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Type-I superconductor
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The interior of a bulk superconductor cannot be penetrated by a weak magnetic field, a phenomenon known as the Meissner effect. When the applied magnetic field becomes too large, superconductivity breaks down. Superconductors can be divided into two types according to how this breakdown occurs. In type-I superconductors, superconductivity is abruptly destroyed via a first order phase transition when the strength of the applied field rises above a critical value Hc. This type of superconductivity is normally exhibited by pure metals, e.g. aluminium, lead, and mercury. Examples of intermetallics exhibiting type-I superconductivity include tantalum silicide (TaSi2) [1], BeAu [2], and β-IrSn4.[3] The covalent superconductor SiC:B, silicon carbide heavily doped with boron, is also type-I.[4]
Depending on the demagnetization factor, one may obtain an intermediate state. This state, first described by Lev Landau, is a phase separation into macroscopic non-superconducting and superconducting domains forming a Husimi Q representation.[5]
This behavior is different from type-II superconductors which exhibit two critical magnetic fields. The first, lower critical field occurs when magnetic flux vortices penetrate the material but the material remains superconducting outside of these microscopic vortices. When the vortex density becomes too large, the entire material becomes non-superconducting; this corresponds to the second, higher critical field.
The ratio of the London penetration depth λ to the superconducting coherence length ξ determines whether a superconductor is type-I or type-II. Type-I superconductors are those with , and type-II superconductors are those with .[6]
References
[edit]- ^ U. Gottlieb; J. C. Lasjaunias; J. L. Tholence; O. Laborde; O. Thomas; R. Madar (1992). "Superconductivity in TaSi2 single crystals". Phys. Rev. B. 45 (9): 4803–4806. Bibcode:1992PhRvB..45.4803G. doi:10.1103/physrevb.45.4803. PMID 10002118.
- ^ Beare, J.; Nugent, M.; Wilson, M. N.; Cai, Y.; Munsie, T. J. S.; Amon, A.; Leithe-Jasper, A.; Gong, Z.; Guo, S. L.; Guguchia, Z.; Grin, Y.; Uemura, Y. J.; Svanidze, E.; Luke, G. M. (2019). "μSR and magnetometry study of the type-I superconductor BeAu". Physical Review B. 99 (13) 134510. arXiv:1902.00073. Bibcode:2019PhRvB..99m4510B. doi:10.1103/PhysRevB.99.134510.
- ^ Ahmad, Nazir; Shimada, Shunsuke; Hasegawa, Takumi; Suzuki, Hiroto; Afzal, Md Asif; Nakamura, Naoki; Higashinaka, Ryuji; Matsuda, Tatsuma D.; Aoki, Yuji (2024-04-15). "Linear Magnetoresistance and Type-I Superconductivity in 𝛽-IrSn4". Journal of the Physical Society of Japan. 93 (4). arXiv:2409.20221. doi:10.7566/JPSJ.93.044706. ISSN 0031-9015.
- ^ Kriener, M; Muranaka, T; Kato, J; Ren, Z. A.; Akimitsu, J; Maeno, Y (2008). "Superconductivity in heavily boron-doped silicon carbide". Sci. Technol. Adv. Mater. 9 (4) 044205. arXiv:0810.0056. Bibcode:2008STAdM...9d4205K. doi:10.1088/1468-6996/9/4/044205. PMC 5099636. PMID 27878022.
- ^ Landau, L.D. (1984). Electrodynamics of Continuous Media. Vol. 8. Butterworth-Heinemann. ISBN 0-7506-2634-8.
- ^ Tinkham, M. (1996). Introduction to Superconductivity, Second Edition. New York, NY: McGraw-Hill. ISBN 0-486-43503-2.
