Effect of Ba Substitution for Sr in the Pb-based 1212 Cuprate Containing Sulfur of (Pb<Subscript>0.75</Subscript>S<Subscript>0.25</Subscript>)Sr<Subscript>2</Subscript>(Y,Ca)Cu<Subscript>2</Subscript>O<Subscript><Emphasis Type="Italic">z</Emphasis></Subscript>

We already reported on the synthesis of new Pb-based 1212 layered cuprates containing sulfur in the (Pb_0.75S_0.25)Sr₂(Y,Ca)Cu₂O _z system. There none of the samples showed superconductivity until after annealing under high O₂ pressure. More recently, we have discovered that the samples could be substituted by Ba for Sr up to x=0.6 in the composition of (Pb_0.75S_0.25)(Sr_2−x Ba _x )(Y_0.4Ca_0.6) Cu₂O _z . Then if the Ba-substitution is performed for Sr, some of the almost-single phase samples are found to show resistivity drops and magnetic anomalies without annealing under high O₂ pressure. Among the samples, a sample with the nominal composition of (Pb_0.75S_0.25)(Sr_1.5Ba_0.5)(Y_0.4Ca_0.6) Cu₂O _z is found to show the highest onset temperatures of a resistivity drop at about 35 K and a magnetic anomaly at about 31.5 K. These are higher than the highest values for the superconducting Ba-free sample of (Pb_0.75S_0.25)Sr₂ (Y_0.4Ca_0.6)Cu₂O _z which was annealed under high O₂ pressure.     

Superconductivity in the Pb-based 1222 Cuprate Containing Boron, (Pb0.5B0.5) Sr2(Y1.9−x Ce x Sr0.1)Cu2O z

We previously reported on the discovery of new Pb-based 1222 cuprates containing boron in the (Pb_0.5B_0.5)Sr₂(RE_2−x−y Ce _x Sr _y )Cu₂O _z (RE = Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, and Y) systems. However, none of the cuprates was a superconductor, but a semiconductor with the conduction process of a three-dimensional variable range hopping at low temperatures, despite annealing under O₂ atmosphere at 100 atm and 400 °C. Recently, we have discovered that some samples showed superconductivity in the (Pb_0.5B_0.5)Sr₂(Y_1.9−x Ce _x Sr_0.1)Cu₂O _z system. Among them, the sample with x=0.45 shows the highest zero resistivity temperature at about 10 K and it shows a diamagnetic signal starting at abut 16 K with lowering temperature. The superconductivity is considered to originate from the 1222 phase.     

Synthesis of New Pb-Based 1232 Cuprate Containing Boron in?the?(Pb0.5B0.5) Sr2(Er3?x?yCexSry)Cu2Oz System

New Pb-based layered cuprates containing boron with the 1232 structure have been synthesized in the (Pb_0.5B_0.5)Sr₂(Er_3−x−y Ce _x Sr _y )Cu₂O _z system. Nearly the single 1232 phase samples are obtained for the nominal composition of 1.6≤x≤1.9 and y=0.2. A sample with the composition of (Pb_0.5B_0.5)Sr₂(Er_1.2Ce_1.6Sr_0.2)Cu₂O _z shows resistivity-dropping phenomenon below 10 K and it shows a diamagnetic signal at about 9.0 K, though the superconducting volume fraction is very small. From these results, the sample may well be a new Pb-based superconductor with the 1232 structure.     

Enhanced Superconductivity of the Pb-Based 1212 Cuprates in the (Pb0.75S0.25)(Sr2?xBax)(Y0.4Ca0.6)Cu2Oz System by High-Pressure O2 Annealing

We have already reported on substitution effects of Ba for Sr in the sulfur contained Pb-based 1212 compound with the composition of (Pb_0.75S_0.25)(Sr_2−x Ba _x ) (Y_0.4Ca_0.6)Cu₂O _z . It was found that each sample with x=0.3–0.6 showed a resistivity drop originating from superconductivity, and the highest onset temperature of the drop was about 32 K for a sample with x=0.5, but the volume fraction was very small. More recently, we have investigated effect of high-pressure O₂ annealing on superconductivity of the Ba-substituted samples with x=0.4–0.6. As a result, the sample with x=0.5 is found to show an onset of the resistivity drop at the highest temperature of about 41.7 K and it shows an onset of the diamagnetic signal at about 42.0 K. These transition temperatures are higher by ∼10 K than those of the previously reported sample with x=0.5. Moreover, the superconducting volume fraction is increasing more by the high-pressure O₂ annealing. These results indicate that the high-pressure O₂ annealing effectively promotes superconductivity of the present (Pb_0.75S_0.25)(Sr_2−x Ba _x )(Y_0.4Ca_0.6)Cu₂O _z system.     

