorder. Based on these experimental
space between the CuO2 planes forming a multilayer may results, we present a qualitative hierarchy of possible disor-
buffer the impact of the disorder. For instance, in single-layer der sites, and then proceed to categorize the hole-doped
materials, any displacement of the ‘‘upper’’ apical oxygen in high-temperature superconductors on that basis.
a CuO6 octahedron creates stress in the CuO2 plane because
ACKNOWLEDGMENTS
the motion of the octahedron is constrained by the ‘‘lower’’
apical oxygen. Double-layer materials contain CuO5 pyra- We thank G. Blumberg, J. Burgy, E. Dagotto, J. C. Davis,
mids rather than CuO6 octahedra, and the separation between D. S. Dessau, T. H. Geballe, E. W. Hudson, A. Iyo, A. Ka-
CuO2 planes relieves this stress, reducing the effects of type pitulnik, G. Kinoda, S. A. Kivelson, R. B. Laughlin, B. Y.
共a兲 disorder. This buffer zone between the outer CuO2 planes Moyzhes, D. J. Scalapino, T. Timusk, and J. M. Tranquada
is further increased in triple-layer materials, with the addi- for helpful discussions. This work was supported by the
tional benefit that the middle layer is somewhat ‘‘protected’’ NEDO grant ‘‘Nanoscale phenomena of self-organized elec-
from the direct effects of pattern 共a兲 关and 共c兲兴 disorder. trons in complex oxides-new frontiers in physics and de-
Cursory examination of Fig. 3 reveals that T c,max gener- vices,’’ by the U.S. DOE under Contract Nos. DE-FG03-
ally increases both across the rows and down the columns of 99ER45773 and DE-AC-03-76SF00515, by NSF Grants
the chart. Indeed, there is no material in 共a-1兲 which pos- Nos. DMR9985067, DMR0071897, ONR N00014-98-0195,
sesses a T c,max higher than 50 K. Furthermore, Bi2201 in and by the DOE’s Office of Basic Energy Science, Divisions
column 共a兲 has a lower T c,max than Tl2201 in column 共c兲, of Materials Sciences and Chemical Sciences, through the
despite their similar crystal structures. Similarly, T c,max of Stanford Synchrotron Radiation Laboratory 共SSRL兲. H.E.
TlBa1⫹x La1⫺x CuO5 共Tl1201兲 is lower than that of was supported by the Department of Applied Physics, Stan-
HgBa2 CuO4⫹ ␦ 共Hg1201兲. ford University.
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Eckstein, and H. Shaked, ibid. 397, 45 共1999兲; 共a-2兲
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Bi2⫹x Sr2⫺x CaCu2 O8⫹ ␦ , Ref. 9; 共b-2兲
the Y site 关T. Miyatake, S. Gotoh, N. Koshizuka, and S. Tanaka,
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work; 共c-2兲 YBa2 Cu3 O7⫺ ␦ , R. Liang, D.A. Bonn, and W.N. doped, and T c,max⫽93.7 K is found for ␦ ⬇0.07 共Ref. 21兲.
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TlBa2 Ca2 Cu3 O9⫹ ␦ , same as above; 共c-3兲 Tl2 Ba2 Ca2 Cu3 O10⫹ ␦ , radius mismatch, Ln and Ba ions usually do not mix with each
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26
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