Type-I superconductor
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Definition
Type-I superconductors are materials that exhibit the phenomenon of superconductivity, characterized by zero electrical resistance to direct current and perfect diamagnetism, when cooled below a critical temperature .[2] In these materials, the superconducting state is abruptly terminated above a single critical magnetic field , resulting in a first-order phase transition to the normal conducting state.[6][7] This behavior contrasts with Type-II superconductors, which feature two distinct critical fields and allow partial magnetic field penetration. Typical examples of Type-I superconductors include pure elemental metals such as mercury, with K, and lead, with K.[4] These materials demonstrate the core prerequisites of superconductivity—dissipationless current flow and complete expulsion of magnetic fields—without the intermediate mixed states observed in other superconductor types.[6]Classification in Superconductivity
Superconductors are categorized into Type-I and Type-II based on their response to applied magnetic fields, a distinction rooted in phenomenological theories of the mid-20th century. Type-I superconductors display a single critical magnetic field , below which they maintain the complete Meissner effect by fully expelling magnetic flux from their interior, and above which superconductivity terminates abruptly in a first-order phase transition to the normal state.[8] This behavior ensures perfect diamagnetism up to , without intermediate states of partial flux penetration.[3] In contrast, Type-II superconductors feature two critical fields, a lower one and an upper one , with a vortex lattice forming in the mixed state between them, permitting quantized flux lines to penetrate while preserving zero electrical resistance.[8] The classification hinges on the Ginzburg-Landau parameter , where is the London penetration depth and is the coherence length; Type-I superconductors correspond to , leading to positive superconducting-normal interface energy and the observed sharp transition.[8] The framework emerged from the 1950 Ginzburg-Landau theory, which provided a macroscopic description of superconductivity near the critical temperature, enabling the prediction of distinct magnetic behaviors.[8] Alexei Abrikosov built upon this in 1957 by theoretically describing Type-II superconductors for larger , initially overlooked but validated experimentally in the 1960s through observations of flux quantization and vortex structures, thus establishing the dual classification by the early 1960s.[8] Material properties significantly determine whether a superconductor is Type-I or Type-II, primarily through their impact on . High purity reduces electron scattering, lengthening and typically yielding smaller values that favor Type-I behavior, as seen in simple elemental metals with clean atomic structures.[9] Conversely, impurities, alloying, or complex crystal structures shorten relative to , increasing and promoting Type-II characteristics.History
Discovery
The phenomenon of superconductivity was first observed on April 8, 1911, by Dutch physicist Heike Kamerlingh Onnes and his team at the University of Leiden in the Netherlands. While investigating the electrical properties of mercury at extremely low temperatures using recently liquefied helium—cooled to about 4.2 K—they noted that the resistance of a solid mercury wire dropped abruptly to zero just below this critical temperature, marking the complete disappearance of electrical resistance.[10][11][12] Building on this breakthrough, Onnes's group extended their experiments to other elements in the following years, confirming superconductivity as a reproducible effect beyond mercury. In 1913, they reported zero resistance in lead at approximately 7.2 K and in tin at around 3.7 K, both achieved through immersion in liquid helium baths that enabled precise temperature control near absolute zero.[13] These findings established superconductivity as an intrinsic property of certain pure metals at low temperatures, with early observations limited to simple elemental samples. At the time, there was no distinction between types of superconductors; the effect was regarded as a uniform characteristic of these materials, without recognition of varying magnetic behaviors. The classification into Type-I and Type-II superconductors emerged only later, in the 1930s, following observations of anomalous intermediate magnetic states in alloys like lead-bismuth, which deviated from the complete flux expulsion seen in pure elements such as mercury, lead, and tin.[14]Early Theoretical Advances
The discovery of the Meissner-Ochsenfeld effect in 1933 marked a pivotal advancement in understanding superconductivity, revealing that Type-I superconductors expel magnetic fields from their interior upon transitioning to the superconducting state, thereby exhibiting perfect diamagnetism. This phenomenon, observed in experiments with lead and tin samples cooled below their critical temperatures in the presence of applied magnetic fields, distinguished superconductivity from mere perfect conductivity and necessitated a theoretical framework accounting for electromagnetic rigidity.[15] In response to this observation, Fritz and Heinz London developed the first phenomenological theory of superconductivity in 1935, introducing the London equations to describe the electromagnetic response of superconductors. The first London equation relates the curl of the supercurrent density to the magnetic field : where is the density of superconducting electrons, and are the electron charge and mass, respectively; this implies that magnetic fields penetrate only to a characteristic depth, known as the London penetration depth. The second equation addresses the time evolution, stating that the time derivative of the current is proportional to the electric field: These equations successfully explained the Meissner effect by predicting the expulsion of magnetic flux and the persistence of supercurrents without dissipation, laying the groundwork for macroscopic descriptions of Type-I superconductors.[16] Building on these foundations, Vitaly Ginzburg and Lev Landau proposed an extension of the phenomenological approach in 1950, valid near the critical temperature , by introducing a complex order parameter to represent the superconducting wave function. Their theory formulated the Gibbs free energy density as a functional expansion: where and are temperature-dependent coefficients, is the effective mass, is the reduced Planck's constant, and is the vector potential; minimization of this functional yields coupled equations for and , enabling predictions of spatial variations in the superconducting state, such as in thin films or near interfaces. This framework generalized the London theory while remaining applicable to Type-I materials, providing deeper insights into thermodynamic properties without relying on microscopic details.[17]Physical Properties