Substitution Effect of Ba for Sr on Superconductivity in?the?(Pb0.75P0.25)(Sr2?xBax)(Y0.4Ca0.6)Cu2Oz System

The Pb-based 1212 compounds containing phosphorus were already discovered by us in the (Pb,P)Sr₂(Y,Ca)Cu₂O _z system. Among the almost-single phase samples, a sample with the nominal composition of (Pb_0.75P_0.25)Sr₂(Y_0.4Ca_0.6)Cu₂O _z was a superconductor with the highest T _c of 38 K in the system. Recently, we have been investigating on substitution effect of Ba for Sr on superconductivity in the (Pb_0.75P_0.25)(Sr_2−x Ba _x )(Y_0.4Ca_0.6)Cu₂O _z system. As a result, it is found that the almost–single 1212 phase samples are obtained in the composition area of 0.0≤x≤0.4. In this area, with increase of x, the lattice parameters a,c and the cell volume V are found to be gradually increasing. This finding can be considered to show that larger Ba²⁺ ions certainly occupied the Sr-sites in the sample. However, we obtain such interesting results as that the T _c value is not so enhanced by the substitution in comparison with that of the sample of x=0.0, and that the maximum value of T _c was 40 K for x=0.2 and 0.3 at the best.     

New Members of the Pb-based 1222 Superconductor Containing Phosphorus: (Pb0.75P0.25)Sr2(Ln1.9?x Ce x Sr0.1)Cu2O z (Ln=Sm and Gd)

We previously reported on the synthesis of new Pb-based 1222 superconductor containing phosphorus in the (Pb_0.75P_0.25)Sr₂(Eu_1.9−x Ce _x Sr_0.1)Cu₂O _z system. Recently, we have discovered new members of the Pb-based 1222 superconductor containing phosphorus in the (Pb_0.75P_0.25)Sr₂(Ln_1.9−x Ce _x Sr_0.1)Cu₂O _z (Ln=Sm and Gd) systems. In each system, it is found that the samples of almost the single 1222 phase can be obtained for a wide composition area of 0.3≤x≤1.0. After annealing under 143 atm O₂ atmosphere at 400 °C, each sample of Ln=Sm and Gd with x=0.3 is found to show an onset of resistivity-drop at about 28 K and at about 24 K, respectively. Moreover, each samples of Ln=Sm and Gd is found to show an onset of diamagnetic signal at about 25 K and about 22 K, respectively. From these facts, these samples of Ln=Sm and Gd are found to be new members of the Pb-based 1222 superconductor containing phosphorus.     

Studies on (Hg0.7Mo0.3)Sr2(Sr1?xLax)Cu2Oz with a Wide Range of Doping State

The single-phased series of Sr-bearing Hg-1212 superconducting cuprate,(Hg_0.7Mo_0.3)Sr₂(Sr_1–x La _x )Cu₂O _z has been prepared. X-ray diffraction showed that, the obtained samples belong to the 1212-structure with tetragonal space group P4/mmm, similar to that of (Hg, Mo)Sr₂(Ca, Y)Cu₂O_z, and stabilized in a wide compositional range of 0.25x0.75. Refinements of the structure are carried out in which the oxygen atoms at the (Hg, Mo) layer is shifted from high-symmetry position (0.5, 0.5, 0) to (x, x, 0). Magnetization and electrical resistivity measurements show that the as-prepared samples exhibit evidence for superconductivity and their superconducting properties were improved after O₂ annealing with T ^onset _c as high as 92 K.     

Synthesis of New Pb-Based 1222 Cuprates Containing Phosphorus, (Pb0.75P0.25)Sr2(RE2–x–y Ce x Sr y )Cu2O z (RE = Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, and Y)

New Pb-based 1222 cuprates containing phosphorus have been synthesized in the (Pb_0.75P_0.25)Sr₂- (RE_2–x–y Ce _x Sr _y )Cu₂O _z (RE = Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, and Y) systems. The almost-single phase samples are obtained for 0.5≤x≤1.0 and y=0.1 in the cases of RE = Nd, Dy, Ho, Er, Tm, Yb and Y, while for 0.3≤x≤1.0 and y=0.1 in the cases of RE = Sm, Eu and Gd. The samples crystallize in a tetragonal lattice, the lattice parameters a and c are decreasing with the decrease of the ionic radius of the RE element. Even after annealing under 143 atm O₂ atmosphere at 400 °C, almost all the samples with the common values x=0.5 and y=0.1 are semiconductors with a transport process followed by three-dimensional variable range hopping. However, the samples of RE = Sm, Eu and Gd, which are of almost single 1222 phase, even for x=0.3 and y=0.1, show superconductivity with the onsets at about 25 K, 20 K and 22 K, respectively. Through this study, we find very important procedure for discovery of new superconducting 1222 compound.     

Solution-sol-gel processing of superconductors

Bulk materials and thin films of pure and homogeneous YBa₂Cu₃O_7−x and Bi₂Sr₂CaCu₂O_8+x compounds were prepared by a nanocomposite solution-sol-gel (SSG) method. The superconducting oxides of YBa₂Cu₃O_7−x and Bi₂Sr₂CaCu₂O_8+x were prepared at very low temperatures i.e. 750°C and 850°C, respectively by SSG method. Pellets sintered from these nanophasic sol powders showed sharp resistivity drops atT _c ∼ 90°K for YBa₂Cu₃O_7−x andT _c∼67°K for Bi₂Sr₂CaCu₂O_8+x . Thin films were prepared using triphasic sol of Y, Ba, Cu and tetraphasic sol of Bi, Sr, Ca and Cu on MgO and SrTiO₃ substrates. The triphasic sol coated on SrTiO₃ substrates and calcined at 800°C for 12h showed the formation of superconducting phase, YBa₂Cu₃O_7−x with preferred orientation along theC-axis. X-ray diffraction patterns of the Bi₂Sr₂CaCu₂O_8+x films on MgO substrate showed the formation of the superconducting phase with preferential orientation along the C-axis and the microwave absorption data as a function of temperature of this film revealed the onset temperature to be 90°K.     

Studies on (Hg0.7Mo0.3)Sr2(Sr1−xLax)Cu2Oz with a Wide Range of Doping State

The single-phased series of Sr-bearing Hg-1212 superconducting cuprate,(Hg_0.7Mo_0.3)Sr₂(Sr_1?x La _x )Cu₂O _z has been prepared. X-ray diffraction showed that, the obtained samples belong to the 1212-structure with tetragonal space group P4/mmm, similar to that of (Hg, Mo)Sr₂(Ca, Y)Cu₂O_z, and stabilized in a wide compositional range of 0.25≤x≤0.75. Refinements of the structure are carried out in which the oxygen atoms at the (Hg, Mo) layer is shifted from high-symmetry position (0.5, 0.5, 0) to (x, x, 0). Magnetization and electrical resistivity measurements show that the as-prepared samples exhibit evidence for superconductivity and their superconducting properties were improved after O₂ annealing with T ^onset _c as high as 92 K.     

Superconducting transition temperatures in the Ru-1232 system, RuSr2(Gd1? x Ln x Ce1.8Sr0.2)Cu2O z (Ln = Sm, Dy, and Ho)

We have investigated effects of the lanthanide element Ln and the composition changes on the superconducting transition temperatureT _c in the Ru-1232 system, RuSr₂(Gd_1−x Ln _x Ce_1.8Sr_0.2)Cu₂O _z (Ln = Sm, Dy, and Ho). At first, in the case of the samples with Ln = Sm among almost the single 1232 phase samples, the values of the superconducting onset temperatureT _co are almost the same forx=0.00−0.15, and each of the lattice parametersa andc is almost constant. While, in each of the cases of the samples with Ln = Dy and Ho, the sample withx=0.05 shows the maximum values for both the superconducting onset temperatureT _co and the zero resistivity temperatureT _cz. Especially for the sample with Ln = Dy, the values ofT _co andT _cz are 18.5 and 6.5 K, respectively. These are higher than those of the mother sample of RuSr₂(GdCe_1.8Sr_0.2)Cu₂O _z . Moreover, from variations ofT _co, lattice parameters ofa andc in the RuSr₂(Gd_1−x Dy _x Ce_1.8Sr_0.2)Cu₂O _z system as a function of Dy contentx, the relationship between the superconducting transition temperature and the lattice parameters in the present system are investigated.     