Electrical Characteristics
Type-I superconductors exhibit zero direct current (DC) electrical resistance below their critical temperature , a defining property first observed in elemental materials like mercury and lead. This vanishing resistivity allows for the flow of persistent currents in closed loops without any energy dissipation, as the Cooper pairs of electrons move coherently without scattering. Such currents have been experimentally sustained for periods exceeding a year, with theoretical estimates suggesting decay times on the order of 100,000 years or more in ideal conditions.[18] For alternating current (AC) responses, Type-I superconductors display a frequency-dependent penetration depth , which governs how electromagnetic fields interact with the material's surface. At low frequencies near DC, the response approximates perfect diamagnetism with minimal penetration, but as frequency increases, the effective skin depth becomes relevant, incorporating both superconducting and normal fluid components. This leads to a complex surface impedance , where a non-zero surface resistance arises from interactions of the AC electric field with normal electrons within the penetration depth, causing energy dissipation. The penetration depth can be approximated as for temperatures well below , with on the order of 50 nm in materials like aluminum, highlighting the material's sensitivity to RF fields in practical devices.[19] The critical current density in Type-I superconductors represents the maximum supercurrent density sustainable before transitioning to the normal state, and it is characteristically low compared to Type-II counterparts due to the presence of a single critical magnetic field . According to Silsbee's rule, superconductivity breaks down when the self-generated magnetic field from the current reaches , limiting to values typically around to A/cm² in elemental Type-I materials like lead or tin at low temperatures. This constraint stems from the material's small and , making high-current applications challenging without exceeding the thermodynamic limit.[20]Magnetic Behavior
Type-I superconductors exhibit a complete Meissner effect, characterized by the total expulsion of magnetic fields from their interior when cooled below the critical temperature in the presence of an external magnetic field. This results in the magnetic induction throughout the bulk of the material for applied fields , where is the thermodynamic critical field.[21] The expelled field lines compress around the exterior of the sample, effectively shielding the interior and demonstrating the material's response as an ideal diamagnet.[16] The critical field defines the boundary beyond which the superconducting state abruptly transitions to the normal state. In Type-I superconductors, this transition occurs sharply at , with the temperature dependence approximately given by the parabolic relation . For fields exceeding , the Meissner state is destroyed, and magnetic flux fully penetrates the material, restoring normal conductivity.[21] This diamagnetic behavior arises from screening currents induced at the surface of the superconductor, which generate an opposing magnetic field to precisely cancel the applied field inside the bulk. These persistent surface currents, confined to a thin layer known as the London penetration depth, maintain in the interior and lead to perfect diamagnetism, quantified by the magnetic susceptibility .[16] The expulsion and screening mechanism underscores the equilibrium nature of the superconducting state in Type-I materials under moderate magnetic fields.[21]Theoretical Framework
Phenomenological Theories
Phenomenological theories provide macroscopic descriptions of the behavior of Type-I superconductors, capturing key electromagnetic and thermodynamic properties through empirical relations without invoking microscopic electron dynamics. These models emerged in the 1930s and 1950s to explain observations such as perfect diamagnetism and the temperature dependence of superconducting properties, laying the groundwork for understanding the distinction between Type-I and Type-II superconductors. The London theory, formulated by brothers Fritz and Heinz London in 1935, posits that superconductors expel magnetic fields (the Meissner effect) and support persistent currents that screen applied fields. The second London equation, , where is the supercurrent density, is the density of superconducting electrons, and are the electron charge and mass, and is the magnetic field, leads to exponential decay of the field inside the superconductor. Combining this with Maxwell's equations yields the London penetration depth, , characterizing the distance over which the magnetic field penetrates from the surface. For a semi-infinite superconductor with an applied field parallel to the surface, the field profile is , where is the distance into the material, illustrating the complete expulsion of flux in the bulk for Type-I materials at low temperatures. This theory successfully predicts the scale of field exclusion but assumes a temperature-independent , limiting its applicability near the critical temperature . To address temperature variations, the two-fluid model, proposed by Cornelis J. Gorter and Hendrik B. G. Casimir in 1934, conceptualizes the superconductor as a mixture of normal and superconducting fluid components, with