Synthesis of New Pb-based 1222 Layered Cuprates in the (Pb,S)Sr2(RE,Ce)2Cu2O z (RE=Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, and Y) System

A new family of the Pb-based layered cuprate with the 1222 structure has been synthesized in the (Pb,S)Sr₂(RE,Ce)₂Cu₂O _z (RE=Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, and Y) system. The almost-single phase samples are obtained for x=0.25 and y=1.0 in the composition of (Pb_1?x S _x )Sr₂(RE_2?y Ce _y )Cu₂O _z . Each of the samples has the crystal structure with a tetragonal symmetry. Both of the lattice parameters a and c are decreasing with the decrease of the ionic radius of RE element. Among these samples, the sample with RE=Er has the smallest resistivity in the whole temperature range and the slope of the resistivity versus temperature is the most gentle. Despite annealing under O₂ atmosphere at high-pressure of 121 atm, this sample is a semiconductor with the transport process characteristics of three-dimensional variable range hopping conduction. Then the samples of RE=Er with smaller y are investigated for the composition of (Pb_0.75S_0.25)Sr₂(RE_2?y Ce _y )Cu₂O _z , the sample with y=0.4 is found to show an onset of resistivity drop phenomenon at about 11 K with the decrease of temperature. Moreover, we also discover that the samples of RE=Ho with y=0.4 show an onset of the resistivity dropping at over 20 K and zero resistivity at 13 K. From these results, the present (Pb_0.75S_0.25)Sr₂(RE_2?y Ce _y )Cu₂O _z system is considered to be a new family of the Pb-based superconducting cuprates with the 1222 structure.     

Enhancement of (Bi,Pb)-2223 HTS Formation by Boron-Doping

Influence of boron-doping on the superconducting properties of (Bi,Pb)-2223 HTS ceramics prepared in an alumina crucibles has been investigated. X-ray diffraction, resistivity, and AC susceptibility measurements were performed on the undoped and boron-doped compounds. Obtained results have shown that B₂O₃ addition in the Bi_1.7Pb_0.3Ca₂Sr₂Cu₃O _y precursor enhances the formation of high-T _c phase. The boron-doped samples with starting composition Bi_1.7Pb_0.3Ca₂Sr₂Cu₃B _x O _y (x=0.05 and 0.5) reveal significant improvement in the zero resistivity temperature compared to the undoped sample (from 72 K up to 100 K). Boron-doping level x=1.5 results in a substantial degradation of the (Bi,Pb)-2223 phase.     

New Pb-based Superconductor with the 1222 Structure in?the?(Pb0.75P0.25)Sr2(Eu1.9?xCexSr0.1)Cu2Oz System

New Pb-based 1222 cuprates containing phosphorus have been synthesized in the (Pb,P)Sr₂(Eu,Ce,Sr)₂ Cu₂O _z system. From X-ray powder diffraction study, almost the single 1222 phase samples are found to be obtained in a considerable wide composition area of 0.3≤x≤1.2 for the nominal composition of (Pb_0.75P_0.25)Sr₂(Eu_1.9−x Ce _x Sr_0.1) Cu₂O _z . The crystal structure for each sample has a tetragonal symmetry and the typical lattice parameters are a=0.3851 nm and c=2.922 nm. After annealing under 143 atm O₂ atmosphere at 400 °C, a sample with x=0.3 among the almost-single phase samples shows an onset of resistivity-drop at the highest temperature of about 22 K and zero-resistivity at the highest temperature of about 12 K, then this sample also shows an onset of diamagnetic signal at about 20 K. These phenomena are found to originate from superconductivity of the new 1222 phase.     

Superconducting Transition Temperatures in the Ru-1232 System, RuSr2(Gd1?xLnxCe1.8Sr0.2)Cu2Oz (Ln = Sm, Dy, and Ho)

We have investigated effects of the lanthanide element Ln and the composition changes on the superconducting transition temperature T _c in the Ru-1232 system, RuSr₂(Gd_{1− x} Ln _x Ce_1.8Sr_0.2)Cu₂O _z (Ln = Sm, Dy, and Ho). At first, in the case of the samples with Ln = Sm among almost the single 1232 phase samples, the values of the superconducting onset temperature T _co are almost the same for x = 0.00–0.15, and each of the lattice parameters a and c is almost constant. While, in each of the cases of the samples with Ln = Dy and Ho, the sample with x = 0.05 shows the maximum values for both the superconducting onset temperature T _co and the zero resistivity temperature T _cz. Especially for the sample with Ln = Dy, the values of T _co and T _cz are 18.5 and 6.5 K, respectively. These are higher than those of the mother sample of RuSr₂(GdCe_1.8Sr_0.2)Cu₂O _z . Moreover, from variations of T _co, lattice parameters of a and c in the RuSr₂(Gd_{1− x} Dy _x Ce_1.8Sr_0.2)Cu₂O _z system as a function of Dy content x, the relationship between the superconducting transition temperature and the lattice parameters in the present system are investigated.     

New Pb-based 1212 Cuprate Superconductors Containing Sulfur, (Pb0.75S0.25)Sr2 (Y1?xCax)Cu2Oz

New Pb-based 1212 layered cuprates containing sulfur have been synthesized in the (Pb_0.75S_0.25) Sr₂ (Y_1−x Ca _x ) Cu₂O _z system. X-ray diffraction analysis shows that the almost single-phase samples are obtained within a region of 0.0≤x≤0.5. The crystal structure of each sample has a tetragonal symmetry with the typical lattice constants a=0.3837 nm and c=1.186 nm. As Ca content x is increasing, the semiconductor-like behavior is suppressed. But after only annealing under ambient O₂ pressure, none of the samples show any trace of superconductivity. On the other hand, when the samples are annealed under high O₂ pressure of about 13.6 MPa, they show resistivity dropping phenomenon in a region of 0.5≤x≤0.7. Among them, the lowest resistivity sample with x=0.6 has an onset temperature of the resistivity dropping at about 22.5 K. Moreover, this sample shows a diamagnetic signal at about 21.5 K. These phenomena are attributed to superconductivity.     

New Pb-Based 1222 Cuprates, (Pb0.5B0.5)Sr2(RE2−x−y Ce x Sr y )Cu2O z (RE = Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, and Y)

New Pb-based layered cuprates with the 1222 structure have been synthesized in the (Pb_0.5B_0.5)Sr₂ (RE_2−x−y Ce _x Sr _y )Cu₂O _z (RE = Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, and Y) systems. The almost-single-phase samples in the systems can be obtained for a nominal composition of x=0.7 and y=0.1. The crystal structure of the samples has a tetragonal symmetry, the lattice parameters of a and c are increasing with increasing the ionic radius of RE element. Despite treatment under high O₂ pressure of 100 atm, the samples are semiconductors with the transport process characteristic of three-dimensional variable range hopping conduction.     

Superconductivity in nearly single-phase Bi-Pb-Sr-Ca-Cu-O samples with different nominal compositions

The preparation conditions, phase composition, and superconducting properties of Bi-Pb-Sr-Ca-Cu oxide materials from different nominal compositions have been investigated. Nearly single-phase samples from Bi₂Pb_0.4Sr₂Ca₃Cu₄O _y , as well as from the proposed compositions Bi_1.8Pb_0.4Sr₂Ca₃Cu₄O _y and Bi_1.8Pb_0.4Sr₂Ca_2.5Cu_3.5O _y were obtained by a solid-state reaction in air. Samples with the third nominal composition showed the best superconducting properties (T _on=111 K and zero resistance atT ₀=103 K). A possible mechanism for the 2223 phase formation in the three investigated compositions has been discussed.     

Effect of Ba Substitution on the Formation of (Tl,Bi)-1234 Superconducting Phase

(Tl_1−x Bi _x )(Sr_2−y Ba _y )Ca₃Cu₄O _z ((Tl,Bi)-1234) samples (x=0.1–0.3, y=0.4–1.5) were synthesized under ambient pressure by using a two-step solid-state reaction method to investigate the effect of Ba substitution on the formation and superconducting properties of the (Tl,Bi)-1234 phase. X-ray diffraction analysis shows that nearly single-phased samples are obtained for (Tl_0.8Bi_0.2)(Sr_2−y Ba _y )Ca₃Cu₄O _z (0.8≤y≤1.2), suggesting that control of the composition ratio of Sr and Ba in the bridging layer is a key to stabilizing the 1234-type structure. The critical temperature for the nearly single-phased samples remained between 106.9 K and 109.1 K and was not significantly affected by the change in the Ba content.     

Prediction ofT c for YBa2Cu3Oz doped with Ca using neural network

In order to predict the superconducting transition temperatureT _c of YBa₂Cu₃O_z doped with Ca, we have constructed a neural network NN which is composed of three layers; we considered 28 constituent elements and their concentration in the input layer to provideT _c in the output layer. The NN was trained by the error-back-propagation method using data from the database “SUPERCON” for high-T_c superconducting materials. The effect of Ca doping onT _c of (Y_1-x-Ca_x)Ba₂Cu₃O_z and Y(Ba_2-xCa_x)Cu₃O_z was investigated using this method. It turned out that a higherT _c is expected for the sample withx = 0.3 andz = 6.5 in the former system and that the oxygen concentrationz can be varied for different Ca contents in the latter system.