the latter carrying dissipationless current. The total electron density , where is the normal fluid density, and the superfluid fraction governs transport properties, such as the fraction of electrons participating in superconductivity. Gorter and Casimir empirically derived , which aligns with experimental heat capacity and penetration depth data across a range of temperatures, providing a simple way to interpolate between the fully superconducting state at and the normal state at . This model complements the London equations by introducing thermal dependence, enabling predictions of properties like the critical field for Type-I superconductors. Building on these foundations, the Ginzburg-Landau (GL) theory, developed by Vitaly L. Ginzburg and Lev D. Landau in 1950, offers a thermodynamic framework valid near by treating superconductivity as a phase transition described by a complex order parameter representing the superconducting wavefunction. The GL free energy functional includes terms like , where , , is the effective mass, and is the vector potential, leading to the GL equations that generalize the London theory. From these, the coherence length emerges as , quantifying the spatial scale over which varies, such as at interfaces or vortices. The GL parameter distinguishes superconductor types: for Type-I, , resulting in a single first-order transition to the normal state under magnetic fields, with complete flux exclusion and no stable vortices. This criterion, derived thermodynamically, explains why pure elements like lead and mercury exhibit Type-I behavior, as their low values prevent partial penetration.Microscopic Explanations
The microscopic theory of Type-I superconductivity is provided by the Bardeen-Cooper-Schrieffer (BCS) theory, developed in 1957, which describes the quantum mechanical pairing of electrons into Cooper pairs through an attractive interaction mediated by lattice vibrations, or phonons. In conventional metals, the screened Coulomb repulsion between electrons is overcome by this phonon-induced attraction for electrons with opposite spins and momenta near the Fermi surface, forming bound Cooper pairs with a characteristic size much larger than the interatomic spacing. The binding energy of these pairs at zero temperature is given by , where is the superconducting energy gap, and in the weak-coupling limit of BCS theory, this satisfies , with the critical temperature and Boltzmann's constant. The superconducting energy gap varies with temperature and is determined self-consistently through the BCS gap equation, which in the standard weak-coupling approximation takes the form where is the effective pairing potential (attractive for energies within the Debye cutoff ), is the Fermi-Dirac distribution, and is the quasiparticle excitation energy with the normal-state kinetic energy relative to the chemical potential . At finite temperature, the equation is solved iteratively, yielding that decreases monotonically from and vanishes continuously at , marking the transition to the normal state where pairing is destroyed by thermal excitations. Near , , consistent with mean-field behavior. For Type-I superconductors, such as clean elemental metals like aluminum and lead, BCS theory predicts uniform Cooper pairing across the material without intermediate mixed states, as the pairing interaction supports a single, coherent superconducting order parameter throughout the sample. This uniformity explains the observation of a single thermodynamic critical field , beyond which superconductivity is abruptly destroyed, and the complete Meissner effect, wherein applied magnetic fields are fully expelled from the interior to maintain the paired state. In the clean limit, where impurity scattering is negligible, the BCS coherence length (with the Fermi velocity) is large due to weak pairing strengths and low , while the penetration depth remains finite, yielding a Ginzburg-Landau parameter that precludes vortex formation and enforces the ideal Type-I response. These length scales, and , derive directly from the microscopic BCS parameters in the clean-metal regime.Materials and Examples
Elemental Type-I Superconductors
Type-I superconductivity is exhibited by several pure elemental metals, primarily simple metals from the p-block and s-block of the periodic table, which display complete expulsion of magnetic fields below a single critical field Hc and transition temperatures typically below 10 K. These materials were among the first superconductors discovered and remain paradigmatic examples of type-I behavior due to their low Ginzburg-Landau parameter κ < 1/√2 ≈ 0.707 near Tc, leading to no mixed state and abrupt transition to the normal state at Hc. Representative elements include mercury, lead, tin, and aluminum, where high-purity samples are essential to observe pure type-I characteristics without intermediate states. Niobium, with the highest Tc among elements (9.5 K), is type-I in high-purity clean-limit form (κ ≈ 0.74), but typically exhibits type-II superconductivity in practical samples due to impurities and disorder that increase κ and enable vortex formation.[22] The superconducting properties of these elements are summarized in the following table, showing critical temperature Tc, zero-temperature critical field Hc(0), and Ginzburg-Landau parameter κ (near Tc unless noted). Values are for high-purity bulk samples under standard conditions, with κ calculated from measured coherence length ξ and penetration depth λ via κ = λ/ξ. These parameters highlight the scale of superconductivity in simple metals with low electron density of states at the Fermi level, where electron-phonon coupling is weak but sufficient for pairing at low temperatures. Note that for borderline cases like lead and mercury, calculated κ slightly exceeds 0.707 at low T, but bulk behavior remains type-I due to limitations of GL theory at low Tc.[23]| Element | Tc (K) | Hc(0) (T) | κ |
|---|---|---|---|
| Mercury (Hg) | 4.15 | 0.041 | 0.42 (near Tc); 0.91 (0 K) |
| Lead (Pb) | 7.19 | 0.080 | 0.49 (near Tc); 0.76 (0 K) |
| Tin (Sn) | 3.72 | 0.031 | 0.11 |
| Aluminum (Al) | 1.14 | 0.0105 | 0.17 |
| Niobium (Nb) | 9.50 | 0.198 | 0.74 |